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Atmospheric Fate and Transport of Mercury
Lake Ontario Contaminant Monitoring & Research WorkshopPlanning for the 2008 Cooperative Monitoring Year
- Contaminants Component –Grand Island Holiday Inn, Grand Island, New York
March 27 & 28, 2007
Mark CohenNOAA Air Resources Laboratory
1315 East West Highway, R/ARL, Room 3316
Silver Spring, Maryland, 20910, USAmark.cohen@noaa.gov
http://www.arl.noaa.gov/ss/transport/cohen.html
Standing (from left): Eric Uram, Gary Foley, John McDonald, Greg Mierle, Sheng-Wei Wang;
Kneeling (from left): Chris Knightes, Elsie Sunderland, Wolfgang Scheider, Mark Cohen
At the Lake Ontario Contaminant Monitoring, Modeling & Research Workshop, Grand Island, NY, March 27-28, 2007
Thanks, John!
MANY THANKS TO:
Gary Foley, J. David Mobley, Elsie Sunderland, Chris Knightes (EPA); Panos Georgopolous and Sheng-Wei Wang (EOSHI Rutgers Univ); John McDonald (IJC): funding and collaboration on multimedia Hg modeling
David Schmeltz, Gary Lear, John Schakenbach, Scott Hedges, Rey Forte (EPA): funding and collaboration on Hg models and /measurements, including new EPA-NOAA Hg monitoring site at Beltsville, MD.
David Ruple, Mark Woodrey (Grand Bay NERR), Susan White , Gary Matlock, Russell Callender, Jawed Hameedi (NOAA), and Durwin Carter (U.S. Fish and Wildlife Service): collaboration at NOAA Grand Bay NERR atmospheric monitoring site
Anne Pope and colleagues (EPA): U.S. mercury emissions inventory
David Niemi, Dominique Ratte, Marc Deslauriers (Environment Canada): Canadian mercury emissions inventory data
Mark Castro (Univ. Md, Frostburg), Fabien Laurier (Univ Md Ches Biol Lab), Rob Mason (Univ CT), Laurier Poissant (Envr Can): ambient Hg data for model evaluation
Roland Draxler, Glenn Rolph, Rick Artz (NOAA): HYSPLIT model and met data
Steve Brooks, Winston Luke, Paul Kelley (NOAA) : ambient Hg data
4
Hg from other sources: local, regional & more distant
emissions of Hg(0), Hg(II), Hg(p)
Hg(0)
Hg(II) Hg(p)
atmosphericchemistry
inter-converts mercury forms
Surface exchange with the watershed
Surface exchange with
the lake
Objectives and Rationale of Atmospheric Modeling in Conjunction with Great Lake Multi-Compartment Mercury Modeling Project
Estimate deposition amount of different mercury species and/or forms to different regions of Lake Ontario lake surface and watershed, for use in ecological assessment and modeling
dry deposition generally estimated with modelsmodeling can help fill in spatial gaps between measurement sitesmodeling can help estimate deposition for other times• past• future (for different emissions scenarios)
Estimate source attribution for deposition of different mercury species and/or forms to different regions of Lake Ontario lake surface and watershed, including estimation of the relative importance of:
different source regions (local, regional, national, continental, global)different jurisdictions (different states and provinces) anthropogenic vs. natural emissionsdifferent anthropogenic source types (power plants, waste incin., etc)
5
Source of emissions data: U.S. EPA and Environment Canada
Largest mercury sources in U.S. and Canadian air emissions inventories (~1999-2000)
Some preliminary results for the atmospheric deposition impact of
U.S. and Canadian anthropogenic mercury air emissions sources on Lake Ontario
Largest modeled atmospheric deposition contributors to Lake Ontario based on 1999-2000 emissions
Modeled atmospheric mercury deposition to Lake Ontario from U.S. and Canadian source sectors based on 1999-2000 emissions
Top 25 Contributors to 1999 Hg Deposition Directly to Lake Ontario
American Ref-Fuel (Niagara) Homer City
KeystoneNiagara Falls Incin.NANTICOKE TGS
Phoenix ServicesKMS Peel Incin.Niagara MohawkC. R. Huntley Shawville Montour Dunkirk Eastlake Mt. Storm
Toronto Sewage Sludge Incin.Bruce MansfieldMedusa CementConesville CardinalUniv. of RochesterW. H. SammisJohn E AmosJERRITT CANYONDOFASCO (Hamilton)Lubrizol Corp.
