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Abstract The deep geological disposal concept is widely accepted by the scientific community for the storage of high activity level nuclear waste. It uses a multi-barrier system to isolate radioactive waste from the hydrosphere and biosphere for hundreds of centuries. The multiple barriers include, from the waste to near- and far-field: metal (e.g., iron or copper) and/or concrete canisters/casks containing the radioactive waste, cement, clay (e.g., smectites) buffer and/or backfill materials, and naturally occurring host rocks (e.g., claystone and granite). The mobility of radionuclides (RNs) is a key issue regarding the safety assessment of nuclear waste repositories, especially for the soluble and mobile RNs, such as 129I, 36Cl, 235, 238U, 79Se, and 99Tc. Among them, 235, 238U, 79Se, 99Mo, and 125Sb are some of the redox-sensitive RNs whose mobility largely depends on their speciation, i.e. , their oxidation states. The interactions of these redox-sensitive RNs with the components of each of the barriers is complex, and it needs to be fully understood for a correct safety assessment. Much progress has been made in the recent years in getting a fundamental understanding of the migration of redox-sensitive RNs in geological media. Here, an overview of the major achievements is presented. In general, the electron donors in repositories can be steel (i.e., zero valent iron), steel reaction products when in contact with groundwater (producing H 2), steel corrosion products (e.g., magnetite, green rust, and ferrous oxyhydroxides), Fe(II)-sulfides (e.g., pyrite, chalcopyrite, and mackinawite), Fe(II)-bearing clays (e.g., Fe-bearing smectites) in claystone, or Fe(II)-bearing mica minerals (e.g., biotite) in granites. All these phases can sorb redox-sensitive RNs and drive reductive immobilization processes. For U and all the redox-sensitive RN oxyanions, the resulting reduced products are the most stable and least soluble phases, such as FeSe 2 for Se or UO 2 for U, which may be favorably formed in the presence of a high solubility of electron donors and fast reaction kinetics. However, with slow reaction kinetics, metastable reduced mixed species in intermediate oxidation states such as Se(0) and hyperstoichiometric uranium oxides are produced. In order to characterize the RN-bearing phases and the uptake and reduction pathway, powerful molecular-scale tools such as X-ray photoelectron spectroscopy (XPS) or X-ray absorption spectroscopy (XAS) are commonly used. Here, we provide a comprehensive perspective on the studies addressing interactions of redox-sensitive RNs with the above-mentioned potential barrier. Highlights • Sorption mechanisms of redox-sensitive RNs on geochemical barriers are reviewed. • Reductive immobilization is an efficient radionuclide removal pathway. • Fe and S bearing minerals act as key reductants in repositories. • Non-redox sorption dominates radionuclide uptake on cement and Fe-free clays. • Minerals with reducing power will create potential reactive interfaces. [ABSTRACT FROM AUTHOR]

Clay rocks are low permeability sedimentary formations that provide records of Earth history, influence the quality of water resources, and that are increasingly used for the extraction or storage of energy resources and the sequestration of waste materials. Informed use of clay rock formations to achieve low-carbon or carbon-free energy goals requires the ability to predict the rates of diffusive transport processes for chemically diverse dissolved and gaseous species over periods up to thousands of years. We survey the composition, properties and uses of clay rock and summarize fundamental science challenges in developing confident conceptual and quantitative gas and solute transport models. [ABSTRACT FROM AUTHOR]

Near-surface biogeochemical systems can oscillate between oxic and anoxic conditions. Under such periodic changes many redox-sensitive inorganic contaminants undergo speciation, mobility and toxicity changes. We investigated the changes to chromium (Cr), arsenic (As), selenium (Se), antimony (Sb) and uranium (U) mobility during a series of laboratory experiments where argillaceous substrates were subjected to successive cycles of oxidizing and reducing conditions. The EH oscillated between -320 and +470 mV, induced via both abiotic and microbial forcings. Chemically induced cydes of oxidation and reduction were achieved via a combination of gas (N2:C02 vs compressed air) and carbon (ethanol) addition, to stimulate the metabolism of a natively present microbial community. The contaminants were added either alone or as contaminant mixtures. Results show dear on-off switch mobility behavior for both major elements such as carbon (C), iron (Fe) and manganese (Mn) and for contaminants. Mn, Fe, and As were mobilized under anoxic conditions, whereas Sb, Se, and U were mobilized under oxic conditions. While As, Sb, and U were reversibly sorbed, Se and Cr were irreversibly sequestered via reductive predpitation. When present in aqueous solutions at high concentrations, Crvl prevented the reduction of Mn and Fe, and inhibited the mobilization of elements with lower EH°. To improve remediation strategies for multiple contaminants in redox-dynamic environments, we propose a mixed kinetic-equilibrium biogeochemical model that can be forced by oscillating boundary conditions and that uses literature rates and constants to capture the key processes responsible for the mobilization of contaminants in soils. [ABSTRACT FROM AUTHOR]

Highlights: [•] We summarized and discussed about As in drinking water for all territories in China. [•] Possible natural As sources in drinking water, were documented. [•] Typical environmental conditions for occurrence of geogenic high-As waters. [•] Anthropogenic As contaminations in China were summarized. [ABSTRACT FROM AUTHOR]

Abstract: Metal ions appear to play an important role in several neurodegenerative (ND) diseases. Evidence suggests that metal ions bind directly to causative amyloidogenic proteins and modulate their aggregation into amyloids, considered to be a key event in the etiology of ND diseases. Apart from this well-documented binding of essential metals to amyloidogenic proteins, other, non-essential metal ions have been considered to be environmental hazards for neuronal disorders, but tight causative relations have yet to be established. The present article provides a review of the potential role of manganese, lead, and mercury as environmental risk factors in ND diseases, and covers in detail environmental availability of these metals, their uptake and distribution in the body and cells, and their role in Alzheimer''s, Parkinson''s and Prion diseases. [Copyright &y& Elsevier]

Understanding the formation of iron sulfides at low temperatures is essential for interpretation of geochemical signatures recorded in sedimentary sulfide minerals related to the evolution of the Earth's surface environment. Observed variations in the precipitation of nanoparticulate metastable phases prior to the formation of the stable-phase pyrite have been discussed from a kinetic perspective only. Here, using the ab-initio thermodynamic scheme to integrate surface thermodynamics with solid–aqueous equilibria, we demonstrate that stability relations among iron sulfides are dependent on particle size. The lower surface energies of metastable mackinawite and greigite than pyrite can drive reversals in relative thermodynamic stability at the nanoparticle scale and also lead to faster nucleation rates of the metastable phases, which are dependent on aqueous Eh-pH and Fe(II)/H 2 S conditions. This study emphasizes the role of surface energy in the formation pathways of iron sulfides and their particle-size dependent redox equilibria in anoxic aqueous solutions. [ABSTRACT FROM AUTHOR]

