Arsenic speciation, oxidation and immobilization in an unsaturated soil in the presence of green synthesized iron oxide nanoparticles and humic acid.

While the availability of arsenic (As) in soil is well known to be highly correlated with the presence of iron (Fe) oxides and humic acid (HA) in the soil, the relationship between Fe oxides and HA and As species in the soil is less well understood. In this study, As speciation in an unsaturated soil in the presence of external HA and green synthesized Fe oxide nanoparticles (FeNPs) showed that As(V) was mainly distributed to the specifically-bound (F2), amorphous and poorly-crystalline hydrous oxides of Fe, Al (F3) and the well-crystallized hydrous oxides of Fe and Al (F4). While As(III). This was the major component in unsaturated soil, and was mainly distributed to F4 and the residual fraction (F5). As bound to F3 and F5 was most sensitive to the addition of HA and FeNPs, while HA/FeNPs treatment increased the F3-bound As(V); however, it decreased the F5-bound As(III). Nonetheless the effect of HA on As is completely different to the HA/FeNPs treatment. The increase of As(V) in F3 resulted from F5-bound As(III) oxidation when treated by HA/FeNPs. Cyclic voltammetry confirmed that HA and Fe3+/Fe2+ redox enhanced As(III) oxidation, while FTIR revealed that HA-bound As(III) was the least available fraction in the soil. Finally, a mechanism involving a combination of HA and FeNPs was proposed for explaining the redistribution of As species in the soil.

Enhanced oxidation and stabilization of arsenic in a soil-rice system by phytosynthesized iron oxide nanomaterials: Mechanistic differences under flooding and draining conditions.

Despite arsenic (As) bioavailability being highly correlated with water status and the presence of iron (Fe) minerals, limited information is currently available on how externally applied Fe nanomaterials in soil-rice systems affect As oxidation and stabilization during flooding and draining events. Herein, the stabilization of As in a paddy soil by a phytosynthesized iron oxide nanomaterials (PION) and the related mechanism was investigated using a combination of chemical extraction and functional microbe analysis in soil at both flooding (60 d) and draining (120 d) stages. The application of PION decreased both specifically bound and non-specifically bound As. The As content in rice root, stem, husk and grain was reduced by 78.5, 17.3, 8.4 and 34.4%, respectively, whereas As(III) and As(V) in root declined by 96.9 and 33.3% for the 1% PION treatment after 120 d. Furthermore, the 1% PION treatment decreased the ratio of As(III)/As(V) in the rhizosphere soil, root and stem. Although PION had no significant effect on the overall Shannon index, the distribution of some specific functional microbes changed dramatically. While no As(III) oxidation bacteria were found at 60 d in any treatments, PION treatment increased As(III) oxidation bacteria by 3-9 fold after 120 d cultivation. Structural equation model analysis revealed that the ratio of Fe(III)/Fe(II) affected As stabilization directly at the flooding stage, whereas nitrate reduction and As(III) oxidation microbial groups played a significant role in the stabilization of As at the draining stage. These results highlight that PION exhibits a robust ability to reduce As availability to rice, with chemical oxidation, reduction inhibition and adsorption dominating at the flooding stage, while microbial oxidation, adsorption and coprecipitation dominant during draining.

Bimetallic Fe/Ni nanoparticles derived from green synthesis for the removal of arsenic (V) in mine wastewater.

Since the incidences of arsenicosis have significantly increased worldwide in the last decade, remediation of arsenic (As) pollution is now imperative. In this study, calcined green synthesized Fe/Ni nanoparticles (C-Fe/Ni NPs) were evaluated for their efficacy for As (V) removal from aqueous solution. Under optimal experimental conditions As (V) removal efficiency reached 87.3%. Analysis of changes in the surface properties of C-Fe/Ni NPs before and after interaction with As (Ⅴ) using a range of advanced characterization techniques including IC-AFS, SEM-EDS, XPS and XRD revealed that the As removal mechanism involved only adsorption. Adsorption kinetics followed a pseudo-second order rate model (R2 > 0.986) and adsorption best fit the Langmuir isotherm model (R2 > 0.958). Thermodynamic studies indicated that adsorption was a spontaneous endothermic process. On the basis of these results, a removal mechanism of As (Ⅴ) by C-Fe/Ni NPs was proposed. Finally, the efficacy of the material for practical remediation of As from aqueous solution was assessed, including the influence of coexisting anions. While Cl-, NO3- and SO42- had little influence on As (V) removal, both H2PO4- and HCO3- significantly negatively affected removal.

