HYDROTHERMAL &

MAGMATIC-HYDROTHERMAL
ORES
Understanding Economic Geology
--Eamon McCarthy Earls
FLUIDS IN THE EARTH
 HYDROTHERMAL FLUID SOURCES
Seawater
Na+, K+, Ca2+ Mg2+
Cl-, HCO3-, SO42- Meteoric (precipitation) water
 Metal redistribution in crust  Main component of groundwater
 Expelled through ‘black smokers’
 HYDROTHERMAL FLUID SOURCES
Connate Water
 Bound in interstitial sed. pores
 Increases in density & salinity with depth
 Bound water in H2O/OH- in clays
Metamorphic Water >200°C
 At 300°C kaolinite metamorphoses to
pyrophylliteproduces water
 At 400°C muscovite & chlorite go to
biotitewater, CO2, methane & sulfur
OTHER METAMORPHIC FLUIDS
 CO2 most common fluid after water
 High concentrations of CO2 in high-grade
metamorphism
 Low/medium grade metamorphism—blend of CO2,
H2O & CH4
 At very high temperatures CO2 & H2O become fully
miscible and form a single fluid, dissolved together
VOLUME OF MINERALS PRECIPITATED
FROM A FLUID
 Assumes equilibrium of pore fluid & host rock

Vm=Ftsinβ(dT/dZ)αT/ρ
Vm=volume mineral precipitated
F=fluid flux
t=time (seconds)
β=angle of direction of flow & isotherms in rock
dT/dZ=geothermal gradient
αT=function of solubility & temperature
ρ=density of material precipitated
FLUID FLOW IN THE CRUST
 Pervasive flow in shallow, porous rock
 Ocean fluid flow driven by heat at mid-ocean ridges—
seawater is superheated after migrating into faults
 Dilatancy: change in volume of rock due to seismic
shifts & shearing
 Orogenies can create dilatancy
LITHOSTATIC VS. HYDROSTATIC
 Lithostatic: pressure gradient of units of rock based on
overlying rock densities
 Can vary slightly based on the dip of rock

 Hydrostatic: pressure on rock at bottom of ocean

MAGMA RELATED
HYDROTHERMAL DEPOSITS
QUARTZ & OTHER VEINS
 Precipitation of silica from hot
fluids
 Water is a more powerful solvent
at higher temp. and pressure
 8 wt% silica solubility in water

 Need pressures of 7 kbar & 900 C

 High temp. water easily dissolves

alkali elements
 Often similar composition to a
silicate melt
 Ligands—electron donors are
dissolved anions
MAGMATIC SOLUTIONS
 10 major oxides make up most rocks
 Alkali+alkali earth metals dominate in magmatic fluids

 Volcanic & geothermal fluids may be best indicators

 Generally low in Sulfur—SO2 partitions into vapor at

high temperatures and boils away
 Oxidized SO4^2- and HS- are mutually exclusive forms

 Cu-Mo porphyrys associated with reduced waters,

chalcopyrite and pyrite
ANALYSIS
 Examine fluid inclusions in quartz
 High temp-high salinity results
common in early stages
 Evidence for boiling

 Microphotographs of daughter
crystals—halite, sylvite (KCl)—
indicate large amounts of alkali
and halogen elements
 Laser-ablation inductively
coupled mass-spectrometry (LA-
ICP-MS)—analyzed tiny
quantities of cations
CO2 IN MAGMATIC FLUID
 Lower solubility in magma than
water
 Carbonate ions—alkaline magmas

 Molecular carbon in felsic/mafic

 Early vapors more CO2 rich than

later due to volatility
 Shallow emplacement—H2O-rich

 N2 & CO2 effervesce easily

OTHER MAGMA PROPERTIES
 Differentiation of magma based on
density
 Chemically distinct phase in granites
due to aqueous saturation
 Bubbles of gas form in magma when
vapor pressure=load pressure
 First boiling—vapor saturation
happens because of decreased pressure
as magma moves to a shallower point
 Second boiling—anhydrous minerals
crystallize, leaving H2O saturation
 Immiscibility—low salinity/high
salinity brine segregation in presence
of CO2 or low pressure
PEGMATITES
 Felsic rocks with large crystals,
possibly formed from highly mobilized
ions in heated fluid
 Very coarse grained—granitic minerals

