Human biomonitoring of pyrethrum and pyrethroid insecticides used indoors: determination of the metabolites E-cis/trans-chrysanthemumdicarboxylic acid in human urine by gas chromatography-mass spectrometry with negative chemical ionization.

This work describes a gas chromatographic-mass spectrometric method employing negative chemical ionization (NCI) for the determination of E-cis/trans-chrysanthemumdicarboxylic acid (CDCA) in human urine used as a biomarker for the exposure to pyrethrum and/or certain pyrethroids in insecticide formulations applied indoors. Mixed-mode solid phase extraction was utilized for sample cleanup. Extraction recoveries ranged from 92 to 104% (2-9% R.S.D.). The acids were esterified with 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) allowing both their gas chromatographic separation and their sensitive mass spectrometric detection under NCI conditions. Detection limits of ca. 0.05 microg/l urine were achieved.

[1]  J. V. Sancho,et al.  Direct determination of chlorpyrifos and its main metabolite 3,5, 6-trichloro-2-pyridinol in human serum and urine by coupled-column liquid chromatography/electrospray-tandem mass spectrometry. , 2000, Rapid communications in mass spectrometry : RCM.

[2]  S. Fustinoni,et al.  Gas chromatography-electron-capture detection of urinary methylhippuric acid isomers as biomarkers of environmental exposure to xylene. , 1999, Journal of chromatography. B, Biomedical sciences and applications.

[3]  J. Angerer,et al.  New gas chromatographic-mass spectrometric method for the determination of urinary pyrethroid metabolites in environmental medicine. , 2002, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[4]  J. Angerer,et al.  Determination of metabolites of pyrethroids in human urine using solid-phase extraction and gas chromatography-mass spectrometry. , 1997, Journal of chromatography. B, Biomedical sciences and applications.

[5]  J. Angerer,et al.  Metabolites of pyrethroid insecticides in urine specimens: current exposure in an urban population in Germany. , 2001, Environmental health perspectives.

[6]  D. Camann,et al.  Analytical methods for detection of nonoccupational exposure to pesticides. , 1988, Journal of chromatographic science.

[7]  J. Angerer,et al.  Gas chromatographic method with mass-selective detection for the determination of 2-isopropoxyphenol in human urine. , 1999, Journal of chromatography. B, Biomedical sciences and applications.

[8]  R. Tsuji,et al.  Pyrethroids, nerve poisons: how their risks to human health should be assessed. , 1995, Toxicology letters.

[9]  T. Class.  Determination of pyrethroids and their degradation productds in indoor air and on surfaces by HRGC-ECD and HRGC-MS(NCI) , 1991 .

[10]  G. Leng,et al.  Determination of pyrethroid metabolites in human urine by capillary gas chromatography-mass spectrometry , 1996 .

[11]  I. S. Gilkison.  Quantitative and qualitative analysis of triglycerides using gradient elution with UV detection , 1988 .

[12]  T. Greibrokk,et al.  Ultra trace determination of fluorinated aromatic carboxylic acids in aqueous reservoir fluids by solid phase extraction in combination with negative ion chemical ionisation mass spectrometry after derivatisation with pentafluorobenzyl bromide , 1998 .

[13]  A. Ramesh,et al.  Monitoring of allethrin, deltamethrin, esbiothrin, prallethrin and transfluthrin in air during the use of household mosquito repellents. , 2001, Journal of environmental monitoring : JEM.

[14]  D. Barr,et al.  A multi-analyte method for the quantification of contemporary pesticides in human serum and plasma using high-resolution mass spectrometry. , 2002, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[15]  J. Pauluhn.  Risk assessment of pyrethroids following indoor use. , 1996, Toxicology Letters.

[16]  Dana B Barr,et al.  Analytical methods for biological monitoring of exposure to pesticides: a review. , 2002, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[17]  A. Fernandez-Gutiérrez,et al.  Monitoring of pyrethroid metabolites in human urine using solid-phase extraction followed by gas chromatography-tandem mass spectrometry , 1999 .

[18]  R. Wintersteiger,et al.  Determination of traces of pyrethrins and piperonyl butoxide in biological material by high-performance liquid chromatography. , 1994, Journal of chromatography. A.

