Ce4+-Substituted Ni-Al mixed oxide: fluoride adsorption performance and reusability.

In this study, Ce4+-doped Ni-Al mixed oxides (NACO) were synthesized and comprehensively characterized for their potential application in fluoride adsorption. NACOs were examined using Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM), revealing a sheet-like morphology with a nodular appearance. X-ray diffraction (XRD) analysis confirmed the formation of mixed oxides of cubic crystal structure, with characteristic planes (111), (200), and (220) at 2θ values of 37.63°, 43.61°, and 63.64°, respectively. Further investigations using X-ray Photoelectron Spectroscopy (XPS) identified the presence of elements such as Ni, Al, Ce, and O with oxidation states +2, +3, +4, and -2, respectively. The Brunauer-Emmett-Teller (BET) analysis indicated that NACO followed a type IV physisorption isotherm, suggesting favorable surface adsorption characteristics. The adsorption kinetics was studied, and the experimental data exhibited a good suit to both pseudo-first order and pseudo-second order, as indicated by high R2 values. Moreover, the Freundlich isotherm model demonstrated a good fit to the experimental data. The result also revealed that NACO has a maximum capacity for adsorption (qmax) of 132 mg g-1. Thermodynamic studies showed that fluoride adsorption onto NACO was feasible and spontaneous. Additionally, NACO exhibited excellent regeneration capabilities, as evidenced by a remarkable 75.71% removal efficiency at the sixth regeneration stage, indicating sustained adsorption capacity even after multiple regeneration cycles. Overall, NACOs displayed promising characteristics for fluoride adsorption, making them potential candidates for efficient and sustainable water treatment technologies.

Kinetics, isotherm, mechanism, and recyclability of novel nano-sized Ce4+-doped Ni-Al layered double hydroxide for defluoridation of aqueous solutions.

Excessive fluoride removal from aqueous solutions is of utmost importance as it has an adverse impact on human health. This study investigates the defluoridation efficiency of a novel nano-sized Ce+4-doped Ni/Al layered double hydroxide (Ni-Al-Ce LDH) for aqueous solutions. The synthesized Ni-Al-Ce LDH exhibited a well-defined nanoscale plate-like morphology and a high surface area with an average size of 11.51 nm, which contributed to its enhanced fluoride adsorption capacity. XRD, SEM, HRTEM, and BET studies confirmed these characteristics. XPS analysis confirmed the presence of Ce4+ ions within the Ni-Al LDH. The experimental results indicated that the process of defluoridation followed a pseudo-second-order model of kinetics, suggesting a chemisorption mechanism. The fluoride adsorption isotherms demonstrated well fits to the Freundlich, Langmuir, and Jovanovic models, indicating both monolayer and multilayer fluoride adsorption on the Ce-doped Ni-Al LDH. The maximum adsorption capacity was found to be 238.27 mg/g (Langmuir) and 130.73 mg/g (Jovanovic) at pH 6.0 and 25 °C. The proposed mechanisms for fluoride adsorption on the LDH include ion exchange, surface complexation, hydrogen bonding, and ligand exchange. The Ni-Al-Ce LDH nanomaterial exhibited good recyclability, maintaining 71% of the fluoride adsorption efficiency even after four consecutive cycles. This study highlights the significant role of Ce doping in improving the performance of Ni-Al LDH as a defluoridation adsorbent.

Arsenic exposure from drinking water and staple food (rice): A field scale study in rural Bengal for assessment of human health risk.

Arsenic is a well-known carcinogen with emerging reports showing a range of health outcomes even for low to moderate levels of exposure. This study deals with arsenic exposure and associated increased lifetime cancer risk for populations in arsenic-endemic regions of rural Bengal, where arsenic-safe drinking water is being supplied at present. We found a median total exposure of inorganic arsenic to be 2. 9 µg/Kg BW/day (5th and 95th percentiles were 1.1 µg/Kg BW/day and 7.9 µg/Kg BW/day); with major contribution from cooked rice intake (2.4 µg/Kg BW/day). A significant number of households drank arsenic safe water but used arsenic-rich water for rice cooking. As a result, 67% participants had inorganic arsenic intake above the JEFCA threshold value of 3 µg/Kg BW/day for cancer risk from only rice consumption when arsenic contaminated water was used for cooking (median: 3.5 µg/Kg BW/day) compared to 29% participants that relied on arsenic-free cooking water (median: 1.0 µg/kg BW/day). Arsenic in urine samples of study participants ranged from 31.7 to 520 µg/L and was significantly associated with the arsenic intake (r = 0.76); confirming the preponderance of arsenic exposure from cooked rice. The median arsenic attributable cancer risks from drinking water and cooked rice were estimated to be 2.4 × 10-5 and 2.7 × 10-4 respectively, which further emphasized the importance of arsenic exposure from staple diet. Our results show that any mitigation strategy should include both drinking water and local staple foods in order to minimize the potential health risks of arsenic exposure.

