ESL-TR-87-09
ENVIRONMENTAL FATE AND
EFFECTS OF SHALE-DERIVED
JET FUEL
P.M. PRITCHARD, T.P. MAZIARZ, L.H. MUELLER,
A.W. BOURQUIN
U.S. ENVIRONMENTAL PROTECTION AGENCY
ENVIRONMENTAL RESEARCH LABORATORY
GULF BREEZE FL 32561
JUNE 1988
FINAL REPORT
OCTOBER 1984 - MARCH 1986
APPROVED FOR PUBLIC RELEASE: DISTRIBUTION UNLIMITED
ENGINEERING & SERVICES LABORATORY
AIR FORCE ENGINEERING & SERVICES CENTER
TYNDALL AIR FORCE BASE, FLORIDA 32403
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UNCLASSIFIED
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Environmental Research Laboratory
Gulf Breeze FL 32561
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ESL-TR-87-09
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HQ AFESC/RDVS
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9. PROCUREMENT INSTRUMENT IDENTIFICATION NUMBER
MIPR N85-16
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PROGRAM PROJECT TASK
ELEMENT NO. NO. NO
62601F 1900 20
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ACCESSION NO.
75
11. TITLE (Include Security Classification)
Environmental Fate and Effects of Shale-Derived Jet Fuel
12. PERSONAL AUTHOR(S)
Pritchard, P.H. ; Maziarz, T.P.; Mueller,
13a. TYPE OF REPORT
Final
13b. TIME COVERED
FROMOct 84 ToMar
L.H.; Bourquin, A.W.
86
14. DATE OF REPORT (Year, Month, Day)
June 1988
15. PAGE COUNT
97
16. SUPPLEMENTARY NOTATION
Availability of this report is specified on reverse of front cover.
17. COSATI CODES
FIELD
06
07
GROUP
13
03
SUB-GROUP
18. SUBJECT TERMS (Continue on reverse if necessary and identify by block
Biodegradation Shale-Derived Fuel
Jet Fuel
number)
19. ABSTRACT (Continue on reverse if necessary and identify by block number)
Tests were conducted to compare the environmental fate of shale oil-derived jet fuel
with that of petroleum-derived jet fuel. These tests included chemical characterization
of the fuels, and the water-soluble fraction of each fuel, also measurement of volatiliza-
tion and biodegradation rates in laboratory systems designed to simulate three disparate
aquatic environments. No major differences in the volatilization and biodegradation rates
of the two fuels were found. Differences in composition were generally small and should
not cause the behavior of the fuels in aquatic environments to differ.
20. DISTRIBUTION /AVAILABILITY OF ABSTRACT
X2 UNCLASSIFIED/UNLIMITED D SAME AS RPT. d DTIC USERS
MICHAEL V. HENLEY
21. ABSTRACT SECURITY CLASSIFICATION
UNCLASSIFIED
22b. TELEPHONE (Include Area Code)
(904) 283-4297
22c. OFFICE SYMBOL
HO AFESC/RDVC
3D Form 1473, JUN 86
Previous editions are obsolete.
SECURITY CLASSIFICATION OF THIS PAGE
j.
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PREFACE
This report was prepared by the Microblal Ecology and Biotechnology
branch of the U.S. Environmental Protection Agency at Gulf Breeze, FL.
The research was supported by an interagency agreement RW57931194-01-1
through the Air Force Engineering and Services Center, Engineering and
Services Laboratory at Tyndall Air Force Base, FL 32403. Captain Robert
C. Beggs and Mr. Michael V. Henley served as Project Officers for the
AFESC/RD.
This report covers work performed between October 1984 and March
1986.
The authors would like to thank C.R. Cripe, W.T. Gilliam, and E.J.
O'Neill for their analytical support and technical review of this work.
The assistance of M. Woehle, A. Quarles, T. Baker and P. Paradis is
greatly appreciated. Val Caston is thanked for her typing and editing.
This report has been reviewed by the Public Affairs Office (PA) and
is releasable to the National Technical Information Service (NTIS). At
NTIS, it will be available to the general public, including foreign
nationals.
This report has been reviewed and is approved for publication.
MICHAEL V. HENLEY
Project Officer
THOMAS J. WALKER, Lt Col, USAF, BSC
Chief, Environics Division
<-— ^
3NNETH T. DENBLEYKER, Maj, USAF
Chief, Environmental Sciences Branch
LAWRENCE D. HOKANSON, Colonel, USAF
Director, Engineering and Services
Laboratory
ill
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TABLE OF CONTENTS
SECTION Page
I INTRODUCTION 1
A. OBJECTIVE 1
B. BACKGROUND 1
C. SCOPE/APPROACH 6
II METHODS
A. JET FUEL 7
B. INSTRUMENT CONDITIONS 7
C. METHOD REFINEMENTS 8
1. Extraction Procedure 8
2. Quiescent Bottle Test 9
D. SAMPLING SITES 12
E. COMPOSITIONAL ANALYSIS 12
1. Neat Fuel 12
2. Water Soluble Fraction 14
F. TOXICITY TESTS 15
G. DISSOLVED ORGANIC CARBON 15
H. JET FUEL EVAPORATION RATES 16
III RESULTS
A. COMPOSITIONAL ANALYSIS 17
1. Neat Fuel 17
2. Water Soluble Fraction 17
B. BOTTLE TEST OPTIMIZATION 22
C. QUIESCENT BOTTLE TESTS 22
1. Range Point 22
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TABLE OF CONTENTS
(CONCLUDED)
Title
Section Page
2. Bayou Chico „ 38
3. Escambia River 56
D. TOXICITY TESTS 56
E. DISSOLVED ORGANIC CARBON 56
F. JET FUEL EVAPORATION RATE 76
IV CONCLUSIONS 80
V RECOMMENDATIONS .... 88
REFERENCES 90
VI
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LIST OF FIGURES
Figure Title Page
1 Extraction Methodology with 500 mg/n Sediment 10
2 Extraction Methodology with 5,000 mg/x. Sediment 11
3 Silica Gel Fractionation 20
4 Effect of Sediment Concentration 23
5 Total Hydrocarbon Loss in Range Point Bottle Test 24
6 Loss of Ethylcyclohexane and Benzene in Range Point Test 27
7 Loss of Cyclohexane and Methylcyclohexane in Range Point Test 28
8 Loss of Methyl benzene and Ethyl benzene in Range Point Test 29
9 Loss of Isopropylbenzene and jri-Xylene in Range Point Test 30
10 Loss of £-Xylene and £-Xylene in Range Point Test 31
11 Loss of 1,3,5-Trimethylbenzene and 1,2,4-Trimethylbenzene
in Range Point Test 32
12 Loss of 1,2,3-Trimethylbenzene and Indan in Range Point Test 33
13 Loss of Heptane and Octane in Range Point Test 34
14 Loss of Naphthalene in Range Point Test 35
15 Loss of Nonane and Decane in Range Point Test 36
16 Loss of Pentadecane and Hexadecane in Range Point Test 37
17 Decane Mineralization Following Escambia River Test 74
18 Toluene Toxicity in Range Point Water 75
19 Solubility of Nonane versus DOC 77
20 Solubility of 1,3,5-Trimethylbenzene versus DOC 78
21 Jet Fuel Evaporation Rate 79
vii
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LIST OF TABLES
Table Title Page
1 PHYSICAL CHARACTERISTICS OF JET FUEL 3
2 COMPARISON OF SHALE-DERIVED JP-4 WITH PETROLEUM-DERIVED JP-4,
LITERATURE VALUES 4
3 LIST OF COMPONENT HYDROCARBON MONITORED THROUGHOUT STUDIES 14
4 COMPARISON OF SHALE-DERIVED JP-4 WITH PETROLEUM-DERIVED JP-4,
ACTUAL VALUES 18
5 WATER SOLUBLE-FRACTION COMPONENTS 21
5a COMPARISON OF DISAPPEARANCE RATES IN STERILE AND ACTIVE
RANGE POINT SYSTEMS 25
6 DATA FROM BAYOU CHICO BOTTLE TEST, STERILE WATER WtTH SJP-4 39
7 DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE WATER WITH SJP-4 41
8 DATA FROM BAYOU CHICO BOTTLE TEST, STERILE SEDIMENT WITH SJP-4 43
9 DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE SEDIMENT WITN SJP-4 45
10 DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE WATER WITH PJP-4 47
11 DATA FROM BAYOU CHICO BOTTLE TEST, STERILE WATER WITH PJP-4 49
12 DATA FROM BAYOU CHICO BOTTLE TEST, STERILE SEDIMENT WITH PJP-4 51
13 DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE SEDIMENT WITH PJP-4 53
14 COMPARISON OF DEGRADATION RATES IN THE BAYOU CHICO TEST 55
15 DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE WATER WITH SJP-4 57
16 DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE WATER WITH SJP-4 59
17 DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE SEDIMENT WITH SJP-4 61
18 DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE SEDIMENT WITH SJP-4 63
19 DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE WATER WITH PJP-4 65
20 DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE WATER WITH PJP-4 67
21 DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE SEDIMENT WITH PJP-4 69
viii
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LIST OF TABLES (CONCLUDED)
Table Title Page
22 DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE SEDIMENT WITH PJP-4 71
23 COMPARISON OF DEGRADATION RATES IN THE ESCAMBIA RIVER TEST 73
24 RATE OF DISAPPEARANCE OF SELECTED SJP-4 HYDROCARBONS IN RANGE
POINT TEST 82
25 RATE OF DISAPPEARANCE OF SELECTED PJP-4 HYDROCARBONS IN RANGE
POINT TEST 83
26 COMPARISON OF BIOTIC DEGRADATION RATES IN RANGE POINT TEST 84
27 COMPARISON OF ABIOTIC DEGRADATION RATES IN RANGE POINT TEST 86
IX
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Section I
INTRODUCTION
A. OBJECTIVE
The Air Force uses large quantities of hydrocarbon fuels and is
currently evaluating the fuels derived from shale oil. The use of these
fuels introduces the possibility of their accidental release into the
environnment and requires that their fate and effects in the environment,
be understood. The information available on shale derived jet fuel is
insufficiently detailed to permit predictions about the extent and
importance of biological degradation in aquatic ecosystems. Therefore,
the purpose of this project was to characterize, in laboratory systems,
the environmental fate of shale-derived jet fuels. Specific objectives
were to:
a. Develop the necessary analytical procedures to chemically
characterize the shale-derived jet fuel.
b. Compare the chemical composition of shale-derived jet fuel
with petroleum-derived jet fuel.
c. Examine the biotic and abiotic fate of shale-derived jet
fuel and compare results with previous studies on petroleum-
derived jet fuel.
d. Characterize some of the factors affecting the biotic and
abiotic fate of shale-derived jet fuel.
B. BACKGROUND
Physical characteristics of shale-derived JP-4 are similar to those
of the petroleum-derived product. This is to be expected as these
characteristics are reflections of the suitability of shale oil products
1
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as a replacement for petroleum-derived JP-4. Several of these physical
characteristics, as reported by Ghasseml _et_ ji]_. (Reference 1), are
summarized In Table 1.
Gas chromatographlc characterization of fuel oil hydrocarbons pro-
vides a means of assessing their compositions. Examination of 33 indivi-
dual hydrocarbons common to the petroleum- and shale-derived fuel oils,
as reported by Hayes and Pitzer (Reference 2), shows some of the simi-
larities in the oils. A comparison of the fuels is shown in Table 2.
The n-alkanes comprise about 54 percent of the analyzed hydrocarbons
in the petroleum-derived JP-4 and about 68 percent in the shale-derived
JP-4.
Branched chain hydrocarbons were generally higher in the petroleum-
derived fuel; they were 3 and 5 times greater for the mono- and di-substi-
tuted alkanes, respectively. The known slow biodegradation of branched
alkanes relative to straight chain alkanes suggests that petroleum-derived
fuels would persist longer in aquatic environments.
The other hydrocarbon groups comprise a much smaller percentage of
the total fuel. Variability in the analysis of these minor hydrocarbons
does not allow generalizations to be made, except that compositional
differences are small.
Hayes and Pitzer (Reference 2) published gas chromatographic results
(area percent) of an extensive analysis of both petroleum-based and shale-
derived JP-4. They found wide compositional differences in the same fuel
type, depending on when samples were taken during the various handling pro-
cesses. High volatility of many of the fuel hydrocarbons makes detailed
comparisons of jet fuel samples difficult.
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TABLE 1. PHYSICAL CHARACTERISTICS OF JET FUELa
SHALE
JP-4
52.3
-81
2.3
18,590
0.001
PARAMETER
API Gravity0
Freezing Point ( °F)
Vapor Pressure (PSIA)
Heating Value (BTU/lb)
Sulfur (wt %)
PETROLEUM
JP-4
53.5
-79
2.5
18,702
0.03
a Values are means: for petroleum JP-4, N = 26; for shale JP-4, N = 3
Source: Ghassemi (Reference 1).
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TABLE 2. COMPARISON OF SHALE-DERIVED JP-4 WITH PETROLEUM-DERIVED JP-4,
LITERATURE VALUES9
Constituent
N-Aklanes
Heptane
Octane
Nonane
Decane
Indane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Total
Mono-Substituted Alkanes
3-Methyl hexane
2-Methyl heptane
3-Methyl heptane
Total
Multi-Substituted Alkanes
2,3-Dlmethyl pentane
2, 5-Dlmethyl hexane
254-D1methyl hexane
Total
Cycl ohexanes
Cyclohexane
Methylcyclohexane
Ethyl cyclohexane
Percent
Shale-derived JP-4
4.73
7.48
7.24
11.25
0.42
16.62
11.49
6.07
3.19
0.96
68.68
3.05
3.08
1.64
7.77
0.18
0.63
0.81
1.52
5.68
Composition
Petroleum-derived JP-4
15.76
6.60
2.54
2.24
0.17
4.17
5.25
4.71
1.02
1.35
53.77
14.39
6.14
7.19
27.72
1.48
2.52
4.00
2.13
2.17
Total 7.20 4.30
Mono-Substituted Aromatlcs
Methylbenzene 3.77 3.41
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TABLE 2. COMPARISON OF SHALE-DERIVED JP-4 WITH PETROLEUM-DERIVED JP-4,
LITERATURE VALUES3 (CONCLUDED).
Percent Composition
Constituent Shale-derived JP-4 Petroleum-derived JP-4
Multi-Substituted Aromatlcs
1,3,5-Trimethylbenzene 1.52 1.09
1,2,4-Tn'methyl benzene 2.00 3.52
1,2,3-Trimethylbenzene 0.30 1.04
Total 3.82 5.65
Xylenes
m-Xylene 2.60 2.71
£-Xylene 1.70 1.63
o-Xylene 2.00 1.89
Total 6.30 6.23
Note: Totals do not necessarily equal 100 percent due to rounding error.
a Reference 2.
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C. SCOPE/APPROACH
The approach of the project was to initially develop analytical
methods to compare the chemical composition of shale-derived jet fuel
with petroleum-derived jet fuel. Capillary gas chromatography would be
used to characterize compositional differences. Differences in the hydro-
carbon composition of the water soluble fraction would be compared using
standard techniques (Reference 3) and chromatographic analysis of solvent
extracts.
Second, the quiescent bottle test, developed for previous JP-4 studies
(Reference 4) would be used to assess the biotic and abiotic fate of shale-
derived jet fuel in water and sediment samples taken from three estuarine
sites. Conditions for optimizing the quiescent bottle test would also
be established. Biodegradation would be verified with mineralization
studies. Relationships between volatility in these tests and volatility
in a system designed to model a jet fuel spill would be further examined.
