New sulfur isotope ratios from South American volcanoes

Four new sulfur isotope ratios of native volcanic sulfur are given and it is shown that isotope distributions are best presented with histograms.Possible causes governing the isotope compositions of native volcanic sulfur are briefly discussed.With 1 Figure     

若干以沉积岩为容矿围岩的热液矿床硫同位素地球化学研究

文章对与沉积岩容矿有关的热液广西高龙微细浸染型金矿、新疆霍什布拉克铅锌矿、广西盘龙铅锌矿和下雷锰矿等矿床硫化物进行硫同位素测定,硫同位素组成分别为-15.3‰~+15.6‰,-18.8‰~+24.2‰,-21.0‰~+26.4‰,-32.6‰~+32.2‰。硫同位素可以达到平衡(高龙、霍什布拉克、下雷),也可以没达到平衡(盘龙)。δ34SΣS值在+13‰~+28‰之间,表明与沉积岩容矿热液矿床中硫来源于海水硫酸盐还原硫,但不排除有岩浆硫的加入。     

Strontium isotope systematics of hydrothermal vein minerals in deposits of West Germany

Vein minerals in West Germany hosted by crystalline basement rocks and Paleozoic and Mesozoic sedimentary rocks are characterized by⁸⁷Sr/⁸⁶Sr ratios which indicate continental derivation of Sr incorporated into the minerals. Neither mantle-derived Sr nor prominent contribution of this element from sea water (except for the strontianites of Münsterland) can be substantiated by the data presented.Minerals in veins hosted by sedimentary rocks have acquired their Sr most plausibly from buried sedimentary rock sequences.Mineralization of veins hosted by Moldanubian crystalline rocks in the Bayerischer Wald is confined to a Permian-Triassic time span. The⁸⁷Sr/⁸⁶Sr ratios of the minerals cover a relatively narrow range reflecting the time-dependent Sr isotopic composition of the host environment.Mineralization of veins in the Schwarzwald crosscutting crystalline basement rocks and partly extending into Mesozoic caprocks obviously occurred episodically or continuously from the Late Variscan event to Tertiary time. Mineral sequences of the Schwarzwald veins incorporated Sr with time-integrated isotopic composition most likely derived predominantly from gneisses.

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Zusammenfassung Gangminerale im kristallinen Grundgebirge und in paläozoischen und mesozoischen Sedimentgesteinen Westdeutschlands zeichnen sich durch⁸⁷Sr/⁸⁶Sr-Verhältnisse aus, die eine kontinentale Herkunft des Sr anzeigt. Weder Sr vom Erdmantel noch ein wesentlicher Beitrag dieses Elementes aus Meerwasser in den Mineralen (abgesehen von den Strontianiten des Münsterlandes) kann aus den vorliegenden Daten abgeleitet werden.Gangminerale in Sedimentgesteinen haben sehr wahrscheinlich Sr aus tieferliegenden Sedimentgesteinsabfolgen eingebaut.Die Mineralisation von Gängen in Gesteinen des kristallinen Grundgebirges im Moldanubikum des Bayerischen Waldes ist auf den Zeitraum Perm-Trias beschränkt. Die⁸⁷Sr/⁸⁶Sr-Verhältnisse umfassen eine relativ enge Spanne und spiegeln die zeitabhängige Isotopenzusammensetzung der umgebenden Gesteine und der des Untergrundes wider.Gänge im Schwarzwald durchschneiden kristallines Grundgebirge und setzen sich teilweise in mesozoisches Deckgebirge fort. Die Mineralisation erfolgte episodisch oder kontinuierlich von der variszischen Orogenèse bis ins Tertiär. Die Mineralabfolgen der Schwarzwaldgänge enthalten Sr mit einer zeitintegrierten Isotopenzusammensetzung, das sehr wahrscheinlich vorwiegend aus Gneisen stammt.

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Résumé Les minéraux des filons hydrothermaux contenus dans le socle cristallin et dans les sédiments paléozoïques et mésozoïques de l'Allemagne occidentale présentent des rapports initiaux⁸⁷Sr/⁸⁶Sr qui indiquent une origine continentale du Sr. Les résultats présentés dans cette note ne permettent d'accepter ni une origine mantellique ni un apport à partir de l'eau de mer (à l'exception des strontianites du Münsterland).Les minéraux des veines contenues dans les roches sédimentaires doivent très probablement leur Sr aux séries sédimentaires profondément enfouies.La minéralisation des veines contenues dans les roches cristallines moldanubiennes du Bayerische Wald date du Permo-Trias. Les rapports initiaux embrassent un éventail relativement étroit qui traduit la composition isotopique, fonction du temps, des roches encaissantes.Les filons de la Forêt Noire, qui traversent le socle cristallin et se prolongent partiellement dans la couverture mésozoïque, se sont foïmés manifestement, par épisodes ou de manière continue, depuis l'orogenèse varisque jusqu'au Tertiaire. Leurs séquences minérales renferment du Sr de composition isotopique temporellement intégrée, qui provient principalement des gneiss.

