ZoBel1, C. E. (1971), "Sources and Biodegradation of Carcinogenic
Hydrocarbons," p. 441 in Proc. Joint Conference on Prevention and
Control of Oi] Spills, June, 1971, Washington, D.C., EPA, API.

ZoBell, C. E. (1963), "Occurrence, Effects, and Fates of Oi]

Polluting the Sea," Int. J. Air and Water Pollution (1963),
pp. 173-198.

14


C. Sedimentation Processes As Weathering Fate lechanism.

The intercalation of organic molecules, including petroleum fractions,
has long been the subject of inquiry. A recent definitive

review, Whitehouse (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 oi] pollution fates.

It is perhaps obvious to state that sinking the oi] slick by application
of stearated talc or CaCO3 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


TABLE 4

Concentrations and enrichment factors of organic compounds and metals in surface microlayer samples from Narragansett Bay, Rhode Island,

Sample 1 Sample 2
Concentration Concentration
Substance ) (uBflitec) Enrichment* (up/liter) Enrichme,
ee factor _ factor
Surface Subsurface Surface Subsurface
Fatty acids 128 +26 360 «+7 36+ 10 4 19 62 +12 15+ 04
Hydrocarbons NAt NAt NAt 8S + 17 $9 + 12 La* 04
PCB'st 42+ 10 0.15 + 0.04 28 +10 0.45% 0.11 = 0.05 Bd
Lead
Particulate 144% 11 0240.17 58 61 15 + 02 0.28 0.10 54% 20
Organic 10+ 08 036+006 27% 22 14 + 06 027+ 0.12 S52 31
Inorganic 17+ 03 +05 06+ 0.2 61 + 14 37 + 10 16% 0.6
Iron
Particulate 820 +47 28 4 ones 33 7 82 + 12 43% 12
Organic 3.7% 15 0.60 + 0.33 62+ 43 SA + 23 38 + 08 13+ 06
Inorganic 28> 04 14 £02 2 . 17 +8 12 +1 142 0.7
Copper
Particulate 12% 23 0.20 + 009 36 £18 13 + 04 0.26% 0.11 50+ 27
Orgamec 56+ 05 0.19 + 0.11 29 +17 16 + 10 O11 + 0.04 53 +i
Inorganic 34% 04 3.3 403 10% 0.2 1S + 06 13 + 04 12+ 0.
Nickel
Particulate 11 + 30 02 +01 50 +30 3025 21 + 03 62+ 25
Organic 49% 26 048 + 0.33 10 + 87 5.0 + 0.6 18 + 0.7 28% 11
Inorganic Wo + 40 4 +10 08+ 0.3 a +5 6 © 2 132 03

* The enrichment factor 1s equal to the surface concentrauon divided by the subsurface concentrauon. NA, hydrocarbons not detected because of

limited sample. {PCB's eapressed as Aroclor 1254,

[Duce, Quinn, 1972]


Sections

I

II

II

Iv

INTRODUCTION

OBJECTIVE

DISCUSSION. 2. 2... eee ee eee
A.

SUMMARY
REFERENCES... 1 2. ee eee eee

CONTENTS

Radiation Chemistry
Hydrocarbon Photolysis
As Precursor to Tar In

Marine Waters... 2.2.2.2...
Carcinogenics Formation. .....
Temperature and Tar Formation...

Rate of Removal of Oi] Slicks--

Photolysis Initiated .......

Trace Material Interactions

In The Surface Layer .......

Sedimentation Processes
As Weathering Fate Mechanism

iii


Sl

Region

NW Atlantic Marginal Sea
Gulf Stream

Sargasso Sea

Total NW Atlantic

Mediterranean (Ref. 5)

Total NW Atlantic and
Mediterranean

(Morris, Butler 1973)

Estimate of Standing Stocks of Pelagic Tar in the Northwest Atlantic

it;
“OF Ole me)

V7
2.5

19.5

TABLE 1

Ocean and Mediterranean Sea

no. of
samples

16
34

58
4

99

range of
samples

(mg/m?)

0.0 - 2.4
0.1 - 9.7
0.1 - 40
0.0 - 40
0.0 - 540

mean tar
conc.

