Arsenic Contamination in Groundwater: Geochemical Basis of Treatment Technologies.

Arsenic (As) is abundant in the environment and can be found in both organic (e.g., methylated) and inorganic (e.g., arsenate and arsenite) forms. The source of As in the environment is attributed to both natural reactions and anthropogenic activities. As can also be released naturally to groundwater through As-bearing minerals including arsenopyrites, realgar, and orpiment. Similarly, agricultural and industrial activities have elevated As levels in groundwater. High levels of As in groundwater pose serious health risks and have been regulated in many developed and developing countries. In particular, the presence of inorganic forms of As in drinking water sources gained widespread attention due to their cellular and enzyme disruption activities. The research community has primarily focused on reviewing the natural occurrence and mobilization of As. Yet, As originating from anthropogenic activities, its mobility, and potential treatment techniques have not been covered. This review summarizes the origin, geochemistry, occurrence, mobilization, microbial interaction of natural and anthropogenic-As, and common remediation technologies for As removal from groundwater. In addition, As remediation methods are critically evaluated in terms of practical applicability at drinking water treatment plants, knowledge gaps, and future research needs. Finally, perspectives on As removal technologies and associated implementation limitations in developing countries and small communities are discussed.

Prevalence of metallo-ß-lactamases as a correlate of multidrug resistance among clinical Pseudomonas aeruginosa isolates in Nepal.

Pseudomonas aeruginosa is an opportunistic human pathogen that has developed antibiotic resistance (AR) and causes a range of illnesses, including respiratory pneumonia, gastrointestinal infections, keratitis, otitis media and bacteremia in patients with compromised immune system. The production of metallo-ß-lactamases (MBLs) is one of the major mechanisms of AR in this bacterium with ensuing infections difficult to treat. The main goal of this study was to provide a quantitative estimate of MBLs producing clinical P. aeruginosa isolates among the Nepalese patients and determine if MBL correlates with multi-drug resistance (MDR). Preferred Reporting Items for Systematic Reviews and Meta-Analysis (PRISMA) guideline was followed for meta-analysis of relevant literature using PubMed, Research4Life, and Google Scholar. The prevalence of MBLs in P. aeruginosa from clinical samples was determined using R 4.1.2 for data pooled from studies published until 2021. The meta-analysis of a total of 19 studies selected (of 6038 studies for which titles and abstracts were reviewed) revealed the prevalence of MBLs producing P. aeruginosa (MBL-PA) was 14 % (95 % CI: 0.10-0.19) while MDR isolates among P. aeruginosa was 42 % (95 % CI: 0.30-0.55) in Nepal. Combined Disc Test was predominantly used phenotypic method for confirming MBLs phenotypes among the studies. Sputum was the most common specimen from which MBL-PA was recovered. A significant positive correlation was observed between MDR and MBL production in P. aeruginosa. We conclude that MBL producing strains are widespread among the clinical isolates of P. aeruginosa in Nepal and responsible for emerging MDR strains. It is paramount that antibiotics prescription against the bacterium should be monitored closely and alternative therapeutic modalities against MBL-PA explored.

Understanding COVID-19 Situation in Nepal and Implications for SARS-CoV-2 Transmission and Management.

