RAPID DETECTION OF CHEMICAL CONTAMINANTS IN FOOD MATRICES BY USING FOURIER-TRANSFORM INFRARED (FT-IR) SPECTROSCOPY

• Sponsoring Institution: National Institute of Food and Agriculture
• Project Status: TERMINATED
• Funding Source: HATCH
• Reporting Frequency: Annual
• Accession No.: 0220440
• Project No.: OHO01225
• Project Start Date: Oct 1, 2009
• Project End Date: Sep 30, 2014

Project Director
Rodriguez-Saona, LU, EN.

Recipient Organization
OHIO STATE UNIVERSITY
1680 MADISON AVENUE
WOOSTER,OH 44691

Performing Department
Food Science & Technology

Non Technical Summary
The contamination of food by chemical and microbial hazards is a worldwide public health concern and a leading cause of trade problems internationally. Rapid and cost-effective techniques for the food industry and food safety agencies are required for effective surveillance. In recent years, the food industry and consumers have experienced several new or unsuspected contamination problems such as acrylamide, phthalates, organic pollutants, Sudan dyes, and recently melamine in dairy products. Rapid, sensitive and cost-effective detection techniques are necessary for surveillance of the food supply to prevent public health situations created by the potentially toxic effects of these hazards. Analysis of chemical food contaminants and toxins requires the development and validation of analytical methods for screening, quantification and identification of contaminants and their implementation as quality control programs and risk management systems by food producers and authorities. Our research will focus in the development of predictive models for the rapid detection, identification and classification of chemical contaminants in foods. Infrared spectral data combined with multivariate analysis techniques have the potential for the determination of food contaminants and changes in food integrity. Infrared spectroscopy allows qualitative or quantitative analysis of samples with little or no sample preparation which greatly speeds sample analysis. Spectral bands arising from functional group vibrations of organic molecules in the mid- infrared (4000-700 cm-1) region can be associated to specific chemical entities allowing for the chemically-based discrimination of organic constituents, producing distinct and reproducible fingerprints. Infrared spectroscopy combined with pattern recognition analysis is uniquely positioned for profiling of complex matrices resulting in reliable, accurate, robust and simple methods for routine analysis of adulterants or hazards in foods involving minimal personnel training and Lab supplies. Due to the use of mid-IR techniques in quality and process control applications, the food industry is familiar with the technology and the potential exists to extend its capabilities to monitor for food tampering. In 2008 Ahura Scientific launched the TruDefenderTMFT, a handheld infrared spectrometer that incorporates the analytical precision of FTIR spectroscopy to field applications, with a spectral resolution equivalent to bench-top instruments.

Animal Health Component

(N/A)

Research Effort Categories

Basic

(N/A)

Applied

(N/A)

Developmental

(N/A)

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
711	5010	1000	60%
711	5010	2000	40%

Knowledge Area
711 - Ensure Food Products Free of Harmful Chemicals, Including Residues from Agricultural and Other Sources;

Subject Of Investigation
5010 - Food;

Field Of Science
1000 - Biochemistry and biophysics; 2000 - Chemistry;

Keywords

contaminants

infrared spectroscopy

chemometrics

handheld infrared sensors

adulteration

Goals / Objectives
The long-term research goal is to develop rapid, simple, sensitive and specific detection strategies to identify contaminated food products to provide reliable and rapid screening methods for control of compliance, in order to ensure the integrity and safety of processed foods. Our central hypothesis is that the infrared sensor combined with chemometric analysis will provide the fingerprint power, reliability and accuracy of expensive, lab-based instruments in portable, rugged, easy-to-use systems designed for field analysis of foods. The significance of the proposed research is to provide the food industry with a system that will allow for the rapid and specific analysis of food chemical contaminants and provide tools for the reliable assessment of quality and safety, based on infrared sensors. It will enable the food manufacturer to rapidly asses the quality of their food, allowing for timely correction measures during manufacture. We expect this system to be simple to use and require minimal or no sample preparation, reducing the assay time and helping to streamline the analytical procedure so that it is more applicable to higher sample throughput and automation. Objectives: To generate highly specific vibrational spectroscopic signature profiles of potential food contaminants by using infrared spectroscopy. To develop multivariate classification models for the reliable and reproducible identification and quantification of contaminants, determining the sensitivity and selectivity of the infrared technique based on HPLC as reference method. To evaluate the feasibility of a handheld portable infrared system for rapid screening of potential contaminants in foods and to validate the infrared sensor performance to the specifications required by industry and regulatory agencies. Expected results: We will develop simple quantitation and classification models for contaminants/toxins levels in foods. Combining SPE to separate and concentrate the target toxic compound and infrared to provide spectral signature profiles will permit the chemically-based determination of contaminant levels in foods, if detected. We anticipate developing an easy-to-use, accurate and rapid system that will allow direct determination of contaminants minimizing the confounding effects of other chemical constituents in the food.

