Upload
daniella-chesser
View
221
Download
0
Embed Size (px)
Citation preview
U.S. Department of the InteriorU.S. Geological Survey
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...
At least, national criteria issued pursuant to the law.
, # 2
March
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 at Eagle, Alaska
USGS Photo
BLM- and hardness based chronic copper criterion, Yukon River at Eagle, AK
0
10
20
30
40
50
60
70
Oct
-20
00
Jan
-20
01
Ap
r-2
00
1
Jul-
20
01
Oct
-20
01
Jan
-20
02
Ap
r-2
00
2
Jul-
20
02
Oct
-20
02
Jan
-20
03
Ap
r-2
00
3
Jul-
20
03
Oct
-20
03
Jan
-20
04
Ap
r-2
00
4
Jul-
20
04
Oct
-20
04
Jan
-20
05
Ap
r-2
00
5
Jul-
20
05
Date
Co
pp
er
(µg
/l)
0
2
4
6
8
10
12
14
16
DO
C (
mg
/L)
BLM-CCC
Hardness-basedCCC (µg/L)Cu CWQG (1987)
DOC
Yukon River
USGS Photo
0
2,000
4,000
6,000
8,000
10,000
12,000
14,000
16,000
18,000
20,000
Oct
-20
00
Jan
-20
01
Ap
r-2
00
1
Jul-
20
01
Oct
-20
01
Jan
-20
02
Ap
r-2
00
2
Jul-
20
02
Oct
-20
02
Jan
-20
03
Ap
r-2
00
3
Jul-
20
03
Oct
-20
03
Jan
-20
04
Ap
r-2
00
4
Jul-
20
04
Date
Flo
w (
m3 /s
)
0
2
4
6
8
10
12
14
16
DO
C (
mg
/L)
Flow DOC
Uncredited photo, www.city-data.com
Columbia River between Northport, WA and Trail, BCBLM-based acute copper criterion, Columbia River
at Northport, WA, 1995-2000
0
2
4
6
8
10
12N
ov-1
995
Feb
-199
6
May
-199
6
Aug
-199
6
Nov
-199
6
Feb
-199
7
May
-199
7
Aug
-199
7
Nov
-199
7
Feb
-199
8
May
-199
8
Aug
-199
8
Nov
-199
8
Feb
-199
9
May
-199
9
Aug
-199
9
Nov
-199
9
Feb
-200
0
May
-200
0
Aug
-200
0
Date
Co
pp
er (
µg
/l)
Ambient Copper
BLM-CCC
Hardness-based CCC
CWQG (1987)
Northwestern soft water salmon stream, Big Soos Creek, WA
Photo King County Department of Parks and Natural Resources
BLM- and hardness based chronic copper criterion, Big Soos Creek, Auburn, WA
0
5
10
15
20
25
30
De
c-1
99
5
Fe
b-1
99
6
Ap
r-1
99
6
Jun
-19
96
Au
g-1
99
6
Oct
-19
96
De
c-1
99
6
Fe
b-1
99
7
Ap
r-1
99
7
Jun
-19
97
Au
g-1
99
7
Oct
-19
97
De
c-1
99
7
Fe
b-1
99
8
Ap
r-1
99
8
Date
Co
pp
er
(µg
/l)
BLM-CCC
Hardness-based CCC (EPA 2002), µg/L)
Ontario 1994 PWQO
CWQG (1987)
Extremely soft water stream
USFS Photo
BLM- and hardness based chronic copper criterion, NF Coeur d'Alene River
0
1
2
3
4
5
6
Mar-1999
Apr-1999
May-1999
Jun-1
999
Jul-1
999
Aug-1999
Sep-1999
Oct-19
99
Nov-1
999
Dec-1
999
Jan-2
000
Feb-2000
Date
Co
pp
er (
µg
/l)
BLM-CCCCWQG (1987)Ontario 1994 PWQO
North Fork Coeur d’Alene River at Enaville, Idaho, Hardness 11-23 mg/L, DOC 0.8 to 1.1 mg/L
