Low-temperature chromium(VI) biotransformation in soil with varying electron acceptors

Effective and low-cost strategies for remediating chromium (Cr)-contaminated soil are needed. Chromium(VI) leaching from contaminated soil into ground water and surface water threatens water supplies and the environment. This study tested indigenous Cr(VI) microbial transformation in batch systems at 10 degrees C in the presence of various electron acceptors. The effects of carbon addition, spiked Cr(VI), and mixing highly contaminated soil with less contaminated soil were investigated. The results indicated that Cr(VI) can be biotransformed in the presence of different electron acceptors including oxygen, nitrate, sulfate, and iron. Sugar addition had the greatest effect on enhancing Cr(VI) removal. Less dissolved organic carbon (DOC) was consumed per amount of Cr(VI) transformed under anaerobic conditions [0.8-93 mg DOC/mg Cr(VI)] compared with aerobic conditions [1.4-265 mg DOC/mg Cr(VI)]. Toxicity of high concentrations (< 160 mg/L) of spiked Cr(VI) were not evident. At Cr(VI) concentrations > 40 mg/L, aerobic conditions promoted faster Cr(VI) reduction than anaerobic conditions with nitrate or sulfate present. Biotransformation of Cr(VI) in highly contaminated soil (22,000 mg Cr/kg) was facilitated by mixing with less-contaminated soil. The study results provide a framework for evaluating indigenous Cr(VI) microbial transformation and enhance the ability to develop strategies for soil treatment.     

In situ reduction of chromium(VI) in heavily contaminated soils through organic carbon amendment

Chromium has become an important soil contaminant at many sites, and facilitating in situ reduction of toxic Cr(VI) to nontoxic Cr(III) is becoming an attractive remediation strategy. Acceleration of Cr(VI) reduction in soils by addition of organic carbon was tested in columns pretreated with solutions containing 1000 and 10 000 mg L(-1) Cr(VI) to evaluate potential in situ remediation of highly contaminated soils. Solutions containing 0,800, or 4000 mg L(-1) organic carbon in the form of tryptic soy broth or lactate were diffused into the Cr(VI)-contaminated soils. Changes in Cr oxidation state were monitored through periodic micro-XANES analyses of soil columns. Effective first-order reduction rate constants ranged from 1.4 x 10(-8) to 1.5 x 10(-7) s(-1), with higher values obtained for lower levels of initial Cr(VI) and higher levels of organic carbon. Comparisons with sterile soils showed that microbially dependent processes were largely responsible for Cr(VI) reduction, except in the soils initially exposed to 10 000 mg L(-1) Cr(VI) solutions that receive little (800 mg L(-1)) or no organic carbon. However, the microbial populations (< or = 2.1 x 10(5) g(-1)) in the viable soils are probably too low for direct enzymatic Cr(VI) reduction to be important. Thus, synergistic effects sustained in whole soil systems may have accounted for most of the observed reduction. These results show that acceleration of in situ Cr(VI) reduction with addition of organic carbon is possible in even heavily contaminated soils and suggest that microbially dependent reduction pathways can be dominant.     

Chromate reduction by chromium-resistant bacteria isolated from soils contaminated with dichromate

Extensive use of hexavalent chromium [Cr(VI)] in various industrial applications has caused substantial environmental contamination. Chromium-resistant bacteria isolated from soils can be used to remove toxic Cr(VI) from contaminated environments. This study was conducted to isolate chromium-resistant bacteria from soils contaminated with dichromate and describes the effects of some environmental factors such as pH, temperature, and time on Cr(VI) reduction and resistance. We found that chromium-resistant bacteria can tolerate 2500 mg L(-1) Cr(VI), but most of the isolates tolerated and reduced Cr(VI) at concentrations lower than 1500 mg L(-1). Chromate reduction activity of whole cells was detected in five isolates. Most of these isolates belong to the genus Bacillus as identified by the 16S rRNA gene sequencing. Maximal Cr(VI) reduction was observed at the optimum pH (7.0-9.0) and temperature (30 degrees C) of growth. One bacterial isolate (Bacillus sp. ES 29) was able to aerobically reduce 90% of Cr(VI) in six hours. The Cr(VI) reduction activity of the whole cells of five isolates had a K(M) of 0.271 (2.61 mM) to 1.51 mg L(-1) (14.50 mM) and a V(max) of 88.4 (14.17 nmol min(-1)) to 489 mg L9-1) h(-1) (78.36 nmol min(-1)). Our consortia and monocultures of these isolates can be useful for Cr(VI) detoxification at low and high concentrations in Cr(VI)-contaminated environments and under a wide range of environmental conditions.     

