Soil Health Book

SOIL
FERTILITY
Henry D. Foth
Boyd G. Ellis
Professors of Soil Science
Michigan State University
WILEY
John Wiley & Sons
New Yor k Chi chest er Bri sbane To r o n t o Si ngapor e
Copyri ght 1988, by John Wi l ey & Sons, Inc.
All rights reserved. Publ i shed simultaneously in Canada.
Reproduct i on or translation of any part of
this work beyond that permi tted by Secti on
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Act wi thout the permission of the copyri ght
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or further i nformati on shoul d be addressed to
the Permissions Department, John Wiley & Sons.
Library of Congress Cataloging in Publication Data:
Foth, H. D.
Soil fertility.
Bibliography: p.
1. Soil fertility. 2. Fertilizers. 3. Soils
Fertilization movement . I. Ellis, Boyd G. II. Ti tl e.
S633. F67 1988 631. 4' 22 88- 17352
ISBN 0- 471- 82507- 7 (pbk.)
Pri nted i n the Uni t ed States of Ameri ca
1 0 9 8 7 6 5 4 3 2 1
This book is dedicated to Dr. R. L. Cooka pioneer in the development
of efficient methods of using fertilizers and the interactions between
fertilizers and tillage operationswith admiration and affection.
Preface
Thi s book has been wri t t en to serve as a t ext for a soil fertility cour se at t he
j u n i o r - s e n i o r level and at t he mast er ' s level for st udent s who have had an
i nt r oduct or y course i n soil science and several basic science courses. We
have chosen t o cover t he most essential topics and not pr oduce an all-inclu-
sive t ext t o serve as a r ef er ence book. T h e t r eat ment i s an evol ut i onar y one
whi ch consi ders soils as dynami c, ever - changi ng bodi es.
Th e r e has been maj or pr ogr ess over t he past t hr ee decades i n t he
accumul at i on of new knowl edge and devel opment of t heor i es i n t he fi el ds
of soil science, agr onomy, pl ant physiology, and pl ant nut r i t i on. Thus , t he
pr oduct i on of this book has been an exci t i ng chal l enge t o i nt egr at e t he most
r ecent i nf or mat i on about soil fertility with t he knowl edge and t heor i es
about weat her i ng and soil evol ut i on, mi ner al ogy, exchange chemi st ry, soil
t axonomy, fertilizer t echnol ogy, and pl ant gr owt h and nut r i t i on.
Soils ar e one of t he worl d' s most i mpor t ant r esour ces. We hope t hat
t he i nf or mat i on put fort h i n this book will hel p t o i ncrease t he food supply
for t he wor l d' s expandi ng popul at i on.
We ext end our special t hanks t o Mary Fot h for t he gr aphi c ar t wor k
and t o Nat e Rufe for phot ogr aphi ng t he mi ner al model s.
He nr y D. Fot h
Boy d G. El l i s
East Lansi ng, Mi chi gan
J u n e 1988
vi i
Contents
C H A P T E R 1
Soil Fertility and Plant Nutrition 1
Soil Fertility Defi ned 1
Hi st ori cal Devel opment 2
Soil as a Nut r i ent Reser voi r 6
Nut r i ent Upt ake from Soils 7
I mpor t ance of Fert i l i zers 14
C H A P T E R 2
Ion Exchange 17
Cat i on Exchange Capaci t y Defi ned 17
Sour ce and Amount of Negat i ve Char ge 18
Cat i on Exchange Capaci t y of Soils 27
I on Di st ri but i on near Cat i on Exchange Surfaces 29
Charact eri st i cs of Cat i on Exchange React i ons 30
Exchangeabl e Cat i on Suites 31
Exchangeabl e Cat i ons as a Sour ce of Pl ant Nut r i ent s 33
Ani on Exchange 34
C H A P T E R 3
Soil pH and Its Management 36
pH Defi ned 36
Det er mi nat i on of Soil pH 37
Th e Soil pH Cont i nuum 38
Ext r eme Weat her i ng Effects on pH and Cat i on Exchange 43
Soil Fertility and Soil Classification 46
Effects of Soil pH on Pl ant Gr owt h 47
ix
x Contents
Use of Li me 50
Aci d Rai n I nput s 58
Soil Acidification 59
C H A P T E R 4
Soil and Fertilizer Nitrogen 62
I nvent or y of t he Ear t h' s Ni t r ogen 62
Th e Soil Ni t r ogen Cycle 63
Ni t r ogen Upt ake 75
Basis of Ni t r ogen Fert i l i zer Recommendat i ons 75
Ni t r ogen Fert i l i zers 79
Ni t r ogen Car r i er Compar i sons 86
C H A P T E R 5
Soil and Fertilizer Phosphorus 88
I nvent or y of t he Ear t h' s Phos phor us 88
Phosphor us Cycling i n Soil Devel opment 89
Phos phor us i n Fert i l i zed Agr i cul t ur al Soils 90
Phos phor us Upt ake by Pl ant s 99
Basis of Phos phor us Fert i l i zer Recommendat i ons 99
Phos phor us Fert i l i zers 101
Use of Phos phor us Fertilizers 104
Envi r onment al Concer ns about Soils Cont ai ni ng Lar ge
Amount s of Phos phor us 108
C H A P T E R 6
Soil and Fertilizer Potassium 111
Th e Pot assi um Cycle 111
For ms of Soil Pot assi um 112
Pl ant and Soil Pot assi um Rel at i onshi ps 120
Fact ors Affecting Upt ake of Pot assi um 126
Basis of Pot assi um Fert i l i zer Recommendat i ons 129
Pot assi um Fert i l i zers 129
C H A P T E R 7
Sulfur and Micronutrients in Soils and Fertilizers 134
Sulfur 134
Mi cr onut r i ent s 138
Essential Mi cr onut r i ent s 139
Tr a c e El ement s Tha t May Be Toxi c 150
Soil Test i ng for Mi cr onut r i ent s 151
Ti ssue Tes t i ng for Mi cr onut r i ent s 152
Mi cr onut r i ent Deficiency Sympt oms 152
Contents xi
C H A P T E R 8
Mixed Fertilizers 160
Gr ade and Rat i o 161
Maj or Fert i l i zer Systems 161
Addi t i on and I ncor por at i on of Mi cr onut r i ent s 170
Salt I ndex 172
Aci di t y and Basicity 172
Fert i l i zer and Pesticide Combi nat i ons 174
C H A P T E R 9
Soil Fertility Evaluation 177
Pl ant Deficiency Sympt oms 177
Soil Test s 178
Pl ant Analysis 185
C H A P T E R 1 0
Application and Use of Fertilizers 191
Fert i l i zer Appl i cat i on Pract i ces 191
Fert i l i zer Recommendat i on Phi l osophi es 198
Fert i l i zer and Pl a n t - Wa t e r Rel at i ons 200
Effect of Fert i l i zers on Soil React i on 202
Economi cs of Fert i l i zer Use 203
Envi r onment al Concer ns 204
INDEX 208
C H A P T E R 1
Soil Fertility and
Plant Nutrition
SOI L F ER T I LI T Y D EF I N ED
Soi l f e r t i l i t y is t he status of a soil with respect to its ability to supply elements
essential for plant growth without a toxic concentration of any element. Thus , soil
fertility focuses on an adequat e and bal anced suppl y of el ement s or nu-
t ri ent s t o satisfy t he needs of pl ant s. Because pl ant s have evol ved i n differ-
ent cl i mat es and on di fferent soils, pl ant s have di fferent needs for t he
essential nut r i ent s and different t ol er ances of t he toxic el ement s. Cassava i s
nat i ve t o t he humi d t ropi cs and grows well on st rongl y acid soils cont ai ni ng
a l ar ge a mount of sol ubl e al umi num. Wheat , by cont r ast , or i gi nat ed on t he
st eppes wher e soils ar e neut r al or alkaline and cont ai n very little soluble
al umi num. As a consequence, a soil can be fertile for cassava and at t he
same t i me be infertile for wheat . In fact, many wheat cul t i vars have low
t ol er ance for sol ubl e al umi num, and t hei r r oot gr owt h i s r est r i ct ed i n its
pr esence.
Soi l Pr od u c t i v i t y .
Soil product i vi t y encompasses soil fertility plus all t he ot her factors affect-
i ng pl ant gr owt h, i ncl udi ng soil management . Soil product i vi t y is a meas ur e
)of t he soil' s ability to pr oduce a par t i cul ar cr op or sequence of cr ops unde r a
specified management system. All pr oduct i ve soils ar e fertile for t he cr ops
bei ng gr own, but many fertile soils ar e unpr oduct i ve because t hey ar e
subj ect ed t o dr ought or ot her unsat i sfact ory gr owt h factors or management
pract i ces. Th e r e is a st r ong positive cor r el at i on in pr oduct i ve soils bet ween
fertility and physical pr oper t i es so t hat hi ghl y pr oduct i ve soils have desir-
abl e physical pr oper t i es as well as hi gh fertility.
1
2 Soil Fertility and Plant Nutrition
H I S T O R I C A L D EV ELO P MEN T
I nt er est in soil fertility likely or i gi nat ed with t he devel opment of agri cul -
t ur e. By Roman t i mes many of t oday' s soil fertility management pract i ces
wer e used, i ncl udi ng manur i ng, l i mi ng, cr op r ot at i ons, and fallowing t o
bui l d up t he supply of available nut r i ent s. For t he next 2 000 years, till t he
end of t he Mi ddl e Ages and t he begi nni ng of t he Renai ssance, t he accumu-
lation of knowl edge and i mpr ovement s i n agr i cul t ur al pract i ce wer e slow.
And even t hough t he devel oped wor l d uses hi gh t echnol ogy i n agr i cul t ur e
t oday, about half of t he wor l d' s f ar mer s still use met hods similar t o t hose of
Roman t i mes or of t he Mi ddl e Ages (see Fi gur e 1.1).
Se a r c h f or t he Nou r i s hme nt of Pl a nt s
Dur i ng t he l at er years of t he Mi ddl e Ages, t he f oundat i ons of mode r n
science wer e bei ng laid, and much at t ent i on was focused on di scoveri ng
how veget at i on or pl ant gr owt h was nour i shed. Many t heor i es had evol ved,
variously pr oposi ng wat er, sal t pet er, soil, and t he j ui ces of t he ear t h as t he
pr i mar y const i t uent s. J a n Baptista Van Hel mont ( 1 5 7 7 - 1 6 4 4 ) , a Belgian
chemi st , put 200 pounds of soil i n an ear t hen vessel and gr ew a 169- pound
willow t r ee in five years by addi ng only wat er . T h e soil lost only 2 ounces, so
he concl uded t hat t he t r ee grew because of t he wat er . J ohn Woodwa r d i n
about 1700 revi ewed t he f i ndi ngs of Van Hel mont and ot her s and set up an
exper i ment with four wat er t r eat ment s i ncl udi ng rai n, r i ver wat er , and t wo
sewage wat er t r eat ment s. In all t r eat ment s t he pl ant s had an abundance of
FIGURE 1.1 Millions of farmers in the worl d today use tillage and soil fertility manage-
ment met hods similar to those used i n Roman times.
Historical Development 3
wat er and shoul d have gr own equally i f wat er was t he nour i s hment of
veget at i on. Pl ant gr owt h, however , i ncreased with an i ncrease i n t he
a mount of t errest ri al mat t er i n t he wat er . Soon aft er 1800 t he analytical
bal ance was i nvent ed and ai ded scientific di scovery because i t became possi-
bl e t o wei gh very small quant i t i es of chemi cal s and sol ut i ons. It was discov-
er ed t hat pl ant s and ani mal s r espi r e by burning organic food, a nd t he basic
concept of phot osynt hesi s was el uci dat ed. Van Hel mont ' s willow t r ee in-
creased i n wei ght largely because i t fi xed car bon. It was pr oved t hat pl ant s
do not i ngest part i cl es of food as ani mal s do, but t hat pl ant r oot s t ake up
nut r i ent el ement s for t he most par t as ions. An analysis of t he pl ant ash
r eveal ed el ement s commonl y or abundant l y f ound i n soils. Just us von Lie-
bi g ( 1803 - 1873) summar i zed t he maj or f i ndi ngs and br ought an e nd t o t he
search for t he nour i s hment of veget at i on. Li ebi g, a Ge r ma n chemi st , wr ot e
t hat pl ant s get most of t hei r car bon from car bon di oxi de, t hat wat er i s a
sour ce of hydr ogen and oxygen, and t hat t he soil i s a sour ce of el ement s i n
t he ash. But he er r oneousl y bel i eved t hat pl ant s absor bed t hei r ni t r ogen as
ammoni a from t he at mos pher e. Li ebi g' s book Organic Chemistry in Its Appli-
cation to Agriculture and Physiology, publ i shed in 1840, mar ks t he begi nni ng
of agri cul t ural science.
Fe r t i l i z e r De v e l op me nt
Some of t he earliest fertilizer mat eri al s used as sources of ni t r ogen, phos-
phor us , and pot assi um i ncl uded sodi um ni t r at e from Chi l ean mi nes, bones
a nd guano t o suppl y P, and wood ashes and evapor i t e salt deposi t s t o supply
K. Th e t r eat ment of bones wi t h sulfuric aci d t o i ncrease t he solubility of t he
P began about 1830, and soon t he mode r n fertilizer i ndust r y was bor n. In
1842 Sir J ohn Lawes of Engl and st ar t ed t he f i r st commer ci al manuf act ur e
of super phosphat e, and i n 1850 t he fi rst mi xed fertilizer was made i n
Bal t i mor e, Mar yl and. T h e famous Rot hams t ed Exper i ment al St at i on nor t h
of London, Engl and began f i el d exper i ment s i n 1843, a nd i n 1855 t he
st at i on decl ar ed t hat soil fertility coul d be mai nt ai ned for many years with
artificial manur es or chemi cal fertilizers. T h e fi rst commer ci al mi ni ng of K
salts occur r ed i n Ger many i n 1861.
Th e di scovery i n t he 1880s of ni t r ogen fi xat i on by bact er i a of t he
genus Rhizobium al l owed agri cul t uri st s t o under s t and why l egumes gr ow
much bet t er t han ot her pl ant s. Wor k by Fritz Ha be r and Karl Bosch led t o
t he devel opment of an efficient process for t he pr oduct i on of synt het i c
ammoni a i n Ger many i n 1913. T h e Ha b e r - Bo s c h process gave Ger many
an advant age i n Wor l d War I for t he pr oduct i on of N used i n explosives.
Today, N i s general l y t he most l i mi t i ng nut r i ent for cr op pr oduct i on, and
nearl y all t he N i n fertilizers i s der i ved from ammoni a synthesis. T h e most
r ecent devel opment s i n fertilizers i ncl ude mor e- concent r at ed a nd lower-
cost mat eri al s, pest i ci de i ncor por at i on, a nd i mpr oved physical a nd chemi cal
pr oper t i es, whi ch have i ncreased t he efficiency of appl i cat i on and
utilization.
Di s c ov e r y of Esse nt i a l a nd T o x i c El e me nt s
An el ement i s essential for pl ant gr owt h when t he pl ant i s unabl e t o com-
pl et e its life cycle wi t hout t he el ement , when no ot her el ement can t ake its
pl ace, and when t he el ement must be di rect l y i nvol ved i n t he pl ant ' s nut r i -
t i on. Al t hough N, P, K, and some ot her nut r i ent s have been r ecogni zed as
essential for a consi der abl e l engt h of t i me, t he dat e appear s t o be lost i n
ant i qui t y. I r on was f ound essential for all pl ant life i n 1860, and many ot her
nut r i ent s wer e f ound essential dur i ng t he first half of t he t went i et h cent ur y,
as shown i n Tabl e 1.1.
Resear ch t hen cent er ed on t he f or ms of t he essential nut r i ent s i n soils
a nd t he factors affecting t hei r availability for pl ant s. Soil tests wer e devel-
oped and used as t he basis for maki ng r ecommendat i ons for fertilizers.
Mor e recent l y, t he rol es of al umi num i n soil acidity and as a t oxi c el ement
i n acid soils have r ecei ved much at t ent i on. T h e pot ent i al l y di sast rous con-
sequences of appl yi ng sewage sl udge t o t he l and encour aged st udi es of t he
upt ake of heavy met al s by pl ant s, t hei r toxicity for pl ant s, and t hei r effects
on food quality. Envi r onment al concer ns r ecei ved publ i c at t ent i on as appli-
cat i on r at es of N and P fertilizers i ncreased. Cur r ent r esear ch in soil fertility
cont i nues t o emphasi ze bet t er soil- and pl ant -t est i ng met hods so t hat t he
best fertilizers can be ascer t ai ned and r e c omme nde d. Resear ch i n fertilizer
t echnol ogy emphasi zes t he devel opment of new manuf act ur i ng processes
and mat eri al s for mor e efficient i mpr ovement of soil fertility.
Ge ne t i c I mp r ov e me nt To Cop e wi t h Mi ne r a l St r e ss
An est i mat ed 22. 5 per cent of t he wor l d' s l and has some f or m of mi ner al
stress, a nut r i ent deficiency, an el ement toxicity, or bot h. Historically, lime
and fertilizers wer e used t o r emove t he mi ner al stress i n or der t o i ncrease
cr op pr oduct i on. Now an exci t i ng new ar ea of r esear ch ai ms at modi fyi ng
TABLE 1.1 Proof of Essentiality of Elements
Element Need proved by Year
Iron Sachs 1860
Manganese McHargue 1922
Boron Sommer and
Lipman 1926
Zinc Sommer and
Lipman 1926
Copper Sommer and
others 1931
Molybdenum Arnon and Stout 1939
Chlorine Broyer and
others 1939
Source: Adapt ed from Viets, 1977.
Historical Development 5
FIGURE 1.2 The iron-efficient Hawkeye soybean on the
left shows no iron chlorosis, but the iron-inefficient T2 0 3
cultivar on the right has severe iron chlorosis. Bot h were
grown in the same calcareous soil. (Photograph courtesy
John C. Brown. )
or i mpr ovi ng pl ant s so t hat t hey can bet t er cope wi t h mi ner al stress and be
pr oduct i ve wi t h mi ni mal use of lime and fertilizers.
I n anci ent t i mes gr ape gr ower s obser ved t he di fferent abilities of gr ape
cul t i vars t o t ol er at e cal careous soils i n Gr eece, Italy, and Fr ance. As a
consequence, t he graft i ng of desi rabl e gr ape scions on efficient root st ocks
became a c ommon me t hod of gr owi ng good wi ne gr apes on cal careous and
al kal i ne soils t hr oughout t he wor l d. Today, most gr apes and most fruit and
nut t r ee t ops ar e graft ed ont o efficient root st ocks t o over come mi ner al
stress, especially mi cr onut r i ent deficiencies associated with al kal i ne soils, as
well as t o pr ovi de pr ot ect i on agai nst soi l -borne r oot diseases. An exampl e of
t he di fference of soybean cultivars t o gr ow i n cal careous soil wi t hout devel-
opi ng i r on chl orosi s is shown in Fi gur e 1.2. Whe n t he iron-efficient t op is
gr af t ed ont o t he r oot s of t he iron-inefficient pl ant (shown i n Fi gur e 1.2), Fe
chl orosi s devel ops. If t he iron-inefficient t op i s gr af t ed ont o iron-efficient
r oot s, chl orosi s does not devel op.
Scientists ar e now t r yi ng t o identify t he genes t hat account for t he
t ol er ance of cer t ai n cul t i vars for toxicities and for t hei r effective upt ake of
nut r i ent s from infertile soils. Resear cher s ar e also maki ng efforts t o t ransfer
t hese genes to ot her cultivars. Success in t hese efforts will have a gr eat
i mpact i n devel opi ng count r i es wher e fertilizers and lime ar e expensi ve and
of l i mi t ed availability.
SOI L AS A N U T R I EN T R ESER V OI R
About 90 per cent of most mi ner al soils, soils ot her t han or gani c soils or
Histosols, consist of oxygen, silicon, and al umi num. The s e el ement s ar e not
i mpor t ant i n pl ant nut r i t i on because pl ant s obt ai n t hei r O from ai r and
wat er, Al is not an essential el ement , and Si is also not consi der ed an
essential el ement , even t hough i t i s somet i mes beneficial for rice and sugar
cane gr own on soils low i n silicate. Th e f our t h most abundant mi ner al soil
el ement i s Fe, whi ch pl ant s use i n small amount s . Thus , chemically speak-
i ng, t he essential nut r i ent s t hat pl ant s r emove from t he soil come f r om a
relatively small per cent age of t he soil.
Soi l Nu t r i e nt s v e r s us Pl a nt Ne e d s
Th e r e ar e gr eat differences i n t he amount s of t he vari ous el ement s i n bot h
soils and pl ant s. In t he soil t her e ar e, for exampl e, about 3 000 t i mes mor e
cal ci um and pot assi um t han mol ybdenum, and pl ant s t ake up annual l y
about 10 000 t i mes mor e Ca and K t han Mo as shown i n Tabl e 1.2. Of t he
six essential el ement s t hat pl ant s i n gener al t ake up i n an a mount over 1
ki l ogr am (kg) per hect ar e per year (multiply by 0. 892 t o conver t t o pounds
per acre), t he r at i o of t he soil' s cont ent t o annual upt ake r anges from a low
TABLE 1.2 Typical Concentrations of Essential Nutrients in Mineral Soils,
Annual Plant Uptake, and Ratio of Content in 10-cm Layer of Soil to Uptake
Annual plant
Soil content,
10-cm layer, to
Soil content, uptake, annual
Nutrient percent by weight kg/ ha uptake
Calcium 1 50 260
Potassium 1 30 430
Nitrogen 0.1 30 50
Phosphorus 0.08 7 150
Magnesium 0.6 4 2 000
Sulfur 0.05 2 320
Iron 4.0 0.5 100 000
Manganese 0.08 0.4 3 000
Zinc 0.005 0.3 2 000
Copper 0.002 0.1 1 000
Chlorine 0.01 0.06 200
Boron 0.001 0.03 400
Molybdenum 0.0003 0.003 1 000
Source: Adapted from Bohn, McNeal, and O'Connor, 1985.
Nutrient Uptake from Soils 7
of 50 for ni t r ogen t o 2 000 for magnesi um. For t he r emai ni ng seven
nut r i ent s with upt ake less t han 1 k g / h a annual l y, t he r at i o of soil cont ent t o
upt ake r anges from 200 t o 100 000. Th e nut r i ent s absor bed i n very small
amount s ar e usually sufficient unless some factor like soil pH causes t he m t o
be insoluble or unavai l abl e. I n gener al , t he gr eat er t he a mount t hat pl ant s
use, t he mor e likely t hat t he soil supply will be insufficient for cr op needs.
Most of t he usabl e or available nut r i ent s or i gi nat e from t he weat her i ng
of mi neral s and t he decomposi t i on of or gani c mat t er . Many pl ow layers
cont ai n 2% t o 4% or gani c mat t er , whi ch resul t s i n about 0 . 1 % t o 0. 2% N.
As t he a mount of or gani c mat t er i ncreases, t her e i s a cor r es pondi ng in-
crease i n N cont ent and decr easi ng cont ent of nut r i ent s t hat exist pri mari l y
i n t he mi ner al fract i on of t he soil. About 0. 9% of t he wor l d' s soils ar e
or gani c soils or Histosols. The s e soils, compar ed t o mi ner al soils, have a
hi gh per cent age of nut r i ent s t hat accumul at e i n humus , such as ni t r ogen,
phos phor us , and sulfur. By cont r ast , Histosols ar e commonl y very deficient
i n K for cr op needs. Th e near absence of silicate mi neral s i n Histosols may
keep t he amount s of soluble Si i n t he soil sol ut i on very small, whi ch means
t hat t he yields of sugar cane and ri ce may i ncrease when Si fertilizer i s
appl i ed, even t hough, as ment i oned earl i er, Si i s not strictly an essential
el ement .
N U T R I EN T U P T A K E F R O M SOI LS
Mov e me nt of Nu t r i e nt s t o Root s
Since nut r i ent s ar e absor bed for t he most par t as ions from t he soil sol ut i on
at t he r oot surface, a discussion of why nut r i ent s occur al ong r oot surfaces
in posi t i on for absor pt i on is i mpor t ant .
As r oot s el ongat e t hr ough soil, t he r oot s di rect l y encount er some of t he
ions t hat exist i n t he soil sol ut i on. For most pl ant s about 1% or less of t he
soil vol ume i s composed of active root s, and about 1% t o 2% of t he nu-
t r i ent s t aken up ar e positionally available at t he r oot surface because r oot s
i nt er cept t hem. Aft er a r oot becomes a r esi dent in a soil r egi on, ions in t he
soil sol ut i on ar e moved t o t he r oot by t he mass flow of wat er . Dur i ng mass
flow bot h wat er and ions ar e moved t o t he r oot surface. Th e gr eat er t he
i oni c concent r at i on i n t he soil sol ut i on, t he gr eat er t he quant i t y t hat will be
br ought t o r oot surfaces by mass flow. Ions i n t he soil sol ut i on ar e also i n
const ant mot i on and move t owar d r oot s by diffusion. Diffusion i s very
i mpor t ant for movi ng ions t o r oot surfaces when t hei r concent r at i on i n t he
soil sol ut i on is very low and little is moved by mass flow. It has been
est i mat ed t hat t he di st ance of diffusion per day t hr ough soil at fi el d capacity
t o r oot s i s 0. 13 cm for K
+
and 0. 004 cm for t he phos phat e i on, H 2 P 0 4
.
Consi der i ng t he slow diffusion r at e of nut r i ent ions, i t r equi r es many days
for some of t he ions to diffuse only 1 cm t hr ough soil. Thi s makes it
necessary for r oot s t o i nvade all soil regi ons f r om whi ch significant nut r i ent
upt ake occurs. Th e rel at i ve i mpor t ance of r oot i nt er cept i on, mass flow, and
diffusion in t he upt ake of several nut r i ent s by cor n is shown in Tabl e 1.3.
TABLE 1.3 Importance of Root Interception, Mass Flow, and Diffusion for the
Production of 9 500 Kilograms of Corn Grain on a Fertile Alfisol
Nutrient
1
a
kg/ ha
Amount
bsorbed
pounds/ acre
Interception,
kg/ ha
Mass flow
kg/ ha
Diffusion
kg/ ha
Nitrogen 190 170 2 150 38
Phosphorus 40 36 1 2 37
Potassium 195 174 4 35 156
Calcium 40 36 60 150 0
Magnesium 45 40 15 100 0
Sulfur 22 20 1 65 0
Source: Adapt ed from Barber, 1984.
Root i nt er cept i on was 2 k g / h a of N or about 1% of t he 190 kg
absor bed to pr oduce a hi gh yield of cor n on a fertile soil in I ndi ana ( Tabl e
1.3). Avai l abl e N exists mai nl y as sol ubl e ni t r at e in sol ut i on, and t he wat er
t hat was absor bed moved 150 k g / h a of N t o r oot s by mass flow. T h e
difference bet ween 152 and 190 i s consi der ed t he a mount of N moved t o
r oot s by diffusion. Al t hough mass flow is very i mpor t ant in N upt ake,
diffusion is t he most i mpor t ant for P and K upt ake because of t hei r low
concent r at i ons i n t he soil sol ut i on. As for Ca, t he cor n absor bed only 40
k g / h a , 60 kg wer e i nt er cept ed by r oot s, and 150 kg wer e moved t o t he
r oot s by mass flow. The s e cal cul at ed values ar e based on t he assumpt i on
t hat t her e wer e 6 000 k g / h a of available (exchangeabl e) Ca, a nd t hat t he
sol ut i on concent r at i on was 60 mi l l i gr ams/ l i t er . Thus , i f r oot s i nt er cept 1%
of t he available Ca, 60 kg will be i nt er cept ed. If t he pl ant s absor b 2. 5
million liters of wat er per hect ar e, 150 k g / h a of Ca (2 500 000 L x 0. 060
mg / L) will be moved t o r oot s by mass flow. T h e amount from r oot i nt er-
cept i on and mass flow is 210 kg, whi ch is over five t i mes t he a mount
absor bed. Unde r t hese condi t i ons an excess of Ca i s moved t o t he r oot
surfaces by mass flow, and a concent r at i on gr adi ent for Ca is est abl i shed
away from t he r oot . Thi s resul t s i n no Ca bei ng suppl i ed by diffusion. T h e
si t uat i on is similar for Mg and S.
Root Mor p hol og y a nd Nu t r i e nt Up t a k e
Root s el ongat e t hr ough t he soil by t he cont i nued division and el ongat i on of
cells i n t he apical mer i st emat i c zone. Cell division and el ongat i on occur
bot h away from and t owar d t he shoot , whi ch means t hat r oot cap cells
cont i nue t o f or m and t he r oot el ongat es. T h e el ongat i on zone i s made up of
i mmat ur e cells near t he r oot t i p wher e nut r i ent s and wat er can freely
diffuse t o t he cent er of t he r oot and ent er t he t r anspi r at i on st r eam of t he
xyl em. T h e cell walls cont ai n much cellulose, whi ch forms chai nl i ke mi cr o-
f i br i l s. Ions and wat er mol ecul es can readi l y diffuse i nt o and t hr ough t he
i nt ermi crofi bri l l ar spaces. Ions absor bed i nt o t he cell walls of cort i cal cells
can mi gr at e cent ri pet al l y by movi ng t hr ough t he cell wall of one cell and
i nt o and t hr ough t he cell wall of an adj acent cell. T h e cell walls ar e t he
apopl ast , t he par t away from t he pl asma, and make up t he apopl ast i c
pat hway. Thus , i n t he i mmat ur e sect i on of t he r oot , ions a nd wat er can
move across t he cor t ex and ent er t he t r anspi r at i on st r eam i n t he xyl em
vessels wi t hout crossi ng pl asma membr anes (see Fi gur e 1.3). I on upt ake i n
t hi s zone i s r api d, and Ca upt ake i s r est r i ct ed t o this zone. Since pl ant s ar e
unabl e t o t r ansl ocat e Ca t owar d t he apex from ol der r oot sect i ons, r oot
el ongat i on i nt o calcium-deficient soil i s i nhi bi t ed. Most cat i ons appear t o be
abs or bed on newly f or med r oot s, and t hei r upt ake i s r est r i ct ed when soils
become dr y because new r oot gr owt h i s great l y rest ri ct ed.
Root s cells quickly ma t ur e a few cent i met er s behi nd t he el ongat i on
FIGURE 1.3 A longitudinal drawi ng of the apical porti on of a root. In the
el ongati on zone many cells are i mmature; ions and water readily diffuse to
the center of the root and enter the transpiration stream i n the xyl em. Ion
movement to the xyl em in the maturati on zone is inhibited by the Casparian
strip in the endodermi s.
zone, and t he Caspari an st ri p forms i n t he endoder mi s t hat lies adj acent t o
t he stele or cent ral cor e of t he r oot . T h e Caspari an st ri p i s a t hi ckeni ng
s ur r oundi ng t he endoder mal cells and forms a bar r i er at t he i nner cor t ex
for t he apopl ast i c movement of nut r i ent s. T h e Caspari an st ri p also inhibits
t he out war d flow of ions from t he xyl em. Al ong t he ma t ur e sect i on of r oot s,
nut r i ent s and wat er may move freely t hr ough t he cor t ex via t he apopl ast i c
pat hway, but t hey event ual l y encount er t he endoder mi s , whi ch pr event s
f ur t her movement t o t he cent er of t he r oot . Thus , t o mi gr at e across t he
endoder mi s , t he nut r i ent s must ent er epi der mal or cort i cal cells and move
i nwar d by t he symplastic pat hway, whi ch consists of t he cyt opl asm and
i nt er connect i ons bet ween cells, called plasmodesmata (see Fi gur e 1.4).
A muci gel sheat h s ur r ounds t he r oot cap and ext ends i nt o t he el onga-
t i on zone. Thi s mat eri al , al ong wi t h r oot exudat es, forms a subst r at e for
mi cr oor gani sms i n t he r hi zospher e. T h e densi t y of mi cr obes i n t he rhi zo-
spher e may be 100 t i mes gr eat er t han t hat i n root -free soil. Thes e or ga-
nisms have an i nfl uence on nut r i ent availability and nut r i ent upt ake near
t he r oot surface. Mycorrhi zal fungus r oot s great l y ext end t he effective
surface ar ea of most r oot s and similarly i nfl uence nut r i ent upt ake from
soils.
Car r i e r The or y of I on Up t a k e
Mass fl ow moves a l arge a mount of Ca t o r oot surfaces rel at i ve t o pl ant
needs. Cal ci um can be t aken up passively al ong a concent r at i on gr adi ent
bet ween t he soil sol ut i on and cent er of t he r oot via t he apopl ast i c pat hway.
For t he ot her nut r i ent s movi ng i n t he symplastic pat hway, t he concent r a-
t i on i n t he xyl em i s commonl y gr eat er t han i n t he soil sol ut i on. Movement
of ions agai nst a concent r at i on gr adi ent , t hat is, by active upt ake, r equi r es
FIGURE 1.4 Di agram of (a) symplastic and (b) apoplastic movement of ions from the
soil solution t hrough the cortical cells. Ions that move apoplastically t hrough the
cortex must enter cortical cells and move from cell to cell symplastically (through a
pl asmodesma) to cross the Casparian strip in the endodermi s. Pl asmodesmata are
cytoplasmic strands that pass t hrough openi ngs in some plant cell walls and provi de
living bri dges bet ween cells.
met abol i c ener gy. Ener gy appear s t o be needed t o move ions across t he
plasmic me mbr a ne j ust inside t he cell wall of epi der mal or cortical cells and
per haps at ot her places al ong t he symplastic r out e bef or e t he ions ent er t he
t r anspi r at i on st r eam i n t he xyl em.
Resear ch wi t h l arge algal cells showed t hat cells coul d accumul at e ions
i n gr eat er concent r at i on t han i n t he ext er nal sol ut i on, while effectively
excl udi ng some ions i n hi gh concent r at i on i n t he ext er nal sol ut i on. Pl ant
r oot s also discriminate i n ion upt ake as shown i n Tabl e 1.4. T h e c ommon
cr op pl ant s excl uded Na and accumul at ed K rel at i ve t o t he nut r i ent solu-
t i on, whi ch cont ai ned 2 5 % equi val ent concent r at i ons of each cat i on. Mag-
nesi um and Ca upt ake wer e mor e i n line with sol ut i on concent r at i ons. T h e
hal ophyt e i s i ndi genous t o saline soil areas and accumul at ed much mor e Na
a nd much less Ca t han t he ot her pl ant s. I n gener al , as t he concent r at i on of
an i on i n t he soil sol ut i on i ncreases, upt ake of this ion i ncreases. Somet i mes
upt ake of an i on i ncreases wi t h a si mul t aneous r educt i on i n t he upt ake of
some ot her ion. Th e upt ake of Mg i s commonl y r educed when fertilization
wi t h K causes an i ncreased upt ake of K.
Th e car r i er t heor y of ion absor pt i on at t empt s t o expl ai n bot h t he need
for met abol i c ener gy and t he ability of pl ant s t o di scri mi nat e i n i on upt ake.
I ons readi l y diffuse t hr ough cell walls and encount er t he plasmic mem-
br ane. At or near t he plasmic me mbr a ne , ions link up wi t h ion-specific
car r i er s t hat t r anspor t t he ions across t he me mbr a ne and deposi t t he ions
i nt o t he cell' s i nt er i or . Car r i er t r anspor t r equi r es ener gy, and t he car r i er s
exhi bi t specificity t o account for t hei r di scri mi nat ory behavi or . As i ndi cat ed
earl i er, t he use of ener gy t o accumul at e ions agai nst a concent r at i on gra-
di ent i s active upt ake; most i on upt ake by r oot s i s act i ve. In gener al , ani ons
a nd cat i ons ar e t aken up si mul t aneousl y. Whe n an excess of cat i ons, com-
par ed t o ani ons, i s t aken up, H
+
ar e excr et ed t o mai nt ai n electrical neut r al -
ity in bot h t he soil sol ut i on and t he cell. Wi t h excess upt ake of ani ons, OH

ar e excr et ed for t he same r eason. Small amount s of nut r i ent s ar e absor bed
as mol ecul es, i ncl udi ng N as ur ea and some mi cr onut r i ent s as chel at ed
compounds .
TABLE 1.4 Discrimination of Plant Roots in Uptake of Four
Cations from a Solution Containing Equivalent
Concentrations of the Cations
Plant
Total cations in plant, percent
Plant Na K Mg Ca
Buckwheat (Fagopyrum) 0.9 39 27 33
Sunflower (Helianthus) 2.3 54 17 27
Corn (Zea mays) 2.9 70 16 11
Potato (Solanum) 4.1 44 25 27
Halophyte (Atriplex) 19.7 39 31 10
Source: After Col l ander, 1941.
Nu t r i e nt Up t a k e a nd Pl a nt Gr owt h
Th e fi rst nut r i ent s of a ger mi nat i ng seed come from t he seed. Aft er ger mi -
nat i on, t he r oot s i nvade t he s ur r oundi ng soil i n search of nut r i ent s a nd
wat er. As r oot s leave t he i mmedi at e vicinity of t he seed and el ongat e i nt o
t he s ur r oundi ng soil, nut r i ent s and wat er ar e absor bed adj acent t o t he
r oot s. Wat er upt ake causes soil dr yi ng. Th e dr yi ng near t he r oot surface
decreases t he soil' s hydr aul i c conduct i vi t y, whi ch r educes t he movement of
bot h wat er and ions t o t he r oot s by mass flow. Lat er - f or med r oot s will t end
t o grow i n unoccupi ed soil wher e wat er and nut r i ent s ar e mor e available.
As a consequence, r oot s t end t o space t hemsel ves r at her uni f or ml y t hr ough
t he soil in a l at eral di r ect i on as shown in Fi gur e 1.5.
Th e penet r at i on of small grai n r oot s, such as oats and wheat , i s typi-
cally less t han for cor n. By t he end of t he gr owi ng season, cor n r oot s will
usually have i nvaded t he soil t o dept hs of a met er or mor e. Thi s i s necessary
t o supply t he wat er needs because t he mobi l i t y of wat er hel d i n soil bet ween
fi el d capacity and t he wilt poi nt i s l i mi t ed. Avai l abl e nut r i ent s and r oot s
t end t o be i n t he hi ghest concent r at i on i n t he Ap hor i zon, whi ch causes a
gr eat er pr opor t i on of t he nut r i ent s t o be absor bed from t he Ap hor i zon.
FIGURE 1.6 Accumul at i on of potassi um, ni trogen, phospho-
rus, and dry matter by corn. (Adapted from Thompson, 2nd
ed. , 1957, used by permission of author. )
Early i n t he devel opment of an annual pl ant , r oot gr owt h i s relatively
mor e r api d t han shoot gr owt h. Gr owt h rat es vary with seasons, however . By
t he t i me cor n r oot s have 50% of t hei r wei ght , only 15% of t he t op cor n
gr owt h may have occur r ed. I n t he shoot s N, P, and K ar e t aken up mor e
rapi dl y, relatively speaki ng, t han gr owt h occurs or dr y mat t er accumul at es.
Thi s means t hat del ayi ng t he appl i cat i ons of fertilizer, aft er t he per i od of
nor mal l y r api d upt ake, will r educe t he oppor t uni t i es for nut r i ent upt ake
and for i ncreases i n yield. Of t he nut r i ent s, K accumul at es i n cor n mor e
rapi dl y t han N, and t he N accumul at es mor e rapi dl y t han t he P (see Fi gur e
1.6). In addi t i on, t he a mount of K i n t he cor n shoot decreases late i n t he
season.
Root gr owt h i n cor n i s especially i nt er est i ng because late i n t he season,
j us t bef or e t he ear devel ops, br ace r oot s e me r ge from t he l ower st em nodes
and br anch profusely upon ent er i ng t he soil. Resear ch has shown t hat 1%
t o 36% of t he P i n pl ant s was absor bed by br ace r oot s. Thes e secondar y
r oot s can be i mpor t ant for nut r i ent upt ake when t he Ap hor i zon i s occa-
sionally r ewet t ed by late season rai ns.
FIGURE 1.5 Oat roots recovered from a 10-centi meter-
thick slab of soil show a uni form distribution laterally at all
soil depths. The scale is in i nches.
Root a nd Soi l Int e r a c t i on
It is a c ommon observat i on t hat or gani sms ar e, in par t , a pr oduct of t hei r
envi r onment . So i t i s wi t h r oot s. Th e soil envi r onment affects t he r oot , and
t he r oot r esponds with vari ous st rat egi es t o cope with t he exi st i ng soil
envi r onment . Th e differential excr et i on of H
+
and OH
ions with cat i on

and ani on upt ake, whi ch was ment i oned earl i er, modifies t he pH i n t he
i mmedi at e envi r onment at t he r oot surfaces. I t has been obser ved t hat some
pl ant s gr owi ng i n i ron-st ressed soils excr et e addi t i onal H
+
, whi ch i ncreases
t he acidity and solubility of Fe. Some pl ant s excr et e l ow-mol ecul ar-wei ght
or gani c mol ecul es t hat mobilize Fe, whi ch i s subsequent l y absor bed. Thes e
mechani sms ar e associated wi t h pl ant s t hat ar e iron-efficient. A wheat
cul t i var t hat is t ol er ant of soil with a hi gh cont ent of al umi num was f ound to
i ncrease t he pH near r oot surfaces, whi ch r esul t ed i n preci pi t at i on of t he Al
and r educed upt ake. Thus , t he i nt eract i ons of r oot s wi t h soils ar e very
compl ex, and r oot s ar e not passive but ar e active i n modi fyi ng t hei r envi-
r onment , t he bet t er t o cope with nut r i ent deficiencies a nd el ement
toxicities.
I MP O R T A N C E OF F ERT I LI Z ERS
Soils can sustain a low level of cr op yields for cent ur i es when soil manage-
ment i nput s ar e mi ni mal . Thi s level i s i n t he r ange of 8 t o 10 bus hel s / acr e
or about 1 000 t o 1 200 k g / h a and i s compar abl e t o wheat yields i n Bri t ai n
bet ween 1 100 and 1 350. Not i ce in Fi gur e 1.7 t hat bet ween 1 350 and
1 550 wheat yields i ncreased slowly as grass was used to i mpr ove pri vat el y
owned l ands t hat had become exhaust ed dur i ng t he feudal per i od. Over t he
next 350 years, yields wer e i ncreased slowly t hr ough trial and er r or . Th e
shar p rise in yields since 1900 reflects t he appl i cat i on of scientific knowl -
edge about pest cont r ol , i mpr oved vari et i es, and soil management .
Lar ge i ncreases i n cr op yields have occur r ed i n many count r i es since
Wor l d War I I . Cor n yields i n t he Cor n Belt of t he Uni t ed States nearl y
doubl ed bet ween 1939 and 1961. Par t i t i oni ng of t he factors t hat caused
yields t o i ncrease showed t hat i mpr ovement of vari et i es account ed for 36%
FIGURE 1.7 Wheat yields i n Britain from 1100 to 1960 i n hundred
wei ghts per acre. (Adapted from Jacks, 1962. )
References 15
of t he i ncrease, followed by t he use of fertilizer for 3 1 %. Several st udi es
have concl uded t hat fertilizer use account s for 2 5 % t o 50% of t he gr ai n
pr oduct i on i n t he Uni t ed St at es.
Whe n a huma n communi t y i nvades new l and, t he exi st i ng bal ance of
nat ur e i s dest r oyed. In pi oneer societies soil fertility t ends t o be expl oi t ed as
nut r i ent s i n or gani c mat t er ar e mi ner al i zed, and t he or gani c mat t er de-
clines aft er t he l and i s cul t i vat ed. Such an expl oi t at i ve society may not have
t he weal t h or means t o i mpr ove soil fertility. Since t he i ndust ri al r evol ut i on
began about 500 years ago, t he accumul at i on of weal t h has r esul t ed i n
i nvest ment s t hat have i ncreased soil fertility. A st udy by t he Food and
Agr i cul t ur e Or gani zat i on of t he Uni t ed Nat i ons ( FAO) of 41 count r i es
f ound a positive rel at i on bet ween a mount of fertilizer used and t he val ue
i ndex (yield) of cr ops pr oduced per hect ar e. T h e most devel oped count r i es
t ended t o use fertilizer at t he hi ghest r at es. Thus , i t i s seen t hat t he fertility
of soils and t he use of fertilizers play an i mpor t ant rol e i n wor l d food
pr oduct i on and ar e r el at ed t o t he overal l economi c activity i n a count r y.
A Look t o t he Fut ur e
In 1876 t he Mor r ow Plots wer e est abl i shed at t he Uni versi t y of Illinois t o
st udy bot h soil fertility depl et i on and i mpr ovement . Th e pl ot s wer e est ab-
lished on Mollisols of hi gh nat ur al fertility, but when t he fi el ds wer e
cr opped t o cont i nuous cor n wi t hout fertilizers or ma nur e , yields quickly
decl i ned and wer e about 20 bus hel s / acr e i n 1954. I n 1955 t he plots wer e
split in half, fertilizers wer e appl i ed accor di ng to soil tests, and t he yield was
86 bus hel s / acr e. Thes e dr amat i c resul t s wer e publ i shed i n a paper ent i t l ed
"Al l t he Way Back in On e Year ?" Because soil fertility is essentially an
i nt egr at i on of t he ki nds and amount s of nut r i ent ions i n t he soil sol ut i on, i t
can be rapi dl y depl et ed. On t he ot her hand, soil fertility can be r est or ed
al most i nst ant aneousl y. For t he f ut ur e, knowl edge of soil fertility and t he
use of fertilizers will play an i ncreasi ngl y i mpor t ant rol e i n expl oi t i ng t he
soil' s food pr oduct i on pot ent i al t o i mpr ove t he living s t andar d of t he
wor l d' s peopl e.
REF ERENCES
Barber, S. A. 1984. Soil Nutrient Bioavailability. John Wiley, New York.
Bohn, H. L., B. L. McNeal, and G. A. O' Connor. 1985. Soil Chemistry. John Wiley,
New York.
Brown, J. C, R. S. Holmes, and L. O. Tiffin. 1957. Iron Chlorosis in Soybeans as
Related to the Genotype of Rootstalk. Soil Sci. 86: 75- 82.
Collander, R. 1941. Selective Absorption of Cations by Higher Plants. Plant Physiol.
16: 691-720.
Ellis, B. G., B. D. Knezek, and L. W. Jacobs. 1983. The Movement of Micronu-
trients in Soils. In Chemical Mobility and Reactivity in Soil Systems. Soil Sci. Soc.
Am., Madison, Wis.
Foth, H. D. 1962. Root and Top Growth of Corn. Agron. four. 54: 49- 52.
Hanway, J. J. 1962. Corn Growth and Composition in Relation to Soil Fertility:
Uptake of N, P, and K and Their Distribution in Different Plant Parts During
the Growing Season. Agron. Jour. 54: 217- 222.
International Fertilizer Development Center and United Nations Industrial Devel-
opment Organization. 1979. Fertilizer Manual. Ref. Manual IDFC-R-1, Muscle
Shoals, Ala.
Jacks, G. V. 1962. Man: the Fertility Maker. Jour. Soil Water Con. 17:146, 148, and
176.
Kellogg, C. E. 1957. We Seek; We Learn. In USDA Yearbook of Agriculture, Soil.
Washington, D.C.
Mengel, K. and E. A. Kirkby. 1982. Principles of Plant Nutrition. 3rd ed. Int. Potash
Institute, Bern, Switzerland.
Robertson, J. A., B. T. Kang, F. Ramirez-Paz, C. H. E. Werkhover, and A. J.
Ohlrogge. 1966. Principles of Nutrient Uptake From Fertilizer Bands: VII.
Uptake by Brace Roots of Maize and Its Distribution Within the Leaves. Agron.
Jour. 58: 293- 296.
Russell, E. W. 1973. Soil Conditions and Plant Growth. 10th ed. Longmans, Green,
London.
Russell, M. B. 1955. All the Way Back in One Year? Plant Food Rev. Washington,
D.C.
Russell, R. S. 1977. Plant Root Systems: Their Function and Interaction with the Soil.
McGraw-Hill, New York.
Sayre, J. D. 1948. Mineral Accumulation in Corn. Plant Physiol. 23: 267- 281.
The White House. 1967. The World Food Problem. U.S. Gov. Printing Office, Wash-
ington, D. C.
Thompson, L. M. 1957. Soils and Soil Fertility. 2nd ed. McGraw-Hill, New York.
Tisdale, S. L., W. L. Nelson, and J. D. Beaton. 1985. Soil Fertility and Fertilizers.
4th ed. Macmillan, New York.
Viets, F. G. 1977. A Perspective on Two Centuries of Progress in Soil Fertility and
Plant Nutrition. Soil Sci. Soc. Am. Jour. 41: 242- 249.
Wright, M. J., ed. Plant Adaption to Mineral Stress in Problem Soils. Proc. Workshop
held at Beltsville, Md. in 1976. USAID, Washington, D.C.
C H A P T E R 2
Ion Exchange
Th e di scovery of ion exchange i n soils occur r ed about 1850 i n Engl and.
Ha r r y St ephen Thomps on, a Yor kshi r e f ar mer , r epor t ed t hat l eachi ng a
soil wi t h an a mmoni um sulfate sol ut i on pr oduc e d l eachat e t hat was pr i mar -
ily cal ci um sulfate. T h e a mmoni um ions i n sol ut i on wer e exchanged for
cal ci um ions from t he soil. Th e cat i on exchange r eact i on t hat occur r ed i s
r epr es ent ed as
( NH4 ) 2 S O4 + CaX = ( NH4 ) 2 X + Ca SO4 (2.1)
wher e X desi gnat es t he exchange surface. Cal ci um ions originally adsor bed
by colloidal part i cl es wer e exchanged by a mmoni um ions and l eached from
t he soil al ong wi t h t he sulfate ions. Thi s showed t hat t he soil preferent i al l y
ads or bed cat i ons as compar ed t o ani ons, and t hat t he soil was negat i vel y
char ged. In cat i on exchange t her e i s an exchange of cat i ons i n sol ut i on wi t h
cat i ons adsor bed ont o a surface-active mat er i al . Th e surface ar ea and
char ge of t he part i cl es ar e l arge so t hat a single colloidal part i cl e or micelle
can be viewed as a gi ant ani on with hundr e ds of t housands of ads or bed
cat i ons.
Wi t hi n t he past fifty years consi der abl e knowl edge has accumul at ed
about t he soil' s positive char ge and ani on exchange capacity. In most soils
t he negat i ve char ge i s much gr eat er t han t he positive char ge. As soils
become ext r emel y weat her ed, however , t he positive char ge becomes mor e
nearl y equal t o t he negat i ve char ge and i n cer t ai n soils may even exceed t he
negat i ve char ge.
C A T I O N EX C H A N G E C A P A C I T Y D EF I N ED
Th e cation exchange capacity, CEC, is a quant i t at i ve expressi on of t he amount
of negative charge per unit quantity of oven-dry soil, or soil components. Or it is
17
18 Ion Exchange Source and Amount of Negative Charge 19
COOH = COO
+ H
+
(2.2)
A small a mount of char ge comes from enolic a nd i mi de N gr oups.
An i ncrease i n hydr oxyl concent r at i on of t he soil sol ut i on, accompany-
i ng an i ncrease i n pH, br i ngs about a gr eat er dissociation of ads or bed H
+
;
mor e wat er forms, and t he CEC i ncreases. As a resul t , t he CEC of or gani c
mat t er i s pH- dependent or vari abl e (CECv ).
Bot h living r oot s and dead or gani c mat t er have CEC. As or gani c
mat t er decomposes i n t he soil, t her e i s an i ncrease i n acidic gr oups, whi ch i n
t ur n i ncreases t he CEC. Histosols ar e composed mai nl y of or gani c mat t er
and have relatively hi gh CEC, typically bet ween 100 and 200 me q / 1 0 0 g.
Fibrists ar e f i br ous Histosols and ar e t he l east -decomposed or most peat y
Histosols wi t h a CEC of about 100. Th e Saprists, t he most - decomposed
Histosols, have a CEC mor e nearl y 200. T h e bul k of humus i n mi ner al soils
i s general l y well decompos ed and has qui t e hi gh CEC aver agi ng about 200
and r angi ng from 100 t o 400. Thus , t he degr ee of decomposi t i on of soil
or gani c mat t er great l y affects t he CEC.
Ne g a t i v e Cha r g e of Mi ne r a l Fr a c t i on
Th e mi neral s of t he clay fraction ar e t he sour ce of most of t he negat i ve
char ge of t he soil' s mi ner al fraction. Th e negat i ve char ge i s bot h pH- de-
pendent and per manent . I s omor phor us subst i t ut i on pr oduces pe r ma ne nt
CEC (CECp ), and t he CECv i s due mai nl y t o depr ot onat i on of edge or
exposed hydroxyl s.
Origin of Clay Minerals in Soils
Clay mi neral s ar e f or med by t he weat her i ng and al t er at i on of exi st i ng
mi ner al s or by neogenesi s, t he crystallization of ions from sol ut i on. Soils
f or med from sedi ment s and sedi ment ar y rocks i nher i t clay mi ner al s pr esent
i n t hese mat eri al s. I n t he gl aci at ed Nor t h Cent r al r egi on of t he Uni t ed
St at es, t he maj or clay mi ner al in t he loess is mont mor i l l oni t e (a smect i t e)
and i n t he till hydr ous mi ca (illite). Many of t he till-derived soils of this
r egi on have a significant a mount of hydr ous mica i nher i t ed from t he till
and vermi cul i t e t hat was pr oduced by t he al t er at i on of hydr ous mi ca.
Mollisols of t he Cor n Belt t hat devel oped from loess have clay fractions
domi nat ed mostly by mont mor i l l oni t e, for this clay was i nher i t ed and has
not been substantially al t er ed or dest r oyed. Vert i sol s of t he Deccan Pl at eau
i n I ndi a, by cont rast , cont ai n mont mor i l l oni t e t hat f or med from t he weat h-
er i ng of under l yi ng basalt (neogenesis). Thus , t he f or mat i on and al t er at i on
of clay mi neral s i n soils ar e compl ex. Ou r consi der at i on of t he ori gi n of t he
negat i ve char ge will focus on t he general l y accept ed weat her i ng sequence
of mi ca t o hydr ous mi ca t o vermi cul i t e and smect i t e t o kaol i ni t e and, fi nal l y,
t o gi bbsi t e. Th e weat her i ng sequence appr oach pr ovi des a uni fyi ng concept
about t he ori gi n of clay mi neral s and t he sour ce and a mount of t hei r
negat i ve char ge.
t he capacity to adsorb cations from solution. T h e CEC is expr essed as milliequi-
val ent s per 100 gr ams ( me q / 1 0 0 g) of oven- dr y soil. A soil wi t h a CEC of 1
meq has 6. 02 X 1 0
2 0
negat i ve char ges per 100 gr ams and can adsor b t hat
many monoval ent cat i ons from sol ut i on. Since each di val ent cat i on can
neut r al i ze t wo char ges, t he soil can t heoret i cal l y adsor b 3. 01 X 1 0
2 0
diva-
l ent cat i ons from sol ut i on. If t he monoval ent cat i on i s K, 0. 039 gr am will be
adsor bed per 100 gr ams. If t he di val ent cat i on i s Ca, 0. 020 gr am of Ca will
be adsor bed per 100 gr ams. Thus , t he CEC i s a measur e of t he soil' s ability
t o adsor b cat i ons i n t er ms of chemi cal equi val ence r at her t han mass or
wei ght .
De t e r mi na t i on of Ca t i on Ex c ha ng e Ca pa c i t y
Th e a mount of CEC or negat i ve char ge of a soil i s pH- dependent . For
exampl e, t he H of vari ous acidic gr oups of soil or gani c mat t er may be
neut r al i zed by O H
, whi ch resul t s i n t he f or mat i on of wat er and an unsatis-