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)
BLM- and hardness based chronic copper criterion, Snake River above Jackson Lake, WY
0
2
4
6
8
10
12
14
16
18
Apr
-199
3O
ct-1
993
Apr
-199
4O
ct-1
994
Apr
-199
5O
ct-1
995
Apr
-199
6O
ct-1
996
Apr
-199
7O
ct-1
997
Apr
-199
8O
ct-1
998
Apr
-199
9O
ct-1
999
Apr
-200
0O
ct-2
000
Apr
-200
1O
ct-2
001
Apr
-200
2O
ct-2
002
Apr
-200
3O
ct-2
003
Apr
-200
4
Date
Co
pp
er
(µg
/l)
BLM-based CCC (µg/L)
Hardness-capped CCC(NTR, µg/L)
Ontario 1994 PWQO
CWQG (1987)
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)
0
5
10
15
20
25
1994
Co
pp
er
(µg
/l)
0
1
2
3
4
5
DO
C (
mg
/L)
BLM-CCC
Hardness-equation criteria
DOC
Data from Stratus Consulting
Copper and DOC concentrations rose together during early snowmelt
0
20
40
60
80
100
120
140
160
1994
Co
pp
er
(µg
/l)
0
1
2
3
4
5
DO
C (
mg
/L)
BLM-CCC
Ambient CuDOC
Data from Stratus Consulting
Extrapolating patterns to post-remedial conditions
0
5
10
15
20
25
December March May July
Season
Cu
(µ
g/L
)
0
1
2
3
4
5
DO
C (
mg
/L)
BLM-CCC (1994)
Cu (2005)
DOC (1994)
0
5
10
15
20
25
December March May July
BLM-CCC (1994)
Cu (2005)
Hardness-CCC(1994)
DOC and pH data quality are important!
Chronic copper criteria: Teton River at St. Anthony, ID USGS 13055000
0
10
20
30
40
50
60
70
80
90
Jan-93 Aug-93 Mar-94 Sep-94 Apr-95 Oct-95
Cu
(µ
g/L
)
0
2
4
6
8
10
12
DO
C (
mg
/L)
BLM-based CCC (µg/L, diss.)
DOC
What’s happened in September 93?
DOC and pH data quality are important!
Beware USGS DOC data prior to 1994!
25%
75%
50%
95%
5% 25%75%50%
95%
5%
Pre-1994 1994 and later0
2
4
6
8
10
12
DO
C (
mg
/L)
Columbia River between Northport, WA and Trail, BC
APre-1994
B1994 and later
0
2
4
6
8
10
12
DO
C (
mg/
L)Colorado River downstream of Glen Canyon Dam, Arizona
25%
75%
50%
95%
5%
25%
75%
50%
95%
5%
Pre-1994 1994 and later0
2
4
6
8
10
12
14
16
18
20
DO
C (
mg/
L)
Neuse River, North Carolina coastal plain
10
100
1,000
10 100 1,000
Measured Cu LC50s (µg/L)
Pre
dic
ted
Cu
LC
50
s (
µg
/L) y = 0.80x + 40
r2 = 0.88
Data originally from Erickson 1996
Assuming DOC as 1.1 mg/L, HydroQual’s 2003 LA50 of 7.32(DOC not measured)
10
100
1,000
10 100 1,000
Measured Cu LC50s (µg/L)
Predicted Cu LC50s (µg/L)
10
100
1,000
10 100 1,000
Measured Cu LC50s (µg/L)
Predicted Cu LC50s (µg/L)
Assuming DOC as 1.35 mg/L, EPA’s 2003 LA50 of 3.56
Fathead minnows in low alkalinity Precambrian Shield Lakes (Data from Welsh et al., 1993).
