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The adsorption of ceftriaxone (CET) and doxycycline (DOX) from aqueous solution using ferrihydrite/plant-based composites (silica rice husk) to reduce their negative impact on the ecosystem was adequately studied. On the other hand, phosphate and humic acid are often found in water and soil; in view of this, their effects on the adsorption of CET and DOX were investigated. The results showed that the removal of ceftriaxone decreased with an increase in pH, while that of doxycycline did not. Ferrihydrite with 10% silica rice husk (Fh-10%SRH) has the highest maximum adsorption capacity of 139 and 178 mg g-1 for CET and DOX, respectively, at room temperature based on Liu's adsorption isotherm. This implies that the presence of silica rice husk increases CET and DOX uptake due to an increase in the pore volume of FH-10%SRH. The results showed that phosphate had a significant inhibition role on CET adsorption and minor on DOX, whereas humic acid salt affected neither case. Increase in temperature up to 333 K favored the adsorption of both contaminants. The proposed adsorption mechanisms of ceftriaxone are electrostatic interaction, n-π interaction, and hydrogen bond, while that of DOX entails n-π interaction and hydrogen bond.

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In this study, four systems (S1, S2, S3, and S4) were evaluated to determine whether basic oxygen furnace sludge (BOFS), mainly composed of Fe (84%, mostly as elemental Fe and FeO), Ca (3%, as CaCO3), and Si (1%), is capable of removing As-spiked, Mn, Mg, and sulfate from an industrial acid mine drainage (AMDi) collected in a gold mine in Minas Gerais, Brazil. In the S1 system (BOFS/deionized water pH 2.5), the stability of the residue was evaluated for 408 h under agitation. The results showed that only Ca and Mg were solubilized, and the pH increased from 2.5 up to 11.4 within the initial 24 h and kept still until the end of the experiment (408 h). The S2 system (BOFS/AMDi) achieved 100% removal of As and Mn, and 70% removal of sulfate after 648 h. In the first 30 min, the pH increased from 2.5 to 10, which was maintained until the end of the experiment. The removal of As, Mn, and sulfate in the presence of hydrogen peroxide (S3 and S4 systems - BOFS/AMDi/H2O2) was similar to that in the S2 system, which contained only BOFS. The formation of iron oxides was not accelerated by H2O2. As regards the removal of arsenic and sulfate species, the formation of incipient calcium arsenate and calcium sulfate dehydrated was indicated by X-ray diffraction analysis and PHREEQC modeling. Dissolved manganese and magnesium precipitated as oxides, according to the geochemical modeling. After contact with AMDi, the raw BOFS, initially classified as hazardous waste, became a non-inert waste, which implies simplified, less costly disposal. Except for sulfate, the concentrations of all the other elements were below the maximum permitted levels.

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An original rationale is proposed to explain the controversial role of aluminum, a common substitutive element in ferrihydrite (Fh), on arsenic adsorption. The adsorption of arsenic on synthetic Al-for-Fe substituted Fh (AlFh) with up to 20 mol% Al was investigated at pH 5 and 8. The reduced interplanar spacings observed by selected area electron diffraction show that all AlFh samples are isomorphically substituted up to 20 mol% Al. A 15 mol% Al incorporation increases the arsenic uptake by 28%. In contrast, the Langmuir binding constants decrease, suggesting weaker bonds. Arsenic uptake reduces by 50% as pH rises from 5 to 8. The Al-for-Fe substitution in ferrihydrite causes structural defects, proton-compensated by OH groups, as indicated by the Vegard rule deviation. X-ray photoelectron spectroscopy demonstrates the increase in the relative amount of surface M-OH sites (45% to 77%) with Al concentration (AlFh-0 to AlFh-20), respectively. The enhanced As(V) uptake was ascribed to the insertion of hydroxyls on the Fh structural defects. Fourier-transformed-infrared spectroscopy showed that the sites modified by Al introduction are involved in As adsorption. These findings help to understand aluminum's role in arsenic adsorption, fixation, and fate in the environment.

