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1322, 2010
2010 Canadian Institute of Mining, Metallurgy and Petroleum.
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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 identication based on molar ratios coincides with petrographic data. In those instances where the molar
ratio and petrographic identications do not agree, the mineralogy might need to be re-examined.
Hydrothermal alteration studies using trace elements could benet from the application of complementary 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 clairement les changements chimiques et minralogiques qui accompagnent les altrations potassique,
phyllique, argillique, chloritique, and alunitique des monzonites quartz et des granodiorites encaissant 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 identier divers types daltration. Dans
la plupart des cas, lidentication 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 ptrographiques, il peut tre ncessaire de rexaminer la minralogie. Les tudes de laltration hydrothermale accompagnes dune tude des lments traces auraient avantage utiliser un diagramme
des rapports molaires alkali/alumine. 2010 Canadian Institute of Mining, Metallurgy and Petroleum. All rights reserved.
1 Department of Earth Sciences, Laurentian University, Ramsey Lake Road, Sudbury, Ontario, P3E 2C6.
Corresponding Author: E-mail: rmehes@laurentian.ca
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Exploration and Mining Geology, Vol. 19, Nos. 12, p. 1322, 2010
Introduction
Alkali/alumina Molar Ratio Trends in Altered Granitoid Rocks Hosting Porphyry and Related Deposits J.F. Davies and R.E. Whitehead
Sericite to alunite:
KAl3Si3O10 (OH) 2 + 4H + + 2SO 4
2 m KAl(SO 4 ) 2 (OH)6 + 3SiO 2
(3)
Muscovite to topaz:
(4)
(5)
Albite to muscovite:
3NaAlSi3O8 + K + + 2H + m KAl3Si3O10 (OH) 2 + 3Na + + 6SiO 2
(6)
Albite to Na-montmorillonite:
(7)
1.17NaAlSi3O8 + H + m
0.5Na 0.33 Al2.33Si3.67 O10 (OH) 2 + 1.67SiO 2 + Na
Na-montmorillonite to kaolinite:
Na 0.33 Al2.33Si3.67 O10 (OH) 2 + 3H 2 O m
(8)
Molar Na2O/Al2O3
Albite
1.00.8
Oligoclase
0.80.6
Andesine
0.60.33
Labradorite
0.330.12
Bytownite
Anorthite
0.120.05
0.050.00
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Exploration and Mining Geology, Vol. 19, Nos. 12, p. 1322, 2010
Alkali/alumina Molar Ratio Trends in Altered Granitoid Rocks Hosting Porphyry and Related Deposits J.F. Davies and R.E. Whitehead
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 predominantly 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 alteration assemblages as (a) moderate potassic, (b) strong potassic, (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 rst, K+ metasomatism to produce moderate potassic alteration (a), and then to
strong potassic alteration (b), followed by H+ metasomatism 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 (reaction 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 Kfeldspar or plagioclase (or both) were involved in the production of the quartz-sericite assemblages. They do, however, note that the argillic assemblages resulted from the
replacement of plagioclase by clay minerals such as montmorillionite, kaolinite, pyrophyllite, and dickite (some examples 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 assemblage (e) do not suggest moderate argillic alteration,
nor does the presence of quartz and sericite. The explanation 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 correspond well with the description of the alteration assemblages.
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-
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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 Zijinshan Cu-Au deposit, China, showing alteration trends: a. weakly altered phyllic argillic; b. argillic alunite and argillic silicic.
replaced by sericite. Within the intermediate zone plagioclase has been completely replaced by sericite, biotite has
been partially replaced by phlogopite and sericite, whereas 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 completely 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 innermost quartz-sericite zone. The pattern portrays a continuous decrease in molar Na2O/Al2O3 and K2O/Al2O3 toward
the innermost phyllic zone. However, this pattern cannot
be reconciled with the interpretation based on eld 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 plagioclase to sericite, leaving K-feldspar unaffected, K+ ions
must have been added from the uid. The decrease in K2O/
Al2O3 suggests that this could not have been the case. From
where, then, were the K+ ions obtained? Alteration of Kfeldspar to muscovite might have released K+ ions (reaction
1) in sufcient quantities to be only partially consumed in
the alteration of plagioclase (reaction 6). The remainder of
the K+ ions would have stayed in the uid 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. Furthermore, X-ray analysis of mica akes did not reveal the presence of paragonite in samples from the intermediate zone.
The absence of plagioclase and paragonite imply the absence of Na2O. Yet Figure 5 reveals a Na2O/Al2O3 value
of about 0.25, suggesting the presence of unaltered plagioclase.
The two discrepancies between molar ratio patterns and
petrographic data might be attributed to misidentication
of the feldspars, a not unlikely possibility considering the
degree of sericitization imposed on these minerals. However, 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 Beaufort 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 conned
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
Fig. 5. K2O/Al2O3 vs. Na2O/Al2O3 molar ratio plot of the phyllic alteration 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.
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Exploration and Mining Geology, Vol. 19, Nos. 12, p. 1322, 2010
Fig. 7. a. K2O/Al2O3 vs. Na2O/Al2O3 molar ratio diagram showing alteration trends (arrows) in leucogranite (Lg) hosting the greisen tin deposit,
Kemptville, Nova Scotia, Canada. b. K2O/Al2O3 trends relative to distance from collar of drillhole from which samples were taken.
Discussion
Alkali/alumina binary molar ratio plots, unlike separate
ternary chemical and ternary mineralogical diagrams, portray 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 chemicalmineralogical trends portrayed by the molar ratio diagrams 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 actinolite-chlorite alteration zone at Bingham have considerably
higher K2O/Al2O3 values than the least-altered quartz monzonite, and some samples coincide with the quartz-orthoclase-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
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