A nanopyrite/greigite composite was synthesized by reacting FeCl3 and NaHS in a ratio of 1:2 (Wei et al. 1996). Following this procedure, the obtained solid phases consisted of 30-50 nm sized particles containing 28% of greigite (Fe2+Fe3+2S4) and 72% pyrite (FeS2). Batch reactor experiments were performed with selenite or selenate by equilibrating suspensions containing the nanosized pyrite-greigite solid phase at different pH-values and with or without the addition of extra Fe2+. XANES-EXAFS spectroscopic techniques revealed, for the first time, the formation of ferroselite (FeSe2) as the predominant reaction product, along with elemental Se. In the present experimental conditions, at pH 6 and in equilibrium with Se0, the solution is oversaturated with respect to ferrosilite. Furthermore, thermodynamic computations show that reaction kinetics likely played a significant role in our experimental system. [ABSTRACT FROM AUTHOR]

Abstract: Massive deleterious impacts to human health are resulting from the use of arsenic-bearing groundwaters in South-East Asia deltas and elsewhere in the world for drinking, cooking and/or irrigation. In Bangladesh alone, a fifth of all deaths are linked to arsenicosis. In the natural and engineered subsurface environment, the fate of arsenic is, to a large extent, controlled by redox potential, pH, as well as total iron, sulfur and carbonate content, via sorption and coprecipitation on a variety of natural and engineered (nano)particles. In the present article, we address: (1) new insights in the sorption mechanisms of As on Fe(II) and Fe(III) nanophases recognized to play an important role in the microbial cycling of As and Fe; (2) artifacts often encountered in field and laboratory studies of As speciation due to the extreme redox sensitivity of the Fe-As-O-H phases; and (3) as a conclusion, the implications for water treatment. Indeed the specific reactivity of nanoparticles accounts not only for the As bioavailability within soils and aquifers, but also opens new avenues in water treatment. [Copyright &y& Elsevier]

Although groundwater arsenic constitutes a major hazard to the health of the people of Southeast Asia, the exact mineralogical origin of the arsenic in these fluvial aquifers is still under debate. Fe(III) oxides are the dominant hosts of mobilizable arsenic in the sediments, with the role of secondary Fe(III)-bearing phases like mackinawite, siderite, vivianite, magnetite, and carbonate green rust (fougerite) still unclear. Based on published field data from Chakdaha (India), the importance of the phases for arsenic mobility is evaluated quantitatively using models of growing complexity. Arsenic heterogeneity can be explained by the presence of two contrasted redox zones in the aquifers, with Fe(III) oxides being the dominant sorbent for arsenic in the less reduced zones and Fe(II) sulfides and/ or Fe(II) carbonates being the solid-phase hosts for arsenic under more reduced conditions below impermeable soils or close to rivers where sulfate is reduced. A 1D reactive transport model which simulates the transition between the two environments has been developed and compared to field data. The results show that microbial sulfate reduction followed by abiotic and/or biotic reduction of As(III)-bearing iron oxides accounts for the spatial heterogeneity of arsenic in such reduced aquifers. [ABSTRACT FROM AUTHOR]

The Charge Distribution MUltiSite Ion Complexation or CD-MUSIC modeling approach is used to describe the chemical structure of carbonate mineral-aqueous solution interfaces. The new model extends existing surface complexation models of carbonate minerals, by including atomic scale information on the surface lattice and the adsorbed water layer. In principle, the model can account for variable proportions of face, edge and kink sites exposed at the mineral surface, and for the formation of inner- and outer-sphere surface complexes. The model is used to simulate the development of surface charges and surface potentials on divalent carbonate minerals as a function of the aqueous solution composition. A comparison of experimental data and model output indicates that the large variability in the observed pH trends of the surface potential for calcite may in part reflect variable degrees of thermodynamic disequilibrium between mineral, solution and, when present, gas phase during the experiments. Sample preparation and non-stoichiometric surfaces may introduce further artifacts that complicate the interpretation of electrokinetic and surface titration measurements carried out with carbonate mineral suspensions. The experimental artifacts, together with the high sensitivity of the model toward parameters describing hydrogen bridging and bond lengths at the mineral-water interface, currently limit the predictive application of the proposed CD-MUSIC model. The results of this study emphasize the need for internally consistent experimental data sets obtained with well-characterized mineral surfaces and in situ aqueous solution compositions (that is, determined during the charge or potential measurements), as well as for further molecular dynamic simulations of the carbonate mineral-water interface to better constrain the bond lengths and the number plus valence contribution of hydrogen bridges associated with different structural surface sites. [ABSTRACT FROM AUTHOR]

We evaluated auditory performance following cartilage tympanoplasty for the management of tympanic membrane retraction pockets. We performed a 230-patient retrospective study over a 10-year period (1990–2000) and compared pre-operative and postoperative audiograms. Postoperative audiograms were better in 49% of cases, identical in 16% and worse in 11%. Cartilage tympanoplasty for the management of tympanic membrane retraction pockets has a good postoperative functional outcome. Cartilage graft is useful for reconstruction of the eardrum and tympanic bone defects. [ABSTRACT FROM AUTHOR]

Suboxic soils and sediments often contain the Fe(II)-bearing minerals mackinawite (FeS), siderite (FeCO3) or magnetite (Fe304), which should be able to reduce aqueous selenite, thereby forming solids of low solubility. While the reduction of selenate or selenite to S (O) by green rust, pyrite and by Fe2~ sorbed to montmorillonite is a slow (weeks), kinetically limited redox reaction as demonstrated earlier, we show here that selenite is rapidly reduced within one day by nanoparticulate mackinawite and magnetite, while only one third of selenite is reduced by micrometer-sized siderite. Depending on Fe(ll)-bearing phase and pH, we observed four different reaction products, red and gray elemental Se, and two iron selenides with structures similar to Fe7Se8 and FeSe. The thermodynamically most stable iron selenide, ferroselite (FeSe2), was not observed. The local structures of the reaction products suggest formation of nanoscale clusters, which may be prone to colloid-facilitated transport, and may have a higher than expected solubility. [ABSTRACT FROM AUTHOR]