Photo courtesy of Paul Welch
1
10
100
1,000
1 10 100 1,000
Measured Cu LC50s (µg/L)
Predicted Cu LC50s (µg/L)
Welsh et al. (1993)
Welsh et al. (1996)
LA50 7.32, no Mg, April 2003DOC 100% reactive as 90% FA, 10% HA
1
10
100
1,000
1 10 100 1,000
Measured Cu LC50s (µg/L)P
red
icte
d C
u L
C5
0s
(µ
g/L
)
Welsh et al. (1993)
Welsh et al. (1996)
Welsh et al. (1993,1996) using HydroQual's 2007 default LA50of 5.48 includes Mg,assuming that 100% DOC is Cu-reactive
1
10
100
1,000
1 10 100 1,000
Measured Cu LC50s (µg/L)
Pre
dic
ted
Cu
LC
50
s (
µg
/L)
Welsh et al. (1993)
Welsh et al. (1996)
Welsh et al. (1993,1996) using EPA's 2003, recalculating a LA50 6.313 assuming that 50% of DOC is Cu-reactive
DOC 50% Cu-reactiveLA50 6.313, no Mg(Recalculated from EPA 2003)
DOC 100% Cu-reactiveLA50 5.48, includes Mg, (6-10-2007) (default)
Model LA50: 7.32 nmol Cu/g gill
Modified LA50: 0.2 nmol Cu/g gill
Fathead minnows in low alkalinity South Carolina piedmont streams
(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
Using EPA’s 2003 updated dataset and assuming 50% of DOC is Cu-reactive
(data from VanGenderen et al., 2005).
1
10
100
1,000
1 10 100 1,000
Measured 48-hr Cu LC50s (µg/L)
Pre
dic
ted
96
-hr
Cu
LC
50
s (
µg
/L)
y = 0.86x + 38
r2 = 0.79
VanGenderen et al. (2005) using EPA's 2003 LA50, recalculated assuming that 50% of DOC is Cu-reactive
Fatmucket, Lampsilis siliquoidea
< 0.3mm
Data from Ning Wang, USGS, Columbia, Missouri, et al., in prep.,
Acute tests in waters with variable hardness and different DOC sources
Photos by Doug Hardesty, USGS
Fatmucket mussel
DOC (mg C/L)
0 2 4 6 8 10 12
Dis
solv
ed C
u E
C50
( g
/L)
0
100
200
300
400Pond, r2=0.92Eagle Bluffs, r2=0.96Ditch #6, r2=0.92Luther Marsh, r2=0.97Humic acid, r2=0.97
A. Assume DOC is 100% reactive as 90% FA, 10% HA, (LA50 0.0605 nmol Cu/g gill)
Fatmucket
1
10
100
1000
1 10 100 1000
Measured Cu EC50s (µg/L)
Pre
dict
ed C
u E
C50
s (µ
g/L)
Pond
Eagle Bluffs
Ditch #6
Luther Marsh
Humic acid
Variablehardness Reference tests
y = 1.376x - 2.67
r 2 = 0.88p <0.001(pooling all groups)
1
10
100
1000
1 10 100 1000
Measured Cu EC50s (µg/L)
y = 0.90x + 12.1
r 2 = 0.87p <0.001(pooling all groups)
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
0 100 200 300 400 5000
100
200
300
400
500
Mea
sure
d E
C50
(µ
g/L)
BLM predicted EC50 (µg/L)
Pond Eagle Bluffs Ditch #6 Luther Marsh Humic Acid Variable Hardness Reference tests
50 100 150 200 250 3000
100
200
300
400
500
Mea
sure
d E
C50
(µ
g/L)
Hardness as mg/L CaCO3
y = 0.37x +27.2r2 = 0.05P =0.2(pooling all groups)
y = 0.96x - 0.207r2 = 0.9P <0.001(pooling all groups)
95% prediction bands
Escanaba River, Michigan photo, wikipedia.org
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
1
10
100
1,000
1 10 100 1,000
Measured Cu LC50s (µg/L)P
red
icte
d C
u L
C5
0s
(µ
g/L
)
Natural waters
Mod hard reference tests
1
10
100
1,000
1 10 100 1,000
Measured Cu LC50s (µg/L)
Pre
dic
ted
Cu
LC
50
s (
µg
/L)
Natural waters
Mod hard water referencetestsDOC 50% Cu-reactive
LA50 0.2378, no Mg(Recalculated from EPA 2003)
DOC 100% Cu-reactiveLA50 0.0701, includes Mg, (6-10-2007) (default)
Ceriodaphnia dubia
Hyalella azteca
1
10
100
1000
1 10 100 1000
Observed Cu LC50s (µg/L)
Pred
icte
d C
u L
C50
s (µ
g/L
)
NOM varies (Welsh 1996)
pH,Ca vary (48hr, Collyard 2002)
pH varies (Schubauer 1993)
NOM series y = 1.3137x - 7.1126r2 = = 0.9923
Doug Hardesty, USGS
Assume DOC is 50% reactive as FA
Assume DOC is 100% reactive as 90% FA, 10% HA
Rainbow trout flow-through tests using natural and lab waters, DOC <0.11 to 2.0 mg/L.
