DOI QR코드

DOI QR Code

Simultaneous Determination of Pesticides in Water Using a GC/MS Coupled with Micro Extraction by Packed Sorbent

MEPS-GC/MS를 이용한 농약류 동시 수질분석

  • Received : 2015.03.18
  • Accepted : 2015.05.15
  • Published : 2015.05.31

Abstract

This study established an analytical method to simultaneously determine six organophosphorous pesticides [methyldemetone-S, diazinon, fenitrothion, parathion, phentoate, and O-ethyl O-(4-nitrophenyl) phenylphosphonothioate (EPN)] and carbaryl in water using a gas chromatography/mass spectrometry (GC/MS) system coupled with on-line micro extraction by packed sorbent (MEPS) and programmed temperature vaporizer (PTV) injector. Polystyrene divinylbenzene (PDVB) was used as a sorbent of MEPS. The effects of elution solvents, pH, elution volume and draw-eject cycles of samples on sample pretreatment process were investigated. Also, quality assurance and quality control (QA/QC) and the recovery of the pesticides in environmental samples were evaluated. The elution was performed using $30{\mu}L$ of a mixed solvent (acetone : dichloromethane = 80 : 20 (v/v)). Sample pretreatment processes were optimized with seven cycles of draw-eject of sample (1 mL) spiking an internal standard and sulfuric acid. At lower pH, the analytical sensitivity of diazinon decreased, but that of carbaryl increased. The method detection limit and the limit of quantification for this method were 0.02~0.18 and $0.08{\sim}0.59{\mu}g/L$, respectively. The method precision and accuracy were 1.5~11.5% and 83.3~129.8%, respectively, at concentrations of $0.5{\sim}5.0{\mu}g/L$. The recovery rates for all the pesticides except carbaryl in various environmental samples ranged 75.7~129.3%. The recovery rate of carbaryl in effluent sample was over 200% whereas carbaryl in drinking water, groundwater, and river water were in the acceptable range.

Keywords

Organochlorine Pesticides;Carbaryl;Micro Extraction by Packed Sorbent (MEPS);Polystyrene Divinylbenzene (PDVB);Gas Chromatography Mass Spectrometry;Limit of Quantification

