International Fertilizer Development Center - Analytical Manual

IFDC
Fertilizer
Analytical
Manual
Foreword
Since fertilizers are sold (and guaranteed) according to their nutrient
composition, it is necessary to have available analytical methods to accurately
determine the plant nutrient content.
Fertilizers provide all essential plant nutrient elements except carbon,
hydrogen, and oxygen. The total number of essential elements is generally agreed to
be 18 and of the 15 that may come from fertilizers, methods of analysis for all but one
(molybdenum) are included in this manual. Several different methods of analysis for
most all of these elements exist with some being more accurate than others and some
being more elaborate or expensive to apply.
The methods of analysis included in this manual are all based on methods
adopted by AOAC International [formerly Association of Official Analytical Chemists
(AOAC)] or the International Organization for Standardization (ISO). AOAC and ISO
methods have been studied rigorously by multi-laboratory groups and exposed to
sophisticated statistical protocols before adoption. They are recognized as world
standards by fertilizer authorities and scientists.
Besides the methods detailed in this manual, there are others that are
recognized internationally and may be more appropriate for your requirements.
Examples are the methods of analysis of the European Union and Japan. Additionally,
because IFDC laboratories are largely research oriented, we have adopted and/or
developed project-specific methods of analysis that are not recognized as standard
national or international methods and are not included in this manual. If you have a
particular need for analyzing a material that is not covered by any of the methods
described in this manual, feel free to contact IFDC to ascertain if we have knowledge
of methodology that may be suitable for analyzing your specific material.
In addition to the individual methods presented, the manual also provides
important general reference material in the appendixes. This information can be a
helpful guide in promoting uniformity and efficiency. Appendix A presents methods
for the preparation of standard acids and bases. Appendix B shows an analytical report
form. Appendix C summarizes some very valuable information on laboratory safety.
Appendix D includes three typical job descriptions that may be useful in classifying
technical personnel in the laboratory.
We believe that the information in this manual is true and accurate. Any
recommendations or suggestions are made without warranty or guaranty of any kind.
Consequently, IFDC shall not be responsible for any incidental or consequential
damages resulting from the use of the procedures in this manual whatsoever.
The procedures in this manual may involve hazardous materials, operations,
and equipment. These procedures do not purport to address the safety problems
associated with their use. It is the responsibility of the user of these procedures to
establish appropriate safety and health practices and determine the applicability of
regulatory limitations prior to use.
This manual was prepared by the International Fertilizer Development Center.
Abbreviations, Acronyms, Definitions,

and Safety Notes
Abbreviations
kg
g
mg
g
L
mL
L
cm
mm
nm
N
A
=
=
=
=
=
=
=
=
=
=
=
=
kilogram
gram
milligram
microgram
liter
milliliter
microliter
centimeter
millimeter
nanometer
normality
absorbance
Acronyms
ISO =
DIS =
CD =
International Organization for Standardization

draft international standard
committee draft
Definitions
1.
"Water" or "H2O" means distilled or deionized water.
2.
In expressions (1 + 2), (5 + 4), etc., used in connection with liquid

reagents, the first number refers to volume of reagent and the second to
volume of water.
3.
In solutions defined in percentage, it is understood that the solution is

prepared as weight of reagent in volume of solution, unless otherwise
described.
4.
"Sulfuric acid, nitric acid," etc., when not further defined, means
concentrated reagent grade.
5.
All reagents, unless otherwise described, are of recognized analytical

grade.
6.
"Ordinary labware" means labware normally stocked in fertilizer

laboratories and includes items such as balances, pH meter, glassware,
stirrers, etc.
7.
All volumetric glassware listed conforms to ISO specifications.
8.
Temperature is expressed as degrees Celsius.
9.
The term "alcohol" means 95% ethanol unless otherwise specified.
Safety Notes
Perchloric Acid WARNING:
WARNING Fuming hot perchloric acid is a powerful
oxidizing agent and will react explosively with organic matter. Many inorganic
salts of perchloric acid are unstable and will decompose violently if taken to
dryness or baked. All perchloric acid dissolutions should be preceded by
preliminary oxidation with nitric acid, and nitric acid should be present in
solution when dilute perchloric solutions are to be concentrated to fuming. If,
in spite of these precautions, such a solution changes color from light yellow
to dark brown or black, dilute immediately with water or leave the vicinity
hurriedly. Fume hoods used for perchloric acid should be constructed of
inorganic material, preferably stainless steel, and equipped to be washed out
periodically. Under no circumstances should such hoods be used for heating
organic solvents or in other situations where combustible fumes or dust are
produced.
Laboratory S a f e t y Refer to Laboratory Safety Guidelines found in
Appendix C.
Table of Contents
Page
Sample Reduction and Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Total Nitrogen Modified Comprehensive Method (N-1) . . . . . . . . . . . . . . . . . . . . . . . 7
Ammoniacal Nitrogen Distillation-Titrimetric Method (N-2) . . . . . . . . . . . . . . . . . . 10
Ammoniacal and Nitrate Nitrogen Devarda Method (N-3) . . . . . . . . . . . . . . . . . . . 12
Biuret Spectrometric Method (N-4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Total Phosphorus Preparation of Sample Solution (P-1) . . . . . . . . . . . . . . . . . . . . . . 16
Water-Soluble Phosphorus Preparation of Sample Solution (P-2) . . . . . . . . . . . . . . 18
Citrate-Insoluble Phosphorus Preparation of Sample Solution (P-3) . . . . . . . . . . . . 20
Direct-Available Phosphorus Preparation of Sample Solution (P-4) . . . . . . . . . . . . 22
Phosphorus Gravimetric Quimociac Method (P-5) . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Phosphorus Alkalimetric Quimociac Method (P-6) . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Phosphorus Spectrometric Molybdovanadate Method (P-7) . . . . . . . . . . . . . . . . . . . 30
Potassium Gravimetric Tetraphenylborate Method (K-1) . . . . . . . . . . . . . . . . . . . . . . 33
Potassium Titrimetric Tetraphenylborate Method (K-2) . . . . . . . . . . . . . . . . . . . . . . . 36
Potassium Atomic Emission Method (K-3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Calcium Potassium Permanganate Method (Ca-1) . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Calcium Atomic Absorption Spectrometric Method (Ca-2) . . . . . . . . . . . . . . . . . . . . 44
Magnesium Atomic Absorption Spectrometric Method (Mg-1) . . . . . . . . . . . . . . . . . 47
Sulfur Gravimetric Barium Sulfate Method (S-1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Boron Azomethine H Spectrometric Method (B-1) . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Chloride Titrimetric Silver Nitrate Method (Cl-1) . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Cobalt Atomic Absorption Spectrometric Method (Co-1) . . . . . . . . . . . . . . . . . . . . . 58
Copper Atomic Absorption Spectrometric Method (Cu-1) . . . . . . . . . . . . . . . . . . . . . 62
Iron Atomic Absorption Spectrometric Method (Fe-1) . . . . . . . . . . . . . . . . . . . . . . . . 66
Manganese Atomic Absorption Spectrometric Method (Mn-1) . . . . . . . . . . . . . . . . . 70
Sodium Atomic Emission Spectrometric Method (Na-1) . . . . . . . . . . . . . . . . . . . . . . 74
Zinc Atomic Absorption Spectrometric Method (Zn-1) . . . . . . . . . . . . . . . . . . . . . . . 76
Free Water Vacuum-Desiccation Method (H2O-1) . . . . . . . . . . . . . . . . . . . . . . . . . . 80
Appendix A.
Appendix B.
Appendix C.
Appendix D.
Preparation of Standard Solutions

Analytical Report Form
Laboratory Safety
Job Descriptions
R-1
Sample Reduction and Preparation

Scope
Samples received in the laboratory must be reduced in mass to 225-500 g,
pulverized, if necessary reduced in mass again, and stored in airtight containers.
Procedures have been developed to standardize those manipulations necessary
to reduce and prepare solid fertilizer samples. It is recommended that these
procedures be carried out in a laboratory environment.
Apparatus
1.
Sample Reducer or Riffle A gated-riffle (Figure 1) constructed of

corrosion-resistant material is required. The size of the riffle shall be
appropriate to the quantity of sample being reduced. Receiving pans must
fit riffle from end to end of partitioned section.
For most unground fertilizer samples, the slot openings should be a
minimum of 12 mm.
2.
Grinder or Sample Pulverizer A grinder shall perform as required for the

procedure without changing the composition of the sample.
3.
Sieves, 2 Each 200 mm in diameter, with openings of 0.5 and 1.0 mm,
constructed of brass or stainless steel. Stainless steel sieves are
recommended for samples to be analyzed for micronutrients.
4.
Containers for Ground Samples Plastic or glass, 250 mL capacity, wide

mouth with airtight cap.
Procedure
Reduction of Unground Sample
1. Make sure that all equipment is clean.
2.
Set gated-riffle in level position, not tilted in any direction.
3.
Place the two empty receiving pans in position beneath the riffle.
4.
Transfer the composite sample to the hopper of the riffle.

1
R-1
5.
Open the gate fully and allow the entire sample to flow into the pans
beneath the riffle, forming two equal portions.
6.
If required, repeat steps 4 and 5, until sample is reduced to approximately

500 g. (If desired, retain the second half as reserve, until the preparation
is completed on the portion to be analyzed.)
7.
Transfer final sample to moistureproof containers and mark for

identification.
Note:
Note The container must be large enough to hold the entire final sample.
None should be discarded.
discarded If the only available container is too small,
sample may be reduced by riffling twice and saving one-half at each step,
resulting in one-fourth of the original sample, but must not be less than
250 g.
8.
Clean equipment before storing or re-use.
Preparation of Sample
1. Grind the entire sample after reduction. If further reduction to less than
250 g is desired, this must be done only on the ground sample.
2.
Grind dry fertilizer mixtures to pass 0.5 mm sieve.
3.
Fertilizer materials and moist fertilizer mixtures may be ground to pass

sieve with 1.0-mm openings.
4.
Grind as rapidly as possible to avoid loss or gain of moisture during the

grinding operation, but avoid overheating the sample.
5.
Periodically check the efficiency of the grinding mill screen by sieving the
entire ground sample, including brushings from grinding mill, through a
0.5 mm sieve. Regrind oversize with a mortar and pestle and install new
screens if necessary.
6.
Place entire sample on flexible rolling sheet of glazed butcher's paper,

smooth oil cloth, or polyethylene sheet for mixing.
R-1
7.
Roll sample slowly from four directions until sample has been thoroughly
mixed 20 times is usually considered adequate. Rolling too rapidly will
cause sliding and no mixing.
8.
After completion of mixing, roll sample into a pile in center of rolling sheet
and spread sample into a flat circle about 2.0 cm deep as shown in
Figure 2.
9.
Transfer about 200 g of sample to a 250 mL airtight, widemouth container

with a scoop such as shown in Figure 3. Scoop carefully from the
circumference toward the center, keeping the scoop edge next to the sheet.
Take portions at equal intervals of about 5-10 cm around the
circumference of the flattened pile. Use a backing plate as shown in
Figure 3.
10. Container must have air space above the sample.

11. Mark sample number on container and copy this on other records as
required.
12. Clean grinding mill after each use.
R-1
Figure 1. Riffle With Cutoff Gate and Two Pans.
R-1
R-1
Figure 3. Technique for Subsampling of Ground Sample.
N-1
Total Nitrogen
Modified Comprehensive Method
Scope
This method determines the total nitrogen content of any fertilizer.
Apparatus
1. Kjeldahl digestion and distillation units.
2. Kjeldahl flask, 800 mL.
3. Ordinary labware.
Reagents
1. Sulfuric acid, 0.5 N H2SO4 (see Appendix A).
2. Sodium hydroxide, 0.25 N NaOH (see Appendix A).
3. Methyl red indicator solution. Dissolve 1.0 g methyl red in 200 mL alcohol.
4. Copper sulfate, CuSO4 or CuSO45H2O.
5. Potassium sulfate, K 2SO4.
6. Sodium hydroxide solution, 45% NaOH. Dissolve 450 g of NaOH in H 2O,
cool, and dilute to 1 L.
7. Boiling stones, alundum or pumice, 1.5-2.5 mm.
8. Chromium metal, powder, of particle size not greater than 250 nm.
9. Sulfuric acid, H 2SO4.
10. Sulfuric acid, 1 + 1 H 2SO4.
11. Hydrochloric acid, HCl.
N-1
Procedure
1. Weigh 0.2-1.6 g 0.5 mg of sample and transfer to a Kjeldahl flask.
Sample must not contain more than 60 mg of nitrate nitrogen. If organics
other than urea or ureaform are present, weigh more than 0.5 g.
2. Add 1.2 g chromium powder and 35 mL H2O. For liquids make total
volume 35 mL. Let stand for 10 minutes with occasional gentle swirling to
dissolve all nitrate salts.
3. Add 7 mL HCl and let stand for at least 5 minutes, but not more than
10 minutes.
4. Place flask on preheated burner adjusted to a 7-7.5 minute boil test.1 After
heating 3.5 minutes, remove from heat and let cool.
5. Add 15 g of K2SO4, 0.4 g of CuSO4 or 0.6 g of CuSO45H2O, and several
boiling stones.
6. Add 37 mL 1 + 1 H 2SO4.
7. Place flask on preheated burner and heat until dense white fumes of
H2SO4 clear the bulb of the flask. Heat another 5-10 minutes. Digestion is
now complete for samples containing ammoniacal, nitrate, and urea
nitrogen. For all other samples, swirl flask gently and continue digestion
for 75 minutes.
8. Remove flask from burner. Allow to cool for 8-10 minutes, then swirl flask
a few times to prevent solidification of the digest. After further cooling, add
about 300 mL H 2O and cool to 25o or below.
9. To a 500 mL Erlenmeyer flask add 1 mL 0.5 N H2SO4 for each 7 mg
nitrogen in the sample plus 2 mL in excess. Add 5 drops of methyl red
indicator solution and sufficient H2O to cover the lower 15 mm of the
distillate delivery tube. Place the receiving flask under the delivery tube of
the Kjeldahl distillation unit.
10. Add boiling stones and with the flask tilted in position on the distillation
unit add sufficient 45% NaOH solution (at least 45 mL) to make contents
Heat required to bring 250 mL of water at 25oC to a rolling boil in 7-7.5 minutes.
N-1
of Kjeldahl flask strongly alkaline. With the flask tilted, the NaOH will
layer under the acid and not react violently.
11. Connect the flask immediately to the connecting bulb of the distillation
unit, swirl the flask so that the contents are mixed well, and heat until 150200 mL of distillate is collected in the receiver. If indicator changes color
during distillation, repeat the determination, using either a smaller sample
size or a larger volume of 0.5 N H2SO4.
12. Lower the receiver flask, wash the delivery tube with a few milliliters of
H2O into the collected distillate, and turn off the burner.
13. Titrate with 0.25 N NaOH to the methyl red end point.
14. Make a blank determination using the same reagents, omitting sample.
Calculation
References
1. Official Methods of Analysis of the Association of Official Analytical
Chemists, 15th Ed., Method 978.02, 1990.
2. Fertilizers Determination of Total Nitrogen Content Titrimetric
Method After Distillation, ISO 5315, 1984.
N-2
Ammoniacal Nitrogen
Distillation-Titrimetric Method
Scope
This method determines all nitrogen present in the ammoniacal form. It is not
applicable in the presence of urea or its derivatives, cyanamide, or organic
nitrogenous compounds.
Apparatus
1. Kjeldahl distillation unit.
2. Kjeldahl flasks, 800 mL.
Reagents
3. Methyl red indicator solution. Dissolve 1.0 g methyl red in 200 mL alcohol.
4. Sodium hydroxide solution, 45% NaOH. Dissolve 450 g of NaOH in water,
5. Boiling stones, alundum or pumice, 1.5-2.5 mm.
Procedure
1. Weigh a sample containing 250 mg of ammoniacal nitrogen and transfer
to a Kjeldahl flask.
2. To a 500 mL Erlenmeyer flask add 1 mL of 0.5 N H2SO4 for each 7 mg of
ammoniacal nitrogen in the sample plus at least 2 mL excess. Add 5 drops
of methyl red indicator solution and enough H2O to cover the lower
15 mm of the distillate delivery tube. Place the flask under the delivery
tube on the distillation unit.
3. Add 5 mL of 45% NaOH, several boiling stones, and 300 mL of H2O to the
Kjeldahl flask and connect immediately to the distillation unit. Swirl to
thoroughly mix the contents.
10
N-2
4. Apply heat and boil until 100-125 mL of distillate is collected in the
receiver flask.
5. Lower the receiver flask and rinse the delivery tube, catching the rinse H2O
in the flask. Turn off the heat.
6. Titrate with 0.25 N NaOH to the methyl red end point.
7. Make a blank determination using the same reagents, omitting sample.
Calculation
References
1. Fertilizers Determination of Ammoniacal Nitrogen Content
Titrimetric Method After Distillation, ISO 5314, 1981.
11
N-3
Ammoniacal and Nitrate Nitrogen