 Quartz, feldspar, muscovite, topaz,

tourmaline, beryl
 Lithophile alkali and transition metals

 Cerny (1991) grouped them by metal

concentrations
 I-type: Nb-Y-F

 S-type: peraluminous, Li-Cs-Ta, Boron

 One of the least understood processes

in igneous petrology
PEGMATITE FORMATION
 Jahns-Burnham model (1969)—H2O fluid
saturation causes the change from granite to
pegmatite
 Volatile-related solidus depression

 Mineral zones—density difference between

fluid & melt
 D. London et. al. (1996)—undercooling
granite magmas can also form pegmatites
 Pegmatites can be replicated in petrology
labs
 Uncommon in mafic rocks because mafics
nucleate crystals too rapidly
 B-F-P+water increase the range of possible
crystals that can form at lower temperatures
FLUIDS & TRACE ELEMENT
PARTITIONING
 Holland (1972) showed that Cl- controls most metal
solubility in water along with temp. and pH
 This ligand must be able to partition into water in the
first place
Cl-(melt)+OH-(melt)HCL (fluid)+O2-(melt)
PORPHYRY DEPOSITS
 Base metal deposits in granite
intrusions
 Cu-Mo or Sn-W (tin & tungsten)

 Calc-alkaline, I-type, arc-related

 Near Andean subduction zones

 S-type granite related to Sn-W—

also partial melting of
metasediment material
 Mo or Cu dominates, in most
porphyrys with the other as a
secondary metal
 Need oxidized I-type conditions
near subduction zones
PORPHYRY DEPOSITS
 Limited fractionation during
crystallization due to low water
content
 Poorly differentiated porphyry
rocks like rhyodacite
 Early vapor-saturation (first
boiling)
 Lack of water limits crystallization
and keeps Cu in a nearly pure form
—ordinarily it’s compatible with
granite
 By contrast, Mo is incompatible
and ends up in the H2O phase—
low partition coefficient helps to
explain why Mo is usually the
secondary metal
TUNGSTEN PORPHYRYS
 Arc related
 Reduced ilmenite-rich S-type
granites
 Deeper below the surface

 W is incompatible—it
fractionates during
crystallization
SKARN DEPOSITS
 Calc/silicate replaces limestone and other
carbonates
 Contact metamorphism OR
metasomatism
 Enriched in Sn, Au, W, Pb, Fe, Cu, Mo

 Dolomite vs. limestone origin determines

calcium vs. magnesium content
 Tungsten mainly from skarns

 Tasmania

 MacTung—Yukon Territory

 Bingham district, Utah—copper skarn

related to porphrys
 Fe skarns in Sverdlovsk & Sarbai, Russia
EPITHERMAL GOLD
 Recent volcanics in the Pacific Rim
 New Zealand—North & South Island

 Shallow depths: 50-1000 m

 Low temp: ~200 C

 Controlled by high or low-sulfidation

 High sulfide: Vapor saturation fluids

from magma—highly oxidized and acidic
 H+ remains in fluid as CO2 & SO2
partition—leaches most elements
 Common in Andes

 Low sulfide: meteoric water nearly

neutral, with low Ph
 Common in western US
HYDROTHERMAL ORES
METALS & LIGANDS
 Ligand: ion or molecule
bonded to a metal atom to form
a coordination complex
CONTROLS ON PRECIPITATION-
TEMPERATURE
 Temperature: cooling of fluid increases chances of ore-
formation
 Not true at depth where rocks & fluids have = temp

 VMS Deposits: rapid cooling of superheated vent brines

in the deep ocean
 Enriched in metals—often with chloride or bisulfide
complexes
 Most efficient ore deposition process for metals
CONTROLS ON PRECIPITATION-
PRESSURE
 Less pressure=more soluble
 Not generally related to ore-formation