Third, environmental conditions which might affect the biotic and
abiotic fate of jet fuel would be tested. Factors such as dissolved organic
carbon and toxicity to microbial communities would be investigated.
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Section II
METHODS
A. JET FUEL
The jet fuel (SJP-4) supplied by the Air Force for our studies
was received in a 55-gallon metal drum labeled with the following
information.
F-40
JP-4
Turbine Fuel Aviation
MIL-T-5624L
NSN 91300-00-256-8617
(Refined From Shale Crude Oil)
Batch No. 1
Geokinetics, Inc.
Caribou Refinery
Woodcross, Utah 84087
Inital boiling pt. 130°F
Flash pt. below -20°F.
Subsamples of this SJP-4 and petroleum-derived jet fuel (PJP-4) were
diluted to a working concentration with methylene chloride (pesticide
grade), and stored in amber glass bottles with Teflon®-lined screw caps.
B. INSTRUMENT CONDITIONS
All hydrocarbon samples were analyzed using the following instrument
conditions:
Instrument: Hewlett/Packard 5730A gas chromatograph
Column: Capillary, approximately 60 m x 0.25 mm
Coating: SPB-1
Injector: Hewlett/Packard 7671A, 1 u£ injection volume
Data Handling: Hewlett/Packard 3357 Lab Automation System
Plotter: Hewlett/Packard 3380A integrator
Detector: Flame lonization at 250°C
Injection: Split/splitless, splitless mode at 250°C
Oven Temperatures:
Initial: 20°C (cyrogenic) for 2 minutes
Rate: 2°C per minute
Final: 190°C for 8 minutes
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C. METHOD REFINEMENTS
1. Extraction Procedure
Preliminary investigations conducted in preparation for full scale
rate testing with shale oil-derived JP-4 jet fuel gave rise to several
questions regarding the efficacy of the extraction procedures used on
sediment/water slurries in previous tests.
In the past, sediment/water slurries were treated as a discrete
sample; they were decanted from the test bottle into a separatory funnel
and extracted with methylene chloride. Spike recovery tests done prior
to previous tests indicated that the method gave good analytical results
if extraction times were 1 hour or greater. The results of prototype
tests with SJP-4, however, indicated that increased contact time between
the fuel and the sediment may have a significant negative impact upon the
ability of methylene chloride to remove hydrocarbons from the sediment.
Additionally, Lake _e_t jil_. (Reference 5) indicated that they found methy-
lene chloride to be less than ideal as an extracting solvent for sediment/
soil systems.
An alternative for analyzing sediment/water slurries in the SJP-4
biodegradation studies was to fractionate the sample by centrifugation of
the sediment, decant the water, then treat the two samples separately.
This procedure will be referred to as the fractionated sample method.
Although several solvents have been used for sediment extractions, aceton-
itrile is probably the most commonly used. Acetonitrile was tested as
the sediment-extracting solvent in this analytical method. Methylene
chloride was retained as the extracting solvent for the water fraction of
these samples.
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To compare the two analytical methods (discrete versus fraction-
ated), a standard quiescent bottle test (all nonsterile systems) was set
up, using two sediment concentrations; 500 and 5,000 mg/t, each in
duplicate. Bottles containing 25 m£ of water were spiked with 250 M£ of
SJP-4, shaken for l hour on a shaker table, then placed on their sides
on a lab bench for 24 hours with the bottle caps removed. Following 24
hours of incubation, the contents were extracted, using the fractionated
and discrete sample methods described above. Extracts were analyzed by
gas chromatography.
The results of the method test (Figures 1 and 2) indicated that
the new fractionation method was more effective in recovering hydrocarbons
that have been in contact with sediment. The new method resulted in
recoveries of 93 percent of the original spike whereas the previous dis-
crete method resulted in maximum recoveries below 60 percent of the
original SJP-4 spike.
The amount of fuel recovered from the water was about the same
(55-60 percent) as that recovered from the total sample by the discrete
method. This suggests that the methylene chloride was leaving much of
the hydrocarbons on the sediment after a short extraction. Therefore,all
subsequent test samples requiring extraction were analyzed using the
fractionation method.
2. Quiescent Bottle Test
Our primary test system consisted of the standard quiescent bottle
test as described by Spain ^t aj_. (Reference 4). The test system used
150 ms, milk dilution bottles with Teflon®-lined plastic screw caps. Each
bottle contained 25 ml of water or sediment/water slurry from the test site
in question. At test initation each bottle was spiked with 250 yf, of jet
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3000
2500
TOTAL
OIL 2000
CONC
1500
1000
500
0
MG/L
METHYLENE CHLORIDE/
ACETONITRILE EXTRACTIONS
METHYLENE
CHLORIDE
ACETO-
NITRILE
102%
500 MG/L SEDIMENT
44%
SEPARATE
COMBINED
EXTRACTION
MODE
Figure 1. Extraction Methodology with 500 mg/£ Sediment
10
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3000
2500
TOTAL
OIL 2000
CONG
1500
1000
500
0
MG/L
METHYLENE CHLORIDE/
ACETONiTRILE EXTRACTIONS
METHYLENE
CHLORIDE
ACETO-
NITRILE
94%
5000 MG/L SEDIMENT
60%
SEPARATE
COMBINED
EXTRACTION
MODE
Figure 2. Extraction Methodology with 5,000 mg/x. Sediment
11
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fuel, Immediately capped, then shaken for 1 hour. The bottles were then
uncapped and placed on their sides on a 1 ab bench. Sterile controls were
similar to nonsterile bottles except for the addition of formalin to a
final concentration of 2 percent. Duplicate bottles of each sample type
(water, sediment/water slurry; active and sterile) were sacrificed at
each sampling interval, analyzed as described above and the duplicate
results averaged.
Where the effect of sediment concentration was tested, 500, 1000,
2000, and 5000 milligrams of sediment per liter of water were used.
Bottles were spiked with 200 y£ of SJP-4, shaken for 1 hour, then incu-
bated with the tops removed. Bottles were sacrificed at 0, 24, 48, and
96 hours. The sediment and water in each bottle were analyzed separately
for hydrocarbon content using methods described above.
D. SAMPLING SITES
Sediment and water were collected from three test sites: Range Point
salt marsh, located on Santa Rosa Island; Bayou Chico, a brackish extension
of Escambia Bay; and Escambia River, a freshwater river adjacent to
Pensacola. Range Point salt marsh and Escambia River are considered to
be relatively pristine having little or no input from industrial or
municipal effluent. Bayou Chico, however, is heavily polluted.
E. COMPOSITIONAL ANALYSIS
1. Neat Fuel
Composition of shale-derived jet fuel was determined by two methods,
First, a sample of the SJP-4 and the PJP-4 were diluted to working con-
centration (3 y£/m£) with methylene chloride and analyzed by gas chromato-
graphy. Concentrations of 32 selected hydrocarbons (Table 3) in each jet
fuel sample were then compared to each other as well as to values for the
12
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same hydrocarbons as reported by Hayes and Pitzer (Reference 2) .
Second, the samples of SJP-4 and PJP-4 were fractionated by silica gel
chromatography into aromatic and aliphatic components. One m£ samples of
each fuel (SJP-4 and PJP-4) were added to the top of 25 cm by 1 cm silica
gel columns which were filled with petroleum ether. Aliphatics were
eluted with two 25 m£ washes of petroleum ether. Aromatics were eluted
with two 25 mst washes of methylene chloride. The combined eluates were
then subjected to gas chromatographic analysis and comparisons made by
summing the total area of all peaks found in each fraction.
2. Water-Soluble Fraction
Experiments were conducted to establish the reproducibility of the
water-soluble fractions (WSF) generated from both PJP-4 and SJP-4 The
method of Hunt (Reference 3) was used to obtain the water soluble fract-
ions. Each WSF was made in a 4-liter aspirator bottle with a tube con-
nector at the bottom of the bottle. Two liters of filtered seawater
(0.45 micron filtration) were placed in each bottle and 200 milliliters
of the JP-4 were gently spread across the surface. The oil/water system
was then stirred overnight with a Teflon®-coated magnetic stirring bar
such that the oil vortex extended down one-third of the water depth. To
circumvent any possible loss due to volatilization the oil content of the
system was increased from 5 to 10 percent of the water volume. Hunt's
investigation indicated that this would have no effect on the hydrocarbon
content of the WSF.
The system was allowed to settle for 1 hour after stirring. A 1-liter
water sample was then removed from the bottom of the bottle through the
tube connection, extracted twice with methylene chloride, and the combined
extracts were analyzed for hydrocarbon content.
13
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TABLE 3. LIST OF COMPONENT HYDROCARBON MONITORED THROUGHOUT STUDIES
BENZENE
CYCLOHEXANE
2,3-DIMETHYLPENTANE
3-METHYLHEXANE
HEPTANE
METHYLCYCLOHEXANE
2,5-DIMETHYLHEXANE
2,4-DIMETHYLHEXANE
METHYLBENZENE (TOLUENE)
2-METHYLHEPTANE
3-METHYLHEPTANE
1,1-DIMETHYLCYCLOHEXANE
OCTANE
ETHYLCYCLOHEXANE
ETHYLBENZENE
m-XYLENE
£-XYLENE
^-XYLENE
NONANE
ISOPROPYLBENZENE (CUMENE)
1,3,5-TRIMETHYLBENZENE
1,2,4-TRIMETHYLBENZENE
DECANE
1,2,3-TRIMETHYLBENZENE
INDAN
UNDECANE
NAPHTHALENE
DODECANE
TRIDECANE
TETRADECANE
PENTADECANE
HEXADECANE
14
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F. TOXICITY TESTS
Toxicity to the natural microbial community was investigated by assess-
ing the ability of the natural microflora to mineralize a test substrate
following exposure to SJP-4.
Water from each test site was exposed to SJP-4 for 48 hours in the
standard quiescent bottle test system. The exposed water was spiked with
20 mg/£ of ^C labeled toluene and then sealed in the milk dilution
bottles. Controls consisted of untreated site water, site water pre-
exposed to SJP-4 plus 2 percent formalin and site water preexposed to
unlabeled toluene. All controls were spiked with 20 mg/£ of ^C labeled
toluene along with the water preexposed to SJP-4.
Following 24 hours of incubation, the contents of each sealed milk di-
lution bottle were acidified by injection of IN HC1 . The acidified
solution was bubbled with nitrogen to purge C02 into traps containing IN
NaOH. 1^002 was quantitated in subsamples of NaOH by liquid scintillation
counting. The water in the bottle was then subsampled for residual
G. DISSOLVED ORGANIC CARBON
The effect of dissolved organic carbon (DOC) on hydrocarbon solubility
was investigated using a fulvic acid solution prepared from digested Range
Point detrital sediment by the procedure of Boehm and Quinn (Reference 6) .
The thick detrital sediment slurry was adjusted to a pH of 9 with NaOH and
allowed to stand 24 hours. The slurry was then acidified with HC1 to a pH
of 1 and again allowed to stand 24 hours, and the resulting solution was
adjusted to pH 7 with NaOH, then filtered through glass fiber filters to
remove any undigested material. This solution was used to amend water
collected from Range Point. DOC concentrations of the unamended water and
the fulvic acid stock solution were measured before testing with a total
15
-------
organic carbon analyzer. Initial DOC of the unamended seawater was 20 mg/A
and the fulvic acid stock solution was 400 mg/m£ .
H. JET FUEL EVAPORATION RATES
Simple experiments were conducted to estimate evaporative loss of SJP-4
in the absence of confusing factors such as solubilization of jet fuel com-
ponents into the water. The test system consisted of glass petri dishes
(10 cm diameter by 1 cm deep) filled with 60 m£ of SJP-4. Five dishes were
set up in a fume hood with a measured air flow of 50 cubic feet/minute. Con
tents of dishes were weighed at intervals and an evaporative loss percent
was obtained by weight difference.
16
-------
Section III
RESULTS
A. COMPOSITIONAL ANALYSIS
1. Fuel
Table 4 compares the concentration (percent of total) of 32 selected
hydrocarbons in each of the jet fuels with the same 32 hydrocarbons found in
shale- and petroleum-derived jet fuels studied by Hayes and Pitzer (Reference
2; Table 2). Compositional differences betweeen the jet fuels were generally
small. N-alkanes accounted for over 50 percent of the total hydrocarbons in
all fuels. Aromatics accounted for an average of 12 percent; substituted
n-alkanes and cycloalkanes made up the remainder of the fuels.
Results of the analysis of the fuels following silica gel fraction-
ation are presented in Figure 3. There was little apparent difference between
the two fuels; SJP-4 consisted of 67 percent aliphatics and 33 percent aro-
matics and PJP-4 consisted of 60 percent aliphatics and 40 percent aromatics.
As the analysis was only accurate to ± 9 percent, differences were considered
insignificant.
2. Water Soluble Fraction
The hydrocarbon compositions of the WSF from each fuel were very simi-
lar both within replicates and between experiments (Table 5). Total hydrocar-
bon concentrations in the WSF were similar to those found by Hunt (Reference
3). Mean hydrocarbon concentration in our experiments were 101 mg/£ and 84
mg/£ for petroleum- and shale-derived JP-4, respectively; Hunt reported a
maximum concentration of 45 mg/a with the JP-4 used in his experiments.
The major compositional difference in the WSF of PJP-4 and SJP-4 was
the concentration of benzene. Benzene concentrations were 44 mg/£ and
17
-------
TABLE 4. COMPARISON OF SHALE-DERIVED JP-4 WITH PETROLEUM-DERIVED JP-4,
ACTUAL VALUES
Constituent
N-Alkanes
Heptane
Octane
Nonane
Decane
Indane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Total
Mono-Substituted Alkanes
3-Methylhexane
2-Methyl heptane
3-Methyl heptane
Total
Multi-Substituted Alkanes
2,3-Dimethyl pentane
2,5-Dimethylhexane
2,4-Dimethylhexane
Total
Cyclohexanes
Cyclohexane
Methyl cyclohexane
Ethyl cyclohexane
Percent
Shale-derived JP-4
2.61
2.99
4.93
6.26
1.00
8.19
10.08
9.35
4.80
1.86
52.07
4.37
1.10
4.22
9.69
1.24
1.13
1.32
3.69
0.97
5.88
3.96
Composition
Petroleum-derived JP-4
7.62
9.94
6.31
5 65
0.48
6.53
7.32
5.77
3.25
1.01
53.88
3.94
5.30
5.71
14.95
1.08
0.82
1.76
3.16
2.20
0.48
2.79
Total 10.81 5.47
Mono-Substituted Aromatlcs
Methyl benzene 5.40 3.27
18
-------
TABLE 4. COMPARISON OF SHALE-DERIVED JP-4 WITH PETROLEUM-DERIVED JP-4,
ACTUAL VALUES (CONCLUDED)
Constituent
Multi-Substituted Aromatlcs
1,3,5-Trimethyl benzene
1,2,4-Trimethyl benzene
1,2,3-Trlmethyl benzene
Total
Xylenes
m-Xylene
£-Xylene
£-Xylene
Total
Percent Composition
Shale-derived JP-4 Petroleum-derived JP-4
3.12
1.41
0.60
5.13
3.61
2.35
3.36
9.32
2.17
0.52
1.48
4.17
2.57
1.88
1.72
6.17
Note: Totals do not necessarily equal 100 percent due to rounding error.
Based on percentage area of gas chromatographic peaks for the selected
32 hydrocarbons only. Values based on the mean of duplicate samples.
