Development of analytical strategies using U-HPLC-MS/MS and LC-ToF-MS for the quantification of micropollutants in marine organisms

Abstract

Organic micropollutants such as pharmaceuticals, perfluorinated compounds (PFCs), and pesticides, are important environmental contaminants. To obtain more information regarding their presence in marine organisms, an increasing demand exists for reliable analytical methods for quantification of these micropollutants in biotic matrices. Therefore, we developed extraction procedures and new analytical methods for the quantification of 14 pesticides, 10 PFCs, and 11 pharmaceuticals in tissue of marine organisms, namely blue mussels (Mytilus edulis). This paper presents these optimized analytical procedures and their application to M. edulis, deployed at five stations in the Belgian coastal zone. The methods consisted of a pressurized liquid extraction and solid-phase extraction (SPE) followed by ultra high-performance liquid chromatography coupled to triple quadrupole mass spectrometry for pharmaceuticals and pesticides, and of a liquid extraction using acetonitrile and SPE, followed by liquid chromatography coupled to time-of-flight mass spectrometry for PFCs. The limits of quantification of the three newly optimized analytical procedures in M. edulis tissue varied between 0.1 and 10 ng g(-1), and satisfactory linearities (≥0.98) and recoveries (90-106%) were obtained. Application of these methods to M. edulis revealed the presence of five pharmaceuticals, two PFCs, and seven pesticides at levels up to 490, 5, and 60 ng g(-1), respectively. The most prevalent micropollutants were salicylic acid, paracetamol, perfluorooctane sulfonate, chloridazon, and dichlorvos.

Occurrence of pharmaceuticals and endocrine disrupting compounds in macroalgaes, bivalves, and fish from coastal areas in Europe

“…The levels found are usually in the low ng/g (i.e. sertraline 1.4 ng/g dw (Dodder et al, 2014), venlanfaxine 2.7 ng/g dw (Martinez Bueno et al, 2014), azithromycin 3.0 ng/g dw (Alvarez-Muñoz et al, 2015), carbamazepine 11 ng/g dw (Wille et al, 2011), but depending on the compound they can reach up to a few hundreds of ng/g (i.e. ciprofloxacin 208 ng/g dw (Li et al, 2012), paracetamol 115 ng/g dw and salicylic acid 490 ng/g dw (Wille et al, 2011).…”

“…However, the number of papers published reporting the occurrence and levels of PhACs in marine organisms is considerably lower. They have been performed mainly in mollusks (Wille et al, 2011;McEneff et al, 2014;Klosterhaus et al, 2013;Martinez Bueno et al, 2013Li et al, 2012;Dodder et al, 2014) and freshwater fish (Gelsleichter and Szabo, 2013;Maruya et al, 2012;Azzouz et al, 2011). The levels found are usually in the low ng/g (i.e.…”

“…sertraline 1.4 ng/g dw (Dodder et al, 2014), venlanfaxine 2.7 ng/g dw (Martinez Bueno et al, 2014), azithromycin 3.0 ng/g dw (Alvarez-Muñoz et al, 2015), carbamazepine 11 ng/g dw (Wille et al, 2011), but depending on the compound they can reach up to a few hundreds of ng/g (i.e. ciprofloxacin 208 ng/g dw (Li et al, 2012), paracetamol 115 ng/g dw and salicylic acid 490 ng/g dw (Wille et al, 2011). Carbamazepine has been the compound most frequently reported in marine organisms, a total of 4 studies has been published (Wille et al, 2011;McEneff et al, 2014;Klosterhaus et al, 2013;Martinez Bueno et al, 2013), followed by sertraline (Klosterhaus et al, 2013;Dodder et al, 2014;Gelsleichter and Szabo, 2013), venlafaxine (Martinez Bueno et al, 2014;Gelsleichter and Szabo, 2013) and diazepam (Klosterhaus et al, 2013;Maruya et al, 2012), all psychiatric drugs.…”

Sources, impacts and trends of pharmaceuticals in the marine and coastal environment

“…Carbamazepine, ciprofloxacin and enrofloxacin were the most frequently reported compounds each being reported in four studies. Only three studies reported concentrations for pharmaceutical transformation products including erythromycin-H 2 O, salicylic acid and metabolites of venlafaxine [62,66,79]. Higher concentrations of venlafaxine metabolites than parent compound were detected in mussels (Mytilus galloprovincialis).…”

Metabolite profiling of carbamazepine and ibuprofen in Solea senegalensis bile using high-resolution mass spectrometry

“…Besides, marine species in coastal areas may also be exposed to pharmaceuticals through effluent discharges, waste disposal, and the use of drugs in aquaculture. The impact of this exposure, however, has received very little attention, and studies reporting the detection of human drug residues in wild marine fish species are very scarce [4][5][6]. This is surprising because the occurrence of pharmaceuticals in estuaries and potential contaminated areas has raised concerns about potential adverse effects on the species living on them.…”