Kinetic evaluation for rapid degradation of dimethylamine enriched with Agromyces and Ochrobactrum sp.

Dimethylamine (DMA) possesses an obnoxious odor which has resulted in public concern during the past several decades. A rare bacterial species proficient to degrade DMA, designated IR-26, was isolated from Indian Oil Corporation Limited (IOCL) and identified as Agromyces and Ochrobactrum sp., which has presented a rapid degradation when compared to other bacterial species which were capable to degrade DMA. The removal efficiency of 100% has been calculated in different concentration of DMA. The kinetic study reveals the maximum reduction rate of DMA was 0.11 per hour and the maximum growth rate of biomass was 0.013 per hour respectively. The saturation constant of DMA was around 1.96 mg/L which shows a high affinity of DMA. The importance of these analyses is offered and conversed in this paper.

Highly improved photoreduction of carbon dioxide to methanol using cobalt phthalocyanine grafted to graphitic carbon nitride as photocatalyst under visible light irradiation.

A substantially improved methanol yield was achieved from the photoreduction of carbon dioxide under visible light by using a hybrid photocatalyst consisting of molecular cobalt phthalocyanine tetracarboxylic acid (CoPc-COOH) complex immobilized to the organic semiconductor graphitic carbon nitride (g-C3N4) and triethylamine as sacrificial electron donor. The structural and morphological features of the hybrid photocatalyst determined by various techniques like FTIR, UV-Vis, Raman, XPS, TGA, BET etc. After 24 h of light irradiation, the methanol yield by using g-C3N4/CoPc-COOH photocatalyst (50 mg) was found to be 646.5 µmol g-1cat or 12.9 mmol g-1cat with conversion rate 538.75 µmol h-1 g-1cat. However, the use of homogeneous CoPc-COOH (6.5 µmol Co, equivalent to g-C3N4/CoPc-COOH) and g-C3N4 (50 mg) provided 88.5 µmol (1770 µmol g-1cat) and 59.2 µmol (1184 µmol g-1cat) yield of methanol, respectively under identical conditions. The improved photocatalytic efficiency of the hybrid was attributed to the binding ability of CoPc-COOH to CO2 that provided the higher CO2 concentration on the support. Further, the semiconductor support provided better electron mobility and charge separation with the integrated benefit of facile recovery and recycling of the material at the end of the reduction process.

Integrated bio-oxidation and adsorptive filtration reactor for removal of arsenic from wastewater.

Recently, removal of arsenic from different industrial effluent discharged using simple, efficient and low-cost technique has been widely considered. In this study, removal of arsenic (As) from real wastewater has been studied employing modified bio-oxidation followed by adsorptive filtration method in a novel continuous flow through the reactor. This method includes biological oxidation of ferrous to ferric ions by immobilized Acidothiobacillus ferrooxidans bacteria on granulated activated carbon (GAC) in fixed bed bio-column reactor with the adsorptive filtration unit. Removal efficiency was optimized regarding the initial flow rate of media and ferrous ions concentration. Synthetic wastewater sample having different heavy metal ions such as Arsenic (As), Cobalt (Co), Chromium (Cr), Copper (Cu), Iron (Fe), Lead (Pb) and Manganese (Mn) were also used in the study. The structural and surface changes occurring after the treatment process were scrutinized using FT-IR and Scanning Electron Microscopy (SEM) analysis. The finding showed that not only arsenic can be removed considerably in the bioreactor system, but also removing efficiency was much more (<90%) for other heavy metals in real wastewater sample. The results from TCPL test confirms that solid spent media was non-hazardous and can be safely disposed of. This study verified that combination of bio-oxidation with adsorptive filtration method improves the removal efficiency of arsenic and other heavy metal ions in wastewater sample.

Biomimetic lipophilic activated carbon for enhanced removal of triclosan from water.

