modeling the atmospheric transport and deposition of ... · modeling the atmospheric transport and...

Modeling the Atmospheric Transport and Deposition of Mercury to the Great Lakes

Dr. Mark Cohen NOAA Air Resources Laboratory (ARL)

College Park, MD, USA

NOAA Air Resources Laboratory Seminar February 7, 2013, NCWCP, College Park MD

2

Acknowledgements

Roland Draxler Glenn Rolph Barbara Stunder Ariel Stein Fantine Ngan

HYSPLIT Development Team at ARL:

Winston Luke Paul Kelley Steve Brooks Xinrong Ren

Mercury Research

Team at ARL:

Great Lakes Restoration Initiative, via Interagency Agreement with USEPA

Funding:

Rick Jiang Yan Huang

IT Team at ARL:

+ numerous collaborations with external partners involving:

o emissions inventory data for model input, and

o atmospheric measurement data for model evaluation

3

Mercury in the Environment

Biodiversity Research Institute (2011): http://www.briloon.org/uploads/hgconnections/glmc/GLMC_FinalReport.pdf

Evers, D.C., et al. (2011). Great Lakes Mercury Connections: The Extent and Effects of Mercury Pollution in the Great Lakes Region. Biodiversity Research Institute. Gorham, Maine. Report BRI 2011-18. 44 pages.

4

Mercury in Great Lakes Fish 0.05 ppm level

recommended by the Great Lakes Fish Advisory

Workgroup (2007)

19

90

19

92

19

94

19

96

19

98

20

00

20

02

20

04

20

06

20

08

Temporal trends of mercury in Lake Erie 45−55 cm walleye collected between 1990−2007

(Bhavsar et al., Environ. Sci. Technol. 2010, 44, 3273-3279)

5

Atmospheric deposition is believed to be the largest current mercury loading pathway to the Great Lakes…

How much is deposited and where does it come from? (…this information can only be obtained via modeling...)

6

7

Different “forms” of mercury in the atmosphere

Elemental Mercury -- Hg(0)

• most of total Hg in atmosphere

• doesn’t easily dry or wet deposit

• globally distributed

Reactive Gaseous Mercury -- RGM

• a few % of total atmos. Hg

• oxidized Hg (HgCl2, others)

• very water soluble and “sticky”

• bioavailable

Particulate Mercury -- Hg(p)


• Hg in/on atmos. particles

• atmos. lifetime 1~ 2 weeks

• bioavailability?

?

Elemental Mercury -- Hg(0)

• most of total Hg in atmosphere

• doesn’t easily dry or wet deposit

• globally distributed

Reactive Gaseous Mercury -- RGM


• oxidized Hg (HgCl2, others)

• very water soluble and “sticky”

• bioavailable

Particulate Mercury -- Hg(p)


• Hg in/on atmos. particles

• atmos. lifetime 1~ 2 weeks

• bioavailability?

?

Type of Emissions Source

coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other

Emissions (kg/yr)

10-50

50-100

100–300

5-10

300–500

500–1000

1000–3000

8

2005 Atmospheric Mercury Emissions from Large Point Sources

Starting point: where is mercury emitted to the air?

2005 Atmospheric Mercury Emissions (Direct Anthropogenic + Re-emit + Natural)

Policy-Relevant Scenario Analysis

9

Dry and wet

deposition of

the pollutants

in the puff are

estimated at

each time step.

The puff’s mass, size,

and location are

continuously tracked…

Phase partitioning and chemical

transformations of pollutants within the

puff are estimated at each time step

= mass of pollutant

(changes due to chemical transformations and

deposition that occur at each time step)

Centerline of

puff motion

determined by

wind direction

and velocity

Initial puff location

is at source, with

mass depending

on emissions rate

TIME (hours)

0 1 2

deposition 1 deposition 2 deposition to receptor

lake

HYSPLIT-Hg Lagrangian Puff Atmospheric Fate and Transport Model

10

Next step: What happens to the mercury after it is emitted?

Uncertainties

Uncertainties

Uncertainties

To simulate the global

transport of mercury,

puffs are transferred to

Eulerian grid after a

specified time downwind

(~2 weeks), and the

mercury is simulated on

that grid from then on…

When puffs grow to sizes

large relative to the

meteorological data grid, they

split, horizontally and/or

vertically

This is how we model the

local & regional impacts.

