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1.
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 δ 34S 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 δ 34S 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.  相似文献   

2.
3.
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 δ34SΣs of 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 +7.5 ± 1.5‰. On the other hand, the concentration and δ34SΣs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and ?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 ?o2 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.  相似文献   

4.
Eleven samples of crude oil from the Molasse Basin of Southern Germany were fractionated and their contents of sulfur and nitrogen as well as the stable isotope compositions of these elements (34S32S and 15N14N, resp.) investigated.According to the δ34S determinations, all crude oils from the Tertiary base of the Western and Eastern Molasse belong to one oil family and differ significantly from the Triassic and Liassic oils in the Western Molasse.An enrichment of 34S was observed with increasing polarity of crude oil fractions. The isotope distributions of sulfur in the polar constituents of the biodegraded oils from the sandstones of Ampfing, however, approach a homogeneous distribution.The nitrogen isotope distribution is rather uniform in Southern German oils. A regional differentiation can be recognized, although the overall isotopic variation is small. The δ15N values of the crudes and asphaltenes do not correlate.  相似文献   

5.
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 34S32S ratio which is 13.0‰ less than that of the undissociated material while the 34S32S 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.  相似文献   

6.
The isotopic composition of strontium of pore water and of authigenic minerals leached from the sediment of core 119K with hot aqua regia is similar to that of the brine in the Discovery deep and differs from that of normal seawater. The average 87Sr86Sr ratio of strontium removed by acid leaching is 0.7077 ± 0.0007 (1σ) compared to a value of 0.70904 for the Red Sea. The detrital silicate fraction exhibits an approximate inverse correlation between 87Sr86Sr ratios and strontium concentrations which provides tentative support for a model in which the detrital silicate fraction of deep-sea sediment is considered to be a mixture of terrigenous dust of sialic composition enriched in radiogenic 87Sr and of volcanogenic material of basaltic composition and low 87Sr abundance. The 87Sr86Sr ratios of the shells of foraminifers and pteropods, expressed as δ 87Sr‰ relative to 0.70904 for seawater, decrease from ?0.23 ± 0.17‰ at 90 cm to ?0.82 ± 0.17‰ at 273 cm and remain constant at this value to a depth of 450 cm. The lowering of the δ 87Sr values is attributed both to the presence of aragonite overgrowths on pteropod shells and to possible isotope exchange with strontium in the connate fluid.  相似文献   

7.
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, S42? and S52?, 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 d(reduction Fe)dt = kSt0.5(J+)0.5 AFeOOH1 where St was the total dissolved sulfide concentration, (H+) the hydrogen ion activity, both in moles/ liter; and AFeOOH 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 d(FeS)dt = kSt1(H+)1 AFeOOH1 where d(FeS)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.  相似文献   

8.
Numerical modeling of the terrestrial oxygen budget based on the revised δ13Ccarb 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 13C12C and 34S32S trends.  相似文献   

9.
Pleistocene and Recent lavas from the Sunda arc range from those showing affinities with the island arc tholeiitic series, through a spectrum of calc-alkaline to high-K alkaline rocks. The tholeiitic rocks have relatively low 87Sr86Sr ratios averaging 0–7043; the calc-alkaline rocks show a wide range (from 0.7038 to 0.7059, averaging 0.7048); the high-K alkaline rocks average 0.7045. A rhyolitic ignimbrite from Sumatra has an 87Sr86Sr ratio of 0.7139.The relationship between 87Sr86Sr and major and trace element geochemistry is variable and complex. Lavas from the same volcano sometimes show significant differences in 87Sr86Sr despite close geochemical relationships. Rocks of the calc-alkaline suite show a regular decrease in 87Sr86Sr from West Java to Bali and there is some evidence for increasing 87Sr86Sr with increasing depth to the Benioff zone. Calc-alkaline and tholeiitic rocks from the Sunda arc have significantly higher 87Sr86Sr ratios than those from other island arcs, except from those arcs where continental crustal involvement has been inferred (e.g. New Zealand).A model of 87Sr enrichment due to isotopic equilibration of oceanic crust with sea water and disequilibrium melting in the slab and/or mantle is favoured to explain the Sr isotopic composition of the tholeiitic and normal calc-alkaline lavas. Calc-alkaline lavas with high 87Sr86Sr ratios are best explained by either sialic contamination, or the presence of alkali basalt as a component of the downgoing slab. The Sr isotopic data for the high-K alkaline lavas suggest a mantle origin. The high 87Sr86Sr ratio in the Lake Toba rhyolite implies a crustal origin.  相似文献   

