Removal process and mechanism of hexavalent chromium by adsorption-coupled reduction with marine-derived Aspergillus niger mycelial pellets

In order to remove hexavalent chromium(Cr(Ⅵ)) from solutions efficiently, the mycelial pellets with a marine-derived fungus Aspergillus niger as a biosorbent were prepared. The effects of removal process parameters such as solution pH, initial Cr(Ⅵ) concentration and biomass concentration on Cr(Ⅵ) removal process were investigated. The results showed that Cr(Ⅵ) removal rate up to 100% could be achieved under optimized conditions, which indicated the excellent Cr(Ⅵ) removal performance of the Asp...     

Effect of pre‐treatments on the biosorption of Chromium (VI) ions by the dead biomass of Rhizopus arrhizus

BACKGROUND: This work fulfils the need to develop an eco‐friendly biosorbent, elucidating the mechanism of biosorption. Removal of Cr(VI) by Rhizopus arrhizus was investigated in batch mode. Enhancement in the performance of the biosorbent was attempted by pre‐treating the biomass with inorganic and organic acids, chelating agent, cross‐linker and an organic solvent followed by autoclaving. The surface characterization of the biomass was carried out by potentiometric titration, surface area analysis, infrared spectroscopy, chemical modification of the biomass and scanning electron microscopy. RESULTS: All the physico‐chemical treatments of the biosorbent improved Cr(VI) uptake compared with the native biomass (21.72 mg g^?1). The highest biosorption capacity (31.52 mg g^?1) was achieved after pre‐treating the biomass with 0.5 mol L^?1 HNO₃ followed by autoclaving. Surface characterization of the biomass using pH_zpc, potentiometry and Fourier transform infrared (FTIR) analysis revealed the role of amino and carboxyl groups in Cr(VI) removal by electrostatic attraction. Chemical modification of amino and carboxyl groups significantly decreased Cr(VI) uptake capacity confirming their role in biosorption. SEM analysis showed adsorption of Cr(VI) on the biosorbent surface. CONCLUSION: Rhizopus arrhizus biomass proved to be an effective and low cost alternative biosorbent for removal of Cr(VI) from aqueous solutions. Copyright © 2011 Society of Chemical Industry     

Re‐use of Exhausted Ground Coffee Waste for Cr(VI) Sorption

Abstract

Exhausted ground coffee waste has been investigated as metal biosorbent for Cr(VI) from aqueous solution. Maximum metal sorption was found to occur at initial pH 3.0. Kinetic studies revealed that the initial uptake was quite rapid; nevertheless, it took five days to reach equilibrium. The value of the Langmuir maximum uptake was found to be 10.2 mg Cr(VI)/g waste. The sorbent is able to reduce hexavalent chromium to its trivalent form. A solution of 1 M NaOH was the most effective desorption agent and after 24 hours contact 42% of total chromium was desorbed in both hexavalent and trivalent oxidation states.     

Reaction rate and electrochemical stability of conducting polymer films used for the reduction of hexavalent chromium

The reduction of toxic hexavalent chromium to its trivalent state at conducting polymers films was studied. The process is based on the capacity of conducting polymers to spontaneously donate electrons to the Cr(VI) species. Electrodes of polyaniline and polypyrrole, deposited as films on reticulated vitreous carbon (RVC), were prepared. The process of Cr(VI) reduction was studied under open and closed circuit conditions. It was observed that polyaniline was only suitable for use only under closed circuit conditions, whereas polypyrrole did not perform well under either open or closed circuit conditions. The electrocatalytic power of polyaniline for Cr(VI) reduction was demonstrated when the reaction rates for bare RVC and RVC/PANI were compared.     

含铬工业废水的绿色回收技术

铬是环境中普遍存在的几种微量金属之一,铬作为环境中的一种主要重金属污染物,主要以三价和六价形态存在,其中的三价铬对人和动物是必需的微量元素,而六价铬则是一种毒性较大的致畸、致突变的有害物。当前含铬废水进入了综合防治、回收利用与总量控制阶段,基于含铬废水的回收是当前较为迫切的任务,本文重点阐述了重金属铬的绿色回收技术。     

地表水环境中六价铬的测定研究

六价铬是地表水环境监测中的一个重要水质指标,其毒性比三价铬高出100倍。采用二苯基碳酰二肼分光光度法对地表水中的六价铬进行测定,对影响六价铬准确测定的各种因素进行了详细的分析,指出了相应的消除干扰的方法,为六价铬的准确测定提供了指导。结果表明,二苯碳酰二肼分光光度法测定地表水中的六价铬,方法灵敏,选择性好,标准曲线线性关系良好,能够准确测定地表水环境中的六价铬。     

