Leaching potential and redox transformations of arsenic and selenium in sediment microcosms with fly ash

The unintended release of coal ash to the environment is a concern due to the enrichment of contaminants such as arsenic (As) and selenium (Se) in this solid waste material. Current risk assessments of coal ash disposal focus on pH as the primary driver of leaching from coal ash. However, redox speciation of As and Se is a major factor for their mobilization potential and has received much less attention for risk assessments, particularly in disposal scenarios where coal ash will likely be exposed to microbially-driven redox gradients. The aim of this study was to demonstrate the differences of aerobic and anaerobic conditions for the leaching of As and Se from coal ash. Batch sediment-ash slurry microcosms were performed to mimic an ash spill scenario and were monitored for changes in As and Se speciation and mobilization potential. The results showed that the dissolved As concentrations were up to 50 times greater in the anaerobic microcosms relative to the aerobic microcosms during the two week incubation. This trend was consistent with As redox speciation determined by X-ray absorption spectroscopy, which indicated that 55% of the As in the solid phase at the end of the experiment was present as As(III) (a more leachable form of arsenic relative to As(V)). In the aerobic microcosms, only 13% of the As was As(III) and the rest was As(V). More than half of the Se was present as Se(IV) in the original fly ash and in the aerobic microcosms, while in the anaerobic microcosms Se was gradually transformed to less soluble Se(0) species. Likewise, dissolved Se concentrations were up to 25 times greater in the aerobic microcosms relative to anaerobic conditions. While the overall observations of As and Se mobilization potential from coal ash were consistent with expectations for aqueous and solid phase speciation of these elements, the findings directly show the relevance of these processes for coal ash disposal. These results highlight the need to select appropriate environmental parameters to include in risk assessments as well as provide potential geochemical monitoring tools through the use of dissolved Se/As ratios to determine the redox conditions of ash storage and spill sites.     

Selenium enrichment in Carboniferous Shales,Britain and Ireland: Problem or opportunity for shale gas extraction?

The Carboniferous Bowland Shale in England, and its correlatives in Ireland, contain anomalously high concentrations of trace elements, including selenium (Se), molybdenum (Mo) and arsenic (As). High levels of these elements reflect high sulphur contents as these elements occur as trace constituents of pyrite. Anomalous Se in particular may have a volcanic provenance, from contemporary volcanic activity and/or drainage from Ordovician volcanogenic sulphide deposits. Following concern over the release of Se and As into groundwater during shale gas extraction in the US, the potential fate of Se and As during any future shale gas extraction from the Bowland Shale merits attention. It is at least an environmental issue that must be managed, but at best it could be an opportunity for extraction of Se in an environmentally sensitive manner.     

Assessing bioaccessible fractions of arsenic,chromium, lead,selenium and zinc in coal fly ashes

The utility of a physiologically based extraction test for evaluating the bioaccessibility of metals from fly ash in the human gastrointestinal system was evaluated in the present research. Calcium-rich and silica-rich fly ashes collected from eight power plants in India and United States of America were assessed for bioaccessibility for arsenic, chromium, lead, selenium and zinc. The results from the physiologically based extraction test were compared with those from a sequential extraction procedure that is often applied to solid wastes. Based on the physiologically based extraction test results, more than 40 % of the arsenic was found to be bioaccessible for all the ashes while selenium was very accessible for the calcium-rich ashes. Lead was found to be insignificantly bioaccessible in calcium-rich as well as silica-rich fly ashes. The mobilization of metals in the first three steps of the sequential extraction procedure was similar to the mobilization in the physiologically based extraction test for selenium for all ashes and for arsenic and chromium for most ashes, but the sequential extraction procedure mobilized more zinc than did the physiologically based extraction test. These results indicate that while sequential extraction procedures can provide good estimates of the bioaccessibility of many elements, extraction tests that more closely simulate physiological conditions can provide more accurate measures of bioaccessible concentrations of metals.     

