The role of iron in hexavalent chromium reduction by municipal landfill leachate

The function of iron (ferric (Fe(III)) and ferrous (Fe(II))) in the hexavalent chromium (Cr(VI)) reduction mechanism by bacteria in municipal landfill leachate (MLL) was assessed. Evidence of an "electron shuttle" mechanism was observed, whereby the Cr(VI) was reduced to trivalent chromium (Cr(III)) by Fe(II) with the resulting Fe(III) bacterially re-reduced to Fe(II). Typically, investigations on this electron shuttle mechanism have been performed in an artificial medium. As MLL comprises an elaborate mixture of bacteria, humic materials and organic and inorganic species, additional complexities were evident within the cycle in this study. Bioavailability of the Fe(III) for bacterial reduction, availability of bacterially produced Fe(II) for chemical Cr(VI) reduction and hydrolysis of Fe(II) and Fe(III) become prevalent during each phase of the shuttle cycle when MLL is present. Each of these factors contributes to the overall rate of bacterial Cr(VI) reduction in this media. This work highlights the need to consider local environmental conditions when assessing the bacterial reduction of Cr(VI).     

Microbial reduction of hexavalent chromium by landfill leachate

The reduction of hexavalent chromium (Cr(VI)) in municipal landfill leachates (MLL) and a non-putrescible landfill leachate (NPLL) was investigated. Complete Cr(VI) reduction was achieved within 17 days in a MLL when spiked with 100 mg l(-1) Cr(VI) or less. In the same period, negligible Cr(VI) reduction was observed in NPLL. In MLL, Cr(VI) reduction was demonstrated to be a function of initial Cr(VI) concentration and bacterial biomass and organic matter concentrations. The bacteria were observed to tolerate 250 mg l(-1) Cr(VI) in MLL and had an optimal growth activity at pH 7.4 in a growth medium. The MLL also possessed an ability to sequentially reduce Cr(VI) over three consecutive spiking cycles.     

Toxicity of hexavalent chromium to Daphnia magna: influence of reduction reaction by ferrous iron

The reaction kinetics of hexavalent chromium with ferrous ions were studied to determine the influence of reduction on the toxicity of chromium to aquatic organisms. The changes in chemical forms of the chromate in the presence of ferrous ions were examined in a bioassay system using Daphnia magna as a test organism. This study demonstrated that the reaction kinetics of chromate with ferrous ions showed a significant decrease of chromate concentration with the second-order rate coefficient (k) for the reduction of Cr(VI) being determined as 55.2M(-1)s(-1). The concentration of Cr(VI) remaining in the solution decreased as the ratio of ferrous ion to chromate increased, revealing a non-stoichiometric reaction due to oxygenation and the moderately alkaline pH of the solutions. The toxicity test indicated that the bioavailability of chromate to D. magna was reduced in the presence of Fe(II) and that it decreased further with increasing Fe(II) concentrations. However, the toxic effect of chromate to aquatic organisms was not controlled kinetically in the presence of ferrous ions. It was also found that LC(50) of chromate to D. magna decreased about 1.5-fold as the test period increased from 24 to 48h in the presence of Fe(II).     

Optical study of the reduction of hexavalent chromium by iron-based nanoparticles

In this paper, a simple method was presented to measure the concentration change in the Cr(VI)-contained waste water during treatment by nanoparticles, based on its optical absorption spectral evolution which exhibits a good linear relationship between the absorbance of the peak at 348 nm and Cr6+ ion concentration. The iron and Fe/Pd bimetal nanoparticles were prepared and used for removal of Cr6+ in waste water. It has been found that presented method for concentration determination based on optical spectral evolution is effective and flexible. The nanoparticles have higher efficiency than normal iron powders and Fe/Pd bimetallic nanoparticles show faster removal of the Cr6+ than iron nanoparticles. The study is of importance in environmental remediation or pollution treatment of heavy metal ions in water and even soil.     

