A Waterbody Specific Approach for

Developing Mercury TMDLs

Tim Wool
Senior Water Quality Modeler
Standards, Monitoring and TMDL Branch
US EPA Region 4
 Who’s Idea was it to do Hg TMDLs

• Lawsuit filed by Sierra Club et. al. in 1994/ settled in 1997

• 1997 Consent Decree requires a schedule for TMDL
development in Georgia:
– 1999/2004 - Savannah/Ogeechee Basins (Completed)
– 2000 – Ochlockonee, St. Marys, Satilla, Suwannee Basins
(Completed)
– 2001 - Oconee/Ocmulgee/Altamaha Basins (Completed)
– 2002 - Chattahoochee/Flint Basins (Propose 8/02)
– 2003 - Coosa/Tallapoosa/Tennessee Basins (Propose 8/02)
 The TMDL Planning Process

• Complete the Last TMDL Assigned to You

• Management HgInforms
TMDL you that Hg TMDL Needs
to be proposed in 45 days
– 15 Days is taken up from getting over the laughter
– 30 Days Spent reaching into the magical hat
– 44 Days Hope you pull something out of the Hat that
looks like a……..
 Mercury TMDLs in Georgia

• Savannah River (7 segments)

• Clarks Hill Lake to Tide Gate
• 7 segments – Fish Consumption Guidelines
• 1 segment – mercury in water
– Savannah River Mercury TMDL
• Proposed 2/8/00
• Granted Extension
• Finalize in 2/28/01
 Mercury TMDLs in GA (cont.)
• South Georgia Four Basins: 22 TMDLs are
Finalized
– Ochlockonee Basin: 4 segments
– St. Marys Basin: 3 segments
– Satilla Basin: 7 segments
– Suwannee Basin: 8 segments
 TMDL Development

• Must do the TMDLs now

• Waters Listed for Fish Tissue Contamination
• Fish Tissue is the Appropriate TMDL End-Point
• Latest Human Health Methodology (BAF)
-Calculate Ambient
• Protective Ambient Concentration Below State
Aquatic Life Standard
 Mercury Characteristics

• Persistent Chemical
– Does Not Degrade
– Naturally Occurring Element
• Weathering
– Readily Changes Form
• Mediated by both Chemical & Biological Processes
• It is not fully understood what controls the changes in form
Mercury Cycling
The Technical Approach
End Point Determination (Original Approach)

• Start with Fish Tissue Concentration (0.23 mg/kg)

Threshold at which Georgia Issue Fish Consumption
Guidelines
• Gather Site Specific Data (fraction MeHg, BAF)
• Back Calculate Water Concentration to Achieve Less than
0.23 mg/kg Total Hg in Fish
• Determine Total Maximum Load of Total Hg to Achieve
Target
• Determine Current Loadings
– Point Sources
– Nonpoint Sources
End Point Determination (Current Approach)

• Using Methylmercury Criterion Trophic Weighed Fish Tissue

Concentration of 0.3 mg/kg. New methodology adopted by
State of Georgia to determine impairment
• Gather Site Specific Data (Total Hg, fraction MeHg, Trophic
Level BAF Values)
• Back Calculate Water Concentration to Achieve Less than 0.3
mg/kg Total Hg in Fish Tissue
• Determine Total Maximum Load of Total Hg to Achieve
Target
• Determine Current Loadings
– Point Sources
– Nonpoint Sources
 Atmospheric Deposition Fish Tissue Concentration
Wet & Dry
1.4
1.2
1

mg/kg (ppm)
0.8
Watershed Loads
0.6

NPDES Sources 0.4

0.2
0
06/15/94 10/28/95 03/11/97 07/24/98 12/06/99 04/19/01 09/01/02
Time

Need to Develop Relationship Between:

Water Concentration & Loads
Forage Fish/Plankton
Hg, HgII, MeHg Fish Tissue & Water Concentration

Interaction with Solids

Settling/Resuspension
 EPA Region 4 Mercury Sampling

• Initiated Sampling Program for Mercury using

ultra low-level analytical procedure (EPA 1631)
– Detection limit approximately 0.5 ng/l
– Previous detection limit much higher
• Sampling 303(d) listed segments in Georgia
– Fish Tissue
– Water Column (Total Hg, MeHg, Filtered/Unfiltered)
– Sediments (Total Hg, MeHg, Filtered/Unfiltered)
– Soils (Total Hg, MeHg, Filtered/Unfiltered)
 EPA Region 4 Mercury Sampling

• Data collected will be used for:

– Determination of appropriate End Point for the TMDL
• Site specific Bioaccumulation Factors
• Fraction of Total Hg that is MeHg
– Aid in the calibration of the watershed model
• Soil Concentration
– Aid in the calibration of the water quality model
• Fraction of Chemical that is MeHg
• Organic Carbon Content
• Site specific partition coefficients
 Water Column Mercury Concentrations Savannah River & Tributaries

Total Hg Fraction
Station (ng/l) MeHg (ng/l) MeHg
Savannah River-Below Clark's Hill Dam 0.27 0.02 0.078
Savannah River-Below Horse Creek 0.68 0.10 0.141
Savannah River-Below Butler Creek 1.19 0.16 0.131
Savannah River-Below Upper Three Runs Creek 3.27 0.07 0.020
Savannah River-Below Lower Three Runs Creek 9.50 0.06 0.006
Savannah River-Below Lower Three Runs Creek(Filtered) 1.47 0.07 0.044
Savannah River-Below Brier Creek 2.80 0.09 0.032
Savannah River-Clyo, USGS Gage 3.28 0.09 0.027
Savannah River-Below Ebenezer Creek 3.44 0.08 0.022
Savannah River-Tide Gate (Freshwater) 4.44 0.09 0.021
Savannah River-Tide Gate (Freshwater) (Filtered) 1.00 0.03 0.032
Savannah River-Tide Gate (Estuary) 4.09 0.06 0.015
Horse Creek 6.16 0.24 0.039
Butler Creek 2.14 0.39 0.182
Upper Three Runs Creek 5.82 0.16 0.027
Lower Three Runs Creek 2.43 0.13 0.051
Brier Creek 2.15 0.11 0.050
Ebenezer Creek 3.34 0.65 0.195
Average 3.19 0.14 0.062
 Step 1 - TMDL Target Determination

• Georgia
– No Human Health Criteria/Interpret Narrative
– “End Point”=Fish Tissue less than 0.3 mg/kg
– Gather Site Specific Data
– Use EPA’s Human Health Methodology
– Back Calculate Water Concentration to achieve 0.3
mg/kg in fish
• South Carolina
– Human Health Criteria = 12 ng/l
 Risk Based Calculation

(Re ference Dose * BodyWeight *Units Conversion)

WQT 
(Consumption Rate * Trophic Level Weighted BAF * Fraction MeHg)

where:
WQT= Water Quality Target
Reference Dose = 0.0001 mg/k MeHg
Body Weight (Average Person) = 70 kg
Units Conversion = 1.0E6
Consumption Rate = 0.0175 kg/day Fish (17.5 g/day)
Bioaccumulation Factor = ((Trophic 3 BAF * 8 g/day) + (Trophic 4 BAF * 5.7 g/day))/13.7 g/day
Fraction of the Total Mercury as Methyl Mercury = 0.21 as measured in the Alapaha Watershed
 Water Water
Water Column Fraction Quality
Average BAF
Average Fish Column Total MeHg MeHg Target
River/Tributary Segment Tissue (ppm) Hg (ng/L) (ng/L) (ng/L)
Savannah River-Below Clark's Hill Dam 0.251 0.27 0.02 0.078 11,710,280 0.44
Savannah River-Below Horse Creek 0.074 0.68 0.10 0.141 768,229 3.68
Savannah River-Below Butler Creek 0.316 1.19 0.16 0.131 2,026,871 1.51
Savannah River-Below Upper Three Runs Creek 0.181 3.27 0.07 0.020 2,744,723 7.21
Savannah River-Below Lower Three Runs Creek 0.180 9.50 0.06 0.006 3,142,770 21.10
Savannah River-Below Brier Creek 0.415 2.80 0.09 0.032 4,703,913 2.70
Savannah River-Clyo, USGS Gage 0.633 3.28 0.09 0.027 7,271,958 2.07
Savannah River-Below Ebenezer Creek 0.665 3.44 0.08 0.022 8,698,953 2.07
Savannah River-Tide Gate (Freshwater) 0.407 4.44 0.09 0.021 4,319,872 4.37
Savannah River-Tide Gate (Estuary) 0.389 4.09 0.06 0.015 6,321,951 4.21
Horse Creek 0.264 6.16 0.24 0.039 1,096,266 9.33
Butler Creek 0.305 2.14 0.39 0.182 780,769 2.81
Upper Three Runs Creek 0.783 5.82 0.16 0.027 4,896,829 2.97
Lower Three Runs Creek 1.085 2.43 0.13 0.051 8,676,761 0.90
Brier Creek 0.493 2.15 0.11 0.050 4,562,963 1.75
Ebenezer Creek 1.269 3.34 0.65 0.195 1,948,651 1.05