Arsenic and chromium removal by mixed magnetite–maghemite nanoparticles and the effect of phosphate on removal

Adsorption of arsenic and chromium by mixed magnetite and maghemite nanoparticles from aqueous solution is a promising technology. In the present batch experimental study, a commercially grade nano-size ‘magnetite’, later identified in laboratory characterization to be mixed magnetite–maghemite nanoparticles, was used in the uptake of arsenic and chromium from different water samples. The intent was to identify or develop a practical method for future groundwater remediation. The results of the study showed 96–99% arsenic and chromium uptake under controlled pH conditions. The maximum arsenic adsorption occurred at pH 2 with values of 3.69 mg/g for arsenic(III) and 3.71 mg/g for arsenic(V) when the initial concentration was kept at 1.5 mg/L for both arsenic species, while chromium(VI) concentration was 2.4 mg/g at pH 2 with an initial chromium(VI) concentration of 1 mg/L. Thus magnetite–maghemite nanoparticles can readily adsorb arsenic and chromium in an acidic pH range. Redox potential and pH data helped to infer possible dominating species and oxidation states of arsenic and chromium in solution. The results also showed the limitation of arsenic and chromium uptake by the nano-size magnetite–maghemite mixture in the presence of a competing anion such as phosphate. At a fixed adsorbent concentration of 0.4 g/L, arsenic and chromium uptake decreased with increasing phosphate concentration. Nano-size magnetite–maghemite mixed particles adsorbed less than 50% arsenic from synthetic water containing more than 3 mg/L phosphate and 1.2 mg/L of initial arsenic concentration, and less than 50% chromium from synthetic water containing more than 5 mg/L phosphate and 1.0 mg/L of chromium(VI). In natural groundwater containing more than 5 mg/L phosphate and 1.13 mg/L of arsenic, less than 60% arsenic uptake was achieved. In this case, it is anticipated that an optimum design with magnetite–maghemite nanoparticles may achieve high arsenic uptake in field applications.     

Microbial reduction of hexavalent chromium under vadose zone conditions

Hexavalent chromium [Cr(VI)] is a common contaminant associated with nuclear reactors and fuel processing. Improper disposal at facilities in and and semiarid regions has contaminated underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those in the vadose zone, and to evaluate the potential for enhancing biological Cr(VI) reduction through nutrient addition. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic C (molasses). Nutrient amendments resulted in up to 87% reduction of the initial 67 mg L(-1) Cr(VI) in an unsaturated batch experiment. Molasses and nitrate additions to 15 cm long unsaturated flow columns receiving 65 mg L(-1) Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-d experiment. All of the immobilized Cr was in the form of Cr(III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy, and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.     

含Cr（Ⅵ）废水生物处理技术及其影响因素

本文综述了微生物还原处理含价铬的废水的研究进展。讨论了影响微生物还原Cr(Ⅵ）因素包括生物体密度、初始Cr（Ⅵ）的浓度、碳源、pH、温度、溶解氧、氧化还原电位、含氧阴离子和金属离子。微生物还原Cr（Ⅵ）技术作为一种富有创新的研究应用于Cr（Ⅵ）污染的环境恢复。     

Effects of plants on the removal of hexavalent chromium in wetland sediments

The effect of two wetland plants, Typha latifolia L. (cattail) and Phragmites australis (Cav.) Trin. ex Steud (common reed), on the fate of Cr(VI) in wetland sediments was investigated using greenhouse bench-scale microcosm experiments. The removal of Cr(VI) was monitored based on the vertical profiles of aqueous Cr(VI) in the sediments. The Cr(VI) removal rates were estimated taking into account plant transpiration, which was found to significantly concentrate dissolved species in the sediments. After correcting for evapotranspiration, the actual Cr(VI) removal rates were significantly higher than would be inferred from uncorrected profiles. On average, the Cr(VI) removal rates were 0.005 to 0.017 mg L(-1) d(-1), 0.0003 to 0.08 mg L(-1) d(-1), and 0.004 to 0.13 mg L(-1) d(-1) for the control, T. latifolia, and P. australis microcosms, respectively. The fate of the removed Cr(VI) was examined by determining the quantity and chemical speciation of the Cr in the sediment and plant materials. Chromium(III) was the dominant form of Cr in both the sediment and plants, and precipitation of Cr(III) in the sediment was the major pathway responsible for the disappearance of aqueous Cr(VI) from the pore water. Incubation results showed that abiotic reduction was the primary mechanism underlying Cr(VI) removal in the microcosm sediments. Organic compounds produced by plants, including root exudates and mineralization products of dead roots, are thought to be the factor that is either directly or indirectly responsible for the gap between Cr(VI) removal efficiencies in the sediments of the vegetated and unvegetated microcosms.     