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A comprehensive characterization was performed to investigate the composition and mineralogy of soils from a gold mining region and their correlation with arsenic (As) total concentration and its bioaccessible fraction. The arsenic bioaccessible (BAC) fraction was determined through in vitro test and calculated as the ratio between the amounts of As released and the total As concentration in the soil sample. Among the minor constituents of environmental concern, only arsenic is significantly higher (median of 748.0 mg kg-1) than the national guidelines (agricultural, 35 mg kg-1 and residential, 55 mg kg-1). All the other trace elements showed concentrations below the investigation values established for residential areas. The mean bioaccessible As was 7.0 mg kg-1, with a median value of 4.4 mg kg-1, and a median As BAC percentage of 0.7%. The Brunauer-Emmett-Teller (BET) surface area showed a consistent increase with the increase of the acid-soluble Al content in the soil samples. The distribution of As in the soil samples is not correlated with the abundance of As-minerals and the fraction of adsorbed As. Arsenic was shown to be trapped in oriented aggregates of crystalline (Al-)Fe-(hydr)oxides nanoparticles (the main metalloid reservoirs), as demonstrated by scanning and transmission electron microscopy analyses. This unique pattern supports the significant difference between total As concentration and the bioaccessible amount. There was a positive correlation between soluble Al (within the Fe-(hydr)oxides phases and minor gibbsite) and As concentration in the soil samples, and a negative correlation with bioaccessible As. Therefore, although Al in the soil is associated with high As levels, it also makes the metalloid less bioaccessible. The risk to human health from As exposure to these soils is low.

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In this work, it was developed three-dimensional (3D) porous hydrogel sponges produced by the freeze-dried process using chitosan polymer functionalized by 11-mercaptoundecanoic acid (MUA). These chitosan-based sponges were used as cationic adsorbents for the removal of anionic methyl orange (MO) dye, simulating a model organic pollutant in aqueous medium. Moreover, these porous 3D constructs were also evaluated as 'antibiotic-free' antibacterial materials against gram-negative and gram-positive bacteria, Pseudomonas aeruginosa and Staphylococcus aureus, respectively, which were used as model pathogens possibly found in contaminated hospital discharges. These 3D hydrogels were comprehensively characterized through morphological methods such as scanning electron microscopy and X-ray micro-computed tomography techniques, combined with FTIR, Raman, and UV-visible spectroscopy analyses. Additionally, the surface area, the degree of swelling, and the adsorption profiles and kinetics of these scaffolds were systematically investigated. The chemically thiolated chitosan (CHI-MUA) hydrogels were successfully produced with a supramolecular polymeric network based on hydrogen bonds, disulfide bonds, and hydrophobic interactions that resulted in higher stability in aqueous medium than hydrogels of pristine chitosan. CHI-MUA exhibited sponge-like three-dimensional structures, with highly interconnected and hierarchical pore size distribution with high porosity and surface area. These architectural aspects of the 3D sponges favoured the high adsorption capacity for MO dye (∼388 mg.g-1) in water with removal efficiency greater than 90% for MO solutions (from 20 mg.L-1-1200 mg.L-1). The adsorption data followed a pseudo-second-order kinetic model and adsorption isotherm analysis and spectroscopy studies suggested a multilayer behaviour with coexistence of adsorbent-adsorbate and adsorbate-adsorbate interactions. Additionally, the in vitro evaluation of toxicity (MTT and LIVE-DEAD® assays) of 3D-sponges revealed a non-toxic response and preliminary suitability for bio-related applications. Importantly, the 3D-sponges composed of chitosan-thiolated derivative proved high antibacterial activity, specificity against P. aeruginosa (model hazardous pathogen), equivalent to conventional antibiotic drugs, while no lethality against S. aureus (reference commensal bacteria) was observed.

