United States
Environmental Protection
Agency
Industrial Environmental
Research Laboratory
Research Triangle Park NC 27711
Research and Development
EPA-600/S7-84-072 Aug. 1984
&ER& Project Summary
Waste Crankcase Oil Heater
Study: Phase II. Organic and
Inorganic Speciation Analyses
M. Cooke, W. E. Bresler, T. L Hayes, R. L. Livingston, C. T. Litsey, B. Paris, and
A. K. Wensky
This study involved measuring
specific chemical species in emissions
from two waste-oil-fired commercial
heaters: one utilized a vaporizing pot;
and the other, an air atomization com-
bustion chamber. Polynuclear aromatic
hydrocarbons (PAHs) were analyzed in
the gaseous emissions of both units.
Elemental analyses (including Pb, Fe,
Cd, Zn, Cl, and Br) were performed on
the air atomization discharges. In
addition, several waste crankcase oils
were tested for baseline levels of these
species and to determine the effect on
metal concentrations of both filtration
and sedimentation during storage.
Tests were also performed on emissions
from the air atomization burner to
measure the amount of organometallic
lead species discharged from the
burner, and to determine the distribu-
tion of iron oxidation states (Fe[IIJ
versus Fe[lll]) in gaseous emissions.
This Project Summary was developed
by EPA 'a Industrial Environmental Re-
search Laboratory, Research Triangle
Park. NC, to announce key findings of
the research project that is fully
documented in a separate report of the
same title (see Project Report ordering
information at back}.
Introduction
This study is an extension of earlier
work on residential appliances designed
specifically for waste oil combustion. In
that investigation, two reference waste
crankcase oils were burned in residential
waste heaters and a Level 1 analysis
performed on the fuels, combustion
residues, and gaseous emissions. The
two types of space heaters tested, a
vaporizing pot and an air atomization
heater, were found to produce high levels
of metallic discharges. The air atomizer
generated the highest gas-phase metal
discharges, and the vaporizing pot pro-
duced high levels of organic discharges
along with a metal-rich pot residue.
Among the metallic species identified for
further study were Pb, Fe, Cd, and Zn:
they were produced in high amounts and
(in certain forms) are potentially harmful
to humans. Since several researchers
have proposed the use of waste oil as
either a direct fuel or a blending agent to
lower the cost of primary fuels, it is of
great interest to investigate the environ-
mental impacts of expanded waste oil
use.
In this study, detailed investigations
were performed on the species identified
or suspected from the Level 1 data
generated in the earlier program. In this
study, samples were taken from both a
vaporizing pot unit (Kroll) and a residential
air atomization heater (Dravo). The experi-
mental portion of this study consisted of:
(1) Analysis of five fuels to determine
their metal content as a function of
storage, batch differences, and fuel
sources.
(2) Analysis of vaporizing pot and air
atomization discharges for poly-
nuclear aromatic hydrocarbons
(PAHs).
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(3) Analysis of air atomization
gaseous discharges for organolead
composition.
(4) Analysis of the Fe(ll)/Fe(lll) ratio in
the air atomizer gaseous effluent.
(5) X-ray fluorescence analysis of the
air atomizer particulate discharges
to show concentration of inorganic
species including Br, I, Fe, Cd, Pb,
and Zn.
Figure 1 shows the two heaters
schematically. The principal difference is
the way the flame is sustained in each
heater's firebox. The air atomization unit
injects aerosolized oil vapor into the burn
chamber, and the combustion gases are
discharged in the gas phase into the flue.
By contrast the vaporizing pot heater
operates through volitilization of heated
oil: the vapors are burned, and a heavy pot
residue is left behind. In the initial study,
this residue was found to contain a major
portion of the metallic species from the
fuel oil.
Experimental Procedures
PAHs were measured in both heaters
by collecting Modified Method 5 samples
and performing high-resolution capillary
gas chromatography/ mass spectrometry
(HRGC/MS) analysis on combustion
sample extracts. An example of the
complex organic matrix observed in these
samples is shown in Figure 2, the total ion
Stack
Damper —«-\
Low Pressure Air
Atomization Burner
Figure 1. Test combustion systems.
