PB84-177898
    Surface Treatment Agents for
    Protection of Shorelines from Oil Spills
    Woodward-Clyde Consultants, San Francisco, CA
    Prepared  for

    Municipal.Environmental Research Lab.
    Cincinnati,  OH
    Apr 8<2
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                                                            FE84-177898


                                                      EPA-600/2-84-085
                                                      April  1984
            SURFACE TREATMENT  AGENTS  FOR PROTECTION
                 OF SHORELINES FROM OIL SPILLS
                               by

Carl R, Foget, Robert M.  Castle,  Susan  Nsughton, James 0. Sartor
                   Woodward-Clyde Consultants
                Sen Francisco,  California  94111

                 Michael  Miller,  Philip Dibner
                      URS Research Company
                  San Mateov  California 94402

   Donald E.  Glowe, Frederick Heber,  B.J.  Yager, P.E. Cassidy
                 Texas Research Institute, Inc.
                      Austin, Texas 78767
                       Grant No.  R804639
                        Project Officer

                      Leo T.  McCarthy,  Jr.
           Oil  and Hazardous  Materials  Spills  Branch
          Solid and Hazardous Waste Research Division
     Municipal  Environmental  Research Laboratory-Cincinnati
                    Edison, Hew Jersey  08837
          MUNICIPAL ENVIRONMENTAL RESEARCH  LABORATORY
               OFFICE CF RESEARCH Af.'O  DEVELOPKtNT
              U.S. EKVIRO^ISHTAL PROTECTION AGENCY
                     CINCINNATI, OHIO  45268

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                                   TECHNICAL REPORT DATA
                            (Pbcst read Imuuctiotu on lilt rei-erw btfort c
1. REPORT NO.
                              2.
                                                            3. RECIPIENT'S ACCEf.Sl
A. TITLE AND StjOTITLE
     SURFACE TREATMENT AGENTS FOR PROTECTION OF
     SHORELINES FfOM OIL SPILLS
                                                            5. REPORT DATE
                                                           6. PERFORMING ORGANIZATION CODE
                                                                  ENT'S ACCESSION. MC,,
                                                                  4   17?89 fa
                                                             April
7. AUTHORS)
   Carl R.  Fogot, et al.
                                                            8. PERFORMING ORGANIZATION REPORT NO.
<>. PERFORMING ORGANIZATION NAME AND ADDRESS
   Woodward-Clyde Consultants
   Three Embarcadero Center, Suite  700
   San Francisco, California 94111
                                                            10. f ROURAM ELEMENT NO.
                                                                    CBKD1A
                                                            11. CONTRACT/GRANT NO.

                                                                  R804639
12, SPONSORING AGENCY NAME AND ADDRESS
   Municipal Environmental Research  Laboratory— Cin., OH
   Office of Research and Development
   U.S. Environmental Protection Agency
   Cincinnati, Ohio 45268
                                                            13. TYPE OF REPORT AND PERIOD COVERED
                                                             Final Report, 1975-1979	
                                                            14. SPONSORING AGENCY CODE
                                                                    EPA/600/14
IS. SUPPLEMENTARY NOTES
            Project Officer: Leo T. Me  Carthy (201-321-6630)
io. ABSTRACT   A literature review and laboratory tests were  conducted to provide a basis
   for analyzing the results of  previous tests on surface treatment agents, compare agent
   effectiveness, and recommend  agents for preliminary field  tests.  The surface treatment
   agents evaluated during the preliminary tests were film-forming agents, dispersing
   agents, anc? a surface collecting agent.  From the results  of  these tests, two film-
   forming agents, polyvinyl acetate and xanthan gum, a  surface  collecting agent, and a
   flowing film of water were recommended and tested during full-scale field tests at
   Sewaren Beach, New Jersey.  The results of the full-scale  field tests showed that
   polyvinyl acetate provided both beach And marsh test  plots with the most effective
   long-term protection.  The toxic effects of the various  agents on the Eastern Blue Crab
   and cord grass  (Spartina foliosa) were also evaluated.   .-•	 .

   This report was submitted in  fulfillment of Grant No. R804639 awarded to the American
   Petroleum Institute under the sponsorship of the U.S. Environmental Protection Agency.
   The API awarded a contract to Woodward-Clyde Consultants,  who, with their subcon-
   tractors, Texas Research Institute, Inc., and URS Research Company, completed the
   research in 1979.  This report covers the period 1975-1979.
17.
                  DESCRIPTORS
                                K6Y WORDS ANO DOCUMENT ANALYSIS

                                             ~fb.lD£NTIFIEfiS/OFEN ENDED TERMS
c. COSATI Fw'd/Group
   Water Pollution
   Shore Protection
   Polyvinyl Acetate
   Xanthanates
   Water
   Dispersants
18. OISTKtUUTlON STATEMENT

   Release to public
                                                Oil Spill Cleanup, Film-
                                                forming Agents, Surface
                                                Collecting Agents
  13/02
  11/09
  11/07
  07/03
  11/11
                                               19. J.ECUKIVY CLASS in
                                                 Unclassified
                                                                          21. no. OF PASC
                                               20. ££CUKITY CLASS ITTlilpc^e 1
                                                 Unclassified	
                                                                          22. 1'HICE
£PA
         20-1 (R»». <-77)   PREVIOUS EDITION is csioucre
                                              1

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                                   DISCLAIMER


     The information in this document has been funded wholly  or in part by the
United States  Environmental Protection  Agency  under  Grant  No.  R804639  to
Woodward-Clyde Consultants.   It has  been  subject to  the Agency1 s peer  and
administrative review,  and it  has been  approved for  publication  as  an  EPA
document.  Mention of  trade names or  commercial  products does  not  constitute
an endorsement or recommendation for use.
                                       ii

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                                    FOREWORD

     The U.S. Environmental Protection Agency was created because of
increasing public and  government concern about  the dangers of:  pollution  to
the health and welfare of the American people.   Noxious  air,  foul water,  and
spoiled land  are  tragic  testimonies to  the deterioration  of  our  natural
environment.  The complexity  of  that environment and the  interplay of  its
components require  a  concentrated  and  integrated  attack   on the  problem.

     Research and  development  is  that  necessary  first  step  in  problem
solution; it  involves  defining  the  problem,   measuring  its  impact,  and
searching for  solutions.   The  Municipal Environmental  Research Laboratory
develops new and improved  technology and systems  to prevent,  treat, and manage
wastewater and solid and hazardous  waste  pollutant  discharges  from municipal
and community sources, to preserve  and treat public driaking water supplies,
and to minimize the adverse economic, social, health, and  aesthetic effects
of pollution. This  publication  is one of the products of that  research  and
provides a most vital communications  link between the researcher and the user
community.

     This report describes  the  laboratory and field  research that evaluated
products and techniques for the protection and restoration of shorelines form
oil spills.  THe  report  will be  of interest to those involved  in oil spill
prevention, control, and ccuntemeasures.


                                    Francis T. Mayo,
                                    Director
                                    Municipal Environmental Research Laboratory
                                       iii

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                                    ABSTRACT


     Surface treatment  agents  for  protecting  shorelines  from  spills  were
evaluated by means of a  literati re review, laboratory tests, and  field tests.
Results of the literature  review and laboratory  tests  were used as  the  basis
for (1) analyzing the results of earlier tests on surface treatment agents for
oil spills, (2)  comparing  effectiveness of  surface treatment agents,  and (3)
recommending agents for  preliminary field  tests.  Preliminary  field tests  of
agent effectiveness,  toxicity,  and  application  techniqes  were undertaken  on
slat-marsh sections and simulated beaches.   The surface treatment agents tested
during the preliminary field tests were film-forming agents (polyvinyl acetate,
xanthum gum) and the surface collecting agents were recommended for and tested
during the full-scale field tests at Sewaren Beach, New Jersey.  In addition, a
flowing film of water was tested for effectiveness as a surface treatment agent.

     The results of  the full-scale  field  tests  showed that  polyvinyl acetate
provided both  beach  and marsh  test plots  with  the most  effective protection
against the test oils (16 fuel oil, #2 fuel oil,  and Arabian crude oil) because
it substantially decreased  oil penetration, and  it allowed surface  oil  to be
easily removed by  flus/iing.  Xanthan gum  was the  least efective  on the beach
test plots  of the  three film-forming agents,  but  it  did provide  sane beach
substrate protection.  On the  marsh test plots,  xanthan gum appeared to be the
most effective  short-term agent  for protecting  the vegetation and substrate
from contamination by Arabian  crude oil,  but it  was removed by flushing.  The
flowing film of  water provided the best protection against beach  surface con-
tamination by  oil,  but  it  tended to erode  channels in  sand  beaches, causing
uneven coverage  and allowing some oil penetration.  The  flowing film of water
was not  effective  as a  surface  treatment  agent  for  salt marshes because it
could not provide a uniform film over the substrate and  vegetation.  The surface
collecting agent was effective in confining oil under nonturbulent conditions.
Turbulent conditions  (caused  by  breaking  waves  impinging  on  the test area)
caused the confined oil  slick to break up.

     Results of  several studies  are  included as  appendices to  this report.
They are: Prelimnary Agent evaluation Tests; Dioassay of Eastern Blue Crab with
Surface Treatment  Agents;   Siedler Beach  Surface Treatment Agents Tests; and
Laboratory Investigation of Improved  Materials  for Shoreline  Protection from
Oil Spills.

     This report was submitted in  fulfillment  of Grant  No.  R804639  by the
American petroleum  Institute under  the  sponscrhsip of the U.S. Environmental
Protection Agency.  The  API awarded a contract  to Woodward-Clyde  Consultants,
who, with their  subcontractors, Texas Research institute,  Inc.,  and  UR3 Research
Conpany, ccwpieted  the  research.  The report  covers the period July, 1975 to
July, 1979, and  work was completed by October, 1979.
                                       iv

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                                  CONTENTS
Foreword	iii
Abstract	   iv
Figures	   vi
Tables	   vi
Acknowledgments. . .	vii

    1.  Introduction	    1
              Scope	    1
              Report Organization	    2
    2.  Conclusions	    3
              Beaches  	    3
              Salt Marshes	    5
    3.  Recoimendations	    7
    4.  Full-Scale Field Tests 	    8
              Test Site	    8
              Test Oils  	    8
              Agent Evaluation Procedures   ...."	   IjJ
              Data Collection	.	   11
              Agent Application Equipment	   11
              Test Results 	   15
              Discussion	   20
              SiEttnary	   30

Appendices      '.

    A.  Literature Review	   32
    B.  Preliminary Agent Evaluation Tests	   43
    C.  Bioassay of Eastern Blue Crab With  Selected
          Surface Treatment Agents	   96
    D.  Surface Treatment Agent Tests - Siedler Beach,
              Jersey, October 18 and 21, 1978	108
              D-l.  SecLbranr Sanpling Procedures	122
              D-2.  Laboratory Investigation of Itproved Materials
                      for Shoreline Protection from Oil Spills	124

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                                  FIGURES



Nuntoer                                                                 Page



   1   location of test site	    9



   2   Location of test plots in four test zones	   14





                                   TABLES



Num&er                                                                 Page



   1   Surface Treatment Agents Evaluated During Program	    2



   2   Ranking of Film-Forming Agents Evaluated During Test Program.  .    4



   3   Characteristics of Test Oils  	   10



   4   Environmsntal Conditions  	   13



   5   Surface Treatment Agent Beach Field Test: 16 Fuel Oil	   16



   6   Surface Treatment Agent Baach Field Test: #2 Fuel Oil	   17



   7   Surface Treatment Agent teach Field Test: Arabian Crude Oil .  .   18



   8   Beach Surface Treatment Agent Conparison	   19



   9   Surface Treatment Agent Marsh Field Test: #6 Fuel Oil	   24



  10   Surface Treatment Agent Marsh Field Test: Arabian Crude Oil .  .   25



  11   Surface Treatment Agent Marsh Field Test: #2 Fuel Oil	   26

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                               ACKNOWLEDGEMENTS


     Acknowledgement is  gratefully  given  for  the cooperation and assistance
provided by the following persons:  Mr.  Eugene Destefano, Director of Fublic
Works, Woodbridge, New Jersey,  for  arranging  logistic  support for the test
program; Mr. Karl  Birns,  Director of  Special  Services, New Jersey Department of
Environmental Protection, for permission  to use the  Sewaren Peach test site;
the Alameda County (California) Flood Control District,  for permission to use
the preliminary field test site at  Coyote Hills Slough in Fremont, California;
the Clean Harbor Cooperative of New York  City, Mr. M.C.  Zwirbla, Manager, and
member companies Gulf Oil, Hess Oil,  and  Chevron USA,  for providing booms for
the Sewaren Beach test site; Mr.  Maurice  Sproul, Mr. Victor Manolio, and Mr.
David Mercer, of the Mason and  Hanger Company,  for providing logistic support
and assorted equipment and for  their  active participation in the full-scale
field test program; and  Chevron USA for providing the  test oils used in both
the preliminary and full-scale  field  tests.

     The authors also gratefully  acknowledge  the support and guidance given by
members of the American  Petroleum Institute's shoreline,  subcommittee, Mr. F.M.
Smith (Chevron USA), Chairman;  Mr.  D. E.  Fitzgerald  (Atlantic Richfield Com-
pany); Mr. F.T. Jones (CITGO);  Mr.  G.P. Mulligan (Shell); Hr. J.S. Dorrler
(EPA); and Hr. W.L. Lewis (Exxon  USA),  Chairman of the Oil Pollution Prevention
and Control Committee; by Mr. Thomas  Kanney,  who served  as contract officer for
the American Petroleum Institute; and hy  Mr.  Leo McCarthy, who served as
Project Officer for the  Environmental Protection Agency.

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                                   SECTION 1

                                  INTRODUCTION
     The state of tne art for cleanup of oil-contaminated shorelines is well
developed only for sandy beaches; cleanup of other oil-contaminated shoreline
types requires extensive use of manual labor.  The procedures for protecting
shorelines from oil contamination are even less well developed and usually
consist of deploying bourns to direct oil away from a specific area.  Wind,
current, and surf action can, however, severely limit boom performance,
allowing oil to escape and causing subsequent contamination of a shoreline.


     In 1974, the American Petroleum Institute and the U.S. Envirorsrental
Protection Agency funded four laboratory projects to obtain information on
materials that might be useful in protecting beaches and salt marshes from
oil contamination.  The results of these studies (1) identified eight natural
and synthetio materials that, if applied to a beach or salt marsh, might
offer the shoreline protection from oil contamination, and (2) recormended
that the candidate agents that were identified be tested in the field under
full-scale conditions.

     The American Petroleum Institute obtained a research grant from the En
vironmental Protection Agency to continue this effort and awarded a contract
to Woodward-Clyde Consultants and their subcontractors, Texas Research Insti-
tute, Inc., and URS Research Coerpany.  The purpose of the project was to
evaluate, under field conditions, the effectiveness of the selected surface
treatment agents in protecting beaches and salt marshes from oil spills and
in assisting in the cleanup of shorelines previously contaminated by oil
spill.  Toxicity screening tests on cordgrass (Spartina foliosa) are dis-
cussed in Appendix B and c.i Eastern Blue Crab (Callinectus sapidus  in
Appendix C.

     The scope of this project involved the following:

       * Correlating data on the eight agents recorsmanded by previous studies
         into a ccsraror, baseline through literature reviews and laboratory
         testing.

       * Conducting preliminary field tests with the agents and three types
         of oil (S2 fuel oil, Arabian crude oil, and £6 fuel oil) on marsh-
         grass plots and siitralated beaches to determine the most effective
         agents for full-scale field testing.

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       * Conducting full-scale field tests by applying the agents to actual
         beach and salt-marsh areas and contaminating the areas with three
         types of oil (#2 fuel oil, Arabian crude oil, and #6 fuel oil)

       * Conducting preliminary toxicity tests of selected agents.

     The surface treatment agents that were tested during the project are
shown in Table 1.
REPORT ORGANIZATION

     The remainder of this report presents specific details and information
on the performance of the project.  Section 2 presents conclusions of the
full-scale field tests, and Section 3 states recommendations for agent use
and additional research.  Section 4 presents the results of the full-scale
field test program at Sewaren, New Jersey.  Specific data from the litera-
ture review, laboratory tests, and preliminary field tests are given in
Appendices A and B.  Appendix C gives the results of the eastern blue crab
bioassay.  Appendix D gives the results of the evaluation of surface treat-
ment agents.


         TABLF. 1.  SURFACE TREATMENT1 AGKNTS EVALUATED DURING PROGRAM
                                                   Preliminary   Full-Scale
                                                   Field Tests   Field Tests
	Agents	Laboratory	Alameda	Sewaren

Sodium silicate                           x             x

Sodium borate/sodium silicate
mixture                                   x             x

Citrus pectic                             x             x

Xanthan gum                               x             x             x

Polyvinyl acetate                         x             x             x

Flowing f.ilm of water                     x                           x

Surface collecting agent (Oil Herder)     x             y             x

Dispersant A (Correxit 7664)              x             x

Dispersant B (BP 1100-X)                                x

Dispersant C (BP 1100 KD)                               x

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                                   SECTION 2

                                  CONCLUSIONS
     The full-scale field tests of surface treatment agents were undertaken as
two  tasl
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               TABLE 2.   RANKING*  OP FILM-FORMING AGENTS EVALUATED DURING TEST PROGRAM
Film-Forminq Aqent Ranking





Agent
Polyvinyl acetate
Xanthan gum
Flowing water
Sand Beach
Oil Type
No. 6 No. 2 Arabian No.
Fuel Oil Fuel Oil Crude Oil Fuel
Short
Term
111 2
333 1
2 22 3

Marsh . . .-
Oil Type
6
Oil
Long
Term
1
2
3
No.
Fuel
Short
Term
1
2
3
2
Oil-
Long
Term
1
3
2
Arabian
Crude
Short
Term
2
1
3
Oil
Long
Term
1
2
3
* Agents are ranked in order of effectiveness  in  each test.

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SALT MARSHES


      1. Two of the ^urface treatment agents  tested,  polyvinyl  acetate  and
         xanthan  gun,  have  definite potential for application in protecting
         salt marshes from oil contonination.

      2. Polyvinyl acetate was particularly effective in protecting  the  salt
         marsh  from  contamination  by  £2  fuel  oil  and Arabian crude oil.
         Flushing of the oil frcta contaminated vegetation and riarsh  substrate
         was easier for PVA than with other agents or the control.

      3. Xanthan gun appeared to  be  a  slightly  more  effective  short-term
         (i.e., hours) agent for protecting the nvjrsh vegetation and substrate
         from contamination by Arabian crude oil.  After  a  single  flushing,
         however,   the  agent  was  largely  removed  fron  both  plants  and
         substrate.

      4. The effectiveness of the continuous film of flowing water in  marshes
         was  limited.   It  was difficult to attain a uniform water flow that
         would protect both the vegetation and the substrate.  Some protection
         was afforded the substrate, especially against the #2 fuel oil.

      5. f6 fuel oil was extremely difficult to renove frczn both  treated  and
         untreated  salt-marsh  sections.   Polyvinyl  acetate and xanthan gun
         eased the flushing of the oil fron the substrate in  ooiparison  with
         control  sections.   "Hie xanthan gun, in particular, appeared to work
         better than polyvinyl acetate in facilitating  16  fuel  oil  removal
         frcni the substrate.

Surface Collecting Agents

     Under the limiting conditions in which the beach and salt  march  surface
collecting agent tests were conducted, the following conclusions were drawn.

     The surface  collecting  agent  was  effective  in  confining  oil  under
nonturbulent  conditions.   Turbulent  conditions  (caused  by  breaking waves
inpinging on the test area) caused the contained oil slick to  break  up.   In
the  absence  of  the confining barriers used in the test, this effect may not
have occurred.  Oil washed into the marsh by turbulent conditions  was  easily
removed from the plants by low-pressure water flushing.

General

     Permit stipulations on the  conduct  of  the  full-scale  field  program,
requiring  that  all  test  oils ba contained within and roioved fron the test
area, disposed restrictions  on  ths  "real-wrld"  evaluation  of  the  agents
tested.   Because  of  this restriction a great deal of effort was expended to
ensure that oil was contained within the surrounding boons.  In  the  case  of
the  surface  collecting  agent  test,  this  constriction interfered with the
actual roschanisn of the naterial being tested, that is, tha surface collecting
agent  tended  to  drive oil away frcm tha shoreline which was counteracted by

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     Toxicity testing of eight agents on Spartina foliosa (cordgrass)
including relative comparisons of plant reaction (e.g., health)  to various
treatments made on the basis of qualitative observations arul quantitative
measurements of growth ratio were inconclusive.

Agent Toxicity

     Toxicity testing of PVA and xanthan gum on juvenile callinect.es (blue
crabs) showed that:

     1.  The acute static bioarsay successfully established 96-hour toxicity
         ranges for the two agents:  PVA (0.45% to 3%) and xanthan gum (3% to
     2.  PVA (as applied at 100%) is seemingly more toxic to first-stage
         juvenile Callinectes than is xanthan gum (as applied at 1%).

     3.  The PVA at 0.45% concentration did not have any apparent physiologi-
         cal effect on the crabs during the 96-hour test period.

     4.  The xanthan gurrt at 3% concentration did not have any apparant
         physiological effect on the crabs during the 96-hour test period.

     5.  The 96-hour TLM for PVA was 0.95%.

     6.  The 96-hour TIM for xanthan gum was 5.5%,

     7.  The PVA seemed to act like a weak acid.  The persistent low pH level
         in the 5%  tank could have contributed to the toxicity of the agent.
         Additional tests on the chemical behavior of PVA in water are
         rcconwended.

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                                  SECTION 3

                               PECOMMEN11WIONS
     Based on the fir.di.rxjs of this study, the following recaitnendations are
offered:

     1. Further research should be conducted to evaluate, under field
        conditions, other types of potential surface protection agents
        such as:

           * additional tests with surface collecting agents

           * dispersing agents

           * new film-forming agents, such as high-density, low-expansion
             foams or a polymeric high-expansion gel or foam

           * polyvinyl acetate with formulation adjectments to make it more
             readily degradable and to accelerate its drying tire

     2. All three film-forming agents should also be evaluated for effective-
        ness of protection against oil contamination on cobble and/or rock
        beaches.

     3. Laboratory tests should be conducted with new agents to define their
        operation limits.

     4. A prototype application system for beach and marsh areas should be
        designed and tests on an oil spill of opportunity using polyvinyl
        acetate as a surface treatment agent.

     5. Additional testing in salt marshes is recommended to verify tests for
        agent toxicity.  Experience gained in the preliminary work should
        permit development of refined and conclusive testing procedures.

     6. Additional acute bioassay tests of PVA in the range of 0.45% to 3%
        and xantham gum in the range of 3% to 1J?% should be performed en
        first stage blue crab juveniles.  Also, testing of post larval crabs,
        generally regarded to be more sensitive than first stage juveniles is
        recommended.

     7. Organism toxicity of oil and oil plus agents should be determined on
        crabs through additional bioassay testing.

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                                   SECTION 4

                            FULL-SCALE FIELD TESTS
TEST SITE

     The full-scale field tests were conducted at Sewaren  Beach,   located  on
the New Jersey side of the Arthur Kill,  between the PuMic Service power plant
on the north and the outlet of Snith Creek on the south (latitude   43  degrees
32  min.   N,  longitude  74  degrees  16 feet W) (Figure 1).   Sewaren Beach is
approximately 670 meters long and has been zoned a park site  by the  town  of
Vfcodbridge.   The area is a former salt marsh that has been used as a disposal
site for dredge spoils by the Corps of Engineers.  The shoreline  is  composed
primarily of gravel and coarse sand beaches interspersed with email patches of
salt marsh on the southern end.  The northern  two-thirds  of  the  intertidal
beach  area  consists  primarily  of  gravel;   the  southern  third  consists
generally of gravel in the  lower  intertidal  area  and  sand  in  the  upper
intertidal area, with scattered salt marsh in the foreshore area of the beach.

     The land areas surrounding the Arthur Kill are heavily industrialized and
densely populated.  The Arthur Kill is an industrial waterway and  is a heavily
traveled conponent of  the  New  York  Harbor  complex.   Extensive  dredging,
landfilling, and bulkheading havs eliminated rcuch of the natural shoreline and
wetlands.

     Sewaren Beach is located along a section  of  the  Arthur  Kill  that  is
subject  to frequent oil spills.  In 1973 the Arthur Kill from Linden to Perth
Amboy was the scene of 147 separate oil spills, ranging in  size  from  a  few
liters  to  336,£^0  liters  of  oil.   Twenty-nine of the 147 oil spills were
greater than 378 liters and 11 were greater than 3,785 liters (USCG  Polliition
Incidence  Importing System).  Because of the frequent oil spills  in the area,
the sand and gravel on Sewaren Beach contain residual weathered oil from  past
spills.

TEST OILS

     Three types of oil wera used to test the  effectiveness   of  the  surface
treatment  agents.   The  three  oils  present  a  wide  spectrum  of physical
characteristics and are representative  of  the  wide  variety  of  crude  and
refined   oils   that   could   be   accidentally  released  onto   the  water.
Characteristics of the three test oils are given in Table 3.
                                      8

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•
                                                                                              i-ju^iy. 4< n«-n i
                                             Figure  1.   Location of test site.

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                   TABLE 3.   CHARACTERISTICS OF TEST OILS
                            t2 Fuel Oil      86 Fuel Oil
  Characteristic	Min	Max	Min	Max	Arabian Crude

Gravity (°API)              32.1   42.8     11.0     16.9          35

Viscosity

  Kinematic (100°F, CS)      2.35    3.0      ~       —            8

  Furol (122°, SFS)          —     ~      101      250

  Pour point  (°F)            —      0       —       35          -20

Sulfur content (wt, %)       —    0.35      —      2.73          2.5

Aromatics content  {wt, %)    48     48

C. cut and lighter  (wt,  %)   —     —       —       —           2.88
 AGENT EVALUATION FKOCEDURES

      The full-scale field tests vere divided into two parts  for the  tv>o tasks.
 The  durability  of  ths  film-forming  surface  treatment   agents   vas tested
 initially.   Each candidate agent  was applied to a marsh and  beach test plot in
 the  upper   intertidal zone of the test site.  Each test plot was observed and
 photographed during a tidal cycle and was sanpled to determine the   length  of
 time  each   candidate  -?gent  remained  on  the  shoreline surface as a viable
 surface treatment agent.

      Ihe second and more ijinportant part of the test program   involved  testing
 each  candidate surface treatment agent for its ability to protect a shoreline
 surface vhen subjected to contamination frcrn three different oils.   This  part
 of the program was further subdivided into two parts:  film-forming  agents and
 a surface collecting agent.

 Film-Forming Agents

      Test plots and control plots were laid out along a  selected portion  of
 the  upper  intertidal zone of the designated rnarrh and beach test zones.  Each
 test plot was coated with a different candidate surface treatment agent,   and
 the  control  areas  were  left  in thair natural state.  Each beach test plot
 measured approximately 9.2 square  maters.   Each  marsh  test plot  measured
 approximately 1.2 by 3 craters.

      Beams  ware deployed in ths water arojnd the perimeter of tha test  zone.


                                       10

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Just  prior  to  the  tidal ebb, a specified volume of oil was released en the
water inside the boomed test zone upwind fron  the  test  plots.   The  ebbing
tidal  action  and  prevailing  wind  deposited  the oil on the surface of the
shoreline test and control plots.  After the tide had receded  fron  the  test
and control plots, data ware collected to assess the performance of each agent
in protecting the shoreline fron oil contamination.   1'ae  conditions  of  the
test  plots  were compared with the conditions of the oil-contaminated control
plots.  Following data collection, half of each oeach test  and  control  plot
and  the entire area of each marsh test and control plot on which oil remained
vKjre flushed with a low-pressure water system to determine the ease with <.'.hich
oil  could  be  removed fron an agent-coated surface.  The other halves of the
beach test and control plots were cleaned to  determine  if  an  agent-treated
surface increases physical cleanup effectiveness.

Surface Collecting Agents

     The surface collecting agent was tested separately because it would  have
affected  the filn-forming agent tests on adjacent plots.  Boons were deployed
in the water around the perimeter of the test zone, and the test oil  (Arabian
crude) was released prior to tidal ebb inside of the bocmed zone.  The surface
collecto:: was applied to tha substrate of the beach and marsh test plots using
an 18.9-liter hand-held garden sprayer, and it was also sprayed into the water
ahead of the approaching oil  slick.   Data  collection  was  conducted  in  a
similar manner as for filir-forming agents.

DATA OXIECTION

     Rvatography  was  the  major  data-collection  technique  and  was   used
primarily  to record observations permanently.  Photographs were taken of each
test and control plot before and after each test to determine  the  degree  of
oil  contamination.   Depth  of  penetration  of  oil  into  the test plot VQS
determined by cutting sections across a test plot, taking  filter-paper  blots
at   7.6-on  and  15.2-on  depths,  and  examining  the  filter  papers  under
ultraviolet light to determine the  presence  of  oil  by  its  characteristic
fluorescence.

AGEOT APPLICATION EQUIPMENT

     Four types of equipment were  used  in  applying  the surface  treatment
agtnts during the full-scale field tests:


       * hydraulic sprayer

       * rotary pump

       * water spray system

       * garden sprayer
                                       1.1

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Film-Forming Agent Application

     Because a hydraulic  sprayer  was  successful  in  applying  film-forming
agents  in  the preliminary field tests, a hydraulic sprayer was used to apply
xanthan gun and polyvinyl acetate for the first day of testing.   Problems with
the  hydraulic  sprayer  occurred when tba high pressure of the  sprayer caused
substrate disturbance of the beach test plots,  and the nozzle of  the  sprayer
clogged  as the agents were being applied, causing lengthy delays.  Therefore,
the hydraulic spraying system was replaced by an alternative  spraying  system
for  the  rest  of  the tests.  The alternative spraying system  consisted of a
high-volune, positive-displacement, reversible rotary punp powered by a  small
(5.85-hp)  diesel engine.  The punping rate was 64.4 liters/ minute at 1.75 to
2.1 kg per sq on (25 to 30 psi) at 1000 rpm.  A  5.1-cm  suction  hose  and  a
1.6-on discharge hose with a hand-activated, adjustable piston-grip nozzle was
used to apply agents.  This conbination provided a spray  that  gave  an  even
coating  to  the  shoreline substrate over a reasonable amount of time.  There
was no disturbance of beach substrate.

Water Film Application

     The water-spray system was fabricated in the  field;   two   3-mater-iong,
3.8-an-diameter PVC pipe sections were joined by a 60-cm-long, 3.8-cm-diameter
fire hose.  A 5.1-cm trash punp (60-100 liters per minute) was  used  to  punp
salt water from a suction hose into the water-spray system.  The 15-meter-long
suction hose was suspended beyond the surf zone, below the water  surface  and
above  the  bottom,  to  keep  oil  and  bottom  sediments  from  entering the
water-spray  system.   Initially,  fan  spray  heads  from  underground   lawn
sprinkling  systems  were  inserted  in  the  PVC  pipe (30.5 cm apart).  This
provided a fine spray that  created  a  continuous  film  of  water  over  the
substrate.   These  spray  nozzles  clogged  with  the algae and the suspended
sediment entrained by the purg? intake within several minutes. Holes measuring
1.2  on in diameter were then drilled into the PVC lips (30.5 cm apart).  This
allowed water to flew freely frcrn the holes, forming a flowing-water film over
the beach and marsh.

Surface Collector Application

     An 18.9-liter low-pressure (1.75 kg per  sq  cm,  25  psi)   hand-cparated
garden sprayer was used to apply tha surface collecting agent.

TEST PROCEDURE

     Table 4 gives the testing sch.»3ule and the  environmental  conditions  at
the  test  site  at  the times of agent application for the 4 days of testing.
Figure 2 shows the test area, including ths four test zones and  the  specific
locations of the beach and mrsh test plots.

     Xanthan gun and polyvinyl acetate were  applied  (using  the  application
techniques previously discussed) to tha beach and marsh test plots between lew
tide and nddtide and allowed to dry.  The water-spray si's ten was turned on  at
high  tide  and before tha test oil was spilled.  Tna surface collecting agent
was applied to tha b&ach and narsh test plats and to the water in front of the


                                      12

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                                   TABLE 4.   ENVIRONMENTAL CONDITIONS
Environmental
Conditions at
Agent Application
Time of agent application
to beach plots
Xanthan gum
Polyvinyl acetate
Water
Surface collecting agent
Air temperature
Wind speed
Wind direction
Water salinity
Height and time of high tide
Clou'd cover
Beach type
Area of beach plots
#6 Fuel Oil
May 21, 1977

0830
0900
1100
24-26°C
Less than
8 kph *
SSE
25-30 ppt**
1.4 m, 1100
Hazy
Sand with
some gravel
9.2 sq m
#2 Fuel Oil
May 23, 1977

0930
0955
1226
24-26°C
Less than
8 kph
SSE
25-30 ppt
1.3 m, 1226
10%
Sand and
gravel
9.2 sq m
Arabian
May 24, 1977

0950
1000
1315
24-26°C
8-16 kph
SSE
25-30 ppt
1.4 m, 1315
Hazy
Sand and
gravel
9.2 sq m
Crude Oil
May 25, 1977

1407
29-32°C
8 kph
SSE
25-30 ppt
1.4 m, 1407
Hazy
Sand and
gravel
9.2 sq m
*   kph = kilometers per hour.




**  ppt = parts per thousand.

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                         P • Potyvlnyl Aceute
                         X • Xmthtn Gum
                         W • Water Sprty
                         C • Control
                         H • Surtacs/Collectlng Agtnt


-
              Plywood Barrier
   •Mewl Stake      /Boom

-a	——»
Plywood Barrier

       Shoreline
             *2M^
         Durability Test
                                    X   P
                                                  test Zone
                                                  Arabian Crude
                                                                              Sand

                                                                              Sand and Gravel

                                                                            3 Gravel with Sand

                                                                            y Gravel with Sand and Mud

                                                                              SaltMatsh
                                       Figure 2.   Location  of  test plots  in  four test  zones.

-------
approaching oiJ slick after the test oil was spilled.

