Chromium speciation in river sediment pore water contaminated by tannery effluent

Cr(VI) is far more soluble and toxic than Cr(III). Sediment pore water was investigated in a river adjacent to the property of a large former tannery, into which Cr-contaminated effluent was discharged over a 55-year period, and where extremely high Cr concentrations have been found in the sediments. Dialysis cells, or peepers, were used to generate depth profiles of Cr concentration in sediment pore water. Samples were analyzed for total Cr using inductively coupled plasma-mass spectrometry (ICP-MS) and for Cr species using high performance liquid chromatography (HPLC)-ICP-MS. The results show an absence of Cr(VI) in all samples. Furthermore, incomplete recovery of Cr(VI) added to the samples collected at the locations with highest sediment Cr concentrations indicate strong reducing conditions at those locations, which are not conducive to the presence of Cr(VI).     

Speciation of Cd and Zn in contaminated soils assessed by DGT-DIFS, and WHAM/Model VI in relation to uptake by spinach and ryegrass

A pot experiment was carried out to investigate the impact of Cd and Zn extractability in soil and speciation in pore water of industrial contaminated soils, on metal concentration in a metal sensitive species like spinach (Spinacia oleracea) and a more metal tolerant species like Italian ryegrass (Lolium multiflorum). For chemical speciation of Cd and Zn in pore water, WHAM/Model VI version 6.0 was used. The DGT technique was used to determine the effective concentration, C(E), of Cd and Zn in soils. The free ion activity in pore water correlated well with the contents in plants, and there was a linear relationship between the C(E) values and the concentration of Cd and Zn in both spinach and ryegrass in the non-toxic range. However, the C(E) values usually overestimated the plant contents when plants, particularly the spinach plants, were subjected to toxic concentration in the pore water. Metal uptake decreased in plants affected by toxicity, whereas metal binding to the Chelex resin did not. Thus, we found no linear relationship between the C(E) and metal contents in spinach, whereas a linear relationship was found between C(E)-Zn and the Zn concentration in ryegrass (r2=0.96, p<0.001). For Cd in ryegrass this relationship was weak (r2=0.53, p=0.18). This study indicates that the transport of metals from labile metal pools to the DGT-resin is linearly related to plant uptake only when plants are growing well, and that the applicability of DGT as an indicator for plant uptake seems species dependent.     

Chromium species behaviour in the activated sludge process

The purpose of this research was to compare trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) removal by activated sludge and to investigate whether Cr(VI) reduction and/or Cr(III) oxidation occurs in a wastewater treatment system. Chromium removal by sludge harvested from sequencing batch reactors, determined by a series of batch experiments, generally followed a Freundlich isotherm model. Almost 90% of Cr(III) was adsorbed on the suspended solids while the rest was precipitated at pH 7.0. On the contrary, removal of Cr(VI) was minor and did not exceed 15% in all experiments under the same conditions. Increase of sludge age reduces Cr(III) removal, possibly because of Cr(III) sorption on slime polymers. Moreover, the decrease of suspended solids concentration and the acclimatization of biomass to Cr(VI) reduced the removal efficiency of Cr(III). Batch experiments showed that Cr(III) cannot be oxidized to Cr(VI) by activated sludge. On the contrary, Cr(VI) reduction is possible and is affected mainly by the initial concentration of organic substrate, which acts as electron donor for Cr(VI) reduction. Initial organic substrate concentration equal to or higher than 1000 mgl(-1) chemical oxygen demand permitted the nearly complete reduction of 5 mgl(-1) Cr(VI) in a 24-h batch experiment. Moreover, higher Cr(VI) reduction rates were obtained with higher Cr(VI) initial concentrations, expressed in mg Cr(VI) g(-1) VSS, while decrease of suspended solids concentration enhanced the specific Cr(VI) reduction rate.     

