1. Forest Herbicide Residues in Surface Water and Plants in the Tribal Territory of the Lower Klamath River Watershed of California P. Wofford, K.S. Goh, D. Jones, H. Casjens Department of Pesticide Regulation H. Feng, J. Hsu, D. Tran, J. Medina, J. White, Center for Analytical Chemistry California Department Food & Agriculture December 9, 2002 Klamath

2. Outline Introduction Objectives Sampling Methods – Water sampling – Plant sampling – Fish tissue sampling Results and Discussion

3. Introduction U.S. EPA grant Herbicide exposure concerns Yurok Environmental Monitoring Work Group

4. Tribal members and staff County Department of Agriculture personnel Timber company personnel CIBA personnel Department of Pesticide Regulation personnel

8. Study Area

9. Herbicides Monitored Atrazine 2,4-D Glyphosate Triclopyr

12. Objectives WATER Monitor aerial herbicide application drift into waterways Monitor herbicide runoff during rainfall events PLANTS Monitor aerial herbicide application drift Measure rate of herbicide dissipation on plants at application sites

13. Water Sampling Methods Grab sample ISCO® autosampler Minimum Detection Limits: – Atrazine = 0.05 ppb – 2,4-D and triclopyr = 0.10 ppb – Glyphosate = 2.00 ppb Water Quality Parameters: – Temperature, pH, dissolved oxygen, and electrical conductivity

15. Drift During Application Monitored waterways which ran through application area Five aerial applications monitored Sampled during entire application

16. Site G 13 acres glyphosate 1100 ft away Site E 40 acres triclopyr In boundary Site F 105 acres triclopyr 1700 ft away Fall 1999

17. Site I 245 acres triclopyr, 2,4-D 200 ft away Site J 230 acres triclopyr, 2,4-D 400 ft away Spring 2000

19. Rainfall Event Monitoring 12 sites monitored Both ground and aerial applications monitored

20. Site A ground 9 acres atrazine 82 ft away Site B ground 36 acres atrazine, triclopyr 2500 ft away Site C ground 25 acres atrazine 2500 ft away Site D aerial 360 acres 2,4-D, atrazine 2 miles away Spring 1999

21. Site G 13 acres glyphosate 1100 ft away Site E 40 acres triclopyr In boundary Site F 105 acres triclopyr 1700 ft away Fall 1999

23. Site H ground 36 acres atrazine, triclopyr 500 ft away Site J aerial 230 acres 2,4-D, triclopyr 400 ft away Site K ground 80 acres atrazine 1300 ft away Site L aerial 20 acres 2,4-D, triclopyr 200 ft away Site M aerial 100 acres 2,3-D, triclopyr 1600 ft away Spring 2000

25. Plant Sampling Methods Only triclopyr and 2,4-D were monitored Composite samples

26. Plants Selected For Monitoring Beargrass (Xerophyllum tenax) - leaves Huckleberry (Vaccinium ovatum) - berries Maidenhair fern (Adiantum pedatum) - stems Manzanita (Arctostaphyllos spp.) - berries Oregon grape (Berberis nevosa) - roots Tanoak (Lithocarpus densiflorus) - acorn Willow (Salix spp.) - shoots Yarrow (Achillea milleforlium) - stems and leaves

27. beargrass

28. huckleberry

29. manzanita

30. Oregon grape

31. tanoak acorns

32. yarrow

33. Minimum Detection Limits for 2,4-D and triclopyr on monitored plants Beargrass = 0.05 ppm Huckleberry = 0.05 ppm Maidenhair fern = 0.05 ppm Manzanita = 0.03 ppm Oregon grape = 0.05 ppm (estimated) Tanoak = 0.05 ppm Yarrow = 0.10 ppm

34. Off-site Movement During Application Four applications monitored Sampling sites on downwind side of application Sampled beargrass, yarrow, and huckleberry

35. Site P 225 acres beargrass Site Q 35 acres Beargrass huckleberry Site S 25 acres yarrow Site V 25 acres beargrass

36. Number of Average Concentration (ppm) SiteDistance (ft)Samplestriclopyr2,4-D P1211ND 2101ND Q185 - 2156ND 220 - 2406ND 250 - 2856ND S20 - 2330.110.10 100 - 1504ND V030.560.41 30 - 4130.140.10 50 - 903ND

37. Dissipation sampling Five application areas monitored Sampled beargrass, huckleberry, manzanita, and yarrow

38. Site N 25 acres beargrass Site O 66 acres beargrass Site R 116 acres huckleberry yarrow Site T 45 acres Manzanita Site W 40 acres beargrass

42. Fish Tissue Sampling with the Department of Fish and Game Chemical analysis by the Department of Fish and Game Sampled fish tissue and water in two creeks downstream from applications Sampled: – sculpin (Cottus gulosus) in McGarvey Creek – steelhead trout (Oncorhynchus mykiss) in the West Fork of Blue Creek

45. sculpin Steelhead trout

46. Fish Tissue Results SiteDateConcentration (ppb) triclopyr 3,5,6-trichloro- 2-pyridinol 2,4-D 2,4- dichlorophenol McGarvey Creek 4/13/01ND 1 ND 2 ND 3 ND 4 5/1/01ND 5/8/01ND West Fork Blue Creek 4/13/01ND 5/1/01ND 5/8/01ND Minimum report limit: 1 1 ppb, 2 5 ppb, 3 2 ppb, 5 5 ppb

47. Water Results SiteDateConcentration (ppb) triclopyr2,4-D McGarvey Creek 4/13/01ND 5/1/01ND 5/8/01ND West Fork Blue Creek 4/13/01ND 5/1/01ND 5/8/01ND Minimum report limit: 0.10 ppb

48. Additional Sampling Plant sampling in Hupa and Kaurk gathering areas – Beargrass, woodwardia fern, willow, tanoak acorns, and huckleberry analyzed for triclopyr and 2,4-D Plant sampling in area treated for spotted knapweed – Deerbrush and Oregon grape roots analyzed for 2,4-D

49. Additional Sampling (continued) Two rain runoff sampling events following atrazine applications Tanoak acorns and huckleberry sampled for 2,4-D and triclopyr

50. ACKNOWLEDGMENTS Yurok Environmental Monitoring Work Group Lori Harder McKinnon, John Melvin, Ken Childs, Sr., Richard Myers, Susan Burdick, Jene McCovey, Kevin McKernan, Marty Geslak, Ora Smith, LaVerne Glaze, Renee Stauffer, Holly Hensher, Ron Johnson, Jennifer Kalt, Wendy George, Bessie Lee, and Chuck Striplen County Department of Agriculture John Falkenstrom, Jeff Dolf Glenn Anderson, Dave Cavyell

51. Simpson Timber Company Bernard Bush, John Pricer, and Dale Miller Center for Analytical Chemistry C. Cooper, L. Ortiz, R. Wichert, I. Aguilar, T. Woreniecka, J. Echelberry, J. Temple and A. Vaques Department of Pesticide Regulation Paul Gosselin, John Sanders, Kathy Brunetti, Carissa Gana, Jesse Ybarra, Roger Sava, Johanna Walters, and Nina Bacey U.S. Environmental Protection Agency Nancy Frost and Annie Yates