Accumulation and speciation of selenium in evaporation basins in California,USA

The accumulation of selenium in evaporation basins (or ponds) in the San Joaquin Valley, California is of a great concern due to its potential hazards to environments. In this study, the accumulation, speciation and concentrations of Se were examined in waters as well as sediments in a system of the evaporation ponds. A significant decrease in the total dissolved Se concentration in Cell 1 in which drainage water with higher Se concentration was pumped from Inlet Channels indicated that the immobilization of Se was active in the Cell 1 and resulted in the higher Se concentration in sediments compared to the terminal cell such as Cell 9. The percentage of reduced Se species such as selenite [Se(IV)] and org-Se of total Se in drainage waters was also found increased in Cell 1 compared to Inlet Channels. The total dissolved Se concentrations in water along flow paths from Cell 1 were relatively constant except for terminal cells such as Cells 9 and 10, which showed higher total dissolved Se concentrations due to evapoconcentration. The percentage of reduced Se forms of total Se was inversely proportional to the percentage of Se(VI) depending on the redox condition of evaporation ponds along the flow paths. Sequential extractions of Se species in sediments indicated that organic associated Se and elemental Se were prevalent forms in sediments in the ponds system. The higher concentrations of elemental Se and organic associated Se in sediments in Cell 1 indicated that the immobilization of Se was active in the sediments compared to Cell 9, while the percentage of both fractions of total Se in sediments in Cells 1 and 9 was relatively constant. The organic materials from algae might provide carbon sources for Se reduction and Se sink in sediments in its elemental and organic associated forms.     

Geochemistry of selenium: formation of ferroselite and selenium behavior in the vicinity of oxidizing sulfide and uranium deposits

The geochemistry of Se is largely controlled by that of iron, with which Se is closely affiliated in both oxidizing and reducing environments. In aerated waters the Se(IV) oxyanions, HSeO^?₃ and SeO^2?₃, are strongly adsorbed by hydrated surfaces of ferric oxides over the pH range 2–8; above pH8 adsorption decreases to complete desorption at pH 11. This adsorption immobilizes Se(IV) in neutral-to-acid waters and increases the range of oxidation potential over which Se(IV) is stable. During experimental aeration of aqueous Fe-S-Se systems, the stability field of Se(IV) is attained and elemental Se is slowly oxidized to this higher valence; oxidation potentials of the Se(VI) stability field were never reached, however, even by continued aeration of an alkaline system. Under reducing conditions, elemental Se either is incorporated within pyrite or forms the mineral ferroselite (FeSe₂.Selenium geochemistry is summarized on an Eh-pH diagram, synthesized from equilibrium calculations, experimental work and reported geologic occurrences. A stability field for ferroselite, constructed for a Gibbs free-energy value of ?23.2 kcal/mole, is in accord both with its geologic occurrence and behavior and with conditions under which ferroselite has been synthesized. Traces on this diagram of Eh-pH variation show the behavior of selenium during oxidation of associated iron-sulfide minerals. Such considerations also demonstrate the manner in which selenium migrates, is deposited and is increasingly concentrated in roll-type sandstone uranium deposits, as well as the relative positions of the several forms of selenium within the deposit.     

Spatial variation of selenium in Appalachian coal seams

Selenium (Se) is a trace element that can cause human physical deformations due to selenosis, and mutagenic changes on a range of sensitive macro-organisms. Previous studies indicated that Se enrichment is significantly greater in coal than in other rock units, suggesting a correlation between Se and coal bed proximity. Since coal extraction can cause a release of Se, some regulatory authorities have responded by requiring sampling of coal seams and adjacent rock for Se prior to issuing coal mining permits. This sampling is done under the assumption that Se in a small number of samples will be correlated to the Se concentrations throughout the strata they represent. For example, in one case a single continuous deep rock core was sampled for Se to estimate the concentrations of Se across a 2.52 km² proposed surface coal mine. This project examined the adequacy of such an approach using univariate statistics and variograms to determine the spatial variability and correlation of Se concentrations collected from six Appalachian coal seams. The results from all analyses showed no significant spatial correlation of Se within any coal seam examined. Given this lack of measured Se spatial correlation in Appalachian coal seams for scales as small as 0.10 km, it is unlikely that a Se spatial correlation exists in adjacent rock units at similar scales either, which is currently the assumption being made for sampling to minimize Se pollution from surface coal mining.     

