EPA 660/3-73-013
SEPTEMBER 1973
Ecological Research Series
PETROLEUM WEATHERING:
SOME PATHWAYS, FATE, AND
DISPOSITION ON MARINE WATERS
Nalittai fiNiroBtneitlai Besearel
Office 9\ Research and Development
If S. Eu^irsniestal ProtectisB Apscjf
Corwilis. fifepir S7338
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. 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 ECOLOGICAL RESEARCH STUDIES
series. This series describes research on the effects of pollution
on humans, plant and animal species, and materials. Problems
are assessed for their long- and short-term influences. Investigations
include formation, transport, and pathway studies to determine
the fate of pollutants and their effects. This work provides
the technical basis for setting standards to minimize undesirable
changes in living organisms in the aquatic, terrestrial and atmospheric
environments.
EPA REVIEW NOTICE
This report has been reviewed by the Office of Research and
Development, U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the U.S. Environmental
Protection Agency, ,nor does mention of trade names or commerical
products constitute endorsement or recommendation for use.
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EPA 660/3-73-013
September 1973
PETROLEUM WEATHERING:
SOME PATHWAYS, FATE, AND DISPOSITION ON MARINE WATERS
By
M. H. Feldman
National Coastal Pollution Research Program
Pacific Northwest Environmental Research Laboratory
Program Element No. 1BA025
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CORVALLIS, OREGON 97330
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ABSTRACT
Three mechanisms of weathering of oil pollution on marine waters are
discussed. Photolysis, interactions with trace materials, and
sedimentation with participate materials are considered as competitive
to other fate of petroleum mechanisms and as having possible ecological
importance.
n
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CONTENTS
Sections Page
I INTRODUCTION 1
II OBJECTIVE 2
III DISCUSSION 3
A. Radiation Chemistry
Hydrocarbon Photolysis
As Precursor to Tar In
Marine Waters 3
Carcinogem'cs Formation 4
Temperature and Tar Formation 4
Rate of Removal of Oil Slicks--
Photolysis Initiated 5
B. Trace Material Interactions
In The Surface Layer 5
C. Sedimentation Processes
As Weathering Fate Mechanism 8
IV SUMMARY 10
V REFERENCES 11
ill
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TABLES
Np_. Page
1 Estimate of Standing Stocks of Pelagic Tar in the
Northwest Atlantic Ocean and Mediterranean Sea 15
2 Heat Balance Due to Sunlight versus Latitude 16
3 (a) Substances Isolated from Seawater Extract of Kerosene. 17
(b) Relative Concentration of Aromatic Species in Kuwait
Oil Seawater Extracts (Slow Stirring) 17
4 Concentrations and Enrichment Factors of Organic Compounds
and Metals in Surface Microlayer Samples from Narragansett
Bay, Rhode Island 18
5 Instrumental Neutron Activation Analysis Results on 16
Different Marine Fuel Oils 19
6 Oil Degradation Rates Under Varying Conditions as Shown
by Selected Authors 20
7 (a) Quantities of PAH Resulting from Combustion of One
Gallon of Commercial Gasoline 21
(b) Quantities of 3,4-Benzpyrene Detected in Bottom
Deposits 21
(c) Quantities of 3,4-Benzpyrene Detected in Marine
Animals 21
iv
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SECTION I
INTRODUCTION
"Weathering" is a term used to express, qualitatively, the idea
that petroleum "oils" or hydrocarbons (HC) when spread upon the sea
are changed in their character with time; it is assumed that the
original material, isolated within its earth strata, had been stable for
long periods of time. The term weathering, involves the idea of
mechanism or process, leading to ultimate disposition or, briefly: Fate.
What biological, chemical, and physical reactions occur to which
may be attributed the (weathering) changes observed? Can the rates
at which these competitive and cooperative possibilities occur
be tabulated so that the behavior of a given petroleum in a given
biogeographic/geochemical locale, and its behavior, its fractionation
and disproportionate on, and its biological, chemical and physical
interactions, and final disposition may be quantitatively predicted?
The answer to this rather lengthy question is that at present even the
possible determinants of the chemical and physical behavior of
hydrocarbons disposed to the sea cannot be tested. At every level
of inquiry there are significant problems of experimental methodology,
mathematical and systems analysis, and even in defining the problem.
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SECTION II
OBJECTIVE
The objective of this report is to discuss some of the possible
mechanisms of weathering of petroleum on marine waters.
Mikolaj (1972) lists some of the generally accepted individual
components of the generic term "weathering", evaporation, leaching of
water solubles, autooxidation, biological degradation. Presented here
are (1) radiation (photolysis, et seq.), (2) trace material
interactions, and (3) participate (sedimentation) interactions.
Discussion of these three modes leading to weathering and ultimate
disposition of HC on the sea will of course involve other variables
(temperature, geographic location) and cannot be all inclusive, as
causes leading to ultimate fates. Thus, the importance of other
mechanisms, solubilization, emulsification, evaporation, is recognized
but they are not discussed here.
1. Photolysis (above 3200 A°) affords an initiating mechanism, and
quite possibly a major mechanism, for:
(a) oxidation of larger more complex molecules (auto-catalytic
oxidation).
