Characterization of scrubber water discharges from ships using comprehensive suspect screening strategies based on GC-APCI-HRMS.

An extended suspect screening approach for the comprehensive chemical characterization of scrubber discharge waters from exhaust gas cleaning systems (EGCSs), used to reduce atmospheric shipping emissions of sulphur oxides, was developed. The suspect screening was based on gas chromatography coupled with high-resolution mass spectrometry (GC-HRMS) and focused on the identification of polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives (alkyl-PAHs), which are among the most frequent and potentially toxic organic contaminants detected in these matrices. Although alkyl-PAHs can be even more abundant than parent compounds, information regarding their occurrence in scrubber waters is scarce. For compound identification, an in-house compound database was built, with 26 suspect groups, including 25 parent PAHs and 23 alkyl-PAH homologues. With this approach, 7 PAHs and 12 clusters of alkyl-PAHs were tentatively identified, whose occurrence was finally confirmed by target analysis using GC coupled with tandem mass spectrometry (GC-MS/MS). Finally, a retrospective analysis was performed to identify other relevant (poly)cyclic aromatic compounds (PACs) of potential concern in scrubber waters. According to it, 18 suspect groups were tentatively identified, including biphenyls, dibenzofurans, dibenzothiophenes and oxygenated PAHs derivatives. All these compounds could be used as relevant markers of scrubber water contamination in heavy traffic marine areas and be considered as potential stressors when evaluating scrubber water toxicity.

High resolution mass spectrometric suspect screening, wide-scope target analysis of emerging contaminants and determination of legacy pollutants in adult black-tailed godwit Limosa limosa limosa in the Netherlands - A pilot study.

The Dutch breeding population of the black-tailed godwit Limosa limosa limosa has declined substantially over recent decades; the role of contaminants is unknown. We analysed liver samples from 11 adult birds found dead on their breeding grounds in SW Friesland 2016-2020, six from extensive, herb-rich grasslands, five from intensive grasslands. We carried out LC and GC wide-scope target analysis of more than 2400 substances, LC suspect screening for more than 60,000 substances, target analysis for Cd, Hg, Ni and Pb, organo-phosphate flame retardants (OPFRs), dechlorane plus compounds and selected polybrominated diphenyl ether flame retardants (PBDEs), and bioassay for polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/PDBFs) and dioxin-like polychlorinated biphenyls (dl-PCBs). Residues of 29 emerging contaminants (ECs) were determined through wide-scope target analysis. Another 20 were tentatively identified through suspect screening. These contaminants include industrial chemicals (personal care products, surfactants, PAHs and others), plant protection products (PPPs) and pharmaceuticals and their transformation products. Total contaminant load detected by wide-scope target analysis ranged from c. 155 to c. 1400 ng g-1 and was generally lower in birds from extensive grasslands. Heatmaps suggest that birds from intensive grasslands have a greater mix and higher residue concentrations of PPPs, while birds from extensive grasslands have a greater mix and higher residue concentrations of per- and polyfluoroalkyl substances (PFAS). All four metals and two OPFRs were detected. All tested PBDEs were below the respective LODs. Bioassay revealed presence of PBDDs, PBDFs and dl-PCBs. Further research is required to elucidate potential health risks to godwits and contaminant sources.

Occurrence of pharmaceuticals in the wastewater of a Greek hospital: Combining consumption data collection and LC-QTOF-MS analysis.

In this article we applied drug consumption approach and chemical analysis in parallel to investigate the concentrations of a large number of pharmaceuticals in different streams of a General Hospital. Drugs consumption data was collected during two periods (Period 1, 2) and the predicted environmental concentrations (PECs) were estimated for the wastewater of a building housing specific medical services (Point A) and for the entire hospital (Point B). Hospital wastewater samples (HWW) samples were also collected from these points and periods and the measured environmental concentrations (MEC) were determined using UHPLC-ESI-QTOF-MS/MS. According to consumption data, the highest number of drugs was consumed in the departments of Hematology, Intensive Care Unit, Cardiology, Internal Medicine, and Oncology, while the number of active substances used in the hospital was 413 (Period 1) and 362 (Period 2). For most substances, much higher PEC and MEC values were found at the HWW of Point A indicating that on-site treatment of this stream could be examined in the future. The application of wide-scope target analysis allowed the quantification of 122 compounds, while 21 additional substances were identified using suspect screening. The highest mean concentrations in Period 1 were found for acetaminophen (1100 µg/L) and rifaximin (723 µg/L), while in Period 2 for iopromide (458 µg/L) and acyclovir (408 µg/L). Among the detected compounds, 19 metabolites were determined. Atenolol acid, 1-hydroxy-midazolam and clopidogrel carboxylic acid were quantified at concentrations much higher than parent compounds indicating the importance of metabolites' monitoring in HWW. Calculation of PEC/MEC ratio for 36 pharmaceuticals showed sufficient correlation of these values for 19 % to 33 % of the substances depending on the examined period and sampling point. The parallel collection of drugs consumption data and chemical analysis give a thorough picture of the substances present in HWW and their main sources, facilitating decision-making for their better management.

Wide-scope target analysis of emerging contaminants in landfill leachates and risk assessment using Risk Quotient methodology.

Raw and treated leachate samples were collected from different landfills in Greece and analyzed for several groups of emerging contaminants using high resolution mass spectrometric workflows to investigate the possible threat from their discharge to the aquatic environment. Fifty-eight compounds were detected; 2-OH-benzothiazole was found at 84 % of the samples and perfluorooctanoic acid at 68 %. Bisphenol A, valsartan and 2-OH-benzothiazole had the highest average concentrations in raw leachates, after biological treatment and after reverse osmosis, respectively. In untreated leachates, Risk Quotients > 1 were calculated for 35 and 18 compounds when maximum and average concentrations were used, indicating an ecological threat for the aquatic environment. Leachates' biological treatment partially removed COD and NH4+-N, as well as 52.3 % of total emerging contaminants. The application of reverse osmosis resulted in a 98 % removal of major pollutants, 99 % removal of total emerging contaminants and a significant decrease of ecotoxicity to Lemna minor. Beside the decrease of the detected micropollutants during treatment, RQs > 1 were still calculated for 13 and 3 compounds after biological treatment and reverse osmosis, respectively. Among these, special attention should be given to 2-OH-benzothiazole and bisphenol A that had RQ values much higher than 1 for all tested organisms.