Page
1
of
3
Memorandum
From:
Ahmar
Siddiqui
USEPA/
OW/
OST
ph:
(
202)
566
1044
siddiqui.
ahmar@
epa.
gov
To:
Public
Record
for
the
Effluent
Guidelines
Program
Plan
for
2004/
2005
Date:
May
10,
2004
Re:
Alternatives
to
Method
1664
for
Quantifying
Light
Hydrocarbon
Pollutant
Loadings
Overview
NPDES
permits
often
control
pollutant
discharges
through
limitations
on
discharges
of
oil
and
grease
(
as
measured
through
EPA
Method
1664).
As
part
of
our
review
of
the
Petroleum
Refining
industry
EPA
will
consider
whether
EPA's
approved
analytical
methods
for
oil
and
grease
(
Method
1664)
adequately
quantify
pollutant
discharges
from
this
industry
(
including
the
pollutant
discharges
from
the
Petroleum
Bulk
Stations
and
Terminals
(
PBST)
(
SIC
5171)
industrial
sector).
This
memorandum
describes
some
limitations
of
Method
1664
and
some
potential
analytical
alternatives
for
better
quantifying
pollutant
discharges
from
the
Petroleum
Refining
industry.

Background
EPA
has
promulgated
Method
1664,
Revision
A:
N­
Hexane
Extractable
Material
(
HEM;
Oil
and
Grease)
and
Silica
Gel
Treated
N­
Hexane
Extractable
Material
(
SGT­
HEM:
Non­
polar
Material)
by
Extraction
and
Gravimetry
as
a
replacement
for
determination
of
oil
and
grease
by
EPA
Method
413.1
for
use
in
EPA's
Clean
Water
Act.
EPA
has
not
developed
replacement
methods
for
EPA
Methods
413.2
and
418.1,
which
determine
oil
and
grease
and
total
petroleum
hydrocarbon
content,
respectively,
via
extraction
of
oil
from
samples
using
Freon
113,
followed
by
quantification
of
oil
content
using
infrared
spectroscopy.
For
all
these
methods,
"
oil
content"
is
a
method­
defined
analyte,
meaning
the
definition
of
oil
content
is
dependent
on
the
procedure
used.
The
nature
of
the
oils,
and
the
presence
of
extractable
non­
oily
matter
in
the
sample
will
influence
the
material
measured
and
interpretation
of
the
results.

Petroleum
Refining
and
PBST
facilities
produce,
collect,
store,
and
distribute
petroleum
and
petroleum
products,
including
crude
oil,
gasoline,
aviation
gasoline,
jet
fuel
(
JP­
4),
diesel
fuel,
fuel
oil,
kerosene,
naphtha,
and
lubricating
oils.
Section
1.3
of
Method
1664A
states
that
"
this
method
is
not
applicable
to
measurement
of
materials
that
volatilize
at
temperatures
below
approximately
85

C.
Petroleum
fuels
from
gasoline
through
#
2
fuel
oil
may
be
partially
lost
in
the
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2
of
3
solvent
removal
operation."
In
addition,
Section
1.4
of
Method
1664A
states
that
"
Some
crude
oils
and
heavy
fuel
oils
contain
a
significant
percentage
of
materials
that
are
not
soluble
in
nhexane
Accordingly,
recoveries
of
these
materials
may
be
low."

Finally,
some
petroleum
refining
and
PBST
facilities
would
likely
produce,
collect,
store,
and
distribute
products
that
include
oxygenates.
Common
oxygenates
include
MTBE,
ethanol,
methanol,
and
tert­
butyl
alcohol.
EPA
will
examine
the
control
of
these
compounds
through
the
use
of
Method
1664.

Alternatives
to
Method
1664
EPA
is
investigating
the
usability
of
Method
1664A
and
other
analytical
methods
to
measure
oil
and
grease,
petroleum,
and
petroleum
products
in
Petroleum
Refining
and
PBST
wastewaters.
This
section
provides
a
listing
and
short
summary
on
each
alternative
analytical
for
quantifying
pollutant
discharges
from
the
Petroleum
Refining
and
PBST
industrial
category.
EPA
will
use
this
information
for
the
final
Effluent
Guidelines
Program
Plan
for
2004/
2005.