10.
The whole-rock δ 18O values of samples from twelve discrete Archean plutons intruding the western Wabigoon granite-greenstone belt, northwestern Ontario, range from 6.8 to 9.5‰. Most samples with δ 18O > 8.7‰, however, come from portions of the Burditt Lake stock, or the Esox Lake area, that have been affected by deuteric or metasomatic activity. The distribution of δ 18O values for the remaining samples is very similar to that known for the large batholithic complexes and gneissic terrains that dominate this portion of northwestern Ontario. The generally low δ 18O values of the discrete granitoid plutons suggest that 18O-rich supracrustal rocks were unimportant in their genesis. Like the granitoids of the batholithic complexes and gneissic terrains, the discrete granitoid plutons represent new additions to the Archean sialic crust.  相似文献   

11.
Sulfur isotopic studies of pyrite from metasediments in the >2.6 Byr old Deer Lake green-stone sequence, Minnesota, have been conducted in order to evaluate the possible importance of sulfate reducing bacteria in sulfide formation. Pyrite occurs as ovules up to 2 cm in diameter within graphitic slates, and as fine disseminations in metagraywacke units. SEM studies indicate the pyrite is framboidal in morphology.δ34S values of pyrite from the Deer Lake sediments range from ?2.3 to 11.1‰, with a peak at ~ +2‰ Isotopic data are consistent with either high temperature inorganic reduction of circulating seawater sulfate, or low temperature bacterial reduction. However, the lack of sulfide bands or massive occurrences in the sediments, the restriction of pyrite mineralization to the sediments, and the absence of evidence for hot spring activity suggest that a diagenetic origin of pyrite is more feasible. Sulfide in such an environment would be produced principally by the action of sulfate reducing bacteria.Results of the study are in agreement with those of Goodwinet al. (1976) who suggest that dissimilatory sulfate reduction was operative in the Archean ocean some 2.75 Byr ago.  相似文献   

12.
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 (δ34S: +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.  相似文献   

13.
A study was undertaken with the thermophilic green alga Cyanidium caldarium which grows optimally at low pH and high concentrations of CO2. Carbon-isotope fractionation was not found to be a simple linear function of temperature. Maximum enrichment of 12C in cellular material occurred under optimum growth conditions (at approximately pH 2 and at temperatures between 40–50°C in a CO2 atmosphere). A maximum measured fractionation of ?24‰ may account for low values (δ 13C < ?30‰ PDB) in Precambrian kerogen presumably derived from algal mats.  相似文献   

14.
DH and 18O16O ratios have been measured for whole-rock samples and mineral separates from the mafic and ultramatic rocks of the Cambro-Ordovician Highland Border Suite. The H- and O- isotopic compositions of these rocks record individual stages in a relatively complex 500 Myr old hydrothermal/metamorphic history. Lizardite serpentinites (δD ~ ? 105‰; δ18O ~ + 6.2‰) record a premetamorphic history and indicate that parent harzburgites, dunites, and pyroxenites were serpentinized through low-temperature interaction with meteoric waters during cooling. The other rocks of the Highland Border Suite record subsequent interaction with metamorphic fluids. Amphibolite facies hornblende schists were produced through thrust-related (dynamothermal) metamorphism of spilitic pillow lavas. During dehydration, D-enriched fluids were driven off from the spilites thus leaving the hornblende schists to equilibrate with a relatively D-depleted internal fluid reservoir (δD ~ ? 45‰). The expelled D-enriched fluids may have mixed with more typical Dalradian metamorphic waters which then exchanged with the remaining mafic rocks and lizardite serpentinites during greenschist facies regional metamorphism to produce antigorite serpentinites (δD ~ ? 62‰; δ18O ~ + 8‰) and greenschist metaspilites (δD ~ ? 57‰; δ18O ~ + 7.3‰) with similar H- and O-isotopic compositions. Serpentinites which have been only partially metamorphosed show intermediate H-isotopic compositions between that of metamorphic antigorite (δD ~ ? 62‰) and non-metamorphic lizardite δD ~ ? 105‰) end members.  相似文献   