fied negat i ve char ge. As soil pH i ncreases, so does OH
concent r at i on (or
activity) and t he f or mat i on of wat er and negat i ve char ge or CEC. For this
r eason t he CEC must be det er mi ned at a st andar d pH t o make valid
compar i sons bet ween soils.
Commonl y, t he soil is t r eat ed wi t h a nor mal a mmoni um acet at e solu-
t i on adj ust ed t o pH 7. 0. Ammoni um repl aces t he adsor bed cat i ons and
occupi es t he exchange sites. T h e excess a mmoni um, al ong wi t h t he ex-
changed or di spl aced cat i ons, i s l eached out with al cohol adj ust ed t o pH
7. 0. Th e a mount of a mmoni um r et ai ned by t he soil i s t hen meas ur ed and
equat ed t o t he CEC. Anot he r pr ocedur e det er mi nes CEC at pH 8.2 usi ng
Na OAc and BaCl 2 pl us t r i et hanol ami ne ( TEA) sol ut i on. Th e Na OAc r e-
places exchangeabl e Ca, Mg, K, and Na, whi ch ar e meas ur ed a nd a dde d t o
t he a mount of acidity neut r al i zed by t he TEA. Anot he r met hod uses an
ext r act i ng sol ut i on of unbuf f er ed KC1 or CaCl 2 t o r epl ace t he exchangeabl e
cat i ons and l each t hem from t he soil. Th e n t he a mount of each exchange-
abl e cat i on i n t he l eachat e i s det er mi ned, and t he sum of t he cat i ons i s
equat ed t o t he CEC. Thi s met hod i s very i mpor t ant for det er mi ni ng t he
CEC of soils at t hei r pr esent or nat ur al pH, part i cul arl y, for acid soils.
SOU R C E A N D A M O U N T O F N EG A T I V E C H A R G E
Or gani c mat t er and clay fractions ar e t he sour ce of most of t he negat i ve
char ge. Th e negat i ve char ge of t he soil or gani c mat t er , SOM, i s pH- depen-
dent , and t he negat i ve char ge of t he clay fraction i s bot h pH- de pe nde nt and
per manent .
Ne g a t i v e Cha r g e of Or g a ni c Mat t e r
Or gani c mat t er has several acidic funct i onal gr oups t hat dissociate H
+
or
depr ot onat e. About 85 per cent or mor e of t he negat i ve char ge i s due t o
carboxyl and phenol gr oups. I n t he pH r ange of most soils ( pH less t han
8.0), carboxyl gr oups pr ovi de most of t he CEC of SOM:
20 Ion Exchange
Hydrous Mica and Vermiculite
Muscovi t e and bi ot i t e ar e micas t hat ar e 2 : 1 layer mi neral s and ar e ubi qui -
t ous i n soils. Bi ot i t e i s t r i oct ahedr al wi t h Mg
2 +
and F e
2 +
as t he domi nant
cat i ons i n t he oct ahedr al sheet . Muscovi t e i s di oct ahedr al with Al
3 +
i n t he
oct ahedr al sheet . Bot h have i s omor phor us subst i t ut ed Al
3 +
i n t he silica
t et r ahedr al sheet t hat pr oduces one negat i ve char ge for every S i
4 +
r epl aced
by Al
3 +
. About one i n four of t he silicon at oms i n t he t et r ahedr al sheet s i s
r epl aced by Al
3
, r esul t i ng i n a hi gh pe r ma ne nt negat i ve char ge. In un-
weat her ed mica this char ge is bal anced by K ions t hat fit bet ween adj acent
layers. T h e i nt er l ayer K ions bal ance t he char ge and act as a bridge hol di ng
t he layers t oget her so t hat t he layers do not expand (see Fi gur e 2. 1).
Dur i ng weat her i ng, i nt erl ayer K i s lost al ong t he part i cl e edges. Th e
loss of K
+
creat es voi ds wher e unsatisfied negat i ve char ge devel ops, t her eby
cr eat i ng CEC. Th e loss of K paral l el s t he i ncrease i n CEC and resul t s i n
about 10 t o 40 me q / 1 0 0 g. T h e loss of K also resul t s i n expansi on or
separat i on of t he 2 : 1 layers al ong t he edges of t he mi ca part i cl es. Thi s
al t er ed mi ca is hydrous mica (see Fi gur e 2. 2).
Whe n t he concent r at i on of hydr at ed K
+
i s hi gh near CEC sites wher e
i nt er l ayer K has been lost, t hese ions r eent er t he voids and become fi xed.
Thi s fi xat i on i s r el at ed t o t he low ener gy of hydr at i on and t he easy loss of
hydr at ed wat er when K ions r eent er t he i nt er l ayer space. T h e fi xat i on of K
l owers t he CEC and causes t he expanded edges of layers t o collapse. Pot as-
sium may become fixed when K fertilizer is appl i ed and t hen pr ot ect s K
from bei ng lost by l eachi ng.
Whe n loss of t he i nt er l ayer K i s compl et e or nearl y compl et e, t he layers
expand, and hydr ous mi ca al t ers i nt o vermiculite wi t h CEC of about 120 t o
FIGURE 2. 1 Model of the 2 : 1 mica mineral (muscovite) with t wo
layers slightly offset to show the location and arrangement of the
interlayer potassium ions (nonhydrated) that neutralize the tetrahe-
dral sheet charge and hol d the layers together.
Source and Amount of Negative Charge 21
FIGURE 2. 2 Model of hydrous mica with two layers slightly offset
to show four interlayer potassi um ions (nonhydrated) exposed
al ong the edges. The loss of interlayer potassium produces cation
exchange sites on the exteri or planar surfaces and edges that ad-
sorb hydrated cations, whi ch are exchangeabl e. Three are shown.
150 me q / 1 0 0 g. Thi s i s about t he hi ghest CEC f ound i n soil clay mi neral s.
T h e surface ar ea of vermi cul i t e i s 600 t o 800 m
2
/ g compar ed t o onl y 70 t o
120 m
2
/ g for nonexpandi ng hydr ous mica (see Fi gur e 2. 3).
T h e hi gh char ge near t he i nt er l ayer space pr oduced by t he adj acent
t et r ahedr al sheet s favors K fi xat i on, similar t o t hat for hydr ous mi ca; i n t he
FIGURE 2. 3 Model of 2: 1 expandi ng clay vermi cul i te showi ng hydrated
cations (each with six water mol ecul es) in the interlayer space. These cations
are exchangeabl e and move freely i nto and out of the interlayer space. In
effect, the interlayer distance is equal to the thickness of two layers of water
mol ecul es. Dryi ng causes a loss of water and contracti on of the interlayer
distance, and rewetti ng causes reexpansi on. Cation exchange sites also occur
on the exteri or planar surfaces and edges.
22 Ion Exchange
l abor at or y vermi cul i t e can be conver t ed t o hydr ous mi ca by t r eat ment wi t h
a sol ut i on cont ai ni ng a l arge numbe r of K ions. T h e t r eat ment resul t s in
much K fixation, loss of CEC, and collapse of t he layers.
SmectitesBeidellite and Montmorillonite
Smectites ar e 2 : 1 expandi ng clays wi t h significantly less CEC t han vermi cu-
lite and little or no ability t o fi x K. Th e CEC i s about 80 t o 120 me q / 1 0 0 g.
Ver mi cul i t e can be al t er ed i nt o smect i t e by deal umi nat i on, r esul t i ng i n a
loss of lattice char ge. Thi s is a likely means of f or mi ng bei del l i t e, whi ch has
a significant a mount of t et r ahedr al Al. Mont mor i l l oni t e has little if any
t et r ahedr al Al, and its f or mat i on by neogenesi s and persi st ence i s favored
by an envi r onment wi t h l i mi t ed l eachi ng and a soil sol ut i on enr i ched wi t h Si
and Mg. Negat i ve char ge originates i n t he oct ahedr al layer by t he i somor-
phor us subst i t ut i on of Mg
2 +
for Al
3 +
. Smect i t es have small-sized part i cl es, a
l arge surface ar ea, and moder at e t o hi gh pe r ma ne nt CEC. T h e model i n
Fi gur e 2. 3 i s r epr esent at i ve of bot h vermi cul i t e and smect i t e, whi ch ar e
bot h 2 : 1 expandi ng clays wi t h hi gh and pr edomi nat el y pe r ma ne nt char ge.
T h e i nt erl ayer di st ance of t he smect i t es, however , i s highly vari abl e and
may be t wo or mor e t i mes gr eat er t han t hat of vermi cul i t e.
Hydroxy-Al-Interlayered Vermiculite and Smectite
For 2 : 1 expandi ng clays, vermi cul i t e and smect i t e, to f or m and cont i nue to
exist t hey need an envi r onment t hat has little or only moder at el y i nt ensi ve
weat her i ng; pH shoul d be about 6 or mor e , and t her e shoul d be l i mi t ed
l eachi ng, whi ch will keep t he soil sol ut i on enr i ched wi t h Si and Mg. Whe n
t he pH dr ops bel ow 6, t he a mount of Al
3 +
i n sol ut i on i ncreases, and l arge
pol ymer i zed h y d r o x y - Al cat i ons with a hi gh char ge ar e f or med and ar e
st rongl y adsor bed. Pol ymeri zat i on i s enhanced near t he surfaces of clay
part i cl es. St rongl y adsor bed h y d r o x y - Al i s not exchangeabl e, and adsor p-
t i on r educes CEC. T h e smallest pol ymer bel i eved t o be nonexchangeabl e
has a si x- member r i ng st r uct ur e and t he f or mul a Al 6 ( OH) 1 5
3 +
. Adsor pt i on
i n t he i nt erl ayer space causes t he layers t o r emai n per manent l y expanded.
T h e clay becomes nonexpandi ng owi ng t o t he at t r act i on of t he positively
char ged h y d r o x y - Al i nt er l ayer and t he negat i vel y char ged 2 : 1 layers (see
Fi gur e 2. 4).
Hy d r o x y - Al i nt er l ayer i ng i s favored by pH of about 5. 0, t he rel ease of
significant Al by weat her i ng, low cont ent of or gani c mat t er , and f r equent
wet t i ng and dr yi ng of t he soil. T h e h y d r o x y - Al occurs fi rst as islands (as
shown i n Fi gur e 2.4) and i n t i me may form a cont i nuous i nt erl ayer. T h e
clays ar e r ef er r ed t o as 2 : 1 : 1 clays. The y have a CEC r angi ng f r om 10 t o
40 me q / 1 0 0 g and a surface ar ea of 70 t o 150 m
2
/ g , compar abl e t o t hose
of hydr ous mica. Hy d r o x y - Al i nt er l ayer clays have gr eat resi st ance t o
weat her i ng and ar e an i mpor t ant component of bot h moder at el y weat her ed
and intensely weat her ed soils, i ncl udi ng Alfisols and Ultisols and some
Oxisols.
FIGURE 2.4 Model of 2 : 1 : 1 nonexpandi ng hydroxy-Al i nterl ayered
clay showi ng adsorpti on of nonexchangeabl e hydroxy-Al in the inter-
layer space, as islands, which prevents expansi on and contracti on of t he
interlayer space, reduces the cation exchange capacity, and reduces the
mobility of hydrated exchangeabl e cations i nto and out of the interlayer
space. Not i ce the adsorpti on of both nonexchangeabl e hydroxy-Al and
an exchangeabl e, hydrated cation on the upper planar surface.
Kaolinite
Kaolinite readi l y forms by neogenesi s from t he ions rel eased by t he weat h-
er i ng of micas, feldspars, 2 : 1 and 2 : 1 : 1 clay mi neral s, a nd ot her mi neral s.
In an aci d-l eachi ng envi r onment pr ef er ent i al loss of Si rel at i ve t o Al , whi ch
i s called desilication, favors t he f or mat i on of kaol i ni t e. Th e Si : Al r at i o
decreases from about 2 : 1 t o 1: 1 dur i ng t he f or mat i on of kaol i ni t e from
2 : 1 clays. Equat i on 2. 3 r epr esent s t he neogenesi s of kaol i ni t e from or t ho-
clase and t he f or mat i on of soluble silica (silicic acid) and K
+
:
2KAl Si 3 O8 + 2H+ + 9 H2 O =
orthoclase
Al 2 Si 2 O5 ( OH) 4 + 4Si ( OH) 4 + 2K+
kaolinite (2.3)
Kaol i ni t e i s nonexpandi ng and has low CEC, 3 t o 10 me q / 1 0 0 g. Th e r e i s
uncer t ai nt y whet her or not kaol i ni t e may i nher i t some i somor phor us sub-
st i t ut i on char ge. Th e part i cl es have one pl anar surface t hat i s all OH;
however , t he CEC i s general l y due t o depr ot onat i on of edge hydroxyl s
coor di nat ed wi t h Al al ong t he edges and i s pH- de pe nde nt (see Fi gur e 2. 5).
Th e expandi ng clays, by cont rast , may have a 90% pe r ma ne nt char ge and a
10% pH dependent char ge at pH 7. Thes e char ges ar e pr oduced by t he
ext ent of i s omor phor us subst i t ut i on and t he l i mi t ed depr ot onat i on of edge
hydroxyl s.
24 Ion Exchange
FIGURE 2. 5 Model of 1: 1 nonexpandi ng kaolinite showi ng t wo off-
set layers whose upper surfaces are hydroxyl -coordi nated, wi th alumi-
num i n the octahedral sheet. The cation exchange sites occur al ong the
edges, and the hydrated exchangeabl e cation i s shown to be adsorbed
on a site created by the deprotonati on of a hydroxyl coordi nated with
al umi num.
T h e gibbsite st r uct ur e i s similar t o t he Al oct ahedr al sheet of t he
al umi num silicate clays wi t h Al i n sixfold coor di nat i on wi t h OH. Th e
mi ner al is di oct ahedr al wi t h Al occupyi ng t wo of every t hr ee cat i on posi-
t i ons. At t he edges some of t he hydroxyl s ar e not fully coor di nat ed wi t h Al ,
and t he exposed hydr oxyl s depr ot onat e t o cr eat e CEC, or t he hydroxyl s can
pr ot onat e t o pr oduce a positive char ge, dependi ng on pH. Gi bbsi t e i s
crystalline and has relatively little surface ar ea and CEC. A model of gi bb-
site is shown in Fi gur e 2. 6.
In all soils Al and Fe ar e rel eased in weat her i ng, and much of t he Al
ent er s i nt o t he f or mat i on of clay mi neral s al ong with Si, as we have j us t
not ed, and gibbsite f or mat i on i s i nhi bi t ed. Some of t he Al and some Fe exist
as free amor phor us hydr oxi des with idealized formul as of Al ( OH) 3 and
Fe ( OH) 3 . I n soils t he hydr ous oxi des r ange from t hose t hat ar e freshly
f or med and a mor phor us t o t hose t hat have varyi ng degr ees of crystallinity
and a vari abl e composi t i on. T h e Al oxi des t end t o be positively char ged
because of i ncompl et e coor di nat i on of OH wi t h Al i n an acid weat her i ng
envi r onment , and t hei r composi t i on i s r el at ed t o soil p H. T h e Al i s i n six
coor di nat i on, wi t h t he sum of t he OH mol ecul es and H2 O equal t o six. Th e
Al - t o- OH r at i o is commonl y in t he r ange 2. 5 to 2. 7, r esul t i ng in a positive
char ge. Th e positively char ged hydr ous oxi des ar e ads or bed and coat t he
negat i vel y char ged surfaces of layer silicate clays. As a resul t , t he t ot al
negat i ve char ge or CEC of t he silicate clay i s r educed. For clays wi t h
pe r ma ne nt char ge, t he adsor pt i on of an oxi de coat i ng will i ncrease t he
per cent age of char ge or CEC t hat i s pH- dependent . T h e ubi qui t ous pr es-
ence of hydr ous oxi des i n soils causes t he layer silicate clays t o have ex-
change pr oper t i es di fferent from t he ideal. Al umi num and Fe f or m com-
pl exes with or gani c mat t er and, i n an anal ogous manner , decr ease t he CEC
of t he SOM.
T h e amor phor us hydr ous oxi des have gr eat er surface ar ea a nd CECv as
compar ed t o t hei r crystalline count er par t s. Over t i me t hese a mor phor us
mi ner al s ar e conver t ed i nt o crystalline gi bbsi t e, Al ( OH) 3 , and goet hi t e,
F e OOH. Bot h t he amor phor us and crystalline forms ar e oxidic clays. Soils
with a bunda nt gibbsite t end t o have a significant a mount of kaol i ni t e be-
cause t hese t wo clays t end t o f or m near t he end of t he weat her i ng sequence.
Allophane
Allophane is an amor phor us , hydr ous al umi num silicate t hat is f or med by
t he weat her i ng of volcanic ash and ot her amor phor us volcanic mat eri al s. I t
FIGURE 2.6 Model (on right) of dioctahedral gibbsite,
Al ( OH) 3 , showi ng al umi num i n two of every three octahedral
positions. Edge hydroxyl s that are not fully coordi nated with
al umi num can deprotonate to produce cation exchange sites, or
edge hydroxyl s can protonate to create positive charge, depend-
ing on pH. On the left is a model of al umi num in six coordi na-
tion with hydroxyl s.
Depr ot onat i on of edge Si OH gr oups usually occurs at very hi gh pH
and cont r i but es little t o t he CEC,, of most soils. Most of t he vari abl e char ge
of silicate clay comes from t he mor e acidic Al OH gr oups al ong t he
part i cl e edges. Th e hydroxyl s of pl anar surfaces depr ot onat e at t oo hi gh a
pH t o make an i mpor t ant cont r i but i on t o t he char ge of layer silicate clays i n
soils.
Gibbsite and the Oxidic Clays
As l ong as soils cont ai n significant soluble silica, t he f or mat i on of silicate
clay i s favored and t hat of gibbsite i s i nhi bi t ed. Over t i me, however , cont i n-
ued desilication r emoves t he t et r ahedr al sheet s of kaol i ni t e. Kaol i ni t e i s
t hus t r ansf or med i nt o gibbsite:
26 Ion Exchange
is a domi nat e component of soils devel oped from volcanic ash such as
Andept s. Al l ophane has been r epor t ed t o have a hi gh a mount of surface
ar ea per gr am and moder at e t o hi gh pH- de pe nde nt CEC owi ng t o hydr oxyl
depr ot onat i on. Over t i me al l ophane crystallizes i nt o kaol i ni t e wi t h great l y
r educed CEC.
Low- Ac t i v i t y Cl a y Soi l s
In intensely weat her ed soils, Ultisols and Oxisols, t he domi nant clay mi n-
eral s ar e kaol i ni t e and gibbsite or ot her oxi di c clays. Fr equent l y, t he nega-
tive char ge pr oper t i es of t he kaol i ni t e i n t hese soils ar e great l y modi fi ed by
oxidic clays because t hey t end t o coat t he surfaces of kaol i ni t e and mask t he
effects of t he kaol i ni t e. Th e soils domi nat ed by t hese clays wi t h low vari abl e
char ge have been called low-activity clay (LAC) soils. T h e upper limit for t he
CEC of LAC can be consi der ed t o be 16 me q / 1 0 0 g det er mi ned at pH 7.
Thi s is t he upper limit for t he clay fract i on of oxic hor i zons of Oxisols. Soils
domi nat ed by LAC have distinctly di fferent fertility charact eri st i cs and
r equi r e distinctly di fferent soil management pract i ces compar ed t o soils
wi t h a much gr eat er CEC t hat i s mostly pe r ma ne nt char ge. Thes e differ-
ences will be emphasi zed i n t he mat er i al cover i ng i on exchange a nd soil p H.
Pos i t i v e Cha r g e a nd Ze r o Poi nt of Cha r g e
Hydr oxyl r epl acement by ot her ani ons, called l i gand exchange, is a signifi-
cant sour ce of positive char ge or ani on exchange capacity (AEC) of oxi di c
clays. Th e r epl acement i s pH- de pe nde nt and i ncreases with i ncreasi ng acid-
ity or decr easi ng p H. Thus , AEC i s r el at ed t o bot h t he ext ent of l i gand
exchange and t he pr ot onat i on of exposed hydroxyl s, whi ch ar e bot h pH-
dependent . In most soils AEC i s mi nor , however ; soil wi t h a bunda nt goet h-
ite and gi bbsi t e may have a CEC-t o-AEC r at i o appr oachi ng 1.0, as do some
oxic hor i zons or subsoils of Oxisols. T h e CEC and AEC of some clay
mi neral s r ecover ed from a soil ar e given i n Tabl e 2. 1.
If i ncreasi ng acidity causes a decr ease i n t he negat i ve char ge and an
i ncrease in positive char ge, t heoret i cal l y, a soil can have a zer o poi nt of
char ge (ZPC) wher e t he AEC and t he CEC ar e equal . I n most soils t he CEC
great l y exceeds t he AEC. In some t he subsoil or oxic hor i zon of Oxisols
may cont ai n little or gani c mat t er and have little negat i ve char ge cont r i b-
ut ed by SOM, r esul t i ng i n a net char ge of zer o or a small positive char ge.
Su mma r y St a t e me nt
Th e negat i ve char ge of soils i s st rongl y associated with t he SOM and clay
mi neral s. Th e char ge i s part l y pH- dependent and vari abl e (CECv ) and i s
usually caused by hydr oxyl depr ot onat i on; par t of t he char ge i s pe r ma ne nt
(CECp), owi ng t o i somor phor us subst i t ut i on. In summar y,
1. Soil or gani c mat t er has hi gh CECv .
Cation Exchange Capacity of Soils 27
Montmorillonite 112 6 118 1
Vermiculite 85 0 85 0
Hydrous mica 11 8 19 3
Kaolinite 1 3 4 2
Gibbsite 0 5 5 5
Goethite 0 4 4 4
Allophanic colloid 10 41 51 17
Source: Data on Kenya soils adapted from Sanchez, 1976.
2. T h e 2 : 1 and 2 : 1 : 1 clays t end t o have moder at e t o hi gh CECp and low
CECv .
3. Kaolinitic clay has low CECv a nd al l ophane has hi gh CECv .
4. Oxi di c clays have low CECv .
5. T h e ion exchange pr oper t i es of layer silicate clays i n soils ar e modi fi ed
by coat i ngs of oxi di c clays.
6. Accor di ng t o t he concept of a mi ner al - weat her i ng sequence, t he CEC of
mi ner al soils t ends t o i ncrease unt i l soils become moder at el y weat her ed
and t he clays ar e pr edomi nat el y 2 : 1 expandi ng t ypes. Th e n t he CEC
decreases to a mi ni mum in i nt ensel y weat her ed soils, such as Ultisols and
Oxisols, whi ch ar e domi nat ed by kaol i ni t e and oxi di c clays (LAC).
7. T h e CEC and AEC appr oach equal i t y as t he pH appr oaches t he zer o
poi nt of char ge i n t he most weat her ed soils, t he Oxi sol s.
C A T I O N EX C H A N G E C A P A C I T Y O F SOI L
Th e CEC of soils i s mai nl y a funct i on of t he a mount and ki nd of clay and
SOM, t hei r i nt er act i on, and soil p H. A soil may occasionally have some clay
mi ner al s i n t he silt fract i on or cont ai n some silt-sized mi caceous mi ner al s
t hat have a significant effect on t he CEC.
Rol e of Or g a ni c Mat t e r a nd Cl a y
A st udy of t he A and B hor i zons of five Cher nozemi c soils or Mollisols on
t he Gr eat Plains of west er n Canada showed t hat t he aver age CEC of t he
clay was 57 me q / 1 0 0 g wi t h a r ange of 55 t o 59. Th e SOM had an aver age
CEC of 250 with a r ange of 214 t o 297. In bot h t he CEC was det er mi ned at
pH 7. Th e dat a i ndi cat ed similar clays i n bot h hor i zons, but t he SOM was
mor e decomposed and had gr eat er CEC i n t he B as compar ed t o t he A
TABLE 2.1 Charge Characteristics of Some Materials Removed from Kenya
Soils
Anion
Cation exchange exchange
capacity, me q / l 0 0 g capacity,
Material Permanent Variable Total me q / l 0 0 g
28 Ion Exchange
hor i zon. Assumi ng t hat t he CEC of t he clay i s 57 and of t he SOM i s 250, an
A hor i zon wi t h 20% clay and 4% or gani c mat t er woul d have a CEC of 21. 4
me q / 1 0 0 g. About half of t he CEC i s due t o t he clay and about half t o t he
SOM. For a B hor i zon wi t h 30% clay and 1% or gani c mat t er , t he est i mat ed
CEC woul d be 19. 6, wi t h 87% at t r i but abl e t o t he clay and only 13% t o t he
SOM.
Histosols commonl y have a CEC bet ween 100 a nd 200 me q / 1 0 0 g.
Thi s does not mean, however , t hat pl ant r oot s have many t i mes mor e CEC
in a given vol ume of r oot envi r onment t han do mi ner al soils. A ki l ogr am of
an or gani c soil may r epr es ent a vol ume t hat i s t en or mor e t i mes l ar ger t han
t hat filled by a ki l ogr am of mi ner al soil. Thus , it is useful to compar e t he
CEC on a wei ght and vol ume basis as shown i n Tabl e 2. 2. Th e dat a i n t he
t abl e reflect bot h a gr eat er CEC and bul k densi t y of muck as compar ed t o
t hose of peat . On a vol ume basis, about t he same a mount of lime i s r equi r ed
for a l oam soil and for woody peat to make a similar change in cal ci um
sat ur at i on of t he CEC. Muck soils, however , r equi r e about four t i mes mor e
lime per uni t vol ume of soil t han do l oamy soils.
T he Ef f e c t i ve Ca t i on Ex c ha ng e Ca pa c i t y
T h e CEC of soils has typically been det er mi ned at pH of 7.0 or 8. 2,
dependi ng on t he met hod. Det er mi nat i on of t he CEC at t he soil' s cur r ent
or nat ur al pH i s called t he effective CEC, ECEC. Th e ECEC mor e accurat el y
reflects condi t i ons encount er ed by pl ant r oot s t han does t he CEC det er -
mi ned at some st andar di zed pH such as 7 or 8. 2.
An ext ensi ve st udy was made of t he rel at i on bet ween t he CEC and t he
pH of t he Ap hor i zons of 60 Mollisols and Alfisols i n Wi sconsi n. Th e soils
aver aged 13. 3% clay, whi ch can be expect ed t o consist mostly of 2 : 1 t ypes
plus lesser amount s of 2 : 1 : 1 clay and mi nor amount s of hydr ous oxi des
(oxidic clay). Th e SOM aver aged 3. 38%. Th e st udy cover ed t he pH r ange
from 2. 5 t o 8. 0, but since soils sel dom have a pH less t han 3. 5, t he dat a i n
Fi gur e 2.7 cover t he r ange of about 3.5 t o 8. 0. As soil pH i ncreases, t he
CEC of bot h t he clay and t he SOM i ncreases wi t h t he SOM showi ng t he
l argest i ncrease. At pH 3.5 t he CEC was 8. 58 me q / 1 0 0 g wi t h 7 1 % of t he
TABLE 2. 2 Comparison of Cation Exchange Capacity on a
Weight and a Volume Basis
Cation exchange capacity
Weight basis, Volume basis,
Soil meq/ 100 g meq/ 100 cc
Loam, mineral soil 12 14
Sphagnum peat 100 8
Woody peat 90 14
Muck 200 60
Source: Data from Lucas, 1982.
Ion Distribution near Cation Exchange Surfaces 29
FIGURE 2. 7 The average source of neg-
ative charge in 60 Wisconsin soils. (Data
from Hel l i ng, Chesters, and Corey,
1964. )
CEC cont r i but ed by t he clay and 29% by t he SOM. At pH 8.0 t he CEC was
14. 8 wi t h 54% of t he CEC cont r i but ed by t he clay and 46% by t he SOM.
Li mi ng soils i ncreases soil pH, whi ch i n t ur n i ncreases t he CEC.
I O N D I S T R I B U T I O N N EA R C A T I O N
EX C H A N G E SU R F A C ES
T h e soil part i cl es ar e s ur r ounde d by wat er f i l ms t hat cont ai n hydr at ed
cat i ons a nd ani ons whi ch ar e i n const ant mot i on. As a cat i on r andoml y
appr oaches t he surface wher e a negat i ve char ge i s l ocat ed, t he closer t he
cat i on appr oaches t o t he surface, t he mor e st rongl y i t i s at t r act ed. Out wa r d
from t he surface t he st r engt h of t he negat i ve char ge decreases very rapi dl y
wi t h i ncreasi ng di st ance. Wi t hi n a cer t ai n spher e or vol ume t hat i s cent er ed
on t he char ged site, t he cat i on moves or oscillates but i s unde r t he i nfl uence
of t he negat i ve char ge and i s consi der ed t o be an ads or bed or exchangeabl e
cat i on. Whe n an ads or bed cat i on i s at t he ext r emi t y of t he spher e of char ge
i nfl uence and anot her cat i on from t he sol ut i on moves i n behi nd it, t he
ads or bed cat i on will be exchanged and t hen become a cat i on i n sol ut i on.
Th e r e i s no shar p line of demar cat i on, however , bet ween cat i ons consid-
er ed ads or bed or exchangeabl e a nd t hose i n sol ut i on.
Th e r api d decl i ne i n t he st r engt h of t he negat i ve char ge as its di st ance
from t he exchange surface i ncreases causes t he ads or bed cat i ons t o concen-
t r at e near t he surface. Th e concent r at i on of cat i ons decreases rapi dl y wi t h
i ncreasi ng di st ance from t he surface. T h e negat i ve- char ged exchange sur-
faces r epel ani ons. T h e net effect i s t o pr oduce an i on di st r i but i on as shown
i n Fi gur e 2. 8. T h e net char ge of t he system i s zer o wi t h t he negat i ve char ge
of t he CEC pl us t he ani ons count er bal anci ng t he positive char ge of t he
cat i ons and t he AEC.
30 Ion Exchange
FIGURE 2. 8 Distribution of cations and ani ons
near the vicinity of a negatively charged surface.
C HA R A C T ER I S T I C S O F C A T I O N
EX C H A N G E R EA C T I O N S
I n gener al , cat i on exchange react i ons ar e r api d, reversi bl e, and st oi chi ome-
t eri c and obey t he mass act i on law. Th e gr eat er t he concent r at i on of any
cat i on, t he mor e likely i s t he cat i on t o cause desor pt i on of compet i ng
cat i ons and be adsor bed.
Ef f ect s of Va l e nc e a nd Hy d r a t i on
Val ence is t he maj or fact or affecting t he l i kel i hood t hat a cat i on will be
adsor bed on colloid surfaces. A t ri val ent i on like Al
3 +
i s mor e st rongl y
adsor bed t han Ca
2 +
, whi ch i s mor e st rongl y adsor bed t han K
+
. I t r equi r es
t wo K ions t o r epl ace one Ca i on. Di val ent cat i ons ar e hel d wi t h about twice
t he ener gy as monoval ent cat i ons. For cat i ons of similar val ence, t he smal l er
cat i on will have t he gr eat er char ge densi t y per uni t vol ume and, t her ef or e,
at t r act mor e wat er mol ecul es. The s e at t r act ed wat er mol ecul es cause t he
hydr at ed r adi us of a smal l er cat i on t o be l ar ger t han t he hydr at ed r adi us of
a l ar ger cat i on. For this r eason Ca i s mor e st rongl y adsor bed t han Mg and K
i s mor e st rongl y adsor bed t han Na. Th e gener al or der of selectivity or
repl aceabi l i t y of some i mpor t ant hydr at ed exchangeabl e cat i ons i s Al
3 +
>
C a
2 +
> Mg
2 +
> K
+
= NH4 + > Na
+
.
Comp l i me nt a r y I on Ef f ect s
Exchange of one cat i on for anot her , i n t he pr esence of a t hi r d or compl i -
ment ar y cat i on, i s easi er i f t he compl i ment ar y cat i on has gr eat er val ence or
ener gy of adsor pt i on. Dur i ng upt ake of cat i ons by r oot s, t he r oot excr et es
H
+
, whi ch i s monoval ent and weakly adsor bed. Thus , when t he H
+
diffuses
t o t he colloid surfaces, i t i s mor e likely t o exchange K
+
t han C a
2 +
i f t he soil
i s acid and many t ri val ent Al
3 +
ions ar e adsor bed. By cont rast , t he H
+
woul d
less likely exchange for K
+
t han C a
2 +
unde r t he following condi t i ons: (1) i f
Exchangeable Cation Suites 31
t he soil was al kal i ne, and (2) i f t her e was no exchangeabl e Al , (3) but much
exchangeabl e Mg and Na as t he compl i ment ar y cat i ons. In effect, as soils
become mor e acid and i ncrease i n exchangeabl e Al bel ow pH 5. 5, t he
exchangeabl e K i s mor e likely t o be i n sol ut i on or t o be mor e avai l abl e. T h e
i mmedi at e effect i s good because t hese soils t end t o be low i n exchangeabl e
K. However , t he l ongt i me effect is gr eat er l eachi ng of K.
Uni q u e Ca t i on Se l e c t i vi t i e s
Cat i on selectivity i s somet i mes affected by uni que space and char ge envi-
r onment s . T h e gr eat er t he char ge densi t y per uni t of surface ar ea, t he
gr eat er t he pr ef er ence for cat i ons of hi gher val ence or ener gy of adsor p-
t i on. Ver mi cul i t e has gr eat er surface char ge densi t y t han mont mor i l l oni t e
a nd preferent i al l y adsor bs mor e C a
2 +
rel at i ve t o Na
+
from a mi xed sol ut i on
t han does mont mor i l l oni t e. Hydr at ed Mg ions f i t well i nt o t he wat er net -
wor k bet ween partially expanded layers of vermi cul i t e, r esul t i ng i n prefer-
ent i al adsor pt i on of Mg over Ca, especially when Mg i s fairly abundant . Th e
weat her ed edges of micas, whi ch become hydr ous mica, cont ai n voi ds t hat
can collapse a r ound a K ion and fix it so t hat it is no l onger exchangeabl e.
Such K fixation is enhanced by t he easy loss of hydr at i on wat er bef or e ent r y
of K
+
i nt o t he voids. Thi s process i s t he r ever se of weat her i ng and occurs
when K fertilizers ar e used. T h e st r ong adsor pt i on of l arge hydroxy-Al
cat i ons bet ween t he layers of 2 : 1 expandi ng clay mi ner al s pr event s i nt er-
layer collapse and decreases K fi xat i on and cat i on adsor pt i on i n t he i nt er-
layer space.
EX C H A N G EA B LE C A T I O N SUI T ES
T h e compl i ment of exchangeabl e cat i ons or t he exchangeable cation suite of
nat ur al soils i s a funct i on of t hei r par ent mat er i al and t he changes t hat
occur r ed dur i ng t hei r genesis. T h e domi nant exchangeabl e cat i ons ar e Al ,
Ca, Mg, K, and Na. An exchangeabl e cat i on i s wr i t t en wi t h an X bef or e t he
i on. For exampl e, XA1 means exchangeabl e Al and XMg means exchange-
abl e Mg. Fur t her , XAL..Na refers t o t he fi ve domi nant exchangeabl e cat-
ions (Al, Ca, Mg, K, Na) , and t hei r sum in mi l l i equi val ent s per 100 g is
equat ed t o t he CEC. Whe n XCa. . Na i s used, i t refers t o exchangeabl e Ca,
Mg, K, and Na (also called exchangeabl e bases). Since exchangeabl e cat i ons
r epr esent t he maj or available suppl y of many pl ant nut r i ent s, t hei r absol ut e
and rel at i ve amount s ar e i mpor t ant i n affecting pl ant gr owt h.
Ca l c a r e ous Soi l s
Young soils i nher i t from t he par ent mat eri al a par t i cul ar chemi cal and
mi neral ogi cal composi t i on, i ncl udi ng t he clay mi ner al sui t e, t he exchange-
abl e cat i on sui t e, and pH. Many par ent mat eri al s ar e cal careous and cont ai n
32 Ion Exchange
an abundance of Ca CO3 a nd smal l er amount s of ot her salts. Fr om t he
dissolution of t he salts come t he cat i ons for adsor pt i on. As salts dissolve, t he
cat i ons ent er i ng sol ut i on ar e at t r act ed t o t he exchange sites usually accord-
i ng t o val ence and mass act i on. Except for very small amount s of mi cr onu-
t r i ent cat i ons a nd some N H 4
+
, i t i s t he Ca, Mg, K, a nd Na i ons t hat
domi nat e t he exchange sites. The i r abundances paral l el t he ener gy of
adsor pt i on sequence, wi t h Ca t he most a bunda nt a nd Na t he least. Th e
CEC of a cal careous C hor i zon devel oped from loess in Iowa was r epor t ed
t o be sat ur at ed 67% by Ca, 30% by Mg, 2% by K, and 1% by Na. T h e
exchangeabl e Ca pl us Mg pl us K and Na, or XCa. . Na, as mi l l i equi val ent s
per 100 g i s equal t o t he CEC and t he soil i s 100% XCa. . Na sat ur at ed. T h e
pH of cal careous soils i s i n t he r ange 7.5 t o 8. 3.
Cal careous soils ar e c ommon wher e young soils have f or med from
cal careous par ent mat er i al . The y ar e pr eval ent i n ar i d and s ubhumi d r e-
gi ons because l eachi ng of car bonat e salts i s l i mi t ed, a nd t he Ca r el eased by
weat her i ng f or ms car bonat e.
Ac i d Soi l s
Leachi ng of cal careous soils r emoves t he car bonat e, sulfate, and chl or i de
salts of Ca, Mg, K, and Na. Addi t i onal l eachi ng resul t s i n t he progressi ve
r emoval of XCa. . Na and i ncreasi ng adsor pt i on of hydr oxy- Al . Below pH
5. 5, adsor pt i on of Al
3 +
(XA1) becomes significant. T h e pe r ma ne nt char ge
i n aci d soils becomes i ncreasi ngl y al umi num- sat ur at ed. Mor e discussion of
t he exchangeabl e cat i on sui t e of acid soils is given in Chapt er 3.
Sa l i ne a nd Sodi c Soi l s
Saline soils cont ai n salts mor e sol ubl e t han t he car bonat e salts f ound i n
cal careous soils. I n ar i d and s ubhumi d r egi ons, wat er moves from one par t
of t he l andscape t o anot her , dependi ng on t opogr aphy. I n some par t s of t he
l andscape, runoff wat er collects i n depressi ons and forms ponds . Subse-
quent l y, wat er evapor at es a nd t he salts t hat wer e i n t he wat er ar e deposi t ed.
T h e upwar d movement of wat er f r om a shallow wat er t abl e t o t he soil
surface may also cause wat er t o evapor at e and salts t o deposi t . Since t he
most soluble salts ar e moved t o t he great est ext ent , soils may become saline
from t he infusion of sol ubl e salt. Saline soils have sufficient sol ubl e salt to
i mpai r pl ant gr owt h.
T h e exchangeabl e cat i on sui t e of saline soils i s hi ghl y vari abl e, depend-
i ng on t he a mount and ki nd of salts. Sodi um salts ar e t he most sol ubl e, and
t hei r preferent i al accumul at i on over t i me may resul t i n over 15% XNa and
t he format i on of sodic soils. T h e st r uct ur e of sodic soils t ends t o di si nt egr at e
because Na i s weakly adsor bed and i s inefficient i n neut r al i zi ng t he negat i ve
char ge. T h e di spersi on of clays and humus great l y r educes per meabi l i t y
and tilth. Wi t h t he addi t i on of gypsum, Ca SO4 2 H2 O, and t he l eachi ng of
sodic soils, Na i s desor bed by Ca and r emoved, and t he soil becomes
nonsodi c.
Exchangeable Cations as a Source of Plant Nutrients 33
Se r p e nt i ne Soi l s
T h e mi neral ogi cal uni queness of t he par ent mat er i al somet i mes gives soils
an unusual exchangeabl e cat i on sui t e. Thi s i s t he case wi t h soils t hat have
devel oped from ser pent i ne par ent mat eri al s. Ser pent i ne mi ner al s have a
1 : 1 st r uct ur e similar to kaol i ni t e and cont ai n consi der abl e i s omor phor us
Mg and Fe. Weat her i ng releases l ar ge amount s of Mg rel at i ve t o t he ot her
cat i ons. Mont mor i l l oni t e i s a c ommon clay f or med f r om ser pent i ne
weat her i ng.
Four soils f or med from ser pent i ni t e rock i n California wer e f ound t o
have C a nd Cr hor i zons wi t h aver age exchangeabl e cat i on rat i os (in milli-
equi val ent s) of Ca : Mg : K: Na of 2 6 : 4 1 0 : 1 : 1 . T h e A hor i zons wer e mor e
weat her ed and l eached, but even so, t hey had hi gh i mbal ance of Mg rel at i ve
t o Ca for pl ant gr owt h, wi t h rat i os of 6 1 : 1 7 4 : 3 : 1 , respect i vel y. Most
pl ant s cannot t ol er at e a cat i on sui t e t hat is part i cul arl y unbal anced in Ca
a nd Mg. Cal ci um deficiencies ar e common. Lands wi t h ser pent i ne soils have
unusual floras and sparse pl ant gr owt h a nd ar e r ef er r ed t o as serpentine
barrens. Ser pent i ne soil mat eri al s exposed by mi ni ng ar e very difficult to
r eveget at e.
In s ummar y, we can st at e t hat
1. Soils devel op from a wi de vari et y of par ent mat eri al s and have gr eat
vari at i on i n degr ee of devel opment . T h e exchangeabl e cat i on sui t e,
however , shows muc h less variability.
2. T h e or de r of exchangeabl e cat i ons is Ca > Mg > K > Na in most soils
wi t h a pH of 5.5 or mor e . Except i ons occur i n sodi c a nd ser pent i ne soils;
i n sodic soils Na may domi nat e t he exchange, and i n ser pent i ne soils Mg.
3. Al umi num becomes an i mpor t ant exchangeabl e cat i on bel ow pH 5.5
a nd i ncreases i n abundance as soil pH decl i nes.
EX C H A N G EA B LE C A T I O N S AS A S OU R C E
O F P LA N T N U T R I EN T S
I n gener al , t he gr eat er t he a mount of an exchangeabl e cat i on, t he gr eat er
its concent r at i on i n t he soil sol ut i on. As a consequence, t he exchangeabl e
cat i ons r epr esent an available supply of Ca, Mg, K, and Na for meet i ng t he
i mmedi at e needs of pl ant s. It has been ment i oned t hat a cal careous C
hor i zon devel oped from loess i n west er n Iowa had a CEC t hat was 67%,
30%, 2%, and 1% sat ur at ed wi t h Ca, Mg, K, a nd Na, respect i vel y. T h e soil
has a CEC of 16 me q / 1 0 0 g. We will consi der next t he adequacy of such
soil for suppl yi ng t he annual needs of crops.
Th e dat a in Tabl e 2. 3 show t hat a layer of soil about 7 or 8 i nches t hi ck
(20 cm) woul d cont ai n e nough exchangeabl e Ca t o meet t he needs of
pr oduct i ve cr ops for 86 years. For Mg a nd K t he suppl y woul d last 38 and
34 Ion Exchange
TABLE 2.3 Amounts of Exchangeable Cations versus Plant
Needs
Cation
Furrow Slice
pounds/ acre kg/ ha Supply,* years
Ca
Mg
K
4 280
1 152
234
4 798
1 291
262
86
38
1.2
*Based on an average value of the annual uptake of producti ve
crops and data for Ida silt l oam, as reported in Soil Survey Investi-
gations Report 3, USDA, 1966.
1.2 years, respectively. T h e soil can be expect ed t o suppl y t he Ca and Mg
needs for many years because weat her i ng const ant l y rel eases addi t i onal Ca
and Mg. On t he ot her hand, t he l arge annual de ma nd for K and t he low
exchangeabl e suppl y rel at i ve t o annual r equi r ement s means t hat K fertilizer
i s likely t o be needed each year t o pr oduce hi gh yields. Th e very small
amount s of exchangeabl e Fe, Mn, Cu, and Zn ar e also i mpor t ant i n meet i ng
t he nut r i t i on needs of pl ant s and mi cr oor gani sms. Thus , i t i s difficult t o
over emphasi ze t he i mpor t ance of t her e bei ng exchangeabl e cat i ons i n soils
to serve as a sour ce of pl ant nut r i ent s.
A N I O N EX C H A N G E
T h e pH i s hi gh enough i n most agri cul t ural soils t hat t he CEC i s much
gr eat er t han t he AEC. As soils become mor e acid and mor e domi nat ed by
low-activity clays, t he CEC decreases and t he AEC i ncreases. Aci d soils
domi nat ed by oxi di c clays may have AEC about equal t o, and i n r ar e cases,
gr eat er t han, t he CEC. Positive char ge ori gi nat es from pr ot onat i on of
hydroxyl s and by l i gand exchange or t he r epl acement of hydroxyl s by ot her
ani ons. A r ecent r epor t i ndi cat es t hat t her e can be positive pe r ma ne nt
char ge i n oxi di c clay t hr ough t he i s omor phor us subst i t ut i on of T i
4 +
for
F e
3 +
. Ni t r at e and chl or i de ions ar e very weakly adsor bed and readi l y leach
from soils. Phos phat e ions i nvol ved i n l i gand exchange ar e so st rongl y
adsor bed t hat t hey ar e fi xed. Sulfate adsor pt i on i s i nt er medi at e.
REF ERENCES
Allen, B. L. and D. S. Fanning. 1983. Composition and Soil Genesis. In Pedogensis
and Soil Taxonomy, Vol. 1. L. P. Wilding, N. E. Smeck, and G. F. Hall, eds.
Elsevier, Amsterdam.
Barnhisel, R. I. 1977. Chlorites and Hydroxy Interlayered Vermiculite and Smec-
tite. In Minerals in the Soil Environment. Soil Sci. Soc. Am., Madison, Wis.
Barrow, N. J. 1985. Reactions of Anions and Cations with Variable Charge Soils.
Advances in Agronomy. 38: 183- 228.
Bohn, H. L., B. L. McNeal, and G. A. O' Connor. 1985. Soil Chemistry. 2nd ed. John
Wiley, New York.
References 35
Douglas, L. A. 1977. Vermiculites. In Minerals in the Soil Environment. Soil Sci. Soc.
Am., Madison.
Fanning, D. S. and V. Z. Keramidas. 1977. Micas. In Minerals in the Soil Environ-
ment. Soil Sci. Soc. Am., Madison.
Helling, C. S., G. Chesters, and R. B. Corey. 1964. Contribution of Organic Matter
and Clay to Soil Cation - Exchange Capacity as Affected by the pH of the
Saturating Solution. Soil Sci. Soc. Am. J. 28: 517- 520.
Jenny, Hans. 1980. The Soil Resource. Springer-Verlag, New York.
Keng, J. C. W. and G. Uehara. 1973. Chemistry, Mineralogy, and Taxonomy of
Oxisols and Ultisols. Soil and Crop Sci. Soc. Florida. 33: 119- 126.
Lucas, R. E. 1982. Organic Soils (Histosols). Research Report 435, Mich. Agr. Exp.
Sta., East Lansing.
Sanchez, P. A. 1976. Properties and Management of Soils in the Tropics. John Wiley,
New York.
Smith, R. F. and B. L. Kay. 1986. Revegetation of Serpentine Soils: Difficult But
Not Impossible. California Agriculture. 40: 18- 19.
Soil Survey Staff. 1975. Soil Taxonomy. USDA Agriculture Handbook 436, Wash-
ington, D.C.
St. Arnaud, R. J. and G. A. Septon. 1972. Contribution of Clay and Organic Matter
to Cation-Exchange Capacity of Chernozemic Soils. Can. four. Soil Sci.
52: 124- 126.
Tessens, E. and S. Sauyah. 1982. Positive Permanent Charge in Oxisols. Soil Sci. Soc.
Am. four. 46: 1103- 1106.
Thomas, G. W. 1977. Historical Developments in Soil Chemistry: Ion Exchange.
Soil Sci. Soc. Am. four. 41: 230- 238.
Thomas, G. W. and W. L. Hargrove. 1984. The Chemistry of Soil Acidity. In Soil
Acidity and Liming. Agronomy 12: 1- 56. Am. Soc. Agron., Madison, Wis.
Thompson, H. S. 1850. On the Absorbent Power of Soils, four Royal Agric. Soc
Engl. 11: 68- 74.
Wildman, W. E., M. L.Jackson, and L. D. Whittig. 1968. Iron Rich Montmorillon-
ite Formation in Soils Derived from Serpentinite. Soil Sci. Soc. Am. Proc.
32: 787- 794.
C H A P T E R 3
Soil pH and Its Management
Soil pH is an i ndi cat or of soil acidity and basicity. Most soils have a pH in
t he r ange of 4 to 10. T h e pH of a par t i cul ar soil, such as 5 or 8, reflects a
cer t ai n chemi cal and mi neral ogi cal envi r onment i n t hat soil, a nd t hus t he
pH i s of gr eat i mpor t ance t o pl ant r oot s and mi crobi al activity. For t hese
reasons soil pH i s one of t he most i mpor t ant factors affecting soil fertility
and so i s commonl y managed t o i ncrease cr op yields.
p H D EF I N ED
Chemi cal l y, t he pH i s an expressi on of t he H i on activity, ( H
+
) . Hydr oge n
ions hydr at e similarly t o ot her cat i ons i n t he soil sol ut i on. T h e wat er
mol ecul es of hydr at i on ar e not shown for simplicity. In sol ut i ons wi t h low
ionic concent r at i ons, t he activity of ions appr oaches t he mol ari t y, al l owi ng
mol ar concent r at i on t o be i nt er changeabl e wi t h activity i n t he following
discussion. T h e pH scale was devi sed t o simplify t he expressi on of ( H
+
) and
i s t he l ogar i t hm of t he reci procal of t he ( H
+
) or H i on concent r at i on:
36
Determination of Soil pH 37
Th e pH of wat er i s 7 because of t he degr ee of dissociation or i oni zat i on of
wat er . Wat er ionizes as
H2O = H
+
+ O H - (3. 5)
T h e i oni zat i on const ant Kw, at 25 degr ees C, i s
Kw = ( H+) ( OH- ) = 1 0
- 1 4
(3. 6)
Si nce t he i oni zat i on of each mol ecul e of wat er pr oduces one H
+
a nd one
O H
-
, t he activity of each i on i s t he same. Th u s
Kw = 1 0
7
X 1 0
- 7
= 1 0
- 1 4
(3.7)
I n s ummar y,
1. T h e effective concent r at i on or mol ar activities of H
+
and OH
i n nor -
mal or pur e wat er i s 1 0
- 7
or 0. 0 0 0 0 0 0 1, a nd t he pH i s 7. 0.
2. Whe ne ve r t he concent r at i on or activity of H
+
i ncreases, t hat of t he s o i l -
decreases, and vice versa, t o mai nt ai n t he equi l i br i um const ant .
D ET ER MI N A T I O N O F SOI L p H
Soil pH i s commonl y det er mi ned i n t he Uni t ed States by mi xi ng soil and
wat er t oget her in a 1: 1 r at i o. Fifty gr ams of ai r-dry soil t hat has passed a
2- mm screen is pl aced in a 100-ml beaker , and 50 ml of distilled wat er is
added. Th e soil and wat er ar e st i r r ed occasionally for an hour . Th e n t he
pH of t he sl urry i s det er mi ned wi t h a glass el ect r ode and pH met er while
t he sl urry i s st i rred. Th e r e ar e i nexpensi ve kits t hat use i ndi cat or dyes t o
det er mi ne soil p H. The s e ar e accur at e t o about a half pH uni t , whi ch i s
sufficiently accur at e t o diagnosis many soil-fertility-related pl ant gr owt h
pr obl ems i n t he f i el d.
Several factors affect t he det er mi nat i on of soil p H. Th e concent r at i on
of H
+
near t he exchange surfaces may be 100 t o 1 000 t i mes gr eat er t han i n
t he bul k sol ut i on. If a s oi l - wa t e r suspensi on i s al l owed t o settle, t he pH as
meas ur ed i n t he s uper nat ant liquid will be hi gher t han i n t he sedi ment
l ayer. Because t he pH val ue i s affected by t he ext ent t o whi ch t he cal omel
el ect r ode encount er s clay and humus part i cl es, t he pH of t he st i r r ed suspen-
sion is measur ed.
Two ot her factors i mpor t ant l y affect t he pH val ue of soils: t he s oi l -
wat er r at i o and t he pr esence of salts. An i ncrease i n each causes pH val ues
t o l ower. I n gener al , t he mor e wat er a dde d t o a gi ven a mount of soil, t he
gr eat er t he di l ut i on of t he H
+
, r esul t i ng i n an i ncrease i n p H.
T h e soluble-salt cont ent of t he soil can affect t he pH val ue, and this
may be over come by usi ng CaCl 2 or KC1 sol ut i ons i nst ead of distilled wat er .
Wh e n salt sol ut i ons i n t he r ange of 0. 07 t o 1 M ar e used, soil pH val ues may
be 0. 5 t o 1.5 uni t s l ower t han when t hey ar e meas ur ed wi t h distilled wat er .
T h e cat i ons from salt sol ut i ons effectively put XA1
3 +
(and per haps some
XH
+
) i n sol ut i on al ong wi t h some hydr oxy- Al , dependi ng on t he degr ee of
soil acidity. Subsequent hydrolysis of t he exchangeabl e Al
3 +
a nd hydr oxy-
wher e ( H
+
) i s H
+
i n mol es per liter, or
p H = - l o g ( H
+
) (3.2)
T h e pH of nor mal or pur e wat er i s 7.0 cal cul at ed as follows:
or
p H = l og 1 0
- 7
= ( 7) = 7 (3.4)
38 Soil pH and Its Management
Al cont r i but es t o an i ncrease of sol ut i on H
+
(see equat i ons 3. 14 and 3. 15).
Soils with a net positive char ge, however , will have a hi gher pH when KC1
sol ut i ons ar e used, for hydr oxyl ions ar e r epl aced by t he chl or i de ions.
Whe n t he pH values of vari ous soils ar e compar ed, i t i s i mpor t ant t hat
t hey wer e det er mi ned by t he same met hod. T h e KC1 met hod i s popul ar i n
t ropi cal areas; i n t he t ropi cs t he values have been used t o est i mat e lime
needs. Soil pH values det er mi ned wi t h wat er ar e popul ar i n t he Uni t ed
St at es. It must be real i zed, however , t hat t he pH of an ai r-dry soil sampl e i n
t he l abor at or y will be di fferent from t he pH t hat exists i n t he same soil i n
t he f i el d dur i ng t he gr owi ng season. Th e r e will be differences i n wat er and
salt cont ent , and r oot s and mi cr oor gani sms will pr oduce C O2 .
T H E SOI L p H C ONT I NUUM
Many par ent mat eri al s and young soils ar e al kal i ne, but ol d and i nt ensel y
weat her ed soils ar e typically acid. Thi s change i n soil pH i s r el at ed t o and
parallels t he changes i n t he mi neral ogi cal and chemi cal pr oper t i es t hat
occur over t i me, as discussed i n Chapt er 2. A numbe r of maj or processes
account for t he devel opment of soil acidity: t he loss of any l i me (essentially
Ca CO3 ) t hat may have been i n t he par ent mat er i al , t he loss of XCa. . Na by
l eachi ng, t he nat ur al i nput s of acidity from preci pi t at i on, nitrification, S
oxi dat i on, t he pr oduct i on of CO2 , and t he accumul at i on of hydr oxy- Al ,
Al -organi c compl exes, and XA1. Weat her i ng of pr i mar y mi neral s i s t he
maj or cont r i but or t o alkalinity t hr ough consumpt i on of H
+
and pr oduct i on
of O H
-
and t he rel ease of Ca
2 +
, Mg
2 +
, K
+
, a nd Na
+
.
Al k a l i ne Soi l s
Sodic soils have 15% or mor e of XNa, and soil pH i s cont r ol l ed by t he
hydrolysis of XNa, of Na salts, or of bot h t o pr oduce a pH i n t he r ange of
8.5 t o about 10. For exampl e,
Na 2 C O3 + H2 O = 2Na+ + H C O 3 - + OH
(3.8)
Whe n soils ar e calcareous and cont ai n a few per cent or mor e of Ca CO3 ,
hydrolysis of Ca CO3 pr oduces OH
in a process similar to t hat shown in

equat i on 3. 8. Th e slow r at e of dissolution of Ca CO3 pr oduces fewer O H
-
i n
cal careous soils as compar ed t o sodic soils. Thi s means t hat cal careous soils
have a maxi mum pH of about 8.3 when t hey ar e i n equi l i br i um wi t h t he
nor mal CO2 cont ent of t he at mos pher e. Th e di ssol ut i on of CO2 rel eased by
r espi r i ng r oot s and mi cr oor gani sms can pr oduce sufficient car boni c acid t o
f or m local pocket s of acidity in al kal i ne soils.
Nitrification, S oxi dat i on, and ot her processes cont i nual l y pr oduce H
+
.
Th e pr eci pi t at i on i s nat ural l y acidic when i n equi l i br i um wi t h t he nor mal
CO2 cont ent of t he at mos pher e, havi ng a pH of 5. 67. Th e preci pi t at i on i s
also a cont i nuous source of acidity for soils. Thes e addi t i ons of acidity ar e
neut r al i zed in al kal i ne soils; in cal careous soil, for exampl e, t he r eact i on is
The Soil pH Continuum 39
Ca CO3 + 2H+ = C a
2 +
+ H2 O + CO2 (3.9)
T h e H
+
i s conver t ed t o wat er . Th e alkaline nat ur e of cal careous soils i s
mai nt ai ned.
For ma t i on a nd Na t u r e of Ac i d Soi l s
Soil pH i s st rongl y cor r el at ed wi t h preci pi t at i on; t hat is, soils of ar i d and
s ubhumi d r egi ons t end t o be al kal i ne or neut r al , and most soils of humi d
r egi ons ar e acid. Let us l ook at t he nat ur al forces and processes t hat
pr oduce acid soils.
In a humi d r egi on t he di ssol ut i on of salts i n cal careous a nd ot her
al kal i ne soils and t hei r r emoval by l eachi ng cause t he soils t o become
nonsal i ne and noncal car eous. Th e soil at this poi nt i s 100% XCa. . Na- sat u-
r at ed and will have a pH of about 7. 5. Such soils, compar ed t o cal careous
soils, have lost much of t hei r ability t o neut r al i ze acids. T h e H
+
f r om t he
aci ds, whi ch ar e const ant l y and nat ural l y bei ng a dde d t o t he soil, gradual l y
r epl ace XCa. . Na, and t hese cat i ons ar e l eached out of t he soil wi t h accom-
panyi ng acid ani ons. In t he si t uat i on shown i n t he following equat i on, t her e
is l eachi ng of Ca ( NO3 ) 2 :
CaX + 2 HNO3 = 2 HX + Ca ( NO3 ) 2 (3. 10)
T h e loss of some of t he XCa. . Na and t he accumul at i on of some hydr oxy- Al
f r om weat her i ng ar e accompani ed by a decr ease i n p H. It i s i nt er est i ng t hat
cer t ai n agr i cul t ur al pract i ces cont r i but e t o t he devel opment of soil acidity
in a ma nne r similar to nat ur al processes. Ni t ri c acid is pr oduced in signifi-
cant quant i t i es by nitrification of t he N t hat is fixed by l egumes and t he N
t hat i s added t o soils i n ma nur e and a mmoni um fertilizers.
Th e nat ur al i nput s of acidity from preci pi t at i on, r espi r at i on, nitrifica-
t i on, and so fort h cont i nue aft er an al kal i ne soil has become acid t hr ough
l eachi ng. Th e gr eat er t he preci pi t at i on, t he gr eat er t he acidic i nput bot h
f r om pr eci pi t at i on a nd from associated biological activity. Acidity, on t he
ot her hand, st i mul at es weat her i ng of pr i mar y mi neral s. Such weat her i ng
t ends t o gener at e alkalinity, as i l l ust rat ed by t he weat her i ng of albitic
fel dspar:
Na Al Si 3 O8 + 4 H2 O + 4 H
+
= Na
+
+ Al
3 +
+ 3Si ( OH) 4 (3. 11)
Alkalinity i ncreases because H
+
i s cons umed and OH
i s pr oduced. Th e Na
(and Ca, Mg, and K) rel eased by weat her i ng can be adsor bed as XNa, and
t he Al is likely to be i ncor por at ed in silicate clay or to accumul at e as
hydr oxy- Al . Th e abr asi on pH, t he pH of t he gr ound mi ner al i n wat er , t hat
is, of al bi t e, i s 9 or 10. T h e abrasi on pH of most of t he weat her abl e mi neral s
of t he sand and silt fract i on i s bet ween 7 and 11, and t hei r weat her i ng
supplies t he soil wi t h alkali and alkaline ear t h cat i ons (Na, K a nd Ca, Mg),
whi ch cont r i but e t o t he mai nt enance of neut ral i t y or alkalinity. At this
poi nt i n soil evol ut i on, t he soil may be about neut r al , and t he soil may
mai nt ai n a pH t hat fluctuates near 7. Th e l ongt i me resul t of cont i nued
l eachi ng and weat her i ng, however , i s an acid soil. Most of t he soils t hat
devel oped from late Wisconsin glacial mat eri al s wer e cal careous at t he
surface about 10 000 years ago and ar e now acid at t he surface and have
been l eached of car bonat es (lime) to a dept h of about 1 to 2 met er s wher e
t he soil moi st ur e r egi me is udi c.
Most of t he acidity of acid soils i s associated wi t h Al. T h e devel opment
or accumul at i on of soil acidity parallels t he mi ner al - weat her i ng sequence i n
whi ch Al is rel eased and accumul at es in t he soil. It was not ed in Chapt er 2
t hat hydroxy-Al accumul at es i n soils as t hey become acid, fi rst as i nt er l ayer
Al , as coat i ngs on clays and as compl exes wi t h or gani c mat t er , and, sec-
ondl y, as exchangeabl e Al
3 +
when soil pH decl i nes bel ow 5. 5. Th e forms of
Al , wi t hout t he hydr at i on wat er , a nd t hei r aver age char ge as a funct i on of
pH ar e shown i n Fi gur e 3. 1.
Th e Al i s i n six coor di nat i on wi t h H2 O, wi t h O H
-
, or wi t h bot h
( H2 O + OH
= 6). Wh e n equat i ons ar e wr i t t en wi t h Al fully hydr at ed, it is

easi er t o follow t he changes t hat occur wi t h pH changes. As pH decl i nes
from 7 and as t he hydr oxy- Al is pr ot onat ed, t he Al serves as a sink for t he
accumul at i on of H
+
(acidity):
Al ( OH) 3 ( 3H2 O) + 3H+ = A1
3 +
( 6 H2 O) (3. 12)
Th e i ncrease i n t he aver age char ge of t he Al i s associ at ed wi t h a decr ease i n
ECEC. An i ncrease i n p H, by cont r ast , causes t he neut r al i zat i on of acidity, a
decr ease i n t he aver age char ge of Al , and an i ncrease i n ECEC:
A1
3 +
( 6H2 O) + 3 O H
-
= Al ( OH) 3 ( 3H2 O) + 3 H2 O (3. 13)
pH
FIGURE 3. 1 Rel ati ve distribution of the forms of soluble al umi num as a func-
tion of pH. (From Marion et al., 1976, used by permission of the Williams and
Wilkins Company. )
The Soil pH Continuum 41
Th e hydrolysis of bot h forms of Al pr oduces H ions t hat cont r i but e t o
t he acidity of t he soil sol ut i on:
Al
3 +
+ H2 O = Al ( OH)
2 +
+ H
+
(3. 14)
Al ( OH)
2 +
+ H2 O = Al ( OH) 2
+
+ H
+
(3. 15)
Th e acidity of acid soils i s commonl y di vi ded i nt o t he weak and st r ong
fract i ons. T h e st r ong acidity i s t he exchangeabl e acidity t hat i s composed
mai nl y of XA1 and makes up a small par t of t he t ot al acidity. T h e weak
aci di t y i s st rongl y ads or bed Al associ at ed wi t h t he hydroxy-Al of t he clay
fract i on and organi c-Al compl exes and makes up t he gr eat bul k of t he t ot al
acidity. Th e weak acidity i s slow t o neut r al i ze and gives t he soil its bufferi ng
charact eri st i cs. Dur i ng t he nat ur al devel opment of aci d soils f r om al kal i ne
par ent mat er i al , t her e i s a progressi ve accumul at i on of hydroxy-Al followed
by t he accumul at i on of XA1 as soil pH decl i nes. Whe n acid soils ar e l i med,
this sequence of event s i s r ever sed a nd t he st r ong or exchangeabl e acidity i s
neut r al i zed fi rst , followed by t he neut r al i zat i on of hydroxy-Al as soil pH
i ncreases.
Ex c ha ng e a b l e Ca t i on Sui t e of Ac i d Soi l s
T h e exchangeabl e cat i on suite of aci d soils varies wi t h p H. Aci d soils wi t h
pH 5.5 or mor e will have little, i f any, XA1. T h e CEC will be sat ur at ed wi t h
XCa. . Na and typically Ca > Mg > K > Na. Monoval ent hydr ogen compet es
ver y poor l y for adsor pt i on on t he exchange sites of clays, and little, i f any, i s
pr esent . Some H ions ar e ads or bed on t he acidic gr oups of t he SOM.
Ads or bed H i s so st rongl y bonded ont o pH- de pe nde nt char ge sites t hat i t
plays little, if any, r ol e in soil acidity.
Whe n t he pH decl i nes bel ow 5. 5, XA1 becomes i ncreasi ngl y a bunda nt
a nd Al sat ur at i on (XA1 as a per cent age of XAL..Na) i ncreases. By cont rast ,
XCa. . Na become i ncreasi ngl y less abundant , a nd sat ur at i on wi t h XCa. . Na
decreases. Whe n t hese acid soils ar e l eached wi t h an unbuf f er ed 1 N KC1
sol ut i on, t he cat i ons r emoved ar e for t he most par t Al , Ca, Mg, K, and Na
(see Tabl e 3.1). Not i ce i n Tabl e 3.1 t hat t he Al sat ur at i on of some hor i zons
TABLE 3. 1 Exchangeable Cations, Effective Cation Exchange Capacity,
Aluminum Saturation, and pH of an Ultisol
Exchangeable cations,
me q/ l 00g
ECEC, Al,
Horizon Ca Mg K Na Al me q/ l 00g percent pH
Ap
2.3 1.1 0.1 0.3 2.4 6.2 39 4.5
Bt21 3.2 1.4 0.4 0.2 8.1 13.3 61 4.6
Bt22 2.0 1.1 0.5 0.2 9.2 13.0 71 4.7
C1 1.3 1.5 0.7 0.2 10.7 14.4 74 4.7
Source: Data for pedon 121, Soil Taxonomy, Soil Survey Staff, 1975.
i s over 70%. Somet i mes Al sat ur at i on can exceed 90%, and XCa. . Na sat ura-
t i on is less t han 10%. Thes e condi t i ons pr oduce a small suppl y of available
XCa. . Na and t he l i kel i hood of an Al toxicity.
An i ncrease i n soil acidity and t he accompanyi ng changes i n t wo soil
pr oper t i es ar e shown i n Fi gur e 3. 2. Not i ce t hat t he decr ease of XCa. . Na
was small compar ed t o t he l arge i ncrease i n t i t rat abl e (buffer) acidity, whi ch
reflects t he accumul at i on of hydroxy-Al wi t h decr easi ng soil p H. Thus , t he
a mount of l i me needed t o i ncrease soil pH i s great l y i ncreased as soils
become hi ghl y aci d.
Soils with pH less t han 4 ar e usually affected by t he f or mat i on of st r ong
acid, sulfuric acid for exampl e, owi ng t o t he oxi dat i on of S and t he forma-
t i on of H2 S O4 as i n mi ne spoil soils and i n cat-clay soils t hat cont ai n sulfides.
In summar y, t he maj or factors cont rol l i ng soil pH over t he r ange of about 4
and less t o 10 ar e
1. Below 4 and 3. 5 to as low as 2, pH is cont r ol l ed largely by t he f or mat i on
of st r ong acids.
2. In t he r ange 4 t o about 7. 5, t he hydrolysis of exchangeabl e and hydr oxy
forms of Al is t he maj or sour ce of H
+
; exchangeabl e H is mi nor .
3. In t he r ange 7.5 t o 8. 3, t he pH i n cal careous soils i s cont r ol l ed mostly by
hydrolysis of Ca CO3 .
4. In t he r ange 8.5 t o 10, pH i s cont rol l ed largely by hydrolysis of Na 2 CO3
and exchangeabl e Na.
5. Th e pr oduct i on of C 0 2 from r oot and mi crobi al r espi r at i on may locally
and t empor ar i l y l ower t he pH of al kal i ne soils a significant amount .
Extreme Weathering Effects on pH and Cation Exchange 43
EX T R EME WEA T H ER I N G
EF F ECTS O N p H A N D C A T I O N EX C H A N G E
Th e concept of i ncreasi ng soil acidity over t i me t hr ough soil evol ut i on a nd
t he gener al i zed rel at i onshi ps bet ween soil pH and some soil pr oper t i es have
been gi ven. Two acid soils, however , can have t he same pH and have
great l y di fferent soil fertility par amet er s . Th u s t he need t o el abor at e on t he
effects of ext r eme weat her i ng on soil p H, ECEC, and t he exchangeabl e
cat i on sui t e as t hey r el at e t o t he fertility of soils.
Low- Ac t i v i t y Cl a y v e r s us Pe r ma ne nt - Cha r g e Cl a y Soi l s
Soils wi t h clay fractions domi nat ed by pe r ma ne nt char ge 2 : 1 and 2 : 1 : 1
clay mi ner al s have a hi gh CEC t hat is due mostly to i s omor phor us subst i t u-
t i on. Low-activity clay (LAC) soils have low CEC because kaol i ni t e ( 1 : 1
clay), gi bbsi t e, and ot her oxi di c clays have a small pH- de pe nde nt char ge.
LAC soils have also been called vari abl e-charge soils. General l y, Ultisols
and Oxisols ar e LAC soils and t he pr oduct of i nt ensi ve or ext r eme weat h-
er i ng. T h e exchange pr oper t i es of most of t he mi ner al soils of t he ot her soil
or der s ar e domi nat ed by per manent - char ge clays. Soils domi nat ed by per -
manent - char ge clays may evolve i nt o LAC soils. It i s commonl y r ecogni zed
t hat Alfisols may over t i me evol ve i nt o Ultisols, whi ch may evolve i nt o
Oxi sol s. T h e CEC, t he a mount of XCa. . Na, and t he a mount of XA1 and Al
sat ur at i on of t he most weat her ed member s of t hese t hr ee or der s will be
compar ed t o illustrate t hei r i mpor t ant differences.
Some of t he ol dest Alfisols i n t he gl aci at ed r egi ons of t he Uni t ed St at es
have been sufficiently weat her ed and l eached t o have hor i zons wi t h a pH of
5 or less and some Al sat ur at i on in all hor i zons to a dept h of 2 met er s or
mor e. Clays ar e most l y 2 : 1 and 2 : 1 : 1 t ypes, and t he weat her i ng of pri -
mar y mi neral s still releases a significant quant i t y of alkali (Na and K) and
al kal i ne ear t h cat i ons (Ca and Mg). The s e soils, compar ed t o LAC soils,
have hi gh CEC and a consi der abl e quant i t y of XCa. . Na. Thes e Alfisols ar e
moder at el y but not ext r emel y weat her ed, and as a r ul e t hey have moder at e
t o hi gh fertility for agr i cul t ur e and forest ry.
Wi t h a significant i ncrease i n weat her i ng and l eachi ng, t he pH may
r emai n t he same or actually i ncrease, but ot her soil fertility par amet er s may
change significantly as Alfisols evol ve i nt o Ultisols ( LAC soils). Many Ulti-
sols (pale gr eat groups) have less t han 10% weat her abl e mi ner al s i n t he 20-
t o 200- mi cr on fract i on (coarse silt and fi ne sand) t hat can weat her and
rel ease alkali and al kal i ne ear t h cat i ons. Th e r e is a small ECEC t hat is hi ghl y
Al -sat urat ed, whi ch means t hat t her e i s a very small a mount of XCa. . Na.
Not i ce i n Fi gur e 3.3 t hat t he pH of t he Ultisol i s similar t o t hat of t he
Alfisol, but t he Ultisol has much less ECEC, a smal l er a mount of exchange-
abl e Ca, Mg, and K, and a much gr eat er Al sat ur at i on. Ultisols ar e nat ural l y
i nfert i l e soils with a t endency to have Al toxicity and to be deficient in Ca
and Mg. The y ar e ext ensi ve i n t he sout heast er n Uni t ed States on t he
Pi edmont and Coastal Plains wher e some l andscapes ar e over 5 million
years ol d.
FIGURE 3. 2 Ti tratabl e acidity and quantity of
XCa. . Na (exchangeabl e bases) as a functi on of
pH i n the Ap hori zon of an Alfisol. (Data from
Wol cott et al., 1965. )
Extreme Weathering Effects on pH and Cation Exchange 45
St r addl i ng t he equat or i n t he humi d t ropi cs of Sout h Amer i ca and
Africa ar e l arge areas of Oxisols ( Or t hox) . Oxisols ar e t he most - weat her ed
soils a nd have an oxic subsoil hor i zon t hat has a clay fract i on wi t h a CEC,
det er mi ned at pH 7, of 16 me q / 1 0 0 g or less. T h e oxic subsoil hor i zon
consists of a mi xt ur e of oxi di c clays wi t h var yi ng amount s of 1: 1 clay and
accessory, hi ghl y i nsol ubl e mi neral s such as quar t z. Onl y a t r ace of feld-
spars, micas, and ot her weat her abl e mi ner al s ar e pr esent . I n t he most -
weat her ed Or t hox, t he gr eat gr oup Acr or t hox, weat her i ng has virtually
come t o an end. Some par t of t he oxic hor i zon cont ai ns 1.5 meq or less of
exchangeabl e cat i ons (i ncl udi ng Al) per 100 gr ams of clay t hat can be
r e move d by l eachi ng wi t h unbuf f er ed KC1. Th e A hor i zons of nat ur al
Acr or t hox have enough or gani c mat t er t o pr oduce a net negat i ve char ge.
Th e low cont ent of or gani c mat t er i n t he l ower par t of t he oxic hor i zon
means t hat i t may have a net positive char ge. Whe n soils become this
weat her ed, t he pH i s hi gher t han t hat of l ess-weat hered soils, like Alfisols
and Ultisols, for exampl e. Such soils, however , have a very small a mount of
XCa. . Na, and t hey may have an insufficient quant i t y of XA1 t o pr oduce Al
toxicity. A compar i son of t hr ee Oxisols wi t h five Ultisols in Puer t o Ri co
showed similar Al sat ur at i on but , because of t he l ower ECEC, t he Oxisols
cont ai ned only one- t ent h as much XA1. Thi s di fference i n a mount of XA1
expl ai ns why Al toxicity is less of a pr obl em for cr op pr oduct i on on Oxisols
t han on Ultisols. Cr op pr oduct i on on Oxisols i s commonl y l i mi t ed by Ca
and Mg deficiencies. A compar i son of t hese i mpor t ant soil fertility par ame-
t ers of an Oxisol wi t h t hose of an Ultisol a nd an Alfisol i s given i n Fi gur e
3. 3. Shifting cul t i vat i on or sl ash-and-burn agr i cul t ur e ar e popul ar systems
for cr op pr oduct i on on nat ural l y infertile Ultisols and Oxisols. Some of t he
wor l d' s most pr oduct i ve soils, however , ar e intensively or ext r emel y weat h-
er ed. Exampl es i ncl ude t he Ultisols of t he Coastal Plains of t he sout heast er n
Uni t ed States for pr oduct i on of cot t on a nd cor n; Oxisols i n Hawai i for
sugar cane and pi neappl es; Oxisols i n Brazil for soybeans, wheat , sugar
cane, and a wi de vari et y of ot her crops (see Fi gur e 3.4).
On t he basis of t he degr ee of weat her i ng, mi ner al soils can be classified
i nt o (1) LAC soils with very low ECEC a nd very low XCa. . Na, (2) LAC soils
wi t h low ECEC and low XCa. . Na, and (3) per manent - char ge soils wi t h hi gh
ECEC and hi gh XCa. . Na. Thus , t hr ee di fferent soils with t he same pH can
have great l y di fferent fertility par amet er s and need di fferent soil manage-
ment , i ncl udi ng l i mi ng pract i ces. In summar y, as soils evolve f r om bei ng
moder at el y weat her ed, as r epr es ent ed by Alfisols, t o becomi ng ext r emel y
weat her ed, as r epr es ent ed by Oxisols, t her e i s
44
1. A decr ease i n 2 : 1 and 2 : 1 : 1 clays a nd weat her abl e mi ner al s and an
i ncrease i n 1: 1 and oxi di c clays.
2. A decr ease in ECEC and an i ncrease in Al sat ur at i on.
3. An i ncrease i n soil p H.
4. A decl i ne in soil fertility for pr oduct i on of most food crops.
The s e general i zat i ons appl y t o soils devel oped i n par ent mat er i al of
FIGURE 3.4 Hi gh-yi el di ng soybeans grown on Oxi sol s in the Brazilian
hi ghl ands.
mi xed mi ner al ogy because some young soils i nher i t low-activity clays. Some
Oxisols, of t he s ubor der s To r r o x and Ust ox, may have a good suppl y of
XCa. . Na. Even so, t he concept of a mi ner al - weat her i ng sequence is well
est abl i shed and i s useful i n r el at i ng t he differences i n soil pH and cat i on
exchange rel at i ons of several of t he soil or der s .
SOI L F ER T I LI T Y A N D SOI L C LA SSI F I C A T I ON
In Soil Taxonomy (Soil Survey Staff, 1975) t he Alfisols and Ultisols ar e
di fferent i at ed, i n par t , by whet her base sat ur at i on as det er mi ned at pH 8.2
i s less t han 3 5 % for Ultisols versus 35% or mor e for Alfisols i n t he l ower
par t of t he r oot zone (1. 8 met er s bel ow t he soil surface or 1.25 met er s
bel ow t he upper boundar y of t he argillic hor i zon) . Base saturation in this
cont ext i s defi ned as t he sum of exchangeabl e Ca pl us Mg plus K pl us Na
(XCa. . Na) di vi ded by t he CEC as det er mi ned at pH 8. 2. About forty years
ago, when wor k on soil t axonomy was st ar t ed, this cri t eri on was devel oped
because i t was commonpl ace t o det er mi ne t he CEC at 7.0 or 8.2 a nd
calculate t he per cent age of base sat ur at i on. T h e r ol e of Al and t he i mpor -
t ance and nat ur e of pH- de pe nde nt char ge i n soils wer e poorl y under s t ood.
Now we r ecogni ze t hat i n soils wi t h pe r ma ne nt char ge, t he CEC varies
much less with changes i n pH, relatively speaki ng, t han i t does i n soils wi t h
pH- dependent char ge ( LAC soils). If bot h an Alfisol and an Ultisol had a
pH of 5.5 and nei t her had any XA1, bot h soils woul d have t he ECEC
sat ur at ed with XCa. . Na and woul d be 100% XCa. . Na- sat ur at ed, or base-
sat ur at ed, accor di ng t o t he ECEC. At pH 8.2 t he Ultisol woul d have a l ower
per cent age of base sat ur at i on t han t he Alfisol because t he relatively gr eat er
Effects of Soil pH on Plant Growth 47
i ncrease i n CEC of t he Ultisol woul d mean a relatively l ar ger denomi nat or
i n t he equat i on. Thi s cr i t er i on, t hen, whi ch uses a base sat ur at i on per cent -
age det er mi ned at a pH of 8. 2, di fferent i at es t he l ess-weat hered, per ma-
nent - char ge and mor e nat ural l y fertile Alfisols from t he mor e- weat her ed
and less nat ural l y fertile Ultisols domi nat ed by vari abl e char ge.
I n Mollisols t he mollic hor i zon must have 50% or mor e base sat ur at i on
det er mi ned at pH 7. 0. In effect, this means t hat Mollisols also consist mostly
of per manent - char ge clays, t hat t her e is less l eachi ng of XCa. . Na as com-
par ed t o Alfisols, and i n gener al , t hat Mollisols ar e nat ural l y mor e fertile
t han Alfisols for t he cr ops commonl y gr own. Thi s does not negat e t he fact,
however , t hat fertilization and l i mi ng may enabl e t he Ultisols and Alfisols t o
become as pr oduct i ve as Mollisols. Because Soil Taxonomy uses per cent age
base sat ur at i on, i t i s i mpor t ant t o under s t and t he historical devel opment of
base sat ur at i on and its significance for soil classification. Now t her e i s much
less emphasi s on per cent age base sat ur at i on because t he CEC of soils at
t hei r cur r ent pH i s essentially 100% base- sat ur at ed unless t her e i s some
XA1. Bel ow pH 5. 5, XA1 sat ur at i on i ncreases, a nd t he XCa. . Na (base)
sat ur at i on decreases wi t h decr easi ng pH. Thi s f eat ur e can be expr essed
with r ef er ence t o Al sat ur at i on.
EF F ECTS O F SOI L p H O N P LA N T G R O WT H
Wi t hi n t he pH r ange of 4 t o 10, t he pr i mar y effect of soil pH on pl ant
gr owt h i s not t he ( H
+
) or ( OH
) per se but t he associated chemi cal envi r on-

ment s. In gener al , t he maj or i nfl uence of pH i s on i on activities t hat affect
t he toxicity of el ement s like Al and Mn or on nut r i ent availability as shown
for mi ner al soils i n Fi gur e 3. 5.
Ni t r ogen availability i s ma xi mum bet ween pH 6 and 8 because t he
mi neral i zat i on of N is ma xi mum in this r ange. Th e availability of P in acid
soil i s r educed by pr eci pi t at i on and adsor pt i on by Fe and Al. Cal ci um
car bonat e i n cal careous soils r educes t he solubility of cal ci um phos phor us
compounds by i ncreasi ng t he activity of C a
2 +
or by adsor pt i on on Ca CO3
surfaces. The s e exampl es specifically show how pH affects nut r i ent avail-
ability. Mor e compl et e discussions for t he vari ous nut r i ent s appear i n l at er
chapt er s. He r e t he goal i s t o focus on t he specific causes of acid and al kal i ne
soil infertility.
Ac i d Soi l Inf e r t i l i t y
Ads or bed hydroxy-Al is so st rongl y adsor bed t hat it is inactive and does not
di rect l y i nfl uence pl ant gr owt h. T h e XA1 i s less st rongl y ads or bed and,
when Al sat ur at i on exceeds 60% in soils wi t h a significant ECEC, t her e is
likely t o be 1 ppm or mor e of Al i n sol ut i on. Many cr op pl ant s will suffer
from Al toxicity. Sol ubl e Al also react s with P to r educe its availability.
Dissolution of Mn at low pH may cause Mn toxicity, especially i n soils wi t h a
hi gh per cent age of Mn mi neral s. In hi ghl y acid Ultisols, pl ant gr owt h i s
commonl y l i mi t ed by t oxi c levels of Al and Mn bef or e Ca and Mg deficien-
cies occur . I n Oxisols, however , t he r ever se t ends t o be t r ue.
Mol ybdenum ani ons ar e st rongl y adsor bed on pH- de pe nde nt clays,
and Mo t ends t o become less available and deficient i n some acid soils. T h e
availability of Mo i s i mpor t ant for l egumes because of t he r ol e Mo plays i n
N fixation.
Al t hough a pH of less t han 4 is general l y consi der ed to affect pl ant
gr owt h di rect l y, t he i nfect i on process of some Rhizobium st rai ns is acid-sen-
sitive, and only moder at e acidity may limit t he gr owt h of cert ai n l egumes.
A summar y of t he t oxi c factors f ound t o limit t he gr owt h of alfalfa i n
some acid soils from Ar kansas and Geor gi a i s given i n Tabl e 3. 2. Pl ant s
show gr eat diversity i n t ol er ance t o and resi st ance t o t oxi c factors; t he
resul t s for a cr op like cowpeas, whi ch is mor e t ol er ant of hi gh levels of
soluble Mn, woul d be di fferent from t hose shown for alfalfa.
St udi es have i ndi cat ed t hat for a given pH, acid soils have less XA1 if
t hey cont ai n mor e or gani c mat t er . Th e Al i s compl exed or chel at ed by t he
SOM. Not i ce t hat i n Tabl e 3.1 t he pH of t he A and B hor i zons ar e similar,
but Al sat ur at i on of t he A hor i zon i s only 39% compar ed t o 60% t o 70% for
t he B hor i zon. Many acid surface soils allow for good r oot devel opment ,
al t hough i n subsoils wi t h t he same pH r oot gr owt h i s poor because of Al
Effects of Soil pH on Plant Growth 49
TABLE 3.2 Toxic Factors Limiting Growth of Alfalfa on Acid Surface
Soils
Soil
pH Region State Factor
Bladen 4.8 Coastal Plain Georgia Al toxicity
Cecil 5.2 Piedmont Georgia Mn toxicity
Leon 4.2 Coastal Plain Georgia Ca deficiency
Loring 5.3 Loess Hills Arkansas Mn toxicity
Zanesville 4.9 Ozarks Arkansas Mn toxicity
Source: From Foy and Burns, 1964.
toxicity. Thi s has been conf i r med by addi ng or gani c mat t er t o mi xes of aci d
and mi ner al soils, not i ng t he r educt i on i n XA1, and obser vi ng t hat pl ant s
can gr ow well, as shown i n Fi gur e 3. 6. In acid Histosols pl ant s ar e unl i kel y
t o suffer from Al toxicity because of t he hi gh cont ent of or gani c mat t er and
t he compl exi ng of Al. Histosols also have a low cont ent of mi ner al mat t er .
The s e factors cont r i but e t o t he availability of pl ant nut r i ent s as affected by
pH i n Histosols, as shown i n Fi gur e 3. 7.
Al k a l i ne Soi l Inf e r t i l i t y
Cal car eous soils ar e frequent l y pr oduct i ve for a wi de r ange of cr ops i ncl ud-
i ng cot t on, cor n, sugar beet , pot at o, and many l egumes. On t he ot her hand,
FIGURE 3. 6 The effect of organi c matter on the growth of plants i n
soil consisting of sand and Al - mont mori l l oni t e mi xtures. (From
Hargrove and Thomas, 1981, used by permi ssi on of the Soil Sci ence
Society of Ameri ca. )
FIGURE 3. 5 The relation bet ween
soil pH and the relative availability
of plant nutrients in mineral soils.
The wi der the bar, the greater the
availability. (From Soil Handbook,
Uni versi ty of Kentucky, 1970. )
Soil pH
FIGURE 3.7 The relation bet ween soil pH and the rela-
tive availability of plant nutrients in organi c soils or Hi sto-
sols. The wi der the bar, the greater the availability. (From
Lucas, 1982. )
many pl ant s, i ncl udi ng roses, pi n oak, gr apes, s or ghum, a nd mapl e, ar e
suscept i bl e t o Fe or Mn deficiencies. Zinc and P may also have low availabil-
ity at hi gh p H. Some al kal i ne soils wi t h soluble salts may cont ai n enough
soluble B to pr oduce B toxicity. Th e low availability of P in cal careous soils
is discussed in Chapt er 5.
USE OF LIME
Agr i cul t ur al lime is a soil a me ndme nt consi st i ng principally of Ca CO3 and
to a lesser ext ent Mg CO3 . It is used to neut r al i ze soil acidity and furni sh Ca
and Mg for t he gr owt h of pl ant s. Li me i s commonl y gr ound l i mest one with
varyi ng amount s of Ca CO3 and Mg CO3 . Ot he r l i mi ng mat eri al s i ncl ude
mar l , chal k, basic slag, and basic oxygen furnace slag from i r on and steel
manuf act ur i ng, f l ue dust from cement pl ant s, and refuse from sugar beet
and paper mill pl ant s.
Use of Lime 51
Ne u t r a l i z a t i on Re a c t i ons
Th e Ca CO3 , and Mg CO3 , i n lime hydrol yze t o pr oduce OH
as follows:
Ca CO3 + H2 O = C a
2 +
+ OH
+ HCO3
(3. 16)
T h e H
+
i n t he soil sol ut i on comes for t he most par t from Al hydrolysis. T h e
H
+
react s wi t h t he OH
t o f or m wat er . T h e overall r eact i on r epr es ent i ng

t he neut r al i zat i on of Al -deri ved soil acidity can be wr i t t en as
2Al X + 3 Ca CO3 + 3 H2 O = 3CaX + 2Al ( OH) 3 + 3 CO2 (3. 17)
If a soil with a pH less t han 5 is l i med to a pH of 7, t her e will be a
progressi ve series of react i ons. T h e exchangeabl e Al , hydr at ed as
Al ( 6 H2 O)
3 +
, will hydrol yze fi rst , followed by t he hydroxy-Al forms, as
follows:
Al ( 6 H2 O)
3 +
+ H2 O = Al ( OH) ( 5 H2 O)
2 +
+ H 3 O
+
(3. 18)
Al ( OH) ( 5 H2 O)
2 +
+ H2 O = Al ( OH) 2 ( 4 H2 O)
+
+ H 3 O
+
(3. 19)
Al ( OH) 2 ( 4 H2 O)
+
+ H2 O = Al ( OH) , ( 3H2 O) + H 3 O
+
(3. 20)
Each r eact i on i s dr i ven t o t he r i ght as t he H
+
, or H 3 O
+
, i s neut r al i zed by t he
OH
suppl i ed by t he l i me. At pH of about 7, t he hydr oxy- Al i s pr eci pi t at ed

