BACKGROUND DOCUMENT
SUPPORTING THE LISTING OP
WASTES FROM THE PRODUCTION, RECOVERY, AND
REFINING OF COKE BY-PRODUCE8 PRODUCED FROM COAL
EPA Contract #68-WO-OC27
Prepared by:
Science Applications International Corporation
760OA Leesburg Pifc.e-.
Falls Church, VA 22043
Prepared for:
Ron Josephson
Listing Section
Characterization and Assessment Division
Office of Solid Waste
U.S. Environmental Protection Agency
401 M Street, S.W,
Washington, D.C. 20460
July 31, 1992
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LISTING BACKGROUND DOCUMENT FOR
COKE BY-PRODUCTS WASTES
K141 Process residues from the recovery of coal tar,
including tar collecting sump residues from the
production of coke or the recovery of coke by-products.
This listing does not include K087 (decanter tank tar
sludge from coking operations).
K142 Tar storage tank residues from the production of coke
from coal or from the recovery of coke by-products
produced from coal.
K143 Process residues from the recovery of light oil,
including those generated in stills, decanters, and
wash oil recovery units from the recovery of coke by-
products produced from coal.
K144 Wastewater sump residuess from light oil refining,
including, but not limited to, intercepting or
contamination sump sludges from the recovery of coke
by-products produced from coal.
K145 Residues from naphthalene collection and from the
recovery of coke by-products produced from coal.
K147 Tar storage tank residues from coal tar refining.
K148 Residues from coal tar distillation, including, but not
limited to, still bottoms.
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TABLE OF CONTENTS
Section
I. SUMMARY OF BASIS FOR LISTING
II. SOURCES OF THE WASTES
A. Profile of the Industries
1. Coke By-Products
a. Overview of Products and
Processes
b. Types of Plants
c. Number and Geographic Location of
Plants
d. Industry Production and Materials
Consumed
2. Tar Refining
a. Overview of Products and Processes
b. Number and Geographic Location of
Plants
c. Industry Production and Materials
Consumed
B. Production Processes and Sources of the
Wastes
1. Coke By-Products
2. Tar Refining
III. QUANTITIES AND COMPOSITION OF THE WASTES
A. Coke By-Products Process Residuals
1. Quantities of Process Sludges or Residuals
and Wastewaters
2. Concentrations of Constituents Present
in Process Sludges or Residuals and
Wastewaters
B. Tar Refining Process Residuals
1. Quantities of Process Sludges or
Residuals and Wastewaters
a. Tar Storage Tank Residues for
Tar Plants (K147)
b. Tar Distillation Residues (K148)
c. Tar Refining Wastewaters
2. Concentrations of Constituents
Present in Tar Refining Process Sludges
or Residuals and Wastewaters
li
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TABLE OF CONTENTS
(Continued)
Section
IV. WASTE MANAGEMENT PRACTICES
A. Waste Management Practices of Coke By-Products
Wastes Proposed for Listing
1. Process Residues from the Recovery of
Coal Tar (K141)
2. Tar Storage Tank Residues (K14 2)
3. Residues from Light Oil Processing
Units (K143)
4. Wastewater Treatment Sludges from Light
Oil Refining (K144)
5. Residues from Naphthalene Collection
and Recovery (K145)
B. Waste Management Practices of Tar Refining
Wastes Proposed for Listing
1. Tar Storage Tank Residues (K147)
2. Tar Distillation Residues (K148)
C. Wastewater Management Practices at Coke
By-Products and Tar Refining Facilities
D. Recycling
V. BASIS FOR LISTING
A. Summary of Basis for Listing
B. Waste Characterization and Selection of
Constituents of Concern
1. Approaches Considered for Evaluating Coke By-
Products and Tar Refining Wastes
a. Leaching Protocols
b. Groundwater Models
2. Evaluation of Coke By-Products and Tar
Refining Wastes for Listing
a. Tar Collecting Sump Residues (K141)
b. Tar Storage Tank Residues (K142)
c. Light Oil Processing Residues (K143)
d. Intercepting Sump Residues (K144)
e. Naphthalene Collection and Recovery-
Residues (K145)
f. Tar Storage Tank Residues (K147)
g. Tar Distillation Residues (K148)
iii
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TABLE OF CONTENTS
(Concluded)
Section
C. Mobility of Constituents of Concern
D. Persistence of Constituents of Concern
E. Health Effects of Constituents of
Concern
F. Mismanagement Case Histories
G. Conclusions
VI. REFERENCES
iv
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LIST OF TABLES
1. Constituents of Concern
2. List of Coke By-Products Plants
3. U.S. Coke Production by State and Plant Type
(1986 - 1988)
4. List of Tar Refining Plants
5. Estimated Nationwide Waste Quantities
6. Estimates of Tar Collecting Sump Residues (K14 1)
7. Estimates of Quantities of Tar Storage Tank
Residue for Coke Plants (K142)
8. Estimates of Quantities of Benzol Plant
Scrubber Residue (K143)
9. Estimates of Quantities of Wash Oil Purifier
Residue (K143)
10. Estimates of Quantities of Wash Oil Decanter
Muck (K143)
11. Estimates of Quantities of Light Oil
Intercepting Sump Residue (K144)
12. Estimates of Quantities of Final Cooler Residue
(K145)
13. Estimates of Quantities of Naphthalene Skimmer
Residue (K145)
14. Tar Collecting Sump Residues (K141)
v
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LIST OF TABLES
(Continued)
15. Tar Storage Tank Residues (K142)
16. Residues from Light Oil Processing (K143)
17. Intercepting Sump Residues from Light Oil Refining
(K144)
18. Naphthalene Collection and Recovery Residues (K145)
19. Coke By-Products Wastewaters
20. Estimates of Quantities of Tar Storage Tank
Residues for Tar Plants (K147)
21. Tar Storage Tank Residues (K147)
22. Tar Distillation Residues (K148)
23. Tar Refining Wastewaters
24. Waste Management Practices for Coke By-Products
Recovery Wastes
25. Waste Management Practices for Tar Refining Wastes
26. Comparison of Concentrations of Hazardous Constituents
in Coke By-Products Wastes Proposed for Listing (K141
through K145, K147, and K148) with Concentrations in K087
27. Coke and Coke By-Product Wastes: Constituents of
Concern and Range of Measured Concentrations
28. Tar Refining Wastes: Constituents of Concern and
Range of Measured Concentrations
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29 .
30 ,
31.
32 .
33
34
35
36
37
38
39
LIST OF TABLES
(Continued)
Organic TCLP Results - Tar Decanter Sludge (K087)
Organic TCLP Results - Tar Storage Tank Residue
(K142)
Organic TCLP Results - Light Oil Process Residues
(K143)
Organic TCLP Results - Intercepting Sump Sludge
(K144)
Organic TCLP Results - Process Residues from the
Final Cooler/Naphthalene Recovery Process (K145)
Organic TCLP Results - Tar Storage Tank Residue
(K147)
Organic TCLP Results - Tar Distillation Residue
(K148)
Basis of Listing: Health Effects of the
Constituents of Concern in K141
Basis of Listing: Health Effects of the
Constituents of Concern in K142
Basis of Listing: Health Effects of the
Constituents of Concern in K143
Basis of Listing: Health Effects of the
Constituents of Concern in K144
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LIST OF TABLES
(Continued)
40. Basis of Listing: Health Effects of the
Constituents of Concern in K145
41. Basis of Listing: Health Effects of the
Constituents of Concern in K147
42. Basis of Listing: Health Effects of the
Constituents of Concern in K148
43. Comparison of Estimated Drinking Well
Concentrations with Health-Based Levels in
Drinking Water for Constituents of K141
44. Comparison of Estimated Drinking Well
Concentrations with Health-Based Levels in
Drinking Water for Constituents of K142
45. Comparison of Estimated Drinking Well Concentrations
with Health-Based Levels in Drinking Water for
Constituents of K143
46. Comparison of Estimated Drinking Well Concentrations
with Health-Based Levels in Drinking Water for
Constituents of K144
47. Comparison of Estimated Drinking Well Concentrations
with Health-Based Levels in Drinking Water for
Constituents of K145
viii
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LIST OF TABLES
(Concluded)
48. Comparison of Estimated Drinking Well Concentrations
with Health-Based Levels in Drinking Water for
Constituents of K147
49. Comparison of Estimated Drinking Well Concentrations
with Health-Based Levels in Drinking Water, for
Constituents of K148
50. Ground Water Mobility and Persistence of Constituents
of Concern
ix
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LIST OF ABBREVIATIONS/ACRONYMS
General
CAG Carcinogen Assessment Group
CERCLA Comprehensive Environmental Response
Compensation and Liability Act
CFR Code of Federal Regulations
COG Coke Oven Gas
CRAVE Carcinogen Risk Assessment Verification
Endeavor
EPA Environmental Protection Agency
EPACML Environmental Protection Agency Composite Model
for Landfills
FR Federal Register
HEEFs Hypothetical Environmental Exposure Factors
IARC International Agency for Research on Cancer
MCLs Maximum Contaminant Levels
NA Not Analyzed
ND Compound was analyzed but not detected.
NPL National Priorities List
NR Not Reported
NTP National Toxicology Program
OLM Organic Leachate Model
OSW Office of Solid Waste
PAHs Polynuclear Aromatic Hydrocarbons
x
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r t nm r>TJ iv t>Tin nrtr % m t- /~s * t ^ /^* >*-i t~> <-« * »» r» » ».
uioi w*¦ nuixuj ? ini i\jno/ nunun ino
General
POTW Publicly Owned Treatment Works
QA/QC Quality Assurance/Quality Control
RA Regional Administrator
RCRA Resource Conservation and Recovery Act
RfDs Reference Doses
RSDs Risk Specific Doses
TC Toxicity Characteristic
TCLP Toxicity Characteristic Leaching Procedure
TEFs Toxicology Equivalence Factors
TR Trace
Units
atm Atmospheres
° C Degrees Celsius
cf Cubic Feet
cm Centimeter(s)
cm2 Square Centimeter(s)
cm3 Cubic Centimeter(s)
*F Degrees Fahrenheit
g/kkg Grains Per Thousand Kilograms
kg Kilogram(s)
kg/m3 Kilograms Per Cubic Meter
xi
-------
Units
kkg
L
1/m3
1/yr
m
2
m
3
III
m3/yr
mg
mg/kg
mm
ppb
ppro
ug/1
yr
LIST OF ABBREVIATIONS/ACRONYMS
(Continued)
Thousand Kilograms (metric ton)
Liter(s)
Liters Per Cubic Meter
Liters Per Year
Meter(s)
Square Meter(s)
Cubic Meter(s)
Cubic Meters Per Year
Milligram(s)
Milligrams Per Kilogram
Millimeter(s))
Parts-Per-Billion
Parts-Per-Million
Micrograms per Liter
Year
xii
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SECTION I
SUMMARY OP BASIS FOR LISTING
EPA has found that certain residuals from the production,
recovery, and refining of coke by-products (K141 through K145,
K147, and K148) typically contain constituents that, when
mismanaged, pose a substantial present or potential threat to
human health and the environment due to their carcinogenic or
toxic properties. In addition, the Agency has compiled evidence
that these wastes contain toxic constituents that are mobile
and/or persistent in the environment and are therefore capable of
reaching receptors in harmful concentrations. The information
that supports these findings is presented in this Background
Document and in other materials available in the RCRA Docket. As
shown in Table 1, the constituents of concern in these wastes
are: benzene and polynuclear aromatic hydrocarbons (PAHs),
including benz(a)anthracene, benzo(a)pyrene, benzo(b and k)
fluorantnene, chrysene, dibenz(a,h)anthracene, indeno(1,2,3-cd)
pyrene, and naphthalene. The constituents of concern were
selected based on two principal factors: their known toxicities
and their typical concentrations measured in the waste (see
Section V.B for details). The findings for each waste are
described below.
1
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TABLE 1
CONSTITUENTS OF CONCERN
CONSTITUENTS
K141
K142
K143
K144
K145
K147
Benzene
X
X
X
X
X
X
Benz(a)anthracene
X
X
X
X
X
X
Benzo(a)pyrene
X
X
X
X
X
X
Benzo(b and k)fluoranthene
X
X
X
X
X
V
/V
Chrysene
X
X
X
X
X
X
Dibenz(a,h)anthracene
X
X
X
X
X
Indeno(1,2,3-cd)pyrene
X
X
X
X
Naphthalene
X
X
X
X
V
4\.
X
NOTE: X indicates that the constituent has been found to be present at levels of
regulatory concern in the individual waste stream.
2
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Section 3001(e)(2) of HSWA requires that EPA determine whether to
list wastes from the coke by-products industry as hazardous. A
wide variety of materials fall within the scope of the term coke
by-products, including coal tar, creosote and other refined tar
products, light oil, naphthalene, phenol, and coke oven gas.
HSWA directed EPA to study the production, recovery, and refining
of these coke by-products and determine whether these processes
result in the generation of hazardous waste according to the
criteria in 40 CFR 261.11. EPA has extensively studied the coke
by-products industry and has made the determination, based on
this evaluation and pursuant to the HSWA mandate, to list as
hazardous the following seven wastes that are associated with the
production, recovery, and refining of coke by-products:
K141 Process residues from the recovery of coal tar,
including tar collecting sump residues from the
production of coke or the recovery of coke by-
products. This listing does not include K087
(decanter tank tar sludge from coking operations).
K142 Tar storage tank residues from the production of
coke from coal or from the recovery of coke by-
products produced from coal.
K143 Process residues from the recovery of light oil,
including those generated in stills, decanters, and
wash oil recovery units from the recovery of coke
by-products produced from coal.
K144 Wastewater sump residues from light oil refining,
including, but not limited to, intercepting or
contamination sump sludges from the recovery of
coke by-products produced from coal.
K14 5 Residues from naphthalene collection and from the
recovery of coke by-products produced from coal.
K147
Tar storage tank residues from coal tar refining.
3
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K148
Residues from coal tar distillation, including, but
not limited to, still bottoms.
These wastes (which are more fully described in Section II)
include process residues and storage tank, residues. The listings
being finalized do not include wastewaters from coke by-products
recovery. The Agency does not have sufficient data showing that
PAHs are typically and frequently present at concentrations of
regulatory concern and subsequently did not propose to list these
wastewaters as hazardous wastes. However, the Agency believes
that these wastewaters may be TC hazardous for benzene.
The Agency also did not propose to list process wastewaters from
the production of creosote (tar refining operations) as
hazardous. Sludges generated from the treatment of these
wastewaters are already regulated under Subtitle C of RCRA, since
they are listed hazardous wastes (EPA Hazardous Waste No. K035) .
According to the information available to the Agency, all units
in which these wastewaters are managed are either 1) wastewater
treatment tanks, which are excluded from permitting and interim
status standards under 40 CFR 264.1(g)(6) and 265.1(c)(10); or 2)
surface impoundments that are already regulated under Subtitle C
due to the generation of K03 5 from wastewaters placed in the
unit. EPA does not believe that any tar refining facility is
land disposing wastewaters. Thus, EPA concludes that no
additional environmental benefit would be derived from listing
these wastewaters as hazardous.
4
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The Agency has collected data showing that the wastes being
listed typically contain significant concentrations of hazardous
constituents that cause carcinogenic, mutagenic, teratogenic, and
chronically toxic effects in laboratory animals. The hazardous
constituents are mobile and persistent in the environment and,
thus, can reach environmental receptors in harmful concentrations
when the wastes are mismanaged. The Agency has evaluated these
wastes using the criteria for listing hazardous wastes, which are
identified in 40 CFR 261.11(a). The Agency has determined that
these wastes are hazardous because they contain toxic
constituents that are capable of posing a substantial present or
potential hazard to human health and the environment when
improperly treated, stored, transported, disposed, or otherwise
mismanaged.
The sources of the wastes being listed as hazardous are described
in Section II. Certain sections of the Background Document,
however, contain confidential business information (CBI) and are
not available to the public. EPA will accept petitions submitted
in accordance with 40 CFR Part 2 for declassifying CBI material.
Many of the residues being listed are recycled by a substantial
segment of the coke by-products industry. Two recycling
techniques are commonly used: (1) applying the residue to coal
prior to or just after charging the coal into the coke oven; and
5
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(«.!) mixing the rcSidiic with coai Cai piioi" i_o its being sold as 3
product.
To address both of these recycling practices, on June 22, 1992
(57 FR 27880), EPA excluded wastes from the coke by-products
process from the definition of solid waste when they are recycled
by being returned to coke ovens, placed into the tar recovery
process, or mixed with coal tar, provided there is no land
disposal of the recycled materials. See Section IV of this
Background Document for details.
6
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SECTION II
SOURCES OF THE WASTES
The following section presents a profile of the coke by-products
and tar refining industries and describes the manufacturing
processes for 1) the production and recovery of coke by-products,
and 2) tar refining.
A. Profile of the Industries
The coking industry most notably produces coke that is used in
the production of iron and steel. Additionally, the coke by-
products industry "co-produces" other products such as coke oven
gas, crude coal tar, and crude light oil. Coke by-products are
used as inputs in other industries, including the tar and light
oil refining industries. The following section profiles the
characteristics of the coke by-products and tar refining
industries. Because operations involving the production and
recovery of coke by-products and tar refining are usually
conducted at separate locations, the industry descriptions of
coke production and coal tar refining are discussed separately in
this section.
7
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1. Coke By-Products
The coking industry is composed of producers of coke and coke by-
products. This section presents a profile of the segment of the
coke by-products industry that is extensively integrated with the
steel industry (SIC 3312). Industry-owned or "captive" plants
produce the greatest share of coke and coke by-products.
Independent or "merchant" plants also exist, producing a
relatively small share of the overall industry's coke production.
The following sections describe selected characteristics of the
coke by-products industry, including products and processes.
a. Overview of Products and Processes
Coke is primarily used in the production of iron and steel. It
is produced as the carbon residue that results from heating coal
or other high-carbon material in the absence of oxygen. The two
basic types of coke produced are (1) furnace coke that is used as
a source of carbon and as a fuel in blast furnaces, and (2)
foundry coke that is used as a fuel in the cupolas of foundries.
Coke is the principal fuel burned in both iron and steel
manufacturing processes.
In 1988, approximately 90 percent of all the coke consumed in the
United States was used in blast furnaces, 5 percent was used in
foundries, and 5 percent was used by other industrial plants
8
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(DPRA, 1990) . Blast furnaces are used in steel mills to make raw
steel products including hot metal, pig iron, silvery pig iron,
and ferroalloys.
Coke production processes typically utilize coal in a
regenerative type of oven called the by-products oven
(technically, a co-products oven). The types of coal used and
the length of time the coal is heated (coking time) are
determined by the end use of the coke. Mixtures of both high and
low volatile coals are carbonized to produce either furnace or
foundry coke. Furnace coke generally is obtained from a coal mix
of 10 to 30 percent low volatile coals, whereas foundry coke is
obtained from a mix of 50 percent or more of low volatile coal.
The coking time for furnace coke averages about 18 hours while
foundry coke requires about 3 0 hours (DPRA, 1990).
b. Types of Plants
Two types of plants exist within the coking industry—captive and
merchant. Integrated iron and steelmaking plants own the captive
plants and consume nearly all their produced coke in the
production of steel in their blast furnaces. This allows the
plants to maintain greater control over the supply and cost of
the raw material needed in the production of iron and steel. In
the last quarter of 1988, about 84 percent of their furnace coke
9
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was used by the producing companies, and only 16 percent sold
commercially (DPRA, 1990).
Merchant plants are smaller independent firms that produce coke
for the commercial market. In the last quarter of 1988, the
producing companies consumed only two percent of their own
production, with 98 percent sold commercially fDPRA 199CM .
Foundries are the major consumers of this coke, using it to melt
iron and reduce iron oxide to iron prior to its casting.
Approximately 90 percent of total coke production is consumed in
blast furnaces associated with the backward-integrated iron and
steel plants, while only five percent is consumed by foundries.
The remaining 5 percent is off-specification coal tar for which
the particle size, hardness, or other properties rendered it
unusable in blast furnaces or foundries. Such coal tar may be
used to produce carbon black or boiler fuel.
c. Number and Geographic Location of Plants
Table 2 lists 30 of the 34 plants in operation in the United
States as of 1992. Twenty-three plants were classified as
captive and eleven as merchant. One plant does not recover by-
products. Table 2 also shows the city and state location of each
facility. There is a downward trend in the number of coke
10
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plants; there were 81 plants in 1960, 65 in 1980, and 40 in 1985.
The location of coke plants is dictated by several factors.
First, is the accessibility to needed raw materials. Thus, many
11
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TABLE 2
LIST OF COKE BY-PRODUCTS PLANTS
COMPANY CITY STATE TYPE
2.
Empire Coke Co.
Holt
AL
M
3.
Sloss Industries
Birmingham
AL
M
4.
Koppers Industries
Woodward
AL
M
5.
Gulf States
Gadsen
AL
C
6.
Acme Inc.
Chicago
IL
C
7.
LTV Steel Corp.
Chicago
IL
c
8.
National Steel Corp.
Granite City
IL
c
9.
Bethlehem Steel
Burns Harbor
IN
c
10.
Citizens Gas & Coke Utility
Indianapolis
IN
M
11.
Inland Steel #1
East Chicago
IN
c
12.
USX
Gary
IN
c
13.
Armco Inc.
Ashland
KY
c
14.
National Steel Corp.
Ecorse
MI
c
15.
Bethlehem Steel Corp.
Lackawanna
NY
c
16.
Tonawanda Coke Corp.
Tonawanda
NY
M
17.
Armco Inc.
Middletown
OH
r*
18.
Toledo Coke Corp.
Toledo
OH
M
19.
LTV Steel Co., #1
Cleveland
OH
C
20.
LTV Steel Co., #2
Warren
OH
C
21.
New Boston Coke Corp.
New Boston
OH
C
??
Bethlehem Steel
Bethlehem
PA
c
23.
Erie Coke Corp.
Erie
PA
M
24.
LTV Steel Co.
Pittsburgh
PA
c
25.
Shenango
Pittsburgh
PA
M
26.
USX
Clairton
PA
C
27.
Sharon Steel
Monessen
PA
c
28.
Geneva Steel
Geneva
UT
c
29.
Jewell Coke and Coal
Vansant
VA
M
30.
Wheeling-Pittsburgh
Follansbee
WV
c
12
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coke plants, in conjunction with the large integrated steel mills,
are sited in states with heavy deposits of coal. A second factor
is that the market for iron and steel products is shifting to the
West. Easy access to rail and water transportation is a third
factor. The American Iron and Steel Institute (AISI) provided the
Agency with updated information from early 1992 regarding the
locations of currently operating coke plants, as shown in Table 2.
Two-thirds of the plants are sited in states bordering the Great
Lakes, six plants in Pennsylvania, six in Ohio, six in Indiana, two
in Michigan, and three in Illinois. Alabama, accounting for five
plants, is the only major exception to this concentration.
d. Industry Production and Materials Consumed
The information presented in the proposed rule on the coking and
tar refining industries was based on data collected from RCRA 3007
Questionnaires (see Table 3) , which remain the most current and
accurate sources available to EPA on the industry. Only the
locations of currently operating coke plants have been updated.
These data indicate that the production of coke declined from 46
million tons in 1980 to 26 million tons in 1986 — a decrease of 45
percent. Production levels increased in 1987 and 1988. The 32
million tons produced in 1988 was the highest production level
since 1981. However, compared to the 1980 level, production is
still down by 30 percent.
13
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table 3
U.S. COKE PRODUCTION BY STATE AND PLANT TYPE
(1986 THROUGH 1988)
U.S Coke Production
1988
1987
1986
Amount
Percent
Amount
Percent
Amount
Percent
(000 MT)1/
(%)
(000 MT)1/
(%)
(000 MTU/
(%)
State
Alabama
2,324
7.9
2,117
83
1,790
7.7
Indiana
7,189
24.4
6,970
27.33
5398
23.3
Kentucky,Missouri
T ennessec,T exas
W
--
W
--
1,058
4.6
Michigan, Wisconsin
W
--
W
--
1,668
7.2
Ohio
4,288
14.6
4,126
16.2
3.535
15.2
Pennsylvania
6.803
23.1
5.308
20.8
4.534
19i
Other
S.855
30.0
6,966
27.4
5,235
22.5
Total U.S.
29,459 2/
100.0
25.4S7
100.0
23,218
100.0
Plant Tvdc
Merchant
3.516
11.9
3,228
12.8
2.990
12.9
Furnace
25,942
88.1
22.260
87.2
20,223
87.1
±! (000 MT) = thousand (metric tons)
2/ From October-December 1988 Quarterly Coal Report, the general production figure for 1988 is 29.2 million metric tons but
when broken down by state and plant type, production is shown at 29.5 million metric tons
W= Witneld to prevent disclosure of individual company data.
Source' DPRA Incorporated, 1990.
14
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Production has surpassed consumption some years and fallen short in
others. Nevertheless, stocks of coke have always been more than
adequate to offset any shortfall in production needs.
Table 3 shows coke production by states for the 1986-1988 period.
Indiana, Pennsylvania, and Ohio dominate, accounting for 24, 23,
and 15 percent of total coke production, respectively. These three
states accounted for 62 percent of the total production for 1988.
This table also shows that nearly 88 percent of coke is
produced in furnace coke plants with the remaining 12 percent
produced in merchant plants. A number of by-products of the
carbonization of coal are recovered at coke by-products facilities.
Coke oven gas, coal tar, light oil, naphthalene, phenols, and
ammonium sulfate represent the major by-products. The by-products
recovery processes vary from plant to plant, resulting in different
by-products recovered. However, U.S. production levels of these
coke by-products have declined over the decade as a result of
reduced coke production.
Coke oven gas is processed to remove coal tars, phenols,
naphthalene, and light oils. It is then used as a fuel for non-
contact heating of the coke ovens or in other processes in the coke
or steel plant. In 1985, about 1,200 million liters of coal tar,
3.7 million liters of sodium phenolate, 7,700 short tons of
naphthalene, and 580 million liters of light oil were produced by
coke plants.
15
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Tcti~ Refining
Tar refining operations are classified under SIC 3312, as are coke
by-products operations. Historically, coal tar refining was a part
of the coke by-products recovery operation at coke producing
facilities. However, most coke plants have eliminated their tar
refining operations. The crude coal tar that is produced at most
coke plants is now sold to independent tar refiners for the
production of other coal tar products. A tar refinery typically
purchases coal tar from one or more coke by-products plants.
a. Overview of Products and Processes
A number of refined products can be obtained from coal tar,
including the following:
The major products produced by all U.S. tar refiners are coal tar
pitch (53 percent of the 1989 aggregate industry estimated level of
production) and creosote oil (28 percent).
