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1.
A field and laboratory study of the accuracy of a method commonly used to determine free sulphide concentrations in the porewater of marine sediments is presented. The method uses an ion-selective electrode (ISE), sensitive to the sulphide ion (S2−), in sediments buffered to high pH (>12) and is commonly used in regulatory monitoring programs to assess the impacts of open net-pen finfish aquaculture on local marine habitats. Here we report that on the timescale of field measurements, the accepted protocol can lead to significant bias of free sulphide measurements, with orders of magnitude higher concentration detected in the buffered sediment–porewater slurry than in porewater samples isolated and analysed separately. Laboratory experiments with model marine sediments and analysis of sediment composition indicate that this bias is likely introduced by the dissolution of particulate sulphides and/or sulphur present in the sediments under the intense alkaline conditions of the protocol. Recommendations for the modification and continued use of this commonly applied field methodology are discussed.  相似文献   

2.
海洋沉积物中氧化亚铁的分析测定   总被引:2,自引:0,他引:2  
郑凯清  张仲平 《岩矿测试》1999,18(3):198-200
海洋沉积物试样用H2O2-HAc浸取,用以除去干扰测定FeO的锰化合物和硫化珠,并以H2SO3-Na2SO3混合溶液破坏过乘的H2O2,不需过滤分离,即可用HF-H2SO4分解试样,K2Cr2O7标准溶液滴定FeO。方法经海洋沉积物国家标准物质分析验证,结果与参考值相符,RSD为6.33%。  相似文献   

3.
Fe (III) reduction is a key component of the global iron cycle, and an important control on carbon mineralization. However, little is known about the relative roles and rates of microbial (biotic) iron reduction, which utilizes organic matter, versus abiotic iron reduction, which occurs without carbon mineralization. This paper reports on the capacity for salt marsh sediments, which typically are rich in iron, to support abiotic reduction of mineral Fe (III) driven by oxidation of sulphide. Sediment was reacted with amorphous FeS under strictly anaerobic conditions at a range of temperatures in biotic and abiotic microcosm experiments. Fe (III) reduction driven by sulphide oxidation occurs abiotically at all temperatures, leading to Fe (II) and elemental sulphur production in all abiotic experiments. In biotic experiments elemental sulphur is also the oxidized sulphur product but higher bicarbonate production leads to FeCO3 precipitation. Abiotic reduction of Fe (III) occurs at rates that are significant compared with microbial Fe (III) reduction in salt marsh sediments. The solid phases produced by coupled abiotic and biotic reactions, namely elemental sulphur and FeCO3, are comparable to those seen in nature at Warham, Norfolk, UK. Furthermore, the rates of these processes measured in the microcosm experiments are sufficient to generate siderite concretions on the rapid time scales observed in the field. This work highlights the importance of abiotic Fe (III) reduction alongside heterotrophic reduction, which has implications for iron cycling and carbon mineralization in modern and ancient sediments.  相似文献   

4.
Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na2S; 1500-2000 ppm S by weight) and the other with H2O (∼3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H2O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H2O) demonstrate that H2O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H2O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments.In Raman spectra a band at 2576 cm−1 appears in the sulphide - H2O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm−1 (on expense of the combination band of molecular H2O at 5225 cm−1) and at 3400 cm−1 was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H2O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S2− - H2O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple experiments. On the contrary, XANES spectra from experiments conducted with a free H2O fluid show complete transformation of sulphide to sulphate near the melt surface and coexistence of sulphate and sulphide in the center of the melt. This can be explained by a lower H2O activity in the diffusion couple experiments or by the need of a sink for hydrogen (e.g., a fluid which can dissolve high concentration of hydrogen) to promote oxidation of sulphide by H2O via the reaction S2− + 4H2O = SO42− + 4H2. Sulphite could not be detected in any of the XANES spectra implying that this species, if it exists in the melt, it is a subordinate or transient species only.  相似文献   