as Al ( 3H2 O) ( OH) 3 . T h e vari ous forms of Al t hat ar e i n sol ut i on for neut r al -
i zat i on, whi ch depend on t he p H, ar e given i n Fi gur e 3. 1. T h e r educt i on of
Al sat ur at i on with i ncreasi ng pH i s given i n Fi gur e 3. 8.
T h e neut r al i zat i on of acidity and t he i ncrease i n pH cause an i ncrease
i n t he CEC and an aver age r educt i on i n t he char ge of t he vari ous f or ms of
FIGURE 3. 8 The effect of l i mi ng on soil pH and
the percentage of al umi num saturation of an Ulti-
sol. (Data from the annual report on tropical soils
research of Nort h Carolina State University, 1976. )
Al, as shown i n Fi gur e 3. 1. Th e ECEC of LAC soils may be i ncr eased four
or mor e t i mes by i ncreasi ng t he pH t o 7. 0. Aft er t he XA1 i s neut r al i zed and
t he pH i s 5. 5, t he soil i s 100% XCa. . Na- sat ur at ed, and any f ur t her i ncrease
i n pH will pr oduce a gr eat er quant i t y of XCa. . Na because t he ECEC will
i ncrease. Th e r e will be a gr eat er suppl y of available Ca a nd Mg when l i me
cont ai ni ng bot h Ca and Mg i s used t o neut r al i ze soil acidity. Usi ng l i me
wi t hout Mg, Ca O, t o i ncrease pH of some Ohi o soils t o 7 r esul t ed i n 17% t o
34% r educt i on i n XMg, whi ch was bel i eved t o have been br ought about by
occlusion or copreci pi t at i on of Mg with Al.
Soi l p H a nd Pl a nt Gr owt h Re s p ons e
As we have not ed, t he pH of most soils i s i n t he r ange of 4 t o 10 and
depends on t he soil par ent mat er i al and t he changes t hat have occur r ed
dur i ng soil genesis. Th e pl ant s t hat have evol ved i n deser t r egi ons have
adapt ed t o t hr i ve on neut r al and alkaline soils, and many deser t pl ant s have
gr eat t ol er ance for sol ubl e salts and soluble Na (hal ophyt es). Pl ant s t hat ar e
nat i ve t o t he humi d t ropi cs, such as cassava, have a t ol er ance for sol ubl e Al.
Some t emper at e r egi on pl ant s t hat do well on hi ghl y aci d soils, such as
r hodode ndr on, appear t o be Al accumul at or s. Gr eat genet i c vari at i on exists
bet ween species and cul t i vars, and this fact i s used t o devel op new vari et i es
t hat can bet t er cope wi t h stressful soil condi t i ons r el at ed t o soil p H. For
exampl e, moder at el y Al -t ol erant wheat vari et i es have been devel oped for
pr oduct i on on Oxisols i n Brazil. T h e pH pr ef er ences of over 1 500 pl ant s
was publ i shed by Spur way (1941).
Fr om Tabl e 3.3 i t can be not ed t hat oats gr ew qui t e well at pH 4. 7 a nd
about as well at 5 as at 5. 7, 6. 8, or 7. 5. Cor n or mai ze gr ew well over t he
r ange of 5.0 t o 7. 5. By cont rast , barl ey failed t o yield at 4. 7 and at t ai ned
maxi mum yield onl y when t he pH was 6.8 or hi gher . Legumes , like cl over
and alfalfa, needed a pH of about 6. 5 or hi gher t o pr oduce ma xi mum
yields. For all cr ops t he rel at i ve aver age yields at pH 4. 7 wer e onl y 32%
compar ed t o 9 8 % at pH 6. 8. Dat a of this nat ur e ar e t he basis for r ecom-
TABLE 3.3 Relative Crop Yields versus Soil pH
Relative yield at indicated pH
Crop 4.7 5.0 5.7 6.8 7.5
Alfalfa 2 9 42 100 100
Barley 0 23 80 95 100
Corn (maize) 34 73 83 100 85
Oats 77 93 99 98 100
Red clover 12 21 53 98 100
Soybeans 65 79 80 100 93
Sweet clover 0 2 49 98 100
Wheat 68 76 89 100 99
Source: Data from Ohi o Agr. Exp. Sta. Spec. Cir. 53, 1938.
Use of Lime 53
me ndi ng lime t o i ncrease t he pH of some acid soils t o a par t i cul ar val ue. For
exampl e, t he pH may be 6.0 for t he pr oduct i on of cont i nuous cor n. How-
ever, i f cor n i s i ncl uded i n a r ot at i on wi t h alfalfa, t he pH shoul d be in-
creased for profi t abl e pr oduct i on of t he alfalfa. T h e yield responses shown
i n Tabl e 3.3 ar e, i n par t , r el at ed t o t he fact t hat t he soil had hi gh CEC a nd
hi gh XCa. . Na. Thus , l i mi ng st rat egi es and l i me r equi r ement s depend, i n
par t , on t he chemi cal and mi neral ogi cal pr oper t i es.
T he Li me Re q u i r e me nt
Th e a mount of lime r equi r ed i s affected by bot h cr op a nd soil. Th r e e
di fferent l i mi ng st rat egi es or lime r equi r ement met hods can be r ecogni zed
for t hr ee di fferent ki nds of mi ner al soil si t uat i ons: very low ECEC and very
low XCa. . Na, low ECEC and low XCa. . Na, and hi gh ECEC and hi gh
XCa. . Na.
Soils with Very Low ECEC and XCa..Na
Th e most weat her ed soils with bot h very low ECEC a nd XCa. . Na t end t o be
most deficient i n t he Ca and Mg ne e de d for cr oppi ng. Even t hough t her e
may be hi gh Al sat ur at i on, t her e t ends t o be t oo little XA1 t o pr oduce Al
toxicity. T h e lime r equi r ement i s t he a mount needed t o cor r ect t he defi-
ciency of Ca and Mg and i s essentially a fertilization pr obl em. T h e goal i s
one of addi ng enough l i me t o cor r ect t he deficiency wi t hout addi ng so
much t hat t he availability of some ot her nut r i ent s, like Zn and B, i s r educed
e nough t hat t he soil becomes deficient i n t hem. Small appl i cat i ons of l i me
ar e desi rabl e wher e lime mat eri al s ar e scarce and must be t r ans por t ed a
l ong di st ance. Th e effects of very small l i me appl i cat i ons, however , ar e
short -l i ved.
Soils with Low ECEC and XCa..Na
Most LAC soils have bot h low ECEC and XCa. . Na. Th e r e i s sufficient
ECEC and Al sat ur at i on t o make Al toxicity t he pr i mar y l i mi t at i on i n
cr oppi ng. T h e l i me r equi r ement i s t he a mount needed t o r emove t he t hr eat
of Al toxicity for Al -i nt ol erant cul t i vars. Exper i ence has shown t hat this is
an a mount of lime equi val ent t o one and a half t o t wo t i mes t he XA1, a nd
t he pH will be i ncreased t o about 5. 5. Thi s si t uat i on i s c ommon for most
Ultisols and many Oxisols, whi ch r equi r e onl y small amount s of l i me. T h e
t ot al a nd available amount s of some mi cr onut r i ent s i n LAC soils t end t o be
very small, and yields may be very sensitive t o i ncreases i n pH t hat affect t he
availability of mi cr onut r i ent s. Not i ce i n Fi gur e 3.9 t hat a small a mount of
l i me, 0. 5 t o n / h a or about t he a mount needed t o neut r al i ze t he XA1,
i ncr eased t he yield of all four cultivars. Addi t i onal l i me sharpl y decr eased
yield for t wo cultivars, but t wo ot her s wer e little affected. Th e LAC soils
t end t o have small ECEC, and l i mi ng may pr oduce a significant i ncrease i n
t he ECEC, as shown i n Fi gur e 3. 10.
FIGURE 3. 9 The response to l i mi ng of four different cassava
cultivars grown on Oxi sol s in Col ombi a. Type 1, normal re-
sponse; type 2, little response; type 3, little positive response
fol l owed by marked negati ve effect; type 4, marked initial re-
sponse fol l owed by drastic negati ve effect.
Soils with High ECEC and XCa..Na
Deficiencies of Ca and Mg and al umi num toxicity ar e sel dom a pr obl em i n
a c i d- mi ne r a l soils wi t h hi gh ECEC and hi gh XCa. . Na. The s e soils ar e
typically no mor e t han moder at el y weat her ed and have a significant cont ent
of pr i mar y mi ner al s t hat can weat her and suppl y bot h macr onut r i ent s and
mi cr onut r i ent s. T h e soils ar e buffered agai nst changes i n availability of
FIGURE 3. 10 The effect of l i mi ng on soil pH and the effective cation
exchange capacity of an Ultisol. (From Sanchez, Villachica, and Bandy,
1983, used by permission of the Soil Sci ence Society of Ameri ca. )
Use of Lime 55
mi cr onut r i ent s with changes i n soil p H, al t hough an i ncrease i n pH may
significantly affect mi cr onut r i ent availability, commonl y t he case for Mo.
For t hese soils a consi der abl e change i n pH may be associated wi t h little
change i n yield, as i ndi cat ed by t he dat a i n Tabl e 3. 3, and injury t hr ough
over l i mi ng i s unlikely. Thus , t he lime r equi r ement i s t he a mount t hat will
adjust t he soil t o some sel ect ed p H, based pri mari l y on t he needs of t he
cr ops t hat ar e pr oduced.
Theor et i cal l y, t he best way t o det er mi ne t he a mount of lime t o add t o
achi eve a par t i cul ar pH i s t o add varyi ng amount s of lime and t hen det er -
mi ne t he equi l i br i um pH (see Fi gur e 3. 11). A r api d met hod i s ne e de d i n
soil-testing labs wher e a l arge numbe r of sampl es ar e t est ed. Commonl y, a
known a mount of buffer sol ut i on wi t h a gi ven pH (7. 0, 7. 5, or 8.0) i s mi xed
with a st andar d a mount of soil. Aft er a s t andar d per i od of st i rri ng and
st andi ng, t he pH of t he soil and buffer suspensi on i s measur ed. Th e depr es-
sion of pH from t hat of t he buffer sol ut i on i s equat ed wi t h t he a mount of
l i me needed t o i ncrease soil pH t o cer t ai n levels, as shown i n Tabl e 3. 4.
T h e Shoemaker , McLean, and Pr at t buffer met hod (SMP) i s r ecom-
me nde d for use i n t he Nor t h Cent r al states and i s used i n about 18 states.
Th e buffer consists of a combi nat i on of p- ni t r ophenol , t r i et hanol ami ne,
pot assi um chr omat e, cal ci um acet at e, and cal ci um chl or i de. T h e buffer
agent i s adj ust ed t o pH 7. 5 wi t h Na OH. Thi s me t hod i s well sui t ed for soils
wi t h appr eci abl e buffer acidity and consi der abl e XA1. In t he sout heast er n
CaCO3 added, tons/acre
FIGURE 3. 11 Soil pH as a functi on of added calcium carbonate. The
soil on the left is the least buffered and the soil on the right is the most
buffered. (Data from Shoemaker, McLean, and Pratt, 1961. )
TABLE 3.4 Lime Requirement To Achieve Various Soil pH Levels for an
Eight-Inch-Thick Plow Layer per Acre
Soil + buffer,
pH
Mineral soils,
tons of limestone* needed for
Organic soils
tons of limestone
needed for
pH 5.2
Soil + buffer,
pH pH 7.0 pH 6.5 pH 6.0
Organic soils
tons of limestone
needed for
pH 5.2
6.8 1.4 1.2 1.0 0.7
6.6 3.4 2.9 2.4 1.8
6.4 5.5 4.7 3.8 2.9
6.2 7.5 6.4 5.2 4.0
6.0 9.6 8.1 6.6 5.1
5.8 11.7 9.8 8.0 6.2
5.6 13.7 11.6 9.4 7.3
5.4 15.8 13.4 10.9 8.4
5.2 17.9 15.1 12.3 9.4
5.0 20.0 16.9 13.7 10.5
*Ground agricultural lime with 90% neutralizing power and 40% t hrough 100 mesh,
50% t hrough 60 mesh, 70% t hrough 20 mesh, and 95% t hrough 8 mesh.
Source: Recommended Chemical Soil Test Procedures for t he Nort h Central Regi on,
1975.
Uni t ed St at es, about four states use t he Adams a nd Evans buffer met hod.
T h e buffer r eagent i s a combi nat i on of p- ni t r ophenol , bor i c acid, pot assi um
chl or i de, and pot assi um hydr oxi de adj ust ed t o a pH of 8. 0. T h e met hod i s
well sui t ed t o soils t hat have a low ECEC and little need for l i me. Th e l i me
r equi r ement of Histosols is similarly det er mi ned with buffer sol ut i ons;
however , l i mi ng t o no mor e t han pH of 5.2 i s r e c omme nde d because above
pH 5.2 t he availability of some of t he mi cr onut r i ent s i s r educed.
Li me s t one as a Li mi ng Ma t e r i a l
Most of t he lime used t o neut r al i ze soil acidity i s gr ound l i mest one. Li me-
st one cont ai ni ng all Ca CO3 i s calcitic, and l i mest one cont ai ni ng varyi ng
amount s of bot h Ca CO3 and Mg CO3 i s dol omi t i c l i mest one. T h e t wo most
i mpor t ant pr oper t i es of gr ound l i mest one ar e its neut r al i zi ng val ue and its
part i cl e size. T h e fi rst det er mi nes how much aci d can be neut r al i zed by a
given a mount of l i mest one, t he second how rapi dl y t he l i mest one will
dissolve and neut r al i ze soil acids.
Th e neut r al i zi ng val ue of l i mi ng mat eri al s i s easily det er mi ned by
addi ng a known a mount of lime t o a known a mount of acid and al l owi ng
neut r al i zat i on t o go t o compl et i on. T h e excess acid i s t i t r at ed wi t h a base,
and t he neut r al i zi ng val ue i s equat ed t o t he a mount of acid neut r al i zed by
t he sampl e. Th e neut r al i zi ng val ue i s expressed as t he cal ci um car bonat e
equi val ent (CCE), wi t h pur e Ca CO3 r at ed as 100. If a l i mest one cont ai ned
only Ca CO3 , and no i mpuri t i es, t he CCE woul d be 100. Th e CCE of ot her
pur e l i mi ng mat eri al s i s given i n Tabl e 3. 5. Wood ashes from har dwoods
have a CCE of about 80 and ar e a good l i mi ng mat eri al for gar dens.
Use of Lime 57
T h e part i cl e size of l i mest one i s det er mi ned by t he fi neness of gr i nd-
i ng. T h e dissolution of l ar ge part i cl es, l ar ger t han t hose abl e t o pass an
8-mesh screen, i s so slow t hat t hey have little or no affect on soil p H. Thi s
fract i on has an effective r at i ng of zer o. Part i cl es passi ng an 8-mesh screen
but r et ai ned on a 60-mesh screen ar e r at ed 50% effective. Part i cl es passing
a 60- mesh screen ar e r at ed 100% effective. T h e CCE and t he cal cul at ed
fi neness factor ar e mul t i pl i ed t oget her t o det er mi ne t he effectiveness of a
gr ound l i mest one or t he effective cal ci um car bonat e (ECC). I f an ent i r e
sampl e passes t he 8-mesh screen and 50% i s r et ai ned on t he 60-mesh
screen, t he fi neness fact or will be 75. For a sampl e wi t h a CCE of 90, t he
ECC will be 67. 5.
Ap p l i c a t i on of Li me
Li me can be appl i ed at any t i me bet ween t he har vest of one cr op and t he
pl ant i ng of t he next . T h e maj or consi derat i ons ar e t he availability of t he
l i me and t he conveni ence of spr eadi ng. Li me i s usually br oadcast on t he soil
surface bef or e tillage oper at i ons so t hat t he soil and l i mest one ar e mi xed t o
i ncrease soil and lime cont act . Cal ci um car bonat e is qui t e i nsol ubl e, dis-
solves slowly, and has very l i mi t ed downwar d mobi l i t y. Calcitic l i me, how-
ever, dissolves mor e rapi dl y t han dol omi t i c l i me. T h e r at e of neut r al i zat i on
i s i mpor t ant l y r el at ed t o fi neness, uni formi t y of di st r i but i on i n t he soil, and
t he r at e of diffusion of Ca from t he l i me part i cl es t o t he sites of neut ral i za-
t i on. A r easonabl e diffusion r at e for C a
2 +
i s 0. 35 cm i n 100 days or 0. 78 cm
in 500 days. If l i mest one is appl i ed at a r at e of 2. 7 t ons / a c r e (6 t ons / ha ) in
part i cl es 0. 60 mm i n di amet er (30 mesh), t he aver age di st ance bet ween
part i cl es of lime will be 1.04 cm. Thi s statistic illustrates t he i mpor t ance of
fi neness and uni f or m di st ri but i on. Subsoils of many Ultisols and Oxisols
limit r oot gr owt h t hr ough Al toxicity, deficient Ca, or bot h. Deep i ncor po-
r at i on of lime or downwar d movement of lime over a l ong per i od of t i me
will hel p t o i ncrease yields by i ncreasi ng t he available wat er supply. T h e
hi gh cost of appl yi ng l i me t o subsoils and t he lack of available equi pment
great l y limit t he deep i ncor por at i on of l i me.
Li mi ng, i n a sense, reverses some of t he nat ur al processes t hat make
soils acid. It i s only nat ur al t o expect t hat once an aci d soil has been l i med,
l eachi ng and pl ant gr owt h will event ual l y l ower t he pH agai n. St udi es
conduct ed i n Ohi o showed t hat t he annual loss of Ca by l eachi ng was
gr eat er t han t he Ca r emoved i n har vest ed cr ops. Whe n r ot at i ons i ncl ude a
TABLE 3.5 Neutralizing Value of Liming Materials
Material Calcium carbonate equivalent
Calcium carbonate 100
Dolomite 109
Calcium hydroxide 136
Calcium oxide 179
Calcium silicate 86
l egume cr op, l i mi ng of acid soils i s r equi r ed every t hr ee t o fi ve years i n
Illinois to mai nt ai n a satisfactory soil p H. In no-till systems t her e is l i mi t ed
mi xi ng of soil by tillage oper at i ons, and surface appl i cat i ons of N fertilizers
will t end t o cause r api d acidification of t he upper 3 i nches of soil. T h e dept h
of soil sampl i ng and t he appl i cat i on of lime will need t o be adj ust ed
accordi ngl y.
Ov e r l i mi ng
Over l i mi ng can be a pr obl em when soils have low CEC and a very small
a mount of buffer or r eser ve acidity, whi ch easily allow an i ncrease i n p H.
Over l i mi ng is most likely on soils wi t h low ECEC, such as sandy soils wi t h
per manent - char ge clays and LAC soils. Pl ant r esponse t o over l i mi ng i s
hi ghl y vari abl e and depends on t he cul t i var. Over l i mi ng i s expensi ve, and
crops ar e i nj ured pri mari l y by t he r educed availability of cer t ai n
mi cr onut r i ent s.
Ef f ect of F l ood i ng on Li me Ne e d s
Li me r equi r ement s for upl and rice ar e det er mi ned i n t he same way as for
ot her crops. Fl ooded or paddy ri ce, however , r ar el y needs lime because t he
consumpt i on of H
+
dur i ng r educt i on i n anaer obi c soil i ncreases soil p H. I n
fact, most paddy soils when fl ooded have an equi l i br i um pH bet ween 6.5
and 7. 5. Whe n t he O2 suppl y of t he soil i s exhaust ed, soil mi cr oor gani sms
ar e forced t o use progressi vel y weaker el ect r on accept or s. Aft er O2 , t he
next st rongest el ect r on accept or available i s ni t r at e, followed by Mn O2 ,
Fe ( OH) 3 , and sulfate. Two exampl es of t he r eact i on ar e
2 N O 3 - + 10e
+ 1 2 H
+
= N2 + 6 Hz O (3. 21)
Mn O2 + 2e
+ 4H+ = Mn
2 +
+ 2 H2 O (3. 22)
A C I D R A I N I N P U T S
Unpol l ut ed r ai n i n equi l i br i um wi t h t he nor mal CO2 cont ent of t he at mo-
spher e has a pH of 5.6 (5. 67 for pur e wat er). A met er of this rai n, whi ch is
about a year' s supply i n humi d r egi ons, can dissolve about 320 t o 400
pounds / a c r e of Ca CO3 ( 400 t o 500 kg/ ha ) , whi ch i s r oughl y equal t o t he
a mount of lime needed t o mai nt ai n t he pH of agr i cul t ur al soils i n Illinois.
T h e bur ni ng of fossil fuel rel eases oxi des of S and N whi ch event ual l y
r et ur n i n t he preci pi t at i on; t hey cause t he pH of t he pr eci pi t at i on t o be less
t han 5.6 and t o become an acid precipitation. In t he nor t heas t er n Uni t ed
St at es t he pr eci pi t at i on i n 1981 cont ai ned an aci d equi val ent , from t he
effects of acid rai n, of 28. 8 pounds / a c r e of Ca CO3 ( 32. 3 kg/ ha ) . At Knox-
ville, Tennes s ee t he annual f i gur e has been r epor t ed t o be 83 pounds / a c r e
(93 kg/ ha ) . By compar i son, t he aci d- pr oduci ng pot ent i al of t he aver age N
fertilizer appl i cat i on i n t he Uni t ed States i s 179 pounds / a c r e (201 kg/ ha ) .
Soil Acidification 59
Th e f i xat i on of N by alfalfa can a mount t o t he equi val ence of 500 p o u n d s /
acr e or mor e of Ca CO3 ( 560 kg/ ha ) . Since only par t of t he t ot al preci pi t a-
t i on i s due t o t he acid rai n component , i t can be seen t hat aci d r ai n
cont r i but es a small a mount t o t he t ot al acid i nput of soils i n t he humi d
r egi on of Uni t ed St at es.
SOI L A C I D I F I C A T I O N
Pl ant s t hat pr ef er qui t e an acidic soil i ncl ude r hodode ndr on, bl ueber r y,
azal ea, cassava, and t ea (see Fi gur e 3. 12). Scab disease of Iri sh pot at oes,
caused by an act i nomycet e, has been cont r ol l ed by mai nt ai ni ng an aci d soil
i n whi ch t he or gani sm i s i nact i ve. Lar ge areas of l and ar e not general l y
acidified i n t he way t hat l i mi ng i s r out i nel y used t o i ncrease t he pH of l ar ge
fi el ds. Acidification i s most frequent l y appl i ed i n nur ser i es and hor t i cul t ur al
si t uat i ons.
Sul fur and sulfur compounds ar e t he most popul ar acidifying com-
pounds . El ement al S i s t he most economi cal and i s oxi di zed t o sulfuric aci d
by bact er i a, mai nl y Thiobacillus:
2S + 3O2 + 2 H2 O = 2 H2 S O4 (3. 23)
Mi crobi al catalysis pr omot es t he r eact i on, whi ch i s i rreversi bl e and occurs
slowly. Al umi num (and Fe) sulfate is commonl y used in hor t i cul t ur al situa-
t i ons. T h e r eact i on i s
Al 2 ( SO4 ) 3 + 6 H2 O = 2Al ( OH) 3 + 3 H2 S O4 (3. 24)
T h e Al ( OH) 3 preci pi t at es, l eavi ng t he aci d t o acidify t he soil. Some of t he
Al 2 ( SO) 4 may r eact wi t h t he soil t o pr oduce addi t i onal acidification:
A12 ( SO4 ) 3 + 3CaX = Al 2 X3 + Ca SO4 + H2 S O4 (3. 25)
FIGURE 3.12 Te a is a calcifuge and dislikes soils contai ni ng free calcium.
Te a grows well on soils that have a pH of 4.5 and a hi gh percentage of
exchangeabl e al umi num saturation.
TABLE 3.6 Finely Ground Sulfur to Lower Plow Layer pH to about 6.5
Broadcast, kg/ ha* Band, kg/ ha
Soil pH Sandy soil Clay soil Sandy soil Clay soil
7.5
8.0
400- 600 800- 1000
1000- 1500 1500- 2000
200- 250 300- 500
300- 500 600- 800
*Multiply by 0. 892 for pounds per acre.
Source: Jones, 1982, used by permi ssi on of Prent i ce- Hal l , Engl ewood Cliffs, N.J.
Gypsum, Ca SO4 , has been f ound t o be effective i n i ncreasi ng s or ghum
yields on cal careous soils i n Kansas. Th e maj or benefi t appear ed t o be
i ncreased availability of Zn. Cal careous soils ar e not usually made acid
because costs ar e hi gh. Whe n soils ar e l eached of salts, t he r equi r ement s for
S ar e r easonabl e, al l owi ng for economi cal soil acidification. Somet i mes S is
appl i ed as a fertilizer to i ncrease acidity in a small fract i on of t he soil mass.
Th e S i s appl i ed i n a band wher e earl y r oot gr owt h occurs. Suggest ed rat es
of S for soil acidification ar e given in Tabl e 3. 6.
Aci d or gani c mat eri al s may be beneficial, but t hey ar e not pract i cal
wher e a significant decr ease in soil pH is desi red. Most N fertilizers i ncrease
soil acidity, and t hei r effects on soil acidity ar e discussed i n t he next chapt er .
REF ERENCES
Bohn, H. L., B. L. McNeal, and G. A. O' Connor. 1985. Soil Chemistry. 2nd ed. John
Wiley, New York.
Follett, R. H. and R. F. Follett. 1983. Soil and Lime Requirement Tests for the 50
States and Puerto Rico. Jour. Agron. Educ. 12: 9- 17.
Foy, C. D. and G. D. Burns. 1964. Toxic Factors in Acid Soils. Plant Food Rev.
10: 1- 2, No. 3. Nat. Plant Food Inst. Washington, D.C.
Hargrove, W. L. and G. W. Thomas. 1981. Effect of Organic Matter on Exchange-
able Aluminum and Plant Growth in Acid Soils. In Chemistry in the Soil Environ-
ment. Am. Soc. Agron. Spec. Pub. 40, Madison, Wis.
Jones, U. S. 1982. Fertilizers and Soil Fertility. 2nd ed. Reston, Va.
Kamprath, E. J. 1972. Soil Acidity and Liming. In Soils of the Humid Tropics. Nat.
Acad. Sci. Washington, D.C.
Kamprath, E. J. 1984. Fertility Management of LAC Soils. Agron. Abstracts. Am.
Soc. Agron., Madison, Wis.
Kamprath, E. J. and C. D. Foy. 1985. Lime - Fertilizer Interactions in Acid Soils.
Fertilizer Technology and Use. Am. Soc. Agron., Madison, Wis.
Krug, E. E. and C. R. Frink. 1983. Acid Rain on Acid Soil: A New Perspective.
Science. 221: 520- 525.
Lucas, R. E. 1982. Organic Soils (Histosols). Research Report 435, Mich. Agr. Exp.
Sta., East Lansing.
Lucas, R. E. and J. F. Davis. 1961. Relationships Between pH Values of Organic
Soils and Availabilities of 12 Plant Nutrients. Soil Sci. 92: 177- 182.
References 61
Marion, G. M., D. M. Hendricks, G. R. Dutt, and W. H. Fuller. 1976. Aluminum
and Silica Solubility in Soils. Soil Sci. 121: 76- 82.
Myers, J. A., E. O. McLean, and J. M. Bigham. 1988. Reductions of Exchangeable
Magnesium with Liming of Acid Ohio Soils. Soil Sci. Soc. Am. four. 52: 131- 136.
North Central Region Soil Testing Committee-13. 1975. Recommended Chemical Soil
Test Procedures. Bull. 499, North. Dak. Agr. Exp. Sta., Fargo.
Sanchez, P. A., J. H. Villachica, and D. E. Bandy. 1983. Soil Fertility Dynamics after
Clearing a Tropical Rainforest in Peru. Soil Sci. Soc. Am. four. 47:1171 - 1178.
Shoemaker, H. E., E. O. McLean, and P. F. Pratt. 1961. Buffer Methods for
Determining Lime Requirement of Soils with Appreciable Amounts of Extract-
able Aluminum. Soil. Sci. Soc. Am. Proc. 25: 274- 277.
Soil Survey Staff. 1975. Soil Taxonomy. USDA Agriculture Handbook 436, Wash-
ington, D.C.
Spain, J. M., C. A. Francis, R. H. Howeler, and F. Calvo. 1975. Differential Species
and Varietal Tolerance to Soil Acidity in Tropical Crops and Pastures. In Soil
Management in Tropical America. Soil Science Dept., North Carolina State Uni-
versity, Raleigh.
Spurway, C. H. 1941. Soil Reaction Preferences of Plants. Spec. Bull. 306, Mich. Agr.
Exp. Sta. East Lansing.
Thomas, G. W. and W. L. Hargrove. 1984. The Chemistry of Soil Acidity. In Soil
Acidity and Liming. Agronomy 12: 1- 58. 2nd ed., F. Adams, ed. Am. Soc.
Agron., Madison, Wis.
University of Kentucky, Soil Handbook, 1970.
Wolcott, A. R., H. D. Foth, J. F. Davis, and J. C. Shickluna. 1965. Nitrogen
Carriers: Soil Effects. Soil Sci. Soc. Am. Proc. 29: 405- 410.
Wolt, J. D. and D. A. Lietzke. 1982. The Influence of Anthropogenic Sulfur Inputs
upon Soil Properties in the Copper Basin Region of Tennessee. Soil Sci. Soc. Am.
four. 46: 651- 656.
C H A P T E R 4
Soil and Fertilizer Nitrogen
Ni t r ogen is a par t of all living cells. In pl ant s N is a const i t uent of chl or o-
phyll, all pr ot ei ns i ncl udi ng t he enzymes, and many ot her compounds . Of
t he nut r i ent s r emoved from t he soil by pl ant s, onl y H at oms ar e pr esent i n a
gr eat er numbe r t han N at oms. A lack of N causes leaves to become yellow
and st unt s gr owt h. Conversel y, wi t h an adequat e suppl y of N, veget at i ve
gr owt h i s r api d and foliage dar k gr een i n col or. T h e l ar ge need of pl ant s for
N and t he l i mi t ed ability of soils to supply available N cause N to be t he
most l i mi t i ng nut r i ent for cr op pr oduct i on on a gl obal basis.
I N V EN T O R Y O F T H E EA R T H ' S N I T R O G EN
About 9 8 % of t he wor l d' s N exists i n t he l i t hospher e (see Tabl e 4. 1).
Ni t r ogen i s a component of coal and many ot her rocks and mi neral s.
Ammoni um i s fi xed i n t he clays of sedi ment s and i n mi ca mi neral s of rocks
in t he same voids wher e K is fixed. T h e second l argest N r eser voi r is t he
at mos pher e, whi ch cont ai ns about 2% of t he t ot al . Most of t he N i n t he
at mos pher e i s bel i eved t o have or i gi nat ed from t he l i t hospher e, and even
t oday volcanic gases cont r i but e N t o t he at mos pher e. By cont rast , t he
a mount of N in soils is very small, bei ng onl y 1/ 5 000t h of t hat of t he
at mos pher e. Many pr oduct i ve mi ner al soils cont ai n about 4 000 k g / h a (or
about 4 000 pounds / a c r e ) in t he furrow slice. About 90% of t he soil N is
unavai l abl e i n or gani c mat t er , and most of t he r emai nder exists as fi xed
a mmoni um in clays. At any one i nst ant about 1 % or less of t he t ot al N in
soils i s available t o pl ant s and mi cr oor gani sms as ni t r at e or exchangeabl e
a mmoni um. T h e a mount of N in t he bi ospher e, like t hat in t he soil, is a very
small par t of t he t ot al , but this N i s very mobi l e and life depends on it.
62
The Soil Nitrogen Cycle 63
TABLE 4.1 Inventory of the Earth' s Nitrogen
Sphere Million metric tons
Lithosphere 1.636 X 10
11
Igneous rocks of crust 1.0 X 10
9
Igneous rocks of mantle 1.62 X 10
11
Core of the earth 1.3 X 10
8
Sediments (fossil N) 3. 5- 5. 5 X l 0
8
Coal 1.0 X 10
5
Sea bottom organic compounds 5.4 X 10
5
Terrestrial soils
Organic matter 2.2 X 10
5
Clay-fixed NH4
+
2.0 X 10
4
Atmosphere 3.86 X 10
9
Hydrosphere 2.3 X 10
7
Biosphere 2.8 X 10
5
Source: Estimates from various sources as given by Stevenson, 1982.
T H E SOI L N I T R O G EN CYCLE
Al t hough t he gr eat bul k of t he ear t h' s N i s i n t he rocks and sedi ment s of t he
l i t hospher e, t he most i mpor t ant r eser voi r of N for pl ant s and ani mal s i s t he
at mos pher e. Pur e, dr y ai r i s about 7 8 % N by vol ume, whi ch means t hat i t
can suppl y 77 350 met r i c t o n s / h a (34 500 t ons / acr e) of N. Consi der i ng t he
aver age biological need for N, t he at mos pher e cont ai ns about a million
year s' supply. Th e annual r at e of r emoval of N f r om t he at mos pher e by
fixation and its addi t i on to soils, is appr oxi mat el y bal anced by an equal
a mount of N r e t ur ne d t o t he at mos pher e by deni t ri fi cat i on. Thus , over
t i me, a quasi -equi l i bri um exists bet ween t he a mount of N i n t he at mos pher e
and t he a mount of N in soils on a global basis.
Th e N cycle in soils is a par t of t he ear t h' s overall N cycle. T h e net
effect of this overall cycle is t hat N ci rcul at es t hr ough t he soil and event u-
ally r et ur ns t o t he at mos pher e t hr ough a series of processes: fi xat i on,
mi neral i zat i on, nitrification, i mmobi l i zat i on, and deni t ri fi cat i on. The s e
processes, as shown i n Fi gur e 4 . 1 , can be vi ewed as a series of i rreversi bl e
react i ons t hat ar e medi at ed by mi crobi al catalysis and t hat shut t l e N back
a nd fort h at t he di scret i on of t he mi cr oor gani sms.
Nonb i ol og i c a l Fi x a t i on
Some N fixation is nonbi ol ogi cal and is caused by l i ght ni ng di scharges.
Ot he r N i n t he at mos pher e ori gi nat es from t he bur ni ng of fossil fuels and
forests and from t he emission of magmat i c gases. Thi s N i s a dde d t o soils as
ni t r at e and a mmoni um i n preci pi t at i on. I t has been est i mat ed t hat of t he
12. 8 k g / h a (11. 4 pounds / a c r e ) of N nat ural l y a dde d t o soils annual l y, 72%
comes from biological N fi xat i on and 2 8 % from t he ot her sources.
Bi ol og i c a l Ni t r og e n Fi x a t i on
Consi der i ng t he l ar ge a mount of N added t o soils by biological fi xat i on and
t he i mpor t ance of N in pl ant gr owt h, biological N fixation can be consid-
er ed one of t he most i mpor t ant processes i n nat ur e. In a way, i t i s similar t o
phot osynt hesi s. Th e r e is a ubi qui t ous need for N in nat ur e, and in every
ecological ni che t her e ar e mi cr oor gani sms t hat f i x N. Th e gr eat di versi t y of
fixation sites and or gani sms is i l l ust rat ed by a fl ooded ri ce field (paddy), as
shown i n Fi gur e 4. 2.
Biological N fixation systems have been gr ouped i nt o f our cat egori es.
The s e systems, t he r epr esent at i ve or gani sms i nvol ved, and t he amount s of
N fi xed annual l y ar e given i n Tabl e 4. 2.
Symbiotic Fixation
In symbiotic systems t he host pl ant supplies t he N-fixing or gani sms with
f i xed C, a_phot osynt hat e, and t he host pl ant s benefi t from t he N f i xed. T h e
N-fixing mi cr oor gani sms ar e bact eri a, act i nomycet es, and bl ue- gr een al gae
FIGURE 4. 2 Di agram of ni trogen-fi xi ng organi sms i n a rice fi el d ecosystem. Bacte-
ria: (1) rhi zosphere, (2) soil, (3) epiphytic on rice. Cyanobacteria (bl ue-green algae):
(4) free fl oati ng, (5) soi l - wat er interface, (6) wat er- ai r interface, (7) epiphytic on
rice. Azolla: (8) floating on surface. (Drawn after Kulasooriya et al., 1980. )
66 Soil and Fertilizer Nitrogen
System and organisms N2 fixed, kg/ ha
Symbiotic systems
Legumes, bacteria
Alfalfa 128- 600
Lupins 150- 169
Clover 104- 160
Soybeans 57- 94
Cowpeas 84
Nonlegume-nodulated, actinomycetes
Alnus (alder) 40- 300
Ceanothus 60
Plant-algal associations
Lichens 3 9 - 8 4
Gunnera 12- 21
Azollas 313
Nonsymbiotic systems, free-living organisms
Blue-green algae 25
Azotobacter 0.3
Clostridium pasteurianum 0. 1- 0. 5
Source: Data from various sources as gi ven by Evans and Barber, 1977.
(cyanobact eri a). All t hese or gani sms, whi ch ar e called di azot r ophs, have a
very si mpl e cell st r uct ur e wi t hout a nucl eus and synt hesi ze t he enzyme
ni t r ogenase. Di ni t r ogen, N2 , i s r educed t o N H 3 (from val ence of 0 t o -3). In
a chemi cal pl ant N i s fi xed by usi ng hi gh t emper at ur e and pr essur e. T h e
di azot r ophs accompl i sh t he same feat at ambi ent t emper at ur e and at mo-
spheri c pr essur e. Biological N fixation is not free because t he ener gy for
fixation is der i ved from a phot osynt hat e. For soybeans it has been est i mat ed
t hat t he ener gy used t o fi x N i s equal t o t he ener gy i n about 20 bus hel s / ha
of gr ai n or 8 bushels/acre.
Since Gr eek and Roman t i mes t he use of l egumes t o i ncrease soil
fertility has been a c ommon pract i ce. He r ma nn Hel l ri egel and H. Wi l fart h
of Ger many i n 1888 f ound t hat nonl egumi nous crops, such as barl ey a nd
oat s, grew i n sand cul t ur e i n di r ect r esponse t o t he a mount of N suppl i ed.
For l egumes, however , t her e was no rel at i on bet ween t hei r gr owt h and t he
addi t i on of fertilizer N. In this way t he link bet ween nodul es on l egume
r oot s and N fi xat i on was di scovered. Legumes ar e di cot s t hat devel op a
symbi ot i c N fixation rel at i on wi t h bact er i a of t he genus Rhizobium. It is
est i mat ed t hat over half of t he biologically fi xed N added t o t he ear t h i s due
t o l egume symbioses i n agr i cul t ur al pr oduct i on, and this i s equal t o t wo
t i mes t he a mount of N a dde d t o soils i n fertilizers. Th e i mpor t ance of
l egumes in agr i cul t ur e is shown by t hei r hi gh r at es of N fixation (see
Tabl e 4. 2).
Rhi zobi a t end t o be host-specific, al t hough some infect several differ-
ent host s, and mor e t han one species may infect a single pl ant . T h e bact eri a
can live in t he soil for l ong per i ods of t i me in a nonsymbi ot i c st at e. How-
ever, t o ens ur e t hat t he pr ope r species i s pr esent , f ar mer s usually pl ant seed
i nocul at ed wi t h bact eri a t hat will f or m an efficient N-fixing system wi t h t he
l egume. Bact eri a living near t he r oot of a host pl ant appar ent l y have a
r ecogni t i on mechani sm t hat t r i gger s a hos t - ba c t e r i a r ecogni t i on event .
T h e pr esence of t he bact eri a adj acent t o a r oot hai r causes br anchi ng and
curl i ng, followed by t he i nvasi on of t he bact eri a. An i nfect i on t hr ead i s
f or med and penet r at es t he r oot as t he bact eri a cont i nue t o di vi de and
mul t i pl y. Th e pl ant ' s r esponse i s t o form a t umor ous nodul e cont ai ni ng
cells t hat become packed with bacteroids, whi ch ar e bact eri a t hat have
unde r gone mor phol ogi cal and met abol i c change. T h e bact er oi ds ar e sup-
pl i ed wi t h a phot osynt hat e, whi ch is used for respi rat i on and N-fixing
activities. T h e N fi xed as ammoni a i s excr et ed from t he bact er oi ds t o t he
l egume cells and i s t hen t r ans por t ed as C - N compounds i n t he vascular
system. Th e rel at i onshi p i s one of t r ue symbiosis, since t her e i s a di r ect
connect i on bet ween t he host and symbi ont for t he t ransfer of phot osynt h-
at e t o t he symbi ont and for t he t ransfer of fi xed N t o t he host (see
Fi gur e 4. 3).
Rhi zobi a f or m associations with many t rees. However , t he most i mpor -
t ant symbi ot i c rel at i onshi ps wi t h di cot yl edonous woody shr ubs and t rees
ar e t hose with cert ai n act i nomycet es of t he Frankia genus. Th e i nfect i on of
r oot s and nodul e f or mat i on have similarities t o t he l e gume - r hi z obi a sys-
t ems. Alnus is a pi oneer genus of l arge t rees t hat gr ow in t he Rocky
Mount ai ns and on t he Pacific slope. The y ar e f ound on freshly exposed
FIGURE 4. 3 Schemati c drawi ng of a l egume root nodul e
and root segment. (From Phillips and DeLong, 1984, used
by permission of the Ameri can Society of Agronomy and the
Soil Sci ence Society of Ameri ca. )
TABLE 4. 2 Relative Annual Rates of Nitrogen Fixation
par ent mat eri al s and ar e an i mpor t ant N cont r i but or i n t he early stages of
soil f or mat i on. Aft er cl ear-cut t i ng of Dougl as fir forests in t he Pacific
Nor t hwest of t he Uni t ed St at es, Ceanothus-Frankia symbiosis cont r i but es a
significant a mount of N for t he r egener at i on of t he Dougl as fir forests (see
Tabl e 4. 2). Nodul es on t he r oot s of Ceanothus, a showy genus of shr ubs and
woody vines, ar e shown i n Fi gur e 4. 4.
On e of t he best -known symbi ot i c algal N-fixing associations consists of
bl ue- gr een al gae and t he fungi i n lichens. T h e al gae fi x N t hat benefi t s t he
fungi, and t he al gae appear t o benefi t from t he bi ot i n and t hi ami ne pr o-
duced by t he fungi. I n wet and t ropi cal envi r onment s bl ue- gr een al gae
i nvade t he stems of her baceous dicots of t he Gunnera genus. Gl ands ar e
f or med on t he st ems, similar t o nodul es on r oot s, and t he al gae fi x N i n t he
gl ands. Th e most i mpor t ant symbi ot i c algal association for agr i cul t ur e i s t he
Azolla-Anabaena association, whi ch is used for rice pr oduct i on in fl ooded
fi el ds. Th e azolla i s a floating fern wi t h r oot s t hat penet r at e bel ow t he wat er
surface (see Fi gur e 4. 2). Th e anabaenas, whi ch ar e bl ue- gr een al gae, live i n
t he fronds of t he fern. Th e r e i s no vascular connect i on bet ween t he t wo
or gani sms. Up t o 60 per cent of t he fern' s N comes from ammoni a pr o-
duced by t he anabaenas. T h e benefits der i ved from t he association by t he
al gae ar e unknown. Th e r api d gr owt h of bi omass t hat i s possible unde r
favorabl e condi t i ons allows for t he pr oduct i on of l ar ge amount s of gr een
ma nur e ri ch in N (see Tabl e 4. 2). In ri ce paddi es t he N is rel eased to t he
rice when t he or gani c mat t er i s mi neral i zed. Th e floating bi omass can also
be ski mmed off t he surface of ponds and used as a hi gh- pr ot ei n ani mal feed.
Thus , gr eat diversity exists i n t he symbi ot i c N-fixing systems t hat account
FIGURE 4.4 Nodul es on the roots of Ceanothus, in whi ch acti nomycetes fix
ni trogen.
for t he addi t i on of l arge amount s of N to soils in nat ur al ecoyst ems as well as
i n agri cul t ural fi el ds.
Nonsymbiotic Fixation
Several ki nds of het er ot r ophi c bact eri a ar e N fi xers and ar e of mi nor
i mpor t ance i n agri cul t ural soils. The s e het er ot r ophs must compet e wi t h
ot her soil or gani sms for t he l i mi t ed suppl y of or gani c subst rat es t hat ar e
available for t hei r C and ener gy. Azotobacter and Beijernickia ar e aer obes
a nd occur in t emper at e and t ropi cal soils, respectively. Clostridium is a
het er ot r ophi c bact er i um t hat t hri ves onl y unde r anaer obi c condi t i ons. Azo-
spirillum is a bact er i um t hat has been f ound to live in t he r hi zospher e of t he
r oot s of t ropi cal grasses and f i x some N.
Bl ue-green al gae live near t he soil surface and fix N nonsymbi ot i cal l y.
Th e y ar e phot osynt het i c and need not compet e for t he l i mi t ed suppl y of
or gani c subst rat es. However , because of shadi ng by t he soil surface and
dr yi ng at t he surface, t hey ar e qui t e inactive i n most soils. In ri ce paddi es
a nd ot her fl ooded areas, bl ue- gr een al gae i n t he wat er f i x l arge amount s of
N and cont r i but e significantly to t he N needs of pl ant s.
Mi ne r a l i z a t i on
All t he mi ner al N added to soils by fixation or fertilizer is subject to upt ake
by r oot s and mi cr oor gani sms and t o conversi on i nt o or gani c soil N. Th e
or gani c N is r econver t ed to mi ner al f or m by a wi de vari et y of het er ot r ophi c
or gani sms bact eri a, fungi, and act i nomycet es in a process called miner-
alization. Thes e organi sms secret e ext racel l ar enzymes t hat decompose pr o-
t ei ns. In many wel l -drai ned mi ner al soils about 2% of t he or gani c N i s
mi ner al i zed annual l y. For soils with 0. 05% t o 0. 10% N, this amount s t o 25
t o 50 k g / h a (22 t o 45 pounds / a c r e ) for a 20-cm-t hi ck pl ow l ayer.
Since ammoni a, NH3 , i s t he f i r st mi ner al f or m pr oduced, t he process
has also been called ammonification. Ammoni a is a gas and can be lost from
t he soil by volatilization when mi neral i zat i on occurs on t he soil surface.
Much of this NH3 may be absor bed by leaves if t her e is a pl ant canopy.
Conversel y, near cat t l e feedl ot s and cer t ai n i ndust ri al sites, t he at mos pher e
may be enr i ched with NHS , and a significant a mount of N H 3 may be
ads or bed by near by soils and lakes. T h e ammoni a mol ecul e i s pol ar and
readi l y combi nes wi t h a pr ot on t o f or m ammoni um, N H 4
+
(see Fi gur e 4. 1).
Ammoni a is stabilized in acid soils, but in al kal i ne soils few pr ot ons ar e
available and volatilization i ncreases as t he soil pH i ncreases.
Factors Affecting Mineralization
T h e a mount of N mi ner al i zed t ends t o be r el at ed t o t he a mount of SOM
a nd envi r onment al condi t i ons. About 1% t o 4% of t he t ot al N i s mi neral -
i zed per year, unless t he soil i s t oo col d or t oo dr y for mi crobi al activity.
T h e opt i mum wat er cont ent for mi neral i zat i on i n wel l -aerat ed soils i s
50% t o 7 5 % of t he wat er - hol di ng capacity. Aft er fl oodi ng of aer obi c soils,
t he anaer obi c or gani sms t ake over a nd mi neral i zat i on may be little affected.
Soils t hat t end t o mi neral i ze a good a mount of N when aer at ed will t end t o
mi neral i ze a good a mount of N when fl ooded. Thus , ri ce f ar mer s com-
monl y appl y ani mal ma nur e bef or e fl oodi ng a nd get a good yield of N from
mi neral i zat i on. Dr yi ng t he soil bel ow t he opt i mum moi st ur e cont ent r e-
duces mi neral i zat i on and r educes t he a mount of N available. Wet t i ng dr y
soils appear s t o st i mul at e mi neral i zat i on a nd br i ngs a per i od of r api d mi ner -
alization or a f l ush i n N availability. T h e l onger t he dr y per i od, t he st r onger
i s this effect aft er wet t i ng, whi ch has not been satisfactorily expl ai ned. It has
been suggest ed t hat r api d mi neral i zat i on i n savannah soils aft er a l ong dr y
per i od pr oduces much N O 3
, and t hat this subst ance cont r i but es t o t he loss

of XCa. . Na by l eachi ng bef or e pl ant s reest abl i sh and actively absor b t he
ani ons f or med dur i ng t he flush per i od. Fr eezi ng followed by t hawi ng also
st i mul at es mi neral i zat i on.
Th e opt i mum t emper at ur e for N mi neral i zat i on i s 40 t o 60 degr ees C.
I n compost piles t he t her mophi l es t ake over and may be active at t emper a-
t ur es exceedi ng 65 degr ees. I n gener al , t emper at ur es favorabl e for r oot
gr owt h ar e favorabl e for mi neral i zat i on. Earl y-growi ng cr ops t hat ar e
pl ant ed in wet and cold soils may be st i mul at ed by earl y appl i cat i ons of N
fertilizer.
Mi neral i zat i on is affected by enzyme activity. T h e fact t hat t her e is a
st r ong positive cor r el at i on bet ween t he clay cont ent of soils and SOM
cont ent suggest s t hat clays may i nact i vat e t he prot eol yt i c enzymes i n some
way.
A mmo n i u m Fi x a t i on
T h e a mmoni um f or med by mi neral i zat i on appear s i n t he soil sol ut i on and
establishes an equi l i br i um wi t h t he exchangeabl e a mmoni um. Th e similar-
ity i n ionic r adi us and ener gy of hydr at i on of N H 4
+
a nd K
+
causes t he ions
t o compet e for fi xat i on sites i n mi caceous mi neral s. Th e upper limit of
fixation in field soils is about 1 to 2 me q / 1 0 0 g of soil. About 10 per cent of
t he N in soils may be fixed, and its di st r i but i on in t he soil profile paral l el s
t hat of t he clay. Just as with K, an equi l i br i um for N H 4
+
exists bet ween t he
ions t hat ar e exchangeabl e a nd t hose t hat ar e i n sol ut i on, and bet ween ions
t hat ar e exchangeabl e and t hose t hat ar e f i xed. Al t hough consi der abl e
fi xed N H 4
+
may exist i n soils, i t i s of mi nor i mpor t ance i n meet i ng t he daily
N needs of gr owi ng pl ant s.
Ni t r i f i c a t i on
Th e st ar t i ng poi nt for nitrification i s t he N H 4
+
pr oduced by mi neral i zat i on.
In aer obi c soils wi t h a pH of 6.0 or hi gher , N H 4
+
i s rapi dl y oxi di zed by
specialized chemoaut ot r ophi c bact eri a, whi ch ar e wi despr ead i n nat ur e.
T h e process i s nitrification, and i t occurs i n t wo steps. Bact eri a of t he genus
Nitrosomonas and several ot her bact er i a oxi di ze t he N H 4
+
t o ni t r i t e as
follows:
2 N H 4
+
+ 3O2 = 2 N O z - + 2 Ha O + 4 H
+
(4. 1)
T h e val ence of N goes from 3 t o + 3 , a nd t he ener gy rel eased i s sufficient
t o enabl e bact eri a t o f i x all t he C t hey need f r om CO2 . Not i ce t hat t he f i r st
st ep in nitrification pr oduces pr ot ons and is a nat ur al soil acidification
process. Ni t ri fi cat i on may significantly l ower soil pH when l arge amount s of
a mmoni um fertilizers ar e appl i ed. Li t t l e i f any ni t ri t e accumul at es because
t he ni t r i t e excr et ed by Nitrosomonas i s quickly pi cked up by bact eri a of
anot her genus, Nitrobacter, and oxi di zed t o ni t r at e as follows:
2 N 0 2
+ O2 = 2 NOs
(4.2)
T h e val ence of N goes from +3 t o + 5 . Ni t r at e i s stable i n t he soil sol ut i on.
However , it r emai ns sol ubl e and is subject to loss from soils by l eachi ng.
Factors Affecting Nitrification
Ammoni f i cat i on or N mi neral i zat i on is qui t e insensitive to t he soil envi r on-
ment , and t he pr oduct i on of N H 4
+
i n soils i s qui t e ubi qui t ous. Ni t ri fi cat i on
i s muc h mor e envi r onment al l y dependent . Whe t he r t he N H 4
+
accumul at es
or i s nitrified depends largely on acidity and t he O2 suppl y. T h e nitrifiers
ar e sensitive t o H
+
. The i r activity i s r educed bel ow pH 6.0 and becomes
negl i gi bl e bel ow 5. 0. Some soils with pH 4. 0 or less, however , may cont ai n
some N O 3
, and i t appear s t hat t he or gani sms der i ved from acid soils ar e
frequent l y mor e t ol er ant of H
+
. Opt i mum pH i s 6. 6 t o 8.0 or hi gher .
All nitrifiers need O2 , and nitrification ceases in its absence. For this
r eason, nitrification i s sensitive t o soil st r uct ur e and wat er cont ent . In
aer obi c soils, opt i mum wat er cont ent i s general l y 50% t o 6 7 % of t he
wat er - hol di ng capacity. Oxygen diffuses very slowly t hr ough wat er so t hat
nitrification may be occur r i ng i n t he out er par t of an aggr egat e at t he same
t i me t hat t her e i s deni t ri fi cat i on i n t he i nt er i or . Wat er l oggi ng or fl oodi ng
suppresses ni t ri fi cat i on, and t he N H 4
+
pr oduc e d i n ri ce paddi es t ends t o be
abs or bed by r oot s and not be nitrified.
Ni t ri fi cat i on is t emper at ur e- sensi t i ve and occurs most l y in t he r ange 5
t o 40 degr ees C wi t h an opt i mum bet ween 30 and 35 degr ees.
In summar y, nitrification occurs rapi dl y i n most wel l -drai ned and moist
agr i cul t ur al soils wi t h a pH 6.0 or hi gher . NO3
is t he mai n f or m of N
abs or bed by r oot s. In acid forest soils nitrification i s commonl y i nhi bi t ed by
acidity, and it is bel i eved t hat pl ant s in forests absor b much of t he N as
N H 4
+
. Un d e r t he anaer obi c condi t i ons of f l ooded soils, t he lack of O2
i nhi bi t s nitrification, and N H 4
+
i s t he pr edomi nant f or m of N absor bed.
I mmob i l i z a t i on
Aft er t he upt ake of N H 4
+
and NO3
by r oot s and t he het er ot r ophi c mi cr o-

or gani sms, t he conversi on of t he mi ner al N i nt o or gani c N is called immobili-
zation (see Fi gur e 4. 1). Mi neral i zat i on and i mmobi l i zat i on ar e t wo opposi ng
and i nt er dependent processes t hat st rongl y cont r ol t he suppl y of available
ni t r ogen i n soils. Nitrification can occur bet ween mi neral i zat i on and i mmo-
bilization, cont r ol l i ng whet her t he available f or m of N will be N H 4
+
or NO3
.
T h e available N i s absor bed by bot h t he het er ot r ophs and pl ant r oot s;
t hus, bot h ar e benefi t ed. Mor eover , r oot exudat es and sl oughed-off r oot
cells pr ovi de a readi l y available sour ce of ener gy and C for t he het er o-
t r ophs. Th e het er ot r ophs ar e t her ef or e addi t i onal l y benefi t ed by t he pl ant s.
Soil condi t i ons favorabl e for gr owt h of t he het er ot r ophs ar e favorabl e for
pl ant gr owt h, whi ch means t hat t her e i s a st r ong cor r el at i on bet ween
mi neral i zat i on and pl ant i mmobi l i zat i on of N. As a consequence, mi neral i -
zat i on and i mmobi l i zat i on compri se a subcycle of t he soil' s N cycle, one t hat
gover ns t he level of available N in unfert i l i zed soils at any given i nst ant .
Since mi neral i zat i on and i mmobi l i zat i on occur si mul t aneousl y, pl ant s may
have an adequat e suppl y of available N, even t hough soil tests i ndi cat e t hat
little N is available at a given i nst ant .
Carbon-to-Nitrogen Ratios
Mi neral i zat i on is car r i ed out by a wi de vari et y of het er ot r ophi c or gani sms
t hat have a di et ary need for bot h C and N. T h e N H S pr oduc e d by mi neral i -
zation r epr esent s an a mount of N i n t he subst r at e i n excess of mi crobi al
needs. T h e C : N r at i o ( %C/ %N) of t he subst r at e provi des an i ndi cat i on of
t he adequacy of N for t he mi neral i zers and t he a mount of N t hat will
appear as excess. Th e SOM has a C : N r at i o typically in t he r ange of 10 to
1 2 : 1 , and when SOM i s mi neral i zed i t pr ovi des an excess of N, whi ch can
be used by r oot s. Resi dues of l egume crops and farm manur es , also pr ovi de
an a mount of N i n excess of mi neral i zat i on needs and a surpl us t hat can be
used by gr owi ng crops. As t he C : N r at i o of subst rat es i ncreases, t her e is
relatively less N for t he C, and subst rat es wi t h rat i os above 30 ar e not likely
t o cont ai n enough N t o meet mi crobi al needs. The s e mat eri al s i n soils ar e
decomposed t hr ough t he r euse of any mi neral i zed N by t he decomposer s or
mi neral i zers, and pl ant r oot s may be st arved for N. Dur i ng t he decomposi -
t i on or r ot t i ng of subst rat es, t her e is a cont i nual loss of C as r espi r at or y
CO2 , wi t h an accompanyi ng i ncrease i n t he N per cent age and a decr ease i n
t he C : N rat i o (see Fi gur e 4. 5). Whe n t he r at i o decreases bel ow 30, excess N
from mi neral i zat i on will agai n appear , and t he per i od of N stress for pl ant s
di sappears.
Many mat eri al s added to soils, such as st raw and sawdust , have C : N
rat i os of about 80 and 400, respectively. The i r addi t i on t o soils bef or e
pl ant i ng can cr eat e a per i od of N st arvat i on for crops. It r equi r es about 20
FIGURE 4. 5 Changes i n ni trogen content and the carbon-to-ni trogen ratio duri ng
the decomposi ti on of barley straw. (From Al exander, 1977, used by permi ssi on of
John Wiley & Sons. )
pounds of N per t on of st raw t o supply t he mi ner al i zat on N deficit of t he
st raw and pr event a per i od of net i mmobi l i zat i on of N.
De ni t r i f i c a t i on
Denitrification i s t he chemi cal r educt i on of ni t r at e and ni t r i t e t o gaseous
forms: ni t ri c oxi de, ni t r ous oxi de, and di ni t r ogen:
T h e val ence of N decreases from 5 or 3 to 2, 1 or 0.
Th e capacity for t r ue deni t ri fi cat i on, t he f or mat i on of N2 , i s r est r i ct ed
t o cer t ai n chemohet er ot r ophi c bact eri a. The s e bact eri a ar e aer obes. Unde r
anaer obi c condi t i on, however , t hey use NO3
for t hei r el ect r on accept or

i nst ead of O2 . The y need a decomposabl e source of or gani c mat t er t o
suppl y C and el ect rons. Thus , t he t wo most i mpor t ant condi t i ons needed
for deni t ri fi cat i on ar e an anaer obi c envi r onment and a C sour ce.
Factors Affecting Denitrification
Because a lack of 2 favors t he chemi cal r educt i on of ni t r at e and ni t ri t e to
gaseous forms, deni t ri fi cat i on i s affected by soil st r uct ur e and wat er con-
t ent , but conversel y t o nitrification. Anaer obi c mi cr oenvi r onment s ar e cre-
at ed i n soils when t he O2 de ma nd exceeds t he suppl y. A significant a mount
of deni t ri fi cat i on and loss of gaseous N occur in many wel l -drai ned soils
t hr ough deni t ri fi cat i on i n t he i nt er i or s of aggr egat es. Fl oodi ng cr eat es
condi t i ons very conduci ve to deni t ri fi cat i on, if ni t r at e is pr esent . Since
NO3
i s pr oduced i n an aer obi c envi r onment and deni t ri fi cat i on occurs i n

an anaer obi c envi r onment , deni t ri fi cat i on i s enhanced by t he al t er nat e
wet t i ng and dr yi ng of soils. Paddy ri ce fi el ds ar e very vul ner abl e t o deni t r i -
fi cat i on losses i n rai n-fed systems because fi el ds ar e likely al t ernat el y t o dr y
a nd r esat ur at e.
Acidity affects bot h t he r at e of deni t ri fi cat i on and t he t ype of gas
pr oduced. Deni t ri fi ers ar e sensitive t o H
+
, al t hough deni t ri fi cat i on has been
r epor t ed t o be r api d i n a soil wi t h a pH of 4. 7. Above pH 6.0 t he maj or gas
pr oduced i s N2 , and i n mor e acid envi r onment s t he l i berat i on of N2 O
becomes pr onounced. Nitrification is very slow at 2 degr ees C and i ncreases
t o a ma xi mum at 25 degr ees or hi gher . Significant deni t ri fi cat i on can occur
when i t i s t oo col d for crops t o be gr owi ng. Dur i ng late fall and very early
spr i ng in t he t emper at e r egi ons, t her e is a subst ant i al loss of N t hr ough
deni t ri fi cat i on.
Th e gr owt h of pl ant r oot s may i nhi bi t deni t ri fi cat i on by servi ng as a
sink for NO3
and cr eat i ng dr i er soil wi t h a gr eat er O2 diffusion r at e. On

t he ot her hand, r oot exudat es pr ovi de a sour ce of car bon and depl et e O2
near t hei r surfaces t o st i mul at e deni t ri fi cat i on. Whe n NO3
moves by
l eachi ng bel ow t he zone of biological activity, or C sour ce, it is beyond t he
spher e wher e deni t ri fi cat i on occurs; i t may r emai n unchanged and move
f ar t her downwar d, and t her e i t pol l ut es t he gr oundwat er . I n agr i cul t ur e,
deni t ri fi cat i on r epr esent s a l arge loss of ni t r ogen, a nd t her e ar e few pract i -
cal t hi ngs t hat can be done t o pr event it.
Ni t r ogen i s cont i nual l y added t o soils by fi xat i on, pr eci pi t at i on a nd gaseous
adsor pt i on. T h e N cont ent of t he soil, however , does not i ncrease cont i n-
ually but t ends t o r each an equi l i br i um or st eady st at e wher e addi t i ons ar e
bal anced by losses. Th e losses or leaks from t he cycle ar e due t o volatiliza-
t i on, l eachi ng, and deni t ri fi cat i on. As a resul t of t hese losses, t her e is a need
for a const ant influx of N to mai nt ai n a st eady N cont ent . Soils do not
become so enr i ched wi t h N (except maybe some Histosols) t hat t hey pr o-
duce hi gh gr ai n yields for decades wi t hout N fertilizer.
Th e r e is gr eat vari at i on in t he par t i t i oni ng of a dde d fertilizer N as
cl i mat e, soils, crops, yields, and soil ma na ge me nt pract i ces vary. Some
est i mat es of t he fate of N fertilizer ar e 30% t o 70% r emoved i n har vest ed
cr op, 5% t o 10% l eachi ng loss, 10% t o 30% gaseous loss, and 10% t o 40%
i ncor por at ed i nt o soil or gani c mat t er . As a gener al r ul e, 50% of fertilizer N
i s absor bed by t he cr op; 2 5 % i s lost by deni t ri fi cat i on, l eachi ng, a nd volatili-
zat i on; and 2 5 % r emai ns i n t he soil as mi ner al N or i s i ncor por at ed i nt o new
or gani c mat t er .
Basis of Nitrogen Fertilizer Recommendations 75
N I T R O G EN U P T A K E
Bot h N H 4
+
and NO3
ar e commonl y pr esent i n soil sol ut i ons, a nd bot h ar e

readi l y t aken up by r oot s. Th e r api d nitrification r at es i n wel l -aerat ed soils
wi t h pH 6 t o 8 means, however , t hat pl ant s absor b pr edomi nat el y N O 3
.
Ni t r at e r emai ns sol ubl e i n t he soil sol ut i on a nd i s readi l y moved t o pl ant
r oot s by a mass flow of wat er . It has been est i mat ed t hat for cor n 79%, 20%
a nd 1% of t he ni t r ogen at r oot surfaces ar e t her e t hr ough mass flow,
diffusion, and r oot i nt er cept i on, respect i vel y.
In some soils acidity or anoxi a has pr event ed nitrification, a nd t he
pr edomi nant f or m of available N i s N H 4
+
. In gener al , calcifuge pl ant s,
whi ch nat ural l y gr ow unde r aci d condi t i ons, pr ef er N H 4
+
. T h e calcioles,
pl ant s wi t h a wi de pH t ol er ance, pr ef er N O 3
. At t he ext r eme ar e cran-

ber r y pl ant s, whi ch ar e unabl e t o absor b or met abol i ze N O 3
. Ri ce gr own
on fl ooded soil, wher e nitrification t ends t o be i nhi bi t ed, i s mor e pr oduct i ve
wi t h a mmoni um t han with ni t r at e fertilizer. I t has not been pr oved, how-
ever, t hat N H 4
+
i s clearly t he most efficient f or m of N for ri ce.
Whe n pl ant s absor b N mai nl y as N H 4
+
, t her e i s an excess of cat i on
upt ake compar ed t o ani on upt ake, and H
+
i s excr et ed, whi ch decr eases t he
pH i n t he r hi zospher e. Whe n upt ake i s mai nl y N O 3
, t her e i s an excess
upt ake of ani ons, and OH
i s excr et ed, whi ch i ncreases t he pH of t he

r hi zospher e. In a r espi r i ng r hi zospher e t he hydr oxyl react s wi t h car bon
di oxi de t o f or m H C O 3
. T h e quest i on whet her NO3
or N H 4
+
i s t he
super i or or mor e efficient f or m of N for pl ant s is still unans wer ed.
BASI S OF N I T R O G EN
F ERT I LI Z ER R EC O MMEN D A T I O N S
Most agri cul t ural soils ar e at or near a st eady st at e in t hei r t ot al N cont ent ,
whi ch varies slightly from year t o year. Th e vari at i ons i n mi neral i zat i on,
deni t ri fi cat i on, and l eachi ng r at es from one soil t o anot her and f r om one
year to anot her compl i cat e t he use of a test for t ot al soil N or N mi neral i za-
t i on r at e as a basis for maki ng N fertilizer r ecommendat i ons . Recommenda-
t i ons for N fertilizers ar e based pr i mar i l y on yield r esponse dat a obt ai ned
from N fertilizer r at e exper i ment s.
Gr a i n Cr ops
Fert i l i zer r at e exper i ment s i n Illinois wer e used t o devel op Tabl e 4. 3, whi ch
gives t he economi cal l y opt i mum cor n yields a nd opt i mum N r at es per
bushel of cor n pr oduced. T h e economi cal l y opt i mum N fertilizer r at e for
cor n i s based on a c o r n : N pr i ce r a t i o t h e pr i ce of a bushel of cor n
di vi ded by t he pri ce of a pound of fertilizer N. Cor n gr own at Br ownst own
had t he least ability t o absor b N fertilizer and profitably i ncrease yields; t he
economi c opt i mum yield was 83 bus hel s / acr e wi t h a c o r n : N r at i o of 10.
Soils at Ur bana wer e t he best for cor n pr oduct i on; t he economi cal l y opt i -
mu m yield was 171 bus hel s / acr e with a c or n: N r at i o of 10. Not i ce i n Tabl e
TABLE 4.3 Economic Optimum Yield* and Optimum
Nitrogen Rate Experimentally Determined for
Continuous Corn at Four Locations in Illinois
Location
Corn : nitrogen price ratio
Location
10: 1 20: 1
Location Yield Rate Yield Rate
Brownstown 83 1.30 86 1.47
Carthage 144 1.22 147 1.29
DeKalb 141 1.28 143 1.31
Urbana 171 1.17 173 1.24
*Yield in bushels per acre and opt i mum N rate in pounds of
ni trogen per bushel.
Source: Data from Illinois Agronomy Handbook, 1986, Urbana, Ill.
4. 3 t hat i t t ook less N per bushel of yield t o pr oduce t he opt i mum yield at
Ur bana as compar ed t o Br ownst own: 1.17 versus 1.3. Based on t he opt i -
mu m N r a t e p o u n d s of N per bushel of yi el dmul t i pl i ed by t he opt i -
mu m economi c yield, t he a mount of N fertilizer r e c omme nde d for Br own-
st own is 108 (83 X 1.3) pounds per acr e of N for a c or n: N r at i o of 10. For
Ur bana t he N fertilizer r ecommendat i on is 200 (171 X 1.17) pounds / a c r e
of N. T h e basic equat i on for t he N fertilizer r ecommendat i on i s
pounds N per acr e = YG X opt i mum N r at e (4. 3)
wher e YG i s t he yield goal (bushels per acre) a nd t he opt i mum N r at e i s t he
pounds of N needed per bushel of yield t o pr oduce t he economi cal l y
opt i mum yield. Some exampl es of equat i ons for N fertilizer r ecommenda-
t i on for cor n and s or ghum pr oduct i on i n Iowa ar e given i n Tabl e 4. 4.
T h e basic N fertilizer r ecommendat i on for cor n i s modi fi ed by consi d-
er at i on of t he pr evi ous cr op a nd t he a mount of ma nur e t o be appl i ed. T h e
equat i on used i n Mi chi gan for cor n N r ecommendat i ons as pounds per acr e
is:
TABLE 4.4 Nitrogen Recommendation Procedure for Corn and
Sorghum Based on Yield Goal and Optimum Nitrogen Rate per
Bushel in Iowa
N equation for pounds of N
Soil association per acre
Moody N = YG X 0.9
Marshall N = YGX 1.1
Clarion - Nicollet - Webster N = YGX 1.2
Tama - Muscatine N = [180 + ( YG- 150)] X 1.3
Source: Data from General Gui de for Fertilizer Recommendat i ons in
Iowa, 1982.
Basis of Nitrogen Fertilizer Recommendations 77
N = [(YG X 1.36) - 27] - [40 + (0. 6 X % ls)] - (4 X fm) (4.4)
Th e l s i s for l egume st and, whi ch i s eval uat ed as t he of numbe r of alfalfa or
cl over pl ant s per uni t ar ea. If an alfalfa st and was r at ed very good, 100%,
t hen 100 pounds [40 + (0. 6 X 100)] woul d be subt r act ed t o account for t he
N cont r i but i on of t he pr evi ous alfalfa cr op. Th e fm refers t o t ons of farm
ma nur e appl i ed per acr e. A 10 t o n / a c r e appl i cat i on of ma nur e woul d mean
a subt r act i on of 40 (4 X 10). For a YG of 150 bus hel s / acr e, when cor n
follows an excel l ent st and of alfalfa or cl over and 10 t ons / a c r e of ma nur e
ar e appl i ed, t he N r ecommendat i on is
pounds N= 177 - 1 0 0 - 4 0 = 3 7 (4.5)
Somet i mes a pr evi ous soybean cr op i s equat ed t o 40 pounds of fertil-
izer N. Thi s basic me t hod i s also used t o make N r ecommendat i ons for
small grai ns and ot her nonl egume cr ops. T h e me t hod can be called t he N
bal ance me t hod i n t hat an at t empt i s made t o det er mi ne cr op N needs and
t he amount of N expect ed t o be available. Th e di fference bet ween need
and availability i s t he fertilizer r ecommendat i on.
Ot he r factors ar e used t o modify t he r ecommendat i on, dependi ng on
t he crops and condi t i ons. I n ar eas of l i mi t ed pr eci pi t at i on a nd l eachi ng,
t her e i s oppor t uni t y for NO3
t o be car r i ed over. A test t o det er mi ne t he

a mount of NO3
i n t he r oot zone i s used i n many of t he west er n states. T h e

sampl es for ni t r at e shoul d be obt ai ned at a mi ni mum dept h of 60 cm (24
inches) and, if possible, at a dept h of at least 120 cm (48 i nches). Mont ana
r ecommends an adj ust ment when st raw wi t h a hi gh C : N r at i o is pl owed
down bef or e pl ant i ng. Twe nt y pounds / a c r e (22 k g / h a ) of N i s r ecom-
me nde d t o account for t he i mmobi l i zat i on of N by mi cr oor gani sms. Ar i -
zona makes an adj ust ment for N in i rri gat i on wat er . A s ummar y of some N
fertilizer eval uat i on systems used i n vari ous r egi ons of t he Uni t ed States i s
given i n Tabl e 4. 5.
Le g u me Cr ops
Le gume cr ops vary i n t hei r N-fixing efficiency. Alfalfa and cl over ar e not
benefi t ed by N fertilizer except , per haps , t o become mor e rapi dl y est ab-
lished when t he N-fixing system i s not fully oper at i ve. St at e agr i cul t ur al
exper i ment stations ar e becomi ng mor e conservat i ve i n r e c omme ndi ng N,
t o avoi d possible gr oundwat er cont ami nat i on, a nd t hey ar e el i mi nat i ng N
r ecommendat i ons for soybeans. In addi t i on, t he appl i cat i on of N fertilizer
to efficient N-fixing l egumes may r educe N fixation wi t hout affecting yields
(see Fi gur e 4. 6). Some of t he least efficient N- fi xi ng l egumes, on t he ot her
hand, ar e r out i nel y fertilized wi t h N such as peanut s i n Geor gi a, peas i n
Washi ngt on, and navy beans i n Mi chi gan.
Cr ops Gr own on Hi s t os ol s
Histosols ar e or gani c soils, and t hey cont ai n a gr eat er quant i t y of t ot al N
t han mi ner al soils. As a consequence, t he N mi neral i zat i on pot ent i al is very
TABLE 4.5 Summary of Some Factors Used in Current Nitrogen Evaluation
Systems in the United States
Region Crop
Average
nitrogen
factor*
Average
Manure
nitrogen credits
Soybeans
**
Alfalfa
Northeast corn 1.16 4.5 NA 134
Mid-Atlantic corn 1.18 6.0 16 71
Southeast corn 1.25 NA 27 49
Midwest corn 1.24 4.8 29 89
West corn 1.41 4.8 32 80
West wheat 2.10
- - -
Southwest wheat 2.15 NA NA 80
Northwest wheat 2.40 NA NA NA
* Pounds of ni t rogen per bushel of yield goal.
** Pounds per ton or pounds of ni trogen per acre. NA refers to i nadequate data or may
mean that i n the regi on the material i s an i nfrequent source of N.
Source: Sel ected data from Mei si nger, 1984.
hi gh, and many crops ar e gr own wi t hout N fertilizer. The s e soils r equi r e
dr ai nage and t end t o be wet and col d i n t he spri ng, causi ng a slow mi neral i -
zat i on r at e. Dur i ng this season some cr ops r espond t o small appl i cat i ons of
N fertilizer.
FIGURE 4. 6 Percent of total ni t rogen i n soybeans deri ved
from fertilizer, soil, and symbiotic fi xati on. (From Johnson,
Wel ch, and Kurtz, 1974. )
Nitrogen Fertilizers 79
N I T R O G EN F ERT I LI Z ERS
Ma nur e was t he domi nant fertilizer for t housands of years i n ar eas wher e
ani mal s wer e used for power and food. Most of t he nut r i ent s i n feed appear
i n t he ma nur e , and i f t he ma nur e i s efficiently managed, i t can be very
effective i n t he mai nt enance of soil fertility. Per uvi an guano was t he fi rst
fertilizer i mpor t ed i nt o t he Uni t ed States i n 1824. Thi s or gani c fertilizer
consi st ed of t he excr et a and r emai ns of bi r ds whose pr i mar y di et consi st ed
of fi sh. Gua no cont ai ns about 13% N, whi ch i s most l y or gani c. In 1830
Na NO3 was i mpor t ed from Chi l e. Thi s i nor gani c mat er i al of nat ur al ori gi n
cont ai ns about 16% N. The s e mat eri al s wer e used i n t he s out her n Uni t ed
St at es largely on speciality crops, such as cot t on and t obacco. In t he ni ne-
t eent h cent ur y t he bypr oduct N H 3 pr oduc e d from t he coki ng of coal used
i n steel manuf act ur i ng was neut r al i zed wi t h H2 S O4 t o pr oduce ( NH4 ) 2 S O4 .
Today, 9 5 % or mor e of t he N i n fertilizers i s pr oduced by di r ect N H 3
synthesis.
A mmo n i a Sy nt he s i s
Moder n N H 3 synthesis had its begi nni ng when Ha be r and Bosch con-
st r uct ed t he f i r st commer ci al pl ant i n Oppau, Ger many, i n 1913. Th e
process react s H and N di rect l y, usi ng hi gh t emper at ur e and pr essur e i n t he
pr esence of an i r on catalyst. Th e r eact i on i s
3 H2 + N2 = 2 NH3 (4.6)
Toda y over 80 per cent of t he pl ant s use t he st eam- r ef or mi ng met hod.
Nat ur al gas, CH4 , i s t he feedst ock for H, and t he N i s obt ai ned from t he
at mos pher e. A fl owchart of t he maj or steps i s given i n Fi gur e 4. 7. In t he
f i r s t step st eam, CH4 , and ai r ar e r eact ed or r ef or med t o pr oduce H2 , N2 ,
a nd CO. The s e gases ar e cool ed and r eact ed wi t h addi t i onal wat er t o
pr oduce mor e H2 by t he shift r eact i on. T h e CO2 pr oduc e d i n t he shift
r eact i on i s r emoved by absor pt i on i n an al kal i ne sol ut i on. Any c a r b o n -
oxygen compounds pr esent must be r emoved because t hey poi son t he
catalyst, and this i s accompl i shed i n t he met hanat i on st ep. Th e gases l eavi ng
met hanat i on cont ai n about 74% H2 , 0. 8% CH4 , and 0. 3% ar gon on a dr y
basis. Ammoni a synthesis occurs when t he N a nd H gases ar e passed over an
i r on catalyst, pr omot e d with pot assi um a nd al umi na, at hi gh t e mpe r a t ur e
and pr essur e.
T he Ma j or Ni t r og e n Car r i e r s
Economi cs dri ves t he pr oduct i on of N t owar d t he mat er i al or car r i er t hat
supplies i t at t he least cost. Thi s car r i er i s anhydr ous ammoni a, NH3 , whi ch
cont ai ns 82% N. Its cost advant age i s due t o low costs bot h i n pr oduct i on
a nd i n t r anspor t at i on, for N H 3 i s t r ans por t ed by pi pel i ne. Two l ar ge pi pe-
lines t r anspor t N H 3 f r om pl ant s i n Loui si ana, Texas , and Ar kansas t o
t er mi nal s as far west as Aur or a, Nebr aska, as far nor t h as Gar ner , Iowa, and
as far east as Hunt i ngt on, I ndi ana. I n 1965 N H 4 N O 3 was t he second most
popul ar car r i er and ur ea was t hi r d. By 1978 t her e was gr eat er consumpt i on
of ur ea t han of N H 4 N O 3 i n t he Uni t ed St at es. The s e 3 car r i er s ar e t he basis
for maki ng N sol ut i ons, whi ch have i ncreased steadily since 1965. Thes e
t r ends ar e shown i n Fi gur e 4. 8.
Anhydrous Ammonia
As al ready ment i oned, N H S i s manuf act ur ed by di r ect synthesis f r om H and
N gases and i s 82% N. At nor mal pr essur e N H S i s a gas a nd i s t r ans por t ed
and handl ed locally as a liquid unde r pr essur e. Specialized equi pment is
r equi r ed t o handl e t he liquid unde r pr essur e. It i s i nj ect ed i nt o t he soil t o
pr event seri ous loss t hr ough volatilization (see Fi gur e 4. 9).
T h e gaseous N H S pr ot onat es t o f or m N H 4
+
i n t he soil a nd becomes
X N H 4
+
, whi ch i s st abl e. Gaseous ammoni a can be lost, dependi ng on t hr ee
fact ors. St udi es have shown t hat volatilization losses at pH 7 ar e low but
i ncrease 10 t i mes when t he pH i s i ncr eased t o 8, a nd 50 t i mes when t he pH
Nitrogen Fertilizers
6
FIGURE 4. 8 Consumpti on, millions of short tons, of sel ected ni trogen
materials for direct application in the Uni t ed States. (Courtesy Nati onal
Fertilizer Devel opment Center, TVA. )
i s i ncr eased t o 9. Loss i ncreases as soils become dr i er or wet t er t han fi el d
capacity. T h e i nt er act i on bet ween t he moi st ur e cont ent of soil and t he
dept h of injection and t hei r affect on N H 3 loss ar e shown i n Fi gur e 4. 10.
Urea
Ur e a i s t he second most popul ar N car r i er and t he most popul ar dr y car r i er .
I t r equi r es no specialized equi pment for st or age and handl i ng and i s pr e-
f er r ed over N H 3 i n si t uat i ons i n whi ch t he fertilizer i s appl i ed by br oadcast
on lawns or fi el d cr ops. Th e CO2 f r om ammoni a synthesis i s used t o
pr oduce ur ea:
2 NH3 + CO2 = N H 2 C O O N H 4 (carbamat e) (4.7)
N H 2 C O O N H 4 = N H 2 C O N H 2 (urea) + H2 O (4. 8)
Ur e a i s mor e expensi ve t han NH3 , because t her e ar e addi t i onal manuf ac-
t ur i ng steps, and has gr eat er t r anspor t at i on costs, because ur ea has a l ower
N cont ent (46%).
A me t hod for maki ng ur ea prills or gr anul es uses t he falling-curtain
t echni que recent l y devel oped at TVA. Small seed ur ea gr anul es ar e pl aced
on l ongi t udi nal shelves i n a r ot at i ng d r u m and spr ayed wi t h a concent r at ed
ur ea sol ut i on as t he d r u m r ot at es and t he gr anul es fall from one shelf t o
Soil moi sture, percent
FIGURE 4. 10 Losses of ammoni a from Putnam silt loam as i nfl uenced by
soil moi sture and depth of application of 112 kilograms of ni t rogen per
hectare ( 100 pounds per acre) i n rows 100 centi meters apart. (From
Stanley and Smi th, 1956, used by permi ssi on of the Soil Sci ence Society of
Ameri ca. )
anot her . Th e t echni que i s efficient i n pr oduci ng a wi de vari et y of part i cl e
sizes. Th e dr i ed prills or gr anul es ar e coat ed wi t h a condi t i oner t o pr event
t he hygroscopi c ur ea from t aki ng up wat er from t he ai r a nd caki ng (to a
solid mass).
Whe n ur ea i s appl i ed t o t he soil, t he hydrolysis of ur ea i s cat al yzed by
ur ease:
CO( NH2 ) 2 + H2 O + ur ease = 2 NH3 + CO2 (4.9)
In effect, t he appl i cat i on of ur ea i s similar t o t he appl i cat i on of NH3 , and
t he N in ur ea is similarly subj ect ed to volatilization loss. Surface appl i cat i ons
of ur ea, i n t he absence of movement i nt o t he soil by wat er , commonl y resul t
i n losses of 20% t o 30% of t he N. On t he ot her hand, ur ea i s widely used t o
fertilize fl ooded rice i n fi el ds wher e anaer obi c condi t i ons i nhi bi t nitrifica-
t i on and t he subsequent loss of N by deni t ri fi cat i on. Super l ar ge ur ea gr an-
ules wi t h a di amet er of about 2 cm have been devel oped for hand applica-
t i on deep i n t he mu d of ri ce paddi es i n Asia.
Bi uret , NH2 - CO- NH- CO- NH2 , i s f or med dur i ng ur ea synthesis a nd i n
t he processi ng of sol ut i ons following ur ea synthesis. T h e a mount of bi ur et
f or med depends on t emper at ur e and ot her condi t i ons and i s commonl y
0. 8% t o 2. 0% of t he fi ni shed pr oduct . For most pl ant s this level of bi ur et i s
not t oxi c when t he ur ea cont ai ni ng i t i s pl aced i n t he soil, for t he bi ur et i s
readi l y decomposed and its N becomes available. If ur ea is pl aced wi t h or
close t o seeds, t hey may be damaged, dependi ng on t he bi ur et cont ent of
t he ur ea. Bi uret i s also t oxi c t o ci t rus pl ant s and some ot her cr ops i f ur ea i s
used as a foliar spray. Ci t rus i s abl e t o t ol er at e up t o 0. 25% bi ur et i n ur ea
used for foliar appl i cat i on. Cor n and soybeans can t ol er at e sol ut i ons made
wi t h ur ea cont ai ni ng 1.5% bi ur et .
Ammonium Nitrate
Ammoni um ni t r at e i s pr oduced by oxi di zi ng N H 3 t o H N O s and neut ral i z-
i ng t he ni t ri c acid wi t h mor e NH3 . Bot h ur ea and N H 4 N O 3 gr anul es can be
made by t he falling-curtain t echni que or by sprayi ng concent r at ed sol ut i ons
f r om t he t op of a t ower and col l ect i ng t he congeal ed part i cl es at t he
bot t om. Bot h processes r equi r e t hat t he prills be dr i ed and coat ed t o
pr event t he adsor pt i on of wat er from t he ai r a nd caki ng. Ammoni um
ni t r at e i s 3 3 % N, wi t h half of t he N i n ni t r at e f or m and t he ot her hal f i n
a mmoni um f or m. I f N H 4 N O 3 i s appl i ed on t he surface, less N H 3 i s lost t o
volatilization, as compar ed t o ur ea; and t he subst ance i s well sui t ed for
t op-dressi ng lawns and so on. Aft er a mmoni um ni t r at e moves i nt o t he soil,
however , t he loss of N by NO3
l eachi ng, and deni t ri fi cat i on is mor e likely.

