PB85-115822
Closure Evaluation for Petroleum
Residue Land  Treatment
Oklahoma Univ.,  Norman
Prepared  for

Robert S.  Kerr  Environmental Research  Lab,
Ada, OK
Oct 84
                   U.S. DEPARTMENT OF COMMERCE
                 National Technical Information Service


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                                                  EE85-115822
                                            EPA-600/2-84-162
                                            October 1984
          CLOSURE EVALUATION FOR PETROLEUM
               RESIDUE LAND TREATMENT

                        by

       Leale E. Streebin, James M. Robertson,
         Alistaire B. Callender, Lynne Doty,
                Kesavalu Bagawandoss
School of Civil Engineering and Environmental Science
               University of Oklahoma
               Norman, Oklahoma 73019
       Cooperative Agreement No. CR 807936010
                 •  Project Officer

                   Don H. Kampbell
              Source Management Branch
  Robert S. Kerr Environmental Research Laboratory
                Ada, Oklahoma  74820
  ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY
         OFFICE OF RESEARCH AND DEVELOPMENT
        U.S. ENVIRONMENTAL PROTECTION AGENCY
                ADA, OKLAHOMA  74820

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                                  TECHNICAL REPORT DATA
                           (Please read Inuructions on the reverse before completing)
1. REPORT NO.

   EPA-600/2-84-162
                             2.
             3. RECIPIENT'S ACC
                    5   i
4. TITLE AND SUBTITLE
 Closure Evaluation  for Petroleum Residue Land
 Treatment
             5. REPORT DATE
               October 1984
             6. PERFORMING ORGANIZATION CODE
 'LA.Uf.HO&Sreebin,  J.M.  Robertson, A.B. Callender,
 L.M. Doty,  K. Bagawandoss
                                                          8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 School of Civil  Engineering & Environmental Science
 University  of  Oklahoma
 Norman, OK   73019
             10. PROGRAM ELEMENT NO.
                 C73D1C
             11. CONTRACT/GRANT NO.
                                                            CR807936-01-0
                                  Coop.Agr.
12. SPONSORING AGENCY NAME AND ADDRESS
 R.S.  Kerr  Environmental  Research Laboratory
 U.S.  Environmental  Protection Agency
 P.O.  Box  1198
 Ada.  OK 74820	    	
             13. TYPE OF REPORT AND PERIOD COVERED
              Final 11/80 - 01/83       	
             14. SPONSORING AGENCY CODE
              EPA/600/15
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
Three  refinery  land treatment sites which had ceased  applications for 6 months,
9 months, and 6 years  previously were sampled to  define  existing conditions.
Samples were collected during a 15-month study  period.   A considerable variation
existed in  oil  content between the 3 sites.  Site 2,  which had received no waste
for 6  years, had 2-3 wt.% oil in the upper 25 cm.  Site  1 and 3 contained 5-6 and
8-9 wt.%  oil respectively.  Concentrations greater than  background were detected as
deep as 45-50 cm at all  sites.  Average oil content remained relatively constant at
each site during the study.  Large variations for individual core samples were
found  within each site.   Possible contributing  factors  to apparent lack of degrada-
tion were long  periods of extremely wet or dry  soil,  low soil N, and presence of
persistent  hydrocarbons.  Thirteen or more organic priority pollutants were identi-
fied at each site; however, only trace quantities were  found below the till zone.
Several priority pollutants also were identified  in background samples.  Metals
were immobilized in top 25 cm of soil at all sites.  Site 2 supported a lush growth
of vegetation while sites 1 and 3 supported little or no vegetative growth.  Grasses
were more tolerant than tree seedlings when planted in  areas having an oil content
of 5-6 wt.%.  Root development was inhibited at levels  of 4-5 wt.%.  In areas  .
having an oil content of 9-13 wt.%, survival rates for  both were very low.
17.
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                             b.IDENTIFIERS/OPEN ENDED TERMS
                                                                          COSATl Reid/Group
     Waste  treatment
     Organic  wastes
     Petroleum refining
    Solid waste
    Land treatment
    Heavy metals
    Petroleum sludge
                                                                            13B
13. DISTRIBUTION STATEMENT

    Release  to public
19. SECURITY CLASS. (This Report I
    Unclassified
                           21 NO OF.PAGES
                                219
                                             20. SECURITY CLASS (This page)
                                                  Unclassified
                                                                        22. PRICE
EPA Form 2220-1 (9-73)

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                         NOTICE

     Although the research described in this document has
been  funded  wholly  or  in  part  by  the  United  States
Environmental Protection Agency  through assistant agree-
ment number  CR  807936010 to The  University  of Oklahoma,
it has not been  subjected  to  Agency review and therefore
does not necessarily reflect  the  views of  the Agency and
no official endorsement should be inferred.
                          ii

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                                FOREWORD
     EPA Is charged by Congress to protect the Nation's land, air and water
systems.  Under a mandate of national environmental laws focused on air and
water quality, solid waste management and the control of toxic substances,
pesticides, noise, and radiation, the Agency strives to formulate and
implement actions which lead to a compatible balance between human activi-
ties and the ability of natural systems to support and nurture life.

     The Robert S. Kerr Environmental Research Laboratory is the Agency's
center of expertise for investigation of the soil and subsurface environ-
ment.  Personnel at the Laboratory are responsible for management of research
programs to:  (a) determine the fate, transport and transformation rates of
pollutants in the soil, the unsaturated zone and the saturated zones of the
subsurface environment; (b) define the processes to be used in characteriz-
ing the soil and subsurface environment as a receptor of pollutants; (c)
develop techniques for predicting the effect of pollutants on ground water,
soil and indigenous organisms;  and (d) define and demonstrate the applica-
bility and limitations of using natural processes, indigenous to the soil
and subsurface environment, for the protection of this resource.

     The report, a product of our research,  contains information useful to
hazardous waste land treatment facilities and regulating agencies on deci-
sion making for waste disposal problems.  An evaluation of existing condi-
tions at closed oily waste land treatment sites is covered by the topics:
(1) degradation of oil, (2) identification and fate of pollutants, and (3)
site revegetation.
                                    Clinton W.  Hall
                                    Director
                                    Robert S. Kerr Environmental
                                      Research  Laboratory
                                         111

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                        ABSTRACT
     The purpose  of the  study  was to  evaluate  existing
conditions at  sites used for the  land  treatment  of oily
residues, after closure.  Three sites, which had not been
used for between  6  months and 6 years,  were  chosen.   No
nutrients were added to the site soil, and the sites were
tilled 3 or 4  times during  the  study.  Soil samples from
these sites were analyzed for oil  content,  pH,  CEC, TDC,
chlorides,  heavy  metals  and  selected   organic  priority
pollutants.  Soil pore  water samples and deep  core sam-
ples were analyzed  for  heavy metals,  oil content  and se-
lected priority pollutants.   This  was  done  to  determine
if pollutants were moving into or through the unsaturated
zone.  Research on  methods  of revegetating  the  sites us-
ing grasses and trees, was also done  at one site.
     The soil  pore  water contained chlorides  at  concen-
trations from  12  mg/1 to 5000 mg/1,  iron,  and manganese
at concentrations from trace amounts  to  12 mg/1, and zinc
and barium at levels up to 5 mg/1.
     The results show:
(1)  no  statistically significant  degradation  of  the oil
     took place over a 15 month period;
(2)  organic priority  pollutants present at  these sites
     were primarily polynuclear aromatics and phenolics;
(3)  metals are generally immobilized in the top 25 cm of
     soil.  However, some metals are  mobilized and could
     present a  ground water  pollution  threat.   Analysis
     of  soil  pore  water  and deep  core samples indicate

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     the presence of trace amounts of several organics in
     the unsaturated zone up to a depth of 150 cm.
     Trees generally did  not survive at  the  oil  concen-
trations used  (4 to 14%).  Grasses grew  at  soil  oil con-
tent levels up  to  5%,  but root development  was inhibited
at levels of 4 and 5%.
     This report was submitted in fulfillment of Coopera-
tive Agreement  No.  CR  807936010  by  the  School of  Civil
Engineering  and  Environmental  Science,  University  of
Oklahoma under  the sponsorship  of  the  U.S.  Environmental
Protection Agency.  This  report  covers  a period  from No-
vember  1980 to July 1983, and  work  was  completed  as of
June 1983.

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                        CONTENTS


Abstract	   iv

Figures	   ix

Tables	   x

Abbreviations and Symbols	xiii

Acknowledgements	".	  xiv

Section 1      Introduction 	  1

Section 2      Conclusions	  4

Section 3      Recommendations	  7

Section 4      Literature Review	  9

Section 5      Site Selection	  25

                 Site Soil Characteristics	  28

Section 6      Experimental Approach	  34

                 Sampling Procedures	  35

Section 7      Evaluation of Site Characteristics	  40

                 Organics	  40

                 Oil Content	  43

                   Variability of Oil Concentrations..  44
                   Oil Content of Site Soil	  44

                 Metals	  52

                 Unsaturated Zone Monitoring	  58

                   Soil Pore Water Analytical Results.  60
                   Deep Core Analytical Results	  78
  Preceding page blank
vii

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                  CONTENTS (continued)


Section 8      Emission Study	  84

Section 9      Runoff Study	  87

Section 10     Revegetation Study	  92

Section 11     Discussion	  120

References     	  123

Appendix A     Analytical Methods	  129

Appendix B     Site Soil Data	  134

Appendix C     Concentrations of Organic Compounds
               FoUnd in Site Soil	  164

                 Quality Assurance/Quality Control...  177

Appendix D     Field Data for Trees	  181

Appendix E     Climatological Data	  192

Appendix F     X-Ray Diffraction Spectra
               of Site Soil	  195
                            viii

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FIGURES
Figure
6.1
7.1
7.2
7.3
7.4
7.5
7.6
7.7
Method oJ
water san
Graph of
moisture
Graph of
moisture
Graph of
moisture
Graph of
moisture
Graph of
moisture
Graph of
moisture
Graph of
moisture
E installation of soil pore
TOC vs time for site 1 soil
TOC vs time for site 2 soil
COD vs time for site 2 soil
Cl vs time for site 2 soil
samples 	
TOC vs time for site 3 soil
samples 	
COD vs time for site 3 soil
samples 	
Cl vs time for site 3 soil
samples 	
Page
38
71
72
73
74
75
76
77
    ix

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                         TABLES
Table 4.1


Table 5.1

Table 5.2

Table 5.3

Table 7.1

Table 7.2


Table 7.4


Table 7.5


Table 7.6

Table 7.7

Table 7.8

Table 7.9

Table 7.10


Table 7.11


Table 7.12

Table 7.13

Table 7.14
Toxic Pollutants Detected in
Refinery Treated Effluents	  16

Site Soil Textural Classification	  29

Soil Permeability Values	  30

Cation Exchange Capacity of Site Soil..  33

Priority Pollutants 	  41
Organic Compounds Indentified
in Soil at Land Treatment Sites,
Variability of Oil Concentration
at Site 3	,
Variability of Oil Concentration
at Site 2	.,
Oil Content Data - Means Site 1	

Oil Content Data - Means Site 2	

Oil Content Data - Means Site 3	

Composition of Oil at Sites 2 and 3...

Nitrogen and Phosphorus in Soil
at Sites	
42


45


46

48

48

50

50


52
Metals Found in Concentrations
Significantly Above Background	 54

Site pH Values	 57

Soil Chloride Concentration	 57

Soil TOC	 59

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                   TABLES (continued)
Table 7.15


Table 7.16

Table 7.17

Table 7.18

Table .7.19


Table 7.20


Table 7.21


Table 7.22


Table 7.23

Table 7.24

Table 7.25


Table 8.1


Table 9.1

Table 9.2


Table 9.3

Table 10.1

Table 10.2

Table 10.3


Table 10.4

Table 10.5
Priority Pollutants Present in
Soil Pore Water	  61

Soil Pore Water Metals (Site 1)	  62

Soil Pore Water Metals (Site 2)	  63

Soil Pore Water Metals (Site 3)	  64

Soil Pore Water Chloride Ion
Concentration	  66

Soil Pore Water Characteristics
Site 1	  68

Soil Pore Water Characteristics
Site 2	  69

Soil Pore Water Characteristics
Site 3	  70

Oil Content of Soil Pore Water	  78

Oil Content Data for Deep Cores	  80

Priority Polluants Present in Un-
saturated Zone Cores	  81

Concentrations of Hydrocarbons
Emitted at Sites 1 and 3	  85

COD/TOC Concentrations of Runoff	  88

Oil and Grease Concentrations
of Runoff	  88

Metal Concentrations in Runoff Water...  89

Oil Content Analysis	103

Mean Values for Tree Height and Width..104

% Oil Content 8 Centimeters from
Tree Base	108

Nutrient Analysis for Field Sites	Ill

Oil Content of Grass Plots	112
                          XI

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                   TABLES (continued)


Table 10.6     Environmental Chamber Soil
               Characteristics	113

Table 10.7     Mean Height Values for Grass	114

Table 10.8     Above Ground Biomass of Grass	115
                         Xll

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                ABBREVIATIONS AND SYMBOLS

TOC       Total Organic Carbon
COD     _  Chemical Oxygen Demand
CEC       Cation Exchange Capacity
GC        Gas Chromotography
GC/MS     Gas Chromatography/Mass Spectrometry
PNA       Polynuclear Aromatic

mg/1      milligrams per liter
ppb       parts per billion
ppm       parts per million
mg/kg     milligrams per kilogram
Ag        silver
Ac        aluminum
As        arsenic
Ba        barium
Cd        cadmium
Co        cobalt
Cr        chromium
Cu        copper
Fe        iron
Mn        manganese
Ni        nickel
Pb        lead
Se        selenium
Zn        zinc

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                    ACKNOWLEDGEMENTS

     The authors would like to acknowledge the assistance
of Dr.  Eric Enwall  and  Dr. Tom  Karns of  the  Chemistry
Department at the University of Oklahoma  for their great
assistance in the identification  of  organic compounds by
GC/MS.  We  would  also like to thank  project officer Dr.
Don Kampbell  and  Mr. Leon  Meyers of the Robert  S.  Kerr
Environmental Research  Laboratory, for their assistance
and guidance during  this project.  We would also like to
acknowledge  the  advice   and  assistance  of  Dr.  R.L.
Dalrymple of  the  Noble Foundation of  Oklahoma,  and Drs.
John  Fletcher,  Elroy Rice  and  George Goodman  for their
advice on the revegetation  study.  We would also like to
express our  appreciation to Cindy James,  Nancy Laudick,
Charles Carpenter and Vickie McFarland for their assis-
tance with  the  analytical  work.    Finally,  we would like
to express  our  sincere  appreciation  to Barbara Jones and
Betty Craig for the  preparation of the manuscript.
                         xiv

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                        SECTION 1
                      INTRODUCTION

     Land treatment as a method of disposal of oily resi-
dues from oil refinery operations has become very popular
in recent years.  The technique has been in use for 15 to
20 years, and several studies  have  been performed to de-
termine  the  fate of  the  oil  and  metals at  active  land
treatment sites.  However  few studies  have  been carried
out on  the long-term effects  on the  site soil  of  land
farming operations,  or on monitoring the unsaturated zone
at closed  sites to see if  a long-term  threat  to ground
water exists at these sites.   The purpose  of this report
is  to  describe a  study  carried  out  at  three  closed
(inactive)  land treatment sites.   The major objectives of
this study were:
1.   To identify priority pollutants present  in the  site
     soil at depths up to 152 cm (60 inches).
2.   To identify priority pollutants present in soil-pore
     water at a depth of 1.2 m (4 feet).
3.   To identify grasses and/or trees which would grow at
     land treatment sites used for oily residues.
4.   To  determine   the  environmental   impacts  resulting
     from land treatment of residues from an oil refinery
     with emphasis  on closure of land treatment sites.
     Specifically the  environmental objectives included
identification  of   the  quality  of   runoff  and  volatile
emissions  from  the sites,  vertical migration  of pollu-
tants, and evaluation of changes  in soil characteristics

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as a result of land treatment activities.
     To  achieve  these  objectives  land treatment  sites
which had been in  use  for  a  number of years were select-
ed.  Soil samples from depths 0-25 and 25-51 cm were ana-
lyzed for oil  content,  metals, TOC,  COD,  pH,  nutrients,
chloride, cation exchange  capacity,  and selected organic
priority pollutants.  The  unsaturated zones at the sites
at depths  from 51-152 cm  were sampled, and  the samples
analyzed  for  oil  content, metals  and  selected organic
compounds.  The  soil-pore  water in  the  unsaturated zone
was sampled using  vacuum  soil-pore water samplers  (lysi-
meters),  and  the  samples  analyzed  for  oil  content,
metals,  TOC, COD and selected organics.
     The  0-25  and  25-51 cm  depths were  chosen, because
land treatment sites are tilled, and the till zone usual-
ly extends  to  a  depth of  about 25  cm.   Since  this depth
is completely mixed during tilling, it was felt that sam-
pling shallower depths would be unproductive.   The depth
25-51 cm  was  chosen since preliminary  sampling  at these
sites indicated the presence of oil  in  some areas of the
sites down to this depth.
     Samples of soil-pore  water were  collected as a part
of  the  unsaturated  zone  monitoring  program,  to  see
whether any pollutants were  passing through the unsatur-
ated zone, and if so,  in what quantities.
     Samples  of  the  0-25  cm   and  25-51  cm  zones  were
analyzed  for  oil  content  over  the duration of  the pro-
ject, in  an attempt  to  determine  rates  of degradation.
In addition a  part  of  each site was tilled periodically,
to  see  if  this  enhanced  the   rate  of  degradation when
compared to the untilled section of the site.
     The  major  thrust in  the  analysis of  the  site soil
and  soil-pore  water   for  priority  pollutants,  was  to
identify qualitatively the compounds present.   Quantita-

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tive  evaluation  was  beyond  the  scope  of  this  project,
although concentrations of the  compounds  identified were
calculated,  to  give  an  idea  of  the concentrations  of
the compounds identified.
     Parameters measured  other  than  priority  pollutants
are all  important  in  determining the rate  of  removal  of
oil through degradation, emission etc.,  and the potential
for mobilization of pollutants..
     The  site  soil  was  also  evaluated  for changes  in
permeability,  soil structure,  soil  texture and  cation
exchange capacity.