Removal mechanism of Sb(III) by a hybrid rGO-Fe/Ni composite prepared by green synthesis via a one-step method.

The annual influx of antimony (Sb) into the environment due to the widespread use of Sb compounds in industry and agriculture has become of global concern. Herein, a functional nanomaterial composite based on loading bimetallic iron/nickel nanoparticles on reduced graphene oxide (rGO-Fe/Ni) was initially prepared in a one-step phytogenic synthesis using a green tea extract. Subsequently, when applied for Sb(III) removal, the removal efficiency of rGO-Fe/Ni reached 69.7% within 3 h at an initial Sb concentration of 1.0 mg·L-1. Advanced materials characterization via scanning electron microscopy-energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that Sb(III) was initially adsorbed onto the surface of rGO and then oxidized to Sb(V). This result was also supported by adsorption isotherm, kinetics, and thermodynamic analysis. These studies revealed that the adsorption was spontaneous and endothermic, following a Langmuir adsorption model with pseudo-second-order kinetics and allowed a Sb(III) removal mechanism based on adsorption and catalytic oxidation to be proposed. Furthermore, when rGO-Fe/Ni was practically used to remove Sb(III) in groundwater a 95.7% removal efficiency was obtained at 1 mg·L-1 Sb(III), thus successfully demonstrating that rGO-Fe/Ni has significant potential for the practical remediation of Sb contaminated groundwater.

Removal of low Sb(V) concentrations from mining wastewater using zeolitic imidazolate framework-8.

Wastewater generated during mining remains a significant source of antimony pollution, because techniques to quickly and efficiently remove antimony from wastewater do not exist. In this study, zeolitic imidazolate framework-8 (ZIF-8), a specific type of Metal Organic Frameworks (MOFs), was successfully used to remove trace levels (1 mg L-1) of Sb(V) with a high removal efficiency when the ZIF-8 dose was 0.5 g L-1. Scanning electron microscopy-X-ray energy dispersive spectrometry (SEM-EDS) indicated that Sb(V) was adsorbed onto the ZIF-8surface. The powder X-ray diffraction (XRD) pattern of ZIF-8 before and after adsorption of Sb(V) indicated that ZIF-8 was successfully synthesized, and remained structurally stable after Sb(V) was adsorbed. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) both suggested complexation of zinc on ZIF-8 with Sb(V), where removal of Sb(V) by ZIF-8 followed the Langmuir adsorption isotherm with pseudo second-order kinetics. Thus, a possible removal mechanism was proposed which involved Sb(V) complexing with the zinc hydroxyl groups on ZIF-8 (Zn-OH-Sb). Practically, ZIF-8, could remove 78.6% of Sb(V) from a mining wastewater containing 20 µg L-1 Sb(V). Furthermore, ZIF-8 could be remain active after repeated uses and could still remove and 42.3% of Sb(V) from wastewater containing 1 mg L-1) Sb(V) even when the ZIF-8 was reused five time. This indicated that ZIF-8 had potential for practical removal of Sb(V) from mining wastewaters.

Removal of As(V) by iron-based nanoparticles synthesized via the complexation of biomolecules in green tea extracts and an iron salt.

While iron-based nanoparticles (nFe) prepared using green tea extracts have been successfully used to degrade many organic contaminants, their application to remove As(V) remains limited. Thus, in this work, nFe (GT-1) prepared using a green tea extract was used to removal As(V). The maximum adsorption capacity of GT-1 for As(V) was 19.9 mg g-1 at 298 K. The formation of GT-1 and the removal mechanism of As(V) by GT-1, was examined using XRD, TEM and SEM, which showed that GT-1 was composed of amorphous particulates sized between 50 and 100 nm. GC-MS and LC-MS analysis also showed that biomolecules presented in the green tea extract, including polyphenols and L-theanine, participated in the formation of GT-1. Mössbauer spectral analysis confirmed that an organo-Fe(III) complex was formed due to the reaction between biomolecules and Fe(III). FTIR and XPS showed that the adsorption of As(V) by GT-1 occurred both via complexation with Fe(III) in GT-1 and via coordination of As(V) with free hydroxyl groups on the surface of GT-1. Batch experiments showed that adsorption was spontaneous and conformed to the pseudo-second order kinetic model. Finally, mechanisms for the formation of GT-1 and the removal of As (V) by GT-1 were proposed.

