首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
The background to recent developments in investigations on coal porphyrins is reviewed. Essentially all the work of the past ten years has been with lignites and coals of the humic series. The concentrations of porphyrins and metalloporphyrins are low (0-ca. 10 μg g−1), which makes for difficulties in isolation and analysis.The preferred methods of isolation and analysis are summarised. The coal porphyrins differ from the porphyrins from crude oil, oil shale and related deposits in a variety of ways which are discussed. The major differences are the predominance of the etio series over the cycloetio series (DPEP series), the presence of Fe and Ga porphyrins (rather than Ni and VO porphyrins), and the presence of mesoporphyrin IX in lignite.Recent results tend to support Treibs' original idea (1935) that, for the coal porphyrins, both chlorophyll and iron porphyrin (haem) sources are important. The application of a weighted mean molecular mass of the porphyrins present as a biological marker in determining coal rank (Porphyrin Index of Coalification) is illustrated. Current activity is directed to the isolation and identification of individual iron complexes, and here a combination of thin layer chromatography and paramagnetically shifted 1H-NMR spectroscopy (of dicyanoferrihaems), together with direct comparison with authentic haems especially synthesised for the purpose, has been rewarding.  相似文献   

2.
Sediments from the Red River and from an adjacent floodplain aquifer were investigated with respect to the speciation of Fe and As in the solid phase, to trace the diagenetic changes in the river sediment upon burial into young aquifers, and the related mechanisms of arsenic release to the groundwater. Goethite with subordinate amounts of hematite were, using Mössbauer spectroscopy, identified as the iron oxide minerals present in both types of sediment. The release kinetics of Fe, As, Mn and PO4 from the sediment were investigated in leaching experiments with HCl and 10 mM ascorbic acid, both at pH 3. From the river sediments, most of the Fe and As was mobilized by reductive dissolution with ascorbic acid while HCl released very little Fe and As. This suggests As to be associated with an Fe-oxide phase. For oxidized aquifer sediment most Fe was mobilized by ascorbic acid but here not much As was released. However, the reduced aquifer sediments contained a large pool of Fe(II) and As that is readily leached by HCl, probably derived from an unidentified authigenic Fe(II)-containing mineral which incorporates As as well. Extraction with ascorbic acid indicates that the river sediments contain both As(V) and As(III), while the reduced aquifer sediment almost exclusively releases As(III). The difference in the amount of Fe(II) leached from river and oxidized aquifer sediments by ascorbic acid and HCl, was attributed to reductive dissolution of Fe(III). The reactivity of this pool of Fe(III) was quantified by a rate law and compared to that of synthetic iron oxides. In the river mud, Fe(III) had a reactivity close to that of ferrihydrite, while the river sand and oxidized aquifer sediment exhibited a reactivity ranging from lepidocrocite or poorly crystalline goethite to hematite. Mineralogy by itself appears to be a poor predictor of the iron oxide reactivity in natural samples using the reactivity of synthetic Fe-oxides as a reference. Sediments were incubated, both unamended and with acetate added, and monitored for up to 2 months. The river mud showed the fastest release of both Fe and As, while the effect of acetate addition was minor. This suggests that the presence of reactive organic carbon is not rate limiting. In the case of the river and aquifer sediments, the release of Fe and As was always stimulated by acetate addition and here reactive organic carbon was clearly the rate limiting factor. The reduced aquifer sediment apparently can sustain slower but prolonged microbially-driven release of As. The highly reactive pools of Fe(III) and As in the river mud could be due to reoxidation of As and Fe contained in the reducing groundwater from the floodplain aquifers that are discharging into the river. Deposition of the suspended mud on the floodplain during high river stages is proposed to be a major flux of As onto the floodplain and into the underlying aquifers.  相似文献   

3.