Fate of Cr(III) during Ozonation of Secondary Municipal Wastewater Effluent

ABSTRACT

In the present study, the fate of trivalent chromium (Cr(III)) during ozonation of ultrapurified water and wastewater effluent was investigated. In experiments conducted in phosphate buffered ultrapurified water, O₃ alone in excess was inefficient to oxidize Cr(III) (only about 10–15% of total Cr(III) content), while in presence of the secondary oxidant, OH radical, almost all Cr(III) was oxidized to hexavalent chromium (Cr(VI)). In a wastewater effluent, spiked with Cr(III), only about 10–20% of Cr(III) was oxidized with specific ozone doses in the range 0.15–1.5 gO₃/gDOC, although O₃ and OH radical were both available for reaction. Cr(VI) formation was monitored in parallel with the abatement of some common micropollutants, reacting with differing apparent second-order rate constants with ozone, decreasing in the order carbamazepine>> benzotriazole> atrazine> p-chlorobenzoic acid (pCBA). Carbamazepine and benzotriazole were abated to >80% for specific O₃ doses of 0.3 gO₃/gDOC and 0.8 gO₃/gDOC, respectively. The more ozone-resistant compounds (atrazine and pCBA) required a specific ozone dose of about 1.25 gO₃/gDOC for the same relative abatement. At this specific ozone dose (i.e., 1.25 gO₃/gDOC), only about 20% of Cr(III) was oxidized to Cr(VI), whereas only 10% of Cr(III) was oxidized to Cr(VI) at a more realistic specific ozone dose for enhanced wastewater treatment for micropollutant abatement (0.5 gO₃/gDOC). Therefore, for typical Cr(III) levels in municipal wastewaters, effluent ozonation only leads to toxicologically insignificant Cr(VI) concentrations.     

Reduction of hexavalent chromium by Bacillus sp. isolated from chromite mine soils and characterization of reduced product

BACKGROUND: The reduction of highly mobile and toxic hexavalent chromium by bacterial strains is considered to be a viable alternative to reduce Cr(VI) contamination, in soils and water bodies, emanating from the overburden dumps of chromite ores and mine drainage. The present study reports the isolation of Cr(VI) resistant bacterial strains from an Indian chromite mine soil and their potential use in reduction of hexavalent chromium. RESULTS: Among the isolates, a bacterial strain (CSB‐4) was identified as Bacillus sp. based on standard biochemical tests and partial 16SrRNA gene sequencing, which was tolerant to as high as 2000 mg L^?1 Cr(VI) concentration. The strain was capable of reducing Cr(VI) to Cr(III) in different growth media. Under the optimized conditions pH ～7.0, 100 mg L^?1 Cr(VI), 35 °C temperature and stirring speed 100 rpm, CSB‐4 reduced more than 90% of Cr(VI) in 144 h. The time course reduction data fitted well an exponential rate equation yielding rate constants in the range 3.22 × 10^?2 to 6.5 × 10^?3 h^?1 for Cr(VI) concentration of 10–500 mg L^?1. The activation energy derived from temperature dependence rate constants between 25 and 35 °C was found to be 99 kJ mol^?1. The characterization of reduced product associated with bacterial cells by SEM‐EDS, FT‐IR and XRD was also reported. CONCLUSION: Reasonably high tolerance and reduction ability of indigenous Bacillus sp. (CSB‐4) for Cr(VI) under a wide range of experimental conditions show promise for its possible use in reclamation of chromite ore mine areas including soils and water bodies. Copyright © 2010 Society of Chemical Industry     

Enhanced photocatalytic reduction of Cr(VI) on silver nanoparticles modified mesoporous silicon under visible light

