Skip to main content
Log in

Matrix Effects in Detection of Phthalate Esters from Wheat by a Modified QuEChERS Method with GC/MS

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

Nowadays, there is a lack of information regarding the occurrence and the content of phthalate esters (PAEs) contamination in wheats. In this study, a QuEChERS-GC/MS method was validated to measure trace levels of 14 PAEs in wheats. The work also focused on the matrix effects (MEs) which were evaluated through the study of slope ratios obtained of solvent and wheat matrix curves. All of the PAEs had positive MEs, and the percentage values were in a range of 5.4% (diisobutyl phthalate) to 53.7% (di-n-hexyl phthalate). The average recoveries (spiked at 0.06, 0.20, and 0.60 mg kg−1) had been considered satisfactory values between 84.8 and 120.3% with relative standard deviations of 0.6–9.0% for intra-day precision and 1.0–8.6% for inter-day precision. The limits of detection and limits of quantification ranged from 0.1 to 2.5 μg kg−1 and 0.13 to 5.0 μg kg−1, respectively. Following the employment of a top-down empirical model, the relative expanded measurement uncertainties were in the range of 21–43% (coverage factor k = 2, at 95% confidence). Based on the established method, PAEs in seven commercial wheat were evaluated, where 5 out of 14 studied PAEs were revealed in all of wheats, ranging from 0.028 to 0.669 mg kg−1. One of them exceeded the upper limits 0.3 mg kg−1 set for dibutyl phthalate in China.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. J AOAC Int 86:412–431

    CAS  Google Scholar 

  • Aranda JM, O'Connor GA, Eiceman GA (1989) Effects of sewage sludge on di-(2-ethylhexyl) phthalate uptake by plants. J Environ Qual 18:45–50. doi:10.2134/jeq1989.00472425001800010008x

    Article  CAS  Google Scholar 

  • Arroyo-Manzanares N, Huertas-Pérez JF, García-Campaña AM, Gámiz-Gracia L (2014) Simple methodology for the determination of mycotoxins in pseudocereals, spelt and rice. Food Control 36:94–101 doi:http://dx.Doi.Org/10.1016/j.Foodcont.2013.07.028

  • Bang DY, Lee IK, Lee B-M (2011) Toxicological characterization of phthalic acid. Toxicol Res (Seoul, Repub. Korea) 27:191–203 doi:10.5487/TR.2011.27.4.191

  • Chai C, Cheng H, Ge W, Ma D, Shi Y (2014) Phthalic acid esters in soils from vegetable greenhouses in Shandong Peninsula, East China. PLoS One 9:e95701. doi:10.1371/journal.pone.0095701

    Article  Google Scholar 

  • Chang L, Bi P, Li X, Wei Y (2015) Study of solvent sublation for concentration of trace phthalate esters in plastic beverage packaging and analysis by gas chromatography-mass spectrometry. Food Chem 177:127–133. doi:10.1016/j.foodchem.2015.01.013

    Article  CAS  Google Scholar 

  • Chatterjee NS, Utture S, Banerjee K, Ahammed Shabeer TP, Kamble N, Mathew S, Ashok Kumar K (2016) Multiresidue analysis of multiclass pesticides and polyaromatic hydrocarbons in fatty fish by gas chromatography tandem mass spectrometry and evaluation of matrix effect. Food Chem 196:1-8 doi:http://dx.Doi.Org/10.1016/j.Foodchem.2015.09.014

  • Chen G, Hu H, Wu T, Tong P, Liu B, Zhu B, Du Y (2014) Rapid and sensitive determination of plasticizer diethylhexyl phthalate in drink by diffuse reflectance UV spectroscopy coupled with membrane filtration. Food Control 35:218-222 doi:http://dx.Doi.Org/10.1016/j.Foodcont.2013.07.009

  • Cousins I, Mackay D (2000) Correlating the physical–chemical properties of phthalate esters using the ‘three solubility’ approach. Chemosphere 41:1389-1399 doi:http://dx.Doi.Org/10.1016/S0045-6535(00)00005-9