Phosphorus (P) plays an important role in the eutrophication of river and marine environments. The adsorption-desorption processes of P by estuarine sediment were studied to better understand the P behaviour in the Loughor Estuary in Carmarthen Bay, UK. Three types of models were used to estimate the P adsorption isotherm for five sediment samples from the Loughor Estuary. The Langmuir adsorption isotherm showed a good fit with the linear (data) isotherm. The P desorption from bed sediment was measured as the easy exchangeable P (MgCl2 extractable). A negative correlation was found between adsorbed P in bed sediment and median particle size. A positive correlation was also found between P adsorbed and metals such as iron (Fe), aluminium (Al) and calcium (Ca) as well as the total organic carbon (TOC).

  相似文献   

4.
The early diagenetic environment of intertidal sandy sediments (sands) and muddy sediments (muds) is described and compared from two cores taken from an unpolluted part of the Manukau Harbour, New Zealand. Extraction techniques characterized the form of the trace elements (Fe, Mn, S, C, Pb, Zn, Cu) at different depths in the sediment. Dissolved forms of Fe, Mn, and S were measured in interstitial water. Nonresidual metal concentrations, humic acid, FeS, and FeS2 are an order of magnitude higher in the muds than in the sands because of dilution by unreactive sand particles. Muds contain a larger proportion of metals in the mobile fractions; exchangeable (Mn), carbonate (Mn, Fe, Zn), and easily-reducible oxide (Fe, Mn, Zn, Pb). This is due to greater surface area (for Mn adsorption); the favorable conditions for MnCO3, FeCO3, and FeS precipitation; and higher concentrations of easily reducible iron oxide and humic acid. Therefore, compared to the sands, muds are more important as reservoirs for toxic metals, both in terms of quantity and availability. At either site there was very little difference between the forms of Zn, Pb or Cu identified by sequential extraction as sediments changed from oxic to anoxic conditions. One reason for this is that the amounts and proportions of some of the important components that bind metals, viz., amorphous iron hydrous oxides, humic acids, and FeS2, do not change much. Other components that do change with redox conditions, for example, manganese phases and FeS, are only minor components of the sediment. Redox conditions, then, have relatively little effect on trace-metal partitioning in the sediment matrix of these unpolluted sediments.  相似文献   

5.
The primary factors that control the concentration of total reduced (inorganic) sulfide in coastal sediments are believed to be the availability of reactive iron, dissolved sulfate and metabolizable organic carbon. We selected nine sites in shallow (<3 m), close to sub-tropical, estuaries and bays along the central Texas coast that represented a range in sediment grain size (a proxy for reactive iron), salinity (a proxy for dissolved sulfate), and total organic carbon (a proxy for metabolizable organic carbon). Based on these parameters a prediction was made of which factor was likely to control total reduced sulfide at each site and what the relative total reduced sulfide concentration was likely to be. To test the prediction, the sediments were analyzed for total reduced sulfide, acid volatile sulfide, and citrate dithionate-extractable, HCl-extractable and total Fe in the solid phase. Using solid-state gold–mercury amalgam microelectrodes and voltammetry, we determined pore water depth profiles of Fe(II) and ΣH2S and presence or absence of FeS(aq). At five of the nine sites the calculated degree of sufildization of citrate dithionite-reactive-iron was close to or greater than 1 indicating that rapidly reactive iron was probably the limiting factor for iron sulfide mineral formation. At one site (salinity = 0.9) dissolved Fe(II) was high, ΣH2S was undetectable and the total reduced sulfide concentration was low indicating sulfate limitation. At the last three sites a low degree of sulfidization and modest total reduced (inorganic) sulfide concentrations appeared to be the result of a limited supply of metabolizable organic carbon. Fe(II)–S(-II) clusters (FeS(aq)) were undetectable in 10 out of 12 bay sediment profiles where ΣH2S was close to or below detection limits, but was observed in all other porewater profiles. Acid volatile sulfide, but not total reduced sulfide, was well correlated with total organic carbon and ranged from being undetectable in some cores to representing a major portion of total reduced sulfide in other cores. Although predicted controls on total reduced sulfide were good for very low salinity water or sandy sediments, they were only right about half the time for the other sediments. The likely reasons for the wrong predictions are the poor correlation of total organic carbon with grain size and differing fractions of metabolizable organic carbon in different sedimentary environments. Differences in sediment accumulation rates may also play a role, but these are difficult to determine in this region where hurricanes often resuspend and move sediments. This study demonstrates the need to examine more complex and often difficult to determine parameters in anoxic “normal marine” sediments if we are to understand what controls the concentration and distribution of sulfides.  相似文献   

