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1.
Arsenic(As) contamination in soil and water poses a serious threat to the ecosystem health and human beings, and is of widespread concern. The main As species found in soil and water are arsenite As(Ⅲ) and arsenate As(Ⅴ). Because As(Ⅲ) is more toxic and often more mobile than As(Ⅴ), many remediation strategies aim to oxidize As(Ⅲ) to As(Ⅴ). In the environment, the reduction of As(Ⅴ) under anaerobic conditions is mainly mediated by microorganisms, but the oxidation of As(Ⅲ) under aerobic conditio...  相似文献   

2.
Disposal of chromium(Cr) hexavalent form,Cr(VI),in soils as additions in organic fertilizers,liming materials or plant nutrient sources can be dangerous since Cr(VI) can be highly toxic to plants,animals,and humans.In order to explore soil conditions that lead to Cr(VI) generation,this study were performed using a Paleudult(Dystic Nitosol) from a region that has a high concentration of tannery operations in the Rio Grande do Sul State,southern Brazil.Three laboratory incubation experiments were carried out to examine the influences of soil moisture content and concentration of cobalt and organic matter additions on soil Cr(VI) formation and release and manganese(Mn) oxide reduction with a salt of chromium chloride(CrCl 3) and tannery sludge as inorganic and organic sources of Cr(III),respectively.The amount of Cr(III) oxidation depended on the concentration of easily reducible Mn oxides and the oxidation was more intense at the soil water contents in which Mn(III/IV) oxides were more stable.Soluble organic compounds in soil decreased Cr(VI) formation due to Cr(III) complexation.This mechanism also resulted in the decrease in the oxidation of Cr(III) due to the tannery sludge additions.Chromium(III) oxidation to Cr(VI) at the solid/solution interface involved the following mechanisms:the formation of a precursor complex on manganese(Mn) oxide surfaces,followed by electron transfer from Cr(III) to Mn(III or IV),the formation of a successor complex with Mn(II) and Cr(VI),and the breakdown of the successor complex and release of Mn(II) and Cr(VI) into the soil solution.  相似文献   

3.

Purpose  

Oxides are ubiquitous in nature and play an important role in scavenging metal ions from soils and sediments. At the common pH range of the natural environment the well-studied Fe and Al oxides mostly carry a positive charge and adsorbed amounts of heavy metals, and their desorption percentages decrease with increasing ionic strength. The less well studied but also important Mn oxides possess negative charges in the natural environment and this will lead to a different behavior. Therefore, it is useful to further investigate how the electrolyte concentration and type affect the metal ion adsorption/desorption by Mn oxides.  相似文献   

4.

Purpose  

The present work concerns the distribution of ten heavy metals (Sb, As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, and Zn) in the surrounding agricultural soils of the world largest antimony (Sb) mine in China. The objective is to explore the degree and spatial distribution of heavy metal pollution of the Sb mine-affected agricultural soils. The presented data were compared with metal concentrations in soils from mining and smelting sites in China and other countries.  相似文献   

5.

Purpose

The primary purpose of this study was to determine how flooding and draining cycles affect the redox chemistry of metal (hydr)oxides and organic matter in paddy soils and how the pH influences these processes. Our secondary purpose was to determine to what extent a geochemical thermodynamic equilibrium model can be used to predict the solubility of Mn and Fe during flooding and draining cycles in paddy soils.

Material and methods

We performed a carefully designed column experiment with two paddy soils with similar soil properties but contrasting pH. We monitored the redox potential (Eh) continuously and took soil solution samples regularly at four depths along the soil profile during two successive flooding and drainage cycles. To determine dominant mineral phases of Mn and Fe under equilibrium conditions, stability diagrams of Mn and Fe were constructed as a function of Eh and pH. Geochemical equilibrium model calculations were performed to identify Mn and Fe solubility-controlling minerals and to compare predicted total dissolved concentrations with their measured values.

