Reduction of hexavalent chromium by ascorbic acid in aqueous solutions

Hexavalent chromium is a priority pollutant in the USA and many other countries. Reduction of Cr(VI) to Cr(III) is environmentally favorable as the latter species is not toxic to most living organisms and also has a low mobility and bioavailability. Reduction of Cr(VI) by ascorbic acid (vitamin C) as a reductant was studied using potassium dichromate solution as the model pollutant. Effects of concentration of vitamin C, pH, temperature, irradiation and reaction time on the reduction of Cr(VI) were examined. Cr(VI) might be reduced by vitamin C not only in acidic conditions but also in weakly alkaline solutions. The reduction of Cr(VI) by vitamin C might occur not only under irradiation but also in the dark. Vitamin C is an important biological reductant in humans and animals, and not toxic. It is water-soluble and can easily permeate through various types of soils. The results indicate that vitamin C could be used in effective remediation of Cr(VI)-contaminated soils and groundwater in a wide range of pH, with or without sunlight.     

Influence of plants on the reduction of hexavalent chromium in wetland sediments

This work addresses the effect that plants (Typha latifolia and Carex lurida) have on the reduction of Cr(VI) in wetland sediments. Experiments were carried out using tubular microcosms, where chemical species were monitored along the longitudinal flow axis. Cr(VI) removal was enhanced by the presence of plants. This is explained by a decrease in the redox potential promoted by organic root exudates released by plants. Under these conditions sulfate reduction is enhanced, increasing the concentration of sulfide species in the sediment pore water, which reduce Cr(VI). Evapotranspiration induced by plants also contributed to enhance the reduction of Cr(VI) by concentrating all chemical species in the sediment pore water. Both exudates release and evapotranspiration have a diurnal component that affects Cr(VI) reduction. Concentration profiles were fitted to a kinetic model linking sulfide and Cr(VI) concentrations corrected for evapotranspiration. This expression captures both the longitudinal as well as the diurnal Cr(VI) concentration profiles.     

Spectroscopic investigation of magnetite surface for the reduction of hexavalent chromium

The reduction of Cr(VI) to Cr(III) by magnetite in the presence of added Fe(II) was characterized through batch kinetic experiments and the effect of Fe(II) addition and pH were investigated in this study. The addition of Fe(II) into magnetite suspension improved the reductive capacity of magnetite. Eighty percent of Cr(VI) was reduced by magnetite (6.5 g l(-1)) with Fe(II) (80 mg l(-1)) within 1 h, while 60% of Cr(VI) was removed by magnetite only. However, the extent of improved reductive capacity of magnetite with Fe(II) was less than that predicted by the summation of each reduction capacity of magnetite and Fe(II). The reduction of Cr(VI) in the magnetite suspension with Fe(II) increased with the increase of molar ratio of Fe(II) to Cr(VI) (0.6, 1, 1.5, 2.3) in the range of 0-2.3 and with the decrease of pH in the range of pH 8.0-5.5. The speciation of chromium, iron, and oxygen on the surface of magnetite was investigated by X-ray photoelectron spectroscopy. Cr 2p3/2, Fe 2p3/2, and O 1s peaks were mainly observed at 576.7 and 577.8 eV, at 711.2 eV, and at 530.2 and 531.4 eV, respectively. The results indicates that Cr(III) and Fe(III) were the dominant species on the surface of magnetite after reaction and that the dominant species covered the magnetite surface and formed metal (oxy)hydroxide.     

Kinetics of the reduction of hexavalent chromium with the brown seaweed Ecklonia biomass

The dead biomass of the brown seaweed, Ecklonia sp., is capable of reducing toxic Cr(VI) into less toxic or nontoxic Cr(III). However, little is known about the mechanism of Cr(VI) reduction by the biomass. The objective of this work was to develop a kinetic model for Cr(VI) biosorption, for supporting our mechanism. The reduction rate of Cr(VI) increased with increasing total chromate concentration, [Cr(VI)], and equivalent concentration of organic compounds, [OCs], and decreasing solution pH. It was found that the reduction rate of Cr(VI) was proportional to [Cr(VI)] and [OCs], suggesting the simple kinetic equation -d[Cr(VI)]/dt=k[Cr(VI)][OCs]. When considering the consumption of organic compounds due to the oxidation by Cr(VI), an average rate coefficient of 9.33 (+/-0.65)microM(-1)h(-1) was determined, at pH 2. Although the function of the pH could not be expressed in a mechanistic manner, an empirical model able to describe the pH dependence was obtained. It is expected that the developed rate equation could likely be used for design and performance predictions of biosorption processes for treating chromate wastewaters.     