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On the usefulness of sulfur isotope ratios in crude oil correlations

Sulfur isotope analyses have been completed for twelve samples of marine Jurassic oils from a single basin, and are presented along with previous chemical analyses of the same oils (Seifert and Moldowan, 1978). Two isotopic anomalies are discussed in light of correlational analyses, and show that sulfur isotope ratios, when used with other chemical variables, are sensitive indicators of subtle changes in initial source input. Measurements of δ³⁴S in correlational studies of crude oil characterization and identification are recommended.     

Concentrations and isotope ratios of carbon,nitrogen and sulfur in ocean-floor basalts

Fresh submarine basalt glasses from Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 22 to 160 ppm carbon and 0.3 to 2.8 ppm nitrogen, respectively, as the sums of dissolved species and vesicle-filling gases (CO₂ and N₂). The large range of variation in carbon content is due to combined effect of depth-dependency of the solubility of carbon in basalt melt and varying extents of vapour loss during magma emplacement as well as in sample crushing. The isotopic ratios of indigenous carbon and nitrogen are in very narrow ranges,?6.2 ± 0.2% relative to PDB and +0.2 ± 0.6 %. relative to atmospheric nitrogen, respectively. In basalt samples from Juan de Fuca Ridge, however, isotopically light carbon (δ¹³C = around ?24%.) predominates over the indigenous carbon; no indigenous heavy carbon was found. Except for Galapagos Ridge samples, these ocean-floor basalts contain 670 to 1100 ppm sulfur, averaging 810 ppm, in the form of both sulfide and sulfate, whereas basalts from Galapagos Ridge are higher in both sulfur (1490 and 1570 ppm) and iron (11.08% total iron as FeO). The δ³⁴S values average +0.3 ± 0.5%. with average fractionation factor between sulfate and sulfide of +7.4 ± 1.6%.. The sulfate/sulfide ratios tend to increase with increasing water content of basalt, probably because the oxygen fugacity increases with increasing water content in basalt melt.     

Oxygen isotope fractionation between hydroxide minerals and water

The modified increment method has been applied to the calculation of oxygen isotope fractionation factors for hydroxide minerals. The results suggest the following sequence of ¹⁸O-enrichment in the common hydroxides: limonite > gibbsite > goethite > brucite > diaspore. The hydroxides are significantly enriched in ¹⁸O relative to the corresponding oxides. The sequence of ¹⁸O-enrichment in the hydroxides and oxides of trivalent cations is as follows: M(OH)₃ > MO(OH) > M₂O₃. There are also considerable fractionations within the polymorphos of Al(OH)₃. The internally consistent fractionation factors for hydroxide–water systems are obtained for the temperature range of 0 to 1200 °C, which are comparable with the data derived from synthesis experiments and natural samples at surficial temperatures. Temperature dependence of oxygen isotope fractionations between goethite, gibbsite, boehmite and diaspore and water are significant enough for the purpose of geothermometry. Thus the hydroxide–water pairs hold great promise of serving as reliable paleothermometers in surficial geological environments. Received: 22 January 1997 / Revised, accepted: 2 June 1997     

Hydrogen isotope fractionation between OH-bearing minerals and water

Hydrogen isotope fractionation factors between hydroxyl-bearing minerals and water were determined at temperatures ranging between 400 and 850°C. The hydrogen isotope exchange rates for the mineral-water pairs examined were very slow. In most cases it was necessary to use an interpolation method for the determination of the hydrogen isotope equilibrium fractionation factor, α_e.For the temperature range of 450–850°C the hydrogen isotope fractionation factors for the mica-water and amphibole-water systems are simply expressed as a function of temperature and the molar fractions of the six-fold coordinated cations in the crystal, regardless of mineral species, as follows: 10³ In α_{e(mineral-water)} = ? 22.4 (10⁶T^?2) + 28.2 + (2X_Al ? 4X_Mg ? 68X_Fe), where X is the molar fraction of the cations. As the equation indicates, for any specific composition of the OH-bearing minerals, the change of α_e with temperature, over the temperature range investigated, is the same for all minerals studied. Thus for any specified values of X_Al, X_Mg, and X_Fe for these minerals, the relationship between α_e and T is 10³ In α_e = αT^?2 + k. Consequently, hydrogen isotope fractionation among coexisting minerals is temperature independent and cannot be used as a hydrogen isotope geothermometer.Some exceptions to the above general observations exist for minerals such as boehmite and kaolinite. In these minerals hydrogen bonding modifies the equilibrium hydrogen isotopic fractionation between mineral and water.     

