Source: MICHIGAN STATE UNIV submitted to NRP
ANIMAL MANURE-DERIVED DISSOLVED ORGANIC MATTER AFFECTS SORPTION AND TRANSPORT OF VETERINARY PHARMACEUTICALS IN SOILS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
0219489
Grant No.
2009-65102-05847
Cumulative Award Amt.
(N/A)
Proposal No.
2009-02877
Multistate No.
(N/A)
Project Start Date
Sep 1, 2009
Project End Date
Aug 31, 2013
Grant Year
2009
Program Code
[94540]- Water and Watersheds
Recipient Organization
MICHIGAN STATE UNIV
(N/A)
EAST LANSING,MI 48824
Performing Department
Plant, Soil and Microbial Science
Non Technical Summary
The overall objective is to understand the impacts of dissolved organic matter derived from land-applied animal manures on sorption and transport of veterinary pharmaceuticals in soils. Veterinary pharmaceuticals are commonly administered to animals for disease control and added into feeds at subtherapeutic levels to improve feeding efficiency. These utilizations have been identified as a primary pollution source of veterinary pharmaceuticals in soil and water. A large fraction of pharmaceuticals administered to livestock are excreted into manures, and the application of the manures as organic plant fertilizers interjects these pharmaceuticals into agricultural lands, where they are subsequently disseminated to the environment. There is a paucity of fundamental knowledge regarding the sorption and transport of manure-borne pharmaceuticals in soils. Such knowledge is required to assess the potential for exposure of at-risk populations. Current assessments of the impacts of pharmaceutical-laden manures on agricultural land and water quality generally rely on the data obtained from unrealistic ??clean?? soil-water binary systems, i.e. in the absence of manures. In reality, veterinary pharmaceuticals released from feeding facilities originate from animal manures; components of these manures may affect their ultimate environmental fate. Animal manure amendments to soil alter many important soil characteristics, especially by increasing water-dissolved organic matter (DOM), and many veterinary pharmaceuticals form associations with such DOM. We hypothesize that the formation of DOM-pharmaceutical associations significantly influences pharmaceutical sorption to solid phases in soils, and results in facilitated transport in the environment. To examine this hypothesis, we propose the following objectives to systematically evaluate the effects of manure-derived DOM on sorption and transport of veterinary pharmaceuticals in soils: Objective 1. Screen representative veterinary pharmaceuticals for their propensities to bind to manure-derived DOM; this information will be used to define a subset of pharmaceuticals for detailed study. Objective 2. Quantify and rank the physicochemical factors determining the extent of DOM interactions with veterinary pharmaceuticals. Objective 3. Quantify the effects of manure-derived DOM on sorption of veterinary pharmaceuticals by soils. Objective 4. Quantify manure-derived DOM-facilitated transport of veterinary pharmaceuticals in soils. The output of this project will produce information that is critically needed to enable accurate environmental fate modeling and risk assessment of veterinary pharmaceuticals originating from land application of animal manure. Knowledge gained from this research will facilitate the development of objective scientifically-informed management practices to minimize the dissemination of veterinary pharmaceuticals in the environment resulting from agricultural production systems.
Animal Health Component
25%
Research Effort Categories
Basic
75%
Applied
25%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
1020110200010%
1025230200020%
1110110200010%
1115230201020%
1335230205020%
1330210200010%
1330210201010%
Goals / Objectives
The overall objective is to understand the impacts of dissolved organic matter derived from land-applied animal manures on sorption and transport of veterinary pharmaceuticals in soils. Currently, there is a paucity of fundamental knowledge regarding the sorption and transport of manure-borne pharmaceuticals in soils. Such knowledge is required to assess the potential for exposure of at-risk populations. Animal manure amendments to soil alter many important soil characteristics, especially by increasing water-dissolved organic matter (DOM), and many veterinary pharmaceuticals form associations with such DOM. The formation of DOM-pharmaceutical associations significantly influences pharmaceutical sorption to solid phases in soils, and results in facilitated transport in the environment. To achive the goal, we will conduct experiments to systematically evaluate the effects of manure-derived DOM on sorption and transport of veterinary pharmaceuticals in soils. The output of this project will produce information that is needed to enable accurate environmental fate modeling and risk assessment of veterinary pharmaceuticals originating from land application of animal manure. Knowledge gained from this research will facilitate the development of objective scientifically-informed management practices to minimize the dissemination of veterinary pharmaceuticals in the environment resulting from agricultural production systems.
Project Methods
(1) We will screen representative veterinary pharmaceuticals for their propensities to bind to manure-derived DOM; this information will be used to define a subset of pharmaceuticals for detailed study. (2) We will quantify and rank the physicochemical factors, such as pH, ion type and concentrations, determining the extent of DOM interactions with veterinary pharmaceuticals. (3) We will conduct batch studies to quantify the effects of manure-derived DOM on sorption of veterinary pharmaceuticals by soils. (4) We will conduct column studies to quantify manure-derived DOM-facilitated transport of veterinary pharmaceuticals in soils.

