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1.
Tidal inundation is a new technique for remediating coastal acid sulfate soils (CASS). Here, we examine the effects of this technique on the geochemical zonation and cycling of Fe across a tidally inundated CASS toposequence, by investigating toposequence hydrology, in situ porewater geochemistry, solid-phase Fe fractions and Fe mineralogy. Interactions between topography and tides exerted a fundamental hydrological control on the geochemical zonation, redistribution and subsequent mineralogical transformations of Fe within the landscape. Reductive dissolution of Fe(III) minerals, including jarosite (KFe3(SO4)2(OH)6), resulted in elevated concentrations of porewater Fe2+ (> 30 mmol L?1) in former sulfuric horizons in the upper-intertidal zone. Tidal forcing generated oscillating hydraulic gradients, driving upward advection of this Fe2+-enriched porewater along the intertidal slope. Subsequent oxidation of Fe2+ led to substantial accumulation of reactive Fe(III) fractions (up to 8000 μmol g?1) in redox-interfacial, tidal zone sediments. These Fe(III)-precipitates were poorly crystalline and displayed a distinct mineralisation sequence related to tidal zonation. Schwertmannite (Fe8O8(OH)6SO4) was the dominant Fe mineral phase in the upper-intertidal zone at mainly low pH (3–4). This was followed by increasing lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) at circumneutral pH within lower-intertidal and subtidal zones. Relationships were evident between Fe fractions and topography. There was increasing precipitation of Fe-sulfide minerals and non-sulfidic solid-phase Fe(II) in the lower intertidal and subtidal zones. Precipitation of Fe-sulfide minerals was spatially co-incident with decreases in porewater Fe2+. A conceptual model is presented to explain the observed landscape-scale patterns of Fe mineralisation and hydro-geochemical zonation. This study provides valuable insights into the hydro-geochemical processes caused by saline tidal inundation of low lying CASS landscapes, regardless of whether inundation is an intentional strategy or due to sea-level rise.  相似文献   

2.
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   

3.
For energetic reasons, iron reduction suppresses methanogenesis in tidal freshwater wetlands; however, when iron reduction is limited by iron oxide availability, methanogenesis dominates anaerobic carbon mineralization. Plants can mediate this microbial competition by releasing oxygen into the rhizosphere and supplying oxidized iron for iron reducers. We utilized a plant removal experiment in two wetland sites to test the hypothesis that, in the absence of plants, rates of iron reduction would be diminished, allowing methanogenesis to dominate anaerobic metabolism. In both sites, methanogenesis was the primary anaerobic mineralization pathway, with iron reduction dominating only early and late in the growing season in the site with a less organic soil. These patterns were not influenced by the presence of plants, demonstrating that plants were not a key control of microbial metabolism. Instead, we suggest that site conditions, including soil chemistry, and temperature are important controls of the pathways of anaerobic metabolism.  相似文献   

4.
Sediment and pore water samples have been collected from the coastal tidal flat in the Shuangtaizi estuary, China, in order to investigate the geochemical behavior of iron, cadmium, and lead during diagenesis and to assess the degree of contamination. The calculated enrichment factors and geoaccumulation indices for separate elements show that anthropogenic activities have had no significant influence on the distribution of Fe and Pb in the study area, whereas the distribution of Cd has been closely influenced in this way. The high percentage of exchangeable Cd (average of 56.34%) suggests that Cd represents a potential hazard to benthic organisms in the estuary. The calculated diffusive fluxes of metals show that the most mobilized metal is Fe (9.22 mg m?2 a?1), followed by Cd (0.54 mg m?2 a?1) and Pb (0.42 mg m?2 a?1). Low Fe2+ contents in surface pore water, alongside high chromium-reducible sulfur contents, and low acid-volatile sulfur, and elemental sulfur contents at 0–25 cm depth in sediments show that Fe2+ is formed by the reduction of Fe oxides and is transformed first to a solid phase of iron monosulfides (FeS) and eventually to pyrite (FeS2). The release of adsorbed Pb due to reductive dissolution of Fe/Mn oxides during early diagenesis could be a source of Pb2+ in pore water. From the relatively low total organic carbon contents measured in sediments (0.46–1.28%, with an average of 0.94%) and the vertical variation of Cd2+ in pore water, sulfide or Fe/Mn oxides (instead of organic matter) are presumed to exert a significant influence on carrying or releasing Cd by the sediments.  相似文献   