Background: The origin of the spatial variability of dissolved As concentrations in shallow aquifers of the Bengal Basin remains poorly understood. To address this, we compare here transects of simultaneously-collected groundwater and aquifer solids perpendicular to the banks of the Hooghly River in Chakdaha, India, and the Old Brahmaputra River in Araihazar, Bangladesh. Results: Variations in surface geomorphology mapped by electromagnetic conductivity indicate that permeable sandy soils are associated with underlying aquifers that are moderately reducing to a depth of 10-30 m, as indicated by acid-leachable Fe(II)/Fe ratios <0.6 in the solid phase and concentrations of dissolved sulfate >5 mg L-1. More reducing aquifers are typically capped with finer-grained soils. The patterns suggest that vertical recharge through permeable soils is associated with a flux of oxidants on the banks of the Hooghly River and, further inland, in both Chakdaha and Araihazar. Moderately reducing conditions maintained by local recharge are generally associated with low As concentrations in Araihazar, but not systematically so in Chakdaha. Unlike Araihazar, there is also little correspondence in Chakdaha between dissolved As concentrations in groundwater and the P-extractable As content of aquifer particles, averaging 191 ± 122 ug As/L, 1.1 ± 1.5 mg As kg-1 (n = 43) and 108 ± 31 ug As/L, 3.1 ± 6.5 mg As kg-1 (n = 60), respectively. We tentatively attribute these differences to a combination of younger floodplain sediments, and therefore possibly more than one mechanism of As release, as well as less reducing conditions in Chakdaha compared to Araihazar. Conclusion: Systematic dating of groundwater and sediment, combined with detailed mapping of the composition of aquifer solids and groundwater, will be needed to identify the various mechanisms underlying the complex distribution of As in aquifers of the Bengal Basin. [ABSTRACT FROM AUTHOR]

Holocene groundwater in many districts of the West Bengal and parts of Bangladesh are enriched in arsenic enhancing poisoning effect on humans. One of the main problems to depict the source of arsenic is that this element is very mobile and can be easily removed and recombined from the source during alteration processes, transport and mobilization in sediments. The Ganga-Brahmaputra river system mainly contributed to the buildup of the Bengal fan, which is considered one of the largest modern deltas of the world, then the possible source of the As has probably to be search within the Himalayan belt. We propose that the Indus-Tsangpo suture zone dominated by arc-related rocks and more particularly by large volume of serpentinites enriched in arsenic could be one of the primary source of arsenic. The fact that, the present day arsenic concentration in the main Himalayan river, and particularly the Siang-Brahmaputra river system is not so high as expected can be explained by strong aridic conditions present day prevailing in the Indus-Suture zone and do not favored the weathering of serpentinites into As rich-smectite and Fe-hydroxydes. For the Ganga basin, the original source of arsenic has to be search in the weathering of arc related rocks in the Indus-Tsangpo suture zone followed by its intermediate storage into the sediments of the Siwalik foreland basin, playing the role of arsenic reservoir from Miocene to Pleistocene. Intense tectonic activity in the front of the Himalayan belt associated with high rainfall conditions during the Holocene allowed the arsenic to be remobilized and transported toward the Bay of Bengal. [ABSTRACT FROM AUTHOR]

Abstract: Extremely high As concentrations in drinking water of the Ganges Delta (West Bengal and Bangladesh) has emerged as an issue of great concern in the past decade because of its serious impact on the health of millions of people. The distribution pattern of As concentrations in the Ganges Delta region is patchy and there are numerous As “hotspots”. The present study is perhaps the first attempt in West Bengal to characterize such a hotspot by geophysical and geochemical methods, and to model the transport of the enrichment plume using a 1D reactive transport model (PHREEQC). The study site is located along the Hooghly River, 60 km north of Kolkota City, near the city of Chakdaha. Total As concentrations in the groundwater range from 0.5 to more than 6μmolL−1; the WHO recommended maximum drinking water concentration is 0.13μmolL−1 (i.e. 10μgL−1). Results show groundwater is in chemical equilibrium with siderite and calcite, a mineral phase previously shown to be an efficient trap for As(III). Groundwater redox potential is controlled by the Fe(OH)3(am)/Fe2+ couple. The As(III) versus As(V) distribution (42% As(III) and 58% As(V), on average) is not at equilibrium with measured Eh values. No evidence of sulfide solid phases, such as As rich pyrite or arsenopyrite, was found. Although amorphous Fe dissolution is confirmed to play an important role in the release of As, selective dissolution extractions indicate that adsorption of As on carbonates and micas may also be an important component of As cycling in the sediment. Modelling results demonstrate the role of and Fe(II) in mobilizing the As plume, thereby increasing the threat to the 75,000 inhabitants of Chakdaha. [Copyright &y& Elsevier]

The GGGTH sequence has been proposed to be the minimal sequence involved in the binding of a fifth Cu(II) ion in addition to the octarepeat region of the prion protein (PrP) which binds four Cu(II) ions. Coordination of Cu(II) by the N- and C-protected Ac-GGGTH-NH2 pentapeptide (P5) was investigated by using potentiometric titration, electrospray ionization mass spectrometry, UV–vis spectroscopy, electron paramagnetic resonance (EPR) spectroscopy and cyclic voltammetry experiments. Four different Cu(II) complexes were identified and characterized as a function of pH. The Cu(II) binding mode switches from NO3 to N4 for pH values ranging from 6.0 to 10.0. Quasi-reversible reduction of the [CuII(P5)H−2] complex formed at pH 6.7 occurs at E 1/2=0.04 V versus Ag/AgCl, whereas reversible oxidation of the [CuII(P5)H−3]− complex formed at pH 10.0 occurs at E 1/2=0.66 V versus Ag/AgCl. Comparison of our EPR data with those of the rSHaPrP(90-231) (Burns et al. in Biochemistry 42:6794–6803, ) strongly suggests an N3O binding mode at physiological pH for the fifth Cu(II) site in the protein. [ABSTRACT FROM AUTHOR]

Abstract: The redox properties of FeII adsorbed onto a series of FeIII (oxyhydr)oxides (goethite, lepidocrocite, nano-sized ferric oxide hydrate (nano-FOH), and hydrous ferric oxide (HFO)) have been investigated by rest potential measurements at a platinum electrode, as a function of pH (−log10[H+]) and surface coverage. Using the constant capacitance surface complexation model to describe FeII adsorption onto these substrates, theoretical values of the suspension redox potential (E H) have been computed, under the assumption that FeII adsorption occurs at crystal growth sites of the substrate surface. Good agreement between calculated and experimental E H values is observed for nano-FOH and HFO, however the redox potentials measured for lepidocrocite and goethite are significantly more oxidizing than predicted. Mössbauer spectroscopic analysis of 57FeII adsorbed onto HFO and goethite shows that in both cases the adsorbed 57FeII is incorporated into the crystal structure of the substrate, in broad agreement with the thermodynamic model, but is almost completely oxidized to 57FeIII. The mechanism by which the adsorbed 57FeII is oxidized is not resolved in this work, but is thought to be due to electron transfer to the substrate, rather than a net oxidation of the suspension. The disagreement between experimental and calculated rest potential measurements in the goethite and lepidocrocite systems is thought to be due to the poor electrochemical equilibration of these suspensions with the platinum electrode, rather than a failure of the thermodynamic model. The model developed for the redox potential of adsorbed FeII allows direct assessment of the reactivity of this species towards oxidized pollutants. [Copyright &y& Elsevier]