Triclosan, an antimicrobial micro-pollutant with a high bio-accumulation potential represented by its high octanol-water partition coefficient (log Kow) of 4.76 is commonly encountered in water and wastewater worldwide. The present study focuses on biomimetic surface modification of commercial activated carbon (PAC) with long chain fatty acid namely docosahexaenoic acid (DHA) resulting in enhanced affinity for the hydrophobic micro-pollutant; triclosan (TCS). The sorption process of the resulting modified lipophilic carbon (PACM) was investigated for the effect of various experimental conditions. The Freundlich isotherm and pseudo-second-order kinetic models had a better fit. PACM exhibited the maximum adsorption capacity of 395.2 mg g-1 in contrast to 71.5 mg g-1 obtained for PAC. The surface morphology in terms of surface area, surface acidity, pore size, contact angle, etc. and were also evaluated. The contact angle of 134.3° obtained for PACM confirmed its highly hydrophobic nature. The efficacy of PACM was also evaluated using real-world secondary treated effluent containing triclosan confirming its applicability for tertiary treatment of wastewater. The study established that the biomimetic approach of creating lipid-like sites on the carbon surface results in the enhanced removal of lipophilic micro-pollutants. It can also be utilized for the removal and recovery of a wide variety of other organic micro-pollutants.

A novel fungal arsenic methyltransferase, WaarsM reduces grain arsenic accumulation in transgenic rice (Oryza sativa L.).

Rice (Oryza sativa L.) grown on arsenic-containing soil and water become a primary dietary source of arsenic and pose a significant health risk. Gene modification is an important and practical approach to reduce arsenic accumulation in rice grains. Here, we reported a WaarsM gene of soil fungus Westerdykella aurantiaca, expressed in rice able to convert toxic inorganic arsenicals to methylated arsenic species, therefore, reduce arsenic accumulation in rice grains. In response to arsenic treatment in hydroponics, WaarsM expressing transgenic lines showed a marked increase in arsenic resistance and reduces its accumulation compared to NT. Also, WaarsM expressing transgenic Line 1 evolved ca. 157ng and ca. 43ng volatile arsenicals (mg-1 fresh weight) after 72h of exposure to 25µM AsIII and 250µM AsV, respectively. Transgenic Line 1, grown in soil irrigated with arsenic-containing water accumulates about 50% and 52% lower arsenic than NT in shoot and root, respectively; while arsenic concentration in polished seeds and husk of the transgenic line was reduced by 52% compared to NT. Thus, the present study demonstrates that the expression of WaarsM in rice induces arsenic methylation and volatilization, provides a potential strategy to reduce arsenic accumulation in rice grain.

Recent advancements in the mitigation of obnoxious nitrogenous gases.

Nitrogenous gaseous emissions commonly have an obnoxious odor associated with it, which when discharged into the environment results in serious environmental problems and health hazards. Several strategies for mitigation of nitrogenous odorants have been reported which include physical, chemical and biological methods. Biological treatments are widely employed because of their efficiency even at low concentration, where physical and chemical methods are not effective. Most commonly used biological treatment methods are biofiltration, biotrickling filters and membrane bioreactors with innovative reactor design, mixing pattern, and air sparging, for example FEBR, ALR, etc. These treatment methods require a critical assessment for the mitigation of obnoxious nitrogen emissions, especially in the context of environmental protection. This review offers a critical evaluation of treatment methods for the mitigation of nitrogenous odorous compound with a key emphasis on biological treatment systems. Also, various mathematical modelling techniques required for optimized operation of biotreatment systems has been discussed.

An improved method for direct estimation of free cyanide in drinking water by Ion Chromatography-Pulsed Amperometry Detection (IC-PAD) on gold working electrode.

In the present work a fast, reliable and safe Ion Exchange Chromatography-Pulsed Amperometry Detection (IC-PAD) method for direct determination of free cyanide in drinking water has been reported. To the best of our knowledge for the first time we are reporting the application of Gold working electrode for detection of free cyanide in a chromatography system. The system shows a wide linear range up to 8000µg/L. The electrode was found to have improved sensitivity and selectivity in the presence of interfering ions. The detection limit of the system was calculated to be 2µg/L. Long term evaluation of the electrode was found to be stable. Reproducible results were obtained from analysis of drinking water samples with recoveries of 98.3-101.2% and Relative Standard Deviations (RSD) of <2%. This study proves the potential application of the newly developed method for the analysis of free cyanide in drinking water.

Effect of hydrophobicity of pharmaceuticals and personal care products for adsorption on activated carbon: Adsorption isotherms, kinetics and mechanism.

