atmospheric fate and transport of mercury lake ontario contaminant monitoring & research...

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, [email protected]

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 models modeling can help fill in spatial gaps between measurement sites modeling 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 emissions different 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

an

k

coal-fired elec gen

other fuel combustion

waste incineration

metallurgical

manufacturing/other

Many uncertainties in these earlier results…

How to refine modeling and link with other

models in a multi-media framework?



atmospheric deposition

to the water surface

Hg(0)

Hg(II) Hg(p)




to the watershed



emissions of Hg(0), Hg(II), Hg(p)emissions of Hg(0), Hg(II), Hg(p)





Hg(0)

Hg(II) Hg(p)



Hg(0)

Hg(II) Hg(p)

Hg(0)

Hg(II) Hg(p)




to the watershed


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/Runoff

Outflow

Settling/Resusp Diffusion

Wet and dry Deposition

MeHg

Hg(0)

Hg(II)

Volatilization

Hg(II) MeHgBioaccumulation

BurialBurial


Source: R. Harris, Tetra-Tech, Inc.

Inflow/Runoff

Outflow


Wet and dry Deposition

MeHg

Hg(0)

Hg(II)

Volatilization

Hg(II) MeHgBioaccumulation

BurialBurial


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-time linkage 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 Model

wet 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

meteorology

Inputs 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


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


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 Data speciated ambient concentrations (need RGM and Hg(p), not just total gaseous mercury)

wet deposition

Emissions inventories complete “accurate” speciated up-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 impacts requires atmospheric models

atmospheric models require: knowledge of atmospheric chemistry & fate emissions data ambient data for “ground-truthing”

24





Hg(0)

Hg(II) Hg(p)




to the watershed

Measurement of ambient air

concentrations

Measurement of wet

depositionWET DEPOSITION complex – hard to diagnose weekly – many events background – also need near-field

AMBIENT AIR CONCENTRATIONS more fundamental – easier to diagnose need continuous – episodic source impacts need 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

De

po

sitio

n (

ug

/m2

-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

De

po

sitio

n (

ug

/m2

-ye

ar)

HYSPLIT

25% added to CMAQ

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).

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

ME

02

ME

09

ME

96

ME

98

NB

02

NS

01

NY

20

PA

13

PA

37**

PA

90*

PA

60*

PQ

04**

IL11

MN

16*

MN

18*

MN

23*

MN

27

WI08

WI09*

WI36**

WI99

NC

08*

NC

42

FL

04

FL

05

FL

11

FL

34

GA

09*

LA

05

LA

10

LA

28

SC

19

TX

21

r v

alu

e

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


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

0

0.2

0.40.6

0.8

1

ME

02

ME

09

ME

96

ME

98

NB

02

NS

01

NY

20

PA

13

PA

37

PA

90

PA

60

PQ

04

IL11

MN

16**

MN

18**

MN

23

MN

27

WI08*

WI09

WI36

WI99*

NC

08*

NC

42

FL

04

FL

05**

FL

11

FL

34

GA

09

LA

05

LA

10

LA

28

SC

19

TX

21r

valu

e

NE SEMW


Random Coefficient Model results for Northeastern and Midwestern annual 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


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 (

μg

/m2

)

MW Deposition

20052004200320022001200019991998

Year

12.50

10.00

7.50

5.00

Hg

(μ

g/m

2)

NE Deposition

Northeast Midwest Southeast

1990

-199

6

1999

-200

1

1990

-199

6

1999

-200

1

1990

-199

6

1999

-200

1

0

10

20

30

40

50

60

70

Em

issi

on

s (m

etr

ic to

ns/

yr)

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

1

0

5

10

15

20

25

30

35

Em

issi

on

s flu

x (g

/km

2-y

r)

Hg(II)

Hg(p)

Hg(0)


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

Illinois

Indiana

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

/m2-

yea

r

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


100

200

300

400

500

600

700

800kg

/yea

r

CAN 2000USA 1999CAN 1995USA 1996


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

19

65

19

70

19

75

198

0

198

5

19

90

19

95

200

0

200

5

Lake Erie 45-cm Walleye

0.00.20.40.60.81.0

19

65

197

0

19

75

198

0

19

85

19

90

19

95

20

00

200

5

Lake Huron 45-cm Walleye

0.00.20.40.60.81.0

19

65

19

70

197

5

198

0

198

5

19

90

19

95

200

0

200

5

Lake Superior 45-cm Walleye

0.00.20.40.60.81.0

196

5

19

70

197

5

19

80

198

5

19

90

199

5

20

00

200

5

Lake Erie Walleye (Ages 4-6)

0.00

0.10

0.20

0.30

0.40

19

77

19

80

19

83

19

86

19

89

19

92

19

95

19

98

20

01

20

04

Figure 101. Mercury concentration trends Great Lakes Walleye.Total mercury concentrations (ppm or 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

hig

an

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

198

2

1984

1986

1988

1990

1992

1994

1996

1998

2000

2002

200

4

Year

ug

/g (

+/-

S.E

.)

