HYDROTHERMAL FLUIDS: HOW THEY FORM AND EVOLVE IN THE EARTHS CRUST

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

FLUIDS IN THE LITHOSPHERE: INDIRECT EVIDENCE ?

Minerals Chlorite Actinolite/ Hornblende Biotite Phlogopite Epidote Calcite Dolomite Pyrite Pyrrhotite Volatiles in the composition (wt %) 10% H2O 2% H2O

3,2 % H2O 3,2 3,5% H2O 1% H2O 45% CO2 40% CO2 50% S 30% S

Hydrous silicates (OH) + carbonates (CO2) + sulphides (H2S) - sulphates (SO4)

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FLUIDS IN THE LITHOSPHERE: INDIRECT EVIDENCE ?

1m

Average grade of 0.3 g/t Au-bearing quartz boudins Morro do Ouro (Paracatu/Brazil)

Loriesfontein area (Karoo Basin, South Africa). Bright blobs hydrothermal pipes filled with brecciated and metamorphosed shale CH4 degassed during contact metamorphism of black, organic-rich shale, some 182.5 million years ago.

Mesh texture generated during serpentinization of olivine in a serpentinized peridotite from the Leka ophiolite complex, Norway

Jamtveit & Austrheim 2010, Elements, 6

1 50 m

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FLUIDS IN THE LITHOSPHERE: DIRECT EVIDENCE ?

ACTIVE GEOTHERMAL SYSTEMS IN THE OCEANIC CRUST

Fumaroles or black smokers

NEPR, SEPR = East Pacific Rise MAR = Mar Crest RR = Iceland SWIR and SEIR = Southwest and Southeast Indian Ridge

FLUIDS IN THE LITHOSPHERE: DIRECT EVIDENCE ?

ACTIVE GEOTHERMAL SYSTEMS CONTINENTAL CRUST
HOT SPRINGS OR GEYSERS

S1 S2

FLUID INCLUSIONS
L V S4 S3

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WHAT IS A FLUID? H2O + salts + volatiles (CO2, CH4, N2, H2S, etc.) vapor/gases + silicate melts (magma)

lIquid +

Viscosity of magma basltico 103 104 P whereas H2O = 10-2 P) Above critical point (Pc), there is no distinction between liquid and vapor phases similar densities = supercritical fluid
Reviews in Mineralogy & Geochemistry Vol. 76 pp. 165-218, 2013

FLUIDS IN THE LITHOSPHERE

Pirajno (2009)

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HYDROTHERMAL SYSTEMS

Wyborn 2005

from the source to the ore !!

HYDROTHERMAL FLUIDS FLUIDS: : HOW DO THEY FORM?

Tivey, M. K. 2007, Oceanography, 20 (1)

Figure 1. Known sites of hydrothermal venting along mid-ocean ridges, in back-arc basins, rifted arcs, and at submerged island-arc volcanoes (red), and areas of activity as indicated by mid-water chemical anomalies (yellow). EPR = East Pacific Rise. TA G= Trans Atlantic Geotraverse, MEF = Main Endeavour Field, and GR-14 = Sea Cliff hydrothermal field on the northern Gorda Ridge.

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pH ~ 3

P > 22 Mpa = 0.22 kb

T= 00C

4000C

HYDROTHERMAL FLUIDS FLUIDS: : HOW DO THEY FORM? Seawater evolution within the oceanic crust

Humphris et al. (1996)

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HYDROTHERMAL FLUIDS FLUIDS: : HOW DO THEY FORM? Seawater evolution within the oceanic crust
Seawater T ( C) pH (25 C) Na (mM) K (mM) Ca (mM) Mg (mM) Si (mM) Cl (mM) SO4 (mM) H2S (mM) Fe (M) Mn (M) Cu (M) Zn (M) 2 7.8 464 9.8 10.2 52.7 0.2 541 27.9 0 <0.0015 0 0.007 0.01 Hydrothermal fluid 360 - 365 3.35 537 17.1 30.8 0 20.75 636 0 2.3 3.5 5590 680 98 - 120 47 - 53

http://www.searchanddiscovery.net/documents/2010/40523humphris/ndx_humphris.pdf

HYDROTHERMAL FLUIDS FLUIDS: : HOW DO THEY FORM? Seawater 2 C Alkaline (pH 8) oxidizing SO42+>> S2Hydrothermal Fluid 350 C Acidic (pH 4.6) Reducing S2- >>SO42-

High Mg2+

Poor Mg2+

Metal poor

Enriched in metals 3.2% NaCl

3.2% NaCl

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HYDROTHERMAL FLUIDS FLUIDS: : HOW DO THEY FORM?

