Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: Equilibrium, kinetics, and regeneration studies

In the present study, an adsorbent was prepared from tamarind seeds and used after activation for the removal of Cr(VI) from aqueous solutions. The tamarind seeds were activated by treating them with concentrated sulfuric acid (98% w/w) at a temperature of 150 °C. The adsorption of Cr(VI) was found to be maximum at low values of initial pH in the range of 1–3. The adsorption process of Cr(VI) was tested with Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan, Tempkin, Dubinin–Radushkevich and Generalized isotherm models. Application of the Langmuir isotherm to the system yielded a maximum adsorption capacity of 29.7 mg/g at an equilibrium pH value ranging from 1.12 to 1.46. The adsorption process followed second-order kinetics and the corresponding rate constants obtained were 2.605 × 10⁻³, 0.818 × 10⁻³, 0.557 × 10⁻³ and 0.811 × 10⁻³ g/mg min⁻¹ for 50, 200, 300 and 400 mg/L of initial Cr(VI) concentration, respectively. The regenerated activated tamarind seeds showed more than 95% Cr(VI) removal of that obtained using the fresh activated tamarind seeds. A feasible solution is proposed for the disposal of the contaminants (acid and base solutions) containing high concentrations of Cr(VI) obtained during the regeneration (desorption) process.     

Factors controlling phosphate interaction with iron oxides

Factors such as pH, solution ion composition, and the presence of natural organic matter (NOM) play a crucial role in the effectiveness of phosphorous adsorption by iron oxides. The interplay between these factors shows a complicated pattern and can sometimes lead to controversial results. With the help of mechanistic modeling and adsorption experiments, the net macroscopic effect of single and combined factors can be better understood and predicted. In the present work, the relative importance of the above-mentioned factors in the adsorption of phosphate was analyzed using modeling and comparison between the model prediction and experimental data. The results show that, under normal soil conditions, pH, concentration of Ca, and the presence of NOM are the most important factors that control adsorption of phosphate to iron oxides. The presence of Ca not only enhances the amount of phosphate adsorbed but also changes the pH dependency of the adsorption. An increase of dissolved organic carbon from 0.5 to 50 mg L can lead to a >50% decrease in the amount of phosphate adsorbed. Silicic acid may decrease phosphate adsorption, but this effect is only important at a very low phosphate concentration, in particular at high pH.     

Removal of Cr(VI) from Cr-contaminated groundwater through electrochemical addition of Fe(II)

The conventional chemical reduction-precipitation technique in the removal of Cr(VI) from contaminated groundwater involves a two-step process whereby Cr(VI) is first reduced to Cr(III) at an acidic pH by a reducing agent and in a subsequent step, Cr(III) is precipitated as insoluble hydroxide at an alkaline pH. In a variation of this method, Fe(II) is added electrochemically to the Cr(VI) containing water. From a pure iron electrode, Fe(2+) ions are released into the solution and bring forth the reduction of Cr(VI). At the cathode, H(2)O is reduced whereby the OH(-) ions entering the solution keep the pH of the solution in the alkaline range. This latter fact greatly facilitates simultaneous reduction of Cr(VI) to Cr(III) and co-precipitation of hydroxides of trivalent Cr and Fe. On the basis of a set of experimental data, it is shown that this process is both thermodynamically and kinetically efficient, meaning, with the electrochemical method, rapid and nearly complete removal of Cr(VI) from a groundwater source with both high and low levels of Cr-contamination can be achieved. These factors make the electrochemical process superior to the conventional chemical process in remediation of Cr-contaminated groundwater.     

The leaching characteristics of selenium from coal fly ashes

The leaching characteristics of selenium from several bituminous and subbituminous coal fly ashes under different pH conditions were investigated using batch methods. Results indicated that pH had a significant effect on selenium leaching from bituminous coal ash. The minimum selenium leaching occurred in the pH range between 3 and 4, while the maximum selenium leaching occurred at pH 12. The release of selenium from subbituminous coal ashes was very low for the entire experimental pH range, possibly due to the high content of calcium which can form hydration or precipitation products as a sink for selenium. The adsorption results for different selenium species indicated that Se(VI) was hardly adsorbable on either bituminous coal ashes or subbituminous coal ashes at any pH. However, Se(IV) was highly adsorbed by bituminous coal ashes under acidic pH conditions and was mostly removed by subbituminous coal ashes across the entire pH range. This result suggests that the majority of selenium released from the tested fly ashes was Se(IV). A speciation-based model was developed to simulate the adsorption of Se(IV) on bituminous coal fly ash, and the pH-independent adsorption constants of HSeO3* and SeO3 2* were determined. The modeling approach is useful for understanding and predicting the release process of selenium from fly ash.     

