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<p>The objectives of this project are:</p>
<p>1) To conduct a survey in the Central Valley of California to measure concentrations of various antibiotics, pesticides, and hormones in soil, surface, and groundwater. Samples will initially be taken in proximity to specific dairy farms and sampling will gradually increase to cover a wide geography of the Central Valley; </p>
<p>2) To determine the sorption, facilitated transport, and degradation of a suite of agrochemical relevant to California agriculture, including natural hormones (e.g., estrone (E1), 17?-estradiol (E2), testosterone), antibiotics (e.g., sulfamethazine, monensin, oxytetracycline), and pesticides (e.g., atrazine, dicofol, lindane) to soils, soil amendments (e.g., manure, biochar), and individual soil minerals (i.e., Mn-oxides, Fe-oxides, kaolinite); </p>
<p>3)To determine how common soil bacteria (i.e., Pseudomonas aeruginosa, Bacillus subtilis), and related isolates from soil and manure, influence agrochemical transport and degradation in batch and flow conditions; </p>
<p>4) To use micro/macro aggregate-scale batch/column studies to determine the role of soil minerals (i.e., Mn-oxides, Fe-oxides, kaolinite) and natural organic matter on sorption and facilitated transport of agrochemicals commonly used in California agriculture; and </p>
<p>5) To probe molecular mechanisms and reaction rates of agrochemical sorption and abiotic degradation by soil minerals using a various spectroscopy tools (e.g, ATR-FTIR, Raman, NMR, STXM). The expected outcomes of this proposed research include an improved understanding of agrochemical transport in the soil environment and to provide recommendations regarding the storage and application pesticides and animal waste.</p>
<p>NON-TECHNICAL SUMMARY:<br/> Land application of pesticides and manures, containing veterinary antibiotics and hormones, from concentrated animal feeding operations (CAFOs) threatens environmental health due to the antibiological and endocrine disrupting properties of these chemicals. Although much of the published research suggests limited mobility, surveys of soil, groundwater, and surface waters reveal detectable concentrations of many agrochemicals. The presence of these chemicals in the soil and water are a source of potential risk to food production, food safety, development of antibiotic resistance by bacteria, and human/animal health (e.g., endocrine disrupters and carcinogens). There is an urgent need for research which addresses transport and sorption mechanisms of agrochemicals present in soil and animal waste, regardless of their perceived mobility. It is
critical that we understand these processes, as maintaining soil and water quality is imperative for us to develop improved agricultural production systems. Ultimately, it is expected that our research will provide essential information for recommendations regarding the storage and land application of pesticides and animal waste.<p>
APPROACH: <br/>The initial field sites for this study located are within eight dairy research sites in the Central Valley of California (Staislaus-Merced and Tulare-Kings Counties). A network of 64 monitoring wells (sampled for ongoing work) are in place within four different management units (i.e., upgradient, manured field, corral, lagoon). Soil samples for batch and column experiments will be collected from the dairy research sites. Groundwater samples have been collected over a 16 month period with four sampling dates (i.e., Jan. 2008, April 2008, Sept. 2008, April 2009) and will be analyzed for the presence of agrochemicals via liquid chromatography-tandem mass (LC-MS/MS) spectrometry with electrospray ionization. Bacteria will be isolated from soil and animal waste using standard techniques for use in laboratory experiments. The sorption/degradation of
agrochemicals will be studies as a function of compound concentration, pH, and ionic strength will be measured. Analysis of solution- and solid-phase agrochemical concentrations will measure sorption/uptake. Concentrations and specific degradation products will be determined through analysis via liquid chromatography and mass spectrometry electrospray ionization. After quantifying the sorption capacity and degradation ability of soil and individual soil components (e.g., mineral phases, organic matter), transport will be studied using column experiments. Transport via colloidal minerals, organic matter, and bacteria will also be studied. The column effluent will be analyzed to determine parent and degradation product concentrations in addition to extracting the solid phase from the column to determine the concentration and speciation of compounds removed from solution. While the above
studies provide macroscopic information, there also exists a need to understand molecular level interactions to evaluate reaction mechanisms. Reaction kinetics and molecular-scale interactions during the sorption and degradation of various agrochemicals will be investigated using various molecular spectroscopy techniques. In particular, attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy will be used to provide in situ kinetic data at the molecular level. ATR-FTIR spectroscopy is a nondestructive tool which can be used to study a range of biogeochemical interactions, including sorption of inorganic/organic compounds to mineral surfaces Since this penetration depth is comparable to the size of mineral particles, molecular-level information on surface interactions between mineral substrates and various contaminants may be obtained by varying the
physical-chemical properties at the IRE interface. In the event of rapid compound degradation via mineral surfaces. </p><p>PROGRESS: <br/>2013/01 TO 2013/09 <br/>Target Audience: The primary target audience for this reporting period is scientists, policy makers, and agricultural stakeholders involved in the use of pharmaceuticals in animal agriculture. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? This research project has provided training and professional development for two graduate students and two undergraduate students. All four individual were involved in conducting this research in order to provide field and laboratory training in soil chemistry. In addition presentations at International Conferences (SSSA, graduate students) and our own lab meetings (all students) serves to assist in professional development for these young scientists. How have the results been disseminated to communities of interest? The
results have been disseminated through peer-reviewed publications and presentations at conferences. What do you plan to do during the next reporting period to accomplish the goals? Proposed project activities include: 1. Laboratory research to investigate binding of pharmaceuticals to soil and various mineral phases; 2. Field research to examine the fate of pharmaceuticals land applied under conditions simulating irrigation of pasture; 3. Prepare manuscripts for publication in order to disseminate research to communities of interest.
