不同价态铬在不同水分条件下的生物有效性及其对水稻的毒性

氧化还原过程在铬的形态转化中起了重要作用,而铬形态的转化能够影响其生物有效性及毒性。通过温室土培试验研究了六价铬(Cr(Ⅵ))与三价铬(Cr(Ⅲ))在淹水与不淹水条件下在土壤溶液中的动态变化及水稻对其吸收的变化。结果表明,土壤中添加Cr(Ⅲ)时,土壤溶液中检测不出Cr;而随着土壤中添加Cr(Ⅵ)浓度的增加,土壤溶液中Cr(Ⅵ)的浓度增加,但是溶液中检测不出Cr(Ⅲ);淹水处理总体上降低了土壤溶液中Cr(Ⅵ)的浓度。而土壤添加Cr(Ⅲ)、Cr(Ⅵ)和水分处理对土壤溶液p H没有显著影响,p H在7.08.0之间变动。土壤添加Cr(Ⅵ)处理的水稻中,只有90 mg·kg-1Cr(Ⅵ)淹水处理的水稻成活,而其余处理水稻没有成活。土壤中添加Cr(Ⅲ)处理,水稻幼苗生物量随Cr(Ⅲ)浓度的增加而显著降低;除了200mg·kg-1Cr(Ⅲ)处理外,其余淹水处理的水稻幼苗生物量明显高于不淹水处理的。土壤添加Cr(Ⅲ)处理的水稻,在不淹水条件下水稻空壳率比较高,淹水条件下,随着土壤中添加Cr(Ⅲ)浓度水平的增加,水稻各部位Cr含量有增加的趋势,但增加不显著,秸秆最高Cr含量达到33.80 mg·kg-1,籽粒中Cr含量最高0.30 mg·kg-1。土壤固定Cr(Ⅲ)的能力远强于Cr(Ⅵ),添加Cr(Ⅵ)处理的土壤溶液中Cr(Ⅵ)的浓度很高,对水稻表现出较强的生长抑制。     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min^?1 when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min^?1 were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.     

Cr (VI) and Fe (III) removal using Cajanus cajan husk

Husk of tur dal (Cajanus cajan) was investigated as a new biosorbent for the removal of Fe (III) and Cr (VI) ions from aqueous solutions. Parameters like agitation time, adsorbent dosage and pH were studied at different initial Fe (III) and Cr (VI) concentrations. The biosorptive capacity of the Tur dal husk was dependent on the pH of the chromium and iron solution, with pH 2 and 2.5 respectively being optimal. The adsorption data fit well with Langmuir and Freundlich isotherm models. The practical limiting adsorption capacity (qmax) calculated from the Langmuir isotherm was 96.05 mg of Cr(VI)/ g of the biosorbent at an initial pH of 2.0 and 66.65 mg/g at pH 2.5. The infrared spectra of the biomass revealed that hydroxyl, carboxyl and amide bonds are involved in the uptake of Cr (VI) and Fe (III) ions. Characterisation of tur dal husk has revealed that it is an excellent material for treating wastewaters containing low concentration of metal ions.     

Bioavailability and metabolism of hexavalent chromium compounds †

Intratracheal instillation of ⁵¹CrCl₃ in anaesthetized rabbits resulted in partial absorption. In blood, the absorbed material was entirely confined to the plasma compartment. Only trace amounts were deposited in liver and kidney. By contrast, after similar application of Na, ⁵¹CrO₄ the bulk of blood radioactivity was present in red blood cells (RBC). Substantial deposition occurred in liver and kidneys. It is concluded that Cr(VI) may enter the body unreduced via the lung and is partially deposited in cells over a prolonged period of time.

Since chromium was accumulated in liver after administration of Cr(VI) we investigated the intracellular disposition of Cr(VI) in the isolated perfused liver. No significant sex differences in chromium distribution were observed. At the end of the experiments (1 h), 60% of the applied dose (312μg Cr/liver) was located in the cytosol, whilst 14% was in the mitochondria, 9% in the microsomal pellet and 2% was associated with the nuclei. Gel chromatography of the cytosolic compartment showed that the overwhelming part of chromium was eluted in fractions with an apparent molecular weight of 6,000 dalton. These fractions exhibited absorption maxima at 410nm and 548nm. It is concluded, that cytosolic reduction might be the main intracellular redox pathway for chromates. This view was confirmed by monitoring the reaction of Cr(VI) with GSH in vitro. GSH reduced Cr(VI) without further cofactors under formation of GSH‐chromium complexes, which possibly represent major intermediates in the metabolism of Cr(VI).     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.     

