Determination of herbicide residues in rice paddy water by solid phase extraction and high performance liquid chromatography with diode array detection

Gonçalves, Fabio Ferreira; Matos, Fabio da Silva de; Zanella, Renato

Palavras-chave: Pesticides, surface water, SPE, HPLC-DAD.

ResumoThe herbicides used on crops are generally persistent and can pollute water supplies. Therefore, this study aimed to develop and validate a method for the determination of residues of the herbicides clomazone, imazethapyr and imazapic in rice paddy water. The method involves sample preparation using Solid Phase Extraction, to allow an appropriate concentration factor, and quantification by High Performance Liquid Chromatography with Diode Array Detection. After optimization of the extraction and analysis parameters, the method was validated by evaluating analytical curve, linearity, limits of detection and quantification, precision (repeatability and intermediate precision) and accuracy. The results showed excellent linearity for all compounds (r2 > 0.99) in the range between the limit of quantification and 2.5 mg L–1. The method showed recoveries between 81 and 107%, with RSD < 9%, and was applied for the determination of residues of herbicides in rice paddy water with limits of quantification (LOQ) of 0.12 μg L–1 for imazapic and imazethapyr, and of 0.25 μg L–1 for clomazone.

Referências Bibliográficas

1. Richardson SD. Environmental Mass Spectrometry: Emerging Contaminants and Current Issues. Analytical Chemistry 2006; 78:4021-4045. http://
2. Carabias-Martinez R, Gonzalo ER, Hernandez EH, Mendez JH. Simultaneous determination of phenyl- and sulfonylurea herbicides in water by solidphase extraction and liquid chromatography with UV diode array or mass spectrometric detection. Analytica Chimica Acta 2004; 517:71-79. http://dx.doi. org/10.1016/j.aca.2004.05.007
3. Kuster M, López de Alda M, Barceló D. Analysis of pesticides in water by liquid chromatography-tandem mass spectrometry techniques. Mass Spectrometry Reviews 2006; 25:900-916. mas.20093
4. Picó Y, Fernandez M, Ruiz MJ, Font G. Current trends in solid-phase-based extraction techniques for the determination of pesticides in food and environment. Journal of Biochemical and Biophysical Methods 2007.; 70:117-131. jbbm.2006.10.010
5. Wells MJM. Principles of extraction and the extraction of semivolatile organics from liquids. In: Mitra S, editor. Sample Preparation Techniques in Analytical Chemistry. Hoboken: Wiley-Interscience; 2003. p. 37-138.
6. Sabin GP, Prestes OD, Adaime MB, Zanella R. Multiresidue Determination of Pesticides in Drinking Water by Gas Chromatography-Mass Spectrometry after Solid-Phase Extraction. Journal of Brazilian Chemical Society 2009; 20:918-925. http://dx.doi. org/10.1590/S0103-50532009000500017
7. Primel EG, Zanella R, Kurz MHS, Goncalves FF, Machado SO, Marchezan E. Poluição das águas por herbicidas utilizados no cultivo do arroz irrigado na região central do estado do Rio Grande do Sul, Brasil: predição teórica e monitoramento. Química Nova 2005.; 28:605-609. 40422005000400010.
8. Zanella R, Primel EG, Goncalves FF, Martins ML, Adaime MB, Marchezan E, Machado SLO. Study of the degradation of the herbicide clomazone in distilled and in irrigated rice field waters using HPLC-DAD and GC-MS. Journal of Brazilian Chemical Society 2008.; 19:987-995. 50532008000500026.
9. Pichon V, Charpak M, Henion MC. Multiresidue analysis of pesticides using new laminar extraction disks and liquid chromatography and application to the French priority list. Journal of Chromatography A 1998; 795:83-92. 9673.(97)01035-2
10. Caldas SS, Gonçalves FF, Primel EG, Prestes OD, Martins ML, Zanella R. Principais técnicas de preparo de amostra para a determinação de resíduos de agrotóxicos em água por cromatografia líquida com detecção por arranjo de diodos e por espectrometria de massas. Química Nova 2011; 34:1604-1617. http://