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                        SECTION 2
                       CONCLUSIONS

     This study suggests a number of factors which should
be considered in any closure monitoring program.
     (1)   The  soil  pore  water passing  through  the  un-
          saturated  zone  may  contain  high  levels  of
          salts,  especially chloride,  as  well  as  high
          levels of iron  and manganese  and other oxidiz-
          able material.  Our  results  show that chloride
          levels  decrease  with  time,  but  persist  for
          longer than the 90 days now  required for moni-
          toring soil pore  water  after  waste application
          has  ceased.   This  information  indicates  that
          monitoring of  the soil  pore  water  for longer
          than 90 days is required.
     (2)   Some  vertical  migration  of  oil  did  occur  at
          the  study sites,  but  this  migration  did  not
          extend below 50 centimeters of the surface.  No
          oil was present in  the  soil  between 50 and 150
          cm, at these sites.
     (3)   Metals  in  land   treatment   site  soils  were
          immobilized in the top  25 cm of the soil.  Some
          soil  pore water  samples  from  the  sites  con-
          tained concentrations of Ba  which exceeded the
          primary drinking  water  standards levels and Fe
          and Mn which exceeded secondary standards.
     (4)   Organic priority  pollutants  in  our land treat-
          ment site soils were primarily polynuclear aro-

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     matic  compounds and  phenols.   Several of  them
     were  found in the  unsaturated  zone in the  ppb
     range.   Apparently movement of pollutants  into
     the unsaturated  zone  occurred.
(5)   Sampling  procedures  at  land  treatment   sites
     must  be  carefully  designed,  since  there  is
     considerable  variability in oil  concentrations
     across  a site.
(6)   Reduction of oil  content  levels to background
     may  not  be  possible  at  land  treatment  sites.
     One  site  in  our  study  was well managed,  had
     nutrient levels  which supported  profuse vegeta-
     tive  growth and had  no  residues applied  for  6
     years.    The  soil   at this  site still  had  an
     average oil content  level  of  between  2}  and  3
     percent.  Thus,  it may be more practical  to re-
     duce  levels  to  the point where leaching,  hydro-
     carbon,  emissions, plant inhibition and  pollu-
     tant  surface  runoff are  no  longer problems.
(7)   Vegetative cover reduces contamination of  run-
     off with site pollutants, and improves appear-
     ance.
(8)   Increased amounts  of  volatile hydrocarbons will
     be  emitted during the  tilling  process   for  an
     extended period  of time  after waste application
     has ceased.
(9)   Revegetation  of land treatment sites  with high
     oil concentrations is not desirable since root
     development  is  inhibited.   Grasses  are the best
     for initial  revegetation.   They  provide a quick
     cover,  aerate the  soil,  have root systems which
     can hold the  top layer of  soil  in place.
(10)  A ground cover using  certain  grasses   can  be
     established  at  oil  concentrations  of 4 to  5

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     percent.   However,  root  development  and  crop
     yield  is  significantly inhibited.
(11)  At  the time of closure the  land treatment  site
     should be  tilled  at  frequent  intervals   and
     nutrients applied until  the' oil  concentration
     has  decreased to a maximum of 3  percent prior
     to  attempting to  establish a ground  cover using
     forage crops  (grasses).

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                        SECTION 3
                     RECOMMENDATIONS

     This study  indicates  the need for  further  research
in the following areas.
(1)   Identification of organic compounds present  at land
     treatment sites both qualitatively and quantitative-
     ly.   A  major  consideration needs  to  be  studies  on
     the  recovery of organics from soil matrices.
(2)   Work is needed  on soil  pore water  monitoring  at
     sites.    Different  methods  of  installation   for  the
     pore water sampler need to be evaluated.  The effect
     of the porous ceramic cup on pollutants in  the soil
     pore water, especially  organic priority pollutants,
     needs evaluation.
(3)   Hydrocarbon  quantities  emitted   at  land  treatment
     sites need to be evaluated.  Air  emissions  could be
     an  important  mode  by which  hydrocarbons are lost
     from sites.
(4)   Research is needed on revegetation of sites  used for
     land treatment of oily  residues.   Areas of  investi-
     gation should include:
     (a)   the  identification of  waste tolerant  species
          including legumes.
     (b)   the determination of waste constituents bio ac-
          cumulated by plants.
     (c)   the  determination  of  good  soil  conditioning
          methods  and  planting  techniques  for revegeta-
          tion.

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(d)   The  selection of proper tilling practices.

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                        SECTION 4
                    LITERATURE REVIEW

     Prior to the development of this research project, a
comprehensive  literature  review was  carried out  on  the
subject of land  treatment  of  oily  residues.   This review
encompassed  management  practices  and  monitoring  tech-
niques used at land  treatment facilities,  as well as any
other relevant information.
     Several researchers have investigated land treatment
of oily  residues in the  last few years.  These include
Meyers and Huddleston,  1979; Huddleston, 1979; Huddleston
and Meyers,  1978;  Cresswell,  1977; Kincannon,  1972;  and
Raymond, Hudson  and  Jamison,  1976.   The results of these
research  projects  have  been  cited  extensively  in  the
literature and will  not  be reviewed  in detail here.  The
general  conclusion  drawn  from  this  work  has  been that
land treatment is an environmentally sound and effective
way to dispose of oily residues.
     The  factors affecting degradation of oily residues
have also been investigated.  Cresswell (1977) identified
the primary  factors affecting  oil degradation  rates  in
the soil as
     1.  petroleum composition    4.   oxygen availability
     2.  temperature              5.   water
     3.  nutrients                 6.   pH.
However, little  data on  the relative importance of these
factors, and their  interrelationships has been reported.
     Most of the data  produced  by  land treatment studies

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has focused on  short-term  effects.   Few researchers have
evaluated  the  potential  for  long-term  impacts  on  the
environment.    These   long  term  impacts  need   to  be
addressed in view of the fact  that  there  is  a buildup of
heavy metals  in the soil during  land  treatment.   Fuller
(1977)  reported  that  under  anaerobic  conditions  the
mobility of several heavy  metals  (As,  Cr,  Fe, Cn,  Zn) is
enhanced.   (Anaerobic conditions can and do occur at land
treatment  sites,  particularly  under conditions of  high
soil  moisture  content, when  leaching  is most  likely to
occur).
     Hahne  and  Kroontje  (1973)  reported  that  in  the
presence of chloride  ion,  the  solubility of  Cd,  Zn, Pb,
and Hg  is  increased  even  at  a pH  as  high   as  9.   They
indicated  that  at a pH  of 9  soluble  chloride complexes
can be  found  at  ion  concentrations of  354  to 28  ppm.
High  chloride  ion concentrations can be  present  at land
treatment  sites because  of  the occurrence of brines with
crude oil  and  the  high  chloride  ion content  of  some of
the wastes which result from refinery operations.
     Huddleston et al. (1982)  reported in a study carried
out at  five closed  refinery  land  treatment  sites,  that
wastes had been degraded without appreciable migration of
degradation products  and also, that metals  in the waste
remained in the waste application zone.
     One problem  which might  arise  from  the  disposal of
oily  residues  by  land  treatment,  is  the   movement  of
leachate through  the  unsaturated zone  to the underlying
ground water.   This could  result  in contamination of the
ground  water.   Thus,  the  unsaturated  zone  at  a   land
treatment  site  needs to be  monitored in order that any
pollutant   movement  can   be  detected.    Current  EPA
regulations require the  use  of monitoring wells, and the
collection  and  analysis  of  soil core samples as a method

                           10

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of  detecting  pollutant  movement.   The  EPA  has  also
required the  use  of soil moisture  samplers  for sampling
soil pore water in the unsaturated zone under active land
treatment sites.
     Soil moisture  samplers using  a porous  ceramic  cup
have been  used for many  years  for  collecting  soil pore
water samples.  Briggs  and McCall  first  reported  on  the
use of porous  ceramic cups  in 1904,  and since that time,
their usage  has  increased,  especially  in the  last 10 to
15 years.  However, with  their  increased usage questions
have arisen  as to  the  validity of  samples  collected in
this way.
     Wagner   (1962)   used  the  porous  ceramic  cup  and
reported no  adsorptive  capacity  of the cup  for  nitrate
ions, but  an appreciable adsorptive capacity  of  about 1
mg of  N for  NH4   ions.  Reeve  and Doering  (1965)  used
ceramic  cups  to  collect soil water  samples  for salinity
determinations.   The  values  obtained  from   the  sampler
agreed with  the  values  obtained  by  the conventional  sa-
turation method.  They also found that the composition of
the sample changed with time, but that consistent and re-
liable values for the  composition  of  the soil solution
were obtained when a  vacuum in  the range  of 0  to  500
millibars was used to collect the sample.
     Grover and Lamborn (1970)  reported that ceramic cups
contributed  excessive  amounts  of  Ca  ,  Na    and   K   to
solutions  drawn  through  them,   and adsorbed  phosphorus
from solutions containing  phosphorus.   They  found that
leaching the  cups with  1 N HC1 reduced Na and K contam-
ination, and  the  amount of phosphorus  adsorbed,  but  ap-
preciable amounts of  calcium contamination  still  occur-
red.  Wood  (1973) also  reported contamination by Ca,  Mg,
Na, HCO.. and SiO_ of the sample.   He  minimized the pro-
blem by  leaching  the ceramic cups with  8 N HC1.

                          11

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     Zimmermann,  Price  and Montgomery   (1978)  reported
loss of nutrients after filtration through porous ceramic
cups  used  to  sample  sediment.   The  most  significant
losses occurred  with  NH. and phosphate  ions.   Levin and
Jackson (1977) also reported screening of NO.-N when they
used porous  ceramic  cups for sampling soil  water.   How-
ever,  Johnson and Cartwright  (1980)  used  soil moisture
samplers  with  porous  ceramic  cups  for  sampling  the
unsaturated zone under landfills in Illinois.  They found
that  samples  taken   with   soil  moisture  samplers  were
representative of the surrounding leachate composition of
major ions.  They point out that while sample variability
or  bias  of  several   milligrams  per  liter  may  be  quite
significant  when  the   concentration of   the  ions  of
interest in  the  soil  water is low, this  is  not the case
when  sampling  highly  contaminated   leachate  with  high
ionic concentrations.
     Questions have been raised .as to the validity of the
samples  collected using  porous  ceramic cups.   England
(1974)  pointed out the following:
     (1)   Concentrations and composition  of  the soil so-
          lution are not homogeneous throughout its mass.
     (2)   Cations vary widely in  the  degree of dissocia-
          tion from the  surface  of  electro  negative col-
          loidal  particles.  Water   drained   from  large
          pores  at low  suctions  may have  a  different
          chemical composition  from  that extracted from
          micropores.
     (3)   Concentrations of various  ions  in  a  soil so-
          lution generally do not vary inversely with the
          soil  water  content.   Dissolved quantities  of
          some  ions  increase  on dilution,  while quanti-
          ties of other ions may decrease.
Hansen and Harris  (1975) ,  did extensive work  on the use

                          12

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of porous ceramic samplers.  They  found  that the rate of
sample uptake was strongly influenced by cup uptake rate,
plugging  of the  cup/  sampler  depth,  and  the  type  of
vacuum  system  used.   They  also found  that a number  of
factors affected  the  sample concentration  as  the  sample
is drawn through the  ceramic cup.   These factors are in-
take rate, leaching,  sorption and screening.
     Van der Ploeg and Beese  (1977)  showed that  the soil
moisture sampler distorts  the existing gradient  patterns
in the  soil in such  a way,  that around  the  ceramic cup
exaggerated  percolation  rates  are  created.   They  state
that  the  composition of  the  collected  sample is  not
representative  for  one  particular  depth, but  reflects
some  average  composition of  the  surroundings.  Van der
Ploeg and Beese  found that extraction rates  with  even a
small vacuum applied  were much higher than the  percola-
tion  rate  under  freely  vertically  draining  conditions.
They  could  find  no relation  between the  amount of soil
water extracted and the freely percolating soil water.
     It thus appears  that a great  deal of care must be
taken in  extrapolating  results  obtained with  the  use of
soil water samplers to conditions which actually exist in
the  unsaturated  zone.    This   is   especially  true  when
dealing with environments where solute concentrations are
low.   Little  has  been  written  on  the  effect of  the
ceramic cups on  low  level organics  which  may  be present
in the  soil water,  and this is an  'area  which needs more
research.
     The soil moisture sampler most commonly used in mon-
itoring the  unsaturated  zone is a  pressure vacuum model
which was  developed  by  Parizek and Lane  (1970) .   This
sample  can  be  effectively used  up  to  depths  of  50 feet,
and can be  used  to collect samples  over a long  period of
time.   This particular model has  the advantage that it

                           13

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can be installed in  a  given  location and the samples re-
moved from the sampler at another location.  For example,
the sampler can be installed under an active landfill and
the samples collected at the side of the landfill.
     Soils  used  for  the  dosposal  of  oily sludges  may
contain a  number of heavy metals which  are potentially
toxic to the  environment.  Contamination to ground water
by heavy metals  is  believed  to be of  minimal  concern if
adequate soil pH is  maintained at a  land treatment site.
Most metals are immobilized  when  soil  pH is greater than
6.5.  The  leaching  of  metals, therefore  is  not of major
concern on treatment sites with proper pH control  (Dibble
and Bartha 1979,  Francsen 1980, Huddleston 1979).
     Leeper  (1978)  believes  that pH is  the single most
important aspect of the reaction between heavy  metals and
soils.  Soil treated with sludges containing heavy metals
should be  medium to fine  textured,  have a  pH  above 6.5
and contain 3-7% organic matter with a C.E.C. of at least
14 in order to be considered acceptable for the retention
of metals  (Huddleston  1979,  Leeper  1978, Loehr  et al. ,
1979) .
     Hydrocarbon Processing  (1980) reports that "virtual-
ly  all  published  information  on landfarming  indicates
that  there Is  little migration of contaminants below the
top  12  inches of  soil".   Little work has  been  done to
date  on  the leaching  of  metals in  soil  containing oily
waste, although the movement of heavy metals in landfills
or in soils  amended with sewage  sludge  has  been  studied
extensively (Schilesky 1979).
     Raymond  et  al.  (1976)  conducted  a  land  treatment
study in which  oil degradation was  monitored  over a one
year  time  period.   The movement  of  lead, which  was the
metal of highest  concentration in the  oil,  was examined
and  no  evidence  was found that  the  nitric acid-soluble
                          14

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form leaches through the soil.
     Dibble and Bartha  (1979)  found  hydrocarbons did not
leach below  a depth at  which oil sludge was  mixed with
sandy soil.   Based on  Raymond et al.'s  studies,  Dibble
and Bartha  concluded  that heavy metal  residues  from oil
sludges would display low mobility in limed soil.
     The  possibility  for  the  leaching  of heavy  metals
through  soil  is great  if  high pH  levels are not  main-
tained at land treatment sites.  Heavy metals can be tox-
ic, therefore suitable oily wastes for land treatment are
those which  do  not contain extremely high  metal concen-
trations  (Huddleston 1979) .
     Refinery waste streams  contain a  wide  variety  of
pollutants.  The EPA has reported a  number  of  toxic pol-
lutants  which have  been detected  in  treated effluents
from refineries.  A list of these pollutants  is  shown in
Table 4.1.  A review of the literature did not reveal any
specific  organic compounds  which had been  identified at
land treatment sites for oily residues.
     Interest in  the effect  of  land  treatment of oily
residues on vegetation has increased as the usage of land
treatment has increased.  Observations  of accidental oil
spills,   from pipelines  or  tankers,  prompted  investiga-
tions into the  effects  of crude oil on  vegetation  prior
to  the  practice of land  treatment.  Much  of  this  re-
search,   however,  focuses  on   coastal  tundra  and  marine
species rather than on terrestrial plants.
     There exists  a lack  of   information concerning  the
affects  of  land-applied oily wastes  upon  vegetation.
Studies have been conducted for crop species, but data on
perennial plants are not readily available.   The majority
of  information  focuses  on  the  germination,   growth  and
yield of a variety  of crop species.
     Dibble and Bartha  (1979)  described a rehabilitation

                          15

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        TABLE 4.1.
               TOXIC POLLUTANTS DETECTED IN
               REFINERY TREATMENT EFFLUENTS
1.   Organics

benzene
1,2-dichloroethane
1,1/2,2-tetrachloroethane
parachlorometacresol
1,2-trans-dichloroethylene
2,4-dimethylphenol
ethylbenzene
fluoranthene
methylene chloride
dichlorobromomethane
naphthalene
4-nitrophenol
phenol
                         bis (2-ethylhexyl)phthalate
                         diethylphthalate
                         benzo(a)anthracene
                         benzo(a)pyrene
                         chrysene
                         anthracene
                         benzo(g,h,i)perylene
                         fluorene
                         phenanthrene
                         pyrene
                         tetrachlorpethylene
                         toluene
                         trichloroethylene
2.
Pesticides
None

3.   Metals

antimony  (total)
arsenic  (total)
chromium  (total)
beryllium  (total)
cadmium  (total)
copper (total)
cyanide  (total)
                         lead (total)
                         mercury  (total)
                         nickel  (total)
                         selenium  (total)
                         silver
                         thallium  (total)
                         zinc (total)
None
Ref;
     Others  (Asbestos, 4AAP Phenol)
 EPA "Development Document for Effluent Limitations
 Guidelines and Standards for the Petroleum Refining
 Point Source Category", EPA 440/1-79/014-b,
 December 1979, Effluent Guidelines Division, E.P.A.
                           16

