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TRANSPORT AND DEPOSITION OF METALS BY HYDROTHERMAL FLUIDS

Roberto Perez Xavier Departamento de Geologia e Recursos Naturais Instituto de Geocincias UNICAMP Campinas (SP) - Brasil

Hydrothermal fluids are subjected to changes in T, P, composition, pH, redox conditions during fluid/rock or fluid/fluid interactions in hydrothermal systems affect metal solubilities and may cause deposition of ore and gangue minerals

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Cu Pb - Zn

10 ppm

METAL SOLUBILITY IN HYDROTHERMAL FLUIDS


Metal concentrations on the basis of fluid inclusions in ore deposits and active geothermal fields. Cu, Pb and Zn (black circles); Ag, Au and Hg (open circles).
Dotted lines = minimum concentration values

Cu Pb - Zn

1 ppm

1 ppb Au e 10 ppb Ag

Au-Ag << base metal in hydrothermal solutions


Ag - Au

May reflect crustal source !!

Seward & Barnes (1997)

METAL SOLUBILITY IN HYDROTHERMAL FLUIDS ....


Magmatic fluids

Yardley (2005)

...... depends upon TEMPERATURE

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Metal solubility in hydrothermal fluids depends upon salinity


magmtico

metamrfico geotermal

bacinal

Yardley (2005)

Ore-forming fluids are chemically similar to other crustal fluids Controlled by reactions with (crustal) rocks

NaCl Dissolution

Cl- enveloped by H2O molecules por molculas de gua (hydration hydration) )

Na+ enveloped by H2O molecules (hydration hydration) ) o)

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SOLUBILIDADE DE METAIS EM FLUIDOS HIDROTERMAIS O fator temperatura

Hydrothermal transport of gold

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HYDROTHERMAL FLUIDS: METAL TRANSPORT Metals ARE NOT transported as single ions but as ionic complexes AuI2AuBr2AuCl2Au(HS)2Au(HS)0 AuNH3)2+ Au(CN)2Ligant must be available in the fluid

Ionic complex must be stable at high P-T condiitons

What complexes would be more important to transport metals in hydrothermal fluids?

Broadlands T(oC) pH ClBrINHn CO2+HCO3-+CO3HSO4- + SO4-2 H2S + HSComplexos AuI2


-

Salton Sea 320 4,2 118.202 91,6 13,6 374 570 3,7 15,9

260 6,2 1184 4,3 0,5 1148 5278 5,4 136

Constante de equilbrio 19 12,4 9,2

AuBr2AuCl2Au(HS)2 Au(HS)0 AuNH3)2 Au(CN)2


+ -

30,1 24,5 26,5 38,7

What complexes would be more important to transport Au in these hydrothermal fluids?

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HYDROTHERMAL FLUIDS: METAL TRANSPORT


Cu&Zn Au

ZnCl2SOLUBILIDADE (log ppm) 2 Au(HS)2AuCl2-2

pH=4, 1m NaCl, aH2S= 10-3, SO4/H2S= 10-1

Cu(HS)2-

CuCl2-

-4

150
Seward & Barnes (1997)

200

250

300

350

TEMPERATURA C

Fluid inclusions and active geothermal systems reveal that Cl- and HS- are the most important ligands for a wide range of metals

FLUIDOS HIDROTERMAIS: TRANSPORTE E DEPOSIO DO OURO

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HOW DO METALS PRECIPITATE FROM HYDROTHERMAL FLUIDS: Au 4 Au(HS)2- + 2 H2O + 4 H+ = 4 Au0 + 8 H2S + O2
temperature

pH

O2

aH2S

300 C

Seward (1982) e Brown (1986)

HOW DO METALS PRECIPITATE FROM HYDROTHERMAL FLUIDS: Au

Sulphide alteration (reduces < S of the fluid) FeO (sillicato ou xido) + Au(HS)-2 + O2 = Au0 + FeS2 + quartz +H2O Interaction with carbonaceous rocks 2C + 2H2O = CH4 + CO2 < fO2

