Mobility of trace elements in a coastal contaminated site under groundwater salinization dynamics

Water pollution is a significant issue resulting from past long-term actions. The remediation projects carried out under law constraints for industrial plants, which have been the major contributors to environmental and water pollution, are currently providing a significant amount of data about contaminated soil, surface waters, and groundwater. Most of such plants worldwide are in coastal zones. Based on a significant amount of chemical and environmental data for a coastal contaminated site subject to variable groundwater salinization, this study aimed to understand the mobility of some trace elements because of coastal zone dynamics. Data concerned 688 groundwater samples, including As, Hg, Cd, Cr_tot, Cu, Ni, Pb, V, Se, Zn, pH, electrical conductivity, chlorides, total organic carbon and organic contaminants as quantitative variables, enhanced by additional qualitative variables such as groundwater salinity, season, water level, precipitation, and industrial activity type to make the dataset as representative as possible of the site under investigation. The study used robust multivariate statistical analyses to analyse the complex dataset and explain the relevant factors influencing contaminant behaviour under different environmental conditions. The Multivariate Statistical Analysis distinguished three clusters of trace elements with diverse reactivity to changes in groundwater salinization. The first includes Se, Cu, Cr_tot, V, and Ni, showing the highest correlation with electrical conductivity and chlorides because of their high affinity to form chloride or organic chloride complexes and for ion competition. Zn and Pb cluster in the second group: they are less reactive to groundwater salinization and more influenced by cation and anion competition and organic matter. The mobility of Hg and As (third cluster) significantly correlates with Fe and Mn, underlining the dominant role of reductive dissolution of trace elements-bearing minerals (Fe/Mn/Al-oxy-hydroxides) and metal-organic complexes. The correlation between the clustering of variables in groundwater and soils shows the influence of sediment structure, mineral composition, and physical and chemical soil conditions on the distribution in soils of trace elements and their transport to groundwater. The study proposes a valuable approach for assessing the effects of salinization in contaminated coastal aquifers. It supports planning multi-purpose characterization and monitoring campaigns of contaminated coastal sites and provides guidance on the correct associated remediation projects.