高硫煤中硫的地质演化模式——以内蒙古乌达矿区为例

以内蒙古乌达矿区为例，通过对高硫煤9煤层中黄铁矿和有机硫同位素的测定（有机硫同位素δ^34S=-12.3‰-5.8‰，黄铁矿硫同位素δ^34S=-18.7‰-1.1‰），结合煤岩学特征的综合分析以及黄铁矿化菌落和蓝藻胶壳的发现，提出了庙充煤中硫的党政军化模式，认为高硫煤中主要来源的硫的同位素由于硫酸盐的异化细菌还原作用导致大规模分馏，使之趋于负值，在高硫煤形成过程中，黄铁矿和有机硫表现出形成初期Fe^2 和有机质对硫离子的争夺性、形成过程中在剖面上的层次性、阶段性和时间上的相向性，层次性和阶段性表现为沼泽体系对SO4^2-和H2S的开放程度及黄铁矿的形成对^32SO4^2-的过滤性，相向性表现为泥炭聚积初期和晚期，Fe^2 和SO4^2-对高硫煤形成做出了贡献，具有剖面上的对称特点。     

硫循环的酶促反应机制及湖泊环境效应

在湖泊沉积物表层存在着强烈的生物作用,使ＳＯ＾２－４转变成Ｓ＾２－,然后和Ｆｅ＾２＋结合而固定在沉积物中,这种ＳＯ＾２－４的清除机制具有重要的环境意义。本文论述了Ｈ２Ｓ的产生和各种形态硫转变成ＳＯ＾２－４的酶促反应机制,并阐述了不同微生物电子传递载体、最终电子受体和电子进入传递链的部位的差异以及生成ＡＴＰ的数目和环境效应的差异。     

贵州晚二叠世煤中硫同位素的组成特征

报道了贵州主要开采矿山晚二叠世煤中不同形态硫的同位素组成特征。形成于海水影响较小环境中的煤以低的硫含量,偏正的δ＾３４Ｓ值为特点,形成于海相或受海水影响较大的环境中的煤,则具有高的硫含量和偏负的δ＾３４Ｓ值;在高硫含量的煤中,有机硫和无机硫具有弱的相关性,可能它们具有一致的来源;煤中有机硫的同位素组成对成煤环境是灵敏的,可作为成煤环境划分指标,根据有机硫含量和同位素组成,可分出海水对煤层的影响程度     

潮控与河控下三角洲平原成煤的岩石学和地球化学特征

从显微煤岩组成特征、不同显微组分中有机硫的含量、伴生元素组成、硫同位素的分布特征等方面对内蒙古乌达矿区潮控下三角洲平原形成的高硫煤 9煤层和河控下三角洲平原形成的低硫煤 13煤层进行了研究。结果表明 ,潮控下三角洲平原形成的煤层较之河控下三角洲平原形成的煤层具有较高的镜质组含量 ;伴生元素中 Na、K、V、Mg等含量偏高 ,而稀土元素含量较低 ,稀土元素的含量与煤中的粘土矿物含量成正比 ;黄铁矿和有机硫同位素都比较轻 ,表明高硫煤中硫的来源主要是海水中细菌还原的硫酸盐。     

滇西羊拉铜矿床稳定同位素地球化学研究

滇西羊拉铜矿是近年来发现的大型铜矿床。作者系统地研究了该矿床的Ｓ、Ｐｂ、Ｃ、Ｏ、Ｓｉ同位素组成,研究表明该矿床不同矿石的硫同位素组成变化范围一致,其平均值靠近零值且具有塔式分布特征,表明硫来源于上地幔或岩浆作用;该矿床矿石中方解石的Ｃ、Ｏ同位素组成与矿区大理岩的Ｃ、Ｏ同位素组成明显不同,其δ＾１３Ｃ（ＰＤＢ）为－３．２７‰～－４．８９‰,与土地幔射气及岩浆作用形成的ＣＯ２的碳同位素组成一致,因此矿石中方解石中碳亦来源于土地幔射气或岩浆作用;铜同位素特征表明早期热水沉积形成的块状硫化物矿石铅主要来源于上地壳,而中晚期形成的夕卡岩型矿石及蚀变破碎带型矿石的铅具有土地幔铅的特征。     

