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fractional crystallization
Roger Mustard* Predictive Mineral Discovery Cooperative Research Centre, Economic Geology Research Unit, School of
Earth Sciences, James Cook University, Townsville, QLD 4811, Australia
Thomas Ulrich* Earth and Marine Science Department, Australian National University, Canberra, ACT 0200, Australia
Vadim S. Kamenetsky School of Earth Sciences and Centre for Ore Deposit Research, University of Tasmania, GPO Box
252-79, Hobart, TAS 7001, Australia
Terrence Mernagh Geoscience Australia, GPO Box 378, Canberra, ACT 0200, Australia
q 2006 Geological Society of America. For permission to copy, contact Copyright Permissions, GSA, or editing@geosociety.org.
Geology; February 2006; v. 34; no. 2; p. 8588; doi: 10.1130/G22141.1; 4 figures; 1 table; Data Repository item 2006022. 85
Figure 3. Repre-
sentative silicate-
melt inclusions in
quartz and time-
resolved laser ab-
lation inductively
coupled plasma
mass spectrometry
(LA-ICP-MS) spec-
tra of unexposed
inclusion. A:
Silicate-melt inclu-
sions define pri-
mary growth zone
within 4-mm-
diameter magmatic
Figure 2. Rb/Sr vs. SiO2 plot from whole- quartz grain zone
rock data of different zones in Timbarra plu- 6. B: Large primary
ton. Data display coherent fractionation silicate-melt inclu-
trend of increasing Rb/Sr with increasing sion containing 1
SiO2. 2 mm molybdenite
daughter crystal
(identified using la-
and intruded each other. Upon emplacement ser Raman spec-
troscopy). Most
the melts underwent in situ crystal fraction-
common phase as-
ation. The early granitic zones are character- semblages within
ized by low contents (,1%) of magnetite, ti- melt inclusions
tanite, and ilmenite, whereas the later zones comprise crystals
contain trace magnetite and ilmenite. of mica, albite (>50
vol%), quartz, ru-
Primary magmatic quartz for silicate melt
tile, pyrophyllite,
inclusion analysis was selected from each of calcite, vapor bub-
the seven distinctive zones. The melt inclu- bles, and intersti-
sions range from 5 mm to ;150 mm and con- tial liquid. Less common phases include biotite, phenacite (Be2SiO4), apatite, tourmaline,
tain numerous solid phases (Fig. 3) that were zircon, senarmontite (Sb2O3), scheelite (CaWO4), wulfenite (PbMoO4), hematite, sassolite/
boric acid (H3BO3), molybdenite, sphalerite, and stibnite. Unidentified opaque with spectrum
distinguished by Raman spectroscopy. The
peak at 250 is thought to be PbBiTe mineral based on Raman analysis. The majority of vapor
quartz phenocrysts show no signs of resorp- bubbles have relatively constant bubble/inclusion volume ratio of 5 vol%, contain no de-
tion or recrystallization or different genera- tectable gases, and are interpreted to represent shrinkage bubbles. Occasionally, larger
tions of melt inclusions. Based on this and the bubble/inclusion volume ratios of 2030 vol% are observed with CO2, >N2, >CH4. C: LA-ICP-
chemical evolution of the Rb/Sr in the melt MS spectra for gold-bearing silicate melt inclusion from zone 6. Note that gold peak has
strong spatial association with Bi, Sb, Sn, W, and Mo.
inclusions, we are confident that the trapped
melt is representative of the zones in which
the inclusions are found. All inclusions were tative information on the daughter phases and and concentrated in those phases rather than
analyzed in quartz, which commonly is a late element affinities could be obtained by obser- dissolved in the silicate melt. Very small
phase to crystallize, and thus minimizes the vation of consistently overlapping peaks in the opaque phases were also found in some melt
chance of trapping melt from a much earlier spectra. For example, a strong Au affinity for inclusions from the most fractionated zones 6
stage in the system. (Ca)-Fe-Ti phases and an unidentified Pb-Bi- and 7, indicating that oxides were present
Te phase has been deduced from overlapping throughout the fractionation.
ANALYTICAL METHODS peaks in several LA-ICP-MS spectra. This is
Individual melt inclusions were analyzed by consistent with the observation that free gold METAL ENRICHMENT DURING
laser ablation inductively coupled plasma occurs in spatial association with Pb-Bi and FRACTIONATION
mass spectrometry (LA-ICP-MS) in quartz Ag-Bi tellurides in the ore zones (Mustard, The results of the melt inclusion analyses
crystals that showed very low trace element 2001). from each increasingly fractionated zone are
content. To quantify the data we used K as an Gold was detected in melt inclusions ana- shown in Figure 4. To assess the metal behav-
internal standard from whole-rock analyses lyzed from the most fractionated phase of the ior during fractionation we compared the Sn,
and microprobe analyses of homogenized and pluton (zone 6B) averaging 0. 12 ppm Au Mo, W, Bi, As, Sb, Cu, Pb, Zn, and Au con-
exposed melt inclusions. A detailed descrip- (range 0.020.96 ppm, Table DR2; see foot- centrations in the whole rock (Table DR1; see
tion of the data processing is given in the Data note 1). These Au values are in agreement footnote 1) and in the melt inclusions for each
Repository (see footnote 1). with the range of experimentally determined zone (Table 1). Although Sn, W, Mo, As, Sb,
gold solubilities in rhyolitic melts in the pres- and Bi are known to be compatible in minerals
GOLD CONTENT OF SILICIC MELT ence of Fe-oxides (Simon et al., 2003). One like titanite, ilmenite, and magnetite (Candela
INCLUSIONS melt inclusion from zone 4C and three from and Bouton, 1990; Tacker and Candela, 1987),
Average melt inclusion concentrations of zone 6B returned very high Au concentrations or in a fluid phase, all metals are either en-
the individual zones are shown in Table 1 and (range 1. 217.2 ppm, Table DR2; see foot- riched in the melt inclusions, that is the resid-
single inclusion analyses from the most frac- note 1) and were excluded from the average. ual melt, or are equal to the concentration of
tionated zone 6B are given in Table DR2 (see These inclusions contained large visible the whole rock (e.g., base metals Pb, Zn). This
footnote 1). The nonhomogenized melt inclu- opaque phases (Pb-Bi-Te and Ca-Ti phases as indicates a generally incompatible behavior of
sions contained several daughter phases and a inferred from the LA-ICP-MS spectrum). The the metals during crystal fractionation at
shrinkage bubble. They showed complex LA- high values are most likely related to a nug- Timbarra.
ICP-MS spectra (Fig. 3) from which quanti- get effect, in which Au is both attached to In order to infer the evolution of those met-
Zone Zone 1 Zone 2 Zone 3 Zone 4A Zone 4B Zone 4C Zone 5A Zone 5B Zone 6A Zone 6B Zone 7
avg stdv avg stdv avg stdv avg stdv avg stdv avg stdv avg stdv avg stdv avg stdv avg stdv avg stdv
n5 9 11 16 10 18 20 10 16 12 31 13
87
(520 3) during fractionation compared to the
base metals Zn, Pb, and Cu (13 3). Gold
shows a slightly higher enrichment factor (40
zone (6B). The whole-rock metal content of