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.     

Cr(VI) sorption by free and immobilised chromate-reducing bacterial cells in PVA–alginate matrix: equilibrium isotherms and kinetic studies

Chromate-resistant bacterial strain isolated from the soil of tannery was studied for Cr(VI) bioaccumulation in free and immobilised cells to evaluate its applicability in chromium removal from aqueous solution. Based on the comparative analysis of the 16S rRNA gene, and phenotypic and biochemical characterization, this strain was identified as Paenibacillus xylanilyticus MR12. Mechanism of Cr adsorption was also ascertained by chemical modifications of the bacterial biomass followed by Fourier transform infrared spectroscopy analysis of the cell wall constituents. The equilibrium biosorption analysed using isotherms (Langmuir, Freundlich and Dubinin–Redushkevich) and kinetics models (pseudo-first-order, second-order and Weber–Morris) revealed that the Langmuir model best correlated to experimental data, and Weber–Morris equation well described Cr(VI) biosorption kinetics. Polyvinyl alcohol alginate immobilised cells had the highest Cr(VI) removal efficiency than that of free cells and could also be reused four times for Cr(VI) removal. Complete reduction of chromate in simulated effluent containing Cu²⁺, Mg²⁺, Mn²⁺ and Zn²⁺ by immobilised cells, demonstrated potential applications of a novel immobilised bacterial strain MR12, as a vital bioresource in Cr(VI) bioremediation technology.     

Biosorption of Cr(VI) by free and immobilized Pediastrum boryanum biomass: equilibrium, kinetic, and thermodynamic studies

Background and purpose

The biosorption of Cr(VI) from aqueous solution has been studied using free and immobilized Pediastrum boryanum cells in a batch system. The algal cells were immobilized in alginate and alginate?Cgelatin beads via entrapment, and their algal cell free counterparts were used as control systems during biosorption studies of Cr(VI).

Methods

The changes in the functional groups of the biosorbents formulations were confirmed by Fourier transform infrared spectra. The effect of pH, equilibrium time, initial concentration of metal ions, and temperature on the biosorption of Cr(VI) ion was investigated.

Results

The maximum Cr(VI) biosorption capacities were found to be 17.3, 6.73, 14.0, 23.8, and 29.6?mg/g for the free algal cells, and alginate, alginate?Cgelatin, alginate?Ccells, and alginate?Cgelatin?Ccells at pH?2.0, which are corresponding to an initial Cr(VI) concentration of 400?mg/L. The biosorption of Cr(VI) on all the tested biosorbents (P. boryanum cells, alginate, alginate?Cgelatin, and alginate?Ccells, alginate?Cgelatin?Ccells) followed Langmuir adsorption isotherm model.

Conclusion

The thermodynamic studies indicated that the biosorption process was spontaneous and endothermic in nature under studied conditions. For all the tested biosorbents, biosorption kinetic was best described by the pseudo-second-order model.     

Feasibility of using microalgal biomass cultured in domestic wastewater for the removal of chromium pollutants

The feasibility of obtaining and using the biomass of a microalga, Chlorella miniata, from domestic wastewater (DW) cultures for the removal of chromium(III) [Cr(III)] and chromium(VI) [Cr(VI)] was compared with that from commercial Bristol medium (BM). Results showed that Chlorella miniata cultured in DW under 16-8 hours light-dark cycle [DW(16-8)] had similar growth to that in BM [BM(16-8)], but these two biomass had different biochemical compositions, and the former one had lower carbohydrate and higher protein content. When cultured in domestic wastewater, a higher biomass was obtained under continuous illumination [DW(24-0)], and the cells had higher carbohydrate and lower protein concentrations than that of DW(16-8). The spectra of the Fourier transform infrared spectrometer revealed that the functional groups on the surface of the three kinds of biomass--DW(16-8), DW(24-0), and BM(16-8)--were comparable, except an additional peak at 1731 cm(-1) was found in the biomass cultured in domestic wastewater, which was probably the result of bacterial contamination. Although biochemical differences were found among the three kinds of microalgal biomass, similar biosorption performances to chromium pollutants were recorded, with approximately 75% Cr(III) and 100% Cr(VI) removed at equilibrium in Cr(III) and Cr(VI) experiments, respectively, when dead biomass was used as a biosorbent. Therefore, it is possible to culture Chlorella miniata in domestic wastewater and use the biomass for the removal of chromium pollutants.     