Catalytic determination of ultratrace chromium based on gallocyanine‐hydrogen peroxide indicator reaction

A highly sensitive catalytic procedure for the determination of ultratrace chromium(VI) was developed based on its catalytic effect on the oxidation of gallocyanine by hydrogen peroxide in hexamine‐hydrochloric acid buffer solution. The reaction was followed spectrophotometrically by measuring the rate of change in the absorbance at 620 nm. The apparent active energy of the catalytic reaction is 6.84 kJ . mol^‐1. The calibration graph is linear for 0–150 ng.ml^‐1, and the detection limit is 0.8 ng.ml^‐1. Most foreign ions have no interfering effect on the determination of chromium(VI) except for Al³⁺, Cu²⁺, Fe³⁺and Fe²⁺. The interference of Al³⁺ is eliminated by masking with F^‐, and those of Cu²⁺, Fe³⁺ and Fe²⁺ are eliminated by adding appropriate amount of EDTA. The present procedure had been used for the determination of trace chromium(VI) in lake water, mine water and electroplating wastewater, and the results were satisfactory.     

Biosorption potential of Cr(VI) by Kocuria sp. ASB107, a radio-resistant bacterium isolated from Ramsar,Iran

Heavy metal pollution in soil and wastewater is a worldwide environmental issue in which microorganisms play a significant role for its removal. In the present study, biosorption of Cr(VI) by the live and dead cells of Kocuria sp. ASB107, a radio-resistant bacterium, was investigated. The effect of contact time, solution pH, initial hexavalent chromium concentration and adsorbent dose on biosorption efficiency was studied. Also, live cells were further immobilised on various matrices by different techniques and then were examined for tolerance to chromium biosorption. Experimental results indicated that the removal efficiency of chromium increased with decrease in pH, initial Cr(VI) concentration, and also increase in adsorbent dose and the contact time. The maximum removal efficiency of live and dead cells at acidic pH of 4–4.5, contact time of 24 hours, adsorbent dose 1.6?g/100?mL and initial chromium concentration 25?mg/L were 82.4% and 69.2%, respectively. The adsorption data was described well by Langmuir isotherm model. Among all immobilisation techniques tested, cross-linking showed the highest biosorption of Cr(VI). Results indicated that live cells of Kocuria sp. ASB107 were better than dead ones.     

Phytoextraction of Cr(VI) from soil using Portulaca oleracea

Cr(VI) represents an environmental challenge in both soil and water as it is soluble and bioavailable over a wide range of pH. In previous investigations, Portulaca oleracea (a plant local to the United Arab Emirates (UAE)) demonstrated particular ability for the phytoextraction of Cr(VI) from calcareous soil of the UAE. In this publication, the results of the evaluation of P. oleracea phytoextraction of Cr(VI) from UAE soil at higher concentrations are reported. P. oleracea was exposed to nine different concentrations of Cr(VI) in soil from 0 to 400 mg kg^?1. The uptake of Cr(VI) increased as its concentration in soil increased between 50 and 400 mg kg^?1, with the most efficient removal in the range from 150 to 200 mg kg^?1. The total chromium concentrations exceeded 4600 mg kg^?1 in roots and 1400 mg kg^?1 in stems, confirming the role of P. oleracea as an effective Cr(VI) accumulator. More than 95% of the accumulated Cr(VI) was reduced to the less toxic Cr(III) within the plant.     