Ammoni um ni t r at e mi xed with 6% fuel oil is used for bl ast i ng in mi nes.
Un d e r pr ope r condi t i ons i t i s expl osi ve but poses no t hr eat i n its nor mal use
as a fertilizer. Thi n layers of N H 4 N O 3 by t hemsel ves will not bur n unless
cont i nuous heat i s appl i ed. Lar ge piles i n bul k st or age or i n bags, however ,
may become sufficiently heat ed t o i gni t e unde r condi t i ons of conf i nement
and gas pr essur e; t hey may, i f i gni t ed, t r ansmi t fire rapi dl y t hr ough t he
mass and possibly cause an expl osi on. Even so, t her e ar e i nt er nat i onal t r ade
rest ri ct i ons on N H 4 N O 3 , whi ch have hel ped make ur ea t he most popul ar
dr y N fertilizer wor l dwi de. In some count r i es t he use of ammoni a ni t r at e i s
pr ohi bi t ed, and i t i s commonl y mi xed wi t h lime t o pr oduce a mat er i al t hat
cont ai ns 7 5 % N H 4 N O 3 a nd has a N cont ent of 26%. Thi s subst ance i s called
cal ci um c a r bona t e - ni t r a t e , CAN.
Nitrogen Solutions
Anhydr ous ammoni a, ur ea, and ammoni a ni t r at e ar e soluble i n wat er and
ar e used t o make fertilizer sol ut i ons. Sol ut i ons usi ng N H 3 have vapor
pr essur e a nd ar e used pri mari l y as a sour ce of N i n t he manuf act ur e of
c ompound fertilizers. Sol ut i ons cont ai ni ng only N H 3 ar e called aqua ammo-
nia. Sol ut i ons wi t hout N H 3 have no vapor pr essur e and can be used as dr y
mat eri al s ar e used, except t hat t hey ar e liquid. It i s easy t o i ncor por at e
herbi ci des at t he t i me of appl i cat i on and t o met er t he fertilizer sol ut i on i nt o
i rri gat i on wat er . Ni t r ogen sol ut i ons ar e desi gnat ed t o i ndi cat e t hei r compo-
sition. A sol ut i on of 28. 0 (0-40-30) cont ai ns 28. 0% N, 0% NH3 , 40%
NH4 NO3 , and 30% ur ea by wei ght . T h e mat eri al cont ai ns 30% wat er . T h e
concent r at i on of N is l i mi t ed by t he crystallization or sal t i ng-out t emper a-
t ur e. T h e composi t i on and pr oper t i es of t hr ee c ommon N sol ut i ons ar e
given i n Tabl e 4. 6.
Ammonium Phosphates
Ammoni um phosphat es ar e pr oduced by t he neut ral i zat i on of phosphor i c
acid with ammoni a and ar e i mpor t ant P fertilizers, whi ch ar e consi der ed i n
Chapt er 5.
Cont r ol l e d - Re l e a s e Ni t r og e n Fe r t i l i z e r s
T h e N fertilizers t hat have been discussed ar e wat er-sol ubl e, and t he N may
be quickly absor bed by pl ant s or lost from t he soil. For t he mai nt enance of
TABLE 4.6 Characteristics of Urea--Ammonium Nitrate Solutions
Grade, percent N 28 30 32
Composition by weight, percent
Ammonium nitrate 40.1 42.2 43.3
Urea 30.0 32.7 35.4
Water 29.9 25.1 20.3
Specific gravity, 60F 1.28 1.30 1.32
Salting-out temperature, F 1 14 28
Source: Data from Fertilizer Manual, International Fertilizer Devel opment
Center, TVA, 1979.
turf, this r api d dissipation of t he N r equi r es several appl i cat i ons of N
fertilizer annual l y. Thus , t her e is a need for cont rol l ed-rel ease N fertilizers
t o r educe t he cost of appl i cat i on and i ncrease t he efficiency of N use, whi ch
i s sel dom gr eat er t han 50 per cent . Cont r ol l ed rel ease i s achi eved by maki ng
i nsol ubl e mat eri al s or coat i ng soluble mat eri al s.
Sul fur-coat ed ur ea, SCU, has been unde r devel opment at t he Te nne s -
see Valley Aut hor i t y for about 20 years. Ur e a i s t he least expensi ve maj or
dr y N car r i er . Sul fur i s also relatively i nexpensi ve, and t he fi nal pr oduct has
good handl i ng charact eri st i cs. Ur ea gr anul es ar e coat ed wi t h sulfur and
t hen coat ed with a seal ant . T h e t hi ckness of t he S coat i ng affects t he r at e of
N di ssol ut i on. A t ot al coat i ng of 20% t o 22% resul t s i n t he di ssol ut i on or
rel ease of 20% t o 2 5 % of t he N i n t he fi rst week. SCU- 10 and SCU- 40
rel ease 10% and 40% of t hei r N by di ssol ut i on i n seven days, respect i vel y.
SCU costs about 3 5 % t o 40% mor e t han ur ea per pound of N a nd i s t oo
expensi ve for gener al agr i cul t ur al use. It has been f ound t o be effective i n
r educi ng N loss for rice pr oduct i on unde r rain-fed condi t i ons wher e soils
ar e subject t o per i odi c fl oodi ng and dr yi ng.
Ur e a - f or ma l de hyde , ur eaf or m, i s t he r eact i on pr oduct of ur ea and
f or mal dehyde i n aqueous sol ut i on. Ur eaf or m commonl y cont ai ns 3 8 % N,
of whi ch 30% i s sol ubl e i n wat er at 25 degr ees C. It i s desi rabl e t o have 50%
t o 70% of t he r emai ni ng N soluble i n boi l i ng wat er .
I sobut yl i dene di ur ea, I BDU, i s pr oduced by t he r eact i on of ur ea with
i sobut yr al dehyde and cont ai ns 32% N. Most I BDU i s manuf act ur ed i n
J apan and Ger many.
Ot he r cont rol l ed-rel ease N fertilizers ar e bei ng devel oped and t est ed
i n vari ous count r i es. All t hese mat eri al s ar e mor e expensi ve t han ur ea and
ar e used mai nl y on lawns, golf courses, hor t i cul t ur al gar dens, and for t he
pr oduct i on of some fruits and veget abl es. Cont rol l ed-rel ease mat eri al s ar e a
component of many lawn and gar den fertilizers.
Mi nor Ni t r og e n Car r i e r s
Ammoni um sulfate was once t he l eadi ng N fertilizer pr oduc e d as a by-prod-
uct of t he coki ng of coal in t he manuf act ur e of steel. It is still pr oduc e d as a
bypr oduct and i n some instances i s manuf act ur ed by neut r al i zi ng H2 S O4
with NH3 . Th e pri nci pal di sadvant age i s its low N cont ent , whi ch i s 2 1 %. Its
advant ages i ncl ude its sulfur cont ent and good physical condi t i on. Th e
fertilizer is st rongl y acidic, whi ch can be a di sadvant age when used on acid
soils or an advant age when used on al kal i ne soils wher e t he acid effect may
be desi rabl e for azaleas, and t he like.
Cal ci um ni t r at e, 15. 5% N, i s pr oduced by r eact i ng H N O 3 a nd Ca CO3 .
Th e ni t r at e is a readi l y available sour ce of N and used for soil appl i cat i on on
wi nt er season veget abl es and as a foliar spray on bot h veget abl es and fruits.
Pot assi um ni t r at e, 13% N, i s manuf act ur ed by r eact i ng H N O 3 wi t h KCl
and i s used i n t he pr oduct i on of fruits and veget abl es.
Or g a ni c Ni t r og e n Fe r t i l i z e r s
Manur e, cr op resi dues, and many ot her or gani c mat eri al s have been added
t o soils t o i ncrease t he nut r i ent suppl y. T h e benefits come largely from
t hei r N cont ent . Ni t r ogen i n or gani c f or m can be st or ed i n t he soil; how-
ever, t he N is available only aft er mi neral i zat i on. Historically, nonl egu-
mi nous crops have been r ot at ed wi t h l egumes so t hat t hey can t ake advan-
t age of t he N r esul t i ng from t he decomposi t i on of l egume resi dues. A cover
cr op t hat grows i n t he fall and early spr i ng t akes up mi ner al soil N and
conver t s i t i nt o or gani c mat t er , t her eby r educi ng l eachi ng and denitrifica-
t i on losses. Pl owi ng unde r t he cover cr op allows a gr adual rel ease of N by
mi neral i zat i on dur i ng t he gr owi ng season. T h e advent of cheap N fertilizer
has great l y r educed t he i mpor t ance of or gani c N fertilizers i n t he wor l d
dur i ng t he t went i et h cent ur y. Gi ven pr esent concer ns about t he envi r on-
ment and t he i nt erest i n sust ai nabl e agr i cul t ur e systems, or gani c fertilizers
may be mor e sought aft er i n t he f ut ur e.
N I T R O G EN C A R R I ER C O MP A R I S O N S
Economi c consi derat i ons play a maj or r ol e in t he selection of N fertilizers
and ar e responsi bl e for t he t r ends shown i n Fi gur e 4. 8. Nitrification of
a mmoni um i n soils t ends t o cause pl ant s t o t ake up N as ni t r at e; t hus, many
shor t - t er m exper i ment s concl ude t hat a mmoni um and ni t r at e forms ar e
compar abl e for i ncreasi ng yields on a per - pound- of - N basis. In fl ooded soils
a mmoni um N is super i or to ni t r at e in i ncreasi ng yields because ni t r at e loses
N t hr ough deni t ri fi cat i on. On t he ot her hand, ammoni a and a mmoni um
forms appl i ed on or at t he soil surface ar e mor e subject t o volatilization loss
t han ni t r at e. T h e maj or pract i cal difference i n N fertilizers i s t hei r affect on
soil pH.
Ac i di t y a nd Ba si c i t y
Nitrification i s an i mpor t ant soil-acidifying process; when a mmoni um fertil-
izers ar e used, t her e i s consi derabl e pot ent i al t o i ncrease soil acidity. Th e
differences i n t he acidity and basicity of a mmoni um and ni t r at e fertilizers
ar e discussed i n Chapt er 8, Mi xed Fert i l i zers.
REF ERENCES
Alexander, M. 1977. Introduction to Soil Microbiology. 2nd ed. John Wiley, New York.
Baethgen, W. E. and M. M. Alley. 1986. Nonexchangeable Ammonium Nitrogen
Contribution to Plant Available Nitrogen. Soil Sci. Soc. Am. Jour. 51: 110- 115.
Delwiche, C. C. 1969. Nitrogen Fixation. The Science Teacher. Jour. Nat. Sci.
Teachers Assoc. 36: 14- 21.
Evans, H. J . and L. Barber. 1977. Biological Nitrogen Fixation for Food and Fiber
Production. Science. 197: 332-339.
Hauck, R. D., ed. 1984. Nitrogen in Crop Production. Am. Soc. Agron., Madison,
Wis.
References 87
International Fertilizer Development Center. 1979. Fertilizer Manual. TVA, Muscle
Shoals, Al.
Iowa State University Cooperative Extension Service 1982. General Guide for Fertil-
izer Recommendations in Iowa. Agronomy Dept., Ames.
Johnson, J. W., L. F. Welch, and L. T. Kurtz. 1974. Soybean's Role in Nitrogen
Balance. Illinois Research. 16: 6- 7.
Keller, G. D. and D. B. Mengel. 1986. Ammonia Volatilization from Nitrogen
Fertilizers Surface Applied to No-Till Corn. Soil Sci. Soc. Am. four
50: 1060- 1063.
Kulasooriya, S. A., P. A. Roger, W. L. Barraquio, and I. Watanabe. 1980. Biological
Nitrogen Fixation by Epiphytic Microorganisms in Rice Fields. IRRI Research Paper
Series 47, IRRI, Manila.
Meisinger, L. L. 1984. Evaluating Plant-Available Nitrogen in Soil-Crop Systems.
In Nitrogen in Crop Production. R. D. Hauck, ed. Am. Soc. Agron., Madison
Wis.
National Fertilizer Development Center. 1983. Fertilizer Trends. TVA, Muscle
Shoals, Ala.
Phillips, D. A. and T. M. Dejong. 1984. Nitrogen Fixation in Leguminous Plants.
In Nitrogen in Crop Production. R. D. Hauck, ed. Am. Soc. Agron., Madison
Wis.
Stanley, F. A. and G. E. Smith. 1956. Effect of Soil Moisture and Depth of Applica-
tion on Retention of Anhydrous Ammonia. Soil Sci. Soc. Am. Proc. 20: 557- 561.
Stevenson. F. J., Ed. 1982. Nitrogen in Agricultural Soils. Agronomy 22. Am. Soc.
Agron., Madison, Wis.
Stevenson, F. J. 1982. Origin and Distribution of Nitrogen in Soil. In Nitrogen in
Agricultural Soils. Agronomy 22, F. J. Stevenson, ed. Am. Soc. Agron., Madi-
son, Wis.
University of Illinois Cooperative Extension Service. 1984. Illinois Agronomy Hand-
book 1985-1986. Cir. 1233, Agronomy Dept., Urbana.
Whittaker, C. W. 1948. Ammonium Nitrate for Crop Production. Cir. 171, USDA,
Washington, D.C.
C H A P T E R 5
Soil and Fertilizer Phosphorus
Whe n scientists began t o add nut r i ent s t o soils t o i mpr ove t hei r fertility,
phos phor us (P) was soon di scovered t o be one of t he l i mi t i ng el ement s.
I ndeed, P became known as t he master key to agriculture because lack of
available P in soils l i mi t ed t he gr owt h of bot h cul t i vat ed and uncul t i vat ed
pl ant s. To cor r ect this deficiency, f ar mer s have added P t o soils i n t he f or m
of manur es , mi neral s, and manuf act ur ed fertilizers. Now many soils have a
sufficient or hi gh cont ent of P, and t he wat ers t hat dr ai n f r om some
agr i cul t ur al l ands also have a l ar ge a mount of P, i ncreasi ng t he gr owt h of
al gae and ot her pl ant s i n surface wat ers. In t he erosi on of hi gh-P soil,
sedi ment s wi t h a hi gh cont ent of P ar e deposi t ed i nt o surface wat er s.
Consequent l y, i n areas of t he wor l d wher e farms ar e managed t o obt ai n
maxi mum yields, envi r onment al concer ns ar e gr eat . Thus , dur i ng t he past
decade, P has become known as t he key t o e ut r ophi c a t i oni n eut r ophi ca-
t i on surface wat er becomes hi ghl y pr oduct i ve i n al gae and aquat i c weeds.
Managi ng our ent i r e r esour ces r equi r es a compl et e under s t andi ng of t he
forms of P in soils, t he changes br ought about when sol ubl e P is a dde d to
soils, and t he i nt eract i ons bet ween soluble P and soil p H.
I N V EN T O R Y O F T H E EA R T H' S P H O S P H O R U S
For conveni ence, t he ear t h' s supply of P can be di vi ded i nt o t wo gr oups.
Th e fi rst gr oup consists of t he P t hat i s sufficiently concent r at ed t o be
mi ned. T h e second gr oup consists of t he P t hat exists i n t he soil and i n ot her
geol ogi c mat er i al wher e t he P concent r at i on i s t oo low t o be mi ned but t he
P becomes slowly soluble for pl ant or ot her biological gr owt h. Nat ur al soils
will cont ai n from 50 to over 1 000 mg of t ot al P per ki l ogr am of soil. Of this
quant i t y, from 30% t o 50% may be i n or gani c f or m i n mi ner al soils.
Deposi t s of r ock phos phat e for mi ni ng ar e relatively common t hr ough-
88
Phosphorus Cycling in Soil Development 89
out t he worl d. T h e l argest deposi t s and pr oduct i on i n t he Uni t ed St at es ar e
i n Fl ori da and Nor t h Carol i na. Significant deposi t s ar e also l ocat ed i n Ut ah,
Wyomi ng, I daho, Tennessee, and Mont ana. Ver y l arge deposi t s of rock
phos phat e exist i n ot her count r i es on t he several cont i nent s: for exampl e,
Mor occo i n Africa, USSR i n Eur ope, Brazil i n Sout h Amer i ca, Chi na i n
Asia, and i n Aust ral i a. Lesser quant i t i es exist i n many ot her count r i es. Th e
deposi t s ar e mar i ne i n ori gi n, and t he rock phos phat e mi ned will be
fl uoroapat i t e, chl or oapat i t e, and hydr oxyapat i t e. Subst i t ut i ons wi t h car-
bonat e ar e common. Mi ni ng of t hese deposi t s forms t he basis of t he phos-
phat e fertilizer i ndust ry.
P H O S P H O R U S CYCLI NG I N SOI L D EV ELO P MEN T
Apat i t e is t he pri nci pal mi ner al suppl yi ng P bef or e soil has been extensively
weat her ed. It account s for mor e t han 9 5 % of t he P i n i gneous rocks.
Apat i t es have a gener al chemi cal form of
Ca 1 0 ( X) 2 ( PO4 ) 6 ,
wher e X can be F
Cl
, O H
, or CO3

F or ms i n Yo u ng a nd Mod e r a t e l y We a t he r e d Soi l s
General l y, mi ner al deposi t s occur largely as fl uoroapat i t e, al t hough chl or o-
apat i t es ar e qui t e common. Fl uor oapat i t e i s t he pr edomi nat e f or m i n soils,
but hydr oxyapat i t e is f ound in many cal careous soils. Before cal careous soils
have been extensively weat her ed, apat i t e i s t hei r onl y sour ce of P; t he lack
of P in sol ut i on will limit biological gr owt h. Mor eover , in t he first stages of
t he evol ut i on of many soils, t he small a mount of P available is a severe
l i mi t at i on t o pl ant gr owt h. Un d e r t hese condi t i ons t he compet i t i on for P
a mong mi cr oor gani sms and macr oor gani sms i s so st r ong t hat t he P weat h-
er i ng from apat i t e will be rapi dl y i ncor por at ed i nt o biological tissue and
t hen slowly accumul at e i n or gani c compounds or humus (SOM). T h e very
low concent r at i on of P in sol ut i on limits t he oppor t uni t y for P to move
wi t hi n t he soil. Thi s st at e for P is depi ct ed by t he left side of Fi gur e 5. 1.
Th e r e i s little soluble P, apat i t e i s t he pr edomi nat e mi ner al f or m, and
or gani c P is slowly accumul at i ng.
How l i mi t i ng t he small a mount of available P can be i n t he earl y stages
of soil evol ut i on is seen by appl yi ng solubility pr oduct pri nci pl es to t he
dissolution of apat i t e. Usi ng, for exampl e, Ca 1 0 ( OH) 2 ( PO4 ) 6 , whi ch has a
pKs o
=
114. 6, in equi l i br i um with Ca F2 wi t h a pK = 10. 41, we may calcu-
late t hat total P is less t han 1 par t per billion (ppb) in sol ut i on, assumi ng t hat
t he soil cont ai ns free Ca CO3 i n equi l i br i um wi t h t he at mos pher e at a pH of
8. 3. At a pH of 7. 0, t he level woul d be about 8 ppb. Thus , at pH bet ween
7.0 and 8. 3, apat i t e has a very low solubility, whi ch t oget her wi t h its
crystalline nat ur e account s for t he persi st ence of apat i t e i n soils t hat ar e
young or only moder at el y weat her ed.
90 Soil and Fertilizer Phosphorus
FIGURE 5.1 The relative distribution of soil phosphate forms as
related to ti me of soil devel opment .
F or ms i n St r ong l y a nd I nt e ns e l y We a t he r e d Soi l s
Hydrol ysi s of soil mi neral s and l eachi ng dur i ng soil evol ut i on r emove cat-
i ons, and soil pH i s l owered. Th e gr eat er acidity at l ower pH i ncreases t he
solubility of apat i t e, giving i ncreased P activity in t he soil sol ut i on. T h e
l ower p H, i n t ur n, i ncreases t he solubility of Fe and Al compounds , whi ch
will pr eci pi t at e wi t h t he P rel eased to t he sol ut i on. Thus , as soil ages (see
Fi gur e 5.1), t her e is a decr ease in apat i t e P and a cor r es pondi ng i ncrease in
Fe and Al phosphor us. T h e i ncrease appear s mor e oft en i n t he F e - P
fract i on t han t he A l - P fract i on. Dur i ng this t ransi t i onal phase, t he or gani c
P fract i on has been accumul at i ng with humus unt i l i t occupi es an i mpor t ant
por t i on of t he t ot al P i n t he soil, per haps as much as 50 per cent of t he t ot al
in surface soils.
Ul t i mat e weat her i ng leads t o t he si t uat i on shown al ong t he r i ght side of
Fi gur e 5. 1. Soils have become al most totally depl et ed of Ca, Mg, and ot her
cat i ons, and t he soil i s very acid. Phos phor us i s ads or bed or pr eci pi t at ed by
Fe and Al, and soil or gani c P has become depl et ed. In many humi d t ropi cal
areas, soil weat her i ng has r eached this st age and has pr oduced LAC soils. It
i s c ommon t o fi nd t hat mor e t han 50 per cent of t he ECEC i s Al -sat urat ed
and t hat t he soil cont ai ns a vari abl e char ge ari si ng from amor phor us Fe and
Al oxi des and hydr oxi des. As shown i n Tabl e 5. 1, t ot al P has decr eased
drastically by this st age of weat her i ng. Th e ul t i mat e weat her i ng of soil
leaves i t acid (For exampl e see Tabl e 5. 1, pH 4. 8), wi t h t he C a - P fract i on
totally depl et ed, wi t h or gani c P very low, and with t he maj ori t y of P pr esent
as F e - P .
P H O S P H O R U S I N F ERT I LI Z ED A G R I C U LT U R A L SOI LS
Addi t i ons of P t o soils began l ong bef or e t he manuf act ur e of commer ci al
fertilizers as we know t hem t oday. T h e use of manur es , and per haps r ock
phos phat e and or gani c sources of P, began as earl y as r ecor ded t i me. Thus ,
Phosphorus in Fertilized Agricultural Soils 91
TABLE 5.1 Change in Phosphorus Forms with Weathering in
Venezuelan Soils
Phosphorus form, mg/ kg of soil
pH Total P Organic P Ca - P Al - P Fe - P
6.9 692 235 70 33 43
5.9 298 79 88 20 33
5.0 144 85 3 14 19
4.8 59 11 0 2 17
Source: Sanchez, 1976, adopt ed from Westi n and deBri to, 1969.
t he fi nal f or m of P t hat exists i n soils depends on t he st at e of weat her i ng of
t he soil and t he t ype and quant i t y of P t hat has been added.
Soils will vary from t he cal careous, relatively unweat her ed forms t o
highly weat her ed t ropi cal soils such as Oxisols. To under s t and what f or m P
will t ake when soils ar e fertilized, we need t o know t he possible forms of P
in soils. The y ar e shown in Fi gur e 5. 2. Each of t hese forms of P may coexist
i n a par t i cul ar soil, and each i s conver t ed from one f or m t o anot her by
component s passi ng t hr ough t he sol ut i on phase. The s e forms coexist be-
cause t he rat es of di ssol ut i on of one c ompound and of pr eci pi t at i on of
anot her ar e many t i mes kinetically very slow. Thus , t he r at e of ei t her
f or mat i on or di ssol ut i on of a par t i cul ar f or m of P may be ext r emel y i mpor -
t ant , even t hough t her e i s no i ndi cat i on of rat es i n Fi gur e 5. 2.
Soi l Sol ut i on P hos p hor u s
Phos phor us i n sol ut i on may exist bot h as or t hophos phat e or as hi gher
pol ymer s. Phos phor us i n t he soil sol ut i on, however , will be al most exclu-
sively as or t hophos phat e, PO4
3
. I f pol yphosphat es ar e a dde d t o t he soil
sol ut i on i n t he f or m of fertilizers, t hey will hydrol yze t o or t hophos phat e i n
a relatively shor t t i me. Thi s r eact i on will be faster if enzyme-act i vat ed, but
it also pr oceeds by chemi cal hydrolysis. It is expect ed t hat 50 per cent of
added pol yphosphat e will be hydr ol yzed t o or t hophos phat e i n 9 t o 16 days.
Th e i ndi vi dual species of or t hophos phat e t hat will be i n sol ut i on vary
wi t h p H, as shown i n Fi gur e 5. 3. In most agr i cul t ur al soils t he pH will be
bet ween 4. 0 and 9. 0; hence, t he i on species pr esent will be H 2 P O 4
and
H P O 4
2
. T h e i on species pr esent i s somewhat r el evant t o pl ant upt ake of P,
since i t has been shown t hat pl ant s pr ef er t he monoval ent i on. But t he r at e
at whi ch H 2 P O 4
i s conver t ed t o H P O 4
2
i n sol ut i on i s so r api d t hat pl ant s
have little difficulty obt ai ni ng t he necessary P for gr owt h, even in soils wi t h
pH of 8 or hi gher , when levels of t ot al P in sol ut i on ar e sufficiently hi gh.
Ot he r i on p a i r s ma d e up of Ca HP O4 , Mg PO4 , and C a P O4
ma y
exist in soil sol ut i on if soil pH is above 7. 0, but agai n t he di ssol ut i on of t hese
i on pai rs will be r api d i f t he sol ubl e H P O 4
2
i s r emoved f r om sol ut i on.
T h e concent r at i on of P f ound i n soil sol ut i on may r ange from <0. 01 t o
7 or 8 mg / L , dependi ng on soil pH, r ecent addi t i ons of fertilizer P, and
ot her soil factors. It woul d be unusual t o fi nd soil sol ut i on concent r at i ons
hi gher t han 8 mg / L since pr eci pi t at i on will limit P t o bel ow this val ue i n
any soil pH r ange. T h e maxi mum level of P in sol ut i on will be in soils wi t h a
pH bet ween 6.5 a nd 8. 0.
Ad s or b e d P hos p hor u s
Th e ads or bed fract i on of soil P is oft en consi der ed to be t he labile soil P.
Ads or bed P is t he por t i on of soil P t hat is bonde d to t he surface of ot her soil
compounds when a di scret e mi ner al phase i s not f or med. For exampl e,
sol ubl e P added t o a soil sol ut i on may be bound t o t he surface of amor -
phor us Al hydr oxi de wi t hout f or mi ng a di scret e A l - P mi ner al . Thi s woul d
be an exampl e of ads or bed P. Labi l e P is defi ned as t he fract i on t hat is
isotopically exchanged with
3 2
P or t hat i s readi l y ext r act ed by some chemi -
cal ext r act ant or by pl ant s. Thus , labile P may i ncl ude some or all t he
adsor bed P in a par t i cul ar soil. On t he ot her hand, in some soils t he labile P
may also i ncl ude some pr eci pi t at ed P, or i t may not i ncl ude all of t he
ads or bed P. Labi l e P has been an i mpor t ant wor ki ng concept for t he soil
scientist in r el at i ng soil P to pl ant -avai l abl e P. It is a measur abl e fract i on,
even t hough it may i ncl ude P f r om several of t he di scret e fractions of P hel d
in soils. Soil tests for P general l y t ry to meas ur e all or par t of t he labile P.
Two appr oaches t o under s t andi ng adsor bed P ar e i mpor t ant i n soil
fertility. Model s t o descri be t he par t i t i oni ng bet ween liquid and solid phases
of soils have been devel oped f r om l abor at or y meas ur ement s . The s e ar e
very i mpor t ant because t hey descri be how P will r eact in soils when br oad-
cast and t hor oughl y mi xed wi t h t hem. Thi s knowl edge i s necessary t o
pr edi ct how much P will be i n sol ut i on for pl ant upt ake and how much will
be i n t he sol ut i on t hat moves f r om t he soil t o runoff wat er s.
Soils vary great l y i n t hei r ability t o adsor b P and i n t he rel at i on be-
t ween sol ut i on P and ads or bed P. Ext r emes ar e i l l ust rat ed i n Fi gur e 5. 4.
General l y, bot h very sandy soils a nd soils wi t h a l arge a mount of or gani c
mat t er hol d only small quant i t i es of P i n t he ads or bed f or m, a nd t hey do not
f or m st r ong bonds wi t h t he ads or bed P. If we assume t hat 0.2 mg / L of P i s
a desi r ed quant i t y for pl ant gr owt h, 25 mg / k g (50 pounds / a c r e ) of P woul d
be adequat e t o raise t he level from near zer o t o adequat e for Grayl i ng sand.
Th e Br ookst on l oam Ap, whi ch i s mor e typical for agr i cul t ur al soils, woul d
r equi r e 61 mg / k g (122 pounds / a c r e ) of P and t he B hor i zon of t he hi ghl y
weat her ed Griffin soil woul d r equi r e 735 mg / k g ( 1470 pounds / a c r e ) .
Dur i ng t he past 100 years when mode r n agr i cul t ur e and t he fertilizer
i ndust ry was devel opi ng, t her e was little concer n about t he consequences of
hi gh levels of ads or bed P i n agri cul t ural soils. I ndeed, t he gr eat er pr obl em
dur i ng t he early par t of this per i od was how t o obt ai n ma xi mum upt ake of P
with l i mi t ed appl i cat i on of P fertilizer. But this si t uat i on has changed dras-
tically for heavily fertilized soils (see Tabl e 5.2). Wi t h gr eat er amount s of
adsor bed P have come gr eat er amount s of P i n t he wat er t hat r uns off
agri cul t ural l ands a nd percol at es t hr ough soils. To this poi nt i n t i me, be-
cause most subsoils have a gr eat capacity t o ads or b P, t her e has been little
i ncrease i n t he P cont ent of agri cul t ural dr ai nage wat ers and of
gr oundwat er s .
A numbe r of equat i ons have been devel oped t o descri be quant i t at i vel y
t he di st ri but i on of P bet ween t he ads or bed and sol ut i on phases. T h e t wo
most c ommon ar e based on wel l -known equat i ons f or mul at ed by He nr y
FIGURE 5.3 Mol e percentage of each ortho-
phosphate species as a functi on of pH.
FI GURE 5.4 Partitioning of phosphorus bet ween the solution and the
solid phase of four soil hori zons varying widely in texture and chemical
properti es. The t ext ure of Griffin B and Ont onagan A is clay, of Brook-
ston A l oam, and of Graying A sand.
Fr eundl i ch and I r vi ng Langmui r for r epr es ent i ng t he vol ume of gas ab
sor bed as a funct i on of pr essur e. Accor di ng t o t he adapt ed Fr eundl i ch
equat i on,
P a d / m = k (Psol )
1 / n
(51)
TABLE 5.2 Median Phosphorus Soil Test Values of Mineral Soils
for Each of Six Geographical Regions in Michigan
Median P soil test value, pp2m
Region 1972 1976 1977 1979 1980
Northern lower 42 44 89
West central 83 104 168
Thumb and eastern 41 55 79
South central 44 46 86
Southwest 72 98 143
Upper Peninsula 36 32 77
Source: Mi ents and Warncke, 1983.
Whe r e P a d / m = P adsor bed per m gr ams of soil,
Psol = P concent r at i on (or activity) in t he equi l i br i um sol ut i on,
a nd k and n ar e const ant s defi ned exper i ment al l y for a gi ven soil.
Th e use of this equat i on may be i l l ust rat ed as follows. If k and n have
been exper i ment al l y det er mi ned as 500 and 3, respectively, for a gi ven soil,
t he quant i t y of P t hat must be adsor bed t o give 0.2 ppm P i n t he soil
sol ut i on is cal cul at ed as follows:
log Pad = l og500 + 1/ 3 l og0. 2 (5.2)
l ogPad = 2. 70 + 1/ 3 ( 0. 699) = 2. 467 (5.3)
Pad = 293 mg / k g soil (5.4)
T h e Langmui r equat i on i s
Pad/m = k(Psol)b / [ 1 + k(Psol)] (5.5)
wher e P a d / m = P ads or bed per m gr ams of soil,
Psol = P concent r at i on (or activity) in t he equi l i br i um sol ut i on,
b = t he ma xi mum P t hat can be adsor bed,
k = a const ant r el at ed to bondi ng ener gy.
A useful f or m of this equat i on is k = / P ( l ) , wher e is t he fract i on
of t he adsor pt i on ma xi mum t hat i s occupi ed by P. Agai n, once b a nd k ar e
exper i ment al l y det er mi ned, it is easy to cal cul at e t he quant i t y of P t hat must
t he adsor bed by a soil to rai se t hat level in sol ut i on to a desi r ed level.
For t he four soils shown i n Fi gur e 5. 4, i t woul d r equi r e 1 470, 150,
122, and 50 pounds per acr e of P for Griffin B, Ont ona gon A, Br ookst on
Ap, and Grayl i ng A hor i zons, respectively, to rai se t he P level in sol ut i on
f r om 0 t o 0.2 mg P / L , a val ue whi ch i s necessary for nor mal pl ant gr owt h.
Fr om anot her poi nt of view, this i s t he quant i t y of P t hat each of t he soils
woul d adsor b from appl i ed wast ewat er bef or e t he soil sol ut i on level woul d
exceed 0.2 mg P / L .
Th e chemi cal f or m of adsor bed P woul d also be useful i nf or mat i on,
since this knowl edge woul d hel p us t o det er mi ne what mi ni mum a mount of
P must be appl i ed t o i ncrease availability. Component s of soils t hat ar e
i mpor t ant i n adsor bi ng P ar e clays, Fe a nd Al oxi des a nd hydr oxi des, and
Ca CO3 . I r on coat i ngs t hat ar e associated wi t h clay mi neral s may account for
much of t he clay' s ability t o adsor b P. Amor phor us oxi des of Fe and Al ar e
much mor e effective at adsor bi ng P t han crystalline compounds . As soils
weat her , t hey become abl e t o ads or b l arge quant i t i es of P because t hey have
f or med amor phor us Fe and Al oxi des and hydr oxi des. But as t he weat her
i ng process cont i nues, t hese amor phor us compounds crystallize, exposi ng
less surface ar ea and fewer hydroxyl s. The y t her ef or e adsor b less t ot al P.
Cal ci um car bonat e is a pri nci pal adsor pt i on site for P in cal careous
soils, but i t has been shown recent l y t hat Fe compounds also funct i on i n
adsor pt i on i n cal careous soils. Phosphat e ads or bed ont o Ca CO3 may l at er
crystallize to pr eci pi t at ed P compounds .
Pr e c i pi t a t e d P hos p hor u s
Many i nsol ubl e compounds cont ai ni ng P f or m i n soils. T h e pri nci pal com-
pounds t hat ar e f ound or ar e pr eci pi t at ed when sol ubl e P fertilizers ar e
a dde d t o soils depend on soil pH and t he ot her ions t hat ar e available for
preci pi t at i on. We will discuss t he preci pi t at es of P in t hr ee gr oups of soils
based on t hei r p H.
Calcareous Soils
Unl ess amount s of soluble P have been added to a cal careous soil, apat i t e P
is expect ed to be t he pr edomi nant pr eci pi t at ed f or m. Since it is a compl ex
mol ecul ar f or m and crystalline i n nat ur e, apat i t es ar e so slow t o dissolve
t hat t hey do not furni sh sufficient sol ubl e P to mai nt ai n a soil in a fertile
condi t i on. Levels of P i n soil sol ut i on depend on pH when apat i t e cont rol s
t he solubility and ar e less t han 0. 01 mg P / L (10 ppb) for soil pH gr eat er
t han 7. 0.
Whe n t he sol ut i on level of P is i ncr eased by addi ng sol ubl e P, for
exampl e, by addi ng 0-45-0, di cal ci um phos phat e di hydr at e,
Ca HP O4 2 H2 O, forms wi t hi n a few mi nut es. Thi s c ompound i s not a
stable phase i n soils, and wi t hi n t hr ee days anhydr ous di cal ci um phosphat e,
C a HP 0 4 , forms. I t has been shown t hat oct acal ci um phosphat e,
Ca 4 H( P O4 ) 3 2 . 5 H2 O, forms i n t wo t o t hr ee mont hs . Di cal ci um phos phat e
and oct acal ci um phos phat e ar e very significant i n mai nt ai ni ng soil fertility
of cal careous soils, since bot h mai nt ai n much mor e sol ubl e P t han does
apat i t e. Conver si on of t hese phosphat es t o less sol ubl e forms, such as apa-
t i t e, r equi r es many mont hs or years. T h e pract i cal significance of this i s t hat
we can fertilize cal careous soils and expect to mai nt ai n sui t abl e levels of P
for pl ant gr owt h for several mont hs or even years, even t hough much of t he
P preci pi t at es.
Mildly Ac i d Soils
I n t he pH r ange of 5.5 t o 7. 0, adsor pt i on may be mor e i mpor t ant t han
preci pi t at i on in cont r ol l i ng t he level of P in soil sol ut i on. It is assumed t hat
t he soluble P mat eri al s whi ch pr eci pi t at e i n this pH r ange will pr eci pi t at e
Fe or Al phosphat es. Th e pr eci pi t at i on pr oduct s t hat f or m will in-
volve many compl ex species. Pot assi um and N H 4
+
t ar anaki t es,
H6 ( K, NH4 ) 3 Al 5 ( PO4 ) 8 1 8 H2 O, f or m as well as mi xed species i ncl udi ng Ca,
Mg, Al, and K. Si mpl e compounds such as st r engi t e, F e P O4 2 H2 O, and
variscite, A1PO4 2 H2 O, ar e likely t o f or m only i n very acid soils.
Strongly Acid Soils
St rongl y acid soils ar e f ound i n many ar eas of t he worl d, i ncl udi ng t he
sout heast er n Uni t ed St at es and t he humi d t ropi cal ar eas of Sout h Amer i ca,
Africa, and sout heast er n Asia. It woul d be a mi st ake t o assume t hat all t hese
soils have similar pr oper t i es. But many do possess sufficient sol ubl e and
exchangeabl e Fe and Al t o pr eci pi t at e P. Al t hough st r engi t e and variscite
become good model compounds for pr eci pi t at ed P i n t he st rongl y aci d soils,
much of t he P i n t hese soils will be occl uded i n a mor phor us Fe a nd Al
oxi des and hydr oxi des. Fr act i onat i on schemes, whi ch i ncl ude an occl uded
or r educt ant - sol ubl e fract i on, will show t he pr edomi nant fract i on of P t o be
in this f or m. Ident i fyi ng specifically pr eci pi t at ed compounds is ext r emel y
difficult, and so i s di st i ngui shi ng bet ween t he ads or bed a nd pr eci pi t at ed
phases. Phos phor us will be st rongl y hel d i n t hese soils, and t he nat i ve soil
fertility will be very l i mi t ed because little P is sol ubl e. The s e aci d soils
r equi r e careful management with respect t o P. The y can be qui t e pr oduc-
tive if adequat e P fertilizer, as well as ot her fertilizer nut r i ent s, ar e utilized.
General l y, band pl acement of P fertilizer is useful because pl ant s will t ake
up mor e P when economi cal P r at es ar e used and t he P is band- pl aced
r at her t han i ncor por at ed. Levels of P may be bui l t up i n t hese soils aft er
r epeat ed appl i cat i ons of fertilizer.
Bi ol og i c a l l y I nc or p or a t e d P hos p hor u s
Pl ant s absor b P di rect l y from t he soil sol ut i on. Th e t ot al quant i t y r emoved
by crops per year i s small compar ed t o t he N and K r emoved, r angi ng from
6.0 t o 26 k g / h a (5 t o 23 pounds / a c r e ) of P, with meadow hay absor bi ng
small amount s and mangol ds l arge amount s . I n most agr onomi c pl ant s t he
P cont ent will be bet ween 0 . 1 % and 0. 4%. Th e concent r at i on i n pl ant tissue
decreases consi derabl y with age; for exampl e, leaves from cor n pl ant s one
foot hi gh cont ai ned 0. 48% P, and t he leaves f r om cor n pl ant s at tasseling
cont ai ned 0. 22% P. Excessively hi gh values of P i n pl ant tissue have been
r epor t ed t o be as much as 1%, but t hese wer e associated wi t h P accumul a-
t i on br ought about by a deficiency of anot her nut r i ent such as Zn.
Moder n hi gh-yi el di ng vari et i es of pl ant s have i ncr eased t he level of P
absor bed by pl ant s. For exampl e, t hr ee hybr i ds Pi oneer 3780, Mi chi gan
5922, and Pi oneer 3572 yi el di ng an aver age of 13. 04 Mg / h a ( 208
bus hel s / acr e) of gr ai n and 8. 32 Mg / h a (5. 82 t ons / acr e) of st over, r emoved
an aver age of 26. 3 kg P / h a i n grai n and 4. 7 kg P / h a i n t he st over. Alfalfa i s
a gr eat accumul at or of P and i s expect ed t o r emove 59 kg P / h a for a
22-met ri c-t on annual yield (10 t ons / acr e) .
Since P is accumul at ed in t he r epr oduct i ve por t i on of t he pl ant , whi ch
is usually har vest ed, t he r esi due r e t ur ne d to t he soil often has a low level of
P. Th e r at i o of P i n t he har vest ed por t i on t o t he r esi due i s usually gr eat er
t han 2 : 1 . Al t hough t he fract i on r e t ur ne d i n t he r esi due i s i mpor t ant , i t i s
nor mal l y less t han 1% of t he t ot al or gani c soil P. Soil mi cr oor gani sms will
also compet e for available P, but little dat a ar e available about t he quant i t y
of P t hat may be i ncor por at ed i nt o living mi cr oor gani sms. It is expect ed
t hat mi cr oor gani sms funct i on mor e i n t ur nover of or gani c P t han i n
r et ent i on.
Soi l Or g a ni c P hos p hor u s
As shown in Fi gur e 5. 2, or gani c soil P will i ncl ude bot h biologically avail-
abl e or gani c P and resi st ant or gani c P. T h e exact chemi cal nat ur e of
Country of organic P of total P
Denmark 46 61
New Zealand 5 - 26 3 0 - 77
Scotland 2 4 - 58 2 2 - 74
Canada 10- 30 9 - 54
United States 10- 25 3 - 52
Source: Halstead and McKercher, 1975.
or gani c soil P has been difficult t o identify precisely. On e f or m, inositol P,
has been meas ur ed and is t he l argest identifiable fraction of or gani c P (see
Tabl e 5.3). T h e st r uct ur e of one inositol c ompound i s shown i n Fi gur e 5. 5.
Th e r e can be from one t o six phos phat e gr oups at t ached t o t he r i ng
st r uct ur e shown, whi ch gives a numbe r of slightly different compounds , all
r ef er r ed t o as inositol P, and all wi t h similar pr oper t i es.
Th e ot her known or gani c compounds such as phosphol i pi ds, nucl ei c
acids, phosphopr ot ei ns, a nd sugar phosphat es may be pr esent , but t hey
usually r epr es ent a small per cent age of t he or gani c P. Th e maj ori t y of t he
or gani c P pr esent i s as par t of t he stable humus mat er i al f or med i n soils.
Li ke t he N in humus , it is stable but difficult to identify as a preci se or gani c
compound; it is rel eased slowly as t he humus decomposes in t he soil.
Or gani c P is i mpor t ant in suppl yi ng P for pl ant gr owt h when fresh
or gani c mat eri al s ar e added t o soils. Fr om 6% t o 16% of l abel ed P added i n
t he f or m of fungal mycelia was t aken up by wheat pl ant s i n a fi ve-week
gr owi ng per i od. Upt ake from an i nor gani c P sour ce unde r similar gr owi ng
condi t i ons was above 20% of t he P added. Whe n ma nur e i s a dde d as t he
source of or gani c P, t he P is slowly rel eased over a l onger por t i on of t he
gr owi ng season, for t he P i n ma nur e has been somewhat stabilized bef or e
FIGURE 5.5 Structure of inositol monophosphat e.
Basis of Phosphorus Fertilizer Recommendations 99
appl i cat i on because mi cr obes act on t he less stable or gani c P compounds i n
fresh ma nur e .
Th e t ur nover of fresh or gani c P undoubt edl y releases P t o t he soluble
a nd labile pool . As such, i t may be very i mpor t ant i n furni shi ng available P
for crops. But much of t he or gani c P in t he soil is in a f or m resi st ant to
decomposi t i on and i s not readi l y available for biological upt ake.
P H O S P H O R U S U P T A K E B Y P LA N T S
Some st udi es wi t h excised r oot s i ndi cat ed t hat pl ant s pr ef er r ed t he mono-
val ent ani on H 2 P O 4
over t he di val ent H P O 4

