selenium naturally occurring metalloid associated with: coal seams phosphate deposits other mineral...
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Selenium› Naturally occurring metalloid› Associated with:
Coal seams Phosphate deposits Other mineral formations
Increased mobilization due to:› Irrigation› Sewage› Fly ash/coal
combustion› Mining
4 Oxidation states› Selenite (SeO3 -2)
› Selenate (SeO4 -2)
› Selenides (Se -2)› Elemental selenium (Se)
Insoluble Poorly assimilated by aquatic plants
Immobilized› Selenate is oxidized to Selenite› Selenite binds to:
Clay Organic particles Forms precipitate with iron
› Precipitate settles out› Sediment can be buried
Remobilized by:› Plant root absorption› Consumption by inverts and fish
Benefits:› Protects DNA, lipids, and
proteins
If fish are deficient:› Loss coordination› Reduced growth› Reduced immune response
Impairs gas exchange› Swollen lamellae
Constricts blood vessels› Binds to hemoglobin
Unable to carry oxygen Induce cataracts Edema Seleno-proteins
Similar to sulfides Cells cannot discriminate Selenium substituted for
sulfur Results in dysfunctional
amino acids/proteins Accumulates in gonads,
kidney, and liver
Seleno-proteins stored in ovarian tissues
Proteins transferred to eggs› Building blocks for tissue
synthesis› Metabolic fuel
External feeding› Critical period› High mortality
Faulty proteins used for development
Results in teratogenesis:› Craniofacial deformities› Spinal deformities› Missing fins› Edema
Inability to feed leading to death
Kyphosis
Lordosis
Scoliosis
1) Determine the effects of selenium on the aquatic ecosystem of the Upper Mud River Watershed, WV
2) Determine the effects of selenium on the survival of bluegill larvae
Lower Guyandotte River Watershed
Lincoln and Boone Counties, WV 124 ha reservoir 4.5-6 m depth Inhabitants:
› Bluegill› Largemouth bass› Crappie› Channel catfish
Paint Creek Watershed Fayette County, WV 81.75 ha reservoir 12.2 m depth Inhabitants:
› Bluegill› Largemouth bass› Channel catfish› White crappie
October 2008-November 2010
Mud River (main stem and tributaries)› 20 total sites› Mined (13)› Unmined (7)
Reference Site› 2 sites
Water quality
Plum Orchard Lake(Reference Site)
YSI: DO, pH, temperature, conductivity
Total and dissolved Fe, total Se, TDS, sulfates, alkalinity, hardness, TSS and TOC
Picture credit: Melissa O’Neal
July 2009 Stantec, Inc. Stream (13) Reservoir (5)
› Transects› Top 5 cm
Picture credit: Stantec, Inc., Lexington, KY
July, August, September 2010
Mud River Reservoir (2)
Reference Site (1) 10-20 min/ tow Surface and mid
depth 95% ethanol
November 2009 and 2010
Mud River (11) Reference Site (2) 2009: 4 kick samples 2010: 6-8 kick
samples Sorted into
functional feeding group (FFG)
Photo credit: Melissa O’Neal
June 2009 and 2010 Spawning Mud River Reservoir
› Whole Body (n=118)› Gonad (n=31)
Reference Site› Whole Body (n=86)› Gonad (n=10)
Egg selenium calculated
Photo credit: John Howell
June 2009 and 2010
2009: Entire redd collected
2010: Only shells, rocks, and branches
Individual redds collected
Transported to WVU wet lab
Nest split into tanks› A Tanks: 28 day early life stage
test for chronic toxicity› B Tanks: 9 day swim-up success
Tanks contained water from original location
3-days after hatching fed fine fish food and brine shrimp twice daily
