Hydrogen and carbon isotopes of petroleum and related organic matter

$\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios were measured for 114 petroleum samples and for several samples of related organic matter. δD of crude oil ranges from ?85 to ?181‰, except for one distillate (?250‰) from the Kenai gas field; δ¹³C of crude oil ranges from ?23.3 to ?32.5‰, Variation in δD and δ¹³C values of compound-grouped fractions of a crude oil is small, 3 and 1.1%., respectively, and the difference in δD and δ¹³C between oil and coeval wax is slight. Gas fractions are 53–70 and 22.6–23.2‰ depleted in D and ¹³C, respectively, relative to the coexisting oil fractions.The δD and δ¹³C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant.     

The enrichment of 34S in the solfataras of the Nea Kameni volcano,Santorini archipelago,Greece

Sulfur isotope investigations carried out on elemental sulfur and sulfates of the Nea Kameni solfataras, Santorini, Aegean Sea, Greece, show a clear enrichment in the heavy sulfur isotope ³⁴S against the assumed primordial ${}^{32}\text{S}{}^{34}\text{S}$ ratio of 22,220. Within the same crater, different vents, only a few meters apart from each other, produced δ differences up to 10‰, which remained constant for several years. This enrichment is most probably due to contamination by heavy sulfur from a nonvolcanic source. An enrichment in the same order of magnitude was observed in sulfur of recent and older lavas ($\text{δ}{}^{34}\text{S}\text{= ?1 ? +11‰}$).Potential contaminants like sulfide sulfur in hydrothermal ore veins of Athinios has a δ ³⁴S mean value close to 0‰, sulfide and sulfate in the sedimentary basement has a δ ³⁴S mean value of $\text{+2.6‰.}$ Seawater sulfate from the area gives a value of $\text{δ}{}^{34}\text{S}\text{= 20‰}$, while sulfide from bacterial reduction of pore-water sulfate in recent iron ore sediments has δ ³⁴S values between ?8 and $\text{?5‰.}$ Sulfate remaining in the pore solutions gave $\text{δ}{}^{34}\text{S}\text{= +27‰}$.The most probable explanation for the observed high δ ³⁴S values in the solfataric sulfur and in some of the lavas of the Santorini area is contamination of the volcanic vents by Mediterranean Sea water.     

Sulfur isotope study of Quaternary volcanic rocks from the Japanese Islands Arc

The sulfide and sulfate contents and their δ³⁴S values were determined in Quaternary volcanic rocks from the Japanese Islands Arc. The total sulfur contents are much lower (less than 40 ppm) and the δ³⁴S values are higher (+4.4 ± 2.1) than those of ocean-floor basalts (800 ± 100 ppm and +0.8 ± 0.5, respectively; Moore and Fabbi, 1971; Sakaiet al., 1982). Lateral variations of both sulfur content and δ³⁴S values were observed in the four volcanic belts in Japan. In the Northeast Japan belt, the sulfur content (30 ± 10 ppm) of the rocks in the inner zone (the Japan Sea side) is 3 to 5 times that in the outer zone (the Pacific side), although the δ³⁴S values of the two zones are almost the same (+4.3 ± 1.0). The δ³⁴S values for the two belts in West Japan are on the average 2%. higher than those of East Japan.This study suggests that the primary magmas that formed the island arc volcanic rocks are initially depleted in sulfur (<120 ppm) and enriched in ³⁴S ($\text{δ}{}^{34}\text{S: +5 ～ +7}$) compared to ocean-floor tholeiitic basalts which formed at mantle under oceanic region. This indicates that the upper-mantle is heterogeneous in sulfur content and isotope composition.     