恩施渔塘坝富硒碳质岩中硒的赋存状态

在渔塘坝富硒碳质岩中发现了自然硒及其系列硒矿物的组合.这些硒矿物有自然硒、方硒铜矿、硒铜蓝、水硒铁石、硒银矿、含硒黄铁矿、含硒黄铜矿和难以确定名称的Fe-Se矿物.其中自然硒、方硒铜矿和硒铜蓝的矿物组合主要分布在断层面附近的碳质硅质岩中,自然硒与方硒铜矿的矿物组合主要分布在高碳质泥岩中,水硒铁石及未确定的Fe-Se矿物主要赋存于露头处的富硒碳质岩中.硒矿物中除自然硒较普遍地存在外,其他矿物并不是均匀地分布于富硒碳质岩中,而是局部性地出现.Cu-Se矿物的大量发育表明铜可能在硒的表生迁移转化中起着某种重要的作用.     

Early diagenetic behaviour of selenium in freshwater sediments

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.     

渔塘坝富硒碳质岩石中硒淋滤实验的初步研究

渔塘坝是中国较为典型的高硒地区之一。从该区选取了4个典型的富硒碳质岩样品,并在常温条件下进行了淋滤实验研究(pH=2.0,4.0和6.5)。初步结果表明:随着液固比的增大和淋滤时间的延长,淋滤液中硒含量变化的总体呈降低趋势。不同岩类间硒的淋失量有所差别,但岩石总量硒并不是影响硒淋失的主要因素。淋滤原液的不同pH值对岩石硒的淋失有显著影响,其淋失量的排列顺序是pH=2.0>pH=6.5>pH=4.0。岩石中碳酸盐与黄铁矿含量之比同淋滤液pH的变化有关,并且极可能是影响岩石风化初始阶段硒淋失的重要因素之一。     

浙江富硒土壤资源调查与评价

浙江省农业地质环境调查发现,浙北、浙东、浙中地区富硒土壤呈大面积分布。不同类型土壤中,以石灰岩土硒含量最高,黄壤和红壤硒含量次之;不同类型成土母质中,以残坡积物硒含量相对较高;不同类型岩石中,以石英砂岩、硅质岩和中深变质岩硒含量较高,高于中国东部地壳丰度值。富硒土壤主要分布于富硒岩石和煤系地层区。硒多富集在土壤表层,由地表向深部含量迅速下降。根据土壤背景值和硒生态景观分级标准,建立了富硒土壤评价标准,划分硒含量等级区,圈定了浙江省富硒土壤分布。     

Arsenic in streams,stream sediments,and ground water,fairbanks area,alaska

Arsenic concentrations of less than 5 ppb to as large as 1,260 ppb in stream waters and from 5 ppm to 4,000 ppm in stream sediments were found in the Pedro Dome-Cleary Summit area, Alaska. Waters from three of 20 wells sampled had arsenic concentrations exceeding the U.S. Public Health Service recommended limit of 50 ppb. The high arsenic levels are a consequence of arsenic enrichment in the rocks of the area. Placer and lode-gold mining may increase the arsenic content of the waters by exposing arsenic-containing rocks to surface waters and by increasing the load of arsenic-rich sediments in the streams. Finding these disturbingly large concentrations of arsenic in the waters of the Fairbanks area was the major result of this work, inasmuch as a subsequent study (to be published) revealed arsenic concentrations as large as 10 ppm in domestic wells and prompted an extensive study by Federal and State agencies of the health hazard posed by these arsenic-rich waters.     

Geochemistry of the Yutangba Se Deposit in Western Hubei, China

1IntroductionThecontentsofSeinthecrustareextremelylow ,onlyabout0 .0 5mg/kg .Innatureitishardtoformindependentminerals,insteaditisdispersedinothermineralsandmedia.Althoughitscon tentsarefarhigherthanthoseofTeinthecrust,seleniumisusuallydispersedinsulfidesinitsas cendingandformingprocesses (D’yachkovaandKhodakovskiy ,1 968) .Thisisthereasonwhyse leniummineralsarefarlessthantelluriummineralsandsulfidesinnature (Simonetal.,1 997) .Forthisreason ,thegeochemicalstudyofseleniumdidnotattractanyat…     

Tellurium,selenium and cobalt enrichment in Neoproterozoic black shales,Gwna Group,UK: Deep marine trace element enrichment during the Second Great Oxygenation Event

