Source and mobility of minor and trace elements in a volcanic aquifer system: Mt. Vulture (southern Italy)

In this paper we provide a geochemical investigation on 34 groundwater samples in the Mt. Vulture volcanic aquifer representing one of the most important groundwater resources of the southern Italy pumped for drinking and irrigation supply. The present study includes the first data on the abundance and mobility of minor and trace elements and the thermodynamic considerations on water–rock interaction processes in order to evaluate the conditions of alkali basalt weathering by waters enriched in magma-derived CO2. The results highlight the occurrence of two hydrofacies: bicarbonate alkaline-earth and alkaline waters deriving from low-temperature leaching of volcanic rocks of Mt. Vulture, and bicarbonate-sulfate-alkaline waters (high-salinity waters) related to prolonged water circulation in alkali and feldspathoids-rich pyroclastic layers interbedded with clay deposits. The Al-normalized relative mobility (RM) of metals in Vulture's aquifer varies over a wide range (10− 1 < RM < 104), confirming that the basalt weathering is not a congruent and isochemical process. Chemical equilibrium studies show that the bicarbonate alkaline-earth and alkaline waters, having a short interaction with silicate minerals, plot very close to the kaolinite–smectite stability boundary, whereas the high-salinity waters fall in the stability field of smectite and muscovite because of prolonged interaction with alkali and feldspathoids-rich pyroclastic layers. Overall, for the bicarbonate alkaline-earth and alkaline waters, the release of toxic metals in solutions is related to the spatial variation of host-rock geochemistry, the high-salinity waters, collected near urban areas, show values higher than legal limits for Ni and As, likely as a consequence of anthropogenic contribution.

► The investigated groundwaters have a bicarbonate alkaline-earth and bicarbonate-sulfate-alkaline composition.
► The former type is due to low-temperature leaching of volcanic rocks and also to the greater dissolved CO2 rich-gases.
► The latter (high salinity waters) is related to water circulation in feldspathoids-rich pyroclastic layers and clays.
► The Al-normalized relative mobility of metals varies over a wide range (10−1 < RM < 104).
► The potentially toxic metals have low concentrations, with the exception of Ni and As contents in high-salinity waters.