Results are presented on a computerized gas chromatograph-mass spectrometer analysis of methylene chloride and n-heptane extracts of a No. 2 fuel oil accommodated estuarine water sample. The analytical method is briefly described, and the limitations on the identifications are categorized. Some attempt was made to determine major and trace constituents in the water accommodate. Altogether 66 hydrocarbon compounds were identified specifically, and 75 compounds were partially identified. Seven compounds could be recognized as major constituents of the water accommodated oil and ten were present only as traces. The aromatic compounds found were alkyl benzenes, naphthalene, tetralin, indane, biphenyl, fluorene, anthracene, and some of their alkyl substituted isomers in the range of carbon numbers C7 to C15. Four n-alkanes, C10 to C13, were found along with four other assorted hydrocarbons

Bieri, R. H.

Lewis, B. W.

Walker, A. L.

English

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NASA TECHNICAL NASA TM X-72009
MEMORANDUM COPY NO.
0
C1Jr-
HYDROCARBONS IDENTIFIED IN EXTRACTS FROM ESTUARINE
WATER ACCOMMODATED NO. 2 FUEL OIL BY
GAS CHROMATOGRAPHY-MASS SPECTROMETRY
by Beverley W. Lewis, Ann L. Walker, and Rudolf H. Bieri
Reproduced by
NATIONAL TECHNICAL
INFORMATION SERVICE
US Department of Commerce
Springeld, VA. 22151
(NASA-TM-X-72009) HYDROCARBONS IDENTIFIED N74-32580
IN EXTRACTS FROM ESTUARINE WATER
ACCOMMODATED NO. 2 FUEL OIL BY GAS
CHROMATOGRAPHY-MASS SPECTROMETRY (NASA): Unclas
12 p HC $3.00 ""-1 07D G3/06 48530
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NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
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https://ntrs.nasa.gov/search.jsp?R=19740024467 2020-03-23T04:56:07+00:00Z
1. Report No. 2. Government Accession No. 3. Recipient's Catalog No.
NASA TM X 72009
4. Title nd Subtitle 5. Report Date
Hydrocarbons Identified in Extracts from Estuarine Wate Sept. 4,, 197.4-
Accommodated No. 2 Fuel Oil by Gas Chromatography-Mass 6. Performing Orgnizatio Code
Spectrometry 67.720
7. Author(s) 8. Performing Organization Report No.
Beverley W. Lewis, Ann L. Walker, & Rudolf H. Bieri
10. Work Unit No.
iz.at o-'Name and Address 176-53-32-03
WNAA, a0n leyResearch Center, Hampton, VA
and 11. Contract or Grant No.
Virgilia Institute of4Marine S'cience, GloucesterPt., V
13. Type of Report and Period Covered
12. Sponsoring Agency Name and Address
NASA, Langley Research Center, Hampton, VA
and 14. Sponsoring Agency Code
Virginia Institute of Marine Science, Gloucester Pt., Vk Data
15. Suplementary Notes
Interim technical information release subject to possible revision or later
formal publication.
16. Abstract
This data report presents the results of a computerized gas chromatograph-
mass spectrometer analysis of methylene chloride and n-heptane extracts of a
No. 2 fuel oil accommodated estuarine water sample. The analytical method
is briefly described and the limitations on the identifications are categorized.
Some attempt was made to determine major and trace constituents in the water
accommodate.
Altogether 66 hydrocarbon compounds were identified specifically and
75 compounds were partially identified. Seven compounds could be recognized
as major constituents of the water accommodated oil and ten were present only
as traces. The aromatic compounds found were alkyl benzenes, naphthalene,
tetralin, indane, biphenyl, fluorene, anthracene, and some of their alkyl
substituted isomers in the range of carbon numbers C7 to C1 5 . Four
n-alkanes, C1 0 to C1 3 , were found along with four other assorted hydrocarbons.
