Liquid Chromatography Mass Spectrometer (LC-MS/MS) Study of Distribution Patterns of Base Peak Ions and Reaction Mechanism with Quantification of Pesticides in Drinking Water Using a Lyophilization Technique

Sukesh Narayan Sinha

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DOI: 10.4236/ajac.2011.25061                

Abstract

In the process of the development of agriculture, pesticides have become an important tool as an insecticide to kill the insect from plant for boosting food production. Therefore the insecticides/pesticides and herbicides have been used in India for agriculture setting. In this connection a sensitive method for the quantification of 5 pesticides in drinking water samples to the µgL–1 level has been developed. The paper also describes the effect of dissociation energy on ion formation and sensitivity of pesticides in water samples. The structure, ion formations, distribution of base peak and fragmentation schemes were correlated with the different dissociation energies. The new ion was obtained at different mass to charge ratio, which was the characteristic ion peak of targeted pesticide. Additionally, a simple solvent lyophilization followed by selective analysis using a liquid chromatography-mass spectrometry method was used. This method was accurate (≥98%) as it possesses limits of detection in the 6 - 38 ngL–1 range, and the percentage relative standard deviations are less than 8.62% at the low µgL–1 end of the method’s linear range. The percentage recovery of all the pesticides at the 0.1 µgL–1 levels of detection ranges from 92% - 104%. This method was used for the quantification of pesticides in water samples collected from different parts from urban city of Hyderabad, India. In this study, 13 water samples were analyzed in which all samples showed detectable level of the malathion and alachlor. The concentration of pesticides ranged from 0.004 µgL–1 to 0.691 µgL–1 exceeded to the maximum residual limit of Indian standard.

