EPA-
Water Quality Assessment of Proposed
Effluent Guidelines for the Pulp,
Paper, and Paperboard Industry
Standards and Applied Science Division
Office of Science and Technology
United States Environmental Protection Agency
Washington, DC 20460
November 1993
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EPA -
Water Quality Assessment of Proposed
Effluent Guidelines for the Pulp,
Paper, and Paperboard Industry
Standards and Applied Science Division
Office of Science and Technology
United States Environmental Protection Agency
Washington, DC 20460
November 1993
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ACKNOWLEDGEMENTS AND DISCLAIMER
This report has been reviewed and approved for publication by the Standards and Applied
Science Division, Office of Science and Technology. This report was prepared with the support
of Tetra Tech, Inc. (contract 68-C3-0303) under the direction and review of the Office of Science
and Technology. Neither the United States Government nor any of its employees, contractors,
subcontractors, or their employees make any warranty, expressed or implied, or assumes any legal
liability or responsibility for any third party's use of or the results of such use of any
information, apparatus, product, or process discussed in this report, or represents that its use by
such party would not infringe on privately owned rights.
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CONTENTS
Tables :. '. v
Figures vii
Executive Summary ix
1. Introduction 1
2. Description of the Industry 3
2.1 Brief Description of the Pulp and Paper Technology : . . . . 4
2.1.1 Chemical Pulping 4
2.1.2 Pulp Bleaching 4
2.2 Process Controls and Changes Considered 8
2.2.1 Oxygen Delignification 8
2.2.2 Extended Delignification 9
2.2.3 Chlorine Dioxide Substitution ". 9
2.2.4 Ozone Delignification 9
2.2.5 Peroxide Delignification 9
2.3 Proposed BPT, BCT, and BMP Controls 10
3. Background . . ' 13
3.1 Pollutants of Concern .......: 13
3.1.1 2,3,7,8-TCDD and 2,3,7,8,-TCDF .".:.- 17
3.1.2 Other Toxic and Nonconventional Contaminants 21
3.1.2.1 AOX .'. 21
3.1.2.2 Color 22
3.1.3 Conventional Pollutants 22
3.2 Recreational Fisheries 24
3.3 Fish Advisories 26
4. Methodology 27
4.1 Estimating In-Stream Concentrations 31
4.2 Estimating Impacts to Aquatic Life 32
111
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4.3
CONTENTS (continued)
Estimating Impacts to Human Health 33
4.3.1 Comparison to AWQCs for the Protection of Human Health 33
4.3.2 Estimation of Carcinogenic Risks and Noncarcinogenic Hazards 33
4.3.2.1 Potential Carcinogenic Risks 35
4.3.2.2 Potential Noncarcinogenic Hazards 36
5. Results 41
5.1 Aquatic Life Impact Assessment 41
5.2 Human Health Impact Assessment 42
5.2.1 Comparison with AWQCs for the Protection of Human Health 42
5.2.2 Potential Carcinogenic Risk 44
5.2.2.1 DRE Model 45
5.2.2.2 Simple Dilution Model 45
5.2.3 Potential Noncarcinogenic Hazards 46
5.2.3.1 DRE Model 46
5.2.3.2 Simple Dilution Model 47
5.2.3.3 Number.of Anglers Potentially Exposed 48
5.2.4 Impacts of BAT Controls on Dioxin-Related Fish Advisories 48
6. Limitations and Uncertainties 51
.6.1 Limitations 51
6.2 Uncertainties Associated with Risk Estimates „ 51
7. References 55
Attachments A-l
IV
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TABLES
Number
1 Selected Process Change Options for Each Subcategory x
2 Estimated Number of Pollutants and Mills Exceeding Aquatic Life AWQCs xi
3 Estimated Number of Pollutants and Mills Exceeding Health-Based AWQCs xii
4 Average Individual Lifetime Cancer Risks for Recreational and Subsistence Anglers
at Baseline and at Selected BAT Estimated Using Two Water Quality Models (Simple
Dilution and DRE) xiv
5 Annual Cancer Cases for Recreational and Subsistence Anglers at Baseline and at
Selected BAT Estimated Using Two Water Quality Models (Simple Dilution and DRE) . . . xv
6 Number of Mills Exceeding RfDs for Recreational and Subsistence Anglers
at Baseline and at Selected BAT Estimated Using Two Water Quality Models
(Simple Dilution and DRE) xvi
7 Number of Receiving Streams That Would Exceed Dioxin-Related State Fish
Advisory Threshold Limits Under Various Regulatory Alternatives, at Current
and Selected BAT Conditions, Estimated Using the Simple Dilution and DRE
Approaches xviii
2-1 Receiving Streams for the 103 BAT Pulp and Paper Mills 7
2-2 Selected Process Options for Each Subcategory 8
3-1 Toxicity Values for the Contsiminants Analyzed in the Pulp and
Paper Assessment . . . 15
3-2 Systemic Human Toxicants Evaluated and Their Target Organ Endpoints 16
3-3 Human Carcinogens Evaluated, Weight-of-Evidence Classifications,
and Target Organs 16
3-4 Affected Organisms and the Physiological and Community
Impacts that Have Been Linked to the Presence of 2,3,7,8-TCDD 18
3-5 Target Organs/Tissues, Effects, and Species-Specific Toxicity
Values for TCDD 19
3-6 Various Methodologies and Their Frequency of Use by States for
Deriving Action Levels for Issuing Fish Advisories - 27
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TABLES (continued)
Number
3-7 State Action Levels for Dioxin 27
3-8 Receiving Streams of Bleaching Pulp and Paper Mills Under Dioxin Fish
Advisories, the Advisory Type, and Species Whose Consumption Is Limited 28
5-1 Estimated Number of Pollutants and Mills Exceeding Aquatic Life AWQCs 41
5-2 Estimated Number of Pollutants and Mills Exceeding Health-Based AWQCs 43
5-3 Average Individual Lifetime Cancer Risk and Annual Increased Incidence of
Cancer for Recreational and Subsistence Anglers at Baseline and Selected
BAT Estimated Using the DRE Approach 44
5-4 Average Individual Lifetime Cancer Risk and Annual Increased Incidence of
Cancer for Recreational and Subsistence Anglers at Baseline and Selected
BAT Estimated Using the Simple Dilution Approach 1 .... 45
5-5 Number of Pollutants and Mills Exceeding RfDs for Recreational and
Subsistence Angler Populations Estimated Using the Simple Dilution and
DRE Approaches 47
5-6 Populations Potentially Exposed to Noncarcinogenic Hazards Under Baseline
Conditions and After Implementation of the Selected BAT Options, Estimated
Using the Simple Dilution and DRE Approaches 48
5-7 Number of Receiving Streams That Would Exceed State Fish Advisory Threshold
Limits Under Various BAT Options Estimated Using the Simple
Dilution and DRE Approaches 49
VI
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FIGURES
Number
2-1 Location of the 103 BAT pulp and paper mills
2-2 Location of BAT mills in the northeast United States . .
2-3 Location of BAT mills in the southeast United States . .
2-4 Location of BAT mills in the northcentral United States
2-5 Location of BAT mills in the northwest United States .
5
5
6
6
7
Vll
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EXECUTIVE SUMMARY
The U.S. Environmental Protection Agency (EPA) is developing revised effluent guidelines and "maximum
achievable control technology" (MACT) standards for the pulp, paper, and paperboard industry. These
proposed regulations would limit the discharge of pollutants into navigable waters of the United States
and the introduction of pollutants into publicly owned treatment works by existing and new facilities that
produce pulp, paper, and paperboard. The proposed regulations would establish effluent limitations
guidelines based on the "best practicable control technology currently available" (BPT), "best conventional
pollutant control technology" (BCT), "best available technology economically achievable" (BAT), effluent
"new source performance standards" (NSPS) based on best available demonstrated technology,
"pretreatment standards for existing sources" (PSES), "pretreatment standards for new sources" (PSNS),
and "best management practices" (BMP). EPA is also proposing to regulate emissions of hazardous air
pollutants from pulp and paper production processes, which are major sources under section 112 of the
Clean Air Act (CAA), as amended in 1990.
This environmental assessment has been prepared in support of EPA's Regulatory Impact Assessment
(RIA) for the pulp, paper, and paperboard industry effluent guidelines in compliance with Executive Order
12866, which requires EPA to assess the costs and benefits of significant rulemaking. Through a mill-
specific analysis of 26 pollutants, this assessment evaluates both qualitatively and quantitatively the
potential aquatic life and human health benefits of controlling the discharges from four bleaching
subcategories that fall under BAT regulations (dissolving kraft, bleached papergrade kraft/soda, dissolving
sulfite, and papergrade sulfite). In addition, the environmental significance of discharges from the non-
bleaching segment of the industry is also qualitatively examined. The environmental impacts of air
emissions are discussed in a separate document prepared in support of regulations limiting the emission
of hazardous air pollutants.
Description of the Industry
There are a total of 565 pulp and paper mills in the United States. The chemical pulping and bleaching
process is conducted by 104 mills, 103 of which are the focus of this environmental assessment. Of the
104 bleaching mills, 94 discharge directly into navigable waterways and will be subject to BAT
regulations, 9 are indirect dischargers and will be subject to PSES regulations, and 1 does not discharge
wastewater into a navigable waterway and therefore-is not counted as a mill subject to BAT (memorandum
from Doug Spengel, Radian Corporation, to Drew Zacherle, Tetra Tech, Inc., June 7, 1993). The 103
bleaching mills being evaluated in this assessment have been grouped by EPA into 4 subcategories
according to the bleaching process used and the resulting end product. The subcategories and the number
of mills in each subcategory are listed below:
Subcategory
Dissolving Kraft (DK)
Bleached Papergrade Kraft/Soda (PK)
Dissolving Sulfite (DS)
Papergrade Sulfite (PS)
Number of Mills
3
86
5
9
103
IX
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The selected regulatory options for BAT mills are designed to reduce or eliminate the formation of
dioxins, furans, and other chlorinated organics that result from the chemical pulping and bleaching process.
Of the wide variety of regulatory options originally evaluated as to their ability to meet the standards of
the proposed rule (Attachment 1), EPA selected what appear to be the most appropriate BAT options for
each subcategory (Table 1).
Table 1. Selected Process Change Options for Each Subcategory
Dissolving
Kraft
Oxygen delignification with
70% substitution of chlorine
dioxide for chlorine
Bleached ^pergrade-^V
Kraft/Soda i-
Oxygen delignification OR
extended delignification with
100% substitution of chlorine
dioxide for chlorine
Dissolving
"„£ Salfife
Oxygen delignification
with 100% substitution
of chlorine dioxide for
chlorine
" "- Pajpergrade
Sulfifcr -
TCP: Totally chlorine-free
bleaching
Approach
This environmental assessment evaluates the potential impacts of bleaching pulp and paper mill effluents
on aquatic life and human health. Potential impacts on aquatic life are evaluated by comparing modeled
in-stream contaminant concentrations to aquatic life water quality criteria or toxic effect values (referred
to as ambient water quality concentrations, or AWQCs, i^' the: protection of freshwater aquatic life).
These aquatic life AWQCs include published EPA water quality criteria or toxic levels derived from the
scientific literature for pollutants for which EPA criteria are not available. Modeled in-stream
concentrations are compared to both acute AWQCs and chronic AWQCs when available.
Potential impacts on human health are evaluated by (1) comparing estimated in-stream contaminant
concentrations to health-based toxic effect values (referred to as ambient water quality concentrations, or
AWQCs, for the protection of human health); (2) estimating the potential reduction of carcinogenic risk
and noncarcinogenic hazards from the consumption of fish tissue; (3) estimating the annual incidence of
cancer in the potentially exposed angler population; and (4) estimating the number of existing dioxin-
related state fish advisories that will potentially be lifted after the implementation of the selected BAT
options. Estimates are also made of the potential increase in recreational angler participation due to the
lifting of fish advisories as a result of implementation of the selected BAT options.
Exposure pathways evaluated in the human health risk assessment (both cancer and noncancer) include
ingestion of fish by recreational and subsistence anglers and their households. Exposure to contaminants
through the water pathway is also evaluated by the comparison of modeled in-stream contaminant
concentrations to health-based AWQCs for the ingestion of water and organisms. The potential human
health cancer risk and noncancer hazards associated with the ingestion of drinking water are not evaluated
because no municipal public water intakes are within the same river reach or within 10 miles downstream
from any bleaching pulp and paper mill effluent discharge (whichever is the greater distance).
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Results
Aquatic Life Benefits
Only one contaminant (pentachlorophenol) at two bleached papergrade kraft/soda mills is pr :ected to
exceed acute aquatic life AWQCs under baseline conditions (Table 2). With the implementation of the
selected BAT options, it is projected that no exceedances of acute aquatic life AWQCs will occur.
The implementation of the selected BAT options for each of four bleaching subcategories eliminates the
exceedances of chronic aquatic life AWQCs for dioxin (with the exception of one mill in the bleached
papergrade kraft/soda subcategory) and eight other chlorinated organic compounds that are projected to
occur as a result of baseline-level discharges (Table 2). The following pollutants are predicted to exceed
chronic aquatic life AWQCs under baseline conditions:
• 4-Chlorocatechol
• Pentachlorophenol
? 2,3,7,8-TCDD
• 2,3,7,8-TCDF
• 3,4,5,6-Tetrachloroguaiacol
3,4,5-Trichloroguaiacol
4,5,6-Trichloroguaiacol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
The estimated number of mills exceeding chronic aquatic life AWQCs at baseline is reduced from 28 mills
to 1 mill after implementation of the selected BAT options.
Table 2. Estimated Number of Pollutants and Mills Exceeding Aquatic Life AWQCs
'fe?,^^ f rop^s,,f r ;
Baseline
Selected BAT Option
Total Number of
Pollutants and Mills
(in parenthesis) with
Exceedances
'V: SL*S?
DK
0
0
fe«^%a^4i^yfg' ^^
PK
1(2)
0
DS
0
0
PS
0
0
Baseline = 1(2)
Selected BAT Options = 0
!^M?^*®M^3w^x^'- =7
DK
3(1)
0
PK
9(27)
1(1)
DS
0
0
Baseline = 9(28)
Selected BAT Options = 1(1)
PS
0
• o
Human Health Benefits
1. Reduction of Health-Based AWQC Exceedances
The implementation of the selected BAT options for each of the four bleaching subcategories is projected
to reduce the number of mills that exceed health-based AWQCs for ingestion of both organisms and water
and organisms from 97 mills at baseline conditions to 78 after BAT implementation (Table 3). Health-
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Table 3. Estimated Number of Pollutants and Mills Exceeding Health-Based AWQCs
Process Change
Option
Baseline
Selected BAT Option
Total Number of
Pollutants and Mills
(in parenthesis) with
Exceed anccs
' Number ef&rtftttan&aiiilMil^ :? °°f
'''::? /"- _WQCI?*^ancesr . V !«*i:i • ^ L .•
(organisms) Human HeiilUi ,~; * ->"-_
DK
3(3)
2(2)
PK
5(80)
2(71)
DS
2(5)
2(5)
PS
2(9)
0
Baseline = 5(97)
Selected BAT Options = 2(78)
/ -, , - »<
- -*~\ --Cwate
DK
7(3)
3(2)
r and organisms) Human Health • ,
PK
8(80)
4(71)
DS
4(5)
4(5)
PS
4(9)
0
Baseline = 8(97)
Selected BAT Options = 5(78)
based AWQCs for protection from the ingestion of contaminated organisms are exceeded under baseline
conditions for the following five contaminants:
• Chloroform
• Pentachlorophenol
• 2,3,7,8-TCDD
• 2,3,7,8-TCDF
• 2,4,6-Trichlorophenol
Not all 97 mills exceed health-based AWQCs for all 5 contaminants under baseline conditions. The
selected BAT chlorine-free option for the papergrade sulfite subcategory eliminates all health-based
AWQC exceedances for ingestion of organisms. The selected BAT options for the dissolving kraft,
bleached papergrade kraft/soda, and dissolving sulfite subcategories reduce the number of contaminants
for which health-based AWQC exceedances are projected to occur to two: 2,3,7,8-TCDD and 2,3,7,8-
TCDF.
Three additional health-based AWQCs, for a total of eight, are projected to exceed health-based AWQCs
for protection from the ingestion of contaminated water and organisms under baseline conditions. These
eight exceedances are for the following contaminants:
• Chloroform
• 4-Chlorophenol
• 2,6-Dichlorophenol
• Methylene chloride
• Pentachlorophenol
• 2,3,7,8-TCDD
• 2,3,7,8-TCDF
• 2,4,6-Trichlorophenol
Not all mills are projected to exceed the health-based AWQCs for all eight contaminants under baseline
conditions. As expected, all exceedances of health-based AWQCs for the ingestion of water and
organisms for the papergrade sulfite subcategory are eliminated with the implementation of the selected
XII
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BAT option (totally chlorine-free bleaching). The selected BAT options for the dissolving kraft, bleached
papergrade kraft/soda, and dissolving sulfite subcategories are projected to reduce the number of
contaminants for which health-based AWQC exceedances occur to five:
• Chloroform (DS mills only)
• 2,6-Dichlorophenol (PK mills only)
• Pentachlorophenol
• 2,3,7,8-TCDD
• 2,3,7,8-TCDF
Not all the mills projected to exceed the health-based AWQCs exceed them for all five contaminants.
2. Reduction of Potential Cancer Risks and Noncancer Hazards
Two different methods—the simple dilution approach and the Dioxin Reassessment Evaluation (DRE)
Model approach—are used to determine fish tissue (i.e., fillet) concentrations for the following 6
carcinogens and 11 systemic toxicants for 100 mills located near 68 receiving streams:
Carcinogens
Chloroform
Methylene chloride
Pentachlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
2,4,6-Trichlorosyringol
Systemic Toxicants
Acetone
2-Butanone
Chloroform
4-Chlorophenol
2,4-Dichlorophenol
Methylene chloride
Pentachlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
2,3,4,6-Tetrachlorophenol
2,4,5-Trichlorophenol
The DRE modeling approach is used only to evaluate cancer risk and noncancer hazards associated with
2,3,7,8-TCDD and 2,3,7,8-TCDF. The simple dilution method is used to evaluate cancer risk and
noncancer hazards for all of the contaminants listed above. The two models are used to evaluate the
potential accumulation of contaminants in fish and the resulting impacts on human health from the
consumption of contaminated fish and to project the effect of the selected BAT options on existing dioxin-
related fish advisories.
The simple dilution approach is a very conservative methodology that assumes that all of the pollutant
loadings discharged to a receiving stream, including TCDD and TCDF, are available to the biota,
particularly fish. The DRE approach uses a model developed by EPA's Office of Research and
Development (currently under EPA review) (USEPA, 1993c). The model assumes that the bioavailability
of dioxins is dependent on 'the levels of suspended solids in the discharge and the receiving stream.
Because two models are used in this assessment, the results are presented as a range. The results from
the DRE model provide the lower end of the range, and the results from the simple dilution approach
provide the upper end.
xm
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Reduction of Cancer Risks
Using the DRE model (which is used in this assessment only to evaluate potential human health impacts
due to exposure to 2,3,7,8-TCDD and 2,3,7,8-TCDF), the average individual lifetime cancer risk after
implementation of selected BAT options for dissolving kraft and bleached papergrade kraft/soda facilities
is predicted to be reduced to the 10"5 level for recreational anglers and to the 10~4 level for subsistence
anglers, as compared to estimated baseline risks at the 10"3 to 10"4 level for recreational anglers and. the
10~2 to 10"3 level for subsistence anglers (Table 4). For dissolving sulfite facilities, the overall cancer risk
for recreational anglers is estimated to decrease to the 10"5 level after BAT implementation as compared
to the 10"4 level under baseline conditions. For subsistence anglers the cancer risk associoated with
dissolving sulfite mills is projected to remain at the 10~3 level, the same as under baseline conditions.
Using the simple dilution approach, the average individual lifetime cancer risk for dissolving kraft facilities
is projected to be reduced to the 10~4 level for recreational anglers and to the 10~3 level for subsistence
anglers as compared to estimated baseline risks at the 10"3 level for recreational anglers and the 10"2 level
for subsistence anglers. The average individual lifetime cancer risk for bleached papergrade kraft/soda
facilities is predicted to be reduced to the 10~5 level for recreational anglers and to the 10"4 level for
subsistence anglers as compared to estimated baseline risks at the 10"4 level for recreational anglers and
10"2 level for subsistence anglers. The individual lifetime cancer risk associated with dissolving sulfite
mills is predicted to remain at the 10"4 level for recreational anglers and the 10"3 level for subsistence
anglers under BAT (the same as under baseline conditions). Using the simple dilution approach, it is
estimated that approximately 99 percent of cancer risk is due to 2,3,7,8-TCDD and 2,3,7,8-TCDF under
both baseline and BAT conditions (Attachment A-23).
The selected BAT option for the papergrade sulfite mills is a totally chlorine-free process that completely
eliminates the formation and subsequent discharge of chlorinated organics. The individual lifetime cancer
risk from these operations for recreational anglers would be reduced to 0 from an estimated baseline risk
at the 10"s level (using both the DRE and simple dilution approaches); the risk for subsistence anglers
would be reduced to 0 from an estimated baseline risk at the 10'4 (DRE approach) to 10'3 (simple dilution
approach) level.
