Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS   总被引：4，自引：0，他引：4  

Paul R. Craddock  Olivier J. Rouxel  Lary A. Ball  Wolfgang Bach   《Chemical Geology》2008,253(3-4):102-113

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.  相似文献   

Estimation of groundwater recharge using the soil moisture budget method and the base-flow model     

Cheng-Haw Lee  Hsin-Fu Yeh  Jin-Fa Chen 《Environmental Geology》2008,53(8):1787-1797

A detailed characterization of the site is crucial to designing an efficient method of managing the risks associated with tailings from abandoned mines. Therefore, samples collected from various depths within tailings in Guryong mine, Korea, were analyzed for their chemical, physical and mineralogical characteristics. All samples of the Guryong tailings had acid-generating potential. However, in the oxidation zone, the net acid generation (NAG) was low (30 kg H₂SO₄ t⁻¹) although the acid neutralization potential (ANP) was less than zero. The ANP values in the unoxidation zone were higher (> −56.0 kg CaCO₃ t⁻¹) than in the other zones. As a result, the amount of alkali ions that are needed to neutralize the acid needs to be considered. In this experiment G3, G4 and G6 drill cores containing fine tailings particles near the unoxidation zone were observed to contain calcite (CaCO₃) with acid-neutralizing capacity. A low pH (2−4) in the oxidation zone of the tailings changed to a neutral pH in the unoxidation zone of the tailings. These results suggest that the acid-neutralizing capacity of the tailings was controlled by particle and mineral composition of tailings.  相似文献   

On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes     

Eric A. Betterton 《Journal of Atmospheric Chemistry》1993,17(4):307-324

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.  相似文献   

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean     

J. P. Putaud  N. Mihalopoulos  B. C. Nguyen  J. M. Campin  S. Belviso 《Journal of Atmospheric Chemistry》1992,15(2):117-131

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.  相似文献   

Carbon, sulfur and O₂ across the Permian–Triassic boundary     

Robert A. Berner   《Journal of Geochemical Exploration》2006,88(1-3):416

A model for the carbon and sulfur cycles across the Permian–Triassic boundary has been constructed from carbon and sulfur isotopic data. Results indicate a drop in global organic matter burial, the formation of an anoxic deep ocean, and a large drop in atmospheric oxygen over the time span 270 to 240 Ma. Much of these changes were probably due to a drop in terrestrial productivity and preservation and an increase in global aridity.  相似文献   

Origin of the Nchanga copper–cobalt deposits of the Zambian Copperbelt     

Ross R. McGowan  Stephen Roberts  Adrian J. Boyce 《Mineralium Deposita》2006,40(6-7):617-638

The Zambian Copperbelt forms the southeastern part of the 900-km-long Neoproterozoic Lufilian Arc and contains one of the world’s largest accumulations of sediment-hosted stratiform copper mineralization. The Nchanga deposit is one of the most significant ore systems in the Zambian Copperbelt and contains two major economic concentrations of copper and cobalt, hosted within the Lower Roan Group of the Katangan Supergroup. A Lower Orebody (copper only) and Upper Orebody (copper and cobalt) occur towards the top of arkosic units and within the base of overlying shales. The sulfide mineralogy includes pyrite, bornite, chalcopyrite, and chalcocite, although in the Lower Orebody, sulfide phases are partially or completely replaced by malachite and copper oxides. Carrollite is the major cobalt-bearing phase and is restricted to fault-propagation fold zones within a feldspathic arenite. Hydrothermal alteration minerals include dolomite, phlogophite, sericite, rutile, quartz, tourmaline, and chlorite. Quartz veins from the mine sequence show halite-saturated fluid inclusions, ranging from ~31 to 38 wt% equivalent NaCl, with homogenisation temperatures (Th_TOT) ranging between 140 and 180°C. Diagenetic pyrites in the lower orebody show distinct, relatively low δ ³⁴S, ranging from −1 to −17‰ whereas arenite- and shale-hosted copper and cobalt sulfides reveal distinctly different δ ³⁴S from −1 to +12‰ for the Lower Orebody and +5 to +18‰ for the Upper Orebody. There is also a clear distinction between the δ ³⁴S mean of +12.1±3.3‰ (n=65) for the Upper Orebody compared with +5.2±3.6‰ (n=23) for the Lower Orebody. The δ ¹³C of dolomites from units above the Upper Orebody give δ ¹³C values of +1.4 to +2.5‰ consistent with marine carbon. However, dolomite from the shear-zones and the alteration assemblages within the Upper Orebody show more negative δ ¹³C values: −2.9 to −4.0‰ and −5.6 to −8.3‰, respectively. Similarly, shear zone and Upper Orebody dolomites give a δ ¹⁸O of +11.7 to +16.9‰ compared to Lower Roan Dolomites, which show δ ¹⁸O of +22.4 to +23.0‰_. Two distinct structural regimes are recognized in the Nchanga area: a weakly deformed zone consisting of basement and overlying footwall siliciclastics, and a moderate to tightly folded zone of meta-sediments of the Katangan succession. The fold geometry of the Lower Roan package is controlled by internal thrust fault-propagation folds, which detach at the top of the lowermost arkose or within the base of the overlying stratigraphy and show vergence towards the NE. Faulting and folding are considered to be synchronous, as folding predominantly occurred at the tips of propagating thrust faults, with local thrust breakthrough. The data from Nchanga suggests a strong link between ore formation and the development of structures during basin inversion as part of the Lufilian Orogeny. Sulfides tend to be concentrated within arenites or coarser-grained layers within shale units, suggesting that host-rock porosity and possibly permeability played a role in ore formation. However, sulfides are also commonly orientated along, but not deformed by, a tectonic fabric or hosted within small fractures that suggest a significant role for deformation in the development of the mineralization. The ore mineralogy, hydrothermal alteration, and stable isotope data lend support to models consistent with the thermochemical reduction of a sulfate- (and metal) enriched hydrothermal fluid, at the site of mineralization. There is no evidence at Nchanga for a contribution of bacteriogenic sulfide, produced during sedimentation or early diagenesis, to the ores.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.Editorial handling: H. Frimmel  相似文献   

