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Groundwater deficits occur in several areas of Central Mexico, where water resource assessment is limited by the availability and reliability of field data. In this context, GRACE and InSAR are used to remotely assess groundwater storage loss in one of Mexico's most important watersheds in terms of size and economic activity: the Lerma-Santiago-Pacifico (LSP). In situ data and Land Surface Models are used to subtract soil moisture and surface water storage changes from the total water storage change measured by GRACE satellites. As a result, groundwater mass change time-series are obtained for a 12 years period. ALOS-PALSAR images acquired from 2007 to 2011 were processed using the SBAS-InSAR algorithm to reveal areas subject to ground motion related to groundwater over-exploitation. In the perspective of providing guidance for groundwater management, GRACE and InSAR observations are compared with official water budgets and field observations. InSAR-derived subsidence mapping generally agrees well with official water budgets, and shows that deficits occur mainly in cities and irrigated agricultural areas. GRACE does not entirely detect the significant groundwater losses largely reported by official water budgets, literature and InSAR observations. The difference is interpreted as returns of wastewater to the groundwater flow systems, which limits the watershed scale groundwater depletion but suggests major impacts on groundwater quality. This phenomenon is enhanced by ground fracturing as noticed in the field. Studying the fate of the extracted groundwater is essential when comparing GRACE data with higher resolution observations, and particularly in the perspective of further InSAR/GRACE combination in hydrogeology.In Mexico, groundwater fulfills more than 70% of the water needs for the 120 million inhabitants [Instituto Nacional de Estad ıstica y Geograf ıa, 2015]. Annual rainfall rates show a smooth transition from high Key Points: InSAR and GRACE observations are compared with the groundwater management scheme Discordance between GRACE, InSAR, and water budgets suggests important wastewater recharge Cointerpreting GRACE and InSAR brings an unprecedented insight into groundwater sustainability Correspondence to: P. Castellazzi,

The high levels of acid extractable organics (AEOs) containing naphthenic acids (NAs) found in oil sands process-affected waters (OSPW) are a growing concern in monitoring studies of aquatic ecosystems in the Athabasca oil sands region. The complexity of these compounds has substantially hindered their accurate analysis and quantification. Using a recently developed technique which determines the intramolecular carbon isotope signature of AEOs generated by online pyrolysis (δ(13)Cpyr), natural abundance radiocarbon, and high resolution Orbitrap mass spectrometry analyses, we evaluated the sources of AEOs along a groundwater flow path from a major oil sands tailings pond to the Athabasca River. OSPW was characterized by a δ(13)Cpyr value of approximately -21‰ and relatively high proportions of O₂ and O₂S species classes. In contrast, AEO samples located furthest down-gradient from the tailings pond and from the Athabasca River were characterized by a δ(13)Cpyr value of around -29‰, a greater proportion of highly oxygenated and N-containing compound classes, and a significant component of nonfossil and, hence, non-bitumen-derived carbon. The groundwater concentrations of mining-related AEOs determined using a two end-member isotopic mass balance were between 1.6 and 9.3 mg/L lower than total AEO concentrations, implying that a less discriminating approach to quantification would have overestimated subsurface levels of OSPW. This research highlights the need for accurate characterization of "naphthenic acids" in order to quantify potential seepage from tailings ponds.

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