An analysis of 70 wells that tap groundwater from depths of up to 260 m in and around the town of Cremona, N. Italy, shows that 50 of them contain more than 10 μg/L of arsenic. Concentrations of As >10 ppb are accompanied by concentrations of Fe ranging from <0.1 to 6 mg/L and high concentrations of NH4 and Mn (<19 and <1.3 mg/L, respectively). The associations suggest that the mechanism of mobilization of As is the reductive dissolution of Fe oxides driven by the degradation of peat, which is commonly found in the aquifer system. Groundwater in the aquifer has a component of downward flow via leakage through aquitards and flow through lateral discontinuities in them. Along these flow paths, As is released by reductive dissolution of Fe oxides in shallow and intermediate aquifers (0-85 m below surface), reaching up to 183 μg/L, and is attenuated (<95 μg/L) at greater depths (100-150 m). Coprecipitation in iron sulfides could play an important role in As attenuation at these depths. The lower As concentration (<37 μg/L) in the deepest aquifer (160-260 m) is less related to the As concentration of the overlying aquifers because the groundwater here has a component of upward flow.
Arsenic contamination of groundwater aquifers is an issue of global concern. Among the affected sites, in several Italian groundwater aquifers arsenic levels above the WHO limits for drinking water are present, with consequent issues of public concern. In this study, for the first time, the role of microbial communities in metalloid cycling in groundwater samples from Northern Italy lying on Pleistocene sediments deriving from Alps mountains has been investigated combining environmental genomics and cultivation approaches. 16S rRNA gene libraries revealed a high number of yet uncultured species, which in some of the study sites accounted for more of the 50% of the total community. Sequences related to arsenic-resistant bacteria (arsenate-reducing and arsenite-oxidizing) were abundant in most of the sites, while arsenate-respiring bacteria were negligible. In some of the sites, sulfur-oxidizing bacteria of the genus
Sulfuricurvum
accounted for more than 50% of the microbial community, whereas iron-cycling bacteria were less represented. In some aquifers, arsenotrophy, growth coupled to autotrophic arsenite oxidation, was suggested by detection of arsenite monooxygenase (
aioA
) and 1,5-ribulose bisphosphate carboxylase (RuBisCO)
cbbL
genes of microorganisms belonging to
Rhizobiales
and
Burkholderiales
. Enrichment cultures established from sampled groundwaters in laboratory conditions with 1.5 mmol L
-1
of arsenite as sole electron donor were able to oxidize up to 100% of arsenite, suggesting that this metabolism is active in groundwaters. The presence of heterotrophic arsenic resistant bacteria was confirmed by enrichment cultures in most of the sites. The overall results provided a first overview of the microorganisms inhabiting arsenic-contaminated aquifers in Northern Italy and suggested the importance of sulfur-cycling bacteria in the biogeochemistry of arsenic in these ecosystems. The presence of active arsenite-oxidizing bacteria indicates that biological oxidation of arsenite, in combination with arsenate-adsorbing materials, could be employed for metalloid removal.
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