(b) polymerization reactions (disproportionation).
(c) carcinogenic hydrocarbon (CMC) compound formation and removal.
(d) tar ball formation.
2. Interaction with trace materials at the surface layer involves:
(a) trace or heavy metals as toxicants.
(b) metabolic atoms.
(c) trace compounds like vitamins, ami no acids, EDTA, formation
and removal of biologically significant nutrient forms of P, N.
(d) trace compounds that are essentially toxic or inhibitory
DDT, PCB, CHC formation and removal. Of course a, b, c, d may be the
guiding lines to what can happen and what does happen to biota at
the beginnings of the ecological pyramid or chain sequence of events
in trophic levels. This will be discussed in terms of trace materials
as ecological determinants.
3. It is possible that geographically variable sedimentation
and particulate interaction processes are a significant factor in
predetermining the ultimate fate of HC pollutants.
The mere removal of HC by intercalation and other sedimentation phenomena
based on interaction with clays, silts, glacial flours is too simple
a view as will be developed. The reason for including this area
in a discussion of 1 and 2 above which are mechanism oriented while
3 apparently is a simple removal comparable to evaporation will be
discussed.
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SECTION III
DISCUSSION
A. Radiation (photolysis) chemistry, (Noyes £. Leighton 1966),
(Burton & Magee 1969 et sea,.) is a well developed science; the lower
molecular weight HC, especially paraffins, are effectively transparent
to wave lengths occurring in sunlight, even down in the region 3200-
4400 A . Thus, to photolyze methane, fluorite windows are required
for the wave lengths necessary; and while the photolysis of ethane
leads to a number of interesting products (many of them of higher
molecular weight) ethane too requires light further in the UV than
is available at the sea surface.
Nitrogen, oxygen, sulfur-containing organics do absorb in the visible,
and naphthenic acids are among the photolytically active petroleum
fractions. The photolysis of fractions of petroleum especially
the naphthenic acids has been observed by a number of workers; ZoBell
(1963, 1971) references some of these observations.
Noyes and Leighton (1966) shows some quantitative data on anthracene, 3-
methyl anthracene, transstilbene, rubrene; all respond to wave lengths
3100 A and longer and are likely suspects for radiation chemical effects.
Acenaphthene, anthracene, dehydroanthracene all reacted in sunlight
(or equivalent wave lengths in glass).
Toluene and related aromatics with side chains have been photolyzed
in the presence of a variety of materials such as FLO, H?02s H20+FeCl«;
tetrahydronaphthalene in presence of HJ) and 02 gave polymeric materials.
Unsaturated hydrocarbons are also absorbers at the longer wave
lengths.
Hydrocarbon Photolysis as Precursor to Tar in Marine Waters.
According to the data accumulated by Morris and Butler (1973) and
shown in Table 1, the tar found in Mediterranean and in Sargasso was
more than N. Atlantic. In the absence of quantitative data on actual ballast
oil inputs, and retention factors in various seas, and the suggested
subsequent chain of events their working hypothesis cannot easily be
tested. Another working hypothesis might be that petroleums of comparable*
average content injected in all three oceanic areas with comparable frequency
end up as tars or tar balls in proportion to the available oil,
UV, oxygenation rates and ambient temperatures. Quite probably the
retention times for petroleum oils (inverse of other removal processes,
currents, etc.) are just not available for firm data analysis.
*Some, however, --e.g. Kuwait origin--as also Santa Barbara seeps,
are known to be high in the tar-genie materials.
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The kind of reactions postulated are:
IV
>-»-
,2
(1) Oil fraction (i) •»-»-»-+• [Active intermediates]
(2) Active intermediates
and products of prior
steps
0'
AT
Auto oxidation
Polymerization and disproportionate
* ' c -"--^ Degradation and/or synthesis by
st.epK K appropriate biota.
Reaction (2), polymerization and disproportionate involves the
formation of smaller molecules plus longer chain/higher M.W. compounds.
Polymeric materials are the typical outcome of initiation by irradiation
and subsequent thermal reactions. [Burton and Magee 1969 et seq.].
While photochemistry is more specific in the initial chemical changes
than radiation chemistry, the longer term outcome of irradiation
not carried to ultimate oxidation (Armstrong et al., 1966) seems
to be similar.
CARCINOGENICS FORMATION
Reaction (3), biodegradation, of course, ultimately leads to C02
but intermediate metabolic steps proceeding from a polycyclic aromatic
base can lead to carcinogenic intermediates. The work of BoyIan and
Tripp (1971) shows the solubilities of various molecular forms found
in kerosine (see Table 3). The review by ZoBell (1971) shows the
ubiquitous nature of the carcinogenic hydrocarbons CMC and their
synthetic and metabolizable properties. The discussion by Parker
(1971) shows that the solubilities of petroleum in equilibrium with
saline water was markedly diminished by sunlight. The formation
of higher M.W. substrates and of carcinogenic materials and tar balls
are interrelated phenomena involving competitive rates of radiation
initiation, thermal reaction, and biosynthetic processes. They are
competitive, as well, with the more usually listed physical weathering
processes such as: chocolate mousse formation, emulsification,
evaporation of lighter fractions.