But for global modeling,

puff splitting overwhelms

computational resources

Deposition explicitly modeled to actual lake/watershed areas

As opposed to the usual practice of ascribing portions of gridded deposition to these areas in a post-processing step

12

Lake Erie

Results scaled to actual RGM emissions of 43.6 g/hr 1 ng/m2-hr = 8.8 ug/m2-yr (if it persisted the entire year) Total deposition to Lk Erie is ~20 ug/m2-yr

Illustrative simulation of reactive gaseous mercury (RGM) emissions from one power plant on the shore of Lake Erie:

hourly deposition estimates for the first two weeks in May 2005

13

14

350,000 sources in global emissions inventory

typical one-year simulation takes ~96 processor hours

~3800 processor years, if ran explicit simulation for each source

Computational Challenge

Would like to keep track of each source individually

~240 years on 16-processor workstation

Spatial Interpolation

15

Chemical Interpolation

16

Standard Points in North America

17

For each standard source location, we do three unit-emissions simulations: o pure Hg(0), o pure HgII

(RGM) o pure Hg(p)

Standard Points Outside of North America

18

…three unit-emissions simulations for each location

19

This analysis done with 136 standard source locations

~4.5 processor years

Computational Solution

3 unit emissions simulations from each location (Hg(0), RGM, and Hg(p)

~3.5 months on 16-processor workstation

instead of 240 years … almost 1000x less!

Type of Emissions Source

coal-fired power plants other fuel combustion waste incineration metallurgical manufacturing & other

Emissions (kg/yr)

10-50

50-100

100–300

5-10

300–500

500–1000

1000–3000

20 2005 Atmospheric Mercury Emissions from Large Point Sources

an example for one source… the Monroe coal-fired power plant on the shore of Lake Erie

Detroit Edison Monroe coal fired power plant on the

shore of Lake Erie

Lake Erie

Monroe emitted 561 kg of mercury in 2005 (EPA’s National Emissions Inventory)

How much of this mercury was deposited into Lake Erie and its watershed?

21

Detroit Edison Monroe coal fired power plant on the

shore of Lake Erie

Lake Erie

Monroe emitted 561 kg of mercury in 2005 (EPA’s National Emissions Inventory)

Modeling results for this specific source:

• 24 kg (~4%) of this emitted mercury was deposited directly into Lake Erie

• 107 kg (~19%) of this emitted mercury was deposited in the Lake Erie Watershed

We make this same type of estimate for every source in the national and global emissions inventories used as model input… using spatial and chemical interpolation

22

HYSPLIT-Hg (with mercury-specific chemistry, …)

Unit Emissions Simulations of Hg(0), Hg(II) and Hg(p) from an array of standard source locations

Emissions Inventory – emissions of Hg(0), Hg(II), and Hg(p) from sources at specified latitudes and longitudes

“Multiplication” of emissions inventory by array of unit emissions simulations using spatial and chemical interpolation

Evaluate overall model results: compare against ambient measurements

Source-attribution results for deposition to selected receptors

HYSPLIT

Outline of Modeling Analysis

23

y = 0.95xR² = 0.59

y = 1.44xR² = 0.15

0

2

4

6

8

10

12

14

16

18

0 2 4 6 8 10 12

Mo

del

ed

Me

rcu

ry W

et

De

po

siti

on

(u

g/m

2-yr

)

Measured Mercury Wet Deposition (ug/m2-yr)

MDN sites in the "western" Great Lakes region

MDN sites in the "eastern" Great Lakes region

1:1 line

Linear (MDN sites in the "western" Great Lakes region)

Linear (MDN sites in the "eastern" Great Lakes region)

Error bars shown are the range in model predictions obtained

with different precipitation adjustment schemes (none, all,EDAS only, NCEP/NCAR only)



Modeled vs. Measured Wet Deposition of Mercury at Sites in the Great Lakes Region

24

After all the standard source simulations have been run, and the impacts of each of the ~350,000 sources worldwide are estimated using spatial and chemical interpolation, is the model giving reasonable results?

Standard source locations, MDN sites, and mercury emissions in the Great Lakes region

25

HYSPLIT-Hg (with mercury-specific chemistry, …)

Unit Emissions Simulations of Hg(0), Hg(II) and Hg(p) from an array of standard source locations

Emissions Inventory – emissions of Hg(0), Hg(II), and Hg(p) from sources at specified latitudes and longitudes

“Multiplication” of emissions inventory by array of unit emissions simulations using spatial and chemical interpolation

Evaluate overall model results: compare against ambient measurements

Source-attribution results for deposition to selected receptors

HYSPLIT

Outline of Modeling Analysis

26

2005 Atmospheric Mercury Emissions (Direct Anthropogenic + Re-emit + Natural)


27

Geographical Distribution of 2005 Atmospheric Mercury Deposition Contributions to Lake Erie


28

Keep track of the contributions from each source, and add them up

-

500

1,000

1,500

2,000

2,500

3,000

3,500

4,000

< 5

00

km

50

0 -

1,0

00

km

1,0

00

-3

,00

0 k

m

3,0

00

-1

0,0

00

km

10

,00

0 -

20

,00

0 k

m

Me

rcu

ry E

mis

sio

ns

(M

g/y

r)

Distance of Emissions Source from

the Center of Lake Erie

Emissions from Natural Sources

Emissions from Re-Emissions

Emissions from Anthropogenic

Sources

A tiny fraction of 2005 global mercury emissions within 500 km of Lake Erie

-

50

100

150

200

250

< 5

00

km

50

0 -

1,0

00

km

1,0

00

-3

,00

0 k

m

3,0

00

-1

0,0

00

km

10

,00

0 -

20

,00

0 k

m

De

po

siti

on

Co

ntr

ibu

tio

n (

kg/y

r)

Distance of Emissions Source from

the Center of Lake Erie

Contributions from Natural Sources

Contributions from Re-Emissions

Contributions from Anthropogenic

Sources

Modeling results show that these “regional” emissions are responsible for a large fraction of the modeled 2005 atmospheric deposition

Important policy implications!