NY PA
PA NY CAN
MD CAN
NY NY PA PA NY OH WV CAN PA PA OH OH NY OH WV NV CAN OH
0% 20% 40% 60% 80%Cumulative Fraction of Hg Deposition
0
5
10
15
20
25R
ank
coal-fired elec genother fuel combustionwaste incinerationmetallurgicalmanufacturing/other
Many uncertainties in these earlier results…
How to refine modeling and link with other models in a multi-media framework?
Hg from other sources: local, regional & more distant
emissions of Hg(0), Hg(II), Hg(p)
atmospheric deposition
to the water surface
Hg(0)
Hg(II) Hg(p)
atmosphericchemistry
inter-converts mercury forms
atmospheric deposition
to the watershed
Hg from other sources: local, regional & more distant
Hg from other sources: local, regional & more distant
emissions of Hg(0), Hg(II), Hg(p)emissions of Hg(0), Hg(II), Hg(p)
atmospheric deposition
to the water surface
atmospheric deposition
to the water surface
Hg(0)
Hg(II) Hg(p)
atmosphericchemistry
inter-converts mercury forms
Hg(0)
Hg(II) Hg(p)
Hg(0)
Hg(II) Hg(p)
atmosphericchemistry
inter-converts mercury forms
atmospheric deposition
to the watershed
atmospheric deposition
to the watershed
12
Hg(0)
Hg(II) Hg(p)
For Lake Ontario:
How to link the atmospheric model and the aquatic fate/cycling model?
Inflow/RunoffOutflow
Settling/Resusp Diffusion
Wet and dry Deposition
MeHg
Hg(0)
Hg(II)
Volatilization
Hg(II) MeHgBioaccumulation
Burial Burial
Settling/Resusp Diffusion
Source: R. Harris, Tetra-Tech, Inc.
Inflow/RunoffOutflow
Settling/Resusp Diffusion
Wet and dry Deposition
MeHg
Hg(0)
Hg(II)
Volatilization
Hg(II) MeHgBioaccumulation
Burial Burial
Settling/Resusp Diffusion
Source: R. Harris, Tetra-Tech, Inc.
Air-Water Interface – at the boundary
between the atmospheric model (over the lake) and the lake fate and
cycling model
Hg(0) Hg(2) Hg(p)
Upward Flux of Hg(2) and Hg(p) is probably small
Surface exchange of Hg(0) from Lake Ontario may not have large impact on overall atmospheric Hg fate-transport (?)
The precise specification of surface exchange of Hg(0) may not have large impact on methyl-mercury production (???)
It may turn out that dynamic, run-timelinkage between lake and atmosphere is not critical for Hg (?)(we will see…)
13
Hg(0)
Hg(II) Hg(p)
atmospheric chemistry
phase partitioning
Atmospheric Mercury Modelwet
deposition
surface exchange
Wet and dry deposition of different
mercury species to lake and watershed
Source attribution
information for deposition
Model Outputs
For model evaluation, emissions and
meteorology must be for the same time period as ambient measurement data
Speciated ambient concentration data
Wet deposition data
Model Evaluation
Speciated ambient concentration data
meteorologyInputs to Model
emissionsemissions
14
95 96 97 98 99 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15
1995 Canada
Inventory
15
speciated atmospheric Hg measurements at site x
speciated atmospheric Hg measurements at site y
speciated atmospheric Hg measurements at site z
2002 US Inventory
1999 US Inventory
2000 Global
Inventory
2000 Canada
Inventory
New York inventory
? Ontario inventory
?
Hypothetical –just for illustration purposes
For model evaluation, inventory must be accurate and for same period as measurements (a big challenge!)
