A platform for archiving liquid chromatography high-resolution mass spectrometry (LC-HRMS) data was developed for the retrospective suspect screening of thousands of environmental pollutants with the ...ambition of becoming a European and possibly global standard. It was termed Digital Sample Freezing Platform (DSFP) and incorporates all the recent developments in the HRMS screening methods within the NORMAN Network. In the workflow, raw mass spectral data are converted into mzML, then mass spectral and chromatographic information on thousands of peaks of each sample is extracted into Data Collection Templates. The ‘digitally frozen’ samples can be retrospectively screened for the presence of virtually any compound amenable to LC–MS using a combination of information on its (i) exact mass, (ii) predicted retention time window in the chromatogram, (iii) isotopic fit and (iv) qualifier fragment ions. Its potential was demonstrated on monitoring of 670 antibiotics and 777 REACH chemicals from the Joint Black Sea Surveys (JBSS).
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•An overview of the current HRMS screening steps is presented in an automatized tool.•Digital archiving and retrospective suspect screening were integrated in DSFP.•DSFP enables enhanced data mining and visualization capabilities.•54 seawater, 19 sediment and 12 biota samples were screened for 1447 substances.•80 chemicals from the REACH registry and 12 antibiotics were detected.
Averaged 7-day composite effluent wastewater samples from twelve wastewater treatment plants (WWTPs) in nine countries (Romania, Serbia, Hungary, Slovenia, Croatia, Slovakia, Czechia, Austria, ...Germany) in the Danube River Basin were collected. WWTPs' selection was based on countries' dominant technology and a number of served population with the aim to get a representative holistic view of the pollution status. Samples were analyzed for 2248 chemicals of emerging concern (CECs) by wide-scope target screening employing LC-ESI-QTOF-MS. 280 compounds were detected at least in one sample and quantified. Spatial differences in the concentrations and distribution of the compounds classes were discussed. Additionally, samples were analyzed for the possible agonistic/antagonistic potencies using a panel of in vitro transactivation reporter gene CALUX® bioassays including ERα (estrogenics), anti-AR (anti-androgens), GR (glucocorticoids), anti-PR (anti-progestins), PPARα and PPARγ (peroxisome proliferators) and PAH assays. The potency of the wastewater samples to cause oxidative stress and induce xenobiotic metabolism was determined using the Nrf2 and PXR CALUX® bioassays, respectively. The signals from each of the bioassays were compared with the recently developed effect-based trigger values (EBTs) and thus allowed for allocating the wastewater effluents into four categories based on their measured toxicity, proposing a putative action plan for wastewater operators. Moreover, samples were analyzed for antibiotics and 13 antibiotic-resistant genes (ARGs) and one mobile genetic element (intl1) with the aim to assess the potential for antibiotic resistance. All data collected from these various types of analysis were stored in an on-line database and can be viewed via interactive map at https://norman-data.eu/EWW_DANUBE.
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•280 out of 2248 target substances were detected.•Detected chemicals were evaluated based on their ecotoxicological properties.•10 in vitro bioassays were applied for assessing the adverse effects in wastewater.•Effect-based risk assessment of WWTP effluents was applied.•13 antibiotic resistant genes were determined in the Danube River Basin.
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•279 out of 2316 target substances were detected and 16 compounds were prioritized.•Passive sampling proved to be a powerful way for monitoring treated wastewater.•Field-scale ...calibration of a novel passive sampler prototype was achieved.•7 transformation products of the 4 prioritized antibiotics were elucidated.•Six antibiotic resistant genes were detected in all collected wastewater samples.
The occurrence of chemical and biological contaminants of emerging concern (CECs) was investigated in treated wastewater intended for reuse in agriculture. An agarose hydrogel diffusion-based passive sampler was exposed to the outlet of a wastewater treatment plant (WWTP) located in Cyprus, which is equipped with membrane bioreactor (MBR). Passive samplers in triplicate were exposed according to a time-series exposure plan with maximum exposure duration of 28 days. Composite flow-proportional wastewater samples were collected in parallel with the passive sampling exposure plan and were processed by solid phase extraction using HORIZON SPE-DEX 4790 and the same sorbent material (Oasis HLB) as in the passive sampler. The analysis of passive samplers and wastewater samples enabled (i) the field-scale calibration of the passive sampler prototype by the calculation of in situ sampling rates of target substances, and (ii) the investigation of in silico predicted transformation products of the four most ecotoxicologically hazardous antibiotics (azithromycin, clarithromycin, erythromycin, ofloxacin). Additionally, the wastewater samples were subjected to the analysis of seven preselected antibiotic resistant genes (ARGs) and one mobile resistant element (int1). All extracts were analyzed for chemicals in a single batch using a highly sensitive method for pharmaceuticals, antibiotics and illicit drugs by liquid chromatography tandem MS/MS (LC-QQQ) and for various other target compounds (2316 compounds in total) by liquid chromatography high-resolution mass spectrometry (LC-HRMS). 279 CECs and all investigated ARGs (except for blaCTX-M−32) were detected, highlighting potential chemical and biological hazards related to wastewater reuse practices. 16 CECs were prioritized following ecotoxicological risk assessment, whereas sul1 and the mobile resistant element (int1) showed the highest abundance. Comprehensive monitoring efforts using novel sampling methods such as passive sampling, wide-scope target screening and molecular analysis are required to assure safe application of wastewater reuse and avoid spread and crop uptake of potentially hazardous chemicals.