Chromium accumulation by the hyperaccumulator plant Leersia hexandra Swartz

Leersia hexandra Swartz (Gramineae), which occurs in Southern China, has been found to be a new chromium hyperaccumulator by means of field survey and pot-culture experiment. The field survey showed that this species had an extraordinary accumulation capacity for chromium. The maximum Cr concentration in the dry leaf matter was 2978 mg kg(-1) on the side of a pond near an electroplating factory. The average concentration of chromium in the leaves was 18.86 times as that in the pond sediment, and 297.41 times as that in the pond water. Under conditions of the nutrient solution culture, it was found that L. hexandra had a high tolerance and accumulation capacity to Cr(III) and Cr(VI). Under 60 mg l(-1) Cr(III) and 10 mg l(-1) Cr(VI) treatment, there was no significant decrease of biomass in the leaves of L. hexandra (p>0.05). The highest bioaccumulation coefficients of the leaves for Cr(III) and Cr(VI) were 486.8 and 72.1, respectively. However, L. hexandra had a higher accumulation capacity for Cr(III) than for Cr(VI). At the Cr(III) concentration of 10 mg l(-1) in the culture solution, the concentration of chromium in leaves was 4868 mg kg(-1), while at the same Cr(VI) concentration, the concentration of chromium in leaves was only 597 mg kg(-1). These results confirmed that L. hexandra is a chromium hyperaccumulator which grows rapidly with a great tolerance to Cr and broad ecological amplitude. This species could provide a new plant resource that explores the mechanism of Cr hyperaccumulation, and has potential for usage in the phytoremediation of Cr-contaminated soil and water.     

Removal of Cr(VI) and humic acid by using TiO2 photocatalysis

The removal efficiencies of Cr(VI) and HA, using a TiO(2)-mediated photocatalytic process, were investigated with variations in the pH, TiO(2) dosage and Cr(VI)/HA ratio. During the photocatalytic reaction, the total removal of Cr(VI) occurred through adsorption onto TiO(2), as well as its reduction to Cr(III). However, oxidation and adsorption were identified as important removal processes for the treatment of HA. Due to the anionic type adsorption onto TiO(2) and its acid-catalyzed photocatalytic reduction, the removal of Cr(VI) decreased with increasing pH, while that of HA increased with increasing pH. The TiO(2) dosage was also an important parameter for the removal of Cr(VI). As the TiO(2) dosage was increased to 2.5 g l(-1), the removal of Cr(VI) was continuously enhanced, but decreased at dosages above 3 g l(-1) due to the increased blockage of the incident UV light used for the photocatalytic reaction. The removal of Cr(VI) was greatly enhanced when the system contained both HA and Cr(VI) compared to Cr(VI) alone. Also, the removal of HA was greatly enhanced when the system contained both HA and Cr(VI) compared to HA alone. The removal of Cr(VI) was continuously enhanced as the HA concentration gradually increased; however, no further increase was observed above 20 mg l(-1) HA due to the increased absorption of the UV light. This result supports that the photocatalytic reaction, with illuminated TiO(2), could be applied to more effectively treat wastewater containing both Cr(VI) and HA than that containing a single species only.     

Accumulation of chromium (VI) from aqueous solutions using water lilies (Nymphaea spontanea)

This study describes an investigation using tropical water lilies (Nymphaea spontanea) to remove hexavalent chromium from aqueous solutions and electroplating waste. The results show that water lilies are capable of accumulating substantial amount of Cr(VI), up to 2.119 mg g(-1) from a 10 mg l(-1) solution. The roots of the plant accumulated the highest amount of Cr(VI) followed by leaves and petioles, indicating that roots play an important role in the bioremediation process. The maturity of the plant exerts a great effect on the removal and accumulation of Cr(VI). Plants of 9 weeks old accumulated the most Cr(VI) followed by those of 6 and 3 weeks old. The results also show that removal of Cr(VI) by water lilies is more efficient when the metal is present singly than in the presence of Cu(II) or in waste solution. This may be largely associated with more pronounced phytotoxicity effect on the biochemical changes in the plants and saturation of binding sites. Significant toxicity effect on the plant was evident as shown in the reduction of chlorophyll, protein and sugar contents in plants exposed to Cr(VI) in this investigation.     