6.
Alkyl porphyrins from five sediment layers deposited under different palaeoenvironmental conditions in the Mulhouse basin (Alsace, France) have been examined by normal-phase high performance liquid chromatography and liquid chromatography–tandem mass spectrometry. The fossil pigments show marked differences in distribution among the different lithological zones, with around 40 major alkyl porphyrin components detected. Assignment of structures to a number of the porphyrins has been achieved through detailed studies involving analysis of successive losses experienced during multistage tandem mass spectrometry. A suite of bacteriochlorophyll-derived alkyl porphyrins has been detected that exhibits fragmentations in tandem mass spectrometry not consistent with the presence of either n-Pr or i-Bu moieties. Instead, these unusual geoporphyrins may be evidence of previously undetected neo-Pent substituted alkyl porphyrins. The distributions in the different horizons of the Mulhouse basin core reveal that the relative abundances of certain alkyl porphyrins respond to changes in environmental conditions, reflecting variations in the primary producer community during the deposition of the core.  相似文献   

7.
《Resource Geology》2018,68(3):287-302
Banded iron formations (BIFs) are the most significant source of iron in the world. In this study, we report petrographic and geochemical data of the BIF from the Meyomessi area in the Ntem Complex, southern Cameroon, and discuss their genesis and the iron enrichment process. Field investigations and petrography have revealed that the studied BIF samples are hard; compact; weakly weathered; and composed of magnetite, subordinate quartz, and geothite. The geochemical composition of the whole rock reveals that iron and silica represent more than 98 wt% of the average composition, whereas Al2O3, TiO2, and high‐field strength elements (HFSE) contents are very low, similar to detritus‐free marine chemical precipitates. The total iron (TFe) contents range from 48.71 to 65.32 wt % (average of 53.29 wt %) and, together with the low concentrations of deleterious elements (0.19 wt % P on average), are consistent with medium‐grade iron ores by global standards. This interpretation is confirmed by the SiO2/Fe2O3total versus (MgO + CaO + MnO)/Fe2O3total discrimination plot in which most of the Meyomessi BIF samples fall in the field of medium‐grade siliceous ore. Only one sample (MGT94) plots in the high‐grade magnetite–geothite ore domain. The high Fe/Ti (376.36), Fe/Al (99.90), and Si/Al (29.26) ratios of the sample are consistent with significant hydrothermal components. The rare earth elements (REE) contents of the studied BIF samples are very low (∑REE: 0.81–1.47 ppm), and the Post‐Archaean Australian Shale (PAAS)‐normalized patterns display weak positive Eu anomalies (Eu/Eu*: 1.15–1.33), suggesting a syngenetic low‐temperature hydrothermal solutions, similar to other BIF worldwide. However, the Meyomessi BIFs show high Fe contents when compared to the other BIFs. This indicates an epigenetic mineralization process affected the Meyomessi BIF. From the above results and based on the field and analytical data, we propose that the genetic model of iron ores at the Meyomessi area involves two stages of the enrichment process, hypogene enrichment of BIF protore by metamorphic and magmatic fluids followed by supergene alteration as indicated by the presence of goethite in the rocks.  相似文献   

