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).     

Sulfur Mass Fractions in Thirty-Seven Geological Reference Materials by Titration,XRF and Elemental Analyser

Although sulfur is a relatively abundant element, measurement results with small uncertainties remain challenging to achieve, especially at S mass fractions below 100 μg g^-1. We report > 1700 measurement results of S for thirty-seven geological reference materials including igneous, metamorphic and sedimentary rocks, and one soil. Measurement results were obtained in two laboratories (Macquarie GeoAnalytical and Géosciences Montpellier) over a long period of time ≈ 25 years (1997–2022), using several measurement procedures: X-ray fluorescence, high temperature iodo titration and elemental analysers equipped with thermal conductivity and/or infra-red detectors. Sulfur mass fractions for these diverse geological reference materials range between 5.5 and 11,395 μg g^-1. While the comprehensive data set reported here should contribute significantly to a better characterisation of the S mass fractions of widely used geological reference materials, computed uncertainties, data distribution and comparison to published values still indicate heterogeneous distribution of S carrier(s) and analytical bias.     

元素分析仪-气体同位素质谱法分析硫酸钙样品的硫同位素组成

硫酸盐硫同位素的常规分析方法是将硫酸盐转化为硫酸钡后搭配双路进样SO2法,该法易于操作、数据稳定,但样品用量大、费时费力,需要繁杂的前处理,无法满足微量分析发展方向的需求。本文以石膏为例,以元素分析仪-气体同位素质谱法(EA-IRMS)直接测定硫酸钙样品硫同位素比值,对同一样品分别采用:①硫酸钙与V2O5混合后包裹于锡杯中密封,直接进行元素分析仪-气体同位素质谱分析;②硫酸钙充分溶于去离子水中,向溶有硫酸钙样品的液体中加入沉淀试剂BaCl2,将生成的硫酸钡沉淀滤出后,用去离子水清洗2~3遍,烘干后与V2O5混合包裹于锡杯中密封再进行质谱测定。实验选取了13件δ34S值变化范围介于-20‰^+30‰之间的天然石膏样品,将获得的硫同位素比值进行对比,二者δ34SV-CDT绝对差值在0.00‰~0.24‰,表明同一样品的硫同位素比值结果在误差范围内基本一致。与常规分析方法相比,本文建立的直接在线分析时无需任何化学前处理,只需直接加入适量的V2O5,V2O5和氧气中的外部氧在瞬间燃烧的过程中替代了硫酸钙本身的氧,生成的SO2气体的氧是均一的,其硫同位素比值能代表样品的硫同位素组成,无需进行氧同位素的校正。经过验证表明,硫酸钙样品的直接在线分析是完全可行的。     

Simultaneous Determination of Total Carbon, Nitrogen, Hydrogen and Sulfur in Twenty-seven Geological Reference Materials by Elemental Analyser

The contents of total carbon, hydrogen, nitrogen and sulfur in twenty-seven geological reference materials, issued by five producer organisations (USGS, CCRMP, ANRT, NIST and GSJ) were determined using an automated simultaneous elemental analyser following combustion. In order to complete gasification of C and N in some geological materials, the combustion temperature needed to be greater than 1150 °C. The calibrator prepared from known amounts of reagent material was not adopted for more than 1.2% m/m of H. Unrealistically high values in certain materials supposed to contain less than 1000 μg g⁻¹ S may be due mainly to memory effects. The limit of detection was 50 μg g⁻¹ for C and N, 500 μg g⁻¹ for H and 1000 μg g⁻¹ for S. Although the blank value of C and N was always stable and less than one third of the detection limit, it had a slightly higher value for N and S. By repeating long-term analysis, high reproducibility for each of the four elements was verified. The method has been applied satisfactorily to a variety of geological reference materials, and recommended values for C, H and N for most of the reference materials studied have been tabulated.     

