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1.
Sediments in the caldera of Santorini are receiving a hydrothermal input of iron and manganese from presently active hydrothermal vents off the Kameni Islands, and are enriched in these elements in their surface layer. However, greater Fe-Mn enrichments occur in discrete layers at depth in the cores separated from the surface by Fe-Mn poor sediments, suggesting that a past hydrothermal event may have been more intense than the present one. The buried Fe-Mn enriched layers occur above a turbidite thought to have resulted from sediment slumping due to a major volcanic eruption and earthquake in 1650, and are thought to have formed consequent on the activation of faults related to the magma chamber by the eruption facilitating seawater-rock interaction processes and the formation of metal-rich hydrothermal solutions.  相似文献   

2.
The distribution of iron in a 6-m core of post-glacial sediment from an oligotrophic lake (Connistonwater, England) was determined, principally by Mossbauer spectroscopy on dried samples. The immediate post-glacial deposits contain 4.8 wt. % of iron, with a Fe2+; Fe3+ ratio ～- 4. The iron there is predominantly in the form of chlorite, but there are small amounts in hematite and illite. The distribution of iron is different, and very variable in the recent sediments (~ < 13,000 BP), which contain 25–35 per cent organic matter and 5.2 wt. % of iron relative to the inorganic fraction. Typically half the iron is present there as chlorite, and the rest is ferric, mostly in the form of an amorphous gel which is also present in undried samples. To explain the observed ferrous:ferric profile, it is proposed that the latter includes iron which was once mobile, having been leached from the Fe2+-bearing clays under reducing conditions in the soils of the drainage basin, or in the sediment itself. It was subsequently precipitated as ferric hydroxide on contact with the oxic lake water. In contrast, the ferrous iron in the sediments is immobile iron, which remained locked in the chlorite phase of the clay particles as they were carried from soil to sediment intact.All the sediments are rather inhomogeneous. Chlorite, and especially hematite, are mechanically concentrated in pink varves in the immediate post-glacial deposits. In the partly inorganic sediments, the concentration of ferrous iron (chlorite) is approximately uniform, but the ferric content may differ by a factor of five between regions only a few millimeters apart.  相似文献   

3.
A survey of hot, acid springs in Yellowstone Park has shown that high concentrations of ferrous and ferric iron are often present. Total ionic iron concentrations in different springs ranged from less than 1 ppm to greater than 200 ppm, and up to 50% of the ionic iron was in the ferrous form. Some of these springs also have high concentrations of reduced sulfur species (S2? and S0). Significant populations of the bacterium Sulfolobus, acidocaldarius, an autotrophic organism able to live and oxidize sulfur compounds at low pH and high temperature, were present in most of these springs. The role of this organism in the oxidation of ferrous iron was investigated by incubating natural samples of water and assaying for disappearance of ferrous iron. Controls in which bacterial activity was inhibited by addition of 10% NaCl were also run. Bacterial oxidation of ferrous iron occurred in most but not all of the spring waters. The temperature optimum for oxidation varied from spring to spring, but significant oxidation occurred at temperatures of 80–85°C, but not at 90°C. Thus, 85–90°C is the upper temperature at which bacterial iron oxidation occurs; a similar upper limit has previously been reported for sulfur oxidation in the same kinds of springs. The steady-state concentrations of ferrous and ferric iron are determined by the rate at which these ions move into the spring pools with the ground water (flow rate), by the rate at which ferric iron is reduced to the ferrous state by sulfide, and by the rate of bacterial oxidation. The bacterial oxidation rate is faster than the flow rate, so that the rate of reduction of ferric iron is probably the rate-controlling reaction. In several springs, no decrease in ferrous iron occurred, even though high bacterial populations were present. It was shown that in these springs, ferrous iron oxidation occurred but the ferric iron formed was reduced back to the ferrous state again. These springs were all high in suspended sediment and the reductant was shown to be present in the sediment. X-ray diffraction revealed that the sediment contained three major ingredients, elemental sulfur, natroalunite, and quartz. Chemical analyses showed a small amount of sulfide, too little to reduce the ferric iron. Elemental sulfur itself did not reduce ferric iron but when elemental sulfur was removed from the sediment by CS2 extraction, the activity of the sediment was abolished. It is hypothesized that the sulfide present in the sediment (possibly bound to natroalunite) reacts with elemental sulfur to form a reductant for ferric iron. The results show that bacteria can have a profound influence on the ferrous/ferric ratios of geothermal systems, but that temperature and mineral composition of the water may significantly influence the overall result.  相似文献   