Background: The pandemic of Coronavirus Disease 2019 (COVID-19), one of the most infectious diseases in the modern history, is caused by Severe Acute Respiratory Syndrome Coronavirus-2 (SARS-CoV-2) and has had a profound health and economic toll, globally. This paper identifies the overall health status associated with COVID-19 pandemic in all 7 provinces of Nepal, a developing country in South Asia, analyzing data from January 2020 to February 2022. It focuses on the SARS-CoV-2 prevalence, transmission through wastewater and other routes, diagnostics, treatment options, and alternative medicines, thereby offering key perspectives for its management. Materials and Methods: Studies regarding coronavirus spanning the 2017 to 2022 period were searched on the web, Nepalese database, and Web of Science. Refined criteria included SARS-CoV-2 in wastewater of Nepal or worldwide. Demographic data (sex, age-group, and geographic location) were also obtained from websites and relevant reports of the Ministry of Health and Population (MOHP) of Nepal, ranging from January 2020 to February 2022. Moreover, trends concerning lockdown, business, and border activities in Nepal between February 2020 and October 2020 were evaluated. The viral dissemination pathways, diagnosis, and available treatment options, including the Ayurvedic medicine, were also examined. Results: Aerosols generated during the hospital, industrial, recreational, and household activities were found to contribute to the propagation of SARS-CoV-2 into environmental wastewater, thereby putting the surrounding communities at risk of infection. When lockdown ended and businesses opened in October 2020, the number of active cases of COVID-19 increased exponentially. Bagmati Province had the highest number of cases (53.84%), while the remaining 6 provinces tallied 46.16%. Kathmandu district had the highest number of COVID-19 cases (138, 319 cases), while Manang district had the smallest number of infections (81 cases). The male population was found to be predominantly infected (58.7%). The most affected age groups were the 31 to 40 years old males (25.92%) and the 21 to 30 years old females (26.85%). Conclusion: The pandemic impacted the public health and economic growth in our study duration. SARS-CoV-2 was prevalent in the wastewater of Nepal. The Terai districts and the megacities were mostly affected by SARS-CoV-2 infections. Working-age groups and males were identified as the highest risk groups. More investigations on the therapeutic and alternative cures are recommended. These findings may guide the researchers and professionals with handling the COVID-19 challenges in developing countries such as Nepal and better prepare for future pandemics.

Per- and polyfluoroalkyl substances in water and wastewater: A critical review of their global occurrence and distribution.

Per- and polyfluoroalkyl substances (PFAS) are a family of fluorinated organic compounds of anthropogenic origin. Due to their unique chemical properties, widespread production, environmental distribution, long-term persistence, bioaccumulative potential, and associated risks for human health, PFAS have been classified as persistent organic pollutants of significant concern. Scientific evidence from the last several decades suggests that their widespread occurrence in the environment correlates with adverse effects on human health and ecology. The presence of PFAS in the aquatic environment demonstrates a close link between the anthroposphere and the hydrological cycle, and concentrations of PFAS in surface and groundwater range in value along the ng L-1-µg L-1 scale. Here, we critically reviewed the research published in the last decade on the global occurrence and distribution of PFAS in the aquatic environment. Ours is the first paper to critically evaluate the occurrence of PFAS at the continental scale and the evolving global regulatory responses to manage and mitigate the adverse human health risks posed by PFAS. The review reports that PFAS are widespread despite being phased out-they have been detected in different continents irrespective of the level of industrial development. Their occurrence far from the potential sources suggests that long-range atmospheric transport is an important pathway of PFAS distribution. Recently, several studies have investigated the health impacts of PFAS exposure-they have been detected in biota, drinking water, food, air, and human serum. In response to the emerging information about PFAS toxicity, several countries have provided administrative guidelines for PFAS in water, including Canada, the United Kingdom, Sweden, Norway, Germany, and Australia. In the US, additional regulatory measures are under consideration. Further, many PFAS have now been listed as persistent organic pollutants. This comprehensive review provides crucial baseline information on the global occurrence, distribution, and regulatory framework of PFAS.

Nanomaterials in the environment, human exposure pathway, and health effects: A review.

Nanomaterials (NMs), both natural and synthetic, are produced, transformed, and exported into our environment daily. Natural NMs annual flux to the environment is around 97% of the total and is significantly higher than synthetic NMs. However, synthetic NMs are considered to have a detrimental effect on the environment. The extensive usage of synthetic NMs in different fields, including chemical, engineering, electronics, and medicine, makes them susceptible to be discharged into the atmosphere, various water sources, soil, and landfill waste. As ever-larger quantities of NMs end up in our environment and start interacting with the biota, it is crucial to understand their behavior under various environmental conditions, their exposure pathway, and their health effects on human beings. This review paper comprises a large portion of the latest research on NMs and the environment. The article describes the natural and synthetic NMs, covering both incidental and engineered NMs and their behavior in the natural environment. The review includes a brief discussion on sampling strategies and various analytical tools to study NMs in complex environmental matrices. The interaction of NMs in natural environments and their pathway to human exposure has been summarized. The potential of NMs to impact human health has been elaborated. The nanotoxicological effect of NMs based on their inherent properties concerning to human health is also reviewed. The knowledge gaps and future research needs on NMs are reported. The findings in this paper will be a resource for researchers working on NMs all over the world to understand better the challenges associated with NMs in the natural environment and their human health effects.