Basic-to-acid and acid-to-basic zonation in the sulfur isotope composition of diagenetic sulfide nodules

The typical for marine sediments decrease in the amount of sulfate ion in interstitial solutions with increasing depth owing to sulfate reduction and attenuation of the diffusion of near-bottom waters is manifested as the basic-to-acid zonation in the sulfur isotope composition of the diagenetic pyrite nodules (increase of δ³⁴S values from the center to edge). In sandstones of the Early Carboniferous Emyaksin Formation, which is developed at middle reaches of the Vilyui River (Sakha-Yakutia), we detected a peculiar sulfide nodule. In contrast to common nodules, this nodule is marked by the δ³⁴S value decreasing from 7.5…8.6‰ at the center to –30…–31.4‰ at the edge. Such acid-to-basic zonation is attributed to the origin of nodule in a freshened basin (delta) with a sulfate-depleted environment, which gave way to a sulfate-enriched environment owing to the expulsion brines from the underlying gypsiferous sequences.     

Fractionation of sulfur isotopes and selenium between coexisting sulfide minerals from the Besshi deposit,Central Shikoku,Japan

Fractionation of sulfur isotopes and selenium was measured between coexisting pyrite and chalcopyrite and between coexisting pyrrhotite and chalcopyrite from the Besshi deposit of Kieslager-type, Central Shikoku, Japan. In all the pyrite-chalcopyrite pairs studied, ³⁴S is enriched in pyrite relative to chalcopyrite, while selenium is enriched conversely in chalcopyrite relative to pyrite. The mean ³⁴S_py-cp value is +0.53±0.36 per mil, and the mean value of the distribution coefficient of selenium, D_cp-py, is 2.58±0.64. In all the pyrrhotite-chalcopyrite pairs studied, the two minerals are very close to each other both in sulfur isotope and Se/S ratios. The mean ³⁴S_po-cp value is –0.08±0.16 per mil and the mean D_cp-po value is 0.99±0.05. The results have been discussed in comparison with similar data obtained for the Hitachi deposits of Kieslager-type, Japan (Yamamoto et al. 1983).     

Hydrogen isotope exchange between clay minerals and sea water

The D/H ratios of separated size fractions of clay minerals in two deep sea sediments taken from depths of 30 and 1100cm in a North Pacific Ocean core were measured to investigate the extent of hydrogen isotope exchange between detrital clay minerals and sea water. The D/H ratio of each size fraction of the shallower sample was compared with that of the corresponding size fraction of the deeper sample. No differences were detected between D/H ratios of corresponding size fractions from the two levels in the core except for the <0.1μm size fraction, which makes up only 5% of the sample. Even in this size fraction only about 8–28% D/H exchange is apparent. This is interpreted as indicating that no significant hydrogen isotope exchange between clay minerals and sea water has occurred during the past 2–3 Myr. Therefore information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the D/H ratios of deep sea sediments younger than 2–3 Myr.     

东太平洋北部胡安·德富卡洋中脊Mothra热液场硫化物烟囱体成矿物质来源:铅和硫同位素组成

对采自Mothra热液场Faulty Towers硫化物烟囱体群(47°57.447,N,129°06.568W)的一个硫化物烟囱体进行了铅和硫同位素组成的研究工作.分析结果表明,铅同位素组成的分布范围为:206Pb/204Pb=18.665～18.828; 207Pb/204Pb=15.460～15.607; 208...     

