Assessment of Trends in Hg- Related Data Sets & Critical Assessment of Cause & Effect for Trends in...

Assessment of Trends in Hg-Related Data Sets & Critical

Assessment of Cause & Effect for Trends in Hg

Concentrations in Florida Biota

C.D. Pollman, Tetra TechD.B. Porcella, Environmental Science & Management

R. Husar, Lantern CorporationJ. Husar Lantern CorporationR. Roberson, RMB Associates

P. Frederick, University of FloridaM. Spalding, University of Florida

13 December 2001

DRAFT PRELIMINARY DATA SUBJECT TO CHANGE- DO NOT CITE OR QUOTE

HOW IT ALL STARTED:

Biota Trend #1 - Recent Declines in Hg in Largemouth Bass collected from the Florida

Everglades. Data from T. Lange (2000).

L-67A CanalAdjusted LS Means

1990 1992 1994 1996 1998 2000

Fille

t Hg

(µg

/g)

0.00

1.00

2.00

3.00


HOW IT ALL STARTED:

Biota Trend #2 - Concomitant Declines in Hg in Feathers of Everglades Great Egret Nestlings.

Data from P. Frederick (2000).

0

5

10

15

20

25

30

1994 1995 1997 1998 1999

Mea

n f

eath

er m

ercu

ry (

mg

/kg

@8c

m b

ill) 3B Mud

JW1

Hidden

Alley North

L-67

*

*

*

*

**

**

*

*

*

Hg in Great Egret Nestling Feathers


HOW IT ALL STARTED:

Biota Trend #3 - Comparatively Rapid Response By Aquatic Biota in Everglades Predicted to Occur in Response to

Reductions in Atmospheric Loading Rates of Hg.

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

0 10 20 30 40 50 60 70

Time After Load Reduction (Years)

Fis

h H

g (u

g/g

wet

mus

cle)

25% Reduction 50% Reduction

75% Reduction 85% Reduction

System Response Time to Load Reduction: E-MCM


HOW IT ALL STARTED:Comparision of measured MSW Hg emissions (concentrations)

in south Florida with the national inventory on MSW emissions compiled by Franklin and Kearney for USEPA

MSW Hg vs. S. Fla. Hg Emissions

0

100

200

300

400

500

600

700

800

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

years

To

ns

0

200

400

600

800

1000

1200

[Hg

} u

g/m

3

National Inventory Flux


Primary Objective BASIC PREMISE: If changes in Hg emissions and deposition have occurred,

and if this in turn produces a comparatively rapid change in biota, contemporaneous trends in a number of media also should be evident, including:

trends in emissions;

trends in atmospheric chemistry and deposition; and

trends in Hg accumulation rates in recent sediments.

OBJJECTIVE: Examine whether the trends in Hg concentrations in south Florida biota are significant, whether the trends (or lack thereof) are consistent with the available data on trends in Hg emissions, atmospheric deposition, and accumulation, and whether other factors need to be invoked to explain the data.


Secondary Objectives

Examine data pertaining to long-range transport and deposition of Hg and establish whether there have been changes in the signal to south Florida from these sources.

Using E-MCM, verify through model hindcasting whether the trends in largemouth bass are consistent with our understanding of changes in atmospheric loadings of Hg in south Florida.

Explore alternative hypotheses using E-MCM: For example, do other perturbations to the Everglades such as hydrologic changes and changes in sulfate loadings offer equally plausible or better explanations of the observed biotic trends.


Overall ApproachTest the hypothesis that recent trends in biota Hg concentrations in south Florida are a direct result of emissions

reductions in the region as well.

CRITICALLY ANALYZE TRENDS IN BIOTA

RECONSTRUCT TRENDS IN LOCAL

EMISSIONS

ESTABLISH LINK BETWEEN THE TIMING AND MAGNITUDE OF EMISSIONS AND THE TIMING

AND MAGNITUDE OF BIOTIC RESPONSE.