Average 0.482 3.44 0.15 0.065 4,604,485 4.26

Median 0.398 3.28 0.10 0.035 4,441,418 2.75
Average (Mean) River 0.351 3.30 0.08 0.049 5,170,952 4.94
Median River 0.352 3.28 0.08 0.024 4,511,893 3.19
Average (Mean) Trib 0.700 3.67 0.28 0.091 3,660,373 3.13
Median Trib 0.638 2.89 0.20 0.051 3,255,807 2.28

Reference Dose 0.0001

Body Weight 70
Consumption Rate 0.0175
 Calculate the Total Allowable Load
• Mercury Air Deposition Runoff Model (Developed by
EPA/ORD)
– Added a soil runoff component (EPA/R4)
– Routes mercury deposition from impervious and water surfaces to
tributaries
– Transports mercury bound to soil from watershed to tributaries
– Delivers mercury through tributary system with
reduction/volatilization Loss
• WASP Model transports mercury in the Waterbody
• Determine annual average load of mercury
– Current loading
– Reductions needed to meet WQS
 Atmospheric Deposition Rates

• RELMAP Coverage
– Atmospheric Model to predict the distribution and
deposition rate of mercury (wet and dry)
– Used in the Mercury Report to Congress
• Based upon older emissions inventory
• Emissions inventory currently being updated
• Mercury Deposition Network (MDN)
– Wet Deposition
– Site Specific
 Preliminary Characterization of Air
Sources and Deposition
• Atmospheric deposition of mercury to this basin is the
main loading
– Deposition by: Wet (rain) and Dry (particles & gases)
– Deposition of mercury is significant across eastern USA
• We used national RELMAP model, 1997 Mercury
Study Report to Congress
– Inventory of emissions: point sources in all States
– Annual emissions data for 1994 -1996 period
– RELMAP models weather, transport, chemistry, & deposition
 Preliminary Characterization of Air
Sources and Deposition
• RELMAP data & results in Report to
Congress got comprehensive review
• For the Savannah River TMDL, we did
– Detailed study of RELMAP deposition (per square
meter) to this basin
– Emissions data on sources in basin + 100 km (60
mi) around the basin
 Preliminary Characterization of Air
Sources and Deposition
• We define “Airshed” as: this basin and 100
km band around the basin
– Includes all/part of 51 Counties in GA and 29
counties in SC
– Emissions data (RELMAP) for 80 point sources in
these Counties
 Preliminary Characterization of Air
Sources and Deposition
• Source categories within the Airshed
– Hospital, medical and infectious waste incinerators [36]
– Electric utility boilers (coal, oil, and gas) [17]
– Chlor-alkali plant (mercury cell) [1]
– Municipal solid waste combustors [3]
– Residential (heat) and Industrial boilers [80 Counties]
– Pulp and paper plant recovery furnaces [12]
– Portland cement manufacturing [3 including 2 that burn
some hazardous waste]
– Municipal sewage sludge incinerators [6]
– Hazardous waste incinerators [2]
 Preliminary Characterization of Air
Sources and Deposition
• Year 2010 : predicted changed emissions
from sources in airshed
– Growth estimate based on state or regional
population growth
– Maximum Achievable Control Technology (MACT)
for 4 categories
• results in reduced emissions
• Closed facilities as of 1999 -2000 given zero emissions
in 2010
 Total Hg Total RGM
Emmissions Emmissions
Number of Base Case % of Base Case % of
Source Sources (kg/yr) Total (kg/yr) Total
MedWIs 36 962.74 25.65% 702.8 39.93%
Power Plants 17 866.2 23.08% 259.86 14.76%
Chlor-alkali 1 597.38 15.92% 179.21 10.18%
MuniWCs 3 589.04 15.69% 353.42 20.08%
Res/Ind Boilers 80* 476.62 12.70% 142.99 8.12%
Pulp and Paper 12 121.07 3.23% 36.32 2.06%
Portland Cement 3 112.94 3.01% 69.55 3.95%
Sew Sludge Incin. 6 25.92 0.69% 15.55 0.88%
HazWIs 2 1.12 0.03% 0.28 0.02%
Total 160 3753.03 100.00% 1759.98 100.00%

This value indicates the number of counties in the study area with residential or industrial boilers.
The emissions inventory for the residential/industrial boiler source category provides total mercury
emissions by county. Of the 80 total counties, 51 Counties are in Georgia and 29 are in South Carolina.
 Preliminary Conclusion :