Devarda Method
Scope
The sum of ammoniacal and nitrate nitrogen is determined by this method. Urea,
calcium cyanamide, and organic matter must be absent.
Apparatus
1. Kjeldahl distillation unit.
2. Kjeldahl flask, 800 mL.
Reagents
3. Devarda alloy, 50% Cu, 45% Al, and 5% Zn.
5. Methyl red indicator. Dissolve 1.0 g methyl red in 200 mL alcohol.
Procedure
1. Weigh 0.5-2.0 g 0.5 mg of sample into a Kjeldahl flask and add 300 mL
of H 2O and 3.0 g of Devarda alloy.
2. To a 500 mL Erlenmeyer receiving flask add 1 mL 0.5 N H2SO4 for each
7 mg nitrogen in the sample plus 2 mL in excess. Add 5 drops of methyl red
indicator solution and sufficient H2O to cover the lower 15 mm of the
distillate delivery tube and place the receiving flask under the delivery
tube.
3. With the Kjeldahl flask containing the sample in position on the distillation
unit, add 5 mL of 45% NaOH by pouring down the side of the flask so that
mixing does not readily occur.
12
N-3
4. Immediately attach the Kjeldahl flask to the connecting bulb and mix the
contents of the flask by a gentle swirl. Place the flask on the heater and
heat slowly. As foaming decreases, increase heat sufficiently to distill
250 mL in about 1 hour.
5. Lower the receiving flask, rinse the delivery tube with H2O, and turn off
heat.
6. Titrate the excess sulfuric acid with 0.25 N NaOH to the indicator end
point.
7. Make a blank determination using the same reagents, omitting the sample.
Calculation
References
1. Fertilizers Determination of Ammoniacal amd Nitrate Nitrogen
Content Modified Devarda Method, ISO/DIS 11792.
13
N-4
Biuret
Spectrometric Method
Scope
This method is based on a colored complex formed when copper is added to a
solution containing biuret under controlled conditions. The method is applicable
to urea and urea solutions only; it cannot be used for mixed fertilizers. Biuret is
a nonnutrient, but it is important because it is an undesirable impurity in certain
applications.
Apparatus
1. Spectrometer capable of reading at 555 nm and utilizing 2- to 4-cm
cells.
2. Water bath, 30 5 o.
Reagents
2. Alkaline tartrate solution. Dissolve 40 g of NaOH in 500 mL of H 2O, cool,
add 50 g of NaKC4H4O64H2O, and dilute to 1 L with H2O. Let stand 1 day
before use.
3. Copper sulfate solution. Dissolve 15 g of CuSO45H2O in CO2-free H2O
and dilute to 1 L.
4. Biuret. To recrystallize, weigh about 10 g of reagent-grade biuret into a
2 L beaker, add 1 L of absolute alcohol, and dissolve. Concentrate by
gentle heating to reduce volume to about 250 mL. Cool and filter through
a fritted glass funnel. Repeat crystallization and dry final product 1 hour
at 105o-110o in an oven. Remove from oven, place in a desiccator, and cool
to room temperature.
5. Biuret standard solution, 1 mg/mL. Dissolve 1.0000 g 0.5 mg of
recrystallized biuret in CO2-free H 2O and dilute to 1 L.
6. Methyl red indicator solution. Dissolve 1.0 g of methyl red in 200 mL of
alcohol.
14
N-4
Procedure
1. Weigh 10 g of sample containing 30-125 mg of biuret into a 250 mL
beaker. Add 150 mL of 50o H2O and stir for 30 minutes, maintaining this
temperature.
2. Filter into a 250 mL volumetric flask, cool, and dilute to volume.
3. Transfer a 50 mL aliquot of the sample solution to a 100 mL volumetric
flask. Also transfer a series of aliquots, 2-50 mL, of the standard biuret
solution to 100 mL volumetric flasks.
4. Adjust the volume to about 50 mL, with CO2-free H2O, and add one drop
of methyl red indicator and 0.1 N H2SO4 until pink color is obtained.
5. Add, with swirling, 20 mL of alkaline tartrate solution and then 20 mL of
CuSO4 solution. Dilute to volume, shake 10 seconds, and place in a H 2O
bath at 30 5 o for 15 minutes. Also prepare a reagent blank.
6. Determine absorbance of each solution against the blank at 555 nm
utilizing a 2- or 4-cm cell.
7. Plot absorbance versus concentration of biuret and determine
concentration of biuret in sample solution.
Calculation
References
15
P-1
Total Phosphorus
Preparation of Sample Solution
Scope
This method details procedures for the preparation of sample solutions for the
determination of total phosphate (P 2 O 5 ) content of fertilizers and fertilizer
materials.
Apparatus
Reagents
2. Nitric acid, HNO 3.
3. Perchloric acid, HClO4.
4. Magnesium nitrate solution. Dissolve 950 g of Mg(NO 3)26H2O in H 2 O
and dilute to 1 L.
Procedure
1. Treat sample by one of the following methods as appropriate:
a.
All fertilizers, especially when the spectrometric method is to be

applied: Weigh 1-2 g 0.5 mg of sample into a beaker, add
20-30 mL HNO 3, and boil gently 30-45 minutes. (If the fertilizer
contains urea, add 20 mL HCl and boil gently for 20-30 minutes prior
to the addition of HNO 3.) Cool slightly, add 15-20 mL HClO4, and
boil very gently until solution is colorless or very nearly so and dense
white fumes fill the beaker. D ANGER! DO NOT BOIL TO
D R Y N E S S ! Cool slightly, add 50-100 mL H2O, and boil for
5-10 minutes. Cool, transfer to a volumetric flask, dilute to volume,
and mix thoroughly. Filter a portion through a dry retentive paper
(Whatman No. 42 or equivalent) and complete by method P-5, P-6,
or P-7.
b.
Materials containing large quantities of organic matter,

matter such as
cottonseed meal: Weigh 1.0 g 0.5 mg of sample into a 50 mL
evaporating dish and add 5 mL of Mg(NO 3)2 solution. Evaporate to
16
P-1
dryness and then ignite to destroy residual organic matter. Cool,
dissolve in 5 mL HCl, and transfer to a volumetric flask. Dilute to
volume and mix thoroughly. Filter a portion through a dry retentive
paper (Whatman No. 42 or equivalent) and complete by method P-5
or P-6.
c.
Materials containing small quantities of organic matter:

matter Weigh
1.0 g 0.5 mg of sample into a beaker and add 30 mL HNO 3 and
5 mL HCl. Boil gently until organic matter is destroyed (absence of
reddish-brown fumes). Cool, transfer to a volumetric flask, dilute to
volume, and mix thoroughly. Filter a portion through a dry retentive
paper (Whatman No. 42 or equivalent) and complete by method P-5
or P-6.
References
17
P-2
Water-Soluble Phosphorus
Scope
This method specifies a procedure for the preparation of a sample solution for
the determination of water-soluble phosphate (P2O5) in fertilizers and fertilizer
materials.
Apparatus
1. Filter paper, 9 cm, fine textured (Whatman No. 5 or equivalent).
2. Filtering funnel, 60o, with minimum of 100 mm stem.
Reagents
Procedure
1. Weigh 1.0 g 0.5 mg of sample and transfer to a 9 cm filter paper fitted
in a funnel.
2. Wash the sample with 10-15 mL portions of H2 O until the combined
washings approximate 225 mL. Add H2O in a fine stream directed around
entire periphery of filter paper in a circular path, ensuring that the H2O
and solids are thoroughly mixed with each addition. Allow each portion to
pass through filter before adding more H2O and use suction if washing
would not otherwise be complete in 1 hour. If filtrate is turbid, add 1-2 mL
HClO4, dilute to 250 mL, and mix thoroughly.
3. Make final determination of phosphate content by one of the following
methods:
a.
Transfer an aliquot containing 25 mg P2O5 to 400 mL beaker, dilute

if necessary to 50 mL, add 10 mL 1 + 1 HNO 3, and boil gently for
10 minutes. Cool, dilute to 100 mL, and proceed with method P-5,
beginning with "add 50 mL of quimociac reagent."
b.
Transfer an aliquot containing 30 mg P2O5 to a 500 mL Erlenmeyer

flask, dilute if necessary to 50 mL, add 10 mL 1 + 1 HNO 3, and boil
18
P-2
gently for 10 minutes. Cool, dilute to 100 mL, and proceed with
method P-6, beginning with "add 20 mL citric acid."
c.
Transfer an aliquot of the sample solution containing 2-5 mg of P 2O5

to a 100 mL volumetric flask. Proceed with method P-7, beginning
with step 7.
Note:
Note If the sample is suspected to contain nonorthophosphate, it must be
hydrolyzed by boiling in a dilute (10%) perchloric acid solution prior to
the final measurement of the P 2O5 content.
References
Chemists, 15th Ed., Methods 977.01, 962.03, 962.04, 970.01, 1990.
19
P-3
Citrate-Insoluble Phosphorus
Scope
This method separates phosphate (P2O5) that is insoluble in neutral ammonium
citrate solution and is considered to be unavailable to plants.
Apparatus
1. Constant temperature bath or oven with shaking apparatus. Shaking action
should be such that dispersion of sample in citrate solution is continually
maintained and entire inner surface of flask and stopper is continually
bathed with solution.
Reagents
1. Neutral ammonium citrate solution. Should have a specific gravity of 1.09
at 20o and a pH of 7.0 measured potentiometrically. Dissolve 370.0 g
crystalline citric acid in 1.5 L H2O and nearly neutralize by adding 345 mL
NH4OH (28%-29% NH3). If the concentration of NH3 is less than 28%, add
correspondingly larger volume of NH4OH and dissolve citric acid in
correspondingly smaller volume of H 2O. Cool and check pH. Adjust with
1 + 7 NH4OH or citric acid solution to pH 7.0 using a pH meter. Dilute
solution, if necessary, to a specific gravity 1.09 at 20o. Store in tightly
stoppered bottle. Check pH frequently and readjust to 7.0 if necessary.
4. Ammonium nitrate solution, 5% NH4NO3. Dissolve 50.0 g of crystalline
NH4NO3 in H 2O and dilute to 1 L.
Procedure
1. After removing water-soluble P2O5, transfer filter and residue within
1 hour to a 250 mL flask containing 100 mL of neutral ammonium citrate
solution previously heated to 65o.
2. Stopper flask tightly and shake vigorously until paper is reduced to pulp.
Relieve pressure in flask by removing stopper momentarily.
20
P-3
3. Continuously agitate stoppered flask in constant temperature apparatus at
65o for exactly 1 hour.
4. Remove flask from apparatus and immediately filter sample solution as
rapidly as possible through a retentive filter paper (Whatman No. 5 or
equivalent) using a Buchner funnel with vacuum.
5. Wash paper and residue with H2O heated to 65o until the volume of filtrate
is approximately 350 mL, allowing time for thorough draining between
each addition of wash H2O. If sample yields a cloudy filtrate, wash with 5%
NH4NO3 solution.
6. Prepare the residue for analysis by one of the following methods:
a.
Place the filter paper and residue in a porcelain crucible or dish. Dry
gently and ignite at 600o to destroy all organic matter. Transfer to a
250 mL beaker, add 5 mL HClO4, cover with a watch glass, and digest
at low temperature for 10 minutes. Dilute to volume in a volumetric
flask, mix, and filter a portion through a dry retentive paper
(Whatman No. 42 or equivalent).
b.
Transfer wet pad and residue to a 250 mL beaker and digest with
successive additions of HNO 3 until all organic matter is destroyed.
Add 5 mL of HClO4 and bring to dense white fumes of HClO4. Cool,
transfer to volumetric flask, dilute to volume, and mix. Filter a
portion through a dry retentive paper (Whatman No. 42 or
equivalent).
7. Make final determination of phosphate content by method P-5, P-6, or P-7.
References
21
P-4
Direct-Available Phosphorus
Scope
This method is used for the preparation of sample solution containing watersoluble and citrate-soluble phosphate (P2O5). The sum of the two is assumed to
be the phosphate that is available to plants.
Apparatus
1. Constant temperature oven or bath with shaking apparatus. Shaking action
should be such that dispersion of sample in citrate solution is continuously
maintained and entire inner surface of flask and stopper is continuously
bathed with solution.
2. Filter paper, 9 cm fine textured (Whatman No. 5 or equivalent).
3. Filtering funnel, 60o, with minimum of 100 mm stem.
Reagents
1. Neutral ammonium citrate solution. Should have a specific gravity of 1.09
at 20o and a pH of 7.0 measured potentiometrically. Dissolve 370.0 g
crystalline citric acid in 1.5 L H2O and nearly neutralize by adding 345 mL
NH4OH (28%-29% NH3). If the concentration of NH3 is less than 28%, add
correspondingly larger volume of NH 4OH and dissolve citric acid in
correspondingly smaller volume of H 2O. Cool and check pH. Adjust with
1 + 7 NH4OH or citric acid solution to pH 7.0 using a pH meter. Dilute
solution, if necessary, to a specific gravity 1.09 at 20o. Store in tightly
stoppered bottle. Check pH frequently and readjust to 7.0 if necessary.
2. Ternary acid mixture. Add 20 mL of H 2SO4 to 100 mL of HNO 3, mix, and
add 40 mL HClO4.
3. Modified molybdovanadate reagent. Dissolve 40 g of (NH 4)6Mo7O24
4H2O in 400 mL of hot H 2O and cool. Dissolve 2 g of NH 4VO3 in 250 mL
of hot H2O, cool, and add 250 mL of HClO4. Gradually add molybdate
solution to vanadate solution with stirring and dilute to 2 L.
22
P-4
Procedure
1. Weigh 1.0 g 0.5 mg of sample and place on a 9 cm filter paper fitted in
a funnel.
2. Wash the sample with 10-15 mL portions of H2O until the combined
washings approximate 225 mL. Add H 2O in a fine stream directed around
the entire periphery of filter paper in a circular path, ensuring that the
water and solids are thoroughly mixed with each addition. Allow each
portion to pass through filter before adding more H 2O and use suction if
washing would not otherwise be complete in 1 hour. Collect all washings
in a 500 mL volumetric flask.
3. Within 1 hour, transfer filter and residue to a 250 mL flask containing
100 mL of neutral ammonium citrate solution previously heated to 65o.
4. Stopper flask tightly and shake flask vigorously until paper is reduced to
pulp. Relieve pressure in flask by removing stopper momentarily.
5. Continuously agitate stoppered flask in a constant temperature apparatus
at 65o for exactly 1 hour.
6. Remove flask from apparatus and quantitatively transfer contents to the
500 mL volumetric flask containing the water-soluble fraction.
7. Immediately cool to room temperature, dilute to volume, and mix
thoroughly.
8. Filter a portion through a dry retentive filter paper (Whatman No. 40 or
equivalent).
9. Complete by one of the following methods:
a.
Transfer aliquot containing 25 mg P2O5 and 10 mL of original