Material Flows Hg Trend Reconstruction - Update

Phase I work supported by FDEP and conducted March – May 2001.

Developed trends in Hg emissions drivers for period 1980 – 2000.

At May 10 meeting in WPB, scope expanded from analysis of emission drivers to a broader scale Hg budgeting.


Material Flows Hg Trend Reconstruction - Update

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.


Approach: Scaling of Development of Hg

Budgets

National

Florida

South Florida


National Hg Trends in Hg Flow Much of analysis derived from

Sznopek and Goonan, 2000 which defines recent trend of the national mercury flow, including the primary production, consumption, recycling as well as mercury flow from stocks.


Production – Consumption Cycle Showing Secondary Consumption

Mining Production Consumption

Recycling

Stock

Mine Production Secondary Production

Net Import

Stock Release

Mining Production Consumption

Recycling

Stock

Mine Production Secondary Production

Net Import

Stock Release


National Hg Flow Trends Apparent Hg supply includes 1 and 2 production,

net imports, and government stockpile releases. 1970 – 1986: Main contributors to Hg flow were 1

mine production and imports. 1986 – 1992: Rapid decrease of apparent Hg

demand caused by reductions in mercury demand for batteries, paint and fungicide industries.

1993 to present: 1 mine production negligible; 2 production (recycling) increased and stock releases were terminated.


National Hg Flow Trends


National Hg Releases to Atmosphere, 1996

From Sznopek and Goonan, 2000; USEPA, 1997.


National Hg Releases to Atmosphere, 1996

Materials flow schematics for 1996. 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, From Sznopek and Goonan, 2000.


Hg in US Goods and Fuel, 1940 – 1995.


Hg in US Goods and Fuel, 1940 – 1995.

1940-1970, consumption of Hg in consumer goods was not well characterized. In 1940 74% of Hg consumption was categorized as "Other".

1970-1990, electrical and electronic instruments category (including batteries) dominant Hg industrial use.

Hg demand for consumer goods drastically reduced beginning ca. 1989. Hg consumption in consumer and industrial goods declined from 1500 Mg/yr in 1989 to 500 Mg/yr in 1995 (U.S. Bureau of Mines, 1940-1995).

Hg mobilization in coal has increased since 1940, from ca. <6% of the total to ca. 20% in 1995.

Mercury mobilization by petroleum products (using 5 to 50 ppb Hg concentration for crude oil) increased since 1940. Wilhelm (in press) indicates range is more likely 5 – 15 ppb.


Trend of Hg Consumption in Coal in Florida


Trend of Hg Consumption in Petroleum in Florida


Trend of Hg Consumption in Electrical Sector

On a national scale, electrical uses of Hg increased steadily between 1947 (< 200 Mg/yr and 1986 (1,000 Mg/yr).

1996 use of Hg was 78 Mg Hg use in electrical sector increased

from 14% in early 1960’s to its peak in 1985 of 63% of the total United States consumption.


Trend of Hg Consumption in Electrical Sector – Approach (Lighting)

< 1978: U.S. Bureau of Mines (BOM) reported a single mercury consumption number for electrical uses.

1978 – Present: BOM gives inside electrical consumption, battery, switches/wiring, and lighting categories with their cumulative value representing the electrical consumption.

Reconstruct Hg in lighting using U.S. Bureau of Census fluorescent and HID lamps domestic shipments. Multiply by Hg 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).


Trend of Hg Consumption in Electrical Sector – Approach (Batteries)

Approach I (Bureau of Mines Hg consumption data)

Electrical switches with Hg not manufactured < 1960 (USEPA, 1997)

Switching/wiring use > 1960 relatively stable ( 100 Mg/yr)

Prior to 1978: Calculate Battery Hg use:Hgbattery = HgTotal Electrical – Hgswitches, lighting

Prior to 1960:Hgbattery = HgTotal Electrical – Hglighting


Trend of Hg Consumption in Electrical Sector – Approach (Batteries)

Approach II (retail battery sales) Based on work published by USEPA (1992) Use battery retail sales data from National

Electrical Manufacturers Association (NEMA) for 1983-1988, and estimates for 1989, and 1992

Based on, trend was established and used to estimate sales 1967-1982 and 1993-2000, respectively. The amount of mercury battery import was assumed at 15 %.


