Exploration and Mining Geology, Vol. 19, Nos. 12, p.

1322, 2010
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Alkali/Alumina Molar Ratio Trends in Altered Granitoid Rocks

Hosting Porphyry and Related Deposits
J.F. Davies1, and R.E. Whitehead1
(Received November 10, 2009; accepted November 30, 2009)

Abstract Alkali/alumina and MgO/alumina molar ratio plots graphically portray both chemical
and mineralogical changes accompanying potassic, phyllic, argillic, chloritic, and alunitic alteration
of quartz monzonites and granodiorites hosting porphyry (as well as lode and greisen) ore deposits.
The molar ratio plots can be used to identify different types of alteration. In most cases, the identi-
fication based on molar ratios coincides with petrographic data. In those instances where the molar
ratio and petrographic identifications do not agree, the mineralogy might need to be re-examined.
Hydrothermal alteration studies using trace elements could benefit from the application of comple-
mentary alkali/alumina molar ratio plots. 2010 Canadian Institute of Mining, Metallurgy and
Petroleum. All rights reserved.

Key Words: Alteration, alkali/alumina molar ratios, granitoids, porphyry deposits.

Sommaire Le diagramme des rapports molaires alkali/alumine et MgO/alumine illustre claire-

ment les changements chimiques et minralogiques qui accompagnent les altrations potassique,
phyllique, argillique, chloritique, and alunitique des monzonites quartz et des granodiorites encais-
sant les gtes de type porphyrique, ainsi que des veines et des greisens qui leur sont associs. Les
diagrammes de rapports molaires peuvent tre utiliss pour identifier divers types daltration. Dans
la plupart des cas, lidentification base sur les rapports molaires est en accord avec celle base sur
les donnes ptrographiques. L ou il y a dsaccord entre les rapports molaires et les donnes ptro-
graphiques, il peut tre ncessaire de rexaminer la minralogie. Les tudes de laltration hydro-
thermale accompagnes dune tude des lments traces auraient avantage utiliser un diagramme
des rapports molaires alkali/alumine. 2010 Canadian Institute of Mining, Metallurgy and Pe-
troleum. All rights reserved.

1 Department of Earth Sciences, Laurentian University, Ramsey Lake Road, Sudbury, Ontario, P3E 2C6.
Corresponding Author: E-mail: rmehes@laurentian.ca
14 Exploration and Mining Geology, Vol. 19, Nos. 12, p. 1322, 2010

Introduction diorites should plot within or near the wedge-shaped area

defined by the line joining albite (Na2O/Al2O3 value of 1.0)
Several methods of assessing the nature and intensity to K-feldspar (K2O/Al2O3 value of 1.0) and the line join-
of hydrothermal alteration utilize various element ratios. ing oligoclaseandesine (Na2O/Al2O3 value of 0.6) and K-
The most common of these involve the use of immobile feldspar (K2O/Al2O3 value of 0.90). Figure 1b shows that
trace elements such as Ti or Zr as standards against which the compositions of several Cenozoic granitoid intrusions
the levels of mobile elements such as Na, K, and Mg are mostly plot within, and the remainder lie adjacent to, the
measured. Early examples using immobile trace elements designated wedge-shaped area (after Davies and White-
are Gresens equations (Gresens, 1967) and Pearce element head, 2006).
ratios (Pearce, 1968). Adaptations of these methods have
been widely used in the study of alteration associated with Molar Ratios and Porphyry Deposits
VHMS deposits (e.g., MacLean, 1990; Barrett and Mac-
Lean, 1991; Barrett et al., 1991; MacLean and Hoy, 1991; Alteration assemblages associated with porphyry de-
Stanley and Madeisky, 1994). posits are potassic (biotite-K-feldspar), phyllic (quartz-
Alkali/alumina molar ratio plots employ oxide ratios in sericite), intermediate argillic (kaolinite, montmorillonite),
which Al2O3 serves as the denominator in place of Ti or Zr. and advanced argillic (dickite and alunite in addition to
Such plots have the advantage of portraying, in a simple kaolinite, montmorillonite).
and direct way, both chemical and mineralogical patterns Outside the boundaries of porphyry mineralization, low
on the same diagram. For example, a single diagram can intensity propylitic alteration (chlorite, albite, epidote, and
illustrate the entire plagioclase series, K-feldspar, biotite, calcite) is analogous to low-grade greenschist regional
muscovite, and kaolin (Fig. 1a). The diagram might be fur- metamorphism. Propylitic alteration yields no well defined
ther expanded by plotting molar K2O/Al2O3 against molar molar ratio patterns because of the variable composition of
MgO/Al2O3 to accommodate such minerals as chlorite and the altered rock resulting from differing amounts of alkalis
phlogopite. added to or removed from the rocks.