Maximum analytical error for any single hydrocarbon was never greater
than ±9 percent.
19
-------
S-JP4
P-JP4
Aromatics
Aliphatics
Aromatics
Aliphatics
Figure 3. Silica Gel Fraction
20
-------
TABLE 5. WATER SOLUBLE-FRACTION COMPONENTS
Constituent
Benzene
Cyclohexane
3-Methylhexane
Heptane
Methylcyclohexane
Methyl benzene
Ethylbenzene
nv-Xylene
jp_-Xylene
j3-Xylene
1,3,5-Trimethylbenzene
1,2,4-Trimethylbenzene
1,2,3-Trimethylbenzene
Indan
n-Undecane
Naphthalene
n-Tridecane
Mean Hydrocarbon Level s ui_ WSF, Mean jcrf
4 Replicates,mg/£ (±/- 1 Standard Deviation)
Petroleum
JP-4
44.2 (0.53)
2.7 (0.15)
13.8 (0.35)
1.6 (0.35)a
1.0 (0.05)
27.8 (1.19)
2.2 (0.10)
5.4 (0.14)3
3.8 (2.40)
3.5 (0.15)b
0.5 (0)b
1.9 (0.29)
0.9 (0.08)
0.3 (0)
1.1 (0.12)
0.2 (0.06)
Shale Oil
JP-4
19.2 (0.89)
0.7 (0.05)
13.2 (0.95)
0.8 (0.05)
33.0 (1.63)
1.7 (0.08)
5.6 (0.22)
2.0 (0.06)
4.4 (0.17)
0.5 (0.14)
1.7 (0.10)
0.4 (0)
0.4 (0.05)
0.3 (0)
Total Hydrocarbons 101.2 (7.45)
aMean and standard deviation of 2 replicates.
&Mean and standard deviation of 3 replicates.
Not Detected
84.2 (3.90)
21
-------
19 mgA, respectively. This difference accounted for the difference in
mean total hydrocarbon concentrations.
B. BOTTLE TEST OPTIMIZATION
As a preliminary test in preparation for quiescent bottle tests with
SJP-4 we determined the optimal sediment concentration to be used in the
bottle test. Previous observations that sediment concentrations might
have a significant impact on test results, required that we delineate the
role of sediment concentration in the quiescent bottle test.
The results of the tests (Figure 4) indicated little effect of sediment
concentrations after the first 24 hours. Although the total recovery seemed
to be affected at 24 hours, ranging from 28 percent in the 500 mg/£ bottle
to 58 percent in the 2000 mgA bottle, by 96 hours, all results were nearly
identical, with total recoveries of about 24 percent and a partitioning of
about 22 percent of that total onto the sediment.
C. QUIESCENT BOTTLE TESTS
1. Range Point
A large decrease in total hydrocarbon concentration during the first
four hours of incubation occurred in all treatments (Figure 5). Volatilization
played a major role in hydrocarbon disappearance, as evidenced by the losses
from sterile systems. As expected, this volatility had a greater impact upon
lower boiling hydrocarbons. Major differences were also seen between sterile
and active water systems, indicating biodegradation (Table 5A). The presence
of sediments generally reduced volatility in sterile systems and effectively
eliminated biodegradation in most of the water systems. We currently have no
explanation for this effect of sediments on biodegradation.
Similar results were observed in previous tests with petroleum-derived
JP-4 (Reference 4), although loss of hydrocarbons in their nonsterile water
22
-------
"=0
WATER
MG/L
2000
0
I
1500
C
0 1000
N
C
500
SEDIMENT
ESSSS
TOTAL
1000 2000
SEDIMENT CONCENTRATION
(MG/U
5000
1=24
WATER
SEDIMENT
TOTAL
MG/L
1000 2000
SEDIMENT CONCENTRATION
(MG/L)
Figure 4. Effect of Sediment Concentration
5000
23
-------
100 r—
cu 80
"a.
CO
^_
O
"o
-t-j
c:
CD
o
i. —
a>
Q_
+ STERILE SEDIMENT
* STERILE WATER
H NONSTERILE SEDIMENT
x NONSTERILE WATER
20
Figure 5. Total Hydrocarbon Loss in Range Point Bottle Test
24
-------
TABLE 5a. COMPARISON OF DISAPPEARANCE RATES IN STERILE AND ACTIVE
RANGE POINT SYSTEMS
Slope of semi -log
Hydrocarbon
2,3-dimethylpentane
3-Methylhexane
Heptane
Methyl cycl ohexane
2,5-Dimethylhexane
2,4-Dimethylhexane
Methyl benzene
2-Methyl heptane
3-Methyl heptane
Octane
Ethyl cycl ohexane
Ethyl benzene
ni-Xylene
£-Xylene
£-Xylene
Nonane
Isopropyl benzene
plot concentration
Sterile9
-.0028
-.0038
-.0030
-.0138
-.0016
-.0017
-.0769
-.0014
-.0015
-.0012
-.0012
-.0018
-.0359
-.0014
-.0020
-.0007
-.0007
(mg/£) versus
Active
-.0496
-.0713
-.0899
-.0775
-.0513
-.0540
-.0746
-.0742
-.0720
-.0679
-.0728
-.0562
-.0691
-.0610
-.0689
-.0709
-.0060
time
Ratio of Active
to Sterile Rates
17.7
18.8
30.0
5.6
32.1
31.8
-0.97
53.0
48.0
56.6
60.7
31.2
1.9
43.6
34.4
101.3
8.6
Disappearance of hydrocarbons from shale-derived JP-4 in quiescent
bottle tests containing water from Range Point salt marsh
aSterilized by addition of formalin to the water to a final concentration
of 2%.
25
-------
systems was less extensive than observed in this test. Figures 6 through
16 present the relative loss rates of the 32 individual hydrocarbons
monitored throughout the test.
Comparison of our results with those reported for previous PJP-4
tests (Reference 4) indicated a significant difference in the disappearance
rates of many of the hydrocarbons. The faster disappearance of the hydro-
carbons in the PJP-4 test was due to a greater volatility of the hydro-
carbons in that test (as evidenced by disappearance rates in the sterile
systems). The SJP-4 data indicated an approximate 5 to 10-fold increase
in rate between sterile and nonsterile water for compounds such as decane,
undecane and naphthalene; the results of the PJP-4 test indicate approxi-
mately two-fold differences. Additionally, 95 percent confidence limits
for the rates indicate that in some cases (decane, for example) the
difference between sterile and nonsterile water systems was significant
in the SJP-4 test (confidence limits do not overlap) but not significant
in the PJP-4 test (confidence limits do overlap), although disappearance
rate in the nonsterile PJP-4 test is over twice as fast as the corresponding
rate in the SJP-4 test. This lack of difference in the PJP-4 test is
likely due to the sampling schedule, i.e., the initial drop in (decane)
concentration within the first 24 hours was such a heavily weighted
portion of the disappearance curve, that any later biodegradation was
below detection limits.
The differences between sampling schedules, possible differences
in test conditions and probable environmental changes at the test site
make comparison of the SJP-4 data with any previous tests difficult.
Mineralization of 14C decane showed that approximately 60,000 dpm
of 14C02 (7 percent of the original spike) were produced in the nonsterile
26
-------
80—1
C
0
N
C
M
5
68 —
40-:
ETHYLCYCLOHEXANE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
DAYS
C
O
N
C
M
5
BENZENE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
2 —
T[II"TII[[II[I[TtIII
E 10 is ze>
DAYS
Figure 6. Loss of Ethylcyclohexane and Benzene in Range Point Test
27
-------
c
0
N
C
M
S
-4
CYCLOHEXANE
r-p-r
ta
DAYS
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
IS
I i 1 i I
20
C
0
N
C
/
L
METHYLCYCLOHEXANE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
DAYS
Figure 7. Loss of Cyclohexane and Methylcyclohexane in Range Point Test
28
-------
aa—i
c
0
N
C
M
6
40 —
20-
a-
METHYLBENZENE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
c
— v~ T— T— r — | — r — r ~
i E
i i | i i i
10
1 1 '
IE
1 1 1 |
20
DAYS
c
0
N
C
M
G
a
ETHYLBENZENE
Sterile Water ---- *
Active Water -.-.A
Sterile Sediment
Active Sediment
X
Figure 8. Loss of Methylbenzene and Ethylbenzene in Range Point Test
29
-------
c
0
N
C
M
S
/
L
3 —
2 —
H
•4
1 . 1
I ' •
-
ra __
ISOPROPYLBENZENE
\ Sterile Water *
\ * Active Water -.-.A
[\ /\ Sterile Sediment ....X
\ */ \ Art.ive Sediment o
•W
W t.::.::.-,.. =<•,
\ x / — —•*•-.>-,..__
. vw-v. X •*
\ \7X
t i / \ »«
\ \t \
i tf , X. ..._^j^- — ,
a
T—r—9—r
ia IE
DAYS
C
O
N
C
M
G
m-XYLENE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
f~¥ — [ — i — t — i — i — [ — i — i — i — i — [ — i — i
E IB IE
DAYS
20
Figure 9. Loss of Isopropylbenze and ni-Xylene in Range Point Test
30
-------
c
o
N
C
M
6
C
O
N
C
M
G
p-XYLENE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
DAYS
o-XYLENE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
0
DAYS
Figure 10. Loss of £-Xylene and £-Xylene in Range Point Test
31
-------
63—r
C
o
N
C
M
G
C
O
N
C
M
1,3,5-TRIMETHYLBENZENE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
T—i—r
~r
IE
T—i—r
-'"I
20
DAYS
ea
1,2.4-TRIMETHYLBENZENE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
za—
(
V.
— i — i—*r
»
-tit*
E
—i — r-
10
J 1 "'T-
IS 2
DAYS
Figure 11. Loss of 1,3,5-Trimethylbenzene and 1,2,4-TMmethylbenzene
in Range Point Test
32
-------
c
0
N
C
M
s
a
1,2,3-TRIMETHYLBENZENE
Sterile Water *
Active Water -.-.a
Sterile Sediment ...
Active Sediment
VN
! """"-A.
| 1 1 I T
a
^-^—
\ ' '
E
. a B""
I I | 1 1 1
ia
PAYS
1 I '
IE
— *
I 1 > 1 |
2B
c
o
H
C
M
C
INDAN
Sterile Water *
Active Water -.-.A
Sterile Sediment X
Active Sediment o
a
PAYS
Figure 12. Loss of 1,2,3-Trimethylbenzene and Indan and Range Point Test
33
-------
200
C
o
N
C
M
G
ice—
tea
sa—
HEPTANE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
SB—i
c
o
N
C
M
C
OCTANE
Sterile Water *
Active Water -.-.A
Sterile Sediment ... .X
Active Sediment o
PAYS
Figure 13. Loss of Heptane and Octane in Range Point Test
34
-------
NAPHTHALENE
C
0
N
C
M
S
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
a
DAYS
Figure 14. Loss of Napthalene in Range Point Test
35
-------
80—i
NONANE
c
0
N
C
a
3
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
C
o
N
C
M
S
DECANE
Sterile Water *
Active Water -.-.A
Sterile Sediment ....X
Active Sediment o
0
3
18
DAYS
T—p-r~Tr*r"t—j
16 20
Figure 15. Loss of Nonane and Decane In Range Point Test
36
-------
C
0
N
C
M
6
PENTADECANE
Sterile Water *
Active Water -.-.A
Sterile Sediment ... .X
Active Sediment o
x
c
o
N
C
M
C
/
u
z.a-^
«
M
l.E —
*•
*•
1 .a—
M
0.S— '
.8
C
HEXADECANE
ft Sterile Water *
A Active Water -.-.A
I \ Sterile Sediment ....X
1 • Active Sediment o
/ \
*' \
/« ^
/K >,.
uJ V \ ^.-^..^^
**»j^»»-*^t^^^ * * ~-~ )ic-_rr^ o
iiiiiiiiiiiiiiiiiitt
i c ia ic 20
PAYS
Figure 16. Loss of Pentadecane and Hexadecane in Range Point Test
37
-------
flask and only 600 dpin (< 0.01 percent of the original spike) were pro-
duced from the sterile flasks. This confirms that partial disappearance
of decane in the bottle test was the result of biodegradation.
2. Bayou Chico
The Range Point test clearly demonstrated difficulties in trying
to compare results of current SJP-4 test with previous PJP-4 tests, con-
sequently the quiescent bottle test system was expanded to include both
SJP-4 and PJP-4. The results are shown in Tables 6 - 13.
Volatilization played a predominant role in hydrocarbon disappear-
ance for this test. Unlike previous tests, however, the volatility
virtually overwhelmed our ability to detect biodegradation as evidenced
by the lack of statistically significant differences in the disappearance
rate between nonsterile and sterile systems (Table 14). Comparison of
results with the two types of jet fuel, SJP-4 and PJP-4, show that there
was no significant difference in disappearance rates although, as one
would expect when volatility plays such a predominant role, the lower
boiling hydrocarbons are lost faster than the higher boiling hydrocarbons.
Subsequent investigations with radiolabeled decane and 2-methyl-
naphthalene showed that, despite the lack of apparent biodegradation based
on the disappearance of parent compound, some biodegradation (mineralization
to C02) was occurring.
3. Escambia River
Data from the quiescent bottle test with both SJP-4 and PJP-4 and
water/sediment samples from Escambia River are presented in Tables 15 - 22.
Volatilization was again the predominant factor in hydrocarbon removal.
Disappearance patterns of the individual hydrocarbons were similar to those
seen in previous tests, i.e., lower boiling hydrocarbons were lost faster
38
-------
TABLE 6. DATA FROM BAYOU CHICO BOTTLE TEST, STERILE WATER WITH SJP-4
OJ
Hydrocarbon
Benzene
Cyclohexane
2,3-dimethylpentane
3-Methylhexane
Heptane
Methylcyclohexane
2,5-Dimethylhexane
2,4-Dlmethyl hexane
Methyl benzene
2-Methylheptane
3-Methylheptane
Day 0 Day 1
9.7 (4- .3)
14.0 (+_ .7)
94.5 (+_ 0)
57.2 (+1.1)
175.8 (+11.4) 72.4b
83.1 (+_ .7)
20.7 (+_ 0)
23.6^
73.4 (+_ .4)
72.6 (+_2.4)
64.6 (+ .2)
1,1-Dimethylcyclohexane 0.7 (+_ 0)
Octane
Ethylcyclohexane
Ethyl benzene
jn-Xylene
2-Xylene
o-Xylene
52.1 (+_ .1)
68.5 (_+ .2)
27.6 (+_ .2)
58.2 (jf .3)
37.0 (+_ .1)
57.8 (+ .3)
Day 2
Day 4
Day 8
Day 13
28.4 (+ 0) 45.8 (^3.6)
1.0 (+_ .1)
7.8 (+ .1)
4.0
3.7 (+ .6) 2.8 (+ .5) 2.3 ( +1.7)
-------
TABLE 6. DATA FROM BAYOU CHICO BOTTLE TEST, STEILE WATER WITH SHP-4 (CONCLUDED)
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 13
Nonane 33.5 (_+ .6) 10.2 (+_ .3)
Isopropylbenzene 0.8 (_+_ 0) -
1,3,5-Trimethylbenzene 57.7 (+_ 0) 13.5 (+_ .3) 1.8 (+_ .6) -
1,2,4-Trlmethylbenzene 19.5 (+_ .4) 1.2 (+_ .4) 2.9 (+_ .9) -
Decane 119.0 (+_ .7) 51.0 (j+ .5) 15.7 (^2.6)
1,2,3-Trimethylbenzene 11.5 (+_ .1) 4.3 (+_ .1) 1.0 (+_ .2) -
Indan 22.0 (+_ .1) 6.1 (+_ .1) 2.2 (+_ .4) -
^ Undecane 53.0 (+1.3) 11.2 (+ .5) 63.2 (+1.7) 07.9 (^19.8)
o ~
Naphthalene 10.4 (_+ .1) 7.7 (+; .1) 13.9 (^1.1) 5.4 (+_!.!)
