Results of the Lake Michigan Mass Balance Study: Atrazine Data Report December 2001 U.S. Environmental Protection Agency Great Lakes National Program Office (G-17J) 77 West Jackson Boulevard Chicago, IL 60604 EPA 905R-01-010 Results of the Lake Michigan Mass Balance Study: Atrazine Data Report Prepared for: USEPA Great Lakes National Program Office 77 West Jackson Boulevard Chicago, IL 60604 Prepared by: Robert N. Brent, Ph.D. Judy Schofield, and Ken Miller DynCorp Science and Engineering Group 6101 Stevenson Avenue Alexandria, VA 22304 December 2001 Acknowledgements This report was prepared under the direction of Glenn Warren, Project Officer, USEPA Great Lakes National Program Office; and Louis Blume, Work Assignment Manager and Quality Assurance Officer, USEPA Great Lakes National Program Office. The report was prepared by Robert Brent, Judy Schofield, and Ken Miller of DynCorp’s Science and Engineering Group, with assistance from Chip McCarty, Heather Wolfe, and Kim Malloy of DynCorp, and with significant contributions from the LMMB Principal Investigators for atrazine. GLNPO thanks these investigators and their associates for their technical support in project development and implementation. GLNPO specifically thanks Clyde Sweet of the Illinois State Water Survey for his written summary of results for atrazine in atmospheric components. GLNPO thanks Bill Sukloff of Environment Canada and Syd Allan for use and implementation of the Research Data Management Quality System (RDMQ). LMMB Principal Investigators for Atrazine Clyde Sweet (atmosphere) Steve Eisenreich (tributary and open lake) Illinois State Water Survey University of Minnesota 2204 Griffith Drive Gray Freshwater Biological Institute and Champaign, Illinois 61820 Rutgers University New Brunswick, New Jersey 08901 Ron Hites and Ilora Basu (atmosphere) Indiana University 1005 East Tenth Street Bloomington, Indiana 47405 Portions of this document were developed using information presented in the following publications and internal reports: Miller, S.M. 1999. Spatial and Temporal Variability of Organic and Nutrient Compounds in Atmospheric Media Collected During the Lake Michigan Mass Balance Study. M.S. thesis. University of New York at Buffalo, Buffalo, New York. 181 pp. Miller, S.M.; Sweet, C.W.; DePinto, J.V.; Hornbuckle, K.C. 2000. Atrazine and Nutrients in Precipitation: Results from the Lake Michigan Mass Balance Study. Environ. Sci. Technol. 34(1): 55- 61. Rygwelski, K.; Richardson, W.; Endicott, D. 1999. A Screening-Level Model Evaluation of Atrazine in the Lake Michigan Basin. J. Great Lakes Res. 25(1): 94-106. Schottler, S.P; Eisenreich, S. 1997. Mass Balance Model to Quantify Atrazine Sources, Transformation Rates, and Trends in the Great Lakes. Environ. Sci. Technol. 31(9): 2616-2625. Sweet, C. 2000. Measurement of Atrazine in Atmospheric Samples in the Lake Michigan Mass Balance Study (LMMB), 1994-1995. Internal document. Great Lakes National Program Office. Table of Contents Table of Contents Executive Summary .................................................................ix Chapter 1 Project Overview.........................................................1-1 1.1 Background ..........................................................1-1 1.2 Description ...........................................................1-1 1.3 Scope...............................................................1-2 1.3.1 Modeled Pollutants..............................................1-2 1.3.1.1Polychlorinated Biphenyls..................................1-2 1.3.1.2 Trans-Nonachlor .........................................1-3 1.3.1.3Atrazine................................................1-4 1.3.1.4Mercury................................................1-4 1.3.2 Other Measured Parameters .......................................1-6 1.3.3 Measured Compartments .........................................1-7 1.4 Objectives ...........................................................1-8 1.5 Design ..............................................................1-9 1.5.1 Organization...................................................1-9 1.5.2 Study Participants...............................................1-9 1.5.3 Workgroups ..................................................1-10 1.5.4 Information Management........................................1-10 1.5.4.1Data Reporting..........................................1-12 1.5.4.2Great Lakes Environmental Monitoring Database...............1-12 1.5.4.3 Public Access to LMMB Data ..............................1-12 1.5.5 Quality Assurance Program ......................................1-13 1.6 Project Documents and Products .........................................1-15 Chapter 2 Atrazine Study Overview..................................................2-1 