Alkali/alumina molar ratio diagrams have been used Summary accounts of alteration of granitoid rocks host-
to portray the compositions of both unaltered and altered ing porphyry deposits might be found in Creasey (1966)
host rocks for several types of mineral deposits. Examples and Lowell and Guilbert (1970). The following types of
include felsic volcanic rocks hosting massive sulfide reaction are involved:
(VHMS) deposits (Davies and Whitehead, 2006), and Se- K-feldspar to sericite:
dex deposits (Davies and Whitehead, 1994).
The present study examines the application of these dia- 1.5KAlSi3O8 + H + 0.5KAl3Si3O10 (OH) 2 + K + (1)
grams to granitoid intrusions hosting porphyry and related
deposits. Sericite to kaolinite:
The essential features of alkali/alumina molar ratio dia- 2KAlSi3O10 (OH) 2 + 2H + + 3H 2 O 3Al2Si 2 O5 (OH) 4 + 2K + (2)
grams are shown in Figure 1a, where
molar K2O/Al2O3 for biotite and K-
feldspar range from 0.9 to 1.0. The
molar ratio value of 0.33 is the ratio of
muscovite and alunite; illite is slightly
less than 0.33. The Na2O/Al2O3 molar
ratios range from 1 for albite to 0 for
Na-free anorthite. The full range of
values for plagioclase is given in Table
1. Minerals such as kaolin, chlorite,
and epidote plot at coordinates (0, 0).
Included on the diagram are sev-
eral joins representing commonly oc-
curring mineral pairs, such as albite
muscovite and albiteK-feldspar. The
join connecting the Na2O/Al2O3 value
of 0.6 (oligoclaseandesine boundary)
and K-feldspar (or biotite) is selected
as appropriate for the lower limit of
felsic volcanic rocks and granitoid in-
trusions in that the plagioclases gener-
ally range from albite to oligoclase Fig. 1. Na2O/Al2O3 vs. K2O/Al2O3 molar ratio diagrams: a. Alkali/alumina molar ratios of feld-
spars, micas, and clay minerals; alunite plots at the same point as muscovite; clay minerals and
andesine. Consequently, most samples other aluminous nonalkali-bearing minerals such as many chlorites, epidote, and topaz lie at the
of unaltered rhyolites, rhyodacites, origin on this diagram; b. Molar ratio plot of unaltered Cenozoic granitoid intrusions (after Davies
granites, quartz monzonites, and grano- and Whitehead, 2006). Abbreviations: Kspar = K-feldspar.
 Alkali/alumina Molar Ratio Trends in Altered Granitoid Rocks Hosting Porphyry and Related Deposits J.F. Davies and R.E. Whitehead 15

Sericite to alunite: case of the Sibert deposit, molar ratios calculated from
KAl3Si3O10 (OH) 2 + 4H + + 2SO 42 KAl(SO 4 ) 2 (OH)6 + 3SiO 2 (3) only four bulk samples trace a progressive decrease in both
Na2O/Al2O3 and K2O/Al2O3 values.
Muscovite to topaz:
2KAl3Si3O10 (OH) 2 +4H + +4.8F (4) Bingham Porphyry Copper Deposit
+
Numerous studies of the Bingham porphyry copper
3Al2SiO 4 [(OH)0.2 F0.8 ]2 + 2K + 3SiO 2 + 2.8(OH) + 2H 2 O
deposit have yielded a large amount of information and
chemical data on hydrothermal alteration of the host Oligo-
Albite (in Na-plagioclase) to K-feldspar: cene equigranular quartz monzonite and quartz monzon-
NaAlSi3O8 + K + KAlSi3O8 + Na + (5) ite porphyry, the two main phases of the Bingham stock
(Moore and Nash, 1974; Bray et al., 1975; Lanier et al.,
Albite to muscovite: 1975, 1978; Moore, 1978; and references within). The
3NaAlSi3O8 + K + + 2H + KAl3Si3O10 (OH) 2 + 3Na + + 6SiO 2 (6) Bingham stock is part of a composite intrusion which also
includes the Last Chance quartz monzonite stock and the
Albite to Na-montmorillonite: Phoenix quartz monzonite dike. The Bingham stock is also
(7) cut by a number of latite and minette dikes. The possible
1.17NaAlSi3O8 + H +
+
significance of these dikes is considered below.
0.5Na 0.33 Al2.33Si3.67 O10 (OH) 2 + 1.67SiO 2 + Na The copper orebody is hosted by the quartz monzonite
porphyry and adjacent parts of the surrounding equigranu-
Na-montmorillonite to kaolinite: lar quartz monzonite. The porphyry, which forms the core

Na 0.33 Al2.33Si3.67 O10 (OH) 2 + 3H 2 O (8) of the Bingham stock, is the most highly altered phase of
+
3.5Al2Si 2 O5 (OH) 4 + Na + 4SiO 2 the stock and is considered to have been the main conduit
of the hydrothermal fluids responsible for mineralization
and accompanying hydrothermal alteration.
