Source: MICHIGAN STATE UNIV submitted to NRP
BENEFICIAL REUSE OF RESIDUALS AND RECLAIMED WATER: IMPACT ON SOIL ECOSYSTEM AND HUMAN HEALTH (FORMERLY W2170)
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
HATCH
Reporting Frequency
Annual
Accession No.
1004794
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
W-3170
Project Start Date
Nov 5, 2014
Project End Date
Sep 30, 2019
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
MICHIGAN STATE UNIV
(N/A)
EAST LANSING,MI 48824
Performing Department
Plant, Soil and Microbial Science
Non Technical Summary
"Consumption of pharmaceutical-tainted fresh produce represents a direct route of human exposure. The pharmaceuticals accumulated in agricultural produce originate primarily from land application of animal manures/sewage biosolids and/or irrigation with reclaimed water. Pharmaceutical intake due to consumption of fresh produce generally indicates minimal risk to human health. However, chronic consumption of agricultural produce containing trace levels of antibiotics could potentially increase the populations of antibiotic-resistant bacteria in the gastrointestinal tracts of animals and humans. Thus, mitigating the uptake of antibiotics by vegetables during agricultural production is a crucial step in improving food safety. We hypothesize that water flow in soils and in vegetables is the major route by which pharmaceuticals are translocated from soils to vegetables. The accumulation of pharmaceuticals depends on vegetable types, plant tissue constituents and growth condition, physicochemical properties of pharmaceuticals, and soil properties. Our goal is to mitigate the uptake of pharmaceuticals in vegetables by reducing their concentrations in the water flow to the vegetables. We are integrating data obtained from hydroponic studies and greenhouse soil-pot experiments to evaluate pharmaceutical uptake by vegetables at environmentally relevant concentrations, and elucidate the mechanistic determinants of vegetable accumulation of pharmaceuticals. The knowledge generated from this project will be utilized to guide novel approaches aimed at minimizing pharmaceutical uptake by vegetables in agricultural production."
Animal Health Component
20%
Research Effort Categories
Basic
60%
Applied
20%
Developmental
20%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
1330110200070%
1024010200030%
Knowledge Area
133 - Pollution Prevention and Mitigation; 102 - Soil, Plant, Water, Nutrient Relationships;

Subject Of Investigation
0110 - Soil; 4010 - Bacteria;

Field Of Science
2000 - Chemistry;
Goals / Objectives
Evaluate the short- and long-term chemistry and bioavailability of nutrients, potentially toxic inorganic trace elements, and pharmaceuticals and personal care products (TOrCs) in residuals, reclaimed water, and amended soils in order to assess the environmental and health risk-based effects of their application at a watershed scale. Specific tasks: (i) To develop and evaluate in vitro (including chemical speciation) and novel in vivo methods to correlate human and ecological health responses with risk-based bioavailability of trace elements and TOrCs in residuals and residual-treated soils. (ii) Predict the long-term bioavailability and toxicity of trace elements and TOrCs in residual-amended urban, agricultural and contaminated soils. (iii) Evaluate long-term effects of residuals application and reclaimed wastewater irrigation on fate and transport of nutrients, trace elements, TOrCs, and emergence/spread of antibiotic resistance in high application rate systems. (iv) Evaluate plant uptake and ecological effects of potentially toxic trace elements and TOrCs from soils amended with residuals and reclaimed wastewater. Evaluate the uses and associated agronomic and environmental benefits for residuals in agricultural and urban systems. Specific tasks: (i) Evaluate the ability of in situ treatment of contaminated soil with residuals to reduce chemical contaminant bioavailability and toxicity. (ii) Determine the climate change impacts of organic residuals end use options (i.e., C sequestration, N2O emissions). (iii) Quantify sustainability impacts such as water quality (reduced N impairment) and quantity benefits (increased plant available water, increased drought tolerance) and soil quality improvements associated with a range of organic residuals end uses. (iv) Explore the potential for waste by-products to be used in urban areas including urban agriculture, stormwater infrastructure, green roofs, and in urban green space. (v)Evaluate ecosystem services of degraded urban soils amended with residuals. (vi) Use tools such as life cycle assessment to understand and compare the impacts of a range of residuals end use/disposal options.
Project Methods
We will measure sorption of pharmaceuticals by soils, and determine their bioavailability for expression of antibiotic resistance genes.

