Photochemistry of Antibiotics and Estrogens in Surface Water: Persistence and Potency

Project Staff

Principal Investigators: Kristopher McNeill, Assistant Professor, Department of Chemistry, William Arnold, Associate Professor, Department of Civil Engineering, and Deborah L Swackhamer, Professor, Department of Environmental Health Sciences and Co-Director of the Water Resources Center, University of Minnesota

Funding

USGS-WRRI 104G National Grants Competition

Project Duration

September 2003 - August 2005

Summary

Antibiotics and estrogens are two classes of wastewater contaminants that have been detected in US surface waters. The potentially adverse effects of these pollutants on water quality are unknown, but will be determined in part by their persistence. The proposed study will assess the effectiveness OD photochemical reactions initiated by sunlight to degrade different classes of antibiotics and estrogens and to modulate their biological activity. Specifically, the goals of this proposal are to determine the importance of photolysis as a loss process for a representative set of antibiotics and estrogens, to assess changes in the antibiotic activity and estrogenicity that occur during photolysis, and to identify the major reaction products and photolysis pathways involved. These goals will be achieved through laboratory kinetic studies, antibiotic activity and estrogenicity assays, as well as product identification through spectroscopic methods, isolation and independent synthesis. The results of this work will provide the scientific basis for informed decisions regarding antibiotic and estrogen pollution and the stewardship of our freshwater resources. The potential recipients of the benefits of this research include state and federal regulatory agencies, utilities responsible for water treatment operations, researchers focusing on treatment processes and toxicologists interested in potential biological effects of these compounds and their impacts on ecosystems.

Publications

Books and Book Chapters

Arnold, W. A., and K. McNeill. 2007. Transformation of pharmaceuticals in the environment: Photolysis and other abiotic processes In M. Petrovic and D. Barcelo, Eds. Analysis, Fate and Removal of Pharmaceuticals in the Water Cycle, Volume 50. Amsterdam, Netherlands, Elsevier Science. 600 pp.

Refereed Scientific Journal Articles

Werner, J. J., K. H. Wammer, M. Chintapalli, W. A. Arnold, and K. McNeill. 2007. Environmental photochemistry of tylosin: efficient, reversible photoisomerization to a less−active isomer, followed by photolysis. Journal of Agricultural and Food Chemistry 55(17): 7062−7068.

Werner, J.J., W.A. Arnold., and K. McNeill. 2006. Water Hardness as a Photochemical Parameter: Tetracycline Photolysis as a Function of Calcium Concentration, Magnesium Concentration, and pH.Environmental Science & Technology 40: 7236−7241.

Edhlund, B. L., W. A. Arnold, and K. McNeill. 2006. Aquatic Photochemistry of Nitrofuran Antibiotics, Environmental Science & Technology 40: 5422−5427.

Wammer, K. H., T. M. LaPara, and K. McNeill, W. A. Arnold, D. L. Swackhamer. 2006. Changes in Antibacterial Activity of Triclosan and Sulfa Drugs due to Photochemical Transformations. Environmental Toxicology & Chemistry, 25: 1480−1486.

Boreen, A. L., W. A. Arnold, and K. McNeill. 2005. Triplet−sensitized photodegradation of sulfa drugs containing six−membered heterocyclic groups: Identification of an SO2 extrusion photoproduct,Environmental Science & Technology 39: 3630−3638.

Werner, J.J., K. McNeill, and W. A. Arnold. 2005. Environmental photodegradation of mefenamic acid. Chemosphere 58: 1339−1346.

Latch, D. E., J. L. Packer, B. L. Stender, J. VanOverbeke, W. A. Arnold and K. McNeill. 2005. Aqueous photochemistry of triclosan: Formation of 2,4−dichlorophenol, 2,8−dichlorodibenzo−p−dioxin and oligomerization products,Environmental Toxicology & Chemistry. 24(3): 517−525.

Boreen, A. L., W. A. Arnold and K. McNeill. 2004. Photochemical fate of sulfa drugs in the aquatic environment: Sulfa drugs containing five−membered heterocyclic groups,Environmental Science & Technology, 38: 3933−3940

Theses and Dissertations

Latch D. E. 2005. Environmental photochemistry: Studies on the degradation of pharmaceutical pollutants and the microheterogeneous distribution of singlet oxygen. Ph.D. Dissertation, Department of Chemistry, University of Minnesota, Minneapolis, MN, 2005, 256 pp.