Table 4. Average Individual Lifetime Cancer Risk for Recreational and
Subsistence Anglers at Baseline and at Selected BAT Estimated Using
Two Water Quality Models (Simple Dilution and DRE)
Subcategory
Dissolving Kraft
Bleached Papergrade
Kraft/soda
Dissolving Sulfite
Papergrade Sulfite
DI
Baseline
10'3
10"4
10"4
io-5
t •: Vf.
Recreation
we 7> '
Selected
; Option
10'5
io-s
io-5
Eliminated
t-Frf '"-'"
^ ' < •f'?
• ' --,-
Baseline ^
io-3
io-4
10*
io-5
?"•;, ,-'; ,
Daoaoa^l
Selected'
Opfionx;
io-4
io-5
io-4
Eliminated
- '™JT •" '" •
;SH • Sjai
°??; „ *^t
•/Baseline:-,
10'2
io-3
10'3
io-4
''s'teir'
^,:?"-'->":'
g$Sr'
;,-Opiion:
io-4
ur»
io-3
Eliminated
sfe'AailW'
- Simple
,- r-1;.
Baseline
io-2
10'2
io-3
io-3
:;-r:'T^ '^%
Diluti^S:
-SelW^l-
OptionS
io-3
10"4
10'3
Eliminated
XIV
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It is estimated that for combined recreational and subsistence anglers, implementation of the selected BAT
options would eliminate between 5 (DRE approach) and 35 (simple dilution approach) cancer cases per
year resulting from the consumption of contaminated fish tissue (Table 5). Using the DRE approach, it
is estimated that the number of cancer cases per year would be reduced from less than six under baseline
conditions to less than one under the selected BAT options. Using the simple dilution approach, it is
estimated that the number of cancer cases per year would be reduced from 37.5 under baseline conditions
to 2.5 under the selected BAT options.
Reduction of Noncancer Hazards
The DRE model is used only to evaluate the noncancer hazard associated with 2,3,7,8-TCDD and 2,3,7,8-
TCDF. The estimated number of mills in the four bleaching subcategories exceeding reference doses
(RfDs) for 2,3,7,8-TCDD and 2,3,7,8-TCDF for recreational anglers using the DRE approach is reduced
from 34 mills under baseline conditions to 7 (a 79 percent reduction) after the implementation of the
selected BAT options (Table 6). The selected BAT totally chlorine-free option for papergrade sulfite mills
Table 5. Annual Cancer Cases for Recreational and Subsistence
Anglers at Baseline and at Selected BAT Estimated Using
Two Water Quality Models (Simple Dilution and DRE)
?£~~ ;''-£ ^
v*'*"1 ^ X" ** •<'
Jj^ 4$$BCirf€|H0Ty°
Dissolving Kraft
Bleached
Papergrade
Kraft/soda
Dissolving
Sulfite
Papergrade
Sulfite
Total
•?•-'$-,, '-1
'I' '"i-i-'pi
'.is
0.14
2.81
0.18
0.07
3.20
Recreation
¥vS-< '
Delected;,
<0.01
0.30
0.17
Eliminated
0.47
''v M?t?''<* ~"J
Baseline';
0.7
19.28
0.53
0.18
20.69
-rl\;\i
ffaufi"'*' ' '
"!s§
0.04
0.91
0.50
Eliminated
1.45
V-'t-kH
^;S-1S
~-°» "~°- -'*<;
, Ba^roite^
0.12
2.36
0.13
0.06
2.67
.".&*£
^:;5il-;i
'%g;
<0.01
0.24
0.12
Eliminated
0.36
i'"simp^
'IIS
0.55
15.73
0.38
0.14
16.80
pxh' ";V-S
T^l.*"-'"''" "^
:^V
0.03
0.70
0.35
Eliminated
1.08
NOTES:
Total estimated number of cancer cases per year (recreational and subsistence) under baseline conditions using the
DRE approach = '5.87
Total estimated number of cancer cases per year (recreational and subsistence) under proposed BAT options using
the DRE approach = 0.83
Total estimated number of cancer cases per year (recreational and subsistence) under baseline conditions using the
simple dilution approach = 37.49
Total estimated number of cancer cases per year (recreational and subsistence) under proposed BAT options using
the simple dilution approach = 2.53
Estimated number of reduced cancer cases per year (recreational and subsistance) using the DRE
approach = 5.04
Estimated number of reduced cancer cases per year (recreational and subsistence) using the simple dilution
approach = 34.96
XV
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Table 6. Number of Mills Exceeding RfDs for Recreational and Subistence
Anglers at Baseline and at Selected BAT Estimated Using Two
Water Quality Models (Simple Dilution and DRE)
Subcategory
Dissolving Kraft
Bleached
Papergrade Kraft
Dissolving
Sulfite
Papergrade
Sulfite
Total:
Percent
Reduction
Recreational Anglers -\
ORE
Bastline
1
29
2
2
34
Selected
Option"
1
4
2
0
7
79%
Simple Dilution":
Baseline
1
54
5
4
64
Selected;
Option
1
17
4
0
22
66%
«?"/ &ttfosi$t«flc«'Angleirt: ;, "•*„
_ ,-,DBE
"BaseMne
2
57
5
4
68
Selected. ;
Option"
1
17
4
0
22
68%
SimpleTOutkw-
Baseline
2
70
5
7
84
'lejected
^Option
1
46
5
0
52
38%
results in the complete elimination of baseline exceedances for two mills. Of the seven mills projected
to exceed RfDs after the implementation of the selected BAT options, one is a dissolving kraft mill, four
are bleached papergrade kraft/soda mills, and two are dissolving sulfite mills.
For subsistence anglers, the estimated number of mills in the four bleaching subcategories exceeding RfDs
for 2,3,7,8-TCDD and 2,3,7,8-TCDF using the DRE approach is reduced from 68 at baseline conditions
to 22 (a 68 percent reduction) after the implementation of the selected BAT options. The selected BAT
totally chlorine-free option for papergrade sulfite mills results in the complete elimination of baseline
exceedances for four mills. Of the 22 mills predicted to exceed RfDs after the implementation of the
selected BAT options, 1 is a dissolving kraft mill, 17 are bleached papergrade kraft/soda mills, and 4 are
dissolving sulfite mills.
2,3,7,8-TCDD and 2,3,7,8-TCDF are estimated to be responsible for more than 99 percent of the projected
noncarcinogenic hazard using the simple dilution approach (Attachment A-23). Two additional pollutants,
4-chlorophenol and 2,4,5-trichlorophenol, are projected to exceed their RfDs using the simple dilution
approach but only at baseline conditions and only for bleached papergrade kraft/soda facilities. One mill
is estimated to exceed the RfD for 4-chlorophenol for recreational anglers under baseline conditions using
the simple dilution approach. Four mills are estimated to exceed the RfD for 4-chlorophenol for
subsistence anglers under baseline conditions using the simple dilution approach. Two mills are estimated
to exceed the RfD for 2,4,5-trichlorophenol for subsistence anglers under baseline conditions.
XVI
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The estimated number of mills exceeding RfDs for recreational anglers for the four bleaching
subcategories using the simple dilution approach is reduced from 64 mills under baseline conditions to
22 (a 66 percent reduction) after the implementation of the selected BAT options. The selected BAT
totally chlorine-free option for papergrade sulfite mills results in the complete elimination of baseline
exceedances for four mills. Of the 22 mills projected to exceed RfDs after the implementation of the
selected BAT options, 1 is a dissolving kraft mill, 17 are bleached papergrade kraft/soda mills, and 4 are
dissolving sulfite mills. All predicted exceedances under the selected BAT options are for 2,3,7,8-TCDD.
For subsistence anglers, the estimated number of mills exceeding RfDs for the four bleaching
subcategories using the simple dilution approach is reduced from 84 at baseline conditions to 52 (a 38
percent reduction) after the implementation of the selected BAT options. The selected BAT totally
chlorine-free option for papergrade sulfite mills results in the complete elimination of baseline exceedances
for seven mills. Of the 52 mills exceeding RfDs after the implementation of the selected BAT options,
1 is a dissolving kraft mill, 46 are bleached papergrade kraft/soda mills, and 5 are dissolving sulfite mills.
All predicted exceedances under the selected BAT options are for 2,3,7,8-TCDD and 2,3,7,8-TCDF.
3. Impact of Proposed BAT Controls on Dioxin-Related Fish Advisories
As of June 1993, 23 receiving streams (including open waterbodies) had fish advisories in place for
dioxins. Twenty-nine chlorine-bleaching pulp and paper mills discharge to these receiving streams in the
vicinity of the fish advisory locations and thus are considered to contribute to the fish tissue concentrations
of dioxins that have resulted in the issuance of the advisories. Because of limitations in available
information, the potential beneficial impacts of the selected BAT options on the lifting of dioxin-related
fish advisories can be assessed for only 25 mills, which affect 20 fish advisories. For 24 facilities that
discharge to 19 receiving streams with fish advisories in place, the impacts of the selected BAT options
are analyzed by comparing modeled 2,3,7,8-TCDD and 2,3,7,8-TCDF fish tissue (i.e., fillet) concentrations
for each selected BAT option, obtained by using the simple dilution and DRE modeling approaches, to
state-specific fish advisory action levels. With the exception of one dissolving kraft facility and one
papergrade sulfite facilty, these mills are all in the bleached papergrade kraft/soda subcategory. The
comparison of estimated fish tissue concentrations to state advisory action levels cannot be done for four
mills because the states in which they are located issue risk-based advisories based on site-specific
determinations rather than using state action levels. However, the risk level used to issue one of the four
advisories is known to be 10~5; therefore, this risk level can be compared to the cancer risk estimated for
that particular mill. In addition, receiving stream flow data are unavailable for one receiving stream.
Three of the receiving streams that currently have dioxin-related fish advisories in place also have
advisories in place in the same locations for other contaminants: two have advisories in place for mercury
and PCBs, and the third has an advisory in place for mercury. These contaminants are not being regulated
by the proposed pulp, paper, and paperboard rule. As a result, even if the dioxin-related advisories are
lifted as a result of BAT implementation, advisories for the other contaminants of concern will remain in
place.
The results of this analysis (Table 7) indicate that 14 (using simple dilution approach) to 19 (using the
DRE approach) existing dioxin-related fish advisories could potentially be lifted after implementation of
the selected BAT options. However, using the DRE approach, two of the receiving streams for which
dioxin-related fish advisories are projected to be lifted after BAT implementation will still have advisories
in place for other contaminants. Using the simple dilution approach, one receiving stream for which the
xvii
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Table 7. Number of Receiving Streams That Would Exceed Dioxin-Related State Fish Advisory
Threshold Limits Under Various Regulatory Alternatives at Current and
Selected BAT Conditions, Estimated Using the
Simple Dilution and DRE Approaches
Discharge Conditions
Current Conditions
Selected BAT Option Conditions
Potentially Eliminated Advisories at
Selected BAT
Simple Dilution
20
6
14
° " ."--. ",: °' "<*>KB " ;v
20
1
19
dioxin-related fish advisory is projected to be lifted after BAT implementation will still have a nondioxin-
related advisory in place.
Based on the number of receiving streams projected to have dioxin-related fish advisories lifted after BAT
implementation and for which no other advisories for other contaminants are in place (i.e., 17 advisories
using the DRE approach and 13 advisories using the simple dilution approach), it is estimated that the
number of recreational anglers using receiving streams that currently have dioxin-related fish advisories
in place could increase from the estimated 135,630 anglers currently fishing these streams to between
161,389 and 162,425 anglers after BAT implementation. These estimates are also based on a limited
number of studies that evaluated changes in angler fishing habits due to the presence of fish advisories.
Based on these studies an estimated 20 percent of recreational anglers change their fishing location or
participation in recreational fishing because of the presence of a fish advisory. For the purpose of this
study, it is assumed that this 20 percent of the recreational angler population will again fish in the
receiving streams in question if and when the dioxin-related fish advisories are lifted.
Limitations and Uncertainties
t
The methodologies used for this environmental assessment are subject to certain limitations and
uncertainties. Some of the problems encountered in the analyses result from lack of available data or lack
of research to evaluate methodological assumptions.
Every effort has been made to use methods and approaches that EPA considers to be standard practice.
Certain assumptions are still required, however. For example, for the evaluation of combined
noncarcinogenic hazards from exposure to a chemical mixture, limited data are available for actually
quantifying the potential synergistic and/or antagonistic relationships between chemicals in a chemical
mixture.
Ninety-nine percent of the estimated carcinogenic risks and noncarcinogenic hazards calculated in this
study can be attributed to 2,3,7,8-TCDD and 2,3,7,8-TCDF. Therefore, the assumptions and methods used
to analyze the dioxin and furan data will affect the interpretation of the results of the regulatory impact
analysis and comparisons. Areas of uncertainty relative to the dioxin and furan risk assessment include:
• Bioconcentration factors used in the risk assessment;
xvm
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• Use of one-half the EPA-designated detection limit to estimate pollutant discharge loadings for
all nondetect congeners; and
• Aquatic life toxic effect values, cancer slope factors (ql*), reference doses (RfDs), and toxic
equivalency factors (TEFs), which are currently under review by EPA, used in the risk assessment.
Also, the methodology used to estimate fish advisory-related benefits assumes that the bleaching pulp and
paper mills are the only source of the dioxin in the stream segment and does not incorporate background
contributions either from contaminated sediments due to'previous discharge practices or from other
upstream sources. Furthermore, although the discharge of these contaminants may cease or may be
minimized, sediment contamination and subsequent accumulation of dioxin in aquatic organisms may
continue for years. Actual improvements can be determined only by site-specific biological monitoring
to assess the appropriateness of eliminating fish consumption advisories.
An additional area of uncertainty involves the estimates of populations exposed to contaminated fish tissue.
For the purpose of this study, angler population estimates were based on data extrapolated from the
number of fishing licenses sold in counties bordering receiving stream reaches and creel survey data. The
actual number of people using these receiving streams for their fishing activities is not known. In
addition, the number of recreational anglers who change their fishing habits as a result of a fish advisory
is based on a few studies with relatively few data.
xix
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1. INTRODUCTION
This document presents the methodology for and results pf the environmental assessment conducted to
estimate potential impacts on aquatic life and human health resulting from exposure to pulp and paper mill
effluents. The environmental assessment has been prepared in support of the U.S. Environmental
Protection Agency's (EPA's) Regulatory Impact Assessment (RIA) for the pulp, paper, and paperboard
industry effluent guidelines in compliance with Executive Order 12866, which requires EPA to assess the
costs and benefits of significant rulemaking. Significant rules are those which impose an annual cost to
industry of $100 million or more or meet certain other economic impact criteria.
The regulations being proposed by EPA would limit the discharge of pollutants into navigable waters of
the United States and the introduction of pollutants into publicly owned treatment works by existing and
new facilities that produce pulp, paper, and paperboard. These proposed regulations would also limit the
emission of hazardous air pollutants by existing and new facilities in the pulp and paper production source
category.
The proposed regulations would establish effluent limitations guidelines based on the "best practicable
control technology currently available" (BPT), "best conventional pollutant control technology" (BCT),
"best available technology economically achievable" (BAT), effluent "new source performance standards"
(NSPS) based on best available demonstrated technology, "pretreatment standards for existing sources"
(PSES), "pretreatment standards for new sources" (PSNS), and "best management practices" (BMP). EPA
is also proposing to regulate emissions of hazardous air pollutants from pulp and paper production
processes, which are considered major sources under section 112 of the Clean Air Act (CAA), as amended
in 1990.
Through mill-specific analyses of 26 pollutants, this assessment evaluates both qualitatively and
quantitatively the potential aquatic life and human health benefits of controlling the discharges from four
bleaching subcategories that fall under BAT regulations (dissolving kraft, bleached papergrade kraft/soda,
dissolving sulfite, and papergrade sulfite). In addition, the environmental significance of discharges from
the non-bleaching segment of the industry is also qualitatively examined. The environmental impacts of
air emissions are discussed in a separate document prepared in support of regulations limiting the emission
of hazardous air pollutants.
For this environmental assessment, potential impacts on water quality are examined for baseline conditions
and for all options under consideration for which loadings were provided, including selected BAT options,
to evaluate the environmental benefit of implementing various BAT control technologies. The effluent
characterization data for BAT mills were obtained from EPA's Office of Science and Technology,
Engineering and Analysis Division (memorandum from Doug Spengel, Radian Corporation, to Drew
Zacherle, Tetra Tech, Inc., June 7, 1993) and covered 103 BAT pulp and paper mills within the United
States. Although the environmental impacts of conventional pollutants (e.g., BOD, TSS) are qualitatively
examined for this environmental assessment, quantification of impacts is conducted only for the bleaching
segment of the industry. Therefore, the primary focus of this document is on toxic pollutants in bleaching
mill effluents, primarily chlorinated organics.
This environmental assessment evaluates the impacts of bleaching pulp and paper mill effluents on aquatic
life and human health. Potential impacts on aquatic life are evaluated by comparing modeled in-stream
contaminant concentrations to acute and chronic ambient water quality concentrations (AWQCs) for the
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protection of freshwater aquatic life. The aquatic life AWQCs used include EPA's aquatic life water
quality criteria and, in cases where water quality criteria have not been developed, other values
representative of the chemicals' aquatic toxicity (Versar, Inc., 1993).
Potential impacts on human health are evaluated by (1) comparing modeled in-stream contaminant
concentrations to health-based toxic effect values (referred to as ambient water quality concentrations, or
AWQCs, for the protection of human health); (2) estimating potential carcinogenic risks and
noncarcinogenic hazards from the consumption offish tissue; (3) estimating the annual incidence of cancer
in the potentially exposed angler population; and (4) comparing estimated fish tissue levels (at BAT
control levels) with state fish advisory action levels. Estimates are also made of the potential increase in
recreational angler participation due to the lifting of fish advisories as a result of implementation of the
selected BAT options. Health-based AWQCs used in this assessment are derived using standard EPA
methodology (USEPA, 1991c).
Exposure pathways evaluated in the cancer risk and noncancer hazard assessment include ingestion offish
by the households of recreational and subsistence anglers. Exposure to contaminants through the water
pathway is also evaluated by the comparison of modeled in-stream contaminant concentrations to health-
based AWQCs for the ingestion of water and organisms. The potential human health cancer risk and
noncancer hazards associated with the ingestion of drinking water are not evaluated because no municipal
public water intakes are within the same river reach or within 10 miles downstream from any bleaching
pulp and paper mill effluent discharge (whichever is the greater distance).
The results of these analyses are used as input in the quantification and monetization of benefits in the
benefits assessment and the RIA for wastewater effluent process technology option analysis.
Chapter 2 of this document presents background information on the pulp, paper, and paperboard industry.
Chapter 3 presents a discussion of the pollutants of concern in pulp and paper mill effluents and their
potential human health and environmental impacts. Chapter 4 describes the methodology for estimating
potential human health and ecological impacts from bleaching pulp and paper mill effluents. Chapter 5
presents the results of the evaluations. Chapter 6 provides a discussion of the limitations and uncertainties
associated with the analyses. Chapter 7 presents the references cited in this assessment. The attachments
to this document include all supporting tables, including results of the analyses performed for each mill.
All data, information, and results of analyses deemed confidential business information (CBI) are part of
the CBI record.
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2. DESCRIPTION OF THE INDUSTRY
There are 565 pulp, paper, and paperboard mills in the United States. The chemical pulping and bleaching
process is conducted by 104 mills, 103 of which are the focus of this environmental assessment. Of the
104 bleaching mills, 94 discharge directly into navigable waterways and will be subject to BAT
regulations, 9 are indirect dischargers and will be subject to PSES regulations, and 1 does not discharge
wastewater into a navigable waterway and therefore is not counted as a mill subject to BAT (memorandum
from Doug Spengel, Radian Corporation, to Drew Zacherle, Tetra Tech, Inc., June 7, 1993). The 103
bleaching mills evaluated in this assessment are grouped into 4 subcategories:
Subcategory
Dissolving Kraft (DK)
Bleached Papergrade Kraft/Soda (PK)
Dissolving Sulfite (DS)
Papergrade Sulfite (PS)
Number of Mills
3
86
5
9
103
Dissolving Kraft: The dissolving kraft subcategory includes mills where a highly bleached wood pulp is
produced by using a "full cook" process that employs a highly alkaline sodium hydroxide and sodium
sulfide cooking liquor. Included in the manufacturing process is a "precook" operation called
prehydrolysis. The principal product is a highly bleached and purified dissolving wood pulp, used
primarily for the manufacture of rayon, viscose, acetate, and other products requiring the virtual absence
of lignin and a very high alpha cellulose content. This subcategory also includes facilities that
manufacture dissolving grade kraft pulps and papergrade kraft pulps at the same site.
Bleached Papergrade Kraft/Soda: The bleached papergrade kraft/soda subcategory includes the integrated
production of bleached kraft wood pulp and board as well as coarse, tissue, and fine papers. Bleached
kraft wood pulp is produced on-site using a "full cook" process that employs a highly alkaline sodium
hydroxide and sodium sulfide cooking liquor. The principal products include papergrade market pulp,
paperboard, coarse papers, tissue papers, and fine papers, which include business, writing, and printing
papers.
This subcategory also includes the integrated production of bleached soda wood pulp and fine papers. The
bleached soda wood pulp is produced on-site using a "full cook" process that employs a highly alkaline
sodium hydroxide cooking liquor. The principal products are fine papers, which include printing, writing,
and business papers, and market pulp.