Progress 11/05/14 to 09/30/19

Outputs
Target Audience:The target audiences include, but not limited to, scientists, policy makers, commodity groups, as well as individuals and the public who are interested in the relevant issues. The materials and results from this project are also disseminated to graduate students and undergraduate students at Michigan State University. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project has provided many opportunities to train postdoctoral research associates and graduate students who have been benefited from this research project by improving their laboratory skills, critical thinking and problem solving capability. The specific training includes the integration of data analysis, manuscript writing, presentations at conferences, publication in peer- review journals, and preparation of research proposals for competitive programs. This has helped trainees to advance their professional development and careers. How have the results been disseminated to communities of interest?The results from this project have been disseminated primarily through publications as peer-reviewed journal articles and presentations at professional conferences to scientists and policy makers. The public could also access the relevant reports and materials. In addition, the research results have been incorporated into the courses that Hui Li is teaching at Michigan State University, which are disseminated to students from multiple disciplines at both graduate and undergraduate levels. What do you plan to do during the next reporting period to accomplish the goals?This is the final report to this project. The project has been renewed as W4170 in 2019.

Impacts
What was accomplished under these goals? The dissemination of pharmaceuticals in agroecosystems originating from land application of animal manure/sewage sludge and irrigation with treated wastewater in agricultural production has raised concern about the accumulation of pharmaceuticals in food products. The pathways of pharmaceutical entries via plant roots, transport to upper fractions, and the factors influencing these processes have yet been systematically elucidated, thus impeding the development of effective measures to mitigate pharmaceutical contamination in food crops. In this study, lettuce uptake of thirteen commonly used pharmaceuticals was investigated using a hydroponic experimental setting. Pharmaceutical sorption by lettuce roots was measured in order to evaluate the influence on pharmaceutical transport from roots to shoots. Small-sized pharmaceuticals e.g., caffeine and carbamazepine with molecular weight (MW) < 300 g/mol and a low affinity to lettuce roots (sorption coefficient <50 L/Kg) manifested substantial transport to shoots. Small-sized molecules lamotrigine and trimethoprim had a relatively strong affinity to lettuce roots (sorption coefficient > 12000 L/K g) and demonstrated a reduced transport to shoots. Large-sized pharmaceuticals (e.g. MW > 400 g/mol) including lincomycin, monensin sodium, and tylosin could be excluded from cell membranes, resulting in the predominant accumulation in lettuce roots. Large-sized oxytetracycline existed as zwitterionic species that could slowly enter lettuce roots; however, the relatively strong interaction with lettuce roots limits its transport to shoots. The mass balance analysis revealed that acetaminophen, β-estradiol, carbadox, estrone and triclosan were readily metabolized in lettuce with >90% loss during 144-h exposure period. A scheme was proposed to describe pharmaceutical uptake and transport in plant, which could reasonably elucidate many literature-reported results. Molecular size, reactivity and ionic speciation of pharmaceuticals, as well as plant physiology, collectively determine their uptake, transport and accumulation in plants. Pharmaceuticals can be taken up by vegetable roots from soils plausibly via soil pore water. Currently, it is not clear about the role of pore water in plant uptake of pharmaceuticals from soils. In this study, the fate, uptake and distribution of fifteen commonly used pharmaceuticals in soil-water-radish systems were investigated to examine the relationship between the accumulation and their physicochemical processes in soils. The results indicate that the distribution of pharmaceuticals between soil and pore water, as well as their biodegradation, combined to govern the bioavailability of pharmaceuticals to plant uptake. Fourteen out of 15 pharmaceuticals could enter radish tissues in which the accumulation ranged from 2.1 to 14080 ng/g. Comparison of bioconcentration factors (BCFs) on the basis of pharmaceutical concentration in bulk soil vs. in pore water implies that pharmaceuticals present in soil pore water are the major bioavailable fractions to plant uptake. The pore water-based BCFs exhibited a positive linear relationship with log Dow for the pharmaceuticals with >90% as neutral species in soil pore water, while such relationship was not observed between bulk soil-based BCFs and log Dow mainly due to sorption by soil. Other than hydrophobicity, the dissociation of ionizable pharmaceuticals in the soil pore water and (or) root cells may lead to the "ion trap" effects and thus influence the uptake and translocation process. The large molecular-size pharmaceuticals (e.g., tylosin) manifested a minimum uptake due plausibly to the limited permeability of cell membranes.