1. Acid pH 2Ca2+ + Fe3+ + 2Al3+ + 3SiO2 + 7H2O = Ca2FeAl2Si3O12(OH) + 13H+ Silicates in mafic rocks 2. Oxidizing to reducing 11Fe2SiO4 + 2SO42- + 4H+ = FeS2 + 7Fe3O4 + 11SiO2 + 2H2O Mafic minerals 3. Fluid- rock interaction = loss of Mg2+ 2NaAlSi3O8 + 5Mg2+ + 8H2O = Mg5Al2Si3O10(OH)8 + 2Na+ + 8H+ + 3SiO2 Albite fluid chlorite quartz fluid pyrite magnetite fluid epidote

SUBMARINE HYDROTHERMAL SYSTEMS Sulphides = 3.9 x 106 ton Fe = 2.3 x 106 ton Cu = 30 - 60 x 103 ton Zn = 15.2 x 103 ton Hydrothermal alteration zone = 0.4 0.7 km3 Required energy = 1000 MW
TAG = Trans-Atlantic Geotraverse (Cadeia Meso-Atlntica 26 08N)

Humphris & Tivey (2000), GSA 349

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TYPES OF HYDROTHERMAL FLUIDS

Barnicoat , A. (2009)

8.7 x 1011 kg/year = mass of H2O incorporated into the lithosphere in subduction zones

GEOTHERMAL FLUIDS: EVOLVED METEORIC H2O

Mostly recycled rainwater

high geothermal gradients orogenic (convergent margins) and nonorogenic areas (intracontinental rifts) Geothermal waters (250 C. 1-2 km) are the present-d ay analogues of nzic.org.nz/ChemProcesses/water/13A.pdf epithermal Au-Ag deposits

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GEOTHERMAL FLUIDS: EVOLVED METEORIC H2O

Composition Na-Cl (mg/kg) Near neutral chloride SiO2 660 Na Ca K Cl HBO2SO42HCO3pH 1200 17.5 200 2156 115 25 32 4.8 SO4 Cl Na-CO3 Seawater River Acid Alkali H2O sulphate carbonate 490 485 1.2 58,5 560 21.6 88 167 3.1 175 220 37 43 57 1.2 <1 3177 6.2 0.005 0.01 10760 411 399 19350 2710 142 8.1 8.3 13 4.8 15 2 5.7 6,7 23 5 6.5

Na Ca Mg - HCO3Ca Mg - HCO3-

alumino silicate rocks

limestone/dolomite
nzic.org.nz/ChemProcesses/water/13A.pdf

GEOTHERMAL FLUIDS: EVOLVED METEORIC H2O

2H+(aq) + 2KAlSi3O8 + 9H2O 2K+(aq) + Al2Si2O5(OH)4 + 4H4SiO4(aq) feldspar rock kaolinite dissolved silica Similar reactions provide Na+(aq) and Ca2+(aq) to the geothermal water that becomes more acidic and oxidising. 2H2S + 3O2 2SO2 + 2H2O H2S + 2O2 SO42- + 2H+ Both hydrogen sulfide ions (HS-) and chloride ions (Cl-) can form complexes with metal cations derived from the magmas or by fluid-rock reactions stable at high temperatures and high concentrations of metals. PbCl3-(aq) + H2S(aq) PbS(s) + 2H+(aq) + 3Cl-(aq) Size of meteoric systems may be huge Transit time for fluid ~2 Myr Generally of low salinity (< 3.2 wt% NaCl) and dont carry a lot of metals, but can be directly important - mixing with other fluids = dilution

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MAGMATIC FLUIDS

MAGMATIC FLUIDS
Vulcanos Magma T( C) H2O CO2 SO2 H2S HCl HF NaCl Augustine (Greece) andesitic 870 83.9 2.4 5.72 1.00 6.0 8.6x10-2 1.4x10-3 Etna (Italy) basaltic 928 91.9 1.4 2.8 0.1 0.5 1.3x10-3 St. Helens (USA) dacitic 710 98.6 0.8 6.7x10-2 9.0x10-2 7.6x10-2 0.03 4.1x10-4
Symonds (1992)

Analyses in moles/100 moles de gs

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MAGMATIC FLUIDS AND VOLCANIC ERUPTIONS Etna (Italy) 1975 to 1987

T ( C) H2O CO2 HCl S Cu Au 900 50 x 106 t / yr 13 x 106 t / yr 0.1 0.5 x 106 t / yr 0.2 0.75 x 106 t / yr 480 580 t / yr 80 1.200 kg / yr
Hedenquist & Lowenster (1994)

MAGMATIC FLUIDS: SALINITY

Salinity depends on DEPTH (PRESSURE) of magma crystallization

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MAGMATIC FLUIDS: VOLATILES (CO2 AND Cl) CO2 is 10 X less soluble than H2O in silicate melts CO2 solubility increases linearly with pressure CO2-rich fluids are generated by magmas that crystallize at deep crustal levels Addition of H2O to a melt decreases the solubility of CO2

Solubility plot for system rhyolite-H2O-CO2 at 675 C.

