EP/W500/-.4-
March 1981
AUTOMOTIVE CRANKCASE OIL:
DETECTION IN A COASTAL WETLANDS ENVIRONMENT
by
John T. Tanacredi
Department of Environmental Health Sciences
Hunter College of the City University of New York
New York, New York 10029
and
Dennis Stainken
Oil & Hazardous Materials Spills Branch
Industrial Environmental.Research Laboratory
U.S. Environmental Protection Agency
Edison, New Jersey 08817
Project Officer
Uwe Frank
Oil, & Hazardous Materials Spills Branch
Soli.d; & Hazardous Was-te Research "ftivi si6*n
Municipal En'vi'ronmental Research Laboratory-Cincinnati
Ed'is^n, N.ew Jersey 088.37 '.
This study was conducted in cooperation with the
.Department of inviroraienta1.Health ServtcSS.
Hunter College;-of th;e Ci ty"Uh.fvefsT ty of New.' York
••'"' lew; yisrk:, :NewYor 1(^10029 •' -;'
MUNICI.PAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE'" OF •^SEARCH AND DEVELOPMENT
U.'S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 4526S
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DISCLAIMER
This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
11
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FOREWORD
The U.S. Environmental Protection Agency was created because of increas-
ing public and government concern about the dangers of pollution to the health
and welfare of the American people. Noxious, air, foul water, and spoiled land
are tragic testimonies to the deterioration of our natural environment. The
complexity of that environment and the interplay of its components require a
concentrated and integrated attack on the problem.
When energy and material resources are extracted, processed, converted,
and.used, the related pollutional impacts on our environment and even on our
health often require that new and increasingly more efficient pollution con-
trol methods be used. The Municipal Environmental Research Laboratory-
Cincinnati (MERL-Ci) assists in developing and demonstrating new and improved
methodologies that will meet these needs both efficiently and economically.
This report is a product of the above efforts. It identifies the pre-
sence of waste automotive petroleum hydrocarbons in the treated wastewater
effluents of water pollution control facilities (WPCF's) which discharge into
Jamaica Bay, New York. It also identifies and quantitates petroleum derived
benthic organisms (bivalves). This report further documents the application
of a novel technique using fluorescence spectroscopy for identification of
waste automotive petroleum hydrocarbons in effluents. This report will be
of interest to those individuals involved in routine monitoring of the envi-
ronment, damage assessment, law enforcement, and industrial wastewater re-
search. Further information about this report is available from the Oil and
Hazardous Materials Spills Branch, MERL-Ci, Edison, New Jersey 98817.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
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ABSTRACT
Samples from four sewage treatment facilities which discharge into
Jamaica Bay, New York, were analyzed for the presence of waste automotive oil
products. UV-fluorescence spectroscopic techniques were utilized to qualita-
tively identify waste petroleum hydrocarbons in effluents of water pollution
control plants by comparison of sample profiles to profiles generated by
standard reference oils. Within the Bay, surface waters and a benthic bi-
valve (Mya arenaria L.) were also analyzed for petroleum hydrocarbons using
fluorescence techniques, and gas chromatography. GC-Massspectroscopy was
used to further aid in establishing the presence of petroleum hydrocarbons in
the bivalves. Synchronized excitation fluorescence spectroscopy was used in
this investigation to confirm the presence of waste automobile oil in the
environmental samples. Results strongly indicated the presence of hydrocar-
bons associated with waste automotive petroleum products in most of the ex-
tracts of effluent samples, surface water samples and bivalves.
This work covers the period September 1973 to April 197*», and was com-
pleted in May 197^. Professor Tanacredi is Adjunct Assistant Professor of
Human Ecology at the Institute of Health Sciences, Department of Environmen-
tal Health Science, Hunter College, City University of New York. At the time
of this project, PrSfessor Tanacredi was on a Department of Health, Education
and Welfare Fellowship Grant. Project support in part was provided by U.S.
Environmental Protection Agency-Edison, New Jersey and Hunter College, C.U.N.Y.
IV
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CONTENTS
Foreward i i i
Abstract • iv
Figures • • vi
Tables ...viii
Abbreviations and Symbols , ix
Acknowledgments. . .• x
1. Introduction 1
2. Conclusions and Recommendations 3
3. Primer on Petroleum Chemistry k
k. Project Approach.. 5
5. Study Area 7
6. Sampling Scheme 10
7. Procedures for Sample Extract Preparation 14
Sewage treatment plant effluents.. 14
Jamaica Bay surface waters 15
Estuarine organism (Mya arenaria) 16
8. Analysis of Sample Extracts 20
Gas chromatography 20
UV-fluorescence spectroscopy , 25
GC-mass spectroscopy as an ancilliary method 30
9. Resu Its ... 35
10. Discussion 53
References 57
Append i ces 65
A. Gas chromatography and UV-fluorescence spectroscopy
background and theory 65
B. Gas chromatograms of petroleum products 72
C. GC-MS data for Hya arenaria L. extracts 75
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FIGURES
Number Page
1 Geographical map of Jamaica Bay 8
2 Drainage areas of water pollution control facilities emptying
into Jamaica Bay 9
3 Surface water sampling sites in Jamaica Bay..... 12
k Benthic organism sampling sites in Jamaica Bay 13
5 Infrared oil absorbance band 16
6 Outline for extraction of petroleum hydrocarbons from
estuarine benthic organisms 17
7 Flow diagram for extraction and analysis of organism
subf ractions 19
8 Gas chromatographic profiles of reference standard oils... 21
9 Weathered waste crankcase oil reference standard 2k
10 Fluorescence emission spectra for waste crankcase oil
reference standard..... 26
11 Fluorescence maxima profile for waste crankcase oil
reference standard 27
12 Maxima profile plots refined and crude oil reference standards.... 28
13 Fluorescence maxima profile fit for environmental samples......... 29
14 Fluorescence emission spectra reference standard sample oils. 31
15 Fluorescence emission "correlation" spectra 32
16 Schematic of UV-fluorescence analysis procedure, 33
17 Gas chromatogram of sewage effluent extract 37
18 Fluorescence maxima profiles for weathered and unweathered
fuel oil reference standards 40
VI
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19 Fluorescence maxima profiles for weathered and unweathered
crude oil reference standards
20 Fluorescence maxima profiles of WPCF effluents
21 Gas chromatograms of surface water extracts from Jamaica Bay.
22 Correlation of emission spectra - surface waters and
weathered reference standards
23 Fluorescence maxima profiles for bay surface water 46
2k Mya II subfraction gas chromatograms 50
25 Mya III subfraction gas chromatograms 51
26 Fluorescence maxima profiles for organism extracts 52
VI I
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TABLES
Number Page
1 Homologous Series for Petroleum Products 4
2 Petroleum Products Utilized as "Reference Standards". - 6
3 Daily Flows from WPCF 10
4 Location of Surface Samples Taken in Jamaica Bay..... 13
5 IR Quantification of Total Extractable Hydrocarbons from WPCF 36
6 "Oils and Grease" Hexane Extractable Material Recorded by
New York City Bureau of Water Resources, Wards Island 36
7 Fluorescence Correlation Data - WPCF Extract 38
8 Jamaica Bay Surface Water Total Extractable Hydrocarbons kk
9 Fluorescence Correlation Data - Surface Water Samples kk
10 High Pollution Potential Organism Extract Results ^8
11 Low Pollution Potential Organism Extract Results... ^8
12 Fluorescence Correlation Data - Mya arenaria Extracts. *»9
VII I
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ABBREVIATIONS AND SYMBOLS
WPCF —Water Pollution Control Facilities
SCOT —support coated open tubular column
ID —inside diameter
WCCO —waste crankcase oil
PNA —polynuclear aromatics
UEP —unresolved envelope portion
ul —microliter
GC-MS —gas chromatography-mass spectroscopy
FMP —Fluorescence Maxima Profile
CCLr —carbon tetrachloride
HPP —high pollution potential
LPP —low pollution potential
HEM —hexane extractable materials
IX
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ACKNOWLEDGMENTS
The continued cooperation through discussions, and critical review pro-
vided by Mr. Jack Foehrenbach, Chief Analytical Chemist, New York State
Department of Environmental Conservation, Dr. M..Alavanja, Department of
Environmental Health Sciences, Hunter College, City University of New York,
and Mr. F. Rubel, U.S. Coast Guard, Marine Environmental Protection Branch,
from conception to final completion of this project is deeply appreciated
and hereby acknowledged. This report has been edited by Dr. Dennis M.
Stainken with explicit recommendations and conclusions being added.
The specialized assistance afforded me throughout this study by Mr. M.
Gruenfeld, Mr. U. Frank of the Municipal Environmental Research Laboratory,
U.S. Environmental Protection Agency, and Dr. B. Dudenbostel of the Surveil-
lance and Analysis Division, Region II, U.S. EPA, Edison, New Jersey was
instrumental in the successful completion of this project.
The weekly collection of the final effluents from the major Water
Pollution Control Facilities emptying into Jamaica Bay could not have been
possible without the cooperation of the Bureau of Water Resources, City of
New York and its then commissioner, Mr. Martin Lang.
Finally, I would like to acknowledge the consistent aid and support
provided by Dr. George J. Kupchik, Program Director of the Department of
Environmental Health Sciences, Hunter College of the City University of New
York, whose insight into the relevancy of this project made it possible.
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SECTION 1
INTRODUCTION
Recent years have shown our aquatic ecosystem to be an invariable dis-
posal ground for an ever increasing number of waste products. Among this
perplexing myriad of disposables is a considerable quantity of waste petro-
leum. As the world demand for petroleum products mushrooms each year, the
probability of greater concentrations of specific hazardous materials such
as petroleum derived hydrocarbons entering the aquatic environment will
increase.
Even though petroleum products are subject to varied degrees of environ-
mental degradative processes such as wind, wave and bacterial action, their
continued disposal into the marine ecosystem makes it imperative..to consider
them in the same context as heavy metals and pesticides. Blumer had noted
that early interpretations and investigations of the environmental effects
of oil pollutants were based on subjective observations over relatively
short periods of time. These data may now have questionable validity since
it has been demonstrated that these oil products are persistent poisons
resembling in their longevity DOT, PCB's and other synthetic materials. The
environmental persistance of these petroleum hydrocarbons has been well
demonstrated . Petroleum hydrocarbons have persisted in offshore sediments
years after significant quantities of fuel oil was spilled. Specific hydro-
carbon incorporation in tissue has been exhibited"* in everything from the
basking shark to species of marine algae.
g
According to U.S. Department of Commerce figures , sales of new oils in
the United States total about 2.5 billion gallons annually of which half goes
to use inqthe automotive industry. The American Petroleum Institute has
estimated that 68% of the automotive lubricating oils uti1ized.leaves car
engines as waste. Of this 850 million gallons, it is estimated that 200
to 400 million gallons is recycled annually, with only 100 million gallons
actually being re-refined. Thus, between 450 and 650 million gallons of
waste crankcase oil (WCCO) is subject to man's re-use or mis-use.
It has been estimated that a substantial quantity of waste petroleum
products, approaching 1,400 million gallons per year, is being lost to the
environment, of which a substantial quantity is being Indescriminately
dumped into our nation's municipal sewerage systems and their receiving
waters. The origin of this oil can be from a variety of sources ranging
from industrial wastes to the individual who changes the oil in his automo-
bile and dumps the wasted crankcase oil into a nearby sewer. Apartment
houses dumping tank bottom wastes from spent home heating fuels, garages,
gas stations, bus depots, truck terminals, railroad yards and marinas whose
vessels all require regular changes of lubricating oils, all generate
1
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substantial quantities of waste oils.
Assuming that a significant quantity of this waste oil is being dis-
carded into municipal sewerage systems of New York City, existing wastewater
treatment technology will not prevent a major portion of this waste petro-
leum from getting into a receiving body of water. This assumption is based
upon the facts that (a) most hydrocarbons are more resistant to-degradation
processes than other organic compounds commonly found in sewage , and (b)
hydrocarbons are only removed by skimming and settling operations which
disregard that portion of waste oil which is finely dispersed . The
effects of exposure to various.petroleum hydrocarbons on a variety of marine
organisms are well documented
Only about kQ% of the estimated 9^ million gallons of automotive and
industrial waste petroleum recorded annually in the New York City metropol-
itan area is being resorocessed; approximately 25 million gallons are actu-
ally being re-refined . Now more than ever, with the continuing energy
dilemma, it seems imperative to consider this waste not only as a potential
detriment to the marine environment but also as a potential energy source.
The analytical methods available for the identifIcatioQ.aqd detection
of oil products in the environment are varied and extensive . However,
no single method of analysis is a confirmation for the identification of a
specific waste petroleum pollutant. Any or all of the methods utilized in
this project may be considered as confirmative evidence for the detection
of petroleum hydrocarbons. Specific pollutant identification can only be
considered in the light of a multi-parameter approach . Accumulation of
as convincing a group of evidence as is possible, aids in pinpointing the
origin of these waste petroleum products. For these reasons UV-fluorescence
spectroscopy and gas chromatography are to be the principal analytical tools
utilized for the detection of waste automotive petroleum products in envi-
ronmental samples. Mass spectroscopy will be utilized for the identifica-
tion of some specific petroleum derived hydrocarbons in biological tissue
of a marine bivalve.
The objective of this study was to determine whether automotive petro-
leum derived hydrocarbons were present in the wastewater final effluents
emitted by water pollution control facilities discharging into Jamaica Bay,
New York.
With the detection of a chronic addition of relatively low levels of
waste petroleum hydrocarbons into the environment, the study examined (by
identification and quantitation) whether these petroleum derived hydrocar-
bons disseminated through the Bay ecosystem. In addition, the petroleum
derived hydrocarbon contents of the surface waters and the tissues of an
intertidal bivalve (Mya arenaria L.) were analyzed.
