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.

-------