Sulfur biogeochemistry and isotopic fractionation in shallow groundwater and sediments of Owens Dry Lake, California

Groundwater and sediment samples (∼ 1 m depth) at sites representative of different groundwater pathways were collected to determine the aqueous speciation of sulfur and the fractionation of sulfur isotopes in aqueous and solid phases. In addition, selected sediment samples at 5 depths (from oxic to anoxic layers) were collected to investigate the processes controlling sulfur biogeochemistry in sedimentary layers. Pyrite was the dominant sulfur-bearing phase in the capillary fringe and groundwater zones where anoxic conditions are found. Low concentrations of pyrite (< 5.9 g kg^− 1) coupled with high concentrations of dissolved sulfide (4.81 to 134.7 mg L^− 1) and low concentrations of dissolved Fe (generally < 1 mg L^− 1) and reducible solid-phase Fe indicate that availability of reactive Fe limits pyrite formation. The relative uniformity of down-core isotopic trends for sulfur-bearing mineral phases in the sedimentary layers suggests that sulfate reduction does not result in significant sulfate depletion in the sediment. Sulfate availability in the deeper sediments may be enhanced by convective vertical mixing between upper and lower sedimentary layers due to evaporative concentration. The large isotope fractionation between dissolved sulfate and sedimentary sulfides at Owens Lake provides evidence for initial fractionation from bacterial sulfate reduction and additional fractionation generated by sulfide oxidation followed by disproportionation of intermediate oxidation state sulfur compounds. The high salinity in the Owens Lake brines may be a factor controlling sulfate reduction and disproportionation in hypersaline conditions and results in relatively constant values for isotope fractionation between dissolved sulfate and total reduced sulfur.     

Sn, B and Pb-Zn Skarn, Vein and Disseminated Deposits in the East Sikhote–Alin, Russia

Abstract: Sn, B and Pb-Zn skarn, vein and disseminated deposits occur in the eastern part of Sikhote-Alin fold system associated with the late Cretaceous-earliest Paleogene volcano-plutonic complexes, which are products of a continental margin-type subduction along the East Sikhote-Alin belt. There are two metallogenic zones where the ore deposits are concentrated. The Taukha metallogenic zone combining B and Pb-Zn skarn, vein and disseminated deposits occurs on the main volcanic chain along the Japan Sea coast. Late Cretaceous-earliest Paleogene calc-alkaline plutonic and volcanic rocks of magnetite series predominate here. Volcanic rocks overlie on the lower Cretaceous Taukha terrane which consists of abundant olistostromes with numerous olistoliths of Triassic limestones. During the middle-late Cretaceous time, an ignimbrite erupted and formed a huge borosilicate skarn deposit. A later subduction related volcanism of the late Cretaceous-earliest Paleogene stage (70–55 Ma) was predominated by andesites and rhyodacites. Many Pb-Zn skarn and vein deposits were formed. Sulfur isotope compositions of galena in the B and Pb-Zn deposits of the Taukha metallogenic zone vary from –1. 3 to +2. 0%, averaging 0% in the δ³⁴S.     

Comparison of Time-Dependent Tracer Ages in the Western North Pacific: Oceanic Background Levels of (SF6, CFC-11, CFC-12 and CFC-113

To verify the actual usefulness of time-dependent tracer dating techniques in the ocean, we simultaneously obtained two cross sections of sulfur hexafluoride (SF₆) and chlrofluoromethanes (CFC-11, trichlorofluoromethane; CFC-12, dichloro-difluromethane; CFC-113, trichlorotrifluoroethane) in the western North Pacific in 1998. The vertical distribution patterns of SF₆ and CFC-113 were similar in shape to those of CFC-11 and CFC-12. Maximum penetration depths of SF₆ and CFC-113 remained around 800 m in the subpolar region and 400 m in the tropical region, while the maximum penetration depths of CFC-11 and CFC-12 were still found below 1000 m depth. We also found all maximum contents of these tracers around 26.6−26.8σ_θ with a gradual decrease southward. This suggested that a new subsurface water mass in the subpolar region spread out over the entire North Pacific, which agrees closely with previous studies based on the salinity minimum. Moreover, we compared the tracer ages (the elapsed period of a water mass from when the water mass left from the ocean surface) using ten time-dependent tracer dating techniques, CFC-11, CFC-12, CFC-113, SF₆, CFC-11/CFC-12, CFC-113/CFC-11, CFC-113/CFC-12, SF₆/CFC-11, SF₆/CFC-12 and SF₆/CFC-113. This quantitative evaluation of multiple tracer dating techniques in the ocean was the first confirmation of its usefulness based on the observational data on the ocean basin-wide scale. We conclude that SF₆/CFC-11, SF₆/CFC-12, SF₆/CFC-113 and SF₆ dating techniques would be the most promising tools for determining the age of water mass not only just for the past several decades but for the future, too. This revised version was published online in July 2006 with corrections to the Cover Date.     

