Geochemistry

of Arc Magmas Associated with Ores

J H Dilles, Antofagasta, 2017
 Outline of PresentaBon

•  Major elements in mineralizing magmas

•  OxidaBon state of arc magmas, and mineralizing
magmas.
•  Trace elements in magmas
•  sources of variaBon: mafic magma, crustal
assimilaBon, mixing, and crystal fracBonaBon
•  EsBmaBon of metal and sulfur content of magmas.
 Porphyry deposits:
Relationship between ore metals
& major element magma composition
Seedorff et al., 2005, classification based on principal metals
Tungsten (W-Mo), rhyolite
Tin (Sn) rhyodacitic
Molybdenum
Mo = rhyolite, granite, trondjemite, syenite, & monzonite
Mo-Cu = quartz monzonite & granite
Copper
Cu(Mo) quartz monzodiorite-granodiorite
Cu (Mo-Au) monzonite
Cu (Au-Mo) tonalite-granodiorite
Cu-(Au) syenite
Gold (Au) dioritic
Porphyry deposits metals & magmas
 Porphyry Magma Normative compositions
•  note wide diversity among compositions
Calc-alkaline & alkaline (high-K) compositions
Metaluminous to peraluminous compositions
Pebble Porphyry Cu-Au-Mo Magmas
Note calc-alkaline rather than tholeiiBc trend (Olson, 2015)
 Pebble Porphyry Cu-Au-Mo Magmas

Rare Earth Elements (REE) Note

decrease of middle REE, that may
be the result of early hornblende
(pyroxene) or late Btanite
removal
 Behavior of Ore Metals in Magmas--Examples
Chiaradia et al. (2014), CompilaBons of GEOROC global data for
Quaternary arc magmas such depleBon of copper in thick crust

 Copper Content of Arc Magma ~50-100 ppm
Jeremy Richards, 2015, Lithos
In both a) Mature Arcs (thick continental crust) and b) Island
Arcs (thin crust) maximum Cu content at 3-6 wt% MgO (andesite)

Oxidized magmas (red, log fO2 > O) have lower Cu contents

Halter et al., Bajo La Alumbrera Copper Contents
Comparison of melt inclusions and whole rock
data; Intrusive rocks have lost copper
 Major Element Variation Diagrams for Yerington Batholith
Smooth plots are consistent with either crystal fractionation or mafic-silicic magma mixing

Weakly alkalic

Smooth variations
majors versus silica

High-K “arc”
alkali content
Zinc behavior differs from copper & decreases slowly with Silica
increase (Zn reduced via hbl, biotite fractionation) .

Yerington: Zn has similar content in the Bear Quartz

Monzonite and Mineralizing Luhr Hill Granite
100

80
Zn (ppm)

60 QMD

40
Zn (ppm) BQM
20 Zn (pg&gp)
PG
&GP
0
55 60 65 70
SiO2 wt%
 Fresh rock copper geochemistry
Luhr Hill granite & ppy associated with Ppy Cu Deposits are
strongly Cu-depleted (Cu lost to HT fluids)
 Yerington batholith metal geochemistry
• Relative to earlier intrusions, Luhr
Hill granite is strongly depleted in
Cu as well as other“ore metals” in
porphyry Cu deposits: Mo & Ag.
• As & Pb are also depleted
• Bi & Zn are not depleted
• Au is very low (<1 ppb), &
depletion is not measured
• Working hypothesis is that
magmatic - hydrothermal fluids
extracted ore metals from magma
during degassing.

• Depletion ratio of Cu:Mo:Ag

is ~ 1,000:6:1 (~ equal PCD ore)
Ayuso et al. 2010

Much data plots

near mantle melts:
(Chile)

Elevated 87Sr/86Sr
iniBal and depleted
εNd suggest
contaminaBon of
magmas by
conBnental crust

 Pebble Porphyry Cu-Au-Mo, Alaska
•  Li_le crustal contaminaBon – plots along OIB mantle array

Olson,
2015)
OxidaBon State of Fe on earth
 Petrologic
buffers

•  Have form
Fe2SiO4 = 2Fe + SiO2 +
O2

log fO2 = A/T + B +
C(P-1)/T
T in (K)
P in bars
Common Oxygen Buffers
 Fe-Ti-oxide minerals

