Multi-residue method for trace level determination of pharmaceuticals in solid samples using pressurized liquid extraction followed by liquid chromatography/quadrupole-linear ion trap mass spectrometry

Department of Environmental Chemistry, IDAEA-CSIC, 08034 Barcelona, Spain.
Talanta (Impact Factor: 3.55). 11/2009; 80(1):363-71. DOI: 10.1016/j.talanta.2009.06.077
Source: PubMed


A simple and sensitive method for simultaneous analysis of 43 pharmaceutical compounds in sewage sludge and sediment samples was developed and validated. The target compounds were extracted using pressurized liquid extraction (PLE) and then purified and pre-concentrated by solid phase extraction (SPE) using a hydrophilic-lipophilic balanced polymer. PLE extraction was performed on temperature of 100 degrees C, with methanol/water mixture (1/2, v/v) as extraction solvent. The quantitative analysis was performed by liquid chromatography tandem mass spectrometry using a hybrid triple quadrupole-linear ion trap mass spectrometer (LC-QqLIT-MS). Data acquisition was carried out in selected reaction monitoring (SRM) mode, monitoring two SRM transitions to ensure an accurate identification of target compounds in the samples. Additional identification and confirmation of target compounds were performed using the Information Dependent Acquisition (IDA) function. The method was validated through the estimation of the linearity, sensitivity, repeatability, reproducibility and matrix effects. The internal standard approach was used for quantification because it efficiently corrected matrix effects. Despite the strong matrix interferences, the recoveries were generally higher of 50% in both matrixes and the detection and quantification limits were very low. Beside the very good sensitivity provided by LC-QqLIT-MS, an important characteristic of the method is that all the target compounds can be simultaneously extracted, treated and analysed. Hence, it can be used for routine analysis of pharmaceuticals providing large amount of data. The method was applied for the analysis of pharmaceuticals in river sediment and wastewater sludge from three treatment plants with different treatment properties (i.e. capacity, secondary treatment, quality of influent waters). The analysis showed a widespread occurrence of pharmaceuticals in the sludge matrices.