四川省石棉县大水沟碲床成矿物质来源的一些证据

该矿床是一个新矿床类型。成矿作用分为磁黄铁矿－黄铁矿、辉碲铋矿和黄铁矿－黄铜矿三个阶段。矿化围三叠纪镁铁质火山岩。在矿脉周围广泛发育有以黑云母、白云母、石英和斜长石为代表的蚀普及分带。磁黄铁矿和辉碲铋矿的硫同位素值δ＾３４Ｓ＝－１．７‰－２．８‰白去石和方解石的δ＾１３ＣＰＤＢ＝－５．３‰－－７．４２，δ＾１８ＯＳＭＯＷ＝１０．９－１３．１‰。根据以硅质、碱和富挥发组分为特征的围岩蚀变和Ｓ、Ｏ?     

沁水盆地晚古生代煤中硫的地球化学特征及其对有害微量元素富集的影响

煤中硫是多种有害微量元素的重要载体。基于形态硫分析、电感耦合等离子质谱及X射线衍射等方法分析沁水盆地晚古生代煤中硫和有害微量元素的分布规律,探讨了煤中硫对有害微量元素富集的影响,运用带能谱的扫描电镜和光学显微镜划分煤中硫化物的微观赋存特征。结果表明,沁水盆地煤中硫整体上以有机硫为主,平均占全硫的78%,只有在太原组个别高硫煤中以黄铁矿硫为占优势。显微镜和扫描电镜下可识别出煤中黄铁矿的微观赋存状态包括莓球状、薄膜状、晶粒状、结核状、团窝状黄铁矿和细粒黄铁矿集合体,白铁矿的微观赋存特征包括聚片状、板状和矛头状白铁矿,部分白铁矿与黄铁矿共生。沁水盆地煤中有害微量元素含量整体较低,黄铁矿是有害微量元素As、Se和Hg的重要载体,而有机硫决定了煤中U的富集。研究认为,成煤时期海水对泥炭沼泽的影响导致太原组煤中全硫和黄铁矿硫较高,太原组煤中硫的来源具有多样性,煤中黄铁矿具有多阶段演化的特点。     

黔中沉积磷灰石的硫碳同位素及其地质意义

本文研究了黔中磷块岩中磷灰石的结构硫同位素组成。磷灰石的δ３４Ｓ值为３４．２‰～４２．４‰，它高于同期海水的δ３４Ｓ（约３４．２‰），也高于共生的成岩黄铁矿的δ３４Ｓ（１５．４‰～１９．８‰），表明磷灰石形成于富有机质沉积物早期成岩作用硫酸盐还原带的最上部，其间同时伴有大量硫酸盐细菌的还原过程。磷灰石的碳同位素组成（δ１３Ｃ＝－３．６３‰～１．０‰），表明它含有微生物有机质分解演化而来的ＣＯ２－３，而磷灰石比胶结白云石更富集轻同位素则反映出沉积阶段生物作用的影响比成岩阶段更为明显     

聚煤环境对煤岩中形态硫赋存的影响

对煤中形态硫的分析测试结果表明，１）碳酸盐台地潮坪成因的煤以有机硫为主，黄铁矿硫占少数，但其类型、产状多样，全硫含量在剖面上虽有波动变化，但幅度较小，硫分布模式说明成煤环境受海水影响强烈且持久稳定。２）下三角洲平原泥炭沼泽成因的煤属以黄铁矿硫为主的高硫煤，按形态和产状可分５种类型的黄铁矿，煤层剖面上全硫含量由底到顶部逐渐增加，说明成煤环境亦受海水影响强烈，但有一逐渐增强的过程。３）上三角洲平原沼泽成因煤为富有机硫的低硫煤，黄铁矿量少、类型单调，全硫含量在煤层剖面上的变化为顶底高、中部低，表明煤层顶、底板性质控制着煤中硫的分布。     