Immediate effects of continuous additions into a marine ecosystem may
not be as dramatic as a major oil spill, however, the final outcome could be
more significant over an extended period of time and in the proper ecologi-
cal conditions.
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SECTION 2
CONCLUSIONS
The results of this study strongly suggest that appreciable quantities
of hydrocarbons attributable to waste automotive crankcase oil were detected
in treated wastewater effluents entering Jamaica Bay, New York.
The weekly occurrence of detectable quantities of petroleum hydrocarbons
in WPCF effluents suggests that the discharge of these hydrocarbons should be
considered as a chronic input of petroleum waste products into Jamaica Bay.
Significant quantities of detectable petroleum derived hydrocarbons are
remaining in solution in the near-surface waters of the Bay.
Compounds isolated from tissue extracts of marine benthic organisms
collected in the Bay appear to be attributable to the aromatic hydrocarbon
portion of automotive petroleum products.
A continuing monitoring system for wastewaters within the New York met-
ropolitan area should be established addressing petroleum derived hydrocar-
bons.
Increased efforts should be made to monitor levels of toxic hydrocarbons,
particularly polynuclear aromatic compounds, in the Jamaica Bay ecosystem.
Critical areas of the Bay sediments, water and key fauna should be analyzed
to determine whether food web transfer, bioconcentration, or hazards to
human health exist.
Research to identify and quantitate specific petroleum derived compounds,
their sources and fate in the environment and biota should be conducted. This
data should be compiled and a hydrocarbon modeling system should be estab-
lished.
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SECTION 3
PRIMER ON PETROLEUM CHEMISTRY
Products derived from crude petroleum are complex organic hydrocarbon
compounds. Table 1 shows the more important of the simpler series for fuels
and lubricants. The compounds in a homologous series have similar chemical
properties, and there is a gradual change in physical properties as the
molecular weight increases. The alkanes contain single bonds only, and
straight chain alkanes are called n-paraffins. Additions of substituent
groups, or the branching of side chains, results in a complex arrangement of
isomeric compounds. In general, the boiling points and densities for the
branched chain isomers are lower than the values for the corresponding normal
isomer . The highly branched paraffins are desirable components in some
petroleum products^". High molecular weight normal paraffins are provided
in lubricating oils so as to maintain a better viscosity state, while the
extremely high molecular weight n-paraffins above C^Q are usually removed in
dewaxing processes. The complex mixture of cycloparaffinic and aromatic com-
pounds (mono and polyalkylated benzenes and polynuclear aromatics) with sub-
stituted and unsubstituted ring structures, are fundmentally found in petro-
leum products^S. The olefinic compounds are present in most refinery pro-
ducts such as the automotive lubricating oilsBO.
TABLE 1. HOMOLOGOUS SERIES FOR PETROLEUM PRODUCTS
Name
Alkanes (paraffins)
Alkenes (olefins)
Cycloalkanes, cycloparaff ins
(naphthenes)
Cyclo-olef ins
Aromatics
Carbon formula
CnH2n+2
CnH2n
CnH2n
CnH2n-2
C H. ,
n 2n-6
Characteristics -
Open chain, saturated
Open chain, one double
bond
Cyclic, saturated
Cyclic, one double bond
Single or multiple ring
structures
Thus, the principle aspect of petroleum chemistry is its complexity of
composition, upon which unique detection parameters are based. It is due to
this complexity that no two petroleum entities will exhibit identical identi-
fication characteristics thus aiding in their detection in the environment.
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SECTION k
PROJECT APPROACH
Any multiparameter oil pollution identification scheme will involve
three basic tasks: (1) the collection of and preparation from a suspected
polluted sample, a representative of a previously established standard;
(2) measurement of specific identification parameters (qualitative or quanti-
tive) on the sample; (3) and the comparison of the measured parameters with
standards. As the state-of-the-art in oil pollutant analysis exists today,
"active" or "passive" identification techniques encompass these tasks as the
two basic approaches which may be utilized when one is concerned with the
detection of petroleum wastes in the environment. An "active" tagging
approach requires the addition of specific chemicals to standard oils. Once
these petroleum products permeate the marine environment, one differentiates
between the suspected origins of the oils by looking for these "tags".
These "chemical tags" are usually unaffected by weathering and will readily
lend themselves to analysis.
Petroleum products can only be described in general terms because they
are such a complex mixture of various hydrocarbons, and a wide range of in-
organic and organic compounds. Whitehead and Breger31 point out that in the
complex structure of a lubricating oil "the compounds may be composed of a
mixture of aromatic, cycloparaffinic and paraffinic structures, whose number
of possible combinations becomes almost infinitely large..." It has been
estimated32 that within some refined petroleum products such as the automo-
tive lubricating oils, some hydrocarbons have molecular weights which reach
as high as 6,000. A refined petroleum product is the end result of various
purification and blending processes. To obtain the properties desired in
automotive oils, refineries use as a starting material specific fractions
from crude oils. Even with the desired fraction from the original crude,
many automotive lubricating oils demand specific, high boiling point, high
molecular weight additives. These long chain polymeric compounds aid in
maintaining a proper viscosity-state when these oils are subjected to the
wide temperature ranges today's various means of transportation may experi-
ence. The addition of "active" tags to various petroleum products in some
instances may have definite advantages, as is the case if the origin of the
oil is known prior to analysis of the polluted sample. However, when one
considers all the possible individual sources of waste automotive lubricating
oils, one realizes that such an approach would be impractical. One must also
consider the fact that little is known concerning the effects of weathering
of these chemical tags33, or for that matter what effect subsequent by-pro-
ducts could have on the environment.
Regardless of all the refining processes and tagging problems, petroleum
products are unique enough to lend themselves to differentiation from other
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petrochemical entities by utilization of a "passive" tagging approach. This
passive detection technique utilizes the inherent chemistry of the oil it-
self. For instance, the qualitative parameters established for instrumental
analyses generate a fingerprint or profile of a WCCO. These fingerprints are
such that upon observing them one may clearly differentiate the WCCO from
other petroleum materials such as crude or fuel oil. Analysis of off-the-
shelf petroleum products, a used crankcase oil and weathered oils will serve
as "reference standards" to compare with environmental sample extracts (Table
2). Those particular portions of the standard fingerprints which remain
stable under environmental conditions will serve as the parameters for in-
strument analysis. For example, WCCO has been characterized3^ by large
quantities of 4- and 5-ring polynuclear aromatic (PNA) compounds. This is
one reason why WCCO has been established35 as one of the major contributors
(450,000 metric tons per year) of hydrocarbons to our ocean waters. Evidence
indicates36 that compounds with carbon numbers of 20 or greater may act as
tags due to the fact that more volatile paraffins (C^g or below) readily
weather by evaporation. The effect of weathering on the PNA portion of
specific fuel oils under simulated, yet vigorous temperature conditions,
indicated no significant changes in the fingerprinting scheme for the C^Q
to C^fc compounds^?. Therefore, by the use of a passive - tagging approach to
detec't such unique petroleum hydrocarbon constituents as PNA's or specific
paraffinic compounds which do not occur naturally in the marine environment,
one can demonstrate their presence in sample extracts through the generation
of characteristic analytical profiles.
TABLE 2. PETROLEUM PRODUCTS UTILIZED AS "REFERENCE STANDARDS"
Refined petroleum products
1. Warco Dexron Automotive Transmission Fluid
2. Fox Head Multi-Grade SAE 10W/30 Motor 051
3. Castrol XLR SAE 20W/50 Motor Oil
Waste crankcase motor oil
1. WCCO from 1966 Buick; 6,000 miles
Fuel
Curde
oil
1.
2.
3.
oi
1.
2.
3.
k.
5.
sa
No. 2 Fuel Oil
No. k Fuel Oi 1
No. 5 Fuel Oil
Is (See Appendix
South Louisiana
Bachaquero Crude
Kuwait Crude Oil
Nigerian Medium
Skidka Crude Oil
B for
Crude
Oil
Crude
chromatrograms)
Oil
These oils were On-Hand reference standards supplied and utilized for
analyses by the Industrial Waste Treatment Research Laboratory, Edison,
New Jersey, a division of the Environmental Protection Agency's National
Environmental Research Center.
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SECTION 5
STUDY AREA
Geographically, Jamaica Bay is approximately six miles long and four
miles wide and receives relatively little fresh water input. There are no
major rivers or streams which empty into the bay, and the major source of
fresh water (besides precipitation and run off) is derived from the water
pollution control facilities (WPCF) emptying into it^ . The Bay's only
connection with the sea is at the Rockaway Inlet (Figure 1).
Jamaica Bay and its drainage area amounts to approximately 52,000 acres
and serves an estimated population of over 1,600,000.39. Within the Bay pro-
per, there are a number of inlets which receive the bulk of the combined
sewer overflow discharges after periods of precipitation, and a portion of
the waste discharges from water pollution control facilities. The final
effluents from some plants enter the Bay at specific outfall sites (Figure 2),
Those inlets which still drain marshland are confined to the central portion
of the Bay within the Jamaica Bay Wildlife Refuge,
Jamaica Bay is an ideal location for this particular study. The Bay's
hydrology affords a long residence time for the treated or untreated efflu-
ents pouring into it. The daily tidal fluctuations (semi-diurnal with a
period of 12.4 hours) involve approximately 31% of the total volume of the
Bay^*0, which should indicate a great deal of mixing and flushing occurring
with such a water exchange. This is true of the Bay waters in that suffi-
cient turbulance exists to create extensive mixing and prevention of strati-
fication. The net exchange of Bay water with ocean water during a tidal
cycle is relatively small. It has been estimated that the net daily flow
out of the Bay from all peripheral inputs is equivalent to an estimated 1% of
the volume of the Bay, whereas the diurnal tidal flux is approximately fifty
times greater than this value. Nearly all the waters entering the Bay on
flood tides are carried by the peripheral channels. On ebb tides, an equiv-
alent quantity of water moves back through the channels and into Rockaway
Inlet.
Samples were not collected from the waters in the back of Grassy Bay,
since such samples may contain oil pollutants attributable to the JFK airport
operations. Jet fuels and other aviation lubricants however, should not
affect established detection parameters for waste automotive lubricating oils.
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oo
JFK- TNTCRNATlOflAL
'O
* ^ X
» \^~S
Figure 1. Geographical map of Jamaica Bay.
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Figure 2. Jamaica Bay Water Pollution Control Faci1ities.(WPCF)
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SECTION 6
SAMPLING SCHEME
The sampling operation consisted of three phases. The first phase in-
volved the collection, on a weekly basis, of the final effluents of the major
water pollution control facilities (WPCF) emptying into Jamaica Bay. Table 3
provides the total daily flows from all the plants pumping wastewater into th
Bay during the period of this project along with their points of discharge^.
TABLE 3. DAILY FLOWS FROM WPCF
Facility Flow (mgd)* Point of discharge
NEW YORK CITY
Coney Island
26th Ward
Jamaica
Rockaway
Total :
(1972 - 73)
77
53
76
16
222
Rockaway Inlet
Hendrix Creek
Grassy Bay
South Channel
MILITARY INSTALLATIONS
Floyd Bennett Field 0.3
Fort Tilden 0.3
NASSAU COUNTY
Inwood 1.3
Cedarhurst 1.0
* 1977-1978 capacities total 360 mgd for NYC facilities.
From this table it can be observed that a relatively small quantity of
treated effluents entering Jamaica Bay is derived from water pollution control
facilities other than NYC plants. The WPCF's sampled were the Coney Island
Plant located at Avenue Z and Knapp Street; the 26th Ward Plant located off
Pennsylvania Avenue; the Jamaica Plant at the southwest corner of JFK Inter-
national Airport; and the Rockaway Water Pollution Plant located along Beach
Channel Drive in Rockaway Beach.
A combined sewer collection and treatment system such as we have in New
York City is usually incapable of handling hydraulic loadings caused by storm
generated flows. In many instances to avoid upsetting conventional treatment
plant operations, such peak flows will be by-passed directly into a receiving
body of water untreated. It was -felt tha^t aftjersa: particular storm.
period, a special effluent sample would be taken as representative of
10
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the combined sewer overflows as well as representative of a high potential oil
content. Waste crankcase oil (WCCO) that has been dumped into a municipal
sewer would remain within the system until rain waters caused this accummula-
tion to be washed-out with overflows. In many instances large stocks of waste
petroleum will be dumped sporadically by larger establishments. These larger
quantities of waste oils have been observed by WPCF personnel as large "oil-
slicks" or as "globules" which will usually go through WPCF's undetected and
for the most part untreated . On the average, secondary treatment, that is
skimming of surface layers and settling-out solid particles upon.which oil
adheres, will remove 48 to 96 per cent of the total hydrocarbons . Thus,
even under normal situations, after some treatment, an average of 10 to 50
per cent of the total hydrocarbons found in sewage will be passed into a
receiving body of water.
Ideally, once a treatment plant experiences a hydraulic rise in flow
after a period of precipitation, a special sample should be taken as repre-
sentative of an elevated level of waste petroleum products in the combined
sewer overflow. Special sample collection without the serious interruption
of normal plant operations, was unattainable for this project. The possibil-
ity of contamination was high for the special samples due to a regular turn-
over of individuals responsible for its collection. It was determined .how-
ever, by the consistency of detectable oil pollutants found in the treated
effluents, that for this project there was no need for such an integrated
sampling scheme. Any subsequent quantitative work concerned with oil in
wastewater effluents will require an extensive automatic sampling system for
the precision monitoring of stormsewer overflows.
