胶西北新城金矿床硫同位素地球化学

新城金矿床是胶西北金矿集区中典型的破碎带蚀变岩型金矿床,其热液成矿作用可划分为四个阶段: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-方解石阶段(IV),其中金主要赋存于II和III阶段的黄铁矿内。该矿床赋矿围岩为郭家岭岩体,岩性为石英二长岩和二长花岗岩,主要为胶东群变质基底经部分熔融形成。胶东群变粒岩硫同位素较为均一(δ34S值介于6.9‰~9.4‰,均值为8.0‰);郭家岭岩体的δ34S值介于6.0‰~16.0‰,均值为8.6‰,反映了其硫同位素组成总体上继承了变粒岩的硫同位素特征;长英质脉岩的δ34S值变化范围为0.8‰~8.5‰(均值为6.7‰),其中4件样品的δ34S值变化范围为7.4‰~8.5‰,反映了其硫主要源自于郭家岭岩体,变粒岩可能提供了部分硫源;而其中1件样品的δ34S值仅为0.8‰,符合岩浆硫来源特征,表明深部岩浆可能也提供了部分硫源。新城金矿床矿石中硫化物δ34S值变化范围较大(4.3‰~10.6‰,均值为8.3‰),表明矿石硫可能源于郭家岭岩体、变粒岩和长英质脉岩,最终主要来源于胶东群变质基底。I阶段黄铁矿颗粒较小(5~600μm),晶形主要为立方体,反映其处于温度较高(300~350℃)、成矿流体的过饱和度较低、低氧逸度和硫逸度、冷却快速、物质供应不足的成矿环境;黄铁矿δ34S值变化范围为8.4‰~10.6‰,均值为9.7‰,反映了矿石硫可能源自于δ34S值较高的郭家岭岩体和变粒岩。II和III阶段黄铁矿粒径变化较大(3μm~2.5mm),晶形主要为五角十二面体,反映其处于中-低温度(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。其中,II阶段黄铁矿δ34S值变化范围为7.7‰~9.7‰,均值为8.7‰,表明矿石硫源除郭家岭岩体和变粒岩外,δ34S值较低的长英质脉岩可能也提供了部分硫源。III阶段硫化物δ34S值变化范围较大(4.3‰~9.4‰,均值为7.1‰),闪锌矿-方铅矿硫同位素热力学平衡温度范围为180~282℃,氧逸度约为10-37.3~10-36.8,反映了矿石硫源自于郭家岭岩体、变粒岩和长英质脉岩,硫化物δ34S值变化范围较大可能是硫同位素分馏达到平衡的结果。IV阶段黄铁矿粒径最小(1~5μm),为晶形完好、表面光滑的立方体晶形,表明其处于较低温度(200℃),成矿流体的过饱和度较低、氧逸度和硫逸度较低、物质供应不足的成矿环境。     