4.
姜福芝 《矿床地质》1983,2(4):11-18
建国以来,我国在火山矿床的地质勘探和研究工作方面都积累了丰富的资料,并且有不少关于矿床成因和类型划分方面的叙述。作者近几年来有机会接触到一些这方面的工作。这里试将海底火山活动的重要产物之一——海相火山铁铜矿床作一个比较系统的成因类型的划分。限于水平,不当之处请批评指正。  相似文献   

5.
东昆仑卡特里西铜锌矿成因   总被引：2，自引：0，他引：2  
卡特里西铜锌多金属矿是新疆东昆仑地区首次发现的海相火山沉积型硫化物矿床,该矿产于下石炭统托库孜达坂群内的火山岩地层中,矿体分布明显受地层控制,含矿岩性为一套双峰式火山岩上部的灰绿色基性凝灰岩,一般呈平行层状、似层状、透镜状夹于灰岩中及灰岩与含炭粉砂岩的接触处。该矿海相火山沉积特征明显,为在相对封闭的浅海盆地内,火山活动形成的成矿物质在火山机构边部洼地内堆集形成。东昆仑下石炭统托库孜达坂群地层中海相火山岩带分布有众多铜多金属矿点,为一较有前景的海相火山岩型铜矿成矿带,卡特里西铜锌矿找矿及成因认识上的突破不但填补了东昆仑一带该矿床类型的空白,而且对在该区广泛分布的托库孜达坂群内火山岩系地层中寻找该类矿床具有重大指导意义。  相似文献   

6.
Deposits of Fe-Si-Mn oxyhydroxides are commonly found on the seafloor on seamounts and mid-ocean spreading centers. At Franklin Seamount located near the western extremity of Woodlark Basin, Papua New Guinea, Fe-Si-Mn oxyhydroxides are being precipitated as chimneys and mounds upon a substrate of mafic lava. Previous studies have shown that the vent fluids have a low temperature (20–30°C) and are characterized by a total dissolved iron concentration of 0.038 mM kg-1, neutral pH (6.26) and no measurable H2S. The chimneys have a yellowish appearance with mottled red–orange patches when observed in situ from a submersible, but collected samples become redder within a few hours of being removed from the sea. The amorphous iron oxyhydroxides, obtained from active and inactive vents, commonly possess filamentous textures similar in appearance to sheaths and stalks excreted by the iron-oxidizing bacteria Leptothrix and Gallionella; however, formless agglomerates are also common. Textural relationships between apparent bacterial and non-bacterial iron suggest that the filaments are coeval with and/or growing outwards from the agglomerates. The amorphous iron oxyhydroxides are suggested to precipitate hydrothermally as ferrosic hydroxide, a mixed-valence (Fe2+-Fe3+) green–yellow iron hydroxide compound. Consideration of the thermodynamics and kinetics of iron in the vent fluid, suggest that the precipitation is largely pH controlled and that large amounts of amorphous iron oxyhydroxides are capable of being precipitated by a combination of abiotic hydrothermal processes. Some biologically induced precipitation of primary ferric oxyhydroxides (two-XRD-line ferrihydrite) may have occurred directly from the fluid, but most of the filamentous iron micro-textures in the samples appear to have a diagenetic origin. They may have formed as a result of the interaction between the iron-oxidizing bacteria and the initially precipitated ferrosic hydroxide that provided a source of ferrous iron needed for their growth. The processes described at Franklin Seamount provide insight into the formation of other seafloor oxyhydroxide deposits and ancient oxide-facies iron formation.  相似文献   

7.
The purpose of this study was to examine structural alterations of finely ground phlogopite, a trioctahedral mica, when exposed to acid, iron- and sulfate-rich solutions typical of bioleaching systems. Phlogopite suspensions were supplemented with ferrous sulfate and incubated with iron- and sulfur-oxidizing bacteria (Acidithiobacillus ferrooxidans) at 22 °C. As bacteria oxidized ferrous iron, ferric iron thus formed partially precipitated as K-jarosite. K-jarosite precipitation was contingent on the preceding ferrous iron oxidation by bacteria and the release of interlayer-K from phlogopite. This chemically and microbially induced weathering involved alteration of phlogopite to a mixed layer structure that included expansible vermiculite. The extent of phlogopite weathering and structure expansion varied with duration of the contact, concentration of ferrous iron and phlogopite, and the presence of monovalent cations (NH4+, K+, or Na+) in the culture solution. NH4+ and K+ ions (100 mM) added to culture suspensions precipitated as jarosite and thereby effectively prevented the loss of interlayer-K and structural alteration of phlogopite. Additional Na+ (100 mM) was insufficient to precipitate ferric iron as natrojarosite and therefore the precipitation was coupled with interlayer-K released from phlogopite. When ferrous iron was replaced with elemental sulfur as the substrate for A. ferrooxidans, the weathering of phlogopite was based on chemical dissolution without structural interstratification. The results demonstrate that iron oxidation and the concentration and composition of monovalent ions can have an effect on mineral weathering in leaching systems that involve contact of phlogopite and other mica minerals with acid leach solutions.  相似文献   

