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 ------- 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. ------- 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 ------- 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 ------- 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 ------- 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 ------- 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. ------- 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. ------- 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. ------- 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 ------- 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 ------- 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. ------- 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. ------- 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 ------- 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. ------- 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 ------- SECTION V REFERENCES Allen, Allen A., R. S. Schlueter, and Paul 6. Mikolaj (1970), "Natural Oil Seepage at Coal Oil 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 Oil," 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 Oil and Crude Oil 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 Oil 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 Oil 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. 11 ------- Floodgate, G. D. (1972, "Microbial Degradation of Oil," Marine Pollution Bulletin 3, p. 41 (1972). Frankenfeld, John W. (1973), "Factors Governing the Fate of Oil 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 Oil at Sea." Interim Report No. 7, October 1970. Garrett, William D., (1969), "Confinement and Control of Oil Pollution on Water With Monomolecular Surface Films," p. 257 Prac. Joint Conf. Prevention and Control Oil 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 Oil 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 Oil 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 Oil 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 Mytil us 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 Oil Slick Identification," Gulf Energy and Environmental Systems Co., San Diego, Report No. AT(04-3)-167 (1971). 12 ------- Mertens, Edward, (private communication). Mikolaj, P. G. (1972), "Investigation of the Nature, Extent, and Fate of Natural Oil 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 Oil 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 Oil on the Sea," Endeavor. V. 27. (No. 100), p. 11 (1968). 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. ------- |