Uwe Kunkel

Dynamics and Attenuation of Acidic Pharmaceuticals along a River Stretch

While substantial knowledge on the occurrence of pharmaceuticals in the environment is available, their behavior and fate in surface waters is still poorly understood. Therefore, the aims of this study were to analyze the short-term dynamics of selected pharmaceuticals along a 13.6 km long river stretch downstream of a wastewater treatment plant (WWTP), and to quantify their attenuation by a mass balance approach. Four acidic pharmaceuticals (bezafibrate, clofibric acid, diclofenac, naproxen) with different attenuation properties were measured over a period of three weeks at high temporal resolution, and in situ photolysis experiments were carried out. The average concentrations of pharmaceuticals were between 9 +/- 4 and 339 +/- 133 ng L(-1), corresponding to loads between 1.9 +/- 1.2 and 63 +/- 37 g d(-1) (n = 134). The temporal dynamics of pharmaceuticals was closely related to discharge of the WWTP and precipitation, and highest concentrations were observed at the beginning of a discharge event. During a dry period, naproxen was eliminated along the river stretch with a dissipation time (DT(50)) of 3.6 +/- 2.1 days while the other compounds did not exhibit significant attenuation. As photolysis and other abiotic processes were of limited quantitative relevance, the attenuation of naproxen can most likely be attributed to biotransformation.

Reactive Tracer Test To Evaluate the Fate of Pharmaceuticals in Rivers

The fate of pharmaceutically active substances in rivers is still only incompletely understood, especially as the knowledge transfer from laboratory experiments to the real world is complicated by factors like turbidity, hydrodynamics, or heterogeneity. Therefore, we performed a tracer test with pharmaceutically active substances to study their fate and the importance of individual attenuation mechanisms in situ. The experiment was carried out at a small stream in central Sweden. Two dye tracers and six pharmaceuticals were injected as Dirac pulse and water was sampled at five downstream sites along a 16-km-long river reach. Ibuprofen and clofibric acid were the only compounds which were eliminated along the study reach at half-life times of 10 h and 2.5 d, respectively. Based on the shape of the breakthrough curves and the low hydraulic conductivity of the river bed, we can assume that exchange of river water with the hyporheic zone was minor. Thus, the contribution of processes in the hyporheic zone to the attenuation of pharmaceuticals was low. We hypothesize that ibuprofen and clofibric acid were transformed by in-stream biofilms growing on submerged macrophytes and at the water-sediment interface. Phototransformation and sorption were ruled out as major attenuation processes. No attenuation of bezafibrate, diclofenac, metoprolol, and naproxen was observed.

Evaluating the fate of six common pharmaceuticals using a reactive transport model: insights from a stream tracer test

Quantitative information regarding the capacity of rivers to self-purify pharmaceutical residues is limited. To bridge this knowledge gap, we present a methodology for quantifying the governing processes affecting the fate of pharmaceuticals in streaming waters and, especially, to evaluate their relative significance for tracer observations. A tracer test in Säva Brook, Sweden was evaluated using a coupled physical-biogeochemical model framework containing surface water transport together with a representation of transient storage in slow/immobile zones of the stream, which are presumably important for the retention and attenuation of pharmaceuticals. To assess the key processes affecting the environmental fate of the compounds, we linked the uncertainty estimates of the reaction rate coefficients to the relative influence of transformation and sorption that occurred in different stream environments. The hydrological and biogeochemical contributions to the fate of the pharmaceuticals were decoupled, and the results indicate a moderate hydrological retention in the hyporheic zone as well as in the densely vegetated parts of the stream. Biogeochemical reactions in these transient storage zones further affected the fate of the pharmaceuticals, and we found that sorption was the key process for bezafibrate, metoprolol, and naproxen, while primary transformation was the most important process for clofibric acid and ibuprofen. Conversely, diclofenac was not affected by sorption or transformation.

Quaternary Triphenylphosphonium Compounds: A New Class of Environmental Pollutants

A nontarget screening using high-resolution mass spectrometry (HRMS) was established to identify industrial emerging contaminants in the Rhine River. With this approach, quaternary triphenylphosphonium compounds (R-Ph3P(+)) were identified as new emerging contaminants in the aquatic environment. The suggested chemical structures were elucidated by MS fragmentation and chemical databank searches and eventually confirmed via authentic standards. R-Ph3P(+) are used worldwide by the chemical industry to synthesize alkenes via the Wittig reaction. In total, five compounds [R = butyl (Bu), R = ethyl (Et), R = methoxymethyl (MeOMe), R = methyl (Me), and R = phenyl (Ph)] were found in German rivers and streams. R-Ph3P(+) were detected only in those rivers and streams that received an appreciable portion of wastewater from the chemical industry. Up to 2.5 μg/L Et-Ph3P(+) was quantified in a small stream from the Hessian Ried, and in the Rhine, up to 0.56 μg/L Me-Ph3P(+) was detected. R-Ph3P(+) were also identified in suspended particulate matter and sediments in the Rhine catchment, with MeOMe-Ph3P(+) concentrations of up to 0.75 mg/kg and up to 0.21 mg/kg, respectively. Because of the lack of ecotoxicological studies, the environmental risks caused by R-Ph3P(+) can be assessed for neither pelagic nor benthic organisms.