Lake Ontario
16
RGM emissions (~1999) in the Lake Ontario region
Source of emissions data: U.S. EPA and Environment Canada
“RGM” = Reactive Gaseous Mercury, the form of atmospheric mercury most readily deposited
Lake Ontario
17Source of emissions data: U.S. EPA and Environment Canada
RGM emissions (~1999) in the Lake Ontario region, and Mercury Deposition Network (MDN) sites
Lake Ontario
18Source of emissions data: U.S. EPA and Environment Canada
RGM emissions (~1999) in the Lake Ontario region, and (some of the) sites where speciated concentrations of atmospheric Hg have been measured
Stockton(Holsen)
Sterling(Holsen)
Potsdam(Holsen)
St,. Anicet(EC – Poissant)
Lake Champlain
(LCRC-Miller)Pt, Petre(CAMNet)
Lake Ontario
19Source of emissions data: U.S. EPA and Environment Canada
RGM emissions (~1999) in the Lake Ontario region, along with MDN and ambient concentration sites
Atmospheric models can potentially provide valuable deposition and source-attribution information.
But… models have not been adequately evaluated, so we don’t really know very well how good or bad they are…
… air pollution model or error pollution model?
Challenges / critical data needs for model evaluation:
Ambient Monitoring Dataspeciated ambient concentrations (need RGM and Hg(p), not just total gaseous mercury)
wet deposition
Emissions inventoriescomplete“accurate”speciatedup-to-date (or at least for the same period as measurements)temporal resolution better than annual (e.g., shut-downs, etc)
Atmospheric models can potentially provide valuable deposition and source-attribution information.
But… models have not been adequately evaluated, so we don’t really know very well how good or bad they are…
… air pollution model or error pollution model?
Thanks!
Extra Slides
policy development requires:source-attribution (source-receptor info) estimated impacts of alternative future scenarios
estimation of source-attribution & future impactsrequires atmospheric models
atmospheric models require:knowledge of atmospheric chemistry & fateemissions dataambient data for “ground-truthing”
24
Hg from other sources: local, regional & more distant
emissions of Hg(0), Hg(II), Hg(p)
atmospheric depositionto the water
surface
Hg(0)
Hg(II) Hg(p)
atmosphericchemistry
inter-converts mercury forms
atmospheric deposition
to the watershed
Measurement of ambient air
concentrations
Measurement of wet
depositionWET DEPOSITION complex – hard to diagnoseweekly – many eventsbackground – also need near-field
AMBIENT AIR CONCENTRATIONS more fundamental – easier to diagnoseneed continuous – episodic source impactsneed speciation – at least RGM, Hg(p), Hg(0)need data at surface and above
Erie Ontario Michigan Huron Superior0
1
2
3
4
5
6
7
8
Dep
ositi
on (u
g/m
2-ye
ar) HYSPLIT
CMAQ
Model-estimated U.S. utility atmospheric mercury deposition contribution to the Great Lakes: HYSPLIT-Hg (1996 meteorology, 1999 emissions) vs. CMAQ-HG (2001 meteorology, 2001 emissions).
25
Erie Ontario Michigan Huron Superior0
1
2
3
4
5
6
7
8
Dep
ositi
on (u
g/m
2-ye
ar) HYSPLIT
25% added to CMAQCMAQ
Model-estimated U.S. utility atmospheric mercury deposition contribution to the Great Lakes: HYSPLIT-Hg (1996 meteorology, 1999 emissions) vs. CMAQ-Hg (2001 meteorology, 2001 emissions).
This figure also shows an added component of the CMAQ-Hg estimates -- corresponding to 30% of the CMAQ-Hg results – in an attempt to adjust the CMAQ-Hg results to account for the deposition underprediction found in the CMAQ-Hg model evaluation.
26
r value for MDN Concentration Trends 1998-2005(-r is declining trend, +r is increasing trend)
* significant slope at p=0.10; **significant slope at p=0.05
-1-0.8-0.6-0.4-0.2
00.20.40.60.8
1
ME02
ME09
ME96
ME98
NB
02
NS01
NY20
PA13
PA37**
PA90*
PA60*
PQ04**
IL11
MN
16*
MN
18*
MN
23*
MN
27
WI08
WI09*
WI36**
WI99
NC
08*
NC
42
FL04
FL05
FL11
FL34
GA
09*
LA05
LA10
LA28
SC19
TX21
r val
ue
NE MW SE
Source: Regional Precipitation Mercury Trends in the Eastern USA, 1998-2005: Declines in the Northeast and Midwest, but No Change in the Southeast. Thomas J. Butler, Mark Cohen, Gene E. Likens and Francoise M. Vermeylen, David Schmeltz and Richard Artz. In preparation, 2007.