Geographical trends of carbon and sulphur isotope abundances in human kidney stones

$\text{δ}{}^{13}\text{C}$ values and $\text{δ}{}^{34}\text{S}$ values in human kidney stones range from ?24 to ?10 and ?10 to + 20 %., respectively, and depend upon geographical location. Although the distributions overlap, the mean $\text{δ}{}^{13}\text{C}$ values in oxalate stones from North America become less negative with decreasing latitude. For Mexico and Hawaii, the distributions appear to be bimodal. Uric acid stones are generally enriched in ¹³C by up to 7%. in comparison to oxalates from the same location, whereas cystine stones tend to span the ranges of both stone types. The geographical trends can be explained by the relative proportions of dietary carbon derived ultimately from plants undergoing various established photosynthetic mechanisms (C₃, C₄, CAM). The differences among the various major stone types may reflect isotope fractionation during biochemical conversions.Exogenic oxalates and uric acid are considered to have little role in precipitating the respective minerals. Whereas, the currently available C isotope data support this contention, more data are desirable, particularly for ingested oxalates. In contrast, S isotope data provide strong evidence that cystine stones are derived from ingested organo-S compounds and bear no relation to inorganic sulphate consumed by the individual. In turn, these organic-S compounds were probably derived from sulphate in the hydrosphere at lower levels in the food chain, e.g., by bacterial assimilation.     

Isotopic abundances of water of crystallization of gypsum from the Miocene evaporite formation,Carpathian Foredeep,Poland

For sulfates of Miocene evaporites in the Carpathian Foredeep, the waters of crystallization of gypsum (w.c.g.) have $\text{δD = ?38 to ?113\%.}$ and $\text{δ}{}^{18}\text{O = 0 to ?11\%.}$ (SMOW). The $\text{δ}{}^{34}\text{S}$ and $\text{δ}{}^{18}\text{O}$ values of the sulfates are uniform and consistent with a marine origin. It is proposed that the original w.c.g. was equilibrated with marine water. Subsequently, it re-equilibrated towards very isotopically light water (δD ～ ?100%., δ¹⁸O ～ ?14%) during a glacial or postglacial period and is now trending towards current waters circulating through the deposits (δD ～ ?50%., δ¹⁸ ～ ?7%). The extent of reequilibration increased with decreasing crystal size.     

Chemistry and isotope ratios of sulfur in basalts and volcanic gases at Kilauea volcano,Hawaii

Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ³⁴S_Σs of $\text{0.7 ± 0.1 ‰}$. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is $\text{+7.5 ± 1.5‰}$. On the other hand, the concentration and δ³⁴S_Σs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and $\text{?0.8 ± 0.2‰}$, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the $\text{?o}{}_2$ and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO₂ from basalt thereby depleting sulfate and ³⁴S in basalt.The volcanic sulfur gases, predominantly SO₂, from the 1971 and 1974 fissures in Kilauea Crater have δ³⁴S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ³⁴S value of sulfur gases (largely SO₂) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ³⁴S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ³⁴S values (+5 to +6%._o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.     

Sulphur isotope effects in the dissociation and evaporation of troilite: A possible mechanism for 34S enrichment in lunar soils

Both the dissociation and evaporation of troilite. heated to its melting point in vacuo, are isotopically selective. The elemental sulphur from the dissociation of troilite has a ${}^{34}\text{S}{}^{32}\text{S}$ ratio which is 13.0‰ less than that of the undissociated material while the ${}^{34}\text{S}{}^{32}\text{S}$ ratio in evaporated troilite is 5.4‰ less than that of the residual material. The two processes occur simultaneously and the isotopic variations during the course of the reaction are in accord with those for a branched reaction where the unreacted material remains isotopically well-mixed, as in a Rayleigh distillation process. This isotopic selectivity must be taken into account, along with that in other lunar surface processes, when considering the heavy isotope enrichment of sulphur in lunar soils.     

