Occurrence and environmental risk assessment of 4 estrogenic compounds in surface water in Belgium in the frame of the EU Watch List.

The presence of natural estrogens estrone (E1), 17ß-estradiol (E2), estriol (E3) and synthetic estrogen 17α-ethynylestradiol (EE2) in the aquatic environment has raised concerns because of their high potency as endocrine disrupting chemicals. The European Commission (EC) established a Watch List of contaminants of emerging concerns including E1, E2 and EE2. The proposed environmental quality standards (EQSs) are 3.6, 0.4, 0.035 ng/L, for E1, E2, EE2, respectively. A thorough evaluation of analytical procedures developed by several studies aiming to perform sampling campaigns in different European countries highlighted that the required limits of quantification in surface water were not reached, especially for EE2 and to a lesser extent for E2. Moreover, data regarding the occurrence of these contaminants in Belgian surface water are very limited. A sampling campaign was therefore performed on a wide range of rivers in Belgium (accounting for a total of 63 samples). The detection frequencies of E1, E2, E3 and EE2 were 100, 98, 86 and 48%, respectively. E1 showed the highest mean concentration (= 4.433 ng/L). In contrast, the mean concentration of EE2 was 0.042 ng/L. The risk quotients (RQs) were calculated based on the respective EQS of each analyte. The frequency of exceedance of the EQS was 31.7% for E1, EE2, while it increased to 44.4% for E2. The extent of exceedance of the EQS, represented by the 95th percentile of the RQ dataset, was higher than 1 for E1, E2, EE2. The use of a confusion matrix was investigated to try to predict the risk posed by E2, EE2, based on the concentration of E1.

Development And Validation Of A Method For Determining Estrogenic Compounds In Surface Water At The Ultra-Trace Level Required By The EU Water Framework Directive Watch List.

Natural estrogens (estrone: E1, 17ß-estradiol: E2, estriol: E3) and the synthetic estrogen (17α-ethinylestradiol: EE2) are endocrine disruptors harmful to aquatic wildlife. The European Commission included these molecules in the surface water Watch Lists issued in 2015 and 2018 under the Water Framework Directive regarding emerging aquatic pollutants, proposing maximum detection limits (LOD) of 0.035 ng/L for EE2 and 0.4 ng/L for E1 and E2. Attaining these limits represents a challenge even with the most up-to-date analytical tools, in particular in surface water. A two-step sample preparation, involving a preliminary extraction of a whole water sample on a solid-phase extraction (SPE) disk and further purification on a Florisil SPE cartridge, was optimized. The purified extract was derivatized subsequently and quantified by LC-MS/MS. The main goal was to maximize the recoveries to achieve the very low LODs required by the European Watch Lists. The method was fully validated in seven surface water. The LODs calculated were below the maximum acceptable limits required by the European Commission.

Trace analysis of estrogenic compounds in surface and groundwater by ultra high performance liquid chromatography-tandem mass spectrometry as pyridine-3-sulfonyl derivatives.

Natural estrogens (estrone: E1, 17ß-estradiol: E2, estriol: E3) and synthetic 17α-ethynylestradiol (EE2) are reported as strong endocrine disruptors even at extremely low concentrations. Therefore, the watch list from the European Commission regarding emerging aquatic pollutants recommended maximum detection limits of 0.035 ng/L for EE2 and 0.4 ng/L for E1 and E2. In this study, a UHPLC-ESI-MS/MS method allowing quantification of E1, E2, E3 and EE2 in aqueous matrices was developed. The analytes were derivatized using pyridine-3-sulfonyl chloride and a broad range of product ions were generated and their specificity was assessed by analyzing both surface and groundwater. At least two product ions for each estrogenic compound were proved to be specific and hence suitable for quantification and confirmation. In complex aqueous matrices, analyte responses were particularly affected by ion suppression. This phenomenon was reduced by optimizing the clean-up and selecting a suitable stationary phase for the chromatographic separation. The limits of quantification assessed in surface water with the optimized method ranged from 0.098 ng/L (EE2) to 2.73 ng/L (E3).

Speciation of five arsenic species (arsenite, arsenate, MMAAV, DMAAV and AsBet) in different kind of water by HPLC-ICP-MS.

A method using Ion Chromatography hyphenated to an Inductively Coupled Plasma-Mass Spectrometer has been developed to accurately determine arsenite (As(III)), arsenate (As(V)), mono-methylarsonic acid (MMAA(V)), dimethylarsinic acid (DMAA(V)) and arsenobetaine (AsBet) in different water matrices. The developed method showed a high sensitivity with detection limits for each arsenic species close to 0.4pg injected. Arsenite and arsenate were the major species found in surface and well waters, but AsBet and DMAA(V) were found in some surface waters, which has never been reported before, while in some natural mineral waters located in volcanic region, the arsenic content exceeded the maximal admissible arsenic content by European legislation standards and the predominant form was As(V).