500
a
1000
15
1500
24
Scan Time (mini
2000
33
2500
41
Figure 2. HRGC/MS chromatogram of vaporizing pot emission sample.
chromatogram from the HRGC/MS
analysis of a vaporizing pot sample.
Volatile lead (alkyllead) compounds
were analyzed by collecting cryogenic
samples from the air atomization heater
Stack
Damper
Vapors
Waste Oil
' Pot Residue
Vaporizing Pot Burner
gas-phase discharges. High lead levels in
engine waste oil probably arise from lead
antiknocking agents added to gasoline.
Analyzing volatile lead compounds in
combustion emissions was important to
determine if organolead compounds
were stable in crankcase oil and subse-
quent combustion, or if ionic lead is
converted to appreciable organometallic
discharges during combustion. Figure 3
shows the cryogenic sampling train
developed for this study. Samples were
extracted with isooctane and analyzed by
combined gas chromatography/atomic
absorption spectrophotometry.
Metal species were analyzed by X-ray
fluorescence (XRF) on filter samples of
combustion gas from the air atomization
heater, and also on raw crankcase oil
samples. The XRF data were used to
confirm the presence of metallic species
that ostensibly arise from engine wear
(e.g., Fe) and elements that are present in
waste oil via contamination from fuel
additives (e.g., Br). The fuel data also
revealed comparative resuIts for waste oil
handling techniques; e.g., sedimentation
and filtration.
Iron speciation was performed to deter-
mine which oxidation state (Fefll] or
Fe[lll]) predominated in the ain
atomization discharges. Fe(ll) was*
analyzed by photometric analysis of
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Trap 2
extended period of time (11 months) had
little or no effect on the level of metallic
species in fuel obtained from the top of
the tank.
Iron Speciation
The iron speciation tests indicated that
most of the air atomizer iron emissions
existed as Fe(lll). This is a cause for great
concern due to the presence of benzo(a)
pyrene (BaP) in the PAH emissions. There
is a documented synergistic effect
between Fe(lll) and BaP which promotes
certain types of mammalian cancers and
is believed to magnify the dangers asso-
ciated with Fe(lll) emissions.
Figure 3. Cryogenic sampling train.
ferrous bathophenanthroline complex.
Since ferric compounds and benzo(a)py-
rene are known to produce a synergistic
promotion of certain tumors, these two
species were important to this study.
Conclusions
This study provided specific speciation
data on major constituents indicated as
being potentially harmful pollutants in
the previous Level 1 analysis of vaporizing
pot and air atomizer residential heater
emissions. Conclusions of this study are
summarized by chemical specie.
Polynuclear Aromatic
Hydrocarbons
Several PAH compounds were found at
elevated levels in the gas-phase
emissions from the two combustion
systems. As predicted from Level 1 data,
the vaporizing pot system produced ap-
preciably higher emissions than either
the air atomizer heater or (based on
literature estimates) residential heaters
fired with commercial fuel oil.
Lead Species
No organolead species were detected
in the cryogenic samples from the air
atomization heater, indicating that lead
exists essentially as Pbfll) in the air
atomization emissions.
Metals/Halogens
X-ray fluorescence analysis of panicu-
late emissions from the air atomization
heater particulate matter confirmed the
elevated Pb, Zn, and Fe found in earlier
Level 1 analyses. In addition, high Br and
Cl levels were found in gas-phase emis-
sions. The Br level was several times the
Cl level, indicating that Br from gasoline
antiknocking additives exists as a major
constituent of crankcase oil, and consti-
tutes a major air contaminant from this
source.
Fuel Studies
Filtration was shown to be effective for
lowering metallic species (such as iron) in
waste crankcase oil and should be a
beneficial pretreatment procedure for
this fuel. Settling by gravity over an
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M. Cooke. W. E. Bresler. T. L Hayes, ft. L Livingston, C. T. Litsey, B. Paris, and A. K.
Wenskyare with Battelle-Columbus Laboratories, Columbus, OH 43201.
Robert £. Hall is the EPA Project Officer (see below).
The complete report, entitled "Waste Crankcase Oil Heater Study: Phase II.
Organic and Inorganic Speciation Analyses," {Order No. PB 84-212 224; Cost:
$10.00, 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:
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
•ft U.S GOVERNMENT PRINTING OFFICE; 1984 — 759-015/7773
CO
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Penalty for Private Use $300
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