Benign zinc oxide betaine-modified biochar nanocomposites for phosphate removal from aqueous solutions.

Phosphate is one of the most costly and complex environmental pollutants that leads to eutrophication, which decreases water quality and access to clean water. Among different adsorbents, biochar is one of the promising adsorbents for phosphate removal as well as heavy metal removal from an aqueous solution. In this study, biochar was impregnated with nano zinc oxide in the presence of glycine betaine. The Zinc Oxide Betaine-Modified Biochar Nanocomposites (ZnOBBNC) proved to be an excellent adsorbent for the removal of phosphate, exhibiting a maximum adsorption capacity of phosphate (265.5 mg. g-1) and fast adsorption kinetics (~100% removal at 15 min at 10 mg. L-1 phosphate and 3 g. L-1 nanocomposite dosage) in phosphate solution. The synthesis of these benign ZnOBBNC involves a process that is eco-friendly and economically feasible. From material characterization, we found that the ZnOBBNC has ~20-30 nm particle size, high surface area (100.01 m2. g-1), microporous (25.79 Å) structures, and 7.64% zinc content. The influence of pH (2-10), coexisting anions (Cl-, CO32-, NO3- and SO43-), initial phosphate concentration (10-500 mg. L-1), and ZnOBBNC dosage (0.5-5 g. L-1) were investigated in batch experiments. From the adsorption isotherms data, the adsorption of phosphate using ZnOBBNC followed Langmuir isotherm (R2 = 0.9616), confirming the mono-layered adsorption mechanism. The kinetic studies showed that the phosphate adsorption using ZnOBBNC followed the pseudo-second-order model (R2 = 1.0000), confirming the chemisorption adsorption mechanism with inner-sphere complexion. Our results demonstrated ZnOBBNC as a suitable, competitive candidate for phosphate removal from both mock lab-prepared and real field-collected wastewater samples when compared to commercial nanocomposites.

Groundwater pollution: Occurrence, detection, and remediation of organic and inorganic pollutants.

Groundwater pollution is a result of natural and anthropogenic activities. While the elevated levels of various inorganic constituents could be attributed to natural processes, such as geological weathering and aquifer characteristics, many times, anthropogenic activities also substantially pollute the groundwater. On the contrary, the occurrence of organic pollutants is primarily due to various anthropogenic activities. Extensive groundwater mining, the hydraulic connection between groundwater and other surface water bodies, and leaking underground buried infrastructure also contribute to groundwater pollution. Water resources are scarce commodities, and preserving groundwater quality is of critical concern. This paper documents instances of groundwater quality impact during the year 2019 due to both natural and anthropogenic activities throughout the world. PRACTITIONER POINTS: Groundwater pollution problems reported during the year 2019 are reviewed and documented. Occurrence of organic, inorganic, and microbial pollutants in groundwater is reported. Remediation technologies for selected inorganic pollutants are reviewed and documented.

Detection of Hydroxyl Radicals Using Cerium Oxide/Graphene Oxide Composite on Prussian Blue.

A composite sensor consisting of two separate inorganic layers of Prussian blue (PB) and the composite of cerium oxide nanoparticles (CeNPs) and graphene oxide (GO), is tested with •OH radicals. The signals from the interaction between the composite layers and •OH radicals are characterized using cyclic voltammetry (CV). The degradation of PB in the presence of H2O2 and •OH radicals is observed and its impact on the sensor efficiency is investigated. The results show that the composite sensor differentiates between the solutions with and without •OH radicals by the increase of oxidation current in the presence of •OH radicals. The redox response shows a linear relation with the concentration of •OH radicals where the limit of detection, LOD, is found at 60 µM (100 µM without the PB layer). When additional composite layers are applied on the composite sensor to prevent the degradation of PB layer, the PB layer is still observed to be degraded. Furthermore, the sensor conductivity is found to decrease with the additional layers of composite. Although the CeNP/GO/PB composite sensor demonstrates high sensitivity with •OH radicals at low concentrations, it can only be used once due to the degradation of PB.