The second phase of the sampling scheme required the assistance of the
Environmental Protection Agency's research vessel Clean Waters to take sur-
face-water samples. Seven sites were selected; five within the Bay, one
within the Rockaway Inlet and one off Breezy Point in the Atlantic Ocean
(Figure 3). Two of these sites were regularly monitored by New York City's
Bureau of Water Resources during the same months, while the other five sites
had been previously sampled by the Federal Environmental Protection Agency's
Region II, Surveillance and Analysis Division, located in Edison, New Jersey
(Table 4). Samples were taken at a depth of 2 feet below the surface with a
Kemmerer grab water sampler at all seven sites. Water samples were placed in
980 ml wide-mouth, glass Mason jars with teflon-lined caps. Since no refrig-
eration space was available for the samples aboard the ship, 5 ml of 1:1 con-
centration sulfuric acid and 20 ml carbon tetrachloride (CCL^) were added to
each sample collection so as to retard bacterial degradation of hydrocarbons.
Samples were kept in ice until returned to laboratories where they were
immediately refrigerated until extraction and analysis. The time period
between collection of samples and extraction never exceeded A8 hours.
The third and final phase of the sampling operation required the collec-
tion of an estuarine benthic organism, Hya arenaria L., at sites felt to be
representatives of (a) a high pollution potentialTHPP) and, (b) a low pollu-
tion (LPP) for waste automotive petroleum wastes. It would be ideal to have
access, for control purpose in this project, organisms reared in an environ-
ment free from contamination. However, when dealing with marine organisms
directly from the ocean or coastal environment, especially from an estuarine
11
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Figure 3. Surface-water sampling sites in Jamaica Bay.
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TABLE 4. LOCATION OF SURFACE SAMPLES TAKEN IN JAMAICA BAY
Sample station
Latitude
Long!tude
Approximate site
NYN16
NYN09A
NYJ01*
NYJ02*
NYJ03*
NYJ05*
NYJ07*
40.31.44
40.33.^3
40.34.22
40.36.27
40.37.33
40.35.45
40.38.43
73.56.45
73.56.45
73.53.05
73.53.11
73.53.03
73.48.41
73.49.16
Atlantic Ocean
Off Rockaway Point
Marine Parkway Bridge
Floyd Bennett Field
Canarsie Pier
IND Train Tressel
Broad Channel
entered as EPA stations; latitude and longitude from EPA directory print-
out.
45
area, there is no certainty of freedom from petrochemical contamination .
Figure 4 indicates locations of organism samples collected in October (Mya I)
and in December (Mya II and Mya III). At each site a total of 15 clams,
ranging in size from 1.0 to 4.0 cm were collected and placed in a glass de-
canter. The clams were shucked within one hour after collection and allowed
to drain so that only body tissue and internal fluids would be used for ex-
traction purposes. Each sample was placed in aluminum foil and immediately
frozen until extraction and analysis.
Figure 4. Benthic organism sampling sites in Jamaica Bay.
13
-------
SECTION 7
PROCEDURES FOR SAMPLE PREPARATION
SEWAGE TREATMENT PLANT EFFLUENTS
The quantity of extractable hydrocarbons in each final effluent sample
was determined by utilizing an infrared (IR) method for the quantification
of total hydrocarbons^".
The samples were collected from the final contact tanks of each of the
WPCF's sampled. Samples were taken in 980 ml, wide-mouth, glass bottles,
each with a teflon-lined cap. The bottles were washed with a detergent (Sur-
gical Instrument and Laboratory Glassware Detergent, Octagon Process Inc.,
Edgewater, N.J.) which has been reported**? not to have any interfering resi-
due on inner-glass surfaces. Each bottle was oven-dried at 120°C to ensure
removal of any possible contaminants. The extent of contamination was deter-
mined by solvent washing bottles with 50 ml of carbon tetrachloride (CCL^)
and measuring solvent absorbance by IR in 10 mm cells. In all instances the
resulting absorbance was negligible, and m no case did the absorbance exceed
0.01. Each sewage treatment facility received a sampling procedure. All
samples from WPCF's were taken at 2:00 PM by plant personnel. All samples
were refrigerated throughout the storage and transfer period prior to analy-
sis. Five mil Iiliters of 1:1 h^SO^ was added to each sample directly after
pick-up at each plant to retard bacterial degradation of hydrocarbons.
Laboratory Procedure
The following procedure was carried out on each of the sewage effluent
samples:
(1) Quantitatively transfer sample to a 2 liter separatory funnel.
(2) Rinse sample bottle with 25 ml of CCL^ and add to separatory funnel.
(3) Add 5 g sodium chloride and allow time for its going into solution.
(k) Shake vigorously for one minute and allow 5-10 minutes for the
phases to separate. (Usually a water/CCL^ emulsion occurs, so that
good separation should be attained before drainage of solvent layer.
Try to prevent water from getting into tared beaker during sample
extract collection.)
(5) Check for acidity; sample acidity should be below pH3. If necessary
adjust pH to 3 by addition of 1:1 solution of sulfuric acid.
-------
(6) Prepare a one inch layer of anhydrous sodium sulfate over a small
washed glass wool plug in a long stem funnel.
(7) Drain the lower phase from the separatory funnel through the sodium
sulfate into a tared 100 ml beaker. Avoid draining upper aqueous
layer.
(8) Perform three additional extractions with 25 ml portions of solvent
using each portion to rinse the sample bottle. Allow the phases to
separate and drain each bottom phase through sodium sulfate into a
100 ml beaker. Bring to volume with CCL^. This is the SAMPLE
EXTRACT (As).
(9) Scan the SAMPLE EXTRACT in the range 3200 cm"1 to 2600 cm"1 with an
IR spectrophotometer, using CCL^ in the reference beam. Select the
appropriate path length cells (in this case 10mm cells) to obtain
maximum_absorbance NOT exceeding 0.9. Measure oil absorbance at
2930 cm" as the difference between the absorption band maximum and
a "base-line" drawn tangent to the band minimum (see Figure 5).
(10) After the measurement, return the extract having UNKNOWN identity
to the original 100 ml beaker.
(11) "Jet-air" evaporate off the solvent from the SAMPLE EXTRACT using
a cool air stream ONLY, to dryness. Keep jet stream low to prevent
possible aerosol formation. Perform this operation in a well venti-
lated hood. When no solvent remains record residue's weight in
milligrams (Cr).
(12) Bring residue to volume (100 ml CCL^). This becomes the SIMULATED
STANDARD SOLUTION (Ar) for the oil with unknown identity. Run IR
as with SAMPLE EXTRACT.
(13) DISPERSED OIL IN WATER (mg/1 ) = Cr x As/Ar.
(14) Jet-air evaporate off the CCL^ to dryness and bring residue up one
or two ml (depending upon concentrations) with hexahes and run gas
chromatographic analysis.
(15) Bring to 50 ml volume in hexane and run UV-f luorescence analysis.
SURFACE WATERS OF JAMAICA BAY
With small quantities of total extractable hydrocarbons (organics) in
sea water, slight modifications in the procedure were required. For example,
10 cm (path length) IR cells were utilized so as to obtain a sensitivity of
10X over the 1 cm cells. Twenty milliliters of CCL^ were added to each sample
bottle prior to col lection, and then each sample was extracted twice with 25
ml of CCLlj to ensure adequate extraction.
The samples were shaken vigorously for one minute in separatory funnels.
After phase separation, the bottom layer was drained through sodTum sulf.ate
15
-------
I
...2.930cm*1
Figure 5. Oil absorbance IR band.
and collected in a tared 50 ml beaker. The extract solution became the.
SAMPLE EXTRACT (As). Samples were scanned in the 3200 cm to 2600 cm
region with an IR-Spectrophotometer using CCL^ in the reference beam. Absor-
bance was again measured at 2930 cm"' and the solution returned to the 50 ml
beaker. The solvent was jet-air evaporated down to dryness and the residue's
weight recorded. This residue was brought to volume and became the SIMULATED
STANDARD SOLUTION (Ar), The solution was scanned in the range 3200 cm"i to
2600 cm"1 for percent absorbance. Each surface water sample extracted was
then analyzed by UV-Fluorescence spectroscopic techniques in a volume of 50
ml hexanes. The hexanes solvent was evaporated off and each sample was con-
centrated to 50 ul for gas chromatographic analysis.
MARINE ORGANISM (Mya arenaria L.)
Hydrocarbons are not unique to.getroleum products, since marine organisms
do synthesize specific hydrocarbons . The presence of waste petroleum
hydrocarbons may be masked to some extent by the presence of naturally occur-
ring hydrocarbons native to the organism itself. Such alteration processes
as dissolution, biochemical oxidation and differentiation of hydrocarbon in-
corporation may also cause some difficulty in differentiation . Therefore,
with an analytical scheme involving a marine organism the specific identifi-
cation parameters established, should be directed at detecting the presence
of those classes of hydrocarbons unique to petroleum that are relatively un-
affected by weathering and, which do not occur naturally in the organism.
Figure 6 is the procedure utilized for the extraction of waste petroleum
in a marine organism. It was felt that by separation of the biological ex-
tracts into the fractions indicated, the specific hydrocarbons attributable
only to oil pollution could be exhibited.
The clam tissue was homogenized with 50 ml of n-hexane (99 Mole % Pure;
Fisher Scientific Co.) in a "VirTis 45" oilless blender (VIRTIS Co., Gardiner,
N.Y.) at medium speed for three minutes. The solvent is jet-air evaporated
16
-------
15 shucked clams, M. arenaria L,
without internal fluids, size range
1-4 cm, frozen until analysis
VIRUS BLENDER
homogenate tissue +. 50 ml n-hexane
evaporate off solvent, add 3 x wet
tissue weight of ^2804 anhydrous
powder, mix and freeze for 24 hours
soxhlet extraction
for 6 hours in hexane
100 ml of extract - jet-air evapo-
rate solvent off - record weight
of residue in mg/100 ml
bring residue to 100 ml volume
hexanes - UV-fluorescence analysis
column chromatography
benzene
fraction
methanol
fraction
cyclic paraffins
branched chain cpds
ight aromatic
saturates
aromatics
NA's, heterocompds
polars
Figure 6. Extraction of hydrocarbons from an estuarine benthic organism.
17
-------
off, and three times the weight of tissue homogenate of Na2SOr (anhydrous pow-
der; Fisher Scientific Co.) is added. The mix is stirred with a spatula until
the tissue is evenly distributed in the sodium sulfate. This entire blend is
placed in a freezer for 2k hours. Upon removal from the freezer, the mix is
added to a Soxhlet extraction thimble. The thimble (Whatman single thickness,
cellulose thimbles) is pre-extracted In a Soxhlet with n-hexane for four hours
to remove any contaminants. The original solvent is discarded and the thimble
is extracted in fresh n-hexane for an additional two hours. A fluorescence
check is conducted on this solvent by setting the sample sensitivity on the
MPF-3 UV-fluorescence spectrometer at 30, exciting the sample at 290 mu while
scanning the emissions from 240 to 5^0 mu. Emission intensity should not ex-
ceed 3% after this clean-up procedure.
Thimbles are then packed to within one-half inch of the top of the homo-
genate mix, and Soxhlet extracted in 150 ml of hexanes for a period of six
hours. After this extraction period, 100 ml portions of the total solvent
extract are removed and placed in 100 ml tared beakers. The solvent is
stripped off and the residue weight recorded. This residue is brought to 100
ml volume with hexanes and UV-fluorescence analysis conducted.
Total extracts obtained from organisms are composed of lipids and natu-
rally occurring hydrocarbons coextracted along with any petroleum derived
hydrocarbons that may be present. To better isolate tine petroleum hydrocar-
bons, a column chromatographic technique was implemented to separate the
original extract into basic saturate groups (normal, cyclic and branched
paraffinic compounds) as well as an aromatic group (polynuclear, polycyclic
aromatics and heterocompounds). This column chromatography technique utilized
solvents to differentially elute desired fractions from hydrocarbon mixtures.
After the column has been prepared, it is prewet with 50 ml of hexanes.
This entire volume is allowed to pass through the column (so as to calibrate
a flow rate of approximately 2 ml/min with dry air pressure) until only a
solvent miniscus remains at the top. A 2 ml volume of sample extract is
added to the top of the miniscus and allowed to be absorbed. Fifty milli-
liters of n-hexane is immediately added to the column as the first elutate
and kS ml are collected in a tared 50 ml beaker. This is the HEXANE PORTION.
Dry air is delivered to the top of the column so as to maintain a flow rate
of approximately 2 ml/min. Once the entire hexane portion is absorbed, 50 ml
of benzene is added and 45 ml are collected in a 50 ml beaker resulting in
the BENZENE PORTION. Finally, 50 ml of methanol is added so as to elute the
aromatic and heterocompounds, and is labeled the METHANOL PORTION. These
solvent fractions are evaporated to dryness and weights of residues recorded.
A flow-chart for the subsequent analyses of these fractions is shown in Figure
7.
18
-------
100 ml
total organism
soxhlet extract
in n-hexane
jet-air
evaporate off
solvent
record weights
bring to 2 ml
volume in n-hexane
and add to top of
chromat o graphi c
column
50 ml
methanol
-short chain
Total saturates
and some PNA's
-long chain and
\branched chain compounds
PNA's, heterocompounds
and polar groups
Figure 7. Extraction and analysis of organism sub fractions: a flow diagram.
-------
SECTION 8
ANALYSIS OF SAMPLE EXTRACTS
GAS CHROMATOGRAPHY
Analytical Approach
Two qualitative approaches to the analysis of chromatograms generated by
sample extracts were utilized in this study. The first sought to qualita-
tively match the chromatograms generated by environmental samples to those
chromatograms obtained from a group of "on-hand" reference petroleum products
including a waste crankcase oil. Specific chromatographic "profiles" of
these reference standards were looked for in the environmental sample.
