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Mercury Toxic trace element Occurs naturally Anthropogenic sources Methyl form of most concern

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Page 1: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

MercuryMercury

Toxic trace element

Occurs naturally Anthropogenic

sources Methyl form of

most concern

Toxic trace element

Occurs naturally Anthropogenic

sources Methyl form of

most concern

Page 2: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Natural sourcesNatural sources

Hg0Hg0

Page 3: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Anthropogenic SourcesAnthropogenic Sources

Hg2+ HgpHg0

Page 4: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Mercury in the EnvironmentMercury in the Environment

Inorganic Hg is now the predominant source of methylated mercury

Fossil fuel burning

Inorganic Hg is now the predominant source of methylated mercury

Fossil fuel burning

Page 5: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Chemical Pollution Chemical Pollution

Inorganic form and methyl form both toxic

Becomes methylated through natural transformations Biomagnification and

bioaccumulation Top piscivorous wildlife

have some of the highest levels

Inorganic form and methyl form both toxic

Becomes methylated through natural transformations Biomagnification and

bioaccumulation Top piscivorous wildlife

have some of the highest levels

Source: USGS modified from Cleckner et al. 1998.

Page 6: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Wetlands and MercuryWetlands and Mercury

Methylmercury production.

Source of methylmercury for freshwaters.

Sink and source

Methylmercury production.

Source of methylmercury for freshwaters.

Sink and source

Page 7: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

HgpHg2+Hg

Hg0

Page 8: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Mercury concentrations in wetlands associated with coal-fired power plants

(CFPPs)

Mercury concentrations in wetlands associated with coal-fired power plants

(CFPPs)

Richard Halbrook and Scott WeirCooperative Wildlife Research Laboratory,

Department of Zoology Southern Illinois University, Carbondale, Illinois

Richard Halbrook and Scott WeirCooperative Wildlife Research Laboratory,

Department of Zoology Southern Illinois University, Carbondale, Illinois

Page 9: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

ObjectivesObjectives

Preliminary information on total mercury (THg) in wetlands associated with coal-fired generating plants in Illinois

H1: Sediment and tadpole THg will be higher downwind than upwind, and that concentrations will increase with increasing distance downwind

H2: Sediment and tadpole THg concentrations will be positively correlated

Specific protocols for monitoring mercury concentrations in wetland habitats

Preliminary information on total mercury (THg) in wetlands associated with coal-fired generating plants in Illinois

H1: Sediment and tadpole THg will be higher downwind than upwind, and that concentrations will increase with increasing distance downwind

H2: Sediment and tadpole THg concentrations will be positively correlated

Specific protocols for monitoring mercury concentrations in wetland habitats

Page 10: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Selection of Power PlantsSelection of Power Plants

Plants were selected on the following factors:Mercury emissionsPrevailing wind dataSuitable wetlands The plants selected are: Joppa, Baldwin,

Newton, and Southern Illinois Power Cooperative (SIPC)

Plants were selected on the following factors:Mercury emissionsPrevailing wind dataSuitable wetlands The plants selected are: Joppa, Baldwin,

Newton, and Southern Illinois Power Cooperative (SIPC)

Page 11: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Sample CollectionsSample Collections 45 total wetlands in May and June 2007 12 wetlands sampled from Baldwin and SIPC,

11 from Joppa, and 10 from Newton3 upwind and between 3-5km9 downwind

Range: 3-5km, 8-10km, and 13-15km

45 total wetlands in May and June 2007 12 wetlands sampled from Baldwin and SIPC,

11 from Joppa, and 10 from Newton3 upwind and between 3-5km9 downwind

Range: 3-5km, 8-10km, and 13-15km

Page 12: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Map of Wetlands, IL counties, CFPPsMap of Wetlands, IL counties, CFPPs

Page 13: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Collection MethodsCollection Methods

Sediment sampled with core augers 3 samples from each wetland Temperature (ºC)

Sediment sampled with core augers 3 samples from each wetland Temperature (ºC)

Tadpoles sampled with dip nets

Species, stage, mass, length

Tadpoles sampled with dip nets

Species, stage, mass, length

Page 14: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Sediment VariablesSediment Variables Oxidation-reduction

potential pH Texture

Oxidation-reduction potential

pH Texture

Page 15: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Mercury AnalysisMercury Analysis Total Hg in tadpoles

determined using a Hydra AF cold vapor mercury analyzer.

Tadpole digested by EPA method 245.7.

Sediment digested by EPA method 3051A. Analyzed at ISTC.

Total Hg in tadpoles determined using a Hydra AF cold vapor mercury analyzer.

Tadpole digested by EPA method 245.7.

Sediment digested by EPA method 3051A. Analyzed at ISTC.