Project Methods
Standards of chemical contaminants (i.e. acrylamide, melamine, pesticides, rodent bait etc.) and toxins (i.e. mycotoxins) will be obtained from Sigma-Aldrich (St. Louis, MO). Stock solutions will be prepared, serially diluted to various concentrations and assayed in triplicate. Spiked samples will be analyzed to determine recoveries, sensitivity and specificity of the technology. Samples will be analyzed directly or after applied to solid-phase extraction (SPE) or immunoaffinity cartridges. For each matrix tested, a control (no toxin) sample will also be analyzed to determine background signal. An aliquot (5uL) of the samples (direct analysis or SPE/IMS concentrated) will be applied onto an ATR-IR crystal and analyzed by handheld infrared spectrometer and infrared microspectroscopy. The handheld infrared spectrometer incorporates the analytical precision of FTIR spectroscopy to field applications, with a spectral resolution equivalent to bench-top instruments. The application of an infinity corrected microscope coupled to a high performance infrared spectrometer (IRMS) will provide unique capabilities for resolving the desired signature structures. Spectra will be analyzed by using multivariate classification models for identification of potential contamination of foods. Analysis by SIMCA, a supervised method for classification, consists of assigning training sets to classes and then a principal component model is created for each class with different confidence regions. The performance of the models will be evaluated by visualization of clustering among samples by using score plots, model misclassification tests and inter-class distances. Probability clouds (95%) are built around the clusters based on PCA scores, allowing SIMCA to be used as a predictive modeling system. By using literature information on fundamental vibrations of specific functional groups and by using standards we will correlate these signals to unique cellular biomarkers. In addition, classification methods will be used to generate prediction models and model accuracy will be evaluated to predict the identities of unknown species. Quantitative models based on infrared spectra will be generated by Partial Least Squares regression (PLSR) based on the levels inoculated into the food samples. The levels will be confirmed by LC-MS or other reference method, using a standard fitted curve generated using contaminants/toxins at various concentrations. Optimum models are selected based on their lowest SECV, highest coefficient of determination, number of PCs and predictive ability. Validation of the models - Predictive ability: Determination of the performance of the PLSR models will be done with spiked food matrices with selected levels of contaminants/toxins. Recoveries will also be determined for each contaminant/toxin. The predictive ability of the generated PLSR models will be compared to the LC-MS values (reference method).

