Basic oxygen furnace sludge to treat industrial arsenic- and sulfate-rich acid mine drainage.

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.

Effects of aluminum and soil mineralogy on arsenic bioaccessibility.

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.

3D sponges of chemically functionalized chitosan for potential environmental pollution remediation: biosorbents for anionic dye adsorption and 'antibiotic-free' antibacterial activity.

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.

Gastric/lung bioaccessibility and identification of arsenic-bearing phases and sources of fine surface dust in a gold mining district.

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.

Versatility of iron-rich steel waste for the removal of high arsenic and sulfate concentrations in water.

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.

Low arsenic bioaccessibility by fixation in nanostructured iron (Hydr)oxides: Quantitative identification of As-bearing phases.

A new analytical protocol was developed to provide quantitative, single-particle identification of arsenic in heterogeneous nanoscale mineral phases in soil samples, with a view to establishing its potential risk to human health. Microscopic techniques enabled quantitative, single-particle identification of As-bearing phases in twenty soil samples collected in a gold mining district with arsenic concentrations in range of 8 to 6354 mg kg-1. Arsenic is primarily observed in association with iron (hydr) oxides in fine intergrowth with phyllosilicates. Only small quantities of arsenopyrite and ferric arsenate (likely scorodite) particles, common in the local gold mineralization, were identified (e.g., 7 and 9 out, respectively, of app. 74,000 particles analyzed). Within the high-arsenic subgroup, the arsenic concentrations in the particle size fraction below 250µm ranges from 211 to 4304 mg kg-1. The bioaccessible arsenic in the same size fraction is within 0.86-22 mg kg-1 (0.3-5.0%). Arsenic is trapped in oriented aggregates of crystalline iron (hydr)oxides nanoparticles, and this mechanism accounts for the low As bioaccessibility. The calculated As exposure from soil ingestion is less than 10% of the arsenic Benchmark Dose Lower Limit - BMDL0.5. Therefore, the health risk associated with the ingestion of this geogenic material is considered to be low.

Dietary arsenic exposure in Brazil: The contribution of rice and beans.

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.