<br/>PROGRESS: <br/>2012/01/01 TO 2012/12/31 <br/>OUTPUTS: Outcomes for this project include presentations at the national and regional meetings. A. Soil Science Society of America National Meetings: Bair, D.A., I.E. Popova, K.W. Tate, and S.J. Parikh. 2012. Sorption, Leaching and Surface Runoff of Rangeland Veterinary Pharmaceuticals From Soil Boxes. Soil Science Society of America National Meetings. October 21-24, Cincinnati, OH. Parikh, S.J., I.E. Popova, D.A. Bair, and K.W. Tate. 2012. Transport of Veterinary Antibiotics in Surface Runoff From Irrigated Pastures. Soil Science Society of America National Meetings. October 21-24, Cincinnati, OH. Popova, I. and S.J. Parikh. Pressurized liquid extraction of chlortetracycline and oxytetracycline from soil with in-cell cleanup. HPLC 2012. June 16-21, Anaheim, CA. B. Western Soil Science Society and the West Regional Cooperative
Soil Survey Conference: Popova, I.E. D.A. Bair, K.W. Tate, and S.J. Parikh. 2012. Leaching of veterinary pharmaceuticals from manure amended soils: Packed soil boxes study. Joint Meeting Western Soil Science Society and the West Regional Cooperative Soil Survey Conference. June 25-27, Davis, CA. Bair, D.A., F.N.D. Mukome, A. Jefferson, T.M. Young, and S.J. Parikh. 2012. How do biochar and biosolid co-amendments impact the mobility of pharmaceuticals, heavy metals, and herbicides in soils Joint Meeting Western Soil Science Society and the West Regional Cooperative Soil Survey Conference. June 25-27, Davis, CA. C. California Plant and Soil Conference Parikh, S.J., F.N.D. Mukome, E. Suddick, E.I.P. Pereira, E. Verhoeven, and J.W. Six. 2012. Investigating Potential Benefits of Soil Biochar Amendments. California Plant and Soil Conference, American Society of Agronomy, CA Chapter. Feb. 7-8,
Visalia, CA. Bair, D.A., T.M. Young, and S.J. Parikh. 2012. Can Biochar Reduce Mobility of Pharmaceuticals in Biosolid Amended Soils California Plant and Soil Conference, American Society of Agronomy, CA Chapter. Feb. 7-8, Visalia, CA. D. A presentation as the USDA-AFRI project directors meeting in 2012: Tate, K., E.P. Kolodziej, R. Atwill, A. Craigmill, T. O'Geen, D. Holstege, S.J. Parikh, and G.D. Jones. 2011. Transport and Mitigation of Beef Cattle Veterinary Pharmaceuticals and Hormones PARTICIPANTS: Thomas Harter (Faculty, UCD) Edwared Kolodziej (Faculty, UN Reno) Toby O'Geen (Faculty, UCD) Ken Tate (Faculty, UCD) Thomas Young (Faculty, UCD) Johan Six (Faculty, UCD) Kate Scow (Faculty, UCD) Daoyuan Wang (Visiting Scholar, UCD) Fungai Mukome (Postdoctoral Scholar, UCD) Ina Popova (Postdoctoral Scholar, UCD) Danny Bair (PhD Student, UCD) Sarah Hafner (PhD Student) Training and professional development of graduate and undergraduate students and postdoctoral scholars has been an important part of this project. To date training has focused on development of experimental protocols, chemical analysis techniques, and critical evaluation of data. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
<br/>PROGRESS: <br/>2011/01/01 TO 2011/12/31 <br/>OUTPUTS: Outcomes for this project include presentations at the national meeting of the Soil Science Society of America: Parikh, S.J., A. Jefferson, N. Ghazal, X.E., Zhang, D.A. Bair, and F.N.D. Mukome. 2011. Soil Science Society of America Annual Meeting. Oct. 16-19, San Antonio, TX. Hafner, S., and S.J. Parikh. 2011. Binding and Degradation of Monensin by Soil Minerals. Soil Science Society of America Annual Meeting. Oct. 16-19, San Antonio, TX. A presentation as the USDA-AFRI project directors meeting in 2011: Tate, K., E.P. Kolodziej, R. Atwill, A. Craigmill, T. O'Geen, D. Holstege, S.J. Parikh, and G.D. Jones. 2011. Transport and Mitigation of Beef Cattle Veterinary Pharmaceuticals and Hormones An overview talk of the subject addressed by this project was also given Plant and Soil Conference of the CA chapter of the Agronomy
