Source: UNIV OF MASSACHUSETTS submitted to
IN SITU AND REAL TIME MONITORING AND CHARACTERIZATION OF PESTICIDE RESIDUES ON AND IN FRESH PRODUCE USING SERS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
TERMINATED
Funding Source
AFRI COMPETITIVE GRANT
Reporting Frequency
Annual
Accession No.
1007558
Grant No.
2016-67017-24458
Project No.
MASW-2015-05731
Proposal No.
2015-05731
Multistate No.
(N/A)
Program Code
A1331
Project Start Date
Nov 1, 2015
Project End Date
Oct 31, 2019
Grant Year
2016
Project Director
He, L.
Recipient Organization
UNIV OF MASSACHUSETTS
(N/A)
AMHERST,MA 01003
Performing Department
Food Science
Non Technical Summary
Pesticide applications on fresh produce are strictly regulated and monitored due to their toxicities to human health. The overall goal of this proposal is to investigate the behaviors and fate of multi-class pesticides on and in fresh produce (i.e. apples, grapes, and spinach leaves). Innovative methods (i.e. surface enhanced Raman spectroscopy,SERS) will be developed and optimized for study surface and internalized pesticides, respectively. We will then use the method to monitor and characterize the pesticide residues on plant surfaces over time and after postharvest washing. We will also investigate the penetration and translocation of pesticides in fresh produce.The objectives outlined are consistent with the call of Program Area Priorities (Code - A 1331) to "Elucidate physical or molecular mechanisms that allow chemicals to internalize into fresh produce" and "Investigate the fate of foodborne hazards in or on fresh produce associated with produce processing;". The successful completion of this study will establish innovativemethods to monitor and characterize pesticides on and in fresh produce, and gain knowledge on the behaviors and fate of pesticide residues on and in fresh produce. Understanding these processes will help us to develop a better strategy to apply pesticides and reduce pesticide exposures from food.
Animal Health Component
0%
Research Effort Categories
Basic
100%
Applied
(N/A)
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
71152202000100%
Knowledge Area
711 - Ensure Food Products Free of Harmful Chemicals, Including Residues from Agricultural and Other Sources;

Subject Of Investigation
5220 - Pesticides;

Field Of Science
2000 - Chemistry;
Goals / Objectives
The Overall Goal is to investigate the behaviors and fate of pesticides on and in fresh produce in situ and in real time.Objective 1: Optimize the SERS methods for in situ and real time monitoring and characterization of multi-class pesticides on and in different fresh produce.Objective 2: Monitor the pesticide residues on fresh produce over time and after postharvest washing.Objective 3: Investigate the penetration and translocation of pesticides in fresh produce.
Project Methods
Objective 1: Optimize the SERS methods for in situ and real time monitoring and characterization of multi-class pesticides on and in different fresh produce. Based on our preliminary data, we have been able to measure the signals of pesticides on and in tea leaves in situ and in real time. In this objective, we will further optimize the method for studying the surface pesticides (objective 2) and the internalized pesticides (objective 3), respectively.Objective 2: Monitor the pesticide residues on fresh produce over time and after postharvest washing. After intentionally contaminating the pesticides on various surfaces of fresh produce (i.e. apples, grapes, and spinach leaves), we will monitor and characterize the surface pesticide residues over time. We will also evaluate the effectiveness of different postharvest washing methods on removing surface pesticide residues.Objective 3: Investigate the penetration and translocation of pesticides in fresh produce. For the penetration study, we will investigate the behaviors of both non-systemic and systemic pesticides into plant tissues at micrometer scales. For the translocation study, we will grow spinach plants in both hydroponic and soil systems with systemic pesticides, and monitor the pesticide signals and characterize their degradations in leaves over time.

