Florida Mercury in Electrical Sector

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Progress Report
Florida FCG PO #
Trends of Mercury Flows in Florida
Submitted by:
Janja D. Husar and Rudolf B. Husar
Lantern Corporation
63 Ridgemoor Dr.
Clayton, MO 63105
Project Officer
Curtis Pollman, PhD
TetraTech, Inc
408 W. University Ave. Suite 308
Gainesville, FL 32608
November 10, 2001
Background
Elevated mercury levels were found in the upper levels of the food chain in southern Florida.
Recently, a significant decline of mercury in birds was observed. The cause of the sharp decline
is not well understood. This Florida Mercury Trends Trend project was initiated to elucidate the
recent mercury emission trends for Florida.
Phase I: Municipal, Medical; Fuel Waste Combustion. In the first phase of the work,
conducted during March-May, 2001 with support from Florida DEP, the mercury emissions
drivers for Florida were estimated based on the existing records for municipal waste combustion,
medical waste combustion and fossil fuel burning. The report of this phase is contained in
PowerPoint presentation: Trends of Mercury Emission Drivers for Southern Florida 1980-2000
(http://capita.wustl.edu/capita/capitareports/Mercury/FlHgEmissDrivers.ppt ).At the meeting in
West Palm Beach, May 10-11, 2001 it was decided to expand the scope and focus of this
mercury trend study from the focus on emission drivers in southern Florida to a broader scale
mercury budgeting study that starts with a national mercury budget a subsequently focuses on
Florida and southern Florida, respectively. The goal of the broader approach, is to explore a more
complete assessment of mercury sources of air emissions and land disposal. The added values of
the broader budgeting approach include:
 Independent estimate of atmospheric Hg emissions in S. Florida.
 Accounting for the total mercury flow in Florida (air, land and water).
 Re-examining, expanding and updating the national Hg budget with new data.
Phase II: National Mercury Flow and Budgeting. The second phase of the work, also
supported by Florida DEP, focused on the national mercury budgeting and trend study with
special emphasis on Florida. The Phase II report ‘Trends of Mercury Flow over the US with
Emphasis on Florida’, contains a review of the recent mercury flow literature.
http://capita.wustl.edu/capita/capitareports/Mercury/Goods_fuel_trend.doc.
Inherently, it was a study of limited scope and results. It does not contain a full account of
mercury trends and flows in Florida. Rather, it is considered to be the beginning of an extended
mercury emission trend study to be conducted jointly by FCG and the Florida DEP.
Phase III. Full Florida Mercury Flow Study. This third phase of the Florida mercury flow and
trend study, evaluates the mercury flow drivers all the major economic sectors. (more description
here).
2
Summary of the National Mercury Budgets and Flows.
The national mercury flow and trend estimates were used extensively in estimating the Florida
mercury trends. For this reason, the relevant section of the previous report ‘Trends of Mercury
Flow over the US’ is summarized below..
Recent work by Sznopek and Goonan, 2000 contains an updated trend of the national mercury
flow that includes the primary production, consumption, recycling as well as mercury flow from
stocks. The apparent mercury supply (Figure 2) includes primary and secondary production, net
imports, and government stockpile releases. From 1970 to 1986, the main contributors to
mercury flow were primary mine production and imports. During 1986-92, there was a rapid
decrease of apparent Hg demand caused by reductions in mercury demand for batteries, paint
and fungicide industries. From 1993 on, the primary mine production was negligible, the
secondary production (recycling) increased and stock releases were terminated.
Net Import
Stock
Stock Release
Mining
Mine Production
Production
Consumption
Secondary
Production
Recycling
Figure 1. Trend of the US ‘apparent’ mercury supply, 1970-1998. (Sznopek and Goonan, 2000).
The EPA Mercury Report to Congress, 1997, addressed the atmospheric emissions of mercury.
The report concluded that the mercury releases to the atmosphere are dominated by coal and oil
combustion (53%). (Figure 2)
3
Figure 2. Mercury atmospheric emission inventory (EPA, 1997).
A different approach to assess the flow of mercury was reported by Sznopek and Goonan, 2000.
