Conversion of Chromium(III) Propionate to Chromate/dichromate(VI) by the Advanced Oxidation Process. Pretreatment of a Biomimetic Complex for Metal Analysis.
ABSTRACT: The use of H(2)O(2) and UV irradiation to remove organic ligands in a chromium(III) complex for the subsequent chromium analysis is reported. The Advanced Oxidation Process (AOP) using a 5.5-W UV lamp, H(2)O(2) and Fe(2+)/Fe(3+) as catalyst (photo Fenton process) was found to give complete and quantitative Cr(III) ? Cr(VI) conversion and removal of ligands in chromium(III) propionate [Cr(3)O(O(2)CCH(2)CH(3))(6)(H(2)O)(3)]NO(3), a biomimetic chromium species, as subsequent chromium analyses by the 1,5-diphenylcarbazide method and atomic absorption revealed. The current process eliminates the need for mineralization and/or dissolution of the matrix in order to remove the organic ligand, the traditional pretreatments of a sample for metal analysis. Studies to optimize the conditions for the oxidation processes, including the use of Fe(2+)/Fe(3+) catalyst, length of UV irradiation, H(2)O(2) concentration, pH, power of UV lamp, and reactor size, are reported.
Project description:We propose a method to enhance the fuel cell efficiency with the simultaneous removal of toxic heavy metal ions. Carbon monoxide (CO), an intermediate of methanol oxidation that is primarily responsible for Pt catalyst deactivation, can be used as an in-situ reducing agent for hexavalent chromium (Cr (VI)) with reactivating the CO-poisoned Pt catalyst. Using electro-oxidation measurements, the oxidation of adsorbed CO molecules coupled with the concurrent conversion of Cr (VI) to Cr (III) was confirmed. This concept was also successfully applied to a methanol fuel cell to enhance its performance efficiency and to remove toxic Cr (VI) at the same time.
Project description:Mesoporous alumina with narrow pore size distribution centered in the range of 4.4-5.0 nm and with a specific surface area as high as 270 m²·g-1 was prepared via the nanocasting approach using a CMK-3 carbon replica as a hard template. Based on this support, a series of catalysts containing 1, 5, 10, 20 and 30 wt % of chromium was prepared by incipient wetness impregnation, characterized, and studied in the dehydrogenation of propane to propene (PDH). Cr species in three oxidation states-Cr(III), Cr(V) and Cr(VI)-were found on the oxidized surface of the catalysts. The concentration of these species varied with the total Cr loading. Temperature-programmed reduction (H?-TPR) and UV-Vis diffuse reflectance spectroscopy (UV-Vis-DRS) studies revealed that Cr(VI) species dominated at the lowest Cr content. An increase in the Cr loading resulted in an appearance of an increasing amount of Cr(III) oxide. UV-Vis-DRS measurements performed in situ during the PDH process showed that at the beginning of the catalytic test Cr(VI) species were reduced to Cr(III) redox species. A crucial role of the redox species in the PDH process over the catalysts with the low Cr content was confirmed. The stability test for the catalyst containing 20 wt % of Cr showed that this sample exhibited the reproducible catalytic performance after the first four regeneration-dehydrogenation cycles. Moreover, this catalyst had higher resistance on deactivation during the PDH process as compared to the reference catalyst with the same Cr loading, but was supported on commercially available alumina.
Project description:The occurrence of chromium (Cr) as an inorganic contaminant in drinking water is widely reported. One source of Cr is its accumulation in iron-containing corrosion scales of drinking water distribution systems as Cr(III)-Fe(III) hydroxide, that is, Fe xCr(1- x)(OH)3(s), where x represents the Fe(III) molar content and typically varies between 0.25 and 0.75. This study investigated the kinetics of inadvertent hexavalent chromium Cr(VI) formation via the oxidation of Fe xCr(1- x)(OH)3(s) by chlorine as a residual disinfectant in drinking water, and examined the impacts of Fe(III) content and drinking water chemical parameters including pH, bromide and bicarbonate on the rate of Cr(VI) formation. Data showed that an increase in Fe(III) molar content resulted in a significant decrease in the stoichiometric Cr(VI) yield and the rate of Cr(VI) formation, mainly due to chlorine decay induced by Fe(III) surface sites. An increase in bicarbonate enhanced the rate of Cr(VI) formation, likely due to the formation of Fe(III)-carbonato surface complexes that slowed down the scavenging reaction with chlorine. The presence of bromide significantly accelerated the oxidation of Fe xCr(1- x)(OH)3(s) by chlorine, resulting from the catalytic effect of bromide acting as an electron shuttle. A higher solution pH between 6 and 8.5 slowed down the oxidation of Cr(III) by chlorine. These findings suggested that the oxidative conversion of chromium-containing iron corrosion products in drinking water distribution systems can lead to the occurrence of Cr(VI) at the tap, and the abundance of iron, and a careful control of pH, bicarbonate and bromide levels can assist the control of Cr(VI) formation.