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program carried  out  for two years at  the  location of an
underground pipeline  break  in a New Jersey  winter wheat
field.  After  emergency cleanup operations  the  1.5 hec-
tare wheat  field which had  been covered by  1.9  million
liters of kerosine  (no. 1 grade fuel  oil)  was rehabili-
tated by liming, fertilizing and frequent tilling.
     In the spill area  all  of the  wheat had been killed.
Attempts were  made  to  reestablish the  plant cover  ten
months after the spill  occurred.  However,  a  good stand
was not developed until two years after the spill.
     Rehabilitation time  was influenced by  the  type  and
quantity of oil, the  nature  of  the contaminated  soil  and
climatic conditions.   Dibble and  Bartha noted  that  de-
crease in oil concentration over time has a definite cor-
relation with  temperature.   They concluded  this  decrease
resulted from  biodegradation  and evaporation and  was  not
due to leaching.
     Dibble  and  Bartha  (1979)  performed  a  greenhouse
study  to  see  if a  low  concentration   (0.34% wt/wt)  of
kerosine in the  soil  one  year after  contamination had an
effect on the  germination of wheat and soybeans.   In  the
first ten days after  planting,  the seeds germinated at a
slower rate compared  to controls.  After 24  days growth
the wheat and soybean plants appeared stunted.
     The authors concluded that  since a nutrient solution
was supplied to  the plants,  the slow  rate of germination
and  stunting   was  due  to  competition  for  oxygen  with
hydrocarbonoclastic microorganisms.
     Murphy (1929) also reported a delay in wheat germin-
ation when it  was grown in  soil containing  small amounts
of crude oil.  Wheat  seeds  which failed to germinate  had
rotted kernels.  Murphy found that mixing crude petroleum
on the  soil  surface  prevented  seed  germination,  whereas
germination was  not  affected when the  petroleum  was  ap-

                          17

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plied four inches below the surface.
     Volatile-oil fractions have  high  "wetting" capacity
and penetrating  power.   If they  come into  contact  with
plant seed, they enter the seed coat readily and kill the
germ.   Seed  viability is  less  apt to decrease  when the
excess of  oil  volatiles  has  escaped from  contaminated
soil prior to planting (Plice 1948) .
     Knowlton and  Rucker  (1979)  analyzed wheat  grown on
an  oil  refinery  land treatment  site.   No  heavy  metals
were  found to  have  accumulated  in the  roots,  stalks /-
leaves and grain of the plants.
     Meyers and Huddleston (1979)  also  found no signifi-
cant  increase  in  the uptake  of  heavy  metals  by  wheat
grown on a land treatment  site.  Wheat germinated only on
sites where  there  were  low  concentrations of  refinery
waste.  Here, the plants developed more  slowly than con-
trol plants  and  the  grain had a  20%  lower  nitrogen con-
tent.
     Meyers  and  Huddleston  (1979)  concluded  that  lower
nitrogen content in the  grain was  the  result of less ni-
trogen being available to  the plants as  a  result  of as-
similation  by  microorganisms  degrading  the  waste  oil.
Ross and Phung  (1977) came to  similar  conclusions  about
nitrogen in  their  case  studies with  ragweed,  ice  plant,
nutgrass and  cocklebur.    These investigators  also  found
unusually  high  levels of  Zn, Mo  and Pb  in  nutgrass and
cocklebur.
     Giddens  (1976)  studied the  effects of  spent  motor
oil on peanuts, cotton,  soybeans and corn.  He postulated
that lubricating oils containing  predominately saturated
hydrocarbons with  20-70  carbons  created  nutrient  imbal-
ances, especially of nitrogen when mixed with  the soil
     At oil rates of up to 31,111 liters/ha.,  Giddens was
successful in growing peanuts, soybeans and corn when am-

                           18

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ply fertilized.  Growth of sorghum and weeds was signifi-
cantly reduced with high oil rates.  The effect of numer-
ous  nitrogen additions  to  oil  applied  to  a  plant-soil
system is not known (Overcash and Pal 1979).
     Carr  (1919)  showed  that  soybean growth was somewhat
improved by  adding  small amounts  (up to  0.75%)  of crude
oil to soil  and may even have been  desirable  in the de-
velopment  of nodules.  A  large  amount  (4%)  of  oil  was
able  to  be  added  before the  soybeans  succumbed  to  the
treatment.   The  damage seemed to  be due  in part  to  the
plants inability  to secure  water  rapidly  enough to meet
its needs.
     A survey of land in Great Britain which was natural-
ly  impregnated  with   hydrocarbons  in  the  form of  oil
shales was done by Gudin and Syratt (1975) .   They found
the  most  abundant  plant species  to be  members  of  the
Leguminosae.   Oil polluted  areas near the British Petro-
leum Company's  Dunkirk refinery also showed  a dominance
of legume  species.  The  abundance  of legumes was thought
to be due  to symbiotic relationships with Rhizobium spe-
cies.  Because of the relationship with Rhizobium, legume
species do not have to compete for nitrogen with microor-
ganisms which break down hydrocarbons in soil.
     McGill  (1976)  believes that it  is  probably advanta-
geous to  plant nitrogen  fixing  species on  partially or
completely reclaimed oil  spill sites.   This,  however, is
questionable because of the high nutrient requirements of
some nitrogen fixers.
     McGill  reports  that trees   are  not very tolerant of
oil spill conditions and  there  is  some  evidence that the
addition of  fertilizer to oil contaminated soil  is detri-
mental to some tree species.  Grasses may be the most de-
sirable type of  plant  to use  for revegetation because of
their root system.

                          19

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     The species  of  plant seeded on  an  oil contaminated
soil should  be adapted to  the soil  and  climatic condi-
tions in the  area.   Native  species  can be used but there
is  difficulty in  obtaining viable  seed  or  rootstocks.
McGill  feels  that "tame" species  are probably  the  best
choice  for  revegetation when  a  quick cover  is  desired.
He  does  caution that  revegetation  of a  site containing
large amounts  of  oil  although  possible,  is not desirable
until much of  the oil has been degraded.
     Plice (1948) studied over several years in Oklahoma,
a variety of plant species and their relationship to soil
fertility when various petroleum materials  were applied
to  the  soil.   These plants included  Darso sorghum,  soy-
beans, field peas, wheat, barley, rye, hairy vetch, crim-
son clover and Hubam clover.  Plice also observed the en-
vironmental effects of pipeline breaks.
     Plice made  some  interesting observations.  He noted
that the amount of damage done and the time which was re-
quired  for  reclamation depended on the  size  of  the area
involved and the degree of saturation by the oil.
          Oil  penetrations  which do  not  go  deeper  into
     the  soil than  plow  depth  can usually  be  overcome
     within  a  year or two  by  cultivation - particularly
     if dry,  sunny weather  can lend a hand.  The present
     study indicates  that,  in the  case  of deep penetra-
     tions of  one foot or more, no attempt should be made
     to make  cultivations until the  oil has  "weathered"
     to a  depth somewhat greater  than the  soil will be
     plowed.   Depending  on  the  extent  of subsequent hot
     and dry  weather, this time  period could be  2  or  3
     years or  even longer.
          Hot  dry  and sunny weather  greatly hastens the
     escape  of volatile fractions  and,  in time, removes
     the  gumminess of  the  soil  so  that  the  soil  will
     scour a plow  (Plice 1948) .
     Plice noted  that soils which were deeply oiled con-
tained  no  vegetation for two  full  years.   He cultivated
such plots and noted  that aggregates had been  broken down

                          20

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even  in clay  soils.   Cultivated  soils were  especially
subject to blowing  after periods of dry,  windy weather.
Uncultivated,  heavily  oiled  soils  were  not  subject  to
wind action.
     In areas  where  oil  spills have occurred,  Plice has
noted  that  deeply oiled soils  react  to  moisture  quite
differently  than  do  shallow oiled  soils.   Shallow oiled
soils come to "moisture equilibrium" within a week or two
after  a good  rain  and will dry  relatively fast  in dry
weather.  Deeply oiled soils rather than being wetted di-
rectly  by  rainfall  are  wetted  from the sides  or moving
ground water and thereby take longer to obtain moist sur-
faces.  Once wet, however, deeply oiled soils,  cultivated
or not  remained wet for  many  weeks.   This  knowledge  is
important  to  the  growing  of  vegetation   on  oil  spill
sites.
     Plice found that  in  the  third  summer  of study crab-
grass and blue grama  grass was being  established on the
        •
cultivated, deeply-oiled soils.  In the fourth summer the
plots were  completely covered with a  variety of natural
grasses.  After four  years  there was  no  growth  of any
sort on the uncultivated deeply-oiled plots.
     Crop planting  is  recommended only  after  friability
is restored  to  an oil  inundated site.   A decreased stand
is almost  inevitable  at first.  Plice  (1948)  and  Carr
(1919)  both  agree  that the presence  of oil in  soil re-
sults in damage  to plants because they are unable to ob-
tain sufficient moisture and air.
     In a  recent study  by  Watts and  Corey  (1981)  crab-
grass  was  found  to be  the  dominant   species  naturally
encroaching  upon  their   land   treatment  site   in  South
Carolina.  The  extreme domination of  crabgrass and total
exclusion of dicots  may  prove  to be  interesting in the
study of species tolerance to oil.
                          21

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     Inhibition  of  natural vegetation  was apparent  for
two years  in oil treated  plots.   After three  years  the
species diversity of ruderal plants  was  very  low.   Small
quantities of Cynadon dactylon, Dioda teres and Richardia
scabra were  observed.  Crabgrass  as  mentioned previously
dominated these sites.
     Watts and Corey  found that the germination of corn
planted on their  land  treatment site one  year  after  ap-
plication  had less than  10% germination on soil with an
                            2
oil concentration of  21  1/m .   The maximum  height that
the corn reached was approximately 40 cm before it  died.
     One of  Watts and Corey's  conclusions  regarding veg-
etation  on  land  treatment sites  was  that  the  primary
inhibitory factor  was the inverse  relationship  between
oil content  and soil water.  In oil treated plots  neither
the C0_  emanation rate nor  the soil moisture  increased
with the  addition  of  water.   Water  either pooled  on  the
top of the soil or penetrated with no apparent wetting.
     In addition, Watts and Corey showed that land  dispo-
sal of  waste oil increased organic  matter, phosphorous,
potassium  and  calcium  content  of the soil and decreased
magnesium  content  for  up  to eight months  after applica-
tion.  Along with these changes was an increased CO- evo-
lution rate  due  to  probable  increases  in microbial popu-
lations .
     Brown et al.f  (1979)  studied the impact of API sepa-
rator  sludges  on  the  emergence  and yield of  ryegrass.
They  found  depressed  results  with  concentrations  of
hydrocarbons as  low as  2% V/V  in  soil.   Poor growth and
yield were attributed   to phytotoxic waste constituents
and impaired water, air and nutrient relations.
     Gudin and  Syratt  (1975)  observed  a competition for
nitrogen  between ryegrass  and  microorganisms  degrading
hydrocarbons in  their greenhouse study  even in the pres-

                           22

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ence of additional nitrogen.  A solid hydrocarbon residue
had  been  incorporated  into the  soil  at a  rate of  500
kg/ha  and  the 50% disappearance  time measured  with  and
without  a  cover crop.   The residue  took   125 days  to
disappear without  a cover  crop  as  compared to only  50
days with a cover.
     Data presented by  Schwedinger  (1968)  clearly  showed
that,  although set  back,  ryegrass can tolerate  up  to  3%
of oil by weight  of  soil  without  showing severe signs  of
damage.  Schwedinger also observed oats, sorghum, tomato,
kale  and  lettuce plants  in growth chamber  studies.   He
noted  the amount of crude oil plants can tolerate in soil
is species  dependent.   Shallow rooted hardy grasses  are
probably  least  susceptible  to  the  treated  soil.   Fur-
thermore, the depth  at which oil contamination occurred
seemed to have no  effect  on the  amount  of  damage  plants
suffered.
     Plants grown  on oil contaminated soil have a slow
rate of water uptake and  exhibit  signs of nutrient  defi-
ciency, i.e. slowing of growth  and  yellowing of the bot-
tom-most leaves.  Schwedinger believes these symptoms  of
nutrient deficiency  are related  to the amount  of  water
uptake.  Damage  is  probably due  to  derangement of  the
relationship between the roots and the water in the soil.
     In Coastal Arctic  tundra studies  by Linkins et al.,
(1976) , oil was  found  to cause significant  decreases  in
root  respiration  and changes in  oxidative  metabolism  of
roots.   These  changes occurred  regardless of  whether
root-oil contact was early or late after oil application.
Oil was found to  cause  greater  perturbation of root res-
piration at lower temperatures.
     Baker  (1970)  discovered  that the  leaves  of  young
beans  and  peas,  which were  grown  in  oil-treated  sand,
showed a higher oil  content than  plants which were grown

                          23

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in normal soil.  Oil absorbed by plant roots can move up-
wards in the plant.  The mode  of  action,  however,  is un-
determined.
     Baker  notes  that most  workers believe  oil  travels
primarily in  the  intercellular spaces with  little move-
ment through the vascular system.   Generally, the smaller
the  hydrocarbon  molecule the  more toxic  the oil  is  to
plants.  Light  oils have been shown to  inhibit  germin-
ation more than heavy oils at high concentrations because
they penetrate the seed coat (Baker 1970).
     Moisture is important for seed germination and plant
growth.  Hunt et al. (1975)  noted that in areas where re-
fined  fuel  oil was  spilled  on permafrost  terrain there
was  extensive vegetative  kill.   Herbaceous plants  are
usually first to  revegetate  such  spill  sites where rain-
fall has leached fuel from the upper soil layers.
     Data in this review of the literature on oil and the
plant-soil  system indicates  that  it  may be  possible  to
identify  and  develop  plants   which  are  oil  tolerant.
These plants would most  likely be hardy  species,  able to
survive the  adverse  environment brought about  by  an oil
spill.  Research and  experimentation to  develop  plants
which  could  be used  to  revegetate land  treatment sites
will require much trial  and  error.   Soil characteristics
of  a land  treatment  site and composition of  the waste
residues applied  to  the soil  will  influence the success
of any revegetation operation.
                           24

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                        SECTION 5
                     SITE SELECTION

     At the  start  of this project, the  intention  was to
select four  sites across  the  country  which  had been used
for  the  land treatment  of  oily residues  from petroleum
refining.  The  idea  was  to select sites  in varying cli-
mates, so  that closed  sites  under differing  conditions
could be evaluated.   However, sites  outside  of Oklahoma
could not be obtained.
     In selecting  sites   for  use  in  this  study,  several
factors  in  addition  to  climate were  considered.   These
factors were
      (1)   The availability of data on what  had been ap-
          plied to the site.
      (2)   The  time  period for  which  the  site had been
          used.
      (3)   The time period for which the site had been in-
          active.
      (4)   The management practices at the site.
     Several refineries  in Oklahoma  which  operated land
treatment sites were visited, and based  on these  visits
and  discussions with plant personnel, three  sites which
best met the criterion were selected  for use in the pro-
ject.  In addition,  these  sites reflected  a range  of oil
loading,  from low (<6%)  to high (=14%).  These values are
based on the oil content of  site  soil  at the  start of
this project.  The sites spanned the range of oil loading
rates which  are encountered  at  operational  facilities.

                           25

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In all three cases, a section of what had previously been
active land treatment sites was selected for use.
     In evaluating  the  sites  one  significant problem was
encountered.   Although  land  treatment  of  oily  residues
has been  used  for many years  at  oil refineries, records
of operational procedures have only been  maintained  at
most refineries  since the late 1970's.   As a  result  of
this,  limited  recorded application  and management  data
was  available  for  the  sites evaluated.   Conversations
with  personnel   responsible   for management   of  these
facilities revealed that  the  sites were  all tilled regu-
larly during operation,  and  nutrients were  added  to en-
hance degradation.  The pH of the site  soil at all three
sites was  in the range  6-8 (Table 7.12).   A synopsis  of
the data available for the three sites selected is pre-
sented below.
Site 1
     This  site had been  used  for  land treatment since
July 1976.   It was used  in  1976, 1977 and  1979,  but  no
analytical work was performed.  The  plot was not used in
1978.   Starting  in February  1980,  records  were  kept  of
the type and quantity of waste being applied to the site.
A tank  farm was  originally located  at this site,  but no
data is  available on spills  etc.,  which  might  have oc-
curred during  the time the tank farm was located here.
     The  last  application of  residues to  the  section of
the site  investigated was on  January 5,  1981.   Available
data shows  that  in 1980, approximately  170 cubic meters
(1091 barrels) of oil were applied, with  an oil content
ranging from 3.3  to 79.2  percent.   In 1981, 7 cubic me-
ters  (42  barrels) were applied  with an  approximate oil
con-tent of  2%.   No  vegetation was present  on the site at
the  start of  the project.   However,  a small  amount  of
growth  was  observed   on   the untilled  portion  of  the
                          26

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research  plot during  the monitoring  activities  at  the
site.  The research was carried out on an area of approx-
imately 0.3 hectares (.75 acres).
Site 2
     This  site  has been  used as  a land  treatment  site
since March 1974.  It was used until  the middle of 1976,
with oil sludge and biosludge being applied in amounts of
157  to  236 cubic  meters  (400 to  600  barrels)  of  oil/
hectare  (2.47 acres).   Precise  analytical  <3ata  is  not
available,  but   laboratory  records  indicate  a  38%  oil
content  for  the  oily sludge, and  a 12%  oil  content  for
the biosludge.  This site supported a luxuriant growth of
vegetation  over  the  entire  area  when  the  project  was
started, and  continued  to support  vegetation during  the
project.   Burrowing  animals  were   also  observed  on  the
site during the  project.   This  site was  tilled and  fer-
tilized  on  a  regular basis  during its  active  life,  and
was a well managed site according to current regulations.
The research was carried out on an area approximately 0.2
hectares (0.5 acres)  in size.
Site 3
     Site  3  has  been  in  operation  as  a  land treatment
site since  1975.   Prior to this,  the oily residues  were
dumped in large pits which had a total capacity of 72,620
cubic meters  (456,814 barrels).  These  pits were emptied
in 1975, and their contents applied to the land treatment
site.   The area  of  the  site  is  2.85  hectares  (7.04
acres),  and personnel  at  the refinery  estimated  a water
content of 60% for the  contents  of the  pits.  This means
that approximately  10,196 cubic meters  (25,955 barrels)
of oily  residue  per  hectare were  applied  to  the  site at
the start of  the land treatment  operation in 1975.  Rec-
ords available for the period 11/25/80 to 1/9/81 indicate
                           27

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a total of approximately 970 cubic meters (6,100 barrels)
of oily residues were applied to.the site over a six week
period.  The research was carried out on an area of ap-
proximately 0.12 hectares (0.3 acres).
     No information was available, from any of the refin-
eries, on the  exact  source  and/or nature of  most of the
residues which  had been applied  to the sites.    In the
few cases where the  source  of the  applied  residues was
recorded, the location on the site where, the residues had
been placed was not noted.
     At  site  2  the  residues  were  applied  to  alternate
strips of land  61 meters long  by 4 meters wide  (200*  x
13'), while at site 1 and 2  the residues were applied to
the whole site.
SITE SOIL CHARACTERISTICS
     The soil at the sites was characterized with respect
to the .following parameters:
      (a) texture
      (b) permeability
      (c) X-ray diffraction
      (d) cation exchange capacity.
     Composite samples were  collected  from  each site, as
well  as  from areas adjacent  to the sites.   The samples
from  adjacent  areas  were analyzed  to  provide background
data by which to evaluate any changes which had taken
place.
Gradation Analysis
     Grain  size  distributions for  the  soils  were de-
termined in accordance  with ASTM Designation 0422-63(72)
(AASHTO  Designation  T-88-78).  The  deflocculating  agent
used  was calgon  solution.    Further dispersion  of clay
particles was accomplished by applying a 10 psi air  pres-

                          28

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sure from  the  Iowa dispersion jet  for  5  minutes.   Grain
size distribution tests were  run  on the fraction of soil
passing sieve  #10  (2mm).   For soils with  oil contamina-
tion it was not possible  to  run  the hydrometer testr be-
cause it was not possible to read the hydrometer correct-
ly while oil was covering it.   Interference  from the oil
occurred even after the samples had been subjected to ex-
traction with freon and dichloromethane for 24 hours.
     Analyses were  performed on  soil  samples taken from
areas adjacent  to  the sites,  and these resulted  in the
following classifications.

