Relative extents, mechanisms, and kinetics of fluoride removal from synthetic groundwater by prevalent sorbents.

Fluoride (F) contamination in groundwater affects millions of people across the world. Although several sorbents have been identified for low-cost F removal, the choice of the optimal sorbent is dictated by the specific chemistry of contaminated groundwater. In this contribution, eight prevalent sorbents-activated alumina (AA), calcite, hydroxyapatite-coated calcite (HCC), natural chitosan, chalk, Mg-Al-CO3 layered double hydroxide (LDH), calcined Mg-Al-CO3 LDH (cLDH), and hydrous ferric oxide (HFO)-were categorized on their relative F removal mechanisms, extents, and kinetics from a typical synthetic groundwater, representative of contaminated aquifers of North India. Initially, batch experiments containing sorbents at 4 g·L-1 were conducted at a high F concentration (2.9 mM). The dominant F removal processes were identified by aqueous- and solid-phase characterization of reaction by-products. While chalk and calcite removed F by secondary precipitation of fluorite, HCC removed F by fluorapatite precipitation, and other sorbents removed F by sorption. Depending on the immobilization mechanism identified, the F uptake kinetics on each sorbent was modeled with either pseudo-second order or generalized rate equations. Among sorptive F uptake, cLDH exhibited the highest (10-2.15 mg·g-1·h-1) and HFO showed the lowest (10-4.15 mg·g-1·h-1) rates. Fluoride removal by precipitation was the fastest with chalk at 10-1.3 (h-1) (0.16). Subsequent experiments with AA and HCC at lower initial F concentration (0.42 mM) suggested increased uptake by ∼30x and ∼7x, respectively, relative to uptake in 2.9 mM initial F systems. For AA, apart from the widely-accepted mechanism of adsorption, an unidentified F-containing surface precipitate was formed. HCC was identified as the most promising sorbent with no sludge generation.

Investigation of Potential Drivers of Elevated Uranium Prevalence in Indian Groundwaters with a Unified Speciation Model.

Elevated uranium (U) (>WHO limit of 30 µg L-1) in Indian groundwaters is primarily considered geogenic, but the specific mineralogical sources and mechanisms for U mobilization are poorly understood. In this contribution, statistical and geochemical analyses of well-constrained metadata of Indian groundwater quality (n = 342 of 8543) were performed to identify key parameters and processes that influence U concentrations. For geochemical predictions, a unified speciation model was developed from a carefully compiled and updated thermodynamic database of inorganic, organic (Stockholm Humic model), and surface complexation reactions and associated constants. Critical U contamination was found at shallow depths (<100 m) within the Indo-Gangetic plain, as determined by bivariate nonparametric Kendall's Taub and probability-based association tests. Analysis of aquifer redox states, multivariate hierarchical clusters, and principal components indicated that U contamination was predominant not just in oxic but mixed (oxic-anoxic) aquifers under high Fe, Mn, and SO4 concentrations, presumably due to U release from dissolution of Fe/Mn oxides or Fe sulfides and silicate weathering. Most groundwaters were undersaturated with respect to relevant U-bearing solids despite being supersaturated with respect to atmospheric CO2 (average pCO2 of reported dissolved inorganic carbonate (DIC) data = 10-1.57 atm). Yet, dissolved U did not appear to be mass limited, as predicted solubilities from reported sediment concentrations of U were ∼3 orders of magnitude higher. Integration of surface complexation models of U on typical aquifer adsorbents, ferrihydrite, goethite, and manganese dioxide, was necessary to explain dissolved U concentrations. Uranium contamination probabilities with increasing dissolved Ca and Mn exhibited minima at equilibrium solubilities of calcite [∼50 mg L-1] and rhodochrosite [∼0.14 mg L-1], respectively, at an average groundwater pH of ∼7.5. A potential indirect control of such U-free carbonate solids on U mobilization was suggested. For locations (n = 37) where dissolved organic carbon was also reported, organic complexes of U contributed negligibly to dominant U speciation at the groundwater pH. Overall, the unified model suggested competitive dissolution-precipitation and adsorption-desorption controls on U speciation. The model provides a quantitative framework that can be extended to understand dominant mobilization mechanisms of geogenic U in aquifers worldwide after suitable modifications to the relevant aquifer parameters.