俯冲带硫的地球化学行为及硫循环SCIEI北大核心CSCD

俯冲带是全球最大的物质循环系统,控制着硫(S)在地球内部圈层及表层的循环,影响着大气圈、水圈、生物圈、岩石圈的稳定性以及地球的宜居性。厘清S在俯冲带中的地球化学行为和循环特征对理解地球各储库的氧化还原状态、岩浆作用与演化、成矿物质聚集、以及地球大气成分等具有重要意义。本文首先总结了进入俯冲带之前的大洋岩石圈的S结构模型,对S在大洋板片中的分布状态和地球化学特征进行了系统归纳。随后,系统阐述了俯冲带高压-超高压变质岩记录的板片变质及脱水过程中硫的地球化学行为。岩石学研究表明俯冲板片中的S多以硫化物相存在,硫酸盐矿物在弧前深度就已被释放或分解。相较于熔体,俯冲带流体中S的溶解度更高,是运移硫的更有效方式。DEW模型计算结果显示,流体中S含量总体较低,但在俯冲板片~90km处其含量有一个峰值(浓度0.5%~1.0%)。岩相学证据、地球化学测试结果、磷灰石S近边吸收结构(S-XANES)特征以及模拟结果都显示俯冲深部流体中S多以HS^(-)及H_(2)S形式存在,不含大量的SO_(4)^(2-)及硫酸盐;中f_(S_(2))流体有利于S迁移出俯冲板片,从而促进俯冲带大规模S循环,而高f_(S_(2))流体在流-岩交换过程沿流体通道发生S的锁固作用而不利于俯冲带S循环。质量平衡计算显示全球俯冲带S输入通量为4.65×10^(13)g/yr,弧下深度板片S输出通量为2.91×10^(12)g/yr,板片-岛弧S循环效率仅6.3%。俯冲板片在弧下深度可能存在一个短暂高效的S释放窗口,释放流体的δ^(34)S值为-2.1±3.0‰。基于高压-超高压变质岩中硫化物的研究,初步厘清了俯冲板片中S的地球化学行为,首次从板片角度全面、定量地限定了俯冲带的脱硫通量、效率、种型和同位素特征,提出俯冲带循环的S不是岛弧岩浆的氧化剂,与岛弧环境的正δ^(34)S值也无直接因果联系,对解析俯冲带S循环和理解地球长期的S循环具有重要意义。最后,本文还展望了俯冲带S循环的未来发展方向,应在俯冲带流体氧化还原性质(硫酸盐的命运)、俯冲沉积物对S循环的制约、俯冲带环境下多硫同位素的分馏效应、S循环与其它挥发分(如C等)循环之间的耦合关系、地球历史上深部S循环等方向做出探索,更深入地理解俯冲带及全球S循环过程。     

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ³⁴S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ³⁴S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ³⁴S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ³⁴S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ³⁴S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ³⁴S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ³⁴S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in ³⁴S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ³⁴S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in ³⁴S relative to those from the parent coal (average 7.5‰). The δ³⁴S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ³⁴S values for SO₄^− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.     

Sulfur redox reactions: Hydrocarbons,native sulfur,Mississippi Valley-type deposits,and sulfuric acid karst in the Delaware Basin,New Mexico and Texas

Hydrocarbons, native sulfur, Mississippi Valley-type (MVT) deposits, and sulfuric acid karst in the Delaware Basin, southeastern New Mexico, and west Texas, USA, are all genetically related through a series of sulfur redox reactions. The relationship began with hydrocarbons in the basin that reacted with sulfate ions from evaporite rock to produce isotopically light ( ³⁴S = -22 to -12) H₂S and bioepigenetic limestone (castiles). This light H₂S was then oxidized at the redox interface to produce economic native sulfur deposits ( ³⁴S = -15 to +9) in the castiles, paleokarst, and along graben-boundary faults. This isotopically light H₂S also migrated from the basin into its margins to accumulate in structural (anticlinal) and stratigraphic (Yates siltstone) traps, where it formed MVT deposits within the zone of reduction ( ³⁴S = -15 to +7). Later in time, in th zone of oxidation, this H₂S reacted with oxygenated water to produce sulfuric acid, which dissolved the caves (e.g., Carlsbad Cavern and Lechuguilla Cave, Guadalupe Mountains). Massive gypsum blocks on the floors of the caves ( ³⁴S = -25 to +4) were formed as a result of this reaction. The H₂S also produced istopically light cave sulfur ( ³⁴S = -24 to -15), which is now slowly oxidizing to gypsum in the presence of vadose drip water.     

