Tracking changes in Mercury Deposition to Maryland and Understanding the impact on its Biota

Andrew Heyes and Cynthia C. Gilmour

Tony Prochaska, Michael Kashiwagi, Helen Stewart, John Sherwell, Mark Castro

Tim Rule

Mark S. Castro*,† and John Sherwell. 2016. Effectiveness of Emission Controls to Reduce the Atmospheric Concentrations of MercuryDOI: 10.1021/acs.est.5b03576 Environ. Sci. Technol. 2015, 49, 14000−14007

Management Questions for Regarding Mercury Deposition in the 1990’s If we reduce inorganic Hg emissions will it have an impact on mercury deposition and methylmercury concentrations in fish? How will we know if methylmercury concentrations in fish are responding to reductions in Hg emissions? What else can we do to mitigate the impact of Hg on aquatic organisms and fisheries?

Mercury Monitoring Program 2006

Approach follows: Mason et al. “Monitoring the Response to Mercury Deposition” Environ. Sci. Tech 2005 And Harris, R., Krabbenhoft, D., D. Engstrom, C. Gilmour,, J. Hurley, R. Mason et al. 2005. “Recommendations For Monitoring And Assessing Environmental Response To A Change In Mercury Loading Using Water- And Sediment- Based Indicators.” In: R.Harris, Ed. “Recommendations for Long-term Mercury Monitoring and Assessment,” SETAC publications.

Controls on deposition and transport: Deposition: Strength and proximity of sources Source type Atmospheric chemistry Transport: Landuse Geology/soil type Catchment:lake area ratio

Controls on net methylation: “Age” and complexation of Hg Basin morphometry -

• extent of shallow sediments and wetlands • surface to volume ratio

Water and sediment chemistry – • sulfate, DOC, nutrients

Temperature Drying and rewetting of soils/sediments

Controls on bioaccumulation: Food web structure

• length of food chain • benthic vs. pelagic

Water chemistry – DOC, Cl Lake stratification Transport of MeHg from sites of methylation

Deposition

Transport

Watershed retention

Deposition

Methylation

Bioaccumulation

Conceptual Diagram of the Controls on MeHg in Fish

Mercury Deposition

Only half the story as about 50 % falls as dry deposition

Precipitation

T-Hg Concentration

2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017

T-H

g n

g L

-1

0

2

4

6

8

10

12 MD00

MD08

MD99

Precipitation

2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017

cm Y

-1

0

20

40

60

80

100

120

140

160MD00

MD08

MD99

T-Hg Deposition

2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017

T-H

g u

g m

-2

0

2

4

6

8

10

12

14MD00

MD08

MD99

SERC Frostburg Beltsville

Mercury Concentration in Precipitation

Mercury Deposition

Mercury Concentration

Annual T-Hg Concentration

2008 2010 2012 2014 2016

T-H

g n

g L

-1

0

2

4

6

8

10

MD00

Annual T-Hg Concentration

2006 2008 2010 2012 2014 2016

T-H

g n

g L

-1

0

2

4

6

8

10

MD08

Annual T-Hg Concentration

2006 2008 2010 2012 2014 2016

T-H

g n

g L

-1

0

2

4

6

8

10

12

MD99

Annual T-Hg Deposition

2008 2010 2012 2014 2016

T-H

g u

g m

-2

0

2

4

6

8

10

12

MD00

Annual T-Hg Deposition

2006 2008 2010 2012 2014 2016

T-H

g u

g m

-2

0

2

4

6

8

10

12

MD08

Annual T-Hg Deposition

2006 2008 2010 2012 2014 2016

T-H

g u

g m

-2

0

2

4

6

8

10

12

14

MD99

Mercury Deposition

SERC

Frostburg

Beltsville

Mercury in Fish

Measure Different Source Contributions to Fish Hg

Hg Isotope 3

(Wetland)

Hg Isotope 2

(Lake)

Hg Isotope 1

(Upland)

Hg added to system at 5 times current deposition rate for 5 years.

