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
ABSTRACT 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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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.Archives of Environmental Contamination and Toxicology 09/2014; 68(2). DOI:10.1007/s00244-014-0080-0 · 1.96 Impact Factor
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ABSTRACT: This work deals with the environmental distribution of nonionic surfactants (nonylphenol and alcohol ethoxylates), their metabolites (NP, nonylphenol; NPEC, nonylphenol ethoxycarboxylates; and PEG, polyethylene glycols) and a selection of 64pharmaceuticals in the Long Island Sound (LIS) Estuary which receives important sewage discharges from New York City (NYC). Most target compounds were efficiently removed (>95%) in one wastewater treatment plant monitored, with the exception of NPEC and some specific drugs (e.g., hydrochlorothiazide). Concentrations of surfactants (1.4-4.5μgL(-1)) and pharmaceuticals (0.1-0.3μgL(-1)) in seawater were influenced by tides and sampling depth, consistent with salinity differences. Surfactants levels in suspended solids samples were higher than 1μgg(-1), whereas only most hydrophobic or positively charged pharmaceuticals could be found (e.g., tamoxifen, clarithromycin). Maximum levels of target compounds in LIS sediments (PEG at highest concentrations, 2.8μgg(-1)) were measured nearest NYC, sharply decreasing with distance from major sewage inputs.Marine Pollution Bulletin 01/2014; 85(2). DOI:10.1016/j.marpolbul.2014.01.022 · 2.79 Impact Factor
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ABSTRACT: Novel methods utilizing liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry were validated for low-level detection of 104 pharmaceuticals and personal care products ingredients (PPCPs) and four alkylphenols (APs) in environmental samples. The methods were applied to surface water, sediment, and mussel tissue samples collected from San Francisco Bay, CA, USA, an urban estuary that receives direct discharge from over forty municipal and industrial wastewater outfalls. Among the target PPCPs, 35% were detected in at least one sample, with 31, 10, and 17 compounds detected in water, sediment, and mussels, respectively. Maximum concentrations were 92ng/L in water (valsartan), 33ng/g dry weight (dw) in sediments (triclocarban), and 14ng/g wet weight (ww) in mussels (N,N-diethyl-m-toluamide). Nonylphenol was detected in water (<2-73ng/L), sediments (22-86ng/g dw), and mussels (<0.04-95ng/g ww), and nonylphenol mono- and diethoxylates were detected in sediments (<1-40ng/g dw) and mussels (<5-192ng/g ww). The concentrations of PPCPs and APs detected in the San Francisco Bay samples were generally at least an order of magnitude below concentrations expected to elicit toxic effects in aquatic organisms. This study represents the first reconnaissance of PPCPs in mussels living in an urban estuary and provides the first field-derived bioaccumulation factors (BAFs) for select compounds in aquatic organisms.Environment international 04/2013; 54:92-9. DOI:10.1016/j.envint.2013.01.009 · 5.66 Impact Factor