Geochemical modeling and multivariate statistical evaluation of trace elements in arsenic contaminated groundwater systems of Viterbo Area, (Central Italy)

Contamination of groundwater by naturally occurring arsenic has recently become a disturbing environmental problem in Viterbo area, Central Italy. Arsenic concentrations in most of the public supply networks exceed the maximum allowable limit of 10 μg/l (WHO) for drinking water. The primary purpose of this paper is to obtain a better understanding of the factors contributing to the high levels of As in water supply networks. This study focuses on (a) the determination of basic hydrochemical characteristics of groundwater, (b) the identification of the major sources and processes controlling the As contamination in public supply networks, (c) to find out possible relationships among the As and other trace elements through principal component analysis (PCA). Groundwater samples from public water supply wells and springs were collected and analysed for physico-chemical parameters and trace elements. Springs and well water samples are predominantly of the Na-HCO3, Na -Ca-HCO3 and Ca-HCO3 types and the highest arsenic concentrations were observed in Na-HCO3 type water. Eh-pH diagrams reveal that H2AsO4 (-) and HAsO4 (2-), As(V) arsenate, are the dominating As species highlighting slightly to moderately oxidizing conditions. Geochemical modeling indicates that arsenic-bearing phases were undersaturated in the groundwater, however most of the samples were saturated with respect to Fe (i.e. magnetite, hematite and goethite) and Al (diaspore and boehmite) oxide and hydroxide minerals. Concentrations of As, Li, B, Co, Sr, Mo, U and Se are highly correlated (r > 0.7) with each other, however in some groundwater samples As show also good correlations (r > 0.5) with Fe and Mn elements reflecting the relationships among the trace elements result from different geochemical processes. Evaluation of the principal component (PCA) analysis and geochemical modeling suggest that the occurrence of As and other trace element concentrations in groundwater are probably derived from (i) weathering and/or dissolution of volcanic source aquifer materials and (ii) adsorption/desorption processes on the Fe and Al oxide and hydroxide minerals.