Microbial community response to addition of polylactate compounds to stimulate hexavalent chromium reduction in groundwater

To evaluate the efficacy of bioimmobilization of Cr(VI) in groundwater at the Department of Energy Hanford site, we conducted a series of microcosm experiments using a range of commercial electron donors with varying degrees of lactate polymerization (polylactate). These experiments were conducted using Hanford Formation sediments (coarse sand and gravel) immersed in Hanford groundwater, which were amended with Cr(VI) and several types of lactate-based electron donors (Hydrogen Release Compound, HRC; primer-HRC, pHRC; extended release HRC) and the polylactate-cysteine form (Metal Remediation Compound, MRC). The results showed that polylactate compounds stimulated an increase in bacterial biomass and activity to a greater extent than sodium lactate when applied at equivalent carbon concentrations. At the same time, concentrations of headspace hydrogen and methane increased and correlated with changes in the microbial community structure. Enrichment of Pseudomonas spp. occurred with all lactate additions, and enrichment of sulfate-reducing Desulfosporosinus spp. occurred with almost complete sulfate reduction. The results of these experiments demonstrate that amendment with the pHRC and MRC forms result in effective removal of Cr(VI) from solution most likely by both direct (enzymatic) and indirect (microbially generated reductant) mechanisms.     

Reliable evidences that the removal mechanism of hexavalent chromium by natural biomaterials is adsorption-coupled reduction

For the last few decades, over 200 papers have been published in the Cr(VI) biosorption research field. Most early studies have claimed that Cr(VI) was removed from aqueous phase through an anionic adsorption, but this approach has been lost old original position. It has been newly explained that these findings were misinterpreted due to errors in measuring the concentrations of different chromium species in the aqueous phase, insufficient contact time required for equilibrium and the lack of information about the oxidation state of the chromium bound to biomaterials. Although 'adsorption-coupled reduction' is now widely accepted as the mechanism of Cr(VI) biosorption by natural biomaterials, a number of researchers still believe that Cr(VI) is removed by anionic adsorption onto the biomaterials. Therefore, the objective of this study was to show reliable evidences that the removal mechanism of Cr(VI) by natural biomaterials is 'adsorption-coupled reduction'. Sixteen natural biomaterials were used to study the Cr(VI) biosorption. Not only Cr(VI) but also total Cr in the aqueous phase were analyzed. X-ray photoelectron spectroscope was also used to verify the oxidation state of the chromium bound to the biomaterials. Finally, the removal behavior of Cr(VI) by each biomaterial was described by a kinetic model based on a redox reaction.     

纳滤处理含Cr(VI)废水的试验研究

采用纳滤对含Cr(Ⅵ)废水进行试验研究,讨论了初始浓度、pH、浓差极化、共存离子对处理效果的影响.试验结果表明,NF90膜对含Cr(Ⅵ)废水有良好的处理效果,去除率超过了98%,出水Cr(Ⅵ)浓度低于0.5 mg/L,可以达标排放或回用于镀件漂洗.     

