Wide-scope target screening characterization of legacy and emerging contaminants in the Danube River Basin by liquid and gas chromatography coupled with high-resolution mass spectrometry.

A state-of-the-art wide-scope target screening of 2,362 chemicals and their transformation products (TPs) was performed in samples collected within the Joint Danube Survey 4 (JDS4) performed in 2019. The analysed contaminants of emerging concern (CECs) included three major categories: plant protection products (PPPs), industrial chemicals and pharmaceuticals and personal care products (PPCPs). In total, 586 CECs were detected in the samples including 158 PPPs, 71 industrial chemicals, 348 PPCPs, and 9 other chemicals. A wide-variety of sample matrices were collected including influent and effluent wastewater, groundwater, river water, sediment and biota. Forty-five CECs (19 PPPs, 8 industrial chemicals, 18 PPCPs) were detected at levels above their ecotoxicological thresholds (lowest predicted no-effect concentration (PNEC) values) in one or more of the investigated environmental compartments, indicating potential adverse effects on the impacted ecosystems. Among them 12 are legacy substances; 33 are emerging and qualify as potential Danube River Basin Specific Pollutants (RBSPs). Moreover, the efficiency of the wastewater treatment plants (WWTPs) was evaluated using 20 selected performance indicator chemicals. WWTPs showed effective removal (removal rate ≥80%) and medium removal (removal rate 25-80%) for 6 and 8 of the indicator chemicals, respectively. However, numerous contaminants passed the WWTPs with a lower removal rate. Further investigation on performance of WWTPs is suggested at catchment level to improve their removal efficiency. WWTP effluents are proven to be one of the major sources of contaminants in the Danube River Basin (DRB). Other sources include sewage discharges, industrial and agricultural activities. Continuous monitoring of the detected CECs is suggested to ensure water quality of the studied area.

Mitigating risks and maximizing sustainability of treated wastewater reuse for irrigation.

Scarcity of freshwater for agriculture has led to increased utilization of treated wastewater (TWW), establishing it as a significant and reliable source of irrigation water. However, years of research indicate that if not managed adequately, TWW may deleteriously affect soil functioning and plant productivity, and pose a hazard to human and environmental health. This review leverages the experience of researchers, stakeholders, and policymakers from Israel, the United-States, and Europe to present a holistic, multidisciplinary perspective on maximizing the benefits from municipal TWW use for irrigation. We specifically draw on the extensive knowledge gained in Israel, a world leader in agricultural TWW implementation. The first two sections of the work set the foundation for understanding current challenges involved with the use of TWW, detailing known and emerging agronomic and environmental issues (such as salinity and phytotoxicity) and public health risks (such as contaminants of emerging concern and pathogens). The work then presents solutions to address these challenges, including technological and agronomic management-based solutions as well as source control policies. The concluding section presents suggestions for the path forward, emphasizing the importance of improving links between research and policy, and better outreach to the public and agricultural practitioners. We use this platform as a call for action, to form a global harmonized data system that will centralize scientific findings on agronomic, environmental and public health effects of TWW irrigation. Insights from such global collaboration will help to mitigate risks, and facilitate more sustainable use of TWW for food production in the future.

Dioxins and dioxin-like compounds in composts and digestates from European countries as determined by the in vitro bioassay and chemical analysis.

