Abteilung Wasserressourcen und Trinkwasser

In einer landesweiten Studie wurde Quecksilber in Abwässern und Klärschlämmen analysiert, jährliche Gesamtmengen des abwasserbürtigen Quecksilbers ermittelt und die Einhaltung der gesetzlichen Vorgaben überprüft. Ebenso wurde die durchschnittliche Fracht pro Einwohner und der Beitrag der Abwasserreinigungsanlagen zur Quecksilberbelastung der Oberflächengewässer ermittelt. Auf nationaler Ebene waren diese Kennzahlen bisher nicht bekannt.

Short-chain chlorinated paraffins (SCCPs) are listed as persistent organic pollutants (POPs) under the Stockholm Convention. Such substances are toxic, bioaccumulating, transported over long distances and degrade slowly in the environment. Certain bacterial strains of the Sphingomonadacea family are able to degrade POPs, such as hexachlorocyclohexanes (HCHs) and hexabromocyclododecanes (HBCDs). The haloalkane dehalogenase LinB, expressed in certain Sphingomonadacea, is able to catalyze the transformation of haloalkanes to hydroxylated compounds. Therefore, LinB is a promising candidate for conversion of SCCPs. Hence, a mixture of chlorinated tridecanes was exposed in vitro to LinB, which was obtained through heterologous expression in Escherichia coli. Liquid chromatography mass spectrometry (LC-MS) was used to analyze chlorinated tridecanes and their transformation products. A chloride-enhanced soft ionization method, which favors the formation of chloride adducts [M+Cl]^- without fragmentation, was applied. Mathematical deconvolution was used to distinguish interfering mass spectra of paraffinic, mono-olefinic and di-olefinic compounds. Several mono- and di-hydroxylated products including paraffinic, mono-olefinic and di-olefinic compounds were found after LinB exposure. Mono- (rt = 5.9–6.9 min) and di-hydroxylated (rt = 3.2–4.5 min) compounds were separated from starting material (rt = 7.7–8.5 min) by reversed phase LC. Chlorination degrees of chlorinated tridecanes increased during LinB-exposure from n_Cl = 8.80 to 9.07, indicating a preferential transformation of lower chlorinated (Cl_<9) tridecanes. Thus, LinB indeed catalyzed a dehalohydroxylation of chlorinated tridecanes, tridecenes and tridecadienes. The observed hydroxylated compounds are relevant CP transformation products whose environmental and toxicological effects should be further investigated.

Dissolved organic matter (DOM) plays a crucial role in the photochemical transformation of organic contaminants in natural aquatic systems. The present study focuses on the characterization of a specific effect previously observed for electron-rich phenols, consisting in an acceleration of the DOM-photosensitized transformation of target compounds at low concentrations (< 1 µM). This effect was hypothesized to be caused by DOM-derived "long-lived" photooxidants (LLPO). Pseudo-first-order rate constants for the transformation of several phenols, anilines, sulfonamide antibiotics and phenylureas photosensitized by Suwannee River fulvic acid were determined under steady−state irradiation using the UVA and visible wavelengths from a medium-pressure mercury lamp. A significant enhancement (by a factor of 2.4 − 16) of the first-order transformation rate constant of various electron-rich target compounds was observed for an initial concentration of 0.1 μM compared to 5 μM . This effect points to a relevant reactivity of these compounds with LLPO. For phenols and anilines the enhancement effect occurred only above certain standard one-electron oxidation potentials. From these data series the standard one-electron reduction potential of LLPO was estimated to be in the range of 1.0 − 1.3 V versus the standard hydrogen electrode. LLPO are proposed to mainly consist of phenoxyl radicals formed by photooxidation of electron-poor phenolic moieties of the DOM. The plausibility of this hypothesis was successfully tested by studying the photosensitized transformation kinetics of 3,4-dimethoxyphenol in aqueous solutions containing a model photosensitizer (2-acetonaphthone) and a model electron-poor phenol (4-cyanophenol) as DOM surrogates.

Snowmelt contributes a significant fraction of groundwater recharge in snow‐dominated regions, making its accurate quantification crucial for sustainable water resources management. While several components of the hydrological cycle can be measured directly, catchment‐scale recharge can only be quantified indirectly. Stable water isotopes are often used as tracers to estimate snowmelt recharge, even though estimates based on stable water isotopes are biased due to the large variations of δ²H and δ¹⁸O in snow and the difficulty to measure snowmelt directly. To overcome this gap, a new tracer method based on on‐site measurements of dissolved He, ⁴⁰Ar, ⁸⁴Kr, N₂, O₂ and CO₂ is presented. The new method was developed alongside classical tracer methods (stable water isotopes, ²²²Rn, ³H/³He) in a highly instrumented boreal catchment. By revealing (noble gas) recharge temperatures and excess air, dissolved gases allow (i) the contribution of snowmelt to recharge, (ii) the temporal recharge dynamics, and (iii) the primary recharge pathways to be identified. In contrast to stable water isotopes, which produced highly inconsistent snowmelt recharge estimates for the experimental catchment, dissolved gases produced consistent estimates even when the temperature of snowmelt during recharge was not precisely known. As dissolved gases are not controlled by the same processes as stable water isotopes, they are not prone to the same biases and represent a highly complementary tracer method for the quantification of snowmelt recharge dynamics in snow‐dominated regions. Furthermore, an observed systematic depletion of N₂ in groundwater provides new evidence for the pathways of biological N‐fixation in boreal forest soils.