Oxidation: it promotes Au transport until saturation at high O2 (H2S + HS- + SO42- see diagram) interaction with oxidized rocks (hematite-bearing), fluid mixing or boiling/immiscibility

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FLUID PHASE SEPARATION: BOILING - IMMISCIBILITY

Audtat et al. (2008)

< S of the fluid = H2S/HS- fraccionate to the vapour phase Au(HS)-2 + 1/2 H2 = Au + H2S + HS-

> pH = CO2 removal H2CO3 HCO3- + H+

O SISTEMA H2O - CO2 NaCl Imiscibilidade (efervescncia)

Gehrig et al. (1986)

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HOW DO METALS PRECIPITATE FROM HYDROTHERMAL FLUIDS: Au 4 AuCl2- + 2 H2O = 4 Au0 + 4 H+ + 8 Cl- + O2
-25
AuCl2-: S= 0,5x10-2 300 C

temperature pH O2

-3

-4 AuCl2-

-30

O2
-35 pirita

hematita

aCl-40 2 4 pirrotita 6 8 10
Seward (1982) e Brown (1986)

pH

Fluid mixing: < aCl-, > fO2

HOW DO METALS PRECIPITATE FROM HYDROTHERMAL FLUIDS: Cu


1m NaCl; Kf+muscovite+qtz; hm+mgt+py (HMP) e mgt+py+po (MPP) 400 C 0,5 kb; hm+mgt+py (HMP) e mgt+py+po (MPP)
Liu & McPhail (2005)

CuClx1-x + 1/2 H2O + FeCly2-y + S29g) = CuFeS2 + (x+y) Cl- + 3H+ + 0,75 O2

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HOW DO METALS PRECIPITATE FROM HYDROTHERMAL FLUIDS: Pb - Zn


3: 103 mg/kg chloride 5: 105 mg/kg chloride

PbCl2 + H2S (aq) 2Cl5 5

PbS + 2H+ +

4 2 log solubility (mg/kg) 0 -2 -4 -6 -8

ZnCln2-n + H2S(aq) 2H+ + nCl-

ZnS +

temperature
3 3 200 250 300 temperature ( C)

pH O2 aCl-

Why is salinity important?


Cl- is the prime ligand for a wide range of metals
400 C 0,5 kb; hm+mgt+py (HMP) and mgt+py+po (MPP)

Highly saline fluids transport metals more efficiently than diluted fluids at the same conditions
If Cl- is the main ion why chlorides are not common gangue minerals in ore deposits?

Liu & Phail (2005)

Na K Ca Mg chlorides are highly solubles !!

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But sulphur is also important !


Necessary for the precipitation of metals as sulphides

Without enough sulphur, metals tend to remain in the hydrothermal fluid

Barton & Johnson (1996)

CuClx1-x + 1/2 H2O + FeCly2-y + S2(g) =CuFeS2 + (x+y) Cl- + 3H+ + 0,75 O2

1. fluids with Cl e S (metals > line S) precipitate Fe oxides and low sulphidation assemblages 2. Cl (meteoric) = not eficient to transport Cu and Fe, but may transport Au, Pb, and Zn

Barton & Johnson (2000)

3. Modrate salinity fluids (e.g., sea H2O) = transport Pb, Zn, Fe

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The Fe solubility would increase with increasing temperature, but if fluids are reduced, the content of dissolved sulphur would limit the concentration of dissolved Fe. The low sulphide-content and abundance of minerals with ferric iron at a deposit, indicates a more oxidized fluid. In na oxidized fluid, more of the sulphur would be present as SO42- and would thus not greatly limit Fe solubility at high temperatures.

AU VERSUS BASE METALS

http://www.unalmed.edu.co

Au, Ag, Zn solubilities as a function of S and Cl concentrations

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REFERENCES
Barnes, H.L..1997. Geochemistry of Hydrothermal Ores Deposits, John Wiley, 972 p. William-Jones, A.E.; Bowell, R.; Migdisov, A.A. (2009). Gold in solution. Elements, 5: 281-287. Yardley, B. (2005). Metal concentrations in crustal fluids and their relationship to ore formation. Econ Geol 11th Anniversary Special Paper, 100: 613 - 632

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