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1.
The kinetics of Cr(Ⅵ) reduction by sulfide in soil suspensions with various pHs, soil compositions, and Fe(Ⅱ) concentrations was examined using batch anaeroblc experimental systems at constant temperature. The results showed that the reaction rate of Cr(Ⅵ) reduction was in the order of red soil 〈 yellow-brown soil 〈 chernozem and was proportional to the concentration of HCl-extractable iron in the soils. Dissolved and adsorbed iron in soil suspensions played an important role in accelerating Cr(Ⅵ) reduction. The reaction involved in the Cr(Ⅵ) reduction by Fe(Ⅱ) to produce Fe(ⅡI), which was reduced to Fe(Ⅱ) again by sulfide, could represent the catalytic pathway until about 70% of the initially present Cr(Ⅵ) was reduced. The catalysis occurred because the one-step reduction of Cr(Ⅵ) by sulfide was slower than the two-step process consisting of rapid Cr(Ⅵ) reduction by Fe(Ⅱ) followed by Fe(Ⅲ) reduction by sulfide. In essence, Fe(Ⅱ)/Fe(Ⅲ) species shuttle electrons from sulfide to Cr(Ⅵ), facilitating the reaction. The effect of iron, however, could be completely blocked by adding a strong Fe(Ⅱ)-complexing ligand, 1,10-phenanthroline, to the soil suspensions. In all the experiments, initial sulfide concentration was much higher than initial Cr(Ⅵ) concentration. The plots of In e[Cr(Ⅵ)] versus reaction time were linear up to approximately 70% of Cr(Ⅵ) reduction, suggesting a first-order reaction kinetics with respect to Cr(Ⅵ). Elemental sulfur, the product of sulfide oxidation, was found to accelerate Cr(Ⅵ) reduction at a later stage of the reaction, resulting in deviation from linearity for the In c[Cr(Ⅵ)] versus time plots.  相似文献   

2.
The objective of this research was to assess the hexavalent chromium (Cr(VI)) reducing efficiency of sulfur-based inorganic agents including calcium polysulfide (CPS), iron sulfide (FeS), pyrite (FeS2) and sodium sulfide (Na2S) in three soils. An alkaline soil (soil 1), a neutral soil (soil 2) and a slightly acid soil (soil 3) constituted the investigated soils. The soils were spiked with two levels of Cr(VI) (100 and 500 mg Cr(VI) kg?1 soil) and incubated at field capacity (FC) for one month. Then, CPS, FeS, FeS2 and Na2S were added at 0, 5 and 10 g kg?1 and the concentrations of exchangeable Cr(VI) were measured after 0.5, 4, 48 and 168 h in a batch experiment. The pH and organic carbon content of the soils played predominant role in Cr(VI) self-reduction by the soil itself. Complete self-reduction of Cr(VI) from soils 1, 2 and 3 was achieved at maximum Cr(VI) levels of 1, 50 and 500 mg kg?1, respectively. Therefore, the concentration of Cr(VI) should not exceed the given levels in order to ensure that Cr(VI) is not released into the environment from contaminated sites. Moreover, decreasing pH in the alkaline soil caused significant increase of Cr(VI) reducing efficiency. Na2S, CPS and FeS, in contrast to FeS2, were efficient Cr(VI) reducing agents in all three soils. For all added amendments the following order of Cr(VI) reducing capacity was observed: Na2S > CPS > FeS > FeS2 in soil 1, Na2S ? CPS ~ FeS > FeS2 in soil 2 and Na2S ? FeS > CPS ~ FeS2 in soil 3.  相似文献   

3.
Reduction of Cr(VI) by soil humic acids   总被引:1,自引:0,他引:1  
The rate of hexavalent chromium reduction by a soil humic acid (SHA) was investigated in aqueous solutions where concentrations of Cr(VI), H+, and SHA were independently varied. Rate experiments were done with a large excess of SHA over Cr(VI). Rates of reduction depend strongly on [H+], increasing with decreasing pH. Typical Cr(VI)-SHA reactions display a nonlinear reduction of Cr(VI) with time that cannot be modelled with simple first- or second-order rate equations. An empirical rate equation is developed for Cr(VI)-soil humic acid reactions over a range of experimental conditions. The model is in part based on a reactive continuum concept developed for soil fulvic acids. The rate equation describing Cr(VI) reduction by SHA is: R= -(k0+k[H+]1/2)[HCrO4?]1/2Xe?1, where k0 is (8·3 ± 1·2) × 10?12, s?1k is (2·04 ± 0·05) × 10?9 l1/2 mol?1/2 s?1, and Xe is the equivalent fraction of SHA oxidized. The rate equation adequately models Cr(VI) reduction in an experiment with [Cr(VI)]0 four times greater than the maximum concentration used in its derivation. Cr(VI) reduction at pH 3 by two other SHAs can also be modelled using the rate equation. The difference between the rate coefficients for the humic acid and the fulvic acid from the same soil was greater than the difference in the rate coefficients for humic acids from different soils.  相似文献   