铁-苹果酸配合物对高价铬的光还原处理

研究了Fe(Ⅲ)-苹果酸配合物体系对Cr(Ⅵ)的光还原处理,考察了光源、初始pH值、Fe(Ⅲ)、苹果酸盐和Cr(Ⅵ)初始浓度等因素对Cr(Ⅵ)光还原效率的影响。结果表明:光照条件下,铁-苹果酸配合物能有效实现对六价铬的光还原。pH=3时Cr(Ⅵ)的光还原处理效果最佳;Fe(Ⅲ)和苹果酸盐初始浓度的增加可提高Cr(Ⅵ)的光还原效率;光还原的初始速率随各组分浓度的增大而增大,Fe(Ⅲ)浓度是影响反应速率的主要因素;Fe(Ⅲ)-苹果酸盐配合物光解产生的Fe(Ⅱ)是Cr(Ⅵ)的主要还原剂。     

锰掺杂硫化锌量子点LED蓝光灯光催化还原六价铬

通过共沉淀法合成了锰掺杂硫化锌量子点(ZnS∶Mn QDs),该催化剂可在450 nm LED蓝光灯下光催化还原Cr(Ⅵ)。采用TEM、XRD、PL分别对ZnS∶Mn QDs的形貌、物相和发光特性进行了表征,结果表明：ZnS∶Mn QDs的尺寸小于10 nm;Mn掺杂没有改变ZnS的晶体结构;ZnS在掺杂Mn后,可在598 nm处产生橘黄色荧光。UV-vis表征结果显示,与纯ZnS相比,ZnS∶Mn QDs具有更强的光吸收能力。考察了不同因素对光催化效果的影响。结果表明,Mn掺杂浓度3%较为合适,酸性pH有利于光催化反应。当Cr(Ⅵ)浓度为25 mg·L⁻¹,pH为5.8时,光催化25 min后Cr(Ⅵ)去除率为99%。与其他光催化剂还原Cr(Ⅵ)相比,ZnS: Mn QDs使用低能耗LED灯作为光源,催化速率高,且能够吸附还原产物Cr(Ⅲ)。探究了光催化机理,发现在450 nm光激发下,Mn²⁺自身能级⁴T₁→⁶A₁发生跃迁产生光生电子,Cr(Ⅵ)捕获光生电子被还原,价带上余留的空穴参与水的氧化。结合表征结果,ZnS可通过掺杂Mn离子改善光吸收能力提高光催化还原Cr(Ⅵ)的性能。     

高价铬及双酚A在铁-乳酸体系中的同时光处理

研究了Fe(Ⅲ)-乳酸配合物体系同时对Cr(Ⅵ)的光还原及双酚A(BPA)的光氧化处理,考察了光源、初始pH值、Fe(Ⅲ)、乳酸盐、Cr(Ⅵ)及BPA初始浓度等因素对Cr(Ⅵ)及BPA光处理效率的影响。结果表明:光照条件下,铁-乳酸配合物能有效实现对六价铬及BPA的同时光处理。同一体系中,Cr(Ⅵ)的光还原快于BPA的光氧化,Fe(Ⅲ)初始浓度的增加可同时提高Cr(Ⅵ)的光还原效率和BPA的光氧化效率;Fe(Ⅲ)-乳酸盐配合物光解产生的Fe(Ⅱ)是Cr(Ⅵ)的主要还原剂,其次级光反应中产生的.OH是BPA的氧化剂。     

Immobilised microbial reactor for the biotransformation of hexavalent chromium

Out of an array of bacterial strains isolated from soil contaminated with effluents from electroplating wastewater, Bacillus coagulans exhibited the maximum Cr(VI) reduction potential. The feasibility of an immobilized B. coagulans bioreactor for hexavalent chromium reduction was investigated. Experimental results demonstrated that near complete removal of Cr(VI) was achieved in the reactor with an initial Cr(VI) concentration of 26 mg/l and reactor time of 24 h. The removal efficiency in the bioreactor was significantly affected by the influent Cr(VI) concentration, the Cr(VI) loading rate, the reaction time and the amount of Cr(VI) reduced by the biomass.     