Peptide Nanotube Encapsulated Enzyme Biosensor for Vapor Phase Detection of Malathion, an Organophosphorus Compound.

This study explores the use of a butyrylcholinesterase (BChE)-based, reversible reaction biosensor using screen-printed electrodes (SPEs) having a smaller working surface area than the single-use electrodes previously studied. Previous research demonstrated the prospective application of a single-use biosensor fabricated with an acetylcholinesterase (AChE) enzyme encapsulated in peptide nanotubes (PNTs) and enhanced with horseradish peroxidase (HRP) to detect organophosphorus compounds (OPCs) in aqueous and gas phases. In the current study, potential improvements to the biosensor are investigated. BChE-based biosensors were fabricated using PNTs, HRP, and Nafion in combination to increase the reactive surface area, enhance sensitivity, and maintain enzyme stability. Cyclic voltammetry (CV) was used along with the new modified sensor to measure malathion concentration in the gas phase. The results show that a BChE-based biosensor could reliably measure gas phase malathion concentrations between 6-25 ppbv by CV with the extent of inhibition linearly proportional to the malathion concentration (R2 = 0.941). This research demonstrated that fabricated BChE-based biosensors could be stored without cold storage requirement for up to six weeks with minimal performance degradation. Moreover, the sensor electrodes were each reused several times, and were still useable at the conclusion of the research. This research demonstrates the potential of fabricating a reusable, inexpensive biosensor that is capable of OPC detection with high sensitivity and a low detection limit without a long-term cold storage requirement.

Novel carbon nanotube (CNT)-based ultrasensitive sensors for trace mercury(II) detection in water: A review.

Infamous for "Mad hatter syndrome" and "Minamata disease", mercury (Hg) is ranked high on the Agency for Toxic Substances and Disease Registry's priority list of hazardous substances for its potent neurologic, renal, and developmental toxicities. Most typical exposures are via contaminated water and food. Although regulations and advisories are exercised at various levels, Hg pollution from both natural and anthropogenic sources has remained a major public health and safety concern. Rapid detection of solvated aqueous Hg2+ ions at low levels is critical for immediate response and protection of those who are vulnerable (young children, pregnant and breast-feeding women) to acute and chronic exposures to Hg2+. Various types of sensors capable of detecting Hg in water have been developed. In particular, the novel use of engineered carbon nanotubes (CNTs) has garnered attention due to their specificity and sensitivity towards Hg2+ detection in solution. In this focused review, we describe the sensitivity, selectivity and mechanisms of Hg2+ ion sensing at trace levels by employing CNT-based various sensor designs, and appraise the open literature on the currently applied and "proof-of-concept" methods. Five different types of CNT-based sensor systems are described: potentiometric, DNA-based fluorescence, surface plasmon resonance (SPR), colorimetric, and stripping voltammetric assays. In addition, the recognized merits and shortcomings for each type of electrochemical sensors are discussed. The knowledge from this succinct review shall guide the development of the next generation CNT-based biochemical sensors for rapid Hg2+ detection in the environment, which is a significant first step towards human health risk analysis of this legacy toxicant.

Chemometrics in assessment of seasonal variation of water quality in fresh water systems.

The chemometric techniques were applied for evaluation of the seasonal variation of water qualities at 17 stations along a stretch of the Bagmati river of Nepal for 23 water quality parameters measured during 1999-2003. The application of discriminant analysis confirmed the classification of the water quality measurements into three seasons: pre-monsoon, monsoon, and post-monsoon affording 93.8% correct classification. Factor analysis and box-whisker plots facilitated to investigate the seasonal variation of water quality and the pattern of pollution sources. Application of FA revealed that the influence of water quality parameters changes from season to season. A parameter that is most important in contributing to water quality variation for one season may not be important for another season. Comparison of the discriminant analysis and factor analysis helped to identify the most important water quality parameters, as water temperature, DO, EC, COD, CL, Ca, alkalinity, PO(4)P, and TP, that are most important for seasonal variation and play a significant role in establishment of water quality control strategy.

Adsorption of humic acid onto nanoscale zerovalent iron and its effect on arsenic removal.