Reactive Gaseous Mercury (RGM) emissions flux changes between 1990-1996 and 1999-2001
Source: Regional Precipitation Mercury Trends in the Eastern USA, 1998-2005: Declines in the Northeast and Midwest, but No Change in the Southeast. Thomas J. Butler, Mark Cohen, Gene E. Likens and Francoise M. Vermeylen, David Schmeltz and Richard Artz. In preparation, 2007.
r value for MDN Deposition Trends 1998-2005(- r is declining trend, +r is increasing trend)
* significant slope at p=0.10; ** significant slope at p=0.05
-1-0.8-0.6-0.4-0.2
00.20.40.60.8
1
ME02
ME09
ME96
ME98
NB
02
NS01
NY20
PA13
PA37
PA90
PA60
PQ04
IL11
MN
16**
MN
18**
MN
23
MN
27
WI08*
WI09
WI36
WI99*
NC
08*
NC
42
FL04
FL05**
FL11
FL34
GA
09
LA05
LA10
LA28
SC19
TX21r v
alue
NE SEMW
Source: Regional Precipitation Mercury Trends in the Eastern USA, 1998-2005: Declines in the Northeast and Midwest, but No Change in the Southeast. Thomas J. Butler, Mark Cohen, Gene E. Likens and Francoise M. Vermeylen, David Schmeltz and Richard Artz. In preparation, 2007.
Random Coefficient Model results for Northeastern and Midwesternannual mercury concentration and deposition for 1998 to 2005.
20052004200320022001200019991998
Year
14.00
12.00
10.00
8.00
6.00
4.00
2.00
Hg(
ng/l)
NE Concentration
Source: Regional Precipitation Mercury Trends in the Eastern USA, 1998-2005: Declines in the Northeast and Midwest, but No Change in the Southeast. Thomas J. Butler, Mark Cohen, Gene E. Likens and Francoise M. Vermeylen, David Schmeltz and Richard Artz. In preparation, 2007.
20052004200320022001200019991998
Year
14.00
12.00
10.00
8.00
6.00
4.00
2.00
Hg(
ng/l)
MW Concentration
20052004200320022001200019991998
Year
14.00
12.00
10.00
8.00
6.00H
g (µ
g/m
2)
MW Deposition
20052004200320022001200019991998
Year
12.50
10.00
7.50
5.00
Hg
(µg/
m2)
NE Deposition
Northeast Midwest Southeast
1990
-199
6
1999
-200
1
1990
-199
6
1999
-200
1
1990
-199
6
1999
-200
10
10
2030
4050
60
70
Em
issi
ons
(met
ric to
ns/y
r)
Hg(II)
Hg(p)
Hg(0)
Northeast Midwest Southeast
1990
-199
6
1999
-200
1
1990
-199
6
1999
-200
1
1990
-199
6
1999
-200
105
1015
2025
30
35
Em
issi
ons
flux
(g/k
m2-
yr)
Hg(II)
Hg(p)
Hg(0)
Source: Regional Precipitation Mercury Trends in the Eastern USA, 1998-2005: Declines in the Northeast and Midwest, but No Change in the Southeast. Thomas J. Butler, Mark Cohen, Gene E. Likens and Francoise M. Vermeylen, David Schmeltz and Richard Artz. In preparation, 2007.