Welsh, Lipton, and Maest, (Stratus Consulting)
Josh Lipton, Stratus Consulting
1
10
100
1 10 100
Measured Cu LC50s (µg/L)
Pre
dic
ted
Cu
LC
50
s (
µg
/L)
Flow through
Renewal
y = 0.99x + 3.27r2 = 0.58
<
1
10
100
1 10 100
Measured Cu LC50s (µg/L)
Pre
dic
ted
Cu
LC
50
s (
µg
/L)
y = 0.85x + 4.0
r2 = 0.61
Chinook salmon, Sacramento River and lab waters (default)
Chinook salmon, Sacramento River and lab waters (50% AFA)
1
10
100
1 10 100
Measured Cu LC50s (µg/L)
Pre
dic
ted
Cu
LC
50
s
(µg
/L)
y = 0.62x + 3.63
r2 = 0.62
Assume DOC is 50% reactive as FA
Assume DOC is 100% reactive as 90% FA, 10% HA
Chinook salmon flow-through tests using natural and lab waters, DOC 0.11 to 1.4 mg/L.
Welsh, Lipton, and Maest, (Stratus Consulting)
Josh Lipton, Stratus Consulting
Rainbow trout, renewal exposures
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.
10
100
1,000
10 100 1,000
Observed Cu LC50s (µg/L)
Pred
icte
d C
u L
C50
s (µ
g/L
)
Rainbow trout 96-h LC50
1:1 Line (perfect agreement)
2:1 Line (0.5X less toxic thanpredicted)1:2 Line (2X more toxic thanpredicted)
y = 0.6847x + 17.233R2 = 0.4752
10
100
1,000
10 100 1,000
Observed Cu LC50s (µg/L)
Pred
icte
d C
u L
C50
s (µ
g/L
)
Rainbow trout 96-h LC50
1:1 Line (perfect agreement)
2:1 Line (0.5X less toxic thanpredicted)1:2 Line (2X more toxic thanpredicted)
y = 0.51x + 33.927R2 = 0.617
Assume DOC is 50% reactive as FA
Assume DOC is 100% reactive as 90% FA, 10% HA
Some Bad News
1
10
100
1000
1 10 100 1000
Observed Cu LC50s (µg/L)
Pre
dic
ted
Cu
LC
50
s (µ
g/L
)
Using BLM v2.1.2 (Mg ignored)
Using v2.2.3 (Mg included)
Rainbow trout 96h LC50s, uniform total hardness with varying Ca and Mg, uniform low DOC, Welsh et al 2000
Rainbow trout 96h LC50s, uniform total hardness with varying Ca and Mg, uniform low DOC, Welsh et al 2000
1
10
100
1000
1 10 100 1000
Observed Cu LC50s (µg/L)
Pre
dict
ed C
u LC
50s
(µg/
L)
DOC cocktail equivalents
Actual DOC cocktail mass
BLM Predicted vs. observed rainbow trout LC50s, varying DOC equivalents from 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 analogue
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
Chronic EC10s
DOC 50% reactive, as AFA
0.1
1
10
100
0.1 1 10 100
Observed Cu LC50s (µg/L)
Pred
icte
d C
u L
C50
s (µ
g/L
)
Rainbow trout
Brook trout
Fathead minnow
Chinook salmon
DOC 50% reactive, as AFA
0
5
10
15
20
25
30
35
40
0 5 10 15 20 25 30 35 40Observed Cu LC50s (µg/L)
Pre
dict
ed C
u L
C50
s (µ
g/L
)
Rainbow trout
Brook trout
Fathead minnow
Chinook salmon
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
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
Median olfaction IC50s assuming 100% of DOC is Cu reactive (model default)
0
5
10
15
20
25
30
35
40
0 10 20 30 40
Median olfaction IC50s (µg/L)
BL
M P
red
icte
d IC
50
s (
µg
/L)
Varying DOC
Varying Ca
Varying alkalinity
McIntyre olfaction IC50s assuming 50% of DOC is Cu reactive as FA
0
5
10
15
20
25
30
35
40
0 5 10 15 20 25 30 35 40
Median olfaction IC50s (µg/L)
Pre
dic
ted
EC
50
s (
µg
/L)
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
0
10
20
30
40
50
60
70
80
90
Feb-70 Aug-70 Mar-71 Sep-71 Apr-72 Oct-72 May-73
