Food Analytical Methods

, Volume 12, Issue 1, pp 41–50 | Cite as

Analytical Method Validation for Determining Organophosphorus Pesticides in Baby Foods by a Modified Liquid–Liquid Microextraction Method and Gas Chromatography–Ion Trap/Mass Spectrometry Analysis

  • Ivan Notardonato
  • Mario Vincenzo Russo
  • Matteo Vitali
  • Carmela Protano
  • Pasquale Avino


Baby food is made specifically for babies between the ages of 4/6 months up to 2 years, and it comes in multiple varieties and tastes. This paper proposes a protocol for a rapid and reliable determination of 19 organophosphorus pesticides (OPs) by means of a method based on ultrasound-vortex-assisted liquid–liquid microextraction coupled with a gas chromatography–ion trap mass spectrometry (UVALLME–GC-IT/MS). The method development starts from the extraction solvent evaluation, i.e., n-heptane; the solution, held for 5 min on the vortex mixer and for 6 min in an ultrasonic bath to 100 W for favoring the solvent dispersion and the determinant extraction, is centrifuged at 4000 rpm for 30 min: 1 μL of the organic extract is injected into the GC-IT/MS. All the analytical parameters investigated are deeply discussed; LODs/LOQs (0.2–1.3 and 0.5–2.9 ng/g) and recoveries (81–109%) are compared with other papers dealing the determination of OPs in baby food matrix. The whole method has been applied to real commercial freeze-dried and soft baby food samples: the results do not show any significant contaminant values.


LLME Vortex GC-IT/MS Organophosphorous pesticides Baby food 


Compliance with Ethical Standards

Conflict of Interest

Ivan Notardonato declares that he has no conflict of interest. Mario Vincenzo Russo declares that he has no conflict of interest. Matteo Vitali declares that he has no conflict of interest. Carmela Protano declares that he has no conflict of interest. Pasquale Avino declares that he has no conflict of interest.

Ethical Approval

This article does not contain any studies with human or animal subjects and so the ethical approval is not necessary and not required.

Informed Consent

Not applicable. This article does not contain any studies with human or animal subjects.