Progress 10/01/09 to 09/30/14

Outputs
Target Audience: The efforts of the project will provide valuable tools for authentication and detection of potential contaminants in foods and was targetted to growers, food manufacturers, government and research community. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Training of Marcal Plans-Pujolrais, a post-doctoral researcher from Universitat Politècnica de Catalunya (Barcelona) working on the application of vibrational spectroscopy for detection of contaminants. Collaborate with associate professor Ayse Demet Karaman, a visiting scholar from Adnan Menderes University, on developing fingerprinting techniques based on infrared spectroscopy for detection of Turkish extra virgin olive oil adulteration by using portable systems. Host visiting scholar Mustafa Mortas from Ondokuz Mayis University that will be developing a rapid and simple method based on mid-infrared (MIR) and Raman spectra and chemometric techniques as a tool for authentication of honey samples from different Turkish geographical origins. Hosted doctoral candidate Susana Restrepo from the Federico Santa Maria University (Chile) to evaluate application of infrared technology for wine authentication. We established collaboration with Agilent for testing state-of-the-art portable and handheld infrared spectrometers. The methods developed for monitoring oil quality and trans levels were demonstrated to the members of snack industry at the 11th Annual Wilbur A. Gould Quality & Innovation Management Course for the snack food industry. In 2014, the project has trained 2 undergraduate students, 3 MS students (graduated) and 2 PhD students that under my supervision have worked in various projects related to the authentication and rapid detection and identification of chemical contaminants in foods. How have the results been disseminated to communities of interest? The results from the project have been disseminated internationally and nationally through events that target scientific andindustrial audiences interested in detection of food adulteration and contaminants. These events provided a perfect setting forexchanging ideas with experts in the field, discuss current work, receive feedback from the scientific community, develop newprofessional networks and disseminate knowledge through multidisciplinary research collaborations. In 2014 I served asChair of the Food Quality, Safety & Analysis Symposium at 28th International forum and exhibition process analyticaltechnology - IFPAC 2014. Arlington, VA. 2014Invited Speaker Presentations:Application of Portable FT-IR Spectrometers for Detection of Minor Food Components.Presented at the 2014 Short Course onAnalytical Techniques: Quality Control, Process Control, and Refinery Optimization, San Antonio TX. Invited Speaker at 2014 Institute of Food Technologists Annual Meeting and Food Expo on Portable FTIR Spectrometers for Monitoring Food Authentication and Adulteration in High-Risk Foods at theFTIR and NIR Spectroscopy Rapidly Assess the Quality of Foods session, New Orleans, LA. Invited SpeakeratThe 2ndInternational Congress on Food Technology onPortable FT-IR spectrometers – Becoming a reality for the food industry, November 05-07, 2014 Kusadasi, Turkey. Students presented their work at the 2014 Institute of Food Tecnlogists Annual Meeting and Food Expo. (1) Mei-Ling Shotts, Ni Cheng, Luis Rodriguez-Saona.COMP16-04.Application of Near-Infrared Spectroscopy (NIRS) in Quality Assurance of Chicken Nuggets. PLaced Second at the Quality Assurance Poster Competition. New Orleans, June 21 – 24,2014. (2) Marcal Plans Pujolras, Luis P Rodriguez-Saona, Michael Wenstrup.206-07 Infrared Models to Predict Fatty Acids Profile Levels in Dietary Oil Supplements.New Orleans, June 21 – 24,2014. (3)Alex M Milligan, Samuel Ryo andLuis Rodriguez-Saona.206-55 Determination of Trans-Fat Content in Baking Food Products Using a Portable ATR-FTIR system.New Orleans, June 21 – 24,2014. (4)Didem P Aykas, Luis Rodriguez-Saona.206-22 Assessing Potato Chip Oil Using a Portable Infrared Spectrometer Combined With Pattern Recognition Analysis.New Orleans, June 21 – 24,2014. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? We have evaluated the application of vibrational spectroscopy for rapid screening, identification and quantification of contaminants and their implementation as quality control programs and risk management systems by food producers and authorities. Our efforts in 2014 have been directed at evaluating the performance of handheld and portable infrared systems for rapid screening of acrylamide in potato chips and to serve as authentication tools for organic products, authentication of oils (vegetable, olive, and fish) and quantitation of trans fat in various bakery products. Premium prices can be charged for organic ingredients, which has led to the growth of certified organic farmland and overall market, becoming more accessible to the general public because they are now sold in mainstream grocery stores instead of only specialty stores. The USDA National Organic Program following the U.S. Organic Standards must certify organic food products in the US. The regulatory and inspection system that is currently in place may not be sufficient enough to confirm the origin and authenticate organic products. We have shown the capabilities of a portable mid-infrared spectrometer combined with multivariate analysis to discriminate between organic and conventional cornmeal and butter products based on unique signature signal associated with carboxylic amino acids and levels of naturally occurring trans fats, respectively. Furthermore, we were able to develop predictive models for estimating viscosity and moisture levels of cornmeal, important quality traits for manufacturing extruded snacks. For butter products, we developed models to predict major fatty acids and conjugated linoleic acid (CLA) levels. We have also developed models for assessing trans fat levels in various bakery products with prediction error of 0.2% trans in the products allowing for rapid screening for nutrition labeling compliance. Samples (cakes, chips, donuts, cookies, etc) were obtained from various grocery stores and evaluated for trans fat content. Although oils in bakery products required extraction before analysis, the method was rapid (~ 1min) and showed excellent predictive accuracy when compared to the reference GC values. Although all products accurately reported 0g trans fat, in products reporting levels >0.5g we found several cases of gross deviation of trans fat levels in labels. Based on concerns from the snack industry regarding mislabeling of premium frying oils such as sunflower or high oleic sunflower oils, with less expensive oils, we authenticated the frying oil used in manufacturing of potato chips. We have developed authenticating tools that allowed rapid screening of oils and quantitation of major fatty acids, free fatty acids and peroxide value of oils. We found few cases of mislabeling of chips that indicated the use of sunflower oil with either canola or mixture of sunflower with other oils (likely corn, soybean or cottonseed). We extended these fingerprinting capabilities to authenticate extra virgin olive oil, an economically important product commonly adulterated with less expensive oils to increase the profit. Olive oil samples were obtained from Turkey and their fatty acid profile was determined by using GC-FAME procedure. Oils formed distinct clusters allowing the evaluation of extra virgin olive oils from lower quality or adulterated oils. Determining oil adulteration and quality characteristics using portable FT-IR unit enables portability and ease-of-use, making it a great alternative to traditional testing methods. Lastly, we report on the ability of a portable infrared equipped with single reflection diamond ATR sampling interface and handheld NIR to screen for acrylamide in potato chips, sweet potato chips and French fries with prediction errors (SEP) of 100 μg/kg. Screening of acrylamide by portable FTIR provides a simpler analysis method for this potentially hazardous by-product than the current mass spectroscopy approach and can be deployed wherever acrylamide needs to be measured, whether in a lab, production facility, or for spot check measurements to determine levels in consumer product.