neutral ammonium citrate solution to a 400 mL beaker, dilute if
necessary to 50 mL, and add 10 mL of 1 + 1 HNO 3. Boil gently for 10
minutes, cool, dilute to 100 mL with H2O, and continue as in method
P-5, beginning with "add 50 mL quimociac reagent."
b.
Transfer aliquot containing 30 mg P2O5 and 10 mL of original

neutral ammonium citrate solution to a 500 mL Erlenmeyer flask,
dilute if necessary to 50 mL, and add 10 mL of 1 + 1 HNO 3. Boil
23
P-4
gently for 10 minutes, cool, dilute to 100 mL with H2O, and continue
as in method P-6, beginning with "add 60 mL quimociac."
c.
Transfer a 10 mL aliquot to a 125 mL Erlenmeyer flask and add 5 mL

of ternary acid mixture. Swirl, boil gently for 15 minutes, and digest
at 150o-200o until clear white salt or colorless solution remains.
Evaporate to white fumes and continue heating for 5 minutes. Cool,
add 15 mL of H2O, and boil for 5 minutes. Transfer to 100 mL
volumetric flask, dilute to 50 mL, and cool to room temperature. Add
20 mL of modified molybdovanadate solution, dilute to volume, and
continue as in method P-7, beginning with Step 7.
References
24
P-5
Phosphorus
Gravimetric Quimociac Method
Scope
This method determines the orthophosphate content of sample solutions
prepared by methods outlined for total, water-soluble, citrate-insoluble, and
direct-available phosphate (P2O5). The method, based on the precipitation of the
phosphate as quinolinium molybdophosphate, is quite tolerant of extraneous
ions normally present in solutions of fertilizers.
Apparatus
1. Crucible, Gooch. Coors No. 4 or equivalent.
2. Filter disc, glass fiber, 2.4 cm.
3. Drying oven, adjusted to 250o.
4. Desiccator.
Reagents
1. Quimociac reagent. Dissolve 70 g of Na2MoO42H2O in 150 mL of H 2O.
Dissolve 60 g of citric acid in a mixture of 85 mL of HNO 3 and 150 mL of
H2O. Cool and gradually add the molybdate solution to the citric-nitric
acid mixture, with stirring. Dissolve 5 mL of synthetic quinoline in a mixture
of 35 mL of HNO 3 and 100 mL of H2 O. Add the quinoline solution
gradually to the molybdate solution, mix, and let stand for 24 hours. Filter,
add 280 mL of acetone, dilute to 1 L, and mix thoroughly.
Procedure
1. Transfer an aliquot of the sample solution containing 25 mg P2O5 to a
400 mL beaker. Dilute to 100 mL with H2O and add 50 mL of quimociac
reagent.
2. Cover the beaker with a watch glass, place on a hot plate in a wellventilated hood, and boil gently for 1 minute.
3. Remove from hot plate and cool to room temperature, stirring 3-4 times
during cooling.
25
P-5
4. Allow the precipitate to settle and filter through a tared Gooch crucible
fitted with a glass fiber disc previously dried at 250o. After complete
transfer, wash the precipitate an additional three times with 15 mL portions
of H 2O allowing the precipitate to suck dry between additions.
5. Dry crucible and contents at 250o for 30 minutes, cool in a desiccator, and
weigh as [(C9H7N)3H3(PO412MoO3)].
6. Determine a blank by carrying all reagents through entire procedure,
omitting the sample.
Calculation
where A = weight of sample precipitate (g).

B = weight of blank precipitate (g).
References
2. Fertilizers Determination of Phosphorus Content Quinoline
Phosphomolybdate Gravimetric Method, ISO 6598, 1985.
26
P-6
Phosphorus
Alkalimetric Quimociac Method
Scope
This method determines the total orthophosphate content of sample solutions
direct-available phosphate (P2O5). It is based on the precipitation of phosphate
as quinolinium molybdophosphate.
Apparatus
Reagents
1. Quimociac. Dissolve 70 g of Na2MoO42H2O in 150 mL of H 2O. Dissolve
60 g of citric acid in a mixture of 85 mL of HNO 3 and 150 mL of H 2O. Cool
and gradually add the molybdate solution to the citric-nitric acid mixture,
with stirring. Dissolve 5 mL of synthetic quinoline in a mixture of 35 mL of
HNO 3 and 100 mL of H2O. Add the quinoline solution gradually to the
molybdate solution, mix, and let stand for 24 hours. Filter, add 280 mL of
acetone, dilute to 1 L, and mix thoroughly.
2. Mixed indicator. Mix 2.2 mL of 0.1 N NaOH with 0.1 g of thymol blue and
dilute to 100 mL with 50% ethanol. Dissolve 0.1 g of phenolphthalein in
100 mL of 50% ethanol. Mix 3 volumes of thymol blue solution with
2 volumes of phenolphthalein solution.
3. Citric acid, 10%.
4. Sodium hydroxide, 0.3663 N NaOH (1 mL
Appendix A).
1 mg P 2 O 5 ) (see
5. Nitric acid, 0.3663 N HNO 3 (see Appendix A).
Procedure
1. Transfer an aliquot of the sample solution containing 30 mg P2O5 and
5 mL acid to a 500 mL Erlenmeyer flask.
2. Add 20 mL citric acid, adjust volume to 100 mL, add 60 mL quimociac,
cover with watch glass, and place on medium-temperature hot plate.
27
P-6
3. When the solution reaches the boiling point, move to a cooler portion of
the hot plate and boil gently for 1 minute.
4. Remove from hot plate and allow to cool until flask can be handled with
bare hand.
5. Prepare a pulped-paper filter pad on a perforated porcelain disk
approximately 7 mm thick by pouring two or more approximately equal
increments of a water suspension of pulped paper onto the disk and
sucking dry between additions.
6. Swirl flask, pour contents on the filter, and wash the flask five times with
15 mL portions of H2O, adding the washings to the filter funnel.
Immediately after the funnel has emptied, wash down the sides with a
15 mL portion of H2O to remove residual acetone which causes excessively
fast drying and subsequent lump formation if allowed to evaporate.
7. Wash precipitate three additional times with 15 mL portions of H 2O,
allowing the funnel to drain between additions.
8. Transfer the precipitate and pad to the precipitation flask and break up pad
with jet of H 2O.
9. Titrate with 0.3663 N NaOH to disappearance of yellow color and add 2to 5 mL excess.
10. Add 1 mL of mixed indicator and titrate with 0.3663 N HNO 3 to gray-blue
end point.
11. Determine a blank on all the reagents by the same procedure with a known
quantity (1-2 mg) of P2O5. Use 1+9 dilutions of standard NaOH and HNO 3
for the titration and subtract from the experimental titer the theoretical
titer equivalent to the P2O5 added. Calculate the difference to 0.3663 N
NaOH and subtract this blank from the 0.3663 N NaOH used in all sample
determinations.
28
P-6
Calculation
References
29
P-7
Phosphorus
Spectrometric Molybdovanadate Method
Scope
This method determines the total orthophosphate content of sample solutions
direct-available phosphate (P2O5). It is based on the intense yellow color of the
molybdovanadate phosphate complex and is relatively free of interference.
However, extraneous color, soluble silica, and oxides of nitrogen interfere and
must be absent.
Apparatus
1. Spectrometer with flow-through cell or matched 1-cm cells.
Reagents
1. Molybdovanadate solution. Dissolve 40 g of (NH 4)6Mo7O244H2O in
400 mL of hot H2O and cool. Dissolve 2 g of NH4VO3 in 250 mL of hot
H2O, cool, and add 450 mL of HClO4. Gradually add the molybdate
solution to the vanadate solution while stirring and dilute to 2 L.
2. Phosphate standard solutions. Dry pure KH 2 PO 4 (52.15% P2O5) for
2 hours at 105o. Prepare solutions containing 0.4-1.0 mg P2O5/mL in
0.1-mg increments by weighing 0.0767, 0.0959, 0.1151, 0.1342, 0.1534,
0.1726, and 0.1918 g of KH2PO4 and diluting each to 100 mL with H2O.
Weekly, prepare fresh solutions containing 0.4 and 0.7 mg P 2O5/mL.
Procedure
1. Transfer 5 mL aliquots of the seven standard phosphate solutions (2-5 mg
P2O5/aliquot) into 100 mL volumetric flasks and add about 45 mL of H2O.
Within 5 minutes for entire series, add 20 mL of molybdovanadate
solution, dilute to volume, mix, and let stand 10 minutes.
2. Fill both reference and sample cells with the 2.0 mg P2O5 standard
solution.
3. Set spectrometer to 400 nm and adjust to read 0 absorbance with standard
cell. Verify that sample cell reads 0 absorbance 0.001.
30
P-7
4. Using the sample cell, determine the absorbance of the other standards
while the instrument is adjusted to 0 absorbance with the 2.0 mg P2O5
standard.
5. Plot absorbance versus concentration (mg P2O5/100 mL) for each
standard.
6. Transfer an aliquot of the sample solution containing 2-5 mg of P 2O5 to a
100 mL volumetric flask.
7. Transfer aliquots of the standard phosphate solutions containing 2.0 and
3.5 mg P 2O5/aliquot to 100 mL volumetric flasks.
8. Dilute solution in each flask to about 50 mL with H2O. Within 5 minutes for
entire group, add 20 mL of molybdovanadate solution, dilute to volume,
and mix. Let stand 10 minutes.
9. Using the standard cell filled with the 2.0 mg P2O5 standard, adjust the
instrument to read 0 absorbance. Using the sample cell, determine the
absorbance of the 3.5 mg P2O5 standard. It should agree with the value on
the standard curve.
10. Read absorbance of the sample solution and determine concentration of
P2O5 from the standard curve.
Calculation
where A = mg P 2O5 from curve.
Notes
1. An instrument equipped with a flow-through cell may be substituted for an
instrument with fixed cells.
2. With some types of spectrometers it may be necessary to empty and refill
the reference cell containing the 2.0 mg P2O5 standard after each
31
P-7
measurement in order to avoid errors that might arise from temperature
changes.
References
32
K-1
Potassium
Gravimetric Tetraphenylborate Method
Scope
This method specifies a procedure for the determination of water-soluble potash
(K2O) in all fertilizers.
Apparatus
1. Drying oven, 120 5 o.
2. Filter crucibles, sintered glass or porcelain disc, of porosity grade P10 or
P16 (pore size 4-16 nm).
Reagents
1. Sodium tetraphenylborate (STPB) solution, ~15 g/L. Dissolve 7.5 g of
NaB(C6H5)4 in 480 mL of H 2O. Add 2 mL of NaOH solution and 20 mL of
MgCl 2 solution (100 g/L of MgCl 26H2O). Stir for 15 minutes and filter
through a fine-textured filter paper. May be stored in plastic for up to
1 month. Filter immediately before use if necessary.
2. Sodium tetraphenylborate wash solution. Dilute 1 volume of the sodium
tetraphenylborate solution with 10 volumes of H 2O.
3. EDTA solution. Dissolve 4.0 g of disodium ethylenediaminetetraacetate
dihydrate in 100 mL of H 2O.
4. Formaldehyde, 30% HCHO. Filter before use if necessary.
6. Phenolphthalein solution. Dissolve 0.5 g of phenolphthalein in 100 mL of
95% ethanol.
7. Bromine water, saturated solution.
8. Charcoal, activated (does not absorb or liberate potassium ions).
33
K-1
Procedure
1. Accurately weigh 5 g 1.0 mg of sample into a 1,000 mL Erlenmeyer
flask. Add 400 mL of H 2O, heat to boiling, and boil for 30 minutes.
2. Cool, transfer to a volumetric flask, dilute to volume, and mix well. Filter
a portion through a dry filter paper, discarding the first few milliliters.
3. Proceed as in a or b below:
a.
Procedure in presence of cyanamide and/or organic materials.