Adsorption of three pharmaceuticals and personal care products (PPCPs), namely caffeine, ibuprofen and triclosan on commercial powdered activated carbon was examined in aqueous medium. The contaminants were chosen based on their diverse log Kow (octanol-water partition coefficient) viz. - 0.07 for caffeine, 3.97 for ibuprofen and 4.76 for triclosan to examine the role of hydrophobicity on adsorption process. The adsorbent characterisation was achieved using BET surface area, SEM, pore size distribution studies and FTIR. Influence of mass of PAC, contact time, solution pH and initial concentration on adsorption capacity of PAC was studied. Adsorption isotherms and kinetics were applied to establish the mechanism of adsorption. The kinetics followed pseudo-second order with physisorption occurring through particle diffusion. The Freundlich model fitted best among the isotherm models. The adsorption capacity increased in the order CFN < IBU < TCS which correlates with increasing hydrophobicity (log Kow), molecular weight and decreasing water solubility, respectively. We conclude that micro-pollutant hydrophobicity contributes towards adsorption on activated carbon.

Overexpression of rice glutaredoxins (OsGrxs) significantly reduces arsenite accumulation by maintaining glutathione pool and modulating aquaporins in yeast.

Arsenic (As) is an acute poison and class I carcinogen, can cause a serious health risk. Staple crops like rice are the primary source of As contamination in human food. Rice grown on As contaminated areas accumulates higher As in their edible parts. Based on our previous transcriptome data, two rice glutaredoxins (OsGrx_C7 and OsGrx_C2.1) were identified that showed up-regulated expression during As stress. Here, we report OsGrx_C7 and OsGrx_C2.1 from rice involved in the regulation of intracellular arsenite (AsIII). To elucidate the mechanism of OsGrx mediated As tolerance, both OsGrxs were cloned and expressed in Escherichia coli (Δars) and Saccharomyces cerevisiae mutant strains (Δycf1, Δacr3). The expression of OsGrxs increased As tolerance in E. coli (Δars) mutant strain (up to 4 mM AsV and up to 0.6 mM AsIII). During AsIII exposure, S. cerevisiae (Δacr3) harboring OsGrx_C7 and OsGrx_C2.1 have lower intracellular AsIII accumulation (up to 30.43% and 24.90%, respectively), compared to vector control. Arsenic accumulation in As-sensitive S. cerevisiae mutant (Δycf1) also reduced significantly on exposure to inorganic As. The expression of OsGrxs in yeast maintained intracellular GSH pool and increased extracellular GSH concentration. Purified OsGrxs displays in vitro GSH-disulfide oxidoreductase, glutathione reductase and arsenate reductase activities. Also, both OsGrxs are involved in AsIII extrusion by altering the Fps1 transcripts in yeast and protect the cell by maintaining cellular GSH pool. Thus, our results strongly suggest that OsGrxs play a crucial role in the maintenance of the intracellular GSH pool and redox status of the cell during both AsV and AsIII stress and might be involved in regulating intracellular AsIII levels by modulation of aquaporin expression and functions.

A novel arsenic methyltransferase gene of Westerdykella aurantiaca isolated from arsenic contaminated soil: phylogenetic, physiological, and biochemical studies and its role in arsenic bioremediation.

Elevated arsenic concentration in the environment and agricultural soil is a serious concern to crop production and human health. Among different detoxification mechanisms, the methylation of arsenic is a widespread phenomenon in nature. A number of microorganisms are able to methylate arsenic, but less is known about the arsenic metabolism in fungi. We identified a novel arsenic methyltransferase (WaarsM) gene from a soil fungus, Westerdykella aurantiaca. WaarsM showed sequence homology with all known arsenic methyltransferases having three conserved SAM binding motifs. The expression of WaarsM enhanced arsenic resistance in E. coli (Δars) and S. cerevisiae (Δacr2) strains by biomethylation and required endogenous reductants, preferably GSH, for methyltransferase activity. The purified WaarsM catalyzes the production of methylated arsenicals from both AsIII and AsV, and also displays AsV reductase activity. It displayed higher methyltransferase activity and lower KM 0.1945 ± 0.021 mM and KM 0.4034 ± 0.078 mM for AsIII and AsV, respectively. S. cerevisiae (Δacr2) cells expressing WaarsM produced 2.2 ppm volatile arsenic and 0.64 ppm DMA(v) with 0.58 ppm volatile arsenicals when exposed to 20 ppm AsV and 2 ppm AsIII, respectively. Arsenic tolerance in rice after co-culture with genetically engineered yeast suggested its potential role in arsenic bioremediation. Thus, characterization of WaarsM provides a potential strategy to reduce arsenic concentration in soil with reduced arsenic accumulation in crops grown in arsenic contaminated areas, and thereby alleviating human health risks.

Nanostructured Mn-Fe Binary Mixed Oxide: Synthesis, Characterization and Evaluation for Arsenic Removal.