Project description:BACKGROUND:Chromium (Cr) is a common skin sensitizer. The use of Cr(VI) in leather is restricted in the EU, but that of Cr(III) is not. OBJECTIVES:To assess whether prolonged exposure to Cr-tanned leather with mainly Cr(III) release may elicit allergic contact dermatitis in Cr-allergic individuals. METHOD:Ten Cr-allergic subjects and 22 controls were patch tested with serial dilutions of Cr(III) and Cr(VI), and with leather samples. They then conducted a use test with a Cr-tanned and a Cr-free leather bracelet over a period of 3?weeks, for 12?h per day. Cr deposited on the skin from the bracelets was measured in the controls, and the diphenylcarbazide test for Cr(VI) and extraction tests for Cr(III) and Cr(VI) were conducted for the different leathers. RESULTS:Four of 10 Cr-allergic subjects developed positive reactions to the Cr-tanned bracelet within 7-21?days, whereas only 1 of 10 had a positive patch test reaction to this leather. Cr released from the Cr-tanned leather was most probably entirely Cr(III), with a quantifiable amount being deposited on the skin. CONCLUSIONS:This study strongly suggests that prolonged and repeated exposure to Cr-tanned leather with mainly Cr(III) release is capable of eliciting allergic contact dermatitis in Cr-allergic individuals.
Project description:Occupational exposure to Cr is concerning because of its myriad of health effects. Assessing chromium exposure is also cost and resource intensive because the analysis typically uses sophisticated instrumental techniques like inductively coupled plasma-mass spectrometry (ICP-MS). Here, we report a novel, simple, inexpensive microfluidic paper-based analytical device (?PAD) for measuring total Cr in airborne particulate matter. In the ?PAD, tetravalent cerium (Ce(IV)) was used in a pretreatment zone to oxidize all soluble Cr to Cr(VI). After elution to the detection zone, Cr(VI) reacts with 1,5-diphenylcarbazide (1,5-DPC) forming 1,5-diphenylcarbazone (DPCO) and Cr(III). The resulting Cr(III) forms a distinct purple colored complex with the DPCO. As proof-of-principle, particulate matter (PM) collected on a sample filter was analyzed with the ?PAD to quantify the mass of total Cr. A log-linear working range (0.23-3.75 ?g; r(2)=0.998) between Cr and color intensity was obtained with a detection limit of 0.12 ?g. For validation, a certified reference containing multiple competing metals was analyzed. Quantitative agreement was obtained between known Cr levels in the sample and the Cr measured using the ?PAD.
Project description:Graphene oxide (GO) contains not only aromatic carbon lattice but also carboxyl groups which enhanced the aqueous solubility of GO. To study the transformation of GO nanosheets in natural environments, GO aqueous dispersion was mixed with Fe<sup>3+</sup> ions to form photoactive complex. Under visible light irradiation, Fe(III) of the complex would be reduced to Fe(II) which could subsequently reduce highly toxic Cr(VI) to Cr<sup>3+</sup>. The electron of the reduction was contributed by the decarboxylation of carboxyl groups on GO and iron was acting as a catalyst during the photoreduction. On the other hand, the consumption of carboxyl groups may convert GO to rGO which are tend to aggregate since the decreased electrostatic repulsion and the increased ?-? attraction. The formed Cr<sup>3+</sup> may be electrostatically adsorbed by the rGO sheets and simultaneously precipitated with the aggregated rGO sheets, resulting the effective removal of chromium and GO nanosheets from the aqueous environment. This study may shed a light on understanding the environmental transformation of GO and guide the treatment of Cr(VI).
Project description:Alternative methods of aqueous chromium removal have been of great research interest in recent years as Cr (VI) is a highly toxic compound causing severe human health effects. To achieve better removal of Cr (VI), it is essential to understand the chemical reactions that lead to the successful removal of Cr species from the solution. Recent studies have demonstrated that graphene oxide (GO) based polymer beads cannot only adsorb Cr (VI) via electrostatic attractions but also reduce it to Cr (III), which is a much less toxic form of chromium. This conversion and the functional groups involved in this conversion, until now, were not elucidated. In the present study, we employed X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy to investigate the conversion pathway of Cr (VI) to Cr (III) in graphene-based polymer beads. The results showed that alcoholic groups are converted to carboxylic groups while reducing Cr (VI) to Cr (III). The inclusion of GO in the polymer beads dramatically increased the potential of Cr (VI) uptake and conversion to Cr (III), indicating polymers and nanomaterials containing alcohol groups can remove and convert chromium in water. Other functional groups present in the polymer bead play an important role in adsorption but are not involved in the conversion of Cr (VI) to Cr (III).
