1. Janja D. Husar and Rudolf B. Husar
Anthropogenic Mercury Mobilization and Emissions in US and Florida,
Janja D. Husar and Rudolf B. Husar
Washington University,
St. Louis, Missouri
Supported by
Florida Department of Environmental Protection
Tetra-Tech, Inc

2. Health and Environmental Concerns
The importance of mercury (Hg) as an environmental contaminant stems from its omnipresent nature, due largely to the magnitude of sources, its volatility, mobility, and persistence.
Elevated mercury concentrations are present in the upper levels of the food chain in southern Florida and Upper Midwest.
Recently, Northeast has been added to the warning list, NY Times, April, 2005
Warnings issued predominantly to pregnant women and children

3. Mercury Sources
Mercury is a building block of planet Earth (trace element).
Mercury metal is liquid and evaporates, depending on temperature and barometric pressure. Natural systems, wind, rain, volcanic disturbances shift mercury location.
MAN-MADE sources add to the environmental burden by taking mercury from its geological deposits and redistributing mercury to AIR , LAND and WATER.
Mercury in environment is either in elemental form or reactive gaseous mercury (RGM).
Atmospheric residence time
Hgo order of 90 days
Hg2+ (RGM) order of days.

4. Biomagnifications of Hg
Atmosphere is a transmission medium – no accumulation
Mercury is concentrated in the food chain.

5. Approach for Assessment of Anthropogenic Mercury
Mercury Inputs
Mercury in goods
Mercury in fuels
Multi-Scale: National, Florida, Southern Florida

6. Mercury mobilized in coal
Each coal mining region has a specific Hg content; USGS has extensive data for each coal region
Hg mobilization = S (Hg Conc. X Coal Production)
Most of coal in FL is from the Appalachian Basin
The total Hg mobilized in coal has been Mg/yr since 1900
The Hg fraction emitted during combustion is 50-75%
The coal Hg emission ranged Mg/year

7. Mercury Mobilized in Petroleum
Unlike for coal, the Hg content of crude oil is highly variable and the data are sparse.
Measured crude oil Hg concentration ranges between 10 and 30,000 ppb.
Fate of Hg in Crude Oil
Assuming 10 ppb in crude oil
“Other” still gas, naphtas, unfinished oils, petroleum coke (consumed at refineries and electric utilities), etc

8. US Mercury Mobilization Trend
Hg Mobilization:
Fuels
- Coal
- Crude Oil
Goods
Chlor-alkali
Pharmaceuticals
Agriculture, fungicide
Paint, fungicide
Lab use
Electrical, batteries
Control, manometers
Dental, amalgamation
Other
Data: Bureau of Mines (BOM), USGS, and DOE

9. Mercury Mobilized in Goods: Electrical Sector
Batteries were dominant until 1990
Hg in alkaline batteries were discontinued, beginning the 1980s
Hg is still used in lights and switches
Consistency of ‘electrical’ Hg use:
Bureau of Mines reports Hg consumption
Franklin reports Hg in discarded goods

10. Mercury in Paint
Phenyl mercuric compounds used as fungicide in water-type (latex) interior and exterior paints
Water-type paint consumption was increasing since the 1950s
The average paint Hg concentration (Hg used/Water Paint shipped) was declining from >300 ppm

11. Mercury NOT distributed with goods Mercury distributed with goods
Mercury Flow in Goods
Mercury NOT distributed with goods
Chlor-alkali - 14,000 Mg/70yrs
Mercury distributed with goods
Pharmaceuticals – 3,400 Mg/70yrs
Agriculture - 5,400 Mg/70yrs
Paint - 8,400 Mg/70yrs
Lab use – 1,800 Mg/70yrs
Electrical – 29,000 tons/70yrs
Control – 10,000 Mg/70yrs
Dental – 3,200 Mg/70yr
Mobilized in 70 years ~112,000 Mg
Data: Bureau of Mines (BOM), USGS, and DOE