Dissolving Sulfite: The dissolving sulfite subcategory includes mills where a highly bleached and purified
wood pulp is produced using a "full cook" process that employs strong solutions of calcium, magnesium,
ammonium, or sodium sulfites. The pulps produced by this process are viscose, nitrate, cellophane, or
acetate grades, and they are used principally for the manufacture of rayon and other products that require
the virtual absence of lignin. This subcategory also includes facilities that produce papergrade wood pulp
and dissolving sulfite pulps at the same site.
Papergrade Sulfite: The papergrade sulfite subcategory includes the integrated production of sulfite wood
pulp and paper, with or without brightening or bleaching. The sulfite wood pulp is produced on-site using
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a "full cook" process that employs an acidic cooking liquor of calcium, magnesium, ammonium, or sodium
sulfites. Following the cooking operations, the spent cooking liquor is washed from the pulp in blow pits
or on vacuum or pressure drums. Also included are mills that use belt extraction systems for pulp
washing. The principal products include tissue papers, fine papers, newsprint, and market pulp.
Figures 2-1 through 2-5 illustrate the geographic location of the BAT mills, and Table 2-1 is a list of the
68 receiving streams for these mills.
2.1 Brief Description of the Pulp and Paper Technology
Wood is composed of cellulose, hemicellulose, lignin, and extractives. Cellulose constitutes 40 percent
of most wood and is the most valuable component. Lignin acts as a bonding agent and provides the
rigidity in the fibers. Hemicellulose is a polysaccharide that is of little or no use. The extractives in
softwood are used to produce turpentine and tall oil.
2.1.1 Chemical Pulping
The chemical pulping process removes the lignin, allowing the fibers to be separated and improving the
resulting quality of the fibers for the papermaking process. The majority of mills chemically pulp wood
by using the kraft (sulfate) or sulfite process. The kraft process uses sodium hydroxide and sodium sulfide
heated to 160-180 °C to cleave the lignin bonds, causing the dissolution of the lignin, as well as the
hemicellulose and extractives. Fifty-five percent of the total weight of the wood and 90-95 percent of the
lignin are removed in the pulping liquor. Sulfite mills dissolve the lignin with a heated mixture of sulfur
dioxide and alkaline oxides (sodium, magnesium, or calcium) in a process known as sulfonation. Both
pulping processes evaporate the cooking liquor and then burn it in a recovery boiler to recover energy and
inorganic chemicals that can be used in reconstituted pulping liquor.
2.1.2 Pulp Bleaching
Bleaching is used to whiten pulp by chemically altering the coloring matter and to impart a higher
brightness. The selection of wood type for pulping, the pulping process used, and the desired qualities
and end use of the paper product greatly affect the type and degree of pulp bleaching required. The
whiteness of pulps is usually determined by measuring the reflectance of nearly monochromatic light by
a standard reflectance meter with a scale of 0 to 100. Unbleached pulps generally exhibit brightness
values in the following ranges:
Sulfite
Groundwood
Semi-chemical kraft
up to 65
40 to 60
25 to 35
Two basic methods are used to increase the brightness of pulps. The first is to use selective bleaching
agents that destroy at least a portion of the chromophobic, or colored, compounds without significantly
reacting with lignin, which binds* wood fibers together. This method is used to brighten pulps with high
lignin content such as groundwood and semi-chemical pulps. Brightness values above 70 are difficult to
achieve without delignification. However, significant delignification of these pulps is not desirable due
to the negative impact on yield. The second method of bleaching includes complete or near-complete
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o Dissolving Kraft and Soda
A Dissolving Sulflde
a Papergrade Sulflde
o Bleached Papergrade Kraft and Soda
Figure 2-1. Location of the 103 BAT pulp and paper mills.
o Dissolving Kraft and Soda
Dissolving Sulflde
a Papergrade Sulflde
o Bleached Papergrade Kraft and Soda
Figure 2-2. Location of BAT mills in the northeast United States.
5
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O Dissolving Kraft and Soda
A Dissolving Sulfide
a Papergrade Sulfide
o Bleached Papergrade Kraft and Soda
Figure 2-3. Location of BAT mills in the southeast United States.
o Dissolving Kraft and Soda
A Dissolving Sulfide
D Papergrade Sulflde
o Bleached Papergrade Kraft and Soda
Figure 2-4. Location of BAT mills in the north central United States.
6
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o Dissolving Kraft and Soda
A Dissolving Sulflde
a Papergrade Sulflde
o Bleached Papergrade Kraft and Soda
CO
Figure 2-5. Location of BAT mills in the northwest United States.
Table 2-1. Receiving Streams for the 103 BAT Pulp and Paper Mills
Alabama River
Altamaha River
Androscoggin River
Angelina River
Arkansas River
Atlantic Ocean
Baker Slough
Bayou La Fourche
Blackwater River
Cedar Creek
Chickasaw Creek
Clarion River
Clark Fork River
Codorus Creek
Columbia River
Conecuh River
Coosa River
Cypress Creek
Escanaba River
Escatawpa River
Fenholloway River
Flambeau River
Flint River
Grays Harbor
Hiwassee River
Holston River
Hudson River
Houston Ship Channel
Jackson River
Juniata River
Kennebec River
Lake Champlain
Leaf River
Menominee River
Mississippi River
Mosquito Creek
Neuse River
North River
Ohio River
Ouachita River
Pacific Ocean
Paint Creek
Pamunkey River
Pee Dee River
Penobscot River
Perdido River
Pigeon River
Port Angeles Harbor
Port Gardner Bay
Potomac River; N. Branch
Presumscot River
Rainy River
Red River
Rice Creek
Roanoke River
Sacramento River
Sampit River
Savannah River
Silver Bay
Spirit Creek
St Joseph Sound
Tombigbee River
Turtle River
Ward Cove
Wateree River
Wheeler Lake (Tennessee R.)
Willamette River
Wisconsin River
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removal of the lignin remaining after chemical pulping, followed by further bleaching of the pulp to a
desired degree of brightness. The latter method is used to bleach kraft, soda, and sulfite pulps to
brightness levels in the range of 80 to 90 and above.
In recent years there has been a major trend in the industry toward reducing both the types and the amount
of chlorine-containing chemicals used for pulp bleaching. Most of these changes have occurred as a result
of product quality considerations and environmental concerns about the formation of dioxins and other
chlorinated compounds during pulp bleaching and the presence of dioxins in pulp and paper products.
At many mills, chlorine dioxide is being used in first-stage bleaching in place of some or all of the
chlorine. The use of hypochlorite has diminished in response to concerns about chloroform emissions,
and many mill operators have made significant efforts to improve delignification prior to bleaching to
minimize bleach chemical use and the attendant formation of unwanted chlorinated by-products.
2.2 Process Controls and Changes Considered
The selected process change options for BAT mills are designed to reduce or eliminate the formation of
dioxins, furans, chloroform, and other chlorinated organics. The selected process changes should reduce
the amount of lignin that needs to be bleached, thereby decreasing the quantities of chemicals needed in
the bleaching process and reducing or eliminating the amount of chlorine used in the bleaching process.
A wide variety of process change options were originally evaluated by EPA as to their ability to meet the
standards of the proposed rule (Attachment 1). The process change options selected for each subcategory
for the proposed regulations are listed hi Table 2-2. A brief synopsis of the selected process change
options follows.
2.2.1 Oxygen Delignification
Oxygen delignification, also known as oxygen bleaching, is a pulp treatment process that precedes the
bleaching process. This process removes the residual lignin by treating the pulp with oxygen under
pressure in an alkaline environment. The removal of residual lignin reduces the downstream chemical
requirements for pulp bleaching and the formation of chlorinated organics. Inorganic chemicals are
removed from the washwaters, and the organic load removed from the pulp is used for generating heat.
Table 2-2. Selected Process Options for Each Subcategory
Dissolving
Kraft
Oxygen delignification
with 70% substitution
of chlorine dioxide for
chlorine
Bleached Papergrade „ ',' l'~
Krsft/Swia ' "7,2
*5 v "Select^ process
Oxygen delignification OR
extended delignification
with 100% substitution of
chlorine dioxide for
chlorine
~7. \<»»«d»g ' -|C
S-<° Cci^t1*!8*6. :••'„,?*?-
<*Chang.&' OfJttfaflfS^,^ '," -z^z?,* - °£
Oxygen deliginification
with 100% substitution
of chlorine dioxide for
chlorine
-.r-vxr ,, yft^^nA^-j^'-.-r.f
Sr" ;/,,s^;:r0:>^
'f / ^v"' „,' 'f**>-'e% s^ffi&f'*^ e?' /
TCP: Totally chlorine-free
bleaching using oxygen
delignification followed by
peroxide
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The oxygen delignification process removes approximately 50 percent of the original residual lignin, which
reduces the number of subsequent bleaching stages. With oxygen delignification, a four-stage bleaching
sequence is sufficient to attain over 90 percent of the desired brightness level for bleached softwood kraft,
and a three-stage bleaching sequence is sufficient to attain an 85-90 percent brightness level. In addition,
oxygen delignification reduces chlorine consumption by approximately 50 percent and has been shown
to reduce absorbable organic halogens (AOX) in untreated effluent concentrations by 41 percent and total
organic chlorine by 35 to 50 percent (USEPA, 1990b). The bleached pulp resulting from this technology
is considered to be equal to or superior in quality to conventionally bleached pulps with respect to tear
strength, brightness stability, pitch removal, beating energy, and cleanliness.
2.2.2 Extended Delignification
Extended delignification, also known as extended cooking, involves extending the kraft cooking process
to reduce the lignin content and the demand for subsequent bleaching. To maintain the quality of the pulp
during the extended cooking process, adjustments are made in the alkali profile, residence time, and
temperature. The two methods most commonly used are modified continuous cook and rapid displacement
heating. Both methods are known to reduce chlorine use by 50 percent, thereby reducing the production
of chlorinated organics. When used in conjunction with 70 percent or higher chlorine substitution (see
below), extended delignification can reduce AOX concentrations in untreated effluents by as much as 76
percent (USEPA, 1990b). Canadian research has demonstrated reductions in AOX and total organic
chlorine by 50 percent and 70 percent, respectively.
2.2.3 Chlorine Dioxide Substitution
Chlorine substitution, the most popular of the new processes, is the partial or complete replacement of
elemental chlorine by chlorine dioxide in the first stage of bleaching. Chlorine dioxide is a much stronger
oxidizing agent than elemental chlorine (2.63 times stronger). Moreover, because it bleaches pulp by a
different chemical reaction pathway than that used by chlorine, it produces much smaller quantities of
chlorinated organic compounds than does chlorine. Chlorine dioxide can replace all of the chlorine in the
first bleaching stage.
2.2.4 Ozone Delignification
Ozone delignification is used prior to the chlorine bleaching stage and involves removing lignin by
subjecting the pulp to ozone (O3) in an alkaline environment and sending the waste liquor to the recovery
system. Although not presently used on a commercial scale, this process is intended to reduce chlorine
use and the subsequent production of chlorinated organics.
2.2.5 Peroxide Delignification
In peroxide delignification, pulp is subjected to peroxide in an alkaline environment prior to the bleaching
sequence to reduce the production of chlorinated organics. Currently, only one mill (in Belgium) employs
this process (USEPA, 1990b).
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2.3 Proposed BPT, BCT, and BMP Controls
In addition to the selected BAT process change options, EPA is also proposing BPT/BCT and BMP
controls for the pulp, paper, and paperboard industry. These treatment alternatives are designed to reduce
effluent; to control conventional pollutants such as biochemical oxygen demand (BOD5) and total
suspended solids (TSS). To prevent and control spills of the black liquors produced during the processing
of the wood.
EPA is proposing to revise the BPT effluent limitations guidelines for biochemical oxygen demand (BOD5)
and total suspended solids (TSS) for all subcategories of the pulp, paper, and paperboard industry. These
proposed revisions are based on the application of secondary wastewater treatment with appropriate water
use and reuse. For each subcategory, the proposed effluent limitations are defined by the performance of
the average of the best 50 percent of mills in that subcategory.
EPA is proposing to revise the BCT effluent limitations guidelines for BOD5 and TSS for all subcategories
of the pulp, paper, and paperboard industry. In most cases, the proposed BCT effluent limitations are
equal to the proposed BPT effluent limitations.
The BMPs that EPA is proposing will require the implementation of certain practices, including pulping
liquor spill prevention, containment, and control measures. BMPs are known to reduce the amount of
pulping liquor that is discharged to the wastewater treatment system, as well as to reduce the process
operation cost through increased chemical recovery. Specific key elements that the BMPs will address
are:
• Employee awareness and training;
• Engineering analyses of problem areas and appropriate prevention and control strategies;
• Preventative maintenance;
• Engineered controls and containment;
• Work practices;
• Surveillance and repair programs;
• Dedicated monitoring and alarm systems; and
• Record keeping to document implementation of these practices.
Other BMPs that will be selected from a menu of practices for individual mills include:
• Secondary containment diking around pulping liquor and storage tanks;
• Covered storage tank capacity for collected spills and spilled liquor diversions;
10
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Automated spill detection systems, such as high level, flow, and conductivity monitors and alarms;
and
Backup equipment capacity to handle process upset conditions.
11
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12
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3. BACKGROUND
Pulp and paper mill effluent discharges contain toxic chemical compounds (including toxic contaminants
on EPA's list of priority pollutants and nonconventional pollutants), as well as conventional pollutants
such as biological oxygen demand (BOD) and total suspended solids (TSS). These contaminants may alter
aquatic habitats, impact aquatic life, and subsequently adversely affect human health through the
consumption of contaminated fish and water.
Toxic and nonconventional pollutants of concern in pulp and paper mill effluent include acetone, ketones,
catechols, guaiacols, aldehydes, chloroform, methylene chloride, chlorinated phenols, polychlorinated
dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), adsorbable organic halogens
(AOX), chemical oxygen demand (COD), and color. Of particular concern are the organochlorides, a class
of compounds known for their resistance to biodegradation, toxicity to aquatic life, and long-range
environmental transport, as well as the level at which they concentrate in the fatty tissues of organisms
through either bioaccumulation or biomagnification (via the food chain). The effects of toxic and
nonconventional pollutants on aquatic life vary with the species, concentration of the chemical, and
duration of exposure. However, a number of studies have linked toxic or other biological effects in fish,
wildlife, and humans to exposure to these contaminants from pulp and paper mill effluents.
Conventional pollutants (e.g., TSS) can also cause site-specific environmental impacts. For example,
habitat degradation can result from increased suspended particulate matter that reduces light penetration
and, thus, primary productivity or from accumulation of fibers that can alter benthic spawning grounds
and feeding habitat. Another conventional pollutant discharged in pulp and paper mill effluents is BOD,
which may alter ecosystem structural complexity and functional relationships as populations of planktonic
and macrobenthic organisms decrease or die out while pollution- or anoxia-tolerant bacteria flourish.
The following discussion presents a summary of the pollutants of concern found in pulp and paper mill
effluents and a review of their chemical characteristics and their potential effects on aquatic life and
human health. The issuance of dioxin-related fish advisories is also discussed.
3.1 Pollutants of Concern
From 1989 through 1993 EPA conducted short-term sampling episodes at several pulp and paper mills
located nationwide. These mills were selected because of their particular pulping or bleaching
technologies or their wastewater treatment systems, or because of particular fiber furnishes used or
products produced. The samples were analyzed for chlorinated didxins and furans; chlorinated phenolics;
volatile organics; semivolatile organics; pesticides/herbicides; metals; conventional pollutants (BOD5 and
TSS); and nonconventional pollutants (COD, AOX, and total organic halogens (TOX)). A total of 159
analytes were detected in samples from 11 mills. Of the 159 compounds identified, 36 are priority
pollutants, 28 exhibit high to moderate acute toxicity in aquatic life, 37 are systemic toxicants in humans,
55 have been identified as carcinogens/mutagens, and 38 have drinking water criteria values (USEPA,
1992e). Fifty-seven of the contaminants do not have aquatic toxicity data, and the effects on humans are
unknown for a majority of the analytes. During the last several years, many mills have made process
technology and/or operating changes in the bleach plant to reduce the formation of 2,3,7,8-
tetrachlorodibenzo-p-dioxin (TCDD), 2,3,7,8-tetrachlorbdibenzofuran (TCDF), and other chlorinated
pollutants. These changes have resulted in much-improved effluents.
13
-------
A cooperative long-term sampling effort involving both the industry and EPA was undertaken from 1991
to 1992. The cooperative agreement provided for the sampling of eight bleaching mills that were chosen
because of their particular pulping or bleaching technologies or their wastewater treatment systems, or
because of particular fiber furnishes used or products produced. Samples were collected to characterize
the bleach plant effluent, plant exports (final effluent, pulp, and sludge), and wastewater treatment system
performance. This sampling effort detected 49 unique analytes in the mills' wastewater during any point
in the production process. Of the 49 contaminants detected, 13 are priority pollutants, 11 exhibit high to
moderate toxicity to aquatic life, 14 are systemic toxicants in humans, 13 have been identified as
carcinogens/mutagens, and 11 have drinking water criteria values (USEPA, 1992c). The effects on
humans are unknown for 50 percent of the contaminants.
The short-term and long-term sampling studies support previous data indicating that most of the priority
pollutants are not present in bleached kraft mill effluents. However, among the priority pollutants that
were detected in bleached kraft mill wastewater during these studies are 2,3,7,8-TCDD, chloroform, and
methylene chloride, as well as pentachlorophenol and trichlorophenols.
Based on an evaluation of the short-term and long-term sampling data, EPA has identified 26 organic
compounds of particular concern (USEPA, 1993b) belonging to three chemical groups—(1) dioxins and
furans, (2) volatile organic compounds, and (3) chlorinated phenolics. Of these 26 contaminants, 6 are
priority pollutants, 11 are systemic human toxicants, 6 are human carcinogens, 24 are aquatic life acute
toxicants, and 26 are aquatic life chronic toxicants. Ambient water quality concentrations (for the
ingestion of organisms and water and organisms) for the protection of human health have been established
for 12 and 13 of the contaminants, respectively (Table 3-1).
Examples of observed effects of some of the systematic human toxicants include reproductive and
developmental effects, liver toxicity, and fetotoxicity (Table 3-2). All of the human carcinogens evaluated
are classified as probable, or B2, carcinogens (indicating an agent for which there is sufficient evidence
of carcinogenicity based on animal studies but inadequate data regarding its carcinogenicity from human
epidemiological studies) (Table 3-3).
The primary focus of this aquatic life and human health risk assessment is on the 26 organic compounds
of particular concern that are produced as a result of the pulp bleaching process (Table 3-1). All 26
organic compounds are evaluated in the assessment for their chronic aquatic life impacts, and 24 are
evaluated for their acute aquatic life impacts. Acute aquatic life toxicity values are unavailable for 2,3,7,8-
TCDD and 2,3,7,8-TCDF. Due to a lack of information on human health toxicity, only the following 13
pollutants are evaluated for their potential human health impacts:
• Acetone
• 2-Butanone
• Chloroform
• 4-Chlorophenol
• 2,4-Dichlorophenol
• 2,6-Dichlorophenol
• Methylene chloride
Pentachlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
2,3,4,6-Tetrachlorophenol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol •
14
-------
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-------
Table 3-2. Systemic Human Toxicants Evaluated and Their Target Organ Endpoints
Systemic Toxicant
Acetone
2-Butanone
Chloroform
2,4-Dichlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
Methylene Chloride
Pentachlorophenol
2,3,4,6-Tetrachlorophenol
2,4,5-Trichlorophenol
4-Chlorophenol
Reference Dose Target Organ and Effects x
Increased liver and kidney weights; neurotoxicity
Fetotoxicity
Fatty cysts in liver; fetotoxicity
Decreased delayed hypersensitivity response
Reproductive and developmental effects
Reproductive and developmental effects
Liver toxicity
Liver and kidney pathology
Increased liver weights and centrilobular hypertrophy
Liver and kidney pathology
Unknown
Table 3-3. Human Carcinogens Evaluated, Weight-of-Evidence
Classifications, and Target Organs
Carcinogen
Chloroform
Methylene Chloride
Pentachlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
2,4,6-Trichorophenol
Weight-of-Eyidence
Classification
B2
B2
B2
B2
B2
B2
Target Organs
Kidney
Liver
Liver
Liver and Other Organs
Liver and Other Organs
Kidney and Blood
A review of potential impacts on aquatic life and human health from exposure to 2,3,7,8-TCDD and
2,3,7,8-TCDF, as well as other toxic pollutants (i.e., priority pollutants and nonconventional pollutants)
and conventional pollutants, is presented below.
16
-------
3.1.1 2,3,7,8-TCDD and 2,3,7,8-TCBF
2,3,7,8-TCDD and 2,3,7,8-TCDF were found to occur at every bleaching mill sampled in EPA's 104-Mill
Study (USEPA, 1990d). The identification of these highly toxic chemicals, and other PCDDs and PCDFs,
in pulp and paper mill effluents where chlorine bleaching is used has led to numerous research efforts on
the effects of these chemicals on aquatic life. Although much of the research has focused on the effects
of TCDD and TCDF on the physiology, life history, and community structure of fish populations, many
of the same impacts have been observed in other aquatic species, as well as in terrestrial species that rely
on aquatic species as a food source (e.g., fish, Crustacea, birds, humans, and other mammals) (Table 3-4).
Both TCDD and TCDF have the same toxic endpoints. However, the toxicity of TCDD to aquatic life
is estimated to be two orders of magnitude greater than that of TCDF, and the toxicity of TCDD to
humans is estimated to be one order of magnitude greater than that of TCDF. Therefore, the following
discussion is primarily focused on the nature and properties of TCDD.