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Bioaccessibility (BAC) of fine surface dust (FSD, particle size ≤10 µm) and surface dust samples (particle size ≤250 µm) collected from a gold mining district was used as a tool to determine the portion of arsenic that would be available via simulated lung and gastrointestinal (G.I) fluids. BAC was considered low for both tests (lung 2.7 ±â€¯1%, n = 5 and G.I 3.4 ±â€¯2%, n = 14 for residential surface dust samples). An analytical procedure was developed to further identify arsenic-bearing phases found in FSD samples and analyze the main components that regulate arsenic solubility. Up to five different arsenic-bearing phases were identified among a total of 35 minerals surveyed by scanning electron microscopy-based automated image analysis (Mineral Liberation Analyzer - MLA). Arsenic-bearing Fe oxy-hydroxides and mixed phases comprised the main arsenic phases encountered in FSD samples, thus likely being responsible for regulating arsenic bioaccessibility. Transmission electron microscopy showed that the mixed phases comprised a mix of oriented nanostructure aggregates formed by hematite and goethite entangled with phyllosilicates. The main As-bearing phases identified in FSD samples are similar to those reported in soil samples in the same region. The predominant arsenic-bearing phase encountered in the ore was arsenopyrite, mostly in large particles (>10 µm in size), and therefore unlikely to be found in residential dust. Arsenic intake from both inhalation and ingestion were minimal when compared to total arsenic intake (considering food and water ingestion), which itself was <7% of the value established by the Food and Agriculture Organization of the United Nations Benchmark Dose Lower Confidence Limit (BMDL0.5) of 3.0 µg per kg-1 body weight per day. These results indicated that the relative risks associated with arsenic exposure by inhalation and oral ingestion in this region are low.

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This study assessed various exposure pathways of arsenic and their health risk apportionment to the residents of Paracatu, a gold mining town in Brazil. We measured arsenic concentrations in 50 groundwater and surface town water samples from nearby residences, 38 surface soil dust from residential/commercial dwellings and roadside of Paracatu, and 600 airborne dust samples including PM10 and total suspended particulates (TSP), in additional to a previous reported food survey containing 90 samples from 15 major food categories. For the surface soil dust, bioaccessibility of arsenic as a surrogate of bioavailability was determined using an in vitro physiologically based extraction test (PBET). Rice and bean were found to contain the highest levels of arsenic in which the arsenic speciation was measured whereas the percentages of inorganic arsenic of other food items were taken from the literature for the risk apportionment calculation. The results show that the contribution of inhaled arsenic is ≤3% of the total daily intake, even assuming 100% BAC. The average bioaccessibility of arsenic in the surface soil dust was 3.4 ±â€¯2.0% (n = 17) with a bioaccessible concentration of 4.1 ±â€¯3.7 mg/kg. Food was the main contributor of the daily total intake of arsenic with rice and beans being the most significant ones. The total arsenic intake (ingestion + inhalation) is about 10% of the JECFA BMDL0.5 of 3 µg/kg b.w. per day, and the combined risk based on the cancer slope calculation is similar to the arsenic intake from the consumption of 2 L of water containing 10 µg/L of arsenic, a maximum concentration recommended by WHO. The holistic approach by addressing multiple pathways of exposure is considered a useful tool for health risk assessment throughout the life of mine including mine closure, and can be applied at legacy sites.

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The aim of this work is to evaluate the application of a steel waste, basic oxygen furnace sludge (BOFS), rich in iron, to treat water contaminated with elevated arsenic and sulfate concentrations. In the first step, three doses (10, 60, and 80 g L-1) of BOFS were tested to investigate the removal of As(III) and As(V) (67 mg L-1) and sulfate (3700 mg L-1) separately from an aqueous solution. In the second step, the efficacies of BOFS (10 g L-1) and commercial ZVI (5 g L-1) were compared to simultaneously remove arsenic and sulfate. The pH of the feed solution was adjusted to 2.5 and monitored during the experiment. The use of BOFS achieved arsenic removal up to 92% and sulfate removal of nearly 40% after 72 h of contact time. Use of BOFS also increased the solution pH to 12. Similar removal levels were achieved with both BOFS and ZVI. These results confirm the potential application of BOFS to remove high arsenic and sulfate concentrations from acidic solutions. The data obtained here should be used as a basis for further studies on the remediation of acid mine drainage with high concentrations of arsenic and sulfate using an abundant and low-cost steel waste.