Page 16: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

StatisticsStatistics

SAS (v 9.1) Normality, Shapiro-Wilks Analysis of covariance ANOVA Pearson Correlation (Bonferroni Correction)

SAS (v 9.1) Normality, Shapiro-Wilks Analysis of covariance ANOVA Pearson Correlation (Bonferroni Correction)

Page 17: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Sediment ResultsSediment Results

Range

1 2 3 4

log S

ed

ime

nt

TH

g (

ng/g

dry

we

igh

t)

1.2

1.4

1.6

1.8

BaldwinJoppaSIPCNewton

Page 18: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Upwind vs DownwindUpwind vs Downwind

Baldwin Joppa SIPC Newton

log S

ed

ime

nt

TH

g (

ng/g

dry

we

igh

t)

0.0

0.5

1.0

1.5

2.0

DownwindUpwind

*

3 7 71 3 9 62

Page 19: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Tadpole Results (29 ponds)*Tadpole Results (29 ponds)*

*Mean + SE (n)

  Bullfrog Green Frog n

Homogenized 56.80 + 6.6 (35)a 45.46 + 5.9 (36)ab 71

Whole 86.52 + 24.8 (13)a 28.23 + 3.7 (16)b 29

n 48 52 100

Page 20: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Tadpole Results Tadpole Results

Range

1 2 3 4

log T

ad

po

le T

Hg (

ng/g

we

t w

eig

ht)

1.2

1.4

1.6

1.8

2.0

BaldwinJoppaSIPCNewton

Page 21: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Tadpole upwind vs downwindTadpole upwind vs downwind

Baldwin Joppa SIPC Newton

log T

ad

po

le T

Hg (

ng/g

we

t w

eig

ht)

0.0

0.5

1.0

1.5

2.0

2.5

DownwindUpwind

2 4 24 1 6 3

Page 22: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

AEisler 1987BTerhivuo et al. 1984CMacDonald et al. 2000DHealth Canada 2007

Concentrations of importance

 

Background conc Current StudyConcentrations

of concern

Sediment THg 20-60 ng/g (dw)A 8-82 ng/g (dw) 180 ng/g (dw)C

Aquatic Vertebrates THg

<80 ng/g (ww)B 5-318 ng/g (ww) 500 ng/g (ww)D

Page 23: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Correlations of Tadpole VariablesCorrelations of Tadpole Variables

  THg Gosner StageTotal Length

(mm)Weight (g)

THg 1      

Gosner Stage -0.25* 1    

Total Length (mm)

-0.47*** 0.71*** 1  

Weight (g) -0.39*** 0.59*** 0.81*** 1

* = p < 0.10, *** = p < 0.01 (Bonferroni correction)

Page 24: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Tadpoles in the field

Author Location Species Tissue Mercury conc

Current study IllinoisBullfrog Green frog

Whole body63.2 ng/g

45.1 ng/g

Burger and Snodgrass

2001

Savannah River, SW Carolina

Southern leopard frog

Body, Tail, Digestive tract

< 0.200 ng/g DL

Bank et al. 2007

Acadia National Park,

Maine

Bullfrog Green frog

Whole body composite

19.1 ng/g 25.1 ng/g

Unrine et al. 2005

Savannah River, W Carolina

Southern leopard frog

Carcass Gut

184 ng/g (dw) 1275 ng/g (dw)

Byrne et al. 1975

Yugoslavia Unspecified Whole body 410, 490 ng/g

Page 25: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Other CFPP studiesOther CFPP studies

Author Place Biological UnitDistance from

CFPPSpecies Conclusions

Anderson and Smith 1977.

Illinois1 Lake,

Terrestrial soil< 15 km

Many fish species

Soil sig. > downwind, Lake sed > after ops began, Fish

conc very low

Wangen and Williams 1978.

New Mexico Terrestrial Soil 8-120 km N/A

Concentration as a function of distance were not significant

for 9 elements

Crockett and Kinnison 1979

Arizona Terrestrial Soil < 30 km N/ANo pattern in

concentric rings

Pinkney et al 1997.

Maryland Ponds 3 - 15 km

Fish (bluegill, green sunfish,

largemouth bass)

No pattern in concentric rings.Field results did not match

model

Current Study Illinois Ponds/Wetlands 3 - 15 kmBullfrog, green

frog larvae

No pattern for 3 of the CFPPs, Slight

pattern downwind of Newton CFPP

Page 26: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Using tadpoles as bioindicatorsUsing tadpoles as bioindicators

log pond mean tadpole THg (ng/g wet weight)

0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2

log p

on

d m

ea

n s

ed

ime

nt

TH

g (

ng/g

dry

we

igh

t)

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

Page 27: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

ConclusionsConclusions Preliminary information on total mercury (THg)

in wetlands associated with coal-fired generating plants in Illinois

H1: Sediment and tadpole THg will be higher downwind than upwind, and that concentrations will increase with increasing distance downwind (Newton CFPP Only)

H2: Sediment and tadpole THg concentrations will be positively correlated (Rejected)

Develop Specific protocols for monitoring mercury concentrations in wetland habitats