 Significant in cases of effervescence or boiling

CONTROLS ON PRECIPITATION-
PHASE SEPARATION
 Liquidvapor transformation due to decreased pressures
 Depressurization causes effervescence—H2O & CO2
separate
 In most metamorphic rocks, H2O & CO2 are mixed, but
may separate in cracks leading to ore precipitation
 Faults, cracks and fissures create reduced pressure
environments needed for deposition
FLUID MIXING
 Two or more fluids of different temperatures can lead to
precipitation when combined
 Blended meteoric & magmatic waters produces some of
the most economically valuable hydrothermal ores
 Connate & meteoric fluids may mix to create sediment
hosted ores near continental rifts
 Ex) SEDEX deposits in eastern Australia

 Fluid Blocks: altered mineral assemblies close to fluid

pathways—metals precipitate on walls
 Changes in redox & pH
ADSORPTION
 OH- (alkaline solutions) can promote cation adsorption
 Broken or damaged minerals with fracture planes, trace
element substitution points or high charge areas invite +
acidic solutions tend to adsorb anions
 Adsorption usually happens at low temps

 Oxides & sulfides play an important role

 Ex) goethite+acidic solution= great adsorption

 Mercury easily adsorbs to sulfides along with Zn & Cd

BIOMINERALIZATION
 Many microbes can interact chemically with metals
 Possible for microbes to influence local metal
precipitation or to take in the metal within their cell
membranes
 Biologically induced: microbes changes local pH & Eh

 Ex) ferric hydroxide (FeOH3) forms due to microbes &

can remineralize as goethite/hematite
 Several species of bacteria concentrate Fe grains
BIOMINERALIZATION
 Biological Control: formation within
the cell
 Ex) magnetite crystals often form in
favorable reducing conditions in bacteria
 SRB—sulfate reducing bacteria:
generate sulfide & accept electrons to
organic sulfates—source of pyrite
 Birnessite & vernadite, Mn-minerals
formed due to bacteria
 Phosphorites in Australia

 Apatite crystals in place of

cyanobacteria
 Carboniferous sea water reduced around
vents to form Irish SEDEX Pb-Ba-Zn
deposits
HYDROTHERMAL ALTERATION
PROPYLITIC ALTERATION
 Most common hydrothermal
alteration
 Closely resembles greenschist
facies metamorphism
 Similar suite of minerals

 Epidote, chlorite, calcite,

clinzoisite, albite
 200-350 C

 H+ metasomatism related

 Also Cu-porphyry related

POTASSIC ALTERATION
 Forms biotite or new K-spars
 Sometimes chlorite, sericite or
quartz
 500-600 C

 Cu-porphyry related

 Hydrolysis & K+ metasomatism

 Yerington, Nevada—Na/Ca
alteration instead of K
SERICITIC/PHYLLIC ALTERATION
 Wide range of temperatures
 Feldspars hydrolyzed

 Forms sericite (white mica)

 Small formations of quartz,

pyrite, chlorite
 Also related to Cu-porphyry
deposits
 Potential associations with
VMS & mesothermal deposits
ARGILLIC ALTERATION
 Mostly plagioclase feldspars
 Forms clays—smectite,
montmorillonite, kaolinite, dickite,
alunite
 250 C

 H+ metasomatism

 Related to several porphyries in

deposit margins
 Base leaching—removes most
alkali elements
 Epithermal or near surface

 Boiling fluids

 Highly-acidic volatiles
SILICATION
(NOT BE CONFUSED WITH
SILICIFICATION)
 Carbonates converted to
silicates by replacement
 Cation metasomatism

 Polymetallic skarn deposits

 Acidic magma-related fluid

invades carbonates
 Carbonates easily form
deposits due to permeability,
susceptibility to acid, and
tendency to neutralize
solutions
 High fluid/rock ratios
SILICIFICATION
(NOT BE CONFUSED WITH SILICATION)
 New quartz or amorphous
(glass) silica forms in rock
 Alteration haloes around many
ore deposits
 Isochemical hydrolysis related