Graphene and Rice-Straw-Fiber-Based 3D Photothermal Aerogels for Highly Efficient Solar Evaporation.

Solar-steam generation is one of the most promising technologies to mitigate the issue of clean water shortage using sustainable solar energy. Photothermal aerogels, especially the three-dimensional (3D) graphene-based aerogels, have shown unique merits for solar-steam generation, such as lightweight, high flexibility, and superior evaporation rate and energy efficiency. However, 3D aerogels require much more raw materials of graphene, which limits their large-scale applications. In this study, 3D photothermal aerogels composed of reduced graphene oxide (RGO) nanosheets, rice-straw-derived cellulose fibers, and sodium alginate (SA) are prepared for solar-steam generation. The use of rice straw fibers as skeletal support significantly reduces the need for the more expensive RGO by 43.5%, turning the rice straw biomass waste into value-added materials. The integration of rice straw fibers and RGO significantly enhances the flexibility and mechanical stability of the obtained photothermal RGO-SA-cellulose aerogel. The photothermal aerogel shows a strong broad-band light absorption of 96-97%. During solar-steam generation, the 3D photothermal aerogel effectively decreases the radiation and convection energy loss while enhancing energy harvesting from the environment, leading to an extremely high evaporation rate of 2.25 kg m-2 h-1, corresponding to an energy conversion efficiency of 88.9% under 1.0 sun irradiation. The salinity of clean water collected during the evaporation of real seawater is only 0.37 ppm. The materials are environmentally friendly and cost-effective, showing great potential for real-world desalination applications.

Medical geology in the framework of the sustainable development goals.

Exposure to geogenic contaminants (GCs) such as metal(loid)s, radioactive metals and isotopes as well as transuraniums occurring naturally in geogenic sources (rocks, minerals) can negatively impact on environmental and human health. The GCs are released into the environment by natural biogeochemical processes within the near-surface environments and/or by anthropogenic activities such as mining and hydrocarbon exploitation as well as exploitation of geothermal resources. They can contaminate soil, water, air and biota and subsequently enter the food chain with often serious health impacts which are mostly underestimated and poorly recognized. Global population explosion and economic growth and the associated increase in demand for water, energy, food, and mineral resources result in accelerated release of GCs globally. The emerging science of "medical geology" assesses the complex relationships between geo-environmental factors and their impacts on humans and environments and is related to the majority of the 17 Sustainable Development Goals in the 2030 Agenda of the United Nations for Sustainable Development. In this paper, we identify multiple lines of evidence for the role of GCs in the incidence of diseases with as yet unknown etiology (causation). Integrated medical geology promises a more holistic understanding of the occurrence, mobility, bioavailability, bio-accessibility, exposure and transfer mechanisms of GCs to the food-chain and humans, and the related ecotoxicological impacts and health effects. Scientific evidence based on this approach will support adaptive solutions for prevention, preparedness and response regarding human and environmental health impacts originating from exposure to GCs.

Household's willingness to pay for arsenic safe drinking water in Bangladesh.

This study examines willingness to pay (WTP) in Bangladesh for arsenic (As) safe drinking water across different As-risk zones, applying a double bound discrete choice value elicitation approach. The study aims to provide a robust estimate of the benefits of As safe drinking water supply, which is compared to the results from a similar study published almost 10 years ago using a single bound estimation procedure. Tests show that the double bound valuation design does not suffer from anchoring or incentive incompatibility effects. Health risk awareness levels are high and households are willing to pay on average about 5 percent of their disposable average annual household income for As safe drinking water. Important factors influencing WTP include the bid amount to construct communal deep tubewell for As safe water supply, the risk zone where respondents live, household income, water consumption, awareness of water source contamination, whether household members are affected by As contamination, and whether they already take mitigation measures.

Arsenic mitigation in Bangladesh: an analysis of institutional stakeholders' opinions.