29

Results can be shown in many ways…

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

1 10 100 1000 10000

Cumulative Fraction of Total

Modeled Mercury

Deposition to Lake Erie

(2005)

Rank of Source's Atmospheric Mercury Deposition Contribution to Lake Erie

30

…350,000

DET

RO

IT E

DIS

ON

MO

NR

OE

PO

WER

CO

NES

VIL

LE REL

IAN

T EN

ERG

Y A

VO

N L

AK

E

FIR

STEN

ERG

Y C

OR

P E

AST

LAK

E

REL

IAN

T EN

ERG

Y K

EYST

ON

E

Nan

tico

ke G

ener

atin

g St

atio

n

PA

PO

WER

CO

BR

UC

E M

AN

SFIE

LD P

LT

DET

RO

IT E

DIS

ON

TR

ENTO

N C

HA

NN

EL

CA

RD

INA

L P

OW

ER P

LAN

T

REL

IAN

T EN

ERG

Y SH

AW

VIL

LE

W. H

. SA

MM

IS P

LAN

T

DU

NK

IRK

STE

AM

GEN

ERA

TIN

G S

TATI

ON

HO

MER

CIT

Y O

L H

OM

ER C

ITY

GEN

STA

CLE

VEL

AN

D E

LEC

TRIC

ASH

TAB

ULA

TOLE

DO

ED

ISO

N C

O. B

AY

SHO

RE

OH

IO P

OW

ER -

MIT

CH

ELL

PLA

NT

ALL

EGH

ENY

ENER

GY

HA

TFIE

LDS

FER

RY

MO

NO

NG

AH

ELA

PO

WER

FO

RT

MA

RTI

N

J R

WH

ITIN

G C

O

DET

RO

IT E

DIS

ON

RIV

ER R

OU

GE

OH

IO P

OW

ER -

KA

MM

ER P

LAN

T

ALL

EGH

ENY

ENER

GY

AR

MST

RO

NG

OR

ION

PO

WER

NEW

CA

STLE

DET

RO

IT E

DIS

ON

ST.

CLA

IR

MO

UN

T ST

OR

M P

OW

ER P

LAN

T

R. E

. BU

RG

ER P

LAN

T

HU

NTL

EY S

TEA

M G

ENER

ATI

NG

STA

TIO

N

AP

PA

LAC

HIA

N P

OW

ER -

JOH

N E

AM

OS

Do

mta

r P

aper

Jo

hn

son

bu

rg M

ill

CLE

VEL

AN

D E

LEC

TRIC

LA

KE

SHO

RE

PLA

NT

Lam

bto

n G

ener

atin

g St

atio

n

PP

G IN

DU

STR

IES

OH

IO C

IRC

LEV

ILLE

Essr

oc

Cem

ent

Co

rp.

LAFA

RG

E SY

STEC

H E

NV

IRO

NM

ENTA

L C

OR

P.

Nia

gara

Fal

ls

RO

SS IN

CIN

ERA

TIO

N S

ERV

ICES

INC

.

Bio

med

ical

Was

te In

cin

erat

ion

_43

20

Bio

med

ical

Was

te In

cin

erat

ion

_42

45

STER

ICYC

LE IN

C

VO

N R

OLL

AM

ERIC

A IN

C

Bio

med

ical

Was

te In

cin

erat

ion

_43

19

CEN

TRA

L W

AYN

E EN

ERG

Y R

ECO

VER

Y

Rep

ub

lic E

ngi

nee

red

Ste

els

Inc

NO

RTH

STA

R B

LUES

CO

PE

STEE

L LL

C

AK

STE

EL C

OR

PO

RA

TIO

N

No

rth

Sta

r St

eel

ISG

CLE

VEL

AN

D IN

C.