L – statewide (1999)
L –statewide
(1993)
L, R –statewide
(1997)
L, R –statewide
(2000)
L –statewide
(2004)R –
statewide (1996)
L, R –statewide
(2002)
L, R – statewide (2001)
L, R –specific
waterbodies
L, R –specific
waterbodies
R - specific waterbodies
Ontario
Minnesota
Wisconsin
IllinoisIndiana
Ohio
Pennsylvania
New York
Erie
OntarioHuron
Superior
Mic
higa
n
Michigan
R – specific waterbodies
In some states, there is a statewide mercury-related fish consumption advisory for lakes (L) and/or rivers (R), and in other cases, advisories have been issued for specific waterbodies. In the case of statewide advisories, the year the advisory was established is given. It is noted that Pennsylvania’s statewide advisory was established for a number of pollutants, including mercury, and is not necessarily considered to be only a mercury-specific statewide consumption advisory. Mercury-related advisories for specific fish species have also been established by one or more states and provinces for each of the Great Lakes. Sources of information for this figure: Illinois Department of Public Health (2006); Indiana State Department of Public Health et al. (2006); Michigan Department of Community Health (2006); Minnesota Department of Health (2006); New York State Department of Health (2006); Ohio EPA Division of Surface Water (2006); Ontario Ministry of the Environment (2006a); Pennsylvania Department of Environmental Protection (2006); USEPA (2005f); and Wisconsin Department of Natural Resources (2006).
Figure 2. Summary of mercury-related fish consumption advisories in the Great Lakes region.
Superior Huron Michigan Erie Ontario0
5
10
15
20
ug/m
2-ye
ar
CAN 2000USA 1999CAN 1995USA 1996
Figure 92. Modeled mercury flux to the Great Lakes (1995-1996 vs. 1999-2001), arising from anthropogenic mercury air emissions sources in the United States and Canada
Superior Huron Michigan Erie Ontario0
100
200
300
400
500
600
700
800kg
/yea
r
CAN 2000USA 1999CAN 1995USA 1996
Superior Huron Michigan Erie Ontario0
5
10
15
20
ug/m
2-ye
ar
CAN 2000USA 1999CAN 1995USA 1996
Modeled mercury flux (ug/m2-yr) to the Great Lakes (1995-1996 vs. 1999-2000), arising from anthropogenic mercury air emissions sources in the U.S. and Canada
Modeled mercury deposition (kg/year) to the Great Lakes (1995-1996 vs. 1999-2000), arising from anthropogenic mercury air emissions sources in the U.S. and Canada
Model results for atmospheric deposition show that:
• U.S. contributes much more than Canada
• Significant decreasebetween 1996 and 1999 (primarily due to decreased emissions from waste incineration)
Erie
Ontario
Huron
Superior
Mic
higa
n
Lake Ontario 45-cm Walleye
0.00.20.40.60.81.0
1965
1970
1975
1980
1985
1990
1995
2000
2005
Lake Erie 45-cm Walleye
0.00.20.40.60.81.0
1965
1970
1975
1980
1985
1990
1995
2000
2005
Lake Huron 45-cm Walleye
0.00.20.40.60.81.0
1965
1970
1975
1980
1985
1990
1995
2000
2005
Lake Superior 45-cm Walleye
0.00.20.40.60.81.0
1965
1970
1975
1980
1985
1990
1995
2000
2005
Lake Erie Walleye (Ages 4-6)
0.000.100.200.300.40
1977
1980
1983
1986
1989
1992
1995
1998
2001
2004
Figure 101. Mercury concentration trends Great Lakes Walleye.Total mercury concentrations (ppmor ug Hg/g).
Sources of data: Ontario Ministry of the Environment (2006b), for 45-cm Walleye data, and Environment Canada (2006), for data on Lake Erie Walleye ages 4-6.
Hg Levels in Lake Superior Rainbow Smelt(ug/g +/- S.E. w et w eight, w hole f ish) Ages 4-6
0
0.02
0.04
0.06
0.08
0.1
0.12
1981
1983
1985
1987
1989
1991
1993
1995
1997
1999
2001
Year
ug/g
(+/-
S.E.
)
Erie
Ontario
Huron
Superior
Mic
higa
n
Hg Levels in Lake Lake Huron Rainbow Smelt(ug/g +/- S.E. w et w eight, w hole f ish) Ages 4-6
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
1979
1981
1983
1985
1987
1989
1991
1993
1995
1997
1999
2001
2003
Year
ug/g
(+/-
S.E.
)
Hg Levels in Lake Erie Rainbow Smelt(ug/g +/- S.E. w et w eight, w hole f ish) Ages 4-6
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
1977
1979
1981
1983
1985
1987
1989
1991
1993
1995
1997
1999
2001
2003
Year
ug/g
(+/-
S.E.