2
by about 10 t o 1. But since
t he conversi on bet ween t he t wo species i n sol ut i on i s very r api d, this prefer-
ence is pr obabl y of little i mpor t ance for soils in t he pH r ange 4 to 8.
Movement of P t o pl ant r oot s i s general l y by diffusion r at her t han by
mass flow. Th e cont r i but i on of mass flow t o t he movement of P t o r oot s can
be easily cal cul at ed i f t hr ee assumpt i ons ar e made, about t he t r anspi r at i on
r at i o, t he aver age concent r at i on of P i n pl ant tissue, and t he aver age
concent r at i on of P in soil sol ut i on. For exampl e, if we assume t hat 350
gr ams of wat er ar e used t o pr oduce 1 gr am of dr y pl ant tissue (t ranspi rat i on
r at i o of 350 t o 1), t hat t he pl ant tissue concent r at i on i s 0. 25% P, and t hat
t he soil sol ut i on cont ai ns on t he aver age 0.1 mg P / L , t hen 350 ml X 0.1 mg
P / L equal s 0. 035 mg P, whi ch will move wi t h t he wat er . On e gr am of tissue
cont ai ns 2. 5 mg P; t her ef or e, 1.4% of t he P woul d r each r oot s by mass flow.
Si nce t he level of P in sol ut i on is general l y less t han 0.2 mg / L , mass flow
will not play an i mpor t ant par t i n P movement t o r oot s i n ot her t han highly
fertilized soils.
It has l ong been known t hat mycor r hi zal fungi will i ncrease t he avail-
ability of nut r i ent s t o many pl ant s. T h e mycelia of t he fungi, t hei r masses of
i nt er woven fi l ament s, will become i nt i mat el y associated with t he pl ant r oot s
and funct i on i n a symbiotic rel at i onshi p. Th e mycelia become an ext ensi on
of t he r oot s. Th e i ncreased availability of P t o t he host pl ant t hr ough
mycor r hi zal fungi i s well known. Al t hough bet t er document ed wi t h t r ee
species, nume r ous st udi es have shown t hat agr onomi c crops pl ant ed i n soil
of low fertility but cont ai ni ng t he mycelia gr ow bet t er , t ake up mor e
nut r i ent s, and have bet t er yields. But evi dence has also shown t hat well-fer-
tilized agr onomi c crops will out yi el d unfert i l i zed cr ops t hat ar e gr own i n
low-fertility soil and have mycorrhi zal fungi associated wi t h t hei r r oot s.
Agr onomi c crops gr own i n less-developed count r i es wher e nat ur al P levels
ar e very low ar e expect ed t o benefi t mor e from t he P t aken up by t he
mycelia of mycorrhi zal fungi t han do hi ghl y fertilized cr ops i n devel oped
count r i es.
BASI S O F P H O S P H O R U S
F ERT I LI Z ER R EC O MMEN D A T I O N S
Recommendat i ons for P fertilizer ar e ma de on t he basis of a soil-testing
pr ogr a m in whi ch P soil tests have been cor r el at ed with field fertility
st udi es. Pr el i mi nar y eval uat i ons of a par t i cul ar soil test for P or compar i -
TABLE 5.3 Inositol Phosphorus Content of Soils
Inositol P, % Organic P, %
sons of di fferent soil tests may involve gr eenhous e st udi es. Dur i ng t he past
f i f t y years, many di fferent ext r act ant s have been devel oped i n at t empt s t o
measur e labile P or P in t he soil t hat woul d cor r el at e wi t h t he yield r esponse
t o P fertilization. Th r e e i n wi despr ead use will be discussed her e. Ot her s
may be equally effective in local si t uat i ons if pr oper l y cor r el at ed wi t h field
trials, and addi t i onal ext r act ant s may be devel oped i n t he f ut ur e.
In 1945 Bray and Kur t z devel oped t wo ext r act ant s for P i n soils, one
for r eser ve P a nd one for available P. T h e available P test ( Br a y- Kur t z P1)
utilized 0. 025 N HC1 + 0. 03 N NH4 F as t he ext r act i ng sol ut i on. Soil-to-so-
l ut i on rat i os have vari ed from 1 : 7 to 1 : 50, and shaki ng t i me has vari ed
from 1 t o 30 mi nut es. Most soil-testing l abor at or i es i n t he Nor t h Cent r al
r egi on of t he Uni t ed St at es ar e now usi ng a 1:10 soil-to-solution r at i o with a
five-minute ext r act i on per i od. A r at i o of 1 : 50 wi t h a one- mi nut e ext r act i on
per i od has been shown t o be much mor e effective on soils t hat ar e calcar-
eous or have recei ved appl i cat i ons of r ock phosphat e. But t he pr ocedur e
utilized i n soil-testing l abor at or i es has been very satisfactory i n di st i ngui sh-
i ng bet ween soils wi t h small, medi um, a nd l arge amount s of available P.
Ol sen devel oped t he sodi um bi car bonat e ext r act abl e P test for use on
cal careous soils. T h e P i s ext r act ed with 0. 5 M Na HCO3 buffered at pH 8.5
wi t h a soil-to-solution r at i o of 1 : 2 and a 30- mi nut e shaki ng or ext r act i ng
t i me.
Th e mor e acid soils of t he Pi edmont ar ea of t he sout heast er n Uni t ed
States as well as t he acid, hi ghl y weat her ed soils of ot her r egi ons of t he
wor l d cont ai n very little P t hat is ext r act ed wi t h ei t her t he Br a y - Ku r t z P1
or Ol sen' s test. For t hese soils, Melich devel oped a st r onger acid ext r act ant
utilizing 0. 05 N HCl + 0. 025 N H2 S O4 and l at er an i mpr oved ext r act ant
usi ng 0.2 N CH3 COOH, 0.2 N NH4 Cl plus 0. 015 N NH4 F pl us 0. 012 N
HC1.
Analytical det er mi nat i on for P in sol ut i on is general l y by t he Mu r p h y -
Riley me t hod utilizing t he bl ue col or of mol ybdenum and ascorbi c acid as
t he r educi ng agent . Thi s met hod i s widely adapt abl e t o col ori met ri c
met hods i ncl udi ng aut oanal yzer s and flow injection anal yzers.
Most ext r act ant s utilized i n soil tests do not r emove t he preci se fract i on
of t he nut r i ent i n t he soil t hat i s absor bed by pl ant s dur i ng a gr owi ng
season. Thi s does not make t he soil test less useful or desi rabl e. But t he
fract i on t hat i s ext r act ed must cor r el at e wi t h t he a mount r emoved by pl ant s
dur i ng t he gr owi ng season. Thus , i n i nt er pr et i ng a soil test, t he most
i mpor t ant fact or i s t hat i t cor r el at e wi t h upt ake of t he nut r i ent and wi t h t he
yield r esponse to t he nut r i ent . General l y, P soil tests ar e eval uat ed as low,
medi um, hi gh, and very hi gh. Soil t hat tests low i n P will r equi r e addi t i ons
of P fertilizer t hat suppl y mor e t han t he quant i t y r emoved by t he cr op
bei ng gr own because t he P added t o t he soil i n fertilizer becomes fi xed.
Soils t est i ng medi um i n P will r equi r e appl i cat i ons of slightly mor e t han t hat
r emoved by t he cr op for adequat e yield and gr owt h. Whe n a soil tests hi gh
i n P, no yield r esponse i s expect ed t o P fertilizer. He r e di fferent appr oaches
t o fertilizer management may be followed. First, a st ar t er fertilizer banded
Phosphorus Fertilizers 101
at pl ant i ng t i me may be used t o appl y a mai nt enance a mount of P. T h e
i nt ent is to appl y t he quant i t y of P t hat is r emoved by t he gr owi ng cr ops so
t hat t he hi gh a mount of P f ound by t he test will be mai nt ai ned. Al t er nat el y,
no P fertilizer is appl i ed, and t he soil is r et est ed at f r equent i nt erval s to
det er mi ne when P must agai n be appl i ed.
Whe n a soil tests very hi gh in P, t he probabi l i t y of P bei ng lost to
surface wat ers t hr ough runoff and erosi on i s gr eat . To r educe t he risk of
envi r onment al degr adat i on, f ar mer s shoul d not appl y P fertilizer t o soils
t est i ng very hi gh in P. A possible except i on is for pot at o pr oduct i on, a cr op
whi ch somet i mes gives yield responses to P fertilizer, even t hough soils test
very hi gh. Th e soil shoul d be r et est ed frequent l y t o det er mi ne when P
levels have been r educed t o t he poi nt of r equi r i ng t he addi t i on of P agai n.
Re c omme nd a t i ons f or P hos p hor u s Fe r t i l i z a t i on of Cr ops
Since fertilizer r ecommendat i ons ar e specific t o t he ar ea a nd cr op, onl y
gener al gui del i nes will be gi ven her e. The y must be modi fi ed t o fi t t he soil
t ype, t he cl i mat e, and t he yield goal of t he f ar mer for a par t i cul ar ar ea. It i s
i mpor t ant for a f ar mer to have realistic yield goals when pl anni ng a fertil-
i zer pr ogr am. Fert i l i zi ng for 200 bushel s of cor n per acr e i s futile and
expensi ve i f t he soil and cl i mat e will suppor t only 120 bus hel s / acr e.
Fr om Tabl e 5. 4, i t i s appar ent t hat soybeans and cor n r equi r e consi der-
ably less P t han does wheat . But t he maj or di fference comes wi t h pot at oes
a nd ot her veget abl e crops. Al t hough i t i s easy t o adj ust and fertilize a cr op
t hat r equi r es a l arge a mount of P, t he danger of excessive resi dual P i n
t hese soils i s gr eat , and this causes concer n about t he envi r onment .
P H O S P H O R U S F ERT I LI Z ERS
T h e begi nni ng mi ner al for most , i f not all, P fertilizers i s apat i t e, or r ock
phos phat e. Th e mi ner al deposi t i s exposed general l y by st ri p mi ni ng, whi ch
r emoves t he surface mat er i al or over bur den. Th e n t he mi ner al deposi t i s
r emoved by l arge shovels, dragl i nes, or wat er unde r pr essur e. T h e mi ner al
TABLE 5.4 Guidelines for Phosphorus Recommendations for Several
Agronomic* Crops
Phosphorus applied, pounds/ acre
Soil P test, mg/ kg Corn Wheat Soybeans Potatoes
15 30 39 22 76
30 13 22 0 70
50 0 0 0 61
80 0 0 0 48
175 0 0 0 0
*Yi el d goal s assumed: corn, 140 bushel s/ acre; wheat, 70 bushel s/ acre; soybeans,
50 bushel s/ acre; and potatoes, 400 cwt / acre.
i s sel dom i n a pur e form and must be separ at ed from i mpuri t i es, i ncl udi ng
i ner t mat eri al , bef or e it is utilized. Onc e it is separ at ed from i mpuri t i es,
r ock phos phat e may be fi nel y gr ound a nd mar ket ed di rect l y as a fertilizer
sour ce of P. Thi s pr oduct general l y cont ai ns from 11. 5% t o 17. 5% t ot al P.
None of t he P will be wat er-sol ubl e, but from 5% to 17% of t he t ot al P is
sol ubl e in citric acid. Th e t er m available P is appl i ed to P fertilizers and
i ncl udes t he P soluble in citric acid.
Th e r e ar e t wo al t er nat i ve manuf act ur i ng processes t o make r ock phos-
phat es i nt o a mor e sol ubl e P fertilizer. T h e first is di r ect acidification of
rock phosphat e; i n t he second t he pr oduct i s phosphor i c aci d or el ement al
P, whi ch becomes a basic mat er i al for f ur t her manuf act ur e.
Di r e c t Ac i di f i c a t i on of Roc k P hos p ha t e
If sulfuric aci d is mi xed wi t h r ock phosphat e, t he P is r e nde r e d sol ubl e by
t he following react i on:
Ca 1 0 F 2 ( P O4 ) 6 + 7 H2 S O4 = 3 Ca ( H2 PO4 ) 2 + 7 Ca SO4 + 2 HF (5.6)
Th e pr oduct i s commonl y called super phosphat e, 0-20-0, and cont ai ns
sol ubl e monocal ci um phosphat e and cal ci um sulfate. T h e HF i s a t oxi c gas
t hat escapes dur i ng manuf act ur i ng and usually is, and cert ai nl y shoul d be,
r ecover ed as a bypr oduct . Al t hough this pr oduct is less c ommon in t he
Uni t ed States t oday because of t he expense of shi ppi ng a low-analysis
fertilizer, it is an excel l ent sour ce of P and carri es bot h Ca and S in addi t i on
t o P.
Partially acidifying rock phos phat e is a pract i ce t hat mer i t s consi dera-
t i on i n devel opi ng count r i es wher e sophi st i cat ed manuf act ur i ng may not be
possible. Wast e sulfuric acid, whi ch i s oft en available, can be used t o r eact
partially wi t h r ock phosphat e, pr oduci ng a mat eri al whi ch cont ai ns consid-
er abl e soluble P. Al t hough this soluble P is not as effective as 0-20-0, it is
much mor e useful t han di r ect appl i cat i on of rock phosphat e.
Acidification of r ock phos phat e wi t h phosphor i c acid pr oduces a hi gh-
gr ade, wat er-sol ubl e pr oduct known as t ri pl e super phosphat e, 0-45-0, ac-
cor di ng t o t he following react i on:
Ca 1 0 F 2 ( P O4 ) 6 + 1 4 H3 P O4 = 1 0 Ca ( H2 PO4 ) 2 + 2 HF (5.7)
Al t hough t he manuf act ur i ng i s similar t o t hat for 0-20-0, this mat er i al does
not car r y gypsum i n t he fi nal pr oduct . It also r equi r es t he pr oduct i on of
phosphor i c acid for manuf act ur e.
Phos p hor i c Ac i d Pr od u c t i on
Phosphor i c acid i s pr epar ed by t he wet -process acid met hod and by t he
electric furnace el ement al P met hod. Wet -process acid is pr epar ed by react -
i ng rock phos phat e with sulfuric acid, al l owi ng sufficient t i me for gypsum t o
crystallize, and fi l t eri ng t he mat eri al t o obt ai n t he phosphor i c acid. Al-
Phosphorus Fertilizers 103
t hough t he r eact i on i s similar t o t hat i n equat i on 5.6 i l l ust rat i ng t he manu-
f act ur e of or di nar y super phosphat e, t he differences ar e significant. As
shown i n t he following equat i on,
Ca 1 0 F 2 ( P O4 ) 6 + 1 0 H2 S O4 + 2 0 H2 O =
10Ca SO4 2 H2 O + 6 HS P O4 + 2 HF (5.8)
addi t i onal sulfuric acid and wat er ar e added t o t he rock phosphat e. Usually
about ei ght hour s ar e al l owed for di gest i on of t he mi xt ur e, aft er whi ch t i me
t he crystals of gypsum, Ca SO4 2 H2 O, ar e sufficiently l arge t o be f i l t er ed
easily. Thi s aci d may be di rect l y used for acidification of rock phos phat e but
r equi r es f ur t her puri fi cat i on and concent r at i on bef or e i t can be used for
t he manuf act ur e of pol yphosphat e fertilizers.
Electric furnace phosphor i c acid i s pr epar ed by heat i ng r ock phos phat e
al ong wi t h car bon and silica to t emper at ur es in excess of 1 400 degr ees C in
a r educi ng at mos pher e. Th e r eact i on pr oduces el ement al P, whi ch may be
oxi di zed t o f or m P 2 O5 , whi ch when hydr at ed becomes phosphor i c acid.
Thi s process will pr oduce a hi gh-puri t y acid and wi t h pr ope r cont r ol one
wi t h t he desi red rat i o of or t hophos phat e t o pol yphosphat e for use i n liquid
fertilizer manuf act ur e. But because t he electric furnace manuf act ur i ng
process i s mor e expensi ve, most of t he phosphor i c acid t hat goes i nt o
fertilizer manuf act ur e i s pr epar ed by t he wet -process met hod.
Ma nu f a c t u r e of A mmo n i u m Phos p ha t e s
In addi t i on t o bei ng used for manuf act ur i ng 0-45-0, whi ch was discussed
previ ousl y, phosphor i c acid i s utilized for t he manuf act ur e of monoam-
moni um phos phat e (MAP), di ammoni um phos phat e (DAP) and a mmoni um
pol yphosphat e (APP). Ammoni um or t hophos phat e can be pr epar ed t o yield
t wo pr oduct s, MAP and DAP, dependi ng on t he degr ee of ammoni fi ca-
t i on. Several met hods ar e used t o manuf act ur e t he pr oduct s . Basically,
phosphor i c acid i s t r eat ed wi t h ammoni a. If t he neut ral i zat i on i s car r i ed out
to a l i mi t ed ext ent , MAP is pr oduced with a typical analysis of 11-48-0, as
follows:
N H 3 + H 3 P O 4 = N H 4 H 2 P O 4 (5.9)
If neut ral i zat i on i s car r i ed out t o obt ai n a hi gher r at i o of ammoni a t o
phosphor i c acid, DAP is pr oduced with a typical analysis of 18-48-0, as
follows:
2 NHS + H 3 P O 4 = ( NH4 ) 2 HP O4 (5. 10)
Gr ades bet ween t he t wo mi xt ur es can be obt ai ned wi t h i nt er medi at e
ammoni fi cat i on.
Wi t h t he devel opment of super phosphor i c acid came t he possibility of
pr oduci ng hi gher-anal ysi s a mmoni um phosphat es, usually called a mmo-
ni um pol yphosphat es, APP. Th e most commonl y used super phosphor i c
acid cont ai ns about 50% or t hophos phat e, with t he r emai nder as hi gher
pol ymer s of phosphor i c acid. Th e maj or por t i on of t he hi gher pol ymer s ar e
pr esent as pyr ophosphat es, maki ng up 4 3 % of t he t ot al P. Ammoni um
pol yphosphat es have f or med an i mpor t ant par t of t he liquid fertilizer in-
dust ry. A r at her simple process of car r yi ng out t he neut r al i zat i on r eact i on
i n a pi pe r eact or allows t he liquid fertilizer t o be pr epar ed on site by
neut r al i zi ng t he super phosphor i c aci d wi t h ammoni a. Typi cal gr ades ar e
11-32-0 a nd 11-37-0. A typical gr ade of APP when t he fertilizer i s i n t he
dr y form woul d be 15-62-0.
USE OF P H O S P H O R U S F ERT I LI Z ERS
Us e of Roc k P hos p ha t e
Rock phos phat e may be di rect l y appl i ed t o soils, usually by br oadcast i ng
and i ncor por at i ng i t i nt o t he soil with tillage. Years of r esear ch wor k
car r i ed out several decades ago showed t hat this mat er i al i s not effective
when utilized in a soil management scheme in whi ch soils ar e l i med to
mai nt ai n soil pH above 6. 0. As shown earl i er i n this chapt er , t he solubility
of rock is so l i mi t ed t hat it is of little use unde r slightly acidic to neut r al
condi t i ons.
Rock phos phat e may be of consi der abl e val ue, however , i f appl i ed t o
hi ghl y weat her ed acid soils t hat have very little available P. Rock phos phat e
added t o t hese soils may be readi l y soluble since t he pH i s low, and very
often t he Ca concent r at i on (activity) i s also low. Th e i mpor t ance of Ca
activity is shown in Fi gur e 5. 6. It is also known t hat Ca activity may not be
closely r el at ed t o pH (see Tabl e 5.5). For this r eason, t he consequences of
usi ng r ock phosphat e, even on very acid soils, ar e somet i mes unpr edi ct abl e.
Nevert hel ess, rock phos phat e i s t he sour ce most often available i n many
l esser-devel oped count r i es. In t hese count r i es t he pri ce of i mpor t i ng solu-
bl e, manuf act ur ed P fertilizers will pr ecl ude t hei r use. Whe n r ock phos-
phat es ar e locally available, t hey may be used t o advant age. But i t must be
emphasi zed t hat t he r ock phosphat es will be mor e soluble on acid soils
cont ai ni ng little Ca. If t he management pr ogr a m for t hese soils i ncl udes
some appl i cat i on of l i me, t he lime shoul d be added after r ock phos phat e has
been appl i ed t o t he soil and has had sufficient t i me t o r eact , a per i od of
mor e t han six mont hs . Un d e r t hese condi t i ons r ock phos phat e may be a
very satisfactory fertilizer.
Us e of Su p e r p hos p ha t e s
Super phosphat es ar e very sol ubl e mat eri al s and hence satisfactory for any
appl i cat i on t hat r equi r es a sour ce of soluble P. Gener al l y t hey ar e excel l ent
sources when coupl ed wi t h a management pr ogr a m t hat utilizes l i mi ng t o
mai nt ai n soil pH above 6. 0, and this i ncl udes cal careous soils. Whe n super-
phosphat es ar e used on acid soil, t he adsor pt i on, and somet i mes t he preci pi -
t at i on, of P will be consi der abl e and r api d as t he soluble P react s wi t h Fe
and Al t hat i s ei t her dissolved or pr esent i n t he amor phor us f or m i n soils.
Use of Phosphorus Fertilizers 105
FIGURE 5.6 The effect of calcium ion activity ( mol / L)
on the solubility (ppmP) of six rock phosphates. (From
Wilson and Ellis, 1984, used by permi ssi on of the Williams
and Wilkins Company. )
Of t en t hese mat eri al s will be band- pl aced near t he seed at pl ant i ng t i me t o
slow down t he process of f i xat i on. I n this pl acement t echni que, t he band of
fertilizer will become very acid as t he fertilizer adsor bs wat er from t he
s ur r oundi ng soil and dissolves. Th e pH i n t he band may become much
l ower t han 3. 0. Al t hough r oot gr owt h cannot penet r at e such an aci d band,
TABLE 5. 5 Calcium Ion Activities in Soils
Ca
2 +
activity
Soil pH ppm m/ L
Warsaw loam 5.38 36 9.1 X 1 0
- 4
Munising sandy loam 4.86 35 8.8 X 1 0
- 4
Bradson 4.22 70 1.7 X 1 0
- 3
Tat um 4.94 1.2 3.0 X 1 0
- 5
Source: Wilson and Ellis, 1984.
t he P diffusing from this band will be i n hi gh concent r at i on and readi l y
available for pl ant upt ake. A r esi due of di cal ci um phosphat e, Ca HP O4 has
been shown t o r emai n i n t he band.
Whe n t hese sol ubl e mat eri al s ar e appl i ed t o a cal careous soil, par t i cu
larly i f i ncor por at ed, t hey will r eact fi rst t o f or m di cal ci um phos phat e
di hydr at e, Ca HP O4 2 H2 O. Th e n t he anhydr ous f or m, C a HP 0 4 , will ap
pear , followed in a few weeks by a less sol ubl e oct acal ci um phos phat e,
Ca 4 H( PO4 ) 3 . Thi s form i s stable for mont hs or years, but r ecent evi dence
suggests t hat bet at ri cal ci um phosphat e, Ca3 (PO4 )2 , will f or m given suffi
ci ent r eact i on t i me. Bot h forms of di cal ci um phos phat e a nd oct acal ci um
phos phat e ar e sufficiently soluble and dissociate with enough rapi di t y t o
furni sh P for pl ant upt ake. Consequent l y, this conversi on t o t he less sol ubl e
P compounds is not a loss to soil fertility. Fur t her conversi on to bet at ri cal
ci um phosphat e and t o apat i t e, i f this l at t er conversi on i ndeed occurs, leaves
P in forms t hat ar e not sufficiently soluble for opt i mum P availability in
cal careous soils.
T h e Fat e o f Ap p l i e d Fe r t i l i z e r P h o s p h o r u s
Th e desi re and goal of every f ar mer i s t o have a hi gh per cent age of appl i ed
fertilizer utilized by t he cur r ent cr op. Wi t h P, however , t hi s i s far from
reality. Th e upt ake of P may be from 5% t o 30% of t hat appl i ed dur i ng t he
cur r ent year. Th e r emai nder conver t s t o i nsol ubl e compounds , ads or bed P,
or or gani c P. The s e compounds may be available for cr ops gr own i n l at er
years.
Initial Reactions of Soluble Fertilizer Phosphorus
Most fertilizers ar e hygroscopi c and at t r act wat er once t hey ar e added t o
soils. Wat er may move t o t he fertilizer gr anul e ei t her by capillary adjust
ment or by t he movement of vapor , but t he resul t i s t he f or mat i on of a
sat ur at ed sol ut i on of fertilizer mat eri al i n wat er . T h e initial react i ons will
t hen depend on t he charact eri st i cs of t he fertilizer. T h e pH of t he soil
s ur r oundi ng t he fertilizer part i cl e reflects t he pH of a sat ur at ed sol ut i on of
t he mat eri al . Th e wi de vari ance t hat may be obt ai ned i s shown i n Ta bl e 5. 6.
Wh e n monocal ci um phosphat e, 0450, is added to a soil, it f or ms a
TABLE 5.6 Content and pH of Saturated
Solutions of Fertilizer
Saturated solution
Compound pH P, mol / L
Ca( H2 PO4 ) 2 H2O 1.0 4.5
( NH4 ) 2 HPO4
8.0 3.8
K2 HPO4
10.1 6.1
Source: Sampl e, Soper, and Racz, 1980.
Use of Phosphorus Fertilizers 107
very acid sol ut i on. If t he i ndi vi dual fertilizer part i cl es have been br oadcast
a nd i ncor por at ed i nt o t he soil, this acidity i s soon neut r al i zed by t he soil.
But i f t he fertilizer mat er i al has been pl aced i n a band, t he soil s ur r oundi ng
t he band will become very aci d a nd may have a pH as low as 2. 2. Preci pi t a
t i on occurs wi t hi n t he fertilizer band, giving a r esi due of di cal ci um phos
phat e, Ca HP O4 . Th e sat ur at ed sol ut i on of P will move slowly i nt o t he soil
wher e P may be absor bed by pl ant s or utilized by mi cr oor gani s ms i f t he
ext r eme pHs a nd hi gh ionic st r engt hs ar e not det r i ment al t o t he organi sms.
T h e P may also be adsor bed by soil part i cl es or conver t ed t o less soluble
compounds .
Th e exact nat ur e of t hese react i ons i s cont r ol l ed by t he soil pr oper t i es
a n d by t he pl acement of t he fertilizer. If t he fertilizer i s br oadcast and
mi xed with a l arge vol ume of soil, it will dissolve quickly, and t he P will
r each an equi l i br i um t hat i s gover ned by t he pr oper t i es of t he soil. For
cal careous soil this will i ncl ude adsor pt i on by Ca CO3 or Fe oxi des and
hydr oxi des and pr eci pi t at i on as di cal ci um phosphat e, oct acal ci um phos
phat e, and t ri cal ci um phosphat e. In acid soils adsor pt i on by Fe and Al
oxi des and hydr oxi des a nd clay mi neral s ar e t hought t o be t he most i mpor
t ant react i ons. Preci pi t at i on as Fe and Al phos phat e compounds will also
occur .
Bandi ng t he fertilizer mat eri al will del ay t he t i me for t he fertilizer t o
r each equi l i br i um wi t h t he soil. Thi s has been part i cul arl y advant ageous
when appl yi ng P to soil t hat has very little available P. Band pl acement
r equi r es less P to r each a satisfactory yield t han br oadcast i ng a nd mi xi ng.
Early season gr owt h effects may also be obt ai ned by band pl acement of
fertilizer, even i n soils t hat have consi der abl e available P. T h e ul t i mat e fate
of fertilizer t hat is band pl aced is to r each equi l i br i um wi t h t he soil. Whe n
pl owi ng was a s t andar d tillage pract i ce, even t he banded fertilizer was well
mi xed with t he soil once a year. But with zerotillage met hods, this may no
l onger be t he case. Resi dual effects of band pl aced fertilizer may persist for
relatively l ong per i ods of t i me unde r reducedt i l l age systems.
Residual Soil Phosphorus
A numbe r of i mpor t ant quest i ons come up concer ni ng resi dual soil P. ( 1)
What is t he fate of P t hat is conver t ed to a resi dual f or m in soils? (2) Do
c ommon soil test met hods accurat el y assess resi dual P? (3) Shoul d addi t i onal
fertilizer P be a dde d for cr op gr owt h, even if resi dual P is hi gh?
Much of t he resi dual P r emai ns in a labile f or m. It may be as adsor bed
P or pr eci pi t at ed P. A por t i on of this P is meas ur ed by most soiltesting
pr ocedur es . But some soils cont ai n mor e P i n t he resi dual f or m, whi ch can
be r emoved by r epeat ed cr oppi ng or meas ur ed by soil t est i ng. For most
agr onomi c crops, when a soil cont ai ns sufficient resi dual P so t hat t he test is
hi gh, little benefi t is gai ned from addi t i onal fertilizer P, even if band pl aced
at pl ant i ng t i me. Cer t ai n cr ops ar e an except i on t o this r ul e: pot at oes, as
i ndi cat ed earl i er, usually give a yield r esponse to a dde d P fertilizer even
when t he soil test levels ar e very hi gh.
Effect of No-Till on Soil Phosphorus
Two condi t i ons t hat occur wi t h no-till systems t hat have an i mpor t ant
bear i ng on soil P. First, P appl i cat i ons must be ma de t o t he soil surface or
appl i ed i n a band close t o t he surface. And second, or gani c mat t er i s
deposi t ed on t he surface of t he soil r at her t han bei ng i ncor por at ed i nt o t he
pl ow layer.
Surface and band appl i cat i ons of P fertilizer wi t hout cul t i vat i on l ead t o
nonuni f or m di st r i but i on of P in t he soils. Thi s is of little concer n if t he soil
initially has a hi gh level of available P. Since most management systems
have j ust recent l y conver t ed t o no-till systems, at pr esent many soils have
hi gh levels of P to a consi der abl e dept h in t he profi l e. It is likely t hat it will
t ake many years of no-till management bef or e P i s r emoved by r oot s f r om
soil layers bel ow t he surface and deposi t ed on t he soil surface as or gani c
resi dues. But ul t i mat el y t he di st r i but i on of P will be less t han desi rabl e for
cr op gr owt h, since r oot gr owt h i s likely t o be much mor e ext ensi ve i n t he
surface layer t hat has a hi gh level of P. If t he P cont ent of l ower layers of
soil becomes so low t hat r oot gr owt h i s r est r i ct ed, management pract i ces
such as an occasional pl owi ng or deep pl acement of P fertilizer woul d need
to be used in no-till systems.
Accumul at i on of or gani c P in t he few surface cent i met er s of soils unde r
no-till systems has t he effect of i ncreasi ng sol ubl e and labile P in t he layer
most exposed t o runoff, whi ch will i ncrease t he P i n t he runoff wat er . Thi s
effect may be relatively uni mpor t ant , however , i n t hat no-till and conserva-
t i on tillage systems ar e very effective i n r educi ng surface r unof f so t hat t he
t ot al P l eavi ng a field will be great l y r educed.
EN V I R O N MEN T A L C O N C ER N S A B O U T SOI LS
C O N T A I N I N G LA R GE A MO U N T S O F P H O S P H O R U S
Levels of P i n surface wat ers gr eat er t han 10 ppb (10 mi cr ogr ams P / L)
have been associated wi t h i ncreased al gae gr owt h i n st r eams and lakes.
Cont i nued hi gh levels of P i nput t o surface wat ers has l ed t o eut r ophi cat i on.
Al t hough agr i cul t ur e may be a cont r i but or t o surface wat er degr adat i on
t hr ough i nput s of P from heavily fertilized fi el ds, i t need not cont i nue t o be
i n t he f ut ur e. Responsi bl e farm manager s must be awar e of how t o cont r ol
P losses. First, runoff wat er and soil erosi on ar e t he pri nci pal means of
movi ng P from agr i cul t ur al l ands t o surface wat er s. Conser vat i on tillage
and no-till systems t hat cont r ol erosi on and wat er runoff ar e effective i n
r educi ng P loss, even t hough t hey may ul t i mat el y i ncrease P concent r at i on
i n t he small quant i t i es of wat er t hat ar e lost.
Second, soil tests shoul d be utilized even when soils cont ai n hi gh levels
of P t o defi ne when P shoul d not be added. Cont i nued appl i cat i on of
fertilizer P when soil tests ar e hi gh is not a sound pract i ce economi cal l y or
envi r onment al l y.
References 109
REF ERENCES
Bowman, R. A. and S. R. Olsen. 1979. A Reevaluation of Phosphorus-32 and Resin
Methods in a Calcareous Soil. Soil Sci. Soc. Am. Jour. 43: 121- 124.
Bray, R. H. and L. T. Kurtz. 1945. Determination of Total, Organic and Available
Forms of Phosphorus in Soils. Soil Sci. 59: 39- 45.
Cory, R. R. 1981. Adsorption versus Precipitation. In Adsorption of Inorganics at
Solid-Liquid Interfaces, pp. 161- 182. M. A. Anderson and A. J. Rubin, eds.
Ann Arbor Science, Ann Arbor, Mich.
Fixen, P. E. and A. E. Ludwick. 1982. Residual Available Phosphorus in Near-Neu-
tral and Alkaline Soils: II. Persistence and Quantitative Estimation. Soil Sci. Soc.
Am. four. 46: 335- 338.
Ellis, B. G. 1985. Phosphorus Cycle and Fate of Applied Phosphorus. In Proc. of
Symposium. Plant Nutrient Use and the Environment. Kansas City, Miss.
Ellis, B. G., C. J. Knauss and F. W. Smith. 1956. Nutrient Content of Corn as
Related to Fertilizer Application and Soil Fertility. Agronomy four.
48: 455- 459.
Gross, D. W. and B. A. Stewart. 1979. Efficiency of Phosphorus Utilization by
Alfalfa from Manure and Superphosphate. Soil Sci. Soc. Am. four. 43: 523- 528.
Griffin, R. A. and J. J. Jurinak. 1973. The Interaction of Phosphate with Calcite.
Soil Sci. Soc. Am. Proc. 37: 847- 850.
Halsted, R. L. and R. B. McKercher. 1975. Biochemistry and Cycling of Phospho-
rus. In Soil Biochemistry. E. A. Paul and A. D. McLaren, eds. Marcel Dekker,
New York.
Howeler, R. H., C. J. Asher, and D. G. Edwards. 1982. Establishment of an Effec-
tive Endomycorrhizal Association on Cassava in Flowing Solution Culture and
Its Effects on Phosphorus Nutrition. New Phytol. 90(2): 229-238.
Jensen, A. 1982. Influence of Four Vesicular-Arbuscular Mycorrhizal Fungi on
Nutrient Uptake and Growth in Barley. New Phytol. 90( l ) : 45- 50.
Juo, A. S. R. and B. G. Ellis. 1968. Particle Size Distribution of Aluminum, Iron and
Calcium Phosphates in Soil Profiles. Soil Sci. 106: 374-380.
Kapoor, K. K. and K. Haider. 1982. Mineralization and Plant Availability of Phos-
phorus from Biomass of Hyaline and Melanic Fungi. Soil Sci. Soc. Am. four.
46: 953- 957.
Kim, Y. K., E. L. Gurney, and J. D. Hatfield. 1983. Fixation Kinetics in Potassium-
Aluminum Orthophosphate Systems. Soil Sci. Soc. Am. four. 47: 448- 454.
Lindsay, W. L. 1979. Chemical Equilibria in Soils. John Wiley, New York.
Lindsay, W. L. and H. F. Stephenson. 1959. Nature of Reactions of Monocalcium
Phosphate Monohydrate in Soils: I. The Solution That Reacts with the Soil. Soil
Sci. Soc. Am. Proc. 23: 12- 18.
Mehlich, A. 1984. Mehlich 3 Soil Test Extractant: Modification of Mehlich 2
Extractant. Commun. in Soil Sci. and Plant Anal. 15: 1409-1416.
Meints, V. and D. D. Warncke. 1983. Changes in Soil Test Levels of Mineral Soils in
Michigan, 1962-1968. Bull. for Crops and Soils Ext. In-Service Training. Mich-
igan State University, East Lansing, Mich.
Murphy, J. and J. P. Riley. 1962. A Modified Single Solution Method for the
Determination of Phosphate in Natural Waters. Anal. Chim. Acta. 27: 31- 36.
Olsen, S. R., C. V. Cole, F. S. Watanabe, and L. A. Dean. 1954. Estimation of
Available Phosphorus in Soils by Extraction with Sodium Bicarbonate. Cir. 939,
USDA, Washington, D.C.
Olsen, S. R. and F. S. Watanabe. 1957. A Method To Determine a Phosphorus
Adsorption Maximum of Soils as Measured by the Langmuir Isotherm. Soil Sci.
Soc. Am. Proc. 21: 144- 149.
Olsen, S. R. and F. S. Watanabe. 1970. Diffusive Supply of Phosphorus in Relation
to Soil Textural Variations. Soil Sci. 110: 318- 327.
Pacovsky, R. S., G. J. Bethlenfalvay, and E. A. Paul. 1986. Comparisons Between
Phosphorus Fertilized and Mycorrhizal Plants. Crop Sci. 26: 151- 156.
Ryan, J., D. Curtin, and M. A. Cheema. 1985. Significance of Iron Oxides and
Calcium Carbonate Particle Size in Phosphate Sorption by Calcareous Soils. Soil
Sci. Soc. Am. Jour. 49: 74- 76.
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Calcareous Soil Chronosequence. Soil Sci. Soc. Am. Jour. 44: 168- 169.
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in Soils. In The Role of Phosphorus in Agriculture. F. E. Khasawneh, E. C. Sample,
and E. J. Kamprath, eds. Am. Soc. Agron., Madison, Wis.
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New York.
Sposito, G. 1979. Derivation of the Langmuir Equation for Ion Exchange Reactions
in Soils. Soil Sci. Soc. Am. Jour. 48: 336- 340.
Sposito, G. 1980. Derivation of the Freundlich Equation for Ion Exchange Reac-
tions in Soils. Soil Sci. Soc. Am. Jour. 44: 652- 654.
Stowasser, W. F. 1983. Phosphate Rock. Mineral Commodity Profiles. U.S. Dept. of
Int., Bureau Mines, Washington, D.C.
Tiessen, H. J., W. B Stewart, and C. V. Cole. 1984. Pathways of Phosphorus
Transformations in Soils of Differing Pedogenesis. Soil Sci. Soc. Am. Jour.
48: 853- 858.
Westin, F. C. and J. C. de Brito. 1969. Phosphorus Fractions of Some Venezuelan
Soils as Related to Their Stage of Weathering. Soil Sci. 107: 194-202.
Wilson, M. A. and B. G. Ellis. 1984. Influence of Calcium Solution Activity and
Surface Area on the Solubility of Selected Rock Phosphates. Soil Sci.
138: 354-359.
Withee, L. V. and R. Ellis. 1965. Change of Phosphate Potentials of Calcareous
Soils on Adding Phosphate. Soil Sci. Soc. Am. Proc. 29: 511- 514.
C H A P T E R 6
Soil and Fertilizer Potassium
Of t he el ement s essential for pl ant s, pot assi um and cal ci um ar e t he t wo
most a bunda nt i n t he ear t h' s crust . Pot assi um account s for 2. 6% of t he
ear t h' s crust , and cal ci um for 3. 6%. It has been est i mat ed t hat t he aver age
pl ow layer i n t he Uni t ed St at es cont ai ns 0. 83% K, whi ch equal s 16 600
p o u n d s / a c r e or 18 600 k g / h a . Most of t he soils i n t he west er n half of t he
Uni t ed States ar e mi ni mal l y or moder at el y weat her ed and cont ai n 1.7% t o
2. 5% K. By cont rast , many soils of t he sout heast er n Coastal Plains cont ai n
onl y 0. 3% K. Ther ef or e, many soils have l arge amount s of t ot al and pl ant -
available K, and responses t o K fertilizers ar e nonexi st ent or small. On t he
ot her hand, t he cont ent s of many soils ar e low i n bot h t ot al and plant-avail-
abl e K, and yield responses t o K fertilizers ar e l arge. For this r eason over
80% of t he K fertilizer appl i ed i n t he Uni t ed States i s used i n t he Lake
St at es, t he Cor n Belt, Appal achi a, and t he Sout heast , ar eas wi t h udi c soil
moi st ur e r egi mes.
Pot assi um i s not compl exed or bound up i nt o or gani c mat t er t o any
degr ee, compar ed t o N; essentially all of i t i s associated wi t h t he mi ner al
fract i on. For this r eason soil K and soil N can be consi der ed opposi t es. Soil
N exists mai nl y as or gani c N, and a mi nor a mount exists as mi ner al N. By
cont r ast , soil K is mostly mi ner al , and t he daily K needs of pl ant s ar e little
affected, if at all, by or gani c associated K, except for exchangeabl e K
adsor bed on or gani c mat t er . As a resul t mi neral i zat i on of or gani c N is t he
maj or sour ce of pl ant -avai l abl e N, and t he weat her i ng of K mi neral s i s t he
maj or process for conver t i ng unavai l abl e K i nt o forms t hat pl ant s can use.
T H E P O T A S S I U M CYCLE
Soil par ent mat eri al cont ai ns K t hat i s mai nl y i n feldspars and micas. Thes e
mi ner al s weat her , and t he K ions rel eased, K
+
, appear as exchangeabl e and
sol ut i on K. Fr om sol ut i on t he K ions may unde r go vari ous changes i n t he
111
112 Soil and Fertilizer Potassium
soil, i ncl udi ng fi xat i on and upt ake by pl ant s or mi coor gani sms, aft er whi ch
t hey may r et ur n agai n t o t he soil sol ut i on. In humi d r egi ons K i s r emoved
by l eachi ng, as shown in Fi gur e 6. 1. A pot assi um ion coul d, hypot het i cal l y,
be rel eased from pr i mar y mi neral s by weat her i ng and occur as an ex-
changeabl e cat i on. I t coul d become f i xed, rel eased from f i xat i on, and
become an exchangeabl e cat i on agai n; desor b i nt o t he sol ut i on; be ab-
sor bed by r oot s, l eached from leaves, and r e t ur ne d t o t he soil sol ut i on
agai n; and t hen be car r i ed t o t he gr oundwat er by l eachi ng.
Over t i me, t heoret i cal l y, all t he K in t he pr i mar y mi neral s is rel eased
and event ual l y r emoved from t he soil by l eachi ng. Th e most - weat her ed
soils have few weat her abl e mi neral s i n t he coarse silt and fi ne sand and ar e
in gener al infertile soils wi t h little capacity to supply K (and Ca, Mg, etc.) for
pl ant gr owt h. In t he l ar ger K cycle, t he K ions l eached from t he soil appear
i n t he oceans wher e t hey encount er and r eent er vari ous 2 : 1 clays, whi ch
may t hen be deepl y bur i ed and t he clays conver t ed i nt o micas or micalike
mi neral s. Whe n sedi ment s cont ai ni ng t hese K mi neral s ar e uplifted for
anot her cycle of soil f or mat i on, t he K begi ns anot her weat her i ng cycle
t hr ough t he soil. T h e a mount of K available i n unfert i l i zed soils t oday
depends on t he a mount and ki nds of K mi neral s t hat wer e i n t he par ent
mat eri al and t he ki nds and degr ee of changes t hat t ook pl ace dur i ng soil
genesis.
F OR MS OF SOI L P O T A S S I U M
Th e maj or forms of soil K consist of t he unavai l abl e K in pr i mar y and
secondar y mi neral s and t he available K composed of exchangeabl e K (XK)
and sol ut i on K.
Pr i ma r y Mi ne r a l s
Th e maj or K pr i mar y mi neral s i n soils ar e feldspars and micas, whi ch have
t he following chemi cal formul as.
Fel dspar
Mi crocl i ne KAlSi3 O8
Or t hocl ase KAl Si 3 O8
Mica
Muscovi t e K( Si 3 Al ) Al 2 O1 0 ( OH) 2
Bi ot i t e K( Si 3 Al ) ( Mg, Fe
2 +
) 3 O1 0 ( OH) 2
T h e K cont ent decreases from about 13% t o 14% for feldspars t o about
10% for micas.
Fel dspar part i cl es i n soils t end t o be l ar ger i n size t han mi ca part i cl es.
In some wel l -drai ned Mollisols devel oped from till i n Saskat chewan, Can-
ada, over 50% of t he mica was i n t he clay wi t h only a mi nor amount i n t he
sand, but over 50% of t he fel dspar was i n t he sand and a mi nor a mount i n
t he clay (see Fi gur e 6. 2). Finer-sized part i cl es have gr eat er specific surface
113
FIGURE 6. 2 Distribution of mica and feldspar potassium among the
sand, silt, and clay in a well-drained Mollisol (Orthi c Black) in Saskatche-
wan, Canada. (Adapted from Somasiri, Lee, and Huang, 1971. )
and weat her mor e rapi dl y t han coarser part i cl es. I n most soils t he mica-
ceous mi neral s ar e mor e i mpor t ant t han feldspars i n r epl eni shi ng t he pl ant -
available K.
Many sandy soils whose clay cont ent is low have low fertility because
most of t he sand and silt part i cl es ar e quar t z. T h e most infertile soil i n
Wi sconsi n is Boone sand, whi ch devel oped from quart zi t i c sandst one. If a
soil has devel oped from ar kose (feldspathic) sandst one, however , i t coul d be
sandy and pr ovi de much mor e available K t han a soil like Boone sand. T h e
weat her i ng of feldspar i n t he sand fract i on cont r i but es t o t he rel ease of
l arge amount s of K in some sandy Ultisols of t he Coastal Plains in Del awar e.
As a gener al r ul e, fi ne-t ext ured soils have gr eat er K-suppl yi ng power t han
coar se- t ext ur ed soils. Thi s gr eat er supply of K is r el at ed, in par t , to t he fact
t hat mi ca is nearl y a uni versal const i t uent of t he clay in soils.
Quar t z i s composed of S i - O t et r ahedr al uni t s, a nd t he chemi cal for-
mul a Si O2 coul d be wr i t t en Si 4 O8 . Compa r e this t o t he feldspar formul a,
KAl Si 3 O8 . I n a sense one of every f our of t he t et r ahedr al s has A l
3 +
substi-
t ut ed for S i
4 +
, a nd t he char ge i s bal anced out by t he inclusion of a K
+
i n t he
feldspar st r uct ur e. Fel dspars ar e qui t e resi st ant t o chemi cal br eakdown and
weat her slowly; t he mi crocl i ne weat her s mor e slowly t han t he or t hocl ase.
Dur i ng weat her i ng t her e i s a compl et e br eakdown of t he crystal st r uct ur e
and rel ease of t he component par t s. Th e K
+
i s rel eased i nt o t he soil solu-
t i on; however , some of t he Al a nd Si f or m a gel t hat coat s t he weat her i ng
surface and forms a pr ot ect i ve bar r i er whi ch inhibits f ur t her dissolution of
t he feldspar. Al t hough fel dspar i s an i mpor t ant sour ce of K
+
, its slow
di ssol ut i on r at e resul t s i n poor cor r el at i ons bet ween t he a mount of fel dspar
in a soil and t he a mount of K absor bed by crops.
Th e K i n micas i s i nt erl ayer K bet ween t he 2 : 1 layers (see Fi gur e 2. 1).
Forms of Soil Potassium 115
Dur i ng weat her i ng a H 3 O
+
i s very effective i n exchangi ng for a K
+
al ong
t he edges, whi ch i s followed wi t h an expansi on of t he i nt erl ayer space i n t he
edges. I nt er nal cryst al -bondi ng di fferences cause t r i oct ahedr al bi ot i t e t o
weat her mor e rapi dl y t han di oct ahedr al muscovi t e. Thi s weat her i ng allows
K t o leave t he st r uct ur e mor e easily i n bi ot i t e t han i n muscovi t e.
Th e four pr i mar y K mi neral s wer e f i nel y gr ound and used i n an
exper i ment t o measur e t hei r ability t o supply K for oat s. T h e r emoval or
upt ake of K by t he oats paral l el ed t he weat her i ng r at e sequence, wi t h
bi ot i t e bei ng t he most easily weat her ed and suppl yi ng t he most K; mi cr o-
cline weat her i ng was t he slowest and suppl i ed t he least K for upt ake.
Removal of K by car bonat ed wat er ext r act i on paral l el ed t he pl ant r emoval s
(see Tabl e 6. 1).
Th e rel at i ve weat her i ng rat es and rel ease of K from mi crocl i ne,
muscovi t e, and bi ot i t e have been r epor t ed t o be 1.0, 1.8, a nd 190, respec-
tively. Many exper i ment er s have f ound t hat bi ot i t e is a good sour ce of K for
gr owi ng pl ant s. Th e r e i s evi dence t hat r oot s play a r ol e i n t he r emoval of K
from bi ot i t e and t hat pl ant s differ i n t hei r capacity t o ext r act or use bi ot i t e
K. T h e r api d weat her i ng r at e of bi ot i t e account s for its low cont ent i n most
soils, wher eas t he very slow weat her i ng r at e of muscovi t e account s for its
pr esence in t he clay fract i on of most soils.
Se c ond a r y Mi ne r a l s
T h e i nt erl ayer K of micas i s lost fi rst al ong part i cl e edges dur i ng weat her -
i ng, as ot her cat i ons diffuse i nt o t he i nt erl ayer space and hydr at e. The s e
processes cause expansi on bet ween layers, and t he partially weat her ed mi n-
eral t hat has lost some K and cont ai ns mor e wat er t han unweat her ed mi ca i s
hydrous mica. Historically, hydr ous mica has been called illite, and t he t wo
names have been used i nt er changeabl y. T h e weat her ed hydr ous mi ca edges
have si t esvoi ds whi ch have lost Kt h a t st rongl y r eads or b K
+
wi t h an
accompanyi ng collapse of t he expanded layer edges. Th e low ener gy of
hydr at i on and t he ease with whi ch t he hydr at i on wat er i s lost facilitate
movement of a K
+
i nt o t he f i xat i on site. Thi s posi t i oni ng conver t s a K
+
i nt o
TABLE 6.1 Availability of Potassium in Freshly Ground Minerals
Source of
K
K removed by oats
(gains over control), grams/ pot
K removed by
five extractions,* ppm
K2 SO4 0.253
Biotite 0.203 217
Muscovite 0.177 141
Orthoclase 0.062 78
Microcline 0.011
51
*30 grams i n 200 ml of carbonated water shaken for 96 hours.
Source: Data of Pl ummer, 1918, and modi fi ed from Rich, 1968.
unavai l abl e or fixed K. Fi gures 2.1 and 2. 2 give model s of muscovi t e and
hydr ous mica, respectively.
Whe n all or nearl y all t he i nt erl ayer K bet ween t wo layers has been
r emoved, t he layers separat e and expand, t hus t r ansf or mi ng hydr ous mi ca
i nt o vermi cul i t e. Th e negat i ve char ge t hat was originally bal anced by K
appear s as CEC. T h e vari ous crystal forms of K ar e i n equi l i br i um wi t h each
adj acent me mbe r i n t he weat her i ng sequence; i n t he l abor at or y sol ut i ons
with hi gh-K concent r at i ons have been used t o r ever se t he sequence. I n f i el d
soils t he appl i cat i on of K fertilizer pr oduces local pocket s of hi gh- K
+
con-
cent r at i on and pr omot es t he r eent r y of K i nt o t he i nt erl ayer space. Hy-
dr ous mica al ong part i cl e edges i s t hen conver t ed t o mi ca. Th e weat her i ng
sequence of mica, changes i n K cont ent , and equi l i bri um rel at i onshi ps ar e
i l l ust rat ed i n Fi gur e 6. 3.
Th e mica mi ner al - weat her i ng sequence, shown i n Fi gur e 6. 3, becomes
a K cont i nuum in t er ms of t he t ransi t i onal pr oper t i es of t he K mi ner al s and
t he availability of K in soils. Whe n a mi ca part i cl e loses K al ong t he edges,
t he edge section i s conver t ed t o hydr ous mi ca. Before t he weat her i ng front
r eaches t he part i cl e i nt er i or or mi ca cor e, t he out er edges may have lost all
t hei r K and may have been conver t ed i nt o vermi cul i t e. It has been t heor -
ized t hat an i nt erl ayer wedge- shaped zone i s cr eat ed i n t he hydr ous mi ca at
its j unc t ur e wi t h t he unweat her ed mi ca cor e. I n this wedge- shaped zone t he
adsor pt i on sites closest t o t he unweat her ed mi ca cor e have t he short est
di st ance bet ween layers and t he great est affinity for K. Th e r e i s decr easi ng
affinity for K i n t he wedge zone t owar d t he part i cl e edge as t he i nt er l ayer
di st ance i ncreases (not e t he wedge- shaped zone of t he hydr ous mi ca i n
Fi gur e 6.3). Thus , a K availability cont i nuum, consi st i ng of unavai l abl e
mica K, fi xed K and XK adsor bed t o sites wi t h different ener gi es of adsor p-
t i on, is cr eat ed. T h e unavai l abl e K occurs in t he i (i nt eri or) positions and
t he exchangeabl e K at t he p (pl anar) and e (edge) posi t i ons, as shown in
Fi gur e 6. 4. T h e e posi t i on, near t he site of a vacat ed st r uct ur al K, has a
special affinity for K
+
and hol ds XK mor e st rongl y t han on t he pl anar
surfaces ( p site). Since t he vari ous forms of K t end t owar d equi l i br i um wi t h
one anot her , t hey oper at e as buffers t o moder at e t he r at e at whi ch sol ut i on
K is depl et ed when K is absor bed by r oot s.
Potassium Fixation
Pot assi um fixation is associated with mica wedge zones. In field soils t he
moi st ur e cont ent and ot her condi t i ons ar e nor mal l y such t hat expandi ng
clays, vermi cul i t e and smect i t e, do not fix a significant a mount of K. If soil
samples ar e artificially dr i ed, t he r emoval of i nt erl ayer wat er and t he subse-
quent cont r act i on of t he layers may cause some K fixation. Thi s fixing of K
has some i mpl i cat i ons for dr yi ng soil sampl es bef or e t est i ng t he m for avail-
abl e K. Dr yi ng t ends t o br i ng t he soil K rel at i onshi ps t o equi l i br i um. If
sampl es ar e col l ect ed j ust aft er harvest and t he XK has been depl et ed by
pl ant upt ake, dr yi ng will i ncrease XK. If sampl es ar e col l ect ed short l y aft er
117
FIGURE 6. 4 The exchangeabl e potassium i s adsorbed at the p or planar position and
at the edge or e position. Nonexchangeabl e potassium is fixed in the interlayer or i
position. Strongl y hydrated cations, like cal ci um, enter t he interlayer space and remai n
exchangeabl e. Hydroxy- Al islands hol d layers apart and may trap ions in the interlayer
space. (After Rich, 1968, used by permission of the Soil Sci ence Society of Ameri ca. )
a l arge appl i cat i on of K fertilizer, dr yi ng will t end to fix K. T h e 2 : 1 clays in
aci d soils may cont ai n some i nt er l ayer hydroxy-Al whi ch pr event s collapse
of layers and K fixation. Thes e clays, however , may cont ai n K t r apped
bet ween t he islands of a hydroxy-Al mat r i x (see Fi gur e 6. 4).
Th e i mpor t ance of K f i xat i on depends on t he si t uat i on. I n some agri -
cul t ural soils K fixation serves to conser ve K because it r educes K loss by
l eachi ng. On t he ot her hand, some agri cul t ural soils have such l arge K-fix-
i ng capacities t hat l arge amount s of K fertilizer have little i nfl uence on
yields. In Mi chi gan, for exampl e, cr op yields wer e little i ncreased, if at all,
by K fertilization in a field t hat occupi ed a downsl ope posi t i on in t he
l andscape. It was f ound t hat hydr oxy- Al - i nt er l ayer ed vermi cul i t e clay had
f or med on t he upper slopes i n an acid envi r onment and was moved down-
slope by erosi on and deposi t ed wher e soils wer e much mor e al kal i ne. Th e
gr eat er alkalinity r emoved much of t he i nt er l ayer hydroxy-Al a nd r est or ed
t he clay' s K-fixing capacity. T h e K fertilizer was satisfying t he soil' s K-fixing
capacity and was not available for cr op gr owt h. Bandi ng of K fertilizer i n
soils with hi gh fi xi ng capacity has been f ound t o i ncrease t he effectiveness
of K fertilizer.
Ex c ha ng e a b l e a nd Sol ut i on F or ms
Whe n a K+ leaves t he i nt er l ayer space, it will very likely be adsor bed ont o a
cat i on exchange site and become XK. T h e XK mai nt ai ns an equi l i br i um
wi t h t he K i n sol ut i on, and t oget her t he exchangeabl e and sol ut i on K make
Forms of Soil Potassium 1 1 9
up t he available K. Aft er r emoval s or addi t i ons of K, t he t i me r equi r ed for
equi l i brat i on bet ween sol ut i on K and XK i s usually less t han an hour ; days
or weeks ar e r equi r ed for equi l i brat i on bet ween exchangeabl e a nd f i xed K.
T h e sol ut i on K is equal to 1% to 3% of t he exchangeabl e K in most soils.
Depl et i on of sol ut i on K by pl ant upt ake or l eachi ng causes XK t o move
quickly i nt o sol ut i on t o reest abl i sh t he equi l i br i um. Since t he XK t ends
t owar d an equi l i br i um with t he fixed K, some fixed K will slowly become
exchangeabl e. T h e r ever se is t r ue when t he sol ut i on K is i ncr eased by K
fertilizer (see Fi gur e 6. 3).
In some ext r emel y weat her ed t ropi cal soils t her e is little if any fel dspar
or mi ca K, and most of t he K i s exchangeabl e. In t he kaolinitic a nd oxi di c
mi neral s of severely weat her ed t ropi cal LAC soils, t her e is little if any K
fi xat i on. Thi s i s t he si t uat i on for t he Mol okai soils, of s ubor der Tor r ox, i n
Hawai i ; t hese soils devel oped from basalt, whi ch cont ai ns few K mi neral s.
On t he ot her hand, some Oxisols i n Africa have devel oped from grani t i c
basement rocks ri ch i n mi ca and still cont ai n enough mica (muscovite) t o
pr ovi de sufficient K for low-intensity f ar mi ng (see Fi gur e 6. 5).
Because t he mi ner al component in Histosols is l i mi t ed, most of t he K
exists as XK, a nd t he soil has little or no capacity t o fi x K. Mi ner al mat eri al s
t end t o occur i n Histosols as cont ami nant s, a nd t he a mount of mi ner al
mat eri al affects t he K rel at i onshi ps in Histosols.
Leaching Loss
T h e loss of K by l eachi ng i s r el at ed t o t he concent r at i on of K i n t he soil
sol ut i on and t he a mount of wat er t hat l eaches t hr ough t he soil. T h e typi-
cally low concent r at i on of sol ut i on K mi ni mi zes t he losses t hat occur . As-
FIGURE 6. 5 The Oxi sol s, of suborder Ust ox, i n this African fi el d contai n
enough mica to provi de adequate potassium for subsistence farming.
1 1 8 Soil and Fertilizer Potassium
sumi ng a K concent r at i on of 4 mg / k g of wat er and t he l eachi ng of 25 cm of
wat er, t he loss i s equal t o 10 k g / h a or 9 pounds / a c r e . The s e losses ar e
typical of soils cont ai ni ng high-activity clay, HAC, and ar e small rel at i ve t o
t he upt ake of hi gh-yi el di ng crops. Leachi ng losses and t he ext ent of K
movement t end t o i ncrease as soils become mor e sandy.
Significant l eachi ng losses ar e mor e likely on LAC soils because of t hei r
low CEC and l i mi t ed K fixation. As much as 2 5 % of t he K was lost by
l eachi ng dur i ng t he fi rst year when 500 k g / h a of K was appl i ed t o Oxisols
on t he savannah i n Brazil. Nor mal l y, K appl i cat i on rat es a nd l eachi ng losses
ar e much less. However , losses of K by l eachi ng appear t o be mor e seri ous
on LAC soils t han on HAC soils, and K f r om fertilizer appl i cat i ons moves
mor e deepl y. I n ar i d ar eas wher e soils ar e only mi ni mal l y weat her ed and
l eachi ng does not occur, K fertilizers ar e usually unnecessary.
F or ms v e r s us Pl a nt Up t a k e
Th e i mpor t ance of t he vari ous forms of K as a K sour ce for pl ant s is
i l l ust rat ed by t he resul t s of a gr eenhous e exper i ment i n whi ch ni ne consecu-
tive cr ops of alfalfa wer e gr own on t hi r t een di fferent soils. Th e soils con-
t ai ned an aver age of 1.62% t ot al K, equal on a furrow slice basis to 36 210
k g / h a (32 302 pounds / a c r e ) . Th e amount s of exchangeabl e, f i xed, a nd
resi dual K (in micas and feldspars) wer e 1%, 3%, and 96% of t he t ot al ,
respectively (see Tabl e 6.2). Th e alfalfa crops r emoved 399 k g / h a ( 356
pounds / a c r e ) with 44% from a depl et i on of XK, 39% from fi xed K, and
17% from t he resi dual K. Th e upt ake of one uni t of K was cor r el at ed wi t h 2
uni t s of XK, 7 uni t s of fi xed K, and 517 uni t s of resi dual K. Dur i ng this
per i od K upt ake was significantly cor r el at ed wi t h exchangeabl e and fixed K
but not wi t h resi dual K.
P LA N T A N D SOI L P O T A S S I U M R ELA T I O N S H I P S
Of t he nut r i ent s r emoved from soils, pl ant upt ake of K i s often second t o
upt ake of N. I t i s not unc ommon for annual crops t o r emove over 224
k g / h a or 200 pounds / a c r e (see Fi gur e 6. 6).
TABLE 6.2 Amounts of Various Forms of Potassium in Thirteen Iowa Soils and
Removal by Thirteen Consecutive Crops of Alfalfa
Soil potassium
Potassium uptake
Form of
potassium kg*/ ha
pounds*/
acre percent kg/ ha
pounds/
acre percent
Exchangeable
Fixed
Residual
Total
358
1 084
34 768
36 210
320
967
31 015
32 302
1
3
96
100
176
156
67
399
157 44
139 39
60 17
356 100
*Kilograms or pounds based on 2 000 000 of soil.
Source: Data from Pratt, 1951.
Plant and Soil Potassium Relationships 121
FIGURE 6.6 The alfalfa for this record noni rri gated yield contai ned 3
percent potassi um, an uptake of potassium equal to 600 pounds per acre
or 673 kilograms per hectare. (Photograph courtesy Dr. M. B. Tesar. )
Up t a k e a nd Rol e i n Pl a nt s
Pot assi um i s absor bed from sol ut i on as an i on, K
+
, and pl ant upt ake i s
closely r el at ed to sol ut i on concent r at i on. Upt ake is active and agai nst a
concent r at i on gr adi ent unless t he sol ut i on concent r at i on K i s hi gh. Pot as-
si um i s associated with many enzymes i nvol ved i n phot osynt hesi s, or gani c
c ompound synthesis, and t ransl ocat i on of or gani c compounds . T h e rel at i ve
upt ake of K earl y in t he gr owi ng season is general l y gr eat er t han t hat for N
and P. Pot assi um i s not compl exed i nt o or gani c compounds i n pl ant s and
may be lost from pl ant s late i n t he season t hr ough l eachi ng of foliage and
l eakage from r oot s. Thus , t he a mount of K i n pl ant s may be gr eat er some
t i me dur i ng t he gr owi ng season t han at harvest (see Fi gur e 1.6).
In cereal s t he K i s concent r at ed i n t he veget at i ve par t s so t hat t he
harvest of cor n for silage r emoves l arge quant i t i es of K compar ed t o t hat
r emoved by t he harvest of cor n grai n. Pot assi um i s mobi l e i n pl ant s. Defi-
ciency sympt oms appear on t he ol dest leaves as a chl orot i c mar gi nal fi ri ng.
In advanced stages t he ent i r e leaf t ur ns yellow and i s necrot i c. Weak stalks
and l odgi ng of gr ai n crops ar e also caused by K deficiency. T h e deficiency
sympt oms for many cr ops i s a yellowing and t he event ual deat h of cells near
leaf mar gi ns.
Pot a s s i u m Up t a k e f r om Soi l s
Var i ous st udi es have shown t hat t he a mount of exchangeabl e K i n many
soils i s about equal t o t he annual upt ake of pr oduct i ve crops, a nd t hat t he
a mount i n sol ut i on at any given i nst ant i s equal t o 1% t o 3% of t he
exchangeabl e K. Assumi ng t hat t he sol ut i on K i s equal t o 2% of t he ex-
changeabl e, t he soil sol ut i on i n effect will have t o be depl et ed and r epl aced
with K about 50 t i mes dur i ng t he gr owi ng season. Assumi ng t hat cr op
needs and exchangeabl e K i n t he pl ow layer ar e bot h 200 k g / h a (or about
200 pounds / a c r e ) and t hat t he sol ut i on K i s equal t o 2% of t he exchange-
abl e, 4 kg of K will be in sol ut i on per hect ar e. Daily maxi mum upt ake r at es
of 8 t o 10 k g / h a have been r epor t ed for cor n. Thus , t he sol ut i on woul d
cont ai n only a 12- hour supply dur i ng t he per i od of maxi mum upt ake.
Obvi ousl y, mass flow will not move enough K
+
t o t he r oot s t o suppl y pl ant
needs. Of t he K t aken up by cor n, i t has been est i mat ed t hat 2% comes from
r oot i nt er cept i on, 20% from mass f l ow, and 7 8 % from diffusion. Most of
t he diffusion occurs wi t hi n 4 mm of t he r oot surface. T h e aver age K i n t he
sat ur at ed ext r act s of 142 soils of t he Nor t h Cent r al r egi on of t he Uni t ed
States was f ound t o be 4 mg / k g wi t h a r ange of 1 t o 80. For t he soil sol ut i on
t o t r anspor t enough K t o r oot s by mass fl ow, t he concent r at i on woul d need
t o be over 40 mg / k g .
Th e upt ake of K i s st rongl y cor r el at ed wi t h t he sol ut i on concent r at i on
of K ions, whi ch depends on t he equi l i br i um rel at i on bet ween t he sol ut i on
and t he exchangeabl e K, and bet ween t he exchangeabl e and t he f i xed K.
Early in t he season pl ant s depl et e t he sol ut i on K, whi ch is rapi dl y r epl aced
from t he exchangeabl e K. As sol ut i on K is depl et ed over t i me, r epl acement
of sol ut i on K slows down, for K ions exchange f r om sites havi ng gr eat er
ener gy of adsor pt i on. Less K comes from p sites and i ncreasi ngl y mor e K
comes from specific adsor pt i on sites on mi ca edges or i n expanded sections
of mica wedges. Over t i me t he sol ut i on concent r at i on of K a nd t he a mount
of exchangeabl e K decr ease. Th e l ower ed XK encour ages t he movement of
fixed K to exchange posi t i ons. The s e event s cr eat e a pat t er n in whi ch XK is
r educed earl y i n t he season and fi xed K l at er i n t he season (see Fi gur e 6. 7).
FIGURE 6. 7 Upt ake of potassium from one kilogram of l oam soil by six
corn plants i n the greenhouse and loss of potassium from exchangeabl e
and nonexchangeabl e forms in the soil. (From Black, 1968, used by
permission of John Wiley & Sons. )
Plant and Soil Potassium Relationships 123
Pot a s s i u m Buf f e r Ca pa c i t y
Removal of K from t he soil sol ut i on by pl ant upt ake dur i ng t he gr owi ng
season is usually associated with a decr ease in XK, whi ch is followed by a
decr ease i n nonexchangeabl e K, as shown i n Fi gur e 6. 7. Changes i n XK ar e
associated with changes in t he concent r at i on of K in sol ut i on, t hat is, wi t h K
availability. Th e ability of t he soil t o mai nt ai n t he sol ut i on concent r at i on of
K dur i ng t he gr owi ng season while XK i s bei ng depl et ed i s t he pot assi um
buffer capacity, KBC. T h e KBC can be ascer t ai ned from gr aphs i n whi ch
ar e pl ot t ed t he a mount of XK on t he or di nat e and t he sol ut i on K concen-
t r at i on on t he abscissa. Th e slope of t he line, or t he r at i o of t he change i n
a mount of XK t o t he change i n sol ut i on K concent r at i on, i s t he KBC. A
st eep line reflects a hi gh KBC, whi ch r ender s t he soil capabl e of mai nt ai ni ng
t he sol ut i on K while exper i enci ng a l arge decr ease in exchangeabl e K.
Wel l -buffered soils t end t o have hi gh CEC and cont ai n l arge amount s of
XK and mi ca wedge K.
Quantity and Intensity Relationships
T h e quant i t y and intensity, or Q/I, r el at i onshi p concept was i nt r oduced i n
1964 t o express t he KBC. Similar gr aphs ar e pr oduced, except t hat on t he
or di nat e is t he change in exchangeabl e K associated wi t h vari ous K activity
rat i os, AR
K
.
To obt ai n t he dat a for t he gr aph i n Fi gur e 6. 8, f i xed quant i t i es of
sol ut i on with t he same aC a
2 +
a nd a M g
2 +
ar e ma de wi t h var yi ng aK
+
. T h e
sol ut i ons ar e mi xed wi t h soil and al l owed t o st and for a per i od of t i me. In
effect, this creat es soils wi t h differing amount s of XK. Th e n t he sol ut i ons
a nd soil ar e separ at ed a nd t he sol ut i ons anal yzed for K, Ca, and Mg. Th e
gai n or loss of K in t he sol ut i on r epr esent s loss or gain f r om t he soil,
respect i vel y. Thi s gain or loss i s at t r i but ed t o a change i n t he a mount of XK
a nd i s expr essed as change i n K, i n mi l l i equi val ent s per 100 gr ams, and
pl ot t ed on t he or di nat e. T h e f i nal sol ut i on concent r at i ons of K, Ca, and Mg
ar e conver t ed i nt o activities and used t o calculate t he AR
K
of t he f i nal
sol ut i ons and ar e pl ot t ed on t he abscissa. Cal cul at i on of t he AR
K
i s as
follows:
Th e slope of t he line i n t he gr aph i s a measur e of t he KBC (see Fi gur e
6. 8). T h e st eep slope for soil A r epr esent s a soil st rongl y buffered wi t h K,
one t hat has a l arge capacity t o mai nt ai n t he AR
K
by changes i n t he a mount
of XK (and f i xed K) dur i ng t he gr owi ng season. Whe r e t he line crosses t he
abscissa at zer o change i n XK, t he soil i s at its equi l i br i um AR
K
. T h e Q/I
r el at i onshi p expresses bot h t he i nt ensi t y ( / ) or i nst ant K availability and t he
subsequent availability (Q).
Ext r emel y weat her ed soils wi t h kaolinitic and oxi di c mi ner al ogy, and
wi t h little or no fi xed K and little exchangeabl e K, ar e poor l y buffered.
FIGURE 6.8 Typi cal quant i t y- i nt ensi t y curves. The
steeper curve for soil A indicates that, compared to
soil B, it has a smaller change in sol uti on K (I) with a
change in the quantity of exchangeabl e K (Q) and,
therefore, a greater potassium buffer capacity (KBC).
Such soils ar e unabl e t o mai nt ai n a satisfactory AR
K
as K i s t aken up dur i ng
t he gr owi ng season.
Lu x u r y Cons u mp t i on
Fi xat i on and l eachi ng t end t o mai nt ai n an AR
K
low enough t o pr event
l uxur y consumpt i on of K in most soils. Lar ge appl i cat i ons of K fertilizer,
however , can br i ng about excessive or l uxur y consumpt i on of K. Th e
resul t s of an exper i ment as shown i n Tabl e 6. 3, illustrate how t he upt ake of
K rises to l uxur y levels.
A l arge quant i t y of fi el d soil was col l ect ed and br ought t o t he gr een-
house. Th e soil was di vi ded i nt o t hr ee sampl es. On e was unt r eat ed; a
second was l eached wi t h a salt sol ut i on, whi ch r emoved t he XK; and t he
t hi r d sampl e was l eached for several hour s with HC1, whi ch r emoved bot h
t he XK and t he f i xed K. The s e t r eat ment s wer e t he f i r st t hr ee listed i n
Tabl e 6. 3. Par t of t he soil from whi ch t he XK and fi xed K had been
r emoved, by t he t hi r d t r eat ment , was t hen given a l arge appl i cat i on of K
fertilizer, whi ch r est or ed t he fi xed K and t he XK. Th e a mount of K appl i ed
was equal t o 800 pounds / a c r e ; this pr ocedur e made up t he f our t h " t r eat ed
plus K fert i l i zer" t r eat ment . Cr ops wer e t hen gr own on t hese parcel s of soil.
Removal of t he XK r educed yields t o 62% of t he unt r eat ed soil yields.
Removal of t he XK and f i xed K r educed yields t o only 2 1 % of t he un-
t r eat ed soil yields. T h e addi t i on of K fertilizer t o t he soil t hat had had bot h
125
t he exchangeabl e a nd fi xed K r emoved pr oduc e d a yield t hat was 149% of
t he yield of t he unt r eat ed soil. Decreases i n t he upt ake of K wer e compar a-
bl e t o t he exchangeabl e and fi xed K r emoved. By cont rast , however , t he K
fertilizer pr oduced such hi gh levels of sol ut i on K t hat upt ake was 9 6 8 % of
t he unt r eat ed soil upt ake. Such an upt ake const i t ut es l uxur y consumpt i on
of K. Th e yield was i ncreased 149%; however , t he i ncrease in K upt ake was
968%.
F A C T OR S A F F EC T I N G U P T A K E O F P O T A S S I U M
Pot assi um upt ake at t he r oot level i s closely r el at ed t o t he concent r at i on
gr adi ent bet ween soil a nd r oot , t he r at e of K diffusion t hr ough soil t o r oot
surfaces, and t he surface ar ea of r oot s. Pl ant s gr own on di fferent ki nds of
soils with t he same exchangeabl e K may t ake up di fferent amount s of K
dur i ng t he gr owi ng season and yield differently owi ng t o differences i n t he
KBC. T h e effect of t e mpe r a t ur e on K upt ake i s very compl ex because
chemi cal t r ansf or mat i ons of K in t he soil ar e t emper at ur e- dependent , and
r oot gr owt h and ot her pl ant processes ar e affected by t emper at ur e. Several
ot her factors t hat affect K upt ake from soils will be discussed.
Soi l Moi s t u r e
Diffusion of K
+
t hr ough soil wat er t o r oot s i s t he most l i mi t i ng st ep i n K
upt ake dur i ng t he gr owi ng season. As soils dr y K diffusion decreases,
maki ng t he available K, in a sense, less available for upt ake. And as soils dr y
t her e is also less wat er in whi ch t he K can diffuse, a nd t he diffusion pat hs
ar e mor e t or t uous .
T h e effects of dr y weat her on yields and K upt ake ar e vari abl e. If dr y
weat her causes mor e deepl y penet r at i ng r oot s t o gr ow and f or age t hr ough
a gr eat er vol ume of soil, yields a nd t ot al K upt ake may i ncrease. T h e resul t s
ar e hi ghl y dependent on t he forms and amount s of subsoil K.
Ca t i on Ex c ha ng e Ca pa c i t y
As t he CEC i ncreases, a given a mount of exchangeabl e K will equi l i br at e
wi t h less K
+
i n sol ut i on, whi ch i s t he di l ut i on effect. Fi ne- t ext ur ed soils
r equi r e a hi gher level of exchangeabl e K t o pr oduce t he same AR
K
a nd
yields t hat coar se- t ext ur ed soils do. Many states account for vari at i ons i n
CEC when maki ng K fertilizer r ecommendat i ons . For exampl e, t he desi r ed
exchangeabl e K level for gener al cr oppi ng in Ohi o is cal cul at ed as follows:
desi r ed soil test level = 220 + (5 X CEC)
Soils wi t h hi gher CEC usually have fi ne t ext ur e and have slower K diffusion
r at es as compar ed t o coar se- t ext ur ed soils wi t h t he same wat er cont ent .
Factors Affecting Uptake of Potassium 127
Ex c ha ng e a b l e Ca t i on Sui t e
An i ncrease i n t he quant i t y of any cat i on i ncreases t he sol ut i on concent r a-
t i on or activity of t hat cat i on when all ot her factors r emai n const ant . In
cal careous soils t he oppor t uni t y for C a
2 +
di ssol ut i on i s gr eat , a nd a low AR
K
may depress K upt ake unde r t hese condi t i ons. Cor n gr own on t he hi ghl y
cal car eous Har ps t er soil i n I owa frequent l y had K deficiency sympt oms
when cor n gr own on near by noncal car eous Webst er soils yi el ded very well.
T h e yield differences wer e associ at ed wi t h significant differences i n pl ant
composi t i on. T h e nor mal and cal careous soils pr oduced different-sized
pl ant s with nearl y identical amount s of K + Ca + Mg in mi l l i equi val ent s
per 100 gr ams. I n t he nor mal pl ant s, however , K made up 60% of t he t ot al
cat i ons as compar ed t o only 13% for pl ant s gr own on cal careous soil.
Soi l p H Inf l ue nc e s
In aci d soils with exchangeabl e Al, i ncreasi ng soil pH decreases t he a mount
of exchangeabl e A l
3 +
and allows K
+
t o compet e mor e effectively agai nst Ca
a nd Mg for exchange sites. Wi t h mor e K ions adsor bed ont o exchange sites,
t her e i s mor e ads or bed K and less K i n sol ut i on. Th e r emoval of t he
i nt er l ayer hydroxy-Al of clays i ncreases t he pot ent i al for K fi xat i on. A pH
i ncrease i s accompani ed by an i ncrease i n pH- dependent CEC, cr eat i ng
mor e sites for cat i on adsor pt i on, i ncl udi ng adsor pt i on of K
+
. Th e addi t i on
of l i me adds C a
2 +
and Mg
2 +
; i t also decreases t he AR
K
. All four of t hese
effects r educe sol ut i on K
+
or I and t he AR
K
. By cont r ast , however , t hese
effects r educe t he loss of K from soils by l eachi ng. If l i mi ng r educes Al
toxicity, pl ant s may gr ow l arger and t ake up mor e K. Thus , t he rel at i on
bet ween soil pH a nd K availability is compl ex, a nd l i mi ng has a hi ghl y
vari abl e affect on K upt ake.
Soi l Ae r a t i on
Act i ve accumul at i on of K by r oot s depends on met abol i c ener gy. Whe n
soils become wat er - sat ur at ed a nd r espi r at i on is r educed for lack of O2 ,
nut r i ent upt ake i s r educed. Of t he nut r i ent s absor bed i n t he gr eat est
amount s , K has its per cent age of composi t i on and upt ake r educed consi der-
abl y mor e by poor aer at i on t han do some of t he ot her nut r i ent s, as shown i n
Tabl e 6. 4. Th e dat a i n Tabl e 6.4 also show how t he upt ake of one i on, i n
t hi s case K, and pl ant gr owt h may be r educed wi t h per haps nor mal upt ake
of ot her ions and an i ncrease i n t hei r per cent age of composi t i on.
Pl a nt Di f f e r e nc e s
A di fference i n t he K-expl oi t i ng ability of grasses and l egumes has r ecei ved
much at t ent i on. Legumes ar e i nferi or t o grasses i n t hei r ability t o ext r act
soil K. Whe n bot h ar e gr own t oget her i n soils wi t h mar gi nal levels of XK,
TABLE 6.4 Effects of Aerating a Saturated Soil on the Percentage of
Composition and Uptake of Nutrients by Corn
Treat ment N
P K Ca Mg
Composition, percent
Aerated 3.33 0.24 1.50 0.63 0.67
Saturated 3.86 0.55 0.65 0.96 0.96
A/ S 0.86 0.44 2.31 0.66 0.70
Uptake, grams
Aerated 0.270 0.026 0.122 0.051 0.054
Saturated 0.181 0.020 0.031 0.045 0.045
A/ S 1.490 1.300 3.935 1.130 1.200
Source: Data from Lawton, 1945.
t he l egumes may encount er K deficiency while t he grasses grow well. Usi ng
bi ot i t e as a K sour ce i n gr eenhous e exper i ment s , r esear cher s f ound t hat
wheat can use bi ot i t e K and alfalfa cannot . Si mi l ar resul t s have been ob-
t ai ned by compar i ng ryegrass and r ed cl over. Differences i n t he K upt ake
from a given soil by di fferent varieties or cul t i vars have also been f ound. It
appear s t hat genet i c i mpr ovement of pl ant s can br i ng mor e efficient use of
soil K wi t h cor r es pondi ng yield i ncreases.
Top s oi l v e r s u s Subsoi l Pot a s s i u m
T h e i mpor t ance of subsoil K depends on t he level of available subsoil K
rel at i ve t o t he topsoil, on r oot densi t y, and on t he r esi dence t i me of r oot s
for K upt ake. Root devel opment occurs fi rst i n t he topsoil, and r oot densi t y
i s typically much gr eat er i n t he topsoil t han i n t he subsoil. By t he t i me r oot s
have become a bunda nt i n t he subsoil, t he st age of pl ant devel opment may
play a r ol e in upt ake. Subsoil K tests ar e usually l ower t han topsoil tests, and
all t hese factors t end t o account for mor e effective use of topsoil K.
Consi der abl e wor k on r oot s and nut r i ent upt ake has been conduct ed at
Pur due Uni versi t y by Bar ber and his col l eagues. Th e y f ound t hat for cor n
(maize) 5 5 % of t he r oot s wer e i n t he subsoil a nd account ed for onl y 10% of
t he total K upt ake. A regi onal fi el d exper i ment i n t he Nor t h Cent r al r egi on
of t he Uni t ed St at es f ound t hat i ncl udi ng subsoil K tests wi t h topsoil tests
di d little t o i mpr ove t he cor r el at i on bet ween soil tests and K upt ake.
T h e opposi t e si t uat i on hol ds for some Ultisols of t he Coastal Plains t hat
have very sandy surface soils overl yi ng much fi ner-t ext ured subsoils; t hese
subsoils r et ai n l arge amount s of pl ant -avai l abl e K. Th e yields of cor n and
soybeans ar e significantly affected by subsoil K. In Del awar e subsurface
sampl i ng of such soils is r out i nel y r e c omme nde d in assessing K fertilizer
needs.
Potassium Fertilizers 129
BASI S OF P OTAS S I UM
F ERTI LI ZER RECOMMENDATI ONS
T h e soil sol ut i on K concent r at i on and t he I val ue have been used as a
meas ur e of K availability. T h e XK and Q ar e r el at ed t o t he ability of t he soil
t o mai nt ai n K
+
i n sol ut i on. Whe n exper i ment s ar e conduct ed t o cor r el at e K
upt ake a nd cr op yield wi t h I a nd Q, t he best cor r el at i ons ar e wi t h Q. Thi s i s
t o be expect ed when cr ops r emove l arge amount s of K rel at i ve t o t he
a mount i n sol ut i on. Many exper i ment s have shown hi gh cor r el at i ons be-
t ween XK and upt ake. To meas ur e K availability most soil-testing labs use
an ext r act i ng sol ut i on of 1 M NH4 OAc adj ust ed t o pH 7. 0. Thi s test i s a
meas ur e of XK. T h e a mount of K ext r act ed i s general l y equat ed t o pounds
of XK in a 2 000 000- pounds / a c r e furrow slice in t he Uni t ed St at es.
Exper i ment s ar e conduct ed t o det er mi ne t he K fertilizer r at e a nd t o de-
vel op curves t hat r el at e yield t o fertilizer r at e for soils wi t h varyi ng soil test
levels. The s e dat a ar e or gani zed i nt o t abl es a nd equat i ons for maki ng K
fertilizer r ecommendat i ons for a par t i cul ar yield goal .
I n hi ghl y weat her ed Oxisols a nd Ultisols t her e may be essentially no
fi xed K t o pr ovi de for t he r epl acement of XK. Compl i ment ar y ions like Ca
a nd Mg may have an i mpact t owar d l ower i ng t he AR
K
. Thus , i t i s some-
t i mes r e c omme nde d t hat t he mi ni mum a mount of XK be at least 2% t o 3%
of t he sum XCa. . Na, i n mi l l i equi val ent s per 100 gr ams.
P OTAS S I UM F ERTI LI ZERS
Wood ashes t hat cont ai ned K2 CO3 wer e an early sour ce of K for i ndust ri al
and agri cul t ural use. T h e fi rst commerci al -scal e pr oduct i on of K fertilizers
began i n Ger many i n 1861, onl y about f i f t een years aft er Li ebi g di scovered
t hat K was an essential el ement for pl ant s. Unt i l t hen salts had been mi ned
i n Ger many for NaCl , and t he accompanyi ng K salts wer e di scar ded (Salz-
bur g means salt city). Because K fertilizers wer e needed, pr oduct i on devel-
oped rapi dl y i n Ger many a nd domi nat ed wor l d t r ade unt i l aft er Wor l d
Wa r I.
Potassium Ore Deposits
Most of t he K or e i s now obt ai ned by mi ni ng evapor i t e deposi t s t hat wer e
cr eat ed by t he evapor at i on of anci ent seas unde r ar i d condi t i ons. Toda y
t hese deposi t s exist unde r over bur dens of var yi ng t hi ckness. Mor e t han half
of t he wor l d' s known reserves occur i n Canada and t he USSR. Ot he r maj or
deposi t s exist i n t he Uni t ed St at es, Eur ope, t he Mi ddl e East, Thai l and,
Zai re (t he Congo) , a nd Sout h Amer i ca.
Th e maj or mi ni ng oper at i ons i n t he Uni t ed States ar e i n s out her n New
Mexi co near Carl sbad. He r e evapor i t e deposi t s occur i n t he Per mi an basin.
Many or e layers ar e pr esent with t he most pr oduct i ve zone bei ng 1.5 t o 3
met er s thick at 250 t o 610 met er s bel ow t he surface. T h e or e i s shaft-
mi ned. Ot he r i mpor t ant oper at i ons i ncl ude sol ut i on mi ni ng of evapor i t e
deposi t s i n Ut ah and r ecover y of br i ne deposi t s i n Ut ah and California.
Canada has t he l argest K reserves in ext ensi ve deposi t s in Saskat chewan.
T h e evapor i t e or e i s 660 t o 3 050 met er s bel ow t he surface. In places t he
or e i s t oo deep for shaft mi ni ng, and sol ut i on mi ni ng i s t hen used. The s e
deposi t s ext end sout hwar d i n Nor t h Dakot a, wher e t hey ar e deeper and not
mi ned. About 9 5 % of all t he K mi ned i s used for fertilizer manuf act ur e.
Or e Comp os i t i on a nd Fe r t i l i z e r Ma nu f a c t u r e
Many di fferent salts ar e f ound i n evapor i t e deposi t s. At Carl sbad t he or e i s
composed largely of sylvinite, a physical mi xt ur e of KCl and NaCl crystals.
Pr esent to a lesser degr ee is l angbei ni t e composed of sulfates of K a nd Mg.
Nearl y all t he K used for fertilizers comes from t he processi ng of sylvinite
and basically r equi r es a separat i on of KCl and NaCl . Over 9 5 % of K
fertilizer is KCl and has a K cont ent of at least 49. 8%. Th r e e met hods for
t he pr oduct i on of KC1 usi ng sylvinite or e ar e flotation, heavy-medi a separa-
t i on, and fractional crystallization.
Fractional Crystallization Method
Fract i onal crystallization i s a hi st ori c met hod devel oped i n Ger many. T h e
separ at i on of KC1 from NaCl i s based on t he di fferent solubilities and
t emper at ur e charact eri st i cs of t he t wo salts. T h e solubility of NaCl r emai ns
qui t e const ant wi t h t emper at ur e, wher eas t he solubility of KC1 i s great l y
i ncreased by an i ncrease i n t emper at ur e. Sat ur at ed sol ut i ons of bot h salts at
ambi ent t emper at ur e ar e heat ed t o boi l i ng. Th e n enough cr ushed or e i s
added t o sat ur at e t he sol ut i on with respect t o KC1. T h e di ssol ut i on of KC1
depl et es t he or e of KC1, but t he NaCl cont ent of t he or e i s little affected.
Th e hot br i ne i s cool ed t o ambi ent t emper at ur e t o crystallize out t he KC1
t hat dissolved from t he or e. Th e recryst al l i zed KCl i s separ at ed from t he
br i ne, dr i ed, and sent t o st or age.
Froth Flotation Method
Th e frot h flotation met hod i s t he most popul ar and economi cal . Ot he r
advant ages i ncl ude ease of cont r ol and flexibility. Fi gur e 6. 9 is a di agr am of
t he flotation process.
Th e or e i s cr ushed f i ne enough t hat relatively pur e grai ns of NaCl and
KC1 ar e pr oduced. The s e ar e a dde d t o a sat ur at ed br i ne of KC1 and NaCl
whi ch pr oduces a pul p cont ai ni ng 50% t o 7 5 % solids. Desl i mi ng separat es
out forei gn subst ances such as clays and ot her i nsol ubl e mat eri al s. T h e or e
i s t hen t r eat ed wi t h hydr ogenat ed tallow ami ne, a hydr ochl or i de soap
whi ch preferent i al l y adher es t o t he KC1 grai ns. Ai r i s bubbl ed t hr ough t he
pul p i n shallow, agi t at ed t anks or flotation cells. T h e KC1 part i cl es float t o
t he t op and ar e cont i nuousl y ski mmed off. T h e NaCl and ot her salts from
Potassium Fertilizers 131
FI GURE 6.9 The fl otati on process for recoveri ng muri ate of potash. (Courtesy TVA. )
t he or e r emai n on t he bot t om of t he cells a nd ar e cont i nuousl y r emoved.
T h e KC1 part i cl es ar e f i l t er ed f r om t he br i ne, dr i ed, and sent t o st or age.
Heavy-Media Separation
T h e heavy-medi a separ at i on me t hod uses l arge or coarse crystal grai ns,
whi ch ar e f ound i n t he Saskat chewan or e deposi t s. Less gr i ndi ng i s re-
qui r ed, and t he KCl i s separ at ed from NaCl based on di fference i n specific
gravity. Th e or e i s coarse-crushed, and part i cl es i n t he size r ange 1.6 t o 6. 5
mm ar e r emoved and used while t he smal l er part i cl es ar e processed by t he
frot h flotation met hod.
T h e heavy-medi a process uses a sat ur at ed br i ne t o whi ch magnet i t e,
F e 3 O4 , wi t h a specific gravi t y of 5. 17, i s added. Enough magnet i t e i s added
t o pr oduce a specific gravi t y of t he sat ur at ed br i ne bet ween 1.98 and 2. 13,
t he specific gravities of KC1 and NaCl , respect i vel y. Sized part i cl es in t he
r ange of 1.6 t o 6.5 mm i n di amet er ar e mi xed wi t h t he specific-gravity-ad-
j us t ed br i ne. Cent ri fugal separ at i on met hods ar e used t o r emove t he KC1,
whi ch i s debr i ned, dr i ed, cr ushed, and sent t o st or age.
Sizing and Granulation
El abor at e scr eeni ng and gr anul at i on facilities ar e used t o pr oduce part i cl es
in sizes appr opr i at e for vari ous uses. Bulk bl ender s r equi r e a part i cl e size
t hat mat ches t he sizes of ot her mat eri al s used i n t he bl end; t he part i cl es
shoul d have di amet er s i n t he r ange 0. 84 t o 3. 36 mm. Suspensi on fertilizer
manuf act ur er s need part i cl es of KC1 wi t h di amet er s i n t he r ange 0. 11 t o
0. 42 mm. Dr um gr anul at i on t o pr oduce compl et e or mi xed fertilizers uses
part i cl es i n t he 0. 2- t o 1.2-mm size r ange. Some part i cl e size needs ar e met
by passing KC1 from t he pr i mar y refi nery oper at i on t hr ough hi gh- pr essur e
compact or rol l ers. T h e dense KC1 flakes pr oduced ar e cr ushed and
scr eened t o pr ovi de t he desi r ed part i cl e size (granul at i on). Under si zed
part i cl es ar e recycl ed.
Other Processes and Materials
Most commer i cal K fertilizer pl ant s pr oduce K2 S O4 by r eact i ng KCl wi t h
H2 S O4 . Langbei ni t e, K2 S O4 2MgSO4 , i s used as a sour ce of K, Mg, and S.
React i ng l angbei ni t e wi t h KCl pr oduces K2 S O4 and MgCl 2 . React i ng KCl
with H N O 3 pr oduces KNO3 . Small amount s of K ar e pr oduced from nat u-
ral br i nes at Searl es Lake i n California, Gr eat Salt Lake i n Ut ah, and t he
Dead Sea i n Israel . At Gr eat Salt Lake and t he Dead Sea br i ne i s t aken from
t he ar ea wher e wat er has been r et ai ned t he l ongest and br i ne concent r at i on
i s t he great est . T h e br i ne i s pumpe d i nt o solar evapor at i on ponds wher e
wat er evapor at es and salt crystallizes.
REFERENCES
Barber, S. A., R. D. Munson, and W. B. Dancy. 1985. Production, Marketing and
Use of Potassium Fertilizers. In Fertilizer Technology and Use. Soil Sci. Soc. Am.,
Madison, Wis.
Beckett, P. H. T. 1964. Studies on Soil Potassium: I. Confirmation of the Ratio
Law: Measurement of Potassium Potential. Jour. Soil Sci. 15:1.
Bertsch, P. M. and G. W. Thomas. 1985. Potassium Status of Temperat e Region
References 133
Soils. In Potassium in Agriculture. R. D. Munson, ed. Am. Soc. Agron., Madison,
Wis.
Black, C. A. 1968. Soil-Plant Relationships. 2nd ed. John Wiley, New York.
Grimes, D. W. 1966. An Evaluation of the Availability of Potassium in Crop Residues.
Ph.D. Thesis, Iowa State University, Ames.
Lawton, K. 1945. The Influence of Soil Aeration on the Growth and Absorption of
Nutrients by Corn Plants. Soil Sci. Soc. Am. Proc. 10: 263- 268.
Martin, J. C, R. Overstreet, and D. R. Hoagland. 1946. Potassium Fixation in Soils
in Replaceable and Nonreplaceable Forms in Relation to Chemical Reactions.
Soil Sci. Soc. Am. Proc. 10: 94- 101.
McLean, E. O. 1978. Influence of Clay Content and Clay Composition on Potas-
sium Availability. In Potassium in Soils and Crops, Chapter 1. Potash Research
Institute of India, New Delhi.
Mengel, K. and E. A. Kirkby. 1980. Potassium in Crop Production. Advances in
Agronony. 33: 59- 110. Am. Soc. Agron., Madison, Wis.
Mortland, M. M. and K. Lawton. 1961. Relationships Between Particle Size and
Potassium Release from Biotite and Its Analogues. Soil Sci. Soc. Am. Proc.
25: 473- 476.
Munson, R. D., ed. 1985. Potassium in Agriculture. Am. Soc. Agron., Madison, Wis.
Ohio State University Cooperative Extension Service. 1986. Ohio Agronomy Guide.
Bull. 472. Agronomy Dept., Columbus.
Pierre, W. H. and C. A. Bower. 1943. Potassium Absorption by Plants as Affected
by Cationic Relationships. Soil Sci. 55: 23- 34.
Plummer, J. K. 1918. Availability of Potassium in Some Common Soil Forming
Minerals, four. Agr. Res. 14: 297- 315.
Pratt, P. F. 1951. Potassium Removal from Iowa Soils by Greenhouse and Labora-
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Madison, Wis.
Ritchey, K. D., ed. 1979. Potassium Fertility in Oxisols and Ultisols of the Humid
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Mechanisms of Potassium Release form Sandy Middle Coastal Plain Soils. Soil
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Somasiri, S., S. Y. Lee, and P. M. Huang. 1971. Influence of Certain Pedogenic
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Sparks, D. L. 1980. Chemistry of Soil Potassium in Atlantic Coastal Plain Soils: A
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Tisdale, S. L., W. L. Nelson, and J. D. Beaton. 1985. Soil Fertility and Fertilizers. 4th
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Truog, E. and O. J. Attoe. 1945. Exchangeable and Acid-Soluble Potassium as
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Am. Proc. 68: 76- 79.
C H A P T E R 7
Sulfur and Micronutrients in
Soils and Fertilizers
Sulfur and t he mi cr onut r i ent s can be di fferent i at ed from N, P, and K i n
t hat t hey ar e much less frequent l y t he l i mi t i ng factor i n soil fertility. Mor e-
over, t he amount s of S and mi cr onut r i ent s a dde d t o soils i n fertilizers ar e
relatively small. Thi s chapt er consi ders S and t he mi cr onut r i ent s as well as
some el ement s t hat may pr oduce toxicity i n pl ant s and ani mal s.
SULFUR
Even t hough pl ant s use a consi derabl e a mount of S, onl y small quant i t i es
must be added t o soils t o i mpr ove t hei r fertility at t he pr esent t i me. Thi s i s a
par adox, since pl ant s r equi r e as much S as P, but P has been consi der ed one
of t he maj or fertilizer el ement s for years. We must consi der t wo fact ors t o
under s t and why onl y small amount s of S ar e needed in fertilizers. First, S
has been added t o soils i ndi rect l y for mor e t han 200 years. Gypsum,
Ca S O4 2 H2 O, was appl i ed t o soils as earl y as 1768. Super phos phat e,
devel oped as a P sour ce a nd appl i ed to soils aft er 1850, cont ai ned 12
per cent S. One of t he fi rst commer ci al N fertilizers, a mmoni um sulfate, also
cont ai ned S. Thus , S was commonl y added to t he soil al ong with N and P. A
second maj or fact or is t hat S is a dde d to soils t hr ough pr eci pi t at i on; r ai n
furni shes all or par t of t he S r equi r ed for gr owi ng crops. I ndust r i al devel op-
ment has put mor e S i nt o t he at mos pher e, and hence gr eat er quant i t i es of S
ar e added t hr ough rainfall.
Mode r n t echnol ogy has devel oped hi gher-anal ysi s N a nd P fertilizers
t hat do not cont ai n S. Cur r ent clean-air st andar ds ar e r educi ng i ndust ri al
emissions of S. Thes e t echni cal advancement s woul d suggest t hat S levels in
soils may be r educed i n t he f ut ur e.
134
Sulfur 135
Sulfur Content of Crops and Atmospheric Deposition
T h e S cont ent of cr ops varies from 45 k g / h a (40 pounds / a c r e ) for alfalfa
t o 6 k g / h a (5. 4 pounds / a c r e ) for ri ce (see Tabl e 7.1). Some general i zat i ons
i n Ta bl e 7.1 ar e wor t hy of not e. First, grai ns r emove relatively little S
compar ed t o a forage cr op. Alfalfa, for exampl e, r emoves fi ve t i mes as
muc h S as wheat a nd 7. 5 t i mes as much as ri ce. Second, t he st over or st raw
por t i on of a cr op, whi ch is oft en r e t ur ne d to t he soil, cont ai ns a significant
a mount of S. Finally, t he par t i cul ar cr op r ot at i on will have a maj or effect on
t he soil fertility level of S. At mospher i c deposi t i on of S is qui t e vari abl e but
usually i n t he r ange of 3 t o 12 k g / h a (2. 7 t o 10. 7 pounds / a c r e ) i n t he
Uni t ed St at es. Thus , a cr op r ot at i on t hat i ncl udes a hi gh per cent age of
alfalfa and forages will r emove much mor e S from t he soil each year t han is
deposi t ed from t he at mos pher e. On t he ot her hand, a r ot at i on wi t h a hi gh
per cent age i n small grai ns may mor e nearl y bal ance r emoval wi t h at mo-
spheri c deposi t i on. Near some i ndust ri al sites enough S has been deposi t ed
to kill all veget at i on.
Sulfur Cycles
A simplified S cycle is shown in Fi gur e 7. I .
1
T h e forms of S added to t he
at mos pher e i ncl ude SO2 , S O 4
2
, H2 S, S, di met hyl sulfide (DMS), and ot her
or gani c sulfides. Th e sources of t he S rel eased t o t he at mos pher e i ncl ude
nat ur al and manuf act ur ed mat eri al s. Vol cani c activity rel eases significant
amount s of S ( 65% of total) as SO2 , H2 S, and S O4
2
. Soils cont r i but e about
one- t hi r d of t he S. Recent l y, i t was r e por t e d t hat t he wet l ands rel ease l arge
quant i t i es of DMS t o t he at mos pher e. Oceans ar e also a source of consi der-
abl e amount s of S ( 24% of total) rel eased t o t he at mos pher e, for t he most
par t as DMS.
Emissions br ought about t hr ough t he activities of huma n bei ngs ar e
1
Those who woul d like a more detai l ed discussion than is gi ven here are referred to Sulfur in
Agriculture, edi ted by M. A. Tabatabai ( 1986) .
TABLE 7.1 Sulfur Content of Agronomic Crops
Crop Yield
S content,
kg/ ha
Alfalfa, hay 8 tons 45
Corn, grain 8 000 pounds 17
stover 20
Rice, grain 7 000 pounds 6
straw 8
Soybean, grain 60 bushels 14
Wheat, grain 60 bushels 9
Source: Adapt ed from Duke and Rei senauer, 1986.
136 Sulfur and Micronutrients in Soils and Fertilizers
FIGURE 7.1 A general i zed di agram of the sulfur cycle.
Sulfur 137
soils. Hydr ous oxi des of Al and Fe, as well as exposed Al from edges of clay
mi neral s, ar e t he pri nci pal sites of adsor pt i on of sulfate. Th e adsor pt i on i s
st rongl y pH- dependent , wi t h t he gr eat est adsor pt i on bei ng f ound i n t he
ver y acid soils. Adsor pt i on for a gi ven soil decreases rapi dl y as pH is
i ncr eased from 4 t o 7. Quant i t i es of ads or bed S O4
2
ar e usually gr eat er i n
t he subsoil t han i n t he surface soil because of t he gr eat er cont ent of clay
mi ner al s and Fe and Al hydr ous oxi des i n t he subsoil. T h e possibility of
adsor bi ng S O4
2
ont o Fe and Al bound t o or gani c mat t er cert ai nl y exists.
Mor e t han 90% of t he t ot al S in t he A hor i zons of soils exits in t he
or gani c f or m. T h e N: S r at i o i n surface soils i s relatively const ant , wi t h a
r at i o of about 1 0 : 1 . 3 . Th e nat ur e of t hi s or gani c S i s qui t e compl ex. To
char act er i ze it, r esear cher s have f r act i onat ed or gani c S i nt o Hi - r educi bl e S,
whi ch is S not di rect l y bonded to C. It is usually bel i eved to be est er sulfates
(-C-O-S) or r el at ed compounds . Most soils will have bet ween 30% and 70%
of t he or gani c S as t he HI - r educi bl e S fract i on, but soils have been r epor t ed
t hat fall consi derabl y out of this r ange. T h e mor e stable or gani c S fract i on
is t he car bon- bonded S fract i on. Usual l y 10% to 20% of t he or gani c S in A
hor i zons is in this fract i on. Th e r emai ni ng fract i on is nonr educi bl e S some-
t i mes r ef er r ed t o as i ner t or resi dual or gani c S.
Whe n soils become poorl y aer at ed (anaerobi c), S O4
2
can be r educed
t o H2 S and ot her r educed S compounds . Thi s r educt i on woul d nor mal l y be
expect ed t o occur onl y aft er ot her el ect r on accept or s such as Mn
4 +
, N O 3
,
and F e
3 +
have been used. T h e H2 S may escape t o t he at mos pher e or f or m
very i nsol ubl e preci pi t at es with Fe, Zn, Cu, and ot her el ement s. I n addi t i on,
DMS i s one of t he maj or r educed S forms pr oduced i n anaer obi c soils, and
its rel ease t o t he at mos pher e has al r eady been not ed.
Pl a nt Re s p ons e s t o Sul f ur
T h e probabi l i t y of obt ai ni ng a r esponse to S fertilization general l y i ncreases
f r om t he east er n t o west er n Uni t ed St at es. Few cases of a r esponse t o S have
been r epor t ed i n t he nor t heas t er n or mi dwest er n states wher e at mospher i c
deposi t i on i s significant. Sulfur responses, however , ar e c ommon i n t he
west er n Uni t ed St at es wher e many soils have devel oped from volcanic
par ent mat eri al s and t her e i s little at mospher i c deposi t i on. I r r i gat i on wat er
may often furni sh S, so deficiencies ar e less oft en f ound on i r r i gat ed l ands.
Sandy- t ext ur ed soils ar e mor e likely t o be deficient t han fi ne-t ext ured soils.
Cr op responses vary wi t h species, but l egumes t end t o be mor e responsi ve
t han cereal s.
Di a g nos i ng Sul f ur De f i c i e nc i e s
As wi t h ot her nut r i ent s, S deficiencies have been det ect ed t hr ough soil
t est i ng and pl ant analysis. T h e l i t er at ur e woul d i ndi cat e t hat pl ant t est i ng i s
t he mor e rel i abl e gui de, al t hough soil t est i ng does identify pot ent i al l y
S-deficient soils.
largely associated wi t h power pl ant oper at i on and aut omobi l es, al t hough
ot her i ndust ri al i nput s cont r i but e some S. Most of t he i nput s ar e as SO4
2
,
H2 S, and S O 4
2
.
Once i n t he at mos pher e, all forms can be expect ed t o be oxi di zed t o
S O4
2
by r eact i on wi t h O H
-
, O2 , O3 , and ot her oxi dant s. But t he l engt h of
t i me necessary for this oxi dat i on can be qui t e vari abl e. Th e maj or S forms
ar e oxi di zed i n less t han one week, but COS (carbonyl sulfide) i s stable i n
t he at mos pher e for many years.
Sulfur from t he at mos pher e ent er s t he soil por t i on of t he S cycle ei t her
t hr ough dr y deposi t i on or t hr ough wet deposi t i on. Sulfate i s a sour ce of
acidity dur i ng wet deposi t i on since i t commonl y associates wi t h H
+
dur i ng
this deposi t i on.
Sol ubl e sulfate, S O 4
2
, i s t he pri nci pal i nor gani c i on i n wel l -aerat ed soil
sol ut i ons. If t he soil sol ut i on cont ai ns sulfate S equal to 3 to 5 mg / L , it is
consi der ed adequat e for pl ant gr owt h. Pl ant s will utilize sulfate, whi ch
r eaches t he r oot s by mass fl ow, diffusion, or bot h. General l y, mass fl ow will
be t he maj or mechani sm i f t her e i s mor e t han 5 mg / L of S i n t he sol ut i on.
Sulfate i n sol ut i on i s also i n r api d equi l i br i um wi t h ads or bed S O4
2
i n
138 Sulfur and Micronutrients in Soils and Fertilizers Essential Micronutrients 139
came c ommon i n t he earl y 1960s, i t l ent itself well t o det er mi nat i ons of t he
t r ace met al s Zn, Cu, Mn, and Fe as well as ot her t r ace met al s, such as
cadmi um and nickel whi ch ar e pot ent i al l y t oxi c. Induct i vel y coupl ed pl asma
emission spect ogr aphs gave us t he ability t o anal yze for many el ement s at
t he same t i me, t hus great l y r educi ng t he cost of analysis.
Cl assi f i c at i on of Mi c r onut r i e nt s a nd Tr a c e El e me nt s
T h e mi cr onut r i ent s t hat ar e essential for pl ant gr owt h ar e zinc, copper ,
i r on, manganese, bor on, mol ybdenum, a nd chl or i ne. Ot her s such as vana-
di um, sodi um, nickel, cobal t , a nd silicon may have some funct i on i n pl ant
gr owt h. It i s obviously very difficult t o puri fy all gr owt h medi a t o t he poi nt
of pr ovi ng essentiality for a t r ace el ement . Consequent l y, ot her s may be
a dde d t o this list at a l at er dat e. T h e t er m trace element may be mor e
appl i cabl e i n t he discussion of cer t ai n met al s t hat ar e essential for ani mal
gr owt h or i n fact t oxi c t o ei t her pl ant s or ani mal s.
Cer t ai n t r ace el ement s ar e essential for ani mal gr owt h and ar e gener -
ally furni shed t he ani mal s (i ncl udi ng huma n beings) by t he pl ant mat eri al
cons umed. I ncl uded i n this list woul d be cobal t , chr omi um, sel eni um, io-
di ne, and per haps tin and nickel. Ot he r el ement s ar e known t o be t oxi c t o
pl ant s, ani mal s, or bot h. The s e i ncl ude mer cur y, lead, a nd cadmi um. For
many ot her s, t he levels will det er mi ne t he t oxi c or beneficial na t ur e of t he
el ement . For exampl e, Cr, whi ch i s r equi r ed i n very low levels for ani mal
gr owt h, may enhance pl ant gr owt h unde r some condi t i ons. But Cr can be
qui t e t oxi c t o bot h pl ant s a nd ani mal s i f pr esent i n very hi gh levels.
A compl et e discussion of all t r ace el ement s is beyond t he scope of this
book.
2
We will focus her e on t he identification of soils a nd cr oppi ng systems
t hat ar e likely t o be infertile because of mi cr onut r i ent deficiencies. We will
also discuss how t o identify and cor r ect t he deficiencies. Th e mi cr onu-
t r i ent s cover ed will be Zn, Cu, Fe, Mn, B, a nd Mo.
ESSEN T I A L MI C R O N U T R I EN T S
Of t he six essential mi cr onut r i ent s t hat will be consi der ed, f o u r Cu , Zn,
Mn, a nd Fe exist as cat i ons i n soils, and t wo B and Moe xi s t as ani ons
or as unchar ged mol ecul ar species. T h e discussion will reflect t hese differ-
ences. A gener al di agr am refl ect i ng t he di fferent pat hways t hat mi cr onu-
t r i ent s may t ake in soils is gi ven in Fi gur e 7. 2.
T h e i mpor t ance of a par t i cul ar pat hway will depend on t he mi cr onu-
t r i ent and t he par t i cul ar soil. Each may be added t o t he soil' s pool of sol ubl e
mi cr onut r i ent s by weat her i ng of mi neral s, by mi neral i zat i on of or gani c
mat t er , or by addi t i on as a sol ubl e salt. Onc e in t he soil as a sol ubl e nut r i ent ,
2
For those interested, Applied Soil Trace Elements, edi ted by B. E. Davies, 1980, and Micronu-
trients in Agriculture, edi ted by J. J. Mortvedt, P. M. Gi ordano, and W. L. Lindsay, 1972, are
recommended.
A numbe r of ext r act i ng sol ut i ons have been used to ext r act soils, all of
which ai m t o r emove soluble a nd adsor bed SO4
2
. A part i al , but cert ai nl y
not compl et e, list woul d i ncl ude CaCL, (0. 01 t o 0. 1 M), Ca ( H2 PO4 ) 2 , 0. 25 M
HOAc pl us 0. 15 M NH4 F , and 2 N acet i c aci d cont ai ni ng 500 ppm of P.
Al t hough vari abl e with l ocat i on and cr op, t he critical level of S is expect ed
to be from 3 to 8 mg / k g . Even when a soil test shows t he a mount of S to be
below t he critical level, crops may not r es pond t o appl i cat i ons of S fertilizer
because (1) t hey obt ai n S from gr eat er dept hs t han wer e sampl ed, (2)
or gani c S is mi ner al i zed dur i ng t he gr owi ng season, (3) S addi t i ons from t he
at mos pher e or wat er ar e not account ed for by t he soil test, and (4) factors
ot her t han S limit yields. In summar y, t he soil test for sulfate is useful as a
gui de but will often fail to i ndi cat e whi ch soils will r espond to appl i cat i ons
of S.
Critical values for t he t ot al S cont ent of pl ant tissue have been devel -
oped. Dat a compi l ed for local areas shoul d be consul t ed for exact critical
values, but a few gui del i nes will be given her e. A t ot al S cont ent of pl ant
tissue t hat exceeds 0. 26% may be consi der ed opt i mum for ryegrass, alfalfa,
a nd cl overs. Val ues t hat exceed 0. 17% may be consi der ed opt i mum for
small gr ai ns, and t he cont ent of an ear leaf of cor n shoul d be mor e t han
0. 12% S t o be opt i mum.
Cor r e c t i ng Sul f ur De f i c i e nc i e s
A numbe r of mat eri al s may be used t o cor r ect S deficiency, i ncl udi ng
a mmoni um sulfate (21-0-0), super phosphat e (0-20-0), pot assi um sulfate,
magnesi um sulfate, cal ci um sulfate (gypsum), and el ement al S. T h e r ecom-
me nde d a mount of S will usually be bet ween 20 and 40 pounds / a c r e .
MI C R O N U T R I EN T S
A numbe r of el ement s t hat ar e r equi r ed by pl ant s i n very small quant i t i es
ar e known as mi cr onut r i ent s or trace el ement s. Thi s t er m usually appl i es t o
el ement s t hat ar e cont ai ned i n pl ant tissues i n amount s less t han 100
mg / k g . Al t hough t r ace el ement s have been known t o affect pl ant gr owt h
for many years, t hey have been st udi ed intensively since 1950. Two fact ors
have account ed for t hi s. First, when t he ot her gr owt h fact ors kept yields at
relatively low levels, sel dom di d mi cr onut r i ent s limit gr owt h and yield. But
with t he advent of mode r n fertilizer t echnol ogy, i rri gat i on, and new vari e-
ties came very hi gh yield pot ent i al s. Mi cr onut r i ent supplies i n soils t hat
wer e adequat e for 40, 50, or even 100 bushel s of cor n per acr e wer e not
adequat e for yields of 200 bushel s or mor e. Thus , t he ne e d t o st udy soil
fertility from t he mi cr onut r i ent st andpoi nt became mor e pressi ng.
Ou r ability t o st udy mi cr onut r i ent s has always been closely t i ed t o our
analytical capabilities. Al t hough col or i met r i c met hods have exi st ed for
many of t he mi cr onut r i ent s, t hey wer e l abor i ous a nd oft en subj ect t o a
vari et y of i nt er f er ences. Whe n at omi c absor pt i on s pect r ophot omet r y be-
t he mi cr onut r i ent may unde r go a numbe r of react i ons. Many of t he mi -
cr onut r i ent s will readi l y pr eci pi t at e in soils. A given mi cr onut r i ent may be
absor bed by a pl ant or mi cr oor gani sm. Cr op harvest obviously r emoves
mi cr onut r i ent s from t he system. Mi cr onut r i ent s ar e also i ncor por at ed i nt o
humus , whi ch i s f or med as pl ant resi dues ar e di gest ed by mi cr oor gani sms.
Thi s process i mmobi l i zes mi cr onut r i ent s j ust as i t does ot her nut r i ent s.
Adsor pt i on of mi cr onut r i ent s, ei t her by soil or gani c mat t er or by clay-
size i nor gani c soil component s , i s an i mpor t ant mechani sm of r emovi ng
mi cr onut r i ent s f r om t he soil sol ut i on. Finally, mi cr onut r i ent s may l each
from soils. But general l y, l eachi ng is a mi nor component of t he mechani sms
by whi ch mi cr onut r i ent s ar e r emoved from t he soil sol ut i on.
Cop p e r a nd Zi nc
Bot h Cu and Zn occur i n t he ear t h' s crust pri mari l y as sulfide mi neral s.
I gneous rocks cont ai n l ar ger amount s of Cu and Zn t han do sedi ment ar y
rocks, and bot h el ement s concent r at e mor e i n basalt t han i n gr ani t e. T h e
ear t h' s crust cont ai ns on t he aver age 55 ppm Cu and 70 ppm Zn. Soils
commonl y vary i n t ot al el ement al cont ent f r om 2 t o 100 ppm Cu and from
10 t o 300 ppm Zn.
Copper
Except for copper ' s occur r ence i n cer t ai n pr i mar y mi neral s, i t i s bound
st rongl y by adsor pt i on, pri nci pal l y by or gani c mat t er , as shown by r eact i on
8 i n Fi gur e 7. 2, r at her t han by preci pi t at i on. Thus , profile di st ri but i ons of
Essential Micronutrients 141
Cu t e nd t o follow t he or gani c mat t er di st r i but i on, wi t h hi gher concent r a-
t i ons i n t he surface hor i zons. The s e di st ri but i ons reflect i ncreases i n Cu i n
hor i zons t hat have accumul at ed or gani c mat t er (as i n spodi c hori zons). It
has been shown t hat carboxyl and phenol gr oups ar e i mpor t ant as t he
funct i onal gr oups bi ndi ng Cu t o soil or gani c mat t er . Copper i s mor e
st rongl y bonded by or gani c mat t er t han ot her met al s, wi t h t he except i on of
Fe a nd Al.
T h e r ol e of or gani c mat t er i n Cu chemi st ry i s also i ndi cat ed by analysis
of t he soil sol ut i on. Mor e t han 99% of t he Cu i n t he soil sol ut i on i s
compl exed by or gani c mat t er . Thi s compl exi ng i s of gr eat i mpor t ance i n
mai nt ai ni ng adequat e Cu i n sol ut i on for pl ant use. Of t he i nor gani c forms
of Cu, C u
2 +
i s t he maj or i on species for pHs less t han 6. 9, and t he i on pai r
Cu( OH) 2 i s t he maj or species for pHs above 6. 8. Al t hough C u O H
+
does
f or m, i t i s never significant rel at i ve t o t he ot her t wo species.
Deficiencies of Cu ar e not commonl y f ound i n mi ner al soils. Or gani c
soils (Histosols) cont ai ni ng little ash ar e mor e likely t o be deficient. Whe n
or gani c soils ar e deficient, any one of a numbe r of Cu car r i er s ar e satisfac-
t ory. Some of t he c ommon car r i er s ar e listed i n Tabl e 7. 2. Th e initial
appl i cat i on of Cu shoul d usually be banded at t he r at e of 6 pounds / a c r e .
Because Cu accumul at es i n soils, no addi t i onal a mount need be a dde d for
cr ops t hat r espond little t o Cu aft er a t ot al of 20 pounds / a c r e has been
appl i ed over a per i od of years. Thi s a mount needs t o be doubl ed for hi ghl y
responsi ve cr ops.
If a Cu deficiency is f ound dur i ng t he gr owi ng season, foliar sprays can
be used at one-hal f t o one pound of Cu per acr e, dissolved i n 30 gal l ons of
wat er . Common car r i er s for this pur pos e ar e Cu S O4 and Cu O. Chel at ed
f or ms of Cu ar e well adapt ed t o foliar appl i cat i on. T h e Cu chel at es used as
sprays shoul d be appl i ed at t he r at e of about 35 g Cu / a c r e dissolved i n 30
gal l ons of wat er .
Zinc
Many dat a have accumul at ed i ndi cat i ng a decr ease i n t he solubility of Zn
with i ncreasi ng p H. But preci se identification of a solid phase t hat cont rol s
TABLE 7.2 Examples of Copper Carriers
Carrier Formula Cu, percent
Basic copper sulfate
xCuS04 . yCu(OH)2
13- 53
Copper sulfate
CuSO4 . H2O
35
Cupric ammonium phosphate
Cu( NH4 ) PO4 . H2O
32
Copper EDTA chelate Na2 CuEDTA 13
Copper HEDTA chelate NaCuHEDTA 9
Copper frit Frit 40- 50
Cupric oxide CuO 75
Cuprous oxide Cu2 O 89
Copper chloride CuCl2 17
Source: Robertson, Warncke, and Knezek, 1981.
FIGURE 7.2 The general cycle for mi cronutri ents in soils.
142 Sulfur and Micronutrients in Soils and Fertilizers Essential Micronutrients 143
TABLE 7.3 Interaction of Phosphorus and Zinc with Navy Bean Yield
Zinc
pounds/ acre Carrier
Yield of
No
Extra P
navy beans, bushels/acre
174 696
Extra P* Extra P*
None - 30.8 20.0 8.8
4.0 Zinc sulfate 39.1 39.8 34.6
4.0 Residual (1 year) 29.7 24.3 12.1
Source: Judy et al.,
*Pounds P/acre.
1964.
yield for t he 3 pounds / a c r e of Zn banded yearly for this site shows t hat this
r at e for appl yi ng Zn was not adequat e for a soil with this degr ee of Zn
deficiency. Ot he r dat a have shown t hat bandi ng Zn i s a satisfactory met hod
of suppl yi ng it if sufficient quant i t y is used.
Car r i er s for Zn ar e gi ven i n Tabl e 7. 5. I nor gani c car r i er s have been
satisfactory for cor r ect i on of Zn deficiency. If t he less sol ubl e forms of Zn,
such as ZnO ar e used, t hey shoul d be f i nel y gr ound. Th e r e i s consi der abl e
evi dence t hat t he less soluble car r i er s shoul d be br oadcast a nd i ncor por at ed
i nt o t he soil, wher eas t he soluble car r i er s such as Zn SO4 and Zn chel at es
shoul d be banded wi t h st ar t er fertilizer at pl ant i ng t i me. Rat es of 3 t o 4
p o u n d s / a c r e of Zn as i nor gani c car r i er s band- appl i ed with a st ar t er fertil-
izer each year ar e satisfactory. Chel at ed mat eri al may be appl i ed at one-fifth
t he r at e of t he i nor gani c car r i er s. A single br oadcast appl i cat i on of 25
pounds Zn / a c r e appear s t o be adequat e for many years.
Consi der abl e success has been obt ai ned by i ncor por at i ng Zn i n st ar t er
fertilizers. For exampl e, ZnO i ncor por at ed i nt o a mmoni um pol yphosphat e
becomes sol ubl e and available t o pl ant s. Al t hough t r ace el ement s such as Zn
have been f ound t o be beneficial i n stabilizing APP liquid fertilizers, we
mus t quest i on t he use of a hi gh- P st ar t er fertilizer as a car r i er of Zn in field
si t uat i ons in whi ch t he Zn deficiency is i nduced by hi gh- P soil levels.
TABLE 7.4 Effect of Residual Zinc on Yield of Pea Beans
Zinc,
Time of
application
Crop
bushel
1966
yield,
/ acr e
1967
None _
4.2 0
3.0 ZnSO4 Yearly 17.1 3.7
25 ZnSO4 1965 19.9 19.0
122 Clinker 1965 17.7 18.6
Source: Brinkerhoff et al., 1967; and Vinande et al., 1968.
Zn solubility has been difficult. However , Zn upt ake by pl ant s decl i nes
rapi dl y as pH i ncreases (see Fi gur e 7. 3).
Of t he i nor gani c Zn species i n t he soil sol ut i on, Z n
2 +
i s t he pr edomi -
nant one for pHs less t han 7. 7, and Z n O H
+
i s t he pr edomi nant species for
pHs bet ween 7.7 and 9. 1. Th e ion pai r Zn( OH) 2 i s i mpor t ant onl y for pHs
above 9. Or gani c mat t er does compl ex Zn i n soil sol ut i on, but t he per cent -
age of Zn t hat i s compl exed varies over a consi der abl e r ange, from 28 t o 99
wi t h a mean of 60 for 20 soils accor di ng t o one st udy.
T h e i mpor t ance of or gani c mat t er i n mai nt ai ni ng available Zn i s oft en
i l l ust rat ed by Zn deficiency, whi ch appear s i n ar eas wher e t he surface soil
has been r emoved, ei t her t hr ough l evel i ng t o pr epar e for i rri gat i on or
dur i ng t he installation of dr ai nage lines. He r e t he effect may also be due t o
i ncreased p H, since r emoval of t he surface layer very oft en exposes calcar-
eous B and C hor i zons.
Hi gh levels of P in soils has been known to intensify Zn deficiency in a
numbe r of cr ops. It was part i cul arl y not i ceabl e i n r ot at i ons of navy beans, a
cr op suscept i bl e t o Zn deficiency, followed by sugar beet s, a cr op r espond-
i ng t o hi gh levels of P fertilization. Dat a i l l ust rat i ng this i nt er act i on ar e
gi ven i n Tabl e 7. 3.
T h e exact cause of t he Z n - P ant agoni sm has been difficult t o det er -
mi ne. Several factors, however , ar e i mpor t ant from a soil fertility st and-
poi nt . T h e Z n - P ant agoni sm occurs on cal careous soils and may be r el at ed
t o Fe availability. Mor eover , this rel at i onshi p may not be a soil r el at i onshi p
but one wi t hi n t he pl ant itself. Appl i cat i ons of Zn will readi l y over come t he
P- i nduced Zn deficiency. T h e Zn appl i cat i ons show a consi der abl e resi dual
effect, i ndi cat i ng t hat t he t ot al Zn available in t he soil is very i mpor t ant in
pr event i ng Zn deficiency (see Tabl e 7.4). T h e exper i ment was i ni t i at ed i n
1965, but severe dr ought i n t he s umme r of 1965 el i mi nat ed yields t hat
year. Resi dual Zn was very effective i n i ncreasi ng yield, not only t hr ough
t he t wo years r ecor ded her e but for several addi t i onal years. Th e l ower
FIGURE 7.3 The relation between the zinc
content of clover and soil pH. (Unpublished
data of Michigan Agricultural Experimental
Station.)
TABLE 7.5 Examples of Zinc Carriers
Carrier Formula Zn, percent
Zinc sulfate
ZnSO4 . H2O
36
Zinc oxide ZnO 78- 80
Zinc carbonate ZnCO3
52- 56
Zinc EDTA chelate Na2 ZnEDTA 14
Zinc HEDTA chelate NaZnHEDTA 9
Raplex Zinc ZnPF 10
Source: Robertson and Lucas, 1976.
Ma ng a ne s e a nd I r on
To a cer t ai n ext ent , manganese and Fe have similar chemi st ri es i n soils.
Bot h will exist i n mor e t han one oxi dat i on st at e: F e
2 +
, F e
s +
, Mn
2 +
, Mn
3 +
,
Mn
4 +
; consequent l y, bot h ar e affected by dr ai nage condi t i ons of t he soils.
Bot h ar e pr eci pi t at ed as oxi des and hydr oxi des, but Fe forms far less
soluble compounds .
Manganese
In wel l -aerat ed, hi gh- pH soils, Mn i s expect ed t o pr eci pi t at e as Mn O2 and i s
r emoved from sol ut i on as shown by r eact i on 2 of Fi gur e 7. 2. But as pH
decreases, Mn CO3 becomes t he mor e stable phase. He r e a par adox de-
velops, since hi gh CO2 levels devel op i n soils when dr ai nage i s poor , whi ch
decreases t he solubility of Mn t hat comes from t he pr eci pi t at i on of Mn CO3 .
But on t he ot her hand, poor aer at i on favors t he r educt i on of Mn
4 +
t o Mn
2 +
,
and r educed Mn compounds ar e mor e sol ubl e.
Sol ubl e Mn i s t hought t o be i n t he f or m of Mn
2 +
, but i t has been shown
t hat 80% t o 90% of t he Mn i n t he soil sol ut i on i s compl exed wi t h or gani c
mat t er . St eam sterilization r epor t edl y makes Mn sol ubl e because i t r educes
and hydr at es Mn compounds . I t i s t r ue t hat st eam sterilization rel eases Mn,
but t he r eason appear s t o be t hat st eam al t ers t he funct i onal gr oups of soil
or gani c mat t er . We do not know whet her al t er i ng t he funct i onal gr oups
releases mor e colloidal or gani c mat t er t o soil sol ut i on, whi ch i s capabl e of
chel at i ng Mn, or whet her i t r educes t he soil' s ability t o adsor b Mn (see
Tabl e 7.6).
T h e availability of Mn i n t he fi el d has always been difficult t o pr edi ct .
A numbe r of reasons may account for t hi s. Since Mn solubility i s r el at ed t o
oxi dat i on- r educt i on r eact i ons i n t he soil, t he availability of Mn i s closely
r el at ed t o weat her . Cool t emper at ur es may slow down t he mi neral i zat i on of
or gani c Mn. On t he ot her hand, cool t emper at ur es associated wi t h hi gh
levels of rainfall i n earl y spr i ng may keep mor e Mn available t hr ough
r educt i on of Mn oxi des.
Th e r e i s an i nt er act i on bet ween Mn and Fe. Hi gh levels of available Fe
i n or gani c soils or hi gh levels of or gani c mat t er i n sands may l ead t o a Mn
TABLE 7.6 Effect of Steam Treat ment on Manganese Fractions
of a Houghton Muck
Mn
added
ppm
Time before
extraction
days
Steam
treatment Water
Mn extracted, pp
Exchangeable
m
Easily
reducible
0 - none 1.0 2.1 16.3
0 5 hours 4.0 20.0 7.8
800 0 none 50.4 326 123
800 35 none 1.0 2.5 232
800 35 5 hours before 51 344 117
extraction
800 35 5 hours before 29.1 301 154
Mn addition
Source: A. Kozakiewicz and B. G. Ellis as gi ven in Applied Soil Trace Elements, 1980, p. 269,
B. E. Davies, ed. Repri nted with permi ssi on of John Wiley & Sons.
deficiency because a hi gh r at i o of Fe t o Mn i s cr eat ed wi t hi n t he pl ant . Thi s
r at i o i s part i cul arl y i mpor t ant since cer t ai n chel at ed Mn car r i er s will act u-
ally make t he si t uat i on worse r at her t han cor r ect i ng t he Mn deficiency.
Dat a i n Tabl e 7.7 show t hat t he appl i cat i on of as little as one pound per acr e
of Mn as Mn EDTA actually r educed t he yield of soybeans by about 50%.
Si mi l ar dat a wer e obser ved for oni ons. T h e r eason i s t hat t he soil had hi gh
levels of available Fe and low levels of available Mn. T h e Mn added as t he
chel at e readi l y di ssoci at ed and was appar ent l y r e nde r e d unavai l abl e, leav-
i ng t he chel at e t o compl ex mor e Fe and t her eby i ncrease t he available Fe.
A numbe r of Mn car r i er s may be used t o cor r ect Mn deficiency, as
shown i n Tabl e 7. 8. Manganese sulfate has been t he most satisfactory
mat er i al for most si t uat i ons. Th e i nor gani c car r i er s Mn O and Mn frit ar e
not wat er-sol ubl e and must be f i nel y gr ound t o be satisfactory; f i ner t han
100 mesh i s essential and fi ner t han 300 mesh i s desi rabl e. Mn EDTA i s not
TABLE 7.7 Interactions Between Manganese Carriers, Soil pH,
and Yield of Soybeans
Mn treatment
Mn,
Planting
time
fertilizer
Yield of soybeans,
bushels/acre
pH 6.4 pH 7.5
0 None Acid 19.2 22.1
10 MnSO4 Acid 30.8 30.1
1 MnEDTA Acid 17.2 24.1
0 None Neutral 19.2 24.0
10 MnSO4 Neutral 23.7 30.9
1 MnEDTA Neutral 10.9 13.4
Source: Rumpel et al., 1967.
TABLE 7.8 Examples of Manganese Carriers
Carrier Formula Mn, percent
Manganese sulfate
MnSO
4
. 3H
2
O
26- 28
Manganous oxide MnO 41- 68
Manganese frit Frit 35
Manganese EDTA chelate MnEDTA 12
Various other organic-manganese complexes Mn- Or gani c 5- 12
Source: Robert son and Lucas, 1976.
satisfactory for or gani c soils and sands wi t h hi gh levels of or gani c mat t er
t hat may cont ai n a hi gh r at i o of available Fe t o Mn.
T h e r e c omme nde d r at e of Mn appl i cat i on when Mn deficiency i s
suspect ed varies wi t h soil pH and mi ner al cont ent . General l y, i f soil pH i s
above 6. 5, from 4 t o 8 pounds / a c r e of Mn i s r e c omme nde d for mi ner al
soils. If soil pH is from 6.0 to 6. 5, from 4 to 6 pounds of Mn is adequat e. In
all cases t he Mn shoul d be band- pl aced at pl ant i ng t i me for best resul t s. For
or gani c soils, if soil pH is above 6. 4, an appl i cat i on of f r om 4 to 16
pounds / a c r e of Mn i s r e c omme nde d, dependi ng on t he severity of t he
deficiency. If t he pH is from 5.8 to 6. 4, t hen 4 to 12 pounds of Mn is
r e c omme nde d. Fol i ar sprays wi t h Mn may also be used i f t hey ar e compat i -
bl e wi t h ot her sprayi ng pr ogr ams or i f t he Mn deficiency appear s after t he
cr op i s pl ant ed. Fol i ar sprays may be part i cul arl y useful for agr onomi c
crops t hat do not recei ve st ar t er fertilizer.
Iron
Few if any soils ar e deficient in t ot al Fe since t he t ot al soil Fe cont ent varies
from 1 000 t o 10 000 ppm. But t he solubility of Fe i n soils may be l i mi t ed by
t he low solubility of Fe hydr oxi des and oxi des i n t he pH r ange i n whi ch
crops ar e gr own.
Soil condi t i ons t hat l ead t o Fe deficiency i n pl ant s i ncl ude pHs above
7. 0, low soil moi st ur e cont ent , and low or gani c mat t er cont ent . The s e
condi t i ons ar e encount er ed i n t he mor e ar i d west er n states of t he Uni t ed
St at es. Whe n Fe deficiency i s seen i n ot her areas, for exampl e i n t he Nor t h
Cent r al r egi on of t he Uni t ed States, i t i s nor mal l y associated wi t h r emoval
of t he surface soil and expos ur e of cal careous subsoil. In t hese ar eas Fe-in-
efficient species, pi n oaks, for exampl e, may exhi bi t severe Fe deficiency.
Because of t he very l i mi t ed quant i t y of F e
3 +
ions i n t he soil sol ut i ons of
cal careous soils, it is obvi ous t hat or gani c mat t er must play a significant r ol e
i n keepi ng Fe i n soil sol ut i on by f or mi ng very st r ong Fe - o r g a n i c mat t er
compl exes. Pl ant s t hen obt ai n Fe f r om t hese compl exes by r educi ng t he
F e
3 +
t o F e
2 +
at t he r oot surface, as shown i n r eact i on 5 of Fi gur e 7. 2, a nd
t her eby freei ng t he Fe f r om t he or gani c compl ex.
T h e r at e of r educt i on of ferric t o f er r ous i r on has been f ound t o be
great l y i ncr eased when a pl ant i s unde r Fe stress. St ai ni ng t echni ques have
been devel oped t o reveal t he l ocat i on of active Fe- r educi ng sites (Bell,
Chaney, and Appl e, 1988). Fi gur e 7. 4 shows t hat t he active sites i n t omat o
pl ant s ar e on t he younger r oot hai rs l ocat ed ei t her on laterals or near t he t i p
of t he pr i mar y r oot . As i s evi dent , t he pl ant s t hat ar e gr own wi t hout Fe a nd
wi t h P a dde d show much mor e of t he st ai ni ng. A hi gh magni fi cat i on of
l at eral r oot hai rs confi rms t hat t he site of t he r educt i on i s on t he r oot hai r
and not on t he epi der mal cells bet ween t he r oot hai rs (see Fi gur e 7. 5). T h e
dar k st ai ni ng i ndi cat es i nt ense activity on t hese r oot hai rs of an Fe-st ressed
pl ant . Th e pl ant ' s ability t o r espond t o Fe-deficient condi t i ons by becomi ng
abl e t o r educe F e
3 +
at t he r oot surface i s r emar kabl e and undoubt edl y
account s for t he r at her low numbe r of soils t hat pr oduce pl ant s wi t h an Fe
deficiency i n t he fi el d, even unde r cal careous condi t i ons.
Cor r ect i ng an Fe deficiency is very difficult because it is caused by
chemi cal condi t i ons wi t hi n t he soil a nd not by low t ot al Fe cont ent . If
sol ubl e Fe i s added t o t he soil, i t i s very quickly pr eci pi t at ed a nd i s t hen not
available t o pl ant s. Consequent l y, t r eat ment of t he deficiency must be
l i mi t ed t o acidification of t he soil, t her eby solubilizing some of t he Fe
pr esent . It is also possible to add Fe as a chel at e t hat is sufficiently st abl e not
to dissociate in t he soil. Spr ayi ng pl ant s wi t h a sol ubl e Fe sour ce is anot her
possible t r eat ment . Th e chel at es Fe EDDHA and Fe HEDTA ar e satisfac-
t or y unde r many soil condi t i ons. Sol ubl e car r i er s ar e useful for sprayi ng
Fe-deficient pl ant s. Some i nf or mat i on about t hese car r i er s i s gi ven i n Ta-
bl e 7. 9.
FI GURE 7.4 Tomat o roots showi ng the location of iron reducti on sites i n response
to iron stress in the plant. Not i ce the staining of the lateral roots (darker areas) on the
-Fe plants. (Photograph courtesy P. F. Bell and R. L. Chaney, University of Maryland
t he USDA, Beltsville.)
FIGURE 7.5 A close-up of iron-stressed lateral root hairs. Not i ce the staining on
the root hairs but not on the epi dermal cells bet ween the root hairs. (Photograph
courtesy of P. F. Bell and R. L. Chaney, Uni versi ty of Maryland and the USDA,
Beltsville.)
Bor on a nd Mol y b d e nu m
Bor on and mol ybdenum ar e uni que mi cr onut r i ent s because t hey exist i n
t he soil as ei t her ani ons or unchar ged mol ecul es. Because t hey t ake t hese
t wo forms, t hei r chemi st r y i n t he soil and t he factors t hat affect t hei r
availability ar e qui t e di fferent from t hose of t he ot her mi cr onut r i ent s. Bot h
B and Mo, however , ar e much mor e st rongl y adsor bed by soils t han ot her
ani ons, such as Cl
and N O 3
.
Boron
Bor on exists as undi ssoci at ed H3 B O3 or as t he ani on B( OH) 4
i n soils and i n
t he soil sol ut i on. Ei t her f or m shoul d be mobi l e i n t he soil sol ut i on. But bot h
forms ar e ads or bed st rongl y by Fe or Al hydr oxi des. Freshl y pr eci pi t at ed
TABLE 7.9 Examples of Iron Carriers
Carrier Formula Fe, percent
Ferrous ammonium phosphate
Fe( NH4 ) PO4 . H2 O
29
Ferrous sulfate
Fe2 ( SO4 ) 3 . 4H2 O
23
Iron chelates FeEDTA 9- 12
FeHEDTA 5 - 9
FeEDDHA 6
Source: Robertson, Warncke, and Knezek, 1981.
Fe or Al hydr oxi des ar e known t o adsor b much mor e B t han t he hydr oxi des
t hat have aged and crystallized. Th e bondi ng i s t hr ough t he hydr oxyl s at
t he surface of t he pr eci pi t at ed Fe and Al hydr oxi des. Hence, t he mor e
crystalline t he hydr oxi des, t he fewer t he numbe r of exposed hydr oxyl s per
uni t wei ght of hydr oxi de. Mi caceous clay mi neral s also adsor b B. Magne-
si um hydr oxi des and coat i ngs of ot her mi ner al s t hat cont ai n Fe, Al , or Mg
hydr oxi des will ads or b B.
Bor on i s associated wi t h SOM, and soils with hi gh levels of or gani c
mat t er usually cont ai n adequat e B for hi gh soil fertility. Al t hough t he exact
way in which or gani c mat t er hol ds B is not clear, it is pr obabl e t hat B is
ads or bed by t he or gani c mat t er . Repl acement by ot her ani ons or mi neral i -
zat i on of t he or gani c mat t er will rel ease t he B.
Bor on deficiency is often accent uat ed when soil cont ai ns little mois-
t ur e. Consequent l y, sympt oms of B deficiency will very often be obser ved
dur i ng dr y per i ods, but after t he soils ar e br ought back t o fi el d capacity by
rai n, t he new gr owt h may not show B deficiency.
In addi t i on t o deficiencies of B, toxicities must also be consi der ed.
Bor on may be a dde d i n i rri gat i on wat ers or i n sl udges and wast ewat ers.
Toxi ci t i es ar e very cr op- dependent ; t hus, beans may show severe toxicity,
wher eas sugar beet s, unde r t he same condi t i ons, will not show toxicity. A
numbe r of B car r i er s ar e shown i n Tabl e 7. 10.
Molybdenum
Concent r at i ons of Mo in soils ar e very low. Its availability is general l y
l i mi t ed by adsor pt i on of MoO4
2
r at her t han by preci pi t at i on. Hydr ous Fe
oxi des and hydr oxi des ar e known t o adsor b Mo st rongl y, whi ch undoubt -
edly expl ai ns why Mo deficiencies ar e most oft en obser ved on very acid
soils. In fact, l i mi ng al one will general l y cor r ect Mo deficiency. But in
cer t ai n areas of t he wor l d wher e lime i s not available, a few ounces per acr e
of Mo will be a subst i t ut e for many t ons of l i me.
Car r i er s for Mo ar e listed i n Tabl e 7. 11. Usually about 1/ 8 t o 1/ 4
p o u n d / a c r e of Mo ar e adequat e t o cor r ect Mo deficiency. Since this small
quant i t y of Mo is very difficult to spr ead evenly, it is bet t er to i ncor por at e
Mo wi t h ot her fertilizer or to use it as a seed coat i ng.
TABLE 7. 10 Examples of Boron Carriers
Carrier
Borax
Form
Na 2 B4 O7
ula
10H2 O
B, percent
11
Boric acid H3 BO3 17
Sodium pentaborate Na 2 B1 0 O1 6 10H2 O 18
Sodium tetraborate Na2 B4 O7 20
Sodium tetraborate pentahydrate
Na2 B4 O7 .
5H2 O 14
Boron frits Frits 10- 17
Source: Robertson, Lucas, and Chri stenson, 1981.
TABLE 7.11 Examples of Molybdenum Carriers
Carrier Formula Mo, percent
Ammonium molybdate ( NH4 ) 6 MO7 O2 4 2H2 O 54
Sodium molybdate Na2 MoO4 2H2 O 39
Molybdenum trioxide M0O3
66
Source: Robert son, Warncke, and Knezek, 1981.
T R A C E ELEMEN T S T H A T MA Y B E T O X I C
A numbe r of mi cr onut r i ent s and ot her t r ace el ement s may be t oxi c t o
pl ant s, t o ani mal s, or t o bot h. Th e r e ar e soils t hat nat ural l y have l arge
quant i t i es of what is usually a t r ace el ement , for exampl e, Se. The s e soils
may pose a t hr eat because of this nat ural l y hi gh level of a par t i cul ar t r ace
el ement . Th e numbe r of acres affected i s usually r at her few, but i n t he case
of Se, many soils i n t he west er n Uni t ed States nat ural l y cont ai n l arge
quant i t i es.
Manuf act ur i ng processes have left waste mat eri al s t hat have hi gh levels
of many el ement s, i ncl udi ng Zn, Cu, Cd, Ni , Hg, Pb, and ot her s. A few of
t hese will be discussed t o illustrate pr obl ems and quest i ons t hat come up
when sl udge is utilized as par t of a soil fertility pr ogr am.
Bot h muni ci pal sl udge and sl udge gener at ed as a waste pr oduct of
i ndust r y may be available for disposal on l and or for recycl i ng on agri cul -
t ur al l and t o obt ai n benefi t from one or mor e component s of t he waste
mat eri al . T h e quest i on i s whet her we can safely use t he waste mat eri al and
obt ai n a benefi t from it? Several rul es shoul d be followed bef or e usi ng a
waste pr oduct . It must be anal yzed t o det er mi ne its exact composi t i on.
Nor mal l y N in t he sl udges will be similar to N in ma nur e in availability and
may be used t o advant age. Phos phor us and ot her nut r i ent s, i f needed by
t he soil, may also be beneficial. Occasionally mi cr onut r i ent s such as Zn may
be needed, and sl udges can supply t hese needs.
Sl udges or waste mat er i al will often cont ai n ot her t r ace met al s t hat ar e
not needed by cr ops and ar e pot ent i al l y t oxi c. He r e t he quest i on i s how
much can be appl i ed t o soils bef or e t hey become a pr obl em. Gui des for soil
l oadi ng based on soil CEC ar e given i n Tabl e 7. 12. Th e r e may be st at e and
local r egul at i ons t hat also appl y.
Cer t ai n met al s such as Zn ar e not part i cul arl y t oxi c t o pl ant s or ani -
mal s. Consequent l y, t he soil can t ol er at e a consi der abl e l oadi ng with little
pr obl em. A heavy l oadi ng of t hese met al s shoul d be accompani ed by pH
cont r ol t o mai nt ai n a pH above 6. 5, whi ch will mi ni mi ze t he solubility of t he
met al .
Ot he r met al s, Cd i n par t i cul ar , must be r est r i ct ed because t hey ar e
pot ent i al l y t oxi c. Cadmi um is a known car ci nogen. Fur t he r mor e , it readi l y
moves from t he soil t o t he pl ant r oot and i s easily absor bed by pl ant s. Thus ,
even relatively low levels in soils become a t hr eat to peopl e consumi ng t he
Soil Testing for Micronutrients 151
food gr own on t hat soil. Ver y careful cont r ol of appl i cat i ons of Cd i s
essential. Lead and Hg, al t hough very t oxi c i f cons umed by ani mal s, i ncl ud-
i ng huma n bei ngs, ar e st rongl y hel d by soils a nd do not solubilize and move
readi l y t o pl ant r oot s. Thi s means t hat Pb and Hg may be appl i ed t o soils i n
l ar ger quant i t i es t han Cd is.
Chr omi um pr esent s an i nt er est i ng case. T h e f or m used i n i ndust r y i s
general l y Cr
6 +
. I n this f or m t he Cr combi nes wi t h oxygen and exists as
Cr ( OH) 4
2
, whi ch i s t oxi c t o bot h pl ant s and ani mal s. Since i t i s an ani on, i t
is mobi l e in t he soil. If Cr ( OH) 4
2
is appl i ed to t he soil, it can move out of
t he r oot zone and t o t he gr oundwat er . But soils have t he ability t o r educe
C r
6 +
t o Cr
3 +
. Thi s r educt i on i s favored by a hi gh cont ent of or gani c mat t er
i n soils and low pH. Once r educed, t he Cr i s hel d as an exchangeabl e ion
and also preci pi t at es as t he very i nsol ubl e Cr 2 O3 . In this f or m i t i s not
available t o pl ant s.
SOI L T ES T I N G F OR MI C R O N U T R I EN T S
Deficiencies of mi cr onut r i ent s ar e r el at ed t o pl ant species, cl i mat e, and soil
pr oper t i es, such as pH and or gani c mat t er cont ent , i n ways t hat have ma de
it very difficult to devel op a single soil ext r act ant for all mi cr onut r i ent s.
Per haps t he most universally used ext r act ant for mi cr onut r i ent s and ot her
nonessent i al t r ace met al s i s t he DTP A test devel oped by Li ndsay and
Norvel l (1978). T h e ext r act consists of 0. 005 M DTP A (di et hyl enet ri -
ami nepent aacet i c acid), 0.1 M t r i et hanol ami ne, and 0. 01 M CaCl 2 wi t h a
pH of 7. 3. Th e DP TA i s a st r ong compl exi ng agent for heavy met al s,
part i cul arl y Z n
2 +
and Cu
2 +
. Al t hough this test has been widely shown t o
cor r el at e well wi t h available Zn in soils, it has been less successful in mea-
sur i ng ot her available mi cr onut r i ent s.
Some ext r act ant s t hat have been used successfully for mi cr onut r i ent s
ar e listed i n Tabl e 7. 13. For t he best eval uat i on and r ecommendat i ons , t hey
must be coupl ed wi t h soil pH, soil t ype, and local yield cor r el at i on st udi es.
T A B L E 7. 13 Extractants for
Micronutrients for Soil testing
Trace element Soil extractant
Zn
DTPA
0.1 N HCl
Mo
Calcium phosphate
Cu
0.1 N HCl
B
Hot water
Mn
Phosphoric acid
0.1 N HCl
Fe
DTPA
TISSUE TESTING FOR MICRONUTRIENTS
Mi cr onut r i ent deficiencies may be di agnosed by anal yzi ng t he pl ant tissue.
T h e met hods will vary widely wi t h t he par t i cul ar cr op a nd gr owi ng condi -
t i ons. General l y, a cer t ai n pl ant por t i on is sel ect ed (e. g. , ear leaf for cor n)
and a cert ai n st age of pl ant gr owt h i s used. T h e tissue i s col l ect ed a nd
anal yzed, and t he values obt ai ned ar e compar ed with values obt ai ned f r om
hi gh-yi el di ng pl ant s. Some dat a ar e given i n Tabl e 7. 14 as gener al gui de-
lines for t he mi cr onut r i ent s.
MICRONUTRIENTS DEFICIENCY SYMPTOMS
Deficiency sympt oms have been used for a l ong t i me t o identify deficiencies
i n t he f i el d. Thi s has been part i cul arl y t r ue for t r ace el ement deficiencies.
But a numbe r of fact ors make t hi s pract i ce difficult a nd at t i mes less t han
desi rabl e. I t must be r ecogni zed t hat when nut r i ent deficiency sympt oms
appear on a pl ant , t her e has al ready been a loss in yield for t hat year' s cr op.
Cor r ect i ng t he deficiency may be i mpor t ant for t hat year' s cr op, even
T A B L E 7. 14 General Guidelines for Evaluating
Micronutrient Content in Mature Leaves
Concentration in leaves,
mg/ kg
Micronutrient Deficient
Sufficient
B <15 20--200
Cu < 4 5--20
Zn <20 25--150
Fe <50 50--250
Mn <20 20--500
Mo <0. 1 0.5-- 5 (?)
Source: Jones, 1972.
Trace Element Deficiency Symptoms 153
t hough a yield r educt i on is expect ed, and it is i mpor t ant to identify what
deficiency t o expect i n subsequent years. Tr a c e el ement deficiencies ar e
often r el at ed t o climatic gr owi ng condi t i ons, and t hese may change f r om
year t o year. I f gr owi ng condi t i ons ar e not t aken i nt o consi der at i on, con-
clusions about appar ent yield responses t o appl i ed t r ace el ement s can be-
come er r at i c.
Deficiencies i n pl ant s ar e most often mani fest ed as gr owt h i r r egul ar -
ities, so t hat di st i ngui shi ng bet ween t wo or mor e deficiencies may be diffi-
cult. In addi t i on, ot her factors t hat affect gr owt h, such as weat her , chemi cal
damage, and pest damage t o crops, may also give similar sympt oms. For
t hese reasons i t i s i mpor t ant t o obt ai n all possible i nf or mat i on f r om t he
gr ower bef or e at t empt i ng t o di agnose a deficiency by pl ant sympt oms.
Once a t ent at i ve identification i s made, i t shoul d be verified by t r eat ment
with t he el ement i n whi ch t he pl ant i s assumed t o be deficient.
Dat a i n Tabl e 7. 15 ar e given t o summar i ze whi ch factors may hel p t o
identify a par t i cul ar deficiency sympt om. Since many deficiency sympt oms
ar e similar, i dent i fyi ng wher e t he deficiency occurs may be very i mpor t ant .
Some t r ace el ement s, such as Mo, ar e relatively mobi l e i n pl ant s. Whe n t he
el ement becomes deficient i n t he soil, t he Mo i n t he pl ant i s t r ansl ocat ed
from t he ol d t o t he new tissue, and t he sympt oms appear f i r st on t he ol d
tissue. On t he ot her hand, i f t he el ement , Fe for exampl e, i s not mobi l e i n
t he pl ant , t he deficiency appear s f i r st on t he new pl ant gr owt h.
TABLE 7.: 15 Guide to Nutrient Deficiency Symptoms for Micronutrients
Trace Plant Deficiency Associated
element mobility symptoms growth changes
Zn Partially Light interveinal tissue in Iron accumulates at
mobile older leaves. Abnormally nodes. Delayed
shaped leaves. Shortened maturity.
internodes of broadleaf
crops.
Mo Yes General yellowing, with Stunted growth.
some mottling and
cupping of older leaves.
Cu No Youngest leaves becoming Iron accumulates in
"olive" and stunted. nodes.
B No Unusual brittleness of Slow growth. Death of
stems, cracking of stems, terminal tissue.
thickening, curling, and
chlorosis of leaves.
Fe No Very light yellow to white New growth is severely
on new growth. Veins are retarded.
green.
Zi nc
Zinc deficiency i s per haps one of t he easiest t o r ecogni ze unde r fi el d condi -
t i ons. It most oft en occurs on cal careous soils and soils t hat have hi gh levels
of phosphat e, ei t her as resi dual or as a cur r ent P appl i cat i on. In gener al , t he
Zn deficiency appear s earl y i n t he gr owi ng season and i s caused ei t her by
cool weat her or by t he r est r i ct ed r oot i ng zone of t he pl ant s. Zinc deficiency
i s also commonl y associated wi t h par t i cul ar cr ops and i n fact wi t h par t i cul ar
varieties. For exampl e, when gr own on t he same soil and i n t he same
r ot at i on, navy beans may show a severe Zn deficiency when sugar beet s
show no deficiency and do not give a yield r esponse t o Zn. Sanilac beans
may show a severe deficiency of Zn when Sagi naw beans gr own side by side
give relatively little r esponse t o Zn. T h e same obser vat i on can be made
about toxicity. Sanilac beans ar e much mor e suscept i bl e t o Zn toxicity t han
Sagi naw beans if Zn levels ar e excessive in soils. It is c ommon to find this
differential susceptibility to Zn deficiency in di fferent vari et i es of navy
beans, cor n, and pr obabl y some ot her crops.
T h e out war d sympt om of Zn deficiency i s light i nt ervei nal tissue. For
di cot cr ops such as navy beans, this di sor der appear s fi rst i n t he ol der leaves
and t o a lesser degr ee i n younger leaves. T h e light i nt ervei nal tissue t akes
on t he appear ance of st ri pi ng i n cor n a nd does not usually affect ol der
leaves but r at her appear s f i r st on leaves of i nt er medi at e age. I n cor n and
s or ghum t he pl ant s will have s hor t ened i nt er nodes (see Fi gur e 7.6) and
dar kened nodal tissue, i ndi cat i ng an accumul at i on of Fe at t he nodes. As
zinc deficiency devel ops, t he shapes of leaves often become abnor mal ,
part i cul arl y i n cr ops such as beans and fruit t rees (see Fi gur e 7.7). Thi s
FIGURE 7.6 Zinc-deficient corn (left) showi ng shortened i nternodes.
sympt om is very useful in separ at i ng Zn deficiency from Mn deficiency
since Mn deficiency does not cause abnor mal l y shaped leaves. Del ayed
mat ur i t y i s also charact eri st i c of Zn deficiency. Th e fi el d resul t s of gr owi ng
navy beans in Mi chi gan r eveal ed a Zn deficiency so severe t hat t her e was
essentially no yield.
Mol y b d e nu m
Th e deficiency of Mo may affect l egume and nonl egume pl ant s qui t e
differently. Mol ybdenum is r equi r ed by rhi zobi a for N fixation. Conse-
quent l y, a Mo deficiency in a l egume pl ant may be mani fest ed as a N
deficiency. It t hen appear s as light col or and st unt i ng i n pl ant s.
Field sympt oms of Mo deficiency i n t he Uni t ed States have most oft en
been obser ved on veget abl e cr ops. T h e youngest leaves ar e t he most oft en
affected. The y become mot t l ed and t hei r leaf mar gi ns ar e nar r ow. Th e
leaves will el ongat e abnor mal l y and i n cauliflower t hey ar e oft en twisted,
whi ch i s t he basis for t he c ommon t er m whiptail appl i ed t o t he deficiency
sympt om. Somet i mes t he leaves may t ake on a cuppi ng appear ance.
Ma ng a ne s e
Manganese deficiency oft en appear s as i nt ervei nal chlorosis. Unl i ke what
happens wi t h Zn deficiency, t he leaves appear nor mal except for col or and
show no abnor mal shape. If a Mn deficiency devel ops when t he pl ant i s very
young, i t may be very uni f or m i n bot h young and ol der leaves. If t he
deficiency devel ops after t he pl ant i s much l arger, however , i t will be much
mor e pr eval ent on t he younger leaves. Thi s di st r i but i on i s uneven because
Mn i s only slightly mobi l e i n t he pl ant . In Mn-defi ci ent bean pl ant s t he
tissue bet ween t he veins becomes i ncreasi ngl y l i ght er i n col or. But t he veins
r emai n dar k, maki ng this Mn deficiency easy t o di st i ngui sh from N defi-
ciency (see Fi gur e 7.8)
Small grai ns qui t e oft en show Mn deficiency. General l y, a gray oval-
shaped spot devel ops on t he edge of a new leaf. T h e gray spot will enl ar ge
unt i l i t covers much of t he leaf and t akes on a yellow appear ance. T h e t i p of
t he leaf will r emai n gr een dur i ng this process. Manganese deficiency i n cor n
and grai n s or ghum appear s as i nt ervei nal chlorosis, usually on t he youngest
leaves. It may be similar t o Fe deficiency, but Mn deficiency usually appear s
on soils wi t h hi gh or gani c mat t er cont ent , wher eas Fe deficiency sel dom
occurs on t hese soils.
On cer t ai n veget abl e cr ops such as broccol i , Mn deficiency causes t he
leaf surface to lose it waxy coat i ng. Thi s loss is qui t e appar ent when com-
par i ng deficient pl ant s wi t h pl ant s sufficient i n Mn.
FIGURE 7.8 Manganese-defi ci ent bean plant grown in a
greenhouse.
Cop p e r
Because Cu i s not t r ansl ocat ed i n t he pl ant , t he deficiency sympt oms appear
on t he new gr owt h. I n small grai ns and cor n t he leaves appear olive or
yellowish gr een i n col or, and oft en t he leaves fail t o unr ol l as t hey emer ge.
Of t en t he leaf tips will appear as t hough t he pl ant s have been frost -dam-
aged, and t her e will be some flags. A flag is a wi l t ed or dead leaf or a br anch
wi t h such leaves on an ot her wi se heal t hy- appear i ng pl ant .
Bor on
Bor on deficiency sympt oms ar e sel dom obser ved except for sensitive cr ops
such as l egumes, sugar beet s, a nd some veget abl e crops. In alfalfa t he
deficiency is shown by yellowing of t he leaves and by rest ri ct i on of t he
t er mi nal gr owt h. Thi s rest ri ct i on gives very shor t i nt er nodes and offers a
me t hod of separ at i ng B deficiency from insect damage, whi ch may give
similar visual sympt oms but wi t h nor mal node l engt hs. Boron-defi ci ent
sugar beet s devel op cross-checked pet i ol es and mi sshapen leaves. T h e leaf
bl ades gr ow uneven on t wo sides of t he pl ant and mor e i n t he hor i zont al
di r ect i on t han i n t he vertical di r ect i on. Whe n t he deficiency i s severe, t he
t er mi nal gr owt h or apical mer i st em tissue dies, and t he r oot s may devel op
hear t r ot .
I r on
I r on i s t he least mobi l e of t he mi cr onut r i ent s i n pl ant s. Whe n t he deficiency
appear s, i t i s on t he new gr owt h a nd may be very severe. T h e pl ant leaves
will fi rst appear yellow i nt ervei nal l y wi t h gr een veins. But when t he defi-
ciency i s severe, t he ent i r e ar ea may appear whi t e (see Fi gur e 7.9). It can be
FIGURE 7.9 Iron-deficient bean plants showi ng severe chlorosis on the new
growth.
References 159
Robertson, L. S., R. E. Lucas, and D. R. Christenson. 1981. Boron: An Essential
Plant Micronutrient. Coop. Ext. Ser. Bull. E1037. Michigan State University,
East Lansing.
Robertson, L. S., D. D. Warncke, and B. D. Knezek. 1981. Copper: An Essential
Plant Micronutrient. Coop. Ext. Ser. Bull. E1519. Michigan State University,
East Lansing.
Robertson, L. S., D. D. Warncke, and B. D. Knezek. 1981. Iron: An Essential Plant
Micronutrient. Coop. Ext. Ser. Bull. E1520. Michigan State University, East
Lansing.
Robertson, L. S., D. D. Warncke, and B. D. Knezek. 1981. Molybdenum: An
Essential Plant Micronutrient. Coop. Ext. Ser. Bull. E1518. Michigan State Uni-
versity, East Lansing.
Rumpel, J., A. Kozakiewicz, B. G. Ellis, G. Lessman, and J. F. Davis. 1967. Field and
Laboratory Studies with Manganese Fertilization of Soybeans and Onions.
Quart. Bull. Mich. Agr. Exp. Sta. 50: 4- 11.
Tabatabai, M. A., ed. 1986. Sulfur in Agriculture Am. Soc. Agron., Madison, Wis.
Vinande, R. B., B. D. Knezek, J. F. Davis, E. C. Doll, and J. Melton. 1968. Field and
Laboratory Studies with Zinc and Iron Fertilization of Pea Beans, Corn, and
Potatoes in 1967. Quart. Bull. Mich. Exp. Sta. 50: 625- 636.
demons t r at ed t hat Fe is very i mmobi l e by pl aci ng a local spot of Fe sol ut i on
on t he surface of a deficient leaf and obser vi ng t hat t he leaf will devel op a
gr een col or i n this ar ea only.
REF ERENCES
Bell, P. F., R. L. Chaney, and J. S. Apple. 1988. Staining Localization of Ferric
Reduction on Roots, Jour. Plant Nutr. 11: (In press.)
Brinkerhoff, F., B. G. Ellis, J. F. Davis, and J. M. Melton. 1966. Field and Labora-
tory Studies with Zinc Fertilization of Pea Beans and Corn in 1965. Quart. Bull.
Mich. Agr. Exp. Sta. 48: 344- 356.
Brinkerhoff, F., B. G. Ellis, J. F. Davis, and J. M. Melton. 1967. Field and Labora-
tory Studies with Zinc Fertilization of Pea Beans and Corn in 1966. Quart. Bull
Mich. Agr. Exp. Sta. 49: 1- 14.
Couch, E. L. and R. E. Grim. 1968. Boron Fixation by Illites. Clays and Clay Miner.
16: 249- 256.
Davies, B. E., ed.. 1980. Applied Soil Trace Elements. John Wiley, New York.
Duke, S. H. and H. M. Reisenauer. 1986. Roles and Requirements of Sulfur in
Plant Nutrition. In Sulfur in Agriculture. M. A. Tabatabai, ed. Am. Soc. Agron.,
Madison, Wis.
Follett, R. H., L. S. Murphy, and R. L. Donahue. 1981. Fertilizers and Soil Amend-
ments. Prent i ce-Hal l , Englewood Cliffs, N.J.
Geering, H. R., J. F. Hodgson, and C. Sdano. 1969. Micronutrient Cation Com-
plexing in Soil Solution: IV. The Chemical State of Manganese in Soil Solution.
Soil Sci. Am. Proc. 33: 81- 85.
Hodgson, J. F., W. L. Lindsay, and J. F. Trierweiler. 1966. Micronutrient Cation
Complexing in Soil Solution: II. Complexing of Zinc and Copper in Displaced
Solution from Calcareous Soils. Soil Sci. Soc. Am. Proc. 30: 723- 726.
Jacobs, L. W. 1981. Agricultural Application of Sewage Sludge. In Sludge and Its
Ultimate Disposal. J. A. Borchardt, W. J. Redman, G. E. Jones, and R. T.
Spregue, eds. Ann Arbor Science Publications Ann Arbor, Michigan.
Jones, J. Benton, Jr. 1972. Plant Tissue Analysis for Micronutrients. In Micronu-
trients in Agriculture. J. J. Mortvedt, P. M. Giordano, and W. L. Lindsay, eds.
Soil Sci. Soc. Am., Madison, Wis.
Judy, W. G., G. Lessman, T. Rozycka, L. S. Robertson, and B. G. Ellis. 1964. Field
and Laboratory Studies with Zinc Fertilization of Pea Beans. Quart. Bull. Mich.
Agr. Exp. Sta. 46: 386- 400.
Knezek, B. D. and H. Greinert. 1971. Influence of Soil Iron and Manganese
Chelate Interactions upon the Iron and Manganese Nutrition of Bean Plants.
Agron. Jour. 63: 617- 619.
Lindsay, W. L. and W. A. Norvell. 1978. Development of a DTPA Soil Test for
Zinc, Iron, Manganese and Copper. Soil Sci. Soc. Am. Jour. 42: 421- 428.
Mortvedt, J. J., P. M. Giordano, and W. L. Lindsay, eds. 1972. Micronutrients in
Agriculture. Soil Sci. Soc. Am., Madison, Wis.
Nriagu, J. O., D. A. Holdway, and R. D. Coker. 1987. Biogenic Sulfur and the
Acidity of Rainfall in Remote Areas of Canada. Science. 237: 1189- 1192.
Robertson, L. S. and R. E. Lucas. 1975. Essential Micronutrients: Zinc. Coop. Ext.
Ser. Bull. E1012. Michigan State University, East Lansing.
Robertson, L. S. and R. E. Lucas. 1976. Essential Micronutrients: Manganese. Coop.
Ext. Ser. Bull. E1031. Michigan State University, East Lansing.
C H A P T E R 8
Mixed Fertilizers
T h e fertilizer i ndust r y devel oped i n stages wi t h phos phat e mat eri al s i n t he
1840s, pot assi um mat eri al s i n t he 1870s and t he ni t r ogen mat eri al s about
1900. Mor e recent l y, mi cr onut r i ent fertilizers have been devel oped. Dur -
i ng t he earl y years of fertilizer manuf act ur i ng, dr y mat eri al s wer e mi xed
t oget her . The s e fertilizers wer e dust y, a nd t he mat eri al s woul d segr egat e
dur i ng t r anspor t and appl i cat i on. Th e n t he addi t i on of anhydr ous ammoni a
t o dr y mi xes and t hei r subsequent gr anul at i on const i t ut ed a maj or advance.
T h e gr anul ar fertilizers ar e dust -free, a nd each gr anul e has similar compo-
sition and part i cl e size. The s e free-flowing fertilizers wer e ne e de d for t he
new fertilizer appl i cat i on equi pment t hat was bei ng devel oped. Mor e r e-
cent l y, fl ui d fertilizers have become very popul ar .
Overal l soil fertility i n t he Uni t ed St at es has been i ncreasi ng, and i n
many i nst ances t he appl i cat i on of onl y one nut r i ent i s desi rabl e. I mpr ove-
ment s and gr eat er use of soil tests have hel ped identify t hese si t uat i ons. As a
resul t , t he use of car r i er s for di r ect appl i cat i on of nut r i ent s t o t he soil,
rel at i ve t o t he use of mi xt ur es , has been i ncreasi ng. Actually, t he applica-
t i on of bot h ki nds of fertilizers has been i ncreasi ng, but , i n 1976 t he di r ect
appl i cat i on of si ngl e-carri er fertilizers surpassed t he use of mi xt ur es. In
1982 i t was est i mat ed t hat 21 million t ons of mi xed fertilizers wer e pr o-
duced i n t he Uni t ed States and t hat this r epr es ent ed 44 per cent of t he t ot al
fertilizer pr oduct i on. Of t he mi xt ur es, bul k bl ends of dr y gr anul at ed mat e-
rials wer e t he most popul ar . Dry gr anul ar homogeneous mi xt ur es wer e t he
second most popul ar followed by f l ui d fertilizers. Thi s chapt er exami nes
t he pr oper t i es of mi xed or c ompound fertilizers and t hei r manuf act ur e by
combi ni ng t wo or mor e fertilizer car r i er s or i nt er medi at es.
160
Major Fertilizer Systems 161
G R A D E A N D R A T I O
T h e fertilizer gr ade i s t he mi ni mum guar ant eed a mount of pl ant nut r i ent s
expr essed i n wei ght per cent ages of t ot al N, available P 2 O 5 (wat er- a nd
ci t rat e-sol ubl e), a nd wat er-sol ubl e K2 O i n t hat or der . T h e gr ade 6-24-24
has a 1-4-4 r at i o. Fert i l i zers ar e pr oduced with vari ous rat i os t o cor r es pond
t o t he di fferent needs of vari ous cr op and soil si t uat i ons. Lawn and t ur f
commonl y r equi r e a l arge a mount of N rel at i ve to P and K. For lawns 4-1-1
or 4-1-0 fertilizers ar e popul ar . Fr equent l y, a small a mount of N and all or
par t of t he P a nd K ar e appl i ed ne a r or at pl ant i ng t i me i n a mi xed fertilizer.
Lat er , when t he cr op' s need of N i s maxi mum, much mor e N may be
appl i ed usi ng a N car r i er such as anhydr ous ammoni a. Thus , many soil
ma na ge me nt pr ogr ams make use of bot h mi xed and si ngl e-carri er
fertilizers.
MA J OR F ERT I LI Z ER SYST EMS
Th e r e ar e t wo over l appi ng organi zat i ons i n t he pr oduct i on and mar ket i ng
of fertilizers i n t he Uni t ed St at es. As discussed i n earl i er chapt er s, t he maj or
N mat er i al , NH3 , i s pr oduced near nat ur al gas wel l heads or pi pel i nes. Th e
maj or P sour ce mat eri al s for f er t i l i zer ssuper phosphat es, a mmoni um
phosphat es, and phosphor i c a c i d a r e pr oduced near t he rock phos phat e
mi nes i n Fl ori da, Nor t h Carol i na, and some west er n states. Unt i l t he 1960s,
when mi nes wer e opened i n Saskat chewan, most of t he KC1 was pr oduc e d
near Carl sbad, New Mexi co. Now 70 per cent or mor e of t he K i n fertilizers
i n t he Uni t ed St at es comes from t he Canadi an mi nes. The s e mat eri al s or
car r i er s ar e frequent l y appl i ed di rect l y t o soils, but t hey ar e called i nt er me-
di at es t o i ndi cat e t hei r r ol e i n t he manuf act ur e of mi xed fertilizers. The s e
fairly concent r at ed i nt er medi at es ar e t r ans por t ed t o r egi onal and local
pl ant s near mar ket s, and t her e t hey ar e combi ned i nt o mi xed fertilizers.
T h e pr oduct i on pat t er n for finished mi xed ( NPK) fertilizers i n t he Uni t ed
St at es has evol ved i nt o t hr ee mai n systems: gr anul at i on, bul k bl endi ng, and
fl ui d fertilizers. T h e rel at i ve i mpor t ance of t hese t hr ee systems i s shown i n
Tabl e 8. 1.
Gr a nu l a t i on
Th e process of gr anul at i ng dr y fertilizers was devel oped t o pr ovi de a mor e
uni f or m pr oduct for use i n l abor-savi ng mechani cal appl i cat ors and t o
r e duc e t he costs of manuf act ur i ng a nd t r anspor t . At f i r st dr y mi xed fertil-
izers wer e moi st ened wi t h wat er and subj ect ed t o mechani cal act i on i n a
mi xer t o f or m mor e or less uni form-si zed part i cl es. Aft er t he bat ch was
gr anul at ed i n t he mi xer , t he part i cl es wer e dr i ed, scr eened, and cool ed.
Oversi zed and under si zed part i cl es wer e recycl ed. A coat i ng mat er i al was
a dde d t o mi ni mi ze l umpi ng and caki ng dur i ng st or age. Thi s me t hod of
gr anul at i on is sui t abl e for small pl ant s and is still i mpor t ant in devel opi ng
count r i es.
162 Mixed Fertilizers
TABLE 8.1 Consumption of Granulated, Bulk-Blended, and
Fluid Fertilizers
Total Total mixed
Type fertilizers, percent fertilizers, percent
Granular NPK 16.6 28.6
Bulk-blended 31.5 54.3
Fluid 9.9 17.1
Source: Unpubl i shed TVA data for the Uni t ed States, 1981.
I n t i me, t he cont i nuous d r u m or t ube gr anul at or , as opposed t o t he
bat ch mi xer , became popul ar . T h e gr anul at or i s a r ot at i ng d r u m about 1 t o
2. 5 met er s i n di amet er and 3 t o 10 met er s l ong. I ncomi ng mat eri al s ar e
scr eened t o r emove l umps, whi ch ar e cr ushed. T h e mat eri al s ar e wei ghed
and cont i nuousl y fed i nt o t he gr anul at or at a cont r ol l ed r at e. St eam i s
di schar ged unde r t he bed of mat eri al and wat er i s spr ayed on t op. Gr anul a-
tion i s cont r ol l ed by t he a mount of wat er added. Di schar ged part i cl es ar e
dr i ed, cool ed, and scr eened and oversi zed and under si zed gr anul es recy-
cled. A flow di agr am of a typical gr anul at i on pl ant is shown in Fi gur e 8. 1,
and some typical f or mul at i ons for gr ades ar e given i n Tabl e 8. 2.
In efforts t o i ncrease t he N cont ent of gr anul ar fertilizers, an ammoni a-
t or was a dde d t o t he process and, mor e recent l y, phosphor i c and sulfuric
acids wer e added. Now many chemi cal r eact i ons occur i n t he gr anul at or ,
and bot h dr y mat eri al s and sl urri es ar e gr anul at ed.
Melt Granulation
Th e mel t gr anul at i on process devel oped i n t he 1960s was f i r st used t o
pr oduce gr anul ar a mmoni um phosphat es. Wet -process super phosphor i c
acid and ammoni a ar e r eact ed i n a confi ned pi pe i n whi ch heat i s rel eased,
evapor at i ng some of t he wat er t hat i s pr esent and pr oduci ng a mel t . Th e
mel t i s t he liquid phase of t he solid fertilizer. Th e r eact or devel oped by
TVA i s called t he pipe-cross r eact or (PCR). Phosphor i c and sulfuric acid
ar e r eact ed si mul t aneousl y with NH3 , wi t h t he rel ease of much heat and t he
f or mat i on of a mel t . Th e mel t i s spr ayed i nt o t he gr anul at or dr um, and wi t h
t he addi t i on of KC1, a compl et e mi xed fertilizer can be pr oduc e d (see
Fi gur e 8.2). Some advant ages of t he PCR and mel t gr anul at i on ar e
1. Reduced costs for dr yi ng, since gr anul es pr oduced from t he mel t of t he
PCR have onl y 1% t o 4% wat er compar ed t o 10% t o 15% for r egul ar
gr anul at i on.
2. Easier compl i ance wi t h envi r onment al r egul at i ons because fewer a mmo-
ni um chl or i de fumes ar e pr oduced.
3. Easier and mor e preci se cont r ol of i ngr edi ent s.
4. Lower pl ant const r uct i on costs.
163
T h e progressi ve devel opment of bet t er manuf act ur i ng met hods has
r esul t ed i n a progressi ve i ncrease i n t he nut r i ent concent r at i on of mi xed
fertilizers from 15% ( N + P 2 O 5 + K2 O) i n 1910 t o 44% i n 1981. The s e
met hods have also achi eved a l ower cost per pound of pl ant nut r i ent .
Caking and Dustiness
Bet ween manuf act ur e a nd appl i cat i on t o t he soil, dr y fertilizers must be
st or ed i n bul k or i n bags. It i s essential t hat t he fertilizers mai nt ai n t hei r
free-flowing char act er and not cake or f or m l umps i n st or age. Fert i l i zer
cakes when crystal bonds gr ow bet ween part i cl es. The s e crystals may de-
vel op dur i ng st or age t hr ough cont i nui ng chemi cal react i ons, or t her mal
effects may pr oduce small crystals from mi nut e amount s of sol ut i ons i n t he
fertilizer. I nt er gr owt h of crystals bet ween part i cl es causes cement at i on or
caki ng. In some i nst ances cohesi ve forces bet ween part i cl es have pr oduced
caki ng. Lar ge gr anul es r educe t he n u mb e r of cont act poi nt s bet ween part i -
cles; gr anul ar mat eri al s have less of a t endency t o cake t han do pul ver i zed
mat eri al s. Soft gr anul es unde r pr essur e i n st or age piles may def or m, whi ch
causes relatively l arge ar eas of cont act bet ween gr anul es and pr omot es
caki ng.
A f r equent mi sconcept i on hol ds t hat moi st ur e absor bed dur i ng st or age
causes caki ng, but excessive moi st ur e left i n t he pr oduct dur i ng manuf ac-
t ur e i s t he t r ue agent . Th e N mat eri al s have t he great est t endency t o cause
caki ng i f t hey ar e not pr oper l y dr i ed. I n gener al , t hey shoul d cont ai n 0. 5%
or less of free wat er ( nonhydr at e wat er).
Solid condi t i oni ng or ant i caki ng dust s i n c ommon use i ncl ude di at oma-
ceous ear t h (ki esel guhr), kaolin clay, t al c, and chalk. Usually 1% t o 4% of
t hese powder ed condi t i oner s i s appl i ed. Clays have good adher ence t o
part i cl es, but di at omaceous ear t hs have gr eat er absor bency. Adher ence of
condi t i oner s can be i mpr oved by sprayi ng t he fertilizer with a small a mount
of oil ei t her bef or e or aft er t he condi t i oner i s appl i ed.
Dust i ness is a very undesi r abl e pr oper t y, especially with our i ncreasi ng
concer n about t he heal t hful ness of t he wor k envi r onment . Gr anul at i on
does much t o r educe t he dust i ness of dr y fertilizers, but dust i ness may still
exist. Th e dust i ness of gr anul ar fertilizers i s caused by poor sizing, whi ch
leaves t oo many f i ne, soft gr anul es, whi ch i n t ur n br eak apar t ; t he poor
adher ence of condi t i oner s; and t he f or mat i on of surface crystals, whi ch may
abr ade t o form dust . Th e adher ence oil j ust ment i oned i s t he maj or way i n
whi ch dust i ness is cur r ent l y cont r ol l ed.
Bu l k Bl e nd i ng
Gr anul at i on i s used t o pr oduce si ngl e-nut ri ent car r i er s as well as compl et e
NPK fertilizers. Bulk bl endi ng i s t he physical mi xi ng of t wo or mor e gr anu-
lar mat eri al s. Th e pract i ce was fi rst st ar t ed i n Illinois i n 1947. Bl ended
fertilizers can be bagged or di st r i but ed i n bul k. Onl y 23 per cent of t he
bl ender s i n t he Uni t ed States have baggi ng facilities.
A maj or advant age of bul k bl endi ng is t he ease wi t h whi ch many
di fferent gr ades a nd rat i os can be f or mul at ed. Pr escr i pt i on mi xes gui ded by
soil analysis ar e popul ar . T h e maj or i nt er medi at es used ar e gr anul ar ur ea,
a mmoni um ni t r at e, di ammoni um phosphat e, t ri pl e super phosphat e, and
pot assi um chl or i de. Thes e mat eri al s ar e shi pped t o a pl ant l ocat ed i n t he
ar ea wher e t he fertilizer will be used. T h e mat eri al s ar e mi xed and com-
monl y l oaded di rect l y i nt o a t r uck and i mmedi at el y spr ead i n t he fi el d (see
Fi gur e 8.3). T h e ent i r e cycle of wei ghi ng, mi xi ng, and di schar gi ng may be
aut omat ed. Low cost i s a maj or r eason for t he popul ar i t y of bul k bl endi ng
whi ch now account s for 54 per cent of all mi xed fertilizers i n t he Uni t ed
St at es.
FIGURE 8. 2 Di agram of a pipe-cross reactor used to make mel ts for the manufacture of
granular fertilizer.
Chemical Incompatibility of Intermediates
T h e chemi cal i ncompat i bi l i t y of i nt er medi at es may cause t he mi xt ur e t o
heat up, wat er t o form, gas t o evol ve, and caki ng. Onl y a few mat eri al s ar e
t r oubl esome (see Fi gur e 8.4). Mi xi ng of ur ea wi t h a mmoni um ni t r at e must
be avoi ded, for i t causes a hi gh degr ee of wet t i ng and i s r el at ed t o t he
critical rel at i ve humi di t y ( CRH) . Th e CRH i s t he rel at i ve humi di t y above
whi ch t he mat eri al spont aneousl y absorbs moi st ur e from t he ai r. Relatively
pur e ur ea does not absor b wat er at 70% rel at i ve humi di t y, but i t t akes up
wat er cont i nuousl y at 75% rel at i ve humi di t y at 30 degr ees C (86 degr ees F).
Thi s CRH i s typical for most fertilizer mat eri al s; however , mi xt ur es of salts
usually have a l ower CRH t han ei t her const i t uent . Whe n ur ea and N H 4 N O 3
wi t h CRHs of 72. 5 and 59. 4, respectively, ar e mi xed t oget her , t he CRH of
t he mi xt ur e i s only 18. 1%. Thus , ei t her al one may st ore well, but when
mi xed t oget her t hey ar e very hygroscopi c and t ake up moi st ur e from t he
ai r at low rel at i ve humi di t y.
Ur ea react s with monocal ci um phos phat e monohydr at e i n super phos-
phat e t o rel ease wat er of hydr at i on and pr oduce severe stickiness:
Ca ( H2 P O4 ) 2 . H2 O + 4 CO( NH2 ) 2 = Ca ( H2 P O4 ) 2 . CO( NH2 ) 2 + H2 O (8.1)
Mi xi ng di ammoni um phos phat e with super phosphat es may cause caki ng
dur i ng l ong- t er m st or age.
Segregation
Bulk handl i ng may i nduce part i cl es of a fertilizer t o segr egat e, wher eupon
its composi t i on becomes nonuni f or m t hr oughout . Segr egat i on of part i cl es
i s undesi r abl e because t he consequent nonuni f or mi t y can make i t impossi-
bl e t o obt ai n pr oper sampl es of fertilizer t o meet analytical guar ant ees.
FIGURE 8. 4 Chemical compatibility of bl end materials. (Courtesy
TV A. )
Agr onomi c responses may be affected and ar e a par t i cul ar pr obl em i f a
mi cr onut r i ent i nt er medi at e i s separ at ed from t he bul k of t he fertilizer.
Segr egat i on occurs because i ndi vi dual part i cl es in a fertilizer r es pond
differently t o mechani cal di st ur bances dur i ng handl i ng. Part i cl es of similar
physical pr oper t i es t end t o congr egr at e t hus dest r oyi ng homogenei t y. Nu-
mer ous tests have shown t hat t he physical pr oper t y br i ngi ng about t he most
segregat i on i s part i cl e size. Nei t her t he densi t y or shape of part i cl es wi t hi n
t he r anges f ound i n fertilizers causes segr egat i on t o an i mpor t ant degr ee.
Dur i ng t he flow of a bul k- bl ended fertilizer i nt o a st or age bi n or t r uck,
part i cl es of t he vari ous i nt er medi at es may segr egat e. T h e f i ner part i cl es
t end t o r emai n wher e t hey fall, t he l arger part i cl es roll down t he pile
t owar d t he per i met er . Thi s process i s called coni ng. Most of t he bul k-
bl ended fertilizer i s l oaded di rect l y i nt o appl i cat ors wi t h l arge flotation t i res
equi pped wi t h a spi nner (fan-type) spr eader a nd i mmedi at el y spr ead ont o
fields.
Vi br at i on i n t he pl ant after mi xi ng and dur i ng t r anspor t and spr eadi ng
may cause part i cl es t o segr egat e. Smal l er part i cl es sift downwar d i nt o t he
voi d spaces bet ween l ar ger part i cl es and collect at t he bot t om. Gr anul es ar e
segr egat ed as t hey ar e pr opel l ed t hr ough t he ai r by fan-type spr eader s.
Lar ge part i cl es t ravel f ar t her t han t he small part i cl es, causi ng uneven appli-
cat i on of nut r i ent s. Thus , part i cl e size i s an i mport ant consi der at i on i n
gr anul at i on (see Fi gur e 8.5). It i s r e c omme nde d t hat 100% of t he mat eri al s
be wi t hi n t he mesh r ange of 6 t o +1 6 , with at least 2 5 % and not mor e
t han 4 5 % of +8- mes h size.
Part i cl e har dness becomes a fact or dur i ng appl i cat i on because soft
gr anul es br eak up i nt o smal l er part i cl es. Pri l l ed ur ea part i cl es t end t o be
por ous and have t he lowest cr ushi ng st r engt h of t he c ommon mat eri al s
used for bul k bl endi ng. New gr anul at i on met hods for ur ea pr oduce ha r de r
gr anul es, compar ed t o prills, and have significantly decr eased caki ng of
ur ea. Part i cl es t hat r emai n i nt act when pressed by t he forefi nger agai nst a
ha r d surface ar e consi der ed t o have satisfactory har dness.
FIGURE 8.5 The poor granule-size match on the right caused di ammoni um
phosphate to segregate from the larger, coarse potassium chl ori de particles.
(Photographs courtesy International Fertilizer Devel opment Center, TVA. )
Fl u i d Fe r t i l i z e r s
Fl ui d fertilizers ar e of t wo types; sol ut i ons and suspensi ons. T h e i mpor t ant
advant ages of pr oduci ng and mar ket i ng fluids ar e t he simplicity of t he
mi xi ng facilities and ease of handl i ng. Th e fluids t hemsel ves ar e dustless,
a nd t hei r ot her advant ages i ncl ude homogenei t y, uni formi t y of appl i cat i on,
t he ease with whi ch mi cr onut r i ent s or pesticides ar e added, t he ease wi t h
whi ch fluids ar e appl i ed wi t h i rri gat i on wat er , and t hei r use as foliar sprays.
Di sadvant ages i ncl ude lower-analysis pr oduct s, i ncr eased shi ppi ng costs,
a nd t he possibility of salting out at low t e mpe r a t ur e (see Fi gur e 8.6).
Liquid Fertilizers
A liquid fertilizer is a cl ear sol ut i on cont ai ni ng pl ant nut r i ent s. Th e pri nci -
pal i nt er medi at es used for maki ng liquid NPK fertilizers ar e ur ea, UAN
( u r e a - a mmo n i u m ni t r at e) sol ut i on, a mmoni um and or t hophos phat e or
pol yphosphat e sol ut i ons, and f i nel y gr ound sol ubl e KC1. Th e liquid fertil-
izers usually have a br own or gr een col or der i ved from t he wet -process
phosphor i c acid used i n t hei r pr epar at i on.
Th e most i mpor t ant sour ce of P i s a mmoni um pol yphosphat e, APP.
Ammoni a and low-cost, wet -process super phosphor i c acid ar e neut r al i zed
i n a pi pe r eact or . Th e heat pr oduced dri ves off most of t he wat er , and t he
hi gh t emper at ur e forms pol yphosphat es i n t he APP mel t . T h e APP mel t i s
processed i nt o 10-34-0 or 11-37-0 sol ut i ons i n whi ch 50% t o 7 5 % of t he P i s
pol yphosphat e. Th e pol yphosphat e has hi gher P cont ent and sequest ers
(hol ds i n sol ut i on) bot h i mpur i t i es of t he acid and any mi cr onut r i ent s t hat
FIGURE 8.6 Simplicity of manufacture and ease of handl i ng are the primary
reasons for the popularity of fluid fertilizers produced at rural fertilizer plants
such as this one.
ar e added. It i s a si mpl e mi xi ng process t o make liquid NPK fertilizer wi t h
APP sol ut i on by addi ng some UAN sol ut i on t o i ncrease t he N cont ent and
by addi ng finely gr ound KCl to supply K.
Th e maj or l i mi t at i on of liquid fertilizers i s t hei r general l y l ower analy-
sis compar ed t o dr y fertilizers. For NP fertilizers, hi gher concent r at i ons of
N and P ar e pr oduced usi ng UAN sol ut i on t han usi ng ur ea. For NPK liquid
fertilizers, hi gher gr ades ar e pr oduced usi ng ur ea r at her t han UAN solu-
t i on. Ur ea pr oduces hi gher gr ades because N H 4 N O 3 react s wi t h KC1 i n
sol ut i on t o pr oduce NH4 Cl and KNO3 . Pot assi um ni t r at e has low solubility
at low t emper at ur e, and crystals form and settle, or t he fertilizer salts out .
Thi s i s mor e of a pr obl em i n t he nor t he r n states t han i n t he sout her n. Most
of t he popul ar liquid fertilizers have sal t i ng-out t emper at ur es of 0 degr ees
C or l ower.
Suspension Fertilizers
Th e general l y low analysis of liquid fertilizers i s over come by t he manuf ac-
t ur e of suspensi ons. Suspensi on fertilizers cont ai n solids hel d i n suspensi on.
Th e suspended part i cl es may be wat er-sol ubl e i n a sat ur at ed sol ut i on, insol-
ubl e or bot h. Hi gher analysis, l ower - pr oduct i on cost, and resi st ance t o
salting out ar e advant ages of suspensi ons compar ed t o liquids. Suspensi on
fertilizers ar e part i cul arl y desi rabl e i n r egi ons wher e hi gh rat es of fertilizer
K ar e common. A di sadvant age is t he need for specialized appl i cat ors; most
suspensi on fertilizers must be appl i ed by cust om appl i cat ors.
Manuf act ur e of suspensi ons i s highly vari ed, but t he process has many
parallels t o liquid manuf act ur e. Similar mat eri al s ar e used, but t hey may be
l ower i n qual i t y and cost less. Th e most c ommon suspensi on agent i s at t a-
pul gi t e clay. T h e usual suspensi on cont ai ns 1% t o 2% clay, whi ch forms a
gel on vi gor ous agi t at i on. Part i cl es t hat settle dur i ng st or age ar e easily
r esuspended when agi t at ed. Suspensi ons may be st or ed weeks or mont hs ,
but i f t hey ar e st or ed t oo l ong, l arge crystals t hat cannot fl ow pr oper l y
t hr ough t he appl i cat ors will gr ow.
A D D I T I O N A N D
I N C O R P O R A T I O N O F MI C R O N U T R I EN T S
Re c omme nde d amount s of mi cr onut r i ent s ar e usually less t han 10 k g / h a
(about 9 pounds / a c r e ) , whi ch makes i t difficult t o appl y t hem separat el y
and uni formi l y i n t he f i el d. For this r eason mi cr onut r i ent s ar e usually
appl i ed i n mi xed fertilizers r at her t han separat el y. Compat i bi l i t y and uni -
f or m di st r i but i on ar e t he maj or objectives of t he successful addi t i on of
mi cr onut r i ent s t o mi xed fertilizers.
Ad d i t i on t o Gr a nu l a r Fe r t i l i z e r s
Th e addi t i on of mi cr onut r i ent s dur i ng t he manuf act ur e of a gr anul ar NPK
fertilizer or as one of t he i nt er medi at es dur i ng bul k bl endi ng pr ovi des gr eat
fl exi bi l i t y, and t he cost i s low. Th e mi cr onut r i ent gr anul e size must mat ch
Addition and Incorporation of Micronutrients 171
t hat of t he ot her mat eri al s i n bul k bl ends t o pr event segr egat i on dur i ng
mi xi ng, t r anspor t , a nd appl i cat i on. T h e rel at i ve numbe r of mi cr onut r i ent
gr anul es compar ed t o t he t ot al numbe r of gr anul es i n t he fertilizer i s very
small, whi ch means t hat t he mi cr onut r i ent gr anul es ar e widely spaced aft er
appl i cat i on. For exampl e, t he use of 8-mesh gr anul es at a r at e of 1 k g / h a
woul d pr ovi de about one gr anul e per 1 000 c m
2
of t he f i el d surface. Some
gr anul es woul d be t oo far away t o hel p some pl ant s and per haps, dependi ng
on t he mat eri al , rel ease t oo much of t he mi cr onut r i ent t o ot her pl ant s. Even
so, bul k bl endi ng of mi cr onut r i ent i nt er medi at es wi t h mi xed fertilizers i s
popul ar .
Addi ng mi cr onut r i ent s as a spray or powder dur i ng t he manuf act ur i ng
process pr i or t o ammoni at i on and gr anul at i on, gives t hem pr esence i n
every gr anul e. T h e pr obl ems of segr egat i on and uni formi t y of di st r i but i on
ar e solved, but t he mi cr onut r i ent i nt er medi at e may r eact unfavorabl y wi t h
ot her i nt er medi at es. Ext r a pr ecaut i ons ar e needed t o mai nt ai n good physi-
cal pr oper t i es of t he f i ni shed pr oduct and keep t he mi cr onut r i ent available.
Whe n a chel at ed mi cr onut r i ent , Zn EDTA for exampl e, i s mi xed wi t h su-
per phos phat e bef or e ammoni at i on, acid decomposi t i on of t he chel at e mol e-
cul e decreases t he availability of t he Zn. Whe n t he process i s changed by
addi ng t he Zn EDTA wi t h t he ammoni at i ng sol ut i on, t he Zn becomes mor e
avai l abl e.
Th e maj or di sadvant age of i ncor por at i ng mi cr onut r i ent s dur i ng man-
uf act ur e is t hat t her e is little flexibility, and it is costly to st or e many gr ades
wi t h a vari et y of mi cr onut r i ent s. If t her e is a regi onal deficiency of a
nut r i ent , this met hod may be t he most economi cal .
Mi cr onut r i ent s ar e coat ed t o gr anul ar pr oduct s t o achi eve a uni f or m
di st r i but i on of t hem t hr oughout t he fertilizer. A fi nel y gr ound mi cr onu-
t r i ent , less t han 100 mesh in size is dr y- mi xed wi t h fertilizer gr anul es, t hen
spr ayed with a liquid bi nder and given addi t i onal mi xi ng. Mechani cal adhe-
sion or t he f or mat i on of r eact i on pr oduct s on t he surface of t he fertilizer
gr anul es makes t he mi cr onut r i ent coat i ng adher e t o t he gr anul es. Bi nder s
i ncl ude wat er, oils, waxes, a mmoni um pol yphosphat e, and UAN sol ut i ons.
Wat er may be used i f i t pr esent s no caki ng hazar d. Oil shoul d not be added
t o N H 4 N O 3 because t he subst ances t oget her mi ght expl ode. No mor e t han
1% oil shoul d be used because t he oil may seep t hr ough fertilizer bags.
I ncor por at ed and coat ed mi cr onut r i ent s appear t o be similar i n agr o-
nomi c effectiveness. T h e coat i ngs do not affect t he availability of t he mi-
cr onut r i ent s, and t hey pr ovi de mor e f l exi bi l i t y compar ed t o i ncor por at i on
dur i ng manuf act ur e. A di sadvant age of coat i ng, compar ed t o i ncor por a-
t i on, i s hi gher cost. Mi cr onut r i ent s ar e not widely coat ed i n t he Uni t ed
St at es.
Ad d i t i on t o Fl u i d Fe r t i l i z e r s
T h e addi t i on of mi cr onut r i ent s t o f l ui d fertilizers has become very popul ar
because t he mi cr onut r i ent s can be added j ust bef or e t he fertilizer i s appl i ed
i n t he fi el d. T h e fact t hat t hese fertilizers ar e used i mmedi at el y allows for
gr eat flexibility in manuf act ur e; a wi de vari et y of fertilizers wi t h mi ni mal
st or age r equi r ement s can be pr oduced. Th e addi t i on of mi cr onut r i ent s t o
liquid fertilizers, however , i s great l y l i mi t ed by t he solubility of t he i nt er-
medi at es. Onl y sodi um bor at e and sodi um mol ybdat e have sufficient solu-
bility to be effective when t he P sour ce is or t hophos phat e. Metallic sources
of mi cr onut r i ent ar e mor e soluble i n pol yphosphat e t han i n or t hophos phat e
i n clear fertilizer sol ut i ons. Even so, t he solubility of salts of Cu, Fe, Mn, and
Zn ar e general l y t oo low t o cor r ect severe deficiencies at usual fertilizer
appl i cat i on rat es. Sequest er i ng agent s t hat r eact wi t h t he mi cr onut r i ent s
have been used t o pr event t hei r pr eci pi t at i on by phosphat e. Ammoni um
pol yphosphat e effectively sequest ers all t he met al l i c mi cr onut r i ent s except
Mn. It is easy to cust om- mi x liquid fertilizers cont ai ni ng a vari et y of ki nds
and amount s of mi cr onut r i ent s. A di sadvant age of some i s t hat r at es of
fertilizer appl i cat i on may not allow sufficient amount s of t he mi cr onut r i ent
t o be appl i ed t o cor r ect cer t ai n deficiencies.
Mi cr onut r i ent i nt er medi at es ar e easily a dde d t o suspensi on fertilizers
with mi ni mal r eact i on wi t h ot her component s or ot her undesi r abl e resul t s.
Sulfates of Cu, Fe, Mn, and S i n fri t t ed f or m have been used. Suspensi ons
shoul d be appl i ed soon aft er pr epar at i on t o avoi d set t l i ng difficulties a nd
crystal gr owt h.
SALT I N D EX
Fertilizers ar e composed for t he most par t of sol ubl e salts t hat i ncrease t he
ion concent r at i on of t he soil sol ut i on. Thi s hi gher i on concent r at i on in-
creases t he osmot i c pr essur e of t he soil sol ut i on and at t he same t i me
decreases t he wat er pot ent i al . Decreases i n wat er pot ent i al ar e associated
with decreases i n t he r at e at whi ch r oot s and seeds absor b wat er . Pl acement
of fertilizer close t o seeds and r oot s may r educe ger mi nat i on and gr owt h
(see Fi gur e 8.7).
Th e salt i ndex i s a meas ur e of t he ext ent t o whi ch vari ous fertilizers or
i nt er medi at es i ncrease t he osmot i c pr essur e of t he soil sol ut i on. Briefly, t he
salt i ndex i s det er mi ned by addi ng fertilizer t o soil and i ncubat i ng for fi ve
days. Th e n t he osmot i c pr essur e of t he di spl aced soil sol ut i on i s det er -
mi ned. T h e salt i ndex i s a rel at i ve val ue compar ed t o Na NO3 as 100, and
t he values of t he most widely used mat eri al s ar e given i n Tabl e 8. 3. Ni t r o-
gen and K salts have much hi gher salt i ndexes t han P salts. T h e cultivar,
pl acement of t he fertilizer, t i me of appl i cat i on, and soil pr oper t i es, and t he
wat er cont ent in par t i cul ar will have some bear i ng on what effect a fertilizer
with a given salt i ndex has. T h e salt i ndex has its great est val ue when
gr ower s ar e selecting fertilizers t hat will be pl aced with or near seeds.
A C I D I T Y A N D B ASI CI T Y
Acids ar e i mpor t ant i nt er medi at es i n fertilizer manuf act ur e and raise t he
possibility t hat fertilizers can al t er soil p H. Whe n ur ea i s hydr ol yzed t o
N H 4
+
, t he pH i n t he i mmedi at e vicinity of appl i cat i on may i ncrease t o 9.
Acidity and Basicity 173
FIGURE 8. 7 Fertilizer pl aced with or cl ose to the
wheat seeds on the left, at a rate comparabl e to 200
pounds per acre ( 224 kilograms per hectare), caused a
delay in germi nati on.
Lat er , t he N H 4
+
may be absor bed by r oot s or nitrified wi t h t he pr oduct i on
of pr ot ons . Whe t he r N i s t aken up by r oot s as ni t r at e or a mmoni um affects
t he a mount of H
+
or O H
-
excr et ed by r oot s. Leachi ng of t he ni t r at e
r esul t i ng from fertilizer use depl et es XCa. . Na. T h e effects of fertilizers on
soil pH ar e compl ex because t he out come i s i nfl uenced by pl ant gr owt h,
soil, and l eachi ng. William Pi er r e di d much of t he earl y wor k and from
gr eenhous e st udi es dr ew his concl usi ons about t he effect of fertilizers on
soil p H. His wor k forms t he pr i mar y basis of t he me t hod adopt ed by t he
TABLE 8. 3 Salt Indexes of Fertilizer Materials
Material and grade Salt index Index per unit*
Ammonium nitrate, 34-0-0 102 2.90
Ammonium sulfate, 21-0-0 69 3.25
Anhydrous, 82-0-0 47 0.57
Sodium nitrate, 16-0-0 100 6.06
Urea, 45-0-0 73 1.56
Monoammonium phosphate, 11-55-0 27 0.41
Diammonium phosphate, 18-46-0 29 0.45
Superphosphate, 0-20-0 8 0.39
Superphosphate, 0-45-0 10 0.22
Potassium chloride, 0-0-60 116 1.94
Potassium nitrate, 14-0-47 74 1.22
Potassium sulfate, 0-0-54 46 0.85
*Per 20 pounds or 9 kg of N + P 2 O5 + K2 O.
Source: Adapt ed from Rader, Whi te, and Whittaker, 1943.
Association of Official Agr i cul t ur al Chemi st s t o det er mi ne t he acidity or
basicity of fertilizers.
Th e acidity or basicity of a fertilizer i s expr essed as uni t s of Ca CO3
equi val ent t o t he acidity or basicity pr oduced by t he fertilizer. It i s assumed
(1) t hat Cl, S, and one- t hi r d of t he N cont r i but e to soil acidification, (2) t hat
t he Ca, Mg, K, and Na cat i ons cont r i but e t o soil basicity; and (3) t hat half of
t he N is absor bed by pl ant s as ni t ri c acid and half is absor bed as a salt, such
as KNO3 . Thus , KNO3 and Ca ( NO3 ) 2 ar e basic and KCl i s neut r al . T h e N
carri ers with an acidic ani on ar e qui t e aci d-formi ng. In gener al , it is t he N
car r i er s wi t h t hei r acidity pot ent i al t hat affect soil pH (see Tabl e 8.4).
A single appl i cat i on of a NPK fertilizer is unlikely to have any det ect -
abl e effect on soil pH. Long- t i me use of N H 3 i n a cont i nuous cor n pr ogr am,
however , may severely l ower pH of acid soils (see Chapt er 10). A maj or
l i mi t at i on of t he acidity values is t hat , because losses by l eachi ng, denitrifi-
cat i on, and volatilization vary, t her e ar e gr eat vari at i ons i n t he fate of
fertilizer N. Some aci d-formi ng fertilizers may pr oduce beneficial effects
when used on al kal i ne or cal careous soils by i ncreasi ng t he solubility of
some mi cr onut r i ent s.
A quant i t at i ve meas ur ement of acidity and basicity enabl es fertilizer
manuf act ur er s t o add some l i mest one t o t he fertilizer as a fi l l er t o count er -
act acidity. It i s general l y mor e economi cal t o add l i mest one t o soils, as
compar ed to pr oduci ng neut r al fertilizers, if soil acidity becomes a pr obl em
when t he fertilizer is used.
F ERT I LI Z ER A N D P EST I CI DE C O MB I N A T I O N S
Th e appl i cat i on of pesticides with fertilizers has obvi ous economi c advan-
t ages. Fewer t ri ps r educe traffic and may r educe soil compact i on. Th e
maj or consi der at i ons of combi ni ng pesticides with fertilizers ar e
TABLE 8.4 Equivalent Acidity(A) or Basicity(B) of Selected
Fertilizers
Fertilizer Grade A or B
Equivalent Ca C0 3
per unit of N*
( NH4 ) 2 SO4 20.5-0-0 A 107
NH4 NO3 33.5-0-0 A 36
NH3 82-0-0 A 36
Urea 46-0-0 A 36
N solution 32-0-0 A 36
Ca(NO3 )2 16-0-0 B 22
KNO3 13-0-44 B 40
NH4 H2 PO4 11-48-0 A 36
( NH) 2 HPO4 18-46-0 A 36
Superphosphate
-
neutral 0
KC1 0-0-60 neutral 0
*Per 20 pounds or 9 kg of N.
Source: Data from Terman, 1982.
Fertilizer and Pesticide Combinations 175
1. T h e appr opr i at eness of t he t i mi ng and pl acement of t he combi nat i on.
2. Chemi cal and physical compat i bi l i t y.
3. Whe t he r t he i nt er act i on of pest i ci de and fertilizer al t ers t hei r
effectiveness.
4. Met al cor r osi on and det er i or at i on of hoses and ot her equi pment .
He r b i c i d e a nd Fe r t i l i z e r Comb i na t i on
Since t he earl y 1970s t he popul ar i t y of her bi ci de and fertilizer combi na-
t i ons has fost ered t he weed and feed concept . One of t he most i mpor t ant
consi der at i ons i s choosi ng t he t i me t hat t he her bi ci de- f er t i l i zer combi na-
t i on shoul d be appl i ed for t he gr eat est effectiveness of each. For many cr ops
it is cust omar y to split t he N appl i cat i on, whi ch oft en means t hat t he t i me of
appl i cat i on for bot h N and her bi ci de i s at pr epl ant i ng, pl ant i ng, or post-
emer gence. Th e most popul ar combi nat i ons ar e N sol ut i ons, UAN, and
herbi ci des such as f l uomet ur on for cot t on and at r azi ne or si mazi ne for
cor n. Ni t r ogen sol ut i on pl us 2, 4-D i s used t o cont r ol weeds i n small grai ns,
s or ghum, and past ur es. T h e N readi l y moves i nt o t he soil wi t h wat er , and
t he surface appl i cat i on of t he her bi ci de i s effective. Th e l ar ger quant i t y of
f l ui d may pr ovi de mor e uni f or m appl i cat i on and r e nde r t he her bi ci de mor e
effective. An appl i cat i on of 140 t o 190 L / h a of UAN used as a car r i er
supplies N at 50 t o 68 k g / h a ( 4 5 - 6 1 pounds / a c r e ) .
Pos t emer gence appl i cat i on causes leaf bur n unless dr op nozzles ar e
used t o di rect t he sol ut i on bel ow t he leaves. Bur n injury i ncreases with t he
r at e of appl i cat i on and i s gr eat er for advanced stages of pl ant gr owt h.
Gr ower s may express concer n about leaf bur n. I f t he leaf bur n occurs earl y
i n t he season, yield may not decr ease significantly. It has been r epor t ed t hat
as much as 134 k g / h a ( 120 pounds / a c r e ) of N has been appl i ed via UAN
on four-leaf cor n wi t hout r educi ng cor n yields. Appl i cat i on aft er t he six-
leaf st age, however , shoul d be r egar ded as a salvage oper at i on.
Pr obl ems of i ncor por at i ng herbi ci des with fl ui d fertilizers i ncl ude pr e-
ci pi t at i on of salts, f or mat i on of t hi xot r opi c gels, and an i ncrease i n t he
sal t i ng-out t emper at ur e of liquids. T h e her bi ci de shoul d be mi xed j ust
bef or e appl i cat i on t o mi ni mi ze pr obl ems. It shoul d also be cont i nuousl y
agi t at ed. A simple field test can be conduct ed to obt ai n some visible evi-
dence of compat i bi l i t y.
1. Pl ace a liter or pi nt of t he fluid fertilizer in a j ar .
2. Add an a mount of t he her bi ci de t o equal t he pr opor t i on of t he
f or mul at i on.
3. Shake t he j a r and i mmedi at el y obser ve separ at i on or gelling. Repeat t he
obser vat i on i n 30 mi nut es.
If an emulsifier i s t o be used, t he test can det er mi ne t he effectiveness of
addi ng t he emulsifier.
Some changes ar e not visible and may appear only when t he effective-
ness of t he her bi ci de i s measur ed. Many herbi ci des ar e compl ex or gani c
mol ecul es t hat have many r eact i on sites for adsor pt i on and r eact i on wi t h
fertilizer salts. Her bi ci dal act i on may be i ncr eased or decr eased. At t apul gi t e
clay i n suspensi on adsor bs par aquat and r ender s i t ineffective.
Her bi ci des ar e also i ncor por at ed i nt o dr y fertilizers. T h e herbi ci des,
di ni t roani l i nes and car bamat es, ar e spr ayed on or i mpr egnat ed i nt o t he
fertilizer j ust bef or e appl i cat i on. Thes e combi nat i ons ar e spr ead on t he soil
and i ncor por at ed by subsequent tillage. Addi ng dr y gr anul ar herbi ci des t o
gr anul ar fertilizers creat es some of t he same segregat i on and r eact i on pr ob-
lems encount er ed i n addi ng gr anul ar mi cr onut r i ent s t o gr anul ar fertilizers.
In addi t i on, t he effectiveness of t he her bi ci de i s likely t o be r educed i n
pr ol onged st orage of gr anul ar combi nat i ons.
Ins e c t i c i de a nd Fe r t i l i z e r Comb i na t i on
Th e combi nat i on of fluid fertilizers wi t h herbi ci des has been much mor e
successful t han t hei r combi nat i on wi t h insecticides. General l y, insecticides
ar e appl i ed t o t he foliage and fertilizers ar e appl i ed t o t he soil. On e applica-
t i on, al t hough not very popul ar , is t he use of a liquid st ar t er fertilizer
insecticide combi nat i on t o cont r ol cor n r oot wor m. Some pr obl ems encoun-
t er er d i ncl ude i ncompat i bi l i t y of mat eri al s, phyt ot oxi ci t y, and poor
insecticide per f or mance.
REF ERENCES
Engelstad, O. P., ed. 1985. Fertilizer Technology and Use. 3rd ed. Soil Sci. Soc. Am.,
Madison, Wis.
Follett, R. H., L. S. Murphy, and R. L. Donahue. 1981. Fertilizers and Soil Amend-
ments. Prent i ce-Hal l , Englewood Cliffs, N. J .
Hoffmeister, G. 1979. Physical Properties of Fertilizers and Methods for Measuring
Them. Bull. Y-147, TVA, Muscle Shoals, Ala.
International Fertilizer Development Center. 1979. Fertilizer Manual. TVA, Muscle
Shoals, Ala.
Jones, U. S. 1982. Soil Fertility and Fertilizers. Prent i ce-Hal l , Reston, Va.
National Fertilizer Development Center. 1983. Fertilizer Trends 1982. TVA, Muscle
Shoals, Ala.
Pierre, W. H. 1933. Determination of Equivalent Acidity and Basicity of Fertilizers.
Industrial and Eng. Chem. 5: 229- 234.
Rader, L. F., L. M. White, and C. W. Whittaker. 1943. The Salt Index: A Measure
of the Effect of Fertilizers on the Concentration of the Soil Solution. Soil Sci.
55: 201- 208.
Terman, G. L. 1982. Fertilizer Sources and Composition. In Handbook of Soils and
Climate in Agriculture. CRC Press, Boca Raton, Fla.
Tisdale, S. L., W. L. Nelson, and J. D. Beaton. 1985. Soil Fertility and Fertilizers. 4th
Young, R. D. 1983. Mixed Fertilizers. Mimeo. TVA, Muscle Shoals, Ala.
C H A P T E R 9
Soil Fertility Evaluation
An eval uat i on of soil fertility is based on observat i ons and tests of bot h soils
and pl ant s. Two pr i mar y pur poses of t he tests ar e t o make fertilizer r ecom-
mendat i ons and t o measur e t he effectiveness of fertilizer pract i ces. Soil tests
can be car r i ed out bef or e cr ops ar e pl ant ed and ar e t he basis of fertilizer
r ecommendat i ons for most annual fi el d and veget abl e crops. Pl ant analysis
is a popul ar way to make r ecommendat i ons for per enni al crops, for sampl es
of tissue ar e col l ect ed after cr ops ar e est abl i shed, and t her e i s a l ong t i me
aft er t est i ng for nut r i ent accumul at i on and gr owt h. I n addi t i on, t he r oot s of
per enni al s, t r ee crops for exampl e, ar e pe r ma ne nt resi dent s t hr oughout a
very l arge vol ume of soil, whi ch makes soil sampl i ng difficult. Bot h ki nds of
tests and pl ant deficiency sympt oms ar e used for di agnost i c pur poses.
P LA N T DEF I CI ENCY S YMP T O MS
Pl ant s, like ani mal s, exhi bi t uni que sympt oms t o vari ous nut r i ent deficien-
cies. Li ght gr een or yel l ow-col ored leaves and slow gr owt h ar e c ommon
ni t r ogen deficiency sympt oms of lawns. Ni t r ogen, P, K, and S ar e mobi l e i n
pl ant s and ar e readi l y moved from t he ol der and l ower leaves t o t he upper
or newl y f or med par t s of pl ant s when a deficiency occurs (see Fi gur e 9.1).
In fact, i t i s nor mal for mobi l e nut r i ent s t o accumul at e i n t he veget at i ve
par t s and be moved t o t he fruit bef or e har vest t i me. As N i s r emoved from
t he leaves of cor n for grai n devel opment late i n t he season, yellowing and
deat h of t he l ower leaves i s nor mal . Deficiency sympt oms of mobi l e nu-
t r i ent s appear fi rst on t he l ower leaves or ol dest tissues. By cont rast , B, Ca,
Cu, Fe, and Mn ar e qui t e i mmobi l e i n pl ant s, and deficiency sympt oms
appear f i r st on t he most recent l y f or med leaves or tissues.
Deficiency sympt oms ar e useful i n di agnosi ng pl ant gr owt h pr obl ems
and in sel ect i ng sites for soil fertility exper i ment s. If det ect ed early enough
177
178 Soil Fertility Evaluation
FIGURE 9.1 Ni t rogen deficiency symptom of corn
(maize) is a yellow midrib of the l ower leaves. Eventually,
the entire leaf may turn yellow and di e.
i n t he season, deficiency sympt oms can be consi der ed when deci di ng
whet her an addi t i onal amount of fertilizer shoul d be appl i ed. Somet i mes
deficiency sympt oms appear earl y i n t he season and t hen di sappear, wi t h no
appar ent r educt i on i n yield. On t he ot her hand, cer t ai n deficiency symp-
t oms may appear i n mi dseason or l at er and be associated with yield r educ-
t i ons as l arge as 50 per cent .
SOI L T EST S
Th e tests for soil pH and lime r equi r ement s and t he r ecommendat i ons for
l i mi ng ar e consi der ed i n Chapt er 3. He r e t he emphasi s i s on t he use of tests
and pr ocedur es desi gned t o make fertilizer r ecommendat i ons .
Th e pr i mar y objective of usi ng a fertilizer is to make a profit. Th e
economi cal use of fertilizer depends on knowl edge t hat can r el at e t he use of
fertilizer t o a pr edi ct ed i ncrease i n yield. Soil can be sampl ed and t est ed and
fertilizer r ecommendat i ons devel oped bef or e t he gr owi ng season begi ns.
Thi s i s of par t i cul ar i mpor t ance t o crops t hat have only about 100 days t o
Soil Tests 179
gr ow and accumul at e nut r i ent s. Since yields ar e also a funct i on of cl i mat e
and management , t he effects of cl i mat e and management must also be
i nt egr at ed i nt o fertilizer r ecommendat i ons . A soil-testing pr ogr a m de-
si gned t o make fertilizer r ecommendat i ons typically has f our par t s: (1)
sampl e collection, (2) chemi cal analysis, (3) i nt er pr et at i on of t he chemi cal
tests, and (4) r ecommendat i ons based on t he tests for t he crops t o be gr own.
Soi l Sa mp l i ng
Most soil tests use only 0.1 to 5 gr ams of soil, yet t he vol ume of soil
r epr es ent ed will likely exceed 10000 t ons. Th e ability t o obt ai n a t rul y
r epr esent at i ve sampl e still r emai ns one of t he weakest links i n eval uat i ng
soil fertility. I nst r uct i ons for sampl i ng shoul d be obt ai ned from t he soil-
t est i ng l abor at or y. Th e l abor at or y will suppl y t he f ar mer with fi el d infor-
mat i on sheet s and soil sampl e cont ai ner s as well as t he pr oper i nst ruct i ons.
Four t hi ngs ar e needed for sampl i ng: sampl i ng t ool ssoi l sampl i ng t ube,
auger , or shovel; a cl ean pai l pl ast i c will r educe t he l i kel i hood of mi cr o-
nut r i ent cont ami nat i on; a fi el d i nf or mat i on sheet ; and soil sampl e
cont ai ner s.
Before obt ai ni ng a sampl e, eval uat e t he field for uni formi t y of soil
charact eri st i cs and past management pract i ces. A sampl i ng uni t or ar ea
shoul d be qui t e uni f or m i n t he charact eri st i cs t hat affect yields. T h e size of
t he sampl i ng uni t may vary but shoul d general l y be fi el d size or sufficiently
l arge t hat i t can be fertilized differently from ot her areas. Avoi d sampl i ng
small areas of unusual dr ai nage, ar eas t hat have unde r gone unusual man-
agement i n t he past, or sites wher e ma nur e or lime piles have been l ocat ed.
T h e sampl i ng ar ea shoul d be sket ched on t he field i nf or mat i on sheet and a
label put on t he cont ai ner s t hat will identify t he sampl es and associate t hem
with t he fi el d. Unusual ar eas may be sampl ed separat el y i f t he f ar mer so
desi res. Th e sampl e shoul d r epr esent t he pl ow layer wher e convent i onal
tillage i s used. Fr om t he sampl i ng ar ea obt ai n 20 t o 30 cores t hat ar e
uni f or m i n size and r epr esent t he same soil dept h. Obt ai n t he cores at
r a ndom as shown i n Fi gur e 9. 2.
Fert i l i zer car r yover and bui l dup of fertility mean t hat sampl es cont ami -
nat ed wi t h soil from bel ow pl ow layer will t end t o be bi ased t o test l ower for
P and K. As shown in Chapt er 5, t he P levels of t he pl ow layers of many
fields is now so hi gh t hat P fertilizers ar e not r e c omme nde d. No-till systems
have cr eat ed gr eat er P soil test gr adi ent s in t he upper 15 cm of soils, as
compar ed to convent i onal tillage, because surface-appl i ed P has l i mi t ed
mobi l i t y. Acidity pr oduced by N fertilizer use has similarly cr eat ed pH
gr adi ent s in t he upper few cent i met er s of soil. As a consequence, some
l abor at or i es r e c omme nd a sampl i ng dept h of 0 t o 7. 5 cm for no-till and
disk-tilled fields. In Geor gi a a 10-cm sampl i ng dept h is r e c omme nde d for
no-till fi el ds, past ur es, lawns, and turf. Addi t i onal r esear ch i s needed t o
devel op bet t er sampl i ng t echni ques and fertilizer and l i me r ecommenda-
tions for no-till fields.
FIGURE 9. 2 Exampl e of how to lay out a field for soil
sampling.
Ni t r at e and sulfate sulfur t end t o be qui t e mobi l e i n soils, and deeper
sampl i ng i s r equi r ed i n or der t o test t hem. Several Gr eat Plains states
r e c omme nd sampl i ng at 60 t o 120 cm i n t est i ng for available N (ni t rat e).
Sampl i ng t o 60 cm i s encour aged i n t he Canadi an Pr ai r i e Provi nces for
t est i ng of ni t r at e, sulfate, and soil salinity.
Place t he cores in a cl ean pail and t hor oughl y mi x. Fill t he soil sampl e
cont ai ner ; t hen send t he sampl e and t he f i el d i nf or mat i on sheet t o t he
soil-testing l abor at or y. If a ni t r at e test is r equest ed, moi st soil sampl es
shoul d be quickly dr i ed wi t hout t he use of artificial heat bef or e t he sampl es
ar e shi pped. Thi s dr yi ng will mi ni mi ze any change i n ni t r at es t hr ough
f ur t her mi crobi ol ogi cal activity. Al l owi ng sampl es to ai r-dry slowly is gener -
ally accept abl e because most l abor at or i es dr y and pul veri ze t he sampl es
bef or e t est i ng. In any case, i t i s i mpor t ant t o follow t he i nst ruct i ons of t he
t est i ng l ab because t hei r i nt er pr et at i on of soil test resul t s is based on a
pr escr i bed handl i ng of sampl es.
Seasonal t r ends i n soil test resul t s have been r epor t ed. T h e seasonal
t r end has been t he most consi st ent for K. Soil sampl es t aken dur i ng t he
gr owi ng season will often test l ower t han sampl es t aken i n t he wi nt er or
early spri ng. Illinois adjusts its K soil test resul t s on sampl es t aken bet ween
Soil Tests 181
Sept ember 30 and May 1. For most soils t he seasonal t r ends ar e small, and
for r out i ne soil tests sampl i ng i s encour aged whenever i t can be done. Most
soil test l aborat ori es r e c omme nd t hat sampl i ng and t est i ng be done every
t wo t o four years.
Ty p e s of Te s t s
T h e ki nds of tests available depend on local soil and cr op condi t i ons. A
s t andar d test usually i ncl udes available P, exchangeabl e K, Ca, and Mg. It
also i ncl udes t hei r sat ur at i on per cent ages, t he CEC, pH, and lime r equi r e-
ment . Gr eenhous e tests usually i ncl ude, i n addi t i on, salinity a nd ni t r at e
ni t r ogen. Some l abor at or i es test for or gani c mat t er cont ent , salinity, sul-
fate, and cer t ai n mi cr onut r i ent s and heavy met al s. Some labs also offer tests
for wat er quality.
Soi l Te s t Cor r e l a t i on
A good soil test for a nut r i ent will effectively meas ur e a quant i t y t hat will
closely cor r el at e wi t h t he amount of t he nut r i ent t hat pl ant s will t ake up;
t hus, it will also cor r el at e well with yields. Thi s soil fraction of t he nut r i ent
i s typically r ef er r ed t o as t he available fract i on. Gr eenhous e exper i ment s
can be used t o do much of t he pr el i mi nar y wor k i n sel ect i ng t he most
efficient soil test met hod. T h e devel opment of a soil test cor r el at i on pr o-
gr am r equi r es f i el d exper i ment s t hat accompl i sh four t hi ngs. First, exper i -
ment al t r eat ment s must be repl i cat ed. Second, t r eat ment s must i ncl ude
rat es of appl i cat i on for a given nut r i ent el ement t o det er mi ne t he quant i t y
of fertilizer r equi r ed for maxi mum yield at a gi ven soil test level. Thi r d,
ot her gr owt h factors shoul d be managed t o obt ai n hi gh yields, i ncl udi ng an
adequat e suppl y of ot her nut r i ent s. Four t h, t he trials must be r epeat ed at
sufficient locations and numbe r of years t o est i mat e variability caused by
cl i mat e and l ocat i on (soil variability). T h e dat a from t he exper i ment s ar e
used t o const r uct fi gures, such as Fi gur e 9. 3, whi ch r el at e soil tests t o yields.
T h e use of rel at i ve yields r at her t han act ual yields enabl es all trials t o be
shown as one fi gure.
T h e dat a in Fi gur e 9.3 show t hat cot t on r equi r es a hi gher K soil test for
a gi ven rel at i ve yield t han does cor n, wher eas soybeans t end t o r equi r e an
i nt er medi at e amount . Similar st at ement s ar e commonl y made for P. For
i nst ance, small grai ns, alfalfa, and cl over r equi r e hi gher soil tests t han
soybeans or cor n for t he same rel at i ve yield. Mor eover , because of soil
differences, i ncl udi ng mi neral ogy, a K test of 20 for soils in gr oup 1 is as
effective as a test of 40 for soils in gr oup 3. T h e soil gr oupi ngs in this
exampl e ar e based on CEC, gr oups 1, 2, and 3 havi ng CECs of 10, 20, and
30 me q / 1 0 0 g, respectively. The s e resul t s from Al abama paral l el f i ndi ngs
in ot her st at es, namel y, t hat finer-textured soils must have a hi gher K test to
pr oduce t he same cr op yield as compar ed t o sandy soils. I n Ohi o t he desi r ed
or opt i mum K test i n pounds per acr e i s 220 pl us fi ve t i mes t he CEC. Thi s
FIGURE 9. 3 Correl ati on bet ween potassium soil tests and the relative
yields of crops grown on three soil groups i n Al abama. (Adapted from
Cope and Rouse, 1973. )
f or mul a wor ks out t o 270, 320, and 370 for soils with CECs of 10, 20, and
30 me q / 1 0 0 g. I n Geor gi a soils ar e gr ouped i nt o t hr ee cat egori es for
maki ng K r ecommendat i ons : (1) Coastal Plains soils, (2) Pi edmont , moun-
t ai n, and l i mest one valley soils, and (3) soils from l andscapi ng, golf gr eens,
gr eenhouses, and flower beds. Similar st udi es ar e conduct ed t o cor r el at e
soil P tests wi t h yields.
Soil test cor r el at i on dat a ar e conver t ed i nt o descri pt i ve t er ms and i nt o
useful i nt er pr et at i ons, as shown i n Tabl e 9. 1. Many di fferent soil test levels
ar e di fferent i at ed, dependi ng on need and si t uat i on. In Tabl e 9.1 a soil test
value associated wi t h a rel at i ve yield of less t han 50% of t he maxi mum is
consi der ed very low. Cr ops gr own on soils wi t h a very low soil test ar e
pr edi ct ed t o yield i n t he r ange of 0 t o 50% of t he maxi mum yield for t he
soil and cr op condi t i ons. Such soils may be t r eat ed wi t h l arge amount s of
fertilizer t o bui l d up soil fertility. Soil tests of low and medi um rat i ngs
r epr esent soils t hat ar e pr edi ct ed t o yield 50% t o 7 5 % and 7 5 % t o 100% of
maxi mum yield. Soils t hat test hi gh ar e expect ed t o pr oduce t he ma xi mum
yield wi t hout fertilizer. Ver y hi gh and ext r emel y hi gh levels i ndi cat e t hat
soils cont ai n mor e of t he nut r i ent i n available f or m t han i s needed t o
pr oduce t he maxi mum yield. Such levels ar e not unc ommon for gar den
sampl es. Ext r emel y hi gh soil tests may be associated wi t h nut r i ent toxicities,
nut r i ent i mbal ances, or envi r onment al cont ami nat i on. Thus , soil test cor r e-
lation exper i ment s pr ovi de t he i nf or mat i on t o cor r el at e tests of vari ous soils
with t he rel at i ve yield expect ed for vari ous crops. T h e next st ep i n maki ng a
specific fertilizer r ecommendat i on is to cal i brat e soil tests with yields pr o-
duced by varyi ng amount s of fertilizer.
Soil Tests 183
TABLE 9.1 Soil Test Rating, Relative Yield, and Recommendations
Rating
Relative yield,
percent Recommendations
Very low <50
Low 50- 75
Medium 75- 100
High 100
Very high 100
Extremely high 100?
Large applications for soil building
Annual applications to produce maximum
yield and increase soil fertility
Normal applications to produce maximum
yields
Small applications to maintain soil fertility
None until soil tests drop to high range
P may be excessive, contaminate the
environment, and cause Fe or Zn
deficiency
Source: Adapt ed from Cope and Rouse, 1973.
Ca l i br a t i on of Soi l Te s t s wi t h Yi e l d Re s p ons e s
Soil test cal i brat i on exper i ment s meas ur e t he cr op r esponse t o var yi ng rat es
of a fertilizer nut r i ent appl i ed to pl ot s wi t h vari ous soil test levels. The s e
exper i ment s pr ovi de t he dat a needed t o const r uct gr aphs like t he one gi ven
i n Fi gur e 9. 4. T h e l ower t he soil test, t he gr eat er t he a mount of fertilizer
needed t o pr oduce a par t i cul ar yield or t he ma xi mum yield. Knowi ng t he
cost of fertilizer and t he pri ce of t he cr op per mi t s a cal cul at i on a nd pr edi c-
t i on of t he a mount of fertilizer t hat will pr oduce t he yield t hat will i n t ur n
ear n t he ma xi mum profit.
I n pract i ce, f ar mer s ar e asked t o r ecor d t hei r yield goals on t he f i el d
i nf or mat i on sheet . Thi s val ue i s based i n par t on weat her expect at i ons,
pr evi ous and cur r ent management pract i ces, and soil condi t i ons. Th e n soil
cal i brat i on dat a ar e used t o r e c omme nd t he a mount of fertilizer t hat i s
pr edi ct ed t o pr oduce t he yield goal . Theor et i cal l y, maxi mum profit i s
ear ned with yields t hat ar e less t han t he maxi mum, usually at 90% t o 9 5 %
of t he maxi mum r ange.
FIGURE 9. 4 Typi cal yield responses from
nutri ent addi ti ons for medi um and low soil
test levels.
Th e curves i n Fi gur e 9. 5 r epr esent four di fferent fertilizer si t uat i ons.
Cur ve A is an adver se si t uat i on in whi ch yields wi t hout fertilizer ar e low,
and little pot ent i al exists for i ncreasi ng t he yield wi t h fertilizer. T h e fertil-
izer opt i mum r at e i s less t han t wo uni t s. Cur ves B, C, a nd D r epr esent
si t uat i ons wi t h i ncreasi ng yield pot ent i al ; differences i n yield pot ent i al s
coul d reflect differences i n soil charact eri st i cs, management , or weat her .
For cur ve C t he ma xi mum profit or opt i mum yield i s obt ai ned wi t h t he use
of 3.6 uni t s of fertilizer. Th e r e is a t endency to r e c omme nd a fertilizer r at e
t hat will pr oduce a yield near t he ma xi mum because wi t h underfert i l i zat i on
loss of profit is gr eat er t han with overfert i l i zat i on as shown in Tabl e 9. 2.
Subsoi l Te s t i ng
It i s general l y accept ed t hat subsoil wat er and nut r i ent s ar e i mpor t ant for
pl ant gr owt h. Even so, very few quant i t at i ve st udi es of t he i mpor t ance of
subsoil fertility have been made. The s e st udi es suggest t hat from 0% t o
80% of t he t ot al nut r i ent upt ake occur r ed i n t he subsoil. I n t he Uni t ed
States it is r out i ne in areas wi t h an ustic soil moi st ur e r egi me to test for
T A B L E 9. 2 Effect of Underfertilizing versus Overfertilizing on Net Returns
Difference
Yield Cost of Net from
Fertilizer Rate value nutrients return optimum
One-fourth less 2.7 120.5 8.1 46.4 - 4 . 3
Optimum 3.6 127.5 10.8 50.7 0
One-fourth more 4.5 129.0 13.5 49.5 - 1 . 2
Source: Adapt ed from Barber, 1973.
Plant Analysis 185
subsoil ni t r at e and use t he test resul t s for maki ng N fertilizer
r ecommendat i ons .
T h e i mpor t ance of subsoil fertility i s r el at ed t o t he r oot i ng habi t of
pl ant s, t he level of subsoil fertility, and t he moi st ur e condi t i ons of t he
subsoil. If t he ent i r e soil profile is kept moist and at a uni f or m level of
fertility, r oot gr owt h and nut r i ent upt ake will be much gr eat er i n t he upper
soil layers t han i n t he deeper soil layers. Whe n t he surface soil dri es,
nut r i ent upt ake t ends t o shift t o l ower soil layers. It has been r epor t ed t hat
i n Nebr aska t he fi rst cut t i ng of alfalfa absor bed onl y 5% of t he P from deep
i n t he subsoil. Th e t hi r d cut t i ng, pr oduced aft er t he surface soil had be-
come dr ought y, absor bed 62% of t he P from deep subsoil layers. A r ecent
exper i ment i n Kansas was desi gned t o measur e P upt ake by s or ghum gr own
in plastic cyl i nders. As t he level of available P in t he topsoil decr eased, mor e
P was t aken up from t he subsoil. In fact, when t he level of P in t he surface
soil was low and t hat in t he subsoil hi gh, most of t he P was absor bed from
t he subsoil. T h e exper i ment er s f ound a close rel at i onshi p bet ween P upt ake
and t he level of available P and r oot densi t y. It has been obser ved t hat t he P
fertilizer needs of alfalfa decr ease when r oot s become est abl i shed i n soils
with hi gh levels of P in t he subsoil P.
At pr esent little subsoil t est i ng i s done, al t hough i t can be an i mpor t ant
di agnost i c t ool . Per haps, i n t he f ut ur e, mor e effort will be di r ect ed t owar d
gr eat er utilization of subsoil fertility, by al t er i ng pl ant s genetically so t hat
t hey t ap t he subsoil. Th e n subsoil t est i ng will become mor e i mpor t ant .
P LA N T A N A LYS I S
T h e nut r i ent concent r at i on of a pl ant i s an i nt egr at ed val ue t hat reflects all
t he factors t hat have i nfl uenced nut r i ent concent r at i on up t o t he t i me of
sampl i ng. Th e nut r i ent concent r at i on i s r el at ed t o gr owt h and changes over
t i me, as shown in Fi gur e 9. 6. Whe n a nut r i ent is deficient for ma xi mum
gr owt h unde r most condi t i ons encount er ed i n t he f i el d, an i ncrease i n t he
suppl y i ncreases bot h gr owt h or yield and t he nut r i ent ' s per cent age of
composi t i on i n t he pl ant . Addi t i onal upt ake of a nut r i ent beyond t he poi nt
of maxi mum yield cont i nues t o i ncrease t he nut r i ent concent r at i on, i nt o t he
zone of l uxur y consumpt i on, with no yield i ncrease. Event ual l y, t he con-
cent r at i on i n t he pl ant may become t oxi c and cause yields t o decl i ne.
T h e rel at i on bet ween pl ant composi t i on and yield or gr owt h i s t he
basic i nf or mat i on t hat i s gai ned t hr ough pl ant analysis and used t o make
fertilizer r ecommendat i ons , as shown i n Fi gur e 9. 7. Th e nut r i ent concen-
t r at i on at t he maxi mum yield i s t he critical nut r i ent concent r at i on (CNC);
t her e i s a t ransi t i on zone i n whi ch t he nut r i ent concent r at i on changes
r at her abr upt l y from deficient t o adequat e or sufficient. Much r esear ch has
been done t o establish t he CNC and t ransi t i on zones for many pl ant s, and
pl ant analysis i s commonl y used t o pr edi ct t he pot ent i al for appl yi ng fertil-
izer t o i ncrease t he yield rel at i ve t o t he maxi mum yield. Some values
r epr esent at i ve of deficiency and sufficiency for a few cr ops commonl y
gr own i n t he west er n par t of t he Uni t ed States ar e given i n Tabl e 9. 3.
F I G U R E 9. 5 Effect of potential yield of four
different soils on yield response to fertilizer.
FIGURE 9. 6 Relation bet ween nutri ent supply, crop yield, and nu-
trient concentrati on in plants. (After Brown, 1970. )
Frui t and forest t rees gr ow over a l ong per i od of t i me, and CNC values
can be of gr eat use i n di agnosi ng pr obl ems and f or mul at i ng management
pract i ces. In Mi chi gan, pl ant analysis was used t o document t he fact t hat
t her e wer e virtually no mi cr onut r i ent short ages, t hat i n fruit or char ds t her e
had been wi despr ead use of compl et e fertilizers, whi ch wer e 90 per cent
unnecessary. Measur i ng changes i n pl ant composi t i on i s a st andar d met hod
of eval uat i ng t he effectiveness of fertilization pract i ces. Whe n tissue analysis
is used to meas ur e a forest ' s r esponse to fertilization, it may t ake several
years bef or e measur abl e differences appear i n foliar di mensi ons, t r ee
hei ght and di amet er , and wood vol ume.
FIGURE 9. 7 Relation bet ween the concentra-
tion of a nutri ent in the plant and its deficiency
and adequacy for maxi mum growth. (Adapted
from Ulrich and Hills, 1967. )
187
In gener al , a nut r i ent ' s per cent age of composi t i on in a pl ant decreases
as t he pl ant ages, and t her e i s gr eat vari at i on bet ween di fferent par t s of t he
pl ant . Resear ch dat a for most economi c crops have been summar i zed and
pl aced i n t abl es, showi ng when and whi ch par t of t he pl ant t o sampl e. For
exampl e, t he CNC values for cor n have been given as 3% for N, 0. 03% for
P, and 2% for K i n t he leaf opposi t e and bel ow t he upper mos t ear (ear leaf)
at silking t i me.
Cr op Log g i ng
Cr op l oggi ng, whi ch consist of peri odi cal l y measur i ng t he pl ant composi -
t i on, has been widely used for hi gh-val ue cr ops i ncl udi ng sugar cane, pi ne-
appl es, and sugar beet s. For cr ops t hat gr ow over a l ong per i od of t i me,
unusual l y heavy rainfall or r educi ng condi t i ons may great l y al t er t he avail-
abl e suppl y of some nut r i ent s. Mai nt ai ni ng an adequat e suppl y of N for
pl ant s over a l ong gr owi ng season wi t hout pot ent i al cont ami nat i on of wat er
supplies is a f r equent pr obl em. Per i odi c pl ant analysis or cr op l oggi ng was
used i n California t o det er mi ne N fertilization pract i ces t hat woul d maxi -
mi ze sugar pr oduct i on and mi ni mi ze wat er pol l ut i on. For ma xi mum sugar
pr oduct i on by sugar beet s, it is desi rabl e to have a l i mi t ed or small a mount
of N available earl y i n t he season t o encour age hi gh sugar cont ent i n t he
r oot s. Lat er i n t he season i t i s desi rabl e t o have a bunda nt N t o i ncrease t he
quant i t y of r oot s. I n an exper i ment 90 kg N/ h a wer e appl i ed at t hi nni ng
t i me, and pet i ol e N r emai ned above t he sufficient level unt i l t he l at er par t
of Jul y, when an addi t i onal appl i cat i on was made (see Fi gur e 9.8). Thi s
met hod pr oduced mor e sugar t han i f all t he N had been appl i ed at pl ant i ng
t i me and mi ni mi zed t he pot ent i al for wat er pol l ut i on.
FIGURE 9.8 Nitrate content i n peti ol es of sugar beets duri ng the growi ng
season i n response to t wo applications of ni trogen fertilizer and no ni trogen
application. (Modified from Ul ri ch and Hills, 1967. )
References 189
Ra p i d Pl a nt Ti s s u e Te s t s
Analytical pl ant analysis is an i ndi spensabl e r esear ch t ool , one whi ch is
useful i n soil management , but t he tests ar e expensi ve and t i me- consumi ng.
I nexpensi ve test kits for N, P, and K ar e available and have been widely
used t o di agnose pl ant gr owt h pr obl ems i n t he f i el d. The y ar e part i cul arl y
useful t o verify a par t i cul ar deficiency sympt om. The y ar e of t wo t ypes.
Sel ect ed tissue is cut up i nt o small pieces and pl aced in a vial wi t h distilled
wat er , or pl ant sap i s squeezed ont o a pr epar ed paper . Chemi cal s ar e used
t o assay t he nut r i ent cont ent , whi ch i n essence i s a meas ur e of t he nut r i ent s
i n pl ant sap. Par t i cul ar pl ant par t s ar e sampl ed at vari ous stages of gr owt h,
t he same as in analytical tests.
Di a g nos i s a nd Re c omme nd a t i on Int e g r a t e d Sy s t e m
An al t er nat e met hod of eval uat i ng t he status of cr op nut r i ent s t hr ough t he
use of tissue analysis, called t he diagnosis and r ecommendat i on i nt egr at ed
system (DRIS), was devel oped by Beaufils (1973). Thi s system i ncor por at es
tissue analysis wi t h ot her yield par amet er s i n maki ng r ecommendat i ons .
Th e DRI S system emphasi zes t he i mpor t ance of nut r i ent bal ance
wi t hi n pl ant tissue and states t hat ma xi mum yield may never be obt ai ned
unless t he pr oper bal ance or r at i o of nut r i ent s i s mai nt ai ned i n pl ant tissue.
Havi ng this pr oper r at i o of all pl ant nut r i ent s does not i n fact guar ant ee a
ma xi mum yield because t he cr op coul d be dest r oyed by hail, fl oodi ng, or
ot her causes. If t he pl ant nut r i ent r at i o i s i ncor r ect , t he yields will be l ower.
Th e DRI S system has an advant age over t r yi ng t o det er mi ne critical
values i n t hat nut r i ent rat i os i n pl ant tissue t end t o be r at her const ant
t hr oughout t he gr owi ng season. Thus , by appl yi ng this system, t he f ar mer
avoi ds havi ng t o sampl e t he cr op at a preci se gr owt h st age and est i mat e t he
change t hat will occur dur i ng t he rest of t he per i od.
For successful use, t he DRI S system must have known norms or i ndexes
for t he maxi mum yields of each cr op. And t he me t hod of cal cul at i ng t he
nor ms must be readi l y car r i ed out . Nor ms have been devel oped for cor n,
soybeans, wheat , sugar cane, pot at oes, and s or ghum; t hey ar e r ef er enced by
Sumne r and his col l eagues (1983). Let zsch and Sumne r ( 1983) have devel -
oped a comput er pr ogr am for cal cul at i on of t he nor ms and offer copies of i t
for a nomi nal cost.
REF ERENCES
Barber, S. A. 1973. The Changing Philosophy of Soil Test Interpretations. In Soil
Testing and Plant Analysis. Soil Sci. Soc. Am., Madison, Wis.
Beaufils, E. R. 1973. Diagnosis and Recommendation Integrated System (DRIS). Dept.
Soil Science and Agronomy, University of Natal, Pietermaritzburg, South
Africa.
Brown, J. R. 1970. Plant Analysis. Bull. SB881, Missouri Agr. Exp. Sta., Columbia.
Comerford, N. B., G. Kidder, and A. V. Mollitor. 1984. Importance of Subsoil
Fertility to Forest and Nonforest Plant Nutrition. In Forest Soils and Treatment
Impacts. Dept. Forestry, Wildlife and Fisheries, University of Tennessee,
Knoxville.
Cope, J. T. and R. D. Rouse. 1973. Intrepretation of Soil Test Results. In Soil
Ellis, B. G. and R. A. Olson. 1986. Economic, Agronomic and Environmental Implica-
tions of Fertilizer Recommendations. North Central Regional Research Pub. 310,
Mich. Agr. Exp. Sta., East Lansing.
Fox, R. L. and R. C. Lipps. 1964. A Comparison of Stable Strontium and
S 2
P as
Tracers for Estimating Alfalfa Root Activity. Plant and Soil. 20: 337- 350.
Gilliam, J. W. , T. J . Logan, and F. E. Broadbent. 1985. Fertilizer Use in Relation to
Environment. In Fertilizer Technology and Use. 3rd ed., O. P. Engelstad, ed. Soil
Sci. Soc. Am., Madison, Wis.
Kenworthy, A. L. 1973. Leaf Analysis as an Aid in Fertilizing Orchards. In Soil
Leaf, A. L. 1973. Plant Analysis as an Aid in Fertilizing Forests. In Soil Testing and
Plant Analysis. Soil Sci. Soc. Am., Madison. Wis.
Letzsch, W. S., and M. E. Sumner. 1983. Computer Program for Calculating DRIS
Indices. Commun. in Soil Sci. Plant and Anal. 14: 811- 815.
Melsted, S. W., and T. R. Peck. 1973. The Principles of Soil Testing. In Soil Testing
and Plant Analysis. Soil Sci. Soc. Am., Madison, Wis.
Munson, R. D., and W. L. Nelson. 1973. Principles and Practices in Plant Analysis.
In Soil Testing and Plant Analysis. Soil Sci. Soc. Am., Madison, Wis.
Peck, T. R., and S. W. Melsted. 1973. Field Sampling for Soil Testing. In Soil
Pothuluri, J. V., D. E. Kissel, D. A. Whitney, and S. J. Thien. 1986. Phosphorus
Uptake from Soil Layers Having Different Soil Test Phosphorus Levels. Agron.
four. 78: 991- 994.
Soil Improvement Committee, California Fertilizer Association. 1985. Western Fer-
tilizer Handbook. 7th ed. Interstate, Danville, Ill.
Sumner, M. E., R. B. Reneau, Jr. , E. E. Schulte, and J. O. Arogun. 1983. Foliar
Diagnostic Norms for Sorghum. Commun. in Soil Sci. and Plant Anal.
14: 817- 825.
Ulrich, A., and F. J. Hills. 1967. Plant Analysis as an Aid in Fertilizing Sugar Crops.
In Soil Testing and Plant Analysis. Soil Sci. Soc. Am., Madison, Wis.
Whitney, D. A., J. T. Cope, and L. F. Welch. 1985. Prescribing Soil and Crop
Nutrient Needs. In Fertilizer Technology and Use. 3rd ed., O. P. Engelstad, ed.
C H A P T E R 1 0
Application and
Use of Fertilizers
I n gener al , about 50% of t he N, 20% of t he P, and 3 5 % of t he K, or less, i n
fertilizers i s absor bed by cr ops dur i ng t he year of appl i cat i on. Achi evi ng t he
ma xi mum biological efficiency i n usi ng fertilizers depends on t he t i me of
appl i cat i on and t hei r pl acement . Fact ors t hat i nfl uence decisions about
when t o appl y a fertilizer and wher e t o pl ace i t i ncl ude nut r i ent mobi l i t y
and fi xat i on i n t he soil; pl ant needs and t he l ocat i on of r oot s; losses by
volatilization and l eachi ng; t he amount of soil moi st ur e and t he t emper a-
t ur e of soils; and salt effects on ger mi nat i on. In gener al , mat chi ng t he t i me
of appl i cat i on t o pl ant nut r i ent demands decreases t he oppor t uni t y for
fi xat i on a nd loss a nd i ncreases t he oppor t uni t y for absor pt i on a nd a yield
r esponse t o t he nut r i ent appl i ed. Rat es of appl i cat i on and use ar e also
affected by economi c a nd envi r onment al consi derat i ons a nd conveni ence.
F ERT I LI Z ER A P P LI C A T I O N P RACT I CES
Fert i l i zers ar e pl aced ei t her on or i n t he soil. Th e maj or met hods of surface
pl acement ar e br oadcast i ng dr y mat eri al s, spr ayi ng liquids, a nd appl y fertil-
izer i n i rri gat i on wat er . Met hods of pl aci ng fertilizer i n t he soil i ncl ude
ba nd pl acement , pl ow down, injection, a nd appl i cat i on i n i rri gat i on wat er .
Onl y a very mi nor a mount of fertilizer is appl i ed to leaves as a foliar spray.
Fert i l i zer pl acement and t he t i me of appl i cat i on ar e i mpor t ant l y af-
fect ed by t he pract i ces used t o establish a nd manage a cr op a nd t he pr oper -
ties of soils and fertilizers. In gener al , dr y and liquid forms ar e of equal
val ue i f t hey ar e similarly pl aced i n t he soil a nd appl i ed at t he same per i od
of t i me. T h e maj or fact or i s t he a mount of nut r i ent appl i ed. Nut r i ent s i n
bot h dr y and l i qui d forms must appear i n t he soil sol ut i on as ions bef or e
t hey can be t aken up. As t he level of soil fertility i ncreases, pl acement of
fertilizer becomes less i mpor t ant .
191
192 Application and Use of Fertilizers
Th e maj or concer n i n appl yi ng fertilizers i s t hat t he nut r i ent s be used
efficiently wi t hout any det r i ment al effects on pl ant s or t he envi r onment .
Th e maj or consi der at i on i n t he pl acement and t i me of appl yi ng N fertilizers
i s t o pr event t he loss of N t hr ough volatilization, l eachi ng, and denitrifica-
t i on. Fi xat i on of P, t he i mmobi l i t y of P, a nd t he l i mi t ed mobi l i t y of K i n soils
ar e t he maj or consi derat i ons i n t he pl acement and t i mi ng of appl i cat i ons of
P and K fertilizers. In some soils K fixation becomes an i mpor t ant consi der-
at i on. Th e r e i s an i nt er act i on bet ween pl acement and t i me of appl i cat i on,
and i t i s desi rabl e t o discuss t he m t oget her .
Inj e c t i on of Anhy d r ou s A mmo n i a
Th e met hod of appl yi ng N H 3 i s r el at ed t o its gaseous nat ur e. Anhydr ous
ammoni a, 82-0-0, has a vapor pr essur e at 0 degr ees C of 47 pounds per
squar e i nch of gauge pr essur e, and at 38 degr ees C of 197. Because it is a
volatile liquid, i t must be pl aced 15 t o 25 cm deep i n t he soil t o mi ni mi ze
loss by volatilization. As shown i n Fi gur e 4. 10, t he a mount lost i s r el at ed t o
soil t ype, moi st ur e cont ent , a nd dept h of appl i cat i on. For r ow cr ops t he
f ar mer usually chooses an appl i cat or knife or i nj ect or t o appl y t he fertilizer
bet ween al t er nat e pai rs of rows, and pesticides may be appl i ed at t he same
t i me. For forages and small grai ns t he injectors need t o be about 30 t o 40
cm apar t t o obt ai n fairly uni f or m di st r i but i on of t he N for t he r oot s.
Appl i cat i on of par t of t he N dur i ng t he gr owi ng season ensur es mor e
efficient use t han if all t he N is appl i ed bef or e or at pl ant i ng t i me. Now for
r ow cr op pr oduct i on i t i s popul ar t o combi ne t he appl i cat i on of N H 3 wi t h
cul t i vat i on or wi t h appl i cat i on of a her bi ci de.
I t has become popul ar t o appl y anhydr ous ammoni a wi t h ot her tillage
oper at i ons, especially pr i or t o pl ant i ng. On t he ot her hand, i n t he Gr eat
Plains, wher e loss of N by l eachi ng is mi ni mal , del i very lines pl ace anhy-
dr ous ammoni a at t he bot t om of t he tilled layer of under cut t i ng sweeps.
Thi s pract i ce after gr ai n harvest effectively cont r ol s weeds and leaves cr op
resi dues on t he surface t o r educe soil erosi on. I n humi d r egi ons wher e
ni t r at e l eachi ng losses ar e likely, t he appl i cat i on shoul d be del ayed unt i l soil
t emper at ur e is bel ow 18 degr ees C (50F) in t he fall. T h e use of nitrifica-
t i on i nhi bi t ors to i nhi bi t nitrification of fall-applied a mmoni um N is unrel i -
abl e. Fr equent l y, t he fall is a t i me of low l abor demand. In some si t uat i ons
soils ar e dr y and fi rm and t he pri ce of t he N may be di scount ed. Fall
appl i cat i on of N in humi d r egi ons, however , is losing favor because of
concer n about ni t r at e pol l ut i on of gr oundwat er .
I n t he Uni t ed St at es t he f i r st injection of anhydr ous ammoni a i nt o t he
soil occur r ed i n t he Mississippi Del t a r egi on i n t he earl y 1940s. T h e advan-
t ages of pl aci ng P and K fertilizer wi t hi n t he soil may encour age f ut ur e
f ar mer s t o combi ne t he injection of N H 3 wi t h t he injection of P and K.
B a nd Ap p l i c a t i on
Dur i ng t he earl y days of usi ng fertilizer, agri cul t ural soils wer e mor e infer-
tile t han t oday, fertilizers wer e relatively mor e expensi ve, and low rat es of
\
Fertilizer Application Practices 193
FIGURE 10.1 Diffusion of nutrients from fertilizer granul es i nto the surroundi ng
soil enri ched the soil and caused greater growt h of the corn roots.
appl i cat i on wer e common. To obt ai n ma xi mum effectiveness, f ar mer s ap-
pl i ed t he fertilizers i n bands al ong wi t h t he seed. Fert i l i zers became mor e
concent r at ed over t i me, and t he salt i ndex a nd r at es of appl i cat i on in-
cr eased. T h e salt affected ger mi nat i on, a nd appl i cat ors t hat separ at ed seed
and fertilizer wer e i nt r oduced. T h e s t andar d r ecommendat i on for r ow
cr ops is a band 2 i nches to t he side a nd 2 to 6 i nches bel ow t he seeds to
make sur e seed and fertilizer ar e separ at ed e nough t o avoi d salt i nj ury. I n
this l ocat i on t he fertilizer i s usually i n moi st soil wher e earl y r oot gr owt h
can pr ovi de t he pl ant with qui ck access t o t he fertilizer. Band pl acement
r educes P fixation and put s a readi l y available sour ce of nut r i ent s close to
r oot s, al l owi ng t he crops to get off to a fast and vi gorous st art . Th e r e is less
cont act bet ween t he P fertilizer and soil, when banded as compar ed t o
br oadcast , cr eat i ng zones or small ar eas of hi gher P availability. Root
gr owt h i n a fertilized soil band or zone has commonl y been obser ved t o be
gr eat er t han r oot gr owt h i n t he s ur r oundi ng unfert i l i zed soil (see Fi gur e
10. 1). Thi s effect i s due mai nl y t o t he P.
Band pl acement of N i s not effective. Ni t r at e i s not fi xed or ads or bed
by t he soil and r emai ns very mobi l e. Surface appl i cat i on i s as good as
pl acement i n t he soil i f t her e i s r ai n or i r r i gat i on t o move t he N i nt o t he soil.
Ammoni um i n fertilizer i s usually rapi dl y nitrified t o NO3
a nd becomes
very mobi l e. Now fertility levels for P a nd K ar e frequent l y so hi gh t hat
band pl acement of P or K does not i ncrease t he yield mor e t han does
br oadcast appl i cat i on. However , pl ant analysis may show slightly gr eat er
upt ake of fertilizer P and K earl y in t he gr owi ng season when it is
band- pl aced.
As i ndi cat ed, t her e is less a nd less benefi t from bandi ng fertilizer as soil
fertility levels i ncrease. Th e r e ar e, however , some i mpor t ant si t uat i ons i n
whi ch band pl acement i s effective. Yield i ncreases with band appl i cat i on of
P on Oxisols wi t h hi gh P-fixing capacity ar e common. Band appl i cat i on of K
is also effective on soils wi t h unusual l y hi gh K-fixing capacity. Band applica-
t i on hel ps t o i ncrease t he upt ake of mi cr onut r i ent s from fertilizers t hat ar e
subject to r api d soil fixation in all soils. Low spr i ng t emper at ur es in soil
appear t o be t he r eason for t he r esponse of spr i ng wheat t o banded P on t he
nor t he r n Gr eat Plains.
Br oa dc a s t Ap p l i c a t i on
Broadcast appl i cat i on i s t he spr eadi ng of t he fertilizer uni forml y over t he
ent i r e soil surface. It is t he only pract i cal way to fertilize lawns, forage and
past ur e f i el ds, and forests on mount ai n slopes. As al ready i ndi cat ed, anhy-
dr ous ammoni a i s not sui t abl e for br oadcast appl i cat i on on t he soil surface.
If t he fertilizer cont ai ns onl y N, subsequent rai ns will move t he fertilizer
i nt o t he soil, a nd br oadcast appl i cat i on may be as effective as any ot her
pl acement . Ur ea i s rapi dl y hydr ol yzed t o N H 4
+
unde r war m and moi st
condi t i ons. Whe n ur ea i s br oadcast unde r al kal i ne condi t i ons, however , t he
N H 4
+
react s wi t h O H
-
t o f or m NH3 and wat er wi t h gr eat pot ent i al for loss
of N by volatilization. It is not unc ommon to lose over 30 per cent of t he N
from surface appl i cat i on of ur ea. As a consequence, t he effectiveness of a
br oadcast appl i cat i on will be i ncr eased i f t he ur ea i s l eached i nt o t he soil or
i ncor por at ed by subsequent tillage.
Phos phor us i s readi l y fi xed i n most soils and t hus moves very little f r om
t he poi nt of appl i cat i on. Broadcast appl i ed P is t her ef or e less effective
because few r oot s ar e active i n t he i mmedi at e surface soil, especially when
t he surface soil dri es. In many forage fi el ds, however , t he surface of t he soil
may r emai n moi st unde r dense foliage for a consi der abl e par t of t he grow-
i ng season, and t he upt ake of P i s effective. For i nsol ubl e phosphat es, i n t he
f or m of r ock phosphat e, br oadcast appl i cat i on, and subsequent i ncor por a-
t i on i nt o t he soil, i s mor e effective t han band pl acement because i t pr ovi des
mor e soil cont act s and oppor t uni t i es for di ssol ut i on. Gypsum and el ement al
S ar e c ommon car r i er s for sulfur and ar e commonl y br oadcast because
S O4
2
i s mobi l e and readi l y moves i nt o t he soil wi t h wat er .
All ai r pl ane and hel i copt er appl i cat i ons ar e by br oadcast i ng. I n t he
Uni t ed States aeri al seedi ng and fertilization of fl ooded ri ce fi el ds i s r ou-
t i ne. Rough t er r ai n a nd t he inaccessibility of many forests makes aeri al
appl i cat i on popul ar . In t hese i nst ances ur ea is commonl y appl i ed, in a l arge
prill size t hat drifts little and can be uni forml y di st r i but ed.
Comb i ni ng Br oa dc a s t Ap p l i c a t i on wi t h Ti l l a g e Op e r a t i ons
Fert i l i zer use i n t he past has great l y i ncreased soil test levels for P, and t he
overall fertility level has i ncreased for many soils. Thus , t o some ext ent t he
negat i ve effects of P fixation from br oadcast appl i cat i ons have been di mi n-
i shed. T h e l ower cost of fertilizer rel at i ve t o l abor and ot her appl i cat i on
costs has encour aged hi gher r at es of fertilizer use as well as less at t ent i on t o
effective pl acement and pr oper t i mi ng. In t he fall and wi nt er mor e l abor i s
available, and, per haps, soils ar e fi rmer for appl i cat i on wi t h bul k spr eader s.
T h e pr i ce of fertilizer i s also mor e at t ract i ve i n t he off-season. T h e br oad-
cast i ng of bul k fertilizer and pl owi ng unde r t he fertilizer i s t her ef or e popu-
lar. Pl owi ng and subsequent tillage oper at i ons mi x t he fertilizer t hr oughout
t he plow layer and cont r i but e t o effective use of t he nut r i ent s.
Ap p l i c a t i on i n No- Ti l l Sy s t e ms
In humi d regi ons r educed tillage t o lessen soil erosi on and l ower t he costs of
pr oduct i on has pr oved popul ar for r ow cr ops, especially for cor n i n t he
s out her n Cor n Belt. In no-till pl ant i ng systems t her e i s no convent i onal
pl owi ng. Cr op resi dues and or gani c mat t er accumul at e at t he soil surface.
Weeds and compet i ng veget at i on ar e cont r ol l ed by chemi cal herbi ci des.
Onl y a st ri p of soil 2. 5 to 7. 5 cm wi de is di st ur bed for each pl ant ed r ow.
Fert i l i zer appl i cat i ons ar e mai nl y by br oadcast on t he surface. T h e system
bui l ds up a concent r at i on of or gani c cr op resi dues and car r yover nut r i ent s
i n t he upper few cent i met er s of soil. Th e r e i s gr eat er mi crobi al a nd r oot
activity i n this upper soil zone a nd gr eat er oppor t uni t y for i mmobi l i zat i on
a nd mi neral i zat i on of N. Th e possibility exists for i mmobi l i zat i on of N t o
decompose cr op resi dues i n t he upper soil layer. Th e acidic effects bot h of
aci d-formi ng N fertilizers and of or gani c mat t er mi neral i zat i on ar e, simi-
larly, concent r at ed i n t he few cent i met er s of surface soil. Thes e effects
woul d appear t o have an i nfl uence on cr op yields; however , yields from
no-till have general l y not been significantly di fferent from yields of conven-
t i onal tillage systems. Per haps t he sameness of yield i s r el at ed t o ot her
effects of no-till pl ant i ng.
In no-till pl ant i ng t her e i s mor e wat er available for cr ops because
infiltration i s gr eat er and surface evapor at i on less. Th e accumul at ed or-
gani c mat t er at t he surface acts as a mul ch and causes l ower soil t emper a-
t ur es i n t he spri ng. Th e effect of l ower soil t emper at ur e, especially i n t he
nor t he r n states, has been t o st i mul at e a r esponse t o some st ar t er K fertilizer
when soil K tests wer e less t han opt i mum. In addi t i on, t he compact i on of
no-till soil and its bl ocki ng effect on aer at i on has appar ent l y r educed K
availability i n some exper i ment s. The s e fi ndi ngs confi rm t he compl exi t y of
t he s oi l - pl a nt - c l i ma t e system; per haps addi t i onal r esear ch will give a
cl ear er pi ct ur e of t he effects of no-till on soil pr oper t i es and t he r esponse of
cr ops t o fertilizers. I n t he f ut ur e t he devel opment of bet t er pl ant er s with
whi ch t o pl ace fertilizer i n t he soil, t oget her wi t h an occasional pl owi ng, will
likely over come any negat i ve aspect s of nut r i ent and pH stratification.
Fe r t i g a t i on
T h e appl i cat i on of fertilizers t o i rri gat i on wat er i s called fertigation. Anhy-
dr ous ammoni a was first di rect l y appl i ed as a fertilizer in t he 1930s in
Cal i forni a when anhydr ous ammoni a was a dde d t o i rri gat i on wat er . Th e
t wo maj or pr obl ems of fert i gat i on have been t he inability t o di st r i but e
nut r i ent s uni forml y, because wat er di st r i but i on i s not uni f or m, and fi xat i on
of P i n t he surface soil wher e r oot activity i s low. Th e r e has been much
pr ogr ess i n solving bot h of t hese pr obl ems so t hat , t oday, appl yi ng fertil-
izers i n t he i rri gat i on wat er i s often t he most conveni ent and i nexpensi ve
met hod of appl i cat i on. Fer t i gat i on may also offer mor e flexibility i n t i mi ng
and i n rat es of appl i cat i on a nd bet t er cont r ol of l eachi ng so t hat fewer
mobi l e nut r i ent s ar e lost from sandy soils. Di sadvant ages i ncl ude loss of
nut r i ent s in runoff wat er; volatilization loss of N from spri nkl er-appl i ed
N H 3 and aqua ammoni a, especially on cal careous soils; t he pr eci pi t at i on of
i ncompat i bl e fertilizer mat eri al s; and t he cl oggi ng of nozzles and emi t t er s.
T h e maj or management decisions for fert i gat i on r el at e t o t he nat ur e of
t he fertilizer mat eri al s and me t hod of wat er di st ri but i on. Wat er di st ri bu-
t i on i s by open or gravi t y systems, such as furrow or flood, or by closed
systems, whi ch i ncl ude spri nkl ers and dr i p or t ri ckl e. Aqua ammoni a and
N H S ar e subject t o seri ous volatilization loss from bot h wat er and soil
surface i n bot h closed and open systems. Losses from spri nkl er appl i cat i on
i n excess of 50 per cent have been r epor t ed. Th e loss i s enhanced by
alkalinity of wat er and soil, by ai r t ur bul ence, and by i ncreases i n t emper a-
t ur e, r at e of appl i cat i on, and l engt h of exposur e. Ammoni a added t o i rri ga-
t i on wat er i ncreases t he pH of t he wat er and, i n t he pr esence of C a
2 +
and
Mg
2 +
, and H C O 3
, causes Ca and Mg salts t o pr eci pi t at e, whi ch can clog