Progress 09/01/09 to 08/31/13

Outputs
Target Audience: scientists and policy makers, as well as 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 multiple opportunities to train two post-doctorates and two graduate students who have been benefited from this research by improving their laboratory skills, critical thinking and problem solving. This has advanced 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 journal articles and presentations in professional conferences to scientists and policy makers, as well as 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? Nothing Reported

Impacts
What was accomplished under these goals? Land application of biosolids derived from livestock production and wastewater treatment plants results in the dissemination of pharmaceuticals to the environment along with higher concentration of dissolved organic matter. The results obtained herein suggest that significant fractions of the pharmaceuticals could be associated with DOM under environmentally relevant settings (DOM concentration at mg/L levels). The association of pharmaceuticals with DOM could alter their sorption, transport, bioavailability, biotic and abiotic transformation processes in the aquatic environment. We have developed a simple and innovative method to determine the interaction of pharmaceuticals with dissolved organic matter. Pharmaceuticals bound to DOM can significantly alter their behavior, fate and mobility in the environment. In order to estimate the distributions of freely dissolved vs. DOM-bound pharmaceuticals in water, the binding coefficients measured by the developed SPE method was used to estimate such distribution. Assume that pharmaceutical concentration was 50 microgram per liter in water and DOM concentration was 5, 50 and 200 mg L-1. At pH 8.0, the presence of 5 mg L-1 of DOM results in 2.8% of carbadox, 7.3% of lincomycin, and 25.9% of tetracycline associated with DOM. As DOM concentration increases to 200 mg L-1, the fractions of pharmaceutical bound to DOM increase to 52.6% for carbadox, 75.9% for lincomycin, and 93.2% for tetracycline. These results indicate that many pharmaceuticals present in water could be partially associated with DOM, hence reducing sorption to soil, and enhancing the corresponding mobility in the environment. Such binding to DOM could also diminish bioavailability and biodegradation of pharmaceuticals in the aqueous phase.

Publications

  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Yuan Tian, Bin Gao, Hao Chen, Yu Wang, and Hui Li, 2013, Interactions between carbon nanotubes and sulfonamide antibiotics in aqueous solutions under various physicochemical conditions. Journal of Environmental Science and Health Part A-Toxic/Hazardous Substances & Environmental Engineering 48:1136-1144.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Yunjie Ding, Brian J. Teppen, Stephen A. Boyd and Hui Li, 2013, Measurement of Associations between Pharmaceuticals and Dissolved Humic Substances using Solid Phase Extraction. Chemosphere 91:314-319.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Wan-Ru Chen, Cun Liu, Stephen A. Boyd, Brian J. Teppen, and Hui Li, 2013, Reduction of carbadox mediated by reaction of Mn(III) with oxalic acid. Environmental Science and Technology 47:1357-1364.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Yuan Tian, Bin Gao, Ver�nica L. Morales, Hao Chen, Yu Wang, and Hui Li, 2013, Removal of sulfamethoxazole and sulfapyridine by carbon nanotubes in fixed-bed columns. Chemosphere 90:2597-2605.