(mg/m?)
0.9
2.2

9.4

5.1
20.0

7.0

probable

error of
mean
0.2
2.4

2.8

1.3

standing stoc
(thousands of
metric tons)
2
18

66

86
50

136


TABLE 7

Quantities of PAH Resulting From Combustion of One Galion
of Commercial Gasoline (calculated from data published by Hoffman and Wynder 40)

PA mg/aal ralkg
1,2,5,6-Dibenzanthracene 0.007 26
10,11-ieaztivoranthere 0.047 17.4
3,A-Berypyrene O0.G88 32.6
1,2-Benzanthr: 0.172 63.6
1,2-Bercy 0.175 64.7
0.179 66.2
1,0-Cenzpyicne 1181 4269

+ Quantities of 3,4-Benzpyrene Detected in Bottom Deposits

Material Geographic location BaP , g/kg
Mud (42 stations) Tyrrheman Sea 1 to 3000
Mud from pyster beds French coast 90 to 2840
Mud (17 stations) Mediterranean coast up to 1800
Mud (8 stations) Villefranche Bay, France 16 to 5000
Mud (12 stations) French coast nil to 1700
Mud and sand Villefranche Bay, France nil to 1700
Calcareous deposits Franch coast 810 59
Surface mud Italian coast nil to 2500
Mud (218 samples) Adniatic coast nil to 3400

Quant-ues of 3,4-Beuzpy rene Detected in Manne Aninials
(Values are expressed as ug/ke dry weight of animal ussue)TM

Kind of avinials Geographic locatiea BeP, ug/ke
Oystcrs Norfotk, Virginia 10 to 20

“ French coast 1io 70
Mussels Toulon Roads, France 2 t0 30
Holothurians Villefranche Bay, France up to 20G0

” West coast of Greenland nil
Codfish and shellfish oe 16 to 60
Fish nad shel!fish Saint-Malo Bay, France 3 to 125
Fish and crustaceans Villefranchs Bay, France nil to 400 [ZoBel1, 1971]
Crustaceans Arctic Ozean nil to 230
Isopod crustaccans Clipperton Lagoon up to 530
Various fishes Adriatic Coast, Italy nil to $00
Invertebrates ” vo nil to 2200



compound Ser
AEMENES
A-wetHve-2-ETHYL BENZENE & 161.3
A-metave-G-eTHyh DENZENE ) 161.99
13. S-TRIMETHYL BENZENE son 164.72
A-mETHYL-2-ETHYL BENZENE oo 165.15
1-2 GerRInETHML, BENZENE og 169.35
1:2:S-TaINETMTL, BENZENE od 176.08
A-netHvL-4-PROPYL BENZENE Cy 183.30
A-neTHYL-2-PROPYL BENZENE om 184,80
2-3-vinenve-5-erwe Bon 183.58
BENZENE
x 188.20
1:2-pinerave-4-etere, y 189.40
‘BENZENE
U:3-pinerune-2-erHM oc 190.01
BENZENE
L-HETHYLINDANE ious 190.6
2-WETMYLINDANE lows 191.4
1. S-Dyneruye 2-eTHee & 190.1
1.2-pinernve-3-ETHYL 193.91
BENZENE
1:2:3.5+TETRAMETHYL oe 198 00
BENZENE
196.80
Somerere INDANE ow) 205.5
1 2.3.4-reTRAPE TAYE, or 205.04
BENZENE
1 3-pineraye-4-paorre O 206.6
BENZENE
2 2-pinernye-4-pRcere 208.5
BENZENE
TETPANYORONAPHTHALENE CO ws
MAPMIRALENES
seven CO ws
aetna OO m5
L-PE TAYE NAPHTHALENE 244.64
aipuenve (Om @) 255.2

1 Z-DIME THY, NAPHTHALENE oo
semen woman SOO)

2 G-DIng Tur, MaPHTMALeNe

TOTAL ARCRATICS

ye" ho

2
> 6.68
2

3
>#0

3

4 mas

5 18.97

6
7
7
8

oe

9 6.21

V

16.57
L
LL.
i 35.39
ey
i
id 152.89
3 85.66
4 63 43
rt) 27,40
ie
18 325
16°

610

TABLE 3

Substances isolated from Seawater Extract of Kerosene

Relative Concentration of Aromatic Species in Kuwait Out
Seawater Extracts (Slow String)

ue/t.
Benzenes and naphthalenes (Fig 1A) 657
Polar aromatics (Fig 1B) 796
Total amount of oil in water 1,453

Concentration of individual compounds

Concentration

Naphthalene . Q.2%)
2-Methy! naphthalene 15.0 0%)
1-Methy! naphthalene 18.0 (1.2%)

[Boylan Tripp 1971]


Floodgate, G. D. (1972, "Microbial Degradation of Oi1," Marine
Pollution Bulletin 3, p. 41 (1972).