For 1996, they report that estimated 144 Mg of mercury was emitted to the atmosphere (Figure 2
and 3) based on combustion of fuels and goods incineration. They also reported that in 1996, 295
Mg mercury in industrial goods were disposed into landfills (Figure 4). Sznopek and Goonan,
2000 reported that in 1996 stocks of mercury totaled 6,800 Mg (private), and 4,600 Mg (U.S.
government), totaling 11,400 Mg of mercury (Figure 5). They also point out that given the 1996
mercury industrial demand of 372 Mg/yr (U.S Bureau of Mines, 1996) for creating goods, the
US has a 27 year stockpile of mercury.
Figure 3. Materials flow schematics for 1996. The blue lines are atmospheric emissions from the EPA
(1997) report, adding to 144 Mg/yr atmospheric emissions. The right hand portion of the
schematics depicts mercury flow in goods (Sznopek and Goonan, 2000).
4
US Mercury in Goods and Fuels
Figure 4 shows the overall mercury flow in the US during the 1940-1995 period. It includes the
flow through goods as well as fuels. In 1940-1970 the demand for mercury for industrial goods
was high during the WWII, slightly decreased in 1945 and then reached maximum in the late
1960s (Figure 4). The consumption of mercury in consumer goods was not well documented in
1940-1970 period. In 1940 74% of mercury consumption was categorized as "Other".
Essentially, the use of mercury was not disclosed. Since 1970, the use of mercury in consumer
goods was disclosed more precisely, and the "Other category represented <10%. 1970-1990
electrical and electronic instruments category (including batteries) was the dominant Hg
industrial consumer. The drastic reduction in mercury demand for consumer goods occurred
since 1989. Hg consumption in consumer/industrial goods was reduced from around 1500 Mg/yr
in 1989 to about 500 Mg/yr in 1995 (U.S. Bureau of Mines, 1940-1995).
Mercury mobilization in coal has increased since 1940. However, the coal contribution in 1940
to the overall mercury input into the system was <6% (Figure 5). In 1995, mercury mobilization
by coal contributed about 20% (Figure 6).
Mercury mobilization by petroleum products (using 50 ppb Hg concentration for crude oil)
increased since 1940. Petroleum contribution is still unresolved, lacking information on more
reliable Hg content in crude oil, and information on fate of mercury in extraction process,
shipping, refining, and ultimately concentration of Hg in petroleum products consumed.
Figure 4. Trend of mercury in industrial/consumer goods and fuels.
5
Summary Trend of Mercury in Coal and Petroleum in Florida
Mercury Flow through Coal
The estimate of Florida trends for mercury emissions from coal is depicted in Figure5. Mercury
emission exhibit a slow increase between 1960 and 1980, followed by a sharp increase between
1980 and 1990, and leveling off in the early 1990s. The 1998 estimated mercury mobilized in
coal consumed in Florida was about 4 Mg/yr. Only a fraction (0.5-0.75) of the mobilized coal
mercury is emitted to the atmosphere. The estimated coal mercury emission to the atmosphere in
the 1990s was in the range of 2-3 Mg/yr (Figure 5).
Figure 5. Trend of coal mercury emissions in Florida.
6
Mercury Flow through Petroleum
Petroleum products carry mercury from a geological reservoir and distribute mercury to the
environment along their passage. This section describes the flow and trend of mercury as carried
by petroleum products. To construct the mass balance of mercury flow, we begin by examining
the origin, Hg concentration and amount of petroleum consumed and .
If we take the 1999 input of crude oil into US refineries at 0.9 billion Mg/yr, and the low
estimate of Hg concentration of 5 ppb, and high estimate of 50 ppb, then lower estimate of 4.5
Hg and higher estimate of 45 Hg Mg/yr mercury mobilized with crude oil.
Figure 6. Mass balance of mercury flow at refineries (Wilhelm, 2001).
Figure 7. US Mercury flow trend in petroleum products.
Using the available mercury concentration data mercury in petroleum products consumed in
Florida was estimated (Figure 8).
7
Figure 8. Florida mercury trend in petroleum products.
8
Mercury in Electrical Sector
Electrical uses of mercury have steadily increased since 1941. There was a sharp peak in
electrical sector consumption in 1944 and 1945, followed by a sharp drop to pre 1941 levels.