Publications

  • Type: Journal Articles Status: Accepted Year Published: 2019 Citation: Yuanbo Li, Cary T Chiou, Hui Li, and Jerald L Schnoor, 2019, Improved Prediction of the Bioconcentration Factors of Organic Contaminants from Soils into Plant/Crop Roots by Related Physicochemical Parameters. Environment International. 126:46-53.
  • Type: Journal Articles Status: Accepted Year Published: 2019 Citation: Yuanbo Li, J. Brett Sallach, Wei Zhang, Stephen A. Boyd, and Hui Li, 2019, Insight into the Distribution of Pharmaceuticals in Soil-Water-Plant Systems, Water Research, 152: 38-46.
  • Type: Journal Articles Status: Accepted Year Published: 2019 Citation: Ya-Hui Chuang, Cheng-Hua Liu, J. Brett Sallach, Raymond Hammerschmidt, Wei Zhang, Stephen A. Boyd, and Hui Li, 2019, Mechanistic Study on Uptake and Transport of Pharmaceuticals in Lettuce from Water, Environment International. 131, 104976.
  • Type: Journal Articles Status: Accepted Year Published: 2019 Citation: Zhirui Qin, Zhenhua Zhao, Liling Xia, Abduelrahman Adam, Yong Li, Deqiang Chen, Sara Margaret Mela, and Hui Li, 2019, The Dissipation and Risk Alleviation Mechanism of PAHs and Nitrogen in Constructed Wetlands: The Role of Submerged Macrophytes and their Biofilms-leaves, Environment International. 131, 104940.
  • Type: Journal Articles Status: Accepted Year Published: 2019 Citation: Cheng-Hua Liu, Ya-Hui Chuang, Hui Li, Stephen A. Boyd, Brian J. Teppen, Javier M. Gonzalez, Cliff T. Johnston, Johannes Lehmann, and Wei Zhang, 2019, Long-term Sorption of Lincomycin to Biochars: The Intertwined Roles of Pore Diffusion and Dissolved Organic Carbon, Water Research, 161:108-118.
  • Type: Journal Articles Status: Accepted Year Published: 2019 Citation: Cheng-Hua Liu, Wenying Chu, Hui Li, Stephen A. Boyd, Brian J. Teppen, Jingdong Mao, Johannes Lehmann, and Wei Zhang, 2019, Quantification and Characterization of Dissolved Organic Carbon from Biochars, Geoderma, 335: 161-169.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Geoff Rhodes, Ya-Hui Chuang, Wei Zhang, Stephen A. Boyd, and Hui Li, 2019, Uptake of Cephalexin from Water to Three Vegetables, International Soil Meeting (Soil Science Society of America, Soil Science Society of Canada, and Soil Science Society of Mexico), San Diego, California. January 6-9.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Yuanbo Li, J. Brett Sallach, Wei Zhang, Stephen A. Boyd and Hui Li, 2019, Insight into the Distribution of Pharmaceuticals in Soil-Water-Plant System. International Soil Meeting (Soil Science Society of America, Soil Science Society of Canada, and Soil Science Society of Mexico), San Diego, California. January 6-9.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Hui Li, Ya-Hui Chuang, Cheng-Hua Liu, J. Brett Sallach, Wei Zhang, Ray Hammerschmidt, and Stephen Boyd, 2018, Uptake, Accumulation and Metabolism of Pharmaceuticals in Vegetables. International Symposium on Agro- Environmental Quality, Nanjing, China, November 3-5. (invited keynote
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Hui Li, Yuanbo Li, J. Brett Sallach, Wei Zhang, and Stephen A. Boyd, 2018, Uptake of Pharmaceuticals by Plant from Soils: Role of Soil Pore Water. 2018 International Conference on Agro-Food Safety and Nutrition, Nanjing, Jiangsu, China. October 20-23. (invited)