     The test oils were spilled manually from an 1.8.9-liter  bucket  and  vere
allowed to drift with the wind and current toward the test plots.  Because the
high tide did not fully cover some marsh test plots,  oil  was  forced  toward
these  plots  by simulated wave action generated by a low-pressure water-spray
system.  Ihis procedure was followed for.each test oil and continued  until  a
uniform  coating  of  oil  covered  the  vegetation and substrate.  It was not
possible to contaminate each plot entirely,  but  enough  of  the  plots  were
covered to produce the desired results.

     After completion of the tests, all test zones were cleaned manually  with
sorbents  and  low-pressure  water  flushing.   The beach test plots vere also
cleaned mechanically by a front-end loader,  which  removed  the  contaminated
beach material.

TEST RESULTS

Beach Tests

     The major observations made and  data  collected  during  the  full-scale
tests  at  Sewaren, New Jersey, are given in Tables 5, 6, and 7.  Included are
;data for each test, including the  agent-applicaticn  method,  the  volume  of
agent  jsed,  agent  density  (volume/sq  meter)  on  each te^-t plot, the time
required to apply the agents, the time required for the film-forming agents to
dry on each test plot, the percentage of oil coverage on each test plot after
tidal deposition of the oil, and ccmnents on the performance of the agents and
the results  of  flushing  oil  frcm  the agent surface.  Drying tiroes of the
film-forming agents varied;  pools of polyvinyl acetate and xanthan gum formed
in depressions  on the bsach and took longer to dry because they were thicker
than the rest of the film.

     Flushing of oil frcm the film-forming agents was  first  attempted  using
sea water  through  a 3.8-on fire hose attached to a 5.1-cm centrifugal trash
pump.  tfcwever, the pressure and volume  of  water  was  too  great,  and  the
fire-hose  stream broke up the polyvinyl—acetate film and flushed oil into the
sand substrate.  A 1.6-on hose with an adjustable pistol-grip nozzle  attached
to the  same  trash purrp  was then tried.   It successfully flushed oil fron the
agent's surface without rupturing the film.                                   :

     The effectiveness of each agent compared with  a control in protecting the
beach  frcm  oil  contamination is given in Table 8.  Ibllowing each test, the
presence of oil on the surface of  the  test  plots and  the  degree  of  oil
penetration  were determined by visual observation  and by a sampling technique
eniploying ultraviolet light.  In this technique, vtiich was developed  by  TRI,
Whatiran f 1 filter paper was used to blot water froa the baach sediments at tha
surface and at 7.6-on and 15.2-cni depths.  Each filter paper was then examined
under  ultraviolet  light for the characteristic fluorescence of the test oil,
and a semiqaantitative determination was mada of the amount of oil present.  A
subjective assessment of  tha degraa to \vhxch oil covered each plat was made by
visual  observation.   In  the   Arabian   crude   oil   test,   xanthan-gua,
polyvinyl-acetate,  and flcwing-water-sheat test plots wsrc significantly less


                                      15

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        TABLE 5.    SURFACE'TREATMENT  AGENT BEACH  FIELD TEST:  $6  FUEL  OIL
                                (volume  spilled: 114  liters)
                                                         JVi*_'l't To;; t •:•
Application
rethod and
s;-ray pressu
Volume of agent
A-lvnt applica-
tion density

Tiv.c required
to spray agent
{nin or sec)

Agent drying
tine
                       viiiv 1 "fro La to
Hydreulic sprayer at
42 kg/sq cm (600 psi);
also poured atj&iit en to
test plot*

3*7 liters sprayed;
3.8 liters poured

1 liter/sq neter
10-15 ran
1.5-2 hr
                                             Xnnthan
                                                                                            Control
Hydraulic sprayer  at   Continuous water flow
•S2 kq/sq en 0o      at «iO-100 lit«_-rs/r:in
psi); aim injured
agent onto test plot*
                                           15  liters sprayed;
                                           19  liters poured

                                           3.7 iiters/sq meter
                         20 min
                         1 hr
                                                                 3-5 liters/sq ir*,-ter
Oil coverage on
test plot after
t€Et

Coments
Results of
surf act:.
flushing
lOOt of area covered
by tide
                 Agent  film in lover
                 intertidal area of
                 test plot was dis
                 solved by tide before
                 it had properly dried
Flushing with a fire
hose ruptured poly-
vinyl acetate filn,
causing oil to pene-
trate beach substrate.
Flushing with garden
hose removed rost of
the oil froci poly-
vinyl acetate filn.
Film regained stained,
however.
40-501 of area cov-
ered by tide
                         Agent filn in lower
                         intertidal area of
                         test plot vas dis-
                         solved by tide
                         before it had
                         properly dried
Flushing reiroved
only some oil from
surface
20-30% of area covered   100% of area
by tide                 covered by tide
Flowing water eroded
channels in sane/
sections of test plot,
Oil did not adhere or
penetrate in areas
where water flowed but
did contaminate areas
where water film did not
cover due to ero&ion
chanrels

                       Oi1  not  removed
                       by  flushing
* The volume of aqonts  sprayed by the hydraulic sp.-ayinq system was  too  small to use on a lan;e s-:.ile.
  Therefore, a different, spraying system was used for other tests.
                                                   16

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                   TABLE 6.  SURFACE TREATMENT AGENT BEACH FIELD TEST:  #2 FUEL OIL
                                     {volume spilled: 190 liters)
                                                        Agent Tested
                    Pglyvinyl Acetate
                                              Xanthan Gum
                                                   Water  Spray
                                                                                            Control
Application
method and
spray pressure
Volume of agent
used

Agent applica-
tion density

Time required
to spray agent
(rain or sec)

Agent drying
time

Oil coverage on
test plot after
test

Comments
Results of
surface
flushing
Viking gear pump and
1.6-cra hose with gar-
den spray nozzle at
1.4-2.1 kg/sq cm
(20-30 psi)

23-30 liters
2.S-J.3 liters/
sq meter

1 rain
1-1.5 hrs
100% of area covered
by tide
Host of oil flushed
from film by garden
hose spray
                       Continuous water flow,
                       60-100 liters/min
Viking gear pump and
1,6-cm hose with
garden spray nozzle
at 1.4-2.1 Jtg/sq on
(20-30 psi)

57 liters
6.2 liters/sq rooter    3-5 liters/sq meter
50 sec
                          45 min
loot of area covered
by tide
                       100% of area covered
                       by tide
                                                 Where water was  flow-
                                                 ing  on  test plot there
                                                 was  no  oil contamina-
                                                 tion (sheen in other
                                                 area");  channel  ero-
                                                 sion a  problem
100%'o£ area cov-
ered by tide
Very little oil
removed with flush-
ing by garden hose
spray
                                               Oil not removed
                                               by flushing

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                   TABLE  7.  SURFACE TREATMENT AGENT  BEACH FIELD TEST: ARABIAN CRUDE OIL
                                           (volume spilled: 95 liters)*

Application
method and
spray pressure
Voluno of agent-
used
Agont applica-
tion density
Time required
to spray ayent
(itiin cr iec)
Agent drying
time
Oil coverage
on test plot
after test
Corinents
Results of
surface
flushing

Polyvinyl Acetate
Gear pump and l.b-cm hose
with gard«n spray nozzle
at 1.4-2.1 k-3/sq cm
(20-30 pal)
15 Uteia
1.6 lite:s/sq meter
SO soc
1-2 nr
loot of area covered
by tide
Polyvinyl arofate had
loss surface oil con-
tamination than x an than
gum but more than flow-
ing water film
Successfully removed
almost all oil from

Xanthan Gun
Gear pump and 1.6-em
hose with garden
spray nozzle at 1.4-
2.1 ky/sq cm (20-30 psi)
57 liters
6 liters/sq meter
50 sec
1-1.5 hr
100\ of area covered
by tide
Morn oil on xanthan
gum tost plot than
Polyvinyl acetate and
flowing water film
Flushing removed some
oil from surface
Agent TVstod
watrr Spray Control
Continuous water flow
at OC-100 litcrs/min
~
3-5 liters/sq motor
— — • — —
•-
Less than 101 of area 100% of area cov-
covered by tide cred by tide
Flowing water film test
plot appeared to hava
least surface contanlna-
tion; loore gravels in
this tost plot, so ero-
sion vas less and there-
fore oil contamination
was less
Flushing did not
remove any oil

Surface? Collector
Sprflyed onto shoreline-
and into vjtnr ahead of
ap,jro. ching oil 9lic!:
1 liter
—
5 mi p.
—
100^. of area covered by
tide


* Tha surface collector was tested separately using 38 liters of Arabian crudo oil.

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TABLE 8.  BEACH SURFACE TREATMENT AGENT COMPARISON
Oil
*6 Fuel
#6 Fuel
#6 Fuel
#6 Fuel
IS Fuel
K6 Fuel
ft 6 Fuel
»6 Fuel ,
86 Fuel
#2 Fuel
#2 Fuel
82 Fuel
«2 Fuel
»2 Fuel
»2 Fuel
«2 Fual
It2 F\sel
#2 Fuel
Arabian crude
Ar&bi&n crude
Arabian crude
AraJaian crude
Arabian crude
Arabia*! crude
Arabian crude
Arabian crudo
Arabian cru?i«
Arabian crude


Agent
Polyvinyl acetate
Xanthan gum
Water
Polyvinyl acetate
Xanthan gum
Water
Polyvinyl acetate
Xanthan gum
Water
Polyvinyl acetate
Xanthan gum
Water
Polyvinyl acetate
Xanthan gum
Water
Polyvinyl acetate
Xanthan gum
Water
Polyvinyl acetate
Xanthan gusn
Water
Polyvinyl acetate
Xanthan gum
Water
Polyvinyl acetate
Xanthan gum
Water
Surface
Collecting
figsat
Sample
Surface
Surface
Surface
7.6-cm cross-section
7.6-cm cross -section
7.6-cra cross-section
15.2-cm deep
15.2-ca deep
15.2-cm deep
Surface
Surface
Surface
7.6-cm cross-section
7.6-cm cross-section
7.6-cm cross-section
15. 2-cm deep
15.2-cm deep
15.2-cm deep
Surface
Surface
Surface
7.6-cm cross-section
7.6-cm cross-section
7.6-cm cross-section
15.2-cm penetration
15.2-crm penetration
15.2-cm penetration
Surface
7.6-cm cross-section
15.2-cra penetration
Presence of Oil (Comparison to Control)
Visual Observation
Ultraviolet Lictht Sanies (Surface Only)
Better Sarae Horse Better Some Worse
X X
x x
x x
X
x
X
X
x
X
X X
X X
X X
X
X
X
X
X
X
X X
X X
X X
X
X
X
X
X
*
x x
X
X

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contaminated by oil than the  control  plot.   Hawever,  surface  sampling  by
filter-paper  blotting  of  these  test  plots  indicated that the presence of
hydrocarbons was equivalent to or greater than that of the control.   This  is
because  the  ultraviolet-light  detection  technique  do&s  not  discriminate
between high and low levels.

     Tho beach-test results indicated that polyvinyl acetate was  superior  in
preventing   oil   from   penetrating   tha   beach  sediment.   Although  oil
contamination of the polyvinyl-acetate surface was greater in some casea  than
for  other agents, it proved to be the agent that could be cleaned most easily
by flushing with a low-pressure water  system.   The  most  difficult  oil  to
protect  the  beach  against was 12 fuel oil;  only polyvinyl acetate provided
protection against $2 fuel oil penetration.

     The surface collecting agent initially was very successful in  preventing
Arabian  crude  oil from reaching the beach test plot.  The surface collecting
agent  formed a barrier in the water in front of the test plot  and  drove  th3
advancing oil slick back against the containment boom that surrounded the test
zone.  A water stream from a fire hose vas used to hold the oil away from  the
containment  boon.  After approximately 20 minutes, breaking waves impinged on
the  test zone, causing the contained oil slick and chemical barrier  to  break
up into numerous small oil slicks, some of vAiich came ashore contaminating the,
test plots.  Without the containment barrier, the surface collecting agent may
have held the slick offshore effectively.

     Beach testa of the  durability  of  tha  film-forming  agents,  polyvinyl
acetate  and xanthan gum, were also conducted during the full-scale field teat
program.   Xanthan  gum  and  polyvinyl  acetate  were  each  applied   to   a
10-square-mster  test  plot  in  the upper  intertidal zone of the test site at
application densities of 6 liters per sq meter for xanthan gun  and  3  liters
per  sq  mater  for polyvinyl acetate.  The xanthan-gun film was intact (i.e.,
maintained  film  integrity)  after  one  tidal  cycle,  but  had  essentially
disappeared  except for an occasional patch after the  second tidal cycle.  The
polyvinyl acetate proved much  more  durable  and  was  still  intact  at  the
          1 of tha test prog*^1 four days and eight tidal cycles later.
 DISCUSSION

 Protection Effectiveness

      The effectiveness of surface  treatment agents   in protecting  bsach  and
 salt  marsh  areas   from  oil  contamination varied with the type of oil spilled
 and the type of beach.

 Balyvinyl Acetate —
:      Of tha  four   agents evaluated,  polyvinyl  acetate  provided  the  most
 effective  protection from the  three  test oils.  The use of polyvinyl acetate
 substantially decreased oil penetration  into the beach substrate  as  compared
 with the control, although surface contamination was similar to the control  in
 two of the three tests.   Balyvinyl acetate dried to a firm, serd-pliant  film
 that  could  be pesled almost intact frcm the beach surface. The agent can  be
 applied full strength (without dilution  or mixing)  at a rate of  approximately


                                       20

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10  sq  meters  per  minute  with a rotary purtp system.   However,  before it is
effective as a film-forming agent, polyvinyl acetate requires time to dry.  If
it  is  still  liquid  or sard-liquid when it contacts water, it will dissolve
into the water col inn.  Once dried, the polyvinyl acetate film is very durable
against  tidal  action and small waves.  liowever, this is only true as long as
waves  do  not  impijjge  on  the  beach  above  the   upper   limic   of   the
polyvinyl-acetate  film,  where  the  wave backwash can get under the film and
destroy it«? integrity.

Xanthan Gun—
     Xanthan gun was less effective  than  either  polyvinyl  acetate  or  the
flowing-water  film  in  protecting the beach test plots from oil penetration,
although in the t6 fuel oil test there was less surface oil  contamination  of
the  xanthan-gun-coated  test  plot than of the polyvinyl-acetate-coated plot.
Xanthan gum was applied in a 1% water solution (by  weight)  with  the  rotary
pump  system,  at  a rate of approximately 10 sq meters per minute (similar to
polyvinyl acetate).  It dried somewhat more rapidly than polyvinyl acetate  to
a soft, jellyliXe film.  Like polyvinyl acetate, if water contacts xanthan gun
before it dries, it will  dissolve  into  the  water  cclurai.   A  xanthan-gura
protective film will last for approximately one to two tidal cycles before its
integrity is lost.  Xanthan gun is cortnercially sold as a dry powder (used  in
drilling  mud)  and does not dissolve easily, requiring mechanical stirring to
effect a solution.  The xanthan-gun powder must  be  sifted  as  it  is  added
slowly  to  the  vortex  of  the  water  or  it  forms  clumps.   It  required
approximately 10 minutes to mix 113.6 liters of 1% xanthan gum solution.

Flowing-Water Film—
     A flowing film of water was  less effective than  polyvinyl  acetate,  but
somewhat  more  effective than xanthan gum in protecting beach test plots from
oil contamination.  Of all the agents tested, the water film provided the best
'protection from surface oil contamination, but it allowed more oil penetration
into the beach substrate than polyvinyl acetate.

     The flowing  film of water, applied at a rate of 3  to   5  liters  per  sq
naeter,  tended  to  cause  channel-type  erosion on sandy sections of the test
plots.  This erosion  resulted in  an uneven  distribution  of the  water  film
:(i.e.,  water flowed  in the channels in the sand).  The high spots between the
channels were not covered by tha  water film, and thay became contaminated  by
oil.    If  channelization  had  not  occurred (as would be the case on gravel,
cobble, or rock beeches), the flowing-water film would have  been an even  more
effective protection  agent.  A recurring problem with the flowing-water systan
was clogging of the water distribution pipes and outlet holes  by  filamentous
algae and sadiment picked up by the water punp suction line.

Surface Collecting Agent

     The surface  collecting agent provided an effective chemical barrier  that
prevented  oil  from  reaching  the  shoreline until wave action disrupted ths
contained oil slick,  allowing seme oil to be carried ashore.   The  inner  oil
boon  surrounding the  test  area vras  only 5 to 8 rceters  from tha high tide
lines.  Ihis close boundary may have interfered vjith  the  evaluation  of  tha
surface   collecting   agent.   Within  seconds  after  applying  tlie  surface


                                      21

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collector, the oil slick contracted into a narrow band against the inner boctn.

     A water stream from a fire lK>se was used throughout the test to hold  the
oil SJ.ick away from the boon.  Hcwever, the contained oil slick was not broken
up until breaking waves passed through the test  area.   Once  the  slick  was
disrupted  into  small  oil  slicks  or spots, the v/ater stream and prevailing
winds helped carry seme of tlie oil ashore.

Oil-Contamination Sampling

     The  ultraviolet-light  detection  technique  used   to   determine   the
penetration  of the agent by a test oil is extremely sensitive to the aromatic
hydrocarbons present in oils, especially light  fractions.   As  performed,  a
blot  sample  is  taken  from  the beach on a VSiatman #1, 9--cm-diameter filter
paper.  This filter paper  absorbs  aromatics  if  present  in  even  a  small
quantity.   Subsequent  examination  of  the  paper under short-wave (2500 A )
ultraviolet light vd.ll show a characteristic fluorescence only in the area  of
test paper contacted by the oil.

     This  test  is  semiquantj.totive  in  nature.   It  will  not  accurately
determine  quantitative  amounts of oil penetrating a beach, but will show the
degree of presence or absence of the oil.  Also, the source of  oils  detected
;is  not  specific  to  those  spilled.  Any contamination present in the beach
strata fron earlier spills may be  detected.   Test  samples  taken  from  the
Sewaren  Beach  test  site  prior  to  agent testing in  fact showed detectable
levels of oil.

     The following conclusions can be nde from the results of the blot  tests:

       * All beach samples examined showed  the  presence  of  oil  under  the
         surface prior to the test series.  Surface examination showed no oil.

       * Comparison of visually observable surface contamination to  blot-test
         penetration   samples   may   not   correlate   because  of  blot-test
         sensitivity and the colorless nature of light components of the oils.

       * General trends of effectiveness can be determined from  the  combined
         results of visual and ultraviolet observations.

Effectiveness of Surface Oil Removal                                          ;

     The degree to which the xanthan-gun  and  polyvinyl-acetate-ccated  beach
test plots could be cleaned of surface oil contamination was evaluated for the
three  test  oils.   This  evaluation  was  undertaken   to  determine  if  the
agent-treated  surface  affected  tho  effectiveness  of cleanup  operations.
Low-pressure water flushing  was  employed  to  clean  oil  from  the  agent's
surface.   In  all  three  cases,  the polyvinyl—acetate film was cleaned more
effectively than the xanthan-gun  film.   The  fuel  oil that  was  the  most
difficult  to  flush  was  #6  fuel  oil;   very  little was removed fron the
xanthan-gun surface and an oil stain remained on  the  polyvinyl-acetate  film
after flushing.
                                      22

-------
     A brief test was performed on the polyvinyl-acetate and xantlian-gun  test
plots  to determine if the use of these film-forming agents would make cleanup
of oil-contaminated beaches by heavy equipment easier.   A  small  rubber-tired
front-end  loader,  using  its powered bucket as a scraper, dragged the bucket
across each beach tost plot.  The  xanthan-gxrn  film broke  up  and  did  not
enhance  removal.   The  polyvinyl-acetate  film  was  peeled  from  the beach
surface, making surface cleanup easier.

Salt Ffarsh Tests

     Each test plot was exposed  to  approximately  one-eighth  of  the  total
volune  of oil spilled.-  There were four marsh test plots tested with each oil
and, depending on the total voluwe of oil spilled, each plot was exposed to 12
to  15  liters.  The results of tie marsh tests are sliown in Tables 9, 10, and
11.

     All of these test results are  based  on  observations  made  during  and
shortly  following  che  application  of  agents  and  oils.   In  the tables,
short-term effectiveness refers to observations made during  and  immediately
following  each  test.   long-term  effectiveness  is  based on a composite of
observations node each day for 3 days after a  particular  test.   Agents  are
ranked  according  to their relative effectiveness,  for the Arabian crude oil
test, the ranking ranged from 1 to 3 and compared the agents with each  other.
An   additional  evaluation  was  made  in  order  to  determine  whether  the
agent-treated test plots produced results better than,  worse than, or the saoie
as the control test plot.

#6 Fuel Oil-
     Four 1.2- by 3-neter marsh plots of Spertina altemi flora were marked off
for  testing  with  16  fuel oil.  Approximately 14 liters cifbil contaminated
each marsh plot.  The test plots consisted of a control plot, a  plot  treated
with  approximately  10 liters of polyvinyl acetate, a plot treated with 30 to
35 liters of xanthan gum, and a plot that used a continuous water film as  the
.surface  treatment  agent.   Because  of initial problems with tha application
system, the polyvinyl acetate and xanthan gun vrere applied  by  both  spraying
and pouring the agents onto the marsh plot.  Table 9 summarizes the results of
this test.

'     Xanthan gum appeared to provide the roast  effective  protection  for  tha
short terra (iinnediately following contamination).  Oil was easily removed from
the substrate by flushing with low-pressure water.  This is in contrast  to  a
fair  to  good flushing result in the polyvinyl-acetate-treated plots and faiv
removal from the  control  plot.   Extensive  adherence  of  the  oil  to  tha
vegetation  was  observed  with  all three agents and the control, with little
distinguishing differences.  The xanthan gun was essentially 10-3%  removed  by
lorf-pressure  flushing on both the vegetation and the substrate.  Observations
of the test plot the day after the test revealed little or no agent present.

     Ihe water-spray  system  did  not  provide  complete  protection  because
obtaining  a uniform flow over the substrate and the vegetation was difficult.
The primary effectiveness of the water spray was  on  the  substrate,  but  as
noted,  it  was limited.  Another prdbloa with the water-spray system occurred


                                     ; 23

-------
                               TABLE  9.   SURFACE  TREATMENT AGENT MARSH  FIELD TEST:  #6 FUEL OIT,
                                                     (volume spilled: 114 liters)
to

Ease of
Oil Removal
Soil by. Flushing
Agent
Folyvinyl
acetate




Xar.than
9Uffl


Control





Penetration Substrate
Pone Fair to qood
observed rciroval:
required
extensive
flushing

None Good re-
obtfcined


*one Fair re-
observed moval;
patches
difficult
to flush
Duration of Protection
(Nonturbulent 1
Vegetation
Poor removal i
extensive
oil ,1'lher-
encei approx-
imately 50-75*
remained
Poor removal;
adherence


Poor removal;
extensive
adherence


Degree cf Agent
Removal by Flushing
Substrate
Integrity of
film disrup-
ted; approx-
imately 50-
751 remained

Most or all
removed
after flush-
ing
N.A.




Response to Waves
(Turbulent)
Vegetation
Eome film dis-
ruption; Croat
still remained



Most of agent
flushing


N.A.




Corwicnts
Relative
Natural Deterioration Ktfetliv»ne» Comparison
>5f Aicnt (After Flushing) Short
Substrate
Slow; approx-
imately 501
still visible
after 3 days


Rapid; agent
rapidly re-
moved by waves
and tides
N.A.





Vegetation Term
Very slow) none 2
observed dur-
ing test; peel-
ing off in 1-2
days

Rapid removal 1
and tides


N.R.





Lonq to
Tern Control
1 Better than
control




2 Better than



-





                          Unlimited
                                            Splashing has a ten-
                                            dency to deposit oil
                                            behind spray system
rrovcetion wai not complete) difficult to
obtain a uniform flow; primary effective-
ness on substrate
                                                                                                                           No difference

-------
                    TABLE 10.   SOBPACE TREATMENT AGENT MARSH FIELD TEST:  ARABIAN  CRUDE  OIL
                                                  (volume  spilled:  95  liters)
i—— ——•*—-»


Age/ jit
Polyvinyl '
ace Cat a




Xanthan
gum







Control



-««,«^r,-.«*«fcr — :

Soil
Penetration
None to lim-
ited; lacK
of penetra-
tion may
reflect
completeness
None to lim-
ited; lack
of penetra-
tion nay
reflect film
completeness



Yes; par-
ticularly in
upper 2-4
cm
*.***..... 	 *.,,, — , — - — ««-^^,-. — «
£aa« of Oil Removal
by Flushing
Substrate Vegetation
Fair to good Nearly complete
renewal.; de-
pendent upon
aucta.cc Ir-
regularities

Fair to good Nearly complete
removal F
dependent
upon surface
irregulari-
ties? rUght-
ly better
than poly-
vinyl acetate
Only fair Fair to good
rorrtoviLi
only on
surface
;.„.,. ™r^..--~.<..- 	 .jr. «;££=,:=, 	
Oaqrifo of A'lant
npirovftl by Flushing
Sufcstr'Ste Vegetation
Integrity of ^omo Tilm di»-
film disrup- ruptionr mo.it
tedj 50-751 atill
rcTr>ai^cA T?:r>ai»tf-d


Most of agent Most or all
removed by of aqent rc-
flushirgi moved rap-
idly by waves
«md tid&s




N.A. N.A.



Duration of Protection Response to Waves
(Wonturhulent) (Turbulent)

* J<*
-------
                             TABLE  11.  SURFACE TREATMENT AGENT MARSH FIELD TEST:  #2 FUEL OIL
                                                  (volume  spilled: 190  liters)*
N)


Agent
Poly vinyl
acetate



Xanthan
gum




Control





Soil
Penetration
None to lim-
ited; film
v<:ry com-
plete, lim-
ited pene-
Nonc to lim-
ited; but
oil may
penetrate
during
flushing
Yes





nf 1 DAIHAU. 1
by Flushing
Substrate
Good; most
oil easily
flushed out


Fair; oil
m«y pene-
trate dur-
ing flushing


Poor i only
oil on aur-
face
removed

Duration of Protection
(Nonturbulent)
Water spray


Unlimited




Von* tat ion
Good; most oil
easily
flushed cff


Good; shiny
appearance
reduced or
disappears


Fair to good;
shiny leaves
indicate oil
still present
after flushing

Removal bv Flushing
Substrate
Integrity of
film'dis-
ruptedr 50-
75% remained

Most of
agent
removed



N.A.




Vegetation
Integrity of
film dis-
rupted; 50-
75* remained

Most or all
of agent
removed by
flushing


N.A.





flelauve
of Anent (After Flurhina) Short
Substrate
Slow; approx-
imately 50%
of agent re-
mained after
3 days
Rapid; agent
not flushed
rapidly re-
moved by tides
and waves

N.A.




Yea-nation T*rm
Slow; agent 1
began to peel
off in 1-2
day*

Rapid i agent 2
not flushed
rapiJly re-
moved by tides
and waves

N.A.




Lcnq to
Tern Control
1 Better than
control



3 Better than
control




-




Responses to Waves
(Turbulent)
Splashing has A
doncy to deposit
behind spray

ten-
oil

Protection wae
Comments

not complete; difficult to 3
obtain a uniform flowi pr^niry
ness on substrate; works better
ef foctive-
than on *6

2 Better than
control

fuel oil, especially to limit substrate-





penetration



      * S'rcaence of thin fllas of oil was extremely difficult to detect visually on both plants and luhstrato.

-------
during periods when large waves were generated by passing tugboats.   The waves
had  a  tendency  to  transport  and  deposit the oil behind the flowing film,
partially negating the effect of the film.

     Flushing with iG^pressure salt water caused disruption of film integrity
on  the  substrate of the polyvinyl-acetate plot;  approximately 50% to 75% of
the film remained.   Most  of  the  film  remained  on  the  vegetation  after
flushing,  and  the  cordgrass retained its brittle texture.  After one to two
days natural deterioration by waves, wind,  and tide began  to  cause  peeling.
Approximately  50% of the polyvinyl acetate was still visible on the substrate
after three days, although it was slowly hydrolyzing.

     No substrate penetration by 16 fuel oil was observed for  either  treated
or  control  marsh plots.  This was due primarily to the high viscosity of the
oil and the low porosity of the substrate.

     Each film-forming agent was ranked  in  terms  of  its  effectiveness  in
protecting  the salt marsh fron contamination by 16 fuel oil.  The xanthan gun
was ranked first because of the slightly better results obtained when flushing
the  substrate.   Polyvinyl  acetate  was  ranked ahead of the flowing film of
water because of the problems with the oil depositing behind the spray  system
during periods of high waves.

     In comparison with the control plot, use of  the  polyvinyl  acetate  and
xanthan  gun  proved more effective than no protection at all.  In particular,
removal of the oil fron the substrate was enhanced by using  the  two  agents.
The  water  film  was  also  slightly better because it prevented the oil fron
adhering to areas where the vater was flowing.  Because of the- nonuniform flow
on  substrate and vegetation and problens with tha waves depositing oil behind
the spray, the water-spray plot  was  considered  little  different  frcm  the
control plot.

Arabian Crude Oil-
     Five 1.2- by 3-neter marsh plots of Spartina were  used  to  conduct  the
tests   with  Arabian  crude  oil.   In  addition  to  the  polyvinyl-acetate,
xanthan-gum, control, and water-spray plots, another plot was tested using the
surface  collecting  agent.   Table  10  summarizes the results of the Arabian
crude oil test.

     Each marsh plot was exposed to  approximately  12  liters  of  oil.   The
pal/vinyl  acetate  and the xanthan gun were applied with a rotary purnp.  More
of each agent  (approximately 15 liters of polyvinyl acetate and 57  liters  of
xanthan  gun)  was  used  in  this  test.  The water-spray system was the same
system used in the #6 fuel tests.                                             :

     Xanthan gum and polyvinyl  acetate  provided  the  most  effective  marsh
protection of all the agents tested, but xanthan gun appeared to work slightly
better than the polyvinyl acetate in enhancing flushing of the  oil  frcsn  the
substrate  (similar to tha 16 fuel oil tests).  Both agents were successful in
providing nearly  casplete  protection  for  the  vegetation  fron  oil  after
flushing;   removal  of oil from the substrate and vegetation was only fair to
'gocd.cn the control plot.  This indicates the effectiveness.of  the  polyvinyl


                                      27

-------
acetate and xantban gun as surface treatment agents.

     The water-spray system did not provide complete protection because of the
lack  of  uniform  water  flow  over  the substrate and the vegetation.  Y&ves
generated by passing tugboats transported and deposited oil behind  the  spray
system.   Water  spray  was most effective on the substrate in vAiich the water
flow prevented penetration of the substrate and adherence to the vegetation.

     Flushing  wirh  low-pressure  water  spray  caused  diuruotion   of   the
polyvinyl-acetate film on both the substrate and vegetation, especially on the
vegetation.  Ihe brittle texture of the plants indicated that most of the film
still  rar*ained on the vegetation.  After three days, approximately 50% of the
polyvinyl acetate remained on  the  substrate,  indicating  the  slow  natural
deterioration  of the agent.  Ihe leaves snowed signs of the polyvinyl acetate
peeling off after one to two days.

     Xanthan gua was easily flushed from both  the  marsh  substrate  and  the
vegetation  imaediately  following  contamination  by  the  oil.  The residual
xanthan gum disappeared rapidly  after  one  tidal  cycle.   This  shows  that
xanthan gun does not provide any lung-lasting protection.

     Polyvinyl acetate and xanthan gun appeared  to  prevent  significant  oil
penetration  into  the  substrate.  Observations under natural and ultraviolet
light indicated that penetration was extremely limited.  In contrast, the  oil
penetrated  the  upper 2 to 4 era of soil in the control plot.  Ihus, polyvinyl
acetate and  xanthan  gum  did  provide  protection  against  significant  oil
penetration  ccn^ared  with tl*e control plot.  Ihe water spray system appeared
to prevent penetration in those areas of ths plot where  the  water  flow  was
continuous,  but  areas  left unprotected ware affected in a manner sJinilar to
the control plot.

     Xanthan gun was ranked as the best short-term  surface treatment agent for
Arabian   crude  oil  because  it worked slightly better tlian polyvinyl acetate
when the  oil was flushed  fron the svabstrate.  Over  the  long  terra  (a  3-day
period),  polyvinyl  acetate  proved  the most effective because it persisted.
The water spray system was ranked third  because  of ths  limited  protection
affbrdad.

     The  surface collecting agent was tested  using  Arabian  crude  oil  only.
The  application  rosthod  consisted  of  sprayitig approximately 1 liter of the
agent  into the water ahead of the approaching oil.   In calm water,  the  agent
kept   the oil  from  advancing  toward  the marsh  plot, contracting the slick
seaward against the inner bocm.  Turbulence   caused by  vjaves  broke  up  and
dispersed the  slick,  and  s:me  of the  slick washed shore.  Cnce in droplet
form,  attempts to reunite the slick with more of the agent were  unsuccessful.
In addition,  the  oil  droplets  were  difficult  to recover with the typa of
polyethylene sorbents used.

$2 Fuel Gil—
     Tha  £2 fuel oil tests were  conducted  using   four  1.2-by-3-W2ter  marsh
plots.    Using  the  rotary puntp, approximately 23  liters of polyvinyl acetate
wsre sprayed on one plot and 57 liters of  xanthan gixn on another.   Ihe  other


                                      28

-------
two  plots  were a control and the water-spray section.  In all,  190 liters of
12 fuel oil ware used in this test, which meant  that  each  marsh  plot  (and
beach  plot)  was  exposed  to  an  average of approximately 24 liters of oil.
Water was used to force the oil onto the salt marsh because of the  relatively
low  tide.   Consequently, as in the other tests, only the outer marsh fringes
were exposed to the #2 fuel oil.  Table 11  summarizes  the  results  ot  this
test.

     In contrast to the 16 fuel oil and Arabian  crude  oil  tests,  polyvinyl
acetate  was found to be the most effective agent in protecting the salt marsh
fron #2 fuel oil contamination.  Most of the oil was readily flushed from  the
substrate  and  vegetation  immediately following contamination.   Flushing the
xanthan-gun-treated  plot  appeared  to  enhance  oil  penetration  into   the
substrate  by  removing  the  protective layer of the agent.  This was not the
case with the polyvinyl-acetate-treated plot.  Polyvinyl acetate  appeared  to
provide  an  effective  protective  film.   The  control  plot  had  extensive
substrate penetration.

