Within human-impacted areas, high levels of inorganic compounds in groundwater are broadly and preventively attributed to local anthropogenic pollution, thoroughly disregarding geogenic natural background levels. Particularly in landfills, a proper evaluation of the significant adverse environmental effects should be completed through a detailed groundwater characterization, and appropriate reference values established prior to landfill onset. However, the monitoring network may lack a full hydrogeological representativeness of the site and of the background conditions of groundwater. This study aimed at disentangling natural and anthropogenic impacts through a synoptic analysis of hydrogeochemical, isotopic and microbiological characteristics of groundwaters from a municipal solid waste landfill area in Central Italy. Samples were collected during four seasonal monitoring surveys from the mostly anoxic aquifer underlying the target area. Field parameters, inorganic and organic compounds, environmental isotopes, faecal contamination, and microbial community characteristics were determined, along with a detailed hydrogeological conceptual model. Key inorganic contaminants (As, Fe and Mn) exceeded the local threshold values in most of the sampling points, while organic contamination was generally very low. Stable isotopes suggested that groundwater originated mainly from local rainfall, except at one monitoring points where tritium levels might indicate moderate impact. Microbiological data and the microbial community characterization, assessed by flow cytometry and BIOLOG assays, provided further supportive information, also highlighting fundamental effects of groundwater quality alterations. Overall, an integrated multi-parametric approach proved suitable to distinguish geogenic and anthropogenic impacts, thus improving strategies and schemes for protection and management of groundwaters in landfills and waste related industrial areas.

Defining natural background levels (NBL) of geochemical parameters in groundwater is a key element for establishing threshold values and assessing the environmental state of groundwater bodies (GWBs). In the Apulia region (Italy), carbonate sequences and clastic sediments host the 29 regional GWBs. In this study, we applied the Italian guidelines for the assessment of the NBLs, implementing the EU Water Framework Directive, in a south-European region characterized by the typical Mediterranean climatic and hydrologic features. Inorganic compounds were analyzed at GWB scale using groundwater quality data measured half-yearly from 1995 to 2018 in the regional groundwater monitoring network (341 wells and 20 springs). Nitrates, chloride, sulfate, boron, iron, manganese and sporadically fluorides, boron, selenium, arsenic, exceed the national standards, likely due to salt contamination along the coast, agricultural practices or natural reasons. Monitoring sites impacted by evident anthropic activities were excluded from the dataset prior to NBL calculation using a web-based software tool implemented to automate the procedure. The NBLs resulted larger than the law limits for iron, manganese, chlorides, and sulfates. This methodology is suitable to be applied in Mediterranean coastal areas with high anthropic impact and overexploitation of groundwater for agricultural needs. The NBL definition can be considered one of the pillars for sustainable and long-term groundwater management by tracing a clear boundary between natural and anthropic impacts.