Determination of carbaryl pesticide in Fuji apples using surface-enhanced Raman spectroscopy coupled with multivariate analysis

Abstract Residual pesticides in fruits and vegetables are one of the major food safety concerns around the world. Surface-enhanced Raman spectroscopy (SERS) coupled with chemometric methods was applied for quantitative analysis of trace levels of carbaryl pesticide in apple. The lowest detectable level for carbaryl in apple was 0.5 μg g −1 , which was sensitive enough for identifying apple contaminated with carbaryl above the maximum residue level. Quantification of carbaryl residues (0–10 μg g −1 ) was conducted using partial least squares regression (PLSR) and support vector regression (SVR) models. Based upon the results of leave-one-out cross-validation, carbaryl levels in apples could be predicted by PLSR ( R 2  = 0.983) or SVR ( R 2  = 0.986) with a low root mean square errors (RMSE = 0.48 μg g −1 or 0.44 μg g −1 ) and a high ratio of performance to deviation (RPD = 7.71 or 8.11) value. This study indicates that SERS has the potential to quantify carbaryl pesticide in complex food matrices reliably.

[1]  Gajendra Pratap Singh,et al.  Investigation of noise-induced instabilities in quantitative biological spectroscopy and its implications for noninvasive glucose monitoring. , 2012, Analytical chemistry.

[2]  Chih-Jen Lin,et al.  LIBSVM: A library for support vector machines , 2011, TIST.

[3]  Louis E. Brus,et al.  Single Molecule Raman Spectroscopy at the Junctions of Large Ag Nanocrystals , 2003 .

[4]  Xichang Wang,et al.  Rapid determination of ractopamine in swine urine using surface-enhanced Raman spectroscopy. , 2011, Journal of agricultural and food chemistry.

[5]  I. Helland.  Partial Least Squares Regression , 2006 .

[6]  M. Moreno,et al.  Correlation study of enzyme-linked immunosorbent assay and high-performance liquid chromatography/tandem mass spectrometry for the determination of N-methylcarbamate insecticides in baby food , 2003 .

[7]  B. Kowalski,et al.  Partial least-squares regression: a tutorial , 1986 .

[8]  Steven R. Emory,et al.  Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering , 1997, Science.

[9]  W. Smith,et al.  Practical understanding and use of surface enhanced Raman scattering/surface enhanced resonance Raman scattering in chemical and biological analysis. , 2008, Chemical Society reviews.

[10]  W. Niessen.  Group-specific fragmentation of pesticides and related compounds in liquid chromatography-tandem mass spectrometry. , 2010, Journal of chromatography. A.

[11]  M. Lin,et al.  Detection of melamine in gluten, chicken feed, and processed foods using surface enhanced Raman spectroscopy and HPLC. , 2008, Journal of food science.

[12]  Richard L. McCreery,et al.  Raman Spectroscopy for Chemical Analysis , 2000 .

[13]  Xichang Wang,et al.  A novel approach to determine leucomalachite green and malachite green in fish fillets with surface‐enhanced Raman spectroscopy (SERS) and multivariate analyses , 2012 .

[14]  Xiaohuan Zang,et al.  Application of dispersive liquid–liquid microextraction combined with high-performance liquid chromatography to the determination of carbamate pesticides in water samples , 2009, Analytical and bioanalytical chemistry.

[15]  B. Rasco,et al.  Determination of tert-butylhydroquinone in vegetable oils using surface-enhanced Raman spectroscopy. , 2014, Journal of food science.

[16]  F. Hernández,et al.  The role of GC-MS/MS with triple quadrupole in pesticide residue analysis in food and the environment , 2013 .

[17]  Mohammad Abdollahi,et al.  Toxic influence of organophosphate, carbamate, and organochlorine pesticides on cellular metabolism of lipids, proteins, and carbohydrates , 2010, Human & experimental toxicology.