Progress 11/01/15 to 10/31/19

Outputs
Target Audience:Scientists and government decision makers were reached through presenting our work in conferences and journal papers. Industrial people and consumers were reached through media reports. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Fivephd students,two undergraduatesandthree postdoc researchers were involved or partially involvedin the research project, and obtained traning through conducting the research experiment. The students and scholarsalso got trained to present their research workin several conferences and publish journal papers. Iincorporated some findings into the lectures in my food chemistry II course, which has ~ 50 students from food science, chemistry, and bio- chemistry. I also ran a short course on Raman/SERS for food application to public with ~40 participantsfrom acdemics and industries. How have the results been disseminated to communities of interest?through papers, conference presentations, invited talks,short course, and media reports. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? 1. Wedeveloped effective SERS mapping methods to study the behaviors (penetration, degradation,translocation, and transimission) of pesticides in various plants. 2. We developed an effective washing method to remove surface pesticides from fresh produce. 3. We filled in the knowledge gap on the penetration depth of pesticides in various produces. This is the first time that such information was obtained which will facilitate us to developeffective and safer pesticide formulations and stratgies to reducepesticide exposure.

Publications

  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Yang, Tianxi, Yanqi Qu, Michael E. Hickey, Weicang Wang, Bin Zhao, Shuilian Bi, Guodong Zhang, and Lili He. "Mapping of Pesticide Transmission on Biological Tissues by Surface Enhanced Raman Microscopy with Gold Nanoparticle Mirror." ACS applied materials & interfaces (2019).https://doi.org/10.1021/acsami.9b16084
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Yang, Tianxi, Jeffery J. Doherty, Huiyuan Guo, Bin Zhao, John M. Clark, Baoshan Xing, Ruyan Hou, and Lili He*. "Real-time monitoring of pesticide translocation in tomato plants by surface enhanced Raman spectroscopy." Analytical chemistry (2019). 91, 3, 2093-2099
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Tu, Qin, Tianxi Yang, Yanqi Qu, Siyue Gao, Zhiyun Zhang, Yilei Wang, Jinyi Wang, and Lili He*. "In situ colorimetric detection of glyphosate on plant tissues using cysteamine-modified gold nanoparticles." Analyst (2019). 144, 2017-2025.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Tu, Qin, Michael E. Hickey, Tianxi Yang, Siyue Gao, Qingmiao Zhang, Yanqi Qu, Xinyi Du, Jinyi Wang, and Lili He*. "A simple and rapid method for detecting the pesticide fipronil on egg shells and in liquid eggs by Raman microscopy." Food Control (2019). 96. 16-21. https://doi.org/10.1016/j.foodcont.2018.08.025
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Lili He. Invited talk. Surface Enhanced Raman Microscopy for Studying the Behaviors of Pesticides and Nanoparticles on/in Plants in Situ. IAFP annual conference. KT. July 2019
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Lili He. Invited talk. A SERS-active fiber containing needle for one-step multiphase sample preparation and minimum invasive detection. TechConnect World Innovation Conference. MA. June 2019
  • Type: Conference Papers and Presentations Status: Other Year Published: 2018 Citation: Lili He. Invited talk. Pesticide analysis using SERS. BASF innovation event. MA. Oct. 2018
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Tianxi Yang, Lili He. Surface-enhanced Raman spectroscopy for food safety applications. Eastern Analytical Symposium (EAS) conference. NJ. Oct. 2018
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Qin Tu, Lili He. Rapid detection of the Pesticide Fipronil on Egg Shells and in Liquid Eggs by Raman Microscopy. EAS conference. NJ. Nov. 2018


Progress 11/01/17 to 10/31/18

Outputs
Target Audience:Scientists and government decision makers were reached through presenting our work in conferences and journal papers. Industrial people andconsumers were reached through media reports. Changes/Problems:We requested a no-cost extension to finishup the translocation and transmission study. What opportunities for training and professional development has the project provided?We have trained 1 phd student and 1 postdoc researcher directly through the research project. We also presented our work in several conferences and journal papers. I also incorporated some findings into the lectures in my food chemistry II course. How have the results been disseminated to communities of interest?Idid more than 30 interviews for talking on my pesticide washing study, requested by media such as CNN, USA today, TIME, New York Daily News, The Boston Globe, Consumer reports, C&EN, Science Daily, KCBS/San Francisco, The Times, London, French national newspaper Le Figaro, Corus, Toronto Canada, Russian federal channel NTV, etc. I provided consultation for several industrial people who are interested in pesticide detection. What do you plan to do during the next reporting period to accomplish the goals?We are planning to further study the translocation of pesticides from plant root to different organs as well as the plant stress during the translocation. We will also study the transmission of pesticides from plant surfaces to the skin.

