PORPHYRY COPPER ENRICHMENT LINKED TO

EXCESS ALUMINIUM IN PLAGIOCLASE

BY SWAGATA CHAKRABORTY
15GG61R16
Mtech. I year
IIT Kharagpur

PORPHYRY Cu-DEPOSIT : AN EXSISTING MODEL

Porphyry Cu-Mo deposits are formed in association with of oxidized I-type,
calc-alkaline magmas, generated adjacent to subduction zones.
Some melt extrude on the
surface crystallize to form
volcanic porphyry suites

At low load pressures the

saturation water content is
relatively low and almost equal
to initial water content :
Vapor-saturation occur early in
the crystallization sequence.

Magma with a relatively low

initial H2O content, rising to
high levels in the crust before
significant crystallization

The vapor phase characterized by

high Cl concentrations efficiently
scavenge Cu from the silicate
melt.

Even though Cu is a compatible

(w.r.t granitic melt), the lack of
crystallization allows very little of
Cu to have been removed till
saturation time.

CASE STUDY: PLAGIOCLASE FROM FERTILE LA

PALOMA AND LOS SULFATOS COPPER PORPHYRY
SYSTEMS , CHILE

Magmatic plagioclase from fertile

(Cu-rich)areas contains excess Al in
comparison to barren Soufrire Hills.

The blue line joining pure albite and anorthite

end members, separates analyses from fertile
system
(excess Al) from barren ones.

Surface or subsurface calc-alkaline rocks

could be individually assessed for plagioclase
excess Al as a low-cost exploration tool.

Fig1: An% versus Al/(Ca+Na+K) from data sets of fertile and barren
systems. The blue line joins albite and anorthite end members.
Source: Reference1

Excess Al as a cause of alteration is ruled out :

Data from the case study mostly fall along the tie line
between albite and anorthite, with very little shift
towards common alteration phases in porphyry systems.

Exception are two groups of

data(with>65wt% SiO22 ) show partial
alteration to muscovite but also shows
low An values (<10%).

Fig2: SiO2 versus CaO+Na2O+K2Owt% showing trajectories towards common plagioclase

alteration phases. Source : Reference1

Moreover plagioclase alteration is patchy, along cleavages or concentrated in high-An

regions. Here excess Al occurs within discrete (relatively low An) concentric zones strongly
suggesting formation by magmatic processes.

EXPLANATION FOR EXCESS ALUMINIUM

General Formula of Plagioclase: (Na,Ca)(Si,Al)4O8
M-site

T-site

Fig4: Ca+Na+K versus Al+Si (a.p.f.u.) showing trajectories towards plagioclase endmembers. Blue cross indicates the ideal
plagioclase, K-feldspar. Error bars (red crosses)

Explanation for excess Al

Substitution of AlAl3SiO8,with cosubstitution of [ ]Si4O8 (where
[ ] =defect on the M site).

Lines of Evidence in support

Compositions mainly lie above the maximum tetrahedral
T-site occupancy of 4 a.p.f.u. (Si+Al), implying that Al
must also be contained within large cation (M-)sites.
Trend of decreasing Ca+Na+K with increasing Si+Al,
suggesting substitution of Al for Ca and Na in M-sites.

EXPLANATION FOR EXCESS ALUMINIUM

Fig5: Excess Al versus Sr/Y. Souce : Reference1

Explanation for excess Al

Excess Al results from high melt

PH2O

Lines of evidence in support

Large vacancies in [ ]Si4O8 are commonly occupied
by H2O, suggesting high PH2O : literature data for hydrothermal
plagioclase (crystallized from H2O-dominated fluids)contain
excess Al.
Excess Al increases with Sr/Y in plagioclase from the pre- to
late-mineralization porphyries: high melt (whole rock) Sr/Y
(inherited by plagioclase) result from elevated PH2O, which
reduces Y via amphibole fractionation & increases Sr due to the
initial suppression and late stage enhanced crystallization of
plagioclase.

Conclusion : Which Calc-Alkaline systems host porphyry Cu-Deposits ?

Exploration Tool: The case study plagioclase shows
increase in AlAl3SiO8 and [ ]Si4O8 and Sr/Y through the
pre- to late-mineralization porphyries, but no increase in
Cu, (average 0.5 ppm), significantly lower than in
plagioclase from barren rocks.
A paradox: Assuming that plagioclase compositions
reflect those of surrounding melts, melt Cu showed no
discernible increase as the system fractionated to higher
Sr/Y; Cu is incompatible in most crystallizing phases so
should increase with fractionation.

Fig6: Excess Al versus Cu ppm ; Source: Reference1

Explanation by previous study: Loss of Cu to an exsolving aqueous phase.

Additional mechanism proposed: The substitution ofAlAl3SiO8 with [ ]Si4O8 and H2O excludes
Cu from plagioclase M-sites. This would enhance Cu incompatibility in plagioclase and so
progressively enrich residual melts and exsolving aqueous fluids.

Conclusion: Whether high-level magma chambers have undergone addition

of H2O-rich melts, producing the high PH2O necessary for Porphyry CuDeposit formation ?
Models proposed for La Paloma & Los Sulfatos: A higher level
chamber (4-10 km depth) and porphyry apophyses that rise to 1-4
km from surface.
Owing to the presence of excess Al in plagioclase, Cu was
particularly incompatible and therefore highly enriched in late
stage melts.
Presence of spatially distinct zones of low Sr/Y and Al, and high
Cu and An, in plagioclase evidences:
The higher chamber was periodically re-fertilized with Cu due
to ingress of less evolved melts.
Injection of less evolved melts was interspersed with intrusions of
hydrous fluids.
Melt H2O contents progressively rose, with periods of fluid
exsolution to produce conventional porphyry mineralization.
Fig7:Section through La Paloma and Los Sulfatos brecciadominated porphyry systems; Source : Reference1

REFERENCES

1. Williamson, B.J, Herrington ,R.J. & Morris A, Porphyry

copper enrichment linked to excess aluminium in plagioclase.
Nature Geosci. 9, 237-241(2016).
2. Kyono, A. & Kimata, M. Refinement of the crystal structure
of a synthetic non-stoichiometric Rb-feldspar. Mineral. Mag.
65, 523-531 (2001).
3. Introduction to Ore-Forming Processes, by Laurence Robb

THANK YOU

Fig3: Quantitative X-ray maps of plagioclase phenocrysts from an

inter-mineralization Porphyry. Black and white arrows point to low
An with high excess Al zones, and high An with low excess Al
zones, respectively. ; Source: Reference1