Progress 10/01/17 to 09/30/18

Outputs
Target Audience:Scientists, and policy makers, as well as individuals and the general public who are interested in the relevant issues. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project has provided many opportunities to train postdoctoral research associates and graduate students who have been benefited from this research project by improving their laboratory skills, critical thinking and problem solving. This training is to helpthem to advance their professional development and careers by intergrating data analysis, writingmanuscripts, publishing peer-review journal articles, and preparing research proposalsfor competitive programs. How have the results been disseminated to communities of interest?The results from this project have been disseminated primarily through publications as peer-reviewed journal articlesand presentations at professional conferences to scientists and policy makers. The general public could also access the relevant reports and materials. In addition, the research results have been incoporated into fourcourses that Hui Li is teaching at Michigan State University, and been disseminated the students at both graduate and undergraduate levels. What do you plan to do during the next reporting period to accomplish the goals?We have plan to conduct more experiments to elucidate vegetable uptake mechanism of pharmaceuticals fromwater and soils. Duringthe next reporting period, we will put more efforts to manuscript writingand publication in peer-review journals. In addition, we will start working on PFAS present in biosolids.

Impacts
What was accomplished under these goals? The dissemination of pharmaceuticals in agroecosystems through land application of animal manure/sewage sludge andirrigation withreclaimed water in agricultural production has raised concern about consumption of pharmaceutical-contaminatedvegetables. Little isknown about the pharmaceutical metabolismin plant after uptake from soil and water.Metabolism of pharmaceuticals in plants is important to evaluate their fate and accumulation in vegetables, and subsequently the riskto human health. However, limited knowledge is available to elucidate the metabolism of pharmaceuticals in plants due to the lack of appropriate research approaches. In this study, radish was selected as a model plant to investigate the metabolism of pharmaceuticals in intact plants (in vivo) growing in hydroponic solution and in plant tissue enzyme extracts (in vitro). For caffeine, six phase-I demethylation metabolites identified in the intact radish plant were also found in the plant enzyme extracts. After 7 days of in vivo exposure, the amount of the identified metabolites was about 5.4 times greater than the parent caffeine in radish roots. Furthermore, the metabolism potential of fifteen pharmaceuticals in radish was evaluated on the basis of mass balance. After 7 days of hydroponic exposure, oxytetracycline, trimethoprim, carbamazepine, lincomycin, monensin and tylosin manifested relatively less metabolism with the mass recoveries ranging from 52.3 to 78.2%. In contrast, 17 β-estradiol, sulfamethoxazole, sulfadiazine, estrone, triclosan, acetaminophen, caffeine, carbadox and lamotrigine underwent extensive metabolism with only 3.0-32.1% of parent compound remaining. In the in vitro system, 17 β-estradiol, estrone, triclosan, oxytetracycline, acetaminophen, sulfadiazine and sulfamethoxazole were readily metabolized in radish root enzyme extracts with 1.8 to 34.0% remaining after 96-h exposure. While in the leaf enzyme extracts, only triclosan was rapidly metabolized with 49.2% remaining, and others pharmaceuticals were ≥ 60%, indicating varying extents of metabolism occurred in the different plant parts. This study suggests that plant tissue enzyme extracts could serve as an alternative tool to evaluatethe pharmaceutical metabolism in plants.