Comparison of Hg Use in Batteries – National Scale

BOM data

NEMA data

Note: BOM data do not reflect the exports and imports of batteries.


Trend of Hg Consumption in Electrical Sector - National


Trend of Hg Consumption in Electrical Sector - Florida

BatteriesLighting

Switches/Wiring

Note: Scaled from National level data by annual population.


Trend of Hg Consumption in Agricultural/Fungicide Use –

Approach

Hg consumption in agriculture compiled and reported by Jasinski (1994) and Murphy and Aucott (1999) based on BOM Yearbook data.

Hg consumption in fungicide compiled by Sharvelle (1961) and Murphy and Aucott (1999).

USDA annual Agricultural Statistics provides drivers for small seed (wheat, barley, oats, rye) consumption in USA.

Hg use in fungicides applied to golf courses was estimated by number of golf courses in USA (Scharff, 1970, Ross, 1979, NGF web site). Assume 80 acres/golf course treated with 43 g Hg/acre.



Approach

Golf courses routinely treated with fungicides late 1950s and 1960s.

Before late 1950s, literature all suggests only affected areas were treated with much higher concentrations of fungicides. In 1970s mercury fungicides were gradually substituted with non-mercury fungicides.

Hg use for foliage treatment started in 1942. Apples and pears were mainly treated with organomercury compounds. Annual acreage of apples was obtained from USDA Agricultural Statistics and 4.5 g/acre (Murphy and Aucott, 1999) was applied since middle 1940s.



Approach Hg use for potato and vegetable seeds (tomatoes,

watermelon, beets), soil treatment for cabbage and cauliflower, and 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.

Production of wheat, barley, oats, rye and apples is not significant in Florida. Thus, only the Vegetable and Other portion of USA Hg 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).


Trend of Hg Consumption in Agricultural/Fungicide Use – Data

Sources

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, foilage treatment

Sharvelle, 1961

Bulbs and corms Bulbs and corms soaking

Sharvelle, 1961


Trend of Hg Consumption in Agricultural/Fungicide Use - National


Trend of Hg Consumption in Agricultural/Fungicide Use - Florida


Trend of Hg Consumption in Paints – Approach

Late 1950s organomercury compounds (principally phenylmercuric acetate) were added to the water type paints to prolong the paint's shelf life.

Use the paint shipment driver and apply the estimated Hg concentration factor to paints.

Information on US paint shipments obtained from U.S. Bureau of Census annual Current Industrial Reports. The historical total paint shipments were obtained from U.S. Bureau of Census, 1975.


Trend of Hg Consumption in Paints – National Trend in Driver


Trend of Hg Consumption in Paints – National


Trend of Hg Consumption in Paints – Florida

Note:Paint Hg estimate for Florida based on U.S. BOM Hg use and Florida population data. Data are subject to change as better information is obtained.


Synthesis of Florida Trend in Hg Use

Use US data and apportion Hg consumption to Florida.

Cl2 and caustic soda manufacturing use of Hg omitted from Florida trends, since manufacturing is external to Florida and the products do not contain Hg.

“Other” category also omitted in Florida trend reconstruction. Category described in 1960 Bureau of Mines Yearbook as containing “the quantity of Hg to initiate new capacity of chlorine-caustic soda plants”.

Hg in coal for Florida included upper and lower estimates. Used average of the two estimates for trend reconstruction.


Synthesis of Florida Trend in Hg Use

Hg in petroleum for Florida was reconstructed using Florida consumption data for petroleum products and mercury content of the particular product (Wilhelm, 2001).

The mercury in paints, pharmaceutical, electrical, control, and dental uses were prorated to Florida population.

