Alteration Geochem Mod

Chemical changes due to hydrothermal
alteration
David R Cooke and Andrew McNeill

M.Econ. Geol. Short course 2013 Slide 1
Outline
Important chemical reactions in
alteration
Whole rock geochemical data in relation
to alteration reactions & assemblages
Alteration indices
Major shortcomings of composition data
and indices closure
Mass change estimation methods that
overcome closure
Disseminated bornite in orthoclase

altered diorite, Waisoi, Fiji
Hydrothermal alteration
Alteration: any change in the mineralogic composition
of a rock brought about by physical or chemical means,
especially by the action of hydrothermal fluids
Nature of the alteration products depends on:
Structure and composition of the wall rock
Chemistry of the mineralising hydrothermal fluid (Eh,
pH, vapour pressure of various volatile species, anion
cation composition, degree of hydrolysis)
Temperature and pressure
Types of chemical reactions
Chemical and thermal gradients are the principal

determinants of the type and extent of wall rock
alteration
alt
er
ati
on
ri
m
Disseminated bornite in orthoclase altered

diorite, Waisoi, Fiji
Hydrothermal alteration
Chemical reactions that occur during alteration include:
Acid neutralization (hydrolysis)
Hydration or dehydration
Alkali or alkali earth metasomatism
Decarbonation
Silicification
Oxidation reduction
Addition and/or removal of components,
e.g.,
carbonation
desulfidation
sulfidation
fluoridation, etc
Acid neutralization (hydrolysis)

Conversion of anhydrous silicates (feldspar) to hydrated silicates
(micas, etc) occurs when acid fluids react with feldspar bearing rocks
These reactions can buffer acidity
e.g. sericitisation of potassium feldspars:
3KAlSi3O8 + 2H+
K feldspar
KAl3Si3O10(OH)2 + 6SiO2 + 2K+

muscovite (sericite) quartz
Centimetre scale halo of pervasive sericite

alteration around quartz + tourmaline vein
and nodules in granite, Heemskirk, Tasmania
Hydrolysis: reactions that consume H+

Sericitisation of plagioclase feldspars:
3NaAlSi3O8 + 2H+ + K+
albite
3KAlSi3O8 + 2H+
K feldspar
KAl3Si3O10(OH)2 + 6SiO2 + 3Na+

sericite
quartz
KAl3Si3O10(OH)2 + 6SiO2 + 2K+

muscovite (sericite) quartz
Note that the hydrolysis of K feldspar provides K+ ions for the sericitisation
of albite
Both reactions produce quartz
Centimetre to metre scale sericite altered zones around gold bearing

quartz + ankerite + pyrite veins and vein breccias at Sunrise Dam Gold
Mine, Yilgarn, WA
This style of alteration is typical of Archean greenstone hosted lode
gold deposits
Further hydrolysis results in alkali stripping

e.g. muscovite altered to kaolinite:
2 KAl3Si3O10(OH)2 + 2H+ + 3H2O
muscovite
3 Al2Si2O5(OH)4 + 2K+
kaolinite
Phase diagrams illustrating influence of pH, aK/aH+and temperature on stability of feldspar & phyllosilicates
5 cm
Hydrolysis
Very important in alteration
and mineralisation
Converts anhydrous silicates
to hydrous silicates
Buffers acidity of fluids
Au
Sericite
this in turn affects metal

solubilities. etc.
Feldspar, mica and clay

stabilities, and the transfer
of K+, Na+, Ca2+ and Mg2+
from silicate minerals into
solution is controlled in large
part by hydrolysis
chna
ging
the
chem
istry
the
rocks
and
the
chem
estry
alter
ation
940 g/t Au ore specimen, Sunrise Dam Gold Mine, WA
Hydrolysis: reactions involving H+

Consumption of H+ by hydrolysis affects:
Acidity of the mineralising fluid
Degree of dissociation of hydrogen complexes, including HCl
Degree of association of Cl complexes (NaCl, KCl, etc.)
Metal solubilities
Transfer of K+, Na+, Ca2+, Mg2+ etc. from silicates into solution and
consequent availability for other reactions
Reaction of metals with aqueous sulfide species causes sulfide
precipitation and releases H+, e.g.:
re
du
ce
flu
id
ZnCl42 + H2S(aq)
ZnS (s) + 2 H+ + 4 Cl
Silicate alteration may actually be a consequence of sulfide

mineralisation
Chlorite magnetite altered diorite cut by

crustiform quartz carbonate veins, Fiji
Hydration: addition of H2O

Transfer of water from fluid to mineral
e.g., simple hydration:
Fe203 + 3 H2O
2 Fe(OH)3
hematite
goethite (limonite)
There are important seafloor alteration processes
that involve both hydration and hydrolysis
2 Mg2SiO4 + 2H2O + 2H+
olivine
Mg3Si2O5(OH)4 + Mg2+
serpentine
Limonitic outcrop of
weathered hematite
body, Pilbara, WA
Serpentinized
ultramafic rock,
western
Tasmania
Dehydration: removal of H2O

Transfer of water from mineral to fluid
usually related to increased temperature and/or pressure
e.g. metamorphism or thermal zonation in hydrothermal systems
co
m
m
on
in
m
et
a
m
or
ph
is
m
an
Al2Si205(OH)4 + 2 Si02
Kaolinite
quartz
Al2Si4010(OH)2 + H20
pyrophyllite
Pyrophyllite: petrographically difficult to distinguish from sericite
kaolinite
pyrophyllite
sericite

reactions involving Ca, Na, K and Mg
e.g., Modification of feldspar compositions :
KAlSi3O8 + Na+
K feldspar
NaAlSi3O8 + K+
albite
Mg metasomatism converting limestone to dolomite:

2 CaCO3 + Mg2+(aq)
calcite
CaMg(CO3)2 + Ca2+(aq)
dolomite
Irregular domains of pale grey dolomite

alteration in dark limestone

reactions involving Ca, Na, K and Mg
Mg metasomatism and hydration converting feldspar to chlorite:
rh
yo
lit
KAlSi3O8 + 6.5Mg+2 + 10H2O