Abstract: Disordered mackinawite, FeS, is the first formed iron sulfide in ambient sulfidic environments and has a highly reactive surface. In this study, the solubility and surface chemistry of FeS is described. Its solubility in the neutral pH range can be described by K s app = {Fe2+}·{H2S(aq)}·{H+}−2 = 10+4.87±0.27. Acid-base titrations show that the point of zero charge (PZC) of disordered mackinawite lies at pH ∼7.5. The hydrated disordered mackinawite surface can be best described by strongly acidic mono-coordinated and weakly acidic tricoordinated sulfurs. The mono-coordinated sulfur site determines the acid-base properties at pH &#60; PZC and has a concentration of 1.2 × 10−3 mol/g FeS. At higher pH, the tricoordinated sulfur, which has a concentration of 1.2 × 10−3 mol/g FeS, determines surface charge changes. Total site density is 4 sites nm−2. The acid-base titration data are used to develop a surface complexation model for the surface chemistry of FeS. [Copyright &y& Elsevier]

Abstract: Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The Kd (L g−1) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility. [Copyright &y& Elsevier]

Hydrous ferric oxide (HFO) colloids formed, in strictly anoxic conditions upon oxidation of Fe2+ ions adsorbed on mineral surface, were investigated under in situ conditions by contact mode atomic force microscopy (AFM). Freshly cleaved and acid-etched large single crystals of near endmember phlogopite were pre-equilibrated with dissolved Fe(II) and then reacted with Hg(II), As(V) and trichlorethene (TCE)-bearing solutions at 25 °C and 1 atm. HFO structures are found to be of nanometer scale. The As(V)–Fe(II) and Hg(II)–Fe(II) reaction products are round (25 nm) microcrystallites located predominantly on the layer edges and are indicative of an accelerated Fe(II) oxidation rate upon formation of Fe(II) inner sphere surface complexes with the phyllosilicate edge surface sites. On the other hand, TCE–Fe(II)–phlogopite reaction products are needle-shaped (45 nm long) particles located on the basal plane along the Periodic Bond Chains (PCBs) directions. Experiments with additions of sodium chloride confirm the importance of the Fe(II) adsorption step in the control of the overall heterogeneous Fe(II)–TCE electron transfer reaction.Kinetic measurements at the nanomolar level of Hg° formed upon reduction of Hg(II) by Fe(II) in presence of phlogopite particles provide further convincing evidence for reduction of Hg(II)aq coupled to the oxidation of Fe(II) adsorbed at the phlogopite–fluid interface, and indicate that sorption of Fe(II) to mineral surfaces enhances the reduction rate of Hg(II) species. The Hg(II) reduction reaction follows a first-order kinetic law. Under our experimental conditions, which were representative of many natural systems, 80% of the mercury is transferred to the atmosphere as Hg° in less than 2 h.The reduction of a heavy metal (Hg), a toxic oxyanion (arsenate ion) and a chlorinated solvent (TCE) thus appear to be driven by the high reactivity of adsorbed Fe(II). This is of environmental relevance since these three priority pollutants are that way reductively transformed to a volatile, an immobilizable and a biodegradable species, respectively. Such kinetic data and reaction pathways are important in the evaluation of natural evaluation scenarios, in the optimization of Fe(II)/mineral mixtures as reductants in technical systems, and in general, in predicting the fate and transport of pollutants in natural systems. [Copyright &y& Elsevier]

Investigates the oxidation of arsenic by hexagonal birnessite. Occurrence of arsenic oxidation by manganese oxides in surface water; Structural formula of hexagonal birnessite; Use of atomic force microscopy to determine the oxidation state of manganese and arsenic.

Focuses on a study which discussed the dissolution of individual hectorite particles in molecular scales in acidic aqueous solution with atomic force microscopy. Identification of reactive surface area of individual hectorite and change during dissolution; Methodology; Results of the study.

Studies the decontamination of ground water by granular iron. Interactions between Fe(II) and iron corrosion products; Characteristics of mineral particles; Experimental conditions for Fe(II) sorption experiments; Features of the Fe0 reactivity in iron walls used against contaminated ground water.

• We summarized and discussed about antimony pollution in water environment and its sources. • Research on toxicity of antimony was documented. • Occurrence and biogeochemistry of antimony in water environment were discussed. Antimony, the compounds of which exhibit toxicity, finds extensive usage in industrial processes for flame retardants, plastics, batteries, electronic components, and mechanical bearings. Consequently, mining and industrial activities contribute to the continuous migration of antimony into aquatic environments, influencing the Earth's biogeochemical cycle. Given China's status as the primary global exporter of antimony, the country confronts the challenge of water pollution arising from intensive antimony mining operations. This paper focuses on the latest advances in research concerning antimony toxicity, identifies potential sources of antimony water pollution, and explores its migration pathways and biogeochemistry. Moreover, the study provides estimations of antimony quantities in different compartments. Finally, we discuss the prospects for enhancing our comprehension of antimony's biogeochemical behavior. [ABSTRACT FROM AUTHOR]

Selenium 0 (Se0) is a powerful anti-proliferative agent in cancer research. We investigated the impact of sub-toxic concentrations of Se0 functionalized nanoparticles (SeNPs) on prostate cancer PC-3 cells and determined their intracellular localization and fate. An in-depth characterization of functionalized selenium nanoparticles composition is proposed to certify that no chemical bias relative to synthesis issues might have impacted the study. Selenium is an extremely diluted element in the biological environment and therefore requires high-performance techniques with a very low detection limit and high spatial resolution for intracellular imaging. This was explored with state-of-the-art techniques, but also with cryopreparation to preserve the chemical and structural integrity of the cells for spatially resolved and speciation techniques. Monodisperse solutions of SeNPs capped with bovine serum albumin (BSA) were shown to slow down the migration capacity of aggressive prostate cancer cells compared to polydisperse solutions of SeNPs capped with chitosan. BSA coating could prevent interactions between the reactive surface of the nanoparticles and the plasma membrane, mitigating the generation of reactive oxygen species. The intracellular localization showed interaction with mitochondria and also a localization in the lysosome-related organelle. The SeNPs-BSA localization in mitochondria constitute a possible explanation for our result showing a very significant dampening of the PC-3 cell proliferation capabilities. The purpose of the use of sublethal compound concentrations was to limit adverse effects resulting from high cell death to best evaluate some cellular changes and the fate of these SeNPs on PC-3. Our findings provide new insight to further study the various mechanisms of cytotoxicity of SeNPs. [ABSTRACT FROM AUTHOR]