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.     

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.     

花生壳对Cr（Ⅵ）的等温吸附模型研究

在花生壳吸附剂量为1.0g、pH2.0、温度30℃、振荡速度140r/min、吸附时间360min条件下,实验研究了不同初始浓度（50 mg/L、75 mg/L、100 mg/L、125 mg/L、150 mg/L）的Cr（Ⅵ）溶液等温吸附曲线。研究结果表明,Langmuir等温吸附模型符合得更好;该吸附是一个优先吸附过程;最大饱和吸附量为6.25mg/g。     

Evaluation of the potential for the natural attenuation of hexavalent chromium within a sub-wetland ground water

In this work, the potential for natural attenuation (NA) of Cr(VI) is evaluated for sub-wetland ground water at a chromium-contaminated site in Connecticut, incorporating the experimental findings of previous work at the site. Experimental data is assessed through long-term attenuation capacity calculations and modeling, which incorporates statistical uncertainty of parametric values. The NA evaluation yielded the following results: (1) Significant increases in Cr(VI) concentration and extremely long chromium source dissolution timeframes are required to exceed the attenuation capacity of the sub-wetland region soils studied in this work; and (2) Based on the 1-D transport modeling and incorporating input parameter uncertainty, there is an approximately 92% and 98% probability that the applicable regulatory criteria will not be exceeded at Point C, near a river which serves as the receptor, for the cases of (1) sorption of Cr(VI) only and (2) pseudo first order disappearance of Cr(VI) from the aqueous phase only, respectively.     

Removal of direct red 12B and methylene blue from water by adsorption onto Fe (III)/Cr (III) hydroxide, an industrial solid waste

Removal of direct red 12B and methylene blue by adsorption onto Fe (III)/Cr (III) hydroxide was studied using various parameters such as agitation time, dye concentration, adsorbent dose and pH. Equilibrium adsorption data followed both Langmuir and Freundlich isotherms. Adsorption followed second-order rate kinetics. The Langmuir adsorption capacity (Qo) was found to be 5.0 and 22.8 mg dye per g of the adsorbent for direct red 12B and methylene blue, respectively. Acidic pH was favorable for the adsorption of direct red 12B and basic pH for methylene blue. Desorption studies showed that chemisorption seems to be the major mode of adsorption.     

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.     

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.     

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.     

Removal of heavy metals in rinsing wastewater from plating factory by adsorption with economical viable materials

The removal of heavy metals from plating factory wastewater with economical materials was investigated by the column method. Montmorillonite, kaolin, tobermorite, magnetite, silica gel and alumina were used as the economical adsorbents to wastewater containing Cd(II), Cr(VI), Cu(II) and Pb(II). This removal method of heavy metals proved highly effective as removal efficiency tended to increase with increasing pH and decrease with increasing metal concentration. The removal percentages by adsorption onto montmorillonite, tobermorite, magnetite, and silica gel showed high values for all metals. From the results for the heat of adsorption, the adsorption process in the present study might be chemisorption. The proposed method was successfully applied to the removal of Cd(II), Cr(VI) and Cu(II) in rinsing wastewater from plating factory in Nagoya City, Aichi Prefecture, Japan. Since the economical adsorbents used can be obtained commercially because they are easily synthesized, the wastewater treatment system developed is rapid, simple and cheap for the removal of heavy metals.     

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.     

Optimization of the removal of chromium and lead by Penicillium chrysogenum using 2k factorial experiments

This study aims to prepare a low-cost, environmentally friendly, and alternative, biosorbent to remove chromium Cr (III) and lead Pb (II) from polluted water and to find out the highest removal efficiencies using 2^k factorial experiments. The Cr (III) and Pb (II) tolerant fungal strain identified as Penicillium chrysogenum was isolated from ceramic industrial sludge. The impact of process variables on biosorption of Cr (III) and Pb (II) by P. chrysogenum was first evaluated with the Taguchi screening design. Factors and levels were determined to optimize Cr (III) and Pb (II) removal efficiency. According to this, five factors; initial concentration, pH, biosorbent dose, temperature, and inactivation methods were determined for both metals, each factor defined as a fixed factor with two levels. Optimization of the parameters affecting the removal process was determined by the Taguchi method and the signal-to-noise (S/N) ratios are calculated. The maximum removal efficiency (99.92%) was observed at pH 7, biosorbent 1 mg L^–1, inactivation with autoclaving, and at 20°C with an initial metal concentration of 50 mg L^–1 Cr (III). On the other hand, the maximum removal efficiency (98.99%) was observed at pH 4, biosorbent 5 mg L^–1, inactivation with autoclaving, and at 20°C with an initial metal concentration of 50 mg L^–1 Pb (II). Furthermore, metal ions removal by P. chrysogenum was also confirmed by scanning electron microscopy (SEM) combined with an energy dispersive X-ray spectrometer (EDS). The presence of functional groups on fungal cells of metal binding was investigated by Fourier transform infrared (FT-IR).     

