EPA-670/2-73-099
February 1974
Environmental Protection Technology Series
Investigation of Surface Films -
Chesapeake Bay Entrance
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
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EPA 670/2-73-099
February 1974
INVESTIGATION OF SURFACE FILMS—CHESAPEAKE BAY ENTRANCE
by
Dr. William 6. Maclntyre
Dr. Craig L. Smith
Dr. John C. Munday
Mrs. Victoria M. Gibson
Mr. James L. Lake
Mr. John G. Windsor
Dr. John L. Dupuy
Dr. Wynam Harrison
and
Dr. John D. Oberholtzer
Project 15080 EJO
Program Element 1BB041
Project Officer
Mr. Robert D. Kaiser
Office of Research and Development, Region III
Sixth and Walnut Streets
Philadelphia, Pennsylvania 19106
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
Washington, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price $2.06
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ABSTRACT
Experimental point source oil releases have been conducted
in the Chesapeake Bay mouth area. Predictions of oil
slick motion were tested, and slicks were sampled and
analyzed to measure their aging rates over periods, up to
32 hours. Remote sensing techniques were used to detect
and measure the spreading rate of oil. Some laboratory
oil film aging experiments were done to further document
and elucidate aging processes. Results indicate a
reasonable motion prediction, an explanation of the ,
non-biological initial aging of oil films, and a fair
corroboration of a theoretical oil spreading model.
Indigenous surface films in the study area were analyzed
for lipid and chlorinated hydrocarbon content. Hydro-
carbons were 300-500 /ug/liter and fatty acids and esters
700-7800 jug/liter in surface film samples. Chlorinated .,
hydrocarbons were generally less than 100 parts per
trillion in surface films, in contrast to some earlier high
concentrations found in Biscayne Bay. Surface film
analysis limitations imposed by sampling methods are
discussed. Plankton in slick, non-slick, and subsurface
water were counted. Populations were higher in surface
than subsurface water, and higher in non-slick than in
slicked surface water.
This report was submitted by the Virginia, Institute of
Marine Science in fulfillment of Project Number 15080 EJ0
under the (partial) sponsorship of the Office of Research and
Monitoring, Environmental Protection Agency. Work was
completed as of March 17, 1972.
ii
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CONTENTS
ABSTRACT
LIST OF FIGURES
LIST OF TABLES
ACKNOWLEDGMENTS
Page
ii
iv
vi
viii
Sections
I CONCLUSIONS
II RECOMMENDATIONS
III INTRODUCTION
IV OIL SLICK MOTION
V INITIAL AGING OF OIL FILMS
ON SEA WATER
VI REMOTE SENSING OF OIL SLICKS
VII PHYTOPLANKTON IN SURFACE SLICKS
AND IN ADJACENT SUBSURFACE
AND NON-SLICK WATER
VIII CHLORINATED HYDROCARBONS IN INDIGENOUS
SURFACE FILMS
IX LIPIDS OF SURFACE FILMS ON CHESAPEAKE
BAY
X REFERENCES
XI LIST OF PUBLICATIONS
XII APPENDICES
I
3
5
10
24
69
81
99
109
130
140
141
iii
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FIGURES
No. , Page
1. Oil release experiment locations. 8
2. Relative wind factor versus wind speed from
data in Table 2. 14
3. Oil slick trajectories at Chesapeake Bay
entrance. Solid lines are observed trajectories,
dotted lines are predicted paths with squares,
circle and triangle indicating zero, three and ten
percent overall wind factor respectively. 16
4. Predicted (•-••) and observed ( ) paths for
Aug. 12, 1970, release. 18
5. Predicted (••••) and observed ( ) paths for
Dec. 3, 1970, release. 19
6. Predicted (••••) and observed ( ) paths for
April 26, 1971, release. 20
7. Predicted (••••) and observed ( ) paths for
Aug. 3, 1971, release. 21
8. Predicted (••••) and observed ( ) paths for
Sept. 14, 1971, release. 22
9. Boiling range composition of No. 2 fuel oil. 26
10. Boiling range composition of No. 4 fuel oil. 28
11. Boiling range composition of No. 6 fuel oil. 29
12. Bubbler assembly for oil film aging. 32
13. n-paraffin standards for gas chromatography. 34
14. Loss of n-paraffins from No. 4 fuel oil release,
Aug. 3, T971. 52
15. Comparison of No. 4 fuel oil aromatic fraction
b.p. 190°-250°C with No. 4 fuel oil water
solubles. 54
iv
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FIGURES (Cont'd)
No. Page
16. Scrubbing of dissolved aromatic species in
bubbler apparatus. 56
17. Change in boiling range of evaporate fraction
in bubbler apparatus. 58
18. Typical gas chromatograms of No. 2, 4, and 6
fuel oil evaporate fractions. 59
19. Loss of volatiles in bubbler apparatus. 60
20. Volatiles remaining in bubbler apparatus. 61
21. Loss of volatile fraction of No. 6 fuel oil
in bubbler and field experiments. 64
22. Loss of volatile fraction of No. 4 fuel oil
in bubbler and field experiments. 65
23. Loss of volatile fraction of No. 2 fuel oil
in bubbler and field experiments. 66
24. Spreading rate of No. 2 and No. 4 fuel oils
on seawater. 79
25. Plankton sample areas. 83
26. Comparison of surface and one meter diversity
in slick areas. 94
27. Comparison of surface and one meter diversity
in non-slick areas. 95
28. Sampling locations and dates. 101
29. Amoco oil spill trajectory. 157
30. Guinea Marsh oil sampling locations. Black
areas are oil exposed beach. 160
31. Boiling range composition of Amoco spill oil. 162
32. Gas chromatogram of Amoco Spill Oil. Integers
are carbon numbers of normal hydrocarbon peaks. 164
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TABLES
Page
!• Experimental Oil Releases 6
2. Oil Slick Motion and Relative Wind Factor 11
3 (a)-(l). Fuel Oil Aging - Loss of Normal Paraffins 37
4. Dissolved Oil Components from Bubbler
Experiment "
5. Boiling Range Composition Coefficients 62
6. Fuel Oil Aging Comparison 67
7. Oil Slick Remote Sensing Experiments 70
8. Results of Sampler Comparison Experiments 85
9. X2 Test for Randomness 87
10. Counts of Five Replicate Subsamples from
Five Samples 38
11. Counts of Ten Replicate Subsamples from
One Sample 88
12. Results of Sample Counts 90
13. Confidence Intervals of 997o Level for
Sample Counts 92
14. Composition of Surface Samples Slick
and Non-Slick 93
15. Affinity Index Values for Pairs of
Samples 93
16. Chlorinated Hydrocarbon Concentration
Results 105
17. Fatty Acid Sample Concentration and
Composition 113
18. Percentages of Predominant Fatty Acids 121
19. Hydrocarbon Sample Concentration and
Composition 122
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TABLES (Cont'd)
No. Page
20. Fatty Acid Concentration in Slicks and
Non-Slicks 129
21. Hydrocarbon Concentrations in Slicks
and Non-Slicks 129
22. Population Statistics of Marsh
Intertidal Fauna 167
vii
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ACKNOWLEDGMENTS
The authors are indebted to Mr. Paul Alfonsi of NASA,
Wallops, for his assistance in design and construction of
a surface film skimmer, and to Mr. Robert Long of NASA,
Wallops, and Captain Alan Hancock, U.S.C.G. Group, Norfolk
Commander, for their ship scheduling efforts.
Assistance in the project by the Region III personnel,
Environmental Protection Agency, especially to Mr. Ralph L.
Rhodes, Mr. Russel H. Wyer, and Mr. Robert D. Kaiser, the
Grant Project Officer, is gratefully acknowledged.
viii
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SECTION I
CONCLUSIONS
A computer program has been developed to enable prediction
of oil slick trajectories from available wind and tidal
current information. The accuracy of prediction depends
on tidal current data quality and knowledge of steady
currents. Significant errors may occur in locations where
current systems are poorly described.
The most important process in initial aging of fuel oils at
sea is the loss of volatile compounds through evaporation.
Loss of material by dissolution into seawater is quite small
and little change is produced in the oils by this aging
mechanism.
The components of a fuel oil slick which dissolve at
greatest concentration into seawater under aerated, agitated
conditions are naphthalene, and the several methyl-
substituted naphthalenes.
Quantitative determination of the degree of aging of a fuel
oil can be made from the boiling range composition of the
original oil and gas chromatographic analysis of n-paraffins
in original and aged oil samples.
Photography is useful for oil slick detection and
discrimination. The near ultraviolet band is best for
imaging edges and thin slicks. The green band best
delineates thick oil regions. Color film is useful, as
it distinguishes thick from thin oil, and fuel oil from
recent lipid slicks.
No. 2 fuel oil is distinguished from No. 4 and 6 fuel oils
by its lack of negative contrast in blue and green band
photographs.
Oil slick spreading was found to fit a theoretical model
for small volume spills of No. 2 and 4 fuel oils. No. 6
fuel oil did not spread in our tests.
In an estuarine environment the surface microlayer contains
more phytoplankton than water at one meter depth, and species
diversity is lower at the surface than at one meter.
Phytoplankton population in the surface microlayer are
lower in slick than non-slick areas. This result was
obtained with both light fuel oil and natural lipid slicks.
Samples were taken seasonally and show the usual temperate
zone species pattern with peak populations in March and
September.
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Chlorinated hydrocarbons (CHP) and polychlorinated biphenyls
(PCB) were detected in indigenous estuarine slicks and
subsurface water. Total chlorinated hydrocarbon and CHP
concentrations were generally higher in surface than sub-
surface water, while PCB concentration was similar in
surface and subsurface water.
Lipid analysis of indigenous surface slicks from
Chesapeake estuarine locations showed them to be predomi-
nantly fatty acids and esters of recent biological origin.
The minor hydrocarbon amounts were petroleum products with
the G.C. characteristics of a light fuel oil.
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SECTION II
RECOMMENDATIONS
Detailed current studies should be conducted in probable
spill areas to permit more accurate prediction of oil
transport. The computer program given here should be used
for oil spills where tidal currents are available, and
slicks will not beach for at least 12 hours.
A quick-deployment air dropped current meter system should
be developed for use at spill locations where prior
information on steady and tidal currents is unavailable.
This would make a rough prediction of slick motion possible,
The validity of the assumption of linear vector addition of
steady current and wind velocity should be tested by
experiment and theoretical analysis, so that conditions
under which the predictive model fails may be understood
with consequent improvement of the model.
Large scale turbulence produces unsteady non-tidal currents
which are not included in the present prediction model.
This phenomenon should be investigated, perhaps by remote
sensing methods, for coastal regions.
Long term aging experiments on air-barrier confined slicks
of crude and residual fuel oils should be designed to
investigate tar ball formation. The aged synthetic tar
balls should be compared with those collected in the
Atlantic Ocean. This work would permit greater under-
standing of semi-permanent oil pollution in the world ocean,
Further oil component dissolution in seawater experiments
should be conducted using GC-MS analysis. This work will
recognize the non-equilibrium nature of release of oil
aromatics and their partitioning between oil and water.
The effect of oil dispersants in keeping otherwise
volatile toxic oil aromatics in the water column should be
investigated.
Photography should be used for daylight remote detection
and discrimination of oil spills. An infrared scanner
should be used for night oil spill detection. Photography
of oils should be conducted with films and filters
suggested in this report.
Further analysis of the oil spreading model verified here
should be made and the viscosity of oil included in the
model.
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Toxicity of oil and oil components on phytoplankton should
?ia ^OT concern, because there is prior evidence that
oil adversely affects the primary aquatic producers. This
work indicates some effects of organic films on surface
phytoplankton populations.
Attempts to establish the importance of organic surface
films in concentration and transport of chlorinated
hydrocarbons should be discontinued until adequate
separation methods for compound classes are developed, a
means of sampling solely the organic surface layer without
water is devised, and methods to determine the age and prior
history of a slick are found. These requirements seem
unsatisfiable in the near future.
Information on indigenous estuarine slick composition
obtained in this study indicates the relatively unpolluted
situation in the sampled region. This work should be
repeated in other areas to establish the petroleum
hydrocarbon content of our coastal surface waters.
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SECTION III
INTRODUCTION
A series of experimental oil releases have been conducted
in the Chesapeake Bay and Virginia coastal waters.
Observations and conclusions from these and ancillary
laboratory studies are presented in this report.
The several objectives of this program were:
1.) Description and prediction of the motion of point
source oil spills under varying wind and tidal
current conditions.
2.) Collection of oil from slicks at serial times after
release, and analysis of these samples to determine
the loss of water soluble and volatile constituents.
3.) Photographic and passive radiation imaging at serial
times after oil release to establish oil spreading.
rates, document slick shape, and fix its orientation
relative to measured winds and currents.
4.) Determination of water surface photoplankton
population and species composition in film covered
and film free areas.
5.) Chemical analysis of natural films collected in the
Chesapeake Bay estuarine system to establish their
content of petroleum compounds, chlorinated organics,
and recently formed lipid substances.
Table 1 is a chronological listing of the experimental oil
releases which yielded information relating to the first
three objectives above. This tabulation should be referred
to subsequently in this report, because oil releases are
identified here by release date.
A map of the Virginia Maritime Area (Fig. 1) shows the
approximate locations of the oil releases. Detailed
navigational data are available on request from the
reporting agency.
Oil sources were: No. 6 and-No. 4 fuel oil from the Norfolk
terminal of ESSO and originating from mixed residues and
distillates of Nigerian and Venezuelan crude processed by
the Lago Refinery, Aruba, N.W.I., No. 2 fuel oil from
various local heating oil company distributors, and
menhaden oil from Haynie Products Co., Reedsville, Virginia.
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Table 1. Experimental Oil Releases
Kind of Volume Observation
Date Oil Type Release Location Observation Released Period
(gal.) (hrs.)
Sept. 12, '69 6 Ches. Lt. Tower
Sept. 25, '69 6/menhaden Bridge Tunnel
Sept. 26, '69 6/menhaden York River
Oct. 27, '69 6 Bridge Tunnel
Nov. 24, '69 6 Bridge Tunnel
Dec. 6, '69 6 Bridge Tunnel
Jan. 28, '70 6 Bridge Tunnel
Feb. 13, '70 6 Bridge Tunnel
Mar. 9, '70 2/6 Bridge Tunnel
May 6, '70 6 Bridge Tunnel
Aug. 12, '70 2 Ches. Lt. Tower
Sept. 14, '70 4 Ches. Lt. Tower
Nov. 6, '70 4 York River
Dec. 3, '70 6 Ches. Lt. Tower
Jan. 21, '71 2 Ches. Lt. Tower
B
A
B
B
A
A
A
A
A
A
B
A
ABC
B C
ABC
100
5/30
5/10
25
25
25
6
5
50
30
200
200
150
200
200
5
-
6
4
7
7
5
7
3
8
24
9
30
7
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Table 1. (Cont'd). Experimental Oil Releases
Date
Kind of Volume Observation
Oil Type Release Location Observation Released Period
(gal.) (hrs.)
Jan.
Mar.
Apr.
Jun.
Aug.
Aug.
Sept
Oct.
22,
18,
26,
23,
3, '
30,
. 14,
13,
'71
'71
'71
'71
71
'71
'71
'71
4
2
4
6
4
2
6
2/6
Ches
; ;•
. Lt.
Tower
A C
York River
Ches
Mid
Ches
Ches
Ches
. Lt.
Ches.
. Lt.
. Lt.
. Lt.
Tower
Bay
Tower
Tower
Tower
Ocean Station
A
A
A
A
A
C
B
C
B
B
B
B
C
C
C
C
C
200
200
250
65
200
200
200
200/200
9
6
16
31
32
10
25
7/24
track B = Remote sensing
Sampling
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.-•• ; &/
fa J /XVS
i/! ; ,'f /,::i
( t ./ \ / \
•BRIDGE TUNNEL^
Fig. 1. Oil release experiment locations.
8
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Oil was obtained in separate batches for each release, and
each batch had a potentially different history of well
source, refining treatment, and aging in storage. Thus,
chemical comparisons are made only within a set of oil
release samples, but it was assumed that bulk physical
properties of all batches of a particular type of fuel
oil were similar.
Releases were made from storage tanks or barrels carried
on board the vessel used to maintain station during
observation of the oil slick. Vessels were provided by
N.A.S.A., the U. S. Coast Guard, and the U. S. Navy. The
N.A.S.A. ship "Range Recoverer" was most often used.
The release vessel served as a navigation and weather
observation platform, a communication center for directing
activities of remote sensing aricraft, and a mother ship
for motorized inflatable boats used to sample the oil and
gather remote sensing ground truth information.
Direct observation and sampling of oil slicks was not
possible during hours of darkness, so flasher drogues
that floated in or near the slicks were deployed in the
evening and followed till morning. The slick could then,
in some cases, be visually relocated and further studied.
A contingency plan, which stated action to be taken by
agencies involved in this study in the event an experi-
mental oil spill should endanger shorelines, was adopted.
Notification was given to E.P.A., U.S.C.G., the U. S.
Army Corps of Engineers, and the Virginia Water Control
Board prior to each release. Weather-slick release point
combinations were selected to minimize the possibility of
beaching the oil. Oil slicks were always followed until
no longer detectable or practical to sample, and, since
there were no unfortunate incidents, the contingency plan
was never applied.
Studies on the latter two of the stated program objectives,
plankton population and chemical composition of occurring
slicks of origin not related to the experimental oil
release program, were conducted entirely in the Chesapeake
Bay. The work was concentrated in the York River and
Chesapeake Bay Bridge-Tunnel regions.
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SECTION IV
OIL SLICK MOTION
Effective control and cleanup of oil slicks often requires
predictions of oil slick motion. In marine areas, slicK
trajectories are the net result of tidal currents, wind
generated currents, and motion due to local wind stress.
To establish the relative importance of these factors,
slug oil releases in this program were tracked throughout
each experiment by the navigational equipment available on
the oil release vessels. These releases are listed in
Table 1.
A few field observations and theoretical treatments
indicate that "oil slicks move with the wind at 2.3 to 5
percent of the wind speed (Batelle, 1969, 1967; Kolpack,
1969; Smith, 1968). This percentage value has been termed
a "wind factor." Wind generated surface currents have a
similar wind factor (Laevastu, 1962; James, 1968; Doebler,
1966; Hela, 1952; Tolbert and Salsman, 1964), so a
distinction must be made between the overall wind factor,
and the relative wind factor. Slick position data can be,
used to^calculate a total slicjc velocity S. The wind
vector W can be divided into S to give the overall wind
factor. If the local surface current vector C is measured,
the sj^ick velocity data can be reduced by subtracting C
from S to give R, the compcpienk slick motion due to local
wind stress. The value ]R|/|W| x 100 is referred to as
the relative wind factor.
-'
In the experiments conducted in Chesapeake Bay on the dates
shown in Table 2, the relative wind factor was calculated.
Overall wind factors were calculatedifor those other
releases in which navigation data were available but
surface currents were not measured.
Local surface currents, C, were determined by tracking a
current drogue from the observation vessel, which provided
simultaneous position fixes. The dorgue had four vertical
orthogonal 25 centimeter square vanes, and was weighted to
place the vanes 1 meter below the water surface. A light,
bamboo pole carrying a diver's flag at 6 ft above the water
surface made the drogue easily visible. The wind drag on
the drogue was 0.25 percent, measured against surface water
masses marked with Rhodamine WT with winds of 20 knots and
white capped waves 0.3 to 0.7 meter high. Data were.not
corrected for this small wind factor.
10
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Table 2. Oil Slick Motion and Relative Wind Factor.
Experiment
Date and
Vol. (gal.)
BUNKER C FUEL
24 Nov. 69
25
6 Dec.
25
28 Jan. 70
6
13 Feb.4
5
Water
Temp.
(°C.)
OIL
10.0
6.6
0.5
3.0
Time1
(hours MT)
1319-1440
1440-1534
1205-1320
1345-1545
1121-1325
1500-1545
1251-1604
Relative
Velocity
(knots)
0.163 NW
0.24 NNW
0.43 NW
0.0
0.02 ESE
0.02 ESE
0.0
Wind
Velod ty
(knots)
15 N
15 N
10 N
7 N
8 ESE
8 ESE
3.5 NW
Relative
Wind
Factor (%)
0.8 (45°Left)2
1.6 (10°Left)2
0.88 (50°Left)2
0.0
0.25
0.25
0.0
Portions of experiments containing most reliable quantitative data.
^Orientation of slick vector relative to wind vector.
^Velocity magnitude value exaggerated by extensive slick spreading and disper-
sion. Simultaneous measurements on two drogues formed the basis for reducing
the value in calculating a wind factor
gallons of SAE 30 oil added to increase slick visibility.
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table 2. (Cont'd.). Oil Slick Motion and Relative Wind Factor,
ro
Experiment
Date and
Vol. (eal.)
BUNKER C FUEL
9 Mar.
505
6 May
30
Water
Temp.
(°C.)
OIL
2.2
15.0
Time1
(hours MT)
111-1152
1321-1404
1404-1417
1339-1408
1408-1448
1448-1510
1510-1533
Relative
Velocity
(knots)
0.3 NE
0.25 SE
0.0
0.184 NNW
0.185 NNW
0.135 NNW
0.257 NNW
Wind
Velocity
(knots)
17 NE
12 NNE
12 N
19.5 NNW
18 NNW
16 NNW
14.5 N
Relative
Wind
Factor (%)
1.7
0.0 (112°Right)2
0.0
0.95
1.03
0.85
1.75 (10°Right)2
NO. 2 FUEL OIL
9 Mar. 2.2
505
MENHADEN FISH OIL
1115-1517
0.0
14 NNE
Reseeded with 50 gallons after three hours.
0.0
25 Sept. 69 21.0
25
1006-1200
1200-1235
0.0
0.4 NE
4 W
8 NW
0.0
0.0 (90°Right)2
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Wind velocities, W, were obtained from anemometers on the
vessel or, in a few cases, on the northern end of Trestle
A of the Chesapeake Bay Bridge and Tunnel. The anemometers
were not intercalibrated, but were regularly serviced and
similarly mounted from 15 to 20 meters above the water
surface.
Slicks enlarged by spreading for a few hours after release
and took various shapes, sometimes linear or pseudopodal,
and often separated into sections. In white cap sea
conditions, oil dissipation at slick edges was rapid, and_»
slicks remained small. To track the slick and establish S,
the vessel was positioned at the downwind edge of the
slick which was taken as the slick position. This
procedure yielded a maximum slick motion.
The Coriolis deflection of C from W is approximately 20°
in offshore areas at medium latitude, and decreases nearer
shore. (Doebler, 1966; Hela, 1952; Mandlebaum, 1955).
Since all water depths occurring^ in tbJLs stuc^y are less
than 30 meters, deflections of C and R from W are assumed
to be zero.
Wind generated surface currents require a few hours to
r^each maximum speed (James, 1968), but a direct coupling of
C with W is assumed here. The study area is not suited to
a check of the degree of coupling because there are
frequent wind vector changes and rather large tidal current
oscillations. Calculated wind factors are slightly over-
valued, due to the wind-produced positive gradient of
horizontal velocities near the water surface. The drogue
did not measure current at the air-water boundary where the
velocity is a maximum.
Figure 2 shows the relative wind factor plotted versus
speed. There is apparently a functional dependence, with a
wind speed intercept of approximately 7 knots. This wind
speed must be exceeded to produce a significant difference
between the surface current motion and the slick motion.
For winds between 15 and 20 knots, the relative wind factor
is about 1.3 percent, and may approach 2.0 percent at
higher wind speeds.
Additional oil release studies would permit more precise
establishment of the relative wind factor, but this
precision will not be needed for oil cleanup purposes.
Given that overall slick speed should be known to 0.25
knot, sufficient accuracy is realizable from a knowledge
of surface currents, plus an approximate 1.3 percent of the
wind speed additional for winds greater than 15 knots.
13
-------
2.0-
1.5-
o:
o
S
2 i.OH
o
_J
UJ
o:
5 10 15
WIND SPEED (knots)
20
Fig. 2. Relative wind factor versus wind speed from data
in Table 2.
14
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Accurate predictions of oil slick motion require knowledge
of local surface currents, tidal currents, oceanic
circulatory currents and wind conditions. The error in
prediction of oil slick motion is directly dependent on the
quality of the available water current information and
weather predictions. In areas of high potential oil spill
threat, detailed long term surface current studies should
be made. The current data would permit better protection
of threatened coastlines.
Sufficiency of existing surface current information for
prediction of oil slick motion near the Chesapeake Bay
Bridge-Tunnel has been tested using the experimental
releases in this region. Tidal currents were obtained
from predictions of the U. S. Coast and Geodetic Survey
(1969, 1970), which include the effect of average seasonal
winds. Wind velocities were taken as measured, and several
overall wind factor values were selected from the
literature and experience obtained in this program.
These data were supplied to a computer program (Appendix 1)
which predicted slick motion after a spill at a stated
location and time. The current path is predicted under the
assumption of uniaxial sine wave tidal oscillations and
using inverse r2 weight-averaging of tidal currents at
U.S.C.&G.S. stations to estimate tidal currents at other
positions in the region. Possible effects due to winds
preceding the spill (James, 1968; Harrison and Pore, 1967;
Johannessen, 1968; Jones and Bellaire, 1962; Bellaire,
1963) were not included in these predictions due to
unavailability of information for lower Chesapeake Bay.
Figure 3 is a chart of the Chesapeake Bay entrance, showing
observed slick motions and predicted current paths calcu-
lated with 0, 3, and 10 percent overall wind factors. In
comparing predicted paths and actual slick motions, it
should be realized that slicks follow the current path and
are only slightly modified by the relative wind factor.