5.
Syngenetic iron sulfides in sediments are formed from dissolved sulfide resulting from sulfate reduction and catabolism of organic matter by anaerobic bacteria. It has been shown that in recent marine sediments deposited below oxygenated waters there is a constant relationship between reduced sulfur and organic carbon which is generally independent of the environment of deposition. Reexamination of data from recent sediments from euxinic marine environments (e.g., the Black Sea) also shows a linear relationship between carbon and sulfur, but the slope is variable and the line intercepts the S axis at a value between 1 and 2 percent S. It is proposed that the positive S intercept is due to watercolumn microbial reduction of sulfate using metabolizable small organic molecules and the sulfide formed is precipitated and accumulates at the sediment-water interface. The variation in slope and intercept of the C to S plots for several cores and for different stratigraphic zones for the Black Sea can be interpreted in relation to thickness of the aqueous sulfide layer or thinness of the oxygen containing layer and to deposition rate, but also may be influenced by availability of iron, and perhaps the type of organic matter (Leventhal, 1979).  相似文献   

6.
We used a combination of porewater and solid phase analysis, as well as a series of sediment incubations, to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark). In the deep portion of the basin, surface Mn enrichments reached 3.5 wt%, and Mn reduction was the only important anaerobic carbon oxidation process in the upper 10 cm of the sediment. In the less Mn-rich sediments from intermediate depths in the basin, Fe reduction ranged from somewhat less, to far more important than sulfate reduction. Most of the Mn reduction in these sediments may have been coupled to the oxidation of acid volatile sulfides (AVS), rather than to dissimilatory reduction. High rates of metal oxide reduction at all sites were driven by active recycling of both Fe and Mn, encouraged by bioturbation. Recycling was so rapid that the residence time of Fe and Mn oxides, with respect to reduction, ranged from 70-250 days. These results require that, on average, an atom of Fe or Mn is oxidized and reduced between 100-300 times before ultimate burial into the sediment. We observed that dissolved Mn2+ was completely removed onto fully oxidized Mn oxides until the oxidation level of the oxides was reduced to about 3.8, presumably reflecting the saturation by Mn2+ of highly reactive surface adsorption sites. Fully oxidized Mn oxides in sediments, then, may act as a cap preventing Mn2+ escape. We speculate that in shallow sediments of the Skagerrak, surface Mn oxides are present in a somewhat reduced oxidation level (< 3.8) allowing Mn2+ to escape, and perhaps providing the Mn2+ which enriches sediments of the deep basin.  相似文献   

7.
The distribution and partitioning of dissolved andparticulate arsenic and phosphorus in the water columnand sediments of the Saguenay Fjord in Quebec, Canada,are compared. In addition, selective and/or sequentialextractions were carried out on the suspendedparticulate matter (SPM) and solid sediments tocontrast their geochemical behaviors in this naturalaquatic system.Results of our analyses show that both arsenic andsoluble reactive phosphate are actively scavenged fromthe water column by settling particles. Upon theiraccumulation at the sediment-water interface some Asand P may be released to porewaters following thedegradation of organic matter to which they areassociated. The porewater concentrations are, however,limited by their strong affinity for authigenic,amorphous iron oxyhydroxides which accumulate in theoxic sediments near the sediment-water interface.The geochemical behavior of arsenic and phosphorusdiverge most strikingly upon the development of anoxicconditions in the sediments. Following their burial inthe anoxic zone, amorphous iron oxyhydroxides arereduced and dissolved, releasing phosphate and arsenicto the porewaters. We observed, however, thatporewater arsenic concentrations increase at shallowerdepths than phosphate in the sediments. The reductionof arsenate, As(V), to arsenite, As(III), and itsdesorption prior to the reductive dissolution of thecarrier phase(s) may explain this observation.Driven by the strong concentration gradientestablished in the suboxic zone, phosphate diffuses uptowards the oxic layer where it is readsorbed byauthigenic iron oxyhydroxides. In the organic-rich andrapidly accumulating sediments at the head of theFjord, porewater sulfate depletion and the resultingabsence of a sulfide sink for Fe(II), may lead to theformation of vivianite in the fermentation zone, apotential sink for phosphate. Arsenite released to theporewaters in the suboxic and anoxic zones of thesediments diffuses either down, where it is adsorbedto or incorporated with authigenic iron sulfides, orup towards the oxic boundary. Arsenite appears tomigrate well into the oxic zone where it may beoxidized by authigenic manganese oxides before beingadsorbed by iron oxyhydroxides present at the samedepth. Whereas, in the absence of authigenic carbonatefluorapatite precipitation, the ability of oxicsediments to retain mineralized phosphate is afunction of their amorphous iron oxyhydroxide content,arsenic retention may depend on the availability ofmanganese oxides, the thickness of the oxic layer and,its co-precipitation with iron sulfides at depth.  相似文献   