      TABLE 5.1.  SITE SOIL TEXTURAL CLASSIFICATION

            Site                  Classification

           Site 1          Silty  loam
           Site 2          Sandy  loam
           Site 3          Clay


Permeability
     Permeability  tests   were conducted   on  samples  of
background soil, as well  as  composite  samples of the top
25 cm  of  site  soil  at each  of   the three  sites.    Soil
samples from the sites were  collected  and standard labo-
ratory permeability tests were run, using a modification
of the  constant head permeability  test (AASHTO Designa-
tion: T 215-70, ASTM  Designation: D 2434-68   (1974)). The
constant head method  is  preferred  over the  falling head
method  for  such fine-grained soils because  of  the rela-
tively low permeability coefficients obtained.
     The procedure  was  modified  somewhat  from  the stan-
dard method in  that a nitrogen cylinder was  used to cre-

                           29

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ate the pressure head instead of the constant head filter
tank.  In this way  it was  possible to control the amount
of  pressure  used  to make  the water  permeate the  soil
matrix and maintain laminar flow.  Before  testing began
the optimum  moisture content for  each  sample was deter-
mined  from a standard proctor  test  (AASHTO Designation:
T-99) .  Water was  then  added to each  sample  to  bring it
up  to  optimum moisture.   The  soils were  compacted  into
the permeameter  mould,  and  tap  water was  added  on  top.
The soils were left to saturate for 48 hours.  At the end
of  the 48 hours  the pressure was  turned  on.   The volume
of water collected  per  time  was recorded  and the coeffi-
cient  of  permeability  was  calculated.   The  samples  on
which these permeabilities were determined were composite
samples taken  from the top  25  cm of  soil.   The  results
are shown in Table 5.2.
     No significant  differences  between the permeability
of  the background  and, site  soil was  observed at  sites 1
and 3.

          TABLE 5.2.  SOIL PERMEABILITY VALUES
Site/Location
Site 1
Site 1
Site 2
Site 2
Site 3
Site 3
- Background
- Site Soil
- Background
- Site Soil
- Background
- Site Soil
Permeability (water)
(cm/ sec)
9.6 x 10"p
5.03 x 10"8
1.3 x 10~1?
1.95 x 10~'
0.91 x 10
X-Ray Diffraction
     Composite  samples  of site soil  and  background soil
were subjected  to  x-ray diffraction analyses.  These an-
alyses  were  performed  using  a Phillips  Electronics APD
3600 Automated Power diffractometer.  A comparison of the
                          30

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site  soil  patterns  with those  of background,  revealed
that some changes had taken place in the site soil struc-
ture.
Site 2
     Soil samples from the site and one background sample
were analyzed.  The crystallinity of the soil samples did
not  change  significantly in  the  site samples  when  com-
pared  to  background.  The decrease  in intensity  of the
montmorillonite and chlorite peaks was more pronounced as
the  oil  content increased.   A possible  explanation for
this is that  oil penetration  into the interplanar layers
of the minerals masked the effect of the crystalline
materials.  The calcite peak increased in intensity.
Site 1
     The same trend as was observed at site 2 is observed
here.  Again the calcite peak increased in intensity.
Site 3
     The general trend of decreased peak intensities with
increased oil content is again evident here, with the ex-
ception once  again  of the calcite peak,  which increased
in intensity  in one  sample and  decreased  in intensity in
the other.
     Generally, the major peaks  either remained the same
or diminished  in  intensity with  increasing  oil content.
The  exception  to this trend was  the  calcite  peak, which
generally increased in intensity with increasing, oil con-
tent.  The X-ray diffraction spectra are shown in
Appendix D.
Cation Exchange Capacity
     The cation  exchange capacity of the site  soil and
background was  determined using  the  ammonium saturation
method.  The CEC of the top 25 cm - zone of incorporation
- was determined.   The results reveal that at sites  1 and
                          31

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2, there was  generally  an increase in CEC  where  oil was
applied to the soil.  However, at site 3, the CEC of site
soil was slightly lower than that of the background soil.
The CEC values of the site soil are listed in Table 5.3.
                          32

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    TABLE 5.3.  CATION EXCHANGE CAPACITY OF SITE SOIL







Location                           CEC (m.equivs./lOOg)





Site 1



  Area 1                                15.4




  Area 3                                16.4



  Area 6                                19.5



  Background                            15.0






Site 2



  Area 6 - Untilled                     14.6



  Area 6 - Tilled                       14.5



  Area 3           •                      7.0



  Background                             7.1






Site 3



  Area 2                                12.1



  Area 3                                14.1



  Area 4                                13.6



  Background                            14.9
                          33

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                        SECTION 6
                  EXPERIMENTAL APPROACH

     Land  treatment  sites which  had been  in use  for  a
number of  years were  selected.   Soil samples from depths
0-25  cm and  25-51  cm were  analyzed  for   oil  content,
metals,  TOC,  COD, pH,  nutrients,  chlorides,  cation  ex-
change  capacity,  and  selected  organic compounds.   The
unsaturated zones at  the  sites 51-152  cm were also sam-
pled,  and  analyzed  for oil content,  metals  and selected
organic  compounds.   The  soil  pore water in  the unsatur-
ated  zone  at a depth  of 4 feet was also  sampled using
soil  pore  water  samplers, and  the  samples  analyzed  for
oil content, metals,  TOC, COD  and selected organics.
     The 0-25 cm and 25-51 cm depths were chosen, because
land treatment sites are tilled, and the till zone usual-
ly extends  to  a depth of about 25 cm.   Since this depth
is  completely mixed  during   tilling,   it was  felt  that
sampling  shallower   depths  would  be unproductive.   The
depth  25-51  cm was  chosen since  preliminary sampling at
these  sites  indicated  the presence of  oil  in some areas
up to this depth.
     Samples  from the  deeper  unsaturated zone were ana-
lyzed to see if any migration of pollutants had occurred.
     Samples of soil pore water  were collected as a part
of  the  unsaturated  zone  monitoring  program,  to  see
whe.ther  any pollutants were passing  through the unsatur-
ated zone, and if so in what quantities.
     Samples  of  the  0-25 cm  and  25-51 cm  zones  were

                          34

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analyzed for  oil  content over  the  duration of  the  pro-
ject, in  an attempt  to  determine rates  of  degradation.
In addition  a part of  each site was  tilled,  to  see  if
this enhanced  the rate  of  degradation when compared  to
the untilled section of the site.
     The major  thrust in the  analysis of the  site  soil
and  soil pore  water  for organics, was  to identify qual-
itatively the compounds present.  Quantitative  evaluation
was beyond the scope of this project, although  concentra-
tions of  the  compounds identified  were  calculated,  to
give an idea of the order of magnitude of the  concentra-
tions of these compounds.
     The other  parameters  measured  are  all  important  as
indicators of  the amount of oil  present,  and  the poten-
tial for mobilization of pollutants,  especially metals.
     The main objective  of  the  revegetation  study was  to
identify trees or grasses which would grow in oily soil
and possibly aid in the recovery of  land treatment sites.
SAMPLING PROCEDURES
     Each site was divided  into six  sections,  after ini-
tial sampling and oil content analysis at sites 1 and  2.
These initial  samples were  collected randomly.  However/
an examination  of the  results  of this  initial  round  of
sampling revealed that there was considerable variability
in oil  content across  the  site.  Thus, to obtain  more
representative  samples,  it  was decided  to subdivide the
                                            •
sites,   and  then  sample  randomly within  each  area,  com-
positing the  samples.   Five  cores  were  composited  from
each section, giving a total of 30 samples {6 composites)
per  site.  This number  of  samples was  enough to yield an
error in the  estimate of the means  of  a  maximum of 1%,
and  usually  less than  0.5% for  the oil  content  of the
site soil.
     A visual inspection of the cores  taken, coupled with
                          35

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the  results  of the  initial oil  content  determinations,
led  to  the  decision to sample  the  top 25 cm  and  the 25
centimeters directly below it, to ascertain the extent to
which the oil  had migrated.  The samples  were collected
using soil sampling tubes.  Initially Hankinson soil sam-
pling tubes were  used, but these proved  too  fragile for
the  types  of  soil  being  sampled, and  stronger  samplers
were  fabricated  in the School  of Civil  Engineering and
Environmental Science.   The soil samples  were  all  col-
lected using these  samplers,  unless  otherwise indicated.
This sampling procedure was used for samples from the
0-25 cm and 25-50 cm depths.
Deep Core Sampling
     The deep  core samples were  obtained by  drilling  a
hole  below  the  zone  of  incorporation  using an  auger,
cleaning out the hole, and then using a soil core sampler
to collect samples  from the desired  depth.   In this way,
samples up to a depth of 152 centimeters (60 inches)  were
collected at each site.  Deep core samples were collected
at each site each of the two years of the project.   These
deep core samples were not composited.
Soil Pore Water Sampling
     The soil water passing through  the unsaturated zone
beneath  the  zone  of  incorporation was  also  sampled.
Sampling of the  soil  pore water was  accomplished  by in-
stalling soil moisture samplers  (lysime'ters)  at a depth
of approximately  1.2  meters (4 feet) at  the  sites.   The
sampler  used  was  Model   1920,   sold   by  Soil  Moisture
Incorporated  of   California.   Before  the  samplers  were
installed,  an  evaluation  was  made  of  the methods  sug-
gested  by  the vendor  for installation of  the samplers,
and  the following method of installation was adopted as a
result of this evaluation.
     A  10  cm (4  inch)  hole was drilled  to the required
                           36

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depth, and thoroughly  cleaned  out,  making sure that none
of the oil contaminated  soil  from the zone of incorpora-
tion was in the hole.  The bottom of the hole was tamped,
and  then  the sampler  was  seated in  very  fine-300  mesh-
silica sand,  so  that the ceramic cup  of  the sampler was
completely covered.   Parent  soil  (15  cm)  was  then put
into  the  hole,   and  tightly  tamped.   A  layer of  dry
bentonite  clay  was  then  put  into  the hole  followed  by
more  parent   soil.   The  hole  was  filled  to  about  20
centimeters  (8  inches)  from the  top with  parent  soil,
which  was added  in  small  amounts  and  tightly tamped.
Another layer' of  dry bentonite clay was  then added (5-8
cm)  and the  hole  filled  with soil.   Figure 6.1 is a dia-
gram of the mode of installation.
     The sampling locations  for  soil  pore water and deep
core  samples  were installed  at  randomly  selected  loca-
tions  in  3 or 4  areas at  each site.  The  areas at each
site  were  chosen to span  the range  at  each  site were
chosen to  span  the  range at oil  concentrations measured
at the site.
     The samples  collected were  all identified by a code
which  identified the  site  from  which  the   sample  was
taken, the date of collection and the type of sample. The
sample could  also be identified as being from a tilled or
untilled area, in the case of site 2.
     The site code consisted of a seven digit number with
1 or 2 letters after it,  e.g. 1111282S or 1111281SW.  The
first digit  identified the  site, the next  six the  date,
and the last  two letters  identified the sample type.  The
code  1111281S would  refer to  a  soil sample  from site 1
collected  11/12/81.    The  areas within   the site  were
identified using the numbers 1 to  6,  and  the letter T or
B  to represent  the  depth 0-25  cm  and 25-51  cm respec-
tively.  An  additional T or U was  used  to differentiate
                          37

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                  Access  tubes
                           Bentonite  clay
                         Ground  surface
                           Soil moisture  sampler
                          Silica  sand   300 Mesh
             10 cm.
Figure "6.1.  Method of installation  of  soil
             pore water samples.
                   30
                   o

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tilled   areas   from   untilled   areas   at   site   2.
Thus:
   IT  - Top  (0-25 cm) sample from area 1
   3TT - Top sample from the tilled section of area 3
   2TU - Top sample from the untilled section of area 2
   S   - Soil sample
   SW  - Soil water sample.
     The soil  samples which were  taken for  purposes of
comparison with  the  soil pore water  samples,  were taken
at a distance of 6 feet from the soil moisture sampler.
                          39

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                        SECTION 7
           EVALUATION OF SITE CHARACTERISTICS

ORGANICS
     The site soil was tested for the presence of select-
ed priority pollutants.  The samples were first extracted
with methylene chloride using the Soxhlet extraction pro-
cedure, and then that extract was subjected to separatory
funnel liquid -  liquid  extraction.   These procedures are
Methods  3540  and  3510  in  "Test  Methods  for  Evaluating
Solid Waste" (2nd edition).
     Three different sets of  samples from each site were
analyzed during  the  project,  to  identify any persistent
organics present as definitely  as  possible.   Table 7.1
lists the organic  compounds evaluated,  and Table 7.2 the
compounds  identified  as present  at  the  sites.   This
identification   is   essentially   qualitative,   since  no
studies  on  the  recovery  of  organics from  soil matrices
were  carried  out  during  this project.   However,  Tables
C-l  to  C-4  in Appendix  C contain  the  concentrations of
the  compounds identified  at the  sites.   These values are
   •
intended as  a guide to  the  order  of  magnitude  of the
concentrations of the compounds identified at the sites.
     At site 1,  many of  the  19 compounds identified were
at very low concentrations in  the <.001 ppm range.  How-
ever, some compounds (polynuclear aromatics) turned up at
quite  high  concentrations.   These  compounds  were  also
the ones present in the highest concentrations at site 3.
Phenol showed a  definite trend at  site  1,  increasing in

                          40

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             TABLE 7.1  PRIORITY POLLUTANTS
                      Base/Neutrals
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachloroethane
1,2-Dichlorobenzene
Hexachlorobutadiene
Naphthalene
Bis(2-chloroethyl) ether
Nitrobenzene
Bis (2-chloroethoxy) methane
Hexachlorocyclopentadiene
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Isophorone
Fluorene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
2,4-Dinitrotoluene
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene
Anthracene
DimethyIphthalate
DiethyIphthalate
Fluoranthene

  Phenolics

2-Chlorophenol
Phenol
2,4-Dichlorophenol
2-Nitrophenol
p-chloro-m-cresol
2,4,6-Trichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
4-Nitrophenol
Pentachlorophenol
 Pyrene
 Di-N-butylphthalate
 ButylbenzyIphthalate
 Benzidene
 Chrysene
 Bis(2-ethylhexyl)phthalate
 Benzo(a)anthracene
 Benzo(b)anthracene
 Benzo(a)pyrene
 Dibenzo(a,h)anthracene
 Indeno(1,2,3-c,d)pyrene
 Benzo(g,h,i)perylene
*Lindane
*Methoxychlor
*Endrin
*2,4-D
*2,4,5-TP Silvex
 Benzo(k)fluoranthene
        Volatiles

   1,4-Dichlorobutane
   2-Bromo-l-chloropropane
   1,1-Dichloroethane
   Trans-1,2-dichloroethene
   Chloroform
   1,2-Dichloroethane
   1,1,1-Trichloroethane
   Carbon tetrachloride
   Bromodichloromethane
   1,2-Dichloropropane
   Trichloroethene
   Dibromochloromethane
   1,1,2-Trichloroethane
   Benzene
   Bromoform
   1,1,2,2-Tetrachloroethene
   1,1,2,2-Tetrachloroethane
   Toluene
   Chlorobenzene
   Ethylbenzene
                           41

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TABLE 7.2
ORGANIC COMPOUNDS IDENTIFIED  IN
SOIL AT LAND TREATMENT SITES

Anthracene
Phenanthrene
Fluoranthene
Pyrene
Naphthalene
Chrysene
Benzo (b) f luoranthene
Benzo (a) anthracene
Benzo(a)pyrene
Dibenzo ( a, h) anthracene
Benzo (g ,h , i) perylene
Isophorone
Bis(2-ethylhexyl)phthalate
Buty Ibenzy Iphthalate
1,2-diphenylhydrazine
Phenol
Pentachlorophenol
4-Nitrophenol
2-Nitrophenol
2 ,6-dinitrotoluene
Benzene
Toluene
Ethylbenzene
Bromoform
Site 1
X
X
X
X
X
X
X
X
X
X
X
X
X
X

X
X



X
X
X

Site 2 Site 3
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
    Denotes compound which was present.
                       42