Boreen, A. L. 2006. Enhanced photolysis in natural waters: naturally occurring sensitizers and substrates and application to the fate of aquatic pollutants. Ph.D. Dissertation, Department of Chemistry, University of Minnesota, Minneapolis, MN, 263 pp.

Werner, J. J. 2006. The environmental photochemistry of pharmaceutical compounds in aqueous solution and on a clay surface. Ph.D. Dissertation, Graduate Program in Water Resources Science, University of Minnesota, Minneapolis, MN, 119 pp.

Conference Proceedings

Werner, J.J., W. A. Arnold, K. McNeill. 2006. Environmental photochemistry of the antibiotic compound tetracycline: dependence on acid−base and metal binding speciation. Paper presented at the Minnesota Water 2005 and Annual Water Resources Joint Conference, Brooklyn Center, MN, October 25−26, 2006.

Werner, J.J., W.A. Arnold, K. McNeill. 2006. The environmental photochemical kinetics of tetracycline as a function of pH and water hardness. Presented in Environmental Chemistry Awards, Environmental Chemistry Division, American Chemical Society National Meeting, San Francisco, CA, September, 2006.

Edhlund, B.L., W.A. Arnold, K. McNeill. 2006. Aquatic Photochemistry of Nitrofuran Antibiotics. Poster Presentation. Environmental Sciences: Water Gordon Research Conference, Plymouth, NH, June 25−June 30, 2006.

Arnold, W.A. and H. Dolliver. 2006. Pharmaceuticals in Groundwater: Fate, Transport, and Effects. Minnesota Groundwater Spring 2006 Conference, St. Paul, MN, April 12, 2006.

Werner, J.J., and K. McNeill. 2005. Water Hardness as a Critical Photochemical Parameter: The Case of Tetracycline Antibiotics, Pacifichem 2005 Congress,Symposium on Environmental Contaminants of Emerging Concern: Anticipating, Understanding and Intercepting Future Environmental Crises, Honolulu, HI, December 15, 2005.

Edhlund B.L., W.A. Arnold, K. McNeill. 2005. Aquatic Photochemistry of Nitrofuran Antibiotics. Poster Presentation. Minnesota ACS Meeting, St. Paul, MN, November 2005.

Edhlund, B.L., W.A. Arnold, K. McNeill. 2005. Aquatic Photochemistry of Nitrofuran Antibiotics. Poster Presentation. Minnesota Water 2005 and Annual Water Resources Joint Conference, Brooklyn Center, MN, October 2005.

Edhlund, B.L., W.A. Arnold, K. McNeill. 2005. Aquatic Photochemistry of Nitrofuran Antibiotics. Poster Presentation. ENVR, 230th ACS National Meeting, Washington, DC, August 2005.

McNeill, K. 2005. Photochemical approaches to environmental pharmaceutical pollutants, American Chemical Society ACS National Meeting Symposium: Strategies and Molecular Mechanisms of Contaminant Degradation Chemistry,Washington, D.C., August 28−Sept. 1, 2005.

Werner, J.J., K. McNeill, W.A. Arnold. 2004. Speciation−dependent photochemistry of tetracycline antibiotics: acid−base speciation and metal−binding effects. Oral Presentation. Midwest Environmental Chemistry Workshop, Madison, WI, October 16−17, 2004.

McNeill, K., W.A. Arnold. 2004. Contribution of photochemistry to the fate of pharmaceuticals and personal care products in surface waters. Oral Presentation. ENVR, Presented at the special symposium on Environmental aspects of pharmaceuticals and personal care products at the 228th ACS National Meeting, Philadelphia, PA, August 2004.

Boreen, A.L., W.A. Arnold, K. McNeill. 2004. Photochemical fate of sulfa drugs in the aquatic environment. Oral Presentation. ENVR, Presented at the special symposium on Environmental aspects of pharmaceuticals and personal care products at the 228th ACS National Meeting, Philadelphia, PA, August 2004.

Wammer, K.H., K. McNeill, T.M. LaPara, W.A. Arnold, D.L. Swackhamer. 2004. Changes in potency of antibacterials in the environment due to photochemical transformations. Poster Presentation. ENVR, Presented at the special symposium on Environmental aspects of pharmaceuticals and personal care products at the 228th ACS National Meeting, Philadelphia, PA, August 2004.

