Multi‐compound methods for the detection of pharmaceutical residues in various waters applying solid phase extraction (SPE) and gas chromatography with mass spectrometric (GC‐MS) detection

Abstract

Multi-compound methods for the detection of pharmaceutical residues in various waters applying solid phase extraction (SPE) and gas chromatography with mass spectrometric (GC-MS) detection This paper describes two highly sensitive analytical methods for the unambiguous determination of pharmaceutical residues and related polar contaminants in environmental water samples. Both analytical methods use solid phase extraction (SPE), chemical derivatization, and detection of the analytes by capillary gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring (SIM). Using the two methods, a total of 19 pharmaceuticals and 7 related polar contaminants, most of them pesticides, can be detected and quantified down to the low ng/L range in sewage, surface, ground, and drinking water. Recoveries between 70 and 110% and standard deviations of less than 15% were determined for 21 analytes when applying the analytical method that uses pentafluorobenzyl bromide (PFBBr) for derivatization. The second method, which employs N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) for derivatization was found to be slightly less sensitive and reproducible but it also permitted the analysis of several other environmentally important compounds such as the antiepileptic drugs carbamazepine or primidone. From spiking experiments, limits of detection (LODs) between less than 1 and 10 ng/L and limits of quantification (LOQs) between 1 and 40 ng/L were calculated.

Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment

“…Bezafibrate was found in STP effluents [91,118] and in the Paraíba do Sul river (Brazil) [22] as was gemfibrozil [17,18,21] and further iden-tified in surface waters [17,21,88]. Due to its greater persistence, clofibric acid has been found in STP influents [19,71] and effluents [19,53,71], surface water [22,24,71], drinking water [71,119] and North Sea water [25]. All of these pharmaceuticals were shown to be present at concentration levels in the order of ng L −1 or low µg L −1 , which indicates that their exposure may represent a threat for non-target organisms.…”

“…Carbamazepine is ubiq-uitously present in the environment, having an extremely low removal rate in STPs (7%) [54] and consequently being detected in rivers [16,20,21,54,92] at concentrations up to 595 ng L −1 [92] (Table 5). In addition to surface waters, carbamazepine has also been found in groundwater [26,119] at concentrations that can reach 900 ng L −1 . A monitoring programme performed on the river Rhine (Germany) over a decade, showed the regular detection of carbamazepine, with an annual average concentration of 100 ng L −1 [168].…”

Practical overview of analytical methods for endocrine-disrupting compounds, pharmaceuticals and personal care products in water and wastewater

“…(i) Liquid chromatography tandem mass spectrometry LC should preferably be applied for the analysis of organic micropollutants only when using tandem MS because this combination is able to produce fragment ions that are necessary for the explicit identification of the analytes (Reddersen & Heberer 2003). LC-MS/MS allows separation and detection of compounds having the same molecular mass but different product ions, even if they co-elute.…”

“…LC is generally suitable for the determination of compounds that are polar, non-volatile or thermodegradable, which cannot be analysed by GC (Díaz-Cruz & Barceló 2005;Baugros et al 2008). For example, the detection of some pharmaceuticals, such as antibiotics or the extremely polar betablocker compounds, can only be achieved using LC-MS/MS (Ternes 2001;Reddersen & Heberer 2003;Díaz-Cruz & Barceló 2005).…”

“…GC/MS has the advantage over LC-MS/MS in that analyte quantification is less prone to water matrix interferences (Reddersen & Heberer 2003). In addition, GC/MS generally has lower LODs when compared with LC-MS/MS but requires more complicated and time-consuming sample preparation owing to the need for derivatization of polar analytes (Díaz & Barceló 2005;Redjenović et al 2007).…”