Keywords

Water, LC-MS/MS, Lyphilization, Pesticides, Dissociation Energy

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	P. C. Abhilash and N. Singh, “Pesticide Use and Applica-tion: An Indian Scenario,” Journal of Hazardous Mate-rials, Vol. 165, No. 1-3, 2009, pp. 1-12. doi:10.1016/j.jhazmat.2008.10.061
[2]	V. K. Bhatnagar, “Pesticides pollution: Trends and Pers-pectives,” ICMR Bull, Vol. 31, 2001, pp. 87-88.
[3]	D. Atkinson, F. Burnett, G. N. Foster, A. Litterick, M. Mullay and C. A. Watson, “The Minimization of Pesticide Residues in Food: a Review of the Published Literature,” Food Standards Agency, London, 2003.
[4]	B. Kumari, R. Gulati, T. S. Kathpal, “Monitoring of Pes-ticidal Contamination in Honey”, The Korean Journal of Apiculture, Vol. 18, No. 2, 2003, pp. 155-160.
[5]	B. Kumari, V. K. Madan, J. Singh, S. Singh and T. S. Kathpal, “Monitoring of Pesticidal Contamination of Farmgate Vegetables from Hisar” Environmental Moni-toring and Assessment,” Earth and Environmental Science, Vol. 90, No. 1-3, 2004, pp. 65-77. doi:10.1023/b:emas.0000003566.63111
[6]	B. Kumari, J. Singh, S. Singh and T. S. Kathpal, “Moni-toring of Butter and Ghee (Clarified Butter Fat) for Pesti-cidal Contamination from Cotton Belt of Haryana, India,” Environmental Monitoring and Assessment, Vol. 105. No. 1-3, 2005, pp. 111-120. doi:org/10.1007/s10661-005-3159-2
[7]	B. Kumari, T. S. Kathpal and E. M. Assess. “Monitoring of Pesticide Residues in Vegetarian Diet,” Environ Monit Assess, Vol. 151, 2009, p.1926.
[8]	B. Kumari, V. K. Madan and T. S. Kathpal, “Monitoring of Pesticide Residues in Fruits,” Environmental Monitor-ing and Assessment, Vol. 123, No. 1-3, 2006, pp. 407-412. doi:org/10.1007/s10661-006-1493-7
[9]	B. Kumari, V. K. Madan, R. Kumar and T. S. Kathpal, “Monitoring of Seasonal Vegetables for Pesticide Resi-dues,” Environmental Monitoring and Assessment, Vol. 74, No. 3, 2002, pp. 263-270. doi:org/10.1023/A:1014248827898
[10]	S. N. Sinha, R. Pal, A. Dewan, M. M. Mansuri and H. N. Saiyed, “Effect of Dissociation Energy on Ion Formation and Sensitivity of An Analytical Method for Determination of Chlorpyrifos in Human Blood, Using Gas Chro-matography-Mass Spectrometer (GC-MS in MS/MS),” International Journal of Mass Spectrometry, Vol. 253, No. 1-2, 2006, pp. 48-57. doi:org/10.1016/j.ijms.2006.02.020
[11]	V. K. Dua, G. Rosy, S. N. Sinha and A. P. Das, “Alleth-rin in the Air during the Use of a Heated Mosquito Re-pellent Mat,” Bullet Environmental Contamination and Toxicology, Vol. 75, No. 4, 2005, pp. 747-750. doi:org/10.1007/s00128-005-0814-9
[12]	A. Dewan, V. K. Bhatnagar, M. L. Mathur, T. Chakma, R. Kashyap and G. H. Sadhu, et al. “Repeated Episodes of Endosulfan Poisoning,” Journal of Toxicology-Clinical Toxicology, Vol. 42, No. 4, 2004, pp. 1-7. doi:org/10.1081/CLT-120039542
[13]	S. N. Sinha, T. S. Patel, N. M. Desai, M. M. Mansuri, A. Dewan and H. N. Saiyed, “GC-MS Study of Endosulfan in Biological Samples,” Asian Journal of Chemistry, Vol. 16, No. 3-4, 2004, pp. 1685-1690.
[14]	S. N. Sinha, “Effect of Dissociation Energy: Signal to Noise Ratio on Ion Formation and Sensitivity of Analytical Method for Quantification and Confirmation of Triazofos in Blood Samples Using Gas Chromatography–Mass Spectrometer (GC–MS/MS),” International Journal of Mass Spectrometry, Vol. 296, No. 1-3, 2010, pp. 47-52. doi:org/10.1016/j.ijms.2010.08.014
[15]	P. Paya, M. Anastassiades, D. Mack, I. Sigalova, B. Tas-delen and J. Oliva, et al. “Analysis of Pesticide Residues Using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) Pesticide Multiresidue Method in Combi-nation with Gas and Liquid Chromatography and Tandem Mass Spectrometric Detection,” Analytical Bioanalytical Chemistry, Vol. 389, No. 6, 2007, pp. 1697-1714. doi:org/10.1007/s00216-007-1610-7
[16]	D. B. Barr, J.R. Barr, V. L. Maggio, Jr. R. D. Whitehead, M. A. Sadowski and R. Whyatt, et al. “A Multi-Analyte Method for the Quantification of Contemporary Pesticides in Human Serum and Plasma Using High-Resolution Mass Spectrometry,” Journal of Chromatography B, Vol. 778, 2002, pp. 9-11.
[17]	S. N. Sinha, K. Vasudev, M. V. Rao and M. Odetokun, “Quantification of Organophosphate Insecticides in Drinking Water in Urban Areas Using Lyophilization and High-Performance Liquid Chromatography–Electrospray Ionization-Mass Spectrometry Techniques,” International Journal of Mass Spectrometry, Vol. 300, 2011, pp. 12-20. doi:org/10.1016/j.ijms.2010.11.006
[18]	S. N. Sinha, V. K. Bhatnagar, P. Doctor, G. S. Toteja, N. P. Agnihotri and R. L. Kalra, “A Novel Method for Pesti-cide Analysis in Refined Sugar Samples Using a Gas Chromatography–Mass Spectrometer (GC–MS/MS) and Simple Solvent Extraction Method,” Food Chemistry, Vol. 126, No. 1, 2011b, pp. 379-386. doi:org/10.1016/j.foodchem.2010.10.110
[19]	K. D. Miller and P. Milne, “Determination of Low-Level Pesticides Residues in Soft Drinks and Sport Drinks by Liquid Chromatography with tandem Mass Spectrometry: Collaborative Study,” Journal of AOAC International, Vol. 91 No. 1, 2008a, pp. 181-201.
[20]	K. D. Miller and P. Milne, “Determination of (0.5 μg/L) in soft drinks and sport drinks by Gas Chro Low-Level Pesticides Residues Monograph with Mass Spectrometry: Collaborative Study,” Journal of AOAC International, Vol. 91, No. 1, 2008b, pp. 202-236.
[21]	A. Sarkar and R. Gupta Sen, “Determination of Orga-nochlorine Pesticides in Indian Coastal Water Using a Mooredin-Situ Sampler,” Water Research, Vol. 23 No. 8, 1989, pp. 975-978. doi:org/10.1016/0043-1354(89)90170-X
[22]	N. Bakore, P. J. John and P. Bhatnagar, “Organochlorine Pesticide Residues in Wheat and Drinking Water Samples from Jaipur, Rajasthan, India,” Environmental Monitor- ing and Assessment, Vol. 98, No. 1-3, 2002, pp. 381-389. doi:org/10.1023/B:EMAS.0000038197.76047.83
[23]	N. Sankararamakrishnan, A. K. Sharma and R. Sanghi, “Organochlorine and Organophosphorous Pesticide Re-sidues in Ground Water and Surface Waters of Kanpur, Uttar Pradesh, India,” Environment International, Vol. 31, No. 1, 2005, pp. 113-120. doi:org/10.1016/j.envint.2004.08.001