电感耦合等离子体发射光谱法测定石膏矿样品中的三氧化硫

样品用稀盐酸处理,在酸性条件下石膏样品中的三氧化硫以硫酸根状态存在于待测溶液中,过滤除去酸不溶物。处理好的待测溶液可直接上等离子体发射光谱仪ICAP-6300(美国热电制造)上测定。方法的检出限为0.01%,采用本法测定国家标准物质GBW03109,GBW03109a,GBW03110,GBW03111a,结果表明标准样品测定的相对误差为-0.411%~0.274%,相对误差允许限为1.07%,能够满足分析质量要求。     

Sources of environmental sulfur in the groundwater system,southern New Zealand

Sulfide minerals commonly occur in sediments and basement rocks in southern New Zealand, as authigenic precipitates from groundwater below the oxygenated surface zone. There are two principal potential sources for sulfur in the groundwater system: weathering of sulfide minerals in the metamorphic basement and rainwater-derived marine aerosols. We present data for these two key sulfur sources: metamorphic sulfide and associated hydrothermal Au-bearing veins within the Otago Schist (average δ³⁴S = −1.8 ± 2.4‰), and an inland saline lake (S derived entirely from rainwater, δ³⁴S = 21.4 ± 0.8‰). We use these two end member δ³⁴S values to estimate the contributions of these sources of sulfur in authigenic groundwater sulfide minerals and in waters derived from oxidation of these sulfide minerals, across a range of environments. We show that authigenic groundwater pyrite along joints in the Otago schist is derived primarily from metamorphic basement sulfur. In contrast, authigenic groundwater pyrite cementing Miocene-Recent aquifers shows a substantial marine aerosol component, and represents a distinct hydrogeological system. We suggest that marine aerosols represent a significant flux to the terrestrial sulfur cycle that has been present through the groundwater system in Otago over the past 20 million years.     

滇西沧源铅锌多金属矿集区成矿地球化学特征

滇西沧源铅锌多金属矿集区位于中缅边境的金腊-金厂一带,是云南省地矿资源股份有限公司新近开发的一个资源产地.本文重点提供了流体包裹体中稀土微量元素和矿石的S、Pb同位素的分析结果,并对成矿流体性质,成矿物质来源等进行了讨论.研究表明,本区流体包裹体中∑BEE变化较大,在0.371～212.1×10-9之间.反映轻重稀土分馏程度的LREE/HREE比值和(La/Yb)N比值变化也比较大,分别落在1.23～31.47和2.87～505之间.矿石的硫同位素除一个重晶石的δ34S偏高,达20.8～22.1‰,其它硫化物的δ34S均落在-0.6～5.1‰范围内,具幔源硫值特征.矿石的铅同位素208Pb/204Pb、207Pb/204Pb和206Ph/204Pb分别变化在38.621～38.993,15.584～15.738和18.568～18.800之间,不同矿段、不同硫化物矿物(方铅矿、闪锌矿、黄铁矿、辉锑矿)之间,Pb同位素组成范围非常相近,表明研究区各矿段,铅的来源和成因是均一的、相同的,而且具有造山带Pb同位素特征.结合区域成矿地质背景及流体包裹体c、H、0同位素研究结果,推测本区成矿流体是以浅部流体为主,并有深源流体参与的一种混合流体.矿石S、Pb同位素组成表明,成矿物质也具有壳幔混合源的特征.     

海陆相蒸发岩硫同位素值变化和地球化学应用

硫同位素作为一种稳定的同位素,几乎遍布各种自然环境,出现于地质上所能跨越的所有温度范围。自然界中,不同环境下δ~(34)S值的差别可达180‰。研究表明,蒸发沉积硫酸盐的δ~(34)S值可以代表相应水体的δ~(34)S值,通过研究蒸发岩中的δ34S值,结合其它指标,可判断沉积环境,示踪成矿物质来源,研究成矿作用过程,为重建古地理古环境提供依据。在前人研究基础上总结了硫同位素分馏的影响因素及其在地球化学方面的应用;分析了陆相盆地蒸发咸化过程中水体δ~(34)S值的变化特征;对比研究了部分海陆相盆地硫酸盐δ~(34)S值特征,并指出对陆相盆地,不同类型的水体中δ~(34)S值变化趋势仍需进一步研究。     

Using sediment geochemistry to infer temporal variation of methane flux at a cold seep in the South China Sea

