Using chromium stable isotope ratios to quantify Cr(VI) reduction: lack of sorption effects

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr(VI) and Cr(VI) adsorbed onto gamma-Al2O3 and goethite is less than 0.04 per thousand (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO4(2-) was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in delta53Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.     

Research Watch: Cr(VI) removal

Remediation.     

Bifunctionalized mesoporous silicas for Cr(VI) reduction and concomitant Cr(III) immobilization

Surfactant-templated thiol-functionalized mesoporous silica adsorbents have been prepared by cocondensation of mercaptopropyltrimethoxysilane and tetraethoxysilane in the presence of cetyltrimethylammonium bromide, which were then partially oxidized to get bifunctionalized materials containing both thiol and sulfonic acid moieties (MCM-41-SH/SO3H). The resulting organic-inorganic hybrid was applied to the uptake of chromium species according to a reduction-sorption mechanism involving reduction of Cr(VI) by thiol groups and immobilization of Cr(III) onto sulfonic acid moieties. These processes were strongly affected by pH, and the optimal conditions for effective chromium sequestration resulted from a compromise between pH values low enough to ensure quantitative reduction of Cr(VI) and not too low to enable Cr(III) binding to sulfonate groups, which was best achieved at pH 2-3. The effect of the solid-to-solution ratio and the relative amounts of -SH and -SO3H groups was also discussed. Even if Cr(VI) reduction by thiol groups resulted in the formation of sulfonic acid moieties, their contentwas not high enough to ensure quantitative Cr(III) immobilization, which was only attained with materials containing already some sulfonic acid groups prior to contacting Cr(VI) solutions. Redox speciation of sulfur and chromium species was analyzed by X-ray photoelectron spectroscopy (XPS) and used to support the proposed mechanism.     

Spectroscopic investigation of Cr(III)- and Cr(VI)-treated nanoscale zerovalent iron

The reaction of hexavalent chromium (Cr(VI)) with zerovalent iron (Fe0) during soil and groundwater remediation is an important environmental process. This study used several techniques including X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy to investigate nanometer scale Fe0 particles (nano Fe0) treated with Cr(III) and Cr(VI). X-ray diffraction and XPS analyses of oxidized nano Fe0 showed the crystalline Fe(III) phase is composed of lepidocrocite (gamma-FeOOH). Results of XPS Cr 2p data and Cr K-edge X-ray absorption near edge spectroscopy (XANES) provided evidence that Cr(VI) was entirely reduced to Cr(III) by nano Fe0 with no residual Cr(VI) after reaction. In addition, XPS and XANES results of Cr(III) precipitated as Cr(OH)3 in the presence of corroding nano Fe0 were nearly identical to the Cr(VI)-nano Fe0 reaction product. Detailed analysis of XPS O 1s line spectra revealed that both Cr(III)- and Cr(VI)-treated nano Fe0 yielded a predominantly hydroxylated Cr(OH)3 and/ or a mixed phase CrxFe(1 - x)(OH)3 product. The structure of the Cr(III)- and Cr(VI)-treated nano Fe0 determined using extended X-ray absorption fine structure spectroscopy (EXAFS) revealed octahedral Cr(III) with Cr-O interatomic distances between 1.97 and 1.98 A for both Cr(III) and Cr(VI) treatments and a pronounced Cr-Cr second interatomic shell at 3.01 A. Our results suggest that the reaction product of Cr(VI)-treated nano Fe0 is either a poorly ordered Cr(OH)3 precipitate or possibly a mixed phase CrxFe(1 - x)(OH)3 product, both of which are highly insoluble under environmental conditions.     