Role of the vitamin E model compound Trolox in the prevention of Cr(VI)-induced cellular damage

Given the wide industrial use of chromium (Cr) and its environmental contamination, chromium represents a risk to humans exposed to the metal. Considering that Cr(VI) is a potent oxidizing agent that increases intracellular oxidation and DNA damage, it would be worth considering the pretreatment of cells with antioxidants as a means of preventing Cr(VI)-induced toxicity. The objective of this study was to pretreat yeast cells with the water-soluble vitamin E analogue Trolox in an effort to increase cell tolerance against reactive chromium and reactive oxygen species formed during Cr(VI) reduction. Results revealed a decrease in Cr(VI)-induced cytotoxicity and mitotic gene conversions in Trolox-pretreated cells. The protective effect of Trolox in Cr(VI) induced genotoxicity was confirmed also with the prokaryotic Salmonella typhimurium SOS/umu test. Pretreatment of cells with Trolox (1) increased total Cr bioaccumulation, (2) decreased Cr(VI)-induced intracellular oxidation, (3) decreased Cr(V) persistence and (4) increased OH^? formation in yeast extracts. These findings might be useful in directing future investigations concerning the use of Trolox as a human antioxidant supplement, and in clinical applications related to Cr-induced genotoxicity in occupational and environmental situations where chromium is a problem.     

Removal of toxic chromium(VI) from aqueous solution by activated carbon using Casuarina equisetifolia

Highly activated carbon from the seed husk of Casuarina Casuarinas equisetifolia, a worldwide famous plant, have been prepared and tested for the removal of toxic Cr(VI) from its aqueous solution. The adsorbent was investigated for influences of initial chromium concentration (75, 100, 125, and 150 mg l^-1), pH, contact time, and quantity of carbon on removal of Cr(VI) from aqueous solution at room temperature (25±2 °C). The adsorption kinetic of Cr(VI) was studied, and the rates of sorption were found to conform to pseudo-second-order kinetics with a good correlation (R²≥0.99). The Langmuir and Freundlich models fit the isotherm data well. Furthermore, the Gibbs free energy was obtained for each system and was found to be-5.29 kJ mol^-1 for removal of Cr(IV). The negative value of Δ G° indicates the feasibility and spontaneous nature of adsorption. The results indicate that acidic pH (1.05) supported the adsorption of Cr(IV) on activated carbon. The maximum adsorption capacity of Cr(VI) on activated carbon was about 172.4 mg g^-1 at pH 1.05.     

Biochemical speciation in chromium genotoxicity

The biochemical speciation of chromium compounds in mammalian cells is discussed with respect to uptake, metabolism, DNA binding and damaging. Whereas soluble hexavalent chromium is taken up rapidly and accumulated intracellularly after its reduction, compounds of trivalent chromium penetrate biomembranes about three orders of magnitude slower. Cr(VI) after its uptake is metabolised by electron donating compounds via Cr(V) to Cr(III) compounds. Chromium from various Cr(III) compounds, but not chromate, binds to chromatin in isolated cell nuclei. The DNA‐protein crosslinks and DNA strand breaks observed in rat liver and kidney after chromate administration are also found in vitro, when Cr(III) compounds (but not chromate) interacts with isolated nuclei. In the Chinese Hamster cell HGPRT mutation assay, three out of four tested Cr(III) complexes were found to be mutagenic. In a direct DNA strand break assay with supercoiled bacteriophage PM 2 DNA, neither chromate nor the four Cr(III) compounds tested caused nicks. However, the combined action of chromate plus glutathione as well as the isolated complex of pentavalent chromium, Na₄Cr(glutathione)₄, did cause DNA breaks. Reactive oxygen species are inferred to be the ultimate DNA nicking agents in this assay. In conclusion there appear to be two mechanisms of chromate genotoxicity; one with direct DNA damage caused by Cr(V) species and one via DNA‐protein crosslinks formed with Cr(III), the final reduction state of chromate.     

Ferrate(VI) oxidation of ibuprofen: A kinetic study

The kinetics of ferrate(VI) (Fe^VIO₄ ²⁻, Fe(VI)) oxidation of an antiphlogistic drug, ibuprofen (IBP), as a function of pH (7.75–9.10) and temperature (25–45°C) were investigated to see the applicability of Fe(VI) in removing this drug from water. The rates decrease with an increase in pH and the rates are related to protonation of ferrate(VI). The rates increase with an increase in temperature. The E _a of the reaction at pH 9.10 was calculated as 65.4±6.4 kJ mol⁻¹. The rate constant of the HFeO₄ ⁻ with ibuprofen is lower than with the sulphur drug, sulfamethoxazole. The use of Fe(VI) to remove ibuprofen is briefly discussed.     