)
Hg Levels in Lake Ontario Rainbow Smelt(ug/g +/- S.E. w et w eight, w hole f ish) Ages 4-6
0
0.02
0.04
0.06
0.08
0.1
0.12
1977
1980
1983
1986
1989
1992
1995
1998
2001
2004
Year
ug/g
(+/-
S.E.
)
Figure 102. Total mercury levels in Great Lakes Rainbow Smelt, 1977-2004.
Source of data: Environment Canada (2006). Note that the scales for the lakes are different.
Hg Levels in Lake Superior Lake Trout(ug/g +/- S.E. w et w eight, w hole fish) Ages 4-6
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
Year
ug/g
(+/-
S.E.
)
Erie
Ontario
Huron
Superior
Mic
higa
n
Hg Levels in Lake Huron Lake Trout(ug/g +/- S.E. w et w eight, w hole fish) Ages 4-6
0
0.1
0.2
0.3
0.4
0.5
0.6
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
Year
ug/g
(+/-
S.E.
)
Hg Levels in Lake Erie Lake Trout(ug/g +/- S.E. w et w eight, w hole fish) Ages 4-6
0.00
0.02
0.04
0.06
0.08
0.10
0.12
1985
1987
1989
1991
1993
1995
1997
1999
2001
2003
Year
ug/g
(+/-
S.E.
)
Hg Levels in Lake Ontario Lake Trout(ug/g +/- S.E. w et w eight, w hole f ish) Ages 4-6
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
1977
1980
1983
1986
1989
1992
1995
1998
2001
2004
Year
ug/g
(+/-
S.E.
)
Figure 103. Mercury concentration trends in Lake Trout in the Great Lakes.
Data from Environment Canada (2006). Note that for Lake Huron, there was an average of 25fish sampled each year from 1980 to 1994, but that the data shown for 2001 represents only 1 fish.
Erie
Ontario
Huron
Superior
Mic
higa
n
1
2
34
5
6
7
89
10
111213
1415
2. Agawa Rock
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
1. Granite Island
0.00.20.40.60.8
1970 1980 1990 2000
3. Big Sister Island
0.00.20.4
0.6
0.8
1970 1980 1990 2000
4. Gull Island
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
5. Channel Shelter Island
0.00.20.40.60.8
1970 1980 1990 2000
7. Chantry Island
0.00.20.40.60.8
1970 1980 1990 2000
6. Double Island
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
8. Fighting Island
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
9. Middle Island
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
10. Port Colborne
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
11. Niagara River
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
12. Hamilton Harbour
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
13. Toronto Harbour
0.0
0.2
0.4
0.6
0.8
1.0
1970 1980 1990 2000
15. Strachan Island
0.0
0.2
0.4
0.6
0.8
1970 1980 1990 2000
14. Snake Island
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1970 1980 1990 2000
Source of data – Canadian Wildlife Service. Total mercury concentrations in eggs from colonies in the Great Lakes region expressed in units of ug Hg/g (wet weight).
From 1971 – 1985, analysis was generally conducted on individual eggs (~10) from a given colony, and the standard deviation in concentrations is shown on the graphs.
From 1986 to the present, analysis was generally conducted on a composite sample for a given colony.
The trend lines shown are for illustration purposes only; they were created by fitting the data to a function of the form y = cxb.
Figure 106. Trends in Herring Gull Egg Hg concentrations.
1
2
34
67
9
1110
1213
14
5
8
15 161718
19
202122 23
24
25
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12 16. Peach Orchard Pt.
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
12. Black River Canal
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12 9. Thunder Bay
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12 11. Sandpoint
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12 4. Calumet Breakwater
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12 6. Holland Breakwater
1992
1994
1996
1998
2000
2002
2004
0.00
0.04
0.08
0.12
5. Hammod Marina
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
7. Muskegon
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.120.160.200.240.28 3. North Chicago
1992
1994
1996
1998
2000
2002
2004
0.00
0.04
0.08
0.128. Leelanau State Park
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12 24. Oswego
Erie
Ontario
Huron
Superior
Mic
higa
n
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
21. Niagara Falls
1992
1994
1996
1998
2000
2002
2004
0.00
0.04
0.08
0.1223. Rochester
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
25. Cape Vincent
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12 10. Saginaw River
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
17. Old Woman Creek
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
15. Reno Beach19
92
1994
1996
1998
2000
2002
2004
0.000.040.080.12 14. Stony Point
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
18. Lorain
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
19. Ashtabula
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
22. Olcott
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
20. Dunkirk
1992
1994
1996
1998
2000
2002
2004
0.00
0.04
0.08
0.12
13. Anchor Bay
1992
1994
1996
1998
2000
2002
2004
0.000.040.080.12
2. Milwaukee Bay19
92
1994
1996
1998
2000
2002
2004
0.00
0.04
0.08
0.121. Bayshore Park
Figure 107. Mercury concentration in Great Lakes region mussels (1992-2004). Total mercury in mussels (ug/g, on a dry weight basis).