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concentration  over  the   sampling   period   11/10/81   to
12/1/82.  Thirteen  of  the 19 compounds  were polynuclear
aromatics (PNA's).
     At site 2, 13 compounds were identified at the site,
6 were PNA's and 4 were phenolics.  The compounds present
at   highest   concentrations  were   again   polynuclear
aromatics.  Trace  amounts of phthalates were  found,  but
no volatiles.
     Thirteen  compounds  were identified at  site  3,  with
6  of   them   being   PNA's.    Four  volatiles  were  also
identified at  this  site.
     Only pyrene, isophorone, bis(2-ethylhexyl)phthalate,
phenol  and  benzene were  identified at  all  three sites.
Volatile  compounds  were  identified  mainly  at sites 1 and
3, which  had residues applied more recently  than  site 2.
     Table  C-l in Appendix  C lists  compounds  which were
found in  the background  samples taken at the three sites.
The  concentrations  of  the compounds identified was quite
low, but  so were most of  the concentrations  at the sites.
The  reason for  the presence of  these  compounds in the
background  samples  is  not clear.  All  of  the  sites were
located at refineries,  and the  background  samples were
taken  near the  land treatment area itself.  It may  be
that the background samples were taken too near to the
treatment area,  and the  soil was slightly  contaminated,
or these  compounds  may be present naturally.   Phthalates,
 for  example,  seem  to  be  present   everywhere,  and bis-
 (2-ethylhexyl)phthalate   was present  in  the  background
 samples from all sites.   Other  compounds  present in the
background  samples  from  all  sites were  chrysene  and
benzo(a)anthracene.
OIL-  CONTENT
      Determinations were made of the  oil  content of  the
 soil at each  of  the 3  sites during  the  course  of the  pro-
                           43

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ject.  The objective of these tests was to determine:
     (1)   The variability in the oil concentration across
          the site.
     (2)   Whether oil was still present at the site.
     (3)   The extent  to  which the oil was  degraded over
          the research period.
     (4)   The extent  to  which the oil had  migrated ver-
          tically.
     A part of each site was tilled during the project to
see if tilling had any effect on the rate of degradation
when compared to the untilled area.
Variability of Oil Concentration
     As  described in  the  section  on  sampling,  the re-
search area  at  each site was divided  in  6  sections, and
composite samples taken from each section.  These compos-
ites  were  made  up  of  5  individual  cores  which  were
thoroughly  mixed before analysis.   It is  apparent from
the oil  concentrations present  in the  different sections
at each  site,  that there was great  variation in the oil
content  across  the site.  However,  there was even great
variation within each section  at the sites.   Table 7.4
shows  some  oil  content  values obtained  from individual
cores taken at site 3.  The cores were from three differ-
ent  areas at site  3.   Table  7.5 shows the  results ob-
tained when  individual cores  were analyzed  from one area
and  compared to  a  composite  sample taken  from the same
area at  site 2.  It can be seen  that  at site 2, the oil
concentration of  the  composite  of 5 cores was very  close
to the mean of the concentrations of 5 individual cores
taken from the  same location.
Oil Content of Site Soil
     The  soil at each site was sampled periodically over
the project period, and  the samples  analyzed  for oil con-
                           44

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  TABLE 7.4  VARIABILITY OF OIL CONCENTRATION AT SITE 3
Area 1          Sample #                      % Oil
1
2
3
4
5
6
7
8
9
10
5.0
8.7
3.6
4.1
2.9
7.7
3.6
3.8
2.3
5.3
(continued)
                   Mean concentration = 4.7
                   Standard deviation = 2.07
                   Variance           =4.28
Area 2          Sample #                      % Oil
1
2
3
4
5
4.1
5.0
4.5
6.2
8.8
                   Mean concentration = 5.7
                   Standard deviation = 1.88
                   Variance           = 3.55
                          45

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                  TABLE 7.4  (continued)
Area 3 Sample #
1
2
3
4
5
6
7
8
% Oil
14.1
8.3
8.3
4.7
12.9
7.2
13.8
5.7
                   Mean concentration =  9.4
                   Standard deviation =  3.71
                   Variance           = 13.74
  Table 7.5 Variability of Oil Concentration at Site 2
Area 6 Top Sample #
1
2
3
4
5
Composite
% Oil
1.5
4.2
6.3
4.5
6.5
4.7
                   Mean concentration = 4.6
                   Standard deviation = 2.02
                   Variance           = 4.07
Area 6 Bottom   Sample f                      % Oil
1
2
3
4
0.9
3.8
0.3
0.4
                   Composite                   1.7
                   Mean concentration = 1.4
                   Standard deviation = 1.65
                   Variance           = 2.74

                          46

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tent.  A part  of  each site was tilled, so  that  the rate
of degradation in the  tilled  vs. the  untilled  sections
could  be  evaluated.  At  site  1,  half of  the  site  was
tilled, and the other half left untilled.   At site 2,  the
land treatment site had had the residue applied to alter-
nate strips  of land.  At  this  site,  half  of  each strip
was tilled, and the other half left untilled.  At site 3,
where the revegetation study was carried out, only a
small portion of the site was tilled - Area 6.
Results
     Table B-4 show  the oil  content  concentration in  the
0-25 cm (T) and 25-51 cm  (B)  layers  of soil at the three
sites.   At site 1, areas 4, 5 and 6 were tilled.   At site
3 only area 6 was tilled,  while half of each area at site
2 was tilled.
Site 1
     At site  1,  there was a  significant  difference (95%
level)between the site oil content and the background for
both the  top  (0-25  cm)  and bottom  (25-51 cm)  levels.
However, there was  no significant difference  in the  oil
concentration  of  the top  and bottom  layer on  April  4,
1982 and December 1,  1982, which  means that little or no
degradation  had  taken  place  over this  period  of time.
The paired t-test at  a  95%  confidence level was  used  for
the latter comparison.  The mean oil content values are
given in Table 7.6.
Site 2
     At site 2, as mentioned  before,  the  strips  with  the
oil applied  had  one  half  of each  strip  tilled  4 times
during the research project.   The oil content of the site
soil did not  change significantly over time.   These  was
no  significant change  between March  1982  and  February
1983 in the  concentration  of oil in  the  top tilled sec-
                          47

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 TABLE 7.6  OIL CONTENT DATA -  MEANS
            SITE 1
Date Mean
*Background Top 0.56
*Background Bottom 0.13
4/8/82
Top 4.90
Bottom 0.64
12/1/82
Top 5.62
Bottom 1.85
* Mean of all background
TABLE 7.7 OIL CONTENT
SITE 2
Date Mean
*Background Top 0.43
*Background Bottom 0.40
4/6/82
Top, tilled 2.63
Bottom, tilled 0.78
Top, untilled 2.95
Bottom, untilled
7/8/82
Top, tilled 2.58
Bottom, tilled 1.08
Top, un-tilled 2.60
Bottom, untilled 1.17
11/19/82
Top, tilled 2.93
Bottom, tilled 1.46
Top, untilled 2.65
Bottom, untilled 1.08
2/L6/83
Top, tilled 2.97
Std. dev.
0.30
0.06
1.52
0.35
2.33
1.40
concentrations
DATA - MEANS
Std. dev.
.152
0.10
0.96
0.37
0.52
0.95
.33
1.72
0.58
1.46
1.31
1.67
1.14
1.70
Variance
0.090
0.003
2.30
0.12
5.45
1.96


Variance
.023
0.01
0.92
.14
0.28
0.902
0.11
2.97
0.34
2.14
1.72
2.79
1.29
2.89
Mean of all background concentrations

                48

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tion of the site.  These was no significant change in oil
concentrations in  either  the tilled or untilled,  top or
bottom areas  over the  period  January to  November 1982.
There was also no  significant  difference  between the oil
content of  the  tilled  and  untilled sections of  a given
strip at the end of a 12 month period.
     The site oil concentrations top (0-25 cm)  and bottom
(25-51 cm)  were all significantly higher - 95% confidence
level  -  than background,  except  for  the bottom tilled
sample of 4/6/82.  The  mean  concentrations of  oil at the
site  are  given  in  Table  7.7.   It should be  noted  that
average oil content of  the  top  samples  at this site were
quite low,  ranging  from 2.58%  to 2.95%.   The oil content
of the background  top sample of 8/5/82 was  not included
in the calculation at the mean background  site concentra-
tion, but was  treated as  an outlier.  This  was done be-
cause the sample was  apparently taken from an area which
was contaminated with oil after we started working at the
site.
Site 3
     The same  trend  as at the  other  two  sites was noted
here.  There  was  no  significant  change   in  average oil
content  of  the  site  between March 1982   and  June 1983.
However, there was a significant  difference between the
oil  concentration of  the site  soil and  the  background
concentrations.  A  95%  confidence  level was  used for the
statistical analysis of the data.  The mean  site  oil
concentration values are given  in  Table 7.8.
Discussion  of Results
     There  was  not  significant degradation of  the oil
present at  the sites  during the research  period.  A  num-
ber  of  factors  could  account  for  this lack of  degrada-
tion.  These include:
                           49

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      TABLE 7.8  OIL CONTENT DATA - MEANS
                 SITE 3
Date
Mean
%
*Background Top
*Background Bottom
3/26/82

6/7/83


Top
Bottom

Top
Bottom
0
0

8
2

9
5
.57
.10

.7
.7

.03
.13
Std.
0.
0.

2.
4.

4.
4.
dev.
50
0

90
57

85
62
Variance
0.
0.

8.
20.

23.
21.
25
00

42
85

56
42
     Mean of all background concentrations.
TABLE 7.9  COMPOSITION OF OIL AT SITES 2 AND 3
    Asphaltenes  Saturates   Polar Compds  Aromatics
Site 2
6T
6B
Site 3
5T
4B
18.0
8.4
12.4
8.2
28.0
27.4
32.4
35.8
32.0
30.5
37.6
34.9
22.0
33.7
17.6
21.1
                     50

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     (1)   The oil  at the  site  contained  appreciable  a-
          mounts of polynuclear  compounds, which are dif-
          ficult  to  metabolize.   Table   7.9  lists  the
          fractions  found  in the  residues from  sites  2
          and 3.
     (2)   There were  long  periods during  which  the site
          soil was quite wet, which  could have inhibited
          the microorganisms by  creating anaerobic condi-
          tions in the soil.
     (3)   The levels of nitrogen in the soil were too low
          and inhibited microbial  metabolism  of  the oil.
          No nutrients were added to the sites during the
          research  period,  except  for the  revegetation
          study at site 3 and low levels of nitrogen were
          found in  the  soil at  sites  1 and  3.  However,
          it  must  be  noted that  at site  2,  vegetation
          grew profusely, indicating that nutrient levels
          were high enough for degradation to take place,
          if  readily  degradeable material  were  present.
          Table  7.10   shows  levels  of   nitrogen  and
          phosphorus found at the sites.

     Oil was  present below what  is  commonly  referred to
as the till  zone  (0-25 cm) at all three  sites.   Oil was
found as deep as 45-50 cms at all 3 sites.  This suggests
strongly that  vertical migration  of oil   below  the till
zone occurs;  occasional deep tilling  or   discing  of the
soil may be necessary to bring this oil up to the aerobic
upper soil layers where it can be degraded.
     The raw oil content data is given in Appendix B.
METALS
     The concentration  of  selected heavy  metals in site
soil was  determined,  and   compared  to background metal
concentration.  A  95% confidence  level  was  used  in all
                          51

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TABLE 7.10  NITROGEN AND PHOSPHORUS IN SOIL -AT SITE*
Location
Site 1
Area 1
Area 2
Area 5
Area 6
Background
Site 2
Area 1
Area 3
Area 4
Area 5
Area 6
Background
Site 3
Area 3
Area 4
Area 5
Area 5
Area 6
Background
ppm N in Soil ppm P in Soil

1.37 140
1.90 182
1.44 193
1.47 245
0.06 875

4.6 171.5
3.8 367.5
5.4 490.0
7.0 _ 280.0
12.7 350.0
12.9 52.5
-
<0.1 <0.1
<0.1 <0.1
<0.1 <0.1
<0.1 <0.1
<0.1 <0.1
<0.1 0.8
        Top 25 cm of soil
                         52

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statistical tests  unless otherwise  stated.   Three  dif-
ferent sets of samples were  taken  over  a  12  month period
and were  analyzed  at  sites  1  and  2,  and  two  sets  of
samples at site 3.  The  site was  sampled  as  described in
the section on oil content.
     At site I, Cu, Pb,  Ag  and  Zn  were  present  at levels
significantly above background  of the  top  25 cm.  in at
least 2 sets of samples.   Cr and Ni showed up as signifi-
cant  in  one  set of  samples.  The data is  presented in
Appendix B.  Table 7.11 lists the metals found at signif-
icant  levels  above background  at all  three sites.   No
samples from the  25-51 cm zone showed  significantly in-
creased metals concentrations at a 95% confidence level.
     At  site  2,  samples collected  in  1981   showed  some
metals at  levels significantly  above  background,  but the
sample collected  in 1982 showed no  significant increase
in metal concentration of either the  top or bottom zones.
Co, Ni and Al showed up at elevated concentrations in all
3 sets of top samples while Cu,  Co and Al show up at ele-
vated concentrations in two sets of bottom samples.
     At site  3  only chromium shows  up  at concentrations
above background in both sets of top samples.
     The raw metals data is listed in Appendix B.
     Even  though several metals  were found at concentra-
tions significantly above background in both top and bot-
tom samples, the concentration in the soil was not neces-
sarily very  high.   At site  1,  the  concentration of Cd,
Ni, Ag, Co were all less than 30 mg/kg, with Cd generally
at a concentration of 1 mg/kg N less.
     At site 2, all metals were present at low concentra-
tions, with the exception of Al.   High Al concentrations
are to be  expected,  since the soil contains  clay.  Thus,
even  though  there are  several  elements  present  at  con-
centrations above  background, this  is  not  very  signifi-

                          53

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 TABLE 7.11  METALS FOUND AT CONCENTRATIONS SIGNIFICANTLY
             ABOVE BACKGROUND

Site 1
Date

7/28/81



11/10/81




6/14/82

a
Top
Cu
Pb
Zn
Ag
Cu
Pb
Zn
Cr
Ag
Ni
Pb
= .05 a
Bottom Top
Co








Cu

= .1
Bottom
Al



Cr






Site 2
Date
7/21/81




11/28/81







6/16/82


a
Top
Co
Ni
Al


Cu
Co
Ni
Pb
As
Al
Cr
Ag
Co
Al
Ni
= .05 a
Bottom Top
Cu Pb
Co Zn
Al Cr
Cr
Ag
Cu
Co
Pb
Zn
Al
Ni





= .1
Bottom
Zn
Ag



As
Al
Cr








 (continued)
                          54

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                 TABLE 7.11   (continued)

Site 3

       Datea=.05a=.1
                     Top        Bottom    Top     Bottom
11/17/81             Cr          Pb       As        Cu
                                 Zn       Cu        Ni
                                 Al       Pb        Cr
                                          Zn        Ag

6/29/82              Zn          Zn
                     Cr          Ni
                          55

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 cant.
     At  site  3,  where  chromium and  zinc  show  up  at  levels
 significantly above background,  the  actual soil concen-
 trations  are  in the 65  mg/kg range for chromuim and  100
 mg/kg  range  for zinc.  Similarly,  the  concentration  of
 metals Pb,  Zn and  Al in  the  bottom  samples, even though
 higher than background,  are  not very high.
 £H
     The  pH of  the  top  (0-25  cm)  and  the bottom  (25-51
 cm)  of site  soil  were determined  during  the project  to
 see  if the  potential for solubilization  of  metals existed
 at the sites.   The mean  site concentrations are  presented
 in Table  7.12.   The pH values at all the sites  are  above
 the  recommended 6.5 except  for site  2  on  7/21/81,  where
 the  pH was 6.4.   However  later pH  readings at  this  site
 yielded values  of  7.2, which is well above  the value of
 6.5  recommended to minimize  metal solubilization.
•Chloride
     The  chloride  ion  concentrations of  the site soil  was
 significantly higher than background at all  three  sites.
 Only 1 set  of determinations were made,  therefore,  varia-
 tion over  time  could  not   be observed.   However,  the
 chloride  ion  concentration  of  the soil  pore  water  did
 decrease  over time, and the  same trend  could be expected
 for  soil  chloride  ion  concentration.  Table 7.13 shows
 the  mean  chloride  ion  concentrations at  the three sites.
 Total  Organic Carbon
     The  average  Total  Organic  Carbon  (TOO  values  for
 the  sites are given in Table 7.14.   The  TOC values  of the
 top  (0-25 cm) of  soil at  sites  1 and 3  are significantly
 greater  than  background.   The bottom (25-51 cm)  sample at
 site 3 is  also greater  than  background.   At site  2  the
 top  sample  of  11/12/81  is  significantly  greater  than

                           56

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               TABLE 7.12  SITE pH VALUES
                     Mean pH Values
Date          Top     Bottom       Bkg Top    Bkg Bottom
Site 1
11/10/81
12/1/82
Site 2
7/21/81
11/12/81
11/19/82
Site 3
7/16/81
11/17/81
3/26/82
7.4
7.1 7.4
6.4 6.6
7.2
7.2 7.3
7.4 6.7
7.4
7.5
7.4
6.8
7.0
7.2
5.8
7.2
7.5
6.8
7.8
;
         TABLE 7.13  SOIL CHLORIDE CONCENTRATION
             Mean Cl  Concentration (mg/kg)
Date        Top      Bottom        Bkg T        Bkg B
Site 1

6/30/82    119.6     103.3          17.6         15.4

Site 2
7/8/82 28.0
Site 3
11/4/82 72.6
33.1 13.7
101.5* 19.8
2
7
.9
.3
     *    Mean of 2 determinations


                          57

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background  top sample.   Sites with  higher  oil  content
have correspondingly  high TOC values.   These TOC values
were  determined   using  the   Walkley-Black  dichromate
oxidation  method   taken  from  methods  of  Soil  Analysis
edited by Black et al..   The  oil  at site 3 extended well
below  the  zone  of  incorporation,  hence   the high  TOC
values of the bottom  sample  at  site 3.  There  was  not
nearly as much penetration of oil at sites 1 and 2, hence
the relatively low TOC values of the bottom samples from
these sites.
UNSATURATED ZONE MONITORING
     The unsaturated zone at  each  of  the three sites  was
monitored  for evidence  of  the  presence  of  pollutants.
The objective  was  to  determine  whether or  not pollutants
were migrating below  the zone  of incorporation.   This
monitoring was accomplished by  taking core samples below
the zone of incorporation at depths between 51 cm and 152
cm  (20-60 inches),  and  by collecting  samples of the soil
pore water  passing  through   the  unsaturated  zone using
soil moisture  samplers.
     The  soil  core and soil pore  water  samples were  an-
alyzed for:
          (1)   oil content
          (2)   heavy metals
          (3)   organics
In  addition to these  tests,  some  soil pore water  samples
were analyzed  for:
          (1)   chloride
          (2)   pH
          (3)   conductivity
          (4)   COD and/or TOC
                           58