The agricultural mercury was deconstructed, and only Florida specific uses were estimated.


Trend of Hg Consumption in Florida


Synthesis of Florida Trend in Hg Emissions

Use coal and petroleum consumption as described previously

Paint: Assume 75% is emitted to the atmosphere (Benazon Environmental, 1998).

Laboratory, Electrical, Dental, and Control products: Assume disposal as municipal solid waste. In 1980 there were 500 open dumps in Florida. Open burning of waste was a common method to save landfill space (Solid Waste Management in Florida, FL DEP, 1996 p63). In 1982 one WTE was operating in Florida. In 1995 there were 13 WTE.

For 1990-1998 percentage of municipal waste burned in WTE is available (Solid Waste Management in Florida, FL DEP). However, prior to 1980 percentage of municipal solid waste burned is not available. A 16% burning rate was assumed.


Trend in Hg Emissions in Florida 1930 – 1999


Trend in Hg Emissions in Florida 1990 – 1999


Comparison of material flow-based estimates of Hg emissions with FDEP

direct emissions estimates

Note:FL DEP estimates of Hg emissions from municipal waste combustion facilities courtesy of Yi Zhu, FDEP.


Major Florida Hg in Biota Data Sets

Lange et al. (FGFWFC) largemouth bass data (n sites = 12, total n = 2001)

Frederick et al. Great Egret nestling feather data (n sites = 7 sites; total n = 558; period 1994 - 2001)

Zillioux et al. raccoon data


Summary of Fish Data Used in Trend Analysis

Data File: Task Through 2000.xls (Lange June 2001 Subsetted.xls)

Data Locations:

Big Lostmans Creek, East Lake Tohopekaliga, Fowlers Bluff, Indian Camp Creek-Rogers, L-35B Canal, Lake Tohopekaliga, Marsh-15, Marsh-GH, Marsh-OM, Marsh-U3, Miami Canal and L-67A, North Prong

Number of Data Points:

1464 measurements of Hg in Largemouth Bass

Number of Age Groups:

0, 1, 2, 3, 4, 5, 6, 7, 8, 9

Period Of Time:

10/31/1988 – 03/14/2001


Statistical Analysis Methods Simple Linear Regression versus

Time

Mann-Kendall Slope Test-of-Sign

Median Slope (computed Sen Slope estimate)


Mann-Kendall Slope Test-of-Sign

j k

j k

j k

j k

j k

C CSlope

T T

1 if C C 0

Sign 0 if C C 0

1 if C C 0

For all j and k such that j > k

where Cj is the mercury concentration at time Tj. If a total of n samples are collected over time, then there are n(n-1)/2 slope calculations.

Sen’s slope estimator is equal the median slope from that of the n(n-1)/2 slope calculations.

Mann-Kendall routine is a non-parametric test for zero slope


Why Use the Mann-Kendall Routine? Standard t-test of simple linear

regression is misleading when Seasonal cycles are present

Data are not normally distributed

Data are serially correlated

The above conditions over predict the significance of the slope when the true slope is actually zero