The development of visible-light photocatalysts with desirable material characteristics and efficient performance is an existing challenge for photocatalysis community. Herein, we report on the synthesis of silver nanoparticles (AgNPs) modified porous silicon (PSi) nanopowder and its effective use in the photo-reduction of hexavalent chromium Cr(VI) to trivalent Cr(III) under direct visible light irradiation in the presence of citric acid. The PSi was prepared via simple stain etching of Si microparticles in HF/HNO₃ aqueous solution, followed by the deposition of AgNPs onto PSi by the immersion plating technique. The developed photocatalyst composed of PSi with <20 nm mesoporous structure, decorated with crystalline 15-50 nm AgNPs. Photocatalytic experiments using unmodified Si microparticles, either PSi or sonicated one, indicated inactive catalytic behavior toward the photo-reduction of Cr(VI). Remarkable photo-reduction efficiency (97.4%) was achieved after 180 minutes irradiation using the AgNPs/PSi sample. The efficient photo-reduction capability of AgNPs/PSi photocatalyst is attributed to the enhanced separation between photo-generated electrons and holes (e⁻-h⁺) enabling better utilization of light, as revealed from the photoluminescence measurement. Additionally, the presence of citric acid in solution promoted greatly the photo-reduction reaction as it acted as a hole scavenger, suppressing further the rate of e⁻-h⁺ recombination through rapid consumption of photo-generated holes. Excellent reusability of the current photocatalyst was evidenced by performing cyclic five runs with minimal reactivity loss. Results of synthesis, characterization, photocatalytic activity and reaction mechanism are thoroughly addressed and discussed.     

Electrolytic removal of hexavalent chromium from aqueous solutions

The removal of hexavalent chromium from a synthetic solution and from an industrial sample by electrolysis using stainless steel plate and titanium mesh cathodes is studied. It is found that the process proceeds in two steps: (1) electroreduction of hexavalent chromium to trivalent chromium in highly acidic medium and (2) electrochemical precipitation of trivalent chromium in an alkaline medium. A comparative study of electroreduction, electrochemical reduction and chemical reduction of hexavalent chromium is carried out and the electroreduction process is shown to be a clean technique. It is concluded that, in the absence of addition of any chemical as reducing agent, the Cr(III) solution formed on the reduction of Cr(VI) can be recycled in other industrial processes. Copyright © 2003 Society of Chemical Industry     

Application of Chattim tree (devil tree,Alstonia scholaris) saw dust as a biosorbent for removal of hexavalent chromium from contaminated water

“Devil tree saw dust”; a novel biosorbent has been utilised successfully for the removal of hexavalent chromium from contaminated water. Batch adsorption procedure is utilised to test the ability of saw dust as an adsorbent for hexavalent chromium (reduction coupled adsorption). The contribution of various parameters on sorption, such as contact time, sorbate concentration, pH of the medium and temperature were estimated and maximum uptake of hexavalent chromium from contaminated water was 333.33 mg g^?1 at pH 2.0 and temperature of 35°C. Hexavalent chromium uptake from contaminated water followed the pseudo‐first‐order rate expression. The standard free energy change (ΔG⁰), standard enthalpy change (ΔH⁰) and standard entropy change (ΔS⁰) have also been evaluated and it has been concluded that the sorption was feasible, spontaneous and endothermic in nature. The process follows well Langmuir isotherm. Fourier Transform Infra‐Red (FTIR) spectroscopy and scanning electron microscopy (SEM) of hexavalent chromium loaded and unloaded saw dust were performed, SEM clearly indicates chromium adsorption. FTIR spectroscopy revealed the involvement of carbonyl, hydroxyl and amide groups on the cell surfaces in chromium binding. Very good adsorption capacity and low cost or cost free of devil tree saw dust makes this biosorbent as one of the best adsorbents for removal of hexavalent chromium from contaminated water. © 2012 Canadian Society for Chemical Engineering     

Utilisation of immobilised activated sludge for the biosorption of chromium (VI)

The objective of this investigation was to study the biosorption of Cr (VI) on immobilised activated sludge (IAS) and calcium alginate (CA) using batch system. The optimal pH for Cr (VI) biosorption by IAS and CA was 2.0 and 4.0, respectively. Equilibrium was attained at approximately 120 min for both biosorbents. For both biosorbents, the equilibrium biosorption capacity (mg/g) increased as the initial metal ion concentration increased and the concentration of biosorbent decreased. The rate of biosorption onto IAS and pure CA (as mg/g) increased from 5.02 to 87.66 and 4.97 to 79.09 as the concentration of Cr (VI) ions increased from 10 to 1000 mg/L, respectively. In the case of biosorbent concentration, as the concentration of IAS and pure CA increased from 1 to 20 g/L, the equilibrium uptake (q_e) decreased from 21.33 to 1.57 and 19.41 to 1.38 mg/g, respectively. The biosorption data showed that the Langmuir model was more suitable than the Freundlich model. Also, the results indicated that the pseudo‐second order model was the most suitable for Cr (VI) biosorption onto IAS and CA. © 2011 Canadian Society for Chemical Engineering     