Werner, J.J., K. McNeill, W.A. Arnold. 2004. Kinetics of the environmental photodegradation of mefenamic acid. Poster Presentation. ENVR, Presented at the special symposium on Environmental aspects of pharmaceuticals and personal care products at the 228th ACS National Meeting, Philadelphia, PA, August 2004.

Arnold, W.A., J.J. Werner, K. McNeill. 2004. Kinetics of the environmental photodegradation of mefenamic acid. Poster Presentation. Environmental Sciences: Water Gordon Research Conference, Plymouth, NH, June 27−July 2, 2004.

McNeill, K. 2004. Photochemical fate of pharmaceutical pollutants. Gordon Research Conference, Environmental Sciences: Water, June 27−July 2, 2004.

Wammer, K.H., D.L. Swackhamer, W.A. Arnold, K. McNeill. 2004. Photochemical transformations of antibacterial compounds. Poster Presentation. Environmental Sciences: Water Gordon Research Conference, Plymouth, NH, June 27−July 2, 2004.

Boreen, A.L., W.A. Arnold, K. McNeill. 2004. Photochemical fate of pharmaceuticals in the environment: Sulfa drugs. Oral Presentation. 9th Biennial MN Water Conference, Minneapolis, MN, March 23, 2004.

Werner, J.J., K. McNeill, W.A. Arnold. 2004. Photochemical fate of pharmaceuticals in the environment. Poster Presentation. 9th Biennial MN Water Conference, Minneapolis, MN, March 23, 2004.

Other Publications

Werner, J.J., A.L. Boreen, B. Edhlund, K.H. Wammer, E. Matzen, K. McNeill, W.A. Arnold. 2005. Photochemical transformation of antibiotics in Minnesota waters, CURA Reporter 35(2): 1−5.

Other Presentations

Edhlund, B.L., W.A. Arnold, K. McNeill. 2006. Aquatic Photochemistry of Nitrofuran Antibiotics. Celebrating Women Chemists Luncheon, University of Minnesota, Minneapolis, MN, February, 2006.

McNeill, K. 2006. Phototransformation Reactions of Antibiotic Pollutants, Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy Symposium on Degradation and Treatment of Pharmaceuticals in the Environment, Orlando, FL, March 12−17, 2006.

McNeill, K. 2005. Photosensitized reactions in natural waters: Implications for pollutant degradation and the carbon cycle, University of Minnesota−Morris, Department of Chemistry, October 27, 2005.

McNeill, K. 2005. Photosensitized reactions in natural waters: Implications for pollutant degradation and the carbon cycle, University of Minnesota, Department of Chemistry, September 20, 2005.

McNeill, K. 2005. Photo−generated Reactive Species and the Degradation of Pharmaceutical Pollutants, Stanford University, Civil and Environmental Engineering Student Seminar Series, May 20, 2005.

McNeill, K. 2005. Mechanistic Environmental Chemistry: Photo−generated Reactive Species and Pollutant Degradation, Cornell University, Department of Chemistry, March 7, 2005.

McNeill, K. 2005. Mechanistic Environmental Chemistry: Photo−generated Reactive Species and Pollutant Degradation, University of Rochester, Department of Chemistry, March 4, 2005.

McNeill, K. 2005. Mechanistic Environmental Chemistry: Photo−generated Reactive Species and Pollutant Degradation, University of California, Berkeley,Department of Chemistry, February 25, 2005.

McNeill, K. 2005. Mechanistic Environmental Chemistry: Photo−generated Reactive Species and Pollutant Degradation, Northwestern University, Department of Chemistry, February 18, 2005.

McNeill, K. 2004. Mechanistic Environmental Chemistry: Photo−generated Reactive Species and Pollutant Degradation, 3M, November 12, 2004.

Boreen, A.L., W.A. Arnold, K. McNeill. 2004. Photochemical fate of sulfa drugs in the aquatic environment. Physics and Chemistry Colloquium, Concordia College, Moorhead, MN, November, 2004.

Boreen, A.L., W.A. Arnold, K. McNeill. 2004. Photochemical fate of sulfa drugs in the aquatic environment. Celebrating Women Chemists Luncheon, University of Minnesota, Minneapolis, MN, September, 2004.