The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

厌氧沉积中有孔虫组合特征

厌氧沉积的有孔虫组合中,底栖有孔虫主要由Bolivina诸种和Buliminella tenuata组成,同时含有少量厌氧标志种Suggrunda eckisi;浮游有孔虫中以Globigerrina bulloides和G.quingueloba为数较多。底栖有孔虫与浮游有孔虫数量相比,浮游有孔虫数量很少。     

Trace metals in suspended particulate matter and in sediment trap material from a permanently anoxic fjord — Framvaren, South Norway

Geochemical studies of the trace metal concentrations in suspended particulate matter (SPM) and sediment trap material from a permanently anoxic fjord, Framvaren, South Norway in 1989 and 1993 indicate that extremely high concentrations of zinc (max = 183920 mg/kg), copper (max = 4130 mg/kg), lead (max = 2752 mg/kg), and cadmium (max= 8.1 mg/kg) sometimes (1993) occur in the SPM collected in the anoxic water layer. The highest concentrations of Zn occur just below the redoxcline at 22 m water depth (in 1993), and copper, lead and cadmium have maximum concentrations between 30 and 80 m depth, where the amount of total SPM is at a minimum (about 0.3 mg/L). On a mass per volume (g/L) basis, the maximum concentrations of Cd, Cu and Fe occur at the interface (21m) and those of Zn occur just below the redoxcline (22 m depth). The SPM and sediment trap data suggest that the metals are precipitated as sulfide minerals in the anoxic water. The presence of particulate sulfides was confirmed by SEM studies that show the occurrence of discrete metal (Cu, Fe, Pb, and Zn) sulfide particles in size from 10–20 m as well as framboidal pyrites (1–5 m in size). Higher levels of metal sulfides at intermediate depths rather than in the deep water of Framvaren (> 100 m), may be due to input of trace metals by water exchange over the sill in the upper part of the water column. In the deep water, less metal sulfide precipitation takes place due to depletion of trace metals, and the dilution of particulate metal concentrations by organic matter and by the chemogenic formation of calcite.     

深海二叠——三叠系界线研究现状

综述了深海二叠（Ｐ）－－三叠系（Ｔ）界线研究现状，介绍了深海Ｐ－Ｔ界线附近岩石地层，生物地层、缺氧事件及生物绝灭和复苏的研究进展，指出了深海Ｐ－Ｔ界线，缺氧事件和生物绝灭研究的分歧、不足及其症结。     

栖霞组沉积地球化学特征及其环境意义

沉积环境的古氧相特征是沉积环境和古海洋特征恢复的重要内容。岩石地球化学特征是判断其形成环境氧化还原条件的重要手段之一。本文以来宾地区铁桥面为重点．通过对栖霞组灰岩的地球化学分析，结合沉积学、古生态学特征．认为栖霞组沉积于贫氧的沉{只背景．是在海水深度和海域的局限程度等沉积条件发生周期性变化的情况下形成的。古氧相地球化学指标V(V十Ni)、Cc/La、U／Th值都适用于该组以钙质沉积为主的沉积物。黄铁矿矿化程度(DOP值)变。化较大．眨映该区多变的古氧相特征。     

湖南省沉积型锰矿地质环境及成矿作用

湖南省沉积型锰成矿时代跨度大,最早由早元古代板溪群马底驿期至早二叠世孤峰期。其中,早南华纪大塘坡期、中奥陶世烟溪期及中二叠世孤峰期为三个最主要成锰集中期,并且大体呈现出朝东南方向成矿时代变新的趋势。成锰沉积盆地是锰矿床就位的重要场所,相应的岩相古地理环境为锰成矿创造了有利条件,即相对缺氧的、滞流的安静环境。这种环境在诸多古地理环境中都可以形成,导致了锰成矿岩相古地理环境的多样性,如浅海陆棚相、次深海棚缘盆地相、次深海台缘斜坡相及陆表次深海海盆相。三个主要成锰期锰成矿作用具有统一性,成矿作用与地壳拉张、海侵事件、缺氧事件等区域性重大地质事件关联密切。     

鱼粪化石特征对早侏罗世托阿尔期湖泊生态系统的启示:以川东大安寨段为例*

早侏罗世托阿尔期早期大洋缺氧事件(Toarcian Oceanic Anoxic Event,~183.8 Ma)是一次全球性的多幕式生物—环境事件,其在四川盆地下侏罗统自流井组大安寨段亦有显示。对采集自川东北地区大安寨段的鱼粪化石进行形态学描述和内含物分析,发现鱼粪化石中含有大量的磷质成分,多为未经消化的鱼骨化石,另有大量介壳类化石与有机质混杂在一起。据露头岩性和显微薄片特征认为: (1)粪化石呈螺旋状,生产该粪化石的鱼类为大型肉食性鱼类,其喜食小型鱼类和软体动物等,推测可能是肺鱼类(角齿鱼);(2)鱼粪化石形成于开放型淡水湖泊中的半深湖—深湖区,其中湖泊表层含氧量丰富,主要由生产者、消费者构成了研究区早侏罗世托阿尔期大型湖泊生态系统,食物链较为复杂,而湖底为水动力条件较弱的还原环境。该研究成果可为早侏罗世托阿尔期大洋缺氧事件在湖泊中的沉积响应及生态影响研究提供依据。     

白垩纪大洋缺氧事件研究进展

系统总结了白垩纪OAEs的研究进展,重点讨论了OAE1a、OAE1b和OAE2时期的有机碳(TOC)含量、碳同位素、古温度和锶同位素特征及其古环境指示意义,综合分析了白垩纪OAEs的成因机制。结果表明白垩纪OAEs的发生可能与该时期海底大规模的火山活动以及由其引起的气温升高、碳水化合物大量分解、水文循环加快和海洋生物生产力提高等一系列变化有关。对于白垩纪OAEs演化特征和成因机制的深入研究具有重要借鉴意义。通过对白垩纪OAEs的综合分析发现,当前的研究区域主要集中在大西洋/特提斯盆地及其周边陆地,而对南半球高纬度地区的研究报道迄今未见,从而无法对白垩纪OAEs进行全球性对比和系统性研究。今后我们将重点围绕南半球高纬度地区白垩纪OAEs的演化特征、成因机制及其古气候环境效应等进行深入研究。