Publications

• Type: Book Chapters Status: Published Year Published: 2014 Citation: Mossoba, MM, Aykas, DP and Rodriguez-Saona, LE. 2014. Application of Vibrational Spectroscopy, Portable Detectors and Hyphenated Techniques to the Analysis of Heat-Induced Changes in Oil and Food Constituents. In "Food Safety Chemistry: Toxicant Occurrence, Analysis and Mitigation" Edited by Liangli (Lucy) Yu and Shuo Wang. CRC Press, Boca Raton, FL.
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Snyder, AB, Sweeney, CF, Rodriguez-Saona, LE and Giusti, MM. 2014. Rapid authentication of concord juice concentration in a grape juice blend using Fourier-Transform infrared spectroscopy and chemometric analysis. Food Chem. 147, 295301.
• Type: Journal Articles Status: Published Year Published: 2015 Citation: Ayvaz, H and Rodriguez-Saona, LE. 2015. Application of handheld and portable spectrometers for screening acrylamide content in commercial potato chips. Food Chem. 174, 154162
• Type: Journal Articles Status: Accepted Year Published: 2015 Citation: Ayvaz, H, Plans, M, Towers, BN, Auer, A and Rodriguez-Saona, LE. The Use of Infrared Spectrometers to Predict Quality Parameters of Cornmeal (Corn Grits) and Differentiate between Organic and Conventional Practices. Accepted J Cereal Sci

Progress 01/01/13 to 09/30/13

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Training of Marcal Plans-Pujolrais, a post-doctoral researcher from Universitat Politècnica de Catalunya, Barcelona. Marcal is working on the application of vibrational spectroscopy for detection of contaminants. Hosted assistant professor Ayse Demet Karaman, a visiting scholar from Adnan Menderes University. Ayse is working on fingerprinting techniques based on infrared spectroscopy for authetication of organic from conventional milk samples and detection of extra virgin olive oil adulteration by using portable systems. Hosted assistant professor Adnan Bozdogan, a visiting scholar from Osmaniye Korkut Ata University that will be developing a rapid and simple method based on mid-infrared (MIR) spectra and chemometric techniques as a tool for authentication of honey samples from different Turkish geographical origins. We established collaboration with Dr. Alejandra Urtubia from the Federico Santa Maria University (Cile) and CREAS (Chile) to evaluate application of infrared technology for wine authentication and other fruit and vegetable products. We have established collaboration with Agilent for testing state-of-the-art portable and handheld infrared spectrometers. How have the results been disseminated to communities of interest? The results from the project have been disseminated internationally and nationally through events that target scientific and industrial audiences interested in detection of food adulteration and contaminants. These events provided a perfect setting for exchanging ideas with experts in the field, discuss current work, receive feedback from the scientific community, develop new professional networks and disseminate knowledge through multidisciplinary research collaborations. What do you plan to do during the next reporting period to accomplish the goals? We will continue evaluating applications of the portable mid-infrared and handheld NIR spectrometers for authentication of high-risk ingredients, including olive oil and pomegranate juices.

Impacts
What was accomplished under these goals? We have continued to evaluate the application of vibrational spectroscopy for rapid screening, identification and quantification of contaminants and their implementation as quality control programs and risk management systems by food producers and authorities. Our efforts in 2013 have been focused on developing authentication tools for differentiation of organic from conventional cornmeal and butter, authentication of oils used in manufacturing of potato chips, quantitation of trans fat in various bakery products and profiling fish oil supplements. We have shown the capabilities of a portable mid-infrared spectrometer combined with multivariate analysis to discriminate between organic and conventional cornmeal based on unique signature signal associated with carboxylic amino acids. Furthermore, we were able to develop predictive models for estimating final viscosity and moisture levels of cornmeal, important quality traits for manufacturing extruded snacks. In the case of butter, we identified that differences in levels of conjugated linoleic acid (CLA) allowed the discrimination of organic from conventional butter. GC analysis was used to confirm our findings. Models were developed to monitor trans fat levels in various bakery products with prediction error of 0.2% trans in the products allowing for rapid screening for nutrition labeling compliance. Based on concerns from the snack industry regarding mislabeling of premium frying oils such as sunflower or high oleic sunflower oils, with less expensive oils, we authenticated the frying oil used in manufacturing of potato chips. We found mislabeling of chips that indicated the use of sunflower oil with either high oleic canola or mixture of sunflower with other oils (likely corn, soybean or cottonseed). Our predictions by using the chemometric models were validated by the GC results of fatty acid profiles. The potential profits and trading advantages from mislabeling prejudice the interests of both consumers and honest manufacturers. Finally, we have characterized the composition of commercial Omega-3/6/9 dietary supplements using mid-infrared spectroscopy, gas chromatography, and chemometrics. Dietary supplements were purchased from retailers that included a large amount of source and processing variability and encompassed a wide range of fatty acid profiles. Pattern recognition analysis using the 2700-3100 wavenumber region, associated with olefinic and aliphatic stretching on the fatty acid backbone, allowed tightly clustering of samples into distinct classes. Regression models correlated between the infrared spectrum and fatty acid composition. Our results indicate that ATR-IR spectroscopy combined with pattern recognition analysis provides robust screening and determination of fatty acid composition of fish oil supplements.