• Deposition of mercury to the basin between

the base year (~1995) and 2010 will be
greatly reduced based on:
– Maximum Achievable Control Technology (MACT)
– Additional reductions expected from air programs
still being developed
– Voluntary controls and Pollution Prevention.
 Overview of Watershed Model

• Extension to Watershed Characterization System

– ArcView Based
• DEM
• Meteorological Stations
• RF1/RF3/NHD
• Landuse
• Hg Deposition/RELMAP Model Predictions
• Soil Data
– Consistent with the approach used in the Mercury
Report to Congress
 Sub Basin Load
Total Mercury Load 225 grams/year

13% 0%
Atmospheric Deposition 28% Imprevious Surface
Sediment
Precipitation 18%
Runoff
Deposition on Water
Point Sources

41%
Reduction/Volatilization

Attenuation

Run
off
Ero
sion

Buildup in Soil Receiving Waterbody Model

Leaching
 Tributary Delivery from Watershed to
Main Waterbody
• Tributary delivery equation accounts for the
attenuation of mercury loadings during the
transport to main waterbody
– This module considers:
• watershed loading along the tributary length
• change in flow
• hydraulic geometry and residence time, TMAX
• reduction and volatilization, KRED
– Delivery Ratio = [1-exp(-Kred Tmax)]/KRED TMAX
– Applied for each subwatershed
 Waterbody Fate and Transport

• Water Quality Model will be used to Determine

Maximum Assimilative Capacity of the Savannah
River
– This Considers:
• Change in Flow
• Chemical Cycling (Oxidation/Reduction,
Methylation/Demethylation)
• Interaction with Sediments
• Volatilization
 Overview of Water Quality Model

• US EPA’s Water Quality Assessment Simulation

Program (WASP5)
– Used in EPA’s Mercury investigation in the Everglades
 Overview of Water Quality Model

NPDES Watershed Load Volatilization

Demethylation State Variables

Oxidation
Hg(0) Silt
Hg(II) Sand DOC
Methylation MeHg
Reduction

Burial
 Watershed River
Terrestrial Tributary Mainstem
Atmospheric Deposition,
Atmospheric Depostion,
Mercury Sources Atmospheric Deposition Tributary Loads, Point
Runoff, Erosion
Source Loads
Reduction / Volatlization, Reduction / Volatilization,
Reduction / Volatilization,
Mercury Sinks Runoff, Erosion, Settling and Burial,
Advective Export
Leaching Advective Export
Hg Deposition, HgT HgT, MeHg (water),
Calibration Data HgT, MeHg (water)
(soil) HgT, MeHg (sediment)
Reduction Rate, Methylation
Reduction Rate, Loading Reduction Rate, Fraction
Calibration Parameters and Demethylation Rates,
Period MeHg
Partition Coefficients
 Fate & Transport
Average Annual Flow Water Column Total Mercury Concentrations

10

8
7

6
Total Hg
ng/l

5
Observed
4

3
2

0
250 200 150 100 50 0
River Mile
 Waynesboro WWTP
Vogtle Southern Nuclear
Tybee WWTP
Torrington Screven
County
Sylvania Yarns
Sylvania WWTP
Savannah WWTP
Richmond County Spirit
Creek WWTP
Richmond County
Landfill
Pooler/Bloomingdale
Sampled NPDES Facilities

Olin Corporation
Kwikset
Kerr-McGee Kemira
(Outfall-4)
Kerr-McGee Kemira
(Outfall-1)
International Paper Co.
Homer Housing
Authority
E.M. Industries
Dogwood Lane MHP
DHR Gracewood
Hospital
Commerce Davis House
Columbia County Health
Dept.
Citgo Asphault
Budget Inn
Augusta Butler Creek

8.00

6.00

4.00

2.00

0.00
20.00

18.00

16.00

14.00

12.00

10.00
 Reduction Analysis

TMDL Air Reductions

Watershed/Waterbody %Reduction Ranges
Alapaha (Near State Line) 64% 17% 25%
Ochlocknee (Hadley Road) 76% 31% 41%
Satilla (Savannah River 252 Bridge) 61% 31% 39%
St. Mary's 56% 1% 6%
Suwannee (Fargo, GA) 58% 9% 15%
Withlacoochee (Near State Line) 40% 33% 43%
Ohoopee 24% 42% 54%
 WASP6 Workshops

Date Location
June 24-28 US EPA Region 4
August 5-9 US EPA Region 10
September 19-23 US EPA Region 3