Experimental data from Hemley and Jones (1964) show Almost all of the Bingham stock has been altered to
that the sequence K-feldspar sericite kaolinite results some extent. According to Lanier et al. (1978), the best
from progressive decreases in aK+/aH+ as a consequence analogue for the original composition of the equigranu-
of increasing aH+. Consequently, mixed assemblages con- lar quartz monzonite might be the unmineralized and un-
taining, for example, K-feldspar and sericite or sericite altered Last Chance quartz monzonite, which consists of
and kaolinite are common. However, assemblages such as orthoclase (30%) and plagioclase (30%), with the remain-
K-feldspar and clay minerals are generally excluded ex- der being augite, amphibole, and biotite.
cept in cases of extreme disequilibrium or when supergene Lanier et al. (1975, 1978) reported well-defined mineral-
processes are superimposed on the original hydrothermal ogical alteration zoning in the equigranular quartz mon-
assemblages. zonite. The zoning is co-axial with respect to the quartz
In the following sections, data from various porphyry monzonite porphyry and copper orebody. Between 2200
deposits are presented. It is important to point out that the and 3400 feet from the porphyry contact, hydrothermal ac-
petrographic descriptions, the identifications of the altera- tinolite after augite comprises about 16% of the rock, and
tion assemblages, and the whole-rock analytical data from is accompanied by about 11% chlorite, which also replaces
which the molar ratios were calculated, were all taken dir- augite and, in part, hydrothermal actinolite. Lanier et al.
ectly from the relevant referenced publications. The molar (1975) reported about 5% magmatic phlogopite in the ac-
ratio patterns for each deposit are then compared with the tinolite-chlorite zone.
interpretations presented by the original authors. Quartz-orthoclase-phlogopite alteration extends out-
The chemical analyses used in the paper have been lim- ward for 2200 feet from the contact of the equigranular
ited mainly to papers published up to the 1980s because quartz monzonite with the quartz monzonite porphyry.
more recent papers contain few published whole rock an- Within this zone, up to 28% hydrothermal phlogopite re-
alyses. It might be said that some of the deposits described places actinolite (Lanier et al., 1975, 1978). Hydrothermal
in this paper also have too few samples. However, in the orthoclase occurs here as rims replacing plagioclase, as ir-
regular patches enveloping Na-rich plagioclase, and as re-
Table 1. Approximate Molar Na2O/Al2O3 Values for the Plagioclase placement perthites (Lanier et al., 1978).
Series Contrary to Lanier et al. (1975, 1978), Moore and Nash
(1974) claimed that hydrothermal orthoclase is not a prom-
Plagioclases Molar Na2O/Al2O3 inent constituent of the equigranular quartz monzonite,
Albite 1.00.8 of which the quartz-orthoclase-phlogopite zone is a part.
Oligoclase 0.80.6 These contradictory statements underscore the problem of
Andesine 0.60.33
distinguishing between hydrothermal and magmatic feld-
spars (and quartz) on the basis of textural interpretations.
Labradorite 0.330.12
Modal analyses by Lanier et al. (1975, 1978) re-
Bytownite 0.120.05
veal a continuous decrease in plagioclase/total feldspar
Anorthite 0.050.00 from the peripheral actinolite-chlorite zone toward and
16 Exploration and Mining Geology, Vol. 19, Nos. 12, p. 1322, 2010

into the quartz-orthoclase-phlogopite

zone. Both quartz and total ferromag-
nesian minerals, largely phlogopite,
are greater in the quartz-orthoclase-
phlogopite zone than in the peripheral
actinolite-chlorite zone.
The quartz monzonite porphyry,
which forms the core of the Bing-
ham stock, has undergone extensive
potassic (biotite-orthoclase) altera-
tion, which is more or less coincident
with the copper orebody (Moore and
Nash, 1974; Moore, 1978). About 25%
hydrothermal biotite is present mainly
as aggregates of small flakes pseudo-
morphing earlier ferromagnesian min-
erals. In places, irregular intergrowths
of orthoclase and quartz permeate the
aplitic groundmass of the porphyry.
Pervasive sericite alteration was
superimposed on the potassic zone
of the quartz monzonite porphyry
and to a lesser extent on the adjacent
quartz-orthoclase-phlogopite zone of
the equigranular quartz monzonite.
Sericite partly replaces plagioclase and
biotite but only to a minor extent; it has
not affected orthoclase. Sericite consti-
tutes about 5% or less of the rock and
does not greatly affect K2O/Al2O3 val-
ues compared to the effects of biotite
and orthoclase.
