Protocol for Quantitative Detection of Elemental Sulfur and Polysulfide Zero-Valent Sulfur Distribution in Natural Aquatic Samples

A HPLC-based protocol has been developed for the determination of zero-valent sulfur (ZVS) speciation, including solid, colloidal elemental sulfur and individual inorganic polysulfides in natural aquatic samples. The protocol includes four experimental procedures: (1) determination of polysulfide speciation by rapid single-phase derivatisation with methyl trifluoromethanesulfonate; (2) determination of the sum of polysulfide and colloidal sulfur by reaction with hydrogen cyanide (cyanolysis); (3) determination of total zero-valent sulfur by treatment with zinc chloride followed by extraction with chloroform; and (4) chromatographic determination of polythionates without sample pre-treatment. With proper sampling and preservation techniques in the field or on board ship, this combination of methods allowed the quantitative determination of: (a) individual polysulfide species; (b) dispersed colloidal sulfur; (c) dispersed solid elemental sulfur; and (d) tetra-, penta- and hexathionates. With minor modification, the method could be expanded to include other polythionates. Sixteen various wet chemical and liquid chromatographic methods were tested on nine synthetic reference samples (including solid elemental sulfur, colloidal elemental sulfur, inorganic polysulfides and polythionates) to establish the optimal protocol. The protocol was further evaluated by analysing the zero-valent sulfur content in microbially-produced sulfur and in sulfur from two natural samples of sulfide-rich seawater from tidal flats pools of the Wadden Sea (Germany).     

Kinetics of Disproportionation of Inorganic Polysulfides in Undersaturated Aqueous Solutions at Environmentally Relevant Conditions

The rate of the reversible homogeneous disproportionation of polysulfides was studied by following the optical absorbance of polysulfide solutions in a continuous plug flow reactor equipped with an on-line photometric detector. In order to avoid heterogeneous slow reactions involving sulfur colloids or precipitate, the reaction was initiated by an abrupt pH change from an undersaturated solution containing predominantly tetrasulfide species to a pH where pentasulfide is the dominant species. The disproportionation was found to follow first order reversible reaction dynamics. At environmentally relevant conditions the characteristic time of the disproportionation reaction is of the order of 10 s. This characteristic time implies that necessary conditions for speciation of the different polysulfide species by chromatography or another separation and subsequent quantification scheme should be of the order of 1 s.     

Speciation of Polysulfides and Zerovalent Sulfur in Sulfide-rich Water Wells in Southern and Central Israel

Zerovalent sulfur and inorganic polysulfides were determined in nine sulfide-rich water wells in central and southern Israel. Although the two locations belong to the same aquifer, they are characterized by different pH and hydrogen sulfide levels. Hydrogen sulfide in the central Israel wells ranged between 19 and 32 μM, and the pH was 7.26 ± 0.07. The southern basin is characterized by lower water circulation, lower pH (around 6.8), and higher hydrogen sulfide levels (>470 μM). Polysulfides were determined by a rapid single-phase methylation using methyl trifluoromethanesulfonate (methyl triflate) reagent. The summary polysulfide concentration for S₄²⁻–S₇²⁻ species was found to be around 0.14–0.75 μM in the central region of Israel and substantially higher, 2.3–4.6 μM in the southern region. The sum of polysulfide zerovalent sulfur and colloidal sulfur was quantitatively detected by cyanide derivatization and compared to polysulfide sulfur determined by methyl triflate derivatization and to the chloroform extraction of zerovalent sulfur. A method for the determination of sulfur undersaturation level—the ratio between dissolved elemental sulfur and its equilibrium concentration in the presence of solid sulfur—based on the observed levels of the major polysulfide species is described. The observed polysulfide speciation was compared with the predicted speciation under sulfur saturation conditions taking into account the water temperature, its ionic strength, and pH. Criteria for sulfur saturation versus unsaturated conditions were established based on (1) the chain length dependence of the ratio between the observed polysulfide concentrations and their predicted value under sulfur saturated conditions, and (2) the difference between the concentration of zerovalent sulfur, as determined by cyanolysis, and the total polysulfide sulfur. According to this dual criterion five of the water wells were classified as being undersaturated with respect to sulfur, though for all the examined water wells the majority of the zerovalent sulfur was in the form of polysulfide sulfur.     