应用元素分析仪测定铅锌矿中的高含量硫

目前对铅锌矿中高含量硫的测定主要采用传统的重量法和容量法,但由于铅锌矿基体复杂,干扰较多,造成操作步骤繁琐;而采用湿法仪器分析又受制于样品的前处理等问题使得测定结果的准确度较差。本文建立了应用元素分析仪测定铅锌矿中的高含量硫(1.0%~32.0%)的分析方法。将样品磨制成粒度小于0.075 mm的粉末,样品制备时加入高纯二氧化硅作为稀释剂以降低铅锌矿的含硫量,仪器测量时加入线状氧化铜作为添加剂以提高硫的氧化效果,优先选用与实际测定样品相同性质的铅锌矿国家标准物质GBW07287(硫的标准值为10.76%)建立标准曲线以减小基体效应。方法精密度(RSD,n=12)小于1%,实际样品分析的测定值与重量法的相对误差小于1%。本方法比化学分析方法的操作简单,几乎没有干扰;比湿法仪器分析方法的样品前处理步骤少,待测元素硫的损失少,测定结果可靠度高。     

Total Sulfur Concentration in Geological Reference Materials by Elemental Infrared Analyser

Total sulfur is an analyte for which there are few determinations published, despite the fact that it is a very important element (e.g., a major element in most ores, an important gas constituent in global warming, an active participant in acid drainage). Most geological reference materials have very poor quality sulfur results, that is with relative standard deviations (RSD) in the range of 30–50%, even for concentrations over 100 μg g⁻¹ S, which compromises their use as calibrators. In order to provide modern results with low RSD, sulfur was determined in twenty-nine geological reference materials with a state-of-the-art elemental S/C analyser using metal chips (certified reference materials with a traceability link) and analytical grade sulfur for high concentration samples. Analytical parameters (sample mass, crucible degassing, calibration strategy, etc.) were optimised by testing. Our results agreed with reference material values provided by issuing bodies. Results for CCRMP SY-2 (129 ± 13 μg g⁻¹ S), which has been proposed as a sulfur reference material, were in agreement with the proposed modern value of 122 ± 3.7 μg g⁻¹ S.     

Determination of Carbon,Hydrogen, Nitrogen and Sulfur in Geological Materials Using Elemental Analysers

This article describes a series of methods developed for the determination of total carbon (C_Total), organic carbon (C_org), hydrogen, nitrogen and sulfur. The following elemental analysers were used: LECO model RC‐412 for the determination of organic carbon, total carbon and hydrogen; LECO model CS‐200 for the determination of total carbon and sulfur; LECO model TN‐400 for the determination of nitrogen; and LECO model TruSpec CHNS for the determination of organic carbon, total carbon, hydrogen, nitrogen and sulfur. Uncertainty and limits of detection and quantification were calculated for each method, as well as the running costs to define the most effective instrument for each material and each analyte. Accuracy was checked by the application of the Sutarno–Steger test. Finally, a compilation of the results obtained in the determination of C_Total, C_org, H, N and S in forty‐nine reference materials is presented.     

红外碳硫仪测定矿石中高含量硫的探讨

探讨了用红外碳硫测定仪测定矿石中高含量硫需注意的一些影响因素,包括标样的选择、减少天平误差、称样量、样品的充分燃烧以及仪器的稳定性,说明了用红外碳硫仪测定矿石中高含量硫的可行性。     

扫描质子探针研究磁铁矿中的元素分布

选取有代表性的磁铁矿样品,研究了Fe、Mn、s、P等元素在500μm×500μm区域内的分布情况,初步探讨了Fe的聚集状态和S、P的均匀分布状况在地球化学、冶金学上的应用。     

莱芜潘西煤矿降低高硫煤含硫量的几点措施

根据目前国内煤炭脱硫技术的发展现状,该文分析研究了潘西煤矿的煤质特征和硫的赋存状态特征。为了降低商品煤中的硫分,潘西煤矿采取了筛选和捡选原煤中黄铁矿结核降低商品煤硫分,上下组煤合理配采降低商品煤硫分,洗选法降低硫分等措施,使煤的质量明显提高,获得了较好的经济效益。     