K feldspar
Mg6.5(Si3Al)O10(OH)8 + K+ + 12H+
chlorite
Andesitic breccia with incipiently

K feldspar altered zones
Pervasively K feldspar altered andesite
Subsequent chloritic alteration

overprinting K feldspar
Decarbonation: removal of CO2

Common during skarn formation
oxides and silicates form during CO2 removal from carbonates:
MgCO3
magnesite
MgO + CO2 (g)

periclase
CaMg(CO3)2 + 2 SiO2
dolomite
quartz
(CaMg)Si2O6 + 2 CO2 (g)

diopside
Banded dolomite + diopside skarn

formed by thermal metamorphism of
impure dolomitic rock.
Silicification and silicate alteration

(sound similar but have different meanings)
Silicification involves the addition or precipitation of a silica mineral
e.g., silicification of limestone by acidic and silica rich fluids
2 CaCO3 + SiO2 (aq) + 4H+
2 Ca2+(aq) + 2CO2 + SiO2 (s) + 2H2O
Calcite
aqueous silica
quartz
Silicate alteration converts rocks to new silicate minerals

e.g., in contact metamorphism:
CaCO3 + SiO2
CaSiO3 + CO2 (g)
calcite quartz wollastonite
Wollastonite in
metamorphic
reaction zones
adjacent to
siliceous beds
Folded sandstone + limestone beds
Carbonation and silicification

e.g., retrograde skarn:
Ca3Fe2(SiO4)3 + 3 CO2
3 CaCO3 + Fe2O3 + 3SiO2
garnet
calcite hematite quartz
calcite
veinlets
garnet
Quartz +
hematite
Retrograde skarn
Oxidation reduction
Redox reactions control:
ferrous(2+) ferric(3+) iron phases
sulfur minerals and complexes
Cu, Au, Mn, V, U, etc.
oxidation of magnetite:
4 Fe3O4 + O2
6 Fe2O3
magnetite
hematite
weathering of pyrite:
FeS2 + 3.5 O2 + 8 H2O
pyrite
Magnetite in banded iron formation

surficially oxidized to hematite
FeSO4.7H2O + H2SO4
melanterite sulfuric acid
Oxidation Reduction
Weathering of pyrite:
3 FeS2 + K+ + 10.25 O2 + 5.5 H2O
pyrite
KFe3(SO4)2(OH)2 + 4 H2SO4 + H+
jarosite
sulfuric acid
Yellowish jarosite stain on walls of Ladolam gold mine,

Lihir Island, PNG
Close up view: jarosite derived from weathering of

pyritic veins
Sulfidation and desulfidation

reactions
These reactions can be vital to the processes of
sulfide alteration and also to base and precious
metal mineralisation
Desulfidation of pyrite:
FeS2 + H2O
FeS + H2S(aq) + O2 (g)
Sulfidation of magnetite:
Fe3O4 + 6 H2S(aq) + O2 (g)
3 FeS2 + 6 H2O
A variation of this reaction can be important for gold

precipitation:
Fe3O4 + 6 Au(HS)2 + 6H+ + 0.25 O2
3 FeS2 + 9 H2O + 6 Au
Pyritic selvedge around quartz vein in
magnetite rich siltstone; Sunrise Dam Gold
Mine, Yilgarn, WA.
What types of reactions occurred here?

Warm, humid tropical climate
km scale pyritic altered zone exposed to weathering
hydrolysis & hydration of sericite to kaolinite

Near surface kaolinite blanket
oxidation & hydration of Fe sulfates
Fe hydroxides
goethite (limonite) stained pit wall

oxidation & hydration of Fe & S in pyrite
Fe sulfates & sulfuric acid
Gold rich sericite pyrite altered

trachybasalts
Western wall of Ladolam gold mine, Lihir Island, PNG
Alteration intensity
WEAK
pumice
Determined subjectively based on

mineralogy and textural preservation
qualitative terms:
plag
weak
moderate
intense, etc.
MODERATE
inherently inconsistent
py
ser
Whole rock geochemical analysis

offers
qz + py
INTENSE
?
1 mm
weakly altered as described by an exploration

geologist may be intensely altered to a
petrologist
a quantitative means of describing alteration

intensity
insight into chemical changes
Thin section photos of increasingly altered feldspar phyric

pumice breccia, Hercules, western Tasmania
(from Gifkins et al. 2005)
Whole rock chemical compositions

Major elements
usually determined by X ray fluorescence or Inductively Coupled Plasma methods
expressed as wt % oxides, listed in decreasing order of cation valency:
Standard ten elements and loss of volatiles on ignition (LOI)
SiO2, TiO2, Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, P2O5, LOI
Useful additions in alteration studies:

S, CO2, H2O+
because sulfides, carbonates & hydrolysed silicates are common in alteration
assemblages
these 13 components are usually adequate; except for unusual altered rocks with F, B
etc., or mineralised rocks with significant Cu, Pb, Zn etc.
Trace elements: <0.1 wt% (1000 ppm);

ch
an
ge
in
hy
dr
ot
he
rm
al
alt
er
particularly including some useful immobile elements (Zr, Nb, Y)

H2O+ = water in lattice of minerals, released at >110C
H2O = dampness in sample, released at < 110C
Typical whole rock chemical analysis

Example of standard analyses with LOI determination:
No.
SiO
TAS granite
W0287 basalt
W0306 basalt
72.47 0.28 13.62 2.21

40.40 0.67 13.58 9.20
46.21 0.70 15.48 8.69
TiO 2 Al 2 O 3 Fe 2O 3 MnO MgO CaO

0.04
0.25
0.17
0.72
5.24
3.68
Na 2O K 2O
1.83 2.75
11.45 1.38
6.72 1.52
4.60
4.39
3.84
P 2 O 5 LOI
Total %
0.11
0.50
0.36
99.37
98.05
97.06
0.73
10.98
9.69
The non altered TAS granite has a low LOI value and acceptable total
However, the altered basalt samples W0287 & W0306 have high LOIs and low totals
In altered rocks, analyses that include S, CO2, H2O+ are more complete:
No.
SiO
W0287
W0306
40.40 0.67
46.21 0.70
TiO 2 Al 2 O 3 Fe 2O 3 MnO
13.58 9.20
15.48 8.69
0.25
0.17
MgO
CaO
Na 2O K 2 O
5.24
3.68
11.45 1.38
6.72 1.52
4.39
3.84
P 2O 5
CO
H 2O
Total %
S vol.
0.50
0.36
0.07
4.69
8.57
4.47
4.29
3.36
100.0
99.89
12.93
12.52
* Note that the original analyses of the two altered basalts underestimated losses
of volatiles by 2 3%
LOI and volatile free?

