Inorganic Contaminants from Past Mining Activity:
Bioaccumulation in Fish and Aquatic MacroInvertebrates, Santa Cruz Watershed, Arizona
Peter N. Reinthal1, Floyd Gray2, and Jessica E. Gwinn1.
1University
of Arizona Department of Ecology and Evolutionary Biology,
2U.S. Geological Survey, Tucson, AZ.
Introduction
• In Arizona alone, there are >
60,000 abandoned and/or
inactive mines
• ~ 320 km of contaminated
surface water.
• Traditional methods for
remediation = capping,
solidification, bioremediation or
removal.
Environmental Remediation a Daunting
and Expensive task
Techniques are needed that can identify:
(i) Important sources of contamination,
(ii) Off-site transport mechanisms
(iii) Pathways of bioaccumulation and biomagnification
(iv) Efficacy of alternative remediation strategies.
Processes Involved in the Release, Transport, and
Deposition Of Metals in Watersheds Within the
Patagonia Mountains, S.E. Arizona
Project Goals
- Watershed approach
- Observe/monitor water quality
-Examine bioaccumulation of
contaminants in biota in the Santa
Cruz watershed near Patagonia Lake
Current Study Location
Town of Patagonia
Santa Cruz River
Sonoita Creek
Patagonia Lake
Nogales
Alum/Flux Canon
World’s Fair Mine
World’s Fair Mine Site,
Looking north at rocky, bare slopes
LOW-WATER
ENVIRONMENTS
Discharge from
portal at World’s Fair
Mine site
Methods
• Water, fish, aquatic macroinvertebrates
• Lakes and streams in the Santa Cruz basin
– Patagonia Mountains
• Alum Gulch – Above and Below World’s Fair Mine
• Harshaw Creek
• Humboldt Creek
– Patagonia Lake
– Pena Blanca Lake
Contaminant Levels
• High Resolution Inductive Coupled Plasma
Mass Spectrometry (HR-ICP-MS)
• 59 inorganic contaminants
– Lead (Pb) and Mercury (Hg)
Magnet
Hexapole
ICP Torch
Motorized Multicollectors
Sources of Lead = largely anthropogenic activities
Average lead concentration in adults & kids is 100
times greater than natural encumbrance.
Existing rates of Pb absorption = 30X level in preindustrial society.
Potentially causing mental retardation, palsy,
partial paralysis, hearing loss, anemia,
reproductive failure and DEATH.
WHERE? - Food, water, direct ingestion of dust
account for most of lead intake by humans
- Pb-containing paints.
- Leaded gasoline - Tetraethyl lead
- Mining and mine waste.
Soil Approach to Lake Patagonia
Soil Metal Concentrations in the Sonita/Patagonia Region
600
500
Sonoita
Creek
Cox 3R
Sonoita
Creek
400
Zn
300
Pb
Cu
As
200
Sb
100
09
-S
O
N9
(S
)
S)
N8
O
09
-S
(3
)(S
N7
(S
S)
)
O
09
-S
N7
O
09
-S
(2
)(S
N7
O
09
-S
09
-S
O
N6
Sample ID
(1
)(S
S)
)
(S
)
O
N5
(S
)
09
-S
O
N4
(S
)
09
-S
09
-S
O
N3
(S
)
(S
N2
O
09
-S
O
N1
(S
)
0
09
-S
Concentration (ppm)
Sonoita Creek
~1000m below
Alum/Flux
Alum/Flux
Harshaw
Creek
Lead Levels in Alum Invertebrates
WHO max water lead content = 10 ppb
Lead (Pb)
60000
50000
Both Sites in Alum > Humboldt/Harshaw
ppb
40000
30000
20000
10000
0
Fish Levels
of Concern
Above WF
Below WF
Humboldt
Invertebrate Average
WF = World’s Fair Mine
Harshaw
Mercury Levels in Alum Invertebrates
FDA Action Level (fish tissue) = 1 ppm
Canadian Limit (fish tissue) = 0.5 ppm
Mercury (Hg)
800
700
600
Humboldt/Harshaw > Both Sites in Alum
Reverse from Lead
ppb
500
400
300
200
100
0
Above WF
Below WF
WF = World’s Fair Mine
Humboldt
Invertebrate Average
Harshaw
Lead Levels in Patagonia Fish
WHO max water lead content = 10 ppb
Lead (Pb)
3000
2500
2000
ppb
Channel Cat
1500
1000
500
Red-ear
Bass
Flathead
MISA (N=8)
PYOL (N=6)
Crappie
0
ICPU (N=2)
Fish Species Average
LEMI (N=3)
POAN (N=1)
Mercury Levels in Patagonia Fish
FDA Action Level (fish tissue) = 1 ppm
Canadian Limit (fish tissue) = 0.5 ppm
Mercury (Hg)
1200
1000
ppb
800
600
400
200
0
MISA (N=8)
PYOL (N=6)
ICPU (N=2)
Fish Species Average
LEMI (N=3)
POAN (N=1)
Mercury Levels in Fish (Patagonia vs
Pena Blanca Lake)
Pena Blanca
p
p
b
FDA Action Level (fish tissue) = 1 ppm
Canadian Limit (fish tissue) = 0.5 ppm
MISA
Lead Point Source
• High Resolution Inductive Coupled Plasma
Mass Spectrometry (HR-ICP-MS)
• Soil, water, and aquatic biota
Why do Pb Isotopes Vary?