(1) Transfer an aliquot portion of the clear sample solution
containing 50-100 mg of K2O to a 250 mL beaker. Add 5 mL of
bromine water and boil until all bromine has been expelled
and the volume is <100 mL.
(2) Cool to room temperature, transfer to a 100 mL volumetric
flask, and add about 0.5 g of charcoal. Shake vigorously, dilute
to volume, and mix well.
(3) Filter the solution through a dry filter paper and transfer 50 mL
to a 250 mL beaker.
b.
Procedure in the absence of cyanamide and/or organic materials.

(1) Transfer an aliquot of the clear sample solution containing 2550 mg of K 2O to a 250 mL beaker and adjust the volume to
50 mL by dilution or evaporation.
4. Add 20 mL of EDTA solution and a few drops (3-5) of phenolphthalein

solution. Add NaOH solution dropwise until the appearance of a red color
and then add an additional 1 mL.
5. Boil for 15 minutes. Add 10 mL of HCHO solution and, if necessary, add
NaOH solution until the red color persists.
6. Cover the beaker with a watch glass and heat for 15 minutes on a steam
bath. If the solution does not remain red, add a few drops of
phenolphthalein and, if necessary, NaOH solution to restore the red color.
34
K-1
7. Remove the beaker from the steam bath and immediately add, dropwise
while stirring, 40 mL of the STPB solution (reagent 1).
8. Continue to stir for 1 minute, cool rapidly to below 20o, and allow to stand
for 10 minutes.
9. Filter through a tared filter crucible previously dried at 120 5o and
cooled in a desiccator. Decant the supernatant liquid through the crucible
and wash the precipitate in the beaker with 40 mL of the wash solution
(reagent 2) and decant. Wash with another 40 mL portion of wash solution
and decant.
10. Quantitatively transfer the precipitate to the crucible with about 40 mL of
wash solution and finally wash the precipitate with 5 mL of H 2O.
11. Dry the crucible and precipitate at 120 5o for 90 minutes, cool in a
desiccator, and weigh.
12. Determine a blank by the same procedure, omitting the sample.
Calculation
where A = the weight of precipitate from the sample.

B = the weight of precipitate from the blank.
References
1. Fertilizers Determination of Potassium Content Potassium
Tetraphenylborate Gravimetric Method, ISO 5318, 1983.
35
K-2
Potassium
Titrimetric Tetraphenylborate Method
Scope
This method specifies a procedure for the determination of potash (K2O) in all
fertilizers after extraction with ammonium oxalate solution. The final
measurement of the potash concentration is made by the titrimetric
tetraphenylborate method.
Apparatus
1. Microbiuret, 10 mL capacity, graduated in 0.02 mL divisions or smaller.
Reagents
1. Sodium hydroxide solution, 20% NaOH. Dissolve 20 g of NaOH in 100 mL
of H 2O.
2. Formaldehyde, 37% HCHO.
3. Sodium tetraphenylborate (STPB) solution, ~12 g/L. Dissolve 12 g of
NaB(C 6 H 5)4 in 800 mL of H2O. Add 20-25 g of Al(OH)3, stir for
10 minutes, and filter. Add 2 mL of 20% NaOH solution to the clear
filtrate, dilute to 1 L, and mix. Let stand 48 hours before standardizing.
Standardization of STPB
a.
Accurately weigh 2.5 g 0.5 mg of KH2PO4 (previously dried at 105o
and cooled in a desiccator), dissolve in H2O, add 50 mL of 4%
(NH 4)2C2O4H 2 O solution, and dilute to volume in a 250 mL
volumetric flask.
b.
Transfer a 15 mL aliquot of the KH2PO4 solution containing 51.92 mg

of K2O to a 100 mL volumetric flask. Add 2 mL of 20% NaOH
solution, 5 mL of 37% HCHO, and 43.0 mL of the STPB solution.
c.
Dilute to volume with H2O, mix thoroughly, and, after 10 minutes,

filter through a dry filter paper.
36
K-2
d.
Transfer a 50 mL aliquot of the filtrate to a 125 mL Erlenmeyer flask,

add 6-8 drops of Clayton yellow indicator, and titrate to a pink end
point with BAC solution.
e.
Calculate a factor (F) by the formula:
4. Benzalkonium chloride (BAC) solution. Dilute 38 mL of 17% Zephiran

chloride (benzalkonium chloride) solution to 1 L. To determine the ratio
between the STPB and BAC solutions, transfer 2.00 mL of the STPB
solution to a 125 mL Erlenmeyer flask. Add 20 mL of H2O, 1 mL of 20%
NaOH solution, 2.5 mL of 37% HCHO, 1.5 mL of 4% (NH 4)2C2O4H2O
solution, 6-8 drops of Clayton yellow indicator and titrate with BAC
solution to the pink end point. Adjust concentration of BAC so that 2.00 mL
= 1.00 mL of STPB.
5. Clayton yellow indicator, 0.04%. Dissolve 0.04 g of Clayton yellow (Titan
yellow, color index No. 19540) in H 2O and dilute to 100 mL.
6. Ammonium oxalate solution, 4%. Dissolve 40 g of (NH 4)2C2O4H2O in
H2O and dilute to 1 L.
7. Charcoal, activated (does not absorb or liberate potassium ions).
Procedure
1. Weigh 2.5 g 1.0 mg of sample (1.25 g if K2O > 50%) into a 400 mL
beaker. Add 125 mL of H 2O and 50 mL of 4% (NH 4)2C2O4H2O solution.
2. Boil for 30 minutes (add ~2 g of charcoal prior to boiling if organic matter
is known or thought to be present), cool, dilute to 250 mL in a volumetric
flask, and mix thoroughly.
3. Filter a portion of the sample solution through a dry filter, transfer a 15 mL
aliquot to a 100 mL volumetric flask, and add 2 mL of 20% NaOH solution
and 5 mL of 37% HCHO.
37
K-2
4. Add 1 mL of STPB solution for each 1% K2O in the sample plus 8 mL in
excess.
5. Dilute to volume with H2O, mix thoroughly, and, after 10 minutes, filter
through a dry filter.
6. Transfer a 50 mL aliquot of the clear filtrate to a 125 mL Erlenmeyer flask,
add 6-8 drops of Clayton yellow indicator solution, and titrate with BAC
solution to the pink end point using a microbiuret.
Precautions
1. The STPB solution is relatively stable. Under normal conditions, biweekly
restandardizations are adequate.
2. Do not premix formaldehyde and sodium hydroxide solution and add as
a single reagent. These mixtures rapidly lose their ability to complex
ammonia.
Calculation
where A = mL STPB solution.

B = mL BAC solution.
F = factor, mg K 2O/mL STPB.
References
38
K-3
Potassium
Atomic Emission Method
Scope
This method specifies a procedure for the determination of potash (K2O) in all
fertilizers after extraction with ammonium oxalate or water. The final
measurement of the potash concentration is made utilizing an atomic emission
spectrometer.
Apparatus
1. Atomic emission spectrometer with capability of reading emission at
766.5 nm using a lean, oxidizing air-acetylene flame.
Reagents
1. Potassium chloride solution, 1,000 mg K/L. Dissolve 1.9070 g of KCl in
H2O, add 10 mL HCl and dilute to 1 L.
2. Ammonium oxalate solution, 4%. Dissolve 40 g of (NH4)2C2O4H2O in
Procedure
1. Prepare a solution of the sample by one of the following methods:
a.
Weigh 2.5 g 1.0 mg of sample into a 400 mL beaker. Add 125 mL

of H2O and 50 mL of 4% (NH 4)2C2O4H2O solution. Boil for
30 minutes, cool, and dilute to volume in volumetric flask. Mix
thoroughly and filter a portion through a dry filter.
b.
Weigh 5.0 g 1.0 mg of sample into a 1,000 mL Erlenmeyer flask,

add 400 mL of H2O, and heat to boiling. Boil for 30 minutes, cool,
transfer to a volumetric flask, and dilute to volume. Mix thoroughly
and filter a portion through a dry filter, discarding the first few
milliliters.
2. Make a dilution of the clear sample solution from 1.a. or 1.b. such that the
concentration of K is 10 mg/L and add sufficient hydrochloric acid so that
the final sample solution contains 1% HCl.
3. Transfer a 25 mL aliquot of the KCl solution (1,000 mg K/L) to a 500 mL
volumetric flask and dilute to volume. Transfer aliquots of 0, 10, 25, and
39
K-3
50 mL of this solution to a series of 250 mL volumetric flasks, add 2.5 mL
of HCl to each flask, and dilute to volume. These solutions contain 0, 2, 5,
and 10 mg K/L.
4. Set instrumental parameters as directed in instrument manual.
5. Compare sample and standards by reading alternately about three times.
6. Read concentration directly (if instrument has capability) or plot emission
versus concentration of potassium.
Calculation
where V = final volume of sample solution.
References
1. Fertilizers Determination of Water-Soluble Potassium Content
Preparation of the Test Solution, ISO 5317, 1983.
Chemists, 15th Ed., Method 958.02C, 1990.
40
Ca-1
Calcium
Potassium Permanganate Method
Scope
This method specifies a titrimetric determination of calcium, expressed as CaO,
applicable to all mineral fertilizers.
Apparatus
1. Boiling water bath.
2. Electric hot plate with stirring capability.
3. Glass filter crucibles of porosity P16 (pore size 10-16 nm).
4. Vacuum filter apparatus with glass frit support screen or PTFE (e.g.,
Teflon) coated support screen and filter paper of about 50 mm diameter.
Reagents
3. Citric acid solution. Dissolve 300 g of citric acid monohydrate in H 2O and
dilute to 1 L.
4. Ammonium chloride solution. Dissolve 100 g of NH 4Cl in H 2O and dilute
to 1 L.
5. Bromophenol blue solution. Triturate 0.4 g bromophenol blue in 30 mL
of 0.02 N NaOH and dilute to 1 L with H 2O.
6. Ammonium oxalate solution (saturated). Slurry approximately 50 g of
(NH 4)2C2O4H2O with H 2O, transfer to a 1 L flask, dilute to volume, and
thoroughly mix. Filter through a glass filter crucible.
7. Ammonium oxalate solution (0.1%). Dissolve 1 g of (NH 4)2C2O4H2O in
41
Ca-1
8. Ammonia solution. Dilute 400 mL of NH 4OH (28%-29% NH3) to 1 L with
H2O.
9. Sulfuric acid, H 2SO4.
10. Sulfuric acid, 1+1 H 2SO4.
11. Potassium permanganate standard solution. Dissolve approximately 3.2 g
of KMnO4 in H2O and boil for 20 minutes. Cool, filter through a glass filter
crucible into a light-protected 1 L flask, and dilute to volume. After several
days filter the solution through a glass filter crucible and standardize using
Na2C2O4 solution.
12. Sodium oxalate solution. Accurately weigh 0.25-0.30 g of Na2C2O4 (dried
for 1 hour at 130o and cooled in a desiccator) into a 250 mL Erlenmeyer
flask. Dissolve in approximately 100 mL of H2O and add 30 mL of
1+1 H 2SO4. Heat in a boiling water bath and immediately titrate with the
standard KMnO4 solution to the first permanent pink color.
Procedure
1. Weigh 2.0-3.0 g 1.0 mg of sample into a 250 mL beaker. Add 15 mL of
H2O, 30 mL of HCl, and 3 mL of HNO 3.
2. Cover beaker with a watch glass and boil, while stirring, for 30 minutes.
Replace evaporated H 2O.
3. Cool, transfer to a 500 mL volumetric flask, dilute to volume, and mix.
4. Filter a portion through a dry paper filter, discarding the first few
milliliters.
5. Transfer an aliquot of the filtrate containing 30-80 mg of CaO to a 400 mL
beaker.
6. If necessary, dilute to 100 mL. Add 10 mL of citric acid solution and 5 mL
of NH 4Cl solution.
42
Ca-1
7. Heat to boiling. Add 10 drops of bromophenol blue indicator and 30 mL
of hot saturated (NH 4)2C2O4H2O solution, with stirring.
8. With constant stirring, slowly add ammonia solution until the indicator
changes color. Place beaker on a boiling water bath and allow to stand for
30 minutes.
9. Cool to room temperature, filter under vacuum, and wash the precipitate
with cold (NH 4)2C2O4H2O solution (0.1%) until washings are free of
chloride. (Acidify a portion of washings strongly with nitric acid prior to
adding silver to test for chloride.)
10. Wash four times with 10 mL portions of ice-cold H2O, breaking the vacuum
before each addition of H 2O to increase efficiency.
11. Using a pair of tweezers, remove the filter paper from the vacuum filter
apparatus and transfer to a 250 mL beaker. Rinse the upper portion of the
filter apparatus with H2O and 10 mL of 1 + 1 H 2SO4, adding the washings
to the beaker containing the filter paper.
12. Add 4 mL of H 2SO4, dilute to 100 mL with H 2O, and heat to 80o.
13. Add 1 mL of KMnO4 solution from a buret and stir until pink color
disappears. Continue titrating with the KMnO4 solution until the pink color
remains stable for about 30 seconds.
14. Determine a blank by following the same procedure, omitting the sample.
Calculation
where V 1 = mL of KMnO4 solution required for sample.