Gross signs of TCDD toxicity in laboratory-exposed fish are species-dependent but may include decreased
growth rate, fin necrosis, cutaneous hemorrhage, hyperpigmentation, and edema. Fish in the early life
stages are more sensitive than adults to TCDD toxicity; thus, environmental levels of TCDD may affect
fish populations through reduced hatchability and the development of hemorrhages and subcutaneous yolk
sac edema (accumulation of fluid in the membrane sac attached to the embryo) similar to blue-sac disease
(Cook et al., 1991). Other impacts on fish exposed to TCDD have also been observed in laboratory
studies (Table 3-5). TCDF has been shown to adversely affect survival, growth, and behavior of fish.
The degree of toxicity of the contaminants found in pulp and paper mill effluents is directly related to the
bioavailability of these compounds and the potential of organisms to accumulate (absorb) the contaminants
in their tissues. Analyses of the tissues of invertebrates and fish downstream from mill effluents have
revealed a variety of xenobiotics (foreign compounds not produced by an organism) compared to
organisms from upstream sites (Owens, 1991; USEPA, 1992d). The highly hydrophobia organic
chemicals, such as TCDD and TCDF, become tightly bound to organic carbon in the water column and
in sediment particulates and may not be detected in water. Significant quantities, however, may be taken
up by organisms from ingestion of sediments or contaminated organisms. Body burdens of these
compounds may reach toxic levels.
Other PCDD and PCDF congeners may be more rapidly metabolized in animals, resulting in lower
accumulations and relatively low toxicities. Examination of representatives from simple food chain/web
organisms have revealed biomagnification of TCDD and TCDF from phytoplankton and zooplankton
through mussels or fish to waterfowl (Broman et al., 1992). Terrestrial wildlife that feed on organisms
exposed to pulp and paper mill effluents are also at risk for toxic and reproductive effects (Gilbertson,
1989; Rabert, 1990).
Because 2,3,7,8-TCDD and 2,3,7,8-TCDF are lipophilic, or readily absorbable by fatty tissues, they may
be concentrated in aquatic organisms that have consumed contaminated food or water. Broman et al.
(1992) noted that the wet weight bioconcentration factor (BCF) for 2,3,7,8-TCDD in fish had
experimentally been determined to be in the range of 7,000 to 29,000, lower than that expected based on
estimates of the water solubility and octanol/water partition coefficient (KDW). Thomann (1989) observed
that the efficiency of uptake from water increases with increasing log Kow to a maximum when log Kow
17
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Table 3-4. Affected Organisms and the Physiological and Community Impacts That Have Been
Linked to the Presence of 2,3,7,8-TCDD
Effect/Impact
1. Enzyme Induction
Z Immunological
3. Wasting Syndrome
4. Hepatic (liver)
5. Growth
6. Developmental (skeletal,
organs)
7. Dermatological (lesions, fin
necrosis)
8. Reproductive (fecundity,
sperm/oocyte development,
spawning)
9. Early Life History (eggs,
embryo, larvae)
10. Gill Function (fused
lamellae)
11. Hematological
12. Bioaccumulation
13. Toxicity (lethal/sublethal)
14. Mutagenicity
15. Carcinogenicity (risk
assessment)
16. Behavioral
17. Community Structure
18. Species Diversity
19. Biomass
20. Distribution
Affected Organisms
Fish
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
4-
+
+
+
Molluscs
+
+
+
+
+
+
+
Crustacea
-------
Table 3-5. Target Organs/Tissues, Effects, and Species-Specific Toxicity Values for TCDD
Organ/Tissue^*
HEMATOLOGIC - CC
Leukocytes
Thrombocytes
LYMPHOMYELOID
Thymus - H
Spleen - H, CC
Head kidney - H
EPITHELIAL
Skin - GV, H
Gill - H
Stomach - H
Liver - H
CARDIOVASCULAR
Cardiac
Lesion -•-
Leukopenia
Thrombocytopenia
Involution
Lymphoid depletion
Hypoplasia
Fin necrosis
Fin necrosis, hemorrhage, and
ascites
Fin necrosis
Hyperpigmentation
Lamellar fusion
Hypertrophy and hyperplasia
Necrosis, atrophy, and
hyperplasia
Submucosal edema
Vacuolization, necrosis
Bile duct hyperplasia
Lipidosis
Glycogen depletion
Hypertrophy
Intracytoplasmic inclusions
Myocyte necrosis
Pericarditis-fibrinous
Hypertrophy and hyperplasia
LOAEL* j
1 ug/lcg
1 ug/kg
10 ug/kg
25 ug/kg
10 ug/kg
5 ug/kg
10 ug/kg
25 ug/kg
10 ug/kg
5 ug/kg
25 ug/kg
lug/kg
13.1 ng/g (food)
10 ug/kg
25 ug/kg
10 ug/kg
26 ug/kg
10 ug/kg '•
2.3 mg/kg (food)
10 ng/1
25 ug/kg
1 ug/kg
25 ug/kg
25 ug/kg
10 ng/1
2.3 mg/kg (food)
10 ng/1 •
' 25 ug/kg
25 ug/kg ,
25 ug/kg f
» * » Species'
RBT
RBT
RBT
YP
RBT
YP
RBT
YP
RBT
YP
RBT, YP, C, LMB, CF, BG
C, LMB
CS
RBT
YP
RBT
YP
RBT
RBT
FHM
RBT
YP
YP
YP
YP
RBT
FHM
YP
YP
YP
*- Refetince^-, fS
Spitsbergen et al., 1986
Spitsbergen et al., 1986
Spitsbergen et al., 1986
Spitsbergen et al., 1988
Spitsbergen et al., 1986
Spitsbergen et al., 1988
Spitsbergen et al., 1986
Spitsbergen et al., 1988
Spitsbergen et al., 1986
Spitsbergen et al., 1988
Kleeman et al., 1988
Kleeman et al., 1988
Miller et al., 1979
Spitsbergen et al., 1986
Spitsbergen et al., 1988
Spitsbergen et al., 1986
Spitsbergen et al., 1988
Spitsbergen et al., 1986
Hawkes and Norris, 1977
Adams et al., 1986
Spitsbergen et al., 1986
Spitsbergen et al., 1988
Spitsbergen et al., 1988
Spitsbergen et al., 1988
Spitsbergen et al., 1988
Hawkes and Norris, 1977
Tietge et al., 1986
Spitsbergen et al., 1988
Spitsbergen et al., 1988
Spitsbergen et al., 1988
"Grossly visible (GV), histological (H), cellular count (CC).
"LOAEL = lowest observed adverse effect level. • ,
"Rainbow trout (RBT), yellow perch (YP), bluegill sunfish (BG), carp (C), largemouth bass (LMB), catfish bullhead (CF), echo salmon (CS), fathead minnow (FHM).
Source: Cooper, 1989. ' ,
19
-------
approximately equals 3 to 6, then decreases with increasing log Kow above 6. He concluded that food
chain biomagnification would be significant for substances with log Kow approximately equal to 5 to 6.5
and that this process explains virtually all of the top predator contaminant concentrations. Complexities
in natural food webs—including mechanisms that control the uptake, metabolism, and clearance rates—and
difficulties in assessing the availability of different toxic compounds as the result of sampling and
analytical chemistry problems and natural variability make extrapolations from BCFs obtained in
laboratory studies to contaminant flux in food webs under field situations difficult (Broman et al, 1992).
Nevertheless, a number of studies have examined bioaccumulation and biomagnification of these
compounds in aquatic environments. For example, in the northern Baltic Sea, biomagnification of the
three most toxic 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans decreased in total
2,3,7,8-PCDDs/PCDFs with increasing trophic level in both the littoral and pelagic food chains. The most
toxic 2,3,7,8-substituted isomers accumulated in the tissue of eider duck, but 80 percent of the consumed
total PCDDs/PCDFs were metabolized or excreted (Broman et al., 1992).
BCF values are dependent on the characteristics of the individual chemicals. Bioconcentration is a
partitioning process between the lipids of the organisms and the surrounding water, and it is dependent
on the amount of freely dissolved chemical available to fish through bioconcentration across the gills.
BCFs, however, may be affected not only by variations in the lipid content of different fish species but
also by the age of the fish; exposure level; how the concentration of the compound in water was measured
(freely dissolved or total chemical); low bioavailability (the dioxins are highly hydrophobic); dissolved
organic carbon content of the water (the higher the organic carbon content, the lower the bioavailability
of hydrophobic chemicals); organic carbon in sediments; slow uptake rates; migration patterns offish; and
other factors, leading to measured BCFs that are lower than those predicted.
The BCF of 50,000 for 2,3,7,8-TCDD used in this assessment is based on a measured value from
laboratory research on rainbow trout, a pelagic freshwater species having a lipid content of approximately
7 percent (Cook et al., 1991). Relative BCFs measured by Mehrle et al. (1988) for TCDD (39,000) and
TCDF (6,049) for the same lowest exposure concentration of TCDD, where fish were least affected, in
the same species of fish, yielded a TCDD-to-TCDF BCF ratio of 6.45. Therefore, for this environmental
assessment, the BCF for 2,3,7,8-TCDD (50,000) is divided by 6.45, resulting in a 2,3,7,8-TCDF BCF of
7,752 (which was rounded to 8,000).
The persistent and lipophilic nature of TCDD facilitates its bioaccumulation in the fatty tissues of aquatic
organisms, particularly fish. In spite of its relative insolubility, TCDD will achieve a steady-state
equilibrium between the water column and the sediments (USEPA, 1993a). Concentrations of TCDD in
the water column can become elevated relative to the concentrations in the sediments because of the
redistribution of contaminated sediments resulting from bioturbation and scouring.
2,3,7,8-TCDD is known to be extremely toxic to aquatic life, with concentrations as low as 0.038 ng/L
producing 45 percent mortality in rainbow trout over a period of 28 days (Mehrle et al., 1988). Although
fewer studies have been conducted on 2,3,7,8-TCDF, it is less toxic than TCDD (Mehrle et al., 1988).
With respect to human health, TCDD is listed as a probable carcinogen and is known to have adverse
effects on reproductive capacity and liver function; TCDF has also been identified as a probable
carcinogen. More than 99 percent of the human health-based risk and noncarcinogenic hazard from
bleached kraft pulp and paper mill effluent estimated in this assessment is directly related to 2,3,7,8-TCDD
and 2,3,7,8-TCDF (see Chapter 5).
20
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3.1.2 Other Toxic and Nonconventional Contaminants
Of the 57 volatile organic compounds sampled in the short- and long-term sampling studies, chloroform,
methylene chloride, methyl ethyl ketone (2-butanone), and acetone were detected at all of the mills
(USEPA, 1992c, 1992e). Chloroform and methylene chloride are toxic (priority) pollutants; methyl ethyl
ketone and acetone are nonconventional pollutants. Twelve of the 20 chlorinated phenolics that were
found in bleach plant and final effluents are associated with the formation and presence of TCDD and
TCDF:
Pentachlorophenol
Tetrachlorocatechol
Tetrachloroguaiacol
Trichlorosyringol
2,3,4,6-Tetrachlorophenol
3,4,5-Trichlorocatechol
3,4,6-Trichlorocatechol
3,4,5-Trichloroguaiacol
3,4,6-Trichloroguaiacol
4,5,6-Trichloroguaiacol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
2,4,6-Trichlorophenol and pentachlorophenol are toxic (priority) pollutants, and the remaining pollutants
are nonconventionals.
3.1.2.1 AOX. Chlorinated compounds can also be measured collectively as AOX, TOX, or TOC1 (total
organic chlorine). The preferred test measure analyzes AOX concentrations. Previous EPA studies (i.e.,
the Five Mill Study (USEPA, 1988) and the Integrated Risk Assessment (USEPA, 1990c)) indicate that
although the AOX concentrations can be used to determine the removal of chlorinated organics to assess
loading reductions, they do not provide information on the potential toxicity of the effluent and therefore
are not appropriate to evaluate the potential impacts on the environment. Although no statistical
relationship has been established between the level of AOX and specific chlorinated organic compounds,
AOX analysis can be an inexpensive method for obtaining the "bulk" measure of the total mass of
chlorinated organic compounds.
Historically, the use of AOX as a universal parameter was based on past environmental studies conducted
in Sweden. Observations from studies in the Gulf of Bothnia off the coast of Sweden indicated decreases
in the density and diversity of fish populations located near the discharges of bleached kraft mills, as
compared to fish populations that were located near discharges of unbleached kraft mills (Neuman and
Karas, 1988). In addition, fish populations near bleached kraft mill effluents exhibited higher incidences
of skin diseases, skeletal deformities, fungal infections, fin erosion, smaller reproductive organs, enlarged
livers, higher levels of liver detoxification enzymes, and alterations in blood chemistry and blood cell
ratios (Andersson et al., 1988).
Several objections have been raised regarding the use of AOX as a regulatory parameter and the
conclusion that the abnormalities found in the Swedish studies could be attributed to the discharge of
organochlorines (Carey et al., 1993). These objections are based on the following:
• A correlation between AOX and the effects on the ecosystem had never been demonstrated.
• The Gulf of Bothnia has long been a source of various pollutants that might have contributed to
the results of the Swedish studies.
21
-------
• The bleached kraft mill that was examined had operations that are atypical of well-operated and
modern North American mills.
• Site-specific factors made the unbleached kraft mill unsuitable as a control for comparative
purposes.
The Canadian government initiated some independent studies to address these objections. Fish collected
from Canadian study sites were compared to fish collected from reference sites located away from the
mills. Fish collected near the mills were found to have smaller reproductive organs, enlarged livers, higher
levels of liver detoxification enzymes, and lower levels of sexual hormones in the blood, and they took
longer to reach maturity and had fewer secondary sexual characteristics (McMaster et al., 1991). From
this evidence, the Canadian government concluded that the findings of the Gulf of Bothnia study were not
unique and that similar effects occurred in the fish communities located near Canadian bleached kraft mills
(Carey et al., 1993).
The distribution of the effects in the study did not correlate with AOX, and the major component of AOX
(>90 percent) failed to induce effects in laboratory studies. This information raised questions as to the
applicability of AOX for judging impacts on the environment and its use as a regulatory parameter.
Because of the lack of data to support the use of AOX in evaluating toxicity, it is not one of the
parameters included in this assessment.
3.1.2.2 Color. Color is also a nonconventional pollutant of concern associated with pulp and paper mill
effluent discharges. The intense brown color associated »..'.. pulp mill effluents is caused by lignin and
its derivatives, which are relatively stable compounds that degrade very slowly in biological treatment
systems and in receiving waters. These compounds absorb light at wavelengths between 400 and 500
nanometers, the same spectral band that contains the two most important wavelength peaks for chlorophyll
a and a majority of the other accessory pigments in algae (Thut and Schmiege, 1991). The absorption
of these important wavelengths can inhibit photosynthesis and, consequently, primary production and can
diminish the visual cues necessary for organisms to feed or to reproduce (Owens, 1991; Thut and
Schmiege, 1991). The effect of color on primary productivity is dependent on the concentration of the
effluent in the receiving stream, seasonal variations, depth distributions, and distance from the discharge
site.
The overall impact of color on aquatic algae is difficult to determine. Algae are capable of adapting over
time to shifts in light levels, or they may become metabolically inactive until they are dispersed out of
the effluent plume. Primary production losses in phytoplankton as the result of color in pulping effluents
reducing light levels have been measured in the Baltic Sea and in freshwater streams. However, total
plankton biomass may remain at the same level as species shift from autotropic (photosynthetic) organisms
to heterotropic organisms that use organic carbon inputs (Owens, 1991).
3.1.3 Conventional Pollutants
Prior to the focus on toxic contaminants found in bleaching pulp and paper mill effluents and their effects
on the aquatic environment, the regulatory community required mills to comply with BPT criteria. As
efforts have shifted to the priority pollutants, the efforts to define the chemical compounds in pulp mill
effluents responsible for causing environmental impacts at the community and population levels have been
greatly complicated by the presence of conventional pollutants such as biological oxygen demand (BOD)
and total suspended solids (TSS) (Owens, 1991). Such pollutants, in addition to the pulping and bleaching
22
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chemicals, can alter the quantity of oxygen in the water column and sediments through biological oxidative
reactions (Poole et al., 1978) and may be assessed by measuring the parameters biochemical oxygen
demand (BOD5) and chemical oxygen demand (COD) in the water column. BOD is the amount of oxygen
required by aerobic (oxygen-requiring) organisms to carry out normal oxidative metabolism or the amount
required by oxidation of metabolic by-products from anaerobic organisms in water containir organic
matter. COD is the amount of oxidizable compounds (composed of carbon and hydrogen) prebc.it in the
water. Another water quality parameter affected by these pollutants is turbidity.
Suspended solids such as bark, wood fiber, dirt, grit, and other debris can cause long-term damage to
benthic habitats in freshwater, estuarine, or marine ecosystems. Solids increase water turbidity and reduce
the amount and quality of light present, reducing the growth of phytoplankton, algae, and submerged
aquatic vegetation. Their presence in the water column can interfere with respiration and feeding by
clogging and abrading delicate gill lamellae in organisms such as bivalve mollusks and fishes (Hart and
Fuller, 1974, 1979; Rand and Petrocelli, 1984). As solids settle out of the water column, they physically
cover and smother stationary or immobile benthic flora and fauna. Freshwater mussels are sensitive to
sedimentation stress, and a number of species in the United States are considered endangered and
threatened (Williams et al., 1993). Feeding and reproductive habitat of more mobile species, such as
crustaceans and fishes, may also be eliminated as the result of solids settling on the bottom. Sediment
in the water column or deposited on the bottom can also increase the oxygen demand on the water column
as the result of microbial respiration and chemical oxidation of compounds. The resulting reduced oxygen
levels (hypoxia) can cause lethal and sublethal effects on sedentary benthic invertebrate populations or lead
to the replacement of sensitive species by species more tolerant of reduced oxygen.
Fiber mats are a particular problem associated with pulping effluents (Owens, 1991; Thut and Schmiege,
1991). Decomposition of organic matter in the debris reduces dissolved oxygen levels in the water column
and may lead to anoxic conditions in the sediment with accompanying buildup of methane, hydrogen
sulfide, and other toxic gases. In the Gulf of Bothnia study off Sweden, oxygen levels in the water
column were reduced nearest the effluent, particularly during the summer, with anoxia found in the fiber
mat as the result of increased bacterial biomass and activity (Owens, 1991). Reduced levels of oxygen
may also complicate efforts to assess chemical toxicity. Studies of fish indicated that decreased oxygen
led to increases in the toxicity of both organic and inorganic chemicals by about 1.5-fold, as a result of
the increased rate of flow across the gills at reduced oxygen levels. The effect on lethal and sublethal
toxicities appeared slight; however, this activity resulted in higher concentrations of pollutants in the
vicinity of gill membranes and accompanying higher diffusion of the toxics across the membrane (Rand
and Petrocelli, 1984).
Where effluent discharge rates are too low for color to inhibit photosynthesis or in streams that are too
shallow for color to significantly attenuate light, algae production can be greatly enhanced by the nutrients
contained in the effluent (Stockner and Costella, 1976). Orthophosphate, and particulate nitrogen and
phosphorus, the most prevalent nutrients in pulp mill effluents, have been shown to enhance algal
productivity at effluent concentrations in the receiving stream of up to 25 percent (Walsh et al., 1982).
However, algal production begins to rapidly decline at particulate nitrogen and phosphorus effluent
concentrations above 25 percent.
The principal sources of soluble BOD materials are the black liquor and associated soluble materials from
the pulp washing, volatile organics from the condensate streams, and various additives (Poole et al., 1978).
A number of studies have investigated improvements in microbial treatment of effluents to reduce BOD,
COD, and AOX (e.g., Haggblom and Salkinoja-Salonen, 1991). The proposed secondary wastewater
23
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treatment BPT controls should reduce levels of total suspended solids (TSS) released in pulp, paper, and
paperboard mill effluents by 110 million kg annually and provide improved aquatic habitat quality by
decreasing turbidity and sedimentation in receiving waters as well as by decreasing levels of toxic
chemicals that bind to the solids. Poole et al. (1978) noted that biological treatment may not be effective
in removing the substances that contribute to the color of the waste stream, although new developments
in reducing color would also reduce the total organic content of the effluent, with subsequent reduction
in BOD. The proposed BMP for chemical oxygen demand (COD) and color effluent limitations will
control losses and discharges of pulping liquors and associated wood extractives to reduce aquatic impacts
from loadings of organic and wood extractive constituents.
3.2 Recreational Fisheries
Two studies conducted by EPA confirm the use of fish tissue as a good indicator of bioaccumulated
TCDD in aquatic ecosystems. The National Dioxin Study, which began in 1983, found concentrations
of TCDD in fish tissue that range from below the detection limit of 1 pg TCDD/g wet weight of whole
organism to a maximum of 85 pg/g (USEPA, 1987). This study found the most frequent occurrences and
highest concentrations of TCDD in fish tissue in fish collected in the Great Lakes and downstream from
kraft paper mills. The National Study of Chemical Residues in Fish (NSCRF) sampled bottom-feeding
fish and game fish from 388 sites located nationwide (USEPA, 1992d). As a result of the National Dioxin
Study, the site locations for the NSCRF were biased toward areas where dioxins were likely to be found
(e.g., below the discharge of bleaching pulp and paper mills). In fact, TCDD was detected in fish from
70 percent of the sites, with a maximum tissue concentration of 204 pg/g and an average concentration
of 6.8 pg/g. TCDF was detected in fish from 89 percent of the sites, with a maximum concentration of
404 pg/g and an average concentration of 13.6 pg/g.