     Both polyvinyl acetate and  xanthan  gum  were  effective  in  preventing
accumulation  of  the  oil  on  vegetation.  After flushing, the shiny or oily
appearance had been significantly reduced or  had  disappeared.   The  control
plot,  on the other hand, still appeared shiny even after flushing, indicating
the persistent nature of the oil.

     Flushing  the  polyvinyl-acetate-  and  xanthan-gum-treated  plots   with
low-pressure  water  caused  the polyvinyl-acetate film to be disrupted on the
svibstrate and most of the xanthan gum to be flushed from  both  tha  substrate
and  vegetation.   These observations are similar to those for the 16 fuel oil
and Arabian crude oil tests.  The  natural  deterioration  of .both  of  these
agents  was  also the same as that observed in tha other tests;  the polyvinyl
acetate was persistent, affording at least 50% protection over a 3-day  period
on  both  substrate  er»l  vegetation,  while  the  xanthan  gum  had  all  but
disappeared after one tidal cycle.

     The water-spray system did show scaie premise in preventing oil  substrate
penetration  in those areas where water flow was uniform.  However, as before,
the protectioii was not. complete because of the inability to achieve a  uniform
,flow  on  the  irregular, substrate.  The water-spray system did appear to work
better with the f2 fuel oil than with either the 16 fuel oil  or  the  Arabian
crude  oil  because  of  the lighter nature of the oil.  large waves did cause
transport and deposition of sane of the oil behind the  spray,  but  this  was
observed in all oils tested.  Little protection '-as provided to the vegetation
except near the base of the plant.

     The three marsh plots protected by surface treatment agents were  not  as
contaminated  as  the  control  plot.   The most effective agent over both the
short and long term was polyvinyl acetate.  By providing an effective  barrier
after  drying,  and  consequently  maintaining at least 50% of the film over a
3-day pariod, polyvinyl acetate shows premise as a  surface  treatment  agent.
Xanthan  gufn  prevented significant oil penetration during the short term, but
upon flushing and removal of ths agent, oil that raiainad or was  rexntroduced
in  the next tidal cycle was able to penetrate the substrate.  Ebr this reason


                                      29

-------
the water-spray system, which can be left in operation  for  long  periods  of
time,  was  ranked above  xanthan gum as a long-term agent for marsh protection
from #2 fuel oil.

SUMMARY

     Of all agents tested,  polyvinyl acetate shows potential for providing the
best  overall  protection  from  all oils tested.  The #6 fuel oil and Arabian
crude oil tests suggest that xanthan gun works, best as a short-term agent  and
polyvinyl  acetate  best   as  a  long-term  agent.   For  12  fuel oil spills,
polyvinyl acetate appeared to  be  both  the  best  short-term  and  the  best
long-term  agent  to  use.   Over Ihe long term, the water-spray system appears
more  effective  against   #2  fuel,  oil  than  xanthan  gum  because  of   the
recontaminatLon problem encountered when xanthan gum is flushed.

     Polyvinyl acetate was more  persistent  than  xanthan  gun  on  both  the
substrate and marsh vegetation.  Xanthan gum had almost completely disappeared
after flushing and one tidal cycle.  Polyvinyl acetate was still at Least  50%
present on the substrate  and 50% to 75% present on the vegetation 3 days after
application.  Because the water-spray system could be  used  continuously,  it
would have to be considered the most persistent of any agent tested.  However,
because of the irregular topography of the marsh, a uniform water film was not
possible.  Ihis was especially true for the vegetation;  it was very difficult
to spray the entire plot so that all  plants  were  covered.   Therefore,  the
primary  effectiveness of  the water spray was on the substrate, and its best
use was against t2 fuel oil.                                                  ;

     The surface collecting agent was tested  with  Arabian  crude  oil  only.
Under   nonturbulent  conditions  the  surface  collecting  agent  effectively
prevented oil from coning ashore when it v.ss applied  just  in  front  of  the
advancing  slick  and to the marsh.  When wave-induced turbulence occurred the
contained oil slick broke up into small spots and the collective effect  could
not  be  reestablished  by  reapplications  of  the  collecting  agent and the
vegetation  became  contaminated.   The  oil-absorbing   properties   of   the
polyethylene  sorbent  were  affected  by the surface collecting agent and oil
adherence to scrbent vas impaired.  However, the  oil-contaminated  vegetation
was  easily  cleaned by low-pressure flushing and the surface collecting agent
appeared to reduce oil adherence to marsh plants.

Protection Effectiveness

     Four major  criteria ware  applied  in  the  evaluation  of  the  relative
effectiveness of polyvinyl acetate and xanthan gun:


       * degree  of substrate penetration by the oil

       * ease of removal of the oil by flushing

       * rotcwal of agent by flushing

       * natural degradation of the sgent over tima


                                  .•;-..  30    .  ..

-------
     The  last  three  criteria  were  used  in  the   evaluation   of   agent
effectiveness  on the marsh substrate and vegetation of Spartina alterniflora.
Since no agents were applied to the control plot,  only  penetration  and  oil
removability could be used as criteria.

     The water-spray system and the surface collecting  agent  were  evaluated
according  to  criteria different from those for polyvinyl acetate and xarithan
gum because of the nature of the  application  and  the  rneans  of  protection
afforded.  Each is designed to prevent oil frcra reaching the marsh grass.  The
criteria  used  to  evaluate  these  agents  was  their  effectiveness   under
nonturbulent and turbulent water conditions.

Modifications

     Modifications will be necessary  to  make  the  water-spray  system  more
effective in preventing marsh contamination.  TVte spray should be nore uniform
in  order  to  protect  both  the  vegetation  and  the  substrate  from   oil
contamination.   The  system should be designed in such a way tl«at the nozzles
or water openings cannot be clogged by sediment picked up by the intake hoses.
A  solution  to  both problems may be provided by a water diverter placed over
the open holes in a pipa.  If such a system could  be  designed,  water  spray
might prove to be an effective, efficient, and inexpensive means of protecting
salt marshes.  However, if a spill threatened a long expanse of  slioreline,  a
spray system would require a rather elaborate distribution systaa.  Deployment
of such a system would be another problem.

     For applications of polyvinyl acetate or xanthan gum on a  larger  scale,
development  of  a  higher-volume  application   system  may be necessary.  The
experience gained using the rotary pump indicates that such a system could  be
designed.

     A polyvinyl-aoetate  formulation  that would  decrease the  drying  time  on
wet marsh substrates and vegetation should be investigated.  In the event of a
spill, it may be necessary to have tha agent sprayed on and dried  in  a  short
period  of  time.   'Jhis  would ba   particularly   ijTgportant  under cloudy sky
conditions.  VSien the  sky is overcast,  tha  temperature  cool,  or  a  slight
drizzle   falling,   drying   time  for   the  polyvinyl  acetate   is  extended
considerably.  Rilyvinyl acetate must cure and acquire a  plastic  consistency
to provide marsh protection.
                                       31

-------
                                  APPENDIX A

                               LITERATURE REVIEW


SURFACE TREATMENT AGENTS

     A literature survey was  conducted  by  Texas  Research  Institute,   Inc.
(TRI)  to  provide  a  basis  for  analyzing  the results of previous tests  of
surface treatment  agents  and  comparing  their  effectiveness.    Sources  of
information  included the final reports of four previous API-sponsored studies
(by Exxon, Shell, and Tracer), other reports, technical product bulletins, and
personal connunicationa with suppliers and otlier informed individuals.  It was
frequently impossible to objectively ccnpare the agents and methods  used  in
the  previous  work because of different testing techniques.  Iherefore, vAiere
possible, estimates and judgments made  by  TRI  on  the previous  work  ware
substituted for hard data so that relatively conplete data  on  each agent could
be presented and compared.

     The nine surface treatment agents reviewad are  listed below.   (In  the
initial phase of this study 10 surface treatment agents ware suggested for tha
literature review.  The tenth agent,  polyvinyl  acetate with  a  degradation
accelerator,  was  to  have  been  developed  through an expanded scope of the
program.  This was not undertaken.)

       * polyvinyl acetate (Borden Polyco 694)

       * xanthan gum (Biopolymar 9700)

       * citrus pectin

       * Microooecus cerificans

       * sodiun silicate  (waterglass)

       * borate-silicate mixture

       * surface collecting agent

       * dispersing agents

       * water

     All of the surface treatment agents were conpared  (using  data  compiled
fron the literature review) for nechanisn of action and effectiveness  on  the
                                      32

-------
substrates on  which tney were tested  and for  limitations on  use imposed by
climatic factors and  environmental impact.;.  A surraaary of  the results of the
literature survey is given in the following paragraphs and shown in Table A-l.

Polyvinyl .ficetate

     Polyvinyl acetate is available in a 55% aqueous suspension  that  can  be
sprayed without dilution from a spraying system.  For an effective solid film,
the coating roust dry to ollow the film to  cure.   This  means  that  ultl-nate
solidification  will  not  occur  in  wet  weather.   The cured film is highly
effective in preventing oil staining or penetration;  it is quite  stable  and
lasted  for  several  days under the wave action of the test, conditions.  When
sprayed, the material gives a milky-white  color  to  the  test  beach.   Upon
drying,  the  film  is  clear  and  firm;   rocks  and  wood appear varnished,
towever, the film will turn white if it becanes wet.

Xanthan Gum

     Polysaccharide/xanthan gun is a high-molecular-veight biopolyroer produced
by  fermentation by the microorganism Xanthomonas campestris.  It is available
commercially in dry form or in a  concentrated  solution.   In  tests  it  was
sprayed on as a 0.5% aqueous solution and allowed to dry.  Xanthan gun forms a
"soft" film because it is swollen with water.  Such a hydrophilic film is  not
attractive   to  oil  staining  and  penetration.   However,  because  of  the
hydrophilic nature of the film, it is easily washed away.  Exxon reported that
most  of the film was washed off by wave action within an hour.  It was tested
on river rocks and marsh grass and was judged to be  effective  in  protecting
them against oil contamination.

Citrus Pectin

     Polysaccharide/citrxis pectin  is a coiplex carbohydrate with limited water
solubility  but  with  water-attracting  groups.   Ihe  mechanism of action of
citrus pectin is similar to that of  the  xanthan  gum.   A   1%  solution  waa
sprayed  on  river rocks and marsh grass in the lab tests.  Ihe advantages and
disadvantages of citrus pectin as veil as the test results are essentially the
same as those for xanthan gum.

Borate-Silicate Mixture and Sodion Silicate

     Borate-silicate mixtures and  sodiun silicate  were investigated separately
by  Siell  Developisnt Company.  Both vrere  found to be effective in protecting
rocky beaches.  S\ell did not reccnroend borates  because  of  reports  of  its
toxicity  to  aquatic flora.  In Shell's testa with sodium silicate and sodiua
borate, l%-3% solutions of each ware sprayed  on   scale  beaches.   Ihe  agent
.dried  to  forra an irorganic film,  lha film was not attractive to oil but was
readily wet by water and was effective in protecting recks, but not sand.   To
be  effective,  the  film must have time to dry;   this limits its application.
However, when silicates and borates are sprayed on sand wet with ocean  water,
they  form  a  soft  gelatinous film that ray be effective in protecting sarrfy
beaches.  This approach was not fully investigated.  Ibe silicates form highly


                                      33

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                       TABLE A-l.    SUMMARY OP  RESULTS OF LITERATURE REVIEW OF  SURFACE AGENTS
Agent Typo
                flechani sm
                                    Form/Application _
                                                                      Possible LiMitatlons
                                                                                                     Sand
                                                                                                                      r e v i pus  1 ny e »t i gat 1
                                                                                                                         Rock«       •  "Marsh Gracs
 Folyvinyl
 acetate
Surface
collecting
agent
Dispersing
agent
Xanthan
Citrus
pectin
Sotiite-
silicate
mixture
                   Synthetic polymer/cone. (55%)
                   aqucoun suspensions; sprayed
                   on,  high-prossuro. airless
                   sprayer; available dry

                   Long-chain alcohols in organic
                   solvent (watar insoluble)
              Solid film
Has greater
spreading force
than oil: liquid
rnonomolecular
layer
Adjusts inter-     Nonionic detergent/aqueous
facial surface     solution  (6%)
tepsionj dovulops
micelles of oil
in water
              Soft polar film
Soft polar filn
                  liprayod on, dilute (0.5»)  aque-
                  ous solution; available a* dry
                  pcvder or concentrated solution

                  Sprayed on, dilute (1\)  aqueous
                  solution; available ai dry
                  powder
Solid film (if     Inorganic coating, diluted (1-3%)
cured)              oquooun solution; sprayed on
                                                             color, rainy/freer-   Effective
                                                     ing weather, must have 1 hr
                                                     to dry before it is effective
Short duration* loss of of*
fectiveness, might nood
continuous supervision
                Effective in  lab
                and beach tests
                                                    Must be applied directly to    Not tested
                                                    oil, large volume required
                                                     Short  duration, 1 hr drying    Not tested
                                                     time necessary
Short duration,  1 hr drying    Not tested
time necessary
                                                    Toxiclty?, pit, drying tiiw     Not  effective
                                                                                                                     Effactive
                                                                                                                                       Not tested
Effective in lab   Not tested
and beach tests
{less effective
on dry rocks)
                                                                                                                    Not tested
                                                                                                                    Effective on
                                                                                                                    dry rocks
                                                                                                                    rocks but less
                                                                                                                    effective than
                                                                                                                    x*nth«n gun

                                                                                                                    Uff-ctivo
                                                                                                                                       Not tested
                                                                     Possibly
                                                                     effective
                                                                                                       Effective en dry   Possibly
                                                                                                                                       effective
                                                                                                                                       Not touted
Sodiun
silicate
Solid barrier
(if cured)
Kicrococcus   UnJcnown
cerificans
Water film    Liquid  film
                  Inorganic coating,  dilute  (1»)
                  aqueous solution; sprayed  on

                  Frecze-dried,  <3*)  aqueous sus-
                  pension; sprayed on,  garden
                  sprayer


                  Sprinkler systeca
Toxicity?, pH,
necessary
drying tin*
                                                     Not commercially available,
                                                     large preparation effort.
                                                     half life, drying
                                                                  Continual application re-
                                                                  quired (countercurrent) ,
                                                                  equipment costs
                                                                                                 Not  effective
                                                                                                 Not  tested
                                                                                                 Not  tested
                                                                                                      Effective
                                                                                                                         Not testod
                                                  Effective on dry   Not tested
                                                  rorXa, less ef-
                                                  fective than
                                                                                                                                       Not tested
                                                                                                                    Not tested

-------
alkaline solutions, which may be.an environmental problem.

Micrccoccus Cerificans

     The  soil  bacterium  Hicroooccus  oerificans  was  cultered   by   Exxon
researchers  and  tested in three forms - live, freeze-dried, and spray-dried.
Only the spray-dried form could be seriously considered because the other  two
pose  storage problems.  The spray-dried material was applied to rocks as a 3%
aqueous solution and  was  moderately  effective  in  protecting  against  oil
contamination.   Its mechanism for protection was not explained.  The material
was not effective in cleaning rocks previously contaminated with  heavy  oils.
Microcoocus cerificuns is not available in ccranercial quantities.  "Riis, along
with its  lack  of  effectiveness,  essentially  eliminated  it  from  further
consideration as a surface treatment agent.

Surface Collecting Agent

;     A surface collecting agent is highly effective in limiting the  spreading
of  oil over water by forming a mononolecular layer on the water surface.  The
chemical is sprayed directly onto the beach or into the water between the  oil
and  the teach.  It may be applied in wat weather, but it solidifies at 2.2°C,
which places  a  low-teanperature  limit  on  its  use.   It  is  effective  in
protecting  sand  and  wat beaches, but less effective in protecting dry rocks
and wood.  It also  appears  effective  in  cleaning  previously  contaminated
beaches.   Its  protection  is of short duration, and it must be applied after
each high tide.

Dispersing Agent

     A nonionic dispersing agent uses the agitation of the  surf  to  mix  the
dispersant  with  oil  and  water  and  its  use  is rarely limited by weather
conditions.  Ihe mechanisa of action depends  on  the  dispersant  interacting
with oil to form dispersed oil micelles.  It was reported that this dispersant
is thought to be effective because it disperses the oil and  carries  it  back
out  to sea in the undertow before it can adhere to the beach.  It is possible
that almost continual application will be required.

Flowing Film of Water

     All of the API reports  on  chemical-agent  shoreline  treatment  methods
mentioned  that  oil  doss  not  stain  wet  beaches  or  rocks.  Indeed, most
contamination of beaches occurs when oil is stranded  by  receding  tides  and
left  on  the  upper  intertidal  zons.   This  would  suggest  the  use of an
oleophobic mechanien of shoreline protection - wetting all surfaces to form an
oil-repelling  liquid  film.   A  sprinkler  system  could  be  used to keep a
continual countercurrent of water wsttirig a shoreline  and  washing  oil  back
into  the surf.  Although this method has not been evaluated specifically as a
surface treatment agent, a flowing  film  of  water  shows  sons  premise  for
protection of shorelines from oil contorrtination.
                                      35

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INFLUENCE OF CLIMATIC CONDITKXCS

     Table A-2 details the influence of climatic conditions  en  each  of  the
surface treatment agents.  Judgments by TRI were based largely on the previous
laboratory experiments and logical extrapolations from these experiments.  For
instance,  rain  is obviously detrimental to materials that must dry to form a
film or that are quite soluble  and  easily  washed  away.   Low  temperatures
(freezing)  prevent  the  spraying  of aqueous solutions and the curing of the
film-forming agents.  Likewise,  low  temperatures  prevent  the  use  of  the
organic-solvent-based  surface  collector  because  it solidifies below 2.2°F.
Thus, none  of  the  surface  treatment  agents  considered  here  is  readily
adaptable to cold climates.

     Tidal and wave action is especially detrimental to the collecting  agents
and  to  the  more  soluble  agents,  such  as  the  polysaccharides, but aids
dispersing action.  Hence with some agents treatment will be needed  at  least
after each tidal cycle.

     High winds are a problem for all agents because they interfere with spray
application.

EMVTICNMHrcAL IMPACT OF AGENTS

     Table A-3 presents the probable  environmental  impact  of  each  of  the
surface treatment agents.  The "Appearance" colunn refers to the visual effect
and feel of the agent on  the  shoreline,  i. e. ,  whether  it  modifies  the
appearance   and   texture  of  the  shorelline  enough  to  be  aesthetically
unacceptable.  Toxicity data vcere taken from published reports  and  technical
information  and  include references both to organisms on the shoreline and to
people who apply the agent.  An additional factor in toxicity is ths secondary
effect  of  the  agent.  For example, if the coating is impern?eable to air and
water and if the agent is  not  toxic,  subsurface  species  can  exist.   The
surface  collector  tested  is  listed  as  low in toxicity because only small
quantities are allowed by regulation to be used;   the  concentrated  solution
requires  care  and  protective  clothing  for  the  application process.  The
toxicity of borates and silicates is sonewhat questionable;   however,  it  is
doubtful that their toxicity is high enough to be of concern once the film has
cured.

     Estimates of the duration of the agents on the shoreline after  the  need
:for  shoreline  protection is over are based largely on laboratory experiments
done in the previous studies.  Thus it is impossible to accurately predict the
duration on a natural shoreline subjected to sisi, wind, rain, surf, tides, and
other factors.  The solid film-forming agents might last for several  days  or
even  weeks.   The  soft film-forming agents and surfactants would probably be
washed away by surf action within hours.

'APPLICATION TECHNIQUES,

     In the previous studies, agents ware either sprayed or poured on tha test
substrates.   All  the agents except polyvinyl acetate could ba applied with a
portable garden-type sprayer.  Due to an  undesirable  foaming  that  occurred


                                      36

-------
TABLE A-2.  INFLUENCE OF CLIMATIC CONDITIONS ON SURFACE TREATMENT AG£NTS
Agent
Polyvinyl
acetate
surface
collecting
agent
Dispersing
agents
Xanthan
Citrus
pectin
Borate-
silicate
nixture
Sodiua
silicate
cerif leans
Water
Sun
Aids in drying
, film; ->ay aid
in degrading
film
No effect
Unknown
Aids drying
Aids drying
Aids drying
Aids drying

Ho effect
Wind
Adversely affects spray-
ing; generates detri-
ments1, surf action; aid*
dry ing
Adverssl- affects spray-
ing; generates detri-
mental surf action
Adversely affects spray-
ing) generates beneficial
surf action
Adversely affects spray-
ing; generates detri-
mental surf actions aids
drying
Adversely affects spray-
ing i generates detri-
mental surf action; aids
drying
Adversely affacts spray-
ing; generates detri-
mental surf action) aids
dryirg
Adversely affects spray-
ing; generates detri-
mntal surf action; aids
drying
inpr lying and/or drying
Solidifies below 2.2°C
Unknown
High temperature aitis drying; low
temperature may prevent spraying
and/or drying
High temperature aid* drying; low
temperature may prevent spraying
and/or drying
High trirperature »K1n drying; low
teni>erat'jre may prevent sprayirg
and/or drying
Hiqh terrporature aids drying; low
temperature nay prevent spraying
and/or drying


Tidal Action
Hay erode film
.Vust renew troat-
rwnt between
tides
No effect
Film quite soluble,
must he renewed
between ticiei
Filn quite soluble,
rrust. t-*.' rencwc'5
between tid^s
kittle effect
Little effect


Wave Action
Degrrdes filffi
effect
Aids dispersion
action
Dissolves film
Dissolves film
Little effect
Little effect



-------
                                  TABLE  A-3.  PROBABLE  ENVIRONMENTAL  IMPACT
   Agant
       Appearance
           Toxicity*
                                                                                                 Duration
Polyvinyl acetate


Surface collect-
ing agent

Dispersing agents

Xanthan gum


Citrus pectin
Borate-silicate
mixture
Sodium silicate
Hicrococcus
cerificans
Water
Hard-coated white surface
when wat

None
Clear, gels with water
Clear, gels with water
Glassy coating on rocks
(probably gels with sea
water
Glassy coating on rocks,
gelatinous coating on sand
when sea water added

None
                       Nona
Nontoxic, air and water perme-
ability unknown

Very low toxicity, care required
in application

Depends on dispersant used

Nontoxic


Nontoxic
Questionable; borates may be
prt.sonous to aquatic flora and
are on list of hazardous sub-
stances, Federal Register, V.39,
August 1974

Silicates on list of hazardous
substances, Federal Reqister,
V.39, August 1974

Probably nontoxic
                                                      None
Estimated long duration
One tide
               or less
One tide cycle or less

Approximately one tide
cycle

Short duration, less than
1-2 hours in contact with
water

Short duration, less than
1 hour in contact with
water
Short duration, less than
1 hour in contact with
water

Short duration, possibly
1-2 hours
* Toxicity data were taken from published reports and technical information and refer both to organisms on the shore-
  line and to people who apply the agent.

-------
when   spraying   polyvinyl  acetate  with  air-pressure  spray  equipment,   a
oomiercial high-pressure airless spray unit was used.

     In seme of the mock-shoreline  experiments,  the  test  oil  was  applied
directly   to  dry  substrates  by  brushing  or  spraying.   Because  oil  is
transported to the shoreline on the surface of water/ this practice  will  not
be continnuad in future testing.

EVAUUA.TION METHODS

     Methods used to evaluate  the  effectiveness  of  the  surface  treatment
agents tested include the following:


       * visual-subjective judgment (all studies)

       * photographic record (all studies)

       * analysis of residual oil by  measuring  oil  removed  from  test  bed
         (Shell studies)

       * analysis  of  penetration  of  oil  through  the  agent  into  porous
         substrates (Shell and Tracor)

       * measurement of wetting and spreading of oil on treated and  untreated
         substrates (Tracor)

      In addition, scene simple laboratory tests   were  employed  by  Tracer  to
evaluate  other parameters,  such as film-forming ability and solubility in oil
and viater, affecting the  suitability  of film-forming  agentj.   Most  of  the
evaluation  methods  used in   the  previous studies can be adapted for future
work.  Unfortunately, none of the previous studies found suitable methods  for
directly determining  how  much  agent remained   on  a   test substrate after
exposure to wave  action or how much  oil   remained on  the  substrate  after
cleanup.

COS!1 O^SICSRATIQNS

      Table A-l presents a breakdown of  costs associated with the use  of  each
agent.   Ihe  costs  are   estimated   for   both  a  2889-square-meter area and  a
50,000-square-fcot area of treated beach.   These areas are equivalent to about.
1 tan and  1  mile,  respectively,   of shoreline  that   is  treated  over   a
S.l-meter-'wide tidal zone.

      Tha costs of agents  vary fron 13 cents per kg (6 cents per  pound) to over
§220 per  Xg   ($100 per  pound), depending in  part on ocmnercial availability.
However, because  the quantity needed  must  also be  considered, a  more realistic
evaluation  of  agent  cost  can bs  found in the fourth column, which lists the
cost of agssits needed for either 1 km or 1 mile of shoreline   treated.   The
effort required to prepares the  agent  for application is included in the table,
although this is  not a factor  for most  agents  since thsy are produced and  can
be  stored  in  a usable  form.  GO!UOTI  7,  .Application Cbst, includes labor an?


                                      39

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                                               TABLE A-4.   ESTIMATED  COST
Aqont
rolyvlnyl
«col«t«



Sur/aca
collecting
«g«nt


Dispersing
agents


Xantluin gun


Citrus
pcctir


Borate-
•ilicate
nvixture


Sodium
silicate



Micrococcus
ceritlcans



Water



Material Cote
60«A<) (27«/
Ib) in volu-
tion


52.44/liter;
(59.25/gal),
208.2-liter
<55-gal)
druifls
51.40/Uter
(SS.30/g.ll);
JOB. 2-liter
(55- diumi
S4.50A9
,,2,50/lb!

S7.72Ag
(53.50/lb)


ISC/Kg (6t/
Ib); dry
powder


15C-26 (49 Ib/
mi) - dry weight;
1361.1 kg/km (4900 Ib/
mi) - 11 solution
G'.O kqAro \220 Ib/
mi) - dry weight;
64^9.3 lit«rn/)rn
(2750 qal/rai) in
solution
62.0 kqAm (220 Ib/
mi ) - dry weight;
6468.3 liters/km
(2750 gal/mi) in
solution
42.3 kqAm (150 Ib/
mi) - dry veight




n nown


Material Cost
S754.97A"
(S1,21S/«1)



$574.77Am
(5925/mi)



S77.67/km
(S12V>i)


$J7.29Am
(S60/iTii )


$105.63Am
(S170/B1)


512.43 A*
($20/ru)



515.53Am
(?25/mil



58,077.B3-
$9,320.67Am
(513,000-
S15,000/m.i)

Hone



Preparation At«blo (tr»t for Nil ?• int 1« *rpl 1 ration Unknown
2-yr fttoro'?*.*) $110-$t?l



Stores indef- Nil Multiple applications Nil
initely anticipated, S&21-
5932


Storuo ind«f- Nil Continuous applica- Nil
initely t ions ant-icipatod
(•snail craft, n^ci^s-
rory) , t-:,n;-SlS^1
iiivrw ^iry - Oianolwn flew* M-jltir^ m-1^*- Cnkrown
mixing required 5621-5932

Stores dry - Dissolves slow- Multiple applications Unknown
stable If dry ly, hinh-sh<**r anticipated, *C2l-
nixinrj roquirijd S9i2

Stores dry _ Difficxilt to put Sintle application rnkncwn
into solution 5310-S6XI



Stores dry - Difficult to put Multiple atrplication* UnVnown
hygroscopic into solution antic ir^t^d, T3IO-
C621


Washea off eas- Must Ixs nixed Multiple apnlications Hone
ily. limited stor- with vnter anticipated
a'je except for
spray-dri»?d form



stall at ion inftall, . 5500 C\500
rviintenanr*
" Approximately 2U69 square rnetofs to be treated per km (50,000 square feet per mile).
  Labor and equipment for first km (excluding standby).

-------
equipment for the first km  of  application.   Subsequent  shoreline  coverage
would  be  considerably  less  expensive.  Excluded from application costs are
standby  costs,   observation   personnel   above   first-level   supervision,
cormtunication  systems,  elaborate  equipment,  etc.   The  cleanup  costs are
unknown for most agents because their  lifetimes  are  also  unknown.   It  is
hoped, however, that these costs can be minimized.

     Table A-4 shows that agent and application costs  are  most  significant.
The  polyvinyl  acetate  has  a  moderate  to  high initial cost., but only one
application is required.  The disadvantage of surfactants is that multiple  or
possibly   continuous   applications   are   required,  but  film  removal  is
unnecessary.  Xanthan gun and citrus pectin will be somewhat costly to prepare
because  it is difficult to form viscous solutions in water and because mixing
equipment is needed.  Hicrococcus cerificans has a prohibitive  purchase  coot
because  it  is  not  ccnmonly  available,  and it requires special laboratory
preparation.  Water itself has no cost because it will be drawn from the  sea,
but  equipment  is necessary to provide a continually flowing film.  Pipes and
pumps to cover 1.6 km  are  estimated  at  $10,000;   these  are,  of  course,
reusable.

AlKOTATED BIBLIOGRAPHY

"Shoreline Protection and Restoration fraa Oil Spills," Final Report  for  API
Ccnmittee  on  Environmental  Affairs, Exxon Research and Engineering Cbnpany,
1974.  (Supported in part  by  EPA.)  Evaluation  of  microbiological  agents,
natural   plant   products,  and  Biopolymer  9700  for  protection  of  rocky
shorelines.

"Shoreline Protection and Restoration Study," Final Report for  API  OomuLttce
on  Environnental  Affairs,  Shell  Development  Company, 1974.  Evaluation of
Borax Waterglass and Shell Oil Herder for protection and restoration of  sandy
and  rocky shorelines.

"Beach Protection Study," Final Report   for API  Cotmittee  on  Environmental
Affairs,  Tracer,  Inc.  , 1974.  Investigation of sprayable polymeric coatings
for  protection of shoreline materials (sand, rocks,  wood).   A  total  of  18
agents were screened.

"Microbiological  and  Natural  Product  Systems  for   the   Protection   and
Restoration  of Salt (tersh Grass Iran Oil Spills and Oil Contamination," Final
Report  to  API  Ocnroittee  on  Enviromsntal  Affairs,  Exxon  Research   and
Engineering  Ctrcpany,  1974.   Evaluation   of the  effect  of treatments with
Bio-polymer 97£&J and citrus pectin on ease of oil cleanup and long-term  growth
of salt-marsh  grass.                                                          ;

"Shell  Herder Trials,"  Ministry  of   Transport  and  Waterways,  North  Sea
Division,  Katherlands,  1974.  Evaluation  of Shell Oil Herder in open-sea oil
spill containment and beach protection and  restoration.

J.  Nightingale  and  J. A. Nichols,  "Beach  Protection:   Shell  Oil  Herder
Chemical,"  Karren  Spring  Laboratory,  Report LR184(OP), 1973.  Assessment of
Shell Oil Harder for protection of  shoreline materials from oil vsshed ashore.


                                      41

-------
"Oil Herder," Shell Product  Data  Sheets.   Review  of  physical  properties,
toxicity, biodegradability, and application data.

"Oorcxit 7G64, a Dispersant for  Treating  Oil  Slicks,"  Exxon  Product  Data
Sheets.   Ravie*'  of  properties,  toxicity, bicdegradability, and appliccition
data.
                                       42

-------
                                  APPENDIX B

                      PRELIMINARY AGENT EVALUATION TESTS
LABORATORY EVALUATION

     Three  types  of  laboratory  tests  on  surface  treatment  agents  vsre
undertaken:   (1) screening tests on the basis of solution and film properties
.(solubility, film formation, etc.);   (2) small-scale tests of beach protection
on  nock  beaches;   and   (3)  percolation  tests (on three of the agents) for
effectiveness in preventing oil  seepage.  The  tests  are  described  in  this
appendix,  and  the results for  each agent are given after the descriptions of
each test.  The agents tested are listed below:

       * polyvinyl acetate - synthetic film-forming agent (Borden  Polyco  694
         and 2113 and l&iion Oil  Jtosco 3006 and 3011 were tested)

       * sodium silicate - inorganic film-forming agent

       * borate-silicate mixture -  inorganic film-forming agent

       * xanthan gum - natural polymeric filnv-forming agent

       * citrus pectin - natural polymeric film-forming agent

       * dispersing agent  - chemical that interacts with oil to form dispersed
         oil micelles (Disparsant A was tested)

       * surface collecting agent - chemical that reduces oil spreading

       * water - continuous film of flowing water

     Synergistic  effects  with   the  surface  collector  and   tws   of   the
'film-forming   agents,   xanthan   gun  and   polyvinyl  acetate,  were  also
investigated.

Laboratory Tests

     The film-forming surface treatment agents   ware  subjected  to  screening
tests  to determine thair  solution  characteristics, film-forming ability, film
solubility, etc., before their effectiveness on  mock beaches vss tested.   The
test  methods are described below,  along with the results for each agent.  Not
all agents are listed for  each test because not  all tests apply to each agent.
Bar  instance,  Polyco G94 was purchased in a 55% water solution.  Hence there


                                       43

-------
is no need to test it for solubility problems.  Results will be listed for all
agents  for  which the test is applicable and are shewn in Table.B-l.  Further
testing of the borate-silicate  mixture  was  not  attempted  because  of  its
solution instability and failure to produce a detectable film.

Solution Process—
     Solutions of desired concentrations were prepared with  tap  water.   The
amount  of heating, agitation, and tka required to effect solution were noted
as well a«j special techniques required and the stability of the solution  once
formed.

      1. Citrus pectin was difficult to dissolve.  In order  to  make  a  0.5%
         solution  (by  weight),  the  solution  had  to  be  heated to 50° C.
         Heating to near boiling (along with vigorous stirring) was  necessary
         to  effect  a  1.0%  solution.   The  solutions  are viscous;  the 1%
         solution has an almost jellylike consistency at rcctn temperature.