17. Key Words (Suggested by Author(s)) (STAR category underlined) 18. Distribution Statement
Shemical Analysis, Oil Pollution, Hydro- Unclassified-Unlimited
!arbon Analysis, Compound Identification,
.o. 2 Fuel Oil, Water Accommodated Oil
PRICES SUBJECT TO CHAMG
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Unclassified Unclassified 10 $3.00
*Available from The National Technical Information 
Service, Springfield. Virginia 22151
SilTIF/NASA Scientific and Technical Information Facility. P.O. Box 33. College Park. MD 20740
HYDROCARBONS IDENTIFIED IN EXTRACTS FROM ESTUARINE
WATER ACCOMMODATED NO. 2 FUEL OIL BY
GAS CHROMATOGRAPHY-MASS SPECTROMETRY
by Beverley W. Lewis and Ann L. Walker
Langley Research Center
and
Rudolf H. Bieri
Virginia Institute of Marine Science
SUMMARY
This data report presents the results of a computerized gas chromatograph-
mass spectrometer analysis of methylene chloride and n-heptane extracts of a
No. 2 fuel oil accommodated estuarine water sample. The analytical method
is briefly described and the limitations on the identifications are categorized.
Major and trace constituents in the water accommodate were determined.
Altogether 66 hydrocarbon compounds were identified specifically and
75 compounds were partially identified. Seven compounds could be recognized
as major constituents of the water accommodated oil and ten were present only
as traces. The aromatic compounds found were alkyl benzenes, naphthalene,
tetralin, indane, biphenyl, fluorene, anthracene, and some of their alkyl
substituted isomers in the range of carbon numbers C7 to C15. Four
n-alkanes, CIO to C1 3 , were found along with four other assorted hydrocarbons.
Northrop Services, Inc. (Contractor to Langley Research Center)
INTRODUCTION
The detailed analyses of petroleum hydrocarbon compounds which dissolve
in or are accommodated by estuarine water systems are needed for ecological
studies of the fate and effect of oil spills. Until recently, the available
analytical techniques and instruments limited the progress in analyzing these
extremely complex samples, each of which contain hundreds of compounds. The
development of computerized gas chromatograph mass spectrometer (GS-MS)
systems has now placed a much more detailed analysis of these types of
samples within reach. This report presents these data resulting from the
investigation of the use of a low resolution GC-MS system to analyze extracts
of York River water which had accommodated a No. 2 fuel oil in a laboratory
equilibration process. Several GC, support coated open tubular (SCOT)
columns were evaluated in the GC-MS. Two columns were selected to separate
the aromatic fractions of oil for the MS analysis. They were Didecyl
phthalate (DDP) and OV-25, the DDP giving better separation of the alkyl
benzenes and the OV-25 giving better separations for the substituted
naphthalenes.
This work was the preliminary phase of a continuing program to develop
analytical capabilities for identifying the major hydrocarbon compounds in
estuarine environmental samples due to oil pollution. One objective was
to identify as many of the gas chromatographically separated compounds as
possible, and to indicate which ones were the most abundant. The results of
this phase have shown that the techniques and equipment are capable of a
rather detailed analysis of this type of sample, and with further refinements
will be satisfactory for ecological studies of the fate and effect of oil in
estuaries. The purpose of this report is to make these data obtained available
rather than to evaluate the method, since the methods are still being developed
and refined.
2
APPARATUS AND PROCEDURES
A System/150 computerized data acquisition unit was used to obtain data
from a Finnigan 1015 quadrupole mass spectrometer interfaced to a Varian
Aerograph gas chromatograph oven. Support coated open tubular (SCOT) GC
columns with either DDP or OV-25 were used under isothermal and temperature-
programed conditions to separate sample components.
The oil-accommodated water was extracted with either n-heptane or
methylene chloride. In the case of n-heptane, the extract was concentrated
at low temperature to a volume on the order of 0.3 ml and injected as the
n-heptane solution. However, the methylene chloride was evaporated completely
and the hydrocarbons were then dissolved in a small amount of n-heptane to
provide the sample for injection.
