Janja D. Husar and Rudolf B. Husar Anthropogenic Mercury Mobilization and Emissions in US and Florida, 1930-2000 Janja D. Husar and Rudolf B. Husar Washington University, St. Louis, Missouri Supported by Florida Department of Environmental Protection Tetra-Tech, Inc

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

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.

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

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

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 80-160 Mg/yr since 1900 The Hg fraction emitted during combustion is 50-75% The coal Hg emission ranged 60- 120 Mg/year

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

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

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

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

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

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

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 1930-1990 Note the the significant paint contribution to the atmospheric emissions, 1960-1990

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

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 2.5 - 4 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

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 (1930-2000).

Waste Combustion Fraction and Rate The emission fraction of municipal waste was between 10 and 30% for the US The decline (1960-1980) was due to closing of incinerators Recent increase is due to regulated incineration (WTE) units Paint mercury in FL occurred in 1960-1990 Assuming 75% emission fraction, the emission rate was ~8 Mg/yr for 1970-1990.

Mercury Emissions: US and Florida The US Hg emission ranged between 300-500 Mg/yr (1940-1990). The Florida Hg emissions have increased from 5 to 15 Mg/yr during the 1940-1990 period. Nationally, coal was a significant contributor throughout the period. In Florida, coal became significant in the 1990s

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.

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

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 1960-1990 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 1960-1990 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.

Waste Combustion Fraction and Rate The emission fraction of municipal waste was between 10 and 30% for the US The decline (1960-1980) was due to closing of incinerators Recent increase is due to regulated incineration (WTE) units Data

Mercury in Agriculture: Florida Florida mercury agriculture use

Comparison of RMB and flow method Three county comparison. Electrical, control, and lab use were incinerated at reported WTE rates, for 1990-1998. 1980-1980 incineration was apportioned using Florida factors

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