References

  1. Cavalheiro, J., Prieto, A., Monperrus, M., Etxebarria, N. and Zuloaga, O., "Determination of polycyclic and nitro musks in environmental water samples by means of microextraction by packed sorbents coupled to large volume injection-gas chromatography-mass spectrometry analysis," Anal. Chim. Acta, 773, 68-75(2013). https://doi.org/10.1016/j.aca.2013.02.036
  2. Rodrigues, M., Alves, G., Rocha, M., Queiroz, J. and Falcaao, A., "First liquid chromatographic method for the simultaneous determination of amiodarone and desethylamiodarone in human plasma using microextraction by packed sorbent (MEPS) as sample preparation procedure," J. Chromatogr. B: Anal. Technol. Biomed. Life Sci., 913-914, 90-97(2013). https://doi.org/10.1016/j.jchromb.2012.11.028
  3. Alves, G., Rodrigues, M., Fortuna, A., Falcaao, A. and Queiroz, J., "A critical review of microextraction by packed sorbent as a sample preparation approach in drug bioanalysis," Bioanalysis, 5, 1-34(2013). https://doi.org/10.4155/bio.12.307
  4. Mercolini, L., Protti, M., Fulgenzi, G., Mandrioli, R., Ghedini, N., Conca, A. and Raggi, M. A., "A fast and feasible microextraction by packed sorbent (MEPS) procedure for HPLC analysis of the atypical antipsychotic ziprasidone in human plasma," J. Pharmaceut. Biomed. Anal., 88, 467-471(2014). https://doi.org/10.1016/j.jpba.2013.09.019
  5. Altun, Z., Abdel-Rehim, M. and Blomberg, L. G., "New trends in sample preparation: on-line microextraction in packed syringe (MEPS) for LC and GC applications Part III: Determination and validation of local naesthetics in human plasma samples using a cation-exchange sorbent, and MEPSLC-MS-MS," J. Chromatogr. B, 813, 129-135(2004). https://doi.org/10.1016/j.jchromb.2004.09.020
  6. Said, R., Pohanka, A., Abdel-Rehim, M. and Beck, O., "Determination of four immunosuppressive drugs in whole blood using MEPS and LC-S/MS allowing automated sample workup and analysis," J. Chromatogr. B, 897, 42-49(2012). https://doi.org/10.1016/j.jchromb.2012.04.006
  7. Bagheri, H., Ayazi, Z., Es'haghi, A. and Aghakhani, A., "Reinforced polydiphenylamine nanocomposite for microextraction in packed syringe of various pesticides," J. Chromatogr. A, 1222, 13-21(2012). https://doi.org/10.1016/j.chroma.2011.11.063
  8. Bagheri, H, Alipour, N. and Ayazi, Z., "Multiresidue determination of pesticides from aquatic media using polyaniline nanowires network as highly efficient sorbent for microextraction in packed syringe," Anal. Chim. Acta, 740, 43-49 (2012). https://doi.org/10.1016/j.aca.2012.06.026
  9. Jafari, M., Saraji, M. and Yousefi, S., "Negative electrospray ionization ion mobility spectrometry combined with microextraction in packed syringe for direct analysis of phenoxyacid herbicides in environmental waters," J. Chromatogr. A, 1249, 41-47(2012). https://doi.org/10.1016/j.chroma.2012.06.024
  10. Quinto, M., Spadaccino, G., Nardiello, D., Palermo, C., Amodio, P., Li, D. and Centonze, D., "Microextraction by packed sorbent coupled with gaschromatography-mass spectrometry: A comparison between "draw-eject" and "extractdiscard" methods under equilibriumconditions for the determination of polycyclic aromatic hydrocarbonsin water," J. Chromatogr. A, 1371, 30-38(2014). https://doi.org/10.1016/j.chroma.2014.10.062
  11. AWWA, Standard Method 6610(1999).
  12. EPA, Method 531.2, Revision 1.0(2001).
  13. Korean Ministry of Environment, Korean Standards Methods on Drinking Water(2013).
  14. Hu, C., He, M., Chen, B. and Hu, B., "A sol-gel polydimethylsiloxane/polythiophene coated stir bar sorptive extraction combined with gas chromatography-flame photometric detection for the determination of organophosphorus pesticides in environmental water samples," J. Chromatogr. A, 1275, 25-31(2013). https://doi.org/10.1016/j.chroma.2012.12.036
  15. Seebunrueng, K., Santaladchaiyakit, Y. and Srijaranai, S., "Vortex-assisted low density solvent based demulsified dispersive liquid-liquid microextraction and high-performance liquid chromatography for the determination of organophosphorus pesticides in water samples," Chemosphere, 103, 51-58(2014). https://doi.org/10.1016/j.chemosphere.2013.11.024
  16. Mauriz, E., Calle, A., Abad, A., Montoya, A., Hildebrandt, A., Barcelo, D. and Lechuga, L. M., "Determination of carbaryl in natural water samples by a surface plasmon of resonance flow-through immunosensor," Biosens. Bioelectron., 21, 2129-2136(2006). https://doi.org/10.1016/j.bios.2005.10.013
  17. Ballesteros, E. and Parrado, M. J., "Continuous solid-phase extraction and gas chromatographic determinatioin of organophosphorus pesticides in natural and drinking waters," J. Chromatogr. A, 1029, 267-273(2004). https://doi.org/10.1016/j.chroma.2003.12.009
  18. Wu, L., Song, Y., Hu, M., Zhang, H., Yu, A., Yu, C., Ma, Q. and Wang, Z., "Application of magnetic solvent bar liquidphase microextraction for determination of organophosphorus pesticides in fruit juice samples by gas chromatography mass spectrometry," Food Chem., 176, 197-204(2015). https://doi.org/10.1016/j.foodchem.2014.12.055
  19. Anwar, Z. M., Rizk, M. A., Khairy, G. M. and EI-Asfoury, M. H., "Determination of organophosphorus pesticides in water samples by using a new sensitive lumine scent probe of Eu(III) complex," J. Luminescence, 157, 371-382(2015). https://doi.org/10.1016/j.jlumin.2014.09.008
  20. Gutierrez Valencia, T. M. and Garcia de Llasera, M. P., "Determination of organophosphorus pesticides in bovine tissue by an on-line coupled matrix solid-phase dispersion-solid phase extraction-high performance liquid chromatography with diode array detection method," J. Chromatogr. A, 1218, 6869-6877(2011). https://doi.org/10.1016/j.chroma.2011.08.011
  21. Cortes-Aguado, S., Sanchez-Morito, N., Arrebola, F. J., Garrido Frenich, A. and Martinez Vidal, J. L., "Fast screening of pesticide residues in fruit juice by solidphase microextraction and gas chromatography-mass spectrometry," Food Chem., 107, 1314-1325(2008). https://doi.org/10.1016/j.foodchem.2007.09.033
  22. Su, P. G. and Huang, S. D., "Determination of organophosphorus pesticides in water by solid-phase microextraction," Talanta, 49, 393-402(1999). https://doi.org/10.1016/S0039-9140(99)00002-8
  23. Farajzadeh, M. A., Djozan,D., Nouri, N., Bamorowat, M. and Shalamzari, M. S., "Coupling stir bar sorptive extraction dispersive liquid-liquid microextraction for preconcentration of triazole pesticides from aqueous samples followed by GCFID and GC-MS determinations," J. Sep. Sci., 33, 1816-1828(2010). https://doi.org/10.1002/jssc.201000088
  24. Zuin, V. G., Schellin, M., Montero, L., Yariwake, J. H., Augustod, F. and Popp, P., "Comparison of stir bar sorptive extraction and membrane-assisted solvent extraction as enrichment techniques for the determination of pesticide and benzo [a]pyrene residues in Brazilian sugarcane juice," J. Chromatogr. A, 1114, 180-187(2006). https://doi.org/10.1016/j.chroma.2006.03.035
  25. Lambropoulou, D. A. and Albanis, T. A., "Liquid-phase microextraction techniques in pesticide residue analysis," J. Biochem. Biophysical Methods, 70, 195-228(2007). https://doi.org/10.1016/j.jbbm.2006.10.004
  26. Pintoa, M. I., Sontag, G., Bernardino, R. J. and Noronha, J. P., "Pesticides in water and the performance of the liquidphase microextraction based techniques. A review," Microchem. J., 96, 225-237(2010). https://doi.org/10.1016/j.microc.2010.06.010
  27. Ferreira, A., Rodrigues, M., Oliveira, P., Francisco, J., Fortuna, A., Rosado, L., Rosado, P., Falcao, A. and Alves, G., "Liquid chromatographic assay based on microextraction by packed sorbent for therapeutic drug monitoring of carbamazepine, lamotrigine, oxcarbazepine, phenobarbital, phenytoin and the activemetabolites carbamazepine-10,11-epoxide and licarbazepine," J. Chromatogr. B, 971, 20-29(2014). https://doi.org/10.1016/j.jchromb.2014.09.010

Acknowledgement

Supported by : 국립환경과학원, 중소기업청