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                  TABLE 7.14  SOIL TOC
                       Mean TOC %
Date        Top      Bottom        Bkg T        Bkg B


Site 1

11/10/81    10.4      1.5*          2.0          1.3

Site 2

7/21/81      3.6      2.6           1.1          0.5
11/12/81     5.2      0.9           0.8          0.3

Site 3

11/17/81    11.2      6.7           1.4          0.3


     *    Mean of 2 values
                          59

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SOIL PORE WATER ANALYTICAL RESULTS
Organic Priority Pollutants
     Samples of soil pore water were analyzed for the B/N
and phenolics as listed  in  Table  7.1.   Samples from site
1  indicated  the presence of  5 organic compounds  in the
soil water.   These  compounds  were phenol,  bis(2-ethyl-
hexyl)  phthalate,  di-n-butylphthalate,  butylbenzylphtha-
late and chrysene.   Bis (2-ethylhexyl)phthalate showed up
at concentrations of 120.8 and 55.64 mg/1 in two samples.
Three  samples  of soil pore water from site  1  were ana-
lyzed.
     At  site  2, a total  of 5 samples were  analyzed for
priority pollutants,  with  only  two samples  showing the
presence  of  any.   The  compounds  found  were  phenol,
chlorophenol and pentachlorophenol, all present at levels
of less  than  1  ppt.   Only  1  sample of  those analyzed at
site 3  showed  any organics present,  and  this was  at  a
concentration of less than 1 ppt.
     Background  soil pore  water  samples  were  analyzed
from sites 2 and 3, and no priority pollutants were found
in these samples.  No background  soil  water samples were
obtained from site 1.  Table  7.15 lists the organic pri-
ority pollutant  identified  at  the sites.   The concentra-
tions of the compounds identified at the sites are given
in Tables B-5 to B-7, Appendix B.
Metals
     Tables 7.16 - 7.18 show the concentrations of metals
found  in the  soil  pore  water.   At site  1,  barium was
present  in  some  samples  at  levels  greater  than  the
drinking water   standards.   Arsenic was  present  in two
samples  from one  sampler  at levels  near  the  drinking
water  standard  of 0.05  mg/1.   Iron  and  manganese were
present  at  quite  high  concentrations.   Iron concentra-
tions  ranged  from 0.20  to  11.99 mg/1, while manganese
                          60

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        TABLE 7.15  PRIORITY POLLUTANTS PRESENT
                    IN SOIL PORE WATER
Compound                  Site 1     Site 2     Site 3


Phenol                       xx          x

4-Nitrophenol                          x

Pentachlorophenol                      x

Chrysene                     x

Bis(2-ethylhexyl)phthalate   x

Di-n-butylphthalate          x
                          61

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                  TABLE  7.16  SOIL PORE WATER (mg/1)  METALS  (Site 1)
Ag Al As Ba Cd Cr Cu
6/14/82
Area 1 .008 .06 .042 5.28 <.001 .060 0.02
Area 3 .011 .71 <.001 .58 <.001 .060 0.01
Area 6 .010 .04 - 1.28 <.001 - 0.04
12/1/82
Ni Pb Zn Fe Mn

.04 <.02 1.44 5.81 1.70
.028 <.02 .35 0.20 .12
.036 <.02 .75 10.31 3.53

Area 1    .011     .53   .089   2.13   <.001    .030  <.002   .035  <.02   2.44    4.62   1.32




Area 4    .011   0.80   .024   1.24   <.001    .060   .010   .035  <.02    .84    3.88   1.37





1/13/83




Area 4    .021   0.09     -    2.15     -      .050  <.002   .08   0.20    .14    0.70   8.0




Area 6    .020   0.04     -    3.50    .001    .040   .01    .09   <.02    .04   11.99  12.00

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                        TABLE 7.17  SOIL PORE WATER  (mg/1)  METALS  (SITE2)
                 Ag     Al     As     Ba     Cd     Cr     Cu      Ni     Pb     Zn     Fe     Mn




       6/16/82
       Bkg        .006   0.58   <.001   .88   <.001   .050   .04     .001   <.02   <.001   .49   <.003




       Area 6U    .009   0.85   0.140   .88   <.001   .070   .04     .023   <.02   0.73   4.44  34.600




       Area 3     .013   0.42    .061  4.63   <.001   .030   .08     .048   <.02   1.04    .33    .006




       Area 6T    .012   0.56    .028   .88   <.001   .030   .03     .015   <.02   4.34    .06    .253




ON      11/19/82




       Area 5T    .012   0.59    .060   .70   <.001   .040   .06    <.001   <.02   0.07   1.38   1.090




       4/11/83




       Area 3     .035   0.29     -    3.82   <.001   .030   .02     .50    0.44   0.08    .09   <.003

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                    TABLE  7.18   SOIL PORE WATER (mg/1) METALS  (SITE 3)


6/15/82
Bkg
Area 2
Area 5
3/8/83
Bkg
Area 2
Ag

.077
.022
.044

.026
.043
Al

<.02
.23
.26

.28
.35
As Ba

.77
.054 2.53
6.63

.62
4.32
Cd

<.001
<.001
<.001

<.001
<.001
Cr

.010
.010
.040

.010
.070
Cu Ni

<.02 .208
.02 .073
.04 .429

.05 .34
.02 .40
Pb Zn Fe

.02 .49 .551
<.02 2.84 .964
<.02. .74 3.594

<.02 .08 .060
<.02 .08 2.090
Mn

.463
7.31
32.40

.01
20.19

-------
concentrations ranged from 0.12 to 12.00 mg/1.
     At  site  2, most  metal concentrations  in the  site
soil pore water  samples  were a little  higher  than  those
in the background soil pore water samples.  However,  with
the exception of a  few values  for  barium,  zinc,  iron and
manganese,  the  concentrations  were  not higher than the
drinking water  standards.   Barium  concentrations  of  3.82
and 4.63  mg/1 were  found  in two  samples  collected  from
the same  sampler at the  site.   As with  site  1  samples,
the values  of iron  were  elevated, ranging from  0.09  to
4.44 mg/1,  with a  background  value  of 0.49  mg/1.   The
manganese values  ranged  from  <0.01  to 34.60  mg/1.   The
34.6  value  seemed  very   high,  but  duplicate  analyses
yielded similar values.
     At site 3, as with the other sites, only the barium,
zinc, iron and manganese values were significantly higher
than background.   The  manganese  values were particularly
high, with  two  different  samples  from the same area giv-
ing  concentrations  of  7.31  and  20.19  mg/1.   Another
sample from a different area, contained 32.4 mg/1 of
manganese.
£H
     At site 1 only  one set of pH values was obtained and
these  were  all  around 7.   At  site  2  the pH  values  of
samples,  taken at  different times,  ranged  from  6.4  to
7.4.  At site 3, pH  values of soil water taken at dif-
ferent times again ranged  from 6.4 to 7.4.
Chloride ion
     The  chloride  ion concentration  of  the  soil  pore
water  at  the  sites  is shown in  Table 7.19.  The concen-
trations  at sites  1  and  3 were  appreciably  higher than
the"  concentrations at site  2.   The  results  indicated  a
decrease  in  the  chloride  ion  concentration  with   time,
with  the  sites with  higher  oil  concentrations having
                           65

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        TABLE  7.19  SOIL PORE WATER

     CHLORIDE  ION CONCENTRATION  (mg/1)
Site 1
Date Location
Area 1 Area 3 Area 4
6/14/82 655.1 600.5
8/4/82 - 522.3
12/1/82 395.6
1/13/83 - - 372
Site 2
Date Location
Bkg Area 3 Area 5 Area 6
(untilled)
6/16/82 14.6 82.1 - 137.9
7/8/82 13.2 52.8 11.5 65.8
11/19/82 -
2/16/83 - - 20.5 30.8
4/11/83 - 21.7
Site 3
Date Location
Bkg Area 2 Area 4
6/15/82 112.8 1056.4
10/19/82 - 759.0
3/3/83 40.9 486.5
6/7/83 28.7 434.9

Area 6
701.0
364.9
Area 6
(tilled)
61.9
21.8
24.9
Area 5
5147.4
2129.3
No sample obtained on this date or no analysis  performed
because of insufficient sample
                     66

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higher chloride ion concentrations.
     This  shows  that sites with  high oil  loading  rates
can leach  significant amounts of  chloride  ion  for a con-
siderable  period  of time.   No  oil  had  been  applied  to
site 2 since 1976, and the chloride ion concentration was
low, while  at  sites  1  and 3, where  the  chloride  ion was
much higher, oil had been applied at high loading rates
up until the beginning of 1981.
COD/TOG
    'The soil pore water contained oxidizable material at
quite high levels when compared to backgound.  At site 1,
the COD values ranged from 400 mg/1 to 2420 mg/1 when the
first COD  samples were analyzed.  Six months  later, the
highest  concentration  was  1690  mg/1.   TOC values  were
consistently lower than COD values,  by a factor of about
3.  Three  TOC  values  taken  from one  location  at  this
site,  indicated a decrease in TOC with time.
     Site  2  showed similar trends, with  a COD/TOC ratio
of  about  3:1.  Again  there  was  a  decrease in  the TOC
values with  time.  The COD  values  also  decreased.   The
amount of  organic carbon  present was lower  than  at site
1, as would be expected from the  lower oil content values
at site  2.   Values ranged from 335 mg/1  to  990 mg/1 for
COD on  the first  set of  samples  with a  background value
of 13 mg/1.
     Site  3  samples  showed  a  general trend of  increasing
COD  at  the  2   locations  where  several   samples  were
collected  over a  12  month period.  Again a COD/TOC ratio
of  approximately  3:1 was  observed.   Tables 7.20  - 7.22
present  the  pH, COD, TOC  and conductivity values of soil
pore water samples.  This data is presented  graphically
in Figures 7.1 -  7.7.
                           67

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       TABLE 7.20  SOIL PORE WATER CHARACTERISTICS
                   SITE 1
Date    Location    pH     COD       TOC    Conductivity
                        (mg/1 as 0,)  (as C)    (umhos/cm
                                 *             at 25°C)
6/14/82  Area 1     7.2    1580
         Area 3     7.0     400
         Area 6     7.2    2420
          458
          110
          751
12/1/82  Area 1
         Area 4
         Area 6
1000
1000
1690
306

503.1
1/13/83  Area 6
          488.7
                           68

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       TABLE 7.21  SOIL PORE WATER CHARACTERISTICS
                   SITE 2
Date    Location    pH     COD        TOC    Conductivity
                       (mg/1 as 09)  (as C)    (umhos/cm
                                 ^             at 25°C)
6/16/82    Bkg       -      13.        8.0
         Area 3     7.2    990       303.0
         Area 6U    7.0    750       232.0
         Area 6T    6.9    335       102.0
7/8/82    Bkg       7.1     50  '       8.0
                                     300.0

                                     198.0
                                      86.0
11/19/82 Area 6U     -     770
         Area 6T     -     460
2/16/83  Area 3     6.6     -        243.3        2400
         Area 5     6.4     -         84.6         900
         Area 6U    6.6     -        187.5        2000
4/11/83  Area 3     6.8    560       212.4
         Area 5     6.5    325       108.8
Bkg
Area 3
Area 5
Area 6U
Area 6T
7.1
6.8
7.4
6.8
6.9
50
960
235
665
300
                          69

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       TABLE 7.22
         SOIL PORE WATER CHARACTERISTICS
         SITE 3
Date

6/15/82


Location

Bkg
Area 2
Area 4
pH

6
7
6


.8
.3
.6
COD
(mg/1
as 02)
93
440
850
TOC
(as C)

41
117
204
Conductivity
(ymhos/cm
at 25°C)

-
_
10/19/82  Area 2     7.0    615
          Area 5     6.4    740
3/8/83     Bkg       7.0     90
          Area 2     7.3    610
          Area 5      -     630
                                        32.8
                                       189.9
                                        1020
                                        1700
5/2/83
 Bkg
Area 2
Area 5
                     6.4
                     6.6
  60
1180
 750
 27.1
352.9
6/7/83
 Bkg
Area 2
Area 5
                     6.8
                     6.8
                     7.4
 125
1220
 850
 23.7
383.3
1000
3500
                          70

-------
  700
-  500
u
-  300
   100
                             e A-e
           C
      «J 00   3

      Z <*   ^
                    en
ai
to
O
z
u
0)
Q
                                             ^^^_^-k.
                    e
                    IB
a ao
Z w
       Figure 7. l  Graph of T.O.C. vs  time for site 1
                     soil moisture samples
                            71

-------
50<
     Figure 7.2  Graph of T.O.C. vs time for site 2
                 soil moisture samples
                      72

-------
   1200
   1000
    800
cT*
m
10
§
U
    600
    400
    200
                                          ©  A-3

                                          &  A-6U

                                          0  A-6T
       CM  -H
       3 CO  3
       fj 
£ (T>
          Figure 7.3   Graph of C.O.D. vs  time for site  2

                        soil moisture samples
                            73

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  140
  120
  100
   80
^  60

01
J
u
   40
   20
                                      O Area  3

                                      A Area  6 untilled

                                      O Area  6 tilled
         O
O    0)
Z    O
c
a
     0)
     u,
a
X
                                                          CLOD
        Figure 7.4   Graph of Cl vs time  for site 2

                      soil moisture samples
                           74

-------
   500
   400
   300
u

m
   200
   100
            ©  Bkg

            A  A-2
      CM  r-t
      90  3

      *3 04  •-}
3
<
           4)
           W
O
O
                     0
                              ,

-------
  1200
  1000
   800
a
a  600
Q
O
U
   400
   200
        0-
      C 


<
a
v
CO
                         u
                         o
>    u
O    0)
z    a
e
a
     0)

     Cu
                                                a
em
3m
          Figure  7.6  Graph of C.O.D.  vs time for site 3

                       soil moisture samples
                              76

-------
                                              O  Bkg

                                              &  A-2

                                              O  A-5
  500(
  400( .
  300(
- 200C
  100C
         Figure  7.7  Graph of Cl vs tine for site 3
                      soil moisture  samples
                                  77

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Oil Content
     Table 7.23  shows oil content  values for  some  soil
pore water samples  from  each of the three  sites.   There
does not  appear  to be much  correlation between the  oil
content and the  TOC/COD  values for the soil  pore  water.
The sample from  area  3 at site  2  had an oil  content of
0.8 mg/1  and  a TOC of 2433  mg/1,  while  the  sample  from
area 6 at site 1, had an  oil content  of 133.2 mg/1 and a
TOC of 488.7 mg/1.
     The values show that oil can be leached from the top
layers of the soil  for   some  time  after application of
residues has ceased at a  site.

       TABLE 7.23  OIL CONTENT OF SOIL PORE WATER
Site No.
1
1
1
2
2
2
3
3
Location
Area
Area
Area
Bkg
Area
Area
Bkg
Area
1
6
6

3
6 U*

2
Date Oil Content (mg/1)
12/1/82
12/1/82
1/13/83
7/8/82
2/16/83
2/16/83
3/8/83
3/8/83
60
73
133
<0
0
71
<0
13
.7
.0
.2
.1
.8
.4
.1
.2
     *    U - untilled.

DEEP CORE ANALYTICAL RESULTS
     Deep cores refer to samples taken below 51 cm depth.
These  samples  were analyzed for oil  content,  metals and
priority pollutants as a part of the unsaturated zone
monitoring program.
Oil Content
     The oil content of the deep cores taken at the  sites
with the exception of  2  samples  at site  2 and at site 1,
were all less  than 0.1%, indicating  that  no  oil had mi-

                          78

-------
grated below  51  cm.   At site 2, two  samples  from area 6
had oil content values of 0.21 and 0.24%.  Site 2 was the
most permeable of the 3 sites, and area 6 was the area at
site  2 with  the highest oil  content.  Thus,  it  is  pos-
sible that oil might  have  reached  the 124 cm  (49 inches)
depth.  The high value at site 1 was in area 1, which had
the lowest oil content at the site.  It appears that this
value was an outlier, since all other concentrations were
very low, and the permeability of the site soil was very
low.  The oil content data is presented in Table 7.24.
Priority Pollutants
     A number of organic priority pollutants were identi-
fied  in  the  core samples at  the unsaturated  zone at the
three sites.   Table  7.25 lists  the  compounds identified
at  the   sites.   No  compounds were   found  at all  three
sites, only  5  were found at  2 sites,  and all other com-
pounds at  only one  site.   Anthracene, 1,2-Diphenylhyra-
zine,  Bis(2-ethylhexyl)phthalate,    Butylbenzylphthalate
and  2,4-Dichlorophenol  were  the  compounds  found  at   2
sites.
     Priority  pollutants were  also  found  in  the back-
ground  cores  at  the  sites.    1,2-Diphenylhydrazine was
found at site  1  and  phenol at site 3.  Site 2 background
cores contained  5  compounds.   The area  from which back-
ground cores  were  taken at site 2, was contaminated with
oil  after  the project  started.   This may  be the reason
for  some  of  the  anomalous  results   obtained  with back-
ground samples taken  from this area.
     Concentrations  of  the  compounds identified  in the
analysis  of  the  deep   cores are  given  in  Tables B-5
through  B-8,  Appendix  B.   These  concentrations  are not
absolute,  but represent  rough guides,  since no study on
recoveries of organics  from soil matrices was  performed.
                          79

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       TABLE 7.24  OIL CONTENT DATA FOR DEEP CORES
Date        Location/Depth(cm)          Oil Content{%)

Site 1

12/30/81       2(114-127)                     .02
               3(81-122)                      .01
               6(81-104)                      .03

6/30/82        Bkg(102-112)                   .05
               Bkg(152-168)                   .11
               1(127-141)                     .74
               6(107-117)                     .06
               6(152-163)                     .05
Site 2

12/21/81       3(66-76)                       .03
               3(76-91)                       .02
               3(91-102)                      .02
               5(66-91)                       .00
               5(124-152)                     .00
               6(66-81)                       .21
               6(81-124)                      .24
               6(124-147)                     .04

7/8/82         2(84-94)                       .04
               4(86-102)                      .03
               4(127-137)                     .02
               6(127-147)                     .02
               Bkg(76-107)                    .07
               Bkg(142-157)                   .04
Site 3