Chemical analyses of the samples
used by Lanier et al. (1975, 1978) to
determine the zones of alteration dis-
cussed above are plotted on alkali/ Fig. 2. K2O/Al2O3 vs. Na2O/Al2O3 molar ratios of least altered (a) and (b) variously altered Bing-
alumina and MgO/alumina diagrams ham equigranular quartz monzonite and quartz monzonite porphyry. c. K2O/Al2O3 and MgO/Al2O3
in Figure 2. The alkali/alumina char- molar ratio plot of the same samples as in a and b. Least-altered samples are omitted from b; they
acteristics of the least-altered Bingham would plot over the actinolite-chlorite and some of the quartz-orthoclase-phlogopite samples. Ab-
breviations: act = actinolite, alt = altered, bio = biotite, chl = chlorite, monz = monzonite, orth =
samples are shown in Figure 2a. The orthoclase, phlog = phlogopite, qmp = quartz monzonite porphyry, qtz = quartz.
actinolite-chlorite and quartz-ortho-
clase-phlogopite alteration assemblages display consider- examination alone. In the case of actinolite-chlorite altera-
able overlap with one another and also with the least al- tion, the increase in K2O/Al2O3 and decrease in Na2O/Al2O3
tered samples (Fig. 2b,c). This overlap is not unexpected relative to the samples of least altered rock might be a re-
because alteration of primary pyroxenes and amphiboles to sult of K2O alteration of plagioclase to orthoclase (reaction
actinolite and chlorite does not involve significant change 5), as well as the growth of hydrothermal phlogopite. The
in the alkali content of the rocks. However, many of the ac- distinction between primary and secondary (hydrothermal)
tinolite-chlorite and quartz-orthoclase-phlogopite samples feldspars is not always a simple matter in altered rocks, and
have molar K2O/Al2O3 ratios that overlap with the most might be easily overlooked.
altered assemblage (quartz-orthoclase-biotite; Fig. 2b,c). Several papers published in 1997 document the pres-
Considerable K2O must have been added to both the actino- ence of latite and minette dikes that cut the Bingham stock
lite-chlorite samples and the quartz-orthoclase-phlogopite (Chesley and Ruiz, 1997; Deino and Keith, 1997; Keith et
alteration zone; this additional K2O most probably exists as al., 1997). Deino and Keith (1997) suggested that minette
hydrothermal orthoclase and phlogopite. If this is the case, magmas might have played a role in the petrogenesis of
the data would support the interpretation of hydrothermal the ore-related intrusions at Bingham. Although this has no
alteration by Lanier et al. (1975, 1978). direct bearing on the central theme of the present paper, the
The value of molar ratio plots in the study of alteration at somewhat unusual Mg-rich quartz-orthoclase-phlogopite
Bingham resides in their ability to indicate possible chan- alteration (Fig. 2c) might be related to minette intrusions
ges in mineralogy not readily recognizable by petrographic and coeval shoshonite lavas.
 Alkali/alumina Molar Ratio Trends in Altered Granitoid Rocks Hosting Porphyry and Related Deposits J.F. Davies and R.E. Whitehead 17

Granite-Mo Systems
Data compiled by Mutschler et al. (1981) on granites
hosting molybdenite deposits in the western U.S. illustrate
the alkali/alumina molar ratio characteristics of a variety
of alteration assemblages associated with many porphyry
deposits. The host rocks of the molybdenum deposits are
epizonal granodiorites, granite, and rhyolite porphyry of
early Cenozoic age.
Only the granite and rhyolite porphyry intrusions are
considered here; chemical data for the granodiorites are
lacking. The phenocrysts in the porphyries are predomin-
antly quartz and alkali feldspars, many of which are
perthitic. Groundmass feldspars are sodic plagioclase and
non-perthitic orthoclase.
Mutschler et al. (1981) report whole-rock analytical data
from various Mo deposits in which they designate altera-
tion assemblages as (a) moderate potassic, (b) strong potas-
sic, (c) moderate quartz-sericite, (d) strong quartz-sericite,
(e) intermediate argillic, and (f) strong argillic; these are
shown in Figure 3. The molar ratio values correspond well
for assemblages (a) to (d), representing first, K+ metasomat-
ism to produce moderate potassic alteration (a), and then to
strong potassic alteration (b), followed by H+ metasomat-
ism to produce assemblages (c) to (f) in which H+ is added
and alkalis are removed from the altered rock. Quartz and
sericite of assemblages (c) and (d) can be produced by the
addition of H+ to and removal of K+ from K-feldspar (reac-
tion 1) or alternatively by the addition of both K+ and H+ to
and the removal of Na+ from plagioclase (reaction 6).