Hg Concentration Data Availability for Largemouth Bass

Location/Age 0 1 2 3 4 5 6 7 8 9 Total

Big Lostmans Creek 8 42 25 20 9 0 0 0 0 0 104

East Lake Tohopekaliga 0 15 59 55 29 26 14 7 2 0 207

Fowlers Bluff 0 7 45 46 33 24 17 5 7 1 185

Indian Camp Creek-Rogers 1 5 4 2 4 5 0 1 0 0 22

L-35B Canal 1 36 41 41 19 17 11 1 1 0 168

Lake Tohopekaliga 0 4 57 39 45 24 12 2 2 3 188

Marsh-15 12 35 11 6 3 0 1 0 0 0 68

Marsh-GH 15 29 21 7 2 1 2 0 0 0 77

Marsh-OM 0 22 8 2 0 0 0 0 0 0 32

Marsh-U3 8 30 12 9 5 0 1 0 1 0 66

Miami Canal and L-67A 1 55 75 43 31 14 4 4 1 0 228

North Prong 3 29 31 26 19 11 0 0 0 0 119

Total 49 309 389 296 199 122 62 20 14 4 1464


Trend-Adjusted Results of Mann-Kendall Test-of-Sign

Location/Age 0 1 2 3 4 5 6 7 8 9

Big Lostmans Creek 0 0 0 0 0

East Lake Tohopekaliga – – – – – – 0

Fowlers Bluff 0 0 – 0 0 – 0 0

Indian Camp Creek-Rogers 0 0 0 0

L-35B Canal 0 – – – – 0

Lake Tohopekaliga 0 – 0 – 0 0 0

Marsh-15 – – 0 0 0

Marsh-GH 0 – 0 –

Marsh-OM – –

Marsh-U3 + + + 0 0

Miami Canal and L-67A – – – – – 0 –

North Prong 0 – 0 – – 0

Blank = Insufficient data (54)

– Accept the alternative hypothesis of a downward trend (29)

+ Accept the alternative hypothesis of an upward trend (3)

0 Accept the null hypothesis of no trend (34)


Typical Examples of Sen’s Non-parametric Estimator of Slope (µg

Hg/g/yr)

– Accept the alternative hypothesis of a downward trend

+ Accept the alternative hypothesis of an upward trend

Location/Age 0 1 2 3 4 5 6 7 8 9

East Lake Tohopekaliga -0.036 -0.042 -0.05 -0.046 -0.063 -0.072 -0.04

Marsh-U3 +0.347 +0.145 +0.106

East Lake Tohopekaliga Data

Marsh-U3 Data


Cocoa Beach

Terra Ceia Bay

Teneroc

Clewiston

Orange Lake

Lake Griffin

Lake Mary Jane

Lake Kissimmee

Alley North

L-67TTW

Hidden

St. Martins

Seahorse Key

JW1

Location of Frederick et al. (2001) Great Egret and White Ibis Sampling

Sites

Long-term Great Egret monitoring stations, 1994 - 2000


Hg Concentrations in Great Egret Nestling Feathers. Data courtesy of P Frederick (2001). N sites per

year ≤ 7.

Relative Hg Concentration

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1992 1994 1996 1998 2000 2002

Ave

rage

Rel

ativ

e H

g C

once

ntra

tion

Year


Zillioux et al. South Florida Raccoon Hair MMHg Study -

Hypotheses

Zillioux et al. South Florida Raccoon Hair MMHg Study -

Hypotheses MMHg levels in raccoon hair have

changed between museum and modern collections.

Raccoon hair MMHg levels are the same when collected from different sites having the same deposition.


Location Museum (n) ug/g Modern (n) ug/g

North Key Largo 1.0 (15) 1.5 (17)

Flamingo 3.8 (20) 7.2 (21)

Long Pine Key 19.6 (9) 9.4 (11)

Shark Valley Sl. 8.0 (8) 14.9 (19)

South Florida Raccoon Hair MMHg South Florida Raccoon Hair MMHg


South Florida Raccoon Hair MMHg Conclusions

Cannot conclude that there has been a temporal change in MMHg raccoon hair levels.

Strong differences between sites with relatively similar deposition.

Location is more important than time: Methylation Feeding behavior

Other factors do not seem important: size, life-stage, sex, other elements, analytical artifacts


Study Tentative Conclusions Estimates of statewide emissions of Hg (based on

materials flow) indicates a large, rapid decline in Hg releases to atmosphere, driven predominantly by reductions in electrical use and cessation of paint product use.

Kendall tau test demonstrates significant declining trends LMB Hg concentrations for a number of sites across the state, but patterns are not ubiquitously observed. Canals appear to be the most consistent showing declining trends, while trends for marsh sites are not uniform.