Mechanism of Hg(II) immobilization in sediments by sulfate-cement amendment

Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO₄ amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg L_III- and S K-edge. In amended sediments, XRD, SEM and sulfur K-edge XANES indicated formation of gypsum in seawater experiments or ettringite-type (Ca₆Al₂(SO₄)₃(OH)₁₂^.26H₂O) phases in fresh water experiments, depending on the final solution pH (seawater ∼8.5; freshwater ∼10.5). Analysis of Hg EXAFS spectra showed Cl and Hg ligands in the first- and second-coordination shells at distances characteristic of a polynuclear chloromercury(II) salt, perhaps as a nanoparticulate phase, in both seawater and fresh water experiments. In addition to the chloromercury species, a smaller fraction (∼20–25%) of Hg was bonded to O atoms in fresh water sample spectra, suggesting the presence of a minor sorbed Hg fraction. In the absence of amendment treatment, Hg sorption and resistance to extraction can be accounted for by relatively strong binding by reduced S species present in the marsh sediment detected by S XANES. Thermodynamic calculations predict stable aqueous Hg–Cl species at seawater final pH, but higher final pH in fresh water favors aqueous Hg-hydroxide species. The difference in Hg coordination between aqueous and solid phases suggests that the initial Hg–Cl coordination was stabilized in the cement hydration products and did not re-equilibrate with the bulk solution with aging. Collectively, results suggest physical encapsulation of Hg as a polynuclear chloromercury(II) salt as the primary immobilization mechanism.     

Sulfur isotopic geochemistry of the huize Pb-Zn ore field in yunnan province北大核心CSCD

In order to constrain sulfur isotope compositions of ore-forming fluids, ore-forming temperature, source of sulfur and mechanism of sulfur reduction in the Huize lead-zinc ore field, based on sulfur isotope compositions from previous studies, new data of sulfur isotopic composition of primary sulfide of upper ore-bodies in Qilinchang and newly-found sulfate outside the deposits were utilized in this study. It show that 5 values of primary sulfide vary from 8. Oft∗ to 17. 68 ft∗ , and sulfur isotopes in ore-forming fluid have reached equilibrium; S'lS values of sulfur out side the deposits vary from 17. 95ft∗ to 24. 30ft∗ with average value of 20. 14ft∗ , yielding sulfur isotopic composition of ore-for ming fluids as 14. 14ft∗ by the Pinekney method for mineral association. The value is close to 5'4S of marine sulfate. Ore-forming temperature is calculated as 1 34 - 388by isotope geological thermometer. The results of fluid inclusion thermometer indicate that barites were crystallized from hydrothermal fluid, which is suggested that sulfur in ore-forming fluid probably originates from marine sulfate of stratum in and outside the deposits or hydrothermal barites found in ore district. Reduction mechanism of sulfate is likely to be themio-chemical sulfate reduction.     

台湾地区湖泊水库悬浮颗粒有机质之碳、氢、氧、氮、硫元素计量分析

对台湾地区１８个湖泊水库水体中悬浮颗粒有机质之碳，氢，氧，氮，硫和叶绿素α的含量进行了分析，其中ＰＯＯ乃首度以元素分析仪直接测量。结果为，ＰＯＣ，ＰＯＨ，ＰＯＯ，ＰＯＮ，ＰＯＳ含量分别介于１３８－８３７０μｇ／Ｌ，１３．７－９２６．１μｇ／Ｌ，３１－２６２３μｍ／Ｌ，１４－１２６５μｇ／Ｌ，１．９－４９．７μｇ／Ｌ之间，Ｃｈ１．ａ含量则介于０．３１－９６．７５μｇ／Ｌ之间，ＰＯＭ元素间原子数关系为     

