Analytical and Bioanalytical Chemistry

, Volume 406, Issue 22, pp 5271–5282 | Cite as

Determination of methylisothiocyanate in soil and water by HS-SPME followed by GC–MS–MS with a triple quadrupole

  • Aranzazu Peruga
  • Joaquim Beltrán
  • Francisco López
  • Félix HernándezEmail author
Research Paper


Methylisothiocyanate (MITC) is the main degradation product of metam sodium, a soil disinfectant widely used in agriculture, and is responsible for its disinfectant properties. Because MITC is highly toxic and volatile, metam sodium has to be applied in a manner that tries to reduce atmospheric emissions but still maintains adequate concentration of MITC in soil to ensure its disinfectant effect. Thus, monitoring of MITC concentrations in soil is required, and to this end sensitive, fast, and reliable analytical methods must be developed. In this work, a headspace solid-phase microextraction (HS-SPME) method was developed for MITC determination in water and soil samples using gas chromatography-tandem mass spectrometry (GC–MS–MS) with a triple-quadrupole analyzer. Two MS–MS transitions were acquired to ensure the reliable quantification and confirmation of the analyte. The method had linear behavior in the range tested (0.026–2.6 ng mL−1 in water, 1–100 ng g−1 in soil) with r 2 over 0.999. Detection limits were 0.017 ng mL−1 and 0.1 ng g−1 in water and soil, respectively. Recoveries for five replicates were in the range 76–92 %, and RSD was below 7 % at the two spiking levels tested for each matrix (0.1 and 1 ng mL−1 for water, 4 and 40 ng g−1 for soil). The potential of using multiple HS-SPME for analyzing soil samples was also investigated, and its feasibility for quantification of MITC evaluated. The developed HS-SPME method was applied to soil samples from experimental plots treated with metam sodium following good agriculture practices.


GC–MS–MS Triple quadrupole Metam sodium Methylisothiocyanate (MITC) Soil Pesticides 



The authors acknowledge the support of Generalitat Valenciana, as research group of excellence (Prometeo 2009/054). The support and advice of J. V. Sancho in MS optimization are greatly appreciated. The authors also acknowledge the cooperation of SynTech Research Spain in soil sampling and characterization.