Dodecane 61.5 (+.1.4) 6.3 (+_ .5) 106.3 (+5.5) 26.8 (+_36.7) 9.3 (+_ .9) 0.5b(+_ .3)
Tridecane 51.1 (+1.4) 3.3 (+2.9} 105.7 (+_1.6) 38.5 (+_45.2) 37.4 (+_7.8) 3.2 (_+ .1)
Tetradecane 39.6 (+1.7) 4.3 (+ .7) 62.4 (+_1.2) 47.5 (+4.3) 41.0 (+_8.1) 16.4 (+1.7)
Pentadecane 18.4 (+ .8) 1.9 (+ .1) 28.0 (+1.7) 41.3 (+_ 3) 23.5 (^4.5) 19.4 (+4.3)
Hexadecane ^_ _^ - z I I
Concentrations (mgA)a of selected hydrocarbons in sterile water bottles from quiescent bottle test,
using water samples from Bayou Chico and shale-derived JP-4.
aAverage of replicate samples.
bBad replicate; n=l
*Parentheses indicate one standard deviation from the mean.
**Dashes (-) indicate not detectable (<0.2 mg/n) .
-------
TABLE 7. DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE WATER WITH SJP-4
Hydrocarbon Day 0 Day 1 Day 2 Day 4C Day 8 Day *
Benzene 9.6 (+_ .2)
Cyclohexane 14.4 (+_ .1)
2,3-Dimethylpentane 92.7 (_+ .2)
3-Methylhexane 56.6 (+_ .2)
Heptane 158.0 (+7.8) -
Methyl cyclohexane 81.0 (+_ .6)
2,5-Dimethylhexane 19.8 (+6.3) -
2,4-Dimethylhexane 22.6 (+_ .5) -
Methylbenzene 69.5 (+1.5) -
2-Methyl heptane 69.0 (+13.1) -
3-Methyl heptane 61.5 (_+5.8) -
Octane 49.2 (+_ .8)
Ethylcyclohexane 65.0 (+_ .7) 1.0& -
Ethyl benzene 26.1 (+_!)-
m-Xylene 54.7 (+1.9) 1.3 (+_ .3)
£-Xylene 34.5 (+_ 1) 1.1 (+_ 0) -
_o-Xylene 54.0 (+1.1) 1.7 (± .2) - - 4.Qb
-------
-p.
ro
TABLE 7. DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE WATER WITH SJP-4 (CONCLUDED)
Hydrocarbon Day 0 Day 1 Day2 Day 4C Day 8 Day 13
Nonane 81.6 (±1.6) 8.6 (±2.4) 1.0 ( + .7) -
Isopropyl benzene 2.5 (± 0)
1,3,5-Trimethylbenzene 53.0 (± .9) 12.1 (±1.9) 2.7 (± .3) -
1,2,4-Trimethylbenzene 3.0 (+_ .9) 1.2 (±2.5) 3.8 (± .5) -
Decane 57.7 (+1.9) 48.3 (±5.8) 17.9 (± .1) 2.8
1,2,3-Trimethylbenzene 10.5 (± .2) 4.0 (± .7) 1.2 (± .1) -
Indan 18.3 (± .3) 8.1 (+_ .9) 2.6 (± 0)
Undecane 47.3 (±2.7) 13.4 (±5.6) 60.7 (±6.5) 135.8 4.3 (±4.9)
Naphthalene 9.9 (± .4) 5.4 (± .6) 12.6 (+ .9) 8.8 1.9 (+1.3)
Dodecane 51.2 (±2.9) 2.5 (±3.2) 94.3 (±10.2) 78.2 26.1 (±9.3) 0.5 (+_ .4)
Tridecane 45.0 (±2.7) 2.5 (± 2) 88.5 (± 12) 87.3 50.0 (± 5) 8.1 (±2.5)
Tetradecane 35.0 (±2.1) 4.8 (±1.1) 52.3 (±1.1) 55.6 42.2 (±2.5) 23.7 (±3.7)
Pentadecane 17.3 (± .7) 1.8 (± .7) 25.4 (±2.2) 38.2 21.2 (±1.1) 21.2 (±2.3)
Hexadecane - ^ - - i -
Concentrations (mg/£)a of selected hydrocarbons in active water bottles from quiescent bottle test,
using water samples from Bayou Chico and shale-derived JP-4S
aAverage of replicate samples.
bBad replicate; n=l
cDay 4. No duplicate sample.
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectabel (<0.2 mg/£).
-------
TABLE 8. DATA FROM BAYOU CHICO BOTTLE TEST, STERILE SEDIMENT WITH SJP-4
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 13
Benzene 4.3 (_+ .6) -
Cyclohexane 11.5 (+_ .2)
2,3-Dimethylpentane 11.3 (+1.1) 2.6 (+_ .2) 3.7 (+ .1) - 10.2b
3-Methylhexane 30.7 (+2.3) 1.7 (+_ .9) 2.3 ( + .1) - 5.9b
Heptane - 11.2 (+4.4) 13.8 (+_1.2) 7.1 (+; .7) 63.4 (^8.5)
Methylcyclohexane 36.1 (+2.4) 2.5 (+_ .2) 3.0 (+_ .7) 1.5 (+_ .4)
2,5-Dlmethylhexane 9.7 (+_ .7)
2,4-Dimethylhexane 15.2 (+1.3) - 1.4 (+_ 1) -
Methylbenzene 26.4 (+2.6) 1.3 (+1.6) -
2-Methyl heptane 14.8 (+1.1) 2.5 (+_ 0) 3.7 (+_ .1) 2.2 (+_ .6) 1.1 (+_ .1)
3-Methylheptane 40.3 (+_2.7) 2.4 (+ .1) 3.5 (+_ .1) 2.0 (+ .6) 1.3 (+ .5)
1,1-Dimethylcyclohexane 0.8 (+_ .1) 0.2b -
Octane 23.5 (+1.7) 2.0 (+_ .1) 3.0 (+_ 0) 1.8 (+_ .5) 0.9 (+_ .1)
Ethyl cyclohexane 27.4 (+_1.8) 2.9 (^ .1) 4.7 (_+ .4) 2.3 (+_ .6) 1.3 (+_ .5)
Ethylbenzene 12.7 (+1.7) 1.0 (+_ .9) 1.0 (+_ .2) -
jn-Xylene 29.6 (+2.7) 2.8 (+_ .9) 1.8 (± .5) -
£-Xylene 13.6 (+2.1) 1.8 (+_ .8) 1.2 (+_ .8) -
2-Xylene 23.7 (+1.9) 2.2 (+_ .7) 1.2 (+ .3)
-------
TABLE 8. DATA FROM BAYOU CHICO BOTTLE TEST, STERILE SEDIMENT WITH SJP-4 (CONCLUDED)
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 13
Nonane 34.4 (^2.5) 16.2 (+_ .3) 6.7 (+_ .4) 3.9 (^1.6) 1.8 (+_ .7)
Isopropylbenzene 0.6 (+_ .2)
1,3,5-Trimethylbenzene 20.5 (+1.4) 10.0 (^ .2) 4.5 (+_ .7) -
1,2,4-Trimethylbenzene 24.9 (+_1.4) 7.3 (+1.8) 5.7 (+1.7)
Decane 49.7 (+4.7) 54.2 (+4.4) 16.3 (+_ 4) 6.7 (+_1.6) 3.3 (+_ .5) 1.0 (+_ .5)
1,2,3-Trimethylbenzene 6.0 (+_ .6) 3.1 (+_ .7) 1.4 (+_ .7) -
Indan 7.0 (_+ .7) 6.5 (+_ 1) 1.9 (+_ .8) -
Undecane 61.4 (+4.4) 15.3 (+11.3) 50.1 (+8.7) 51.3 (+13) 4.6 (+_ .8) 1.8 (+ .7)
Naphthalene 8.4 (+_ .5) 6.5 (+JL.9) 12.3 (+_3.4) 5.7 (+_ .8) 0.5 (+_ 0)
Dodecane 68.3 (+_ 4)c 18.5 (+17.3) 78.1 (+_42.8) 53.9 (+7.1) 10.3 (+_ .2) 2.6 (+_ 1)
Trldecane 61.8 (+_7.9)^ 17.7 (+_ 18) 78.8 (+_45.5) 78.3 (+_7.9) 23.5 (+_ .1) 4.1 (+_ .8)
Tetradecane 47.1 (+2.1)c 13.7 (+11.8) 47.9 (+24.7) 46.9 (+ 5) 36.3 (+1.3) 8.9 (+6.3)
Pentadecane 21.6 (+1.4)c 24.1 (+5.5) 21.8 (+11.3) 25.1 (+_1.7) 20.0 (+_ 1) 9.3 (+3.9)
Hexadecane - - - - - -
Concentrations (mg/£)a of selected hydrocarbons in sterile sediment bottles from quiescent bottle
test, using sediment samples from Bayou Chico and shale-derived JP-4.
aAverage of replicate samples.
bBad replicate; n=l
cNo duplicate water samples.
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mg/£).
-------
TABLE 9. DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE SEDIMENT WITH SJP-4
Hydrocarbon Day 0
Benzene
Cyclohexane
2,3-Dlmethyl pentane
3-Methyl hexane
Heptane 21
Methyl cyclohexane
2,5-Dimethyl hexane
2,4-Dimethyl hexane
Methyl benzene
2-Methyl heptane
3-Methyl heptane
1,1 -Dimethyl cyclohexane
Octane
Ethyl cyclohexane
Ethyl benzene
m-Xyl ene
£-Xylene
o-Xylene
1
2
1
3
0
1
3
2
5
3
4
1
6
1
4
-
-
.5
.0
.3
.5
.8
.1
.1
.6
.5
-
.6
.4
.3
.4
.1
.1
(±-
(± •
(+8.
(± •
(± •
(± •
(± •
(± -
(± •
(± -
(± -
(± •
(± •
(± •
(± -
Day 1 Day 2 Day 4 Day 8 Day 13
_
_
1) -
1) - 1.2 (+ 0) - 1.5 (+ .2)
1) - - 20.3 (+4.1)
2) - 1.4 (+_ 0) 1.7 (+_ .6) 1.4 (+_ .2)
1) -
1) -
2) -
1) - 1.7 (+_ .1) 2.1 (+_ .6) 2.5 (+ .7)
5) - 1.5 (+_ .1) 2.1 (+_ .7) 2.6 (+_ .7}
- - - - -
3) - 1.3 (+_ .1) 1.8 (_+ .5) 1.9 (+; .5)
5) 1.3 (+_ .3) 1.7 (+_ .2) 2.4 (+_ .6) 2.1 (+_ .6)
1) -
8) -
1) 0.8 (_+.!)-
4) 2.2 (+_ .2)
-------
TABLE 9. DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE SEDIMENT WITH SJP-4 (CONCLUDED)
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 13
Nonane 8.3 (+_ 1) 7.8 (+_ .5) 2.6 (+; .8) 3.0 (+; .6) 1.1 (+_ 1)
Isopropylbenzene - _____
1,3,5-Trimethylbenzene 7.5 (+_!.!) 10.0 (_+ .1) 3.1 (+_ .2) 1.2 (_+ .3)
1,2,4-Trimethylbenzene 9.7 (+_ 1) 25.0 (+_ .3) 4.4 (+_ .3) 1.1 (+_ .3)
Decane 25.3 (+2.9) 92.0 (+_ .1) 13.9 (+_ .7) 6.0 (+ .9) 4.3 (j- 2) 0.8 (+ .2)
1,2,3-Trimethylbenzene 2.8 (+_ .4) 4.1 (+_.!)-
Indan 3.5 (_+ .5) 6.8 (+_ .1) 1.7 (+_ .3) -
Undecane 48.2 (+1.3) 76.6 (+1.3) 43.7 (+2.3) 25.9 (+9.1) 6.6 (+2.6) 1.2 (+_ .3)
Naphthalene 7.4 (+_ .3) 15.1 (+_ .9) 8.5 (+_ .6) 7.2 (+_2.5) 0.8 (+_ .3)
Dodecane 62.0 (+1.6) 107.0 (+6.5) 70.7 (+_3.6) 67.6 (^ 15) 13.4 (+_ 5) 2.0 (+_ .9)
Tridecane 55.1 (+_ 0) 91.0 (jf3.3) 75.5 (+4.6) 84.9 (+_10.2) 37.4 (+6.4) 3.8 (j+1.6)
Tetradecane 42.8 (+_ .5) 62.9 (+2.9) 43.4 (+2.1) 55.2 (+_3.6) 42.6 (+_ 2) 9.3 (+_ 10)
Pentadecane 18.6 (_+ .3) 26.2 (+ 0) 19.0 (_+ .2) 30.1 (^1.6) 23.5 (+_ .4) 8.1 (+_6.7)
Hexadecane - - - - - -
Concentrations (mg/£)a of selected hydrocarbons in active sediment bottles from quiescent bottle test,
using sediment samples from Bayou Chico and shale-derived JP-4.
aAverage of replicate samples.
^Bad replicate; n=l
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mg/£) .
-------
TABLE 10. DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE WATER WITH PJP-4
Hydrocarbon
Benzene
Cyclohexane
2,3-Dimethylpentane
3-Methylhexane
Heptane
Methylcyclohexane
2,5-Dimethylhexane
2,4-Dimethylhexane
Methyl benzene
2-Methylheptane
3-Methylheptane
Day Oc
20.9 (+4.3)
89.9 (+14.4)
32.9 (+6.2)
88.0 (+14.3)
2751.3 (+310.1)
91.7 (+16.5)
19.8 (+4.1)
46.3 (+9.8)
47.5 (+13.3)
131.2 (+_25.3)
160.3 (+32.4)
Day 1
Day 2
Day 4
Day 8
Day 13
1,1-Dimethylcyclohexane 6.3 (+1.5)
Octane
Ethylcyclohexane
Ethyl benzene
jn-Xylene
_p_-Xylene
_o-Xyl ene
216.4 (+41.1)
56.8 (+13.2)
28.5 (+8.9)
54.4 (+17.7)
36.2 (+10.5)
35.3 (+11.3)
-------
TABLE 10. DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE WATER WITH PJP-4 (CONCLUDED)
Hydrocarbon Day Oc Day 1 Day 2 Day 4 Day 8 Day 13
Nonane 132.4 (+34.3) 11.1 (+1.7) 1.4&
Isopropylbenzene 4.0 (+_1.4) -
1,3,5-Trimethylbenzene 39.3 (+12.1) 9.1 (+1.1) 1.7 (+_ .8) -
1,2,4-Trimethylbenzene 52.2 (+17.3) 15.3 (+JL.2) 3.3 (+JL.5)
Decane 128.7 (+41.6) 50.7 (+4.8) 19.7 (+4.6)
1,2,3-Trimethylbenzene 23.1 (+8.2) 3.4 (+_ .7) 2.3 (+_ .5) -
Indan 8.4 (+3.3) 3.4 (+_ .2) 1.1 (+_ .3) -
^ Undecane 153.2 (+_50.5) 99.2 (+_7.3) 68.9 (+.2.3) 51.2 (+2.4) 1.2 (+_ .6)
oo
Naphthalene 32.1 (+9.4) 11.6 (+1.5) 21.5 (+2.3) 7.4 (+_ .2) 1.1 (+_ .5)
Dodecane 150.9 (+54.5) 5.4 (+_ 6) 96.0 (+_ .5) 55.5 (+1.6) 18.0 (+_5.5)
Tridecane 133.4 (+48.3) 46.1 (+_2.9) 84.2 (+1.8) 77.7 (+_3.3) 37.7 (+7.2) 3.3 (+_ 4)
Tetradecane 100.5 (+34.6) 53.2 (+_2.5) 50.9 (+_ .8) 50.7 (+_ 1) 35.3 (+.5.2) 13.5 (+_8.3)
Pentadecane 36.2 (+11.3) 16.9 (+_ .2) 17.9 (+_ .1) 25.6 (+ .2) 14.3 (+1.6) 11.9 (+3.2)
Hexadecane 2 I " - I ~
Concentrations (mg/£)a of selected hydrocarbons in active water bottles from quiescent bottle test,
using water samples from Bayou Chico and petroleum-derived JP-4.
aAverage of replicate samples.
bBad replicate; n=l
cAverages recalculated from repeated test data; standard deviations calculated from
repeated test data.
