Document ID: EPA-HQ-OW-2003-0074-0600
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2003-12-24T05:00Z

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MEMORANDUM
TO:
304(
m)
Record
(
EPA
Docket
Number
OW­
2003­
0074)

FROM:
Arash
Hooshangi
DATE:
December
11,
2003
SUBJECT:
Toxic
Weighting
Factor
for
Petroleum
Refining
Polycyclic
Aromatic
Compounds
Definition
of
PACs
and
Reporting
Requirements
Polycyclic
Aromatic
Compounds
(
PACs),
sometimes
known
as
Polycyclic
Aromatic
Hydrocarbons,
are
a
class
of
organic
compounds
consisting
of
two
or
more
fused
aromatic
rings.

EPA's
Toxic
Release
Inventory
(
TRI)
program
has
identified
21
chemicals
that
are
included
in
the
PAC
category
(
see
Table
1).
Facilities
with
10
or
more
employees
in
specified
Standard
Industrial
Classification
(
SIC)
codes
that
manufacture,
process,
or
use
more
than
100
pounds
of
PACs
per
year
must
report
the
releases
of
these
compounds
to
EPA.
Facilities
report
the
combined
mass
of
PACs
released
and
do
not
report
releases
of
individual
compounds.

Toxic
Weighting
Factors
EPA's
Office
of
Water/
Engineering
and
Analysis
Division
(
EAD)
uses
Toxic
Weighting
Factors
(
TWFs)
to
compare
pollutants
discharged
by
various
industrial
categories.
The
pounds
of
pollutant
discharged
are
multiplied
by
the
TWF
to
calculate
equivalent
pounds.
The
weighted
pounds
can
be
added.
For
example,
toxic
equivalent
pounds
of
lead
can
be
added
to
toxic
equivalent
pounds
of
mercury.
Also,
the
equivalent
pounds
released
by
one
facility
or
industry
can
be
compared
to
other
facilities
or
industries.
As
listed
in
Table
1,
EAD
has
TWFs
for
eight
of
the
21
individual
compounds
comprising
the
TRI
PAC
category.
Memorandum
11
December
2003
Page
2
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Calculating
Equivalent
Pounds
of
PACs
Facilities
report
to
TRI
the
combined
mass
of
PACs
released,
but
EAD
has
TWFs
for
individual
compounds.
Thus,
to
calculate
the
equivalent
pounds
of
PACs
released,
EAD
must
identify
which
individual
compounds
comprised
the
reported
PACs.
EAD
made
two
different
assumptions
about
the
identity
of
the
compounds
comprising
the
PACs,
resulting
in
the
two
methods
for
calculating
equivalent
pounds
of
PACs,
described
below.

Method
1:

EAD
assumed
that
the
only
compound
in
the
PAC
category
discharged
by
refineries
was
benzo(
a)
pyrene.
The
equivalent
pounds
of
PACs
was
calculated
by
multiplying
the
reported
PAC
releases
by
4283.56,
the
benzo(
a)
pyrene
TWF.
Of
all
the
PACs,
benzo(
a)
pyrene
has
the
highest
TWF.
Thus,
this
method
represents
a
worst­
case
estimate
of
the
pound­
equivalents
of
PACs
released
by
petroleum
refineries.

Method
2:

EAD
assumed
that
composition
of
PACs
released
by
refineries
is
proportional
to
the
composition
of
raw
materials
(
crude
oil)
and
products
throughput
at
U.
S.
refineries.

Available
Data:
The
PACs
composition
of
a
number
of
petroleum
products
and
crude
oils
is
available
in
the
literature
(
see
Tables
2
and
3).
In
addition,
the
Energy
Information
Administration
(
EIA)
publishes
a
yearly
report
of
the
amount
of
petroleum
products
produced
in
all
U.
S.
petroleum
refineries
as
well
as
the
amount
of
crude
oil
consumed
(
see
Table
4).
Memorandum
11
December
2003
Page
3
1EIA:
Petroleum
Supply
Annual
2000,
Vol
1,
Page
6
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Assumptions.
EAD
made
the
following
assumptions:

1)
PACs
will
be
present
in
wastewater
in
the
same
proportion
that
they
are
present
in
the
crude
oil
and
products
throughput
at
U.
S.
refineries.
These
proportions
are
presented
in
Table
4.