2.1 Atrazine Introduction ...................................................2-1 2.1.1 Physical/Chemical Properties......................................2-1 2.1.2 Atrazine Use...................................................2-1 2.1.3 Regulatory Background ..........................................2-2 2.1.4 Fate and Effects.................................................2-2 2.2 Study Design .........................................................2-3 2.2.1 Description ....................................................2-3 2.2.2 Scope.........................................................2-3 2.2.3 Organization/Management........................................2-4 2.3 Sampling Locations....................................................2-5 2.3.1 Atmospheric Components .........................................2-5 2.3.2 Tributaries.....................................................2-7 2.3.3 Open Lake.....................................................2-9 2.4 Sampling Methods .....................................................2-9 2.4.1 Atmospheric Components .........................................2-9 2.4.2 Tributaries....................................................2-10 2.4.3 Open Lake....................................................2-11 2.5 Analytical Methods ...................................................2-11 2.5.1 Atmospheric Components ........................................2-11 2.5.2 Tributaries and Open Lake.......................................2-11 v Results of the LMMB Study: Atrazine Data Report 2.6 Quality Implementation and Assessment ...................................2-12 Chapter 3 Atrazine in Atmospheric Components .......................................3-1 3.1 Results..............................................................3-1 3.1.1 Vapor Fraction .................................................3-2 3.1.1.1Seasonal Variation........................................3-4 3.1.1.2Geographical Variation ....................................3-4 3.1.1.3 Analysis of Breakdown Products .............................3-4 3.1.2 Particulate Fraction..............................................3-4 3.1.2.1Seasonal Variation........................................3-5 3.1.2.2Geographical Variation ....................................3-6 3.1.2.3 Analysis of Breakdown Products .............................3-9 3.1.3 Precipitation Fraction............................................3-9 3.1.3.1Seasonal Variation.......................................3-10 3.1.3.2Geographical Variation ...................................3-14 3.1.3.3 Analysis of Breakdown Products ............................3-16 3.2 Data Interpretation....................................................3-17 3.2.1 Atmospheric Sources and Concentrations ...........................3-17 3.2.2 Seasonality ...................................................3-18 3.2.3 Regional Considerations.........................................3-18 3.2.4 Atrazine Breakdown Products ....................................3-19 3.3 Quality Implementation and Assessment ...................................3-20 Chapter 4 Atrazine in Tributaries....................................................4-1 4.1 Results..............................................................4-1 4.1.1 Seasonal Variation ..............................................4-1 4.1.2 Geographical Variation...........................................4-5 4.1.3 Analysis of Breakdown Products ...................................4-8 4.2 Data Interpretation....................................................4-10 4.2.1 Atrazine Levels in Lake Michigan Tributaries........................4-10 4.2.2 Comparison to Regulatory Limits..................................4-11 4.2.3 Seasonality ...................................................4-11 4.2.4 Regional Considerations.........................................4-11 4.2.5 Atrazine Breakdown Products ....................................4-13 4.3 Quality Implementation and Assessment ...................................4-13 Chapter 5 Atrazine in the Open-Lake Water Column ...................................5-1 5.1 Results..............................................................5-1 5.1.1 Geographical Variation...........................................5-1 5.1.2 Seasonal Variation ..............................................5-2 5.1.3 Vertical Variation...............................................5-5 5.1.4 Analysis of Breakdown Products ...................................5-5 5.2 Data Interpretation.....................................................5-6 5.2.1 Atrazine Levels in Lake Michigan..................................5-6 5.2.2 Comparison to Regulatory Limits...................................5-7 5.2.3 Lateral Variation................................................5-7