Sorption of hazardous metals from single and multi-element solutions by saltbush biomass in batch and continuous mode: interference of calcium and magnesium in batch mode

Batch studies were performed to determine the interference of calcium (Ca) and magnesium (Mg) on the sorption of Cu(II), Cd(II), Cr(III), Cr(VI), Pb(II), and Zn(II) [from CuSO(4), K(2)Cr(2)O(7), Pb(NO(3))(2), Cr(NO(3))(3), ZnCl(2), and Cd(NO(3))(2)] by saltbush (Atriplex canescens) biomass. The results demonstrated that Ca and Mg at concentrations of at least 20 times higher than the concentration of most of the target metals did not interfere with the metal binding. The data show that the batch binding capacity from a multimetal solution at pH 5.0 was (micromol/g) about 260 for Cr(III) and Pb, and about 117, 54, and 49 for Cu, Zn, and Cd, respectively. The use of 0.1M HCl allowed the recovery of 85-100% of the bound Cu, Cr(III), and Pb, and more than 37% of the bound Cd and Zn. The column binding capacity for Pb was about 49 micromol/g from both the single and multimetal solutions, while it was, respectively about 35 and 23 micromol/g for Cr(III). The binding capacity for Cu and Zn from the single and multimetal column experiments was 35 micromol/g and less than 10 micromol/g, respectively. The stripping data from the single column experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and Zn, 90% and 74% of the bound Pb and Cr(VI), respectively, and less than 25% of the bound Cd and Cr(III), while the stripping from the multimetal experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and about 74%, 54%, 43%, and 40% of the bound Pb, Zn, Cd, and Cr(III), respectively.     

Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI)

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.     

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.     

Perfluorinated phosphine oxide and sulfides as extractants for heavy metals and radionuclides

New highly fluorinated monodentate and bidentate phosphine oxide compounds of the type {CF(3)(CF(2))(n)CH(2)CH(2)}(3)PO (n = 5, 9) and [{CF(3)(CF(2))(5)CH(2)CH(2)}(2)P(O)CH(2)CH(2)P(O){CH(2)CH(2)(CF(2))(5)CF(3)}] have been prepared. Their ability to extract a number of metals and radionuclides from aqueous solutions into perfluorinated solvents has been established and the extractable species investigated. All extractants extract the metals As(V), Cd(II), Co(II), Cr(VI), Hg(II), Pb(II), and Sn(II) with >75% removal. In addition, the radioisotopes (90)Sr(II), (133)Ba(II), and U(VI) have been investigated, whilst (59)Fe(III) has been used to model the extraction of plutonium. (133)Ba(II) shows a high distribution ratio for monodentate phosphine oxides, whilst for UO(2)(2+) and (59)Fe(III) bidentate phosphine oxides are superior.     

Soil,water and plants contamination by total chrome and chrome VI

The chrome (Cr) is a metal utilized in various industrial sectors and its investigation in the environment is necessary, for the Cr (III) contain aessential micronutrients in the human nourishment and the Cr (VI), on the other hand, is toxic. In the present work soil contamination with Cr was realized in drainagelysimetersset in concentrations of 0, 200, 400, 600, 800 and 1000 mg kg⁻¹ of total Cr, with the intuition to determine the total Cr and Cr (VI) flux in leached water, in soil and in plants of lettuce (Lactuca sativa L.). In the lysimeters were cultivated four plants, in three cultivation circles. In the end of the cultivations was observed, that the total applied Cr leached in the soil, evidencing the Cr mobility in latossoil with simulant characteristics to the ones utilized in this paper. The Cr (VI) concentrations in the soil increased soon after the treatment applications, but tend to decrees in the time elapse, the same tendences were observed for the total Cr concentrations in the leached water. The Cr absorption by plants was related to the Cr disponibility in the soil, for the soil concentration and the plants decreased with time passing. The Cr mobility in the soil possibilitated the groundwater contamination presenting risks to the water quality and, consequently to public health.