After 1947 the use of mercury in electrical sector has steadily increased, reaching levels of 1,000
Mg/year from 1976 to 1986. In the late 1980s and early 1990s mercury use in the electrical
sector dropped dramatically, falling to 78 Mg/yr in 1996.
Figure 1.
Figure 2.
9
The mercury use in electrical sector increased dramatically since 1960s from 14% to its peak in
1985 of 63%, thus in 1984 and 1985, the battery industry accounted for more than 60% of the
total United States consumption (Figure 2) of mercury (US Bureau of Mines).
The battery industry has been driven by two major types of batteries, mercury-zinc and alkaline
batteries. The mercury-zinc batteries pre-date the alkaline batteries. The mercury-zinc batteries
were originally used in hearing aids, and their use has been expanded to transistorized
equipment, watches, calculators, etc. Alkaline batteries were invented and 1967 and their
consumption has grown exponentially. Beginning in the late 1980s, state legislatures began to
enact laws to phase out mercury use in batteries. Mercury use in alkaline batteries has been
eliminated in early 1990s. However, mercury-zinc batteries were eliminated in 1996, except in
limited non-household uses (Figure3).
Figure 3.
Approach and Results
Until 1978 the U.S. Bureau of Mines (BOM) reported a single mercury consumption number for
electrical uses. In 1978 BOM started reporting inside electrical consumption, battery,
switches/wiring, and lighting categories with their cumulative value representing the electrical
consumption.
Lighting category according to EPA 1992 has doubled since 1960s, but their overall contribution
to mercury consumption in electrical sector was between 1-2%. The contribution of lighting in
1996 was at the same level as in 1960s <20 Mg/yr Hg. The mercury in lighting was
reconstructed using U.S. Bureau of Census fluorescent and HID lamps domestic shipments and
multiplying with mercury content of fluorescent lamps (0.75, 0.55, 0.30) for different time
periods, and HID mercury content (0.33 and 0.25) (EPA, 1992, Benazon Environmental, 1998).
10
Figure 4.
The EPA' Mercury Study Report to Congress noted that the electrical switches containing
mercury were not manufactured prior to the 1960 The switching/wiring industry according to
Sznopek and Goonan, 2000 has not changed much since 1960s contributing around 100 Mg/yr
in 1960-1990, and representing 10-20% of total electrical consumption of mercury. In 1996 the
switches/wiring sector contribution was 49 Mg/yr
Battery sector was the most dominant sector since invention of alkaline batteries. The pre 1967
period was dominated by mercury-zinc batteries (Figure 3). Prior to 1960 switches/wiring sector
was not using any mercury. To obtain the battery mercury consumption prior to 1978, switches
and lighting consumption was substracted from total consumption. Prior to 1960, only lighting
consumption was subtracted on the 1960s level.
11
Another approach to estimate mercury burden to the environment was used by EPA 1992.
Battery retail sales were provided by the National Electrical Manufacturers Association
(NEMA) for 1983-1988, and estimates for 1989, and 1992. Based on these sales figures a trend
was established and used to estimate sales 1967-1982 and 1993-2000, respectively. The amount
of mercury battery import was assumed at 15 %.
Figure
These two drivers, one, mercury consumption in battery industry and another battery retail sales
vary within a factor of two or less. At this time we can only speculate for reasons of discrepancy.
A plausible explanation is that the BOM data do not reflect the exports and imports of batteries.
To elucidate this factor of two discrepancy, export data on batteries would be of great interest.
Bureau of Census does not provide those data in physical units.
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Florida Mercury in Electrical Sector
The mercury consumption in electrical sector is prorogated by population percentage. The
maximum contribution of mercury in 1980s was in the range of 50 Mg/yr.
13
Mercury Fungicides in Agriculture
In agriculture mercury was primarily used as fungicide. The fungicidal properties of mercurial
compounds have been recognized since the latter part of the 18th century. Originally the major
usage of inorganic mercury compounds was for seed protection. Mercury fungicides, containing
2 to 4% of metallic mercury were used for application to seeds, cotton, rice, wheat, rye, barley,
oats, flax, peanuts, safflower. Also mercury fungicides were used as seed protectants for potato
seed pieces, for cabbage seedlings, for gladiolas, and other bulbs. Mercurous chloride was
continued to be recommended for turf and golf course treatment (Sharvelle, 1961) throughout the
1970s (Murphy and Aucott, 1999.