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)
BLM chronic criterion
Safe from adverse effects (range)
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
0
3
6
9
12
15
18
Aug Oct Jan Apr Jul Oct
BLM-chronic criterion (DOC 3.7 mg/L)
Stream eco-strucure LOEC
Stream eco-function LOEC; eco-structure NOEC
BLM-chronic criterion (avg. high lakes DOC, 1.8 mg/L)
BLM and field effects - Sierra Nevada stream
Copper (µg/L)
1979 1980
Sources:Leland and Carter, Freshwater Biology,1984, 1985, 1989Brooks and others, Ecosystems, 2005
BLM and experimental streams
New River near Blacksburg, VA, New River Valley Bird Club
Chronic BLM-based copper criteria and macroinvertebrate effects concentrations: New River at Glen Lyn, VA
0.0
5.0
10.0
15.0
20.0
25.0
23-Aug-96 1-Dec-96 11-Mar-97 19-Jun-97 27-Sep-97 5-Jan-98
Dis
solv
ed C
op
per
(u
g/L
)
BLM-based chronic criteria (µg/L,diss.)
Loss of 96% of mayflies, 60% of totalabundance, and 47% of taxa; 42-dexposure10-d EC50 (total individuals)
10-d EC50 (total individuals)
Loss of 96% of mayflies, 60% of totalabundance, and 47% of taxa; 42-dexposure
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
30 week aquatic microcosm experiment
S.F. Hedtke, Aquatic Tox., 1984
0.1
1
10
100
1000
Control NOEC LOEC Severe Severe Severe
Microcosm community effects
Dis
s. C
u (
ug
/L)
BLM-CCC-high
BLM-CCC Low
Treatments (µg/L)
I think I learned ...
1. BLM performed well across a broad range of waters and with diverse taxa
2. Paucity of chronic toxicity data from varied waters. Chemosensory testing valuable, esp. tests of whether effects are ecologically relevant
3. Experimental stream studies could be compelling4. BLM too sensitive to DOC?
Assuming 100% of DOC is Cu-reactive may be a factor.Overprotective at low DOC and underprotective higher DOC.
5. 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.
6. Adding Mg to the model not helpful in these datasets. Perhaps limit to site-specific situations where Mg is important.
7. Emphasis on equilibrating waters in FT tests seems misplaced.8. 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
Besser, J. M., N. Wang, F. J. Dwyer, F. L. Mayer, and C. G. Ingersoll. 2005. Assessing contaminant sensitivity of endangered and threatened fishes: 2. Chronic toxicity of copper and pentachlorophenol to two endangered species and two surrogate species. Archives of Environmental Contamination and Toxicology. 48(2): 155-165.
Brooks, P. D., C. M. O’Reilly, S. A. Diamond, D. H. Campbell, R. Knapp, D. Bradford, P. S. Corn, B. Hossack, and K. Tonnessen. 2005. Spatial and temporal variability in the amount and source of dissolved organic carbon: implications for ultraviolet exposure in amphibian habitats. Ecosystems. 8(5): 478 - 487.
Chapman, G. A. 1982. Chinook salmon early life stage tests with cadmium, copper, and zinc. Letter of December 6, 1982 to Charles Stephan, U.S. EPA Environmental Research Laboratory, Duluth. U.S. Environmental Protection Agency, Environmental Research Laboratory, Corvallis, Oregon (obtained via the USEPA Water Docket, http://www.epa.gov/ow/docket.html).
