RESUMO
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.
Assuntos
Arsênio , Poluentes do Solo , Alumínio , Arsênio/análise , Humanos , Mineração , Solo , Poluentes do Solo/análiseRESUMO
Bioaccessibility (BAC) of fine surface dust (FSD, particle size ≤10⯵m) and surface dust samples (particle size ≤250⯵m) 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%, nâ¯=â¯5 and G.I 3.4⯱â¯2%, nâ¯=â¯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⯵m 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⯵g 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.
Assuntos
Arsênio/análise , Exposição Ambiental/análise , Poluentes do Solo/análise , Poeira/análise , Exposição Ambiental/estatística & dados numéricos , MineraçãoRESUMO
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% (nâ¯=â¯17) with a bioaccessible concentration of 4.1⯱â¯3.7â¯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 (ingestionâ¯+â¯inhalation) is about 10% of the JECFA BMDL0.5 of 3⯵g/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 2â¯L of water containing 10⯵g/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.
Assuntos
Arsênio/análise , Exposição Ambiental/análise , Poluentes do Solo/análise , Brasil , Exposição Ambiental/estatística & dados numéricos , Monitoramento Ambiental , Humanos , Mineração , Medição de RiscoRESUMO
Use of lime to mitigate acid mine drainage is, in general, accompanied by precipitation of iron (Fe) and aluminium (Al) (hydr)oxides which may increase the removal of trace elements from water. This work aimed to evaluate the precipitation of Fe/Al (hydr)oxides to remove rare earth elements (REE) from contaminated water and the stability of precipitates. Two sets of 60-day syntheses were carried out using different Fe/Al/REE molar ratios, for europium (Eu) and holmium (Ho). The pH was periodically adjusted to 9.0, and the stability of the resulting precipitates was evaluated by water-soluble and BCR extractable phases, namely (1) acid soluble, extracted by 0.11 mol L-1 acetic acid; (2) reducible, extracted with 0.5 mol L-1 hydroxylamine hydrochloride; and (3) oxidisable, extracted with 8.8 mol L-1 hydrogen peroxide efficiencies of the water treatments for both Eu and Ho that were higher than 99.9% irrespective to the Fe/Al/REE molar ratios. Water-soluble phases of Eu and Ho were lower than 0.01% of the total contents in the precipitates. Recoveries from precipitates by Bureau Communautaire de Référence (BCR) sequential extractions increased with increasing concentrations of Eu and Ho. Acetic acid extracted higher amounts of REE, but Eu recovery was superior to Ho. Lepidocrocite was formed as Eu concentration increased which decreased its stability in the precipitates.
Assuntos
Óxido de Alumínio/química , Európio/isolamento & purificação , Compostos Férricos/química , Hólmio/isolamento & purificação , Mineração , Poluentes Químicos da Água/isolamento & purificação , Ácidos , Compostos de Cálcio , Ferro , Oxirredução , Óxidos , Poluentes Químicos da Água/análise , Purificação da ÁguaRESUMO
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.
Assuntos
Arsênio/análise , Exposição Ambiental/análise , Contaminação de Alimentos/análise , Oryza/química , Phaseolus/química , Agricultura , Brasil , Dieta , HumanosRESUMO
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.