Cl is less volatile than CO2 limited solubility in exsolving vapors Fe, Na, K chloride complexes remain in the melt until saturation of an aqueous phase

MAGMATIC FLUIDS: VOLATILES (CO2 AND Cl)

CO2- H2O Brine
vv v v v v v

0 km

+ +

+ + + +

5 km

+ + + + + + + + + + + + + + + +
+

10 km

Baker (2002)

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FLUID PHASE SEPARATION: BOILING IMMISCIBILITY

Audtat et al. (2008)

Efficient mechanism for the precipitation of metals by hydrothermal fluids !!

MAGMATIC HYDROTHERMAL SYSTEMS

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BASINAL FLUIDS (OIL(OIL-FIELD BRINES)

Formation water
water

present in pores and fractures significance to origin or age

no

Connate water
water

trapped with the sediment and subsequently unmodified.

Sedimentary basin waters have a range of origins connate, (modified) meteoric water Most basinal fluids (formation waters) are of recent meteoric origin

BASINAL FLUIDS (OIL(OIL-FIELD BRINES)

Conc. (ppm) TDS Na+ Ca2+ K+ Fe2+ Mg2+ SiO2 Zn2+ Pb2+ ClH2 S SO42HCO3T(C) pH Louisiana 235.700 78000 10250 1065 84 1140 48 143000 0.4 0.4 450 150 6.2 Mississippi Seawater 230.000 54200 27600 485 181 1770 42 143 28 143600 248 150 6.2 35.200 10760 412 399 0,002 1294 6,2 0,02 0,00003 19350 2712 45 2 8,2
Hanor (1995)

Variable composition, but generally Na-CaCl-rich salinity up to 6.6 higher than seawater: origin of high salinity?
Seawater evaporation to the halite saturation point = bittern fluids Interaction with evaporites= halite dissolution

Fe, Zn, Pb seawater

103 to 106 higher than

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BASINAL FLUIDS AND ORE DEPOSITS

Sediment-hosted Pb-Zn deposits: SEDEX and MVT

METAMORPHIC FLUIDS
PELITIC ROCKS Clay minerals (15-20 % H2O)

metamorphism

chlorite (10-12 % H2O) biotite + muscovite (3-4 % H2O) staurolite + cordierite (2 % H2O) CARBONATE ROCKS

CaMg(CO3)2 + 2SiO2 = CaMgSi2O6 + 2CO2 dolomite quartz diopside

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GERAO DE FLUIDOS NO METAMORFISMO

Folhelho

granada mica xisto

(Jamtveit, 2010)

COMPOSITION OF METAMORPHIC FLUIDS

H2O + (CO2 + CH4 + N2 + H2S), 5-6 % NaCl Salinities may be higher if evaporites are involved in the metamorphic process Metamorphic fluids tend to be metamorphic facies (e.g. granulite) CO2-rich in higher

Maximum fluid flux ~10-11 m3/m2/s (very small) Duration << 1 million years Time-integrated flux is ~1000 times smaller than flux required for mineralisation (Cox, 1999) Metamorphic fluid must be FOCUSED for mineralisation

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METAMORPHIC FLUIDS AND OROGENIC GOLD DEPOSITS

Low-salinity, mixed aqueous-carbonic fluid broadly uniform over deposits formed at different crustal levels (6 km to 20 km)

HYDROTHERMAL FLUIDS ?
Aqueous solutions Variable temperatures: 50 C to >500 C Diluted (0.2 - 0.5% salts) to highly concentrated (> 25% salts) solutions abundant Na+ e ClpH: acid to slightly alkaline Volatiles: CO2 (CH4, N2, H2S, SO2) state (O2) and metal solubility control the redox

Metals: ionic complexes [e.g. Au(HS)-2 ; AuCl-2 ] and redox control solubility NO GENETIC IMPLICATION !!

T, pH

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MECHANISMS OF FLUID FLUX IN THE CRUST

Etheridge et al. 1983

MECHANISMS OF FLUID FLUX IN THE CRUST

log fluid flux (m/yr) -8 Deformation Convection Topographic/meteoric Metamorphism
Intrusions

-6

-4

-2

Compaction

There is considerable overlap in flow rates, making it difficult to predict which one will dominate.
Heather Sheldon (2008 )

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HYDROTHERMAL FLUIDS: SUMMARY

Kesler (2005)

TECTONIC SETTINGS, CRUSTAL FLUIDS AND ORE DEPOSITS

basinal

Groves et al. (1998)

Magmatic magmatic + meteoric Evolved seawater + metamorphic meteoric

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FLUIDS IN DIFFERENT CLASSES OF GOLD DEPOSITS

Ridley & Diamond (2000)

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