V2 = mL of KMnO4 solution required for blank.
References
1. Fertilizers Determination of Calcium Content Titrimetric Method,
ISO/CD 10151-2.
43
Ca-2
Calcium
Atomic Absorption Spectrometric Method
Scope
This method determines the calcium content of fertilizers by atomic absorption
spectrometry. It is applicable to the full range of calcium found in fertilizers.
Note:
Note Atomic absorption spectrometry is used for the determination of many
trace elements in fertilizers. It can also be applied to the determination of macro
quantities of various elements by giving sufficient attention to standards, samples,
and instrument operating parameters.
Apparatus
1. Atomic absorption spectrometer with a 10 cm air-acetylene burner
adjusted to a reducing flame (rich, red). A wavelength of 422.7 nm is the
most sensitive resonance line for calcium.
Note:
Note Less sensitivity may be obtained by rotating the burner head away
from the optical axis of the light beam or by substituting a smaller burner
head.
2. Hollow cathode lamp for calcium.
Reagents
1. Hydrochloric acid, 1 + 1 HCl.
2. Lanthanum solution, 100 g/L. Weigh 235 g of La2O3 into a 3 L beaker. Add
700 mL of H 2O and 1,000 mL of 1 + 1 HCl. Stir until dissolved, filter into
a 2 L volumetric flask, and cool to room temperature. Dilute to volume
with H 2O and mix thoroughly.
3. Primary calcium standard solution, 500 mg/L. Dissolve 1.2490 g of CaCO3,
previously dried at 105o, in 20 mL of 1 + 1 HCl and 50 mL of H2O.
Transfer quantitatively to a 1 L volumetric flask, dilute to volume, and mix
thoroughly. This solution may be stored safely in a polyethylene bottle for
approximately 1 year.
44
Ca-2
4. Secondary calcium standard solution, 50 mg/L. Transfer 50 mL of the
primary calcium standard solution to a 500 mL volumetric flask and dilute
to volume with H2O. This solution may be safely stored in a polyethylene
bottle for about 2 months.
5. Working calcium standard solutions, 5 mg/L, 10 mg/L, 15 mg/L, and
20 mg/L. Transfer 10 mL, 20 mL, 30 mL, and 40 mL of the secondary
calcium standard solution to four 100 mL volumetric flasks. To each flask
add 10 mL of the La2O3 solution and dilute to volume with H 2O.
Procedure
1. Weigh 2.5 g 1.0 mg of sample into a 250 mL beaker, add 50 mL of 1 + 1
HCl, cover with a watch glass, place on a hot plate, and bring to a boil.
2. Continue boiling for 30 minutes. Replace evaporated H 2O.
3. Cool, transfer quantitatively to a 500 mL volumetric flask, and dilute to
volume with H 2O.
4. Mix thoroughly and filter through a dry paper.
5. Transfer a 50 mL aliquot of the clear filtrate to a 250 mL volumetric flask,
dilute to volume with H 2O, and mix thoroughly.
6. Transfer a 10 mL aliquot to a 100 mL volumetric flask, add 10 mL of La2O3
solution, dilute to volume, and mix.
7. Prepare a blank solution in the same manner, omitting the sample.
8. Prepare the atomic absorption spectrometer in accordance with the
manufacturer's instructions and allow to warm up until stable operating
conditions are reached.
9. Adjust the spectrometer to zero while aspirating the blank solution. Then
obtain readings for the standard solutions and sample solution alternately,
about three times each, without interruptions or changing instrument
settings. Take each reading after a stable signal is obtained.
10. Average the three readings for each standard solution and the sample
solution. Plot absorbance versus calcium concentration for the four
standard solutions.
45
Ca-2
11. Determine the concentration of the sample solution from the standard
curve.
Note:
Note If the spectrometer is equipped with a curve corrector, direct digital
readout, or similar accessory, these systems may be used after appropriate
verification.
Calculation
where V 1 = initial sample volume in mL.

V2 = second sample volume in mL.
V3 = final sample volume in mL.
V4 = initial sample aliquot in mL.
V5 = final sample aliquot in mL.
When all aliquots and dilutions are followed, then:
References
1. Fertilizers Determination of Calcium by Atomic Absorption
Spectrometry, ISO/CD 10151.
46
Mg-1
Magnesium
Scope
This method determines the magnesium content of all fertilizers by atomic
absorption spectrometry.
Apparatus
1. Atomic absorption spectrometer with a 10 cm air-acetylene burner
adjusted to an oxidizing flame (lean, blue). A wavelength of 285.2 nm is
the most sensitive resonance line for magnesium.
Note:
Note Less sensitivity may be obtained by rotating the burner head away from
the optical axis of the light beam or by substituting a 5 cm nitrous oxide burner
head.
2. Hollow cathode lamp for magnesium.
Reagents
2. Lanthanum solution, 100 g/L. Weigh 235 g of La2O3 into a 3 L beaker. Add
700 mL of H 2O and 1,000 mL of 1 + 1 HCl. Stir until dissolved, filter into
a 2 L volumetric flask, and cool to room temperature. Dilute to volume
with H 2O and mix thoroughly.
3. Primary magnesium standard solution, 1,000 mg/L. Dissolve 1.0000 g
0.5 mg of pure magnesium metal (acid washed and dried) in 20 mL of
1 + 1 HCl and 50 mL of H 2 O in a covered 600 mL tall-form beaker.
Transfer quantitatively to a 1 L volumetric flask, dilute to volume, and mix
thoroughly. This solution may be stored in a polyethylene bottle for
approximately 1 year.
4. Secondary magnesium standard solution, 10 mg/L. Transfer 10 mL of
primary magnesium standard solution to a 1 L volumetric flask and dilute
to volume with H2O. This solution is stable for about 2 months in
polyethylene.
47
Mg-1
5. Working magnesium standard solutions, 0.5 mg/L, 1.0 mg/L, 1.5 mg/L,
and 2.0 mg/L. Transfer 5 mL, 10 mL, 15 mL, and 20 mL of the secondary
magnesium standard solution to four 100 mL volumetric flasks. To each
flask add 10 mL of La2O3, dilute to volume with H2O, and mix thoroughly.
Procedure
1. Transfer a 2.5 g 1.0 mg of sample to a 250 mL beaker and add 50 mL of
1 + 1 HCl.
2. Cover with a watch glass, place on a hot plate, and bring to a boil.
3. Continue to boil for 30 minutes. Replace evaporated H 2O.
4. Cool the solution, transfer to a 500 mL volumetric flask, and dilute to
volume with H 2O.
5. Thoroughly mix and filter a portion through a dry paper, discarding the
first few milliliters.
6. Transfer a 50 mL aliquot to a 250 mL volumetric flask, dilute to volume
with H 2O, and mix thoroughly.
7. Transfer 10 mL to a 100 mL volumetric flask, add 10 mL of La2O3 solution,
dilute to volume, and mix.
solution. Plot absorbance versus magnesium concentration for the four
standard solutions.
48
Mg-1
curve.
Note:
verification.
Calculation

V2 = second sample volume in mL.
V4 = first sample aliquot in mL.
V5 = second sample aliquot in mL.
When all aliquots and dilutions are followed, then:
References
1. Fertilizers Determination of Magnesium by Atomic Absorption
Spectroscopy, ISO/CD 10152.
49
S-1
Sulfur
Gravimetric Barium Sulfate Method
Scope
This method determines mineral acid-soluble sulfate sulfur in fertilizers.
Apparatus
1. Oven controlled at 120 5 o.
2. Furnace controlled at 800 50o.
3. Crucible filter crucible with porcelain disc, porosity grade P10 (pore size
index 4 nm to 10 nm).
Reagents
2. Barium chloride solution. Dissolve 122 g of BaCl 22H2O in H2O and dilute
to 1 L.
3. Silver nitrate solution. Dissolve 5 g of AgNO 3 in H 2O and dilute to 1 L.
Procedure
1. Accurately weigh a sample containing 400 mg of SO3 into a 400 mL
beaker.
2. Add 200 mL of H 2O and 25 mL of HCl.
3. Heat to boiling, boil for 10 minutes, and cool.
4. Transfer quantitatively to a 250 mL volumetric flask, dilute to volume with
H2O, and mix thoroughly.
5. Filter a portion of the sample through a dry filter and transfer 50 mL of the
clear filtrate to a 600 mL beaker.
Note:
Note The amount of sample utilized for the precipitation of barium sulfate
should contain 25-85 mg of SO3 and 5 mL of HCl.
50
S-1
6. Dilute to 300 mL with H 2O and heat to boiling.
7. With continuous stirring, slowly add 10 mL of BaCl 2 solution, cover with
a watch glass, and continue boiling for several minutes.
8. Remove from heat and allow the precipitate to settle for a minimum of
3 hours (preferably 12-16 hours) at 50o-60o.
9. Filter through a tared filter crucible previously heated at 800o 50o and
cooled in a desiccator.
10. Decant the clear supernatant liquid and wash the precipitate several times
by decanting with hot H 2O (50o-60o).
11. Transfer the precipitate to the crucible with hot H2O and continue washing
until the washings are free of chloride ions as determined with the AgNO 3
solution.
12. Dry the crucible containing the precipitate at 120o 5o for 1 hour and then
heat at 800o 50o for 30 minutes.
13. Remove from the furnace, cool in a desiccator, and weigh.
Note:
Note Total sulfur may be determined in samples containing non-sulfate sulfur
by this method provided that all the sulfur in the sample is first oxidized to the
sulfate form.
Calculation
where A = wt. of crucible and precipitate.

B = wt. of crucible.
51
S-1
References
1. Solid Fertilizers Determination of Mineral Acid-Soluble Sulfate
Content Gravimetric Method, ISO 10084, 1992.
52
B-1
Boron
Azomethine H Spectrometric Method
Scope
This method determines water-soluble and acid-soluble boron in fertilizers. It is
sensitive to slight procedural deviations, and care must be exercised in its
application.
Apparatus
1. Spectrometer capable of reading absorbance at 420 nm and equipped with
a 1 cm or flow-through cell.
2. Pipet, 100 L.
3. Erlenmeyer flask, 10 mL.
Reagents
1. Primary boron standard solution, 100 mg/L. Dissolve 0.5716 g of H 3BO3
in H 2O and dilute to 1 L. Mix thoroughly and transfer to plastic bottle.
2. Working boron standard solutions, 0 mg/L, 5 mg/L, 10 mg/L, 15 mg/L,
20 mg/L, 25 mg/L, 30 mg/L, and 45 mg/L. Pipet 0 mL, 5 mL, 10 mL,
15 mL, 20 mL, 30 mL, and 45 mL of primary boron standard solution into
separate 100 mL volumetric flasks and dilute to volume with 1% HCl. Mix
thoroughly and transfer to plastic bottles. Solutions are stable.
3. Azomethine H solution. Dissolve 0.9 g azomethine H and 2.0 g of ascorbic
acid in 100 mL of H 2O. Store in refrigerator and discard after 14 days.
4. Buffer-masking solution. Dissolve 140 g of CH 3COONH 4, 10 g of
CH3COOK, 4 g of nitrilotriacetic acid, disodium salt, 10 g of (ethylenedinitrilo) tetraacetic acid, and 350 mL of 10% CH3COOH (V/V) in H2O
and dilute to 1 L. Solution is stable.
5. Transfer 35 mL of azomethine H solution and 75 mL of buffer-masking
solution to a 250 mL volumetric flask and dilute to volume with H2O.
Prepare fresh daily.
53
B-1
Procedure
A. Acid-Soluble Boron
1. Weigh 2.0 g 1.0 mg of sample into a 100 mL volumetric flask and add
30 mL of H 2O and 10 mL of HCl.
2. Stopper and shake for 15 minutes.
3. Dilute to volume with H2O, mix, and filter immediately through a dry
paper into a plastic bottle. Dilute, if necessary, so that final solution for
color measurement falls within the boron concentration range of the
standard curve.
B. Water-Soluble Boron
1. Weigh 2.0 g 1.0 mg of sample into a 250 mL beaker, add 50 mL of
H2O, and boil for 10 minutes.
2. While hot, filter through a retentive paper (Whatman No. 40 or
equivalent) into a 100 mL volumetric flask.
3. Wash paper and residue with hot, boiled water until total volume is
about 95 mL.
4. Cool, add 1.0 mL of HCl, dilute to volume with H2O, and mix thoroughly.
5. Transfer to a plastic bottle immediately.
6. Dilute, if necessary, so that final solution for color measurement falls
within the boron concentration range of the standard curve.
Determination
1. Transfer 100 L aliquots of 0 mg/L, 5 mg/L, 10 mg/L, 15 mg/L, 20 mg/L,
25 mg/L, 30 mg/L, and 45 mg/L working boron standard solutions and
a 100 L aliquot of the sample solution to separate 10 mL Erlenmeyer
flasks.
2. Add 5.0 mL of color-developing reagent by automatic pipet dispenser (if
unavailable use 5 mL pipet), mix thoroughly, and let stand for 1 hour at
room temperature.
54
B-1
3. Read absorbance at 420 nm against H2O and correct for reagent blank
(0 mg/L standard).
4. Plot absorbance versus boron concentration of standards.
5. Determine concentration of boron in sample from the standard curve.
Calculation
where F = sample dilution factor.
References
Chemists, 15th Edition, Method 982.01, 1990.
55
Cl-1
Chloride
Titrimetric Silver Nitrate Method
Scope
This method determines water-soluble chloride in all fertilizers.
Apparatus
Reagents
1. Silver nitrate solution. Dissolve 5 g of AgNO 3 in H2O and dilute to 1 L.
Standardize against pure, dry NaCl and adjust so that 1 mL of solution =
1 mg of Cl.
2. Potassium chromate indicator solution. Dissolve 5 g of K 2CrO4 in H 2O and
dilute to 1 L.
3. Sodium bicarbonate, NaHCO3.
Procedure
1. Place 2.5 g 1.0 mg of sample on 11 cm filter paper and wash with
successive portions of boiling water into a 250 mL volumetric flask.
2. Continue washing until total volume is about 250 mL.
3. Cool, dilute to volume with H 2O, and mix thoroughly.
4. Transfer an aliquot containing between 10 mg and 40 mg of Cl to a 250 mL
Erlenmeyer flask and adjust volume to about 50 mL.
5. Add 50 mL of H 2O to a 250 mL Erlenmeyer flask to be used as a blank.
6. Add 1 mL of K 2CrO4 indicator solution to the blank and sample.
7. Titrate the blank solution with the standard AgNO 3 solution until a
reddish-brown color persists.
8. Titrate the sample solution in the same manner to the same reddish-brown
end point.
56
Cl-1
Calculation
where A = mL AgNO 3 required for sample.