Transformation of arsenic compounds in modern intertidal sediments of Iriomote Island, Japan   总被引：1，自引：0，他引：1  

Harue Masuda  Yoshito Yamatani  Mitsuru Okai   《Journal of Geochemical Exploration》2005,87(2):587-81

The arsenic accumulation process in intertidal sediments of Iriomote Island, Japan, is analyzed as a naturally balanced arsenic-fixation system. Major and minor element chemistry is analyzed by X-ray fluorescence photometry, mineralogy is investigated by X-ray diffractometry, and four arsenic compounds are characterized by hydrogen-generated atomic absorption photometry. It is found that arsenic is accumulated by iron hydroxides/oxides precipitated following the decomposition of humic acids in the shallower sediment, and is subsequently incorporated into iron sulfide minerals at depth. The arsenic is immobile during incorporation into arsenic-bearing phases, suggesting that arsenic is unlikely to be released into the porewater under natural conditions in early diagenesis. The formation and decomposition of arsenic-bearing organic compounds appear to be associated with the formation and decomposition of arsenic in oxyhydroxides/oxides, suggesting that microbial activity may play an important role in controlling the behavior of arsenic and arsenic-bearing phases in the sediment column.  相似文献   

胶西北大尹格金矿床成矿机理:载金黄铁矿标型及硫同位素地球化学约束   总被引：4，自引：3，他引：1  

张瑞忠  王中亮  王偲瑞  刘育  秦文凯 《岩石学报》2016,32(8):2451-2464

胶东是我国最重要的金矿集中区,破碎带蚀变岩型金矿床是区内最主要的金矿床类型,该类型金矿床已探明金资源量占全区的90%以上,其巨量金的来源是引人瞩目的关键科学问题。招平断裂带是该区内规模最大的断裂-成矿带,位于招平金矿带中段的大尹格庄金矿床是该金矿带最具代表性的破碎带蚀变岩型金矿床之一,已探明金金属量约283t。大尹格庄金矿床严格受沿胶东群与玲珑花岗岩接触带发育的NNE向招平断裂带控制,矿体赋存在招平断裂下盘黄铁绢英岩化和碎裂岩化玲珑花岗岩中,主要由Ⅰ号和Ⅱ号矿体组成,其具有相似的矿物组成,矿石主要矿物是绢云母、石英、黄铁矿,次要矿物是钾长石、斜长石、黑云母、方解石、黄铜矿、方铅矿、闪锌矿、磁黄铁矿、黝铜矿和自然金、自然银、金银矿、碲银矿等;其中黄铁矿是最主要的载金矿物。根据穿插关系和矿物共生组合,大尹格庄金矿床内成矿作用可划分为4个成矿阶段,分别是黄铁矿-石英-绢云母阶段(I)、石英-黄铁矿阶段(Ⅱ)、石英-多金属硫化物阶段(Ⅲ)和石英-方解石-多金属硫化物阶段(Ⅳ)。各个成矿阶段的黄铁矿的晶体形态标型研究表明,成矿Ⅰ阶段黄铁矿以粗粒自形立方体为主,含有少量五角十二面体;成矿Ⅱ和Ⅲ阶段黄铁矿以细粒五角十二面体为主,且具有更多五角十二面体、八面体和立方体形成的聚形;成矿Ⅳ阶段主要为细粒立方体晶形。不同矿体各个成矿阶段的硫化物的δ~(34)S值集中在4.58‰~7.54‰,具有一定的塔式效应,正向偏离陨石硫,与胶东地区胶东群变质岩、围岩花岗岩类δ~(34)S比较接近,指示大尹格庄金矿床各个成矿阶段的矿石硫源总体一致,与胶东群变质岩和中生代花岗岩间具有继承演化关系。此外,从成矿Ⅰ阶段→Ⅱ阶段→Ⅲ阶段→Ⅳ阶段,大尹格庄金矿床矿石硫化物δ~(34)S呈现出逐渐降低的趋势,反映了成矿过程中物理化学条件的演化趋势:Ⅰ阶段为较高温度(330~350℃)、快速冷却、低过饱和度、低氧逸度和硫逸度的成矿环境;Ⅱ和Ⅲ阶段黄铁矿形成于中-低温(200~300℃)、成矿流体过饱和度高、高氧逸度和硫逸度、缓慢冷却同时物质供应充分的成矿环境;Ⅳ阶段处于较低温度(200℃)、热液流体过饱和度较低、低氧逸度和硫逸度、同时物质供应不足的成矿环境。  相似文献   

热液中硫化物与硫代硫酸盐的同位素交换机制及多硫化物的作用     

储雪蕾 《岩石学报》1993,9(3):255-266

  相似文献   

气态SO_2转化及其数值模型研究     

杨礼荣  任阵海  林子瑜 《大气科学》1993,17(3):328-337

本文基于对室外烟雾箱实验,探讨了SO_2的转化机制及影响SO_2转化的因素,由此并借助于烟团模型,建立了SO_2转化和硫酸盐气溶胶细粒子生成的数值模型,用于估算从排放源排入大气的SO_2浓度及其转化成硫酸盐细粒子的浓度以及它们的空间分布,与实测结果相比,两者有较好的一致性.同时指出,由于大气中细粒子(粒径小于1μm)可通过人体呼吸进入并沉积在肺泡中而对健康有不利影响,从而说明研究大气中细粒子污染的迫切性.  相似文献