Kinetics of the reduction of hexavalent chromium with the brown seaweed Ecklonia biomass

The dead biomass of the brown seaweed, Ecklonia sp., is capable of reducing toxic Cr(VI) into less toxic or nontoxic Cr(III). However, little is known about the mechanism of Cr(VI) reduction by the biomass. The objective of this work was to develop a kinetic model for Cr(VI) biosorption, for supporting our mechanism. The reduction rate of Cr(VI) increased with increasing total chromate concentration, [Cr(VI)], and equivalent concentration of organic compounds, [OCs], and decreasing solution pH. It was found that the reduction rate of Cr(VI) was proportional to [Cr(VI)] and [OCs], suggesting the simple kinetic equation -d[Cr(VI)]/dt=k[Cr(VI)][OCs]. When considering the consumption of organic compounds due to the oxidation by Cr(VI), an average rate coefficient of 9.33 (+/-0.65)microM(-1)h(-1) was determined, at pH 2. Although the function of the pH could not be expressed in a mechanistic manner, an empirical model able to describe the pH dependence was obtained. It is expected that the developed rate equation could likely be used for design and performance predictions of biosorption processes for treating chromate wastewaters.     

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.     

Comparative study of chromium biosorption by red, green and brown seaweed biomass

Dried biomass of the macroalgae Fucus vesiculosus and Fucus spiralis (brown), Ulva spp. (comprising Ulva linza, Ulva compressa and Ulva intestinalis) and Ulva lactuca (green), Palmaria palmata and Polysiphonia lanosa (red) were studied in terms of their chromium biosorption performance. Metal sorption was highly pH dependent with maximum Cr(III) and Cr(VI) sorption occurring at pH 4.5 and pH 2, respectively. Extended equilibrium times were required for Cr(VI) binding over Cr(III) binding (180 and 120min, respectively) thus indicating possible disparities in binding mechanism between chromium oxidation states. The red seaweed P. palmata revealed the highest removal efficiency for both Cr(III) and Cr(VI) at low initial concentrations. However, at high initial metal concentrations F. vesiculosus had the greatest removal efficiency for Cr(III) and performed almost identically to P. lanosa in terms of Cr(VI) removal. The Langmuir Isotherm mathematically described chromium binding to the seaweeds where F. vesiculosus had the largest q(max) for Cr(III) sorption (1.21mmol g(-1)) and P. lanosa had the largest Cr(VI) uptake (0.88mmol g(-1)). P. palmata had the highest affinity for both Cr(III) and Cr(VI) binding with b values of 4.94mM(-1) and 8.64mM(-1), respectively. Fourier transform infrared analysis revealed interactions of amino, carboxyl, sulphonate and hydroxyl groups in chromium binding to Ulva spp. The remaining seaweeds showed involvement of these groups to varying degrees as well as ether group participation in the brown seaweeds and for Cr(VI) binding to the red seaweeds.     

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.     

Photochemical reduction of hexavalent chromium in glycerol-containing solutions

Hexavalent chromium [Cr(VI)] in the form of potassium dichromate was photochemically reduced to trivalent chromium [Cr(III)] in aqueous solutions containing glycerol. This reaction occurred rapidly during irradiation with either unfiltered sunlight or a UVA-emitting light source. Photochemical reduction of Cr(VI) was pH-dependent and did not occur in dilute solutions of sodium hydroxide. In acidified solutions, the reduction occurred at elevated rates and at lower concentrations of glycerol. This reaction was found to be dependent on the unsubstituted alcohol groups of glycerol since alpha-phosphoglycerol and beta-phosphoglycerol did not support the photochemical reduction of Cr(VI). These findings suggest that glycerol or related polyols can be used for the remediation of hexavalent (toxic) chromium at contaminated environmental sites.     

Speciation of arsenic and chromium metal ions by reversed phase high performance liquid chromatography

The speciation of arsenic [As(III) and As(V)] and chromium [Cr(III) and Cr(VI)] was carried out by high performance liquid chromatography. The column used was Econosil C18 (250 x 4.6 mm i.d., particle size 10 microm). The mobile phases consisted of water-acetonitrile (80:20, v/v) for arsenic and 10 mM ammonium acetate buffer (6.0 pH)-acetonitrile (10:90, v/v) for chromium speciation separately and respectively. The detection was carried out by UV-Vis at 410 nm and atomic absorption spectrometer (AAS) respectively and separately. The values of alpha and Rs of As(III) and As(V) species were 1.4 and 1.5 respectively while the values of alpha and Rs for Cr(III) and Cr(VI) were 1.35 and 0.2 respectively. The effect of the acetonitrile percentages was also carried out on the speciation of arsenic only. The relative standard deviation and limit of detection were in the range of 0.01-0.02 and 0.4-1.0 microg/ml respectively.     

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%.     