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detected (<0.2 mg/S.) .
-------
TABLE 11. DATA FROM BAYOU CHICO BOTTLE TEST, STERILE WATER WITH PJP-4
Hydrocarbon
Benzene
Cyclohexane
Day 0 Day 1 Day 2 Day 4 .PJLLJL
23.7 (+3.2) -
52.9 (+11.7) -
Day 13
-
2,3-Dimethylpentane 102.2 (+3.9)
3-Methylhexane 79.0 (+11.5)
Heptane 722.7 (+_332.2)
Methyl cyclohexane 102.9 (+12.2)
2,5-Dimethylhexane 22.7^
2,4-Dimethylhexane 33.6 (+6.4)
Methylbenzene 67.2 (+7.3)
2-Methylheptane 137.9 (+17.4)
3-Methyl heptane 153.8 (+21.6)
1,1-Dimethyl cyclohexane 0.3 (+_ .9)
Octane 253.4 (+_27.4)
Ethyl cyclohexane 70.4 (+_7.8)
Ethylbenzene 31.2 (+_4.7)
m-Xylene 60.0 (+_ 9)
£-Xylene 42.7 (+_5.5)
o-Xylene 44.7 (+_5.9) 1.0 (+_ .1)
-------
TABLE 11. DATA FROM BAYOU CHICO BOTTLE TEST, STERILE WATER WITH PJP-4 (CONCLUDED)
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 13
Nonane 27.6 (+18.4) 10.7 (+1.9) 1.6 (j+1.1)
Isopropylbenzene 7.3 (+_ .7) -
1,3,5-Trimethylbenzene 55.5 (+5.8) 8.6 (+_ 1) 2.5 (±1.7)
1,2,4-Trimethylbenzene 84.2b 14.8 (+1.4) 3.0 (+2.7)
Decane 153.2 (+20.1) 49.7 (+4.9) 18.4(^11.5) -
1,2,3-Trimethylbenzene 4.1 (+.3.9) 5.9b 2.1 (+_ 1.3)
Indan 13.4& 3.6 (+_.2) 1.5 (+_!.!)
Undecane 73.8 (+22.5) 113.2 (+6.8) 72.0(^18.9) 155.2 (+20.6)
o
Naphthalene 7.1 (^3.1) 4.5 (+1.7) 21.7(+_ 3.9) 9.7 (+• .2)
Dodecane 11.0 (+20.6) 3.9 (+.5.6) 102.7(+16.1) 61.7 (+1.2) 3.9 (^3.5) 0.5 (+_ .4)
Trldecane 2.8 (+15.1) 108.3 (+_2.4) 95.3 (+.2.8) 77.0 (+_3.6) 21.5 (^9.6) 9.5 (+_2.1)
Tetradecane 76.4 (+_11.7) 57.4 (+_1.4) 57.0 (+ .9) 50.8 (+28.8) 29.9 (+6.5) 15.9 (+_3.2)
Pentadecane 1.2 (+4.7) 18.8 (+_ .4) 19.4 (+_ .6) 34.7 (+22.9) 14.4 (+_2.4) 14.3 (^1.5)
Hexadecane - - - - - -
Concentrations (mg/Ji)a of selected hydrocarbons in sterile water bottles from quiescent bottle test,
using water samples from Bayou Chico and petroleum-derived JP-4.
aAverage of replicate samples.
^Bad replicate; n=l.
Parenthesis indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mgA) .
-------
TABLE 12. DATA FROM BAYOU CHICO BOTTLE TEST, STERILE SEDIMENT WITH PJP-4
Hydrocarbon
Benzene
Cyclohexane
2,3-Dimethyl pentane
3-Methylhexane
Heptane
Methyl cycl ohexane
2,5-Dimethyl hexane
2,4-Dimethyl hexane
Methyl benzene
2-Methyl heptane
3-Methyl heptane
Day 0
9.9 (± ,1}
31.0(±12.3)
21.7 (+11)
30.7 (±2.8)
_c
34.0(^15.7)
10.2 (± 1)
20.7 (+2.2)
24.2 (±2.1)
64.2 (±7.6)
78.5 (4-9.5)
Day 1
-
-
-
-
161.2(±57.7)
1.1 (± .2)
-
-
1.1 (± .1)
2.1 (±1.3)
2.8 (+1.7)
Day 2
-
-
-
2.7 (+2.5)
40.7(4-25.1)
4.1 (+,3.2)
-
-
-
7.1 (+4.7)
5.2 (±5.5)
Day 4
-
-
-
1.6 ( + .8)
24.8(±10.4)
2.1 (±1.1)
-
-
-
4.2 (±1.9)
5.1 (±2.2)
Day 8 Day 13
-
-
-
-
12.38(±13.3) 25.3 (±4.1)
1.6 (± .8)
-
-
-
3.9 (±1.9) 1.8 (± .5)
6.1 (±2.3) 2.8 (± .7)
1,1-Dimethyl cycl ohexane 2.6 (+ .4) -
Octane
Ethyl cycl ohexane
112.1(^13.7)
28.8 (+3.6)
4.9 (±2.9)
1.1 (± .5)
15.3 (±9.6)
4.4 (±2.6)
8.9 ( + 3)
2.3 (± .9)
8.3 (±3.3) 3.7 (± .8)
1.9 (± .8) 0.6 (± 0)
Ethylbenzene 14.1 (±1.5) 0.9 (+_ .2)
m-Xylene 26.1 (±6.8) 1.8 (±1.1) 3.1 (±1.7) 1.1 (± .2)
_p_-Xylene 20.6 (±1.8) 1.0 (± .3)
o-Xylene 19.1 (±1.6) 0.9 (± .3)
-------
TABLE 12. DATA FROM BAYOU CHICO BOTTLE TEST, STERILE SEDIMENT WITH PJP-4 (CONCLUDED).
Hydrocarbon
Nonane
Isopropyl benzene
1 ,3,5-Trimethylbenzene
1 ,2,4-Trimethyl benzene
Decane
1,2,3-Trimethyl benzene
Indan
Undecane
Naphthalene
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Concentrations (mgA)a
quiescent bottle test,
Day 0
68.2
2.1
20.5
28.7
63.9
13.4
4.2
72.6
16.4
70.0
56.8
42.0
15.2
_
(+8.6)
(± .1)
(±2.6)
(±2.9)
(±8.5)
(+1.4)
(± .5)
(±9.5)
(± .9)
(±8.8)
(±+.5)
(±3.8)
(±1.7)
Day 1
6.0 (±2.2)
-
3.3 (+_ 1)
5.3 (±3.4)
20.6(±10.7)
3.7 (+_ 1)
0.9 (± .2)
45.2(±12.7)
11.1 (±3.9)
51.7 (± 15)
45.5 (± 12)
34.2 (±8.1)
11.8 (±2.9)
-
of selected hydrocarbons in
using sediment samples from
Day 2
11.8
-
4.0
6.6
18.8
3.4
0.8
57.4
19.8
85.1
78.2
48.6
16.8
-
(±6.6)
(±1.9)
(± 3)
(±5.8)
(±1.1)
(± .1)
(±7.2)
(±1.8)
(±6.7)
(±5)
(±2.4)
(±1.2)
Day
6.3
-
1.8
1.0
6.2
-
-
41.8
6.8
45.7
58.5
36.3
16.0
-
sterile sediment
Bayou Chico
and
4_
(±1.7)
(± -5)
(± -3)
(±1.1)
(±9.1)
(± 2)
(±8.6)
(±3)
(± .7)
(± .8)
bottles
Day £
5.4
-
-
-
4.9
-
-
6.0
0.7
8.5
18.9
27.4
12.3
-
from
!
(±2
(±1
(±
(±
(±1
(±9
(±5
(±2
petrol eum-deri ved
Day 1
.2) 2.4
-
-
-
.4) 2.3
-
-
3) 3.2
.2)
.5) 3.6
.8) 3.5
.5) 7.5
.4) 6.1
_
JP-4.
3
(+ .5)
(± .5)
(± -5)
(± -7)
(± -4)
(±6.5)
(± 4)
aAverage of replicate samples.
bBad replicate; n=l.
clnterferences prevent accurate integration.
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mgA) .
-------
TABLE 13. DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE SEDIMENT WITH PJP-4
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 13
Benzene - -
Cyclohexane 3.3 (± .8)
2,3-Dlmethylpentane 1.1 (± .3) - - 2.2 (± .4)
3-Methylhexane 4.1 (+1.8) 1.2 (±1.2) 1.5 (± .2) 1.7 (± .3) 2.9 (+1.5)
Heptane 336.3(±50.1) 16.7(^29.6) 18.7 (±4.5) 11.9 (± .2) 117.6(^66.1) 23.6 ( ± 5)
Methyl cyclohexane 5.7 (± .7) 3.4 (±1.4) 2.2 (+_ .9) 2.0 (± .4) 2.4 (+1.3)
2,5-Dlmethylhexane 1.1 (± .2)
2,4-Dimethylhexane 2.1 (+ .3) -
—
Methyl benzene 3.6 (± .3)
2-Methyl heptane 9.3 (±1.2) 3.5 (+1.4) 3.8 (+1.3) 3.6 (+ .5) 5.7 (±3.2) 1.5 (± .2)
3-Methyl heptane 12.0 (+1.1) 4.4 (^2.1) 3.1 (+_!.!) 4.6 (+_ .4) 7.7 (±4.3) 1.8 (+ .2)
1,1-Dimethylcyclohexane - -
Octane 18.2 (+_ .9) 8.3 (±3.4) 8.4 (+_ 2) 8.3 (+ .2) 11.3 (+5.7) 2.7 (± .3)
Ethyl cyclohexane 4.9 (± .1) 5.5 (+_ .7) 2.3 (+_ .8) 2.2 (+_ .1) 2.6 (+1.5)
Ethylbenzene 2.2 (± .1) 3.6 (+_ .3)
m-Xylene - 1.3 (+_ .4) 1.0 (±1.5) 1.3 (± 0) -
£-Xylene 8.5 (±1.3) 1.5 (± .3) - - 0.9 (± .5)
o-Xylene 3.7 (+ .7) 1.7 (+ .2)
-------
TABLE 13. DATA FROM BAYOU CHICO BOTTLE TEST, ACTIVE SEDIMENT WITH PJP-4 (CONCLUDED).
on
-Pi
Hydrocarbon
Nonane
Isopropylbenzene
1,3,5-Trimethyl benzene
1, 2, 4-Tri methyl benzene
Decane
1, 2, 3-Tri methyl benzene
Indan
Undecane
Naphthalene
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Day Q
14.6 (4-
0.5 ( +
7.1 (+_
11.8 (±
29.4 (±
7.1 ( +
1.7 (±
54.8 (±3
14.0 (±
60.4 (±1
51.9 (±1
38.3 (±1
13.1 (±
-
.2)
.1)
0)
.5)
.8)
0)
.1)
.7)
.3)
.6)
.6)
.3)
.7)
Day 1
17.0 (±
-
9.6 (±
26.0 (±
116.1 (±
8.7 (±
2.9 (±
87.0 (±
25.9 (±
101.0 (±
86.3 (±2
54.5 (±
17.0 (±
-
1)
.1)
0)
0)
.1)
-1)
.1)
•2)
.2)
.9)
.5)
.2)
Day 2
5.9
-
2.2
3.2
11.8
2.0
-
42.1
14.3
67.5
64.7
40.7
13.4
-
(±1.3)
(± -3)
(± -4)
(± -3)
(± .1)
(±1.7)
(±1.1)
(±4.1)
(±6.9)
(±2.7)
(±1.2)
Day
5.9
-
1.3
1.0
5.5
-
-
14.5
6.7
48.0
63.6
44.3
20.2
-
£
(± .2)
(± 0)
(± -2)
(± .2)
(±1.1)
(± -8)
(±3.4)
(+3.9)
(± 2)
(+1.1)
Day {
6.4
-
1.1
-
5.4
-
-
6.6
0.8
7.3
15.4
25.5
12.2
-
I
(+3.1)
(± -6)
(+2.6)
(±3.2)
(± -4)
(+2.9)
(± 4)
(± .6)
(± -7)
Day 13
1.6 ( 0)
-
-
-
1.4 ( .1)
-
-
2.1 ( .5)
-
2.5 ( .4)
2.9 ( 1.1)
7.2 ( 8.2)
5.3 ( 4.6)
-
Concentrations (mg/£)a of selected hydrocarbons in active sediment bottles from quiescent bottle test,
using sediment samples from Bayou Chico and petroleum-derived JP-4.
aAverage of replicate samples.
bBad replicate; n=l
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mgA).
-------
TABLE 14. COMPARISON OF DEGRADATION RATES IN THE BAYOU CHICO TEST
Hydrocarbon
Methyl cycl ohexane
Ethyl cyclohexane
Ethyl cycl ohexane
p-Xylene
en
en
Hydrocarbon
Decane
Ethyl cycl ohexane
Ethyl cycl ohexane
Dodecane
Source
Shale
Shale
Petroleum
Shale
Sample
Steril e
Sterile
Active
Steril e
Sample
Type
Sediment
Sediment
Sediment
Sediment
Type
water
sediment
sediment
water
Sterile
Confidence
Ratefh'1) Limits
-.0118 +.0065 to -.0300
-.0048 +.0006 to -.0101
-.0032 +.0004 to -.0067
-.0035 +.0177 to -.0246
Shale-derived
Confidence
Rate(h-1) Limits
-.018 +.004 to -.040
-.005 +.001 to -.010
-.0003 +.0030 to -.0035
-.0056 +.0014 to -.0096
Rateslh'1)
-.0008 +.
-.0003 +.
-.0015 +.
-.0008 +.
Petrol
Rates(h-1)
-.019 +.
-.003 +.
-.0015 +.
-.0047 +.
Active
Confidence
Limits
0275 to -.0290
003 to -.0035
001 to -.0039
0275 to -.029
eum derived
Confidence
Limits
004 to -.034
0004 to -.0067
001 to -.0039
0006 to -.0099
Significant
Difference
None
None
None
None
Significant
Difference
None
None
None
None
Comparison of rates of disappearance of selected hydrocarbons in shale-derived and petroleum-derived jet fuels from
quiescent bottle tests containing water and sediment from Bayou Chico relative to sterile and active systems (top) and
fuel types (bottom).
