Abteilung Wasserressourcen und Trinkwasser

Substituted para-benzoquinones and hydroquinones are ubiquitous transformation products that arise during oxidative water treatment of phenolic precursors, for example through ozonation or chlorination. The benzoquinone structural motive is associated with mutagenicity and carcinogenicity, and also with induction of the oxidative stress response through the Nrf2 pathway. For either endpoint, toxicological data for differently substituted compounds are scarce. In this study, oxidative stress response, as indicated by the AREc32 in vitro bioassay, was induced by differently substituted para-benzoquinones, but also by the corresponding hydroquinones. Bioassays that indicate defense against genotoxicity (p53RE-bla) and DNA repair activity (UmuC) were not activated by these compounds. Stability tests conducted under incubation conditions, but in the absence of cell lines, showed that tested para-benzoquinones reacted rapidly with constituents of the incubation medium. Compounds were abated already in phosphate buffer, but even faster in biological media, with reactions attributed to amino- and thiol-groups of peptides, proteins, and free amino acids. The products of these reactions were often the corresponding substituted hydroquinones. Conversely, differently substituted hydroquinones were quantitatively oxidized to p-benzoquinones over the course of the incubation. The observed induction of the oxidative stress response was attributed to hydroquinones that are presumably oxidized to benzoquinones inside the cells. Despite the instability of the tested compounds in the incubation medium, the AREc32 in vitro bioassay could be used as an unspecific sum parameter to detect para-benzoquinones and hydroquinones in oxidatively treated waters.

Study region: Northeastern Iran.
Study focus: In northeastern Iran, water needed for municipal and agricultural activities mainly comes from groundwater resources. However, it is subject to substantial anthropogenic and geogenic contamination. We characterize the sources of groundwater contamination by employing an integrated approach that can be applied to the identification of large-scale contamination sources in other regions. An existing dataset of georeferenced water quality parameters from 676 locations in northeast of Iran was analyzed to investigate the geochemical properties of groundwater. Gridding of the parameters graphically illustrates the areas affected by high concentrations of As, Cl⁻, Cr, Fe, Mg²⁺, Na⁺, NO₃⁻, Se, and SO₄^2-. We then identified potential anthropogenic and geogenic contamination sources by employing random forest (RF) regression modeling.
New hydrological insights for the region: Random forest (RF) models show that the major ions, As, Cr, Fe, and Se content of groundwater are mainly determined by geology in the study area. Modeling also links groundwater NO₃⁻ contamination with sewage discharge into aquifers as well as the application of nitrogenous and animal-waste fertilizers. Areas of high salinity result from evaporate deposits and irrigation return flow. Medium to high non-carcinogenic health risk is found in areas with high concentrations of geogenic As and Cr in groundwater. Our approach can be applied elsewhere to analyze regional groundwater quality and associated health risks as well as identify potential sources of contamination.

Land-use changes often have significant impact on the water cycle, including changing groundwater/surface-water interactions, modifying groundwater recharge zones, and increasing risk of contamination. Surface runoff in particular is significantly impacted by land cover. As surface runoff can act as a carrier for contaminants found at the surface, it is important to characterize runoff dynamics in anthropogenic environments. In this study, the relationship between surface runoff and groundwater recharge in urban areas is explored using a top-down water balance approach. Two empirical models were used to estimate runoff: (1) an updated, advanced method based on curve number, followed by (2) bivariate hydrograph separation. Modifications were added to each method in an attempt to better capture continuous soil-moisture processes and explicitly account for runoff from impervious surfaces. Differences between the resulting runoff estimates shed light on the complexity of the rainfall–runoff relationship, and highlight the importance of understanding soil-moisture dynamics and their control on hydro(geo)logical responses. These results were then used as input in a water balance to calculate groundwater recharge. Two approaches were used to assess the accuracy of these groundwater balance estimates: (1) comparison to calculations of groundwater recharge using the calibrated conceptual HBV Light model, and (2) comparison to groundwater recharge estimates from physically similar catchments in Switzerland that are found in the literature. In all cases, recharge is estimated at approximately 40–45% of annual precipitation. These conditions were found to closely echo those results from Swiss catchments of similar characteristics.