closed-system equi pment . Ur e a - a mmo n i u m ni t r at e ( UAN) sol ut i ons ar e
popul ar because t he N is less volatile and t her e is mor e efficient use of N. If
dr y N car r i er s ar e dissolved i n wat er and used i n closed systems, t hey must
be free of any coat i ng mat eri al s t hat will pl ug or clog nozzles and emi t t er s.
Little P is appl i ed by fert i gat i on because t he P t ends to accumul at e at
t he soil surface wher e r oot activity i s mi ni mal . In al kal i ne wat er t he P may
pr eci pi t at e Ca and Mg, agai n causi ng a cl oggi ng pr obl em. Acids can be
added t o wat er t o r et ar d pr eci pi t at i on of salts; however , t he acids ar e
corrosi ve and r equi r e special handl i ng. Resear ch i s bei ng conduct ed t o
eval uat e t he effectiveness of acids for r educi ng ammoni a loss a nd t he
pr eci pi t at i on of salts i n t he appl i cat i on equi pment . Th e K carri ers, KCl and
K2 S O4 , can be a dde d t o i rri gat i on wat er wi t h no appar ent pr eci pi t at i on
pr obl ems. Sol ubl e sulfate car r i er s ar e used t o add S. Some soluble chel at ed
forms of mi cr onut r i ent s ar e also used.
A maj or l i mi t at i on of fert i gat i on is t he nonuni f or m di st r i but i on of
wat er and t he t her ef or e nonuni f or m di st ri but i on of nut r i ent s i n open sys-
t ems. T h e maj or advant age of fert i gat i on i s t he i ncr eased oppor t uni t y t o
add fertilizer. Since N i s t he maj or nut r i ent appl i ed, this means bet t er
t i mi ng of N i n rel at i on t o pl ant needs dur i ng t he gr owi ng season. In
addi t i on, on sandy soils wi t h pi vot spri nkl er systems, t her e i s gr eat er cont r ol
over ni t r at e N loss by l eachi ng and over gr oundwat er cont ami nat i on.
Fol i a r Ap p l i c a t i on
Fol i ar appl i cat i on can be used for t he qui ck cor r ect i on of a nut r i ent defi-
ciency i n pl ant s. Th e amount of fertilizer nut r i ent s t hat can be appl i ed t o
t he foliage is l i mi t ed by t he solubility of t he mat eri al s, t he salt t ol er ance of
t he foliage, and t he a mount of liquid t hat adher es t o t he leaves. Most of t he
i nt erest in foliar sprays is for t he appl i cat i on of mi cr onut r i ent s. Some of
t hese, Mn and Fe for exampl e, ar e rapi dl y f i xed or conver t ed i nt o i nsol ubl e
f or m i n al kal i ne soils, and pl ant s have a very small r equi r ement . Of t en t her e
must be r epeat ed sprayi ngs, whi ch limits t he use for t he mor e val uabl e
cr ops, such as t r ee fruits. If t he cr op i s i r r i gat ed with over head spri nkl ers,
t he mi cr onut r i ent can be appl i ed i n t he i rri gat i on wat er . Pi neappl es i n
Hawai i ar e r egul ar l y sprayed with f er r ous sulfate t o suppl y i r on. Ur ea i s
readi l y absor bed by t he leaves, and pi neappl es have a hi gh t ol er ance for
foliar salts. As much as 75 per cent of t he t ot al N needs of pi neappl es have
been suppl i ed from foliar appl i cat i on of ur ea. Th e hi gh pl ant r equi r ement s
for N, P, and K general l y make foliar appl i cat i on of limited use for t he
appl i cat i on of fertilizers cont ai ni ng t hese nut r i ent s.
Dur i ng t he seed-filling st age of grai ns, t her e i s consi der abl e movement
of N, P, and K t o t he seeds. Thes e nut r i ent s ar e qui t e mobi l e i n pl ant s;
however , leaves ar e depl et ed of t hese nut r i ent s. Some nut r i ent s like Ca,
Mg, a nd Mn ar e not effectively t r ansl ocat ed from leaves t o seeds. Thus , i t
woul d seem t hat t he addi t i on of cer t ai n nut r i ent s by foliar appl i cat i on
dur i ng seed-filling t i me mi ght have a significant effect on gr ai n yield.
Recent r esear ch on t he appl i cat i on of foliar nut r i ent s dur i ng t he seed-filling
t i me of grai ns has at t i mes shown a significant i ncrease in yield. Some
gener al concl usi ons from this wor k ar e as follows.
1. Ur e a is t he most effective form of N for foliar appl i cat i on. Th e ur ea
shoul d not be appl i ed when t he sun i s shi ni ng bri ght l y, and bi ur et i n t he
ur ea may cause leaf bur n and r educe yield. T h e maxi mum r at e of ur ea
t hat can be appl i ed at one t i me wi t hout causi ng seri ous leaf bur n i s N at
t he r at e of 22 k g / h a (20 pounds / a c r e ) .
2. Whe r e foliar fertilization has i ncreased grai n yields, t he four nut r i ent s,
N, P, K, and S, wer e appl i ed. A r at i o of 10N-1P-3K-0. 5S was t he most
effective for soybeans.
3. I ncl udi ng mi cr onut r i ent s or t he less phl oem- mobi l e nut r i ent s (Zn, Cu,
Mn, B, Ca, Mg) di d not i ncrease soybean yields.
De e p Soi l Pl a c e me nt
If surface soils ar e dr y and subsoils ar e moi st , t he gr eat er wat er pot ent i al i n
t he subsoil encour ages gr eat er r oot gr owt h t her e and subsequent l y gr eat er
use of t he nut r i ent s pl aced i n t he subsoil. Root penet r at i on i s i nhi bi t ed i nt o
soil layers devoi d of Ca. In some very aci d and highly weat her ed soils, deep
pl acement of Ca i s necessary i n or der t o pr omot e deep r oot i ng and t he use of
subsoil wat er. Deep pl acement as used her e general l y means pl acement i n
t he subsoil; it is expensi ve and used only occasionally (see Fi gur e 10. 2). It is
to be expect ed t hat a pl ant ' s use of nut r i ent s pl aced deep in t he soil is less
efficient, because maxi mum r oot activity is usually in t he plow layer.
FIGURE 10. 2 Fertilizer applicator mount ed on a disk pl ow for placing lime and
fertilizer up to 75 centi meters deep i n the soil.
F ERT I LI Z ER R EC O MMEN D A T I O N P H I LO S O P H I ES
Fert i l i zer r ecommendat i ons based on soil tests ar e of t hr ee t ypes. First, now
t hat many soils test hi gh for P and K, a mai nt enance phi l osophy is em-
pl oyed. Second, soil tests ar e used as a meas ur e of nut r i ent sufficiency and
ar e t he basis for det er mi ni ng t he a mount of fertilizer needed. Finally,
fertilizer r ecommendat i ons ar e based on a consi der at i on of cat i on bal ance.
Ma i nt e na nc e Fe r t i l i z e r Re c omme nd a t i ons
On e of t he most st ri ki ng effects of huma n occupancy and t he agr i cul t ur al
use of l and i s t he soil' s i ncr eased cont ent of phos phor us . Anci ent campsi t es
and ki t chen mi ddens have been l ocat ed i n t he Uni t ed States and Eur ope by
a systematic sampl i ng of soils and a det er mi nat i on of t hei r P cont ent . Thi ck,
dar k- col or ed A hor i zons with pr oper t i es similar t o mollic hor i zons, except
t hat t hey cont ai n 250 ppm or mor e of P 2 O 5 soluble i n 1% citric acid, qualify
as anthropic hori zons, Ant hr opi c hor i zons ar e f or mat i ons great l y affected by
huma n activity. In villages and campsi t es P i s di scar ded as bones and ot her
refuse, and t he P is subsequent l y fixed and accumul at es in t he soil. Agri cul -
t ur al l and accumul at es P from l ongt i me manur i ng and fertilization. In
Mi chi gan t he medi an soil test for P i ncreased from 23 t o 105 pounds / a c r e
bet ween 1962 and 1986. Lar ge i ncreases in soil P over a relatively shor t
t i me for a vari et y of maj or cr ops ar e gi ven i n Tabl e 10. 1.
Th e ext ent of P car r yover depends on soil f i xat i on and cr op r emoval .
In Illinois t he addi t i on of 9 pounds of P 2 O 5 (4 pounds of P) i ncreases soil
Fertilizer Recommendation Philosophies 199
County Major crop 1972
P in soil, pp 2
1976- 1977
m
1979- 1980
Grand Traverse Fruit 48 58 83
Montcalm Potatoes 137 173 246
St. Joseph Corn 82 109 171
Ingham Cash crop 44 62 84
Ontonagon Forage 17 18 34
Source: From Ellis and Ol son, 1986.
tests by about 1 p o u n d / a c r e . Thus , for many soil and cr oppi ng si t uat i ons
t he P soil test may become hi gh in a few years, for a hi gh test is frequent l y
only 30 t o 60 pounds / a c r e . It i s very c ommon for gar dens t o test very hi gh
i n P. Some st at e soil-testing l abor at or i es now r epor t t hat 50 per cent or
mor e of t he soil sampl es test hi gh or very hi gh. Pot assi um car r yover i s also
very c ommon and r el at ed t o soil f i xat i on and cr op r emoval . Several states
r epor t t hat about 4 pounds of fertilizer K2 O (3. 3 pounds of K) will i ncrease
t he K soil test 1 p o u n d / a c r e . Ni t r ogen car r yover is st rongl y r el at ed to
l eachi ng and deni t ri fi cat i on losses. Th e r e may be significant car r yover of
ni t r at e N from one year t o t he next i n soils wi t h ari di c and ustic soil
moi st ur e r egi mes. Soils i n gener al , however , do not show cont i nui ng in-
creases of available N to very hi gh levels as t hey do for P a nd K.
Because soil tests ar e frequent l y hi gh for P and K, it is becomi ng
popul ar t o make mai nt enance r ecommendat i ons for t hese nut r i ent s. T h e
a mount r e c omme nde d i s based on an est i mat i on of about 1.5 t i mes t he
a mount r emoved i n t he har vest ed crops. Soil tests every t wo t o fi ve years
ar e r e c omme nde d t o det er mi ne whet her r ecommendat i ons need t o be
adj ust ed.
Nu t r i e nt Suf f i c i e nc y Re c omme nd a t i ons
Sufficiency r ecommendat i ons ar e based on t he soil test cor r el at i on and
cal i brat i on pr ocedur es discussed i n Chapt er 9. T h e soil test val ue i s used t o
pr edi ct or est i mat e t he a mount of fertilizer needed t o achi eve t he desi red
yield goal.
Ba si c Ca t i on Sa t ur a t i on Ra t i o
Th e basic cat i on sat ur at i on rat i o (BCSR) or cat i on bal ance met hod at t empt s
t o adj ust t he di st r i but i on of t he exchangeabl e Ca, Mg, and K t o about 6 5 %,
10%, and 5% sat ur at i on, respectively. T h e per cent age of sat ur at i on r at i o of
Ca : Mg, Ca : K, and Mg : K woul d be 6. 5, 13, and 2, respectively. T h e rat i os
for t he plow layers of fi el ds on whi ch wor l d r ecor d cor n yields wer e pr o-
TABLE 10. 1 Me d i a n Phos p hor u s Soi l Te s t Le v e l s f or Se l e c t e d Count i e s a nd
Ma j or Cr ops i n Mi c hi g a n
duced i n 1973 and 1977 wer e 4, 23, and 6 i n 1973 and 3, 18, and 5 i n
1977. Resear ch on soils whi ch have a significant a mount of CEC a nd i n
whi ch t he amount s of XCa and XMg ar e l arge rel at i ve t o annual cr op needs
(Alfisols and Mollisols) has failed to show a significant rel at i on bet ween cr op
yields and t he per cent age of sat ur at i on of Ca, Mg, and K. Ver y wi de
differences i n t he rat i os of t hese exchangeabl e cat i ons wi t h one anot her
have been obser ved wi t h no negat i ve effect on yields. Recommendat i ons
based on t hese rat i os t end t o resul t i n overfert i l i zat i on and i ncrease t he cost
of pr oduct i on.
I n some si t uat i ons t he rat i os ar e i mpor t ant . Th e excessively hi gh XMg
rel at i ve t o t he ot her exchangeabl e cat i ons i s associated wi t h infertility i n
ser pent i ne soils. Hi gh K fertilization can br i ng on a Mg deficiency for some
crops gr owi ng on soils wi t h a mar gi nal cont ent of XMg. Oxisols have very
little CEC and small absol ut e amount s of XCa. . Na. Cr ops gr owi ng on
Oxisols ar e mor e sensitive t o small soil fertility differences as compar ed t o
crops gr owi ng on Alfisols and Mollisols. On e exampl e of a r ecommendat i on
for cr oppi ng on Oxisols i s an absol ut e mi ni mum a mount of K equal t o 0.1
me q / 1 0 0 g of soil and a rel at i ve mi ni mum a mount of K equal t o 2% t o 3%
of t he XCa. . Na.
An ei ght -year st udy was conduct ed on four di fferent soils and l ocat i ons for
cor n pr oduct i on i n Nebr aska. Soil sampl es from each l ocat i on wer e r ou-
tinely sent t o fi ve di fferent soil-testing l abor at or i es for fertilizer r ecommen-
dat i ons. All t hr ee phi l osophi es wer e r epr esent ed, and all t he cor n yields
wer e similar. Th e r e wer e, however , l arge differences i n t he ki nds and
amount s of fertilizer r e c omme nde d. Consequent l y, t her e wer e l arge differ-
ences i n t he fertilizer costs. T h e resul t s general l y s uppor t ed t he nut r i ent
sufficiency phi l osophy as bei ng agronomi cal l y and economi cal l y sound.
F ERT I LI Z ER A N D P L A N T - WA T E R R ELA T I O N S
Evapot r anspi r at i on ( ET) is a physical process cont r ol l ed by t he met eor ol ogi -
cal condi t i ons or t he a mount of heat available for evapor at i ng wat er f r om
t he soil and veget at i on. Whe n wat er i s nonl i mi t i ng, t he ET or wat er con-
sumed by a cr op is a funct i on of met eorol ogi cal condi t i ons and not of t he
r at e of pl ant gr owt h. Un d e r t hese condi t i ons any management pract i ce t hat
i ncreases yield will i ncrease t he efficiency of wat er use. Whe n wat er is
l i mi t i ng and soils become dr y, soil nut r i ent s ar e not as available and wat er
use is less efficient.
Wa t e r Us e Ef f i ci ency
Th e wat er consumed for each uni t of yield i s a measur e of t he efficiency
wi t h whi ch wat er i s used. In compar i sons of fertilized a nd nonfert i l i zed
Fertilizer and Plant-Water Relations 201
f i el ds or exper i ment al pl ot s, t he heat available for evapor at i on of wat er can
be consi der ed a const ant . As a consequence, t he ET woul d be expect ed t o
be t he same on bot h cont r ol pl ot s and fertilized pl ot s. On e agr onomi c
modi fi er of t he act ual ET i s t he ext ent of veget at i ve cover. Once an
adequat e veget at i ve cover i s est abl i shed, however , addi t i onal pl ant gr owt h
or cover has no effect or very little effect on ET. Lar ger pl ant s can i nt er cept
mor e advect i ve or hori zont al l y t r ansf er r ed heat , but this effect i s small.
Thus , any yield i ncrease br ought about by usi ng fertilizer i nvari abl y in-
creases t he efficiency of wat er use. Repor t s of a 50 per cent or gr eat er
i ncrease i n cr op yield per i nch of wat er used ar e c ommon when t he r e-
sponse to fertilizer is l arge. I ncr eased wat er use efficiency is also verified by
t he casual obser vat i on t hat doubl i ng t he aver age yields of a cr op in a st at e
does not doubl e t he use of wat er or doubl e t he wat er deficit. As wat er for
i rri gat i on becomes mor e expensi ve and less available, i t becomes mor e
i mpor t ant t o maxi mi ze pr oduct i on from t he l i mi t ed suppl y of available
wat er .
Ef f ect of Wa t e r on Nu t r i e nt Av a i l a bi l i t y
Pl ant s can obt ai n t hei r nut r i ent s and wat er from a very small soil vol ume if
bot h nut r i ent s and wat er ar e hi ghl y available. Whe n soils dr y, however , t he
mat r i c wat er pot ent i al a nd hydr aul i c conduct i vi t y decr ease. Decr eased hy-
dr aul i c conduct i vi t y r educes t he movement of wat er t hr ough soil t o r oot s,
t her eby r educi ng t he r at e of wat er upt ake and t he r at e at whi ch nut r i ent s
move t o r oot s by mass flow and diffusion. Pl ant s unde r wat er and nut r i ent
stress phot osynt hesi ze less. Bot h t op and r oot gr owt h may be r est r i ct ed.
Dr ought y condi t i ons, t her ef or e, may rest ri ct r oot gr owt h and decr ease t he
pot ent i al suppl y of nut r i ent s (and wat er) positionally available for upt ake.
I ncr eased soil fertility, on t he ot her hand, may i ncrease t he gr owt h r at e and
t he ext ent of t he r oot system, t her eby i ncreasi ng t he a mount of nut r i ent s
and wat er t hat ar e positionally available for upt ake (see Fi gur e 10. 3).
T h e Cisne soil r ef er r ed to in Fi gur e 10. 3 is a cl aypan soil, Albaqualf,
wi t h smectitic clays in t he cl aypan. Resear ch in Missouri on similar soils
showed t hat br eaki ng up t he cl aypan with deep tillage dur i ng t he dr y season
pr oduc e d only t empor ar y resul t s. Fert i l i zat i on, however , pr oved t o be t he
most effective means of i ncreasi ng deep r oot gr owt h and yields.
As soils dr y, t her e i s a decr ease i n t he movement of nut r i ent s t o t he
r oot s by mass flow and diffusion. In dr y soils, compar ed t o moist soils, fewer
nut r i ent ions move t o r oot s by mass flow because t her e i s less wat er movi ng.
Th e diffusion pat h for nut r i ent s (and wat er) becomes mor e t or t uous as t he
soil dri es, so t hat fewer ions move t o r oot s by diffusion. And t he a mount of
nut r i ent s rel eased when or gani c mat t er mi neral i zes decreases when soils
dr y, affecting t he supply of N in par t i cul ar and somet i mes decr easi ng B to
t he poi nt of deficiency. Th e r e i s an i nt er act i on bet ween soil fertility and soil
wat er so t hat i t may be difficult t o det er mi ne i n t i mes of dr ought whet her
yields ar e r educed mor e by a lack of wat er or by a lack of nut r i ent s.
EF F ECT OF F ERT I LI Z ERS ON SOI L R EA C T I O N
Fertilizers as soluble salts ar e acid, neut r al , or al kal i ne. Most of t he net or
l ong- t er m effects of fertilizer on soil pH ar e caused by t r ansf or mat i ons t hat
occur i n t he soil. T h e addi t i on of N H S pr oduces an i mmedi at e al kal i ne
affect owi ng to hydrolysis; however , subsequent nitrification pr oduces a
l ong- t er m acidic effect. Ammoni um sulfate and NH4 Cl i n par t i cul ar ar e
aci d-formi ng because of t he accompanyi ng acidic ani on; t hey ar e somet i mes
selected as t he N fertilizer when an i ncrease in soil acidity is needed. Ni t r at e
accompani ed by Ca, Mg, K, or Na i s basic. Pot assi um chl or i de and K2 S O4
have a neut r al effect. Of t he P mat eri al s, only t hose cont ai ni ng a mmoni um
ar e aci d-formi ng owi ng t o t he nitrification of t he a mmoni um.
In gener al , t he P and K car r i er s in fertilizers do not significantly affect
soil pH. Th e concer n i n agr i cul t ur e cent er s on t he N fertilizers because t he
most popul ar N mat eri al s ar e NH3 , NH4 NO3 , and ur ea, whi ch ar e acid-
f or mi ng. Th e effects of t he aci d-formi ng fertilizers depend on t he r at es of
appl i cat i on and t he pH and bufferi ng capacity of t he soil. The i r appl i cat i on
on alkaline and cal careous soils may be beneficial. On acid sandy soils,
however , changes may be r api d and t he effects qui t e negat i ve.
Th e negat i ve effects shown i n Fi gur e 10. 4 ar e ext r eme because t he
bufferi ng capacity of t he soil was small and t he r at e of N appl i cat i on hi gh.
Economics of Fertilizer Use 203
FIGURE 10. 4 Photograph of a plot that recei ved 1 500 pounds of ni trogen from
ammoni um sulfate over fi ve years. The treatment produced a soil pH of 3.9, and
few if any corn plants grew. Iron was mobi l i zed and moved to form a crust on the
ridges. (Photograph courtesy Mi chi gan Agricultural Experi ment Station.)
In t he exper i ment t he devel opment of a pH of about 4 pr oduced Mn
toxicity and Mg deficiency. The s e resul t s show t hat when acid sandy soils
ar e not l i med t o i ncrease soil pH and t he cr oppi ng system excl udes l egumes,
t he cont i nued hi gh r at es of appl yi ng N fertilizer may great l y i ncrease t he
lime r equi r ement and negat i vel y affect yields.
EC ON OMI C S OF F ERT I LI Z ER USE
Two maj or decisions r el evant t o t he economi cs of fertilizer use ar e t he pr i ce
of fertilizer rel at i ve t o t he pr i ce of cr ops and t he pri ce of fertilizer rel at i ve
t o t he pri ce of ot her factors of pr oduct i on. I n r ecent decades t he pri ce of
l abor, machi ner y, and l and have i ncr eased much mor e rapi dl y t han t he cost
of fertilizers. As a consequence, f ar mer s have t ended t o subst i t ut e fertilizer
for ot her factors of pr oduct i on, and this has account ed i n l arge par t for t he
r api d i ncrease i n fertilizer use since Wor l d War I I . In t he past few years,
however , t he effect of i ncreasi ng soil test values and t he adver se economi c
si t uat i on have moder at ed t he t r end.
Pr of i t Ma x i mi z a t i on f r om Fe r t i l i z e r U s e
Th e ent i r e pl ant gr owt h cur ve i s si gmoi dal . I n t he r ange wher e decisions
about fertilizer use ar e made, t he addi t i on of fertilizer causes i ncreasi ng
gr owt h at a decr easi ng r at e. Ret ur ns ar e di mi ni shi ng. Th e fi rst uni t s of
fertilizer pr oduce a gr eat er yield r esponse t han l at er uni t s. Profits from t he
use of a fertilizer ar e at t he maxi mum when t he last or mar gi nal uni t of
fertilizer pr oduces a yield i ncrease whose pri ce is equal to t he cost of t he
FIGURE 10. 3 Fertilizer greatly increased deep root
growt h of corn i n the claypan of the Cisne silt l oam
(Albaqualf). (Photograph courtesy J. B. Fehrenbacher. )
uni t of fertilizer. T h e r at i o of t he pri ce of t he cr op t o t hat of t he fertilizer i s
1.0, and t he poi nt of maxi mum profit occurs at a r at e less t han t hat needed
t o pr oduce t he maxi mum yield, as shown i n Fi gur e 10. 5.
Th e r e ar e several ot her factors t hat affect t he act ual deci si on r egar di ng
fertilizer r at e. Since t he mar gi nal r e t ur n f r om addi t i onal uni t s of fertilizer
becomes less and less profi t abl e, havi ng an al t ernat i ve, mor e profi t abl e
i nvest ment i n whi ch t o put t hei r money woul d i nfl uence f ar mer s t o appl y
fertilizer at less t han t he poi nt of ma xi mum profi t . Somet i mes a lack of
capital and risk ar e i mpor t ant fact ors. In many devel opi ng count r i es t her e i s
little or no oppor t uni t y t o make a profit from t he use of a fertilizer because
its cost i s t oo hi gh rel at i ve t o t he pr i ce of t he cr op.
EN V I R O N MEN T A L C O N C ER N S
Th e r e ar e t wo i mpor t ant envi r onment al concer ns r egar di ng fertilizer use.
Th e first is t he effect of N and P on t he eut r ophi cat i on of surface wat er s,
and t he second i s t he accumul at i on of ni t r at e i n bot h surface wat er and
gr oundwat er .
Ni t r og e n
Th e r at e and t i me of appl i cat i on ar e t he t wo maj or issues i n t he use of N
fertilizers. General l y, t he rat es r e c omme nde d by soil-testing l abor at or i es
ar e accept abl e if t he soil profile is low in ni t r at e. In soils wi t h ustic and ari di c
Environmental Concerns 205
soil moi st ur e r egi mes, t he ni t r at e levels i n t he soil shoul d be measur ed.
Th e quant i t y i n t he profile shoul d be subt r act ed from t he nor mal
r ecommendat i on.
Ti mel i ness of appl i cat i on i s an i mpor t ant concer n i n humi d r egi ons. To
be envi r onment al l y accept abl e, N shoul d be appl i ed so t hat i t will be r e-
t ai ned i n t he r oot zone dur i ng t he gr owi ng season. Th e pot ent i al for ni t r at e
l eachi ng i s cr eat ed when mor e NO3
exists i n t he soil t han pl ant s can use.