Rhombohedral solid
solution
•  Fe-Ti-O (>750-800°C):
triangular Spinel solid solution:
composition diagram:
Hematite & 2ilmenite
•  rutile (TiO ), Magnetite and
have same (Fe
•  hematite structure:
3+ O ),
2 3 ulvospinel are
(Fe 2+,Ti4+) ilmenite =
•  ilmenite (FeTiO3), isostructural;
(2Fe 3+) hematite
•  magnetite (Fe3O4),
(oxidized)
•  ulvospinel (Fe2TiO4) 2Fe3+ (magnetite)
•  Plot using molar substitute for Fe2+ +
proportions Fe3+
substitution: Ti4+(ulvosp);
• (0.63A), Fe2+ (0.68A),
Note colinearities--e.g.,
Ti4+ O to TiO2 join.
(0.74A);
Fe2+ complete solid solution
above ~560°C
OxidaBon State from Fe-Ti Oxides

Oxidized Reduced






reduced

Oxidized
Tie lines connect coexisBng phases at a given T & P

•  Note Fe-rich
magneBte-
ulvospinel may
coexist with
ilmenite or
hemaBte-rich ilm-
hmSS
Oxidized
 Ilmenite-hemaBte solvus

•  Reduced condiBons=milmenite
•  Oxidized condiBons = hemaBte

Solvus
 ExsoluBon

•  When ilmenite-hemaBte
SS cools below the solvus,
it may “unmix” into two 0.1 mm = 100 um
minerals.
•  Process is exsoluBon
•  Reflected light Photos
•  HemaBte = white
•  Ilmenite = brown (gray)
 Trellis Texture in Mag-Usp

•  Note octahedral
parBngs
•  Ulvospinel forms on
Oct parBngs, and is
“reduced” to form
ilmenite.
•  Common texture in Fe-
Ti deposits
 May calculate T & fO2

•  CoexisBng composiBons
•  Mag-Usp & Ilm-hmSS
Mag80Hem15
•  Two reacBons

Increase fO2

oxidaBon
6Fe2O3 = 4Fe3O4 + O2
exchange
Fe2O3 + Fe2TiO4 =
FeTiO3 + Fe3O4

Buddington and Lindsley, 1962 Temperature, °C

 Yerington Btholith Petrology (Dilles, 1987)

Strongly Oxidized

MGT-ILM:
MagneBte-Ilmenite
ComposiBons

ILM/SPH: Presence
of MagneBte +
Sphene (Btanite)


Cpx + Ilmenite + O2
= MagneBte +
Sphene + Quartz
Yanacocha, Peru; Chambefort et al. 2013
OxidaBon state of NNO+1 to NNO+3
 MagmaBc tracers of mineralizing arc magmas

• High V/Sc of melts? Oxidized magmas

• High Sr/Y of melts? Thick crust, water-rich magma

 Porphyry Magmas are Oxidized
•  Most Sulfur occurs as sulfate SO4 (S6+) in magma
•  Oxidized conditions are required by titanite + quartz + magnetite
fO2 Constraints – Emigrant Pass Volcanics, Carlin
Early Primeaux Andesites
-  MagneBte >> ilmenite suggests relaBvely oxidized magmas, likely >NNO+1
 fO2 Constraints
Late Mack Creek Dacites
-  Abundant magneBte, no ilmenite phenocrysts, and sparse Btanite require
fO2 condiBons ≥ NNO+2 (Dilles, 1987; Wones, 1989)
V/Sc as indicator
of highly oxidized oxidized
magmas (Loucks, 2014) V5+




V & Sc normally behavior
similarly in magmatic
differentiation
Normal arc
In oxidized magmas,
V3+ ! V5+ the latter V3+
which acts incompatibly
during fractionation
resulting in high V/Sc
 fO2 Constraints-Emigrant Pass Volcanics (Carlin)
-  High V/Sc may track highly oxidizing condiBons typically >NNO+1
-  V3+ is compaBble and is incorporated into hornblende & bioiBte
-  Oxidized V5+ acts incompaBbly in magmas
Pebble Porphyry Cu-Au-Mo, Alaska
(Olson, MS, 2015; thin crust)
R. Ayuso (in John et al., 2010): The case for deep-crustal generation of trace
element characteristics of porphyry magmas (on thick crust>30 km)
•Hi Sr/Y: Source lacks plagioclase (Sr), has garnet (Y,Yb); ga-amph zone
The case for deep-crustal generation of trace element
characteristics of porphyry magmas (on thick crust>30 km)
•Hi Sr/Y: Water-rich source lacks plagioclase (Sr-rich), has garnet (Y,Yb-rich);
•Melts derived from the ga-amph zone are therefore Sr-rich and Y-poor

70km

35 km
 Pebble Porphyry Cu-Au-Mo, Alaska
RelaBvely low Sr/Y, consistent with thin crust
Note that Sr is commonly removed by hydrothermal alteraBon