Chromium(VI) bioremoval by Pseudomonas bacteria: role of microbial exudates for natural attenuation and biotreatment of Cr(VI) contamination

Laboratory batch and column experiments were conducted to investigate the role of microbial exudates, e.g., exopolymeric substance (EPS) and alginic acid, on microbial Cr(VI) reduction by two different Pseudomonas strains (P. putida P18 and P. aeuroginosa P16) as a method for treating subsurface environment contaminated with Cr(VI). Our results indicate that microbial exudates significantly enhanced microbial Cr(VI) reduction rates by forming less toxic and highly soluble organo-Cr(III) complexes despite the fact Cr(III) has a very low solubility under the experimental conditions studied (e.g., pH 7). The formation of soluble organo-Cr(III) complexes led to the protection of the cells and chromate reductases from inactivation. In systems with no organic ligands, soluble organo-Cr(III) end products were formed between Cr(III) and the EPS directly released by bacteria due to cell lysis. Our results also provide evidence that cell lysis played an important role in microbial Cr(VI) reduction by Pseudomonas bacteria due to the release of constitutive reductases that intracellularly and/or extracellularly catalyzed the reduction of Cr(VI) to Cr(III). The overall results highlight the need for incorporation of the release and formation of organo-Cr(III) complexes into reactive transport models to more accurately design and monitor in situ microbial remediation techniques for the treatment of subsurface systems contaminated with Cr(VI).     

U(VI) sorption and reduction kinetics on the magnetite (111) surface

Sorption of contaminants onto mineral surfaces is an important process that can restrict their transport in the environment. In the current study, uranium (U) uptake on magnetite (111) was measured as a function of time and solution composition (pH, [CO(3)](T), [Ca]) under continuous batch-flow conditions. We observed, in real-time and in situ, adsorption and reduction of U(VI) and subsequent growth of UO(2) nanoprecipitates using atomic force microscopy (AFM) and newly developed batch-flow U L(III)-edge grazing-incidence X-ray absorption spectroscopy near-edge structure (GI-XANES) spectroscopy. U(VI) reduction occurred with and without CO(3) present, and coincided with nucleation and growth of UO(2) particles. When Ca and CO(3) were both present no U(VI) reduction occurred and the U surface loading was lower. In situ batch-flow AFM data indicated that UO(2) particles achieved a maximum height of 4-5 nm after about 8 h of exposure, however, aggregates continued to grow laterally after 8 h reaching up to about 300 nm in diameter. The combination of techniques indicated that U uptake is divided into three-stages; (1) initial adsorption of U(VI), (2) reduction of U(VI) to UO(2) nanoprecipitates at surface-specific sites after 2-3 h of exposure, and (3) completion of U(VI) reduction after ~6-8 h. U(VI) reduction also corresponded to detectable increases in Fe released to solution and surface topography changes. Redox reactions are proposed that explicitly couple the reduction of U(VI) to enhanced release of Fe(II) from magnetite. Although counterintuitive, the proposed reaction stoichiometry was shown to be largely consistent with the experimental results. In addition to providing molecular-scale details about U sorption on magnetite, this work also presents novel advances for collecting surface sensitive molecular-scale information in real-time under batch-flow conditions.     

Hydrogarnet: a host phase for Cr(VI) in chromite ore processing residue (COPR) and other high pH wastes

For understanding both the environmental behavior and developing remediation treatments for chromium ore processing residue (COPR) it is important to identify all the potentially soluble sources of Cr(VI). Hydrogarnet has been identified as a major phase in COPR and it has been previously speculated that it has a capacity to host Cr(VI). Here we provide direct evidence of this capacity by demonstrating the incorporation of Cr(VI) into laboratory synthesized hydrogarnet. Electron microscopy and energy dispersive X-ray microanalysis show incorporation of approximately 17000-22000 mg Cr(VI) kg(-1) hydrogarnet. X-ray powder diffraction data show that peak intensities are altered by chromium substitution and that chromium substituted hydrogarnets have a smaller unit cell than the pure Ca-Al end member. This is consistent with substitution of hydroxyl tetrahedra by smaller chromate tetrahedra. Electron energy loss spectroscopy confirms the tetrahedral coordination and hexavalent oxidation state of chromium in the hydrogarnets. The maximum amount of hexavalent chromium that can be introduced synthetically corresponds to a replacement of about one out of every eight hydroxyl tetrahedral per unit cell by a CrO4(2-) tetrahedra and tallies closely with the amount of chromium measured in hydrogarnets from COPR. Chromium-bearing hydrogarnet is the most abundant crystalline phase in millions of tons of COPR contaminating land around Glasgow, Scotland, and was recently identified in COPR from sites in North America. Calculations based on its abundance and its Cr(VI) content indicate that hydrogarnet can host as much as 50% of the Cr(VI) found in some COPR samples.     