5.
Potential hydrolysis rates of three different polysaccharides, pullulan, laminarin, and xylan, were measured in intact sediment cores from Cape Lookout Bight, North Carolina, in order to constrain the rates at which a fraction of the high-molecular-weight sedimentary carbon pool may be hydrolyzed to lower molecular weights. Potential hydrolysis rates of pullulan were somewhat higher than those of laminarin and xylan. Highest potential rates were measured in surface sediments; rates at depths of 5–7 and 14–16 cm differed relatively little from one another. Total dissolved carbohydrates, dissolved organic carbon (DOC), sulfate, and sulfate reduction rates were also measured and compared with data previously collected at Cape Lookout Bight in order to investigate carbohydrate dynamics and establish the relative contribution of carbohydrates to the sedimentary carbon budget. Total porewater carbohydrates constitute a disproportionate fraction of DOC, ranging from a maximum of 85% in near-surface intervals to 24% at depths of 14–16 cm. A comparison of potential hydrolysis rates, dissolved carbohydrate concentrations, DOC, and sulfate reduction rates, along with results from a wide range of studies previously conducted at this site suggests that hydrolysis of high-molecular-weight polysaccharides can potentially be very rapid relative to carbon remineralization rates. Dissolved porewater carbohydrates form a dynamic pool that is likely turned over on short timescales in Cape Lookout Bight sediments.  相似文献   

6.
《Applied Geochemistry》2001,16(7-8):781-791
Fine-scale solid-phase trace metal and acid-volatile sulphide profiles are presented for sediment cores taken at four locations in Lake Ketel, a dynamic sedimentation basin of the river Rhine in The Netherlands. The purpose of this study was to relate these profiles to the dynamics of sediment transport in the lake. The internal cycling of solids in the lake affects the distribution of trace metals and acid-volatile sulphide in the sediments. Comparison of vertical profiles of trace metals and sulphide indicates significant spatial variation in the dynamics of sediment transport in Lake Ketel. The construction of a dredge spoil storage depot in 1996 seems to have significantly influenced the hydrodynamic and sediment dynamics in Lake Ketel. Consequently, deposition rates in Lake Ketel based on comparison of solid-phase trace metal concentrations in the sediments and historical levels in Rhine suspended matter can only be used as rough estimates.  相似文献   

7.
The high-resolution mapping of dissolved sulphide in modern sediment of a permanently stratified (meromictic) lake is possible using a novel sulphide imaging technique (called a 'sulphur print'). The technique is simple, easy to use and can map a relatively large area (up to several dm2). In situ sulphur prints from anoxic fine-grained sediments are able to reveal internal structures in apparently homogeneous materials. Sulphur prints have been used to examine the formation and distribution of dissolved sulphide in the sediment and water column of the meromictic Lake Cadagno (southern Switzerland). The prints show clearly that a previously unknown laminar convective flow of sulphide-free porewater occurs across the sediment–water interface. Such convective flow out of the sediment must be accompanied by convective flow of sulphide- and sulphate-rich lake water into the sediment, and may be an important mechanism for the accumulation of sulphur in the sediment.  相似文献   

8.
A qualitative and partly quantitative survey of the carbohydrates encountered in acid hydrolyzates of some recent marine sediments reveals the presence of a large variety of known and hitherto unknown monosaccharides. Apart from the well known major monosaccharides a great number of minor components (notably O-methyl and deoxy monosaccharides) are encountered. These minor components are considered to originate from bacteria. Since significantly larger amounts of major monosaccharides are encountered in carbohydrates associated with bacterial cell-walls the greater part of the carbohydrate carbon in these sediments is ascribed to these structures. Superimposed on the bacterial contribution the characteristics of the carbohydrates originating from the primary producers are recognizable. The results indicate that bacterial biopolymers formed by de novo synthesis in the sediment should be considered as a potential source for the insoluble organic matter in these sediments.  相似文献   

