Method Development and Validation for the Determination of Pesticide Residues in Water by GC-NPD

Abstract

A multi-residue method was developed for the determination of organophosphorous pesticides and

Herbicide by liquid-liquid extraction (LLE) and followed by gas chromatography-nitrogen-phosphorus detector

(GC/NPD). The method was evaluated with respect to the limit of detection and quantification, linearity and accuracy

(repeatability, reproducibility, recovery). The method is linear over the range 2.5 -25 μg L-1 for eleven pesticides

and 5-25 μg L-1 for methamidophos. Correlation coefficients were higher or equal to 0.992. The limits of detection

(LODs) were between 0.67 and 2.23 μg L-1. The limits of quantification (LOQs) ranged from 2.24 and 7.45 μg L-1.

Recoveries of fortified water samples in two different concentration levels with 12 organophosphorous pesticides

and herbicide were over 95% in high concentration and 80% in low concentration. For repeatability, relative standard

deviation (RSD%) ranged between 2.79 and 10.99%, and for reproducibility (RSD%) ranged between 1.56

and 10.36 %. The developed method is suitable for routine application in water samples in accordance with the

validation data and the parameter as the high sample throughput and cost effective.

Keywords

• Environmental pollution,GC/NPD,method validation,multi-residue analysis,pesticide

Sudaki Pestisit Kalıntılarının Belirlenmesi için GC-NPD Kullanılarak Method Geliştirilmesi ve Validasyonu

Abstract

Organik fosforlu pestisitlerin ve herbisitlerin sıvı-sıvı ekstraksiyonu (LLE) ve ardından gaz kromatografisiazot-

fosfor dedektörü (GC / NPD) ile belirlenmesi için bir çoklu kalıntı yöntemi geliştirildi. Metod; dedeksiyon

ve miktar sınırı, doğrusallık ve doğruluk (tekrarlanabilirlik tekrarüretilebilirlik, geri kazanma) limitine göre

değerlendirildi. Yöntem, on bir pestisit için 2.5-25 μg L-1 aralığında ve metamidofos için 5-25 μg L-1 aralığında

doğrusaldır. Korelasyon katsayıları 0.992’ ye eşit veya daha yüksektir. Dedeksiyon limitleri (LOD) 0.67 ve 2.23 μg L-1

arasındadır. Miktar sınırlamaları (LOQ) 2.24 ve 7.45 μg L-1 arasında değişmektedir. 12 organofosforlu pestisit

ve herbisit ile iki farklı konsantrasyon seviyesinde zenginleştirilmiş su numunelerinin geri kazanımı, yüksek

konsantrasyonda %95’in üzerinde ve düşük konsantrasyonda %80’ in üzerindedir. Tekrarlanabilirlik için, relatif

standart sapma (RSD%) 2.79 ile 10.99 arasında ve tekrarüretilebilirlik için (RSD%), 1.56 ile %10.36 arasında

değişmektedir. Geliştirilen yöntem, validasyon verilerine ve yüksek numune akışı ile uygun maliyetli oluşu gibi

parametrelere göre su numunelerinde rutin uygulama için uygundur.

Keywords

• Çevre kirliliği,çoklu kalıntı analizleri,GC/NPD,metod validasyonu,pestisit

References

1. Beltran, J., Lopez, F., Cepria, O., Hernandez, F., 1998. Solid-phase microextraction for quantitative analysis of organophosphorus pesticides in environmental water samples. Journal of Chromatography A 808, 257-263.
2. Bempelou, E.D., Liapis, K.S., 2006. Validation of a multi-residue method for the determination of pesticide residues in apples by gas chromatography. International Journal of Environmental Analytical Chemistry 86, 63-68.
3. Cabrera, L.d.C., Costa, F.P., Primel, E.G., 2008. Estimativa de risco de contaminação das águas por pesticidas na região sul do estado do RS.
4. Canbay, H., Öğüt, S., Yılmazer, M., 2014. Pesticide residues analysis in lake water and sediment samples from the Golcuk National Park. Water resources 41, 97-104.
5. Castilho, J., Fenzl, N., Guillen, S.M., Nascimento, F., 2000. Organochlorine and organophosphorus pesticide residues in the Atoya river basin, Chinandega, Nicaragua. Environmental Pollution 110, 523-533.
6. Costa, L.L., Sant ana, E.S., Suchara, E.A., Benato, V.S., Carasek, E., 2008. Determinação de herbicidas usados no cultivo de arroz irrigado na região sul do estado de Santa Catarina através da SPME-GC-ECD. Química Nova 31, 79.
7. Dorea, H., Tadeo, J., Sanchez-Brunete, C., 1996. Determination of organophosphorus pesticide residues in fruits by gas chromatography with ITD and NPD detection. Chromatographia 43, 380-386.
8. Dömötörová, M., Matisová, E., 2008. Fast gas chromatography for pesticide residues analysis. Journal of Chromatography A 1207, 1-16.

9. Driss, M., Hennion, M.-C., Bouguerraca, M., 1993. Determination of carbaryl and some organophosphorus pesticides in drinking water using on-line liquid chromatographic preconcentration techniques. Journal of Chromatography A 639, 352-358.
10. Environmental Protection Agency (EPA), 1990. National survey of pesticides in drinking water wells. Phase I Report. Office of Water and Office of Pesticides Programs, U.S. Government Printing Office Washington, DC.
11. Jin, B., Xie, L., Guo, Y., Pang, G., 2012. Multi-residue detection of pesticides in juice and fruit wine: a review of extraction and detection methods. Food research international 46, 399-409.
12. Komatsu, E., Vaz, J.M., 2004. Otimização dos parâmetros de extração para determinação multiresíduo de pesticidas em amostras de água empregando microextração em fase sólida. Química Nova 27, 720-724.
13. Menezes Filho, A., dos Santos, F.N., Pereira, P.A.d.P., 2010. Development, validation and application of a method based on DI-SPME and GC–MS for determination of pesticides of different chemical groups in surface and groundwater samples. Microchemical Journal 96, 139-145.
14. Park, J.H., Iqbal Rouf Mamun, M., Abd El‐Aty, A., Na, T.W., Choi, J.H., Ghafar, M., Kim, K.S., Kim, S.D., Shim, J.H., 2011. Development and validation of a multiresidue method for determination of 37 pesticides in soil using GC‐NPD. Biomedical Chromatography 25, 1003-1009.
15. Rocha, M.J., Ribeiro, M.F., Cruzeiro, C., Figueiredo, F., Rocha, E., 2012. Development and validation of a GC-MS method for determination of 39 common pesticides in estuarine water–targeting hazardous amounts in the Douro River estuary. International journal of environmental analytical chemistry 92, 1587-1608.
16. SANCO, 2004. Quality control procedures for pesticide residue analysis. Document N8. SANCO/10476/2003. European Commission, Directorate General Health and Consumer Protection.
17. Suman, P., Singh, D.K., 2011. Estimating the uncertainty of pesticide residue analysis from mango using multi-residue analysis and validation of method. Toxicological & Environmental Chemistry 93, 1880-1896.
18. Tian, F., Liu, W., Fang, H., An, M., Duan, S., 2014. Determination of six organophosphorus pesticides in water by single-drop microextraction coupled with GC-NPD. Chromatographia 77, 487-492.
19. Vidal, J., Liébanas, F., Rodríguez, M., Frenich, A.G., Moreno, J., 2006. Validation of a gas chromatography/triple quadrupole mass spectrometry based method for the quantification of pesticides in food commodities. Rapid communications in mass spectrometry 20, 365-375.