Hexavalent chromium removal by a novel Serratia proteamaculans isolated from the bank of Sebou River (Morocco)

The novel Serratia proteamaculans isolated from a chromium-contaminated site was tolerant to a concentration of 500 mg Cr(VI)/l. The optimum pH and temperature for reduction of Cr(VI) by S. proteamaculans were found to be 7.0 and 30 °C, respectively. The Cr(VI) reduction rate decreased with the increase in Cr(VI) concentration from 100 to 400 mg/l, suggesting the enzymatic chromium reduction. Resting and permeabilised cell assays provided the better evidence that chromate reduction in S. proteamaculans is enzymatic. Reduction by cell-free filtrate shows no extracellular chromate-reducing activity, revealing that this activity may be associated to membrane fraction and/or cytosolic fraction. Assays conducted with cytosolic and particulate fraction of S. proteamaculans confirmed the role of membrane-bound proteins in Cr(VI) reduction. Furthermore, chromium reduced by heat-treated cells suggests that membrane-associated chromate reductase activity of S. proteamaculans is preceded by its adsorption on the cell surface.     

Chromate reduction on humic acid derived from a peat soil--exploration of the activated sites on HAs for chromate removal

Humic substances are a major component of soil organic matter that influence the behavior and fate of heavy metals such as Cr(VI), a toxic and carcinogenic element. In the study, a repetitive extraction technique was used to fractionate humic acids (HAs) from a peat soil into three fractions (denoted as F1, F2, and F3), and the relative importance of O-containing aromatic and aliphatic domains in humic substances for scavenging Cr(VI) was addressed at pH 1. Spectroscopic analyses indicated that the concentrations of aromatic C and O-containing functional groups decreased with a progressive extraction as follows: F1>F2>F3. Cr(VI) removal by HA proceeded slowly, but it was enhanced when light was applied due to the production of efficient reductants, such as superoxide radical and H(2)O(2), for Cr(VI). Higher aromatic- and O-containing F1 fraction exhibited a greater efficiency for Cr(VI) reduction (with a removal rate of ca. 2.89 mmol g(-1) HA under illumination for 3 h). (13)C NMR and FTIR spectra further demonstrated that the carboxyl groups were primarily responsible for Cr(VI) reduction. This study implied the mobility and fate of Cr(VI) would be greatly inhibited in the environments containing such organic groups.     

Biosorption of Cr(VI) and Zn(II) ions from aqueous solution onto the solid biodiesel waste residue: mechanistic, kinetic and thermodynamic studies

In this present study, the biosorption of Cr(VI) and Zn(II) ions from synthetic aqueous solution on defatted J atropha oil cake (DJOC) was investigated. The effect of various process parameters such as the initial pH, adsorbent dosage, initial metal ion concentration and contact time has been studied in batch-stirred experiments. Maximum removal of Cr(VI) and Zn(II) ions in aqueous solution was observed at pH 2.0 and pH. 5.0, respectively. The removal efficiency of Cr(VI) and Zn(II) ions from the aqueous solution was found to be 72.56 and 79.81 %, respectively, for initial metal ion concentration of 500 mg/L at 6 g/L dosage concentration. The biosorbent was characterized by Fourier transform infrared, scanning electron microscopy and zero point charge. Equilibrium data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models and the best fit is found to be with the Freundlich isotherm for both Cr(VI) and Zn(II) metal ions. The kinetic data obtained at different metal ion concentration have been analysed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion models and were found to follow the pseudo-second-order kinetic model. The values of mass transfer diffusion coefficients (D _e) were determined by Boyd model and compared with literature values. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were analysed using the equilibrium constant values (K _e) obtained from experimental data at different temperatures. The results showed that biosorption of Cr(VI) and Zn(II) ions onto the DJOC system is more spontaneous and exothermic in nature. The results indicate that DJOC was shown to be a promising adsorbent for the removal of Cr(VI) and Zn(II) ions from aqueous solution.     

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.     

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%.     

