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Analytical and Bioanalytical Chemistry

, Volume 404, Issue 5, pp 1517–1527 | Cite as

Sampling of organophosphorus pesticides at trace levels in the atmosphere using XAD-2 adsorbent and analysis by gas chromatography coupled with nitrogen–phosphorus and ion-trap mass spectrometry detectors

  • Mario Vincenzo Russo
  • Pasquale Avino
  • Giuseppe Cinelli
  • Ivan Notardonato
Original Paper

Abstract

This paper shows an analytical methodology based on solid-phase extraction by XAD-2 adsorbent and gas chromatography (GC) coupled with nitrogen–phosphorus (NPD) and ion-trap mass spectrometry detectors (ITMS) in negative chemical ionization (NCI) mode analyses for investigating organophosphorus pesticides (OPs) at trace levels (in nanograms per cubic meter) in the atmosphere: in particular, we set up a procedure for analyzing 38 OPs. For the analytical methodology linearity responses have been obtained in GC-NPD (r > 0.9982) and GC-NCI/ITMS (r > 0.9974) in a large linearity range (0.10–500 pg μL−1 in both cases) whereas the limits of detection range between 0.01 and 0.03 pg μL−1 in both the techniques with a relative standard deviation (RSD) below 9.0 in both cases. Particular attention has been devoted to investigate the effect of different solvents (n-hexane, benzene, chloroform, carbon disulfide, acetonitrile) on the OP recovery as well the breakthrough volumes have been evaluated (100 % recovery up to 4,286 L g−1). The study has also investigated the OP recoveries at different sampling flow rates (1.5 and 2.0 L min−1) for determining the optimal conditions for sample collection. Finally, the whole approach has been successfully applied to real samples collected in four different areas in the Molise region (Central Italy) during different seasons: the results show that parathion-ethyl, dimethoate, omethoate, and malathion are present in all periods at low levels (ranging between 70 and 10 ng m−3): their levels in such periods can be correlated with spraying as well atmospheric conditions favoring the dispersion/accumulation of these pollutants

Figure

Sampling system of organophosphorus pesticides in atmosphere and relative GC-NPD chromatogram

Keywords

Organophosphorus pesticides Adsorbent XAD 2 GC-NPD GC-NCI/ITMS Atmospheric pollution 

Supplementary material

216_2012_6205_MOESM1_ESM.pdf (80 kb)
ESM 1 (PDF 80.3 kb)