-------
than higher boiling ones. No significant difference in disappearance rates
was noticed between SJP-4 and PJP-4 (Table 23).
Subsequent tests with radiolabeled substrates indicated that mineral-
ization of hydrocarbons to C02 was occurring (Figure 17).
D. TOXICITY TESTING
The results of our toxicity testing are presented in Figure 18. The test
results clearly indicate a toxic effect as a result of exposure to SJP-4.
Toluene was mineralized by the substrate, but the addition of SJP-4 to the
environmental sample resulted in almost no C02 production indicating a
toxic effect.
E. DISSOLVED ORGANIC CARBON
Results from quiescent bottle tests in which SJP-4 and PJP-4 were in-
cubated with water samples from several locations showed unexplained vari-
ability in hydrocarbon evaporation rates. We hypothesized that variations
in DOC from one sample to another may be responsible for the variations in
the evaporation rates observed in our experiments because hydrocarbons evap-
orated less rapidly when dissolved in water than when incorporated into a
surface slick.
Hydrocarbon solubility increased with the addition of DOC as evidenced
by decreasing evaporation rates (greater persistence in sterile systems)
with increasing DOC concentrations (Figure 19). The increase in solubility
of alkanes was approximately proportional to DOC concentrations at both
24 and 48 hours. The solubilities of aromatic compounds were similarly
affected (Figure 20).
F. Jet Fuel Evaporation Rate
Ninety percent of the SJP-4 evaporated within 6 days (Figure 21). This
represents an idealized situation since, in the field, wind currents will
56
-------
TABLE 15. DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE WATER WITH SJP-4
Hydrocarbon
Benzene
Cyclohexane
2,3-Dlmethyl pentane
3-Methylhexane
Day 0 Day 1 Day 2 Day 4 Day 8
4.2 (+2.4) -
15.5 (+0.4) -
75.4 (+0.3) -
33.5(+13.2) - 11.3 (+9.6)
Day 12
-
-
-
-
Heptane 487.3(+82.0) 324.5(+_19.2) 181.2(+_68.9) 167.1(^11.5) 57.5(^12.7)
Methylcyclohexane 50.5 (+1.9)
2,5-Dimethylhexane 17.4 (+_0.0) -
2,4-Dimethylhexane 36.0 (+0.4) -
Methylbenzene 16.4 (+0.2) -
2-Methylheptane 50.5 (+1.4) -
3-Methylheptane 34.7(^15.6) -
1,1-Dimethylcyclohexane 1.3 (+0.0)
Octane 50.4(+_24.6) -
Ethylcyclohexane 38.3 (+1.4) -
Ethylbenzene 10.5 (+_2.6) -
ni-Xylene 28.6 (+1.6)
£-Xylene 18.3 (+_0.2) 0.3b -
o-Xylene 22.8 (+7.4) - 2.7 (+4.5) 3.7 (+0.1) 3.8 (+0)
-------
TABLE 15. DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE WATER WITH SJP-4 (CONCLUDED).
en
CO
Hydrocarbon
Nonane
Isopropylbenzene
Day (
42.7
1.1
)
(±2.5)
(±0.6)
Day 1 Day 2 Day 4
1.9 (±0.2)
Day 8 Day 12
-
1,3,5-Trimethylbenzene 24.5 (±1.2) 2.3 (±1.6)
1,2,4-Trimethylbenzene 27.5 (±1.9) 4.9 (±0.3) 0.6 (+_ 0)
Decane 50.3(±10.8) 17.2 (±8.5) 5.9 (±1.0) 0.!
1,2,3-Trimethylbenzene 6.5 (+0.4) 2.1 (+0.9)
Indan
Undecane
NapHthalene
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
7.
69.
12.
76.
62.
49.
22.
-
6
6
7
0
6
6
it
(±0.3)
(±2.8)
(±2.9)
(±0.9)
(±2,6)
(±1.5)
>
2.7
56.0
9.2
75.1
71.6
59.3
26.3
-
(±0.1)
(±4.1)
(±0.7)
(±5.2)
(±9.7)
(±4.8)
(±2.6)
0.
45.
9 =
72.
78.
54.
46.
-
8 (+0.3)
2 (+8.2)
5 (±1.0)
8(±10.9)
0(±10.8)
8 (+8.5)
4 (+5.7)
-
16.5
4.1
46.4
57.7
49.1
20.2
-
(±4.5)
(±0.6)
(±2.9)
(±0.7)
(±3.4)
(±1.2)
.-
-
-
2.3 (+1
22.0 (+_9
42.4 (+1
21.5 (+2
-
-
-
-
.8)
.8)
.9)
.5)
-
Concentrations (mgA)a of selected hydrocarbons in sterile water bottles from quiescent bottle test,
using water samples from Escambia River and share-derived JP-4.
aAverage of replicate samples.
^Bad replicate; n=l
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mgA) .
-------
TABLE 16. DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE WATER WITH SJP-4
01
Hydrocarbon
Benzene
Cyclohexane
2,3-Dimethylpentane
3-Methylhexane
Heptane
Methylcyclohexane
2,5-Dlmethylhexane
2,4-Dlmethylhexane
Methyl benzene
2-Methylheptane
3-Methy"! heptane
Day 0
5.7 (+0.2)
14.4 (+0.4)
72.8 (+0.3}
40.6 (+0.7)
481.6 (+1.3)
50.0 (±0.1)
16.1 (+0.1)
20.6 (+0.2)
31.2 (+1.3)
48.8 (+0.9)
47.4 (+0.8)
1,1-Dimethylcyclohexane 1.3 (+_ 0)
Octane
Ethylcyclohexane
Ethyl benzene
m-Xylene
_p_-Xylene
o-Xylene
32.9 (+0.6)
38.4 (+1.5)
13.4 (+0.7)
28.7 (+1.8)
18.4 (+1.0)
28.1 (+1.8)
Day 1
Day 2
Day 4
Day 8
Day 12
14.6 (+ .2)
-------
TABLE 16. DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE WATER WITH SJP-4 (CONCLUDED).
CT>
O
Hydrocarbon
Nonane
Isopropyl benzene
1, 3, 5 -Tri methyl benzene
1, 2, 4-Tri methyl benzene
Decane
1,2, 3-Trimethyl benzene
Indan
Undecane
Napthalene
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Day
46.
1.
25.
28.
63.
7.
8.
74.
11.
81.
70.
50.
23.
-
:_c
5
i
4
8
4
4
8
5
4
5
4(
7
4
)
(±2
(±0
(±1
(±2
(±4
(±0
(±0
(±5
(±1
(±6
±10
(±5
(±2
.5)
.6)
.7)
.1)
.4)
.6)
.7)
.9)
.0)
.8)
.2)
.0)
.3)
Day
1.
-
3.
3.
18.
1.
2.
47.
7.
62.
56.
46.
21.
-
4
0
8
5
*
1
!_
(±1.2)
(±1.9)
(±2.4)
(±8.6)
(±0 . 8)
(±1.2)
0(±10.6)
1
2
9
0
5
(±1.3)
(±8.0)
(±6.4)
(±4.0)
(±1.7)
Day 2
-
0.4
0.5
7.2
0.5
0.5
42.5
8.2
67.3
68.1
49.0
31.9
-
(±0.5)
(±0.7)
(±1.9)
(± 0)
(±0.3)
(±2.9)
(±0.1)
(±0.1)
(±5.6)
(±0.9)
(±0.8)
Day 4
-
-
-
0.5 (±
-
-
15.5 (±0.
4.2 (±0.
44.1 (±0.
50.5 (±1.
40.9 (±0.
Day 8 Day 12
-
-
-
0)
_
-
3)
1) 0.2 (± .4)
8) 7.4 (±6.3)
7) 33.6(±11.6)
3) 44.1 (± 6)
16.7 (±0.1) 21.5 (±1.9)
-
-
Concentrations (mg/£)a of selected hydrocarbons in active water bottles from quiescent bottle test,
using water samples from Escambia River and shale-derived JP-4.
aAverage of replicate samples.
DBad replicate; n=l
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mg/£).
-------
TABLE 17. DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE WATER FROM SEDIMENT SAMPLES WITH SJP-4
Hydrocarbon
Benzene
Cyclohexane
2,3-Dimethylpentane
3-Methylhexane
Day 0 Day 1 Day 2 Day 4C Day 8
5.1 (+0.2) -
12.3 (+0.5) -
64.7 (+_2.6) -
36.3 (+1.4) 24.8 (+1.8) 28.7 (+1.5)
Day 12
-
-
-
-
Heptane 472.6(^15.9) 286.7(+29.2) 204.1(^78.5) 189.9 67.0(^16.7)
Methylcyclohexane 44.9 (+1.7) 0.4 (+0.1) -
2,5-Dimethylhexane 14.3 (+0.6) -
2,4-Dlmethylhexane 18.2 (+0.7) -
Methylbenzene 28.7 (+1.0) -
2-Methyl heptane 44.5 (+1.9) 4.1 (+0.2) 2.5 (+0.8) 2.2 0.7 (+_ 1)
3-Methyl heptane 43.4 (+2.0) 3.7 (+0.1) 2.4 (+0.8) 2.0 0.8 (+1.1)
1,1-Dimethylcyclohexane 1.1 (+0.1)
Octane 30.4(+_1.0) 2.6 (+0.2) 1.6 (+0.6) 1.5
Ethyl cyclohexane 35.3(+1.4) 3.3 (+0.1) 1.9 (+_0.7) 2.1 0.1 (+_ 1)
Ethylbenzene 10.4(^3.0) 0.6 (+_0.1) -
£-Xylene 27.2(+_1.0) 0.8 (+0.1)
2-Xylene 16.4 (+_0.6) 0.9 (+0.1) 0.8 (+0.1) 0.5
o-Xylene 26.1 (+0.6) 0.9 (+0.2) -
-------
TABLE 17. DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE WATER FROM SEDIMENT SAMPLES WITH SJP-4
(CONCLUDED).
dh
Hydrocarbon
Nonane
Isopropyl benzene
1 , 3, 5 -Trl methyl benzene
1 , 2, 4-Tri methyl benzene
Decane
1,2, 3-Trimethyl benzene
Indan
Undecane
Naphthalene
Dodecane
Trldecane
Tetradecane
Pentadecane
Hexadecane
Day 0
42.7 (+1.4)
1.2 (+0.0)
23.0 (+0.6)
26.6 (+0.6)
56.2 (+0.1)
6.6 (+0.1)
7.6 (+0.1)
66.0 (+0.4)
9.2 (+0.6)
70.3 (+0.5)
61.5 (+1.6)
45.1 (+2.2)
21.0 (+1.3)
Concentrations (mg/£)a of selected
test, using sediment samples from
Day 1
6.2 (+0.9)
-
5.6 (±1.2)
6.9 (+2.1)
24.5 (+4.7)
1.9 (+0.5)
2.9 (+0.9)
50.3 (+8.1)
7.7 (+2.0)
67.7(+11.2)
63.7 (+.4.2)
48.6 (+4.3)
23.0 (+2.1)
hydrocarbons
Escambia River
Day 2
2.9 (+1.1)
-
1.7 (+.0.6)
1.6 (+0.6)
8.3 (+.2.4)
-
0.8 (+0.3)
28.8 (+7.9)
4.7 (+1.5)
42.7(+ll.l)
41.2 (+8.2)
30.2 (+7.4)
17.3 (+4.3)
Day 4C
2.9
-
-
0.6
4.1
-
-
15.5
3.8
42.7
61.5
49.7
22.4
in sterile sediment bottles
and shale-deri
ved JP-4.
Day 8 Day 12
1.1 (jf 1.5)
-
-
-
2.1 (±1.9)
-
-
3.1 (+2.6)
-
5.0 (+1.4)
18.7(^10.2)
34.5(+_12.6)
19.5(± 5.1)
from quiescent bottle
aAverage of replicate samples.
t>Bad replicate; n=l
C0ay 4 - no duplicate sample.
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mgA) .
-------
TABLE 18. DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE SEDIMENT WITH SJP-4
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 12
Benzene 5.0 (+0.1) -
Cyclohexane 11.7 (+0.2)
2,3-Dimethylpentane 59.5 (+0.2) -
3-Methylhexane 33.8 (+1.0) - 1.3 (+1.8)
Heptane 408.2(+_15.9) - 14.1(+13.1)
Methylcyclohexane 42.1 (+1.7)
2,5-Dimethylhexane 13.3 (+0.3) -
2,4-Dimethylhexane 17.3 (+0.9) -
Methyl benzene 28.2 (+0.1) -
2-Methyl heptane 39.9 (+3.9) - 0.9 (+3.2)
3-Methyl heptane 41.7 (+2.2) 1.8 (+.1.4) 2.4 (+.6.4)
1,1-Dimethylcyclohexane 1.0 (+.0.1)
Octane 28.9 (+2.2) - 2.0(+_36.5)
Ethyl cyclohexane 34.1 (+2.4) 1.6 (+1.3) 1.6 (+.1.8)
Ethyl benzene 10.2 (+.2.0) -
rri-Xylene 28.5 (+0.2)
£-Xylene 14.8 (+.2.2) -
o-Xylene 24.3 (+.3.2)
-------
TABLE 18. DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE SEDIMENT WITH SJP-4 (CONCLUDED).
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 12
Nonane 41.7 (4-3.3) 3.3 (±1.6) 2.3 (±2.4)
Isopropylbenzene 1.1 (+0.2) -
1,3,5-Trimethylbenzene 23.0 (±1.2) 3.8 (+0.6) 1.2 (±1.8)
1,2,4-Trimethylbenzene 27.3 (±1.3) 6.6 (+0.2) 1.4 (+2.2)
Decane 57.1 (+4.1) 20.2 (±0.4) 4.8 (± 5) 2.3 (±2.4) 0.9 (± 2)
1,2,3-Trimethylbenzene 6.7 (+0.6) 1.5 (+0.1)
Indan 7.8 (+0.6) 2.4 (±0.1) -
Undecane 66.9 (+.6.7) 47.9 (+1.6) 16.1 (±9.4) 7.1 (+4.2) 1.5 (±1.1)
Naphthalene 8.8 (±2.0) 7.3 (± 0) 3.7 (± 1) 2.3 (± .3) 0.5 (+• .3)
Dodecane 75.6 (±7.8) 65.7 (+5.4) 31.9(+_10.4) 29.4 (+4.8) 11.0 (+4.2)
Tridecane 63.8 (±4.3) 66.8 (±6.0) 36.5 (±9.5) 48.7 (±5.9) 35.3 (±3.6)
Tetradecane 49.2 (±2.1) 52.5 (±3.7) 28.3 (±7.7) 40.1 (±1.9) 39.1 (± .7)
Pentadecane 21.9 (±1.0) 24.6 (±1.6) 12.4 (±4.2) 18.1 (±1.3) 19.5 (± .4)
Hexa-decane - - - - - -
Concentrations (mg/£)a of selected hydrocarbons In active sediment bottles from quiescent bottle test,
using sediment samples from Escambia River and shale-derived JP-4.
aAverage of replicate samples.
bBad replicate; n=l
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mg/£).