Temperature and Tar Formation.
Allen, et al., (1970) point out how irregular is the seepage
contribution to "beach tar" on the Southern California Coast. ZoBell
(1963) indicates a definite temperature component in the frequency of
occurrence of tar on the beaches of Southern California. Both writers
indicate that the temperature or seasonal correlation is to the
seepage rates. But as the temperature rises in the water off Santa
Barbara, in summer, see Figure 1, it is difficult to see how the temperature
of the earth volume from which seepage occurs can respond so quickly.
An alternative hypothesis is that the temperature increase (as
the summer season increases in sunlight occur) is reflected in
increased reaction rates in the postulated series indicated previously
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on page 4, resulting then in more apparent tar availability during
warm seasons and in warmer waters. The higher radiation and temperatures
will result, of course, in faster agglomeration as suggested here,
as well as faster evaporation as suggested by Morris and Butler
(1973). Their data indicate the temperature, seasonal increase
in tar ball formation. Large, fairly hard, dense pieces may not
be fully accounted for by radiation initiation, followed by thermal
polymerization, but evaporation alone seems quite incomplete as
mechanism. Munday, (1971) finds that tar balls are significantly
warmed by radiation absorption. Because of their black nature,
the tar balls, once initiated, will have their energy absorption
efficiency increase.
The Rate of Oxidation Removal of Oil Slicks - Photolysis Initiated.
The rate of oxidation of hydrocarbons and nitrogen, oxygen, sulfur-
(NOS) compounds varies with their chemical nature (Koons 1973).
For example a tertiary hydrogen is oxidized more readily than a
primary or secondary hydrogen; thus, alkyl substituted naphthenes
will be oxidized more rapidly than normal paraffins. Acceleration
of oxidation rates may occur by photolysis initiation followed by
thermal chain steps, or by catalysis caused by traces of metallic
ions of variable valence, or maybe slowed by chain stopping steps
due to sulfur atoms.
Experimental estimates of the actual removal rates of slicks attributable
to the photolysis initiated and thermal chain reactions subsequent to
the initiation have been made. Using light sources resembling the
spectrum of sunlight, whose internal relative intensities are within
a factor of two, the total rate of decomposition corresponds to
the destruction of a 2 1/2 ym thick slick in 100 hours. (Freegarde
and Hatchett 1970).
A slick of thickness 2 1/2 ym has about 2000 kg/km2 (1300 gal/mi'2, Garrett
1969). Assuming an effective day of sunlight less than eight hours,
sunlight photolysis can initiate sufficient oxidation reaction to
remove the slick in a few days.
It has been noted that approximately the top 2 um layer of a freshly
laid asphalt roadway is oxidized in about one day (E. Mertens).
B. Trace Material Interactions In The Surface Layer.
Garrett (1967) has pointed out the existence and composition of
a trace material rich surface layer other than petroleum on the sea.
Williams (1967 has shown the existence of a variety of nutrient materials,
both organic and inorganic, and probably including amino acids in the
surface film. Duce and Quinn (1972) showed the significant enrichment
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of this layer in trace elements (trace metals and other pollutant
materials) see Table 4. Feldman (1970) has discussed the set of trace
materials (TM) comprised of trace elements or metals (I.E.) and trace
organic compounds (T.C.) defining, T.M. = I.E. + T.C. Guinn and coworkers
(1970) have shown that the usual trace elements, nickel and vanadium,
generally measured in petroleums, are by no means all that can be
observed. See Table 5. For purposes of fate and mechanism it is
important to note that the trace element composition of various petroleums
is distinctive. Filby and Shah (1971) showed further that the various
naphthenic and other fraction of petroleums can be characterized
by their T.E. content. These workers were intent on a system of
analysis, for government regulatory purposes, based on neutron activation
analysis "fingerprinting". Lukens, et al., (1971) organized the
pioneer work of Guinn and of Filby and Shah into a coherent reliable
identification of petroleum system. The true utility, of the work of
Filby, Shah, and Guinn, in addition to regulatory agency usage,
is as a means of following the petroleum and its interactions in
the surface layer with preexisting trace elements and compounds through
its fate and transport processes to tar balls, carcinogenics formation,
and phytoplankton, bacterial and faunal interactions.
Feldman (1970) has explained how the trace element composition of
the sea is not as relatively constant as the major constituents' relative
composition due to chemical processes, biological interactions, and
pollutional influences. The changes in the relative quantities of trace
materials, which may be essential, nutrient, or toxic, and which may
be trace metals, trace compounds (vitamins, amino acids) or large
molecular aggregates (humic and fulvic substances) determine the
phytoplankton successions that can occur. These, in turn, determine
which subsequent trophic levels and species can occur.
It is noted, therefore, that the interactions, or the pathways,
of trace materials, influence the biodegradation, as well as the
synthesis, of hydrocarbon materials. The succession of biota, each in
its turn utilizing a particular fraction of petroleum, or an intermediate
product, can be interfered with by the presence of trace compounds
(herbicides and biocides of all descriptions), as well as trace materials
in general which tend to concentrate in the surface layer already
rich in trace materials and now also in petroleum.