Frankenfeld, John W. (1973), "Factors Governing the Fate of 0i1
At Sea," p. 485 in Proc. Joint Conf. Prevention and Control of
Oil Spills, March 13, 1973, Washington, D.C. API/EPA.

Freegarde, M. and C. G. Hatchett, Admiralty Materials Laboratory
"The Ultimate Fate of Crude 0i] at Sea." Interim Report No. 7,
October 1970.

Garrett, William D., (1969), "Confinement and Control of 0i1 Pollution
on Water With Monomolecular Surface Films," p. 257 Prac. Joint
Conf. Prevention and Control 0i7 Spills, New York, December
1969.

Garrett, W. P. (1967), "The Organic Chemical Composition of the
Ocean Surface," Deep Sea Res. 14, p. 221 (1967).

Guinn, V. P., and S. C. Bellanca (1970), "Neutron Activation
Analysis Identification of the Source of 0i] Pollution of Waterways,"
NBS. Special Pub. No. 312, 1, 185 (1970).

Hites, R. A., and K. Biemann, "Water Pollution: Organic Compounds
in the Charles River, Boston," Science, V. 178, p. 156 (1972).

Horn, M. H., J. M. Teal, and R. Backus (1970), Science, V. 168,
p. 245 (1970).

Lasaga, A. C., and H. D. Holland (1971), "Primordial O11 Slick,"
Science, V. 174, p. 53 (1971).

Kinney, D. J., D. K. Button, D. M. Schell, B. R. Robertson, J. Groves
(1970), "Quantitative Assessment of Oi] Pollution Problems in Alaska's
Cook Inlet," University of Alaska, Institute of Marine Science,
College, Alaska, Report R-69-16, January, 1970.

Koons, C. Bruce, "Chemical Composition, A Control on the Physical and
Chemical Processes Acting on Petroleum in the Marine Environment."
In Press. Gulf Coast Association of Geological Societies Prodeedings
November 1973, Houston, Texas.

Lee, R. F., R. Sauerheber, and A. A. Benson (1972), "Petroleum
Hydrocarbons: Uptake and Discharge by Marine Mussel Mytilus
Edulis," Science, V. 177, p. 344 (1972).

Lukens, H. R., D. Bryan, N. A. Hiatt, H. L. Schlesinger (1971),
“Development of Nuclear Analytical Techniques for 011 Slick
Identification," Gulf Energy and Environmental Systems Co., San
Diego, Report No. AT(04-3)-167 (1971).

12


The kind of reactions postulated are:

(1) O11 fraction (1) by {Active intermediates]
2
(2) Active intermediates ieee Auto oxidation
and products of prior
steps AT . . . .
>>> Polymerization and disproportionation
(3) Active intermediates B D . .
. _ egradation and/or synthesis by
are ucts of prior appropriate biota.

Reaction (2), polymerization and disproportionation involves the
formation of smaller molecules plus longer chain/higher H.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 CO.

but intermediate metabolic steps proceeding from a polycyclic afomatic
base can lead to carcinogenic intermediates. The work of Boylan 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 CHC 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 sunmer, 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


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 disproportionation, 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.


TABLES

Estimate of Standing Stocks of Pelagic Tar in the
Northwest Atlantic Ocean and Mediterranean Sea... ....

Heat Balance Due to Sunlight versus Latitude. .......
(a) Substances Isolated from Seawater Extract of Kerosene.

(b) Relative Concentration of Aromatic Species in Kuwait
Oil Seawater Extracts (Slow Stirring). ........

Concentrations and Enrichment Factors of Organic Compounds
and Metals in Surface Microlayer Samples from Narragansett
Bay, Rhode Island... 1. 2. ee eee ee ee ew ee

Instrumental Neutron Activation Analysis Results on 16
Different Marine Fuel Oils. ...... ee ee we ee

Oil Degradation Rates Under Varying Conditions as Shown
by Selected Authors... 2... 2 2 ee ee we eee .

(a) Quantities of PAH Resulting from Combustion of One
Gallon of Commercial Gasoline... ... 2... es eee

(b) Quantities of 3,4-Benzpyrene Detected in Bottom
Deposits ©... eee tt ee et et es

(c) Quantities of 3,4-Benzpyrene Detected in Marine
Animals. 2. 6 6 6 ee ee ee ee ee te wh ee ee

iv

15
16
V7

W7

18

19

20

21

21

21


Mertens, Edward, (private communication).