Removal of chromium (VI) from aqueous solution using walnut hull

In this study, removal of chromium (VI) from aqueous solution by walnut hull (a local low-cost adsorbent) was studied. The extent of adsorption was investigated as a function of solution pH, contact time, adsorbent and adsorbate concentration, reaction temperature and supporting electrolyte (sodium chloride). The Cr (VI) removal was pH-dependent, reaching a maximum (97.3%) at pH 1.0. The kinetic experimental data were fitted to the first-order, modified Freundlich, intraparticle diffusion and Elovich models and the corresponding parameters were obtained. A 102.78 kJ/mol Ea (activation energy) for the reaction of chromium (VI) adsorption onto walnut indicated that the rate-limiting step in this case might be a chemically controlled process. Both the Langmuir and Freundlich isotherms were suitable for describing the biosorption of chromium (VI) onto walnut hull. The uptake of chromium (VI) per weight of adsorbent increased with increasing initial chromium (VI) concentration up to 240-480 mg/L, and decreased sharply with increasing adsorbent concentration ranging from 1.0 to 5.0 g/L. An increase in sodium chloride (as supporting electrolyte) concentration was found to induce a negative effect while an increase in temperature was found to give rise to a positive effect on the chromium (VI) adsorption process. Compared to the various other adsorbents reported in the literature, the walnut hull in this study shows very good promise for practical applicability.     

Occurrence of metals in soil and ground water near chromated copper arsenate-treated utility poles

To thoroughly investigate the metal contamination around chromated copper arsenate (CCA)/polyethylene glycol (PEG)-treated utility poles, a total of 189 soil samples obtained from different depths and distances near six treated poles in the Montreal area (Canada) were analyzed for Cu, Cr, and As content. Various soil physicochemical properties were also determined. Ground water samples collected below the poles were analyzed for metals and bioassays with Daphnia magna were conducted. Generally, sandy soils had lower contaminant levels than clayey and organic soils. Copper concentrations in soil were highest followed by As and Cr. The highest Cu (1460 +/- 677 mg kg(-1)), As (410 +/- 150 mg kg(-1)), and Cr (287 +/- 32 mg kg(-1)) concentrations were found at the ground line and immediately adjacent to the pole. Contaminant levels then decreased with distance, approaching background levels within 0.1 m from the pole for Cr and 0.5 m for Cu and As. Chromium and Cu levels generally approached background levels at a depth of 0.5 m. Average As content near the pole on all study sites was three to eight times higher than Quebec's Level C criterion (50 mg kg(-1)), although it dropped to 31 mg kg(-1) at 0.1 m. Results also showed that As persisted up to 1 m in soil depth (17-54 mg kg(-1)). Copper and Cr concentrations in ground water samples were always <1.000 mg L(-1) and <0.05 mg L(-1), respectively and Cr(VI) was <0.02 mg L(-1). One sample contained an As concentration >0.025 mg L(-1) but bioassays showed that, overall, ground water had a low ecotoxic potential.     

Structure and thermal stability of toxic chromium(VI) species doped onto TiO2 powders through heat treatment

Chromium(VI)-containing sorbents in the form of sludge or solid residue from treatment processes are often landfilled or used as fill materials, therefore the long-term stability of metal binding is important. The reduction of Cr(VI)–Cr(III) through heat treatment may be a useful detoxification method. After heating at 500, 900, 1000, and 1100 °C for 4 h, the transformation of chemical states of chromium on 105 °C-dried, 7.9% Cr(VI)-doped TiO₂ powders was studied on the basis of surface area measurements, scanning electron microscopy (SEM) images, X-ray diffraction (XRD), and extended X-ray absorption fine structure (EXAFS) spectra. It was shown that Cr(VI) was reduced to Cr(III) in the Cr(VI)-doped samples after heating within 500–900 °C. The present results also suggested that the chromium octahedral was bridged to the titanium tetrahedral and was incorporated in TiO₂ minerals formed after 1000 °C treatment.     

