Research Project: Development, Evaluation, and Validation of Technologies for the Detection and Characterization of Chemical Contaminants in Foods

Location: Microbial and Chemical Food Safety

2021 Annual Report

Objectives
1. Develop, validate, and transfer multiclass, multiresidue methods for pesticides, environmental, and emerging contaminants in FSIS-regulated foods, and conduct a survey of food samples for the contaminants. 1A. Simultaneous analysis method for diverse pesticides, legacy and emerging environmental contaminants in meats. 1B. Multiresidue method for food packaging (FP) contaminants in packaged foods. 1C. Conduct a survey of food samples for emerging environmental and FP contaminants. 2. Develop qualitative screening and identification criteria with automated data processing that meets regulatory needs to minimize/avoid false positives and negatives. 3. Develop sample processing methods for regulatory analysis that improve the ability to detect combinations of veterinary drug residues in the same sample preparation. 3A. Simultaneous analysis method for diverse veterinary drugs residues, including aminoglycoside antibiotics, in meats. 3B. Evaluate cryogenic sample processing to achieve meaningful representative sample size of 100 mg in multiresidue analysis of pesticides and veterinary drug residues in foods. 4. Develop automated high-throughput sample processing, preparation, and analysis methods using flow-injection and/or open probe techniques coupled with mass spectrometry to monitor >500 veterinary drugs, pesticides, and environmental contaminants in foods. 5. Develop novel analytical methods for inorganic and organometallic heavy metals [for example forms of mercury (Hg) and arsenic (As)] in foods. 5A. Develop novel analytical methods for mercury speciation and quantification in foods. 5B. Develop novel analytical methods for arsenic speciation and quantification in foods. 6. Develop and use bioanalytical methods (including mass spectrometry) to monitor for antibiotic resistant organisms and/or their biomarkers in conjunction with antibiotic residues in seafood and meats.

Approach
The specific approaches for meeting the project’s objectives and milestones are as follows: 1) develop, validate, and transfer multiclass, multiresidue methods for pesticides, environmental, and emerging contaminants in FSIS-regulated foods, and conduct a survey of food samples for the contaminants; 2) develop qualitative screening and identification criteria with automated data processing that meets regulatory needs to minimize/avoid false positives and negatives; 3) develop sample processing methods for regulatory analysis that improve the ability to detect combinations of veterinary drug residues in the same sample preparation; 4) develop automated high-throughput sample processing, preparation, and analysis methods using flow-injection and/or open probe techniques coupled with mass spectrometry to monitor >500 veterinary drugs, pesticides, and environmental contaminants in foods; 5) develop novel analytical methods for inorganic and organometallic heavy metals [for example forms of mercury (Hg) and arsenic (As)] in foods; and 6) develop and use bioanalytical methods (including mass spectrometry) to monitor for antibiotic resistant organisms and/or their biomarkers in conjunction with antibiotic residues in seafood and meats.

Progress Report
This is the final report for Project 8072-42000-080-00D, which ended January 18, 2021. New approved project 8072-42000-088-00D, entitled “Technology Development, Evaluation, and Validation for the Detection and Characterization of Chemical Contaminants in Foods,” has been established. Chemical residue monitoring of food is required in laboratories worldwide to ensure food safety, protect the environment, meet laws, and avoid liabilities. This project addressed the need to detect multiple chemical residues and other toxic compounds in foods most effectively and efficiently. The project met the needs of the USDA Food Safety Inspection Service (FSIS), Food and Drug Administration (FDA), and other organizations that monitor chemical residues in food, including industry, consumer groups, and academic scientists. Altogether, 63 peer-reviewed publications resulted from this project since 2016, and numerous abstracts, proceedings, lectures, and training courses. The ARS scientists developed and validated advantageous analytical methods which were transferred to and implemented by FSIS in the National Residue Program, including the “extract & inject” analytical method for veterinary drugs in catfish, ready-to-eat meats, liquid and powdered eggs, and cattle, chicken, and pork muscle, kidney, and liver. The newest ARS method, known as the “quick, easy, cheap, effective, rugged, safe, efficient, and robust” (QuEChERSER) mega-method has been extensively validated and is being transferred to FSIS to monitor for pesticides, veterinary drugs, and environmental contaminants in the same procedure. In this way, at least two methods are being combined into one method, which has the most impact on reducing the time, costs, and labor associated with analyses in the laboratory. The outcome of this research will be faster, simpler, and more accurate monitoring of pesticides, veterinary drugs, toxins, endocrine disruptors, and mercury and arsenic species in all types of foods. A noticeable impact of this research will be improved human health and more responsible food production practices through enhanced food safety due to better regulatory enforcement, more effective control of food trade, and higher quality of data for risk assessment and other purposes. Comparison of different mass spectrometric identification criteria for regulatory analysis of chemical residues in food. Chemical analysis requires both qualitative and quantitative information for a regulatory agency to make an enforcement action. Tandem mass spectrometry (MS/MS) is the most common analytical tool used for monitoring the food supply for toxic chemicals. Certain MS/MS criteria need to be met for qualitative identifications to be made, and several entities worldwide have devised different criteria for regulatory purposes. ARS scientists in Wyndmoor, Pennsylvania, compared the three most common sets of identification criteria in the validation of a simple “extract & inject” sample preparation method for 169 veterinary drugs in eggs. Although the current MS/MS identification criteria used by the USDA performed just as well as the other sets of criteria, one of the European criteria were simpler to implement. The USDA National Residue Program should adopt the simpler qualitative identification criteria evaluated in this study to improve monitoring efficiency and harmonize with global standards. Development of a contactless polytetrafluoroethylene membrane gas-liquid separator (GLS). Membrane GLS has problems with clogging, structural deterioration, and operation disruption. ARS scientists in Wyndmoor, Pennsylvania, developed a new GLS that eliminates liquid-membrane contact to greatly extend the ruggedness of the device. For elements with unstable hydrides, such as lead and cadmium, the small interior volume of the GLS also reduces residence time and sample degradation. This research will improve the analysis of toxic metals in foods, which helps to increase food safety. All objectives and milestones of the 5-year project were fully met, except for Objective 6, which was ended due to the resignation and abolishment of the position in 2018 of the scientist leading investigations on antimicrobial resistance. Analytical methods using mass spectrometry for the detection of biomarkers indicating antimicrobial resistance were developed, but the planned correlation with samples containing antibiotic residues could not be conducted. The COVID-19 pandemic and closure of the lab in March 2020 for more than 15 months limited the monitoring of samples for pesticides, veterinary drugs, and environmental contaminants, but the food packaging analyses were completed before the lab closure.