Tar refining primarily involves distillation processes that
separate the various products. Multiple distillation phases are
normally involved in order to capture light, middle, and heavy
creosote distillates. Both liquid and solid pitch fractions may
Coal tar pitch
Creosote oil
Naphthalene
Solvent naphtha
Refined tar
Other Droducts
16
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also be produced. Other processes such as distillation, scrubbing,
or precipitation are utilized to recover other coal tar products.
b. Number and Geographic Location of Plants
A total of six companies operate 12 tar refining plants in 1992.
Table 4 shows these plants and their locations in the U.S. As
indicated, these plants are distributed in ten states, many of
which also are leading states in coke by-products plants that
generate crude coal tar (i.e. . the primary feedstock for tar
refining plants). The number of tar refining plants appears to
have remained steady; however, many tar refining plants were owned
by coke facilities in 1984 and, thus, were not accounted for in
1984. A number of coke facilities may have sold tar refining
plants, while independent tar refineries have ceased operation.
c. Industry Production and Materials Consumed
Aggregate data for the 12 tar refining plants in operation in 1984
show that the industry had a crude tar refining capacity of
approximately 428 million gallons. However, the amount processed
was reported as approximately 258 million gallons or about 60
17
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rn i r» t a
1ADLLH
LIST OF TAR REFINING PLANTS
TAR REFINING COMPANY
CITY
STATE
1.
Aristech
Clairton
PA
2.
Koppers Tar
Woodward
AL
3.
Koppers Tar
Cicero
IL
4.
Reilly Tar
Granite City
rL
5.
Allied Tar
Detroit
MI
6.
Reilly Tar
Cleveland
OH
7.
Western Tar
Memphis
TN
8.
Koppers Tar
Houston
TX
9.
Reilly Tar
Lone Star
TX
10.
Witco Chemical
Point Comfort
TX
11.
Reilly Tar
Provo
UT
12.
Koppers Tar
Follansbee
wv
Source: DPRA Incorporated, 1990.
18
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percent of the overall production capacity (EPA RCRA 3007
Questionnaires, 1985). Utilization rates of at least
70 to 80 percent were achieved regularly during normal periods.
Examination of the same data for the 14 facilities still in
operation as of 1992 suggests an annual capacity of 336 million
gallons. Tar distillation rates for 1992 were 313.9 million
gallons, with 256.8 million gallons of crude coal tar produced by
coke plants in 1991 (ACCCI, 1992). It is assumed that the
additional crude coal tar was obtained through imports.
Crude coal tar is the primary raw material consumed in tar
refining. Substantial energy also is consumed to heat the crude
tar in various distillation processes and to transport cooling
water to condensers. Various wastewater streams are generated
including oil-water phases that must be separated prior to final
treatment.
The 1985 production of refined tar products was approximately 500
million liters of creosote oils, 550 million liters of refined tar
(excluding tar used as road tar), and 470,000 MT of tar pitch.
19
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B. Production Process and Sources of the Wastes
1. Coke Bv-Products
As stated earlier, coke by-products recovered from coke oven gas
include coal tar, naphthalene, light oil, and other marketable
products. Light oil is further fractionated to produce benzene,
toluene, and xylene. The by-products from the fractionation of
light oil to produce these products are not included in the final
listing of wastes from the coke by-products industry, since
benzene, toluene, and xylene are not by-products in the manufacture
of coke.
While coke-making operations vary somewhat with respect to the
products formed, oven size, and coking time, the general process is
common to all plants. Coke by-products recovery processes,
however, do vary from plant to plant and each plant is unique in
terms of the coke by-products recovered and the specific steps used
for coke by-products recovery. The most common processes involve
recovery of light oil and coal tar, as well as production of
ammonia, naphthalene, and phenol. Further refining of light oil
and coal tar also may occur at coke plants, but generally these
products are sent to off-site refiners for further processing. The
following process description provides an overview of the coke
production and coke by-products recovery process. For completeness
20
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and continuity, brief information on the sources of currently
listed wastes (i.e.. EPA Hazardous Waste Nos. K035, K060, and K087)
also is presented.
Figure 1 is a generalized process diagram and shows the points
where the listed wastes are usually generated. This process flow
diagram is presented for illustration purposes only, and wastes may
be generated at different points in the process at individual
facilities. As shown in Figure 1, coal is charged to the coke oven
and heated to temperatures between 7 00" and 900°C to produce coke
and coke oven gas (COG). Coking temperatures will vary with the
coking time, the rate of underfiring, the coal mixture, the
moisture content of the coal, and the desired properties of the
coke and coke by-products. In coke ovens, the carefully blended
coal charge is heated on both sides so that heat travels toward the
center, producing shorter and more solid pieces of coke. Air is
excluded so that no burning takes place within the oven; the heat
is supplied completely from the flues on the sides. The raw coke
oven gas exits the oven at temperatures ranging from 760° to 870°C
through the collecting main where it is sprayed with flushing
liquor. The flushing liquor, composed primarily of water, tar,
light oils, and heavy hydrocarbons, cools the coke oven gas to
temperatures between 80° and 100°C. At these temperatures, the tar
precipitates, and most of the nonvolatile organics condense from
the gas. Coal tar, water, and ammonia are carried with the
flushing liquor to the tar decanter tank (i.e., flushing liquor
-------
decanter tank) . The uncondensed gas flows from the collecting main
through crossover mains to the suction main, from which it enters
the primary cooler.
22
-------
Figure
-------
In the tar decanter tank, the material separates into three phases:
the top layer is a dilute ammonia flushing liquor; the middle layer
is coal tar; and the bottom layer contains heavy carbonaceous
deposits that were entrained with tar and liquor in the collecting
main. The accumulated carbonaceous deposits at the bottom of the
decanter tank are currently listed as EPA Hazardous Waste No. K087
(Decanter Tank Tar Sludge). This residue is continuously collected
by scrapers and is either recycled via ball mills or treated and
disposed. Dilute ammonia flushing liquor is skimmed from the top
of the mixture, and a portion of it is recycled back to the
collecting main. The flushing liquor system is a net generator of
water. The aqueous residue, generally called excess ammonia
liquor, is sent to the excess ammonia liquor tank. Phenols can be
extracted from the weak ammonia liquor by direct contact with a
countercurrent flow of light oil from the light oil recovery unit.
The phenolized light oil flows to the phenol column where the
phenols are removed by reaction with caustic (sodium hydroxide or
NaOH) t_ form sodium phenolate. The sodium phenolate and the
separated light oil fraction are both sold as by-products. Ammonia
also is recovered from the excess ammonia liquor stream. The waste
ammonia liquor resulting from the ammonia recovery is ultimately
sent to a wastewater treatment system.
The tar is drained from the middle layer of the tar decanter,
undergoes tar dewatering and then is stored. Tar dewatering
reduces the water content of the tar through the process of gravity
24
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separation. The water obtained from this process is sent to the
wastewater treatment system.
Over time, a tar residue (K142), accumulates at the bottom of the
tar storage tanks. This tar residue must be removed periodically
to maintain storage capacity.
The uncondensed gas that leaves the collecting main enters the
primary cooler where the gas temperature is reduced to
approximately 40°C. The temperature reduction causes condensation
of additional tar and liquor. Primary cooling is accomplished
directly, by contacting the gas with cooling liquor in a baffled
tower, or indirectly, by using a countercurrent water flow in a
heat exchanger. The condensate from the primary cooler flows into
a tar collecting sump and is discharged to a tar decanter. Tar
collection sump residue or sludge (K141) accumulates at the bottom
of the collecting sump and must be removed periodically. In most
cases, this residue is recycled to the flushing liquor decanter.
The gas that exits the primary cooler is compressed in an exhauster
and sent to an electrostatic precipitator (ESP) that removes
entrained coal tar. The coal tar typically is routed to the tar
collecting sump. In some facilities, tar from the primary cooler
and ESP is discharged directly into the flushing liquor decanter
tank, thereby eliminating the tar collecting sump.
25
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The recovery of ammonia from coke oven gas and excess ammonia
liquor is practiced at most coke by-products plants. Ammonia may
be recovered from the gas stream using either the direct or
indirect recovery process. The direct process involves contacting
the entire gas stream with a solution of sulfuric acid (H2SOJ in
an absorber to produce ammonium sulfate crystals (after a series of
drying and crystallization steps). When indirect ammonia recovery
is used, the gas is scrubbed with cooling water to absorb the
ammonia,, and the scrubbing liquor is distilled with steam in
ammonia stills to yield ammonia vapor. In many plants, the waste
ammonia liquor also is sent to the ammonia stills as a wastewater
treatment step. The ammonium sulfate crystals are either sold or
disposed, depending on market conditions.
The ammonia stills employ either caustic (NaOH) or lime (calcium
hydroxide, or Ca(OH)2) to react with any fixed ammonium salt to
render 'free' ammonia. Alternatively, lime can be added to the
ammonia liquor before it enters the ammonia still in a vessel
called a prelimer. Ammonia still lime sludge is generated in the
ammonia stills. This ammonia still lime sludge is currently listed
as EPA Hazardous Waste No. K060. No sludge is generated if only
NaOH is used in the process.
26
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Coke oven gas exiting the ammonia absorber (saturator) is sent to
the final cooler for naphthalene removal. Coke by-products plants
use one of two distinct processes for final cooling. The most
common method is direct contact final cooling (see Figure 2), which
uses water as a cooling medium. The alternative cooling process
uses wash oil as a cooling/collection medium in a counterflow
direction.
When water is used in the final cooler, naphthalene in the coke
oven gas condenses and must be removed from the recirculating
cooling water. The effluent stream from the final cooler is first
sent to a sump called the naphthalene separator where the
naphthalene is skimmed mechanically from the surface of the water.
Naphthalene collection and recovery residues (K145) accumulate at
the bottom of the naphthalene separator sump over a period of time.
From the separator sump, the water is discharged to a hot sump,
which acts as a collection or surge vessel for the cooling tower.
From the hot sump, the water is routed at a constant flow rate
through the cooling tower to a cold sump, which serves as a
collection or surge tank for the cooled water before it reenters
the final cooler. K145 residues also accumulate in the hot and
cold sumps and on the surfaces of the cooling tower.
Naphthalene also may be separated from the final cooler water by
sending the final cooler water through a layer of tar at the bottom
of the final cooler. This process, which is called a tar-bottom
27
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final cooler, iillows the naphthalene to uisbuivt; in the tar and to
be included with the tar in any further refining operation. The
same effect can be produced by sending the final cooler effluent
stream to the tar collecting sump where naphthalene dissolves in
the tar, and the water separates out by gravity. This separated
water can either be recycled back to the cooling process or sent
for wastewater treatment.
When the alternative wash oil cooling process is used, the material
recovered from the final cooler contains naphthalene and some light
oil. This stream is sent to a wash oil decanter (to remove
condensed water) and then to a wash oil circulation tank. Some of
the wash oil from the recirculation tank is recycled back to the
final cooler through an indirect heat exchanger. The remainder is
eventually routed to the light oil recovery plant (or benzol
plant) , which is described below, for removal of both the
naphthalene and the light oil.
After final cooling, the gas stream enters the light oil recovery
stage. The gas is scrubbed countercurrently with petroleum wash
oil in a scrubber called the light oil scrubber (or benzol plant
scrubber) to absorb the light oil. Materials that build up in this
scrubber over time are listed as light oil recovery residues (EPA
Hazardous Waste No. K143). From the scrubber, the 'benzolized'
wash oil is sent to the light oil stripping still or stripper to
separate the wash oil from the light oil. Light oil recovery
28
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residues (EPA Hazardous Waste No. K143) also include material that
accumulates in the still. Recovered light oil is then stored and
subsequently sold. The wash oil is recycled to the light oil
scrubber.
As the wash oil recycles through the light oil recovery process, a
high-boiling-point resin is formed through polymerization
reactions. This resin degrades the quality of the wash oil. A
portion of the wash oil is continuously removed and treated to
separate this polymerized resin. The cleanup can be accomplished
thermally in a wash oil purifier or gravitationally in a wash oil
decanter or by using the difference in densities between the resin
and the wash oil to separate them in a centrifuge (only
gravitational separation in a decanter is shown in Figure 2). The
polymerized resin known as wash oil muck or muck oil (EPA Hazardous
Waste No. K143) accumulates over time and is removed periodically
from the decanter. The cleaned wash oil is recycled to the light
oil recovery cycle via the wash oil storage or recirculation tank.
The material that accumulates in the storage or recirculation tank
is also referred to as a light oil recovery residue (EPA Hazardous
Waste No. K143). The coke oven gas that exits from the light oil
plant has a relatively high heating value. At captive plants,
about 40 percent of the COG is used as fuel for the coke ovens, and
the remainder is used as fuel in other steel plant operations.
Merchant plants use about 40 percent of the COG as fuel for the
coke ovens, and the remainder is sold as a fuel or flared.
29
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Historicaliv, the gas from the light oil scrubber has been used as
a fuel without further pretreatment. However, because the COG
contains significant quantities of hydrogen sulfide (H2S), many
plants now practice COG desulfurization to reduce S0X emissions.
The three basic types of COG desulfurization processes are (a)
liquid absorption processes, (b) wet oxidative processes, and (c)
dry oxidative processes.
Liquid absorption processes include three basic steps: (1)
absorption of acid gases (e.g.. absorbing hydrogen sulfide into a
recirculating solution); (2) steam stripping of acid gases to
regenerate the absorbing solution; and (3) acid gas conversion of
H2S to elemental sulfur or sulfuric acid. The three liquid
absorption processes used by coke plants in the United States are
the Vacuum Carbonate1", Sulfibanim, and Firm a Carl Still1Q
processes. The absorbing solutions used in these processes are
sodium carbonate solution, alkanolamine solution, and ammonia
solution, respectively.
Wet oxidative processes also involve three basic steps: (1)
absorption of acid gases into a recirculating solution; (2)
oxidation of absorbed sulfide to elemental sulfur or soluble sulfur
salts; and (3) recovery of sulfur as elemental sulfur or ammonium
sulfate. The wet oxidative processes used by American or Canadian
coke' plants are the Stretford:°, Takahax1", and PeroxTm processes.
The oxidizing agents used in these processes are anthraquinone
30
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disulfonic acid and sodium vanadate, naphthoquinone sulfonic acid,
and hydroquinone, respectively.
The dry oxidative process used in the coke industry is the Iron
OxideTm (also called the Dry BoxTm) process. In this process, H2S is
adsorbed by a solid and either held as a sulfide or oxidized to
elemental sulfur. The resulting compound may be sold or disposed
depending on market conditions.
Most plants that practice light oil recovery have a sump that
collects wastewaters generated in the light oil recovery area.
Such wastewaters would include decanter water from the primary,
intermediate, and secondary separators, as well as equipment and
floor wash water. The primary purpose of the intercepting sump is
to provide sufficient residence time for oil and water to separate.
The separated light oil fraction is recovered by skimming and
returned to the process. Sludge that accumulates in the bottom of
the intercepting sump typically is removed on a periodic basis.
These settled solids are residues that are defined as intercepting
sump sludges from light oil recovery (EPA Hazardous Waste No.
K144) .
Wastewater from the intercepting sump usually is treated on-site
prior to disposal or is used to extinction in the coke quench
system. In the coke by-products recovery plant, wastewaters from
the light oil recovery process, waste ammonia liquor, and final
-------
coolsr bIov=down uunstitutc ma juiity o£ liquid wastes. Other
minor sources of aqueous waste are barometric condenser wastes from
ammonia crystal1izers, desulfurization wastes, and contaminated
waters from air pollution emission scrubbers used at charging,
pushing, preheating, or screening stations.
2. Tar Refining
Coal tars typically are refined at facilities other than coke
plants. Coal tar is refined by either batch or continuous
distillation into a number of products, including pitch, creosote,
naphthalene, and tar acids.
Tar is stored in tanks, and over time a tar residue accumulates at
the bottom of the storage tanks and is removed periodically. This
tar residue is identified as EPA Hazardous Waste No. K147.
When coal tar is refined using continuous distillation, the crude
material first is heated in a dehydration column, then flashed to
separate its components. The heavy liquid components such as pitch
and creosote are sent to a distillation column for further
refining. Vapors from the flash chambers and distillation columns
are sent to a fractionating column. Finished commercial products
include heavy naphtha, naphthalene, creosote, and anthracene oil.
Still residues are not generated from the continuous process.
32
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A batch still is a horizontal tank used to heat the crude coal tar.
Vapors from the material to be distilled leave the top of the still
and pass through a water-cooled condenser. The pitch is heated
until it reaches the desired softening point. At that point, the
pitch is discharged from the still, cooled, and poured into barrels
for storage. In the batch distillation process, high-boiling-point
residues accumulate on the fire tubes and at the bottom of the
still and must be removed periodically. This residue is called tar
distillation bottoms or tar distillation residue (EPA Hazardous
Waste No. K14 8) .
33
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SECTION III
QUANTITIES AND COMPOSITION OF THE WASTES
This section describes the composition of the wastes and the
quantities generated during the production, recovery, and refining
of coke by-products. The quantities of wastes generated and their
typical composition are presented for each of the newly listed coke
by-products wastes (K141 through K145, K147, and K148) as well as
other waste streams evaluated by EPA.
Table 5 presents estimates of the quantities of wastes generated
from the production, recovery, and refining of coke by-products and
the factors used to calculate these estimates. These estimates are
based on data supplied to EPA by the industry in response to the
questionnaires sent to each operating facility in 1985, and
supplemental data collected from all tar refiners and approximately
50 percent of the existing coke plants in 1987. The industry
questionnaires were issued under the authority of Section 3007 of
RCRA. The estimates were calculated using a best-estimate,
production-normalized, waste generation rate for each residual
stream. A plant-specific waste/residual determination was made
based on the process description or residual characterization
supplied by each plant. Waste quantities were estimated using
plant-specific production rates for those plants that were known to
generate the residual stream.
34
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TAHLE5
ESTIMATED NATIONWIDE WASTE QUANTITIES
WASTE STREAM
WASTE GENERA"! ION FACTOR
APPLICABLE
PRODUCTION MULTIPLIER
AMOUNT
RESIDUAL
GENERAIED
1. Piocess residues fiorri coal Inr recovery (K141)
N/A
N/A
2 0 x 10 3 MT/yr
2 Coke plant tar storage tank residuals (K142)
360 g/MT coke produced
2.4 x 107 coke produced /year
8 6 x 103 Ml /yi
3 Uyfil oil plant processing (K143)
a Benzol plant scrubber residue
24 g/ MT coke produced
1 5* 107 MT coke produced/yr
3 6 x 102 MT/yr
b Wash oil purifier residue
05 g/MT coke produced
1 Ox 10 1 MT coke produced/yr
8 5 x 10 2 MT/yr
c. Wash oil decanter muck
160 g/MT coke pioduced
1 5 x 107 M r coke produced/yr
2 4 x 10 3 MT/yr
4 Intercepting sump sludges Irorn
light oil processing (K144)
52 g/MY coke pioduced
1 5 x 107 MT coke produced/yr
7 0 x 10 2 MT/yr
5 Naphthalene collection and lecovery residues
(K145)
a Final cooler sump residue
20 g/MT coke produced
1.5* 10 7 MT coke produced/yr
3 0 x 10 2 MT/yr
b Naphthalene skimmer residue
9 9 g/MT coke produced
1.4 x 107MP coke produced/yr
1 4 x 10 2 MT/yr
6 Tar plants ¦ Tar storage tank residuals (K147)
49 g/L tar processed
5 5 x 107 L tai/yr
2 7 x 10 3 MT/yr
7. Tar distillation residues (K14G)
5 1 g/L tai processed
5 2 x 107 L tai/yr
2 7 x 10 2 MT/yr
Source RCRA 3007 Questionnaires
35
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The assumptions made and data used to generate these estimates are
provided in the following sections.
Estimates of the amounts of wastes generated were developed from
information received in the 1985 and 1987 RCRA 3007 questionnaire
responses that were completed by all affected coke by-products
recovery plants. Estimates of nationwide amounts of generated
wastes were made by developing capacity-based emission factors.
Note that some facilities have claimed their information to be
confidential business information (CBI); therefore, calculations
pertaining to these facilities are included in the CBI version of
the Background Document. Information on quantities and composition
of wastes generated from the production and recovery of coke by-
products is discussed below in Section III.A. Information on
quantities and composition of wastes generated from tar refining is
presented in Section III.B.
A. Coke By-Products Process Residuals
1. Quantities of Process Sludges or Residuals and
Wastewaters
Estimates of nationwide quantities of coke by-product residuals
were made by developing capacity-based emission factors. Capacity-
based emission factors for each waste stream were first developed
for those plants that reported generating that particular waste
-------
stream. Then, nationwide quantities generated for each waste
stream were calculated from the nationwide total annual quantity of
coke produced by plants and the corresponding capacity-based
emission factor.
Tables 6 through 13 present, the estimates of quantities of some of
the waste streams from the production and recovery of coke by-
products. Data collected in the RCRA 3007 "clarification
responses" submitted in 1937 were used to estimate the rate at
which these waste streams are generated. Regression plots of waste
generation factors versus coke production yielded high values of
correlation coefficient (r), demonstrating that the generation of
these wastes can be closely related to the amount of coke produced.
The total amount of wastes generated nationwide was calculated
using the arithmetic average (i.e.. the waste generation factor)
multiplied by the expected annual production rate of coke.
The expected annual production rate of coke was established by the
RCRA 3007 responses. If facilities specifically reported that a
residual stream was not generated, then the production rate of the
facility was not included in the nationwide coke production
summary. If a waste stream was expected to be produced, and no
quantity was reported, then the facility's production rate was
included in the nationwide summary. Production numbers are for
1984. Please note that some facilities have changed name and/or
ownership since the questionnaire responses were received.
37
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TABLE 6
ESTIMATES OF QUANTITIES OF TAR COLLECTING
SUMP RESIDUES (K141)
Reported amount
Amount,
Coke
g residual/
generated
metric
production,
ton coke
Facility"
tons/yr.
tons/yr.
production
N/A
2.8 x 103
N/A
N/A
a Data were derived from the TSDR survey. These were supplemented by data from RCRA 3007
Questionnaire responses and the K0S7 Background Document. K141 waste generation rates of individual
plants were unavailable.
38
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TABLE 7
ESTIMATES OF QUANTITIES OF TAR STORAGE TANK RESIDUES
FOR COKE PLANTS (K142)
Reported
Coke
g residual/
amount
Amount
production
mcinc ion coke
Facility
gencrated/vT
g/yra
metric lons/yr
produced
Bethlehem Slecl, BeLhlchem, Pa.
50,000 gal
2.5 x 108
1.2 x 106
210
USX, Geneva, Utah
50,000 gal
2.5 x 108
8.2 x 105
300
Armco, Ashland, Ky.
9,000 gal
4.6 x 107
9.1 x 105
50
Inland No. 2
b
3.6 x 108
1.0 x 106
360
Inland No. 11
305 yd3
3.1 x 108
73 x 105
420
USX, Gary, ind.
b
2.3 x 109
1.5 x 106
1,500
Tonawanda Coke
b
1.4 x 107
1.8 x 105
78
National Steel, Granite City
30,000 gal
1.5 x 10s
5.4 x 10s
280
LTV Steel-Cleveland No 1
30 yd3
3.1 x 107
45 x 105
69
Specific gravity of tar tank sludge is taken as 1.3375 from analytical data supplied by
Bethlehem Steel.
Not supplied in volumetric units.
Source: RCRA 3007 Questionnaires.
Arithmetic average of quantities of tar storage tank residues generated by coke plants per MT of
coke produced = 360 g/MT coke produced.
Sample Calculations:
For Bethlehem Steel in Table 7, quantity of tar storage tank residues generated = (50,000
gal/vr)(ft3/7.4S gal)(62.4 lb/ft3)(454 g/lb)( 1.3375) = 2.5 xr 10s g/yr.
For Inland No. 11, quantity of tar tank storage residues generated = (305 yd3/yr)(27 ft3/yd3)(62.4
lb/ft3)(454 g/lb)( 1.3375) = 3.1 x 10s g/yr.
For Bethlehem Steel, quantity of tar storage tank residue per MT of coke produced = (2.5 x 10s
g/yr)(yr/1.2 x 106 MT coke produced) = 210 g/MT coke produced.
39
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TABLE 8
ESTIMATES OF QUANTITIES OF BENZOL PLANT
SCRUBBER RESIDUE (K143)
Facility
Reported
amount
generated/yr
Amount
g/>T8
Coke
production
metric lons/yr
g residual/
metric ton coke
produced
Bethlehem Steel, Pa.
100 gal
3.4 x 105
1.2 x 106
0.28
USX, Utah
0.6 tons
5.4 x 105
8.1 x 105
0.67
Interlake, 111.
6,000 gal
2.0 x 107
4.5 x 10s
44
Inland Steel, Pa.
24,000 gal
8.2 x 107
1.4 x 106
59
LTV Steel, III.
7.5 tons
6.8 x 106
4.5 x 105
15
Source: RCRA 3007 Questionnaires.
a Assuming a specific gavity of benzol plant scrubber residue = 0.9.
Arithmetic average of quantities of benzol plant scrubber residue per MT of coke produced = 24
g/metric ton cuce produced.
Sample Calculations:
For USX, Utah, quantity of benzol plant scrubber residue generated = (0.6 T/vr)(2000 lb/t)(454
g/lb)(0.9) = 4.5 x 105 g/yr.
For LTV Steel, quantity of benzol plant scrubber residue per MT of coke produced = (7.5
T/yr)(2000 lb/T)(454 g/lb)(0.9)(yr/4.5 x 105 MT coke produced) = 15 g/MT coke produced.
40
-------
table 9
ESTIMATES OF QUANTITIES OF WASH OIL PURIFIER
RESIDUE (K143)
Facility
Reported
amount
generated/yr
Amount
g/yra
Coke
production
metric tons/yr
g residual/
metric ton coke
produced
Bethlehem Steel, Md.b
60,000 gal
23 x 108
1.4 x 106
160
Bethlehem Steel, N Y.b
12,000 gal
4.5 x 107
7.2 x 10s
62
LTV Steel Warren, Ohiob
3S,400 gal
1.5 x 10s
45 x 105
330
Bethlehem Steel, Pa.c
5,200 gal
2.0 x 107
1.2 x 106
17
Inland SteeL 111.0
1.200 gal
4.5 x 106
7.2 x 105
6.2
National Steel, Ill.c
5,000 gal
1.9 x 107
5.4 x 105
35
LTV Steel, Pa.c
24,000 gaJ
9.1 x 107
1.4 x 10f>
65
LTV Steel, No 1, Ohioc
6.500 lb.