Hexavalent chromium reduction with scrap iron in continuous-flow system Part 1: effect of feed solution pH

The reduction of hexavalent chromium by scrap iron was investigated in continuous system, using long-term column experiments, for aqueous Cr(VI) solutions having low buffering capacities, over the pH range of 2.00-7.30. The results showed that the initial pH of Cr(VI) solution significantly affects the reduction capacity of scrap iron. The highest reduction capacity was determined to be 19.2 mg Cr(VI)/g scrap iron, at pH 2.50, and decreased with increasing the initial pH of Cr(VI) solution. A considerable decrease in scrap iron reduction capacity (25%) was also observed at pH 2.00, as compared to pH 2.50, due to the increased contribution of H(+) ions to the corrosion of scrap iron, which leads to a rapid decrease in time of the scrap iron volume. Over the pH range of 2.50-7.30, hexavalent chromium concentration increases slowly in time after its breakthrough in column effluent, until a steady-state concentration was observed; similarly, over the same pH range, the amount of solubilized Cr(III) in treated column effluent decreases in time, until a steady-state concentration was observed. The steady-state concentration in column effluent decreased for Cr(VI) and increased for Cr(III) with decreasing the initial pH of Cr(VI) solution. No steady-state Cr(VI) or Cr(III) concentrations in column effluent were observed at pH 2.00. Over the entire studied pH range, the amount of Fe(total) in treated solution increases as the initial pH of column influent is decreased; the results show also a continuously decrease in time of Fe(total) concentration, for a constant initial pH, due to a decrease in time of iron corrosion rate. Cr(III) concentration in column effluent also continuously decreased in time, for a constant initial pH, over the pH range of 2.50-7.30. This represents an advantage, because the amount of precipitant agent used to remove Fe(total) and Cr(III) from the column effluent will also decrease in time. The optimum pH for Cr(VI) reduction with scrap iron in continuous-flow system was established at the value of 2.50.     

Removal of hexavalent chromium from aqueous solution by agricultural waste biomass

In the present study adsorption of Cr(VI) from aqueous solutions onto different agricultural wastes, viz., sugarcane bagasse, maize corn cob and Jatropha oil cake under various experimental conditions has been studied. Effects of adsorbent dosage, Cr(VI) concentration, pH and contact time on the adsorption of hexavalent chromium were investigated. The concentration of chromium in the test solution was determined spectrophotometrically. FT-IR spectra of the adsorbents (before use and after exhaustion) were recorded to explore number and position of the functional groups available for the binding of chromium ions on to studied adsorbents. SEMs of the adsorbents were recorded to explore the morphology of the studied adsorbents. Maximum adsorption was observed in the acidic medium at pH 2 with a contact time of 60min at 250rpm stirring speed. Jatropha oil cake had better adsorption capacity than sugarcane bagasse and maize corn cob under identical experimental conditions. The applicability of the Langmuir and Freundlich adsorption isotherms was tested. The results showed that studied adsorbents can be an attractive low cost alternative for the treatment of wastewaters in batched or stirred mode reactors containing lower concentrations of chromium.     

Palladium nanoparticles supported on amine-functionalized glass fiber mat for fixed-bed reactors on the effective removal of hexavalent chromium by catalytic reduction

Palladium nanoparticles were deposited on the amine-grafted glass fiber mat (GFM-NH₂) catalyst support by a conventional impregnation process followed by the borohydride reduction in aqueous solution at room temperature to create the designed Pd/GFM-NH₂ catalyst. By the use of large size glass fiber mat without nano/mesopores as the catalyst support, the internal mass transfer limitations due to the existence of nano/mesopores on the catalyst support were eliminated and the Pd/GFM-NH₂ catalyst could be easily separated from treated water due to the large size of the catalyst support. Batch experiments demonstrate its good catalytic reduction performance of Cr(VI) with formic acid as the reducing agent. It also demonstrated an efficient Cr(VI) removal and stability in a lab-prepared, packed fixed-bed tube reactor for the continuous treatment of Cr(VI)-containing water. Thus, it has a good potential for the catalytic reduction of Cr(VI) in the water treatment practice.     

Mechanisms of the removal of hexavalent chromium by biomaterials or biomaterial-based activated carbons

Three papers published during recent 2 years in Journal of Hazardous Materials made a mistake in analyzing chromium species in aqueous solution, resulting in incorrect elucidation of Cr(VI) biosorption; the Cr(VI) was removed from aqueous solution systems by 'anionic adsorption'. However, it has been proved that Cr(VI) is easily reduced to Cr(III) by contact with organic materials under acidic conditions because of its high redox potential value (above +1.3 V at standard condition). Therefore, it is strongly possible that the mechanism of Cr(VI) removal by biomaterials or biomaterial-based activated carbons is not "anionic adsorption" but "adsorption-coupled reduction". Thus, for researches of Cr(VI) biosorption, researchers have to analyze not only Cr(VI) but also total Cr in aqueous solution and to check the oxidation state of chromium bound on the biomaterials or activated carbons.     