2)
If
no
data
were
available
for
a
specific
PAC
compound,
its
concentration
in
the
crude
oil
or
product
was
assumed
to
be
zero.
If
a
PAC
compound
was
not
detected,
its
concentration
in
the
crude
oil
or
product
was
assumed
to
be
zero.

3)
Where
PAC
composition
is
not
available,
it
can
be
estimated
using
the
composition
from
similar
products.
Table
5
presents
a
list
of
the
products
for
which
PAC
composition
is
not
available
and
the
similar
product
used
to
estimate
the
composition.

4)
For
crude
oil,
representative
domestic
and
foreign
oils
can
be
used
to
calculate
a
weighted
average
PAC
composition
for
crude
oil.
According
to
EIA1,
39.09
percent
(
volumetric
basis)
of
the
total
consumed
crude
oil
in
the
U.
S.
in
the
year
2000
was
domestic
while
60.91
percent
(
volumetric
basis)
was
imported.
EAD
selected
South
Louisiana
Oil,
for
which
PAC
composition
is
available,
as
a
representative
domestic
oil
and
Alberta
Oil
as
a
representative
foreign
oil.
EAD
assumed
that
a
weighted
average
of
the
composition
of
these
two
crude
oils
is
a
reasonable
representation
of
crude
oil
composition
for
the
purpose
of
this
study.

EAD
also
used
a
specific
weight
of
0.92
for
crude
oil
in
order
to
convert
PAC
concentrations
reported
as
mg/
kg
to
mg/
l.
Memorandum
11
December
2003
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4
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5)
For
refined
products,
EAD
assumed
a
specific
weight
of
1.0
(
i.
e.,
no
need
to
convert
between
mg/
kg
and
mg/
l).

Calculations.
Based
on
the
above
assumptions,
EAD
calculated
the
proportion
of
each
of
the
21
TRI
PACs
that
would
be
present
in
refinery
wastewater.
EAD
accomplished
this
by
multiplying
each
product
percentage
(
shown
in
Table
4)
by
its
chemical
concentration
(
from
Table
2,
for
products,
or
Table
3
for
crude
oils).
EAD
then
summed
all
the
mass
of
each
PAC,
and
calculated
percentages
for
each
chemical
relative
to
the
total
mass
of
all
21
chemicals.
These
percentages
are
presented
in
Table
6.
For
example,
EAD
estimated
that
17.47
percent
of
the
PACs
released
in
refinery
wastewater
are
benzo(
a)
anthracene.