Publications

  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Yuanbo Li, Ya-Hui Chuang, J. Brett Sallach, Wei Zhang, Stephen A. Boyd, and Hui Li, 2018, Potential Metabolism of Pharmaceuticals in Radish: Comparison of in vivo and in vitro Exposure. Environmental Pollution, 242:962-969.
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Anping Peng, Juan Gao, Zeyou Chen, Yi Wang, Hui Li, Lena Q. Ma, and Cheng Gu, 2018, Interactions of Gaseous 2-Chlorophenol with Fe3+-Saturated Montmorillonite and their Toxicity to Human Lung Cells. Environmental Science and Technology. 52: 5208-5217.
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Gemini D. Bhalsod, Ya-Hui Chuang, Sangho Jeon, Wenjun Gui, Hui Li, Elliot T. Ryser, Andrey K. Guber, and Wei Zhang, 2018, Uptake and Accumulation of Pharmaceuticals in Overhead- and Surface-Irrigated Greenhouse Lettuce. Journal of Agricultural and Food Chemistry. 66: 822-830.
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Ya-Hui Chuang, Cheng-Hua Liu, Raymond Hammerschmidt, Wei Zhang, Stephen A. Boyd, and Hui Li, 2018, Metabolic Demethylation and Oxidation of Caffeine during Uptake by Lettuce. Journal of Agricultural and Food Chemistry, 66:7907-7915.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Yuanbo Li, Jonathan Brett Sallach, Wei Zhang, Stephen A. Boyd, and Hui Li, 2017, Insight into distribution of pharmaceuticals in soil-water-radish systems. International Annual Meeting of American Society of Agronomy (ASA), Crop Science Society of America (CSSA), and Soil Science Society of America (SSSA), Tampa, Florida. October 22-25.


Progress 10/01/16 to 09/30/17

Outputs
Target Audience:The results from this project have been disseminated primarily through publications in peer-reviewed journal articles and presentations at professional conferences to scientists and policy makers. The results are also reported to the general public who are interested in the relevant issues. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project has provided many opportunities to train postdoctoral research associates and graduate students who have been benefited from this research by improving their laboratory skills, critical thinking, data analysis, manuscript writing, and problem solving. These trainings have helped them to advance their professional development and careers. How have the results been disseminated to communities of interest?The results from this project have been disseminated primarily through publications in peer-reviewed journal articles and presentations in professional conferences to scientists and policy makers. The results are also reported to the general public who are interested in the relevant issues, and have been incorporated in several grduate and undergraduate-level courses taught at Michigan State University. What do you plan to do during the next reporting period to accomplish the goals?We have plan to conduct more experimentste conducted to elucidate vegetable uptake mechanism of pharmaceuticals from water and soils. In the next reporting period, we will focus more on manuscript wring and publication.

Impacts
What was accomplished under these goals? The dissemination of pharmaceuticals in agroecosystems through land application of animal manure/sewage sludge and irrigation with reclaimed water in agricultural production has raised concern about consumption of pharmaceutical-contaminated vegetables. Little is known about the major mechanism of plant uptake of pharmaceuticals from soil and water. In this study, uptake of thirteen commonly used pharmaceuticals by lettuce from water was investigated including acetaminophen, β-estradiol, caffeine, carbadox, carbamazepine, estrone, lamotrigine, lincomycin, monensin sodium, oxytetracycline, triclosan, trimethoprim, and tylosin. Pharmaceutical sorption by lettuce roots was also measured to evaluate the influence on their translocation to shoots. Pharmaceuticals of small size could enter lettuce via symplast pathway, and pharmaceuticals with low affinity to lettuce roots manifested strong translocation to shoots such as caffeine, carbamazepine, lamotrigine and trimethoprim. Large-sized pharmaceuticals such as lincomycin, oxytercycline, monensin sodium and tylosin could be inhibited from diffusing into cell membranes, and hence moved primarily via apoplast pathway as evidenced by accumulation primarily in lettuce roots. The mass balance analysis indicated that acetaminophen, β-estrodiol, carbadox, estrone and triclosan were readily easily metabolized in lettuce with ≥90% loss during the 144-h exposure period. Pharmaceutical molecular size and ionic state, as well as sorption to root constituents, collectively determine pharmaceutical uptake, translocation and accumulation in plants.

