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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

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

in the states it s not just a model it s the law

March

, # 2

In the States, It’s not just a model, it’s the law...

At least, national criteria issued pursuant to the law.

blm promoted to provide less stringent effluent limits
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)

yukon river
Yukon River

USGS Photo

columbia river between northport wa and trail bc
Columbia River between Northport, WA and Trail, BC

Uncredited photo, www.city-data.com

slide7

Northwestern soft water salmon stream, Big Soos Creek, WA

Photo King County Department of Parks and Natural Resources

slide8

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

slide9

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)

slide10

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

slide11

Copper and DOC concentrations rose together during early snowmelt

Data from Stratus Consulting

doc and ph data quality are important
DOC and pH data quality are important!

What’s happened in September 93?

beware usgs doc data prior to 1994
Beware USGS DOC data prior to 1994!

Columbia River between Northport, WA and Trail, BC

slide20

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

slide21

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).

slide22

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)

slide23

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

slide24

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

fatmucket lampsilis siliquoidea

< 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

fatmucket
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.

fatmucket mussel hardness vs blm as predictor of toxicity
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

slide29

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

slide30

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)

hyalella azteca
Hyalella azteca

Doug Hardesty, USGS

slide32

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

slide33

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

rainbow trout renewal exposures
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

some bad news
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

chronic ec10s
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
slide37

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

shayler run ohio usa
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

blm and field effects ohio stream

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)

convict creek california usa
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

blm and field effects sierra nevada stream
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

blm and experimental streams

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
i think i learned
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