Evaluation of hexavalent chromium removal in a continuous biological filter with the use of central composite design (CCD)

Hexavalent chromium is frequently found in industrial effluents as a result of the industrial applications of this compound and its anti-corrosive features. However, hexavalent chromium is extremely toxic, and its discharge in water is regulated, with a maximum limit of 0.1 mg/L in accordance with legislation established by CONAMA-Brazil (no. 397, April 3, 2008). To achieve lower discharge values, it is necessary to reduce from Cr(VI) to Cr(III), which is less toxic, and an economic alternative involves biological removal of this compound. Residence time distributions (RTDs) were measured to evaluate the behavior of actual biofilter operation conditions in a biofilter flow. The medium residence time distributions used were 8 and 24 h (recommended by the legislation). To optimize this process, a central composite design was used, considering the initial chromium concentration and pH as the independent variables and the removal of hexavalent chromium as the response. The boundary curves and surface response showed optimal behavior at 3.94 mg/L [Cr(0)] and a pH of 6.2. The removal process of hexavalent chromium is mathematically described by the Michaelis-Menten kinetic model. This model appropriately represents the variation of chromium concentration along the bioreactor.     

The influence of biochar and black carbon on reduction and bioavailability of chromate in soils

The widespread use of chromium (Cr) has a deleterious impact on the environment. A number of pathways, both biotic and abiotic in character, determine the fate and speciation of Cr in soils. Chromium exists in two predominant species in the environment: trivalent [(Cr(III)] and hexavalent [Cr(VI)]. Of these two forms, Cr(III) is nontoxic and is strongly bound to soil particles, whereas Cr(VI) is more toxic and soluble and readily leaches into groundwater. The toxicity of Cr(VI) can be mitigated by reducing it to Cr(III) species. The objective of this study was to examine the effect of organic carbon sources on the reduction, microbial respiration, and phytoavailability of Cr(VI) in soils. Organic carbon sources, such as black carbon (BC) and biochar, were tested for their potential in reducing Cr(VI) in acidic and alkaline contaminated soils. An alkaline soil was selected to monitor the phytotoxicity of Cr(VI) in sunflower plant. Our results showed that using BC resulted in greater reduction of Cr(VI) in soils compared with biochar. This is attributed to the differences in dissolved organic carbon and functional groups that provide electrons for the reduction of Cr(VI). When increasing levels of Cr were added to soils, both microbial respiration and plant growth decreased. The application of BC was more effective than biochar in increasing the microbial population and in mitigating the phytotoxicity of Cr(VI). The net benefit of BC emerged as an increase in plant biomass and a decrease in Cr concentration in plant tissue. Consequently, it was concluded that BC is a potential reducing amendment in mitigating Cr(VI) toxicity in soil and plants.     

Bioconversion of selenate in methanogenic anaerobic granular sludge

The capacity of anaerobic granular sludge to remove selenate from contaminated wastewater was investigated. The potential of different types of granular sludge to remove selenate from the liquid phase was compared to that of suspended sludge and contaminated soil and sediment samples. The selenate removal rates ranged from 400 to 1500 microg g VSS(-1) h(-1), depending on the source of biomass, electron donor, and the initial selenate concentration. The granular structure protects the microorganisms when exposed to high selenate concentrations (0.1 to 1 mM). Anaerobic granular sludge "Eerbeek," originating from a UASB reactor treating paper mill wastewater, removed about 90, 50, and 36% of 0.1, 0.5, and 1 mM of Se, respectively, from the liquid phase when incubated with 20 mM lactate at 30 degrees C and pH 7.5. Selenite, elemental Se (Se(o)), and metal selenide precipitates were the conversion products. Enrichments from the anaerobic granular sludge "Eerbeek" were able to convert 90% of the 10-mM selenate to Se(o) at a rate of 1505 microg Se(VI) g cells(-1) h(-1), a specific growth rate of 0.0125 g cells h(-1), and a yield of 0.083 g cells mg Se(-1). Both microbial metabolic processes (e.g dissimilatory reduction) as well as microbially mediated physicochemical mechanisms (adsorption and precipitation) contribute to the removal of selenate from the Se-containing medium.     

