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Legislative Decree 152/2006 requires Public Authorities to identify the subjects who are responsible for soil and groundwater contamination. In highly urbanized areas with a long industrial history and an elevated number of potential contaminant sources, as in N-W Milano Functional Urban Area (FUA), their identification can be difficult. Since the groundwater flow has showed consistent changes in the last 30 years as in Milan, the problem became even more complicate. The Public Authorities put in charge by the law, i.e., Regione Lombardia and Città Metropolitana Milanese, need new methodologies to assist them in finding the source locations and implementing remediation actions. The aim of this study is, coupling unsteady flow with fate and transport model of Chlorinated Hydrocarbons, to reconstruct the potential impact of a former chemical plant on public wells in the N-W area of Milano. The proposed methodology consists in (a) reconstruction of the piezometric trend over time (1980–2018) by means of a transient flow model (MODFLOW2005 + Parameter Estimation - PEST) and (b) simulation of transport as a function of the flow variations in time. The obtained results were compared with the previous ones obtained with a quasi-steady model (no changes in time-dependent parameters). Finally, a predictive scenario was performed to assess the potential evolution of tetrachloroethylene (PCE) in groundwater; on this frame, strategies to monitor and remediate the contamination were proposed.

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Water Framework Directive and Groundwater Directive (2006/118/CE) represent the main European regulations on water resources quality, requiring the identification and management of contamination sources threatening the achievement of acceptable groundwater quality status. The sources of groundwater contamination can be classified into two different categories: 1) point sources (PS), which are identified areas releasing plumes of high/very high concentrations (i.e. hot-spots) and 2) multiple-point sources (MPS) constituted by a series of unidentifiable small sources clustered in a large area, generating a diffuse contamination. The latter category predominates in European Functional Urban Areas and cannot be managed with the usual remediation techniques such as those conceived for large/medium contaminated sites, mainly because of the difficulty to identify the many different source areas releasing small contaminant mass. Consequently, the usual remediation procedures are not economically sustainable and often fail to provide results in an acceptable time frame. A powerful tool in this context is transport modeling, as it can be used in combination with statistical methods to assess MPS groundwater contamination even in a highly undetermined setting. Due to the uncertainty related to the exact position and intensity of MPS, a numerical model (MODFLOW/MT3DMS) was implemented in a pilot area in the North-Eastern sector of the Milano FUA. Using the inverse calibration code PEST, a model was calibrated representing the diffuse PCE source field (Italian Law limit is within 1.1 mg/l). This was then used as input to a statistical process based on the Null-Space Monte Carlo (NSMC) method, which allows to generate unlimited sets of sources, all respecting the measured concentrations. 99 different realisations were thus obtained, each attributing a contaminant inflow (with varying concentrations) to every cell of the model top layer. The model minimizing the objective function (composed by the diffuse concentration targets in monitoring wells), gives useful information to assess the overall contaminant sources distribution and to identify the probability of each domain sector to contribute to the contaminant mass inflow