Microbial degradation of oil, it is assumed, is adequate and complete.
But the data do not support it. Floodgate (1972) has assembled
data on this point. See Table 6. This fact is emphasized by the
findings of Blumer (1972) of surprising persistence of even light
fuel oil (#2) paraffinic fractions in sediments. The implication
of the relations of petroleum to the active surface layer in terms
of trace materials which guide and control all biotic responses is
clear. The interferences with pheromone and general chemotaxic
reactions is a specific instance.
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If the trace materials array can, in fact, determine not the biomass
achievable (that depends on physical arrangements and total nutrient
available) but the nature, i.e., the identity of the successful species,
then, the trace materials at the surface is a most significant determinant
of fate and mechanism and it is essentially unknown. For example, the
typical petroleum analysis, in an effort to study petroleum fates
and mechanisms, is by gas chromatography. Making quantitative assertions
by such procedures is difficult. Apparently, no one has analyzed
tar balls for trace elements though Filby and Shah (I.e.) have analyzed
some weathered higher molecular weight fractions.
The concentration of other trace materials in the surface layer
described by Garrett (1967), Williams (1967), Duce (1972), Hites (1972),
for such obvious items as DDT, and PCB, which are known to concentrate
in surface oils and are known to hinder biodegradation in accumulated
oily sediments in gulf coast areas with petroleum industry pollution
sources, and thought to change succession and the relative viability
of algal species, [Mosser et al., 1972], seem to be inherent questions
in any consideration of fates of pollutant petroleums on the sea.
An interesting and possibly very important issue for radiation and
biosynthesis in weathering mechanisms is the question: "Is the oxidized,
photolyzed, polymerized, and biosynthesized set of intermediate or final
compounds more or less deleterious than the source materials?"
The relative rates of photochemical degradation or building versus the
synthesis, uptake, or metabolism by the marine bacteria, algae,
and higher plants operating in a randomly repetitive oil milieu
is unknown, but to pollution discussants this ought to be a significant
question. Carcinogenic materials are present in many crude petroleums.
In addition they may be biosynthesized or degraded though available
laboratory rates are not applicable, (ZoBell 1971). These same materials
may be removed by photolysis (Suess 1972) and given the data on
their formation in the internal combustion engine (ZoBell 1971), which
is essentially a spark of initiation followed by chain thermal reaction
steps, it is probable that sunlight initiated reactions in the oil
slick can be followed by chains of reasonable length to form carcinogenic
molecules. Unfortunately, no rate of formation data are available,
though the marine inventory of carcinogens in sediment and biota is
impressive, (ZoBell 1971). ZoBell (1971) has pointed up the ubiquitous
character of the CHC and it is apparent that some of the polymeric
and other photolysis resultants are of this nature. The retention
and possible toxicity of some petroleum fractions has been discussed
by Blumer, et al., (1970). ZoBell (1971) points out that some oxidation
reactions of fossil fuels lead to CHC. See Table 7. The synthesis,
bioformation, uptake, and the metabolism and removal of these potentially
catastrophic materials in the case of hv, AT, and bacterial reactions
in the surface films, where a variety of organics and inorganics
is known to occur, is eminently worthy of detailed study.
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C. Sedimentation Processes As Weathering Fate Mechanism.
The intercalation of organic molecules, including petroleum fractions,
has long been the subject of inquiry. A recent definitive
review, Uhitehouse (1969) discusses this subject. It has, of course,
long been known that trace elements are to be found associated with clay
layers. But in recent years the influx of large quantities of significant
metallic ions to the coastal waters has been associated with organic
particulate carriers in the river and estuary waters as the fresh waters
meet the saline waters in the zone of rapid mixing of coastal oceanic
waters. The changes in sorption and desorption of specific metals in
the region of the change of salinity as formerly defined, is now further
complicated. There are organics on the surface, as sequestrants,
coordinators, chelators, also intercalated, and in some instances
coacervated, and these are not just humic and fulvic substances,
but include vitamins, amino acids and other key substances.
The addition of petroleum at the surface where free radical and thermal
disproportionation, and possibly catalyzed reactions are occurring,
the concentration of biocidal materials, the presence of a store
of trace elements in the petroleum, makes for a unique phase of
considerable interest to students of oil pollution fates.
It is perhaps obvious to state that sinking the oil slick by application
of stearated talc or CaC03 can produce quite different ecological
impacts 200 miles at sea, or in a bay with a large nursery population
and an important marshland periphery. It is perhaps obvious to
state that the utilization of the organic and inorganic N, P in
the surface films of the Eastern Pacific (Williams 1967) may be
radically altered by the interference in this base of the trophic
pyramid or at the source of the trophic chains (Feldman, 1970) by
the presence of oil undergoing its fate processes, and interacting
at each step with the normal biologically mediated and photosynthetically
supported series.
The fate and interaction of petroleum and its fractions at the surface
during the weathering process, is competitive with other removal systems.
Thus, no assertion is made concerning solubilization, evaporation,
droplet diffusion and emulsification, and the myriad phase phenomena
whose rates are not well known, and which require research, as fate
determinants. They actually constitute another class of weathering
rates: removal to other phases or milieux where of course chemical
and biological interactions may be equally as interesting as in
the surface layer.