The predicted paths do not match or bracket the observed
motions. Discrepancies are not regular and amount to
several miles in a single flood or ebb tide.
For Chesapeake Bay entrance, tidal currents permit
predicting the general directions of slick travel but are
inadequate for accurate prediction of oil slick trajec-
tories. Better prediction will require analysis based on
long time series observations of local currents and winds.
It is doubtful that acquisition of these data could be
financially justified for prediction of oil slick motion
alone. If there are other environmental problems that also
15
-------
Fig. 3. Oil slick trajectories at Chesapeake Bay
entrance. Solid lines are observed trajectories,
dotted lines are predicted paths with square,
circle and triangle indicating zero, three and
ten percent overall wind factor respectively.
16
-------
require this series data, consideration should be given to
installation of long term monitoring stations.
The oil slick motion prediction program was used to predict
the path followed by oil on releases near Chesapeake Light
Tower on August 12, 1970, December 3, 1970, April 26, 1971,
August 3, 1971, and September 14, 1971.
Tidal current information for this area was obtained from
Haight (1942) and U.S.C.G. tidal height tables for 1970
and 1971 by referring tidal currents at the light tower in
hours after Greenwich transit of the moon to tidal heights
and times at Hampton Roads on the spill dates. It is
fortunate that tidal currents here are linear reversing and
can be used directly in the program. The program is now
being modified to accommodate radial tides which occur in
other continental shelf areas. The tidal currents used here
are based on more than a year of observations, so transient
phenomena are quite well filtered.
The overall wind factor used in the program was 3.7
percent, a value suggested by our observations and the
experiments of Schwartzberg (1971). The predicted and
observed slick motion paths are given' for each slick in
Figures 4 through 8.
The predictions for the August 12, 1970, and December 3,
1970, releases are acceptably close to the observed motion.
The predicted motion for April 26, 1971, is totally wrong,
and on August 3, 1971, the direction but not the total
displacement was correctly predicted. The observed path
for September 14, 1971, made a sudden 90 degree course
change that did not appear in the prediction.
Large deviations of predicted from observed slick motion
were anticipated in the Chesapeake Light Tower vicinity,
because tidal information was obtained 5 miles north of
the present light tower, large scale current systems in
the region are poorly known, spring and neap tide
situations were not considered, the wind history prior to
release was not available, and local surface currents were
not obtained as current meters were not deployed. The
predictions were surprisingly good in view of the above
limitations. The simple program used here predicts motion
fairly accurately in the absence of large scale current
fields, excepting tides, generated outside the area of
observation.
Research on oil slick motion is continuing, and releases in
proximity to fixed current meters are being planned.
17
-------
36°
FINISH 1530.
56'
AUGUST 12, 1970
FINISH
1530
36*
LIGHT
TOWER
54'
START
0742
75e
45'
75'
Fig. 4. Predicted (••••) and observed (.
Aug. 12, 1970, release.
43'
-) paths for
18
-------
75*
45'
NOTE:
75*
14.9 MILES AT 14° 15' TRUE
TO FINAL SLICK POSITION AT
IMS DEC. 4T 1970
FINISH 1700
DEC. 3, 1970
START 0903
Fig. 5. Predicted (••••) and observed ( ) paths for
Dec. 3, 1970, release.
43'
36*
55'
LIGHT
TOWER
36*
54'
36'
53'
19
-------
10
O
s,
»-»!*
O
N>rt
VO
(D a.
&>
co o
(6 O*
• CO
(D
13
ft)
CD
Hi
O
36°
56'
FINISH
1950
36*
54'
36°
52'
75° 44
START 0801
LIGHT
• TOWER
APRIL 26, 1971
FINISH
1950
75*
42'
75"
40'
-------
FINISH
1935
FINISH 1935
'54
LIGHT TOWER
AUGUST 3f 1971
75* 45'
START
0905
Fig. 7. Predicted (••••) and observed (-
Aug. 3, 1971, release.
-) paths for
21
-------
FINISH
1800
LIGHT
TOWER
FINISH
1800
SEPTEMBER 14, 1971
10
NJ
START 1000
75° 43'
75° 41'
52.5'
Fig. 8. Predicted (••••) and observed (-
Sept. 14, 1971, release.
-) paths for
-------
Parachute drogues may be used to measure,surface displace-
ment of oil from the underlying water mass. The objective
of this work is to develop a more complete system of
equations for oil motion prediction. These equations will
only be useful if concurrent wind and current data is
available.
To implement a more accurate prediction than demonstrated
above, an instant delivery current meter-anemometer system
must be deployed at the spill site and data from the system
telemetered to a computer which will use the data to make
motion predictions. The spill must be at least 6 hours
away from any beaching area in order for this type of
prediction to be achieved.
If such a prediction system proves too costly, current
surveys should be made to establish average large scale
currents. Predictions based on these averages will be
imperfect, but certainly better than what can now be
achieved. Prediction of slick motion on the continental
shelf is only possible where tidal currents are available,
which limits any present predicting ability to a few
selected regions.
23
-------
SECTION V
INITIAL AGING OF FUEL OILS ON SEAWATER
INTRODUCTION
Fuel oils can be classified into two main types. The
distillate fuels are the distilled fraction of _a selected
boiling range of crude petroleum. Representative
distillate fuel oils are kerosene and diesel fuels, and
No. 2 fuel oil. Residual fuel oils, on the other hand,
are generally mixtures of the asphaltic residue from the
distillation of crude petroleum with selected distillate
fractions of the crude petroleum. The exact formula varies
from one producer to another and often varies between
batches from the same producer. ASTM specifications for
these residual fuels, such as No. 4, 5, and 6 (Bunker C)
fuel oils are concerned primarily with the viscosity
range, and permit large variations in composition.
e
Oil spilled on the water undergoes a process called "aging"
or "weathering," which has the effects of reducing the
total volume of oil, and of changing its physical
characteristics. This aging is the result of at least four
distinct processes:
1.) Evaporation of volatile constituents.
2.) Dissolution of oil constituents into the
water column.
3.) Microbial degradation or modification.
4.) Photochemical oxidation.
Little is known about the effect of light on oils, but
photochemical oxidation of individual hydrocarbons usually
requires considerable amounts of ultraviolet irradiation in
the vapor phase. The effect of photochemical oxidation is
expected to be minimal for oils in relatively thick films
or clumps. Microbial degradation (Kator, 1971), though an
important process in the ultimate fate of oil spilled on
the sea, requires seeding and addition of nutrients for
rapid effect. This mechanism should not be an important
factor in the initial aging of oil spilled on the sea for
at least the first 48 hours. Thus, evaporation and
dissolution will be major mechanism of initial aging of
fuel oil on seawater.
24
-------
Information on the initial aging of fuel oils can be
valuable for the estimation of the remaining volume of an
oil slick by the time men and equipment can be assembled to
deal with it. Additionally, one can predict the change of
character of the spilled oil from its residence time at sea,
and estimate the amount of oil components which have been
released to the atmosphere by evaporation, and to the water
column by dissolution.
Two different approaches have been utilized in this study
of initial oil aging. The primary line of study was the
observation and analytical sampling of small volume spills
of No. 2, 4, and 6 fuel oils at sea. Twelve releases,
ranging from 60-200 gal. of oil, four for each oil type,
were conducted under a variety of climatic conditions.
Nine releases were made in the Atlantic Ocean in the
vicinity of the Chesapeake Light Tower, and three releases,
one of each oil type, were made in the more sheltered
waters of the Chesapeake Bay, near the York River entrance.
Samples of oil were taken from the slicks' at regular
intervals and preserved for later analysis.
A laboratory aging experiment for each oil type was carried
out as an adjunct to the field studies. The experiment
consisted of periodic sampling of the effluent air stream
and aqueous phase of a carboy bubbler apparatus in which
air was bubbled through an oil film floating on artificial
seawater.
METHODS AND MATERIALS
Fuel oils used in this study were procured locally. No. 2
fuel oil was a straight run distillate derived, as far as
can be determined, from various Texas crudes. It had a
boiling range of 170-370°C/760 torr, determined by actual
distillation under reduced pressure in a distillation unit
with a 24" Widmer column constructed according to
specifications from the ESSO Baytown Refinery. Head
temperatures at reduced pressure ,were converted to
atmospheric, using tables from the ASTM Method for
Distillation of Crude Petroleum (D2892-70T). Boiling
range was confirmed by the ASTM Test for Boiling Range
by Gas Chromatography (D-2887-70T). A boiling range
composition is included in Figure 9. The aromatic
character of this fuel was determined by the ASTM
Fluorescent Indicator Adsorption Test (D-1319-70).
25
-------
O
s
O
o
CL
CD
O
UJ
h-
o
UJ
or
tr
o
o
300-
200-
10 20 30 40 50 60 70 80 90 100
PERCENT DISTILLED
Fig. 9. Boiling range composition of No. 2 fuel oil,
26
-------
No. 4 and 6 fuel oils, purchased from the Humble Norfolk
Terminal, were formulated by the Lago Oil and Trmsport
Co., Aruba, Netherlands Antilles, as C401 and C552,
respectively. Both were derived from tar produ/ed from
mixtures of Venezuelan crudes by thermal crack^ig and
blended with diluents composed of a number of refinery
streams to achieve an appropriate viscosity. /Soth fuel
oils had initial boiling points near 170°C/76f torr, and
actual reduced pressure distillation showed n6 major
discontinuities in the boiling range composi/ion for
either fuel. Boiling range compositions are/shown in
Figures 10 and 11. -The aromatic character of each was
determined by the Fluorescent Indicator Ads/rption Test
(ASTM D-1319-70) on the distillate fractioi/, b.p.
170-270°C/760 torr. This test is not possible for the
whole fuel oils, which contain considerable proportions
of high molecular weight components. The/aliphatic and
aromatic portions of some fractions of the oil distillate
were separated on a silica gel column, eZuted with pentane
to remove the aliphatics, then with benzene to remove the
aromatics from the column. Progress of/the separation was
monitored with gas chromatography. /
/
/
In the field studies, oil samples were collected in a
separator scoop which allowed the partial separation of
water from the oil. Sample collection was biased toward
the thicker oil layers in the slick. Oil samples,
together with small volumes of unseparated water were
stored in quart Mason jars with aluminum foil lid liners.
Samples in the jars were then frozen and temporarily stored
in portable ice chests packed with dry ice. The samples
were later stored in a commercial freezer chest until
analyses could be made. /
Analyses were carried out by gas phromatography. Oil
samples were treated in the following manner. No. 2 fuel
oil samples were chromatographed .directly. No. 4 and 6
fuel oil samples, which were too/viscous to permit direct
syringe injection, were injected in pentane solution.
To aliquots of frozen samples weighing approximately 5 g
each, 30 ml of Baker "Baker Grade pentane was added, and
the mixture was stirred and triturated until a homogeneous
solution or suspension was achieved. The solutions or
suspensions were each gravity filtered through Whatman
#42 filter paper'to remove precipitated asphaltenes and
other pentane insoluble matter. The filtrates were then
stored in glass-stoppered flasks and portions of these
filtrates were then chromatographed.
27
-------
40C-i
O
(0
O
e
0.
CD
O
UJ
O
UJ
or
or
O
u
300-
200-
10 20 30 40 50 60 70 80 90 100
PERCENT DISTILLED
Fig. 10. Boiling range composition of No. 4 fuel oil.
28
-------
460-n
400-
o
CO
O
o
QD
Q 300-
UJ
6
kJ
o:
a:
o
o
200
0 10 20 30 40 50 60 70 60 90 JOO
PERCENT DISTILLED
Fig. 11. Boiling range composition of No. 6 fuel oil.
29
-------
Gas chromatography was done using a Perkin-Elmer Model 900
Gas Chromatograph fitted with dual 1/8" x 6' copper columns
packed with 5% SE 30 or 60/80 mesh Chromosorb P-NAW, and
with flame ionization detectors. The carrier gas was
helium, at a nominal flow rate of 20 ml/min, and the
temperature was programmed from 100-280°C at a rate of
4°C/min, and permitted to hold at 280°C until all volatile
components had been eluted.
The peaks in the chromatograms of the oil samples which
corresponded to the normal paraffins were determined by
comparison of retention times with the authentic samples of
normal paraffins. Interpolation of retention times between
the even-carbon paraffins which were available was used to
estimate the retention times for the odd carbon paraffins.
Aging of the fuel oils was followed by calculating this
percentage loss of the individual normal paraffins, which
constitute a series of compounds in rather high initial
concentrations with boiling points evenly distributed
throughout the boiling range of the fuel oils.
Quantitative analysis of normal paraffin concentration
was accomplished by determination of the peak height for
each individual compound relative to that of n-eicosane
(n-C20H42)> which was chosen as an internal standard
because: 1) it has a sufficiently low vapor pressure at
ambient temperature that minimal loss by evaporation will
occur; 2) it is quite insoluble in water; 3) of the
possible compounds in the oil which could meet the first
requirement, it is present in all three oils in sufficient
concentration for the peak height comparison.
Peak heights were considered to be the vertical distance
from the top of the peak to a baseline constructed by
drawing a straight line connecting the shoulders of the
peak in question. This baseline was generally, but not
in every case, tangent to the background of the
chromatograms.
Peak height for each n-paraffin in each chromatogram were
normalized by dividing the n-paraffin peak height by that
of n-eicosane. The normalized peak heights of each
n-paraffin were then divided by the normalized peak
Height of the corresponding n-paraffin in the chromatogram
of the unaged oil to give (%Ci)t» the percentage of
n-paraffin remaining in the oil sample taken at time t.
The following equation expresses this procedure:
30
-------
t - 100 x x
where [Ci]t represents the peak height of the normal
paraffin CiH2i+2 at time t.
The reproducibility of this procedure was tested by
calculating (%Cj_)t using chromatograms from repetitive
injections of the same sample of No. 2 fuel oil.
Successive determinations showed that (%C^) varied ±3% of
the value determined from the initial sample.
The bubbler experiments were carried out using a specially
constructed apparatus (Figure 12). Air from an aquarium
pump at the rate of 2 1/min was passed through a tubular
filter containing equal volumes of 16 mesh indicating
silica gel and activated carbon granules to remove
contaminating substances from the sweep gas. The filtered
air was then bubbled up through a glass tube at the bottom
of a carboy containing 30 ml of oil on 10 1 of artificial
seawater (33%0 NaCl) . An opening at the bottom of the carboy
permitted removal of the seawater for analysis without
danger of contamination from the surface film. The effluent
air stream from the bubbler was then passed through a plug
of extra fine glass wool to remove small droplets of water
and oil, and then into a concentric-type vapor trap, which
was chilled in a dry ice/acetone cooling bath.
In operation, the bubbler was permitted to run until the
ice crystals in the vapor trap began to reduce the sweep
gas flow rate. The trap was then removed from the cooling
bath and warmed to room temperature, causing the
obstruction to melt and collect at the bottom of the trap.
This procedure of trapping and warming was repeated as
necessary. At selected intervals the trap contents were
removed, and extracted 5 times with 1 ml of pentane. The
combined extracts were allowed to evaporate to a volume of
4 ml and transferred to a 5 ml and the sample used for
fas chromatographic analysis. Samples of the seawater
ayer were removed at the termination of the bubbler aging,
filtered through a plug of extra fine glass wool to remove
suspended oil droplets, and extracts were allowed to
evaporate at room temperature to a volume of less than
1 ml, then transferred to a 3 ml volumetric flask and
adjusted to exactly 3 ml. This sample was used for gas
chromatographic analysis.
31
-------
to
FILTER^
AIR
2 liters/min.
30ml.
01 L
10 liters
33%o NaCI
SOLUTION
SPRAY TRAP
VAPOR TRAP-^
EXHAUST
•t
DRY ICE, ACETONE
ffi. '
Fig. 12. Bubbler assembly for oil film aging.
-------
Samples from both the vapor trap and the seawater layer,
prepared as above, were chromatographed on a Perkin-Elmer
Model 900 Gas Chromatograph fitted with dual 1/4" x 3'
copper column packed with 5% SE 30 on Chromosorb W-HMDS
treated support. The temperature was programmed from
50-300°C at 8°/min, which produced the required resolution
for the ASTM Boiling Range Distribution of Petroleum
Fraction by Gas Chromatography (D-2887-70T) . Samples of
the vapor trap were analyzed in the following manner.
A plot of boiling point (atmospheric) versus retention
time was constructed from the chromatogram of a mixture of
authentic n-paraffins (Figure 13). Then, initial and final
boiling points were calculated according to the ASTM
D-2887-70T test, by planimetry of chromatograms of vapor
trap samples. By comparison of the total area under the
sample chromatograms with the area under the peak of the
n-octadecane concentration standard chromatogram, the
total weight of the oil -derived hydrocarbons in the pentane
solution was calculated. The following formula illustrates
the calculation:
oil weight = Peak area oil _ x Volume Pentane extract
3.69 Peak area//Ltg n-Cig Volume injected
The factor 3.69 in the equation derives from a calibration
run, in which a standard solution of 9.704 g/1 of
n-octadecane in pentane produced a ratio of 3.69 peak area
units per yg n-octadecane.
Samples produced by extraction of the seawater layer were
chromatographed under similar conditions to those of the
vapor trap, and the area under the 'chromatogram was
integrated by planimetry. The weight of oil hydrocarbons
in the pentane extract was determined by a formula analogous
to that above:
oil weieht = Pea^ area oil x Volume Pentane extract
B 2.75 peak area/pg naphthalene x Volume injected
The factor 2.75 is derived from the calibration chromatogram,
in which a standard solution of 1.354g/l of naphthalene in
pentane produced an integrated peak area of 2.75 area units
per j/g of naphthalene. Naphthalene was chosen for this
standard because the oil components extracted from the sea-
water appeared to consist of naphthalene and its derivatives.
In certain instances, large volumes of 10 pi or more of the
pentane extracts of the seawater layer were injected into
the gas chromatograph fitted with a fraction splitting
accessory. Samples corresponding to major component peaks
33
-------
350-1
300-
o
o
O
QL
O
- 250
*j
o
CD
O
UJ
200-
150
13
'12
'II
'10
8
10 12 14 16 18 20 22 24 26
0246
RETENTION TIME (minutes)
Fig. 13. n-paraffin standards for gas chromatography
34
-------
were condensed in 2-3 mm diameter glass capillary tubing.
These sample tubes were sealed off, and used for mass
spectrometric analysis. The tubes were broken open, and
fitted into the solid sample introduction device of a
CEC 21-104 Mass Spectrometer, and the 70eV mass spectrum
recorded. Although the mass spectroscopic study of the
chromatographically separated components was incomplete,
due to poor separations, basic structural units were
identified. Further investigation of these dissolved
components should be carried out when suitable instru-
mentation becomes available.
An additional experiment was designed to determine the
rates of which certain representative aromatic compounds
are scrubbed out of aqueous solution in the bubbler
apparatus. Ten liters of 33i& aqueous NaCl solution was
stirred for 24 hrs with a mixture of 5 g each of cumene
(i-propylbenzene), naphthalene, and 1-methyl naphthalene.
The excess organics were then removed, and the aqueous
solution filtered through a plug of extra-fine glass wool
to remove suspended droplets of organic compounds. The
seawater was then returned to the bubbler apparatus.
After removing a time-zero sample, the air sweep, at a
rate of 2 1/min was initiated. Samples were removed at
periodic intervals. The samples, 1 1 each, were extracted
four times with 10 ml of pentane, and the combined extract
reduced in volume by evaporation at room temperature to
less than 3 1. The extracts were then transferred to 3 ml
volumetric flasks and adjusted to exactly 3 ml. The
concentrations of the three organic components in the
extracts were determined by gas chromatography, comparing
the peak areas to those of known concentrations of
naphthalene.
RESULTS AND DISCUSSION
Twelve experimental releases were conducted, employing the
three fuel oil types, No. 2, 4, and 6 (Bunker C) fiel oils.
Samples of oil from the slicks were collected at regular
intervals as long as possible. Because of the low
solubilities of the oil components and the enormous
dilution factor involved, sampling of the water column
beneath the slick was not attempted. The samples obtained
were analyzed by gas chromatography for the relative
amounts of the normal paraffin hydrocarbons, which were
selected to be model oil components. The n-paraffins
consist of a homologous series of compounds in these fuel
oils, whose members produce distinctive, sharp peaks at
regular intervals throughout the boiling range in the gas
35
-------
chromatograms of oil samples.
Results of the n-paraffin analyses for the twelve field
releases are given in Tables 3(a) through 3(1). The
entries in the tables are the percentage of the given
n-paraff in remaining in the oil at time t: (%Ci)t. The
average local conditions during the sampling period are
also recorded.
The (%Ci)t for a given n-paraff in in an oil slick would be
expected to decrease in some sort of monotonic fashion with
time. Inspection of the tables show, however, that fluctu-
ations occur, and in some instances, the (%Ci)t is greater
than 100%. No reasonable mechanism can account for a net
increase of the n-paraffin content of an oil slick, so such
anomalously high values must not reflect the true concen-
trations. Several factors inherent in the method of
analysis seem likely to contribute to such errors. One
problem is the necessity to use four separate peak height
measurements in the calculation of (%C.£)t. A test of
reproducibility using a single oil sample showed that
(%Ci)t could be determined to ±3%; however, since the
estimation of peak heights is not better than ±5% for most
peaks, the maximum uncertainty in the (%Cj[)^ would be
propagated to ±20% by the mathematical treatment. Another
problem associated with the quantitative gas chromatography
of fuel oils is the fact that the n-paraffin peaks are not
completely separated from the background of aromatic,
isoprenoid, isoparaffin and naphthene hydrocarbons. Peak
heights are measured from the peak maximum to an estimated
baseline, which depends upon the detailed nature of the
background. Although a highly reproducible baseline
estimate can be made for imaged samples, problems arise
when the concentrations of the various petroleum compounds
change by aging. Then, changes in overlapping and
underlying peaks greatly affect the estimation of the
n-paraffin baseline, and hence the determination of peak
Height.
A final possible source of error comes from the variation of
sampling location in the slick itself. Since a thin oil
film will age more rapidly than a thicker one, the
thickness of the oil being sampled has considerable import.
In actual practice, the samples were collected from the
thickest layers of the slick that could be found. It was
not possible to tell whether a particular layer had been
thick since the spill, or was the result of coalescence of
thinner films.
36
-------
Table 3 (a)
Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons, No. 6 Fuel Oil
Release: 0900 hrs, EST, 12/3/70
Water Temp: 13°C. Air Temp: 60°F.
u>
% Paraffin
C9
CIO
Cll
C12
C13
C14
C15
C16
C17
CIS
C19
C21
C22 .
C23-
C24
1:00
156.5
158.0
101.8
118.9
109.0
105.0
118.2
100.4
101.4
98.2
99.5
101.2
102.6
99.4
102.5
Time After Release (hrs)
2:00 3:00 4:00 5:45
70.7
65.3
69.9
97.8
106.0
102.4
109.8
101.2
105.5
102.2
102.9
102.4
103.8
129.0
n.a.
119.6
173.2
102.6
140.5
142.4
116.4
132.7
116.1
115.0
100.2
106.7
98.6
101.7
96.6
113.0
70.7
94.2
86.1
106.4
103.8
104.8
128.6
109.8
106.2
95.7
103.4
111.3
103.7
98.0
119.4
32.1
91.0
61.2
105.5
122.5
113.0
123.5
108.0
107.2
95.7
101.1
110.4
106.7
95.2
107.2
24:15
n.d.
n.d.
n.d.
n.d.
16.0
31.4
56.3
70.3
91.2
95.7
92.8
104.3
102.6
110.1
106.3
26:30
n.d.
n.d.
n.d.
n.d.
25.0
43.5
74.1
85.6
103.8
98.1
101.5
107.8
103.1
103.8
110.7
n.a. = not available
n.d. * not detected
-------
Table 3(b).
Ui
00
Fuel Oil Aging - Loss of Normal Paraffin
Location: Mid-Chesapeake Bay/New Point Comfort
Oil: 66 gallons No. 6 Fuel Oil
Release: 0830 hrs, DST, 6/23/71
Water Temp: 76°F. Air Temp:
°L Normal
Paraffin
C9
CIO
Cll
C12
C13
C14
C15
C16
C17
CIS
C19
C21
C22
C23
C24
C25
2:10
6 3". 6
71.4
88.1
102.4
107.5
61.6
104.2
105.9
103.5
100.8
103.2
96.7
99.5
113.2
102.3
104.2
4:10
4.2
10.1
19.2
41.1
51.3
145.9
94.1
96.8
101.7
93.1
97.0
95.5
100.4
111.0
98.7
94.1
Time From Release (hrs)
6:10 8:10 10:10 12:10
9.9
26.9
48.0
78.6
86.3
114.0
102.3
99.8
105.4
89.3
99.1
97.1
98.3
110.8
99.7
97.4
n.d.
n.d.
n.d.
11.1
30.7
118.3
87.6
97.0
106.6
94.4
100.6
101.7
105.3
121.9
105.1
105.1
n.d.
n.d.
5.4
32.7
52.1
167.2
99.4
98.3
100.9
79.6
88.7
90.5
95.2
105.4
90.9
86.6
n.d.
n.d.
n.d.
12.8
35.1
137.4
89.8
94.7
99.5
83.9
91.9
89.5
92.9
102.4
88.6
89.8
26:00
n.d.
n.d.
n.d.
n.d.
2.6
23.3
26.8
31.3
76.4
75.7
94.9
90.7
99.3
110.6
93.1
96.7
28:00
n.d.
n.d.
n.d.
n.d.
n.d.