8.
It is shown that peat bogs, which accumulate coal- and siderite-bearing sediments, serve as a generator of ferruginous solutions with the significant part of Fe migrating from them in the form of metalloorganic compounds. The stability of organic Fe-bearing complexes provides favorable conditions for the late diagenetic–catagenetic siderite formation in adjacent sea basins. It has been established that the formation of Phanerozoic coals, oil shales, and black shales was nearly coeval with the formation of goethite–chlorite–siderite ores. The paper discusses the influence of volcanic activity on the formation of Precambrian–Phanerozoic iron ore deposits and emphasizes the significance of siderite formation in the general evolution of the sedimentary iron ore formation.  相似文献   

9.
Accumulation of manganiferous rocks in the history of the Earth’s lithosphere evolution began not later than the end of the Middle Archean. Primary manganese sediments were accumulated at that time in shallow-water sedimentation basins with the active participation of organic matter. The concentration of Mn in the primary sediments usually did not reach economic values. The formation of genuine manganese ores is related to later processes of the transformation of primary ores—diagenesis, catagenesis, metamorphism, and retrograde diagenesis. Types of basins of manganese ore sedimentation and character of processes of the formation of manganese sediments during the Earth’s shell evolution changed appreciably and correlated with the general evolution of paleocontinents. Major periods, epochs, and phases of manganese ore genesis are defined. At the early stages of lithosphere formation (Archean-Proterozoic), manganese was deposited in basins commonly confined to the central part of Western Gondwana and western part of Eastern Gondwana, as well as the western part of the Ur paleocontinent. Basins of manganese ore sedimentation were characterized by the ferruginous-siliceous, carbonaceous-clayey, and carbonaceous-carbonate-clayey composition. The Early-Middle Paleozoic epoch of manganiferous sediment accumulation was characterized by the presence of several small sedimentation basins with active manifestation of volcanic and hydrothermal activity. Since the formation of Pangea in the Late Paleozoic until its breakup, accumulation of Mn was closely associated with processes of diagenesis and active participation of the oxidized organic matter.  相似文献   

10.
国外浅变质碎屑岩型金矿床的含矿岩系以含碳和黄铁矿,夹火山物质和热水沉积物,金含量高为特征.在含矿岩系的沉积、成岩过程中,局部可以形成贫金的含矿层,少数情况下以至于形成金矿体.含矿岩系的变质作用可能形成金矿化,或为后来的成矿作用造成有利的物理和化学环境.岩浆作用为成矿作用提供了部分成矿物质,或为改造成矿作用提供热源和动力.金矿床受构造控制,位于地热正异常区,金矿床的形成与热水沉积成矿作用、变质成矿作用、岩浆期后热液成矿作用和大气降水改造成矿作用等有关.超大型浅变质碎屑岩金矿床的形成过程持续时间长,具有多期多阶段的特点.改造成矿作用在超大型浅变质细碎屑岩型金矿床形成中起重要作用,中生代形成的超大型金矿床中,构造岩浆活化作用叠加十分重要.  相似文献   

11.
Extensive transgression of lake water occurred during the Cretaceous Qingshankou Stage and the Nengjiang Stage in the Songliao basin, forming widespread deep-water deposits. Eleven types of microfacies of deep-water deposits have been recognized in the continuous core rocks from the SKII, including mudstone of still water, marlite, dolostone, oil shale, volcanic ashes, turbidite, slump sediment, tempestite, seismite, ostracoda limestone and sparry carbonate, which are divided into two types: microfacies generated due to gradually changing environments (I) and microfacies generated due to geological events (II). Type I is composed of some special fine grain sediments such as marlite, dolomite stone and oil shale as well as mudstone and Type II is composed of some sediments related to geological events, such as volcanic ashes, turbiditie, slump sediment, tempestite, seismite, ostracoda limestone. The formation of sparry carbonate may be controlled by factors related to both environments and events. Generally, mudstone sediments of still water can be regarded as background sediments, and the rest sediments are all event sediments, which have unique forming models, which may reflect controlling effects of climatics and tectonics.  相似文献   