Table I gives the GC parameters for the three pertinent runs.
The entire effluent from the column was fed directly into the ionization
chamber of the mass spectrometer. The filament in the ion source was turned
off just prior to solvent elution and remained off three-four minutes until
the pressure on the manifold had returned to its normal operating level of
<5 X 10- 5 torr. A real time total ion current chromatogram was obtained on a
Houston Instruments digital plotter, and at the completion of a run, a
reconstructed chromatogram, normalized to the highest peak, was also pro-
duced. Generally several series of mass searches were then made to detect
compound classes having specific molecular weights and to determine if any
components had been partially or completely obscured by simultaneous elution
of other material. Mass spectral data in the form of ion current intensities
and m/e for each ion fragment were printed out numerically on the teletype for
each GC peak of interest.
3
Whenever possible, identifications were made by comparing the actual
GC retention time and the mass spectral data of standard compounds with that
of the sample. These compounds are listed in the a sections of tables II, III
and IV. When standard compounds were not available, the mass spectral data were
compared with literature-data for compound classification, and further
identification by isomers was made from boiling point data and GC retention
times. Such compounds are listed in the b sections of the tables. In
cases where neither standards nor boiling point data were available, partial
identifications were made on the basis of literature mass spectral data
alone. The similarity of mass spectral fragmentation patterns of aromatic
isomers, often coupled with the large number of isomers (e.g. C5-substituted
benzenes), made it extremely difficult to identify the nature and position of
the alkyl substituents. Partially classified compounds are found in the c
sections of the tables. All identifications were made by manual comparisons
with mass spectra given in the Aldermaston collection or obtained by running
standards on our Finnigan GC-MS'system.
RESULTS AND DISCUSSION
Tables II, III, and IV list the compounds identified along with the mode
of identification (a, b, or c) and an indication of whether the compound was
a major (M) or trace (T) constituent.
Table II lists the benzene compounds found in the methylene chloride
extract of the No. 2 fuel oil accommodated York River water. It is noted
that all isomers of dimethyl-, diethyl-, methyl-ethyl-, methyl-isopropyl-,
trimethyl-, and tetramethyl-benzenes were found. All dimethyl-ethyl benzenes
were found except the 1, 3-5-isomer. Altogether 30 substituted benzenes were
identified and 16 more were separated and partially identified.
4
Table III shows the napthalenes and tetralins (1, 2, 3,
h-tetrahydronapthalenes) found in the methylene chloride and a n-heptane
extract of the accommodate. The monoalkyl naphthalenes containing either a
methyl or ethyl group are complete. Four of the ten possible isomers of
dimethylnapthalene are not identified with respect to their structure, but
two of these were separated. The missing two isomers were either not
present above the detection limits or were co-eluted with a relatively
abundant compound. Only two of the 15 possible trimethylnaphthalenes could
be specifically identified. Others may be among the seven separated
C -substituted naphthalenes. All naphthalenes of either higher substitution
or molecular weight remain of unknown specific structure because their
mass spectra do not allow further distinction. All of the possible
methyltetralins were identified and, together with tetralin itself, they
were among the most abundant compounds found in the water extracts. Ethyl-,
dimethyl-, and trimethyl-tetralins were separated and identified by their
mass spectra but no specific isomers could be assigned. Thus, 18 naphthalenes
and tetralins could be identified completely, while 30 more were separated
and partially identified.
Table IV contains the indanes, biphenyls, and a few polyaromatic
compounds and some of their alkylated forms which were found in the methylene
chloride extract. Only a few of the compounds in this group were specifically
identified, among which were two methyl indanes, biphenyl (a major constitutent),
three methyl biphenyls, acenaphthene, fluorene, anthracene, four n-alkanes and
dibenzofuran (the only heterocompound found). A total of 18 compounds were
specifically identified with 28 others separated and partially identified.