8.
T. Praharaj  D. Fortin   《Applied Geochemistry》2008,23(12):3728-3740
Several studies have shown that SO4-reducing bacteria (SRB) are active in acidic sulfide-rich mine tailings and sediments impacted by mining activities. SRB activity in acidic tailings has been shown to vary with seasons as a result of fluctuating in situ physico-chemical conditions. Iron-reducing bacteria (FeRB) also play an important role in Fe cycling in sediments impacted by mining activities, but their activity in mine tailings is poorly understood, despite the fact that geochemical evidence indicates that they might be active. The present study was undertaken to assess the seasonal changes in SRB and FeRB abundance and activity in alkaline Pb–Zn mine tailings (Calumet tailings) located near Ottawa, ON, Canada. Results showed that FeRB and SRB populations were present throughout the year at two different sampling sites at the Calumet tailings, but SO4 reduction rates (SRR) were lower in the spring than in the summer, indicating that SRB activity was affected by organic C availability and/or temperature. Surface agricultural runoff at one site provided ample nutrients and organic C to the tailings, but SRB activity remained lower than the site not impacted by nutrient runoff, suggesting that the type of organic C was different between the two sites and that less labile organic substrates were available to SRB in the organic-rich site. High SRB activity in the site containing low organic C inhibited the abundance of FeRB, and possibly their activity, as a result of abiotic reduction of Fe(III)-rich minerals by biogenic sulfides, which lowered the pool of final electron acceptors. The abiotic reduction pathway was consistent with the porewater data which showed that sulfide was consumed and SO4 produced, along with Fe(II). These results show a strong interdependence between SRB and FeRB activity, as observed in other environments, such as saltmarsh sediments. Low temperature did not appear to hinder FeRB abundance in alkaline tailings. Finally, despite evidence that SRB populations were active at both sites, the |S isotopic composition of the AVS and CRS fractions were not representative of biogenic sulfides, indicating that the overall S-isotope signature of mine tailings is more representative of abiotic sulfides originating from the ore body.  相似文献   

9.
《Applied Geochemistry》2003,18(1):25-36
The controls on the internal neutralization of low productivity, highly acidified waters by sulfide accumulation in sediments are yet poorly understood. It is demonstrated that the neutralization process is constrained by organic matter quality and thermodynamic effects which control the relative rates of SO4 and Fe reduction, and the fate of the reduced Fe and S in the sediments. The investigated sediments were rich in dissolved Fe(II) (0.005–12 mmol l−1) and SO4 (1.3–22 mmol l−1). The pH ranged from 3.0 to 6.8. Contents of reduced inorganic S (0.1–9.5%), molar C/N ratios of the organic matter (12–80) and metabolic turnover rates (1–110 μeq cm−3 a−1) varied strongly. Substantial amounts of Fe sulfides were only found at a simultaneous partial thermodynamic and solubility equilibrium of the involved biogeochemical processes. Sulfide oxidation was apparently inhibited, and SO4 and Fe reduction coexisted. In this type of sediment increases in C availability cause enhanced neutralization rates. In the absence of a partial equilibrium, the sediments were in a sulfide oxidizing and Fe reducing state, and did not accumulate Fe sulfides. The latter type of sediment will increase neutralization rates in response to decreasing deposition of reactive Fe oxides but not necessarily in response to increases in lake productivity by e.g. fertilization measures.  相似文献   