The habitat and physiology of aquatic organisms determine the exposure routes. Water acts as the medium
for the transport and partitioning of dioxins and furans between particulate organic matter, sediments, and
the biota (USEPA, 1993a). Cook et al. (1990) reported that food ingestion contributed to 75 percent of
the total TCDD uptake in fish and that the uptake from water was considered negligible in the absence
of contaminated sediments. Laboratory exposure studies showed that when TCDD was added to water
containing contaminated sediments, there was no observed increase in TCDD uptake (Cook et al., 1990).
It was concluded that the ingestion of sediment and direct gill contact with suspended sediment were more
important in uptake rates than the direct uptake of freely dissolved TCDD via gill ventilation.
The physical and chemical degradation of dioxins and furans occurs very slowly. Fish are exposed to
dioxins and furans through the ingestion of contaminated sediments and prey species associated with
sediments (USEPA, 1993a). Many species offish, such as minnows and suckers whose diets include large
quantities of detritus, readily ingest sediment and/or suspended sediments. Gizzard shad (Dorosomd
cepedianum) consume 20 percent of their wet weight in dry sediment daily and are capable of digesting
50 percent to 66 percent of the organic matter contained therein (Mundahl, 1991). The NSCRF found that
TCDD was found more commonly and at higher average concentrations in bottom-feeding species such
as carp (Cyprimis carpio) than in fish species that live higher in the water column (USEPA, 1992d). The
concentrations reported in the NSCRF were not normalized for percent lipid concentration, and therefore
conclusions regarding the relationship between high tissue concentration and bottom-feeding fish have not
been validated.
Human exposure to waterborne pollutants usually occurs through the ingestion of contaminated drinking
water or fish tissue. Because of the virtual insolubility and lipophilic nature of 2,3,7,8-TCDD and 2,3,7,8-
24
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TCDF, the primary exposure route for these pollutants is through the ingestion of contaminated fish tissue
(USEPA, 1984). Human health impacts resulting from the other pollutants in pulp and paper mill effluents
are also primarily the result of exposures through contaminated drinking water and ingestion of
contaminated fish. A variety of compounds may cause toxic reactions, are suspected of producing
abnormal reproductive function, or may be human carcinogens, such as chloroform, methylene chloride,
chlorinated phenolics, and dioxins and furans.
International investigations of the effects of dioxins and furans on humans have suggested that several
unusual mechanisms are involved in the development of acute and chronic impacts resulting from exposure
to these compounds. Epidemiological studies suggest that dioxins are carcinogenic to humans through
increased expression of oncogenes and/or decreases in the expression of tumor suppressor genes through
the action of the aryl hydrocarbon (Ah) or dioxin receptors; by affecting the regulation of other steroid
hormone and growth factor receptors, such as estrogen or epidermal growth factor receptors, to alter cell
differentiation and proliferation; or by compromising immune surveillance and viral defense (Silbergeld,
1991). Further work on the noncarcinogenic effects of dioxins indicates that reproductive function may
be altered at low levels of exposure.
The potential impacts caused by the ingestion of contaminated drinking water are not evaluated for this
assessment because there are no municipal public water intakes within the same river reach or 10 miles
downstream from any pulp and paper mill effluent discharge (whichever was the greater distance). For
these reasons, the population used to determine the potential impacts to human health was based on the
portion of the population that is involved in recreational and subsistence fishing.
3.3 Fish Advisories
Fish advisories and bans are the management tools used by state agencies to reduce the health risks to
recreational and subsistence anglers that are associated with eating contaminated fish. Fish advisories
perform a dual function: (1) they inform the public of the high levels of pollutants found to occur in
locally caught species, and (2) they provide guidance as to the safe levels of consumption for various
subgroups in the population (e.g., children, adults, pregnant or nursing women).
The two procedures currently available for developing fish consumption advisories are from the U.S. Food
and Drug Administration (FDA) and EPA. The FDA is charged with regulating the risks to the general
public from contaminants contained in fish that are sold in interstate commerce. The FDA action levels
are designed to address national needs, and they are based on national consumption patterns. Also, the
FDA takes a risk management approach that considers the economic impact the action levels may have
on the commercial fishing industry. In contrast, the EPA approach is designed to provide states with a
methodology that assesses the health risk to the state's recreational and subsistence anglers and allows the
development of action levels based on the region-specific fishing habits of the groups at risk. FDA action
levels are much higher than EPA-derived action levels because of the FDA's national perspective. Action
levels derived using the EPA risk assessment approach typically indicate a much higher risk associated
with fish consumption because the scope is local, is concerned only with protecting the health of the
public, and does not give any consideration to economic impacts. The availability of these two methods
has led to inconsistencies in action levels from state to state, which can be particularly confusing to
anglers when waterbodies cross interstate boundaries.
From the 1960s through the 1980s, most state agencies used the FDA action levels for setting their fish
advisories (Reinert et al., 1991). With the promulgation of the 1987 amendments to the Clean Water Act,
25
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EPA developed water-quality-derived procedures based on risk assessment techniques. Some of the states
replaced their FDA action levels with those derived by using the EPA procedures. However, a 1989
survey (Table 3-6) showed that of the 37 states reporting to have waterbodies under some sort of fish or
shellfish consumption advisory, 34 states still derived some or all contaminant levels of concern from the
FDA action levels (Cunningham et al., 1990). Thirty states acknowledged the use of or intent to use a
risk assessment methodology, and only 11 states based all of their advisories on risk assessments.
The disparity of state action levels is evident among the fish advisories for streams affected by pulp and
paper mills. Twenty-nine bleaching mills discharge into receiving streams that are presently under fish
advisories for dioxins (as of June 1993). These 29 mills are located in 15 states, for which there are 10
different action levels (Table 3-7).
Fish advisories provide the species offish that may contain the contaminants of concern, recommendations
regarding the amount of fish tissue that is safe to consume, and the population subgroups that may be at
risk. As of June 1993, 23 receiving streams of bleaching pulp and paper mills had fish advisories in place
for dioxins (Table 3-8).
26
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Table 3-6. Various Methodologies and Their Frequency of Use by States
for Deriving Action Levels for Issuing Fish Advisories
,;'"\; -^-;;.v~r. "A>/;psieflbds\,;r' • '£ _r>,:,,:
Derive some or all contaminant levels of concern
from FDA action levels
Base all advisories on risk assessment
Base advisories on risk assessment only when FDA
action levels do not exist
Currently developing a risk assessment approach
Do not plan to use a risk assessment approach
Method unknown
, -, ~Nsbl>«ar'oi? Stites ': * - ~~
34
11
10
9
10
11
NOTES: 1. Some states may use more than one method.
2. EPA's risk assessment guidelines were used as written or in modified form by 18 states;
3 states used a state method independent of EPA's approach; 8 states used two or more
risk assessment methods; 1 state did not specify which risk assessment method was used.
Source: Reinert et al., 1991.
Table 3-7. State Action Levels for Dioxin
'"ri?*?; .*
/State,
" Level
Arkansas
California
Florida
Louisiana
Maine
Maryland
Michigan
Minnesota
Mississippi
New Hampshire
North Carolina
Pennsylvania
Texas
Virginia
Wisconsin
0.007
Conducts site-specific risk
assessments
0.009
0.002
0.0015
0.0013
0.01
0.000032
0.005
Sets advisories based on risk
0.003
25.00 (FDA action level)
0.007
0.003
0.01
27
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Table 3-8. Receiving Streams of Bleaching Pulp and Paper Mills Under Dioxin Fish Advisories,
the Advisory Type, and Species Whose Consumption Is Limited3
Receiving Stream
Blackwater River, VA
Houston Ship Channel, TX
Kennebec River, ME
Escatawpa River, MS
Ouachita River, AR
Escanaba River, MI
Androscoggin River, ME
Bayou La Fourche, LA
Red River, AR
Fenholloway River, FL
Codorus Creek, PA
Neches River, TX
Penobscot River, ME
St. Louis River, MN°
Androscoggin River, NH
Pacific Ocean, CA
Potomac River; N. Branch, MD
Leaf River, MS
Roanoke River, VA
Rainy River, MNC
Pigeon River, NC
Sacramento River, CA
Wisconsin River, WI
Advisory TypAe
NCGP
NCSP
RGP
NCSP, RGP
RGP
NCSP, RGP
NCGP
NCSP
RGP
NCGP
NCGP
RGP
NCGP
NCSP, RGP
NCSP
NCSP, RGP
NCGP
NCGP
NCGP
RGP
NCSP
NCGP, RGP
NCGP
NCGP
NCGP
- ~f'\ _, Fish Species Coveredjbf Advisory- ;
Bottom-feeding species
Catfish, blue crabs
All fish species
All fish and shellfish species
All fish species
All fish species
All fish species
All fish and shellfish species
Catfish fillet
All fish species
Green sunfish
All fish and shellfish species
All fish species
All fish species
All fish species
All fish and shellfish species
Bottom-feeding fish, channel catfish, bullhead
catfish
Bottom-feeding species (>22 in or >5 Ib)
All fish species, except herring, shad, and shellfish
All fish species
All fish species
All fish species
Carp, white bass
28
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Table 3-8. (Continued)
''Based on data contained in EPA's Fish Advisory Database as of June 1993.
Codes that indicate the advisory type:
NCGP: No consumption fish advisory or ban: Advises against consumption of fish or shellfish species by the general population.
NCSP: No consumption fish advisory or ban for a subpopulation: Advises against consumption of fish or shellfish species by a subpopulation
that could be at potentially greater risk (e.g., pregnant women, nursing mothers, or children).
RGP: Restricted consumption fish advisory or ban: Advises restricted consumption (e.g., a limited number of meals or limited sizes of meals
per unit time) of fish or shellfish species by the general population.
RSP: Restricted consumption fish advisory or ban for a subpopulation: Advises restricted consumption (e.g., a limited number of meals or
limited sizes of meals per unit time) offish or shellfish species by a subpopulation that could be at potentially greater risk (e.g., pregnant
women, nursing mothers, or children).
°Advisory also covers PCBs and mercury in the same fish species.
Separate advisory in place for mercury covering same geographic area
29
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30
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4. METHODOLOGY
This chapter summarizes the methodology used in the environmental assessment and risk assessment
conducted to estimate potential impacts on aquatic life and human health resulting from exposure to the
effluents of bleaching pulp and paper mills. Potential impacts are evaluated on a site-specific basis for
each selected BAT option and for baseline conditions for four subcategories of the pulp, paper,.and
paperboard industry (dissolving kraft, bleached papergrade kraft/soda, papergrade sulfite, and dissolving
sulfite) in order to evaluate the environmental benefit of implementing BAT controls. Potential impacts
on aquatic life are evaluated by comparing modeled in-stream contaminant concentrations to EPA's aquatic
life water quality criteria. Where water quality criteria have not been developed, other values
representative of the chemical's aquatic toxicity are used. These values (criteria and other values) are
referred to in this document as aquatic life ambient water quality concentrations (aquatic life AWQCs).
Modeled in-stream concentrations are compared to both acute AWQCs and chronic AWQCs when
available. Potential impacts on human health are evaluated by (1) comparing modeled in-stream
contaminant concentrations to health-based toxic effect values derived using standard EPA methodology
(referred to as human health ambient water quality concentrations, or health-based AWQCs); (2) estimating
potential carcinogenic risks and noncarcinogenic hazards due to the consumption of contaminated fish;
(3) estimating the annual incidence of cancer in the potentially exposed angler population; and
(4) estimating the number of existing dioxin-related state fish advisories that will be lifted after the
implementation of the selected BAT options. Estimates are also made of the potential increase in
recreational angler participation due to the lifting of fish advisories as a result of implementation of
selected BAT options.
Exposure pathways evaluated in this assessment include ingestion of fish by recreational and subsistence
anglers and their households. Exposure to contaminants through the water pathway is also evaluated by
the comparison of modeled in-stream contaminant concentrations to human health-based AWQCs for the
ingestion of water and organisms. An evaluation of the potential human carcinogenic risk and
noncarcinogenic hazards associated with the ingestion of drinking water is not included because there are
no municipal public water intakes within the same river reach or 10 miles downstream from any bleaching
pulp and paper mill effluent discharge (whichever is the greater distance).
All 26 chemicals selected as chemicals of potential concern for which loadings have been provided by
EPA's Office of Science and Technology, Engineering and Analysis Division (BAD), are included in this
environmental assessment (memorandum from Doug Spengel, Radian Corporation, to Drew Zacherle, Tetra
Tech, Inc., June 7, 1993). However, the actual number of pollutants included in each type of analysis
varies because of the availability of data related to pollutant characteristics (e.g., carcinogenicity, BCFs,
toxicity).
4.1 Estimating In-Stream Concentrations
Estimating in-stream contaminant concentrations for various flow conditions is the first step in evaluating
impacts on aquatic life and human health. Loadings data have been obtained from BAD in kilograms of
pollutant discharged per year for each chemical discharged from a facility under baseline conditions and
each selected BAT option. The loadings data are used to derive effluent concentrations for each chemical.
The effluent concentrations are derived by dividing the loading by the plant flow. The in-stream
concentration is then calculated by multiplying the effluent concentration by the stream dilution factor,
i.e., plant flow/(plant flow + stream flow). Stream dilution factors are derived for three measures of low-
31
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flow conditions of the stream at the mill effluent: 1Q10 flow (i.e., the lowest flow measured over a 10-
year period), 7Q10 flow (i.e., the lowest 7-day average flow in a 10-year period), and harmonic mean flow
(HMF) (USEPA, 1991c). Site-specific 7Q10 flows and HMFs are obtained for each of the mills, as
reported in Risk Assessment for 2,3,7,8-TCDD and 2,3,7,8-TCDF Contaminated Receiving Waters from
U.S. Chlorine-Bleaching Pulp and Paper Mills (USEPA, 1990a). Site-specific 1Q10 flows are derived
by multiplying gage-specific 1Q10 flows measured downstream of mill effluents by the percent
contribution of the gage flow associated with the site-specific stream (i.e., site-specific stream flow/gage
flow). Given the limited data available, the percent contribution of the gage flow is calculated by dividing
the mill-specific 7Q10 flow by the gage-measured 7Q10 flow.
Surrogate flows are derived for 17 mills that discharge to open waters (e.g., oceans, estuaries, lakes).
These flows are calculated by using the following equation:
F0 = (D • Fj- Fp
where:
F0 = surrogate open water body flow;
D = dilution factor (as provided by USEPA (1990a) and regional EPA personnel); and
Fp = mill plant flow.
A dilution factor for one mill is not available; therefore, a surrogate flow cannot be calculated. Also,
because no HMF flow is available for one mill, no human health risk estimates are calculated for that mill.
Facility-specific effluent flows and receiving stream flows for all of the mills evaluated in this assessment
are included as part of the CBI record.
4.2 Estimating Impacts to Aquatic Life
Aquatic life impacts are evaluated for 101 mills discharging to 68 receiving streams for the following 26
pollutants:
• Acetone
• 2-Butanone
• 4-Chlorocatechol
• Chloroform
• 4-Chlorophenol
• 6-Chlorovanillin
• 4,5-Dichlorocatechol
• 2,4-Dichlorophenol
• 2,6-Dichlorophenol
• 2,6-Dichlorosyringaldehyde
• 5,6-Dichlorovanillin
• Methylene chloride
• Pentachlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
3,4,5,6-Tetrachlorocatechol
3,4,5,6-Tetrachloroguaiacol
2,3,4,6-Tetrachlorophenol
3,4,5-Trichlorocatechol
3,4,6-Trichlorocatechol
3,4,5-Trichloroguaiacol
3,4,6-Trichloroguaiacol
4,5,6-Trichloroguaiacol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
3,4,5-Trichlorosyringol
Potential impacts on aquatic life are evaluated on a site-specific basis by comparing modeled in-stream
contaminant concentrations with aquatic life criteria and toxicity values (acute and chronic AWQCs) for
these 26 pollutants (Table 3-1 and Attachment A-4). The in-stream concentrations under 1Q10 flow
32
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conditions are compared to acute AWQCs for each chemical discharged from each mill under each
selected BAT option and baseline conditions. The in-stream concentrations under 7Q10 flow conditions
are compared to chronic AWQCs. Exceedances of AWQCs are quantified by dividing the modeled in-
stream concentrations for each flow condition by the respective AWQC for each chemical.
4.3 Estimating Impacts to Human Health
Potential impacts on human health are evaluated on a site-specific basis by (1) comparing estimated in-
stream contaminant concentrations to health-based AWQCs; (2) estimating the potential carcinogenic risk
and noncarcinogenic hazards from the consumption of contaminated fish tissue; (3) estimating the annual
incidence of cancer in the potentially exposed angler population; and (4) estimating the number of existing
dioxin-related state fish advisories that will potentially be lifted after the implementation of the selected
BAT options. Estimates are also made of the potential increase in recreational angler participation due
to the lifting of fish advisories as a result of implementation of selected BAT options.
4.3.1 Comparison to AWQCs for the Protection of Human Health
For 100 mills that discharge into 68 receiving streams, the in-stream contaminant concentrations under
HMF conditions are compared to health-based AWQCs for ingestion of aquatic organisms (12 pollutants)
and ingestion of water and aquatic organisms (13 pollutants) (Table 3-1, Attachment A-4). The
contaminants are listed below:
Acetone
2-Butanone
Chloroform
4-Chlorophenol
2,4,-Dichlorophenol
2,6-Dichlorophenol (water and organisms
only)
Methylene chloride
Pentachlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
2,3,4,6-Tetrachlorophenol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
The HMF concentration, which is more reflective of average in-stream concentrations, is used for this
assessment because health-based AWQCs are derived for lifetime exposure conditions rather than for
subchronic or acute conditions. Exceedances of health-based AWQCs are quantified by dividing the
predicted in-stream concentration under HMF conditions by the health-based AWQC for each chemical
discharged from each facility under each selected BAT option and baseline conditions.
4.3.2 Estimation of Carcinogenic Risks and Noncarcinogenic Hazards
Potential impacts on human health are also evaluated by estimating potential carcinogenic risks and
noncarcinogenic hazards. This assessment, conducted in accordance with available EPA guidance
including Risk Assessment Guidance for Superfund (USEPA, 1989a) and Assessing Human Health Risk
from Chemically Contaminated Fish and Shellfish: A Guidance Manual (USEPA, 1989b), is performed
for the following contaminants:
33
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Systemic Pollutants with Reference Doses
Acetone Pentachlorophenol
2-Butanone 2,3,7,8-TCDD
Chloroform 2,3,7,8-TCDF
4-Chlorophenol 2,3,4,6-Tetrachlorophenol
2,4-Dichlorophenol 2,4,5-Trichlorophenol
Methylene chloride
Carcinogens
Chloroform
Methylene chloride
Pentachlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
2,4,6-Trichlorophenol
As outlined in EPA guidance, the technical approach for conducting a risk assessment involves a three-step
process:
(1) Toxicity Assessment An attempt was made to obtain human health toxic effect values for the 26
contaminants of potential concern using EPA data sources such as IRIS (USEPA, 1992a) and
HEAST (USEPA, 1992b). Based on the list of chemicals of potential concern, only 11 of the total
number of chemicals have available reference dose values (RfDs) and 6 have cancer slope factors
(ql*s)(Table 3-3 and Attachment A-3.).
(2) Exposure Assessment. The exposure assessment involves identifying exposure pathways of
concern, estimating exposure point concentrations, and estimating chronic daily intakes.
• Identifying Exposure Pathways of Concern. Water-related exposure pathways and target
populations are identified as part of this step. Pathways quantitatively evaluated include only
ingestion of fish by recreational and subsistence anglers. Potential risks associated with
ingestion of drinking water were to be evaluated only for mills upstream and within the same
reach or within 10 miles of a municipal public water intake. None of the mills evaluated for
this assessment meet these criteria, however, and therefore potential exposure, cancer risk, and
noncarcinogenic hazards associated with ingestion of drinking water are not evaluated.
• Estimating Exposure Point Concentrations. The exposure point concentration (EPC) is the
average concentration contacted over the duration of the exposure period. For the fish ingestion
pathway, fish tissue EPCs are calculated using two separate approaches. In the first approach,
EPCs are calculated by multiplying the contaminant-specific BCF (Table 3-3) by the estimated
in-stream concentration under HMF conditions for 11 systemic pollutants and 6 carcinogens
using a simple dilution calculation. The second approach, which involves the use of the Dioxin
Reassessment Evaluation (DRE) Model developed by EPA's Office of Research and
Development (still under EPA review) (USEPA, 1993c), is applicable only for estimating EPCs
for 2,3,7,8-TCDD and 2,3,7,8-TCDF. Rather than using an in-stream contaminant concentration
and the above water-based BCF, the DRE model estimates fish tissue concentrations of dioxin
and furan by calculating the equilibrium between the contaminants in fish tissue and those
adsorbed to the organic fraction of sediments suspended in the water column. The in-stream
concentration under HMF conditions is used to estimate exposure point concentrations because
the exposure pathways evaluated represent lifetime exposure conditions rather than subchronic
or acute conditions.
