Speciation Analysis of Cr(VI) and Cr(III) in Water with Surface-Enhanced Raman Spectroscopy.
ABSTRACT: Identifying and quantifying chromium in water are important for the protection of precious water resources from chromium pollution. Standard methods however are unable to easily distinguish toxic hexavalent chromium, Cr(VI), from innocuous trivalent chromium, Cr(III), are time-consuming, or require large sample quantity. We show in this report that Cr(VI) and Cr(III) in water can be differentiated based on their distinct spectral features of surface-enhanced Raman scattering (SERS). Their SERS signals exhibit different pH dependences: the SERS features of Cr(VI) and Cr(III) are most prominent at pH values of 10 and 5.5, respectively. The obtained limit of detection of Cr(VI) in water is below 0.1 mg/L. Both concentration curves of their SERS signals show Langmuir sorption isotherm behavior. A procedure was developed to quantify Cr(VI) concentration based on the direct retrieval or addition method with an error of 10%. Finally, the SERS detection of Cr(VI) is shown to be insensitive to co-present Cr(III). The developed SERS procedure offers potential to monitor toxic chromium in fields.
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: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:With the excellent solubility, mobility, bioaccumulation and carcinogenesis, hexavalent chromium Cr (VI), widely exists in various industrial effluents such as chrome plating, metal finishing, pigments, and tanning. Cr (VI) is one of the toxic metal pollutants among all the heavy metals. Therefore, the purpose of this work was to convert highly water-soluble Cr (VI) into Cr (III) species using electrocoagulation (EC) process. The Box-Behnken design (BBD) as was applied to investigate the effects of major operating variables and optimization conditions. The predicted values of responses obtained using the model is agreed well with the experimental data. This work demonstrated that the Cr (VI) is entirely converted into Cr (III) in solid-phases in electrocoagulation process. It was also found that reduction increased with current density that suggesting that the reduction efficiency is closely related to the generation of floc.
Project description:Recently, two-dimensional transition metal dichalcogenides (TMDs) have received tremendous attention in many fields including environmental remediation. Magnetic nanoparticles (Fe3O4NPs) decorated with MoS2 (MoS2@Fe3O4NPs) have been synthesized via a new one-step synthesis route and utilized as an efficient adsorbent for removal of Cr(VI)/Cr(III) from aqueous solutions. The obtained MoS2@Fe3O4NPs with numerous surface hydroxyl groups show uniform size and shape, excellent water-dispersibility, and superior magnetic property to enhance the adsorption. The physicochemical properties of the adsorbent prior to and after adsorption of Cr(VI)/Cr(III) were extensively characterized using several advanced instrumental techniques.The adsorption of Cr(VI)/Cr(III) on MoS2@Fe3O4NPs was performed under batch conditions aiming at identification of optimal contact time, pH value of chromium solution, and influence of the presence of competitive ions. This study was supported by modeling of adsorption equilibrium and kinetics by using empirical equations.
Project description:Chromium is a potentially toxic metal occurring in water and groundwater as a result of natural and anthropogenic sources. Microbial interaction with mafic and ultramafic rocks together with geogenic processes release Cr (VI) in natural environment by chromite oxidation. Moreover, Cr (VI) pollution is largely related to several Cr (VI) industrial applications in the field of energy production, manufacturing of metals and chemicals, and subsequent waste and wastewater management. Chromium discharge in European Union (EU) waters is subjected to nationwide recommendations, which vary depending on the type of industry and receiving water body. Once in water, chromium mainly occurs in two oxidation states Cr (III) and Cr (VI) and related ion forms depending on pH values, redox potential, and presence of natural reducing agents. Public concerns with chromium are primarily related to hexavalent compounds owing to their toxic effects on humans, animals, plants, and microorganisms. Risks for human health range from skin irritation to DNA damages and cancer development, depending on dose, exposure level, and duration. Remediation strategies commonly used for Cr (VI) removal include physico-chemical and biological methods. This work critically presents their advantages and disadvantages, suggesting a site-specific and accurate evaluation for choosing the best available recovering technology.
Project description:For the first time, the heat dried biomass of a newly isolated fungus Arthrinium malaysianum was studied for the toxic Cr(VI) adsorption, involving more than one mechanism like physisorption, chemisorption, oxidation-reduction and chelation. The process was best explained by the pseudo-second order kinetic model and Redlich-Peterson isotherm with maximum predicted biosorption capacity (Q m ) of 100.69?mg?g-1. Film-diffusion was the rate-controlling step and the adsorption was spontaneous, endothermic and entropy-driven. The mode of interactions between Cr(VI) ions and fungal biomass were investigated by several methods [Fourier Transform-Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD) and Energy-Dispersive X-ray spectroscopy (EDX)]. X-ray Photoelectron Spectroscopy (XPS) studies confirmed significant reduction of Cr(VI) into non-toxic Cr(III) species. Further, a modified methodology of Atomic Force Microscopy was successfully attempted to visualize the mycelial ultra-structure change after chromium adsorption. The influence of pH, biomass dose and contact time on Cr(VI) depletion were evaluated by Response Surface Model (RSM). FESEM-EDX analysis also exhibited arsenic (As) and lead (Pb) peaks on fungus surface upon treating with synthetic solutions of NaAsO2 and Pb(NO3)2 respectively. Additionally, the biomass could also remove chromium from industrial effluents, suggesting the fungal biomass as a promising adsorbent for toxic metals removal.