地质样品扫描质子探针元素分布图的本底值剔除研究

建立了一个简便、可靠的扫描质子探针元素分布图本底值剔除方法,编制了逐点本底计数值剔除计算程序。结合实际地质样品的扫描质子探针元素分布成图,对方法的有效性做了对比实验。结果表明,与传统的成图方法相比,新方法具有图像清晰、真实的优点。同时讨论了方法的误差和误差的减小途径。     

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。     

苏鲁造山带A型花岗岩的元素地球化学及其成因

苏鲁造山带花岗岩SiO2质量分数变化范围为71.3%~74.5%,以富碱(Na2O+K2O为8.66%~9.60%)、高钾(K2O为4.95%~5.89%)、富轻稀土元素而亏损重稀土元素、明显的负铕异常(δEu=0.51~0.61)、较高的Ga/Al(×104)比值(2.85~3.41)和Zr+Nb+Ce+Y值(384~714)×10-6、富集Rb、Th、K、La、Nd、Hf、Zr和Pb以及亏损Ba、Ta、P和Ti为特征。主微量元素研究表明,所研究花岗岩为过铝质(A/KNC为1.90~2.17)A型花岗岩,为华北板块富集岩石圈地幔的部分熔融的产物。岩浆在上升侵位的过程中没有受到地壳物质的混染,但在成岩过程中存在斜长石、钾长石、黑云母、磷灰石和钛铁矿等矿物的分离结晶作用,锆石饱和温度计算表明岩浆的结晶温度大致为876~961℃。     

Elemental Geochemistry of a Soil Chronosequence on Basalt onNorthern Hainan Island, China

With increasing soil age, the contents of Sr, Ba and ratios of Sr/Be in soils tend to decrease, whereas the contents of V, Sc, Ni, Cr, Co and ratios of Fe/Ni and Fe/Co tend to increase, as evidenced from a study on soils of different ages, developed on basahs in the northern part of Hainan Island. Ba/Nb, significantly correlative with soil age, can be used to evaluate soil evolution. By using the mass-balance method, the element migration was discussed with Ti as an immobile element. The results showed that element leaching was most intensive in the early pedogenic period. In this period (Primosols) , over 90% of Ca, Mg, K and Na was leached out of soils till Ferrosol formation. The leaching of P occurred mainly at the beginning of soil development. About 60% of Si was mobilized in the stage of Cambosol formation and 80% in the stage of Ferralosol formation.     

热解硫酸钡制备硫同位素分析试样二氧化硫

改进了硫同位素分析中由ＢａＳＯ４制备ＳＯ２的方法：ＢａＳＯ４和Ｖ２Ｏ５及ＳｉＯ２混合后覆盖铜丝,在真空状态９８０℃加热２０ｍｉｎ,用液氮捕集ＳＯ２。与火焰直接加热分解法相比,用高温炉方便,改善了制样环境,避免污染。经国际标样和国家标准物质分析验证,结果与标准值相符,标准偏差（１σ）在±００９‰～±０２０‰,符合分析要求。     

塔西南缘铅锌矿硫同位素特征及硫的来源探讨

通过塔西南缘铅锌矿带金属硫化物(方铅矿、黄铁矿、黄铜矿、闪锌矿)的硫同位素测试研究,结果显示δ34S值范围在-38.3‰～24.0‰,具双峰式分布,推测两种或两种以上流体相混合是导致矿床硫同位素组成变化的主要原因,一类硫化物的δ34S值集中在-6‰～6‰,组成的矿石呈细粒、草莓状结构及浸染状构造;另一类硫化物的δ34S值集中在-32‰～-24‰,组成的矿石呈粗粒、脉状或角砾状构造。两种流体受构造应力和压实作用的影响,沿着断裂或岩石的裂隙运移并相混合,发生热化学硫酸盐还原反应,产生的HS-与Zn2+、Pb2+结合形成闪锌矿、方铅矿,在有利部位沉淀成矿。硫主要来源于海水硫酸盐。     