Only one site, U3, in the entire data set shows increasing trends, and only for year classes 0 to 2


Study Tentative Conclusions The widespread distribution of declining trends suggests

a regional factor, such as atmospheric deposition, or perhaps long-term climatic variables (e.g., changes in hydrology and concomitant effects on geochemistry.

Likewise, the within region variability in trends evidenced both in the LMB and raccoon data indicate local biogeochemistry and hydrology appears to play a strong role, perhaps more than deposition.

Declines may have stabilized, and limited data from one bird colony suggests perhaps an “uptick” in the trends.


Project Timeline

July Aug Sept NovOct Dec Jan Feb Mar Apr

Jan 1, 2002Submit 1st Draft

To FCG

Feb 23, 2002Comments

Back From FCG

Mar 15, 2002Submit Final

To FCG

Aug 1 to Oct 31, 2001. Main Hg emission trend analysis.

Submit trends to Tt.

Nov 1 to Dec 31, 2001. Refine

analysis. Draft Report

Jul 1-31, 2001. Preliminary

analysis of LMB data

Oct 1 to Nov 15, 2001. Seasonal Kendall

analysis of fish trends.

Analyze bird data. Integrate

raccoon results.

Dec. 1 to Jan 1, 2002. Integrate biota and emission

trend results. Prepare

draft white paper


Revised Project Timeline

July Aug Sept NovOct Dec Jan Feb Mar Apr

Materials Flow Analysis of Hg Trends. National and Florida scale

Preliminary analysis of LMB

data

Seasonal Kendall

analysis of fish trends.

Meet with FDEP and submit data request

Work with FDEP to try and expedite data

transfer

Obtain and analyze raw bird data. Integrate raccoon results.

? ?

Complete Regional (south

Florida) analysis.

Update and revise report


QuickTime™ and aGIF decompressor

are needed to see this picture.

NADP/MDNSite

Assessment of Changes in Large-Scale Hg Signal - Phase II Analysis


MD

NP

reci

pita

tion

Dep

th (

mm

)

0

20

40

60

80

100

120

140

0 20 40 60 80 100 120 140

Glass and SorensenPrecipitation Depth (mm)

Precipitation Depth

Comparison of Glass & Sorensen (1999) results for Ely, MN with MDN results from same site. Period of overlap is for 1/16/96 through 10/8/96 (n = 25)


Comparison of Glass & Sorensen (1999) results for Ely, MN with MDN results from same site. Period of overlap is for 1/16/96 through 10/8/96 (n = 25)

MD

N H

g (n

g/L

)

0

20

40

60

80

100

120

0 20 40 60 80 100 120

Glass Hg (ng/L)

Hg in Wet Deposition


0

2,000

4,000

6,000

8,000

10,000

1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000

Hg

Dep

osit

ion

(ng/

m2-

yr)

Year

Glass & Sorensen MDN

Annual Hg Deposition Rates, Ely, MN1990 - 2000


0.0

2.0

4.0

6.0

8.0

10.0

0

20

40

60

80

100

1990 1992 1994 1996 1998 2000

SO

4 D

epos

itio

n (k

g/ha

)P

recipitation Depth (cm

)

Year

Precipitation

SO4 Deposition


Parameter F Ratio Prob > F

Time 2.703 0.1010

Month (sin

transformed)

48.103 <0.0001

Precipitation (ln

transformed)

134.347 <0.0001

Results for ANOVA Model


Plot of ANOVA Deposition Model Residuals vs. Time for Ely, MN. Data from Glass and Sorensen

(1999) and MDN.

m = +0.025p = 0.101

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

4.00

1990 1992 1994 1996 1998 2000 2002

Res

idua

l Ln

Hg

Dep

Time


-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

1990 1992 1994 1996 1998 2000

Res

idua

l Ln

SO

4 D

ep

Time

NADP Trend Analysis - Model Residuals vs. Time

m = -0.018p = 0.065

Assessment of Trends in Hg- Related Data Sets & Critical Assessment of Cause & Effect for Trends in...

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