Metal transport mechanisms

1
METALOGENESIS
SISTEMAS, MINERALIZACION, EVOLUCION
DEL PERU Y SU RELACION CON DEPOSITOS
Dr. JORGE OYARZUN MUOZ

Consultor Intercade
TRANSPORTE DE LOS
METALES
Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade
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CONSULTANCY & TRAINING
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GEMM - (J,O.) - E - TRANSPORTE DE LOS

METALES (T)
En esta seccin examinaremos dos mecanismos. El primero
corresponde al transporte en fase neumatoltica,
neumatoltica bajo la forma de
halogenuros voltiles. El segundo es respecto al transporte de los
metales, bajo la forma de iones complejos.
Es muy conocido el hecho de que muchos metales forman
halogenuros voltiles. Incluso esos halogenuros se utilizan en la
separacin de los istopos 235 y 238 del uranio, que se lleva a cabo
bajo la forma (en fase gas) de UF6.
UF6
La misma conducta presentan elementos como el Mo, Sn, Fe, etc.
Por ejemplo, se ha observado, en volcanes activos, la presencia de
abundante CuCI2, el cual es posteriormente lixiviado por las lluvias.
Los halogenuros metlicos pueden actuar como un nexo entre las

fases magmtica e hidrotermal, o bien dar lugar a la precipitacin
del metal como xido a travs de la reaccin del halogenuro con
agua (gas), precipitando el xido del metal y liberando el cido
respectivo El primer caso corresponde al Mo y el segundo a
respectivo.
metales como Sn, U y Fe.
La baja solubilidad de los sulfuros no permite el transporte de iones
metlicos simples en soluciones que contienen ion sulfuro. En
estas condiciones, la formacin de iones complejos con exceso de
ion sulfuro (p. ej. Hg S2=) o con ion cloruro protege al metal de la
precipitacin y permite su migracin.
En el caso del oro, la formacin del ion complejo Au (HS)2 permite
su estado inico en condiciones de oxidacin inferiores a las
requeridas para la oxidacin al ion simple Au+, lo que favorece su
migracin y concentracin por procesos hidrotermales.
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3
KILOM
METERS
2
1
0
-1
-2
-3
-4
METERS
-5
Figure 26. Conceptual model of topographically driven fluid flow in

sedimentary basins initiated by the elevated thrust-faulted landmass to the
left (from Garven and Freeze, 1984a). (Reproduced from Economic
Geology, 1985, v. 80, p. 308.)
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Fig. 1-16. Dbordement de la nappe fissurale captive dun socle le long de

sa bordure faille contre le bassin sdimentaire adjacent.
1.Carbonates.
1 Carbonates
2.Argiles (impermables).
3.Conglomrat de base.
4.Socle fissur.
5.Niveauy hydrostatique.
6.Cirulation de leau.
7.Terrain satur en eau.
Srie sdimentaire
10
impermables
Socle
Terrains sdimentaires
permables
p
Echelle indtermine
Schma de la vindage permanente des nappes captives la bordure des

bassins sdimen
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Placers Au, PGE, Sn, REE
Laterites Fe, Al, Au
Banded Iron Form.
Mn nodules + bogs
Supergene enrichment
Surface Processes
Roll front
Unconformity
U, V, Cu, PGE
Sedimentary
Basins
Stratabound
Pb, Zn, Cu, Ag
structural
dislocation
Volcanic centers
Hydrotherm
mal
Ore Fluid
d
Earths Cru
ust
Seawater/
Meteoric
Water
Wall rock
Leaching
Marine
Massive sulfide
Cu, Zn, Pb,
Ba, Au, Ag
Continental
Veins-Cu, As,
Zn, Pb, Au, Ag
Geothermal
Hot springs
Veins, sinters
Au, Ag, Hg,
As, Sb, Tl
Metamorphic
Devolatization
Shear Veins
quartz-carbonate
Au, As, W
Skarns
Fe, W, Cu, Au, Ag
Zn-Pb, Mo, W, U
Magmatic
Water
Pegmatites
Sn, Be, Li, U, B
Mica, quartz
feldspar
Exsolution
Source variations:
water, volatiles
metals, redox
T, P, % melting
Partial
Magma
Crystallization
Porphyry
Cu, Mo, Au, Ag,
Sn-W
Immiscible
liquid
melting
Ti
(anorthosite)
Volatile
rich
Kimberlites
Carbonites
Diatremes
Cu, Au, REE, U
Cr
(peridotite)
Ni-Cu-PGE
(komatiite,
gabbro)
Fe-P
(diorite,
syenite)
COMPOSITIONS OF SOME METALLIFEROUS