  1. Amendola G, Pelosi P, Barbini DA (2015) Determination of pesticide residues in animal origin baby foods by gas chromatography coupled with triple quadrupole mass spectrometry. J Environ Sci Health B 50:109–120CrossRefGoogle Scholar
  2. Anagnostopoulos CJ, Aplada Sarli P, Miliadis GE, Haroutounian CA (2010) Validation of the QuEChERS method for the determination of 25 priority pesticide residues in cereal-based baby foods by gas chromatography with electron capture and nitrogen phosphorous detection. Hell Plant Protect J 3:71–80Google Scholar
  3. Ault JA, Schofield CM, Johnson LD, Waltz RH (1979) Automated gel permeation chromatographic preparation of vegetables, fruits, and crops for organophosphate residue determination utilizing flame photometric detection. J Agric Food Chem 27:825–828CrossRefGoogle Scholar
  4. Authority of Ireland (2004) Report on surveillance of infant food for pesticide residues. Available online: (accessed on November 2017)
  5. Cartoni GP, Goretti G, Monticelli B, Russo MV (1986) Evaluation of capillary gas chromatographic columns in series: analytical application to lemon oil. J Chromatogr A 370:93–101CrossRefGoogle Scholar
  6. Cartoni GP, Castellani L, Goretti G, Russo MV, Zacchei P (1991) Gas–liquid microcapillary columns precoated with graphitized carbon black. J Chromatogr A 552:197–204CrossRefGoogle Scholar
  7. Cinelli G, Avino P, Notardonato I, Russo MV (2014a) Ultrasound-vortex-assisted dispersive liquid–liquid microextraction coupled with gas chromatography with a nitrogen–phosphorus detector for simultaneous and rapid determination of organophosphorus pesticides and triazines in wine. Anal Methods 6:782–790CrossRefGoogle Scholar
  8. Cinelli G, Avino P, Notardonato I, Centola A, Russo MV (2014b) Study of XAD-2 adsorbent for the enrichment of trace levels of phthalate esters in hydroalcoholic food beverages and analysis by gas chromatography coupled with flame ionization and ion-trap mass spectrometry detectors. Food Chem 146:181–187CrossRefGoogle Scholar
  9. Codex Alimentarius Commission (2009) Pesticide maximum residue limit (MRL) legislation around the world. Ministry of Primary Industries, New Zealand. Available online: (accessed on January 2018)
  10. Cojocariu C, Hetmanski MT, Silcock P, Fussell RJ (2015) Three-fold increase in productivity for pesticide residue analysis in baby food using fast triple quadrupole GC-MS/MS. application note 10432, Thermo Scientific. Available online: (accessed on November 2017)
  11. D’Souza PE (2011) Concentrations of pesticide residues in baby foods: understanding a common pathway of exposure for infants. Master’s thesis, Emory University, 22 April 2011. Available online (accessed on 10 October 2017)
  12. Erney DR (1995) Determination of organophosphorus pesticides in whole/chocolate/skim-milk and infant formula using solid-phase extraction with capillary gas chromatography/flame photometric detection. J Sep Sci 18:59–62Google Scholar
  13. Eskenazi B, Rosas LG, Marks AR, Bradman A, Harley K, Holland N, Johnson C, Fenster L, Barr DB (2007) Pesticide toxicity and the developing brain. Basic Clin Pharmacol Toxicol 102:228–236CrossRefGoogle Scholar
  14. European Commission (2005) Commission Regulation (EU) No 396/2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EC, 16/03/2005Google Scholar
  15. European Commission (2013) Method validation and quality control procedures for pesticide residues analysis in food and feed. SANCO/12571/2013. 2013, pp. 42. Available online (accessed on June 2017)
  16. Fenske RA, Kedan G, Lu C, Fisker-Andersen JA, Curl CL (2002) Assessment of organophosphorous pesticide exposures in the diets of preschool children in Washington state. J Expo Anal Environ Epidemiol 22:21–28CrossRefGoogle Scholar
  17. Gelardi RC, Mountford MK (1993) Infant formulas: evidence of the absence of pesticide residues. Regul Toxicol Pharmacol 17:181–192CrossRefGoogle Scholar
  18. Georgakopoulos P, Mylona A, Athanasopoulos P, Drosinos EH, Skandamis PN (2009) Evaluation of cost-effective methods in the pesticide residue analysis of non-fatty baby foods. Food Chem 115:1164–1169CrossRefGoogle Scholar
  19. Georgakopoulos P, Zachari R, Mataragas M, Athanasopoulos P, Drosinos EH, Skandamis PN (2011) Optimisation of octadecyl (C18) sorbent amount in QuEChERS analytical method for the accurate organophosphorus pesticide residues determination in low-fatty baby foods with response surface methodology. Food Chem 128:536–542CrossRefGoogle Scholar
  20. González-Curbelo MÁ, Hernández-Borges J, Borges-Miquel TM, Rodríguez-Delgado MÁ (2013) Determination of organophosphorus pesticides and metabolites in cereal-based baby foods and wheat flour by means of ultrasound-assisted extraction and hollow-fiber liquid-phase microextraction prior to gas chromatography with nitrogen phosphorus detection. J Chromatogr A 1313:166–174CrossRefGoogle Scholar
  21. Hercegová A, Dömötörová M, Matisová E, Kirchnera M, Otrekala R, Stefuca V (2005) Fast gas chromatography with solid phase extraction clean-up for ultratrace analysis of pesticide residues in baby food. J Chromatogr A 1084:46–53CrossRefGoogle Scholar
  22. Hercegová A, Dömötörová M, Kruzlicová D, Matisová E (2006) Comparison of sample preparation methods combined with fast gas chromatography-mass spectrometry for ultratrace analysis of pesticide residues in baby food. J Sep Sci 29:1102–1109CrossRefGoogle Scholar