恒山鹿沟金矿形成的物理化学条件及同位素地球化学

本文对恒山东段鹿沟金矿形成的温度，压力，ｆＣＯ２，ｆＯ２，成矿溶液的成分，盐度，ｐＨ值，Ｅｈ值进行了系统的论述。同时利用硫、铅、氧、氢、锶同位素资料，对成矿时代、物质来源进行了论证，得出成矿物质主要来自围岩，成矿溶液以变质水为主的结论。溶液性质属Ｎａ＾＋－Ｃａ＾２＋－ＣＩ＾－ －ＳＯ＾２－４型，富ＣＯ２，高盐度，偏酸性。成矿时代与区域变质年龄一致，为２２１４．５±６４．１Ｍａ。燕山期岩浆活动对其有     

Fractionation of multiple sulfur isotopes during phototrophic oxidation of sulfide and elemental sulfur by a green sulfur bacterium

We present multiple sulfur isotope measurements of sulfur compounds associated with the oxidation of H₂S and S⁰ by the anoxygenic phototrophic S-oxidizing bacterium Chlorobium tepidum. Discrimination between ³⁴S and ³²S was +1.8 ± 0.5‰ during the oxidation of H₂S to S⁰, and −1.9 ± 0.8‰ during the oxidation of S⁰ to , consistent with previous studies. The accompanying Δ³³S and Δ³⁶S values of sulfide, elemental sulfur, and sulfate formed during these experiments were very small, less than 0.1‰ for Δ³³S and 0.9‰ for Δ³⁶S, supporting mass conservation principles. Examination of these isotope effects within a framework of the metabolic pathways for S oxidation suggests that the observed effects are due to the flow of sulfur through the metabolisms, rather than abiotic equilibrium isotope exchange alone, as previously suggested. The metabolic network comparison also indicates that these metabolisms work to express some isotope effects (between sulfide, polysulfides, and elemental sulfur in the periplasm) and suppress others (kinetic isotope effects related to pathways for oxidation of sulfide to sulfate via the same enzymes involved in sulfate reduction acting in reverse). Additionally, utilizing fractionation factors for phototrophic S oxidation calculated from our experiments and for other oxidation processes calculated from the literature (chemotrophic and inorganic S oxidation), we constructed a set of ecosystem-scale sulfur isotope box models to examine the isotopic consequences of including sulfide oxidation pathways in a model system. These models demonstrate how the small δ³⁴S effects associated with S oxidation combined with large δ³⁴S effects associated with sulfate reduction (by SRP) and sulfur disproportionation (by SDP) can produce large (and measurable) effects in the Δ³³S of sulfur reservoirs. Specifically, redistribution of material along the pathways for sulfide oxidation diminishes the net isotope effect of SRP and SDP, and can mask the isotopic signal for sulfur disproportionation if significant recycling of S intermediates occurs. We show that the different sulfide oxidation processes produce different isotopic fields for identical proportions of oxidation, and discuss the ecological implications of these results to interpreting minor S isotope patterns in modern systems and in the geologic record.     

The microbial sulfur cycle and some of its implications for the geochemistry of sulfur isotopes

Qualitatively most microbial processes of the sulfur cycle are well known, but the extent to which specific groups of microbes take part in sulfate reduction and sulfide oxidation is at present difficult to estimate and the same holds for the role played by purely chemical sulfide oxidation.The capacity of an organism to differentiate between sulfur isotopes is genetically determined and probably strain-specific; whether or not, and to what extent, fractionation actually occurs is codetermined by physiological conditions inside the cell and by ecological conditions, i.e. the parameters of the environment.For conclusive interpretation of sulfur fractionation data of natural deposits further microbiological studies on the enzymatic, cellular and ecological level are necessary; such studies would be technically feasible today. The study of isotope effects of relevant, purely chemical reactions should not be neglected.