Chromium sorption on grape stalks encapsulated in calcium alginate beads

A novel sorbent based on 2% grape stalk wastes encapsulated in calcium alginate beads was investigated for the removal of Cr(VI) and Cr(III) from aqueous solutions. The sorbent proved to be efficient for chromium removal in both hexavalent and trivalent forms from aqueous solution at pH 3.0. In binary mixtures, the presence in solution of one of the forms enhances the sorption of the other which results in an increase of the amount of total chromium removed. This study suggests that the proposed sorbent can be used for the removal of chromium from wastewaters through a cost-effective and environmentally friendly process.     

Uptake,distribution and loss of Cr in the crab Xantho hydrophilus

Uptake of ⁵¹Cr(III) is faster than uptake of ⁵¹Cr(VI), but it occurs mainly on the surface of the animals. Steady state is attained after 28 d. The resulting concentration factor is about 200. Although the uptake of ⁵¹Cr(VI) is slower, it is more intensively distributed into the organs and tissues of the animals. Steady state was not attained during the experiments (35 d); the highest concentration factor reached was about 10. The uptake of both ⁵¹Cr(III) and ⁵¹Cr(VI) seems to be passive. For both chemical forms of chromium, the loss rate is inversely proportional to the exposure time. When the uptake lasted longer, owing to the distribution of Cr(VI) into the organs and tissues, the loss rate of Cr(III) is somewhat faster relative to the loss rate of ⁵¹Cr(VI). The opposite is the case when the uptake of both forms lasts only two days. On the basis of the distribution and loss experiments, we argue that hexavalent chromium in living organisms is reduced to the trivalent form and then complexed with organic molecules.     

Equilibrium,kinetics and thermodynamics of hexavalent chromium biosorption on pristine and zinc chloride activated Senna siamea seed pods

Hexavalent chromium contamination in water is an issue of huge concern due to its use at a high scale, toxicity and non-biodegradability. Biosorption is a cost effective and unconventional strategy for the elimination of Cr(VI). Here, a novel biosorbent Senna siamea seed pod biomass and its chemically activated form have been investigated for the elimination of hexavalent chromium from aqueous solution. The biosorbent was characterized by using BET, FTIR, FESEM-EDX and TGA techniques. Parameters controlling the biosorption process were optimized as pH 2.0, temperature 30°C, initial Cr(VI) concentration 500?mg/L, biosorbent dose 0.5?g/L. Optimized contact time was 210 and 180 min for pristine biomass and activated carbon, respectively. Langmuir isotherm correlated well with experimental data revealing that the biosorption occurred in monolayer pattern. Maximum biosorption capacity calculated by Langmuir biosorption isotherm was 119.18 and 139.86?mg/g for S. siamea pristine biomass and activated carbon, respectively. Pseudo-second order kinetic model correlated well with experimental data. Thermodynamic studies suggested that the biosorption process occurs in a non-spontaneous, stable and endothermic manner. These interesting findings on Cr(VI) biosorption by S. siamea seed pod biomass and S. siamea zinc chloride activated carbon vouches for its potential application as an unconventional biosorbent.     

Stabilization of hexavalent chromium with pretreatment and high temperature sintering in highly contaminated soil

• Separate reduction and sintering cannot be effective for Cr stabilization. • Combined treatment of reduction and sintering is effective for Cr stabilization. • Almost all the Cr in the reduced soil is residual form after sintering at 1000°C. This study explored the effectiveness and mechanisms of high temperature sintering following pre-reduction with ferric sulfate (FeSO₄), sodium sulfide (Na₂S), or citric acid (C₆H₈O₇) in stabilizing hexavalent chromium (Cr(VI)) in highly contaminated soil. The soil samples had an initial total Cr leaching of 1768.83 mg/L, and Cr(VI) leaching of 1745.13 mg/L. When FeSO₄ or C₆H₈O₇ reduction was followed by sintering at 1000°C, the Cr leaching was reduced enough to meet the Safety Landfill Standards regarding general industrial solid waste. This combined treatment greatly improved the stabilization efficiency of chromium because the reduction of Cr(VI) into Cr(III) decreased the mobility of chromium and made it more easily encapsulated in minerals during sintering. SEM, XRD, TG-DSC, and speciation analysis indicated that when the sintering temperature reached 1000°C, almost all the chromium in soils that had the pre-reduction treatment was transformed into the residual form. At 1000°C, the soil melted and promoted the mineralization of Cr and the formation of new Cr-containing compounds, which significantly decreased subsequent leaching of chromium from the soil. However, without reduction treatment, chromium continued to leach from the soil even after being sintered at 1000°C, possibly because the soil did not fully fuse and because Cr(VI) does not bind with soil as easily as Cr(III).     