-------
TABLE 19. DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE WATER WITH PJP-4
Ol
en
Hydrocarbon
Benzene
Cyclohexane
2,3-Dimethylpentane
3-Methylhexane
Heptane
Methylcyclohexane
2,5-Dlmethylhexane
2,4-Dlmethylhexane
Methyl benzene
2-Methylheptane
3-Methylheptane
1,1-Dimethylcyclohexane 4.3 (+0.2)
Octane 170.0 (+4.0)
Ethylcyclohexane 36.9 (+8.1)
Day 0
13.6 (+0.8)
52.9 (+5.3)
76.5 (+2.2)
56.4 (+2.8)
2110.8(+37.0)
63.0 (+1.6)
18.5 (+0.4)
30.3 (+0.1)
28.9 (+0.4)
97.6 (+1.4)
Ethyl benzene
ni-Xylene
jj-Xylene
o-Xylene
15.7 (+0.7)
27.3 (+6.3)
21.0 (+2.8)
20.5 (+3.8)
Day 1
Day 2
Day 4
Day 8
Day 12
14.5 (+ .1)
-------
TABLE 19. DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE WATER WITH PJP-4 (CONCLUDED).
CTi
Hydrocarbon
Nonane
Isopropyl benzene
1 , 3,5-Trimethyl benzene
1,2, 4-Tri methyl benzene
Decane
1,2,3-Trimethyl benzene
Indan
Undecane
Naphthalene
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Concentrations (mg/£)a
Day
83.
2.
21.
28.
78.
16.
4.
84.
18.
73.
62.
48.
17.
_
of
8
7
4
3
8
3
6
9
3
3
5
1
8
0
(+19
(+0
(+6
(±7
(±5
(±2
(±1
(+6
(±o
(±5
(±1
b
b
-8)
.2)
.9)
.4)
.6)
-0)
-0)
• 1)
.2)
.6)
.6)
selected
Da
3
3
5
26
3
1
60
12
66
56
43
16
JLJ
.3
-
.4
.1
.6
.2
.3
.2
.3
.6
.8
.0
.0
-
L_
(+0.
(+0.
(+0.
(+1.
(+p.
(±
(+1.
(+0.
(+2.
(+0.
(+0.
(+0.
3)
3)
6)
3)
2)
0)
8)
2)
0)
9)
4)
2)
hydrocarbons
Day 2
-
-
-
-
4.3
0.2
-
40.0
9.7
59.6
60.1
44.5
23.0
-
in acti
(I1
(+0
(+5
(±1
(+6
(+4
(+3
(+2
ve
Day 4 Day 8 Day 12
_
_
_
_
.4) -
.3)
_
.8) 5.9 (+1.8)
.7) 3.1 (+0.3)
.7) 30.4 (+1.5) 0.5 (+_ .6)
.0) 40.5 (+0.7) 10.5 (+,2.4)
.2) 34.2 (+1.0) 27.7 (+1.4)
.1) 11.7 (+,0.6) 13.0 (+_ .1)
-
water bottles from quiescent bottle test.
using water samples from Escambia River and petroleum-derived JP-4.
aAverage of replicate samples.
bBad replicate; n=l
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mg/£).
-------
TABLE 20. DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE WATER WITH PJP-4
Hydrocarbon
Benzene
Cyclohexane
2,3-Dimethylpentane
3-Methylhexane
Day 0 Day 1
14.3 (+2.6)
60.2 (+4.0)
85.0 (+_8.6)
61.2 (+5.9)
Day 2 Day 4 Day 8 Day 13
23.7 (+0.1)
Heptane 2,310.0(+292.3) 322.1(^26.1) 212.1 (+7.0) 142.6(+15.5) 50.9(+11.1)
Methylcyclohexane 65.2 (+9.2)
2,5-Dlmethylhexane 18.5 (+3.0) -
2,4-Dimethylhexane 30.8 (+4.7) -
Methyl benzene 27.7 (+6.3) -
2-Methyl heptane 94.3(+_16.4) -
3-Methylheptane 114.2(^21.6) - - 0.4^
1,1-Dimethylcyclohexane 4.0 (+0.8) -
Octane 160.8(+_31.7) - - 0.9 (+0.3)
Ethyl cyclohexane 38.8 (+_8.1) -
Ethylbenzene 14.5 (+3.4) -
m-Xylene 27.9 (+_6.9) -
2-Xylene 20.5 (+_4.7) -
o-Xylene 21.5 (+5.2) - 4.1 (+_0.3) - 4.0 (+• .6)
-------
CTi
CO
TABLE 20. DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE WATER WITH PJP-4 (CONCLUDED).
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 13
Nonane 85.2(+19.1) 1.4 (+_ .4) - 0.6 (j+0.2)
Isopropylbenzene 2.5 (+0.6) -
1,3,5-Trimethylbenzene 22.9 (+5.8) 1.8 (+0.4) 0.2 (+0.3)
1,2,4-Trimethylbenzene 29.0 (+7.8) 3.1 (+0.8) 0.4 (+0.6)
Decane 71.9(+17.4) 19.4 (+3.0) 6.2 (+4.6) 0.4b
1,2,3-Trimethylbenzene 12.9 (+_3.3) 2.3 (+0.4) 0.5 (+0.6) -
Indan 4.7 (+1.4) 0.9 (+0.1) 0.2 (+0.3)
Undecane 77.0(^17.2) 55.7 (+5.9) 44.9 (+.8.1) 8.2 (+5.9)
Napthalene 16.3 (+3.9) 11.9 (+1.2) 11.1 (+0.7) 3.4 (+1.6)
Dodecane 66.9(+_14.0) 66.0 (+6.5) 63.6 (+0.4) 35.0(+11.0) 0.5 (+_ .8)
Tridecane 56.0(+10.6) 60.7 (+6.4) 64.3 (+3.3) 48,4 (+8.1) 11.1 (+5.8)
Tetradecane 43.1 (^7.8) 49.8 (+4.7) 50.7 (j+4.6) 44.8 (+.6.7) 32.3 (+_6.1)
Pentadecane 16.4 (+2.7) 18.2 (+2.0) 32.7 (+2.2) 14.7 (+2.4) 19.3 (+_ .9)
Hexadecane - - - - - -
Concentrations (mg/£)a of selected hydrocarbons in sterile water bottles from quiescent bottle test,
using water samples from Escambia River and petroleum-derived JP-4.
aAverage of replicate samples.
bBad replicate; n=l
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mg/Ji) .
-------
TABLE 21. DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE SEDIMENT WITH PJP-4
Hydrocarbon
Benzene
Cycl ohexane
2,3-Dimethyl pentane
3-Methylhexane
Day 0 Day 1 Day 2 Day 4
13.2 (+_ 0)
48.5 (+0.5) ..-
71.4 (+1.3)
51.6 (+1.0) 25.4 (+0.6) 32.9 (+4.3)
Day 8C Day 13
-
-
-
-
Heptane 2310.0(+48.1) 270.5 (+_5.9) 326.8(+_28.0) 176.0(+39.1)
Methylcyclohexane 58.4 (+1.5) - 1.0 (+0.1)
2,5-Dimethylhexane 16.8 (+0.3) -
2,4-Dimethylhexane 28.2 (+0.8)
Methylbenzene 28.1 (+0.9) - 0.6 (+0.2)
2-Methyl heptane 91.6 (+3.7) - 2.6 (+0.0) 3.9 (+2.5)
3-Methylheptane 114.2 (+4.5) - 3.5 (+_0.3) 5.1 (+_3.3)
1,1-Dlmethylcyclohexane 3.7 (+0.2) -
Octane 161.1 (+_6.9) 1.1 (+_0.6) 4.8 (+_0.7) 7.9 (+_4.8)
Ethyl cycl ohexane 40.0 (+1.8) - 1.1 (+0.8) 1.0 (+_1.3)
Ethylbenzene 15.3 (+0.7) -
rri-Xylene 28.6 (+_1.7)
2-Xylene 23.5 (+_0.8) - - 0.7 (+ .3)
o-Xylene 22.9 (+1.0)
-------
TABLE 21. DATA FROM ESCAMBIA RIVER BOTTLE TEST, STERILE SEDIMEN1 WITH PJP-4 (CONCLUDED).
Hydrocarbon
Nonane
Isopropyl benzene
1 , 3 ,5-Trimethyl benzene
1 , 2, 4-Trimethyl benzene
Decane
1,2, 3-Trimethyl benzene
Indan
Undecane
Naphthalene
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
91.
2.
24.
31.
77.
14.
4.
83.
16.
72.
60.
43.
15.
_
Concentrations (mgA)a of
test, using sediment samp!
- 0
5 (±4.6)
5 (±0.4)
7 (±1.2)
9 (+1.4)
4 (±3.9)
6 (±0.6)
9 (±0.1)
5 (±3.6)
6 (±0.5)
3 (±2.6)
6 (±3.0)
1 (+ 0)
9 (±0.4)
selected
es from
Day 1
1.5
-
1.4
2.5
15.8
1.8
0.7
49.3
10.7
60.9
55.3
43.6
15.9
-
(±
(±0
(±0
(±2
(±0
(±0
(±3
(±0
(±2
(±2
(±1
(±0
0)
.3)
• 7)
.6)
.3)
.1)
.2)
•6)
.5)
.0)
.6)
.7)
hydrocarbons i
Escambia River
Day
3.
-
0.
1.
8.
0.
-
45.
11.
70.
69.
50.
21.
-
3 (±0.
8 (±0.
0 (±0.
1 (±5.
8 (±0.
3 (±20.
6 (±3.
2 (±24.
2(±24.
9(±15.
8 (±9.
n sterile
and
petrol
8)
7)
9)
0)
7)
6)
9)
4)
3)
8)
6)
Day
5.4
-
0.9
-
4.7
-
-
10.4
3.8
30.6
37.6
30.6
11.2
-
sediment
eum-deri
4_
(±3
(±
(±2
(±4
(±
(±5
(±5
(±3
(±
Day 8C Day 13
.1)
-
.5) -
-
.7)
-
-
.5)
1)
.9)
.4) 7.5
.5) 8.2
.9) 5.9
_ _
bottles from quiescent bottle
ved
JP-4.
aAverage of replicate samples.
bBad replicate; n=l
^Day 8 - No duplicate sample.
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mg/£).
-------
TABLE 22. DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE SEDIMENT WITH PJP-4
Hydrocarbon
Benzene
Cyclohexane
2,3-Dimethyl pentane
3-Methylhexane
Heptane
Methyl cyclohexane
2,5-Dimethylhexane
2,4-Dimethyl hexane
Methyl benzene
2-Methyl heptane
3-Methyl heptane
Day 0
13.2 (+0.1)
43.8 (+3.4)
65.3 (+_5.0)
48.1 (+3.2)
1874.3(+86.3)
56.1 (+2.3)
16.6 (+0.5)
27.7 (+0.7)
29.0 (+0.7)
92.1 (+_ 0)
113.1 (+0.2)
1,1-Dlmethyl cyclohexane 3.8 (+_ 0)
Octane
Ethyl cyclohexane
Ethyl benzene
m-Xyl ene
jD-Xylene
o-Xylene
165.2 (+4.1)
41.3 (+1.4)
16.0 (+0.7)
31.3 (+0.8)
23.2 (+3.5)
22.8 (+1.3)
Day 1 Day 2 Day 4 Day 8 Day 13
_
-----
3.1 (+4.5)
47.2(+56.3) - 13.2 (+_ .5)
41.3(+36.6) 318.3(+167.0) -
55.9(+_68.3) - - -
3.1 (+3.5)
_
8.3(^11.8)
2.3 (+2.2) 55.7(+_57.0) -
3.4 (+_3.3) 66.4(^63.0) - 0.7 (+_ 1)
0.8 (+1.1) -
5.1 (+_4.9) 187.6(+_178.2) - 1.1 (^1.5)
16.9(+17.0) -
9.0(+12.8)
6.2 (+8.8)
13.9(+16.1) -
9.4(+_13.3)
-------
TABLE 22. DATA FROM ESCAMBIA RIVER BOTTLE TEST, ACTIVE SEDIMENT WITH PJP-4 (CONCLUDED).
Hydrocarbon Day 0 Day 1 Day 2 Day 4 Day 8 Day 13
Nonane 96.2 (+_5.7) 4.7 (+0.3) 46.7(+43.3) - 0.7 (+_ 1)
Isopropylbenzene 2.6 (+0.7) -
1,3,5-Trimethylbenzene 26.2 (+1.7) 6.7 (+2.7) 9.9 (+.9.4)
1,2,4-Trimethylbenzene 34.9 (+2.3) 4.9 (+1.2) 20.0(^19.7)
Decane 83.9 (+_5.7) 23.3 (+.1.4) 28.7(^14.6) - 0.7 (+_ 1)
1,2,3-Trimethylbenzene 15.7 (+1.1) 3.1 (+0.6) 3.8 (+.3.1)
Indan 5.2 (^0.5) 1.0 (+.0.1) 1.9 (^1.8)
^ Undecane 90.3 (+6.2) 57.1 (+4.5) 32.8 (+4.7) 14.7 (+3.8) 1.0 (+1.5)
PO
Napthalene 17.5 (+1.0) 12.6 (+.1.1) 8.6 (+0.7) 4.7 (+_ .2)
Dodecane 78.4 (+5.1) 70.1 (+.7.6) 35.4(+_13.5) 41.4 (+3.9) 1.4(+1.2)
Tridecane 65.8 (+3.8) 59.5 (+6.8) 28.7(+_13.9) 44.9 (^2.8) 7.8 (+4.7)
Tetradecane 47.4 (+4.0) 48.0 (+6.0) 19.4(^13.0) 36.0 (+.1.8) 20.1 (+.5.8)
Pentadecane 16.7 (+1.1) 18.7 (+2.5) 6.3 (+4.4) 12.9 (+_ .6) 10.3 (+1.5)
Hexadecane - - - - - -
Concentrations (mgA)a of selected hydrocarbons in active sediment bottles from quiescent bottle test,
using sediment samples from Escambia River and Petroleum-derived JP-4.
aAverage of replicate samples.
t>Bad replicate; n=l
Parentheses indicate one standard deviation from the mean.
Dashes (-) indicate not detectable (<0.2 mg/a).
-------
TABLE 23. COMPARISON OF DEGRADATION RATES IN THE ESCAMBIA RIVER TEST
--J
CO
Sterile
Hydrocarbon
Undecane
Ethyl cyclohexane
Decane
Decane
j
>
Hydrocarbon
Decane
Decane
Nonane
Undecane
Source
Shale
Shale
Petroleum
Shale
Sample
Steril
Active
Active
Active
Sample
Type
Sediment
Sediment
Water
Sediment
Type
e water
water
sediment
sediment
Confidence
Rate(h~!) Limits
-.0069
-.011
-.0233
-.0116
Shal
+.0056
+ .005
+.0188
+.0006
e-de rived
to -
to -
to -
to -
.008
.0168
.0276
.0224
Active
Confidence
RatesCh'1) Limits
-.0086
-.0276
-.0262
-.0096
+.0062
+.1019
+.0104
+.054
to -
to -
to -
to -
.0108
.157
.0627
.0731
Significant
Difference
None
None
None
None
Petroleum derived
Confidence
Rate(h'l) Limits
-.0208
-.0216
-.0261
-.0086
+.0164
+.0159
+.0674
+.0062
to -
to -
to -
to -
.025
.0271
.1195
.0108
Rates(
-.0233
-.0262
-.0087
-.0100
Confidence
h'1) Limits
+.0188
+.0104
+.045
+.0075
to -
to -
to -
to -
.0276
.0627
.0623
.0123
Significant
Di f ference
None
None
None
None
Comparison of rates of disappearance of selected hydrocarbons from quiescent bottle
tests containing water and sediment from Escambia River relative to sterile and active systems
(top) and fuel types (bottom).
-------
DPM(XIOOO)
100
75
50
25
0
\
\
BOTTLE CONTROL
SEAWATER CONTROL
SJP4 EXPOSED
Figure 17. Decane Mineralization Following Range Point Test
74
-------
C02
WATER
...
