United States
Environmental Protection
Agency
Industrial Environmental
Research Laboratory
Research Triangle Park NC 27711
1
Research and Development
EPA-600/S7-84-056 June 1984
Project Summary
Comparative Analysis of
Contaminated Heating Oils
Robert R. Hall, RoseMary J. Ellersick, Marilyn Hoyt, Mary F. Kozik, and
Deborah F. McGrath
An exploratory investigation was
conducted of the possible contamina-
tion of virgin heating oils by hazardous
waste in the New Jersey/New York
area. Twenty oil samples, including
some that were suspected to be con-
taminated, were analyzed for 39 volatile
organic compounds. In addition, total
chlorine and water extractable chlorides
were measured in 13 samples. A statis-
tically valid sampling program was
developed to determine the extent of
heating oil contamination in New York
City.
This Project Summary was developed
by EPA's Industrial Environmental
Research Laboratory. Research Triangle
Park, NC. to announce key findings of
the research project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering
information at back).
Introduction
The report gives results of an investiga-
tion of the potential contamination of
virgin heating oil by hazardous waste.
Residual oils (No. 5 and 6) and No. 4 oil
are more likely to be contaminated than
light distillate oils (No. 1 and 2). The
heavier oils tend to mask contaminants,
and the contaminants may not create any
gross deterioration of burner performance.
New York and New Jersey account for
42.8 percent of U.S. deliveries of residual
and No. 4 heating oils to the commercial
sector (apartments, offices, general
retail, etc.). Much of this oil is used in the
winter heating season. In addition, the
northeastern New Jersey and New York
metropolitan areas are very densely
populated. The presence of major hazard-
ous waste generators in the area and
consideration of the above factors
indicate the potential for more severe
problems in the^New Jersey/New York
area than in most other areas.
A sampling strategy was developed to
determine, in a statistically valid manner,
the extent of heating oil contamination in
New York City. Because it was suspected
that only a few percent of the heating oil
may be contaminated and there were
more than 30,000 sites (heating units or
storage tanks), many samples would have
been required. Specifically, if the true
fraction of contaminated oil was 1
percent, there were 32,400 sites, and a
relative error of ±30 percent (a result of
1±0.3 percent) was acceptable, then
5,774 random samples would have been
required. The many samples required for
a statistically valid sampling program
precluded its implementation.
Therefore, program objectives were
redefined to conduct an exploratory
analytical program using samples that
had been previously collected by the
states of New Jersey and New York and
the city of New York. A primary objective
of the final program was to analyze a
collection of virgin oil samples for 39
selected volatile organic compounds. No
concentration data for these volatile
organic compounds in virgin oils were
available. A second, equally important,
objective was to investigate chlorine
speciation (organic vs. inorganic forms) in
selected virgin oil samples. Unexpectedly
high levels of chlorine had been recently
found in some samples, but no data were
available to indicate if the high chlorine
levels were caused by salts (possibly from
salt water) or contamination by chlorinated
organic compounds. In addition, analyses
of the samples for tojal bromine and
fluorine were planned.
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Results and Discussion
Twenty samples (13 virgin oils and 7
waste oils) were selected for analysis of
volatile organic compounds. Selection of
the samples was based on the type of oil
(No. 2, No. 4, No. 6, or waste), the source
(terminal, refinery, apartment house,
industry), the state or city where the
sample was collected (New York, New
Jersey, New York City), and preliminary
indications of contamination or noncon-
tamination.
Any general conclusions drawn from the
exploratory analyses of such a limited
collection of samples should only be
made with extreme caution. In addition,
some loss of volatile organic compounds
may have occurred between the time that
the samples were collected by the states
in the fall of 1982 and the analysis by
GCA in the spring of 1983. During this
period, the samples were opened and
analyzed under a separate program
conducted by EPA Region II. When
received at GCA, the sample containers
were typically less than 50 percent full.
In this study, "contamination" means
that the sample was found to contain at
least one compound at a relatively high
concentration compared to other oils of
the same type. It does not imply any
harmful environmental effect which
must depend on toxicity, the effects of
combustion, the extent of exposure, etc.
Similarly, statements that an oil is not
contaminated imply that it is similar to
other oils of the same type but not
necessarily that the normal components
of an uncontaminated oil are not harmful.
The ultimate impact of the volatile
organic compounds found in contaminated
and uncontaminated oil was not intended
to be assessed in this study.