4.
The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO4 2– and PO4 3–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K f was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.  相似文献   

5.
In the present paper, α-FeOOH and α-Fe(Al)OOH were prepared, and the adsorption of Cr(VI) on the two samples was investigated. The influence of pH, initial concentration, and some anions such as SO4 2?, H2PO4 ?, C2O4 2?, CO3 2?, and SiO3 2? on the adsorption of Cr(VI) on α-FeOOH and α-Fe(Al)OOH was studied by batch techniques. The results show that the adsorption capacity of Cr(VI) on α-Fe(Al)OOH increases with the introduction of aluminum, but decreases with the increase of pH. The adsorption irreversibility of Cr(VI) on α-Fe(Al)OOH is much higher than that on pure α-FeOOH. The adsorbed Cr(VI) species mainly exists in the form of *Fe(wk)-OHCrO4 2? on the surface of the samples. With the presence of SiO3 2?, CO3 2?, C2O4 2?, SO4 2?, and H2PO4 ?, the binding of Cr(VI) is inhibited by different degree. The inhibition of those anions is larger in the pure goethite than that in the Al-substituted goethite system. After Al was introduced into α-FeOOH, Cr(VI) ions are preferentially adsorbed on Al sites rather than Fe sites on α-Fe(Al)OOH.  相似文献   

6.
Adsorption of Cr (VI) as CDC-complex from aqueous solution by activated C has been investigated. Factors like pH and presence of Cr (III) which affect the adsorption of CDC-complex were studied. The increase in particle size and surface area of activated C does not enhance the removal of CDC-complex. For different concentrations of Cr, the optimum quantity of Diphenyl Carbazide has been determined. The reduced Cr e.g. Cr (III) decreases the CDC-complex removal. The Langmuir and Freundlich isotherms constant as calculated are γm=1.8932 and b=0.2305 and n=0.036, log K=0.0266, respectively.  相似文献   

7.
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   

8.
The influence of culture medium composition on chromium(VI) quantification according to diphenylcarbazide (DPC) colorimetric determination was evaluated. Considering the eventual biospeciation of Cr(VI) as a mechanism of microbial bioremediation, the possibility to quantify Cr(III) in culture medium was also explored. Yeast nitrogen base (YNB) was identified as the least interferent culture medium for Cr(VI) quantification by DPC and it was applied to compare different strategies for Cr(III) oxidation. The most appropriate oxidation protocol consisted in the reaction with 80 mM KIO4 at room temperature for 30 min prior to DPC. Parameters like basal culture medium (vitamins + salts + oligoelements), C and N source were systematically evaluated, either independently or in combination. Results demonstrated that C source was the most interferent culture medium component, being the use of sucrose preferable to glucose. A medium arbitrarily named as YNB′ (YNB without amino acids and ammonium sulfate plus 50 g L?1 sucrose and 0.6 g L?1 (NH4)2SO4) was defined for Cr(VI)-amended fungal cultures. Kinetics of growth, Cr(VI) removal, and nutrient consumption for isolates A. pullulans VR-8, filamentous fungus PMF-1, and Lecythophora sp. NGV-1 were obtained. The order of Cr(VI) removal efficiency was as follows: A. pullulans VR-8 > Lecythophora sp. NGV-1 > filamentous fungus PMF-1, and a similar trend was observed for biomass yield and nutrients consumption. Studies on biospeciation by means of the selected Cr(III) oxidation protocol were unsuccessful, leading to Cr(VI) values much lower than expected. It revealed that this kind of protocols should be cautiously evaluated when studying microbial Cr(VI) bioremediation.  相似文献   