Photochemical transformation of azoxystrobin in aqueous solutions

The photochemical behaviour of azoxystrobin fungicide (AZX) in water was studied under laboratory conditions. Photodegradation was initiated using a solar simulator (xenon arc lamp) or a jacketed Pyrex reaction cell equipped with a 125 W, high-pressure mercury lamp. HPLC/MS analysis (APCI and ESI in positive and negative modes) was used to identify AZX photoproducts. The calculated polychromatic quantum efficiencies (phi) of AZX at pH 4.5, 7 and 9 were 5.42 x 10(-3), 3.47 x 10(-3) and 3.06 x 10(-3) (degraded molecules per absorbed photon), respectively. The relatively narrow range of values indicates the stability of AZX with respect to photodegradation in the studied pH range. Results from the HPLC/MS analysis suggest that the phototransformation of AZX proceeds via multiple, parallel reaction pathways including: (1) photo-isomerization (E-->Z), (2) photo-hydrolysis of the methyl ester and of the nitrile group, (3) cleavage of the acrylate double bond, (4) photohydrolytic ether cleavage between the aromatic ring giving phenol, and (5) oxidative cleavage of the acrylate double bond.     

Characterization of adsorbent composition in co-removal of hexavalent chromium with copper precipitation

Mechanisms of hexavalent chromium co-removal with copper precipitation by dosing Na2CO3 were studied with a series of well-designed batch tests using solutions containing 150 mg l-1 Cu(II) and 60 mg l-1 Cr(VI). It was found that direct precipitation of chromium through formation of copper-chromium bearing precipitates (in the form of CuCrO4) was one of the main mechanisms contributing to chromium co-removal at pH close to 5.0, and adsorption of chromium at a higher pH by freshly formed copper-carbonate precipitates (adsorbent) contributed to further chromium co-removal. Since, according to solubility products, neither copper-carbonate nor copper-hydroxide precipitates can be produced at pH around 5.0 for a pure 150 mg l-1 copper precipitation, characterization of copper-carbonate precipitates (adsorbent) was carried out through developing pC-pH curves of the systems by both equilibrium calculations and MINEQL+ 4.5 (a chemical equilibrium modeling software), and also through laboratory determination of the precipitate composition, such as gravimetric analyses, inorganic carbon percentage and EDAX spectrum analyses. CuCO3.Cu(OH)2, or a combination of CuCO3.Cu(OH)2 (in majority) and Cu(OH)2 (in minority) were suggested to be the major constituent of the precipitates obtained from the copper solution with Na2CO3 dosing.     

柚皮粉对水中Cr(Ⅵ)的吸附性能研究

采用柚皮粉吸附去除水中Cr(Ⅵ)。考察了pH、吸附时间、柚皮粉用量和Cr(Ⅵ)初始浓度等因素对吸附效果的影响,测定了吸附等温线,对等温吸附规律及吸附机理进行了探讨。结果表明,pH、吸附时间、柚皮粉用量、Cr(Ⅵ)初始浓度、温度等因素对柚皮粉吸附水中Cr(Ⅵ)有显著影响。适宜的吸附条件为:pH 1.5,吸附时间6 h,柚皮粉用量0.5 g/100 mL,Cr(Ⅵ)初始浓度不大于10 mg/L,温度25℃。在该条件下,Cr(Ⅵ)的去除率可达98%以上。柚皮粉对水中Cr(Ⅵ)的等温吸附规律可用Freundlich、Langmuir和Temkin模式较好地描述,吸附呈单分层形式,吸附性能良好,吸附易于进行。柚皮细胞成分中的活性基团与Cr(Ⅵ)发生表面络合作用是吸附的主要机理。     

Soil humic acids may favour the persistence of hexavalent chromium in soil

The interaction between hexavalent chromium Cr(VI), as K₂CrO₄, and standard humic acids (HAs) in bulk solution was studied using three complementary analytical methods: UV-Visible spectroscopy, X-ray absorption spectroscopy and differential pulse stripping voltammetry. The observed UV-Vis and X-ray absorption spectra showed that, under our experimental conditions, HAs did not induce reduction of Cr(VI) to its trivalent chemical form. The interaction between Cr(VI) and HAs has rather led to the formation of Cr(VI)-HAs micelles via supramolecular chemical processes. The reported results could contribute towards explaining the relative persistence of ecotoxic hexavalent chromium in soils.     

Biological reduction of hexavalent chromium--a field study.