Mikolaj, P. G. (1972), “Investigation of the Nature, Extent, and
Fate of Natural 011 Seepage off Southern California," Paper No. OTC-
1549, 4th Annual Offshore Technology Conference, Houston, Texas,
May 1, 1972.

Morris, B. F. (1971), "Petroleum: Tar Quantities Floating in the
N.W. Atlantic Taken with New Quantitative Neuston Net," Science.
V. 173, p. 430 (1971).

Morris, B. F., and J. N. Butler (1973), "Petroleum Residues in the
Sargasso Sea and on Mediterranean Beaches," API, EPA, Proceedings of
1973 Conference on Prevention and Control of 0i1 Spills, Washington,
D.C., March 12, 1973.

Mosser, J. L., N. S. Fisher, C. F. Wurster (1972), “Polychlorinated
Biphenyls and DDT Alter Species Composition in Mixed Culture of
Algae," Science, V. 176, 533 (1972).

Munday, J. C. (1971), "Oil Slick Studies Using Photographic and
Multispectral Scanner Data," p. 1027-43, in 7th International
Symposium on Remote Sensing of Environment, Proceedings, Ann Arbor,
Michigan, May 17, 1971.

Noyes, W. A., and P. A. Leighton (1966), "Photochemistry of Gases,"
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
Oil at Sea," in Proceedings of a Seminar Held at Aviemore, Scotland
(1970), (Ed. P. Hepple), Inst. of Petrol. (1971).

Pilpel, N. (1968), "The Natural Fates of Oi] on the Sea," Endeavor,
V._27, (No. 100), p. 17 (1968).

Suess, Michael, Laboratory experimentation with 3, 4-Benzpyrene in
aqueous systems and the environmental consequences. Aus
(isn and Praxis, Zb1 Bkt. Hyg., I Abt Orig B 155, 541-546,

1972).

Whitehouse, Ulysses Grant (1969), "Adsorption Mechanism: Aluminositicate
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


SECTION III
DISCUSSION

A. Radiation (photolysis) chemistry, (Noyes & Leighton 1966),

(Burton & Magee 1969 et seq.) 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, 6-
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 H,0, H,0,, Ho0+FeC] 3
tetrahydronaphthalene in presence of H,0 and 05 gavé polgméric materials.
Unsaturated hydrocarbons are also absofbers atTMthe 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-genic materials.


TABLE 5

Instrumental Neutron Activation Analysis Results

Oil Number

on rn sw wn we

eer.)
anu kw nN & Oo

on 16 Different Marine Fuel Oils

ppm Concentration Found

Vv Mn Na Co
17.5 <0. 30 35 0.92
175 0.043 7.9 0. 39
220 0.020 1.69 0. 62
470 0.077 44 0.41
17.6  <0.37 108 1. 84
170 0.011 2.12 <0.07
3.8 0. 002 0. 36 0.08
865 <0.19 38 0.13
91 <0. 39 25.0 0.40
250 <0. 24 19.0 0.40
126 <0. 23 7.0 0.23
284 0.08 12.4 0.25
292 <0. 28 85 0. 35
208 0.07 6.3 0.21
152 0.24 -32 0.57
57.5 0.113 13.3 <0.08

[Guinn, 1970]


EPA 660/3—73—013
SEPTEMBER 1973

Ecological Research Series



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 (T.E.) and trace
organic compounds (T.C.) defining, T.M. = T.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 al] 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 wel] 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 oi1, 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 oi] (#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.


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 011 Slicks - Photolysis Initiated.

The rate of oxidation of hydrocarbons and nitrogen, oxygen, sul fur-
(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, alky] 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 um has about 2000 kg/km2 (1300 gal/mi2, 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


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 {photolysiss et seq.), (2) trace material
interactions, and 3) particulate (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) .

tS} carcinogenic hydrocarbon (CHC) 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.

" "metabolic atoms.

(e) trace compounds like vitamins, amino 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
gyaparently is a simple removal comparable to evaporation will be
iscussed.


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


TEMPERATURE, °C

QUANTITY OF TAR, srams/metar?