7.7
26.1
39.5
71.5
72.9
87.1
92.3
99.4
112.4
96.2
95.1
30:00
n.d.
n.d.
n.d.
n.d.
n.d.
8.8
13.6
27.6
70.7
72.0
85.1
93.6
100.5
111.8
94.0
95.2
-------
Table 3(c). Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons No. 6 Fuel Oil
Release: 1000 hrs, DST, 9/14/71
Water Temp: 23.8°C. Air Temp: 74°F.
Time After Release (hrs)
% Normal Paraffin 2:15 4:15 6:00 9:00 23:00 25:00
O)
vO
CIO
Gil
C12
C13
C14
CIS
C16
C17
CIS
C19
C21
C22
C23
C24
C25
24.5
14.1
37.6
60.0
85.2
88.0
98.0
94.9
95.6
100.6
101.5
99.1
101.4
n.a.
n.a.
n.d.
6.2
22.9
43.3
72.2
82.8
94.7
91.1
106.0
97.5
100.5
98.3
98.8
103.1
104.8
n.d.
n.d.
9.1
25.0
56.1
69.5
85.6
86.7
98.1
95.9
100.5
98.2
98.8
101.3
103.8
n.d.
n.d.
9.7
32.4
60.9
81.2
90.4
94.0
100.6
97.9
102.7
97.1
102.7
103.1
104.2
n.d.
n.d.
n.d.
n.d.
n.d.
11.3
18.2
36.8
70.7
85.9
104.4
101.7
107.4
110.6
112.5
n.d.
n.d.
n.d.
nid.
n.d.
5.2
18.1
27.8
61.4
81.7
108.3
105.7
108.3
110.3
109.8
-------
Table 3(d). Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons No. 6 Fuel Oil
Release: 1015 hrs, DST, 10/13/71
Water Temp: 71°F. Air Temp: 75°F.
Time After Release (hrs)
% Normal Paraffin 2:15 4:30 6:15 22:15 24:15
•P*
o
CIO
Cll
C12
C13
C14
C15
C16
C17
CIS
C19
C21
C22
C23
C24
C25
n.d.
69.9
20.1
37.2
61.8
73.3
85.1
91.5
102.4
98.7
102.2
99.2
106.0
117.7
117.7
n.d.
n.d.
11.2
27.2
56.3
74.7
86.2
95.4
96.4
96.5
101.2
97.0
100.2
107.7
111.0
n.d.
n.d.
9.7
35.6
63.4
81.5
82.3
94.5
93.6
96.0
102.1
100.3
100.0
107.5
104.5
n.d.
n.d.
n.d.
9.2
36.8
61.9
76.7
91.9
92.8
97.2
101.6
99.8
110.6
118.8
110.9
n.d.
n.d.
n.d.
14.5
40.8
66.9
79.4
89.7
93.1
97.3
102.1
98.2
101.2
102.9
104.8
-------
Table 3(e). Fuel Oil
Aging
: York
- Loss of Normal Paraffin
Location: York River Mouth
Oil: 200 gallons No. 4 Fuel Oil
Release: 0900 hrs, EST, 11/6/70
Water Temp: 15.4°C. Air Temp: 60°F.
% Normal
Paraffin
CIO
Cll
C12
C13
C14
C15
C16
C17
CIS
C19
C21
C22
C23
C24
C25
1:00
117.8
93.0
98.9
99.9
126.0
105.6
106.7
108.5
107.5
106.4
102.8
99.2
101.1
105.0
95.4
1:50
73.7
87.8
103.5
100.6
115.3
105.7
104.2
103.5
117.2
104.3
101.7
99.3
101.6
109.7
104.3
Time After Release (hrs)
3:00 4:00 5:00 6:00
71.8
93.9
106.4
100.9
118.2
103.8
107.3
95.9
105.6
105.3
106.0
102.3
101.8
112.2
96.9
55.9
84.7
91.4
100.8
116.9
103.0
104.6
104.6
105.8
106.9
105.8
101.8
102.6
109.0
99.1
59.5
100.9
147.7
107.3
124.1
114.9
109.6
100.2
99.4
97.7
98.7
93.2
92.9
98.9
92.3
9.8
45.1
94.3
95.7
103.8
106.4
103.6
97.5
99.9
97.8
101.5
98.3
97.5
116.5
98.2
7:00
n.d.
31.6
50.0
74.2
113.0
95.2
104.8
109.7
103.8
109.5
106.5
103.5
100.5
102.2
101.8
8:00
n.d.
26.3
34.5
63.3
125.7
78.9
117.3
125.9
107.1
111.4
109.8
104.8
91.5
99.5
112.2
-------
Table 3(f).
Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons No. 4 Fuel Oil
Release: 0730 hrs, EST, 1/22/71
Water Temp: 3.85°C. Air Temp: 47°F.
7o Normal
Paraffin 1:00
Cll
C12
C13
C14
C15
C16
C17
CIS
C19
C21
C22
C23
C24
C25
20.0
54.3
49.4
94.9
96.7
101.7
88.6
86.0
89.8
99.7
104.8
128.0
n.a.
n.a.
2:00
155.8
102.0
97.8
96.3
88.7
94.4
84.3
88.6
89.7
98.5
102.8
156.1
100.0
100.0
3:00
20.0
50.0
76.8
91.2
95.1
101.3
90.8
90.8
92.9
97.1
104.3
124.2
95.2
94.3
Time After Release (hrs)
4:00 5:00 6:00 7:00
n.d.
2.4
45.5
75.8
88.9
100.6
85.3
90.8
84.3
93.7
99.1
120.7
94.8
84.4
75.1
80.5
87.9
93.9
89.1
95.6
88.5
85.3
90.7
99.7
100.7
124.6
92.6
87.6
144.8
130.5
84.4
97.2
96.3
97.9
90.1
91.4
95.2
99.4
107.8
128.3
96.4
102.3
79.3
91.4
93.5
83.3
88.3
91.4
89.5
102.2
99.0
99.4
112.7
129.8
96.8
92.3
8:00
5.0
74.3
91.1
87.3
89.3
97.0
93.7
114.3
101.3
106.4
109.6
124.6
102.6
89.9
9:00
5.2
81.0
85.3
89.0
84.0
80.6
91.9
118.8
105.4
104.5
113.4
124.4
93.8
97.2
-------
Table 3(g). Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons No. 4 Fuel Oil
Release: 0800 hrs, EST, 4/26/71
Water Temp: 12°C. Air Temp: 62°F.
70 Normal
Paraffin 1:00
Cll
C12
C13
C14
C15
C16
C17
C18
C19
C21
C22
C23
C24
C25
105.5
152.8
141.5
112.6
106.0
104.6
100.5
104.4
100.8
99.9
112.9
95.8
103.2
99.7
3:00
49.7
89.0
99.9
104.0
105.0
99.2
101.5
101.3
100.3
99.9
113.5
98.4
111.2
98.1
4:00
68.1
108.0
107.5
105.4
106.1
96.0
100.4
98.4
99.6
95.3
107.2
87.3
103.4
89.3
Time After Release (hrs)
5:00 6:00 7:00 8:00
55.2
93.4
103.9
97.8
104.8
96.8
103.8
98.2
101.2
95.7
109.0
89,9
90.5
84.5
74.7
105.0
105.9
104.6
101.8
95.1
98.0
95.6
95.3
97.1
111.4
96.7
99.1
91.5
18.0
46.8
84.2
87.5
99.3
89.0
97.0
91.0
95.3
84.7
112.5
97.2
102.3
90.1
22.7
64.8
93.2
87.5
102.1
86.6
98.4
92.5
96.8
96.6
115.0
102.4
99.5
94.5
9:00
n.d.
28.8
72.7
81.7
97.5
86.8
96.6
92.2
98.2
93.1
110.6
96.6
95.0
85.7
10:00
11.0
49.5
78.4
86.1
101.3
94.9
100.3
100.0
100.2
96.8
109.5
95.5
93.9
88.7
11:00
n.d.
42.9
70.7
76.0
92.2
80.2
95.0
89.2
95.1
98.3
111.5
96.0
106.0
94.2
-------
Table 3(h). Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower*Avg. of two analyses
Oil: 200 gallons No. 4 Fuel Oil
Release: 0830 hrs, DST, 8/3/71
Water Temp: 25.5°C. Air Temp:
% Normal
Paraffin
CIO
Gil
C12
C13
C14
C15
C16
C17
C18
C19
C21
C22
C23
C24
C25
1:00
75.7
89.7
96.1
109.3
84.4
92.4
95.7
95.5
98.0
96.1
103.0
101.8
101.2
98.5
100.5
2:00
53.6
77.7
84.1
108.5
89.5
96.9
99.7
92.2
98.6
100.5
100.5
103.4
96.8
94.8
96.9
Time After
3:30
9.4
50.3
64.0
101.2
83.5
95.8
99.9
96.6
98.7
100.4
100.7
99.8
89.0
95.8
100.8
Release
4:45
13.1
46.1
65.3
90.2
89.5
95.8
99.6
96.9
96.1
99.6
98.7
98.4
97.6
96.5
93.9
(hrs)
6:00
3.8
34.0
50.4
83.6
79.5
92.4
96.3
95.0
94.7
99.7
101.8
101.4
99.7
98.9
102.5
6:45
n.d.
5.0
46.6
75.9
80.8
92.3
98.5
96.6
98.6
98.9
100.0
99.3
98.7
100.0
100.9
9:00
n.d.
n.d.
32.8
71.2
74.1
87.8
95.3
92.8
94.7
95.6
98.5
97.1
96.0
93.7
98.6
-------
Table 3(h). (Cont'd).
Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons No. 4 Fuel Oil *Avg. of two analyses
Release: 0830 hrs, DST, 8/3/71
Water Temp: 25.5°C. Air Temp:
% Normal
Paraffin
CIO
Cll
C12
C13
C14
C15
C16
C17
C18
C19
C21
C22
C23
C24
C25
10:00
n.d.
n.d.
21.9
28.9
65.9
87.3
96.4
93.5
94.8
97.6
99.0
96.5
95.8
95.2
99.1
Time
11:00
n.d.
n.d.
13.7
24.8
68.4
86.8
92.6
91.7
92.8
96.9
103.6
104.5
102.8
104.7
103.5
After Release
25:00
n.d.
n.d.
n.d.
3.8
21.8
58.9
83.8
86.7
91.8
95.0
101.2
100.3
100.4
100.4
100.6
(hrs)
27:30
n.d.
n.d.
n.d.
2.4
15.8
52.1
81.2
85.9
92.6
96.7
97.8
96.9
95.6
97.4
96.1
28:45
n.d.
n.d.
n.d.
1.4
14.5
42.0
75.8
82.9
92.6
94.4
98.9
98.7
95.0
96.7
98.2
-------
Table 3(i). Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons No. 2 Fuel Oil
Release: 0730 hrs, EST, 1/20/71
Water Temp: 5°C. Air Temp: 40°F.
ON
% Normal
Paraffin
CIO
Cll
C12
CIS
C14
C15
C16
C17
CIS
C19
C21
C22
1:00
28.5
76.5
92.8
93.4
103.1
85.7
99.9
99.2
111.9
99.0
100.6
79.9
Time After Release (hrs)
3:00
17.1
73.6
92.2
n.a.
n.a.
n.a.
n.a.
101.9
114.1
100.1
100.0
86.7
5:00
n.d.
13.4
44.7
63.1
107.8
95.9
112.9
114.2
126.9
111.2
109.4
103.1
-------
Table 3(j). Fuel Oil Aging - Loss of Normal Paraffin
Location: Mobjack Bay
Oil: 200 gallons No. 2 Fuel Oil
Release: 0845 hrs, EST, 3/16/71
Water Temp: 8.3°C. Air Temp: 40°F.
7o Normal
Paraffin
C9
CIO
Cll
C12
C13
C14
CIS
C16
C17
CIS
C19
C21
C22
0:20
91.1
96.7
112.0
107.6
101.3
119.8
116.6
113.0
115.3
111.8
107.7
98.2
101.2
0:50
19.9
74.7
118.5
126.2
127.3
140.5
139.6
139.0
134.6
129.7
115.8
90.4
92.5
Time After Release (hrs)
1:25 1:45 2:00 3:00
n.d.
23.6
56.4
50.0
104.2
130.8
124.0
118.5
139.2
118.8
120.4
103.1
85.4
n.d.
3.8
13.1
23.4
59.2
100.8
112.5
121.3
139.8
121.6
122.5
89.0
87.2
n.d.
8.3
7.2
17.0
50.1
114.6
120.8
125.0
152.8
131.8
132.5
82.7
77.8
n.d.
n.d.
n.d.
n.d.
4.3
37.5
75.2
99.3
131.9
121.0
121.5
85.7
79.7
3:25
n.d.
n.d.
n.d.
n.d.
2.9
11.3
44.9
98.7
137.3
127.7
145.5
84.7
78.6
3:40
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
18.1
85.8
154.0
151.3
141.2
84.7
n.a.
5:25
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
0.9
23.6
88.5
113.1
117.8
85.8
82.7
-------
Table 3(k)
CO
Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons No. 2 Fuel Oil
Release: 0900 hrs, DST, 8/30/71
Water Temp: 23°C. Air Temp: 76°F.
7o Normal
Paraffin
CIO
Cll
C12
C13
C14
C15
C16
C17
CIS
C19
C21
C22
1:30
42.3
68.6
74.9
84.9
88.2
87.6
91.5
91.9
95.9
95.3
93.1
103.6
3:20
36.4
69.8
73.5
86.5
91.5
92.6
97.3
96.7
98.3
96.6
95.7
90.6
Time
4:45
8.0
28.6
43.8
72.8
87.7
88.9
98.5
95.4
97.2
96.6
86.2
103.6
After Release
5:45
18.6
55.9
61.7
83.5
90.9
90.5
95.6
93.6
98.1
94.0
80.5
80.5
(hrs)
6:45
n.d.
7.0
12.6
41.1
72.4
80.1
91.6
83.7
92.3
90.6
90.6
97.2
7:40
4.3
27.9
34.7
64.4
81.4
85.2
93.3
86.7
91.7
90.1
96.5
96.8
10:30
n.d.
20.9
31.5
74.6
94.9
110.5
124.1
109.3
113.4
106.0
80.5
80.5
-------
Table 3(1). Fuel Oil Aging - Loss of Normal Paraffin
Location: Chesapeake Light Tower
Oil: 200 gallons No. 2 Fuel Oil
Release: 1045 hrs, DST, 10/13/71
Water Temp: Air Temp:
% Normal
Paraffin
CIO
Cll
C12
C13
C14
CIS
C16
C17
CIS
C19
C21
C22
1:00
83.0
101.4
105.9
109.5
106.4
107.4
106.5
107.4
104.0
106.6
93.3
98.3
2:09
28.6
70.3
97.7
109.0
106.8
108.6
110.1
111.0
108.8
110.1
89.7
67.5
4:30
8.3
54.9
103.1
121.8
123.0
127.0
128.7
128.2
123.7
119.7
0.765
0.572
5:30
n.d.
28.8
77.7
94.8
103.4
107.5
106.3
107.4
106.7
109.4
90.3
81.3
6:30
n.d.
30.2
69.6
92.1
99.9
104.9
107.5
106.9
105.5
105.5
93.6
93.5
-------
The loss of oil components from an oil film is a complex
problem to treat mathematically. A simple model is
considered here, as a basis for comparison with the aging
study. The model system chosen is an oil film of fixed
volume and surface area which is losing components by
evaporation to an air stream passing over it. Preliminary
assumptions are made that the heat input is sufficient to
maintain the oil film at constant temperature, and that^the
oil components are in continuous equilibrium with a finite
air volume above the film. A further assumption is that
the total number of moles of all compounds in the oil film
is not appreciably changed by the evaporative loss of
volatile compounds.
Define:
Cfc = number of moles of component C in the oil
at time t.
K = Henry's Law constant.
M = Total number of moles of all components in
the oil.
F = flow rate of the air stream.
V = volume of air in equilibrium with the oil.
P = partial pressure of C in V at time t.
The rate of loss of C from the oil will be given by the
amount of C evaporated into V per unit time. Therefore,
using the ideal gas law:
Henry's Law states that the partial pressure of a component
in the vapor phase is directly proportional to the mole
fraction of that component in the liquid phase with which
the vapor is in equilibrium. Thus:
p t = CfcK
*c M
and since V = Ft, the equation becomes:
dC m RFC
Dt MRT
Integrating from t = 0 to t = t ,
= In Cfc - In C°
50
-------
And the ln(70C)t, that is, the log percent C remaining at
time t, will be a linear function of t:
ln(%C)t - - H| + ln(100)
For aging experiments in the field, then one might expect,
to a first approximation, that linear relationships between
log (%C*)t vs time would be obtained. Data of several
n-paraffin analyses from one of the field experiments are
shown plotted in the above manner (Figure 14) . These plots
of log (%C^)t vs t are not linear, but curve downward.
This non-linearity may have resulted from a number of
causes:
1.) The temperatures of the oil films and air
are not constant.
2.) The wind speed in the field is not constant.
3.) Neither the surface area nor the thickness of
the oil film is constant, because of the
spreading tendency of unconfined oil on the
sea surface.
The temperature of the oil film is not explicit in the
model equation of oil aging, but the Henry's Law
proportionality constant is an exponential function of
temperature. The gigher the temperature of the oil film,
the larger the value of K becomes. The effect of
increasing wind speed will be to increase the magnitude of
the factor F, but the relation may not be a linear one at
high wind speeds. Finally, there is the problem of
changing surface area and thickness of the oil film.
Although the assumption was made that the oil components
are in continuous equilibrium with the passing air volume,
this situation will be approached only at low wind speeds
and very thin film thickness. The effect of oil spreading,
then, will be to increase the magnitude of the factor KF.
The effect of increased temperature, wind speed, and
surface area, then, is to increase the magnitude of the
slope coefficient - J™ , and to increase the rate at which
C is lost from the oil film.
51
-------
0.4
15
10 15 20
TIME (hrs.)
Fig. 14. Loss of n-paraffins from No. 4 fuel oil release,
Aug. 3, T971.
52
-------
In the field releases, which were generally initiated in
the cool, still, early morning, the usual conditions
experienced were increasing temperature, wind speed, and
surface area. Thus, plots of log (%Ci)t show increasing
curvature as a function of time.
Laboratory aging of the three fuel oil types in the bubbler
aging apparatus was conducted to get information on the
relative importance of loss of oil components by
evaporation and by dissolution in seawater. The amount of
material from the oil film which was dissolved in the
seawater after a period of aging was determined by
quantitative gas chromatography of pentane extracts of the
seawater. This information is listed in Table 4. The
extracts of the seawater which was in contact with the
three oil types produced qualitatively similar gas
chromatograms of the aromatic portions of the oils.
Figure 15 compares the chromatogram of the seawater extract
from the No. 4 fuel oil aging experiment with the aromatic
portion of the No. 4 fuel oil distillate fraction, b.p.
190-250°C/760 torr.
Table 4. Dissolved oil components from bubbler experiment.
Concentration of Percentage of
Fuel Oil oil components total oil
No. 2 1.425 x 1CT3 g/1 0.048%
No. 4 7.47 x 10'4 g/1 0.025%
No. 6 1.26 x 10'4 g/1 0.004%
The major water-soluble components from all three oil types
were naphthalene and the isomeric monomethyl- and dimethyl-
naphthalenes. The naphthalene and monomethylnaphthalene
peaks were identified from their mass spectra, and by
comparison of their gas chromatographic retention times
with those of authentic samples. The identity of the
isomeric dimethylnaphthalenes was inferred from their
retention times relative to that of naphthalene and the
monomethylnaphthalene, with reference to reported gas
chromatograms (Boylan & Tripp, 1971).
The differences noted in the weights of dissolved oil
compounds among the three oil types is probably related to
concentrations of water-soluble aromatic compounds in the
original oil. The No. 2 fuel oil contains the highest
53
-------
#4 fuel oil
aromatic fraction
#4 fuel oil
aqueous extract
I
200°C
240°C
I
280° C
SIMULATED BOILING POINT (ASTM D2887-70T)
Fig. 15. Comparison of No. 4 fuel oil aromatic fraction
b.p. 190°-250°C with No. 4 fuel oil water
solubles.
54
-------
naphthalenes found (218-262°C), whereas No. 4 and No. 6
fuel oils contain respectively less.
Several interesting features were noted of the character of
the seawater extracts from the bubbler aging experiments.
One is the relatively low concentration of naphthalene in
the seawater. In all three experiments, the concentration
of naphthalene was one to two orders of magnitude lower
than the maximum calculated solubility of naphthalene in a
33&o aqueous sodium chloride solution, 1.9 x 10-2g/l (Gordon
and Thome, 1967). The other is the noticeable absence of
the lower boiling, rather water-soluble alkyl-benzenes.
Boylan & Tripp (1970) found considerable quantities of
these species in seawater which had been equilibrated with
various types of fuel oils and crude oils in closed systems.
It is postulated that in the bubbler apparatus, and also in
open water oil spills, the volatile water soluble aromatic
compounds are lost preferentially by evaporation. The
evaporative loss might be occurring directly from the oil
film, or could come from the scrubbing of the seawater by
the bubbler, or wave action.
The possibility that dissolved aromatic compounds could be
scrubbed out of seawater solution by interaction with the
air was demonstrated in a quantitative manner. A solution
of cumene (isopropyl benzene, b.p. 152°C), naphthalene
(b.p. 218°C), and 1-methylnaphthalene (b.p. 241°C) was
allowed to age in the bubbler apparatus. The content of
these species in the seawater was determined by gas
chromatographic analysis of the pentane extracts of the
seawater as a function of time. Figure 16 shows the plot
of log (% remaining) vs time for the three species. The
scrubbing action of the bubbler followed an exponential
decay, and produced straight line plot. The lowest boiling
component, cumene, was lost beyond detectability by the
process in less than four hours. The naphthalene and
1-methylnaphthalene were lost at slower, though appreciable
rates.
Therefore, in the bubbler experiments, and presumably in
the oil releases at sea as well, the lower boiling aromatic
compounds, though rather soluble in seawater, are lost
through an evaporative process, either directly, or by
scrubbing of the water column, leaving the less volatile,
higher molecular weight aromatics as the major dissolved
species. Since solubility in water of aromatic compounds
generally decreases as the molecular weight and size of the
compound increases, it seems that the naphthalene,
monomethylnaphthalenes, and dimethylnaphthalenes occupy a
prominent position of favorable compromise between the
55
-------
I - METHYLN APHTH ALENE
NAPHTHALENE
4567
TIME (hrs.)
Fig. 16. Scrubbing of dissolved aromatic species in
bubbler apparatus.
56
-------
opposing characteristics of volatility and solubility in
seawater.
The boiling ranges of the trapped evaporate fractions from
the bubbler apparatus for the three oil types were
determined by ASTM D2887-70T Boiling Range Test by Gas
Chromatography. Figure 17 shows the changes in the initial
and final boiling points with time. The results from all
three oil types were similar, so that single lines were
drawn to fit points from the three experiments. The final
boiling point of the fraction levels off in the vicinity of
270°C, while the initial boiling point continues to
increase. Presumably, the lines will eventually converge.
Because of this behavior, the term volatile fraction is
introduced to describe that fraction of the fuel oil which
has a boiling point of 271°C or less. The boiling range
of the volatile fraction was defined to include
n-pentadecane, b.p. 271°C as its upper limit, as this
compound was detected in the evaporate fraction.
Although the boiling ranges of the evaporate fraction is
similar for the three oil types, the detailed nature of
their components is not. Figure 18 compares the gas
chromatogram of the evaporate fractions from the three oil
types at comparable aging times. It should be noted that
the three were recorded at different relative amplifications,
however. The horizontal axis is in units of simulated
boiling point, derived from ASTM D2887-70T instead of the
more usual retention time.
The loss of the components from the oil is shown in
Figure 19. The loss of weight is greatest for No. 2 fuel
oil, and respectively less for No. 4 and No. 6 fuel oils.
This result is no doubt related to the relative sizes of
the volatile fractions, i.e., b.p. £ 271°C, in the three
oils.
Although the derivation for model aging which was treated
above considered the loss of a single compound, its main
point, that the aging process should be an exponential
function of time, may be applied here. If the volatile
fraction is treated as a single entity rather than a
variety of compounds, one can plot log (% volatile fraction
remaining) vs time instead of (*/£$)t- Such a plot is shown
in Figure 20. Here, the loss of the volatile fraction is
not quite linear with respect to time, and shows curvatures,
particularly in the early hours of aging. This presumably
is due to the loss of the extremely volatile compounds.
The slopes of No. 4 and No. 6 fuel oils become quite similar,
though that of No. 2 fuel oil is larger, reflecting its
57
-------
3001
o
o
O
O.
d 200
O
ffi
o
UJ
100
INITIAL
10 20 30 40
TIME (hours)
Fig. 17. Change in boiling range of evaporate fraction
in bubbler apparatus.
58
-------
n-Cn
I50°C 200°C 250°C
SIMULATED BOILING POINT (ASTM D2887-70T)
Fig. 18. Typical gas chromatograras of No. 2, 4, and 6
fuel oil evaporate fractions.
59
-------
100
86
20 30 40
TIME (hrs.)
50
Fig. 19. Loss of volatiles in bubbler apparatus.
60
-------
2.00
1.86
NO. 4
FUEL OIL
NO. 2
FUEL OIL
10 20 30 40
TIME (hrs.)
Fig. 20. Volatiles remaining in bubbler apparatus.
61
-------
greater content of more volatile compounds.