Erie

Ontario

Huron

Superior

Mic

hig

an

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

199

6

1998

2000

2002

200

4

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

200

1

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 25 fish 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

1112

13

14

15

2. Agawa Rock

0.0

0.2

0.4

0.6

0.8

1970 1980 1990 2000

1. Granite Island

0.0

0.2

0.4

0.6

0.8

1970 1980 1990 2000

3. Big Sister Island

0.0

0.2

0.4

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

0.0

0.2

0.4

0.6

0.8

1970 1980 1990 2000

7. Chantry Island

0.0

0.2

0.4

0.6

0.8

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

3

4

67

9

1110

1213

14

5

8

15 161718

19

20

2122 23

24

25

19

92

19

94

19

96

19

98

20

00

20

02

20

040.00

0.04

0.08

0.12 16. Peach Orchard Pt.1

992

199

4

199

6

1998

200

0

200

2

2004

0.00

0.04

0.08

0.1212. Black River Canal

199

2

199

4

199

6

1998

200

0

200

2

2004

0.00

0.04

0.08

0.12 9. Thunder Bay

199

2

1994

1996

1998

200

0

200

2

200

40.00

0.04

0.08

0.12 11. Sandpoint

19

92

19

94

19

96

19

98

20

00

20

02

20

040.00

0.04

0.08

0.12 4. Calumet Breakwater

19

92

19

94

19

96

19

98

20

00

20

02

20

04

0.00

0.04

0.08

0.12 6. Holland Breakwater

1992

199

4

1996

199

8

2000

2002

200

40.00

0.04

0.08

0.12

5. Hammod Marina

199

2

1994

1996

1998

200

0

200

2

200

40.00

0.04

0.08

0.127. Muskegon

199

2

199

4

199

6

199

8

200

0

20

02

200

4

0.00

0.04

0.08

0.12

0.16

0.20

0.24

0.28 3. North Chicago

1992

199

4

1996

199

8

2000

2002

200

40.00

0.04

0.08

0.12

8. Leelanau State Park

199

2

19

94

199

6

199

8

200

0

200

2

20

040.00

0.04

0.08

0.12 24. Oswego

Erie

Ontario

Huron

Superior

Mic

hig

an

1992

199

4

199

6

199

8

2000

2002

200

40.00

0.04

0.08

0.1221. Niagara Falls

1992

1994

199

6

1998

2000

200

2

2004

0.00

0.04

0.08

0.1223. Rochester

1992

199

4

199

6

199

8

2000

2002

200

40.00

0.04

0.08

0.1225. Cape Vincent

199

2

199

4

199

6

19

98

200

0

200

2

20

040.00

0.04

0.08

0.12 10. Saginaw River

199

2

19

94

199

6

199

8

200

0

200

2

20

040.00

0.04

0.08

0.1217. Old Woman Creek

19

92

19

94

19

96

19

98

20

00

20

02

20

04

0.00

0.04

0.08

0.1215. Reno Beach

199

2

1994

1996

1998

200

0

200

2

200

40.00

0.04

0.08

0.12 14. Stony Point

1992

199

4

199

6

199

8

2000

2002

200

40.00

0.04

0.08

0.1218. Lorain

199

2

1994

1996

1998

200

0

200

2

200

40.00

0.04

0.08

0.1219. Ashtabula

1992

199

4

199

6

199

8

2000

2002

200

40.00

0.04

0.08

0.1222. Olcott

199

2

1994

1996

1998

200

0

200

2

200

40.00

0.04

0.08

0.1220. Dunkirk

1992

199

4

1996

199

8

2000

2002

200

40.00

0.04

0.08

0.12

13. Anchor Bay

199

2

199

4

199

6

19

98

200

0

200

2

20

040.00

0.04

0.08

0.12

2. Milwaukee Bay19

92

199

4

1996

199

8

2000

2002

200

40.00

0.04

0.08

0.12

1. 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

http://www8.nos.noaa.gov/cit/nsandt/download/mw_monitoring.aspx

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


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


1999 113 some of the incinerator emission reductions may not have occured till 2000-2001


no


2002 ? We have been unable to obtain summary or detailed information from this inventory, as of December 2006.


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





to the watershed

Measurement of ambient air

concentrations

Measurement of wet

deposition

Resolution: 2.5 min Duration: 11 Days

0

2

4

6

8

10

12

25-Aug 26-Aug 27-Aug 28-Aug 29-Aug 30-Aug 31-Aug 01-Sep 02-Sep 03-Sep 04-Sep 05-Sep

Hg

- (

ug

/m3 )

HgT

Hg0

Hg2

Series 3300 CEM - Continuous Speciated Mercury Data

Resolution: 2.5 min Duration: 11 Days

0

2

4

6

8

10

12

25-Aug 26-Aug 27-Aug 28-Aug 29-Aug 30-Aug 31-Aug 01-Sep 02-Sep 03-Sep 04-Sep 05-Sep

Hg

-

(ug

/m3 )

HgT

Hg0

Hg2

Series 3300 CEM - Continuous Speciated Mercury Data

Thanks to Marty Keller, Senior Applications Engineer, Tekran Instruments Corporation, for providing this graph!

Variations on time scales of minutes to hours CEM’s needed – and not just on coal-fired power plants CEM’s must be speciated or of little use in developing

critical source-receptor information Clean Air Mercury Rule only requires ~weekly total-Hg

measurements, for purposes of trading

We don’t have information about major events e.g., maintenance or permanent closures, installation

of new pollution control devices, process changes Therefore, difficult to interpret trends in ambient data

Temporal Problems with Emissions Inventories

Long delay before inventories released 2002 inventory is being released this year in U.S.;

till now, the latest available inventory was for 1999 How 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


49

adapted 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)


interconverts mercury forms

HYSPLIT-Hg Atmospheric Fate and Transport Model

atmospheric fate and transport of mercury lake ontario contaminant monitoring & research...

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