Publications

• Type: Journal Articles Status: Published Year Published: 2013 Citation: Ayvaz, H; Plans, M; Riedl, KM; Schwartz, SJ; Rodriguez-Saona, LE. Application of infrared microspectroscopy and chemometric analysis for screening the acrylamide content in potato chips. ANALYTICAL METHODS. Vol. 5, no. 8: 2020-2027.
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Maurer, NE, Rodriguez-Saona, LE. Rapid Assessment of Quality Parameters in Cocoa Butter Using ATR-MIR Spectroscopy and Multivariate Analysis. J Am Oil Chem Soc. Vol. 90, no. 4: 475-481.
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Santos, PM; Pereira-Filho, ER; Rodriguez-Saona, LE. Rapid detection and quantification of milk adulteration usinginfrared microspectroscopy and chemometrics analysis. FOOD CHEM. Vol. 138, no. 1: 19-24.

Progress 01/01/12 to 12/31/12

Outputs
OUTPUTS: The results from the project have been disseminated internationally and nationally through events that target scientific and industrial audiences interested in detection of food adulteration and contaminants. These events provided a perfect setting for exchanging ideas with experts in the field, discuss current work, receive feedback from the scientific community, develop new professional networks and disseminate knowledge through multi-disciplinary research collaborations. Products also include 1 MS students graduated in 2012 in Food Science at The Ohio State University working on oil authentication. We have established key collaborations with Thermo Nicolet (formerly Ahura Scientific) and Agilent (formerly A2 Technologies) to explore the applications of state-of-the-art portable handheld/portable mid-infrared spectrometers for real-time sensing of food contamination/adulteration. Invited Speaker Presentations: IFPAC 2012. Food Symposium. Fingerprinting Food Ingredients for Food Authentication by Vibrational Spectroscopy Technologies. In "Emerging Technologies with Focus on Traceability and Contamination" Session. Baltimore, MD. SCIX 2012. Opportunities of Portable FT-IR Instrumentation for the Food Industry. In "Applications and Advances in Handheld and Portable Spectroscopy" Session. Kansas City, MO. October 1-4. Montana SA. 2011. Application of infrared spectroscopy in quality control and detection of food contaminants. Dec 19-20th, Lima, Peru. Poster Presentations Poliana Macedo dos Santos, Edenir R. Pereira-Filho, Luis Rodriguez-Saona. 2012. Application of handheld and portable infrared spectrometers in bovine milk analysis. Food, Bio-Extract, and Materials Characterization Poster session. SCIX sponsored by FACSS, Kansas City, MO, October 1-5th. Poliana Macedo Dos Santos, Edenir R. Pereira-Filho, and Luis Rodriguez-Saona. 2012. 1160-18 Rapid Determination and Quantification of Adulteration in Milk by Mid-Infrared. Food Science 1, The Pittsburgh Conference (Pittcon), March 11-15, Orlando, FL. Ting Wang and Luis Rodriguez-Saona. 2012. 2110-13 The Development of Infrared Spectroscopy and Chemometrics on Rapid Detection of Cocoa Butter Adulteration. Food Science IV, The Pittsburgh Conference (Pittcon), March 11-15, Orlando, FL. Huseyin Ayvaz, Maria M Giusti, Luis Rodriguez-Saona. 2012. 193-12 Application of Infrared Sensors for Screening Acrylamide Content in Snack Products. IFT Food Chemistry Division Poster Session, June 26-28, Las Vegas, NV. Natalie Maurer, Luis E Rodriguez-Saona. 281-01 Rapid Assessment of Quality Parameters in Cocoa Butter Using ATR-IR Spectroscopy and Multivariate Analysis. IFT Food Chemistry Division Poster Session, June 26-28, Las Vegas, NV. Ting Wang, Luis E Rodriguez-Saona. 