Coupling among the terrestrial sulfur,carbon and oxygen cycles: numerical modeling based on revised Phanerozoic carbon isotope record

Numerical modeling of the terrestrial oxygen budget based on the revised δ¹³C_carb record by Veizeret al. (1980) has shown that total photosynthetic oxygen has varied between ±7% and ±10% of its average reservoir size (～3.2 × 10²² g) during the last 800 myr as a result of oscillations of the sedimentary reservoir of organic carbon. Calculated curves of oxygen evolution display a distinct minimum in the Early Paleozoic framed by two maxima in the Latest Proterozoic and the Mesozoic. The sympathetic relationship observed between the curves of total oxygen evolution and respective functions for the partial reservoir of sulfate-bound oxygen suggests that the O₂ required for an additional conversion of sulfide to sulfate was most probably provided by excess burial of organic carbon, the results of the modeling thus adding credence to current interpretations proposed for the negative correlation between the secular ${}^{13}\text{C}{}^{12}\text{C}$ and ${}^{34}\text{S}{}^{32}\text{S}$ trends.     

Stable isotopic investigations of early development in extant and fossil chambered cephalopods I. Oxygen isotopic composition of eggwater and carbon isotopic composition of siphuncle organic matter in Nautilus

Eggwaters from the chambered cephalopod Nautilus are depleted in both ¹⁸O and deuterium relative to ambient seawater. Eggwaters from six other species, including the related chambered cephalopod Sepia, do not show such depletion. These observations indicate that the previously observed step towards more positive $\text{δ}{}^{18}\text{O}$ values in calcium carbonate laid down after Nautilus hatches, relative to carbonate precipitated prior to hatching, can be explained by equilibration of the carbonate with water in the egg before hatching and with seawater after hatching. The presence of an oxygen isotope difference between eggwater and seawater for Nautilus and its absence for Sepia suggest that hatching will be recorded in the $\text{δ}{}^{18}\text{O}$ values of shell carbonates for some but not all extinct and extant chambered cephalopods.The $\text{δ}{}^{13}\text{C}$ values of the organic fraction of the siphuncle in Nautilus do not show any consistent pattern with regard to the time of formation before or after hatching. This observation suggests that the minimum in $\text{δ}{}^{13}\text{C}$ values previously observed for calcium carbonate precipitated after Nautilus hatches is not caused by a change in food sources once the animal becomes free-swimming, as has been suggested.     

Source rock-crude oil correlation by isotopic type-curves

An isotopic type-curve has been defined based on the ${}^{13}\text{C}{}^{12}\text{C}$ ratios of the saturated, aromatic, heterocomponent (NOSs), and asphaltene fractions of crude oils. These fractions show ¹³C enrichments with increasing polarity or polarizability. This systematic pattern can be used to estimate the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of the kerogen from which the oil had been generated. Genetically associated source rock oil pairs have been used to show that the difference between the measured and the estimated δ-values of kerogen is about ?0.5%., and between the δ-values of the kerogen and the asphaltene fraction is approximately +0.6%.     

Nitrogen isotopes in the solar system

Measurements of the isotopic composition of nitrogen in the solar system are summarized. We show that the 30% change, during the last 3 to 4 billion years, of ${}^{15}\text{N}{}^{14}\text{N}$ in solar-wind-bearing lunar soils and breccias probably does not reflect changes in this ratio at the solar surface. Such changes, whether by spallation or thermonuclear reactions are ruled out by comparing the yields of ¹⁵N with those of other rare isotopes such as ⁹Be, ¹¹B, ³He or ¹³C, even if an arbitrary degree of solar mixing is introduced. Moreover, we calculate that the solar activity required for producing significant amounts of ¹⁵N by spallation at the solar surface should have resulted in a particle bombardment of the Moon of an intensity that would have produced amounts of spallation isotopes (e.g.¹⁵N, ²¹Ne, ³⁸Ar, ¹³¹Xe) several orders of magnitude in excess of what is actually found in the whole regolith.We argue that accretion of interstellar matter also does not work as a cause for a significant change of the photospheric ${}^{15}\text{N}{}^{14}\text{N}$ ratio. Evidence is presented that the mixing depth at the solar surface on a time scale of ?10⁹ years is (10^?2 ?10^?1) M_⊙ Mixing to this depth renders accretion of interstellar matter as a source of compositional changes at the solar surface inefficient, even if allowance is made for the expected large difference in the accretion rates of condensed and gaseous matter. A quantitative treatment of several alternatives of solar accretion leads to serious contradictions (e.g. with the low Ne abundances in planetary atmospheres or with the amounts of nitrogen that should have been directly accreted by the Moon), and we conclude that accretion during the main sequence life of the Sun is an unlikely source of changes in ${}^{15}\text{N}{}^{14}\text{N}$ at the solar surface.A ratio of ${}^{15}\text{N}{}^{14}\text{N}\text{= (4.0 ± 0.3) × 10}{}^{\mathrm{?3}}$ is our best estimate for average solar system material and for the Sun. We propose that a rare, very light nitrogen component (called LPN) is admixed in varying amounts to planetary matter. Undiluted LPN has not been found in meteorites or planetary atmospheres, but we show that the combined effects of LPN admixture and isotope fractionation can in principle account for the variability of ${}^{15}\text{N}{}^{14}\text{N}$ observed in the planetary system. Determination of the Jovian ${}^{15}\text{N}{}^{14}\text{N}$ ratio with an accuracy of ~10% would crucially test our interpretation of the nitrogen isotope observations.     