Only recently, (Sharvelle, 1961), with introduction of organic mercurials the range of their
application has been expanded from seeds to foliage protection. Mercurial fungicides were used
as foliar fungicides for scab of apples, pears, strawberries and other fruits.
Mercury consumed in agriculture in 1930-1940 ranged between 50 Mg/yr, representing 13% of
total US mercury consumption Murphy and Aucott, 1999). Between 1940-1960 mercury
consumption in agriculture steadily increased, reaching 350 Mg/yr in 1956, representing 9% of
total US mercury consumption. Since 1956 agriculture mercury declined to 50 Mg/Year in 1970,
and steadily declining from 9% of total US mercury consumption to less than 1% in 1975. In
1970, the use of mercury fungicides in agriculture was banned. However, the use of mercury
fungicides remained legal for specific diseases and for turf management. By 1980 only 1
Mg/year was reported as used in agriculture.
Approach and Results
The consumption of mercury in agriculture was documented in Bureau of Mines Yearbooks, and
later compiled and reported by Jasinski, 1994 and Murphy and Aucott, 1999. The uses of
mercury as fungicides was documented by Sharvelle, 1961 and Murphy and Aucott, 1999. Table
1. was assembled to account for mercury use in agriculture.
US Department of Agriculture (USDA) annual Agricultural Statistics provides drivers for small
seed (wheat, barley, oats, rye) consumption in USA. Using Sharvelle, 1961, 0.3g of mercury
application per bushel, the consumption trend of mercury for USA was reconstructed in Figure 1.
For 1930-1946 the use of mercury fungicide was overestimated compared to Bureau of Mines
estimate of mercury use in agriculture. For 1947-1970, the mercury use for seeds slowly
declined, due to decline in tonnage of seeds used in agriculture. In the absence of newer
information of mercury concentration in fungicides of 0.3 g/bushel was used.
The use of fungicides for golf courses was estimated by number of golf courses in USA (Scharff,
1970, Ross, 1979, NGF web site). and 80 acres/golf course treated with 43gr Hg/acre. This
estimate is an upper limit. The routine treatment of golf courses with fungicides was prevalent in
late 1950s and 1960s. In previous years, all the literature suggests that only affected areas were
treated with much higher concentrations of fungicides. In 1970s mercury fungicides were
gradually substituted with non-mercury fungicides.
The use of mercury for foliage treatment started in 1942. Apples and pears were mainly treated
with organomercury compounds. Annual acreage of apples was obtained from USDA
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Agricultural Statistics and 4.5 g/acre (Murphy and Aucott, 1999) was applied since middle
1940s.
Table 1. Mercury use in agriculture
Seed
Hg estimate
Reference
Wheat, barley, oats, rye
0.3-0.6 g/bushel
Sharvelle, 1961
Apples
4.5-9 g/acre
Murphy and Aucott, 1999
Turf
43 gr/acre
Sharvelle, 1961
Potatoes
Seed soaking
Sharvelle, 1961
Cabbage
Soil treatment
Sharvelle, 1961
Vegetables and Fruits
Seed soaking,
Sharvelle, 1961
foilage treatment
Bulbs and corms
Bulbs and corms
Sharvelle, 1961
soaking
The use of mercury for potato seeds, vegetable seeds (tomatoes, watermelon, beets), for soil
treatment for cabbage and cauliflower, for flower bulbs and corms is not well documented to
apportion the mercury use. Therefore, the remaining mercury (after subtracting small grain,
apple, and turf use) in the 1950 and 1960 was apportioned to vegetables and others.
The production of wheat, barley, oats, rye and apples is not significant in Florida. Thus, only the
Vegetable and Other portion of USA mercury consumption was prorated to Florida, using
vegetable acreage ratio of Florida compared to USA vegetable acreage.
The golf course mercury fungicide was estimated using Florida golf course statistics (Bureau of
Census, annual 1959-2000).
