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The accuracy and protectiveness of Biotic Ligand Model (BLM) toxicity predictions with copper

The accuracy and protectiveness of Biotic Ligand Model (BLM) toxicity predictions with copper. Christopher A. Mebane U.S. Geological Survey, Boise, Idaho, USA. Workshop on Biotic Ligand Model Principles and Applications Wilfrid Laurier University, Waterloo, Ontario, Canada May 12-14, 2008.

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The accuracy and protectiveness of Biotic Ligand Model (BLM) toxicity predictions with copper

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  1. The accuracy and protectiveness of Biotic Ligand Model (BLM) toxicity predictions with copper Christopher A. Mebane U.S. Geological Survey, Boise, Idaho, USA Workshop on Biotic Ligand Model Principles and Applications Wilfrid Laurier University, Waterloo, Ontario, Canada May 12-14, 2008 All analyses and data summaries shown in this talk are provisional and subject to revision

  2. March , # 2 In the States, It’s not just a model, it’s the law... At least, national criteria issued pursuant to the law.

  3. BLM promoted to provide less stringent effluent limits “Using the new [BLM-based copper] criteria effectively” “It is expected that the BLM-based criteria will be less stringent in low hardness waters, but possibly more stringent in harder waters. Therefore, wastewater treatment plants discharging into waters with low hardness, especially with high dissolved organic carbon, should consider performing a BLM and proposing alternative copper effluent limits as appropriate.” http://www.cdm.com/knowledge_center/monthly_viewpoint/epa_copper_criteria.htm (viewed April 29, 2008)

  4. Yukon River at Eagle, Alaska USGS Photo

  5. Yukon River USGS Photo

  6. Columbia River between Northport, WA and Trail, BC Uncredited photo, www.city-data.com

  7. Northwestern soft water salmon stream, Big Soos Creek, WA Photo King County Department of Parks and Natural Resources

  8. Extremely soft water stream North Fork Coeur d’Alene River at Enaville, Idaho, Hardness 11-23 mg/L, DOC 0.8 to 1.1 mg/L USFS Photo

  9. Snake River leaving Yellowstone National Park, Wyoming (hardness 25-60 mg/L, pH 7 to 8.5, DOC 0.9 to 4.5 mg/L)

  10. Copper contaminated western mountain stream, Panther Creek, Idaho (DOC 1.1 to 4.6 mg/L, hardness 25-50, pH 7.5 to 8.6) Data from Stratus Consulting

  11. Copper and DOC concentrations rose together during early snowmelt Data from Stratus Consulting

  12. Extrapolating patterns to post-remedial conditions

  13. DOC and pH data quality are important! What’s happened in September 93?

  14. DOC and pH data quality are important!

  15. Beware USGS DOC data prior to 1994! Columbia River between Northport, WA and Trail, BC

  16. Colorado River downstream of Glen Canyon Dam, Arizona

  17. Neuse River, North Carolina coastal plain

  18. Data originally from Erickson 1996

  19. Assuming DOC as 1.1 mg/L, HydroQual’s 2003 LA50 of 7.32 (DOC not measured) Assuming DOC as 1.35 mg/L, EPA’s 2003 LA50 of 3.56

  20. LA50 7.32, no Mg, April 2003 DOC 100% reactive as 90% FA, 10% HA Photo courtesy of Paul Welch Fathead minnows in low alkalinity Precambrian Shield Lakes (Data from Welsh et al., 1993).

  21. DOC 100% Cu-reactive LA50 5.48, includes Mg, (6-10-2007) (default) DOC 50% Cu-reactive LA50 6.313, no Mg (Recalculated from EPA 2003)

  22. Fathead minnows in low alkalinity South Carolina piedmont streams (VanGenderen et al., 2005). Model LA50: 7.32 nmol Cu/g gill Modified LA50: 0.2 nmol Cu/g gill

  23. Using EPA’s 2003 updated dataset and assuming 50% of DOC is Cu-reactive (data from VanGenderen et al., 2005). (top) DOC 50 % Cu-reactive,LA50: 6.313 nmol Cu/g gill (bottom) DOC 100% Cu-reactive,LA50: 0.2 nmol Cu/g gill

  24. < 0.3mm Fatmucket, Lampsilis siliquoidea Acute tests in waters with variable hardness and different DOC sources Data from Ning Wang, USGS, Columbia, Missouri, et al., in prep., Photos by Doug Hardesty, USGS

  25. Fatmucket mussel

  26. Fatmucket A. Assume DOC is 100% reactive as 90% FA, 10% HA, (LA50 0.0605 nmol Cu/g gill) B. Assume DOC is 50% reactive as FA ((LA50 0.1916 nmol Cu/g gill) B. A.

