United States
Environmental Protection
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S4-85/053 Sept. 1985
Project Summary
Evaluation of Ignitability
Methods (Liquids)
M. Umana, W. Gutknecht, C. Salmons, R. Chapman,
R. Handy, and E. Pellizzari
The purpose of this research was to
evaluate the ignitability Methods 1010
(Pensky-Martens) and 1020 (Setaflash)
as described by Office of Solid Waste
(OSW) Manual SW846. This effort was
designed to provide information on ac-
curacy and precision of the two meth-
ods. During Phase I of this task, six
standards and simple mixtures were
tested. In addition during Phase II,
twelve actual wastes were tested.
The results of Phase I determined
that both methods are applicable to
characterize the ignitability of liquid
wastes. During Phase I, no significant
interferences were identified. During
Phase II experiments, however, water-
containing wastes could not be tested
using Method 1020. No direct compari-
son of Phase I results and data pub-
lished in literature reports was made
due to the uncertainty associated with
the previously published data. A search
of the Chemical Abstract Data Base
provided more reliable information
than previously published data for p-
xylene flash point.
Based on standards and simple mix-
tures results, no significant difference
existed between the accuracy and pre-
cision of the two methods. The results
of actual waste experiments, however,
showed significant differences be-
tween the methods. The Setaflash
method, when applicable, was deter-
mined to be more accurate and more
precise than the Pensky-Martens. The
Pensky-Martens method is not applica-
ble for wastes which have flash points
below 13°C (55°F). The Setaflash
method is not applicable to complex
mixtures with substantial amounts of
water and high surface tension.
This Project Summary was devel-
oped by EPA's Environmental Monitor-
ing and Support Laboratory, Cincinnati,
OH, to announce key findings of the re-
search project that is fully documented
in a separate report of the same title
(see Project Report ordering informa-
tion at back).
Introduction
Disposal of solid wastes at landfill
sites presents several potential hazards
apart from intrinsic toxicity of the dis-
posed materials. The ignitability of
waste substances is of concern because
of the imminent danger of uncontrolled
burning, and the probable toxicity of the
combustion products.
A waste has been defined in the Re-
source Conservation and Recovery Act
(RCRA) (40 CFR 261.21) as hazardous if
it exhibits any of the following ignitabil-
ity characteristics:
1. "It is a liquid, other than an aqueous
solution containing less than 24% al-
cohol by volume, and has a flash
point less than 60°C (140°F), as deter-
mined by a Pensky-Martens Closed-
Cup Tester, using the test method
specified in American Society of
Testing Materials (ASTM) Standard
D-93-79 or D-93-80, or a Setaflash
Closed-Cup Tester, using the test
method specified in ASTM Standard
D-3278-78, or as determined by an
equivalent test method approved by
the Administrator under the proce-
dures set forth in RCRA section
260.20 and 260.21.
2. It is not a liquid and is capable, under
standard temperature and pressure,
of causing fire through friction, ab-
sorption of moisture, or sponta-
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neous chemical changes and, when
ignited, burns so vigorously and per-
sistently that it creates a hazard.
3. It is an ignitable compressed gas as
defined in 49 CFR 173.300 and as de-
termined by the test methods de-
scribed in that regulation or equiva-
lent test methods approved by the
Administrator under RCRA section
260.20 and 260.21.
4. It is an oxidizer as defined in 49 CFR
173.151."
Specific ignitability tests have been
developed and refined under several
previous work assignments to this con-
tract, "Development and Evaluation of
Test Procedures for Ignitability Criteria
for Hazardous Waste."
The directions for using the Pensky-
Martens Closed-Cup tester and the
Setaflash Closed-Cup tester to deter-
mine ignitability are set down in
Method 1010 and Method 1020 respec-
tively in the OSW publication SW846.
In order to identify wastes which are
subject to this hazard, this work assign-
ment, "Evaluation of Ignitability Meth-
ods (Liquids)," was undertaken. The
purpose of this task was to evaluate Ig-
nitabillty Methods 1010 and 1020 as de-
scribed in OSW Manual SW846 using
standards during Phase I and waste
samples during Phase II and to provide
precision and accuracy data for these
methods.
