Quantitative Determination and Environmental Risk Assessment of 102 Chemicals of Emerging Concern in Wastewater-Impacted Rivers Using Rapid Direct-Injection Liquid Chromatography—Tandem Mass Spectrometry

Abstract

The rapid source identification and environmental risk assessment (ERA) of hundreds of chemicals of emerging concern (CECs) in river water represent a significant analytical challenge. Herein, a potential solution involving a rapid direct-injection liquid chromatography–tandem mass spectrometry method for the quantitative determination of 102 CECs (151 qualitatively) in river water is presented and applied across six rivers in Germany and Switzerland at high spatial resolution. The method required an injection volume of only 10 µL of filtered sample, with a runtime of 5.5 min including re-equilibration with >10 datapoints per peak per transition (mostly 2 per compound), and 36 stable isotope-labelled standards. Performance was excellent from the low ng/L to µg/L concentration level, with 260 injections possible in any 24 h period. The method was applied in three separate campaigns focusing on the ERA of rivers impacted by wastewater effluent discharges (1 urban area in the Basel city region with 4 rivers, as well as 1 semi-rural and 1 rural area, each focusing on 1 river). Between 25 and 40 compounds were quantified directly in each campaign, and in all cases small tributary rivers showed higher CEC concentrations (e.g., up to ~4000 ng/L in total in the R. Schwarzach, Bavaria, Germany). The source of selected CECs could also be identified and differentiated from other sources at pre- and post- wastewater treatment plant effluent discharge points, as well as the effect of dilution downstream, which occurred over very short distances in all cases. Lastly, ERA for 41 CECs was performed at specific impacted sites, with risk quotients (RQs) at 1 or more sites estimated as high risk (RQ > 10) for 1 pharmaceutical (diclofenac), medium risk (RQ of 1–10) for 3 CECs (carbamazepine, venlafaxine, and sulfamethoxazole), and low risk (RQ = 0.1–1.0) for 7 CECs (i.e., RQ > 0.1 for 11 CECs in total). The application of high-throughput methods like this could enable a better understanding of the risks of CECs, especially in low flow/volume tributary rivers at scale and with high resolution.

An Alternative Strategy for Screening and Confirmation of 330 Pesticides in Ground- and Surface Water Using Liquid Chromatography Tandem Mass Spectrometry

“…The mobile phase consisting only of ammonium formate as eluent additives enabled the simultaneous analysis of 480 pesticides using scheduled multiple reaction monitoring (MRM) detection in the MS/MS instrument ( Table S1 ). This eluent composition is rather different from those used earlier [ 2 , 14 , 15 , 16 , 18 , 19 , 20 , 21 , 26 , 29 , 30 , 31 , 32 ].…”

“…A recent Hungarian study on pesticides in ground- and surface water reported that more than half samples contained detectable levels of pesticides, and about 5% of the samples contained pesticides at levels exceeding the 100 ng/L maximum concentration level for individual pesticides, and 500 ng/L maximum concentration level for the sum of pesticides as specified by EU directives [ 11 , 12 , 13 ]. Additionally, numerous research articles have reported the frequent detection of pesticides in water worldwide [ 2 , 3 , 4 , 5 , 7 , 8 , 9 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. The other environmental concern is the fate of pesticides, which can lead to harmful metabolites with unknown toxicity to animals and humans [ 3 , 8 , 9 ].…”

“…However, the target concentration levels in food are much higher than 100 ng/L, the individual maximum level of pesticides in water [ 12 , 13 ]. Consequently, sample pre-concentration should be carried out during sample preparation before instrumental analysis [ 2 , 18 , 19 , 20 , 21 ]; however, the direct injection of water samples has been used in some published methods [ 14 , 15 , 16 ]. Gas chromatography (GC) or ultra/high performance liquid chromatography (UHPLC) coupled with mass spectrometric detection (GC-MS or LC-MS) are the most suitable techniques for the analysis of a high number of pesticides [ 2 , 3 , 4 , 11 , 17 , 26 , 27 , 28 ].…”

A year-long study of the occurrence and risk of over 140 contaminants of emerging concern in wastewater influent, effluent and receiving waters in the Republic of Ireland

“…In terms of transport, CECs arising from WWTP effluents can dilute rapidly depending on the size of the receiving river (Egli et al, 2021), but compounds such as ibuprofen, paracetamol and trimethoprim have been found up to 10 km downstream from WWTPs (Letsinger et al, 2019). Other compounds such as UV-filters have been reported at higher concentrations in river water globally, for example during the summer season in Korea (Ekpeghere et al, 2016), and occurrence therefore related to consumption habits (Carrao et al, 2021).…”

A rapid evidence assessment of the potential risk to the environment presented by active ingredients in the UK’s most commonly sold companion animal parasiticides

“…Although not noted in the EPAR, immunotoxicity was observed in laboratory mice (Badgujar et al 2013 ) and in vitro testing (Shi et al 2018 ). Other signs of toxicity in mice included decreased body weight, gut microbiome and endocrine system disruption, increased oxidative stress, and apoptosis (Yang et al 2020 ; Yuan et al 2020 ). Developmental toxicity was also observed, with offspring of treated mice found to exhibit altered brain development, brain function, and behaviour (Burke et al 2018 ; Nakayama et al 2019 ).…”