193-147 Rapid Detection of Chemical Adulteration in Cocoa Butter Using Spectrometry Method. IFT Food Chemistry Division Poster Session, June 26-28, Las Vegas, NV. PARTICIPANTS: We established collaboration with the Dr Edenir R Pereira-Filho from UFSCar, Brasil to evaluate application of infared technology for detecting milk adulteration. We have established collaboration with Agilent for testing state-of-the-art portable and handheld infared spectrometers. TARGET AUDIENCES: This project provides graduate students and associates with a broadly interdisciplinary education in fields of food safety, quality assurance and fundamentals of sensing technology. Our target are the Food Industry, Regulatory Agencies and Scientific community by developing sensor technologies directed at improving efficiency, throughput and reliability of critical processes, such as authentication of incoming raw materials. Ultimately these authentication programs would enable for real-time and field-based measurements for controlling the raw material stream, addressing safety and brand equity. We are developing education modules to disseminate the newfound knowledge to the food industry, regulatory agencies and the public at large. By establishing industry partnerships to stimulate and accelerate technology transfer from research laboratory to industry of validated and demonstrated prototype sensors to meet the specific demands of food authentication. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Economic adulteration and counterfeiting of global foods may cost the industry an estimated $10 to $15 billion per year. According to results summarized in the US Pharmacopeial Convention's Food Chemicals Codex (JFS, 2012), olive oil, milk, honey, and saffron were the most common targets for adulteration. We are evaluating the application of vibrational spectroscopy for rapid analysis of chemical food contaminants and toxins for screening, identification and quantification of contaminants and their implementation as quality control programs and risk management systems by food producers and authorities. Our efforts in 2012 have been focused on oil authentication. The vegetable-oil sector encompasses products of differing value and sales volume and adulteration may comprise the dilution of expensive oils with cheaper oils. We have shown the capabilities of a handheld mid-infrared spectrometer combined with multivariate analysis to characterize oils, monitor chemical processes occurring during oxidation, and to determine fatty acid composition. Models were developed to classify vegetable oils (corn, peanut, sunflower, safflower, cottonseed, and canola) and estimate oil stability parameters based on unique fingerprint spectra. In addition, we investigated the ability of portable handheld spectrometers to characterize sacha inchi oils, a Peruvian seed rich in ω-3's, and detect adulteration. Sources of omega-3 fatty acids (ω-3's), whether from fish oils, flax or supplements, are expensive because of their associated health benefits such as protection against cardiovascular disease. Pure oils formed distinct clusters allowing the detection of some prevalence of adulteration with corn oil in commercial samples. Our efforts were also directed to the application of infrared technology as a screening tool for the cocoa butter supply. Cocoa butter samples encompassing an acceptable range of compositional variability for the chocolate industry was classified using pattern recognition analysis. Furthermore, pure cocoa butter samples were melted and spiked with palm oil, mineral oil, and heptanes separately at 1%, 0.1%, and 0.01% levels. Analysis of spectra by pattern recognition successfully discriminated all contaminated samples at level >0.01%. ATR-MIR spectroscopy combined with chemometrics provides robust models for characterization oils/fats permitting screening for adulteration and quality parameters. We also continued the application of NIR and mid-infrared (ATR-IR) spectroscopy as an alternative to HPLC/MS/MS current methods to measure acrylamide content. We evaluated 40 commercial potato chip products and our data supports the application of mid-infrared microspectroscopy for acrylamide analysis in potato chips, reporting the lowest prediction errors (SECV ~ 18 ppb) as compared to research studies conducted using NIR spectroscopy, predicting acrylamide levels with SECV of ~270 ppb. Implementation of FT-IR technique can simplify and reduce the time required for analysis of acrylamide reducing the investment in chemicals and reagents.