      2. Xanthan gum was easy to  put  into  solution  in  both  0.5%  cjid  1%
         concentratins if cold water was stirred and tne powdered gun added to
         the vortex.  The  solutions  became  viscous  as  the  powder  became
         hydrated.  Viscosities were approximately the same as with the citrus
         pectin.

      3. Sodium silicate was impossible to dissolve  directly  to  fern  l%-3%
         solutions.   According to literature on the material, sodium silicate
         is more soluble in concentrated solution than  in  diluted  solution.
         Thus  a   50% ccranercial sodiua-silicate solution was used as a source
         of dissolved silicates, and dilutions were nsade tn form 1%,  2%,  and
         3%  solutions.  These solutions showed sons cloudiness after standing
         for several days.

      4. Borate-silicate mixture   (sodium  silicate/sodiun  borate)  solutions
         were  initially  made  by adding the required weight of borate to the
         sqdian-silicate solution.  HDMsver, this is  not  a  simple  process.
         Addition  of  dry  sodium borate to the concentrated sodium silicate
         resulted  in the formation of a glassy precipitate on the  surface  of
         the   silicate  which  would  not dissolve even \£ien heated.  (Keating
         caused flocculation of undissolved borate  but  did  not  affect  the
         glassy surface.) Solution was effected ly first dissolving the borate
         in vater  and  then  adding  this  solution  to  a  diluted  silicate
         solution.   Using this technique, colvrtions containing equal portions
         of silicate and borate salts in the total asotnts of 1.0%, 2.0%,  and
         3.0%  ware prepared.  After one day some cloudiness and precipitation
         were  noted in all  silicate  solutions.   Tha  3.0%  solution  turned
         oonpletsly into a white gelatinous suspension after one day.


Film Formation—
     Microscope slides were di£jped two-thirds of thair length into a  solution
of  the  agent and  allcwsd  to dry-  Ifce atpsarance of the film (if any) was
noted and its  thickness measured with a ndcrcsTteter.
                                      •44

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               TABLE B-l.   SOLUTION AND  FILM PROPERTIES OF SELECTED FILM-FORMING AGENTS
Agent
Concentration
range
Preparation of
solution
Characteristics
of solution
Film formation on
glass slides
Film formation on
screens (dipped)
Properties of films
Sprayability with
conventional
paint sprayer
Citrus Pectin
0.5%-1.0%

Boating required
Viscous to
jellylike
Dipped - very thin
but detectable;
sprayed - fair-
good
Good

Poor-fair
OK

Xanthan Gum
0.5%-1.0%.

Dissolves readily
Jiscous to
jellylike
Dipped - same as
pectin; sprayed -
better than pectin
Good

Good
OK

Sodium Silicate
Undetectable

Difficult (see
text)
Becomes cloudy
after a few days,
pH: 9-11
Dipped - undetect-
able; sprayed -
not tested
No film formed

None formed
OK

Borate-Silicate
Mixture
l%-3%*

Difficult (BOO
text)
3% solution gels
overnight
Dipped - unde-
sprayed -
blotchy, iso-
lated crystal
formation
No film formed

None formed
OK

* 50:50 ratio of sodium silicate to sodium borate,  with total  concentration  in  the  range  of  1%  to 3%.

-------
      1. Citrus pectin at a 0.5% solution formed  a  very  thin  film.   Slide
         appeared slightly dirty.

      2  Xanthan gun at a 0.5% solution did not form a complete film on  slide
         but  seenvad  to  be  thicker than the 0.5% solution of citrus pectin.
         The 1.0% solution formed a cloudy, thin film (25 microns).

      3. Sodiun silicate and borate silicate -  no  detectable  or  observable
         film on the microscope slides.

Film Solubility—
     The slides from the film-formation test were placed in  beakers  of  salt
water  and  agitated  gently.  The appearance of the film was noted as well as
its durability.

     Dip-formed films of citrus  pectin  on  glass  slides  could  be  readily
removed  in  30  minutes  by  immersion  in salt water, especially with slight
agitation.  Those films made from xanthan  gun  yielded  films  that  remained
after overnight inmersion.

'•     Since dip-formed films of sodium-silicate and  silicate-borate  solutions
could not be detected, the imraersion tests on than gave no data.

Screen Film formation and Penetration—
     Small squares of fine-mash copper  screen  ware  dipped  into  each  test
solution  and  allowed to dry*  The film that formed (if any) was evaluated as
to appearance and continuity.  Continuous films were tested for vater and  oil
penetration by simply placing a  few drops of water (or oil) on the surface and
checking for its penetration to tha other side.

      1. Citrus pectin at a  0.5%  solution  formed  an  incomplete  film  but
         covered over 70% of screen.  1.0% - complete film.

      2. Xanthan gvra - same as citrus pectin;  1.0$ solution was  particularly
         good.

      3. Sodium silicate and borate silicate ~ no films were  formed;   agents
         crystallized on screen.

Sprayability and Spraysd Film Formation—
     Tha test solutions were sprayed onto 10xl0-cm glass plates  to  test  for
spray   characteristics.   Pressure  necessary  for spraying, the type of spray
pattern, size of droplets, coverage, etc., were noted.

     Citrus pectin, xanthan gun, and borate-silicate films  were  prepared  by
spraying  the  solutions  using a conventional ccn^jressad-air-operated (4.2kg
par sq  cm,  €3  psi)  paint  spray  gun.   All   solutions  could  ba  sprayed
effectively.  Observations of the films were as follows:

      1. The 3.0% borate-silicate solution  did   not  form  a  corpiate  film.
         There ware isolated areas of crystals.
                                      46

-------
      2.  the  1.0% solution of xanthan gun gave  a more complete  film than  that
         of  the borate-silicate  solution.   Film was complete in the center of
         the  glass  plate.    The  coating  density decreased   as  the  radial
         distance frcxn the center increased.

      3.  The  film of  0.5% solution  of xanthan gum  was barely observable.   It
         had  the same density vs.  radius relation as in tlia solution.

      4.  The  film of  0.5% solution  of citrus pectin was ccrnplete but not  very
         dense.  Blotches formed  near the perimeter of  the plate.

      5.  The  film of  1% solution  of citrus pectin   was   complete.   It  formed
         concentric  areas   of low-density   coverage   that were  separated by
         ridges or  barriers  of slightly liigher  density.   Blotches formed  at
         plate edges.

Film Sol'-Mlity-Durability—
     Dry films on the glass  plates  frcm the  sprayability tasts  were used.  The
slides were propped at a 45-degree  angle below a buret  filled with salt water.
Water vas dropped from a height of  approximately 20 cm  onto the film, and  its
effect %as noted both at the point  of impact and on the runoff  area.

      1. Borate-silicate 3.0% solution - Water droplets appeared to wash  away
         any film that may have been present.

      2. Citrus-pectin 1.0% solution - The citrus pectin film migrated  to tha
         lowest edge  of the glass plate with the addition of water droplets,
         but  accumulation  at  the  edge  was  not  as  great  as with   the
         accumulation from the 1.0% citrus- pectin solution.

      .3. Xanthan-gun 0.5% solution - The xanthan gum film became swollen  with
         the addition of water but it did not migrate.   After drying,  the film
         was intact.

      4. Xanthan-gun 1.0%   solution  -  Parts  of  the  film  frcm  the   1.0%
         xanthan-gun solution migrated slightly toward the edge of ths plate,
         but most of it remained intact.

Mock-Beach Tests

     Mxk beaches were constructed in approximately 75-cm-square plastic  pools
that  were mounted  in a rocking mechanism.  The beach was constructed of sand
and gravel« with some larger rocks and pieces of wood  added  to  the  surface.
The total surface area was  0.427 sq meters.  Water was added to the pool,  and
the rccsing mechanism simulated wave action.  The durability  of  film-forming
agents  vas  evaluated  before   any  oil  was added to the pool.  As a result,
several agents were  not considered for  further testing because they failed tha
durability test.  Surfactants were also tested in the  nock-beach tests.  There
was a control mock beach for each of the mock-beach tests.   Detailed  results
of the cock-beach tests are  given in Table  B-2.
                                      47

-------
                                            TABLE  B-2.   RESULTS OF MOCK BEACH  TESTS
 Agent Tested
                              Application Method
                                                                   Film Durability
                                                                                                               Fila Resistance to Oil
 Citrus pectin,
 1%  solution in
 water

 CitruB pectin,
 21  solution in
 water
Xanthan gum, 1*
solution in
Xanthan gun
dry powder
Xanthan gum.
dry powder
Xanthan gum,
1* solution in
water
600 ml at 2.8 k>
-------
                                                         TABLE  B-2  (Continued)
Agent Tested
                          Application Method
                                                                     Film Durability
                                                                                                             Film Resistance to Oil
 Bcrden Polyco
 694
Borden Polyco
694
Borden Police
694
Borden Polyco
2113

Union Oil
Ansco 3006

Union Oil
AF.SCO 3011
                   950 ml  of  694 was sprayed on the baach.
                   This is a  heavy  coat. The beach wan
                   dried with the (lid of IR heat lamps
                   for approximately 20 hours. The film
                   was still  not dry all the way through,
                   as  w»s  noted from the characteristic
                   milky color of undried 694.
                   <90 ml of 694 sprayed on the beach.
                   This is  a light coat. The film dried
                   to a clear  film after 20 hours under
                   IR heat  lamps.
                  600 ml of 694 sprayed on the beach.
                  This is a medium  (standard) coat.
                  Film dried to a clear film in 3.5
                  hours vith aid of IR heat lamps.
                  500 ml sprayed on beach and allowed
                  to dry.

                  SOO ml sprayed on beach and allowed
                  to dry with aid of IR heat lamps.

                  £00 ml sprayed on beach. Dried to a
                  clear film in 1.5 liours under IR heat
                  lamps .
Film was slightly hydrated and water became
slightly milky, but the film remained in-
tact for the duration of the test.
Film re.iainc-d intact for the duration of the
test.
Film turned from clear to slightly milky, but
remained Intact for the duration of the test.
After 30 ainutes the film began to dis-
solve. Furthar teats discontinued.
Film dissolved within 30 minutes.
tests discontinued.
                                   Further
Film ra.nained intact. Film did not get the
milky hue that 694 gets when in contact
witn water.
500 irl of »2 fuel oil added.
Oscillations continued for 2 hours.
There was good cleanatility of sur-
face oil; UV Itqht indicated oil
permeation at all depths. Oil
probably penetrated because so
much was applied that It was dif-
ficult to qet the film totally dry.

500 ir.l of »2 fuel oil added. Oscil-
lations continued for £ hours. The
film exhibited good cleanability
characteristics. IP/ light indicated
only slight traces cf oil increas-
ing with the depth. Thic would in-
dicate seepage around the sides of
the film, i.e., at the interface
between the film and the wall of
the j.l, rather ti.a.i jt-cnetration
through the nain body of the film
itself.

500 nl of #: fuel oil added. Oscil-
lations continued for 4 houra. Film
exhibited good cloanobilicy char-
acteristics. Traces of oil were
found just under the film layer at
the Siiiid surface and at a 2.5-cra
depth. Surface traces could have
beun due to pinholes in the film
itself.

Hot tested.
                                                Not tested.
SOO ml of »2 fuel oil added and
oscillations continued for 2 hours.
Film exhibited good cleanability.
Oil trace? were detected at the
sand surface under the film layer.
Penetration into the beach was not
detected.
                                                                                                                            (continued)

-------
                                                                     TABLE  B-2  (Continued)
         Aqent Tasted
                                  Application Method
                                                                               Film Durability
                                                                                                                         film  Resistance to Oil
in
O
         Soc"iuiri-Bi licate
         Holution, SO*
         Vn water

         Sodi ura-s i 1 i cat 9
         solution, 6*
         in water

         Sodium-silicate
         solution, l.S\
         in vrater
         Union Oil
         3011  with sur-
         face  collector
         as syner-jist
         Xan'han ijun
         wit \ surface
         collector as
         synergist
         2»  solution
         in  water
        Bispersant A
        J0\  solution
        in watar
300 ml sprayed on beach.  Dried with IR   Film dissolved immediately upon water  con-
heat  lamps to a  crusty  film.
4no ml sprayed on beach.  Dried with
IR heat lamps to a  crusty film.
600 nl sprayed on beach.  Dried 1.5
hours with  IR heat  lamps.
600 ml of  3011 sprayed  on  a mock
beach. Dried under  IR heat lairps for
1 hcur. After the oil was  added, 20
droi- surfactant/collector applied
at the wash line to see if there were
any syncrqiatic effects from cowbin-
at'on of these ij^ntfi.
150 g of xanthan-gua  povder applied,
on wet bQach. 40 drops  surfactant/
collector «dded at  the  wash line
when the oil was added.
                            100 ml sprayed over the surface of
                            the nock beach.
100 .nl of this solution was  sprayed
over the surfaco of th4 sand.
                                          tact. Further tests discontinued,
j'iln dlstolved immediately  upon  contact with
water* Further tests discontinued.
Severe erosion within  10  minutes.  Further
testa discontinued.
                                                                      Film remained intact.
                                                                     Xarithan gum dissolved almost
                                                                     Not applicable.
                                                                     Not  applicable.
                                                                                                                      Not  tested.
                                                                                           Not tooted.
                                                                                           Not tested.
                                                 500 ml of 12 fuel <5il  *j.pli«J to
                                                 synthetic sea water, oscillation^
                                                 continued for 2 hvjrs.  After .^; —
                                                 plication of surfactant/collector'
                                                 a Elight "herdinu"  <"iC*-:or. tijo1'.
                                                 place. The confining effect of
                                                 the h»rder discii atei  with timu
                                                 dun to the constant c^urnin'i ac*
                                                 tio^ of the waves.  Oil  j>f-noti-ation
                                                 tests showed no c!iai.-jt-  in iJietce-
                                                 tive ability ol the- flln.

                                                 SCO ral c: *r fual oil  aid..-d.
                                                 There was a slj"ht  <:oll^ct:n':
                                                 action u;«n a.n^licattan of »ha
                                                 aurfactant/'-oll»-rtt-:.  The co;;-
                                                 t'inenent of the oil J-.'.rf-j^'i-i as
                                                 tho O'cillation tine  incit-n-'-S;
                                                 soon rio her'.!in*) effect  vir= o\j-
                                                 dcnt. UV expo^'irer  thowcii litllc
                                                 or no surface oil re-.; i-iu'-s, biit
                                                 siqrii f .dint rc^id^c.^ ^r derth.^
                                                 of 2.5 and 7.15 LT..

                                                 500 ml of »2 fuol oil  aJdc-.i av.'i
                                                 oscillations contir.uevi Cox* 2 hcn.rs.
                                                 irv analysis indicate:',  oil penetra-
                                                 tion at all lev^i':,

                                                 too rl t.f «;' fu...J oil  aJ-lp'i. I1ii«
                                                 oil Wd*5 ertulsi f i<-'.i  w[t:i.*n !x rur,-
                                                 iit**s. ''V f?x;X5sur<'';  i': 'i^T'11.! 01}
                                                 jt-r.^t/at icn ot *ilj  ]''V'-lu.

-------
                                                         TABLE  B-2  (Continued)
Agent Tested
                        Application Method
                                                                     Film Durability
                                                                                                               F'iltn  resistance  to  Oil
Surface collector  20 drops of surface collector were
                   applied to the oscillating beach
                   at the wash line
hater {flowing
over the beach
in a continuous
sheet)
Water continuously flowed from «
spray head while excess was simul-
taneously removed.
Wot1 ajjplicable, although there was a consid-
erable asxmnt of beach erosion due to chan-
nels formed by flowing water.
SOU nl cf f~ fin.--1 fii a.i->."! tf, Tho
&i.-a wciVu r f c^ ci J 1 a t;or.» cor *.inuoJ
for T hears. I'V analysis indirated
oil j-iMietraticit at ail levcis.

Oil waa detoctt'.! at all levels.
Tes t r;c thoJ ]- rci^ably doos not sir.-
ulate actual cor.di tic-"5 .

-------
Construction of Mock Beaches—
     The same general construction procedures ware used in building all of the
mock   beaches.   Twenty  liters  of  sand  and  gravel  were  added  to  each
75-cm-square plastic wading pool.  'Ihe beach material was about. .15.2  cm  deep
above  the wash line and sloped gradually downward toward the other end of the
pool (Figure B-l).  The mock beaches were then settled with approximately  7.5
liters  of  salt  solution  (3.5%  NaCl), which oscillated en the teach for 30
minutes.  The excess sea water was then pumped out  and,  except  vtoen  a  dry
application  of  xanthan  gum was to be tested, seme drying of the beaches was
allowed to occur.

     Depending on their physical nature, surface treatment agents were applied
in one of two ways:

       * If the agent to be applied was a dry powder, it was sprinkled on  the
         beach surface through a 200-mesh U. S. standard sieve.

       * If the agent was a liquid, it was applied to the beaches  as  a  fine
         spray  with  a  Sears Craftsman paint sprayer (700-ml capacity).  The
         pressure (2.8 to 4.2  kg/sq  on,  40  to  60  psi)  depended  on  the
         viscosity  of  the liquid being sprayed.  The agents were then dried.
         The drying time was frequently accelerated with the aid  of  infrared
         heat lamps.

Test Procedures for Film-Forming Agents—
     Tests of film durability and resistance to oil ware used to evaluate  the
effectiveness  of  each  surface  treatment  agent.   Ihe film-durability test
determined the ability of the egent  to  withstand  the  effects  of  constant
simulated wave action and sea voter.  If an agent did not function effectively
in this test, no further testing of that agent was undertaken.

     In the film-durability test, 5.6 liters  of  synthetic  sea  water  (3.5%
NaCl) was added bo a mock beach on which an agent had been applied.  Simulated
wave action was initiated at a constant rate of 10 oscillations per minute for
all  tests  and  was  continued  for 30 minutes.  Evaluation of each agent was
based on the loss  of  film  integrity   (developnent  of  holes,  tears,  film
dissolving)  and  on  adhesive   failure of the film on the beach (formation of
bubbles or wrinkles between sand and film).

     The oil-resistance test determiiiad the degree of  oil  penetration  on  a
mock  beach  and the ease with v.hich any surface oil was resnovod.  Only agents
passing the film durability test were tested for resistance to  oil.   In  ths
oil-resistance  test,  500 ml of oil was added to the water of each bsach, and
wave action was continued at 10  oscillatins per minute  for  up  to  2  hours.
During  this  time  the  effects of ths oil on ths agent were observed.  After
vave action stopped, the oil/water mixture was drained.  The ease  with  which
the surface oil could be rsnoved fron the bsach was then determined by washing
tha surface with a light stream  of water fran a waeh bottle.  The  panstration
of  oil  into  tha mock beach was determined by taking  "blots" of the bsach at
the surface and at various depths within ths beach colirnn.  These  blots  were
taken  with  Whatman  fl  filter paper, v.?iich when pressed to tha beach colusn
absorbs a representative saispling of any liquid within  the  beach  column  at


                                      52

-------
Motor wrth Variable
Epss:! Trensreiition
  x-~^\
                                                                                                   15.2 cm
                                   Figure B-.l.  Mock-beach design.

-------
that  depth.   The blots were then examined under short-wavelength ultraviolet
light.  Under ultraviolet light, aronatic residues  from  the  oil  exhibit  a
characteristic  fluorescence that can be photographed.  The approximate depths
of oil penetration was then determined.

     Evaluation of each agent in the oil resistance  test  was  based  on  the
following criteria:

       * If oil remaining on the surface of th& agent  could  be  washed  away
         with  a  gentle water stream, the agent was classified as having good
         cleanability characteristics for that grade of oil.

       * If the oil penetrated the agent throughout the beach (at two or  more
         depths), the agent was considered unsuccessful.

Test Procedures for Surfactants—
     The surface collector was sprayed into .he wash line  of  an  oscillating
mock beach.  DLspersant A was sprayed over the surface of the mock beach.

Percolation Tests

     The percolation test beach consisted of a  circular  container  that  was
fitted  with a bottom drain.  The container, which was 52.1 on in diameter and
25.4 on deep, was inclined at an angle of approximately  11.5  degrees.   Sand
was  placed  in the test bed so that the surface was also inclined as shown in
Figure &-2.  Ihe purpose of this construction was to simulate the  seepage  of
water through a beach that occurs when a wave recedes from a high-water point.
Testing was therefore done by carefully adding water to the top  of  the  test
bed and allowing the water to drain frcm the bottom.

     A sand/gravel mixture was placed in the container to a depth of 15.2  on.
Synthetic sea water was then poured into the container until all the beach was
submerged, allowing the beach material to settle.  Water was then drained to a
level below the beach surface.  The beach material was replaced for each tost.

     The agents tested (Polyco 694, jcanthan gun, and  Ttosco  3011)  were  then
applied  to the  entire  surface  of  each  beach.  Dry agents were sprinkled
through  a  U.S. standard  200-mesh  sieve,  and   solutions   were   sprayed.
Post-treatment  of  the  films  (drying,  heating,  etc.)  was  then  done, if
necessary.  Salt water was carefully introduced into the test beach  from  the
top so that the film remained intact.  Oil (#2, Kuwait, or #6) was then added,
and the water was allowed to drain frcra the bottom, thus seeping  through  the
beach.   Water  was  introduced  two additional tines, allowing the previously
applied oil either to float or to penetrate the film and beach.   After  three
cycles,  the bsach was drained, sectioned, and ex&»tiined for oil penetration at
1-inch intervals.  Table B-3 gives the results of the percolation test for the
selected agents.
                                       54

-------
'.n
                                         Surface Arsa S: d.2\ sg. metsr
                                     Figure B-2.   Percolation test  beach design.

-------
                         TABLE B-3.   PERCOLATION TEST
    Agent,
Concentration,                            Oil    Maximum
    Volume      Application  Conditions  Added  Penetration    Comments
Polyco 694
2,346 inl/ni
218 ml
Xanthan gum
516.7 gm/m2
48 gm
Amsco 3011
2,346 ml/m
218 ml
Spray Film
dried
Dry powder Misted
with H20
Spray Film
dried
£2
fuel
#2
Fuel
Kuwait
crude
Surface
under-
coating
Total pene-
tration
Surface
undercoat-
ing
Deep traces, prob-
ably from edge
seepage
Film appeared
intact
Ho oil found at
depth
Other Tests

     Tests were conducted on tha mock beaches to determine the most economical
application  volume  for  the  Amsco  3011.  Beaches were sprayed with 3011 in
volumes equivalent to 300 ml, 500 ml, and 600 ml over a surface area of  0.427
sq  m.   It  was  found  that  a  300-ml  film  was insufficient for effective
coverage, but 500 ml or roughly 0.11 liter per 0.09 sq m produced an  adequate
film.   it is important to note that a film of 3011 will not form if the beach
is too wet.  It therefore may be necessary in  actual  field  applications  to
apply  two light coatings of 3011.  Both light coatings would dry more quickly
than ono heavy coating.

PRELIMINARY FIELD TESTS - SALT MARSHES

     Surface treatment agents selected for the  preliminary  field  tests  are
listed below:

     1.  Synthetic film-forming agent

         A.  Polyvinyl acetate

     2.  Natural film-forming agents

         A.  Xanthan gum

         B.  Citrus pectin
                                      56

-------
     3.   Inorganic film-forming agents

         A.   Sodium silicate

         B.   Borate-silicate mixture

     4.   Surface collecting agent

     5.   Dispersing agents

         A.   Agent A

         B.   Agent B

         (Dispersant B, a hydrocarbon solvent-based dispersant, was added
         to the dispersing agent tests to determine if a hydrocarbon-based
         solvent dispersant behaves differently from the water-based
         dispersant, Agent A.)

     A series of four laboratory tests was performed prior to the  preliminary
field  tests  to obtain qualitative and quantitative data on selected physical
parameters that influence the application of these agents to  stalks  of  cord
grass   (Spartina  foliosa).   Adherence  to  stalks,  drying  time,  relative
durability,  and appearance were exftmned on wst and dry plants.

     For the preliminary field tests, an outdoor test tank was constructed and
placed  at the preliminary  field test site at Cbyote Hills Slough in south San
Francisco Bay.  Marsh plots were placed in the tank, coated with each  surface
treatment  agent,  and  tested  to determine their resistance to contamination
from an oil spill.  Arabian crude oil, #2 fuel oil, and 16 fuel oil were  used
as   the  test  oils.   The  effects  of  wave and tidal action and the ease of
flushing  were  sane  of  the  parameters  evaluated  during  the  test   tank
simulation.   Ibxic effects of the surface treatment agents on the marsh plots
was  examined over a 6-month period.

Laboratory Tteata

Experiment 1: Film-Forming  Properties of Film-Forming Agents
on Vfet and Dry  Specimens of goartina foliosa—
     Wet and dry stalks of  Spartina  tbliosa  were  dipped  in  each  of  five
film-forming  agents  -  0.5%  and 1% xanthan gum;  0.5% and 1% citrus peccin;
IS,  2%,  and 3% borate-silioate mixture;  1.902, 2§, and 3% sodium-silicate and
100% polyvinyl  acetate.   Six  stalk  samples, three wst and thr^e  iry, were
dipped in each agent at the above concentrations and placed on paper towels to
dry.  All  samples,  with  the  exception  of  the  polyvinyl acetate, formed
colorless films" that were difficult, if not iitpossible,  to  detect visually.
Use  of a hand microscope did not enhance detection efficiency.

     The seanthan-gum samples  (0.5% and 1%) exhibited traces of film where the
agent  had  accumulated, e.g., between the culm and leaves.  In sane instances
•the  agent had not ootpletely dried overnight.   Ifo samples of citrus pectin  or


                                      57

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sodium silicata produced visually detectable films.

     The samples that were treated with the borate-silicate  mixture  (1%  and
2%)  showed some milky spots, denoting the presence of a partial film.   The 3%
solution  revealed  crystals  on  two  plants,  denoting   poor   film- forming
capabilities.

     The samples treated with polyvinyl acetate were almost completely covered
by a white film.  Little difference was noted between the wet and dry samples.

Experiment 2: Film-Forming Capabilities on Wet and Dry
Surfaces of Cellulose Before Drying—
:     Shall pieces of Sipartina foliosa cellulose of approximately equal  length
and  diameter  ware dipped in the agents enumerated in Experiment 1 and at the
concentrations indicated.  Three wet and three dried culm  sections  with  the
outer  sheath  removed  were used as samples in this experiment for the agents
and concentrations shown in Table B-4.  Ifoodamine-B  dye  was  added  to  each
agsnt before the dip test in order to enhance visual inspection of the film.

     The presence of film was evaluated on a yes-no basis only.  A  film  that
appeared  continuous  or  that  covered at least 90% of the sample was given a
"yes" response.  Table B-4 presents the results of this  experiment;   xanthan
gum  and  polyvinyl  acetate  produced  the  best  films  on  both wet and dry
surfaces.  The 3% sodium silicate exhibited an almost complete film on the dry
Spartina,  and  the  1%  citrus-pectin  film was about 90% complete on the wet
Spartina.

Experiment 3: Film-Forming Capabilities on Wet and
Pry Surfaces of Cellulose After Drying—
     The agents applied to the culm sectins in Experiment 2  were  allowed  to
dry  for  2  hours.   Each  culm  section  was then visually inspected in both
natural and ultraviolet light for the presence of a film.  The results of this
experiment are shown in TSble B-5.

     In general, the  test  results  showed  that  the  3%  solutions  of  the
borate-silicate  mixture  and  the  sodium silicate formed very light films of
almost 100% coverage on  the  wet  surfaces  and  somewhat  less  on  the  dry
surfaces.   The  ultraviolet  light  provided little assistance with these two
agents.  The xanthan-gun samples exhibited at least 75% film coverage for both
wet and dry samples, although the wat samples appeared to be covered batter.

     The film formed by the  citrus  pectin  was  most  ccnplete  on  the  wet
surface.  The ultraviolet light showed little evidence of film except for soma
areas where the agent had accumulated.

     The polyvinyl acetate formed a 100% film on both the wet and dry surface*
from  natural  light  observations,  but  the  black light snowed that the dry
section had a less complete  film than the wet.

Experiment 4:  Simulated Wave and Tidal Action on Dry Agents—
     The culm sections from  Experiment 3 that ware. protected  by  dry  agents
      subsequently washed with water by a device that simulates wave and tidal


                                      58

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                     TABLE B-4.  FILM-FORMING CAPABILITIES OF FILM-FORMING AGENTS ON
                             DRY AND WET VEGETATIVE SURFACES, BEFORE DRYING
Agent
0;5% Xanthar ^jum
1.0% Xanthan gum
0.5% Citrus pectin
1.0% Citrus pactir
1.0% Sodium silicate
2.0% Sodium silicate
3.0% Sodium silicate
1.0% Borate-silicate mixture
2.0% Borate-silicate mixture
3.0% Borate-silicate mixture
100% Polyvinyl acetate
Dry
Soartina
Yes
Yes
HO
No
No
No
Yes
No
No
No
Yes
Wet
S£artina
Yes J
Yes )
No )
Yes )
No
No >
No
*
No >
/
Wo
'. Yes
Notes
1% solution formed better overall film.
1% solution produced 100% coverage; 0.5%
approximately 90%.
1% solution formed better overall film.
1% solution on wet plants produced approx-
imately 90% film coverage.
3% solution formed best film on both wet
and dry Spartina. Dry Spartina most.
amenable to film covering entire treated
area.
3% solution formed best film on both wet
and dry Spartina. Films quite incomplete -
up to 50% coverage of treated area

Wet Spartina better covered than dry.
Note:  Phodaraine-B dye was used to enhance visual inspection.

-------
         TABLE B-5.   FILM-FORMING CAPABILITIES  OF  FILM-FORMING AGENTS
                ON WET AND DRY VEGETATIVE SURFACES,  AFTER  DRYING
      Agent
                                 Natural Light
                                                 Black Light
0.51 Xanthan gum
1.0I Xanthan gum
0.5% Citrus pectin
1% Citrus pectin
1% Sodium silicate
2% Sodium silicate
3% Socliura silicate
1* Borate-silicate
mixture
 2% Borate-silicate
 mixture
 3* Borate-sllicato
 mixture
 100* Tolyvinyl
 acetate
Wet: Licjht film approximately lOOi
complete
Dry: Light film with heavier
blotchus, approximately 75% complete

Wet: Light film, approximately 100\
complete with some heavier concen-
tration
Dry: Heavier film than wet plant;
almost lOOt complete

Wet: Very thin film, about SOt com-
plete if scraped off
Dry: Incomplete film

Wot: Very thin film with some
incomplete areas
Dry: Incomplete film - approxi-
mately 50% coverage

Wet: Very thin film with areas of
no covdrage
Dry: More incomplete than wet,
splotchy appearance

Wet: Very thin film with areas of
no coverage
Dry: More incomplete than wet;
grainy appearance

Wets Very light film, almost 100*
complete
Dry: Less complete film than wet
plan*:; blotchy appearance for both

Wet: Very light film with many areas
not covered at all
Dry: Film less uniform than wet;
poor coverage

Wet: Very light film with patches
of no coverage
Dry: Film less uniform than wet)
poor coverage

Wet: Light film with almost 1001
coverage
Dry: Not a complete film; poor
coverage

Wet: 100% covered by a light  film
Dry: 100% covered by a light  film
Very difficult to sc-e  treated ureas
on both wet and dry  plants;  somu
areas of heavy concentration
fluoresced well

Heavy accumulations  of aqont were
visible, but liyht film,  if  present,
was difficult to detect
Little evidence of film present;
some bright spots on both wc-t  and
dry plants where agent accumulated

Little evidence of film present;
some bright patches on both wet and
dry plants where agent accumulated
Little evidence of film present
Little evidence of film present
Little evidence of film present;
some bright patches
Little evidence of film present;
some bright spots on both wet and
dry plants
 Film noticeable but very incomplete
 (approximately 50%)» better coverage
 on wet  than on dry
 Light  film discernible on both wet
 and dry, almost complete on wet;
 some bright patches present
 Very complete  film - visible on wet
 plant;  dry plant appeared to have
 50% to  75% complete film
 Note:  Ehodomine-B dye used to enhance visual inspection in both natural  and ultraviolet light.
                                              60

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action.  The culm sections were washed for 5 minutes each.  Each  section  was
washed  with  250  ml of water every 15 seconds during the 5~minute period.  A
schematic of the wave device is sliowm in Figure B-3.  The results of this test
are shown in Table B-6.

     The xanthan-gum samples showed almost 100% removal of the agent for  both
wet  and  dry surfaces;  only in areas where the agent had heavily accumulated
did a residua remain.  The citrus pectin appeared to maintain a thin  film  on
the  dried culm sections.  The wet culm sections had almost 100% film removal.

     The samples of the sodiun-silicate and borate-silicate mixture had almost
100% film removal fron the wet samples, while a slight residue remained on the
dried samples.  The 3% agent solutions left a very thin film on both  the  wet
and dried plants.

     The polyvinyl acetate was almost completely renewed from both the wet and
dry  samples,  although  inspection  under the ultraviolet light showed that a
very light, continuous film was still visible on both the wet and dry samples.
The  ultraviolet  light  was  used  only  on  these samples because it did not
enhance detection of the other agents in previous experiments.

fcesults—
     In general, the films formed better on the wet cellulose sections than on
the  dry  sections.   This was observed both before and after the agent dried.
The 3% sodium-silicate solution was something of an anoaaly because it  formed
a  better  film  on  the  dry cellulose sections.  The best films overall were
'formed by the xanthan gum (1%) and  the  polyvinyl  acetate.   Generally,  the
highest  concentration  of  the  agent  formed  the  best  film.   The  use of
KhcdsRiine-B  dye  and  ultraviolet  light  erQianced   film   detection.    The
concentrations  of each agent selected for the preliminary field tests were 1%
ixanthan gum, 1% citrus pectin,  3%  sodium  silicate  and  3%  borate-silicate
mixture.   The  polyvinyl  acetate  was  tested  only at full strength.  Theses
concentrations were chosen on t3ie basis of film-forming ability and durability
under simulated wave and tidal action.

Field Tests

     The preliminary field tests were carried out in a tank.  Each  test  slot
     separated  by  a  barrier  to  prevent  contamination of individual marsh
sections by the agents applied.  A 10-degree slope roughly simulated the slopa
of a salt marsh.  A separate holding basin at the end of the tank retained the
oil until a test was ready to be conducted.  A wave generator, located in  the
rear  of  the tank, was hand-operated and deliverted 10.2- to 15.2-on waves at
the rate of about 60 per minute.