Van

dM

STA

R

ASH

TA C

HEM

ICA

LS IN

C

GE

RA

VEN

NA

LA

MP

PLA

NT

MI

OH

OH

OH

OH

OH

PA O

N

PA M

I OH P

A OH N

Y PA OH O

H WV IN P

A WV OH M

I MI

WV NY PA PA M

I

WV OH OH OH OH NY

OH

WV

ON ON PA

OH

OH

ON

OH

ON M

I

OH

OH

OH M

I

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

0 5 10 15 20 25 30 35 40 45 50

Cu

mu

lati

ve F

ract

ion

of

Tota

l M

od

ele

d D

ep

osi

tio

n (

20

05

)

Rank of Source's Atmospheric Mercury Deposition Contribution to Lake Erie

Top 50 Atmospheric Deposition Contributors to Lake Erie

coal fired power plants

other fuel combustion

waste incineration

metallurgical

manufacturing and other

Based on estimated 2005 mercury emissions, e.g., from the 2005 USEPA National Emissions Inventory, and atmospheric fate and transport simulations with the NOAA HYSPLIT-Hg model

31

Natural 23%

Ocean

Re-emission 14%

U.S. 32%

China 14%

Canada 3%

India 2%

Other Countries 12%

Sources of Mercury Deposition to the Great Lakes Basin 2005 Baseline Analysis

Total = 11,300 kg/yr

32

Natural 17%

Ocean Re-emission

10%

U.S. 49%

China 10%

Canada 4%

India 1%

Other Countries 9%

Sources of Mercury Deposition to the Lake Erie Basin

2005 Baseline Analysis

Total = 2,300 kg/yr

33

Natural 23%

Ocean

Re-emission 14%

U.S. 32%

China 14%

Canada 3%

India 2%

Other Countries

12%

Sources of Mercury Deposition to the Great Lakes Basin 2005 Baseline Analysis

Total = 11,300 kg/yr

Natural 17%

Ocean Re-emission

10%

U.S. 49%

China 10%

Canada 4%

India 1%

Other Countries

9%

Sources of Mercury Deposition to the Lake Erie Basin

2005 Baseline Analysis

Total = 2,300 kg/yr

34

Jan 1, 2010

Jan 1, 2011

Jan 1, 2012

Jan 1, 2013

Jan 1, 2014

Jan 1, 2009

Jan 1, 2015

Jan 1, 2016

ARL’s GLRI Atmospheric Mercury Modeling Project

FY12 $ Scenario Analysis

FY13 $ (proposed) Update Analysis (~2008)

FY11 $ Sensitivity Analysis + Extended Model Evaluation

FY10 $ Baseline Analysis for 2005

Initial Inter- and Intra-Agency Planning for FY10 GLRI Funds

FY14 $ (proposed) Update Analysis (~2011)

35

A multi-phase project

Using 2005 meteorological data and emissions, the deposition and source-attribution for this deposition to each Great Lake and its watershed was estimated

2005 was chosen as the analysis year, because 2005 was the latest year for which comprehensive mercury emissions inventory data were available at the start of this project

Phase 1: Baseline Analysis for 2005 (Final Report Completed December 2011)

The model results were ground-truthed against 2005 Mercury Deposition Network data from sites in the Great Lakes region

36

Modeling Atmospheric Mercury Deposition to the Great Lakes. Final Report for work conducted with FY2010 funding from the

Great Lakes Restoration Initiative. December 16, 2011. Mark Cohen, Roland Draxler, Richard Artz. NOAA Air Resources Laboratory, Silver Spring, MD, USA. 160 pages.

http://www.arl.noaa.gov/documents/reports/GLRI_FY2010_Atmospheric_Mercury_Final_Report_2011_Dec_16.pdf

http://www.arl.noaa.gov/documents/reports/Figures_Tables_GLRI_NOAA_Atmos_Mercury_Report_Dec_16_2011.pptx

37

One-page summary: http://www.arl.noaa.gov/documents/reports/GLRI_Atmos_Mercury_Summary.pdf

Some Key Features of this Analysis

Deposition explicitly modeled to actual lake/watershed areas

Uniquely detailed source-attribution information is created

As opposed to the usual practice of ascribing portions of gridded deposition to these areas in a post-processing step

deposition contribution to each Great Lakes and watersheds from each source in the emissions inventories used is estimated individually

The level of source discrimination is only limited by the detail in the emissions inventories

Source-type breakdowns not possible in this 1st phase for global sources, because the global emissions inventory available did not have source-type breakdowns for each grid square

Combination of Lagrangian & Eulerian modeling

allows accurate and computationally efficient estimates of the fate and transport of atmospheric mercury over all relevant length scales – from “local” to global.

38

Some Key Findings of this Analysis

Regional, national, & global mercury emissions are all important contributors to mercury deposition in the Great Lakes Basin

For Lakes Erie and Ontario, the U.S. contribution is at its most significant

For Lakes Huron and Superior, the U.S. contribution is less significant.

Local & regional sources have a much greater atmospheric deposition contributions than their emissions, as a fraction of total global mercury emissions, would suggest.

“Single Source” results illustrate source-receptor relationships

For example, a “typical” coal-fired power plant near Lake Erie may contribute on the order of 1000x the mercury – for the same emissions – as a comparable facility in China.