Some refinements of the procedures
were necessary to perform the evalua-
tion. However, since the goal of this
project was to evaluate existing meth-
ods rather than improve them, only
small modifications, if any, were made.
Since the equipment is designed for
such measurements, all of the experi-
ments measured temperatures in de-
grees Fahrenheit (°F). When data were
reported in degrees Centigrade (°C), the
data were calculated and approximated
to the nearest decimal unit.
Experimental Procedures
Setaflash Experiments
The standards and simple mixtures
were tested in triplicate using the
Setaflash equipment, following the pro-
cedure specified by Method 1020. Using
a 2 ml syringe, the sample (2 ml) was
introduced through a tight port into the
closed test chamber, which had been
previously heated to within 3°C below
the expected flash point. No stirring is
provided. After allowing approximately
one minute for temperature equilibra-
tion, a small flame (4 mm in diameter)
was directed into the cup through a
small window. Careful observation was
made as to whether the sample flashed
or not. If there was no flash, the temper-
ature was sequentially increased by
0.5°C until a flash was observed. A re-
peat determination was then performed
using a fresh sample.
Pensky-Martens Experiments
Standard samples were analyzed in
triplicate for flash point by the Pensky-
Martens closed-cup tester in accord-
ance with the procedure given in ASTM
D-93. In this procedure, the sample cup
was cleaned, dried, and filled to the
mark with sample. Approximately
50 mL of sample are required. The cup
was then placed in the neater, and the
cup lid was lowered and locked into
place. The thermometer was inserted.
The test flame was lit and adjusted to
4mm in diameter. The heater was
turned on and set so that the tempera-
ture of the solution rose 5-6°C (9 to 11°F)
per minute. The stirrer was turned on.
Every 1°C (~2°F), the shutter was
opened, and the test flame was lowered
into the vapor space of the cup. The
sample was not stirred while the flame
was lowered into the cup. The flash
point was the temperature at which the
test flame application caused a distinct
flash in the interior of the cup.
Results and Discussion
The six standards and simple sam-
ples selected for use during Phase I of
this task were analyzed in triplicate and
the results were corrected for baromet-
ric pressure.
Preliminary Experiments
Preliminary experiments with waste
samples acquired during Phase I were
performed. During these tests, it was
determined that all of the wastes had a
flash point below room temperature as
measured with the Setaflash method. A
modification of Methods 1010 (Pensky-
Martens) and 1020 (Setaflash) was im-
plemented to allow for flash point mea-
surements below 21°C (70°F). The
modification consists of cooling the
testing cup with dry ice, introducing the
sample once the testing cup is cold,
then allowing the temperature of the
testing cup to raise slowly as the exper-
iment begins. This modification has
proven successful for a very wide range
of temperatures using the Setaflash
method. For the Pensky-Martens
method, however, it was determined
that this procedure is practical only
down to about 10 to 13°C (50° to 55°F
due to the fact that Pensky-Marten
equipment has a very massive cu|
which cools and reheats very slowl'
making the operation impractical.
The decision was made that wast
samples with measured flash points be
low 55°F would be spiked with a wasti
oil and/or carbon tetrachloride (CCU) ii
order to raise the temperature of mea
surement above the minimum permit
ted by the Pensky-Martens method
This decision was based upon the fac
that the purpose of this task was to de
termine accuracy (measured for stand
ard samples) and precision of the meth
ods under consideration and not to tes
the wastes. The fact that some of th<
collected wastes had low flash points
was purely circumstantial and spikinc
them with a waste oil would not altei
the goal of this task.
Waste Mixtures
A 5-gallon waste motor oil sample
was collected from a local service sta-
tion. Varying amounts of this waste oi
were added to those waste samples
which had low flash points. Mixtures oi
the wastes and carbon tetrachloride
were also prepared.
