This is the first hydro-geochemical investigation carried out on the Roccamonfina Volcanic Complex groundwaters. The chemistry of Roccamonfina waters is defined by water-rock and water-rock-gas interactions. In fact, interactions between rocks of the first eruptive high-K formations and circulating groundwaters are recognized by high K concentrations. On the other hand, inverse concentration of calcium versus alkali metals is related to two different rock interactions occurring in different areas of the volcano: (a) within the caldera where groundwaters flow within latite and pyroclastic formations releasing calcium, and (b) similarly at the base of the volcano where groundwaters flowing from surrounding carbonates got strongly enriched in Ca. These geochemical processes are also associated with K (SE of caldera) and Mg/Ca (in sites located at the NE base of the volcano) decrease. Completely different dynamics occurs at Riardo groundwaters (SE). Here waters are the result of a mix between the Roccamonfina deep aquifer and the carbonate aquifer of the Riardo plain. Rich-CO 2 emissions make these waters strongly mineralized. Minor elements show a similar geochemical behavior of major ions and are crucial defining interactions processes. The evolution of Roccamonfina groundwaters is also evident along the simultaneous enrichment of Ba, Sr, and Ca. Ba increase is the result of deep local carbonate alteration enhanced by CO 2 emissions and, the lower Sr/Ca ratio, from 10 to 2 (ppb/ppm), is also due to the same process. In the light of our results the Roccamonfina aquifer can be schematically divided into two main reservoirs: (a) a superficial aquifer which basically follows the volcanic structure morphology and tectonics and (b) a deeper reservoir, originating within the oldest Roccamonfina volcano ultra potassic lavas and then flowing into the carbonate aquifers of the neighboring plain. Eventually, the chemistry of the Roccamonfina aquifer does not show any specific and visible pollution, contrary to what happens in the volcano surrounding plains. In fact, only 14% of the samples we collected (206) show a NO 3 content[30 mg/l. These sites are all located at the base of the volcano, near the plain.

The Campanian Plain (CP) shallow aquifer (Southern Italy) represents a natural laboratory to validate geochemical methods for differentiating diffuse anthropogenic pollution from natural water-rock interaction processes. The CP is an appropriate study area because of numerous potential anthropogenic pollution vectors including agriculture, animal husbandry, septic/drainage sewage systems, and industry. In order to evaluate the potential for geochemical methods to differentiate various contamination vectors, 538 groundwater wells from the shallow aquifer in Campanian Plain (CP) were sampled. The dataset includes both major and trace elements. Natural water-rock interactions, which primarily depend on local lithology, control the majority of geochemical parameters, including most of the major and trace elements. Using prospective statistical methods in combination with the traditional geochemical techniques, we determined the chemical variables that are enriched by anthropogenic contamination (i.e. NO3, SO4 and U) by using NO3 as the diagnostic variable for detecting polluted groundwater. Synthetic agricultural fertilizers are responsible for the majority of SO4 and U pollution throughout the CP area. Both SO4 and U are present in the groundmass of synthetic fertilizers; the uranium concentration is specifically applicable as a tracer for non-point source agricultural fertilizer contamination. The recognition of non-geological (anthropogenic) inputs of these elements has to be considered in the geochemical investigations of contaminated aquifers.

No abstract

No abstract