  • Eurachem (2000) CITAC, quantifying uncertainty in analytical measurement, guide CG4 (3nd ed.). Research Gate

  • Fankhauser-Noti A, Grob K (2007) Blank problems in trace analysis of diethylhexyl and dibutyl phthalate: investigation of the sources, tips and tricks. Anal Chim Acta 582:353–360. doi:10.1016/j.aca.2006.09.012

    Article  CAS  Google Scholar 

  • Fasano E, Bono-Blay F, Cirillo T, Montuori P, Lacorte S (2012) Migration of phthalates, alkylphenols, bisphenol A and di(2-ethylhexyl)adipate from food packaging. Food Control 27:132–138. doi:10.1016/j.foodcont.2012.03.005

    Article  CAS  Google Scholar 

  • Fasano E, Cirillo T, Esposito F, Lacorte S (2015) Migration of monomers and plasticizers from packed foods and heated microwave foods using QuEChERS sample preparation and gas chromatography/mass spectrometry. LWT Food Sci Technol 64:1015–1021. doi:10.1016/j.lwt.2015.06.066

    Article  CAS  Google Scholar 

  • Ferreira I, Fernandes JO, Cunha SC (2012) Optimization and validation of a method based in a QuEChERS procedure and gas chromatography–mass spectrometry for the determination of multi-mycotoxins in popcorn. Food Control 27:188–193. doi:10.1016/j.foodcont.2012.03.014

    Article  CAS  Google Scholar 

  • González-Curbelo MÁ, Hernández-Borges J, Borges-Miquel TM, Rodríguez-Delgado MÁ (2012) Determination of pesticides and their metabolites in processed cereal samples. Food Addit Contam , Part A 29:104–116. doi:10.1080/19440049.2011.615032

    Article  Google Scholar 

  • Grande-Martínez Á, Arrebola-Liébanas FJ, Martínez-Vidal JL, Hernández-Torres ME, Garrido-Frenich A (2016) Optimization and validation of a multiresidue pesticide method in rice and wheat flour by modified QuEChERS and GC–MS/MS. Food Anal Methods 9:548–563. doi:10.1007/s12161-015-0214-7

    Article  Google Scholar 

  • Guedes JAC, RdO S, Lima CG, MAL M, do Nascimento RF (2016) Matrix effect in guava multiresidue analysis by QuEChERS method and gas chromatography coupled to quadrupole mass spectrometry. Food Chem 199:380–386. doi:10.1016/j.foodchem.2015.12.007

    Article  CAS  Google Scholar 

  • Guo Y, Kannan K (2012) Challenges encountered in the analysis of phthalate esters in foodstuffs and other biological matrices. Anal Bioanal Chem 404:2539–2554. doi:10.1007/s00216-012-5999-2

    Article  CAS  Google Scholar 

  • Herrmann SS, Poulsen ME (2015) Clean-up of cereal extracts for gas chromatography–tandem quadrupole mass spectrometry pesticide residues analysis using primary secondary amine and C18. J Chromatogr A 1423:47–53. doi:10.1016/j.chroma.2015.10.086

    Article  CAS  Google Scholar 

  • Huang G, Sun J, Chen Z, Chen XI, Jing J, Liu J, Zhang Y (2012) Levels and sources of phthalate esters in shallow groundwater and surface water of Dongguan city, South China. Geochem J 46:421–428. doi:10.2343/geochemj.1.0172

    Article  CAS  Google Scholar 

  • Keith L, Telliard W (1979) ES&T Special Report: priority pollutants: I—a perspective view. Environ Sci Technol 13:416–423. doi:10.1021/es60152a601

    Article  Google Scholar 

  • Kolberg DI, Prestes OD, Adaime MB, Zanella R (2011) Development of a fast multiresidue method for the determination of pesticides in dry samples (wheat grains, flour and bran) using QuEChERS based method and GC–MS. Food Chem 125:1436–1442. doi:10.1016/j.foodchem.2010.10.041

    Article  CAS  Google Scholar 

  • Langseth W (1998) Mycotoxin production and cytotoxicity of Fusarium strains isolated from Norwegian cereals. Mycopathologia 144:103–113. doi:10.1023/A:1007016820879