10.
Microbial processes within the ocean crust are of potential importance in controlling rates of chemical reactions and thereby affecting chemical exchange between the oceans and lithosphere. We here assess the oxidation state of altered ocean crust and estimate the magnitude of microbial biomass production that might be supported by oxidative and nonoxidative alteration. Compilations of Fe2O3, FeO, and S concentrations from DSDP/ODP drill core samples representing upper basaltic ocean crust suggest that Fe3+/ΣFe increases from 0.15 ± 0.05 to 0.45 ± 0.15 within the first 10-20 Myr of crustal evolution. Within the same time frame 70 ± 25% of primary sulfides in basalt are oxidized. With an annual production of 4.0 ± 1.8 × 1015 g of upper (500 ± 200 m) crust and average initial concentrations of 8.0 ± 1.3 wt% Fe and 0.125 ± 0.020 wt% S, we estimate annual oxidation rates of 1.7 ± 1.2 × 1012 mol Fe and 1.1 ± 0.7 × 1011 mol S. We estimate that 50% of Fe oxidation may be attributed to hydrolysis, producing 4.5 ± 3.0 × 1011 mol H2/yr.Thermodynamic and bioenergetic calculations were used to estimate the potential chemolithoautotrophic microbial biomass production within ridge flanks. Combined, aerobic and anaerobic Fe and S oxidation may support production of up to 48 ± 21 × 1010 g cellular carbon (C). Hydrogen-consuming reactions may support production of a similar or larger microbial biomass if iron reduction, nitrate reduction, or hydrogen oxidation by O2(aq) are the prevailing metabolic reactions. If autotrophic sulfate reduction or methanogenesis prevail, the potential biomass production is 9 ± 7 × 1010 g C/yr and 3 ± 2 × 1010 g C/yr, respectively. Combined primary biomass production of up to ∼1 × 1012 g C/yr may be similar to that fueled by anaerobic oxidation of organic matter in deep-seated heterotrophic systems. These estimates suggest that water-rock reactions may support significant microbial life within ridge flank hydrothermal systems, These estimates suggest that water-rock reactions may support significant microbial life within ridge flank hydrothermal systems.  相似文献   

11.
Roof successions above two coal seams from the Mansfield Formation (Lower Pennsylvanian) in the Indiana portion of the Illinois Basin have been studied with regard to sedimentary structures, organic petrology and organic geochemistry. The succession above the Blue Creek Member of the Mansfield Formation is typical of the lithologies covering low-sulphur coals (< 1%) in the area studied, whereas the succession above the unnamed Mansfield coal is typical of high-sulphur coals (>2.%). The transgressive-regressive packages above both seams reflect the periodic inundation of coastal mires by tidal flats and creeks as inferred from bioturbation and sedimentary structures such as tidal rhythmites and clay-draped ripple bedforms. Geochemistry and petrology of organic facies above the Blue Creek coal suggest that tidal flats formed inland in fresh-water environments. These overlying fresh water sediments prevented saline waters from invading the peat, contributing to low-sulphur content in the coal. Above the unnamed coal, trace fossils and geochemical and petrological characteristics of organic facies suggest more unrestricted seaward depositional environment. The absence of saline or typically marine biomarkers above this coal is interpreted as evidence of very short periods of marine transgression, as there was not enough time for establishment of the precursor organisms for marine biomarkers. However, sufficient time passed to raise SO42− concentration in pore waters, resulting in the formation of authigenic pyrite and sulphur incorparation into organic matter.  相似文献   

12.
沉积过程对自生黄铁矿硫同位素的约束   总被引：6，自引：3，他引：3  
自生黄铁矿是海洋沉积物中还原态硫的主要赋存形式,其形成过程与有机质矿化相关,影响全球的C-S-Fe生物地球化学循环。自生黄铁矿硫同位素分馏主要受微生物硫酸盐还原的控制,但近期的研究成果表明局部沉积环境的改变也可以影响黄铁矿硫同位素的组成,特别是在浅海环境。在浅海非稳态沉积环境内,物理再改造和生物扰动作用,导致硫酸盐还原带内生成的硫化物被再氧化,进而影响黄铁矿的硫同位素值。浅海沉积过程容易受到古气候和海平面变化的影响,引起沉积速率的剧烈波动,导致有机质和活性铁输入的不稳定,进而影响成岩系统的开放性和硫酸盐还原速率,最终影响黄铁矿的硫同位素值。另外,沉积速率的改变还影响硫酸盐—甲烷转换带的迁移,造成有机质和甲烷厌氧氧化硫酸盐还原的相互转化,产生不同的硫同位素信号。东海内陆架泥质区为研究沉积过程对自生黄铁矿的形成及其硫同位素组成的约束机制提供了很好的研究材料。该区域有很好的沉积学研究基础,自生黄铁矿丰富、并且个别层位有生物气（甲烷为主）存在,是研究边缘海C-S-Fe循环的理想场所。  相似文献   

