ABSTRACT
It was demonstrated that four out of six of the very polar organophosphorus pesticides (OPs), i.e. acephate, methamidophos, monocrotophos, omethoate, oxydemeton-methyl and vamidothion, could not be extracted from water using commonly available SPE cartridges. In addition, GC analysis on all six compounds was found to be troublesome due to their polar and thermolabile character. This initiated the development of an alternative highly sensitive and selective method for the determination of the above mentioned very polar OPs in water, based on LC-MS. Large volume (1 ml) water samples were directly injected onto an RP18 HPLC column with a polar endcapping. The latter was essential for obtaining retention and maintaining column performance under 100% aqueous conditions during the sampling. The compounds were ionized using atmospheric pressure chemical ionization and detected on a tandem mass spectrometer operated in multiple reaction-monitoring mode. The detection limits were in the range of 0.01-0.03 microg/l. Compared to conventional GC methods, the developed LC-MS procedure is very straightforward, fast and more reliable. This application demonstrates the applicability of LC-MS for analysis of polar OPs in surface, ground and drinking water, as a more favourable alternative to GC.
Subject(s)
Chromatography, High Pressure Liquid/methods , Insecticides/analysis , Mass Spectrometry/methods , Organophosphorus Compounds , Water/chemistry , Chromatography, Gas , Reproducibility of Results , Sensitivity and SpecificityABSTRACT
The combined gas chromatographic determination of a number of hydroxyl-group containing endocrine disruptors, including 4-octylphenol, 4-nonylphenol, 2,4-dichlorophenol, pentachlorophenol, 4-tert.-butylbenzoic acid, bisphenol-A, 17beta-estradiol and 17alpha-ethynylestradiol, was investigated. Derivatization, required for sensitive determination of these compounds, was carried out using N-methyl-N-(tert.-butyldimethyltrifluoroacetamide). A number of parameters affecting the derivatization reaction, like temperature, time, matrix, solvent, and amount of reagent were studied in detail. Quantitative yields were obtained for real-life extracts after optimization, but the hormones were only mono-substituted. Both solid-phase extraction (SPE) and liquid-liquid extraction were studied as extraction methods, with emphasis on SPE material and effect of pH. Recoveries and RSD for analysis of surface water samples were 58-106 and 6-16% (n=4), respectively, when using SPE, and 109-117 and 6-14% (n=6) when using liquid-liquid extraction. The method developed allows routine analysis of surface water for traces of endocrine disruptors. The limits of detection of were 4-6 ng/l but higher for the hormones.
Subject(s)
Endocrine Glands/drug effects , Gas Chromatography-Mass Spectrometry/methods , Water Pollutants, Chemical/analysis , Xenobiotics/analysisABSTRACT
A straightforward and reliable method was developed for the determination of chlormequat in pears by liquid chromatography/mass spectrometry (LC/MS). Water and methanol were compared as extraction solvents. Because no significant differences in extraction efficiency or repeatability were found, water was chosen as the extraction solvent. The extracts were analyzed without cleanup by either an ion-trap liquid chromatograph/mass spectrometer in the single MS mode or a triple-quadrupole instrument in the MS/MS mode, using electrospray ionization. Both instruments were equally suitable for quantitation and confirmation of identity. Recoveries were 76-103%, and reproducibility was < or = 12%. The lowest detection limit (0.007 mg/kg) was obtained with the triple-quadrupole instrument in the MS/MS mode.
Subject(s)
Chlormequat/analysis , Chromatography, Liquid/methods , Fruit/chemistry , Mass Spectrometry/methods , Methanol , Reproducibility of Results , WaterABSTRACT
A straightforward and efficient method was developed for the determination of intact daminozide in apples and apple leaves. After extraction with methanol and a clean-up step using a graphitized carbon cartridge, the extract was analysed by ion-trap liquid chromatography-tandem mass spectrometry (LC-MS-MS) using atmospheric pressure chemical ionisation in the positive ion mode. Recoveries for apple were 98-102% with a R.S.D. < or = 11% (n = 6) and for leaves were 112-116% with a R.S.D. < or = 18% (n = 6). The limits of detection were 0.008 and 0.02 mg/kg for apples and leaves, respectively.