Thus, why discuss sedimentation which is apparently also a removal
mechanism? Particulate interactions with cellular species, on organic
aggregates of humic materials, on and with larger molecular aggregates
that have undergone at least some of the reactions of Section A all
8
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constitute unknown but important territory for consideration of sea
surface fates. Practical considerations of course are the prime reason
for pollution students to be aware of these questions: are the silt
of the Southwest (Santa Barbara), the glacial flour of Alaska (Valdez),
and the clays of Southeast and gulf coasts of USA, all similar in this
regard? How could this be so? The sandy silicious grain may act
as a nucleus for evolution of a surface polymeric system but a clay
will sequester the organics in sheets and in its layers and what is
more the trace element and trace compound interactions will be different
in the two cases.
The practical question of the impact of petroleum industrial systems
on coastlines with varying sedimentation regimes has great theoretical
and practical implications for ecological impact evaluations. No
rational government regulation of oil industry practices is possible
without at least some investigation and understanding of these unknowns.
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SECTION IV
SUMMARY
Three mechanisms, photochemical, trace material interactions, and
particulate interactions, have been considered as competitive pathways
for the fate of petroleum pollution on the sea surface.
Phenomena observed by a number of researchers have been related to
the postulated reactions and mechanisms, and the need for research
pointed out in several instances.
Knowledge and understanding of fates and pathways, and ecological
and health determining interactions of petroleum pollution and trace
materials is a prerequisite for rational governmental regulatory
functions.
10
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SECTION V
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Blumer, M. (1972), "Oil Pollution Persistence and Degradation of
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Blumer, M. (1972), "Submarine Seeps: Are They A Major Source of
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Blumer, M., G. Souza, and J. Sass (1970), Marine Biology 5. p. 195
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Boylan, D. B., and B. W. Tripp (1971), "Determination of Hydrocarbons
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Duce, R. A., et al., (1972), "Enrichment of Heavy Metals and Organic
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Feldman, Milton H. (1970), "The 50 Mile Ballast Oil Dumping
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Floodgate, G. D. (1972, "Microbial Degradation of Oil," Marine
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Frankenfeld, John W. (1973), "Factors Governing the Fate of Oil
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Garrett, William D., (1969), "Confinement and Control of Oil Pollution
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Garrett, W. P. (1967), "The Organic Chemical Composition of the
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Mertens, Edward, (private communication).
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Morris, B. F. (1971), "Petroleum: Tar Quantities Floating in the
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Morris, B. F., and J. N. Butler (1973), "Petroleum Residues in the
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Mosser, J. L., N. S. Fisher, C. F. Wurster (1972), "Polychlorinated
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Dover Publications, NY (1966).
Parker, C. A., M. Freegarde, and C. G. Hatchard (1971), "The Effect
of Some Chemical and Biological Factors on the Degradation of Crude
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Suess, Michael, Laboratory experimentation with 3, 4-Benzpyrene in
aqueous systems and the environmental consequences. Aus
Wissenschaft and Praxis, Zbl Bkt. Hyg., I Abt Orig B 155, 541-546,
(1972).
Whitehouse, Ulysses Grant (1969), "Adsorption Mechanism: Aluminosilicate
Organic Interactions in Saline Waters," A.C.S. Tour M 21 (1969-70),
to be published, Advances in Chemistry Series.
Williams, P. M. (1967), "Sea Surface Chemistry: Organic Carbon and
Organic and Inorganic Nitrogen and Phosphorus in Surface Films and
Subsurface Waters," Deep Sea Res. 14. p. 791 (1967).
13
-------
ZoBell, C. E. (1971), "Sources and Biodegradation of Carcinogenic
Hydrocarbons," p. 441 in Proc. Joint Conference on Prevention and
Control of Oil Spills, June, 1971, Washington, D.C., EPA, API.
ZoBell, C. E. (1963), "Occurrence, Effects, and Fates of Oil
Polluting the Sea," Int. J. Air and Water Pollution (1963),
pp. 173-198.