39

Some Key Findings of this Analysis (…continued)

Reasonable agreement with measurements

Despite numerous uncertainties in model input data and other modeling aspects

Comparison at sites where significant computational resources were expended – corresponding to regions that were the most important for estimating deposition to the Great Lakes and their watersheds – showed good consistency between model predictions and measured quantities.

For a smaller subset of sites generally downwind of the Great Lakes (in regions not expected to contribute most significantly to Great Lakes atmospheric deposition), less computational resources were expended, and the comparison showed moderate, but understandable, discrepancies.

40

Ground-truthing the model against additional ambient monitoring data, e.g., ambient mercury air concentration measurements and wet deposition data not included in the Mercury Deposition Network (MDN)

Examining the influence of uncertainties on the modeling results, by varying critical model parameters, algorithms, and inputs, and analyzing the resulting differences in results

Phase 2: Sensitivity Analysis + Extended Model Evaluation (current work, with GLRI FY11 funding)

41

0%

2%

4%

6%

8%

10%

12%

14%

bas

elin

e

afte

r cr

ash

; ne

w c

om

pile

rar

ray

fix

mat

h o

pt.

= 0

(vs

2),

arr

ay f

ixar

ray

pat

ch, g

rid

exp

ansi

on

= f

ull

(vs

1.5

x)m

ath

op

t. =

0 (

vs 2

), a

rray

fix

, gri

d e

xp =

fu

ll (v

s.…

rele

ase

ele

vati

on

= 5

0 m

(vs

25

0)

EDA

S re

gio

nal

me

t d

ata

(vs

NA

RR

)

tim

e st

ep

= 2

0 m

in (

vs 1

2)

tim

e st

ep

= 3

0 m

in (

vs 1

2)

max

pu

ff li

feti

me

= 2

wks

(vs

3)

max

pu

ff li

feti

me

= 4

wks

(vs

3)

PU

F +

GEM

(vs

PU

F o

nly

)

max

nu

mb

er

of

pu

ffs

= 1

0K

(vs

20

K)

max

nu

mb

er

of

pu

ffs

= 4

0K

(vs

20

K)

1 p

uff

pe

r 7

hrs

(vs

3),

sp

lit a

fter

7 h

rs (

vs 2

4)

1 p

uff

pe

r 7

hrs

(vs

3),

sp

lit a

fter

48

hrs

(vs

24

)

Hg0

dry

de

p =

0 (

vs m

od

ele

d)

wet

dep

was

ho

ut

par

ame

ter

*0

.5w

et d

ep w

ash

ou

t p

aram

ete

r *

2

hv

red

uct

ion

aq

* 2

hv

red

uct

ion

aq

* 0

.5o

3 o

xid

atio

n g

as *

2o

3 o

xid

atio

n g

as *

0.5

oh

oxi

dat

ion

aq

* 2

oh

oxi

dat

ion

aq

* 0

.5o

h o

xid

atio

n g

as *

2o

h o

xid

atio

n g

as *

0.5

so2

red

uct

ion

aq

* 2

so2

red

uct

ion

aq

* 0

.5so

ot

par

titi

on

eq

lbrm

* 2

soo

t p

arti

tio

n e

qlb

rm *

0.5

soo

t p

arti

tio

n r

ate

* 2

soo

t p

arti

tio

n r

ate

* 0

.5

Fraction of RGM

emissions deposited in

Lake Erie from a

hypothetical source

in Detroit

Fort

ran

co

mp

ilati

on

Ch

em

istr

y an

d

Par

titi

on

ing

De

po

siti

on

m

od

elin

g

Tim

e s

tep

Pu

ff li

feti

me

Nu

mb

er

of

pu

ffs

Met data (EDAS vs. NARR)

Release height 50 m vs 250 m

42

0.000%

0.001%

0.002%

0.003%

0.004%

0.005%

0.006%

bas

elin

e

afte

r cr

ash

; ne

w c

om

pile

r

rele

ase

ele

vati

on

= 5

0 m

(vs

25

0)

max

nu

mb

er

of

pu

ffs

= 1

0K

(vs

20

K)

max

nu

mb

er

of

pu

ffs

= 4

0K

(vs

20

K)

Hg0

dry

de

p =

0 (

vs m

od

ele

d)

wet

dep

was

ho

ut

par

ame

ter

*0

.5

wet

dep

was

ho

ut

par

ame

ter

*2

hv

red

uct

ion

aq

* 2

hv

red

uct

ion

aq

* 0

.5

o3

oxi

dat

ion

gas

* 2

o3

oxi

dat

ion

gas

* 0

.5

oh

oxi

dat

ion

aq

* 2

oh

oxi

dat

ion

aq

* 0

.5

oh

oxi

dat

ion

gas

* 2

oh

oxi

dat

ion

gas

* 0

.5

so2

red

uct

ion

aq

* 2

so2

red

uct

ion

aq

* 0

.5

soo

t p

arti

tio

n e

qlb

rm *

2

soo

t p

arti

tio

n e

qlb

rm *

0.5

soo

t p

arti

tio

n r

ate

* 2

soo

t p

arti

tio

n r

ate

* 0

.5

Fraction of Hg(0)

emissions deposited in

Lake Erie from a

hypothetical source

in China

Co

mp

ilati

on

Ch

em

istr

y an

d

Par

titi

on

ing

De

po

siti

on

m

od

elin

g

Nu

mb

er

of

pu

ffs

Emit

he

igh

t

43

We will work with EPA and other Great Lakes Stakeholders to identify and specify the most policy relevant scenarios to examine