12.
Mineral concentration and ilmenite characterization of the Thothapally — Kayamkulam Barrier Island of the southern Kerala has been studied. 96.86% concentrations of heavy minerals are recorded in the surficial and core samples (4 m) in the southern Kayamkulam and northern Thothapally areas. The total heavy mineral content decreases with depth. The primary heavy mineral suite of the surficial and core samples consists of ilmenite, sillimanite, zircon, garnets, rutile, monazite and magnetite. Longshore current and onshore-offshore movements of sediment during the southwest monsoon are primarily responsible in sorting of the heavy minerals. TiO2 content in ilmenite is significantly higher in the Kayamkulam core sediments than the surface samples. XRD analysis supports intensive weathering and alteration leading to the higher TiO2 concentration. Higher percentage of ferric iron than ferrous iron in the core samples reveals that considerable weathering occurred under burial condition. SEM examination of ilmenite grains reveal the presence of solution pit, chemical leaching, corrosion and replacement textures, supporting the intense epigenetic alteration and weathering under subaerial condition and post-depositional changes by water-table condition.  相似文献   

13.
钾长石粉酸浸除铁的实验研究   总被引：8，自引：1，他引：8  
郑骥  马鸿文等 《地球科学》2001,26(6):657-660
在利用钾长石粉合成沸石分子筛和制取碳酸钾技术中，铁的存在会降低沸石的白度。对北京平谷、天津蓟县、内蒙白云鄂博三地钾长石粉进行硫酸酸浸除铁实验，获得最大铁浸出率分别为88．6％、93．2％和64．6％，且前两地钾长石粉中铁的浸出行为相似，酸浸除铁效果均优于白云鄂博钾长石粉。采用正交实验法研究硫酸浓度、酸浸温度和时间对除铁效果的影响，表明三者对不同地区钾长石粉酸浸除铁效果的影响程度各不相同。钾长石酸浸除铁反应开始时，铁的溶解极快，反应速率主要由化学反应控制；其后溶解相对缓慢，反应速率则由扩散作用控制。  相似文献   

14.
本区原岩建造是-套基性—酸性火山凝灰岩（主要）+铁硅质岩+沉积岩组合。整个层序反映了一个较完整的火山喷发沉积旋回。含铁建造与沉积旋回在时空和物源上存在着密切的成因联系。铁矿的形成及分布并非受控于某一种岩石,而是受控于火山喷发沉积旋回。本文从岩浆分异、火山活动、沉积作用及构造运动等的发生、发展、演化的角度较全面地分析了火山喷发沉积旋回的控矿作用。  相似文献   

15.
The Mars Global Surveyor, Mars Exploration Rover, and Mars Express missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major recent mission findings are the presence of jarosite (a ferric sulfate salt), which requires formation from an acid-sulfate brine, and the occurrence of hematite and goethite on Mars. Recent ferric iron models have largely focused on 25 °C, which is a major limitation for models exploring the geochemical history of cold bodies such as Mars. Until recently, our work on low-temperature iron-bearing brines involved ferrous but not ferric iron, also obviously a limitation. The objectives of this work were to (1) add ferric iron chemistry to an existing ferrous iron model (FREZCHEM), (2) extend this ferrous/ferric iron geochemical model to lower temperatures (<0 °C), and (3) use the reformulated model to explore ferrous/ferric iron chemistries on Mars.The FREZCHEM model is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Ferric chloride and sulfate mineral parameterizations were based, in part, on experimental data. Ferric oxide/hydroxide mineral parameterizations were based exclusively on Gibbs free energy and enthalpy data. New iron parameterizations added 23 new ferrous/ferric minerals to the model for this Na-K-Mg-Ca-Fe(II)-Fe(III)-H-Cl-SO4-NO3-OH-HCO3-CO3-CO2-O2-CH4-H2O system.The model was used to develop paragenetic sequences for Rio Tinto waters on Earth and a hypothetical Martian brine derived from acid weathering of basaltic minerals. In general, model simulations were in agreement with field evidence on Earth and Mars in predicting precipitation of stable iron minerals such as jarosites, goethite, and hematite. In addition, paragenetic simulations for Mars suggest that other iron minerals such as lepidocrocite, schwertmannite, ferricopiapite, copiapite, and bilinite may also be present on the surface of Mars. Evaporation or freezing of the Martian brine led to similar mineral precipitates. However, in freezing, compared to evaporation, the following key differences were found: (1) magnesium sulfates had higher hydration states; (2) there was greater total aqueous sulfate (SO4T = SO4 + HSO4) removal; and (3) there was a significantly higher aqueous Cl/SO4T ratio in the residual Na-Mg-Cl brine. Given the similarities of model results to observations, alternating dry/wet and freeze/thaw cycles and brine migration could have played major roles in vug formation, Cl stratification, and hematite concretion formation on Mars.  相似文献   