The example below illustrates how LOI was underestimated in two (real) analyses of altered basalts (from previous slide)
No.
SiO 2 TiO 2 Al 2 O 3 Fe 2 O 3 MnO
W0287 40.40 0.67 13.58 9.20 0.25
W0306 46.21 0.70 15.48 8.69 0.17
MgO
5.24
3.68
CaO Na 2O K 2 O
11.45 1.38 4.39
6.72 1.52 3.84
P 2O 5
0.50
0.36
S 11 S
LOI
10.98 98.05 0.07
9.69 97.06 4.69
CO 2
8.57
4.47
H 2O
4.29
3.36
S 13
100.00
99.89
Loss on ignition (LOI) usually determined during fusion

for XRF analyses
LOI is NOT USEFUL in analyses of hydrothermally altered rocks:
some minerals are difficult to dehydrate at 1000C; e.g. talc, topaz, epidote
oxidation may produce weight gain; e.g. oxidation of ferrous iron
incomplete volatilisation; e.g. in samples containing both sulfides and calcium
carbonates, reaction between SO3 and CaO may produce sulfate that remains in the
ignited sample
Recalculation to 100% volatile free?

OK for petrogenetic comparison of relatively fresh igneous rocks
for altered rocks because of unreliability of LOI
NOT APPROPRIATE
It is better to do S, C and H, run quality control on all elements, and then trust the
accuracy of the data
H2O+ = water in lattice of minerals, released at >110C
H2O = dampness in sample, released at < 110C
Metasomatic reactions and

major element data
Some metasomatic changes are directly

apparent in whole rock composition data
For example:
Metasomatic addition of pyrite is
associated with increases in sulfur
and iron
Sericitisation of plagioclase is usually
evident by Na2O depletion:
3 NaAlSi3O8 + 2 H+ + K+
albite
KAl3Si3O10(OH)2 + 6 SiO2 + 3 Na+

muscovite
quartz
Clear beryl with albite and muscovite from Mt Xuebaoding, Pingwu County, Mianyang
Prefecture, Sichuan Province, China. Source: http://commons.wikimedia.org/wiki/File:Beryl
Albite Muscovite 172386.jpg
Example: altered rhyolites in footwall of Thalanga VHMS

deposit
No. Description
SiO2 TiO2
A1 Least altd Rhyolite
77.00 0.10
A3 Qtz+Ser+Py altd Rhy. 71.62 0.07
Least altered
rhyolite
A1
Al2O3 Fe2O3 MnO MgO CaO

12.30 1.76 0.05 1.40 0.48
8.13 9.66 0.04 1.49 0.15
Qtz+Ser+Py
altered rhyolite
A3
Na2O K2O
2.63 3.57
0.12 2.31
P2O5 S
0.02 0.11
0.02 6.58
CO2
0.10
0.15
Total
99.52
100.34
3 NaAlSi3O8 + 2 H+ + K+
albite
muscovite
quartz
Na2O decreased (sericitisation of plag)
Fe2O3 and S increased (addition of pyrite)
Reaction suggests that K2O should be added
(increased) but analyses suggest slight decrease?
K2O was probably available in the rock, from
breakdown of K feldspar or volcanic glass.
Al2O3 is not involved in reaction, but it appears to
have decreased ? because of closure (We will
look at this more closely later)
V
H
M
S
de
po
Na2O depletion halos

Recognition of alteration zones and
geochemical haloes increases the size of
exploration targets
May provide exploration vectors based
on:
compositional gradients; e.g. Na2O depletion
Multi component alteration indices; e.g.
Ishikawa AI = 100(K2O+MgO)/
(K2O+MgO+CaO+Na2O)
1.2% Na2O
mass changes of mobile components

recognition of deep semi conformable
alteration zones in VHMS districts
exhalite geochemistry in laterally extensive
ore equivalent units
Contours of Na2O % in footwall dacite around Ezuri

massive sulfide deposits, Hokuroko, Japan (Date et al.,
1983)
Alteration indices
Alteration indices use two or more components of geochemical data to
quantify the intensities of specific types of alteration.
Most widely applied in VHMS related alteration assemblages
General form:
(sum of components gained)
(sum of components lost)
low vales = low alteration intensity
high vales = high alteration intensity
Often normalised to 100: values range between 0 and 100
100 x (sum of components gained)
(sum of components gained + components lost)
Intense biotite alteration, porphyry Mo deposit, China
Alteration index of Ishikawa et al. (1976)

This index, known as AI, was designed to reflect the hydrolysis and alkali
exchange reactions that typically alter feldspars to phyllosilicates in the footwall
zones of VHMS deposits.
Alteration of plagioclase to sericite and chlorite typically involves reactions:
3 NaAlSi3O8 + 2 H+ + K+
albite
NaAlSi3O8 + 6.5 Mg+2 + 10 H2O
albite

muscovite
Quartz
Mg6.5(Si3Al)O10(OH)8 + Na+ + 12 H+
chlorite
Gains of K2O & MgO

Loss of Na2O (and CaO, from calcic plagioclase)
Alteration Index (AI)
100 x (K2O + MgO)