Progress 09/01/11 to 08/31/12

Outputs
OUTPUTS: The overall objective is to evaluate the impacts of land-applied animal manures on sorption and transport of manure-borne veterinary pharmaceuticals in agricultural ecosystems. Recently, we developed an innovative method to determine association of pharmaceuticals, i.e. carbadox, lincomycin and tetracycline, with dissolved humic acids using solid phase extraction (SPE). Dissolved organic matter (DOM) and DOM-bound pharmaceuticals passed through the SPE cartridge while the cartridge retained freely dissolved pharmaceuticals from water. This method was validated by comparison with the results measured using the common equilibrium dialysis technique. For the SPE method pharmaceutical interaction with DOM required ~30 h to approach the equilibration, whereas 50 to 120 h was needed for the equilibrium dialysis technique. The uneven distributions of freely membrane-penetrating pharmaceuticals and protons inside vs. outside of the dialysis cell due to the Donnan effect resulted in overestimates of pharmaceutical affinity with DOM for the equilibrium dialysis method. The SPE technique eliminates the Donnan effect, and demonstrates itself as a more efficient, less laborious and more accurate method. The measured binding coefficients with DOM followed the order of carbadox, lincomycin, tetracycline. Pharmaceutical bindings with Leonardite humic acid were greater than those with Aldrich humic acid due to more interaction sites, i.e. carboxylic and phenolic functional moieties, present in the Leonardite humic acid. PARTICIPANTS: Collaborators: Stephen A. Boyd, and Brian J. Teppen, Department of Plant, Soil and Microbial Sciences, Michigan State University; Irene Xagoraraki, Department of Civil and Environmental Engineering, Michigan State University; Bin Gao, Department of Agricultural and Biological Engineering, University of Florida. Trainee: Yunjie Ding (Post-doctoral fellow), Pin Gao (Graduate student), and Cuiping Wang (Graduate student). TARGET AUDIENCES: The audiences are scientists and policy makers, as well as the general public who are interested in the related scientific issues. PROJECT MODIFICATIONS: Not relevant to this project.

Impacts
Land application of biosolids derived from livestock production and wastewater treatment plants results in the dissemination of pharmaceuticals to the environment along with higher concentration of dissolved organic matter. The results obtained herein suggest that significant fractions of the pharmaceuticals could be associated with DOM under environmentally relevant settings (DOM concentration at mg/L levels). The association of pharmaceuticals with DOM could alter their sorption, transport, bioavailability, biotic and abiotic transformation processes in the aquatic environment.

Publications

  • Gao, P., Ding, Y. Li, H. and Xagoraraki, I. 2012. Occurrence of Pharmaceuticals in a Municipal Wastewater Treatment Plant: Mass Balance and Removal Processes. Chemosphere 88: 17-24.
  • Wang, C., Teppen, B. J., Boyd, S. A. and Li, H. 2012. Sorption of Lincomycin at Low Concentrations from Water by Soils. Soil Science Society of America Journal 76: 1222-1228.
  • Yao, Y., Gao, B., Chen, H., Jiang, L., Inyang, M., Zimmerman, A. R., Cao, X., Yang, L., Xue, Y. and Li, H. 2012. Adsorption of Sulfamethoxazole on Biochar and Its Impact on Reclaimed Water Irrigation. Journal of Hazardous Materials. 209: 408-413.


Progress 09/01/10 to 08/31/11

Outputs
OUTPUTS: The overall objective is to evaluate the impacts of land-applied animal manures on sorption and transport of manure-borne veterinary pharmaceuticals in agricultural ecosystems. Lincomycin is an antibiotic most frequently detected in effluents from wastewater treatment plants and surface runoff at agricultural production systems. Land application of biosolids results in the dissemination of lincomycin to the environment A better understanding of lincomycin sorption by soil is beneficial to assessing its environmental fate, transport and potential impacts to human and ecosystem health. Systematic batch studies were conducted to characterize sorption of lincomycin by soils with aqueous concentrations at microgram per liter levels. The effects of varying solution pH, background salt compositions and ionic strength on lincomycin sorption were evaluated. Cation exchange is the primary mechanism for lincomycin sorption by soils. Lincomycin sorption increased as soil solution pH increased from 5.8 to 7.8, then decreased significantly at pH 8.9. The maximum sorption occurred at pH between 7.3 and 7.8, near the pKa of lincomycin (7.6). The presence of K+ and Ca2+ in aqueous solution (0.02 M) greatly suppressed lincomycin sorption, with more suppression observed as soil cation exchange capacity decreased. These results suggest that inorganic cations commonly present in surface and ground waters could effectively compete with trace levels of ionic pharmaceuticals for sorption sites in soil, hence altering their transport and transformation processes in the environment. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Land application of biosolids derived from livestock production and wastewater treatment plants results in the dissemination of pharmaceuticals to the environment. The information obtained herein improves our knowledge of fate and transport of pharmaceuticals in soil and water. The presence of environmentally occurring inorganic cations could effectively compete with trace levels of ionic pharmaceuticals for sorption sites in soils, hence altering their transport and transformation processes in the environment. Understanding these processes enhances our capability to more accurately predict and control the contamination of emerging pollutants.

