Investigation of pharmaceutical metabolites in environmental waters by LC-MS/MS

Abstract

Pharmaceuticals, once ingested, are commonly metabolized in the body into more polar and soluble forms. These compounds might not be completely removed in the wastewater treatment plants and consequently being discharged into the aquatic ecosystem. In this work, a multi-class sensitive method for the analysis of 21 compounds, including 7 widely consumed pharmaceuticals and 14 relevant metabolites, has been developed based on the use of UHPLC-MS/MS in selected reaction monitoring (SRM) mode. The method was validated in six surface waters (SW) and six effluent wastewaters (EWW) at realistic concentration levels that can be found in waters. The optimized method was applied to the analysis of different types of water samples (rivers, lakes and effluent wastewater), detecting nearly all the parent compounds and metabolites investigated in this work. This fact illustrates that not only pharmaceuticals but also their metabolites are commonly present in these types of waters. Analytical research and monitoring programs should be directed not only towards parent pharmaceuticals but also towards relevant metabolites to have a realistic overview of the impact of pharmaceuticals in the aquatic environment.

Analysis, occurrence, fate and risks of proton pump inhibitors, their metabolites and transformation products in aquatic environment: A review

“…Meanwhile, the use of HR-MS (Q-TOF and hybrid linear ion trap (LTQ) FT Orbitrap mass spectrometer) is steadily increased in recent years and have been also successfully performed either for structure elucidation or/and screening and quantification of PPIs and their TPs in aqueous environmental samples (Boix et al, 2013(Boix et al, , 2014Boleda et al, 2013;Gómez et al, 2007;Gracia-Lor et al, 2014;Hernández et al, 2011;Ibáñez et al, 2009Ibáñez et al, , 2016Kosma et al, 2014aKosma et al, , 2014bLópez et al, 2014;Martínez Bueno et al, 2007;Petrovic et al, 2006;Ibáñez et al, 2016). More specifically, in a very interesting study, LC coupled to HR LTQ Orbitrap MS was performed for the identification of omeprazole and 23 metabolites of omeprazole in Italian municipal influent wastewater .…”

“…Boleda et al (2013) studied the occurrence of omeprazole and its metabolites 4-OH-omeprazole and 5-O-desmethyl omeprazole in surface and drinking water in Spain, using commercial available standards. In addition Gracia-Lor et al (2014) reported the identification of omeprazole and its metabolites 4-hydroxy omeprazole sulfide and 5-hydroxy omeprazole in surface waters and effluent wastewaters in Spain, using also commercial available standards. Confirmation of the analytes identity was guaranteed by acquiring three SRM transitions and evaluating their Q/q ratios and retention time.…”

“…For instance, Gracia-Lor et al (2014) reported concentrations ranging from LOQ-0.028 ng/L and 0.004 ng/L, for 4-hydroxy omeprazole sulfide and for 5-hydroxy omeprazole respectively, in surface waters, while reported also 0.06-0.29 ng/L and 0.12-0.25 ng/L, for 4-hydroxy omeprazole sulfide and for 5-hydroxy omeprazole, respectively, in effluent wastewaters, in Spain. Furthermore, Boleda et al (2013) found concentrations ranging from bLOQ-60 ng/L for 4-OH-omeprazole, in surface waters in Spain, while 5-O-desmethyl omeprazole was not detected.…”

“…Although, PPIs are not regularly detected, considering their high use (Godman et al, 2009(Godman et al, , 2011Woldegiorgis et al, 2009) its analytical monitoring becomes relevant. In addition, in view of the recent reports dealing with the detection of many metabolites and environmental Transformation Products (TPs) in aqueous samples (Boix et al, 2013(Boix et al, , 2014Boleda et al, 2013;Hernández et al, 2011;Gracia-Lor et al, 2014;Ibáñez et al, 2016;López et al, 2014;Ibáñez et al, 2016), environmental contamination by PPIs should be checked and evaluated more thoroughly.…”

Modeling of sorption and degradation of selected pharmaceuticals: Case study of Belgrade groundwater source

“…Higher concentrations of 4-AAA have been detected in surface water samples of the Velika Morava River (Serbia) -512 ng/L (KOVAČEVIĆ et al 2016), as well as in Spain -811 ng/L (GRACIA-LOR et al 2011). Previously, 4-FAA was detected in the Tisa River in Serbia, with a concentration of 186 ng/L (RADOVIĆ et al, 2015) and in considerably higher concentrations in Spain -871 ng/L (GRACIA-LOR et al, 2014). 4-AAA and 4-FAA were detected in low concentrations in BGS well Rb-16, compared to other studies (TEIJON et al, 2010;DE JONGH et al, 2012).…”