  23. Knoll JE (1985) Estimation of the limit of detection in chromatography. J Chromatogr Sci 23:422–425CrossRefGoogle Scholar
  24. Meeker JD (2012) Exposure to environmental endocrine disruptors and child development. Arch Pediatr Adolesc Med 166:E1–E7CrossRefGoogle Scholar
  25. Melgar MJ, Santaeufemia M, García MA (2010) Organophosphorus pesticide residues in raw milk and infant formulas from Spanish northwest. J Env Sci Health B 45:595–600CrossRefGoogle Scholar
  26. Mezcua M, Repetti MR, Agüera A, Ferrer C, García-Reyes JF, Fernández-Alba AR (2007) Determination of pesticides in milk-based infant formulas by pressurized liquid extraction followed by gas chromatography tandem mass spectrometry. Anal Bioanal Chem 389:1833–1840CrossRefGoogle Scholar
  27. Mirabelli MF, Wolf J-C, Zenobi R (2016) Pesticide analysis at ppt concentration levels: coupling nano-liquid chromatography with dielectric barrier discharge ionization-mass spectrometry. Anal Bioanal Chem 408:3425–3434CrossRefGoogle Scholar
  28. Mukherjee I, Gopal M (1996) Insecticide residues in baby food, animal feed, and vegetables by gas liquid chromatography. Bull Environ Contam Toxicol 56:381–388CrossRefGoogle Scholar
  29. National Research Council (1993) Committee on Pesticides in the Diets of Infants and Children. Pesticides in the diets of infants and children. ISBN: 0-309-58535-X. Available online: (accessed on January 2018)
  30. Pérez-Ortega P, Lara-Ortega FJ, Gilbert-López B, Moreno-González D, García-Reyes JF, Molina-Díaz A (2017) Screening of over 600 pesticides, veterinary drugs, food-packaging contaminants, mycotoxins, and other chemicals in food by ultra-high performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC-QTOFMS). Food Anal Methods 10:1216–1244CrossRefGoogle Scholar
  31. Petrarca MH, Fernandes JO, Godoy HT, Cunha SC (2016) Multiclass pesticide analysis in fruit-based baby food: a comparative study of sample preparation techniques previous to gas chromatography-mass spectrometry. Food Chem 212:528–536CrossRefGoogle Scholar
  32. Russo MV, Goretti G, Soriero A (1996) Preparation and application of fused-silica capillary microcolumns (25–50 μm ID) in gas chromatography. Ann Chim 86:115–124Google Scholar
  33. Russo MV, Campanella L, Avino P (2002) Determination of organophosphorus pesticide residues in human tissues by capillary gas chromatography-negative chemical ionization mass spectrometry analysis. J Chromatogr B 780:431–441CrossRefGoogle Scholar
  34. Russo MV, Avino P, Cinelli G, Notardonato I (2012) Sampling of organophosphorus pesticides at trace levels in the atmosphere using XAD-2 adsorbent and analysis by gas chromatography coupled with nitrogen-phosphorus and ion-trap mass spectrometry detectors. Anal Bioanal Chem 404:1517–1527CrossRefGoogle Scholar
  35. Russo MV, Avino P, Centola A, Notardonato I, Cinelli G (2014a) Rapid and simple determination of acrylamide in conventional cereal-based foods and potato chips through conversion to 3-[bis(trifluoroethanoyl)amino]-3-oxopropyl trifluoroacetate by gas chromatography coupled with electron capture and ion trap mass spectrometry detectors. Food Chem 146:204–211CrossRefGoogle Scholar
  36. Russo MV, Notardonato I, Avino P, Cinelli G (2014b) Fast determination of phthalate ester residues in soft drinks and light alcoholic beverages by ultrasound/vortex assisted dispersive liquid–liquid microextraction followed by gas chromatography–ion trap mass spectrometry. RSC Adv 4:59655–59663CrossRefGoogle Scholar
  37. Russo MV, Notardonato I, Avino P, Cinelli G (2014c) Determination of phthalate esters at trace levels in light alcoholic drinks and soft drinks by XAD-2 adsorbent and gas chromatography coupled with ion trap-mass spectrometry detection. Anal Methods 6:7030–7037CrossRefGoogle Scholar
  38. Russo MV, Avino P, Perugini L, Notardonato I (2015) Extraction and GC-MS analysis of phthalate esters in food matrices: a review. RSC Adv 5:37023–37043CrossRefGoogle Scholar
  39. Russo MV, Avino P, Notardonato I (2016) Fast analysis of phthalates in freeze-dried baby foods by ultrasound-vortex-assisted liquid–liquid microextraction coupled with gas chromatography–ion trap/mass spectrometry. J Chromatogr A 1474:1–7CrossRefGoogle Scholar
  40. Shimadzu (2013) Analysis of organophosphorus pesticides in baby foods using a triple-quadrupole GC/MS/MS system. Appl. Note No. GCMS-1304. Available online: (accessed on 10 December 2017)
  41. Vukovic G, Shtereva D, Bursic V, Mladenova R, Lazic R (2012) Application of GC-MSD and LC-MS/MS for the determination of priority pesticides in baby foods in Serbian market. LWT- Food Sci Technol. 49:312–319CrossRefGoogle Scholar
  42. Yang A, El-Atya AMA, Park J-H, Goudah A, Rahman MM, Do J-A, Choi O-J, Shim J-H (2014) Analysis of 10 systemic pesticide residues in various baby foods using liquid chromatography-tandem mass spectrometry. Biomed Chromatogr 28:735–741CrossRefGoogle Scholar
  43. Yiantzi E, Psillakis E, Tyrovola K, Kalogerakis N (2010) Vortex-assisted liquid–liquid microextraction of octylphenol, nonylphenol and bisphenol-a. Talanta 80:2057–2062CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Agriculture, Environment and FoodUniversity of MoliseCampobassoItaly
  2. 2.Department of Public Health and Infectious DiseasesSapienza University of RomeRomeItaly

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