 Tends to fill in fractures

 SiO2 leaches out of country

rock into hot fluid
 Cation metasomatism—high-
grade conditions mobilize Si4+
 Common in high-grade
epithermal zones
GREISENIZATION
 Related to ‘cupola’ zones in S-type granites
 Need highly-differentiated country rock

 Sn-W, F, Li, B enrichment

 Altered sequence of muscovite, topaz, quartz

 Less commonly fluorite & maline

 Form in close proximity to quartz-wolframite-wolfenite

zones
HEMATIZATION
 Related to oxidizing fluids
 Mineral associations with seracite, hematite, chlorite,
epidote & K-spar
 Cu-Au-Fe-U deposits in South Australia

 Cu-Co ores in Central African copperbelt

 High salinity, oxidized fluids come in contact with

reducing country rock
 High Fe2+ & Fe3+
METAL ZONING
 Zoning: Regular patterns of metals/minerals in ore
deposits
 Can happen across 100s of kilometers

 Can be subduction related (Andes)

 Ex) Cornubian batholith, UK—Sn-W-Pb-Zn-Ag-Sb-U

sequence etends laterally
 Related to evolving hydrothermal fluid

 Precipitation follows a defined sequence

PARAGENESIS
 Guilbert & Park (1968)—paragenetic sequences are
minerals/metals related to the same original source
 Hypothermal: SN-W-Mo precipitate first

 Mesothermal: Zn-Pb-Cu-Mn precipitate later

 Epithermal: Au-Hg-Sb, near surface fluids

 Emmons precipitation sequence developed in 1933

 Metal-sulfide presence promotes Emmons precipitation

sequence
 With metal-chlorides, a smaller sequence of Cu-Ag-Pb-
Zn is likely to form
METAL/MINERAL REPLACEMENT
 Need pore space or microfractures
 Oxides are less likely to be fully sulfidated—Ex)
ilmenite, magnetite
 At depth, molar volume is the biggest control on
replacement
 Small volume minerals must replace large volume
minerals
VMS & SEDEX
VMS
 Volcanogenic/volcanic-hosted massive
sulfide deposits
 Volcanically related hydrothermal fluids
formed during orogenies
 Modern analogues or still ongoing

 “black smokers” discovered in 1977 on

ocean floor on East Pacific Rise
 400 C—highly reduced with high metal
content
 Contact 2 C ocean water, oxidized with
low metal contents
 Tube-like chimneys

 Cu-Zn deposits like Troodoos Massif,

Cyprus related to mid-ocean ridge vents
(hosted in ophiolite)
VMS
 Cyprus-type: common in Norway &
Finland, leached from mafic source rock
 Kuroko-type: common in Japan, Iberian
Pyrite belts, & Newfoundland, arc-related
‘bimodal’—felsic & mafic source rocks
 Most fluids from ocean water, small
amounts from magma
 Clear zonation: Fe-Cu-Pb-Zn

 Increasingly high temps as ore-body

grows
 Low temps incapable of dissolving
enough metal
 Can grow as chimneys collapse, sulfide
precipitates out of seawater or dissolved
metals arrive from below
VMS
 Organisms may support sulfate
reduction in and around vents
 Possibly true in Pb-Zn-Ba deposits in
Ireland
 Local fluid dynamics control whether
the ore-body is dome-shaped
(common) or table-shaped
(uncommon)
 When seawater & hot fluid have
similar densities, precipitation hands in
nearby low-topography
 Rapid quenching before boiling for
most metals
 In faulted systems, hot fluids brecciate
the footwall and deposit metals
VMS—HOW DOES IT GET ON LAND?
 Ex) Troodos Massif in Cyprus
 Obduction—oceanic
lithosphere is thrusted onto
continental crust
 Associated with:

 Pillowed basalt (common on

the ocean floor)
 Sheeted dikes

 Pelagic (mid-ocean) sediments

SEDEX
 More than half of all Pb & Zn deposits
 Sedimentary exhalative

 Paleoproterozoic & Mesoproterozoic

 British Columbia, South Africa, Australia, India

 Modern examples—Salton Sea

 East Pacific Rise junction with North American plate in

Salton Sea area of California—geothermal fields
 Man-made lake ‘Salton Sea’ caused after a dam break
flooded a massive low-lying salt pan
 Brine now mobilizes metals in lacustrine sediments and
percolates down to temperatures of 350 C depositing
metals
OROGENIC GOLD (ARCHEAN)
 Largely in greenstone/granite rocks dating to the
Archean
 Ex) Yilgarn, Zimbabwe, & Superior Provinces/Cratons

 Brittle-ductile transformation areas

 Plate collisions & subduction

 Magmatic fluids—highly reduced and able to move

AuHS2-
 Fault ‘valves’ move fluid and are marked by
chloritized/carbonated minerals
 Large amounts of wall-rock alteration
OROGENIC GOLD
(PROTEROZOIC +PHANEROZOIC)
 Relatively rare in Proterozoic except West Africa, South
Dakota, Western Australia, & Sabie-Pilgrim field in
South Africa
 Housed in thrust faults

 Clusters in Silurian-Devonian & Cretaceous

 Related to converging plates

 Cut through shales that have metamorphosed to

greenschist facies
 AKA Slate-belt hosted gold

 California, Uzbekistan, Ural moutnains, Nova Scota

CARLIN-GOLD
 Formed due to extension not compression
 First discovered around Carlin, NV in the 1960s

 Paleogence 42-30 Ma

 Also in China

 Associated with Basin & Range crustal thinning and carbonate aquifer rocks

 Medium acid, low salinity metamorphic-style fluids

 150-250 C

 Carbonates neutralize fluids along with argillic, silicification, and sulfidation processes
QUARTZ-PEBBLE GOLD
 Archean & Proterozoic
 Witwatersrand gold field, South
Africa
 35% of all gold ever produced

 Poorly understood

 Detrital gold?

 Fluids in sediments causing

precipitation?
 Large haloes indicate multiple fluid
cycles
 Slow neutralization and precipitation?

 Low salinity, moderate acidity fluids

 Closely matched CO2 & H2O

CONNATE & METEORIC
DEPOSITS
STRATIFORM SEDIMENT-HOSTED
COPPER (SSC)
 2nd main source of copper after porphyry deposits
 Abundant Pb, Zn, Ag, PGE & R

 Kuperschiefer—Central Europe

 Central African copperbelt

 Rift related

 Oxidized eolian & evaporite sediments buried and modified

 Neutral, saline, oxidized connate fluid altered sediments

 Copper leached out of biotite, magnetite, and pyroxene

 Deposition in shallow marine or red-bed environments

MVT (MISSISSIPPI VALLEY TYPE
DEPOSITS)
 Pb-Zn
 Happen long after sediments
deposited
 Mainly sphalerite instead of galena

 Exception to the rule—Viburnum

Trend is balanced toward galena
 Sandstone or carbonate host-rock

 Other large deposits in Tennessee,

Illinois, Oklahoma and Missouri
 Australia, South Africa, Poland,
Austria
 Devonian-Permian

 Compression+ orogenies in Pangaea

 High rainfall in sabkha zones—high

salinity groundwater
METEORIC FLUID
 Rarely a source of ore transport
 U6+ uranium ion mobilized best in rainwater

 Precipitates as uraninite under low pH conditions

 Precipitates due to reduction at low temps

 By contrast, U4+ is very incompatible except in

monazite and a few other minerals
SANDSTONE-HOSTED URANIUM
 Colorado Plateau, Southwest, South Dakota & Wyoming
 Colorado Plateau: U-V, Jurassic rocks

 Related to low temp mixing of meteoric water

 Uranous silicate & coffinite from plant material

 30-40 C related to basinal brines

 V-rich clay layers welded with dolomite

 Coffinite/plant material naturally reducing and helsp to

feed sulfate reducing bacteria
REFERENCES
REFERENCES
 Robb, L. (2005). Introduction to ore-forming processes.
Blackwell Publishing.