Determination of pharmaceuticals and antiseptics in water by solid-phase extraction and gas chromatography/mass spectrometry: analysis via pentafluorobenzylation and stable isotope dilution.
ABSTRACT A sensitive yet robust analytical method is presented for the simultaneous determination of 12 human pharmaceuticals (valproic acid, phenytoin, ibuprofen, gabapentin, acetaminophen, gemfibrozil, naproxen, ketoprofen, secobarbital, phenobarbital, 5-fluorouracil, and diclofenac) and 6 antiseptics (biosol, biphenylol, p-chloro-m-cresol, p-chloro-m-xylenol, chlorophene, and triclosan). The method employs solid-phase extraction (SPE) followed by a novel pentafluorobenzylation using a mixture of acetontrile/water (1/1, v/v). The method is simple to perform (derivatization can be completed in a single test tube) and eliminates the need for any solvent/SPE cartridge drying or blow-down. It affords excellent resolution, high sensitivity and reproducibility, and freedom from interference even for matrices as complex as untreated sewage. The method was applied to the analysis of sewage samples using 15 isotopically labeled surrogates, which resulted in the detection of 10 of the 12 pharmaceuticals and all of the antiseptics sought. Ten of 15 surrogates were synthesized from pure analytes by a simple H-D exchange reaction employing D(2)O and D(2)SO(4). Measured recoveries were sensitive to matrix effects and varied substantially among analytes, indicative of the limitations associated with using a single surrogate standard.
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ABSTRACT: As part of the continuing effort to collect baseline information on the environmental occurrence of pharmaceuticals, and other organic wastewater contaminants (OWCs) in the Nation's water resources, water samples were collected from a network of 47 groundwater sites across 18 states in 2000. All samples collected were analyzed for 65 OWCs representing a wide variety of uses and origins. Site selection focused on areas suspected to be susceptible to contamination from either animal or human wastewaters (i.e. down gradient of a landfill, unsewered residential development, or animal feedlot). Thus, sites sampled were not necessarily used as a source of drinking water but provide a variety of geohydrologic environments with potential sources of OWCs. OWCs were detected in 81% of the sites sampled, with 35 of the 65 OWCs being found at least once. The most frequently detected compounds include N,N-diethyltoluamide (35%, insect repellant), bisphenol A (30%, plasticizer), tri(2-chloroethyl) phosphate (30%, fire retardant), sulfamethoxazole (23%, veterinary and human antibiotic), and 4-octylphenol monoethoxylate (19%, detergent metabolite). Although sampling procedures were intended to ensure that all groundwater samples analyzed were indicative of aquifer conditions it is possible that detections of some OWCs could have resulted from leaching of well-construction materials and/or other site-specific conditions related to well construction and materials. Future research will be needed to identify those factors that are most important in determining the occurrence and concentrations of OWCs in groundwater.Science of The Total Environment 07/2008; 402(2-3):192-200. · 3.26 Impact Factor
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ABSTRACT: Sewage influents and effluents of different urban areas of Greece, were analyzed for polar pharmaceutical residues, used in human medicine. Drugs investigated were the anti-inflammatory drugs diclofenac and ibuprofen, the metabolite of the drugs clofibrates used as blood lipid regulators, clofibric acid and the analgesics phenazone and propyphenazone. Analysis was carried out using capillary gas chromatography-mass spectrometry with selected ion monitoring. The method used was involved solid phase extraction (C(18)) and derivatization with pentafluorobenzyl bromide. Diclofenac was detected in every sewage effluent sample.Chemosphere 05/2003; 51(2):69-75. · 3.14 Impact Factor
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ABSTRACT: This paper reviews current information on the chronic aquatic toxicity of human pharmaceuticals and how it should be measured. Chronic toxicity tests with Cyanobacteria are likely to be sensitive surrogates for both algae and other unicellular organisms, although possibly not for higher plants. In contrast, there is little evidence of a general need to perform chronic aquatic invertebrate tests for all human pharmaceuticals, although further acute-to-chronic ratio data are required for the main therapeutic classes and modes of action of pharmaceuticals before this issue can be fully resolved. Chronic fish tests may be necessary for some substances, but it is likely that these can be focused more accurately through use of information in mammalian toxicity datasets. For some substances and modes of action, life-cycle or partial life-cycle fish tests may be more relevant than reliance on early life-stage (ELS) tests, because the ELS test is unlikely to respond adequately to all pharmaceutical modes of action. Biomarkers may be useful in focusing research and testing efforts by identifying active substances and receptors of interest in aquatic species, and they may also be useful in field surveys for helping to establish possible cause and effect relationships. QSARs have been used by several authors to predict acute toxic effects, but predictions of chronic effects are currently hampered by the paucity of available chronic data to build predictive models. There seems to be no obvious reason why mixtures of pharmaceuticals in the environment should be treated in a different way to mixtures of other potentially hazardous substances. If mixture toxicity is considered to be an important environmental issue then all substances should be considered within an appropriate risk assessment framework.Science of The Total Environment 09/2006; 367(1):23-41. · 3.26 Impact Factor