     The  basic   test   procedure   for   tha   citrus-pectin,   xanthan-gum,
sodium-silicate, borate-silicate mixture, and polyvinyl-acetate experiments is
outlined below.

       * Applying the film-forming  agsnts  to  marsh  sections,  drying,  and
         observing the tidal variation and wave action
                                      61

-------
Figure B-3.  Laboratory wave device.

-------
TABLE  B-6.   FILM  RETENTION AFTER SIMULATED  HAVE AND TIDAL  ACTION
                                                  of kumoval
      0.5t Xantl.an gum


      It Xajtthan cjum



      0.5^ citrus ttictin



      1* Citru8 pectin



      11. Sodium silicate




      2% Sodium silica..u


      3* Sodium silicate
      1* Boratu-silicate
      mixture
      2* Borato-silicate
      mixture
      3* Borate-silicate
      mixture
      100V Polyvinyl
      acetate
      100» Polyvinyl
      acetate*
Wot: Almost 100. rciroval  of  film
Dryt 'Almost 100*. rumov.il  of  film

Wot: Almost lOO'i removal  of  film
Dry: Areas whore- film was heaviest  still con-
tained some tilm after washing

Wet:  1001 removal estimated
Dry: Heavier concentration workt-d off, but  thin
film still remained                    .

Wet: Almost 10O% removal  of  film
Dry: Not too discernibly  affected by washing
thin film still remained

Wet: Almost lOOt removal  of  film, althouqh  2 of
the 3 samples did show a  slight film remaining
Dry: Fairly uniform loss  of  almost  all  the  filn
in all 3 samples

Wet: Almost 100% removal  of  film
Dry: Very light residue noticeable  on  2 samples

Wet: Very thin film still partially visible
Dry: Slightly more film remained than  on wet
plant surface

Wet: 100* removal estimated; very slight traces
of  film
Dry: Almost 1001 reuoval  of  film, although
slightly more prominent traces  than on wet
surface

Heti Very light filn still visible, although
almost completely removed
Dryt Little difference between  wet  and dry  plants

Wet. Very light film still visible
Dryi Somewhat less removal of film  than on  the
wet sample  (averags of the 3 samples)

Wet: Film almost 1001 removed,  although slight
film partially visible
Dry: Slightly more film remained than  on wet
surface

Wet: Very thin film still visible  and  appeared
continuous
Dry: Thin film remained and  appeared  continuous
      • Ultraviolet light observation.
                                         63

-------
       * Applying the three reference oils to marsh  sections  without  agents
         and observing the effects of tidal and wave action

       * •Applying the film-forming agents to marsh sections,  drying,  adding f2
         fuel oil, simulating wave action, and flushing

       * Applying the film-forming agents to marsh sections,  drying,  adding #6
         fuel oil, simulating wave action, and 'flushing

       * Applying the film-forming agents to marsh  sections,  drying,  adding
         Arabian.crude oil, simulating wave action* and flushing

     Similar tests were conducted for the surfactants.   However,  a  5-minute
drying  time  was  allowed  for  the surface collector, while dispersant B and
dispersant A were applied to the plants and to the water directly in front  of
the plants as the oil approached.

     The tank was filled with approximately 500 gallons of sea water prior  to
each  testing  session.   At  each  testing  session,  the  salinity and water
temperature were recorded, as well as the wind  speed,  air  temperature,  and
relative humidity as shown in Tables B-7 through B-10.

     Marsh sections of Spartina foliosa were removed frcm a nearby test  plot.
Sections  were  approximately 91.5 on long by 30.5 on wide and were trinraad at
the bottom to a 15.2- to 20.3-cm tiiickness.   This  depth  was  judged  to  be
sufficient  to  keep  the major portion of the rhizomes or root system intact.
Each marsh section was placed on a portable tray and carried to the  tank  for
testing.   Infrared photographs were taken of each marsh section at this point
in order to document the plants in their natural state.  Infrared photos  were
taken  after  each  test  in  order to determine the efficacy of the agents in
protecting the plants and the effects of the oil  and  agents.   Eight  agents
jwere tested in all, each in conjunction with three different types of oil:  $2
fuel oil, $6 fuel oil, and Arabian crude oil.  The  film-forming  agents  have
been described previously and were used in concentrations that formed the best
filros in the laboratory testing.  Each agent was applied by spraying, although
jthe  actual msans varied slightly (see Tables B-ll thrown B-14).  Application
•2quipment is discussed in this appendix under Preliminary Field Tests -  Beach
Data.  The volume and concentration of each agent were recorded and each agent
applied evenly to the marsh plants and substrate.  After application, with the
jexception  of the surface collector, dispersant fl and dispersant A, the agents
Were allowed to dry for up to 2 hours. , The surface collector was  allowed  to
dry  for  5  minutes,  but  the dispersants were applied simultaneously to the
marsh section and to the water immediately in fronont of the  section  as  the
oil approached the samples.

     After the applied  agents  had  dried,  the  trays  were  placed  in  the
appropriate  slot  in  the  tank  and  submerged  until approximately half the
section was under vater to simulate tidal action.  This procedure allowed  the
oil  to  contaminate  the  plants that were partially submerged and those that
remained above the water line but were splashed by waves?  it also allowed  the
oil  to  contaminate  the  substrate during the simulated wavt; action.  In the
initial„tests the placement of the marsh sections allowed  inspection  of  the


                                      64

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        TABLE B-7.  WEATHER AT TIME OF AGENT APPLICATION  TO CONTROL MARSH PLOTS  (no oil used)*
Temperature ( C)
Agent Tested
3% Sodium silicate
1% Xanthan gum
1% Citrus pectin
3% Borate-silicate mixture
100% Polyvinyl acetate
100% Surface collector
100% Dispersant B
2% Dispersant A
Date
12 Jan 77
12 Jan 77
12 Jan 77
12 Jan 77
12 Jan 77
21 Jan 77
21 Jan 77
21 Jan 77
Air
12
12
12
12
12
14
14
14
Water
9
9
9
9
9
11
11
11
Wind
Speed
(km/hr)
8.0
8.0
8.0
8.0
8.0
6.4
6.4
6.4
Drying
Time
(min)
120
105
105
90
75
. —
—
'
'* Salinity - 32 ppt.

-------
    TABLE B-8.  WEATHER AT TIME OF AG2NT APPLICATION TO MARSH PLOTS CONTAMINATED BY #2 FUEL OIL*
Temperature ( C)
Agent Tested
1% Citrus pectin
3% Borate-silicate
mixture
3% Sodium silicate
1% Xanthan gum
100% Polyvinyl
acetate
Control section
100% Surface
collector
100% Dispersant B
2% .Dispersant A
Date
13 Jan 77
13 Jan 77
13 Jan 77
13 Jan 77
13 Jan 77
13 Jan 77
21 Jan 77
21 Jan 77
21 Jan 77
Air
10.0
10.0
10.0
10.0
10.0
10.0
14
14
14
Water
7
7
7
7
7
7
11
11
11
Wind
Speed
(km/hr)
3-5
3-3
3-5
3-5
3-5
3-5
8.0
8.0
8.0
Humidity
80
80
80
80
80
80
75
75
75
Drying
Time
(min)
90

90


90


--
* Salinity - 32 ppt.

-------
   TABLE  B-9.  WEATHER AT TIME OP AGENT APPLICATION TO MARSH PLOTS CONTAMINATED BY ARABIAN CRUDE OIL*
Temperature ( C)
Agent Tested
3% Sodium silicate
1% Citrus pectin
1% Xanthan gun
3% Borate-silicate
mixture
100% Polyvinyl acetate
Control section
100% Polyvinyl acetate
Control section
2% Dispersant A
100% Dispersant B
1% Xanthan gum
100% Polyvinyl acetate
Control section
100% Surface collector
100% Dispersant B
2% Dispersant A
Date
14 Jan 77
14 Jan 77
14 Jan 77
14 Jan 77
14 Jan 77
14 Jan 77
18 Jan 77
18 Jan 77
19 Jan 77
19 Jan 77
20 Jan 77
20 Jan 77
20 Jan 77
20 Jan 77
20 Jan 77
20 Jan 77
Air
16
16
16
16
16
16
—
—
17
17
17
17
17
14
14
14
Water
9
9
9
9
9
9
—
—
6
6
8
8
8
7
7
7
Wind
Speed
(km/hr)
8.0
8.0
8.0
8.0
8.0
8.0
5.0
—
5.0
5.0
3.0
3.0
3.0
8.0
8.0
3.0
Humidity
75
75
75
75
75
75
85
—
85
85
85
85
85
80
80
«0
Drying
Time
(min)
120
120



—

—




—



* Salinity - 32 ppt.

-------
        TABLE B-10.  WEATHER AT TIME OF AGENT APPLICATION TO MARSH PLOTS CONTAMINATED BY #6 FUEL OIL*
CO
Temperature ( C)
Agent Tested
1% Xanthan gum
3% Sodium silicate
3% Bora te -silicate
mixture
1% Citrus pectin
100% Poly vinyl
acetate
Control section
100% Surface collector
100% Dispersant B
2% Dispersant A
Date
17 Jan 77
17 Jan 77
17 Jan 77

17 Jan 77
17 Jan 77
17 Jan 77
21 Jan 77
21 Jan 77
21 Jan 77
Air
17
17
17

17
17
. 17
14
14
14
Water
10.0
10.0
10.0

10.0
10.0
10.0
11.0
11.0
11.0
Wind
Speed
(km/hr)
6.4-8.0
6.4-8.0
6.4-8.0

6.4-8.0
6.4-8.0
6.4-8.0
8.0
8.0
8.0
Humidity
70
73
70

70
70
70
75
75
75
Drying
Time
(min)

90


75

—



    * Salinity — 32 ppt.

-------
                      TABLS  B-ll.    CONTROL MARSH  PLOTS TEST DATA
                                            (no oil  used)
Aqent Tested
3» Sodium silicate
1% Xanthan gun
1% Citrus pectin
3t Borate-silicate
mixture
1004 Polyvinyl Acetate
Plant Appearance
Thin fi'-m on plant (dry)
but no. .st surface
Hant and surface still
wet
Thin film on plant (dry)
but moiat surface
Thin film on plant (dry)
but moist surface
Film-covered (dry) on
both plant and surface
Volu™
Aqort of Aq^.-.t
Durability (P!) Notes
Tear - no fiin
visible
Cood - jellylika
surface on soil
Poor - no film
visible
Poor - no file
visible
Excellent - good
cover
SOO Wave ac'.ion only (10 min),
garden *i •' '/or on dry plants
1000 Kav« 'Ction only (!•> Pin),
yardcn sprayer on dry plants
" • '- Wave action only HO min),
garden sprayer on dry plants
450 Wave action only (10 Kin),
garden sprayer on dzy plants
i'.'l Kave action only (10 Mini,
spray gur. on dry plants
3V Sodiun silicate


1% Xanthan gum


1% Citrus pectin


It Bozate-silicate
fixture

1001 rolyvinyi acetate


100* Surface collector


100X Dispersant B


21 Dispersant A
Thin film en plant  (dry)
but moist surface

Plant and surface still
wet

Thin f'lu! on plant  (dry)
but moist sMrfaee

Both plant and surface
still wet

Hot quite as good as
when wet, but still 0
cover

                      JO
                      50
                     500
Tidal action only (15 Bin),
garden sprayer on wet plants

Tidal action only (15 min),
gsrtlen sprayer on vet plants

Tida! action oi.ly (IS min),
garden sprayer on wcf plants

Tid-1 action onl1. (15 Bin),
garden sprayer en wet plants

Tidal action only (15 -in),
spray gun on wet plants

Garden spray
                             Spray gun
                                                                                        spray
                                                     69

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        TABLE B-12.   MARSH PLOTS  CONTAMINATED  BY #2  FUEL  OIL  -  TEST  DATA



Acient Tostod
	

Plant
Appearance

Substrate
Penetration
by Oil


Aicr.t
Durability
hase of
Flushing Oil
with
Water Spray

Volume
of Agent
(nil



J.'ot^s
It Citrus  pectin    Oily sheen on
                   plants
                                     Vury llflc
                                                               Pair*
                                                                                  500
                                                                                          /-minute wavo act Jon ,
                                                                                          Ei/raycil on giants a.vi
mixture
                    Oily sheen on     Very little
                    plants
3* Sodium silicate   oily sheen on     Very little
                    plants
   Xanthan gum      Light oil  sheen   Very littla
                    on plants
100* Polyvinyl      Light oil  sheen   Very little
acetate             on plants
Control section     Heavy oil sheen   Very little

100% Surface        Light oil shean   Very little
collector           on plants
100% Diaporsant B   Light oil  she«n   Very little
                    on plants
2» Dispersant A     Light oil shaen   Very little
                    on plants
                                                     Good
                                                               Fair"
                                                               Fair*
                                                               Fair*
                                                     Excellent Fjir*
                                                               Pair*
                                                                                         spr*»yei or. plants ar.J
                                                                                         soil, Tir-^tn opray

                                                                                  450     7-nir.;jle vave action,
                                                                                         BJ.rayed on plants anA
                                                                                         Boil, g^rd«n spray

                                                                                  500     7-nlnu»a wjvo action,
                                                                                         fipi;d on pldrits and
                                                                                         soil, qarc.cn spray

                                                                                  150     7-tninute v.we action,
                                                                                         spraytd on plants and
                                                                                         soil, gar
-------
TABLE B-13.  MARSH PLOTS CONTAMINATED BY ARABIAN
              CRUDE OIL - TEST DATA
Aqent Tested
•
3* Sodium silicate

It citrus pectin


1* Xantn&n tjun


3t Borate-sllicate
mixture

loot Polyvinyl
acetate

Control section'


2t Dispersant A




loot Dispersant B


It Xanthan gun



1001 Polyvinyl
acetate

Control section


lOOt Surface
col lector



lOOt Dispersant B



2t Oispersant A



Plant
Appearance

Heavy oily layer
on plants and
soil
Heavy oil layer
on plants and
soil
Heavy oil layer
on soil but less
on plants

Very heavy oil
on plants and
soil
A little less
oil on plants
than on control
Heavy oily layer


Heavy oily layer
on soil and
plants


Moderate oil
layer on plants
and soil

Heavy oil layer
on toil but
less on plants

A little less
on plants thn
on control
Heavy oil layer


Little oil on
plants and soil



Some oil on
surface but
little on plant

Little oil on
plants and soil


Substrate
Penetration
by Oil

Very little

Very little


Vtiry little


Very little


Vary little


Very little


Very little




Vejry little


Very little



Very little


Very little


Very little




Very little



Very little



Ksse of
Flushing Oil Volume
Agent with of Aycnt
Durability Water Snii.y (ml)

Poor Fair — similar 500
to control plot

foot Fair - similar 500
to control plot
f-fiftA Ow^ thn -iftl lu-» ^m
uooj
liXe layer helps
the flushing to a
degree
Poor Fair - similar to 500
control plot

Excellent Very good - 150
although some was
fairly clean
Fair - flushing
seemed to remove
over SOt of the oil
Fair - similar 500
to control plot


— — Vcrv flood — the 100
oil seemed to be
exulsilied by the
surfactant
Good Good - the Jelly- 100O
likn layer helps
the flushing to
• a degree
Excellent Very good - 200
although some
was fairly clean
— Pair - flushing
seemed to remove
over SOt of the oil
Very goo<< - oil 30 -So
formed snail
droplets that
were easily washed
off
Very good - oil 75
was emulsified and
easy to remove
by flushi-g
Very good - oil 500
was emulsified
and easy to remove
by flushing
Notes

sprayed on plants ^nd
coil, garden spray
7-rr.inute wave action.
sprayed on plants and
soil, qarclcn cpray
sprayed on plants and
soil, qardcn spray

7-minute wave action.
epraycd on plants ar.d
soil, garden spray
7-minute wave action.
sprayed on plants and
soil, garden spray
7-winute wave action


10 -minute wave action.
sprayed on plantf how-
ever* this method not
recommended j garden
spray
spirayed on plant; how-
ever, this method not
recommended t spray gun
7-minute wave action.
sprayed on plants and
soil, hydraulic spray

7-minute wave action.
sprayed on plants and
soil, hydraulic spray
7-minute wave action


7-ninute wave action.
sprayed on plants and
soil, spray gun


7-minute wave action.
sprayed in front of
'•'1, spray yun

7 -minute wave action.
sprayed in front of
oil, garden sprayer

                        71

-------
                          TABLE  B-14.  KARSH PLOTS  CONTAMINATED  BY
                                      #6  FUEL OIL -  TEST DATA
                                                                  F-'ose of
                                      Substrate                  Flushing oil    Vulunc
                       Plant         Pr-netr&tion     Agent          with       of A^rjt
  Aggnt TPStod	Rppearanc*	t-y Oil	Durability	WJter Spray	Imlt

1» Xanthai. qum      Heavy oil layer   Very little     Good      Fair  - oil did     500
                   on plants and                               flush i'roA soil
                   soil


3t Sodium riljcate  Heavy oil layer   Very little     Poor      roor  - little      WO
                   on plants and                               to.no oil flushed
                   soil


3% Porate-sllicste  Heavy oil layer   Very little     Poor      Poor  - little to   5C?0
mixture            rn plants and                               r.o oil flusi.ej
                   soil


1* Citrus pectin   Heavy oil layer   Very little     Poor      Poor  - little to   500
                                                               no oil flushed
100\ Polwinyl
acetate
Control section
lOOt Surface
collector
Heavy oil layer   Very little
on plants and
soil
Heavy oil layer   Very littl«
on pl&nts and
soil

Moderate oil      Very little
layer on plants
100% Dispersant B   Heavy oil  layer   Very  little
                    on plants  and
                    soil
2\ Dispersant A     Heavy oil  layer   Very  little
                    on plants  and
                    soil
Excellent Fair  -  little      200
          did flush  from
          soil
                                                               t-oor - littlo  to
                                                               no oil flushed
          Good - oil  flushed  SO
          fairly well  from
          plants but not as
         'well from soil

          Poor - little to    f5
          no oil flushed
                                           Fair - oil diJ     500
                                           not flush from
                                           plant* but a little
                                           did flush from soil
                                                                     7 min'jtr;s of wave
                                                                     action, sprayed on
                                                                     soil and plants,
                                                                     garden sprayer

                                                                     7 nit.utcs of vave
                                                                     action, sj»rayed on
                                                                     sell And plants,
                                                                     yardtn sprayer

                                                                     7 Fiir.utes of wave
                                                                     action, sprayed on
                                                                     soil and plants,
                                                                     garden
7 minutes of wave
action,  sprayjd  on
soil and plants,
garden sprayer

7 minutes of VMve
action,  sprayed  on
soil and plants,
garden sprayer

7 minutes of wave
action
7 minutes of wave
action, sprayed on
soil and plants,
qardcn sprayer

7 minutes of wave
action, sprayed in
front of oil, spray
gun

7 minutes of wawe
action, sprayed in
front of oil, spray
gun
                                                      72

-------
^relative degree of removal  of each agent by tidal  and wave action.   In besting
 the control sections  in which the agent was applied without  oil,   Rhodamine-B
 dye  end  food coloring were  used  to  facilitate  the determination of the
 relative durability of each agent on cellulose.  These  results  v*>re compared
 with the laboratory evaluation results.

      For those tests  involving oil, a holding basin was used to retain tho oil
 behind  a  movable dam. This allowed the oil to  spread quite evenly over the
 water surface, subjecting each marsh section to  approximately equal volumes of
 oil.   The  volume of oil  used in each test varied with the oil being tested.
 For the #6 fuel oil test, 6 liters were used; for the  Arabian crude oil  test,
 4  liters;  and for the #2  fuel oil test, 2 liters.  This difference in volume
 was due to the relative viscosity of each  oil  and  its  ability   to form  a
 uniform  film  on  the water.  At the beginning  of each test with oil, the daw
 was lifted and the oil "waved" into the vegetation for  5 to 7 minutes with  a
 wave  generator  located at the end of the tank.   Each wave was approximately
 10.2 on high, and the waves were produced at a rate of  about  60 per minute.
 This  frequency  and   time  allowed the oil to move toward and contaminate each
 marsh section to  the  maximum extent possible with   the   volume  of   oil   used.
 Each  tray  was  then  pulled  out  of  the  tank, and  the marsh sections were
 observed visually for oil coverage, section appearance, and agent   durability.

      After the tray was removed from the test tank,  each  marsh section was
 flushed  by  a low-pressure  water  spray  in  order  to estimate  the ease of
 flushing of the oil from the plants and their substrate.  Infrared  photos were
 then taken of each marsh section to provide a comparison with the photos  taken
 prior to agent application  or oil contamination.   Oil   penetration  into the
 substrate  was checked  by  ultraviolet  light  after   flushing by removing a
 ^section of the oiled  substrate.  The fluorescent properties of the   oil   could
 be  distinguished  from the fluorescence caused  by some of the agents, thereby
 determining the penetration of the oil.  Since #6  fuel  oil does not fluoresce,
 no  penetration data  were directly obtained for  this  oil, but the viscosity of
 the oil is such that  actual penetration would be negligible.

      After each test  the marsh sections were returned to their original   plots
 and  marked  for   future observation.  Oil was removed  frcrn the tank by use of
 sorbent pads and  steam cleaning.  Any contaminated oil/water mixture was run
 through  a  separator  and   embiber  beads  to  remove  the last traces of oil.
 Uncontaminated water  was returned to a nearby slough.

      The entire test  site was  cleaned  and  policed  after  all testing was
 concluded.   All   debris vas  disposed  of  in accordance  with   recomended
 procedures.

 Results

 Unoiled Control Plots—
      Surfc.ce treatment agents were sprayed onto both  wet  and dry SSpartina
 •without  any  oil  being used.  In both cases,  the marsh soil was  moist. The
 ;environmental conditions at the time of agent  application  and their  drying
 times  are  given  in Table B-7.  A suarary of the control marsh-plot tests  is
 given in Table B-ll.


                                      '73

-------
     After being sprayed on dry plants and over a period of 1 to 2 hours,   the
citrus pectin, sodiun silicate, borate-silicate mixture, and polyvinyl acetate
all formed a dry film on the dry plants.  The xanthan gum, however, retained a
jellylike consistency on both the plants and substrate.  The surface collector
and dispersant B, each having an organic base, formed  an  oily  film  on  the
plants  and  soil.  Except for polyvinyl acetate, which formed a rubbery crust
on the soil, all agents remained moist on the marsh soil an a  result  of  the
retained moisture in the marsh mud.

     Xanthan gun, citrus pectin, sodiun silicate, borate-silicate mixture, and
polyvinyl  acetate  were  tested to determine their durability under simulated
wave action for 10 minutes.  After this time no film was visible on  the  soil
or  plants  sprayed  with  citrus  pectin, sodiun silicate, or borate-silicate
mixture.  A thick film of xanthan gun was still visible on thr marsh soil, but
little  was  observed  on the vegetation in the surf zone.  Ralyvinyl acetate,
however, maintained an excellent film on the soil and a very good film on  the
plants  after  the  simulated  wave  action.   A week later, polyvinyl acetate
remained on the marsh soil, although approximately 50% had dissolved or eroded
away.

     The same concentrations and volunes  of  sodiun  silicate,  xanthan  gun,
citrus  pectin, borate-silicate mixture, and polyvinyl acetate were sprayed on
wet plants to determine their durability under tidal action.  Sodiun silicate,
citrus  pectinf borate-silicate mixture, and polyvinyl acetate were almost dry
after 1 to 2 hours on the  plants.   Otherwise,  no  difference  was  observed
between the agents sprayed on wet or dry marsh plants.

     The agents were  then  tested  under  simulated  tidal  action  by  being
submersed  in  sea water for 15 minutes.  After this time, no film was visible
for  sodiun  silicate,  citrus  pectin,  or  borate-silicate   mixture.    The
xanthan-giro  film  was  observed on the soil but not on the plants.  Polyvinyl
acetate naintained an excellent film on the soil cover end a very good film on
the march plants.

Plots Tested With *2 Fuel Oil—-
     Surface treatment agents were applied to eight marsh plots.  An untreated
marsh  section  was  used as a control plot.  All of the agents except for the
surface collector, dispersant B, and disperjant A, were  allowed  to  dry  for
approximately  1-1/2  hours before being tested.  The environmental conditions
at time of agent application and their drying times are shown  in  Table  B-8.
The test results are shown in Table B-12.

     The #2 fuel oil was very difficult to observe on  the  plants.   However,
careful  observation could detect contaminated plants by a shiny appearance or
sheen on the leaves.  A moderate oil sheen was  noted  on  the  citrus-pectin,
sodiisn-silicate,  borate-silicate mixture, and control marsh sections.  Only a
very light oil sheen was observed  on  the  sections  sprayed  with  polyvinyl
acetate,  xanthan  gun, the surface collector, dispersant B, and dispersant A.
It was very difficult to determine if the sheen on the  surface  collector  or
the  dispsrsant B sections was due to the agent or the oil because both agents
are hydrocarbon-based.


                                      74

-------
     Citrus pectin, sodiun silicate,  arid  borate-silicate  mixture  exhibited
poor  durability  during  this  test.   Polyvinyl acetate was the most dumble
agent;  xanthan gum, the surface collector, dispersant B, and dispersant A had
good  durability.   The durability of the surface collector, dispersant B, and
dispersant A relates both to the protective layer that remained on the  plants
and  substrate  and  to  the  ability of these agents to break up the oil film
before it reached the marsh section.

     Substrate penetration by the oil,  determined  by  using  an  ultraviolet
light  on  cores,  was found to be slight on all marsh sections, includjjig the
conturol.  This may be because this test was conducted shortly after oiling and
the  oil  did  not have a chance to penetrate, or because the substrate itself
acted as an efficient barrier.

     The marsh sections were  sprayed  with  a  low-pressure  water  spray  to
determine  the  ease of flushing the oil from the plants and soil.  Little, if
any, difference in oil removal was observed between the  control  section  and
the  sections  protected by citrus pectin, borate-silicate mixture, and sodium
silicate.  The sections sprayed with xanthan gum  and  polyvinyl  acetate  had
less  of a sheen after flushing.  This could indicate that the oil was removed
from these sections by flushing  or  that  the  oil  did  not  adhere  to  the
vegetation.  The sections protected by Shell Oil Harder caused the oil to form
small droplets, which were easily washed from the plants and substrate by  the
water  spray.   The  sections  treated with dispersant B and dispersant A were
easily cleaned by water spray.  Only slight contamination was still noticeable
after flushing.

Plots Tested With Arabian Crude Oil—
     Surface treatment agents were applied to marsh plots.  An untreated marsh
section  was  used  as a control plot.  Some agents were tested more than once
with Arabian crude oil because they were used for denonstration purposes.  All
agents  except  dispersant  B,  the  surface  collector, and dispersant A were
Allowed to dry for up to 2 hours before testing with oil.   The  environmental
conditions  at  the time of agent application and their drying times are shown
in Table B-9.  The results of this phase are shown in Table B-13.
                ;              '         .'
     The test for agent durability was subjective and  consisted  of  visually
observing  the  agent  film  before  and after wave and tidal action.  In most
cases the oil film covered the plant and soil, and deductions were made on the
basis  of laboratory experiments.  The most persistent agent was the polyvinyl
acetate.  Once this agent had cured,  it  formed  a  rather  solid  protective
surface.   The  xanthan  gum  was more persistent on the substrate than on the
plants, thereby affording protection against significant oil penetration.  The
surface  collector, dispersant A, and dispersant B results on agent durability
were somewhat inconclusive because their manner of application  differed  frcm
the  other  five  agents.  Hawever, based on the light oiling observed, it was
assumed that the agents had persisted quite well.  It should be noted that for
surfactants,  durability relates both to the protective layer that remained on
the plants and substrate and to the ability of these agents to  break  up  the
Oil before it reached the marsh section.
                                      75

-------
     Most of the marsh sections were quite heavily oilod upon removal from the
test tank.  The oil appeared to adhere to the plants and substrate despite the
presence of the agents, i.e., there was little  difference  fron  the  control
section.  The exceptions to this were the surface collector, dispersant B, and
dispersant A.  Ihe method of application and the  nature  of  the  surfactants
kept  the  oiling  of  the  marsh  section  to a minimum.  There was generally
somewhat less oil on both the vegetation and substrate of the sections treated
with polyvinyl acetate than on the control section.

     Ease of flushing was  tested  using  a  low-pressure  water  spray.   The
easiest  to  flush  were  sections treated with polyvinyl acetate, the surface
collector, dispersant A, and dispersant B.  Ihe others were not much different
from  the  control,  although the jellylike consistency of the xanthan gun did
help  somewhat  in  flushing  the  oil  fron  the  substrate.   Oil   on   the
polyvinyl-acetate-treated  sections, especially the substrate, flushed easily;
some oil traces were  left  on  the  plants.   The  surface  collector  caused
formation  of  small oil droplets that were easily flushed from the plants and
substrate.  In the case of dispersant A and dispersant B, the oil was somewhat
emulsified, which made its removal by flushing quite easy.

.     Substrate penetration by oil was determined by cutting a portion  of  the
oiled substrate away from the marsh section and observing it under ultraviolet
light.  Since seme of the agents fluoresce,  it  was  necessary  to  carefully
distinguish  the agent from the oil when looking for oil on the surface and in
the soil column.  However, even though different volumes of oil and agent were
observed  on the surface of the samples, little or no penetration was observed
in any of the marsh sections, including the control sections.

Plots Tested With #6 Fuel Oil-
     Surface treatment agents were applied to eight marsh plots.  An untreated
marsh  section  was  used  as  a control plot.  Each agent, except the surface
'collector, dispersant B, and dispersant A, was allowed to  dry  between  1-1/4
and  2 hours before testing with oil.  The environmental conditions at time of
agent application and their drying  tiroes  are  shown  in  Table  B-10.   Test
results are shown in Table B-14.

     Except for  the  citrus  pectin,  sodium  silicate,  and  borate-silicate
mixture,  all  of  the  agents  showed  sane  durability during simulated wave
action*  Polyvinyl acetate was the most durable agent.  Xanthan  gun  and  the
'surface  collector  vere also good.  Dispersant B and dispersant A showed fair
durability.  It should be noted that for the surface collector, dispersant  B,
and  dispersant  A,  durability  relates  both  to  the  protective layer that
remained on the plants and substrate and to the ability  of  these  agents  to
break up the oil film before it reached the marsh section.

     Ml  marsh  sections,  except  the  section  treated  with  the   surface
collector,  had  a  thick layer of #6 fuel oil on the vegetation and substrate
after simulated wave action.  The surface collector tended  to  bead  the  oil
into thick, round globules;  this resulted in less contamination than with the
bther agents.

     Little difference was observed between low-pressure water flushing of the


                                      76

-------
control  section  and citrus pectin, sodiun silicate, borate-silicate mixture,
and dispersant B.  Xantlian gun and polyvinyl acetate exhibited somewhat better
results when flushing oil frctn the substrate, and the dispersant A flushed oil
from the plants the most easily.  The surface collector seemed superior to all
the  other  agents in aiding the flushing of oil from the plants.  It was also
superior, but to  a  lesser  extent,  in  aiding  flushing  of  oil  from  the
substrate.

     Substrate penetration by the #6 fuel oil was not observed in any  of  the
marsh  sections  tested, including the control.  The high viscosity of the oil
prevented penetration from occurring.

Results—
     All of the film-forming  agents  formed  a  film  on  the  dry  cordgrass
(Spartina  foliosa),  although not all films were complete.  The effectiveness
of the fiL-a-forming agents in protecting wet cordgrass and marsh soil from oil
contamination  varied  significantly.   Only xanthan gun and polyvinyl acetate
formed a reasonable, effective, and long-lasting film over the  cordgrass  and
marsh  soil.   It  was  reccnwended  that xanthan gun and polyvinyl acetate be
tested  during  the  full-scale  field   tests   to   fully   evaluate   their
effectiveness.    The   surfactants   tested   showed  promise  in  preventing
ixwtamination of salt marshes by oil.

Toxicity of Agents to Marsh Plants

Test Procedures—
!     Tbxicity tests  were  performed  on  47  plots  of  cordgrass,  (Spartina
foliosa),  which  were growing adjacent to San Francisco Bay near the mouth of
Coyote Hills Slough in Fremont, California.  Each sample was removed fron  the
ground  with  a  plug of marsh soil measuring approximately one-third meter in.
Width by one meter in length.  A few of the plugs were cut in half to  provide
the  requisite  number  of  samples  frcm the limited amount of test material.
Pare was taken to remove enough soil so that damage to roots and rhizomes  was
minimized.

     Each plug was set in a specially constructed test tank at an angle to the
horizontal  in order to simulate the slope of a marsh surface into an adjacent
body of water.  Surface treatment agents and teat oils were  applied  to  each
plot,  as  surrmarized in Tfcble B-15, and wave action was simulated.  The plots
were then replaced in their original locations in  the  marsh  for  subsequent
periodic examination.  The location of each plot is shown in Figure B-4.

Data Collection—
     TVo types of data were collected throughout the sampling period;

       * Each plot was qualitatively assessed for relative health and  density
         of plants.

       * Measurements were taken of the height  of  selected  plants  in  each
         plot.

      Initially, the turgor and color of  the  marsh  grass  provided  adequate


                                      77

-------
   TABLE B-15.   SURFACE TREATMENT AGENTS, TEST OILS, AND MARSH TEST PLOTS*
Dry Dry
Agent Control Control
3% Sodium 1 6
Silicate
1% Xanthan 2 7
gum-
1% Citrus 3 8
pectin
3% Borate-silicate 4 9
mixture
100% Polyvinyl 5 10
acetate

Surface 39
collector
Dispersant B 40

Dispersant A 41

Control


#2 Fuel
Oil
13

14

11

12

15


42

43

44

16


Arabian
Oil
17

19
33
18

20

21


36

32
37
31
38
22
30
35
#6 l-'uel
Oil
24

23

26

25

27
29
34
45

46

47

28


* Entries signify plot numbers;  see Figure B-l for location of test plots.
                                      78

-------
                            Mudflats
                                                     N
                                Water

                                     Mudflats
                                        Water
Figure  B-4.  Location of marsh  test plots.
                        79

-------
qualitative  indicators  of health.  Healthy plants had resilient,  green stems
and leaves, and flaccid, brown stems typified unhealthy or dead  plants.   Ihe
relative  density  of the steins was also noted.  Saniquantitative records were
kept of each of these characteristics and were sunned to  provide  an  overall
index of the health of each plot.