Th e ext r a N O 3
_
becomes l eachabl e, as shown i n Fi gur e 10. 6. Thus , i f N
fertilizer rat es ar e j us t sufficient t o meet yield goals, little pot ent i al for
ni t r at e l eachi ng i s cr eat ed. Many f ar mer s, however , set optimistically hi gh
yield goals and t end t o use mor e N fertilizer t han i s needed.
Excessive ni t r at e i n dr i nki ng wat er can pr oduce vari ous di sor der s i n
livestock and met hemogl obi nemi a, lack of oxygen i n bl ood, i n i nfant s.
Met hemogl obi n i s a bl ood pi gment t hat differs from hemogl obi n. Th e
Uni t ed States Publ i c heal t h st andar d for domest i c use i s 10 ppm (10 milli-
gr ams / l i t er ) N as ni t r at e in wat er .
In t he earl y 1970s i t was di scovered t hat N2 O rel eased i nt o t he at mo-
s pher e causes react i ons t hat decr ease t he a mount of ozone ( O3 ) . Loss of
ozone r educes t he at mos pher e' s ability t o screen out ul t ravi ol et r adi at i on.
Th e pr oduct i on of N2 O is a nat ur al event t hat occurs by deni t ri fi cat i on in
t he N cycle. Anyt hi ng t hat i ncreases N fixation, i ncl udi ng N fixed by
l egumes, i ncreases t he f or mat i on of N2 O. At t he pr esent t i me loss of ozone
appear s t o be a valid concer n, and t he magni t ude of t he pr obl em i s not
F I G U R E 10. 6 Extensive losses of ni trogen by
denitrification and loss of excess i norgani c ni-
t rogen by l eachi ng occur from rates of N appli-
cation i n excess of plant needs. (From Boswell,
Meisinger, and Case, 1985, used by permi ssi on
of the Soil Sci ence Society of Ameri ca. )
F I G U R E 10. 7 Partitioning of phosphorus
bet ween the solution and the solid phase.
(From Ellis and Ol son, 1986. )
F I G U R E 10. 5 The maxi mum profit from using a fertilizer
occurs at a yield that is less than the maxi mum yield.
known. But any fertilizer pract i ce t hat cont r i but es t o mor e efficient use of
N will mi mi mi ze N2 O pr obl ems.
P hos p hor u s
General l y, t he P concent r at i on of t he soil sol ut i on is very low and P r emai ns
qui t e i mmobi l e i n t he soil. In r ecent years t he car r yover of P, however , has
great l y i ncreased t he level of P in soil tests. T h e rel at i on bet ween t he P
r eveal ed by a soil test and t he concent r at i on of P in sol ut i on for t wo soils is
shown i n Fi gur e 10. 7. Th e Hoyt vi l l e soil i s fi ne-t ext ured and t he Hillsdale i s
a sandy soil. A given a mount of P in t he sandy soil made t he concent r at i on
of P in sol ut i on hi gher . Thus , hi gh soil tests on some soils cause concer n for
eut r ophi cat i on from P in runoff. Recent r esear ch has shown significant
downwar d movement of P in sandy soils wi t h very hi gh soil test levels.
Th e pract i ce of no-till cr oppi ng has i nt r oduced an addi t i onal way i n
whi ch P can be lost t o t he envi r onment . Cont i nuous no-till cr oppi ng bui l ds
up gr eat er amount s of P i n t he i mmedi at e soil surface and t he pot ent i al for
gr eat er movement of P by erosi on. On t he ot her hand, runoff and erosi on
ar e general l y much less t han from soils on whi ch convent i onal tillage pr ac-
tices ar e used because mor e cr op resi dues r emai n on t he soil surface.
REF ERENCES
Aldrich, S. R. 1984. Nitrogen Management to Minimize Adverse Effects on the
Environment. In Nitrogen in Crop Production. Am. Soc. Agron., Madison, Wis.
Boswell, F. C, J. J. Meisinger, and N. L. Case. 1985. Production, Marketing and
Use of Nitrogen Fertilizers. In Fertilizer Technology and Use. 3rd ed., O. P.
Engelstad, ed. Soil Sci. Soc. Am., Madison, Wis.
Ellis, B. G., and R. A. Olson. 1986. Economic, Agronomic and Environmental Implica-
tions of Fertilizer Recommendations. North Central Regional Research Pub. 310,
Mich. Agr. Exp. Sta., East Lansing.
Follett, R. H., L. S. Murphy, and R. L. Donahue. Fertilizers and Soil Amendments.
Prentice-Hall, Englewood Cliffs, N. J.
Foth, H. D. 1974. Effect of Plow Depth and Fertilizer Rate on Yields of Corn, Barley,
Soybeans and Alfalfa and on Soil Tests. Research Report 241, Mich. Agr. Exp.
Sta., East Lansing.
Gilliam, J. W., T. J. Logan, and F. E. Broadbent. 1985. Fertilizer Use in Relation to
the Environment. In Fertilizer Technology and Use. 3rd ed., O. P. Engelstad, ed.
Iowa State University Cooperative Extension Service. 1982. General Guide For
Fertilizer Recommendations in Iowa. Agronomy Dept., Ames.
National Research Council. 1972. Soils of the Humid Tropics. Nat. Acad. Sci., Wash-
ington, D.C.
Ohio State University Cooperative Extension Service. 1986. Ohio Agronomy Guide.
Bull. 472. Agronomy Dept., Columbus.
Olson, R. A., K. D. Frank, P. H. Grabouski, and G. W. Rehm. 1982. Economic and
Agronomic Impacts of Varied Philosophies of Soil Testing. Agron. Jour.
74: 492- 499.
References 207
Plank, C. O., 1985. Soil Test Handbook for Georgia. University of Georgia Coopera-
tive Extension Service, Athens.
Randall, G. W., K. L. Wells, and J. J. Hanway. 1985. Modern Techniques of
Fertilizer Application. In Fertilizer Technology and Use. 3rd ed., O. P. Engelstad,
ed. Soil Sci. Soc. Am., Madison, Wis.
Robertson, L. S., D. D. Warncke, and D. L. Mokma. 1978. Test Levels in Profiles of
Two Soils Producing World-Record Corn Yields. Research Report 363, Mich. Agr.
Exp. Sta., East Lansing.
Terman, G. L. 1982. Fertilizer Sources and Composition. In Handbook of Soils and
Climate in Agriculture. CRC Press, Boca Raton, Fla.
Tisdale, S. L., W. L. Nelson, and J. D. Beaton. 1985, Soil Fertility and Fertilizers. 4th
University of Illinois Cooperative Extension Service. 1984. Illinois Agronomy Hand-
book 1985-1986. Cir. 1233, Agronomy Dept., Urbana.
Viets, F. G. 1961. Fertilizers and the Efficient Use of Fertilizers. In Advances in
Agronomy. Vol. 14. Am. Soc. Agron., Madison, Wis.
Viets, F. G. 1971. Fertilizer in Relation to Surface and Ground Water Pollution. In
Fertilizer Technology and Use. Soil Sci. Soc. Am., Madison, Wis.
Wolcott, A. R., H. D. Foth, J. F. Davis, and J. C. Shickluna. 1965. Nitrogen
Carriers: Soil Effects. Soil Sci. Soc. Am. Proc. 29: 405- 410.
Woodruff, C. M. and D. D. Smith. 1946. Shattering and Subsoil Liming for Crop
Production on Claypan Soils. Soil Sci. Soc. Am. Proc. 11: 539- 542.
Index
Aci di fi cat i on, of soil, 59
Aci di t y a nd basicity, of fert i l i zers, 172
Aci d r ai n, 58
Aci d soil:
causes, 3 9 - 4 1
exchangeabl e a l umi num, 32
exchangeabl e cat i ons, 41
i nfert i l i t y, 47
r ol e of a l umi num, 40
Al kal i ni t y:
causes, 38
i nfert i l i t y, 49
Al l ophane, 25, 27
Al umi num:
exchangeabl e, 40
hydrol ysi s, 4 1 , 51
i nt er l ayer , 22, 40
neut r al i zat i on by l i me, 51
t oxi ci t y, 4 3 - 4 6 , 4 9
Al umi num sul fat e, t o acidify soil, 59
Ammoni a , f or mat i on in soil, 69. See also An-
hydr ous a mmoni a i nj ect i on i n soil
Ammoni f i cat i on, 69
Ammo n i u m:
f i xat i on, 70
upt ake by pl ant s, 75
Ammo n i u m ni t r at e, 83
Ammo n i u m phos phat es , 103
Ammo n i u m sul fat e, 85
Anhydr ous a mmoni a :
i nj ect i on i n soil, 8 0 - 8 2 , 192
pr oper t i es , 80
synt hesi s, 79
use i n fert i l i zer manuf act ur e, 103, 162
Ani on exchange, 26, 34
Ani on exchange capaci t y, 26, 27, 34
Apat i t e, 89
Az ol l a - Ana ba e na , 65, 66, 68
Azot obact er , 69
Base sat ur at i on, 4 6 - 4 7
Basic cat i on sat ur at i on r at i o, 199
Bei del l i t e, 22
Bet a t r i cal ci um phos phat e, 106
Bi ot i t e, 112, 115
Bi ur et , 83
Bl ue- gr een al gae, ni t r ogen f i xat i on, 6 5 , 66
Bor on:
a mo u n t i n pl ant s and soils, 6, 152
deficiency s ympt oms , 157
fact ors affect i ng availability, 148, 149
fert i l i zer car r i er s and use, 149
f or ms i n soils, 148
Br oadcast , fert i l i zer appl i cat i on, 194
Bul k bl ended fert i l i zers, 165
Ca dmi um, t oxi ci t y, 150
Cal car eous soil, pr oper t i es , 3 1 , 32, 38
Calcitic l i me, 56
Cal ci um:
a mo u n t i n pl ant s, 6
a mo u n t in soils, 6
defi ci ency i n s er pent i ne soils, 33
exchangeabl e, 3 1 - 3 4
pl ant upt ake, 8, 34
Cal ci um car bonat e equi val ent , 56
208
Index 209
Cal ci um ni t r at e, 85
Ca r bon t o ni t r ogen r at i o, 72
Ca r r i e r t heor y, of i on upt ake, 10
Cat i on bal ance, fert i l i zer r e c omme nda t i ons ,
199
Cat i on exchange:
def i ned, 17
fact ors affect i ng, 3 0 , 3 1
uni que selectivities, 31
Cat i on e xc ha nge capaci t y:
of clay, 1 9 - 2 7
def i ned, 17
de t e r mi na t i on, 18
effective, 28
effect on pot assi um availability, 126
of or gani c mat t er , 18
pe r ma ne nt , 19
pH de pe nde nt or var i abl e, 19, 54
of soils, 2 7 - 2 9
Chel at es:
i r on, 147
ma nga ne s e , 146
Chl or i ne, 6
Ch r o mi u m, t oxi ci t y, 151
Clay mi ner al s, or i gi n a nd pr oper t i es , 1 9 - 2 7
Compl i ment ar y i on effect, 30
Coppe r :
a mo u n t i n pl ant s, 6, 152
defi ci ency s ympt oms , 157
fert i l i zer car r i er s a nd use, 141
pl ant upt ake, 141
Cri t i cal nut r i e nt concent r at i on, 186
Cr op l oggi ng, 188
Cr op r ot at i on, 86
Defi ci ency s ympt oms , mi cr onut r i ent s ,
1 5 2 - 1 5 8
Deni t ri fi cat i on, 73
De pr ot ona t i on, 18, 24, 26
Di a mmoni um phos phat e, 103
Di cal ci um phos phat e, 96, 106
Diffusion, of nut r i ent s t o r oot s , 8
Dol omi t i c l i me, 56
DRI S i ndi ces, 189
Economi cs, of fert i l i zer use, 2 0 3
Effective cat i on e xc ha nge capaci t y, 28
Envi r onment al affects, of fert i l i zer use, 108,
150, 204
Essent i al el ement s:
a mo u n t i n pl ant s, 6
a mount s in soils, 6
Exchangeabl e a l umi num:
compar i s ons i n soils, 4 3 - 4 6
r ol e i n aci di t y, 40, 41
Exchangeabl e bases, 3 1 , 46
Exchangeabl e cat i ons:
i n aci d soils, 4 1 , 51
i n al kal i ne soils, 38
a mount s i n soils, 33
i n cal car eous soils, 3 1 - 3 4
i n sodi c soils, 32, 38
sour ce of nut r i ent s , 33, 34
Exchangeabl e cat i on sui t es, 3 1 - 3 3
Fer t i gat i on, 195
Fer t i l i zer appl i cat i on:
band, 1 9 2 - 1 9 4
br oadcast , 194
de e p i n soil, 197
f er t i gat i on, 195
foliar, 196
i nj ect i on of a mmoni a , 80, 192
wi t h tillage oper at i ons , 194
Fer t i l i zer manuf act ur e:
ni t r ogen, 7 9 - 8 6
phos phor us , 1 0 1 - 1 0 4
pot assi um, 1 2 9 - 1 3 2
Fer t i l i zer pl acement , see Fer t i l i zer appl i ca-
t i on, ba nd
Fert i l i zers:
aci di t y a nd basicity, 86, 172
appl i cat i on pr act i ces, 1 9 1 - 1 9 7
bul k bl endi ng, 165
caki ng a nd dust i ness, 164
car r yover , 77, 198, 199
chemi cal compat i bi l i t y, 167
economi cs of use, 203
effect on soil p H, 202
effect on wat er use efficiency, 200
envi r onment al concer ns , 204
f l ui d, 84, 169
gr a de a nd r at i o, 161
gr anul ar , 1 6 1 - 1 6 4
i mpor t ance, 14
maj or syst ems, 161
mel t gr anul at i on, 162
mi cr onut r i ent s , 1 4 1 , 144, 146, 1 4 8 - 1 5 0 ,
170
mi xed, 160- 176
n i t r o g e n , 7 9 - 8 6
pest i ci de i ncor por at i on, 174
phos phor us , 101- 104
pl acement i n soil, 191- 197
pot assi um, 1 2 9 - 1 3 2
salt i ndex, 172
segr egat i on, 167
210 Index
Fer t i l i zer s (Continued)
suspensi ons, 170
Fol i ar fert i l i zer appl i cat i on, 196
Fl ui d fert i l i zer, 169
Fr eundl i ch equat i on, 94
Gi bbsi t e:
f or mat i on, 24
pr oper t i es , 24, 25, 27
Goet hi t e, 27
Gyps um, 60, 102
Heavy met al s, i n sl udges, 150
Her bi ci de, i n fert i l i zer, 175
Hi st osol , see Or ga ni c soils
Hydr ous mi ca:
f or mat i on, 20, 115
pot assi um fi xat i on, 20, 116
pr oper t i es , 20, 27
Hydr oxy- al umi num:
hydrol ysi s, 4 1 , 51
i nt er l ayer , 22
Il l i t e, see Hydr ous mi ca, f or mat i on
I mmobi l i zat i on, of ni t r ogen, 72
Inosi t ol phos phor us , 98
I on di st r i but i on, ne a r char ged surfaces, 29
I on exchange, 1 7 - 3 5
I on move me nt , t o r oot s, 7, 8
I on upt ake, car r i er t heor y, 10
I r on:
defi ci ency s ympt oms , 5, 157
fact ors affect i ng availability, 146
fert i l i zat i on, 147
I r on sul fat e, t o acidify soil, 59
I sobut yl i dene di ur ea, 85
I s omor phor us subst i t ut i on, 20
Kaol i ni t e, 2 3 , 27
La ngmui r equat i on, 95
Legumes , ni t r ogen fi xat i on, 65
Li ebi g, 3
Li me:
appl i cat i on, 57
cal ci um car bonat e equi val ent , 56
use, 5 0 - 5 9
Li me r e qui r e me nt , det er mi nat i on, 5 3 - 5 5
Li mes t one:
as l i mi ng mat er i al , 56
neut r al i zi ng val ue, 56
qual i t y, 56, 57
Li qui d fert i l i zer, 169
Low act i vi t y clay soils, 26, 4 3 , 53, 90
Luxur y cons umpt i on:
def i ned, 185
of pot assi um, 124
Magnes i um:
a mo u n t in pl ant s, 6
a mo u n t i n soils, 6, 34
exchangeabl e cat i on, 3 1 - 3 4
i n s er pent i ne soils, 33
Manganes e:
fert i l i zat i on, 145, 146
i r on i nt er act i on, 145
t oxi ci t y, 4 8 , 49
Mass fl ow, move me nt of i ons t o r oot s , 8
Mi cr ocl i ne, 112, 115
Mi cr onut r i ent s :
essent i al , 139
i ncor por at i on i n fert i l i zer, 170
pl ant defi ci ency s ympt oms , 1 5 2 - 1 5 8
i n soils a nd fert i l i zers, 1 3 8 - 1 5 8
soil tests, 151
t oxi ci t y, t o pl ant s a nd ani mal s, 150
Mi l l i equi val ent , 17
Mi xed fert i l i zers, 1 6 0 - 1 7 6
Mol ybde num:
Mont mor i l l oni t e:
f or mat i on, 22
pr oper t i es , 22, 27
Mor r ow pl ot s, 15
Muscovi t e, 20, 112, 115
Ni t ri fi cat i on i nhi bi t or s, 192
Ni t r ogen:
a mmo n i u m vs. ni t r at e f or ms, 75
bi ol ogi cal f i x a t i o n , 6 5 - 6 9
deficiency s ympt oms , 62, 178
deni t ri fi cat i on, 73
fert i l i zer r e c omme nda t i ons , 7 5 - 7 8
f i x a t i o n , 6 3 - 6 9
i mmobi l i zat i on, 72
i nvent or y of ear t h, 62
mass fl ow, of ni t r at e, 8, 75
mi ner al i zat i on, 69
Index 211
ni t ri fi cat i on, 70
pl ant upt ake, 75
r ol e i n pl ant s, 62
soil cycle, 63
Ni t r ogen fert i l i zers, 7 9 - 8 6
aci di t y a nd basicity, 86, 172, 202
a mmo n i a synt hesi s, 79
a mmo n i u m ni t r at e, 83
a mmo n i u m phos phat es , 103
a mmo n i u m sul fat e, 85
car r i er compar i sons, 86
cont r ol l ed r el ease, 84
gaseous loss, 192, 194, 196
maj or car r i er s, 79
sol ut i ons, 84
ur ea, 82
Nut r i e nt upt ake:
car r i er t heor y, 10
vs. pl ant gr owt h, 12
r ol e of diffusion, 7
r ol e of mass flow, 8
r ol e of r oot i nt er cept i on, 7
Oct acal ci um phos phat e, 96, 106
Or ga ni c mat t er :
affect on a l umi num t oxi ci t y, 4 8 , 49
cat i on exchange capaci t y, 28
as ni t r ogen r eser voi r , 62
Or ga ni c soils, pH vs. nut r i ent availability, 49,
50
Or t hocl as e, 112, 115
Over l i mi ng, 58
Oxi di c clay, 2 4 - 2 7 , 43
Oxi sol s, 26, 4 3 , 5 3 , 9 1 , 129
Pest i ci des, i n fert i l i zers, 174
p H, def i ned, 36
pH d e p e n d e n t char ge, var i abl e, 18, 19, 28
Phos phor i c aci d, pr oduct i on, 102
Phos phor us :
a ds or be d, 93
bi ol ogi cal i ncor por at i on, 89, 97
cycl i ng i n soils, 89
e a r t h' s i nvent or y, 88
effect on zinc upt ake, 142
fi xat i on by pr eci pi t at i on, 91
f or ms:
i n aci d soils, 96
i n cal car eous soils, 96
i n fert i l i zed soils, 90
i n sol ut i on, 92
i n st r ongl y we a t he r e d soils, 90
i r on and a l umi num f or ms, 90
or gani c, 97
pr eci pi t at ed f or ms, 93
resi dual f or ms, 107
soil, ads or pt i on capaci t y, 9 3 - 9 5
soil tests, 100
Phos phor us fert i l i zers, 1 0 3 - 1 0 6
a mmo n i u m phos phat es , 103
appl i cat i on, 1 0 4 - 1 0 8
car r yover , 107
fate in soils, 106
pr oduct i on processes, 1 0 1 - 1 0 4
r e c omme nda t i ons for var i ous cr ops, 101
r ock phos phat e, 104
use in no-till syst ems, 108
Pol yphosphat es, 103
Posi t i ve char ge, of soils, 26, 27
Pot assi um:
activity r at i o, 123
a mo u n t i n soils, 6, 111, 120
buf f er i ng capaci t y of soil, 123
cycle i n soils, 1 1 1 - 1 1 3
exchangeabl e a nd sol ut i on f or ms, 118
f i xat i on, 116
f or ms in soils, 112
l eachi ng, 119
l uxur y cons umpt i on, 124
r ol e i n pl ant s, 121
soil t est s, 129
Pot assi um fert i l i zers:
basis for r e c omme nda t i ons , 129
car r y over , 199
manuf act ur e, 1 2 9 - 1 3 2
pr oper t i es and use, 1 2 9 - 1 3 2
Pot assi um upt ake:
affect of aer at i on, 127
grass vs. l egumes, 127
r ol e of diffusion, 122
vs. soil f or ms, 120
Pr ot onat i on, 26, 34
Quant i t y a nd i nt ensi t y r el at i onshi p, for po-
t assi um, 123
Rock phos phat e:
maj or deposi t s, 88
pr oper t i es , 89
soil appl i cat i on, 104
use i n fert i l i zer manuf act ur e, 101
212 Index
Root , mor phol ogy, 8
Root i nt er cept i on of nut r i ent s , 7
Sal i ne soil, 32
Salt i ndex, of fert i l i zers, 172
Ser pent i ne, ba r r e ns a nd soils, 33
Smect i t es, 22
Sodi c soil, 32, 38
Sodi um, exchangeabl e, 32, 38
Soil fertility:
Alfisols vs. Ultisols a nd Oxi sol s, 4 3 - 4 5
def i ned, 1
eval uat i on, 1 7 7 - 1 9 0
hi st ori cal , 2
r el at i on t o Soil Ta x o n o my , 46, 47
Soil p H:
causes, 3 8 - 4 1
c ont i nuum, 38
det er mi nat i on, 37
effect:
on nut r i ent availability, 4 7 - 5 0 ,
1 4 1 - 1 4 9
on phos phor us i n sol ut i on, 92
on pl ant gr owt h, 47
fl oodi ng affects, 58
pl ant pr ef er ence, 52
r a nge i n soils, 42
r el at i on t o pot assi um upt ake, 127
Soil pr oduct i vi t y, 1
Soil tests:
cal i br at i on, 183
cor r el at i on, 181
l i me r e qui r e me nt , 5 3 - 5 5
sampl i ng, 179
Sul fur:
i n pr eci pi t at i on, 135
for soil aci di fi cat i on, 59
Sul fur coat ed ur ea, 85
Supe r phos phat e:
pr oduc t i on, 102
use, 104
Suspensi on fert i l i zers, 170
Syl vi ni t e, 130
Ta r a nki t e s , 96
Ti l l age, a nd fert i l i zer appl i cat i on, 195
Toxi ci t y, heavy met al s, 150
Tr a c e el ement s, 139
Ultisols, 26, 4 3 , 53, 114, 129
Ur e a , 82
Ur e a f or mal dehyde, 85
Ver mi cul i t e:
f or mat i on, 20
pr oper t i es , 20, 2 1 , 27
Vol cani c ash, 25
Vol i t al i zat i on, of ni t r ogen, 64, 69, 192, 194,
196
Wa t e r pot ent i al , effect on nut r i e nt upt ake,
201
Wa t e r use efficiency, affect ed by fert i l i zer
use, 200
We a t he r i ng, effect on soil p H, 39, 43
Zer o poi nt of char ge, 26
Zi nc:
effect on phos phor us upt ake, 142