    Article  Google Scholar 

  • Leng G, Chen W, Zhang M, Huang F, Cao Q (2014) Determination of phthalate esters in liquor samples by vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction followed by GC-MS. J Sep Sci 37:684–690. doi:10.1002/jssc.201301033

    Article  CAS  Google Scholar 

  • Lu Y, Cheng Z, Liu C, Cao X (2016) Determination of sulfonamides in fish using a modified QuEChERS extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry. Food Anal Methods 9:1857–1866. doi:10.1007/s12161-016-0477-7

    Article  Google Scholar 

  • Ma TT, Wu LH, Chen L, Zhang HB, Teng Y, Luo YM (2015) Phthalate esters contamination in soils and vegetables of plastic film greenhouses of suburb Nanjing, China and the potential human health risk. Environ Sci Pollut Res 22:12018–12028. doi:10.1007/s11356-015-4401-2

    Article  CAS  Google Scholar 

  • Mastovska K, Dorweiler KJ, Lehotay SJ, Wegscheid JS, Szpylka KA (2010) Pesticide multiresidue analysis in cereal grains using modified QuEChERS method combined with automated direct sample introduction GC-TOFMS and UPLC-MS/MS techniques. J Agric Food Chem 58:5959–5972. doi:10.1021/jf9029892

    Article  CAS  Google Scholar 

  • Pei XQ, Song M, Guo M, Mo FF, Shen XY (2013) Concentration and risk assessment of phthalates present in indoor air from newly decorated apartments. Atmos Environ 68:17–23. doi:10.1016/j.atmosenv.2012.11.039

    Article  CAS  Google Scholar 

  • Russo MV, Notardonato I, Cinelli G, Avino P (2012) Evaluation of an analytical method for determining phthalate esters in wine samples by solid-phase extraction and gas chromatography coupled with ion-trap mass spectrometer detector. Anal Bioanal Chem 402:1373–1381. doi:10.1007/s00216-011-5551-9

    Article  CAS  Google Scholar 

  • Salvia MV, Cren-Olivé C, Vulliet E (2013) Statistical evaluation of the influence of soil properties on recoveries and matrix effects during the analysis of pharmaceutical compounds and steroids by quick, easy, cheap, effective, rugged and safe extraction followed by liquid chromatography–tandem mass spectrometry. J Chromatogr A 1315:53–60. doi:10.1016/j.chroma.2013.09.056

    Article  CAS  Google Scholar 

  • Sebők Á, Vasanits-Zsigrai A, Helenkár A, Záray G, Molnár-Perl I (2009) Multiresidue analysis of pollutants as their trimethylsilyl derivatives, by gas chromatography–mass spectrometry. J Chromatogr A 1216:2288–2301. doi:10.1016/j.chroma.2009.01.056

    Article  Google Scholar 

  • Shi LK, Zhang MM, Liu YL (2016) Concentration and survey of phthalic acid esters in edible vegetable oils and oilseeds by gas chromatography-mass spectrometry in China. Food Control 68:118–123. doi:10.1016/j.foodcont.2016.03.027

    Article  CAS  Google Scholar 

  • Słowik-Borowiec M (2014) Validation of a QuEChERS-based gas chromatographic method for multiresidue pesticide analysis in fresh peppermint including studies of matrix effects. Food Anal Methods 8:1413–1424. doi:10.1007/s12161-014-0027-0

    Article  Google Scholar 

  • Walorczyk S (2014) Validation and use of a QuEChERS-based gas chromatographic–tandem mass spectrometric method for multiresidue pesticide analysis in blackcurrants including studies of matrix effects and estimation of measurement uncertainty. Talanta 120:106–113. doi:10.1016/j.talanta.2013.11.087

    Article  CAS  Google Scholar 

  • Xian Y, Dong H, Wu Y, Guo X, Hou X, Wang B (2016) QuEChERS-based purification method coupled to ultrahigh performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) to determine six quaternary ammonium compounds (QACs) in dairy products. Food Chem 212:96–103. doi:10.1016/j.foodchem.2016.05.151