Release of methane from the seafloor throughout the world's oceans and the biogeochemical processes involved may have significant effects on the marine sedimentary environment. Identification of such methane release events in marine sediment records can hence provide a window into the magnitude of ancient seeps. Here, we report on analysis of the geochemical composition of samples in a 12.3 m long sediment core (DH-5) collected from a seep site in the South China Sea (SCS). Our aim has been to investigate whether the evidence for the presence of methane release event within sediments is discernible from solid-phase sediment geochemistry. We show that sedimentary total sulfur (TS), δ³⁴S values of chromium reducible sulfur (δ³⁴S_CRS) along with total organic carbon (TOC) and total inorganic carbon (TIC) content can be used to infer the presence of methane release events in cold seep settings. At least three methane release events were identified in the studied core (Unit I at 400–550 cm, Unit II at 740–820 cm, and Unit III at 1000–1150 cm). According to the characteristic of redox-sensitive elements (eg., Mo, U and Mn), we suggest that methane flux has been changed from relatively high (Unit I) to low (Unit II and III) rates. This inference is supported by the coupled occurrence of ³⁴S-enriched sulfides in Unit II and III. AMS ¹⁴C dates from planktonic foraminifera in Unit I suggest that high methane flux event occurred at ∼15.4–24.8 kyr BP, which probably resulted in locally-focused aerobic methane oxidation. Overall, our results suggest that TS, TOC, TIC and δ³⁴S_CRS have potential for identifying present and fossil methane release events in marine sediments.     

新疆塔里木西南缘塔木铅锌矿硫同位素特征与成因

塔木铅锌矿位于塔里木西南缘,为碳酸盐岩容矿型铅锌矿。矿床形成经历了沉积期、成岩期和后生期。沉积期以内碎屑角砾和纹层构造为标志。成岩期以成岩角砾、重结晶白云石为标志。后生期以崩塌角砾、后生角砾及管/脉构造为标志。成矿期介于成岩期和后生期并具有溶蚀-交代和充填两个阶段。细粒闪锌矿和方铅矿多为溶蚀-交代阶段产物。粗粒闪锌矿和方铅矿多为充填阶段产物。本次研究对来自14个标本的沉积期和成矿期51件闪锌矿、方铅矿、黄铁矿和黄铜矿样品进行了硫同位素测试。塔木铅锌矿硫化物硫同位素值具有较大的变化范围。沉积期形成的金属硫化物(δ34SCDT介于-17.6‰～-7.3‰)较成矿期金属硫化物(δ34SCDT介于-5.7‰～+10.2‰)多富集轻硫同位素。充填阶段形成的硫化物(δ34SCDT介于+5.1‰～+10.2‰)较溶蚀-交代阶段硫化物(δ34SCDT介于-5.7‰～+9.2‰)富重硫,并且硫同位素达到平衡。结合地质背景、矿物生成顺序、矿石结构、流体包裹研究资料和硫同位素特征可以得出热化学硫酸盐还原作用(TSR)是成矿期HS-形成的主要机制,含硫有机质热裂解硫也是成矿期硫源之一,溶蚀-交代阶段硫储库效应和硫化物溶度积(Ksp)制约硫同位素值的变化。通过本次研究厘定了塔木铅锌矿矿化形成机制、硫酸盐还原特征和硫的来源,并进一步指出其硫同位素特征支持矿床流体混合成因模型。     

Alkali and halogen chemistry in volcanic gases on Io

We use chemical equilibrium calculations to model the speciation of alkalis and halogens in volcanic gases emitted on Io. The calculations cover wide temperature (500-2000 K) and pressure (10⁻⁶ to 10⁺¹ bars) ranges, which overlap the nominal conditions at Pele (T=1760 K, P=0.01 bars). About 230 compounds of 11 elements (O, S, Li, Na, K, Rb, Cs, F, Cl, Br, I) are considered. The elemental abundances for O, S, Na, K, and Cl are based upon observations. CI chondritic elemental abundances relative to sulfur are used for the other alkalis and halogens (as yet unobserved on Io). We predict the major alkali species in Pele-like volcanic gases and the percentage distribution of each alkali are LiCl (73%), LiF (27%); NaCl (81%), Na (16%), NaF (3%); KCl (91%), K (5%), KF (4%); RbCl (93%), Rb (4%), RbF (3%); CsCl (92%), CsF (6%), Cs (2%). Likewise the major halogen species and the percentage distribution of each halogen are NaF (88%), KF (10%), LiF (2%); NaCl (89%), KCl (11%); NaBr (89%), KBr (10%), Br (1%); NaI (61%), I (30%), KI (9%). We predict the major halogen condensates and their condensation temperatures at P=0.01 bar are NaF (1115 K), LiF (970 K); NaCl (1050 K), KCl (950 K); KBr (750 K), RbBr (730 K), CsBr (645 K); and solid I₂ (200 K). We also model disequilibrium chemistry of the alkalis and halogens in the volcanic plume. Based on this work and our prior modeling for Na, K, and Cl in a volcanic plume, we predict the major loss processes for the alkali halide gases are photolysis and/or condensation onto grains. Their estimated photochemical lifetimes range from a few minutes for alkali iodides to a few hours for alkali fluorides. Condensation is apparently the only loss process for elemental iodine. On the basis of elemental abundances and photochemical lifetimes, we recommend searching for gaseous KCl, NaF, LiF, LiCl, RbF, RbCl, CsF, and CsCl around volcanic vents during eruptions. Based on abundance considerations and observations of brown dwarfs we also recommend a search of Io's extended atmosphere and the Io plasma torus for neutral and ionized Li, Cs, Rb, and F.