Effects of organic amendments on the reduction and phytoavailability of chromate in mineral soil

In this study, seven organic amendments (biosolid compost, farm yard manure, fish manure, horse manure, spent mushroom, pig manure, and poultry manure) were investigated for their effects on the reduction of hexavalent chromium [chromate, Cr(VI)] in a mineral soil (Manawatu sandy soil) low in organic matter content. Addition of organic amendments enhanced the rate of reduction of Cr(VI) to Cr(III) in the soil. At the same level of total organic carbon addition, there was a significant difference in the extent of Cr(VI) reduction among the soils treated with organic amendments. There was, however, a significant positive linear relationship between the extent of Cr(VI) reduction and the amount of dissolved organic carbon in the soil. The effect of biosolid compost on the uptake of Cr(VI) from the soil, treated with various levels of Cr(VI) (0-1200 mg Cr kg(-1) soil), was examined with mustard (Brassica juncea L.) plants. Increasing addition of Cr(VI) increased Cr concentration in plants, resulting in decreased plant growth (i.e., phytotoxicity). Addition of the biosolid compost was effective in reducing the phytotoxicity of Cr(VI). The redistribution of Cr(VI) in various soil components was evaluated by a sequential fractionation scheme. In the unamended soil, the concentration of Cr was higher in the organic-bound, oxide-bound, and residual fractions than in the soluble and exchangeable fractions. Addition of organic amendments also decreased the concentration of the soluble and exchangeable fractions but especially increased the organic-bound fraction in soil.     

Exploitation of Trichoderma harzianum mycelial waste for the removal of rhodamine 6G from aqueous solution

The harvested mycelial waste of Trichoderma harzianum was used as an adsorbent for the removal of rhodamine 6G and was studied in batch mode. The effects of agitation time and initial dye concentration, adsorbent dosage and pH were examined. The study revealed that the amount of dye adsorbed (mgg(-1)) increased with increase in agitation time and reached equilibrium after 120 min, for dye concentrations of 10-50 mg L(-1). The adsorbent dosage of 1.0 g/50 mL and pH of 8.0 were found to be optimum for maximum dye removal. The batch mode adsorption data followed both the Langmuir and Freundlich isotherms. The pseudo first- and second-order rate kinetics were applied to the adsorbent system. The adsorption kinetics of rhodamine 6G showed that the pseudo-second-order kinetic model provided the best correlation of the equilibrium data. The study implies that it is possible to develop a dye removal system by using T. harzianum biomass, which occurs as sludge in waste stream of fermentation industries.     

Removal of basic dye (Astrazon Blue FGRL) using macroalga Caulerpa lentillifera

The macroalga Caulerpa lentillifera was found to have adsorption capacity for a basic dye, Astrazon Blue FGRL. For the whole range of concentrations employed in this work (20-1280 mgl(-1)), the adsorption reached equilibrium within the first hour. The kinetic data corresponded well with the pseudo second-order kinetic model where the rate constants decreased as initial dye concentrations increased. At low dye concentrations (20-80 mgl(-1)), an increase in the adsorbent dosage resulted in a higher removal percentage of the dye, but a lower amount of dye adsorbed per unit mass (q). The adsorption isotherm followed both the Langmuir and Freundlich models within the temperature range employed in this work (18-70 degrees C). The highest maximum adsorption capacity (q(m)) was obtained at 50 degrees C. The enthalpy of adsorption was estimated at 14.87 kJmol(-1) suggesting a chemical adsorption mechanism.     

Removal of Fe(II) from the wastewater of a galvanized pipe manufacturing industry by adsorption onto bentonite clay

Bentonite clay has been used for the adsorption of Fe(II) from aqueous solutions over a concentration range of 80-200 mg/l, shaking time of 1-60 min, adsorbent dosage from 0.02 to 2 g and pH of 3. The process of uptake follows both the Langmuir and Freundlich isotherm models and also the first-order kinetics. The maximum removal (>98%) was observed at pH of 3 with initial concentration of 100 mg/l and 0.5 g of bentonite. The efficiency of Fe(II) removal was also tested using wastewater from a galvanized pipe manufacturing industry. More than 90% of Fe(II) can be effectively removed from the wastewater by using 2.0 g of the bentonite. The effect of cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium and copper) on the removal of Fe(II) was studied in the concentration range of 10-500 mg/l. All the added cations reduced the adsorption of Fe(II) at high concentrations except Zn. Column studies have also been carried out using a certain concentration of wastewater. More than 99% recovery has been achieved by using 5 g of the bentonite with 3M nitric acid solution.     