Chromate-reducing activity of Hansenula polymorpha recombinant cells over-producing flavocytochrome b₂

In spite of the great interest to studies of the biological roles of chromium, as well as the toxic influence of Cr(VI)-species on living organisms, the molecular mechanisms of chromate bioremediation remain vague. A reductive pathway resulting in formation of less toxic Cr(III)-species is suggested to be the most important among possible mechanisms for chromate biodetoxification. The yeast l-lactate:cytochrome c-oxidoreductase (flavocytochrome b(2), FC b(2)) has absolute specificity for l-lactate, yet is non-selective with respect to its electron acceptor. These properties allow us to consider the enzyme as a potential candidate for chromate reduction by living cells in the presence of l-lactate. A recombinant strain of thermotolerant, methylotrophic yeast Hansenula polymorpha with sixfold increased FC b(2) enzyme activity (up to 3μmolmin(-1)mg(-1) protein in cell-free extract) compared to the parental strain was used for approval our suggestion. The recombinant cells, stored in dried state, as well as living yeast cells were tested for chromate-reducing activity in vitro in the presence of l-lactate (as an electron donor for chromate reduction) and different low molecular weight, redox-active mediators facilitating electron transfer from the reduced form of the enzyme to chromate (as a final electron acceptor): dichlorophenolindophenol (DCPIP), Methylene blue, Meldola blue, and Nile blue. It was shown that the highest chromate-reducing activity of the cells was achieved in the presence of DCPIP. The ability of chromate to catch electrons from the reduced flavocytochrome b(2) was confirmed using purified enzyme immobilized on the surface of a platinum electrode. The increasing concentration of Cr(VI) resulted in a decrease of enzyme-mediated current generated on the electrode during l-lactate oxidation. The shift and drop in amplitude of the peak in the cyclic voltammogram are indicative of Cr(VI)-dependent competition between reaction of chromate with reduced FC b(2) and direct electron transfer from the enzyme to the electrode surface. The application of the chromate-reducing ability of FC b(2)-over-producing recombinant cells of H. polymorpha toward chromate bioremediation and the construction of cells-based biosensor for chromate monitoring in the environment are discussed.     

Studies on hexavalent chromium biosorption by chemically-treated biomass of Ecklonia sp

The biomass of the brown seaweed, Ecklonia sp., is capable of reducing Cr(VI) to Cr(III). However, very little is known about the mechanism of Cr(VI) reduction by the biomass. The aims of the present investigation were to enhance the Cr(VI)-reducing capacity of the biomass using various chemical treatments and to elucidate the mechanisms governing Cr(VI) reduction. Among the various chemical treatments, acid-treatment showed the best performance with regards the improvement of Cr(VI) removal from the aqueous phase, while organic solvent-treatment significantly improved the removal efficiency of total Cr in the equilibrium state. Based on FTIR study, the biomass was subjected to chemical modification of its amino and carboxyl groups, to examine their roles in the Cr(VI) removal from the aqueous phase. Methylation of the amino group significantly decreased the Cr(VI) removal rate, but amination of the carboxyl group significantly increased the Cr(VI) removal rate. Meanwhile, esterification of the carboxyl group and carboxylation of the amino group decreased the Cr(VI) removal rate, but the former showed a more negative effect than the latter. These findings indicated that the amino and carboxyl groups take part in the Cr(VI) removal from the aqueous phase. In conclusion, mechanisms for direct and indirect Cr(VI) removal are proposed, and some aspects for the application of this biomass to Cr(VI) detoxification are discussed.     

Graphical estimation of the dual-enzyme kinetic parameters for Cr(VI) reduction

Chromium(VI) (Cr(VI)) contamination of soil and groundwater is a major environmental concern. Bioreduction of Cr(VI) by Shewanella oneidensis MR-1 (MR-1) can be considered a feasible option to reduce the toxic and mobile Cr(VI) to the less toxic and less mobile chromium(III) (Cr(III)). The reaction rate expression for Cr(VI) reduction is nonlinear and the rate constants are evaluated by employing nonlinear optimization techniques. The outcome of the optimization techniques, in general, depends on the initial estimate of the kinetic parameters which is not always available. A graphical approach based on sound mathematical reasoning has been developed which is accurate, simpler to use, and can provide the best initial estimate for nonlinear optimization.     

Influence of plants on the reduction of hexavalent chromium in wetland sediments

This work addresses the effect that plants (Typha latifolia and Carex lurida) have on the reduction of Cr(VI) in wetland sediments. Experiments were carried out using tubular microcosms, where chemical species were monitored along the longitudinal flow axis. Cr(VI) removal was enhanced by the presence of plants. This is explained by a decrease in the redox potential promoted by organic root exudates released by plants. Under these conditions sulfate reduction is enhanced, increasing the concentration of sulfide species in the sediment pore water, which reduce Cr(VI). Evapotranspiration induced by plants also contributed to enhance the reduction of Cr(VI) by concentrating all chemical species in the sediment pore water. Both exudates release and evapotranspiration have a diurnal component that affects Cr(VI) reduction. Concentration profiles were fitted to a kinetic model linking sulfide and Cr(VI) concentrations corrected for evapotranspiration. This expression captures both the longitudinal as well as the diurnal Cr(VI) concentration profiles.     