A modeling analyses such as this is the only way to quantitatively examine the potential consequences of alternative future emissions scenarios

Phase 3: Scenarios (next year’s work, with GLRI FY12 funding)

For each scenario, we will estimate the amount of atmospheric deposition to each of the Great Lakes and their watersheds, along with the detailed source-attribution for this deposition

44

Thanks!

45

46

EXTRA SLIDES

0

2

4

6

8

10

12

14

16

18

20

Erie Ontario Michigan Huron Superior

Atm

osp

he

ric

Me

rcu

ry D

ep

osi

tio

n(u

g/m

2-yr

)

Great Lake

Natural

Ocean Re-Emit

All Other Countries

Canada

China

United States

47

CLOUD DROPLET

cloud

Primary Anthropogenic

Emissions

Hg(II), ionic mercury, RGM

Elemental Mercury [Hg(0)]

Particulate Mercury [Hg(p)]

Re-emission of previously deposited anthropogenic

and natural mercury

Hg(II) reduced to Hg(0) by SO2 and sunlight

Hg(0) oxidized to dissolved Hg(II) species by O3, OH,

HOCl, OCl-

Adsorption/ desorption of Hg(II) to /from soot

Natural emissions

Upper atmospheric halogen-mediated oxidation?

Polar sunrise “mercury depletion events”

Br

Dry deposition

Wet deposition

Hg(p)

Vapor phase: Hg(0) oxidized to RGM and Hg(p) by O3, H202, Cl2, OH, HCl

Multi-media interface

Atmospheric Mercury Fate Processes

Reaction Rate Units Reference

GAS PHASE REACTIONS

Hg0 + O3 Hg(p) 3.0E-20 cm3/molec-sec Hall (1995)

Hg0 + HCl HgCl2 1.0E-19 cm3/molec-sec Hall and Bloom (1993)

Hg0 + H2O2 Hg(p) 8.5E-19 cm3/molec-sec Tokos et al. (1998) (upper limit

based on experiments)

Hg0 + Cl2 HgCl2 4.0E-18 cm3/molec-sec Calhoun and Prestbo (2001)

Hg0 +OH Hg(p) 8.7E-14 cm3/molec-sec Sommar et al. (2001)

Hg0 + Br HgBr2

AQUEOUS PHASE REACTIONS

Hg0 + O3 Hg+2 4.7E+7 (molar-sec)-1 Munthe (1992)

Hg0 + OH Hg+2 2.0E+9 (molar-sec)-1 Lin and Pehkonen(1997)

HgSO3 Hg0 T*e((31.971*T)-12595.0)/T) sec-1

[T = temperature (K)]

Van Loon et al. (2002)

Hg(II) + HO2 Hg0 ~ 0 (molar-sec)-1 Gardfeldt & Jonnson (2003)

Hg0 + HOCl Hg+2 2.1E+6 (molar-sec)-1 Lin and Pehkonen(1998)

Hg0 + OCl-1 Hg+2 2.0E+6 (molar-sec)-1 Lin and Pehkonen(1998)

Hg(II) Hg(II) (soot) 9.0E+2 liters/gram;

t = 1/hour

eqlbrm: Seigneur et al. (1998)

rate: Bullock & Brehme (2002).

Hg+2 + hv Hg0 6.0E-7 (sec)-1 (maximum)

Xiao et al. (1994);

Bullock and Brehme (2002)

(Evolving) Atmospheric Chemical Reaction Scheme for Mercury

?

?

?

new

What year to model?

Mercury Emissions Inventory

Meteorological Data to drive model

Ambient Data for Model Evaluation

Need all of these datasets for the

same year

Dataset Available for 2005

U.S. anthropogenic emissions inventory Canadian anthropogenic emissions inventory Mexican anthropogenic emissions inventory Global anthropogenic emissions inventory Natural emissions inventory Re-emissions inventory

Wet deposition (Mercury Deposition Network) “Speciated” Air Concentrations

NCEP/NCAR Global Reanalysis (2.5 deg) NCEP EDAS 40km North American Domain North American Regional Reanalysis (NARR)

2005 chosen for baseline

analysis

50

Getting good ground-truthing results harder

than estimating deposition to the Great Lakes One Standard Source Location (green dot) would do a decent job of estimating deposition to the receptor, for all of the hypothetical, “actual” source locations shown (numbered boxes) But the same Standard Source Location would be completely inadequate to estimate deposition and concentrations at the monitoring site (red star)