15.
Carbon isotope values of 260 Precambrian limestones and dolomites (most of them being substantially unaltered) have yielded an overall mean of δ 13C = +0.4 ± 2.7‰ vs. PDB; the corresponding oxygen values average at δ 13O = +20.0 ± 4.2‰ vs. SMOW. Like the overall mean, the δ 13C values furnished by individual carbonate occurrences are, as a rule, fairly “modern” and almost constant as from the very beginning of the sedimentary record. A remarkable exception are the “heavy” dolomites of the Middle Precambrian Lomagundi Group, Rhodesia, with δ 13C = +9.4 ± 2.0‰ vs. PDB. As a result of our measurements, the sporadic occurrence in the geological past of anomalously heavy carbonates seems to be established.The approximate constancy around zero per mill of the δ 13C values of marine carbonates through geologic time would imply a corresponding constancy of the relative proportion of organic carbon in the total sedimentary carbon reservoir since about 3.3 · 109 y ago (with Corg/Ctotal ? 0.2). Utilizing this ratio and current models for the accumulation of the sedimentary mass as a function of time, we get a reasonable approximation for the absolute quantity of organic carbon buried in sediments and, accordingly, of photosynthetic oxygen released. Within the constraints of our model (based on a terrestrial degassing constant λ = 1.16 · 10?9 y?1) close to 80% of the amount of oxygen contained in the present oxygen budget should have been released prior to 3 · 109 y ago. Since geological evidence indicates an O2-deficient environment during the Early and most parts of the Middle Precambrian, there is reason to believe that the distribution of this oxygen between the “bound” and the “molecular” reservoir was different from that of today (with effective O2-consuming reactions bringing about an instantaneous transfer to the crust of any molecular oxygen released). Accordingly, the amount of Corg in the ancient sedimentary reservoir as derived from our isotope data is just a measure of the gross amount of photosynthetic oxygen produced, withholding any information as to how this oxygen was partitioned between the principal geochemical reservoirs. As a whole, the carbon isotope data accrued provide evidence of an extremely early origin of life on Earth since the impact of organic carbon on the geochemical carbon cycle can be traced back to almost 3.5 · 109y.  相似文献   

16.
230Th-238U disequilibrium systematics reveal several important characteristics of the mantle source regions and petrogenesis of volcanic rocks in the presumed hot spots of Hawaii, Marion Island (Prince Edward hot spot), and Samoa. The (230Th232Th) activity ratios of lavas from these three hot spots (1.06 ± 0.07, 1.04 ± 0.08, and 0.81 ± 0.06, respectively) imply that the source regions are each nearly homogeneous with ThU weight ratios of 2.9, 3.0, and 3.8. For Marion Island and Mauna Kea, Hawaii, negligible secular variation occurs in the (230Th232Th) initial ratios. This supports other evidence for very short transfer time between source and surface. Significant residence time at depth prior to eruption cannot be ruled out for the Samoan lavas we have studied; however, the data for one of these flows deviate from the proposed (230Th232Th)-87Sr86Sr correlation (Condomineset al., 1981a) in the opposite sense from that expected for such residence. If it is assumed that the measured (230Th232Th) ratios of the young lavas reflect ThU in their mantle sources, then the observed variations among these three hot spots, combined with those reported by other workers for Iceland, the Azores and Tristan de Cunha, suggest that these sources are characterized by ThU ratios ranging from values similar to that of MORB source (~2.5) to values similar to those of bulk earth (~3.8). Mixing of different proportions of depleted and enriched mantle may be responsible for the observed range.  相似文献   

17.
For sulfates of Miocene evaporites in the Carpathian Foredeep, the waters of crystallization of gypsum (w.c.g.) have δD = ?38 to ?113%. and δ18O = 0 to ?11%. (SMOW). The δ34S and δ18O 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.  相似文献   

18.
143Nd144Nd ratios measured in Quaternary lavas from Java and the Banda arc of Indonesia range from 0.51242 to 0.51280 and exhibit an inverse correlation with 87Sr86Sr. Isotopically, the Indonesian samples resemble Andean rather than island arc lavas. The samples from Java plot either within, or adjacent to the mantle array, towards higher 87Sr86Sr ratios. Samples from the Banda arc and the anomalous calc-alkaline volcano Papandajan are characterized by relatively low 143Nd144Nd and high 87Sr86Sr ratios. These characteristics are consistent with the interpretation that subducted terrigenous material was involved in the genesis of these lavas. Furthermore the Banda arc samples appear to lie on a mixing line between isotopic compositions characteristic of the mantle and upper continental crust. A high-K trachyte from the alkaline volcano Muriah, Java, has isotopic characteristics of the mantle (143Nd144Nd = 0.51270, 87Sr86Sr = 0.70424), which implies that the extreme enrichment in large-ion-lithophile elements in its source must have occurred only shortly before its formation. The inferred 143Nd144Nd ratio of the unmodified mantle beneath Java and the Banda arc is lower than that observed in mid-ocean ridge basalt, which may have important implications for a better understanding of the geochemical structure of the mantle.  相似文献   