Simultaneous reduction of Cr(VI) and oxidation of As(III) by Bacillus firmus TE7 isolated from tannery effluent

Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are the most toxic forms of chromium and arsenic respectively, and reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) has great environmental implications as they affect toxicity and mobility of these toxic species. Bacillus firmus strain TE7, resistant to chromium and arsenic was isolated from tannery effluent. The strain exhibited ability to reduce Cr(VI) and oxidize As(III). It reduced 100 mg L^?1 Cr(VI) within 60 h in nutrient broth and oxidized 150 mg L^?1 As(III) within 10 h in minimal medium. It also completely reduced 15 mg L^?1 Cr(VI) and oxidized 50 mg L^?1 of As(III) simultaneously in minimal medium. To the best of our knowledge, this is the first bacterial strain showing simultaneous reduction of Cr(VI) and oxidation of As(III) and is a potential candidate for bioremediation of environments contaminated with these toxic metal species.     

Mobility and recalcitrance of organo-chromium(III) complexes

Hexavalent chromium [Cr(VI)] is a major industrial pollutant. Bioremediation of Cr(VI) to Cr(III) is a viable clean-up approach. However, Cr(VI) bioreduction also produces soluble organo–Cr(III) complexes, and little is known about their behavior in the environment. When tested with soil columns, citrate–Cr(III) showed little sorption to soil; malate–Cr(III) had limited partitioning with soil; and histidine–Cr(III) exhibited significant interaction with soil. It appears that the mobility varies depending on the organic ligand. Further, Ralstonia eutropha JMP 134 and Pseudomonas aeruginosa pAO1 readily degraded malate, citrate, and histidine, but not the corresponding organo–Cr(III) complexes. The recalcitrance is not due to toxicity, but the complexes are likely to cause hindrance to enzymes, as malate dehydrogenase and amino acid oxidase could not use malate–Cr(III) and histidine–Cr(III), respectively. The data are in agreement with the reports of soluble organo–Cr(III) complexes in the environment.     

Waste Fe(III)/Cr(III) hydroxide as adsorbent for the removal of Cr(VI) from aqueous solution and chromium plating industry wastewater

Fe(III)/Cr(III) hydroxide, a waste material from the fertilizer industry, has been used for the adsorption of Cr(VI) from aqueous solution, over a range of initial metal ion concentrations (5-30 mg litre(-1)), agitation times (1-180 min), adsorbent dosages (100-1200 mg per 50 ml), temperatures (24, 29 and 38 degrees C) and pH values (4.5-10). The adsorption of Cr(VI) increased with the initial concentration of Cr(VI) and with temperature. The process of uptake follows both the Langmuir and the Freundlich isotherm models. The applicability of Lagergren and empirical kinetic models has also been investigated. Almost quantitative removal of Cr(VI) at 10 mg litre(-1) in a 50-ml solution by 500 mg of adsorbent was found at an equilibrium pH of 5.6. The efficiency of chromium removal was also tested using wastewater from the chromium plating industry.     

A comparative study on metal sorption by brown seaweed

This study compared the sorption of Ag, Cd, Co, Cd, Mn, Ni, Pb and Zn by a Ca-treated Sargassum biomass at pH 5.0, under low and high ionic strength (IS) conditions. The sorption isotherms of As [As(V)] and Cr [Cr(III) and Cr(VI)] were also determined at low IS. The isotherm data for the eight cationic metals and Cr(III) were well fitted by Langmuir equations. Generally, the maximum metal uptake (Umax) followed: Cr(III) > Pb approximately Cu > Ag approximately Zn approximately Cd > Ni approximately Mn approximately Co > Cr(VI) > As(V) at low IS and Pb > Cu > Co > Mn approximately Cd > Zn approximately Ag > Ni at high IS. As(V) did not bind to the seaweed at pH 5.0. The results indicated that sorption of Pb was not affected by the increasing IS, though the percentage of free Pb ions in the water was greatly reduced as predicted by the speciation model. High IS lowered Umax by 10-36% (except Co and Pb), and lowered the affinity constant of the metal by 33-91% for all cationic metals, as compared to low IS. Moreover, the removal efficiency of the cationic metals and Cr decreased exponentially with initial metal concentrations and was lower at high IS. Ion-exchange was the mechanism responsible for the cationic metal sorption onto the seaweed, and Na ion interfered with the cationic metal binding through electrostatic interaction. In conclusion, this study showed the differential binding capacity of the Sargassm biomass for different metals and oxidation states and the differential effects of IS. According to the present results, Sargassum may be considered a good biosorbent for cationic metals (especially Pb) in both low and high-salt containing wastewater.     

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.     

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.     

Sorption of Cr(VI) from dilute solutions and wastewater by live and pretreated biomass of Aspergillus flavus

Sorption of Cr(VI) was carried out from dilute solutions using live and pretreated biomass in a batch mode. Effects of agitation time, adsorbent dosage and pH were examined. The autoclaved biomass that showed maximum adsorption capacity (Q(0)=0.335 mg g(-1)) was used as an adsorbent in column studies. The optimized flow rate of 2.5 ml min(-1) and bed height 10 cm were used to determine the effect of metal ion concentration on removal of Cr(VI). Applying the BDST model to calculate the adsorption capacity (N(0)) of column, which showed 4.56 x 10(-5), 7.28 x 10(-5), 6.89 x 10(-5), 3.07 x 10(-5), 2.80 x 10(-5)mg g(-1) for 4, 8, 12, 16 and 20 mg dm(-3) of Cr(VI), respectively. Batch sorption proved to be more efficient than the column sorption and hence batch sorption was used to remove Cr(VI) from a textile dyeing industry wastewater. The phytotoxic effect of treated and untreated wastewater was studied against Zea mays. Toxicity was reduced by 50% in the treated effluent.     