Fate and toxicity of endosulfan in Namoi River water and bottom sediment

Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P < 0.05) more concentrated on the large (>63 microm) particle fraction compared with smaller size fractions (<5 microm and 5-24 microm) of bottom sediments from the Namoi River, Australia. Following completion of the particle size fractionation (6 to 12 wk) and a sediment toxicity assessment (2 wk), the sediments showed large decreases in concentrations of alpha-endosulfan that coincided with an increase in endosulfan sulfate concentrations and minimal changes in beta-endosulfan concentrations. In the Namoi River, similar patterns were observed in the composition of total endosulfan in monthly measurements of bottom sediments and in passive samplers placed in the water column following runoff from cotton (Gossypium hirsutum L.) fields. The toxicity of endosulfan sulfate in river water indicated by the nymphs of the epibenthic mayfly Jappa kutera, was more persistent than the alpha- and beta-endosulfan parent isomers due to its longer half-life. This suggests that endosulfan sulfate would contribute most to previously observed changes in population densities of aquatic biota. Measured concentrations of total endosulfan in river water of up to 4 microg L(-1) following storm runoff, exceed the range of the 96-h median lethal concentration (LC50) values in river water for both alpha-endosulfan (LC50 = 0.7 microg L(-1); 95% confidence interval [CI] = 0.5 to 1.1) and endosulfan sulfate (LC50 = 1.2 microg L(-1); 95% CI = 0.4 to 3.3). In contrast, the 10-d LC50 value for total endosulfan in the sediment toxicity test (LC50 = 162 microg kg(-1); 95% CI = 120 to 218 microg kg(-1)) was more than threefold higher than the highest measured concentration of total endosulfan in field samples of bottom sediment (48 microg kg(-1)). This suggests that pulse exposures of endosulfan in the water column following storm runoff may be more acutely toxic to riverine biota than in contaminated bottom sediment.     

Removal of selenate from water by zerovalent iron

Zerovalent iron (ZVI) has been widely used in the removal of environmental contaminants from water. In this study, ZVI was used to remove selenate [Se(VI)] at a level of 1000 microg L(-1) in the presence of varying concentrations of Cl-, SO(2-)4, NO(-)3, HCO(-)3, and PO(3-)4. Results showed that Se(VI) was rapidly removed during the corrosion of ZVI to iron oxyhydroxides (Fe(OH)). During the 16 h of the experiments, 100 and 56% of the added Se(VI) was removed in 10 mM Cl- and SO(2-)4 solutions under a closed contained system, respectively. Under an open condition, 100 and 93% of the added Se(VI) were removed in the Cl- and SO(2-)4 solutions, respectively. Analysis of Se species in ZVI-Fe(OH) revealed that selenite [Se(IV)] and nonextractable Se increased during the first 2 to 4 h of reaction, with a decrease of Se(VI) in the Cl- experiment and no detection of Se(VI) in the SO(2-)4 experiment. Two mechanisms can be attributed to the rapid removal of Se(VI) from the solutions. One is the reduction of Se(VI) to Se(IV), followed by rapid adsorption of Se(IV) to Fe(OH). The other is the adsorption of Se(VI) directly to Fe(OH), followed by its reduction to Se(IV). The results also show that there was little effect on Se(VI) removal in the presence of Cl- (5, 50, and 100 mM), NO(-)3 (1, 5, and 10 mM), SO(2-)4 (5 mM), HCO(-)3 (1 and 5 mM), or PO(3-)4 (1 mM) and only a slight effect in the presence of SO(2-)4 (50 and 100 mM), HCO(-)3 (10 mM), and PO(3-)4 (5 mM) during a 2-d experiment, whereas 10 mM PO(3-)4 significantly inhibited Se(VI) removal. This work suggests that ZVI may be an effective agent to remove Se from Se-contaminated agricultural drainage water.     

Thermochemical esterifying citric acid onto lignocellulose for enhancing methylene blue sorption capacity of rice straw

In this paper, rice straw was esterified thermochemically with citric acid (CA) to produce potentially biodegradable cationic sorbent. The modified rice straw (MRS) and crude rice straw (CRS) were evaluated for their methylene blue (MB) removal capacity from aqueous solution. The effects of various experimental parameters (e.g., initial pH, sorbent dose, dye concentration, ion strength, and contact time) were examined. The ratio of MB sorbed on CRS increased as the initial pH was increased from pH 2 to 10. For MRS, the MB removal ratio came up to the maximum value beyond pH 3. The 1.5g/l or up of MRS could almost completely remove the dye from 250mg/l of MB solution. The ratio of MB sorbed kept above 98% over a range from 50 to 450mg/l of MB concentration when 2.0g/l of MRS was used. Increase in ion strength of solution induced decline of MB sorption. The isothermal data fitted the Langmuir model. The sorption processes followed the pseudo-first-order rate kinetics. The intraparticle diffusion rate constant (k(id)) was greatly increased due to modification.