9.
The pH dependency of Cd, Cr(III), Cr(VI), Hg, and Pb uptake by 14 different types of minerals and soil materials has been studied. The solids were interacted with metal solutions separately in a batch procedure, and the percentage of metal uptake of different metal-solid combinations was compared and evaluated. The results were quantified by the pH values at which 10, 50 and 90% of the metal uptake took place. Physical and chemical characteristics of the solids were correlated with metal uptake. The results verify the importance of geochemical parameters of soils such as organic content, type of clay mineral, presence of complexing ions, and redox-potential for controlling metal uptake. Retention of Cd, Cr(VI), Hg, and Pb was found to be strongly dependent on organic content of the materials studied. Montmorillonite (in bentonite and smectite) showed the highest uptake of Cd, Cr(III) and Pb among all minerals and soil materials, while illite and kaolinite showed lower uptake than the soils. At low pH, the uptake percentage of Cr(VI) by organic soils was higher than that of any of the other metal ions. The uptake of Hg was low in comparison to other cations, which may be explained by formation of soluble Hg(CI)2° or Hg(CI)4 2? complexes.  相似文献   

10.
Abstract

The adsorption of Cr(VI) ion on synthetic hydrated oxides of iron (goethite (α-FeOOH) and lepidocrocite (γ-FeOOH)) with different crystallinities was studied in order to remove the Cr(VI) ion from polluted water. At pH 4.5, the amounts of the adsorbed Cr(V1) ion on goethite and lepidocrocite were 51.9 and 62.2 mmol g?, respectively. Probably, this is due to the fact that the structure of lepidocrocite is more open than that of goethite. Lepidocrocite, therefore, is more effective for the removal of Cr( V1) ion from Cr(Vl)-contaminated and acidic groundwater and sewage.  相似文献   

11.
Increasing the mobilization and root uptake of chromium (Cr) by synthetic and plant‐borne chelators might be relevant for the design of phytoremediation strategies on Cr‐contaminated sites. Short‐term uptake studies in maize roots supplied with 51CrCl3 or 51Cr(III)‐EDTA led to higher apoplastic Cr contents in plant roots supplied with 51CrCl3 and in Fe‐sufficient plants relative to Fe‐deficient plants, indicating that Fe stimulated co‐precipitation of Cr. Concentration‐dependent retention of Cr in a methanol:chloroform‐treated cell‐wall fraction was still saturable and in agreement with the predicted tendency of Cr(III) to precipitate as Cr(OH)3. To investigate a possible stimulation of Cr(III) uptake by phytosiderophores, Fe‐deficient maize roots were exposed for 6 d to Cr(III)‐EDTA or Cr(III)‐DMA (2'‐deoxymugineic acid). Relative to plants without Cr supply, the supply of both chelated Cr species in a subtoxic concentration of 1 µM resulted in alleviation of Fe deficiency–induced chlorosis and higher Cr accumulation. Long‐term Cr accumulation from Cr(III)‐DMA was similar to that from Cr(III)‐EDTA, and Cr uptake from both chelates was not altered in the maize mutant ys1, which is defective in metal‐phytosiderophore uptake. We therefore conclude that phytosiderophores increase Cr solubility similar to synthetic chelators like EDTA, but do not additionally contribute to Cr(III) uptake from Cr‐contaminated sites.  相似文献   

12.
Abstract

Chromium (Cr) appears in two stable forms in nature as Cr(III) and Cr(VI). Hexavalent chromium (CrO4 2‐; Cr2O7 2‐) is very toxic and carcinogenic, while inorganic Cr(III), however, is essential for mammals. Only two methods, atomic absorption and inductively coupled plasma atomic emission (ICP) spectrometry, provide information on the total amount of Cr in a test solution. This is the reason that several efforts have been made with regard to Cr speciation. Either an acidic or a basic activated aluminum oxide and a reversed phase C‐18 column or an ion exchanger column are used for the separation of chromium(III) from chromium(VI) in FIA and HPLC analyses. In our experiments, acidic‐activated aluminum oxide was used for separation. This alumina was placed into a silicon tube and connected to an ICP spectrometer between the nebulizer and peristaltic pump. The average grain size of the alumina was large enough that the solution could be pumped through the micro column. Acidic‐activated aluminum oxide in the 2.0 to 8.0 pH range adsorbs the chromate anion but not the Cr(III) cation. During this stage, the Cr(III) content of a sample is measurable. The adsorbed chromate can be eluted with a strong acid. The height or area of the elution peak can be used for the calibration of Cr(VI). Detection limits of 4 μg/kg and 0.5 μg/kg were obtained for Cr(III) and Cr(VI), respectively. The effects of sulphate and phosphate anions on the surface of the alumina on chromate adsorption were also evaluated. This method was used for the measurement of Cr(VI) concentration by 0.01M CaCl2 extraction of soil.  相似文献   