A scheme has been devised to allow comparison of the aging
of fuel oils in the bubbler apparatus with the open ocean
aging experiments. Assume that, to a first approximation,
the evaporative aging is restricted to the loss of the
volatile fraction, i.e., b.p. ^ 271°C. The percentage of
the fuel oil volatile fraction remaining in the oil film
at any given time t can be calculated from the values of
(%Ci)t listed in Tables 3(a) to 3(1) in the following
manner. Coefficients a through e are calculated from the
boiling range compositlon diagram, Figures 9 through 11:
a = % volatile fraction, b.p. * 196°C
b = % volatile fraction, 196°C <* b.p. ^ 216°C
c = % volatile fraction, 216°C < b.p. ^ 235°C
d = % volatile fraction, 235°C.< b.p. * 253°C
e = % volatile fraction, 253°C < b.p. ^ 271°C
The actual values of the coefficients are listed in Table 5
for each type of oil.
Table 5. Boiling Range Composition Coefficient
Fuel
No.
No.
No.
Oil
2
4
6
0.
0.
0.
a
080
000
000
0.
0.
0.
b
140
067
300
0.
0.
0.
c
230
233
250
0
0
0
d
.310
.367
.200
0.
0.
0.
e
240
333
250
Now, the percentage in each of the above portions of the
volatile fraction at time t is approximated by the gas
chromatographically determined (/>Ci)t, where C^ is the
n-paraffin which has its boiling point in that portion:
volatile fraction remaining) t = a^C-ii)*. + b(%Ci9)r
c(%C13)t + d(7oC14)t + e(7oC15)t.
The tabulated values of (%C4)t are used except
7oC^ > 100%, in which case the value is assumed
where
to be 100%,
The resulting data are plotted in the usual manner as log
(% volatile fraction) vs time. The plots from each oil
release, along with the corresponding bubbler aging plot
are shown in Figures 21 through 23. The slope of the
visually fitted straight line through the points for each
experiment was determined and recorded in Table 6. The
values of the slopes gives a rough estimate of relative
62
-------
aging. When correlated in this manner, the open water oil
films aged consistently faster than the bubbler films,
ranging from 2-180 times as fast.
63
-------
0 5 10 15 20 25 30
TIME (hrs.)
Fig. 21. Loss of volatile fraction of No. 6 fuel oil
in bubbler and field experiments.
64
35
-------
o. 2.0
BUBBLER
4/71 j 11/70} 1/71 (A)
10 15 20
TIME (hrs.)
Fig. 22. Loss of volatile fraction of No. 4 fuel oil in
bubbler and field experiments.
65
-------
BUBBLER (•)
0.0
10 15 20
TIME (hrs.)
Fig. 23. Loss of volatile fraction of No. 2 fuel oil in
bubbler and field experiments.
66
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Table 6. Fuel Oil Aging Comparison.
Slope Aging Rate
Experiment log (% remaining) Units/hr Relative to Bubbler
No. 2 Fuel Oil
Bubbler
1/71 Release
3/71 Release
8/71 Release
10/71 Release
No. 4 Fuel Oil
Bubbler
11/70 Release
1/71 Release
4/71 Release
8/71
2.94 x 10"3
2.45 x 10'2
5.28 x 10"1
2.09 x 10"2
6.67 x 10"3
1.96 x 10"3
7.02 x 10"3
7.02 x 10'3
7.02 x 10~3
2.33 x 10"2
1.00
8.33
179.59
7.11
2.27
1.00
3.58
3.58
3.58
11.89
-------
Table 6. (Cont'd). Fuel Oil Aging Comparison.
Slope
Aging Rate
Experiment
No. 6 Fuel Oil
Bubbler
12/70 Release
6/71 Release
9/71 Release
10/71 Release
log (% remaining) Units /hr
2.27 x 10"3
2.13 x 10'2
3.66 x 10"2
7.66 x 10"2
2.50 x 10"2
Relative to Bubbler
1.00
9.38
16.12
33.74
11.01
00
-------
SECTION VI
REMOTE SENSING OF OIL SLICKS
Oil remote sensing techniques have been applied to the
deliberate oil releases, natural films, and accidental
oil spills observed in this project. Oil types included
menhaden fish oil and numbers 2, 4, and 6 fuel oils.
Overflights of oil slicks have been made by a C-54 and
a helicopter provided by NASA Wallops Station. These
aircraft were equipped with multiple nadir view 9-in.
format Fairchild T-ll cameras. In one experiment,
coverage was also provided by the University of Michigan
C-47 aircraft, which carried two 70 mm format cameras and
two multispectral scanners to collect data in 17 spectral
channels.
Remotely sensed and surface collected data have been used
to analyze oil slick temperature, thickness, and spreading
rate, and to evaluate techniques for remote detection and
discrimination of various oils. Accurate surface measure-
ments have made the evaluation of remote sensing data
especially reliable. The oil slick remote sensing program
is continuing and other observation frequencies and modes
are being evaluated. Passive microwave radiometric oil
thickness measurements are now being processed by the Naval
Research Laboratory, which operates the instrument.
REMOTE SENSING COVERAGE
There were twelve experiments with remote sensing coverage.
Film-filter combinations and non-photographic detectors are
listed in Table 7, which includes photography of No. 6 oil
from an accidental 10,000 gallon spill on May 6, 1971, from
the Amoco Refinery at Yorktown, Virginia. Remote sensing
records are available at NASA Wallops Station. Surface
data are located at the reporting agency.
SURFACE DATA COLLECTION
Surface data was collected from small inflatable boats
stationed in the slicks, so observations were generally
conducted in fair weather with winds less than IS^knots
and wave heights less than one meter. Meteorological data
were collected from the oil release vessel. Extent of haze,
water color and turbidity, apparent current boundaries, and
biological features were noted.
69
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Table 7. Oil Slick Remote Sensing Experiments
Date Oil Type Coverage
12 Sept. 69 6 Tri-X/47B
Kodachrome II
8443/15
26 Sept. 69 6 and menhaden 8403/47B
8443/1A
27 Oct. 69 6 8403/47B
Kodachrome II
12 Aug. 70 2 2405/15
8442/1A
2403/47
8443/15
6 Nov. 70 4 2492/18A
2403/57
2403/47
8443/12
2424/89B
SO-397/1A
2443/12
multispectral
scanner
3 Dec. 70 6 2403/47
2448/pol.
2448/1A
21 Jan. 71 2 2403/47+pol.
2445
2445/pol.
2443/12
2403/18A
26 Apr. 71 4 2403/47
2403/57
SO-397
2443/12
6 May 71 6 2443/1A
2443/15,20B
SO-397/1A
3 Aug. 71 4 SO-397/1A
2443/12
2403/47
2403/57
microwave radiometer
infrared scanner
70
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Table 7. (Cont'd.). Oil Slick Remote Sensing Experiments
Date Oil Type Coverage
30 Aug. 71 2 microwave radiometer
2443/1A
SO-397/1A
2403/57
2403/47
4 Sept. 71 6 2443/1A
V 2403/47
2403 /
13 Oct. 71 2 and 6 microwave radiometer
71
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A floating thermistor device was used to measure water
surface and oil slick temperatures. The thermistor
(L type, 5000 Q at 25 C, Applied Research Austin, Inc.,
Austin, Texas) was attached to the end of a spinal tap
needle mounted with vertical adjustment in a triangle
frame of stainless steel rod. Flotation of the frame was
provided by a ping-pong ball glued to each apex. The
design was similar to MarlattYs (1967), but did not damp
capillary waves, and should indicate more closely the
undisturbed surface temperature. A fishing pole was used
to place the device at least one meter away from the boat
hull, and carried the wires leading from the thermistor
to the temperature readout unit. The thermistor was
calibrated against a mercury stem thermometer, using the
freezing point of distilled water as a reference. This
technique measured temperature in the upper 2 mm of the
surface layer. Subsurface temperatures with the unit were
compared occasionally with those taken by stem thermometer.
Oil film thickness was calculated from the volume collected
in a 10 ml graduated pipette blown to the stem of a glass
funnel. The funnel, when pushed through the slick, acted
as a thickness amplifier, and was calibrated over the
thickness range 0.5-2.5 mm with No. 2 oil. Other funnel
pipettes were calibrated down to 30 /LOU thickness. The
funnels were limited to use in calm water, produced erratic
field data despite good prevision in the laboratory, and
worked poorly with No. 6 oil which adhered to glass surface
,even when they were precoated with photo-flow solution.
More accurate thickness data for heavy oils can be obtained
by weighing retrieved film samples, or by solvent
extracting them for colorimetric analysis. For thickness
less than 50 jum, appearance was converted to thickness
using the graph of Allen (1969), or Allen and Schleuter
(1969).
Each oil type used had its own visual characteristics,
which are described in the following paragraphs. In
general, these characteristics were present in aerial color
photographs, but much of the fine detail was lost, for
example, the distinction between No. 4 from No. 6 fuel oil
was lost.
Number 2 fuel oil spread rapidly. The slicks were thin
and symmetrical with interference rings near the edge, and
a large lens area in the center with an obvious yellow
color. This lens was broken only by vigorous wave action.
Aggregation into lumps or fibrils was never observed.
Number 4 fuel oil spread more slowly, and the resulting
slicks were much less regular in shape. Interference
colors were present around the slick edge and between areas
72
-------
where there were lenses of thicker oil. These thin regions
were compressed by wave action and formed thin brown
fibrils of oil that mixed below the water surface and
spread again when the forces leading to their compression
were removed. The lenses were visually thicker than with
No. 2 oil and were very dark brown. These slicks did not
fragment and clump.
Number 6 fuel oil was not observed to spread after initial
hydrodynamic energies of introducing the oil were
dissipated. The interference portions of the slick were
much smaller in area than for the other two fuel oils.
The lens portions of slick were difficult to disturb and
appeared like a crinkled warm asphalt when waves passed
under them. Lens were of irregular shape and their number
and extent depended on the manner of introduction of the
oil. Number 6 oil had a high coherence with itself, but,
when the lens were broken by breaking waves, small frag-
ments of oil did not reform the lens structure. The oil
mixed down into the water column as irregular fragments,
with the tendency to fragment increasing in experiments
conducted at lower water temperatures.
The appearance of these oils should vary with the source,
but the physical characteristics, such as viscosity, pour
point and other properties of the fuel oil types are
sufficiently different to allow visual distinction on water.
This situation might be changed as the oil ages, but the
oils generally dissipated before obvious changes occurred
in these small releases. The only aging change was that
No. 6 fuel oil aged over 1 day at sea was present in
fragments with much less thin oil and interference rings
than was present immediately following release.
REMOTE SENSING ANALYSIS
Photographic film was developed by the laboratory at NASA
Wallops Station and their contractors. Images were not
rectified for aircraft attitude. Multispectral scanner
data were reduced at the Willow Run Laboratories of the
University of Michigan. Data from all channels were
processed to a continuous-tone photographic format.
Ultraviolet and thermal infrared signals were processed
by voltage-slicing to give a radiance-contoured
photographic format. The contour intervals were assigned
ranges of equivalent black body temperature based on
scanner readings of two thermostated black body reference
plates (Hasell and Larsen, 1968).
73
-------
INFRARED SCANNER CALIBRATION
Infrared scanner temperatures from the oil release of
November 6, 1970, have been compared with temperatures
simultaneously measured on the surface. The scanner was
operated at 2000 ft altitude at 0900 and 1145, after oil
release at 0840. Corresponding surface temperatures were
measured at 0900 and 1200. The tabulation below shows the
scanner temperature (Teq), and the temperature of the top
2 mm layer of water (Tsw) .
Aircraft Pass Time Teq Tsw AT
1 0858 14.2-14.5 15.4 0.9-1.2
2 0902 13.2-13.6 15.4 1.8-2.2
3 1144 13.5-14.3 15.5 1.2-2.0
Between passes 1 and 2, Tsw was constant, Teq varied by 1 C,
the instrument reference temperature varied by 2.5 C and
there were apparent power supply problems. Passes 1 and 2
can be used only as indicators of relative temperatures.
There was no difficulty in calibration of pass 3, so its
AT value should be attributable to water emissivity value,
reflection of sky radiance, absorption and emission in the
atmospheric path to the passive infrared sensor, and
vertical temperature gradients near the water surface.
The surface air temperature was generally lower than Tsw
and the water temperature increased to 16.7 at 20 mm depth.
This temperature gradient is caused by evaporation, and
water-to-air heat conduction (McAlister, 1969). Assuming
the gradient continues linear from 2 mm depth to the 20 mm
infrared measurement depth, 0.15 C of the observed AT is
explained.
The Teq value is uncertain because of poor accuracy of
water emissivity and sky radiance information.
Emissivities reported range from 0.970 to 0.993 (Buettner
and Kern, 1965; Buettner, Kern, and Cronin, 1965; Saunders
and Wilklns, 1966; Saunders, 1967; Griggs, 1968; Lee, 1969;
Anding and Kauth, 1970) and caused an uncertainty in Teq
greater than the observed AT. From the field data of Weiss
(1963), Oshiver, et al. (1965), and Saunders (1967), 0.5 C
of AT is explained" By the above uncertainties.
Atmospheric radiation absorption and emission a 1.0 C
error in Teq at 2000 ft altitude, as indicated by Oshiver,
et al. (1965), Gamier (1971), and Marlatt and Harlan (1971)
74
-------
This explains 1.0 C of AT. The total explained AT is
1.65 C, which is close to the observed value and the AT of
2.2 C given by the equation of Pickett (1966). It is
apparent that Run 3 contains a consistent temperature data
set.
OIL SLICK TEMPERATURES
In slicks of No. 4 and 6 oils, oil surface temperatues
(Ts°) were equal to Tsw for thin films. Tso was up to
7.5 C higher than Tsw for millimeter thick portions of the
slicks. The greatest temperature differences were at
mid-day for slicks several hours old. Subsurface open
water temperatures were lower than the corresponding values
under warm oil.
During the 0848 pass on November 6, 1970, Ts° equaled Tsw.
Ts° for thick regions was measured 80 minutes later, but
still was only 0.3-0.6 C above Tsw. Comparison of infrared
and ultraviolet scanner outputs showed that the infrared
did not record slick edges. The scanner temperatures for
oil and water (Teq° and Teqw) differed by up to about 3.0 C,
but differences were not consistent due to scanner
calibration problems.
For the 1145 pass Ts° ranged from 15.5 C in thin films to
23.0 C in thick oil lenses. In moderate oil thicknesses,
TeqO was less than Teqw by 0.9-2.5 C. This difference was
reversed for very thick oil.
The Teq° - Teqw differences can be explained in terms of
the temperatures and emissivities (eo and ew) of oil and
water. Buettner, et al. (1965) reported eo for a oil film
of unknown type ancTthTckness as 0.972, compared to
ew = 0.993. In view of the uncertainty in ew, eo = 0.972
must be regarded as a rough estimate, and using this value
with Ts° - Tsw gives calculated differences considerably
smaller than those observed. The proposed eo value is
evidently too large, and a dependence of eo on oil
thickness is indicated, as suggested by Chandler (1970).
The rise in Tsw with time due to solar heating was less
than for Ts° of thick oil, because water has a lower
visible light absorbance than oil. It has been suggested
(Chandler, 1969; Estes and Golomb, 1970; Stewart, et al.,
1970) that the thermal infrared information might correlate
with slick thickness, but such correlations must be
ambiguous because of surface temperature variations and
uncertainty in e values and in the unknown eo - film
thickness relation.
75
-------
OIL FILM THICKNESS
Thickness of films was measured on November 6, 1970,
December 3, 1970, and January 21, 1971, and in later
experiments which involved the NRL microwave radiometer.
Stewart, et al (1970) have shown that oil spectral radiance
changes with thickness are small for films greater than
0.5 mm thick and that dark oil should be at least this
thickness. Thickness of dark regions were 0.1-0.8,
0.1-2.4, and 0.3-0.6 mm for numbers 2, 4, and 6 oil,
respectively. These values permit a photographic estimate
of the minimum volume of oil in dark areas of heavy oil
spills.
DETECTION AND DISCRIMINATION OF OIL TYPES
Photographic and scanner imagery have been examined
according to spectral region and observed oil type, but
number- 4 oil was the only type studied in all bands.
Photographic sensing bands are identified here by the
Kodak film - Wratten filter combination used. The term
positive contrast means that oil displayed more radiance
than water. Some photographs from this program are given
by Munday, et aL (1971).
In the near ultraviolet (0.32-0.40 jum, 2403, 2492/ISA),
number 2 oil showed positive contrast. Interference rings
were expected, but not detected. Number 4 oil showed
interference rings, sharp slick edges, large positive
contrast for films thinner than 50 jum, and small negative
contrast for thicker regions.
In the blue band (0.40-0.50 jjn; 2403/47), No. 2 oil showed
strong interference rings, and moderate positive contrast
in the main body of the slick. There was little radiance
variation across the slick, so thickness regions were not
distinguishable. Numbers 4 and 6 oil also showed strong
interference colors. Thin regions showed moderate positive
contrast and thick regions moderate negative contrast.
In the green-yellow band (0.50-0.62 iim, 2403/57), numbers
4 and 6 oil showed moderately. Thick regions showed large
negative contrast.
In the red-near infrared band (0.62-0.80 jum, 2424/89B),
number 4 oil was barely visible and thick regions showed
small negative contrast, so oil detection was not
practicable.
76
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Ordinary color (SO-397, 8442, 2448/1A), infrared color
(8443, 2443/12i 15) and infrared color with haze filter
(8443/1A) photography of oils was tested. Infrared color
was difficult to expose properly and gave poor contrast.
Ordinary color for No. 2 oil showed interference rings but
did not distinguish thick and thin regions. For No. 4 and
6 oil the interference rings were seen, edges appeared
light blue, thin regions appeared blue, yellow or brown, and
thick regions appeared gray or black. The infrared color
with haze filter gave the best image and color contrast.
For number 6 oil, interference rings showed well, thin
regions were pink with positive contrast, thick oil dark
red. Menhaden fish oil was white on a magenta water
background, thin oils were not imaged, and, as noted by
Barringer (1968), intermediate thicknesses were not
present.
Photography is useful for oil slick detection and
discrimination, a conclusion at variance with that of Estes
and Golomb (1970), who state that oil slicks do not
photograph well on color film. Photographic results here
agree with Lowe and Hasell (1969) and with the radiance
model of Stewart, et aL (1970) which predicts a change from
positive to negative oil/water contrast at 0.4 jum wave
length, a value close to the value 0.46 /urn derived from
observations in the present study. The results also agree
with Catoe's (1970) statement that thin slicks are detected
efficiently by UV-blue band photography.
The near ultraviolet band is best for imaging edges and
thin slicks, while the green band is best for delineating
thick oil regions. Number 2 oil can be distinguished from
No. 4 and 6 because it does not show negative contrast in
the blue and green bands. Menhaden oil can be distinguished
from the fuel oils by its lack of interference colors.
Ordinary color film is a good accessory record for all oil
spills. It distinguishes thick from thin oil, and helps
differentiate between oil and natural slicks. Color
infrared film may sometimes be needed to distinguish
between oil and floating vegetation.
OIL SLICK SPREADING
Slick areas were measured with a polar planimeter on Tri-X
film with a Wratten 47 filter or on color film. The slick
edge was taken as the edge of the outer dark interference
ring. True areas were calculated from vessel lengths in
photographs. Hourly area values were used to calculate oil
spreading rates, which were compared with rates predicted
77
-------
by the model of Fay (1969). This model predicts three
phases of spreading of point oil releases on calm water.
In phase three, spreading is caused by surface tension,
and retarded by viscous drag of the boundary water layer.
A small spill should quickly enter, phase three, whose
spreading law is r = k (a2t^/p2v)^ , where r is the slick
radius, k is a constant, a is the surface tension spreading
coefficient, t is time since release, p is water density
and v is water kinematic viscosity. Assuming slick area is
7rr2 and using the above equation,
A = at 3/2
where a represents a group of constants including k. Thus,
log A versus lot t should have an intercept of log a and a
slope of 1.5.
A vs t has been plotted on a logarithmic scale for releases
on August 12, 1970, November 6, 1970, December 3, 1970,
January 21, 1971, April 26, 1971, August 3, 1971, August 30,
1971, September 14, 1971. This plot is shown in Figure 24.
A line of slope 1.5 has been drawn through the points. The
intercept of this line, -1.072, was calculated from the
average of log a. values for all data points and differs by
a factor of 6 from that used by Fay. However, his value
involved an estimation of k without experimental verification,
The fit of the line to the data suggests that the phase
three spreading law is applicable. Guinard (1971) found
that a linear spreading law fit his observations, but no
linear relation has appeared in experiments here. At short
times after release, there is scatter in the data points
because the releases actually were not point sources of
oil, but were released over a 5 to 10 minute interval, and
because near the start of spreading the phase two conditions
stated by Fay may be more realistic than the phase three
assumption.
The number 2 oil spill on January 21, 1971, was made in high
wind conditions. Only one data point was obtained before
the slick was broken up. Number 6 oil did not spread in a
regular and monotonic manner. Much of the oil remained in
fixed patches, perhaps due to the high oil viscosity.
Fay's model does not treat the effect of oil viscosity, and
he acknowledges (personal communication) that there is some
oil viscosity limit above which his model fails. The lack
of spreading of number 6 oil is a useful criterion for its
remote sensing detection, particularly in the case of
recent spills. Number 4 oil, spilled on November 6, 1970,
78
-------
N
E
(T
©
o
D
#2 OIL (Aug '71)
OIL (Aug '70)
OIL (Jan '71)
-#4 OIL (Apr '71)
•#4 OIL (Nov '70)
OIL (Aug '71)
a
10s
10=
TIME (seconds)
Fig. 24. Spreading rate of No. 2 and No. 4 fuel oils
on sea water.
79
-------
failed to spread regularly after the first hour. This lack
of spreading may be caused by chemical confinement by
natural surface-active organic material or by physical
confinement between current convergence zones. These
factors are likely to be operative in the estuarine water
of the York River, where the release was made. All other
number 4 and 2 oil spills spread regularly.
Other spreading models (Murray, et aL, 1970; Blokker, 1964;
Abbot and Hayashi, 1967; Berridge, et aL, 1968) should be
applied to the spreading data, but lEEe nearly calm
conditions during experiments indicated that Fay's model
was most applicable to the present work.
80
-------
SECTION VII
PHYTOPLANKTON IN SURFACE SLICKS AND IN ADJACENT
SUBSURFACE AND NON-SLICK WATER
The surface microlayer of the ocean is being recognized as
an environment which possesses certain unique chemical,
physical, and biological properties. Of these, the first
two have, to date, been given the most attention.
Both naturally occurring and man-made surface films have
been investigated. Blanchard (1964) proposed that the
surface active organic material has its source in the
dissolved organic matter of the sea, and that it is
transformed into particulate form and transported to the
surface by bubbles. Sturdy and Fischer (1966) studied the
surface tension of slick patches produced by large beds of
kelp. Jarvis, Garrett, Schieman and Timmons (1967)
collected samples of surface active material from different
locations and found that all the material collected was
similar in surface properties, indicating chemical
similarities. Further study showed slick material to
contain fatty esters, acids, alcohols, and hydrocarbons
(Garrett, 1967a), as well as high concentrations of organic
carbon, nitrogen, and phosphorous.
The need for better understanding of the biology of the
surface microlayer has only recently been stated. Parker
and Barsom (1970) stressed the probability that the micro-
layer was of considerable ecological importance because of
the interaction between this layer and the air-sea
interface. Ahlstrom (1969) stated that although surface
films and slicks must contain communities different from
those in the rest of the water column, there is little
known about these organisms. David (1965) pointed out
that the surface layer is of particular significance
because the local environmental conditions are liable to
such great and rapid changes.
Biological investigations of surface layers have been
limited by problems associated with obtaining an adequate
surface sample. Recently, some sampling devices have been
developed which helped overcome this difficulty. Harvey
(1965) originated a rotating drum sampler capable of
collecting a layer of water and surface film from the upper
60 microns of sea surface. He compared samples taken by a
bucket dipped to a ten centimeter depth with samples taken
by his drum sampler, and found a higher concentration of
organic material, including live phytoplankton, in the
81
-------
surface microlayer. A second type of sampling device, a
screen apparatus, has been successfully used by Garrett
(1965).
The present study investigates the phytoplankton found in
the surface microlayer of the water column of an estuary.
A Garrett-type screen collection is used to make a
quantitative comparison between the phytoplankton present
in this thin layer, and that found in the water one meter
below. It also attempts to discover phytoplankton changes
brought about by the presence of a film of slick material
over the water surface.
SAMPLING PROCEDURE
Collections were made in two areas (Figure 25): the York
River (I), near the Virginia Institute of Marine Science
(VIMS), and, in one case, close to the Chesapeake Bay
Bridge-Tunnel (II). Collection intervals were irregular
because sampling was possible only in calm weather. A
total of 10 sets of samples were collected on the dates
shown in Table 5.
Each set of collections consisted of four samples: a pair
of surface and subsurface samples in an area of water
covered by a monolayer (designated a "slick" area); and a
similar pair of samples in an adjacent "normal" or
"non-slick" area.
One set of samples departed from this procedure. In
Collection 3 a non-slick environment was sampled, then a
quantity of No. 2 fuel oil was released in the area.
Another set of samples (corresponding to the usual slick
samples) was taken after 30 minutes.
SAMPLING DEVICES
Surface samples were taken with a screen device constructed
and used according to Garrett (1965). It consisted of a
24 in. square of 16 mesh monel screen in a brass frame with
upright handles and cross-bar. It is claimed that the
upper 0.15 mm of surface water is sampled by this method,
that sea slick material can be collected in sufficient
quantity for study, and that the method is about 70 percent
efficient after the first dip of the screen.