12. Mercury Mobilization -> Atmospheric Emissions
Electrical
Control
Lab use
Dental
Pharmaceuticals
100%
AIR
Petroleum
Coal
50-75% Air
Air+Land
66% Air
Paint
Agriculture
100%
Land
Atmospheric emission fraction is estimated for each mercury flow category
Emission = Hg flow in goods and fuels * Emission fraction

13. Mercury Emissions: USA
The US mercury emissions were estimated based on the Hg flow and emission fractions
Nationally, coal combustion and electrical use contributed the bulk during
Note the the significant paint contribution to the atmospheric emissions,

14. Mercury Flow: US -> Mercury Flow: Florida
Electrical
Control
Lab use
Dental
Pharmaceuticals
Paint
Population prorated
Acreage use prorated
Agriculture
Florida specific
Coal
Petroleum

15. Mercury in Coal and Petroleum: Florida
Source of Coal Hg
E Kentucky
The Hg mobilized in coal increased to about 5 Mg/yr
The coal Hg emission ranged Mg/year in the 1990s
The Hg in oil products reached ~0.2 Mg/yr
Motor gasoline and residual fuel oil are the main contributors
Note that petroleum Hg is <<< Coal Hg

16. Mercury Flow in Florida
Cumulative Hg Flow: ~2000 Mg/70 yrs
Mercury flow in Florida has been steadily increasing until the 1980s
The electrical sector (batteries) was dominant throughout the period
The electrical sector contributed 50% of the cumulative Hg flow ( ).

17. Waste Combustion Fraction and Rate
The emission fraction of municipal waste was between 10 and 30% for the US
The decline ( ) was due to closing of incinerators
Recent increase is due to regulated incineration (WTE) units
Paint mercury in FL occurred in
Assuming 75% emission fraction, the emission rate was ~8 Mg/yr for

18. Mercury Emissions: US and Florida
The US Hg emission ranged between Mg/yr ( ).
The Florida Hg emissions have increased from 5 to 15 Mg/yr during the period.
Nationally, coal was a significant contributor throughout the period.
In Florida, coal became significant in the 1990s

19. Mercury Emissions: Comparison of Florida DEP – Material Flow Method
The mercury emissions were estimated by the Florida DEP for Waste to Energy (WTE) incinerators.
The corresponding (electrical, lab, control) emission estimates by the material flow method yield similar results.
In the 1990s, the Hg content of goods and paints has declined dramatically due to environmental regulations.
Hg from coal combustion became comparable to the Hg in goods.

20. Broward County mercury flow and emissions
Paint and electrical goods contribution was the largest in the Broward County.

21. Summary
Hg mobilization is driven by combustion of Hg containing fuels (coal and oil) and by Hg use for goods (batteries, instruments, paints) .
The US mercury mobilization peaked in period at about 2000 Mg/yr, followed by sharp decline in the 1990s due to environmental regulations.
The peak US atmospheric mercury emission rate was about 400 Tons/yr in the period.
In Florida, the mercury flow and emission rate has increased rapidly in the late 1960s, and dropped sharply in the 1990s.
The Hg flow and emission trends for Florida are now being reconciled with other data as part of the FCG and FL-DEP Mercury Trend Project.

22. Waste Combustion Fraction and Rate
The emission fraction of municipal waste was between 10 and 30% for the US
The decline ( ) was due to closing of incinerators
Recent increase is due to regulated incineration (WTE) units
Data

23. Mercury in Agriculture: Florida
Florida mercury agriculture use

24. Comparison of RMB and flow method
Three county comparison. Electrical, control, and lab use were incinerated at reported WTE rates, for incineration was apportioned using Florida factors

25. Mercury Flow Methodology
Flow method is based on mass balance applied to environmental compartments
Mercury flow through the ‘environment’ begins by mining of minerals and fuels
Along the flow, mercury is discarded to air, land and water