广东大降坪硫(铅锌)矿床岩浆热液叠加作用——来自闪锌矿Rb-Sr年龄及硫同位素的证据

广东大降坪硫(铅锌)矿床位于与岩浆作用有关的大绀山多金属矿田的中部,主矿体为赋存在震旦纪变质岩中的层状、透镜状黄铁矿矿体,最近在两个不同产状的黄铁矿矿体下部又新发现了脉状及层状铅锌矿体。文章通过对铅锌矿体的年龄及硫同位素研究,探讨其与主矿体的成因关系,获得了脉状铅锌矿体中闪锌矿的Rb-Sr等时线年龄为(88.5±3.9)Ma,即晚白垩世,与上部黄铁矿矿体的年龄(约630 Ma)相差较大,而与整个大绀山多金属矿田的成矿作用时限一致。三种不同产状的矿体硫同位素组成差异明显:层状黄铁矿矿体富集硫的轻同位素(δ34S=-10.90‰~-25.55‰),且与围岩的硫同位素范围一致,说明硫来自生物的细菌还原硫;透镜状黄铁矿矿体δ34S组成范围较宽(-9.38‰~22.69‰),具多源性硫的特征;铅锌矿体的δ34S在-7.1‰~6.4‰之间变化,硫可能来自深源岩浆,并受围岩成分混染。多方面的证据表明,大降坪黄铁矿矿体下部的铅锌矿体形成于晚白垩世的岩浆热液成矿作用,透镜状黄铁矿矿体受到岩浆热液的叠加。     

S K- and L-edge XANES and electronic structure of some copper sulfide minerals

The S K and L-edge x-ray absorption near-edge structures (XANES) of low bornite, cubanite, chalcocite, covellite, enargite and tetrahedrite have been measured with synchrotron radiation. The near-edge features are interpreted based on comparison with the S K- and L-edge spectra of chalcopyrite and a MO/energy band structure model. The XANES spectra of these sulfides reflect the DOS of unoccupied S s-, p- and d-like states near and above the Fermi level. In tetrahedral Cu-Fe sulfides, the Fe³⁺ 3d crystal field band has much more significant DOS of unoccupied S 3p-and 3s-like states than the Cu⁺ 3d crystal field band. For Cu sulfides, the Cu⁺ 3d crystal field band has the higher DOS of S 3p- and 3 s-like states in tetrahedral structure than in structures with the triangular CuS₃ cluster. The shifts in both S K- and L-edges correlate approximately linearly with the energy gap.     

The importance of sulfur isotope ratios in the differentiation of Prudhoe Bay crude oils

Sulfur isotopic analyses have been completed for eight Triassic, Jurassic and Lower Cretaceous oils from the Prudhoe Bay field, Alaska. Results presented complement earlier work and further indicate the diagnostic importance of δ ³⁴S values in correlation studies of crude oils. The present work supports an earlier contention that Kuparuk River, Sadlerochit and Lisburne crude oils have a similar source of origin, distinct from that of Kingak oil. If Kingak and Shublik Formations contribute to the Sag River Sand crude oil in the Prudhoe Bay area of Alaska, the same may not be the case for Sag River Sand oil in the Point Barrow area which apparently originated from a different source or combination of sources.     

与火山岩容矿有关的海底热水沉积矿床硫同位素地球化学证据

对国内与火山岩容矿有关的海底热水沉积矿床新疆阿巴宫、铁-铅锌矿、甘肃桦树沟铁-铜矿床、新疆阿舍勒铜锌矿、新疆阿尔泰可可塔勒铅锌矿等矿床硫化物进行硫同位素测定,这些矿床硫化物和硫酸盐的硫同位素组成分别为-4.3‰~1‰(阿巴宫)、+8.1‰~+33.4‰(桦树沟)、-3.3‰~+8.2‰(阿舍勒矿床硫化物)、-20.6‰~5.1‰(阿尔泰可可塔勒)。硫化物的硫同位素变化范围较小,硫同位素可以达到平衡,也可以没有达到平衡,获得的δ34SΣS值有+18‰~29‰之间,δ34SΣS值高;表明与火山岩控矿有关的海底热水沉积矿床热液中硫的来源,不是直接来源岩浆去气的硫,而是岩浆去气硫与海水硫酸盐硫混合而成的硫。     

Influence of sedimentary environments on sulfur isotope ratios in clastic rocks: a review

Strata-bound sulfide deposits associated with clastic, marine sedimentary rocks, and not associated with volcanic rocks, display distributions of S³⁴ values gradational between two extreme types: 1. a flat distribution ranging from S³⁴ of seawater sulfate to values about 25 lower; and 2. a narrow distribution around value S³⁴ (sulfide)=S³⁴ (seawater sulfate) –50, and skewed to heavier values. S³⁴ (seawater sulfate) is estimated from contemporaneous evaporites. There is a systematic relation between the type of S³⁴ distribution and the type of depositional environment. Type 1 occurs in shallow marine or brackish-water environments; type 2 occurs characteristically in deep, euxinic basins. These distributions can be accounted for by a model involving bacterial reduction of seawater sulfate in systems which range from fully-closed batches of sulfate (type 1) to fully open systems in which fresh sulfate is introduced as reduction proceeds (type 2). The difference in the characteristic distributions requires that the magnitude of the sulfate-sulfide kinetic isotope effect on reduction be different in the two cases. This difference has already been suggested by the conflict between S³⁴ data for modern marine sediments and laboratory experiments. The difference in isotope effects can be accounted for by Rees' (1973) model of steady-state sulfate reduction: low nutrient supply and undisturbed, stationary bacterial populations in the open system settings tend to generate larger fractionations.