9.
Auriferous quartz pebble conglomerates (QPC) formed during Tertiary sedimentary recycling in the Waimumu district, Southland, New Zealand. These sediments contain fine-grained gold of detrital origin with abundant surface textures and gold-forms associated with authigenic gold remobilisation. Most authigenic gold contains no detectable silver and occurs as overgrowths on detrital Au–Ag and Au–Ag–Hg alloys that contain up to 13 wt.% Ag, and 9 wt.% Hg. Fine-grained Au–Ag and Au–Ag–Hg alloys are compositionally heterogeneous, exhibiting both well-defined silver-depleted and silver-enriched rims. Rare coarse Au–Ag alloy is intergrown with quartz and is homogenous. Discrete grains of authigenic, porous, sheet-like gold occur in carbonaceous mudstone within a QPC sequence. Some QPC contain abundant sulphide minerals. Some of these sulphides (pyrite and arsenopyrite) are of long-distance detrital origin, presumably from the Otago Schist, whereas the bulk of the sulphide suite is marcasite of variably transported diagenetic origin, derived from the erosion of QPC and underlying Tertiary sediments. There has also been authigenic deposition of sulphide minerals in the QPC themselves. These diagenetic sulphides include framboidal and anhedral marcasite, and framboidal and euhedral pyrite. Sulphur isotope data for the sulphide minerals range from − 45‰ to + 18‰ (relative to VCDT). Sulphur isotope data for euhedral detrital pyrite and arsenopyrite range from − 9‰ to − 1‰ and are most likely derived from the Otago Schist to the north. Both framboidal and anhedral marcasite have lower values (< − 20‰) reflecting microbial sulphate reduction as a source for the precursor hydrogen sulphide. Anhedral marcasite contains elevated concentrations of Ni, Co, As and Cr, commonly with compositional banding of these metals.Both the gold and diagenetic sulphides from the Belle-Brook QPC are compositionally similar to gold and sulphides from Archaean QPC. Porous, sheet-like authigenic gold is morphologically similar to gold associated with carbonaceous material in the Witwatersrand. In addition, Southland marcasite textures resemble the rounded and banded pyrite in Witwatersrand QPC placers. There is abundant evidence from these Tertiary QPC in southern New Zealand for sedimentary transport of sulphide minerals and post-depositional sulphide mineralisation in the surficial environment despite an oxygen-rich atmosphere. These young deposits thus provide an example of authigenic gold and sulphide textures formed during diagenesis in unmetamorphosed placers. Many of these textures are similar to those commonly ascribed to metamorphic processes in Archaean auriferous QPC.  相似文献   

10.
论硫化氢生成的地质条件   总被引:1,自引:0,他引:1  
根据硫化氢的赋存环境、组成特征和热还原反应模拟试验等,提出硫化氢生成需具备五项基本地质条件:(1)地层中富含石膏;(2)富含还原剂—烃类物质;(3)较大埋深或较高的地温条件;(4)地层水作为介质和反应场所;(5)严密的封存体系。热还原反应必须在有水条件下才能进行,硫酸盐水解后的硫酸根是硫化氢的直接供体。硫化氢的生成实际经历了一个天然气向地层水的溶入和脱出过程,两者的密切关系造成含硫化氢天然气通常出现在气-水界面附近,密封条件极好的岩性气藏或构造气藏当中,构造低部位或气藏下倾方向。但是,后期构造抬升有可能造成硫化氢与地层水的分离。  相似文献   

11.
Dump groundwaters in the former East-German lignite-mining district are characterized by high amounts of ferrous iron and sulphate. Both the pyrite weathering products endanger the surface water quality when discharged into lakes. Only the precipitation of both contaminants in the subsurface can prevent the further contamination of surface waters. The two-step process of microbial catalyzed sulphate reduction and iron sulphide precipitation is limited by the low availability of natural organic substances as electron donators. Therefore, a new remediation technique is developed based on the injection of a liquid organic electron donator (methanol) into the contaminated aquifer. The saturated aquifer is used as a bioreactor, where iron monosulphides are precipitated in the groundwater-filled pore space. Column experiments were performed under natural pressure and temperature conditions with natural anoxic groundwater and original sediments to test the remediation technology. The test showed that a complete iron removal (4 mmol/l), even under rather acid conditions (pH 3.8), is possible after having established an active sulphate reducer population. The turnover of the added organic substance with sulphate is complete and the amount of the resulting sulphide controls the effluent pH. In addition, intensified microbial activity triggers the turnover of natural organic substances. Also, natural Fe(III) hydroxides react with the sulphide produced. Considering the long natural retention times (decades), artificially enhanced FeS precipitation is spontaneous, although it shows kinetic behaviour in the range of days. In light of the promising results, the development of a field scale application of this technique is considered to be necessary. It will have to focus on the improved precipitation control of the FeS in the subsurface.  相似文献   

12.
13.
Greigite has been identified in the sediments of Loch Lomond using X-ray diffraction. Greigite is the dominant magnetic mineral in the oldest sediments recovered, while magnetite predominates in the younger sediments which had previously been used for palaeomagnetic secular variation studies. A layer of sediment in between these two magnetic mineral regimes has very low magnetic concentrations, probably as a consequence of magnetite dissolution associated with sulphide rich pore-waters produced at the time of a marine incursion. The greigite largely oxidises once the sediment is exposed to air, but if freeze dried the greigite becomes surprisingly stable. Following freeze drying the greigite can be heated to 280°C in air before it alters and loses its strong ferrimagnetic properties.  相似文献   

