Determination of pharmaceuticals and antiseptics in water by solid-phase extraction and gas chromatography/mass spectrometry: Analysis via pentafluorobenzylation and stable isotope dilution
Department of Geography and Environmental Engineering, Johns Hopkins University, Baltimore, MD 21218-2686, USA. Analytical and Bioanalytical Chemistry
(Impact Factor: 3.44).
02/2012; 403(2):583-91. DOI: 10.1007/s00216-012-5846-5
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.
Available from: John Struger
- "Although it is known to have 90e99% removal in WWTPs with activated sludge systems (Martín et al., 2012; Nakada et al., 2006; Radjenovi c et al., 2009), ibuprofen is still detected in the effluents at relatively high concentrations varying from 384 to 4000 ng/L (Lishman et al., 2006; Metcalfe et al., 2003). Naproxen has also been shown to have high removals in WWTPs (Bueno et al., 2012; Fernandez-Fontaina et al., 2012; Kasprzyk-Hordern et al., 2009; Yu et al., 2012), but it was still detected in the Grand River watershed. Unlike ibuprofen, naproxen was present at lower concentrations in the upper section of the study area. "
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ABSTRACT: Correlation analysis suggests that occurrences of AMPA in streams of southern Ontario are linked mainly to glyphosate in both urban and rural settings, rather than to wastewater sources, as some previous studies have suggested. For this analysis the artificial sweetener acesulfame was analyzed as a wastewater indicator in surface water samples collected from urban and rural settings in southern Ontario, Canada. This interpretation is supported by the concurrence of seasonal fluctuations of glyphosate and AMPA concentrations. Herbicide applications in larger urban centres and along major transportation corridors appear to be important sources of glyphosate and AMPA in surface water, in addition to uses of this herbicide in rural and mixed use areas. Fluctuations in concentrations of acesulfame and glyphosate residues were found to be related to hydrologic events.
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- "These are often accompanied by sample pre-concentration and/or pre-treatment steps such as enzymatic hydrolysis and derivitization [12–33]. Indeed the quest for more sensitive and reliable methods continues unabated, usually with a focus on hyphenated separations and mass spectrometric approaches                . While many recent papers have focused on glucuronide and sulfate conjugates of steroids, these types of metabolites are relevant for most performance-enhancing drugs, and drugs of abuse, even ethanol     . "
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ABSTRACT: The detection window for drugs of abuse, including performance-enhancing drugs, is limited by the sensitivity of analytical methodologies. Herein, paired ion electrospray ionization mass spectrometry (PIESI-MS) was employed for sensitive analysis of performance-enhancing drugs and drugs of abuse by detecting their glucuronide and sulfate conjugates. The proposed approach provides enhanced sensitivity for these drug metabolites, and overcomes the drawbacks of the less sensitive negative ion mode ESI-MS by detecting the anionic metabolites in the positive ion mode at higher m/z where the background noise is less. Absolute LODs down to sub-pg levels were obtained with the use of the optimal symmetrical or unsymmetrical ion pairing reagents. One to three orders of magnitude improvement were obtained compared to other reported methods performed in the negative ion mode. Structurally similar steroid conjugates were chromatographically separated and detected by HPLC coupled with PIESI-MS. Finally, an off-line solid phase extraction (SPE) protocol was successfully developed to eliminate any matrix effects in the analysis of human urine samples.
Available from: Rim Said Haggag
- "A highly sensitive UPLC–MS/MS method for the quantitative analysis of KTP in dialyzes from topical preparations has been published (Tettey-Amlalo and Kanfer, 2009). KTP has been determined simultaneously with other pharmaceuticals, from these we can mention GC-MS/MS for the analysis of KTP and other NSAID including IBP, and/or naproxen in waste water and environmental water samples, after derivatization (Hashim and Khan, 2011; Yu et al., 2012), GC- MS/MS in urine and blood samples (Azzouz and Ballesteros, 2012), the use of capillary electrochromatography coupled with UV or mass spectrometry in water samples (Hsu et al., 2011), GCtandem mass spectrometry in bovine milk (Dowling et al., 2008), HPLC for the simultaneous determination of KTP and mefenamic acid in tablets (Hung and Hwang, 2008), with IBP and other NSAID (Jedziniak et al., 2012) (Patrolecco et al., 2013). A simple new chemiluminescent method for the determination of IBP and KTP is described using the Fenton system in the presence of europium(iii) ions (Kaczmarek and Lis, 2012). "
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ABSTRACT: The objective of the work was to establish a new, rapid and sensitive HPLC–DAD method for simultaneous
determination of three most commonly prescribed drugs; hyoscine, ketoprofen, and ibuprofen. The HPLC
separation of the analytes was performed on a hypersil - Gold C18 (150 mm × 4.6 mm, 8 μm) column, using
gradient elution of the mobile phase composed of 0.01 M potassium phosphate dibasic containing 2 g/L heptane
sulphonic acid sodium salt maintained at pH 3.5 (Pump A) and acetonitrile 80% v/v (pump B) with a flow rate of
2 mL/min. The multiple wavelength detector was set at 210 nm for measurement of all compounds.
Quantification was based on measuring the peak areas. The three compounds were resolved with retention times
6.42 ± 0.009, 10.63 ± 0.006 and 16.43 ± 0.008 min for hyoscine, ketoprofen and ibuprofen, respectively.The
calibration curves were linear in the range of 0.64 – 96, 0.64 – 400 and 1.28 – 640 μg/mL for hyoscine,
ketoprofen and ibuprofen, respectively, all of them with coefficients of determination above 0.9995. The
methodology recoveries were higher than 95.0%. The limits of detection (LODs) were 0.11, 0.17 and 0.17 μg/mL
for hyoscine, ketoprofen, and ibuprofen, respectively. The intra- and inter-day coefficients of variation were less
than 2%. The method is accurate, sensitive and simple for quality control as well as for stability indicating
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