K2O + MgO + CaO + Na2O
AI typically ranges from about 20 to 60, in non altered volcanic rocks
Hellyer
Que River
Chester
Rosebery
Murchison
Hercules
Whole rock analyses

contoured for Alteration
Index values
AI effectively quantifies
intensity of alteration in the
large altered zones around
known ore deposits
AI
0 - 30
30 - 40
40 - 50
50 - 60
60 - 70
70 - 80
80 - 95
95 - 100
No Data
Hellyer to Mt Darwin
Western Tasmania
Mt Lyell
Mt Darwin
Chlorite carbonate pyrite index

(Large et al., 2001)
CCPI was developed to:
distinguish between chlorite and sericite alteration
avoid the effect of Ca phases, which lower values of AI index
(e.g. Ca Fe Mg carbonates are common in alteration assemblages with
sericite & chlorite)
CCPI =
100* (FeO + MgO)

(FeO + MgO + K2O + Na2O)
Like the AI, the CCPI measures plagioclase destruction (Na in denominator)
CCPI distinguishes between chlorite and sericite (Mg in numerator, K in
denominator)
CCPI values are high for assemblages dominated by Fe &/or Mg rich phases
(eg: chlorite, pyrite, siderite, ankerite, dolomite)
CCPI is affected by primary rock compositions non altered mafic rocks have
higher values than non altered felsic rocks
Box plot combining AI & CCPI indices

calcite
<---- pyrite, magnetite, siderite etc. ---->

dolomite
tremolite
chlorite
CCPI i ndex
100 * (FeO+MgO) / (FeO+MgO+Na2O+K2O)
100
Compositions of common
alteration minerals plot
around the frame edges
Non altered volcanics have
limited ranges of:
AI
~ 20 60
CCPI
~ 10 90
ankerite
90
Least
altered box
80
Basalt <52%
70
Andesite 52-63%
60
Dacite 63-69%
Rhyolite >69%
50
40
Volcanic rock compositions

that plot outside the box are
likely to have been
metasomatically altered
30
20
sericite
10
0
albite
Kfeldspar
10
20
30
40
50
AI CCPI boxplot of data from 1734

modern volcanic arc rocks (mostly
non altered), colour coded by SiO2
content
60
70
80
90
100
Ishikawa Alteration Index

100 * (MgO+K2O) / (MgO+K2O+CaO+Na2O)
Thalanga VHMS deposit, Nth Qld
Herrmann & Hill, 2001
Altered facies
Thalanga VHMS
deposit, N Qld
Altered facies
footwall volcanics,
Thalanga VHMS
deposit, N Qld
1 cm
0.5 mm
Samples from the footwall

of the Thalanga VHMS deposit
least altered
rhyolite
weakly
ser > chl
altered rhyolite
Feldspar phenocrysts
intact, & no pyrite
strongly
qz + ser + chl + py
altered rhyolite
intensely qz + ser + py
altered rhyolite
Disseminated
py 1 2%
Py stockwork 5 10%
A1
A5
A2
A3
Exercise 1
CCPI AI Boxplot (Fig. Ex1 and Table Ex2)
Does the AI CCPI box plot in Figure Ex1 successfully represent the mineralogy of the
altered rhyolite samples, A1 to A5 and the CTC assemblages at Thalanga?
What are the mineralogical and chemical differences (see Table Ex2) that give A3 a higher
CCPI than A2 and A5?
Why does A4 have a lower CCPI than all others?
What is the main chemical component, and mineralogical change that causes the high AI
values in samples A2 to A5?
Are the positions of CTC 1 to 3 in the boxplot consistent with their mineralogy?
What mineralogical difference might be responsible for different placement of the altered
footwall rhyolites and the single altered hangingwall dacite sample?
Why do the basaltic andesites plot at much higher CCPI than least altered rhyolites and
dacites?
<
pyrite, magnetite, siderite etc.
ankerite
dolomite
tremolite
CTC3
calcite
CCPI i ndex
100
>
chlorite
CTC2
90
CTC1
A3
80
70
A2
60
A5
50
40
A1
30
20
sericite
A4
10
0
albite
Kfeldspar
10
20
30
40
50
60
70
80
90
100

hangingwall Dacite
altered hangingwall Dacite

Basaltic Andesite
Rhyolites A1 to A5
undiff. f'wall Rhyolites
CTC 1 to 3
Figure Ex1
AI CCPI Box Plot
Thalanga altered volcanics
Chl Trem Carbonate rocks
Exercise 1 Answers
Does the AI CCPI box plot in Figure Ex1 successfully represent the mineralogy of the
altered rhyolite samples, A1 to A5 and the CTC assemblages at Thalanga?
Yes
What are the mineralogical and chemical differences (see Table Ex2) that give A3 a
higher CCPI than A2 and A5?
A3 is more strongly pyrite altered than the ser chl py alteration of A2 and A5 =
Higher Fe2O3, lower Na2O and K2O in A3
Why does A4 have a lower CCPI than all others?
High K2O, low Fe2O3 and low MgO sericite (Kf?) alteration with little or no
chlorite or pyrite
What is the main chemical component, and mineralogical change that causes the high
AI values in samples A2 to A5?
Loss of CaO (plagioclase destruction)
Exercise 1 Answers
Are the positions of CTC 1 to 3 in the boxplot consistent with their mineralogy?
Yes
What mineralogical difference might be responsible for different placement of the
altered footwall rhyolites?
chl ser py altered
possibly some Kf alteration too
and the single altered hangingwall dacite sample?
albite altered
Why do the basaltic andesites plot at much higher CCPI than least altered rhyolites and
dacites?
mafic rocks have higher MgO and Fe2O3
felsic rocks have higher K2O and Na2O
Box plot & VHMS environments

calcite
ankerite
<---- pyrite, magnetite, siderite etc. ---->

dolomite
tremolite
chlorite
enables graphic
recognition of the (likely)
major alteration
minerals
allows discrimination
between diagenetic and
VHMS related
hydrothermal alteration
trends
Note positions of A1 &
A3 Thalanga footwall
rhyolites
CCPI i ndex
AI plotted against CCPI in a

box plot enables:
100
90
Least
altered
box
80
Hydrothermal
trends
A3
70
60
50
40
30
Diagenetic
trends
A1
20
sericite
10
0
albite
Kfeldspar
10
20
30
40
50
AI CCPI boxplot of data from 276

variably altered volcanic rocks from
Mt Read Volcanics, Tasmania.
60
70
80
90
100