Species-dependent chromium accumulation, lipid peroxidation, and glutathione levels in germinating kiwifruit pollen under Cr(III) and Cr(VI) stress

The accumulation of chromium by germinating kiwifruit pollen appears to be significantly affected by Cr species, Cr concentration and calcium availability. Cr(III) accumulation always occurred in a linear manner while Cr(VI) uptake followed a logarithmic model. In the absence of exogenous calcium, Cr(III) accumulation was much higher than that of Cr(VI). It was observed that, as the Cr(III) concentration increased, there was a significant decrease in the endogenous calcium content of pollen, ultimately leading to complete calcium depletion after 90 min of incubation at 150 microM Cr(III). This loss of calcium could be responsible for the strong inhibition of tube emergence and growth following exposure of pollen to Cr(III). Indeed, when exogenous calcium was added to the kiwifruit pollen culture medium, significant growth recovery and reduced Cr(III) uptake occurred; the opposite was true in Cr(VI)-treatments. A significant rise in lipid peroxide production occurs in the presence of both Cr species; the effect was more pronounced following Cr(VI) exposure. Finally, glutathione pool dynamics appears to be differentially affected by chromium species and concentrations. In conclusion, results of the present study have provided important information regarding the different activity profiles of Cr(III) and Cr(VI) in relation to kiwifruit pollen performance, and have also demonstrated differences in some biochemical responses of pollen to metal stress.     

Effect of sulfate reduction activity on biological treatment of hexavalent chromium [Cr(VI)] contaminated electroplating wastewater under sulfate-rich condition

Electroplating wastewater (EW) containing heavy metals was treated by a two-stage packed-bed reactor system. The EW was highly contaminated with hexavalent chromium and other heavy metals as well as sulfate because sulfuric acid had been mainly used to polish the surface of metals to be electroplated. This acidic EW was effectively neutralized in an alkaline reactor where limestone had been packed. The neutralized wastewater together with organic wastewater from a starch-processing factory (SPW) was fed to a bioreactor packed with waste biomass. The SPW was used to supplement the electron donor in the sulfidogenic bioreactor. During the whole operation, we investigated the stoichiometry of electron to see what could be a major factor to remove Cr in the wastewater. The removal rates of sulfate and Cr(VI) were dependent on the consumption rate of organic materials in the wastewater. The stoichiometric studies also showed that about 63% of electrons from oxidation of organic materials were used to reduce sulfate. When the electrons of sulfide oxidation to elemental sulfur was at least 1.3 times higher than that of Cr(VI) reduction to Cr(III), Cr(VI) was completely removed. This result suggests that Cr(VI) reduction can be expected to take place under sulfate-rich anaerobic conditions, and sulfide produced by sulfate reducing bacteria could be used to immobilize soluble chromium through Cr(VI) reduction.     

In vitro Cr(VI) reduction by cell-free extracts of chromate-reducing bacteria isolated from tannery effluent irrigated soil

Four efficient Cr(VI)-reducing bacterial strains were isolated from rhizospheric soil of plants irrigated with tannery effluent and investigated for in vitro Cr(VI) reduction. Based on 16S rRNA gene sequencing, the isolated strains SUCR44, SUCR140, SUCR186, and SUCR188 were identified as Bacillus sp. (JN674188), Microbacterium sp. (JN674183), Bacillus thuringiensis (JN674184), and Bacillus subtilis (JN674195), respectively. All four isolates could completely reduce Cr(VI) in culture media at 0.2 mM concentration within a period of 24–120 h; SUCR140 completely reduced Cr(VI) within 24 h. Assay with the permeabilized cells (treated with Triton X-100 and Tween 80) and cell-free assay demonstrated that the Cr(VI) reduction activity was mainly associated with the soluble fraction of cells. Considering the major amount of chromium being reduced within 24–48 h, these fractions could have been released extracellularly also during their growth. At the temperature optima of 28 °C and pH?7.0, the specific activity of Cr(VI) reduction was determined to be 0.32, 0.42, 0.34, and 0.28 μmol Cr(VI)?min^?1?mg^?1 protein for isolates SUCR44, SUCR140, SUCR186, and SUCR188, respectively. Addition of 0.1 mM NADH enhanced the Cr(VI) reduction in the cell-free extracts of all four strains. The Cr(VI) reduction activity in cell-free extracts of all the isolates was stable in presence of different metal ions tested except Hg²⁺. Beside this, urea and thiourea also reduced the activity of chromate reduction to significant levels.     

