The distribution of arsenic in shallow alluvial groundwater under agricultural land in central Portugal: Insights from multivariate geostatistical modeling

In this study multivariate and geostatistical methods are jointly applied to model the spatial and temporal distribution of arsenic (As) concentrations in shallow groundwater as a function of physicochemical, hydrogeological and land use parameters, as well as to assess the related uncertainty. The study site is located in the Mondego River alluvial body in Central Portugal, where maize, rice and some vegetable crops dominate. In a first analysis scatter plots are used, followed by the application of principal component analysis to two different data matrices, of 112 and 200 samples, with the aim of detecting associations between As levels and other quantitative parameters. In the following phase explanatory models of As are created through factorial regression based on correspondence analysis, integrating both quantitative and qualitative parameters. Finally, these are combined with indicator-geostatistical techniques to create maps indicating the predicted probability of As concentrations in groundwater exceeding the current global drinking water guideline of 10 μg/l. These maps further allow assessing the uncertainty and representativeness of the monitoring network. A clear effect of the redox state on the presence of As is observed, and together with significant correlations with dissolved oxygen, nitrate, sulfate, iron, manganese and alkalinity, points towards the reductive dissolution of Fe (hydr)oxides as the essential mechanism of As release. The association of high As values with rice crop, known to promote reduced environments due to ponding, further corroborates this hypothesis. An additional source of As from fertilizers cannot be excluded, as the correlation with As is higher where rice is associated with vegetables, normally associated with higher fertilization rates. The best explanatory model of As occurrence integrates the parameters season, crop type, well and water depth, nitrate and Eh, though a model without the last two parameters also gives quite satisfactory results.

► We studied arsenic levels in shallow alluvial groundwater under agricultural land.
► Multivariate geostatistics is used to model spatio-temporal arsenic occurrence.
► Results indicate the dominant role of reductive dissolution of Fe (hydr)oxides.
► Redox state is linked to rice crops, fertilizers can provide additional As source.
► Best regression model for As uses season, crop, well and water depth, Eh and NO3−.