1981–2020 winter ozone trends,Erzgebirge, Central Europe

Tropospheric ozone (O₃) acts as greenhouse gas and air pollutant. Over the last 100 years, tropospheric O₃ levels increased above background by factor 2.5 in the northern hemisphere and by factor 3–4 across Europe. The gas poses a potential risk to forest ecosystems in many mountain areas. There, O₃ concentrations result from long-range transport and are influenced by removal processes (dry deposition, gas phase and cloud removal, reduction on wet aerosols). Most trend studies analyzed annual-mean concentrations. We focus on winter O₃ trends at high altitudes in the German/Czech Erzgebirge (period 1981–2020) to avoid major noise from photochemical reactions and to better explain recent O₃ behavior in Central Europe. Hourly air quality and meteorological data from four stations (Carlsfeld, CAR; Fichtelberg, FIB; Schwartenberg, SWB; Zinnwald, ZIW) were used to analyze O₃ trends. The data can explain the complex O₃ formation and removal behavior.Three distinct periods of O₃-concentration trends can be discerned: i) Until the late 1980s, characterized by relatively low O₃ concentrations. ii) Dramatic transformation in the 1990s with changing air pollution in Central Europe. Strong O₃-concentration increase at FIB is corroborated by data from CAR and ZIW. iii) Stabilization as of 1997/98, when O₃ concentrations remained at the same level for all four stations, despite general regional air pollution decrease. Key results are:a) Winter O₃ trends mainly depend on O₃ concentration of air masses transported to the stations and on the O₃-removal potential (ORP) of clouds, not on local formation processes.b) ORP differs between clouds and fog, depending on droplet chemical composition. Fog from the North Bohemian Basin showed the highest ORP due to reaction with liquid phase S(IV). However, O₃ reactions with O₂⁻ in fog droplets showed high ORP, too, depending on cloud-water pH values and NO_x concentrations.c) So-called “Bohemian fog” decreased, and with it related ORP, while that of clouds from westerly and northwesterly air masses remained nearly unchanged since 1997/98.d) Decreasing ORP in clouds and fog (= higher O₃ concentration) oppose decreasing O₃ concentrations in westerly air masses. Both effects lead to unchanged O₃ levels in the Erzgebirge since 1997/98.     

Reconstruction of paleo-redox conditions and early sulfur cycling during deposition of the Cryogenian Datangpo Formation in South China

In South China, the Datangpo black shales (663 Ma–654.5 Ma) were deposited during the Cryognian interglacial time between the Sturtian and Marinoan glaciations. Multi-geochemical proxies, including different iron speciation and relevant ratios (Fe_HR/Fe_T, Fe_P/Fe_HR and Fe_T/Al ratios) and molybdenum concentrations, were used to reconstruct the paleo-depositional environment of this black shale horizon. The ratios of different iron species (Fe_HR/Fe_T > 0.38 and Fe_P/Fe_HR < 0.80) suggest an overall anoxic conditions (ferruginous) over the deposition of the black shales, although intermittent euxinic (Fe_HR/Fe_T > 0.38 and Fe_P/Fe_HR ≈ 0.80) and oxic (Fe_HR/Fe_T < 0.38) intervals could have occurred. Furthermore, Fe_T/Al ratios (Fe_T/Al ≤ 0.51) confirm that water column may not be persistent euxinia during the deposition of the Datangpo black shales. Meanwhile, molybdenum concentrations show a decreasing trend towards the top of the black shales, reconciling the gradual oxygenating trend during this period as stated above. Compared to δ³⁴S_Py values in the Mesoproterozoic deep ocean, more positive δ³⁴S_Py values of this study may result from a small size of sulfate reservoir. The small-size sulfate reservoir and concurrent enrichment of molybdenum indicate that the ocean chemistry in the Cryogenian Period is similar to that in the Archean Eon.     

Microbial response to surface microtopography: the role of metabolism in localized mineral dissolution

We examine the role of microtopographical surface features on sulfide minerals in localizing and aligning bacterial adhesion. Experimental data shows strong correlation between bacterial cell alignment and principal crystallographic axes of pyrite (100 and 110). While bacteria often adhere to visible surface imperfections such as scratches, in many cases no associated surface features are visible. Additionally, the size of the surface imperfection does not unambiguously determine its effect in localizing and aligning bacterial cells. We theoretically model bacterial adhesion. We find that the depth of a surface feature such as a scratch is less important than its cross-sectional shape. Surface features that conform to the bacterial shape can strongly alter local bacterial adhesion energies, even with heights of only 10 nm. Hence, small local surface alterations due to bacterial metabolism could strongly affect local adhesion parameters, and may account for the observed bacterial distributions on mineral surfaces.