52

Standard Source Locations for Illustrative Modeling Results

53

1.0E-11

1.0E-10

1.0E-09

1.0E-08

1.0E-07

1.0E-06

1.0E-058 97

86

10

91 7 9 1 90 6 87

94 5 33

11

7

88 4 93

35

74

32

26

22

20

12

19

21

17

37

16

27

18

10

5

10

6

10

4

54

50

72

14

70

13

67

15

68

66

56

84

49

Great Lakes Regional Inset Map North American Regional Inset Map Global Map

Tran

sfe

r Fl

ux

Co

eff

icie

nt

to L

ake

Eri

e (

1/k

m2

)

Standard Source Location Number

Transfer Flux Coefficient to Lake Erie for a "Typical" Coal-Fired Power Plant

Transfer Flux Coefficient to Lake Erie for a Coal-Fired Power Plant with a higher RGM emissions fraction

The "Transfer Flux Coefficient" is calculated as the atmospheric deposition flux to a given receptor (in this case, Lake Erie) in units of g/km2-yr, divided by the total emissions from the source, in units of g/yr.

With this transfer flux coefficient, if one knows the emissions of the source in the given location, then the atmospheric dep osition fluximpact of the source on the receptor can be estimated, by simply multiplying the emissions by the transfer flux coefficient.

Lake Erie Transfer Flux Coefficients for two kinds of Generic Coal-Fired Power Plants (logarithmic scale)

54

0.0E+00

2.0E-07

4.0E-07

6.0E-07

8.0E-07

1.0E-06

1.2E-06

1.4E-06

1.6E-06

1.8E-06

2.0E-068 97

86

10

91 7 9 1 90 6 87

94 5 33

11

7

88 4 93

35

74

32

26

22

20

12

19

21

17

37

16

27

18

10

5

10

6

10

4

54

50

72

14

70

13

67

15

68

66

56

84

49


Tran

sfe

r Fl

ux

Co

eff

icie

nt

to L

ake

Eri

e (

1/k

m2

)


Transfer Flux Coefficient to Lake Erie for a "Typical" Coal-Fired Power Plant

Transfer Flux Coefficient to Lake Erie for a Coal-Fired Power Plant with a higher RGM emissions fraction



Lake Erie Transfer Flux Coefficients for two kinds of Generic Coal-FIred Power Plants (linear scale)

55

In order to conveniently compare different model results, a “transfer flux coefficient” X will be used,

defined as the following:

56

Transfer Flux Coefficients For Pure Elemental Mercury Emissions at an Illustrative Subset of Standard Source Locations, for Deposition Flux Contributions to Lake Erie

58

Transfer Flux Coefficients For Pure Reactive Gaseous Mercury Emissions at an Illustrative Subset of Standard Source Locations, for Deposition Flux Contributions to Lake Erie

59

1.0E-11

1.0E-10

1.0E-09

1.0E-08

1.0E-07

1.0E-06

1.0E-058 97

86

10

91 7 9 1 90 6 87

94 5 33

11

7

88 4 93

35

74

32

26

22

20

12

19

21

17

37

16

27

18

10

5

10

6

10

4

54

50

72

14

70

13

67

15

68

66

56

84

49


Tran

sfe

r Fl

ux

Co

eff

icie

nt

to L

ake

Eri

e (

1/k

m2

)


Transfer Flux Coefficient to Lake Erie for Pure Hg(II) Emissions

Transfer Flux Coefficient to Lake Erie for Pure Hg(p) Emissions

Transfer Flux Coefficient to Lake Erie for Pure Hg(0) Emissions



Transfer Flux Coefficients For Hg(0), Hg(II), and Hg(p) to Lake Erie (logarithmic scale)

60

0.0E+00

5.0E-07

1.0E-06

1.5E-06

2.0E-06

2.5E-06

3.0E-068 97

86

10

91 7 9 1 90 6 87

94 5 33

11

7

88 4 93

35

74

32

26

22

20

12

19

21

17

37

16

27

18

10

5

10

6

10

4

54

50

72

14

70

13

67

15

68

66

56

84

49


Tran

sfe

r Fl

ux

Co

eff

icie

nt

to L

ake

Eri

e (

1/k

m2

)


Transfer Flux Coefficient to Lake Erie for Pure Hg(II) Emissions

Transfer Flux Coefficient to Lake Erie for Pure Hg(p) Emissions

Transfer Flux Coefficient to Lake Erie for Pure Hg(0) Emissions



Transfer Flux Coefficients For Hg(0), Hg(II), and Hg(p) to Lake Erie (linear scale)

61

Anthropogenic Mercury Emissions (ca. 2005)

Natural mercury emissions

Figure 55. Mercury Deposition Network Sites in the Great Lakes Region Considered in an Initial Model Evaluation Analysis