3.0 x 106
4.5 x 105
6.7
Assuming specific gavity of wash oil purifier residue = 1.
From 1985 RCRA 3007 Questionnaire responses.
From 1987 RCRA 3007 clarification responses.
Arithmetic average of quantities of wash oil purifier residue per MT of coke produced = 85
g/metric ton coke produced.
Sample Calculations:
For LTV Steel, Warren, Ohio, quantity of wash oil purifier residue generated = (38,400
gal/yr)(8.34 lb/gal)(454 g/lb) = 1.5 x 10s g/yr.
For National Steel, 111., quantity of wash oil purifier residue per MT of coke produced = (5000
gal/yr)(8.34 lb/gal)(454 g/lb)(yr/5.4 x 105 MT coke produced) = 35 g/MT coke produced.
41
-------
TABLE 10
ESTIMATES OF QUANTITIES OF WASH OIL DECANTER
MUCK (K143)
Reported
Coke
g residual/
amount
Amount
production
metric ton coke
Facility
generated/yr
g/yra
metric tons/yr
produced
Armco, Ohiob
50,000 gal
1.9 x 108
9.1 x 105
210
Bethlehem Steel, Pa.c
10,400 gal
3.9 x 107
1.2 x 106
33
Inland Steel No. 2b
47,800 gal
1.8 x 108
1.0 x 106
180
LTV Steel No. 2, Ohioc
100,000 lb
4_5 x 107
4_5 x 10s
100
Rouge SteeL, Mich.c
48,000 gal
1.8 x 108
6.4 x 105
280
Assuming specific gavity of wash oil decanter muck = 1.0
From 1985 RCRA 3007 Questionnaire responses.
c From 1987 RCRA 3007 clarification responses.
Arithmetic average of quantities of wash oil decanter muck per MT of coke produced = .160
g/metric ton coke produced.
Sample Calculations:
For Inland Steel No. 2, quantity of wash oil decanter muck generated = (47,800 gal/yr)(8.34
lb/gal)(454 g/lb) = 1.8 x 108 g/yr.
For Armco, quantity of wash oil decanter muck per MT of coke produced = (50,000 gal/yr)(8.34
ib/gal)(454 g/lb)(yr/9.1 x 105 MT coke produced) = 210 g/MT coke produced.
42
-------
TABLE 11
ESTIMATES OF QUANTITIES OF LIGHT OIL INTERCEPTING
SUMP RESIDUES (K144)
Facility
Reported
amount
generated/yr
Amount
g/yra
Coke
production
metric tons/yr
g residual/
metric ton coke
produced
USX, Utah
144 tonsc
13 x 10s
8.2 x 105
160
National Steel, III.
5,000 gal
2.1 x 107
55 x 10s
38
Interlake, 111.
3,000 gal
1.2 x 107
4.5 x 105
27
LTV' Steel, Pa.
24.000 gal
1.0 x 10s
1.4 x 106
71
LTV Steel No. 1, Ohio
1.000 lb
4.5 x 106
4.5 x 105
10
Armco, Ohio
200 gai
8.3 x 10s
9.1 x 105
0.91
Data are from the 1987 RCRA 3007 clarification requests.
Assuming specific gravity of light oil intercepting sump residues = 1.1.
All wash oil processes blow down to a sump.
Arithmetic average of quantities of light oil intercepting sump residue per MT of coke produced
= 52 g/metric ton coke produced.
Sample Calculations:
For Interlake, 111., quantity of light oil intercepting sump residues = (3,000 gal/yr)(8.34 lb/gal)(454
g/Ib)( 1.1) = 1.2 x 107 g/vr.
For LTV Steel, Pa., quantity of light oil intercepting sump residues per MT of coke produced =
(24,000)(8.341b/gal)(454 g/lb)(l.l)(yr/1.4 x 106 MT coke produced) = 71 g/MT coke produced.
43
-------
TABLE 12
ESTIMATES OF QUANTITIES OF FINAL COOLER
RESIDUE (K.145)
Facility
Reported
amount
generated/yr
Amount
g/yrB
Coke
production
metric tons/yr
g residual/
metric ton coke
produced
USX, Utah"
133 tons
1.2 x 107
8.2 x 105
15
National Steel, 111.8
5,000 gal
1.9 x 107b
55 x 105
35
Gulf States, Ala.c
5.2 tons
4.7 x 106
4.5 x 105
10
From 1987 RCRA 3007 clarification requests.
Assuming specific gravity of final cooler residue = 1.0.
c From 1985 RCRA 3007 questionnaire.
.Arithmetic average of quantities of final cooler residue per MT of coke produced = 20 g/metric
ton coke produced.
Sample Calculations:
For USX, quantity of final cooler residue generated = (13.3 T/yr)(2000 lb/T)(454 g/lb) = 1.2 x
107 g/yr.
For Gulf States, Ala., quantity of final cooler residue per MT of coke produced = (5.2 T)(2000
lb/T)(454 g/lb)(yr/4.5 x 105 MT coke produced) = 10 g/MT coke produced.
44
-------
TABLE 13
ESTIMATES OF QUANTITIES OF NAPHTHALENE SKIMMER
RESIDUE (K145)
Facility
Reported
amount
generated/yr
Amount
s/yra
Coke
production
metric tons/yr
g residual/
metric, ton coke
produced
National Steel, 111.8
2,500 gal
9.5 x 1066
5.5 x 105
17
USX, Utah"
4.666 lb
2.1 x 106
8.2 x 10s
2.6
Gulf States, Ala.c
5.2 tons
4.7 x 106
4_5 x 10s
10
From 1987 RCRA 3007 clarification requests.
Assuming specific gravity of naphthalene skimmer residue = 1.0.
c From 1985 RCRA 3007 Questionnaire.
.Arithmetic average of quantities of naphthalene skimmer residue = 9.9 g/MY coke produced.
Sample Calculations:
For National Steel, quantity of naphthalene skimmer residue generated = (2500 gal/yr)(8.34
lb/gal)(454 g/lb) = 9.5 x 106 g/yr.
For USX, quantity of naphthalene skimmer residue per MT of coke produced = (4,666 lb)(454
g/lb)(yr/8.2 x 105 MT coke produced) = 2.6 g/MT coke produced.
-------
The wastewater generation factor for coke by-products wastewaters
provided in the Effluent Limitations Guidelines Document for this
industry was used to estimate wastewater volumes from data provided
in the 1987 RCRA Section 3007 clarification responses. This
wastewater generation factor is 177 gal/ton of coke produced. For
27 million tons of coke produced, the total annual quantity of
wastewater generated by coke by-products plants, using this factor,
is estimated to be 1.8xl07 m2/yr.
2 . Concentrations of Constituents Present in Process Sludges or
Residuals and Wastewaters
EPA sampled ten coke by-products facilities from 1985 to 1989. The
Sampling and Analyses Plans and Analytical Data Reports summarizing
the sampling activities performed and the analytical results
obtained for the samples collected are available in the docket for
the proposed rule.
The constituents present in coke by-products residuals can be
divided into three groups: volatiles, polynuclear aromatic
hydrocarbons (PAHs) and phenolics. Tables 14 through 19 present
the ranges and averages of measured concentrations for the
constituents analyzed in these wastes.
46
-------
TABLE 14 : TAR COLLECTING SUMP RESIDUES (KM I)
MEASURED CONCENTRATIONS OE CONSTITUENTS (ALL VALUES IN PPM)
CONSTITUENT
SAMPLE
NUMBER 1
SAMPLE
NUMBER 2
RANGE
AVERAGE
Acenaphthene
800
NA
800
800
Acenaphthylene
21,000
NA
21,000
21,000
Anthracene
10,000
NA
10,000
10,000
Benzene
NA
3,900
3,900
3,900
Benz(a)anthracene
7,900
NA
7,900
7,900
Benzo(a)pyrene
8,500
NA
8,500
8,500
Benzo(b and k)fluoianthene
5,500
NA
5,500
5,500
Benzo(g,h,i)perylene
6,700
NA
6,700
6,700
Chrysene
8,000
NA
8,000
8,000
Dibenz(a,ti)antliiacene
1,800
NA
1,800
1,800
2,4-Dimethylphenol
200
NA
200
200
2.4- Dinitiotoluene
2,000
NA
2,000
2.000
Ethylbenzene
21
26
21-26
24
Eluoranthene
25,000
NA
25,000
25,000
Eluurene
8,100
NA
8,100
8,100
ldeno( 1,2,3-cd )pyrene
6,200
NA
6,200
6,200
1 - Methyl naphthalene
4,700
NA
4,700
4,700
2-Methyl naphthalene
8,500
NA
8,500
8,500
2-Methyl phenol
200
NA
200
200
4-Methyl phenol
5,500
NA
5,500
5,500
m-Xylene
420
340
340-420
380
Naphthalene
95,000
NA
95,000
95.000
o/p-X ylene
290
210
210-290
250
Phenanthrene
36,000
NA
36,000
36,000
Phenol
5,900
NA
5,900
5,900
Pyrene
21,000
NA
21,000
21,000
Styrene
NA
NA
NA
NA
Toluene
ND
1 500
ND-I 5D0
7 50
NA : Not Analyzed
-------
TABLE 15 : TAR STORAGk ANK RESIDUES (KI42)
MEASURED CONCENTRATIONS OF CONSTITUENTS (ALL VALUES IN PPM)
CONSTITUENT
SAMPLE
SAMPLE
SAMPLE
SAMPLE
SAMPLE
RANGE
AVERAGE
NUMBER 3
NUMBER 4
NUMBER 5
NUMBER 6
NUMBER 7
Acenaphlhene
1,200
1,200
1,000
690
NA
690-1.200
1.000
Acensphthytene
5,000
1.500
9,300
8,900
NA
1,500-9,300
6,400
1 Anthracene
5,900
3,200
6,500
7.700
NA
3.200-7,700
5.800
1 Benzene
290
260
230
250
270
230-290
260
Benz(a)anthracene
7.400
5,400
6,400
7,300
NA
5.400-7,400
6.600
Benzo(a)pyrene
6,000
4.500
0,300
7,300
NA
4.500-8,300
6.500
Benzo(b and k)fluoranthene
10,000
6,600
7,900
5,200
NA
5,200-10,000
7.500
Benzo(g.h.()pery1ene
2,800
1.800
2.700
4,500
NA
1,000-4,500
3,000
Chrysene
5,600
4,000
7,100
7,400
NA
4,000-7,400
6,000
Dibe»iz(a.h)aritl)raceiie
t .300
720
< 1.000
1,600
NA
720-1,600
1.000
2,4-Dlmethylphenol
600
1.400
300
140
NA
140-1,400
600
2.4-Dinitrotoluene
NA
NA
<2.000
<200
NA
<200-<2,000
500
Ethylbenzene
19
20
7 8
<40
4 9
4 9-<40
14
Fluoranthene
21.000
1 7.000
10.000
21,000
NA
17,000-21,000
19.000
Fluorene
14.000
8,700
8.500
9,600
NA
8,500-14,000
10.000
ldeno( 1,2.3-cd)pyt ene
2.900
2,000
2.500
4,100
NA
2,000-4,100
2,900
1-Methyl naphthalene
NA
NA
4.900
3,600
NA
3,600-4,900
4.200
2-Methyl naphthalene
9,900
6,900
11.000
6,400
. NA
6,400-11,000
8,600
2-Methyt phenol
870
1.200
650
360
NA
360-1,200
780
4-Melhyi phenol
2,500
1,400
2.900
1,200
NA
1,200-2,900
2.000
m-Xylene
230
91
66
100
110
66-210
120
Naphthalene
53,000
32,000
84,000
50,000
NA
32,000-84,000
55,000
o/p-Xytene
100
60
59
77
85
59-160
90
Phenanthrene
35.000
23,000
31,000
30,000
NA
23,000-35,000
30.000
Phenol
3.200
3,300
3,500
1,500
NA
1,500-3,500
2,900
Pyrene
14.000
10,000
17,000
16,000
NA
10,000-17,000
14,000
Styrene
06
<17
NA
NA
NA
<17-86
47
Toluene
270
130
140
160
160
130-270
170
detected below the
b NA = Not Analyzed
c ND = Not Detected
Source: Analytical Data Reports
48
-------
I ABLE 16: RESIDUES FROM LIGHT OIL PROCESSING (K 143)
MEASURED CONCENTRA TIONS OF CONSTITUENTS (ALL VALUES IN PPM)
CONS1WUEN1
SAMPUE
NUMBER
0
SAMPLE
NUMBER
9
sample
NUMBER
10
SAMPLE
NUMBER
11
sample
NUMBER
12
SAMPLE
NUMBER
13
SAMPLE
NUMBER
14
SAMPLE
NUMOEn
15
SAMPLE
NUMBER
1G
SAMPLE
NUMBER
17
SAMPLE
NUM8ER
18
RANGE
AVERAGE
« 0 7
4 ;
NO
51
<25
NA
8
<30
<10
370
(JO 370
59
AcenapMhene
< 40
* 3 '
Acenaphlhylc'ie
300
590
040
210
390
250
NA
260
700
260
5.700
200 ¦ 5 700
950
AntfHacerve
<40
170
86
3-Uj
00
4Q
NA
40
1 10
53
' 100
<4Q - J4U
10 J
Benzene
120
39
1 600
NA
4/0
ISO
160
0 500
NA
NA
NA
39 - 6.500
1 500
Ben7(o)amh'acene
ND
150
55
320
7(J
'25
NA
<10
<30
<5
<100
ND - 320
G9
G«!f\zo(n)p)'ef)e
,40
<97
<40
130
- 20
'25
NA
<20
<50
< 10
'100
<10 • 130
34
0enzo(b and
60
120
4Q
2 JO
4 2
<25
NA
< 10
'30
<5
< 100
'5 2 JO
59
Ben/o(g h.l)pe*>leoe
ND
<97
<40
-97
' 100
-25
NA
< 10
<30
<5
<500
NO - ' 500
45
Chfyscne
45
110
56
250
46
'25
NA
< 10
'30
'5
<100
<5 ¦ 250
59
Olbeaz(«.h)arrttuflcef»e
ND
ND
ND
<97
< 100
<25
NA
< 10
<30
'5
<500
NO ¦ '500
38
2.4-Olmelhylpheno!
ND
ND
ND
NO
<6
NA
<10
< 10
' 10
'100
ND - ' 100
7
2.4-Olfrttrotoiuene
NA
NA
NA
NA
'200
-250
TiA
'30
<100
<30
1.000
'30 - • 1.000
130
Ethyibenzene
C 6
11
f J A
NO
<40
6 3
60
NA
NA
NA
'2 - G8
16
* /
Fluoranthenc
120
530
NO
1 500
210
too
NA
41
230
65
<100
NO - 1 500
290
Fluorene
87
190
220
190
190
75
NA
31
02
32
340
J1 • 340
140
lndeno(l.2 3-cd)pyrene
<40
NO
ND
<97
<100
•25
NA
< 10
'30
<5
<500
NO - ' 500
40
nflphlfiolene
NA
NA
NA
NA
290
230
NA
190
360
170
11.000
190-1 l.Otfl
2.000
2 Methyl r^aphttiaiene
190
7 SO
900
330
650
350
NA
490
080
450
23 OCO
190 ¦ 23 000
2.000
2-Metfiyl phenol
no
ND
ND
NO
24
'5
NA
26
' 10
'10
< 100
NO ' 100
11
4-Methyl phenol
NO
NO
NO
NO
J2
<5
NA
70
10
25
' 100
NO - 78
20
m-Xylene
31
170
280
NA
NA
170
120
2.000
r;A
NA
NA
3 1 - 2 OCO
460
Neplrttolene
2.GOO
3,600
6.000
1.400
7.000
2.500
NA
6.500
7 200
5.000
460 000
1,400 ¦ 400.000
52 000
o/p-Xylene
2?
140
2O0
NA
NA
130
97
1,300
NA
NA
NA
22 • 1 30J
310
F^enanttM ene
170
570
460
2 000
640
330
NA
130
590
200
640
130 - 2.000
500
fticnol
ND
'97
<40
NO
30
<5
NA
320
22
94
<100
ND 320
59
Pytene
150
300
120
600
190
91
NA
34
190
55
100
34 - 600
2u0
27
120
190
NA
riA
NA
NA
NA
NA
NA
NA
27 -190
110
Styr ene
35 ¦ 4 /CO
Toluene
35
190
790
NA
390
150
15U
4,700
NA
NA
NA
920
When calculating averages, values delected below the detection limit were taken as one-Malt the detect,on
NA » Not Analyzed
ND - Not Delected
ource : Analytical Data Reports
49
-------
TABLE 17 INTERCEPTING SUMP RESIDl j FROM LIGHT OIL REFINING (KI44)
MEASURED CONCENTRATIONS OF CONSTITUENTS (ALL VALUES IN PPM)
CONSTITUENT
SAMPLE
NUMBEn 19
SAMPLE
NUMBER 20
SAMPLE
NUMGER 21
SAMPLE
NUMBER 22
SAMPLE
NUMBER 23
SAMPLE
NUMBER 24
RANGE
AVERAGE
Acenaplithene
ND
<20
16
30
23
NA
ND - 30
16
Acenaphthylene
340
490
440
300
190
NA
190 - 490
350
Anthracene
160
93
80
40
65
NA
48 - 160
90
Benzene
1 .too
14.000
200
260
1.200
1,100
200 - 14,000
3,000
Benz(a)anthra eerie
140
<15
110
42
42
NA
<15 - 140
68
Benzo(a)pyrene
130
<20
110
40
39
NA
<20 - 130
65
Benzofb and kjfluoratilhene
220
<15
91
26
30
NA
<15 - 220
75
Benzo(g.li.i)pery1ene
03
<15
63
20
28
NA
<15 - 80
40
Chrysene
120
-¦15
110
51
43
NA
<15 - 120
66
Dibenz(a,h)anll>jacene
<61
<15
1 t
22
<7
NA
<7 ¦ <61
15
2,4-Dhnctliylphenol
ND
<20
24
<8
<2
NA
ND - 24
7.8
2,4-Dmltrotoluene
NA
<100
<10
<00
<70
NA
<10 - <100
33
Ethylbenzene
25
44
<1
26
<40
11
<1-44
17
Fluoranthene
4)0
110
160
110
140
NA
110 - 410
190
Fluorene
ND
62
160
75
100
NA
ND- 160
79
lndeno(l ,2,3-cd)pyrene
n
<15
59
17
22
NA
<15 - 77
37
1-Methyl naphthalene
NA
3B0
60
280
340
NA
60 - 380
260
2-Methyl naphthalene
970
970
97
730
t ,200
NA
97 - 1.200
790
2-Methyf phenol
ND
<10
57
<8
20
NA
ND - 57
17
4-Methyl phenot
ND
<10
78
<8
30
NA
ND - 78
23
m-Xylene
470
1,100
61
52
190
190
52 - 1.100
350
Naphthalene
53.000
12,000
360
21,000
48,000
NA
360 - 53,000
27,000
o/p-Xylene
340
790
35
34
120
130
34 - 790
240
Phenanthrene
620
320
300
210
3I0
NA
2)0 • 620
350
Phenol
ND
32
04
to
33
NA
ND- 84
32
Pyrene
250
93
100
89
110
NA
89 - 250
130
Styrene
ND
NA
NA
NA
NA
NA
ND
ND
Toluene
900
4,200
120
140
540
520
120 - 4,200
1,100
a When calculating averages, values detected below the detection limit were taken as one-ha/f the detection limit,
b NA- Not Analyzed
c ND » Not Detected
Source: Analytical Data deports
50
-------
TABLE 18 : NAPHTHALENE COLLECTION AND RECOVERY RESIDUES (K145J
MEASURED CONCENTRATIONS OF CONSTITUENTS (ALL VALUES IN PPM)
CONSTITUENT
SAMPLE
NUMBER 25
SAMPLE
NUMBER 26
SAMPLE
NUMBER 27
SAMPLE
NUMBER 28
RANGE
AVERAGE8
Acenaphthene
<96
30
1 10
0.1
0.1-1 10
47
Acenaphthylene
2,600
610
3.900
8.9
8.9-3,900
1,800
Anthracene
230
94
150
0.9
0 9-230
120
Benzene
120
150
3,000
NA
120-3,000
1,100
Beriz(a)anthracene
<96
26
14
<3
<3-<96
22
Benzo(a)pyrene
ND
22
<10
1.3
ND-22
7
Benzo(b and k)fluoranthenc
<96
37
17
2 3
2.3-<96
26
Benzo(g,h,i)perylenc
ND
10
4,600
1.5
ND-4,600
1.200
Clirysene
<96
23
13
2.7
2.7-<96
22
Dibenz(a,h)anthracene
ND
ND
<10
0.3
ND-<10
1 3
2,4-Dimethylplienol
ND
250
45
1.4
ND-250
73
2,4-Diriitrololuene
NA
NA
<20
<10
<10-<20
7 5
Ethylbenzene
5.500
1.5
6,700
0.8
0.8-6,700
3.100
riiioranthene
140
110
98
0.2
0 2-140
87
Fluorene
690
240
440
0.8
0 8-690
340
Indeno( 1,2,3-cd)pyrene
ND
9.9
<10
1.2
ND-9.9
4
1-Methyl naphthalene
NA
NA
3,300
<4
<4-3.300
1.700
2-Methyl naphthalene
5,500
1 5
6,700
0.8
0 8-6,700
3,100
2-Methyl phenol
<96
96
66
6.5
6.5-96
54
4-MethyI phenol
<96
230
120
" '
11-230
100
ni-Xylene
79
160
1,000
NA
79-1,000
410
Naphthalene
240,000
24,000
300,000
5.7
5.7-300,000
140.000
o/p-Xylene
77
150
860
NA
77-860
360
Phenanthrene
750
260
400
2.6
2.6-750
.350
Phenol
210
70
180
15
15-210
120
Pyrene
79
70
63
2.1
2.1-79
53
Styrene
140
90
NA
NA
90-140
120
Toliipup
1 20
170
2 000
NA
120-2 000
760
si
-------
When calculat. averages, values detected below the detection limit were take i one-half the detection limit.
52
-------
TAiJLE 19 : COKE BY-PRODUCTS WASTEWATERS
MEASURED CONCENTRATIONS OF CONSTITUENTS (ALL VALUES IN PPM)
CONSTITUEN T
SAMPL£
NIJM 29
SAMPLE
NUM 30
SAMPLE
NUM 31
SAMPLE
MUM 32
sample
NUM 36
sample
NUM 36
SAMPLE
NUM 33
SAMPLE
NUM. 37
SAMPLE
NUM 39
SAMPLE
NUM 40
SAMPLE
NUM. 34
SAMPLE
NUM. 35
RANGE
A'.HrtAGE
Acenaphthene
<0 05
ND
<0 16
<0 14
NA
NA
<0.05
<1
NA
NA
ND
<0.06
z
o
A
0 09
Acenaphthylene
'0 05
<0 I
0 57
0 70
2 7
0 33
0.39
<1
0 02
1 2
ND
0 05
ND-2 7
0.55
Anthracene
0.06
<0 1
<0 16
<0 14
NA
NA
0.06
<1
NA
NA
ND
<0 06
ND-<0 16
0 11
Benzene
<0 002
<0 002
0 44
26
21
38
37
23
40
86
03
0.1
<0 002-06
21
Benz(a)anthracene
<0 05
0 32
<0 16
<0 14
NA
0 11
<0 05
<1
ND
1 2
<0 04
<0 06
ND-1 2
0 12
Benzo(a)pyrene
<0 05
021
ND
ND
NA
0 08
ND
<1
ND
ND
ND
<0 06
ND-0 21
0.08
8enzo(b and kjfluoranthene
¦¦0 05
0 36
ND
ND
NA
NA
ND
<1
NA
NA
ND
<0.06
ND-0 36
0.1 1
Bonzo(g.h,l)pefy1e!ie
ND
0 t
ND
ND
NA
NA
ND
<2 5
NA
NA
ND
ND
ND-<2 5
0 17
Chiysene
<0 05
0 25
<0.16
<0 14
NA
006
<0 05
<1
ND
1.5
<0 04
<0.06
ND-1 5
0 23
Dibenz(a.h)anthracene
ND
<0 t
ND
ND
NA
NA
NO
-.2.5
NA
NA
ND
ND
ND-<2.5
0.16
2.4-Olinethytphenol
4 7
10
21
10
6 3
ND
4.9
2 8
4 7
1 5
0 16
1.1
ND-21
6 3
2.4-Dinlliololuene
NA
NA
NA
NA
NA
1 9
NA
<5
ND
ND
NA
NA
ND-<5
1 1
Elhyibenzetie
<0 002
<0.002
<0 01
<0 02
NA
ND
001
<2
04
0 005
<0 01
0 002
ND-<2
0 13
Fluornnlhene
<0 05
0 32
<0 16
<0 14
NA
1.1
0.06
<1
0.45
0 95
<0 04
<0 06
<0 04-1.1
0 33
Fluorene
ND
ND
<0.16
<0 14
1 1
0 16
0.1
<1
0.16
0 10
<0.04
<0.06
ND-1 1
0 2
lndeno(1,2,3-cd)pyre(ie
ND
0 11
ND
ND
NA
NA
ND
NA
NA
NA
ND
ND
ND-0 11
0 02
1-Methyl naphthalene
NA
NA
NA
NA
3 9
NA
NA
<1
NA
NA
NA
NA
<1-3.9
22
2-Methyl naphthalene
ND
ND
0 33
0 42
3.7
NA
0 17
<1
NA
NA
0.64
<0.06
ND-3 7
0 64
2-Methy) phenol
24
47
60
61
23
NA
30
75
NA
NA
064
50
0 64-61
29
4-Methyl phenol
01
190
120
150
26
NA
37
13
NA
NA
1 2
28
1 2-190
72
m-Xylene
ND
<0 002
0 03
0 07
1 3
ND
0 32
NA
NA
NA
0.02
0 000
ND-13
0 19
Naphthalene
ND
ND
6 3
4 9
17
39
3.3
110
2 8
28
<0 04
0.63
ND-110
18
o/p-Xylene
ND
<0 002
0.03
0 06
1 1
NA
0 28
NA
NA
NA
0 02
0 005
ND-1 1
0 19
Phenanthrene
<0 05
<0 1
<0.16
<0 14
NA
NA
0.22
<1
NA
NA
<0.04
0 07
<0 04- < 1
0 13
Phenol
200
400
260
300
21
60
96
26
82
40
2
120
2-400
130
Pytene
<0 05
0 28
<0 16
ND
NA
0 09
<0.05
<1
ND
1
<0 04
<0 06
ND-1
0 19
Styrene
ND
NA
NA
0 00
NA
NA
0.39
NA
NA
NA
0013
0 49
ND-0 49
0 19
Toluene
<0 002
<0.002
0 12
0 39
6
i_i
17
__ ii-ii a.-
2.4
26
5.7
12
006
0 02
<0 002-17
39
b NA « Not Analyzed
c ND - Not Deleded
Source' Analytical Data Reports
53
-------
Table 20 presents concentrations of constituents detected in coke
by-products wastewaters. In particular, final cooler blowdown and
wastewaters from light oil recovery contain benzene levels ranging
from <0.002 to 86 ppm. EPA found that out of twelve samples, seven
analyzed by EPA had benzene levels higher than the promulgated
Toxicity Characteristic (TC) level of 0.5 ppm. Wastes exhibiting
the TC are regulated under RCRA Subtitle C as hazardous wastes.
