Factors Controlling Sulfide Geochemistry in Sub-tropical Estuarine and Bay Sediments

The primary factors that control the concentration of total reduced (inorganic) sulfide in coastal sediments are believed to be the availability of reactive iron, dissolved sulfate and metabolizable organic carbon. We selected nine sites in shallow (<3 m), close to sub-tropical, estuaries and bays along the central Texas coast that represented a range in sediment grain size (a proxy for reactive iron), salinity (a proxy for dissolved sulfate), and total organic carbon (a proxy for metabolizable organic carbon). Based on these parameters a prediction was made of which factor was likely to control total reduced sulfide at each site and what the relative total reduced sulfide concentration was likely to be. To test the prediction, the sediments were analyzed for total reduced sulfide, acid volatile sulfide, and citrate dithionate-extractable, HCl-extractable and total Fe in the solid phase. Using solid-state gold–mercury amalgam microelectrodes and voltammetry, we determined pore water depth profiles of Fe(II) and ΣH₂S and presence or absence of FeS_(aq). At five of the nine sites the calculated degree of sufildization of citrate dithionite-reactive-iron was close to or greater than 1 indicating that rapidly reactive iron was probably the limiting factor for iron sulfide mineral formation. At one site (salinity = 0.9) dissolved Fe(II) was high, ΣH₂S was undetectable and the total reduced sulfide concentration was low indicating sulfate limitation. At the last three sites a low degree of sulfidization and modest total reduced (inorganic) sulfide concentrations appeared to be the result of a limited supply of metabolizable organic carbon. Fe(II)–S(-II) clusters (FeS_(aq)) were undetectable in 10 out of 12 bay sediment profiles where ΣH₂S was close to or below detection limits, but was observed in all other porewater profiles. Acid volatile sulfide, but not total reduced sulfide, was well correlated with total organic carbon and ranged from being undetectable in some cores to representing a major portion of total reduced sulfide in other cores. Although predicted controls on total reduced sulfide were good for very low salinity water or sandy sediments, they were only right about half the time for the other sediments. The likely reasons for the wrong predictions are the poor correlation of total organic carbon with grain size and differing fractions of metabolizable organic carbon in different sedimentary environments. Differences in sediment accumulation rates may also play a role, but these are difficult to determine in this region where hurricanes often resuspend and move sediments. This study demonstrates the need to examine more complex and often difficult to determine parameters in anoxic “normal marine” sediments if we are to understand what controls the concentration and distribution of sulfides.     

水体中硫化物测定方法探讨

通过对测定硫化物标准曲线的质量保证及不同污染程度水样的前处理方法的探讨,得出硫化物标准溶液需现用现配及针对污染程度不同的水样分别采取直接测定、抽滤测定和酸化-吹气法测定的结论.     

硫化物矿物溶解度与溶液pH值的关系

硫化物作为自然界常见的一大类矿物 ,由于溶解度很小 ,硫化物对水pH值的影响以及水对它的溶解度影响往往被人们所忽视。通过计算常见硫化物矿物的自由能ΔG0f、溶度积Ksp和溶解度S、绘制logS—pH曲线 ,得出硫化物矿物在不同 pH值条件下的溶解规律 ,水溶液的pH值受硫化物矿物的控制 ;反过来 ,水溶液的pH值也影响着矿物溶解度的大小。此外 ,对硫化物矿物饱和溶液的缓冲范围、缓冲容量和硫化物与溶液pH值相互作用的机理进行了探讨     

Petrochemical Investigation of the Antique Ophiolite (Philippines): Implications on Volcanogenic Massive Sulfide and Podiform Chromitite Deposits

Abstract: The Antique ophiolite, located in Panay island (west‐central Philippines), corresponds to several tectonic slices within the suture zone between the Philippine Mobile Belt (PMB) and the North Palawan Block (NPB). It includes dismembered fragments of a basaltic sequence, dominantly pillow‐lavas with minor sheet flows, rare exposures of sheeted dikes, isotropic gabbros, subordinate layered mafic and ultramafic rock sequences and serpentinites. Most of the ophiolite units commonly occur as clasts and blocks within the serpentinites, which intrude the whole ophiolitic body, as well as, the basal conglomerate of the overlying Middle Miocene sedimentary formation. The volcanic rock sequence is characterized by chemical compositions ranging from transitional (T)‐MORB, normal (N)‐MORB and to chemistry intermediate between those of MORB and island arc basalt (IAB). The residual upper mantle sequence is harzburgitic and generally more depleted than the upper mantle underlying modern mid‐oceanic ridges. Calculations using whole‐rock and mineral compositions show that they can represent the residue of a fertile mantle source, which have undergone degrees of partial melting ranging from 9‐22.5 %. Some of the mantle samples display chondrite‐nor‐malized REE and extended multi‐element patterns suggesting enrichments in LREE, Rb, Sr and Zr, which are comparable to those found in fore‐arc peridotites from the Izu‐Bonin‐Mariana (IBM) arc system. The Antique ultramafic rocks also record relatively oxidizing mantle conditions (Δlog f_O2 (FMQ)=0.9‐3.5). As a whole, the ophiolite probably represents an agglomeration of oceanic ridge and fore‐arc crust fragments, which were juxtaposed during the Miocene collision of the PMB and the NPB. The intrusion of the serpentinites might be either coeval or subsequent to the accretion of the oceanic crust onto the fore‐arc. Volcanogenic massive sulfide (VMS) deposits occur either in or near the contact between the pillow basalts and the overlying sediments or interbedded with the sediments. The morphology of the deposits, type of metals, ore texture and the nature of the host rocks suggest that the formation of the VMS bodies was similar to the accumulation of metals around and in the subsurface of hydrothermal vents observed in modern mid‐oceanic ridge and back‐arc basin rift settings. The podiform chromitites occur as pods and subordinate layers within totally serpentinized dunite in the residual upper mantle sequence. No large coherent chromitite deposit was found since the host dunitic rocks often occur as blocks within the serpentinites. It is difficult to evaluate the original geodynamic setting of the mineralized bodies since the chemistry of the host rocks were considerably modified by alteration during their tectonic emplacement. A preliminary conclusion for Antique is that the VMS is apparently associated with a primitive tholeiitic intermediate MORB‐IAB volcanic suite, the chemistry of which is close to the calculated composition of the liquid that coexisted with the podiform chromitites.     