Other indices
Simple indices: ratios of wt% data
S
hi
gh
,
N
a
e.g. S / Na2O: shows high contrast in VHMS systems; from <0.1 in non altered
volcanics rising several orders of magnitude in footwall zones (Large et al.
2001).
Multi component indices: combine major & trace element data

e.g. potassic index of Wolfe (1994): quantify K feldspar and biotite
alteration associated with Goonumbla porphyry Cu deposits:
100 x (K2O + 1000 Rb) / (K2O + 1000 Rb + CaO + 100 Sr)
Molar ratios: wt% data are first converted to molar proportions (by dividing
by molecular weights)
Supposedly more easily related to stoichiometry of alteration reactions and
assemblages (Eilu et al., 1997).
e.g., molar ratio indices used in exploration for lode gold deposits:
3 K / Al sericitisation index
CO2 / CaO carbonation index
Closure in compositional data

(the constant sum effect)
MA
Closure affects all geochemical

composition data expressed as
proportions of a whole, e.g.
2MP
wt %
ppm
Chemical mass transfers (e.g.

hydrothermal alteration) that
change the net mass of a system by
adding or removing some
components, will affect the
proportions of all components
precursor
altered
even those not involved in mass

transfers
Although the amount of component i has not changed,

its proportion has diminished, because of addition of
other components.
(after Eilu et al., 1997)
Exercise 2
Compositional changes in Thalanga footwall rhyolites
This is an exercise designed to highlight the deceptive effects of closure we will
revisit the same samples and composition data with more rigorous and quantitative
mass change calculations, in a subsequent exercise.
Compare the composition of the least altered rhyolite (A1) with the compositions of the four altered
rhyolites (A2A5) and subjectively estimate which components underwent the greatest changes of
mass during hydrothermal alteration
Write your qualitative estimates of change for each major component in the empty columns to the
right of each of the A2 A5 analyses (e.g. small or large gain, loss, or negligible change) on Table Ex2.
least altered
rhyolite
weakly
ser > chl
altered rhyolite
strongly
qz + ser + chl+ py
altered rhyolite
intensely qz + ser + py
altered rhyolite
py stockwork
5 10%
Feldspar phenocrysts
intact, & no pyrite
A1
A5
dissem Py 1 2%
A2
A3
SG small gain; LG large gain; SL small loss,

LL large loss; NC negligible change; no change
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
S
CO2
Ba
Cu
Pb
Zn
H2O+
Total
A1
A2
A3
A4
A5
Least
altered
rhyolite
Mottled
rhyolite
stringer
zone
white
rhyolite
stringer
zone
A2 change
A3 change
A4 change
77.00
0.10
12.30
1.76
0.05
1.40
0.48
2.63
3.57
0.02
0.11
0.10
0.09
0.00
0.00
0.01
0.50
100.12
75.33
0.07
11.30
4.17
0.05
1.89
0.06
0.48
3.31
0.02
1.13
0.10
0.10
0.01
0.01
0.01
1.99
100.03
SL
SL
SL
LG
71.62
0.07
8.13
9.66
0.04
1.49
0.15
0.12
2.31
0.02
6.58
0.15
0.25
0.11
0.01
0.07
0.10
100.88
SL
SL
SL
LG
SL
SG
LL
LL
SL
79.89
0.05
9.69
1.16
0.02
0.42
0.34
0.52
6.27
0.02
0.40
0.27
0.23
0.01
0.01
0.03
0.20
99.53
SG
LL
SL
SL
LL
LL
SL
LL
LG
64.34
0.15
19.10
2.76
0.02
4.67
0.27
1.21
4.30
0.02
0.18
0.08
0.20
0.00
0.01
0.01
2.65
99.97
SG
LL
LL
SL
LG
SG
SG?
SG?
LG
SL
LG
LG
LG
SG?
SG?
LG
LL
SG
SG small gain; LG large gain; SL small loss, LL large loss;

NC negligible change; no change
LG
LG
LG
SG?
SG?
LG
LL
SL
A5
change
SL
LG
LG
LG
LL
LG
SL
LL
SG
LG
SL
LG
SG?
LG
SL
Closure obscures mass changes

Consequences of closure:
apparent differences in compositional data
between non altered and altered rocks do
not accurately reflect the real material
changes except in systems with zero net
mass change
Closure particularly obscures or distorts
mass changes in dominant components
e.g., Si, Al and Fe
Least altered
rhyolite
A1
qz + ser + py
altered rhyolite
A3
Less of a problem for components of low

initial proportion:
e.g. Na, Ca and trace elements
SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO

A1 Lst alt Rhyolite 77.00 0.10 12.30 1.76 0.05 1.40 0.48
A3 Qtz+Py alt Rhyolite 71.62 0.07 8.13 9.66 0.04 1.49 0.15
No. Description
Na2O K2O
2.63 3.57
0.12 2.31
P2O5
0.02
0.02
S
CO2 Total
0.11 0.10 99.52
6.58 0.15 100.34
Closure obscures mass changes

Consequences of closure:
The composition data for rhyolites A1 & A3
suggest losses of Si & Al in the qz + ser + py
altered sample
Not so!
They are closure phenomena related to
large additions of Fe and S
On the other hand, gains of Fe and S and

losses of Ca and Na are real, although not
accurately indicating mass changes
Least altered
rhyolite
A1
qz + ser + py
altered rhyolite
A3
Low initial proportions

less affected by closure
SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO

No. Description
Na2O K2O
2.63 3.57
0.12 2.31
P2O5
0.02
0.02
S
CO2 Total
0.11 0.10 99.52
6.58 0.15 100.34
Closure and alteration indices