---

Zusammenfassung In qualitativer Hinsicht sind die meisten mikrobiellen Vorgänge des Schwefelkreislaufs gut bekannt. Jedoch ist es gegenwärtig noch schwierig zu sagen, in welchem Ausmaß die verschiedenen Mikroorganismengruppen an der Reduktion der Sulfate und an der Oxidation der Sulfide teilnehmen. In wieweit die Oxidation der Sulfide rein chemisch erfolgt, ist ebenso schwer einzuschätzen.Die Fähigkeit einer Mikrobe zwischen verschiedenen Schwefelisotopen zu unterscheiden, ist genetisch festgelegt und ist wahrscheinlich stammspezifisch. Ob überhaupt und, wenn ja, in welchem Ausmaß eine Fraktionierung tatsächlich stattfindet, wird von den physiologischen Verhältnissen innerhalb der Zelle und von ökologischen Verhältnissen, d. h. den Parametern der Umwelt, mitbestimmt.Um eine endgültige Interpretation der Fraktionierungsdata in der Natur abgelagerter Schwefelverbindungen zu ermöglichen, sind weitere mikrobiologische Forschungen auf enzymatischer, zellularer und ökologischer Stufe erforderlich, die heute ohne weiteres durchgeführt werden könnten. Isotopeneffekte bei rein chemischen Reaktionen sollten dabei ebenfalls untersucht werden.

---

Résumé La plupart des processus microbiologiques du cycle du soufre est qualitativement assez connue mais il est encore difficile de déterminer quantitativement dans quelle mesure des microbes spécifiques contribuent à la réduction des sulfates et à l'oxidation des sulfides. La même difficulté se présente quant à l'oxidation des sulfides purement chimique.Le pouvoir d'un organisme de distinguer entre les isotopes de soufre est déterminé par voie génétique et probablement est spécifique pour la souche individuelle. Dans quelle mesure un fractionnement des isotopes est vraiment réalisé sous les conditions expérimentales ou. naturelles est déterminé par des conditions physiologiques dans les cellules et des conditions écologiques, c'est à dire par les paramètres du milieu.Pour une interprétation conclusive des dates de fractionnement du soufre des dépôts naturels, il est nécessaire d'étudier les processus microbiens relevants au niveau enzymatique, cellulaire et écologique, des études qui sont aujourd'hui tout à fait réalisables. D'autre part, l'étude des effets isotopiques des réactions purement chimiques ne devrait pas être négligée.

---

, . .

---

---

Edited version of a lecture held at the Colloquium on the Geochemistry of Sulfur Isotopes, Bad Sooden-Allendorf, 1964; the references given provide entrances to the literature of the topics discussed rather than exhaustive documentation.     

我国酸沉降地区硫源的硫同位素组成研究

我国同世界大部分地区的酸雨类型一致,均为典型的硫酸型酸雨,因此硫同位素组成是示踪酸雨来源的重要手段。在前人研究的基础上,对酸雨硫同位素组成研究的思路和实验方法进行综述,重点介绍燃煤过程中硫同位素的分馏效应和大气SO2、气溶胶、大气降水、苔藓和小麦等植物中的硫同位素组成等,对环境地球化学的研究具有重要意义。     

Biogeochemical implications of inverse sulfur isotope effects during reduction of sulfur compounds by Clostridium pasteurianum

Large inverse sulfur isotope effects such as those encountered during SO₃^2? reduction by the non-symbiotic dinitrogen fixing soil anaerobe C. pasteurianum may induce ambiguity into calculations of isotopic and mass balance of sulfur compounds in the environment.     