14
-------
Region
NW Atlantic Marginal Sea
Gulf Stream
Sargasso Sea
Total NW Atlantic
Mediterranean (Ref. 5)
TABLE 1
Estimate of Standing Stocks of Pelagic Tar in the Northwest Atlantic
Ocean and Mediterranean Sea
area (units
of 1012 m2)
2
8
7
17
2.5
no. of
samples
8
16
34
58
41
range of
samples
(mg/m2)
0.0
0.1
0.1
0.0
0.0
- 2.4
- 9.7
- 40
- 40
- 540
mean tar probable
cone. error of
(mg/m2) mean
0.9 0.2
2.2 2.4
9.4 2.8
5.1
20.0 1.3
standim
(thousai
metric
2
18
66
86
50
Total NW Atlantic and
Mediterranean
19.5
99
7.0
136
(Morris, Butler 1973)
-------
TABLE 2
Latitude Heat Balance Due To Sunlight
Mediterranean 30°-40°N +.014 to -.005 g cal/cm2/min
Sargasso 30°N +.014
N. Atlantic 40°-50°N -.005 to -.026
16
-------
TABLE 3
CWPOUND
BCh7rt.CS
1-CETHYL-2-ETMYL BENZENE
l-HETMYL-4-ETHYL DEN2ENE
1 3.5-TRIMETHYL BENZENE
1-HETHYL-2-ETHVL BENZENE
1-2 4-THIMETHYL BENZEhE
1:2:3-TRIMETM»L BENZENE
l-HETHVL-4-PROPYL BENZENE
l-HETMYL-2-PROPYL BENZENE
1-3-BlnETHYL-S-ETHYL
BENZENE
1 • 3-PmETHYL-4-£TMYL
BENZENE
l;2-OIMETHYL-4-£THYL
BENZENE
l:3-l>IMETHrL-2-ETHYL
BENZENE
1-METHYLINDANE
2-HETHVLINOANE (f
1.5-DIM.ETHYL-2-ETHYL
SESZENE
1.2-DIHETNYL-3-ETHYL
DENZENE
1 2:3.5-TETRAHETHYL
BENZENE
1-2:4 3-TETRAHETHYL
BENZENE
4-METHYL INDAIIE
1 2.3.4-TETHATETHYL
BEhZENE
1 3-DlnETMYL-l-PROPfL
EEIIZE-IE
1 2-DI«eTMYL-4-PJ!G»YL
6ENZENE
TETPAKYSROhAPHTHALENE
e PEAK CONC.
B.PT. » fua/L>
161.3 2 ,.
\ 6.68
161.99 2 ""^
164.72 3
^>8.10
165.15 3 ^
169.35 4 20.15
176.03 5 18.07
6
183.30 7v
184.80 7—^5.93
183.58 l'
188.20 8
189.40 8 \
190.01 8 -^18.17
190.6 8 /
191. 4 8 /
190,1 8
193.91 9 6.21
193 00 Hv
196.80 10-^
205.5 1L
205.04 11\
205.6 11—^35.39
208.5 1J I
207.57 I/
Substances isolated from Seawater Extract of Kerosene
Relative Concentration of Aromatic Species in Kuwait Oil
Seawater Extracts (Slow Stirring)
ug/l. Concentration
Benzenes and naphthalenes (Fig M) 657 45.2%
Polar aromatics (Fig IB) 796 54.8%
Total amount of oil in water 1,453
Concentration of individual compounds
Naphthalene 32.3 (2.2%)
2-Methyl naphthalene IS.O (1.0%)
1 -Methyl naphthalene 18.0 (1.2%)
FBovlan Trioo 19711
217.96 i: 152.89
241.05 13 85.66
244.64 14 63 43
255 2 15 27.40
-------
TABLE 4
Concentrations and enrichment factors of organic compounds and metals in surface microlayer samples from Narragansett Bay, Rhode Island.
Substance
Fatty acids
Hydrocarbons
PCB'st
Lead
Participate
Organic
Inorganic
Iron
Paniculate
Organic
Inorganic
Copper
Paniculate
Organic
Inorganic
Nickel
Paniculate
Organic
Inorganic
Sample 1
Concentration
j (^g/liter)
Surface
128 ±26
NAt
4.2 ± 1.0
J.4± 1.1
10± 08
1.7 ± 03
320 ±47
3.7 ± 1.5
2.8 ± 0.4
7.2 ± 2.3
56 ± 0.5
3.4 ± 0.4
11 ± 3.0
4.9 ± 2.6
11 ± 40
Subsurface
36 ±7
NAt
0.1 5 ±0.04
024 ±0.17
0 36 ± 0 06
2,7 ±0.5
28 ±4
0.60 ± 0.33
1.4 ±0.2
0.20 ±009
0.19 ±0.11
3.3 ±0.3
02 ±0.1
048 ±0.33
14 ± 1.0
Enrichment*
factor
3.6 ±
1.0
NAt
28 ±
58±
2.7 ±
0.6 ±
29 ±
6.2 ±
2.0 ±
36 ±
29 ±
1.0 ±
50 ±
10 ±
0.8 ±
10
6.1
2.2
0.2
5
4.3
0.3
18
17
0.2
30
8.7
0.3
Sample
2
Concentration
(^g/liter)
Surface
94
8.5
0.45
1.5
1.4
6.1
35
5.1
17
1.3
1.6
1.5
13
5.0
21
±
±
-+-
±
^
±
±
;£
±
±
±
±
±
±
±
19
1.7
0.11
02
0.6
1.4
7
2.3
8
0.4
1.0
0.6
5
0.6
5
Subsurface
62 ±
5.9 ±
^ 0.05
0.28 ±
0.27 ±
3.7 ±
8.2 ±
3.8 ±
12 ±
0.26 ±
0.11 ±
1.3 ±
2.1 ±
1.8 ±
16 ±
12
1.2
0.10
0.12
1.0
1.2
0.8
1
0.11
0.04
0.4
0.3
0.7
2
Enrichme,
factor
1.5 ±
1.4 ±
*s9
54±
5.2 ±
1.6 ±
4.3 ±
1.3 ±
1.4 ±
5.0 ±
15 ±
1.2 ±
62±
2.8 ±
1.3 ±
0.4
0.4
2.0
3.1
0.6
1.1
06
0.7
2.7
11
0.6
2.5
1.1
0.3
• The enrichment fjclor is equal (o the surface concentration divided by the subsurface concentration.
