# Presentation: 367791

## Atmospheric Fate and Transport of Mercury 

**Atmospheric Fate and ****Transport of Mercury **

**Lake Ontario Contaminant Monitoring & Research Workshop**
**Planning for the 2008 Cooperative Monitoring Year**
** ****- Contaminants Component  –**
**Grand Island Holiday Inn, Grand Island, New York**
**March 27 & 28, 2007**

**Mark Cohen**
**NOAA Air Resources Laboratory**
**1315 East West Highway, **
**R/ARL, Room 3316**
**Silver Spring, Maryland, 20910, USA**
***mark.cohen@noaa.gov***
***http://www.arl.noaa.gov/ss/transport/cohen.html***

## Thanks, John!

*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*

## Slide 4

## 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)**** **

## Largest mercury sources in U.S. and Canadian air emissions inventories (~1999-2000)

***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

**Largest modeled atmospheric deposition contributors to Lake Ontario based on 1999-2000 emissions**

## Modeled atmospheric mercury deposition to Lake Ontario 

**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

## Many uncertainties in these earlier results...

***How to refine modeling and link with other models in a multi-media framework?***

## For Lake Ontario:

**For Lake Ontario:**
**How to link the atmospheric model and the aquatic fate/cycling model?**

## Air-Water Interface – at the boundary between the atmospheric model (over the lake) and the lake fate and cycling model

**Air-Water Interface – at the boundary between the atmospheric model (over the lake) and the lake fate and cycling model**

**It may turn out that dynamic, *****run-time***** linkage between lake and  atmosphere is not critical for Hg (?)**
**(we will see...)**

## Speciated ambient concentration data

**Speciated ambient concentration data**

**emissions**

## For model evaluation, inventory must be accurate and for same period as measurements 

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***For model ***_***evaluation***_***, inventory must be accurate and for same period as measurements ***
***(a big challenge!)***

## RGM emissions (~1999) in the Lake Ontario region 

**Lake Ontario**

**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 ***

## RGM emissions (~1999) in the Lake Ontario region, 

**Lake Ontario**

***Source of emissions data: U.S. EPA and Environment Canada***

**RGM emissions (~1999) in the Lake Ontario region, **
**and Mercury Deposition Network (MDN) sites**

## RGM emissions (~1999) in the Lake Ontario region, and (some of the) sites where speciated concentrations of atmospheric Hg have been measured

**Lake Ontario**

***Source 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)**

## RGM emissions (~1999) in the Lake Ontario region, 

**Lake Ontario**

***Source 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?

## 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”**

## WET DEPOSITION 

**WET 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**_

## 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). 

**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). **

## 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). 

- 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.

## 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.

**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 

**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.

## 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.

**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 Midwestern annual mercury concentration and deposition for 1998 to 2005.

**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.

## 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.

**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.

## Figure 2. Summary of mercury-related fish consumption advisories in the Great Lakes region.

- 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.**

## 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

**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**

## Model results for atmospheric deposition show that:

**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 decrease**
**	****between 1996 and 1999 ****(primarily due to decreased emissions from waste incineration)**

## Figure 101. Mercury concentration trends Great Lakes Walleye.

**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.**

## Figure 102. Total mercury levels in Great Lakes Rainbow Smelt, 1977-2004.

**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.**

## Figure 103. Mercury concentration trends in Lake Trout in the Great Lakes.

**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.**

## Figure 106. Trends in Herring Gull Egg Hg concentrations.

- 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.**

## Figure 107. Mercury concentration in Great Lakes region mussels (1992-2004). Total mercury in mussels (ug/g, on a dry weight basis). 

**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)_

## All of these analytical approaches are needed – 

**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***

## We need to understand Hg 

**Wet and dry deposition**
**of 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

**Diffusion**
**22-100 kg/yr**

**Solids Settling**
**1100 kg/yr**

**Resuspension**
**1700 kg/yr**

**Burial**
**2500 kg/yr**

**Inflow**
**680 kg/yr**

**Evasion**
**800 kg/yr**

**Outflow**
**100 kg/yr**

**Atmospheric **
**Deposition**
**360 kg/yr**

*slide courtesy of Elsie Sunderland, USEPA*

## Slide 43

## 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

**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**

**Three sites committed **
**to speciated mercury ambient concentration measurement network**

## Slide 45

## Thanks to Marty Keller, Senior Applications Engineer, 

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

**Notes:**
Marty Keller, Senior Applications Engineer, Tekran Instrument Corporation

## Temporal Problems with Emissions Inventories

**Temporal Problems with Emissions Inventories**

## Amortize over 4 yrs: ~$50,000/yr

**Amortize over 4 yrs: ~$50,000/yr**

**~$50,000/yr to operate**

## Where does the mercury come from that is depositing to any given waterbody or watershed? 

**Mercury transforms into methylmercury in soils**
** ****and water, then can****bioaccumulate in fish**

**Humans and wildlife affected primarily by**
**eating 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**

- 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?***** **