Screening of contaminants of emerging concern in surface water and wastewater effluents, assisted by the Persistency-Mobility-Toxicity Criteria

Contaminants of emerging concern (CECs) are compounds of diverse origins that have not been deeply studied in the past which are now accruing growing environmental interest. The NOR-Water project aimed to identify the main CECs and their sources in the water environment of Northern Portugal–Galicia (located in northwest Spain) transnational region. To achieve these goals, a suspect screening analytical methodology based on the use of liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) was applied to 29 sampling sites in two campaigns. These sampling sites included river and sea water, as well as treated wastewater. The screening was driven by a library of over 3500 compounds, which included 604 compounds prioritized from different relevant lists on the basis of the persistency, mobility, and toxicity criteria. Thus, a total of 343 chemicals could be tentatively identified in the analyzed samples. This list of 343 identified chemicals was submitted to the classification workflow used for prioritization and resulted in 153 chemicals tentatively classified as persistent, mobile, and toxic (PMT) and 23 as very persistent and very mobile (vMvP), pinpointing the relevance of these types of chemicals in the aqueous environment. Pharmaceuticals, such as the antidepressant venlafaxine or the antipsychotic sulpiride, and industrial chemicals, especially high production volume chemicals (HPVC) such as ε-caprolactam, were the groups of compounds that were detected at the highest frequencies.This research was funded by Xunta de Galicia (ED431C 2021/06) and the European Regional Development Fund through the Interreg V-A Spain-Portugal Programme (POCTEP) 2014-2020 (ref. 0725_NOR_WATER_1_P). R. M. acknowledges Banco Santander and Universidade de Santiago de Compostela for her outstanding researcher contract and N. A. acknowledges the Portuguese Foundation for Science and Technology (FCT) for his Ph.D. grant DFA/BD/6218/2020.S

Combination of different chromatographic and sampling modes for high-resolution mass spectrometric screening of organic microcontaminants in water

This study explores the combination of two sampling strategies (polar organic compounds integrative sampler (POCIS) vs. spot sampling) and four chromatographic retention modes (reversed-phase liquid chromatography (RPLC), hydrophilic interaction liquid chromatography (HILIC), mixed-mode liquid chromatography (MMLC) and supercritical fluid chromatography (SFC)) for high-resolution mass spectrometry (HRMS) screening of organic pollutants in water samples. To this end, a suspect screening approach, using iterative data-dependent tandem mass spectrometry (MS/MS) driven by a library of 3227 chemicals (including pharmaceuticals, pesticides, drugs of abuse, human metabolites, industrial chemicals and other pollutants), was employed. Results show that POCIS can afford a larger number of positive identifications as compared to spot sampling. On the other hand, the best suited retention mechanisms, in terms of identified analytes, are SFC, and followed by RPLC, MMLC and HILIC. However, the best combination (POCIS + SFC) would only allow the identification of 67% of the detected analytes. Thus, the combination of the two sampling strategies, spot and passive sampling, with two orthogonal retention mechanisms, RPLC and SFC, is proposed in order to maximize the number of analytes detected (89%). This strategy was applied to different surface water (river and estuary) samples from Galicia (NW Spain). A total of 155 compounds were detected at a confidence level 2a, from which the major class was pharmaceuticals (61%).This research was funded by Xunta de Galicia (ED431C2017/36 and V.C. predoctoral contract: ED481A-2017/156), the Spanish Agencia Estatal de Investigación (ref. CTM2017-84763-C3-R-2 and CTM2017-90980-REDT) and FEDER/ERDF funds. This research has been co-financed by the European Regional Development Fund through the Interreg V-A Spain-Portugal Programme (POCTEP) 2014-2020 (ref. 0725_NOR_WATER_1_P). It only reflects the author’s view; thus, Programme authorities are not liable for any use that may be made of the information contained therein.S

Development and application of an in-house library and workflow for gas chromatography–electron ionization–accurate-mass/high-resolution mass spectrometry screening of environmental samples

This work presents an optimized gas chromatography–electron ionization–high-resolution mass spectrometry (GC-EI-HRMS) screening method. Different method parameters affecting data processing with the Agilent Unknowns Analysis SureMass deconvolution software were optimized in order to achieve the best compromise between false positives and false negatives. To this end, an accurate-mass library of 26 model compounds was created. Then, five replicates of mussel extracts were spiked with a mixture of these 26 compounds at two concentration levels (10 and 100 ng/g dry weight in mussel, 50 and 500 ng/mL in extract) and injected in the GC-EI-HRMS system. The results of these experiments showed that accurate mass tolerance and pure weight factor (combination of reverse-forward library search) are the most critical factors. The validation of the developed method afforded screening detection limits in the 2.5–5 ng range for passive sampler extracts and 1–2 ng/g for mussel sample extracts, and limits of quantification in the 0.6–3.2 ng and 0.1–1.8 ng/g range, for the same type of samples, respectively, for 17 model analytes. Once the method was optimized, an accurate-mass HRMS library, containing retention indexes, with ca. 355 spectra of derivatized and non-derivatized compounds was generated. This library (freely available at https://doi.org/10.5281/zenodo.5647960), together with a modified Agilent Pesticides Library of over 800 compounds, was applied to the screening of passive samplers, both of polydimethylsiloxane and polar chemical integrative samplers (POCIS), and mussel samples collected in Galicia (NW Spain), where a total of 75 chemicals could be identifiedOpen Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This research was funded by Xunta de Galicia (ED431C 2021/06 and V.C. predoctoral contract: ED481A-2017/156), the Spanish Agencia Estatal de Investigación—MCIN/AEI/10.13039/501100011033 (ref. CTM2017-84763-C3-R-2 and PID2020-117686RB-C32), and FEDER/ERDF fundsS