V-/EPA
United States
Environmental Protection
Agency
Municipal Environmental Research
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S2-81-045 Apr 1981
Project Summary
Automotive Crankcase Oil
Detection in a Coastal
Wetlands Environment
John T. Tanacredi
The marine environment has become
the primary disposal ground for an
increasing quantity of petroleum wastes.
Although a continuous, low-level
discharge of waste petroleum hydro-
carbons into the marine environment
may not be as dramatic as a major oil
spill, the consequences could be more
devastating over an extended period.
Continued addition of these hydrocar-
bons can only lead to a further deterio-
ration of this ecosystem. Tidal wetland
areas provide food and shelter for a
variety of indigenous and migratory
wildlife and thus provide critical sup-
port to marine food chains reaching all
the way to man.
The analytical results of this study
suggest that appreciable quantities of
hydrocarbons attributable to waste
automotive petroleum products are
present in treated wastewater efflu-
ents entering Jamaica Bay. The dis-
charge of petroleum hydrocarbons in
the effluent is chronic. Significant
quantities of detectable hydrocarbons
remain in solution in the surface waters
of the Bay while aromatic hydrocar-
bons from waste petroleum are found
in tissue extracts of marine benthic
organisms collected in the Bay.
This Project Summary was developed
by EPA's Municipal Environmental
Research Laboratory, Cincinnati, 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
Of the estimated 0.3 mil m3 (994 mil
gal) of automotive and industrial waste
petroleum purchased annually in the
New York metropolitan area, only 40%
is being reprocessed. The sources of
this petroleum in municipal wastewater
systems and their receiving waters
range from individuals who change the
oil in their automobiles and indiscrimi-
nately dump the wasted crankcase oil
into a nearby sewer to large establish-
ments that sporadically discard accu-
mulated stocks of waste oils. On many
occasions, especially during periods of
plant by-pass, large "oil slicks" pass
through water pollution control facilities
undetected and untreated.
This study attempted to determine:
1. whether waste automotive petro-
leum hydrocarbons are present in
the treated effluents discharged by
water pollution control facilities into
Jamaica Bay,
2. whether the quantity of petro-
leum-derived hydrocarbons present
in the Jamaica Bay waters is sufficient
to warrant immedicate attention,
3. whether a significant portion of
this waste petroleum persists in the
surface waters of the Bay and causes
a chronic exposure of the ecosystem
to petroleum derived hydrocarbons,
and
4. whether petroleum hydrocarbons
are being incorporated in biological
tissue of a Bay marine organism, Mya
arenaria.
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Methodology
Because of the complex chemistry of
the oil, each oil sample lends itself to
differentiation from others. This passive-
tagging approach establishes specific
qualitative parameters for oil samples in
the form of "fingerprints" that can be
compared with a "standard profile."
Thus, positive correlations for environ-
mental samples are either established
or not established with standards de-
pending on those portions of the petro-
chemical waste that exhibit themselves
in fingerprints and remain stable under
environmental conditions.
Jamaica Bay was chosen as the study
site because its unique hydrological
characteristics afford a long residence
time for treated or untreated effluents.
The sampling scheme involved final
effluent samples from the four major
water pollution control facilities emptying
into the Bay, surface water samples of
the Bay, and marine organism samples,
Mya arenaria Three analytical methods
were used for sample analyses: gas
chromatography, UV-spectroscopy, and
GC-MS.
GC retention times and relative peak
heights were used to identify petroleum
hydrocarbons in environmental samples.
A "spike" was added to samples after
noting the original samples'profiles and
retention times for resolved peaks.
Increases in peak heights of previously
noted sample components indicated its
presence in the sample extract.
For all fluorescence analyses, a UV-
fluorescence spectrophotometer with
two independent monochromators and
a constant temperature cell bath were
used. A fluorescence technique was
also used to excite each sample at
successive excitation wavelengths from
240 mu to 440 mu while scanning for
the maximum fluorescence emission.
Correlation was determined by visually
comparing the maxima profile plots of
known oil standards to the maxima
profile plots of environmental samples.
When these maxima profiles fit, in
addition to exhibiting the other qualitative
characteristics established by standards,
detection was established lor the partic-
ular sample.
A computerized GC/MS combination
with 1.52 M X 2 mm ID glass, packed
with3%OV-1 onaChromsorbWcolumn
was used. Only organism subfractions
were analyzed for specific petroleum-
derived aromatic compounds by this
method.