EPA does not have analytical data on the concentrations of benzene
and other hazardous constituents of concern in sludges generated
from the treatment of coke by-product wastewaters.
B. Tar Refining Process Residuals
1. Quantities of Process Sludges or Residuals and Wastewaters
Estimates of nationwide quantities of tar refining residuals was
made by developing capacity-based emission factors. Capacity-based
emission factors for each waste stream were first developed for
those plants that reported generating a particular waste stream.
Then, nationwide quantities generated for each waste stream were
calculated from the nationwide total annual quantity of crude coal
tar processed by plants known to generate that waste stream
(including those plants that did not report the quantity of that
waste stream generated by them) and the corresponding capacity-
based emission factor.
54
-------
table 20
ESTIMATES OF QUANTITIES OF TAR STORAGE TANK RESIDUES
FOR TAR PLANTS (K147)a
Reported
Amount of
Residual
Amount
Tar processing
g residual/
Generated
generated, g/yr
rate. L/vr
L tar processed6
6,500 gal
33 x 107
6.8 x 106
4.9
6,105 gal
3.1 x 107
8.2 x 10s
38
128,441 gal
GS x 10s
52 x 106
130
19.056 gal
9.7 x 107
3.9 x 106
25
Names of facilities that reported generating this residue are CBI.
Assuming specific gravity of 1.3375 for tar storage tank residues.
.Arithmetic average of quantities of tar storage tank residue generated per liter of tar processed =
49 g residual/liter tar processed.
Sample Calculations:
For Row 1, quantity of tar storage tank residues generated = (6,500 gal/yr)(8.34 lb/gal)(454
g/lb)(1.3375) = 3.3 x 107 g/yr.
For Row 3, quantity of tar storage tank residues per liter of tar processed = (128,441 gal)(8.34
lb/gal)(454 g/ib)(1.3375)(yr/5.2 x 10fa L of tar processed) = 130 L.
55
-------
a. Tar Storage Tank Residues for Tar Plants (K147)
Of the tar refining plants that responded to the 1985 RCRA 3007
questionnaires and the 1987 clarification requests, four reported
generating quantities of tar storage tank residuals. Table 21
presents the waste generation factor calculations for tar storage
tank residue from the amount of coal tar processed in the plants,
and the reported amounts of tar storage tank residuals generated
(K147).
Nine tar refining facilities are expected to produce this residual
(based on the RCRA Section 3007 data). The total tar processing
rate from these facilities is 2.1xl08 gal/yr. Therefore, the
amount of tar storage tank residual produced at tar refining plants
is (2.1xl0e gal/yr) (12.8 g/gal tar) = 2.7 x 103 Mg/yr.
b. Tar Distillation Residues (K148)
Five tar refining facilities reported generating quantities of
K148. Based on RCRA 3007 responses and the 1987 clarification
responses, a total of nine facilities are expected to generate this
residual. Tar processing rates (in gal/yr) and a waste stream
generation factor for tar distillation residue derived from data
supplied by the five tar refining plants are presented below.
56
-------
TABLE 21 : TAR STORAGE TANK RESIDUES (KI47)
MEASURED CONCENTRATIONS OF CONSTITUENTS (ALL VALUES IN
PPM)
CONST! 1UENT
SAMPLE
SAMPLE
SAMPLE
SAMPLE
SAMPLE
RANGE
AVERAGE
NUMBEn 3
NUMBER 4
NUMBER 5
NUMBER 6
NUMBER 7
Acenaphthene
1.200
1,200
1,000
690
NA
690-1,200
*.000
Aconaphthylene
5.000
1,500
9,300
0,900
NA
1,500-9,300
6,400
Anthracene
5.900
3,200
6,500
7,700
NA
3,200-7,700
5,800
Benzene
290
260
230
250
270
230-290
260
Benz(a)anthracene
7.400
5,400
6,400
7.300
NA
5,400-7,400
6,600
Benzo(a)pyiene
6,000
4,500
8,300
7,300
NA
4.500-6.300
ei 500
Ben7.o(b and k)fluo(anthene
10.000
6.000
7,900
5,200
NA
5,200-10,000
7,500
Benzo(g,h,l)pery1ene
2,800
1,000
2,700
4,500
NA
1,800-4,500
3,000
Chrysene
5,600
4,000
7,100
7,400
NA
4,000-7,400
e.ooo
Dlbenz(a,h)anthracene
1,300
720
d.000
1,600
NA
720-1,600
1.000
2.4-D(methylphenol
600
1,400
300
140
NA
140-1.400
600
2.4-Dfnltrotoluene
NA
NA
<2.000
<200
NA
<200-<2,000
500
Ethyfbenzene
19
20
7 0
<40
4 9
4 9-<40
14
Fluotanthene
21,000
1 7,000
18,000
21,000
NA
17,000-21.000
19.000
Fluorene
14,000
8,700
8,500
9,600
NA
8,500-14,000
10,000
ldeno(t ,2.3-cd)pyiene
2,900
2,000
2,500
4,100
NA
2,000-4,100
2,900
1-Methyl naphthalene
NA
NA
4,900
3,600
NA
3,600-4,900
4,200
2-Methyl naphthalene
9,900
6,900
11,000
6,400
NA
6,400-11,000
8,600
2-Methyl phenol
870
1,200
650
360
NA
380-1,200
reo
4-Melhyl phenol
2,500
1,400
2.900
1,200
NA
1,200-2,900
2,000
m-Xytene
230
91
66
100
110
66-210
120
Naphthalene
53,000
32,000
84,000
50,000
NA
32,000-84,000
55,000
o/p-Xylene
180
68
59
77
85
59-160
90
Phenanthrene
35,000
23,000
31,000
30,000
NA
23,000-35,000
30,000
PhencH
3,200
3,300
3,500
1,500
NA
1,500-3,500
2.900
PyTene
14,000
10,000
17,000
16,000
NA
10,000-17,000
14,000
Sty? ere
66
< 17
NA
NA
NA
<17-86
¦17
ToJuene
270
r . . 1 L _l "TT _
130
140
r> nx nnn lialt Ilia notA<-
160
ll.lllt
1G0
130-270
170
b NA » Not Analyzed
c ND - No! Detected
Souice: Analytical Data Reports
-------
Waste generation estimate
Tar processing g tar distillation residue/
rate, aal/vr gal tar processed"
25,661,000 0.27
3,091,000 0.37
19,650,000 1.03 Average = 1.37 g (tar
14,700,000 0.37 distillation residue)
8,500,000 4.80 gal tar processed
Assume specific gravity of 1.5 for tar distillation residue.
1.98x10s gal/yr of tar is processed at tar refining plants
generating this waste stream, yielding a waste generation estimate
for tar distillation residue of (1.98xl0e gal/yr of tar) = 270
Mg/yr.
c. Tar Refining Wastewaters
The wastewater generation factor for tar refining plants is
0.48 gal/gal of coal tar processed. Using this factor, the total
quantity of wastewater generated by tar refining plants is
estimated to be 4.2xl05 m3/yr.
2 . Concentration of Constituents Present in Tar Refining Process
Sludges or Residuals and Wastewaters
EPA sampled two tar refining facilities from 1985 to 1989. The
Sampling and Analyses Plans and Analytical Data Reports,
summarizing the sampling performed and the analytical results
obtained for the samples collected, are available in the docket for
this rulemaking.
58
-------
The constituents present in tar refining residues and wastewaters
can be divided into three groups: volatiles, polynuclear aromatic
hydrocarbons (PAHs), and phenolics. Tables 22 and 23 present the
ranges and averages of measured concentrations for the constituents
analyzed in residues and wastewaters from tar refining processes.
Volatiles, including benzene, were not analyzed in tar distillation
residues (K148) because volatiles are not expected to be present in
distillation residues that have been heated to high temperatures.
59
-------
TABLE 22 : TAR DISTILL/ .ON RESIDUES (KM8)
MEASURED CONCENTRATIONS OF CONSTITUENTS (ALL VALUES IN PPM)
CONSTITUENT
SAMPLE
SAMPLE
SAMPLE
RANGE
AVERAGE
NUMBER 41
NUMBER 42
NUMBER 43
Acenaplithene
360
1,500
6.6
6.6-1,500
610
Acenaplitliylene
ND
ND
<5
ND-<5
2.5
Anthracene
960
3,600
24
24-3,600
1,500
Denzene
NA
NA
NA
NA
NA
Benz(a)anthracene
3.000
10,000
160
160-10,000
4,500
Benzo(a)pyrcne
3,300
7,300
330
330-7,300
3,600
Benzo(b and
5,400
13.000
150
150-13,000
6,100
Benzo(g,h,i)perylene
2,000
3,200
130
130-3,200
1,800
Chrysene
3,200
7,900
240
240-7,900
3,800
Dibenz(a,h)anthracene
960
1,400
36
36-1,400
800
2,4-Diinethylphenol
ND
ND
<5
ND-<5
2.5
2,4-Dinitrotoluene
NA
NA
<15
<15
7.5
Ethylbenzene
NA
NA
NA
NA
NA
Fluoranthene
7,000
15,000
310
310-15,000
7,300
Fluorene
ND
2,100
6.6
6.6-2,100
1,000
Ideno( 1,2,3-cd)pyrene
1,800
3,300
110
110-3,300
1,700
I-Methyl naphthalene
NA
NA
2
2
2
2-Methyl naphthalene
ND
540
4
4-540
270
2-Methyl phenol
ND
ND
<5
ND-<5
2.5
4-Methyl phenol
ND
<2 00
<5
ND-<200
51
m-Xylene
NA
NA
NA
NA
NA
Naphthalene
<330
2,400
17
17-2,400
850
o/p-Xylene
NA
NA
NA
NA
NA
Phenanthrene
4,300
12,000
130
130-12,000
5,300
Phenol
ND
<200
<5
ND-<200
51
Pyrene
5,100
12,000
580
580-12,000
5,900
Styrene
NA
NA
NA
NA
NA
Toluene
¦¦¦ ¦¦ 1 ¦' ' —1
NA
NA
" , . - i.. . . ... -
NA
NA
—i n—r-—' —'————
NA
b NA ~ Not Analyzed
c ND = Not Detected
Source: Analytical Data Reports
-------
TABLE 23 : TAR REFINING WASTEWATERS
MEASURED CONCENTRATIONS OF CONSTITUENTS (ALL VALUES IN PPM)
CONSTITUENT SAMPLE
NUMBER 44
SAMPLE
NUMBER 45
SAMPLE
NUMBER 46
SAMPLE
NUMBER 47
RANGE
AVERAGE
Acenaphthene
3
4.6
<4
9.6
2 - 9.6
4.8
Acenaphthylene
0.3
5.2
<3
1.4
0.3 - 5.2
2.1
Anthracene
0.8
3.1
<2
9.6
0.8 - 9.6
3.6
Benzene
190
NA
NA
0.031
0.031 - 190
95
Benz(a)anthracene
NA
NA
NA
5.4
5.4
5.4
Benzo(a)pyrene
NA
NA
NA
<1
<1
0.5
Benzo(b and k)fluoranthene
NA
NA
NA
2.3
2 3
2.3
Benzo(g,h,i)perylene
NA
NA
NA
ND
ND
ND
Chrysene
NA
NA
NA
3.4
3.4
3.4
Dibenz(a,h)anthracene
NA
NA
NA
ND
ND
ND
2,4-Dimetliylphenol
5.5
20
<1
7.6
<1-20
8.4
2,4-Dinitrololuene
NA
NA
NA
NA
NA
NA
Ethylbenzene
10
NA
NA
0.025
0.025 - 10
5
Fluoranthene
2
4.6
<2
24
<2 - 24
7.9
Fluorene
2
2.7
<2
14
<2-14
4.9
Ideno( 1,2,3-cd)pyrene
NA
NA
NA
ND
ND
ND
1-Methyl naphthalene
2
1.7
<4
NA
1.7-2
1.9
2-Methyl naphthalene
3
3 6
<3
6.5
<3 - 6.5
3.7
2-Metliyl phenol
18
77
<1
65
<1-77
40
4-Methyl phenol
53
250
3.2
40
3.2 - 250
87
m-Xylene
160
NA
NA
0.097
0.097 - 160
80
Naphthalene
24
51
52
25
24 - 52
38
o/p-Xylene
140
NA
NA
0.067
0.067 - 140
70
Phenanthrene
4.5
12
<2
35
<2 - 35
13
Phenol
91
22,000
210
140
91 - 22,000
5,600
Pyrene
1
4.1
<3
24
1 - 24
7.7
Styrene
NA
NA
NA
NA
NA
NA
-------
jj Toluene 310 NA 0.033 0.033 - 310 160
SECTION IV
WASTE MANAGEMENT PRACTICES
This section describes the
each listed residual (K141 through K145, K147 and
practices were determined on a plant specific basis
stream and on an industry wide basis for recycling,
sources of information on current waste management
the responses to the 1985 RCRA 3007 questionnaires
current waste management practices for
K14 8). These
for each waste
The principal
practices were
and the 1987
clarification responses.
Guidelines Data were used
practices for coke by-products
Impact Analysis Report (DPRA,
for determining the management
wastes. Table 24 summarizes
practices for the coke plant
In addition, Effluent Limitations
for determining current management
wastewaters. The Cost and Economic
1990) used best engineering judgement
practices for each of the proposed
the information obtained on management
residual streams. Coal tar refining
waste management practices are summarized in Table 25.
A. Waste Management Practices of Coke By-Products Wastes
Proposed for Listing
62
-------
The following discussion provides a summary of management practices
for each waste proposed for listing. This information is
summarized in Table 24. The four primary waste management
practices for coke plant residual streams other than wastewaters,
in order of the most frequently used practice, are reuse in the
process, combustion as a fuel, landfilling, and removal by
63
-------
TABL. A
WASTE MANAGEMENT PRACTICES FOR
COKE BY-PRODUCTS RECOVERY WASTES (PERCENT)"
WASTE MANAGEMENT
PRACTICE
K 141
RESIDUES
FROM TAR
RECOVERY15
KH2
TAR STORAGE
TANK
RESIDUES
K 143
RESIDUES
FROM LIGHT
OIL PROCESSING
K 144
WASTEWATER
TREATMENT
SLUDGES FROM
LIGHT OIL REFINING
K 145
RESIDUES FROM
NAPHTHALENE
COLLECTION
RECOVERY
j Discharge to POTW
0
0
0
0
0
Discharge to Surface Water
0
0
0
0
0
Reuse, Returned to Process
I00b
31
53
43
100
Removed by Waste Removal
: Contractor
0
8
13
29
0
Burned in Boiler/Used as
Feul
0
31
19
14
0
Landfill
0
31
6
14
0
Other
0
0
6C
0
0
No. of Facilities Reporting
1
13
17
8
5
Percent of Total Coke
Production By Responding
Facilities
5
44
27
27
16
Percentages are based on number of facilities responding to the RCRA 3007 questionnaire which reported management practices, not number of facilities
that generated waste. Totals may exceed 100 percent because many facilities reported more than one waste management practice.
Only one plant reported management practices for tar collecting sump residues and that plant indicated that residues are recycled to the decanter. This
number may not be representative of all facilities.
Sold or sloied.
>ource: RCRA 3007 Questionnaire.
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TAULE 25
WASTE MANAGEMENT PRACTICES FOR
TAR REFINING RESIDUES (PERCENT)a
WASTE MANAGEMENT
PRACTICE
K 147
TAR STORAGE
TANK RESIDUAL
K1 <18
TAR DISTILLATION
RESIDUE
Discharge to POTW
0
0
Discharge to Surface Water
0
0
Reuse, Returned to Process
0
33
Removed by Waste Removal Contractor
50
33
Burned in Boiler/Used as Fuel
0
0
Landfill
50
33
Thermal Evaporation in Tanks
0
0
Other
0
0
No. Of Facilities Responding
4
6
Percent of Total Tar
Production by Responding
Facilities
50
55
Percentages aie based on number of facilities responding (o the RCRA 3007 questionnaires, which reported management piactices, not
number of facilities that generated waste. Totals may exceed 100 percent because many facilities reported more than one waste management
practice.
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designated contractors for off-site disposal. Further details on
off-site waste management practices utilized by the contractors
were not reported in the RCRA 3007 questionnaires, but presumably
the wastes are either landfilled or used as a fuel because of their
high heating value (>12,000 BTU/lb).
1. Process Residues from the Recovery of Coal Tar (K141)
Only one plant reported management practices for tar collecting
sump residues. That plant reported recycling those residues back
to the process.
2. Tar Storage Tank Residues at Coking Facilities (K142)
The most frequent management practice for tar storage tank residues
at coking facilities that provided information is recycling those
residues back to the coke oven (31%). Eight percent of the
facilities reported removal of the wastes by designated
contractors; 31 percent of the facilities reported burning the
wastes in boilers or using them as fuels? and 31 percent of the
facilities reported landfilling these wastes.
3. Residues from Light Oil Processing Units (K143)
Benzol plant scrubber residues, wash oil purifier residues, and
decanter muck currently are being managed in a variety of ways.
66
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These residues are ij recycled back to the coke oven, the tar
decanter, or the tar sump; 2) dissolved in the wash oil and
recycled to the light oil recovery process; 3) burned as fuel in an
on-site boiler or blast furnace, or 4) sent off-site for
reclamation. Of the facilities which provided information on this
waste stream, 53 percent reported recycling these wastes by
returning them to the process, 13 percent reported removal of the
wastes by designated contractors, 19 percent reported burning these
wastes in boilers or using them as fuels, and 6 percent reported
landfilling these wastes. The remaining facilities sell these
wastes. Some facilities do not recycle this material because of
concerns with flash point and/or polymerization reactions with this
material and other coking wastes.
4 . Wastewater Sump Residues from Light Oil Refining ('K144^
The primary management practice for these residues is recycling
back to the coke oven. Other practices reported include recycling
to the tar decanter, recycling to the tar sump, and dissolving in
the wash oil and recycling to the light oil recovery process. Of
the facilities providing information on this waste stream, 43
percent reported recycling these wastes to the process, 29 percent
reported removal of the wastes by designated contractors, 14
percent reported management of the residues by landfilling, and 14
percent reported burning these wastes in boilers or using them as
fuels.
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5. Residues From Naphthalene Collection and Recovery CK145)
Residues from naphthalene collection and recovery are currently
managed by recycling them back to the tar decanter, the coke oven,
or the crude coal tar tank.
B. Waste Management Practices of Tar Refining Residues
Following is a discussion of each waste proposed for listing
generated at tar refining plants. These practices are summarized
in Table 25.
1. Residues from the Storage of Coal Tar (K147)
Waste management practices reported for tar storage tank residues
at tar refiners include recycling back to the coke oven, recycling
to the process using circulation pumps, and landfilling, both on-
site and at a commercial sanitary landfill. Out of the facilities
that reported their waste management practices, two facilities have
their wastes hauled by contractors and two dispose of the material
by landfilling. Many facilities are now minimizing the generation
of this waste by fitting stirring devices in the tar storage tanks
and keeping the residues in suspension. Thus, the materials go
through the refining process and become part of the products.
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Waste management practices for coal tar still bottoms and residues
include recycling to the process (i.e. . back to the coke oven or to
the tar distillation process along with the crude tar) (33
percent); landfilling, both on-site and at a commercial sanitary
landfill (33 percent); and removal of the wastes by designated
contractors (33 percent).
C. Wastewater Management Practices at Coke By-Products and Tar
Refining Facilities
The RCRA Section 3007 data provided the following information
regarding coke by-products wastewater management practices. This
information indicated that 49 percent of the facilities discharge
these wastewaters to publicly owned treatment works (POTW), 25
percent of the facilities discharge these wastewaters to surface
water, 21 percent reuse these wastewaters in their process (e.g..
use as quench water) , and the remaining four percent of the
facilities dispose of these wastewaters in underground injection
wells. Quenching is a direct-contact, evaporative cooling process
used to cool the coke from approximately 700°C to between 100° and
150 °C to prevent combustion. Waters used in the quenching
operation are recycled until completely eliminated via evaporation
(extinction). Consequently, any contaminants contained in the
wastewaters used for quenching are either transferred to the coke
69
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or emitted to the atmosphere with the steam plume from the quench
tower.
According to the information available to the Agency, a significant
number of coke by-products facilities use biological treatment for
these wastewaters before discharging them to a POTW or through
their NPDES permitted outfall. However, some facilities discharge
their wastewaters to a POTW without any treatment on-site. Most of
the facilities treat their wastewaters in tanks.
Wastewaters generated at coke plants are generally managed via a
RCRA-exempt wastewater treatment unit (i.e.. treatment in tanks
prior to discharge). Based on previous surveys, some facilities
reported treatment of wastewater via surface impoundments prior to
discharge. Based on the limited information available to the
Agency, four facilities have reported storing sludges resulting
from wastewater treatment in surface impoundments, one facility has
reported storing sludges from wastewater treatment in waste piles,
three facilities have reported disposing of sludges from wastewater
treatment in landfills, one facility has reported incinerating
sludges from wastewater treatment. Some plants did not report any
sludge generation.
According to the information available to the Agency, all units in
which tar refining wastewaters are managed are either 1) wastewater
treatment tanks, which are excluded from permitting and interim
70
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status standards under 40 CFR 264.1(g)^6) and 265.1(c)(10); or 2)
surface impoundments that are already regulated under Subtitle C
because they are used to manage K03 5 sludges. EPA does not have
any information indicating that any tar refining facility is land
disposing wastewaters or wastewater treatment sludges.
D. Recycling
Several recycling exclusions were proposed on July 26, 1991 (56 FR
35758) for coke by-products and tar refining residues that are
recycled to coke ovens or combined with coal tar. The proposed
exclusions were to be effective at the point of reinsertion to the
coke oven or mixing with coal tar. In response to commenter
concerns over the effective date of the BIF rule, and because the
Agency did not want to disrupt the legitimate recycling of coke by-
product residues, EPA then issued an Administrative Stay on
September 5, 1991 (56 FR 43874) to stay the permitting standards of
the BIF rule as they apply to coke ovens that process TC hazardous
residues in the production of coke. EPA also issued a final rule
outlining the applicability of recycling exclusions to TC hazardous
wastes in this industry (57 FR 27880, June 22, 1992).
A number of the residuals being listed in this final rule are
recycled by a substantial segment of the coke by-products industry.
Two recycling techniques are generally used: (1) using mixtures of
71
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the wastes and coal to charge coke ovens and (2) mixing the
residuals with coal tar prior to its being sold. These recycling
practices also are commonly used for tar decanter sludge, which is
already listed as a hazardous waste (EPA Hazardous Waste No. K087).
The recycling of wastes from this industry is affected by the
combined promulgation of two major rules. One of them, the
Toxicity Characteristic, was promulgated on March 29, 1990 (55 FR
11798) . The other, the Boiler and Industrial Furnace (BIF) rule,
was promulgated on February 21, 1991 (56 FR 7134). Because these
rules were promulgated before this listing rule (with its attached
exclusions), the Agency promulgated an exclusion from the
definition of solid waste (§261.4(a)(10)) for wastes from the coke
by-products industry that are recycled in certain ways.
EPA has analyzed the recycling practices for each of the residuals
being listed to determine (a) whether these practices constitute
waste management and, therefore, should be regulated as such or (b)
whether the sludges and by-products are being used in ongoing,
continuous manufacturing processes and, therefore, should not be
regulated under RCRA when these recycling practices are used.
Based on this analysis, the Agency has decided to exclude EPA
Hazardous Waste Nos. K141 through K145, K147, and K148 from the
definition of solid waste when these materials are reinserted into
coke ovens, recycled to the tar recovery process, or blended with
coal tar prior to its sale or refining. As explained fully below,
72
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EPA believes thai: regulation of these materials upon reuse is not
necessary to protect human health and the environment and will not
further the objectives of waste minimization and pollution
prevention.
The effect of this exclusion is that the coking process, using
mixtures of these residuals as feedstock, is not regulated under
Subtitle C of RCRA. Also, the tar refining process, using mixtures
of these residuals and coal tar as feedstock, is not subject to
Subtitle C controls. EPA's rationale for providing this exclusion
is presented in Section D.2 below.
The exclusions proposed on July 26, 1991 would have applied at the
point of reinsertion of residues into coke ovens or mixing with
coal tar, and not before those activities. In response to industry
concerns, the Agency promulgated a more flexible exclusion,
conditioned on no land disposal of the residues, on June 22, 1992
(57 FR 27880). That rule provided an exclusion from the definition
of solid waste for coke by-product plant residues that exhibit the
TC when those by-products are recycled by being returned to coke
ovens directly or by being mixed with coal tar prior to its
refining or sale as a product. This exclusion includes residues
from the coal tar refining process, as well as residues otherwise
classified as K087 (provided, of course, that these residues are
recycled within the terms of the exclusion). The exclusion applies
subsequent to the point of generation of the residues and also
73
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applies to residues whether or not generated at the site of the
coke oven or tar refiner. Importantly, the exclusion is
conditioned on there being no land disposal of the residues at any
point from residue generation to reinsertion to the coke oven or
tar recovery or refining process. Materials that are stored in
piles on the land are thus considered to be solid wastes and are
not excluded from regulation. Similarly, materials used in a
manner constituting disposal or incinerated are fully regulated
under RCRA Subtitle C and all units managing these wastes must meet
applicable RCRA regulations. Conditioned in this way, the Agency
believes the exclusion is a reasonable exercise of its discretion
to determine whether materials are "discarded."