limned sample. tPCB's expressed as Aroclor J254.
t NA, hydrocarbons not delected because of
[Duce, Quinn, 1972]
-------
TABLE 5
Instrumental Neutron A diva I ion Analysis Results
on 16 Different
Marine Fuel Oils
ppm Concentration Found
Oil Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
V
17
175
220
470
77
170
3
865
91
250
126
284
292
208
152
57
Mn
.5 <0. 30
0.043
0.020
0. 077
.6 <0.37
0.011
.8 0.002
<0. 19
<0. 39
<0. 24
<0.23
0.08
<0. 28
0.07
0.24
.5 0. 113
Na
35
7.9
1.69
44
108
2. 12
0. 36
38
25.0
19.0
7.0
12.4
85
6. 3
32
13. 3
Co
0.92
0. 39
0.62
0.41
1.84
<0.07
0.08
0. 13
0.40
0.40
0.23
0.25
0. 35
0.21
0.57
<0.08
[Guinn, 1970]
-------
TABLE 6
Oil degradation rates under varying conditions as shown by selected authors. It should be noted that seawater temperatures
around the U.K. vary from about 2*C to 16*C. The inorganic nitrogen concentration varies from <1 to around 500 /igN I-1.
Bacteria
involved
Garden soil
acrobes of
several
genera
Soil aerobes
Kind of oil
Hydrocarbon
mixtures in
common use
Emba crude
and lubricat-
ing oils
Experimental conditions
Batch culture. Mineral salts media.
Several temperatures between
20°C and 37'C
Batch culture Nilrale or ammonia
in mineral sails media. 23 "C
Summary of results
0.4-0.75 g m-* d-1 of some materials
measured at 28 "C
1 2 g m- d-1 for crude oil (45% of
added oil)
0.4 g m— d-1 for lubricating oil
Reference
Sohngen. N. L. (1913)
Zcntralbl. Bakt.
Parasitkdc. Ab. II:
37, 595.
Tausson, V. O. and
Shapiro, S. L. (1934)
Mikrobiologiya, 3:
79.
Enriched
culture
consisting
predomin-
antly of a
marine
Pscudomonas
Clear refined Probably batch culture 25'C
mineral oil Aged sea water plus 0.5% KNOi.
The oxidation of the mineral oil
was indicated by O. uptake, CO;
output and bacterial growth. The
Qio is given as about 3.0 for tem-
peratures between 0 and 40°C The
average amount of oil degraded at
25 °C is given as 1.2 X IO-IB mg per
day per bacterial cell. Hence it is
calculated that if the oil is uniformly
distributed in the water and the
population is constant at 8 X 10s
organisms mlj then the rale of oil
degradation will be about
350 g mj yr-1 at 25"C and about
36.5 gnHyr1 at 5°C.
ZoBell. C E. (1964)
Advances in Water
Poll. Res.. 3: 85.
This paper also
appears in Air &
Water Poll.. (I960),
7: 173.
Mixed American Batch culture, aerated by shaking.
culture of crudes 25*C. Sea water medium reinforced
oil oxidizing with 0.01% (N Hife HPOi. About
bacteria 1 g placed in 100ml medium. Oil
dispersed on ignited asbestos.
Between 17.8% and 98.8% by
weight of oil removed in 30 days.
Average around 45%.
ZoBell. C. E. and
Prolcop, J. V. (1966V
Z. allg. Mikroblol. 6:
143.
Natural sea Crudes and Batch culture. 18'C. Sea water
water several re- medium reinforced with NHiCl
population fined products and phosphates.
The influence of various physical
and chemical factors on oil
degradation is illustrated. The pre-
sence of nitrogen and phosphate
was shown to increase markedly the
breakdown of diesel oil in 8 weeks.
The presence of easily degraded
material 'spared' the oil. The effect
of temperature is also shown.
Gunkel, W. (1967)
Helgolander wist.
Meeresunters, 15:
210
Natural 'Atmospheric Sea water percolated through
marine residue* of columns of beach sand (median
populations Kuwait oil grain size 250/0 with natural meio
and micro fauna. Sands were lightly
or heavily oiled. 10'C.
Oxygen uptake used as indication
of degradation. Using a 'B.O.D.'
value of 5.0, the author calculates a
loss of oil from 0 09 g oil m-* d-1
to 0.04 g oil m-4 d-1 depending
upon dosing. These rates applied for
several months and accounted for
10% of the oil. Preliminary gas
chromatograms suggested the main
loss was of the alkane fraction. The
remaining 90% decayed 'immeasur-
ably slowly*.
Johnston. R. (1960).
/. mar. biol. Ass. UK,
SO: 925.
Selected Louisiana
mixed cultures crude
of oil
oxidizing
organisms
Shaken flasks with sea water en-
riched with inorganic nitrogen,
phosphates and yeast extract.