  1. 1.
    Gan J, Papiernik S, Yates S, Jury W (1999) Temperature and moisture effects on fumigant degradation in soil. J Environ Qual 28:1436–1441CrossRefGoogle Scholar
  2. 2.
    Dungan R, Gan J, Yates S (2003) Accelerated degradation of methyl isothiocyanate in soil. Water Air Soil Pollut 142:299–310CrossRefGoogle Scholar
  3. 3.
    Smelt J, Leistra M (1974) Conversion of metham-sodium to methyl isothiocyanate and basic data on behavior of methyl isothiocyanate in soil. Pestic Sci 5:401–407CrossRefGoogle Scholar
  4. 4.
    Saeed I, Rouse D, Harkin J (2000) Methyl isothiocyanate volatilization from fields treated with metam-sodium. Pest Manag Sci 56:813–817CrossRefGoogle Scholar
  5. 5.
    Bretaudeau Deguigne M, Lagarce L, Boels D, Harry P (2011) Metam sodium intoxication: the specific role of degradation products–methyl isothiocyanate and carbon disulphide–as a function of exposure. Clin Toxicol 49:416–422CrossRefGoogle Scholar
  6. 6.
    Zheng W, Yates SR, Papiernik SK, Nunez J (2006) Conversion of metam sodium and emission of fumigant from soil columns. Atmos Environ 40:7046–7056CrossRefGoogle Scholar
  7. 7.
    Ou L, Thomas J, Allen L, Vu J, Dickson D (2006) Effects of application methods of metam sodium and plastic covers on horizontal and vertical distributions of methyl isothiocyanate in bedded field plots. Arch Environ Contam Toxicol 51:164–173CrossRefGoogle Scholar
  8. 8.
    Simpson CR, Nelson SD, Stratmann JE, Ajwa HA (2010) Surface water seal application to minimize volatilization loss of methyl isothiocyanate from soil columns. Pest Manag Sci 66:686–692CrossRefGoogle Scholar
  9. 9.
    Wang D, Juzwik J, Fraedrich SW, Spokas K, Zhang Y, Koskinen WC (2005) Atmospheric emissions of methyl isothiocyanate and chloropicrin following soil fumigation and surface containment treatment in bare-root forest nurseries. Can J For Res 35:1202–1212CrossRefGoogle Scholar
  10. 10.
    Littke MH, Lepage J, Sullivan DA, Hebert VR (2013) Comparison of field methyl isothiocyanate flux following Pacific Northwest surface-applied and ground-incorporated fumigation practices. Pest Manag Sci 69:620–626CrossRefGoogle Scholar
  11. 11.
    LAISOL. Desinfectante de suelos (2013).
  12. 12.
    Pesticide Action Network Europe (2011) Essent use soil fumigant Metam Sodium 1–20.
  13. 13.
    European Commission Directorate General Health and Consumer Protection (2010) Guidance document on pesticide residue analytical methods. Document N° SANCO/825/00 rev.8.1Google Scholar
  14. 14.
    Candole BL, Csinos AS, Wang D (2007) Concentrations in soil and efficacy of drip-applied 1,3-D plus chloropicrin and metam sodium in plastic-mulched sandy soil beds. Crop Prot 26:1801–1809CrossRefGoogle Scholar
  15. 15.
    Zhang Y, Spokas K, Wang D (2005) Degradation of methyl isothiocyanate and chloropicrin in forest nursery soils. J Environ Qual 34:1566–1572CrossRefGoogle Scholar
  16. 16.
    Zheng W, Yates SR, Guo MX, Papiernik SK, Kim JH (2004) Transformation of chloropicrin and 1,3-dichloropropene by metam sodium in a combined application of fumigants. J Agric Food Chem 52:3002–3009CrossRefGoogle Scholar
  17. 17.
    Stiles CL, Sams CE, Robinson DK, Coffey DL, Mueller TC (2000) Influence of metam sodium on the dissipation and residual biological activity of the herbicides EPTC and pebulate in surface soil under black plastic mulch. J Agric Food Chem 48:4681–4686CrossRefGoogle Scholar
  18. 18.
    Beltran J, Lopez FJ, Hernandez F (2000) Solid-phase microextraction in pesticide residue analysis. J Chromatogr A 885:389–404CrossRefGoogle Scholar
  19. 19.
    Mee Kin C, Guan Huat T (2010) Headspace solid-phase microextraction for the evaluation of pesticide residue contents in cucumber and strawberry after washing treatment. Food Chem 123:760–764CrossRefGoogle Scholar
  20. 20.
    Chai MK, Tan GH (2009) Validation of a headspace solid-phase microextraction procedure with gas chromatography-electron capture detection of pesticide residues in fruits and vegetables. Food Chem 117:561–567CrossRefGoogle Scholar
  21. 21.
    Sang Z, Wang Y, Tsoi Y, Leung KS (2013) CODEX-compliant eleven organophosphorus pesticides screening in multiple commodities using headspace-solid phase microextraction-gas chromatography-mass spectrometry. Food Chem 136:710–717CrossRefGoogle Scholar
  22. 22.
    Tsoutsi C, Konstantinou I, Hela D, Albanis T (2006) Screening method for organophosphorus insecticides and their metabolites in olive oil samples based on headspace solid-phase microextraction coupled with gas chromatography. Anal Chim Acta 573–574:216–222CrossRefGoogle Scholar
  23. 23.
    Lambropoulou DA, Albanis TA (2002) Headspace solid phase microextraction applied to the analysis of organophosphorus insecticides in strawberry and cherry juices. J Agric Food Chem 50:3359–3365CrossRefGoogle Scholar
  24. 24.
    Durovic RD, Dordevic TM (2012) Effects of soil composition on solid phase microextraction determination of triazine and organophosphorus pesticides. J Environ Sci Health Part B Pestic Food Contam Agric Wastes 47:851–857CrossRefGoogle Scholar
  25. 25.
    Carvalho PN, Rodrigues PNR, Alves F et al (2008) An expeditious method for the determination of organochlorine pesticides residues in estuarine sediments using microwave assisted pre-extraction and automated headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry. Talanta 76:1124–1129CrossRefGoogle Scholar
  26. 26.
    Chai X, Jia J, Sun T, Wang Y, Liao L (2007) Application of a novel cold activated carbon fiber-solid phase microextraction for analysis of organochlorine pesticides in soil. J Environ Sci Health B Pestic Contam Agric Wastes 42:629–634CrossRefGoogle Scholar
