In this article, a dataset from a collaborative non-target screening trial organised by the NORMAN Association is used to review the state-of-the-art and discuss future perspectives of non-target ...screening using high-resolution mass spectrometry in water analysis. A total of 18 institutes from 12 European countries analysed an extract of the same water sample collected from the River Danube with either one or both of liquid and gas chromatography coupled with mass spectrometry detection. This article focuses mainly on the use of high resolution screening techniques with target, suspect, and non-target workflows to identify substances in environmental samples. Specific examples are given to emphasise major challenges including isobaric and co-eluting substances, dependence on target and suspect lists, formula assignment, the use of retention information, and the confidence of identification. Approaches and methods applicable to unit resolution data are also discussed. Although most substances were identified using high resolution data with target and suspect-screening approaches, some participants proposed tentative non-target identifications. This comprehensive dataset revealed that non-target analytical techniques are already substantially harmonised between the participants, but the data processing remains time-consuming. Although the objective of a “fully-automated identification workflow” remains elusive in the short term, important steps in this direction have been taken, exemplified by the growing popularity of suspect screening approaches. Major recommendations to improve non-target screening include better integration and connection of desired features into software packages, the exchange of target and suspect lists, and the contribution of more spectra from standard substances into (openly accessible) databases.
Graphical Abstract
Matrix of identification approach versus identification confidence
•Bisphenol A (BPA) was completely removed in 10min by chlorination in our conditions.•A non-targeted approach was developed to reveal 21 transformation products.•Brominated intermediates were ...reported for the first time for BPA chlorination.•We evidenced a decrease of estrogenic activity after chlorination by ER-CALUX.
Besides the performance of water treatments on the removal of micropollutants, concern about the generation of potential biologically active transformation products has been growing. Thus, the detection and structural elucidation of micropollutants transformation products have turned out to be major issues to evaluate comprehensively the efficiency of the processes implemented for drinking water treatment. However, most of existing water treatment studies are carried out at the bench scale with high concentrations and simplified conditions and thus do not reflect realistic conditions. Conversely, this study describes a non-targeted profiling approach borrowed from metabolomic science, using liquid chromatography coupled to high-resolution mass spectrometry, in order to reveal potential chlorination products of bisphenol A (BPA) in real water samples spiked at 50μgL−1. Targeted measurements first evidenced a fast removal of BPA (>99%) by chlorination with sodium hypochlorite (0.8mgL−1) within 10min. Then, the developed differential global profiling approach enabled to reveal 21 chlorination products of BPA. Among them, 17 were brominated compounds, described for the first time, demonstrating the potential interest of this innovative methodology applied to environmental sciences. In parallel to the significant removal of BPA, the estrogenic activity of water samples, evaluated by ER-CALUX assay, was found to significantly decrease after 10min of chlorination. These results confirm that chlorination is effective at removing BPA in drinking water and they may indicate that the generated compounds have significantly lower estrogenic activity.
► We noticed the impact of chlorination on ethinylestradiol in water. ► We developed a new tool to reveal the by-products generated. ► New chlorination by-products of EE2 have been highlighted and ...identified.
The detection and structural elucidation of micropollutants treatment by-products are major issues to estimate efficiencies of the processes employed for drinking water production versus endocrine disruptive compounds contamination. This issue was mainly investigated at the laboratory scale and in high concentration conditions. However, potential by-products generated after chlorination can be influenced by the dilution factor employed in real conditions. The present study proposes a new methodology borrowed to the metabolomic science, using liquid chromatography coupled to high-resolution mass spectrometry, in order to reveal potential chlorination by-products of ethinylestradiol in spiked real water samples at the part-per-billion level (5
μg
L
−1). Conventional targeted measurements first demonstrated that chlorination with sodium hypochlorite (0.8
mg
L
−1) led to removals of ethinylestradiol over 97%. Then, the developed differential global profiling approach permitted to reveal eight chlorination by-products of EE2, six of them being described for the first time. Among these eight halogenated compounds, five have been structurally identified, demonstrating the potential capabilities of this new methodology applied to environmental samples.