  27. Fatmucket mussel: hardness vs. BLM as predictor of toxicity y = 0.96x - 0.207 r2 = 0.9 P <0.001 (pooling all groups) y = 0.37x +27.2 r2 = 0.05 P =0.2 (pooling all groups) 95% prediction bands

  28. Ceriodaphnia dubia ~25 natural waters, Mostly hardwater, (17-185 mg/L CaCO3), DOC 0.8 to 30 mg/L GLEC, 2006 (Tyler Linton) Escanaba River, Michigan photo, wikipedia.org

  29. Escanaba River, Michigan photo, wikipedia.org Ceriodaphnia dubia DOC 100% Cu-reactive LA50 0.0701, includes Mg, (6-10-2007) (default) DOC 50% Cu-reactive LA50 0.2378, no Mg (Recalculated from EPA 2003)

  30. Hyalella azteca Doug Hardesty, USGS

  31. Rainbow trout flow-through tests using natural and lab waters, DOC <0.11 to 2.0 mg/L. Welsh, Lipton, and Maest, (Stratus Consulting) Assume DOC is 100% reactive as 90% FA, 10% HA Assume DOC is 50% reactive as FA < Josh Lipton, Stratus Consulting

  32. Chinook salmon flow-through tests using natural and lab waters, DOC 0.11 to 1.4 mg/L. Welsh, Lipton, and Maest, (Stratus Consulting) Assume DOC is 100% reactive as 90% FA, 10% HA Assume DOC is 50% reactive as FA Josh Lipton, Stratus Consulting

  33. Rainbow trout, renewal exposures Assume DOC is 50% reactive as FA BLM Predicted vs. observed rainbow trout LC50s, in renewal tests using lab and site waters, hardwater, DOC from <1 to 11 mg/L, 3 of 4 seasonal rounds of testing (all data from the 1st of 4 rounds discarded for questionable DOC data). ENSR. 1996. Development of site-specific water quality criteria for copper in the upper Clark Fork River: Phase III WER Program testing results. ENSR Consulting and Engineering, 0480-277, Fort Collins, Colo. Assume DOC is 100% reactive as 90% FA, 10% HA

  34. Some Bad News Testing DOC “equivalents” that matched natural DOM for binding affinity and complexation. DOC equivalents ranged O.3 to 16 mg/L, (actual DOC mass 0.11 to 0.84 mg/L) in lab water of with hardness of 24 mg/L CaCO3, Marr et al 1999, Panther Creek DOC Rainbow trout 96h LC50s, uniform total hardness with varying Ca and Mg, uniform low DOC, Welsh et al 2000

  35. Chronic EC10s Rainbow trout (30-120d growth) • Besser et al, 2005 • Hansen et al, 2002 • Marr et al., 1996 • Seim et al. 1984 Brook trout (2-22 months) • McKim et al. 1971, 1974 • Sauter et al. 1976 Fathead Minnow (21-days to 11 months) • Mount 1968 • Welsh 1996 • Besser et al. 2005 Chinook salmon, 120d (treated as a rainbow trout) • Chapman 1982

  36. Reductions in the olfactory response to a natural odorant (serine) following short-term (30 min) exposure to 20 µg/L dissolved copper (McIntyre et al., ES&T, 2008) Photo: Carla Stehr, National Marine Fisheries Service, Seattle

  37. Shayler Run, Ohio, USA • Stream experimentally dosed with copper, 1968-1972 • Integrated long-term field, streamside, and laboratory toxicity studies • High calcium limestone geology • DOC from natural and sewage sources Geckler and others, 1976. Validity of laboratory tests for predicting copper toxicity in streams. EPA 600/3-76-116 Photo from Geckler and others, 1976

  38. BLM chronic criterion Safe from adverse effects (range) BLM and field effects –Ohio Stream • Threshold for adverse effects from • Full life cycle streamside toxicity tests with native fish • Fish behavioral changes in stream Cu (µg/L)

  39. Convict Creek, California, USA • Sierra Nevada stream experimentally dosed with copper for 1 yr • Measured effects on stream metabolism and macroinvertebrate community • Low calcium granitic geology • Most BLM parameters measured – except DOC • Single DOC site value of 3.7 mg/L; average DOC in High Sierra Lakes estimated at 1.8 mg/L. Photo courtesy of Daniel Dawson, Sierra Nevada Aquatic Research Laboratory

  40. BLM and field effects - Sierra Nevada stream Copper (µg/L) Sources: Leland and Carter, Freshwater Biology, 1984, 1985, 1989 Brooks and others, Ecosystems, 2005 1979 1980

  41. Macroinvertebrate exposures in August 1987, no DOC data. 1997 pH and inorganic data similar, assuming DOC is similar Clements et al., CJFAS., 1988 Clements et al., Aq. Tox., 1989 New River near Blacksburg, VA, New River Valley Bird Club BLM and experimental streams

  42. 30 week aquatic microcosm experimentS.F. Hedtke, Aquatic Tox., 1984

  43. I think I learned ... • BLM performed well across a broad range of waters and with diverse taxa • Paucity of chronic toxicity data from varied waters. Chemosensory testing valuable, esp. tests of whether effects are ecologically relevant • Experimental stream studies could be compelling • BLM too sensitive to DOC? Assuming 100% of DOC is Cu-reactive may be a factor. Overprotective at low DOC and underprotective higher DOC. • Assuming 50% of DOC is Cu-reactive fulvic acid improved predictions in most datasets from natural waters. No datasets were made much worse by the 50% AFA assumption. • Adding Mg to the model not helpful in these datasets. Perhaps limit to site-specific situations where Mg is important. • Emphasis on equilibrating waters in FT tests seems misplaced. • Quality of DOC and pH measurements critical. Recommend DOC detection to at least 0.3 mg/L in field data, 0.1 if testing synthetic waters

  44. References mentioned in the slides:

  45. References mentioned in the slides

  46. References mentioned in the slides

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