Identification and Genome Analysis of an Arsenic-Metabolizing Strain of Citrobacter youngae IITK SM2 in Middle Indo-Gangetic Plain Groundwater.

Whole-genome sequencing (WGS) data of a bacterial strain IITK SM2 isolated from an aquifer located in the middle Indo-Gangetic plain is reported here, along with its physiological, morphological, biochemical, and redox-transformation characteristics in the presence of dissolved arsenic (As). The aquifer exhibits oxidizing conditions relative to As speciation. Analyses based on 16S rRNA and recN sequences indicate that IITK SM2 was clustered with C. youngae NCTC 13708T and C. pasteuri NCTC UMH17T. However, WGS analyses using the digital DNA-DNA hybridization and Rapid Annotations using Subsystems Technology suggest that IITK SM2 belongs to a strain of C. youngae. This strain can effectively reduce As(V) to As(III) but cannot oxidize As(III) to As(V). It exhibited high resistance to As(V) [32,000 mg L-1] and As(III) [1,100 mg L-1], along with certain other heavy metals typically found in contaminated groundwater. WGS analysis also indicates the presence of As-metabolizing genes such as arsC, arsB, arsA, arsD, arsR, and arsH in this strain. Although these genes have been identified in several As(V)-reducers, the clustering of these genes in the forms of arsACBADR, arsCBRH, and an independent arsC gene has not been observed in any other Citrobacter species or other selected As(V)-reducing strains of Enterobacteriaceae family. Moreover, there were differences in the number of genes corresponding to membrane transporters, virulence and defense, motility, protein metabolism, phages, prophages, and transposable elements in IITK SM2 when compared to other strains. This genomic dataset will facilitate subsequent molecular and biochemical analyses of strain IITK SM2 to identify the reasons for high arsenic resistance in Citrobacter youngae and understand its role in As mobilization in middle Indo-Gangetic plain aquifers.

Smartphone-enabled field monitoring tool for rapid hexavalent chromium detection in water.

Chromium contamination of soil and water is a serious environmental and public health concern as the hexavalent form of chromium [Cr(VI)] is readily soluble in water and is a confirmed carcinogen. There is an imminent need for a robust, low-cost, and simple analytical technique to facilitate in situ monitoring of Cr(VI) in water. Current quantitative methods of Cr(VI) detection are largely laboratory-based, time-consuming, expensive, and require training for implementation. In this contribution, a portable, easy-to-use, and compact measuring tool is presented that provides Cr(VI) concentration within 10 min of water sampling over a linear range of 0-3 mg L-1. This tool utilizes a relatively inexpensive camera-enabled smartphone with a custom-made test chamber attachment to seamlessly perform Cr(VI) measurements on water samples in the field. For analysis, an android-based software application was developed that directs the user to perform a simple series of steps following the diphenylcarbazide-based colorimetric method prescribed by the American Public Health Association. The tool was validated against a standard UV-visible spectrophotometer for a variety of synthetic and naturally contaminated water samples, with correlation factors greater than 0.993 (p < .001). The colorimetric method was also validated against a non-colorimetric Cr(VI) detection technique-ion chromatography-inductively coupled plasma mass spectrometry. Furthermore, Cr(VI) detection limits for the smartphone-enabled colorimetric method were found to be within 1.3-11.6 µg L-1, which were significantly better than reported for commercially available field test kits, and even surpassed the limits exhibited by a typical spectrophotometer (25-50 µg L-1). Finally, real-time mapping of source waters at a contaminated site was demonstrated by remote logging of Cr(VI) water quality data and corresponding GPS coordinates into a cloud server. This study highlights the potential role of smartphone-based monitoring tool in providing information to the affected community and enabling safe access to drinking water. An accurate, robust, simple-to-use, and economic method to measure hexavalent chromium in water within 10 min of sampling at site.