[19]  J. Pauluhn.  Hazard identification and risk assessment of pyrethroids in the indoor environment. , 1999, Toxicology letters.

[20]  G. Leng,et al.  Human dose-excretion studies with the pyrethroid insecticide cyfluthrin: urinary metabolite profile following inhalation. , 1997, Xenobiotica; the fate of foreign compounds in biological systems.

[21]  K. Levsen,et al.  The Behaviour of Pyrethroids Indoors: A Model Study , 1997 .

[22]  Y. Matoba,et al.  Indoor behavior and risk assessment following residual spraying of d-phenothrin and d-tetramethrin. , 1998, American Industrial Hygiene Association journal.

[23]  D A Kalman,et al.  Improved cleanup and determination of dialkyl phosphates in the urine of children exposed to organophosphorus insecticides. , 1999, Journal of analytical toxicology.

[24]  B D Hammock,et al.  Enzyme-linked immunosorbent assay for the pyrethroid permethrin. , 2000, Journal of agricultural and food chemistry.

[25]  J. Chambers.  An introduction to the metabolism of pyrethroids. , 1980, Residue reviews.

[26]  John D. Roberts,et al.  Nuclear Magnetic Resonance Spectroscopy. Cyclopropane Derivatives , 1963 .

[27]  N. Moriyama,et al.  Simple Method for Determining Trace Pesticides in Air Using Extraction Disks , 2000 .

[28]  K. Levsen,et al.  Development of a gas chromatography-mass spectrometry method for the determination of household insecticides in indoor air. , 2003, Journal of Chromatography A.

[29]  W. Taylor,et al.  Capillary gas chromatographic determination of permethrin insecticide by transesterification. , 1997, Journal of Chromatography B: Biomedical Sciences and Applications.

[30]  J. Angerer,et al.  Metabolites of organophosphorous insecticides in urine specimens from inhabitants of a residential area. , 2001, Environmental research.

[31]  J. Leahey.  The pyrethroid insecticides. , 1985 .

[32]  J. Siebers,et al.  Determination of airborne residues in greenhouses after application of pesticides , 1996 .

[33]  G. Leng,et al.  Determination of trace levels of pyrethroid metabolites in human urine by capillary gas chromatography-high resolution mass spectrometry with negative chemical ionization , 1997 .

[34]  L. Crombie,et al.  Nuclear magnetic resonance spectra of the natural pyrethrins and related compounds. , 1969, Tetrahedron.

[35]  J. Louis,et al.  Determination of pesticides in indoor air and dust. , 1993, Journal of AOAC International.

[36]  C. Aprea,et al.  Multiroute Exposure Assessment and Excretion of Urinary Metabolites of Fenitrothion During Manual Operations on Treated Ornamental Plants in Greenhouses , 1999, Archives of environmental contamination and toxicology.

[37]  J. L. Vidal,et al.  Analysis of N-methylcarbamates insecticides and some of their main metabolites in urine with liquid chromatography using diode array detection and electrospray mass spectrometry , 2000 .

[38]  W. Hoffmann,et al.  Biozide im Hausstaub : Ergebnisse eines repräsentativen Monitorings in Innenräumen , 1999 .

[39]  A. Herrmann,et al.  Analysis of polychlorinated biphenyls, pyrethroid insecticides and fragrances in human milk using a laminar cup liner in the GC injector , 2001 .

[40]  D. Breuer,et al.  Determination of permethrin in indoor air by liquid chromatography with enzyme linked immunosorbent assay , 1999 .

[41]  G. Leng,et al.  Metabolism of (S)-bioallethrin and related compounds in humans. , 1999, Toxicology letters.

[42]  D. Bissacot,et al.  HPLC determination of flumethrin, deltamethrin, cypermethrin, and cyhalothrin residues in the milk and blood of lactating dairy cows. , 1997, Journal of Analytical Toxicology.

[43]  H. Sochor,et al.  Rapid multimethod for verification and determination of toxic pesticides in whole blood by means of capillary GC-MS. , 2000, Journal of analytical toxicology.

[44]  C. Schlatter,et al.  Human Exposure to Airborne Pesticides in Homes Treated with Wood Preservatives , 1997 .