238U
--> 206Pb+ 84He + 6B- + Q
235U --> 207Pb + 74He + 6B- +Q
232 Th --> 208Pb + 64He + 4B- +Q
204Pb; primordial
Decay
Chain for
238U
Half-Life
~4.468 billion yrs
~0.738 billion yrs
~14.010 billion yrs
Data Presentation
208Pb/204Pb
207Pb/204Pb
208Pb/206Pb
207Pb/206Pb
206Pb/204Pb
204Pb
non-radiogenic, least abundant isotope
Ratios of 206Pb, 207Pb and 208Pb to 204Pb vary
due to age and geochemistry of Pb deposit or geology.
Strontium Isotopes - 87Sr/86Sr
Lead Isotopes (Patagonia vs Alum)
Patagonia/Alum
39.8
39.6
Patagonia
Lake Fish
39.4
208/204
39.2
Invertebrate (Above WF)
Invertebrate (Below WF)
Invertebrate (Lake)
39
Water
Alum
Invertebrates
and Water
38.8
Flathead catfish (Lake)
Largemouth Bass (Lake)
38.6
38.4
18.5
18.6
18.7
18.8
206/204
18.9
19
19.1
Lead Isotopes (Patagonia vs Alum)
Patagonia/Alum
39.8
39.6
PATAGONIA
FISH
39.4
208/204
39.2
Invertebrate (Above WF)
Invertebrate (Below WF)
Invertebrate (Lake)
39
Water
Flathead catfish (Lake)
Alum Invertebrates and Water
38.8
Largemouth Bass (Lake)
38.6
38.4
18.5
18.6
18.7
18.8
206/204
18.9
19
19.1
Lead Isotopes (with Alum)
Alum
38.6
38.58
208/204
38.56
38.54
Invertebrate (Above WF)
Invertebrate (Below WF)
38.52
Invertebrate (Lake)
Water
38.5
38.48
38.46
18.54
18.56
18.58
18.6
18.62
18.64
18.66
206/204
18.68
18.7
18.72
18.74
18.76
0.841
2.074
0.84
2.072
Worlds Fair Adit
0.839
0.838
2.068
January Adit
2.066
2.064
207/206
208/206
2.07
Invertebrates
Worlds Fair Adit
0.836
0.835
2.062
2.06
2.058
0.833
Stream below
Worlds Fair Adit
0.837
0.834
Trench Mine Tailings
0.834
0.835
0.836
0.837
0.838
0.839
0.84
0.841
0.833
0.71000
0.71050
0.71100
87/86
207/206
Wetlands
0.71150
Strontium
Stream Head
January Adit (Blocked)
Trench Mine Tailings
Worlds Fair Adit
.25 mi
0
Scale
Invertebrates
UPPER ALUM GULCH
2.074
2.072
208/206
207/206
2.07
2.068
Wetlands
Series1
Series2
Worlds Fair Adit
2.066
2.064
Stream below
Worlds Fair Adit
2.062
Invertebrates
January Adit
(Blocked)
2.06
2.058
1
10
100
Pb
1000
10000
Stream Head
Pb conc
Conc
(ppb)
Trench Mine Tailings
Worlds Fair Adit
.25 mi
0
Scale
UPPER ALUM GULCH
Conclusions
• Metal contaminants
concern in aquatic
systems
• Dust is major concern
• Alum/Patagonia different
sources
• Do not eat Pena Blanca
fish
• Need to develop tools and
extend analyses
Future Direction
• Expansion of study site –
need to look at entire
watershed – including
other watersheds
(Providencia) and entire
Santa Cruz
• Investigation into other
isotopic systems used in
geology/geochemistry:
–
–
–
–
–
–
87Sr/86Sr
57Fe/54Fe
63Cu/65Cu
196Hg/202Hg
143Nd/144Nd
116Sn/118Sn/120Sn
Acknowledgments
• We would like to
thank: USDA Forest
Service
• U of A ALEC Lab,
• Dr. John Chesley
(retired)
• Mark Baker,
(GeoScience UA).