[18]  Chetan Shende,et al.  Analysis of pesticides on or in fruit by surface-enhanced Raman spectroscopy , 2004, SPIE Optics East.

[19]  B. Rasco,et al.  Detection of triphenylmethane drugs in fish muscle by surface-enhanced raman spectroscopy coupled with Au-Ag core-shell nanoparticles , 2014 .

[20]  Zhongpin Zhang,et al.  Shell thickness-dependent Raman enhancement for rapid identification and detection of pesticide residues at fruit peels. , 2012, Analytical chemistry.

[21]  Royston Goodacre,et al.  Quantitative Analysis of the Banned Food Dye Sudan-1 Using Surface Enhanced Raman Scattering with Multivariate Chemometrics† , 2010 .

[22]  Feng Liu,et al.  Detection of melamine in liquid milk using surface‐enhanced Raman scattering spectroscopy , 2010 .

[23]  Barbara Rasco,et al.  Application of surface enhanced Raman spectroscopy for analyses of restricted sulfa drugs , 2011 .

[24]  R. Corn,et al.  Fluorescence and Fourier Transform surface-enhanced Raman scattering measurements of methylene blue adsorbed onto a sulfur-modified gold electrode , 1993 .

[25]  Barbara Rasco,et al.  Analyses of phosmet residues in apples with surface-enhanced Raman spectroscopy , 2014 .

[26]  Yande Liu,et al.  Analyses of enrofloxacin, furazolidone and malachite green in fish products with surface-enhanced Raman spectroscopy. , 2012, Food chemistry.

[27]  Guofeng Wu,et al.  Comparison of multivariate methods for estimating soil total nitrogen with visible/near-infrared spectroscopy , 2012, Plant and Soil.

[28]  Luis M Liz-Marzán,et al.  Traps and cages for universal SERS detection. , 2012, Chemical Society reviews.

[29]  B. Liu,et al.  Detection of Pesticides in Fruits by Surface-Enhanced Raman Spectroscopy Coupled with Gold Nanostructures , 2013, Food and Bioprocess Technology.

[30]  Richard Jensen,et al.  Ant colony optimization as a feature selection method in the QSAR modeling of anti-HIV-1 activities of 3-(3,5-dimethylbenzyl)uracil derivatives using MLR, PLS and SVM regressions , 2009 .

[31]  Shuo Wang,et al.  Development of enzyme linked immunoassay for the simultaneous detection of carbaryl and metolcarb in different agricultural products. , 2010, Analytica chimica acta.

[32]  S. Chung,et al.  Determination of organochlorine pesticide residues in fatty foods: a critical review on the analytical methods and their testing capabilities. , 2011, Journal of chromatography. A.

[33]  Bernhard Schölkopf,et al.  A tutorial on support vector regression , 2004, Stat. Comput..

[34]  B. Rasco,et al.  Analyses of Trace Crystal Violet and Leucocrystal Violet with Gold Nanospheres and Commercial Gold Nanosubstrates for Surface-Enhanced Raman Spectroscopy , 2014, Food Analytical Methods.

[35]  M. Vohland,et al.  Comparing different multivariate calibration methods for the determination of soil organic carbon pools with visible to near infrared spectroscopy , 2011 .

[36]  Benjamin Saute,et al.  Gold nanorods as surface enhanced Raman spectroscopy substrates for sensitive and selective detection of ultra-low levels of dithiocarbamate pesticides. , 2012, The Analyst.

[37]  Vladimir N. Vapnik,et al.  The Nature of Statistical Learning Theory , 2000, Statistics for Engineering and Information Science.

[38]  Yan-ping Shi,et al.  Carbon nanotubes-reinforced hollow fibre solid-phase microextraction coupled with high performance liquid chromatography for the determination of carbamate pesticides in apples. , 2013, Food chemistry.

[39]  G. Pang,et al.  Determination of residues of 446 pesticides in fruits and vegetables by three-cartridge solid-phase extraction-gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry. , 2006, Journal of AOAC International.