Publications

  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Bingyu Wang, Wei Zhang, Hui Li, Heyun Fu, Xiaolei Qu, Dongqiang Zhu, 2017, Micropore Clogging by Leachable Pyrogenic Organic Carbon: A New Perspective on Sorption Irreversibility and Kinetics of Hydrophobic Organic Contaminants to Black Carbon. Environmental Pollution 220: 1349-1358.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Cheng-Hua Liu, Ya-Hui Chuang, Hui Li, Brian J. Teppen, Stephen A. Boyd, Javier M. Gonzalez, Cliff T. Johnston, Johannes Lehmann, and Wei Zhang, 2016, Sorption of Lincomycin by Manure-derived Biochars from Water. Journal of Environmental Quality 45:519-527. (DOI: 10.2134/jeq2015.06.0320).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Ya-Hui Chuang, Cheng-Hua Liu, Jonathan Brett Sallach, Ray Hammerschmidt, Wei Zhang, Stephen A. Boyd, and Hui Li, 2017, Uptake and Metabolization of Caffeine in Lettuce. The 4th International Symposium on the Environmental Dimension of Antibiotic Resistance (EDAR), August 1317, Lansing, Michigan.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Yuanbo Li, Jonathan Brett Sallach, Wei Zhang, Stephen A. Boyd, and Hui Li, 2017, Uptake of Pharmaceuticals by Radish from Soil, The 4th International Symposium on the Environmental Dimension of Antibiotic Resistance (EDAR), August 1317, Lansing, Michigan.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Ya-Hui Chuang, Cheng-Hua Liu, Jonathan Brett Sallach, Ray Hammerschmidt, Wei Zhang, Stephen A. Boyd, and Hui Li, 2017, Uptake, accumulation and metabolization of caffeine in lettuce. The 14th Annual LC-MS/MS Workshop on Environmental and Food Safety, June 11-12, Buffalo, New York.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Ya-Hui Chuang, Cheng-Hui Liu, Ray Hammerschmidt, Wei Zhang, Stephen A. Boyd, and Hui Li, 2016, Accumulation and Metabolism of Caffeine in Lettuce. International Annual Meeting of American Society of Agronomy (ASA), Crop Science Society of America (CSSA), and Soil Science Society of America (SSSA), Phoenix, Arizona, November 6-9.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Ya-Hui Chuang, Cheng-Hui Liu, Ray Hammerschmidt, Wei Zhang, Stephen A. Boyd, and Hui Li, 2016, Influence of Transpiration Stream on Plant Uptake and Translocation of Pharmaceuticals. International Annual Meeting of American Society of Agronomy (ASA), Crop Science Society of America (CSSA), and Soil Science Society of America (SSSA), Phoenix, Arizona, November 6-9.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Wei Zhang, Gemini D. Bhalsod, Ya-Hui Chuang, Sangho Jeon, Wenjun Gui, and Hui Li, 2016, Assessing and Managing Impact of Pharmaceuticals in Irrigation Water on Fresh Produce Safety. International Annual Meeting of American Society of Agronomy (ASA), Crop Science Society of America (CSSA), and Soil Science Society of America (SSSA), Phoenix, Arizona, November 6-9, 2016.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Hui Li, 2016, Uptake of Chemicals of Emerging Concern by Vegetable Crops from Soil and Water. The 2016 China-US Joint Annual Symposium International Nexus of Food, Energy, Water, and Soil, Yixin, Jiangsu Province, China, October 26-29.