Accomplishments
1. Identifying chemicals migrating from food packaging. ARS scientists in Wyndmoor, Pennsylvania, in collaboration with USDA Food Safety and Inspection Service (FSIS), studied the migration of chemicals from paper and plastic food contact materials, including pizza boxes, butcher paper, egg containers, oven bags, and microwave and meal trays. A novel approach for the confident identification of chemicals using high-resolution mass spectrometry was developed. Over 100 migrated chemicals were identified, including substances intentionally added to food contact materials worldwide and their derivatives and degradation products. Concentrations of the identified chemicals with established migration limits were below the regulatory levels, suggesting no health concerns. However, some chemicals were reported for the first time, warranting future investigations.

Review Publications
Sapozhnikova, Y.V. 2021. Non-targeted screening of chemicals migrating from paper-based food packaging by GC-Orbitrap mass spectrometry. Talanta. Volume 226: 1-10. https://doi.org/10.1016/j.talanta.2021.122120.
Michlig, N., Lehotay, S.J., Lightfield, A.R., Horacio, B., Maria, R. 2021. Validation of a high-throughput method for analysis of pesticide residues in hemp and hemp products. Journal of Chromatography A. 1645. https://doi.org/10.1016/j.chroma.2021.462097.
Lehotay, S.J., Lightfield, A.R. 2021. Comparison of four different multiclass, multiresidue sample preparation methods in the analysis of veterinary drugs in fish and other food matrices. Analytical and Bioanalytical Chemistry. 3223–3241. https://doi.org/10.1007/s00216-021-03259-x.
Sapozhnikova, Y.V., Nunez, A., Johnston, J. 2021. Screening of chemicals migrating from plastic food contact materials for oven and microwave applications by LC- and GC-Orbitrap MS. Journal of Chromatography A. 462261. https://doi.org/10.1016/j.chroma.2021.462261.
Lehotay, S.J., De Zeeuw, J., Sapozhnikova, Y.V., Michlig, N., Rousova, J., Konschnik, J.D. 2020. There is no time to waste: low-pressure gas chromatography–mass spectrometry is a proven solution for fast, sensitive, and robust GC–MS analysis. LC GC North America. 38(8):457-464.
Ninga, E., Sapozhnikova, Y.V., Lehotay, S.J., Lightfield, A.R., Monteiro, S. 2020. High-throughput mega-method for the analysis of pesticides, veterinary drugs, and environmental contaminants in catfish by UHPLC-MS/MS and robotic mini-SPE cleanup + LPGC-MS/MS. Journal of Agricultural and Food Chemistry. https://doi.org/10.1021/acs.jafc.0c00995.
Ji, M., Jixin, L., Xuefei, M., Chen, G., Chunsheng, L., Yongzhong, Q. 2020. A portable and field optical emission spectrometry coupled with microplasma trap for high sensitivity analysis of arsenic and antimony simultaneously. Talanta. available online:Talanta 218 (2020)121161. https://doi.org/10.1016/j.talanta.2020.121161.
Sapozhnikova, Y.V., Zomer, P., Gerssen, A., Nunez, A., Mol, H.G. 2020. Evaluation of flow injection mass spectrometry approach for rapid screening of selected pesticides and mycotoxins in grain and animal feed samples. Food Control. 116. https://doi.org/10.1016/j.foodcont.2020.107323.
Rodriguez-Ramos, R., Lehotay, S.J., Michlig, N., Socas-Rodriguez, B., Rodriguez-Delgado, M.A. 2020. Critical review and re-assessment of analyte protectants in gas chromatography. Journal of Chromatography A. https://doi.org/10.1016/j.chroma.2020.461596.