胶原纤维固化黑荆树单宁吸附Cr(VI)的研究

研究了胶原纤维固化黑荆树单宁对Cr(VI)的吸附.采用不同温度、pH值等条件进行吸附研究,并进一步探讨了固化黑荆树单宁的吸附动力学和吸附柱动力学及其吸附机理.结果表明,该材料对Cr(VI)的吸附平衡符合Freundlich方程,温度对吸附平衡的影响不明显;吸附动力学可用拟二级速度方程来描述,该材料同时具有良好的柱动力学特性;Cr(VI)的吸附过程可能存在3个反应,即Cr(VI)与吸附剂之间发生氧化还原反应生成Cr(III),Cr(III)和-COOH之间发生离子交换反应,以及Cr(III)与单宁的邻位羟基发生螯合.图8表2参10     

Changes in chromium distribution during the electrodialytic remediation of a Cr (VI)-contaminated soil

A laboratory study has been carried out to determine the feasibility of in situ remediation of chromium (VI)-contaminated soil using electrodialysis in relation to its speciation in soil. This technique is best suited for low-permeability soils or sediments, which may be difficult to remediate by other means and implies the application of a low-intensity direct current to the soil, which is separated from the electrode compartments by ion-exchange membranes. A clayey soil was prepared for use in the experiments and was characterized before being mixed with a solution of potassium dichromate for several days to produce a final Cr content of 4,056 mg/kg of soil dry wt. Remediation tests were carried out under constant-voltage conditions for periods of 7–14 days and the evolution of applied current to the cell, pH, and conductivity of the electrolytes were recorded periodically. Fractionation of chromium was determined for soil samples before and after remediation using a standardized four-step sequential extraction procedure (SEP) with acetic acid, hydroxylamine, hydrogen peroxide, and aqua regia solutions. Results show that chromium is mobilized from the most labile phases (soluble/exchangeable/carbonate). In a 15 V test, SEP results show that the amount of chromium extracted in the first step drops from 80% to 9%, but also that changes in the total chromium distribution occur during the treatment with some transferred to other soil phases that are more difficult to mobilize.     

Biosorption of hexavalent chromium and malachite green from aqueous effluents,using Cladophora sp.

Biosorption potential of green macroalgae Cladophora sp., (GAC) for the removal of hexavalent chromium (Cr(VI)) and malachite green (MG) from aqueous medium was investigated. Optimal conditions for biosorption experiments were determined as a function of initial pH, GAC dosage, temperature and initial concentration of Cr(VI) and MG. The biosorption equilibrium data were fitted with the isotherm models of Langmuir, Freundlich, Kiselev, Frumkin and Jovanovic, while the experimental data were analysed using the kinetic models such as pseudo-first-order, pseudo-second-order, Ritchie's and intraparticle diffusion. The Langmuir maximum biosorption capacity was calculated as 100.00?mg/g (Cr(VI)) and 142.85?mg/g (MG). The biosorption kinetic data showed better agreement with the pseudo-second-order kinetic model. The thermodynamic parameters indicated spontaneous and endothermic nature of the biosorption process for Cr(VI) removal, whereas exothermic in the case of MG removal. Furthermore, the biosorption efficiencies of the GAC reusability were found significant up to five cycles and tested using 0.1, 0.5 and 1.0?M HCl, respectively. The results of the present study indicated that GAC is a suitable biosorbent for the sequestration of Cr(VI) and MG from aqueous solutions.     

Removal of Cr(VI) from aqueous solutions by the culm of bamboo grass treated with concentrated sulfuric acid

We prepared a carbonaceous sorbent for Cr(VI) from the culm of Sasa kurilensis by dehydration with concentrated H₂SO₄. The removal of Cr(VI) by the sorbent was highly solution pH dependent and mainly governed by physicochemical sorption. The equilibrium data fit well in the Langmuir isotherm model and indicate the endothermic nature of the Cr(VI) sorption. The desorption experiments suggest that the Cr(VI) sorption is generally irreversible, owing to strong interaction of HCrO₄⁻ with the active sites of the sorbent.