Results
To see if detection parameters estab-
lished for standard oils would be appre-
ciably affected by weathering, standard
oils were weathered in filtered' sea
water for 32 days. Profiles generated in-
dicated no significant changes in fluo-
rescence detection criteria even though
some profiles exhibited decreases in
intensity because of concentration factors.
Treated Wastewater Samples
Thirty-nine treated effluent samples
were analyzed for total CCUextractable
hydrocarbons (Table 1).
Surface Water Samples
Average background levels of petro-
leum hydrocarbons in oceanic water
have been established at approximately
2 Aig/L; greater than average or excessively
high levels ranged between 20 and 10
/ug/L. The values obtained for the
Jamaica Bay surface waters are signif-
icantly above normal background
oceanic levels of hydrocarbon concen-
trations (Table 2).
Organism Samples
Results of analyses clearly demon-
strate that the presence of petroleum-
derived hydrocarbons from Mya arenaria
tissue extracts are considered to be of
high pollution or contamination poten-
tial.
Discussion
Chromatograms generated by waste
automotive lubricating oil and refined
petroleum have been shown to be
characteristic and differentiable from
Chromatograms of other petroleum
entities. Once a waste oil enters the
environment, it seems that weathering
phenomena such as evaporation and
bacterial degradation will have little
effect on the less soluble aromatic and
higher molecular weight components.
Thus, detection parameters are pre-
served. The wide-boiling range, variety
of substituents separated, and unre-
solved envelope portions of Chromato-
grams indicate the presence of crank-
case oil, although they are not conclusive.
Though the specific sources of the de-
tected waste petroleum could not be
established, the accumulated evidence
from all analyses strongly indicates a
crankcase oil origin.
Gas Chromatograms of a pollution
control plant extracts did show a wide
range of hydrocarbon compounds above
Czo, a characteristic of lube oils. The
Chromatograms generated by organism
extracts strongly exhibited the presence
of aromatic compounds in body tissue.
Tentative GC/MS identification of or-
ganism subfractions indicated the pre-
sence of alkyl-substituted benzene
structures, which are highly toxic sub-
stances indicative of petroleum contam-
ination. UV-fluorescence analysisf ur-
nished dramatic evidence for the
presence of crankcase oil in environ-
mental samples and greatly strengthened
the other analytical results obtained.
Emission spectra of environmental
samples consistently demonstrated the
presence of polynuclear aromatics,
compounds that could only be attribut-
able to petroleum pollution.
Tablet. IR
Water Pollution
Plant
Coney Island
26th Ward
Jamaica
Rockaway
Quantification of Total Extractable Hydrocarbons from Treated Effluents3 '
9-10
1.50
29.7
9-15
16.4
20.0
10.7
9-17
7.1
34.9
12.0"
4.9
9-24
2.0
28. 3b
7.2
1.3
9-29
3.5
22.9
5.3
4.7
Date
10-1
15.6
12.3
4.7
0.5
10-8
3.0
19.2
9.6
W.Qf
10-15
39. 8*
19.1
4.6
13.8
10-22
10.5
9.3
9.4
8.5
10-29
416
14.2
7.7
11-5
8.6
18.8
3.2
*AII values in mg/1.
hGas chromatographic analysis.
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The results presented give a strong
indication that hydrocarbons that are
discharged with treated wastewater
into Jamaica Bay and that ultimately
accumulate in biological tissue are of a
waste automative petroleum origin.
Table 2. Jamaica Bay Surface Water
Total Extractable Hydro-
carbons'1
Sample
Site
NYN16
NYN09A
NYJ01
NYJ02
NYJ03
NYJ05
NYJ07
11-7
0.94
1.20
2.10
1.17
3.10
0.50
1.08
1-8
1.13
0.88
2.16
2.20
5.10
1.50
1.40
John T. Tanacredi is with the Department of Environmental Health Sciences,
Hunter College of the City University of New York, New York, NY 10029.
Uwe Frank is the EPA Project Officer (see below).
The complete report, entitled "Automotive Crankcase Oil: Detection in a Coastal
Wetlands Environment," (Order No. PB 81-171 662; Cost: $9.50, 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:
Oil & Hazardous Materials Spills Branch
Municipal Environmental Research Laboratory—Cincinnati
U.S. Environmental Protection Agency
Edison, NJ 08837
*AII values in mg/L
a US GOVERNMENT PRINTING OFFICE. 1861 -757-012/7085
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