Reactive iron and its buffering capacity towards dissolved sulfide in sediments of Jiaozhou Bay,China

Reactive iron (Fe) oxides in marine sediments play a critical role in removal of free sulfide. In this study, 0.5 and 6 N HCl-extractable Fe, acid volatile sulfide (AVS), and pyrite were examined in sediments at three sites of eutrophic Jiaozhou Bay to investigate the interactions of sulfur and Fe and possible influences of eutrophication on free sulfide removal. The results indicate that formation and accumulation of AVS and pyrite are limited by low availability of labile organic matter, despite eutrophication of the bay water. Quick buffering of free sulfide proceeded mainly via consumption of 0.5 N HCl-extractable Fe (labile Fe), however, the consumption did not result in a depletion of the Fe pool. High residual buffering capacity enables a quick removal of free sulfide in porewater, and thereby it is difficult for sulfide to accumulate and to cause detrimental effects on benthic organisms at the present steady state. Significant effects of eutrophication on Fe and sulfur geochemistry is restricted only to the estuarine sediments which were subject to direct wastewater discharges, whereas no such effects were observed in other sediments of the bay.     

珠江口淇澳岛海岸带沉积物中硫酸盐还原和不同形态硫的分布

对珠江口淇澳岛海岸带3个站位(QA-11,QA-9和QA-14)的沉积物中不同形态的还原硫(酸可挥发性硫,黄铁矿和有机硫)、总有机碳(TOC)和孔隙水中SO42-,甲烷浓度进行了测定,并且利用稳态扩散模型计算其中2个站位(QA-9和QA-14)硫酸盐还原通量[1.74和1.14 mmol/(m2.d)]和甲烷厌氧氧化通量[0.34和0.29 mmol/(m2.d)]。研究结果表明由于潮间带沉积物受到SO42-供给的限制,因此位于潮间带的QA-11站位硫酸盐还原带较浅(约16 cm);在潮下带的QA-9和QA-14站位,随离海岸距离和水深的增加,硫酸盐还原通量呈现减小的趋势,并且硫酸还原逐渐受到可利用活性有机质的限制;甲烷厌氧氧化对硫酸盐还原的贡献表现出增加的趋势,由19.2%增加至25.5%。三个站位沉积物中按不同形态还原硫含量由大到小列出,它们是有机硫(OS)、黄铁矿(DS)、酸可挥发性硫(AVS)。沉积物中AVS的空间分布与硫酸盐还原通量有正相关性。QA-11和QA-14站位的黄铁矿与AVS硫的含量比值大于3,分别为7.9和3.6,表明两个站位的黄铁矿形成可能受硫酸盐还原作用的控制;QA-9站位黄铁矿与AVS硫的含量比值为2.2,暗示AVS向黄铁矿转化受到可利用活性铁的限制。     

Relation of asid-volatile sulfide and clay content of sediment to the bioavailability of zinc and cadmium: laboratory plus field experiment

Organic matter and iron and maganese oxides have been considered as the major affecting factors for metals in anoxic or oxidized sediment. In recent research, clay and sulfide are found as major factors in oxic or oxidized sediments that might affect bioavailability of metals. To test this hypothesis, the influence of sulfide, measured as acid-volatile sulfide （AVS）, and clay content on the bioavailability of zinc and cadmium in sediments was examined. Laboratory simulative experiment and field verification experiment were conducted, showing that the bioavailability of zinc and cadmium is strongly correlated to AVS and clay content in sediments. Taking into account both AVS and clay parameters in sediments together can better indicate the bioavailability of zinc and cadmium rather than considering one of them alone.     

Trace metal solubility in salt marsh sediments contaminated with sewage sludge

As part of a study to investigate the effect of nutrient and metal pollution on salt marshes, a sewage sludge fertilizer has been applied to experimental plots in Great Sippewissett Marsh, MA, since 1974. The concentration of nutrients, soluble sulfides, and metals were measured in porewater from these plots every 4–6 weeks from April to December in 1980. Metal and nutrient concentrations in these plots were consistently greater than in corresponding control plots. Nutrients stimulated growth of Spartina alterniflora, the dominant vegetation on these plots, and higher grass production increased sediment oxidation. Concentrations of soluble sulfide in fertilized plots were an order of magnitude lower than in surrounding areas. For much of the year sulfides could not be detected in porewater from surface sediments of fertilized plots.The solubility of metals in sediments in fertilized plots was greatly increased by the decrease in sulfide concentrations. For much of the year, the top 4 cm of the sediments in fertilized plots were undersaturated with respect to all metal sulfide minerals. This undersaturation may account for the large loss of metals observed on these plots. It appears that in the surface sediments of these plots the retention of metals may be governed in part by adsorption onto iron oxyhydroxides.Precipitation of metal sulfides may be important in limiting the penetration of metals deeper into the sediment. At 6 cm, Zn and Cd were always close to the solubility of their respective sulfide minerals. Below 4 cm, iron was undersaturated with respect to all iron monosulfide minerals but supersaturated with respect to pyrite. Copper was supersaturated with respect to CuS and Cu₂S in all samples where sulfide was above the detection limit. Gel filtration experiments indicated that significant amounts of iron and copper were organically complexed in the porewater and may have been partially responsible for the large supersaturations.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Microscopic analysis of pyrite in the sediments of two Brazilian mangrove ecosystems