Sedimentary iron monosulfides: Kinetics and mechanism of formation

The reaction between hydrous iron oxides and aqueous sulfide species was studied at estuarine conditions of pH, total sulfide, and ionic strength to determine the kinetics and formation mechanism of the initial iron sulfide. Total, dissolved and acid extractable sulfide, thiosulfate, sulfate, and elemental sulfur were determined by spectrophotometric methods. Polysulfides, S₄^2? and S₅^2?, were determined from ultraviolet absorbance measurements and equilibrium calculations, while product hydroxyl ion was determined from pH measurements and solution buffer capacity.Elemental sulfur, as free and polysulfide sulfur, was 86% of the sulfide oxidation products; the remainder was thiosulfate. Rate expressions for the reduction and precipitation reactions were determined from analysis of electron balance and acid extractable iron monosulfide vs time, respectively, by the initial rate method. The rate of iron reduction in moles/liter/minute was given by $\text{d(}\text{reduction}\text{Fe)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^{0.5}\text{(J}{}^{\mathrm{+}}\text{)}{}^{0.5}\text{A}{}_{\mathrm{FeOOH}}{}^1$ where S_t was the total dissolved sulfide concentration, (H⁺) the hydrogen ion activity, both in moles/ liter; and A_FeOOH the goethite specific surface area in square meters/liter. The rate constant, k, was 0.017 ± 0.002m^?2 min^?1. The rate of reduction was apparently determined by the rate of dissolution of the surface layer of ferrous hydroxide. The rate expression for the precipitation reaction was $\text{d(FeS)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^1\text{(H}{}^{\mathrm{+}}\text{)}{}^1\text{A}{}_{\mathrm{FeOOH}}{}^1$ where $\text{d(FeS)}\text{dt}$ was the rate of precipitation of acid extractable iron monosulfide in moles/liter/minute, and k = 82 ± 18 mol^?1l²m^?2 min^?1.A model is proposed with the following steps: protonation of goethite surface layer; exchange of bisulfide for hydroxide in the mobile layer; reduction of surface ferric ions of goethite by dissolved bisulfide species which produces ferrous hydroxide surface layer elemental sulfur and thiosulfate; dissolution of surface layer of ferrous hydroxide; and precipitation of dissolved ferrous specie and aqueous bisulfide ion.     

Hydrogen,oxygen and carbon isotopic evidence for the origin of rodingites in serpentinized ultramafic rocks