Formation of sulfur and nitrogen cross-linked macromolecules under aqueous conditions

Polysulfides and ammonia are abundant in young depositional environments and play an important role in the formation of macromolecular structures such as protokerogen and humics. In this work, we study the co-incorporation of polysulfides and ammonia into simple carbonyl model compounds, octanal and trans 2-octenal, in order to study their effect on the formation of a cross-linked macromolecule and suggest a feasible mechanism. The reactions, performed in aqueous solutions at ambient temperature and pH ∼6 to 9, simulate formation of S and N cross-linked polymers in the natural environment. The complex S and N containing polymer was studied by ¹⁵N enrichment coupled to 2D NMR (¹H, ¹³C, ¹⁵N) techniques and chemical degradation of S-S bonds followed by deuterium labeling and GC-MS analyses. In addition, molecular modeling techniques were used to provide theoretical interpretations and important insights at the molecular level. The results indicate that polysulfide out competes ammonia in the formation of Michael adducts while ammonia is equally competitive with polysulfides when the reaction is addition to the carbonyl position. The co-incorporation of ammonia and polysulfides into carbonyls rapidly forms N and S cross-linked polymers. The effects of ammonia and amines on the polymerization processes are by two means: (i) reaction with carbonyls through an imine functionality to form oligomers and polymers and (ii) catalysis of sulfur nucleophiles onto carbonyls by transfer of a proton which enhances the rate of polymerization. A similar catalytic effect is observed when glycine is used instead of ammonia. This mechanism is especially important under basic to neutral conditions like those that prevail in marine environments. The results show that ammonia and glycine or possibly other amino acids and/or peptides are intimately involved with sulfur nucleophiles throughout the polymerization processes that occur at low temperatures and thus are suggested as key reactants in diagenetic formation of protokerogen and humics.     

Mechanisms of sulfur introduction chemically controlled: δS imprint

Organic sulfur in marine sediment is ³⁴S enriched relative to the co-existing pyrite. This phenomenon is still enigmatic. Timing of the sulfur incorporation, immobilization and different sulfur species involved are part of the explanations. The reduced sulfur species incorporation into organic matter (OM) is generally assumed to have negligible δ³⁴S fractionation. This assumption has never been confirmed by laboratory experimental data. The present study measures the δ³⁴S changes resulting from reduced sulfur species (sulfides and polysulfide anions) incorporation into organic model compounds in an aquatic and low temperature (25 °C) system that simulates diagenetic marine environment. In addition, we also investigate the δ³⁴S fractionation and the isotope chemical mixing in the formation of polysulfide anions produced from elemental sulfur and sulfide anions. The results showed total isotope mixing between the two species in the formation of polysulfides. Acidification of the polysulfides solution caused δ³⁴S fractionation between the released elemental sulfur and H₂S. The incorporation of polysulfides and sulfides into carbonyl groups, caused ³⁴S enrichment relative to the starting polysulfides and sulfide of 4–5‰. The ³⁴S enrichment of the sulfurized carbonyl groups showed a minimal effect by temperature (0–70 °C) and is not affected by salinity, polysulfides composition, reaction time or solubility in water. The incorporation of polysulfides and sulfides into brominated organic compounds was negligibly ³⁴S enriched. The chemical mechanisms controlling the polysulfides incorporation into OM depend mostly on the functional groups and determine the ³⁴S enrichment of the sulfurized OM. The results presented in this study can explain part of the difference between pyrite δ³⁴S and sulfurized OM δ³⁴S in natural marine sediments.     

Equilibria in a sulfide rich water from Enghien-les-Bains,France

A complete analysis of a sulfide rich water from a sedimentary area has been achieved. The formation of metastable sulfur species (polysulfide ions, colloidal sulfur and thiosulfate) is very important. The relative concentrations of the sulfur species is controlled by bacterial processes (Desulfovibrio and Thiobacteriaceae). Electrochemical measurements and results of the analyses are in agreement. A possible repartition of polysulfide ions is S^2?₆ ≈- S^2?₅ >S^2?₄. This repartition, although out of equilibrium, is characteristic of the processes leading to the formation of the metastable sulfur species.The water is in equilibrium with amorphous FeS formation. When sulfide, polysulfide and thiosulfate complexing of trace metals Cu, Cd and Pb is taken into account, an agreement is reached between their concentrations in water and their concentrations in the FeS precipitate.     