16.
The Proterozoic Soldiers Cap Group, a product of two major magmatic rift phases separated by clastic sediment deposition, hosts mineralised (e.g. Pegmont Broken Hill‐type deposit) and barren iron oxide‐rich units at three main stratigraphic levels. Evaluation of detailed geological and geochemical features was carried out for one lens of an apatite‐garnet‐rich, laterally extensive (1.9 km) example, the Weatherly Creek iron‐formation, and it was placed in the context of reconnaissance studies of other similar units in the area. Chemical similarities with iron‐formations associated with Broken Hill‐type Pb–Zn deposit iron‐formations are demonstrated here. Concordant contact relationships, mineralogy, geochemical patterns and pre‐deformational alteration all indicate that the Soldiers Cap Group iron‐formations are mainly hydrothermal chemical sediments. Chondrite normalised REE patterns display positive Eu and negative Ce anomalisms, are consistent with components of both high‐temperature, reduced, hydrothermal fluid (≥250°C) and cool oxidised seawater. Major element data suggest a largely mafic provenance for montmorillonitic clays and other detritus during chemical sedimentation, consistent with westward erosion of Cover Sequence 2 volcanic rocks, rather than local mafic sources. Ni enrichment is most consistent with hydrogenous uptake by Mn‐oxides or carbonates. Temperatures inferred from REE data indicate that although they are not strongly enriched, base metals such as Pb and Zn are likely to have been transported and deposited prior to or following iron‐formation deposition. Most chemical sedimentation pre‐dated emplacement of the major mafic igneous sill complexes present in the upper part of the basin. Heating of deep basinal brines in a regional‐scale aquifer by deep‐seated mafic magma chambers is inferred to have driven development of hydrothermal fluids. Three major episodes of extension exhausted this aquifer, but were succeeded by a final climactic extensional phase, which produced widespread voluminous mafic volcanism. The lateral extent of the iron‐formations requires a depositional setting such as a sea‐floor metalliferous sediment blanket or series of brine pools, with iron‐formation deposition likely confined to much smaller fault‐fed areas surrounded by Fe–Mn–P–anomalous sediments. These relationships indicate that in such settings, major sulfide deposits and their associated chemical sediment marker horizons need not overlie major igneous sequences. Rather, the timing of expulsion of hydrothermal fluid reflects the interplay between deep‐seated heating, extension and magmatism.  相似文献   

17.
Processes controlling metal ion attenuation in acid mine drainage streams   总被引：1，自引：0，他引：1  
Two acid mine drainage streams have been investigated by detailed analysis of their sediments and waters, to obtain an understanding of the dominant processes which control the transport and attenuation of heavy metals under conditions of chronic high-level pollutant input. One of the water-courses has a thick hydrous iron oxide crust on its bed, where biotically mediated oxidation of ferrous iron resulted in precipitation of amorphous ferric hydroxide, along with substantial quantities of adsorbed silica, sulphate and Al and lesser quantities of As. Small amounts of K and Pb (and possibly hydronium) jarosites were also present in the sediments. Changes in pH and in the concentrations of Cu, Zn, and Cd appear to be mainly the result of dilution by seeps and tributaries.Although no sediment was recovered during collection of water samples from the second stream, saturation index calculations imply that precipitation should have been occurring. The observed down-stream loss of a number of elements supported this conclusion. The solids predicted to be precipitating were A1(OH)3, Cu2(OH)2CO3, and Fe(OH)3. Observed decreases in the concentrations of Cd, Zn and Mn can be accounted for on the basis of dilution alone. However, the additional mechanism of neutralization by higher pH inflows is required to account for the decrease in hydrogen ion concentration downstream.The basis for a potentially useful new technique (congruent element analysis) which enables the identification of conservative components in streams is presented. Comparison of logarithmic concentration versus distance plots delineates the point where chemical removal mechanisms become important for each element.  相似文献   