Batch experiments were performed to investigate the feasibility of humic acid (HA) removal by synthetic nanoscale zerovalent iron (NZVI) and its interaction with As(III) and As(V), the most poisonous and abundant of groundwater pollutants. High-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) were used to characterize the particle size, surface morphology of the pristine NZVI and HA-treated NZVI (NZVI-HA), and the zero valence state of the pristine NZVI. It was determined that HA was completely removed by NZVI (0.3 g/L) within a few minutes, at a wide range of initial pH values (approximately 3.0-12.0). Fourier transform infrared (FTIR) and laser light scattering (zeta potential measurement) studies confirmed that NZVI-HA forms inner-sphere surface complexation at different initial pH conditions. The effects of competing anions showed that there was complete removal of HA in the presence of 10 mM NO(-3) and SO4(2-) whereas HA removal was observed 0%, 18% and 22% in presence of 10 mM H2PO4(2-), HCO(3-) and H4SiO4(0), respectively. However, the presence of 2 mM CA2+ and Mg2+ enhanced HA removal from 17 mg g(-1) to 76 mg g(-1) and 55 mg g(-1), respectively. Long-term time-resolved studies of XRD and field emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray (EDX) revealed the formation of various types of new iron oxides (magnetite, maghemite, and lepidocrocites) during the continuous reaction of HA in the presence of water and NZVI at 1, 30, 60, and 90 days. In addition, the surface-area-normalized rate constant (ksa) of adsorption of As(III) and As(V) onto NZVI was reduced in the presence of HA (20 mg L(-1)), from 100% to 43% and 68%, respectively. Our results show the potential use of NZVI in removing HA and its possible effects on arsenic removal during the application of NZVI in groundwater remediation.

Chemometric application in classification and assessment of monitoring locations of an urban river system.

The study presents the application of selected chemometric techniques: cluster analysis, principal component analysis, factor analysis and discriminant analysis, to classify a river water quality and evaluation of the pollution data. Seventeen stations, monitored for 16 physical and chemical parameters in 4 seasons during the period 1999-2003, located at the Bagmati river basin in Kathmandu Valley, Nepal were selected for the purpose of this study. The results allowed, determining natural clusters of monitoring stations with similar pollution characteristics and identifying main discriminant variables that are important for regional water quality variation and possible pollution sources affecting the river water quality. The analysis enabled to group 17 monitoring sites into 3 regions with 5 major discriminating variables: EC, DO, CL, NO(2)N and BOD. Results revealed that some locations were under the high influence of municipal contamination and some others under the influence of minerals. This study demonstrated that chemometric method is effective for river water classification, and for rapid assessment of water qualities, using the representative sites; it could serve to optimize cost and time without losing any significance of the outcome.

Application of water quality indices and dissolved oxygen as indicators for river water classification and urban impact assessment.

The usefulness of water quality indices, as the indicators of water pollution, for assessment of spatial-temporal changes and classification of river water qualities was verified. Four water quality indices were investigated: WQI (considering 18 water quality parameters), WQI(min) and WQI(m) (considering five water quality parameters: temperature, pH, DO, EC and TSS) and WQI(DO) (considering a single parameter, DO). The water quality indices WQI(min), WQI(m) and WQI(DO) could be of particular interest for the developing countries because of the minimum analytical cost involved. As a case study, water quality indices were used to evaluate spatial and temporal changes of the water quality in the Bagmati river basin (Nepal) for the study period 1999-2003. The results allowed us to determine the serious negative effects of the city urban activity on the river water quality. In the studied section of the river, the water quality index (WQI) was 71 units (classified as good) at the entry station and 47.6 units (classified as bad) at the outlet station. For the studied period, a significant decrease in water quality (mean WQI decrease = 11.6%, p = 0.042) was observed in the rural areas. A comparative analysis revealed that the urban water quality was significantly bad as compared with rural. The analysis enabled to classify the water quality stations into three groups: good water quality, medium water quality and bad water quality. WQI(min) resulted in overestimation of the water quality but with similar trend as with WQI and is useful for the periodic routine monitoring program. The correlation of WQI with WQI(min) and DO resulted two new indices WQI(m) and WQI(DO), respectively. The classification of waters based on WQI(m) and WQI(DO) coincided in 90 and 93% of the samples, respectively.

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.

