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1 Analysis of Organophosphorus
2 Pesticides in Whole Milk by
3 Solid Phase Microextraction
4 Gas Chromatography Method
5 Zenilda de Lourdes Cardeal and Claudia Maria Dias Paes
6 Chemistry Department, ICEx, Federal University of Minas Gerais, Belo Horizonte, M.G.,
7 Brazil
8 Solid phase microextraction (SPME) was used for the extraction of residual coumaphos
9 and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatog-
10 raphy equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder
11 with a 100-µm polyacrylate fiber was used. The optimized conditions for extraction
12 by SPME method were: sample agitation, absorption temperature of 30◦ C, absorp-
13 tion time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in
14 the vial. Under these conditions, the calibration graphs were linear in the range of
15 0.17 µgL−1 to 1.75 µgL−1 for coumaphos and 0.69 µgL−1 to 6.90 µgL−1 for dichlorvos.
16 Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos.
17 The detection limits (LOD) were 0.060 µgL−1 for dichlorvos and 0.052 for coumaphos.
18 The quantification limits (LOQ) were 0.086 µgL−1 for dichlorvos and 0.066 µgL−1 for
19 coumaphos. The results obtained in this study suggest that SPME is a suitable tech-
20 nique for residual pesticide analysis of milk. The data demonstrate that particular
21 OP pesticides used in dairy farming in the region of Minas Gerais were found to
22 contaminate cow whole milk, and the residues are not removed by treating the milk
23 by boiling.
24 Key Words: Milk analysis; OP residues; Solid phase microextraction; Gas chromatogra-
25 phy.
26 INTRODUCTION
27 The external application of organophosphorus (OP) pesticides as insecticides
28 directly on dairy cattle for ectoparasite control within dairy farms may add to
1
TFJD448-05-163454 703.cls March 13, 2006 21:10
99 Instrumentation
100 The gas chromatographic analyses were performed on a 3800 Varian gas
101 chromatograph (Walnut Creek, CA, USA) equipped with a HP-5 capillary col-
102 umn (30 m × 0.32 mm × 0.25 µm film thickness, Hewlett Packard Company,
103 Avondale, PA, USA). The split/splitless injector was used in splitless mode at
104 240◦ C for 5 min. The oven temperature was programmed from 150◦ C held for
105 4 min, 20◦ C min−1 up to 280◦ C held for 30 min. A nitrogen-phosphorus (NPD)
106 detector was used with temperature set at 290◦ C. The gas carrier used was
107 helium at a flow rate of 0.8 mL min−1 .
Precision, linearity, detection, and quantification limits were studied under 127
optimal extraction and desorption conditions. Retention times in the chro- 128
matogram of whole milk (Fig. 1A) identified the dichlorvos at 3.97 min and the 129
coumaphos at 13.85 min. The values of relative standard deviation (%RSD), 130
also known as variation coefficient, were 14% RSD for dichlorvos and 13% 131
RSD for coumaphos, indicating that this method has good precision. Regres- 132
sion equations and correlation coefficients calculated were: Y = 2.77 + 196.05 X 133
and R2 = 0.996 for dichlorvos and Y = 82.87 + 9729.15 X and R2 = 0.999 for 134
coumaphos. The values of correlation coefficients show that the equations have 135
Q4