Aerobic composting and anaerobic digestion plays an important role in reduction of organic waste by transforming the waste into humus, which is an excellent soil conditioner. However, applications of chemical-contaminated composts on soils may have unwanted consequences such as accumulation of persistent compounds and their transfer into food chains. The present study investigated burden of composts and digestates collected in 16 European countries (88 samples) by the compounds causing dioxin-like effects as determined by use of an in vitro transactivation assay to quantify total concentrations of aryl hydrocarbon receptor-(AhR) mediated potency. Measured concentrations of 2,3,7,8-Tetrachlorodibeno-p-dioxin (2,3,7,8-TCDD) equivalents (TEQbio) were compared to concentrations of polycyclic aromatic hydrocarbons (PAHs) and selected chlorinated compounds, including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), co-planar polychlorinated biphenyls (PCBs), indicator PCB congeners and organochlorine pesticides (OCPs). Median concentrations of TEQbio (dioxin-like compounds) determined by the in vitro assay in crude extracts of various types of composts ranged from 0.05 to 1.2 with a maximum 8.22µg (TEQbio)kg(-1) dry mass. Potencies were mostly associated with less persistent compounds such as PAHs because treatment with sulfuric acid removed bioactivity from most samples. The pan-European investigation of contamination by organic contaminants showed generally good quality of the composts, the majority of which were in compliance with conservative limits applied in some countries. Results demonstrate performance and added value of rapid, inexpensive, effect-based monitoring, and points out the need to derive corresponding effect-based trigger values for the risk assessment of complex contaminated matrices such as composts.

Triazines in the aquatic systems of the Eastern Chinese Rivers Liao-He and Yangtse.

The results of a one-year monitoring program on the two Eastern Chinese River systems, i.e. the Liao-He and the Yangtse, with special emphasis on the presence of triazine herbicides are presented. Sediment, suspended solids and water samples from both rivers were analyzed. Additionally, recovery experiments on the SPE-in-field-enrichment procedure and the extraction methods were performed. The samples were measured by gas chromatography coupled with mass spectrometry, electron capture detection and a newly developed mu-plasma atomic emission detector. A typical result of a one-year monitoring was obtained in case of the Liao-He: During winter, at low water period, low triazine values were found. A similar situation was found in early spring. Highest concentrations of atrazine up to 1600 ng/l were found in late spring in the water samples. Maximum concentrations of atrazine, simazine, propazine, simetryn and prometryn were observed in this season as a result of the actual use of triazines. Finally, after the high water period in autumn the triazine concentrations decreased. Additionally, atrazine adsorbed on sediment (up to 2.8 ng/g) and suspended solids was determined (up to 8 ng/l) during late spring sampling. Therefore, the logarithm of the organic carbon based sorption coefficient of atrazine could be calculated. Low levels of atrazine were measured in the water of Yangtse (up to 18.3 ng/l). The concentrations from all sampling points and sampling stations of a particular sampling date were similar, which indicates a homogeneous distribution of this herbicide. Due to the high discharge rate of up to 79,000 m3/s in case of the Yangtse a considerable mass transport of up to 57.5 kg per day atrazine may take place, even at concentrations below the European drinking water limit of 100 ng/l.

Europe-wide survey of estrogenicity in wastewater treatment plant effluents: the need for the effect-based monitoring.

A pan-European monitoring campaign of the wastewater treatment plant (WWTP) effluents was conducted to obtain a concise picture on a broad range of pollutants including estrogenic compounds. Snapshot samples from 75 WWTP effluents were collected and analysed for concentrations of 150 polar organic and 20 inorganic compounds as well as estrogenicity using the MVLN reporter gene assay. The effect-based assessment determined estrogenicity in 27 of 75 samples tested with the concentrations ranging from 0.53 to 17.9 ng/L of 17-beta-estradiol equivalents (EEQ). Approximately one third of municipal WWTP effluents contained EEQ greater than 0.5 ng/L EEQ, which confirmed the importance of cities as the major contamination source. Beside municipal WWTPs, some treated industrial wastewaters also exhibited detectable EEQ, indicating the importance to investigate phytoestrogens released from plant processing factories. No steroid estrogens were detected in any of the samples by instrumental methods above their limits of quantification of 10 ng/L, and none of the other analysed classes of chemicals showed correlation with detected EEQs. The study demonstrates the need of effect-based monitoring to assess certain classes of contaminants such as estrogens, which are known to occur at low concentrations being of serious toxicological concern for aquatic biota.

Substance-related environmental monitoring strategies regarding soil, groundwater and surface water - an overview.