Phytotoxicity of wastewater-born micropollutants – Characterisation of three antimycotics and a cationic surfactant

Sewage sludge applied to soil may be a valuable fertiliser but can also introduce poorly degradable and highly adsorptive wastewater-born residues of pharmaceuticals and personal care products (PPCPs) to the soil, posing a potential risk to the receiving environment. Three azole antimycotics (climbazole, ketoconazole and fluconazole), and one quaternary ammonium compound (benzyldimethyldodecylammonium chloride, BDDA) that are frequently detected in municipal sewage sludge and/or treated wastewater were therefore characterised in their toxicity toward terrestrial (Brassica napus) and aquatic (Lemna minor) plants. Fluconazole and climbazole showed the greatest toxicity to B. napus, while toxicity of ketoconazole and BDDA was by one to two orders of magnitude lower. Sludge amendment to soil at an agriculturally realistic rate of 5 t/ha significantly reduced the bioconcentration of BDDA in B. napus shoots compared to tests without sludge amendment, although not significantly reducing phytotoxicity. Ketoconazole, fluconazole and BDDA proved to be very toxic to L. minor with median effective concentrations ranging from 55.7 μg/L to 969 μg/L. In aquatic as well as terrestrial plants, the investigated azoles exhibited growth-retarding symptoms presumably related to an interference with phytohormone synthesis as known for structurally similar fungicides used in agriculture. While all four substances exhibited considerable phytotoxicity, the effective concentrations were at least one order of magnitude higher than concentrations measured in sewage sludge and effluent. Based on preliminary hazard quotients, BDDA and climbazole appeared to be of greater environmental concern than the two pharmaceuticals fluconazole and ketoconazole.

Biotransformation of gabapentin in surface water matrices under different redox conditions and the occurrence of one major TP in the aquatic environment

Laboratory-scale incubation experiments in water/sediment systems were conducted to test the transformation behavior of the anticonvulsant gabapentin (GBP) under different environmental conditions (aerobic, anaerobic, with abiotic controls). GBP was transformed by biological processes as it was eliminated quickly under aerobic conditions (dissipation time 50% of initial concentration (DT50): 2-7 days) whereas no decrease was observed under anaerobic conditions. Measurements via high resolution mass spectrometry (LC-Orbitrap-MS) revealed eight biological transformation products (TPs). Three of them were identified with reference standards (GBP-Lactam, TP186, TP213), while for the other five TPs tentative structures were proposed from information by MS2/MS3 experiments. Furthermore, the quantitatively most relevant TP GBP-Lactam was formed via intramolecular amidation (up to 18% of initial GBP concentration). Incubation experiments with GBP-Lactam revealed a higher stability against biotic degradation (DT50: 12 days) in contrast to GBP, while it was stable under anaerobic and abiotic conditions. Besides GBP, GBP-Lactam was detected in surface water in the μg L-1 range. Finally, GBP and GBP-Lactam were found in potable water with concentrations up to 0.64 and 0.07 μg L-1, respectively. According to the elevated environmental persistence of GBP-Lactam compared to GBP and its presumed enhanced toxicity, we recommend to involve GBP-Lactam into monitoring programs.

Quaternary (triphenyl-) phosphonium compounds: Environmental behavior and toxicity

An analytical method based on high resolution mass spectrometry coupled with liquid chromatography (LC-HRMS) for 25 quaternary phosphonium compounds (QPCs) and derived phosphine oxides (POs) was developed and validated. To investigate the occurrence and fate of QPCs in the aquatic environment, water, suspended solids and sediments from the rivers Rhine and Elbe (upper and middle Elbe as well as tidal Elbe) were analyzed, as well as samples from tributaries bearing significant loads of QPCs. For the first time, the quaternary phosphonium compound tetrabutylphosphonium (Bu4P+) was detected. In the river Elbe concentrations were determined of up to 4700 ng/L (surface water) and 1000 μg/kg (sediment), respectively. Analysis of a time series of suspended solids (2005-2015) showed that QPCs have been present in the Elbe and Rhine catchment for at least one decade, with partly rising tendency. A degradation experiment with Rhine sediment revealed that triphenylphosphonium compounds (R-Ph3P+) and Bu4P+ are persistent in contact with sediment and suspended solids and tend to sorb onto sediment particles. Toxicological studies (reactive oxygen species (ROS) after substance exposure, Ames test, Micronucleus test, determination of cytotoxicity) with selected QPCs confirmed that all of them exhibit cytotoxicity and some even genotoxic potential at elevated concentrations, which emphasizes the need for an emission regulation of these compounds.