B = mL AgNO 3 required for blank.
Note: Store the AgNO 3 solution in a glass-stoppered bottle away from light.
References
57
Co-1
Cobalt
Scope
This method determines the total cobalt content of all fertilizers by atomic
absorption spectrometry.
Apparatus
1. Atomic absorption spectrometer with an air-acetylene burner adjusted to
an oxidizing (lean, blue) flame. A wavelength of 240.7 nm is the most
sensitive resonance line for cobalt. Less sensitivity may be obtained by
rotating the burner head or selecting an alternate resonance line.
2. Hollow cathode lamp for cobalt.
Reagents
4. Primary cobalt standard solution, 1,0000 mg/L. Dissolve 1.0000 g
0.5 mg of cobalt metal or 4.0530 g of CoCl 26H2O in 20 mL of 1 + 1
HCl. Cool, dilute to volume in a 1 L volumetric flask, and mix thoroughly.
5. Secondary cobalt standard solution, 25 mg/L. Transfer a 25 mL aliquot of
the primary cobalt standard solution to a 1 L volumetric flask, dilute to
volume with H 2O, and mix thoroughly.
6. Working cobalt standard solutions, 2.5 mg/L, 5.0 mg/L, 7.5 mg/L, and
cobalt standard solution to four 100 mL volumetric flasks, adjust the
acidity of each to approximately equal that of the sample, dilute to volume
58
Co-1
Procedure
Sample Preparation
A. Hydrochloric Acid Dissolution Method
1. Accurately weigh 2.5 g 1.0 mg of sample into a 250 mL beaker, add
50 mL of 1 + 1 HCl, and cover with a watch glass.
2. Heat to boiling and continue to boil until volume is reduced to about
25 mL.
3. Dilute to about 100 mL with H 2O and bring to a boil.
4. Cool, transfer to a 500 mL volumetric flask, and dilute to volume with
H2O.
5. Mix thoroughly and allow to stand until clear or filter a portion through
a dry retentive paper.
6. Transfer a 25 mL aliquot to a 250 mL volumetric flask, dilute to volume,
and mix thoroughly.
8. Continue under determination.
B. Nitric-Perchloric Acid Dissolution Method
1. Accurately weigh 2.5 g 1.0 mg of sample into a 250 mL beaker and add
10 mL of H 2O and 25-30 mL of HNO 3. Boil until brown fumes cease and
volume is reduced to about 15 mL.
2. Add 10 mL of HNO 3 and 20 mL of HClO4 (see safety note), place on hot
plate, and boil until dense white fumes of HClO4 fill the beaker.
3. Cool, dilute to about 100 mL with H 2O, and bring to a boil.
H2O.
59
Co-1
Determination
1.
Prepare the atomic absorption spectrometer in accordance with the
2.
Adjust the spectrometer to zero while aspirating the blank solution.

Then obtain readings for the standard solutions and sample solution
alternately, about three times each, without interruptions or changing
instrument settings. Take each reading after a stable signal is obtained.
3.
Average the three readings for each standard solution and the sample
solution. Plot absorbance versus cobalt concentration for the four
standard solutions.
4.
Determine the concentration of cobalt in the sample solution from the

standard curve.
Note:
verification.
Calculation

V3 = sample aliquot volume in mL.
* If a fertilizer fails to meet guarantee for this element, the determination should
be repeated using the nitric-perchloric acid dissolution method (B). Also, this
method should be applied if the fertilizer is known to contain a significant
60
Co-1
quantity of organic matter. Otherwise, the hydrochloric acid dissolution method
(A) should be used on a regular basis.
61
Cu-1
Copper
Scope
This method determines copper in all fertilizers by atomic absorption
spectrometry.
Apparatus
1. Atomic absorption spectrometer with an air-acetylene burner adjusted to
an oxidizing (lean, blue) flame. A wavelength of 324.7 nm is the most
sensitive resonance line for copper. Less sensitivity may be obtained by
2. Hollow cathode lamp for copper.
Reagents
4. Primary copper standard solution, 1,000 mg/L. Dissolve 1.0000 g 0.5 mg
of copper metal in a minimum of HNO 3. Add 5 mL of HCl and evaporate
to near dryness. Add 40 mL of 1 + 1 HCl, cool, and transfer to a 1 L flask.
Dilute to volume with H 2O and mix thoroughly.
5. Secondary copper standard solution, 10 mg/L. Transfer 10 mL of primary
copper standard solution to a 1 L volumetric flask, dilute to volume with
6. Working copper standard solutions, 0.5 mg/L, 2.0 mg/L, 3.5 mg/L, and
5.0 mg/L. Transfer 5 mL, 20 mL, 35 mL, and 50 mL of the secondary
copper standard solution to four 100 mL volumetric flasks, adjust the
acidity to be approximately equal to that of the sample, dilute to volume
62
Cu-1
Procedure
Sample Preparation
25 mL.
H2O.
and mix thoroughly.
plate, and boil until dense white fumes of perchloric acid fill the beaker.
H2O.
63
Cu-1
Determination
obtain readings for the standard solutions and sample solution
solution. Plot absorbance versus copper concentration for the four
standard solutions.
curve.
Note:
readout, or similar accessory, use these systems after appropriate verification.
Calculation

*
If a fertilizer fails to meet guarantee for this element, the determination

should be repeated using the nitric-perchloric acid dissolution method (B).
Also, this method should be applied if the fertilizer is known to contain a
significant quantity of organic matter. Otherwise, the hydrochloric acid
dissolution method (A) should be used on a regular basis.
64
Cu-1
References
65
Fe-1
Iron
Scope
This method determines total iron in all fertilizers by atomic absorption
spectrometry.
Apparatus
1. Atomic absorption spectrometer with air-acetylene burner adjusted to an
oxidizing flame (lean, blue). A wavelength of 248.3 nm is the most
sensitive resonance line for iron.
2. Hollow cathode lamp for iron.
Reagents
4. Primary iron standard solution, 1,000 mg/L. Dissolve 1.0000 g 0.5 mg
of iron wire in 15 mL of HCl with the aid of a few drops of HNO 3. Transfer
to a 1 L volumetric flask and dilute to volume with H 2O.
5. Secondary iron standard solution, 25 mg/L. Transfer a 25 mL aliquot of the
primary iron standard solution to a 1 L volumetric flask, dilute to volume
6. Working iron standard solutions, 2.5 mg/L, 5.0 mg/L, 7.5 mg/L, and
iron standard solution to four 100 mL volumetric flasks, adjust the acidity
of each to approximately equal that of the sample, dilute to volume with
66
Fe-1
Procedure
Sample Preparation
25 mL.
H2O.
and mix thoroughly.
H2O.
67
Fe-1
Determination
solution. Plot absorbance versus iron concentration for the four standard
solutions.
curve.
Note: If the spectrometer is equipped with a curve corrector, direct digital
Calculation

* If a fertilizer fails to meet guarantee for this element, the determination
68
Fe-1
References
69
Mn-1
Manganese
Scope
This method determines total manganese in all fertilizer by atomic absorption
spectrometry.
Apparatus
oxidizing (lean, blue) flame. A wavelength of 279.5 nm is the most
sensitive resonance line for manganese. Less sensitivity may be obtained by
2. Hollow cathode lamp for manganese.
Reagents
4. Primary manganese standard solution, 1,000 mg/L. Dissolve 1.5825 g
0.5 mg of MnO 2 in about 30 mL of 1 + 1 HCl and boil to volatilize
chlorine. Cool, dilute to 1 L with H 2O, and mix thoroughly. This solution
may be stored in a polyethylene bottle for about 1 year.
5. Secondary manganese standard solution, 25 mg/L. Transfer a 25 mL
aliquot of the primary manganese standard solution to a 1 L volumetric
flask, dilute to volume with H 2O, and mix thoroughly.
6. Working manganese standard solutions, 2.5 mg/L, 5.0 mg/L, 7.5 mg/L, and
manganese standard solution to four 100 mL volumetric flasks, adjust the
acidity of each to approximately equal that of the sample, dilute to volume
70
Mn-1
Procedure
Sample Preparation
25 mL.
H2O.
and mix thoroughly.
H2O.
71
Mn-1
Determination
solution. Plot absorbance versus manganese concentration for the four
standard solutions.
curve.
Calculation

72
Mn-1
References
73
Na-1
Sodium
Atomic Emission Spectrometric Method
Scope
This method determines sodium in all fertilizers by atomic emission
spectrometry.
Apparatus
1. Atomic emission spectrometer with an air-acetylene flame is recommended.
An emission wavelength of 589.0 nm is the most sensitive resonance line
for sodium. Reduced sensitivity may be obtained by rotating the burner
head.
Reagents
1. Ammonium oxalate solution. Dissolve 40 g of (NH 4)2C2O4H2O in H2O
and dilute to 1 L.
2. Primary sodium standard solution, 1,000 mg/L. Dissolve 2.5421 g
0.5 mg of NaCl (previously dried for 2 hours at 105o and cooled in a
desiccator) in H 2O and dilute to 1 L in a volumetric flask.
3. Secondary sodium standard solution, 10 mg/L. Transfer 10 mL of primary
sodium standard solution to a 1 L volumetric flask, dilute to volume with
water, and mix thoroughly.
4. Working sodium standard solutions, 0.5 mg/L, 1.0 mg/L, 1.5 mg/L, and
sodium standard solution to four 100 mL volumetric flasks, dilute to
volume with H 2O, and mix thoroughly.
Procedure
1. Weigh 2.5 g 1.0 mg of sample into a 400 mL beaker.
2. Add 125 mL of H 2O and 50 mL of (NH 4)2C2O4H2O solution.
3. Boil for 30 min, cool, quantitatively transfer to a 500 mL volumetric flask,
dilute to volume with H 2O, and mix thoroughly.
74
Na-1
4. Filter a portion through a dry retentive paper and transfer 10 mL of the
clear filtrate to a 250 mL volumetric flask.
5. Dilute to volume with H 2O and mix thoroughly.
7. Prepare the spectrometer in accordance with the manufacturer's
instructions and allow to warm up until stable operating conditions are
reached.
solution. Plot emission versus sodium concentration for the four standard
solutions.
curve.
Calculation

References
75
Zn-1
Zinc
Scope
This method determines total zinc in all fertilizers utilizing atomic absorption
spectrometry.
Apparatus
oxidizing (lean, blue) flame. A wavelength of 213.9 nm is the most
sensitive resonance line for zinc.
2. Hollow cathode lamp for zinc.
Reagents
4. Primary zinc standard solution, 1,000 mg/L. Dissolve 1.0000 g 0.5 mg
of pure zinc metal (acid washed and dried) in about 10 mL of 1 + 1 HCl
and dilute to 1 L in a volumetric flask. This solution is stable for about
1 year when stored in polyethylene.
5. Secondary zinc standard solution, 10 mg/L. Transfer 10 mL of primary zinc
standard solution to a 1 L volumetric flask and dilute to volume with H 2O.
6. Working zinc standard solutions, 0.5 mg/L, 2.0 mg/L, 3.5 mg/L, and
5.0 mg/L. Transfer 5 mL, 20 mL, 35 mL, and 50 mL of the secondary zinc
standard solution to four 100 mL volumetric flasks, adjust acidity of each
to be approximately equal to that of the sample, dilute to volume with
76
Zn-1
Procedure
Sample Preparation
25 mL.
H2O.
and mix thoroughly.
plate, and boil until dense white fumes of perchloric acid fill the beaker.
H2O.
77
Zn-1
Determination
solution. Plot absorbance versus zinc concentration for the four standard
solutions.
curve.
Note:
Calculation

78
Zn-1
References
79
H2O-1
Free Water
Vacuum-Desiccation Method
Scope
This method determines free water in fertilizers by drying under reduced

pressure in the presence of a strong desiccant.
Apparatus
1. Vacuum pump, fitted with gauge.
2. Weighing bottle, 70-80 mm in diameter, fitted with a stopper.
3. Vacuum desiccator, with internal diameter about 200 mm.
Reagents
1. Magnesium perchlorate, anhydrous Mg(ClO4)2.
Procedure
1. Weigh 2.0 g 0.5 mg of sample into a tared weighing bottle.
2. Place the unstoppered bottle containing the sample along with the stopper
in a vacuum desiccator previously charged with anhydrous magnesium
perchlorate.
3. With the desiccator behind a safety screen, connect to the vacuum pump
and reduce the pressure in the desiccator to 50-55 cm of Mercury (2025 cm absolute pressure).
4. Dry at this pressure for 16-18 hours, maintaining the temperature at 25o30o.
5. Allow the pressure in the desiccator to equilibrate with that of the
atmosphere by gradually admitting desiccated air.
6. Open the desiccator, quickly stopper the bottle containing the sample, and
weigh.
80
H2O-1
Calculation
where A = wt. of bottle and sample before drying.

B = wt. of bottle and sample after drying.
Note:
Note P 2O5 or BaO may be substituted for Mg(ClO4)2 as the desiccant.
References
1.
Official Methods of Analysis of the Association of Official Analytical

Chemists, 15th Ed., Method 965.08A, 1990.
81
Appendix A

Standard Acid Solutions
Scope
This method is for the preparation and standardization of acid solutions
required for volumetric titrations.
Apparatus
1.
Constant temperature oven.
2.
Desiccator containing anhydrous magnesium perchlorate or other

suitable desiccant.
3.
Weighing bottles, glass stoppered.
4.
Ordinary labware.
Reagents
1.
Acids for standardization colorless concentrated reagent grade.
2.
THAM [Tris(Hydroxy Methyl) amminomethane], Certified analytical

reagent Dry the primary standard powder for 2 hours at 100o-103o.
Store in desiccator.
Procedure
1.
Pour into the storage bottle an amount of water equal to three-fourths

of the volume of the solution to be made.
2.
Using an appropriate measuring device, slowly and carefully add to the

water the required volume of concentrated acid (see Calculations,
Item 1).
3.
Add balance of water required to bring solution to the total volume

desired. Mix thoroughly and allow to cool to room temperature.
4.
Carefully weigh to the nearest 0.1 mg a suitable amount of the dry

THAM into a 250 mL beaker or suitable flask. Calculate proper amount
of THAM to use (see Calculations, Item 2).
5.
Add 50 mL CO2-free water to dissolve the THAM.
6.
Titrate the THAM solution with the prepared acid solution from a 50 mL
buret to a pH of 4.70 using a calibrated pH meter.
7.
Read volume of acid solution used to nearest 0.01 mL and calculate the
normality of the prepared solution (see Calculations, Item 3).
Calculations
1.
Volume of concentrated acid required for any desired volume and

normality of standard solution.
Where: N1 = Normality of concentrated acid.