13.
The pore waters of sediments from a salt marsh along the Delaware estuary have been analyzed for sulfur species and associated trace metals. Since the sediment interface is usually in contact with the atmosphere, the sulfur species are dependent on the production of hydrogen sulfide by sulfate reduction and subsequent oxidation by diffusing oxygen. The most important species observed are hydrogen sulfide, polysulfide ions and thiosulfate. Secondary reactions of hydrogen sulfide and polysulfides with decomposing organic matter yield significant concentrations of both thiols and organic polysulfides. Upon isolation of the sediment from the atmosphere due to tidal inundation, bacterial sulfate reduction becomes the dominant process. This results in the reduction of the polysulfides in agreement with thermodynamic predictions, and suggests that the redox couple sulfide/polysulfide is a good redox indicator under such reducing environments.The concentrations of trace elements Cu and Fe in the pore waters are mainly controlled by sulfide formation. Calculations show that copper is strongly complexed probably with organo-sulfur ligands. Iron might be complexed as such sulfur species to a much lesser extent than copper.  相似文献   

14.
以长江口崇明岛北支潮滩的3个潮滩为对象,在粒度测量和磁性分析的基础上,揭示了现代潮滩表层沉积物的磁性变化,探讨了磁性矿物、尤其是自生亚铁磁性矿物—硫复铁矿（Fe3S4）在潮滩沉积微相的分布规律及机制。研究结果表明：长江口潮滩表层沉积物的磁性特征由亚铁磁性矿物及超顺磁颗粒(SP)主导。淤积型中高潮滩磁铁矿以单畴(SD)和SP为主,侵蚀型潮滩的中低潮滩则更多假单畴/多畴(PSD/MD)晶粒,反映了水动力的分选及以细颗粒矿物溶解为主的早期成岩作用。此外,最东侧的北四滧港剖面潮上带—高潮滩芦苇带普遍存在自生亚铁磁性硫复铁矿,北堡港和新卫剖面的高潮滩也局部存在硫复铁矿,反映了本区高潮滩—潮上带丰富的有机质及细颗粒沉积物、加上有限的海水淹没时间,是早期成岩作用过程中生成硫复铁矿的主要机制。  相似文献   

15.
苏北潮滩湿地不同生态带碳、氮、磷分布特征*   总被引：1，自引：0，他引：1  
通过对比苏北潮滩湿地不同生态带的表层以及柱状沉积物中总有机碳、总氮、总磷和有机磷含量,并结合不同植被不同植株部位中碳、氮、磷的含量变化,分析了潮滩沉积物中碳、氮、磷的垂向和水平分布特征与规律,探讨了不同生态带以及潮滩植被对碳、氮、磷等生源要素的富集作用。对比分析结果表明:苏北潮滩湿地各生态带对不同的测量指标有着不同的富集作用,互花米草滩的总有机碳、总氮和有机磷含量要远大于其他几个生态带,光滩沉积物中总磷的含量最高; 粒度效应是控制互花米草前缘地带以及互花米草滩沉积物中有机碳和氮分布的一个重要因素,盐蒿和芦苇滩中有机碳和氮的分布更多的是受粒度之外的其他因素影响; 不同生态带表层沉积物中的C/N比值分布,大致可反映其有机物来源的差异,而不同生态带中柱状沉积物中的C/N比值相对接近,很难根据C/N比值大小来对不同生态带中的有机物来源进行判断,这可能是埋藏在柱状沉积物中的有机物更多的受到了早期成岩作用造成的。植被对潮滩湿地中碳、氮、磷的分布有着重要影响,3种物质在互花米草、盐蒿和芦苇中的含量差别不是很大,因此潮滩植被对沉积物中上述3种物质的贡献差别主要是由不同植被的生物量和其所处环境的沉积动力差异造成的。  相似文献   