Black shales of the late Neoproterozoic Gwna Group (570–580 Ma), UK, contain enrichments of tellurium (Te), selenium (Se) and cobalt (Co) relative to average shale compositions. The Te and Co enrichments bear comparison with those of ferromanganese crusts in the modern deep ocean. Gwna Group deposition coincides with the Second Great Oxidation Event, which had a significant effect on trace element fixation globally. Selenium and Te concentrations within these black shales indicate increased continental weathering rates, high biological productivity and corresponding increases in atmospheric O₂ concentrations. Cobalt, nickel (Ni) and arsenic (As) enrichments in this succession are secondary mineralisation phases. Demand for many of the trace elements found enriched in the Gwna Group black shales make their mechanisms of accumulation, and variations through the geological record, important to understand, and suggests that new resources may be sought based on black shale protoliths from this period.     

四川省沐川县北部土壤硒地球化学特征与成因探讨

通过对四川省沐川县北部土地质量地球化学调查,查明了工作区土壤Se的地球化学特征,并对其成因进行了初步研究.结果表明,工作区土壤Se含量范围为0.06×10-6-1.49 ×10-6,平均值为0.41× 10-6,主要以富硒土壤为主,满足富硒土壤条件的土壤面积占工作区总面积的60％.不同成土母岩中土壤Se含量差异较大,趋...     

Distribution of Selenium in Corn and Its Relationship With Soil Selenium in Yutangba Mini—Landscape

Within the range of 0.01 km mini-landscape in Yutangba, Enshi, Hubei Province, the content of Se in corn is very high. The average Se contents in root, stem, leaf and seed of corn were estimated to be 4.36±3. 27mg/kg, 3.08±2.24 mg/kg, 9.74±7.62mg/kg, and 8.07±5.02mg/kg, respectively. The research results show that there is a significantly positive correlation between corn selenium and soil selenium, and thus according to the distribution of Se in corn, three subregions can be divided in Yutangba. The content of selenium in corn is controlled by that of soil. A little variation in selenium content in soil will lead to a considerable corresponding variation in corn. So it is deduced that the organs that contain relatively high Se in plants may be used as a sensitive selenium indicator of Se levels in the environment.     

Distribution of selenium and arsenic in differentiated multicellular eukaryotic fossils and their significance

We present variation patterns of trace elements within different sequences of the Ediacaran Doushantuo Formation(DST,635-551 million years ago),and inside the cells of the earliest differentiated multicellular eukaryotic fossils of the Weng'an biota in the Weng'an County of Guizhou Province.The results showed that selenium is the most enriched and significantly varied trace element among the 22 trace elements throughout the DST,followed by arsenic.The highest selenium and arsenic content sequences are consistent with the first appeared sequence of the earliest differentiated multicellular eukaryotic fossils Megasphaera at the middle to upper parts of the DST.Nanoman secondary ion mass spectrometry analyses show that selenium and arsenic have an inhomogeneous and punctate distribution in the nucleus and cytoplasm.The nucleus has anomalously enriched levels of selenium and arsenic among the organelles.The selenium and arsenic concentrations exhibit a positive correlation with the diversity of fossilized Megasphaera.These new findings give us a clue that the anomalous enrichment of selenium and arsenic might contributes to the cell differentiation in Ediacaran Doushantuo period.     

Removal of dissolved selenium by siderite,pyrite, and sphalerite: Implications to selenium sequestration in water-saturated,anoxic coal waste rock

The mechanisms of abiotic sequestration of Se(VI) and Se(IV) on a sample of coal waste rock collected from the Elk Valley, Canada and on three pure mineral species (i.e., siderite, pyrite, and sphalerite) present in coal waste rock were assessed using sterile batch testing under water-saturated, anoxic conditions. Only siderite removed measurable Se(VI) from the test solutions with ~90% removal after 100 d attributed to initial adsorption to the siderite surface as Se(VI) and subsequent reduction to Se(IV) and Se(0). In contrast to Se(VI), all samples removed Se(IV) from the aqueous solutions. The rate of Se(IV) removal was pyrite > siderite > waste rock > sphalerite. The waste rock sample removed Se(IV) from solution in two stages: up to ~40% of the aqueous Se(IV) was rapidly removed (by day 1) followed by slower removal of Se(IV) with up to ~97% removal after 99 d. Se(IV) removal is attributed to the adsorption of Se(IV) and subsequent reduction to Se(0) onto the siderite and pyrite phases of the waste rock. The initial (1 d) removal of Se(IV) by waste rock was characterized using a distribution coefficient (K_d) of 15.5 L/kg. Longer-term Se(IV) removal was fitted with zero and first order removal rates. The removal of Se(IV) by sphalerite was minor and deemed to have a minimal effect on Se sequestration in the waste rock. Desorption tests on waste rock showed that the fraction of sequestered Se susceptible to desorption decreased with time as adsorbed Se(IV) was reduced to insoluble Se(0). These findings show that abiotic Se sequestration can occur in saturated, anoxic zones in coal waste rock dumps.     