U. - - >. v _-^ J
600000
DPM
ORIGINAL SPIKE = 1 X 10(
400000 -
200000»-
SJP-4
SJP-4 and
FORMAUN
TOLUENE
PRE-EXPOSURE
SUBSTRATE
Figure 18. Toluene Toxiclty In Range Point Water
NONE
75
-------
be variable. Gas chromatographic analysis of the fuel remaining at each
sampling time indicated enrichment of high boiling hydrocarbons as the
test progressed. Gas chromatographic analysis of jet fuel from the day-2
sample indicated that all the aromatics were below detection limits; the
remaining fuel was composed entirely of aliphatic hydrocarbons.
76
-------
STERILE
24 HOURS
ACTIVE
24 HOURS
SRERILE
48 HOURS
ACTIVE
48 HOURS
20
LU
.
O
^
LL
O
z
o
t?
-------
LJJ
Z
LU
NJ
Z
LLJ
CD
X
LLJ
2
cc
15
10
LL
O
Z
O
<
cc
LU
O
z
O
O
STERILE
24 HOURS
ACTIVE
24 HOURS
STERILE
48 HOURS
ACTIVE
48 HOURS
NATURAL WATER
1,3,5-TRIMETHYLBENZENE
+400 MG/L DOC
+800 MG/L DOC
DISSOLVED ORGANIC CARBON
Figure 20. Solubility of 1,3,5-Trimethylbenzene Versus DOC
78
-------
100
90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Time
Hours
Figure 21. Jet Fuel Evaporation Rate
79
-------
Section IV
CONCLUSIONS
Little difference was found between shale-derived JP-4 and petroleum-
derived JP-4. Under virtually all conditions tested, volatility was the
overwhelming determining factor in the fate of the component hydrocarbons.
The physical similarity of the two fuels, as seen in the compositional
analysis, precludes the possibility of detecting any differences under
these test conditions. Coupled with the importance of volatility, this
indicates that there would be little difference in the fates of the two
fuels under most environmental conditions.
The similarity of the fuels extends to the water-soluble fractions
derived from PJP-4 and SJP-4. Except for one hydrocarbon component,
benzene, the water-soluble fractions, which cause environmental damage if
a spill occurs, are essentially identical.
The results from the quiescent bottle tests suggest that volatility
is the principal loss mechanism of the hydrocarbons in shale-derived jet
fuel from water but (Range Point water) biodegradation is sometimes
important. In fact, we believe that biodegradation will only be detected
in the quiescent bottle test if the hydrocarbons are relatively slow to
evaporate; i.e., the lack of any detectable biodegradation of SJP-4 in
samples from two of the three sampling sites, was largely because hydro-
carbons were lost so rapidly by evaporation. The apparent absence of
biodegradation of SJP-4 hydrocarbons at these sites, differs somewhat
from the results of tests with PJP-4, where some biodegradation of certain
hydrocarbons in water samples from Escambia River was apparent. It is
possible that the difference in results was because SJP-4 was more volatile
than PJP-4 and thus no biodegradation was detected. Despite the large
80
-------
part played by volatilization, mineralization studies using 14C-labeled
hydrocarbons indicated that biodegradation probably was occurring and
thus^played a role in removal of JP-4 hydrocarbons. Circumstances that
reduce volatility, such as increased hydrocarbon solubility as a function
of water chemistry, would make the role of microbial degradation more
important.
The unusually high number of hydrocarbons that degraded in the quie-
scent bottle tests containing water samples from Range Point was probably
due to either an artifact in the biodegradation test procedure or a unique
environmental factor associated with the Range Point water rather than to
the hydrocarbon compostion of the SJP-4. An attempt was made to distinguish
between the two possibilities. Disappearance rates for 10 selected hydro-
carbons, cyclohexane, ethylbenzene, £-Xylene, 1,2,4-Trimethylbenzene, decane,
undecane, naphthalene, dodecane, tridecane and tetradecane, in quiescent
bottle experiments with SJP-4 and PJP-4 were calculated (Tables 24 and 25).
Confidence intervals calculated from the slopes of semilog plots indicate
that, in most cases, differences in rates between sterile and active systems
with each experiment were significantly different (confidence intervals do
not overlap).
Comparison of results with SJP-4 to results from previous studies with
PJP-4 and samples from Range Point salt marsh showed that biodegradation
rates of the indicated hydrocarbons were probably the same, regardless of
the fuel source (Table 26). This was determined by subtracting the rate
of disappearance of each hydrocarbon in the sterile water tests from its
disappearance rate in the active water test (i.e., separating out the true
biotic component). What appears to be the difference between active and
sterile systems in the SJP-4 experiment is due largely to a lower volatility
81
-------
TABLE 24. RATE OF DISAPPEARANCE OF SELECTED SJP-4 HYDROCARBONS IN RANGE POINT TEST
CO
ro
Hydrocarbon
Cyclohexane
Ethyl benzene
_p_-Xylene
1,2,4-Trimethyl-
benzene
Decane
Undecane
Napthalene
Dodecane
Tridecane
Tetradecane
Rate
-.024
-.002
-.002
-.004
-.001
-.0015
-.0004
-.0007
-.0008
-.0006
Sterile
Confidence Limits3
+.098 to
-.0004 to
-.001 to
-.0015 to
+.0002 to
+.0001 to
+.0001 to
Od to
-.0002 to
Od to
-.146
-.003
-.0025
-.0051
-.0009
-.001
-.0008
-.0012
-.0012
-.001
Rate
C
C
c
-.017
-.009
-.005
-.005
-.005
-.004
-.003
Confidence Limits3
+ .005
-.0052
-.0021
-.003
-.0035
-.0026
-.0013
to
to
to
to
to
to
to
-.035
-.0134
-.0067
-.0056
-.0067
-.005
-.0039
Significant
difference*3
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Rates of disappearance of selected hydrocarbons in shale-derived jet fuel from quiescent bottle tests containing
water from range point salt marsh.
^Confidence intervals do not overlap.
^Hydrocarbons not detected after t=o sampling.
dlnsufficient data points to calculate complete confidence limits.
-------
TABLE 25. RATE OF DISAPPEARANCE OF SELECTED PJP-4 HYDROCARBONS IN RANGE POINT TEST
oo
GO
Hydrocarbon
Cyclohexane
Ethyl benzene
£-Xylene
1,2,4-Trimethyl-
benzene
Decane
Undecane
Napthalene
Dodecane
Tridecane
Tetradecane
Rate
-.324
-.008
-.005
-.009
-.010
-.009
-.008
-.006
-.003
-.002
Sterile
Confidence Limits'5
+.9694
-.0021
-.0096
-.0045
-.0055
-.007
-.005
-.004
-.0016
-.0008
to
to
to
to
to
to
to
to
to
to
-1.6163
-.0125
-.100
-.0133
-.0135
-.0106
-.010
-.0072
-.004
-.0028
Rate
d
-.163
-.063
-.051
-.021
-.023
-.016
-.011
-.007
-.004
Confidence Limits'5
-.0903
-.0185
-.0428
-.0154
-.0174
-.0143
-.0093
-.005
-.0024
to
to
to
to
to
to
to
to
to
-.2343
-.1061
-.0592
-.0268
-.0290
-.0179
-.0119
-.0092
-.0054
Significant
difference0
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Rates of disappearance of selected hydrocarbons in petroleum-derived jet fuel from quiescent bottle tests
containing water from Range Point salt marsh3
aSource: Spain, J.C., C.C. Somerville, T.J. Lee, L.C. Butler, A.W. Bourquin, "Degradation Jet Fuel
Hydrocarbons by Aquatic Microbial Communities," interim report, 23 October, 1981 to 30 September 1982,
pp. 182-185.
t> a=0.05
cConfidence intervals do not overlap.
^Hydrocarbons not detected after t=o sampling.
-------
TABLE 26. COMPARISON OF BIOTIC DEGRADATION RATES IN RANGE POINT TEST
Hydrocarbon
Cyclohexane
Ethyl benzene
_p_-Xylene
1,2,4-Trimethyl-
benzene
Decane
Undecane
Napthalene
Dodecane
Tridecane
Tetradecane
Active
SJP-4
-
-.155
-.058
-.042
-.011
-.014
-.008
-.005
-.004
-.002
Water3
PJP-4
-
-
-
-.013
-.008
-.0035
-.0046
-.0043
-.0032
-.0024
PJP-4/SJP-4
-
-
-
.31
.73
.25
.58
.86
.80
1.2
Comparison of biotlc rates of hydrocarbon disappearance from quiescent bottle
tests containing either shale-derived (SJP-4) or petroleum derived (PJP-4) jet
fuel and water samples from Range Point salt marsh.
aActive water rates corrected for losses due to volatilization (sterile water)
84
-------
of hydrocarbons in this test than in the previous PJP-4 experiment
(Table 27). Previously, then, if volatility had been reduced in the
PJP-4 experiment, we would have seen a similar contribution of the biotic
component. These results are important relative to the fate of jet fuels
in the environment because under conditions in which volatilization might
be restricted, for whatever reasons, biodegradation appeared sufficient
to maintain at least some continued loss of the hydrocarbons from the
environment.
The difference in volatility rates between the two experiments could
be the result of differences in fuel composition. For example, unidentified
volatile hydrocarbons present in the SJP-4, but not in the PJP-4 may have
saturated the head space in the bottles and,thereby, reduced volatility.
However, it is more likely that experimental variability caused by such
factors as differences in temperature, air flow into and out of the bottles
and even sampling schedules, had the major impact on volatility.
The slower volatility rates may also be of environmental significance
because the underlying mechanism may shed light on factors that control
hydrocarbon residence time in the affected environment. Although, air move-
ment in and out of the bottle was not tightly controlled, we do not believe
that laboratory conditions during the incubation period were responsible
for the slower volatility; repeating the test, for example, with aluminum
foil closures to restrict evaporation losses did not result in an increased
amount of biodegradation. These results ruled out the possibility of an
artifact in the fate test system.
The addition of inorganic nutrients to the test waters, did not affect
biodegradation rates. Under the assumption that Range Point water may have
had higher concentrations of dissolved organic carbon (DOC), a condition
85
-------
TABLE 27. COMPARISON OF ABIOTIC DEGRADATION RATES IN RANGE POINT TEST
Hydrocarbon
Cyclohexane
Ethyl benzene
£-Xylene
1,2,4-Trimethyl-
benzene
Decane
Undecane
Naphthalene
Dodecane
Trldecane
Tetradecane
Sterile
SJP-4
-.024
-.002
-.002
-.004
-.001
-.0015
-.004
-.0007
-.0008
-.0006
Water
PJP-4
-.324
-.008
-.005
-.009
-.010
-.009
-.008
-.006
-.003
-.002
PJP-4/SJP-4
14.2
4
2.5
2.1
10.0
6.1
20.0
8.5
3.5
3.3
Comparison of abiotic rates of hydrocarbon disappearance from quiescent
bottle tests containing either shale-derived (SJP-4) or petroleum-derived
(PJP-4) jet fuel and water samples from range point salt marsh.
86
-------
that we and others (Reference 6) have shown will increase the solubility of
the hydrocarbons and decrease their volatility, a degradation test was per-
formed using a humic acid preparation from sediment to artificially increase
the DOC. Biodegradation in the test was increased by the presence of the
additional DOC but the concentration of the DOC required was unrealistically
high (Figures 19, 20). The effect we observed, however, was roughly linear
and consequently the effect of DOC we observed was probably operational at
environmentally realistic DOC levels (Figures 19,20). DOC concentration in
environmental samples should be checked because it could reduce losses of
spilled jet fuel by volatilization.
Finally, certain other circumstances also present the possibility of
increased environmental risk. According to the results of our quiescent
bottle tests, fuel hydrocarbons may strongly sorb to sediments and remain
in the receiving environment for longer periods. This result was also
observed in previous PJP-4 studies. If these hydrocarbon carrying sediments
fall into the anoxic areas of a body of water, they may represent a signifi-
cant sink of potentially damaging hydrocarbons (Reference 7).
87
-------
Section V
RECOMMENDATIONS
Our test results indicated that SJP-4 and PJP-4 should be treated in a
similar fashion in the event of a spill. Most small-scale spills require
little treatment other than those precautions normally taken for safety
reasons. In larger spills containment and recovery operations would prob-
ably be necessary. Other than those two general guidelines, specific
recommendations are not possible with our present data base, either as to
SJP-4 versus PJP-4 or to jet fuels in general. Our investigations indicate
that a variety of environmental factors can and do effect the fate of jet
fuels in aquatic environments. A spill in a placid, pristine marsh may
result in a drastically different situation than a similar spill in an
actively flowing, heavily impacted river. Recommendations for one situ-
ation could prove disastrous in the other.
Further research is indicated in four areas: (1) the fate of hydro-
carbons sorbed* to particulates especially in terms of oxygen availability;
(2) the role of water chemistry in the solubility/fate of hydrocarbons; (3)
toxicity of the water soluble fraction of fuels to representative aquatic
species as a function of time and concentration; (4) toxicity of the WSF
to the resident microbial population and the ability of the bacteria to
recover from this effect (i.e., determine the toxic threshold concentration
under different environmental conditions); (5) an investigation into the
causes of the variability in test results from site to site. Our data indi-
cate that parameters we do not as yet understand have a significant impact
on the fate of jet fuels in aquatic environments. Environmental factors
such as dissolved organic carbon, dissolved oxygen, pH, salinity, etc.,
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are all potential determining factors in the ultimate fate of jet fuels
in aquatic systems. Until the effect (or lack of it) of these parameters
on the fate of jet fuels is understood, it will be difficult, if not
impossible to make any valid site-specific predictions about the outcome
of a fuel spill of any proportion.
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REFERENCE
1. Ghassemi, M., A. Panahloo and Oulivan, S., "Comparison of Physical
and Chemical Characteristics of Shale Oil Fuels and Analogous Petroleum
Products," Environmental Toxicology and Chemistry, vol 3, pp. 511-535.
1984.
2. Hayes, P.C, and Pitzer, E.W., Characterizing Petroleum- and Shale-
Derived Jet Fuel Distillates via Temperature-programmed Kovats Indices.
Chromatography, vol. 253, pp. 179-198, 1982.
3. Hunt, T.P., Standard procedure for preparing saturated water soluble
fractions of jet fuels. Unpublished report, Environmental Quality Branch,
Toxic Hazards Division, Air Force Aerospace Medical Research Laboratory,
Wright-Patterson AFB, Ohio 45433.
4. Spain, J.C., Somerville, C.C., Lee, T.J., Butler, L.C., and Bourquln,
A.W., Degradation of Jet Fuel Hydrocarbons by Aquatic Microbial Communities,
EPA-600/X-83-059, U.S. Environmental Protection Agency, Gulf Breeze, FL, 1983.
5. Lake, J.L., Dimock, C.W. and Norwood, C.B., A Comparison of Methods for the
Analysis of Hydrocarbons in Marine Sediments. Advances in Chemistry Series,
#185, L. Petrakes and F.T. Weiss (eds.) Petroleum In the Marine Environment,
1980.
6. Boehm, P.O. and Quinn, J.G., "A Chemical Investigation of the Transport
and Fate of Petroleum Hydrocarbons in Littoral and Benthic Environments
of the Tsesis Oil Spill," vol. 6, pp. 157-173, 1982.
7. Pritchard, P.H., Mueller, L.H,. Spain, J.C. and Bourquin, A.W., Degradation
of Jet and Missle Fuels by Aquatic Microbial Communities, Report to the Air
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