While Bangladesh made significant achievements in safe water coverage via installation of shallow tubewells (STWs) nationwide, this success was shattered by the discovery of arsenic (As) in the STWs. The extent and severity of As groundwater contamination throughout Bangladesh and its detrimental effects on human health are well known and demand long-term sustainable mitigation. It is an immensely complex and expensive task to bring tens of millions of arsenic exposed people under safe water coverage. While various mitigation measures have been undertaken by various organizations, most have not achieved their expected outcomes due to technical, spatial and socio-economic challenges. Better understanding of these challenges by institutional stakeholders is crucial for sustainable arsenic mitigation in Bangladesh. In this study, institutional stakeholders' opinions on various aspects of As mitigation were elicited to identify their preferences for and reservations of specific mitigation measures. The current status of As mitigation activities and the factors influencing the success of As mitigation were also explored. Institutional weakness, lack of accountability and a latency period were the major factors hindering sustainable As mitigation. The results also suggested that the stakeholders' understanding of the As problem and their preferences for the different mitigation measures have a significant impact on the effectiveness of As mitigation. Mitigation of As contamination is a complex issue that requires a coordinated effort from various levels of stakeholders. The concept of "paying for water", which is currently potentially unknown in the rural areas of Bangladesh, also needs to be developed as this will create a stronger sense of user ownership of As safe water and thus better water management.

An effective dietary survey framework for the assessment of total dietary arsenic intake in Bangladesh: part-A--FFQ design.

The accurate assessment of dietary intake patterns is important for the determination of total dietary arsenic (As) exposure in As-contaminated regions of Bangladesh. Food intake questionnaires are a common means of assessing food intake. A food frequency questionnaire (FFQ) was designed to assess the daily intake of frequently consumed food items and was successfully implemented to assess dietary patterns and intake of the rural populations in 18 villages from three Districts of Bangladesh (Comilla, Manikganj Sadar, and Munshiganj). The FFQ presented in this paper comprises a complete set of tools which allowed not only collection of information on dietary patterns but also information on the spatial characteristics of the landscape, socio-demographic indicators, and geographic locations of the identified environmental media of the contaminants, which resulted in As exposure to humans. The FFQ was designed in three sections: (1) general household information, (2) household water and rice information, and (3) individual dietary intake of other foods. The dietary intake of other food was then further subdivided into five different food subgroups: (i) grain intake, (ii) protein intake, (iii) fruit intake (iv), vegetable intake, and (v) dal (pulse) intake. During the design and development of the FFQ, emphasis was given to the source of food, the frequency (day/week/month) of consumption, and the daily amount of food consumed by each adult male, adult female, and child to accurately determine the dietary pattern and intake of arsenic in the rural population of Bangladesh.

Human arsenic exposure and risk assessment at the landscape level: a review.

Groundwater contaminated with arsenic (As), when extensively used for irrigation, causes potentially long term detrimental effects to the landscape. Such contamination can also directly affect human health when irrigated crops are primarily used for human consumption. Therefore, a large number of humans are potentially at risk worldwide due to daily As exposure. Numerous previous studies have been severely limited by small sample sizes which are not reliably extrapolated to large populations or landscapes. Human As exposure and risk assessment are no longer simple assessments limited to a few food samples from a small area. The focus of more recent studies has been to perform risk assessment at the landscape level involving the use of biomarkers to identify and quantify appropriate health problems and large surveys of human dietary patterns, supported by analytical testing of food, to quantify exposure. This approach generates large amounts of data from a wide variety of sources and geographic information system (GIS) techniques have been used widely to integrate the various spatial, demographic, social, field, and laboratory measured datasets. With the current worldwide shift in emphasis from qualitative to quantitative risk assessment, it is likely that future research efforts will be directed towards the integration of GIS, statistics, chemistry, and other dynamic models within a common platform to quantify human health risk at the landscape level. In this paper we review the present and likely future trends of human As exposure and GIS application in risk assessment at the landscape level.

Implementation of food frequency questionnaire for the assessment of total dietary arsenic intake in Bangladesh: part B, preliminary findings.

Dietary intake of water and food has been identified as one of the major pathways for arsenic (As) exposure in the rural population of Bangladesh. Therefore, realistic assessment and measurement of dietary intake patterns are important for the development of an accurate estimate of As exposure and human health risk assessment. One important consideration is to identify an appropriate tool for measuring dietary intake. In this study an interviewer-administered Food Frequency Questionnaire (FFQ) was implemented to determine age and gender specific dietary intake. The developed FFQ was unique because it developed a synergy between field dietary assessment and As concentration measurements in various environmental media. The resulting integrated database provided an accurate framework for the process of As exposure and human health risk assessment. The preliminary results reported here from the FFQ demonstrated that this technique could be used in rural areas as a tool to assess As exposure and the associated human health risk.