13.
This paper presents a comparative study of the performance of ferrate(VI), FeO 4 2? , and ferric, Fe(III), towards wastewater treatment. The ferrate(VI) was produced by electrochemical synthesis, using steel electrodes in a 16 M NaOH solution. Domestic wastewater collected from Hailsham North Wastewater Treatment Works was treated with ferrate(VI) and ferric sulphate (Fe(III)). Samples were analysed for suspended solids, chemical oxygen demand (COD), biochemical oxygen demand (BOD) and P removal. Results for low doses of Fe(VI) were validated via a reproducibility study. Removal of phosphorous reached 40% with a Fe(VI) dose as low as 0.01 mg/L compared to 25% removal with 10 mg/L of Fe(III). For lower doses (<1 mg/L as Fe), Fe(VI) can achieve between 60% and 80% removals of SS and COD, but Fe(III) performed even not as well as the control sample where no iron chemical was dosed. The ferrate solution was found to be stable for a maximum of 50 min, beyond which Fe(VI) is reduced to less oxidant species. This provided the maximum allowed storage time of the electrochemically produced ferrate(VI) solution. Results demonstrated that low addition of ferrate(VI) leads to good removal of P, BOD, COD and suspended solids from wastewater compared to ferric addition and further studies could bring an optimisation of the dosage and treatment.  相似文献   

14.
The sorption of Pb(II), Cr(III) and Cr(VI) from aqueous solution using alum-derived water treatment sludge was investigated using the batch adsorption technique. Samples of sludge from two separate water treatment plants were used (one where alum was used alone and one where it was used in combination with activated C). The sorption characteristics of the two samples were generally very similar. Sorption isotherm data for all three ions fitted equally well to both Freundlich and Langmuir equations. Maximum sorption capacity and indices of sorption intensity both followed the order: Cr(III)?>?Pb(II)?>?Cr(VI). Kinetic data correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. Sorption was pH-dependant with percentage sorption of Cr(III) and Pb(II) increasing from <30% to 100% between pH?3 and 6 whilst that of Cr(VI) declined greatly between pH?5 and 8. HNO3 at a concentration of 0.1?M was effective at removing sorbed Cr(III) and Pb(II) from the sludge surfaces and regeneration was successful for eight sorption/removal cycles. It was concluded that water treatment sludge is a suitable material from which to develop a low-cost adsorbent for removal of Cr and Pb from wastewater streams.  相似文献   

15.
Abstract

The effects of heating on the solubility and plant uptake of Cr from three soils variously influenced by ultramafic parent materials were evaluated. Chromium extracted by 2 M HNO3 and by M KCl increased with degree of serpentine influence and with temperature of ignition in air. In contrast, solubility of the element was only slightly influenced by ignition in a N2 atmosphere. Heating enhanced the solubility of soil Cr by at least two oxidative reactions: (1) the destruction of a relatively heat‐stable, probably organic, complex with the release of Cr(III), and (2) the oxidation of free Cr(III) to Cr(VI).

Corn (Zea mays L.) grew poorly in the ignited soils, but normally in ignited and leached soils. Growth depression from ignition was related to shoot Cr levels (r2 = 0.494) and is attributed to the readily absorbed and translocated chromate formed at elevated temperatures. Under more usual soil conditions, as in the untreated and ignited then leached soils, the less readily soluble forms of the element are the principal contributors to available Cr.  相似文献   

16.
A study has been conducted on the transformation of Cr(III) and Cr(VI) in simulated natural water conditions. It has been found that these forms are readily interconvertible under natural water conditions. The results of this study indicate that Cr(VI) is reduced by Fe(II), dissolved sulfides, and certain organic compounds with sulfhydryl groups, while Cr(III) is oxidized by a large excess of MnO2 and at a slow rate by Oz under conditions approximating those in natural waters. Based on the results of these studies, water quality standards for Cr should be based on total Cr rather than on Cr(VI), as has been frequently done in the past.  相似文献   