In a few cases (e.g. for several sites in 2003), mercury concentrations were below the detection limit. In these cases the concentrations are shown with a white cross-hatched bar at a value of one-half the detection limit; in reality, the mercury concentration could have been anywhere between zero and the detection limit.
Source of data: NOAA Center for Coastal Monitoring and Assessment (CCMA) (2006) and “Monitoring Data - Mussel Watch” website: http://www8.nos.noaa.gov/cit/nsandt/download/mw_monitoring.aspx
Ambient atmospheric
concentrations measurements
water-column measurements
Ambient atmospheric
wet deposition measurements
Receptor Modeling (e.g., Back-Trajectory)
Forward atmospheric fate
and transport modeling from a comprehensive
inventory
Tributary and runoff water
measurements
Modeling the chemo-dynamics of mercury
in the water-body
Data analysis (trends,
correlations, etc)
Mass Balance Ecosystem
Models
Sediment, Biota, and other Ecosystem Measurements
Meteorological measurements and modeling
All of these analytical
approaches are needed –
and must be used in coordination --to understand Hg in a given water-
body enough to be able to fix problems
Hg(0)
Hg(II) Hg(p)
Wet and dry depositionof Hg(0), Hg(p), Hg(II)
watershed processing
We need to understand Hg in the environment enough to be able to fix the problem
Many scientific disciplines need to work in collaboration to achieve this understanding
Total Mercury Fluxes Lake Ontario
Active Sediment Layer
Buried Sediments
Water
Diffusion22-100 kg/yr Solids Settling
1100 kg/yr
Resuspension1700 kg/yr
Burial2500 kg/yr
Inflow680 kg/yr
Evasion800 kg/yr
Outflow100 kg/yr
Atmospheric Deposition360 kg/yr
slide courtesy of Elsie Sunderland, USEPA
Table 4. Summary of U.S. anthropogenic mercury emissions inventories
Inventory
Avail-able for this
study
Geo-graphical resolution
Nominal Time
period for inventory
Total U.S. direct anthro-
pogenic emissions (tons/yr)
Notes and/or References
1990 Cumulative Outdoor Exposure Study
no point and area sources 1990 266 Rosenbaum et al., 1999ab.
1990 National Toxics Inventory (NTI)
yes national totals only 1990 220
EPA (2005a, 2006). These data are based on the 1990 National Toxics Inventory. We have not been able to find any detailed documentation for this inventory.
Mercury Study Report to Congress (MSRTC, Vol. 2)
yes point and area sources 1994-95* 158
The geographically resolved version of this inventory was used as input to the RELMAP atmospheric fate and transport model (MSTRC, Vol. 3), EPA, 1997. It does not include gold mining, estimated in later inventories to be on the order of 13 tons/year
1996 National Toxics Inventory (NTI)
no
point sources and county-level area sources
1996 195
This inventory has been withdrawn by the EPA due to data quality concerns. The 195 ton total value was obtained from EPA (2006).
hybrid “1996” inventory yes
point sources and county-level area sources
1996 162
used in NOAA atmospheric mercury simulations with the HYSPLIT-Hg model (Cohen et al, 2004). It contains elements of the MSRTC inventory (for municipal and medical waste incinerators and commerical/industrial boilers), 1999 estimates for coal-fired power plants, and the 1996 NTI for other point and area sources.
1999 National Emissions Inventory (NEI)
yes
point sources and county-level area sources
1999 113 some of the incinerator emission reductions may not have occured till 2000-2001
2002 National Emissions Inventory (NEI)
no
point sources and county-level area sources
2002 ? We have been unable to obtain summary or detailed information from this inventory, as of December 2006.