液液萃取电感耦合等离子体光谱法测定碳酸盐岩中的单质硫

建立了碳酸盐岩样品中单质硫的分析方法,此法以正己烷为萃取剂,在180.7 nm和182.0 nm波长下用电感耦合等离子体光谱法(ICP-AES)测定国家标准物质GBW(E)07108和碳酸盐岩样品。正己烷萃取碳酸盐岩中单质硫的回收率在90%～110%之间;每个样品测定7次,相对标准偏差(RSD)<5.0%。结果表明,此法满足实验要求,可用于大批量碳酸盐岩样品中单质硫的测定。      

Quantitative Recovery of Elemental Sulfur and Improved Selectivity in a Chromium-Reducible Sulfur Distillation

Chromium-reducible sulfur (CRS) distillations are intended to recover only reduced inorganic sulfur compounds (RIS) including elemental sulfur. However, the quantitative recovery of elemental sulfur is not ensured in common CRS-distillations. The new method presented here was designed to remedy this deficiency. An increase in ethanol concentration assured the quantitative recovery of elemental sulfur in various forms and, in addition, all other RIS-compounds were quantitatively recovered. Furthermore, the selectivity of the procedure was improved by an additional filtration step to eliminate zinc particles from the Cr(II)-solution. Thus, the recovery of sulfates and organic sulfur compounds was significantly decreased by a factor of up to 35, depending on the compound analysed. Exhaustive testing with a variety of pure phases, rock and soil samples demonstrated the precision and accuracy of the new method. The new protocol eliminated the constraints of previous procedures. The improved distillation efficiency for elemental sulfur ensured the quantitative recovery of all RIS-compounds in a single-step distillation.     

Sulfur speciation and associated trace metals (Fe,Cu) in the pore waters of Great Marsh,Delaware

The pore waters of sediments from a salt marsh along the Delaware estuary have been analyzed for sulfur species and associated trace metals. Since the sediment interface is usually in contact with the atmosphere, the sulfur species are dependent on the production of hydrogen sulfide by sulfate reduction and subsequent oxidation by diffusing oxygen. The most important species observed are hydrogen sulfide, polysulfide ions and thiosulfate. Secondary reactions of hydrogen sulfide and polysulfides with decomposing organic matter yield significant concentrations of both thiols and organic polysulfides. Upon isolation of the sediment from the atmosphere due to tidal inundation, bacterial sulfate reduction becomes the dominant process. This results in the reduction of the polysulfides in agreement with thermodynamic predictions, and suggests that the redox couple sulfide/polysulfide is a good redox indicator under such reducing environments.The concentrations of trace elements Cu and Fe in the pore waters are mainly controlled by sulfide formation. Calculations show that copper is strongly complexed probably with organo-sulfur ligands. Iron might be complexed as such sulfur species to a much lesser extent than copper.     

中国煤中硫的地球化学研究

燃烧过程中,煤中硫会以硫氧化物等形式释放出来,污染大气以至形成酸雨,对环境造成极大的影响。本文在对中国煤中硫全面分析的基础上．总结并分析了中国煤中硫在不同地区、不同煤层和不同形成环境中的含量与分布规律,阐述煤中硫形成的地质成因和影响因素．以及育机硫、无机硫和元素硫的赋存状态．概述了煤利用过程中硫的转化机理及其对环境的影响．提出了对煤中硫的研究趋势和今后研究方向与热点问题。     

四川拉拉铁氧化物铜金矿床硫同位素地球化学

硫的来源对于了解铁氧化物铜金矿床的形成过程和成因具有重要的意义。文中统计了拉拉铁氧化物铜金矿硫化物的 硫同位素数据,并结合地质特征和矿相学研究,分析和讨论了硫的同位素组成特征和硫的来源。结果表明,拉拉铜金矿硫 同位素组成变化较大(不考虑一个异常样品,δ34S 值极差达到 14.9‰),表明成矿硫来源的多样性;其中,黄铁矿 δ34S 值范 围为 -1.4‰ ~4.9‰(平均 1.8‰),黄铜矿的 δ34S 值范围为 -5.9‰ ~9‰(平均 1.5‰)。结合硫化物的生成机制分析,并与其 他典型矿床硫同位素数据对比,表明海水沉淀的蒸发岩是黄铁矿和黄铜矿的重要硫来源,但也不能排除岩浆硫的贡献。目 前没有证据支持变质作用减少拉拉矿区硫化物的硫同位素组成差异。     