The Agency notes further that these materials become solid and
hazardous wastes if they are accumulated speculatively. See 40 CFR
261.2(c)(4) and 261.1(c)(8). This constraint guards against
prolonged accumulation without recycling of the residues, a
situation that has lead to repeated severe damage incidents in
other recycling industries. (See 50 FR 658-61; January 4, 1985.)
1. Classification as a Solid Waste
The definition of solid waste (40 CFR 261.2) states that certain
secondary materials, when used as or to produce a fuel, are solid
wastes (see 40 CFR 261. 2 (c) (2) (i) (B) ) . The regulations also state
that materials that are reused as ingredients in an industrial
74
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process or as substitutes for commercial products are not solid
wastes; however, those used to produce a fuel are considered to be
solid wastes, even if the recycling involves use, reuse, or return
to the original process (see §261.2(e) (2) (ii)) . Waste-derived coke
and coal tar are considered by-products for regulatory purposes and
are burned, albeit not exclusively or necessarily, for energy
recovery. Since some energy recovery ultimately occurs, they are
solid wastes under the current classification scheme.
2. Rationale for Exclusions from the Definition of Solid Waste
for Coke Bv-Products Residuals Recycled to the Coke Oven or Mixed
with Coal Tar
The residuals being listed as hazardous wastes act as feedstock to
the coking process when recycled, providing a source of carbon that
is needed for the manufacture of coke. Although the iron and steel
industry generally uses only small volumes of residuals with
respect to the amount of coal used, the Agency believes that the
practice of reinserting these residuals into coke ovens serves to
replace the raw material (i.e.. coal). Similarly, the practice of
mixing the residuals with coal tar prior to its sale constitutes
replacing a product (i.e. . coal tar) . The Agency has concluded
that the quality (i.e.. levels of hazardous constituents) of the
coke produced is unaffected by the use of residuals in the
feedstock. Similarly, EPA believes that the quality of coal tar is
unaffected by mixing certain wastes with the coal tar prior to its
75
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sale, as typically practiced by the industry (50 FR 49170; November
29, 1935). For these reasons, the Agency believes that reinsertion
of these residuals into coke ovens and mixing of these residuals
with coal tar to be sold as a product are recycling practices that
do not increase the levels of hazardous constituents in the final
coke product and, therefore, do not pose any significant increased
risk to human health and the environment.
EPA has evaluated whether concentrations of toxic constituents in
the residuals were likely to have a significant effect on the
products of the recycling processes as compared with the products
derived solely from raw materials (i.e. . coal that is feedstock for
coke ovens and coal tar that is feedstock for tar refining). This
evaluation was performed by using the results and supporting data
considered in developing the Agency's proposal to exclude coke and
coal tar produced from or containing recycled tar decanter sludge
(EPA Hazardous Waste No. K087) from the definition of solid waste.
This proposal was based on the Agency's findings that: (1) the
recycling of tar decanter sludge by application to the coal charge
does not appear to have a significant effect on the chemical make-
up of coke, (2) the organic chemical make-up of the sludge does not
appear to be significantly different from the coal tar, and (3)
although the concentration of one metal, lead, appears to be
slightly higher in the sludge than in the coal tar, the increase
does not appear to be statistically significant. EPA, therefore,
determined that recycling of EPA Hazardous Waste No. K087 does not
76
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significantly affect the concentrations of toxic metals and organic
constituents in coal tar or coke. Based on this determination and
on the fact that coke, coal tar, and sludge arise from a single
process, are similar materials, and contain the same constituents,
EPA proposed that coke and coal tar containing or produced from
K087 be classified as products and not wastes (see 52 FR 17019-
17020; May 6, 1987).
Since EPA does not have analytical data for coke or coal tar
produced from feed containing the wastes being listed, the Agency's
approach for evaluating these wastes was to compare the
concentrations of the hazardous organic constituents in these
wastes with the same constituents in EPA Hazardous Waste No. K087.
In performing this comparative analysis, the Agency used data
available for K087 that demonstrate the effects of using recycled
materials on the quality of coke and coal tar produced. The Agency
believes the same results would apply to wastes that are recycled
in the same manner, are physically similar to K087, and have
concentrations of hazardous constituents similar to or lower than
the concentrations of these constituents in EPA Hazardous Waste No.
K087. The results of this comparative analysis are provided in
Table 26. In general, EPA found that typical concentrations of the
constituents of regulatory concern in the wastes C i.e.. organic
constituents) were similar to or lower than the concentrations of
the same constituents in EPA Hazardous Waste No. K087. The
Agency's general understanding of the process indicates that the
77
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levels of toxic metals would not increase from K087 to the other
wastes being listed.
78
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TABLE 26
COMPARISON OF CONCENTRATIONS OF HAZARDOUS CONSTITUENTS IN COKE BY-PRODUCTS WASTES
(K 141 THROUGH K145, KI47, AND K.148)
PROPOSED FOR LISTING WITH CONCENTRATIONS IN K087
CONCENTRATION ('> CONCENTRATIONIN COKE BY PRODUCTS WASTES PROPOSED FOR LISTING (ppm)
CONSTITUENT IN K087 (ppm) K141(,) KM2(?) K143(7) K144(?) K145(2) K147!?) KMfl!2'
Arsenic
0 20-20
Cadmium
1 7-2 1
1 1
1 1
Chromium
<2 0
1 2 2
1-2 2
Lead
31 154
29-43 5
29-43 5
Mercury
2 9-4 2
Anthracene
6,700-14.200
10,400
3,220-5.850
<40-343
162
94 4-226
3.220-5,850
955-3 630
Phenanthrerie
15.000-43,200
36,000
23,300-34,100
160-2,040
623
242-609
23,300-34,100
4.300-11.500
Benz(a)an1hiacerte
4,600-0.465
7,050
5.400-7,440
ND-323
<15-140
<3-26
5,400-7,440
160-10.200
Chrysene
4,400-7.950
7,950
3.990 5.560
<5-247
120
22 6-<9G
3,990-5,560
3,1 '50-7,930
Benzo(a)pyrene
3,600-8,450
8,450
4,450-0.300
<10-134
<20-133
ND-22
4,450-8.300
330-7.270
Fluoranthene
<982-20.200
25,000
17,000-21,400
ND(<40)-1,530
411
107-141
17,000-21,400
6.9£0-14,700
Pyrene
5.900 20.500
20,500
10,200-13.700
116-805
250
69.5-79
10.200-13.700
5.140-12,100
Naphthalene
36.000-95,000
95,000
31,600-04,200
1,400-460,000
350-53,400
5 7-300,000
31,600-84.200
17 5.380
Phenol
490-5.900
5,900
3,240-3,250
ND(<40)-<97 1
ND(<61)
69 5-206
3,240-3,250
ND(<200)
(1) Reference: Best Demonstiated Available Teclinology (UDAT) Background Document for K087
(2) Source: Analytical Data Reports
ND -- Not Detected
79
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3. Description of the Recycling Process Including Pretreatment
and Management Practices for Excluded Wastes
The coke by-product wastes to which the recycling exclusion applies
require certain management and processing steps in order to obtain
a homogeneous material suitable for recycling. These preliminary
steps are considered one integral part of the recycling process
and, as such, are included in the recycling exclusion under 40 CFR
261.6(c)(1). The section describes the existing management and
processing steps practiced in the coke by-products industry.
(These practices apply to K087 wastes as well as to the wastes
being listed in today's rule.) The Agency considers the recycling
exclusion at 40 CFR 261.4(a)(10) to encompass the manner in which
the residuals are handled, the transport of residuals from the
point of generation to the point of recycling, any intermittent
storage, and all processing used to obtain a homogeneous material.
However, if any of these preliminary processing steps involve
placement of the materials on the land, then the exclusion does not
apply to those materials. The processing and management practices
are discussed immediately below. The technical descriptions of the
processes are not exclusive of other available recycling
technologies; however, the wastes and processes are covered by the
exclusion provided the wastes are not land disposed.
80
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a. Management Practices for Residuals from their Point of
Generation to the Point of Reinsertion into Coke Ovens
(i) Conveyance to storage or blending unit
Based on the information available to EPA, the transportation of
these residuals from their point of generation to the storage or
blending site typically takes place in trucks or hopper cars.
Facilities involved in recycling these residuals transport them to
the blending site or store them in tanks (see 40 CFR 260.10 for
EPA's definition of tank). Fork lifts or trucks are used to
transport the hopper cars or tanks from the point of generation to
the blending site. In some cases, residues may be directly
transported through pipes. Interim management practices include
storage of the residuals and mixing with coal. Wastes recycled on-
site may be stored without a permit, as long as the terms of the
exclusion are met.
Some of the materials being listed also may be transported from one
facility to another. Such transportation may occur across a
property boundary of adjacent facilities or over several hundred
miles and across state lines. If the terms of the exclusion are
met, these materials are not solid wastes and consequently, are not
hazardous wastes. Therefore, the transport of the materials does
not require a manifest and the storage of wastes received from
another facility does not require a permit..
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(ii) Blending of residuals with coal
The blending of these residuals with a portion of the coal feed is
typically practiced to make the recyclable material physically
similar to the coal feed (i.e.. to give the feedstock blend a solid
consistency as opposed to the semisolid form in which some of the
residuals are generated). Most of the processing steps involved in
preparing the residual/coal mixture are carried out to avoid "hot
spots" in the coke oven, operational problems that may be
encountered, and any long-term damage to the coke oven as a result
of using these residuals as a part of the feedstock. The recycling
process also is carried out in a way such that the quality of coke
manufactured is unaffected. After blending, subsequent holding or
mixing tanks may be used to incorporate additional coke by-product
residues into the mixture. A homogenizing agent may be added
during the blending process.
From the point of generation, the hoppers may be transported to
"heater huts" (metal sheds heated by steam pipes) prior to
blending. The residues are then generally added to heated batch
tanks where grinding and blending occur or to such units as ball
mills. To comply with the Land Disposal Restrictions (LDR, 40 CFR
Part 268), many facilities have had to discontinue placing K087
wastes on the ground, in a pit, or on a low-walled concrete pad to
mix these wastes with coal. Instead, these wastes must be managed
in a unit such as a tank to accommodate K087 (and other) wastes.
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For facilities without such units, the Agency believes that
recycling the wastes without land placement will cause minimal
extra requirements over and above what already exists. The final
homogenized residual mixture is then transported to the coal feed
site.
(iii) Feeding the coke oven or mixing with coal tar
The first step of the recycling process is feeding the coke oven or
mixing the homogenized mixture with coal tar. When used as coke
oven feed, the residual mixture is generally put on the conveyor
that feeds the coke oven, or it is sprayed on the coal as it
ascends a conveyor belt. The entire process described above,
including transportation, heating, conveyance, blending, and
feeding, is excluded from regulation under 40 CFR 261.4(a)(10),
provided there is no placement of materials on the land.
Management Practices for Residuals Proposed for Listing as
Hazardous Prior to Blending with Crude Coal Tar
EPA included K087 in the exclusion from the definition of solid
waste at §261.4(a)(10). Several commenters to the July 26, 1991
proposed rule expressed concern over the rescission of the
exclusion for coke and coal tar products containing K087 at 40 CFR
261.6(a)(3)(vii). This provision was rescinded in the BIF rule,
wherein the Agency also promulgated an exclusion from the
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definition of solid waste for coke and coal tar produced from K087.
This exclusion negated the need for the exemption at
§261.6(a) (3) (vii). Likewise, the exclusion promulgated on June 22,
1992 (57 FR 27880) replaces the exclusion published in the BIF rule
at §261.4(a)(10) and makes it unnecessary to mention the coke and
coal tar products in the exclusionary language. Since the residues
are not solid wastes when they are recycled (provided no land
disposal occurs), the products made from those residues cannot be
solid or hazardous wastes.
Conclusions
In conclusion, the practice of reinserting these residuals, K141
through K145, K147, and K148 back into coke ovens serves to replace
the raw material coal, and the practice of mixing these residuals
with coal tar serves to replace or augment the product coal tar.
The practice, based on available information, seems to pose no
additional hazard to human health and the environment. Therefore,
the Agency has excluded these residuals from the definition of
solid waste when reinserted into coke ovens, reused in the tar
recovery process, or mixed with product coal tar under 40 CFR
261.4(a)(10), conditioned on no land disposal of the residues.
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SECTION V
BASIS FOR LISTING
A. Summary of Basis for Listing
Each of the seven wastes from the production and recovery of coke
by-products or from tar refining meets the criteria for listing a
waste as hazardous presented in 40 CFR §2 61. 11 (a) (3) .
Consequently, EPA is adding these wastes to the list of hazardous
wastes from specific sources appearing at 40 CFR 261.32. Hazardous
constituents are typically present in these wastes at such levels
that ground-water concentrations of these constituents are expected
to exceed health-based levels of concern when the wastes are
improperly managed. As discussed below, all of the constituents of
concern are carcinogens and/or systemic toxicants. In addition,
all of the constituents of concern are listed as hazardous
constituents at 40 CFR Part 261, Appendix VIII. Under plausible
mismanagement scenarios, the Agency believes that these hazardous
wastes (EPA Hazardous Waste Nos. K141 through K145, K147, and K148)
are capable of posing a substantial present or potential hazard to
human health or the environment.
Table 1 (Section 1) presents the selected constituents of concern
in each of the wastes. Table 27 presents the ranges of measured
concentrations of constituents of concern in coke by-products and
tar refining wastes. EPA selected the constituents of concern
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TABLE 27
COKE AND COKE BY-PRODUCT WASTES!CONSTITUENTS OF CONCERN
AND RANGE OF MEASURED CONCENTRATIONS
(ALL VALUES IN PPM)
CONSTITUENT
Benzene
K141
PROCESS RESIDUES
FROM COAL TAR RECOVERY"
K142
TAR SIORAGE TANK
RESIDUES
BAunF a \ir.
K143
RESIDUES FROM LIGHT
OIL PROCESSING
PAwr.F tvr.
K144
WASTEWATER TREATMENT
SLU0GES FROM LIGHT
OIL REFINING
DAMCF Aun
K145
RESIDUES FROM
NAPHTHALENE
COLLECTION AND
RECOVERY
RAHPJ AUi:
3,850
230 - 290
260
39 - 8,500
1,600
200 - 14,000
3,000
120 - 3,000
1,000
Benz( a) anthracene
7,850
5,400 - 7,400
6,600
NO - 320
69"
<15 - 140
63°
<3 - <96
22"
Benzo(a)pyrene
8,450
4,500 - 8,300
6,500
<10 - 130
34"
<20 - 130
65"
ND - 22
r
Benzolb)fluorenthene'
Benzo(k)fluoranthene'
5, <.50
5,200 - 10,000
7,500
<5 - 230
59"
<15 - 220
75"
2.3 - 48
26"
Chrysene
7,950
4,000 - 7,400
6,000
<5 - 250
59"
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TABLE 27 CtBITIKUCD
COKE AKD COXE BY-PRODUCT UASTES:CDHSI ITUEMTS OF COHCERH
AH) RAMGE Of MEASURED CONCENT RAT I COTS
(AIL VALUES IB PPtl)
KU.7
K148
CONSTITUENT
Benzene
TAR STORAGE
RESIDUES
PAUr.F
TANK
Avr.
TAR DISTILLATION
RESIDUALS
PANHF A \ir.
230 - 290
260
NA
NA
Benz(a)anthracer»e
5,400 - 7,400
6,600
160 - 10,000
4,500
Benzo(a)pyrene
4,500 - 8,300
6,500
330 - 7,300
3,600
Benzo(b)fluoranthene"
Benzo(k)f luoranthene"
5,200 - 10,000
7,500
150 - 13,000
6,100
Chrysene
4,000 - 7,400
6,000
240 - 7,900
3,800
D ibenzC a,h)anthracene
720 - 1,600
1,000
36 - 1,400
800
lr>deno( 1,2,3-cd)pyrerve
2,000 - 4,100
2,900
110 - 3,300
1,700
Naphthalene
32,000 - 84,000
55,000
17 - 2,400
850
*GC peak resolution was not adequate to provide quantitation of the two isomers i ndi v iduol I y. llie results shown are the sum of the two isomers.
HA - Constituent not analyzed (volatiles were not anticipated in still bottoms thot have been heated to high tenperatures).
8 7
-------
based on two principal factors: their known toxicity and their
average concentrations in the waste. Other constituents were
detected in these wastes but were not selected as constituents of
concern because either their health-based levels are not available
or they typically are not present at concentrations of regulatory
concern. Data on these constituents are presented in Sections III
and V.B of this Background Document.
B. Waste Characterization and Selection of Constituents of
Concern
The Agency lists a waste as hazardous if the waste poses a
potential hazard to human health or the environment. In order to
assess the potential hazard that a waste may pose, the Agency
evaluates the human health and environmental risk that a waste may
pose when disposed of improperly. This risk is estimated as a
function of the amount of exposure and the toxicity of hazardous
constituents present in the waste stream of concern. In evaluating
the risk posed by wastes from the coke by-products industry, the
Agency considered exposure to environmental receptors from
contaminated ground water. The amount of exposure to environmental
receptors via ground water is estimated from the expected
concentrations of hazardous constituents in drinking water and the
average amount of water consumed over the entire life span of an
individual.
88
-------
The expected drinking water concentrations of hazardous
constituents from the wastes can be estimated as follows. First,
the concentrations of these constituents released to a leachate
generated from the wastes are estimated. Then, the concentrations
of these constituents in drinking water are estimated after
transportation of the leachate to a drinking-water well. Various
alternatives, discussed below, were considered for estimating the
exposure concentrations.
1• Approaches Considered for Evaluating Coke Bv-Products and
Tar Refining Wastes
In order to estimate the concentration of the constituents of
regulatory concern present in the proposed coke by-products wastes,
EPA considered the use of leachability models and subsurface fate
and transport models to estimate concentrations of these
constituents in drinking water. Specifically, the Agency
considered the use of the Organic Leachate Model (OLM) and the
Toxicity Characteristic Leaching Procedure (TCLP) to estimate the
leachate concentrations that are likely to result from the wastes.
This would be followed by the use of EPA' s Composite Model for
Landfills (EPACML) to estimate the migration of the hazardous
constituents to the drinking water well.
However, due to limitations in the applicability of these models to
a number of the wastes being generated by coke by-products and tar
89
-------
refining facilities,, -he Agency
inappropriate for these wastes,
below.
a. Leaching Protocols
On November 27, 1985, the Agency proposed an Organic Leachate Model
(OLM) to estimate the amount of organic contaminants that will
leach from a waste (see 51 FR 41082 and 50 FR 48886). The OLM is
an empirical equation which was developed through application of
modeling techniques to a data base of waste constituent
concentrations and experimentally measured leachate concentrations.
The OLM takes into account the concentrations of organic
constituents and their aqueous solubility.
However, the OLM does not consider cosolvency effects and therefore
tends to underestimate pollutant mobility in waste matrices where
cosolvency may be significant. EPA believes that, with the possible
exception of tar distillation residues, the wastes proposed for
listing may be subject to significant cosolvency effects.
EPA also analyzed samples of these wastes for selected organic
constituents, using the TCLP (see 55 FR 11798-11862 for details on
this procedure). Problems were encountered in applying the
leaching procedure to some of these wastes. The principal problem
was that some of the samples of these wastes are associated with
90
has determined that they are
These limitations are discussed
-------
variable amounts of tar (i.e. . percent solids) . Tarry samples pose
problems with sample homogenization, filtration, and dispersion of
solids in the leaching medium when performing the TCLP. The
tendency of tar to adhere to surfaces causes mass balance problems.
Because of these difficulties, EPA believes that the TCLP procedure
tends to provide analytical results which may understate the
concentrations of hazardous constituents in leachates from some of
these wastes if they are disposed of in a landfill environment.
Tables 28 through 34 present the TCLP results for the proposed coke
by-proposed wastes. TCLP results for tar collecting sump residues
(K141) are not available. Tar collecting sump residues (K141) are
similar to tar decanter sludge (K087), as they are generated at
similar points in the manufacturing process. Hence, TCLP results
for tar decanter sludge (K087) have been used in place of tar
collecting sump residues (K141) for illustrative purposes.
b. Groundwater Models
EPACML has been used to estimate the attenuation and dilution of
specific constituents during their migration through the
unsaturated zone beneath a municipal landfill and their transport
through the saturated zone to a potential drinking water source
(exposure point). EPACML accounts for dispersion in the
longitudinal, lateral, and vertical directions; one-dimensional
91
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TABLE 28. ORGANIC TCLP RESULTS-TAR DECANTER SLUDGE (K087) (mg/l)a
Acetate
Water
Constituent
TCLP Extract
TCLP Extract
Benzene
3.9
4.2
Ethvlbenzene
TR
TR
m-Xylene
0.16
0.15
o/p-Xylene
0.15
0.14
Styrcne
0.26
0.25
Toluene
0.73
0.71
Quantitation limit
0.05
0.05
Accnaphthene
TR
TR
Acenaphlhvlene
2.6
2.2
Anthracene
038
TR
Benz(a)anthracene
0.2
TR
Benzo(a)pyrene
TR
ND
Benzo(b)fiuoranthene
0.28
ND
Benzo(k)fiuoranthene'"
--
-
Benzo(g,h,i)pyrene
TR
ND
Chrysene
TR
ND
Dibenz(a,h)anthracene
TR
ND
2,4-Dimethylphenol
4.4
5.2
2,4-Dinitrotoluene
NA
NA
Fluoranlhene
TR
TR
Fluorene
0.34
TR
Ideno(l,23-cd)pyrene
ND
ND
1-Methyl naphthalene
NA
NA
2-Methyl naphthalene
0.66
0.55
2-Methvl phenol
12
11
4-Methyl phenol
51
39
Naphthalene
14
D
Phenanthrene
TR
0.22b
Phenol
81
55
Pyrene
TR
TR
Quantitation limit
0.26
0.27
" All numbers have been rounded to two significant figures.
b One of the replicated used to produce this average was below the quantitation limit. To obtain an average the value used
for fhi.c. replicate was 50% of the detection limit.
c Included with Benzo(b)fluoranthene.
NA = Not analyzed
ND = Not detected
TR = Trace; analyte detected below quantitation limit.
Source : Analytical Data Reports
92
-------
TABLE 29
ORGANIC TCLP RESULTS-TAR STORAGE TANK RESIDUE (K142) (mg/l)a
Sample No. 49 Sample No. 50
Acetateb
Acetate6
Water"
Constituent
extract
extract
extract
Benzene
3
1.4
2.0
Ethylbenzene
TR
TR
1.1
m-Xylene
031
0.18
0.21
o/p-Xylene
03
0.19
0.21
Styrene
0.17
TR
ND
Toluene
1.1
0.51
0.68
Quantitation limit
0.05
0.1
0.1
Acenaphthene
ND
0.16
0.097
Acenaphthylene
TR
0.086
TR
Anthracene
ND
TR
ND
Benz(a)antliracene
ND
ND
ND
Benzo(a)pyrene
ND
ND
ND
Benzo(b)fluoranthene
ND
ND
ND
Benzo(k)fluorantlienel1
-
--
--
Benzo(g.h,i)pyrene
ND
ND
ND
Chrysene
ND
ND
ND
Dibenz(a,h)anthraccne
ND
ND
ND
2,4-Dimethylphenol
19
73
10
2,4-Dinitrotoluene
NA
NA
NA
Fluoranthene
ND
TR
ND
Fluorene
TR
0.20
0.19
Indeno(l,2,3-cd)pyrene
ND
ND
ND
1-Metbyl naphthalene
NA
NA
NA
2-Methyl naphthalene
ND
0.76
0.61
2-Methyl phenol
36
12
12
4-Methvl phenol
94
44
34
Naphthalene
26
73
83
Phenanthrene
TR
0.20
0.22
Phenol
120
45
40
Pyrene
ND
ND
ND
Quantitation limit
0.52
0.078
0.08
a AlJ numbers have been rounded to two significant figures.
b Combined Tiltrate and leachate.
c One of the replicated used to produce this average was below the quantitation limit. To obtain an average the value used
for this replicate was 50% of the detection limit.
d Included with Benzo(b)fluoranthene.
NA = Not analyzed
ND = Not detected
TR = Trace; analyte detected below quantitation limit.
Source : Analytical Data Reports
93
-------
TABLE 30
ORGANIC TCLP RESULTS-LIGHT OIL PROCESSING RESIDUES (K143) (mg/!)a
Constituent
Sample No. 51
Wash oil decanter muck
Acelateb
Sample No. 50
Licht Oil Scrubber residue
Acetate
Water
Benzene
Ethylbenzcne
m-Xylene
o/p-Xylene
Stvrene
Toluene
Quantitation limit
Acenaphthene
Acenaphthylcne
Anthracene
Benz(a)anthracenc
Benzo(a)pyrene
Benzo(b)fiuoranthene
Benzo(k)f!uoranthene
-------
TABLE 31. ORGANIC TCLP RESULTS-INTERCEPTING SUMP
SLUDGE (K144) (mg/l)a
Sample No. 53
Constituent
Acetateb
Benzene
15
Ethylbenzene
TR
m-Xylene
0.61
o/p-Xylene
0.51
Styrene
TR
Toluene
3.8
Quantitation limit
0.105
Acenaphthene
ND
Acenaphthylene
9.8
Anthracene
23
Benz(a)anthracene
4.4
Benzo(a)pyrene
4.4
Benzo(b)fluoranlhene
6.7
Benzo(k)fluoranthene
--
Benzo(g.h,i)pYrene
TR
Chrysene
4.2
D i be nz( a, h) an thr a ce n e
ND
2,4-Dimelhylphenol
ND
2,4-Dinilrotoluene
NA
Fluoranthene
16
Fluorene
9.6
Ideno(l,2,3-cd)pyrene
TR
1-Methyl naphthalene
NA
2-Methyl naphthalene
29
2-Methyl phenol
TR
4-Methyl phenol
3.4
Naphthalene
430
Phenantnrene
ND
Phenol
6.6
Pvrene
11
Quantitation limit
3.1
8 All numbers have been rounded to two significant figures.
b Combined filtrate and leachate.
c Included with Benzo(b)fluoranlhene.
NA = Not analyzed
ND = Not delected
TO = Trace; anaiyte detected below quantitation limit.