Figure 1. Apportionment of mercury use in U. S. agriculture
15
Figure 2. It is estimated that the mercury use for golf turf maintenance was increasing. For other
agricultural uses of mercury it could be assumed that about 2 Mg/yr was used in 1950s and about
1 Mg/yr in 1970s. Data are subject to change as better information is obtained.
16
Mercury Fungicides in Paints
Two largest categories of mercury use in products in 1990 were latex paint and batteries (Barr
Engineering, 2001). In the late 1950s organomercury compounds, and phenylmercuric acetate in
particular, were added to the water type paints to prolong the paint's shelf life. EPA provided
certain guidelines for the paint industry, restricting interior water type paints to 300 ppm Hg, and
exterior water type paints to 2000 ppm Hg. The paint industry was not required to report on
mercury concentration of its products. Apparently it varied, reaching sometimes >900 ppm for
interior latex paint (CDC, 1990). The Benazon Engineering Company, 1998 reports interior latex
paint Hg concentration of 45 ppm, and exterior 1050 ppm (estimate that only 20% of exterior
latex contained mercury), based on interviews of paint companies in 1990s.
Approach and Results
The approach used was to use the paint shipment driver and apply the estimated Hg
concentration factor to paints.
The information on US paint shipments is available from U.S. Bureau of Census annual Current
Industrial Reports. The historical total paint shipments were obtained from U.S. Bureau of
Census, 1975
The total paint shipments were increasing since 1950s. In 1965 the Bureau of Census started
reporting gallons of paints shipped as architectural paint, and intermittently classified in various
types of architectural paint. In early 1960 solvent based paints were dominant. However, water
type paints took over the market and by 1990 contributed to more than 60% of architectural
paints. The percentage of architectural paints of total paints used in US remained relatively
constant in this time period at about 42% (Figure 1).
17
Figure 1 U.S. trend of shipment of all paints, architectural paints, including water-type, and
solvent type paints (in 1000 of gallons).
Figure 2 shows the (1) trend of of total Hg use in paints based on Bureau of Mines and Jasinski,
1994, (2) estimated Hg flow if water-type paint with an average of 300 ppm Hg, (3) the late
1980's estimates of the interior water-type using Hg concentration of 45ppm plus 20% of exterior
water-type times Hg concentration of 1050 ppm (Benazon Environmental, 1998). Therefore, it
was concluded that the mercury content in water-type paints varied over time: it decreased from
about 300 ppm in 1970s to about 100 ppm in 1990. In 1990 the use mercury fungicides in paints
was banned.
The fate of mercury after paint application is somewhat uncertain. According (Taylor and Tickle,
1969, Taylor et al., 1969, Taylor and Hunter, 1972) as quoted in Benazon Environmental, 1998,
60% of the mercury of indoor paint and 75% of the outdoor paint is volatilized into the
atmosphere. The Minnesota Mercury Emission Inventory, 1999 states that 50% of mercury is
evaporated in the first year of application. Therefore, for the post 1990 years first-order
degradation will be applied to estimate emissions for 1990-2000.
Figure 2. a) Mercury use in paints industry; mercury in water-type paints, assuming 300 ppm; c)
interior water-type (45 ppm) and exterior water-type (1050, 20%); d) estimated water-type
average mercury concentration.
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Figure 3. Florida mercury in paints.
The paint mercury estimate for Florida is based on U.S. Bureau of Mines mercury use data and
Florida population data. Data are subject to change as better information is obtained.
References
CDC, 1990. (http://www.cdc.gov/mmwr/preview/mmwrhtml/0001566htm)
http://www.census.gov/prod/ec97/97numlist/325.pdf
Barr Engineering Co, Substance Flow Analysis of Mercury in Products, Report to Minnesota
Pollution Control Agency, 8/15/2001.
Benazon Environmental, Inc Historical Mercury Consumption and Release Estimates for the
Province of Ontario., April, 1998.
U.S. Bureau of Census, http://www.census.gov/prod/2manmin/mp94.pdf
U.S. Bureau of Census , Current Industrial Reports, Manufacturing Profiles,
http://www.census.gov/prod/2001pubs/mp98.pdf or
http://www.census.gov/ftp/pub/industry/1/ma28f99.pdf
U.S. Bureau of Census Historical Statistics of the United States, Colonial Times to 1970,
Bicentennial Edition, Washington, DC 1975.