Publications

• Maurer, NE;, Hatta-Sakoda, B;, Pascual-Chagman, G;, Rodriguez-Saona, LE. 2012. Characterization and authentication of a novel vegetable source of omega-3 fatty acids, sacha inchi (Plukenetia volubilis L.) oil. Food Chem. 134(2): 1173-1180. Hassel, S., Rodriguez-Saona, LE. 2012. Application of a Handheld Infrared Sensor for Monitoring the Mineral Fortification in Whole Grain Cornmeal. Food Analytical Methods, 5(3): 571-578 Allendorf, M; Subramanian, A; Rodriguez-Saona, L. 2012. Application of a handheld portable mid-infrared sensor for monitoring oil oxidative stability. JAOCS, 89: 79-88.

Progress 01/01/11 to 12/31/11

Outputs
OUTPUTS: We are evaluating the application of vibrational spectroscopy for rapid analysis of chemical food contaminants and toxins for screening, identification and quantification of contaminants and their implementation as quality control programs and risk management systems by food producers and authorities. The results from the project have been disseminated internationally and nationally through events that target scientific and industrial audiences interested in detection of food adulteration and contaminants. These events provided a perfect setting for exchanging ideas with experts in the field, discuss current work, receive feedback from the scientific community, develop new professional networks and disseminate knowledge through multi-disciplinary research collaborations. Products also include 1 MS students graduated in 2011 in Food Science at The Ohio State University working on detection of trans-fat levels in foods. We have established key collaborations with Thermo Nicolet (formerly Ahura Scientific) and Agilent (formerly A2 Technologies) to explore the applications of state-of-the-art portable handheld/portable mid-infrared spectrometers for real-time sensing of food contamination/adulteration. Invited Speaker Presentations: IFPAC 2011. Detection of Adulteration in Food. In "Benefits and Challenges of PAT in the Food Industry: Drivers for the Adoption of PAT in Food" Session. Jan 17-19th, Baltimore, MD. Universidad Nacional Agraria La Molina (UNALM). 2011. Chromatographic and Spectroscopic Applications in the Characterization of Natural Products, Monitoring Athenticity and Quality Control - (Aplicaciones Cromatograficas y Espectroscopicas para la Caracterizacion de Productos Naturales, Monitoreo de Autenticidad y Calidad de Alimentos). Workshop, Aug 8-11th, Lima, PE. Enrollment: 25. San Antonio Abad de Cusco (UNSAAC). 2011. II International Workshop on Modern Analysis of Foods and Natural Produscts - (II Curso Internacional. Analisis Moderno de Alimentos y Productos Naturales). Aug 1-5th, Cusco, Peru. Enrollment: 65 students attended the lectures, 30 of them also participated in the laboratory. Montana SA. 2011. Applicaciones espectroscopicas para el Control de Calidad y Deteccion de contaminantes (Application of infrared spectroscopy in quality control and detection of food contaminants). Dec 19-20th, Lima, Peru. Poster Presentations Emily Birkel and Luis Rodriguez-Saona. 2010. Detection and quantitation of trans fat in fats and oils using a portable handheld infrared spectrometer. Food Chemistry poster session. IFT Annual Meeting, July 17 - 20, Chicago, IL. Emily Birkel and Luis E. Rodriguez-Saona. 2011. A rapid screening method for acrylamide in potato chips using mid- and near-infrared spectroscopy. Food Chemistry poster session. 2011 IFT Annual Meeting, June 11 - 14, New Orleans LA. PARTICIPANTS: The PD, Dr. Luis E. Rodriguez-Saona, is responsible for supervising the project which will include development of sample preparation protocols, IR data collection and multivariate analysis. Professional development: Emily Birkel, MS students TARGET AUDIENCES: Our target is the food industry that will obtain tools for simple, rapid and high-throughput determination of food contaminats. This would enable detection and characterization of potential chemical food contaminants via unique spectral signature profiles, permitting real-time and field-based control of the product stream to enhance safety and brand equity. By establishing industry partnerships we aim at stimulating and accelerating technology transfer from research laboratory to industry of validated and demonstrated prototype sensors to meet the specific demands of food processing. Our research can reduce the assay time and help streamline the analytical procedure so that it is more applicable to higher sample throughput and automation. PROJECT MODIFICATIONS: Not relevant to this project.

Impacts
The contamination of food by chemical and microbial hazards is a worldwide public health concern and a leading cause of trade problems internationally. Rapid and cost-effective techniques are required for effective surveillance. In recent years, the food industry and consumers have experienced several new or unsuspected contamination problems and rapid, sensitive and cost-effective detection techniques are necessary to prevent public health situations created by the potentially toxic effects of these hazards. We are evaluating the application of vibrational spectroscopy for rapid analysis of chemical food contaminants and toxins for screening, identification and quantification of contaminants and their implementation as quality control programs and risk management systems by food producers and authorities. Trans fat has been under scrutiny in the past several years and its inclusion on nutrition labels has been mandatory for the past 5 years. The use of infrared spectroscopy for determining the amount of trans fat in fat and oil samples has been established as an AOAC official analytical method. We have found that a handheld, portable infrared system could be used to measure trans fat at levels ≥1% (w/w), comparable to values obtained with benchtop systems. This method would be useful for producers interested in "real-time" trans measurements, i.e. a batch of oil, rather than sending the sample to a lab for analysis. We have also evaluated the application of NIR and mid-infrared (ATR-IR) spectroscopy as an alternative to HPLC/MS/MS current methods to measure acrylamide content. For potato chips, NIR and ATR-IR results provided comparable limits of detection (~300 ppb) with a total analysis time required for sample preparation and IR analysis of less than 5 minutes per sample, compared to several hours required for acrylamide content by reference methods. Thus, implementation of FT-IR technique can simplify and reduce the time required for analysis of acrylamide reducing the investment in chemicals and reagents. Infrared spectroscopy shows promise as a rapid screening and detection method in the food industry offering an alternative to traditional measurement methods that will enable the food industry to more quickly monitor and control product quality and safety.

Publications

• Rodriguez-Saona LE and Allendorf ME. 2011. Use of FTIR for Rapid Authentication and Detection of Adulteration of Food. Ann Rev Food Sci Technol. 2: 467-483.
• Birkel, E; Rodriguez-Saona, L. 2011. Application of a Portable Handheld Infrared Spectrometer for Quantitation of trans Fat in Edible Oils. J Amer Oil Chem Soc. 88 (10): 1477-1483.
• Mossoba M.M., Seiler A., Steinhart H., Kramer J. K. G., Rodriguez-Saona L., Griffith A. P., Pierceall R., van de Voort F.R., Sedman J., Ismail A.A., Barr D., Da Costa Filho P.A., Li H., Zhang Y., Liu X., Bradley M. 2011. Regulatory infrared spectroscopic method for the rapid determination of total isolated trans fat: A collaborative study. J Am Oil Chem Soc. 88:39-46.