EAD
calculated
the
overall
TWF
by
multiplying
the
chemical
proportions
by
their
respective
TWFs
and
summing
all
the
values
obtained
from
21
PACs
(
see
Table
6).
This
calculation
resulted
in
a
TWF
value
of
230.43.
The
toxic
pound
equivalent
of
the
combined
mass
of
PACs
reported
to
TRI
by
petroleum
refineries
can
then
be
calculated
by
multiplying
the
reported
PAC
releases
by
230.43.
Memorandum
11
December
2003
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5
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Table
1:
PACs
and
their
TWF's
Chemical
Name
Toxic
Weighting
Factor
Benzo(
a)
anthracene
180.9752
Benzo(
a)
phenanthrene
(
chrysene)
2.1038
Benzo(
a)
pyrene
4283.5600
Benzo(
b)
fluoranthene
421.3560
Benzo(
j)
fluoranthene
Benzo(
k)
fluoranthene
42.1356
Benzo(
j,
k)
fluorene
(
fluoranthene)
0.8030
Benzo(
r,
s,
t)
pentaphene
Dibenz(
a,
h)
acridine
Dibenz(
a,
j)
acridine
Dibenzo(
a,
h)
anthracene
1693.0160
Dibenzo(
a,
e)
fluoranthene
Dibenzo(
a,
e)
pyrene
Dibenzo(
a,
h)
pyrene
Dibenzo(
a,
l)
pyrene
7H­
Dibenzo(
c,
g)
carbazole
7,12­
Dimethylbenz(
a)
anthracene
Indeno(
1,2,3­
cd)
pyrene
1.1388
3­
Methylcholanthrene
5­
Methylchrysene
1­
Nitropyrene
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2003
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Table
2:
PAC
Composition
of
a
Number
of
Petroleum
Products
Chemical
Name
Gasoline1
Kerosene2
No.
2
Diesel
Fuels3
Bunker
C
No.
6
Oil4
Paving
Asphalt5
Lube
Oil6
mg/
L
ppm
(
wt/
vol)
mg/
L
or
mg/
kg
mg/
kg
Benzo(
a)
anthracene
4.30
0.75
0.80
90.00
90.00
0.68
Benzo(
a)
phenanthrene
(
chrysene)
2.00
2.00
3.40
196.00
80.00
3.20
Benzo(
a)
pyrene
1.80
0.50
nd
44.00
1.30
0.23
Benzo(
b)
fluoranthene
0.75
0.62a
Benzo(
j)
fluoranthene
Benzo(
k)
fluoranthene
0.50
1.80
Benzo(
j,
k)
fluorene
(
fluoranthene)
6.50
4.00
2.80
240.00
2.00
Benzo(
r,
s,
t)
pentaphene
Dibenz(
a,
h)
acridine
0.20
Dibenz(
a,
j)
acridine
Dibnezo(
a,
h)
anthracene
0.75
4.60
Dibenzo(
a,
e)
fluoranthene
Dibnezo(
a,
e)
pyrene
0.45
Dibenzo(
a,
h)
pyrene
1.00
Dibenzo(
a,
l)
pyrene
7H­
Dibenzo(
e,
g)
carbazole
7,12­
Dimethylbez(
a)
anthracene
Indeno(
a,
2,3­
cd)
pyrene
2.00
3­
Methylcholanthrene
0.10
5­
Methylchrysene
6.00
1­
Nitropyrene
nd
=
nondetect
a
Value
for
benzofluoranthenes.
Source:
Data
compiled
in
the
American
Petroleum
Institute's
(
API's)
Transport
and
Fate
of
non­
BTEX
Petroleum
Chemicals
in
Soil
and
Groundwater
(
API
Publication
number
4593,
September
1994,
Appendix
A).
See
Docket
Section
4.6,
DCN
00407.
1
See
Table
A­
8
(
Guerine,
1977).
2
See
Table
A­
11
(
Goodman
and
Haribons
198?).
3
See
Table
A­
14
(
Page
et
al,
1994).
4
See
Table
A­
15
(
Pancirov
and
Brown,
1975).
5
See
Table
A­
15
(
Malaiyandi
et
al
1982).
6
See
Table
A­
16
(
Eisenberg
et
al,
1988).
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11
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2003
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7
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Table
3:
PAC
Composition
of
Crude
Oils
(
mg/
kg)

Chemical
Name
South
Louisiana
Crude
Oil7
Alberta
Crude
Oil8
Weighted
Average
Benzo(
a)
anthracene
1.7000
0.6645
Benzo(
a)
phenanthrene
(
chrysene)
17.5600
30.0000
25.1372
Benzo(
a)
pyrene
0.7500
nd
0.2932
Benzo(
b)
fluoranthene
0.5000
4.0000
2.6319
Benzo(
j)
fluoranthene
0.9000
0.3518
Benzo(
k)
fluoranthene
1.3000
0.5082
Benzo(
j,
k)
fluorene
(
fluoranthene)
5.0000
6.0000
5.6091
Benzo(
r,
s,
t)
pentaphene
Dibenz(
a,
h)
acridine
Dibenz(
a,
j)
acridine
Dibenzo(
a,
h)
anthracene
Dibenzo(
a,
e)
fluoranthene
Dibenzo(
a,
e)
pyrene
Dibenzo(
a,
h)
pyrene
Dibenzo(
a,
l)
pyrene
7H­
Dibenzo(
c,
g)
carbazole
7,12­
Dimethylbenz(
a)
anthracene
Indeno(
a,
2,3­
cd)
pyrene
3­
Methylcholanthrene
3.0000
1.8273
5­
Methylchrysene
1­
Nitropyrene
nd
=
nondetect
Source:
Data
compiled
in
the
American
Petroleum
Institute's
(
API's)
Transport
and
Fate
of
non­
BTEX
Petroleum
Chemicals
in
Soil
and
Groundwater
(
API
Publication
number
4593,
September
1994,
Appendix
A).
See
Docket
Section
4.6,
DCN
00407.
7
See
Table
A­
3
(
Pancirov
and
Brown,
1975).
8
See
Table
A­
4
(
Benner
et
al.
1990).
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11
December
2003
Page
8
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Table
4:
Supply
and
Disposition
of
Crude
Oil
and
Petroleum
Products
Finished
Petroleum
Products
1000
bbl/
year
%
(
products
only)
volume
%
(
Total)
Finished
Motor
Gasoline
2,910,056
48.08%
25.16%
Reformulated
939,493
Oxygenated
2,221
Other
1,928,342
Finished
Aviation
Gasoline
6,543
0.11%
0.06%
Jet
Fuel
587,974
9.71%
5.08%
Naphtha­
Type
75
Kerosene­
Type
587,899
Kerosene
23,860
0.39%
0.21%
Distillate
Fuel
Oil
1,310,158
21.65%
11.33%
0.05%
Sulfur
and
under
905,064
Greater
than
0.05%
sulfur
405,094
Residual
Fuel
Oil
254,843
4.21%
2.20%
Naphtha
For
Petro.
Feed.
Use
74,039
1.22%
0.64%
Other
Oils
For
Petro.
Feed
Use
71,762
1.19%
0.62%