19.
In the northwestern margin of the Youjiang basin(NWYB)in SW China,many Carlin-like gold deposits are highly antimony(Sb)-rich,and many vein-type Sb deposits contain much Au.These deposits have similar ages,host rocks,ore-forming temperatures,ore-related alterations and ore mineral assemblages,but the Au and Sb metallogenic relations and their ore-forming process remain enigmatic.Here we investigate the large Qinglong Sb deposit in the NWYB,which has extensive sub-economic Au mineralization,and present a new metallogenic model based on in-situ trace elements(EPMA and LA-ICP-MS)and sulfur isotopes(NanoSIMS and fs-LA-MC-ICPMS)of the ore sulfides.At Qinglong,economic Sb ores contain coarse-grained stibnite,jasperoid quartz and fluorite,whilst the sub-economic Au–Sb ores comprise dominantly veined quartz,arsenian pyrite and fine-grained stibnite.Three generations of ore-related pyrite(Py1,Py2 and Py3)and two generations of stibnite(Stb1 and Stb2)are identified based on their texture,chemistry,and sulfur isotopes.The pre-ore Py1 is characterized by the lower ore element(Au,As,Sb,Cu and Ag)contents(mostly below the LA-ICP-MS detection limit)and Co/Ni ratios(average 0.31)than the ore-stage pyrites(Py2 and Py3),implying a sedimentary/diagenetic origin.The Py2 and Py3 have elevated ore element abundance(maximum As=6500 ppm,Au=22 ppm,Sb=6300 ppm,Cu=951 ppm,Ag=77 ppm)and Co/Ni ratios(average 1.84),and have positive As vs.Au–Sb–Cu–Ag correlations.Early-ore Stb1 has lower As(0.12–0.30 wt.%)than late-ore Stb2(0.91–1.20 wt.%).These features show that the progressive As enrichment in ore sulfides is accompanied by increasing Au,Sb,Cu and Ag with the hydrothermal evolution,thereby making As a good proxy for Au.As-rich,As-poor and As-free zones are identified via NanoSIMS mapping of the Au-bearing pyrite.The As-rich zones in the Qinglong Au-bearing pyrites(Py2 and Py3)and ore stibnites(Stb1 and Stb2)have narrowδ34SH2S ranges(-8.9‰to +4.1‰,average-3.1‰)and-2.9‰to +6.9‰,average + 1.3‰),respectively,indicating that the Au-rich and Sb-rich fluids may have had the same sulfur source.Published in-situ sulfur isotopic data of pyrite As-rich zones from other Carlin-like Au deposits(Shuiyindong,Taipingdong,Nayang,Getang and Lianhuashan)in the NWYB have similar ore-fluidδSH2S values(-4.5‰to +6.7‰,average-0.6‰)to those of Qinglong.Therefore,we infer that the sulfur of both Au and Sb mineralization was derived from the same magmatic-related source(0±5‰)in the NWYB.Moreover,the core of pyrites(Py1)has variable S isotope fractionation(-18.9‰to +18.1‰,mostly +3‰to +12‰),suggesting that the higher-34S H2S was produced by bacterial sulfate reduction(BSR).The hydrothermal pyrite(Py2 and Py3)δ34S values gradually decrease with increasing As concentrations,and ultimately,within the restricted range(-5‰to +5‰)in As-rich zones.This variation implies that the As-rich pyrite was formed through ongoing interactions of the magmatic-hydrothermal fluid with pre-existing sedimentary pyrites,causing the progressive decreasing δ34S values with As content increase,Hence,the fluid/mineral interaction may have generated the observed variation in δ34S and As contents.Overall,comparing the Au and Sb deposits in the NWYB,we favor a magmatic-related source for the Au–Sb–As-rich fluids,but the Au-and Sb-ore fluids were likely evolved at separate stages in the ore-forming system.  相似文献   

20.
CaCO3Ca(OH)2CaS serves as a model system for sulfide solubility in carbonatite magmas. Experiments at 1 kbar delineate fields for primary crystallization of CaCO3, Ca(OH)2 and CaS. The three fields meet at a ternary eutectic at 652°C with liquid composition (wt%): CaCO3 = 46.1%, Ca(OH)2 = 51.9%, CaS = 2.0%. Two crystallization sequences are possible for liquids that precipitate calcite, depending upon whether the liquid is on the low-CaS side, or the high-CaS side of the line connecting CaCO3 to the eutectic liquid. Low-CaS liquids precipitate no sulfide until the eutectic temperature is reached leading to sulfide enrichment. The higher-CaS liquids precipitate some sulfide above the eutectic temperature, but the sulfide content of the melt is not greatly depleted as the eutectic temperature is approached. Theoretical considerations indicate that sulfide solubility in carbonate melts will be directly proportional to ?S212 and inversely proportional to ?O212; it also is likely to be directly proportional to melt basicity, defined here by aCO32??CO2. A strong similarity exists in the processes which control sulfide solubility in carbonate and in silicate melts. By analogy with silicates, ferrous iron, which was absent in our experiments, may also exert an important influence on sulfide solubility in natural carbonatite magmas.  相似文献   

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