The screen was dipped into the water, withdrawn, and
drained through a funnel into a wide-mouthed polyethylene
jar. Ten dips were required for a sample volume of
82
-------
10 20 30
I I I
NAUTICAL MILES
Fig. 25. Plankton sample areas
83
-------
approximately one liter.
Subsurface samples were taken at a depth of one meter with
a one liter Frautschy bottle.
The sampling problems presented by the irregular horizontal
distribution and abundance of phytoplankton are well known
(Ahlstrom, 1969; McAlice, 1970). Patchiness makes it
nearly impossible to obtain an accurate representation of
the phytoplankton in a given area from a single sample.
Holmes and Widrig (1956) stated that in order to reduce the
time required for the analysis of additional samples, the
samples may be pooled and treated as one, without damaging
the precision of the estimate. Sample pooling has been
used in this study. In each surface collection the ten
dips of the screen were combined into a single one liter
sample, and for every subsurface sample three Frautschy
bottle casts were made and pooled into one sample.
COMPARISON OF SAMPLERS
In order to make quantitative comparisons of surface and
one meter collections, it was necessary to compare
Frautschy bottle and screen sampler cell counts. A 420
liter tank was filled with filtered seawater, and a
unialgal culture of the diatom Phaeodactylum tricornutum,
of a known concentration, was added. The water was
agitated to insure a homogeneous distribution of cells
throughout the tank, and samples were taken at the
surface with the screen, and at one meter with the
Frautschy bottle. A second set of samples was taken after
remixing. The experiment was later repeated with a
different volume of algae. All samples were counted on the
inverted microscope. There were no significant differences
between the samples obtained with the two devices when the
standard F, or Variance Ratio, Test was applied. Both
samplers gave good estimates of the population in the tank
(Table 8).
QUANTITATIVE SAMPLE TREATMENT
All field samples were stored in wide-mouthed polyethylene
jars, preserved with five percent neutralized formalin,
and returned to the laboratory for concentration. After
three days of settling the supernatant was siphoned off,
leaving a volume of approximately 500 ml. Further
concentration reduced the volume to 150 ml. An additional
procedure was carried out for Collection 3A (the surface
slick sample taken 30 minutes after an oil spill) . After
84
-------
Table 8. Results of Sampler Comparison Experiments-?-
oo
Exper .
I
II
III
Screen F. Btl. Actual #
Cell Cell Cells Screen F. Btl. F
Counts Counts in Tank Est. Est. Value
Cells /ml Cells /ml Cells /ml Cells /ml Cells /ml
2,014
1,862
1,475
2,038
1,593
1,421
1,681
10,010
12,118
11,760
1,912
1,970
1,446
2,102
2,372
2,102
2,087
12,871
13,661
10,932
2,000 1,847 1,857 81,579 ^ i o06 N s
67,659 ' '
2,000 1,565 2,187 25,725 _ -, 471 „'
17,48> i'4/i N-0>
10,000 11,296 12,488 197,187,700 _ -, ,, 7 „ q
136,274,535 L'^! n§s'
-------
settling, the No. 2 fuel oil formed a layer at the top of
the sample jar. A portion of the oil was pipetted off and
examined separately from the rest of the sample.
Phytoplankton cells were enumerated quantitatively by the
Utermohl method, which the National Academy of Sciences
(Ahlstrom, 1969) called "probably the best method known
for this purpose.
A detailed treatment of the statistical procedures involved
in the Utermohl method is found in Lund, Kipling and
Le Cren (1958). Assuming a random distribution of cells,
the counting and sampling errors can be estimated. The
Chi Square (X^) test for randomness was applied to ten sets
of five replicate counts each. Since none of these had a
significant X^ value (Table 9) the hypothesis of random
distribution was supported. An estimate of the variation
due to subsampling was made by counting five subsamples
from each of five different samples. Confidence limits at
the 95 percent level were ±3.7, ±3.3, ±2.5, ±4.8, ±3.6
percent (Table 10) . The personal counting error was
determined by ten replicate counts of a single subsample
(Table 11) , and the confidence interval at the 95 percent
level was ±2.9 percent. Since this variation was within
the range expected from a series of random samples, this
source of error was insignificant.
For every concentrated field sample three one ml subsamples
were counted. Each subsample was pipetted into a
cylindrical chamber with an inside diameter of 25 mm, and
allowed to settle overnight. Counts were made of a 100 mnr
section of each chamber. The median number of phytoplankton
cells per ml of water sample was calculated by the formula:
where N = number of organisms per ml of original water
samples
n = median number of organisms from the three
counts
c - volume of the concentrate in ml
s = original volume of sample before concentration
x = area of bottom of counting chamber
area of counted portion
Ricker (1937) gave a formula for calculating the confidence
intervals of a count, and Lund, et al (1958) stated that if
the organisms have been shown to be randomly distributed,
the confidence limits can be used to compare counts. There
is a significant difference between two counts if their
86
-------
00
•-J
Table 9. X2 Test for Random Distribution.
I II III IV V VI VII VIII IX X
1.
2.
3.
4.
5.
X2
163
166
173
178
167
.86
N.S.
1130
1212
1197
1222
1190
4.3
N.S.
982
1002
1032
1028
1016
1.7
N.S.
345
369
378
375
357
1.3
N.S.
1328
1446
1334
1372
1361
6.5
N.S.
1189
1198
1200
1155
1221
1.9
N.S.
1772
1790
1718
1792
1834
5.2
N.S.
337
347
327
360
332
2.0
N.S.
2586
2398
2551
2546
2537
8.3
N.S.
1902
1912
1868
1931
1899
1.1
N.S.
-------
Table 10. Counts of Five Replicate Subsamples from
Samples. Figures represent cells/ml.
B
Five
1.
2.
3.
4.
5.
Mean
Stand, dev.
Stand . error
Interval est.
1130
1212
1197
1222
1190
1190
35.89
16.05
±44.55
or
± 3.7%
1790
1718
1792
1834
1732
1773
37.63
21.30
±59.13
or
± 3.3%
982
1002
1032
1028
1016
1012
20.45
9.10
±25 . 26
or
± 2.02%
337
347
327
360
332
341
13.13
5.87
±16.29
or
± 4.8%
354
369
378
375
357
367
10.70
4.79
±13.29
or
± 3.6%
Table 11. Counts of Ten Replicate Subsamples from One
Sample. Figures represent cells/ml.
Mean
Stand, dev.
Stand, error
Interval est
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
•
770
763
812
798
733
801
774
807
746
724
773
31.
9.
±22.
or
± 2.
5
9
39
9%
88
-------
confidence intervals do not overlap. This criterion was
used to compare samples.
POPULATION STATISTICS
The phytoplankton cells in each sample were enumerated and
identified, where possible, to species. The percentage
composition of the samples was determined by a method
recommended by Morse (1947) . The first 200 cells of each
sample were identified and the total number of each species
divided by two to find the percentage for each species.
Diversity was calculated according to Shannon (1948):
H1 = - E p± Iog2 p±
where H1 = a proportion between the number of individuals
of each species and the total number of
individuals in the sample.
Pi * n£ / N.
n^ = number of individuals in the ith species.
N = total number of individuals in the sample.
This index is cited by Pielou (1966) as appropriate for
situations, such as plankton samples, in which a collection
is too large for all of its members to be counted. It is
improbable that all species present in the samples were
identified since the number of cells enumerated was limited
to 200, but, when H1 is used as a measure of diversity, the
rare species have little influence on the result.
Further comparison between samples was made using Sander's
(1960) dominance-affinity index. Two samples are compared
by computing the percentage of the total sample represented
by each species present in both samples, and summing the
smaller percentage for each species. The resultant value,
the index of affinity, is a measure of the percentage of
organisms common to the pair of samples.
RESULTS AND DISCUSSION
Table 12 summarizes results of plankton counts. With one
exception (Collection 7) all non-slick samples showed an
abundance of phytoplankton that was 1.5 to 5.4 times greater
than in samples from adjacent slicks. Similarly, nine of
89
-------
Table 12. Results of Sample Counts, in cells/ml.
Collection Location Date Slick
Non-Slick
#
1 I
2 II
3 I
4 I
5 I
6 I
7 I
8 I
9 I
10 I
29 VIII 69
25 IX 69
12 XII 69
22 IV 70
1 VI 70
28 VII 70
28 VII 70
17 IX 70
17 IX 70
17 IX 70
Surface
1561
250
284
4700
421
665
870
1356
1686
62
1 Meter
674
245
351
1920
1268
658
891
523
460
55
Surface
2074
492
544
8281
2257
1000
732
2202
3026
131
1 Meter
1312
207
316
1555
781
483
619
355
721
64
-------
ten non-slick surface samples had a greater abundance of
phytoplankton than the-corresponding samples from one
meter--ranging from 1.2 to 6.2 times greater. The
reliability of Collection 7 was doubtful because it was
collected in unfavorable weather. Confidence intervals
(Table 13) show that in all cases these differences were
statistically significant, since their intervals never
overlapped.
The cell count in the fuel oil fraction of the slick sample
in Collection 3 was compared with that in the normal slick
sample. It was found that the oil fraction contained a
higher number of cells.
The total number of cells in each sample is divided into
its component parts (Table 14) to show the percentage of
the sample that is composed of diatoms, dinoflagellates,
and other types of phytoplankton (including silicoflagel-
lates and Euglenophytes). The diatoms displayed peaks of
population in April and August-September. Dinoflagellates
reached a population maximum in August, with a lesser
increase in June. The August dinoflagellate abundance is
not from the regular sampling program, but represents a
surface sample taken during a dinoflagellate bloom.
Ninety-eight species were identified. Of these, 36
occurred with sufficient frequency to be considered major
components of the flora. Skeletonema costatum was the
dominant organism in 92.5 percent of the samples, and the
second most abundant species in an additional 27.5 percent.
It was totally absent from only two samples, or five
percent of the total.
T[
Comparison of diversity values for slick and non-slick
areas did not show any significant trend. Comparison of
values from surface and one meter samples showed that the
diversity in the surface microlayer was generally lower
than at one meter, as can be seen in Figures 26 and 27.
Comparison of sample pairs (surface slick and non-slick;
non-slick surface and one meter) by the affinity-dominance
index are given in Table 15. Values range from 53.5 to
100 percent. Over half of the sample pairs have affinities
over 75 percent, indicating a very homogeneous flora.
Chemical analysis of two of the slicks showed that they
consisted of naturally occurring slick material. It is
probable that the other samples (except Collection 3) were
of similar composition.
91
-------
Table 13. Confidence Intervals, at the 99% Level, for Sample Counts.
Collection
Surface
Non-Slick
ro
# Slick
1
2
3
4
5
6
7
8
9
10
1172
212
243
4526
371
601
797
1264
1583
44
- 1357
- 295
- 331
- 4880
- 478
- 735
- 950
- 1455
- 1796
- 86
Non-Slick
1959
438
487
8049
2137
921
665
2085
2887
104
- 2195
- 553
- 608
- 8519
- 2383
- 1085
- 806
- 2328
- 3172
- 165
Surface
1959 -
438 -
487 -
8049 -
2137 -
921 -
665 -
2085 -
2887 -
104 -
2195
553
608
8519
2383
1085
806
2328
3172
165
1 Meter
1069 -
173 -
273 -
1456 -
712 -
429 -
557 -
309 -
665 -
46 -
1245
248
366
1661
857
543
686
408
794
89
-------
Table 14. Composition of Surface Samples, Slick and
Wnrn-ol -I r»tr
Non-slick.
Sample #
1A
1C
2A
2C
3A
3C
4A
4C
5A
5C
6A
6C
7A
7C
8A
8C
9A
9C
10A
IOC
Diatoms
1210
1588
194
475
275
506
4606
8199
246
902
572
580
644
681
1288
2203
1686
3026
53
112
Dinoflagellates
226
238
56
17
9
30
71
139
1140
93
420
226
51
68
_
_
.
7
14
Other
125
•&» «^
248
*•» V \f
8
23
•M*^
82
\J AM
36
214
^
_
_
_
^
_
—
2
5
Slick C = Non-slick
Table 15. Affinity Index Values for Paris of Samples.
Collection # Slick/Non-Slick Surface/1 Meter
(Surface) (Non-Slick)
1
2
3
4
5
6
7
8,
9
10
75.0%
74.5%
64.5%
89.5%
60.5%
71.0%
78.5%
94.0%
94.0%
71.0%
53.5%
99.0%
71.5%
77.0%
80.5%
74.0%
82.5%
100.0%
100.0%
72.5%
93
-------
3.51
3.0-
2.5-
>
5 2.0-
o
t 1.5-
0)
DC
UJ
1.0-
0.5-
0.0-
SURFACE
I METER
I I | I
i n ni 12
3Zi 3zn. 3znr TK
COLLECTION NO.
Fig. 26. Comparison of surface and one meter diversity
in slick areas.
94
-------
3.5-1
_i
<
3.0-
2.5-
2.0-
^ 1.5
CO
o:
UJ
1.0-
0.5-
0.0
n
SURFACE
I METER
rz: 2 si mr snr ix z
COLLECTION NO.
Fig. 27. Comparison of surface and one meter diversity
in non-slick areas.
95
-------
This study shows that, in an estuary, the surface micro-
layer of the water column differs substantially from the
underlying subsurface water (one meter), both in the
phytoplankton concentration and species diversity. The
data support Harvey (1965), who reported that microlayer
samples had at least four times the total number of algae
and protozoans as samples from 10 cm. This information on
the vertical distribution of phytoplankton should be
considered when designing a phytoplankton sampling program,
and is significant in studies attempting to estimate the
standing crop of phytoplankton. This estimate requires
accurate determination of the amount of phytoplankton in a
sample, and collection of samples that are representative
of the area being studied (Small, 1961). A typical
"surface" sample consists predominantly of water lying at
some depth beneath the actual surface layer. This extra
volume of water dilutes the number of cells present and
results in an underestimation of the abundance of
phytoplankton per unit area of surface.
It is possible that previous estimates of primary
production have erred in the same way. Depth samples for
Carbon-14 measurements standardly include the surface
(Steeman Nielsen, 1952a), and in some cases are restricted
entirely to the surface (Doty, 1956). It remains to be
shown if the cells in the surface microlayer are photo-
synthesizing at a maximal level. David (1965) suggested
that there must be a permanent flora in the surface layer
despite high light intensity, and stated two hypotheses:
first, that the cells of this population would be highly
specialized and able to utilize intensities that are
normally thought to be inhibiting; and second, that
photosynthesis would take place only when light intensity
was low. There is a third possibility—that the inhibitory
effect of high light intensity has been overemphasized,
since most data has been obtained through laboratory
studies in simulated conditions (Steeman Nielsen, 1952b,
1962; Sorokin and Krauss, 1958; Brown and Richardson,
1968) .
All observations here indicate that the cells of the micro-
layer are healthy and active. When samples were examined
live the cells appeared in good phytiological condition.
Chloroplasts were abundant, and organisms capable of
locomotion (dinoflagellates and some diatom species) were
moving. In examination of preserved material, cells were
often observed that had recently divided, or had been
preparing to do so.
The lower diversity in the surface microlayer was caused by
an increase in abundance of the one or two most dominant
96
-------
organisms (most often Skeletonema costatum but
occasionally Cerataulina bergonTI or Rhizosolenia
faeroense) . The rare species that occurred in the one
meter samples did not appear in the surface samples. This
implies that certain species select the surface environ-
ment, possibly due to the light conditions.
A normal environment is assumed to support a diverse
assemblage of species, while one that has been subjected
to any type of pollution suffers a reduction in diversity,
with an increase in numbers of individuals of the remaining
species. Patrick (1949) stated that this is the first
effect produced by a pollutant, and described a system
which employs the distribution of species and specimens of
the diatom population as an index of water pollution. This
system has been successfully applied in several studies
(Patrick, et al, 1954; Hohn, 1959; Patrick and Strawbridge,
1963). Wilhm and Dorris (1968) agreed that pollution
results in depressed diversity, and stated that the
properties of diversity indices (the fact that they are
dimensionless, independent of sample size, etc) make them
well suited for use as criteria for judging water quality.
A study of the effect of oil pollution in a river
(McCauley, 1966) found that oil produced the typical result
by eliminating the plankton organisms sensitive to the
toxicity, while permitting the more tolerant species to
thrive.
It seems significant that there is no pattern discernible
in diversity values of the four samples in each of the
collections. This indicates that, although the presence of
a slick does have a measurable influence on the phytoplank-
ton in that area, it does not act in the manner usually
associated with pollutants. Comparison of sample pairs by
means of the affinity-dominance index supports the data
obtained from diversity comparisons. In all cases the
slick and non-slick pairs of samples had high affinity
values, showing that their populations were very similar
in composition.
Slick material might produce its effect through purely
physical factors. The fact that more cells were discovered
in the oil fraction of Collection 3 than in the rest of the
slick sample suggests that some phytoplankton cells may
have been physically entrapped in the oily layer. ^This^
would explain the absence of a reduction in diversity since
the cells would, presumably, be caught at random, rather
than selectively by species. Mironov and Lanskaja (1958)
stated that floating organisms, such as zooplankton and
phytoplankton, are particularly susceptible to injury from
oil because they cannot move actively to avoid a polluted
area.
97
-------
There is some disagreement as to the effect of oil on the
organisms of the phytoplankton, but few actual experiments
have been carried out. Zobell (1964) stated that diatoms
seemed to be harmed only by "prolonged exposure to large
amounts of oil." In one experiment (Galtsoff, Prytherich,
Smith, and Koehring, 1963) the diatom Nitzschia closterium
was found to grow almost as well in medium overlayed with
various kinds of oil as in the controls. However, a
water-soluble extract from 25 percent crude oil was shown
to retard growth of diatom cultures, and a !50 percent
extract stopped growth entirely. Mironov and Lanskaja
(1966) conducted experiments on 20 species of planktonic
algae and showed that various oils exhibited a definite
toxic effect, causing retardation in cell division and,
ultimately, death.
Further investigation is necessary to determine what is
causing the reduction in number of phytoplankton cells
in the presence of a slick, and if there actually is a
physical entrapment of the cells. Another area that
requires examination is the probable correlation between
the percentage of the population found in the surface
microlayer on a given day, and the amount of incident
radiation on that day. One would predict an inverse
relationship: on a cloudy day more cells would be at the
surface in order to obtain sufficient energy for
phytosynthesis, especially in murky inshore waters.
98
-------
SECTION VIII
CHLORINATED HYDROCARBONS IN INDIGENOUS SURFACE FILMS
Ecological and human health problems resulting from the use
of chlorinated hydrocarbon pesticides and polychlorinated
biphenyls make it desirable to know the role of surface
films in concentrating and transporting these substances.
The distribution of chlorinated hydrocarbons between
surface slick and subsurface (1 meter) water samples from
the York River estuary has been evaluated and compared with
data obtained by Seba and Corcoran (1969) in an attempt to
establish the behavior of these compounds in a relatively
unpolluted environment. Slicks were sampled by a drum
skimmer (Harvey, 1965), but, as in Seba and Corcoran's
work, the ratio of dissolved organics to slick organics in
the sample was not measurable. Preliminary analyses of
surface and subsurface samples indicated the presence of
detectable concentrations of polychlorinated biphenyls
(PCB) and chlorinated hydrocarbon pesticides (CHP). The
similarities of chemical structure of PCB's and CHP's
(especially the DDT family) caused extensive masking and
interference of peaks when the samples were analyzed on the
gas chromatograph. Several methods for total separation of
PCB's and CHP's were tested in an attempt to obtain
quantitative data on both groups. Although several
researchers (Holden and Marsden, 1969, and Reynolds, 1969)
have claimed success in this separation, difficulties are
well known and documented (Zitko, 1971a). To date,
consistent and practical total separation of PCB's and
chlorinated hydrocarbon pesticides at low concentration
levels (effective at 10~10g//il) has not been achieved at
this laboratory. Without total separation of chlorinated
hydrocarbon pesticides and PCB's, the concentration
estimates for PCB's are less accurate and the concentration
of some pesticides cannot be evaluated. In this work, the
DDT concentration was determined by converting it to DDE by
dehydrochlorination in methanolic KOH, and the PCB
concentrations were estimated from uninterfered peaks in
the chromatograms.
SAMPLING METHODS
Surface and subsurface samples were collected from the York
River estuary at irregular intervals from November 1970 -
November 1971. Slicks sampled were observed and classified
as: (1) Light slick - capillary wave dampening under 0-5 ^
mph winds, (2) medium slick - capillary wave dampening with
99
-------
winds estimated 5-10 mph (usually contained light debris),
(3) heavy slick - capillary wave dampening with winds
estimated at 10-15 mph (usually contained much debris).
Non-slick surface and subsurface samples were taken for
comparison of chlorinated hydrocarbon content with the
different slick types. Sampling dates and locations are
shown on Figure 28.
Twelve liter surface samples were taken with a boat-mounted
ceramic coated drum skimmer built by NASA Wallops Island
Station. This apparatus avoided contamination while
sampling, and samples were taken easily and quickly. When
sampling, the boat was operated in the upcurrent direction
to avoid collection of engine oils. The water surface
layer was picked up in a stainless steel trough and drawn
under vacuum into an 18 liter glass bottle. The sampling
apparatus was washed with chloroform before each day's use
and flushed with new sample at each station. Only
stainless steel, glass, and teflon contacted the sample;
this prevented contamination of the sample by grease, oils,
fats, etc, that might have high chlorinated hydrocarbon
concentrations.
The subsurface samples were taken by a diver who immersed
an 18 liter glass bottle to approximately 1 meter and
allowed it to fill with 12 liters of water.
ANALYTICAL PROCEDURE
In the laboratory, the 12 liter sample was transferred from
the sample bottle to a 20 liter glass carboy with a bottom
drain stoppered with a clamped teflon tube. The sample
bottle was washed three times with 250 ml of pesticide-pure
petroleum ether and these washings were also added to the
carboy. The carboy was stoppered and the sample and
petroleum ether were shaken vigorously for 5 minutes; at
the end of shaking the water layer had become cloudy. The
sample was allowed to stand overnight in the carboy. The
next day the clear water layer was discarded through the
bottom spigot and the ether portion was collected in a
2000 ml round bottom flask. Three grams of anhydrous
Na2S04 was added to remove the remaining water, and the
sample was redissolved and transferred to a 50 ml beaker by
three 15 ml washings of pesticide pure petroleum ether.
The petroleum ether was allowed to evaporate to a volume
of about 0.5 ml. The 0.5 ml sample and two 1 ml ether
washings of the 50 ml beaker were then added to a 3.0 ml
centrifuge tube, evaporated to 0.25 ml in a jet of
prepurified nitrogen, spotted on TLC plates, and developed
100
-------
•8.SEPT. 9,1971
37
25'
20
37
II,OCT.5,I97I
14,NOV. 3,1971
12,OCT. 5,1971
I3.NOV.3, 1971
6, FEB. 6,1971
2, NOV. 27,1970
I, NOV. 27, 1970
5, JAN. 30, 1971
3, JAN. 30,1971
4, JAN. 30,1971
7, SEPT. 6,1971
FIGURE 28. SAMPLE LOCATIONS AND DATES
-101-
-------
in CC1-4 to the 10 cm line in a TLC chamber according to the
procedure of Breidenbach, et al (1966). Silica gel on the
plate from 2 cm to 10 cm was scraped off and collected by a
vacuum silica gel collection assembly. Chlorinated hydro-
carbons absorbed on the silica gel were eluted into a
graduated centrifuge tube by 15 ml of 50% petroleum ether-
acetone solution. The samples were again reduced to 1.0 ml
in a jet of prepurified nitrogen and analyzed in a Perkin-
Elmer 900 gas chromatograph fitted with an electron capture
detector. Two columns were used for sample analysis, one
was 3% D.C. 200 on Varaport 30 80/100 mesh, the other was
5% QF-1 on Chromosorb G AW DMCS 80/100 mesh. Identifi-
cations of PCB's and DDT family pesticides were made by
comparing retention times of sample peaks with the
retention times of known standards on both columns.
The DDT content of the samples was determined by comparing
the reduction in the area of the DDT peak, following
dehydrochlorination of DDT to DDE in methanolic KOH, with
the DDT peak area of a known concentration standard.
The concentrations of PCB's were determined by measuring
the heights of four peaks that were not interfered with by
members of the DDT family and comparing these heights with
the four corresponding peak heights of a known concentra-
tion standard of Aroclor 1254. Although this analysis
involves error in the quantitation of PCB's because the
electron capture detector response can vary widely for each
polychlorinated biphenyl, Aroclor 1254 is composed mostly
of tetra-, penta-, hexa-, and heptachlorobiphenyls (Koeman,
et al, 1970) and our error would be relatively small
because the electron capture detector response to these
compounds does not vary by more than a factor of 2 (Zitko,
1971b).
Pesticide and PCB standards of known concentration were
mixed into 12 liters of distilled water, extracted with
petroleum ether, and run through the procedure with the
samples to provide information on extraction efficiencies.
Twelve liters of distilled water was extracted and analyzed
as a blank. A 750 ml petroleum ether blank was evaporated
in the rotary evaporator and treated as a sample extract.
No interfering substances were found in the petroleum ether
blank, but peaks corresponding to Aroclor 1254 were found
in the distilled water at a concentration 6 ng/liter.
These peak heights were subtracted from the pesticide and
PCB standards to obtain procedure efficiencies. The
efficiencies were: PCB's (Aroclor 1254) - 50% (all peaks in
same ratios as standard), DDE - 6%, ODD - 20%, and DDT -
18%. The appropriate efficiencies were used for
102
-------
determining the concentrations of PCB's and DDT in the
samples.