Mutschler et al. (1981) do not comment on whether K-
feldspar or plagioclase (or both) were involved in the pro-
duction of the quartz-sericite assemblages. They do, how-
ever, note that the argillic assemblages resulted from the
replacement of plagioclase by clay minerals such as mont-
morillionite, kaolinite, pyrophyllite, and dickite (some ex-
amples are given in reactions 7 and 8).
Designation of the argillic assemblages as strong and
intermediate is perhaps puzzling. Except in the presence
of alunite, which is absent, the K2O/Al2O3 values for as-
semblage (e) do not suggest moderate argillic alteration,
nor does the presence of quartz and sericite. The explana-
tion might reside in how Mutschler et al. (1981) classify
strong, viz. 25 to 75 volume percent of the index clay
minerals. Allowing for this, the molar ratio values cor-
respond well with the description of the alteration assem-
blages.
Zijinshan Copper-Gold Deposit, China
The Zijinshan epithermal Cu-Au deposit occurs within
Jurassic biotite granites intruded by a Cretaceous dacite
porphyry pipe. Both rock types display similar alteration
and mineral zoning according to So et al. (1998). Only the
granites and their ores are discussed here.
Phyllic alteration (sericite-quartz) is developed in the
lower and outer parts of the deposit. Argillic alteration
(mainly quartz-dickite) forms a narrow band between
the phyllic and overlying alunite zone. Alunite alteration
(quartz-alunite) overlies the argillic zone, is the largest of
the alteration assemblages, and is host to most of the high-
Fig. 3. K2O/Al2O3 vs. Na2O/Al2O3 molar ratio plot of alteration in various
Cordilleran intrusions hosting Mo deposits. The letters a to f indicate: a
= moderate potassic alteration, b = strong potassic alteration, c = moder-
ate phyllic alteration, d = strong phyllic alteration, e = moderate argillic
alteration, f = strong argillic alteration.
sulfidation ore (mainly digenite and enargite). Alunite is
described as replacing both sericite and dickite. The low-
er phyllic and argillic zones contain pyrite, chalcopyrite,
bornite, sphalerite, and galena.
The high sulfidation ores and alunite alteration are over-
lain by a Au-bearing silica capping of quartz and opal re-
sulting from extreme acid leaching. Inward and upward
toward the center of mineralization, the spatial sequence of
alteration is phyllic argillic alunite and silicic. This
sequence parallels the paragenetic sequence as well as the
change from low-grade Cu-Pb-Zn-Mo ores to high-sulfida-
tion Cu ores, to dominantly Au ores in the silicic zone.
The sequence of alteration at Zijinshan is illustrated on
the molar ratio alkali/alumina diagrams (Fig. 4). The se-
quence weakly altered phyllic argillic (dickite)
alunitic is common in porphyry deposits. Extreme acid
leaching and production of a silicic capping is less com-
mon. The molar ratio plot in Figure 4b reveals unusually
high molar Na2O/Al2O3 values in the silicic zone, values
which are not readily apparent from a cursory scan of the
weight percent oxide values. Examination of weight per-
cent oxides shows that the absolute amount of Na2O de-
creases from 0.45 wt.% in the alunite zone (average of
5 samples) to 0.32 wt.% in the silicic zone (average of 2
samples); however, Al2O3 deceases more substantially,
from 12.77 wt.% in the alunite zone (average of 5 samples)
to 1.48 wt.% in the silicic capping (average of 2 samples),
indicating that Al2O3 was diluted almost 8-fold in the ex-
tremely altered silicic zone, compared to a factor of only
1.5 for Na2O. This is puzzling because Na2O is much more
mobile than Al2O3. So et al. (1998) offer no explanation
18 Exploration and Mining Geology, Vol. 19, Nos. 12, p. 1322, 2010
Fig. 4. K2O/Al2O3 vs. Na2O/Al2O3 molar ratio plot of alteration at the Zi-
jinshan Cu-Au deposit, China, showing alteration trends: a. weakly al-
tered phyllic argillic; b. argillic alunite and argillic silicic.
for this incongruity. In any case, the unusually high Na2O/
Al2O3 molar values only become readily apparent when the
whole-rock analyses are converted to molar ratios.
Sibert Porphyry Cu-Mo Deposit, France
The Sibert deposit at Rhone, France, occurs in a porphy-
ritic granite that has been variably altered over an area of
1 by 2 km (Beaufort and Meunier, 1983). Although not a
major deposit, it constitutes an uncomplicated example of
alteration trends as portrayed by alkali/alumina molar ratio
diagrams.
Early narrow quartz-orthoclase-pyrite-chalcopyrite-
(molybdenite) veins were accompanied by pervasive po-
tassic alteration. Transecting the potassic alteration are
narrow (12 cm) quartz-sericite-pyrite veinlets bordered
by phyllic alteration envelopes containing white micas re-
placing the orthoclase, plagioclase, and biotite of the ear-
lier potassic alteration.