     As  time  progressed,  it  became  necessary  to  change  the  method  of
qualitative  evaluation.   Differences  were  no  longer  apparent in color or
turgor of stems and leaves.  Stern density remained the single semiquantitative
index of each plot's health.

     Height measurements were initiated when it  became  clear  that  the  new
(1977)  growing season was underway.  Ten individual plants, distributed along
the central axis of each plot at intervals approximately  equal  to  one-tenth
the  length  of  the  plot,  were  tagged for continued observation.  The tags
consisted of grey duct tape attached to one end of a twisted loop of wire that
loosely  encircled  the stem.  Cne untwisted end of the wire was inserted into
the marsh soil.  The tags were difficult to maintain during the study  period,
and  some  tags  were lost.  It was necessary to resample the plants each tiire
height measurements were taken.  Records were kept on those plants whose  tags
were not lost but were considered insufficient for meaningful data analysis.

     In keeping with the objectives of this study, the observations  contained
in  this  report  should  be  considered  only  as  initial  indicators of the
potential harm or benefit to be derived from the use of a  given  iilm-forming
or other agent.

Qualitative Data.—
     Relative  comparisons  of  plant  reaction  (e.g.,  health)  to   various
treatments  were  made  on  the  basis  of  qualitative  observations.   These
comparisons are presented in Table B-16.  In  the  first  observation  period,
Various  degrees  of  plant mortality were observed in seme test plots.  These
mortalities are shown in Table B-16 and were incorporated  into  the  relative
comparisons.  V£iile by no means conclusive, the distribution of lethal effects
suggests  possible  agent  toxicity  in  the  concentrations  used,   possible
bil/agent   synergistic  effects,  or  ;inccmplete  protection  by  the  agent.
Subsequent recovery of most plots where plant mortality was  observed  further
suggests  that the root and rhizcrae masses survived the treatment and that the
"mortality" was  only  an  aerial  expression.   Ito  toxic  responses  to  the
film-forming agents were observed in the agent-treated control plots.

     In general, most plots had recovered to approximately  normal  appearance
by  the  final  sampling  period.   A notable exception applies to same of the
plots that were contamiiiated with #2 fuel oil.  Ihe control plot  (no  surface
.treatment  agent applied) exposed to this oil remained very scantily vegetated
'throughout the sampling period.  In contract, the plots that ware very heavily
piled  with  #6  fuel oil remained in relatively good condition throughout the
sampling psriod.  Except for the  portions  of  leaves  and  stems  that  were
heavily  oil-encrusted,  the  plants  appeared to be healthy.  It seems, then,
that the oil that contains the greatest proportion of low-boiling fractions is
most  toxic to the marsh grass, whereas the heavier oil's impacts are  physical
in  nature.  (This is consistent with the observations  of  Jennifer  M. Baker,


                                      80

-------
          TABLE  B-16. RELATIVE  CONDITION OF PLANT HEALTH VS. TIME?
                              QUALITATIVE OBSERVATIONS
              10
                         March 22
                                            April 7-
                                                                Kay 11

)'.
3.
4.
S.
6.
1,
8.
1.
2
3.
4.
5.
1.
2.
3.
A.
5.
6.
7.
8.
-J.
1.
2.
3.
4.
S.
G.
7.
8.
9.
1.
2.
3.
4.
5.
6.
7.
8.
y.

Xanthan qua
I'olyvinyl acetate
C'itruf. pectin
J*.M\itu silicate
S-jrfaci! collector
r>isp«rsant fc
Dini.'orsa.it A
Sodium silicate
Boraco silicate
Polyvinyl acetate
Citrus pectin
Xanthan yun
Sodium silicate
Derate silicate
I'o 1 y v i r.y 1 ace t ate
Dispersant B
•Citrus pectin
"Control
Surface collector
Dispersant a
* Xanthan 'jun
Sodium silicate
Control
FOrate silicate
Xanthun qum
I'oly vinyl acetate
Dispcrsant D
*Citrus pectin
Dispersant A'
fEurface collector
Xanthan gum
Citrus pectin
rolyvinyl acetate
Bora to silicate
Dispcrsant D
Sodium silicate
•Surface collector
Dispersant A
^Control


Xanthan qum
Citrus pet-tin
Surf acts collector
Oisporsanc. B
Dispersant A
bo rate silicate
Polyvinyl acetate
Citrus pectin
Sodium silicate
. Xanthan gum
Falyvinyl acetate
Borate silicate
Sodium silicate
Dispereant A
Dispersant B
Surface collector
Polyvinyl acetate
Citrus pectin
Borate silicate
Xanthan gum
Control
r tor ate silicate
Xanthan gum
Sodium silicate
Citrus pectin
Surface collector
Dispcrsart A
Polyvinyl acetate
Control
Pispersant B
Sodium silicate
Citrus pectin
Polyvinyl acetate-
Surface collector
Dispersant B
Xaninan qum
Dispcrsant A
Control^
Borate silicate

Poratc silicate
Surface collector
Xanthan gun
Dispcrsiint A
I'olyvinyl acetate
Citrus pectin
Dispersanf h
Poly vinyl acetate
Sodium silicate
citrus p*;ctin
liorate Silicata
Xanthan qum
Sodium silicate
Pisrcrs*nt A
Surface collector
Xanthan gun
Dispersant B
Citrus pectin
Polyvinyl acetate
Berate silicate
Control
Borate silicate
Podium silicate
Citrus pectin
Xanthan gum
Polyvinyl acetate
Di spcrsent A
Control
Dispersant B
Surface collector
Surface collector
Xanthan qum
Borate silicate
Dispcrsant &
Dispersant A
Con trol
Sodium silicate
Polyvinyl acetate
Citrus pectin

di fference






h'o observable
difference



Sodium silicate
Xanthan gum
C:trus pectin
Pol yviny 1 ace tat«
Surface collector
Di&persant B
Dispersant A
Eorate silicate
Control
No observable
difference







Sodium silicate
Xanthan qum
Citrus pectin
Borate silicate
Polyvinyl acetate
Control
Surface collector
Dispersant D
Dispersant A

x^!thai,s'!,r'jt''
Citrus txjr.-Ljr.
Horat'_ s.iiotr^
I'olyvi n/1 ace i :»:.';.
Surface- conC'-.",'.-r
Disi-crsiinv A
Uisr^rsant !i
Mo oUerva4.lt
dif fercnc*.'



Sodium silicate
Xanthda -jum
Citrus j-cctir.
I'olyvinyl acetate
Surface collector
Dispersant B
Dispoisant A
borate si^ica'.c
Control
Sodium silicate
Xanthan quro
Citrus pectin
Borate silicate
Polyvinyl acetate
Dispcrsant B
Dispersant A
Control
Surface collector
No observable
difference







 •  The lowest nuirJuer  indicates the healthiest plot and the highest number indicates the unhealtliiest p
   (i.e., 1  « healthiest plot; 9 » unhealthiest plot).

••No observable difference among bracketed agents.

 ff  Dead plants observed in t&tit plots.
                                              81

-------
"Comparative  Ibxicities  of  Oils, Oil Enactions and Bnulsifiers," Ecological
Effects of Oil  Pollution,  ed.E.B. Cowell,  London  Institute  of  Petroleun,
1971.)  Although not observed during testing, it is suggested that #2 fuel oil
may have penetrated the soil and killed the plants' roots and rhisranes as wall
as stems and  leaves.  Subsequently, rhizomes from the surrounding soil invaded
the plot, giving rise to the scant vegetation later observed there,  the  more
viscous  #6   fuel  oil  probably  did  not  penetrate the soil.  Consequently,
underground portions of plants exposed to this oil were not affected.

      The semiqupntitative indexes described previously  provided  a  means  to
suggest  airi  rank the relative toxic response of each surface treatment agent
for each test oil  and control condition.  The results are presented  in  Table
B-16.   A  few trends are apparent.  Note the relative position of the control
plots.  In the first observation period (February 10), the data  suggest  that
most  agents were associated with better-tnan-control plant response for the #2
and f& tuel oils,  and most produced diminished results with Arabian crude oil.
Over  the longer term, the data suggest that most agents are associated with a
better-than-control or an equivalent-to-control recovery.  It should be noted,
however,  that  marsh reaction to various kinds of disturbances (including oil
pollution) is cottnonly manifested by heavy growth and speciation changes.

      The increased difficulty over time in  distinguishing  between  different
agent effects  is apparent.   Sodium  silicate appears to be the least toxic
agent,  ^ilthough it seems that the surfactants may be toxic, it  is  difficult
to extract more detailed conclusions frcm the limited data.

      Many of  the test  plots  became  overgrown  with  pickleweed  (Salicornia
virganica)  during the  course  of  investigations.  It is possible that this
resulted from sane subtle effect of oil contamination.   However,  examination
of  the  surrounding  area  revealed  that  pickleweed  was  probably about to
colonize the  test  area independently from human activity.

Quantitative  Data—
      Regression  coefficients  of  height  vs.time  (i.e.,growth  rates)  were
calculated  for  all data points on each plot and for the three smallest stems
within each plot at each sampling period.  (Calculations were based on methods
developed  by Robert  R.Sokal  and  F. James  Rohlf, Biometry, San Francisco:
W.H.  Freeman  and Company.) Although the latter analysis  wao  strongly  biased
toward  young steins,  the same bias applies to all plots.  Furthermore, it is
reasonable to assume that if long-term stunting occurred, it would be detected
as  a shorted  minimal  stem  length in adversely affected plots.  Short-term
stunting that affected only stems that were growing when test agents and  oils
were  applied  might remain undetected.

      Results  of these regression analyses are displayed  in  Tables  B-17  and
B-18, along  with the nuribar of times that plants on each plot were measured,
and the statistical significance of the difference of growth coefficients frcm
zero.  Statistical  significance  Jepsnds  on  the  number  of  samples,  the
variation in  growth rate among grass stems, and the growth rate of  individual
plants.   Differences  in  the  number ; of  times  each  plot  was sampled are
attributable  to   tidal  inundation  of  the  test  area  during   the   first
height-measurement sanrpling  and, to .bank  erosion that undercut some plots,


                                      82

-------
                 TABLE B-17. REGRESSION COEFFICIENT - GROWTH RATE (cm/day)  USING ALL DATA
                 3
                                                                               '
 agent
Wet Control
                                                             Fuel Oil
                                                                               Arabian Crude
                                                                                                 t
                                                                                             <4-J
                                                                                             1   i
                                                                                                       16 Fuel Oil   to
3% Sodium (1) .0398 ns 3* (6)
silicate
1» Xanthan (2) .0288 ns 3 (7)
gun
1* Citrus (3) .0129 ns 3 <8)
pectin
3» Borate- (4) .0564 «* 3 (9)
silicate
W mixture
u>
100» Voly- (5) .0573 ns 3 (10)
vinyl
acetate
Surface (39) .0573 ns 3
collector
t
Dispersant B (40) .0366 ns 3

Dispersant A (41) .0546 ns 3

Control


-.0180 ns 3 (13) .0730 . ** 3 (17)

.0411 •* 3 (14) .0971 ns 3 (19)
(33)
.0433 ns 3 (11) .0357 ns 3 (18)

.0056 ns 3 (12) .1137 ns 3 (20)



.0345 ns 3 '15) .0282 ns 3 (21)
(29)
<34)
(42) .0463 ns 2 (35)


(43) .0670 ns 2 (32)
(37)
(44) .0968 ** 3 (31)
(38)
(15) .1242 ns 3 (22)
(30)
(35)
.0643

.0863
.0522
.0748

.C917



.09BO
.0496
.0598
.0284


.0841
.0777
.0032
.1103
.0825
.0309
.0729
ns

ns
ns
ns

ns



ns
ns
ns
***


ns,
ns
ns
***
ns
ns
na
3

'.3
;3
'3

3



3
3
3
3


3
3
3
4
:3
3
3
(24) .0997 ns

(23) .1022 ns

(26) -.0058 ns

(25) .1096 ns



(27) .0478 ns


(45) .0815 ns


(46) .1141 ••

.(47! .0650 ns

(28) .C479 ns


3

3

3

3



4


3


3

3

3


  * 10 stems measured at each sample.
1 ** Probability less than .05 that true growth rate is equal to 0.
*** Probability less than .01 that true growth rate is equal to 0.
na • Growth rate is not significantly different fron 0.

-------
                                   TABLET B-18. REGRESSION  COEFFICIENT -  GROWTH RATE  (cm/day)
                                              USING THREE SHORTEST  STEMS IN EACH PLOT
                                                                                                         s   I
                                                                                                        •H   'US
                       Dry Control
                                              Wet Control
                                                          'I
                                                                     #2 Fuel Oil   ra
                                                                                          Arabian Crude
                                                                                                    0!


                                                                                                    '(->
                                                                                                                  '*6 Fuel Oil
CD
3


.0614 •* 4


.0899 *** 4

.0037 na 4

.P642 ** 4

,0246 ns 4


           * 10 stems measured at each sample.
          *• Probability less than .05 that true growth rate is equal to 0.
         *** Probability less than .01 that true g«-th rate is equal, to 0.
        ***• Probability less than .001 that true growthirate 1« equal to 0.
         na » Growth rata is not significantly different from 0.

-------
 causing them to fall to the tidal  flats below the marsh.  These plots were no
 longer  growing  under  equivalent  conditions  and  could   therefore   not be
 considered valid samples.

      For most agents and agent/oil combinations, no  statistically  significant
 growth  rate  coefficients are apparent in the data.  However, it is important
 to exercise caution in interpreting these data, and  the  variations suggested
 should  not  be regarded as conclusive.  Observed  (nonsignificant)_differenceH
 may result from factors other than treatment differences,    Figure  D-5  shows
 the location of all plots  that displayed  a significant growth rate coefficient
 in the regression analyses.  Some  scatter is apparent, but  there  also seems to
 be some clustering toward  the shoreline.

      In plots that were severely affected by agents and/or oil,   many  dead
 plants  (height  recorded  as 0. on) were  initially present.   The  later  samples
 included stems that were  equivalent  in   height   to many   in  less severely
 affected  plots.   It  is   not  known  whether  these steins grew  frcra rhizomes
 initially present in t)ie soil and  stimulated by the  testing or  from rhizomes
 that  invaded  from  adjacent  areas of the marsh.   Whatever their origin, the
 sudden presence of tall stems is reflected in a high calculated   growth  rate
 that may not reflect the true situation.

      Further  testing  using  modified techniques  will    be  necessary  to
 conclusively identify and  quantify toxic  responses.

 PRELIMINARY WIELD TESTS -  BEACHES

      Preliminary field tests of surface   treatment  agent   effectiveness  and
 application  techniques were conducted in the  beat  tank previously described.
 Most of the beach tests were performed concurrently  with tests  of  agents on
 salt  marsh.   Mavable 0.3-square-meter trays that held simulated beaches made
 of sand and of cobble/gravel/sand  mixtures were used in ths tank.

      The purposes of the preliminary field tests were:

        * To gain operational experience in the  use of surface treatment agents

        * To evaluate the durability of agents on various beach  substrates

        * To evaluate different agent  application  .equipment and  methods of
          relieving the agent

        * To determine which agents should be recommended  for full-scale -field,
          tests

      Three series of preliminary field tests were  conducted. The  purpose of
 the first series was to evaluate the durability of the film-forming agent*, and
 the  ease  of  flushing of  oil  from ;  these   agents   on   sand   and. on
 bobble/gravel/sand  test beaches,  under both wst and dry substrate conditions.
 |Itie film-forming agents tested were sodiun silicate, borate-silicate mixture,
 citrus pactin, xanthan gum, and polyvinyl acetate.  Tide and wave actions were
> simulated in the tank for  these tests.  In the  second series, additional tests


                                       85

-------
                                Mud f Us
                                                         I
                                    Water
                                         Mudflats
                                            Water
                                        ~ From analysis of all data

                                        - From analysis using three
                                         smallest stems
Figure  B-5.  location of  plots with growth rates
        significantly different from zero.
                           86

-------
mere  conducted with the tvo film-forming agents that proved successful in the
first series, polyvinyl acetate and  xanthan  gum.   In  the  tests  different
application  techniques,  agent  concentrations,  and  agent drying times ware
evaluated and  the  two  agents'  resistance  to  oil  contamination  and  oil
penetration  was  assessed.  The third test series evaluated four surfactants,
usir*j two  application  techniques  to  determine  the  effectiveness  of  the
surfactants  in ; preventing  or  reducing  oil  contamination on test beaches*
Surfactants tested ware the surface collector, dispersant A, dispersant B, and
dispersant C.

Test Procedures

Test Beach Construction—
     Test beaches were constructed on 0.3-square-meter trays that  slide  into
individual cells in the test tank.  Tne sand beaches were ccniposed of about 23
kg of counercially available sand about 75 nm  deep.   Vne  ccfcble/gravel/sand
beaches  consisted  of  a 25-mn layer of sand overlaid with a layer of rounded
gravel (less than 25-nrn diameter) and with 10 to 15 cobbles (75-ran  to  150-wtn
maximum diameter).

Test Series JL

       * Test beaches were constructed for each test.

       * The lower half of each beach was sprayed with salt water.

       * Borate-fcdlioate mixture, sodium silicate, citrus pectin, and  xanthan
         gum  were premixed (using an electric blender) into water suspensions
         at the concentrations recommended  by  TRI.   The  agents  ware  than
         applied  to  r-ach test beach by spraying at 1.75 kg per sq era (25 psi)
         with a garda} sprayer (7.6-liter capacity).   The  polyvinyl  acetate
         was  used  undiluted  and applied with a point-sprayer/air-corpressor
         system at 4.2 kg per sq on (60 psi).

       * The agents were allowed to dry for varying, periods of time  and  then
         each  beach was submerged under water in the test tank for 10 minutes
         to simulate tidal action.

       * The test beaches were retracted to a higher position in the tank  and
         subjected to simulated wave action for 5 minutes.

       * The agent on each test bsach  was  examined  to  determine  the  film
         durability and integrity.

       * No oil was used in test scries 1.

Test Series 2_

       * Test beaches ware constructed and prepared for each test as  in  test
         series 1.

       * Xanthan gum, when applied dry, was sprinkled  by  hand  on  the  test
         beaches.

                                      37

-------
       * A hydraulic spraying  system  was  used  for  polyvinyl  acetate  and
         xanthan gum solutions.

       * After application, each agent was alleged to dry for a  given  period
         of  time,  and  the test beaches were then partially submerged in the
         tank.  Five hundred mis of Arabian crude oil was added to  each  test
         cell, and simulated wave action was sustained for 5 minutes.

       * Jifter the wave action ceased, the test beaches  were  retracted  fron
         the  water  and  flushed  with a water spray at 1.75 kg per sq on (25
         psi) to test the ease of flushing the agent-coated beach.

       * A segment of test beach was cut and  renewed  fron  a  representative
         area  and  examined under shortwave ultraviolet light to test for oil
         penetration.   Ihe  aromatic  content  of  crude   oil   exhibits   a
         characteristic  fluorescence  which, when detected on the side of the
         sample segment, indicates the degree of oil penetration.

Test Series 3^. Surfactants

       * Test beaches were constructed and prepared for each test as  in  test
         series 1.

       * Two agent application techniques were tried with the surfactants.

          - All four agents wers sprayed onto partially submerged test
            beaches and into the water in front of the beaches.  Five hundred
            mla of crude oil was then introduced into each test cell, and
                 action was sustained for 5 minutes .
          - The test beaches were partially submerged in the tank, and
            503 or 750 ml of crude oil was placed into each test cell.

          - Wave action was initiated and the agent sprayed onto the
            foreshore of the beach and into the water in the surf zone in
            front of the advancing oil slick.

       * Oil  penetration  into  the  simulated  beaches  was  determined   as
         described in test series 2.

Results

     Detailed results of the test series on beaches are given in Tables  B-19,
B-20, and B-21 and discussed below.

     Biefjfective  Agents.   Three  film-forming   agents   proved   ccsnpleteJ.y
ineffective  acT surface  treatment  agents  on  sand  or  gravel/cobble/ sand
beaches.  These were sodim  silicate,  borate-silicate  mixture,  and  citrus
pectin.   All three agents either dissolved or were mechanically fragmented by
wave action arid/or by suteaergence in water.  Further tests of the three agents.
were discontinued.
                                      88

-------
                            TABLE B-19.  SURFACE TREATMENT AGENT BEACH TEST, SERIES 1
m
vo
Tost fluHb«r 1.1
•ilicate
BcacJj Type Sand

Hater tern" 10
Future ( C)
Wind speed 0.0
(si/ see)

Spray 1.75 kg/
(25 psij
Volum? of 50O
A-jent Used (ml)
Percent 1
D i 1 ut ion
Titfw Hequited 60
to Spray
Agent (» (60 psiJ (C3 p-ii:
455 500 20O£> 5OO 3CO ;00

3311 100 100

40 SO 50 SO 1LO 90


1,40 2.25 2.05 2.4* ),4O 1:40


unfl) none ypm; none dry beech dry tection rcrjir,«-i, but . a (nl rcr>ainrj
en beach on beach BOOT vni aectionj en ccbtlfs «f*ii
roraoved fro» Dvcrallj 3ei» tc*t
wet beach re?.alnrd than
Foaa and — tone froth — Difficult Difficult
on Burfaca poored on Bpray^r. s; rayor
during test teach clo-ia^d c to(?'-i<*j



t*ats


-------
TABLE B-20.  SURFACE TREATMENT AGENT BEACH TEST, SERIES  2
Test Number
Agent Tested
Beach type
Water tem-
perature ( C)
Air tem-
perature ( C)
Wind apeed
(si/sec)
Percent
Cloud Cover
Applicatic.i
Method and
Spray
rreinuro
Volume of
Agent
Percent
Dilution
Application
Hite
Time Required
to Spray
Agent (sec)
Agent Dry-
ing Tiirj
(hr:ir.in)
2.1
Xanthan
gum (d y
powdei-)
Sand
9
10
1.0
None
Sprinkled
powder on
beach; ap-
plied water
spray
50 g
N.A.
166 g/iq m
120
(dust and
spray)
0:10
2.2
Xanthan
gum (dry
povder )
Cobble/
gravel/sand
9
10
1.0
None
Sprinkled
powder on
beach ; ap-
plied w uer
• pray
50 g
N.A.
166 g/sq n
120
(dust and
spray)
0:10
2.3
Xanthan
gun
Sand
9
10
3.5
None
Hudson
sprayer,
1.75 kg/
ca (25 psi)
1000 ml
N.A.
33 g/sq m
90
2:40
2.4
Xanthan
gum (dry
powder)
Sand
9
10
3.5
None
Sprinkled
powder on
beach; ap-
plied water
• pr«y
100 9
N.A.
333 7/sq m
120
(dust and
spray)
2:30
2.5
Xanthan
gum (dry
powder)
. Cobble/
gravel/sand
9
10
3.5
None
Sprinkled
powder on
beach; ap-.
plied water
spray
100 g
N.A.
333 g/sq m
120
(dust and
spray)
,2:30
2.6
Xanthan
gura
Sand
7
19
1.0
50% hazy
sprayed
agent on
beach with
hydraulic
sprayer,
14 Kg/sq en
(200 pal)
1000 ml
1
33 g/sq n
5
0:30
2.7
Puly vinyl
acetate
(Amsco 3011)
Sand
9
10
1.0
None
Hudson
sprayer,
1.75 kg/sq cm
(25 psi)
400 ml
100
1333 ml/sq m
240
2:30
2.8 2.9 2.10
acetate
(Amsco 3011)
Sand Sand Sand
7 6.5 7
19 18 16
1.0 1.0 1.0
50% hazy None 50% hazy
Sprayed N.A. N.A.
aqent on
beach with
hydraulic
Bprayor,
14 Kg/sq cm
(200 psi)
500 ml N.A. N.A.
100 N.A. N.A.
1666 ifll/sq m N.A. N.A.
15 N.A. N.A.
0:30 N.A. N.A.
                                                                      (Continued)

-------
                                                            TABLE B-20  (Continued)
vo
Test, Nuober
Agent
Tested

Volume and
Typo of oil
Applied (mi)
Percent Oil
Coverage
on Beach
After Test
Depth of
oil Pene-
tration (en)
Results
of Accent
Test










Consents








2.1
Xanthan
gum (dry
powder)
None


N.A.



N.A.


No ditfer-
encc in
jelling on
vet and dry
surfaces;
»o«t of
'agent fiim
broke up in
wave action

-------
TABLE B-21.  SURFACE TREATMENT AGENT BEACH TEST, SERIES 3
Test Number
Agent
Tested
' Beach Type

Water Ten-
parature (°c>
Air Ten-
pcrature ( c)
Kind Speed
Cn/sec)
Percent
Cloud Cover
Application
Method and
Spray







Volume of
Agent
Percent
Dilution
Application
a»te
Tine Rcodired
to Spray
Agent (sec}
3.1
Dispersant
C
Sand

6.5

IS

o.a

Clear

Sprayed
agent on
beach with
pr«ssor
spray gun
at 4.2 kg/
sq cm
(60 psi)


560 g

10

186 »l/sq n

90


3.2
Oispersant
B
Sand

6.5

-18

O.8

Cloar

Sprayed
agent on
beach with
pressor
spray gun
at 4.2 kg/
sq cn
(60 pst)


100 g

105

33J ffll/sij m

30


3.3
Dispersant
A
Sand

6.5

13

0,8

Clear

Sprayed
agent on
beach with
pressor
spray gun -
at 4.2 kg/
sg. cn
(60 psi)


500 g

2

33 ml/jq n

24O


3.4
Surface
collector
Sand

10

IB

2.2

eo

Sprayed
agent on
beach and
with Hudson
sprayer at
1.75 kg/
9<3 OB
(25 psi)


40 ad

100

133 al/sq r

10


3.S
Dispersant
B
Sand

10

IS

2,2

80

Spra/ed
agent on
beach and
ahead of
advancing oil
.•'lick with
Hudson spray-
er at 1.75
kQ/aq cm
(25 psi)
75 ml

100

2£0 mi/sa fl

30


3.3
Oispersant
A
Cobble/
gravel/sand
10

1.8

2.2

00

Air compres-
sor and
spray gun
bles at 4.2
kg/sq cm
(60 psi) and
and into
water ahoad
of oil slick

200 ml

2

13 ail/sq m

30


3.7
Dispersant
A
Cobble/
9"vel/sand
B

12

0.5

20

Sprayed
agejit into
water ahead
ing oil
slick with
Hudson
fipray^r at
1.75 kg/
sq cm (25
psi)
SOO ml

2

33 »l/Bc; u

60


3.8
Dispersant
A
Sand

S

12

0.5

;o

Sprayed
aqcnt into
water ahead
ing oil
slick with
Hudson
sprayer at
1.75 kg/
sq on (25
psi)
500 ml

2

33 Ell/sq TT

60


3.9 3.10
Dispersant Control
C baach
Sand Sand with sev-
eral cobbles
8 B

12 i:

0.5 0.5

20 ;a

Sprayed N.A.
37°nt into
water ahead
oil slick vith
Hudson sprayer
at 1.75 kg/
aq en (25 psil



500 ml N.A.

10 N.A.

166 nl/:nj IB W.A.

iO N.A.



-------
                                                         TABLE B-21   (Continued)
Test number
Agent
Tested
Percent Oil
Coverage on
Beach After
Teat.
Depth of Oil
Penetration
(cm)

Results of
Agent Test







Commnti










3.1
Dispcrsant
C
30



1.3



Some oi-'
dispersion
on water
however*
oil pene-
trated
beach



Spraying
surfactant
diapersartts
cnto beach
prior to
arrival of
oil is not
effective
in reducing
oil con-
tamination
3.2
Dispersant
B
30



1.3



Oil dis-
persed to
some ex-
water sur-
face; how-
ever, oil
penetrated
beach


..










3.3
Dispcrsant
A
80



1.3-1.9



No oil dis-
persion on
water sur-
oil pene-
tration
similar to
control
beach


„










3.4
Surface
collector
<5



Occasional
spot: 0.6
cm below
surface
Very effec-
tive i only
some oil
splash zone;
tended to
trtve oil
off in
snail
slicks

..










3.5 3.6
Dispersant Dispcrsant
B A
1-10 30



Occasional Some pene-
spots 0,3- tration
0*6 cm below
surface
Excellent Fair effec-
oil dispersed cobbles re-
column; little free; some
remained on oil on sand
beach and gravel




..










3.7
Diapersant
A
60



N.A.



Sand and
lower half
were coated
with a light
covering
«f Oil!
pebbles had
more oil
than rocks
—










3.8 3.9
Disoersart Dispersant
A C
<10 80-100



No pcne- Penetration
tration greater than
control - 3.8

Excellent Not effective;
ness on contamination
was dis-
persed into
water co':':jnn;
very little
on beach


..










3.10
Control
beach
80-100



?,3



Cobbles on
beach coated
with oil







—










NOTES:  Water salinity - 32 ppt
       Surface conditivn - 100» wet for Test 3,4, 50* w«t and 50% dry for all other tests
       Agent drying time - in Test 3.9, 8P 100-WD was allowed to diy for 10 minutes
       Volume an'i type of oil applied  - 500 ml Arabian crude oil
       N.A. - not applicable

-------
      Xanthan Gum and Polyvinyl Acetate.  Xanthan gum proved fairly  effective.
 It provided a soft,  jellylike barrier film on both sand and gravel/cobble/sand
 test beaches and was most effective when applied to  dry  test  beaches  in  a
 premixed  1%  solution.    It retained film integrity scrnewhat less effectively
 when applied to wet surfaces.  When xanthan gun was applied as  a  dry  powder
 and than sprayed with water, it formed a more rigid film;   but the film tended
 to break easily under wave action on a sand test beach.  On cobble/gravel/sand
 test  beaches  the  film  formed  from  dry powder was more successful and did
 maintain film integrity.  In all cases where film integrity was maintained,  a
 water spray easily flushed oil from the surface coated by xanthan gim.

      When allowed sufficient time to dry, polyvinyl acetate also  provided  an
 effective  protective  film on both sand and cobble/ gravel/sand test beaches.
 The drying time is critical in the use of polyvinyl acetate.  On  tests  where
 polyvinyl  acetate  was still wet, it dissolved into the water column and lost
 film integrity.  Polyvinyl acetate tended to dry faster on cobble  and  gravel
 than  on sand.  Where the polyvinyl acetate film integrity was maintained, oil
 penetration into the beaches was limited, and oil was easily flushed from  the
 agent-coated beach surface by a water spray.

      The films of both xanthan gum and polyvinyl acetate can be removed from a
 sand  test  beach with a high-pressure water spray, which breaks the film into
 snail particles.  Itowever, it is considerably more difficult to remove xanthan
 gun and palyvinyl acetate films from cobble and gravel surfaces.

      Several cobbles coated with xanthan gum and with polyvinyl  acetate  were
 left  to cry for. 24 hours.  The xanthan gun dried to a firm, nonbrittie crust,
 and polyin/1 acetate dried to a hard, paintlike  coating.   The  agent-coated
 cobb''-i3  ware  subjected  to  steam cleaning by a portable steam cleaner for 5
 minutes v.th no apparent effect on either agent.

      Surscace Collecting Agent.  Ihe surface collector proved very effective in
 reducingoTl  contamination of the test beach, although this result was quite
 different from those of the tests performed on the  collecting  agent  in  the
 laboratory.    TRI   tested   it  in  the  concentration  reccmmended  by  the
 manufacturer, which is 1 gallon per 2 linear miles of oil slick perimeter,  or
 approximately  1.2  ml  per  linear meter of beach.  At this concentration the
 surface collector proved ineffective.  In  the  tank  tests,  however,  higher
 concentrations  ware used.  The agent was sprayed onto tha test beach and into
 the water in front of the beach, where ,it successfully repelled oil from  most
 'of the beach surface.

      Dispersing agents.  When  they  were  applied  properly,  the  dispersing
 agents.  A,  B,  and  C,  effectively  protected  the  test  beaches  fron oil
 contamination.  When they were used  like  the  film-forming  agents  and  the
 collecting agent (i.e., when they were sprayed onto the shoreline before tidal
 and wave actions were begun), the dispersing agents were  ineffective  and  in
 one  case caused more oil penetration than occurred on the control test beach.
 When they were sprayed into the water {i.e., surf zone) ahead of the advancing
; oil  slick,  the  dispersing agents effectively prevented contamination of the
                                       94

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sandy  test  beaches.   These  agents  were   scmewhat   less   effective   on
cobble/gravel/cand test beaches;  sctne oil contaminated the cobble/gravel/sand
substrate,, but there was considerably less contamination than on  the  control
beach.

     Application Eqaipment.  Three types  of  equipment  for  applying  liquid
agents were evaluated during the preliminary tests.  They were:

       * Hand-operated garden-type sprayer

       * Air compressor (pneumatic) paint spray gun

       * Hydraulic sprayer

     The hydraulic sprayer was the most effective system for applying the  two
film-forming  agents,  xanthan  gum,  and  polyvinyl  acetate.   Due  to their
viscordty, both agents require high-pressure application to  provide  an  even
coatim  in  a  reasonable  amount  of  time.   When the lower pressure garden
sprayer (1.75 kg per sq cm, or 25 psi) and the pneumatic paint sprayer (4.2 kg
per  sq  cm,  or  60  psi)  were  used to apply these agents, the spray nozzle
clogged frequently, which increased spraying time and  made  it  difficult  to
aPPly  the  agent  evenly.   However, the lower pressure spraying systems were
effective in applyingrthe surfactants.
                                      95
                                                    rVfMNG GUIDE

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                                  APPENDIX C

                      BIOASSAY OF EASTERN BLUE CRAB WITH
                       SELECTED SURFACE TREATMENT AGEOTS
INTRODUCTION

     Two surface treatment agents - polyvinyl acetate (PVA) and xanthan gum  -
were  selected  for  the  static  bioaasay testing  (96-hour TIM).  First-stage
ijuveniles of the cotmercially important blue crab,  Callinectus  sapidus,  were
used  as test organisms.  The concentrations tested were in ranges believed to
occur in seawater after an agent film had been  removed  from  the  beach  and
marsh shorelines.

