Validation of a QuEChERS-Based Gas Chromatography-Mass Spectrometry (GC-MS) Method for Analysis of Phthalate Esters in Grain Sorghum.

A modified QuEChERS method coupled with gas chromatography-mass spectrometry (GC-MS) was developed for analysis of 14 phthalate esters (PAEs) in grain sorghum (GS). Chemical extraction was done with acetonitrile followed by dispersive-solid phase extraction technique with a mixture of sorbents including primary secondary amine and octadecyl silica. Under the optimized condition, the matrix-matched calibration curves for all PAEs showed good linear relationship in the concentration range between 5 and 500 μg/L with correlation coefficients (R2 ) better than 0.99. Mean recoveries were between 82.0% and 120.2% at spiking levels of 0.06, 0.6, and 2.0 mg/kg with RSD of 0.3% to 7.8% (n = 5) for intra-day precision and 1.2% to 7.6% (n = 5) for inter-day precision. The LODGS and LOQGS for 14 PAEs were between 0.4 and 10.0 μg/kg and 0.5 and 20.0 μg/kg, respectively. Analysis of 32 commercial GS samples revealed that dimethyl-, diethyl-, diisobutyl-, dibutyl-, and di- (2-ethylhexyl) phthalate esters were detected in all of the analytes. In addition, content-color scale model was applied to visualize the concentration differences of PAEs in real GS samples. Principal component analysis of PAEs revealed that the GS samples did not have a distinctive cluster based on their geographic origins. The established method was proven to be simple, accurate, and effective for analysis of PAEs in GS, which might also be applied for analysis of PAEs in other matrices. PRACTICAL APPLICATION A modified QuEChERS-based GC-MS method was developed for the determination of phthalate esters (PAEs) in grain sorghum (GS). The ubiquitous presence of PAEs can migrate into GS. Therefore, evaluation of the total content of PAEs in GS is helpful to understand its impact of overall pollution level on other foods. This study has provided some basic information in terms of the content and contamination of PAEs in GS, which is helpful to establish relevant standards and risk assessment of GS for the government.

[1]  C. Raynaud,et al.  Matrix-Matching as an Improvement Strategy for the Detection of Pesticide Residues. , 2016, Journal of food science.

[2]  V. Queiroz,et al.  Resistant starch content among several sorghum (Sorghum bicolor) genotypes and the effect of heat treatment on resistant starch retention in two genotypes. , 2016, Food chemistry.

[3]  Karl J. Jobst,et al.  A modified QuEChERS approach for the screening of dioxins and furans in sediments , 2016, Analytical and Bioanalytical Chemistry.

[4]  Kaushik Banerjee,et al.  Multiresidue analysis of multiclass pesticides and polyaromatic hydrocarbons in fatty fish by gas chromatography tandem mass spectrometry and evaluation of matrix effect. , 2016, Food chemistry.

[5]  Li Xun,et al.  A modified QuEChERS method coupled with high resolution LC-Q-TOF-mass spectrometry for the extraction, identification and quantification of isoflavones in soybeans , 2016 .

[6]  Ángel Grande-Martínez,et al.  Optimization and Validation of a Multiresidue Pesticide Method in Rice and Wheat Flour by Modified QuEChERS and GC–MS/MS , 2016, Food Analytical Methods.

[7]  Shurui Cao,et al.  Cleaning Up Vegetable Samples Using a Modified “QuEChERS” Procedure for the Determination of 17 Plant Growth Regulator Residues by Ultra High Performance Liquid Chromatography–Triple Quadrupole Linear Ion Trap Mass Spectrometry , 2016, Food Analytical Methods.

[8]  Shanjun Song,et al.  Optimization of selective pressurized liquid extraction and ultrasonication-assisted QuEChERS methods for the determination of polybrominated diphenyl ethers in sediments , 2015 .

[9]  M. Soumanou,et al.  IMPROVEMENT OF AFRICAN TRADITIONAL SORGHUM BEERS QUALITY AND POTENTIAL APPLICATIONS OF PLANTS EXTRACTS FOR THEIR STABILIZATION: A REVIEW , 2015 .

[10]  C. Weller,et al.  Advances in grain sorghum and its co-products as a human health promoting dietary system , 2015 .

[11]  Yaling Yang,et al.  Dispersive Micro-Solid-Phase Extraction Based on Decanoic Acid Coated-Fe₃O₄ Nanoparticles for HPLC Analysis of Phthalate Esters in Liquor Samples. , 2015, Journal of food science.

[12]  M. Danaher,et al.  Development and validation of an UHPLC-MS/MS method for the determination of mycotoxins in grass silages , 2015, Food additives & contaminants. Part A, Chemistry, analysis, control, exposure & risk assessment.

[13]  Yuan-Jia Hu,et al.  Trace determination of five organophosphorus pesticides by using QuEChERS coupled with dispersive liquid–liquid microextraction and stacking before micellar electrokinetic chromatography , 2015 .

[14]  P. Avino,et al.  Extraction and GC-MS analysis of phthalate esters in food matrices: a review , 2015 .

[15]  Xiaowei Liu,et al.  Multiresidue analysis of over 200 pesticides in cereals using a QuEChERS and gas chromatography-tandem mass spectrometry-based method. , 2015, Food chemistry.