8.
The aim of this study was to investigate the influence of mining on the geochemical composition of the alluvial sediments of the Gualaxo do Norte River Basin, located in the eastern-southeastern portion of the Quadrilátero Ferrífero (Minas Gerais State, Brazil). The analysis of the sedimentological succession was carried out using 16 stratigraphic sections (cutbanks and alluvial terraces) and analysis of 111 sediment samples for major- and trace-elements by ICP-OES. The stratigraphic analysis revealed the deposition history of the collected sediments. Anomalous concentrations of certain elements such as As and Pb were found, which are associated with stratigraphic facies with evidences of gold artisanal mining, and Fe anomalies associated with iron ore mining. The classification of the sections was possible by means of principal component analysis. From the sediment characteristics, three groups were identified: (1) those influenced by iron ore mining and gold artisanal mining; (2) those influenced by iron ore mining and (3) those with no influence of human activities.  相似文献   

9.
The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens-like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy.All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of FeTOT. The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments.  相似文献   

10.
A section through the late Archean Mt. McRae Shale comprising, in ascending order, a lower shale interval (LSI), a banded iron formation (BIF), an upper shale (USI) and a carbonate (C1) has been analyzed for total Fe and Al contents and authigenic Fe present as carbonate, oxide, sulfide and silicate phases. The authigenic mineralogy is controlled by the episodic addition of Fe from hydrothermal activity and removal of Fe by sulfide, relative to rates of clastic sedimentation. The LSI and BIF have mean FeT/Al values of 2 and 5, respectively, that record iron enrichment from hydrothermal sources. Iron was precipitated primarily as siderite accompanied by Fe-rich chlorite from anoxic bottom waters rich in dissolved Fe. Pyrite formation was probably limited by the availability of sulfate, which was present at low concentrations and became rapidly depleted. The USI has generally lower FeT/Al values (0.6-1.3), similar to those found in Paleozoic shales, with the exception of one interval where enrichment may reflect either a weak hydrothermal source or the operation of an iron shuttle. This interval contains authigenic Fe predominantly as pyrite, where high values for DOP (>0.8) indicate the existence of a water column that became rich in dissolved sulfide (euxinic) when sulfate concentrations increased due to a transient or secular increase in ocean/atmosphere oxygenation. High concentrations of dissolved sulfide maintained low concentrations of dissolved Fe, which allowed only minor amounts of Fe to be precipitated as carbonates and silicates. The USI also has elevated concentrations of organic matter that most probably reflect increased productivity and likely limited euxinia to midportions of the water column on the basin margin. The carbonate C1 represents a basinal chemistry where sulfide has been removed and FeT/Al values are ∼1 indicating that hydrothermal activity again produced dissolved Fe-rich bottom waters. Detailed iron speciation of the Mt. McRae Shale can be used to recognize spatial and temporal variations in iron and sulfur inputs to the late Archean Hamersley Basin, just prior to the Paleoproterozoic rise in atmospheric oxygenation, and our refined methods have relevance to all Fe-rich deposits.  相似文献   

11.
The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO4·2H2O), ferric arsenates, arseniosiderite (Ca2Fe3(AsO4)3O2·3H2O), Ca-Fe arsenates, pharmacosiderite (KFe4(AsO4)3(OH)4·6-7H2O), jarosite (K2Fe6(SO4)4(OH)12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%.Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 Å and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides.The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore.  相似文献   

12.
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   

13.
Sediment samples were analyzed as part of ongoing environmental investigations of historical U mining impacts within Custer National Forest in Harding County, South Dakota. Correlations between As and U content, grain size and soil mineralogy were determined to identify contaminant fate and transport mechanisms. Soil samples collected near the mining source zone and up to 61 km downgradient of the minesites were analyzed. Samples were homogenized and wet sieved through polymer screens, and metal(loid) concentrations were determined using inductively coupled plasma mass spectrometry (ICP-MS). Powder X-ray diffraction (XRD) analysis identified quartz as the primary mineral for all size fractions, with varying amounts of analcime, indicative of volcanic origin. Selected samples were examined for trace mineral composition using scanning electron microscopy (SEM). The presence of Fe sulfides and Fe (hydr)oxides indicate heterogeneity in redox potentials on a microscopic scale. Elevated metal(loid) concentrations were associated with trace concentrations of Fe sulfide, indicating an influence on metal transport during weathering. Sequential chemical extractions (SCE) performed on source sediment fractions demonstrated that most As and U was adsorbed to Fe- and Mn-oxides and carbonates with lesser amounts bound by ion exchange, organics and Fe sulfides. Large changes in U/Th and As/Th ratios were observed to coincide with geochemical changes in the watershed, suggesting that metal(loid)–Th ratios may be used in environmental investigations to identify geochemically-significant watershed conditions.  相似文献   