Investigation of Cr(VI) reduction in continuous-flow activated sludge systems

The aim of this research was to investigate hexavalent chromium, Cr(VI), reduction by activated sludge and to evaluate the use of continuous-flow activated sludge systems for the treatment of Cr(VI)-containing wastewater. Three series of experiments were conducted using two parallel lab-scale activated sludge systems. During the first experiment, one system was used as a control, while the other received Cr(VI) concentrations equal to 0.5, 1, 3 and 5mg l(-1). For all concentrations added, approximately 40% of the added Cr(VI) was removed during the activated sludge process. Determination of chromium species in the dissolved and particulate phase revealed that the removed Cr(VI) was sorbed by the activated sludge flocs mainly as trivalent chromium, Cr(III), while the residual chromium in the dissolved phase was mainly detected as Cr(VI). Activated sludge ability to reduce Cr(VI) was independent of the acclimatization of biomass to Cr(VI) and it was not affected by the toxic effect of Cr(VI) on autotrophic and heterotrophic microorganisms. During the second experiment, both systems were operated under two different hydraulic residence time (theta equal to 20 and 28h) and three different initial organic substrate concentration (COD equal to 300, 150 and 0mg l(-1)). Cr(VI) reduction was favored by an increase of theta, while it was limited by influent COD concentration. Finally, at the last experiment the effect of anoxic and anaerobic reactors on Cr(VI) reduction was investigated. It was observed that the use of an anoxic zone or an anaerobic-anoxic zone ahead of the aerobic reactor favored Cr(VI) reduction, increasing mean percentage Cr(VI) reduction to almost 80%.     

PBTCA稳定零价纳米铁的制备及其去除水中Cr(Ⅵ)

以2-膦酸丁烷-1,2,4三羧酸(PBTCA)为稳定剂,通过FeCl3.6H2O与NaBH4反应,利用液相还原法制备稳定纳米级零价铁颗粒(P-NZVI),并用透射电子显微镜(TEM)、扫描电子显微镜(SEM)及X射线衍射(XRD)进行表征,颗粒平均粒径为73 nm。考察了Cr(Ⅵ)溶液初始浓度、pH、NZVI投加量、温度等条件对Cr(Ⅵ)去除效果的影响,并与同等条件下不加稳定剂制备的纳米铁(N-NZVI)进行对比。结果表明:Cr(Ⅵ)的去除率随温度和纳米铁投加量增加而升高,随pH和Cr(Ⅵ)溶液初始浓度升高而降低。在相同实验条件下,P-NZVI对Cr(Ⅵ)的去除效果明显优于N-NZVI,表明改性后纳米铁在地表水原位修复领域具有较好的应用前景。     