Removal of Cr(VI) and Cr(lll) from aqueous solutions and industrial wastewaters by natural clino-pyrrhotite

This paper introduced a simple method of treating Cr(Vl)-bearing toxic wastewaters using a natural mineral: clino-pyrrhotite. Laboratory bench-scale mixing experiments were carried out in both Cr(VI)-bearing artificial solutions and industrial wastewaters under controlled conditions. The effects of solution pH, Cr(VI) concentration, mineral grain size, mineral/solution ratio, and reaction time on the Cr(VI) removal were studied. Chromium was effectively removed from the solutions and wastewaters. After the treatment, the liquid was clean enough to be discharged directly into the natural environment. The Cr(VI) removal process involved sequentially the adsorption of Cr(VI), in the form of Cr2O7(2-) or CrO4(2-), onto the mineral surface, the reduction of the adsorbed Cr(VI) to Cr(lll), catalyzed at the vacant Fe sites of the mineral, and finally the precipitation of Cr(lll) as Cr2S3, Cr2O3, and Cr(OH)3 solid phases. Conditions such as a fine mineral grain size, an excessive quantity of clino-pyrrhotite and a weak acidic media, favored the removal process. For clino-pyrrhotite with a restricted grain size, the minimum required quantity of the mineral was proportional to the total quantity of Cr(VI) to be removed. Quantitatively, one cubic meter of industrial wastewater that contained approximately 1 mmol dm(-3) of Cr(VI) and had a pH value between 1 and 10 would be effectively treated after it was in contact with 220 kg of 145 +/- 28 microm clino-pyrrhotite for an hour. Furthermore, the quantity of the final solid waste byproduct was small, and the solid residue of clino-pyrrhotite could be reused after a simple rinse with water. Compared to the previous Cr(VI)-bearing wastewater treatment schemes, this method was simple, effective, economical, and environmentally sound. It has great potential for use in industrial-scale applications.     

Cr stable isotopes in Snake River Plain aquifer groundwater: evidence for natural reduction of dissolved Cr(VI)

At Idaho National Laboratory, Cr(VI) concentrations in a groundwater plume once exceeded regulatory limits in some monitoring wells but have generally decreased over time. This study used Cr stable isotope measurements to determine if part of this decrease resulted from removal of Cr(VI) via reduction to insoluble Cr(III). Although waters in the study area contain dissolved oxygen, the basalt host rock contains abundant Fe(II) and may contain reducing microenvironments or aerobic microbes that reduce Cr(VI). In some contaminated locations, (53)Cr/(52)Cr ratios are close to that of the contaminant source, indicating a lack of Cr(VI) reduction. In other locations, ratios are elevated. Part of this shift may be caused by mixing with natural background Cr(VI), which is present at low concentrations but in some locations has elevated (53)Cr/(52)Cr. Some contaminated wells have (53)Cr/(52)Cr ratios greater than the maximum attainable by mixing between the inferred contaminant and the range of natural background observed in several uncontaminated wells, suggesting that Cr(VI) reduction has occurred. Definitive proof of reduction would require additional evidence. Depth profiles of (53)Cr/(52)Cr suggest that reduction occurs immediately below the water table, where basalts are likely least weathered and most reactive, and is weak or nonexistent at greater depth.     

Electroreduction of Cr(VI) to Cr(III) on reticulated vitreous carbon electrodes in a parallel-plate reactor with recirculation

The reduction of Cr(VI) to Cr(III) is achieved in a flow-by, parallel-plate reactor equipped with reticulated vitreous carbon (RVC) electrodes;this reduction can be accomplished by the application of relatively small potentials. Treatment of synthetic samples and field samples (from an electrodeposition plant) results in final Cr(VI) concentrations of 0.1 mg/L (i.e., the detection limit of the UV-vis characterization technique used here) in 25 and 43 min, respectively. Such concentrations comply with typical environmental legislation for wastewaters that regulate industrial effluents (at presenttime = 0.5 mg/L for discharges). The results show the influence of the applied potential, pH, electrode porosity, volumetric flow, and solution concentration on the Cr(VI) reduction percentage and on the required electrolysis time. Values for the mass transfer coefficient and current efficiencies are also obtained. Although current efficiencies are not high, the fast kinetics observed make this proposed treatment an appealing alternative. The lower current efficiency obtained in the case of a field sample is attributed to electrochemical activation of impurities. The required times for the reduction of Cr(VI) are significantly lower than those reported elsewhere.     