Progress 10/01/15 to 09/30/16

Outputs
Target Audience:The results from this project have been disseminated primarily through publications in peer-reviewed journal articles and presentations at professional conferences to scientists and policy makers. The results are also reported to the general public who are interested in the relevant issues. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project has provided many opportunities to train postdoctoral research associates and graduate students who have been benefited from this research by improving their laboratory skills, critical thinking and problem solving. This training has helped them to advance their professional development and careers. How have the results been disseminated to communities of interest?The results from this project have been disseminated primarily through publications in peer-reviewed journal articles and presentations in professional conferences to scientists and policy makers. The results are also reported to the general public who are interested in the relevant issues. What do you plan to do during the next reporting period to accomplish the goals?More experiments have been planned and will be conducted to elucidate vegetable uptake mechanism of pharmaceuticals from water and soils.

Impacts
What was accomplished under these goals? Land application of animal manure and biosolids from wastewater treatment plants to agricultural fields could supply plant nutrients for crop growth, and improve soil quality as well. Agricultural irrigation with reclaimed water mitigates the stress of insufficient fresh water supplies. However, these practices can result in the potential uptake and accumulation of pharmaceuticals in plants. In this study, an efficient and more environmental friendly QuEChERS method was validated and applied to quantify the accumulation of selected pharmaceuticals in lettuce. The extraction recovery of the QuEChERS method ranged from 91.7 to 119.2% for caffeine, carbamazepine, lamotrigine, trimethoprim, monensin and tylosin in lettuce roots, and from 86.3 to 105.3% in shoots. In the kinetic uptake study of pharmaceuticals by well-developed lettuce, the results revealed that the relatively large amounts of caffeine and carbamazepine were distributed in lettuce shoots that that in roots. Lamotrigine and trimethoprim manifested a greater accumulation in lettuce roots than in shoots. The relatively large-sized pharmaceuticals such as monensin and tylosin demonstrated a weak affinity to lettuce root constituents, but were dominantly accumulated in lettuce roots. The analysis of pharmaceutical mass balance in the systems showed that the amount of caffeine and lamotrigine in lettuce roots and shoots kept on decreasing with time, suggesting the occurrence of formation of metabolites in the lettuce. To further elucidate the metabolization processes occurred in lettuce, we developed a reasonable work flow to identify and quantify metabolites of caffeine. This method could be also extended to analyze the metabolites of other types of pharmaceuticals and agrochemicals accumulated in agricultural crops.

Publications

  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Cun Liu, Cheng Gu, Kai Yu, Hui Li, Brian J. Teppen, Cliff T. Johnston, Stephen A. Boyd, and Dongmei Zhou, 2015, Integrating structural and thermodynamic mechanisms for sorption of PCBs by montmorillonite. Environmental Science and Technology 49:2796-2805.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Ya-Hui Chuang, Cheng-Hua Liu, Ray Hammerschmidt, Wei Zhang, Stephen A. Boyd, and Hui Li, 2016, Application of QuEChERS Method to Evaluate Accumulation and Metabolism of Pharmaceuticals in Vegetables, 252nd American Chemical Society National Meeting, Philadelphia, Pennsylvania, August 22-25.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Ya-Hui Chuang, Cheng-Hua Liu, Wei Zhang, Stephen A. Boyd, and Hui Li, 2015, Uptake and Accumulation of Pharmaceuticals in Vegetables. International Annual Meeting of American Society of Agronomy (ASA), Crop Science Society of America (CSSA), and Soil Science Society of America (SSSA), Minneapolis, Minnesota. November 15-18.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ya-Hui Chuang, Yingjie Zhang, Wei Zhang, Stephen A. Boyd, and Hui Li, 2015, Comparison of accelerated solvent extraction and quick, easy, cheap, effective, rugged and safe method for extraction and determination of pharmaceuticals in vegetables. Journal of Chromatography A 1404:1-9.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Haoting Tian, Juan Gao, Hui Li, Stephen A. Boyd, and Cheng Gu, 2016, Complete Defluorination of Perfluorinated Compounds by Hydrated Electrons Generated from 3-Indole-acetic-acid in Organomodified Montmorillonite. Scientific Reports, 6:32949.