12/28/81      2(76-91)                        .03
              3(81-91)                        .01
              5(69-76)                        .02

6/29/82       Bkg(76-89)                      .03
              Bkg(117-130)                    .05
              2(114-122)                      .02
              6(132-142)                      .03
                           80

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 TABLE 7.25  PRIORITY POLLUTANTS PRESENT IN UNSATURATED
             ZONE CORES
Compound                  Site 1     Site 2     Site 3

Acenaphthene                x
1.2-Disphenylhydrazine      x          x
2,4 Dinitrotoluene          x
Anthracene                             x           x
Bis(2-ethylhexyl)phthalate             x           x
Isophorone                             x
Acenaphthylene                         x
Fluorene                               x
Diethylphthalate                       x
Butylbenzylphthalate                   x           x
2-Nitrophenol                          x
4-Nitrophenol                          x
2.4-Dichlorophenol                     x           x
Phenol                                 x
Phenanthrene                                       x
Pyrene                                             x
Chrysene                                           x •
Benzo(a)anthracene                                 x
Benzo(b)fluoranthene                               x
Benzo(k)fluoranthene                               x
Benzo(a)pyrene                                     x
2,6-Dinitrotoluene                                 x
Di-n-butylphthalate                                x
                           81

-------
Metals
     The metal concentrations  in  the  deep cores were not
significantly above background concentrations, except for
the nickel concentrations  in  both the first set of cores
from the  (127-152) cm depth at site  1,  and the first set
of cores from the (114-142) cm depth at site 3.  However,
the concentrations  were quite  low,   33  and 49  mg/kg  at
site  1  and  3,  respectively.   Thus,  it appears  that  no
buildup of metals occurred in the unsaturated zone.   The
raw metal data is given in Table C-6, and the mean con-
centrations in Table C-7,  in Appendix C.
Discussion of Results
     Monitoring  of  the unsaturated  zone at  these three
sites revealed some interesting facts.  The water passing
through  the  unsaturated zone  contained high  amounts  of
chloride,  and appreciable  amounts of  Freon  extractable
compounds  (oil  and  grease).   Some metals  are apparently
solubilized  under the  conditions which  exist  at these
sites.  Even though the pH of the soil pore water and the
pH of  the soil  in  the top 51  cm (20  inches)  were  both
above  6.5  (usually  above  7.0),  barium,  zinc,  iron and
manganese  were  found  at  fairly  high  concentrations,
especially iron  and manganese,  in the  soil  pore water.
Further monitoring  of  soil pore  water  at land treatment
sites is necessary to verify these results.
     No evidence of migration of oil  into the soil of the
unsaturated  zone (below 50 cm)  was  found.   However the
results  suggest  that there is some  movement  of organic
priority pollutants  into  the   unsaturated  zone.   It must
be  stressed  that the  quantitative values  presented for
these  priority  polluants  are  intended as guides only,
since no work  on recovery  of  organics from soil matrices
was  performed.   The  deep  soil  cores  contained  more
compounds than the soil pore water.  Whether this may due
                           82

-------
to better recoveries from the soil matrices as opposed to
the aqueous phase,  or to the absence  of  these compounds
in the aqueous phase has not been determined.
     The soil  pore  water also  showed  levels of  TOC  and
COD much above  background  at  all  sites.   However,  it
appears  that  the  oxidizable material present may have  a
large  inorganic  component,   since  the  TOC/COD values  at
site 2  are  in the  same  range  as those at  site  3,  where
the soil organic content  is very  much  higher.    If  the
oxidizable  material were  primarily organic,  one  would
expect  site  3 to have much higher TOC/COD values  than
site 2.
     At  site  2, where the  soil  moisture  samplers  were
located under tilled and untilled sections of area 6,  the
TOC, COD and  Cl  concentrations,  as presented  in Figures
7.3-7.5, are  higher under  the  untilled  area  than under
the tilled area.
     This suggests  that tilling  the  soil does  have  the
effect of reducing the concentration of substances in the
soil pore water.   This  is  probably because the permea-
bility of the tilled area is increased, resulting in less
leaching of  the till  zone  by  infiltrating  water.   This
results  in  lower contaminant  concentration in  the  soil
pore water,  since  most  of  the  contaminants are  in  the
till zone.
                          83

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                        SECTION 8
                     EMISSIONS STUDY

     During the course  of the closure study, it  was  ob-
served that after tilling the soil at the landfarm sites,
a strong smell of hydrocarbons was  present  in the tilled
areas.  It  was  decided  to  attempt  to determine  whether
significant  levels  of  hydrocarbons  were  being  emitted
from  the  site  as a result  of the  tilling  operation.   A
hydrocarbon monitor  called  a Bacharach TLV-Sniffer  was
used.  This  is  not  a standard  procedure,  but has  been
used  by Radian  Corporation to assess  emissions  from  the
land  treatment  of  oily  sludges.  The TLV Sniffer has  a
sensitivity  range  from  1  to 10,000  ppm  of gas.   The
Sniffer functions by  catalytically  oxidizing the  gas  in
the  air  sample.  The  catalyst  is  coated  on  an  element
whose resistance charges with the amount of oxidized gas,
and this change in resistance is compared to an identical
element not subject to  oxidized  gas.   An electrical  sig-
nal is generated, which  depends  on  the difference in re-
sistance between the  two elements,  which in turn depends
on  the  amount  of hydrocarbon present originally.  Table
8.1 presents data obtained  by using the  Sniffer at sites
1 and 3 on  background soil, and  site soil  before and af-
ter tilling.  It should  be  noted that the  soil at site  1
was  fairly  wet  when these  readings  were taken,  while at
site  3 the site was dry.  At  site 1, the soil was too wet
to till, and so readings were taken from a section of the
site  which  had  been  tilled before, and a  section which

                           34

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TABLE 8.1  CONC. OF HYDROCARBONS EMITTED AT SITES 1 AND 3
     Location
Hydrocarbons Emitted



     (mg/hr/M2)
     Site 1, Control Area



     Site 1, Untilled Area



     Site 1, Tilled Area






     Site 3, Background



     Site 3, Before Tilling



     Site 3, After Tilling
         1.2




         1.2



         1.7






         1.2




        10.2




        25.2
Site 1 - Site soil was wet



Site 2 - Site soil was dry
                          85

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had never been tilled.  At site 3 the same area was test-
ed before and after tilling.
     The results obtained  from  site  3,  which had not had
any residues  applied for  18  months when  these readings
were taken, suggest  that  hydrocarbons  are  emitted from a
land treatment site  for a  long  time  after  application of
residues,  and  that tilling  increases  the rate  of these
emissions.  The data  from  site  1  suggests  no appreciable
increase in emissions occurs.   However,  the  soil at site
1 was  wet  and could  not  be tilled just prior  to taking
the readings.  This  could have affected the quantity of
hydrocarbons emitted  from the tilled area.
                           86

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                        SECTION 9
                      RUNOFF STUDY

     The objective of this study was to determine whether
runoff  from closed  land treatment  sites  contained  any
selected  hazardous  constituents.   To  carry  out  this
study, a wooden  frame  was installed at  each  site.   This
frame consisted  of four  (4)  2  x 12 pieces of. board 3.7
meters  (12  feet) ,  connected  together  to form  a square
with one end open.  The  open  end was attached to a metal
flume 5 cm. (2 inches)  wide, 15 cm.  (6 inches) deep and 1
meter (38 inches)  long.   The  frame was installed at each
site so that the corner with the flume was down slope, so
that any rain  which fell inside the  flume  would run off
towards the open end to which the flume was attached.
     Water was then applied  inside the frame  in the form
of a  spray,  to simulate  the  25 year, 24 hour storm for
the particular area in Oklahoma.  Site  one received the
equivalent  of  15 cm.   (6  inches) ,  and sites  2  and  3 re-
ceived  18  cm.  (7  inches) ,  since these  were  the amounts
that  would  be the equivalent  of  the  25 year,  24  hour
storm as obtained  from Technical Paper No.  40, published
by the  Weather Bureau   (Hersfield, 1981).   The water was
applied over a period  of about two hours, and the runoff
collected at  fixed intervals  until  the  runoff  stopped,
and  composited.    Samples  from  the  composite  were  then
analyzed for
      (1)  priority pollutants      (2)  metals
      (3)  oil content

                           87

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     (4)  COD/TOC
     Table  9.1  shows the  COD/TOC  values,  Table  9.2  oil
and grease  and Table 9.3  metals  shown to be  present in
the runoff from the three sites.

           TABLE 9.1  COD/TOC CONC. OF RUNOFF
Site No.
, 1
2
3
COD
(mg/1 as 0.)
120
5
540
TOC
(mg/1 as
18
<5
495
C)



     The  runoff area  at  site 1  was  untilled with  no
grass, site  2  was  grass covered,  site  3  was  tilled with
no grass  cover.  Runoff started at sites  1 and 2,  which
were untilled,  quite soon  after application of the spray
water.  However,  at site  3,  which was tilled,  it took
much  longer  for runoff  to start,  and  the color  of  the
runoff was much darker than  at either  of the  other  two
sites.

    TABLE 9.2  OIL AND GREASE CONCENTRATION OF RUNOFF
Location
Site
Site
Site
1
2
3
Results and
, Runoff
, Runoff
, Runoff
Discussion
Oil and Grease mg/1
8.4
10.8
35.8

     The  color  of the  runoff  from site  3  was brownish,
with  suspended  particulate  material.   The  runoff  from
                           88

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                          'TABLE 9.3  METAL CONCENTRATIONS IN  RUNOFF WATER
oo

Site 1
Applied water
Runoff 1
Runoff 2
Site 2
Applied water
Runoff 1
Runoff 2
Site 3
Applied water
Runoff 1
Runoff 2
Ag

0.015
.019
.025

.006
.013
.017

.019
.004
.005
Al

.04
1.63
1.19

.09
0.07
.28

.19
.86
.34
Cd Cr

<.01 .04
<.01 .09
<.01 <.003

< .01 < .003
<.01 .04
<.01 <.003

<.01 .02
<.01 .01
<.01 <.003
Cu

.05
.09
.10

.01
.01
.01

.01
<.002
.01
Fe

.150
1.863
0.830

< .005
.323
.294

.050
.490
.373
Mn

<.003
.008
.011

< .008
.033
2.72

.020
1.51
.021
Ni

.010
.046
<.008

< .02
<.008
<.008

.045
<.008
<.008
Pb

<.02
<.02
.02

< .02
<.02
<.02

0.17
<.02
<-. 02
Zn

<.001
<.001
.050

.34
.060
.220

<.001
<.001
<.001

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site 2 was almost colorless with little suspended materi-
al.  The runoff  from  site  3 was  a  pale brown color,  with
suspended particulate material.
     The COD  and oil and  grease data  indicate  that the
runoff  from tilled  areas without  grass cover  contains
more  organic  material  than  runoff  from untilled  areas
without grass cover.  Even though  the oil content of the
areas under study  at  site 1  (s8%)  and  site  3  (s!4%)  was
appreciably different,  the reason  for  the  difference in
the concentrations of oil  and  grease  and  COD of  the  run--
off from these sites, appears  to be  the longer time  that
it  takes  to get runoff at  site 3.   Here  the  soil  was
tilled, and the water first had to saturate the soil, be-
fore  runoff  could begin,  resulting  in a darker colored
runoff  with higher  organic  concentrations.   At  site  1
where  no  tilling had occurred,  the  soil was  compacted,
resulting in low infiltration rates and immediate runoff.
Site  2 was  grass covered,  and had   a  low oil content
(s3%) .  These factors combined to  produce a runoff which
was low in organic content.
     Duplicate determinations of metal ion concentrations
were carried out on samples of the runoff from each site.
The concentration  of  metals  in  the water applied to the
sites was  also  determined.  Table 9.3  lists the results
of  these  analyses.   There were  differences  in the metal
ion  concentrations  between duplicates for  some metals.
This  variation  between  samples  is probably due  to the
fact  that the runoff  contained particulate  material, and
the determinations were made  for  total metal concentra-
tions.  Thus, it is  possible  that  the different samples
contained varying  amounts of  particulate material,  des-
pite  the fact that the  sample  containers were thoroughly
mixed prior to sampling.
     Two metals  appeared  in  the  runoff from all three

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sites at appreciable higher concentrations than in the ap-
plied water.   These metals  are  aluminum and  iron.   The
runoff from the  sites  did  not contain any of the organic
priority pollutants evaluated  (Table 7.1) above detection
limits (0.1 ppb).   Only  base neutrals and phenolics were
evaluated.  In this particular study,  only  two of the 11
metals determined  showed  up at  increased  concentration
levels in the  runoff.   These metals were  aluminum and
iron.
                           91

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                       SECTION 10
                   REVEGETATION STUDY

     The purpose of the revegetation study was to develop
an insight  into  the  process of site closure  by studying
the  effect  of oil  refinery  residues  on  selected  plant
species.   At  the  time  this  study was  conducted  very
little knowledge was  available for the closure of  sites
and  no  formal  guidelines concerning the  revegetation of
sites existed.   Although grasses were the obvious primary
choice for revegetation, the OU/EPA cooperative team also
agreed  that trees  should be  included in  the  study in
order to determine whether certain species of trees  could
successfully be grown  in  the  closure  and  early post clo-
sure periods.  Trees  are useful in minimizing  wind ero-
sion and  have  aesthetic value.  Because  most  trees grow
slowly in relation to  grass it was felt  that  an attempt
should be made to investigate the feasibility of planting
trees as soon as conditions in the closure site per-
mitted.
Species Descriptions
     Several species  of trees and  grasses  were selected
for  field  study.   The  plants  which were  selected  had a
number of attributes which made them suitable for revege-
tation purposes.   The most important attribute, common to
all species, was their known hardiness.
     In addition, trees were  selected  which have shallow
roots  in  order to  reduce  the  possibility of  the  roots
acting as channels for the contamination of ground water.
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Five tree species and four grass species were chosen from
a survey of vegetation growing  in  the  state of Oklahoma.
Colonial  bentgrass,  however,  was  an  exception.   The
selected  species  are listed  below.   A  brief  charac-
terization of each also follows.
Black Locust (Robinia pseudoacacia L.)
          The black locust is a member of the Legume fam-
     ily.  The natural range of this species is the cen-
     tral Appalachian and Ozark mountains but it has been
     cultivated  widely -and  now  reproduces  on  its  own
     throughout  Eastern  North  America  and parts  of  the
     West (Elias 1980).  The black locust has been plant-
     ed extensively in the  state  of Oklahoma.  It can be
     found  in  moist  woodlands,  farm lots,  along  fences
     and  roads,  and  in  urban  environments  (Phillips
     1959) .
          Reclamation studies have shown the black locust
     to be widely adapted to  all  classes of mine spoils.
     The black locust has the ability to fix nitrogen and
     grows  rapidly  giving  quick cover.  This species is
     valuable as a nurse crop for forest planting because
     it  improves soils  by  adding  nitrogen  and  organic
     matter.  Black locusts can be attacked by the locust
     borer  beetle  which  results in  multiple  stem shoots
     sprouting  after  the main  stem deteriorates   (Thames
     1977).
Hackberry (Celtis occidentalis  L.)
          The hackberry tree  is a member of the elm fami-
     ly.  It is  widely distributed in the Eastern United
     States.  The  hackberry  is adapted to  a variety of
     soils.  In Oklahoma it may be  found on slopes, rocky
     hills and bottom lands.
          The  hackberry  frequently  grows  in  limestone
     soils and on limestone outcrops.   In  good soils  this

                           93

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     tree is  fast  growing and may live  up  to 200 years.
     Because  of  its drought  resistance  this  species  is
     often  planted  in  the  Midwest  (Elias  1980).   The
     hackberry  has  good  adaptation  to  disturbed  areas
     (Thames 1977).
Osage Orange  (Madura pomifera (Raf.) Schneid)
          The osage  orange,  "Bodark",  is a  member of the
     mulberry family.   The  native range of this species
     is  uncertain,  but  it  is  found   from  Southwest
     Arkansas to East  Oklahoma and  Texas.   This tree  is
     widely  planted  in  the  Eastern  and  Northwestern
     states (Little  1980)  .
          The osage orange  is  basically a  lowland tree
     that grows  best in  deep  rich bottom  lands,  but  it
     will tolerate a wide  range of  soils.   In Oklahoma
     this stout tree is considered to be quite hardy and
     has been planted as  a windbreak and hedgerow species
     (Phillips 1959) .
Red Cedar (Juniperus Virginiana L.)
          The eastern  red  cedar  is the  most widespread
     conifer  of  eastern North America.   This species  is
     also the most drought resi-stant conifer  found  in the
     east.  The tree is rather slow growing and lives to
     a moderate age  of 200-350 years  (Elias  1980) .
          The red  cedar is found scattered  throughout the
     state  of Oklahoma  in all classes and.conditions  of
     soils  -  from   low, wet,  swampy areas  to dry, rocky
     ridges containing  thin  soils.  This tree is said to
     "seemingly  thrive  on  barren  soils  where  few other
     trees  are  found"   (Phillips  1959).    Reclamation
     studies  in the state have shown the red cedar to be
     especially  well  adapted to  high  clay  mined land
     (Thames  1977)  .
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Russian Olive (Elaeagnus anqustifolia L.)
          The russian olive  is a member of  the oleaster
     family.  This tree  is native  to Southern Europe and
     Central  Asia.   It  was  introduced  into  the  United
     States  during  colonial times.   This  tree  has  been
     planted  and naturalized  from  New  England west  to
     California  (Little 1980) .
          The  russian  olive  is tolerant  of  soils  from
     salty  to alkaline.   Because of its  dense branches,
     extreme  hardiness and resistance to  drought,  it has
     been planted extensively  as a windbreak  in the prai-
     rie states  (Elias 1980) .  The russian olive has good
     adaptation  to disturbed areas and maintains a fairly
     fast growth rate (Thames  1977) .
Bermudagrass  (Cynadon dactylon Pers.)
          Bermudagrass is a warm season, sod  forming, pe-
     rennial  turfgrass  which  propagates  and spreads by
     stolons  as  well as  by underground rootsta'lks.  Seed-
     ing of  bermudagrass is dependable only where winters
     are  not extremely  cold  and there are   no  prolonged
     drought periods.   For vigorous growth  and root de-
     velopment,  sodding  or  sprig planting is  the desired
     method  of propagation  (Archer and Bunch, 1953) .
           Introduced  from  India, bermudagrass  grows  from
     Massachusetts  to  Missouri and  Oklahoma.   It is  cul-
     tivated for grazing or  lawn  use.  It  is a weed  of
     ditches, vacant  lots,  roadways, and is  well adapted
     to clayey bottomlands which are occasionally  subject
     to flooding (Gould  1978) .
           Bermudagrass  sod  is used  extensively for  ero-
      sion  control on streambanks, earthfills and  slopes.
     This  species  does  best  on  moderately  well  drained
      soil  and has a wide pH range tolerance.  One  of the
      primary uses of bermudagrass in Oklahoma is  for re-
                           95

