Validation and application of an LC-MS/MS method for the simultaneous quantification of 13 pharmaceuticals in seawater

Abstract

Knowledge of the presence of micropollutants such as pharmaceuticals, in coastal areas, is very limited; therefore, the main objective of this study was to optimize and validate a new analytical method for the quantitative analysis of 13 multiclass pharmaceuticals in seawater. Target compounds included antibiotics, non-steroidal anti-inflammatory drugs, beta-blockers, lipid regulators and one psychiatric drug. A combination of solid-phase extraction and liquid chromatography coupled with multiple mass spectrometry enabled their detection at the low nanogram per litre level. The limits of quantification varied between 1 and 50 ng L(-1), for most components the linearities were more than 0.99 and the recoveries obtained in seawater (95-108%) were satisfactory. This method was applied to seawater and estuarine water samples collected in the Belgian coastal zone, to assess the prevalence of common pharmaceuticals in this marine environment. Seven pharmaceuticals, including compounds of which the presence in marine environments had not been reported earlier, were detected, with salicylic acid and carbamazepine being the most abundant, in concentrations up to 855 ng L(-1).

Assessment of non-steroidal anti-inflammatory and analgesic pharmaceuticals in seawaters of North of Portugal: Occurrence and environmental risk

“…These low levels might be justified by its ready biodegrada-tion in the aquatic environment, forming salicylic acid, a more active metabolite (Cleuvers, 2004;Rabiet et al, 2006) together with its high removal efficiency in WWTPs that may range from 80 to 98% (Ziylan and Ince, 2011). No data on the occurrence of acetylsalicylic acid in sea-waters is available in literature, though the presence of its main metab-olite salicylic acid had been reported in the Belgian coastal area (North Sea) (Wille et al, 2010) and in the Mediterranean Sea (Spain) , at levels up to 660 ng L −1 .…”

“…Several therapeutic groups were studied, including, for example, non-steroidal anti-inflammatory drugs (NSAIDs) Wille et al, 2010), analgesics Nödler et al, 2010), antibiotics (Nebot et al, 2007;Wille et al, 2010), β-blockers Wille et al, 2010), lipid regulators (Fang et al, 2012;Gros et al, 2012) and psychiatric drugs Wille et al, 2010). Diclofenac (Rodriguez-Navas et al, 2013), ibuprofen (Loos et al, 2013b), naproxen , ketoprofen , salicylic acid (Wille et al, 2010), acetaminophen and codeine are among the most de-tected NSAIDs/analgesics in seawaters of the North, Mediterranean and Adriatic Seas and even in the Pacific and Indian Oceans at levels up to few hundred ng L −1 . Some examples of levels of NSAIDs/analgesics detected in seawaters are present in Table 1.…”

“…Coastal areas represent a major asset due to the economic activities that may take place, including tourism, commercial ports and harbours and certain types of traditional fishing. Due to their location, coastal sea-waters may be more prone to present higher pharmaceutical concentra-tions than other seawater samples (Loos et al, 2013b;Wille et al, 2010). In Portugal, coastal areas are the most densely populated regions where the largest cities and the most important industries are situated.…”

Occurrence and risks of antibiotics in the coastal aquatic environment of the Yellow Sea, North China

“…These antibiotics and/or the residues used in mariculture cause various degrees of antibiotic pollution in the coastal environment. For example, as shown in Table 1, the maximum concentration (c max ) of roxithromycin (RTM) was up to 630 ng L − 1 in Bohai Bay (Zou et al, 2011) of the of sulfamethoxazole (SMX) was up to 77 ng L − 1 in Liaodong Bay of the BS, the c max of dehydrated erythromycin (ETM-H 2 O) was up to 1730 ng L − 1 in Victoria Harbour of Hong Kong, China (Minh et al, 2009), the c max of SMX was up to 43 ng L − 1 in Belgian coastal harbours (Wille et al, 2010), and so on. However, the most recent studies mainly pay attention to semi-enclosed areas with poor water-exchange ability, such as the coastal areas of the three main bays (Bohai Bay, Laizhou Bay and Liaodong Bay) of the BS Zhang et al, 2012b;Zou et al, 2011) and Victoria Harbour of Hong Kong (Gulkowska et al, 2007;Minh et al, 2009;Xu et al, 2007b).…”

Antibiotics in the offshore waters of the Bohai Sea and the Yellow Sea in China: Occurrence, distribution and ecological risks

“…Among the ten detected antibiotics, the three predominant antibiotics also presented the highest concentrations. The mean and maximum concentrations of the three predominant antibiotics were from 0.69 to 1.4 ng L À1 and from 6.7 , respectively, which were obviously lower than those in the coastal water, such as the Bohai Bay (Zou et al, 2011), Laizhou Bay (Zhang et al, 2012b), Liaodong Bay (Jia et al, 2011), Victor Harbor (Minh et al, 2009), Hong Kong coasts (Gulkowska et al, 2007) and Belgian coastal harbors (Wille et al, 2010) (Supplementary Table S6). Compared with the three predominant antibiotics, the other antibiotics showed much lower concentrations.…”