Adsorption of arsenic on bimetallic Mn and Fe mixed oxide was carried out using both field as well as simulated water. The material was synthesized using hydrothermal method and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Langmuir and Freundlich adsorption isotherms were computed using batch adsorption studies to determine the adsorption capacity of Mn-Fe binary mixed oxide for arsenic. Adsorption capacity for MFBMO obtained from Freundlich model was found to be 2.048 mg/g for simulated water and 1.084 mg/g for field water. Mn-Fe binary mixed oxide was found to be effective adsorbent for removal of arsenic from water.

Removal of As(III) and As(V) from water by copper oxide incorporated mesoporous alumina.

In the present manuscript a new adsorbent namely copper oxide incorporated mesoporous alumina (COIMA) for removal of arsenic from water is reported. The COIMA was prepared by treating mesoporous alumina with copper sulphate solution followed by calcination at 450°C in the presence of air. Various adsorption isotherm and kinetic parameters were computed using batch adsorption studies to determine the adsorption capacity for As(III) and As(V) and to understand the mechanism of adsorption. It was observed that incorporation of copper oxide improves the adsorption capacity of unmodified alumina from 0.92 to 2.16 mg g(-1) for As(III) and from 0.84 to 2.02 mg g(-1) for As(V). The results revealed that the adsorption follows Langmuir isotherm and pseudo-second-order kinetic models for both As(III) and As(V). The material is capable of simultaneously removing As(III) and As(V) with removal efficiencies of more than 95% for both As(III) and As(V). Assessment of the water quality before and after treatment with COIMA also confirmed that the there is no leaching of copper and other parameters were also within permissible limits of Indian drinking water standard indicating that the COIMA can be used for treatment of arsenic contaminated drinking water.

Fluoride removal using lanthanum incorporated chitosan beads.

Highly selective material based on naturally occurring biomaterial namely chitosan has been designed for the defluoridation of water. Lanthanum incorporated chitosan beads (LCB) were prepared using precipitation method. The synthesis was optimized by varying different synthesis parameters namely lanthanum loading, complexation and precipitation time, strength of ammonia solution used for precipitation, drying time, etc. Lanthanum incorporated chitosan beads were characterized using SEM, FTIR, XRD and EDX. Surface area of LCB was observed to be 2.76 m(2)g(-1). The equilibrium adsorption data fitted well to Langmuir adsorption isotherm and showing maximum fluoride adsorption capacity of 4.7 mg g(-1) with negligible lanthanum release. Kinetic study reveals that adsorption of fluoride is fast and follows pseudo-first-order kinetics. The effect of pH was also studied and the best efficiency was observed at pH 5. Presence of sulphate, nitrate and chloride marginally affected the removal efficiency, however drastic reduction in fluoride uptake was observed in the presence of carbonate and bicarbonate. Negative value of change in free energy (DeltaG degrees) and positive value of change in entropy (DeltaS degrees) suggest the adsorption of fluoride by LCB is feasible and spontaneous process. Positive value of change in enthalpy (DeltaH degrees) suggests the process of fluoride adsorption is endothermic in nature. Regeneration study reveals that 1M ammonium chloride solution appears to be the promising regeneration media showing 81.22% regeneration. The adsorption capacity of LCB was similar in fluoride-contaminated ground water collected from Dhar district of Madhya Pradesh, India, as compared to simulated water.

Surfactant-modified zeolite as a slow release fertilizer for phosphorus.

The feasibility of using surfactant-modified zeolite (SMZ) as a carrier for fertilizer and for slow release of phosphorus (P) was investigated. Zeolite-A was modified by using hexadecyltrimethylammonium bromide, a cationic surfactant, to modify its surface to increase its capacity to retain anion, namely, phosphate (PO4(3-)). SMZ was thoroughly characterized using X-ray diffraction, Fourier transform infrared, and scanning electron microscopy to study the effect of surfactant modification. Zeolite-A and SMZ were then subjected to P loading by treating them with fertilizer (KH2PO4). It was observed that the P loading on SMZ increased by a factor of 4.9 as compared to the unmodified zeolite-A. A comparative study of the release of P from fertilizer-loaded unmodified zeolite-A and SMZ and from solid KH2PO4 was performed using the constant flow percolation reactor. The results show that the P supply from fertilizer-loaded SMZ was available even after 1080 h of continuous percolation, whereas P from KH2PO4 was exhausted within 264 h. The results indicate that SMZ is a good sorbent for PO4(3-), and a slow release of P was achievable. These properties suggest that SMZ has a great potential as the fertilizer carrier for slow release of P.