Characteristics and mechanisms of hexavalent chromium removal by biochar from sugar beet tailing

Removal of Cr(VI) from aqueous solutions using biochar from sugar beet tailing (SBT) was investigated as a function of pH, contact time, and biochar mass via batch experiments. The surface characteristics of SBT biochar before and after Cr(VI) sorption was investigated with scanning electron microscopy equipped with energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy. Desorption and X-ray photoelectron spectroscopy studies showed that most of the Cr bound to SBT biochar was Cr(III). These results indicated that the electrostatic attraction of Cr(VI) to positively charged biochar surface, reduction of Cr(VI) to Cr(III) ion, and complexation between Cr(III) ion and SBT's function groups were probably responsible for Cr(VI) removal by SBT biochar. An initial solution with a pH of 2.0 was most favorable for Cr(VI) removal. The sorption process can be described by the pseudo-second order equation and Langmuir isotherm. The maximum sorption capacity for Cr(VI) was 123 mg/g under an acidic medium, which was comparable to other low-cost sorbents.     

Reduction of hexavalent chromium by Sphaerotilus natans a filamentous micro-organism present in activated sludges

Wastewaters produced by various industries may contain undesirable amounts of hexavalent chromium (Cr(VI)), as chromate and dichromate, a hazardous metal affecting flora and animals of aquatic ecosystems as well as human health. One removal strategy comprises the microbial reduction of Cr(VI) to Cr(III), a less soluble chemical species that is less toxic than Cr(VI). In this work, the ability to reduce Cr(VI) of Sphaerotilus natans, a filamentous bacterium usually found in activated sludge systems, was evaluated. In aerobic conditions, S. natans was able to efficiently reduce Cr(VI) to Cr(III) from dichromate solutions ranging between 4.5 and 80 mg Cr(VI)l(-1) in the presence of a carbonaceous source. A simultaneous evaluation of the microbial respiratory activity inhibition was also carried out to analyze the toxic effect of Cr(VI). Cr(VI) reduction by S. natans was mathematically modeled; chromium(VI) reduction rate depended on both Cr(VI) concentration and active biomass concentration. Although it is known that S. natans removes heavy metal cations such as Cr(III) by biosorption, the ability of this micro-organism to reduce Cr(VI), which behaves as an oxyanion in aqueous solutions, is a novel finding. The distinctive capacity to reduce Cr(VI) to Cr(III) than remain soluble or precipitated becomes S. natans a potential micro-organism to decontaminate wastewaters.     

Continuous automated measurement of hexavalent chromium in airborne particulate matter

An automated continuous instrument for the collection and measurement of aerosol Cr(VI) is described. The system alternately collects the sample on one of two glass fiber filters. After 15-min sample collection on one filter, the sampling switches over to the second filter. The freshly sampled filter is washed for 8.5 min, and the washings are preconcentrated on a minicolumn packed with anion exchange resin. The washed filter is dried with filtered hot air for the next 6.5 min so that it is ready for sampling at the end of the 15-min cycle. The preconcentrated Cr(VI) on the column is eluted with 0.1 M sodium perchlorate and then reacted with sym-1,5-diphenylcarbazide prior to absorbance detection with a light emitting diode-based dedicated flow-through absorbance detector. The detection limit (S/N = 3) is 5 ng of Cr(VI)/m3, orders of magnitude lower than current regulatory requirements. The instrument operates unattended over long periods. In continuous round-the-clock operation, filter replacement frequency is every 24-72 h, depending on dust loading. The system is portable for facile field deployment and permits fully automated rapid determinations at a very low analysis cost per sample.     