Substance-related monitoring is an essential tool within environmental risk assessment processes. The soundness of policy decisions including risk management measures is often directly related to the reliability of the environmental monitoring programs. In addition, monitoring programs are required for identifying new and less-investigated pollutants of concern in different environmental media. Scientifically sound and feasible monitoring concepts strongly depend on the aim of the study. The proper definition of questions to be answered is thus of pivotal importance. Decisions on sample handling, storage and the analysis of the samples are important steps for the elaboration of problem-oriented monitoring strategies. The same applies to the selection of the sampling sites as being representative for scenarios to be investigated. These steps may become critical to handle for larger international monitoring programs and thus trigger the quality of their results. This study based on the work of an IUPAC (International Union of Pure and Applied Chemistry) task group addresses different kinds and approaches of substance-related monitoring of different compartments of soil, groundwater and surface water, and discusses their advantages and limitations. Further important aspects are the monitoring across policies and the monitoring data management using information systems.

EU-wide monitoring survey on emerging polar organic contaminants in wastewater treatment plant effluents.

In the year 2010, effluents from 90 European wastewater treatment plants (WWTPs) were analyzed for 156 polar organic chemical contaminants. The analyses were complemented by effect-based monitoring approaches aiming at estrogenicity and dioxin-like toxicity analyzed by in vitro reporter gene bioassays, and yeast and diatom culture acute toxicity optical bioassays. Analyses of organic substances were performed by solid-phase extraction (SPE) or liquid-liquid extraction (LLE) followed by liquid chromatography tandem mass spectrometry (LC-MS-MS) or gas chromatography high-resolution mass spectrometry (GC-HRMS). Target microcontaminants were pharmaceuticals and personal care products (PPCPs), veterinary (antibiotic) drugs, perfluoroalkyl substances (PFASs), organophosphate ester flame retardants, pesticides (and some metabolites), industrial chemicals such as benzotriazoles (corrosion inhibitors), iodinated x-ray contrast agents, and gadolinium magnetic resonance imaging agents; in addition biological endpoints were measured. The obtained results show the presence of 125 substances (80% of the target compounds) in European wastewater effluents, in concentrations ranging from low nanograms to milligrams per liter. These results allow for an estimation to be made of a European median level for the chemicals investigated in WWTP effluents. The most relevant compounds in the effluent waters with the highest median concentration levels were the artificial sweeteners acesulfame and sucralose, benzotriazoles (corrosion inhibitors), several organophosphate ester flame retardants and plasticizers (e.g. tris(2-chloroisopropyl)phosphate; TCPP), pharmaceutical compounds such as carbamazepine, tramadol, telmisartan, venlafaxine, irbesartan, fluconazole, oxazepam, fexofenadine, diclofenac, citalopram, codeine, bisoprolol, eprosartan, the antibiotics trimethoprim, ciprofloxacine, sulfamethoxazole, and clindamycine, the insect repellent N,N'-diethyltoluamide (DEET), the pesticides MCPA and mecoprop, perfluoroalkyl substances (such as PFOS and PFOA), caffeine, and gadolinium.

Continental scale inverse modeling of common organic water contaminants in European rivers.

The paper presents an analysis of measured riverine concentrations of 16 common organic water contaminants. From observed concentrations we back-calculate emissions and chemical half lives through a simple inverse model. The analysis does not allow identifying a single half life/emission factor combination, but a set of combinations which are Pareto-optimal (or "non-dominated"). The approach is shown to provide a rational basis for the screening of chemicals in rivers: with reference to the 16 chemicals considered here, estimated emission factors and half lives are consistent with the ones reported in other studies. For more precise estimates, prior knowledge about either emission factors or half lives is necessary. For the considered chemicals, loads to European seas can be subsequently estimated with an uncertainty usually within a factor of 2. The approach can be proposed for the inventorying of catchment-specific chemical pollutant emissions required for European environmental policies.