Groundwater quality trend and trend reversal assessment in the European Water Framework Directive context: an example with nitrates in Italy.

Groundwater resources are of utmost importance in sustaining water related ecosystems, including humans. The long-lasting impacts from anthropogenic activities require early actions, owing to the natural time lag in groundwater formation and renewal. The European Union (EU) policy, within the implementation of the Water Framework Directive (WFD), requires Member States to identify and reverse any significant and sustained upward trend in the concentration of pollutants, defining specific protection measures to be included in the River Basin Management Plans (RBMP). In Italy, official guidelines for trend and trend reversal assessment have been published recently. Statistical methods, such as the Mann-Kendall test for trend analysis and the Sen's method for estimating concentration scenarios, should be applied at the fixed terms stated by the WFD implementation cycles to identify upward trends, while the Pettitt test is proposed for the identification of trend reversal. In this paper, we present an application of a slightly modified version of the Italian Guidelines to a groundwater body in Northern Italy featuring nitrate pollution and discuss its advantages and limitations. In addition to Pettitt test, for the trend reversal analysis, we apply the Mann-Kendall test in two sections and compare the results. We conclude that this method seems more reliable than Pettitt test to identify a reversal point in quality time series. The overall procedure can be easily applied to any groundwater body defined at risk across Europe, for the assessment of the upward trends of pollutants and their reversal, even with little chemical monitoring data. Although focused on the EU legislative framework, this procedure may be relevant for a wider context, allowing to individuate upward trend as early warning for contamination processes in an integrated water resources management context.

Evaluation of groundwater contamination sources by plant protection products in hilly vineyards of Northern Italy.

In Europe, 25% of groundwater has poor chemical status. One of the main stressors is agriculture, with nitrates and plant protection products (PPPs) causing failure in 18% and 6.5%, respectively, of groundwater bodies (by area). EU legislation for the placement of the PPPs on the market is one of the most stringent in the world. However, recent monitoring studies in hilly vineyards of Tidone Valley, north-west of Italy, show presence of PPPs used for grapevine cultivation in 15 out of 26 groundwater wells monitored, at values above the Environment Quality Standard (EQS) for groundwater (0.1 µg/L). However, no information about the contamination sources are available. Therefore, the objective of the present work is to evaluate the groundwater contamination sources by PPPs, in a small catchment with intensive viticulture, by collecting and integrating monitoring data, sub-surface water movement data and territorial characteristics. The results show that in wells used for PPP's mixture preparation and sprayer washing located at the top of hilly vineyards, with low slope and no water movement in the surrounding soil, the contamination is most likely from point sources. On the contrary, for wells located in a fenced area at the bottom of the hill, far away from vineyards and being used for drinking water production, the contamination is most likely from diffuse sources. Our results were used to raise awareness on groundwater contamination from PPPs among farmers in the study area; moreover a waterproof platform for sprayers washing, equipped with wastewater recovery and disposal system, able to avoid point-source contamination, was implemented in a local demonstration farm. Several demonstration activities were then organised with the farmers of the entire Valley in order to show its functionality and promote its diffuse use.

Climate-change potential effects on the hydrological regime of freshwater springs in the Italian Northern Apennines.

In large areas of the Italian Northern Apennines, hundreds of low-yield springs provide water for drinking and industrial purposes, with short groundwater flow paths being formed within fractured sedimentary rock units. This hydrogeological setting results in spring water discharges that closely follow meteoric water recharge patterns, leading to low-flow periods concentrated in the summer/early autumn. Therefore, the springs' outflow can be very sensitive to a shortage in water recharge, as it was the case in 2003 and 2017, when a prolonged period of drought caused severe water management issues. This work analyses how a group of such springs responds to climate change. In particular, we first validated a hydrological rainfall-runoff model on the basis of daily discharge data collected between 2013 and 2016. Then, outflows were simulated for baseline (1984-2013) and future periods (2021-2050) using weather data provided by five RCM-GCM combinations. Finally, we performed statistical analyses aiming to examine the intra-annual variability in discharge rates, low-flow indices, flow-duration curves and the length of low-flows. Results show no evidence of change in mean annual discharges, but future climate estimates suggest a slight change to seasonal discharges in the future, with a marked increase of discharge during winter and spring, and a decrease in summer and autumn. Q(95) and 7Q10 low-flow indices (i.e. the daily discharge exceeded 95% of the time and the minimum weekly discharge associated with a 10-year recurrence interval, respectively) are significantly affected by the climate change (-21.8% and -25.0%, respectively), while droughts are expected to be more frequent: the number of years with a consecutive low-flow between 51 and 100days to increase by a third, and between 101 and 150 to duplicate.

Natural background levels and threshold values of chemical species in three large-scale groundwater bodies in Northern Italy.

We analyze natural background levels (NBLs) and threshold values (TVs) of spatially distributed chemical species (NH(4), B and As) which may be a potential pressure and concern in three large scale alluvial and fluvio-deltaic aquifers at different depths of the Apennines and Po river plains in Emilia-Romagna, Northern Italy. Our results are based on statistical methodologies designed to separate the natural and anthropogenic contributions in monitored concentrations by modeling the empirical distribution of the detected concentration with a mixture of probability density functions. Available chemical observations are taken over a 20 years period and are associated with different depths and cover planar investigation scales of the order of hundreds of kilometers. High concentration values detected for NH(4) and B appear to be related to high natural background levels. Due to interaction with the host rock in different geochemical environments we observed that concentration vary in time and space (including in depth) consistently with the hydrogeochemical features and the occurrence of natural attenuation mechanisms in the analyzed reservoirs. Conversely, estimated As NBLs are not consistent with the conceptual model of the hydrogeochemical behavior of the systems analyzed and experimental evidences of As content in aquifer cores. This is due to the inability of these techniques to incorporate the complex dynamics of the processes associated with the specific hydrogeochemical setting. Statistical analyses performed upon aggregating the concentration data according to different time observation windows allow identifying temporal dynamics of NBLs and TVs of target compounds within the observation time frame. Our results highlight the benefit of a dynamic monitoring process and analysis of well demarcated groundwater bodies to update the associated NBLs as a function of the temporal dependence of natural processes occurring in the subsurface. Monitoring protocols could also include the detailed evaluation of the geochemistry (redox) of the aquifers.

Heavy metal in sediments and bioaccumulation in the bivalve Corbula gibba in a drilling discharge area.

The longterm bioavailability of heavy metals in sediments of a Northern Adriatic Sea shelf area affected by drilling mud and cutting discharges was discussed. Levels of Mn, Cu, Cr, Zn and Pb in different geochemical phases of the sediment and in soft tissues of the bivalve Corbula gibba were recorded and the relationships between biological and geochemical metal investigated. Total metal content, acetic acid extractable-, exchangeable-, carbonate-, easily reducible-, moderately reducible-, oxidable- and residual-fractions were determined on sediment samples. Corbula gibba was collected from wet sediments at the same times and sites, and the soft-tissue metal contents were determined. Correlations show that the fractions with greatest bioavailability are the exchangeable and carbonate for Cr and the exchangeable, carbonate, easily and moderately reducible fractions for Zn. Data also show a possible bioavailability of Pb only from the residual fraction, consisting of very resistant matter of more recent anthropogenic origin. Near the platform, total Mn content in sediments and in C. gibba tissues show a strong correlation suggesting that this organism is sensitive to variations of the Mn-oxi-hydroxides superficial film. No relationships were found between biological and sediment-bound Cu, however the discharged muds did not cause Cu enrichment. The metal fraction determined by weak acetic acid extraction at no point seems related to metal levels in Corbula gibba.