Alteration indices are not immune to effects of
closure
Each component of composition data is affected by

closure
Therefore, major components, such as Si and Al,
(which are most strongly affected) are rarely used in
alteration indices
Key Points:
We can use major element composition data and

alteration indices to:
provide quantitative estimates of alteration
intensity
provide insights to the chemical reactions
involved
However, both wt % composition data and indices are

affected by closure, which may obscure or distort
alteration related chemical changes
Immobile element techniques

These eliminate closure and enable estimation of actual mass changes of
chemical components in alteration processes
There are several possible approaches:
Isocon method (Grant, 1986; modified by Huston, 1993)
Reconstructed composition method (MacLean & Barrett, 1993)
Pearce element ratio analysis (Stanley & Madeisky, 1996)
All depend on recognition of

immobile elements and
composition of the precursor (non
altered) rock
compatible
Although closure affects the

proportions (concentrations) of
immobile elements in systems that
have net mass change, the ratios of
immobile elements do not change
incompatible
Immobile elements
Al, Ti, Zr, Nb, Y, heavy REE (Lu, Yb), Hf, Ta and Th are essentially immobile in
VHMS and most other hydrothermal alteration systems
In some cases Sc, V, Cr and P are also immobile
Ti, Zr, Nb, Y are immobile in hydrothermal, diagenetic, weathering and
metamorphic alteration up to mid amphibolite facies. Therefore useful in
tectono magmatic discrimination diagrams
Zr is considered to be immobile in all systems except some metamorphic and
carbonatite systems, which have CO2 rich fluids
Zr is easily and accurately detectable by XRF on pulverised sample
Need to test for element immobility for each sample suite
The gold dish analogy
proportions of
/
and
vary, but
irrespective of the amount of gravel in the

dish
8'++ &"')*# #+.%$'.%/)

C#T'(0 2#,Z(#5 ] Y#00(''O 9AA;H
2'
! ;)%.%'( $'++ /A -)'(.#1#, 1/&5 %+ VWW *

! L"# <1/</1.%/) /A %$$/?%(# &/$</)#). %)
."# '(.#1#, 1/&5 %+ ,%$%)%+"#, ?#&'-+# /A '
)#. *'%) %) ."# $/?%(# &/$</)#). I&(/+-1#K
! L"# %$$/?%(# &/$</)#). %+ 1#+./1#, ./ %.+
%)%.%'( &/).#). ?0 $-(.%<(0%)* ?0 ."# A'&./1
b1WOb1' IVPXK
!W n
b1W
!' n
b1'
! L"# <1/</1.%/)+ /A $/?%(# &/$</)#).+ %) ."# '(.#1#, +'$<(# '1# 1#',@-+.#, ?0

."# +'$# A'&./1 ./ <1/,-&# ."# E1#&/)+.1-&.#, &/$</+%.%/)G b1WOb1' M !'nF IV^WK
! 8'++ &"')*# /A ."# $/?%(# &/$</)#).F 'F %+ ."# 1#&/)+.1-&.#, &/$</+%.%/)
$%)-+ ."# <1#&-1+/1 <1/</1.%/) Ib1WOb1' M !'nK !WnF IXW *OVWW*K
!"#$%&" '(%)" *+%,- $%.,/( 0123 *)45( ?0
Outline of reconstructed composition method

(after MacLean & Barrett, 1993)
1. Tabulate composition data

major components and potentially immobile trace elements (Zr, Nb, Y)
A1
Least alt Rhyolite
A3
Qz+ser+py alt Rhy
SiO2 77.00
CaO 0.48
Total 99.52
SiO2 71.62
CaO 0.15
Total 100.34
TiO2 0.10
Na2O 2.63
Zr 157
TiO2 0.07
Na2O 0.12
Zr 111
Al2O3 12.30
K2O 3.57
Fe2O3 1.76
P2O5 0.02
MnO 0.05
S 0.11
MgO 1.40
CO2 0.10
Al2O3 8.13
K2O 2.31
Fe2O3 9.66
P2O5 0.02
MnO 0.04
S 6.58
MgO 1.49
CO2 0.15
Because of space limitations, data for only two

samples are shown
In practice, data for all samples from a single
litho stratigraphic unit would be tabulated and
plotted, as in scatter graphs on the following
slide.
A1
A3

2. Plot x y diagrams of potentially immobile elements:

Ti, Al, Zr, Nb, etc.
3. Identify single precursor groups (exclude outliers)

4. Test for immobility
fit linear trend lines and calculate correlation coefficients
r > 0.85 is indication of immobility
select immobile monitor element (Zr in this case))
TiO2 %
Al2O3 %
TiO2
0.20
20.00
0.20
r = 0.947
0.15
0.10
A1
A3
0.00
A3
0.05
0.00
0
50
100
150
200
250
Zr ppm
A1
0.10
A3
5.00
r = 0.904
0.15
10.00
A1
0.05
r = 0.946
15.00
0.00
0
50
100
150
200
250
Zr ppm
10
15
20
Al2O3
Exercise 3
MacLean & Barrett reconstructed composition method
TESTING IMMOBILITY
Inspect the ten scatter plots, linear regressions and correlation factors of
Thalanga footwall rhyolite data in Figure Ex3
Determine whether these data are consistent with a single precursor system
are the samples likely to be cogenetic and derived from a single
protolith? (yes or no)
Determine which element(s) and oxide(s) satisfy the Barrett & MacLean
(1994) test for immobility in a single precursor system (r >0.85)
Rank the elements and oxides in order of immobility, from most to least
immobile
Select which component(s) would be most suitable as an immobile monitor
for mass change calculations
justify your selection
TiO2 %
Al2O3 %
0.20
20.00
Fig. Ex3
y = 0.080x + 0.986 r = 0.954
y = 0.001x - 0.005 r = 0.946
0.15
15.00
A1
5.00
0.05
0.00
0.00
Scatter plots of potentially