Silver nanowires (AgNW) are attractive materials that are anticipated to be incorporated into numerous consumer products such as textiles, touchscreen display, and medical devices that could be in direct contact with skin. There are very few studies on the cellular toxicity of AgNW and no studies that have specifically evaluated the potential toxicity from dermal exposure. To address this question, we investigated the dermal toxicity after acute exposure of polymer-coated AgNW with two sizes using two models, human primary keratinocytes and human reconstructed epidermis. In keratinocytes, AgNW are rapidly and massively internalized inside cells leading to dose-dependent cytotoxicity that was not due to Ag+ release. Analysing our data with different dose metrics, we propose that the number of NW is the most appropriate dose-metric for studies of AgNW toxicity. In reconstructed epidermis, the results of a standard in vitro skin irritation assay classified AgNW as non-irritant to skin and we found no evidence of penetration into the deeper layer of the epidermis. The findings show that healthy and intact epidermis provides an effective barrier for AgNW, although the study does not address potential transport through follicles or injured skin. The combined cell and tissue model approach used here is likely to provide an important methodology for assessing the risks for skin exposure to AgNW from consumer products. [ABSTRACT FROM AUTHOR]

[Display omitted] The wettability of carbonate rocks is expected to be affected by the organic components of biominerals which are complex, nanostructured organo-mineral assemblages. Elucidating the nanoscale mechanisms driving the wettability of solid surfaces will enable a better understanding of the role of biominerals in the wetting properties of carbonate rocks to control various geological, environmental and industrial processes. Using Atomic Force Microscopy and Spectroscopy (AFM/AFS) we probed the wettability properties of carbonate rocks with different amounts of organic material. The adhesion properties of two types of limestones were determined in liquid environments at different length scales (nm to mm) using functionalized tips with different chemical groups to determine the extent of surface hydrophobic and hydrophilic organo-mineral interactions. We observed homogeneous hydrophobic areas at length scales below < 5 µm. The origin of this hydrophobicity is linked to the presence of organics, whose amount and spatial distribution depend on the rock composition. Specifically, our results reveal that the biogenic vs non-biogenic origin of the mineral grains is the main rock property controlling the wettability of the solid surface. Overall, our methodology offers a multi-scale approach to unravel the role that organic moieties and biominerals play in controlling the wettability of rock-water interfaces. [ABSTRACT FROM AUTHOR]

In this article, the authors ponder on the impact of proposed trade agreements on international environmental research in 2014. Topics discussed include a Trans-Pacific Partnership (TPP) agreement and a Trans-Atlantic Trade and Investment Partnership (TTIP) agreement that were inspired by the North American Free Trade Agreement (NAFTA). Also mentioned is a dispute between Canada and the U.S. concerning the gasoline additive methylcyclopentadienyl manganese tricarbonyl (MMT).

The use of printed paper electronics in consumer goods is expected to experience a mass development in the next future. The ink used in these devices contains silver nanomaterials that may be released into the environment at the product end-of-life. We report here the first evaluation of the fate of silver during a pilot-scale recycling of printed paper electronics, made of paper printed with a cellulose nanofibrils-silver nanowire ink. We show that the released effluents are mainly free from silver, which is retained in the pulp conserved for recycling. We use atomic force microscopy experiments to show that this strong pulp-silver bond is due to the embedding of the silver nanowires in the pulp by coils of cellulose nanofibrils. We propose an estimate of the resulting adhesion stress of the nanowires to the ink, high enough to keep the silver inside the pulp during the recycling procedure. [ABSTRACT FROM AUTHOR]

The interaction of an As-rich natural pyrite (FeS2.08As0.043) with aqueous Se(IV) was investigated as a function of pH, ferrous iron concentration, and reaction time. Arsenic is often the most abundant minor constituent of natural pyrite, and is believed to substitute for S in the pyrite structure. EXAFS measurements confirmed the presence of AsS dianion group, with arsenic in the same local configuration as in the arsenopyrite. Speciation studies indicated that Se(0) was the unique reduction product in the pH range 5.05-8.65 over a reaction period of >1month, while trace amounts of FeSeO3 might be formed at pH⩾6.10. At pH>6.07, the formation of Fe(III)-(oxyhydr)oxide is kinetically favored, and it consumed nearly all the aqueous iron, including the extra added Fe2+, thereby inhibiting the formation of the thermodynamically most stable product: FeSe2. After oxidation by Se(IV), the occurrence of surface S0, significant aqueous sulfur deficit, and excessive leaching of arsenic in solution, indicate the preferential release of As impurity via arsenopyrite oxidation. The data suggest that the polysulfide-elemental sulfur pathway, which prevails in acid-soluble metal sulfides, is an important pathway in the oxidation of As-rich pyrite, in addition to the thiosulfate pathway for acid-insoluble pyrite. Control experiments on As-free natural pyrite further support this mechanism. This study confirms the potential of reductive precipitation to attenuate the mobility of Se in the environment and demonstrates that minor elements commonly present in natural pyrite can play a significant role on its dissolution pathway. [ABSTRACT FROM AUTHOR]

Little is known about the distributionof the intercalated moleculeswithin the interstratified layers resulting from the pH-dependentinterlayer adsorption of ionizable organic molecules, including antibiotics,within smectite-type clay minerals. Here we employed experimentaland simulated X-ray diffraction (XRD) to characterize interstratification(or mixed layering) from the intercalation of oxytetracycline (OTC),a commonly used tetracycline antibiotic, within Na-montmorillonitelayers at pHs 4, 5, 6, and 8. Our XRD data reveal that OTC is distributednonrandomly in the interlayers such that Na- and OTC-saturated interlayerscoexist. The profile of the full width at half-maximum intensity (fwhm),monitored as a function of increasing layer-to-layer distance (d001), resulting from an increasing amount ofintercalated OTC, reflects such mixed-layer crystals under the acidicpH conditions. A minimum in fwhm occurs at a d spacing of about 1.8nm, which is to be the optimal d001forOTC-saturated layers, in agreement with molecular modeling results.Using the coordinates of the thermodynamically favorable configurationof the adsorptives in a model montmorillonite interlayer, we simulatedXRD profiles to unravel the different patterns of interstratificationfrom the experimental data. At both pHs 4 and 5, Na- and OTC-interlayersare randomly interstratified, whereas at pH 6, these layers are clustered,as characterized by a segregated interstratification pattern. Thetheoretical layer stacking sequences of the simulated XRD illustrate,as pH increases, the clustering of similar layer types with the exclusionof OTC intercalation from clay populations enriched in Na. At pH 8,both fwhm and d001indicate OTC adsorptionprimarily on external surface sites, not within interlayers. Our findingsimply that, in addition to chemical speciation, a pH-dependent formationof montmorillonite crystallites with unexfoliated layers may be responsibleboth for the decreased OTC intercalation and for the increased bindingon external sites, thus resulting in the different patterns of interstratificationas a function of increasing pH. [ABSTRACT FROM AUTHOR]