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Zusammenfassung Schichtgebundene Sulfid-Lagerstätten in Begleitung von klastischen, marinen Sedimentgesteinen ohne Beteiligung vulkanischer Gesteine zeigen kontinuierliche Verteilungen der S³⁴-Werte zwischen zwei Extremtypen: 1. Eine flache Verteilung im Bereich von S³⁴-Werten des Seewasser-Sulfats bis zu Werten, die etwa 25 niedriger liegen. 2. Eine eng begrenzte Verteilung um den S³⁴ (Sulfid)-Wert=S³⁴ (Seewasser-Sulfat) –50 und asymmetrischer Verteilungskurve mit stärkerer Besetzung bei den schwereren Werten. Das S³⁴ (Seewasser-Sulfat) wird von gleichaltrigen Evaporiten abgeleitet. Es besteht eine systematische Beziehung zwischen der Art der S³⁴-Verteilung und dem Milieu des Ablagerungsraumes. Typ 1 tritt im marinen Flachwasser oder in brackischer Umgebung auf. Typ 2 ist charakteristisch für tiefe euxinische Becken. Diese Verteilungen können erklärt werden mit Hilfe eines Modells mit bakterieller Reduktion von Meerwasser-Sulfat in Systemen, die von völlig abgeschlossenen Sulfat-Mengen (Typ 1) bis zu völlig offenen Systemen reichen, in die bei fortschreitender Reduktion frisches Sulfat zugeführt wird (Typ 2). Der Unterschied in den charakteristischen Verteilungen setzt voraus, daß die Stärke der kinetischen Sulfat-Sulfid-Isotopen-Wirkung auf die Reduktion in beiden Fällen verschieden ist. Dieser Unterschied wurde bereits wegen der Widersprüche zwischen den verschiedenen S³⁴-Werten heutiger mariner Sedimente und Laborexperimente vermutet. Der Unterschied in der Isotopen-Wirkung kann durch das Modell von Rees (1973) für kontinuierlich ablaufende Sulfat-Reduktion erklärt werden. Geringes Nahrungsangebot und ungestörte, gleichbleibende Bakterien-Populationen in offenen Systemen neigen zur Erzeugung stärkerer Fraktionierungen.

     

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.     

硫化物及硫酸盐中硫同位素制样装置及其反应器研制

研制了一种新型硫化物及硫酸盐中硫同位素制样装置及其反应器。实验证明,采用该装置及其反应器制样具有真空度好、使用方便、无污染、制样效率高和成本低等优点。所生成的二氧化硫具有纯度高,分析结果准确、可靠等特点,完全能满足硫化物和硫酸盐中硫同位素分析测试的制样要求。     

新疆东天山小热泉子铜锌(硒)矿床硒的赋存状态及硫硒比值研究

小热泉子矿床是中-大型富铜、锌(硒)多金属矿床。文章通过电子探针较系统地分析了该矿床不同矿体中的不同容矿岩石的各种硫化物(241件)的微量元素。测定结果表明,该矿床的硫化物明显富硒,硫化物中w(Se)平均为0.045%,S/Se比值平均为829。经初步计算,该矿床硒资源量为813吨,已达大型规模。首次发现硫化物中方铅矿含硒最高,w(Se)最高可达11%,为硒方铅矿;其他硫化物黄铜矿、闪锌矿、铜蓝、黄铁矿中平均w(Se)分别为0.048%、0.041%、0.034%、0.054%;S/Se平均值分别为717、803、955、976。毒砂含硒最低,w(Se)均小于0.001%。不同矿体、不同容矿岩中硫化物的含硒量也有明显差别。Ⅰ号矿床硫化物的硒含量明显高于Ⅲ号矿床,二者硒平均含量分别为0.076%与0.013%,S/Se平均值分别是495和2802。不同容矿岩中凝灰质碎屑岩、绿泥石岩、石英脉中的硫化物w(Se)平均分别是0.056%、0.047%、0.018%;S/Se平均值分别为635、495、2102。这些数据表明该矿床的硫化物形成于较高温度,具岩浆热液作用的特征;Ⅰ、Ⅲ号矿床具不同的成矿环境及成矿多期性的特点,它对该矿床的成因及硒的赋存状态研究具有重要意义。