铁屑材料压制工艺及性能研究

为研究铁屑热压成型工艺,将表面处理后的Q195切屑经压实、加热、热复压工序,得到具有一定强,度和塑性的金属材料.通过压缩试验和金相观察,考察工艺参数对材料组织及性能的影响.研究表明:冷压烧结不能使金属切屑之间实现冶金结合,必需进行热复压;随着压制力及压制温度的提高,材料的密度和变形抗力增大;在小变形情况下,试件的变形抗...     

Biosorption of hexavalent chromium by raw and acid-treated green alga Oedogonium hatei from aqueous solutions

The hexavalent chromium, Cr(VI), biosorption by raw and acid-treated Oedogonium hatei were studied from aqueous solutions. Batch experiments were conducted to determine the biosorption properties of the biomass. The optimum conditions of biosorption were found to be: a biomass dose of 0.8 g/L, contact time of 110 min, pH and temperature 2.0 and 318 K respectively. Both Langmuir and Freundlich isotherm equations could fit the equilibrium data. Under the optimal conditions, the biosorption capacities of the raw and acid-treated algae were 31 and 35.2 mg Cr(VI) per g of dry adsorbent, respectively. Thermodynamic parameters showed that the adsorption of Cr(VI) onto algal biomass was feasible, spontaneous and endothermic under studied conditions. The pseudo-first-order kinetic model adequately describe the kinetic data in comparison to second-order model and the process involving rate-controlling step is much complex involving both boundary layer and intra-particle diffusion processes. The physical and chemical properties of the biosorbent were determined and the nature of biomass-metal ions interactions were evaluated by FTIR analysis, which showed the participation of -COOH, -OH and -NH(2) groups in the biosorption process. Biosorbents could be regenerated using 0.1 M NaOH solution, with up to 75% recovery. Thus, the biomass used in this work proved to be effective materials for the treatment of chromium bearing aqueous solutions.     

Field method for the determination of hexavalent chromium by ultrasonication and strong anion-exchange solid-phase extraction

A simple, fast, sensitive, and economical field method was developed and evaluated for the determination of hexavalent chromium (CrVI) in environmental and workplace air samples. By means of ultrasonic extraction in combination with a strong anion-exchange solid-phase extraction (SAE-SPE) technique, the filtration, isolation, and determination of CrVI in the presence of trivalent chromium (CrIII) and potential interferents was achieved. The method entails (1) ultrasonication in basic ammonium buffer solution to extract CrVI from environmental matrixes; (2) SAE-SPE to separate CrVI from CrIII and interferences; (3) elution/acidification of the eluate; (4) complexation of chromium with 1,5-diphenylcarbazide; and (5) spectrophotometric determination of the colored chromium-diphenylcarbazone complex. Several critical parameters were optimized in order to effect the extraction of both soluble (K2CrO4) and insoluble (PbCrO4) forms of CrVI without inducing CrIII oxidation or CrVI reduction. The method allowed for the dissolution and purification of CrVI from environmental and workplace air sample matrixes for up to 24 samples simultaneously in less than 90 min (including ultrasonication). The results demonstrated that the method was simple, fast, quantitative, and sufficiently sensitive for the determination of occupational exposures of CrVI. The method is applicable for on-site monitoring of CrVI in environmental and industrial hygiene samples.     

Copper foams in water treatment technology: Removal of hexavalent chromium

Open-cell copper foams were prepared using a space holder technique and tested as filter-beds for the uptake and reduction of Cr(VI) in drinking water. The use of raw cane sugar as a space holder provides an environmentally friendly method for the production of foams with controllable porous network characteristics. Specifically, by applying a sugar volume of 70–80% with particle sizes in the range of 0.35–0.70 mm, it was possible to obtain final porosity of 65%, high structural stability, and enhanced interconnectivity of macropores required for the free flow of treated water. Smaller sugar particles ensure a smaller pore size and a higher specific surface area, favoring the interaction of water with the effective copper surface. Column tests indicated that a realistic filtering system using the Cu-foam can operate with complete Cr(VI) removal and minimum Cu leaching in the pH 7 ± 0.2 range, capturing chromium in the form of Cr(III) and Cr(VI) oxides. Chromium is homogeneously distributed and incorporated into the copper porous network allowing an almost unlimited lifetime of effective use compared to common adsorbents.     