Impacts
What was accomplished under these goals? Understanding the behavior of pesticide translocation is significant for effectively applying pesticides and reducing pesticide exposures from treated plants. Herein, we applied surface-enhanced Raman spectroscopy (SERS) for real-time monitoring of pesticide translocation in tomato plant tissues, including leaves and flowers, following root exposure in hydroponic and soil systems. Various concentrations of the systemic pesticide, thiabendazole, was introduced into hydroponic systems used for growing tomato plants. At selected time internals, tomato leaves and flowers were picked and thiabendazole measured directly under a Raman microscope after pipetting a 5 µL aliquot of a gold nanoparticle-containing solution onto the plant tissue surface to enhance pesticides signals. We found that the pesticide signals first appeared along the midrib in the lowest leaves and moved distally to the edge of the leaves. As the concentration of pesticide applied to the root was increased, the time necessary to detect the signal was decreased. Liquid chromatography tandem-mass spectrometry (LC-MS/MS) determined that there was approximately 2 μg/g of thiabendazole on leaves following either a 48-h exposure to a 10 mg/L (ppm) solution or a 12 h exposure to a 200 mg/L solution, respectively. The SERS surface mapping method was also able to detect thiabendazole in the trichomes of the leaves. In addition, we found a unique SERS peak at 737 cm-1 on both leaves and flowers at 4 and 6 days following the application of 200 mg/L of thiabendazole to the hydroponic system. The peak at 737 cm-1 appears to be coming from adenine-containing materials and may be related to the plant's response to pesticide toxicity, which could be used as a potential marker for monitoring plant responses to stresses. The SERS method thus provides a rapid and effective way to study the real-time translocation behavior of pesticides in a plant system. The information obtained here could provide useful guidance for effective and safe applications of pesticides to plants.

Publications

  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Tianxi Yang, Jeffery Doherty, Bin Zhao, Amanda J. Kinchla, John M. Clark, and Lili He*. 2017. Effectiveness of Commercial and Homemade Washing Agents in Removing Pesticide Residues on and in Apples. 65 (44), pp 97449752.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Haoxin Chen, Chunrong Wang, Zhiyun Zhang, and Lili He*. Combining Headspace Solid-Phase Microextraction and Surface-Enhanced Raman Spectroscopy To Detect the Pesticide Fonofos in Apple Juice. Journal of food protection. 81, no. 7 (2018): 1087-1092.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Lili He. Real-time and in situ investigation of pesticide behaviors in plants using surface enhanced Raman spectroscopy. SciX. Oct. 9. 2017 Reno, NV
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Tianxi Yang and Lili He. In situ and real-time monitoring and characterization of pesticide residues on and in fresh produce using SERS. ACS spring meeting. March. New Orleans, LA
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Tianxi Yang and Lili He. Mapping of Pesticides on Biological Samples by Surface Enhanced Raman Spectroscopy with Gold nanoparticle mirror. IAFP annual meeting. July. Salt lake city, UT.
  • Type: Theses/Dissertations Status: Published Year Published: 2018 Citation: Tianxi Yang. PhD Dissertation. IN SITU AND REAL-TIME MONITORING AND CHRACTERIZATION OF PESTICIDE RESIDUES ON AND IN FRESH PRODUCE USING SERS.