Approx 70 mg oil added to 200 ml
medium, 20°C and 30°C. Also
simulated field studies of large tanks
(900 1 ). Sea water enriched with
(N H.) SO,. 50-100 ml of crude
added Temperature ambient
J5-15-C. Seeded with oil oxidizing
bacteria.
Initial oxidation attributed to break-
down of n-alfcanes smaller than
Ci«. The initial rate was followed
by a decrease and then another
increase. Up to approx 50% of the
crude was lost No evidence of
utilization of aromatics was found.
In the large tanks the bacteria
accelerated the loss of oil and
changed its physical character.
Kator, H, Oppcn-
heimer, C. H. and
Miget, R. J. (1971).
Prevention and con-
trol of oil spills.
American Petroleum
Institute Conference,
1971. pp. 287.
[Floodgate, 1972]
-------
TABLE 7
Quantities of PAH Resulting From Combustion of One Gallon
of Commercial Gasoline (calculated from data published by Hoffman and Wynder
PAii
nig/gal
1 ,2 ,5 .6-Dibt:v anthracene
lO.ll-i.'c.izliuoran there
3,4-i*en-/pyrer.ij
J^-Gcn^anthrcire'ie
l,2-Bcic;p:i-:n^i.(hrciie
3,4-H-.'nznuor:jnihcne
),2-Ccn/.p>!cne
0.007
0.047
O.OP.8
0.172
0.175
0.179
1 131
26
17.4
32.6
63.6
64.7
66.2
426.9
Quantities of 3,4-Benzpyrene Detected in Bottom Deposits
Material
Geographic location
BaP,
Mud (42 stations)
Mud from pyster beds
Mud (17 stations)
Mud (8 stations)
Mud (12 stations)
Mud and sand
Calcareous deposits
Surface mud
Mud (218 samples)
Tyrrhenian Sea
French coast
Mediterranean coast
Villefranche Bay, France
French coast
Villefranche Bay, France
Franch coast
Italian coast
Adriatic coast
1 to 3000
90 to 2840
up to 1800
16 to 5000
nO to 1700
nil to 1700
8 to 59
nil to 2500
nil to 3400
Qi!2iit.ties of 3,T-3wii/.p>rene Detected IP Marine AnL"idls
(Values arc expressed as Aig/kt: 'Jry weight »f ar.im.il tissue)*
Kind of animals
Oysters
**
Mussels
Holothurians
"
Codfish and shellfish
Fish nad shellfish
Fish and crustaceans
Crustaceans
Isopod crustaceans
Various fishes
Invertebrates
Geographic locjt.'cn
Norfolk, Virginia
French coast
TouJon Roads, Francs
Villefranche Kay, France
Wjst coast of Greenland
** >i *» **
Saint-MaJo Bay, France
Villcfr<)nchj Bay, France
Arctic Oeean
Chpperton Lagoon
Adriatic Coast, Italy
" " "
i3aP, ^g/kg
!0 to 20
1 to 70
2 to 30
up to 2000
nil
16 to 60
3 to 125
nil to 400
ml to 230
up to 530
nil to 900
nil to 2200
[ZoBell, 1971]
-------
FIGURE 1
22
o
0
uT 20
a:
oc
UJ
a.
£ I6
0.3
u.
O
0.2
O.I
Temperolure ef woler
In surf. Averoge of five
beeches
Surface woler temperature
(After Scrippi Inititulion of Oceonogrophy)
Tor deposited on Southern Colilornla beaches
Season overoqe ol d«poi!ts collected
from s'n sampling areas
(Coal Oil Paint not Included)
/ \^GroupJt lor deposits
' * (Pebble tor)
Summer
Fall
Wintor
Spring
MAY
JUNE
JULY
AUO
SEPT
OCT
NOV
DEC
JAN
FEE
MAR
APR
MONTHS WHEN TAR WAS COLLECTED
. Beach tar deposits compared to ocean water temperatures.
[ZoBell, 1963]
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
•l&Repof$;$>•:•
•titt-v:*-- ;vrt;r
--/, TVr/e
Petroleum Weathering: Some Pathways,
Fate, and Disposition On Marine Waters.
S.^ Report Ddte
1 i
vfl.'
7. Aurhor(s)
Milton H. Feldman
P. Organization
Pacific Northwest Environmental Research Laboratory
200 SW 35 St. Corvallis Oregon 97330
• Report No.f
/0. Pro/cat No
/?. Contract/Grant No.
Environmental Mt
- - •'
fl3. Jype sf Repot 4 and
Period Covered
1$.
eatary Notes
Abstract
mechanisms of weathering of oil pollution on marine waters are
discussed. Photolysis, interactions with trace materials, and
sedimentation with particulate "Materials are considered as competitive
to other fate of petroleum mechanisms, and as having possible
ecological importance. Generation of carcinogenlcs from close
molecular precursors is considered probable.
I7a Descnptof*etroleum, photolysis, sedimentation, trace metal, ocean,
degradation, trace material, oil pollution
I7b. Ideatiiiers
Surface;,marine, carcinogenics
05-A.B.C.
IS. Availability
author
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 2O240
author
-Pacific NW Environmental Research lab.
------- |