Hexavalent chromium reduction kinetics in rodent stomach contents

Reduction of hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)) in the stomach prior to absorption is a well-recognized detoxification process thought to limit the toxicity of ingested Cr(VI). However, administration of high concentrations of Cr(VI) in drinking water cause mouse small intestinal tumors, and quantitative measures of Cr(VI) reduction rate and capacity for rodent stomach contents are needed for interspecies extrapolation using physiologically-based toxicokinetic (PBTK) models. Ex vivo studies using stomach contents of rats and mice were conducted to quantify Cr(VI) reduction rate and capacity for loading rates (1-400 mg Cr(VI) L⁻¹ stomach contents) in the range of recent bioassays. Cr(VI) reduction was measured with speciated isotope dilution mass spectrometry to quantify dynamic Cr(VI) and Cr(III) concentrations in stomach contents at select time points over 1 h. Cr(VI) reduction followed mixed second-order kinetics, dependent upon concentrations of both Cr(VI) and the native reducing agents. Approximately 16 mg Cr(VI)-equivalents of reducing capacity per L of fed stomach contents (containing gastric secretions, saliva, water and food) was found for both species. The second-order rate constants were 0.2 and 0.3 L mg⁻¹ h⁻¹ for mice and rats, respectively. These findings support that, at the doses that caused cancer in the mouse small intestine (?20 mg Cr(VI) L⁻¹ in drinking water), the reducing capacity of stomach contents was likely exceeded. Thus, for extrapolation of target tissue dose in risk assessment, PBTK models are necessary to account for competing kinetic rates including second order capacity-limited reduction of Cr(VI) to Cr(III).     

Use of waste iron metal for removal of Cr(VI) from water

Cr(VI) removal from water was evaluated using waste iron particles in batch experimental mode. The reaction rates were inversely proportional to the initial Cr(VI) concentrations, and the reaction rates of Cr(VI) removal with the waste iron metal were faster than those with Peerless iron, a commercial zero-valent iron. The loss in iron reactivity due to the oxidation, from Fe(0) to Fe(II), ultimately to Fe(III), could be recovered by adding iron-reducing consortium (IRC) to the oxidized iron. Bacterial reduction of Cr(VI) also helped to decrease the aqueous concentration of Cr(VI), but the reduction of oxidized iron by IRC and the consequent reduction of Cr(VI) to Cr(III) by the reduced iron was more significant. Thus, reusing waste iron metal for Cr(VI) removal can reduce the cost of reactive media. Furthermore, the addition of IRC to the waste iron metal can accelerate the removal rate of Cr(VI), and can recover the reactivity of irons which were oxidized by Cr(VI).     

Simultaneous Cr(VI) reduction and phenol degradation using Stenotrophomonas sp. isolated from tannery effluent contaminated soil

This study presents simultaneous hexavalent chromium (Cr(VI)) reduction and phenol degradation using Stenotrophomonas sp., isolated from tannery effluent contaminated soil. Phenol was used as the sole carbon and energy source for Cr(VI) reduction. The optimization of different operating parameters was done using Placket–Burman design (PBD) and Box–Behnken design (BBD). The significant operating variables identified by PBD were initial Cr(VI) and phenol concentration, pH, temperature, and reaction time. These variables were optimized by a three-level BBD and the optimum initial Cr(VI) concentration, initial phenol concentration, pH, temperature, and reaction time obtained were 16.59 mg/l, 200.05 mg/l, 7.38, 31.96 °C and 4.07 days, respectively. Under the optimum conditions, 81.27 % Cr(VI) reduction and 100 % phenol degradation were observed experimentally. The results concluded that the Stenotrophomonas sp. could be used to decontaminate the effluents containing Cr(VI) and phenol effectively.     

Chromium transport, oxidation, and adsorption in manganese-coated sand

We examine how the processes of advection, dispersion, oxidation-reduction, and adsorption combine to affect the transport of chromium through columns packed with pyrolusite (beta-MnO2)-coated sand. We find that beta-MnO2 effectively oxidizes Cr(III) to Cr(VI) and that the extent of oxidation is sensitive to changes in pH, pore water velocity, and influent concentrations of Cr(III). Cr(III) oxidation rates, although initially high, decline well before the supply of beta-MnO2 is depleted, suggesting that a reaction product inhibits the conversion of Cr(III) to Cr(VI). Rate-limited reactions govern the weak adsorption of each chromium species, with Cr(III) adsorption varying directly with pH and Cr(VI) adsorption varying inversely with pH. The breakthrough data on chromium transport can be matched closely by calculations of a simple model that accounts for (1) advective-dispersive transport of Cr(III), Cr(VI), and dissolved oxygen, (2) first-order kinetics adsorption of the reduced and oxidized chromium species, and (3) nonlinear rate-limited oxidation of Cr(III) to Cr(VI). Our work supplements the limited database on the transport of redox-sensitive metals in porous media and provides a means for quantifying the coupled processes that contribute to this transport.     