The reductive immobilization of Se(IV) by micrometer-sized (100-200 μm) calcite containing sorbed or coprecipitated Fe(II) was investigated at pH 7 under anoxic conditions (O2 < 1 ppmv) using X-ray absorption near-edge structure (XANES) spectroscopy. The Se(IV) sorption on calcite increased in the presence of sorbed Fe(II) compared to that of Fe-free pure calcite. XANES spectra of Se K-edge shows that nearly half of the total sorbed Se(IV) is reduced to Se(0) by Fe(II) sorbed on calcite within 24 h. The extent of reduction decreases with increasing equilibration time of calcite with Fe(II) solution before Se(IV) addition. The combined results of field emission scanning electron microscopy and X-ray diffraction have shown that needle-shaped red monoclinic elemental Se with diameters of 30-50 nm and lengths of up to 100 nm is precipitated on the calcite surface. Fe(II) coprecipitated calcite does not contribute to Se(IV) reduction within 72 h. Therefore, the reduction capacity of Fe(II) linked to calcite critically depends on its location (either on the surface or in the bulk solid), and less extensively on the pre-equilibration time of calcite with Fe(II) solution. Such understanding is important to predict the transport, transformation, and attenuation of Se in subsurface and in nuclear waste repositories. [ABSTRACT FROM AUTHOR]

Abstract: The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds–minutes) was followed by (b) a slower incorporation (hours–weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4mol% Fe:Ca and a mixed carbonate layer thickness of 25nm (after 168h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA 51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA 57 (1993), 3505; Pokrovsky et al., Langmuir 16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO3Fe+ and >CO3FeCO3H0. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15h, the oxidation kinetics was comparable to a calcite-free system (t 1/2 =145±15min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t 1/2 =41±1min and t 1/2 =100±15min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO3FeCO3H0, for which the species specific rate constant was estimated. [Copyright &y& Elsevier]

To describe the anatomical bases of the surgical access to the higher part of the thyroid lobe, with first location of the inferior laryngeal nerve at its laryngeal penetration, to discuss the advantages and disadvantages of this surgical technique and to determine the operational indications. A prospective study of surgical anatomy performed over a period of 18 months was conducted. A total of 25 (22 women and 3 men) patients with cervicothoracic goitre underwent total thyroidectomy. Thyroid lobectomies were performed using the technique of “capsular thyroidectomy”, with first location and complete dissection of the inferior laryngeal nerve. A neurostimulator was systematically used for the location of the inferior laryngeal nerve and also the external laryngeal nerve. The first detection of the inferior laryngeal nerve at the top of the thyroid lobe was positive in 49/50 cases. A superior parathyroid gland was found in 75% of cases and an inferior parathyroid gland in 37.5% of cases. The external laryngeal nerve was stimulated and respected in 12,5% of cases. No voice trouble, no laryngeal palsy and no definitive hypoparathyroidism occurred after surgery. Safeguarding of the inferior laryngeal nerve is the principal and obligatory stake in thyroid surgery. Locating the inferior laryngeal nerve at the level of its laryngeal penetration at the superior pole of the thyroid region is necessary in cases of particular situations: huge cervicothoracic goitres, re-operative procedures and various anatomical variations. The use of a neurostimulator secures this technique. [ABSTRACT FROM AUTHOR]

Abstract: The dissolution behavior of montroydite (HgO) has been studied using a fully automated system. Dissolution data under equilibrium conditions are in agreement with previously published data and indicate that HgO solubility is relatively high and constant between pH 4 and 10.1 and increases markedly at pH<4. The dissolution rate also has similar behavior: it is relatively high and constant between pH 4 and 10.1 and increases sharply at pH<4. The dissolution process obeys a three-dimensional contraction or attrition mechanism. The dissolution rate increases with increasing temperature and stirring rate and is the result of mixed transport and reaction control. The rate of HgO dissolution is considerably higher than that of other divalent metal oxides at low pH. This high rate is due to the ability of Hg(II) to rapidly exchange its ligands. Data suggest that montroydite will only occur in nature in highly contaminated sites and indicate that Hg oxidation products that are formed at the liquid Hg/water interface may dissolve rapidly. [Copyright &y& Elsevier]

Nanoscale zero-valent iron (NZVI) was synthesized and tested for the removal of As(llI), 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(lll)-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(lll) adsorption kinetics were rapid and occurred on a scale of minutes following a pseudo-first-order rate expression with observed reaction rate constants (kobs) of 0.07-1.3 min-1 (at varied NZVI concentration). These values are about 1000 × higher than kobs literature values for As(lll) adsorption on micron size ZVI. Batch experiments were performed to determine the feasibility of NZVl as an adsorbent for As(lll) treatment in groundwater as affected by initial As(lll) concentration and pH (pH 3-12). The maximum As(lll) adsorption capacity in batch experiments calculated by Freundlich adsorption isotherm was 3.5 mg of As(lIl)/g of NZVI. Laser light scattering (electrophoretic mobility measurement) confirmed NZVI-As(lIl) inner-sphere surface complexation. The effects of competing anions showed HCO3-, H4SiO40, and H2PO42- are potential interferences in the As(Ill) 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. [ABSTRACT FROM AUTHOR]

The surface properties of ferrihydrite were studied by combining wet chemical data, CdK EXAFS data, and a surface structure and protonation model of the ferrihydrite surface. Acid–base titration experiments and Cd(II)–ferrihydrite sorption experiments were performed within 3<−log[H+]<10.5 and 0.5<[Cdt]<12 mM in 0.3 M NaClO4 at 25 °C, where [Cdt] refers to total Cd concentration. Measurements at −5.5&les;log[Cdt]&les;−1.4 at fixed pH completed the wet chemical data set. The acid–base titration data could be adequately modeled by &z.tbnd;Fe&z.sbnd;OH2+1/2−H+↔&z.tbnd;Fe&z.sbnd;OH−1/2, logk(int)=−8.29, assuming the existence of a unique intrinsic microscopic constant, logk(int), and consequently the existence of a single significant type of acid–base reactive functional groups. The surface structure model indicates that these groups are terminal water groups. The Cd(II) data were modeled assuming the existence of a single reactive site. The model fits the data set at low Cd(II) concentration and up to 50% surface coverage. At high coverage more Cd(II) ions than predicted are adsorbed, which is indicative of the existence of a second type of site of lower affinity. This agrees with the surface structure and protonation model developed, which indicates comparable concentrations of high- and low-affinity sites. The model further shows that for each class of low- and high-affinity sites there exists a variety of corresponding Cd surface complex structure, depending on the model crystal faces on which the complexes develop. Generally, high-affinity surface structures have surface coordinations of 3 and 4, as compared to 1 and 2 for low-affinity surface structures. [Copyright &y& Elsevier]

Investigates the mechanisms of zinc uptake in dilute suspensions of hectorite. Use of kinetic experiments and extended X-ray absorption fine structure spectroscopy; Value of the hydrogen-ion concentration; Adsorption of zinc on exchange sites; Dissolution of hectorite.