FIGURE 1

T T T T T T T T T

.
zeb Porn ae

-Temperoture o|
In surt, Averog ~ 4
beoche SO
ma
~
a
te Cr tal 4
Surtoce woter temperoture “ sek =

1a] (After Scripps Institution of Oceanography)
2 4

Tor deposited on Southern California beaches
Season overoge of deoosits collected

trom six sampling oreas

(Coal Oil Point not included)

0.2} Group! tar deposits

Summer Foll Winter Spring
} n | | i

it it 1 L 1 _
May UUSUNE JULY aus) SEPT oct nov ' DEC YAN fee =| MAR APR

MONTHS WHEN TAR WAS COLLECTED
. Beach tar deposits compared to ocean water temperatures.

[ZoBel1, 1963]


ABSTRACT

Three mechanisms of weathering of oi] 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,

ii


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 oi] industry practices is possible
without at least some investigation and understanding of these unknowns.


SECTION V
REFERENCES

Allen, Allen A., R. S. Schlueter, and Paul G. Mikolaj (1970),
"Natural 011 Seepage at Coal Oi] Point, Santa Barbara, California,"
Science, V. 170, p. 974 (1970).

Armstrong, F. A. J., P. M. Williams, and J. D. H. Strickland
(1966), "Photooxidation of Organic Matter in Sea Water by
Ultraviolet Radiation, Analytical and Other Applications," Nature,
No. 5048, p. 481 (1966).

Blumer, M. (1972), "Oil Pollution Persistence and Degradation of
Spilled Fuel Oi1," Science, V. 76, p. 1120 (1972).

Blumer, M. (1972), "Submarine Seeps: Are They A Major Source of
Open Ocean Oil Pollution?" Science, V. 176, p. 1257 (1972).

Blumer, M., G. Souza, and J. Sass (1970), Marine Biology 5, p. 195
(1970).

Boylan, D. B., and B. W. Tripp (1971), "Determination of Hydrocarbons
in Sea Water Extracts of Crude 0i1 and Crude Oi] Fractions," Nature,
V. 230, No. 5288, p. 44 (1971).

Burton, M., and J. Magee (1969), "Advances in Radiation Chemistry,"
John Wiley, NY (1969). See also M. B. et al., "Comparative Effects
of Radiation," John Wiley, NY (1960).

Duce, R. A., et al., (1972), "Enrichment of Heavy Metals and Organic
Compounds in the Surface Microlayer of Narragansett Bay,"
Science, V. 176, p. 161 (1972).

Feldman, Milton H. (1970), "The 50 Mile Ballast Oi1 Dumping
Prohibited Zone off Alaska, Reconsidered," F.W.P.C.A., Pacific
Northwest Water Laboratory, Working Paper, No. 77, October, 1970.

Feldman, Milton H. (1970), “Trace Materials in Wastes Disposed

to Coastal Waters; Ecological Guidance and Control". F.W.P.C.A.,
Pacific Northwest Water Laboratory, Working Paper, No. 78, July,
1970.

Filby, R. H., and K. R. Shah, (1971), "Mode of Occurrence of Trace Elements
in Petroleum and Relationship to 0i1 Spill Identification Methods,"
Proc. Am. Nucl. Soc. Meeting, Nuclear Methods In Environmental
Research, [ed. J. R. Vogt, T. F. Parkinson, R. L. Carter], August
23-24 1971, University of Missouri.

i}


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


TABLE 6

Ou degradation rates under varying conditions as shown by selected authors. It should be noted that seawater temperatures

°C. The inorganic nitrogen concentration varies from <1 to around 500 »gN 1”.