Figure 8 exhibits these petroleum entities and shows their unique chro-
matographic profiles. For example, chromatograms of the WCCO all exhibited
a large unresolved envelope above the baseline. This envelope portion has
been established53 as being caused by the presence of a complex mixture of
polynuclear aromatic hydrocarbon structures (PNA's). Gas chromatographic
analyses of WCCO have indicatedS^ the presence of a variety of k- and 5-ring
PNA compounds.
Also characteristic of the chromatograms generated by the WCCO standard
is a "light-end" region containing those petroleum hydrocarbons with carbon
numbers under Cj£« These are accumulated in the crankcase after thermal
breakdown of original polymeric add it ivies and basic lubricating oil hydro-
carbon constituents.
There is also the possibility of contamination from lower boiling range
gasolines. Peaks atop the envelope portion of the chromatograms are attribu-
table to mixtures of paraffinic, olefinic heterocompounds over a wide range
of boiling points. Chromatograms of refined lubricating oils (Figure 8 B-E)
do not exhibit the "light-end" or low molecular weight portion present in the
WCCO chromatogram. These processed petroleum products usually do not contain
many low boiling point n- alkanes because of dewaxing processes^S. However,
many homologous isomers (branched alkanes) are present in petroleum pro-
ducts5°.
Mono- and polyalkylated benzenes and mixtures of polynuclear aromatics
are not found normally in the environment, and because of their relative
stability pose potential environmental threats. The gas chromatographic
profiles generated by the constituents of refined petroleum products exhibit
markedly different characteristics when compared to profiles of crude or fuel
oils (see Appendix B for gas chromatograms of crude oils). The
extensive unresolved envelope portion (UEP) can be attributable to the com-
20
-------
B
Figure 8. Chromatographic profiles of reference standards,
A. Waste crankcase oil D. Crude oil
B. 10W/30 oil
C. Transmission fluid
E. No. 2 fuel oil
F. C6-C_6 "SPIKE"
21
-------
2-
g:
o;
01
o
LU
o
o
o
INCREASING TIME AND TEMPERATURE
Figure 8. (cont.)
22
-------
plex, high boiling additives and natural constituents of these processed
petroleum products. The high temperatures refined petroleum products are
being subjected to in today's automobiles cause the breakdown of their sub-
stituent hydrocarbons. These high temperatures are similar to catalytic
breakdown or "cracking" (the breaking down of large hydrocarbon molecules in-
to smaller molecules by heat) and other refining processes (such as isomeri-
zation where there is an alteration of the arrangement of atoms in a molecule)
to which the original crude oil may have been subjected. This is exhibited
in chromatograms of fresh (non-weathered) WCCO by the presence of a "light-
end" portion which is absent from chromatograms generated by the unused motor
oils.
The rigors of environmental weathering will cause alterations to the
WCCO profile. Volatile "light-ends" will be the first to be lost to evapora-
tion. Bacterial degradation will utilize n-paraffins most readily and then
sequentially utilize other petroleum derived hydrocarbons at a slower pace^?.
Therefore, what chromatographic profile will look like for the detection of
oil in the environment, will depend on the extent of weathering of this oil.
Reference standard samples of WCCO, 10W/30, 20W/50 and transmission fluid
(200 ml of each/1 of filtered sea water) subjected to 32 days of environmental
weathering resulted in chromatograms exhibited in Figure 9.
The environmental persistence of the aromatic portion is indicated by
the presence of the resultant envelope. That these high molecular weight
paraffins and aromatic compounds are stable is confirmed by reports of samples
taken from the Torrey Canyon disaster where it was foundSo that petroleum
derived compounds above C£0 were stable after exposure to the environment
for a month. Recent investigations59 into the aromatic fractions in surface
tars, show them to be composed mainly of alkylated naphthalenes. These com-
pounds have been shown to be toxic to some marine species and to cause shifts
in the species composition of phytoplankton. The recent Argo Merchant spill
should be studied for such phytoplankton species shifts.
The second chromatographic approach involved the use of retention time
indices. On a chromatogram the distance from the point of injection on the
time axis to the peak of an eluted component emerging from the column is
called the "retention time" for that particular component. Retention data
are dependent upon the proper functioning of the gas chromatographic equip-
ment as well as the inherent dependence upon column temperature, carrier
gas flow rate and the affinity between sample component and the stationary
phase. There are techniques to reduce variability to some degree in generated
chromatograms such as injecting a sample while noting the retention values
as well as the relative peak heights. A second injection of the sample is
then made maintaining the same operating conditions, however, this time a
standard Cg-Cjfc "spike" is added to the sample solution. The retention times
are noted again and any increase in peak heights of those sample components
noted on the previous chromatograms by the corresponding- reference carbon
compound, should indicate its presence in the sample. The use of retention
data was also utilized to detect hydrocarbons present in the organism extract
samples after these extracts were eluted through an absorption column and
separated into specific hydrocarbon fractions. The chromatograms generated
by this technique will be discussed in another section of this report.
23
-------
LABORATORY WEATHERING - 120 days
ENVIRONMENTALLY WEATHERED
-32 days
x
a
Figure 9. Gas chromatograms of weathered waste crankcase oil.
-------
UV-FLUORESCENCE SPECTROPHOTOMETRY
Analytical Approach
All petroleum products wi 11 fluoresce when excited by ultraviolet light
due to the presence of a mixture of hydrocarbon compounds with multi-ring
configurations, such as fused-ring polynuclear aromatics^O. Whether or not an
environmental sample was considered containing waste petroleum pollutants was
determined by its profiles ability to "correlate" visually with profiles gen-
erated by reference sample oils under the same analytical conditions. Each
reference sample oil (10 mg/100 ml n-hexane solutions 10W/30, 20W/50, trans-
mission fluid and waste crankcase oil) was excited at 290 mu, while scanning
the emission spectrum from 240 to 540 mu (Figure 10). Previous investiga-
tors® had utilized 340 mu as the excitation wavelength for the characteriza-
tion of petroleum entities, however it has been shown62 that Raman scattering,
a peak generated by inherent characteristics of the solvent itself, at that
frequency will obscure and otherwise alter the fluorescence profile to a
degree that sample differentiation is made difficult. Excitation of the
various petroleum products utilized in this project at 290 mu allowed for
greater differentiation and for unique characterizations.
A synchronous excitation fluorescence spectroscopic technique was imple-
mented for sample analysis^S. Each standard oil was excited at successive
excitation wavelengths (at 20 mu intervals) from 240 mu to 440 mu while scan-
ning for the maximum fluorescence emission at each of the respective excita-
tion wavelengths. Each maxima peak can be utilized as a point to be plotted
graphically generating a "fluorescence maxima profile" (FMP) for each sample
(Figure 11). Once the FMP's for reference standard oils are obtained and the
environmental sample FMP's generated, a qualitative correlation can be made.
A correlation was determined visually by comparing the FMP plots of known oils
to the maxima profile plots of the environmental samples (Figure 12). If
these maxima profiles "fit" each other (Figure 13), then the presence of a
waste petroleum product is established for the particular sample under inves-
tigation. This passive detection scheme depends upon the presence of fluo-
rescent petroleum compounds, such as polynuclear aromatics and permits the
differentiation between waste lubricating petroleum products and other petro-
leum entities. In addition, the ability to differentiate between a lubrica-
ting oil and a crude or fuel oil64 as well as the ability to differentiate
between different motor oils by UV-fluorescence spectroscopy have been docu-
mented^ and supports the aforementioned criteria.
Once a WCCO enters the environment, it is immediately subjected to
environmental weathering processes. Evaporation and bacterial degradative
processes begin immediately. If this waste petroleum product remains in the
environment long enough it will begin to lose some of its passive identifica-
tion characteristics (i.e. "light-ends" are lost in gas chromatograms of
weathered WCCO). Weathering has less of an overall effect on fluorescence
analysis due to the environmental resistance of polynuclear aromatics (PNA)
and aromatic portions of waste automotive lubricants. Since ppb levels of
PNA's will be detected by fluorescence analyses, those sample profiles which
exhibit similar emission characteristics as those profiles generated by stan-
dard oils, allow for their correlation.
25
-------
o 5 o o o o o o
Wavelength
00°
Figure 10. "Reference Standard" waste crankcase oil.
26
-------
70-
60-
50-
40-
30i-
20H
(73
z-
LU,
I-
LU
240 260 280 300 320 340 360 380 400 420
EXCITATION FREQUENCY
Figure 11. Fluorescence maxima profile (FMP) for WCCO,
27
-------
n-hexane solvent blank
10W/30
20W/30
transmission fluid
Standard WCCO
Arabian Light Crude
B Bachaquero Crude
K Kuwait Crude
2^0 2to 2&> 3cc a^fi 3
-------
100-
90-
80-
70-
60—
S 5°-
- 40-
O
CO
CO
j| 30-
uu
20-
10-
KEY
• = WCCO Standard
o = 26th. Ward
& = Jamaica
x = Coney Island
• = Rockaway
I
o
I I
o o
CO 00
If)
X (m/z)
Figure 13. Fluorescence Maxima Profiles (FMP) for environmental sample extracts,
29
-------
In every case where a sample's profile met the qualitative criteria
established by the reference samples, it was noted in a "correlates" column.
When the profiles generated were inconsistent with the qualitative criteria
for a correlation, it was noted, in a "slight correlation" category. It should
be emphasized that the correlation criteria are purely formulative in that
direct source identification (whether gas station, marina, etc.) of particular
petroleum waste products could not be established by this analysis technique.
The fluorescence method was developed to identify suspect oils using known
and reference oil samples. Further investigation into the effectiveness of
these methods in the detection of unknown oils is needed. Correlation is
based solely upon profiles generated and information gained through fluores-
cence analysis of reference samples. In some cases the environmental samples
which exhibited fluorescence responses to that of the standard WCCO, also
exhibited additional fluorescence responses similar to other oils. It was
for this reason that a category entitled "slight correlation" was utilized
instead of "no correlation", since there was the possiblity of the presence
of a mixture of petroleum entities within the sample extracts. The source
of these oils could be from home heating fuels discarded as tank-bottom
wastes, since No. k and No. 6 fuel oils are utilized as heating fuels for
housing complexes in this area. Yet, fluorescence differentiation of these
fuel oils and waste automotive lubricants can be clearly observed in 290 mu
excitation emission profiles (Figures ^k and 15).
Operating Procedures
In the operation of the UV-fluorescence spectrophotometer, low fluores-
cence silica cells were utilized. All solvents were analyzed for contami-
nants by fluorescence at maximum sensitivities before use. Figure 16 is a
schematic for the fluorescence analysis procedure as well as the instrument
settings utilized.
GAS CHROMATOGRAPHY - MASS SPECTROSCOPY (GC-MS) AS A CONFIRMATION METHOD
The use of mass spectroscopy far the analysis,pfxhydrocarbons derived
from petroleum products has been well established " . UsgqOf high resolu-
tion mass spectroscopic equipment has enabled investigators to determine as
many as 2900 components in a single petroleum fraction sample. For such
extensive data acquisitions, the use of a computerized system has greatly
increased speed of analysis and identification ' . Fractions obtained
from column chromatography of marine organism extracts were evaporated to
approximately 50 ul with 1-5 ul portions being injected into the system.
The following list outlines the GC-MS computerized system utilized.
Column dimensions
5 foot x 2 mm ID, glass, packed 3% OV-1 on Chromsorb W.
Program
Temperature programmed 100 C to 280 C at 6 C/min, run isothermally at 280 C
for approximately 10 minutes.
Carrier Gas
Helium; flow at 1.5 ml/min at column outlet.
30
-------
No. 4 Fuel Oil
Bachaquero Crude
90
No. 2 Fuel Oil
0W/30
Figure
"Reference Standard" samples.
31
-------
Rockaway WPCF
O O & S O
Wavelength (
Figure 15. Correlation with WCCO reference standard.
32
-------
Fluorescence Profiles
IA«J
vA-IA
V
W_
• •
.
1A
^
^
^
q .,.,
w
»^
^
ac
<<
CO
Excitation at each wavelength between
240 and 440 mu; scan maximum emissions
at each excitation frequency
Excitation slit - 12
Emission- slit - 10
Scan speed - 4
Sample sensitivity settings - 1«0 to 3.0
Excitation at 290 mu
Scan emissions from 240 to 540 mu
Scan speed - 3
Excitation slit - 12
Emission slit - 3
Sample sensitivity not to exceed 10
Figure 16. Flourescence analysis procedures.
-------
Mass Spectrometer
Computerized Finnigan Gas Chromatrograph Quadrupole Mass Spectrometer
Combination, Model 1015.
It should be noted that the column in this particular GC-MS system did
not have the resolving power of the SCOT OV-101 columns utilized under the
regular chromatographic analysis of this project. For this reason, mass
spectral data for identification was restrained to some degree, and only a
few compound classes were tentatively identified. Subsequent studies in this
area should integrate SCOT columns with GC-MS computerized networks similar
to work done by Raymond and Guiochon .
-------
SECTION 9
RESULTS
WASTEWATER EFFLUENTS
The collection of WPCF's final effluents emptying into Jamaica Bay, ran
for a period commencing September 10, 1973 extending through November 5» 1973
with a total of thirty-nine samples being taken. Table 5 gives the quantita-
tive results of the CCL^ extraction and infrared analysis of these samples.
Table 6 gives the hexane extractable materials (HEM) that the City of New
York, Bureau of Water Resources had recorded since August 1972. As of May
1973 the City had utilized an infrared quantification method for analysis
and records the results as "oils and grease" in its monthly records for each
WPCF.