Reliable evidences that the removal mechanism of hexavalent chromium by natural biomaterials is adsorption-coupled reduction

For the last few decades, over 200 papers have been published in the Cr(VI) biosorption research field. Most early studies have claimed that Cr(VI) was removed from aqueous phase through an anionic adsorption, but this approach has been lost old original position. It has been newly explained that these findings were misinterpreted due to errors in measuring the concentrations of different chromium species in the aqueous phase, insufficient contact time required for equilibrium and the lack of information about the oxidation state of the chromium bound to biomaterials. Although 'adsorption-coupled reduction' is now widely accepted as the mechanism of Cr(VI) biosorption by natural biomaterials, a number of researchers still believe that Cr(VI) is removed by anionic adsorption onto the biomaterials. Therefore, the objective of this study was to show reliable evidences that the removal mechanism of Cr(VI) by natural biomaterials is 'adsorption-coupled reduction'. Sixteen natural biomaterials were used to study the Cr(VI) biosorption. Not only Cr(VI) but also total Cr in the aqueous phase were analyzed. X-ray photoelectron spectroscope was also used to verify the oxidation state of the chromium bound to the biomaterials. Finally, the removal behavior of Cr(VI) by each biomaterial was described by a kinetic model based on a redox reaction.     

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.     

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.     

Electro-migration of heavy metals in an aged electroplating contaminated soil affected by the coexisting hexavalent chromium

Cr(VI) was often reported to oxidize soil organic matter at acidic environments due to its high ORP, probably thus changing cationic metal species bound to soil organic matter, and influencing their electro-migration patterns. However, such an effect on the electro-migration was not confirmed in most previous studies. Therefore, this study applied a fixed voltage direct current field on an aged electroplating contaminated clayed soil, with a special interest in the direct or indirect influence of Cr(VI) on the electro-migration of other coexisting metals. After 353 h electrokinetic process, 81% of Zn, 53% of Ni and 22% of Cu in the original soil were electro-migrated into the electrolyte, and most of the remaining concentrated near the cathode. The Cr(VI) oxidized some soil organic matter along its migration pathway, with a pronounced reaction occurred near the anode at low pHs. The resulting Cr(III) reversed its original movement, and migrated towards the cathode, leading to the occurrence of a second Cr concentration peak in the soil. Metal species analyses showed that the amount of metals bound to soil organic matter significantly decreased, while a substantial increase in the Cr species bound to Fe/Mn (hydro-)oxides was observed, suggesting an enhancement of cationic metal electro-migration by the reduction of Cr(VI) into Cr(III). However, the Cr(VI) may form some stable lead chromate precipitates, and in turn demobilize Pb in the soil, as the results showed a low Pb removal and an increase in its acid-extractable and residual fractions after electrokinetic remediation.     

Reduction of Cr(VI) by malic acid in aqueous Fe-rich soil suspensions

Detoxification of Cr(VI) through reduction by organic reductants has been regarded as an effective way for remediation of Cr(VI)-polluted soils. However, such remediation strategy would be limited in practical applications due to the low Cr(VI) reduction rate. In this study, the catalytic effect of two Fe-rich soils (Ultisol and Oxisol) on Cr(VI) reduction by malic acid was evaluated. As the results shown, the two soils could obviously accelerate the reduction of Cr(VI) by malic acid at low pH conditions, while such catalytic effect was gradually suppressed as the increase in pH. After reaction for 48 h at pH 3.2, Oxalic acid was found in the supernatant of Ultisol, suggesting the oxidization of hydroxyl in malic acid to carboxyl and breakage of the bond between C₂ and C₃. It was also found that the catalytic reactivity of Ultisol was more significant than that of Oxisol, which could be partly attributed to the fact that the amount of Fe(II) released from the reductive dissolution of Ultisol by malic acid was larger than that of Oxisol. With addition of Al(III), the catalytic effect from Ultisol was inhibited across the pH range examined. On the contrary, the presence of Cu(II) would increase the catalytic effect of Ultisol, which was more pronounced with the increase in pH. This study proposed a potential way for elimination of the environmental risks posed by the Cr(VI) contamination by use of the natural soil surfaces to catalyze Cr(VI) reduction by the organic reductant such as malic acid, a kind of organic reductant originating from soil organic decomposition process or plant excretion.     

Influence of complex reagents on removal of chromium(VI) by zero-valent iron

The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).