u.s. department of the interior u.s. geological survey bioavailability of metals from mining and...
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U.S. Department of the InteriorU.S. Geological Survey
Bioavailability of Metals from Mining and Effects on Aquatic OrganismsChristopher J. Schmitt* U.S. Geological SurveyColumbia Environmental Research CenterColumbia, MO 65201 [email protected]
*Acknowledgements
• FWS: D. Heckathorne, D. Martin, S. Dudding, T. Nash, C. Charbonneau, G. Allen, V. Tabor, J. Dwyer
• EPA: M. Doolan• Assistance (2001) from J.
Dalgarn (BIA, Miami, OK); D. Sappington (Quapaw Tribe of OK); and A. Donahue and J. Arms (CERC)
• CERC colleagues and co-authors S. Finger, M. Wildhaber, W. Brumbaugh, T. May, J. Whyte, D.Tillitt
Spring River, Cherokee Co., KS
Spring River, Ottawa Co., OK
Pb-Zn Mining Areas in MO, OK, & KS
MO
KS
OK
From Ferderer, D.A., 1996. U.S. Geological Survey, Open-File Report 96-549
IA
IL
Old Lead Belt
(Pb/Zn; Inactive)
Tri-States District (Zn/Pb;
Inactive)
New Lead Belt
(Pb/Zn; Active)
Prospecting Area
Bioavailability Not all the metals in sediment are available
for uptake by aquatic organisms – two parts• Chemical component
• Metal association (binding) with or to particles• Assessment = sequential / partial extraction
• Particle size component• Aquatic ecosystems are particle-driven; different size
particles are utilized by organisms to differing degrees• Metals not distributed uniformly among particle sizes;
difficult to assess and often ignored• Measure uptake / accumulation by organisms
Sequential Extraction (ca. 1981)
1-N HCl(AVS-SEM)
Modified from Tessier et al. (1979, Anal Chem 51:884)
Sulfide Minerals
Pore Water
Schmitt, C.J., S.E. Finger, T.W. May, and M.S. Kaiser, 1987. Bioavailability of lead and cadmium from mine tailings to the pocketbook mussel (Lampsilis ventricosa). Pp. 115-142 in R.J. Neves, ed. Proceedings of the Workshop on Die-offs of Freshwater Mussels in the United States. U.S. Fish and Wildlife Service and Upper Mississippi River Conservation Committee. Rock Island, IL.
Big R. Pb Fractions, 1981; also Zn
Schmitt, C.J., S.E. Finger, T.W. May, and M.S. Kaiser, 1987. Bioavailability of lead and cadmium from mine tailings to the pocketbook mussel (Lampsilis ventricosa). Pp. 115-142 in R.J. Neves, ed. Proceedings of the Workshop on Die-offs of Freshwater Mussels in the United States. U.S. Fish and Wildlife Service and Upper Mississippi River Conservation Committee. Rock Island, IL.
Big R. Cd Fractions, 1981
Schmitt, C.J., S.E. Finger, T.W. May, and M.S. Kaiser, 1987. Bioavailability of lead and cadmium from mine tailings to the pocketbook mussel (Lampsilis ventricosa). Pp. 115-142 in R.J. Neves, ed. Proceedings of the Workshop on Die-offs of Freshwater Mussels in the United States. U.S. Fish and Wildlife Service and Upper Mississippi River Conservation Committee. Rock Island, IL.
Big R. Crayfish vs. Sediment Pb, 1981
Total Sediment Pb (ug/g dw)
Cra
yfis
h P
b (u
g/g
dw)
Schmitt, C.J., and S.E. Finger, 1982. The transport, fate, and effects of trace metals in the Big and Black River watersheds, Southeastern Missouri. U.S. Fish and Wildlife Service, Columbia National Fisheries Research Laboratory, Columbia, MO. Project Completion Report to the St. Louis District, U.S. Army Corps of Engineers, St. Louis, MO. 167 p.
Orconectes luteus
Uptake of Pb and Cd by LampsilisT
issu
e P
b, u
g/g
dw
Tis
sue
Cd
, ug
/g d
w
Indigenous Mussels Indigenous
Mussels
Schmitt, C.J., S.E. Finger, T.W. May, and M.S. Kaiser, 1987. Bioavailability of lead and cadmium from mine tailings to the pocketbook mussel (Lampsilis ventricosa). Pp. 115-142 in R.J. Neves, ed. Proceedings of the Workshop on Die-offs of Freshwater Mussels in the United States. U.S. Fish and Wildlife Service and Upper Mississippi River Conservation Committee. Rock Island, IL.
