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.