HYDROTHERMAL WATERS
12
Composition (mgkg1 solution)

Sample
T(C)
p
pH
Na
K
Ca
Mg
SiO2
Cl
Br
SO4
H 2S
CO2
Fe
Mn
Z
Zn
Cu
Pb
Ba
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
305
60
135
138
102
54
291
5.5
52,700
16,500
26,500
36
>475
154,000
99
110
7
1,660
1,550
1,390
506
6
95
194
5.5
55
92,600
1,870
5,150
764
60
156,000
n.r
840
n.r
140
81
82
5.4
0.3
n.r.
0.9
nr
n.r
76,200
970
36,500
2,400
34
193,400
1,510
3
n.r
n.r
294
102
342
n.r.
96
109
6.5
65
38,000
840
9,100
660
120
80,600
82
5.4
0.5
365
62
25
1.5
n.r.
1.1
760
51
5.1
61,700
990
48,600
3,050
28
198,000
649
64
<0.09
206
465
48.5
243
n.r.
70
60
5.5
76,430
560
17,740
3,426
n.r.
161,000
n.r.
247
4.0
15.8
23.8
n.r.
5
2
<2
n.r.
5.9
10,994
1,810
1,148
0.0
750
20,850
n.r.
0.0
n.r.
n.r.
2.7
12.2
01
0.1
<0.01
0.06
<3
7.8
10,790
395
413
1,280
10
19,355
67
2,745
<1
103
<1
<1
<1
<1
<1
<1
Note: n.r., not recorded.; (1) Salton Sea (McKibben et al., 1988b); (2) Red Sea (Shanks and Bischoff, 1977); (3)
Mississippi oil field brine, Raleigh 5 (arpenter et al., 1974); (4) Texas oil field brine, Pleasant Bayou (Kharaka et al.,
1980); (5) Pennsyvania oil well brine, W.M.H. Geiger No. 2-1 (Kharaka et al., 1986); (6) Cheleken geothermal field,
former Soviet Union (Lebedev, 1972); (7) Hydrothermal vent waters, Guaymas Basin, site 2 (von Damm et al.,
1985); (8) Average seawater (Janecky and Seyfried, 1984)
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Ion
ppm
ClNa+
SO42
Mg2+
Ca2+
K+
HCO3Br
H2BO3
Sr22+
18.800
10.770
2 715
2.715
1.290
412
380
140
67
26
8
% sel total
55,05
30,61
7 68
7,68
3,69
1,16
1,10
0,41
0,19
0,07
0 03
0,03
Tableau 1-5. Principales substances dissoutes dans leau de mer, daprs

KRAUSKOPF, 1979
14
Teneur en chlorures de leau de mer normale
10
Teneurs des saum