immobile element data from
Thalanga rhyolites
A1
10.00
0.10
50
100
150
200
250
50
100
150
200
Nb ppm
250
Zr ppm
Zr ppm
Y ppm
25.00
80.00
y = 0.102x + 0.643 r = 0.938
20.00
y = 0.195x + 10.782 r = 0.514
60.00
15.00
A1
40.00
10.00
A1
20.00
5.00
0.00
0
50
100
150
200
250
Zr ppm
TiO2
50
100
150
200
250
Zr ppm
Nb
25.00
0.20
0.15
0.00
y = 0.008x - 0.006 r = 0.910
20.00
A1
15.00
y = 1.194x + 0.232 r = 0.927
A1
0.10
10.00
0.05
5.00
0.00
0.00
0
10
15
Al2O3
TiO2
10
15
20
Al2O3
Y
80.00
0.20
y = 2.274x + 10.112 r = 0.506
y = 0.006x - 0.000 r = 0.907
0.15
20
60.00
A1
0.10
40.00
A1
20.00
0.05
0.00
0.00
0
10
15
20
25
10
15
20
Al2O3
Nb
TiO2
80.00
0.20
y = 0.001x + 0.050 r = 0.493
y = 2.195x + 5.560 r = 0.629
60.00
0.15
A1
0.10
40.00
0.05
20.00
A1
0.00
0.00
0
20
40
60
80
10
15
20
25
Nb
Exercise 3 Answers
Determine whether these data are consistent with a single precursor system
are the samples likely to be cogenetic and derived from a single
protolith? YES
Determine which element(s) and oxide(s) satisfy the Barrett & MacLean
(1994) test for immobility in a single precursor system (r >0.85) TiO2, Zr,
Al2O3, Nb
Rank the elements and oxides in order of immobility, from most to least
immobile Zr > Al2O3 > TiO2 > Nb >>> Y
Select which component(s) would be most suitable as an immobile monitor
for mass change calculations
justify your selection
Zr highest correlation coefficients obtained from bivariate plots

involving Zr, suggesting that this element was the least mobile during
alteration at Thalanga

5. Select least altered precursor composition:

based on textural & mineralogical preservation, alteration indices, sample
location etc.
may be a single sample, or average of several samples
6. Calculate mass changes for major chemical components using formula (easily
done in spreadsheet):
Da = [ Zo/ Za x Ca ] Co
where:
Da is absolute mass change in g/100g.

Ca = % proportion of component in altered rock,
Co = % proportion of component in precursor,
Za = proportion of immobile element in altered rock,
Zo = proportion of immobile element in precursor.
TiO2 Al2O3 Fe2O3 MnO MgO CaO

%
No. Description
A1 > A3 (g/100g)
SiO2
24.3
0.0
0.8
11.9
0.0
0.7
0.3
Na2O K2O
P2O5
CO2 Total
0.02
0.02
Zr
ppm
0.11 0.10 99.5 157
6.58 0.15 100.3 111
2.63
0.12
3.57
2.31
2.5
0.3
0.0
9.2
0.1
42.4
Comparison of composition & mass change data

TiO2 Al2O3 Fe2O3 MnO MgO CaO
%
No. Description
A1 > A3 (g/100g)
SiO2
24.3
0.0
0.8
11.9
0.0
0.7
0.3
Na2O K2O
P2O5
CO2 Total
0.02
0.02
Zr
ppm
0.11 0.10 99.5 157
6.58 0.15 100.3 111
2.63
0.12
3.57
2.31
2.5
0.3
0.0
9.2
0.1
42.4
g/100g
Large net mass change