Results and discussion

Flooding led to strong Eh gradients in the columns of both soils. In the acidic soil, pH increased with decreasing Eh and vice versa, whereas pH in the alkaline soil was buffered by CaCO3. In the acidic soil, Mn and Fe solubility increased during flooding due to reductive dissolution of their (hydr)oxides and decreased during drainage because of re-oxidation. In the alkaline soil, Mn and Fe solubility did not increase during flooding due to Mn(II) and Fe(II) precipitation as MnCO3, FeCO3, and FeS. The predicted levels of soluble Mn and Fe in the acidic soil were much higher than their measured values, but predictions and measurements were rather similar in the alkaline soil. This difference is likely due to kinetically limited reductive dissolution of Mn and Fe (hydr)oxides in the acidic soil. During flooding, the solubility of dissolved organic matter increased in both soils, probably because of reductive dissolution of Fe (hydr)oxides and the observed increase in pH.

Conclusions

Under alternating flooding and draining conditions, the pH greatly affected Mn and Fe solubility via influencing either reductive dissolution or carbonate formation. Comparison between measurements and geochemical equilibrium model predictions revealed that reductive dissolution of Mn and Fe (hydr)oxides was kinetically limited in the acidic soil. Therefore, when applying such models to systems with changing redox conditions, such rate-limiting reactions should be parameterized and implemented to enable more accurate predictions of Mn and Fe solubility.  相似文献   

6.

Purpose

Arsenite and arsenate leaching from iron (hydr)oxides is one major parameter affecting the mobility of arsenic in the natural environment. In the process of arsenic transfer to groundwater, the retention capacity of arsenic by different iron (hydr)oxides needs to be investigated. The aim of this study is to determine the retention capacity of arsenite or arsenate from the ferrihydrite, lepidocrocite, or magnetite-coated sand column in the leaching process as well as the influence factors on leaching.

Materials and methods

The leaching of arsenite and arsenate from columns loaded with ferrihydrite, magnetite, or lepidocrocite-coated quartz sand was examined, and the influence factors such as pH, phosphate, and humic acid (HA) contents on leaching and retention were also investigated.

Results and discussion

The retention performance of As(III) and As(V) depended on the type of iron (hydr)oxides: ferrihydrite?>?magnetite?>?lepidocrocite. The retention capacities of As(III) and As(V) by amorphous ferrihydrite versus magnetite and lepidocrocite are 3.25, 5.63 (As(III)) and 1.75, 3.65 (As(V)) times higher. The retention capacity of arsenic is largely affected by the pH of leaching solutions. The retention of As(III) by ferrihydrite is efficient in near-neutral or slightly acidic environments. The addition of phosphate or HA significantly affected the leaching and retention. The addition of phosphate severely inhibited the leaching and retention of As(III) and As(V) by ferrihydrite, and the inhibitory effect was more obvious along with the increase of phosphate concentration. The retention of As(III) and As(V) by ferrihydrite was significantly enhanced by the addition of low-dose HA but was inhibited by the addition of excessive HA.

Conclusions

Retention performance of As(III) and As(V) from a ferrihydrite-coated sand column is greater than a magnetite- or a lepidocrocite-coated sand column, and the influence factors such as pH, phosphate, and HA affect the leaching and retention of As(III) and As(V). The results theoretically underlie the application of iron (hydr)oxide in arsenic pollution control.
  相似文献   

7.

Purpose

Chromium, a potentially harmful element, occurs commonly within the urban sediment cascade as a result of abundant industrial and transport-related sources. The risks that Cr-bearing particles pose to ecosystems and humans depend on the solid-phase chemical speciation of Cr and its environmental mobility. In this study, we adopt an integrated geochemical approach to investigate and determine the long-term fate of Cr in the urban sediment cascade.

