Abstract
An efficient and selective automated analytical method for the determination and quantification of a selected group of 12 organochlorine and organophosphorous pesticides in milk-based infant formulas has been developed. The samples were extracted by pressurized liquid extraction (PLE) and analysed using GC-MS/MS. The use of alumina as the fat retainer in the PLE extraction cell, together with the application of an injector temperature program during the GC injection process, avoided typical matrix interferences without the application of additional cleanup steps. Mean recoveries of between 70 and 110% were achieved for most of the compounds, except for chlorpyrifos methyl (50%), vinclozoline (48%), fenitrothion (56%) and procymidone (53%), with relative standard deviations ranging from 9 to 17%. Low limits of quantification were obtained for the studied compounds, from 0.01 to 2.6 μg kg−1, thus guaranteeing their accurate determination within the rigorous requirements established for baby food. The validated method was applied to a pilot monitoring study in Spain. Twenty five samples of different brands of powdered infant formulas were obtained from supermarkets. Positive findings of endosulfan I, endosulfan II, fenitrothion, chlorpyrifos ethyl and bifenthrin were detected at concentrations ranging from 0.03 to 5.03 μg kg−1.
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Commission directive 2003/13/EC of 10 February 2003 amending Directive 96/5/EC on processed cereal-based foods and baby foods for infants and young children
Yess NJ, Houston MG, Gunderson EL (1991) Food and Drug Administration pesticide-residue monitoring of foods - 1978–1982. J Assoc of Anal Chem 74:265–272
Kituyi EN, Wandiga SO, Jumba IO (1997) Occurrence of chlorfenvinphos residues in cow’s milk sampled at a range of sites in western Kenya. Bull Environ Cont Toxicol 58:969–975
Röbrig L, Meish HU (2000) Application of solid phase microextraction for the rapid analysis of chlorinated organics in breast milk. Fresenius J Anal Chem 366:106–111
Covaci A, Hura C, Shepens P (2001) Determination of selected persistent organochlorine pollutants in human milk using solid phase disk extraction and narrow bore capillary GC-MS. Chromatographia 54:247–252
Martínez MP, Angulo R, Pozo R, Jodral M (1997) Organochlorine pesticides in pasteurized milk and associated health risks. Food Chem Toxicol 35:621–624
Yague C, Bayarri S, Lazaro R, Conchello P, Arino A, Herrera A (2001) Multiresidue determination of organochlorine pesticides and polychlorinated biphenyls in milk by gas chromatography with electron-capture detection after extraction by matrix solid-phase dispersion. JAOAC Int 84:1561–1568
Pagliuca G, Serraino A, Gazzotti T, Zironi E, Borsari A, Rosmini R (2006) Organophosphorus pesticides residues in Italian raw milk. J Dairy Res 73:340–344
Cardeal de Lourdes Z, Dias CD (2006) Analysis of organophosphorus pesticides in whole milk by solid phase microextraction method. J Environ Sci Health 41:369–375
Picó Y, Viana E, Font G, Mañes J (1995) Determination of organochlorine pesticide content in human-milk and infant formulas using solid-phase extraction and capillary gas-chromatography. J Agricult Food Chem 43:1610–1615
Barkatina EN, Murokh VI, Kolomietz ND, Pertsovskii AL, Shulyakovskaya OV (1998) Determination of residual chlorinated organic pesticides in foodstuff by gas chromatography. J Anal Chem 53:861–864
Izquierdo P, Allara M, Torres G, García A, Pinero M (2004) Organochlorine pesticide residues in infant formulas. Revista científica-Facultad Ciencias Veterinarias 14:147–152
Cressey PJ, Vannort RW (2003) Pesticide content of infant formulae and weaning foods available in New Zealand. Food Add Contam 20:57–64
Campoy C, Jiménez M, Olea-Serrano MF, Moreno Frías M, Cañabate F, Olea N, Bayés R, Molina Font JA (2001) Analysis of organochlorine pesticides in human milk: preliminary results. Early Hum Dev 65:S183–S190
Focant JF, Sjodin A, Turner WE, Patterson DG Jr (2004) Measurement of selected polybrominated diphenyl ethers, polybrominated and polychlorinated biphenyls, and organochlorine pesticides in human serum and milk using comprehensive two-dimensional gas chromatography isotope dilution time-of-flight mass spectrometry. Anal Chem 76:6313–6320