When ferrochromium is produced at Varg?n Alloys AB (Varg?n, Sweden), an offgas dust is generated as a byproduct. A leachate that contains hexavalent chromium (Cr6+) is formed when rainwater percolates through the dust deposit. In this study, Cr6+ in the leachate was reduced to trivalent chromium (Cr3+) by biological treatment in a biofilm process operated under anaerobic conditions. The reactor volume was 26 m3 and it was filled with 16 m3 plastic packing. Acetic acid was added as an electron donor. The Cr6+ was reduced from 10 to 20 mg/L to below 0.03 mg/L when the reactor was operated at a hydraulic retention time of 11 hours. The reduction activity in the process gradually decreased as the water temperature dropped below 10 degrees C.     

乙酰化小麦秸秆吸附水中六价铬

研究了乙酰化小麦秸秆对水中六价铬的吸附特性。用傅里叶红外光谱（FTIR）对改性前后的小麦秸秆进行表征,通过静态序批实验探究了改性小麦秸秆对六价铬的吸附机理及影响因素。FTIR结果显示,改性后小麦秸秆表面乙酰化程度提高,有酯基产生;改性前后的吸附材料表面零电荷点（pHPZC）分别为2.8与6.3,相比于未改性的小麦秸秆,改性后的pHPZC升高;在温度298 K,溶液pH=1时改性小麦秸秆对六价铬的去除率达到最大值78.83%,并且在酸性条件下改性小麦秸秆均能较好的吸附六价铬;Langmuir等温吸附方程能更好的描述吸附过程,在温度298 K和308 K时,最大吸附量分别为240.213 9 mg·g-1和288.082 3 mg·g-1;吸附为吸热自发过程,遵循准二级动力学方程。     

改性天然菱铁矿去除水中六价铬

六价铬Cr(Ⅵ)是地下水污染的重要组分之一。近几年吸附法除铬被广泛应用。为了强化Cr(Ⅵ)的去除效率,对成本低廉的天然菱铁矿进行了改性,并研究了最优改性条件及其对Cr(Ⅵ)的吸附特性。经过不同温度的灼烧改性发现,在500℃灼烧20 min时改性材料去除地下水中Cr(Ⅵ)的效率最高,在25℃时其吸附容量可达0.092 mg/g,吸附效率为92%。通过一系列的静态批实验,考察了最优改性菱铁矿对水中Cr(Ⅵ)的吸附效果。结果表明,二级吸附动力学模型可以更好地描述不同温度下的吸附过程。与Langmuir等温吸附模型相比,等温吸附数据更好地符合Freundlich等温吸附模型。溶液pH对改性天然菱铁矿的吸附效果影响较大,pH在2~8之间吸附容量基本稳定;当pH=8~11时,随着pH升高吸附量明显减小。SEM、比表面积、ZPC测定等结果表明,改性菱铁矿比表面积增大,pHzpc在7.8左右。因此,比表面积、表面电荷的分布等表面性质是改性天然菱铁矿除铬性能强的主要原因。     

Studies on hexavalent chromium biosorption by chemically-treated biomass of Ecklonia sp

The biomass of the brown seaweed, Ecklonia sp., is capable of reducing Cr(VI) to Cr(III). However, very little is known about the mechanism of Cr(VI) reduction by the biomass. The aims of the present investigation were to enhance the Cr(VI)-reducing capacity of the biomass using various chemical treatments and to elucidate the mechanisms governing Cr(VI) reduction. Among the various chemical treatments, acid-treatment showed the best performance with regards the improvement of Cr(VI) removal from the aqueous phase, while organic solvent-treatment significantly improved the removal efficiency of total Cr in the equilibrium state. Based on FTIR study, the biomass was subjected to chemical modification of its amino and carboxyl groups, to examine their roles in the Cr(VI) removal from the aqueous phase. Methylation of the amino group significantly decreased the Cr(VI) removal rate, but amination of the carboxyl group significantly increased the Cr(VI) removal rate. Meanwhile, esterification of the carboxyl group and carboxylation of the amino group decreased the Cr(VI) removal rate, but the former showed a more negative effect than the latter. These findings indicated that the amino and carboxyl groups take part in the Cr(VI) removal from the aqueous phase. In conclusion, mechanisms for direct and indirect Cr(VI) removal are proposed, and some aspects for the application of this biomass to Cr(VI) detoxification are discussed.