Mass-dependent fractionation of quadruple stable sulfur isotope system as a new tracer of sulfur biogeochemical cycles

Sulfur isotope studies of post-Archean terrestrial materials have focused on the ratio ³⁴S/³²S because additional isotopes, ³³S and ³⁶S, were thought to carry little information beyond the well-known mass-dependent relationship among multiple-isotope ratios. We report high-precision analyses of Δ³³S and Δ³⁶S values, defined as deviations of ³³S and ³⁶S from ideal mass-dependent relationships, for international reference materials and sedimentary sulfides of Phanerozoic age by using a fluorination technique with a dual-inlet isotope ratio mass spectrometer. Measured variations in Δ³³S and Δ³⁶S are explained as resulting from processes involve branching reactions (two or more reservoirs formed) or mixing. Irreversible processes in closed systems (Rayleigh distillation) amplify the isotope effect. We outline how this new isotope proxy can be used to gain new insights into fundamental aspects of the sulfur biogeochemical cycle, including additional constraints on seawater sulfate budget and processes in sedimentary sulfide formation. The isotope systematics discussed here cannot explain the much larger variation of Δ³³S and Δ³⁶S observed in Archean rock records. Furthermore, Phanerozoic samples we have studied show a characteristic Δ³³S and Δ³⁶S relationship that differs from those measured in Archean rocks and laboratory photolysis experiments. Thus, high precision analysis of Δ³³S and Δ³⁶S can be used to distinguish small non-zero Δ³³S and Δ³⁶S produced by mass-dependent processes from those produced by mass-independent processes in Archean rocks and extraterrestrial materials.     

The isotopic composition of plant sulfur

The isotopic composition of sulfur has been studied in plants representative of various regions of the U.S.S.R., two oceanic islands, and atmospheric precipitations on land and in marine areas. In soils, the isotopic composition of sulfur in the atmospheric water varies as a result of sulfate reduction (increase of δ³⁴S of the soil sulfate) and sulfate regeneration from hydrogen sulfide. The sulfur in plants from the oceanic islands has characteristically higher values of δ³⁴S than the sulfur in the plants and in the atmospheric water of the continents. Compared to sea water, the sulfur from the island plants that were studied contains a considerably lesser proportion of the ³⁴S isotope. This can be explained by the significant role in such plants of the sulfur of the atmospheric air masses coming from the continents.     

The distribution of sulfur and organic matter in various fractions of peat: origins of sulfur in coal

The peat-forming systems of the Okefenokee Swamp are viewed as modern progenitors of coal. Taxodium and Nymphaea-derived peat-forming systems were characterized in terms of (1) organic fractions and (2) the distribution of organic/inorganic sulfur in each organic fraction (water soluble, benzene/methanol soluble, humin, humic acid, fulvic acid). The humin fraction is the largest organic fraction in both environments, approaching 70% of the total organic matter in the Nymphaea-derived environment. Humin origins are discussed in terms of a humic acid precursor, and undecomposed plant material. It is suggested that each depth of peat represents a diagenetic history of events which the authors believe occurred primarily when the currently buried peat was at the surface. The sulfur content of both peat-forming areas is low (0.23–0.27%); organic sulfur is the dominant sulfur form. Humin contains 50–80% of the total sulfur and of this, 80% is organic sulfur. Ester-sulfate appears to be especially prevalent in the fulvic acid fraction. The sulfur content of freshwater-derived peats is similar in quantity and distribution to that found in low sulfur coals.     

太湖大气气溶胶中硫稳定同位素组成分析

用 MAT-253同位素质谱仪对太湖大气气溶胶中的硫稳定同位素组成特征进行了分析.结果显示,太湖大气气溶胶中δ34S 数值变化范围为4.46‰~9.87‰,表明该地区大气气溶胶的主要硫源与当地燃煤排放直接相关.Δ33S 绝对值普遍大于0.1‰,说明太湖大气气溶胶中存在显著的硫稳定同位素非质量分馏效应;基于正Δ33S 和负Δ36S 的关联,揭示太湖气溶胶中硫稳定同位素的分馏异常主要与平流层 SO2发生的光化学反应有关,该科学问题迫切需要做进一步系统深入的研究.