ExTech 2013 15th International Symposium on Advances in Extraction Technologies

A simple and quick method for determination of pesticides in environmental water by HF-LPME-GC/MS
Helvcio C. Menezes ; Breno, P. Paulo; Maria J. N. Paiva; Zenilda L. Cardeal
Departamento de Qumica, Universidade Federal de Minas Gerais, UFMG, Belo Horizonte, MG 31270-901, Brazil *helveciomenezes@hotmail.com Keywords: pesticides, HF-LPME, GC/MS
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INTRODUCTION Contamination of surface and ground waters by pesticides increased dramatically during the past two decades. In order to control unwanted species of plants or animals that cause damage or interfere with the production or storage several pesticides, are used. Pesticides and their degradation products may spread through the environment and frequently contaminate surface and ground waters . The determination of pesticides in environmental
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EXPERIMENTAL The pesticides studied in this work are the following: Parathion-methyl, Chlorpyriphos, Captan, Procymidone, Endosulfan, Protiophos, Cipronazole, Etion, Triazophos, Phosmet, and Mirex. The extractions were performed with propylene fibre of 6 cm length, internal diameter of 600 m and a wall thickness of 200 m. Before extraction the hollow fibre was filled with 30 L of solvent using a microsyringe. Then, the solvent-filled fibre was immersed into the vial containing 15 mL of aqueous pesticides solutions for extraction under magnetic stirring. RESULTS AND DISCUSSION The acceptor phases 1-octanol, ethyl decanoate, and ethyl octanoate were tested for extraction of pesticides by HF-LPME, and ethyl octanoate showed highest ability of extraction. Different agitation speeds were tested using ethyl octanoate as acceptor phase. The speed chosen as the most suitable for extraction was 200 rpm. Figure 1 shows the study of pesticides efficiency extraction using HF-LPME with ethyl octanoate at 200 rpm with different exposure times. The results shows that after 30 minutes there is no significant increase in extraction estimated by the peak area. The Figure 2 shows the chromatogram obtained after extraction of selected pesticides under the optimized conditions of extraction.

samples is of great interest due to their toxicity, carcinogenicity, or endocrine disrupting effects . Since the pesticides are present at trace level and wide distribution in complex water environment, it is required to develop efficient sample extraction and preconcentration methods for their determination. Liquidliquid extraction (LLE), solid-phase extraction (SPE), solid-phase microextraction (SPME), singledrop microextraction (SDME), and hollow fibre liquidphase microextraction (HF-LPME) are the methods that have been commonly used for the sample preparation of pesticides and related compounds in water samples . HF-LPME is an attractive sample preparation that use a single hollow fibre connected with a syringe needle . This method presents high preconcentration factors using really small amounts of extraction solvent. This study proposes a simple and quick sampling of eleven pesticides in environmental water matrix using gas chomatography coupled to mass spectrometry (GC/MS).
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36a Reunio Anual da Sociedade Brasileira de Qumica

ExTech 2013 15th International Symposium on Advances in Extraction Technologies

Table

1.

Performance

characteristics

of

the

optimised two-phase HF-LPME-GC/MS procedure for determination of selected pesticides in water.

Figure 1. Effect of exposure times on the extraction efficiency of pesticides from the aqueous donor phase using HF-LPME-GC/MS. The method HF-LPME-GC/MS was applied to the analysis of three real samples of surface water collected in a rural area of Minas Gerais, Brazil. Only one sample showed a concentration of Parathionmethyl of 0.15 g L . Cipronazole and Triazophos were also detected in this sample. CONCLUSION The two-phase HF-LPME-GC/MS method was
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developed, optimized and applied to the analysis of eleven pesticides in environmental water samples. This procedure is selective, simple, quick, and no Figure 2. Chromatogram of pesticides GC/MS analysis using HF-LPME extraction for 30 minutes in aqueous donor solution spiked at 50 g L , and ethyl octanoate as acceptor phase. 1, Parathionmethyl; 2, Chlorpyriphos; 3, Captan; 4, Procymidone; 5, Endosulfan; 6, Protiophos; 7, Cipronazole; 8, Etion; 9, Triazophos; 10, Phosmet; 11, Mirex. Table 1 shows the merit parameters of the optimized two-phase HF-LPME procedure for determination of selected pesticides in water.
1. T.B. Jordan, D.S. Nichols, N.I. Kerr, Anal. Bioanal. Chem. 394 (2009) 22572266. 2.F.E. Ahmed, Tr Anal Chem 20 (2001) 649 661. 3.M.I. Pinto, Gerhard Sontag, R.J. Bernardino, J.P. Noronha, Microchem J 96 (2010) 225237. 4. S. Pedersen-Bjergaard, K.E. Rasmussen, Anal Chem 71 (1999) 26502656.
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require pretreatment of the sample. In addition the proposed method showed good linearity, low detection and quantification limits, high selectivity and good repeatability for the pesticides selected. ____________________

25a Reunio Anual da Sociedade Brasileira de Qumica - SBQ