NOAA Air Resources Laboratory 64 Discussion July 5, 2012

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0N

Y68

PA7

2

NY2

0

IN2

8

IN2

6

PQ

04

PA6

0

PA4

7

IN2

1

PA9

0

PA0

0

PA3

7

PA1

3

PA3

0

PQ

05

IL1

1

IN2

0

OH

02

MN

27

WI3

6

MN

23

MN

22

MI4

8

MN

18

MN

16

WI9

9

WI3

1

WI2

2

WI0

9

IN3

4

WI3

2

ON

07

Me

asu

red

an

d M

od

ele

d P

reci

pit

atio

n (m

/yr)

max sample or rain gauge precip

sample precip

rain gauge precip

NCEP/NCAR Reanalysis precip

EDAS precip

Figure 56. Comparison of Total 2005 Precipitation Measured at each of the Great-Lakes Region MDN Sites with the Precipitation in the Meteorological Datasets Used as Inputs to this Modeling Study


Comparison of 2005 precipitation total as measured at MDN sites in the Great Lakes region (circles) with precipitation totals assembled

by the PRISM Climate Group, Oregon State University


y = 1.11x

0

2

4

6

8

10

12

14

16

18

0 2 4 6 8 10 12

Mo

del

ed

Me

rcu

ry W

et

De

po

siti

on

(u

g/m

2-yr

)

Measured Mercury Wet Deposition (ug/m2-yr)

model result (136 std pts)

1:1 line

Linear Regression





0

2

4

6

8

10

12

14

16

18

IN2

1

IN2

6

IN2

8

MN

27

OH

02

WI2

2

MN

22

MN

23

IL1

1

WI9

9

IN2

0

WI3

1

IN3

4

MI4

8

WI3

2

WI0

9

WI3

6

MN

18

MN

16

WI0

8

NY6

8

PA3

0

PA6

0

PA0

0

PA7

2

PA4

7

PQ

04

PA3

7

PA9

0

PA1

3

NY2

0

ON

07

2005

To

tal W

et

Me

rcu

ry D

ep

osi

tio

n(u

g/m

2-yr

)

Mercury Deposition Network Site

measurement

model result (136 std pts)

Error bars shown are the range

in model predictions obtainedwith different precipitation

adjustment schemes (none, all,EDAS only, NCEP/NCAR only)

MDN sites in the "western"

Great Lakes region

MDN sites in the "eastern"

Great Lakes region



Inventory domain Number

of records

Hg(0) emissions

(Mg/yr)

RGM emissions

(Mg/yr)

Hg(p) emissions

(Mg/yr)

Total mercury

emissions (Mg/yr)

U.S. Point Sources United States 19,353 50.6 35.5 9.1 95

U.S. Area Sources United States 44,848 4.5 1.8 1.1 7.4

Canadian Point Sources Canada 166 3.0 1.7 0.4 5.1

Canadian Area Sources Canada 12,372 1.0 0.96 0.42 2.4

Mexican Point Sources Mexico 268 28 0.81 0.46 29

Mexican Area Sources Mexico 160 1.25 0.38 0.25 1.9

Global Anthropogenic Sources not in U.S., Canada, or Mexico

Global, except for the U.S., Canada, and Mexico

52,173 1,239 434 113 1,786

Global Re-emissions from Land

Global land (and freshwater) surfaces

129,180 750 0 0 750

Global Re-emissions from the Ocean

Global oceans 43,324 1,250 0 0 1,250

Global Natural Sources Global 64,800 1,800 0 0 1,800

Total 366,804 5,127 475 125 5,728

Summary of Mercury Emissions Inventories Used in GLRI Analysis

0

500

1,000

1,500

2,000

2,500

3,000

3,500

4,000

Un

ited

Sta

tes

Ch

ina

Can

ada

Ind

ia

Ru

ssia

Mex

ico

Ind

on

esia

Sou

th K

ore

a

Jap

an

Co

lom

bia

Tota

l Atm

osp

he

ric

De

po

siti

on

to

the

Gre

at L

ake

s B

asin

(kg

/yr)

anthropogenic re-emissions

from land

direct anthropogenic

emissions

Model-estimated 2005 deposition to the Great Lakes Basin from countries with the highest modeled contribution from direct and re-emitted anthropogenic sources

0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

Un

ited

Sta

tes

Ch

ina

Can

ada

Ind

ia

Ru

ssia

Mex

ico

Ind

on

esia

Sou

th K

ore

a

Jap

an

Co

lom

bia

Tota

l Atm

osp

he

ric

De

po

siti

on

to

th

e

Gre

at L

ake

s B

asin

(u

g/y

r-p

ers

on

)

anthropogenic re-emissions

from land

direct anthropogenic

emissions

Model-estimated per capita 2005 deposition to the Great Lakes Basin from countries with the highest modeled contribution from direct & re-emitted anthropogenic sources

modeling the atmospheric transport and deposition of ... · modeling the atmospheric transport and...

Documents