Clements, W. H., D. S. Cherry, and J. Cairns, Jr. 1988. The impact of heavy metals on macroinvertebrate communities: a comparison of observational and experimental results. Canadian Journal of Fisheries and Aquatic Sciences. 45(11): 2017-2025.
Clements, W. H., J. L. Farris, D. S. Cherry, and J. Cairns, Jr. 1989. The influence of water quality on macroinvertebrate community responses to copper in outdoor experimental streams. Aquatic Toxicology. 14(3): 249-262.
Collyard, S. A. 2002. Bioavailability of copper to the amphipod Hyalella azteca. MSc. Department of Zoology and Physiology, University of Wyoming, Laramie, Wyo.
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.
Erickson, R. J., D. A. Benoit, V. R. Mattson, H. P. Nelson, and E. N. Leonard. 1996. The effects of water chemistry on the toxicity of copper to fathead minnows. Environmental Toxicology and Chemistry. 15(2): 181-193.
Geckler, J. R., W. B. Horning, T. M. Nieheisel, Q. H. Pickering, E. L. Robinson, and C. E. Stephan. 1976. Validity of laboratory tests for predicting copper toxicity in streams. U.S. EPA Ecological Research Service, EPA 600/3-76-116, Cincinnati, OH. 208 pp.
GLEC. 2006. Development of a copper criteria adjustment procedure for Michigan’s Upper Peninsula waters. Great Lakes Environmental Center, Traverse City, Michigan and Columbia, Ohio, Prepared for the Michigan Department of Environmental Quality. 44 pp.
Hansen, J. A., J. Lipton, P. G. Welsh, J. Morris, D. Cacela, and M. J. Suedkamp. 2002. Relationship between exposure duration, tissue residues, growth, and mortality in rainbow trout (Oncorhynchus mykiss) juveniles sub-chronically exposed to copper. Aquatic Toxicology. 58: 175-188.
Hedtke, S. F. 1984. Structure and function of copper-stressed aquatic microcosms. Aquatic Toxicology. 5(3): 227-244. Leland, H. V. and J. L. Carter. 1984. Effects of copper on species composition of periphyton in a Sierra Nevada, California, stream. Freshwater
Biology. 14(3): 281-296. Leland, H. V. and J. L. Carter. 1985. Effects of copper on production of periphyton, nitrogen fixation and processing of leaf litter in a Sierra
Nevada, California, stream. Freshwater Biology. 15(2): 155-173. Leland, H. V., S. V. Fend, T. L. Dudley, and J. L. Carter. 1989. Effects of copper on species composition of benthic insects in a Sierra Nevada,
California, stream. Freshwater Biology. 21(2): 163-179.
References mentioned in the slides:
Maest, A., D. J. Beltman, D. Cacela, J. Lipton, J. Holmes, K. LeJeune, and T. Podrabsky. 1995. Spring 1994 surface water inju ry assessment report: Blackbird Mine site NRDA. Submitted by: RCG/Hagler Bailly, Boulder, CO. Submitted to: State of Idaho and Na tional Oceanic and Atmospheric Administration. 214 pp.
Marr, J. C. A., J. Lipton, D. Cacela, J. A. Hansen, H. L. Bergman, J. S. Meyer, and C. Hogstrand. 1996. Relationship between copper exposure duration, tissue copper concentration, and rainbow trout growth. Aquatic Toxicology. 36(1): 17-30.
Marr, J. C. A., J. Lipton, D. Cacela, J. A. Hansen, J. S. Meyer, and H. L. Bergman. 1999. Bioavailability and acute toxicity of copper to rainbow trout (Oncorhynchus mykiss) in the presence of organic acids simulating natural dissolved organic carbon. Canadian Journal of Fisheries and Aquatic Sciences. 56(8): 1471-1483.
McIntyre, J. K., D. H. Baldwin, J. P. Meador, and N. L. Scholz. 2008. Chemosensory deprivation in juvenile coho salmon expose d to dissolved copper under varying water chemistry conditions. Environmental Science and Technology. 10.1021/es071603e.