Progress 01/01/10 to 12/31/10

Outputs
OUTPUTS: The results from the project have been disseminated internationally and nationally trough events that target scientific and industrial audiences interested in screening and detection of food contaminants: International Presentations: Rodriguez-Saona, L.E. (2010). Application of infrared spectroscopy for detection of food contaminants. Seminars at Universidad Nacional Agraria, La Molina (Lima, Peru) and Universidad Nacional San Antonio de Abad (UNSAAC, Cusco, Peru). International Seminar Series. Oral Presentations. National Presentations 1. Emily Birkel, Luis Rodriguez-Saona. 2010. 070-02 - Detection and quantitation of trans fat in fats and oils using a portable handheld infrared spectrometer. Food Chemistry Division: Emerging technologies and ingredient innovations posters. Institute of Food Technologists Annual Conference. Sunday, July 18, 2010. Chicago, IL. 2. Meghan Allendorf, Luis Rodriguez-Saona. 2010. 070-19 - Application of handheld portable infrared and Raman sensors for characterizing and monitoring quality of edible oils. Food Chemistry Division: Emerging technologies and ingredient innovations posters. Institute of Food Technologists Annual Conference. Sunday, July 18, 2010. Chicago, IL. Placed 1st in the Food Chemistry Division poster competition. 3. Meghan Allendorf, Luis Rodriguez-Saona, David Min. 2010. 1690-3P - Application of a handheld portable infrared sensor for monitoring oil quality. Food Science - Components and Contaminants I Poster Session. Pittcon, Tuesday March 2, 2010. Orlando, FL. 4. Emily Birkel, LuisRodriguez-Saona. 2010. 1690-5P - Application of a portable handheld infrared/Raman spectrometer for quantitation of trans-fat. Food Science - Components and Contaminants I Poster Session. Pittcon, Tuesday March 2, 2010. Orlando, FL. 5. Emily Birkel and Luis Rodriguez-Saona. 2010. "Application of a Portable Handheld Infrared/Raman Spectrometer for Quantitation of trans-Fat". Placed first at the 2010 Graduate Student Poster Competition. The Ohio Agricultural Research and Development Center (OARDC). April 2010. Wooster, OH. Also, Emily Birkel placed 1st place at the OVIFT Food Safety Symposium - Master's /Undergraduate Poster Award. April, 2010. Columbus, OH. PARTICIPANTS: The PD, Dr. Luis E. Rodriguez-Saona, is responsible for supervising the project which will include development of sample preparation protocols, IR data collection and multivariate analysis. Professional development: Meghan Allendorf and Emily Birkel, MS students. TARGET AUDIENCES: This project provide graduate students and associates with a broadly interdisciplinary education in fields of food safety and fundamentals of sensing technology. Our target are food industry and suppliers that will obtain tools for simple, rapid and high-throughput screening and detection of potential adulteration by chemical contaminants. We anticipate obtaining a protocol that will provide early and rapid information about toxic substances in foods. The results should provide a simple, rapid and non-destructive infrared (FT-NIR & mid-IR) diagnostic tool that can be easily implemented by the industry and regulatory agencies. We are developing education modules to disseminate the newfound knowledge to the food industry, regulatory agencies and the public at large. By establishing industry partnerships to stimulate and accelerate technology transfer from research laboratory to industry of validated and demonstrated prototype sensors to meet the specific demands of food processing. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
The contamination of food by chemical and microbial hazards is a worldwide public health concern and a leading cause of trade problems internationally. Rapid and cost-effective techniques are required for effective surveillance. In recent years, the food industry and consumers have experienced several new or unsuspected contamination problems and rapid, sensitive and cost-effective detection techniques are necessary to prevent public health situations created by the potentially toxic effects of these hazards. We are evaluating the application of vibrational spectroscopy for rapid analysis of chemical food contaminants and toxins for screening, identification and quantification of contaminants and their implementation as quality control programs and risk management systems by food producers and authorities. Monitoring of raw materials and their changes during processing and storage is very important from quality, functionality, and economic-value stand points. Lipid oxidation has a negative impact on product flavor, shelf life, and nutrition. We have evaluated handheld portable infrared sensors and our results strongly suggest the ability of simultaneous analysis of oxidative indicators independent of the type of oil. Overall, models developed from reference tests and handheld spectra slightly overestimated the prediction errors compared to benchtop instrument but their portability and ease-of-use makes the handheld device a great alternative to traditional methods. Trans fat has been under scrutiny in the past several years and its inclusion on nutrition labels has been mandatory for the past 5 years. The use of infrared spectroscopy for determining the amount of trans fat in fat and oil samples has been established as an official analytical method. In order to adapt this method to be more suitable for industry use, we investigated the application of a handheld, portable infrared spectrometer to the measurement of trans fat. We compared the handheld spectrometer combined with chemometric statistical analysis to a traditional benchtop infrared system, and found that the handheld system could be used to measure trans fat levels as low as 1% (w/w). This method would be useful for producers wishing to take the spectrometer to the sample, i.e. a batch of oil, rather than sending the sample to a lab for analysis. Infrared spectroscopy shows promise as a rapid screening and detection method in the food industry offering an alternative to traditional measurement methods that will enable the food industry to more quickly monitor and control product quality and safety.

Publications

• No publications reported this period