Project description:Chromium contamination has been an increasing threat to the environment and to human health. Cr(VI) and Cr(III) are the most common states of chromium. However, compared with Cr(III), Cr(VI) is more toxic and more easily absorbed, therefore, it is more harmful to human beings. Thus, the conversion of toxic Cr(VI) into Cr(III) is an accepted strategy for chromium detoxification. Here, we isolated two Bacillus cereus strains with a high chromium tolerance and reduction ability, named B. cereus D and 332, respectively. Both strains demonstrated a strong pH and temperature adaptability and survival under 8 mM Cr(VI). B. cereus D achieved 87.8% Cr(VI) removal in 24 h with an initial 2 mM Cr(VI). Cu(II) was found to increase the removal rate of Cr(VI) significantly. With the addition of 0.4 mM Cu(II), 99.9% of Cr(VI) in the culture was removed by B. cereus 332 in 24 h. This is the highest removal efficiency in the literature that we have seen to date. The immobilization experiments found that sodium alginate with diatomite was the better method for immobilization and B. cereus 332 was more efficient in immobilized cells. Our research provided valuable information and new, highly effective strains for the bioremediation of chromium pollution.
Project description:Water pollution caused by the highly toxic metal hexavalent chromium (Cr(VI)) creates significant human health and ecological risks. In this study, a novel adsorbent was used to treat Cr(VI)-containing wastewater; the adsorbent was prepared using red mud (RM) generated from the alumina production industry and the rare earth element lanthanum. This study explored adsorption performance, kinetics, and mechanisms. Results showed that the adsorption kinetics of the RM modified by lanthanum (La-RM), followed the pseudo-second-order model, with a rapid adsorption rate. Cr(VI) adsorption was positively associated with the absorbent dose, pH, temperature, and initial Cr(VI) concentration; coexisting anions had little impact. The maximum Cr(VI) adsorption capacity was 17.35 mg/g. Cr(VI) adsorption on La-RM was a mono-layer adsorption pattern, following the Langmuir isotherm model. Thermodynamic parameters showed the adsorption was spontaneous and endothermic. The adsorption of Cr(VI) on La-RM occurred as a result of LaOCl formation on the RM surface, which in turn further reacted with Cr(VI) in the wastewater. This study highlighted a method for converting industrial waste into a valuable material for wastewater treatment. The novel absorbent could be used as a potential adsorbent for treating Cr(VI)-contaminating wastewater, due to its cost-effectiveness and high adsorption capability.
Project description:The current study aimed to isolate and characterize a chromate-resistant bacterium from tannery effluent, able to reduce Cr(VI) aerobically at high pH and salinity. Environmental contamination by hexavalent chromium, Cr(VI), presents a serious public health problem. Enrichment led to the isolation of 12 bacteria displaying different degrees of chromate reduction. Phenotypic characterization and phylogenetic analysis based on 16S rDNA sequence comparison indicated that the most potent strain belonged to the genus Halomonas. The new strain designated as Halomonas sp. M-Cr was able to reduce 82% of 50 mg L(-1) Cr(VI) in 48 h, concomitant with discolouring of yellow colour of the medium and formation of white insoluble precipitate of Cr(III). It exhibited growth up to 3500 mg L(-1) Cr(VI), 20% NaCl and showed strong Cr(VI) reduction under alkaline condition, pH 10. Scanning electron microscopy revealed precipitation of chromium hydroxide on bacterial cell surfaces, which showed characteristic peak of chromium in energy-dispersive X-ray analysis. Plackett-Burman design was used to evaluate the influence of related parameters for enhancing Cr(VI) reduction. Glucose, yeast extract and KH2PO 4 were confirmed as significant variables in the medium. Data suggest Halomonas sp. M-Cr as a promising candidate for bioremediation of Cr(VI) contaminated effluents particularly in saline and alkaline environments. Up to our knowledge, this is the first report on isolation of haloalkaliphilic Halomonas sp. from tannery effluent.
Project description:Hexavalent chromium contamination of groundwater is a worldwide problem caused by anthropogenic and natural processes. We report the rate of Cr(VI) removal by two humic acids (extracted from Miocene age lignite and younger peat soil) in aqueous suspensions across a pH range likely to be encountered in terrestrial environments. Cr(VI) was reduced to Cr(III) in a first-order reaction with respect Cr(VI) concentration, but exhibited a partial order (~?0.5) with respect to [H+]. This reaction was more rapid with the peat humic acid, where Cr(VI) reduction was observed at all pH values investigated (3.7???pH???10.5). 13C NMR and pyrolysis GC-MS spectroscopy indicate that the reaction results in loss of substituted phenolic moieties and hydroxyl groups from the humic acids. X-ray absorption spectroscopy indicated that at all pH values the resulting Cr(III) was associated with the partially degraded humic acid in an inner-sphere adsorption complex. The reaction mechanism is likely to be controlled by ester formation between Cr(VI) and phenolic/hydroxyl moieties, as this initial step is rapid in acidic systems but far less favourable in alkaline conditions. Our findings highlight the potential of humic acid to reduce and remove Cr(VI) from solution in a range of environmental conditions.