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SOIL

ions with cat i on

, whi ch resul t s i n t he f or mat i on of wat er and an unsatis-

in a process similar to t hat shown in

= 6). Wh e n equat i ons ar e wr i t t en wi t h Al fully hydr at ed, it is

) per se but t he associated chemi cal envi r on-

t o f or m wat er . T h e overall r eact i on r epr es ent i ng

suppl i ed by t he l i me. At pH of about 7, t he hydr oxy- Al i s pr eci pi t at ed

, and t hat this subst ance cont r i but es t o t he loss

by r oot s and t he het er ot r ophi c mi cr o-

for t hei r el ect r on accept or

i s pr oduced i n an aer obi c envi r onment and deni t ri fi cat i on occurs i n

and cr eat i ng dr i er soil wi t h a gr eat er O2 diffusion r at e. On

ar e commonl y pr esent i n soil sol ut i ons, a nd bot h ar e

. At t he ext r eme ar e cran-

i s excr et ed, whi ch i ncreases t he pH of t he

. T h e quest i on whet her NO3

t o be car r i ed over. A test t o det er mi ne t he

i n t he r oot zone i s used i n many of t he west er n states. T h e

l eachi ng, and deni t ri fi cat i on is mor e likely.

over t he di val ent H P O 4

, causes Ca and Mg salts t o pr eci pi t at e, whi ch can clog

exists i n t he soil t han pl ant s can use.

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