[16]  Weiping Liu,et al.  Status of phthalate esters contamination in agricultural soils across China and associated health risks. , 2014, Environmental pollution.

[17]  P. Avino,et al.  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 , 2014 .

[18]  Hongping Chen,et al.  Determination of 16 phthalate esters in tea samples using a modified QuEChERS sample preparation method combined with GC-MS/MS , 2014, Food additives & contaminants. Part A, Chemistry, analysis, control, exposure & risk assessment.

[19]  H. Langenhove,et al.  Development of a Sensitive and Accurate Stable Isotope Dilution Assay for the Simultaneous Determination of Free 4-Hydroxy-2-(E)-Nonenal and 4-Hydroxy-2-(E)-Hexenal in Various Food Matrices by Gas Chromatography–Mass Spectrometry , 2014, Food Analytical Methods.

[20]  Q. Cao,et al.  Determination of phthalate esters in liquor samples by vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction followed by GC-MS. , 2014, Journal of separation science.

[21]  Yaling Yang,et al.  Vortex-Assisted Liquid–Liquid Microextraction Combined with HPLC for the Simultaneous Determination of Five Phthalate Esters in Liquor Samples , 2014, Food Analytical Methods.

[22]  S. Oueslati,et al.  Presence of mycotoxins in sorghum and intake estimation in Tunisia , 2014, Food additives & contaminants. Part A, Chemistry, analysis, control, exposure & risk assessment.

[23]  R. Ito,et al.  Analytical Methods for the Quantification of Bisphenol A, Alkylphenols, Phthalate Esters, and Perfluoronated Chemicals in Biological Samples , 2014, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[24]  Tae Myoung Kim,et al.  Toxicological Evaluation and Anti-Inflammatory Activity of a Golden Gelatinous Sorghum Bran Extract , 2013, Bioscience, biotechnology, and biochemistry.

[25]  Xueyou Shen,et al.  Concentration and risk assessment of phthalates present in indoor air from newly decorated apartments , 2013 .

[26]  Chih-Feng Chen,et al.  Distribution of Phthalate Esters in Sediments of Kaohsiung Harbor, Taiwan , 2013 .

[27]  Yongsoon Park,et al.  Anti-diabetic effect of sorghum extract on hepatic gluconeogenesis of streptozotocin-induced diabetic rats , 2012, Nutrition & Metabolism.

[28]  E. Ferrer,et al.  Co-occurrence and risk assessment of mycotoxins in food and diet from Mediterranean area. , 2012, Food chemistry.

[29]  H. Zhang,et al.  Multi-residue method for determination of seven neonicotinoid insecticides in grains using dispersive solid-phase extraction and dispersive liquid-liquid micro-extraction by high performance liquid chromatography. , 2012, Food chemistry.

[30]  S. Cunha,et al.  Determination of bisphenol A and bisphenol B in canned seafood combining QuEChERS extraction with dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry , 2012, Analytical and Bioanalytical Chemistry.

[31]  I. Ferreira,et al.  Optimization and validation of a method based in a QuEChERS procedure and gas chromatography–mass spectrometry for the determination of multi-mycotoxins in popcorn , 2012 .

[32]  Yoko S Johnson.  Determination of polycyclic aromatic hydrocarbons in edible seafood by QuEChERS-based extraction and gas chromatography-tandem mass spectrometry. , 2012, Journal of food science.

[33]  B. Lee,et al.  Toxicological Characterization of Phthalic Acid , 2011, Toxicological research.

[34]  A. Uyama,et al.  Development of a Multi-mycotoxin Analysis in Beer-based Drinks by a Modified QuEChERS Method and Ultra-High-Performance Liquid Chromatography Coupled with Tandem Mass Spectrometry , 2011, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[35]  Marek Biziuk,et al.  Determination of pesticide residues in food matrices using the QuEChERS methodology , 2011 .

[36]  Katerina Mastovska,et al.  Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. , 2010, Journal of chromatography. A.

[37]  Jin-Ming Lin,et al.  Determination of phthalates in fruit jellies by dispersive SPE coupled with HPLC-MS. , 2010, Journal of separation science.

[38]  M Triassi,et al.  Assessing human exposure to phthalic acid and phthalate esters from mineral water stored in polyethylene terephthalate and glass bottles , 2008, Food additives & contaminants. Part A, Chemistry, analysis, control, exposure & risk assessment.

[39]  G. Shephard,et al.  Relative severity of fumonisin contamination of cereal crops in West Africa , 2007, Food additives & contaminants. Part A, Chemistry, analysis, control, exposure & risk assessment.

[40]  Steven J Lehotay,et al.  Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce. , 2003, Journal of AOAC International.

[41]  M. Hanna,et al.  Properties, composition, and analysis of grain sorghum wax , 2002 .

[42]  J. Knoll.  Estimation of the limit of detection in chromatography , 1985 .

[43]  W. Kong,et al.  A multiresidue method for simultaneous determination of 44 organophosphorous pesticides in Pogostemon cablin and related products using modified QuEChERS sample preparation procedure and GC-FPD. , 2015, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.