$\text{D}\text{H}$, ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ analyses were made of 14 whole rock and 28 mineral samples of rodingites associated dominantly with lizardite-chrysotile serpentinites from the West Coast of the U.S.A., New Zealand, and the Northern Appalachian Mtns. The δD values of the rodingite minerals are in three groupings: 5 monomineralic veins of pectolite, ?281 to ?429; 8 monomineralic veins of xonotlite, ?112 to ?135; all other minerals, including hydrogarnet, idocrase, prehnite, actinolite, nephrite, and chlorite, ?34 to ?80. Most calcites in rodingites have δ¹⁸O (+9.3 to +14.4) and (δ¹³C (?6.7 to +0.9) values similar to calcites in other Franciscan rocks, but distinct from the very low temperature calcite veins in serpentinites. The $\text{D}\text{H}$ data, combined with δ¹⁸O values of xonotlite (+5.7 to +10.9) and pectolite (+8.9 to +12.4) suggest formation from meteoric-type waters at low temperatures; the $\text{D}\text{H}$ depletion of pectolite, however, is anomalous. Rodingite whole rock values range from δ¹⁸O = +4.1 to +11.5 and δD = ?50 to ?86; one sample containing minor amounts of lizardite-chrysotile serpentinite has δD = ?92, outside this range. However, most rodingites of basaltic or gabbroic parentage are more restricted in δ¹⁸O (+4.1 to +8.6). Such a wide range in δ¹⁸O is consistent with the idea that most rodingites form over a relatively broad range of hydrothermal temperatures. Hydrogen isotopic data for most rodingite minerals (except xonotlite and pectolite) and for whole rocks are suggestive of non-meteoric waters. These $\text{D}\text{H}$ data overlap those observed for veins of hydrous minerals found in Franciscan igneous rocks studied by Margaritz and Taylor (1976, Geochim. Cosmochim. Acta40, 215–234), possibly suggesting evolved D-enriched, connate type metamorphic waters generated during high P, low T Franciscan-type metamorphism at temperatures (250–500°C) comparable to estimates based on mineral stabilities. Such an interpretation is supported by the ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ data for calcite in rodingites.The isotope data appear to contradict some of the conclusions derived from geologic and petrologic studies that indicate concomitant metasomatism and serpentinization of their presently observed host rock. These data appear most consistent with the interpretation that most rodingite minerals, with the exception of late-stage veins of xonotlite and possibly pectolite, may involve metasomatism in association with antigorite serpentinization of ultramafic rock. Subsequent upward tectonic transport in many instances may result in incorporation of the rodingites into their presently observed lizarditechrysotile host rock during or subsequent to pervasive shallow level serpentinization by meteoric waters.     

Carbon,nitrogen and sulfur in lunar fines 15012 and 15013: abundances,distributions and isotopic compositions

Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. In the former case, it was released by mineral grains to which it was adsorbed or from cavities within which it had been captured. Hydrogen released during hydrolysis had largely resulted from dissolution of metallic iron.By comparison of the distribution frequencies of C, N, S, H₂ and Fe with ⁴He, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteoritic contribution to these samples.Solar wind interaction also has a marked effect on the stable isotope distribution of ¹³C/¹²C, ¹⁵N/¹⁴N, and ³⁴S/³²S. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction. During stepwise pyrolysis, CH₄, CO₂, CO and N₂ were obtained at different temperatures and displayed different isotopic ratios. The carbon fraction most enriched in ¹³C, was CH₄ liberated at 600–800°C with $\text{δ}{}^{13}\text{C = +45.7\%.}$. Between 400 and 600°C, N₂ was liberated with (δ¹⁵N ≈ +119% and at 600–800°C, N₂ was liberated with $\text{δ}{}^{15}\text{N = +75\%.}$ relative to terrestrial atmospheric nitrogen.     