All glassware was washed, rinsed with distilled water,
dried with acetone, and rinsed with petroleum ether before
each use. Samples 6 and 7 were contaminated by lubricant
mistakenly applied to the rotary evaporator. Because a
procedure efficiency was calculated and care was taken that
each sample was treated identically, the DDT and PCS
concentrations and the total chlorinated hydrocarbon count
(on Table 1) represent the chlorinated hydrocarbon concen-
trations found in slick, non-slick, and subsurface samples.
Separations similar to Reynolds' (1969) Florisil column
separation of Aroclor 1254 and CHP were tested in the
laboratory and found unsatisfactory because of solvent
contamination and the variability of Florisil and pesticide
pure solvents. Volumes of 200 ml of hexane or 200 ml of
20% diethyl ether in hexane solution from the elution of
the Florisil column in the Reynolds' procedure must be
concentrated to approximately 0.5 ml in order to analyze
the small amounts of chlorinated hydrocarbons obtained in
this study. Gas chromatographic peaks of contaminants
interferring with chlorinated hydrocarbon analysis were
observed from evaporation of 200 ml pesticide standard
hexane (Nanograde, Mallinckrodt) or 2070 diethyl ether
hexane solution to 0.5 ml. Unpredictable and incomplete
elutions resulting from the variability of Florisil and the
different elution properties of pesticide grade solvents
(Zitko, 1971a) made the Reynolds separation technique
further undesirable for this study.
The Holden (1969) silica gel procedure for separating PCB's
and CHP's uses smaller amounts of solvents, avoiding
solvent purity problems, but silica gel columns, like
Florisil columns, vary in their elution properties. Two
types of silica gel, different column loadings, and
different silica gel deactivations (by shaking with
distilled H20 for 30 minutes) , were used in an attempt to
separate Aroclor 1254 from DDT and ODD, but no reliable
separation was found.
Thin layer chromatography procedures similar to Mulhern s
(1968) for the separation and removal of organochlorine
insecticides from thin layer plates were tested using
Aroclor 1254 and a DDE, ODD & DDT standard, but the
separations were ineffective.
Differentiation and identification of PCB's and CHP's in
the samples by gas chromatography of nitrated sample_
extracts was not attempted because some PCB s also nitrate
103
-------
and clear cut identification cannot be made (Reynolds,
1969).
RESULTS AND DISCUSSION
The DDT concentrations shown in Table 16 are similar to
those found in western streams by other workers (Brown and
Nishioka, 1967). Duke, et s& (1970) have shown that
Aroclor 1254 concentrations in water can at times be great
(275 ppb) due to accidental introduction by industry, but
they found values in the range of our data (100 ppt in
Escambia River to non-detection in Escambia Bay) following
correction of the 1254 leak.
There was an average of 16 ppt (range trace to 54 ppt) DDT
o,p, and p,p' in our transitory slicks; Seba and Corcoran
(1969) found 19 ppt DDT in a transitory slick in the main
axis of the Florida current. The DDT content of the only
semi-permanent slick sampled by this study varied from
12 ppt - 41 ppt on the two sampling dates. Seba and
Corcoran found 61 ppt to 3465 ppt DDT in semi-permanent
slicks associated with the mouths of drainage canals in the
Biscayne Bay. They found 2-35 ppt Dieldrin and 5-34 ppt
Aldrin in slick samples, but neither of these pesticides
were detected here.
Corcoran (personal communication) states that PCB's
occurred in very low concentrations in their samples.
PCB's corresponding in retention times to Aroclor 1254
were present in our samples as indicated on Table 16.
Seba and Corcoran (1969) sampled with jars by immersing
them just below the surface. Neither this method nor the
drum skimmer permitted determination of the relative
amounts of surface film material and water obtained in the
samples. Depending on whether the slick is spread out
thinly over a large area or is relatively thick but
covering a small area, the chlorinated hydrocarbon
concentrations in the samples could vary according to the
slick area exposed to the environment. The first
priorities for any future work on surface films should be
the development of a field surface film thickness measuring
device.
Although the data show that our classification of slick
type cannot be used to determine the amount of chlorinated
hydrocarbons present in the surface film, it does indicate
that the concentration of total chlorinated hydrocarbons in
surface films are generally higher than the subsurface
concentrations. The DDT concentrations were generally
104
-------
o
Ul
Table 16. Chlorinated Hydrocarbon Concentration Results
Total
Chlorinated
Sample #
1 Surface
I Subsurface
2 Surface
2 Subsurface
3 Surface
3 Subsurface
4 Surface
4 Subsurface
5 Surface
5 Subsurface
Date
11/27/70
ii it ii
11/27/70
H it ii
1/30/71
ii ti H
1/30/71
ii ii ii
1/30/71
H H II
Slick Hydrocarbon PCB**
Type Count* (ppt)
1
-
3
No
Slick
3
No
Slick
530
156
640
202
28
34
256
264
338
302
51
16
37
17
2
3
21
26
33
29
DDT
(ppt)
17
1
54
3
3
6
26
5
3
2
Slick Origin
Unknown
Probably
West Point
Pulp Mill
American Oil
Pier
(recent origin)
6 Contaminated
7 Contaminated
-------
Table 16. (Cont'd). Chlorinated Hydrocarbon Concentration Results
Total
Chlorinated
Sample #
8 Surface
8 Subsurface
9 Surface
9 Subsurface
10 Surface
10 Subsurface
11 Surface
11 Subsurface
12 Surface
12 Subsurface
13 Surface
13 Subsurface
Date
9/9/71
n n n
9/9/71
n n n
9/9/71
ii n n
10/5/71
n n n
10/5/71
n it n
11/3/71
n n n
Slick
Type
3
-
2
2
-
3
-
3
3
Hydrocarbon
Count*
178
108
Spilled
86
43
59
120
58
118
152
325
172
PCS**
(ppt)
12
8
7 Not
4
5
5
9
7
11
24
12
DDT
(ppt)
Trace
Trace
Measured
Trace
Trace
Trace
Trace
12 ,
4
41
27
Slick Origin
Pulp Mill
Pulp Mill
•
Unknown
Unknown
Mouth of
Queen ' s
Creek
Mouth of
Queen ' s
Creek
-------
Table 16 (Cont'd). Chlorinated Hydrocarbon Concentration Results.
Sample #
14 Surface
14 Subsurface
Date
11/3/71
II It M
Slick
Type
2
Total
Chlorinated
Hydrocarbon
Count*
208
124
PCB**
(ppt)
13
6
DDT
(ppt)
45
44
Slick Origin
VIMS
Ferry
Pier
Distilled H20
(Blank)
66
Trace
* Peak height (in graph units) of all identifiable chlorinated hydrocarbons in
Chromatograms
** Peaks corresponding in retention time to Aroclor 1254.
-------
higher in surface samples and lower in the subsurface
samples; the PCB's seem to be more uniformly distributed.
Possible explanations for this difference are: PCB's and
DDT are likely carried in different physical states in the
atmosphere, PCB's as a gas and DDT on dust particles
(Harvey, 1971); PCB's and DDT enter the environment by
different methods; PCB's and DDT have differing surface
chemical properties. Concentration mechanism, for PCB's
and CHP's in surface films and subsurface water, and the
exact role the surface film has in concentrating and
transporting chlorinated hydrocarbons can only be determined
by extensive and expanded further studies.
108
-------
SECTION IX
LIPIDS OF SURFACE FILMS ON CHESAPEAKE BAY
The objective of this work was to provide more complete
information regarding lipid material in surface water and
surface films. The 100 micron surface layer was sampled
in the York River and Chesapeake Bay, and the samples were
analysed for hydrocarbons and fatty acids by thin layer
and gas-liquid chromatography.
In the past, sampling of surface water was carried out by
dipping a container under the surface of the water. In
Garrett's work (1965), sampling techniques were greatly
refined through the use of stainless steel mesh screens
that sampled the top 0.15 mm surface layer. Again using
screens, Garrett (1967) took samples for chemical analysis
and estimated the total lipid material to be 0.2-1.0
milligrams per liter. He tentatively identified one
hydrocarbon (C29H52) and reported the existence of several
fatty acids at eight stations. Garrett's work was
primarily involved with the total dissolved organic
material that could be extracted from seawater with
chloroform. The analyses were not quantitative and
comparisons between fresh and salt water were not
considered.
Jarvis, et al (1967) postulated the existence of fatty
esters, free fatty acids, fatty alcohols and hydrocarbons
in samples taken with screens. He made no chemical
analyses. From Garrett's work (1967) and from physical
parameters (film pressures, surface potentials, surface
viscosities, and damping coefficients) Jarvis arrived at
his conclusions.
MATERIALS AND METHODS
Samples were taken along the York River and nearby areas
of the Chesapeake Bay. Dates, positions and descriptions
are given in Appendix 2. Some preliminary samples were
taken along the Chesapeake Bay Bridge-Tunnel, but the
sampling boat was unable to sample regularly due to rough
sea conditions.
A rotating drum mechanism was used to take the samples.
It was designed by Harvey (1965), who reported it collected
larger plankton populations in surface samples in slick
areas than in subsurface water. Monolayers can be taken
from the water's surface and transferred to a rotating
109
-------
cylinder with an appropriate hydrophilic surface (Ries and
Grutsch, 1968, and Ries, 1968). The drum used here was
designed and built by the National Aeronautics and Space
Administration's Wallops Station. It was necessary that
no organic contamination be present, so all surfaces in
contact with the sample had to be stainless steel and
coated with Solaramic S5210-ZC (a product of the Solar
Company, San Diego, California).
It is supported 3 feet off the bow of an 18 ft Thunderbird
Cheyenne outboard boat by a tubular aluminum structure and
a boom and winch. A stainless steel trough with a teflon
blade is mounted in such a fashion as to scrape the drum
as it rotates through the water, in a counterclockwise
sense as viewed from the right side of the boat. The drum
is normally immersed to a depth of about 4 inches in the
water.
The drum is turned by an electric motor at a slightly
faster rate than the boat speed, which usually requires
between 8 and 10 drum revolutions per minute. Water
scraped from the drum is deposited in the stainless steel
trough and pumped to a sample bottle by a hand operated
vacuum pump.
Slightly more than 18 liters of seawater were taken at each
sampling site. Immediately upon return to the laboratory,
the samples were gravity filtered through Gelman Type A
glass fiber filter pads. Gravity filtration was chosen
over vacuum filtration to avoid rupture of cells and
release of cellular material to the filtrate. The pH of
the filtrate was adjusted to 2.0-2.5 with 12N HC1 to
convert salts of fatty acids to the free fatty acids. At
this point, 50 cc of chloroform was added to retard
bacterial degradation of the sample, since it is sometimes
several days before extraction can be carried out.
Next, the filtrate was placed in a continuous extraction
device and bubbled through 1500 milliliters of chloroform
for approximately three hours. The chloroform was then
drained off and reduced in volume to about one milliliter
in a vacuum rotary evaporator.
The extract was then subjected to preparative thin-layer
chromatography according to Stahl (1969). This preparative
thin-layer chromatography was used to "clean up" the sample
and separate the various classes of compounds. Plates were
coated with Silica Gel G (Merck, Darmstadt, Germany). A
rapidly prepared mixture of silica gel and water was placed
on 20 cm x 20 cm glass plates in a 0.25 millimeter layer by
means of a spreading device (Brinkmann, Westbury, New York) .
110
-------
The sample spotted plate was then developed with a 90:10:1
hexane, diethy1 ether, acetic acid solution. The hydro-
carbon band migrated with the solvent front while the fatty
acids migrated slightly less than halfway up the plate.
The bands of organic material was made visible by a 0.354
nanometer light. The hydrocarbon band was then vacuumed
off the plate with a thin-layer plate vacuuming device
(Brinkmann). The vacuumed silica gel was washed with
methanol to remove the hydrocarbons from the relatively
polar base. The methanol was evaporated to a very small
volume and then extracted with hexane to remove the
hydrocarbons from the methanol. This micro extraction was
necessary to remove the methanol soluble calcium sulfate
binder. The hydrocarbon in hexane solution was reduced to
dryness by air evaporation and then redissolved in a known
volume of hexane for gas chromatographic analysis.
The gas chromatographic analyses were carried out on a
Perkin-Elmer Model 900 Gas Chromatograph, equipped with
dual columns and flame ionization detectors, and operated
under dual column compensated conditions.
For work with hydrocarbons, a 6 ft x 1/8 in. O.D. copper
column was used. It was packed with a 10% SE-30 on a
non-acid washed Chromosorb P (mesh 60/80) both from Applied
Science, State College, Pa. A temperature program of 4 C
per minute was used from 100 C to 280 C with an initial
time of two minutes and final time of eight minutes. The
temperature of the injectors was set at 320 C and of the
manifold was set at 290 C. Helium was used as carrier gas.
The fatty acid band was also vacuumed off the plate and the
silica gel washed with methanol to remove the free fatty
acids which were converted to their methyl esters by the
method of Metcalf and Schmitz (1961). The esters were then
redis solved in a known amount of hexane and were now ready
for injection in the gas chromatograph.
Fatty acid methyl esters were run with the same program as
the hydrocarbons (100 C - 280 C at 4 C per minute, injector
at 320 C, manifold at 290 C, initial time 2 minutes, final
time 8 minutes). Glass columns (1/4 in. O.D. x 6 ft) were
used to reduce any possible oxidation. The columns were
packed with 5% SE-30 on Chromosorb G (AW DMCS, 80/100 mesh)
prepared by Perkin-Elmer (Norwalk, Conn.).
Peaks were identified by retention time comparison with a
series of standards purchased from Applied Science of State
College, Pa. Areas under peaks were determined on both the
standards and unknowns with the areas of each being
111
-------
directly proportional to their concentrations. Repeat
chromatograms were made frequently on standards and blanks
were also run.
RESULTS
Good separations were obtained for saturated and unsaturated
mixtures of the fatty acid standards. On blank runs base-
line drift was held at a minimum.
The fatty acids from 10:0 to 23:0 are reported (see Table
17). The 14:0, 16:0, 16:1, 18:0, 18:1, and 22:0 fatty
acids predominate. The percentage contribution of these
acids to the total free acid concentration ranged from 55
to 98% with most falling in the 70% to 90% range, as can be
seen in Table 18. The amounts of fatty acid material
ranged from 700 micrograms per liter to 7800 micrograms per
liter. These results are very dissimilar to the results of
Stauffer (1969), who investigated the fatty acids at 2
meter depths in the James River. Differences may, in part,
be a consequence of high surface concentrations of lipid
material. The unidentifiable material ranged from 2% to
187o with an average of less than 1070.
Normal paraffinic hydrocarbons from CIQ to C24 are listed
in Table 19. No concentration data was available for the
first eleven samples due to difficulties with sample
handling. The concentrations of the last eight samples
ranged from 300 to 500 micrograms per liter. The unknown
materials ranged from 20 to 45 percent with most in the 25
to 40 percent category. All the gas chromatograms of the
hydrocarbon samples were rather similar to gas chromatograms
of number 2 fuel oil.
The total amount of organic material collected varied from
sample to sample but the variations were not related to
cause in this work because fluctuations in biological
communities or pollutants were not measured. The concen-
trations were independent of salinity. Samples were taken
from the Chesapeake Bay to the Pamunkey River with
salinities varying more than 20 &,, but no geographical
pattern of hydrocarbon concentrations was apparent.
o
A 50 A thick slick or surface film represents about 0.005
percent by volume of a 100 micron thick water sample.
Depending on the state of compression of the organic
compound in the surface film, this layer should contain
sufficient amounts of organics to considerably affect, by
its presence or absence, the concentrations measured in the
100 micron thick sample.
112
-------
Table 17. Fatty Acid Sample Concentration and Composition.
Sample #1
IK/1 %
10:0
11:0
12:0
13:0
14:0
14:1
15:0
16:0
16:1
16:2
17:0
18:0
18:1
18:2
19:0
20:0
21:0
22:0
23:0
?
Total
-
Oil
104
147
567
112
207
2510
720
-
095
874
1142
-
020
043
046
363
106
742
7861
-
0.14
1.32
1.87
7.21
1.43
2.64
31.93
9.80
-
1.21
11.12
14.53
-
0.25
0.55
0.58
4.62
1.35
9.44
Sample #2
-
017
024
tr
248
-
094
1503
135
-
052
728
628
-
050
013
033
052
Oil
346
3935
0
0
6
2
38
3
1
18
15
1
0
0
1
0
8
-
.44
.61
tr
.31
-
.38
.21
.43
-
.33
.50
.95
-
.27
.33
.83
.33
.27
.80
Sample #3
UK/1 %
_
-
010
-
173
mm
091
1754
159
tr
062
782
627
-
Oil
Oil
024
024
015
314
4058
0
4
2
43
3
1
19
15
0
0
0
0
0
7
_
-
.24
-
.27
-
.25
.22
.92
tr
.53
.27
.46
-
.27
.27
.59
.59
.37
.73
Sample #4
ug/1 %
-
028
148
148
-
052
852
116
-
048
399
379
-
013
028
013
205
009
063
2501
1.
5.
5.
2.
34.
4.
1.
15.
15.
0.
1.
0.
8.
0.
2.
—
-
13
92
92
-
09
06
62
-
92
94
16
-
52
13
52
19
35
53
113
-------
Table 17. (Cont'd). Fatty Acid Sample Concentration and
Composition.
Sample #5
LlR/1 7o
10:
11:
12:
13:
14:
14:
15:
16:
16:
16:
17:
18:
18:
18:
19:
20:
21:
22:
23:
0
0
0
0
0
1
0
0
1
2
0
0
1
2
0
0
0
0
0
Total
005
005
037
135
228
-
077
1316
274
-
061
625
603
-
017
Oil
013
227
015
113
3764
0
0
0
3
6
2
34
7
1
16
16
0
0
0
6
0
3
.12
.14
.98
.59
.05
mm
.05
.96
.29
-
.62
.61
.03
-
.46
.29
.35
.02
.41
.01
Sample #6 Sample #7 Sample #8
ttg/1 % us/1 % us/1 "1°
- No concen- - -
trations*
004
051
085
-
061
1142
222
-
035
407
333
-
008
030
010
101
023
151
2665
0.
1.
3.
-
2.
42.
8.
-
1.
15.
12.
-
0.
1.
0.
3.
0.
5.
16
92
19
29
85
34
31
29
51
29
14
37
80
86
60
030
tr 013
2.89 370
039
0.72 035
31.05 1052
1.44 314
-
1.08 018
22.74 166
31.05 383
-
-
0.36 tr
_
8.66 061
-
261
2743
1
0
13
1
1
38
11
0
6
13
2
9
.11
.48
.50
.43
.27
.36
.44
-
.64
.04
.98
-
-
tr
-
.22
-
.53
*No concentration values available.
114
-------
Table 17. (Cont'd)
Fatty Acid Sample Concentration and
Composition.
Sample #9
UK/I 7o
10:0
11:0
12:0
13:0
14:0
14:1
15:0
16:0
16:1
16:2
17:0
18:0
18:1
18:2
19:0
20:0
21:0
22:0
23:0
?
Total
-
050
040
-
019
339
040
-
014
130
162
-
tr
016
tr
064
tr
023
897
i
i
i
5
4
2
37
4
1
14
18
1
7
2
•»
••
M
.58
.49
-
.06
.74
.49
-
.58
.44
.08
-
tr
.82
tr
.16
tr
.55
Sample #10
«/l %
tr
tr
071
-
029
615
tr
-
061
361
050
-
019
040
tr
117
tr
029
1392
tr
tr
5
2
44
4
25
3
1
2
8
2
.09
-
.11
.21
tr
-
.38
.90
.60
-
.33
.89
tr
.37
tr
.11
Sample #11
MB/1 %
013
tr
111
-
043
342
026
-
048
249
122
-
019
028
tr
117
tr
035
1151
4
I
1
•*
V
.13
tr
9
3
29
2
4
21
10
1
2
10
.65
-
.69
.71
.27
-
.16
.67
.60
MB
.70
.27
tr
.12
tr
3
.03
Sample #12
MR/1 %
*•
016
020
102
009
037
428
027
-
075
287
117
-
016
075
388
424
010
453
2485
0.63
0.79
4.10
0.35
1.49
17.23
1.10
-
3.02
11.57
4.73
-
0.66
3.02
15.62
17.05
0.39
18.24
115
-------
Table 17. (Cont'd)
Fatty Acid Sample Concentration and
Composition.
Sample #13 Sample #14 Sample #15 Sample #16
_ l\ oi _ /i et ' _ /I 07 _/1 "I
10:0
11:0
12:0
13:0
14:0
14:1
15:0
16:0
16:1
16:2
17:0
18:0
18:1
18:2
19:0
20:0
21:0
22:0
23:0
9
Total
tr
tr
031
017
220
tr
083
806
tr
-
157
577
146
-
tr
660
128
603
tr
636
4065
tr
tr
0.75
0.43
5.41
tr
2.04
19.83
tr
-
3.86
14.20
3.59
-
tr
16.24
3.16
14.84
tr
15.65
-
-
tr
-
059
tr
028
311
069
-
059
212
718
-
013
247
024
204
tr
114
2058
2
1
15
3
2
10
34
0
12
1
9
5
-
-
tr
-
.86
tr
.38
.09
.33
-
.86
.32
.89
-
.63
.02
.16
.90
tr
.56
-
-
010
026
063
015
017
183
028
-
078
094
138
-
008
023
025
357
010
146
1222
0
2
5
1
1
14
2
6
7
11
0
1
2
29
0
11
-
-
.80
.14
.17
.25
.43
.97
.32
-
.42
.66
.32
-
.62
.87
.05
.23
.80
.94
-
-
tr
tr
035
005
Oil
098
014
-
032
049
085
-
tr
Oil
008
205
008
099
659
5
0
1
14
2
4
7
12
1
1
31
1
15
-
-
tr
tr
.29
.74
.65
.89
.15
-
.80
.44
.90
-
tr
.65
.16
.10
.16
.05
116
-------
Table 17. (Cont'd).
Sample #17
Fatty Acid Sample Concentration and
Composition
Sample #18 Sample #19
ug/1
10:
11:
12:
13:
14:
14:
15:
16:
16:
16:
17:
18:
18:
18:
19:
20:
21:
22;
23;
0
0
0
0
0
1
0
0
1
2
0
0
1
2
:0
:0
;0
;0
:0
?
Total
-
009
019
052
-
018
179
019
-
042
097
129
-
007
028
010
386
004
199
1197
•
•
•
M
0.73
1
4
•
1
14
1
3
8
10
0
2
0
32
0
16
.55
.32
••
.50
.97
.59 i
-
.50
.15
.79
-
.55
.32
.86
.23
.32
.61
tr
Oil
026
063
014
033
113
342
-
091
209
551
-
013
098
044
536
Oil
309
2465
•
*
tr
0.44
1
.06
2.56
0
1
4
13
3
8
22
0
3
1
21
0
12
.57
.33
.59
.87
- •"''
.71
.48
.36
-
.53
.98
.77
.74
.44
.55
003
007
016
045
-
022
126
008
-
050
059
061
-
003
016
003
282-
010
117
827
•
•
0.39
0.86
1.91
5.47
•
2
•
.63
15.22
0
•
6
7
7
0
1
0
34
1
14
.92
•»
.06
.18
.38
-
.33
.91
.33
.12
.19
.10
117
-------
Table 17. (Cont'd). Fatty Acid Sample Concentration and
Composition.
Sample #20 Sample #21 Sample #22 Sample #23
Ug/1 7o Ug/1 % UK/1
10:0
11:0
12:0
13:0
14:0
14:1
15:0
16:0
16:1
16:2
17:0
18:0
18:1
18:2
19:0
20:0
21:0
22:0
23:0
?
Total
1
1
3
12
33
-
7
67
21
16
234
14
242
-
1
13
8
-
-
41
716
0.18
0.19
0.42
1.66
4.58
-
0.97
9.43
2.95
2.29
32.71
1.99
33.76
-
0.18
1.76
1.15
-
-
5.77
9
10
16
148
59
-
14
270
26
11
2343
167
1697
-
40
39
-
-
-
116
4967
0.
0.
0.
2.
1.
-
0.
5.
0.
0.
47.
3.
34.
-
0.
0.
-
-
-
2.
18
20
32
98
19
28
40
52
22
17
36
16
81
79
33
3
-
7
-
42
-
16
83
37
32
57
52
135
-
21
114
64
-
-
68
732
0.
-
1.
-
5.
-
2.
11.
5.
4.
7.
7.
18.
-
2.
15.
8.
-
-
9.
40
02
77
18
38
00
39
76
06
44
92
52
78
28
16
11
8
29
30
-
17
36
45
23
27
25
-
-
5
15
16
-
-
90
395
3.
2.
2.
7.
7.
-
4.
9.
11.
5.
6.
6.
-
-
1.
3.
4.
-
-
22.
97
86
07
35
67
30
09
49
75
86
33
27
82
15
83
118
-------
Table 17. (Cont'd).
Sample #24
Fatty Acid Sample Concentration and
Composition.
Sample #25 Sample #26
to
10:0
11:0
12:0
13
14
14
15
16
16
16
17
18
18
18
19
20
21
22
23
:0
:0
:1
:0
:0
:1
:2
:0
:0
:1
:2
:0
:0
:0
:0
:0
9
Total
7
4
9
21
34
-
18
98
39
21
511
30
783
«••
16
57
tr
-
-
96
1745
0
0
0
1
1
1
5
2
1
29
1
44
0
3
5
.39
.25
.54
.19
.95
-
.01
.64
.24
.20
.27
.70
.86
-
.94
.25
tr
-
-
.49
10
4
6
45
-
6
69
16
18
4
1
45
-
5
19
19
-
-
37
305
(
3
1
2
14
2
22
5
5
1
0
14
1
6
6
-------
Table 17. (Cont'd). Fatty Acid Sample Concentration and
Composition.