11. Bruzzoniti MC, Sarzanini C, Mentasti E. Preconcentration of contaminants in water analysis. Journal of Chromatography A 2000; 902:289-309.
12. Zanella R, Primel EG, Machado SLO, Gonçalves FF, Marchezan E. Monitoring of the Herbicide Clomazone in Environmental Water Samples by Solid-Phase Extraction and High-Performance Liquid Chromatography with Ultraviolet Detection. Chromatographia 2002; 55:573-577. http://dx.doi. org/10.1007/BF02492903
13. Rissato SR, Libânio M, Giafferis GP, Gerenutti M. Determinação de pesticidas organoclorados em água de manancial, água potável e solo na região de Bauru (SP). Química Nova 2004; 27:739-743. http://dx.doi. org/10.1590/S0100-40422004000500012
14. Shukla G, Kumar A, Bhanti M, Joseph PE, Taneja A. Organochlorine pesticides contamination of ground water in the city of hyderabad. Environmental International 2006; 32:244-247. http://dx.doi. org/10.1016/j.envint.2005.08.027
15. Marques MN, Cotrim MB, Faustino MAP, Beltrame O Fº. Avaliação do impacto da agricultura em áreas de proteção, pertencentes à bacia hidrográfica do rio Ribeira de Iguape, São Paulo. Química Nova 2007; 30.:1171-1178. 40422007000500023.
16. Bortoluzzi EC, Rheinheimer DS, Gonçalves CS, Pellegrini JBR, Maroneze AM, Kurz MHS, et al. Investigation of the occurrence of pesticides residues in rural wells and surface water following application to tobacco. Química Nova 2007, 30, 1872-1876. http://
17. Donato FF, Kemmerich M, Facco JF, Friggi CA, Prestes OD, Adaime MB, et al. Simultaneous determination of pesticide and antibiotic residues at trace levels in water samples by SPE and LC-MS/MS. Brazilian Journal of Analytical Chemistry 2012, 07, 331-340.
18. Martins ML, Donato FF, Prestes OD, Adaime MB, Zanella R. Determination of pesticide residues and related compounds in water and industrial effluent by solid-phase extraction and gas chromatography coupled to triple quadrupole mass spectrometry. Analytical and Bioanalytical Chemistry 2013; 405.:7697-7709.
19. Carvalho JJ, Jeronimo PCA, Gonçalves C, Alpendurada MF. Evaluation of a multiresidue method for measuring fourteen chemical groups of pesticides in water by use of LC-MS-MS. Analytical Bioanalytical Chemistry 2008; 392:395-368. http://
20. Kowal S, Balsaa P, Werres F, Schmidt TC. Determination of the polar pesticide degradation product N,N-dimethylsulfamide in aqueous matrices by UPLC-MS/MS. Analytical Bioanalytical Chemistry 2009., 395:1787-1794. s00216-009-2861-2
21. Ayano E, Kanazawa H, Andoa M, Nishimura T. Determination and quantitation of sulfonylurea and urea herbicides in water samples using liquid chromatography with electrospray ionization mass spectrometric detection. Analytica Chimica Acta 2004.; 507:211-218. aca.2003.11.027
22. Zanella R, Primel EG, Kurz MHS, Gonçalves FF, Martins ML, Machado SLO, et al. Risk assessment of surface water contamination by herbicide residues: monitoring of propanil degradation in irrigated rice field waters using HPLC-UV and Confirmation by GC-MS. Journal of Brazilian Chemical Society 2007.; 18:585-589. 50532007000300014.
23. Tran ATK, Hyde RV, Doble P. Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC. Chemosphere 2007.; 67:944-953. chemosphere.2006.11.002
24. Bruzzoniti MC, Sarzanini C, Costantino G, Fungi M. Determination of herbicides by solid phase extraction gas chromatography-mass spectrometry in drinking waters. Analytica Chimica Acta 2006; 578:241-249.
25. Estévez E, Cabrera MC, Molina-Díaz A, Robles- Molina J, Palacios-Díaz MP. Screening of emerging contaminants and priority substances (2008/105/EC) in reclaimed water for irrigation and groundwater in a volcanic aquifer (Gran Canaria, Canary Islands, Spain). Science of The Total Environment 2012; 433:538- 546..