Reduction of hexavalent chromium using polyaniline films. Effect of film thickness, potential and flow velocity on the reaction rate and polymer stability

Reduction of very toxic hexavalent chromium (Cr(VI)) to its trivalent state (Cr(III)) is necessary to facilitate the treatment of wastewater by precipitation or adsorption. The present study proposes the use of thin films of polyaniline on a conducting substrate for this purpose. The reduction rate of hexavalent chromium and the degree of degradation of the polyaniline film were studied as a function of the solution flow velocity, applied potential and film thickness. The reduction rate was significantly affected by the flow velocity, while the film thickness was observed to have little effect. The potential had no effect on the reduction rate within the range studied. The current efficiency was 100% in all experiments and no significant degradation of polyaniline was observed.     

基于石墨烯纳米材料的水质Cr(Ⅵ)电化学传感器

针对我国水质重金属六价铬（Cr（Ⅵ））污染问题突出,提出了一种基于石墨烯纳米材料的水质Cr（Ⅵ）电化学传感器。采用电化学方法还原氧化石墨烯,构建石墨烯纳米材料修饰金电极（rGO/Au）。采用扫描电子显微镜（SEM）和透射电子显微镜（TEM）技术表征了rGO/Au的表面形貌和结构;采用方波伏安法、循环伏安法和线性扫描伏安法等电化学方法研究了Cr（Ⅵ）在rGO/Au表面的直接电催化还原行为,优化了氧化石墨烯的电化学还原电位和还原时间,以及支持电解质pH、浓度和检测电位等实验参数;采用计时电流法,在无须预富集的条件下,考察了Cr（Ⅵ）浓度与rGO/Au响应电流之间的线性关系。实验结果表明,石墨烯纳米材料对Cr（Ⅵ）有明显的电催化还原活性,计时电流响应值与Cr（Ⅵ）浓度呈良好的线性关系,线性范围为5～2000μg·L^-1,最低检测限为0.5 μA·L^-1（S/N≥3）。所制备的rGO/Au具有对常见其他重金属干扰离子（Cr（Ⅲ）、Ni（Ⅱ）、Cu（Ⅱ）、Mg（Ⅱ）和Mn（Ⅱ））较好的抗干扰性能,11次连续测定后,响应值相对初始值下降幅度小于10%,表明该修饰电极具有较好的稳定性。本研究提出的电化学传感器具有检测方法简单、快速、环保以及可重复使用的优点,能够应用于水质重金属Cr（Ⅵ）的快速测定。     

Bioaccumulation and biosorption of copper(II) and chromium(III) from aqueous solutions by Pichia stipitis yeast

BACKGROUND: Bioaccumulation and biosorption by Pichia stipitis yeast has not yet been explored. This paper evaluates, for the first time, the use of both viable and nonviable P. stipitis yeast to eliminate Cu(II) and Cr(III) from aqueous solutions. The effect of Cu(II) and Cr(III) ions on the growth and bioaccumulation properties of adapted and nonadapted biomass is investigated as a function of initial metal concentration. Binding capacity experiments using nonviable biomass are also performed as a function of temperature. RESULTS: The addition of Cu(II) and Cr(III) had a significant negative effect on the growth of yeast. Nonadapted cells could tolerate Cu(II) and Cr(III) ions up to a concentration of 75 ppm. The growth rate of nonadapted and adapted cells decreased with the increase in Cu(II) and Cr(III) concentration. Adapted P. stipitis biomass was capable of removing Cu(II) and Cr(III) with a maximum specific uptake capacity of 15.85 and 9.10 mg g⁻¹, respectively, at 100 ppm initial Cu(II) and Cr(III) concentration at pH 4.5. Adsorption data on nonviable cells were found to be well modeled by the Langmuir and Temkin isotherms. The maximum loading capacity of dry biomass predicted from Langmuir isotherm for Cu(II) and Cr(III) at 20 °C were 16.89 and 19.2 mg g⁻¹, respectively, at pH 4.5. Biosorptive capacities were dependent on temperature for Cu(II) and Cr(III) solutions. CONCLUSION: Cu(II)‐ and Cr(III)‐adapted cells grow and accumulate these ions at high ratios. On the other hand, nonviable P. stipitis was found to be an effective biosorbent for Cu(II) and Cr(III) biosorption. Copyright © 2008 Society of Chemical Industry     