18.
Abstract. The study based on microscopic and microprobe techniques reveals that ilmenite of Manavalakurichi deposit has generally reached the alteration phase of 'leached ilmenite'. The XRD and bulk chemical analysis confirm the limited alteration undergone by ilmenite grains. Ilmenite alteration has been found to be a process of continuous leaching of iron from the mineral lattice and hydroxylisation. The enrichment of trace elements with progressive alteration is discussed. Si and Al are enriched by more than 100 fold. The prevalence of reducing environment at present in the deposit indicates that the oxidation of ferrous iron leading to pseudorutile formation would have occurred during transportation of sediments.  相似文献   

19.
The geological complexities of banded iron formation (BIF) and associated iron ores of Jilling-Langalata iron ore deposits, Singhbhum-North Orissa Craton, belonging to Iron Ore Group (IOG) eastern India have been studied in detail along with the geochemical evaluation of different iron ores. The geochemical and mineralogical characterization suggests that the massive, hard laminated, soft laminated ore and blue dust had a genetic lineage from BIFs aided with certain input from hydrothermal activity. The PAAS normalized REE pattern of Jilling BIF striking positive Eu anomaly, resembling those of modern hydrothermal solutions from mid-oceanic ridge (MOR). Major part of the iron could have been added to the bottom sea water by hydrothermal solutions derived from hydrothermally active anoxic marine environments. The ubiquitous presence of intercalated tuffaceous shales indicates the volcanic signature in BIF. Mineralogical studies reveal that magnetite was the principal iron oxide mineral, whose depositional history is preserved in BHJ, where it remains in the form of martite and the platy hematite is mainly the product of martite. The different types of iron ores are intricately related with the BHJ. Removal of silica from BIF and successive precipitation of iron by hydrothermal fluids of possible meteoric origin resulted in the formation of martite-goethite ore. The hard laminated ore has been formed in the second phase of supergene processes, where the deep burial upgrades the hydrous iron oxides to hematite. The massive ore is syngenetic in origin with BHJ. Soft laminated ores and biscuity ores were formed where further precipitation of iron was partial or absent.  相似文献   

20.
Arsenic sequestration by sorption processes in high-iron sediments   总被引：3，自引：0，他引：3  
High-iron sediments in North Haiwee Reservoir (Olancha, CA), resulting from water treatment for removal of elevated dissolved arsenic in the Los Angeles Aqueduct system, were studied to examine arsenic partitioning between solid phases and porewaters undergoing shallow burial. To reduce arsenic in drinking water supplies, ferric chloride and a cationic polymer coagulant are added to the aqueduct upstream of Haiwee Reservoir, forming an iron-rich floc that scavenges arsenic from the water. Analysis by synchrotron X-ray absorption spectroscopy (XAS) showed that the aqueduct precipitate is an amorphous hydrous ferric oxide (HFO) similar to ferrihydrite, and that arsenic is associated with the floc as adsorbed and/or coprecipitated As(V). Arsenic-rich floc and sediments are deposited along the inlet channel as aqueduct waters enter the reservoir. Sediment core samples were collected in two consecutive years from the edge of the reservoir along the inlet channel using 30- or 90-cm push cores. Cores were analyzed for total and extractable arsenic and iron concentrations. Arsenic and iron speciation and mineralogy in sediments were examined at selected depths by synchrotron XAS and X-ray diffraction (XRD). Sediment-porewater measurements were made adjacent to the core sample sites using polyacrylamide gel probe samplers. Results showed that sediment As(V) is reduced to As(III) in all cores at or near the sediment-water interface (0-4 cm), and only As(III) was observed in deeper sediments. Analyses of EXAFS spectra indicated that arsenic is present in the sediments mostly as a bidentate-binuclear, inner-sphere sorption complex with local atomic geometries similar to those found in laboratory studies. Below about 10 cm depth, XAS indicated that the HFO floc had been reduced to a mixed Fe(II, III) solid with a local structure similar to that of synthetic green rust (GR) but with a slightly contracted average interatomic Fe-Fe distance in the hydroxide layer. There was no evidence from XRD for the formation of a crystalline GR phase. The release of dissolved iron (presumably Fe2+) and arsenic to solution, as monitored by in situ gel probes, was variable but, in general, occurred at greater depths than arsenic reduction in the sediments by spectroscopic observations and appears to be near or below the depth at which sediment GR was identified. These data point to reductive dissolution of the sorbent iron phase as the primary mechanism of release of sorbed arsenic to solution.  相似文献   

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