Four WPCF final effluent extracts were analyzed by gas chromatography.
Table 5 indicates those samples chosen at random and analyzed by the two
gas chromatographic techniques outlined in this project. Each sample chroma-
togram was observed for unique qualitative characteristics as well as for re-
tention data of resolved peaks. A spiked sample (effluent sample plus Cg -
C36 n-paraffin standards) was then injected, again noting retention times.
In all cases (Figure 17) chromatograms indicated an unresolved envelope por-
tion above 200°C. Spiked samples exhibited increases in peak heights for a
major portion of the resolved peaks. Those peaks that occurred between stan-
dard peaks were labeled.
Normal paraffins are removed as a common practice of petroleum refineries
since they give a waxy consistency which is undesirable in lube oil products.
This dewaxing process usually removes a portion of the high molecular weight
paraffins above C^Q, as well. Some low molecular weight paraffins do however
remain in the oil product to aid in the maintenance of proper viscosity. The
presence of normal paraffins of the Cg - C^g standard solution were indicated
by increased heights of extract components in generated chromatograms. Peaks
on chromatograms which occurred between normal paraffin peaks are attributable
to the presence of series of isomeric compounds and branched chain compounds.
Another criteria used to detect waste petroleum hydrocarbons in chroma-
tographic profiles is to exhibit the partial ly resolved C^-pr istane, C^-
phytane hydrocarbon peak-pairs indicative of petroleum contamination. Insuf-
ficient data was recorded here. Some indication of these petroleum derived
hydrocarbons were illustrated in some sewage effluent chromatograms (Figure
17 26th Ward gas chromatogram).
Each of the WPCF effluent sample extracts were analyzed by UV-fluores-
cence spectroscopy and the results of correlation with profiles generated by
reference oils under the same analytical parameters are shown in Table 7.
35
-------
TABLE 5. IR QUANTIFICATION OF TOTAL EXTRACTABLES (HYDROCARBONS) FROM WPCF TREATED EFFLUENTS*
Water pol lut ion
control facility
Coney Island Plant
26th Ward Plant
Jamaica Plant
Rockaway Plant
9/10
1.5
29.7
9/15
16.4
20.0
10.7
9/17
7.1
34.9
12.0
4.9
9/24
2.0
28.9
7.2
1.3
Date
9/29
3.5
22.9
5.3
4.7
10/1
15.6
12.3
4.7
0.5
10/8
3.0
19.2
9.6
|io.o|
10/15
| 39. 8 |
19.1
4.6
13.8
10/22
10.5
9.3
9.4
8.5
10/29
41.6
14.2
7.7
11/5
8.6
18.8
3.2
* all values in mg/1
= GC analysis
TABLE 6. "OILS AND GREASE" - HEXANE EXTRACTABLES*
WPCF
Coney Island Plant
26th Ward Plant
Jamaica Plant
Rockaway Plant
8/72
13.0
21.0
7.0
11.0
9/72
6.0
12.0
9.0
9.0
10/72
7.0
7.0
11.0
7.0
11/72
15.0
24.0
18.0
11.0
12/72
6.0
37.0
8.0
4.0
1/73
10.0
30.0
20.0
9.0
2/73
11.0
19.0
7.0
11.0
5/73
4.0
30.0
20.0
80.0
6/73
11.8
180.
430.
170.
7/73
19.7
250.
280.
150.
8/73
6.4
410.
115.
95.
9/73
11.3
280.
180.
160.
* all values inmg/1;from Ward Island, Bureau of Water Resources, City of New York
-------
0
0?
«*
,
<• U
o
BASELINE -
* dark areas are C6-C~6 spike above peak heights - 26th Ward STP
Figure 17. Gss chromatogram of sewage effluent extract*.
-------
TABLE 7. UV-FLUORESCENCE DATA FROM WATER POLLUTION CONTROL FACILITIES
Date Sample Fluorescence Maxima 280 - 300 mu 332 mu
Profile Fit Maxima Region Fit Peak Fit
Slight Slight Slight
1973 Correlate correl. Correl. correl. Correl. correl.
9/7 26th + + +
CIP + + +
Jam + + +
Rock + + +
9/10 26th + + +
CIP -i- + +
9/15 26th + + +
CIP + + +
Jam + + +
Rock No Sample Available This Date
9/17 26th + + +
CIP + . + +
Jam + + +
Rock -i- + +
9/2A 26th + + +
CIP + + +
Jam + + +
Rock + + +
9/29 26th + + +
CIP + + +
Jam •»• + +
Rock + + +
10/ 1 26th + + +
CIP + + +
Jam + + +
Rock + + +
10/ 8 26th + + +
CIP + + +
Jam + + +
Rock + + +
10/15 26th + + +
CIP + + +
Jam + + +
Rock + + +
10/22 26th + + +
CIP + + +
Jam + + +
Rock + + +
10/29 26th No Sample Available This Date
CIP + + +
Jam + + +
Rock + + +
11/5 26th No Sample Available This Date
CIP + + +
Jam + + +
Rock + + +
38
-------
The sensitivity of fluorescence spectroscopy to polynuclear aromatics
(PNA's) permits the unique characterization of different petroleum products
in the environment. To see if the weathering phenomena would affect identi-
fication criteria for WCCO, fluorescence analysis was conducted on the vari-
ous fresh automotive lubricating oils weathered in filtered sea water on the
roof of the laboratory for a period of 32 days. Even after this weathering
period, differentiation of lubricating oils from other petroleum products was
accomplished by use of the fluorescence techniques outlined in this project.
It has been demonstrated73 that a variety of weathered oil products do not
lose their specific identification characteristics under UV-fluorescence
analysis. Profiles may in some instances exhibit a decrease in intensity due
to concentration factors (Figures 18 and 19)• Crude and fuel oils weathered
for a period of 5 days open to air exhibited no change in identification
characteristics in analyses performed at the Industrial Waste Treatment Lab-
oratory, U.S. EPA, Edison, New Jersey. The lubricating oils weathered for
this project did show a decrease in fluorescence intensities. When these
samples were excited at 290 mu, the resultant emission profiles were not al-
tered. The graphic representations of the maxima profiles obtained from
wastewater sample extracts are shown in Figure 20.
Jamaica Bay Surface Waters
The quantity of CCL^ total extractables from each of the surface water
samples collected in the Jamaica Bay area were in the milligram per liter
concentration range. Average background levels of petroleum hydrocarbons in
oceanic waters uti1izing a similar solvent extraction method7^ have been
estimated at 2 ug/1 concentration levels. Greater than average concentrations
or what was considered as high concentrat ions of petroleum hydrocarbons were
in the range of 10 to 20 ug/1. Table 8 shows the values obtained for the
Jamaica Bay surface waters to be above normal background levels of hydrocarbon
concentrations. It should be emphasized that non-petroleum derived organic
compounds are extracted with carbon tetrachloride and are not all lost during
the jet-air evaporation step. Therefore, some portions of the extracts may
be attributable to either biologically generated hydrocarbons or to some
other petroleum entity. Care was taken to prevent contamination from waste
petroleum products generated by the research vessel, extraction procedures and
in storage.
Gas chromatographic analyses were made on all samples obtained on the
January 8, 197^ sampling run through Jamaica Bay. Attenuation and sample
injection quantities were the same for each sample so that visual comparison
could be made on the chromatograms generated. It was noted that samples
collected in the interior portions of the Bay showed significant increases in
the broadness of unresolved envelope as compared to ocean samples. The
characterization of specific peaks above the unresolved portion also increased.
Specific attention should be directed toward the sample analyzed from the
-NYJ03 site whose chromatogram exhibited these characteristics. This sample
concentration is attributable to petroleum hydrocarbon contamination. The
chromatogram produced by the NYN09A sample indicated the least contamination.
By maintaining the same attenuation settings and operating conditions, the
chromatograms accentuate a gradient response of contamination much of which
the fluorescence analysis indicates is attributable to petroleum (Figure 21).
39
-------
100
-C-
o
10
260
X Weathered • Non-weathered
Figure 18. Maxima profiles weathered and unweathered fuel oil simulated standards.
-------
280 300 320 340 360 380 400 420 440 460 48Q
X Weathered
Non-weathered
Figure 19. Maxima profiles weathered and unweathered crude oils,
-------
2 #2 Fuel Oil
0 WCCO
O Jamaica STP (9/7/73)
Z^ 26th Ward STP
(9/10/73)
* Rockaway STP
(9/24/79)
• Coney Island STP
(11/5/73)
240
260 280 300 320 400 420 440
Figure 20. Maxima profiles of WPCF
42
effluents.
-------
z
o
280° C
280°C
NYJOSi
NYJ07
Figure 21. Surface water GS analysis.
-------
TABLE 8. JAMAICA BAY SURFACE WATER TOTAL CCLL EXTRACTABLES*
Sample Site
November 7, 1973
January 8, 1974
NYN16
NYN09A
NYJ01
NYJ02
NYJ03
NYJ05
NYJ07
0.94
1.20
2.10
1.17
3.10
0.50
1.08
1.13
0.88
2.16
2.20
5.10
1.50
1.40
al1 values in mg/1
Fluorescence analysis of surface waters reveal the presence of petroleum
fractions in those samples from the Bay proper. Again, depending upon the
degree of weathering to which the oil had been subjected the intensity of the
fluorescence response varied. In no instance did any profile correlate with
other types of petroleum entities such as the fuel or crude oils. In all
cases when surface sample extracts were excited at 290 mu, the generated
emission profiles peaked at 332 mu (Figure 22). Figure 23 exhibits the plot-
ted fluorescence maxima profiles generated by the surface water extracts of
Jamaica Bay for the two sampling runs (see Table 9.).
TABLE 9. FLUORESCENCE CORRELATION DATA FOR SURFACE WATER SAMPLES
Date Source
11/7/73 NYNI6
NYN09A
NYJ01
NYJ02
NYJ03
NYJ05
NYJO?
1/8/74 NYN16
NYN09A
NYJ01
NYJ02
NYJ03
NYJ05
NYJ07
Fluorescence Maxima Maxima Region Fit 332 mu Peak
Profile Fit Fit
Slight Slight Slight
Correlate corr. Corr. corr. Corr. Corr.
+ + ' +
+ 4- +
+ ' + +
+ + +
+ + +
+ + +
+ + +
+ + +
+ •+• +
+ + +
+ + +
+ + +
+ + +
+ + +
-------
Weathered WCCO - 32 days
Weathered 10W/30, 20W/50 - 32 days
NYJ03 (1/8/74)
Reference WCCO
o oSS
Wavelength (mu.}
Figure 22. Corelation of emission spectra of surface water sample and
weathered reference standards.
-------
• NYN09A
X NYN16
D NYJ01
•0 NYJ02
A NYJ03
A NYJ05
9 NYJO?
Note: See graphs - 1/8/74
240 260 280 300 320 340 360
Figure 23. Maxima profiles for Jamaica Bay surface waters.
46
-------
Marine Benthic Organism (Mya arenaria)
Table 10 shows column chromatographic results obtained for the Mya II
extract (High Pollution Potential Sample). Column chromatography resulted
in approximately 48% recovery of substituents for the Mya II sample. .The
test was duplicated with the Mya II (Table 11) extract (Low Pollution Poten-
tial Sample) at a slower flow rate (1 ml/min) for the eluted solvents. The
results obtained using the slower flow rate exhibited approximately 80%
recovery of hydrocarbon constituents from this total organism extract. The
difference in recovery percentages indicate that a portion of the samples'
hydrocarbons remained on the column. It was felt however, that because of
the high pollution potential of the Mya II extract even with the relatively
low recovery percentages, the eluted portions would lend themselves to the
qualitative detection of petroleum hydrocarbons. Though recovery of the
aromatics was not complete, gas chromatographic profiles exhibited a number
of peaks for the aromatic portions. Subsequent quantitative studies should
seek to recover as great a percentage of hydrocarbons as is obtainable.
It has been demonstrated75 that hydrocarbons isolated from shellfish
sampled in an area presumably free of petroleum contamination have all exhib-
ited very simple compositions. Organisms have very specific biosynthetic
pathways which favor the production of hydrocarbons with very specific carbon
ranges. For example, some species of copepods exclusively contained hydro-
carbons with 19 carbon atoms in a branched chain7°. Petroleum products, on
the other hand, consist of a wide boiling range mixture of evenly distributed
hydrocarbon constituents. Gas chromatograms exhibiting extensive unresolved
portions are indicative of a samples content of these mixtures of branched,
cyclic and aromatic compounds. Normal paraffins are the most abundant biolog-
ical alkanes77. Of the major types of hydrocarbons in organisms, olefins
(alkenes) are the most abundant and aromatics generally the least abundant78.
Along with the mixture of simple normal and iso-alkanes, one or a few hydro-
carbons exceed all others by several orders of magnitude in an organism's
hydrocarbon pool79. The presence of complex mixtures of polycyclic aromatic
hydrocarbons in soils and sediments has been established"". That they are
not produced biologically but rather as the result of anthropogenic combustion
process has also recently been expressed"^.
Distribution of n-alkanes in biological tissue exhibit a preference of
odd-numbered n-paraffins over even-number n-paraffins°2, 83, Indications of
petroleum pollution arise when the oddreven ration approaches 1.0 as is the
case of Mya IIR(1.02). The Mya III extract did suggest contamination by pe-
troleum hydrocarbons, but to a lesser degree.
Thus, the appearance in gas chromatographic profiles of a complex, unre-
solved hydrocarbon envelope covering a wide boiling range, exceeded by numer-
ous peaks indicative of homologous alkanes and their isomers, will suggest a
mixed derivation of the hydrocarbons from petroleum pollution and biochemical
sources.