滇东北镇雄硫磺矿区环境地质问题及其对策与意义

硫磺渣是硫磺矿区主要的矿业固废,其随意堆放可产生一系列的环境地质问题,并对山水林田湖草等自然资源、环境及人的健康构成较大危害。滇东北地区长期以硫铁矿为原料、以煤炭为燃料,土法炼硫生产硫磺,导致巨量硫磺渣堆积,产生了严重的环境地质问题。本文针对该地区镇雄县硫磺矿区,调查了小硫磺生产形成硫磺渣的规模和特征,梳理了该硫磺矿区主要环境地质问题及其对当地生态环境的影响,认为目前镇雄硫磺矿区存在的环境污染、自然资源破坏及可能形成的矿渣性泥石流等环境地质现状与过去40多年的小硫磺生产密切相关。基于以上认识,强调应结合矿业固废无害化、减量化和资源化技术政策,从资源回收利用、生态环境恢复、地质灾害防治和文化遗产保护方面探讨和提出镇雄硫磺矿区矿渣治理和生态修复的新理念和新对策。     

Oxidant-elemental sulfur as an effective promoter for transformation of organic matter to hydrocarbons at moderate-low temperatures

Elemental sulfur is widely dispersed in the hydrocarbon source rocks and its depositional environment is usually thought as a reducing environment. The presence or absence of free oxygen is a key to identify oxidizing or reducing environment. But elemental sulfur is often present as an oxidant in this environment. When elemental sulfur meets with organic matter, redox reaction will occur. In our simulation experiments at 200 -400℃ , the existence of elemental sulfur can sharply increase the amounts of hydrocarbons, hence leading to the production of immature or low-mature oils and natural gases. At the temperature of 300℃ , the addition of elemental sulfur will further enhance the relative yields of hydrocarbons,and the final yield of total extracts and gaseous hydrocarbons of similitude kerogens by more than 463% and 2760% , respectively, while those of oil shales are increased by about 71% and 2044% , respectively. But at the temperature of 450℃, elemental sulfur plays a negative role in liquid hydrocarbon formation. The presence of elemental sulfur is probably a key factor in the gypsolyte environment leading to the formation of immature or low-mature oils, as well as the coexistence of immature or low-mature oils and natural gases.     

煤中硫的地质特征和洁净煤技术的发展(英文)

媒中硫的含量大都由煤层的沉积环境控制,并取决于成煤物质是否曾受过海水影响及其受海水影响的程度。煤中硫的含量对于煤的有效利用甚为重要。这主要是因为燃煤时有相当量的二氧化硫释放到大气中造成对环境有害的酸雨。因此,煤层中硫的分布和地质特征是评估煤的品质及解决有关环境问题的一个重要参数。洁净煤技术是为了有效解决能源需求并减少用煤对环境的影响而发展起来的。它包括煤燃烧前的洁净方法（物理、化学和微生物的煤洁净法）、烟气脱硫、吸附剂喷撒和各种媒燃烧技术（流化床、气化联合循环等）。     

滨海红树林泥炭沉积物中硫的赋存特点及其控制因素

海南和厦门两地滨海红树林沉积物和埋藏泥炭中硫的成分分析表明,滨海红树林沉积物和泥炭中的硫以硫化铁硫为主,有机硫次之,硫酸盐硫含量最低。泥炭沉积物中硫的赋存形式和特点与沉积环境密切相关。海南福田地区红树林泥炭沉积物主要形成于红树林潮上坪和泥炭坪,硫含量较高,平均为2.60%,且有机硫含量与有机碳含量呈正相关,而硫化铁硫含量与有机碳含量没有明显的相关性;厦门海沧镇红树林泥炭沉积物形成于红树林潮间坪以及潮道环境,硫含量较低,平均值仅为0.43%,形态硫和有机质的相关性与海南红树林泥炭地沉积物相反。红树林泥炭沉积物中铁的硫化物主要以黄铁矿形式产出,且以莓球状形态为主。研究表明,黄铁矿与次生有机硫的生成与微生物活动密切相关,造成红树林泥炭中硫含量差异最主要的原因不是硫源,而是有机质的供给与沉积微环境的影响。现代滨海红树林泥炭沼泽中硫的赋存特征将对煤中硫成因的研究提供重要的科学依据。     