The mixtures were than tested using
the Setaflash method which required
only a 2 ml sample per determination,
In order to raise the flash point above
room temperature, a considerable
amount of spiking material was re-
quired, in most cases more than 70% o1
either used motor oil or CCU. These re-
sults demonstrated that the spiking oi
the waste samples was impractical and
this strategy was abandoned.
All the data have been corrected for
atmospheric variations. The data ob-
tained by the Setaflash method for
waste 2258-14-08-3 were corrected by
adding 1°F in order to compensate for
the difference obtained for the p-xylene
control which was 1°F below that value
allowed by the Method 1020 (Seta-
flash) description.
Several wastes tested by the Seta-
flash method showed no measurable
flash point below 110°C (230°F). This
phenomenon was observed primarily
on those wastes that contained sub-
stantial amounts of an aqueous phase
and had a large surface tension as de-
termined by empirical observation; the
high surface tension prevented the
waste from dispersing evenly through-
out the cup and since only 2 mL of sam-
ple was required, part of the cup re-
mained empty. If agitation was
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provided, then a flash occurred (note
that the Pensky-Martens method in-
cludes stirring). If a larger flame than
the one specified by the method was
applied, a flash was observed, however,
this flash was usually at a higher tem-
perature than expected. This observa-
tion may constitute a severe interfer-
ence to the Setaflash method because it
may determine that some ignitable
wastes do not flash.
The Setaflash method did not deter-
mine a flash point for two of the three
replicates performed on waste 2258-14-
08-1. This was attributed to the evapora-
tion of some volatile component before
the measurement was performed and
the residue did not flash. This phenom-
enon may be enhanced by the small
amount of sample required (2 ml).
Conclusions
Comparison and evaluation of Meth-
ods 1010 and 1020 during Phase I and
Phase II gave the following conclusions:
a. Based on the testing of standards
and simple mixtures, both Meth-
ods 1010 and 1020 were found to
be applicable to characterize the
ignitability of liquids.
b. No significant interferences were
found in the measurement of ig-
nitability of standards and simple
liquid mixtures.
c. A comparison of open-cup and
closed-cup experiments shows
that open-cup values are approxi-
mately 7°C (20°F) higher than
those obtained in closed-cup ex-
periments.
d. No statistically significant differ-
ence was found between the re-
sults obtained during Phase I
using standards and simple mix-
tures for the two methods under
consideration.
e. From the results of experiments
with actual waste samples, it was
also determined that the Pensky-
Martens method is not practical to
use with wastes of low flash points
(13°C or 55°F) and the Setaflash
method is not applicable to com-
plex aqueous mixtures which have
high surface tension.
f. Experiments with actual waste
samples also established that flash
point measurements made with
the Setaflash method were more
precise than the Pensky-Martens
method. Also, the Setaflash was
found to be more accurate based
on tests with p-xylene. Finally, it
was concluded that the Setaflash
system is easier to use and re-
quires much less sample than the
Pensky-Martens system.
Recommendations
From the results presented in this re-
port, the authors recommend:
a. The use of Method 1010 (Pensky-
Martens) to test the flash point of
ignitable wastes, despite the fact
that the method does not easily al-
low measurement of flash points
below room temperature. The
Pensky-Martens system can iden-
tify those samples that flash at or
below room temperature and this
is enough to label them haz-
ardous. Although the Setaflash
method is more accurate and
more precise, the Pensky-Martens
method has a wider range of appli-
cability to the needs of EPA.
b. The use of Method 1020 (Seta-
flash) when a determination of low
temperature flash points is re-
quired.
c. Further research, using synthetic,
well characterized, complex mix-
tures to confirm the conclusions
obtained during this study.
M. Umana. W. Gutknecht, C. Salmons, R. Chapman. R. Handy, andE. Pellizzariare
with Research Triangle Institute, Research Triangle Park, NC 27709.
John D. Pfaff is the EPA Project Officer (see below).
The complete report, entitled "Evaluation of Ignitability Methods (Liquids), "(Order
No. PB 85-241 255/AS; Cost: $11.50, subject to change) will be available only
from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
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United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
BULK RATE
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PERMIT No G-35
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EPA/600/S4-85/053
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