The chromatograms on the following pages indicated the presence of petro-
leum derived hydrocarbons in the body tissue of Mya arenaria obtained within
Jamaica Bay. The aromatic portions of Mya II (HPP) exhibit a wide range of
aromatic compounds with boiling points above 250°C. Mass-spectral analysis
47
-------
TABLE 10. HIGH POLLUTION POTENTIAL EXTRACT (HPP)
TABLE 11. LOW POLLUTION POTENTIAL EXTRACT (LPP")
oo
1/18/74; 100 ml of Mya II Total Extract
Column Chromatography Results:
100 ml beaker A?. 5336 g
47.7626 g
residue .2291 g = 229.1 mg
50 ml n-hexane @ 2 ml/min 28.4420
collect 45 ml in #1 beaker 28.4446
2.6 mg
50 ml benzene @ 2 ml/min 2?. 4513
collect 45 ml in #2 beaker 27.5373
86.0 mg
50 ml methanol @ 2 ml/min 27.
collect 45 ml in #3 beaker 27.^660
21.6 mg
Total recovery = 110.2 mg or 48.1? extract.
1/25/7^; 100 ml of Mya III Total Extract
Column Chromatography Results:
100 ml beaker 47.5748 g
47.5989 g
residue .0241 g = 24.1 mg
50 ml n-hexane @ 1 ml/min 27.5240
collect ItS ml in #1 beaker 27.5265
.0025 9
2.5 mg
50 ml benzene @ 1 ml/min 28.8972
collect A5 ml in #2 beaker 26.907
mg
50 ml methanol @ 1 ml/min 27.3710
collect 45 ml in #3 beaker 27.3830
.0120 g
12.0 mg
Total recovery = 19.0 mg or 79? extract.
-------
of the aromatic portion from Mya II (HPP) indicates the presence of substitu-
ted alkyI benzenes. These types of aromatic hydrocarbons have been found
only in extremely small amounts or not at all in marine organisms. They pre-
dominate in the aromatic portions of petroleum products"^' °5 (Appendix C,
Mass Spectral Data). The saturate portions of Mya II (HPP) extract exhibit
the presence of isomeric compounds probably of a branched paraffinic nature
(Figure 2k, Mya II Benzene portion). The Mya III extracts (LPP) (Figure 25)
portion, was considerably simpler than the Mya II aromatic portion, indicating
possibly less exposure to petroleum hydrocarbons outside the Bay than in the
Bay.
The results of the fluorescence analyses on Mya^ arenaria extracts are
shown in Table 12. Those samples collected from the Bay proper produced
excellent correlations with reference oils. The Mya III extract did not
correlate successfully with the reference standards, yet there was some indi-
cation of the presence of a petroleum fraction when one observed its maxima
profile (Figure 26). When the Mya III extract was excited at 290 mu not only
did an emission peak occur at 332 mu, but a peak of greater intensity occurred
at 370 mu. This peak could be indicative of contamination from other petro-
leum pollutants derived from oceanic waters. For example residual fuel oils
peak at 350-400 mu86.
TABLE 12. FLUORESCENCE DATA FOR Mya arenaria L. EXTRACTS
Date Source Fluorescence max profile Max region fit 290 mu excitation
1973 Correlation Slight corr. Corr. SI. corr. Corr. SI. corr.
10/23 Mya la
12/ 3 Mya I lb
+
+
•f +
12/ 3 Mya III
a Collected at Egg Harbor, Jamaica Bay
b Collected at Diamond Point, Jamaica Bay
c Collected off Rockaway Point, Atlantic Ocean
If no recent oceanic oil contamination has occurred in the vicinity of
Jamaica Bay, this result raises some interesting questions as to the origin
of these residues. If these derived residues are attributable to past pollu-
tion incidents, the persistence of these petroleum derived hydrocarbons in
the environment or their ability to become incorporated in biological tissue
has been demonstrated by these results. Further investigation is needed to
see whether or not similar data could result from some non-petroleum derived
materials in such samples. Further study of specific compound identification
is needed as well as work on the particular species distribution and diversity
pattern In this petroleum hydrocarbon burdened ecosystem.
-------
A benzene portion
B methanol portion
Figure 2k. Mya II (HPP).
50
-------
r ^V J ) [
N _~>^1'W^U^^^^AA-*^^, __^j( X U
A benzene portion
B methanol portion
Figure 25. Mya III (LPP)
-------
X Mya I I (HPP) - 12/73
0 Mya I I I (LPP) - 12/73
Mya I - 10/22/73
10
240 260 280 300 320 3^0 360 380 AGO 420
Figure 26. Maxima profiles for organism extracts,
52
-------
SECTION 10
DISCUSSION
It should be stated at the outset that the gas chromatographic methodol-
ogy that was utilized for this study was not directed toward a routine program
of analysis, but rather was directed toward the specific and immediate problem
of detection of waste automotive lubricating oils. Any shortening of the life
of the chromatographic column by loading with high-boiling materials upon in-
jection was felt to be justified as long as the resolution of resultant chro-
matograms was not appreciably affected. Any long range, large scale or highly
quantitative study could not afford such a luxury.
The gas chromatograms generated by WCCO and refined petroleum products
have been shown to be characteristic and differentiable from chromatograms of
other petroleum entities. Weathering appears to have little effect upon some
of the specific detection parameters for waste crankcase oils. The continued
existence of an unresolved envelope portion, of a number of wide-boiling range
compounds, of C^-pristane/C-|g-phytane peaks, and of a series of n-paraffins
above the unresolved portion in chromatographic profiles, together indicate
the presence of a specific oil product. All gas chromatograms of sewage ef-
fluents and surface waters did not reveal these criteria. Though not conclu-
sive the boiling range of substituents separated and the unresolved portions
of the sample chromatograms seem to indicate the presence of a waste petroleum
product in samples. Further investigation is needed to generate definite gas
chromatographic corroboration with standard WCCO chromatograms. Those chroma-
tographic data for sewage effluents and surface waters may be considered at a
preliminary level of assessment and a consequence of sample concentration
problems. It is hopeful that these problems will be investigated in subse-
quent work.
Though the specific source of the waste petroleum detected could not be
established in this project, sample analyses strongly indicated that the waste
petroleum hydrocarbons detected were derived from waste automotive petroleum
products. What was detected could not have been' attributable to any other
petroleum entity since other standard oil profiles were clearly differentiable
from profiles generated by WCCO. Gas chromatograms generated by WPCF efflu-
ents did show a range of hydrocarbon compounds above C2g; a characteristic of
lubricating oils is that they have very few hydrocarbons boiling below n-
eicosane°7. The chromatographic characteristics of an unresolved envelope
portion due to the presence of complex PNA compounds was indicated in all en-
vironmental extracts taken.
88
It has been illustrated by previous investigators , and in this project
that the weathering phenomenon that affects a petroleum product once it enters
the environment, have less of an effect upon'the less soluble and more persis-
53
-------
t'ant aromatic portions of an oil. Bacterial degradative processes have been
shown to preferentially attack straight chain, lower molecular weight compo-
nents with the higher molecular weight compounds being less affected^S. These
aromatic hydrocarbon portions have been known-*" to adhere to suspended parti-
cles in the water column and settle out into bottom sediments with possible
subsequent effects upon benthic populations. Gas chromatograms generated by
the organism extracts strongly indicated the presence of aromatic compounds
from body tissue. Tentative gas chromatographic-mass spectroscopic identifi-
cation of sub-fractions derived from organism extracts exhibited the presence
of alkyl-substituted benzene structures which are indicative of petroleum
contamination.
UV-f luorescence spectroscopic analyses furnished the most conclusive evi-
dence for the presence of petroleum in samples and greatly strengthened the
analytical results obtained from gas chromatographic analyses. Emission spec-
tra of all samples studied consistently indicated the existence of PNA com-
pounds which could only be attributable to petroleum pollution. With WCCO's
unique fluorescence character and characteristic profiles, its presence in
environmental samples was established. Further development is needed for
future attempts to demonstrate the presence of oil where the existence of oil
is only suspect.
The results presented strongly indicate that hydrocarbons discharged into
Jamaica Bay, occurring in the surface waters and ultimately becoming incorpor-
ated in biological tissue is of a waste petroleum origin. Whether this oil
is from intentional or accidental dumping of WCCO into sewers is still un-
known. The unique characteristics of the study area and the fact that the
major contribution of fresh water input to the Bay comes from WPCF, provides
an indication that the detected hydrocarbons are originating from waste crank-
case oils and not from other types of petroleum products. Atmospheric wash-
ings and JFK airport operations could contribute significant quantities of
hydrocarbons to the water column. Further investigation is needed here and
subsequent work should note background levels of atmospheric derived hydro-
carbons entering Bay waters.
Though the detection of waste petroleum hydrocarbons in the marine envi-
ronment was a major concern in this project, my ultimate regard lies within
the biological significance of this addition to the marine ecosystem. It has
been suggested^1 that at least some of the petroleum hydrocarbons retained by
an aquatic organism would be an obvious advantage. It could be a means to
prevent a loss of equilibration of important biogenic hydrocarbons. On the
other hand, recent data indicates^ that some marine mussels do not metabolize
the hydrocarbons taken up but retain significant amounts in their tissues.
These aromatic compounds have been shown not to be found in the environment
naturally and would almost exclusively be from a petroleum originS3.
In addition to the known toxicitv of such aromatic compounds as benzene
and its alkyl-substituted derivatives^, specific PNA compounds found in oil
waste products have been shown ' to be potent carcinogens. Detection of
PNA's by UV-fluorescence spectroscopic techniques used in this study and by
other investigators were based upon the stability of these aromatics in
the environment and their ability to fluoresce. Detection of such potent and
ubiquitous PNA compounds as 3»^-benzopyrene have been exhibited at various
-------
levels in a variety of marine organisms " . Investigation into the quan-
tities of such PNA compounds in this environment are needed.
Recent observations exhibited before a meeting of the National Insti-
tute of Environmental Health Services in Washington, D.C. by scientists of
the National Marine Water Quality Laboratory in Narragansett, R.I., revealed
a high incidence of histopathological effects such as malignant neoplasmic
growths and cardiovascular abnormalities in marine organisms exposed to petro-
leum hydrocarbons.
Physiological responses of marine organisms have been shown to be affec-
ted by the presence of aromatic compounds in the marine environment. It has
been suggested that microscopic chemoreceptors in bivalves will detect the
presence of these substances and bring about changes in their filtration
rate. The effects on feeding rates, growth rates and reproductive processes
should be investigated. The ultimate here being the possible impacts upon
marine food chains. Fish and other organisms taken from areas with a history
of oil contamination have been found to exhibit elevated levels of compounds
which:"bioactivate" complex aromatic compounds found in waste crankcase oils,
into mutagens . The possible long-term adverse effects on the health of
human consumers of fish requires greater scrutiny in light of this potential
mutagenic burden.
Therefore, gas chromatography, UV-f luorescence spectroscopy and gas
chromatography-mass spectroscopy in combination have collectively aided in
the detection of petroleum derived hydrocarbons attributable to WCCO in waste-
water effluents entering the marine environment. The composition of extrac-
ted hydrocarbons from a marine organism, especially the content of a series .
of wide boiling range aromatic compounds, strongly indicates that these sam-
ples were polluted by petroleum. The continued addition and existence of
these petroleum wastes can only lead to a further deterioration of this
marine ecosystem.
Assuming a basis has been established by the results of this project of
a large hydrocarbon burden in Jamaica Bay, further steps should be taken in
the research of this ecosystem. A total community response to chronic petro-
leum derived hydrocarbon input should be undertaken. Our coastal areas pro-
vide food and shelter for a wide variety of wildlife, both indigenous and
migratory. Many commercially valuable fish maturate in our estuarine areas.
This provides critical support to marine food chains reaching all the way to
man. The effects of hydrocarbons on physiology, population dynamics and
functions of marine organisms within these wetlands, as well as the public
health aspects of chronic hydrocarbon pollution to this area, have yet to be
explored.
Finally, Jamaica Bay is one of the few natural resources that remain in
the New York metropolitan area. The immediate problems in aquatic pollution
that confront these wet lands wi 1 1 be magnified in the future. Even with the
Bay's inclusion in the Gateway National Recreation Area, it will be no pro-
tection against added pol lution. New housing developments, airport operations,
offshore oil drilling and deep water ports all threaten the possible irre-
versible burden of increased hazardous chemicals to this ecosystem. An in-
55
-------
creased effort should be aimed at restoring these local waters to the point
where they may support a much greater variety of marine life. The idea of
fostering a shell-fishery in Jamaica Bay should not be unimaginable.
It is hopeful that this project can initiate an awareness of the increas-
ing quantities of waste oil discharging into our coastal waters through treated
and untreated municipal wastewaters and storm sewers. Further investigation
and consideration is necessary to understand the overall impact of our urban
centers on the environment.
.56
-------
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35. MIT Press, (1970) "Man's Impact on the Global Environment". Table 5, 10.
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Department Water Resources, Environmental Protection Administration, City
of New York (1970) Final Report - Year I, Spring Creek Auxiliary Water
Pollution Control: Development of Scientific Parameters for the Control
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and the Quantitative Assessment of the Ecology of Jamaica Bay, p. III-4.
39. Ibid., p. III-7.
59
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40". Ibid., "Tides", P. MI-3.
41. Ibid., "Hydrographic and Hydraulic Characteristics", P. MI-3.
42. Ibid., p. I 11-6, Table I 11-3.
43. Personal Communications with Water Pollution Control Facility Personnel
and Plant Superintendents, Oct. 1973.