This study has used scanning electron microscopy coupled with X-ray micro-analysis to compare the morphology of diagenetic pyrite formed in the sediments of two contrasting Brazilian mangroves. The Sepetiba Bay site is influenced by marine conditions, and pore waters show lower dissolved iron and higher dissolved total sulfide concentrations. The Paraíba do Sul River site, on the other hand, is influenced by fluvial waters, and shows higher dissolved iron and lower dissolved sulfide concentrations in pore waters. At both sites, pore waters were oversaturated for pyrite, and pyrite morphology was similar. The finding that pyrite morphology was similar despite marked differences in pore-water chemistry can be explained by the low solubility product of pyrite and the daily exposure of surficial sediments to air, conditioned by tidal cycles. This implies that oxygen input to the sedimentary environment is a key factor in the pyrite formation mechanism.     

Pyrite formation under conditions approximating those in anoxic sediments: II. Influence of precursor iron minerals and organic matter

In the paper (Wang and Morse, 1996) that preceded this study, we presented results of experiments performed using a silica gel crystal growth technique to produce pyrite under conditions approximating those commonly occurring in anoxic marine sediments. The primary focus of that study was on the chemical pathways that pyrite formation follows and how differing conditions influenced reaction kinetics and morphology of pyrite crystals. In this paper, we present results of further long-term (up to 1 y) studies of pyrite formation, using the silica gel experimental technique, in which we investigated the role that different precursor iron (hydr)oxide minerals and marine organic matter play in pyrite formation. The minerals studied were akaganeite (β-FeOOH), ferrihydrite (Fe₅HO₈ · 4H₂O), goethite (α-FeOOH), hematite (α-Fe₂O₃), lepidocrocite (γ-FeOOH), and magnetite (Fe₃O₄). Marine organic matter used in this study was freeze-dried plankton collected from near-surface water in the Gulf of Mexico. The influence of precursor iron (hydr)oxide mineralogy, although important for initial iron sulfidization rates, was relatively minor compared to other variables, such as solution pH and sulfide concentration, in controlling the rate of pyrite formation. Consequently, major variations in the observed rate of pyritization of different iron (hydr)oxide minerals in sediments (e.g., Canfield and Berner, 1987) may reflect large differences in surface areas of the minerals rather than their intrinsic reactivity and is a confirmation of the estimates of Canfield et al. (1992) that most iron oxides have similar reactivity. The presence of marine organic matter (freeze-dried plankton) caused an increase in the sulfidization rate of goethite and a major (about 20 ×) decrease in the rate of pyrite formation. This can be interpreted as indicating that organic matter-iron interactions are important in both iron (hydr)oxide dissolution, and pyrite nucleation and growth. A possible explanation for this behavior is that dissolved organic matter produced during the long experiments (up to 1 year) increased the rate of goethite dissolution while inhibiting pyrite nucleation and growth by complexing iron. The lessons learned in the study of other mineral reaction kinetics (e.g., calcite and aragonite), that rates determined in pure inorganic systems, may not always be reliably applied to natural systems where organic matter can significantly influence mineral dissolution and growth rates, are, alas, repeated here for pyrite.     