14.
We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (∼94 Ma) and the Paleocene-Eocene thermal maximum (∼55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.  相似文献   

15.
Sediment samples were collected from streambeds in an undisturbed watershed in eastern Quebec (Gaspé Peninsula). Two sampling sites were located on a stream draining an area of known mineralization (Cu, Pb, Zn) and two on a control stream. The sediment samples were separated into 8 distinct size classes in the 850 μm to <1 μm size range by wet sieving, gravity sedimentation or centrifugation. Each sediment subsample was then subjected to a sequential extraction procedure designed to partition the particulate heavy metals into five fractions: (1) exchangeable; (2) specifically adsorbed or bound to carbonates; (3) bound to Fe-Mn oxides; (4) bound to organic matter; (5) residual. The following metals were analyzed in each extract: Cu, Pb, Zn; Fe, Mn.Comparison of samples from the mineralized area with control samples revealed the expected increase in total concentrations for Cu, Pb and Zn. Non-detrital metals were mainly associated with Fe oxides (specifically adsorbed; occluded) and with organic matter or resistant sulfides. For a given sample, variation of trace metal levels in fractions 2 and 3 with grain size reflected changes in the available quantities of the inorganic scavenging phase (FeOx/MnOx); normalization with respect to Fe and Mn content in fraction 3 greatly reduced the apparent dependency on grain size.The results of this study suggest that a single reducing extraction (NH2OH.HCl) could be used advantageously to detect anomalies in routine geochemical surveys. A second leaching step with acidified H2O2 could also be included, as the trace metal concentrations in fraction 4, normalized with respect to organic carbon content, also showed high {anomaly/background} ratios.  相似文献   

16.
Many studies have proposed that silicic acid and phosphate (PV) can displace arsenic sorbed to iron oxides leading to elevated As concentrations in aquatic systems. While surface complexation models are adept at quantifying sorption to synthetic oxides in laboratory systems their application to complex natural systems remains challenging. In this study we provide a systematic approach to developing a robust use of models for understanding AsV distribution in natural systems in which hydrated iron oxides are the main adsorptive phase. The Waikato River provides a useful laboratory for this work because it contains high H4SiO4, AsV and PV loadings due to geothermal and agricultural inputs. A 15 min oxalate extraction and a 48 h ethylenediaminetetraacetic acid (EDTA) extraction of river sediment contained the same ratios of As:Fe, P:Fe and Si:Fe. Both of these extracts target the poorly ordered iron oxide phases (typically ferrihydrite) and by following the release of elements over time in the EDTA extraction it was possible to demonstrate that the extracted As, P, and Si were associated with the ferrihydrite. This demonstrates for the first time that a single oxalate extraction can quantify ferrihydrite sorbed H4SiO4, As and PV and provides a basis to quantify the role of these ligands in inhibiting AsV sorption to sediments. The measured concentrations of ferrihydrite sorbed AsV, PV and H4SiO4 for the Waikato River suspended sediment allow for the informed selection of appropriate model parameters for applying the Diffuse Layer Model to the system. In this way it was possible to quantify the effect of the individual components in the river water on AsV sorption. This study provides an explanation for the observation that the proportion of sorbed As in the Waikato River is generally significantly lower than that observed in rivers closer to the world average concentrations. More generally the study provides a method to quantify the role of individual water chemistry components on AsV distribution in natural systems.  相似文献   