One
approach
to
refining
analysis
for
oil
and
grease
and
total
petroleum
hydrocarbon
content
in
wastewaters
involves
the
use
of
a
gas
chromatography
procedure
using
photoionization/
flame
ionization
detectors
(
GC­
PID/
FID).
This
general
approach
is
being
used
in,
among
other
places,
Connecticut,
Florida,
and
Oregon/
Washington,
and
has
been
submitted
for
public
comment
in
Massachusetts.

The
Connecticut
method
("
Analysis
of
Extractable
Total
Petroleum
Hydrocarbons
(
ETPH)
Using
Methylene
Chloride
Gas
Chromatograph/
Flame
Ionization
Detection")
was
approved
on
June
22,
1999
for
use
in
measuring
hydrocarbons
ranging
from
C
9
to
C
36.
As
such,
it
addresses
the
one
noted
shortcoming
of
Method
1664A
(
its
inability
to
detect
lighter
hydrocarbons).
However,
given
the
range
of
the
Connecticut
method,
it
may
not
be
appropriate
for
use
in
detecting
the
very
lightest
fractions
of
gasoline.

The
Florida
method
("
Characterization
of
C
6
to
C
35
Petroleum
Hydrocarbons
in
Environmental
Samples")
is
similar
to
the
Connecticut
method
in
its
use
of
GC­
FID.
In
this
case,
the
extraction
solvent
is
n­
pentane.
The
method
reliably
detects
hydrocarbons
with
boiling
points
between
70

C
and
500

C,
thereby
detecting
some
of
the
lighter
fractions,
along
with
some
of
the
heavier
fractions,
missed
by
Method
1664A.
However,
as
in
the
case
with
the
Connecticut
method,
truly
light
fractions
are
likely
to
be
missed.

The
Oregon/
Washington
approach
is,
in
fact,
a
combination
of
methods
("
NWTPH­
Gx
Volatile
Petroleum
Products
Method
for
Soil
and
Water"
and
"
NWTPH­
Dx
Semi­
Volatile
Petroleum
Products
Method
for
Soil
and
Water").
Both
methods
use
GC­
FID.
Lighter
fractions,
such
as
gasolines
and
naphthas,
are
detected
by
NWTPH­
Gx.
Heavier
fractions
(
jet
fuels
through
heavy
fuel
oils)
are
measured
using
NWTPH­
Dx.
Water
samples
being
analyzed
using
NWTPH­
Gx
may
be
directly
introduced
into
a
purge/
trap
concentrator
and,
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3
of
3
thereafter,
analyzed
using
GC­
FID.
The
method
used
for
detection
of
heavier
fractions,
NWTPHDx
involves
extraction
with
methylene
chloride
(
much
like
the
Connecticut
method)
and
then
the
use
of
GC­
FID.

The
Massachusetts
method
(
MADEP­
VPH­
03­
1)
is
much
like
NWTPH­
Gx
(
direct
injection
into
a
purge
trap/
concentrator
and
then
GC­
FID).
The
method
effectively
detects
hydrocarbon
fractions
with
boiling
points
between
36

C
and
220

C
and
is,
therefore,
suitable
for
detecting
lighter
hydrocarbons
than
any
of
the
previously
described
methods.

Another
option
for
detecting
lighter
fractions
using
GC­
FID
involves
the
use
of
hexadecane
as
the
extraction
solvent.
It
is
believed
that
this
will
allow
detection
of
very
light
fractions
(
C
2
to
C
12).
EPA
is
not
aware
of
any
entities
currently
using
this
method,
though
it
expects
to
study
its
feasibility.
In
addition,
EPA
is
seeking
data
from
Connecticut,
Oregon,
and
Washington
to
further
assess
the
use
of
methylene
chloride
as
an
extraction
solvent
for
TPH.

A
final
option
for
light
fraction
detection
involves
the
use
of
an
infrared
spectroscopy
method
recently
approved
by
The
American
Society
for
Testing
and
Materials
(
ASTM),
D3414­
98(
2004),
Standard
Test
Method
for
Comparison
of
Waterborne
Petroleum
Oils
by
Infrared
Spectroscopy.
EPA
has
not
evaluated
this
method
and
further
information
may
be
found
directly
from
ASTM.