Experimental paleotemperature equation for planktonic foraminifera

Small live individuals of Globigerinoides sacculifer which were cultured in the laboratory reached maturity and produced garnets. Fifty to ninety percent of their skeleton weight was deposited under controlled water temperature (14° to 30°C) and water isotopic composition, and a correction was made to account for the isotopic composition of the original skeleton using control groups.Comparison of. the actual growth temperatures with the calculated temperature based on paleotemperature equations for inorganic CaCO₃ indicate that the foraminifera precipitate their CaCO₃ in isotopic equilibrium. Comparison with equations developed for biogenic calcite give a similarly good fit. Linear regression with Craig's (1965) equation yields: $\text{t = ?0.07 + 1.01}\text{t}\text{?}\text{(r= 0.95)}$ where t is the actual growth temperature and $\text{t}\text{?}$ Is the calculated paleotemperature. The intercept and the slope of this linear equation show that the familiar paleotemperature equation developed originally for mollusca carbonate, is equally applicable for the planktonic foraminifer G. sacculifer.Second order regression of the culture temperature and the delta difference (δ¹⁸Oc ? δ¹⁸Ow) yield a correlation coefficient of r = 0.95: $\text{t}\text{?}\text{= 17.0 ? 4.52(δ}{}^{18}\text{Oc ? δ}{}^{18}\text{Ow) + 0.03(δ}{}^{18}\text{Oc ? δ}{}^{18}\text{Ow)}{}^2$$\text{t}\text{?}\text{, δ}{}^{18}\text{Oc}$ and δ¹⁸Ow are the estimated temperature, the isotopic composition of the shell carbonate and the sea water respectively.A possible cause for nonequilibnum isotopic compositions reported earlier for living planktonic foraminifera is the improper combustion of the organic matter.     

Isotopic and textural discrimination between hypogene,ancient supergene,and modern sulfates at the Questa mine,New Mexico

Chemical and mineralogical changes due to pyrite weathering are of interest with respect to understanding long-term physical stability of mine rock piles at the Questa mine, New Mexico. The ability to discriminate between ancient and modern processes is important for establishing the extent of modern weathering within the piles. Initial inventories of sulfur minerals and representative isotope compositions in rocks from orebodies, the hydrothermal alteration zones associated with orebodies, hydrothermal alteration scars, and mine rock piles were determined. Ore body sulfides have δ³⁴S_CDT of 0 ± 4‰, typical for sulfides formed by magmatic processes in stockwork Mo systems. Pyrite from alteration scars has a wide range of δ³⁴S values from 0.0‰ to −13.6‰. Sulfate from the ore body has markedly positive δ³⁴S (5–10‰) accompanied by positive δ¹⁸OSO₄${\delta }^{18}{\text{O}}_{{\text{SO}}_4}$ values (6–15‰) reflecting equilibrium formation from magmatic fluids. Sulfates from alteration scars have δ³⁴S values over a broad range, similar to alteration scar pyrites, from −10.6‰ to 0‰ and δ¹⁸OSO₄${\delta }^{18}{\text{O}}_{{\text{SO}}_4}$ of 0 ± 3‰. Sulfates with fine grained, delicate, and euhedral mineral habits suggesting recent formation within the mine rock piles, have δ³⁴S values similar to orebody pyrite and alteration scars but more negative δ¹⁸OSO₄${\delta }^{18}{\text{O}}_{{\text{SO}}_4}$ values (−3‰ to −10‰). Sulfates from all three sources occur in these piles, and their stable isotope values have proven useful in differentiating them and their environments of formation (i.e., hypogene, ancient supergene, and recent weathering). Correlating the isotopic compositions with textures allows petrographic assessment for the origins of sulfate minerals in the rock piles, but this must be applied with caution because some sulfate mineral recycling has occurred.     

A corundum-rich inclusion in the Murchison carbonaceous chondrite

A corundum-hibonite inclusion, BB-5, has been found in the Murchison carbonaceous chondrite. This is the first reported occurrence of corundum as a major phase in any refractory inclusion, even though this mineral is predicted by thermodynamic calculations to be the first condensate from a cooling gas of solar composition. Ion microprobe measurements of Mg isotopic compositions yield the unexpected result for such an early condensate that ²⁶Mg excesses are small: δ_N²⁶Mg = 7.0 ± 1.6%. for hibonite and 5.0 ± 4.8%. for corundum, despite very large ${}^{27}\text{Al}{}^{24}\text{Mg}$ ratios, 130 and 2.74 × 10⁴, respectively. Within the errors, δ_N²⁶Mg does not vary over this exceedingly large range of ${}^{27}\text{Al}{}^{24}\text{Mg}$ ratios. The extreme temperature required to melt this inclusion makes a liquid origin unlikely, except possibly by hypervelocity impact involving refractory bodies. If, instead, BB-5 is a direct gas-solid condensate, textural evidence implies that corundum formed first and later reacted to produce hibonite. In this model, BB-5's uniform enrichment in ²⁶Mg must be a characteristic of the reservoir from which it condensed. Because severe difficulties are encountered in making such a reservoir by prior decay of ²⁶Al, nebular heterogeneity in magnesium isotopic composition is a preferred explanation.     