Publications

  • Yunjie Ding, Weihao Zhang, Cheng Gu, Irene Xagoraraki, and Hui Li, 2011, Determination of Pharmaceuticals in Biosolids using Accelerated Solvent Extraction and Liquid Chromatography/Tandem Mass Spectrometer. Journal of Chromatography A, 1218:10-16.
  • Yunjie Ding, and Hui Li, 2011, Investigation of Interactions between Dissolved Organic Matter and Pharmaceuticals by Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry. International Annual Meeting of American Society of Agronomy (ASA), Crop Science Society of America (CSSA), and Soil Science Society of America (SSSA), San Antonio , TX, October 16-19.


Progress 09/01/09 to 08/31/10

Outputs
OUTPUTS: The overall objective is to evaluate the impacts of land-applied animal manures on sorption and transport of manure-borne veterinary pharmaceuticals in agricultural ecosystems. Veterinary pharmaceuticals are commonly administered to animals for disease control and added into feeds at subtherapeutic levels to improve feeding efficiency. As a result of these practices, a certain fraction of pharmaceuticals are excreted into animal manures. Land application of these manures contaminates soil with the veterinary pharmaceuticals that can subsequently lead to contamination of surface and ground waters. Information on the occurrence and fate of pharmaceuticals in soil and water is needed to assess the potential for exposure of at-risk populations and the potential impacts on agricultural ecosystems. In this study, we investigated the occurrence and fate of amprolium, carbadox, monensin and tylosin in a farm. Amprolium and monensin were frequently detected in nearby surface water with concentrations ranging from several to hundreds of nanograms per liter of water, whereas tylosin or carbadox was rarely found. These pharmaceuticals were more frequently detected in surface runoff during non-growing season (October to April) than during growing season (May to September). Pharmaceuticals resulting from post-harvest manure application appeared to be more persistent than those from spring application. High concentrations of pharmaceuticals in soils were generally observed in the sites where the respective concentrations in surface water were also high, suggesting that soil is a sink for veterinary pharmaceuticals that can be disseminated to nearby surface waters. To further evaluate pharmaceuticals in land-applied biosolids, analytical method was developed to quantitatively determine pharmaceuticals in biosolids. Pharmaceuticals were extracted from biosolids using accelerated solvent extraction under optimized conditions, followed by cleanup using solid-phase extraction and determination by LC-MS/MS. For the fifteen commonly used pharmaceuticals the overall method extraction recoveries from biosolid ranged from 49% to 95%. The developed method was validated and applied to biosolid samples. Among the fifteen target pharmaceuticals, fourteen pharmaceuticals were detected in the collected biosolid samples. The average concentrations ranged from 2.6 g/kg for lincomycin to 743.6 g/kg for oxytetracycline. These results indicated that pharmaceuticals could survive wastewater treatment processes, and accumulate in sewage sludge and biosolids. Subsequent land application of the contaminated biosolids could lead to the dissemination of pharmaceuticals in soil and water environment, which poses potential threats to at-risk populations in the receiving ecosystems. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Apparently, land application of biosolids for their fertilizer values can cause the dissemination of veterinary pharmaceuticals to soil and water. The information obtained improves our knowledge of occurrence, fate and transport of pharmaceuticals. Understanding the processes of pharmaceutical occurrence and sorption in soils enhances our capability to more accurately predict and control the contamination of emerging pollutants. The results could potentially help direct the development of biosolid application guideline to minimize the release of pharmaceuticals into surrounding waters.

Publications

  • Yunjie Ding, Weihao Zhang, Cheng Gu, Irene Xagoraraki, and Hui Li, 2010, Determination of Pharmaceuticals in Biosolids using Pressurized Liquid Extraction and Liquid Chromatography/Tandem Mass Spectrometer. Journal of Chromatography A. doi:10.1016/j.chroma.2010.10.112 (in press).
  • Joseph J. Pignatello, Brian Katz, and Hui Li, 2010, Organic Contaminants in Water, Soil and Sediment: Sources, Interactions and Ecological Impacts: An Introduction to the Special Series. Journal of Environmental Quality, 39:1133-1138.
  • Wenlu Song, Yunjie. Ding, Cary T. Chiou, and Hui Li, 2010, Selected Veterinary Antibiotics in Agricultural Water and Soil Resulting from Animal Feeding Operations. Journal of Environmental Quality, 39:1211-1217.