14.
A comparative study of lignin and neutral carbohydrate compositions, combined with C, N and δ13C analyses, was carried out on sedimentary cores, and on various vascular plant species collected in mangrove swamps of French Guiana. The main purpose of this study was to assess the diagenesis of carbohydrates and lignin in brackish to hypersaline fine-grained mangrove sediments characterized by great changes in redox conditions. Distribution of carbohydrates in sediments reflects both the lability of these compounds and their efficient recycling. They are subject to selective degradation, cellulosic glucose and xylose appearing to be the two most labile neutral sugars. In contrast a relative increase in arabinose, rhamnose, fucose and hemicellulosic glucose between plants and sediments, suggests that they may be more refractory and/or that they also derive from microbial synthesis. The total carbon from lignin-derived phenols is higher in sediments than in mangrove plants as a consequence of their rather refractory character. Nevertheless, evidence of lignin decomposition was found to be independent of local environmental conditions. The various redox processes that occur in mangrove sediments depend on plant species, stages in forest development and season. Different redox conditions induce different mechanisms for the decomposition of lignin and thus induce changes in phenol distributions. At depth, in most mangroves, an increase in (Ad/Al)v ratios and in deoxy sugars (fucose and rhamnose) content was significantly correlated with increased proportions of oxidized allochthonous organic debris deriving from the Amazonian detrital discharge, thus suggesting a specific source effect rather than a diagenesis induced change. Therefore, this study illustrates that both lignin and cellulose, derived from vascular plant debris, can be degraded in waterlogged mangrove sediments, and that their distribution depends on environmental conditions.  相似文献   

15.
The application of organic-rich lake sediment (gyttja) to exploration geochemistry is discussed. Gyttja was collected from some 42 lake sites in the Red Lake-Uchi Lake volcanic-sedimentary sequences.The existance of free sulphide ion in most gyttja is confirmed and theoretical calculations are used to define the approximate concentrations of sulphide ion which determine whether the accumulation of Cu+, Cu2+, Zn2+ and Fe2+ is by metal sulphide precipitation, organic complexing or both. These calculations show that in the sediments collected in this study, the accumulation of copper will probably be by metal sulphide formation, whereas for zinc, organic complexing and possibly sulphide precipitation are likely mechanisms.It is shown that the background concentrations of copper and zinc on a dry matter basis increase with the content of organic matter in the sediment and it is further shown that the quantity of interstitial water in the sediment increases linearly with the organic content. Also it is demonstrated that the organic matter in the sediment is dispersed in the interstitial water in approximately the same concentration irrespective of the sediment composition.On the assumption that copper sulphide colloids are dispersed in the interstitial water of the sediment, it is suggested that the copper content of gyttja should be expressed as μg/g interstitial water for meaningful interpretation. Similarly, the zinc content should be expressed relative to the organic matter content.The ability of reagents to selectively extract only chemically dispersed metals and not silicate lattice metals from gyttja is discussed.Both the analytical procedures and the interpretations are applied to the samples collected.  相似文献   

16.
A model is developed to explain the isotope fractionation effects produced in laboratory experiments involving the reduction of sulphate to hydrogen sulphide by the bacterium Desulfovibrio desulfuricans. The approach differs from previous ones in its use of zero-order kinetics to describe the uptake of sulphate by the bacterium. Expressions are developed which relate the overall isotope effects produced by the bacterium to the ratios of backward to forward flows between its internal sulphur reservoirs. Other applications of this type of model are discussed, including the differences of isotopic composition between sulphate and hydrogen sulphide in the Black Sea and an unusual isotope effect observed in the course of bacterial nitrate reduction.  相似文献   

17.
Formation and dissolution of authigenic Fe and Mn (oxyhydr)oxides influence cycling of trace metals in oxic/suboxic surface sediments. We used the diffusive gradients in thin films technique (DGT) to estimate the association of cobalt with iron and manganese oxides. We compared Co, Fe and Mn maxima measured by DGT in the pore waters of fresh and aged marine sediment cores and estimated the Co/Fe and Co/Mn ratios in the metal oxides. A Mn maximum was not visible in DGT concentration profiles of freshly collected sediment cores, but after ageing the sediment, we observed a distinct Mn peak, presumably due to broadening of the depth range over which the various electron acceptors occur. Estimated Co/Mn ratios from both experiments are within the range of literature values for marine sediments, but the value from the aged experiment is at the lower end of the range. This is attributed to stimulation of sulphate reduction and precipitation of cobalt sulphides. The good correlation between Co and Fe maxima in the fresh sediments is attributed to the similarity of their reactions with sulphide rather than Co being released during authigenic Fe oxide reduction.  相似文献   