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The human health risk associated with arsenic in food in Southeast Brazil was quantified. Based on the most commonly consumed food types in the Brazilian diet, the maximum inorganic As (iAs) daily intake from food (0.255 µg kg-1 body weight per day) is approximately 9% of the Benchmark Dose Lower Limit (BMDL0.5) of 3 µg kg-1 body weight per day set by the World Health Organization (WHO) and Food and Agriculture Organization (FAO) Joint Expert Committee in Food Additives (JECFA). When water is included, the contribution of food to the total intake varies from 96.9% to 39.7%. Rice and beans, the main Brazilian staple food, contribute between 67 and 90% of the total As intake from food (46-79% from rice and 11-23% from beans). The substantial contribution of beans to total As food intake is reported for the first time. The broad range of As concentrations in rice and beans highlights the variable and potentially large contribution of both to As food intake in places where diet consists largely of these two food categories.

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In this study, a composite with magnetic properties has been successfully synthesized by a novel and environmentally friendly route and is applied to Cd(II) adsorption for water decontamination. The quantification of the phases obtained by Rietveld refinement has shown the presence of 84% of Mn3O4 and 16% of Fe3O4. Transmission electron microscopy image shows an aggregate of Mn3O4 nanoparticles without specific orientation and the predominance of octahedral morphology with nanoparticles size estimated around 25-30 nm. The Cd(II) adsorption isotherm is fitted using the Langmuir-Freundlich model. The estimated maximum adsorption capacities of Cd(II) at pH 6 and 7 are similar (0.28 ± 0.02 and 0.31 ± 0.02 mg/m2, respectively). The kinetic results show that the studied system follows the pseudo-second-order model. The Raman results indicate that Cd is being specifically adsorbed by the Mn3O4 in the composite. The hysteresis curve of the composite Mn3O4/Fe3O4 has changed when compared to the pure magnetite; however, the coercive field after the addition of manganese oxide remains unaltered and does not change with a value around 158 Oe. The turbidity tests showed that the magnetic sedimentation was efficient and promising for wastewater treatment in large scale. These materials can be conveniently recovered by magnetic separation, avoiding the filtration steps, which will make easier the solid-liquid separation operation that follows the adsorption process.

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Doping calcium phosphates with ionic species can play an important role in biological responses promoting alkaline phosphatase activity, and, therefore inducing the generation of new bone. Thus, in this study, the synthesis of niobium-doped hydroxyapatite (Nb-HA) nanosize particles obtained by the precipitation process in aqueous media followed by thermal treatment is presented. The bioceramics were extensively characterized by X-ray diffraction, wavelength dispersive X-ray fluorescence spectrometry, Fourier transform infrared spectroscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy analysis, transmission electron microscopy, atomic force microscopy and thermal analysis regarding their chemical composition, structure and morphology. The results showed that the precipitate dried at 110 °C was composed of amorphous calcium phosphate and HA, with polidisperse particles ranging from micro to nano dimensions. After the thermal treatment at 900 °C, the bioceramic system evolved predominantly to HA crystalline phase, with evident features of particle sintering and reduction of surface area. Moreover, the addition of 10 mol% of niobium salt precursor during the synthesis indicated the complete incorporation of the Nb(V) species in the HA crystals with detectable changes in the original lattice parameters. Furthermore, the incorporation of Nb ions caused a significant refinement on the average particle size of HA. Finally, the preliminary cytocompatibility response of the biomaterials was accessed by human osteoblast cell culture using MTT and resazurin assays, which demonstrated no cytotoxicity of the Nb-alloyed hydroxyapatite. Thus, these findings seem promising for developing innovative Nb-doped calcium phosphates as artificial biomaterials for potential use in bone replacements and repair.