More than 100 million people around the world are endangered by geogenic arsenic (As) in groundwater, residing in sedimentary aquifers. However, not all sedimentary aquifers are groundwater As enriched, and the ultimate source of As in enriched aquifer sediments is yet-unknown, globally. A reconnaissance of the major aquifers suggests that major As enriched aquifers are predictably systematic on a global scale, existing in sedimentary foreland basins in the vicinity of modern or ancient orogenic systems. In conformity with the Principle of Uniformitarianism, we demonstrate that the groundwater As comes from magmatic arcs (primary source) in present (e.g. Andes) or ancient (e.g. Himalaya) continental convergent margins of some of the most prominent orogenic systems across the globe, and ends up in sediments (secondary source) in adjoining foreland or related basins that eventually act as aquifers. These arc magmas scavenge As while rising through the deep continental crust. Erosion of such orogens ultimately increases the bulk As content in sediments of adjoining basins, leading to groundwater As enrichment in downstream aquifers. Such As-polluted aquifers are eventually extensively used for groundwater exploitation, for drinking and other human purposes. Surface geological and biogeochemical processes, like redox reactions, are conducive to such groundwater As enrichment. We suggest this model by integrating our study of long-time observations in Himalayan and Andean basin aquifers, and generalizing 63 major aquifers across the globe, to demonstrate the source-to-sink transport of As, thereby delineating it's geogenic cycling in the subsurface. This work outlines the specifics of the mechanisms that would drive the processes of groundwater As enrichment across spatio-temporal scales, i.e. tectonic-scale taking place over millions of years on continental-scale and groundwater pollution taking place at human time-scales on village to household scale. Thus, in this work, we demonstrate a direct evidence of connectivity between global geological processes and individual human health. Unlabelled Image • Establish link between tectonics and groundwater arsenic pollution • Demonstrate the model of geogenic As cycle with examples across the world • Evaluate the geologic framework of major arsenic-enriched aquifers • Propose link between global geological processes with human health [ABSTRACT FROM AUTHOR]

Fibrous particles interact with cells and organisms in complex ways that can lead to cellular dysfunction, cell death, inflammation, and disease. The development of conductive transparent networks (CTNs) composed of metallic silver nanowires (AgNWs) for flexible touchscreen displays raises new possibilities for the intimate contact between novel fibers and human skin. Here, we report that a material property, nanowire-bending stiffness that is a function of diameter, controls the cytotoxicity of AgNWs to nonimmune cells from humans, mice, and fish without deterioration of critical CTN performance parameters: electrical conductivity and optical transparency. Both 30- and 90-nm-diameter AgNWs are readily internalized by cells, but thinner NWs are mechanically crumpled by the forces imposed during or after endocytosis, while thicker nanowires puncture the enclosing membrane and release silver ions and lysosomal contents to the cytoplasm, thereby initiating oxidative stress. This finding extends the fiber pathology paradigm and will enable the manufacture of safer products incorporating AgNWs. [ABSTRACT FROM AUTHOR]

Contaminant removal from (waste)waters by magnetite is a promising technology. In the present experimental study, a magnetite recycled from the steel industry waste (zero-valent iron powder) was used to investigate the sorption of As, Sb and U in phosphate-free and -rich suspensions, i.e. as a remediation for the acidic phosphogypsum leachates derived from the phosphate fertilizer industry. The results showed up to 98% U removal under controlled pH conditions, while phosphate did not hinder this immobilisation. In contrast, the results confirmed the limited uptake of As and Sb oxyanions by magnetite in presence of phosphate as the competing anion, displaying only 7–11% removal, compared to 83–87% in the phosphate-free sorption experiments. To limit this wastewater problem, raw ZVI anaerobic oxidation was examined as mechanism to increase the pH and as a source of Fe2+ in a first step, and in a second step to remove phosphate via vivianite precipitation, therefore prior to the reaction with magnetite. UV–Vis, XRD and SEM-EDS showed that vivianite precipitation is feasible at pH > 4.5, mainly depending on the phosphate concentration. The higher the [PO 4 3−], the lower is the pH at which vivianite precipitates and the higher the % removal of phosphate from solution. It is anticipated that an optimum 3-steps design with separate reactors controlling the conditions of ZVI oxidation, followed by vivianite precipitation and finally, reaction with magnetite, can achieve high contaminant uptake in field applications. [Display omitted] • Sorption of As, Sb, and U by magnetite in acidic, PO 4 3− rich waters is shown. • PO 4 3− does not hinder U sorption, on the contrary to As and Sb. • (N)ZVI is used to increase the water pH and produce Fe2+ to form vivianite. • Phosphate ions precipitate as vivianite at pH > 4.5, depending mainly on [PO 4 3−]. • A novel, eco-friendly remediation route of acidic, PO 4 3--rich waters is suggested. [ABSTRACT FROM AUTHOR]

Abstract The impact of seasonal fluctuations linked to monsoon and irrigation generates redox oscillations in the subsurface, influencing the release of arsenic (As) in aquifers. Here, the biogeochemical control on As mobility was investigated in batch experiments using redox cycling bioreactors and As- and SO 4 2−-amended sediment. Redox potential (E h) oscillations between anoxic (−300–0 mV) and oxic condition (0–500 mV) were implemented by automatically modulating an admixture of N 2 /CO 2 or compressed air. A carbon source (cellobiose, a monomer of cellulose) was added at the beginning of each reducing cycle to stimulate the metabolism of the native microbial community. Results show that successive redox cycles can decrease arsenic mobility by up to 92% during reducing conditions. Anoxic conditions drive mainly the conversion of soluble As(V) to As(III) in contrast to oxic conditions. Phylogenetic analyses of 16S rRNA amplified from the sediments revealed the presence of sulfate and iron – reducing bacteria, confirming that sulfate and iron reduction are key factors for As immobilization from the aqueous phase. As and S K-edge X-ray absorption spectroscopy suggested the association of Fe-(oxyhydr)oxides and the importance of pyrite (FeS 2(s)), rather than poorly ordered mackinawite (FeS (s)), for As sequestration under oxidizing and reducing conditions, respectively. Finally, these findings suggest a role for elemental sulfur in mediating aqueous thioarsenates formation in As-contaminated groundwater of the Mekong delta. Graphical abstract Unlabelled Image Highlights • Microbial sulfate reduction was found to contribute to arsenic (As) sequestration. • During anoxic conditions, the conversion of soluble As(V) to As(III) was observed. • The formation of pyrite, rather than mackinawite was observed in redox cycles. • Absorption/desorption of aqueous As on Fe-(oxyhydr)oxides and pyrite was observed. [ABSTRACT FROM AUTHOR]

