Pyrite isotope ratios

Komuro, K. and Sasaki, A. (1985) Sulfur isotope ratio of framboidal pyrite in Kuroko ores from the Ezuri mine, Akita Prefecture, Japan. Mining Geology, 35, 289-293. 

Fig. 2.56. Sulfur isotope ratios of pyrite from the deposits of the Fujimi and Fudotaki groups of the Hitachi mine (Kase and Yamamoto, 1985).

Sulfur, carbon and hydrogen stable isotope ratios of pyrite, kerogens, and bitumens of two high-sulfur Monterey formation samples from the onshore Santa Maria Basin in California were determined. Kerogens from these were pyrolyzed at 300°C for periods of 2, 10 and 100 hours in closed systems and the yields and isotopic compositions of S-containing fractions (residual kerogens, bitumens and hydrogen sulfide) were determined. 

Sulphur isotopic ratios were measured on two samples from Murgental and Altishofen (Lower Freshwater Molasse). In the pervasive pyrite cements from Murgental, both the edge and the centre of a patch were measured, yielding cdt (Canyon Diablo Troilite) values of -14.4%o and +1.1 %o, respectively. In Altishofen, two spots of mica replacement were measured, yielding 6 S cdt values of-28.1%0 and -22.1%o. 

Several lines of evidence suggest the involvement of TSR. Partially dissolved remnants of early diagenetic anhydrite cement are found embedded in quartz cement (Fig. 12). Fluid inclusion data indicate that nodular quartz cement with anhydrite inclusions (Fig. 15) formed at elevated temperatures, suggesting that anhydrite dissolution may have coincided with high temperature TSR. Post-pyrobitumen carbonate and pyrite cements and nodules are also present in the Norphlet and may represent late diagenetic precipitates associated with TSR. Pyrite cement from the Norphlet has sulphur isotope ratios that are identical to those of the Pine Hill Anhydrite (Table 3) and within the range reported for Jurassic seawater (Hoefs... 

Two Type II-S kerogens (as defined by Orr (i)) from the onshore Santa Maria Basin Monterey formation were pyrolyzed in this study to determine (a) the distribution of sulfur and its isotopic composition among the various products formed during artificial maturation, and (b) maturation trends reflected in the sulfur isotopic and elemental S/C ratios of kerogens, and in the variation of C and H isotopes. In addition, S isotopes in pyrites, kerogens and bitumens from the two Monterey shale samples were examined to speculate on the mode of S incorporation into Santa Maria Basin sediments. 

In addition to SO2 self-shielding many other possible sources of S-MIF can be identified. The model A S/results for the case of a I0W-O2 atmosphere (e.g.. Figure 5.7b) are in qualitative but not quantitative agreement with the ancient rock record. Elemental S, derived from S(D, is predicted here to have > 0 and < 0, which is consistent with observations of most pyrites [4], but the magnitude of the A S/A S ratio is about a factor of 2 to 3 too high ( -2.5 vs. 0.9). This is a significant discrepancy, and may indicate that MI processes in addition to SO2 photodissociation are at work. One such MI process almost certain to be important in a I0W-O2 atmosphere is SO photodissociation. Isotope-selective photolysis will occur in SO at wavelengths 190-230 nm, but rotationally-resolved spectra, either laboratory or synthetic, are needed to estimate the MI effect. In addition to S-MIF due to SO photolysis, SO2 photoexcitation ( 280-330 nm) and SO3 photolysis [18] must also be considered as possible contributors to S-MIF in the ancient atmosphere. S-MIF due to these photo-processes will be considered in future work. 

Details of sulfur isotope geochemistry are presented elsewhere in this volume (see Chapter 7.10) and are only highlighted here as related to paleo-environmental interpretations of finegrained siliciclastic sequences. Formation of sedimentary pyrite initiates with bacterial sulfate reduction (BSR) under conditions of anoxia within the water column or sediment pore fluids. The kinetic isotope effect associated with bacterial sulfate reduction results in hydrogen sulfide (and ultimately pyrite) that is depleted in relative to the ratios of residual sulfate (Goldhaber... 

Most of the information on S S values of the reduced sulfur in sediments derives from both acid volatile sulfide (FeS) and pyrite (Fe 2). In a few cases, both sulfate and other sulfur species were isotopically compared. Due to analytical difficulties, organic sulfur and elemental sulfur isotope (S S) ratios were studied only in cases where the secondary enrichment led to OM rich in sulfur. This secondary enrichment forms type II-S kerogens. 

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