Materials and methods

We use bulk chemical digests, sequential chemical extraction analysis, electron microscopy, electron microprobe and microfocus XANES analysis to describe the solid-phase speciation, geochemical characteristics and potential long-term behaviour of Cr in urban particulate matter from both aquatic sediment and road dust sediment (RDS) in Manchester, UK.

Results and discussion

Cr-bearing grains within RDS and aquatic sediment are predominantly iron oxides and alumino-silicate glass grains. Electron microprobe analysis indicates Cr concentrations up to 3300 and 133,400 μg g?1 in the RDS and aquatic grains, respectively. XANES analysis indicates that Cr(III) is the dominant oxidation state, with only trace amounts of Cr(VI). Importantly, Cr speciation does not appear to have changed between sedimentary environments and the dominance of Cr(III) suggests limited bioavailability or toxicity under predominant environmental (anoxic and neutral pH) conditions in the aquatic sediment sink. Furthermore, geochemical analyses suggest the environmental mobility of Cr in the aquatic sediment sink is low (compared to other toxic metals) due to its association mainly with alumino-silicate glass grains and its inclusion as an integral part of the glass structure.

Conclusions

Industrial glass grains are a major component of urban sediment worldwide. The speciation and geochemical investigations performed in this study suggest most Cr within the urban sediment cascade may be resistant to environmental processes that could mobilise other toxic metals.
  相似文献   

8.

Purpose  

Fe(III) has been reported as a strictly competitive electron acceptor with respect to other substrate reductions by dissimilatory Fe(III)-reducing bacteria (DIRB). However, the effect of Fe(III) oxides on the substrate reduction by other microorganisms remain unknown. The aims of this study were to investigate the effects of iron oxides on the nitrate reduction and current generation by Bacillus sp., in which the nitrate and carbon anodes served as soluble and insoluble electron acceptors, respectively.  相似文献   

9.

Purpose

The aim was to study Cu (II), Zn (II), and Pb (II) forms in technogenically transformed soils adjacent to the Karabashmed copper smelter.

Materials and methods

Studies were performed in the plume zone of the Karabash smelter and in the floodplains of Ryzhii Brook and Sak-Egla River. Geomorphological and geochemical migration processes prevail in technogenic landscapes. The differentiation of landscape-geochemical conditions plays the dominant role, which determines the localization of metals. The total Mn, Cr, Ni, Cu, Zn, Pb, Cd, and As contents and the macroelement compositions of soils were determined by X-ray fluorescence. The composition of Cu, Pb, and Zn compounds in soils was determined by the Tessier sequential fractionation. The determination of the geochemical fractions of heavy metals in soils is a key issue in the study of their mobility. The metals were fractionated into the following five fractions: exchangeable, bound to carbonates, bound to Fe and Mn oxides, bound to organic matter, and residual fractions.

Results and discussion

It is shown that the total Zn and As contents in the 0- to 5-cm layer of soils on monitoring plots exceed their lithosphere clarks in hundreds of times, and the total Cu, Pb, and Cr contents exceed their lithosphere clarks in tens of times. Factors and processes controlling the distribution and transport of Cu, Pb, and Zn forms in soils were determined. According to landscape-geochemical differentiation, the eluvial (automorphic) catena (plot T4) takes the main technogenic load of dust fallouts from the Karabash copper smelter. The accumulation of material brought from above and the geochemical precipitation of discharges from tailings dumps occur in superaqual catenas (plots T1, T2, and T3). In the technogenically transformed soils, the basic stabilizers of the mobility of Cu is organic matter, for Pb it is Fe-Mn (hydro) oxides, and for Zn - it is clay minerals.

Conclusions

The distributions of Cu, Zn, and Pb forms in the studied technogenically transformed soils are due to a number of factors: First, these are the composition of technogenic pollutants contaminating ecosystems and the time during which the contamination occurred, and second, this is the combination of physicochemical properties controlling the buffer properties of the polydisperse system of soils and parent materials.
  相似文献   

10.