McKim, J. M. and D. A. Benoit. 1971. Effects of long-term exposure to copper on survival, growth and reproduction (Salvelinus fontinalis). Journal of the Fisheries Research Board of Canada. 28(5): 655-662.
McKim, J. M. and D. A. Benoit. 1974. Duration of toxicity tests for establishing "no effect" concentrations for copper with b rook trout (Salvelinus fontinalis). Journal of the Fisheries Research Board of Canada. 31: 449-452.
Mount, D. I. 1968. Chronic toxicity of copper to fathead minnows (Pimephales promelas, rafinesque) Water Research. 2(3): 215-223. Santore, R. C., P. R. Paquin, D. M. Di Toro, H. E. Allen, and J. S. Meyer. 2001. Biotic ligand model of the acute toxicity of metals. 2. Application
to acute copper toxicity in freshwater fish and Daphnia. Environmental Toxicology and Chemistry. 20(10): 2397-2402. Sauter, S., K. S. Buxton, K. J. Macek, and S. R. Petrocelli. 1976. Effects of exposure to heavy metals on selected freshwater fish: toxicity of
copper, cadmium, chromium and lead to eggs and fry of seven fish species. U.S. Environmental Protection Agency, EPA -600/3-76-105, Duluth, Minnesota. 85 pp.
Schubauer-Berigan, M. K., J. R. Dierkes, P. D. Monson, and G. T. Ankley. 1993. pH-dependent toxicity of Cd, Cu, Ni, Pb, and Zn to Ceriodaphnia dubia, Pimephales promelas, Hyalella azteca, and Lumbriculus variegatus. Environmental Toxicology and Chemistry. 12(7): 1261-1266.
Seim, W. K., L. R. Curtis, S. W. Glenn, and G. A. Chapman. 1984. Growth and survival of developing steelhead trout (Salmo gairdneri) continuously or intermittently exposed to copper. Canadian Journal of Fisheries and Aquatic Sciences. 41(3): 433 -438.
Stratus. 1996. Preliminary toxicological evaluation, U.S. v. Iron Mountain Mines, Inc. Stratus Consulting, Inc. (formerly Hagler Bailly Services), Boulder, Colo. http://www.stratusconsulting.com.
Stratus. 1998. Data report: Acute copper toxicity to salmonids in surface waters in the vicinity of the Iron Mountain Mine, California. Stratus Consulting, Inc. (formerly Hagler Bailly Services), Boulder, Colo. http://www.stratusconsulting.com.
USGS, 2005, National Water Data - NWIS Web: U.S. Geological Survey, Accessed October 2005, http://waterdata.usgs.gov/nwis/ Van Genderen, E. J., A. C. Ryan, J. R. Tomasso, and S. J. Klaine. 2005. Evaluation of acute copper toxicity to larval fathead minnows (Pimephales
promelas) in soft surface waters. Environmental Toxicology and Chemistry. 24(2): 408–414. Welsh, P. G. 1996. Influence of dissolved organic carbon on the speciation, bioavailability and toxicity of metals to aquatic biota in soft water
lakes. Ph.D., University of Waterloo, Waterloo, Ontario, Canada.
References mentioned in the slides
Welsh, P. G., J. Lipton, T. L. Podrabsky, and G. A. Chapman. 2000. Relative importance of calcium and magnesium in hardness-based modification of copper toxicity. Environmental Toxicology and Chemistry. 19(6): 1624–1631.
Welsh, P. G., J. L. Parrott, D. G. Dixon, P. V. Hodson, D. J. Spry, and G. Mierle. 1996. Estimating acute copper toxicity to larval fathead minnow (Pimephales promelas) in soft water from measurements of dissolved organic carbon, calcium, and pH. Canadian Journal of Fisheries and Aquatic Sciences. 53(6): 1263-1271.
Welsh, P. G., J. F. Skidmore, D. J. Spry, D. G. Dixon, P. V. Hodson, N. J. Hutchinson, and B. E. Hickie. 1993. Effect of pH and dissolved organic carbon on the toxicity of copper to larval fathead minnow (Pimephales promelas) in natural lake waters of low alkalinity. Canadian Journal of Fisheries and Aquatic Sciences. 50(7): 1356–1362.
References mentioned in the slides