Genome Sequence of Bacillus subtilis subsp. subtilis Strain IITK SM1, Isolated from Kitchen Waste Compost.

We report here the complete genome sequence of Bacillus subtilis subsp. subtilis strain IITK SM1, isolated from kitchen waste compost. We have sequenced the whole genome of this strain to identify and characterize the enzymes that participate in efficient composting activity.

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

Chromium pollution of soil and water is a serious environmental concern due to potential carcinogenicity of hexavalent chromium [Cr(VI)] when ingested. Eucalyptus bark biochar (EBB), a carbonaceous black porous material obtained by pyrolysis of biomass at 500 °C under oxygen-free atmosphere, was used to investigate the removal of aqueous Cr(VI) upon interaction with the EBB, the dominant Cr(VI) removal mechanism(s), and the applicability to treat Cr(VI)-contaminated wastewater. Batch experiments showed complete removal of aqueous Cr(VI) at pH 1-2; sorption was negligible at pH 1, but ~55% of total Cr was sorbed onto the EBB surface at pH 2. Detailed investigations on unreacted and reacted EBB through Fourier transform infrared spectroscopy and X-ray photoelectron spectrometry (XPS) indicate that the carboxylic groups in biochar played a dominant role in Cr(VI) sorption, whereas the phenolic groups were responsible for Cr(VI) reduction. The predominance of sorption-reduction mechanism was confirmed by XPS studies that indicated ~82% as Cr(III) and ~18% as Cr(VI) sorbed on the EBB surface. Significantly, Cr(VI) reduction was also facilitated by dissolved organic matter (DOM) extracted from biochar. This reduction was enhanced by the presence of biochar. Overall, the removal of Cr(VI) in the presence of biochar was affected by sorption due to electrostatic attraction, sorption-reduction mediated by surface organic complexes, and aqueous reduction by DOM. Relative dominance of the aqueous reduction mechanism depended on a critical biochar dosage for a given electrolyte pH and initial Cr(VI) concentration. The low-cost EBB developed here successfully removed all Cr(VI) in chrome tanning acidic wastewater and Cr(VI)-contaminated groundwater after pH adjustment, highlighting its potential applicability in effective Cr(VI) remediation.

Environmental status of groundwater affected by chromite ore processing residue (COPR) dumpsites during pre-monsoon and monsoon seasons.

Chromite ore processing residue (COPR) is generated by the roasting of chromite ores for the extraction of chromium. Leaching of carcinogenic hexavalent chromium (Cr(VI)) from COPR dumpsites and contamination of groundwater is a key environmental risk. The objective of the study was to evaluate Cr(VI) contamination in groundwater in the vicinity of three COPR disposal sites in Uttar Pradesh, India, in the pre-monsoon and monsoon seasons. Groundwater samples (n = 57 pre-monsoon, n = 70 monsoon) were taken in 2014 and analyzed for Cr(VI) and relevant hydrochemical parameters. The site-specific ranges of Cr(VI) concentrations in groundwater were <0.005 to 34.8 mg L-1 (Rania), <0.005 to 115 mg L-1 (Chhiwali), and <0.005 to 2.0 mg L-1 (Godhrauli). Maximum levels of Cr(VI) were found close to the COPR dumpsites and significantly exceeded safe drinking water limits (0.05 mg L-1). No significant dependence of Cr(VI) concentration on monsoons was observed.

Molecular-scale structure of uranium(VI) immobilized with goethite and phosphate.