26. Lagana A, Fago C, Marino A. Simultaneous determination of imidazolinone herbicides from soil and natural waters using soil column extraction and off-line solid-phase extraction followed by liquid chromatography with UV detection or liquid chromatography electrospray mass spectroscopy. Analytical Chemistry 1998; 70:121-130. http://dx.doi. org/10.1021/ac9707491
27. Bezemer E, Rutan S. Study of hydrolysis of a sulfonylurea herbicide using liquid chromatography with diode array detection and mass spectrometry by three-way multivariate curve resolution-alternating least squares. Analytical Chemistry 2001; 73:4403- 4409..
28. Zanella R, Primel EG, Gonçalves FF, Kurz MHS, Mistura CM. Development and validation of a highperformance liquid chromatographic procedure for the determination of herbicide residues in surface and agriculture waters. Journal of Separation Science 2003; 26.:935-938.
29. Liu JF, Chao JB, Jiang GB, Cai YQ, Liu JM. Trace analysis of sulfonylurea herbicides in water by on-line continuous flow liquid membrane extraction-C18 precolumn liquid chromatography with ultraviolet absorbance detection. Journal of Chromatography A 2003.; 995:21-28. 9673.(03)00515-6
30. Zanella R, Adaime MB, Peixoto SC, Friggi CA, Prestes DP, Machado SLO, et al. Herbicides Persistence in Rice Paddy Water in Southern Brazil, Herbicides – Mechanisms and Mode of Action, Dr. Mohammed Nagib Hasaneen (Ed.). InTech; 2011.. Available from: books/herbicidesmechanisms-and-mode-of-action/ herbicides-persistence-in-rice-paddy-water-insouthern- brazil.
31. Vencill WK. Herbicide Handbook. 8th ed. Lawrence: Weed Science Society of America; 2002.
32. Mervosh TL, Simms GK, Stoller EW. Clomazone fate as affected by microbial activity, temperature, and soil moisture. Journal of Agricultural and Food Chemistry 1995.; 43:537-543. jf00050a052
33. Hatrik S, Tekel J. Extraction methodology and chromatography for the determination of residual pesticides in water. Journal of Chromatography A 1996.; 733:217-233. 9673.(95)00725-3
34. Santos FM, Marchesan E, Machado SLO, Avila LA, Zanella R, Gonçalves FF. Persistência dos herbicidas imazethapyr e clomazone em lâmina de água do arroz irrigado. Planta Daninha 2008; 26:875-881. http://
35. Martini LFD, Caldas, SS, Bolzan CM, Bundt AD, Primel EG, Avila LA. Risco de contaminação das águas de superfície e subterrâneas por agrotóxicos recomendados para a cultura do arroz irrigado. Ciência Rural 2012; 42:1715-1721. http://dx.doi. org/10.1590/S0103-84782012001000001
36. Ribani M, Bottoli CBG, Collins CH, Jardim ICSF, Melo LFC. Validação em métodos cromatográficos e eletroforéticos. Química Nova 2004; 27:771-780.
37. Hubert P, Rozet E, Ceccato A, Hubert C, Ziemons E, Oprean R, et al. Analysis of recent pharmaceutical regulatory documents on analytical method validation. Journal of Chromatography A 2007; 1158:111-125.
38. Mamun MdIR, Park JH, Choi J-H, Kim HK, Choi WJ, Han S-S, et al. Development and validation of a multiresidue method for determination of 82 pesticides in water using GC. Journal of Separation Science 2009; 32:559-574. jssc.200800606
39. Vigna CR, Morais LS, Collins CH, Jardim IC. Poly(methyloctylsiloxane) immobilized on silica as a sorbent for solid-phase extraction of some pesticides. Journal of Chromatography A 2006; 1114:211-215.
40. Furlong ET, Burkhardt MR, Gates PM, Werner SL, Battaglin WA. Routine determination of sulfonylurea, imidazolinone, and sulfonamide herbicides at nanogram-per-liter concentrations by solid-phase extraction and liquid chromatography mass spectrometry. Science of the Total Environment 2000.; 248:135-146. 9697.(99)00537-9
41. COMISSION OF THE EUROPEAN COMMUNITIES. Document nº SANCO/12495/2011. Method validation and quality control procedures for pesticide residues analysis in food and feed. SANCO; 2011.
42. Zanella R, Primel EG, Gonçalves FF, Martins AF. Development and validation of a high-performance liquid chromatographic method for the determination of clomazone residues in surface water. Journal of Chromatography A 2000; 904(2):257-262. http://