MATERIALS AND METHODS

     Juvenile* blue crabs were furnished  by  Sea   Plantations,  Inc.,  Salem,
Massachusetts   Approximately 140 crabs were collected fron the tidal flats of
Delaware Bay on 16 October 1977 and 24 October 1977, packed  in  seawafcer  and
seaweed,  and air-shipped to Salem.  The crabs were held in aquarium tanks (pH
=7.6, salinity = 32 ppt, temperature =* 21 C) and fed  euphausiid  shrimp  and
small  pieces  of  fish.   On  3  Novatiber 1977, the crabs were air-shipped in
plastic bags containing wet seaweeds to  Pacific  Environmental  Labs  in  San
Francisco.   There  was  no  apparent  ;stress or mortality of the crabs due to
shirroant.

     The crabs were acclimated to test conditions in  a  30-gallon  plexiglass
aquarium  tank  for  90  hours.   Compartments within the tank kept the larger
crabs separated from the smaller ones.  The tank  contained  filtered  Pacific
Ocean  seawater  (pH  =  7.8 and salinity = 30 ppt) from Steinhart Aquarium at
Golden Gate Park  in  San  Francisco.   Temperature of  the  seawater  during
acclimation was maintained at 18 +1 C.  The crabs were fed brine shrimp during
the acclimation pariod but were not fed during the  96-hour teat period.
* Because of the severe 1976 winter in the east, post-larval (megalops) crabs,
the  prescribed test organism, ware 1 to 2 months late.  When they finally did
appear in the water column, the msgalops populations were extremely sparse and
difficult  to  locate.   After  nutieroiis  plankton  tows failed to produce any
megalops, and efforts to hatch eggc fron five sponge crabs  similarly  failed,
Sea  Plantations  turned  thsir efforts in October to obtaining snail juvenile
crabs.

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     The bioassay test was performed in accordance witi; the method as outlined
in  "Standard  Methods  for  the  Examination  of  Water and Waotewater," 14th
Edition, APHA-AWWA-WPCF,  and "Guidelines for Performing Static Acute Bioassays
in  Municipal  and  Industrial  Wastewaters,"  1976,  of  the California Water
Resources Control Board and Department of Fish and Game.

     The tests were performed  in  seven  19-liter  plexiglass  aquaria.   The
volume of the control and each of the test concentrations were 10 liters.  The
control and dilution water used was filtered seawater from Steinhart Aquarium.
The  liquid  depth of each tank was 12.5 ^3.2 on.  Compressed air was used for
aeration.

     The test concentrations used were selected (1) to reflect  concentrations
that  would  occur  after  the  agents  were  flushed frcm the beach and marsh
shorelines, (2) to bracket the lethal and nonlethal toxicity levels of the two
agents,  and  (3) to make the best use of what turned out to be a small sample
size.  Estiniates of agent concentration after flushing were obtained by taking
the  application  quantities  per unit area established during the field tests
and estimating the runoff from this area  into  a  small  marsh  channel.   By
assuming  that  this  receiving water was a closed unit and of minimum volur.e,
worst-case concentrations were estimated (10%  for  xanthan  gum  and  5%  for
PVA) .*  The  maximum  PVA concentration was estimated at half that for xanthan
gum because PVA tends to adhere better to  the  plant  surface  and  less  was
applied per unit area.

     In an attenpt to locate the sublethal toxicity limits  for  both  agents,
the  remaining  test  concentrations  were obtained by multiplying tha maximum
concentrations by a factor of  0.3.   In  this  way,  a  geometric  series  of
boncentrations,   with  the  lower  limits  below  1%,  were  obtained.   Test
concentrations by volume of EVA were 5, 1.5, and 0.45%;   test  concentrations
by volume of xanthan gum were 10, 3, and 0.9%.

     So that size differential would not become a confounding variable, 70  of
the  snallest  blue  crabs  received from Sea Plantations were selected as the
jbest organisms.  These crabs were between 6 millimeters and 32 millimeters  in
length  (average  = 12 millimeters) and approximately 45 to 75 days old.  With
only 70 organisms, the tests were limited  to  three  concentrations  of  each
agent, 10 organisms per tank.  One 10-crab tank served ar the control for both
agents.  Crabs were placed in the tanks so that each tank contained conparabla
size  distributions  which,  in  turn, ; reflected the distribution of the test
population.
* Concentrations referred to in this report reflect the percent by  volune  of
the  teat  agents  in seawater.  The pre-dilution strengths of the agents ware
the same as they were tested in the field:  100% for the PVA and  1%  for  the
xanthan gisu
                                      97

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RESULTS AND DISCUSSION

     Mortality data for the 96-hour TLM are listed in Table C-l and  displayed
graphically  in Figures C-l and C-2.  Goth the PVA and xanthan gun agents were
acutely to.xic to all organisms in the highest concentration  tanks.   The  PVA
seemingly  affected  the  crabs more quickly than did the xanthan guni.  Though
only two of the crabs in 10% xanthan gum were dead after 24 hours, six  others
were  moving  very  slowly by that time.  By 48 hours, all 10 crabs in the 10%
xanthan gum had died.

     Kfo mortality occurred in the tanks subjected to the lowest concentrations
of  each  agent.   The  intermediate  PVA  concentration  (1.5%)  was  not  as
immediately toxic to the crabs as was the 5%  concentration,  but  four  crabs
died  between  the 48- and 72-hour reading ?.nd another four died by the end of
the  test.   The  10  crabs  subjected  to  the   intermediate   xanthan   gun
concentration  all  survived.   All 10 of the control crabs survived,  btone of
the surviving crabs in the test showed  any  signs  of  paralysis  or  stress.
Although  the  sizes  of the crabs varied between 6 nm and 32 inn, there was no
apparent correlation between the size and mortality of the test animals  used.

     During the test, two of the blue crabs molted (one each in  3%  and  0.9%
xanthan  gum  concentrations).   Both  of these molted blue crabs survived the
96-hour test period with no apparent paralysis or stress.

     Water quality data taken during the tests (Table C-2) suggest that a  low
pH might have contributed to FVA's rapid and acute toxicity.  Figure C-3 shows
:that as the concentration of FVA  increased,  initial  pH  and  alkalinity  (a
measure  of the solution's buffering capacity) decreased.  In the 5% PVA tank,
the pH decreased to 4.2 and remained at that level  for  at  least  48  hours.
iVJhile  the  pH  decreased  to 5.9 in tha 1.5% tank, within 24 hours the pH had
Iclimbed back to more than 7 with no apparent effect on mortality.

     Dissolved oxygen levels  fluctuated  considerably  throughout  the  tests
(Figures C-4 and C-5).  At all three concentrations of xanthan gun, the oxygen

               TABLE C-3.   STATIC ACUTE BIOASSAY MORTALITY (%)

Control
Initial
0
24 Hours
0
48 Hours
0
72 Hours
0
96 Hours
0
PVA
.0%
.5%
                0.45%
Xanthan gum    10.0%
                3.0%
                0.9%
0
0
0

0
0
0
 80
 0
 0

20
 0
 0
100
 0
 0

100
 0
 0
100
 40
 0

100
 0
 0
100
 80
 0

100
 0
 0
                                      98

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             9 -
             8 -
  Number of   7
Test Animals
    Dead
             6 -
                                                                      10%
1.5Z
                                                                      0.45*1
             Initial
    Figure C-l.  Static acute bioassay  mortality — polyvinyl acetate.


                                   :   99

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            10
  Kumber of
Test Aclmals
    Dead
               Initial       24
 /•a

Hours
72
                               10%
                                                                       3Z& 0.9*
                                                                     96
        Figure C-2.  Static acute bioassay mortality — xanthan  gum.



                                      100

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TABLE C-2.  ALKALINITY,  pH, AND DISSOLVED OXYGEN DURING  THE  96-HOUR TLM
Initial

Control
PVA


Xanthan
gum



5.0%
1.5%
0.45%
10.0%
3.0%
0.9%
Alk.
144
1.0
89
126
146
146
146
pH
8.0
4.2
5.9
6.9
8.0
8.1
8.1
D.O. Alk.
8.6
8.3
8.5
8. 6
8.4
8.5
8.6
24 Kours
pH
7.9
4.2
7.2
7.4
7.1
7.6
7.8
D.O.
8.1
8.9
8.3
2,6
3.0
6.2
7.4
48 Hours
Alk. pH
7.8
4.3
7.2
7.8
7.7
7.7
7.9
D.O. Alk.
3.0
8.6
3.4
8.0
7.8
7.6
8.4
72 Hours
pH D.O.
7.8 8.0
_-
7.2 2.6
7.9 9.2
7.8 7.6
7.9 8.2
96 Hours
Alk. pH D.O.
7.7 7.7

7.5 4.5
7.9 8.0
7.7 7.0
7.9 7.R

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pH
             \
              \
                \
                 \
                   \
                    \
                      \
\
                           \
                             \
                               \
                                 \ Alkalinity

                                      X
                                        N
                                          \
                                            \
                                                         160
                                  .120
80  Alkalinity
        mg/1
                                  40
                           23

                          Z Concentration
       Figure C-3.  Effect of different concentrations of PVA
               on alkalinity and pH in the test tanks.
                                 102

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Dissolved
  Oxygen

   mg/1
            Initial      24
  48

Hours
72
                                                                     0.9%
                                                                     Control
96
       Figure C-4.   Dissolved  oxygon fluctuations —  xanthan gum.
                                    103

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Dissolved
  Oxygea
   mg/1
            Initial       24
 48
Hours
72
                                                                    0.45%
                                                                    Control
                                                                    1.5%
96
    Figure C-5.   Dissolved oxygen fluctuations — polyvinyl acetate.
                                   104

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level decreased during the first 24 hours of  the  test  before  returning  to
control  levels.   The  dissolved  oxygen  in  the  10%  tank  dropped  to 3.0
milligrams per liter, possibly contributing to the narcosis observed in six of
the  surviving  eight  crabs  in  that  tank.   Oxygen sags, however, were not
necessarily associated with mortality.  The oxygen level in the 0.45% PVA tank
dropped  to 2.6 milligrams per liter during the first 24 hours with no adverse
effects.  Thus, wliile it  is  possible  that  the  loss  of  dissolved  oxygen
contributes to the mortality of the crabs, especially when the crabs are under
stress due to the presence of high concentrations of the agent, data frctn this
bioassay  are not extensive enough to implicate oxygen sags as a factor in the
toxicity.
     Ihe TLMs for the two agents were estimated graphically (Figure C-6).   In
this  case,  the TLM is an integrated value approximating the concentration at
which 50% of the experimental animals survived.  The 96-hour TTM for  PVA  was
0.95%;   the  48-hour TLM for PVA was 2.3%.  Both the 48- and 96-hour TLMs for
xanthan gun were 5.5%.

     Ihese TIM values, and particularly those for the high  concentrations  of
the  agents,*  probably  reflect  the crab's response to conditions worse than
would occur in the natural environment.  Whereas  the  initial  concentrations
Delected  probably  are realistic estimates of their potential strength in the
natural environment, the chances of these  concentrations  persisting  for  96
hours  are  extremely  low.   Tidal  flushing of the beach and marsh shoreline
would effectively dilute the agent  concentrations.   Thus,  the  24-hour  and
48-hour  TLMs  are  more  likely to reflect the worst-case conditions that the
crabs would encounter.  Similarly, the crabs in the natural environment  could
move out of and/or avoid any pockets of high agent concentrations.  .Additional
testing with concentrations intermediate to those used in this test would more
precisely  define  the  TLMs  for  these  agents, and would produce additional
information on 24- and 48-hour toxicity.

     The results of the bioassay apply only to  the  acute  effects  of  these
Agents  and  do  not  provide  any information about the effects of long-term,
chronic exposure.  The toxicity data generated also do not apply to any  other
marine  organisms,  or  even  to  other  Callinectes  of  different size, age,
location, or physiological condition.  Similarly,  the  data  do  riot  provide
information  about  possible  synergistic  and  antagonistic effects.  Oil and
oil/agent bioassays vould provide va-.uable information in this regard.
<* Researchers observing the bioassay who hM worked with the agents  comvsnted
that the lowest PVA concentration (0.45%) was most similar in appearance (like
(skimmed milk) to the PVA/water mixture  that  occurred  in  the  field  during
flushing.   In  contra?t,  the  5%  PVA tank had a thick and milky appearance.
Jmnediately after the introduction of the xanthan gum agent into the 10% tank,
the water thickened to a consistency more like the agent than water.
                                      105

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             10
            5.5
            5.0
Z Concentration

            3.0
            2.8
           1.5
           0.95
           0.45
           0.1
10       30      50       70

              % Survival
                                          1	1	1	L
                                                       90
                                         Xan.ch.an Gun
                                         48 & 95 - hour
                                                            PVA  48 -  hour
                                         PVA  96 - hour
           Figure C-6.  Estimations of 50% tolerance limits by
                 straight-line graphical interpolation.
                                    106

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FINDINGS AND REXXMMEHCIAT1ONS
      1. The acute static bioassay successfully established  96-hour  toxicity
         ranges  for the two agents:  FVA (0.45% to 3%) and xanthan gin (3% to
         10%).

      2. PVA (as applied at 100S)  is  seemingly  more  toxic  to  first-stage
         juvenile Callinectes than is xanthan gum (as applied at 1%).

      3. The  PVA  at  0.45%  concentration  did   not   have   any   apparent
         physiological effect on the crabs during the 96-hour test period.

      4. The xanthan gum  at  3%  concentration  did  not  have  any  apparent
         physiological effect on the crabs during the 96-hour test period.

      5. The 96-hour TIM for EVA was 0.95%.

      6. The 96-hour T£M for xanthan gun was 5.5%.

      7. The PVA seemed to act like a weak acid.  The persistent low pH  level.
         in  the  5% tank could have contributed to the toxicity of the agent.
         Additional tests on  the  chemical  behavior  of  PVA.  in  water  are
         recommended.

      8. Acute bioassay tests with first-stage blue crab juveniles using  five
         or six concentrations in the ranges delineated in (1) above should be
         performed.  Additional  testing  with  post-larval  crabs,  generally
         regarded  to  be  more  sensitive  than first-stage juvenile, is also
         recarroended.

      9. Organism toxicity of oil and oil plus  agents  should  be  determined
         through additional bioassay work.
                                     107

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                                  APPENDIX D

                SURFACE TREATMENT AGENT TESTS - SIEDLER BEACH,
                      NEW JERSEY, OCTOBER 18 AND 21, 1978
INTRODUCTION
     Since 1976 Woodward-Clyde Consultants  has  been  conducting  a  research
program to  evaluate the effectiveness of various natural and chemical agents
in protecting shorelines from oil  contamination.   This  program  is  jointly
funded  by  research  grants  from the Environmental Protection Agency and the
American Petroleum Institute.

     As a continuation  of  this  program,  field  tests  of  several  surface
protection  agents  ware  held at Seidler Beach, New Jersey, on October 18 and
21, 1978.

SCOPE

     The  field  test  program  was  originally  planned   to   evaluate   the
jeffectiveness  of  the  following  four  agents and a flowing film of water in
protecting shorelines from oil contamination:

        * Oil Herder, a surface collecting agent

        * Corexit 7664, a dispersant

        * BP 110SK, a disparsant

        * Polyvinyl Alcohol/Borate-Gel, a film-forming chemical

     Initially, the tests were to be conducted in the  following  manner.   On
four  -test  areas  the  surface collecting agent, the BP 1100X dispersant, and
Corexit 7664 undiluted ware to be applied onto the water surface in  front  of
an  oil slick  being carried 
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     In the revised  test  program  the  water  spray  system,  the  polyvinyl
alcohol/horate-gel, and the educted Corexit 7864 v-Tere applied to the shoreline
as planned.  Based on reccrtmendations of the  manufacturers'  representatives,
Oil  Herder  and BP 1102K were not tested.  Undiluted Cbrexit 7664 was sprayed
on the shoreline test area rather than applied to the water surface.   In  the
three  tests  conducted,  oil  was  physically forced onshore with containment
boons.

CONCLUSIONS

     Based on the results of the October  1978  test  program,  the  following
conclusions are offered:

      1. The flowing water film produced by the water spray  system  was  most
         effective   and   provided  the  best  protection  from  surface  oil
         contamination and oil penetration into the substrate.

      2. Palyvinyl   alcohol/bora te-gel   did   not   reduce    surface    oil
         contamination.   However,  it  did  prevent  oil from penetrating the
         substrate and appeared to facilitate removal of oil by flushing.   As
         a  surface  barrier, the gel remained on the beach for only one tidal
         cycle.

      3. The tests of Cbrexit 7664 as a protection  agent  were  inconclusive.
         Visual  observations  indicated that although Cbrexit 7664 applied to
         the shoreline prior to oil contact did not reduce the initial  amount
         of  surface  oil contsmination, it appeared to facilitate the removal
         of oil.  The use of Cbrexit 7664 did not reduce the bearing  capacity
         of the test areas, i.e., make it quicksand.
     Based on the findings of this study  the  following  recommendations  are
Offered:

       * Additional field  tests  to  evaluate  Cbrexit  7664  and  the  other
         products  (BP  1100X and Oil Herder) should be conducted when the oil
         is moved ashore by onshore winds and currents.

       * In future testing a larger sediment sampling program will  be  needed
         to provide ctatistically significant samples..

       * Sediment samples should be taken from the test plots for several days
         after  a  test  to  determine  if  the  agents facilitate the natural
         cleaning of a shoreline by t.''.dal action.

       * Ebr sand/gravel application, external  flushing  should  be  avoided.
         Any  ensuing  test  program  should  be  designed to evaluate several
         periods of natural tidal flushing.
                                      109

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       * Tho logistics and operational procedures for deploying  and  using  a
         water spray system on a large scale should be investigated.

FIELD TESTS

Test Site

     Field tests were conducted at Seidler Beach, located on  the  New  uersey
coastline of Raritan Bay between Laurence Harbor and Cliftwood Beach (latitude
4cP 27' 20", longitude 74° 14').  The beach is situated in the west corner  of
Raritan  Bay, just southeast of the c..—mergence of the Arthur Kill and Raritan
River, and is bordered by the outfall of Marquis Creek  to  the  northwest,  a
sewage  treatment  plant to the north, and Raritan Bay Beach to the southwest.
Seidler Beach is approximately 1600 feet long and is owned by the Township  of
Old  Bridge.   The shoreline is primarily ccmposed of coarse sand in the upper
intertidal zone with large  pebbles  dominating  the  lower  intertidal  zone.
Access to the beach is through an undeveloped 60-acre lot fronting Highway 35.

Test Oil

     A light Iranian crude oil  with  similar  characteristics  to  test  oils
previously  used  was  selected  as  the repr ssentative oil for the testing of
shoreline protection agents.  Characteristics for thits oil are given in  Table
D-l.

Dontrolleg Spilling of Oil

     Approximately 170 to 190 liters (45 to 50 gallono) of Iranian  crude  oil
were spilled for each daily agent test.  These volumes would provide a uniform
oil loading of approximately 2 to 4 liters/ mater of sloreline, or about 50 to
75 liters of oil for each individual test area.

     During each test the oil was spilled within the containment  boons  on  a
flooding tide just prior to high tide.  The boons were then pulled up onto the
beach, drawing  -Jhe oil onto the test areas.

                TABLE D-l.  CHARACTERISTICS OF IRANIAN CRUDE
            Characteristic                      Value

            Gravity                          35.5 °API

            Viscosity

                 Kinematic                   6.4 CS at

                 Pour Point                  -20°F
                                     110

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  ent Evaluation Procedures
     Three surface protection agents were evaluated during the  test  progrc-on.
Ihese were tested on the following days:

     10/18/78         Polyvinyl Alcohol/         Film-forming agent
                      Borate Gel

                      Water Spray                Flowing water film

     10/21/78         Corexit 7664               Water-based dispersant

Film-Forming Agent and Water Spray

     Two 25-meter-long test plots  (one  for  the  control  and  one  for  the
fVA/borate-gel)  and  one  10-meter-long  test plot (for the water spray) were
laid out along the upper intertidal aroa at the southern end of Seidler Beach.
Each  test  plot  was separated by booms that were set in the beach sediments,
extending into the water perpendicular to the beach (see Figure D-l).

     The  water  spray  system  was  constructed  of  a  10-meter  section  of
5-centimeter  (2-inch) diameter PVC pipe with 1.27 centimeters (0.5 inch) flat
fan jet spray nozzles fitted on 1.8-meter  (6-foot)  centers  connected  to  a
;378-liter/minute  (100-gpm)  centrifugal  pump.  The pump drew seawater from a
suction line placed approximately 3  meters  offshore.   The  spray  pipe  was
placed  on  supports  approximately  0.5 meter high along the upper intertidal
area, with the spray nozzles oriented to give a  flat  spray  angled  downward,
jtoward  the  water.   This  orientation provided an even flowing film of water
over the beach sediments.

     The polyvinyl alcohol/borate-gel was  applied  in  two  parts  using  two
Separate  spray  systems  over  a  25- by 3-meter area in the upper intertidal
zone.  A premixed 5% solution of polyvinyl alcohol was sprayed across the test
area  using  a  gear  pump  and hose.  Cnce the polyvinyl alcohol solution was
'applied, it was sprayed with a saturated borax solution, causing it to gel  in
jplace.  Concentration and application rates of the film-forming chemicals used
were:

                                 Concentration           application

HV-Polyvinyl Alcohol             50 grams/liter      600 ml/m2 (30 g/m2)

fcorax (sodium tetraborabe        25 grams/liter      30 ml/m2 (0.75 g/m2)
decahydrate)

Corexit 7664 ^ Dispursant

     One 25-meter-long control plot and two 12.5-meter-long  test  plots  were
laid  out long the upper intertidal area of the northern part of Seidler Beach
(Figure D-li).  One 12.5-meter test plot was sprayed with 5 liters  of  Cbrexit
7664  eductad in a 2% solution through a fire hose.  The other 12.5-reater test
plot was sprayed with 5 liters of. Oorexit 7664 applied neat (undiluted) with a


                                     111

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Figure D-l.  Film-forming agent test configuration.
                        112

-------
                                               Secondary booms
       Spilled oil
Spilled oil
Figure D-2.   Dispersant test  configuration.

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backpack sprayer.

Test Procedure and Data Collection

     All of the agent evaluation tests ware conducted  in  a  similar  manner.
The test procedure was:

      1. Spill oil inside of boans for each test and control area.

      2. Apply agent onto test areas.

      3. Bring oil onto shoreline usi^j containment oocrcs, create waves on the
         shoreline  using  the wake of a small workboat driven parallel to the
         beach.

      4. Approximately 45 minutes  after  oil  is  brought  ashore,  test  and
         control areas are flushed with seawater using a fire hose and 100 gpn
         fire pump.  (The water spray test area  was  not  flushed  after  the
         shoreline  was  contaminated.)  Flushing is conducted to determine if
         the agents prevent the oil frcm adhering to the sediment.

     Table D-2 summarizes the test conditions and  procedures.   Data  on  the
effectiveness  of  each  surface protection agent was obtained visually and by
taking sediment samples which were analyzed for oil content.

     The sediment sampling program involved taking two surface samples and two
subsurface  samples  (at  a  depth  of . 10 to 15 centimeters) in each test and
bontrol area, at two different times:  !(1) after  oil  came  ashore,  and  (2)
after  each  test  and  control  plot  was  flushed  (Figure  D-3 shows sample
locations).  Samples were also taken in  the  lower  intertidal  area  several
Jours  after  flushing  when  the  receding  tide  had exposed the tide flats.
jSeveral background samples were taken on the test beach  and  on  the  control
beach prior to the tests.

     Obne pentrcflteter readings were taken on the dispersant test sites  before
and  after  the  teats  to  determine if the use of tlispersants on a shoreline
altered the bearing strength (and the trafficability) of the beach.

     A detailed description of the sediment sampling procedure is contained in
Appendix D-l.

Biological Testing Program

     A biological sampling and analysis program was conducted  in  conjunction
with  the  dispersant  tests.   A  description of this program and the results
obtained is contained in Appendix D-2.
i
Taat Results
l.
General—
;     In all the tests, oil contamination of tha  substrata  was  very  uneven.
Because  of  the  sporadic  nature  of  tha  oil  contamination  tha number of


                                     114

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TABLE D-2.  SUMMARY OF TEST CONDITIONS - TEST AGENT
Test Condition
Time of agent
application
Amount of
agent used

Aniount of oil
spilled
Time of oil
spill
Length and
width of test
area (meters)
Wind direction
Kind Speed
Polyvinyl
Alcohol Borate
10/16/73
Start 9:10
Stop 9:15
2250 grams - PVA
(45 liters - 5% soln)
50 grains - Borate
57 liters

9:03
9:04
25 x 3




Control tl
10/18/78
_

-


57 liters

Start 9s 00
Stop 9:01
25 x 5


Ea?t 	
0-10 roph — — —
Water Flush
10/18/78
N/A

378 liters/
minute

57 liters

9:06
9:07
10 x 3




Cosrexit 76G4
Control #2 Neat
10/21/78 10/21/78
Start 11:17
Stop 11:25
5 liters


95 liters

Start 11:08
Stop 11:10
25 x 5 12.5 x 5

	 	 	 	 East 	


Corexit 7664
Kducted
10/21/78
11:26
11:31
5 liters educted
at 2%

95 liters for
both plots
Start 11:14
Stop 11:16
12.5 x 5





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 LEGEriD
     Upper intertida! series of samples

     Lower intertidai series of samples
fi

Lower
intertidai
                        Clam cages
                         n  n©    ©
                             ©      ©     ©
   12.5 12.5
    m   m
                                                                           Clam cages
                                                                             DD
3- 25m -w-25 m—di
                         m—t|3-25m-«H—KJ—«—25m-» H-25m-J»-25m-iifc-25m-5J«-25m-sJ3— 25m-? 4— 2
                                                      5m-; >3— 25m HS>
                                Figure D-J.   Sample location map.

-------
substrate  samples  collected  were  insufficient  to  provide   statistically
significant  results.  In order to provide statistically significant data, the
number of samples collected and analyzed would have had to have been increased
by  an  order  of  magnitude  which  was beyond the funding limitations of the
program.  Therefore, care must be taken when interpreting or  using  the  data
presented in this report.

     Although the test area appeared to be free of oil contamination prior  to
the tests, background (baseline) samples of the test beach and a control beach
a mile away indicated background oil contimination  levels  in  the  substrate
ranging from 8 to 39 rag/kg (ppn).

Polyvinyl Alcohol/Borate-Gel and Water Spray System—
     The results of the  polyvinyl  alcohol/borate-gel  and  the  water  spray
system  are shown in Table I>3.  The polyvinyl alcohol/borate-gel film did not
prevent the substrate from becoming contaminated;   however,  it.  appeared  to
prevent  oil  from  adhering  to  the  shoreline  sediment  as both the visual
observations and sediment sample results indicate.   The  film  prevented  oil
from  penetrating  the  substrate.  A preliminary test application of the film
suggested its persistence to be less than one or tvo tidal cycles.  The  water
spray  system  proved  to be quite effective, prevnting oil from contaminating
the test zone by countercurrent flow of water over the beach.

     Both the polyvinyl alcohoborate-gel and the water spray  system  appeared
to  prevent  oil  from penetrating the beach sijbstrate.  However, the beach is
composed of firm sand and gravel and oil penetration of the control  area  was
also minimal.

Gorexit 7664—
     The results of the educted and neat  applications  of  Cbrexit  7664  are
shown  in Table 1>4.  The disparity in sane of the replicate samples of one to
two orders  of  magnitude  make  the  results  very  difficult  to  interpret.
Educting  ths same volume of dispersant onto the beach was faster and appeared
to give  more  even  coverage  than  applying  the  dispersant  neat.   Visual
observations indicated that oil deposition on the dispersant-treated plots was
only marginally less than on the control plot, with the least  amount  of  oil
present on the tiest plot where Oorexit 7664 was educted in a 2% solution.

     Visual observations of the test and control plots after they were flushed
with  ssawater  indicated  that  the disparsant-treated plots were more easily
cleaned.

     The sediment samples analyses indicate that there was  more  oil  on  the
test  and  control  plots  after  flushing than before flushing.  This was not
confirmed by visual observations and is an example of sampling error.

     This use of dispersants did not appear to cause oil to  deeply  penetrate
'the  sediments.   The  samples  and  visual observation taken at a depth of 10
centinietors indicate very little oil contamination of either the control  plot
or  the  dispsrsant-treated  plots.  However, after the test and control plots
were flushed, a diffused sporadic band of oil was observed 3 to 5  centimeters
below  the surface in all three test plots, apparently.related to ths flushing
operation.

                                     117

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TABLE D-3.  SAMPLE RESULTS AND VISUAL OBSERVATIONS OF POLYVINYL ALCOHOL/
                 BORATE-GEL AND WATER SPRAY AGENT TESTS
Oil Contamination
Before Flushing





P
CO








Test
Series
and
Sarco? es
_
P
c«
3
•i


*2
rt
r^ ffl
•5 5 a
£a
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               TABLE D-4.   SAMPLE RESULTS  AND VISUAL OBSERVATIONS OF COREXIT  7664 TEST
Oil Contamination
on Test Area Oil Contamination on Test
Test Backyround Samples Before Flushing Area After Blushing Surface Sample
ana upcer Lower Surface 10-15 cm Surface 10-15 cm Several Hours




Numbers nqA5 n.jA3 ir.qAa i»gA<3 JMA" mqAl mgAg Visual Observations and Comments

L
Q
*1 14 8 G97 29 2990 79 Before flush - 1.5-cm band of oil contamin-
ation
*2 39 64550 89 17290 83 After
beach

SM
33
8 ^
55
91 13 12 48 15 Z1480 23 S-l 13 Bnfore
oil 0.
S-2 5 After
beach

at surface dift'jsing downward.
flush - some visible oil remained
sediments.
flush - occa5ional t*uried band of

OI.


75 en; thick. Some dispersed oil on
flush - oil appeared to flush off
fairly easily.




*1
         15
                              191
                             1140
                                          26
                                                     903

                                                    1130
                                                    124O
                                                                219
S-3  13       Some oil stain reiaained on  substrate.

            Before flush - 1-cm band of oil contamin-
            ation at surface.  Test area received larg-
            est amount of oil contamination.  Some
            dispersed oil on water adjacent to test area.

            After flush'- oil appeared  to flush off
            beach. Some oil stain remained on sediments*

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Bearing Strength Tests—
     Cone pantrcmeter readings were taken of the control and  dispersant  test
plots  before  and  after  the tests were conducted to determine if the use of
dispersants would affect the bearing strength and trafficability of  a  beach.
The  results  of  the  bearing strength survey are shown in liable D-5.  As the
table indicates, the use of dispersants did not change the bearing strength of
the test areas.

Discussion

Water Spray System—
     The countercurre k. flowing water film produced by the  spray  system  was
the  most  effective  of  the  three  agents  in protecting the shoreline from
surface  oil  contamination,  and  preventing  penetration  of  oil  into  the
sediments.  Seme beach erosion did occur when the water spray impinging on the
beach eroded a ; *u How trench approximately 15 centimeters  wide  by  2  to  3
centimeters  deep along the length of the spray bar.  Although the water spray
system proved to be very effective, it might be  difficult  and  expensive  to
implement  on  a  large  scale.  At the flowrate tested, a punping capacity of
11,340 liters/minute (3000 gpm) woul"! 'oe required for every 300  meters  (1000
feet)  of  shoreline  to  protect.   It is uncertain whether the high flowrate
tested is required.  Water spray systems could  be  used  to  protect  smaller
shoreline  areas  of  high  amenity  or  biologically significant value if the
systems were already constructed and could be ernplaced in a short time.
              TABLE D-5.   BEARING STRENGTH SURVEY OF TEST AREAS
                  Averaged Cone Pentrometer*     Averaged Cone Pentrometer
    Area            Readings Before Test	Readings After Test

 Control                     72                             75

 Corexit 7664
 Educted                     74                             75

 Corexit 7664
 Nea.:                        74                             83
 * The cone pentrometer readings are a measure of the shearing resistance of
 the sediments, and can be directly related to the ability of earth-moving
 equipment to operate on the sediments without becoming immobilized.   The
 range of pentrometer readings (72-83) from Siedler Beach indicate that
 rubber-tired earth-moving equipment could operate successfully on that
 particular beach.
                                     120..

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 Pdlyvinyl Alcohcl/Borate-Gel—
        '        •!
      The polyvinyl alcdlTOl/borate-gel agent did not appreciably reduce surface
 pil  contamination  of the shoreline but did appear to prevent oil penetration
 into the substrate  and  to  facilitate  removal  of  oil  by  flushing.   The
 persistence  of : the agent as an intact filir. was approximately one tidal cycle
1 when applied to the upper intertidal area  of  a  low-energy  beach *   Several
 hours  to  several  days  are  required  to  formulate  the  polyvinyl alcohol
 solution, depending on how much agent is  needed.   The  formulation  requires
 that  (5%  by weight) dry polyvinyl alcohol powder be added to cold water, and
 stirred.  The water is then heated to 93°C (200°F) /md allowed to cool to room
 •temperature.   Ihe  resulting  solution will remain stable for approximately 4
 weeks.   The  time  required  for  formulation  and  the  short  duration   of
 persistence  may  severely  limit the use of polyvinyl alcohol/borate-gel on a
 large scale.

 jOorexit 7664—

      The Corexit 7664 tests were inconclusive in determining its effectiveness
 as   a  protection  agent.   Gorexit  7664  appeared  to  reduce  initial  oil
 jcontamination of the beach surface somewhat, as  indicated  by  the  cloud  of
 dispersed  oil  formed  in  the  surf zone.  Kb significant differences in the
 .amount of oil initially dispersed as a function of near or diluted application
 Was visually detectable.