due to addition of Si, Fe &
S (as quartz and pyrite)
Gain of Si is not evident in
composition data
(because of closure)
Near complete losses of
Na & Ca (sericitisation of
plagioclase) but these are
relatively small masses
50
A1 -> A3
40
30
20
10
-10
SiO2
Fe2O3
Na2O
Total
Summary
1. Hydrolysis reactions (H+) are amongst the most important in rock alteration
processes:
They influence fluid pH, metal solubilities, transfer of alkalis K+, Na+, Ca2+
& Mg2+ and mineralisation
2. Major element composition data, and alteration indices derived from them,
can be used to quantify intensity of alteration
However, both data and indices are affected by closure, which may
obscure or distort alteration related chemical changes
3. Mass change techniques overcome the problem of closure to provide
quantitative estimates of the amounts of chemical components transferred
in alteration:
Mass changes of chemical components can be directly related to
alteration reactions, precipitation and dissolution.
Mass change techniques are based on recognition of immobile
components and the composition of the non altered precursor rock
Exercise 4
MacLean & Barrett single precursor system
Use the analytical data in Table Ex6 to calculate major
component mass changes in the altered rhyolites A2 to A5 by
the MacLean and Barrett method
Use the composition of sample A1 for the least altered
precursor composition and a suitably immobile element or
oxide (determined in Exercise 3) as the immobile monitor
Complete the calculations for at least two altered samples to
gain familiarity with the process
Plot the results on the absolute mass change diagram
how do the calculated mass changes compare with those
you estimated in Exercise 2?
Exercise 4 Answers
(g/100 g mass changes)
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
A2
mot
10.6
-0.019
0.8
3.1
0.01
0.8
-0.41
-2.1
0.3
0.003
A3
stri
24.3
-0.001
-0.8
11.9
0.01
0.7
-0.27
-2.5
-0.3
0.008
A4
whi
33.0
-0.031
1.0
-0.2
-0.02
-0.8
-0.01
-1.9
5.1
0.008
A5
foli
-31.9
0.005
1.1
0.2
-0.04
1.9
-0.29
-1.8
-0.6
-0.006
CO2
Ba
Cu
Pb
Zn
H2O+
Nb
Zr
Total
A2
mot
1.20
0.02
0.03
0.012
0.012
0.002
1.8
1.3
0.1
0.0
16.2
A3
stri
9.20
0.11
0.26
0.156
0.014
0.089
-0.4
0.6
-10.5
0.0
42.6
A4
whi
0.44
0.27
0.23
0.014
0.014
0.031
-0.2
0.1
-5.7
0.0
37.0
A5
foli
0.02
-0.04
0.05
0.000
0.007
-0.003
1.4
1.8
-17.1
0.0
-30.1
Absolute mass change (g/100 g)
50
40
30
20
A2
10
A3
A4
A5
-10
-20
-30
-40
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
Absolute mass change (g/100g)
50
40
30
20
A2
10
A3
A4
A5
-10
-20
-30
-40
CO2
Ba
Cu
Pb
Zn
H 2O +
Nb
Zr
Net
References
Cooke, D. R., and Simmons, S. F., 2000, Characteristics and genesis of epithermal gold deposits: Reviews in Economic
Geology, v. 13, p. 221 244.
Eilu, P., Mikucki, E. J., and Groves, D. I., 1997, Wallrock alteration and primary geochemical dispersion in lode gold
exploration: Notes from short course, Fourth biennial meeting of the Society for Geology Applied to Mineral
Deposits, Turku, Finland, 11 13 August, 1997, p. 65.
Grant, J. A., 1986, The isocon diagram; a simple solution to Gresens' equation for metasomatic alteration: Economic
Geology, v. 81, p. 1976 1982.
Guilbert , J. M., and Park, C. F., 1986, The geology of ore deposits: New York, W.H. Freeman, 985 p.
Huston, D. L., 1993, The effect of alteration and metamorphism on wall rocks to the Balcooma and Dry River South
volcanic hosted massive sulfide deposits, Queensland, Australia: Journal of Geochemical Exploration, v. 48, p.
277 307.
Ishikawa, Y., Sawaguchi, T., Iwaya, S., and Horiuchi, M., 1976, Delineation of prospecting targets for Kuroko deposits
based on modes of volcanism of underlying dacite and alteration halos: Mining Geology, v. 26, p. 105 117, (in
Japanese with English abstract).
Large, R. R., Gemmell, J. B., and Paulick, H., 2001, The Alteration Box Plot: a simple approach to understanding the
relationship between alteration mineralogy and lithogeochemistry associated with volcanic hosted massive
sulfide deposits.: Economic Geology, v. 96, p. 957 971.
MacLean, W. H., and Barrett, T. J., 1993, Lithogeochemical Techniques Using Immobile Elements: Journal of
Geochemical Exploration, v. 48, p. 109 133.
Stanley, C. R., and Madeisky, H. E., 1996, Lithogeochemical exploration for metasomatic zones associated with
hydrothermal mineral deposits using Pearce element ratio analysis, short course notes, Mineral Deposit
Research Unit, University of British Columbia.
Winchester, J. A., and Floyd, P. A., 1977, Geochemical discrimination of different magma series and their
differentiation products using immobile elements: Chemical Geology, v. 20, p. 325 343.
Wolfe, R. C., 1994, The geology, paragenesis and alteration geochemistry of the Endeavour 48 Cu Au porphyry,
Goonumbla, NSW: Unpub. B.Sc. Hons thesis, University of Tasmania.

Alteration Geochem Mod

Diunggah oleh

Informasi Dokumen

Deskripsi Asli:

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Alteration Geochem Mod

Diunggah oleh

Hak Cipta:

Format Tersedia

Chemical changes due to hydrothermal

David R Cooke and Andrew McNeill

Disseminated bornite in orthoclase

M.Econ. Geol. Short course 2013 Slide 2

Chemical and thermal gradients are the principal

Disseminated bornite in orthoclase altered

M.Econ. Geol. Short course 2013 Slide 3

Acid neutralization (hydrolysis)

KAl3Si3O10(OH)2 + 6SiO2 + 2K+

Centimetre scale halo of pervasive sericite

M.Econ. Geol. Short course 2013 Slide 5

Hydrolysis: reactions that consume H+

KAl3Si3O10(OH)2 + 6SiO2 + 3Na+

KAl3Si3O10(OH)2 + 6SiO2 + 2K+

Centimetre to metre scale sericite altered zones around gold bearing

Further hydrolysis results in alkali stripping

M.Econ. Geol. Short course 2013 Slide 7

this in turn affects metal

Feldspar, mica and clay

940 g/t Au ore specimen, Sunrise Dam Gold Mine, WA

M.Econ. Geol. Short course 2013 Slide 8

Hydrolysis: reactions involving H+

Silicate alteration may actually be a consequence of sulfide

Chlorite magnetite altered diorite cut by

M.Econ. Geol. Short course 2013 Slide 9

Hydration: addition of H2O

Dehydration: removal of H2O

Pyrophyllite: petrographically difficult to distinguish from sericite

M.Econ. Geol. Short course 2013 Slide 11

Alkali or alkali earth metasomatism

Mg metasomatism converting limestone to dolomite:

Irregular domains of pale grey dolomite

M.Econ. Geol. Short course 2013 Slide 12

Alkali or alkali earth metasomatism

KAlSi3O8 + 6.5Mg+2 + 10H2O

Andesitic breccia with incipiently

Pervasively K feldspar altered andesite

Subsequent chloritic alteration

M.Econ. Geol. Short course 2013 Slide 13

Decarbonation: removal of CO2

MgO + CO2 (g)

(CaMg)Si2O6 + 2 CO2 (g)

Banded dolomite + diopside skarn

M.Econ. Geol. Short course 2013 Slide 14

Silicification and silicate alteration

Silicate alteration converts rocks to new silicate minerals

Folded sandstone + limestone beds

M.Econ. Geol. Short course 2013 Slide 15

Carbonation and silicification

3 CaCO3 + Fe2O3 + 3SiO2

calcite hematite quartz

M.Econ. Geol. Short course 2013 Slide 16

Magnetite in banded iron formation

Yellowish jarosite stain on walls of Ladolam gold mine,

Close up view: jarosite derived from weathering of

Sulfidation and desulfidation

A variation of this reaction can be important for gold

M.Econ. Geol. Short course 2013 Slide 19

What types of reactions occurred here?

hydrolysis & hydration of sericite to kaolinite

oxidation & hydration of Fe sulfates

goethite (limonite) stained pit wall

Fe sulfates & sulfuric acid