5
CONCLUDING REMARKS
This work has demonstrated the capabilities of the computerized GC-MS
to separate and analyze many of the compounds in a complex environmental
sample and has indicated some areas where improvements or refinements in
techniques are needed to optimize the utility of the method. These data are
presented as a guide to the compounds found in a water accommodate of a
No. 2 fuel oil for use in related research.
Altogether 66 hydrocarbon compounds were identified specifically and
75 compounds were partially identified. Some seven compounds could be
recognized as major constituents of the water accommodated oil and ten
were present only as traces.
6
TABLE I
GC PARAMETERS FOR PERTINENT RUNS
Run GULF 3 GULF 7 GULF 8
Column DDP OV-25 OV-25
Length 100 ft 50 ft 50 ft
Diameter 0.02 in 0.02 in 0.02 in
Temperature
Injection Port 2080 C 2050 C 2050 C
Oven-Isothermal 1400 C for 121 min 1080 C for 45 min 1080 C for 45 min
1200 C for 210 min
Oven-Programed --- 10 /min to 2200 C 10 /min to 2200 C
Sample Size 1.50 pk 0.45 ml 1.05 Pk
Sample Solvent n-heptane n-heptane n-heptane
Carrier Gas 1.5 cc/min He 1.5 cc/min He 1.5 cc/min He
Extraction Solvent methylene chloride methylene chloride methylene chloride
7
TABLE II
BENZENE COMPOUNDS FOUND IN A METHYLENE CHLORIDE EXTRACT OF AN ESTUARINE
WATER ACCOMMODATE OF A NO. 2 FUEL OIL BY GC - MS
MONOSUBSTITUTED BENZENES, C7 to C10 TRISUBSTITUTED BENZENES, C9 & C10
a ETHYLBENZENE T a 1,2,3 - TRIMETHYLBENZENE
n-PROPYLBENZENE T 1,2,4 - TRIMETHYLBENZENE
ISOPROPYLBENZENE T 1,3,5 - TRIMETHYLBENZENE
SEC -BUTYLBENZENE T b 1, 2 - DIMETHYL-3-ETHYLBENZENE
ISOBUTYLBENZENE T 1,2 - DIMETHYL-4-ETHYLBENZENE
BISUBSTITUTED BENZENES, C8 to C10 1,3 - DIMETHYL-2-ETHYLBENZENE1,3 - DIMETHYL-4-ETHYLBENZENE
a o - XYLENE 1,4 - DIMETHYL-2-ETHYLBENZENE
m - XYLENE TETRASUBSTITUTED BENZENES, Cp - XYLENE 10
o - DIETHYLBENZENE a 1,2,4,5 - TETRAMETHYLBENZENE
m -DIETHYLBENZENE T b 1,2,3,4 - TETRAMETHYLBENZENE
p - DIETHYLBENZENE 1,2,3,5 - TETRAMETHYLBENZENE
o - ETHYLTOLUENE C & C ISOMERS SEPARATED, NOT SPECIFICALLYm -ETHYLTOLUENE 12
m -ETHYLTOLUENE IDENTIFIEDNO.