Variations of methane induced pyrite formation in the accretionary wedge sediments offshore southwestern Taiwan

The accretionary wedge of offshore southwestern Taiwan contains abundant deposits of gas hydrate beneath the sea floor. High concentrations of methane in pore waters are observed at several locations with little data concerning historical methane venting available. To understand temporal variation of methane venting in sediments over geologic time, a 23-m-long Calypso piston core (MD05-2911) was collected on the flank of the Yung-An Ridge. Pore water sulfate, dissolved sulfide, dissolved iron, methane, sedimentary pyrite, acid volatile sulfide, reactive iron, organic carbon and nitrogen as well as carbonate δ¹³C were analyzed.Three zones with markedly different pyrite concentration were found at the study site. Unit I sediments (>20 mbsf) were characterized with a high amount of pyrite (251–380 μmol/g) and a δ¹³C-depleted carbonate, Unit II sediments (15–20 mbsf) with a low pyrite (15–43 μmol/g) and a high content of iron oxide mineral and Unit III sediments (<10 mbsf) by a present-day sulfate–methane interface (SMI) at 5 m with a high amount of pyrite (84–221 μmol/g) and a high concentration of dissolved sulfide.The oscillation records of pyrite concentrations are controlled by temporal variations of methane flux. With an abundant supply of methane to Unit I and III, anaerobic methane oxidation and associated sulfate reduction favor diagenetic conditions conducive for significant pyrite formation. No AOM signal was found in Unit II, characterized by typical organically-limited normal marine sediments with little pyrite formation. The AOM induced pyrite formation near the SMI generates a marked pyrite signature, rendering such formation of pyrite as a useful proxy in identifying methane flux oscillation in a methane flux fluctuate environment.     

黄东海沉积物中的还原无机硫

Cold diffusion methods are used to separate and quantify the three reduced inorganic sulfur species into acid volatile sulfide(AVS), pyrite–S and element sulfur(ES) in the sediments of the Yellow and East China Seas. The results show that up to 25.02 μmol/g of AVS, 113.1 μmol/g of pyrite–S and 44.4 μmol/g of ES are observed in the sediments of the Yellow Sea and East China Sea. Pyrite–S is the predominant sulfide mineral in the sediments, while the concentration of AVS is quite low at most stations in the study area. The amounts and reactivity of organic matter are the primary limited factor for the sulfide formation, while an iron limitation and a sulfate limitation are not observed in the sediments of the Yellow Sea and East China Sea. The irregular profiles of the three reduced inorganic sulfur species also reflected the comprehensive influence of sediment composition and sedimentation rates.     

Determination of inorganic sulphur speciation with polarographic techniques: Some preliminary results for recent hypersaline anoxic sediments

Polarographic techniques have been used to determine reduced inorganic sulphur speciation in recent anoxic marine sediments from two hypersaline basins, the Tyro and the Bannock Basins, in the Eastern Mediterranean. The following phases were determined: acid volatile sulphur (AVS), pyritic sulphur and zerovalent sulphur. The determination of AVS and pyrite was based respectively on the acidification and Cr(II) reduction of these sulphur components to H₂S. H₂S was collected in base and the sulphide concentration was measured by polarography. Standard Na₂S and pyrite gave recoveries of 99.6% ± 3.9% and 97% ± 12% respectively. Total zerovalent sulphur in a sediment sample was measured by the reaction of sulphite with thiosulphate. Thiosulphate was measured directly by polarography.

Pyrite is the main phase of inorganic reduced sulphur in the sediments from the Tyro and the Bannock Basins, and it has about the same average level (125 υmoles per gramme dry weight) in the cores recovered from the two areas. However, the distribution of pyrite in the top 100 cm of the two cores differs significantly. In the Bannock Basin a sharp increase is observed with depth, whereas in the Tyro Basin there is a small decrease with depth.

The total amount of reduced inorganic sulphur is less than the total amount of sulphur in the sediments. This indicates that there must be additional sulphur-bearing phases. One of these phases may be gypsum, and indeed, gypsum crystals have been observed in the Bannock Basin.

In neither basin is there a significant correlation between reduced sulphur and organic carbon. The pyrite that occurs in these basins may have been formed syngenetically at the interface of the anoxic brine and oxic seawater. Diagenetic pyrite may have been formed within the sediments of the basins. AVS and total zerovalent sulphur are still observed at depth. We therefore suggest that this may be due to the incomplete transformation of AVS and zerovalent sulphur into pyrite.     

Sulfide control of cadmium and copper concentrations in anaerobic estuarine sediments

Equilibrium concentrations of the toxic trace metals copper and cadmium were calculated for the physico-chemical conditions characterizing pore waters of anaerobic estuarine sediments using available thermodynamic data and assuming simple sulfide minerals control solubilities. Polysulfide complexes are responsible for the solubility of copper in the cuprous (Cu(I)) oxidation state. Predicated copper concentrations, assuming covellite (CuS) is the controlling solid phase, are in reasonable agreement with copper analyses in a wide range of sulfidic waters and sediment pore waters. In the absence of thermodynamic data, no account could be taken of possible polysulfide complexes of cadmium. However, bisulfide complexes appear to account satisfactorily for observed solubilities assuming the existence of greenockite (CdS) as the controlling solid phase. Anaerobic estuarine sediments may act as a sink for copper and cadmium in the common situation in which free sulfide concentrations are controlled by the coexistence of iron sulfide and iron oxide minerals. However, where free sulfides reach high concentrations of 10^?3 M or more, the concomitant increase in concentration of bisulfide and polysulfide complexes may result in the sediments acting as a source of copper and cadmium.     