Multiple full water changes done daily
Ammonia (daily)
Nitrite, alkalinity, hardness (weekly)
Temperature, DO, and pH (subset daily)
Variable Mined Unmined Reference
Temperature (oC) 14.19 ± 0.42a 13.60 ± 0.57a 17.83 ± 1.45b
Conductivity (µs/cm)
1059.93 ± 33.91a 152.23 ± 7.16b 38.38 ± 0.66c
pH 7.77 ± 0.02a 7.26 ± 0.05b 7.05 ± 0.09b
DO (mg/L) 8.91 ± 0.32a 8.23 ± 0.20a 9.63 ± 1.88a
Hardness (mg/L
CaCO3)640.81 ± 31.91a 60.14 ± 5.49b 13.35 ± 0.302c
Alkalinity (mg/L
CaCO3)159.45 ± 5.54a 37.09 ± 2.05b 16.87 ± 1.37c
Variable Mined Unmined Reference
TDS (mg/L) 1416.57 ± 217.61a 139.16 ± 16.52b 16.87 ± 1.37c
Sulfate (mg/L) 462.24 ± 17.11a 39.87 ± 8.64b 12.14 ± 0.64c
Dissolved Iron (mg/L)
0.068 ± 0.007a 0.131 ± 0.009b 0.208 ± 0.023c
Total Iron (mg/L)
0.606 ± 0.189a 0.566 ± 0.093ab 0.336 ± 0.037b
Total Selenium (µg/L)
6.52 ± 0.289a 0.262 ± 0.015b 0.194 ± 0.021b
TOC (mg/L) 3.46 ± 0.36a 3.22 ± 0.308a 3.15 ± 0.079a
a
a
Site Type
Unmined Mined
Sel
eniu
m (
µg
/g D
W)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
a
a
Reservoir Transect
MudR16 MudR17 MudR18 MudR19 MudR14
Sel
eniu
m (
µg
/g D
W)
0
1
2
3
4
a
a
a aa
Site Type
Mined Unmined Reference
Sel
eniu
m (
µg
/g D
W)
0
2
4
6
8
10
12
14
16
18
a
a
b
Site Filterer Gatherer Scraper Shredder Composite
Unmined 2.69 ± 0.4a 3.90 ± 1.0a 3.7 ± 0.52a 1.9 ± 0.72a 3.4 ± 0.42a
Mined 11.7 ± 1.4b 12.44 ± 1.8b 8.1 ± 0.93b 11.5 ± 2.45b 11.1 ± 0.87b
Reference N/A 2.67 ± 0.04a N/A 0.88 ± 0.12a 2.1 ± 0.50a
*
Mud Reservoir Reference
05
1015
2025
3035
Site
Sel
eniu
m (
µg
/g D
W)
a
b
*
Mud Reservoir Reference
05
1015
2025
30
Site
Sel
eniu
m (
µg
/g D
W)
a
b
Variable ReferenceMud River Reservoir
Temperature (oC) 21.41 ± 0.12* 22.69 ± 0.12
Dissolved O2 (mg/L) 7.87 ± 0.09 7.99 ± 0.05
pH 7.73 ± 0.03* 8.36 ± 0.008
Ammonia (mg/L)0.766 ± 0.059* 0.308 ± 0.041
Nitrite (mg/L) 0.01 ± 0.001* 0.017 ± 0.002
Hardness (mg/L CaCO3) 20 ± 0.0* 250 ± 0.0
Alkalinity (mg/L CaCO3) 16.35 ± 1.13* 80 ± 0.0
The mine boundary is a good delineation for site types› Sites in the mine and
downstream were of high (> 5 µg/L) or moderate hazard (3-5 µg/L) based on the hazard profile by Lemly (1995)
Levels as low as 2 µg/L can be bioaccumulated in the food chain and cause reproductive failure
All sediment samples considered no to low hazard (≤ 2 µg/g DW)
Reservoir transects› All samples also considered low to
no hazard at < 2 µg/g DW› Selenium seems to remain in the
water column
Mud River Reservoir (mined and unmined) sites differed from the reference siteNot sorted to species
(zooplankton, etc.)
Mined areas greater than dietary threshold for fish
(3 µg/g) and birds (7 µg/g) Did not see a significant
difference between the reference site and unmined sites
No hazard category for whole body/gonad selenium concentrations
Egg selenium (68.76 ± 1.95 µg/g ) High hazard (>20 µg/g)
20 40 60 80 100
01
02
03
04
0
Weight (g)
Se
len
ium
(µ
g/g
DW
)
Toxic Effect Threshold
ReferenceMud Reservoir
Toxic EffectThreshold:
5 ug/g is considered the threshold for the health and reproductivesuccess of freshwater fish(Lemly 1995)
Did not observe deformities in larval fish
Low survival possibly due to temperature and ammonia levels
No observations of deformaties
Mined areas had higher selenium levels in the following categories:› Water selenium concentrations› Benthic macroinvertebrates› Whole body/gonad/egg
concentrations