The quality of the Dniester River Basin has been seriously impacted by the chemicals released by agriculture, industry, and wastewater discharges. To assess its current chemical pollution status, a ...transboundary monitoring campaign was conducted in May 2019. Thirteen surface water, 13 sediment, and three biota samples were collected and analyzed using generic sample preparation methods for the determination of organic substances by liquid chromatography high-resolution mass spectrometry (LC-HRMS) and metals by inductively coupled plasma mass spectrometry (ICP-MS). Wide-scope target and suspect screening resulted in detection of Water Framework Directive (WFD) priority substances and emerging contaminants, whereas the raw data were stored in NORMAN Digital Sample Freezing Platform (DSFP) for future retrospective screening. Furthermore, risk assessment was performed to prioritize detected substances and propose a draft list of river basin–specific pollutants. All studied metals (As, Hg, Zn, Cu, Cr, Cd, Pb, Ni) were detected in the surface water and sediments. In total, 139 organic contaminants belonging to various chemical classes (pesticides, pharmaceuticals, drugs of abuse, stimulants, sweeteners, industrial chemicals, and their transformation products) were detected. The highest cumulative concentration of contaminants was observed in surface water from the Byk River, a tributary of the Dniester (Moldova). Concentrations of WFD priority substances diuron and mercury and EU Watch List neonicotinoid compounds imidacloprid and thiamethoxam exceeded their environmental quality standards (EQS), whereas concentrations of 23 emerging substances exceeded their predicted no-effect concentration (PNEC) at minimum one site. Emerging contaminants telmisartan, metolachlor, terbuthylazine, and 4-acetamidoantipyrine were prioritized as potential river basin–specific pollutants.
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Siverskyi Donets is the fourth longest river in Ukraine and its ecosystem is heavily affected by numerous agricultural and industrial activities. An impact of the on-going armed military conflicts in ...the Eastern Ukraine to the overall pollution by the chemicals has been studied. Considering the uncontrolled activities in the catchment due to the conflict, there is a high demand to assess the contamination status of the Siverskyi Donets basin. In this study, the occurrence of the EU Water Framework Directive priority substances, selected physicochemical parameters and wide-range emerging contaminants were investigated in surface water, groundwater, biota and river sediments samples from 13 sampling sites in the river basin. The study included metals, inorganic, non-polar and polar organic contaminants. The wide-scope target screening of 2316 substances and suspect screening of 2219 substances revealed occurrence of 83 compounds in the studied samples. A few industrial chemicals such as plasticizers bisphenol A and DEHP, as well as flame retardant brominated diphenylethers were found to be potentially hazardous to the ecosystem, exceeding the established legacy environmental quality standards (EQS) or the provisional no-effect concentration (PNEC) values. River sediment samples contained traces of long-term banned chemicals such as polychlorinated biphenyls (PCBs) and degradation products of DDT (p,p'-DDD and p,p'-DDE). A simplified risk assessment based on comparison of measured concentration of the detected compounds against their (eco)toxicity threshold values from the NORMAN Ecotoxicology Database has been performed to aid their prioritization in future monitoring and, eventually, establishing the list of Siverskyi Donets River Basin Specific Pollutants. A comparison with the recent similar studies in the Dniester and Dnieper river basins in Ukraine has shown that the overall pollution by chemicals in the Siverskyi Donets basin is significantly lower.
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•Lower levels of emerging contaminants were detected in the conflict zone.•High local concentrations of heavy metals were detected in the warzone of Donbass.•Bisphenol A, DEHP and prometryn exceeded their ecotoxicological thresholds.•Brominated diphenylethers were detected above their EQS thresholds in biota.•High levels for PAHs, PCBs and degradation products of DDT were found in sediments.
•586 of the studied 2362 contaminants were detected in the Danube River Basin.•Risk assessment prioritized 12 legacy and 33 emerging contaminants.•The 33 emerging contaminants are Danube River Basin ...Specific Pollutants.•20 performance indicators were checked in wastewater treatment plants.•The plants showed medium or efficient removal for 70% of the studied compounds.
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.
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