N2 = Normality of desired solution.
V = Volume of desired solution in mL.
2.
Acid
Specific Gravity @
25
HCl
HNO 3
H2SO4
1.19
1.42
1.84
Assay (%)
38
70
96.6
Normality
12.4
15.8
36.2
Grams THAM needed for standardization of prepared acid solution of

N normality may be estimated:
3.
Normality of the standardized solution is calculated:

Molecular weight of THAM = 121.136. Each milliequivalent =
0.121136 g THAM.
Where: W = weight of THAM used in g.

M = mL of acid solution used for the titration.
Notes
1.
CAUTION: Care must be taken in handling all concentrated acids.
Always add acids to water slowly and cautiously as heat may be
generated. NEVER ADD WATER TO CONCENTRATED ACIDS.
2.
If storage bottle is vented to atmosphere, the solution must be protected

by providing storage bottle with suitable guard tube filled with suitable
desiccant.
3.
A further check on the normality of the prepared acid solution may be

made by titrating a known volume of standard base (NaOH) of
approximately the same normality to a pH of 8.6.
Where Va = mL of standard acid used in titration.

Vb = mL of standard base titration (25-30 mL).
Nb = normality of standard base.

Standard Base Solutions
Scope
This method is for the preparation and standardization of sodium hydroxide
solutions required for volumetric titrations.
Apparatus
1.
Desiccator containing anhydrous magnesium perchlorate or other

suitable desiccant.
2.
Weighing bottles, glass stoppered.
3.
Storage bottles, polyethylene, volume as required for solutions to be

prepared.
4.
Ordinary labware.
Reagents
1.
Sodium hydroxide solution, 50% NaOH, low carbonate. Dissolve

reagent grade NaOH pellets in water. Cool, allow carbonates to settle,
and filter through suitable filter paper or fritted-glass funnel using
suction. Quickly transfer to polyethylene storage bottle and keep
tightly closed.
2.
Potassium acid phthalate (PAP). Crush (do not grind) a few grams of
PAP to a fineness of approximately 0.25 mm and dry for 1-2 hours at
120. Place in weighing bottle and cool in desiccator.
Procedure
1.
Pour into storage bottle an amount of water equal to one-half of the

volume of solution to be prepared.
2.
Measure 50% NaOH with appropriate measuring device and add to

water (see Calculations, Item 1).
3.
Add balance of water required to bring solution to the total volume

desired. Mix thoroughly.
4.
Carefully weigh to the nearest 0.1 mg a suitable amount of the dry PAP
into a 250 mL beaker or suitable flask. Calculate proper amount of PAP
to use (see Calculations, Item 2).
5.
Add 50 mL of CO2-free water to dissolve the PAP.
6.
Titrate the PAP solution with the prepared NaOH solution from a 50 mL
buret to a pH of 8.6 using a calibrated pH meter.
7.
Read the volume of the NaOH solution used to the nearest 0.01 mL and
calculate the normality of the prepared solution (see Calculations,
Item 3).
Calculations
1.
Volume 50% NaOH solution required for any desired volume and
normality of standard solution
Where: N = Desired normality of solution.

V = Volume of solution in liters.
2.
Grams PAP needed for standardization of prepared NaOH solution of

N normality may be estimated:
3.
Normality of the standardized solution is calculated:

Molecular weight of PAP = 204.23. Each milliequivalent = 0.20423 g
PAP.
Where: W = weight of PAP in g.

M = mL of NaOH solution used for the titration.
Note:
Note If storage bottle is vented to atmosphere, the solution must be protected
by providing storage bottle with suitable guard tube filled with Ascarite or
other suitable CO2-absorbing reagent.
Appendix B
Analytical Report Form
Appendix C
Laboratory Safety
Laboratory Safety
The following guidelines on laboratory safety are generally in keeping with the
requirements outlined in the Occupational Health and Safety Act, Title 29, of the U.S.
Code of Federal Regulations, part 1910.1450.
Standard Operating Procedures for Laboratories

The following procedures shall be used for all laboratory work with chemicals. Material
Safety Data Sheets (MSDS) shall be consulted prior to work with any chemical.
A.
B.
Accidents and Spills

1.
Eye C ontact:
ontact Promptly flush eyes with water for 15 minutes and seek
medical attention.
2.
Ingestion:
Ingestion Seek medical attention immediately.
3.
Skin Contact:
Contact Flush the affected area with water and remove any
contaminated clothing. If symptoms persist after washing, seek medical
attention.
4.
Cleanup:
Cleanup Promptly clean spills and properly dispose of wastes utilizing
appropriate protective apparel and equipment.
Avoidance of Routine Exposure

1.
Develop and encourage safe habits; avoid unnecessary exposure to

chemicals.
2.
Do not smell or taste chemicals. Avoid skin contact,
3.
Inspect gloves and test glove boxes before use.
4.
Do not allow release of toxic substances into recirculated atmospheres. All

apparatus (vacuum pumps, distillation columns) that discharge hazardous
chemicals will be vented into local exhaust devices.
1
C.
D.
Eating and Smoking

1.
Avoid eating, drinking, gum chewing, use of tobacco products, or application

of cosmetics in areas where laboratory chemicals are present; wash hands
before conducting these activities.
2.
Avoid storage of food or beverages in refrigerators, glassware, or utensils

that are also used for laboratory operations. Avoid handling or consumption
of food or beverages in chemical storage areas.
Equipment and Glassware

Handle and store laboratory glassware with care to avoid damage; do not use
damaged glassware. Use extra care with Dewar flasks and other evacuated glass
apparatus; shield or wrap them to minimize dispersal of chemicals and fragments
should implosion or breakage occur. A glass tubing manipulator or holder should
be used when inserting glass tubing into stopper. Use equipment only for its
designed purpose.
E.
Exiting
Wash areas of exposed skin thoroughly before leaving the laboratory.
F.
Horseplay
Avoid practical jokes or other behavior that might confuse, startle, or distract
another worker.
G.
Mouth Suction
Do not use mouth suction for pipeting or siphoning.
H.
Personal Apparel
Confine long hair and loose clothing. Wear appropriate shoes at all times in the
laboratory; do not wear sandals or perforated shoes. Lab coats or long-sleeve
clothing should be worn when practical.
I.
Personal Housekeeping
Keep the work area clean and uncluttered and keep chemicals and equipment
properly labeled and stored; clean the work area on completion of an operation
or at the end of the day.
J.
K.
Personal Protection
1.
Ensure that appropriate eye protection is worn by all persons, including

visitors, where chemicals are stored or handled and in all designated areas.
2.
Wear appropriate gloves when the potential for contact with hazardous
materials exists; inspect the gloves before each use, wash them before
removal, and replace them periodically. Consult manufacturer's
specifications to determine appropriate glove material.
3.
Use any other protective and emergency apparel and equipment as

appropriate. Consult manufacturer's specifications where appropriate.
4.
Avoid use of contact lenses in the laboratory.
5.
Remove laboratory coats immediately if they become saturated with a

chemical or otherwise lose their protective property.
Planning
Seek information and advice about hazards; plan appropriate protective and
emergency procedures; plan positioning of equipment before beginning any new
operation.
L.
Unattended Operations
Leave lights on and place an appropriate sign on the door. Information on the sign
should include the name and phone number of a responsible person in case of an
emergency. Provide for containment of hazardous substances in the event of
failure of a utility service to an unattended operation.
M.
N.
Use of Hood
1.
Use the hood for operations that might result in release of hazardous
chemical vapors or dust.
2.
As a rule of thumb, use a hood or other local ventilation when working with
any volatile substance.
3.
Confirm adequate hood performance before use; keep hood sash lowered
to or below established safe level except when adjustments within the hood
are being made; keep materials stored in hoods to a minimum and do not
allow them to block vents or airflow.
4.
Leave the hood ON when it is not in active use if toxic substances are stored
in it or if it is uncertain whether adequate general laboratory ventilation will
be maintained when it is OFF.
Vigilance
Be alert to unsafe conditions and see that they are corrected when detected.
O.
Waste Disposal
1.
Ensure that each laboratory operation includes plans and training for waste
disposal.
2.
Deposit chemical waste in appropriately labeled receptacles and follow all

other waste disposal procedures.
3.
Do not discharge to the sewer: concentrated acids or bases; highly toxic,

malodorous, or lachrymatory substances; or any substance that might
interfere with the biological activity of wastewater treatment plants, create
fire or explosion hazards, cause structural damage, or obstruct flow.
P.
Working Alone
Avoid working alone in a building; do not perform chemical work alone in the
laboratory. A supervisor or another laboratory worker should maintain periodic
contact throughout the day with any individual who is the sole worker in a
laboratory.
Q.
Hazard Posting
Any novel chemical or safety hazard will be posted at the entry to each
laboratory.
Protective Equipment Requirements

A.
Fume Hoods
1.
Minimum Requirements
a.
Fume hoods shall meet or exceed the limits of 75 cm of hood space

per person and an airflow of 18 meters per minute minimum. In the
case of hazardous chemical usage, the minimum face velocity shall be
30 meters per minute. No areas of stagnant air should be present in a
properly functioning hood.
b.
The location of the hood sash at which this face velocity is achieved
shall be clearly marked and shall be high enough to permit necessary
activities to be carried out safely.
c.
A device for checking the hood face velocity should be readily

accessible.
d.
Hoods shall be vented to the outside of the laboratory building and

shall have appropriate scrubbing and filtering devices, if feasible, to
minimize contamination of the outside air. Hood exhausts shall be
located far enough away from building air intakes to prevent fumes
from entering the laboratory building or other nearby buildings.
e.
2.
3.
B.
The manual Industrial Ventilation, 20th Ed., American Conference of

Governmental Industrial Hygienists, Cincinnati, Ohio, U.S.A., 1988,
shall be consulted to establish acceptable guidelines.
Use
a.
Fume hoods shall be used with the sash at or below the marked safe
face velocity setting. No portion of the worker's body except the hands
and arms shall be inside a fume hood that contains hazardous
chemicals.
b.
Use of hoods for chemical storage shall be discouraged. In no case

shall chemicals or labware in the hood impede proper airflow through
the hood.
c.
Hood sashes shall be kept closed to the extent that this is compatible
with the work in progress.
Maintenance
a.
Yearly appraisals of each hood for face velocity and proper

functioning shall be made by a qualified person. This person shall be
responsible for the marking of the maximum safe sash height.
b.
If a problem with face velocity or proper functioning of a hood is

suspected, the hood shall be tagged out of use and checked. Until the
hood has been recertified as properly functional, it shall not be used.
Other Protective Equipment

1.
Minimum Requirements
a.
Appropriate protective apparel, such as aprons or lab coats, gloves,

safety glasses or goggles, and face shields, shall be required for all
areas where work involving hazardous chemicals is performed.
b.
Protective apparel shall be chosen to protect against the expected

chemical and physical hazards. Chemical literature and, if necessary,
6
the manufacturer shall be consulted about the compatibility of

chemicals.
2.
c.
Equipment, such as eyewashes, safety showers, fire extinguishers, and

a telephone or communication device for emergency use, will be
required for all areas where work involving hazardous chemicals is
performed. The above equipment shall be accessible to the worker
without the need for passage through any doors.
d.
Respiratory equipment appropriate to the exposure shall be made

available to the worker and others in the work area as necessary.
e.
Self-contained breathing apparatus (SCBA) should be available in the

hallways outside the laboratories.
f.
Appropriate protective equipment and apparel as well as spill kits

should be available outside but near the laboratory, for use by trained
personnel in case of a spill or accident involving hazardous chemicals.
g.
Glove boxes and similar containment devices shall be made available

and used if warranted by the degree of chemical hazard or by the
nature of the chemicals in use.
Use
a.
Appropriate protective apparel and equipment must be properly used

when working with hazardous chemicals. The wearers/users must be
informed about the limitations of such protection.
b.
Respiratory equipment may not be used without the required training

on proper fit, testing, and use. Facial hair that interferes with the
peripheral fit of the mask will not be allowed. Also, in some cases, a
particular person will not be able to use a respirator if he/she cannot
receive medical clearance.
3.
Maintenance
a.
All apparel and equipment should be inspected prior to and

immediately after each use (excluding eyewashes or showers) by the
person using it. They should be clean and functional. Disposable items
designed for only one use should be marked as used and properly
discarded immediately after use.
b.
Fire extinguishers shall be inspected at least annually for proper

function and be tagged with the inspection date and inspector's name.
c.
Eyewashes, safety showers, and SCBAs shall be inspected at least

monthly by the individual responsible for the lab area where they are
located. At the same time, the inspection tags on fire extinguishers,
showers, and hoods should be checked, as should the availability of
spill kits and similar emergency supplies.
References
A.
General Laboratory Safety

1.
American Chemical Society. Safety in Academic Chemistry Laboratories, 4th

edition, 1985.
2.
Fawcett, H. H., and W. S. Wood. Safety and Accident Prevention in Chemical

Operations, 2nd edition, Wiley-Interscience, New York, 1982.
3.
Flury, Patricia A. Environmental Health and Safety in the Hospital Laboratory.

Charles C. Thomas Publisher, Springfield IL, 1978.
4.
Green, Michael E., and Turk, Amos. Safety in Working With Chemicals, Macmillan
Publishing Co., NY, 1978.
5.
Kaufman, James A. Laboratory Safety Guidelines, Dow Chemical Co., Box 1713,
Midland, MI 48640, 1977.
6.
National Institutes of Health. NIH Guidelines for the Laboratory Use of Chemical
Carcinogens, NIH Pub. No. 81-2385, GPO, Washington, DC 20402, 1981.
7.
National Research Council. Prudent Practices for Disposal of Chemicals From

Laboratories, National Academy Press, Washington, DC, 1983.
8.
National Research Council. Prudent Practices for Handling Hazardous Chemicals

in Laboratories, National Academy Press, Washington, DC, 1981.
9.
Renfrew, Malcolm, Ed. Safety in the Chemical Laboratory, Vol. IV, J. Chem. Ed.,
American Chemical Society, Easlon, PA, 1981.
10.
Steere, Normal V., Ed. Safety in the Chemical Laboratory, J. Chem. Ed., American
Chemical Society, Easlon, PA, 18042, Vol. I, 1967, Vol. II, 1971, Vol. III, 1974.
11.
Steere, Norman V. Handbook of Laboratory Safety, the Chemical Rubber

Company, Cleveland, OH, 1971.
12.
B.
Young, Jay A., Ed. Improving Safety in the Chemical Laboratory, John Wiley &
Sons, Inc., New York, 1987.
Hazardous Substances
1.
American Conference of Governmental Industrial Hygienists. Threshold Limit

Values for Chemical Substances and Physical Agents in the Workroom
Environment With Intended Changes, P.O. Box 1937, Cincinnati, OH 45201
(latest edition).
2.
Annual Report on Carcinogens, National Toxicology Program, U.S. Department

of Health and Human Services, Public Health Service, U.S. Government Printing
Office, Washington, DC (latest edition).
3.
Best Company. Best Safety Directory, Vols. I and II, Oldwick, NJ, 1981.
4.
Bretherick, L. Handbook of Reactive Chemical Hazards, 2nd Edition, Butterworths,

London, 1979.
5.
Bretherick, L. Hazards in the Chemical Laboratory, 3rd Edition, Royal Society of

Chemistry, London, 1986.
6.
Code of Federal Regulations, 29 CFR part 1910 subpart Z, U.S. Govt. Printing
Office, Washington, DC 20402 (latest edition).
7.
LARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to

Man, World Health Organization Publications Center, 49 Sheridan Avenue,
Albany, New York 12210 (latest editions).
8.
NIOSH/OSHA Pocket Guide to Chemical Hazards, NIOSH Pub. No. 85-114, U.S.
Government Printing Office, Washington, DC, 1985 (or latest edition).
9.
Occupational Health Guidelines, NIOSH/OSHA NIOSH Pub. No. 81-123, U.S.