* Estimating Chronic Daily Intakes. Chronic daily intakes (GDIs) are estimated using exposure
models presented in EPA guidance (USEPA, 1989a, 1989b) for each chemical discharged from
a facility under each regulatory alternative and baseline conditions. GDIs are expressed in terms
34
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of milligrams of contaminant contacted per kilogram of body weight per day (i.e., mg/kg/day).
The GDI is calculated by combining the EPC and exposure parameter estimates (e.g., ingestion
rate, exposure frequency, exposure duration, body weight, averaging time) using a chemical
intake equation. GDIs are estimated for evaluating both carcinogenic risks (based on a lifetime
average daily dose) and noncarcinogenic hazards (based on an average daily dose during the
exposure period). GDIs are estimated for both baseline conditions and estimated future
conditions assuming implementation of various selected BAT options.
The equation and exposure parameter values used to estimate GDIs for ingestion of fish
presented below:
are
GDI =
where:
GDI =
EPC =
BCF =
CF, =
CF2 =
CF3 =
IR =
EF
ED
BW
AT
(BW)(AT)
Chronic daily intake (mg/kg/day);
Exposure point concentration (in-stream concentration under HMF conditions) (ug/L);
Bioconcentration factor (unitless);
Conversion factor (103 mg/g);
Conversion factor (L/kg);
Conversion factor (10~9 kg/ug); and
Ingestion rate. At this time no site-specific fish ingestion studies are available for
quantifying ingestion patterns in the vicinity of specific mill effluents. Therefore,
several studies were compiled to assess average ingestion rates for recreational and
subsistence angler populations. For recreational anglers an ingestion rate of 25 g/day,
which represents the midpoint of the reported range of average ingestion rates for
recreational anglers of approximately 20 to 30 g/day (Connelly et al., 1990; Pierce
et al., 1981; West et al., 1989) is used. For subsistence anglers an average daily
ingestion rate of 145 g/day, which assumes that an individual eats one average-size
fish meal per day, is used. The ingestion rate for subsistence anglers is also
supported by a study conducted by Pao et al. (1982).
Exposure frequency (365 days/year) (USEPA 1989a, 1989b);
Exposure duration (30 years for recreational anglers and 70 years for subsistence
anglers) (USEPA 1989a, 1991a);
Body weight (70 kg) (USEPA 1989a, 1991a); and
Averaging time (70 years x 365 days/year for carcinogens and 30 years [for
recreational anglers] or 70 years [for subsistence anglers] x 365 days/year for
noncarcinogens).
(3) Risk Characterization. Carcinogenic risks and noncarcinogenic hazards are estimated for
chemicals with available toxicity criteria for the pathways quantitatively evaluated in this study.
4.3.2.1 Potential Carcinogenic Risks. The potential carcinogenic risks associated with the discharges
of 100 mills and 6 pollutants are expressed as an increased probability of developing cancer over a lifetime
(i.e., excess individual lifetime cancer risk) (USEPA, 1989a). Carcinogenic risks are quantified using the
equation below:
35
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Cancer riskt = CDIi * SFi
where:
Cancer riskj = The potential carcinogenic risk associated with exposure to chemical i (unitless);
CDIj = Chronic daily intake for chemical i (mg/kg/day); and
SFj = Slope factor for chemical / (mg/kg/day)"1.
If the carcinogenic risk exceeds 10"2, then EPA guidance (USEPA, 1989a) recommends using the
following equation to estimate carcinogenic risk:
where:
Cancer risk;
CDIj
SF,
Cancer risk, = 1 - e(-CDI> * SFi)
= Increased carcinogenic risk associated with exposure to chemical i (unitless);
= Chronic daily intake for chemical i (mg/kg/day); and
= Slope factor for chemical / (mg/kg/day)"1.
Chemical-specific cancer risks are summed in accordance with EPA guidance (USEPA, 1989a) in order
to quantify the combined cancer risk associated with exposure to a chemical mixture. The total potential
carcinogenic risk is estimated for each exposure pathway, for each facility, and for each selected BAT
option and baseline conditions.
4.3.2.2 Potential Noncarcinogenic Hazards. Noncarcinogenic hazards are evaluated for 100 mills and
11 systemic human toxicants by comparing the estimated dose (i.e., GDI) with a reference dose (RfD)
(Table 3-3). The hazard quotient, which is used to quantify the potential for an adverse noncarcinogenic
effect to occur, is calculated using the following equation:
GDI,
where:
= Hazard quotient for chemical i (unitless);
= Chronic daily intake for chemical i (mg/kg/day); and
= Reference dose for chemical i (mg/kg/day).
If the hazard quotient exceeds unity (i.e., 1), then an adverse health effect may occur. The higher the
hazard quotient, the more likely that an adverse noncarcinogenic effect will occur as a result of exposure
to the chemical. If the estimated hazard quotient is less than unity, then an adverse noncarcinogenic effect
is highly unlikely to occur.
EPA recommends summing chemical-specific hazard quotients for contaminants with similar endpoints
to evaluate the combined noncarcinogenic hazard from exposure to a chemical mixture (USEPA, 1989a).
The sum of the chemical-specific hazard quotients is called the hazard index. Using this approach
assumes that chemical-specific noncarcinogenic hazards are additive. Limited data are available for
actually quantifying the potential synergistic and/or antagonistic relationships between chemicals in a
36
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chemical mixture. For this assessment, only the hazard quotients that had similar target organs and
lexicological mechanisms that may result in the effect were summed (i.e., 2,3,7,8-TCDD and 2,3,7,8-
TCDF).
Estimation of Increased Incidence of Cancer. In addition to estimating the potential carcinogenic risk
associated with consuming contaminated fish tissue, an attempt is made to estimate the increased annual
incidence of cancer that would occur at the estimated risk levels. For the purpose of this assessment, the
potentially exposed population is considered to be a fraction of the recreational and subsistence anglers
that reside in the vicinity of the discharge and thus might be expected to use the receiving stream for their
recreational and subsistence fishing activities. Estimates of the number of recreational and subsistence
anglers potentially exposed are based on site-specific recreational fishing license data and creel survey data
for several receiving streams for chlorine bleaching pulp and paper mills.
The number of recreational fishing licenses sold in counties bordering the river reaches where each
discharge occurs was obtained from state fishery officials. For the purpose of this assessment, it is
assumed that 95 percent of these licenses were sold to recreational anglers and 5 percent were sold to
subsistence anglers. Actual creel survey data (Attachment A-5) from eight receiving streams with
bleaching pulp and paper mills are used to estimate the fraction of the total number of licensed anglers
who reside in the vicinity of a discharge and who actually use the particular receiving stream for their
recreational and subsistence fishing activities (Attachment A-6). The estimated number of anglers using
the stream based on creel survey data is compared to the total number of licensed anglers in counties
surrounding the reach where the discharge occurs. The resulting ratio represents an estimate of the
fraction of all licensed anglers in the area who fish on the receiving stream. These ratios range from 0.69
to 0.005. The average of these ratios (0.29) is used to extrapolate for all of the mills the number of
licensed anglers who actually fish on the receiving stream in question by multiplying the total number of
licensed anglers in counties bordering the receiving stream by 0.29.
For receiving streams with fish advisories in place, it is assumed that many recreational anglers would
adhere to the advisory and not use the stream in question. However, based on the existing literature, it
is assumed that most anglers are unaware of fish advisories or continue to use receiving streams for their
fishing activities in spite of the presence of fish advisories.
Only a limited number of studies that examine angler behavior in response to fish consumption advisories
are available. In general, these studies have produced relatively similar results, finding a significant (but
not complete) level of awareness of advisories by anglers and some degree of behavioral change.
However, the results do not substantiate an assumption that most recreational anglers would stop eating
contaminated fish altogether. Studies conducted by Silverman (1990) and Knuth and Velicer (1990)
indicate that approximately 54 to 90 percent of all anglers are aware of state fish advisories in place on
receiving streams where they fish. These studies indicate that between 10 and 31 percent of anglers who
are aware of fish advisories either change their fishing location or participation in fishing activities as a
result of the fish advisories. The remainder of those anglers aware of the fish advisories continue to fish
and either change their consumption habits or change their preparation methods. The studies by Knuth
and Velicer (1990) also found that there was confusion as to which waters were considered contaminated
(37 percent of anglers actually fishing in contaminated waters said they were fishing in uncontaminated
waters), and other studies indicate that fewer anglers are aware of fish advisories than those found in
studies conducted by Silverman (1990) and Knuth and Velicer (1990). For example, Belton et al. (1986)
found that as few as 50 percent of anglers in New York and New Jersey were aware of fish advisories
in place on receiving streams where they fish.
37
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For the purpose of this environmental assessment, a conservative estimate of a 20 percent decrease in
fishing activity due to the presence of a fish advisory is assumed based on the changes in fishing location
and participation reported in the literature (Silverman, 1990; Knuth and Velicer, 1990). The actual number
of anglers still fishing on receiving streams with fish advisories in place is calculated by multiplying the
total number of licensed anglers in counties bordering the receiving stream reach by 0.95 (i.e., percent of
total licensed anglers considered to be recreational anglers), then multiplying the result by 0.29 (i.e.,
percent of recreational anglers estimated to actually use the receiving stream in question for their fishing
activities) and by 0.80 (i.e., percent of anglers who continue to use a receiving stream for their fishing
activities in spite of the presence of a fish advisory). It is assumed that fish advisories do not change the
fishing habits of subsistence anglers.
In addition to the anglers themselves, it is assumed that families of anglers would also be exposed to
contaminated fish. Therefore, for each mill, the estimated number of recreational and subsistence anglers
are each multiplied by 2.63, the size of the average U.S. household as determined by the 1990 census
(U.S. Census Bureau, 1992), to estimate the size of the total potentially exposed population. The total
number of potentially exposed recreational and subsistence anglers and their family members for each mill
is then multiplied by the estimated increased individual lifetime cancer risk for each mill. These values
are then divided by 70 (i.e., approximate number of years in a lifetime) to estimate the annual increased
incidence of cancer in recreational and subsistence anglers and their families.
Comparison with State Action Levels. Twenty-three fish advisories for dioxins were in place as of June
1993 on stream segments located downstream of 29 bleaching pulp and paper mills (including 2 open
ocean locations in close proximity to pulp mill outfalls). For this assessment, modeled fish tissue (fillet)
levels of 2,3,7,8-TCDD and 2,3,7,8-TCDF in the receiving stream are compared to the state action levels
(Table 3-7) to estimate whether the selected BAT options by themselves are sufficient to eliminate the fish
advisories. Fish tissue concentrations are estimated using two separate approaches. First, fish tissue
concentrations are calculated by multiplying the estimated in-stream concentrations (expressed as 2,3,7,8-
TCDD and 2,3,7,8-TCDF toxicity equivalents) under HMF conditions by the chemical-specific
bioconcentration factor (BCF = 50,000 for 2,3,7,8-TCDD and 8,000 for 2,3,7,8-TCDF). Fish tissue
concentrations are also estimated using ORD's Dioxin Reassessment Evaluation Model, as described
previously. Exceedances of state action levels are quantified by dividing the estimated fish tissue
concentration by the state action level for each selected BAT option. Because it is not the purpose of this
assessment to determine the validity of the current fish advisories, baseline conditions are not evaluated.
Two states, in which four dioxin/furan-related fish advisories are in place, do not have specific state
threshold values for initiating fish advisories. One of these states currently issues fish advisories when
the potential increased individual cancer risk associated with the consumption of fish tissue reaches 10"6
(a daily consumption rate of 6.5 g/day is assumed). The one advisory examined for this assessment,
however, was set based on a potential increased individual cancer risk of 10"5. The second state has fish
advisories in place for rivers as well as ocean waters. Fish advisories issued for rivers are based on the
results of site-specific risk assessments. Risk assessments are not performed for fish advisories issued in
ocean waters; instead, generic advisories are issued by the state. In addition, receiving stream flow data
are unavailable for one of the receiving streams. Therefore, threshold exceedance comparisons can be
conducted for only 24 of the 29 mills. The advisory issued in the one state that was based on a 10"5 risk
level is affected by only one facility and is evaluated based on estimated individual cancer risk. Therefore,
the total number of facilities examined in this assessment is 25. These 25 mills are assumed to have an
impact on the fish advisories on 20 receiving streams.
38
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For those fish advisories affected by discharges from more than one facility, no attempt is made to
estimate the cumulative effect of the combined discharges. Instead, each faculty is evaluated separately
to determine whether the fish advisory threshold limits would be exceeded under selected BAT options.
The potential increase in recreational angler participation due to the lifting of fish advisories as a result
of implementation of the selected BAT options is also estimated. This estimate is based on the total
number of licensed recreational anglers (TLRA) used in the cancer risk assessment for mills with
advisories. The analysis estimates the increase in recreational angler participation by comparing the
potential TLRA after the lifting of the advisories with the estimated TLRA with the advisories in place.
The risk assessment assumes that the fishing habits of recreational anglers are affected by fish advisories,
whereas the habits of subsistence anglers remain unchanged.
As mentioned previously, the potential lifting of the existing advisories is projected by comparing modeled
fish tissue concentrations for the selected BAT options (using the two approaches described above) to the
state-specific advisory action levels or the cancer risk level (one state). The total number of licensed
anglers in counties bordering the fish advisory location is first multiplied by 0.95 to estimate the number
of licensed recreational (as opposed to subsistence) anglers in these counties. This product is multiplied
by the ratio representing an estimate of the fraction of all licensed recreational anglers who actually fish
on the receiving stream in question. As mentioned previously, this ratio is 0.29. For receiving streams
with fish advisories, this product is then multiplied by 0.80 (the estimated percent of recreational anglers
who continue to use a receiving stream in spite of the presence of a fish advisory). If it is estimated that
after implementation of selected BAT options the fish advisory could be lifted, the 0.80 multiplier is not
used, thereby increasing the potential recreational angler participation on that particular receiving stream
segment by 20 percent. The result represents the estimated number of recreational anglers using the
receiving streams for their fishing activities when advisories are in place and after they are lifted.
The equations used for this analysis are:
TLRA with advisory = total licensed anglers (TLA) * 0.95 * 0.29 * 0.80
TLRA without advisory = total licensed anglers (TLA) * 0.95 * 0.29
Three of the receiving streams that currently have dioxin-related fish advisories in place also have
advisories in place in the same locations for other contaminants: two have advisories in place for mercury
and PCBs, and the third has an advisory in place for mercury. These contaminants are not being regulated
by the proposed pulp, paper, and paperboard rule. As a result, even if the dioxin-related advisories are
lifted as a result of BAT implementation, advisories for the other contaminants of concern will remain in
place. The populations of recreational anglers fishing these streams, therefore, are assumed not to change
as a result of the lifting of the dioxin-related advisories.
39
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40
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5. RESULTS
5.1 Aquatic Life Impact Assessment
The aquatic life-related benefits analyzed for this environmental assessment include the reduction of
exceedances of contaminant-specific aquatic life water quality criteria or toxicity concentrations for the
protection of aquatic life (aquatic life AWQCs). The aquatic life assessments involve comparing mill-
specific modeled in-stream contaminant concentrations to both acute and chronic aquatic life AWQCs for
101 bleaching mills (Table 5-1). Twenty-four pollutants are analyzed for acute impacts, and 26 pollutants
are analyzed for chronic impacts under baseline conditions and selected BAT options. Detailed results
(including all evaluated options) are provided in Attachments A-8 through A-l 1. Mill-specific results are
considered confidential business information (CBI) and are part of the CBI record.
Two mills in the bleached papergrade kraft/soda subcategory are projected to exceed the acute aquatic life
AWQCs for pentachlorophenol under baseline conditions (Table 5-1). After the implementation of the
selected BAT options, however, no acute AWQCs are projected to be exceeded.
At baseline conditions the chronic aquatic life AWQCs are projected to be exceeded at 28 mills
(Table 5-1) for the following 9 chlorinated organics:
4-Chlorocatechol
Pentachlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
3,4,5,6-Tetrachloroguaiacol
3,4,5-Trichloroguaiacol
4,5,6-Trichloroguaiacol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Not all of the 28 bleaching mills that exceed aquatic life AWQCs exceed them for all 9 contaminants.
Excluding one mill in the bleached papergrade kraft/soda subcategory that exceeds the chronic AWQC
for 2,3,7,8-TCDD, the implementation of the selected options for the dissolving kraft and bleached
papergrade kraft/soda subcategories eliminates chronic AWQC exceedances. There are no projected
Table 5-1. Estimated Number of Pollutants and Mills Exceeding Aquatic Life AWQCs
DK
PK
DS
PS
DK
PK
DS
PS
Baseline
1(2)
3(1)
9(27)
Selected BAT Option
0
0
KD
0
Total Number of Pollutants and
Mills (in parenthesis) with
Exceedances
Baseline = 1(2)
Selected BAT Options = 0
Baseline = 9(28)
Selected BAT Options = 1(1)
41
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exceedances of aquatic life AWQs for facilities in the dessolving sulfite subcategory under baseline or
under the selected BAT option conditions.
The selected BAT option for the papergrade sulfite subcategory is totally chlorine-free processes. The
implementation of such processes is assumed to completely eliminate the formation of chlorinated
organics, as well as to eliminate all of the projected aquatic life impacts at baseline conditions.
5.2 Human Health Impact Assessment
Impacts to human health are evaluated using site-specific analyses for baseline conditions and for the
conditions that are estimated to be achieved with the implementation of the selected BAT options. Human
health benefits are quantified by (1) comparing estimated in-stream concentrations to health-based water
quality toxic effect values (referred to in this document as health-based AWQCs), (2) estimating the
potential reduction of carcinogenic risk and noncarcinogenic hazards from the consumption of fish tissue;
(3) estimating the annual incidence of cancer in the potentially exposed angler population; and
(4) estimating the number of existing dioxin-related state fish advisories that could potentially be lifted
after the implementation of the selected BAT options. Also estimated is the potential increase in
recreational angler participation due to the lifting of fish advisories as a result of the implementation of
the selected BAT options. Detailed results (including all evaluated options) are provided in Attachments
A-12 through A-26. Mill-specific results are confidential and are provided in the CBI record.
5.2.1 Comparison with AWQCs for the Protection of Human Health
The water quality-related benefits analyzed for the environmental assessment include the reduction in the
number of exceedances of human health-based water quality toxic effect concentrations (health-based
AWQCs) for the protection of human health. Mill-specific modeled in-stream contaminant concentrations
are compared to AWQCs derived for the protection of human health from (1) ingestion of aquatic
organisms and (2) ingestion of water and aquatic organisms for baseline conditions and under selected
BAT options (Table 5-2). Detailed results are provided in Attachments A-12 through A-14. Mill-specific
results are confidential and are provided in the CBI record.
Modeled receiving water concentrations for 97 of a total of 100 mills are projected to exceed AWQCs for
human health for both organisms and water and organisms at baseline conditions for 5 and 8 pollutants,
respectively (Table 5-2). The AWQCs for protection from the ingestion of contaminated organisms only
are exceeded for the following five contaminants:
• Chloroform
• Pentachlorophenol
• 2,3,7,8-TCDD
• 2,3,7,8-TCDF
• 2,4,6-Trichlorophenol
However, not all 97 mills exceed the AWQCs for all 5 contaminants (Attachment A-12).
The selected BAT totally chlorine-free process change option for the papergrade sulfite subcategory
eliminates all projected baseline health-based AWQC exceedances for the ingestion of organisms. The
selected BAT options are also projected to reduce the number of mills with exceedances in the dissolving
42
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Table 5-2. Estimated Number of Pollutants and Mills Exceeding Health-Based AWQCs
BAT Process Change Options •
Baseline
Selected BAT Option
Total Number of Pollutants and
Mills (in parenthesis) with
Exceedances
Number of Pollutants and Mills (in parenthesis) with Projected AWQC Exceedances -
Human Health {Organisms)
DK "
3(3)
2(2)
PK
5(80)
2(71)
DS
2(5)
2(5)
PS
2(9)
0
Baseline = 5(97)
Selected BAT options = 2(78)
Human Health (Water and Organisms) :
DK""
7(3)
3(2)
PK
8(80)
4(71)
'DS -'
4(5)
4(5)
- JPS'"
4(9)
0
Baseline = 8(97)
Selected BAT Options = 5(78)
kraft, bleached papergrade kraft/soda, and dissolving sulfite subcategories to 78 and the number of
contaminants with projected exceedances to 2: 2,3,7,8-TCDD and 2,3,7,8-TCDF.
Three additional pollutants, for a total of eight, are projected to exceed the health-based AWQCs for
protection from the ingestion of contaminated water and organisms under baseline conditions:
• Chloroform
• 4-Chlorophenol
• 2,6-Dichlorophenol
• Methylene chloride
• Pentachlorophenol
• 2,3,7,8-TCDD
• 2,3,7,8-TCDF
• 2,4,6-Trichlorophenol
However, not all mills exceed the AWQCs for all eight contaminants (Attachment A-12).
All projected baseline exceedances for the papergrade sulfite subcategory are eliminated with the
implementation of the selected totally chlorine-free BAT option. The selected BAT options also reduce
the number of mills exceeding AWQCs in the dissolving kraft, bleached papergrade kraft/soda, and
dissolving sulfite subcategories at baseline to 78 and the number of contaminants to 5:
• Chloroform (DS mills only)
• 2,6-Dichlorophenol (PK mills only)
• Pentachlorophenol
• 2,3,7,8-TCDD
• 2,3,7,8-TCDF
Not. all the mills exceed the AWQCs for ingestion of water and organisms for all five contaminants
(Attachment A-12).