44. Loehr, R. C. and deNavarra, C. T., (1969) op. cit., p. R144.
45. Farrington, J., (1973) op. cit., p. 7.
46. Gruenfeld, M., (1973) E.S.ST., "Extraction of Dispersed Oils from Water
for Quantitative Analysis by Infrared Spectrophotometry", Vol. 7, No. 7,
p. 637.
47. Analytical Quality Control Laboratory Newsletter, (EPA, Cincinnati,
Ohio), No. 18, July 1973, p. 8.
48. Blumer, M., Mull in, M. M., and Thomas, D. W., (19&3) "Pristane in Zoo-
plankton". In: Science, Vol 140, p. 974.
49. Youngblood, W. W. and Blumer, M., (1973) "Alkanes and Alkenes in Marine
Benthic Algae". In: Mar. Bio., Vol. 21, p. 163-172.
50. Blumer, M. and Thomas, 0. W., (1965) "Phytodienes in Zooplankton". In:
Science, Vol. 147, p. 1148-1149.
51. Blumer, M. and Thomas, D. W., (1965) "Zamene, isomeric C-Q mono-olefins
from Marine Zooplankton, Fishes and Mammals". In: Science, Vol. 148,
p. 370-71.
52. Farrington, J., (1973) op. cit., p. 8.
53. Brown, R. A., (1972) "Identification Based Upon Gas Chromatograms of Tri-
cyclic aromatics In Petroleum". In: Analytical and Information Div.,
ESSO Research and Engineering Co., prepared for office RSM, EPA, Wash.,
D. C., p. 42-43.
54. Begeman, C. R, and Colycci, J. M., (1970) op. cit., p. 1782.
55. Personal Communication with Dr. B. Dudenbostel, Surveillance and Analy-
sis Division, Region II Environmental Protection Agency, Edison, New
Jersey (March, 1974).
56. Farrington, J., (1973) op. cit., p. 3.
57. Kator, H., (1973) "Utilization of Crude Oil Hydrocarbons by Mixed Cul-
tures of Marine Bacteria". In: The Microbial Degradation of Oil Pollu-
tants, Ahearn, D. G. and Meyers, S. P., eds, Workshop held at Georgia
State University, Atlanta, December, 1972, p. 60.
60
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58. Brunnock, J. V., Duckworth, D. F., and Stephens, G. G., (1968) op. cit.,
p. 318.
59. Ocean Affairs Board, "Petroleum in the Marine Environment" (National
Academy of Sciences, Washington, D. C.) 1975.
60. Riecher, R. E., (1962) American Assoc. Petrol. Geol. Poll., Vol. 46,
p. 60-65.
61. Thurston, A. D. and Knight, R. W., (1971) op. cit., p. 64.
62. Frank, U.,. Analytical Quality Control Laboratory Newsletter (EPA, Cin-
cinnati, Ohio) No. 15, Oct. 1972, p. 4.
63. Frank, U., and Gruenfeld, M., "Use of Synchronous Excitation Fluorescence
Spectroscopy for In Situ Quantifications of Hazardous Materials in Water"
In: Proceedings of 1978 National Conference on Control of Hazardous
Materials Spills, April 1978, p. 119.
64. Goldberg, M. C. and Devonald, D, H., (II , (1973) "Fluorescent Spectro-
scopy - A Technique for Characterizing Surface Films", J. Res. U.S.
Geol. Survey, Vol. 1, No. 6, p. 714.
65. Smith, H. F., (1968) op. cit., p. 23-24, Figure 7.
66. Lumpkin, B. H. and Aczel, T., (1964) "Low Voltage Sensitivities of Aroma-
tic Hydrocarbons", Anal. Chem., Vol. 36, No. 1, p. 181-184.
67. Johnson, B. H., Aczel, T., (1967) "Analysis of Complex Mixtures of
Aromatic Compounds by High Resolution Mass Spectroscopy, at Low loniza-
tion Voltages". In: Anal. Chem., Vol. 39, No. 6, p. 682-684.
68. Heller, S. R., McGuire, J. M., and Budde, W. L., (1975) "Trace Organics
by GC/MS". In: Env. Sci. & Tech., Vol. 9, p. 210-213.
69. Aczel, T., and Johnson, B. H., (1967) Proceedings 153rd National Meeting
of the American Chemical Society, meeting held at Miami Beach, Florida
Conference, April 9-13, 1967, Vol. 12, No. 2, p. 8-83.
70. Aczel, T., et al., (1970) "Computerized Techniques for Quantitative High
Resolution Mass Spectral Analysis of Complex Hydrocarbon Mixtures". In:
Anal. Chem., Vol. 42, No. 3, p. 341-347.
71. Seminar, "Computerized Gas Chromatography/Mass Spectroscopy presented
under the auspices of the Region II Surveillance and Analysis Lab., EPA,
Edison, New Jersey, by Dr. B. Dudenbostel, Oct. 9, 1973.
72. Raymond, A., and Guiochon, G., (1974) "Gas Chromatographic Analysis of
Co-C.g Hydrocarbons in Paris Air". In: Env. Sci. and Tech., Vol. 8,
No. 2,.p. 143-148.
73. Frank, U., (1973) UV-Fluorescence Spectroscopy, AQCS Newsletter, No. 18,
P. 9.
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74. Keizer, P. D. and Gordon, D. C., Jr., (1973) "Detection of Trace Amounts
of Oil in Sea Water by Fluorescence Spectroscopy". In: J. Res. Brd.
Canada, Vol. 30, No. 8, P. 1039-1046.
75. Burns, K. A. and Teal, J. M., (1971) "Hydrocarbon Incorporation Into the
Salt Marsh Ecosystem from the West Falmouth Oil Spill", Unpublished
Manuscript, WHOI Public. No. 71-69, p. 8.
76. Blumer, M., Souze, G. and Sass, J., (1970) op. cit., p. 201.
77. Koons, C. B., Jamieson, G. W. and Ciereszko, L. S., (1965) "Normal Alkane
Distribution in Marine Organisms: Possible Significance to Petroleum
Origin". In: Pull. Am. Assoc. Petrol. Geologists, Vol. 49, p. 301.
78. Meinschein, W. G., (1969) "Hydrocarbons: Saturate, Unsaturated and Aro-
matic". In: Organic Geochemistry, Elington, G. and Murphy, M. I. J.,
eds., (Svinger-Verlag, New York), p. 346.
79. Erhardt, M. and Blumer, N., (1972) "The Source Identification of Marine
Hydrocarbons by Gas Chromatography". In: Env. Poll., Vol. 3, p. 179-194.
80. Hites, R. A., (1976) "Sources of Polycylic Aromatic Hydrocarbons in the
Aquatic Environment". In: Sources, Effects and Sinks of Hydrocarbons
In the Aquatic, AIBS, Wash., D.C., p. 325-332.
81. Hites, R. A., LaFlemme, R. E., and Farrington, J. W., (1977) "Sedimentary
Polycyclic Armatic Hydrocarbons: The Historical Record". In: Science,
Vol. 198, No. 4319, p. 829.
82. Zafirious, 0., Blumer, M., and Meyers, J., (1972) op. cit., p. 32.
83. Clark, R. C. and Blumer, M. (1967) "Distribution of n-paraffins in Marine
Organisms and Sediments". In: J. Limn, and Oceanog., Vol. 12, p.310-325.
84. Meinschein, W. G., (1959) "Origin of Petroleum". In: Bull. Am. Assoc.
Petrol. Geologists, Vol. 32, p. 925.
85. Meinschein, W. G., (1969) op. cit., p. 336.
86. Zitko, V., (1971) "Determination of Residual Fuel Oil Contamination of
Aquatic Animals". In: Bull. Env. Contam. and Tox., Vol. 5, No. 5, p. 560.
87. Meinschein, W. G., (1969) op. cit., p. 338-339.
88. Boyland, D. and Tripp, B., (1971) "Determination of Hydrocarbons in Sea-
water Extracts of Crude Oils and Crude Oil Fractions". In: Nature,
Vol. 230, p. 44-47.
89. Davis, J. B., (1967) Petroleum Microbiology (Elsevier Press),Chpt.8,p.350.
90. Mileikovsky, S. V., (1970) "The Influence of Pollution on Pelagic Larvae
of Bottom Invertebrates in Marine Nearshore and Estuarine Waters". In:
Mar. Biol., Vol. 6, p. 350-356.
62
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•91. Stegeman, J. J. and Teal, J. M., (1973) "Accumulation, Release and Re-
tention of Petroleum Hydrocarbons by the Oyster Crassostrea virginica".
In: Marine Biology, Vol. 22, p. 43.
92. Lee, R. F., Sauerheber, R. and Benson, A., (1972) "Petroleum Hydrocar-
bons: Uptake and Discharge by the Marine Mussel Mytilus edulis". In:
Science, Vol. 117, p. 344-356.
93. B.lumer, M., et al., (1969) "Phytol-Derived C Di- and Tri-olefinic Hy-
drocarbons in Marine Zooplankton and Fishes". In: Biochem., Vol. 8,
p. 4067-4074.
94. Browing, E., (1965) Toxicity and Metabolism of Industrial Solvents
(Elsevier Press, New York), p. 98-102.
95. Carruthers, W., et al., (1967)."1, 2-Benzanthracene Derivatives in a
Kuwait Mineral Oil".. In: Nature, Vol. 213, p. 691-692.
96. Cahnmann, H. J., (1955) "Detection and Quantitative Determination of
Benzopyrene in American Shale Oil". In: Anal. Chem., Vol. 27, p. 1235-
1240.
97. Wedgewood, P., and Cooper, R. L., (1955) "Detection and Determination
of Traces of Polynuclear Hydrocarbons in Industrial Effluents and
Sewage". In: Analyst, Vol. 80, p. 652-654.
98.- Kuratsune, M., and Hirahato, T., (1962) "Decomposition of Polynuclear
Aromatics under Laboratory Illuminations". In: Nat. Cancer Inst.
Monograph, No. 9, p. 117-125.
99. Sawicki, E., et al., (1964) "Application of Thin-Layer Chromatography
to the Analysis of Atmospheric Pollutants and Determination of Benzo(a)
pyrene". In: Anal. Chem., Vol. 36, No. 3, p. 497.
100. Cahnmann, H. J. and Kuratsune, M., (1957) "Determination of Polycyclic
Hydrocarbons in Oysters Collected in Polluted Waters". In: Anal.
Chem., Vol. 29, No. 9, p. 1312-1317.
101. Koe, B. K. and Zechmeister, L., (1952) "The Detection of Carcinogenic
and Other Polycyclic Aromatic Hydrocarbons from Barnacles. II. The
Goose Barnacles (Mitel la polymerous)". In: Arch. Biochem. and
Biophys., Vol. 41, No. 2, p. 396-^03.
102. Cicatelli, Scaccini, (1965) "Studio dei Fenomeni Di Accumulo Del Benzo
3-4 Pirene Nel1'Organism Di Tubiflex". In: Boll, de Pesca.
Piscicolyura e Idrobiologia, Vol. 20, p. 245-250.
103. Andelman, J. B. and Suess, J., (1970) "Polynuclear Aromatic Hydrocarbons
in the Water Environment". In: Bull. W.H.O., Vol. 43, p. 479-508.
104. "The Specter of Cancer", A Special Report. In: E.S.ST., Dec. 1975,
Vol. 9, No. 13, p. 1119.
63
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105. Purchon, R. D., (1968) The Biology of the Mollusca (Pergamon Press,
Oxford), p. 111-125.
106. Payne, J. F., et al., (1978) "Crankcase Oils: Are They a Major Muta-
genie Burden in the Aquatic Environment?" In: Science, Vol. 2004,
p. 329-330.
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APPENDIX A
GC BACKGROUND AND THEORY
As an analytical tool, gas chromatographic effectiveness relies for the
most part upon the type and construction of the column utilized. In the
analysis of petroleum products, it becomes particularly important to know
the restraint that such compounds may impose upon a column due to their
extensively wide range of high boiling polar and non-polar substances. The
type of column utilized in this study was of the open tubular variety where
the absorbant is disposed in a thin film or layer on the inner wall, leaving
an open, unrestricted path through the column for carrier gas flow. The
superiority of open tubular columns for the analysis of a wide boiling range
sample mixture in which closely related isomers and homologs are present,
has been clearly demonstrated!>2. The use of3~° capillary columns for
analysis of complex mixtures is also well documented. In addition, the use
of open tubular capillary columns for the analysis of such wide boiling range
substances from poly-substituted aromatic homologs of benzene and naphtha-
Iene7, to light petroleum oil products , have produced superior chromatogra-
phic results.
The particular type of open tubular column utilized is a SCOT 50 foot x
0.02 inch ID capillary column, coated with the non-polar silicone oil OV-101.
This column was used with particular success by scientists at the Woods Hole
Oceanographic Institute^ for the passive identification of a variety of crude
and processed petroleum products.
The use of an ionization detector with the open tubular capillary column
has been substantiated^. Flame ionization detectors (FID) are detecting
devices which produce a current proportional to the number of ions or elec-
trons formed upon combustion of sample molecules. Hydrogen and oxygen gases
mix at the detector, and are ignited to produce a small flame. As the efflu-
ent enters the burner base and mixes with the gases the flame induces ioniza-
tions of all organic compounds, with its greatest responses to hydrocarbons.
GC Operating Procedures
Set-up and check-out procedures for the Perkin-Elmer 900 GC
Column
50 ft. x 0.02 in. stainless steel SCOT OV-101 Capillary Column
Injector
Temperature set at 250 C + 10 C; use of silicone septum suggested
65
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Carrier Gas
Nitrogen; flow at k ml/min measured at column outlet
Oven . oo
^Temperature programmed from 75 C to 300 C at 6 C/min with isothermal opera-
tion at 300 C for a minimum of 12 minutes or until chromatogram returns to
baseline
Detector
Flame lionization Detector (FID): manifold temperature set at 300 C + 10°C.