南秦岭柞水—山阳矿集区夏家店金矿床黄铁矿微量元素和氢、氧、硫同位素对矿床成因的制约

为了研究柞水—山阳矿集区夏家店金矿床成因,采用LA-ICP-MS和LA-MC-ICP-MS技术分析夏家店金矿床矿体及围岩样品中黄铁矿原位微量元素及氢、氧、硫同位素组成特征。结果表明,该矿床黄铁矿的Co/Ni 比值为0.11~0.76,说明其与沉积作用有关。矿石中黄铁矿的δ³⁴S值(-9.40‰~7.16‰)与围岩碳质板岩的δ³⁴S值(-8.84‰~10.64‰)接近,黄铁矿的δ³⁴S均值(2.47‰)基本落在岩浆硫的范围内,指示矿石硫可能由地层硫和岩浆硫混合而成。氢、氧同位素测试结果表明,夏家店矿床成矿流体可能主要来自岩浆水,成矿后期有大气降水的加入。综合矿床地质特征、成矿温度、金赋存状态等特征和黄铁矿微量元素、硫同位素组成可知,夏家店金矿床属于卡林型金矿,其成矿流体主要来自岩浆水,成矿后期有大气降水加入;其成矿物质是由深部岩浆与地层混合而成。     

山东济宁高硫煤与低硫煤煤层剖面地球化学特征研究

运用电感耦合等离子质谱（ICP-MS）、X射线荧光光谱（XRF）、离子选择电极（ISE）、显微镜光度计和煤化学等方法,对山东济宁矿区的高硫煤（太原组16号煤层）与低硫煤（山西组3上煤层）剖面的煤岩、煤质和煤地球化学特征进行研究。高硫煤中微量元素在垂向上呈现显著的变化规律：（1）Sr含量从煤层底板到顶板呈增高趋势,而Ba含量则相反;因而Sr/Ba比值从下向上呈逐渐变大趋势（0.04～47.7）;（2）Th/U比值从下向上也呈逐渐变大趋势（0.2～37.1）;（3）As含量在煤层顶板石灰岩（26.1μg/g）、透镜状黄铁矿夹层（14.7～19.3μg/g）中较高;（4）V、Cr、Co、Ni、Cu、Pb、Zn等元素在煤层底部和顶部分层中含量较高,而在煤层中部分层中含量较低;（5）Nb、Ta、Zr、Hf、Ga等元素从煤层的底部到顶部呈逐渐降低趋势;（6）煤中稀土元素总量（REE）,除透镜状黄铁矿夹层（第2、4、11分层）外,其它分层（第1、3、5、6、7、8、9、10分层）显示从上往下逐渐增高之规律性。低硫煤中微量元素的分布和垂向变化与高硫煤明显不同：As含量在14个煤分层中都较低（1.03～3.37μg/g）,Sr/Ba比值从下向上变化不大（0.4～2.2）,各个煤分层中稀土元素总量（REE）呈现随灰份含量增高而增高的变化趋势,低硫煤与高硫煤的稀土元素分布模式差别很大。上述研究结果表明济宁矿区高硫煤与低硫煤在地球化学特征上的差别,反映了上石炭统太原组与下二叠统山西组沉积环境和聚煤条件的差别,具有指相意义;太原组16号煤层中富集的硫及有害微量元素,对环境具有潜在危害。     

韩城石炭——二叠系原煤的自身固硫率和硫的烧失率

对陕西韩城矿区的石炭－－二叠系4个主采煤层的原煤自身固硫率和硫的烧失率进行了研究，其中11号煤96％的煤，5号煤98％，3号煤92％和2号煤94％的硫在800－850℃温度下的灼烧2h已分解释放。其燃渣中的硫主要以硫酸盐的形式存在。煤自身的固硫率和灰分含量密切相关，特别是与煤灰分中的氧化钙关第最为密切，原煤中硫的烧失率与煤中全硫、有机硫和无机硫的含量关系密切。     