43
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5.2.2 Potential Carcinogenic Risk
As outlined in Chapter 4 (Methodology), two approaches are used to determine 2,3,7,8-TCDD and 2,3,7,8-
TCDF concentrations in fish tissue and the potential increased cancer risk associated with these
contaminants for 100 mills. Only the simple dilution approach is used to estimate fish tissue concentration
and potential increased cancer risk associated with four other probable carcinogens (i.e., chloroform,
methylene chloride, pentachlorophenol, and 2,4,6-trichlorophenol). Using the simple dilution approach,
it is estimated that 2,3,7,8-TCDD and 2,3,7,8-TCDF contribute more than 99 percent of the cancer risk
(Attachment A-23).
The simple dilution approach is a conservative methodology that assumes that all carcinogenic pollutants
discharged to a receiving stream, including the dioxins and furans, are available to the biota, particularly
fish. The Dioxin Reassessment Evaluation (DRE) Model approach, developed by EPA's Office of
Research and Development (still under EPA review), assumes that the bioavailability of dioxins and furans
is dependent on the levels of suspended solids in the discharge and the receiving stream and the
partitioning of contaminants between the sediment and fish tissue. The DRE approach is applicable for
evaluating 2,3,7,8-TCDD and 2,3,7,8-TCDF only; therefore, the other four contaminants are evaluated
using the simple dilution approach. Because of the use of two models, the results are presented as a
range, with the DRE model representing the lower end of the risk and the simple dilution approach
representing the upper end.
The subcategory-specific results, including both the projected individual cancer risks and the projected
number of individual annual cancer cases for recreational and subsistence anglers under baseline and
selected BAT option conditions, are summarized for the DRE approach and simple dilution approach
(Tables 5-3 and 5-4, respectively). Detailed results are provided in Attachments A-17 through A-20.
Mill-specific results are confidential and are provided in the CBI record.
Table 5-3. Average Individual Lifetime Cancer Risk and Annual Increased Incidence of Cancer
for Recreational and Subsistence Anglers at Baseline and Selected BAT
Estimated Using the DRE Approach
Proofs*
Change
Option
Baseline
Selected
BAT
Option
Potential Increased Average Individual Cancer Risk Over a Lifetime :
Recreational Anglers
DK
1.5E-03
3.7E-05
PK
I.8E-04
1.7E-05
DS
1.2E-04
9.3E-5
Baseline avg (4 subcategorics) =
Combined BAT avg for DK,
DS = 2.2E-05
" ~ . <-,-
PS
3.3E-OS
0
2.0E-04
PK,and
*•? - " . """"„-„
- Subsisteace Aagle*sL/«;v
, DK
1.9E-02
5.0E-04
PK -
2.4E-03
2.2E-04
[Potential Increased Incidence of Cancer in Ejjwstd:'
. " <• '•-""< Population ~,f,~I, """'
-.J'ReereMon^jiiigtBrs <•„
""DS ps
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Table 5-4. Average Individual Lifetime Cancer Risk and Annual Increased Incidence of Cancer
for Recreational and Subsistence Anglers at Baseline and Selected BAT
Estimated Using the Simple Dilution Approach
Baseline
7.3E-03
8.8E-04
4.9E-04
8.2E-OS
8.6E-02
1.1E-02
6.6E-03
UE-03
0.7
19.28
0.53
0.18
0.55
15.73
0.38
0.14
Selected
BAT
Option
3.4E-04
6.7E-05
3.6E-04
4.5E-03
9.1E-04
4.8E-03
0.04
0.91
0.5
0.03
0.70
0.35
Baseline avg (4 subcategories) = 9.4E-04
Combined BAT avg for DK, PK, and
DS = 9.2E-05
Baseline avg (4 subcategories) = 1.2E-02
Combined BAT avg for DK, PK, and DS
= 1.2E-03
Baseline total = 20.69
Total at selected BAT =
1.45
Baseline total = 16.80
Total at selected BAT =
1.08
Increased Cancer Cases Per Year for Recreational and Subsistence Anglers at Baseline Conditions
and After Proposed BAT Process Changes, and the Number of Cancer Cases Eliminated After the
Proposed BAT Process Change Options Are in Place
Recreational and Subsistence Anglers Baseline Total =
37.49
Recreational and Subsistence Anglers BAT Total = 2.53
Cancer Cases Eliminated for Recreational and
Subsistence Anglers = 34.96
5.2.2.1 DRE Model. Using the DRE model, projected increased average individual cancer risk for
recreational anglers at baseline conditions ranges from 10~3 (dissolving kraft) to 10~5 (papergrade sulfite)
and the average recreational angler risk for all four bleaching subcategories under baseline conditions is
estimated to be at the 10"4 level (Table 5-3). The projected baseline cancer risk associated with the
bleaching mills in the papergrade sulfite subcategory is eliminated with the implementation of the totally
chlorine-free selected BAT option. Under the selected BAT options, the average combined risk for mills
in the dissolving kraft, bleached papergrade kraft/soda, and dissolving sulfite subcategories is reduced to
a level of 10~5. The total increased annual incidence of cancer cases in the recreational angler population
across the four bleaching subcategories at baseline conditions is estimated to be 3.20. This total is reduced
to 0.47 after the selected BAT options are in place.
For the subsistence angler population, using the DRE approach the estimated increased average individual
cancer risk at baseline conditions ranges from 10"2 (dissolving kraft) to 10" (papergrade sulfite) and the
average risk level is estimated to be 10~3 for the four bleaching subcategories. The selected totally chlorine
free BAT option eliminates the risk for the papergrade sulfite mills, and the estimated combined risk for
the dissolving kraft, bleached papergrade kraft/soda, and dissolving sulfite mills is reduced to a level of
10"4. The total increased annual incidence of cancer in the subsistence angler population for all four
subcategories is estimated to be 2.67 under baseline conditions, and it is reduced to 0.36 after the selected
BAT options are in place. For the combined recreational and subsistence angler population, the selected
BAT options are projected to eliminate about five cancer cases per year.
5.2.2.2 Simple Dilution Model. Using the simple dilution approach, the average estimated increased
individual baseline cancer risk for all four subcategories for recreational anglers is at the 10"4 level (Table
5-4), and the estimated risk ranges from 10~3 (dissolving kraft) to 10"5 (papergrade sulfite). The selected
BAT options are projected to reduce the combined risk for dissolving kraft, bleached papergrade kraft/
soda, and dissolving sulfite mills to a level of 10"5 and completely eliminate the risk associated with mills
in the papergrade sulfite subcategory. The estimated total annual incidence of cancer across all
45
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subcategories for recreational anglers is reduced from 20.69 at baseline to 1.45 after selected BAT option
implementation.
The estimated increased individual average cancer risk to subsistence anglers under baseline conditions
ranges from 10'2 (dissolving kraft and bleached papergrade kraft/soda) to 10'3 (dissolving sulfite and
papergrade sulfite) and averages 10'2 for the four bleaching subcategories. After selected BAT option
implementation, the combined estimated cancer risk for dissolving kraft, bleached papergrade kraft/soda,
and dissolving sulfite mills is reduced to the 10'3 level. The totally chlorine-free BAT option proposed
for the papergrade sulfite subcategory completely eliminates the estimated baseline cancer risk for this
subcategory. The projected total increased annual incidence of cancer cases for subsistence anglers is
reduced from a four-subcategory total of 16.80 at baseline to 1.08 after the implementation of the selected
BAT options. For the combined recreational and subsistence angler population, implementation of the
selected BAT options is estimated to eliminate about 35 cancer cases per year.
A comparison of the two approaches used in this assessment indicates that the number of cancer cases per
year estimated by the simple dilution approach is higher than that estimated by the ORE model. The
simple dilution model estimates total cancer cases per year for all four subcategories and exposed
populations to be 37.49 at baseline conditions and 2.53 after selected BAT option implementation. In
comparison, the DRE model predicts a baseline value of 5.87 cancer cases per year and a reduction to 0.83
after selected BAT option implementation. Combining the results of both modeling approaches,
implementation of the selected BAT options is estimated to eliminate about 5 to 35 cancer cases per year.
5.2.3 Potential Noncarcinogenic Hazard
The potential noncancer hazard associated with the discharge of 11 systemic toxicants from 100 bleaching
pulp and paper mills are also evaluated for recreational and subsistence angler populations. This hazard
is estimated by using the simple dilution approach and the DRE model approach to estimate concentrations
of 2,3,7,8-TCDD and 2,3,7,8-TCDF in fish tissue and to determine the number of mills and contaminants
for which the RfDs are exceeded. Nine other systemic pollutants of concern are also included in the
simple dilution analysis:
Acetone
2-Butanone
Chloroform
4-Chlorophenol
2,4-Dichlorophenol
Methylene chloride
Pentachlorophenol
2,3,4,6-Tetrachlorophenol
2,4,5-Trichlorophenol
The subcategory-specific results for the DRE and simple dilution models for baseline and selected BAT
options are summarized below (Table 5-5). Detailed results are provided in Attachments A-21 through
A-26. Mill-specific results are confidential and are provided in the CBI record.
5.2.3.1 DRE Model. The estimated number of mills exceeding the 2,3,7,8-TCDD and 2,3,7,8-TCDF RfDs
for recreational anglers for the 4 bleaching subcategories is reduced from 34 mills under baseline
conditions to 7 (an 79,percent reduction) after the implementation of the selected BAT options (Table 5-5).
The selected BAT totally chlorine-free option for papergrade sulfite mills results in the complete
elimination of baseline exceedances for two mills. Of the seven mills projected to exceed RfDs after the
implementation of the selected BAT options, one is a dissolving kraft mill, four are bleached papergrade
kraft/soda mills, and two are dissolving sulfite mills.
46
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Table 5-5. Number of Pollutants and Mills (in Parenthesis) Exceeding RfDs for
Recreational and Subsistence Angler Populations Estimated Using
the Simple Dilution and DRE Approaches
•3. - Sr;
• Proce$i'€£atttge :
>-~';OjjScm ' y,'j
Baseline
Selected BAT
Option
Total Number of
Mills with
Exceedances
"- '^'"'l','^ -t'~~\ -^uj^fof?^^^^ '„• ,^F:,; ;;;,
..£• s-2l* a" -^^atwijilA^eeS _*, ^ggi '•£?.' t.
"•P'.-'xr 'O^l-; -''-'-',-,? -""«'
/,-DK"-
2(1)
1(1)
' **?
2(29)
1(4)
£&&<';-
2(2)
1(2)
"PS;
2(2)
0
Baseline = 34
Selected BAT Options = 7
% Reduction = 79
„ P7 SSwpte'Dnuteyy?; ':<;°
i-DST
2(1)
1(0
"•Pfe
3(54)
1(17)
'o&,~.
2(5)
1(4)
-'^
1(4)
0
Baseline = 64
Selected BAT Options = 22
% Reduction = 66
'-^4/Mfei''"'" „; ', .^jrSMbstsleoee Aijgijf^" j,;txs^^.t?'A*r _,'^^c,
^Sf£:s,i»E^l,:a:;;
"ksc-
2(2)
KD
iC-w
2(57)
2(17)
t$&
2(5)
2(4)
§Pt;
2(4)
0
Baseline = 68
Selected BAT Options = 22
% Reduction = 68
•t'/ -.Simpe'-DaiitioV ,,3K'
syjNsC'
2(2)
2(2)
>?$£',
4(70)
2(45)
1 J>S,'l'
2(5)
2(5)
«BS -
2(7)
0
Baseline = 84
Selected BAT Options = 52
% Reduction = 38
For subsistence anglers, the estimated number of mills exceeding 2,3,7,8-TCDD and 2,3,7,8-TCDF RfDs
for the 4 bleaching subcategories using the DRE approach is reduced from 68 at baseline conditions to
22 (a 68 percent reduction) after the implementation of the selected BAT options. The selected BAT
totally chlorine-free option for papergrade sulfite mills results in the complete elimination of baseline
exceedances for four mills. Of the estimated 22 mills exceeding RfDs after the implementation of the
selected BAT options, 1 is a dissolving kraft mill, 17 are bleached papergrade kraft/soda mills, and four
are dissolving sulfite mills.
5.2.3.2 Simple Dilution Model. Using the simple dilution approach, the estimated number of mills
exceeding RfDs for recreational anglers for the 4 bleaching subcategories is reduced from 64 mills under
baseline conditions to 22 (a 66 percent reduction) after the implementation of the selected BAT options
(Table 5-5). The proposed BAT totally chlorine-free option for papergrade sulfite mills results in the
complete elimination of baseline exceedances for four mills. Of the estimated 22 mills exceeding RfDs
after the implementation of the selected BAT options, 1 is a dissolving kraft mill, 17 are bleached
papergrade kraft/soda mills, and four are dissolving sulfite mills.
For subsistence anglers, the estimated number of mills exceeding RfDs for the 4 bleaching subcategories
using the simple dilution approach is reduced from 84 at baseline conditions to 52 (a 38 percent reduction)
after implementation of the selected BAT options. The selected BAT totally chlorine-free option for
papergrade sulfite mills results in the complete elimination of baseline exceedances for seven mills. Of
the estimated 52 mills exceeding RfDs after the implementation of the selected BAT process change
options, 2 are dissolving kraft mills, 45 are bleached papergrade kraft/soda mills, and five are dissolving
sulfite mills.
Greater than 99 percent of the noncancer hazard estimated using the simple dilution approach can be
attributed to 2,3,7,8-TCDD and 2,3,7,8-TCDF (Attachment A-23). Only two bleached papergrade
kraft/soda mills exceed the RfD for 2,4,5-trichlorophenol, and four bleached papergrade kraft/soda mills
exceed the RfD for 4-chlorophenol under baseline conditions. All post-BAT exceedances are limited to
2,3,7,8-TCDD and 2,3,7,8-TCDF.
A comparison of the two modeling approaches used in the analyses indicates that the DRE model predicts
greater reductions in RfD exceedances overall. The estimated reduction in noncarcinogenic hazard
47
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exceedances for subsistence anglers is much larger using the DRE model: 68 percent using the DRE model
versus 38 percent using the simple dilution model. For recreational anglers, the DRE model estimates the
reduction of noncancer hazard exceedances to be 79 percent as opposed to 66 percent estimated using the
simple dilution approach.
5.2.3.3 Number of Anglers Potentially Exposed. The estimated number of people potentially
exposed to contaminant levels exceeding RfDs (Table 5-6) is based on the total number of
recreational/subsistence anglers and their family members who reside in counties bordering river reaches
into which bleaching mills discharge and for which exposure to fish tissue contaminant levels is predicted
to result in exceedances of RfDs for contaminants of concern. The total population exposed for each mill
is the same as that used to estimate the potential increased incidence of cancer. However, only those
populations potentially exposed to contaminants from mills for which RfDs are exceeded are counted.
It should be noted that this method results in an estimate that exceeds the actual number of people
expected to incur a noncancer effect. It reflects only the estimated number of people exposed to
contaminant levels that exceed RfDs. Using the DRE approach, there is a predicted 59.2 percent reduction
in the size of the population exposed to contaminant levels exceeding RfDs under selected BAT options
as compared to baseline conditions. There is a predicted 68.1 percent reduction using the simple dilution
approach.
5.2.4 Impacts of BAT Controls on Dioxin-Related Fish Advisories
As of June 1993 a total of 23 receiving streams (including open water bodies) into which 29 bleaching
mills discharge had dioxin-related fish advisories in place. With the exception of one dissolving kraft
facility and one papergrade sulfite facility, these mills are all in the bleached papergrade kraft/soda
subcategory. The impact of the selected BAT controls on these advisories is projected by comparing
modeled dioxin and furan fish tissue concentrations estimated for the selected BAT options (using the two
modeling approaches described in Section 4) to state advisory action levels or state-specific risk levels (as
appropriate) (Table 5-7).
The comparison of estimated fish tissue concentrations to state advisory action level is performed on 19
fish advisories related to bleaching pulp and paper mill facilities for selected BAT discharge levels only.
The comparison of estimated fish tissue concentrations to state advisory action levels cannot be done for
three receiving streams because they are located in states where risk-based advisories are issued based on
site-specific determination, not state action levels. However, the risk level used to issue one of the four
Table 5-6. Populations Potentially Exposed to Noncarcinogenic Hazards Under Baseline
Conditions and After Implementation of the Selected BAT Options,
Estimated Using the Simple Dilution and DRE Approaches
Baseline
Selected BAT Options
Percent reduction
DRE * ~ iT.. ,„, „
Recreational
Angler
511,488
210,387
„ Subsistence
-Angler «
51,363
19,534
."-Total
562,851
229,921
59.2%
" "" V:; „-„ lSfi»p>,t»i»«0o r—\-i>vP'"
" RecreaU<3na3
. < An$*ir.<
964,547
288,646
>SuW&0Tisr-
-A%ter x<
63,994
39,477
•f< ^c ' •/:*
'^^R*I£F>< "
1,028,541
328,123
68.1%
48
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Table 5-7. Number of Receiving Streams That Would Exceed State Fish Advisory Threshold
Limits Under Various BAT Options Estimated Using the Simple Dilution
and DRE Approaches
it£ Process Change Options '';.
Existing Advisories
Analyzed
Exceedances under Selected
BAT Option
Advisories Potentially
Eliminated at Selected BAT
• ;: ; 0RE • "\;
20
1
19
°:JSunple Dilation" < '-
20
6
14
advisories is known to be 10~5; therefore, this risk level is compared to the cancer risk estimated for that
particular mill. In addition, receiving stream flow data are unavailable for one receiving stream and
therefore in-stream contaminant concentrations cannot be calculated. The total number of advisories
evaluated is 20. These advisories are affected by discharges from 25 mills.
Implementation of the selected BAT options is projected to eliminate 19 dioxin-related fish advisories
using the DRE modeling approach and 14 advisories using the simple dilution approach (Table 5-7 and
Attachments 15 and 16).
There are limitations regarding fish advisories and the estimated reduction of advisories expected as a
result of the implementation of the selected BAT options. Estimated fish tissue concentrations after BAT
option implementation assume that the mills are the exclusive source of dioxins and furans; other potential
sources are not considered. In addition, although the discharge of dioxins and furans may cease,
contaminated sediments may continue to be a long-term source of contamination to the biota that live in
or on the sediment or that feed on sediments, as well as to those organisms which feed on contaminated
biota. Actual determinations of continued fish tissue contamination must be made on a site-specific basis.
For those fish advisories affected by discharges from more than one facility, no attempt is made to
estimate the cumulative effect of the combined discharges. Rather, each facility is evaluated separately
to determine whether the fish advisory threshold limits would be exceeded under proposed BAT limits.
An estimate is also made of the increase in recreational angler participation due to the lifting of dioxin-
related fish advisories after the implementation of the selected BAT options. As mentioned previously,
of the 20 fish advisories evaluated, 19 are predicted to be lifted under selected BAT options using the
DRE approach and 14 are predicted to be lifted using the simple dilution approach. However, using the
DRE approach, two of the receiving streams for which dioxin-related fish advisories are projected to be
lifted after BAT implementation will still have advisories in place for other contaminants (mercury and/or
PCBs). Using the simple dilution approach, one receiving stream for which the dioxin-related fish
advisory is projected to be lifted after BAT implementation will still have a nondioxin-related advisory
in place.
Based on the number of receiving streams that are projected to have dioxin-related fish advisories lifted
after BAT implementation and for which no other advisories for other contaminants are in place (i.e. 17
49
-------
advisories using the DRE approach and 13 advisories using the simple dilution approach), using the DRE
approach it is estimated that the number of recreational anglers using receiving streams that currently have
dioxin-related fish advisories in place may increase by 26,795 anglers (from an estimated 135,630 under
baseline conditions to 162,425 under BAT conditions) as a result of the lifting of fish advisories on the
receiving streams in question; the simple dilution approach predicts that the recreational angler
participation may increase by 25,759 anglers (from an estimated 135,630 under baseline conditions to
161,389 under BAT conditions (Attachment 7).
50
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6. LIMITATIONS AND UNCERTAINTIES
6.1 Limitations
The methodologies used for the water quality and environmental assessments are subject to certain
limitations and uncertainties. Some of the problems encountered in the analyses resulted from lack of
available data or lack of research to evaluate methodological assumptions.
For example, because a dilution factor is missing for one mill that discharges to an open water body, a
surrogate flow cannot be calculated. In addition, 1Q10 flow data are not available for five mills and
therefore 7Q10 flows are used to estimate acute aquatic life risks for those mills. No human health risk
estimates are calculated for the mill lacking HMF flow data. Neither potential risks to aquatic life nor
potential risks to human health are evaluated for one mill because contaminant loadings data are
unavailable.
Every effort was made to use methods and approaches that EPA considers to be standard practice. Certain
assumptions may still be required, however, for the evaluation of combined noncarcinogenic hazards from
exposure to a chemical mixture. EPA recommends summing chemical-specific hazard quotients to obtain
a hazard index (USEPA, 1989a). Using this approach assumes that chemical-specific noncarcinogenic
hazards are additive. Limited data are available for actually quantifying the potential synergistic and/or
antagonistic relationships between chemicals in a chemical mixture. Other areas of uncertainty are
inherently associated with the risk assessment process (USEPA, 1989a, 1989b) but will not be discussed
here. Key uncertainties identified during the environmental assessment are discussed below.