Background  

Aims. Pollution of sediment and soil by heavy metals is still an environmental problem. In order to assess the actual environmental risk, the mobile and biologically available content of heavy metals needs to be determined rather than the total content. This requires an analytical strategy preserving the actual binding forms of the heavy metals. Sampling and sample preparation are usually carried out in the presence of oxygen. As a consequence, oxidation of the metal and/or its binding partners is possible under these conditions, changing the original binding character. Therefore, sampling and sample preparation must be performed under inert conditions. The influence of atmospheric oxygen on the heavy metal mobility in sediment and soil for Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn is shown for samples of different origin. By means of a case study, an alternative for the extensive inert sampling and sample preparation is given; also, a mobility correction factor for the heavy metals mentioned is determined.  相似文献   

11.

Purpose  

Dissimilatory iron reduction is an important iron biogeochemical process in subsurface soils. Many researchers have studied the effects of various factors on this process. However, this process in the natural environment is complicated; thus, all the factors should be investigated systematically and simultaneously. The aims of this study were to investigate the effects of Fe(III) availability, surface areas, and crystallinity on Fe(III) reduction in different buffers and to characterize the surface properties of iron minerals.  相似文献   

12.

Purpose

Remediation of soils contaminated with Cr (as Cr(III) complexes/precipitates and/or Cr(VI) oxyanion) and cationic metals (Cu, Ni, Zn, and Pb) by ethylenediaminetetraacetate (EDTA) flushing has been challenging and rarely investigated. This study aimed to evaluate the efficiency of EDTA flushing for metal extraction of soil from an electroplating site, with a specific focus on chromium release and soil dissolution.

Materials and methods

Column flushing tests were performed on a sandy soil contaminated by electroplating activities in the field. Three EDTA concentrations (5, 10, and 20 mM) and flow interruptions were employed to investigate the operation of EDTA flushing.

Results and discussion

Results demonstrated that Cr, Cu, and Ni were continuously released along with dissolution of Fe, Al, Mg, and Mn throughout the entire flushing process (up to 600 pore volumes), whereas Zn and Pb removal primarily occurred in the first 50–200 pore volumes. By comparing the Cr and Fe release patterns, the observed Cr release by EDTA flushing possibly resulted from a combination of dissolution of Fe oxides, dissolution of metal–chromate precipitates, and ligand competition for the surface sites (substitution reaction). The latter two mechanisms appeared to be more influential at the early stage. It was also revealed that soil dissolution was predominant, and metal extraction became inefficient at the later stage of flushing, especially with the concentrated EDTA solution. On the other hand, when the flushing process was temporarily paused (i.e., flow interruptions), Cr, Cu, Ni, and Zn concentrations elevated, whereas Pb levels in the effluent decreased, indicating the significance of rate-limited metal exchange of newly formed metal–EDTA complexes.

Conclusions

In consideration of EDTA utilization efficiency and potential ecological risks, diluted EDTA solution is recommended for field applications.  相似文献   

13.
Mineralogy and geochemistry of manganese: A review of publications   总被引:2,自引:0,他引:2  
The relatively low hydrolyzing capacity of Mn(II) leads to the formation of oxides rather than hydroxides of this element in soils. The formation of vernadite, birnessite, todorokite, and lithiophorite was recently proved in soils. Vernadite with an Fe admixture and Mn-containing iron minerals, i.e., ferroxyhyte, ferrihydrite, and magnetite, were also found. Fe-vernadite and Mn-ferroxyhyte are the most abundant in soils. Manganese oxidogenesis is the most intensely pronounced in the soils of steppe and forest-steppe zones, in which the assemblage of Mn-containing minerals is wider than in taiga soils. Carbonates are able to inhibit the development of Mn oxidogenesis. The bulk of Mn compounds are confined to the silt rather than to the clay fraction, since manganese oxides are negatively charged in the pH interval typical of the bulk of soils. Manganese oxides are able to retain heavy metals, i.e., Co, Ni, Zn, and others. The active participation of Mn oxides in Cr(III) oxidation raises its mobility and toxicity. Manganese oxides may favor humus formation by taking part in phenol oxidation.  相似文献   

14.