Sample #27 Sample #28 Sample #29
ue/1 % u.s./l
10:
11:
12:
13:
14:
14:
15:
16:
16:
16:
17:
18:
18:
18:
19:
20:
21:
22:
23:
0
0
0
0
0
1
0
0
1
2
0
0
1
2
0
0
0
0
0
?
Total
8
6
4
29
24
-
14
105
-
-
519
68
134
-
11
56
11
-
-
90
1080
0
0
0
2
2
1
9
48
6
12
0
5
1
8
.70
.58
.41
.69
.22
-
.29
.76
-
-
.05
.31
.42
-
.99
.20
.05
-
-
.36
7
15
11
23
53
-
8
109
24
11
-
119
145
-
6
49
8
-
-
78
665
1
2
1
3
7
1
16
3
1
17
21
0
7
1
11
.04
.18
.61
.42
.97
-
.23
.42
.61
.61
-
.85
.83
-
.85
.41
.23
-
-
.77
-
-
1
-
26
-
18
53
44
18
-
9
417
-
-
-
35
-
-
32
653
-
-
0.14
-
4.03
-
2.71
8.12
6.77
2.80
-
1.45
63.81
-
-
-
5.32
-
-
4.88
120
-------
Table 18. Percentages of Predominant Fatty Acids.
Sample 14:0 16:0 16:1 18;0 18:1 22:0 Total
1 7.21 31.93 9.80 11.12 14.53 4.62 79.21
2 6.31 38.21 3.43 18.50 15.95 1.33 83.73
3 4.27 43.22 3.92 19.27 15.46 0.59 86.73
4 5.92 34.06 4.62 15.94 15.16 8.19 83.89
5 6.05 34.96 7.29 16.61 16.03 6.02 86.96
6 3.19 42.85 8.34 15.29 12.51 3.80 85.98
7 2.89 31.05 1.44 22.74 31.05 8.66 97.83
8 13.50 38.36 11.44 6.04 13.98 2.22 85.58
9 4.49 37.74 4.49 14.44 18.08 7.16 86.40
10 5.09 44.21 tr 25.90 3.60 8.37 87.17
11 9.65 29.71 2.27 21.67 10.60 10.12 84.02
12 4.10 17.23 1.10 11.57 4.73 17.05 55.78
13 5.41 19.83 tr 14.20 2.59 14.84 57.78
14 2.86 15.09 3.33 10.32 34.89 9.90 76.39
15 5.17 14.97 2.32 7.66 11.32 29.23 70.67
16 5.29 14.89 2.15 7.44 12.90 31.10 73.77
17 4.32 14.97 1.59 8.15 10.79 32.23 72.25
18 2.56 4.59 13.87 8.48 22.36 21.74 73.60
19 5.47 5.47 15.22 0.92 7.18 7.38 70.29
121
-------
Table 19. Hydrocarbon Sample Concentration and Composition,
Carbon Sample #1* Sample #2* Sample #4* Sample #5*
No. % % "% %
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
?
Total
-
1.80
5.93
0.19
9.09
0.68
2.16
7.80
5.48
9.60
5.67
8.76
10.31
4.64
27.89
100.00
0.23
0.12
0.25
0.21
1.13
1.06
3.28
6.68
7.90
12.79
13.96
10.03
-
1.58
-
40.74
99.96
0.10
0.08
0.07
0.31
0.18
0.76
1.38
9.24
11.62
16.10
9.30
7.11
9.20
, 4.81
1.36
28.35
99.97
0.15
0.41
0.16
1.07
6.31
4.20
6.97
10.41
8.41
9.68
6.54
5.14
3.87
5.21
1.87
29.60
100.00
*Samples #1 thru #11 have no concentration values available
for the hydrocarbons.
Sample #3 lost due to spillage.
122
-------
Table 19. (Cont'd).
Hydrocarbon Sample Concentration and
Composition.
Carbon
No.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Total
Sample #6*
0.26
0.11
0.33
0.61
2.58
4.58
7.40
9.00
8.37
14.29
7.19
5.37
7.50
4.49
3.39
24.60
100.00
Sample #7*
0.45
0.18
0.23
0.68
3.12
3.76
5.12
8.21
8.00
14.37
7.37
6.28
5.31
1 6.88
0.97
29.07
100.00
Sample #8*
0.32
-
0.10
0.47
2.50
3.61
4.66
8.21
9.70
10.74
5.95
4.32
4.93
3.72
0.88
39.88
99.99
Sample #9*
0.23
0.13
0.13
1.53
6.36
8.25
8.49
11.40
9.75
8.62
5.43
3.58
4.77
1.59
-
29.23
100.00
123
-------
Table 19. (Cont'd). Hydrocarbon Sample Concentration and
Composition.
Carbon Sample #10* Sample #11* Sample #12 Sample #13
No. tig/1 % ug/1 %
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
?
Total
0
0
0
-
.08
.06
.16
14.30
36
21
6
1
19
99
.47
.04
.75
.61
-
-
-
-
-
-
.52
.97
0
0
12
26
15
5
2
2
1
1
1
1
28
-
-
.20
.32
.40
.09
.54
.88
.58
.41
.13
.61
.93
.29
-
.62
tr
tr
-
-
-
001.
Oil.
028.
056.
017.
019.
Oil.
046.
025.
068.
166.
449.
tr
tr
0.
2.
6.
12.
3.
4.
2.
10.
5.
15.
36.
100
-
-
-
32
48
27
53
68
25
55
34
52
15
92
.00
004.
002.
-
-
-
002.
010.
017.
029.
019.
029.
Oil.
016.
008.
009.
133.
289.
1
0
0
3
5
10
6
10
3
5
2
3
46
.26
.27
-
-
-
.55
.41
.71
.16
.70
.22
.85
.49
.64
,08
.15
,
124
-------
Table 19. (Cont'd). Hydrocarbon Sample Concentration and
Composition.
Carbon
No.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
1
Total
Sample #14
UK/1 %
tr
001.
-
001.
007.
025.
027.
052.
016.
051.
014,
033.
012.
016.
166.
423.
0.
0.
0.
1.
5.
6.
17.
3.
17.
3.
7f
2.
3.
39.
tr
30
-
23
11
73
86
50
35
83
17
31
81
85
76
18
Sample #15
uR/1 %
tr
tr
-
002.
009.
018.
020.
044.
008.
031.
006.
034.
010.
027.
067.
276.
tr
tr
-
0.
0.
3.
6.
7.
15.
2.
11.
2.
12.
3.
9.
24.
78
14
22
67
13
92
76
26
18
41
68
77
07
Sample #16
U8/1 %
tr
-
001.
001.
007.
022.
019.
046.
023.
099.
017.
027.
013.
017.
239.
529.
tr
i
0
0
1
4
3
8
4
18
3
5
•
.09
.18
.32
.11
.63
.77
.26
.73
.12
.16
2.40
3
45
.12
.09
Sample #17
U8/1 %
tr
tr
001.
003.
001.
004.
019.
048.
063.
037.
065.
023.
041.
Oil.
020.
216.
552.
0.06
tr
0.09
0.55
0.13
0.66
3.53
8.75
11.40
6.68
11.75
4.15
7.37
2.07
3.69
39.14
125
-------
Table 19. (Cont'd). Hydrocarbon Sample Concentration and
Composition.
Carbon Sample #18 Sample #19 Sample #20 Sample #21
No. ug/1 % ug/1 % /l % itg/1 %
10 tr 0.03 -
11 tr tr
12 tr 0.04 -
13 tr tr ----- -
14 tr tr - - 2 0.84 36 27.21
15 005. 1.19 004. 0.81 2 0.74 16 11.56
16 023. 5.14 036. 8.14 25 12.62 29 21.44
17 020. 4.54 025. 5.61 27 13.12
18 061. 13.69 052. 11.86 33 16.37
19 012. 2.70 020. 4.60 21 10.38 10 7.15
20 054. 12.06 029. 6.62 9 4.53 2 1.68
21 023. 5.11 Oil. 2.59 8 3.96 3 2.10
22 033. 7.38 046. 10.50 15 7.55 7 5.04
23 010. 2.27 020. 4.60 9 4.53
24 028. 6.24 059. 13.23 21 10.18
? 178. 39.69 139. 31.39 31 15.28 0.32 23.53
Total 448. 442. 202 1.36
126
-------
Table 19. (Cont'd). Hydrocarbon Sample Concentration and
Composition.
Carbon Sample #22 Sample #23 Sample #24 Sample #25
vf— ..«. /"i oy —./i o/ /£ -*• «— —
/o Ug/1 /o (^ft/1
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
7
Total
-
12
21
-
-
52
27
15
6
90
-
1.14
3.32
-
-
3.
6.
-
-
12.
8.
4.
1.
27.
-
34.
77
99
90
52
14
80
12
62
3
50
45
80
-
-
52
50
9
18
35
23
130
4.95
0.54
10.12
9.09
16.25
-
-
10.47
10.16
1.85
3.70
7.09
4.62
26.18
9
16
20
-
-
16
10
9
4
5
12
39
141
6.
11.
14.
-
-
11.
7.
6.
2.
3.
8.
27.
49
35
33
22
30
76
97
24
38
57
**"* -
3
65
71
77
-
-
51
11
11
17
25
44
153
528
0.
12.
13.
14.
-
-
9.
2.
2.
3.
4.
8.
28.
51
24
36
65
67
11
17
18
77
37
97
127
-------
Table 19. (Cont'd). Hydrocarbon Sample Concentration and
Composition.
Carbon Sample #26 Sample #27 Sample #28 Sample #29
No. ug/1 7o tig/1 7o «g/l 7o ug/1 7,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
7
Total
-
2
59
37
34
-
-
53
54
8
7
9
40
135
437
0
13
8
7
12
12
1
1
2
9
BO
—
.44
.52
.46
.79
-
-
.04
.39
.74
.59
.09
.07
.79
*
tr
23
13
47
-
-
19
18
9
14
3
11
65
222
10
5
21
8
8
4
6
1
4
29
*•
tr
.47
.84
.29
-
-
.41
.24
.12
.18
.37
.72
.14
-
9
75
31
86
-
-
81
75
27
197
93
31
296
1000
0
7
3
8
8
7
2
19
9
3
*•>
29
-
.86
.53
.13
.56
-
-
.08
.47
.74
.67
.30
.13
.64
•*
-
51
77
84
-
-
40
34
10
16
69
64
139
535
-
-
9.62
4.99
15.75
-
-
7.41
6.41
1.85
2.99
12.97
11.97
26.01
128
-------
Depending on the state of compression of the organic
f?Ce fUm' this lflyer shouSFSEL
of organics to considerably affect, by
100 the
In Tables 20 and 21 fatty acid and hydrocarbon concentra-
tions are reported for samples taken in a slick, out of the
slick and in the slick with a bottle dipped under the
surface. The fatty acids are more concentrated in the slick
samples than in non-slick samples. Just the opposite is
true for the hydrocarbon samples, indicating the slick may
force more hydrocarbons into solution outside and under the
slick.
The fatty acid concentrations for non-slick areas and
bottle samples are in the same range as reported by Slowey,
Jeffrey, and Hood (1962) for the Gulf of Mexico surface
waters. At this point, it seems these results do not
support Garrett's claim (1967) that surface fatty acid
concentrations are independent of slicks in the area.
Table 20. Fatty Acid Concentrations in Slicks and
Non-Slicks.
Slick
(Skimmer)
mg/1
1
2
3
(Samples
(Samples
(Samples
21,
24,
27,
22,
25,
28,
23)
26)
29) '
4
1
1
.967
.745
.080
Non-Slick
(Skimmer)
mg/1
0
0
0
.732
.305
.665
Bottle
(SHck)
mg/1
3.
0.
0.
95
608
653
Table 21. Hydrocarbon Concentrations in Slicks and
Non-Slicks.
Slick
( Skimmer)
mg/1
1
2
3
(Samples
(Samples
(Samples
21
24
27
,22,
,25,
,28,
23)
26)
29)
0.
0.
0.
136
141
222
Non-Slick
(Skimmer)
mg/1
0
0
1
.332
.528
.000
Bottle
(Slick)
mg/1
0
0
0
.495
.437
.535
129
-------
SECTION X
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139
-------
SECTION XI
LIST OF PUBLICATIONS
Munday, J.C.; Harrison, W.; and Maclntyre, W.G., 1970.
Oil slick motion near Chesapeake Bay Entrance.
Jour. Am. Water Res. Assn., j6, 879-884.
Munday, J.C.; Maclntyre, W.G.; Penney, M.E.; and
Oberholtzer, J.D., 1971. Oil slick studies using
photographic and multispectral scanner data.
Proc. 7th Int. Symp. on Remote Sensing of the
Environment, Willow Runn Labs., Univ. of Michigan,
p. 1027-1043.
Roy, V.M.; Dupuy, J.L.; Maclntyre, W.G.; and Harrison, W.,
1970. Abundance of marine phytoplankton in surface
films: a method of sampling. Proc. Nat. Symp. on
Hydrobiology, A.W.R.A., Miami, Fla., p. 381-389.
Smith, C.L., and Maclntyre, W.G., 1971. Initial aging of
fuel oil films on sea water. Joint Conf. on
Prevention and Control of Oil Spills, Washington,
D.C., API-EPA-USCG, p. 457-461.
140
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SECTION XII
APPENDICES
Page
A. Program Description for Oil Slick Motion 142
B. Lipid Analyxis 152
C. Effects of an Accidental Spill of No. 6 156
Fuel Oil on a Salt Marsh
141
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APPENDIX
PROGRAM DESCRIPTION
FOR
OIL SLICK MOTION
The program computes current paths from input wind and tidal
current data; and predicts the motion of surface water
masses or oil slicks on surface water masses, in the case
when the motion is due to wind and to surface tidal
currents. Suitable tidal current data can be obtained from
tables of the U. S. Coast and Geodetic Survey. In a single
run, current paths can be computed for any number of sets
of input data. The program is processed by an IBM 1130
computer.
The program first reads housekeeping data and labels the
printer output page. Then, tidal current data from up to
ten stations are read, consisting of station latitude and
longitude, times of slacks and maximum currents, and
current velocities. Finally, the initial location of
interest, a start and stop time, wind factor, and wind
velocity versus time are read as input.
The bulk of computation takes place in a cycle within a
loop, in which each pass of the cycle accounts for a single
station. For each station, the phase of the tidal cycle is
determined by comparing the time of interest with the times
of slack waters, maximum flood, and maximum ebb. The
current magnitude between maxima is calculated by inserting
the phase in a sine wave and multiplying by the appropriate
current maximum. The resulting magnitude is weighted by
the inverse square of the distance between the station and
the location of interest. Orthogonal components (weighted)
of current velocity are formed from the product of this
magnitude and the sine or cosine of the appropriate input-
current direction.
Orthogonal (weighted) components are computed and summed
only for stations as close as 5 nautical miles to the
location of interest. The sums are divided by the sum of
weights. To these sums are added wind velocity components
multiplied by the wind factor. The resulting sums are
multiplied by a time increment. The distance components
are algebraically added to the coordinates of the initial
location to produce a new location, and the time increment
is added to the initial (start) time to produce a new time.
The new time and new coordinates are printed and control
142
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returns to the beginning of the Do-loop to allow repetition
of all computations using the new location and time.
Repetition ceases when a stop time is reached.
If allowed by an input control number, control returns to
nearly the beginning of the program in order that a new
current path can be computed based on a new set of input
data.
INPUT DATA
A. Card, Column, Format, and Description
Card Column Format Description
1 1-10 2A5 Dl, D2, label or title to be speci-
fied by user. A blank card is
permissible.
2 1-4 14 K, number of tidal current data
stations per data set. The number
must be right-adjusted in the
field. The number of stations
allowed is limited only by the
input format 14.
3 1-4 KK, number of sets of data to be
processed, equal to the number of
current paths to be computed, where
each current path requires a data
set. The number of data sets
allowed is limited only by the
input format 14. The number must
be right-adjusted.
A 12F6.0 ((A (I, J), I = 1, 12), J = 1, K),
tidal current data for each of the
K stations. All data fields
requires a decimal point.
1-6 F6.0 A(1,J), degrees latitude of the
station.
7-12 F6.0 A(2, J), minutes (plus decimal
fraction) latitude.
13-18 F6.0 A(3, J), degrees longitude.
143
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Card Column Format Description
19-24 F6.0 A(4, J), minutes (plus decimal
fraction) longitude.
25-30 F6.0 A(5, J), time of slack water in
hours. All times must be in hours
of military time (with a decimal
point). The slack water may be
that before either flood or ebb,
where the choice is made by the
user so that the input data times
bracket the desired start and stop
time.
31-36 F6.0 A(6, J), time of the maximum
current succeeding the slack time
A(5, J), in hours military time.
37-42 F6.0 A(7, J), magnitude of the maximum
current A(6, J) in knots.
43-48 F6.0 A(8, J), direction of the maximum
current A(6, J) in degrees
(toward).
49-54 F6.0 A(9, J), time of succeeding slack
water in hours military time.
55-60 F6.0 A(10, J), time of succeeding
maximum current in hours military
time.
61-66 F6.0 A(ll, J), magnitude of the maximum
current A(10, J) in knots.
67-72 F6.0 A(12, J), direction of the maximum
current A(10, J) in degrees
(toward).
Additional cards A as needed,
controlled by K.
B 12F6.0 (B(I), 1=1, 6), initial data, and
F, wind factor.
1-6 F6.0 B(l), degrees latitude of initial
location.
144
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Card Column Format Description
7-12 F6.0 B(2), minutes (plus decimal
fraction) latitude of initial
location.
13-18 F6.0 B(3), degrees longitude of initial
location.
19-24 F6.0 B(4), minutes (plus decimal
fraction) longitude of initial
location.
25-30 F6.0 B(5), start time in hours military
time.
31-36 F6.0 B(6), stop time in hours military
time.
37-42 F6.0 F, wind factor, as a fraction
(F £ 1.0) of wind speed assumed by
the moving object or water mass,
over and above the movement due to
tidal currents alone.
W 12F6.0 «W(I, J), I - 1, 2), J = 1, JJ),
the hourly wind velocity, where JJ
is the number of on-the-hour wind
velocities needed to bracket the
start and stop times.
1-6 F6.0 W(l, J) , wind magnitude in knots
during hour J-% to J + %.
7-12 F6.0 W(2, J), wind direction in degrees
during hour J-% to J + %.
Additional columns as needed for
additional pairs of wind magnitude
and direction, controlled by JJ.
Cards A, B, and W are repeated as
needed, controlled by KK.
B. Preparation of Input Data
Card 1: The label is included for convenience of the user,
It can include the date or any code number.
145
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Card 2: The number of tidal current data stations must be
decided by the user. The decision should be based on the
proximity of stations to the initial location and to
estimated subsequent locations. The density of stations in
the area of interest may need to be high, if the area has a
detailed current structure. Stations further than 5
nautical miles from a location along the current path are
neglected in the computations.
Card 3: A number of data sets may be processed to yield a
current path for each set. The number is decided by the
user.
Cards 4 to 3 + K: Tidal current data can be obtained from
Tidal Current Tables of the Coast and Geodetic Survey,
published by the U. S. Department of Commerce. Data from
each station are input on a separate card. The latitude
and longitude are obtained from Table 2. Slack water and
maximum current times are obtained from Table 1 with time
difference corrections obtained from Table 2. Magnitudes
of maximum currents are obtained from Table 1 with velocity
ratio corrections obtained from Table 2. Directions of
currents are obtained from Table 2.
Card 4 + K: Initial location data, start and stop times,
and wind factor F are decided by the user. The literature
suggests that F = 0.05 is the maximum wind factor
encountered in the field. The initial location must be
within 5 nautical miles of (at least) one station.
Card 5 + K: The hourly wind velocity data must be supplied
by the user.
OUTPUT DATA
A. Line, Column, Format, and Description
Description
User label.
Column headings: TIME (in) HOURS,
LATITUDE (in) DEGREES (and) MINUTES,
LONGITUDE (in) DEGREES (and)
MINUTES.
4 Blank
D 1-6 F6.0 Time in hours military time.
Line Column Format
146
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Line Column Format Description
13-17 F5.0 Degrees latitude.
27-31 F6.2 Minutes (plus decimal fraction)
latitude.
40-44 F5.0 Degrees longitude.
54-58 F6.2 Minutes (plus decimal fraction)
longitude.
The first line D includes the
start time plus the initial
location. Subsequent lines D
include time and current path
location at quarter-hour
intervals, up to the stop time.
LIMITATIONS AND VALIDATION
The following details of the program limit its applicability
to a general situation:
1) The program has not been tested for extended precision.
2) Input tidal current data and the program method do not
account for rotary current fields. Single directions are
assumed for flood and ebb flow.
3) The program converts (forward and backward) from degrees
latitude into 59.881 nautical miles, and from degrees
longitude into 48.031 nautical miles. Hence, the program is
presently suited (in North America) for only the Chesapeake
Bay entrance. For use at other locations, the conversion
factors must be changed in statements 18+2, 70+6, and
70 + 7.
4) If a computed current path moves more than 5 nautical
miles away from all data stations, points of the path are
determined from the last available computations in which
the path was within 5 nautical miles of a data station.^
This peculiar feature is a result of allowing only stations
within 5 nautical miles to influence the current path.
5) If the stop time exceeds the latest maximum current time
of any station, computation of current components will be
based on the latest maximum current velocity.
147
-------
The operation was validated by 5 digit hand calculations on
simulated data. The hand calculations were based on the
program method as described in OUTPUT DATA, but not on the
program statements themselves.
SYMBOLS DEFINITION, EXPLANATION OF CONSTANTS, AND LIBRARY
ROUTINES
A. Definition of Symbols in Alphabetical Order:
A(I, J) Tidal current data for J stations.
B(I) Initial location data; start and stop times.
Cl, C2 Longitude and latitude of a station in
fractional degrees.
Dl, D2 a) Label or title;
b) Longitude and latitude of a point on a
current path in fractional degrees.
F Wind factor.
Gl, G2 Longitude degrees and fractional minutes of a
current path point.
G3, G4 Latitude degrees and fractional minutes of a
current path point.
H Current direction in radians (from north).
J Number of time intervals, based on start and
stop times, and intervals of 0.25 hours.
JJ a) Number of hourly wind velocities needed to
bracket start and stop times.
b) Numbered hour for selection of wind velocity.
K Number of tidal current data stations.
KK Number of data sets to be processed.
KKK Counter of data sets processed.
N Counter of stations processed.
R Distance between a current path point and a
station.
S Current magnitude.
148
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T Time in fractional hours.
TA , Stop time in fractional hours.
TB The on-hour time preceding start time.
TT Time in military hours.
Tl, T3 First and second slack water times in
fractional hours.
T2, T4 First and second maximum current times in
fractional hours.
U Sum of weighting factors, 1/R .
W(I, J) Wind velocities for J hours.
WM Wind magnitude in knots.
WD Wind direction in degrees.
X Sum of north-south components of weighted
surface current speed.
Y Sum of east-west components of weighted surface
current speed.
B. Explanation of Constants in Order of Appearance:
48.031
59.881
1.5708
0.0174533
3.14159
239.524
192.124
Nautical miles per degree longitude.
Nautical miles per degree latitude.
7T/2, radians per 90 degrees.
tr/180, radians per degree.
TT , radians per 180 degrees.
59.881 times 4, where 4 results from a
numerator factor of 1/4 hour.
48.031 times 4, where 4 results from a
numerator factor of 1/4 hour.
149
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Program Listing
*IOCS(CARD,KEYBOARD,TYPEWRITER,113 2 PRINTER)
*LIST SOURCE PROGRAM
*ONE WORD INTEGERS
DIMENSION A(12,10),B(6),W(2,10)
KKK=0
WRITE(3,4)
READ(2,2)D1,D2
WRITE(3,3)D1,D2
READ(2,6)K
7 READ(2,6)KK
8 WRITE(3,5)
READ(2,10) ((A(I,J),I=1,12),J=1,K)
READ(2,10)B,F
T=IFIX(B(5)/100.)
T=T+(B(5)-T*100.)/60.
TB=IFIX(T)
TA=IFIX(B(6)/100.)
TA=TA+(B(6)-TA*100.)/60.
JJ=TA-TB+1.5
READ(2,10)((W(I,J),I=1,2),J=1,JJ)
WRITE(3,11) B(5),B(1),B(2),B(3),B(4)
J=4.*(TA=T)+1
DO 80 1=1,J
U=0.
X=0.
Y=0.
N=0.
15 N=N+1
IF(N-K)16,16,70
16 IF (1-1)17,17,18
17 D1=B(1)+B(2)/60.
D2=B(3)+B(4)/60.
18 C1=A(1,N)+A(2,N)/60.
C2=A(3,N)+A(4,N)/60.
R=((D2-C2)*48.031)**2+((D1-C1)*59.881)**2
R=SQRT(R)
IF (R) 19,19,21
19 R=0.01
21 IF(R-5.)20,15,15
20 T1=IFIX(A(5,N)/100.)
T1=T1+(A5,N)-Tl*100.)/60.
T2=IFIX(A(6,N)/100.)
T2=T2+(A(6,N)-T2*100.)/60.
T3=IFIX(A(9,N)/100.)
T3=T3+(A(9,N)-T3*100.)/60.
IF(T-T2)25,29,30
25 S=A(7,N)*SIN(1.5708*(T-T1)/(T2-T1))/R**2
GO TO 50
150
-------
30 T4=IFIX(A(10,N)/100.)
T4=T4+(A(10,N)-T4*100.)/60.
