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

Page 1

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

Page 2

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)

Page 3

SOLUBILIDADE DE METAIS EM FLUIDOS HIDROTERMAIS O fator temperatura

Hydrothermal transport of gold

Page 4

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?

Page 5

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

Page 6

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

Page 7

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)

Page 8

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

Page 9

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 !!

Page 10

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

Page 11

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

Page 12

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

Page 13