Special
Naphthas
21,868
0.36%
0.19%
Lubricants
65,687
1.09%
0.57%
Waxes
6,478
0.11%
0.06%
Petroleum
Coke
266,107
4.40%
2.30%
Asphalt
and
Road
Oil
192,223
3.18%
1.66%
Still
Gas
241,365
3.99%
2.09%
Miscellaneous
Products
19,957
0.33%
0.17%
Total
Products
6,052,920
100%
52.33%

Crude
Oil
5,514,395
­­
47.67%

TOTAL
VOLUME
OF
PRODUCTS
&
CRUDE
OIL
11,567,315
­­
100%

Source:
EIA:
Petroleum
Supply
Annual
2000,
Vol
1,
Page
34
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11
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2003
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Table
5:
Products
for
Which
PAC
Composition
Is
Not
Available
Product
PAC
Composition
taken
from
Finished
Aviation
Gasoline
Gasoline
Jet
Fuel
Gasoline
Miscellaneous
Products
Gasoline
Naphtha
For
Petro.
Feed.
Use
Gasoline
Other
Oils
For
Petro.
Feed
Use
Gasoline
Petroleum
Coke
Paving
Asphalt
Special
Naphtha
Gasoline
Still
Gas
Gasoline
Waxes
Lube
Oil
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2003
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Table
6:
Calculation
of
Toxic
Weighting
Factor
for
PACs
Chemical
Name
Toxic
Weighting
Factor
Chemical
Percentage
Adjusted
TWF
Benzo(
a)
anthracene
180.9752
17.47%
31.62
Benzo(
a)
phenanthrene(
chrysene)
2.1038
46.29%
0.97
Benzo(
a)
pyrene
4283.5600
4.17%
178.46
Benzo(
b)
fluoranthene
421.3560
2.74%
11.54
Benzo(
j)
fluoranthene
0.36%
Benzo(
k)
fluoranthene
42.1356
0.70%
0.29
Benzo(
j,
k)
fluorene(
fluoranthene)
0.8030
24.32%
0.20
Benzo(
r,
s,
t)
pentaphene
Dibenz(
a,
h)
acridine
0.00%
Dibenz(
a,
j)
acridine
Dibezo(
a,
h)
anthracene
1693.0160
0.43%
7.35
Dibenzo(
a,
e)
fluoranthene
Dibenzo(
a,
e)
pyrene
0.00%
Dibenzo(
a,
h)
pyrene
0.00%
Dibenzo(
a,
l)
pyrene
7H­
Dibenzo(
c,
g)
carbazole
7,12­
Dimethylbenz(
a)
anthracene
Indeno(
1,2,3­
cd)
pyrene
1.1388
0.01%
0.00
3­
Methylcholanthrene
0.00%
5­
Methylchrysene
3.50%
1­
Nitropyrene
Total
230.43
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2003
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