IF (T-T3)35,39,40
35 S=A(7,N)*SIN(1.5708*(T-T3)/(T2-T3))/R**2
GO TO 50
39 S=0
GO TO 55
40 S=A(11,N)*SIN(1.5708*(T-T3)/(T4-T3))/R**2
55 H=A(12,N)*0.0174533
GO TO 60
50 H=A(8,N)*0.0174533
60 X=X-S*SIN(H)
Y=Y+S*COS(H)
U=U+1/R**2
GO TO 15
70 T=T+0.25
TT=IFIX(T)
TT=TT*100.+(T-TT)*60.
JJ=*T-TB+1.5
WM=W(1,JJ)
WD=W(2,JJ)
D1=D1+(Y/U+F*WM*COS (WD*0.0174533+3.14159) ) /239.524
D2=D2+(X/U+F*WM+SIN (WD*0.0174533) ) /19 2.124
G1=IFIX(D1)
G2=(D1-G1)*60.
G3=IFIX(D2)
G4=(D2-G3)*60.
WRITE(3,11)TT,G1,G2,G3,G4
80 CONTINUE
KKK=KKK+1
IF(KKK-KK) 82,83,83
82 WRITE (3,4)
GO TO 8
83 CALL EXIT
2 FORMAT(16A5) -
3 FORMAT(/16A5/)
4 FORMAT(1H1)
5 FORMAT(5H TIME,7X,8HLATITUDE,20X9HLONGITUDE/6H HOURS,
6X,2(7HDEGREE IS7X7HMINUTES 7X)/)
6 FORMAT(1014)
10 FORMAT(12F6.0)
11 FORMAT(F6.0,6X,2(F5.0,9X,F6.2,8X))
151
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APPENDIX B
3
LIPID ANALYSIS
Sampling Site Locations, Dates, and Descriptions.
Sample #1: August 18, 1970 0940 hrs
Long. 76°32?05" Lat. 37°15I33"
Water temp. 28.0°C Ambient temp. 27°C
The slick extended from the Yorktown Naval Weapons Station
(N.W.S.) to about 1/2 mile northeast of the N.W.S. dock.
The slick also extended to mid-channel. Light slick
material, no particulate matter and no foam were noted.
Sample #2: August 18, 1970 1105 hrs
Long. 76°28?37" Lat. 37°14f30"
Water temp. 28°C Ambient temp. 27°C
The slick was in the vicinity of the Coleman Bridge, and
was about 2 miles long and 40 feet wide. Little
particulate material, no foam and heavy damping of
capillary waves was reported. Increasing winds were
experienced.
Sample #3: August 18, 1970 1215 hrs
Long. 76°28?37" Lat. 37015'29"
Water temp. 29.5°C Ambient temp. 30°C
Due to increasing winds, this sample was taken in the
Sarah's Creek area. The slick was reported as very light
with some particulate material and very little foam.
Sampling was discontinued due to the wind conditions.
Sample #4: August 27, 1970 1200 hrs
Long. 76°34755" Lat. 37°17'35"
Water temp. 28°C Ambient temp. 29°C
A slick was found off Cheatham Annex. It was very large
but it was light, with little foam and particulate
material. The slick extended in both directions from the
pier, up and down river and well out into the main channel.
The winds were light.
Sample #5: August 27, 1970 1330 hrs
Long. 76°3r48lf Lat. 37°15f22fl
The slick was located off the Naval Weapons Station in
Yorktown in up and down river directions. It was light and
had little foam and particulate matter.
152
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Sample #6: August 28, 1970 1200 hrs
Long. 76°48Y25" Lat. 37°31'54"
Water temp. 28.5°C Air temp. 29°C
The slick was located just south of the Pamunkey River
Bridge at West Point near the Chesapeake Corporation Plant.
Particulate material and some foam was noted in a heavy
slick.
Sample #7: August 28, 1970 1245 hrs
Long. 76°45?10" Lat. 37°29f8"
Water temp. Ambient temp.
Down river from West Point a heavy slick with much
particulate material and foam was noted.
Sample #8: August 28, 1970 1430 hrs
Long. 76°32T57" Lat. 37°16f37"
Water temp. 29°C Ambient temp. 29°C
A very large slick with much particulate material and foam.
It extended up and down river for several miles with a
width about 50 yds.
Sample #9: September 24, 1970 1030 hrs
Long. 76°26*39" Lat. 37013'34"
Water temp. 27°C Ambient temp. 24°C
A slick was sampled off the Amoco (Yorktown) pier. It was
light with some foam and particulate material.
Sample #10: September 24, 1970 1145 hrs
Long. 76°30f18" Lat. 37014'30"
Water temp. 27°C Ambient temp. 24°C
This sample was taken under the Coleman Bridge. The slick
was light with no foam and little particulate material.
Sample #11: September 24, 1970 1300 hrs
Long. 37°15^34" Lat. 76°32I07"
Water temp. 27°C Ambient temp. 25°C
This slick was light with some foam and little particulate
material. The sample was taken in the Naval Weapons
Station area.
Sample #12: May 15, 1971 0915 hrs
Long. 76°23V Lat. 37°14'20M
Water temp. 18°C Ambient temp. 20°C
153
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The sample was taken in the Chesapeake Bay near the mouth
of the York River. The slick was very light with no foam
or particulate material.
Sample #13: May 15, 1971 0945 hrs
Long. 76°251 Lat. 37°13f55"
Water temp. 18°C Ambient temp. 20°C
Down river from the Amoco (Yorktown) Refinery a slick was
noted. There was some foam but the slick was light.
Sample #14: May 15, 1971 1015 hrs
Long. 76026133" Lat. 37013'32"
Water temp. 18°C Ambient temp. 21°C
A very heavy foamy slick was sampled just west of the
Amoco Refinery pier. Hundreds of dead jellyfish were noted
in the slick.
Sample #15: May 15, 1971 1050 hrs
Long. 76°29125" Lat. 37014!17"
Water temp. 18°C Ambient temp. 21°C
A slick was noted close to the Virginia Institute of Marine
Science pier. Winds were increasing. There was some foam
and some particulate material.
Sample #16: May 15, 1971 1125 hrs
Long. 76°32'I2011 Lat. 37°17'
Water temp. 19°C Ambient temp. 21°C
This slick was light but had much organic material. Winds
were increasing.
Sample #17: May 15, 1971 1205 hrs
Long. 76°35130" Lat. 37°19'55n
Water temp. 19°C Ambient temp. 21°C
Conditions are very similar to a no-slick sample due to
increasing wind. A very slight dampening effect was
reported. There was much organic material and little foam.
Sample #18: May 15, 1971 1245 hrs
Long. 76°38fl Lat. 32°21135"
Water temp. 18°C Ambient temp. 19°C
Conditions were the same as Sample #17.
154
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Sample #19: May 15, 1971 1400 hrs
Long. 76°44'50n Lat. 37°29'
Water tern p. 18°C Ambient temp. 19°C
Conditions were the same as Samples #17 and #18.
155
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APPENDIX C
EFFECTS OF AN ACCIDENTAL SPILL OF
NO. 6 FUEL OIL ON A SALT MARSH
An accidental release of about 800 barrels of a No. 6
fuel oil prepared by cutting a catalytic cracking residue
with a light distillate fraction occurred on or about 2000
hours on May 5, 1971, at the Yorktown, Virginia, Amoco
Refinery. The oil issued from a ruptured pipeline directly
into the York River and was carried by wind driven currents
through the Guinea Marsh where considerable amounts of oil
beached. A portion of the oil passed through channels in
the marsh and moved into Mob jack Bay where it was sampled
on May 6, 1971. The fraction of the spill volume confined
by the marshes is unknown, but observations from vessels
and a U.S.C.G. C-130 on May 6 led to an estimate of 3/4 of
the total oil remaining in the marshes. The spill trajec-
tory is shown in Figure 29. Wind and tidal current
information were available near the spill point, but could
not be used to justify the slick trajectory because the
spill time was uncertain to ±4 hours.
From 1200 hours on May 5 to 1200 hours on May 6 the wind
blew from 230°, averaging 9 knots, using hourly data taken
at the Ft. Eustis, Virginia, weather station. This wind
direction is in qualitative accord with the observed 50°
slick direction to beaching. The tidal current influence
on the oil motion may not have been great because, if the
slick moved at 3.7% of the wind speed, almost exactly one
tidal cycle would have been required for it to travel the
4.5 nautical miles to the beaching site.
E.P.A. investigators arrived on site on May 6, and were
transported to Guinea Marsh and assisted in sampling by
project personnel. An investigation to determine the
effects of a No. 6 fuel oil in the marsh was commissioned
by E.P.A. as a supplement and extension to planned project
activities. Amoco used a dispersant, Jansolv-60, at the
release point. The presence, potential toxicity, and
synergistic effects of the dispersant in the marsh were
studied, and a general analysis of dispersant composition
was conducted.
The composition of Jansolv-60 dispersant was not disclosed
upon request to the manufacturer, so analyses were
conducted at this laboratory. Atmospheric pressure
distillation to 128°C showed these percentages by volume.
156
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^GUINEA ,/
MARSHES
Fig. 29. Amoco oil spill trajectory
157
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Water 51%
Light hydrocarbons 33%
Pine oil., trace
Surfactant 16%
Silica gel and gas chromatography indicated the light
hydrocarbons were saturated aliphatics boiling between
125-235°C at 760 torr which approximates a deodorized
kerosene such as Jet B turbine fuel.
Infrared spectra of the surfactant indicated a predominantly
saturated hydrocarbon structure with carboxyl anion groups.
Aqueous solutions of the surfactant gave positive magnesium
urany! acetate tests for sodium. The ignition residue of
the surfactant was strongly basic. Tests for presence of
phosphate groups were negative. A portion of the
surfactant residue from the distillation was subjected to
Kjeldahl digestion and found to contain at least 3% nitrogen
by weight. Qualitative tests for the presence of tertiary
amines using the Hinsberg test, and N-bromosuccinimide were
positive. A titration of 1 ml of surfactant in 20 ml of
water with 0.1 N HC1, using pH electrode H+ detection,
showed the neutralization of the amine, but did not clearly
indicate the proton addition to carboxyl groups at low pH.
Original pH of dispersant and surfactant solution was 8.9
±0.1 depending on dilution.
Tests for ion charge characteristics of the dispersant
(Greenberg, 1962) showed it was cationic or amphoteric.
The presence of amine and carboxyl groups implies that the
surfactant is a long chain amino acid. A search of
commercial products uncovered Deriphat 160 (General Mills,
Inc.), an amphoteric compound (disodium N-lauryl beta
iminodipropionate) used as a down-hole petroleum surfactant.
It is suspected that this, or a compound of similar structure,
is the principal surfactant in Jansolv-60, but considerable
further purification and analysis would be required to prove
the exact surfactant structure.,
(' •' • ; ' - — '.•"," __
Dispersant composition studies were discontinued, as,no .
potentially toxic compounds or functional groups were
detected that would bring to question the manufacturer's
toxicity claims.
' '" '.'"• '\''-
OIL SAMPLING
Samples of oil, oiled grass, and oil exposed sediment were
taken for chemical analysis at the locations listed
below. Location numbers and names refer to the detailed
158
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map of Guinea Marsh (Figure 30).
Pate Time Location Sample Description
May 6 1320 37°17l12ll-76°17l30lt Slick
1405 37°15I39"-76°20I06" Slick
May 7 1230 37°15l36"-76°24f4811 Slick
1240 37°15I36"-76°24t33lt Slick
1420 1 Oil pool
May 9 1 Oiled grass
1 Intertidal sediment
1 Oil slick bordering marsh
1 Oil pool at high tide
time
2 Oiled grass
3 Snails on oiled grass
4 Intertidal sediment core
5 Intertidal sediment core
6 Intertidal sediment core
7 Intertidal sediment core
1 Oiled peat core
1 Intertidal sediment core
May 18 1 Oiled grass
1 Oil covered peat
37°13I17II-76°25I1911 Goodwin Is. Oiled grass
June 1 1 Grass and peat with
entrained oil
8 Oiled grass and mud
Samples on June 1 were at the only places where oil was
visible, so samples for chemical analysis were discontinued,
It is certain that oil remains absorbed in the peat and
buried in sediments, but problems relating to the sampling
and subsequent analysis of dispersed oil at uncertain
locations made further study of a very slowly aging
residual portion of the oil impractical. Beaches were
surveyed completely for oil exposure on May 11, 1971.
Areas with oil coverage are blackened in Figure 30. All
samples were frozen in dry ice immediately upon collection
and returned to the laboratory for analysis.
159
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MOBJACK BAY
\....~, — .....•"•*• "9 *!"• **\
YORK RIVER
7—
Fig. 30. Guinea Marsh oil sampling locations. Black areas are oil exposed
beach.
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BIOLOGICAL SAMPLING
The sampling location 1 was the most heavily coated above
the high tide line detected in the survey. Aerial
photography from a commercial helicopter showed the most
heavily oiled beaches, but did not show any oil not seen in
the surface survey. A program to sample inter tidal
organisms near location 1 and at two areas of significantly
lower oil exposure was begun on July 14-16, 1971. The
biological collection stations are shown as capital letters
on Figure 30. Station B is the most heavily exposed to oil,
while stations A and C were free of visible oil. At each
station a transect of five equally spaced substations was
established in the intertidal zone. Ten cores were taken
at each substation with a plexiglas corer (cores 15 cm long
x 8 cm diameter).
The cores were sieved through a 1.0 mm mesh screen, and the
material remaining on the screen was preserved in formalin
diluted with seawater for later species identification and
enumeration. Counts from individual cores were pooled and
averaged for each substation for population statistics.
In December 1971, the same transects were repeated to
determine the possible recovery of regions apparently
adversely affected by oil.
COMPOSITION AND AGING OF THE OIL
Distillation and gas chromatographic analysis showed the
oil to be a mixture of catalytic cracked crude residue and
a light recycled oil. The residue consisted primarily of
aromatic compounds boiling above 300°C at 1 atm, and was
quite unlike residual oils from crude distillation which
show obvious normal hydrocarbon peaks on gas chromatograms.
The May 18 sample taken near Goodwin Island was found by
gas chromatography to be a distillation residual of a
paraffinic crude and not related to the Amoco spill. No
Amoco oil was detected in marshes on the south bank of the
York River.
A fresh sample of oil from the pipeline was provided
by the Amoco Refinery. This oil was vacuum distilled and
gave the boiling range composition shown in Figure 31. The
lighter cuts of this oil were subjected to the F.I.A.
silica gel chromatography to establish relative aromatics
and saturates and portions of the aliphatic and of the
aromatic efflux were collected for G.D. and G.C.-M.S.
analysis.
161
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Q.
m
450n
400-
350-
300-
250-
200-
150-
100-
10
20
30
40
50
60
70
PER CENT OF TOTAL OIL DISTILLED
Fig-. 31. Boiling range composition of Amoco spill oil.
162
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Fraction b.p. (°C. 1 atm) . % Aliphatic % Aromatic
Gas Trap 83 17
1 209 8 92
2 209-221 < 1 > 99
3 221-238 0 100
A gas chromatogram of the unaged oil is shown in Figure 32.
It was run on a 1/8" x 6f copper column packed with 5%
SE-30 on Chromosorb G AW DMCS in a Perkin-Elmer 900 Model
Gas Chromatograph programmed from 100 C to 250 C at 4 C per
minute. Operation was dual column compensated with F.I.D.
detection. The unusual nature of this oil is indicated by
the lack of easily distinguished normal hydrocarbon peaks
and the bimodal distribution of peaks. Silica gel column
chromatography was used to separate aliphatics from
aromatics in the pentane soluble fraction of the oil.
Aliphatics and aromatics were gas chromatographed separately.
It was found that components boiling between 216° C and
317°C were approximately 70% aromatic with very high
aromatic contents (> 90%) up to 280 C. Aromatics in this
boiling range correspond to the naphthalene-anthracene
range including long chain alkyl substituted benzenes and
substituted naphthalenes that are not easily lost from the
oil by volatilization and are low enough in molecular
weight to be reasonably water soluble.
The lower molecular weight species in the first distillation
cut were identified. The major components, in descending
order of concentration were meta-xylene, ortho-xylene,
para-xylene, ethylbenzene, and toluene. Lesser amounts of
the ethyltoluene isomers, n-propylbenzene, and cumene
(jL-propylbenzene) were also present. These analyses were
performed at NASA Langley Research Center. Samples were
chromatographed through a 100 ft DPP open tubular capillary
column, then introduced into a Finnegan quadrupole mass
spectrometer.
The nature of the Amoco spill oil was such that little change
of character could be achieved, even by lengthy aging.
Pentane extracts of each of the samples listed above were
analyzed by gas chromatography. By May 6, the day following
the spill, the sampled oil had lost nearly all the light
recycle oil, but the catalytic-cracked residue retained its
original composition. Little or no further change could be
noted in samples taken as late as June 1. Hence, the only
observable aging of this oil spill was the rapid, immediate
loss of the light recycle oil by evaporation.
163
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24
Fig. 32. Gas chromatogram of Amoco Spill Oil. Integers are carbon numbers of
normal hydrocarbon peaks.
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The ^oil had disappeared from sight by June 1, 1971, by
various processes, including entrainment in the sediments,
absorption into the peaty root network of the Spartina
grass, and attachment to debris which was subsequently
washed out of the area. Much of the residue remained in
the area for the slow process of dissolution into the
surrounding water.
The catalytic cracked residue appears to consist of various
substituted benzenes and polynuclear aromatic species such
as naphthalenes, anthracenes, etc. A program of research
into the solution behavior of these aromatic species is
being designed at this laboratory. However, it is probable
that the alkylbenzenes present in this residue are less
soluble in water, and less toxic than polynuclear aromatics
of similar molecular weight. Boylan and Tripp (1971) have,
for example, compiled data indicating that the naphthalenes
are more toxic than the alkylbenzenes.
Gas chromatograms of the Goodwin Island oil sample showed
it was a normal No. 6 fuel oil unrelated to the Amoco spill
and of unknown source. Only a small area (200 ft of beach)
was affected. This oil showed a bluer and less intense
fluorescence of the pentane extract with 350 mm exitation
than did the Amoco oil. The Amoco oil has never, to this
date of reporting, lost its strong yellow-green fluorescence
due to weathering. This strong fluorescence is in keeping
with the highly aromatic residual character of the oil.
It should be noted that because of the highly unusual
nature of the Amoco oil spill, the results of its
contamination of marsh areas will not approximate that of
a "normal" No. 6 fuel oil. The Amoco oil, because of its
catalytic cracking treatment, does not contain a large
fraction of normal paraffins, and is almost entirely
aromatic.
BIOLOGICAL EFFECTS ON GUINEA MARSH
Several workers (reviewed by Cowell, 1971) have observed
that heavy oil has little effect on marine grasses with
rhizome systems. The predominant Guinea Marsh grass
exposed to oil was Spartina alterniflora. In areas with
heavy oil, leaf blades were coated and died apparently due
to respiratory failure. The rhizomes survived and produced
new young shoots within one month. There were no permanent
kill areas and the rhizomes prevented erosion of oil
exposed marsh. It is doubtful that marsh grasses would
survive repeated dosing (Cowell, 1971), but recovery was
165
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prompt during the growing season.
Intertidal algae were not investigated, as there were few
attached forms present above the low tide line, probably
due to wave action on the sandy bottom. There were
extensive Zpstera beds below the low tide line, but these
were not oil coated and always were at least 50 ft from
the oiled shoreline.
Survival of animals exposed to the oil appeared to be the
most sensitive indicators of effects, but highly motile
animals which avoided the oil or fled after being affected
could not be used as indicators. The intertidal macrofauna
in near surface sediments were exposed to oil and unable to
escape, so were sampled at the lettered locations shown on
Figure 2. Intertidal sediment cores taken at stations A
and B were extracted with pentane and the extracts gas
chromatographed to prove the presence of oil at station B
and its absence at station A. This was not done for station
C because no oil beached on that island.
Organism counts at each substation were pooled for each
station and the number of species (S), the number of
individuals (N), and the number of individuals of the ith
species (nj_) were recorded for each station for the July
and December samplings.
The above count information was used to calculate:
Species Richness ~
O 001 Q S
Species Diversity (H1) = *'2 (N log N - E n* log n...
w i-1 *
TT !
Evenness Component (J1) =
log/
The Affinity Index was calculated from data at pairs of
stations according to Sanders (1960). Statistical parameters
for July and December are listed in Table 22.
Population indices for stations A and C are quite similar,
while those for station B show great reductions in number
of organisms, species, and species richness. The affinity
index for stations A and C is high. The situation was
nearly the same for July and December collections. It is
assumed that the Amoco oil caused population reductions and
166
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Table 22.
Population Statistics of Marsh Intertidal Infauna
for July (December).
Station A Station B
Station C
N
S
Species
Richness
H'
J'
Affinity
Index
482 (536) 88 (107) 611 (2481)
32 (34) 14 (19) 34 (60)
5.02 (5.25) 2.90 (3.85) 5.14 (7.55)
3.02 (3.21) 3.28 (3.21) 3.02 (4.03)
0.605 0.631 0.861 0.756 0.594 0.684
to Sta. A - 38.7 (27.4) 62.0 (46.8)
to Sta. B 38.7 (27.4) - 48.2 (46.8)
to Sta. C 62.0 (46.8) 48.2 (42.1)
structure alteration of the intertidal community at station
B, but this is difficult to prove in the absence of a
detailed survey at the stations immediately prior to the
oil spill (Foster, et al., 1971). Biological collections
will be repeated in May 1972 to demonstrate the recovery of
station B intertidal fauna, but recovery may require
several years because the oil is still present in the
sediments and may exhibit the long term toxic effects of
soluble aromatic compounds observed by Blumer, et al. (1970)
In conclusion, immediate effects of the oil spill on Guinea
Marsh were not great. Long term effects cannot be
documented as there was no baseline information to describe
the previous condition of the marsh. A before and after
study of a previously well sampled salt marsh which is
exposed to controlled amounts of number 6 oil is being
designed at this laboratory to prove long term effects.
Results here, taken from similar sedimentary environments,
strongly indicate a toxic effect of the Amoco oil spill.
There is no present means of assessing the ultimate marsh
ecosystem damage, and, were this possible, such damage
could not be estimated in dollars.
167
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REFERENCES
Blumer, M., Souza, G., and Sass, J. (1970). Hydrocarbon
pollution of edible shellfish by an oil spill. Mar.
Biol., 5.» PP- 195-202.
Cowell, E.B. (1971). Some effects of oil pollution in
Milford Haven, U.K. Joint Conf. on Prevention &
Control of Oil Spills, Washington, D.C., pp. 429-435,
Foster, M., Neushul, M., andZingmark, R. (1971). The
Santa Barbara Oil Spill, Part 2: Initial effects on
intertidal and kelp bed organisms. Environmental
Pollution, 2, pp. 115-134.
168
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SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
,1. Report No.
w
INVESTIGATION OF SURFACE FILMS - CHESAPEAKE BAY
ENTRANCE,
Maclntyre, W. G.; Smith, C. L.; Munday, J. C.;
Gibson, V. M.; Lake, J. L.; Windsor, J. G.; Dupuy, J. L; et. al.
5. Report Date
\6. ' .
[ S. Performing Organization
Report No, • '~
9. Organization
"*" Virginia Institute of Marine Science
Gloucester Point, Virginia 23062
!'"':. PtOJf'il NO
15080 EJO
'13^ Type vf Repot ,. and
..JTTrT...r-, „ .—PH ««—»>, «.^«-««». *-...» »~M«—«JL»»C » -~ — • *••„.. * Period Covered
•^n^"80™^^ Protectio'n}Agency, WQO
15. Supplementary Notes
U.S. Environmental Protection Agency report
number EPA 670/2-73-099
16. Abstract
Experimental point source oil releases have been conducted in the Chesapeake
Bay mouth area. Predictions of oil slick motion were tested, and slicks were sampled
and analyzed to measure their aging rates over periods up to 32 hours. Remote sen-
sing techniques were used to detect and measure the spreading rate of oil. Some
laboratory oil film aging experiments were done to further document and elucidate
aging processes. Results indicate a reasonable motion prediction, an explanation
of the non-biological initial aging of oil films, and a fair corroboratiori of a
theoretical oil spreading model.
Indigenous surface films in the study area were analyzed for lipid and chlori-
nated hydrocarbon content. Hydrocarbons were 300-500 microgram per liter and fatty
acids and esters 700-7800 microgram per liter in surface film samples. Chlorinated
hydrocarbons were generally less than 100 parts per trillion in surface films, in
contrast to some earlier high concentrations found in Biscayne Bay. Surface film
analysis limitations imposed by sampling methods are discussed. Plankton in slick,
non-slick, and subsurface water were counted. Populations were higher in surface
than subsurface water, and higher in non-slick than in slicked surface water.
i?a. Descriptors *oil Spills, *Estuarine Environment, *Chesapeake Bay, Oil Pollution,
Estuaries, Currents, Sampling, Chemical Analysis, Chromatography, Chlorinated
Hydrocarbons, Pesticides, Liquids
i7b. identifiers *Surface films, *0i 1 slicks, Remote sensing, Hydrocarbon analysis,
oil aging, fatty acids
17c: COWRR Field & Group 05A
18. A vailability
-Security Ctes$; s
fRsptnti) ••'- '
Se&triiy Ot,$$. ' «
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 2O24O
Dr. Win. G. Maclntvre
I institution Virginia Institute og Marine Science
U.S. GOVERNMENT PRINTING OFFICE: 1974-544-317:311
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