16.
The vertical distributions of dissolved Se species [Se(IV), Se(VI) and organic Se] and diagenetic constituents [Fe(II) and Mn(II)] were obtained in porewater samples of two Sudbury area lakes (Clearwater and McFarlane). The sedimentary concentration profiles of total Se, Se species bound to Fe–Mn oxyhydroxides and to organic matter, and of elemental Se were also determined along with the concentrations of Fe, Mn and S in different extractable fractions. Results indicated that the concentrations of total dissolved Se in porewater samples were very low, varying from around 2.0 nM to a maximum level of 6.5 nM, while the concentrations of total Se species in the solid phase varied between 2 and 150 nmol/g on a dry weight basis. The two lakes showed striking differences in the presence of Se(IV) and Se(VI) at the sediment–water interface (SWI). In Clearwater Lake, Se(VI) was present at this interface and Se(IV) was not detectable, whereas the opposite was found in McFarlane Lake. This suggests that reducing conditions might have existed near the SWI of McFarlane Lake at the sampling time; this hypothesis was confirmed by several other measured chemical parameters. The profiles of total dissolved Se of both lakes suggest upward and downward diffusion of dissolved Se species along the concentration gradients. Assuming that no precipitation occurred at the SWI, the fluxes of dissolved Se species across the SWI in Clearwater and McFarlane lakes were estimated to be 0.108 and 0.034 nmol cm−2 a−1, respectively. These values do not include the possible losses of volatile Se species due to microbial methylation. In the reducing sediments of both lakes, the formation of elemental Se and pyritic Se were found to be important mechanisms for controlling the solubility of Se in this environment. The main geochemical processes involving Se identified in this study are: the adsorption of Se onto Fe–Mn oxyhydroxides at or near the SWI, the release of adsorbed Se by the reduction of the same oxyhydroxides and the mineralization of organic matter, and the removal of Se from porewaters to form elemental Se and a S mineral phase such as Se–pyrite or pure ferroselite.  相似文献   

17.
The paper presents the results of study of ferromanganese carbonate rocks in the Sob area (Polar Urals), which is located between the Rai-Iz massif and the Seida–Labytnangi Railway branch. These rocks represent low-metamorphosed sedimentary rocks confined to the Devonian carbonaceous siliceous and clayey–siliceous shales. In terms of ratio of the major minerals, ferromanganese rocks can be divided into three varieties composed of the following minerals: (1) siderite, rhodochrosite, chamosite, quartz, ± kutnahorite, ± calcite, ± magnetite, ± pyrite, ± clinochlore, ± stilpnomelane; (2) spessartite, rhodochrosite, and quartz, ± hematite, ± chamosite; (3) rhodochrosite, spessartite, pyroxmanite, quartz ± tephroite, ± fridelite, ± clinochlore, ± pyrophanite, ± pyrite. In all varieties, the major concentrators of Mn and Fe are carbonates (rhodochrosite, siderite, kutnahorite, Mn-calcite) and chlorite group minerals (clinochlore, chamosite). The chemical composition of rocks is dominated by Si, Fe, Mn, carbon dioxide, and water (L.O.I.): total SiO2 + Fe2O 3 tot + MnO + L.O.I. = 85.6?98.4 wt %. The content of Fe and Mn varies from 9.3 to 55.6 wt % (Fe2O 3 tot + MnO). The Mn/Fe ratio varies from 0.2 to 55.3. In terms of the aluminum module AlM = Al/(Al + Mn + Fe), the major portion of studied samples corresponds to metalliferous sediments. The δ13Ccarb range (–30.4 to–11.9‰ PDB) corresponds to authigenic carbonates formed with carbon dioxide released during the microbial oxidation of organic matter in sediments at the dia- and/or catagenetic stage. Ferromanganese sediments were likely deposited in relatively closed seafloor zones (basin-traps) characterized by periodic stagnation. Fe and Mn could be delivered from various sources: input by diverse hydrothermal solutions, silt waters in the course of diagenesis, river discharges, and others. The diagenetic delivery of metals seems to be most plausible. Mn was concentrated during the stagnation of bottom water in basin-traps. Interruption of stagnation promoted the precipitation of Mn. The presence of organic matter fostered a reductive pattern of postsedimentary transformations of metalliferous sediments. Fe and Mn were accumulated initially in the oxide form. During the diagenesis, manganese and iron oxides reacted with organic matter to make up carbonates. Relative to manganese carbonates, iron carbonates were formed under more reductive settings and higher concentrations of carbon dioxide in the interstitial solution. Crystallization of manganese and iron silicates began already at early stages of lithogenesis and ended during the regional metamorphism of metalliferous sediments.  相似文献   