Project description:Chromium contamination is a serious environmental issue in areas affected by leather tanning and metal plating, and green rust sulfate has been tested extensively as a potential material for in situ chemical reduction of hexavalent chromium in groundwater. Reported products and mechanisms for the reaction have varied, most likely because of green rust's layered structure, as reduction at outer and interlayer surfaces might produce different reaction products with variable stabilities. Based on studies of Cr(III) oxidation by biogenic Mn (IV) oxides, Cr mobility in oxic soils is controlled by the solubility of the Cr(III)-bearing phase. Therefore, careful engineering of green rust properties, i.e., crystal/particle size, morphology, structure, and electron availability, is essential for its optimization as a remediation reagent. In the present study, pure green rust sulfate and green rust sulfate with Al, Mg and Zn substitutions were synthesized and reacted with identical chromate (CrO42-) solutions. The reaction products were characterized by X-ray diffraction, pair distribution function analysis, X-ray absorption spectroscopy and transmission electron microscopy and treated with synthetic ?-MnO2 to assess how easily Cr(III) in the products could be oxidized. It was found that Mg substitution had the most beneficial effect on Cr lability in the product. Less than 2.5% of the Cr(III) present in the reacted Mg-GR was reoxidized by ?-MnO2 within 14 days, and the particle structure and Cr speciation observed during X-ray scattering and absorption analyses of this product suggested that Cr(VI) was reduced in its interlayer. Reduction in the interlayer lead to the linkage of newly-formed Cr(III) to hydroxyl groups in the adjacent octahedral layers, which resulted in increased structural coherency between these layers, distinctive rim domains, sequestration of Cr(III) in insoluble Fe oxide bonding environments resistant to reoxidation and partial transformation to Cr(III)-substituted feroxyhyte. Based on the results of this study of hexavalent chromium reduction by green rust sulfate and other studies, further improvements can also be made to this remediation technique by reacting chromate with a large excess of green rust sulfate, which provides excess Fe(II) that can catalyze transformation to more crystalline iron oxides, and synthesis of the reactant under alkaline conditions, which has been shown to favor chromium reduction in the interlayer of Fe(II)-bearing phyllosilicates.
Project description:Chromium (Cr) release from Cr-tanned leather articles is a major cause of Cr contact dermatitis. It has been suggested that Cr(VI) release from leather is not necessarily an intrinsic property of the leather, but is strongly dependent on environmental conditions.To test this hypothesis for long-term (8?months) simulated use.The release of total Cr and Cr(VI) from Cr-tanned, unfinished leather was analysed in subsequent phosphate buffer (pH?8.0) immersions for a period of 7.5?months. The effect of combined ultraviolet treatment and alkaline solution (pH?12.1) was tested. Dry storage [20% relative humidity (RH)] was maintained between immersions. Atomic absorption spectroscopy, X-ray fluorescence and diphenylcarbazide tests were used.Cr(VI) release was dependent on previous dry storage or alkaline treatment, but not on duration or number of previous immersions. Cr(III) release decreased with time. Fifty-two percent of the total Cr released during the last immersion period was Cr(VI). Cr(VI) release exceeded 9?mg/kg in all immersion periods except in the first 10-day immersion (2.6?mg/kg).Cr(VI) release is primarily determined by environmental factors (RH prior to immersion, solution pH, and antioxidant content). The RH should be kept low prior to testing Cr(VI) release from leather.
Project description:It is essential and important to determine the adsorption mechanism as well as removal efficiency when using an adsorption technique to remove toxic heavy metals from wastewater. In this research, the removal efficiency and mechanism of chromium removal by a silica-based nanoparticle were investigated. A PEI-silica nanoparticle was synthesized by a one-pot technique and exhibited uniformly well-dispersed PEI polymers in silica particles. The adsorption capacity of chromium ions was determined by a batch adsorption test, with the PEI-silica nanoparticle having a value of 183.7?mg/g and monolayer sorption. Adsorption of chromium ions was affected by the solution pH and altered the nanoparticle surface chemically. First principles calculations of the adsorption energies for the relevant adsorption configurations and XPS peaks of Cr and N showed that Cr(VI), [HCrO4]- is reduced to two species, Cr(III), CrOH2+ and Cr3+, by an amine group and that Cr(III) and Cr(VI) ions are adsorbed on different functional groups, oxidized N and NH3+.