Although the alteration envelopes are only 1 cm or less
wide, where the quartz-sericite veinlets are abundant and
form an interconnecting network, the phyllic alteration is
pervasive over areas of several square meters.
Beaufort and Meunier (1983) described and interpreted
zoning around the quartz-sericite veinlets in the follow-
ing manner. In the outermost zone, orthoclase and biotite
are mostly unaffected and plagioclase is only partially
replaced by sericite. Within the intermediate zone plagio-
clase has been completely replaced by sericite, biotite has
been partially replaced by phlogopite and sericite, where-
as K-feldspar is only partially replaced by sericite. In the
innermost envelope, closest to the veinlets, only quartz and
sericite are present. This was interpreted as K-feldspar and
phlogopite of the intermediate zone having been complete-
ly replaced by sericite.
Figure 5 illustrates the molar ratios calculated from bulk
whole-rock analyses reported by Beaufort and Meunier
(1983). The plot traces the progressive increase of phyllic
alteration from the early potassic assemblage to the inner-
most quartz-sericite zone. The pattern portrays a continu-
ous decrease in molar Na2O/Al2O3 and K2O/Al2O3 toward
the innermost phyllic zone. However, this pattern cannot
be reconciled with the interpretation based on field and
petrographic evidence presented by Beaufort and Meunier
(1983).
If the transition from the early potassic phase to the
outer phyllic assemblage involved only alteration of pla-
gioclase to sericite, leaving K-feldspar unaffected, K+ ions
must have been added from the fluid. The decrease in K2O/
Al2O3 suggests that this could not have been the case. From
where, then, were the K+ ions obtained? Alteration of K-
feldspar to muscovite might have released K+ ions (reaction
1) in sufficient quantities to be only partially consumed in
the alteration of plagioclase (reaction 6). The remainder of
the K+ ions would have stayed in the fluid phase. The end
result would be a decrease in both Na2O/Al2O3 and K2O/
Al2O3 in the solid phase of the outermost phyllic envelopes.
This scenario, involving the alteration of both K-feldspar
and plagioclase, is consistent with the molar ratio pattern.
The process suggested by Beaufort and Meunier (1983),
requiring addition of K+ ions from an external source is not
consistent with the molar ratio pattern.
A second problem at Sibert concerns the composition of
the intermediate phyllic assemblage. Beaufort and Meunier
(1983) claimed that all of the plagioclase had been altered
to sericite in the intermediate phyllic assemblage. Further-
more, X-ray analysis of mica flakes did not reveal the pres-
ence of paragonite in samples from the intermediate zone.
The absence of plagioclase and paragonite imply the ab-
sence of Na2O. Yet Figure 5 reveals a Na2O/Al2O3 value
of about 0.25, suggesting the presence of unaltered plagio-
clase.
The two discrepancies between molar ratio patterns and
petrographic data might be attributed to misidentification
of the feldspars, a not unlikely possibility considering the
degree of sericitization imposed on these minerals. How-
ever, this can only be determined by re-examination of the
samples studied by Beaufort and Meunier (1983). In that
context, it is perhaps worth noting that the study by Beau-
fort and Meunier (1983) was concerned mainly with the
composition and structure of the micas and not with the
feldspars.
San Rafael Tin Deposit, Peru
Cassiterite lodes of the San Rafael stock are confined
to major shear zones within Late Oligocene peraluminous
 Alkali/alumina Molar Ratio Trends in Altered Granitoid Rocks Hosting Porphyry and Related Deposits J.F. Davies and R.E. Whitehead 19
Fig. 5. K2O/Al2O3 vs. Na2O/Al2O3 molar ratio plot of the phyllic altera-
tion trend at the Sibert porphyry Cu-Mo deposit, France. Arrows trace the
trend from early potassic alteration to phyllic; degrees of superimposed
phyllic alteration increase toward the veins.
granitoid rocks described as porphyritic quartz monzonite
and granodiorite of the Andean Tin Belt (Kontak and Clark,
2002). These deposits are of Late Oligocene age. The main
cassiterite lodes contain abundant gangue chlorite, which
also occurs as relatively narrow (<2 cm) selvages to veins.
In some places, the chlorite grades outward into a sericite-
quartz assemblage. The most widespread alteration, how-
ever, occurs above the Sn lodes.
Within the upper 750 m of the San Rafael stock, the
alteration is mainly potassic and pervasive, consisting of
orthoclase replacing plagioclase and alkali feldspar pheno-
crysts as well as groundmass plagioclase. Less abundant
and more erratically distributed than the potassic alteration
is albitization of groundmass plagioclase and of the rims
of some perthitic alkali feldspars. Hydrolytic alteration of
San Rafael granitoid rocks takes the form of muscovite re-
placing both orthoclase and plagioclase.