    Article  CAS  Google Scholar 

  • Xie Q, Liu S, Fan Y, Zhang X (2013) Development of a dispersive liquid–liquid microextraction method for the determination of α-tocopherol in pigmented wheat by high-performance liquid chromatography. Food Anal Methods 7:21–30. doi:10.1007/s12161-013-9592-x

    Article  CAS  Google Scholar 

  • Xu D et al (2014) Determination of 23 phthalic acid esters in food by liquid chromatography tandem mass spectrometry. J Chromatogr A 1324:49–56. doi:10.1016/j.chroma.2013.11.017

    Article  CAS  Google Scholar 

  • Xu X, Zhang X, Duhoranimana E, Zhang Y, Shu P (2016) Determination of methenamine residues in edible animal tissues by HPLC-MS/MS using a modified QuEChERS method: validation and pilot survey in actual samples. Food Control 61:99–104. doi:10.1016/j.foodcont.2015.09.030

    Article  CAS  Google Scholar 

  • Ye Q, Liu L, Chen Z, Hong I (2014) Analysis of phthalate acid esters in environmental water by magnetic graphene solid phase extraction coupled with gas chromatography–mass spectrometry. J Chromatogr A 1329:24–29 doi: 10.1016/j.chroma.2013.12.086

  • Yin P, Liu X, Chen H, Pan R, Ma G (2014) Determination of 16 phthalate esters in tea samples using a modified QuEChERS sample preparation method combined with GC-MS/MS. Food Addit Contam, Part A 31:1406–1413. doi:10.1080/19440049.2014.933490

    Article  CAS  Google Scholar 

  • Yudthavorasit S, Meecharoen W, Leepipatpiboon N (2015) New practical approach for using an analyte protectant for priming in routine gas chromatographic analysis. Food Control 48:25–32. doi:10.1016/j.foodcont.2014.05.005

    Article  CAS  Google Scholar 

  • Zainudin BH, Salleh S, Mohamed R, Yap KC, Muhamad H (2015) Development, validation and determination of multiclass pesticide residues in cocoa beans using gas chromatography and liquid chromatography tandem mass spectrometry. Food Chem 172:585–595. doi:10.1016/j.foodchem.2014.09.123

    Article  CAS  Google Scholar 

  • Zhao P, Huang B, Gu K, Zou N, Pan C (2015) Analysis of triallate residue and degradation rate in wheat and soil by liquid chromatography coupled to tandem mass spectroscopy detection with multi-walled carbon nanotubes. Int J Environ Anal Chem 95:1413–1423. doi:10.1080/03067319.2015.1114103

    Article  CAS  Google Scholar 

  • Zhou J, Qi Y, Wu H, Diao Q, Tian F, Li Y (2014) Simultaneous determination of trace migration of phthalate esters in honey and royal jelly by GC–MS. J Sep Sci 37:650–657. doi:10.1002/jssc.201300778

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors gratefully acknowledge the financial support received from the National Natural Science Foundation of China (grant number 31601556 and 31301466) and the Natural Science Foundation Program of Beijing and the Scientific Research Key Program of Beijing Municipal Commission of Education (grant number KZ201410011015).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Xiaotao Sun.

Ethics declarations

Conflict of Interest

Wei Dong declares that she has no conflict of interest. Baoguo Sun declares that he has no conflict of interest. Jinyuan Sun declares that she has no conflict of interest. Fuping Zheng declares that he has no conflict of interest. Xiaotao Sun declares that he has no conflict of interest. Mingquan Huang declares that he has no conflict of interest. Hehe Li declares that she has no conflict of interest.

Ethical Approval

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

Informed Consent

Informed consent was obtained from all individual participants included in the study.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Dong, W., Sun, B., Sun, J. et al. Matrix Effects in Detection of Phthalate Esters from Wheat by a Modified QuEChERS Method with GC/MS. Food Anal. Methods 10, 3166–3180 (2017). https://doi.org/10.1007/s12161-017-0892-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-017-0892-4

Keywords

Navigation