Society of America. This talk provided an opportunity for outreach to the CA agricultural stake holders. Parikh, S.J. 2011. Understanding the Fate of Antibiotics in Concentrated Animal Feeding Operations. Plant and Soil Conference, American Society of Agronomy, CA Chapter. Feb. 1-2, Fresno, CA. PARTICIPANTS: Thomas Harter (Faculty, UCD) Edwared Kolodziej (Faculty, UN Reno) Toby O'Geen (Faculty, UCD) Ken Tate (Faculty, UCD) Thomas Young (Faculty, UCD) Fungai Mukome (Postdoctoral Scholar, UCD) Ina Popova (Postdoctoral Scholar, UCD) Christopher Alaimo (Staff Research Associate, UCD) Danny Bair (PhD Student, UCD) Sarah Hafner (PhD Student) Allie Jefferson (Undergraduate Student, UCD) Training and professional development of graduate and undergraduate students and postdoctoral scholars has been an important part of this project. To date training has focused on development of experimental
protocols, chemical analysis techniques, and critical evaluation of data. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.<br/>
PROGRESS: <br/>2010/01/01 TO 2010/12/31 <br/>OUTPUTS: Outcomes for this project include presentations at the national meeting of the Soil Science Society of America: Bair, D., and S.J. Parikh. 2010. Adsorption and Transformation of Ivermectin with Soil Minerals. Soil Science Society of America Annual Meeting. Oct. 31 - Nov. 3, Long Beach, CA. Hafner, S., and S.J. Parikh. 2010 Mechanisms of Binding and Abiotic Degradation of Sulfamethazine to Iron and Manganese Oxides. Soil Science Society of America Annual Meeting. Oct. 31 - Nov. 3, Long Beach, CA. A presentation as the USDA-AFRI project directors meeting in 2011: Tate, K., E.P. Kolodziej, R. Atwill, A. Craigmill, T. O'Geen, D. Holstege, S.J. Parikh, and G.D. Jones. 2011. Transport and Mitigation of Beef Cattle Veterinary Pharmaceuticals and Hormones An overview talk of the subject addressed by this project was also given
Plant and Soil Conference of the CA chapter of the Agronomy Society of America. This talk provided an opportunity for outreach to the CA agricultural stake holders. Parikh, S.J. 2011. 2011. Understanding the Fate of Antibiotics in Concentrated Animal Feeding Operations. Plant and Soil Conference, American Society of Agronomy, CA Chapter. Feb. 1-2, Fresno, CA. PARTICIPANTS: Thomas Harter (Faculty, UCD) Edwared Kolodziej (Faculty, UN Reno) Toby O'Geen (Faculty, UCD) Ken Tate (Faculty, UCD) Thomas Young (Faculty, UCD) Fungai Mukome (Postdoctoral Scholar, UCD) Christopher Alaimo (Staff Research Associate, UCD) Danny Bair (PhD Student, UCD) Lina Bachert (MS Student, Univ. Duisburg-Essen, Germany) Sarah Hafner (PhD Student) Brian Mathison (MS Student, UCD) Allie Jefferson (Undergraduate Student, UCD) Training of graduate and undergraduate students has been a specific component of this project.
Training has focused on method for analysis of agrochemicals in soil and water samples. Protocols have largely followed EPA specific methods but have been modified for our specific research projects and equipment. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.</p>