Source : Analytical Data Reports
95
-------
TABLE 32. ORGANIC TCLP RESULTS-- PROCESS RESIDUES FROM THE FINAL
COOLER/NAPHTHALENE RECOVERY PROCESS (K145) (mg/l)a
Sample No 55
Sample No 54 Final cooling lower
Constituent Naphthalene skimmer sludge sump sludge
Acetate15 Acctateb
Benzene
11
8
Ethylbeazcne
TR
0.062
m-Xylcne
0.50
0.85
o/p-Xylcne
0.60
0.81
Styrcnc
1.1
0.49
Toluene
19
3.0
Quantitation limit
0.1
0.06
Acenaphthene
TR
ND
Acenaphthyiene
1.8
1.4
Anthracene
ND
TR
Benz(a)anthrac£ne
TR
ND
Benzo(a)pyTene
ND
ND
Benzo(b)fluoranthene
TR
ND
Benzo(k)fluoranthenec
--
--
Benzo(g,h7i)pyrene
ND
ND
Chrysene
ND
ND
Dibenz(a,h)anthracene
ND
ND
2,4-Dimethvlphenol
3.8
15
2,4-Dinjtrotoluene
NA
NA
Fluoranlhene
ND
ND
Fluorene
TR
TR
Ideno( l,2^-cd)pyrene
ND
ND
1-Methyl naphthalene
NA
NA
2-Methyl naphthalene
2.4
3.2
2-Methyl phenol
00
00
13
4-Methvl phenol
17
22
Naphthalene
9.4
11
Phenanthrene
ND
TR
Phenol
30
25
Pvrene
ND
ND
Quantitation limit
0.10
0.24
a All numbers have been rounded to two significant figures.
b Combined filtrate and leachate.
c Included with Benzo(b)fluoranthcne.
NA = Not analyzed
ND = Not detected
TR = Trace; analyte detected below quantitation limit.
Source : Analytical Data Reports
96
-------
TABLE 33
ORGANIC TCLP RESULTS--TAR STORAGE TANK RESIDUE (K147) (mg/l)a
Constituent
Sample No. 49
Acetatcb
extract
Sample No. 50
Acetate
extract
Water0
extract
Benzene
Ethylbenzene
m-Xylene
o/p-Xylene
Styrene
Toluene
Quantitation limit
Acenaphthene
Acenaphthylene
Anthracene
Benz(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthened
Benzo(g,h,i)pyrene
Chrysene
Dibenz(a,h)anthracene
2,4-Dimethylphenol
2,4-Dinitrotoluene
Fluoranthene
Fluorene
lndeno( 1,2,3- cd)pyrene
1-Methyl naphthalene
2-Methyl naphthalene
2-Methyl phenol
4-Methyl phenol
Naphthalene
Phenanthrene
Phenol
Pvrene
TR
031
03
0.17
1.1
0.05
ND
TR
ND
ND
ND
ND
ND
ND
ND
19
NA
ND
TR
ND
NA
ND
36
94
26
TR
120
ND
1.4
TR
0.18
0.19
TR
0.51
0.1
0.16
0.086
TR
ND
ND
ND
ND
ND
ND
73
NA
TR
0.20
ND
NA
0.76
12
44
73
0.20
45
ND
2.0
1.1
0.21
0.21
ND
0.68
0.1
0.097
TR
ND
ND
ND
ND
ND
ND
ND
10
NA
ND
0.19
ND
NA
0.61
12
34
8.5
0.22
40
ND
Quantitation limit
0.52
0.078
0.08
a . All numbers have been rounded to two significant figures.
b Combined filtrate and leachate.
c One of the replicated used to produce this average was below the quantitation limit. To obtain an average the value used
for this replicate was 50% of the detection limit.
d Included with Benzo(b)fluoranthene.
NA = Not analyzed
ND = Not detected
TR = Trace; analyte detected below quantitation limit.
Source : Analytical Data Reports
97
-------
TABLE 34
ORGANIC TCLP RESULTS--TAR DISTILLATION RESIDUES (K148) (mg/l)a
Sample No. 56 Sample No 57
Acetateb
Waterb
Acetate1'
Constituent
extract
extract
extract
Benzene
NA
NA
NA
Ethvlbenzcne
NA
NA
NA
m-Xylene
NA
NA
NA
o/p-Xylcne
NA
NA
NA
Styrene
NA
NA
NA
Toluene
NA
NA
NA
Quantitation limit
NA
NA
NA
Acenaphthene
0.05
0.05
0.1
Accnaphthylene
NT)
ND
TR
Anthracene
0.022
0.024
0.062
Benz(a)anthracene
ND
ND
0.006
Benzo(a)pyrene
ND
ND
ND
Benzo(b)fiuoranthene
ND
ND
ND
Benzo(k)fluoranthened
--
--
-
Beczo{g,h,i)pyrene
ND
ND
ND
Chrysene
TR
TR
TR
Dibenz(a,h)anthracene
ND
ND
ND
2,4-Dimethvlphenol
0.026
0.023
NA
2,4-Dinitrotoluene
NA
NA
NA
Fluoranthene
0.02S
0.029
0.08
Fluorene
0.031
0.03
0.11
Indeno(l,2.3-cd)pyrene
ND
ND
ND
1-Methyl naphthalene
NA
NA
NA
2-Methyl naphthalene
0.018
0.023
0.054
2-Mcthy! phenol
0.025
0.02
0.05
4-Methyl phenol
0.06
0.056
0.12
Naphthalene
0.14
0.21
022
PhenanLhrene
0.11
0.12
0.25
Phenol
0.05
0.05
0.11
Pyrene
0.021
0.023
0.05
Quantitation limit
0.005
0.005
0.005
a All numbers have; been rounded to two significant figures.
b Combined filtrate and ieachate.
c One of the reolicated used to produce this average was below the quantitation limit. To obtain an average the value used
for this replicate was 50% of the detection limit.
d Included with Benzo(b)fluoranthene.
NA = Not analyzed
ND = Not detected
TR = Trace; analyte detected below quantitation limit.
Source : Analytical Data Reports
98
-------
steady and uniform advective flow; sorption; and chemical
degradation from hydrolysis. EPACML accounts for the unsaturated
zone transport modules and implements them using the Monte Carlo
(probabilistic) framework. The input concentration to the
unsaturated zone transport module of EPACML corresponds to the
leachate concentration at the bottom of the landfill. Under
certain conditions, particularly very high constituent
concentrations, immiscible liquid flow can occur. For such
situations, the model's inability to account for the immiscible
flow condition may result in an underestimation of the receptor
well concentrations. As discussed below, the wastes generated at
coke by-product and tar refining facilities typically have very
high concentrations of certain hazardous constituents. Therefore,
use of EPACML may result in an underestimate of concentrations of
these constituents at drinking well sites.
2. Evaluation of Coke Bv-Products and Tar Refining Wastes for
Listing
For the reasons stated above, EPA believes that use of available
leaching and subsurface fate and transport models are not
appropriate for wastes generated at coke by-products and tar
refining facilities. In addition, analytical results from the
application of the TCLP to some of the waste samples tend to
understate the concentrations of hazardous constituents in
leachates which may possibly originate from the wastes. However,
99
-------
in spite of the limitations of available methodologies for
evaluating the specific migratory phenomena of these wastes, the
Agency continues to believe that the wastes are hazardous based on
1) consideration of the high concentrations of hazardous
constituents in these wastes, 2) the toxicity of these
constituents, 3) the mobility of the hazardous constituents and 4)
the persistence of the constituents in the environment.
Pursuant to 4 0 CFR §261.11(a) (3), EPA cannot conclude that these
wastes are not capable of posing a substantial present or potential
hazard to human health or the environment when improperly treated,
stored, transported, or disposed. The concentrations and
toxicities of hazardous constituents in the wastes are of such a
magnitude that, even under conservative assumptions regarding the
potential for release of these constituents to the environment and
their subsequent transport in the subsurface environment, improper
management of the wastes poses an unacceptable health risk. The
following discussion illustrates this concern.
Tables 35 through 41 summarize the average concentrations of
hazardous constituents in the wastes and the health-based
concentrations of these constituents in drinking water at specified
risk levels. For illustrative purposes, the tables also indicate
the concentrations of these constituents when hypothetical
environmental exposure factors (HEEFs), ranging from
100
-------
TABLE 3 5
BASIS FOR LISTING:
CONSTITUENTS
HEALTH EFFECTS OF
OF CONCERN IN K141
THE
HAZARDOUS
CONST 1TUENT
AVERAGE
WASTE CONC.
DETECTED
HEALTH-BASED
WATER CONCEH-
T R A T ION
BASIS"
ESTIMATED
DRINKING
CONC."
WELL
(PJ*n)
CALCULATED
BASED LIMIT
CONC. TO
RATIOS'
IIEALTH-
(ppm)
LIMITS (ppm)
HEEF 1UU
HEEF 1UUU
HEEF
1U.UUU
HEEF 10U
HEEF 1UU0
" HEEF 1U,(JU0
Bemene
3,850
5 X 10 '
MCL CA)
38.5
3.85
0.385
7,700
770
77
Beni(a)anthracene
7,850
2 X 10 *
RSD CB.)
78.5
7.85
0.785
39,000,000
3,900,000
390,000
Benzo(a)pyrene
8,450
2x10'
MCL (B.)
84.5
8.45
0.845
420,000
42,000
4,200
Benio(b)fluoranthene
Beruo( k) f I uoranthe»>ed
5,450
4x10'
RSD (B,)
54.5
5.45
0.545
1,400,000
140,000
14,000
Chrysene
7,950
5 x 10 '
RSD (B,)
79.5
7.95
0.795
160,000
16,000
1,600
Dibeni(8,h)anthracene
1,750
7x10'
RSD (B.)
17.5
1.75
0.175
25,000,000
2,500,000
250,000
I r>deno( 1,2,3-cd)pyrene
6,150
4 x 10 '
RSO (8.)
61.5
6.15
0.615
150,000
15,000
1,500
Maphthalene
95,000
1
RfD
950
95
9.5
950
95
9.5
"Reference Dose (RfD), Risk-Specific Dose (RSU), and Maxfnwn Contaminant Level (MCL) ai e explained in the Oockground Docuncnt to todoy'a rule, eo ore the classon of
carcinogens. Class A and B carcinogens are based on exposure limits at a 10' risk level.
"Calculated for three hypothetical environmental exposure factors (HEEFs).
'Ratio obtained by dividing values in estimated drinking well concentration colimn by values In health-based, water concentration limit column for all three HEEFs.
"GC peak resolution was not adequate to provide quantitation of the two isomers indlvicfcjal ly. The results show the sum of the two Isomers.
101
-------
TABLE 3 6
BASIS FOR LISTING: HEALTH EFFECTS OF THE
CONSTITUENTS OF CONCERN IN K142
HAZARDOUS
CONSTITUENT
AVERAGE
WASTE CONC.
DETECTED
HEALTH-BASED
WATER CONCEH-
T R A T 1 0 N
BASIS"
ESTIMATED
DRINKING
CUttC."
WELL
(ppm)
CALCULATED
BASED LIMIT
CONC. TO
RAT IOSe
HEAL T H-
(ppm)
LIMITS (ppm)
HEEF 1UU
HEEF 1UUU
HEEF
1U.U00
HEEF 1U0
HEEF 100U
HEEF 1(1,000
Benzene
260
5 K
10 '
MCL
(A)
2.6
0.26
0.026
520
52
5
Benz(a)anthracene
6,600
2 *
10 •
RSD
IB, J
66
6.6
0.66
33,000,000
3,300,000
330,000
Benzo(a)pyrene
6,500
2 n
10 •
MCL
(B,)
65
6.5
0.65
330,000
33,000
5,300
Benzo(b)f1uoranthene
8enxo(k)fIuoranthene"
7,500
t, X
10 '
RSO
(BJ
75
7.5
0.75
1,900,000
190,000
19,000
Chrysene
6,000
5 x
10 •
RSO
«U
60
6
0.6
120,000
12,000
1,200
Dlbenz(a,h)anthrocene
1,000
7 X
10 '
RSD
(Bj)
10
1
0.1
K,000,000
1,400,000
HO,000
Indeno(1,2,3 -cd)pyrene
2,900
A x
10 '
RSD
(B.)
29
2.9
0.29
73,000
7,300
730
Naphthalene
55,000
1
RfD
550
55
5.5
550
55
5.5
"Reference Dose (RfD), R Ink-Speci f ic Dosa (RSD), Bnd Maximum Contaminant Level (HCL) are explained In the Background Docunent to today's rule, as are the classes of
carcinogens. Class A and B carcinogens ore based on exposure limits at a 10"* risk level.
^Calculated for three hypothetical environmental exposure factors (IIEEFs).
'Ratio obtained by dividing values in estimated drinking well concentration colurai by values In health-based, water concentration limit colurai for all thref HEEFs.
°GC peak resolution was not adequate to provide quantitation of the two Isomers Individually. The results show the sun of the two Isomers.
102
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TABLE 37
BA8I8 FOR LISTING: HEALTH EFFECTS OF THE
CONSTITUENTS OF CONCERN IN K14 3
HAZARDOUS
CONSTITUENT
AVERAGE
WASTE CONC.
DETECTED
HEALTH-BASED
WATER CONCEN-
T R A T 1 O N
BASIS'
ESTIMATED
DRINKING
CONC."
WELL
(ppm)
CALCULATED
BASED LIMIT
CONC. TO
RATIOS'
HEALTH-
(ppm)
LIMITS (ppm)
IIEEF 1UU
IIEEF 10UU
IIEEF
10',DUO
IIEEF TOO
IIEEF 1000
HEEF 1U,0UU
Benzene
1,600
5 x 10 1
MCL
(A)
16
1.6
0.16
3,200
320
32
Beni(a)anthracene
69
2 x 10*
RSD
(B.)
0.69
0.069
0.007
350,000
35,000
3,500
Benzo(a)pyrene
34
2 x 10 '
HCL
(B,)
0.34
0.034
0.003
1,700
170
17
8enzo(b)fluorenthene
Benzo( k) f I uoratit hene"
59
4 x 10 '
RSD
(B.)
0.59
0.059
0.006
15,000
1,500
150
Ctirysene
59
5 x 10'
RSD
(B,)
0.59
0.059
0.006
1,200
120
1.2
Naphthalene
52,000
1
RfD
520
52
5.2
520
52
5.2
Deference Dune (RfD), Risk Specific Dose (RCO), and Hoximun Contaminant Level (MCL) are explained In the Background Docunent to today'o rule, as are the classes of
carcinogens. Class A and B carcinogens are based on exposure limits at 0 10"' risk level.
"Calculated for three hypothetical environmental exposure factors (HEEFs).
'Ratio obtained by dividing values in estimated drinking well concentration colum by values in health-based, water concentration limit colim for all three HEEFs.
"GC peak resolution was not adequate to provide quantitation of the two Isomers Individual ty. The results show the turn of the two Isomers.
103
-------
TABLE 38
BASIS FOR LISTING: HEALTH EFFECTS OF THE
CONSTITUENTS OF CONCERN IN Kl-94
HAZARDOUS
CONSTITUENT
AVERAGE
WASTE CONC.
DETECTED
HEALTH-BASED
WATER CONCEH-
T R A T 1 0 N
BASIS'
ESTIMATED
DRINKING
CONC."
WELL
(ppm)
CALCULATED
BASED LIMIT
CONC. 10
RATIOS'
HEALTH-
(ppm)
LIMITS (ppm)
IIEEF 1UU
IIEEf 1000
MEET
10.U0U
HEEF 100 "
HEEF 1000
HEEF lcruoo
Benzene
3,000
5 x 10 '
MCL
(A)
30
3.0
0.30
6,000
600
60
Benz(a)anthracene
68
2 x 10*
RSD
0.68
0.068
0.007
W0,000
34,000
21, 500
Benzo(a)pyrene
65
2 * 10'
MCL
(B.)
0.65
0.065
0.007
3,300
330
33
Benzo(b)fluoranthene
Benzo(k)fluoranthene"
75
4x10'
RSD
(B,)
0.75
0.075
0.008
19,000
1,900
200
Chrysene
66
5x10'
RSD
(B.)
0.66
0.066
0.007
1,300
130
K
Dlbenz(a,h)anthracene
15
7 x 10'
RSD
(B,)
0.15
0.015
0.002
210,000
21,000
?, 100
lndeno(1,2,3-cd)pyrene
37
4 x 10 '
RSD
(B')
0.37
0.037
0.0037
930
93
9.3
Naphthalene
27,000
1
RfD
270
27
2.7
2,70
27
2.7
"Reference Dose (RfD), Risk-Spec11 ic Dose (HSU), end maxlnun Cumwiiiiiaiil Level (HCL) «i e explained in the Background Document to today's rule, as ore the cl.jnaea of
carcinogens. Class A and B carcinogens are based on exposure limits at a 10'# risk level.
"Calculated for three hypothetical environmental exposure factors (HEEFs).
""Ratio obtained by dividing values in estimated drinking well concentration coluin by values In health-based, water concentration limit colum for all three HEEfs.
"GC peak resolution was not adequate to provide quantitation of the two Isomers indlvlcfcjally. The results show the sun of the two Isomers.
104
-------
TABLE 39
BASIS FOR LISTING: HEALTH EFFECTS OF THE
CONSTITUENTS OF CONCERN IN K145
HAZARDOUS
CONSTITUENT
AVERAGE
WASTE CONC.
DETECTED
HEALTH-BASED
WATER CONCEN-
T R A T 1 0 N
BASIS'
ESTIMATED
DRINKING
CONC."
WELL
(ppm)
CALCULATED
BASED LIMIT
CONC. TO
RATIOS'
HEALTH-
(ppm)
LIMITS (ppn)
HEEF 100
IIEEF 1U00
HEEF 1U.UUU
HEEF 1U0
HEEF 10U0
IIEEf 1U.UU0
Benzene
1,000
5 x 10'
MCL
(A)
10
1 .0
0.10
2,000
200
20
8enz(a)anthrecer>e
22
N
X
o
RSD
(B.)
0.22
0.022
0.002
110,000
11,000
1,000
Benro(a)pyrene
7
2 x 10 '
MCL
(B.)
0.07
0.007
0.001
350
350
3.5
Benio(b)fluoranthene
Benio(k)fluoranthene"
26
4 x 10 '
RSD
(B,)
0.26
0.026
0.0026
6,500
650
65
Dibeni(a,h)anthracene
15
7x10'
RSD
(B,)
0.15
0.015
0.002
210,000
21,000
2,100
Naphthalene
HO,000
1
RfD
1,400
HO
14
1,400
140
14
"Reference Dose (RfD), Risk-Spec i f i c Dose (RSD), and Haxirajn Contaminant Level (MCI) are explained in the Background Docunent to today'8 rule, as are the classes of
carcinogens. Class A end B carcinogens are based on exposure limits at a 10"* risk level.
"Calculated for three hypothetical envirormental exposure factors (HEEFs).
'Ratio obtained by dividing values in estimated drinking well concentration colimn by values In health-based, water concentration limit colum for all three HEEFs.
"GC peak resolution was not adequate to provide quantitation of the two isomers individual ly. The results show the sun of the two Isomers.
105
-------
TABLE 40
BASIS FOR LISTING: HEALTH EFFECTS OF THE
CONSTITUENTS OF CONCERN IN K147
HAZARDOUS
CONSTITUENT
AVERAGE
UASTE COHC.
DETECTED
HEALTH-BASED
WATER CONCEN-
T R A 1 1 0 N
BASIS"
EST 1 HATED
DRINKING
CONC."
WELL
(ppm)
CALCULATED
BASED LIMIT
CONC. TO
RATIOS'
HEALTH-
(ppm)
LIMITS (ppm)
IIEEF 1U0
IIEEF 10UU
IIEEF
10.DUO
HEEF 1UU "
IIEEF 10UU
HEEF 10,DUO
Benzene
260
5x10'
MCL
(A)
2.6
0.26
0.026
520
52
5
Benz(a)anthracer»e
6,600
2 x 10 '
RSO
(B,)
66
6.6
0.66
33,000,000
3,300,000
330,000
Benzo(a)pyrer>e
6,500
2 x 10'
MCL
(B,)
65
6.5
0.65
330,000
3,300
330
Benzo(b)fluorenthene
Benzo(k)fIuoranthene"
7,500
4 x 10 '
RSD
(B,)
75
7.5
0.75
1,900,000
190,000
19,000
Chrysene
6,000
5 x 10 *
RSI)
CB,J
60
6
0.6
120,000
12,000
1,200
01 benzCa,h)anthracene
1,000
7x10'
RSO
o( 1,2,3-cd)pyrene
2,900
4x10"
RSD
(B.)
29
2.9
0.29
73,000
7,300
730
naphthalene
55,000
1
RfD
550
55
5.5
550
55
5.5
"Reference Dose (RfDj, Risk-Specifiu Dose (RSO), and Maximum Contaminant Level (MCL) are explained in the Background Document to today's rule, as are the clauses of
carcinogens. Class A and B carcinogens are based on exposure limits at a 10"' risk level.
'Calculated for three hypothetical environmental exposure factors (HEEFs).
flntlo obtained by dividing values in estimated drinking well concentration column by values in health-based, water concentration limit colurm for all three HEEFs.
*GC peak resolution was not adequate to provide quantitation of the two isomers Individually. The results show the sum of the two Isomers.
106
-------
TABLE 41
BASIS FOR LISTING: HEALTH EFTECTS Of THE
OMSIIIUEHIS Of COS1CEIM IN KH8
HAZARDOUS
CONSTITUENT
AVERAGE
WASTE CONC.
DETECTED
HEALTH-BASED
WATER CONCEN-
T R A T ION
BASIS"
ESTIMATED
DRINKING
CONC.*
WELL
(ppm)
CALCULATED
BASED LIMIT
CONC. TO
RATIOS'
HEAL1H-
(ppm)
LIMITS (ppm)
HEEF 100
HEEF 1000
HEEF 10,000
HEEF 100
HEEF 1000
HEEF 10.0UU
Benz(a)anthracene
4,500
2x10*
RSD
(B,)
45
4.5
0.45
23,000,000
2,300,000
230,000
Benzo(a)pyrene
3,600
2 x 10 '
HCL
(B.)
36
3.6
0.36
180,000
18,000
1,800
Benio(b)fIuoranthene
Betizo(k)f luor ant her >e°
6,100
4x10'
RSO
(B,)
61
6.1
0.61
1,500,000
150,000
15,000
Chrysene
3,800
5x10'
RSD
(B,)
38
3.8
0.38
76,000
7,600
760
D f beiiz( a, h) anthracene
800
7 x 10 '
RSD
(B,)
8
0.8
0.08
11,000,000
1,100,000
110,000
lndeno( 1,2,3-cd)pyrene
1,700
A x 10 '
RSD
(C)
17
1.7
0.17
43,000
4,300
430
"Reference Dose (RfD), R i sk-Spec i f i c Dose (RSO), and Haximun Contaminant Level (MCL) are explained in the Background Oocunent to today's rule, as are the classes of
carcinogens. Class A and B carcinogens are based on exposure limits at a 10'* risk level.
"Calculated for three hypothetical environmental exposure factors (HEEFs).
'Ratio obtained by dividing values in estimated drinking well concentration colunn by values in health-based, water concentration limit column for all three HEEFs.
*GC peak resolution was not adequate to provide quantitation of the two isomers individually. The results show the sun of the two isomers.
107
-------
100 to 10,000, are applied to the concentrations in the wastes.
The purpose of this illustration is to indicate rhe concentrations
of the constituents which result under a range of assumptions
regarding the release of these constituents and their fate and
transport in the environment.
The constituent concentrations, with the varying HEEF multipliers,
are compared to their health-based numbers, which are discussed in
Section V.E. If the calculated concentration of the constituent in
a well is greater than the health-based number, the Agency
considers the constituent to be one of concern and, therefore, part
of the basis for listing.
The data in the tables illustrate that the examined wastes pose a
potential threat to human health and the environment across a range
of assumptions regarding the mobility, fate, and transport of
constituents in the wastes. Tables 35 through 41 show that for
each of the wastes, the concentrations of the constituents of
concern in ground water could exceed the corresponding health-based
levels of concern. The calculated ratios of estimated drinking
water concentration values to health-based limits presented in
these tables also demonstrate that even if only 0.01 percent of the
average constituent levels in the wastes (i.e., a HEEF of 10,000)
reaches environmental receptors, the exposure concentrations could
exceed the health-based levels of concern by up to five orders of
magnitude.
108
-------
In addition to the high concentrations of hazardous constituents
and the toxicity of the hazardous constituents in the wastes, the
Agency also considered the mobility and persistence of the
constituents in the environment. Information on the mobility and
persistence of the constituents of concern are provided in Sections
V.C and V. D, respectively. Information on the toxicity of these
constituents is provided in Section V.E. Based on considerations
of the concentrations of hazardous constituents in the wastes, the
toxicity of these constituents, and the mobility and persistence of
these constituents in the environment, EPA is listing these wastes
as hazardous.
Tables 1 and 27 list selected constituents of concern found in
wastes from the production and recovery of coke by-products and tar
refining, as well as the range in concentrations and averages for
these constituents. The constituents of concern listed in the
tables are carcinogens and/or systemic toxicants and are listed as
hazardous constituents in 40 CFR §261, Appendix VIII. Waste
composition data were obtained from sampling and analysis of
streams at various coke plants and tar refineries. All of the
selected constituents of concern were found in concentrations of
regulatory concern (i.e.. under plausible improper management
scenarios, the constituent concentrations likely to be present in
ground waters are expected to be significantly higher than their
health-based levels).
109
-------
Other constituents that were detected in the waste streams were not
selected as constituents of concern because they were not present
in concentrations of regulatory concern or there is not an
available health-based number. Following is a list of constituents
known to be present in the wastes that were not selected as
constituents of concern: acenaphthene, acenaphthylene, anthracene,
benzo(g,h,i)perylene, 2,4-dimethyl phenol, 2,4-dinitrotoluene,
ethyl benzene, fluoranthene, fluorene, 1-methyl naphthalene, 2-
methyl naphthalene, 2-methyl phenol, 4-methyl phenol, phenanthrene,
phenol, pyrene, styrene, toluene, and xylenes. The measured
concentrations of these compounds in K141 through K145, K147, and
K148 wastes, and available health data on their toxicity are
presented in Sections III and V.E, respectively, of this Background
Document.