Di Muccio A, Pelos P, Camoni I, Barbini DA, Dommarco R, Genrah T, Ausili A (1996) Selective, solid-matrix dispersion extraction of organophosphate pesticide residues from milk. J Chromatogr A 754:497–507
Di Muccio A, Pelosi P, Barbini DA, Generali T, Ausili A, Fergori F (1997) Selective extraction of pyrethroid pesticide residues from milk by solid-matrix dispersion. J Chromatogr A 765:51–60
Zhu L, Fe KH, Zhao L, Lee HK (2002) Analysis of phenoxy herbicides in bovine milk by means of liquid-liquid-liquid microextraction with a hollow-fiber membrane. J Chromatogr A 963:335–343
Lake IR, Foxall CD, Lovett AA, Fernandes A, Dowding A, White S, Rose M (2005) Effects of river flooding on PCDD/F and PCB levels in cow’s milk, soil, and grass. Environ Sci Technol 39:9033–9038
Bennett DA, Chung AC, Lee SM (1997) Multiresidue method for analysis of pesticides in liquid whole milk. J AOAC Int 80:1065–1077
González-Rodríguez MJ, Arrebola Liébanas FJ, Garrido Frénich A, Martínez Vidal JL, Sánchez López FJ (2005) Anal Bioanal Chem 382:164–172
Grob KJr (1984) Effect of dirt injected on-column in capillary gas-chromatography - analysis of the sterol fraction of oils as an example. J Chromatogr 287:1–14
Grob KJr, Bossard M (1984) Effect of dirt on quantitative-analyses by capillary gas-chromatography with splitless injection. J Chromatogr 294:65–75
Ferrer C, Ramos MJ, García-Reyes JF, Ferrer I, Thurman EM, Fernández-Alba AR (2005) Determination of pesticide residues in olives and olive oil by matrix solid-phase dispersion followed by gas chromatography/mass spectrometry and liquid chromatography/tandem mass spectrometry. J Chromatogr A 1069:183–194
García-Reyes JF, Ferrer C, Ramos MJ, Fernández-Alba AR, Molina-Díaz A (2007) Determination of pesticide residues in olive oil and olives. Trends Anal Chem 26:239–251
Hsu JF, Leon Guo Y, Liu CH, Hu SC, Wang JN, Liao PC (2007) A comparison of PCDD/PCDFs exposure in infants via formula milk or breast milk feeding. Chemosphere 66:311–319
Loran S, Bayarri S, Concello P, Herrera A (2007) Evaluation of GC-ion trap-MS/MS methodology for monitoring PCDD/Fs in infant formulas. Chemosphere 67:513–520
Ramos L, Torre M, Laborda F, Marina ML (1998) Determination of polychlorinated biphenyls in soybean infant formulas by gas chromatography. J Chromatogr A 823:365–372
Hercegova A, Domotorova M, Matisova E (2007) Sample preparation methods in the analysis of pesticides in baby food with subsequent chromatographic determination. J of Chromatogr A 1153:54
Björklund E, Sporring S, Wiberg K, Haglund P, Von Holst C (2006) New strategies for extraction and clean-up of persistent organic pollutants from food and feed samples using selective pressurized liquid extraction. Trends Anal Chem 25:318–325
Sporring S, Björklund E (2004) Selective pressurized liquid extraction from fat-containing food and feed samples. Influence of cell dimensions, solvent type, temperature and flush volume. J Chromatogr A 1040:155–161
Björklund E, Müller A, Von Holst C (2001) Comparison of fat retainers in accelerated solvent extraction for the selective extraction of PCBs from fat-containing samples. Anal Chem 73:4050–4053
Stan HJ, Linkerhägner M (1996) Large-volume injection in residue analysis with capillary gas chromatography using a conventional autosampler and injection by programmed-temperature vaporization with solvent venting. J Chromatogr A 727:275–289
Korenková E, Matisová E, Slobodnik J (2003) Study on the feasibility of coupling large-volume injection to fast gas chromatography with mass spectrometric detection for analysis of organochlorine pesticides. J Sep Sci 26:1193–1197
Acknowledgements
This work has been supported by the European Commission (Alfa project No: AML/B7-311/97/0666/II-0461-FA-FCD-FI). M. Mezcua acknowledges the “Juan de la Cierva” research contract from Spanish Ministry of Science and Technology.
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Mezcua, M., Repetti, M.R., Agüera, A. et al. Determination of pesticides in milk-based infant formulas by pressurized liquid extraction followed by gas chromatography tandem mass spectrometry. Anal Bioanal Chem 389, 1833–1840 (2007). https://doi.org/10.1007/s00216-007-1501-y
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DOI: https://doi.org/10.1007/s00216-007-1501-y