METAALICUS unpublished Under review Please do not cite or display See published paper for earlier plot

We can see this clearly because we used enriched isotope

Harris, R.C., Rudd., J.W.M., Amyot, M., Babiarz, C.L., Beaty, K.G., Blanchfield, P.J., Bodaly, R.A., Branfireun, B.A., Gilmour, C.C. Graydon, J.A., Heyes, A. Hintelmann, H., Hurley, J.P., Kelly, C.A., Krabbenhoft, D.P., Lindberg, S.E., Mason, R.P. Paterson, M.J. Podemski,C.L., Robinson, A., Sandilands, K.A., Southworth, G.R., St. Louis, V.L., Tate, M.T. 2007. Whole ecosystem study shows rapid fish mercury response to changes in mercury deposition. Proc. Nat. Acad. Sci. 104:16586-16591. 10.1073/pnas.0704186104.

Site Latitude Longitude Map Number

Sharptown-nanticoke 38.53876 75.72741 1

Plum-Point Head of Bay 39.48696 76.11385 2

Mill Town Patuxent River 38.63302 76.69111 3

Eagle Harbor Patuxent River 38.57051 76.68219 4

Tuckahoe Lake 38.96854 75.94462 5

Piney Reservoir 39.70842 79.0018 6

Savage River Reservoir 39.54327 79.13751 7

Liberty Reservoir 39.44576 76.88376 8

Prettyboy Reservoir 39.65239 76.74183 9

Cash Lake 39.03199 76.79729 10

Lake Lariat 38.37774 76.42265 11

Deep Creek 39.55807 79.35482 12

Loch Raven 39.46250 76.57814 13

Young of the Fish Year Study

White Perch

Bass

Largemouth Bass MeanHg Concentration

Savage R

iver R

eserv

oir

Piney Rese

rvoir-

Fro

stburg

Liberty R

eserv

oir

Pretty

boy Rese

rvoir

Cash L

ake

Lake Laria

t

Tuckahoe L

ake

Deep Cre

ek

Loch R

aven

Hg (

ng g

-1 w

et

wt)

0

50

100

150

200

250

2008

2009

2010

2011

2012

2013

2014

2015

2016

2017

2018

White Perch

Largemouth Bass

Nanticoke

Year

2008 2010 2012 2014 2016 2018

Hg (

ng

g-1

)

0

5

10

15

20

25

30

Cash Lake

Year

2008 2010 2012 2014 2016 2018

Hg

(n

g g

-1)

0

50

100

150

200

250

Largemouth Bass

Fish Size

Fish Hg

Savage Reservoir

Year

2008 2010 2012 2014 2016 2018

Fis

h L

eng

th (

mm

)30

40

50

60

70

80

90

Savage Reservoir

Year

2008 2010 2012 2014 2016 2018

Hg

(n

g g

-1)

0

50

100

150

200

250

300

Controls on net methylation: “Age” and complexation of Hg Basin morphometry -

• extent of shallow sediments and wetlands • surface to volume ratio

Water and sediment chemistry – • sulfate, DOC, nutrients

Temperature Drying and rewetting of soils/sediments

Controls on bioaccumulation: Food web structure

• length of food chain • benthic vs. pelagic •Fish growth rate

Water chemistry – DOC, Cl Lake stratification Transport of MeHg from sites of methylation

Impact of Land-use

109

110

Total-Filterable-Hg concentrations in surface water of two SERC watersheds

1/1/2007 1/1/2008 1/1/2009 1/1/2010 1/1/2011 1/1/2012 1/1/2013 1/1/2014

Filt

era

ble

T-H

g n

g L

-1

0

2

4

6

8

10

12

14110

109

110 109

2X wet deposition?

Filterable MeHg Concentrations in Stream water 2007-2013

1/1/2007 1/1/2008 1/1/2009 1/1/2010 1/1/2011 1/1/2012 1/1/2013 1/1/2014

Filt

era

ble

MeH

g n

g L

-1

0.001

0.01

0.1

1

10

110

109

High nitrate Lower Hg

Respiration Denitrification Sulfate reduction

Low nitrate

High Hg

Forested

Stream

Schematic Model of Biogeochemical Processes in Riparian Zone – Hg Methylation

Carbon Pool Transformations

Timing of processes are different between the two watersheds

Agriculture

Decrease in Hg Bioavailability with reduction of DOC?

MeH

g n

g g

-1

0

100

200

300

400

500

600

T-H

g n

g g

-1

0

200

400

600

800

1000

Amphipods Isopods

109

110

109 110

SERC Stream Invertebrates 2016

Concentration and deposition decreasing slowly Watershed variables have an impact There is a couple between Hg load and Hg in biota Need to investigate dry deposition and role of forest and transit time of Hg with watersheds To my knowledge there are no studies like these being conducted elsewhere in the world!

Questions?