Engineering biogenic magnetite for sustained Cr(VI) remediation in flow-through systems

In this work, we report a route to enhance the reactivity and longevity of biogenic magnetite in Cr(VI) remediation under continuous-flow conditions by combining functionalization of the biomagnetite surface with a precious metal catalyst, nanoscale palladium, and exposure to formate. Column influent conditions were varied to simulate oxic, anoxic, and nitrate cocontaminated environments. The addition of sodium formate as an electron donor for Pd-functionalized magnetite increased capacity and longevity allowing 80% removal of Cr(VI) after 300 h in anoxic conditions, whereas complete breakthrough occurred after 60 h in anoxic nonformate and nonfunctionalized systems. Removal of Cr(VI) was optimized under anoxic conditions, and the presence of oxidizing agents results in a modest loss in reductive capacity. Examination of reacted Pd-functionalized magnetite reveals close association of Fe with Cr, suggesting that Pd-coupled oxidation of formate serves to regenerate the reactive surface. XMCD studies revealed that Cr(III) is partially substituted for Fe in the magnetite structure, which serves to immobilize Cr. No evidence for a mechanistic interference by nitrate cocontamination was observed, suggesting that this novel system could provide robust, effective and sustained reduction of contaminants, even in the presence of common oxidizing cocontaminants, outperforming the reductive capacity of nonfunctionalized biogenic magnetite.     

Reduction of Cr(VI) at a polyaniline film: influence of film thickness and oxidation state

Hexavalent chromium [Cr(VI)] is highly toxic, carcinogenic, and mutagenic to living organisms. In this paper, the reduction of Cr(VI) to the much less toxic trivalent state [Cr(III)] was studied at polyaniline films grown to different thickness. Much higher rates of Cr(VI) reduction were observed for the "thick" polyaniline films. This was explained in terms of the morphology of the polymer and the higher surface area of polymer in contact with the Cr(VI) solution. For "thin" polyaniline films, the Cr(VI) reduction reaction was found to obey pseudo-first-order kinetics for the duration of exposure. However, in the case of thick polyaniline layers, the Cr(VI) reduction reaction followed a two-stage process, with each stage obeying pseudo-first-order kinetics. This was explained in terms of oxidation of the polymer from the leucoemeraldine to the emeraldine state and then further oxidation of the polymer from the emeraldine to the pernigraniline state. Much higher rates of Cr(VI) reduction were observed on oxidation of the polymer from the leucoemeraldine to the emeraldine state.     

Kinetic desorption and sorption of U(VI) during reactive transport in a contaminated Hanford sediment

Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, U(VI)-contaminated (22.7 micromol kg(-1)) capillary fringe sediment from the U.S. Department of Energy (DOE) Hanford site. Saturated column experiments were performed under mildly alkaline conditions representative of the Hanford site where uranyl-carbonate and calcium-uranyl-carbonate complexes dominate aqueous speciation. A U(VI)-free solution was used to study contaminant U(VI) desorption in columns where different flow rates were applied. Sorbed, contaminant U(VI) was partially labile (11.8%), and extended leaching times and water volumes were required for complete desorption of the labile fraction. Uranium-(VI) sorption was studied after the desorption of labile, contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic effects were observed for both U(VI) sorption and desorption, with half-life ranging from 8.5 to 48.5 h for sorption and from 39.3 to 150 h for desorption. Although U(VI) is semi-mobile in mildly alkaline, subsurface environments, we observed substantial U(VI) adsorption, significant retardation during transport, and atypical breakthrough curves with extended tailing. A distributed rate model was applied to describe the effluent data and to allow comparisons between the desorption rate of contaminant U(VI) with the rate of shortterm U(VI) sorption. Desorption was the slower process. We speculate that the kinetic behavior results from transport or chemical phenomena within the phyllosilicate-dominated fine fraction present in the sediment. Our results suggest that U(VI) release and transport in the vadose zone and aquifer system from which the sediment was obtained are kinetically controlled.     

Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment

The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] = 10(-7)-10(-5) mol/L and final pH = 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 +/- 0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3(0)(aq) at pH < 8.4 and thatformation of Ca2UO2(CO3)3(0)(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3(4-) in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity.     

Electrically regenerated ion exchange for removal and recovery of Cr(VI) from wastewater

Ion exchange is widely used for removal and recovery of Cr(VI) from wastewater. Generally, the exhausted ion exchanger is regenerated using chemicals. Although chemical regeneration is efficient, contaminants are introduced, leading to difficulty for the subsequent recovery of Cr(VI). To overcome such a problem, a new regeneration method, namely electrical regeneration, which is carried out on the principle of electrodialysis, is presented in this paper. Experimental results showed that the weak-base resin used could be effectively regenerated electrically. About 93% capacity of the resin was restored under a constant current of 0.25 A over a period of 24 h. The pure chromic acid was recovered in the anode chamber with a concentration of 5.03 g Cr(VI)/L. It was found that the weak-base resin regenerated electrically could remove Cr(VI) from wastewater as effectively as that regenerated chemically. The Cr(VI) concentration was reduced from initial 50 mg/L to lower than the detectable limit, 0.01 mg/L, after treatment.     

黑曲霉菌丝体-壳聚糖的制备及对Cr(Ⅵ)的吸附性能研究

研究了黑曲霉菌丝体-壳聚糖对Cr(Ⅵ)的吸附特性。以废弃黑曲霉菌丝体、壳聚糖作为吸附剂制备原料,采用环氧氯丙烷进行交联,三聚磷酸钠进行固化,制备成黑曲霉菌丝体-壳聚糖复合型吸附剂。探究了pH值、黑曲霉菌丝体-壳聚糖的投加量对Cr(Ⅵ)的吸附影响。实验结果表明,黑曲霉菌丝体-壳聚糖的用量为0.5 g时对Cr(Ⅵ)吸附率最高达到92.30%,pH=6时对Cr(Ⅵ)吸附率最高达84.32%。动力学数据分析表明黑曲霉菌丝体-壳聚糖生物吸附剂对Cr(Ⅵ)的吸附过程符合准二级动力学模型(R2=1)。同时该吸附过程符合Freundlich等温线模型,最大吸附量为108.23mg/g;扫描电镜和红外光谱证实吸附反应发生吸附剂的颗粒表层,主要活性基团为-OH,-COOH。上述结果表明,黑曲霉菌丝体-壳聚糖对Cr(Ⅵ)吸附性能良好,绿色环保,应用前景广泛。     

Enhanced reduction of Cr(VI) by direct electric current in a contaminated clay

The probable relation between diffuse double-layer processes and redox reactions that enhance degradation or conversion of contaminants under an applied electric field were examined in a clay medium. Kaolinite clay, precontaminated with hexavalent chromium, was the test soil medium. Analyte, containing ferrous iron, was transported through the kaolinite clay using direct electric current. The Cr(VI) reduction to Cr(III) was followed by measuring the soil redox potential and pH at discrete locations in the clay bed. The post-test distribution of Cr showed significantly more Cr(III) than Cr(VI) at low to slightly acidic pH distribution (2 < pH < 6) in clay. The stoichiometric analyses of measured chromium and iron species concentrations versus the measured redox potentials were compared to Nernst equation predictions of an equivalent aqueous system. An average of +0.37 V shift was measured from the linear Nernstian prediction of cell potential. The applied electric field appeared to provide additional "cathodic current" to drive forth the redox reactions. The redox potential shift was explained by possible overpotential development at the clay-water interfaces due to double-layer polarization under the applied field.