17.
Hexavalent chromium [Cr(VI)] is highly toxic, teratogenic and carcinogenic to man and other animals. Some bacterial species have the ability to reduce Cr(VI) to a stable speciation state of trivalent chromium [Cr(III)], which is insoluble and comparatively less toxic. Therefore, the reduction of Cr(VI) thus provides potential as a means for environmental bioremediation of Cr(VI) pollution. In the present study bacteria isolated from chromium and diesel contaminated sites were found to have the ability to rapidly reduce highly toxic concentrations of Cr(VI) to Cr(III) when grown in minimal medium supplemented with glucose as the sole carbon source. Partial chromate reductase gene sequences were retrieved after PCR amplification of genomic DNA extracted from three Gram positive isolates which were highly similar (>99% sequence similarity) to chromate reductase genes found in Gram negative bacteria, more specifically those identified from Escherichia coli and Shigella spp. whole-genome studies. The isolated bacteria were putatively identified by 16S rRNA gene sequencing as Arthrobacter aurescens strain MM10, Bacillus atrophaeus strain MM20, and Rhodococcus erythropolis strain MM30.  相似文献   

18.
The effect of cadmium(II) on the transformation of ferrihydrite[with Cd(II):Fe(III) ratios ranging from 0 to 5 mole %] in neutral and alkaline media (pH 7-11), combined with the effects of electrolyte type (NO3 -, Cl-, and SO4 -2), was investigated at 20 °C over a period of 1 yr. The presence of Cd(II) strongly retards the conversion of ferrihydrite into hematite and/or goethite at pH 7–10, with decreases in the rate of transformation dependent on the amountof Cd(II). At a Cd(II):Fe(III) mole ratio of 1%, the transformation rate is NO3 - > Cl- > SO4 -2, which correlates with the relative affinitiesof the anions for the ferrihydrite surface. The presence of Cd(II) promotes hematite formation at pH 9 and 10, whereas atpH 11 goethite is almost the sole product. With increasinginitial Cd(II) concentrations, increasing incorporationof Cd(II) into the products is observed. For 5 mole %Cd(II), ~ 2.5 mole % of Cd(II) is included in thetransformation products, principally hematite, while at pH 11, with 1 mole % Cd(II), all of the Cd(II) incorporates into thegoethite lattice. Transmission electron micrographs show that the presence of Cd(II) leads to a reduction in size and promotesthe twinning of goethite crystals, and can result in ellipsoidal-shaped hematite crystals. Leachability of Cd(II) fromfresh and aged coprecipitated Cd(II)-ferrihyrdite is dependent onthe extent of transformation of the ferrihydrite, with 70–90% of the Cd(II) leachable from ferrihydrite, while goethite is ableto incorporate and remove more Cd(II) than hematite.  相似文献   

19.
Bush beans (Phaseolus vulgaris L. cv Contender) were grown on perlite with nutrient solution and 0, 1, 2.5 and 5 ppm levels of Na2CrO4 Significant decrease of top growth and chlorosis in trifoliated leaves were observed for 2.5 and 5 ppm Cr, with Cr concentrations (μg/g) in tops:≥ 12.1, in roots:≥ 509.9. Cr decreased K, Na, Mg and Fe concentrations, and increased P and Mn concentrations in roots. In tops decreased N, K, Na and Fe concentrations and increased Mn and Ca concentrations were observed, Translocation of P, Zn, Cu and Fe was inhibited; Ca and Mn translocation was generally enhanced. P/Fe ratio was increased up to 60% in chlorotic plants, indicating a shift from Fe2+ to Fe3+.  相似文献   

20.
The influence of inoculum preparation and cell density on the efficiency of Cr(VI) removal was assessed with two chromate-resistant yeasts, Pichia jadinii M9 and Pichia anomala M10, isolated from textile wastewaters. Batch cultures in yeast nitrogen base (YNB)′ liquid medium (YNB without amino acids and ammonium sulfate plus sucrose and ammonium sulfate) containing 1-mM initial Cr(VI) concentrations revealed that heavy metal removal in both isolates was substantially affected by the inoculation procedure. Inocula with high initial density or pregrown in a nutritionally rich medium (Malt Czapek) were found to be key factors in order to achieve successful Cr(VI) decontamination. In contrast, low-density inocula and/or synthetic media-precultured cells were shown to negatively influence Cr(VI) disappearance, either by increasing the time for complete degradation or by reducing the percentage of heavy metal removed. These results emphasized the relevance of the selection of an appropriate inoculum culture medium and the positive influence of increasing one order of magnitude inoculum cell density in order to achieve successful and rapid Cr(VI) removal. Under these considerations, the selected yeasts, P. jadinii M9 and P. anomala M10, exhibited a remarkable ability to tolerate and completely remove Cr(VI) concentrations up to 1 mM, thus being candidates for potential applications in bioremediation of Cr(VI)-contaminated environments.  相似文献   

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