(Olson, MS, 2015)

 Sr/Y indicator
(Loucks, 2014) Thick Crust

In water-rich magmas
plagioclase crystallization
is suppressed, and Sr is

not incorporated into plag
so increases with silica
Thin Crust
Y is incorporated in garnet
in deep crustal magma
processes (>25-30 km) &
in hornblende (>4% water)

High Sr/Y is typical of

porphyry magmas in thick
crust, but not in thin crust
(e.g., Pebble, AK)
 H2O Content Constraints-Emigrant Pass Volc (Carlin)
-  High whole rock Sr/Y indicates high magmaBc H2O contents >4 wt. %
-  Stabilizes crystallizaBon of hornblende (±garnet) rich in Y;
-  Suppresses Sr-compaBble plagioclase
MagmaBc Sulfide ComposiBons--Carlin

MSS MSS
MagmaBc Sulfide ComposiBons

iss

Aser Cabri (1973)

 Why do we care about MagmaBc Sulfide ComposiBons?
-  FracBoning sulfide phases strongly parBBon chalcophile metals like Au, Cu,
thereby influencing metal budget of remaining melts (100 ppm Cu, 2 ppb Au)

-  Two dominant sulfide species observed in igneous rocks:

-  Monosulfide solid soluBon (MSS) or pyrrhoBte (FeS) at low T
-  Intermediate solid soluBon (ISS) (Sulfide melt at High T)

-  MSS preferenBally takes up Cu relaBve to Au (Yi and Audetat, 2013)

-  Sulfide Melt (now present as ISS ± MSS in rocks) takes up Au relaBve to Cu

MSS: DAu mss/silicate melt ~ 180, DCumss/melt ~300

Sulf Melt: DAu sulfide melt/silcate melt ~ 8,000 DCusulfide melt/Silic melt ~ 900

~0.1% (1000 ppm) MSS present, then silicate melt ~ 1.6 ppb Au (80% remaining),
70 ppm Cu (70% remaining)
~0.1% (1000 ppm) Sulf Melt present,!silicate melt <0.1 ppb Au (<1% remaining),
10 ppm Cu (10% remaining)

-  So, MSS is effecBve at enriching the melt Au/Cu, while depleBng it less than
ISS; which is later available to magmaBc-hydrothermal fluids
Aser Cabri (1973)
 Deep Arc Magma
Processes
MASH of Hildreth & Moorebath (1988)
Or Hot Zone of Annen et al. (2006)

Hot zone has long-lived

melt near base of crust

Hydrous melts in deep

thick crust crystallize Px +
Gar ± Plag ± Hbl

On Ascent are water-rich

& crystallize early
hornblende
 Modeling magma recharge & crystal
fractionation to enrich incompatible Cu (&S)
In deep hot zone, multiple events of hydrous basalt injection and crystal
fractionation, can successively increase the water, sulfur and incompatible
metal contents (Cu, Au, Mo) in absence of Cu-Au-rich sulfide phase
(MSS, ISS, or Sulfide melt grabs Cu & Au: (DAuSulf/slic>100; DcuSulf/silic>100)
350

DAUGHTER
300
MAGMAS
SiO2 vs Cu
250

removed components
Cu (ppm)

200

MIXTURES
150

PARENT MAGMA
100
Melt composition
changes with crystal
fractionation
50

FRACTIONATES
0
45 55 65
SiO2 (wt.%)
 Schematic XS
Transient, upper crustal
magma chambers:
•Sulfur stored as
anhydrite
•Low-T volatile saturation
of hydrous melt,
•Degassing of H2O,
Sulfur (SO2), ± Cu ± Cl-
rich fluids.

Mid-crustal magma
chambers or reactions
zones; magma evolution (to
increase Sr/Y, H2O, Cu, Cl,
SO42-

Deep source of magmas,

most volatiles Chambefort et al., 2013- J. Petrol
 Conclusions
•  Shallow dacite/granodiorite magmas commonly are
depleted in chalcophile elements that are lost to the
separating magmatic-hydrothermal fluids.
•  Arc magmas are commonly strongly oxidized, and
porphyry magmas are amount the most oxidized.
Titanite + magnetite, and high V/Sc may record.
•  Elevated Sr/Y records water-rich magmas in thick crust;
may be useful for prospecting.
•  Prolonged hydrous arc magmatism, in oxidized
conditions may produce water, S, & Cu-rich ore-forming
dacite magmas in the deep crustal “hot zones”—
especially where crust is thick & hydrous basalt
injection, crustal melting & crystal fractionation occur
over long time spans