Kontak and Clark (2002) noted that although potassic
alteration was not accompanied by deposition of dissemin-
ated cassiterite, K-metasomatism was part of the overall
hydrothermal process responsible for the cassiterite lodes.
Furthermore, because potassic alteration is much more
widespread than the chloritic envelopes surrounding the
veins, it might serve to identify those Andean intrusions
that are more likely to contain lode tin deposits than those
lacking such alteration. The problem is that it is difficult
to distinguish between unaltered and altered specimens in
outcrop and hand specimens because of only minor tex-
tural or color differences. Kontak and Clark (2002) used
feldspar staining techniques to distinguish K-bearing from
Ca-bearing feldspars and to indicate the degree of altera-
tion. They classified the samples as fresh, weakly altered,
moderately altered, or strongly altered, depending on the
amount of secondary K-feldspar (or alternatively, albite).
Kontak and Clark (2002) presented chemical analyses
of samples belonging to the categories noted above and
stated that the chemical data correlate reasonably well with
these petrographically determined categories. Their plots
of wt.% K2O versus Na2O show arrays of moderately and
strongly altered samples trending towards higher K2O or
Na2O than the unaltered samples.
Modal mineralogical data for the particular samples
analyzed were not presented by Kontak and Clark (2002).
Instead they calculated normative albite, orthoclase, and
quartz, which were plotted as a ternary diagram. The tern-
ary plot illustrates the same trends as the K2O versus Na2O
plot, as it should, because the normative minerals were cal-
culated from the chemical data.
Perhaps a more direct yet similar way of illustrating
the relationship between degrees of alteration and chem-
istry is by using molar ratio plots (Fig. 6). A linear trend
from high Na2O/Al2O3 and low K2O/Al2O3 to high K2O/
Al2O3 and low Na2O/Al2O3 is clearly discernible. In addi-
tion, it is noted that the trend is not directly toward K2O/
Al2O3 in the range for K-feldspar or biotite (0.9 to 1.0).
Rather, the trend is toward K2O/Al2O3 between 0.6 and 0.7.
Similarly, the linear pattern also trends toward oligoclase
(Na2O/Al2O3 ratio of approximately 0.7). The potassic to
sodic trend from K2O/Al2O3 of 0.65 and Na2O/Al2O3 of 0.0,
to Na2O/Al2O3 of 0.7 and K2O/Al2O3 of 0.0, reflects the
presence of hydrothermal muscovite after K-feldspar and
hydrothermal chlorite after biotite in the granitoid rocks.
Another feature shown on the plots by Kontak and Clark
(2002) is the fact that moderate alteration tends to be sodic
whereas strong alteration tends to be potassic. The molar
ratio plot (Fig. 6) displays the same tendency.
Figure 6 supports the contention of Kontak and Clark
(2002) that chemical data correlate reasonably well with
the degrees of alteration. However, both their plots and
Figure 6 also reveal several moderately altered samples
and one strongly altered sample lying in the field of fresh
samples, perhaps illustrating the difficulty in distinguish-
ing altered hydrothermal minerals from those of magmatic
origin.
Cassiterite Greisen, Kemptville, N.S.
This tin deposit, in contrast to the previously discussed
lode cassiterite orebody of the Andean Tin Belt, occurs
within a greisen derived from a Devonian leucogranite
(Williams-Jones and Kontak, 1998). Two types of greisen
are present, a quartz-sericite greisen and a quartz-topaz gre-
isen. Other minerals present in the greisen include fluorite,
cassiterite, apatite, and minor sulfides. In the vicinity of
the greisens, the leucogranite is pervasively sericitized.
The alteration process involved the replacement of K-feld-
spar by albite and subsequently the replacement of albite
by muscovite and quartz (quartz-sericite greisen). Mus-
covite was finally replaced by topaz to form quartz-topaz
greisen.
Williams-Jones and Kontak (1998) provided chemical
data for core samples from an 851 m drillhole that extends
20 Exploration and Mining Geology, Vol. 19, Nos. 12, p. 1322, 2010
Fig. 6. K2O/Al2O3 vs. Na2O/Al2O3 molar ratio plot of degrees of alteration
in the upper 750 m of the San Rafael tin deposit, Peru.
downward from greisen at the surface to weakly sericitized
leucogranite at depth. The alkali/alumina data are plotted
in Figure 7, where the sequence from weakly and per-
vasively sericitized leucogranite through the three main
stages of alteration are shown by arrows as follows: (1)
K-feldspar to albite, (2) albite to quartz-sericite, and (3)
sericite (muscovite) to quartz-topaz. Figure 7b shows the
changes in K2O/Al2O3 relative to depth within the drillhole.