Stratigraphic Correlation of the Malusok Volcanogenic Massive Sulfide Deposits, Southern Mindanao, Philippines

Abstract: Two adjacent volcanogenic massive sulfide (VMS) deposits, the Main Malusok and the Malusok Southeast, are delineated within Barangay Tabayo, Siocon, Zamboanga del Norte, Mindanao, Philippines. These deposits comprise massive to semi-massive sulfide lenses representing the down-dip equivalent of oxidized gossans. The massive sulfides have a primary mineral assemblage of pyrite-chalcopyrite-sphalerite with significant amounts of supergene copper in the form of chal-cocite. Owing to structural and metamorphic overprinting combined with intense alteration, primary textures are generally obliterated. Rock types are classified according to dominant mineral assemblages whereas the main lithologic units comprising the Malusok volcanic package are divided based on the position of each unit relative to the mineralized zone. The main lithologic units are designated as the hanging wall, the host, and the footwall sequences. In correlating the stratigraphy of the Main Malusok zone with that of the Malusok Southeast zone, a chlorite/epidote-rich interval located at the base of the hanging wall sequence serves as a distinct stratigraphic marker from which all lithologies are referred to. Comparisons between the stratigraphy of the two areas show that massive to semi-massive sulfide lenses are confined within a single stratigraphic interval representing the favorable horizon for the entire Malusok area. However, differences exist relative to style of mineralization and configuration of the altered interval between the Main Malusok and the Malusok Southeast VMS deposits. Based on characteristics exhibited by each individual deposit, it is inferred that the Main Malusok VMS deposit overlies a feeder zone whereas the Malusok Southeast sulfide lenses represent satellite deposits and transported blocks.     

我国一些铜镍硫化物矿床主要金属矿物的特征

镍、铜共生的铜镍硫化物矿床是镍矿也是铜矿的重要矿床类型。磁黄铁矿，镍黄铁矿、黄铜矿是这类矿床的主要金属矿物。它们的某些矿物学特征，特别是微量元素Ｃｏ／Ｎｉ比值，与其他铜矿类型明显不同，这三种矿物组成不同于任何其他铜矿类型的典型矿物共生组合， 形成特殊的海绵损铁状、球滴状构造。     

蓝藻聚铁作用的模拟实验

实验模拟前寒武纪大气的高二氧化碳分压(P_CO2),低氧浓度条件下,加入较低浓度(6μg/g)铁的Zarronk培养液培养蓝藻Spirulina platensis,观察铁的沉淀与凝聚。藻在生长过程中不断改变环境的离子平衡系统以及pH,Eh等,造成铁的氧化、还原、络合和Fe³⁺沉淀。实验组与未加蓝藻的对照组有显著差别。实验证实藻在聚铁和铁矿形成中起重要作用。     

瑞典硫化物矿山尾矿淋滤水的控制

在瑞典,硫化物矿尾矿污染水的淋滤造成巨大的环境污染问题。本文概述一项利用天然土覆盖尾矿、最大限度地减少淋滤水的调查报告。研究表明,天然土渗水性是如此之高,以致于起不到明显的隔水效果。天然土盖层只能减少高降雨量期或迅速化雪期的渗水量,而且只对淋滤水峰值有作用。但是,作为一种蓄水体,位于尾矿顶部的密封盖层具有重要意义,它可以增加蒸腾损失。     

Studies on the Tolerating Mechanism for Sulfide in Urechis Unicinctus (Echiura:Urechidae)-cytological observation on Urechis Unicinctus in Different Hydrogen Sulfide Environment

This study on the cytological changes of the body wall ,aspiratory intestine and crissal bursa in Urechis unicincuts by light microscope(LM) and transmission electron microscope(TEM) showed that the difference between the body wall and the natural environment rich in H2S was not obvious,that the wall color of the aspiratory intestine in H2S rich environment changed from normal semitransparency to dark brown.that its epithelia were disassembled and the electron density of its cytoplasm matrix was lower;and that in H2S rich environment many basoplhilic granules occurred in the epithelia of the crissal bursa.Granules with single membrane and myelinefingure were found with TEM.