Biosorption of hexavalent chromium from aqueous solution by pristine and CaCl2-modified erythromycin production residues

Environmental Science and Pollution Research - In this study, the adsorptive removal of hexavalent chromium [Cr(VI)] from aqueous solutions by the pristine and salt-treated (CaCl2) erythromycin...     

Nopalea cochenillifera, a potential chromium (VI) hyperaccumulator plant

Hexavalant chromium [Cr(VI)] tolerance and accumulation in in vitro grown Nopalea cochenillifera Salm. Dyck. plants was investigated. A micropropagation protocol was establish for a rapid multiplication of N. cochenillifera and [Cr(VI)] tolerance and accumulation was studied in in vitro grown cultures. Cr concentration was estimated by atomic absorption spectroscopy in roots and shoots to confirm plant’s hyperaccumulation capacity. Plants showed tolerance up to 100 μM K₂Cr₂O₇ without any significant changes in root growth after 16 days treatment; whereas, chlorophyll content in plants treated with 1 and 10 μM K₂Cr₂O₇ were not so different than the control plant. The levels of lipid peroxidation and protein oxidation increased significantly (p?<?0.01) with increasing concentration of chromium. Exposures of N. cochenillifera to lower concentrations of K₂Cr₂O₇ (≤10 μM) induced catalase (CAT) and superoxide dismutase (SOD) significantly (p?<?0.001) but higher concentrations of K₂Cr₂O₇ (>100 μM) inhibited the activities of CAT and SOD. Roots accumulated a maximum of 25,263.396?±?1,722.672 mg?Cr?Kg^?1 dry weight (DW); while the highest concentration of Cr in N. cochenillifera shoots was 705.714?±?32.324 mg?Cr?Kg^?1?DW. N. cochenillifera could be a prospective hyperaccumulator plant of Cr(VI) and a promising candidate for phytoremediation purposes.     

Removal of hexavalent chromium upon interaction with biochar under acidic conditions: mechanistic insights and application

Environmental Science and Pollution Research - Chromium pollution of soil and water is a serious environmental concern due to potential carcinogenicity of hexavalent chromium [Cr(VI)] when...     

Both trivalent and hexavalent chromium strongly alter in vitro germination and ultrastructure of kiwifruit pollen

Due to its widespread industrial use, chromium is considered a dangerous environmental pollutant. It is known to inhibit plant growth and development. The present study provides the first evidence of the toxicity of this metal on the male haploid generation of a higher plant. Both Cr(III) and Cr(VI) species, supplied as CrCl(3) and CrO(3), respectively, exerted a strong dose-dependent inhibitory effect on kiwifruit pollen tube emergence and growth. Cr(III) resulted more effective than Cr(VI) in the 16-75microM interval; moreover, complete inhibition of germination was attained at much lower doses than Cr(VI). Also tube morphology was affected. While the plasma membrane was still undamaged in the large majority of the treated pollen grains, dramatic ultrastructural alterations were induced by chromium including chromatin condensation, swelling of mitochondria, cytoplasmic vacuolization, and perturbed arrangement of endoplasmic reticulum cisternae. Thus, it seems that the impact of the two chromium species on kiwifruit pollen may result in severe compromission of both essential structures and functions of the male gametophyte.     

Molecular study of thermal immobilization of chromium(VI) with clay

Clay that contains kaolinite has been used extensively as a raw material for manufacturing of bricks and china at 900-1100 degrees C. This study used clay to stabilize the contaminant chromium(VI) [Cr(VI)] through a heating process at 500-1100 degrees C. X-ray absorption spectroscopic results indicated that the 500-900 degrees C heating process transformed hazardous Cr(VI) to nontoxic Cr(III); Cr2O3 was the species detected as most abundant. The 1100 degrees C heating process caused the formation of Cr2SiO5, which was not detected in the samples heated at 500-900 degrees C. Fourier transformed extended X-ray absorption fine structure spectra were fitted by use of WinXAS software. Phase shifts and backscatter(ing) amplitudes for specific atom pairs, based on the crystallographic data for CrO3 and Cr2O3, were theoretically calculated with the FEFF software. The processed XAS data show that the first shell coordination numbers were similar to each other as the temperature was increased from 500 to 900 degrees C and 1100 degrees C, implying that their Cr(III) crystallite size was relatively similar. The interatomic distance between the target center element and the first shell for the 500-1100 degrees C samples was 1.98 A. The Debye-Waller factor for the 1100 degrees C sample was increased compared with the 500 and 900 degrees C samples and probably indicates the formation of Cr2SiO5.