mures
normes leau de mer
Ca
Na
K
Mg
0.1
HCO3
SO4
0
20
40
60
80
100
120
140
Chlorures, /
Fig. 1-49. Variation de la teneur des lments principaux DES EAUX DU BASSIN DE
iIllinois, normalise par rapport la teneur en chlorures de leau de mer en fonction de la
teneur en chlorures, daprs GRAF et al., (1966).
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B
H2O
CO2
solid
lid liquid
gas
P/105 Pa
PA
(not to scale)
221
ice(l)*
ice(l)
supercritical
fluid
Tb
Tm
PA
0.06
liquid water
vapour
0.008 100
T/C
374
16
CP
LIQUID
P
SOLID
VAPOR
T
Figure 2.2a. Schematic P vs T diagram for water. C.P. = critical point.
0
200
400
DEPTH (meters)
600
-10
800
1000
10
1200
20
1400
30
1600
40
90
0%
5%
10%
15%
20%
25%
0%
5%
10%
15%
20%
25%
100
110
120
130
140
150
1800
100
150
200
250
300
TEMPERATURE (C)
Figure 2.2b. Bolling-point curves for H2O liquid (0 wt percent) and for brine of constant
composition given in wt percent NaCl. The insert expands the relations between 100 and
150C. The temperature at 0 meteres for each curve is the boiling point for the liquid at
1.013 bars (1.0 atm) load pressure which is equivalent to the atmospheric pressure at sea
level. The uncertainty is contained within the width of the lines. (Reproduced with
permission from Haas, 1971)
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a
b
oxidizing
sulphide
deposits
Cu4(OH)6Cl2
+ 0.8
dissolved
Cu2+
+ 0.4
ACIDIC
Cu2(OH)2CO3
(malachite)
Eh/vo
olt
ALKALINE
A
CuCl32+ + CuCl2
di
dissolved
l d
rain
streams
sea water
peat
and
bog
waters
0.0
ground
water
-0.4
10
12
10
12
pH
Figure 4.1 Eh-pH diagrams, showing a approximate stability fields of copper minerals in equilibrium with watter, S, Cl- and CO2
(simplified fromRose, 1976) Econ. Geol., 71. With malachite data from Garrels and Christ (1965), after J. Anderson (1958)); b.
approximate Eh-pH ranges of some natural aquatic environments: the stippled margins denote conditions beyond those normally
encountered in near-surface waters (Krauskopf, 1979)
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h
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Cmo se puede explicar la diferenciacin en los

diagramas FM?
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A
2,0
S
1,8
Cl
Ca
1,6
Rayon ionique
Rb
b
OH
F
1,4 O
Ba
Pb
Sr
1,2
1,0
Na
0,6
Th
U
Ca
Mn
Fe
Co
Ni
Li Mg
0,8
La
Lu
Sc
V
Fe
Cr
Al
0,4
Zr
Ti
Mn
Ge
Si
Be
P
B
0,2
Fig. 1-5. Diagramme rayon ionique versus charge

lectrique pour un certain nombre dlments
chimiques. Daprs Mason (1966)
0
2
+1
+3
+4
+2
Charge ionique
+5
+6
26
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Major elements are shown bold.
OXY-ANIONS
HYDROLYSATES
Normal cation charge
Nb Ta
Ti Sn Zr Hf
Si
Aliv Alvi
U Th
Ga V Sc
Cr Fe
Lu Y
SOLUBLE
CATIONS
La
REE
Mn Mg Co Fe
Ni Cu Zn
Be
Ca Eu Sr Pb
Na
Li
0.05
0.10
Ionic radius / nm
Rb Cs
2.0 A
1.0 A
0
0.00
Ba
0.15
0.20
28
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GEOTHERMAL FLUID COMPOSITION

Change in equivalent
wt%
NaCl due to
addition of Co2
VOLCANIC HOSTED SYSTEMS

Andesitic
FREQUENCY
Silicic
Seawater
recharged systems
Arima
EVOLVED CONTINENTAL BRINES

Salton Sea 25 wt%
Cheleken 26 wt%
Cesano 13 wt%
EPITHERMAL FLUID COMPOSITIONS

Correction to average
equivalent wt%NaCl
for CO2
Kuroko ores
Gold-silver ores
Base metal ores
Equivalent wt% NaCl