Spinifex Texture of Native Sulfur: A Cooling Product of Sulfur Flow Eruptions at Shiretoko-Iwozan Volcano, Hokkaido, Japan

Abstract: Several native sulfur specimens, collected from Shiretoko-Iwozan volcano, eastern Hokkaido, Japan, exhibit spinifex texture, which appears to resemble that often observed in komatiite. The spinifex texture is exhibited by yellow-colored elongated skeletal native sulfur crystals up to 5 cm long settled in medium gray-colored fine–grained clayey matrix. One surface of a specimen is coated by layers of micro pillow lava of native sulfur. Such specimens were rarely found as clasts or fragments around the 1936 No. 1 crater that erupted native sulfur flows, together with the most common monomineralic native sulfur fragments of native sulfur flows having pahoehoe surface and of native sulfur dikes. The elongated spinifex native sulfur crystals presently consist of aggregated polygrains of orthorhombic sulfur crystals formed through crystallo-graphic transition from the single crystal of monoclinic sulfur initially crystallized. The spinifex texture exhibited by elongated skeletal native sulfur crystals is a product of rapid cooling of sulfur melt. Many lithic fragments of altered country rocks are present in the specimens exhibiting native sulfur spinifex texture. This suggests that segregation of the sulfur melt from the mixture of lithic fragments and sulfur melt was incomplete because the mixture was chilled before the melt segregation. Elongated skeletal native sulfur crystals may have nucleated and crystallized directly from the molten sulfur liquid. Lithic fragments mixed in the melt are supposed to have acted as nuclei for the nucleation of the native sulfur crystals. On the other hand, the most of native sulfur flows consist of monomineralic massive native sulfur with very scarce lithic fragments. Such massive monomineralic native sulfur crystallized from the supercooled, solidified amorphous sulfur. Such supercooled amorphous state may have been attained due to the lack of nuclei because of the scarcity of lithic fragments. The unique structures exhibited by native sulfur lava flow, including pahoehoe surface and spinifex texture, are due to the characteristic physical property of molten sulfur liquid, that is, low viscosity.     

膏盐层在Ni-Cu-PGE硫化物矿床成矿中的作用 ——以俄罗斯诺里尔斯克矿床为例

与基性-超基性侵入体有关的Ni-Cu-PGE硫化物矿床是镍-铜-铂族元素矿床的最重要类型。传统观点认为,Ni-Cu-PGE硫化物矿床是由成矿岩浆分异演化、熔离形成的,与围岩性质关系不大。实际上,大部分基性-超基性岩浆是硫化物不饱和的,在岩浆自身演化过程中难以聚集大量硫化物而形成有经济价值的大型高品位NiCu-PGE硫化物矿床。因此,壳源硫的加入是基性-超基性岩浆中硫化物浓度达到过饱和,熔离形成Ni-Cu-PGE硫化物矿床的关键。膏盐层是富含石膏等硫酸盐(SO24-)的蒸发沉积建造,除SO24-外,还富含Cl-、CO23-、Na+、K+等盐类物质,在自然界分布广、面积大,是地壳中重要的硫源层和氧化障。但膏盐层在Ni-Cu-PGE硫化物矿床中的作用长期被忽视,制约了Ni-Cu-PGE硫化物矿床成矿找矿理论的发展。文章以世界最大的俄罗斯诺里尔斯克Ni-CuPGE硫化物矿床为例,介绍了膏盐层与矿床分布的空间关系、石膏等硫酸盐矿物在矿床和蚀变围岩中的分布、成矿元素和硫同位素组成特征及变化规律,阐明了膏盐层在成矿中的作用和控矿机理。膏盐(SO24-)的加入,可以大幅度提高成矿系统的氧逸度,将成矿岩浆中Fe2+氧化成Fe3+,形成铁氧化物,SO24-自身被还原,向成矿系统提供还原硫S2-,与Cu2+、Ni2+等结合,形成铜镍硫化物等,使基性-超基性成矿岩浆由硫化物不饱和变为过饱和,形成硫化物小液滴,在岩浆房经聚集-熔离-富集,形成岩浆型Ni-Cu-PGE硫化物矿床。除膏盐层外,富含硫化物的地层也是形成Ni-Cu-PGE硫化物矿床的重要硫源层。