18.
Analysis of 3-m sediment cores revealed that profiles of carbon (C), sulfur (S), and iron (Fe) varied with relative distance from marine and terrestrial sediment sources in Tomales Bay California. Despite relatively high sedimentation rates throughout the bay (historically 3–30 mm yr−1), sulfate reduction of deposited organic matter led to free-sulfide accumulation in sediments only at the location farthest from terrestrial runoff, the source of reactive iron. Acid-volatile sulfide concentrations in all sediments (<10 μmol g−1) were low relative to concentrations of chromiumreducible sulfide (up to 400 μmol g−1 farthest from the reactive iron source). A calculated index of iron availability, used to describe sediment resistance to build-up of free sulfide, was lowest at this location. Recent, upward shifts in reactive Fe concentration and in the relative contribution of terrestrial orgnic carbon (measured as a shift in δ13C of bulk sediment organic matter) in all cores indicated that erosion and transport of sediments from the watershed surrounding Tomales Bay increased after European settlement in the 1850s.  相似文献   

19.
Five temperate seagrasses (Amphibolis antartica, Halophila ovalis, Posidonia australis, Posidonia sinuosa and Zostera nigricaulis) were surveyed along the south-west coast of Western Australia. These morphological different seagrasses grow in contrasting sediments with large variations in sedimentary organic matter, carbonate and iron contents. We tested if sulfur composition in the plants responded to sulfur dynamics in the sediments and if plant morphology affected the sulfur composition of the plants. The sediments were characterized by low sulfate reduction rates (<9 mmol m?2day?1), low concentrations of dissolved sulfides in the pore waters (<74 μM) and low burial of sulfides (total reducible sulfur <0.8 mol m?2) in the sediments. However, all seagrasses showed high intrusion in the below-ground parts with up to 84 % of the sulfur derived from sedimentary sulfides. There were no direct links between sulfur in the plants and sulfur dynamics in the sediments, probably due to low iron contents in the sediments limiting the buffering capacity of the sediments and exposing the plants to sulfides despite low rates of production and low pools of sulfides. The intrusion was linked between plant compartments (roots, rhizomes and leaves) for the two small species (H. ovalis and Z. nigricaulis), whereas the intrusion into the leaves was limited for the larger species (P. australis and P. sinuosa) and for A. antarctica, where extensive rhizomes and roots and the long stem for A. antarctica separate the leaves from the sediment compartment. Elevated intrusion was observed at two study locations, where natural deposition of organic matter or nutrient enrichment may be contributing factors to enhanced sulfide pressure.  相似文献   

20.
Our modeling objective was to better define the relationship between subtropical seagrass and potential water column and sediment stressors (light, organic and particle sedimentation, sediment nutrients, and the porewater sulfide system). The model was developed and optimized for sediments inThalassia testudinum seagrass beds of Lower Laguna Madre, Texas, U.S., and is composed of a plant submodel and a sediment diagenetic submodel. Simulations were developed for a natural stressor (harmful algal bloom,Aureoumbra lagunensis) and an anthropogenic, stressor (dredging event). The observed harmful algal bloom (HAB) was of limited duration and the simulations of that bloom showed no effect of the algal bloom on biomass trends but did suggest that sediment sulfides could inhibit growth if the bloom duration and intensity were greater. To examine this hypothesis we ran a simulation using data collected during a sustained 4-yr bloom in Upper Laguna Madre. Simulations suggested that light attenuation by the HAB could cause a small reduction inT. testudinum biomass, while input of organic matter from the bloom could promote development of a sediment geochemical environment toxic toT. testudinum leading to a major reduction in biomass. A 3-wk dredging event resulted in sedimentation of a layer of rich organic material and reduction of canopy light for a period of months. The simulations suggested that the seagrass could have recovered from the effects of temporary light reduction but residual effects of high sulfides in the sediments would make the region inhospitable for seagrasses for up to 2.5 yr. These modeling exercises illustrate that both natural and anthropogenic stressors can result in seagrass losses by radically altering the sedimentary geochemical environment.  相似文献   

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