Pb Cd
Carcass Pb vs. Sediment Pb, 1989
Log Total Sediment Pb
Log Carcass Pb
Schmitt, C.J., M.L. Wildhaber, J.B. Hunn, T. Nash, M.N. Tieger, and B.L. Steadman, 1992. Lead in Missouri streams: Monitoring pollution from mining with an assay for δ-aminolevulinic acid dehydratase (ALA-D) in fish blood. U.S. Fish and Wildlife Service, Columbia, Missouri Field Office. 43 p.
Hypentelium nigricans
Moxostoma duquesnei
Center Creek
Big River
Blood Pb vs. Sediment Pb, 1989
Log Total Sediment Pb
Log Blood Pb
Hypentelium nigricans
Moxostoma duquesnei
Center Creek
Big River
Schmitt, C.J., M.L. Wildhaber, J.B. Hunn, T. Nash, M.N. Tieger, and B.L. Steadman, 1992. Lead in Missouri streams: Monitoring pollution from mining with an assay for δ-aminolevulinic acid dehydratase (ALA-D) in fish blood. U.S. Fish and Wildlife Service, Columbia, Missouri Field Office. 43 p.
Effects Span many levels of biological organization
• Biochemical / physiological to community• Contaminant penetrates to target sites (tissue)• Exposure pathway [Sediment-(Invertebrate?)-Fish]
Documentation = laboratory + field studies• Lab studies with field-collected sediments, spiked
sediments, pore waters, waterborne metals• Isolate effects of contaminants from other factors
• Field studies -- long-term cumulative effects• Other factors difficult to tease out – Neosho madtom• Resilience
Heme Biosynthesis and Pb
Hb Fe
Joselow, M. M. 1980. Blood zinc and lead poisoning. Pp. 171-181 in J. O. Nriagu, ed. Lead in the Environment.
-Aminolevulinic Acid Dehydratase (ALA-D) Catalyzes condensation of porphobilinogen (PBG), a
porphyrin / heme precursor, from ALA Present in most cells; greatest in blood & other heme-
rich tissues (liver, spleen, kidney, etc.) Activity inhibited by Pb; affected at Pb-B ≤0.5 mg/L
(50 µg/dL) in fish Requires Zn for activation; activity inversely correlated
w/ Zn-B in previous fish studies; reactivated by Zn (?) Activity can be measured; assay has a long history
of use as Pb biomarker in humans, birds, and fish
ALA-D Activity vs. Blood Pb in Big R. Suckers, 1981
C. J. Schmitt et al., 1984. Can. J. Fish. Aquat. Sci. 41:1030-1040.
Blood Pb (ug/g ww)
ALA
-D/H
b (n
mol
/mg/
h)
ALA-D Activity vs. Blood-Pb in Big R. Longear Sunfish, 1980
F. J. Dwyer et al., 1988. J Fish Biol 33:307-313.
Blood Pb (ug/g ww)
ALA
-D/H
b (n
mol
/mg/
h)Lepomis megalotis
ALA-D/Hb vs. Sediment Pb, 1989
Log ALA-D/Hb (nmol/mg/h
Log Total Sediment Pb (ug/g dw)
Schmitt, C.J., M.L. Wildhaber, J.B. Hunn, T. Nash, M.N. Tieger, and B.L. Steadman, 1992. Lead in Missouri streams: Monitoring pollution from mining with an assay for δ-aminolevulinic acid dehydratase (ALA-D) in fish blood. U.S. Fish and Wildlife Service, Columbia, Missouri Field Office. 43 p.
Center Creek
Big River
MO
AROK
KS
Picher Field (mines & tailings; Tribal lands)
3
Gauge
Elm Ck.
Neosho R.
Miami
6
3 mi. 5
Grand L.
Tar Ck.
Spring R.