      Application of the agent using a hand sprayer was  fairly  time-consuming
 and  would  probably  not  be practical for actual use.  Eduction using a fire
 hose provided a more acceptable rate of coverage*

      "Hie oil was removed by flushing with seawater.  Flushing appears to be  a
 ifactor  in  the  success  of  the  technique.  When aimed directly at the oily
 {sediment, some oil was removed, but sane also appeared to be mixed more deeply
 [into  the  sediments.  Application of water just outside the edge of the oiled
 Jzone appeared to float the oil free without this mixing effect.  Flushing  far
 •from  the  waterline  (in  dry  sediment  above the beach water table) was not
 successful.   The  dispersant  did  not  reduce  the   bearing   capacity   or'
 jtrafficability of the test areas where it was used.
                                      121

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                                  APPENDIX D-l

                          SEDIMENT SAMPLING PROCEDURES


      1.  During lew tide on the day before  each  oil  spill  test,   a  single
 sediment  sample  is taken frctn the Icwsr intertidal area of each test plot to
 be tested en the following day (with the exception of the test plots for OON1,
 PVAB,  and WFA-B which are to be teted on the first day of the test).

      2.  Sample collection is carried out using a  metal  trowel.   Sufficient
 sample volone is taken frcm the top 6 inches of the substrate to fill a 250-ml
 sarnplf. jar (each jar is prewashed with hexane and fitted with an aluninum foil
 inner seal to avoid contamination).

      3.  Chce fitted, each jar is closed and frozen, using dry ice,  and storrsd
 for analysis at a later date by the EPA.

      4.  Prior to the daily spill test, the above procedure  is  repeated  for
 the  q?per  intertidal  area  of  each  test plot to be tested that day.  This
 sample and the above-mentioned lower intertidal  sample  are  to  be  used  as
 indicators of background hydrocarbon levels.  Again, no background samples are
 taken for OCN1, PVAB, and WFA-B, which are to be tested on the  first  day  of
 the program.

      5.  Upon completion of the oil spill test, two sets of  sediment  samples
 (four  samples  in  total) are taken in the upper intertidal area of each test
 plot,   The two locations sampled are situated roughly 1  mater  apart  in  the
 middle of the oiled test band in an area showing high oil contamination.

      6.  Frcni each location, two different samples are taken:   one  surficial
 sample  (0-2-inch  interval)  and  one  from  a  depth  of  7 inches (5-7-inch
 interval).  All four samples are collected and stored in the manner  described
 previously.

      7.  Fallowing the oonpletion of the flushing portion of  the  test,  this
 process  is  repeated with tvo surface and two subsurface samples taken in the
 upper intertidal portion of each test plot (no such sample is taken from WFA-B
 since it already involved flushing).

      8.  A final set of sediment samples (four samples in total) is  taken  in
 the  lower intertidal area during the next low tide following the test.  These
 samples are taken from the area adjacent to the clam cages (roughly 30  to  40
 rosters  out  frcra  the base of the beach scarp).  Again, two samples are taken
rfron each location sampled, placed in sample jars, and frozen.


                                      122

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          NOTE: No post-test lower intertidal samples were taken
          for CON2, GORE, or CORN, since oil spilled in these test
          plots was prevented fran reaching the lower intertidal area
          by boons and the prevailing winds.

     9.  In addition, two sediment samples are taken from the  control  beach:
one  prior  to the onset of the test program and one following its completion.
These samples are taken  from  the  top  6  inches  of  substrate  immediately
adjacent  to  the clam cages.  Two additional clair. cage samples are also taken
from the substrate adjacent  to  the  two  test  beach  clam  cages  following
completion of the test program.
                                     123

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                                 APPENDIX D-2

                LABORATORY INVESTIGATION OF IMPROVED MATERIALS
                   FOR SHORELINE PROTECTION FPOM OIL SPILLS
BACKGROUND AND APPROACH

     The API/EPA has  sponsored  two  series  of  investigations  to  identify
materials that can be used to prevent contamination of shorelines in the event
of an offshore oil spill.  The  first  program  initiated  research  into  the
mechanism  of  shoreline protection, devloped procedures to evaluate candidate
materials, and recomiended premising agents for use in  protecting  sandy  and
rocky  shorelines  and salt marsh areas threatened by oil.  Three laboratories
(Tracer, Exxon, and Shell) worked independently  in  this  first  program  and
evaluated    polymeric    film-forming    materials,    polysaccharide   gels,
microorganisms, inorganic coatings, and surface-active agents.

     The second program was contracted to Woodward-Clyde Consultants with  URS
Research  Company  and  Texas Rasearch "Instituter Inc. as subcontractors, with
assignee! tasks to compare to a camion baseline  reagents  reccmnended  by  the
first  investigating laboratories, determine relative agent effectiveness, and
conduct field tests of tha nore premising  agents  on  salt  marsh  and  sandy
beach.   A test site was located on Arthur Kill in Vfoodbridge, tfew Jersey, and
tests were conducted during  May  1977.   The  materials  selected  for  field
evaluation  represented  the  protective  mechanisms of a continuous polymeric
film, a gelatinous organic coating,  a  low-concentration  surfactant,  and  a
flowing liquid barrier.  The field-tested agents were:

      1. Polyvinyl acrylate emulsion, AMSCO-REZ 3011 spray coated

      2. 1% solution of xanthan gur spray coated

      r-!. Oil Herder sprayed at the shoreline

      4. Continuously flowing water

     Of these, the  polymer  film  and  the  polysaccharide  gel  showed  good
protective  qualities  but, more importantly, the tests indicated deficiencies
in these materials which, if corrected,  would  greatly  improve  the  overall
performance.   Application of the polymer emulsion to a sandy surface resulted
in good coverage but on a  rocky  or  uneven  surface  tha  coverage  was  not
complete  and  resulted  in coating gaps and subsequent oil penetration.  This
effect v«o not noted with the polysaccbaride gel.  In  addition,  the  polymer
film  did  not  dry or set ir.ma3iat
-------
j.ifor several months". " The"xanthan gum  solution  "did  not  require  drying  but
 lacked tenacity on the beach and was easily removed by wave action.

      The objective for the current program- was,  therefore,  to  improve  the
 Applied _ materials'  long-  and short-term stability, setting characteristics,
 and application properties, without expending a large effort on new  materials
 development.   The approach taken was to rely heavily on the previous programs
 for guidance in selecting materials as well as test and evaluation methods.

 SUMMARY, CONCLUSIONS,  AND RECOMMENDATIONS

      The present study was directed to gelatinous materials,  polymeric  films
 with  improved  properties, and new classes of materials that could be applied
 as foam.  The project was organized in three phases:   identification  of  new
 materials,  screening  of  these  materials  in the laboratory, and testing on
 simulated beaches.  On the  basis  of  previous  EPA/API  report.:  and  recent
 literature,  five  new materials were selected for study:  polyvinyl alcohols,
 modified polyvinyl acetate/acrylate, silicic acid gel, soluble starch,  and  a
 polyacrylamide gel.  Gelling of polyvinyl alcohol with cross-linking agents to
 decrease its solubility .and increase  its  mechanical  strength  was  studied.
 These  materials were screened in laboratory tests for ease of preparation and
 Application, solubility in salt water,  resistance to  erosion,  resistance  to
 oil  penetration  and  staining,  foam-forming  ability,  and  ability to form
 continuous coating.  Those with potential for field application were subjected
 to testing in an oil spill on a beach simulator.  Additionally, studies of the
 ultimate degradability of cross-linked polyvinyl alcohol  ware  made  and  its
 manufacturers  were queried  for their best opinion of its ultimate breakdown
 behavior.

      Vfe have concluded from these studies that a high-molecular-'weight,   fully
 hydrolyzed  polyvinyl   alcohol,  cross-linked with sodium borate,  will serve as
 jan effective agent to  protect beaches from  staining  and  penetration  by  an
 impinging  off store oil spill,  is environmentally acceptable,  and is free front
 (drawbacks  observed in  the   application , of  polyvinyl  acetate  emulsions  and
 xanthan gum gels.  Foamed polyvinyl alcohol performed best on a rocky,  uneven
 beach?   an unfoamed gel performed best  on a flat,  sandy beach.  We also  noted
 jthat the  polyacrylamide emulsion,  cjeiAod with a cross-linking agent,  had many
 desirable  characteristics,  but was flawed by the need for  special  procedures
 and equipment for its  application.

     Our recoranendations are as  follows*:

     Highest rank—recommended for field testing:

          Cross-linked polyvinyl alcohol  foams for rocky shorelines

          Cross-linked polyvinyl alcohol  gels  for  sandy beaches

     Sicw promise  but  require special equipment  development—not reconmended
 for field tests;

          Palyvinyl acrylamide gel


                                     125

-------
          Soluble starch

     lowest raiJi—recommend dropping from further consideration:

          Silicic acid gel

RESULTS AND DISCUSSION

Literature Review

     A review of  pertinent  literature  including  previous  API  reports  on
shoreline  protection,  manufacturer's data, and other literature dealing with
shoreline protection, oil spills, or hazardous chemical spills  was  made.   A
search of the OTIS data bank for related publications was also conducted.  The
literature review is listed in Appendix D-2-1.

Selection of Materials

     Data from the previous beach protection program showed that a  continuous
polymeric  film  will  prevent  oil fron penetrating into the beach and, also,
that gelatinous materials similar to the xanthan gum solution could  also  act
as  a  protective  agent.   More importantly, however, the previous field test
pointed out several deficiencies in both  of  these  materials.   The  polymar
emulsion  used  as  a  continuous  film-forming  agent  worked so wall that it
persisted on tha beach through several norths' exposure to the weather.   Film
formation,  being dependent on the drying of the applied emulsion, was slow on
a wst beach;  in the event of rain it is assumed that film formation will  not
occur at all.  On the other fand, xanthan gun, while not requiring drying, was
not sufficiently durable en an open  beach  to  provide  protection.   At  the
Sewaren  test site, during the application of these tvo materials, xanthan gum
gel was observed to form a mere continuous coating on uneven,  rocky  sections
of  beach  than  the less viscous polyvinyl acrylate emulsion.  In the present
study the  following characteristics were sought for a protective agent:

      1. The ability to form a continuous polymeric film without the necessity
         of drying

      2. The ability to form a film tough enough to withstand wave action, but
         that can be expected to degrade in a reasonable length of time

      3. To have viscosity characteristics  that will enable  the  material  to
          flow  over  and  fill  gaps  in rocky, uneven beach areas, as veil as
         cover sand

      4. To hava sufficient tenacity  for the beach to withstand wind and vave
         motion

       5.  To have  short-term resistance  to solubilization by salt water

      6.  Tb prevent  penetration  and staining by oil
                                      126

-------
      7. Be relatively nontoxic ^rd environmentally acceptable

     Using these characteristics as a basis,  five  materials  were  initially
selected:

      1. Polyvinyl alcohol cross-linked with Oongo Red

      2. Folyvinyl alcohol cross-linked with sodium borate

      3. Sodium silicate solution, neutralized to form a gel

      4. A proprietary film agent manufactured by Whale Chemical Co.

      5. Polyvinyl acrylate emulsion, as in the previous program but with  the
         addition of a drying and/or degradation accelerating agent

     The literature  review  resulted  in  the  selection  of  two  additional
materials—soluble  starch  (a  high-molecular -weight  polysaccharide)  and  a
low-molecular-weight polyacrylamide  vAiich  can  be  cross-linked  to  form  a
sticky/  gelatinous  mass.   Both  of  t^se  satisfied  the requirements of a
protective agent and ware tested in the Laboratory.  Materials, suppliers, and
costs are summarized in Table D-6.

Gelling Polyvinyl Alcohol with Cross-Linking Agents

     A separate study vras ma^e to determine applicable cross-linking agents to
enhance gelation of polyvinyl alcohol solutions.  Stable, as wall as thermally
reversible gels can be formed by reaction of polyvinyl alcohol with  a  muter
of  reagents.  Ebur cross-linking agents were investigated:  Congo Red, sodium
borate, boric acid, and gallic acid.

;     After cross-linking, polyvinyl alcohol becones  insoluble  in  wat»r  and
increases in tensile strength.  Thus, the advantage of cross-linking polyvinyl
alcohol as applied to the beach is  that  the  cross-linked  material  resists
dissolution  by : impinging  waves and maintains its mechanical integrity.  TWo
methods were used to introduce the cross-linking agent into the solution.  One
was  to  mix  a concentrated solution of the cross-linking agent directly into
the polyvinyl alcohol solution.  The second was to apply the polyvinyl alcohol
to  a beach substrate and to spray a cross-linking agent over the EVA.  In the
first instance, cross-linking  agents  blended  directly  into  the  polyvinyl
ialcohol  solution  resulted in an uncontrolled reaction.  Small concentrations
of cross-linking agents gel polyvinyl alcohol.  As agitation and concentration
of  the  cross-linking  material  increase,  the  solutions  solidified into a
rubbery mass.  Cverepraying polyvinyl alcohol solution with ths  cross-linking
agent  produced  a  gel  with  a  tough surface film;  polyvinyl alcohol foams
became rubbery.  Overspraying was the preferred method used for the  remainder
of the testa.  The physical characteristics of the cross-linked FVA using each
of the three agents varied and are shown i.» Txible D~7.  Briefly,  gallic  acid
in  concentrations  up  to 10% by weight of resin, slightly hardened polyvinyl
alcohol  films wrvsn cversprayod and only thickened a PVA solution.  Congo  Red,
in  concentrations  of  frcm 0.2% to 2% by weight of resin, coagulated the FVA
into a galatirdus rod mass in solution and produced a gelatinous surface  when


                                     127

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                                     TABLE D-6.   MATERIALS StiMMARY
Material
Foiyvinyl Alcohol
Elvar.ol HV-L7DQOG
Polyvinyl Alcohol
Elvanol 90-50 F
Polyvinyl Alcohol
Geluatol 20-30
Polyvinyl Alcohol
Vir.ol 165
H
oo Poly vinyl Alcohol
Vinol 205
Polyvinyl Alcohol
Vinol 523
Polyvinyl Acrylate
Amsco-Res 3011
Polyacrylamide
XD- 30123. 01
Soluble Starch

Sodium Silicate

Form (as Supplied)
Powder
Powder

Powder

Powder

Powder

Powder

Liquid Emulsion
55% Solids
Liquid

Powder

Powder

Supplier
DuPont
DaPont

Monsanto

Air Products

Air Products

Air Products

Union Oil

Dow Chemical

Bon Ami Co.

Baker Chemical

Cost (?/lb)
S/kg
(1.47)
3.24
(1.52)
3.35
(0.875)
1.93
(0.805)
1.78
(0.735)
1.62
(0.775)
1.71
(0.32)
0.706
(0.30)
0.662
(0.436)
0.961
(0.475)
1.05
Cost as Applied
($/gal) $/liter
(0.612)
0.162
(0.633)
0.167
(0.364)
0.140
(0.3i?)
0.089
(0.306)
O.OB1
(O.J23)
0.085
(2.930)
0.774
(1.250)
0.330
(0.0728)
0.0192
(0.187)
0.0494
Cost (5/mile)
1436
1481

1242

783

718

754

6865

2927

170

438

* Beach area 1 mile long x 10 feet wide.

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            TABLE D-7.-  POLYVINYL ALCOHOL CROSS-LINKING AGENTS
Agent
Congo Red
Congo Red
Boric Acid
Boric Acid
Borax
Borax
PVA Cone.*
(Wt. %)
5
5
5
5
5
5
Agent Cone.
(% Resin)
.2
2
Saturated
Solution
Saturated
Solution
Saturated
Solution
Saturated
Solution
Results
Red gelatinous clots formed.
Thicker clots formed.
Dripped into PVA with stirring —
thickened and formed solid clumps .
Misted over PVA — formed surface
skin on contact — PVA thickened on
standing
Dripped into PVA with stirring —
. thickened and formed solid clumps.
Misted over PVA — formed surface
skin on contact — PVA thickened on
                                         standing.
Gallic Acid
Gallic Acid
5
5
10
10
Slow thickening of PVA solution.
Thin gelled skin formed when
sprayed over PVA surface.
* Elvanol HU-L7D006.
                                    129

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over sprayed  on  a  coated  beach.  The borates, sodium borate and boric acid,
both produced very rapid coagulation of F/ft in solution, and when  oversprayed
on  a  coated  surface,  inmediately  hardened  the surface into a tough film.
Because of  the  durability  of  the  borate-treated  polyvinyl  alcohol,  the
relative  low  cost  of  the  borates,  the  rapidity  of the reaction and low
toxioity, sodium borate was chosen as a cross-linking agent  for  use  in  the
remainder of the tests.

Laboratory Screening

     Samples of the materials enumerated on  page  127,  excepting  the  Whale
Chemical  Co.   agent  which  was  not available, were obtained for laboratory
testing.  Polyvinyl alcohols of low to high molecular weight and low  to  high
degrees  of  hydrolysis  were  received.  In general, molecular weight affects
vater solubility viscosity, and dry strength;  degree-  of  hydrolysis  affects
the  alcohol's  reactivity  in cross-linking.  While polyvinyl alcohol is only
slightly soluble in cold water, the solubility limit is approximately  20%  in
hot  water.   Five  percent  solutions  of  six  different  polyvinyl  alcohol
formulations were prepared for laboratory screening.  Gels of soluble  starch,
cross-linked polyacrylairu.de, and silicic acid were also prepared.  Bench-scale
procedures designed to test  for  the  criteria  set  out  on  page  126  were
performed.   Detailed  descriptions  of these tests and preparation procedures
are presented  in  D-2-2.   Since  little  of  the  data  gathered  was  of  a
quantitative  nature,  a  scoring  protocol of pluses or minuses was utilised.
Ihe better results are indicated  by  more  pluses;   negative  attributes  by
minuses.  Ihe results of these tests are presented in Table D-8.

Simulated Beach Tasting

     The simulated beach system  used  to  test  agents  in  this  program  is
essentially  the same as that used on the previous API program.  Three beaches
with an area of 0.334 square meters each were attached  to  a  mechanism  that
pocked  the  beaches  through  a  30-degree  arc  every  2 seconds.  The beach
surfaces were made of unwashed river sand and placed in the  beach  containers
to a depth of approximately 3 inches.  The agents to be tested were applied to
one half of the beach surface;   the  untreated  half  served  as  a  control.
Agents  were applied to beaches prewetted with 3.5% salt water.  After drying,
the appearance and texture of the  coatings  were  noted.   Approximately  2.0
liters  of salt vster were then added to the beaches and rocking was continued
for  1  hour.   Observations  were  then  made  of  erosion,  dissolution,  or
displacement of the coatings.  Test oils, Kuwait crude and No. 2 fuel oil -were
fcdded and the beaches again rocked for another hour.  After the  second  hour,
the  water  was drained from the beach, appearance was noted, and residual oil
was washed fron the beach surface with a stream of water.  Observations  again
Were  made  on  the  ability  to  remove  the  oil fron the surface.  Vertical
Sections of the beaches were then examined for oil penetration  and  staining.
The results of these teats are given in liable D-9.

Additional Tasting

     It became apparent during the course of  the  laboratory  phase  of  this
program  that  materials  not  tested  or combinations of materials not tested


                                     130

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                                    TfcELE D-8.   IABORRTORY SCREENING SUMMARY
Material
Elvsr.ol
KN-L7DC06

Elvanol
30-50F

Vinol 105

Vinol 205

H1
W Vinol 523

Gelvatol
20-30

AKSCO-REZ
3011
Soluble
Starch
Sodium
Silicate
Polyacryl-
amide
Fort"
Gel

Foam
Gel

F&ara
Gel
Foam
Gel
Foam
Gel
Foam
Gel

Foaa
Emulsion

4% gel

Gel

Gel

preparation
Foam Expansion
Application % * at
Erosion Resistance* Staining/
Method Rating Hethod Rating Initial 17 Hrs Rating Coverability* ml Ratir.q Clt-anability
Mix w/heat +

Mix w/hcat +
Mix w/heat +

Mix w/heat +
Mix w/he^t +
Mix w/hcat +
Mix w/heat +
Mix w/heat +
Mix w/heat +
Mix w/lieat +
Mix w/heat +

Mix w/heat +
As Rcvd. +

Mix s heat +

Mix & Acidify

Crosslink
w/rcagents
four/spray + 137 50 *

Pour/spray +
Pour/spray •<- 175 25 +

Pour/spray +
Pour/spray + 137 SO +
Pour/spray +
Pour/spray + 312 Trace +
Pour/spray +
Pour/spray + 237 75 +•
Pour/spray +
Pour/spray + 337 0 +

Pour/spray +
Pour/spray +0

Pour hot. - • 0
allow to cool
Poar +0

Preaiix and - 0 -
rapidly pour
+ 2GO * +


200 + -f


90 +

180 + +

* 130 + *

100 + +


+ Did not erode + +

+ 50 -

5 - -

N/A N/A N/A N/A

* Polyvinyl alcohol cross-linked with borax
+ - Acceptable
- - Unacceptable

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TABLE D-9. ^SIMULATED BEACH SUMMARY
Material
Elvanol
KV-L7D006


Elvanol
90-50F
Vinol 105

Vinol 205

Vinol 523

Gelatol 20-30

AMCO-REZ 3011
Sodium
Silicate
Application Erosion Kuwait #2 Oil
Gel - .N/A N/A
not cross-
linked
Gel/Borax + + +
Foam/Borax + + +
Gel/Borax + . + +
Foam/Borax + +
Gel/Borax - + +
Foam/Borax - + +
Gel/Borax + + +
Foam/Borax - + +
Gel/Borax + + +
Foam/Borax + + +
Gel/Borax + +
Foam/Borax - + +
Emulsion + + +
Gel - - -
Overall
- (rapid erosion)
+
+ (edges tended to lift from sand)
- (low strength)
- (low strength)
- (low strength)
+
- (low strength)
+
+
- (low strength)
- (low strength)
- (long drying time required)
- (very short persistence)

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showed promise for use in shoreline protection.  Included in  these  materials
is a inixture of polyvinyl alcohol, and silicate gel, a mixture of water-soluble
starch and rDlyvinyl  alcohol,  and  other  polyelectrolytes  similar  to  the
polyacrylamide.   Brief  laboratory  observations  were  made  but  a detailed
investigation of these materials could not be made within  the  scope  of  the
program.  These observations are given in Table D-10.

     None of the procedures outlined  under  laboratory  screening  and  beach
simulation  testing  address  the ultimate degradability of coating materials.
Ihis was determined, in the Sewaren  field  tests,  to  be  a  defect  of  the
polyvinyl  acetate/acrylate  coatings.   To gain insight into this process two
mini-tests were conducted.  First, test patches  of  sand  were  prepared  and
coated  with polyvinyl alcohol solution, polyvinyl alcohol foam, both of these
cross-linked with sodium  borate,  and  polyvinyl  acetate/acrylate  emulsion.
These patches were allowed to dry thoroughly.  Sections were cut from the test
plots, iinmersed in salt water, and allowed to soak.  Intermittent observations
showed  the uncross-linked polyvinyl alochol to hydrate to a mucilaginous film
that could be broken or separated between the fingers after a day or two,  and
the  acetate/acrylate copolyirar film to lose little of its initial strength or
toughness after 3 weeks.
                  TABLE D-10.  MIXTURES AND OTHER MATERIALS



       1.   5% Polyvinyl alcohol, uncross-linked - 1% Silicic Acid Gel

            Can be foamed.  Foam stabilized by silicic acid gel.

            Drying time increased.

            Dried foam discontinuous and crumbly.

       2.   28% Polyvinylacetate/acrylate - 2% Soluble Starch

            Dries to a hard, tough film.

            Film softens only slightly during one-week exposure to salt
            water.

       3.   Polyacrylamide Gel

            Forms dense gel that cannot be poured.

            Dries very slowly, but rehydrates to its original form.

            High resistance to erosion by salt water.
                                     133

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     To study the breakdown of dried film of these materials, these films were
prepared  by  dipping  circular  loops of stainless steel wire.  Dried samples
were exposed to bright sunshine all day  for  one  week  while  controls  were
stored  in  a  dark  cabinet.  Daily observations during tMs period showed no
change in the color, texture, or brittleness of the exposed samples.   At  the
end  of a week's exposure infrared trarisnittance spectra of the film showed no
evidence of ultrviolet-induced chemical decomposition.  On the eighth  day  of
exposure  the  outdoor  samples  were inadvertently briefly subjected to brief
morning mist, after which they were brought inside to dry.  On drying, all  of
the  polyvinyl alcohol films shrunk and curled—the polyvinyl acetate/acrylate
films were unaffected.  Ws feel the capacity of the polyvinyl alcohol films to
readily  hydrate  and  their  tendency to shrink and curl on drying will cause
mechanical degradation of applied film in a reasonably  short  period  in  the
moist environment of the beach.

EQUIPMENT REQUIRED FOR CM-SITE APPLICATION

     The solutions recommended for field test  of  this  program  can  all  be
pumped  through standard centrifugal or positive-displacement purps.  However,
for application of foam,  special  pumping  systems  must  be  used.   Several
varieties   of   foam-generating  equipment  are  commercially  available  for
application of foam to fires,  application  of  insecticides,  and  for  other
purposes  where  expanded solutions are required.  In general, foam generators
work by injecting air into a stream of the fluid being pumped  and  dispensing
the  fluid/air  mixture  through  a sized screen to control the resulting foam
bubbles.  For the purpose  of  field  testing,  a  limited  amount  of  foamed
material  could bs generated by using a carcnercial foam pump, or by foaming in
a container, such as a 55-gallon drum fitted with  a  high-speed  mixer.   The
resulting  foam could then ba poured on the surface to be coated.  Application
of cross-linking agents required for polyvinyl  alcohol  can  be  accomplished
through use of hand-held garden-type sprayers.
                                     134

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                           APPENDIX D-2-1

                          " BIBLIOGRAPHY"
 1. Sunmary Report of Phase I Evoluat-Lon of  Selected  Surface  Treatment
    and Agents.  Vtoodward-Clyde Consultants.  August 1970.

 2. Sumnary Report of Phase II Laboratory and Preliminary  Field  Testing
    of  Selected  Surface  Treatment Agents.  Woodward-Clyde Consultants.
    February 1977.

 3. Final Report, Beach Protection Study.  Tracer, Inc.  July 26, 1974.

 4. Methods to Treat, Control and Monitor  Spilled  Hazardous  .Materials.
    Calspan Corp.  June 1975.  (OTIS PB-243 386)

 5. Control of Hazardous  Chemical  Spills  by  Physical  Barriers.   MSA
    Research Corp.  March 1973.  '(OTIS P 13— 221 493)

 6. Toxic Substances List.  NI.OSH.1  1977.

 7. Toxicologic Investigations of Polyacrylsmids .  D  D. McCollister,  et
    al.   Toxicology  and Applied Pharmacology, Vol. 7, ND. 5.  September
    1965.

 8. The Chesnistry  of  Silicic  Acid.   S. A. Greeriberg,  J. of  Chemical:
    Education.  Vol. 36, No. 5.  May 1959.

 9. Control of Spillage of Hazardous Polluting Substances.  . G. W. Dawson
    et  al.  Battelle Manorial Institute. Richland, Washington.  Ndveraber:
    1970.  (NTIS PB 197 596)

10. PolyvinylalcolTol .  C. A. Finch, John Wiley & Sons, Naw York.  1973.

11. The Ecological Significance of Boron.  Sprague.  U. S. Borax Research.
    Corp., Anaheim, California.  1972.

12. Shoreline Protection and Restoration Fran Oil Spilla.  Final  Report.
          Research and Engineering Co.  September 1974.
13. Review o£ Agents and tethodo fior Ehorelina Protection.  Final Report.'
    Texas Research Institute, Inc.  February 11, 1977.
                                135

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14. PDly(vinylalcx3hol).   J. G. Prichard.   Gordon  and .Breach   Science
    Publishers.  New York.  1970.

15. Evaluation of Selected Surface Treatment Agents for the Protection of
    Beaches  and  Salt  Marshes  fran  Oil  Contamination.. Final .Report.
    Woodward-Clyde Consultants.

16. Development  of  a  Nfcbile  Treatment.  System  for  Handling  Spilled
    Hazardous  Materials.   M. K. Gupta.  " Envix-ex,  Inc.  " EPA  Contract
    No. 68-01-0099.  July 1976.  (NTIS EPA-600/2-76-109)
                                 136

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                                 APPENDIX D-2-2

                  PREPARATION.OF MATERIALS AND SCREENING TESTS-


. PREPARATION

 Polyvinylaloohol Solutions

      Polyvinylalcohols (5% by-weight), granular or powder, was added  to  cold
 water  with stirring to form a slurry. "The slurry was heated under continuous
 stirring until all turbidity disappeared.   This  occurred  at  65°-70^C.   Kb
 significant  increase in viscosity was noted in eolution of this concentration
 on cooling.

 Polyvinylacrylate (AMSCO RES-3011)

      No preparation necessary.  Apply as received.

 Soluble Stfjrch

      Soluble starch (4% by weight) was added to cold water  with  stirring  to
 form  a  suspension.  The suspension was heated with stirring until no further
 decrease in turbidity could be  noticed.   This  occurred  near  10sPc. •  Upon
 cooling/ the solution fornied a viscous gel.

 Silicic Acid Gal

      A solution of soditm  rneta-silicabe  (1%,  based  on  SiO-  content)  was
 prepared  in  cold  water.   Th.e  pH  of  this solution was adjusted to 8.5 by
 dropwise addition of concentrated 1321 vath-stirring,  -The  solution, was  then
 pillowed  to stand.  A dense mucilaginous driable gel formed vathiii 15 minutes.

 gQlyacrylcgnida (Dow XD-30123.01)

      TVJO solutions were prepared:

       1* 0.75 ml; of 40% glyoxal was addad to 10-0 g of polyacrylcmlde emulsion.

       2. 1.5 g of Na3P04 12^0 in 100 g of ILp.


      The two solutions were poured together and rapidly stirred.  A  tenacious
 gel formed with 2 to 3 minutes.
                                      137

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FOAMABIIJTY./POAM STABILITY

     Two hundred ITI! of each agent were placed in a Vfering blender and  stirred
at  high  speed for 60 seconds.  The volume of the resulting foam was measured
in a graduated vessel and the time required  for  the  foam  to  collapse  was
observed.

RESISTANCE TO STAINING AND OIL PENETRATION

     Test objects (a wooden stick, a glass microscope slide, a patch of  glass
fixer  cloth) wera coated with the protective agent.  The objects were allowed
to dry, dipped briefly into a solution of  salt  water,  then  dipped  into  a
vessel  of  =rude  oil.  The tenacity of the oil was observed.  The object was
then rinsed with a stream of water and again  examined  for  oil  staining  or
penetration.

COVERING ABILITY AND EROSION RESISTANCE

     Twenty-cm squares of screen wire were  dipped  in  preparations  of  each
protective  agent  and  withdrawn.   The  squares  were  then  allowed to dry.
Con^jleteness of coverage was noted.  A  3.5%  salt  solution  (simulating  sea
water)  was  allowed  to  drip  onto  each" material  at  a"  rate  of 60 to 70
drops/minute fran a height of 30 on.  The volune of solution required to break
through the coating was recorded.
                                    ••138

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                                APPENDIX D-2-3

              DETAILED PREPARATION PROCEDURES, RECOMMENDED AGENTS


     The  recormended  agent  is   high-molecular-weight,   fully   hydrolized
polyvinyl  alcohol  (DuPont  Elvanol  HV  or  equivalent).   This  material is
available as a powder in 50-lb bags.

     The PVA is prepared as a 5% by weight solution (0.44 Ib  PVA  per  gallon
tiJD in fresh vater) using the following procedure:

      1. Add the weighted powder to a taiown volume of fresh, cold water  Vvhile
         mixing.   A  55-gallon  drum  can  be used with an electric drun-type
         mixer.

      2. Heat the mixture vJiile stirring to approximately  200°F  to  dissolve
         the  PVA.   The solution will become clear when the powder dissolves.
         Two or three external band heaters, Chrcmalox PFD-130 SG  (120  volt,
         1500  watt)  or  equivalent/ should be used along with a minimum of 2
         inches of external fiberglass insulation.

      3. Allow the solution to cool with  the  container  covered  to  prevent
         evaporation.   The solution can be stored for 4 to 6 weeks before use
         if desired.
                                                                2
     PVA application to the beach is at the rate of 1/2 gall'on/m .

     The  borate  solution  is  made  using  sodiun  tetraborute   decahydrate
(dissolved  in water at the rate of 30 cjn/liter (.25 Ib/gal).  This is ordinary
borax available  at  a  grocery  store.   Stir  or  shake  the  mixture  until
completely dissolved.

     Apply the borax solution over the PVA on sand or gravel in a  fine  spray
at  the  minimm rate of 30 ml/m  (1/8 oz/cn ).  Excess borax will not decrease
the effectiveness of the FVA coating.  .;
                                     139

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                                APPPENDIX D-2-4

                          RECOMMENDED AGENT TCKTCITY
POLYA/INYL ALCOHOL

     Polyvinyl alcohol is generally considered nontoxic.  It  is  approved  toy,
the  FDA for food contact applications and is widely used in contact with skin
as a textile sizing.  PVA is  not  listed  in  the  NTOSH  Registry  of  Toxic
Materials.

     In water, PVA has baen reported (Long-Term Biochemical Oxygen  Danand  of,
Elvanol  Polyvinyl Alcohol, E. I. DuPont de Nsmours & Co., 1970) to have a BOD
(% by weight oxygen consvsned) of 1% at 5 daya and 3% at 30  days.   PVA  would
therefore have little, if any, effect can aquatic life.

BORAX

     Data has baen presented  (R. W. i^ragua. The  Ecological  Significance  of
Boron, U. S. Borax Research Corporation, JSjiahsim, California, 1972) indicating
the toxicity of borax as follows:      '                                       i

          iJDgg (rats):  4.5 - 6.1 gra/kg

          Minimum lethal dose (minnows):  1.9% in HJ3

     Boron compounds can affect plant growth.  Tolerant crops can be grown  in
soils  containing  up to 3.75 ppn boron (32 pptn as borax).  Sea water contains
an average concentration of 4.6 ppm boron.  The amount  of  borax  recommended
for  beach  applications  .(900  itg/m ),  when  dispersed  in sea water, is no*-
expected to adversely affect  marine plant growth.

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