All-solid-state MoS2/WO3 photoelectrodes as high-efficiency catalysts for reductive/sorptive/recycling of hexavalent chromium

Photoelectrocatalysis (PEC) is an effective approach to eliminate carcinogen hexavalent chromium (Cr(VI)) in wastewater, in which high-performance catalysts are crucial. Herein, controlled growth of thin molybdenum disulphide (MoS₂) nanosheets on self-supported tungsten trioxide (WO₃) created an all-solid-state MoS₂/WO₃ heterojunction serving as electrode and catalyst simultaneously for removing Cr(VI). Countless small and thin MoS₂ nanoflakes build in a huge and porous interface for harvesting lights and adsorbing chromium species. And the highly conductive WO₃ substrate facilitates the transfer of those photoexcited-electron and therefore suppresses the recombination between electrons and holes. Furthermore, assisted by bias potential, electron streams from external circuit render an electron-rich interface at the MoS₂/WO₃ cathode, accelerating the Cr(VI) reduction by PEC. At −1.2 V, the PEC reduction efficiency of Cr(VI) reaches 100% within 30 min, surpassing the pristine WO₃ by 2.7 times. The generated Cr(III) ions can be immobilized on the porous MoS₂/WO₃ cathode through electrostatic attraction, enabling removal of total chromium. More importantly, the Cr(III) anchored to the catalyst can be effortlessly recovered by eluting with clean water, which also refreshes the MoS₂/WO₃ cathode. This study provides a new approach to fabricating photoelectrodes for sustainable PEC reduction and treatment of Cr(VI) containing wastewater.     

Chromium(VI) Biosorption and Bioaccumulation by Live and Acid-Modified Biomass of a Novel Morganella morganii Isolate

Conventional methods of chromium removal are often insufficient for the remediation of chromium-contaminated natural environments, necessitating the development of alternative strategies. In this paper, we report the isolation of a novel Morganella morganii strain capable of reducing hexavalent chromium to its less-toxic and less-soluble trivalent form. Cr(VI) reduction by this strain was evaluated in both acidic environments and conditions reflecting natural freshwater sources. The isolate achieved equilibrium within 3 h and displayed a specific uptake rate of 24.30 ± 1.67 mg Cr(VI)/g biomass following HCl treatment. Without acid treatment, a reduction of over 90% was recorded within 72 h for an initial Cr(VI) concentration 20 mg/L, corresponding to a Cr(VI) removal capacity of 19.36 ± 1.89 mg/g. Absorption data of acid-treated STB5 biomass most closely followed the Toth and Langmuir models. FTIR results indicate that hydroxyl groups and extracellular or cell membrane polysaccharides may be potential adsorption sites for hexavalent chromium. Our results suggest that the isolate may be used in situ for treatment of polluted freshwater environments.     

铬的分析方法研究进展

本文概述了近年来铬的测定方法,包括总铬、三价铬、六价铬、三价铬与六价铬的同时测定方法,并对今后的发展进行了展望。     

Chrome dyeing using anionic bivalent chromium complexes as mordants

Chrome dyeings are normally produced by first applying an acid dye containing ligand groups and then afterchroming with hexavalent chromium derivatives such as dichromate salts. The latter can damage wool fibres and also are toxic components in dyehouse effluents, so afterchroming with mixtures of Cr(III) salts and organic acids has been studied. It has been shown that the anionic complexes that form from trivalent chromium and the organic acids are fibre substantive at pH 2–4 and have the correct stability profile for exchanging ligands to bind the chromium with ligand groups in the dye. Dyeings produced generally show colour yields and fastness properties similar to the normal Cr(VI) dyeing process; the exception are these chromophores which undergo oxidative change in the dichromate process.     

Removal of Cr(VI) from Model Solutions by a Combined Electrocoagulation Sorption Process

The elimination of hexavalent chromium from synthetic effluents in a batch stirred electrocoagulation cell with aluminum electrodes coupled with a sorption process using red onion skin adsorbent is addressed. The effect of process variables such as medium pH and adsorbent concentration was investigated in an attempt to optimize the removal capacity. Adsorption and electrocoagulation were first considered separately, with maximum Cr(VI) removal yields of 47 % and 78 %, respectively, at pH 2. When combining the two processes, a removal of 97 % of the total Cr(VI) in a pH range of 3–6 was achieved. The almost total elimination observed for the considered pollutant demonstrated the feasibility and the synergistic effect of the coupled process.