Purpose

The use of fossil fuels, cement production and the reduction of forest areas cause a high amount of CO2 emissions to the atmosphere which in turn causes the ocean to be acidified. Acidity of seawater can directly change sediment properties. It is expected that the average pH value of the ocean surface water will decrease between 0.3 and 0.5 pH units according to the projection to year 2100. This study aimed to make a contribution to the understanding of long-term pollution trends. In the study, sediment samples from Neolithic Era, Early Byzantine Era and Byzantine Era from archaeological excavations jointly conducted by Istanbul Archaeological Museums and the Istanbul University Department of Conservation of Underwater Cultural Heritages were investigated.

Materials and methods

The sediment samples were taken from ancient Theodosius Harbour (5000 BC). Major elements (Si, Al, Fe, Mg, Ca, K, Na, Mn, Ti), rare earth elements (Tb, Yb, Eu, Dy, Tm) and toxic elements (As, Cr, Co, Cu, Ni, Pb and Zn) in sediment samples were determined by X-ray fluorescence spectrometer. The chemical abundance of the ancient sediments was evaluated with the ecological risk factor and geo-accumulation index.

Results and discussion

The sediment samples from the Neolithic Era reflect the contribution of both parent rock and also anthropogenic pollution. In the Early Byzantine and Byzantine Era, the development of the industry has increased the basic element concentrations in the environment and potential ecological risk and geo-accumulation indices. As, Cu, Cr, Zn, Ni and Co contents of Neolithic Era samples were found to be lower than Early Byzantine and Byzantine Era.

Conclusions

The obtained the results showed that the toxic elements in the Neolithic Era, which the industry never developed, started to rise and increased concentrations of Ni by about two and a half times, Zn four times, Pb two times, Cr two times, Co six times and As three times in the Early Byzantine and Byzantine Eras. The concentrations of major elements (Al, Ba, Ca, Fe, K, Mg, Mn, Na, Si) did not show any significant difference during these three eras.
  相似文献   

15.

Purpose  

The oxidation of ammonium (NH4+) to nitrate (NO3) in the soil is an important biogeochemical process, which has major environmental implications as it can contribute to NO3 leaching and nitrous oxide (N2O) emissions. Nitrification inhibitors have been used to slow down this process to reduce NO3 leaching and N2O emissions from agricultural land. The objective of this study was to determine the effectiveness of a liquid formulation of 3,4-Dimethylpyrazole phosphate (DMPP) compared with a dicyandiamide (DCD) solution in inhibiting the growth of ammonium-oxidizing bacteria (AOB) and ammonium oxidizing archaea (AOA) and slowing down the rate of NH4+ oxidation in soil.  相似文献   

16.

Purpose

Todorokite is one common manganese oxide in soils and sediments and is commonly formed from layered Na-buserite. Aging processes can alter the physicochemical properties of freshly formed Na-buserite in natural environments. However, it is not clear whether and how aging affects the formation of todorokites. In the present paper, Na-buserite with aging treatment was employed to prepare todorokite at atmospheric pressure to investigate the effects of aging treatment of Na-buserite on the formation of todorokite.

Materials and methods

Four aged Na-buserite samples, which are produced through oxidation of Mn2+ in concentrated NaOH medium by O2 with aging for 3, 6, 9, and 12 months, were employed to investigate the effects of aging processes on the transformation from Na-buserite to todorokite by Mg2+-templating reaction at atmospheric pressure. The manganese oxides were examined using X-ray diffraction (XRD), elemental analysis, determinations of the average manganese oxidation number, infrared spectroscopy (IR), and transmission electron microscopy (TEM).