Progress 11/05/14 to 09/30/15

Outputs
Target Audience:Scientists and policy makers, as well as individuals and the general public who are interested in the relevant issues. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project has provided many opportunities to train postdoctoral research associates and graduate students who have been benefited from this research by improving their laboratory skills, critical thinking and problem solving. This training has helped them to advance their professional development and careers. How have the results been disseminated to communities of interest?The results from this project have been disseminated primarily through publications in peer-reviewed journal articles and presentations in professional conferences to scientists and policy makers. The results are also reported to the general public who are interested in the relevant issues. What do you plan to do during the next reporting period to accomplish the goals?More experiments will be conducted to elucidate the bioavailability of soil-sorbed tetracycline to E. coli for development and enrichment of antibiotic resistance.

Impacts
What was accomplished under these goals? Tetracyclines are frequently found in soil and water environment, which could exert selective pressure on surrounding bacteria for development and enrichment of antibiotic resistant strains. Tetracycline contains ionizable functional groups that manifest several species with charges at different locales and differential net charges. We used an E. coli bioreporter to investigate tetracycline uptake and evoke antibiotic resistance genes from solution under varying conditions of pH, salt composition and organic acid ligands. The expression of antibiotic resistance gene in the E. coli bioreporter responded linearly to intracellular tetracycline concentration. Both Mg2+ and Ca2+ in solutions reduced uptake of tetracycline by E. coli hence diminishing the bioresponse. The presence of organic acid ligands altered tetracycline speciation in a manner that enhanced tetracycline uptake by E. coli. Increasing bacterial uptake of tetracycline and concomitant enhanced antibiotic resistance response were positively related to the degree of organic acid ligand complexation of metal cations in the order: citric acid > oxalic acid > malonic acid > succinic acid > acetic acid. Among the various tetracycline species present in solution, including both metal-complexed and free (noncomplexed) species, zwitterionic tetracycline was identified as the predominant species that most readily passed through the cell membrane eliciting activation of the antibiotic resistance gene in the E. coli. Impact Statement The current risk assessment of antibiotics and antibiotic resistance suffers from the lack of appropriate models to link environmental exposure and bioresponse. These studies indicate that the same total tetracycline concentration in ambient solution can evoke very different expression of antibiotic resistance genes in the exposed bacteria due to differential antibiotic uptake. Accordingly, environmental factors such as pH, metal cations and organic acid ligands can modulate the selective pressure exerted by tetracyclines for development and enrichment of antibiotic resistant bacteria. We suggest that tetracycline speciation analysis should be incorporated into the risk assessment framework for evaluating environmental exposure and the corresponding development of antibiotic resistance.

Publications

  • Type: Journal Articles Status: Accepted Year Published: 2015 Citation: Zeyou Chen, Yingjie Zhang, Yanzheng Gao, Stephen A. Boyd, Dongqiang Zhu, and Hui Li, 2015, Influence of Dissolved Organic Matter on Tetracycline Bioavailability to an Antibiotic Resistant Bacterium. Environmental Science and Technology 49:xxxx-xxxx
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Yingjie Zhang, Stephen A. Boyd, Brian J. Teppen, James M. Tiedje, and Hui Li, 2014, Role of Tetracycline Speciation in the Bioavailability to Escherichia coli for Uptake and Expression of Antibiotic Resistance. Environmental Science and Technology 48: 4893-4900.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Yingjie Zhang, Stephen A. Boyd, Brian J. Teppen, James M. Tiedje, and Hui Li, 2014, Organic Acids Enhance Bioavailability of Tetracycline in Water to Escherichia coli for Uptake and Expression of Antibiotic Resistance. Water Research. 65:98-106.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Hao Chen, Bin Gao, and Hui Li, 2015, Removal of sulfamethoxazole and ciprofloxacin from aqueous solutions by graphene oxide. Journal of Hazardous Materials, 282:201-207.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Zeyou Chen, Hui Li, Anping Peng, and Yanzheng Gao, 2014, Oxidation of Polycyclic Aromatic Hydrocarbons by Horseradish Peroxidase in Water containing an Organic Cosolvent. Environmental Science and Pollution Research. 21:10696-10705.