Progress 11/01/16 to 10/31/17

Outputs
Target Audience:Scientists and govenment decision makers were reached through presenting our work in conferences and journal papers Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?We have trained 1 phd student and 1 undergraduate student directly through the research project. We also presented our work in several conferences and journal papers. I also incorporated some findings into the lectures in my food chemistry II course. How have the results been disseminated to communities of interest?I provided consultation for several industrial people who are interested in pesticide detection What do you plan to do during the next reporting period to accomplish the goals?We are planning to study the traslocation of pesticides from plant root to different organs in the next year

Impacts
What was accomplished under these goals? Removal of pesticide residues from fresh produce is crucial for reducing hazards to environment and humans. We investigated the effectiveness of commercial and homemade washing agents to remove the surface and internalized pesticide residues from apples. For elimination of surface pesticides, sodium bicarbonate (baking soda, NaHCO3) solution reduced more pesticide residues than tap water and Clorox bleach. With 1% baking soda washing solution, it took 12 min and 15 min to completely remove the surface thiabendazole and phosmet, respectively when pesticides applied in the concentration of 125 ng/cm2 on apples after 24 h exposure. Meanwhile, HPLC-MS results showed that there were 20 % of thiabendazole and 4.4 % of phosmet penetrated into apples after 24 h exposure. Thiabendazole, a systemic pesticide, penetrated further than the non-systemic pesticide phosmet into apple peel overtime, which led to more residues inside the apples that could not be washed away. This study gives us the information that standard postharvest washing method with Clorox bleach solution for washing 2 min cannot effectively wash off pesticide on apples. Baking soda is more effective in removing pesticides on apples, but not those in apples. The higher degree of pesticide penetration, the lower effectiveness of overall removal of the pesticides from fresh produce.

Publications

  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Tianxi Yang, Bin Zhao, Ruyan Hou, Zhiyun Zhang, Amanda J. Kinchla, John M. Clark, and Lili He*. 2016. Evaluation of the penetration of multiple classes of pesticides in fresh produce using surface-enhanced Raman scattering mapping. Journal of Food Science. 81,11, T2891T2901.
  • Type: Book Chapters Status: Published Year Published: 2016 Citation: Yang, T., Wang, P., Guo, H., He, L.*, 2016. Surface-Enhanced Raman Spectroscopy: A Tool for All Classes of Food Contaminants. Reference Module in Food Sciences. Elsevier, pp. 18. doi: http://dx.doi.org/10.1016/B978-0-08-100596-5.21090-1
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Yang, T., Zhao, B., Kinchla, A. J., Clark, J. M., & He, L.* (2017). Investigation of Pesticide Penetration and Persistence on Harvested and Live Basil Leaves Using Surface-Enhanced Raman Scattering Mapping. Journal of Agricultural and Food Chemistry, 65(17), 3541-3550.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Yang, Tianxi, Guo, Huiyuan, Doherty, Jeffery, Zhao, Bin, Xing, Baoshan, Clark ,John M. and Lili He*. poster. In Situ and Real-Time Monitoring of Pesticide Translocation and Persistence in Tomato Plants by Surface Enhanced Raman Spectroscopy. SERS, faraday discussion. Glasgow, Scotland. Aug. 2017
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Lili He. invited talk. Real-time and in situ investigation of pesticide behaviors in plants using surface enhanced Raman spectroscopy. ACS conference. DC. Aug. 2017
  • Type: Other Status: Published Year Published: 2017 Citation: Invited talk. Surface-enhanced Raman spectroscopy: One tool for multiple food contaminants. Thermo Fisher Scientific Webinar. June. 2017.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Lili He. In situ and real time study of pesticide behaviors in live plants using SERS. NIFA food safety program grantee meeting. Florida. July 2017
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Tianxi Yang and Lili He. Investigation of pesticides penetration and persistence on harvested and live basil leaves using surface enhanced Raman scattering mapping. IFT. Las Vegas, NV, June, 2017
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Tianxi Yang and Lili He. Oral presentation. Real-Time and In-Situ Monitoring of Pesticide Penetration in Edible Leaves by SERS Mapping. Eastern Analytical Symposium & Exposition. Somerset, New Jersey. Nov. 2016