  27. 27.
    Herbert P, Morais S, Paíga P, Alves A, Santos L (2006) Development and validation of a novel method for the analysis of chlorinated pesticides in soils using microwave-assisted extraction-headspace solid phase microextraction and gas chromatography-tandem mass spectrometry. Anal Bioanal Chem 384:810–816CrossRefGoogle Scholar
  28. 28.
    Navalón A, Prieto A, Araujo L, Vílchez JL (2004) Determination of pyrimethanil and kresoxim-methyl in soils by headspace solid-phase microextraction and gas chromatography-mass spectrometry. Anal Bioanal Chem 379:1100–1105CrossRefGoogle Scholar
  29. 29.
    Navalon A, Prieto A, Araujo L, Vilchez JL (2002) Determination of oxadiazon residues by headspace solid-phase microextraction and gas chromatography-mass spectrometry. J Chromatogr A 946:239–245CrossRefGoogle Scholar
  30. 30.
    Doong RA, Liao PL (2001) Determination of organochlorine pesticides and their metabolites in soil samples using headspace solid-phase microextraction. J Chromatogr A 918:177–188CrossRefGoogle Scholar
  31. 31.
    Sakamoto M, Tsutsumi T (2004) Applicability of headspace solid-phase microextraction to the determination of multi-class pesticides in waters. J Chromatogr A 1028:63–74CrossRefGoogle Scholar
  32. 32.
    Li HP, Li GC, Jen JF (2003) Determination of organochlorine pesticides in water using microwave assisted headspace solid-phase microextraction and gas chromatography. J Chromatogr A 1012:129–137CrossRefGoogle Scholar
  33. 33.
    Lambropoulou DA, Albanis TA (2001) Optimization of headspace solid-phase microextraction conditions for the determination of organophosphorus insecticides in natural waters. J Chromatogr A 922:243–255CrossRefGoogle Scholar
  34. 34.
    Di Primo P, Gamliel A, Austerweil M, Steiner B, Beniches M, Peretz-Alon I, Katan J (2003) Accelerated degradation of metam-sodium and dazomet in soil: characterization and consequences for pathogen control. Crop Prot 22:635–646CrossRefGoogle Scholar
  35. 35.
    Triky-Dotan S, Austerweil M, Steiner B, Peretz-Alon Y, Katan J, Gamliel A (2009) Accelerated degradation of metam-sodium in soil and consequences for root-disease management. Phytopathology 99:362–368CrossRefGoogle Scholar
  36. 36.
    Triky-Dotan S, Austerweil M, Steiner B, Peretz-Alon Y, Katan J, Gamliel A (2007) Generation and dissipation of methyl isothiocyanate in soils following metam sodium fumigation: impact on verticillium control and potato yield. Plant Dis 91:497–503CrossRefGoogle Scholar
  37. 37.
    Sanon A, Garba M, Auger J, Huignard J (2002) Analysis of the insecticidal activity of methylisothiocyanate on Callosobruchus maculatus (F.) (Coleoptera : Bruchidae) and its parasitoid Dinarmus basalis (Rondani) (Hymenoptera : Pteromalidae). J Stored Prod Res 38:129–138CrossRefGoogle Scholar
  38. 38.
    Fuster S, Beltran J, López FJ, Hernández F (2005) Application of solid phase microextraction for the determination of soil fumigants in water and soil samples. J Sep Sci 28:98–103CrossRefGoogle Scholar
  39. 39.
    Serrano E, Beltran J, Hernandez F (2009) Application of multiple headspace-solid-phase microextraction followed by gas chromatography-mass spectrometry to quantitative analysis of tomato aroma components. J Chromatogr A 1216:127–133CrossRefGoogle Scholar
  40. 40.
    Ezquerro O, Ortiz G, Pons B, Tena M (2004) Determination of benzene, toluene, ethylbenzene and xylenes in soils by multiple headspace solid-phase microextraction. J Chromatogr A 1035:17–22CrossRefGoogle Scholar
  41. 41.
    Tena MT, Carrillo JD (2007) Multiple solid-phase microextraction: theory and applications. TrAc Trends Anal Chem 26:206–214CrossRefGoogle Scholar
  42. 42.
    Hernandez F, Cervera MI, Portoles T, Beltran J, Pitarch E (2013) The role of GC–MS–MS with triple quadrupole in pesticide residue analysis in food and the environment. Anal Methods 5:5875–5894CrossRefGoogle Scholar
  43. 43.
    Woodrow JE, Seiber JN, LeNoir JS, Krieger RI (2008) Determination of methyl isothiocyanate in air downwind of fields treated with metam-sodium by subsurface drip irrigation. J Agric Food Chem 56:7373–7378CrossRefGoogle Scholar
  44. 44.
    Pawliszyn J (1997) Solid phase microextraction: theory and practice. Wiley-VCH, Inc., USAGoogle Scholar
  45. 45.
    Pawliszyn J (2007) Handbook of solid phase microextraction. University of Waterloo, Ontario. Ed. Janusz PawlyszynGoogle Scholar
  46. 46.
    Ai J (1997) Headspace solid phase microextraction. Dynamics and quantitative analysis before reaching a partition equilibrium. Anal Chem 69:3260–3266CrossRefGoogle Scholar
  47. 47.
    Barcelo D (1993) Extraction, clean-up and recoveries of persistent trace organic contaminants from sediment and biota samples. Environ. Anal. Tech. Appl. Qual. Assur. Elsevier Science Publishers B.VGoogle Scholar
  48. 48.
    Theocharopoulos SP, Wagner G, Sprengart J, Mohr ME, Desaules A, Muntau H, Christou M, Quevauviller P (2001) European soil sampling guidelines for soil pollution studies. Sci Total Environ 264:51–62CrossRefGoogle Scholar
  49. 49.
    European Commission Directorate General Health and Consumer Protection (2013) Analytical Quality Control and Method Validation Procedures for Pesticide Residues Analysis in Food and Feed. Document N° SANCO/12571/2013Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Aranzazu Peruga
    • 1
  • Joaquim Beltrán
    • 1
  • Francisco López
    • 1
  • Félix Hernández
    • 1
    Email author
  1. 1.Research Institute for Pesticides and WaterUniversity Jaume ICastellónSpain

Personalised recommendations