Subject(s)
Chromatography, Liquid/methods , Fruit/chemistry , Mass Spectrometry/methods , Plant Growth Regulators/analysis , Succinates/analysis , Sensitivity and SpecificityABSTRACT
The synthesis of a new acridinium sulphonylamide label for the liquid chromatographic determination of carboxylic acids is described. The label 10-methyl-N-(p-tolyl)-N-(p-iodoacetamidobenzenesulphonyl)-9-acr idi nium carboxamide iodide is synthesized from 9-acridine-carboxylic acid by a seven-step reaction. Ibuprofen, used as test compound, is coupled to the reactive iodoacetamide group of the label by means of an alkylation reaction in dry acetonitrile for 20 min at 50 degrees C in the presence of 18-crown-6 and potassium carbonate as base catalyst. The reaction mixture is injected into a liquid chromatographic system with chemiluminescence detection. Separation is performed on a Zorbax C18 column with acetonitrile-water-tetrahydrofuran (39:57:4, v/v/v) containing 10 mmol/L TBABr and 0.035% H2O2 as the mobile phase at a flow rate of 1.0 ml/min. Chemiluminescence detection is achieved by the post-column addition of 200 mmol/L potassium hydroxide dissolved in methanol-water (1:1, v/v) at a flow rate of 20 microL/min. The detection limit (S/N = 3) of derivatized ibuprofen is 60 pg (3 pg injected).
Subject(s)
Acridines/chemistry , Carboxylic Acids/analysis , Molecular Probes/chemistry , Sulfonamides/chemistry , Acridines/chemical synthesis , Chromatography, Liquid/methods , Hydroxides/chemistry , Ibuprofen/analysis , Luminescent Measurements , Molecular Probes/chemical synthesis , Potassium Compounds/chemistry , Solvents , Sulfonamides/chemical synthesisABSTRACT
A fully automated method is described for the determination of amoxicillin and cefadroxil in bovine serum and muscle tissue. The method is based on the on-line combination of dialysis and solid-phase extraction for sample preparation, and column liquid chromatography with ultraviolet detection. In order to enhance the UV detectability of the analytes, post-column addition of 0.1 M sodium hydroxide is performed. The method shows good linearity and repeatability for both analytes in serum as well as in muscle tissue; the limits of detection in these samples are 0.05 microgram/ml and 0.2 microgram/g, respectively. The method has a sample throughput of 30 samples per 24 h.
Subject(s)
Amoxicillin/analysis , Cefadroxil/analysis , Muscles/chemistry , Amoxicillin/blood , Animals , Cattle , Cefadroxil/blood , Chromatography, Liquid , Hydrogen-Ion Concentration , Meat/analysis , Microdialysis , Spectrophotometry, UltravioletABSTRACT
N-(4-Aminobutyl)-N-ethylisoluminol was used for labelling of carboxylic acids. The derivatization reaction was carried out with 1-hydroxybenzotriazole as pre-activator of the carboxylic acid function and N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide as the coupling reagent. Optimum conditions for the derivatization were determined by using factorial design analysis, with ibuprofen as the test compound. Chemiluminescence detection was carried out using a post-column on-line electrochemical hydrogen peroxide generation system and the addition of microperoxidase as the catalyst. The detection limit of derivatized ibuprofen in human saliva was 0.7 ng per 0.5 ml of saliva, with a recovery of 96.1 +/- 1.3%. The method was linear over at least three decades (2.5 ng to 2.5 micrograms) and the repeatability was satisfactory (R.S.D. = 5.2% at the 25 ng level; n = 4).