References

  1. 1.
    IPCS (2002) The WHO recommended classification of pesticides by hazard. Guidelines to classification 2000-2002 (available at www.inchem.org/documents/pds/pdsother/class.pdf)
  2. 2.
    Fan AM, Jackson RJ (1989) Pesticides and food safety. Regul Toxicol Pharmacol 9:158–174CrossRefGoogle Scholar
  3. 3.
    Jelinek CF (1985) Control of chemical contaminants in foods: past, present, and future. J AOAC Int 68:1064–1068Google Scholar
  4. 4.
    Chambers WH (1992) In: Chambers JE, Levi PE (eds) Organophosphates: chemistry, fate, and effects. Academic, New YorkGoogle Scholar
  5. 5.
    Racke KD (1992) In: Chambers JE, Levi PE (eds) Organophosphates: chemistry, fate, and effects. Academic Press, New YorkGoogle Scholar
  6. 6.
    National Resource Council (1993) Pesticides in the diets of infants and children. National Academy Press, Washington, DCGoogle Scholar
  7. 7.
    World Health organization (2008) Pesticides—children’s health and the environment (available at www.who.int/ceh)
  8. 8.
    Canada H (1998) Health and the environment: handbook for health professionals. Ministry of Public Work and Government Services, OttawaGoogle Scholar
  9. 9.
    US EPA (2011) Pesticides industry sales and usage: 2000 & 2001 market estimates (available at www.epa.gov/oppbead1/pestsales/01pestsales/market_estimates2001.pdf)
  10. 10.
    Mansour M, Barceló D, Albaiges J (1992) Analytical methodology for screening organophosphorus pesticides in biota samples. Sci Total Environ 123:45–56CrossRefGoogle Scholar
  11. 11.
    Lacorte S, Molina C, Barceló D (1993) Screening of organophosphorus pesticides in environmental matrices by various gas chromatographic techniques. Anal Chim Acta 281:71–84CrossRefGoogle Scholar
  12. 12.
    Dogheim SM, Gad Alla SA, El-Syes SMA, Almaz MM, Salama EY (1996) Monitoring pesticide residues in Egyptian fruits and vegetables in 1995. J AOAC Int 79:948–955Google Scholar
  13. 13.
    Shimizu K, Shiono H, Fukushima T, Sasaki M, Akutsu H, Sakata M (1996) Tissue distribution of DDVP after fatal ingestion. Forensic Sci Int 83:61–66CrossRefGoogle Scholar
  14. 14.
    Juhler RK (1997) Optimized method for the determination of organophosphorus pesticides in meat and fatty matrices. J Chromatogr A 786:145–153CrossRefGoogle Scholar
  15. 15.
    Hyötyläinen T, Jauho K, Riekkola M-L (1998) Analysis of pesticides in red wines by on-line reversed-phase liquid chromatography–gas chromatography with vaporiser/precolumn solvent split/gas discharge interface. J Chromatogr 813:113–119CrossRefGoogle Scholar
  16. 16.
    Dogheim SM, Gad Alla SA, El-Marsafy AM (2001) Monitoring of pesticide residues in Egyptian fruits and vegetables during 1996. J AOAC Int 84:519–531Google Scholar
  17. 17.
    Tarbah FA, Mahler H, Temme O, Daldrup T (2001) An analytical method for the rapid screening of organophosphate pesticides in human biological samples and foodstuffs. Forensic Sci Int 121:126–133CrossRefGoogle Scholar
  18. 18.
    van Wyk E, Bouwman H, van der Bank H, Verdoorn GH, Hofmann D (2001) Persistent organochlorine pesticides detected in blood and tissue samples of vultures from different localities in South Africa. Comp Biochem Physiol C 129:243–264Google Scholar
  19. 19.
    Russo MV, Campanella L, Avino P (2002) Determination of organophosphorus pesticide residues in human tissues by capillary gas chromatography-negative chemical ionization mass spectrometry analysis. J Chromatogr B 780:431–441CrossRefGoogle Scholar
  20. 20.
    Porte C, Barceló D, Albaiges J (1992) Monitoring of organophosphorus and organochlorinated compounds in a rice crop field (Ebro Delta, Spain) using the mosquitofish Gambusia affinis as indicator organism. Chemosphere 24:735–743CrossRefGoogle Scholar
  21. 21.
    Leoni V, Caricchia AM, Chiavarini S (1992) Multiresidue method for quantitation of organophosphorus pesticide in vegetable animal food. J AOAC Int 75:511–518Google Scholar
  22. 22.
    Molina C, Horning M, Barceló D (1994) Determination of organophosphorus pesticides in water by solid-phase extraction followed by liquid chromatography/high-flow pneumatically assisted electrospray mass spectrometry. Anal Chem 66:4444–4449CrossRefGoogle Scholar
  23. 23.
    Lacorte S, Barceló D (1996) Determination of parts per trillion levels of organophosphorus pesticides in groundwater by automated on-line liquid-solid extraction followed by liquid chromatography/atmospheric pressure chemical ionization mass spectrometry using positive and negative ion modes of operation. Anal Chem 68:2464–2470CrossRefGoogle Scholar
  24. 24.