17.
Core sediments from two boreholes and groundwater from fifty four As-contaminated well waters were collected in the Chapai-Nawabganj area of northwestern Bangladesh for geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10 to 40 m of depth) range from 2.76?C315.15 mg/l (average 48.81 mg/l). Arsenic concentration in sediments ranges from 3.26?C10 mg/kg. Vertical distribution of arsenic in both groundwater and sediments shows that maximum As concentration (462 mg/l in groundwater and 10 mg/kg in sediments) occurs at a depth of 24 m. In January 2008, 2009 and 2010, maximum As concentration occurs at the same depth. Environmental scanning electron microscope (ESEM) with EDAX was used to investigate the presence of major and trace elements in the sediments. The dominant groundwater type is Ca-HCO3 with high concentrations of As and Fe, but with low levels of NO3 ? and SO3 ?2. Statistical analysis clearly shows that As is closely associated with Fe (R2 = 0.64) and Mn (R2 = 0.91) in sediments while As is not correlated with Fe and Mn in groundwater samples. Comparatively low Fe and Mn concentrations in some groundwater, suggest that probably siderite and/or rhodochrosite precipitated as secondary mineral on the surface of the sediment particles. The correlations along with results of sequential leaching experiments suggest that reductive dissolution of FeOOH and MnOOH mediated by anaerobic bacteria represents mechanism for releasing arsenic into the groundwater.  相似文献   

18.
With the progradation of Godavari delta in the east coast of India, increase in iron (Fe) concentrations in the groundwater was observed. High concentrations of Fe (>10 mg/l) were observed in khondalite and charnockite formations. A lower portion of the Godavari river basin, viz. East Godavari district was chosen for the study of the distribution of iron with special reference to the existing geological formations and the geomorphology of the area. The concentration of iron was observed to vary from below detection limit to 69 mg/l in the groundwater while it was less than 1 mg Fe/l in river and spring waters. The Fe of river water was reduced due to seawater mixing and the electrical conductivity (EC) was increased approximately to half of the seawater conductivity. Unlike the mixing of seawater at the surface, the same seawater mixing with groundwater yielded a water having similar order of EC with relatively high Fe. Fe was inversely related with nitrate in the groundwater. Fe was found to correlate considerably better with manganese in fluvial and coastal alluvium zones. The locations having higher Fe in delta are suspected to be related to palaeo channels. The association between Fe and Mn and their negative association with NO3 may be due to the possible autotrophic denitrification that might have taken place in the subsurface.  相似文献   

19.
To understand the mechanism of arsenic mobilization from sediment to groundwater mediated by microorganism, vertical distribution of bacterial populations in aquifer sediments of the Hetao plain, Inner Mongolia was investigated by a two-step nested PCR-DGGE and 16S rRNA gene clone libraries, combined with sediment geochemistry. A borehole to 30 m depth was drilled and 11 sediment samples were collected. Lithological profile and different geochemical characteristics of sediments indicated a distinct transition of oxidizing–reducing environment along the depth of the sediment core. As(III) and Fe(II) concentrations elevated progressively from 10 m, simultaneously coupling with decrease of As(V) and Fe(III) concentrations, implying that reductive dissolution of arsenic-rich Fe(III) oxyhydroxides led to arsenic release. Results of DGGE displayed that sediment samples with higher concentrations of total arsenic and total organic carbon had lower population diversity, which suggested total arsenic concentrations were important to determine the population diversity of sediments. Bacterial communities of a sediment sample with the highest diversity and ratio of As(III) to total As were dominated by aerobic and facultative anaerobic bacteria and belonged to Alpha-, Beta-, and Gammaproteobacteria and Firmicutes group. Most of the retrieved sequences were closely related to high arsenic-resistance organisms, sulfide/thiosulfate oxidizers, denitrifiers, and aromatic hydrocarbon degraders. Thiobacillus distinctly predominated in clone library, which suggested that arsenic might be released by oxidized dissolution of sulfide minerals coupled to arsenate reduction or nitrate reduction in anaerobic condition. These data have important implications for understanding the microbially mediated arsenic mobilization in aquifers.  相似文献   

20.
《Applied Geochemistry》2004,19(7):995-1009
Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号