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Raman and IR spectra were recorded of the As-loaded Mn(3)O(4) magnetic composites obtained from the adsorption studies performed with As(III). XANES results for the composite after As(III) removal tests show that the As adsorbed is at the oxidized arsenic form, As(V). Monodentate and bidentate surface complexes are suggested for arsenic adsorption onto the composite (5-16 mg/g). Precipitation of manganese arsenate is observed for high As loading (35 mg/g).

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Long-term stability of arsenic residues is investigated by determining arsenic phases remaining in gold mining residues after two decades of impoundment. The residues, generated by arsenic coprecipitation with iron and lime, were disposed of in-lined sites for 9-16 years (pit C) and 16-23 years (pits A and B). Arsenic is present in the residues as As(V) species, predominantly in the form of amorphous iron arsenate (55-75% As(total,) pits A and B; 55-70% As(total), pit C) and sorbed onto amorphous iron-oxyhydroxides (20-33% As(total), pits A and B; 22-37% As(total), pit C). The presence of minor Ca-arsenate phases (undefined composition) and Al-arsenate coprecipitates is also indicated. The passive enrichment of iron in pits A and B, and the relative low concentration of calcium, sulfur and arsenic if compared to those of pit C, suggest that a soluble Ca-arsenate phase (e.g. CaHAsO(4).H(2)O), a fraction of gypsum and As(III) were dissolved along 16-23 years of residue disposal. The presence of As(V) only and excess iron demonstrates the importance of the oxidation state and high Fe/As ratio on long-term stability of arsenic residues.

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The geochemical fates of Fe and As are so closely correlated that methods of As removal from contaminated water are in general based on the high affinity of this metalloid for Fe (hydr)oxides. Dissimilatory Fe reducing bacteria, however, play a fundamental role in catalysing the redox transformations that ultimately control the mobility of As in anoxic environments. The potential of Al-goethites in adsorbing As(V) compared with hematite, goethite, ferrihydrite, and gibbsite, and the stability of As retained by the Fe compounds under anoxic conditions were investigated in this study. The (hydr)oxides were synthesised, and adsorption isotherms and As(V) adsorption maxima at different pH were measured. Arsenic loaded samples were anaerobically incubated in the presence of Shewanella putrefaciens, and periodically sampled to evaluate the contents of soluble As and Fe. The As(V) adsorption maxima decreased in the following order: Fh > AlGt(13) > AlGt(20) > AlGt(23) > Gb > Hm > Gt. In terms of surface area, Gb, Gt, and Hm showed higher As(V) loading capacity than Fh, suggesting available reactive sites not fully occupied by arsenate on Fh. The same hypothesis can be considered for Al-goethites, as they showed even lower arsenate loading capacity per surface area. The presence of structural Al in the goethites enhanced considerably the As uptake capacity and stability under reducing conditions. Therefore, the Al-goethites showed good potential as adsorbents to remove As from water. S. putrefaciens cells were able to utilise both noncrystalline and crystalline Fe (hydr)oxides as electron acceptors, releasing As into solution. Al-goethites showed a decrease in Fe and As mobilisation as structural Al increased.

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A fast and accurate microwave-assisted digestion method for arsenic determination by flame atomic absorption spectrometry (FAAS) in typical, complex residues from gold mining is presented. Three digestion methods were evaluated: an open vessel digestion using a mixture of HCl:HNO(3):HF acids (Method A) and two microwave digestion methods using a mixture of HCl:H(2)O(2):HNO(3) in high (Method B) and medium-pressure (Method C) vessels. The matrix effect was also investigated. Arsenic concentration from external and standard addition calibration curves (at a 95% confidence level) were statistically equal (p-value=0.122) using microwave digestion in high-pressure vessel. The results from the open vessel digestion were statistically different (p-value=0.007) whereas in the microwave digestion in medium-pressure vessel (Method C) the dissolution of the samples was incomplete.