19
Minnesota Pollution Control Agency, Options and Strategies for Reducing Mercury Releases,
Source Reduction Feasibility and Reduction Strategies Commitee Report,
http://www.pca.state.mn.us/hot/legislature/reports/1999/mercury.pdf
Engstrom Daniel and Edward Swain, Recent declines in Atmospheric Mercury deposition in the
upper Midwest, Environ. Sci and Techn., 31, 960-967., 1997
Jasinski, Stephen M. The Materials Flow of Mercury in the United States, Bureau of Mines
Information Circular , IC 9412, 1994.
Chu P. and Porcella D.B. (1995) Mercury stack emissions from US electric power plants, in
Porcell, D.B. Huckabee J.W. and Wheatley B, eds., Mercury as a Global Pollutant, Water, Air
and Soil Pollution, 80, 134-144.
Finkelman R.B. And Tewalt S.J. (1998) Mercury in U.S. coal, U.S.G.S. Open-File Report 980772 (http://energy.er.usgs.gov/products/openfile/OFR98-0772/index.htm).
Husar R.B. and Husar J.D. (1990) Sulfur. In The Earth as Transformed by Human Action
(edited by Turner B.L., et al.). Cambridge University Press with Clark University, Cambridge.
Jasinski S. M. (1994) The materials flow of mercury in the United States, Bureau of Mines
Information Circular 9412, http://geology.cr.usgs.gov/pub/circulars/c9412/index.html.
Kelly, W. R. and Long, S. E. (2001) An estimate fo mercury emissions to the atmopshere from
petroleum refining, submitted to Environ, Sci. & Tech., 2001.
Liang, L., Horvat M., and Danilchik (1996) A novel analytical method for determination of
picogram levels of total mercury in gasoline and other petroleum related products, Sci. Tot.
Environ., 1987, 57.
Liang, L., Lazoff, S,. Gilkeson J., Swain E., Horvat M. (1999) A simple combustion method for
determination of total mercury (THg) in crude oil and related products, In Mercury as Global
Pollutant-5th International Conference , May 23-28, Rio de Janeiro, Brazil.
Milici R. C. (1997) Coal-producing regions of the conterminous United States, compiled by
Robert C. Milici, U.S.G.S. Open-File Report 97-447
(http://energy.er.usgs.gov/products/openfile/OFR97-447/index.htm).
Sznopek J.L. and Goonan. T. G. (2000) The materials flow of mercury in the economies of the
United States and world, USGS Survey Circular 1197
http://geology.cr.usgs.gov/pub/circulars/c1197/index.html.
U.S. Bureau of Mines, US Department of Interior, Minerals Yearbook, annual books.
U.S. DOE Energy Information Administration, Annual Energy Review,
http://www.eia.doe.gov/emeu/aer/petro.html.
U.S. DOE Energy Information Administration (2000) Petroleum Supply Annual 2000, Volume
1.
U.S. DOE Energy Information Administration (1999) State Energy Data Report,
http://www.eia.doe.gov/emeu/sedr/contents.html#PDF Files.
20
U.S. EPA (1997), Mercury Study Report to Congress, Volume II An inventory of anthropogenic
mercury emissions in the United States, EPA-452/R-97-004. OAQPS and ORD.
Wilhelm, S. M. (2001) An estimate of mercury emissions to the atmosphere from petroleum,
submitted to Environ, Sci. & Tech., 2001.
Murphy, Eileen. Aucott, Michael. A Methodology to Assess the Amounts of Pesticidal Mercury
Used Historically in New Jersey,Journal of Soil Contamination, 8, 131-14, 1999.
Sharvelle, Eric. The Nature and Usase of Modern Fungicides, Burgess Publishing Company,
Minneapolis, 1961.
Scharff Robert (ed) Encyclopedia of Golf, Harper &Row, New York, 1970
Ross John M. (ed) Encyclopedia of Golf, Harper &Row, New York, 1979
http://www.ngf.org/faq/growthofgolf.html
U. S. Bureau of the Census County Business Patterns, Florida, GPO annual, 1959-2000
Jasinski, Stephen M. The Materials Flow of Mercury in the United States, Bureau of Mines
Information Circular , IC 9412, 1994.
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