2005 National Emissions Inventory (NEI)
no
point sources and county-level area
sources (?)
2005 ?
This inventory will be released in the future. The EPA reports that it will represent a reduced level of effort, to allow additional resources to be devoted to developing a re-engineered 2008 inventory. Earlier announced plans called for the inventory to be released in Dec 2006, but it does not appear to be available at this time.
Largest sources of total mercury emissions to the air in the U.S. and Canada, based on the U.S. EPA 1999 National Emissions Inventory
and 1995-2000 data from Environment Canada
Canaan Valley Institute-NOAA
BeltsvilleEPA-NOAA
Three sites committed to speciated mercury
ambient concentration measurement network
Grand BayNOAA
45
Hg from other sources: local, regional & more distant
atmospheric depositionto the water
surface
atmospheric deposition
to the watershed
Measurement of ambient air
concentrations
Measurement of wet
deposition
R e s o l u t i o n : 2 . 5 m i n D u r a t i o n : 1 1 D a y s
0
2
4
6
8
1 0
1 2
2 5 - A u g 2 6 - A u g 2 7 - A u g 2 8 - A u g 2 9 - A u g 3 0 - A u g 3 1 - A u g 0 1 - S e p 0 2 - S e p 0 3 - S e p 0 4 - S e p 0 5 - S e p
Hg
- (u
g/m
3 )
H g TH g 0H g 2
S e r i e s 3 3 0 0 C E M - C o n t i n u o u s S p e c i a t e d M e r c u r y D a t a
R e s o lu t io n : 2 .5 m in D u ra t io n : 1 1 D a y s
0
2
4
6
8
1 0
1 2
2 5 -A u g 2 6 -A u g 2 7 -A u g 2 8 -A u g 2 9 -A u g 3 0 -A u g 3 1 -A u g 0 1 -S e p 0 2 -S e p 0 3 -S e p 0 4 -S e p 0 5 -S e p
Hg
- (u
g/m
3 )
H g TH g 0H g 2
S e r ie s 3 3 0 0 C E M - C o n tin u o u s S p e c ia te d M e r c u ry D a ta
Thanks to Marty Keller, Senior Applications Engineer, Tekran Instruments Corporation, for providing this graph!
Variations on time scales of minutes to hoursCEM’s needed – and not just on coal-fired power plantsCEM’s must be speciated or of little use in developing critical source-receptor informationClean Air Mercury Rule only requires ~weekly total-Hg measurements, for purposes of trading
We don’t have information about major eventse.g., maintenance or permanent closures, installation of new pollution control devices, process changesTherefore, difficult to interpret trends in ambient data
Temporal Problems with Emissions Inventories
Long delay before inventories released2002 inventory is being released this year in U.S.; till now, the latest available inventory was for 1999How can we use new measurement data?
Amortize over 4 yrs: ~$50,000/yr
~$50,000/yr to operate
Speciation Continuous Emissions Monitor (CEM):
~$200,000 to purchase/installCost of Electricity
0.10/kw-hr 0.10001/kw-hr
1000 MW x $0.10/kw-hr = $1,000,000,000 per year
Overall Budget of Power Plant
Total: ~$100,000/yr
$1000/yr $1000.10/yr
Mercury transforms into methylmercury in soils
and water, then canbioaccumulate in fish
Humans and wildlife affected primarily byeating fish containing mercury
Best documented impacts are on the developing fetus: impaired motor and cognitive skills
atmospheric deposition to the watershed atmospheric deposition
to the water surface
49adapted from slides prepared by USEPA and NOAA
• How much from local/regional sources?
• How much from global sources?
• Monitoring alone cannot give us the answer
• atmospheric models required, “ground-truthed”by atmospheric monitoring
Where does the mercury come from that is depositing to any given waterbody or watershed?
Hg(0)
Hg(II) Hg(p)
Hg(0) from distant sources
atmospheric emissions of Hg(0), Hg(II), Hg(p)
atmosphericchemistry
interconvertsmercury forms
HYSPLIT-Hg Atmospheric Fate and Transport Model