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    • "As the property of sediment is different with seafood and seawater, a suitable pretreatment method to efficiently extract LMTs from marine sediments should be developed. Several methods, such as ultrasonicassisted extraction (Peng et al., 2006; Ternes et al., 2002), Soxhlet extraction (Peng et al., 2006), and pressurized liquid extraction (PLE) (Jelić et al., 2009; Preud'homme and Potin-Gautier, 2003; Vazquez-Roig et al., 2010) have been used to extract organic pollutants in environmental solid samples. Compared with Soxhlet extraction and other preparation methods, pressurized liquid extraction uses high temperature and pressure automate extraction of organic pollutants in a solid matrix, which is a rapid and effective sample extraction technology (Richter et al., 1996). "
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    ABSTRACT: A method based on sample preparation by accelerated solvent extraction and analysis by liquid chromatography-tandem mass spectrometry was validated and used for determination of seven typical lipophilic marine toxins (LMTs) in marine sediment samples collected from three typical coastal bays in China. Satisfactory specificity, reproducibility (RSDs≤14.76%), stability (RSDs≤17.37%), recovery (78.0%-109.0%), and detection limit (3.440pg/g-61.85pg/g) of the developed method were achieved. The results obtained from the analysis of samples from Hangzhou Bay revealed okadaic acid as the predominant LMT with concentrations ranging from 186.0 to 280.7pg/g. Pecenotoxin-2 was quantified in sediment samples from Laizhou Bay at the concentrations from 256.4 to 944.9pg/g. These results suggested that the proposed method was reliable for determining the typical LMTs in marine sediments and that the sediments obtained from Hangzhou Bay, Laizhou Bay and Jiaozhou Bay were all contaminated by certain amounts of LMTs.
    No preview · Article · Oct 2015 · Marine Pollution Bulletin
    • "PAH content was analysed according to USEPA, United States Environmental Protection Agency (2007). Selected pharmaceuticals and secondary alkane sulfonates (SAS) were measured following the methods proposed by Jelic et al. (2009) and Baena-Nogueras et al. (2013). 2.5. "
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    ABSTRACT: Marine sediment quality of wastewater discharges areas was determined by using in situ caged clams Ruditapes philippinarum taking into account the seasonality. Clams were caged in sediment directly affected by wastewater discharges at four sites (P1, P2, P3, P4) at the Bay of Cádiz (SW, Spain), and one reference site (P6). Exposure to contaminated sediments was confirmed by measurement of metals and As, PAH, pharmaceutical products and surfactants (SAS) in bottom sediments. Biological effects were determined by following biomarkers of exposure (activities of 7-ethoxyresorufin O-deethylase - EROD, dibenzylfluorescein dealkylase - DBF, glutathione S-transferase - GST, glutathione peroxidase - GPX, glutathione reductase - GR and acetylcholinesterase - AChE), effects (lysosomal membrane stability - LMS, DNA damage and lipid peroxidation - LPO), energy status (total lipids - TLP and mitochondrial electron transport - MET), and involved in the mode of action of pharmaceutical products (monoamine oxidase activity - MAO, alkali-labile phosphates - ALP levels and cyclooxygenase activity - COX). In winter, urban effluents were detoxified by phase I biotransformation (CYP3A-like activity), phase II (GST), and the activation of antioxidant defence enzymes (GR). Urban effluents lead to the detoxification metabolism (CYP1A-like), oxidative effects (LPO and DNA damage), neurotoxicity (AChE) and neuroendocrine disruption (COX and ALP levels) involved in inflammation (P1 and P2) and changes in reproduction as spawning delay (P3 and P4) in clams exposed in summer. Adverse effects on biota exposed to sediment directly affected by wastewater discharges depend on the chemical contamination level and also on the reproductive cycle according to seasonality.
    No preview · Article · Sep 2015 · Science of The Total Environment
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    • ". Further details can be found in Jelic et al. (2009). The main modification of the method was that a different ultra-performance liquid chromatography (UPLC)-tandem mass spectrometry system was used, which consisted of a Bruker EvoQ Elite liquid chromatographer coupled to a UPLC Bruker Advance tandem mass spectrometer ( "
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    ABSTRACT: Lethal and sublethal responses related to different phases of metabolism (phases I and II enzymatic activities), neurotoxicity (acetylcholinesterase activity), oxidative stress (lipid peroxidation and antioxidant enzyme activities), and genetic damage (DNA strand breaks) were analysed to assess the possible adverse effects of pharmaceuticals bound to marine sediments. The crustacean amphipod Ampelisca brevicornis was chosen as the bioindicator species. Organisms were exposed for 10 days to sediment spiked with pharmaceutical compounds frequently used and previously detected in the environment: carbamazepine (CBZ), ibuprofen (IBP), fluoxetine (FX), 17α-ethynylestradiol (EE2), propranolol (PRO), and caffeine (CAF). Short-term bioassay to evaluate amphipod mortality was recommended to assess pollution by CBZ, FX, and PRO. IBP and PRO were metabolized by phases I and II detoxification enzymatic activities. Oxidative stress was caused by PRO and CAF. Contrary to expected results, DNA damage (strand breaks) decreased after the exposure of amphipods to sediment spiked with IBP, FX, EE2, PRO, and CAF (including environmental concentrations). FX was neurotoxic to amphipods. The battery of biomarkers tested allowed the assessment of bioavailability, oxidative stress, genotoxicity, and neurotoxicity of the pharmaceuticals analysed. The results of this study suggested that pharmaceutical products at concentrations currently found in the environment might cause a wide variety of adverse effects (based on laboratory studies). The results obtained here are useful for environmental risk assessment of marine sediments contaminated by pharmaceuticals. Nevertheless, more research is needed using field-based marine sediments.
    Full-text · Article · Sep 2014 · Archives of Environmental Contamination and Toxicology
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