Argillaceous geological formations are considered promising repositories for waste containing inorganic contaminants. However, the sequestration capacity of an argillaceous natural barrier may change as a result of dynamic environmental conditions, in particular changes in redox state. Here, we imposed redox cycles to argillaceous suspensions amended with a mixture of the inorganic contaminants As(V), Sb(V), Cr(VI), by alternating 7-day cycles of sparging with either oxic or anoxic gas mixtures. During the redox cycles, we assessed the relative importance of different contaminant sequestration mechanisms under sterile and non-sterile conditions. The non-sterile experiments were carried out 1) with the argillaceous material as is, that is, containing the native microbial population, 2) with the addition of ethanol as a source of labile organic carbon, and 3) with the addition of both ethanol and a soil microbial inoculum. In order to capture the observed solid-solution partitioning trends, a series of mixed thermodynamic-kinetic models representing the dynamic conditions in the experiments were developed using PHREEQC. Parameter values for processes such as adsorption, which occurred in all experiments, were kept constant across all the simulations. Additional formulations were introduced as needed to account for the microbial detoxification and respiration of the contaminants in the increasing complexity experiments. Abiotic adsorption of As and abiotic reductive precipitation of Cr dominated sequestration of these two contaminants under all experimental conditions, whereas the presence of microorganisms was essential to decrease the aqueous Sb concentration. Once reduced, As(III), Sb(III), and Cr(III) were not re-oxidized upon exposure to dissolved O 2 in any of the experiments. Neither the mineralogy nor the native microbiota catalysed contaminant oxidation processes. Thus, kinetically, the reduction of As(V), Sb(V), and Cr(VI) was irreversible over the experimental duration (49 days). The capacity of the argillaceous matrix to reduce and sequester the aqueous contaminants, without subsequent remobilization to the aqueous phase during the oxic periods, supports the use of argillaceous barriers for geologic waste storage. [ABSTRACT FROM AUTHOR]

Layered double hydroxides (LDHs) are anion exchangers with a strong potential to scavenge anionic contaminants in aquatic environments. Here, the uptake of selenite (SeO32-) by Ca-Al LDHs was investigated as a function of Se concentration. Thermodynamic modeling of batch sorption isotherms shows that the formation of SeO32--intercalated AFm (hydrated calcium aluminate monosubstituent) phase, AFm-SeO3, is the dominant mechanism controlling the retention of Se at medium loadings. AFm-Cl2 shows much stronger affinity and larger distribution ratio (Rd ~ 17800 L kg-1) toward SeO32- than AFm-SO4 (Rd ~ 705 L kg-1). At stoichiometric SeO32- loading for anion exchange, the newly formed AFm-SeO3 phase results in two basal spacing, i.e., 9.93 ± 0.06 Å and ~11.03 ± 0.03 Å. Extended X-ray absorption fine structure (EXAFS) spectra indicate that the intercalated SeO32- forms inner-sphere complexes with the Ca-Al-O layers. In situ X-ray diffraction (XRD) shows that basal spacing of Ca-Al LDHs have a remarkable linear relationship with the size of hydrated intercalated anions (i.e., Cl-, SO42-, MoO42-, and SeO32-). Contrary to AFm-SeO3 with inner-sphere SeO32- complexes in the interlayer, the phase with hydrogen-bonded inner-sphere complexed SeO32- is kinetically favored but thermodynamically unstable. This work offers new insights about the determination of intercalated anion coordination geometries via XRD analyses. [ABSTRACT FROM AUTHOR]

Layered double hydroxides (LDHs) have been considered as effective phases for the remediation of aquatic environments, to remove anionic contaminants mainly through anion exchange mechanisms. Here, a combination of batch isotherm experiments and X-ray techniques was used to examine molybdate (MoO42-) sorption mechanisms on CaAl LDHs with increasing loadings of molybdate. Advanced modeling of aqueous data shows that the sorption isotherm can be interpreted by three retention mechanisms, including two types of edge sites complexes, interlayer anion exchange, and CaMoO4 precipitation. Meanwhile, Mo geometry evolves from tetrahedral to octahedral on the edge, and back to tetrahedral coordination at higher Mo loadings, indicated by Mo K-edge X-ray absorption spectra. Moreover, an anion exchange process on both CaAl LDHs was followed by in situ time-resolved synchrotron-based X-ray diffraction, remarkably agreeing with the sorption isotherm. This detailed molecular view shows that different uptake mechanisms edge sorption, interfacial dissolution-reprecipitation are at play and control anion uptake under environmentally relevant conditions, which is contrast to the classical view of anion exchange as the primary retention mechanism. This work puts all these mechanisms in perspective, offering a new insight into the complex interplay of anion uptake mechanisms by LDH phases, by using changes in Mo geometry as powerful molecular-scale probe. [ABSTRACT FROM AUTHOR]

We report on the synthesis and As adsorption properties of a novel chitosan – iron (oxyhydr)oxide composite material for the remediation of arsenic-contaminated water supplies. FE-SEM, Mössbauer spectroscopy, ICP-OES and synchrotron (Bulk XAS, μXRF) techniques were applied to determine the composition of the new material and investigate the As uptake efficiency and mechanism. The iron (oxyhydr)oxide phase has been identified as a nano-sized goethite, well dispersed in the chitosan matrix, leading to the name ‘chitosan goethite bionanocomposite’ (CGB). The CGB material is prepared in the form of beads of high density and excellent compression strength; the embedding of the goethite nanoparticles in the chitosan matrix allows for the high adsorption capacity of nanoparticles to be realized. CGB beads remove both As(III) and As(V) efficiently from water, over the pH range 5–9, negating the need for pre-oxidation of As(III). Kinetic studies and μXRF analysis of CGB bead sections show that diffusion-adsorption of As(V) into CGB beads is faster than for As(III). Using CGB beads, synthetic high-arsenic water (0.5 mg-As/L) could be purified to world drinking standard level (<0.01 mg-As/L) using only 1.4 g/L CGB. When considered in combination with the advantages of the low-cost of raw materials required, and facile (green) synthesis route, CGB is a promising material for arsenic remediation, particularly in developing countries, which suffer a diversity of socio-economical-traditional constraints for water purification and sanitation. [ABSTRACT FROM AUTHOR]