18.
Trends in the spatial distribution of chlorophylla (chla) and colloidal and total carbohydrates on the Molenplaat tidal flat in the Westerschelde estuary, Netherlands, reflected spatial differences in physical properties of the sediment. Results from a Spearman Rank Order Correlation indicated that many of the physical and biological measures covaried. Multiple regression analyses describing the relationship between colloidal carbohydrates and sediment properties resulted in several highly significant equations, although in all cases chla was able to predict colloidal carbohydrate content. Relationships between sediment surface chla and colloidal carbohydrate, and sediment erodibility (i.e., critical erosion threshold, Ucrit, and mass of sediment eroded at a velocity of 30 cm s?1) determined in annular flume experiments were examined. Overall sediment erodibility was lowest (i.e., high thresholds, low mass eroded) for the siltiest sediments in June 1996 when chla and colloidal carbohydrates were high (56.9 μg gDW?1 and 320.6 μg gluc.equ. gDW?1, respectively), and greatest (i.e., low thresholds, high mass eroded) at the sandier sediments in September 1996, when chla and colloidal carbohydrates were low (1.0 μg gDW?1 and 5.7 μg gluc.equ. gDW?1, respectively). When sediments were grouped according to relative silt content, the most significant relationships were found in muddy sand with a finegrained fraction (<63 μm) of 25–50%. Thresholds of erosion increased, while mass of sediment eroded decreased, with increasing chla and colloidal carbohydrate. A similar trend was observed for the sand-muddy sand (63 μm 10–25%). In the sand (63 μm 0–10%), there were no relationships for Ucrit, whereas mass eroded appeared to increase with increasing chla and colloidal carbohydrate. The increased carbohydrate may stick sand grains together, altering the nature of erosion from rolling grains to clumps of resuspension.  相似文献   

19.
Summary Banded sulphide ores of the McArthur River type are characterized by large numbers of conformable, monomineralic sulphide bands. These appear to have formed prior to consolidation of the host sediments. This paper describes a series of laboratory experiments designed to test the possibility that the bands could have been generated by the migration of metal, sulphide, and possibly carbonate ions through unconsolidated sedimentary materials or slowly settling suspensions. It is concluded that ionic migration processes probably occur during the formation of these banded sulphide ores, in conjunction with the deposition of metalliferous mud layers.
Zusammenfassung Die Schichten der Schwefelerze des Typs vom McArthur Fluß sind charakterisiert durch eine Vielzahl von Parallelen, die ausschließlich aus Schwefelschichten bestehen. Diese scheinen sich vor der Verfestigung der Sedimentenmasse gebildet zu haben. Dieser Aufsatz beschreibt eine Reihe von Laboratoriums-Experimenten, die die Möglichkeit untersuchen sollten, ob diese Schichten entstehen konnten durch die Wanderung von Metall-, Schwefeloder möglicherweise Kohlensäure-Ionen durch noch nicht verfestigtes oder sich langsam setzendes Sedimentmaterial. Es wird daraus gefolgert, daß wahrscheinlich während der Formation dieser Schwefelerz-Schichten in Verbindung mit der Ablagerung metallhaltiger Schlammlagen Ionenwanderungen stattfinden.
  相似文献   

20.
Seven units of carbonaceous shale or sulphide-facies iron-formation have been sampled. They are associated with Proterozoic iron-formations that range in age from ~ 1.9 to ~2.5 Ga: Sokoman and Gunflint (Canada), Riverton (United States), Penge (South Africa) and Brockman (Australia). Sulphur isotope ratios have been determined on the sulphides removed from these shales by both physical and chemical means.The mean δ34S composition of the seven units varies between ?4.9%. and +6.6%. and the sample variance is low within each unit. These distributions are more characteristic of hydrothermal sulphide than sulphide produced by biogenic reduction. This hydrothermal sulphide is believed to have originated from high temperature reduction of seawater sulphate and from magmatic sulphide. A model is suggested whereby this sulphide was exhaled into stratified anoxic/oxic basins. The sulphide and associated base metals were deposited in the reduced sediments beneath the anoxic waters, while some iron and manganese was deposited on oxygenated shelves.The data support, but do not prove, a hydrothermal exhalative origin for lower Proterozoic iron-formation.  相似文献   

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