Sulphur isotope geochemistry of carbonatites

Sulphur isotopic data for sulphides and barite from several carbonatites (Mountain Pass, Oka, Magnet Cove, Bearpaw Mountains, Phalabora) show that individual carbonatites have different mean sulphide or barite isotopic compositions which deviate from the meteoritic mean $\text{δ}{}^{34}\text{S(0‰)}$.Classification of carbonatites in terms of T,?O₂ and pH during formation of the sulphur-bearing assemblages indicates that with decreasing T and increasing relative ?O₂ the mean δ³⁴S sulphide becomes increasing negative relative to the mean magma δ³⁴S. Only barite-free high temperature carbonatites (Phalabora) in which the mean δ^34S sulphide approaches the mean magmaδ³⁴S as a consequence of the paucity of oxidized anionic sulphur species in the magma can be used to directly estimate the mean isotopic composition of the source material.Barites from the Mountain Pass carbonatite show an increase in δ³⁴S with sequence of intrusion of the carbonatite units; dolomitic carbonatite (mean δ³⁴S, + 5.4‰), calcitic carbonatite (+ 4.8%.), silicified carbonatite (+ 6.9‰), tabular carbonatite dikes (+ 8.7‰), mineralized shear zones (+ 9.5‰). Within each of these units a spread of 6.8%. is evident. Isotopic trends in this low temperature (300°C) carbonatite are evaluated by treating the system as a hydrothermal fluid. The observed isotopic variations can be explained by removal of large amounts of sulphur from a fluid whose mean δ³⁴S is 0 to + 1‰     

Isotopic evidence for the origin of sulfur in the Herrin (no. 6) coal member of Illinois

The sulfur isotopic composition of the Herrin (No. 6) Coal from several localities in the Illinois Basin was measured. The sediments immediately overlying these coal beds range from marine shales and limestones to non-marine shales. Organic sulfur, disseminated pyrite, and massive pyrite were extracted from hand samples taken in vertical sections.The $\text{δ}{}^{34}\text{S}$ values from low-sulfur coals (< 0.8% organic sulfur) underlying nonmarine shale were +3.4 to +7.3%₀ for organic sulfur, +1.8 to +16.8%₀ for massive pyrite, and +3.9 to +23.8%₀ for disseminated pyrite. In contrast, the $\text{δ}{}^{34}\text{S}\text{values from high-sulfur coals}$ (> 0.8% organic sulfur) underlying marine sediments were more variable: organic sulfur, ?7.7 to +0.5%₀, pyrites, ?17.8 to +28.5%₀. In both types of coal, organic sulfur is typically enriched in ³⁴S relative to pyritic sulfur.In general, δ ³⁴S values increased from the top to the base of the bed. Vertical and lateral variations in δ ³⁴S are small for organic sulfur but are large for pyritic sulfur. The sulfur content is relatively constant throughout the bed, with organic sulfur content greater than disseminated pyrite content. The results indicate that most of the organic sulfur in high-sulfur coals is derived from post-depositional reactions with a ³⁴S-depleted source. This source is probably related to bacterial reduction of dissolved sulfate in Carboniferous seawater during a marine transgression after peat deposition. The data suggest that sulfate reduction occurred in an open system initially, and then continued in a closed system as sea water penetrated the bed.Organic sulfur in the low-sulfur coals appears to reflect the original plant sulfur, although diagenetic changes in content and isotopic composition of this fraction cannot be ruled out. The wide variability of the δ ³⁴S in pyrite fractions suggests a complex origin involving varying extents of microbial H₂S production from sulfate reservoirs of different isotopic compositions. The precipitation of pyrite may have begun soon after deposition and continued throughout the coalification process.