The following discussion provides a summary of hazardous
constituents in each waste proposed for listing.
a. Tar Collecting Sump Residues (K141)
Of the 27 constituents analyzed in the K141 waste stream, the
following constituents do not have an Agency established health-
based number: acenaphthylene, benzo(g,h,i)perylene, 1-methyl
naphthalene, 2-methyl naphthalene, and phenanthrene. Of the
remaining 22 constituents, as shown in Table 42, the estimated
drinking well concentrations (using a hypothetical environmental
110
-------
TABL 2
COMPARISON OF ESTIMATED DRINKING WELL CONCENTRATIONS
TO HEALTH-BASED LEVELS IN DRINKING WATER FOR CONSTITUENTS OF K141
CONSTITUENTS'
CLASS"
AVERAGE
CONCENTRATIONS
(ppni)
ESTIMATED
DRINKING WELL CONCCNTT1A1 IONS (ppm)
HEEF-10.000
HEALTH-BASED LEVELS
(ALLOWABLE CONCENTRATIONS) IN DRINKING WATER
(ppm)
Acenaphlhene
S
000
0.08
2d
Anthracene
D/S
10.000
1.0
1 x 101d
Benzene
A
3 050
0.39
5* 10 3c
Baizlalanthracene
B2
7.050
0.79
2 X lO"6'
BenzoIalDvrene
B2
8.450
0.05
2 x 10^c
Benzolband klfluoianlheiie
B2
5.450
0.55
4 x 10'5e
Chrvsene
B2
0.000
0.0
5X10""5
Dibetizla.hlanlhracene
B2
1.750
0.10
7 x 10 "7 e
2.4-DtniethvtDhenol
S
200 b
0.02
7x 10"1d
2.4-Dtnltrololuene
B2
2000b
0.20
5 x 10 5 e
Ethvlbenzene
s
24
0.0024
7x 10'1c
Fluofanlheiie
D/S
25.000
2.5
1d
Fluorene
D/S
8 050
CO
©
1d
lndeno(1.2.3-cd)oviene
B2
6.150
0.62
4 x 10"4 e
2-Methvl Dhenol
C/S
200 b
0.02
2d
4-Methvl Dhenol
c/s
5.500
0.55
2d
NaDhthalene
D/S
95.000
9.5
1d
Phenol
s
5.900
0.59
2 x 10 ' d
Pvrene
D/S
20.500
2.1
1d
Stvrene
B2/S
ND
_
1 x 10'1c
Toluene
s
750
0.075
1c
Xylenes
s
300
0 030
1 x10 1 c
D Non detect
A, B, C, and D indicate classes of carcinogens; S indicates a systemic toxicant.
Average concentrations were calculated using one-half the detection limit for values reported as less than the detection limit.
Health-based level is a promulgated MCL.
Health-based level is based on an RfD and an oral intake assumption of 2 L/day by a 70 kg adult.
Health-based level is based on an RSD with a risk level of 10^and an oral intake assumption of 2 L/day by a 70 kg adult.
-------
exposure factor of 10,000 for estimating drinking well
concentrations from average waste concentrations) of the following
constituents were greater than their health-based numbers:
benz(a)anthracene, benzene, benzo(a)pyrene, benzo(b and
k)fluoranthene, naphthalene, fluoranthene, pyrene, chrvsene,
dibenz(a,h)anthracene, 2,4-dinitrotoluene, and inaeno(1,2,3-cd)
pyrene. Concentrations of 2,4-dinitrotoluene were reported as less
than the detection limit and therefore, are not of regulatory
concern. Pyrene and fluoranthene have not been included as
constituents of concern, because they are Class D carcinogens and
as such, have inadequate animal evidence of carcinogenicity. An
exception to the need for carcinogenicity data was made for
naphthalene, which is a Class D carcinogen and systemic toxicant.
Naphthalene was proposed as a constituent of concern, because it is
a major contaminant present at percent levels in all proposed waste
streams except K148. The Agency believes that, because of the high
concentrations, naphthalene poses as much of a hazard to human
health and the environment as the constituents of concern that are
carcinogens. Also, the Agency did not receive any public comments
indicating that naphthalene should not have been included as a
constituent of concern.
Thus, the following constituents that are present at concentrations
of regulatory concern and are known for their toxicity, have been
included in the list of constituents of concern in K141 waste
stream: benz(a)anthracene, benzene, benzo(a)pyrene, benzo(b and
112
-------
k)fluoranthene, chrysene, dibenz(a,h)anthracene, indeno(1,2,3-
cd)pyrene, and naphthalene.
b. Tar Storage Tank Residues (K142)
Of the 27 constituents analyzed in the K142 waste stream, the
following constituents do not have an Agency established health-
based number: acenaphthylene, benzo(g,h,i)perylene, 1-methyl
naphthalene, 2-methyl naphthalene, and phenanthrene. Of the
remaining 22 constituents, as shown in Table 43, the estimated
drinking well concentrations (using a hypothetical environmental
exposure factor of 10,000 for estimating drinking well
concentrations from average waste concentrations) of the following
constituents were greater than their health-based numbers:
benz(a)anthracene, benzene, benzo(a)pyrene, benzo(b and
k)fluoranthene, chrysene, dibenz(a,h)anthracene , 2,4-
dinitrotoluene, fluoranthene, indeno(1,2,3-cd) pyrene, naphthalene,
and pyrene. Concentrations of 2,4-dinitrotoluene were reported as
less than the detection limit and therefore, are not of regulatory
concern. Pyrene and fluoranthene have not been included as
constituents of concern because they are Class D carcinogens and as
such, have inadequate animal evidence of carcinogenicity.
113
-------
TABLE 43
COMPARISON OF ESTIMATED DRINKING WELL CONCENTRATIONS
10 HEALTH-BASED LEVELS IN DRINKING WATER FOR CONSTITUENTS OF K142
CONSTITUENTS
CLASS'
AVERAGE
CONCENTRATIONS
(ppm)
ESTIMATED
DRINKING WELL CONCEN fRATIONS (ppm)
HEEF-10,000
HEALTH-BASED LEVELS
(ALLOWADLC CONCENTRATIONS) IN DRINKING WATER *
(ppm)
Acenaphthene
S
050
0 085
2 d
Anthracene
D/S
4.000
0.40
1 x I01 d
Benzene
A
260
0.026
5 x 10'3c
Betuffllanthracene
B2
6.600
0 66
2x 10'6e
Bemolalovrene
B2
6.500
0.65
2 x 10^c
Benzolband klduoranlhene
B2
7.500
0.75
4x10 5e
Chrvsene
B2
6.000
0.6
5 x 10"4 e
Dlbenzfa.tilanthracene
B2
1000
0.1
7 x 1Q"7 *
2.4-Dtmethvtohenol
s
350
0.035
7x 10 1d
2.4-DtnltrotoHjene
B2
370 b
0.037
5 x 10 5 "
Ethvlbenzene
s
13
00013
7 x 10 "1 c
Fluoranthene
D/S
14.000
1.4
1d
Fluorene
D/S
6.100
0 61
1«
Indenod 2 3-cdlovrene
B2
2.900
0.29
4 x 10Me
2-Methvl ohenol
CIS
700
0.078
2d
4-Metlivl Dhenol
CIS
2.000
0.2
2d
Naohthalene
D/S
55.000
5.5
1d
Phenol
S
2.900
0.29
2 x 10 1 d
Pvrene
D/S
11.000
1.1
1a
Stvrene
B2/S
47
0.005
1 x 10 '1 c
Toluene
S
170
0.02
1c
Xylenes
s
120
0.012
1 x 101 c
A, B, C. and D Indicate dassesot carcinogens; S indicates a systemic toxicant.
Average conccntrationswere calculated using one-half the delection limit for values reported as less than the detection limit.
Health-based level Is a promulgated MCL
Health-based level Is based on an RfD and an oral intake assumption of 2 L/day by a 70 kg adult.
He*t1h-based level Is based on an RSD with a risk level of tO^and an oral Intake assumption ol 2 L/dny by s 70 kg adult.
-------
Thus, the following constituents that are present at concentrations
of regulatory concern and are known for their toxicity, have been
included in the list of constituents of concern in K142 waste
stream: benz(a)anthracene, benzene, benzo(a)pyrene, benzo(b and
k)fluoranthene, chrysene, dibenz(a,h)anthracene, indeno(1,2,3-
cd)pyrene, and naphthalene.
c. Light Oil Processing Residues (K143)
Of the 27 constituents analyzed in the K143 waste stream, the
following constituents do not have an Agency established health-
based number: acenaphthylene, benzo(g,h,i)perylene, 1-methyl
naphthalene, 2-methyl naphthalene, and phenanthrene. Of the
remaining 22 constituents, as shown in Table 44, the estimated
drinking well concentrations of the following constituents were
greater than their health-based numbers: benz(a)anthracene,
benzene, naphthalene, 2,4-dinitrotoluene, benzo(a)pyrene, benzo(b
and k)fluoranthene, chrysene, dibenz(a,h)anthracene, and
indeno(1,2,3-cd) pyrene. Concentrations of dibenz(a,h)anthracene,
indeno(1,2,3-cd)pyrene, and 2,4-dinitrotoluene were reported as
less than the detection limits and therefore, were not of
regulatory concern. The following constituents that are present at
concentrations of regulatory concern and are known for their
toxicity, have been included in the list of constituents of concern
in K14 3 waste stream:
115
-------
TABLE 44
COMPARISON OF ESTIMATED DRINKING WELL CONCENTRATIONS
TO HEALTH-BASED LEVELS IN DRINKING WATER FOR CONSTITUENTS OF K143
CONSTITUENTS
CLASS'
AVERAGE
CONCENTRATIONS
(ppm)
ESTIMATED
DRINKING WELL CONCENTRAT IONS (ppni)
HEEF-10,000
HEALTH-BASED LEVELS
(ALLOWABLE CONCENTRATIONS) IN DRINKING WATER
(ppm)
Acenaphthene
S
50
0 0058
2d
Anthracene
D/S
100
0.010
1 x 101 d
Benzene
A
1.600
0.16
5 x 10 3 c
Benzlalanthracene
B2
69
0.0069
2 x 10"6 e
BenzofalDvrene
B2
34
0.0034
2 x 10^c
Benzolband klfluoranthene
B2
59
0.0059
4 x 10'5e
ChrYsene
B2
59
0.0059
5 x 10 e
Dibenzla.hlanthiaceiie
B2
36 b
0.0038
7x10'7c
?.4-Dime1hvtDhenol
s
7
0.0007
7 x 10 1 d
2.4-Dinltratoluene
B2
I30b
0.013
5 x 10 5 e
Elhvtbenzene
s
10
0.0010
7x10"'°
Fluoranlhene
D/S
290
0.029
1"
Fluotene
D/S
140
0.014
1"
Indenoll .2.3-cdlDvrene
B2
40"
0.0040
4 x 10 e
2-Methvl Dhenol
CIS
1 1
0.0011
2d
4-Methvl nhenol
CIS
20
0.0020
2
-------
TABL 5
COMPARISON OF7 ESTIMATED DRINKING WELL CONCENTRATIONS
TO HEALTH-BASED LEVELS IN DRINKING WATER FOR CONSTITUENTS OF KI44
CONST RUENTS
CLASS"
AVERAGE
CONCENTRATIONS
(ppni)
ESTIMATED
DRINKING WELL CONCENTRATIONS (ppm)
HEEF-10,000
HEALTH-BASED LEVELS
(ALLOWABLE CONCENTRATIONS) IN DRINKING WAITER
(ppm)
Ac«naphthene
S
16
0 0016
2d
Anthracene
D/S
90
0.009
1 X 10,d
Benzene
A
3.000
0.3
5* 10-3c
Benzlalanthracene
B2
68
0.0060
2 x 10 6 0
BenzofalDvrene
B2
65
0.0065
2x 10-"c
Benzolband kllluoranthene
B2
75 '
0.0075
4 x 10 "5 e
Chrvsene
B2
60
0.0066
5 x 10"4 e
Dibenzfa.hlanlfiracene
B2
15
0.0015
7* 10'7e
2.4-Dtmethvtohenol
s
70
0.00070
7x 10'1d
2.4-Dhiltrololuene
B2
33 b
0.0033
5 x 10 "5 e
Elhvlbenzene
S
17
0.0017
7 x 10 1 c
Fluoranthene
D/S
190
0.019
1d
Fluorene
D/S
79
0.0079
1d
IndenoM ,2.3-cdlDViene
B2
37
0.0037
4 x 10"1 e
2-Methvl ohfifiol
C/S
17
0.0017
2d
4-Methvl Dhenol
CIS
23
0.0023
2d
Nnnhthalenn
D/S
27.000
2.7
1d
Phenol
S
32
0.0032
2 x 101 d
Pvrene
D/S
130
0.013
1d
StVTWIC
B2/S
ND
_.
1 x 10"1 c
Tolnprm
S
1.100
0.11
1c
Xylenes
S
300
0.03
t x TO1 c
ID Non detect
A, B, C, and D indicate classes of carcinogens; S indicates a systemic toxicant.
Average concentrations were calculated using one-half the detection limit for values reported as less than the detection limit.
Health-based level is a promulgated MCL.
Health-based level is based on an RfD and an oral intake assumption of 2 L/day by a 70 kg adult.
Health-based level is based on an RSD with a risk level of 10 6 and an oral intake assumption of 2 L/day by a 70 kg adult.
117
-------
benz(a)anthracene, benzene, benzo(a)pyrene, benzo(b and k)fluo-
ranthene, chrysene, and naphthalene.
d. Intercepting Sump Residues (K144)
Of the 27 constituents analyzed in the K144 waste stream, the
following constituents dc not have Agency established health-based
numbers: acenaphthvlene, benzo(g,h,i)perylene, 1-methyl
naphthalene, 2-methyl naphthalene, and phenanthrene. Of the
remaining 22 constituents, as shown in Table 45, the estimated
drinking well concentrations of the following constituents were
greater than their health-based numbers: benz-
(a)anthracene,benzene, benzo(a)pyrene, benzo(b and k)fluoranthene,
chrysene, dibenz(a,h)anthracene, 2,4-dinitrotoluene, indeno(1,2,3-
cq) pyrene, and naphthalene. Concentrations of 2,4-dinitrotoluene
were reported as less than the detection limit and therefore, are
not of regulatory concern. The following constituents that are
present in concentrations of regulatory concern and are known for
their toxicity, have been included in the list of constituents of
concern in K144 waste stream: benz(a)anthracene, benzene,
benzo(a)pyrene, benzo(b and k)fluoranthene, chrysene,
dibenz(a,h)anthracene, indeno(1,2,3-cd) pyrene, and naphthalene.
118
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e. Naphthalene Collection and Recovery Residues (K145)
Of the 27 constituents analyzed in the K145. waste stream, the
following constituents do not have an Agency established health-
based number: acenaphthylene, benzo(g,h,i)perylene, 1-methyl
naphthalene, 2-methyl naphthalene, and phenanthrene. Of the
remaining 22 constituents, as shown in Table 46, the estimated
drinking well concentrations of the following constituents were
greater than their health-based numbers: benz(a)anthracene,
benzene, benzo(a)pyrene, benzo(b and k)fluoranthene, chrysene,
dibenz(a,h)anthracene, 2,4-dinitrotoluene, and naphthalene.
Concentrations of 2,4-dinitrotoluene were reported as less than the
detection limit and therefore, are not of regulatory concern. The
following constituents that are present at concentrations of
regulatory concern and are known for their toxicity, have been
included in the list of constituents of concern in K145 waste
stream: benz(a)anthracene, benzene, benzo(a)pyrene, benzo(b and
k)fluoranthene, chrysene, dibenz(a,h)anthracene, indeno(1,2,3-
cd)pyrene, and naphthalene.
f. Tar Storage Tank Residues (K147)
Of the 27 constituents analyzed in the K147 waste stream, the
following constituents do not have an Agency established health-
based number: acenaphthylene, benzo(g,h,i)perylene , 1-methyl
naphthalene, 2-methyl naphthalene, and phenanthrene. Of the
119
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TABLIZ 46
COMPARISON or ESTIMATED DRINKING WELL CONCENTRATIONS
TO HEALTH-BASED LEVELS IN DRINKING WATER TOR CONSTITUENTS OF KI45
CONSTITUENTS
CLASS"
AVERAGE
CONCENIT1A1 IONS
(ppm)
ESTIMATED
DRINKING WELL CONCEN TRATIONS (ppm)
IIEEF-10,000
HEALTH-BASED LEVELS
(ALLOWABLE CONCENTRATIONS) IN DRINKING WATER e
(ppm)
Aconnphthene
S
47
0 0047
2d
Anthracene
D/S
120
0.012
1 X 101 d
Benzene
A
1.100
0.11
5 x 10"3c
Benzlalanthracene
B2
22
0.0022
2 x 10Ge
BenzolalDvrene
B2
7
0.0007
2* lO"^
Benzolband klfluoranlherie
B2
26
0.0026
4 x I0"5e
Chrvsene
B2
22
0.0022
5 X 10"4 e
Dlbenzfahlanthracene
B2
1.3
0.0001
7 x 10 '7 e
? 4-DlmethviDhenol
S
73
0.0073
7x 10',d
2.4-Dlnltrotoluene
B2
7.5"
0.0000
5x I0'5e
Ethvlbenzene
S
20
0.0020
7x 10,c
Fluotanthene
D/S
07
0.0007
1'
Fluorene
D/S
4
0.0004
1d
Indenod -2.3-cdlDviene
B2
4
0.0004
4 x 10"4 5
2-Methyl ohenol
CIS
54
0.0054
2d
4-Methvt ohenol
CIS
100
0.01
2d
D/S
140.000
14
1«
S
120
0.012
?* 101d
D/S
53
0.0053
1d
B2/S
120
0.012
1 x 10"' c
S
760
0.076
1c
Xylenes
S
390
0.039
1 x 10 ' c
' A, B, C, and D Indicate classes ol carcinogens. S Indicates a systemic toxicant.
'Average concentration 3 wet e calculated using one-half the detection limit (or values leported as less than the detection limit.
Heefth-based level Is a promulgated MCL.
1 Health-based (eve) Is based on an RfD and an oral intake assumption ot 2 L/day by a 70 kg adult.
1 Health-based levo) Is based on an DSD with a risk level ot 10 6 and an oral Intake assumption o( 2 L/day by a 70 kg adult
-------
remaining 22 constituents, as shown in Table 47, the estimated
drinking well concentrations of the following constituents were
greater than their health-based numbers in drinking water:
benz(a)anthracene, benzene, benzo(a)pyrene, benzo(b and
k)fluoranthene, chrysene, dibenz(a,h)anthracene, 2,4-
dinitrotoluene, fluoranthene, indeno(1,2,3-cd) pyrene, naphthalene,
and pyrene. Concentrations of 2,4-dinitrotoluene were reported as
less than the detection limit and therefore, were not of regulatory
concern. Pyrene and fluoranthene have not been included as
constituents of concern because they are Class D carcinogens and as
such, have inadequate animal evidence of carcinogenicity. The
following constituents that are present at concentrations of
regulatory concern and are known for their toxicity, have been
included in the list of constituents of concern in K147 waste
stream: benz(a)anthracene, benzene, benzo(a)pyrene, benzo(b and
k)fluoranthene, chrysene, dibenz(a,h)anthracene, indeno(1,2,3-
cd)pyrene, and naphthalene.
g. Tar Distillation Residues (K148)
Of the 27 constituents analyzed in the K147 residuals, the
following constituents do not have an Agency established health-
based number: acenaphthylene, benzo(g,h,i)perylene, 1-methyl
naphthalene, 2-methyl naphthalene, and phenanthrene. Of the
remaining 22 constituents, as shown in Table 48, the estimated
drinking well concentrations of the following constituents were
121
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TABLE 47
COMPARISON OF ESTIMATED DRINKING WELL CONCENTRATIONS
TO HEALTH-BASED LEVELS IN DRINK ING WATER FOR CONSTITUENTS OF KI47
CONSTITUENT S
CLASS8
AVEITAGE
CONCENI HAT IONS
(ppni)
ESTIMATED
DRINKING WELL CONCENTRA1 IONS (ppm)
HEEF-10.000
HEALTH-DASED LEVELS
(ALLOWABLE CONCENTRATIONS) IN DRINKING WA1ER 8
(ppm)
Acenaphthene
S
850
0.005
2d
Anthracene
n/s
4.000
0.40
1x 10,d
Benzene
A
260
0.026
5 x 10 '3 c
Benzlalanthracene
B2
G.600
0.60
2 x 10 5 {
Benzolalovrene
B2
6.500
0.65
2 x 10"*1 c
Beruofband klfluoranthene
B2
7.500
0.75
4x 10 5e
Chrvsene
B2
6 000
0.6
5x 10"^
Dfbenzfa.hlanlhi scene
B2
1000
0.1
7 x 10 '7 e
2.4-Dlmethvlohenol
S
350
0.035
7 x 10 1 "
?.4-Dtnitrotoluene
B2
370 6
0.037
5 x 10 5 e
Fthvfbenzene
S
13
0.0013
7 x 10",c
Fluorarithene
D/S
14.000
1.4
l"
Fluotene
D/S
6.100
0.61
1«
Indenof 1 _2.3-cd)Dvrene
B2
2.900
0.29
4 x 10 e
p-Methvt Dhenol
CIS
700
0.070
2d
4-Melhvl Dhenol
CIS
2.000
0.2
2d
Naohthalene
D/S
55.000
5.5
1"
Phenol
s
2.900
0.29
2 x 10 1 d
Pvrfirip
D/S
11.000
1.1
1d
B2/S
47
0.005
1 x 10 1 c
S
170
0.02
1c
Xylenes
S
120
0.012
1 x 101 c
* A, B, C, and D Indicate dasses of carcinogens, S Indicates a systemic toxicant
3 Average concentrations were calculated using one-halt the detection limit lor values reported as less than the detection limit
: Health-based level Is a promulgated MCL
1 Health-based level Is based on an RfD and an oral Intake assumption of 2 L/day by a 70 kg adult.
s Health-based level Is based on an RSD with a risk level ol 10 6 and an oral intake assumption of 2 LVday by a 70 kg adult
-------
TABL. ,8
COMPARISON OF ESTIMATED DRINKING WELL CONCENTRATIONS
TO HEALTH-BASED LEVELS IN DRINKING WATER FOR CONSTITUENTS OF KH8
CONSTITUENTS '
CLASS"
AVERAGE
CONCENTRATIONS
(ppm)
ESTIMATED
DRINKING WELL CONCENTRATIONS (ppm)
HEEF = 10,000
HEALTH-BASED LEVELS
(ALLOWABLE CONCENTRATIONS) IN DRINKING WATER 8
(ppm)
Acenaphthene
S
610
0 001
2d
Anthiacene
D/S
1.500
0 15
1 x 10 ' d
Benzene
A
NA
NA
5 x 10 '3 c
Benzfalan'.hracene
B2
4.500
0.45
2 x 10"6 e
BenzolalDvrene
B2
3.600
0.36
2 x 10"40
Benzolband klfluoranthene
B2
6.100
0.61
4 x 10 5 c
Chrvaene
B2
3.800
0.30
5 x 10 e
Dibenzla.hlanthracene
B2
000
0.08
7 X 10 7 "
2.4-DtmelhvlDlietiol
S
2.5 b
0.00025
7 x 10"1d
2.4-Dlnltiotoluene
B2
7.5 b
0.00075
5 X 10 "5 e
Ethvfbenzene
S
NA
NA
7 x 10"' c
Fluoranthene
D/S
7.300
0.73
1d
Fluor ene
D/S
1.000
0.1
1d
Indenofl 2.3-ccflDvrene
B2
1.700
0.17
4 x 10"4 e
2-Methvi ohenol
C/S
2.5
0.00025
2d
4-Metlivl uhenol
CIS
51
0.0051
2d
Naohthaleiie
D/S
850
0.005
1d
Phenol
S
51
0.0051
2 x 101 d
FVrene
D/S
5.900
CD
\n
o
1d
Stviene
B2/S
NA
NA
1 x10'1c
Toluene
s
NA
NA
1c
Xylenes
S
NA
NA
1 x 101c
A, B, C, and D Indicate dasses ol carcinogens; S indicates a systemic toxicant.
Average concentratlon3were calculated using one-hall the detection limit (or values reported as less than the detection limit.
Heotth-based level Is a promulgated MCL
Heelth-based level Is based on an RfD and an oral intake assumption ol 2 L/day by a 70 kg adult
Health-based level Is based on an DSD with a risk level of 10 ^ and an oral Intake assumption of 2 IVday by a 70 kg adult.
123
-------
greater than their health-based numbers in drinking water:
benz(a)anthracene, benzo(a)pyrene, benzo(b and k)fluoranthene,
chrysene, dibenz(a,h)anthracene, 2,4-dinitrotoluene, and indeno-
(1,2,3-cd) pyrene. Concentrations of 2,4-dinitrotoluene were
reported as less than the detection limit and therefore, were not
of regulatory concern. The following constituents that are present
at concentrations of regulatory concern and are known for their
toxicity, have been included in the list of constituents of concern
in K147 waste stream: benz(a)anthracene, benzo(a)pyrene, benzo(b
and k)fluoranthene, chrysene, dibenz(a,h)anthracene, and
indeno(1,2,3-cd)pyrene.
C. Mobility of Constituents of Concern
The exposure pathway of principal concern is leaching and migration
to ground water. The water solubility of a given hazardous
constituent is one indicator of its mobility potential (i.e.. the
likelihood that it will be released from a management site
dissolved in water and reach a water resource of concern) .
Leaching is of concern because several of these compounds are
soluble in water and could, therefore, leach from the wastes and
potentially contaminate ground water. For example, the water
solubility of benzene is significantly greater than its
corresponding health-based level in drinking water. Thus, this
constituent is capable of existing in water at significant
concentrations. The solubilities and projected ground-water
124
-------
mobilities of the selected constituents of concern from coke by-
products production, recovery, and refining and tar refining wastes
are presented in Table 49.
Many of the toxic constituents found in the production and recovery
of coke by-products and in tar refining wastes are soluble in
water, and have solubility values greater than their health-based
levels of concern. Seven constituents of concern have water
solubilities that are at least one order of magnitude greater than
the corresponding health-based levels of concern. Therefore,
wastes containing these constituents could pose a significant
threat to the environment if mismanaged in ways that may result in
migration to ground water. One constituent of concern has a water
solubility that is of the same order of magnitude as the health-
based level of concern.
Data available to the Agency indicate that toxic PAHs are present
in ground water at concentrations that far exceed their water
solubility. At one site, benzo(a)pyrene was measured in ground
water at a concentration of 0.08 ppm, which is greater than its
reported solubility. Although the exact reason for this phenomenon
is not fully understood, it is believed that the presence of these
constituents in ground water is due to the oily nature of the
wastes and solvent-assisted transport, as discussed in greater
detail later in this section.