The molecular-scale immobilization mechanisms of uranium uptake in the presence of phosphate and goethite were examined by extended X-ray absorption fine structure (EXAFS) spectroscopy. Wet chemistry data from U(VI)-equilibrated goethite suspensions at pH 4-7 in the presence of ~100 µM total phosphate indicated changes in U(VI) uptake mechanisms from adsorption to precipitation with increasing total uranium concentrations and with increasing pH. EXAFS analysis revealed that the precipitated U(VI) had a structure consistent with the meta-autunite group of solids. The adsorbed U(VI), in the absence of phosphate at pH 4-7, formed bidentate edge-sharing, ≡ Fe(OH)(2)UO(2), and bidentate corner-sharing, (≡ FeOH)(2)UO(2), surface complexes with respective U-Fe coordination distances of ~3.45 and ~4.3 Å. In the presence of phosphate and goethite, the relative amounts of precipitated and adsorbed U(VI) were quantified using linear combinations of the EXAFS spectra of precipitated U(VI) and phosphate-free adsorbed U(VI). A U(VI)-phosphate-Fe(III) oxide ternary surface complex is suggested as the dominant species at pH 4 and total U(VI) of 10 µM or less on the basis of the linear combination fitting, a P shell indicated by EXAFS, and the simultaneous enhancement of U(VI) and phosphate uptake on goethite. A structural model for the ternary surface complex was proposed that included a single phosphate shell at ~3.6 Å (U-P) and a single iron shell at ~4.3 Å (U-Fe). While the data can be explained by a U-bridging ternary surface complex, (≡ FeO)(2)UO(2)PO(4), it is not possible to statistically distinguish this scenario from one with P-bridging complexes also present.

Nanoscale size effects on uranium(VI) adsorption to hematite.

U(VI) adsorption on aerosol-synthesized hematite particles ranging in size from 12 to 125 nm was studied to explore nanoscale size effects on uranium adsorption. Adsorption on 70 nm aqueous-synthesized particles was also investigated to examine the effect of the synthesis method on reactivity. Equilibrium adsorption was measured over pH 3-11 at two U(VI) loadings. Surface complexation modeling, combined with adjustment of adsorption equilibrium constants to be independent of site density and surface area, provided a quantitative reaction-based framework for evaluating adsorption affinity and capacity. Among the aerosol-synthesized particles, the adsorption affinity decreased as the particle size increased from 12 to 125 nm with similar intermediate affinities for 30 and 50 nm particles. X-ray absorption fine structure spectroscopy measurements suggest that the differences in adsorption affinity and capacity are not the result of substantially different coordination environments of adsorbed U(VI).

Dissolution of biogenic and synthetic UO2 under varied reducing conditions.

The chemical stability of biogenic UO2, a nanoparticulate product of environmental bioremediation, may be impacted by the particles' surface free energy, structural defects, and compositional variability in analogy to abiotic UO(2+x) (0 < or = x < or = 0.25). This study quantifies and compares intrinsic solubility and dissolution rate constants of biogenic nano-UO2 and synthetic bulk UO2.00, taking molecular-scale structure into account. Rates were determined under anoxic conditions as a function of pH and dissolved inorganic carbon in continuous-flow experiments. The dissolution rates of biogenic and synthetic UO2 solids were lowest at near neutral pH and increased with decreasing pH. Similar surface area-normalized rates of biogenic and synthetic UO2 suggest comparable reactive surface site densities. This finding is consistent with the identified structural homology of biogenic UO2 and stoichiometric UO2.00 Compared to carbonate-free anoxic conditions, dissolved inorganic carbon accelerated the dissolution rate of biogenic UO2 by 3 orders of magnitude. This phenomenon suggests continuous surface oxidation of U(IV) to U(VI), with detachment of U(VI) as the rate-determining step in dissolution. Although reducing conditions were maintained throughout the experiments, the UO2 surface can be oxidized by water and radiogenic oxidants. Even in anoxic aquifers, UO2 dissolution may be controlled by surface U(VI) rather than U(IV) phases.