Targeted and suspect screening of contaminants in coastal water and sediment samples in Qatar.

In recent years, high resolution mass spectrometry (HRMS) combined with separation techniques has allowed comprehensive analysis of contaminants of emerging concern (CECs) as well as their metabolites and transformation products in various environmental samples via retrospective screening. However, to date, only a few suspect or non-targeted studies on the occurrence of CECs in marine aquatic system are reported. In this study, two methods, based on direct injection for seawater, or ultrasound-assisted extraction for sediments, followed by LC-Q-TOF-MS analysis were developed and applied for the simultaneous targeted and screening of contaminants in coastal samples (seawater, particulates and sediment) from Qatar collected in 2017-2018. Among the twenty-one target analytes (pesticides, PPCPs and a plasticizer), two compounds only were detected in seawater. Caffeine was detected in seawater samples at all sampling sites, and cotinine was detected in seawater samples collected in Umm Bab in 2018 and seawaters receiving stormwater. Traces of trimethoprim and carbamazepine were detected in sediment samples collected at four sites in 2017. These results suggest some inputs of domestic wastewater in the coastal waters in Qatar. In total, twelve molecular features were tentatively identified from suspect screening at concentration levels significantly higher than that in procedure blanks. The presence of four plasticizers and one pesticide were further confirmed using reference standards: diethyl phthalate (DEP), dibutyl phthalate (DBP), and tributyl phosphate (TBP) in seawater samples; bis(2-ethylhexyl) phthalate (DEHP) in sediment and particulate samples; and dinoterb in seawater after storm event and particulate samples. Overall, this study demonstrated the potential of high resolution LC-Q-TOF-MS/MS for combined targeted and non-targeted analyses of trace contaminants in marine systems over a broad range of log P values.

Development of a liquid chromatography-quadrupole-time-of-flight-mass spectrometry based method for the targeted and suspect screening of contaminants in the pearl oyster Pinctada imbricata radiata.

A rapid method based on solvent extraction followed by direct injection in liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-Q-TOF-MS) was developed for the targeted and suspect screening of contaminants in the soft tissues of the pearl oyster Pinctada imbricata radiata. The quantification method was first validated for the targeted analysis of 21 contaminants including some pharmaceutically active compounds, with the relative recoveries ranging from 88 to 123%, and method detection limits generally below 1 ng g-1 on the wet weight (ww) basis. This targeted analysis method was then applied to oyster samples collected around the Qatari coast between 2017/2018, and none of the 21 compounds were detected in these samples. The post-acquisition data treatment based on the accurate mass measurement in both full MS scan and All Ions MS/MS was further used for mining other contaminants in oyster extracts, as well as 21 targeted compounds spiked in oyster extracts (suspect screening). The 21 spiked compounds were identified successfully and the estimated limit of identification for the individual 21 compounds ranged from 0.5 to 117 ng g-1 ww of oyster tissues. A phthalate, di(2-ethylhexyl) phthalate (DEHP) was identified to be present in oyster extracts from 2018 batches, at a concentration level significantly higher than that in procedure blanks. These results confirmed that high resolution MS data obtained using the targeted method can be exploited through suspect screening workflows to identify contaminants in the tissues of bioindicator mollusks. However, a number of false identifications could be obtained and future work will be on improving the success rate of the correct identifications using this workflow.