The characterization of iron sulfide minerals in anoxic marine sediments

The performance of extractants commonly used in the determination of acid volatile sulfide minerals (e.g., ‘amorphous-FeS’, mackinawite and greigite) and pyrite has been evaluated using pure mineral phases and anoxic sediments. ‘Amorphous-FeS’ and mackinawite are quantitatively recovered by most cold acid extractions, but greigite recovery is incomplete. Harsher extractants with reducing agents are necessary for the complete recovery of greigite, but dissolution of fine-grained synthetic pyrite occurs under such conditions. A quantitative separation between greigite and pyrite is not possible using these techniques, but the use of ‘acid volatile sulfide’ and ‘pyrite’ as operational categories is adequate for most field studies.     

磁性矿物还原成岩作用述评

许多海洋－湖泊环境中的沉积物受到还原成岩作用的影响发生磁性颗粒的溶解和自生现象。根据最近二十多年的研究成果,简要介绍了磁性矿物发生还原作用的基本过程、产物和控制因素,成岩作用对沉积物地球化学和磁学特征的改变,成岩自生亚铁磁性铁硫化物的磁学特征以及成岩作用对古地磁和环境磁学记录的影响。     

Mineralogical characteristics of polymetallic sulfides from the Deyin-1 hydrothermal field near 15°S,southern Mid-Atlantic Ridge

A seafloor hydrothermal field, named Deyin-1 later, near 15°S southern Mid-Atlantic Ridge(SMAR) was newly found during the 22 nd cruise carried out by the China Ocean Mineral Resources Research Development Association(COMRA). Sulfide samples were collected at three stations from the hydrothermal field during the26 th cruise in 2012. In this paper, mineralogical characteristics of the sulfides were analyzed with optical microscope, X-ray diffractometer, scanning electron microscope and electron microprobe to study the crystallization sequence of minerals and the process of hydrothermal mineralization. According to the difference of the ore-forming metal elements, the sulfide samples can be divided into three types:(1) the Ferich sulfide, which contains mainly pyrite and chalcopyrite;(2) the Fe-Cu-rich sulfide consisting predominantly of pyrite, chalcopyrite and isocubanite, with lesser amount of sphalerite, marmatite and pyrrhotine; and(3) the Fe-Zn-rich sulfide dominated by pyrite, sphalerite and marmatite, with variable amounts of chalcopyrite, isocubanite, pyrrhotine, marcasite, galena and gratonite. Mineral precipitations in these sulfides are in the sequence of chalcopyrite(isocubanite and possible coarse pyrite), fine pyrite,sphalerite(marmatite), galena, gratonite and then the minerals out of the dissolution. Two morphologically distinct generations(Py-I and Py-II) of pyrite are identified in each of the samples; inclusions of marmatite tend to exist in the coarse pyrite crystals(Py-I). Sphalerite in the Fe-Zn-rich sulfide is characterized by a"chalcopyrite disease" phenomenon. Mineral paragenetic relationships and a wide range of chemical compositions suggest that the environment of hydrothermal mineralization was largely changing. By comparison, the Fe-rich sulfide was formed in a relatively stable environment with a high temperature, but the conditions for the formation of the Fe-Cu-rich sulfide were variable. The Fe-Zn-rich sulfide was precipitated during the hydrothermal venting at relatively low temperature.     

Diagenetic deposition of manganese in sediment of a historically meromictic lake,Lake Suigetsu,Japan

Vertical profiles of manganese concentration in interstitial waters and of manganese and iron contents in five chemically-separated fractions of sediments have been studied in a sediment core (73 cm long) from a meromictic lake, Lake Suigetsu, which changed from freshwater to brackish conditions in 1664 A.D. The interstitial waters show a minimum manganese concentration of 0.13 ppm near a depth of 10 cm and a maximum of 26 ppm near 65 cm in the core. A predominant amount of manganese, up to 0.17%, is found in the hydrogen peroxide-soluble fraction of sediments in layers above a depth of 52 cm. It is suggested that the manganese is included in stable iron sulfides such as pyrite. Manganese, which diffuses upward from the lower layer, is thought to be deposited along with stable iron sulfide during diagenetic formation of the latter near a depth of 10 cm in the core.     