Selected examples of volatile organic
compounds that were detected in the 13
virgin oil samples are presented in Table
1. Samples E, F, and N clearly appear to be
contaminated. These three samples
contain chlorinated organic compounds
that are not found in other samples while
sample E also contains relatively high
concentrations of benzene, ethylbenzene,
toluene and xylene. Note that samples E,
F, and N were supplied as samples that
were suspected to be contaminated.
Sample K shows some slight evidence of
contamination: it contains detectable
concentrations of methylene chloride and
1,1,1-tnchloroethane. Although Sample
B appears to contain unusually high
levels of ethylbenzene, toluene, and
xylene, the data base (consisting of only
two samples of No. 2 oil) is too small to
develop any firm conclusions.
Selected examples of volatile organic
compounds detected in the waste oil
samples are presented in Table 2. These
waste oil samples included automotive
and industrial wastes that are apparently
used as fuels. Some of the samples
contain percentage levels of chlorinated
organic compounds.
Thirteen of the 20 samples analyzed for
volatile organics were analyzed for total
bromine, fluorine, and chlorine, and
investigated for chlorine speciation. Total
bromine concentrations in all samples
were below the detection limit of 600
mg/kg. Except for two waste oil samples
which contained 96 and 182 mg/kg,
fluorine concentrations were below the
detection limit of 50 mg/kg.
The results of the halogen analyses are
summarized in Table 3. Many of the virgin
oil samples do contain inorganic chlorides
(water extractable chlorides), but these
do not appear to account for the total
chlorine. The unaccounted for chlorine
may be attributable to the precision of the
analytical methods, or some of these
samples may contain inorganic chlorides
that are not extractable, semivolatile
chlorinated compounds, or volatile chlori-
nated organics for which analyses were
not performed.
Conclusions
A small group of virgin fuel oil and
waste oil samples were analyzed for 39
selected volatile organic compounds,
chlorine, bromine, and fluorine. There
may have been significant loss of volatile
organic compounds prior to analysis by
GCA because the samples were opened,
partially analyzed under another project,
and not maintained at4°C in a headspace-
free condition. Many of the samples were
selected for analysis because they were
suspected or known to be contaminated.
The results provide examples of the types
of compounds and indications of the
Table 1, Selected Examples of Compounds Detected in Virgin Oil Samples, mg/kg"
Compound
Sample Identification ABODE F G H I J K L M N
Oil Grade 224 4 4 4 6 ' 6 6 6 6664
Oil Source Terminal Refinery terminal Terminal Terminal Terminal Terminal Terminal Terminal Terminal Terminal Refinery Refinery Apartment
Benzene
Ethylbenzene
Toluene
Xylene (isomersj
Methylene chloride
Tetrachloroethene
1. 1. 1 -tnchloroefhene
Trichloroethene
<20
24O
44O
590
<20
<20
<20
<20
no
970
910
4,100
<2
<2
<2
<2
46
160
230
110
<1
<1
<1
<1
45
120
110
79
<1
<1
<1
<1
590
2,500
7.900
7.9OO
10
14O
95O
40
14O
240
490 .
16O
180
14O
1.90O
26
23
94
87
67
<1
<1
<1
<1
<2
<2
<2
22
<2
<2
<2
<2
15
47
49
47
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Table 3. Summary of Halogen Results, mg/kg"
Compound
Sample Identification B C D £ H I J L M N O Q T
Oil Grade 2 4 4 4 6 66 66 4 Waste Waste Waste
Oil Source Rpfln*>rv Terminal Terminal Terminal Terminal Terminal terminal Refinery Refinery Apartment
TOJAL CHLORINE
Water extractable chloride
Chlorine detected in volatiles
TOTAL FLUORINE
Fluorine detected in volatiles
"Total bromine was below 600 mg/kg in all samples
<8
<2
<50
<2
99
44
81 1,360
20 187
<1 915
<50 <50
<7 '40
768
936
<2
<50
<2
149
101
<4
<50
<-09
81
44
<5
<50
<>
86
27
<7
<50
<'
74
44
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R. R. Hall, R. J. Ellersick, M. Hoyt. M. F. Kozik, and D. F. McGrath are with
GCA/Technology Division. Bedford. MA 01730.
Joseph A. McSorley is the EPA Project Officer (see below).
The complete report, entitled "Comparative Analysis of Contaminated Heating
Oils," (Order No. PB 84-190 990; Cost: $19.00, 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
U.S. GOVERNMENT PRINTING OFFICE, 1984 — 759-015/,7732
United States
Environmental Protection
Agency
Center for Environmental Research
Information
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Official Business
Penalty for Private Use $300
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