The cassiterite deposit occurs between 0 m and 100 m from
the collar of the hole.
The least altered leucogranite at about 850 m depth (Fig.
7b) was described by Williams-Jones and Kontak (1998)
as a homogeneous assemblage of quartz, muscovite, albite,
and K-feldspar. The leucogranite becomes increasingly
sericitized upward as a result of replacement of K-feldspar
by sericite. The decrease in K2O/Al2O3 in the leucogranite
(Lg) as predicted by reaction 1 is shown in Figure 7a,b
(more clearly on 7b). This decrease K2O/Al2O3 in the leuc-
ogranite does not involve a significant increase in Na2O/
Al2O3.
The initial alteration of sericitized leucogranite involved
replacement of K-feldspar by albite (reaction 5, going to
the left), resulting in a decrease in K2O/Al2O3 and a small
increase in Na2O/Al2O3 (trend 1 in Fig. 7). The samples of
rocks showing albitization, which contain quartz, musco-
vite, and albite, lie on or near the albitemuscovite join of
Figure 7a. Replacement of albite by muscovite and the for-
mation of quartz-muscovite greisen is represented by trend
2, where K2O/Al2O3 increases and Na2O/Al2O3 decreases
as predicted by reaction 6. Subsequent leaching of K+ ions
from muscovite to form topaz (reaction 4) is manifested
by trend 3.
Fig. 7. a. K2O/Al2O3 vs. Na2O/Al2O3 molar ratio diagram showing altera-
tion trends (arrows) in leucogranite (Lg) hosting the greisen tin deposit,
Kemptville, Nova Scotia, Canada. b. K2O/Al2O3 trends relative to dis-
tance from collar of drillhole from which samples were taken.
The trends displayed in Figure 7a,b correspond closely
to the mineralogical changes reported by Williams-Jones
and Kontak (1998).
Discussion
Alkali/alumina binary molar ratio plots, unlike separate
ternary chemical and ternary mineralogical diagrams, por-
tray both chemical and mineralogical trends on the same
diagram, thus facilitating interpretation of alteration data.
K2O/Al2O3 versus Na2O/Al2O3 diagrams are particularly
useful for rocks consisting dominantly of quartz, feldspars,
and micas. Examples are altered rhyolites hosting VHMS
deposits (Davies and Whitehead, 2006) and granites, quartz
monzonites, and granodiorites hosting porphyry deposits.
In most of the cases considered in this paper, the chem-
icalmineralogical trends portrayed by the molar ratio dia-
grams agree well with the observed mineralogical changes
accompanying alteration.
However, in some examples, the plots do not support
the mineralogical changes reported: for example Bingham
(Fig. 2) and Sibert (Fig. 5). Many samples from the actino-
lite-chlorite alteration zone at Bingham have considerably
higher K2O/Al2O3 values than the least-altered quartz mon-
zonite, and some samples coincide with the quartz-ortho-
clase-phlogopite alteration (Fig. 2). However, authors of
papers on Bingham (e.g., Lanier et al., 1975, 1978) made
 Alkali/alumina Molar Ratio Trends in Altered Granitoid Rocks Hosting Porphyry and Related Deposits J.F. Davies and R.E. Whitehead 21
no mention of a hydrothermal K-bearing mineral in the
actinolite-chlorite zone. This suggests the possible failure
to recognize introduced hydrothermal orthoclase.
The difference between the molar ratio and field-petro-
graphic interpretations of alteration of the Sibert deposit
(Fig. 5) are striking. If the petrographic interpretation mis-
identified the feldspars, that is K-feldspar versus plagio-
clase, the reason might have been the result of a sericite
alteration that obscured the optical properties of the feld-
spars. In any case, the molar ratio interpretation cannot be
reconciled with the petrographic interpretation of the ori-
ginal authors, Beaufort and Meunier (1983).
Kontak and Clark (2002) employed staining tech-
niques in an attempt to alleviate the problem of identify-
ing feldspars in a pervasively altered granitoid rock at the
San Rafael lode tin deposit. That this approach appears to
have been only partially successful is suggested by an al-
kali/alumina molar ratio plot of fresh to strongly altered
samples (Fig. 6). Pervasive alteration was mainly potas-
sic with some isolated areas of albitization. Most samples
plot where expected on the alkali/alumina diagram, but two
samples of moderately altered rocks and one identified as
strongly altered plot in the same region as fresh granite.
This study has shown that alkali/alumina molar ratio
plots are a convenient way of correlating chemical and
mineralogical characteristics in altered granitoid rocks
hosting porphyry ore deposits and in identifying possible
discrepancies between chemistry and mineralogical iden-
tification.
Alkali/alumina molar ratio plots make a significant con-
tribution to the study of hydrothermal alteration whether or
not trace element data are available.
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