Preliminary information on total mercury (THg) in wetlands associated with coal-fired generating plants in Illinois

H1: Sediment and tadpole THg will be higher downwind than upwind, and that concentrations will increase with increasing distance downwind (Newton CFPP Only)

H2: Sediment and tadpole THg concentrations will be positively correlated (Rejected)

Develop Specific protocols for monitoring mercury concentrations in wetland habitats

Page 28: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Management ImplicationsManagement Implications

Concentrations of THg measured in sediment and tadpoles in wetlands surrounding Newton, Baldwin, Joppa, and SIPC CFPPs were are below levels of concern

Concentrations of THg measured in sediment and tadpoles in wetlands surrounding Newton, Baldwin, Joppa, and SIPC CFPPs were are below levels of concern

Page 29: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

AcknowledgementsAcknowledgements

Illinois Sustainable Technology Center

Gary Bordson and the metals group at ISTC

Marvin Piwoni Cooperative Wildlife

Research Lab Department of Zoology

and Graduate School

Illinois Sustainable Technology Center

Gary Bordson and the metals group at ISTC

Marvin Piwoni Cooperative Wildlife

Research Lab Department of Zoology

and Graduate School

Page 30: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Questions?Questions?

Page 31: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

ConclusionsConclusions

With the exception of Newton, CFPPs did not have a significant pattern of THg concentrations in ponds 3-15 km downwind

Tadpole THg was negatively correlated with length

With the exception of Newton, CFPPs did not have a significant pattern of THg concentrations in ponds 3-15 km downwind

Tadpole THg was negatively correlated with length

Page 32: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Sediment THg and distanceSediment THg and distance

Range

1 2 3 4

log S

ed

ime

nt

TH

g (

ng/g

dry

we

igh

t)

1.2

1.3

1.4

1.5

1.6

1.7

1.8

9 9

10

10

Page 33: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Sediment VariablesSediment Variables

A = Pond means were used in these correlations*** = p < 0.01 (Bonferroni correction)

  Sediment THgTemperature

(°C)pH

Redox potential

Pond area (m2)A Tadpole THgA

Sediment THg 1          

Temperature (°C)

-0.16 1        

pH -0.21 -0.22 1      

Redox potential

0.24 0.16 -0.85 1    

Pond area (m2)A 0.01 -0.26 0.23 -0.33 1  

Tadpole THgA -0.05 -0.41 0.35 -0.14 0.01 1

Page 34: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

TextureTexturelo

g s

ed

ime

nt

TH

g (

ng/g

dry

we

igh

t)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

6 15 1 2 1 13 20 8

Page 35: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Mercury across taxa

Mammals Birds Amphibians

MechanismMeHg causes

central nervous system damage

Central nervous system damage

Neurotoxicity (?)

Physiological effects

Behavioral impairment:

anorexia, lethargy

Weight loss, muscular

incoordination

Adults: ? Tadpoles:

swimming behavior

ReproductionReadily crosses placental barrier

Reduced hatchability and

clutch size, eggshell thinning

Effects on embryos (?)

Page 36: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Mercury and AmphibiansMercury and Amphibians

MeHgMeHgHg2+Hg2+200-400 ng/g 200-400 ng/g

THg THg body body burdenburden

Concentrations Concentrations similar to similar to fishfish

Page 37: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Local vs Regional vs GlobalLocal vs Regional vs Global

Contradicting results regarding the local effects of coal-fired power plants

Studies have reported local impacts Some have stated that local impacts are

overestimated Atmospheric lifespan of mercury species

Contradicting results regarding the local effects of coal-fired power plants

Studies have reported local impacts Some have stated that local impacts are

overestimated Atmospheric lifespan of mercury species

Page 38: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Quality Assurance/Quality ControlQuality Assurance/Quality Control

Laboratory Blanks Laboratory Reagent Spikes Replicates

Laboratory Blanks Laboratory Reagent Spikes Replicates

Tadpole Only:Tadpole Only:Matrix Quad Matrix Quad StudyStudy

Tadpole Only:Tadpole Only:Matrix Quad Matrix Quad StudyStudy

Sediment Only:Sediment Only:Matrix SpikeMatrix SpikeReference Reference MaterialMaterial

Sediment Only:Sediment Only:Matrix SpikeMatrix SpikeReference Reference MaterialMaterial

Page 39: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Tadpoles are kind of a painTadpoles are kind of a pain

Feeding behavior

Predation escape

Metamorphosis/Physiology

Feeding behavior

Predation escape

Metamorphosis/Physiology

Page 40: Mercury  Toxic trace element  Occurs naturally  Anthropogenic sources  Methyl form of most concern  Toxic trace element  Occurs naturally  Anthropogenic

Newton Power PlantNewton Power Plant

Range

1 2 3 4

log T

Hg (

ng/g

)

1.0

1.2

1.4

1.6

1.8

2.0

SedimentTadpole