125
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1 ABLE 49
GROUJffl-UAlER ROBILITY AND PERSISTENCE Of
COtJST I TUEWTS Of CTMCERM
Constituents of
Concern
Health-based
water
concentr at Ion
limits (ppnt)
Water Solubility
(ppm)
log KJ
Log
Mobi 11 tye
Persistence"
SIightty
con t am i na t ed
mediun
Highly
contaminated
medl un
Benzene
5 x 10 '
1.78 x 10'
2.13
1.92
moderate
high
low
Benzo(a)anthracene
2 x 10"
5.7x10'
5.61
6.14
low
high
high
Benzo(a)pyrene
2 x 10 *
3.8 x 10 '
6.04
5.60 - 6.29
low
high
l> i gh
Benzo(b)fluoranthene'
4 x 10"
1.4 x 10 '
6.57
5.74
low
h Igh
high
Benzo(k)fluoranthene'
4 » 10"
5.5 x 10 '
6.85
6.64
low
high
high
Chrysene
5 x 10"*
1.0 x 10 '
5.60
5.39
low
high
high
Di benz(a,h)anthracene
7 x 10 ' *
5.0 x 10 '
6.50
6.22
low
high
high
lndeno(1, 2,3-cd)pyrer>e
4x10"
5.3 x 10 "
5.97
7.49
1 ow
h igh
high
Naphthalene
1°
3.17 x 10'
3.30
3.04
low
high
high
Source: Montgomery, John H., Groundwater Chemicals Desk Reference. 1990.
* Octanol-water partition coefficient.
*K„. « Soil sorption coefficient.
'Qualitative relative evaluation of mobility and persistence, based on water solubility, log K„., and log
"Slightly contaminated mediim represents a mismanagement scertario where release of hazardous constituents does not result in saturation of the underlying A
by organic hazardous constituents.
'Highly contaminated mediun represents a mismanagement scenario where release of hazardous constituents results in saturation of the underlying soil by aye
hazardous constituents.
'ihe health-bosed lifnlt for benzo(b)fluoranthene was also applied to benzo(k)fluoranthene because the GC peek resolution woo not adequate to provide qflOtttui
of the isomers Individually, and therefore, the results are the sum of the two isomers.
"Does not constitute an Agency decision in providing health-based nuitoers or decisions.
12 6
-------
Another factor that can provide an indication of the mobility of
each constituent is its log octanol/water partition coefficient
(log K^) . The log K^, value for benzene is 2.13. According to
Briggs (1977) , this value indicates that benzene is moderately
mobile in soil.
The PAHs (i.e.. benz(a)anthracene, benzo(a)pyrene,
benzo(b)fluoranthene, benzo(k)fluoranthene, chrysene, dibenz(a,h)
anthracene, indeno(1,2,3-cd)pyrene, and naphthalene) have high log
octanol/water partition coefficients and may be predicted to be
relatively immobile in soil and sediment. However, available
evidence indicates that these constituents may move more readily
than would be predicted when they are present in soil with other
organics, codisposed with other solvents or oils, or when the waste
itself is of an oily nature. They can also be transported while
suspended on particulate matter in air or water.
The subsurface transport of toxic constituents from their disposal
site through the unsaturated soil zone to and within ground water
may take place by several mechanisms. The toxicants may exist as
water-dissolved substances that are transported by advection (i.e..
with the moving water phase), the least complex transport
mechanism.
A second mechanism for the transport of coke by-products wastes is
migration in a discreet oil (or other nonaqueous solvent) phase.
127
-------
Subsurface investigations at some sites described in the damage
cases (found in the docket) have revealed the presence of a
discrete oil phase. These phases may exist as oil sludges, lenses,
or a floating oil layer on the water table. Because the oil
differs from ground water in its chemical and physical properties,
including density, the nonaqueous phase may migrate in the
subsurface independently of ground water flow. For example, dense
materials will tend to migrate vertically through an aquifer until
buoyancy is achieved or a vertical barrier is encountered. These
materials may also migrate laterally faster or slower than the rate
of ground water flow, due to effects of differing chemical and
physical properties on attenuation mechanisms.
It should be stressed that those ground water samples where PAHs
have been detected at levels above their solubilities did not
contain a separate oil phase (contaminant concentrations in
subsurface oil phases are, in general, much higher than those
described above). Clearly, the distinct aqueous phase and oil
phase transport mechanisms do not fully explain the migration of
toxic constituents of organic wastes. The actual mechanism or
mechanisms at work are not understood. Hypotheses include
transport of the organics as oil micelles (microdroplets) or
emulsions suspended in water, transport of the organics sorbed onto
humic acids or colloidal solids which are suspended in ground
water, pH effects, and co-solvent effects.
128
-------
The mobilities in Table 49 have been presented based both on low-
contaminated soil medium and high-contaminated soil medium. At low
contamination, leaching of water-soluble constituents from the
waste to the ground water predominate with less water-soluble
constituents being adsorbed by the surrounding soil, or migrating
via other less understood mechanisms. However, as the
contamination of the soil medium with organics increases, the soil
will become saturated, eliminating further adsorption of the
nonpolar constituents and creating a separate organic phase. This
organic phase will dissolve the nonpolar constituents and
facilitate transport from the management site.
The exact transport mechanisms for the constituents of concern in
proposed EPA Hazardous Waste Nos. K141 through K145, K147 and K148
are not fully understood. However, under the plausible types of
improper management to which the wastes could be subjected, the
constituent concentrations that reach ground waters could be
significantly higher than corresponding health-based numbers. This
is shown by concentrations of PAHs found in ground water samples at
sites described in Section V.F of this Background Document, which
discusses the damage incidents. This conclusion is also consistent
with the conclusions derived from application of HEEFs in the broad
range of 100 to 10,000 for these wastes, as discussed in Section
V.A of this document.
129
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D. roraiotcuCa Of COustitUuiitS Of CoacBrn
The persistence of a constituent in the environment is an important
criterion considered by the Agency when determining the potential
of a waste to pose a threat to human health and the environment.
The chemical and biological reactivity of the constituents of
concern present in coke by-products production, recovery, and
refining wastes indicate that they are persistent and, thus,
capable of posing a significant hazard to human health and the
environment. The Agency considers a compound to be persistent if
it persists in the environment long enough to be detected since, if
a chemical can be detected in ground water, exposure to humans is
possible. All the constituents of concern in coke by-products
wastes are sufficiently persistent to result in human exposure if
they are released into ground water. The principal processes that
limit the persistence (half-life) of these constituents in ground
water are hydrolysis and biodegradation.
None of the constituents are expected to hyarolyze in water between
pH 2 and 12 at ambient temperature at a rate high enough to be a
limiting factor in human exposure. This is because none of the
constituents of concern have structural components that would be
expected to react with water under those conditions. Benzene, for
example, does not react with acidic (pH 2) or alkaline (pH 14)
water. Therefore, it is unlikely that hydrolysis is a significant
fate for benzene. The PAHs of concern do not contain groups
130
-------
amenable to hydrolysis. Hydrolysis is, therefore, not thought to
be a significant fate process for PAHs (Radding et al., 1976) .
Biodegradation is another potential degradation mechanism for each
of the organic constituents of concern. Under certain aerobic
conditions, organic hazardous constituents are biodegradable, as
shown in controlled laboratory experiments. Although benzene is
expected to biodegrade in biologically active surface water
systems, it is not expected to undergo biodegradation in ground
water due to the relatively low level of biological activity in
ground water systems.
PAHs are known to be persistent in the environment. PAHs have also
been detected in drinking water, surface water, ground water,
soils, sediments, and air. Biological degradation processes are
not known to occur at a rate sufficient to prevent the spread of
PAHs in the environment. Three studies reported no appreciable
degradation of BaP in contaminated water and sediment (Herbes and
Schwall, 1977; Muller and Korte, 1975; Herbes, 1981).
Persistence of benzene and PAHs in the environment has been
confirmed by detection of these constituents in ground water,
surface water, drinking water, soil, and air.
131
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E. Health Effects of Constituerifcs of Concern
The Agency has obtained data demonstrating that certain
constituents found in the wastes generated by the production,
recovery, and refining of coke by-products and tar refining are
systemic toxicants and/or carcinogens.
These toxic constituents are present in concentrations capable of
causing adverse health effects as shown by Tables 35 through 41.
These tables illustrate that even if only 0.01 percent of the
average constituent concentrations in the wastes reaches
environmental receptors, the exposure concentrations could exceed
the health-based levels of concern by up to five orders of
magnitude.
For the purpose of listing wastes as hazardous under RCRA, the
Agency can use three basic indicators of toxic levels of concern:
(1) Maximum Contaminant Levels (MCLs); (2) Risk-Specific Doses
(RSDs) for known carcinogens; and (3) Reference Doses (RfDs) for
systemic toxicants. Based on different criteria, each of these
measures indicates maximum doses or levels of exposure that are
acceptable.
MCLs are Drinking Water Standards promulgated under Section 1412 of
the Safe Drinking Water Act of 1974, as amended in 1986, for both
carcinogenic and noncarcinogenic compounds. In determining MCLs,
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EPA considers a range of pertinent factors, such as technology and
economic feasibility as well as health effect. (For more details,
see 52 FR 25697-25701, July 8, 1987.)
Where MCLs are not yet established, the Agency has developed oral
RSDs for many carcinogenic constituents. The RSD is a dose that
corresponds to a specified risk level for an individual contracting
cancer over a 7 0-year lifetime due to the presence of the
carcinogen in drinking water. RSDs are derived from carcinogenic
slope factors (CSFs), which describe the slope of the extrapolated
line from animal experiments to human application. (For more
details regarding the Agency's approach for determining potential
human carcinogenicity of compounds, see "Guidelines for Carcinogen
Risk Assessment", September 24, 1986 (51 FR 33992).) In order to
calculate an RSD from a CSF, a risk level must be specified. The
oral RSDs for carcinogenic agents are calculated at the 10~6 risk
level for Class A, B, and C carcinogens, which means that if one
million people were exposed to an A, B, or C level carcinogen for
their lifetime, an average of one cancer case could occur. This
risk level is consistent with the risk level used to delist
specific waste streams.
EPA specifies the class for a carcinogen of concern by using a
weight-of-evidence scheme that is based on an assessment of the
quality and adequacy of experimental data and the kinds of
responses induced by a suspect carcinogen. In the "Guidelines for
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Carcinogen Risk Assessment" (51 FR 33992), EPA defined a scheme to
characterize substances based on the experimental weight-of-
evidence of carcinogenicity. This scheme is based on
considerations of the quality and adequacy of the experimental data
and the kinds of responses induced by a suspect carcinogen. This
guideline specifies the following five classifications:
Group A - Human carcinogen (sufficient evidence from
epidemiological studies);
Group B - Probable human carcinogen;
Group B, - At least limited evidence of
carcinogenicity in humans;
Group B2 - Usually a combination of sufficient
evidence in animals and inadequate data in humans;
Group C - Possible human carcinogen (limited evidence of
carcinogenicity in the absence of human data);
Group D - Not classified (inadequate animal evidence of
carcinogenicity); and
Group E - No evidence of carcinogenicity for humans (no
evidence of carcinogenicity in at least two adequate
animal tests in different species or in epidemiological
and animal studies).
The carcinogenic constituents of concern in proposed EPA
Hazardous Waste Nos. K141 through K145, K147, and K148 for which no
MCLs exist are all probable human carcinogens (Class B2) , except
naphthalene, which is a Class D carcinogen and systemic toxicant.
In addition, oral Reference Doses (RfDs) are used for non-
carcinogenic constituents (systemic toxicants) for which MCLs have
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not been developed. A systemic toxicant, which is any chemical
that adversely affects the function of an organ, but does not cause
cancer or gene mutations, must surpass a certain threshold before
its effect is toxic to the body. An individual can be exposed to
a systemic toxicant for some finite amount of time before any
deleterious effects occur.
An RfD is an estimate of the daily exposure to a substance for the
human population (including sensitive subgroups) that appears to be
without an appreciable risk of deleterious effects during a
lifetime of exposure. If frequent exposures that exceed the RfD
occur, the probability that adverse effects may be observed
increases. The method for estimating the RfD for non-carcinogenic
end points was described in the proposed rule for the Toxicity
Characteristic (51 FR 21648, June 13, 1986).
The health-based concentration limits for the constituents of
concern without MCLs in Tables 3 5 through 41 were derived from RSDs
and RfDs and are based on well-established and widely-accepted
assumptions. Specifically, the average person has a mass of 70 kg,
and drinks, on average, 2 liters of water daily over a 70 year
lifetime. The calculations are as follows:
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for carcinogens:
HBL = (RSD X W x LT) / (I X A x ED)
where: HBL = Health-based limit (mg/L)
RSD = assumed risk level/CSF = 10~6/CSF
(mg/kg/day)
W = body weight = 70 kg
LT = assumed lifetime = 70 years
I = intake assumption = 2 L/day
A = absorption factor = 1
ED = exposure duration = 70 years
for systemic toxicants:
HBL = (RfD x W) / (I x A)
where: HBL = Health-based limit (mg/L)
RfD = reference dose (mg/kg/day)
W = body weight = 70 kg
I = intake assumption = 2 L/day
A = absorption factor = 1
All EPA-verified health-based numbers are listed on the Integrated
Risk Information System (IRIS). The information listed on IRIS is
designed to be a guide for the evaluation of potential health
problems and is included on IRIS only after an intra-office work
group of EPA toxicologists and other scientists have reviewed the
facts. IRIS provides verified information for oral and/or
inhalation reference doses, risk estimates for carcinogenicity,
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drinking water health advisories, risk management summaries, and
other supplemental data. Various EPA programs use the verified
health-based numbers and consider specific factors to suit the
needs of that particular program.
Unverified health-based numbers come from a variety of sources.
The Health Effects Assessment Summary Tables (HEAST) provide a
summaries of data that are not yet Agency verified. Other
documents routinely used for unverified health-based numbers
include health and environmental effects documents (HEEDs), Office
of Drinking Water (ODW) health advisories, Carcinogen Assessment
Group (CAG) profiles, and Office of Health and Environmental
Assessment (OHEA) Potential Carcinogenicity Evaluations. The
toxicity descriptions below indicate the references for each of the
health-based numbers used.
The hazardous constituents of concern found in the coke by-products
wastes proposed for listing have produced carcinogenic or other
chronic systemic effects in laboratory animals or humans. EPA has
established RfDs, RSDs, or MCLs for all of the constituents of
concern in coke by-products and tar refining wastes. These
constituents have been detected in the wastes from the production,
recovery, and refining of coke by-products in concentrations
sufficient to pose a substantial threat to human health and the
environment.
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The Agency has determined that there is substantial evidence to
suggest that benz (a) anthracene , benzene, benzo (a) py-rene, benzo(b
and k) fluoranthene, chrysene, dibenz(a,h)anthracene, and
indeno(1,2,3-cd)pyrene are carcinogens. The carcinogenic class
designations have been added to IRIS for all of these compounds.
Epidemiologic evidence from studies of coke oven workers and tar
roofers demonstrates the carcinogenic potential of the materials
generated by coke ovens and tar refining. A discussion of the
toxicity and health effects of these constituents is presented
below.
Benz(a)anthracene (BA) is a Class B2 carcinogen. As stated on
IRIS, BA "administration caused an increase in the incidence of
tumors by gavage (Klein, 1963); dermal application (IARC, 1973);
and both subcutaneous injection (Steiner and Faulk, 1951; Steiner
and Edgecomb, 1952) and intraperitoneal injection (Wislocki et al.,
1986) assays". The health-based number for BA is based on a USEPA
report (USEPA, 1988a).
Benzene is a Class A carcinogen. Benzene is carcinogenic in rats
after exposure by gavage (Maltoni and Scarnato, 1979; Maltoni et
al., 1983 ; NTP, 1986) and in mice following exposure by inhalation
(IARC, 1982; Snyder et al., 1981; Maltoni et al., 1983). In
addition, there are numerous epidemiological studies that correlate
benzene exposure with the incidence of leukemia (NTP 85-002; Aksoy
et al. 1974; Infante et al., 1977a,b; Rinsky et al., 1981; Ott et
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al., 1978; Wong et al., 1983). The health-based level for benzene
is a promulgated MCL.
Benzo(a)pyrene (BaP) is a Class B2 carcinogen. BaP is perhaps one
of the most potent animal carcinogens known. Microgram quantities
have been shown to induce tumors in a number of experimental animal
species via several routes of exposure, including oral, inhalation,
and dermal application (IARC, 1973). The types of tumors seen
after exposure to BaP include mammary tumors in rats (IARC, 1973) ;
carcinomas of the forestomach in mice (Rigdon and Neal, 1967) ; and
skin tumors in mice (Poel, 1963). BaP can also act as a
transplacental carcinogen in mice (Bulay and Watenberg, 1971). A
verified CSF is listed on IRIS for BaP, and the health-based number
is based on a promulgated MCL.
Benzo(b and k)fluoranthenes (BbF and BkF) are Class B2 carcinogens,
as stated on IRIS. BbF and BkF have both been shown to be dermal
carcinogens in mice (IARC, 1973) and induce tumors when injected
intraperitoneally (LaVoie et al., 1987) in mice and directly into
the pulmonary tissue of rats (Deutsch-Wenzel et a_l. , 1983). BkF
also induces tumor formation when injected subcutaneously
(Lacassagne et aA., 1963). The health-based number for BbF/BkF is
based on the health-based number for BaP and a USEPA document
(USEPA, 1982). This document describes a relative potency approach
for deriving HBNs for PAHs from the slope factor for benzo (a) pyrene
(which is 5.79 /mg/kg/day, as stated on IRIS). According to the
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document, BbF is 17% as potent a carcinogen, as benzo(a)pyrene.
This percentage, which is at the 95% upper confidence limit, was
derived based on the potency estimate q^, which is dependent only
upon tumor incidence rates (rather than tumor-to-time incidence
rates and Q,*) . The Agency could have chosen any of three other
relative potency factors for this calculation. However, q,* was
chosen, as it has historically been used as the index of choice for
determining relative potency. Regardless of the index chosen, the
potency indexes are within one order of magnitude of one another.
Thus, 17% of 5.79 /mg/kg/day is 0.984 /mg/kg/day, which is the
calculated carcinogenic slope factor for BbF. The subsequent
health-based number is then calculated according to the methodology
described previously.
Chrysene is a Class B2 carcinogen, as stated on IRIS. According to
IRIS, "chrysene produced carcinomas and malignant lymphoma in mice
after intraperitoneal injection (Wislocki et al., 1986; Buening et
al., 1979) and skin carcinomas in mice following dermal exposure
(Wynder and Hoffman, 1959)". The health-based number for chrysene
is based on the health-based number for BaP (5.79 /mg/kg/day) and
a USEPA document (USEPA, 1982). According to the document and the
q,*, chrysene is 1.3% as potent a carcinogen as benzo(a)pyrene.
Thus, 1.3% of 5.79 /mg/kg/day is 0.075 /mg/kg/day, which is the
calculated carcinogenic slope factor for chrysene. The subsequent
health-based number is then calculated using the CSF according to
the methodology described previously.
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Dibenz(a,h)anthracene (DBA) is a Class B2 carcinogen. DBA produced
tumors in mice following oral, dermal, subcutaneous and
intramuscular administration (IARC, 1973; USEPA, 1990). The types
of tumors seen in mice after exposure to DBA by various routes
include adenomas carcinomas of the skin (Wonder and Hoffman, 1959);
mixed-type mammary tumors (Biancifiori and Caschera, 1962;
Berenblum and Haran, 1955); pulmonary alveologenic carcinomas and
adenomatosis; hemangioendotheliomas involving the pancreas and
mesenteric and abdominal lymph nodes; and precancerous lesions of
the small intestine (Snell and Stewart, 1962). The health-based
number for DBA is based on two USEPA documents (USEPA 1983a,b).
Indeno(1,2,3-cd)pyrene (IP) is a Class B2 carcinogen, as stated on
IRIS. This information was added to IRIS in December of 1990, and
is based on sufficient data from animal bioassays. IP is
considered carcinogenic to experimental animals based on dermal
application (Hoffman and Wynder, 1966; Rice et al., 1985a, 1986),
lung implantation (Deutsch-Wenzel et al. , 1983), intraperitoneal
injection studies (LaVoie et al. , 1987), and subcutaneous injection
studies (Lacassagne et al., 1963) on the mouse. The health-based
number for IP is based on the health-based number for BaP (5.79
/mg/kg/day) and a USEPA document (USEPA, 1982). According to the
document, IP is 1.7% as potent a carcinogen as benzo(a)pyrene.
Thus, 1.7% of 5.79 /mg/kg/day is 0.098 /mg/kg/day, which is the
calculated CSF for IP. The subsequent health-based number is then
calculated according to the methodology described previously.
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Several of the constituents of concern, including benzene (IAJRC,
1982), BaP (Shum et aJL. , 1979), DBA (Wolfe and Byran, 1939), and
naphthalene (Harris et aJL. , 1979) have also been shown to be
embryotoxic ana/or teratogenic in experimental animals. Also,
naphthalene has been shown to be embryotoxic in humans (Zinkham and
Childs, 1958; Anziulewisc et al., 1959).
Naphthalene has been shown to be a systemic toxicant. In one
gavage study of rats, diarrhea, lethargy, hunched posture, rough
coats and a decrease in body weight gain were noted (NTP, 1980).
Schmahl (1955) performed a chronic oral toxicity study for the
development of a NOEL. No data were available to indicate that
naphthalene is carcinogenic (USEPA, 1986). The health-based number
for naphthalene is from the 1992 Annual HEAST. As stated in the
preamble to the final rule, the HBN for naphthalene was decreased
one order of magnitude between the proposal and the final rule.
According to the 1992 HEAST, "the chronic oral [RfD] was changed
for reflect the evaluation by the RfD/RfC Work Group (1989). For
the chronic [RfD], an uncertainty factor of 1000 represents 10 each
for intraspecies and interspecies extrapolation and cataract
formation."
In addition to their ability to act as carcinogens, several of
these constituents (as well as other PAHs that express no
carcinogenicity on their own) have been found to act as initiators
or promoters (cocarcinogens) of skin tumors in mice. Chemicals
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found to initiate skin tumors after a single application or
multiple applications followed by croton oil treatment include BA
(Hadler et al. , 1959) ; BbF (Van Duuren et a_l, 1966) ; BkF (LaVoie et
al. , 1982); DBA (Klein, 1960); and IP (IARC, 1973).
It is important to note that many PAHs identified in the wastes
proposed for listing have the ability to act as cocarcinogens.
PAHs such as benzo(g,h,i)perylene (BghiP) , fluoranthene, and pyrene
are not carcinogenic in pure form. When applied to the skin of
mice along with a carcinogen such as BaP, they can often enhance
the carcinogenic effect of BaP alone (e.q.. IARC, 1983; Van Duuren
and Goldschmidt, 1976). This cocarcinogenic phenomenon is of
concern because many of the waste streams proposed for listing
contain mixtures of PAHs comprising carcinogens and cocarcinogens.
This factor indicates that the health-based levels of concern
presented earlier (which are based on exposure to individual
compounds) may underestimate the toxicity of these compounds when
found in the wastes as mixtures of PAHs.
Almost all of the PAHs considered here possess some degree of
mutagenicity in short-term tests for genotoxicity. Chemicals found
to induce mutations in at least one strain of Salmonella
typhimurium include BA (e.g. . Claxton, 1983); BaP (e.g.. McCann et
al. 1975) ; and IP (e.g. . LaVoie et a_l. , 1979) . Other evidence for
genotoxicity includes induction of sister chromatid exchanges by BA
(Tong e£ a_l. , 1981a, 1981b) and by BaP, BbF, and DBA (Rozinski and
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Kocher et al., 1979) ; and morphological transformation in a number
of in vitro test systems by DBA and IP (Chen and Heidelberger, 1969
and Emura et al.. 1982).
F. Mismanagement Case Histories
A number of mismanagement case histories will be presented in this
Background Document. They are examples of incidents which have
caused environmental damage due to the mismanagement of coke by-
products and tar refining wastes in the past. These incidents are
presented in Appendix A.
G. Proposal Kot to List Coke By-Products Wastewaters
EPA is not listing coke by-products wastewaters as hazardous
wastes. This decision is based on the Agency's expectation that at
least some of the wastewater streams at coke by-products facilities
will typically and frequently fail the TC test for benzene. EPA,
therefore, expects that the wastewaters will be effectively
regulated under the TC rule. In particular, final cooler blowdown
and wastewater from light oil recovery contain benzene levels
ranging from 0.44 to 86 ppm. Table 18 presents the ranges of
concentrations found for the hazardous constituents present in
these wastewaters. EPA found that out of 12 samples analyzed, 7
had benzene levels higher than the promulgated TC level of 0.5 ppm.
Therefore, these wastes are not regulated Subtitle C wastes because
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they are characteristically hazardous. As shown in Table 18,
wastewaters do not typically and frequently contain PAHs at levels
of regulatory concern.
Pursuant to 40 CFR §261.11 (a) (1) the Agency could have listed other
wastewater streams from coke by-products plants (e.g., final cooler
blowdown and wastewaters from light oil recovery) on the basis of
the concentrations of benzene present in these waste streams.
However, the Agency has decided not to list them and considers
their regulation by the promulgated TC rule to be sufficiently
protective of human health and the environment (for details on the
TC rule, see 55 FR 11798-11862) . EPA does not have analytical data
on the concentrations of benzene and other hazardous constituents
of concern in sludges generated from the treatment of coke by-
product wastewaters. However, since concentrations of most of
these constituents in wastewaters with the exception of benzene are
not typically and frequently present at levels of regulatory
concern, the Agency does not believe that listing of sludges is
warranted.
H. Conclusions
The criteria in 40 CFR §261.11(a)(3) specify that the Agency will
list a waste as hazardous if it contains constituents listed in
Appendix VIII unless, after consideration of one or more of the
eleven factors enumerated in 40 CFR §261.11(a) (3) , the Agency
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concludes that the waste is not capable of posing a substantial
present or potential hazard to human health or the environment when
improperly managed. After considering a number of these factors,
including the toxicity, mobility, persistence, and the
concentration of hazardous constituents in these residuals, the
Agency concludes that these residuals meet the criteria for
listing. The Agency, therefore, is adding the wastes described in
this Background Document (K141 through K145, K147, and K148) to the
list of hazardous wastes in 40 CFR 261.32.
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SECTION VI
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