Raman spectroscopic study of hexavalent chromium in some silicate and borate glasses

The polarized Raman spectra of chromium-doped silicate and borate glasses have been measured and interpreted. It is shown that hexavalent chromium exists in silicate glasses as isolated chromate anions (CrO₄⁼). In binary sodium borate glasses there is a change of species from chromate to dichromate as the B₂O₃ concentration is increased.     

Fixed-bed column study for hexavalent chromium removal and recovery by short-chain polyaniline synthesized on jute fiber

Fixed-bed column studies were conducted to evaluate performance of a short-chain polymer, polyaniline, synthesized on the surface of jute fiber (PANI-jute) for the removal of hexavalent chromium [Cr(VI)] in aqueous environment. Influent pH, column bed depth, influent Cr(VI) concentrations and influent flow rate were variable parameters for the present study. Optimum pH for total chromium removal was observed as 3 by electrostatic attraction of acid chromate ion (HCrO(4)(-)) with protonated amine group (NH(3)(+)) of PANI-jute. With increase in column bed depth from 40 to 60 cm, total chromium uptake by PANI-jute increased from 4.14 to 4.66 mg/g with subsequent increase in throughput volume from 9.84 to 12.6L at exhaustion point. The data obtained for total chromium removal were well described by BDST equation till 10% breakthrough. Adsorption rate constant and dynamic bed capacity at 10% breakthrough were observed as 0.01 L/mgh and 1069.46 mg/L, respectively. Adsorbed total chromium was recovered back from PANI-jute as non-toxic Cr(III) after ignition with more than 97% reduction in weight, minimizing the problem of solid waste disposal.     

Reduction of hexavalent chromium by Pannonibacter phragmitetus LSSE-09 coated with polyethylenimine-functionalized magnetic nanoparticles under alkaline conditions

A novel cell separation and immobilization method for Cr (VI)-reduction under alkaline conditions was developed by using superparamagnetic Fe(3)O(4) nanoparticles (NPs). The Fe(3)O(4) NPs were synthesized by coprecipitation followed by modification with sodium citrate and polyethyleneimine (PEI). The surface-modified NPs were monodispersed and the particle size was about 15 nm with a saturation magnetization of 62.3 emu/g and an isoelectric point (pI) of 11.5 at room temperature. PEI-modified Fe(3)O(4) NPs possess positive zeta potential at pH below 11.5, presumable because of the high density of amine groups in the long chains of PEI molecules on the surface. At initial pH 9.0, Pannonibacter phragmitetus LSSE-09 cells were immobilized by PEI-modified NPs via electrostatic attraction and then separated with an external magnetic field. Compared to free cells, the coated cells not only had the same Cr (VI)-reduction activity but could also be easily separated from reaction mixtures by magnetic force. In addition, the magnetically immobilized cells retained high specific Cr (VI)-reduction activity over six batch cycles. The results suggest that the magnetic cell separation technology has potential application for Cr (VI) detoxification in alkaline wastewater.     

Reduction of hexavalent chromium by Pannonibacter phragmitetus LSSE-09 stimulated with external electron donors under alkaline conditions

A novel Cr (VI) resistant bacterial strain LSSE-09, identified as Pannonibacter phragmitetus, was isolated from industrial sludge. It has strong aerobic and anaerobic Cr (VI)-reduction potential under alkaline conditions. At 37 °C and pH 9.0, growing cells of strain LSSE-09 could completely reduce 100 and 1000 mg L(-1) Cr (VI)-Cr (III) within 9 and 24h, respectively under aerobic condition. Resting cells showed higher anaerobic reduction potential with the rate of 1.46 mg g(-1)((dry weight))min(-1), comparing with their aerobic reduction rate, 0.21 mg g(-1)min(-1). External electron donors, such as lactate, acetate, formate, pyruvate, citrate and glucose could highly increase the reduction rate, especially for aerobic reduction. The presence of 3000 mg L(-1) acetate enhanced anaerobic and aerobic Cr (VI)-reduction rates up to 9.47 mg g(-1)min(-1) and 4.42 mg g(-1)min(-1), respectively, which were 5 and 20 times faster than those without it. Strain LSSE-09 retained high activities over six batch cycles and NO(3)(-) and SO(4)(2-) had slightly negative effects on Cr (VI)-reduction rates. The results suggest that strain LSSE-09 has potential application for Cr (VI) detoxification in alkaline wastewater.