Progress 11/01/15 to 10/31/16

Outputs
Target Audience:Scientists and govenment decision makers were reached through presenting our work in conferences and journal papers. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?We have trained 1 phd student and 1 undergraduate student directly through the research project. We also presented our work in several conferences and journal papers. I also incorporated some findings into the lectures inmy food chemistry II course. How have the results been disseminated to communities of interest?I provided consultation forseveral industrial people who are interested in pesticide detection What do you plan to do during the next reporting period to accomplish the goals?We are working on the evaluation of the effectiveness of different produce washing solution on removing the surface and internalized pesticides in fresh produce. We will use both SERS and HPLC-MS to qualitatively and quantitatively measure the pesticide residues.

Impacts
What was accomplished under these goals? We have optimized and applied the SERS methods forin situand real time monitoring and characterization of two systemic pesticides,thiabendazole and acetamiprid, and two non-systemic pesticides,ferbam and phosmet,on and in three fresh produce,apples, grapes and spinach leaves. The result showsystemic pesticides penetrated more rapidly and deeply after 48 h exposure into the tested fresh produce than the non-systemic pesticides. The fact that two non-systemic pesticides were also able to penetrate over time into all three fresh produce tested may raise additional safety concerns. Comparatively, grapes were generally more resistant for pesticide penetration compared to apples and grapes. The information obtained here could provide technical support and guidance for accurate, effective and safe application of pesticides and reduction of pesticide exposure from fresh produce.

Publications

  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Yang, Tianxi, Zhiyun Zhang, Bin Zhao, Ru-Yan Hou, Amanda Kinchla, John M. Clark, and Lili He*. "Real-time and in situ monitoring of pesticide penetration in edible leaves by surface-enhanced Raman scattering mapping." Analytical Chemistry. 2016, 88 (10), pp 5243-5250.
  • Type: Journal Articles Status: Accepted Year Published: 2016 Citation: Tianxi Yang, Bin Zhao, Ruyan Hou, Zhiyun Zhang, Amanda J. Kinchla, John M. Clark, and Lili He*. 2016Evaluation of the penetration of multiple classes of pesticides in fresh produce using surface-enhanced Raman scattering mapping. Journal of Food Science.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Lili He. invited talk. Surface enhanced Raman Spectroscopy: one tool for all food contaminants. ACS C&EN Talented 12 symposium. Aug 2016
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Lili He. oral presentation. In situ SERS detection of multiclass insecticides on plant surfaces. Pacifichem 2015. Dec. 2015
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Lili He. oral presentation. Real-time and in situ monitoring of pesticide penetration in edible leaves by surface-enhanced Raman scattering mapping. NIFA food safety project director annual meeting. July 2016
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Tianxi Yang and Lili He. oral presentation. Real-time and in situ monitoring of pesticide penetration in edible leaves by surface-enhanced Raman scattering mapping. ACS-AGFD international student symposium. Aug 2016
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Tianxi Yang and Lili He. Poster presentation. Evaluation of the penetration of multiple classes of pesticides in fresh produce using surface-enhanced Raman scattering mapping. 13th internaitonal phytotechnologies conference, Hangzhou, China. Sept 2016.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Pang, Shintaro, Tianxi Yang, and Lili He*. 2016. "Review of surface enhanced raman spectroscopic (SERS) detection of synthetic chemical pesticides."TrAC Trends in Analytical Chemistry. doi:10.1016/j.trac.2016.06.017
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Lili He. invited talk. Development and applications of surface enhanced Raman spectroscopy in food safety. College of Chemistry and Chemical Engineering. Xiamen University. March, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Lili He. invited talk. Development of Surface enhanced Raman Spectroscopy for Food Safety Applications. Umass Stockbridge School of Agriculture seminar. Feb. 2016.