around the U.K. vary from about 2°C to 16
Bacteria
involved Kind of oi} — Experimental conditions . Summary of results Reference
Garden soi! Hydrocarbon Batch culture. Mincral salts media. 0.4-0.75 ¢ m= d- of some materials Sohngen, N. L. (1913)
acrobes of mixtures in Several temperatures between measured at 28°C Zentralbl. Bakt.
several common use 20°C and 37°C Parasitkde. Ab. H:
genera 37, 595.
Soit aerobes Emba crude Batch culture Nitrate or ammonia 1 2 g m= d-" for crude oil (45% of  Tausson, V. O. and
and lubricat- in mineral salts media. 23°C added oil) va Shapiro, S. L. (1934)
ing oils 0.4 g m= d~ for lubricating oil Mikrobiologiya, 3
Enriched Clear refined Probably batch culture 25°C The oxidation of the mineral oil ZoBell, C. E. (1964)
culture mineral oil Aged sca water plus 0.5% KNOs was indicated by O, uptake, CO: Advances in Water
consisting output and bacterial growth. The Poll. Res., 3: 85.
predomin- Quo is given as about 3.0 for tem- This paper also
antly of a peratures between 0 and 40°C. The appears in Air &
marine average amount of cil degraded at Water Poll., (1960),
Pseudomonas 25°C is given as 1.2 x 10° mg per 7: 173.
day per bacterial cell. Hence it is
calculated that if the oil is uniformly
distributed in the water and the
population 1s constant at 8 X 10°
organisms ml-! then the rate of oil
degradation will be about
50 g m2 syrt at 25°C and about
36.5 g m= yr” at 5°C.
Mixed American, Batch culture, aerated by shaking. Between 17.8% and 98.8% by ZoBell. C. E. and
culture of crudes 25°C. Sca water medium reinforced weight of o1l removed in 30 days. Prokop, J. V. (1966).
oil oxidizing with 0.01% (N Hi: HPO. About Average around 45%. Z. allg. Mikrobiol. 6:
bacteria 1 g placed in 100 ml medium. Oil 143,
dispersed on ignited asbestos.
Natural sea Crudes and. Batch culture. 18°C. Sea water The influence of various physical Gunkel, W. (1967)
water several re- medium reinforced with NHiC1 and chemical factors on oil Helgolander wiss.
population fined products and phosphates. degradation is ilJustrated. The pre- Meeresunters, 15:
sence of nitrogen and phosphate 210
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.
Natural ‘Almospheric Sea water percolated through Oxygen uptake used as indication Johnston. R. (1960).
marine | residue’ of columns of beach sand (median of degradation. Using a ‘B.O.D.’ J. mar. biol. Ass. UK,
populations Kuwait oi] grain size 250) with natural meio _value of 5.0, the author calculates a 3 a
and micro fauna. Sands were lightly loss of oil from 0 09 § oil m2 d
or heavily oiled. 10°C. to 0.04 g oil m2 d+ lepending
upon dosing. These rates applied for
several months and accounted for
10% of the oil. Preliminary gas
chromatograms suggested the main
Joss was of the alkane fraction. The
remaining 90% decayed ‘:mmeasur-
ably slowly’.
Selected Louisiana Shaken flasks with sea water cn- Initial oxidation attributed to break- Kator, H_, Oppen-
mixed cultures crude riched with inorganic nitrogen, down of n-alkanes smaller than heimer, C. H. and
of oil phosphates and yeast extract. Cw. The initial rate was followed Miget, R. J. (1971).
oxidizing Approx 70 mg o1] added to 200 mI by a decrease and then another Prevention and con-
organisms medium, 20°C and 30°C. Also increase. Up to approx 50% of the trol of oil spills.
simulated field studies of fatge tanks crude was lost. No evidence of American Petroleum

(900 1). Sea water enriched with utihzation of aromatics was found.

(N_H,) SOx. 50-100 ml of crude In the large tanks the bacteria

added Temperature ambient accelerated the loss of ot! and

esc. Seeded with oif oxidizing changed its physical character.
acteria.

[Floodgate, 1972]

Institute Conference,
1971, pp. 287.


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.


3} 3. Accession No.

SELECTED WATER
RESOURCES ABSTRACTS

INPUT TRANSACTION FORM
4 Title

Petroleum Weathering: Some Pathways,
Fate, and Sisposition On Marine Waters.

* Aurhor’s) Mitton H. Feldman 10. Project No.

9 Organization

Pacific Northwest Environmental Research Laboratory/!. Contract/Grant No.
200 SW. 35 St. Corvallis Oregon 97330

Type of Repost and
iPaned Covered :

5

16. Abstract Three mechanisms of weathering of of] 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 carcinogenics from close
molecular precursors is considered probable.

17a. Descrivtofetroleum, photolysis, sedimentation, trace metal, ocean,
degradation, trace material, of] pollution

17b. Identifiers . . .
Surfacei marine, carcinogenics

A,B,C.
17e. COWRR Fisio & Group 05-A,B,

18, Availabiliey Send To:

WATER RESOURCES SCIENTIFIC INFORMATION CENTER
author 28," Sed US. DEPARTMENT OF THE INTERIOR
(Page) f WASHINGTON. D. C, 20240

tseafe: author enctinte: Pacific NW Environmental Research Lab


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 (1.c.) 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 oi] 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 oi]

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.


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