0
NaCl
wt%
10
Figure 1.8. Distribution of fluid salinities in the earths crust in relation to host-rock and crustal
environment. A normal frequency distribution has been assumed for each fluid type in the absence of
evidence for a continuity of compositions. For discussion, see text and Hedenquist and Henley,
1985b.
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Table 1. Summary of Fluid Inclusion Compositions and Pressure Estimates (from Baker and Lang, unpub, data)
Area: style
P (kbar)
CO2 fluids
Saline brines
CH4
Mike Lake:
sheeted veins
~0.5
Abundant
Abundant
Minor
None
Emerald Lake:
sheeted veins
>1.0
Abundant
Common
Minor
None
>1.5
Abundant
Common
Significant
Significant
??
Minor
None
Abundant
Minor
1.25-1.50
Abundant
Minor
Minor
??
~2.5
Abundant
None
Significant
Significant
~2.5
Abundant
None
Significant
None
Dublin Gulch:
sheeted veins
Dublin Gulch:
W skarn
Fort Knox:
Sheeted veins1
Scheelite dome:
Sheeted veins
Scheelite dome:
Sed-hosted veins
MacTung:
sheeted veins
N2
>2 3
>2.3
Abundant
None
Significant
Significant
Si ifi
t
MacTung:
W skarn
2.0 2.5
Minor
None
Abundant
Minor
Pogo: veins and

replacements2
1.7 2.0
Abundant
1 Data
Abundant
2Data
reported in McCoy et al. (1997)
reported in Smith et al. (1999)
32
P
(BAR)
TEMPERATURE(C)
200
250
300
450
(1)
350
(2)
250
(3)
200
(4)
400
(5)
Figure 5.12. Room temperature (25C) phase

relations of H2O-CO2 fluid inclusions trapped at
temperature of 200C, 250C and 300C and
pressures of 100, 200, 250, 350 and 450 bars,
corresponding to points 1-5 on Figure 5.11. The
innermost phase in each inclusion (black)
represents a CO2-rich vapor and the outer
phase (white) represents an H2O liquid. The
phase between the CO2-rich vapor and the
H2O-rich liquid in the inclusions trapped at
200C and 250 and 350 bars ((stippled
pattern))
pp
p
represents
a
CO2-rich
liquid.
Room
temperature phase relations of thes inclusions
were calculated using the method described in
the text and are listed along with calculated
temperatures of various phase changes in
Table 5.2.
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SCIENTIFICCOMMUNICATIONS
Deposit
&Style
Paleodepth
(km)
Setting
Low salinity
CO2(H2O)
Early immiscible CO2bearing

vapour andbrine,abundant
later low salinity H2Oinclusions
Epithermal
Dyke/sill/dome
Kori Kollo
Brewery Creek
Donlin Creek
Relative fluidabundance
Low salinity
Brine
H2O(CO2)
Fluidinclusion
types
Immiscible CO2bearing
vapour andbrine
Porphyry
Breccia/stockwork
Shotgun
Kidston
~5
Early CO2richinclusions,
later moderate to high salinity
inclusions,decreasing CO2
Plutonic/m
mesothermal
Sheeted
FortKnox
Dublin Gulch
Mokrsko
Jilau
Vasilkovskoe
Disseminated
Timbarra
Salave
Flatveins
Pogo
Abundant CO2richinclusions,
Commonly immiscible
Fluidinclusion legend
CO2rich
Halitebearing
H2Orich
Halite+syvite
bearing
10
Fig.1.Schematic geologicalmodel showing the relationship between intrusionrelated gold styles,paleodepth,andhydrothermal fluidtypes
(derived from acombination ofLanf etal.,2000;Bakerandlang 2001;Lang andBaker,2001).
34
D%
EAUMETAMORPHIQUE(300600C)
SMOW
CALIFORNIA300C
MACASSA200KERRADDISON250C
50
MARCASSA
380490C
EAUXMETEORIQUES
EAUJUVENILE
100
BORYEON
TAECHANG
JUNGWON,COREE
150
20
15
10
+5
+10
+15
S18O/
Fig. 5-18. Composition isotopique des fluides associs aux minralisations