For a few years, the concern of water treatment companies is not only focused on the removal of target micropollutants but has been extended to the investigation of potential biologically active ...by-products generated during the treatment processes. Therefore, some methods dedicated to the detection and structural characterization of such by-products have emerged. However, most of these studies are usually carried out under simplified conditions (e.g. high concentration levels of micropollutants, drastic treatment conditions, use of deionized or ultrapure water) and somewhat unrealistic conditions compared to that implemented in water treatment plants. In the present study, a real field water sample was fortified at the part-per-billion level (50 μg L−1) with estrone-3-sulfate (E1-3S) before being ozonated (at 1 mg L−1) for 10 min. In a first step, targeted measurements evidenced a degradation of the parent compound (>80%) in 10 min. Secondly, a non-targeted chemical profiling approach derived from metabolomic profiling studies allowed to reveal 11 ozonation by-products, among which 4 were found predominant. The estrogenic activity of these water samples spiked with E1-3S before and after treatment was assessed by the ER-CALUX assay and was found to decrease significantly after 10 min of ozonation. Therefore, this innovative methodological strategy demonstrated its suitability and relevancy for revealing unknown compounds generated from water treatment, and permitted to generate new results regarding specifically the impact of ozonation on estrone-3-sulfate. These results confirm that ozonation is effective at removing E1-3S in drinking water and indicate that the by-products generated have significantly lower estrogenic activity.
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•Estrone-sulfate was mostly decomposed (80%) by ozone within 10 min in our conditions.•A non-targeted approach based on metabolomic was developed to reveal 11 by-products.•Major by-products were structurally assigned by H/D exchange and multistage HRMSn.•We evidenced a decrease of estrogenic activity after ozonation by ER-CALUX.
The aquatic environment can contain numerous micropollutants and there are concerns about endocrine activity in environmental waters and the potential impacts on human and ecosystem health. In this ...study a complementary chemical analysis and in vitro bioassay approach was applied to evaluate endocrine activity in treated wastewater, surface water and drinking water samples from six countries (Germany, Australia, France, South Africa, the Netherlands and Spain). The bioassay test battery included assays indicative of seven endocrine pathways, while 58 different chemicals, including pesticides, pharmaceuticals and industrial compounds, were analysed by targeted chemical analysis. Endocrine activity was below the limit of quantification for most water samples, with only two of six treated wastewater samples and two of six surface water samples exhibiting estrogenic, glucocorticoid, progestagenic and/or anti-mineralocorticoid activity above the limit of quantification. Based on available effect-based trigger values (EBT) for estrogenic and glucocorticoid activity, some of the wastewater and surface water samples were found to exceed the EBT, suggesting these environmental waters may pose a potential risk to ecosystem health. In contrast, the lack of bioassay activity and low detected chemical concentrations in the drinking water samples do not suggest a risk to human endocrine health, with all samples below the relevant EBTs.
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•Wastewater, surface water and drinking water grab samples from 6 countries analysed.•Applied bioassays for 7 endocrine pathways in agonist and antagonist mode.•Endocrine activity only above LOQ in two wastewater and two surface water samples.•Estrogenic and glucocorticoid activity in wastewater may pose ecological risk.•Lack of endocrine activity in drinking water indicates negligible risk to humans.
For a few years, the concern of water treatment companies is not only focused on the removal of target micropollutants but has been extended to the investigation of potential biologically active ...by-products generated during the treatment processes. Therefore, some methods dedicated to the detection and structural characterization of such by-products have emerged. However, most of these studies are usually carried out under simplified conditions (e.g. high concentration levels of micropollutants, drastic treatment conditions, use of deionized or ultrapure water) and somewhat unrealistic conditions compared to that implemented in water treatment plants. In the present study, a real field water sample was fortified at the part-per-billion level (50 mu g L-1) with estrone-3-sulfate (E1-3S) before being ozonated (at 1 mg L-1) for 10 min. In a first step, targeted measurements evidenced a degradation of the parent compound (>80%) in 10 min. Secondly, a non-targeted chemical profiling approach derived from metabolomic profiling studies allowed to reveal 11 zonation by-products, among which 4 were found predominant. The estrogenic activity of these water samples spiked with E1-3S before and after treatment was assessed by the ER-CALUX assay and was found to decrease significantly after 10 min of ozonation. Therefore, this innovative methodological strategy demonstrated its suitability and relevancy for revealing unknown compounds generated from water treatment, and permitted to generate new results regarding specifically the impact of ozonation on estrone-3-sulfate. These results confirm that ozonation is effective at removing E1-3S in drinking water and indicate that the by-products generated have significantly lower estrogenic activity. (C) 2013 Elsevier Ltd. All rights reserved.
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