福建近岸浅海沉积物元素丰度及含量变化特征

通过福建省沿海经济带生态地球化学调查,在福建近岸浅海区域共采集479件沉积物样品,分析测试了52种化学元素以及pH值和有机碳等指标。总结了该区域浅海沉积物化学元素的丰度、含量变化及其区域分布,并分不同沉积物类型统计有害元素的污染起始值。福建近岸浅海沉积物与中国浅海沉积物对比,大部分元素的含量高于中国浅海沉积物,含量变化基本遵循“元素的粒度控制律”,除Si元素相反外,Al、Fe、Cu、Co、Ni等绝大多数元素的含量随沉积物粒度变细（砂→粉砂→泥）而升高,有些元素在泥质沉积物中的含量常高出砂质的数倍;其高值、高背景区的区域分布也总是与细粒沉积物有关,而低值、低背景区则明显地与砂质沉积物的分布相关。     

高灵敏度元素分析仪-连续流同位素质谱法对硅酸盐岩中碳及碳同位素组成的精确测定

硅酸盐岩中含有微量的碳,对其精确地分析可以示踪流体的来源和形成过程。元素分析仪-同位素质谱方法(EA-IRMS)是一种使用样品量小、快速的分析方法,本文将EA-IRMS技术应用于硅酸盐岩中微量碳同位素组成的测定,基于一系列条件实验,确认了硅酸盐岩中微量碳分析的EA-IRMS连续流方法的关键条件参数。标准物质选择和归一化处理使用以下方法:(1)选择较宽碳同位素组成范围且合理的碳同位素分布的标准物质,以高纯石英粉末与之混合来模拟天然样品中的基质。(2)利用与样品类似含量的3个标准物质的测量值和标准真值建立校准曲线,对天然样品的测量值进行标准化,从而实现了对硅酸盐岩中低至600!g/g微量碳含量和同位素组成的精确测定。用国家标准物质GBW04416作为未知样品检验了不同含量下拟合的线性方程,在碳含量不低于600!g/g时,标准偏差分别约为0.02‰、0.04‰、0.05‰、-0.07‰、0.11‰;在MERCK+USGS24混合物中,测量的δ13C值在标准误差范围内与理论值是一致的。因此,对于碳含量不低于600!g/g的30 mg硅酸盐岩样品,本方法能够获得高精准度的碳同位素分析结果。根据不同碳含量的标准混合物的峰面积(峰强度)和相对应的含量所建立的线性曲线获得样品的碳含量,碳含量的分析误差在10%以内。     

Elemental and isotopic carbon and nitrogen records of organic matter accumulation in a Holocene permafrost peat sequence in the East European Russian Arctic

A peat deposit from the East European Russian Arctic, spanning nearly 10 000 years, was investigated to study soil organic matter degradation using analyses of bulk elemental and stable isotopic compositions and plant macrofossil remains. The peat accumulated initially in a wet fen that was transformed into a peat plateau bog following aggradation of permafrost in the late Holocene (～2500 cal a BP). Total organic carbon and total nitrogen (N) concentrations are higher in the fen peat than in the moss‐dominated bog peat layers. Layers in the sequence that have lower concentrations of total hydrogen (H) are associated with degraded vascular plant residues. C/N and H/C atomic ratios indicate better preservation of organic matter in peat material dominated by bryophytes as opposed to vascular plants. The presence of permafrost in the peat plateau stage and water‐saturated conditions at the bottom of the fen stage appear to lead to better preservation of organic plant material. δ¹⁵N values suggest N isotopic fractionation was driven primarily by microbial decomposition whereas differences in δ¹³C values appear to reflect mainly changes in plant assemblages. Positive shifts in both δ¹⁵N and δ¹³C values coincide with a local change to drier conditions as a result of the onset of permafrost and frost heave of the peat surface. This pattern suggests that permafrost aggradation not only resulted in changes in vegetation but also aerated the underlying fen peat, which enhanced microbial denitrification, causing the observed ¹⁵N‐enrichment. Copyright © 2012 John Wiley & Sons, Ltd.     

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。