4Gauge
2
1PicherZincville
TSMD-OK 2001
TSMD
Willow Creek
Tar Creek
Center Creek
BR / Desloge, MO
Pb >1200 µg/g dw
LB / Macon, MO
BR
LB
CERCOzCf
112 Fish / 6 Spp. / 10 Sites
SR NR REF BR
Sp 1 2 4 3(R) 5 6 (TC) 7(C) 8(O) 10(L) 9 Σ
Carp 4 4 3 4 3 5 6(b,l) 2 31
ChC 5 1 5 4 2 3 3(b) 12 35
FhC 2 2 4
LmB 2 5 4 12 1 21
SpB 3 3 1 2 9
WhC 3 2 4 3 12
Field Procedures
1
2 3
4
Laboratory Methods (Individual Fish) Age (scales only; cf not aged) Hb by azide-methemoglobin (HemoCue®) Blood metals (Fe, Pb, Cd, Zn)
• Freeeze-dried and digested in tube (clean!)• Analyzed by ICPMS
Liver (carp only) and carcass metals (Pb, Cd, Zn; not LB) by ICPMS (dw liver only)
ALA-D by microtiter plate method (modified from Granick 1972 and Hodson 1976; described by Whyte et al. 2002)
PBG Standard Curve (X 3)
Blank (X 3)
ALA (X 3))
ALA-D Assay, 96-Well Microtiter Plate (12 samples + 9 standards)
Color results from Ehrlich’s reagent binding with PBG
Plate is scanned with an automated plate reader
Nmol PBG/µL blood/h
Nmol PBG/mg Hb/h
Si t e 1 2 3 45 6 9 10
l pbbd
- 1
0
1
2
l pbl d
- 1. 0 - 0. 8 - 0. 6 - 0. 4 - 0. 2 0. 0 0. 2 0. 4 0. 6 0. 8
BR
LBSite 6
(NR-TC)
Site 6(NR-TC)
Pb
-B (
ug
/g d
w)
NAWQA carp range (0.05-2.20 μg/g dw, n = 182)
5.4 μ/g (n = 1)
Pb-B vs. Pb-L in Carp, 2001*
Pb-L (ug/g dw)
y = x
Site 3(NR-Ref)
n = 30, r = 0.88, p < 0.01
*2002 for LB
Pb*, Cd*, and Zn* in Carp, 2001**
W. G. Brumbaugh et al. 2005, Arch Environ Contam Toxicol (in press).
0.1
1
10
110
1000.1
1
10
Liv
er
Blood
Car
cass
Pb
0.1
1
10
100
1000
0.010.1
10.01
0.1
1
Liv
erBlood
Car
cass
Cd
100
1000
10000
100200
300
100
200
300
Liv
er
Zn
* Blood, liver and carcass; all ug/g dw
** 2002 for LB
R2 = 0.78 – 0.88 (L), 0.49 – 0.72 (C)
R2 = 0.69 (L), 0.61 (C)
NS
SR & NRDischarge,Jun-Nov 2001
Collections originally scheduled for July ’01
Postponed until October due to unusually high flows
High flow may have induced carp to move
Site 3 (SR)
Site 4 (NR)
Speci es Car p ChC FhCLmB SpB WhC
l al ad
- 0. 4
- 0. 3
- 0. 2
- 0. 1
0. 0
0. 1
0. 2
0. 3
0. 4
0. 5
0. 6
0. 7
0. 8
0. 9
1. 0
1. 1
l pbbw
- 3 - 2 - 1 0 1
ALA-D/Hb vs. Pb-B, 2001*
Pb-B (ug/g ww)
All MicropterusALA-D/Hb = 0.258 – 0.219 Pb-B ,
n = 29, r2 = 0.68, p <0.01
BR
AL
A-D
/Hb
(n
mo
l/mg
/h)
All catfish (mostly ChC)ALA-D/Hb = -1.206 – 0.237 Pb-B +
0.868 Zn-B, n = 35, R2 =0.65
C. J. Schmitt et al., 2005. Environ Toxicol Chem 24, in press. *2002 for LB
Speci es Car p ChC FhCLmB SpB WhC
l f ebw
2. 0
2. 1
2. 2
2. 3
2. 4
2. 5
2. 6
2. 7
l pbbw
- 3 - 2 - 1 0 1
Fe-B (or Hb) vs. Pb-B, 2001*
BR
Carp
Pb-B (ug/g ww)
LB
CERC
Fe-
B (
ug
/g w
w)
C. J. Schmitt et al., 2005. Environ Toxicol Chem 24, in press. *2002 for LB
Summary (Bioavailability) Contamination by metals evident in TSMD fish
• Pb concentrations greater than background, but lower than in other historic mining areas (BR, etc.)
• Metals bioavailability issue resolved (blood, liver metals; correlations)• Penetration to active sites / tissues• Redundancy / QA vs. efficiency
• Variable results for carp suggest fish movement, possibly induced by flooding
ALA-D activity differed among sites (some taxa) • Relationship vs Pb-B well documented in catfish and
bass, less so in carp• Differences among taxa apparent• Sensitivity of ictalurids re. Neosho madtom?
• Bioavailability, unique biochemical response • No detectable effects on Hb or Fe-B• Exposure indicator*
Higher level effects also evident (fish, invertebrates; dns)
Future studies: Aquatic effects of Cd, Zn, and ?
Summary (Effects)