Adsorption studies for the simultaneous removal of arsenic and selenium using naturally prepared adsorbent materials

The adsorption properties of eggshell membranes (ESM), eggshells (ES) and orange peels (OP) were studied for the removal of arsenic (total As) and selenium (total Se). The effect of chemical treatment of these adsorbents by HNO₃ and NaOH was also investigated using Fourier transform infrared spectroscopy (FT-IR). Analysis of the FT-IR spectra showed that treatment with NaOH and HNO₃ had an effect on the functional groups present in the materials and also on the adsorption by extension. Thermal analysis showed that ES were more thermally stable than the others with no water molecules in their matrix, which could have caused a substantial weight loss at around 70 °C. In terms of adsorption capacities, chemical treatment increased the adsorption capacities of ESM and OP achieving up to 170 μg g^?1 (As) and 160 μg g^?1 (Se), and 120 μg g^?1 (As) and 70 μg g^?1 (Se), respectively, with not much activity for ES in terms of adsorption. The two adsorbents (NaOH-treated OP and ESM) were then tested in environmental water samples and the results showed that 68.9 % of As and 74.8 % of Se, and 54.1 % of As and 47.3 % of Se were removed from domestic wastewater samples investigated using OP and ESM, respectively. Moreover, better selectivities towards the compounds of interest were achieved.     

中国西南地区二叠纪乐平世陆生生物大灭绝期煤中砷和硒的演化及古环境意义

为了探讨中国西南地区二叠系乐平统(上二叠统)龙潭组中下部煤系不同煤组分中砷、硒的含量和演化及古环境意义,对近10年来采集于中国西南扬子地台的二叠系乐平统龙潭组主采煤层的原煤、亮煤、煤矸石、黄铁矿结核等样品中砷、硒元素含量进行了测定和分析,并与中国华北地台一些煤矿的上石炭统-下二叠统太原组、山西组的原煤、镜煤、亮煤、煤矸石、黄铁矿结核等样品中砷、硒含量进行对比分析。结果表明：西南地区乐平统龙潭组煤的砷、硒含量变化较大,但总体高于华北晚石炭世和早二叠世煤的砷、硒含量;西南二叠系乐平统龙潭组大多数的亮煤中砷、硒含量高于原煤全煤样(刻槽样)中的砷、硒含量,也远远高于同煤层煤矸石的含量,龙潭组部分亮煤的砷含量尤其高,为55～338 mg/kg,还发现砷含量为89 mg/kg的亮煤。但华北上石炭统-下二叠统的镜煤中的砷、硒含量与之相反,低于原煤全煤样的砷、硒含量,其中砷含量非常低,为063～129 mg/kg。说明西南地区上二叠统煤中的砷和硒与煤的有机质密切相关,可能主要来源于成煤古植物。在西南乐平世早、中期第Ⅰ幕陆生生物集群灭绝事件期间,陆生动物的食物--植物中有毒有害元素砷、硒含量明显增加,陆生环境或泥炭沼泽中可溶性砷、硒含量增加。     

硒在干酪根中的两种不同赋存状态:TEM证据

对拉尔玛Se—Au矿床和渔塘坝硒矿床中干酪根的高分辨透射电镜(TEM)研究表明，两个矿床的Se在干酪根中的赋存状态是截然不同的。前者Se在干酪根中的富集可能主要以有机结合态的形式存在，主要是取代干酪根中的硫；而后者Se在干酪根中的富集主要以超微包体Se的形式吸附在干酪根中。两种不同的赋存状态可能主要取决于干酪根中硫含量的多少以及成矿时氧化还原条件的变化。研究表明，TEM是研究元素在干酪根中赋存状态的有效手段。