discordantes dans le Greenstones Belts (donnes de BOHLKE et KISTLER, 1986;
KISHIDA ET KER-RICH, 1987; KERRICH et WATSON, 1984; SHELTON et al.,
1988).
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35
0
Wairakei
Larderello
The Geysers
50
Hekla
D(%)
Iceland
Niland
LassenPark
100
Steamboat Springs
150
15
10
180(%)
Fig. 1-42. Comparaison entre les compositions isotopiques des fluides gothermaux chlorurs
(cercles blancs) et les eaux mtoriques locales (cercles pleins), daprs CRAIG (1963).
36
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18O/
0
10
20
+10
+20
*Ocean Water (SMOW)
0
Meteoric Water Line
20
40
TF
Geysers
Iceland
D/
60
80
100
140
WC
CP
TU
Salton Sea
Mt. Lassen
B
M
BU
TE
IB
120
Magmatic
Water
Walrakel/Broadlands
Larderello
Steamboat Springs
A
CL
Geothermal H2O
CO
Surface
Subsurface
J,W,TD
CA
Yellowstone
Hydrothermal H2O
Epithermal
160
5.4.Fraccionamientosisotpicosenfuentestermalesydepsitosepitermales.
38
34S/
Environment
20
Meteorites
Igneous Rocks: total-S
Cu-Fe-Ni sulfides of
layered mafic intr.
Volcanic Emanations
SO2
native sulfur
H2S
Sea Water SO-4
Sedimentary Rocks
sulfates
sulfides
Mississippi Valley Deposits
sulfates
sulfides
Hydrothermal Deposits
Cordilleran: sulfates
sulfides
Volc. Mass: sulfates
sulfides
Ocean Ridge: sulfates
sulfides
10
+10
50
+20
+30
+40
+50
5.6.ValoresdeistoposdeSparavariasmuestras.
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39
lneade
condensacinS
10
HSO4
LogS2
S=
14
SO4 =
18
18
42
34
38
30
LogO2
2.6. Diagrama de campos de las especies sulfuradas en solucin. Lneas delgadas corresponden a las del diagrama 1.5.
40
Predomini
odeagua
Predomini
odevapor
Agua
termal
Paso
geotrmic
o
Agua
superficia
l
Roca
Impermeabl
e
Fractura
s
rellenas
devapor
Roca
almac
nde
agua
calient
e
Roca
cristali
na
Fuentedecalor
(magma)
(A)
(B)
Figure 6.36. (A) La energa geotrmica se pone de manifiesto giseres naturales, como los del Parque de Yellowstone, en
Wyoming (cortesa de J.D. Rimstidt). (B) Diagrama esquemtico que muestra las caractersticas geolgicas de campos
geotrmicos de vapor seco y vapor hmedo.
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Metal transport mechanisms

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1

Dr. JORGE OYARZUN MUOZ

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

GEMM - (J,O.) - E - TRANSPORTE DE LOS

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Los halogenuros metlicos pueden actuar como un nexo entre las

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Figure 26. Conceptual model of topographically driven fluid flow in

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Fig. 1-16. Dbordement de la nappe fissurale captive dun socle le long de

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Schma de la vindage permanente des nappes captives la bordure des

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

COMPOSITIONS OF SOME METALLIFEROUS

Composition (mgkg1 solution)

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Tableau 1-5. Principales substances dissoutes dans leau de mer, daprs

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Teneurs des saum

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Cmo se puede explicar la diferenciacin en los

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Fig. 1-5. Diagramme rayon ionique versus charge

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Normal cation charge

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

GEOTHERMAL FLUID COMPOSITION

VOLCANIC HOSTED SYSTEMS

EVOLVED CONTINENTAL BRINES

EPITHERMAL FLUID COMPOSITIONS

Base metal ores

Equivalent wt% NaCl

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Pogo: veins and

reported in McCoy et al. (1997)

reported in Smith et al. (1999)

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Figure 5.12. Room temperature (25C) phase

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Early immiscible CO2bearing

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Fig. 5-18. Composition isotopique des fluides associs aux minralisations

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

*Ocean Water (SMOW)

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade

Dr. Jorge Oyarzun Muoz - joyarzun@expo.intercade.org ConsultorIntercade