p - ETHYLTOLUENE
c C5 - SUBSTITUTED BENZENES 16
b . o-n- PROPYLTOLUENE C6 - SUBSTITUTED BENZENE T 1
p -n-PROPYLTOLUENE
T = TRACE, M = MAJOR CONSTITUENT
o - ISOPROPYLTOLUENE T
a INDICATES IDENTIFICATION BY COMPARISON WITH
m- ISOPROPYLTOLUENE STANDARDS RUN ON SAME GC - MS
p - ISOPROPYLTOLUENE T b IDENTIFIED BY B.P. & GC RETENTION TIME DATA
AND COMPARISON WITH M. S. DATA IN LITERATURE
c CORRELATED WITH M.S. LITERATURE DATA
NAPHTHALENE COMPOUNDS FOUND IN A METHYLENECHLORIDE OR HEPTANE EXTRACT
OF AN ESTUARINE WATER ACCOMMODATE OF A NO. 2 FUEL OIL BY GC-MS
a NAPHTHALENE, C10 H8 1,2,3, 4-TErRAHYDRONAPHTHALENES (TETRALINS)
b 1, 2, 3,4-TETRAHYDRONAPHTHALENE, C 10H12MONOSUBSTITUTED NAPHTHALENES, C & C12
MONOSUBSTITUTED-TETRALINS, C11
a 1- METHYLNAPHTHALENE M
-2- METHYLNAPHTHALENE b 1 - METHYLTETRALIN
1- ETHYLNAPHTHALENE 2 - METHYLTETRALIN M
5 - METHYLTETRALIN M2- ETHYLNAPHTHALENE M6 - METHYLTETRALIN M
BISUBSTITUTED NAPHTHALENES, C
C12 12& C13 ISOMERS SEPARATED, NOT SPECIFICALLY
a 1,6,& 1,3 - DIMETHYLNAPHTHALENE M IDENTIFIED
1,5 - DIMETHYLNAPHTHALENE NO.
2,6 - DIMETHYLNAPHTHALENE c ETHYLTETRALIN 1
2,3 - DIMETHYLNAPHTHALENE DIMETHYLTETRALINS 9
1,4 - DIMETHYLNAPHTHALENE TRIMETHYLTETRALIN 1
C -SUBST'D TETRALIN 1
TRISUBSITUTED NAPHTHALENES, C13STD TETRALIN 1
a 2,3,5 - TRIMETHYLNAPHTHALENE
2, 3,6 - TRIMETHYLNAPHTHALENE
C12 to C15ISOMERS SEPARATED,NOT SPECIFICALLY
IDENTIFIED
NO.
c DIMETHYLNAPHTHALENES 2
C -SUBST'D. NAPHTHALENES 7
C -SUBST'D. NAPHTHALENES 8
C5-SUBST'D.NAPHTHALENE 1
~~5-
TAbLiE IV
INDANES, BIPHENYLS, AND OTHER ORGANICS FOUND IN A METHYLENECHLORIDE EXTRACT OF
AN ESTUARINE WATER ACCOMMODATE OF A NO. 2 FUEL OIL BY GC-MS
INDANES, C9 to C11 HIGHER CONDENSED RING HYDROCARBONS,C12to C15
b INDANE, C H T
- METHYL1INNE a ACENAPHTHENE C12HIo
2- METHYLINDANE FLUORENE, C 3H10
ISOMERS SEPARATED, NOT SPECIFICALLY ANTHRACENE, C14H10IDENTIFIED
cNO. ISOMERS SEPARATED, NOT SPECIFICALLY IDENTIFIED NO
c METHYLINDANES 2 NO.
ETHYLINDANE 1 c METHYLFLUORENES 4
DIMETHYLINDANES 6 C -SUBST'D FLUORENES 3
I THYLANTHRACENES 4
BIPHENYLS, 12 15 SATURATED ALIPHATIC HYDROCARBONS, C to C
a BIPHENYL, C12H 10 M a n - DECANE, C10H22
b 2 - METHYLBIPHENYL
3 - METHYLBIPHENYL n - UNDECANE, C1 1H24
4 - METHYLBIPHENYL n - DODECANE, C12H26
ISOMERS SEPARATED,NOT SPECIFICALLY b n - TRIDECANE, C13H28IDENTIFIED
c DIMETHYLBIPHENYLS 3 OTHER ORGANICS, 12 to 14
C -SUBST'D BIPHEN.YLS 2C -SUBST'D aBPHEN DIBENZOFURAN, C1H 0C -SUBST'D BIPHENYLS 3 12 8
DIPHENYLMETHANE, C13H12
c PHENYLCYCLOHEXANE, C12H16
1,1 - DIPHENYLETHENE,C 14H12 T


Hydrocarbons identified in extracts from estuarine water accommodated no. 2 fuel oil by gas chromatography-mass spectrometry

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