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Arsenite adsorption onto a protein-rich biomass and, more specifically, the chemical groups involved in the uptake were investigated using Raman spectroscopy and DFT calculations. The study was based on spectroscopic analyses of raw and arsenic-loaded biomass as well as standard samples of amino acids and arsenic salts. The predominant secondary structure of the protein was identified as the beta-sheet type, with some contribution from alpha-helix structures. The participation of sulphydryl groups from cystine/cysteine molecules during the adsorption of arsenite was demonstrated. Only the gauche-gauche-gauche (g-g-g) conformation type of the disulfide bonds was involved in arsenic complexation. The formation of a pyramidal trigonal As(HCys)(3) complex was modeled according to the density functional theory (DFT). The agreement of the DFT harmonic frequencies with the RAMAN spectra of the As(HCys)(3) complex demonstrated the relevant features of the cysteine-rich biomaterial regarding arsenic uptake as well as of the mechanism involved in the As(III)/biomass interaction at a molecular level. The results also illustrate that Raman spectroscopy can be successfully applied to investigate the mechanism of metal adsorption onto amorphous biomaterials.

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The arsenic removal capacity of a natural oxide sample consisting basically of Mn-minerals (birnessite, cryptomelane, todorokite), and Fe-oxides (goethite, hematite), collected in the Iron Quadrangle mineral province in Minas Gerais, Brazil, has been investigated. As-spiked tap water and an As-rich mining effluent with As-concentrations from 100 microg L(-1) to 100 mg L(-1) were used for the experiments. Sorbent fractions of different particle sizes (<38 microm to 0.5 mm), including spherical material (diameter 2 mm), have been used. Batch and column experiments (pH values of 3.0, 5.5, and 8.5 for batch, and about pH 7.0 for column) demonstrated the high adsorption capacity of the material, with the sorption of As(III) being higher than that of As(V). At pH 3.0, the maximum uptake for As(V) and for As(III)-treated materials were 8.5 and 14.7 mg g(-1), respectively. The Mn-minerals promoted the oxidation of As(III) to As(V), for both sorbed and dissolved As-species. Column experiments with the cFeMn-c sample for an initial As-concentration of 100 microg L(-1) demonstrated a very efficient elimination of As(III), since the drinking water limit of 10 microg L(-1) was exceeded only after 7400 BV total throughput. The As-release from the loaded samples was below the limit established by the toxicity characteristic leaching procedure, thus making the spent material suitable for discharge in landfill deposits.

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This work describes a biological route for direct sorption of aqueous As(III) species, which are the most toxic and mobile arsenic species found in soils. Based upon the biochemical mechanisms that explain arsenic toxicity, we propose that a waste biomass with a high fibrous protein content obtained from chicken feathers can be used for selective As(III) adsorption. Prior to adsorption, the disulfide bridges present in the biomass are reduced by thioglycolate. Our investigations demonstrated that As(III) is specifically adsorbed on the biomass and, contrary to the behavior observed with inorganic sorbents, the lower is the pH the more effective is the removal. Arsenic uptake reaches values of up to 270 micromol As(III)/g of biomass. Analyses by synchrotron light techniques, such as XANES, demonstrated that arsenic is adsorbed in its trivalent state, an advantage over conventional techniques for As uptake, which usually require a previous oxidation stage. EXAFS analyses showed that each As atom is directly bound to three S atoms with an estimated distance of 2.26 A. The uptake mechanism is explained in terms of the structural similarities between the As(III)-biomass complex structure and that of arsenite ions and Ars-Operon system encoded proteins and phytochelatins. The biological route presented here offers the perspective of a direct removal of arsenic in its reduced form.

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