Compressed air at kQ psi. Hydrogen at 22 psi. Sensitivity 1 x 10~10 amps/mv
Injections
0.5 to 5.0 ul injections of sample solutions by Hamilton 10 ul syringe de-
pending upon concentrations (split ratio 15:1 installed with a capillary
splitter)
Recorder
1 mv, 0.5 in. span; 1 second response; operated at 0.5 in/min chart speed
with response positive left to right
* Temperature program dial was calibrated periodically to monitor proper
increase in temperature.
Chromatograph are indicated in the operating manual. Unless indicated
to be otherwise, all parameters indicated for operation of the gas chromato-
graphic analyses were adhered to for all samples in this study so that visual
comparison could be made.
The SCOT column was pre-conditioned at 160°C by Perkin-Elmer Co., how-
ever, due to the higher operating temperatures utilized in this study, further
conditioning was required. The following is an outline of the column condi-
tioning operation*:
Nitrogen carrier gas flow through column at k ml/min
(1) 220°C for 2 hours
(2) 250°C for 2 hours
(3) Four injections standard No. 2 fuel oil; temperature program 75°C-
250 C at 6 C/min
(4) 225°C for 20 hours
(5) 250°C for 30 minutes
(6) Five injections standard No. 2 fuel oil; temperature program 75 C-
250°C at 6°C/min
(7) 275°C for 3 hours
(8) 300°C for 1 hour
66
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(9) Two injections No. 2 fuel oil; temperature program 75°C-275°C at
6 C/min, isothermal operation at 275 C for 12 minutes
(10) Two injection standard WCCO in petroleum ether (2:1 dilution) tem-
perature program 75 C-300 C at 6 C/min, isothermal operation at
300°C for 2k minutes
* During this entire operation, the column should be disconnected from the
detector and a plug placed into the detector inlet port.
The recommended operating range on the SCOT capillary column was no
greater than 250 C, however with the high boiling points of the compounds,
the operating temperature range for analysis was extended to 300°C. No glass
liner in the injector port was utilized as a clean-up procedure and only
during the analysis of marine organism extracts was there any sample fraction-
ization performed. Special care was taken to utilize the capillary splitter
for standard sample runs. In addition, a "bake-out" procedure (with column
not attached to the detector) was conducted after an analysis period to remove
high boiling components that may have accumulated on the column.
The practical sample capacity per injection using a capillary splitter is
usually in the order of 10~3 ul for the frequently utilized 0.01 inch I.D,
(.25 mm) open tubular columns. It has been demonstrated^1 however, that by
doubling the diameter of the column used, a direct sample injection without
use of splitter may be possible. Some overloading of the column was experi-
enced and was alleviated by reducing the injection volume on subsequent runs.
After each conditioning period, as a precaution it would be advisable to
run a program sequence to assure that there is no sign of excessive bleed
from the column and to establish a baseline. Subtraction of baseline from a
chromatographic signal response indicates the unresolved portions in sample
profiles.
Analyses of a No. 2 fuel oil or the Cg-C3$ standards several times con-
secutively can serve as a check on procedure and the working conditions of
the gas chromatographic system so that any fouling or increases in variability
in chromatograms will be detected. A temperature program run without in-
jecting any sample to observe the extent of column contamination or bleeding
characteristics after a series of injections is also a good check on system
performance, and should be conducted periodically.
Since the cold column (75 C at the start of the program) is attached to
a hot injector, many high boilers are trapped on the columns front-end and
may accumulate in sufficient quantities to cause septum bleed or exhibit
"memory effects" on the next program. These "memory effects" could be attri-
butable to poor syringe technique, contaminated gases entering the instrument,
improper maintenance, or the build-up of residues on the septum12. As a stan-
dard procedure, the septum was changed after a set of 10 to 12 injections.
To eliminate the problem of "memory effects" a bake-out procedure was again
performed after periods of disuse by heating the oven to 300°C for 24 minutes,
cooling to 75°C and then programming to 300°C at 6°C/min. The baseline was
observed for any contamination on the column.
67
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LJV-F luorescence Spectroscopy Background and Theory
Fluorescence spectroscopy as an analytical tool has found extensive use
in a variety of clinical and research projects. Its original application had
been directed at such diversified studies as the structural state of pro-
teins1^ as well as the characterization of specific petrochemical prod-
ucts^* '5. Recent investigations^" have exhibited the technique's ability to
detect trace quantities of petroleum derived products in oceanic waters.
The theory of fluorometric analysis is that energy absorbed by molecules
cause them to move to a condition of higher energy or what has been termed an
"excited state". The particular wavelength of radiation (light quantum)
emitted by these excited molecules is specific for their particular electronic
characteristics. This quantity of light emitted in the fluorescence process
is usually of a lower energy than the amount absorbed by the molecule. There-
fore, the corresponding loss of energy by a molecule upon returning from the
excited state to the ground state becomes the characterizing fluorescence for
the molecular species under investigation. The uniqueness of UV-fluorescence
analysis is that by exciting any two fluorescing compounds at a specific exci-
tation frequency, unique emission profiles for those compounds will be pro-
duced. It is the use of these profiles along with their correlation with
standard profiles that determines whether or not a particular class of com-
pounds exists in an environmental sample.
It has been noted that some radiation-free processes occur where mole-
cules return to their ground state after being excited without the emission
of a photon, converting all the excitation energy into heat. Little is
understood of this process, and due to the inherent inefficiency of this
"internal conversion" process, it is believed1? to be responsible for a rela-
tively small portion of the total excitation energy in most molecules. It is
believed^ that this radiationless process does not exist in aromatic hydro-
carbons and therefore should not interfere with analyses.
Fluorescence spectroscopic instrumentation is usually characterized by
the use of two monochromators functioning independently of each other. The
fluorescence process first requires that energy at a particular wavelength
excite a molecule by some external source (excitation monochromator). In the
case of the MPF-3 UV-fluorescence spectrophotometer (Perkins-Elmer Co., Nor-
walk, Conn.) this is accomplished by a 150 Watt Xenon arc. The excited
sample, with emission of light at a long wavelength, is now the source of
emitted energy for the emission monochromator. The MPF-3 has independent
monochromators that may be used to produce from a sample, both emission and
excitation frequency on the excitation monochromator and then scanning a .
range of emission wavelengths, the emission spectrum of the sample may be
recorded. It is also possible to excite a particular sample at all possible
excitation frequencies while manually scanning the emissions at each of these
particular excitation wavelengths. Both of these techniques were utilized in
the fluorescence phase of this study.
Light from the sample is emitted in all directions. The optical set-up
of the emission monochromator is usually arranged to take fluorescence from
the sample at an angle other than 180° in relation to the exciting light. The
68
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density of the sample being analyzed dictates the angle at which the incident
light will be measured (Figure A1). For example, the low density solution,
analyzed in this study, required fluorescence radiation from the sample to be
emitted at 90 relative to the exciting light. At higher densities, such as
with highly viscous or turbid samples, an angle of kS° or less may be used.
Due to the unique selectivity (especially for compounds with aromatic
ring structures) and high sensitivity, fluorescence spectroscopy has been
utilized as an analytical technique for samples with concentrations ranging
from nanograms to milligrams per mi 11i1i
fxcirto
Figure Al.
69
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REFERENCES FOR APPENDIX A
1. Zlatkis, A. and Lovelock, J. E., (1959) "Gas Chromatography of Hydrocar-
bons Using Capillary Columns and lonization Detectors". In: Anal. Chem.
Vol. 31, p. 620-621.
2. Lipskey, S. R., Landowne, R. A. and Lovelock, J. E., (1959) "Separation
of Lipids by Gas Chromatography". In: Anal. Chem., Vol. 45, p. 825-856.
3. Desty, D. H., Goldrup, A. and Whyman, B. H. F., (1959) "Potentialities of
Coated Capillary Columns for Gas Chromatography in the Petroleum Indus-
try". In: J. Instit. of Petrol., Vol. 45, p. 287-298.
4. Durrett, L. P., et al., (1963) "Component Analysis of Isoparaffin-01efin
Alkylate by Capillary Gas Chromatography". In: Anal. Chem., Vol. 35,
p. 637-641.
5. Schwartz, R. D. and Brassaux, D. J., (1963) "Resolution of Complex Hydro-
carbon Mixtures by Capillary Column Gas-Liquid Chromatography". In:
Anal. Chem., Vol. 35, p. 1374-1382.
6. Merchant, P., Jr., (1968) "Resolution of C^-C^ Petroleum Mixture by
Capillary Gas Chromatography". In: Anal. Chem., Vol. 40, p. 2153-2158.
7. Ettre, L. S., (1965) Open Tubular Columns in Gas Chromatography (Plenum
Press, New York), Figure 5, p. 19.
8. Ibid., p. 57, Figure 25.
9. Zafirious, 0., Blumer, M., and Meyers, J., (1977) "Correlation of Oils
and Oil Products by Gas Chromatography". In: USEPA Publ. (-600/2-77-
163).
10. Zlatkis, A., (1963) "lonization Detectors and Capillary Columns". In:
Lectures on Gas Chromatography - 1962, Szymanski, H. A., ed., (Plenum
Press, New York), p. 87-104.
11. Ettre, L. S., (1965) op. cit., p. 70-71.
12. Downs, H. D., Puree M., J. E. and.Condon, R. D., (1-969) "Identification
and Elimination of Contaminants in a High Sensitivity Gas Chromatographic
System". Presented at the Pittsburgh Conference on Analytical Chemistry
and Applied Spectroscopy, Cleveland, Ohio, p. 4-5.
13. McCluore, W. 0. and Edelman, G. J., (1966) "Fluorescent Probes for Con-
formational States of Proteins". In: Biochem., Vol. 5, No. 6, p. 1908.
70
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14. Thurston, A. D. and Knight, R. W., (1971) "Characterization of Crude and
Residual-Type Oils by Fluorescence Spectroscopy". In: Env. Sci. and
Tech., Vol. 5, No. 1, p. 64-69.
15. Zitko, V. and Carson, W. W., (1970) "The Characterization of Petroleum
Oils and Their Determination in the Aquatic Environment". In: Fish.
Res. Brd. Can. Technical Report No. 217, p. 2-27.
16. Keizer, R. D. and Gordon, D. C., Jr., (1973) "Detection of Trace Amounts
of Oil in Sea Water by Fluorescence Spectroscopy". In: J. Fish. Res.
Bd. of Canada, Vol. 30, No. 8, p. 64-69.
17. Hercules, B. H., (1966) Fluorescence and Phosphorescence Analysis (Inter-
science Publishers, John Wiley Press, New York), p. 19.
18. Kellogg, R. E. and Bennett, R. G., (1964) "Radiationless Intermolecular
Energy Transfer". In: J. Chem. Phys., Vol. 41, p. 3042.
19. Smith, H. F., (1968) "Luminescence Spectroscopy - A Versatile Analytical
Tool". In: Research and Development, p. 23.
71
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APPENDIX B. GAS CHROMATOGRAMS OF SOME CRUDE OIL PRODUCTS.
Bachaquero Crude
72
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South Louisiana Crude
-------
Nigerian Medium Crude
-------
APPENDIX C. GC-MS DATA ON Mya arenaria L. EXTRACTS
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77
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
4. TITLE AND SUBTITLE
AUTOMOTIVE CRANKCASE OIL IN WASTEWATER EFFLUENTS:
DETECTION IN A COASTAL WETLANDS ENVIRONMENT
7. AUTHOR(S)
John T. Tanacredi and Dennis Stainken
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Department of Environmental Health Sciences
Hunter College of City University of New York
| New York, New York 10029
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory-Cin. , OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 1*5263
3. RECIPIENT'S ACCESSION>NO.
5. REPORT DATE
March 1981
6. PERFORMING ORGANIZATION CODE
3. PERFORMING ORGANIZATION REPORT N
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERE
Final Report
14. SPONSORING AGENCY CODE
EPA/600/li»
15. SUPPLEMENTARY NOTES
Project Officer: Uwe Frank (201-321-6626)
Samples from four sewage treatment facilities which discharge into Jamaica Bay,
New York, were analyzed for the presence of waste automotive oil products. UV-
fluorescence spectroscopic techniques were utilized to qualitatively identify waste
petroleum hydrocarbons in effluents of water pollution control plants by comparison
of sample profiles to profiles generated by standard reference oils. Within the
Bay, surface waters and a benthic bivalve (Mya arenaria L.) were also analyzed for
petroleum hydrocarbons using fluorescence techniques, and gas chromatography. GC-Mas
spectroscopy was used to further aid in establishing the presence of petroleum hydro-
carbons in the bivalves. Synchronized excitation fluorescence spectroscopy was used
in this investigation to confirm the presence of waste automobile oil in the environ-
mental samples. Results strongly indicated the presence of hydrocarbons associated
with waste automotive petroleum products in most of the extracts of effluent samples,
surface water samples and bivalves.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Chemical analysis
Wastes
Clams
Oils
18. DISTRIBUTION STATEMENT
Release to Publ ic
b.lOENTIFIERS/OPEN ENDED TERMS
Fingerprinting
Crankcase oi 1
Automot i ve oil
Fluorescence Spectro-
scopy
Fate 5 Effect
19. SECURITY CLASS (This Repon)
Unclassified
20. SECURITY CLASS (This page)
Unclassi f ied
c. COSATI Field/Group
07C
11H
21. NO. OF PAGES
88
22. PRICE
EPA Form 2220-1 (9-73)
78
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