    Moate TF, Jenkis JJ (1997) Gas chromatographic determination of airborne residues of azinphosmethyl and azinphosmethyl-oxon by cool on-column injection. J Chromatogr A 775:307–312CrossRefGoogle Scholar
  25. 25.
    Pogačnik L, Franko M (1999) Determination of organophosphate and carbamate pesticides in spiked samples of tap water and fruit juices by a biosensor with photothermal detection. Biosens Bioelectron 14:569–578CrossRefGoogle Scholar
  26. 26.
    Pogačnik L, Franko M (2001) Optimisation of FIA system for detection of organophosphorus and carbamate pesticides based on cholinesterase inhibition. Talanta 54:631–641CrossRefGoogle Scholar
  27. 27.
    Amendola L, Botrè F, Carollo AS, Longo D, Zoccolillo L (2002) Analysis of organophosphorus pesticides by gas chromatography–mass spectrometry with negative chemical ionization: a study on the ionization conditions. Anal Chim Acta 461:97–108CrossRefGoogle Scholar
  28. 28.
    Pogačnik L, Franko M (2003) Detection of organophosphate and carbamate pesticides in vegetable samples by a photothermal biosensor. Biosens Bioelectron 18:1–9CrossRefGoogle Scholar
  29. 29.
    Franko M, Sarakha M, Čibej A, Boškin A, Bavcon M, Trebše P (2005) Photodegradation of pesticides and application of bioanalytical methods for their detection. Pure Appl Chem 77:1727–1736CrossRefGoogle Scholar
  30. 30.
    Russo MV, Goretti G, Nevigato T (1999) Sequential solid-phase extraction with cyanopropyl bonded-phase cartridges for trace enrichment of PCBs and chlorinated pesticides from water samples. Chromatographia 50:446–452CrossRefGoogle Scholar
  31. 31.
    Russo MV (2000) Diol Sep-Pak cartridges for enrichment of PCBs and chlorinated pesticides from water samples; determination by GC-ECD. Chromatographia 52:93–98CrossRefGoogle Scholar
  32. 32.
    Russo MV, Avino P (2001) Determination of 1,2,4- and 1,3,5-trichlorobenzenes in water samples by solid-phase extraction and gas chromatography coupled to electron capture. Anal Lett 34:883–891CrossRefGoogle Scholar
  33. 33.
    Russo MV, Campanella L, Avino P (2003) Identification of halocarbons in Tiber and Marta rivers by static headspace and liquid-liquid extraction analysis. J Sep Sci 26:376–381CrossRefGoogle Scholar
  34. 34.
    Russo MV, De Leonardis A, Macciola V (2005) Solid phase extraction–gas chromatographic method to determine free cholesterol in animal fats. J Food Combin Anal 18:617–624CrossRefGoogle Scholar
  35. 35.
    Russo MV, Avino P, Notardonato I, Cinelli G (2009) Cyanopropyl bonded-phase cartridges for trace enrichment of dioxins and chlorinated pesticides from water. Chromatographia 69:709–717CrossRefGoogle Scholar
  36. 36.
    Avino P, Notardonato I, Cinelli G, Russo MV (2009) Aromatic sulfur compounds enrichment from seawater in crude oil contamination by Solid Phase extraction. Curr Anal Chem 5:339–346CrossRefGoogle Scholar
  37. 37.
    Avino P, Cinelli G, Notardonato I, Russo MV (2011) Evaluation of different adsorbents for large-volume pre-concentration for analyzing atmospheric persistent organic pollutants at trace levels. Anal Bioanal Chem 400:3561–3571CrossRefGoogle Scholar
  38. 38.
    Russo MV, Cinelli G, Notardonato I, Avino P (2011) Evaluation of an analytical method for determining phthalate esters in wine samples by solid-phase extraction and gas chromatography coupled with ion-trap mass spectrometer detector. Anal Bioanal Chem. doi: 10.1007/s00216-011-5551-9, in press
  39. 39.
    Cartoni GP, Goretti G, Neri B, Russo MV (1989) Evaluation of small diameter capillary columns for gas chromatography. J Chromatogr 475:145–151CrossRefGoogle Scholar
  40. 40.
    Russo MV, Goretti G, Soriero A (1996) Preparation and application of fused-silica capillary microcolumns (25–50 μm I.D.) in gas chromatography. Ann Chim (Rome) 86:115–124Google Scholar
  41. 41.
    Knoll JK (1985) Estimation of the limit of detection in chromatography. J Chromatogr Sci 23:422–425Google Scholar
  42. 42.
    Dettmer K, Engewald W (2002) Adsorbent materials commonly used in air analysis for adsorptive enrichment and thermal desorption of volatile organic compounds. Anal Bioanal Chem 373:490–500CrossRefGoogle Scholar
  43. 43.
    Dettmer K, Engewald W (2003) Ambient air analysis of volatile organic compounds using adsorptive enrichment. Chromatographia 57:S339–S347CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  • Mario Vincenzo Russo
    • 1
  • Pasquale Avino
    • 2
  • Giuseppe Cinelli
    • 1
  • Ivan Notardonato
    • 1
  1. 1.Facoltà di Agraria (DISTAAM)Università degli Studi del MoliseCampobassoItaly
  2. 2.DIPIA, INAIL ex-ISPESLRomeItaly

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