6.2 Uncertainties Associated With Risk Estimates
Several uncertainties specific to this study notably affect the results of the dioxin and furan risk
assessment. Ninety-nine percent of the estimated carcinogenic risks and noncarcinogenic hazards
calculated in this study can be attributed to 2,3,7,8-TCDD and 2,3,7,8-TCDF. Therefore, the assumptions
and methods used to analyze the dioxin and furan data will affect the interpretation of the results of the
regulatory impact analysis and comparisons. Areas of uncertainty relative to the dioxin and furan risk
assessment include:
• Bioconcentration factors used in the risk assessment;
• Use of one-half the EPA-designated detection limit to estimate loadings for all nondetect
congeners for each selected BAT option and to develop pollutant discharge levels;
• Aquatic life toxic effect values, cancer slope factors (ql*), reference doses (RfDs), and toxic
equivalency factors (TEFs), which are currently under review by EPA, used in the risk assessment.
The bioconcentration factor (BCF) of 50,000 used in these calculations for 2,3,7,8-TCDD is based on a
measured value from laboratory research on rainbow trout, a pelagic freshwater species having a lipid
content of approximately 7 percent (Cook et al., 1991). A higher BCF may be more appropriate for fish
with a higher lipid content. Bioconcentration factors for 2,3,7,8-TCDD may be estimated on the basis of
the ratio of 10,000 per 1 percent lipid when the total amount of the chemical in water is considered
(telephone conversation between P.M. Cook, USEPA, Duluth, MN, and Esther Peters, Tetra Tech, Inc.,
51
-------
February 17, 1993). The BCF of 8,000 used for 2,3,7,8-TCDF was based on the following rationale:
relative BCFs measured by Merhle et al. (1988) for TCDD (39,000) and TCDF (6,049) for the same
lowest exposure concentration of TCDD where fish were least affected, in the same species of fish, yield
a ratio of 6.45. Dividing 50,000 by 6.45 yields 7,752, which rounds to 8,000.
BCF values are dependent on the characteristics of individual chemicals. Bioconcentration is a partitioning
process between the lipids of the organisms and the surrounding water, and is based on the amount of
freely dissolved chemical available to fish through bioconcentration across the gills. BCFs, however, may
be affected not only by variations in lipid content of different fish species but also by age of the fish;
exposure level; how the concentration of the compound in water is measured (freely dissolved or total
chemical); low bioavailability (the dioxins are highly hydrophobic); dissolved organic carbon content of
the water (the higher the organic carbon content, the lower the bioavailability of hydrophobic chemicals);
organic carbon in sediments; slow uptake rates; migration patterns of fish; and other factors that may lead
to measured BCFs lower than those predicted.
EPA recommends that BCF values calculated from the log P-log BCF relationship be used in the
calculation of reference tissue and ambient concentrations (USEPA, 1991b). However, the report also
notes that methods for calculating BCF values do not include metabolism, which will reduce the BCF.
Thus, calculated BCFs will be conservative, and measured values may be necessary to obtain more precise
values for chemicals that are metabolized. Furthermore, uptake of strongly hydrophobic compounds such
as dioxins and furans will also be governed by bioaccumulation, the net uptake of the chemical from
exposure to food and sediments as well as water. Because of these factors, many of the TCDD/TCDF
congeners do not bioaccumulate in fish (Cook et al., 1991).
The simple dilution approach used in this analysis assumes that using the loadings for dioxins and furans
and mill-specific dilution factors allows estimation of an appropriate water concentration for these
chemicals and permits the use of BCFs. However, this approach ignores the complexity of the interactions
of these highly hydrophobic chemicals with sediment organic carbon and suspended particulates in the
effluent, resulting in reduced bioavailability, losses to sediments through sorption and deposition, and
losses from volatilization and photolysis reactions. Thus the simple dilution approach oversimplifies the
processes involved in the uptake of contaminants by fish.
A number of studies are currently under way to assess alternative measures of the potential for
accumulation of dioxins and furans in fish (bioaccumulation factors, bioavailability indices, biota-to-
sediment accumulation factors, regulatory bioaccumulation multipliers) based on water column and bottom
sediment concentrations that can be used in the absence of site-specific measurements (e.g., Sherman et
al., 1992; USEPA, 1993a). Therefore, the new model developed by EPA's Office of Research and
Development (which is still under EPA review) is also used in this assessment to calculate fish tissue
concentration by calculating the equilibrium between dioxin in fish tissue and dioxin adsorbed to the
organic fraction of sediments suspended in the water column. The use of the biota-to-sediment
accumulation factor (BSAF) should predict more consistently the bioaccumulation potential of these
chemicals, although some assumptions are still necessary (USEPA, 1993a). The BSAF is calculated based
on the following equation:
BSAF = "
52
-------
where:
BSAF = biota-to-sediment accumulation factor (unitless)
Cupid = concentration of contaminant in lipid of fish (mg/kg)
C,,,. = concentration of contaminant in bottom sediment organic carbon (mg/kg)
The BSAF used for 2,3,7,8,-TCDD in this assessment was 0.09, which was based on the BSAF estimated
for lake trout in Lake Ontario. A biota suspended solids accumulation factor (BSSAF) is similar to a
BSAF except that the organic carbon normalized concentration is that of suspended solids rather than
bottom sediments. EPA has stated that there are currently no data available for assignment of BSSAFs
(USEPA, 1993a). However, using data from Lake Ontario, EPA estimates that the BSSAF would be 0.3
for lake trout, which is three-fold higher than the BSAF estimated for lake trout in Lake Ontario (i.e.,
0.09). EPA, however, suggests the use of available BSAFs as a lower bound for BSSAFs (USEPA,
1993a). Therefore, for this assessment, the BSSAF for 2,3,7,8-TCDD is assumed to be the same as the
BSAF.
The loadings values for 2,3,7,8-TCDD and 2,3,7,8-TCDF used in this analysis included one-half detection
limit values for those contaminants which were not detected in the effluent. As shown in the simple
dilution results, 2,3,7,7-TCDD and 2,3,7,8-TCDF contributed the vast majority of the total carcinogenic
risk for all the selected BAT options. A significant portion of this risk is associated with the use of one-
half the EPA-designated detection limit for these congeners. A recent report by Loftus et al. (1992) noted
that the level of detection of the method used is important in the usefulness of the results for assessment
of human risk.
EPA is currently reassessing the human health risk associated with exposure to dioxin. The dioxin slope
factor and reference doses, as well as the TEF approach, used in this assessment are based on previously
published values and do not represent the results of the dioxin reassessment, which are currently being
developed.
The estimated reduction in fish consumption advisories resulting from process change implementation
determined in this study assumes that the pulp and paper mill effluents are the only source of 2,3,7,8-
TCDD and 2,3,7,8-TCDF. Furthermore, although the discharge of these compounds may cease or be
minimized, sediment contamination may continue for years, with pollutants continuing to accumulate in
organisms. Site-specific monitoring may be required to determine actual fish tissue concentrations and
to assess the appropriateness of fish consumption advisories following process changes.
An additional area of uncertainty involves the estimates of populations exposed to contaminated fish tissue.
For the purpose of this study, angler population estimates were based on data extrapolated from the
number of fishing licenses sold in counties bordering receiving stream reaches and creel survey data. The
actual number of people using these receiving streams for their fishing activities is not known. In
addition, the number of recreational anglers who change their fishing habits as a result of a fish advisory
is based on a few studies with relatively few data.
53
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54
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Reinert, R.E., B.A. Knuth, M.A. Kamrin, and Q.J. Stober. 1991. Risk assessment, risk management, and
fish consumption advisories in the United States. Fisheries 16(6):5-12.
Sherman, W.R., R.E. Keenan, and D.G. Gunster. 1992. A re-evaluation of bioconcentration and
bioaccumulation factors for regulatory purposes. J. Toxicol. Environ. Health 37:211-229.
Silbergeld, E.K. 1991. Carcinogenicity of dioxins. J. Nat. Cancer Inst. 83(17):! 198-1199.
Silverman, W.M. 1990. Michigan's sport fish consumption advisory: A study in risk communication.
M.S. thesis, University of Michigan, 103 pp.
Spitsbergen, J.M., J.M. Kleeman, and R.E. Peterson. 1988. 2,3,7,8-tetrachlorodibenzo-p-dioxm toxicity
in yellow perch (Perca flavescens). J. Toxicol. Environ. Health 23:359-383.
Spitsbergen, J.M., K.A. Schat, J.M. Kleeman, and R.E. Peterson. 1986. Interactions of 2,3,7,8-
tetrachlorodibenzo-p-dioxin (TCDD) with immune responses of rainbow trout. Vet. Immunol.
Immunopathol. 12:263-280.
Stockner, J.G., and A.C. Costella. 1976. Marine phytoplankton growth in high concentrations of pulpmill
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Thomann, R.V. 1989. Bioaccumulation model of organic chemical distribution in aquatic food chains.
Environ. Sci. Technol. 23(6):699-707.
Thut, R.N., and D.C. Schmiege. 1991. Processing mills. In Influences of forest and rangeland
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U.S. Census Bureau. 1992. U.S. 1990 Census Data. U.S. Census Bureau Public Relations Office,
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USEPA. 1984. Ambient water quality criteria for 2,3,7,8-tetrachlorodibenzo-p-dioxin. U.S. Environmental
Protection Agency, Office of Water Regulations and Standards, Washington, DC.
USEPA. 1987. The national dioxin study. U.S. Environmental Protection Agency, Office of Water
Regulations and Standards. Washington, DC.
57
-------
USEPA. 1988. USEPA/paper industry cooperative dioxin screening study ("Five Mill Study"). EPA-
440/1-88-025. U.S. Environmental Protection Agency, Office of Water Regulations and Standards.
Washington, DC. March.
USEPA. 1989a. Risk assessment guidance for Superfund. Volume I: Human health evaluation manual
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USEPA. 1989b. Assessing human health risk from chemically contaminated fish and shellfish: A
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Water Regulations and Standards, Washington, DC. August.
USEPA. 1990b. Summary of technologies for the control and reduction of chlorinated organicsfrom the
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Agency, Office of Water Regulations and Standards, Office of Water Enforcement and Permits,
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58
-------
USEPA. 1992c. Categorization assessment report for pulp and paper analytes detected during the long-
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pulp, paper, and paperboard point source category U.S. Environmental Protection Agency,
Washington, DC.
USEPA. 1993c. Estimating exposure to dioxin-like compounds. Vol. Ill: Site-specific assessment
procedures. Draft. U.S. Environmental Protection Agency, Office of Health and Environmental
Assessment, Exposure Assessment Group, Washington, DC. July.
Versar, Inc. 1993. Toxicity data for pulp and paper analytes. Versar, Inc., Springfield, VA.
Walsh, G.E., K.M. Duke, and R.B. Foster. 1982. Algae and crustaceans as indicators of bioactivity of
industrial wastes. Water Res. 16:879-883.
West, P.C., J.M. Fly, R. Marans, and F. Larkin. 1989. Michigan sports anglers fish consumption
survey, Supplement I, Non-response bias and consumption suppression effect adjustment. Natural
Resource Sociology Research Lab, Technical Report No. 2. School of Natural Resources, University
of Michigan, Ann Arbor. September.
Williams, J.D., M.L. Warren, Jr., K.S. Cummings, J.L. Harris, and RJ. Neves. 1993. Conservation status
of freshwater mussels of the United States and Canada. Fisheries 18(9):6-22.
59
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-------
-------
ATTACHMENT A-2. LIST OF THE RECEIVING STREAMS FOR THE 103 BAT
PULP AND PAPER MILLS
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-3. MILL-SPECIFIC EFFLUENT AJND RECEIVING STREAM
FLOWS USED IN THE ENVIRONMENTAL ASSESSMENT
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
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-------
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ATTACHMENT A-5. SUMMARIZATION OF CREEL SURVEY DATA
Harvest Rates and Exposed Population Multipliers
Receiving Stream
Angelina River, TX 398995 anglers/year
884436.5 Ibs harvested/year
(Not used because 884436.5/398995 = 2.2 Ibs/angler/year or 2.74 grams/angler/day
majority of anglers
from counties not
bordering receiving
stream segment)
Leaf River, MS
990 Ibs harvested/183 days
53 anglers/183 days
990 lbs/53 anglers = 18.7 Ibs/angler
(18.7 lbs/angler)/183 days = 0.10 Ibs/angler/day or 45.4 grams/angler/day
106 anglers (creel survey) *-extrapolated for a year
1630 total licensed anglers
106/1630 = 0.065
Chickasaw Creek, Al 748,702 Ibs harvested/year
3817 anglers/year
748,702/3817 = 196 Ibs/angler/year or 244 grams/angler/day
Two mills discharge
to the same receiving 3817 anglers (creel survey)
stream segment 23158 total licensed anglers
3817/23158 = 0.16
Tombigbee River, AL 632,947 Ibs harvested/year
1595 anglers/year
Three mills discharge
to different stream 632,947/1595 = 397 Ibs/angler/year or 494 grams/angler/day
segments, each within
the vicinity of the 1595 anglers (creel survey)
creel survey location 5525, 2304, 6305 total licensed anglers for mills 1, 2, 3 respectively
Mill 1
Mill 2
Mill 3
1595/5525 = 0.29
1595/2304 = 0.69
1595/6305 = 0.25
-------
ATTACHMENT A-5 (cont). A SUMMARIZATION OF CREEL SURVEY DATA
Exposed Population Multipliers (Harvest Rates Unavailable for these Mills)
Receiving Stream
Menaminee River, MI 358 anglers (creel survey)
24,446 total licensed anglers
358/24,446 = 0.015
Peshtigo River, WI
87 anglers (creel survey)
16,873 total licensed anglers
87/16,873 = 0.005
Wisconsin River, WI 13,154 anglers (creel survey)
21,335 total licensed anglers for mills 1 and 2, and
Three mills discharge 34,801 total licensed anglers for mill 3
to two separate stream
segments, each within
the vicinity of the
creel survey location
Mills 1 and 2
MiU 3
13,154/21,335 = 0.62
13,154/34,801 = 0.38
Lake Champlain, NY 1146 anglers (creel survey)
6282 total licensed anglers
1146/6282 = 0.182
-------
ATTACHMENT A-6. POTENTIALLY EXPOSED POPULATIONS DERIVED FROM
THE NUMBER OF TOTAL LICENSED ANGLERS FOR EACH MILL
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-7. RECREATIONAL ANGLER POPULATION ESTIMATES FOR
RECEIVING STREAMS WITH FISH ADVISORIES IN PLACE
4 * "'
Receiving Stream
Blackwater River (VA)
Houston Ship Channel (TX)
Kennebec River (ME)
Escatawpa River (MS)
Ouachita River (AR)
Escanaba River (MI)
Androscoggin River (ME)
Bayou La Fourche (LA)d
Red River (AR)
Fenholloway River (FL)
Codorus Creek (PA)
Neches River (TX)
Penobscott River (ME)
St. Louis River (MM)
Androscoggin River (NH)
Pacific Ocean (CA)d
Potomac River (MD)
Leaf River (MS)
Roanoke River (NC)
Rainy River (MM)
Pigeon River (NC)
Sacramento River (CA)d
Wisconsin River (WI)
TOTAL POPULATION
Total
Licensed
Anglers*
4,713
190,726
27,230
16,030
17,950
10,687
31,091
26,393
28,956
3,897
36,566
74,597
24,182
99,876
1,849
19,096
5,001
1,630
5,999
7,887
5,188
31,953
21,335
692,832
»•>"
# Anglers
w/Advisory*
1,039
42,036
6,001
3,533
3,956
2,355
6,852
—
6,382
859
8,059
16,441
5,330
22,013
408
_.
1,102
359
1,322
1,738
1,143
—
4,702
135,630
,." # Anglers
w/o „
Advisory*
1,298
52,545
7,502
4,416
4,945
2,944
8,566
_.
7,977
1,074
10,074
20,551
6,662
27,516
509
__
1,378
449
1,653
2,173
1,429
—
5,878
—
Advisory Lifted
, ,„ , After BAT?
'j&Kfir' '
Yes
Yes
Yes
Yes
Yes
Yes
Yes
_.
Yes
Yes
Yes
Yes
Yes
Yesf
Yes
_
Yes
Yes
Yes
No
Yes
—
Yesf
_.
SD
No
Yes
Yes
Yes
Yes
Yes
Yes
_
Yes
No
Yes
Yes
Yes
No
Yes
—
No
Yes
Yes
No
No
_
Yesf
—
.Population After BAT
7 E>RE -
1,298
52,545
7,502
4,416
4,945
2,944
8,566
_.
7,977
1,074
10,074
20,551
6,662
22,013
509
_.
1,378
449
1,653
1,738C
1,429
—
4,702
162,425
sb
l,039e
52,545
7,502
4,416
4,945
2,944
8,566
—
7,977
859e
10,074
20,551
6,662
22,013"
509
—
l,102e
449
1,653
l,738e
l,143e
—
4,702
161,389
a Total number of fishing licenses sold in counties bordering river reach where discharge occurs
b Total licensed anglers x 0.95 x 0.29 x 0.8
c Total licensed anglers x 0.95 x 0.29
d Evaluation not conducted
° Advisory not lifted after BAT implementation
f Advisory lifted for dioxin, but advisory still in place for other contaminants
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-------
-------
ATTACHMENT A-9. ESTIMATED NUMBER OF CONTAMINANTS
EXCEEDING AQUATIC LIFE AWQCs FOR EACH FACILITY
UNDER BASELINE CONDITIONS AND EACH EVALUATED
BAT OPTION BASED ON A SIMPLE
DILUTION ANALYSIS
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-10. ESTIMATED HIGHEST LEVEL OF EXCEEDANCE OF AQUATIC
LIFE AWQCs FOR EACH FACILITY UNDER BASELINE CONDITIONS
AND EACH EVALUATED BAT OPTION BASED ON A
SIMPLE DILUTION ANALYSIS
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
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ATTACHMENT A-13. ESTIMATED NUMBER OF CONTAMINANTS EXCEEDING
HUMAN HEALTH AWQCs FOR EACH FACILHTY UNDER BASELINE
CONDITIONS AND EACH EVALUATED BAT OPTION BASED ON
A SIMPLE DILUTION ANALYSIS
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-14. ESTIMATED HIGHEST LEVEL OF EXCEEDANCE OF HUMAN
HEALTH AWQCs FOR EACH FACILITY UNDER BASELINE CONDITIONS
AND EACH EVALUATED BAT OPTION BASED ON A
SIMPLE DILUTION ANALYSIS
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-15. COMPARISON OF STATE FISH TISSUE CONCENTRATION
THRESHOLDS FOR ISSUING FISH ADVISORIES TO ESTIMATED FISH
TISSUE CONCENTRATIONS DERIVED BY SIMPLIFIED DILUTION
ANALYSIS AND CONTAMINANT-SPECIFIC BCFS.
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-16. COMPARISON OF STATE FISH TISSUE CONCENTRATION
THRESHOLDS FOR ISSUING FISH ADVISORIES TO ESTIMATED FISH
TISSUE CONCENTRATIONS DERIVED BY DIOXIN REASSESSMENT
EVALUATION (USEPA/ORD) ANALYSIS
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-17. ESTIMATED INCREASED INDIVIDUAL CANCER RISKS AND
POTENTIAL INCREASED INCIDENCE OF CANCER IN EXPOSED
RECREATIONAL ANGLER POPULATIONS UNDER BASELINE
CONDITIONS AND EACH EVALUATED BAT OPTION
USING SIMPLE DILUTION APPROACH
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-18. ESTIMATED INCREASED INDIVIDUAL CANCER RISKS AND
POTENTIAL INCREASED INCIDENCE OF CANCER IN EXPOSED RECREATIONAL
ANGLER POPULATIONS UNDER BASELINE CONDITIONS AND EACH
EVALUATED BAT OPTION USING SIMPLE DILUTION APPROACH
TO ESTIMATE 2,3,7,8-TCDD AND 2,3,7,8-TCDF
FISH TISSUE CONCENTRATIONS
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-19. ESTIMATED INCREASED INDIVIDUAL CANCER RISKS AND
POTENTIAL INCREASED INCIDENCE OF CANCER IN EXPOSED SUBSISTENCE
ANGLER POPULATIONS UNDER BASELINE CONDITIONS AND EACH
EVALUATED BAT OPTION USING SIMPLE DILUTION APPROACH
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-20. ESTIMATED INCREASED INDIVIDUAL CANCER RISKS AND
POTENTIAL INCREASED INCIDENCE OF CANCER IN EXPOSED SUBSISTENCE
ANGLER POPULATIONS UNDER BASELINE CONDITIONS AND EACH EVALUATED
BAT OPTION USING DRE APPROACH TO ESTIMATE 2,3,7,8-TCDD
AND 2,3,7,8-TCDF FISH TISSUE CONCENTRATIONS
This table contains confidential business information (CBI)
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-21. ESTIMATED NONCANCER HAZARD QUOTIENTS
FOR INGESTION OF FISH UNDER BASELINE CONDITIONS AND
EACH EVALUATED BAT OPTION USING SIMPLE
DILUTION APPROACH
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
ATTACHMENT A-22. ESTIMATED NONCANCER HAZARD QUOTIENTS
FOR INGESTION OF FISH UNDER BASELINE CONDITIONS AND
EACH EVALUATED BAT OPTION USING DRE APPROACH TO
ESTIMATE 2,3,7,8-TCDD AND 2,3,7,8-TCDF FISH
TISSUE CONCENTRATIONS
This table contains confidential business information (CBI).
It has therefore been included in the CBI record.
-------
-------
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