Immobilised microbial reactor for the biotransformation of hexavalent chromium

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

Reduction of hexavalent chromium by ascorbic acid in aqueous solutions

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

XANES study of Cr sorbed by a kitchen waste compost from water

A kitchen waste compost was used to sorb Cr for various times from water containing either Cr(NO3)3 or CrO3 in different concentrations. Scanning electron microscopy (SEM) results show that the composts have been partially oxidized by Cr(VI) during the sorption experiments. X-ray absorption near edge structure (XANES) simulation suggests that about 54.1-61.0% Cr sorbed on the compost is in form of organic Cr(III) through ionic exchange process with the rest being existent as Cr(NO3)3 in the Cr(III) sorption case; no Cr(OH)3 is observed or expected because the solution pH after sorption experiments is or= 5.94. Moreover, organic Cr(III) represents about 51.7-69.0% of the total sorbed Cr, and the rest (6.1-28.5%) is Cr(VI).     

Chromium (VI) remediation in aqueous solution by waste products (peel and seed) of mango (Mangifera indica L.) cultivars

The surface group characteristics of mango cultivar peels and seeds were evaluated by infrared spectra, PZC, and functional group composition. The adsorption/reduction of chromium (VI) in aqueous solutions was investigated by varying pH, contact time, initial Cr(VI) concentration, and adsorbent amount. The results show that both peel and seed powders of the mango cultivars showed significant adsorption/reduction capacity for Cr(VI) and that the desorption process obeys pseudo-second-order kinetics. Optimal adsorption occurred at pH 1.0, using a Cr(VI) concentration of 100 mg/L. On average, at pH 1.0, and a concentration of 3 g/L, the maximum adsorption/reduction capacity of Cr(VI) was 83% (peels 76%, seeds 90%). Of the mango powders tested, the most efficient were Tommy seed (100%) and Coite peel (98%) followed by Coite seed (96%) and Tommy peel powders (95%). The adsorption/reduction of Cr(VI) was complete (100%) by the mango seed, in comparison to the peel powders (97%) after 180 min. The data indicates that mango waste products, such as seed and peel powders, are both excellent candidates for the remediation of Cr(VI) from aqueous systems and due to the higher concentration of gallates and galloyl glucosides, the mango seed powders should be the powders of choice for future remediation projects.

     

Effect of chromium species on phytochemical and physiological parameters in Datura innoxia

In soil, chromium can be found in two main valence states: hexavalent Cr(VI) and trivalent Cr(III). In this study, we investigated the impact of Cr on photosynthetic gas exchange, photosystem II (PSII) activity, Cr translocation and accumulation, proline content and alkaloids production, i.e. scopolamine and hyoscyamine, in Datura innoxia. Cr uptake was influenced by its oxidation state and its concentration in growth medium. The plant roots were determined as being the main organ of Cr accumulation. Cr(VI) was more toxic than Cr(III) as indicated by reduction in plant biomass and net photosynthesis. The stomatal conductance showed a similar trend to that of photosynthetic capacity. Cr(III) and Cr(VI) had a different impact on substomatal CO(2) concentration then Cr toxicity was related to its oxidation states. In plants stressed with a Cr(VI) excess, a down regulation of PSII activity was observed with an impairment of photochemical activity. Indeed, the maximum quantum yield of PSII (F(v)/F(m)), the quantum yield of PSII (PhiPSII) and the efficiency of excitation capture by open centers (F'(v)/F'(m)) decreased. Cr(III) had little effects on PSII primary photochemistry, whatever its form induces an increase of scopolamine content without changes in hyoscyamine content in leaves of D. innoxia. These results provide that chromium contamination can change the secondary metabolites composition of leaves, thereby, impacting the quality, safety and efficacy of natural plant products synthesized by D. innoxia plants.