Government Printing Office, Washington, DC, 1981.
10.
Patty, F. A. Industrial Hygiene and Toxicology, John Wiley & Sons, Inc., New York,
NY (Five Volumes).
10
C.
11.
Registry of Toxic Effects of Chemical Substances, U.S. Department of Health and

Human Services, Public Health Service, Centers for Disease Control, National
Institute for Occupational Safety and Health, Revised Annually, for sale from
Superintendent of Documents, U.S. Govt. Printing Office, Washington, DC 20402.
12.
The Merck Index: An Encyclopedia of Chemicals and Drugs. Merck and Company
Inc., Rahway, NJ, 1976 (or latest edition).
13.
Sax, N. I. Dangerous Properties of Industrial Materials, 5th edition, Van Nostrand

Reinhold, NY, 1979.
14.
Sittig, Marshall, Handbook of Toxic and Hazardous Chemicals, Noyes

Publications, Park Ridge, NJ, 1981.
Ventilation
1.
American Conference of Governmental Industrial Hygienists Industrial Ventilation,

16th edition, Lansing, MI, 1980.
2.
American National Standards Institute, Inc. American National Standards

Fundamentals Governing the Design and Operation of Local Exhaust Systems
ANSI Z 9.2-1979 American National Standards Institute, NY, 1979.
3.
Imad, A. P., and Watson, C. L. Ventilation Index: An Easy Way to Decide About
Hazardous Liquids, Professional Safety, pp. 15-18, April 1980.
4.
National Fire Protection Association, Fire Protection for Laboratories Using

Chemicals NFPA 45, 1982.
Safety Standard for Laboratories in Health Related Institutions, NFPA, 56c, 1980.
Fire Protection Guide on Hazardous Materials, 7th Edition, 1978.
National Fire Protection Association, Batterymarch Park, Quincy, MA 02269.
5.
Scientific Apparatus Makers Association (SAMA), Standard for Laboratory Fume

Hoods, SAMA LF7-1980, 1101 16th Street, NW, Washington, DC 20036.
11
D.
Availability of Referenced Material

1.
American National Standards Institute (ANSI), 1430 Broadway, New York, NY

10018.
2.
American Society for Testing and Materials (ASTM), 1916 Race Street,
Philadelphia, PA 19103.
12
Appendix D
Typical Job Descriptions
Typical Job Description

Title
Laboratory Technician.
Duties
The duties of the employee will include sample preparation, some independent
analyses by standard procedures, and assisting an analytical chemist with his
or her assignment. Analyses performed may be titrimetric, gravimetric, or
instrumental and the types of samples will be fertilizer materials.
In assisting chemists with their assignments, the duties will include:
1.
Weighing liquid and solid samples.
2.
Digestion of samples by specified procedures.
3.
Dilution, filtration, or other handling of sample digests.
4.
Titration, weighing of precipitate, or instrument measurement of

analyte.
5.
Calculation of final result with programmable calculator.
6.
Checking calculations of chemists or other technicians.
Job Requirements
1.
A general knowledge and understanding of the basic principles and

techniques of quantative analysis.
2.
Knowledge of proper care and utilization of laboratory equipment,

glassware, instrumentation, and reagent chemicals.
3.
Knowledge of mathematics associated with analytical chemistry.
4.
Ability to accurately follow oral and written instruction.
5.
Ability to work cooperatively with a team.
Complexity of Work
Make decision on planning assignments to complete work in most efficient
manner. Judgments on reasonableness of results are normally left to
supervisor, but apparent problems should be noted and suggested to the
supervisor.
Supervision of Others
None.
Supervisory Control
Supervisor gives instructions for assignments. Incumbent proceeds
independently unless problems arise. Work is partially reviewed during
progress and in detail when completed.
Guidelines
IFDC's Fertilizer Analytical Manual is the guideline to follow for the work in the
laboratory.
Impact of Work
The analytical results obtained and reported have a major impact on the
fertilizer industry. If errors go undetected and incorrect results are reported, a
grave injustice can be done to an individual or company.
Contacts
Contacts outside the immediate work group are very limited.
Work Environment
The position may be exposed to hazardous chemicals and possibly dangerous
equipment. All precautions should be taken to ensure compliance with safety
guidelines.
Qualification
Some training at the university level in the field of science and an aptitude to
work in a laboratory environment.

Title
Analytical Chemist.
Duties
Performs quantitative chemical analysis of fertilizer samples.
Determines appropriate methods of analysis based on requested information.
Uses methods available in IFDC's Fertilizer Analytical Manual, adapts existing
methods or searches the chemical literature for methods applicable to the
assignment. Evaluates results (statistically if necessary) and reports
observations and conclusions to supervisor. If warranted, a revised method may
be drafted and submitted to the supervisor.
Determinations performed include the utilization of any methods applicable to
fertilizer-related material and for which the necessary instrumentation and
equipment are available.
Occasionally provides technical supervision for employees of lower grades.
Job Requirements
1.
Detailed knowledge and understanding of basic principles, theories, and

techniques in analytical chemistry, especially as applied to fertilizer
methodology.
2.
A working knowledge of the principles and theories of the operation of

electronic, optical, and analytical instrumentation.
3.
Knowledge of mathematics associated with analytical chemistry,

including probability and statistics.
4.
Familiarity with specific problems associated with the analysis of

fertilizers and related materials.
5.
Knowledge of chemical literature pertaining to analytical chemistry of

fertilizers and related materials.
3
Complexity of Work
Determines whether samples should be reanalyzed after reviewing results.
Decision is made after considering the precision and accuracy of the
determination and the reasonableness of the results when compared with
results for other elements determined on the same sample by other chemists
or analysts. If apparent problems occur during analysis, suggestions may be
offered to the supervisor concerning whether the problems were due to the
reagents, standards, apparatus, instrument conditions, or interferences. Makes
decisions on planning assignments to complete work in most efficient manner.
May provide technical supervision for analytical chemists with less experience
and technicians when necessary to coordinate and expedite work.
Supervisory Control
Supervisor provides general instructions for each assignment. When all or a
significant portion of an assignment is complete, the work is subject to general
review and approval with regard to work methods and subject to a more
detailed review with regard to conclusion.
Guidelines
IFDC's Fertilizer Analytical Manual is the primary guideline for the work of the
laboratory. Other internationally recognized sources such as AOAC
International and ISO are used when applicable. Chemical literature reference
material may be used when special problems are encountered.
Impact of Work
Contacts
Contacts are generally internal but may involve external contacts to obtain
additional information regarding samples received.
Work Environment
This position may be exposed to hazardous chemicals when working in the
laboratory. This position is responsible for ensuring that safety procedures are
followed when handling hazardous chemicals.
Qualification
Bachelor's degree in chemistry or equivalent with 1-2 years of experience in
analytical chemistry.

Title
Analytical Laboratory Supervisor.
Duties
This position involves the day-to-day supervision of the Fertilizer Analytical
Laboratory by providing administrative and technical guidance to all laboratory
personnel. The duties include but may not be restricted to:
1.
Overseeing personnel that receive, record, and prepare fertilizer

samples for analysis.
2.
Assigning fertilizer samples for analysis and reviewing analyses when

complete.
3.
Reporting results and maintaining complete record of analysis and

methods used.
4.
Selecting methods of analysis for all nutrients.
5.
Providing training for laboratory staff on new methods and

procedures.
6.
Modifying existing methods or developing new ones to provide

additional capability or to upgrade the quality of data produced.
Job Requirements
This position requires a detailed knowledge of the basic principles, theories,
and techniques in analytical chemistry and the ability to apply these principles
and techniques to the chemical analysis of fertilizers. This job may involve the
following:
1.
Knowledge and application of the principles, theories, and operation of

analytical instrumentation, such as optical spectrometers and atomic
absorption and emission spectrometers.
2.
Knowledge of mathematics associated with analytical chemistry to

complete the analytical process, calculate final results, and present
findings.
3.
Ability to utilize chemical literature and other sources of technical

information to remain abreast of new analytical developments and
techniques.
4.
Technical writing ability to prepare reports, technical papers, and

manuals.
5.
Ability to plan workload to accomplish maximum efficiency of the

laboratory staff.
6.
Skill in maintaining excellent interpersonal relations among all

laboratory personnel.
Complexity of Work
This position involves detailed knowledge of analytical chemistry, mathematics,
and analytical instrumentation. This position evaluates current methods and
develops new or modified methods of analysis when necessary to provide
additional capability or increased quality of data. Innovative methodologies
may create new opportunities or save money. This position provides technical
guidance to the analytical chemist and helps solve problems not specifically
covered by procedures (e.g., problems relating to safety and environmental
contamination).
When requested by subordinate, this incumbent will render decision as to the
reasonableness of an analytical result and offer advice to determine correctness
of same.
Provides administration and technical supervision for all employees in the
Fertilizer Analytical Laboratory.
Guidelines
IFDC's Fertilizer Analytical Manual is the primary guideline for the work of the
laboratory. Other internationally recognized sources such as AOAC
International and ISO are used when applicable. Chemical literature reference
material may be used when special problems are encountered.
Impact of Work
Contacts
Contacts are generally internal but may involve external contacts to obtain
additional information regarding samples received.
Work Environment
This position may be exposed to hazardous chemicals when working in the
laboratory. This position is responsible for ensuring that safety procedures are
followed when handling hazardous chemicals.
Qualifications
Masters degree in chemistry or equivalent with 3-5 years of experience in
analytical chemistry.

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IFDC

Abbreviations, Acronyms, Definitions,

International Organization for Standardization

"Water" or "H2O" means distilled or deionized water.

In expressions (1 + 2), (5 + 4), etc., used in connection with liquid

In solutions defined in percentage, it is understood that the solution is

All reagents, unless otherwise described, are of recognized analytical

"Ordinary labware" means labware normally stocked in fertilizer

All volumetric glassware listed conforms to ISO specifications.

Temperature is expressed as degrees Celsius.

The term "alcohol" means 95% ethanol unless otherwise specified.

Preparation of Standard Solutions

Sample Reduction and Preparation

Sample Reducer or Riffle A gated-riffle (Figure 1) constructed of

Grinder or Sample Pulverizer A grinder shall perform as required for the

Containers for Ground Samples Plastic or glass, 250 mL capacity, wide

Set gated-riffle in level position, not tilted in any direction.

Transfer the composite sample to the hopper of the riffle.

If required, repeat steps 4 and 5, until sample is reduced to approximately

Transfer final sample to moistureproof containers and mark for

Clean equipment before storing or re-use.

Grind dry fertilizer mixtures to pass 0.5 mm sieve.

Fertilizer materials and moist fertilizer mixtures may be ground to pass

Grind as rapidly as possible to avoid loss or gain of moisture during the

Place entire sample on flexible rolling sheet of glazed butcher's paper,

Transfer about 200 g of sample to a 250 mL airtight, widemouth container

10. Container must have air space above the sample.

Figure 1. Riffle With Cutoff Gate and Two Pans.

Figure 3. Technique for Subsampling of Ground Sample.

Ammoniacal and Nitrate Nitrogen

All fertilizers, especially when the spectrometric method is to be

Materials containing large quantities of organic matter,

Materials containing small quantities of organic matter:

Transfer an aliquot containing 25 mg P2O5 to 400 mL beaker, dilute

Transfer an aliquot containing 30 mg P2O5 to a 500 mL Erlenmeyer

Transfer an aliquot of the sample solution containing 2-5 mg of P 2O5

7. Make final determination of phosphate content by method P-5, P-6, or P-7.

Transfer aliquot containing 25 mg P2O5 and 10 mL of original

Transfer aliquot containing 30 mg P2O5 and 10 mL of original

Transfer a 10 mL aliquot to a 125 mL Erlenmeyer flask and add 5 mL

where A = weight of sample precipitate (g).

5. Nitric acid, 0.3663 N HNO 3 (see Appendix A).

where A = mg P 2O5 from curve.

Procedure in presence of cyanamide and/or organic materials.

Procedure in the absence of cyanamide and/or organic materials.

4. Add 20 mL of EDTA solution and a few drops (3-5) of phenolphthalein

where A = the weight of precipitate from the sample.

Transfer a 15 mL aliquot of the KH2PO4 solution containing 51.92 mg

Dilute to volume with H2O, mix thoroughly, and, after 10 minutes,

Transfer a 50 mL aliquot of the filtrate to a 125 mL Erlenmeyer flask,

Calculate a factor (F) by the formula:

4. Benzalkonium chloride (BAC) solution. Dilute 38 mL of 17% Zephiran

where A = mL STPB solution.

Weigh 2.5 g 1.0 mg of sample into a 400 mL beaker. Add 125 mL

Weigh 5.0 g 1.0 mg of sample into a 1,000 mL Erlenmeyer flask,

where V = final volume of sample solution.

where V 1 = mL of KMnO4 solution required for sample.

where V 1 = initial sample volume in mL.

When all aliquots and dilutions are followed, then:

where V 1 = initial sample volume in mL.

When all aliquots and dilutions are followed, then:

where A = wt. of crucible and precipitate.

where F = sample dilution factor.

where A = mL AgNO 3 required for sample.