Fluid inclusion volatile analysis by heated crushing, on-line gas chromatography; applications to Archean fluids

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Abstract

Eighteen fluid inclusion volatile peaks have been detected and identified from 1–2-g samples (quartz) by gas chromatography using heated (∼ 105°C) on-line crushing, helium carrier gas, a single porous polymer column (HayeSep R; 10′ × 1/8″; 100/120#; Ni alloy tubing), two temperature programme conditions for separate sample aliquots, micro-thermal conductivity (TCD) and photoionization detectors (PID; 11.7 eV lamp) and off-line digital peak processing. In order of retention time these volatile peaks are: N2, Ar, CO, CH4, CO2, C2H4, C2H6, C2H2, COS, C3H6, C3H6, C3H4 (propyne), H2O (22.7 mins at 80°C), SO2, ±iso-C4H10±C4H8 (1-butene) ± CH3SH, C4H8 (iso-butylene), (?) C4H6 (1,3 butadiene), and ±n-C4H10 ±C4H8 (trans-2-butene) (80°C and −70°C temperature programme conditions combined). H2O is analysed directly. O2 can be analysed cryogenically between N2 and Ar, but has not been detected in natural samples to date. H2S, SO2, NH3, HCl, HCN and H2 cannot be analysed at present. Blanks determined by crushing heat-treated Brazilian quartz (800–900°C/4hrs) are zero for 80°C temperature programme conditions, except for a large, unidentified peak at ∼ 64 mins, but contain H2O, CO2 and some low molecular weight hydrocarbons at −70°C temperature conditions due to cryogenic accumulation from the carrier gas and subsequent elution. TCD detection limits are ∼30 ppm molar in inclusions; PID detection limits are ∼ 1 ppm molar in inclusions and lower for unsaturated hydrocarbons (e.g. ∼ 0.2 ppm for C2H2; ∼ 0.3 ppb for C3H6). Precisions are ∼±1–2%, except for H2O (∼±13%). Major fluid inclusion volatile species have been successfully analysed on a ∼50 mg fluid inclusion section chip (∼ 7 m × ∼ 10 m × ∼ 100 μm).

Two distinct end-member Archean fluids, one internal and one external, have been found related to the Tanco zoned, granitic pegmatite, SE Manitoba. The former is an H2O (∼96%)-CO2 (∼40%)-CH4-N2 fluid (S species not included) with a moderate salinity of 6.6 ± 1.3 eq. wt.% NaCl which is interpreted to be magmatic in origin, whereas the latter is an H2O (∼97%)-CH4 (∼2%)-CO2 (∼0.4%)-C2H6-N2 fluid with a distinctly higher salinity of ∼10–20 eq. wt% NaCl which is interpreted to be of metamorphic/lower crustal (∼2,900 bar/∼10km) origin. The volatile compositions of H2O (∼87–94%)-CO2 (∼6–13%)-CH4-N2 fluids with ∼5–6 eq. wt.% NaCl from primary inclusions from three structurally controlled, mafic-ultramafic rock hosted Archean Au-quartz vein deposits in the Barberton greenstone belt, southern Africa (n=9) are distinctly different from the composition of the Tanco external fluid, but similar to the composition of primary fluids of interpreted

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