Spatial-temporal variation and comparative assessment of water qualities of urban river system: a case study of the river Bagmati (Nepal).

The study presents the assessment of variation of water qualities, classification of monitoring networks and detection of pollution sources along the Bagmati River and its tributaries in the Kathmandu valley of Nepal. Seventeen stations, monitored for 23 physical and chemical parameters in pre-monsoon, monsoon, post-monsoon and winter seasons, during the period 1999-2003, were selected for the purpose of this study. The study revealed that the upstream river water qualities in the rural areas were increasingly affected from human sewage and chemical fertilizers. In downstream urban areas, the river was heavily polluted with untreated municipal sewage. The contribution of industries to pollute the river was minimal. The higher ratio of COD to BOD (3.74 in the rural and 2.06 in the urban) confirmed the increased industrial activities in the rural areas. An increasing trend of nitrate was found in the rural areas. In the urban areas, increasing trend of phosphorus was detected. The water quality measurement in the study period showed that DO was below 4 mg/l and BOD, COD, TIN, TP and TSS above 39.1, 59.2, 10.1, 0.84 and 199 mg/l, respectively, in the urban areas. In the rural areas, DO was above 6.2 mg/l and BOD, COD, TIN, TP and TSS below 15.9, 31, 5.24, 0.41 and 134.5 mg/l, respectively. The analysis for data from 1988 to 2003 at a key station in the river revealed that BOD was increasing at a rate of 1.8 mg/l in the Bagmati River. A comparative study for the water quality variables in the urban areas showed that the main river and its tributaries were equally polluted. The other comparison showed the urban water qualities were significantly poor as compared with rural. The cluster analysis detected three distinct monitoring groups: (1) low water pollution region, (2) medium water pollution region, (3) heavy water pollution region. For rapid assessment of water qualities using the representative sites could serve to optimize cost and time without loosing any significance of the outcome. The factor analysis revealed distinct groups of sources and pollutions (organics, nutrients, solutes and physicochemical).

Application of QUAL2Kw for water quality modeling and dissolved oxygen control in the river Bagmati.

A stream water quality model, QUAL2Kw, was calibrated and validated for the river Bagmati of Nepal. The model represented the field data quite well with some exceptions. The influences of various water quality management strategies have on DO concentrations were examined considering: (i) pollution loads modification; (ii) flow augmentation; (iii) local oxygenation. The study showed the local oxygenation is effective in raising DO levels. The combination of wastewater modification, flow augmentation and local oxygenation is necessary to ensure minimum DO concentrations. This reasonable modeling guarantees the use of QUAL2Kw for future river water quality policy options.

Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material.

The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. Mössbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation.

Removal of arsenic(III) from groundwater by nanoscale zero-valent iron.

Nanoscale zero-valent iron (NZVI) was synthesized and tested for the removal of As(III), which is a highly toxic, mobile, and predominant arsenic species in anoxic groundwater. We used SEM-EDX, AFM, and XRD to characterize particle size, surface morphology, and corrosion layers formed on pristine NZVI and As(III)-treated NZVI. AFM results showed that particle size ranged from 1 to 120 nm. XRD and SEM results revealed that NZVI gradually converted to magnetite/maghemite corrosion products mixed with lepidocrocite over 60 d. Arsenic(III) adsorption kinetics were rapid and occurred on a scale of minutes following a pseudo-first-order rate expression with observed reaction rate constants (K(obs)) of 0.07-1.3 min(-1) (at varied NZVI concentration). These values are about 1000x higher than K(obs) literature values for As(III) adsorption on micron size ZVI. Batch experiments were performed to determine the feasibility of NZVI as an adsorbent for As(III) treatment in groundwater as affected by initial As(III) concentration and pH (pH 3-12). The maximum As(III) adsorption capacity in batch experiments calculated by Freundlich adsorption isotherm was 3.5 mg of As(III)/g of NZVI. Laser light scattering (electrophoretic mobility measurement) confirmed NZVI-As(III) inner-sphere surface complexation. The effects of competing anions showed HCO3-, H4SiO4(0), and H2P04(2-) are potential interferences in the As(III) adsorption reaction. Our results suggest that NZVI is a suitable candidate for both in-situ and ex-situ groundwater treatment due to its high reactivity.