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Solid-phase extraction combined with high-performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry analysis of pesticides in water: method performance and application in a reconnaissance survey of residues in drinking water in Greater Cairo, Egypt.

Monitoring of water resources for pesticide residues is often needed to ensure that pesticide use does not adversely impact the quality of public water supplies or the environment. In many rural areas and throughout much of the developing world, monitoring is often constrained by lack of testing facilities; thus, collection of samples and shipment to centralized laboratories for analysis is required. The portability, ease of use, and potential to enhance analyte stability make solid-phase extraction (SPE) an attractive technique for handling water samples prior to their shipment. We describe performance of an SPE method targeting a structurally diverse mixture of 25 current-use pesticides and two common degradates in samples of raw and filtered drinking water collected in Greater Cairo, Egypt. SPE was completed in a field laboratory in Egypt, and cartridges were shipped to the United States for elution and high-performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry analysis. Quantitative and reproducible recovery of 23 of 27 compounds (average = 96%; percent relative standard deviation = 21%) from matrix spikes (1 microg L-1 per component) prepared in the field and from deionized water fortified similarly in the analytical laboratory was obtained. Concurrent analysis of unspiked samples identified four parent compounds and one degradate in drinking water samples. No significant differences were observed between raw and filtered samples. Residue levels in all cases were below drinking water and "harm to aquatic-life" thresholds, indicating that human and ecological risks of pesticide contamination were relatively small; however, the study was limited in scale and scope. Further monitoring is needed to define spatial and temporal variation in residue concentrations. The study has demonstrated the feasibility of performing studies of this type using SPE to extract and preserve samples in the field. The approach should be broadly applicable in many settings.

Chromatography, High Pressure Liquid↗

Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS) in toxicological analysis. Studies on the detection of clobenzorex and its metabolites within a systematic toxicological analysis procedure by GC-MS and by immunoassay and studies on the detection of alpha- and beta-amanitin in urine by atmospheric pressure ionization electrospray LC-MS.

GC-MS is the method of choice for toxicological analysis of toxicants volatile in GC while non-volatile and/or thermally labile toxicants need LC-MS for their determination. Studies are presented on the toxicological detection of the amphetamine-like anorectic clobenzorex in urine by GC-MS after acid hydrolysis, extraction and acetylation and by fluorescence polarization immunoassay (FPIA, TDx (meth)amphetamine II). After ingestion of 60 mg of clobenzorex, the parent compound and/or its metabolites could be detected by GC-MS for up to 84 h or by FPIA for up to 60 h. Since clobenzorex shows no cross-reactivity with the used immunoassay, the N-dealkylated metabolite amphetamine is responsible for the positive TDx results. The intake of clobenzorex instead of amphetamine can be differentiated by GC-MS detection of hydroxyclobenzorex which is detectable for at least as long as amphetamine. In addition, the described GC-MS procedure allows the simultaneous detection of most of the toxicologically relevant drugs. Furthermore, studies are described on the atmospheric pressure ionization electrospray LC-MS detection of alpha- and beta-amanitin, toxic peptides of amanita mushrooms, in urine after solid-phase extraction on RP-18 columns. Using the single ion monitoring mode with the ions m/z 919 and 920 the amanitins could be detected down to 10 ng/ml of urine which allows us to diagnose intoxications with amanita mushrooms.

Amanitins↗

[Determination of aliphatic amines by high performance liquid chromatography with fluorescence and atmospheric pressure chemical ionization detection and identification by mass spectrometry].

Aliphatic amines exist widely in nature. Therefore, quick and precise determination of aliphatic amines is of great significance. A simple and highly sensitive method based on the derivatization of aliphatic amines utilizing 1,2-benzo-3,4-dihydrocarbazole-9-acetic acid (BCAA) as the novel pre-column derivatization reagent followed by high performance liquid chromatography with fluorescence detection and online mass spectrometric identification was developed. Optimum derivatization was obtained by the reaction of aliphatic amines with BCAA at 50 degrees C for 15 min in the presence of 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDAC) in acetonitrile solvent. The condition of derivatization was mild and the yield of derivative each aliphatic amine was higher than 94%. Derivatives were sufficiently stable to be efficiently analyzed by high performance chromatography without pretreatment. On a reversed-phase BDS-C18 column, twelve aliphatic amine derivatives (C8 - C12) were separated under gradient elution with baseline resolution. The precise determining aliphatic amines from soil and wastewater samples was obtained by post-column online mass spectrometric identification with atmospheric pressure chemical ionization (APIC) source under positive mode detection. The established method exhibited excellent reproducibility and recovery. Linear responses were observed with coefficients over 0.999 3. The detection limits (at signal-to-noise ratio of 3: 1) were 12 - 28 fmol.

Acetonitriles↗