Results and discussion

The XRD, IR, and elemental analyses indicate that aging treatment can alter the substructure of the freshly synthesized Na-buserite. During the aging process, some of the Mn(III) may migrate into the interlayer region or disproportionate to form Mn2+ and Mn4+ from the layer of Na-buserite and the concomitant formation of layer vacancies. The interlayer Mn3+ or Mn2+ occupied above or below the layer vacancy sites and become corner-sharing octahedral. XRD analyses and TEM clearly show that the transformation from Na-buserite to todorokite was promoted by aging treatments. The alterations of substructure of aged Na-buserites can promote the rearrangement of manganese to construct a tunnel structure during the transformation from layered manganese oxides to tunnel-structure todorokite at atmospheric pressure.

Conclusions

The transformation from Na-buserite to todorokite was promoted by aging treatments at atmospheric pressure, and it is more suitable to explore the origination of natural todorokite in Earth surface environments using aged layered manganese oxides.  相似文献   

17.
Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH2PO4–K2HPO4 buffer solutions (0.015 up to 0.2 mol l?1), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l?1 and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g?1 of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g?1.  相似文献   

18.
Manganese dioxide (birnessite) was coated with two levels of Fe and Al oxides and CaCO3, and the influence of these coatings on the surface features and the reactivity of MnO2 with respect to the oxidation and sorption of As(III) (arsenite) was examined. For all untreated and coated MnO2 samples, the depletion (oxidation plus sorption) of As(III) by the samples follows first-order kinetics. The rate constants are smaller for the samples with the high levels of coating of Fe and Al oxides and CaCO3 on MnO2 than they are for the untreated MnO2 and the MnO2 with the low levels of coating. The extent of masking of the electron-accepting sites on the MnO2 for converting the toxic As(III) to the less toxic As(V) significantly varies with the kinds and levels of coatings. Coatings of Fe and A1 oxides and CaCO3, on MnO2 distinctively affect the sorption of As. Manganese oxide evidently catalyzes the sorption of As by Al oxide through oxidation of As(III) to As(V). The relative affinities of the oxides of Mn, Fe, and Al and CaCO3, toward As(III) and As(V) account for the coating effects.  相似文献   

19.

Purpose  

Sulfur is distributed widely in soils and sediments. Sulfide oxidation causes acid mine wastewater, toxicity, and corrosion. Manganese oxide minerals usually affect the migration, transformation, and fate of sulfur. To understand the oxidation behaviors of S2− and influence factors, reaction process and kinetics were investigated by using different manganese oxides.  相似文献   

20.
The influence of some complexing agents of (poly)aminopolycarboxylic acids (diethylenetriaminopentaacetic acid (DTPA), ethylenediaminotetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) on the sorption of Cu2+ by crystal and amorphous (hydr)oxides of Fe(III), Al(III), and Mn(IV) that are widespread mineral components of soils was studied. The obtained results are considered in terms of complex-formation in the solution and on the sorbent’s surface. The effect of the complexing agents on the metal sorption (mobilization/immobilization) is determined by (1) the stability, structure, and sorption capability of compexonates formed in the solution; (2) the acidity, and (3) the nature of the sorbent. The desorption effect on Cu2+ cations was found to change in the following sequence of complexing agents: EDTA > DTPA ? NTA > IDA. The high-dentate complexing agents (EDTA, DTPA) had the greatest impact on ?u2+ cations bound with crystalline (hydr)oxides of Fe, Al, and Mn. The low denticity of the complexing agents (IDA, NTA) and binding of ?u2+ with amorphous sorbents leads to the weakening of desorption. The decrease in acidity promoted the mobilization of the metal under the influence of complexing agents; the increase in acidity caused its immobilization. The growth in the mobility of heavy metals bound with soil (hydr)oxides of Fe, Al, and Mn due to the complexing agents entering the surface and ground water is considered a factor of ecological risk.  相似文献   

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