太平洋三海区热液硫化物中黄铁矿的形态标型和矿物标型特征研究

以成因矿物学的理论和方法,围绕太平洋三区四地海底热液硫化物和烟囱物中黄铁矿为主线的形态标型(扫描电镜)、矿物标型(粉晶X射线衍射法)及矿物组合,揭示了黄铁矿及伴生矿物在不同热液喷发类型中的标型特征,并由此反证了不同标型特征的热液矿物与热液喷发环境相互依存的紧密关系。     

海洋沉积物中酸溶硫化物对二价金属镉的地球化学特征及生物毒性的影响

通过海洋沉积物镉加标实验、沉积物间隙水分析和对加标沉积物毒性的10天底栖端足类生物检验，重点探讨在硫化物存在条件下，二介有毒金属镉在沉积物－间隙水系统中的地球化学分配和化学活性，及镉在沉积物中的化学活性与生物毒性间的关系。研究结果表明，镉加标沉积物的毒性与间隙水中镉浓度呈正相关，而与沉积物镉总量无关。在硫化物存在条件下，沉积物－间隙水系统中，二价镉在固、液两相同的分配主要受酸溶硫化物（AVS）影响。AVS归一化沉积物中二价镉含量可作为预测和评价二价有毒金属镉的化学分配行为和生物可获性或毒性的有效方法。酸解硫化物时同步提取的金融镉SEMCd^2 与AVS的摩尔浓度之比[SEMCd^2 ]/[AVS]可用作评价缺氧状况下镉沾污沉积物的环境质量和毒性的判据。     

应用平衡分配模型评价渤海湾和莱州湾沉积物重金属潜在生物毒性

为探讨渤海沉积物中重金属的生物毒性,采集了渤海湾和莱州湾共72个站点的表层沉积物,测定了酸可挥发性硫化物(AVS)、同步萃取金属(SEM)、有机碳(TOC)等参数,应用平衡分配模型(EqP Model)评价了沉积物中重金属的潜在生物毒性。研究显示,有8个站点超过了EqP Model的毒性阈值,显示潜在生物毒性,而61%的站点应无生物毒性。本研究同时测定了沉积物的总含量,应用几种常用的沉积物质量基准进行了评价虽然有部分站点的Cu、Ni、Cr超过了基准值,但与渤海的背景值比较,这些基准值可能并不适用于评价渤海沉积物。研究显示,EqP Model可以更有效的评价沉积物中重金属的活性和生物毒性,尤其针对我国近岸海域的沉积物,TOC和AVS含量偏低而重金属生物毒性偏高的情况可能普遍存在,更应积极考虑应用EqP Model进行重金属生物毒性的评价。     

西南印度洋龙旂、断桥热液区沉积物中重矿物空间分布特征及其意义

以中国大洋第34航次在西南印度洋龙旂与断桥热液区采集的洋底表层沉积物样品为研究对象,为洋中脊热液硫化物勘查重砂找矿工作提供一定的理论与工作基础,开展了沉积物自然重砂矿物的相关研究。绘制了研究区重砂矿物分布图,并根据研究区已探明热液矿体(喷口)的位置,对沉积物重分散晕的形成与分布规律进行了分析;从研究区沉积物的34种矿物中,筛选出3种沉积物重砂找矿的指示性矿物(重砂总量、黄铜矿、黄铁矿)及5种参考性矿物指标(帘石类矿物、透闪石、磁铁矿、铬铁矿、钛铁矿);运用统计学方法,建立了沉积物中指标矿物含量与矿源距离之间的线性方程,提出了根据测站沉积物中指标矿物含量,初步推算矿源距离的方法。     

胶州湾李村河口沉积物中重金属分布特征及其控制因素

对胶州湾李村河口4个站点沉积物中的酸可挥发性硫化物(AVS)以及同步提取金属元素(SEM,包括Cu,Cd,Ni,Pb和Zn)的含量进行测定,以研究重金属元素在河口海湾沉积物中的分布特征及影响其分布的因素。结果表明,J1站表层沉积物中同步提取金属含量高于其它站点;除J1站外其他站点的同步提取金属的总量随沉积物深度变化范围不大;J1站的SEM/AVS比值始终小于1,其他站点SEM/AVS比值只在沉积物浅表层大于1。此外,AVS和同步提取Fe的含量对沉积物中同步提取金属的分布有着重要影响,其他的因素如有机质的含量等也会对沉积物中同步提取金属的分布产生影响。