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     vegetation  of strip  mines.   Bermudagrass  requires
     high amounts of nitrogen for superior yields and may
     become  sod  bound  if  not  cultivated  after  four  to
     seven years (Thames 1977).
Colonial Bentgrass (Agrostis tenuis Sibth.)
          Colonial bentgrass  is a cool  season  perennial
     species.  It is loosely tufted with short rootstalks
     and  abundant  fibrous  roots.   Mat  forming  charac-
     teristics make  this a  favorable species  for  lawns
     and golf courses.   Colonial  bentgrass  is one of the
     many  bentgrasses  common  to Great  Britain  (Vasey
     1893) .
          Colonial bentgrass  is  able  to thrive  on  lime
     poor  soils  in New England  and many  parts of  the
     northern  and  middle  Atlantic  states.   This  hardy
     species  is  most  known  for its tolerance  for  heavy
     metals.  Populations of colonial bentgrass  have been
     used  for  the  reclamation  of  metalliferous  mine
     wastes  in England.   Bentgrass has been used to re-
     claim  acid  and  calcareous wastes  containing  lead,
     zinc and copper  (Smith and Bradshaw, 1979) .
Crabgrass (Digitaria Sanguinalis  (L.) Scop.)
          Large  crabgrass  is  a   warm  season,   shallow-
     rooted  annual  species.  It  reproduces by  seed and
     its  tufts   increase in  size by  rooting where  the
     nodes touch the  soil.   Crabgrass  can  be found grow-
     ing in a wide variety of soils throughout the United
     States,  especially  in  the East  and  South   (Phillips
     Petroleum 1963).
          Crabgrass volunteers  well on  disturbed soils.
     It  is  a common  invader  on abused  native  ranges and
     has been found to  be  palatable to livestock.  Crab-
     grass prefers well drained  conditions  and  will not
     survive  on  water  logged  soil.   This  grass  is very
                           96

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     drought resistant and responds rapidly to precipita-
     tion and nitrogen addition (Dalrymple).
          Bermudagrass is easily confused with crabgrass.
     Crabgrass is  larger  than bermudagrass and  tends  to
     sprawl  on  top  of the  ground  rather than  forming
     dense mats.   Crabgrass  is the  most  unpopular  lawn
     and garden weed.   It does, however,  possess  nutri-
     tive  qualities  which make it  useful  as a  forage
     crop.  Watts  et  al.  (1981) found that  this  species
     did well on their land treatment site.
Weeping Lovegrass  (Eragrostis curvula)
          Weeping  lovegrass is  a stout,  warm  season,  pe-
     rennial bunchgrass with  narrow, weeping  blades  and
     extensive fibrous  roots.   This  grass was  first  in-
     troduced from South Africa and was  planted  exten-
     sively  in  the Southwest  and  Southcentral parts  of
     the United  States during  1936  to  1945 where  it  is
     well adapted  (Archer 1953).
          Weeping  lovegrass is easily established by seed
     and spreads by tillering.  Young  seedlings  are vig-
     orous and quickly form  a  ground cover.   This grass
     is  often  planted  for erosion control  and  grazing.
     Weeping  lovegrass does  well  on  any  type  of  well
     drained  soil  but  prefers  sandy loam.   Good  stands
     can  be  obtained  on  soils with undesirable  charac-
     teristics (Dalrymple 1976) .
          Weeping  lovegrass  is one  of   the  best  grasses
     for marginal  low potential soils.    It  does  well  on
     low  fertility soil but  does  best  on  fertile soil.
     Soil  pH  has  little  influence on the  adaptation  of
     lovegrass.   Weeping lovegrass will grow on acid mine
     spoils  and  on soils which are highly  basic.  This
     grass is heat and drought  resistant but has a higher
     water  requirement  when   grown  on  clay  soils  as

                          97

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     opposed to sandy ones.  The hardiness of this grass
     increases with precipitation (Dalrymple 1976) .
MATERIALS AND METHODS
Site Characterization
     The  field  studies were  conducted  on an  11,700  ft
section  of  site 3.   The  land treatment  area of site  3
totaled  7.04  acres.   No residues had been  placed on  the
study site  for  ten months  before revegetation tests were
conducted.  The southern part of the study site contained
a higher oil concentration  than  the  northern one and  was
designated  area B.   The northern section which  had less
oil content was designated  area A.   Thus,  a comparison
could be  made  between a lighter and  heavier oil content
with  subsequent  effects   on  revegetation.   Lime  and
fertilizer were applied to  the  treatment  area to satisfy
the  needs  of  the plants  and  soil  microorganisms.  The
fertilizer  applications were  made as  needed at a rate of
300 Ib/acre of 10:20:10 or 40-0-0.
     The soil  in  the study area is classified  as a clay
soil and contains  20% sand, 32% silt and  48% clay.  The
cation exchange capacity is 14 ce/lOOcm.  All of the soil
used for laboratory investigations was taken from the
land treatment and control sites.
Trees
     Field  site 3 was prepared  and  trees  were planted on
March 26, 1982.   The control site was  prepared  by  first
clearing away  brush  and weeds with a bulldozer  and then
tilling  the soil  to a  46 centimeter  depth.   Care  was
taken during  the  cleaning operation to remove  as  little
topsoil  as  possible.  The  land  treatment area  was also
tilled to the same depth.
     The selected tree  species were  donated for study by
the Oklahoma State Forestry  Division.   Trees were all in

                           98

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the first year seedling stage.  The seedlings were placed
in holes which were 46 centimeters deep by 20 centimeters
wide.  All of the  holes were  filled upon planting with a
mixture of soil from the control area and peat moss, then
thoroughly watered.
     Trees were  spaced at  1.2 meter  intervals  in rows
which  ran from  north to  south  for  each species.   The
trees were planted in the  following order  from  west to
east:   black locust,  osage  orange,  hackberry,  russian
olive, and red  cedar.   Herein, the northern  part of the
land   treatment   site has  been  designated  area  A,  the
southern  part  area  B,  and  the   control site   area  C.
Forty-five trees,  nine  of each species,  were planted in
area A.   Fifty  trees,  ten of  each  species,  were planted
in area B and  in  area  C.   Individual trees were numbered
from north to south,  1-10, for each species.
     A thin layer  (9,346 cubic centimeters) of an organic
mulch  (tradename  Permagreen)  was  spread  around  the base
of each  tree to  counteract some  of  the  ill  effects of
summer heat.   The mulch was applied  July 14,  1982 to all
trees and was mainly composed of composted cotton plants.
A weedeater and lawnmower were employed to control weeds
in area C.  Photographs were taken periodically to record
the development of individual trees.
     Measurements  of  growth   were  made  for  each  tree
through the  month of November 1982.  November  marked a
time of  natural leaf abscission,  at this stage,  it was
difficult to distinguish a  dormant  tree from a dead one.
The  measurements   that  were  taken were  for  height  and
basal width were made using a standard tape measure and a
vernier caliper.  Trees were hand watered to supplement
rainfall.
Grasses
     Grasses were  planted after  a long  period  of heavy
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spring rains on  June  29,  1982.   All areas were tilled to
a depth of 10 centimeters.  In each of the three areas A,
B and C, four 1.83 meter by 1.83 meter plots, were marked
off and a 1.22 meter space left between each plot.  These
plots were located adjacent to the tree study areas.
     The crabgrass seed that was used was a hardy experi-
mental  variety,   selection  RR-174.   Crabgrass seed  was
donated by the Samuel  Roberts  Noble Foundation, Ardmore.
Weeping lovegrass  and  colonial  bentgrass  seeds were pur-
chased from local dealers.  The bermudagrass sod was tak-
en from fairly pure stands growing within one mile of the
study site.
     A 1.9 centimeter layer of commercially processed cow
manure  was spread  on  each  of  the  tilled plots.   The
manure  contained  1%   total   nitrogen,    1%   available
phosphorous acid  and  1%  available  potassium.   Grass seed
for  all   species  was  broadcast  at  a   rate  of  3.4
kg/hectare.   A  final  0.6  centimeter  covering  of  the
manure was  spread over the  seeds.   The bermuda  sod  was
cut with a sod stripper and placed on the prepared manure
bed by the solid sodding method.  All plots were watered.
     Due to unforeseen weather related delays,  a second
attempt was made to establish the grass plots on July 27,
1982.  The techniques employed were basically the same as
before with  only  two  exceptions.  First,  the  soil  was
tilled only to a depth of 1.5 centimeters  for all plots
prior  to  seeding.   Second,  bales  of  wheat  straw  were
mulched and a  thin layer  placed over  the  prepared seed
beds.
     Visual observations were made  to determine if seeds
were germinating and maturing.   Photographs were taken to
assist  in  monitoring  the progress  of  the study  plots
during the remainder of the growing season.  Samples were
analyzed  for  depth  of  root  penetration  by  digging  up

                         100

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plants with a shovel and measuring the length of the
roots.
Environmental Chamber Studies
     Environmental chambers  were  used to  provide  a con-
trolled environment in which plant responses to soil from
areas A,  B and C  could  be studied under  optimum  condi-
tions.  Crabgrass seed and bermudagrass sod were selected
because of their ability to survive at the land treatment
site.
     Soil was collected  from each  of  the  three study ar-
eas at the   field  site   and  placed  in 114 liter plastic
containers.  Dow  Fume MC-2  was  used  to  kill  extraneous
weed  seeds  in  the control soil.   This penetrating fumi-
gant contains 98% methylbromide and 2% chloropicrin.  The
soil was tested for nutrients and oil content as shown in
Table 10.6.
     Plastic pans  which  had  small drainage  holes  in the
bottom of them  served   to contain the  soil .and  grass.
Crabgrass seed, at a rate of  O.lg/pan, was placed in each
of nine pans which were  23x23x7  centimeters. Bermuda sod
was  placed in  the nine deep  pans  which were  23x23x13
centimeters.  Triplicate pans were set up for  soils from
each of the three areas.
     Soil that was placed  in the plastic  pans  was first
forced through a  0.95 centimeter sieve.   The  small pans
were  filled  with soil to  within  1.3 centimeter  of the
top.  The  deep pans  were filled with  soil  to  within 5.1
centimeters of the top.
     Based on  the  results  of nutrient analysis,  nitrate
nitrogen was added to the soils to the equivalent rate of
277 kg/hectare.  Nitrogen  was  added  to the  soil  in each
pan-  by  first  weighing  out  the   appropriate  amount  of
nitrate  nitrogen  and diluting  it with  water  and then,
spraying the solution onto the  soil surface.
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     The pH  of  the control soil was  slightly lower than
the test sites (6.4).  Limestone was added to the control
soil,  in  field  area  prior  to  planting,  as  calcium
carbonate to  bring the pH up  to  6.9.  The  soil  in each
pan  was mixed  with  water  to ensure  optimum  moisture
conditions.
     A 1.3 centimeter  layer of composted  cow manure was
spread on top of each pan of soil  The crabgrass seed was
spread  across the  top  of  the manure  and  a  final  0.6
centimeter layer of  manure  was spread over  the  seed and
watered.  The bermudagrass  sod  was  cut  from  an  area
adjacent to the field control site.  The sod was cut into
15 centimeter by 15  centimeter  squares  and laid into the
deep pans of  soil.   The sod was pressed  down firmly and
soil was packed in  around  the  edges of  the pans.  Final-
ly, sod was thoroughly watered.
     Pans with  soil from  area C  were  placed in  an en-
vironmental chamber which was  separate  from the one that
the soil from areas A and B were  placed  in.  Both cham-
bers had an approximate  relative humidity of 60% and had
temperatures  of  28°C for 16 hours of daylight  and 22°C
for  8  hours   of  darkness.   Incandescent  and fluorescent
lights  were   used  to provide  daylight conditions.   The
pans were watered as needed throughout the study.
     The plants  were  allowed   to  grow  for  two  months.
During this  time  period they  were measured  for height.
The above ground biomass was calculated on a dry weight
basis via standard procedure.
RESULTS AND DISCUSSION
Field Studies
Trees
     Soil samples were collected for oil content analysis
at the  time  when  trees and grasses  were  planted.   These
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samples were collected and composited for each of the ar-
eas containing trees  and  grass.   Table  10.1 contains the
percent oil  content  for  these locations.   The concentra-
tions of oil present at  the  land  treatment site far ex-
ceeds  the  values  commonly  used  in  other  studies  which
were reviewed  in the literature  (Brown  1979,  Carr  1919,
Giddens 1976, Schwedinger 1968).

          TABLE  10.1   OIL CONTENT ANALYSIS
Date
3/26/82
3/26/82
6/29/82
Sample
Location
Trees
Trees
Grass
0-25 cm.
25-51 cm.
0-25 cm.
% Oil Content
Area A
5.3-5
0.0-0
4.1-5
.6
.2
.0
Area B
9.6-12
0.2-10
14.4-15
Area C
.8 <0 . 1
.7 <0 . 1
.4 <0 . 1
     Table  10.2  summarizes  the  growth  measurements  for
the five tree species planted at the research site. Field
measurements  for  the growth of  individual  trees appears
in  Appendix D.   When  the  trees were  initially planted
there was  no  significant difference between  the size of
the trees  planted in the  land treatment area  and those
planted in the control area.
     During the months of April  and May the trees in all
three areas appeared to  be developing  normally.   There
was one noticeable difference  however  with  the red cedar
trees.  The cedar trees in area B were pale in color com-
pared to  the ones  in  area  C.   This  distinction became
more pronounced as the months passed until finally in Au-
gust all of the needles were red and  dry.   In area A the
color difference was not noticed until June.  The red ce-
dars in area A remained pale green throughout the summer.
By  September,  the branches  on  most  of the  cedar trees
were a mottled red and green.  The  cedar trees in area A
                         103

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     TABLE 10.2   MEAN  VALUES FOR TREE HEIGHT  AND  WIDTH


Date

Area
No.
HEIGHT (cm)
Trees Mean Std. Dev.
WIDTH
(cm)
Mean Std. Dev
BLACK LOCUST
April 7, 1982

July 27, 1982


Sept. 8, 1982
•

A
B
C
A
B
C
A
B
C
9
10
10
9
8
10
4
0
10
24.122
21.490*
27.480
41.267*
21.138*
193.550
49.225
—
218.850
2.422
6.214
4.739
16.384
3.889
40.957
23.216
—
48.194
0.532
0.336*
0.653
1.048*
0.878*
1.824
1.118
—
2.325
0.209
0.091
0.202
0.295
0.154
0.325
0.180
—
0.591
HACKBERRY
April 7, 1982

July 27, 1982


Sept. 8, 1982


A
B
C
A
B
C
A
B
C
9
10
10
9
10
8
1
1
9
26.887
23.370
28.690
20.356*
21.260*
34.250
29.500
24.500
26.233
6.885
5.939
7.974
7.572
6.734
10.866
—
—
11.831
0.302
0.256
0.350
0.313
0.233*
0.380
0.410
0.380
0.372
0.096
0.083
0.100
0.093
0.053
0.066
—
—
0.060
OSAGE ORANGE
April 7, 1982


July 27, 1982


Sept. 8, 1982


A
B
C
A
B
C
A
B
C
9
10
10
9
8
10
6
2
10
21.767
18.160
21.010
20.467*
19.162*
62.550
16.600*
7.150*
78.900
5.278
3.338
5.904
6.915
4.579
20.818
6.856
4.596
30.540
0.988
1.031
1.190
0.495*
0.238*
0.748
0.550*
0.210*
0.869
0.271
0.186
0.155
0.144
0.063
0.134
0.101
0.283
0.152
(continued)
                          104

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                         TABLE  10.2   (continued)
Date
Area
No.
Trees
                                   HEIGHT (cm)
Mean
Std. Dev.
                                       WIDTH (cm)
Mean
Std. Dev
                             RED CEDAR
April 7, 1982


July 27, 1982


Sept 8, 1982


A
B
C
A
B
C
A
B
C
9
10
10
9
10
10
9
10
10
31.811
33.200
34.240
33.922
33.770
36.150
30.833*
27.480*
46.000
2.970
3.752
3.555
3.376
3.137
13.090
2.919
3.635
16.598
0.690
0.764
0.763
0.913
0.583
0.828
0.788
0.572*
0.894
0.222
0.323
0.244
0.488
0.215
0.292
0.224
0.192
0.318
                           RUSSIAN OLIVE
April 7, 1982


July 27, 1982


Sept. 8, 1982


A
B
C
A
B
C
A
B
C
9
10
10
8
9
8
2
0
8
20.233
22.300
22.860
23.700*
19.200*
42.438
21.250
—
43.312
7.443
6.909
4.344
7.191
4.514
16.790
10.960
—
19.806
0.726
0.654
0.544
0.677
0.643
0.651
1.055
—
0.676
0.346
0.228
0.154
0.432
0.196
0.143
0.629
—
0.182
          statistically significant at 0.05 level  when compared
          to control  area C
                               105

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regained  a  healthy green  color  after the  winter months
passed.   All of the red cedar trees in area C remained a
deep green throughout the study.
     The  color  differences  noted for the  cedar  trees in
the three areas  were  due to the effects of  heat and the
amount of oil  in the  soil.  In area B where the oil was
heaviest, the plants  appeared  to  be severely dehydrated.
The presence  of oil  in the soil   has  a  negative effect
upon the wetting ability of the soil.
     The  spring months  were  unseasonably  harsh.   Heavy
wind gusts damaged the tops of some seedlings by removing
the leaves,  buds,  and  growing tips.  Rain  caused  minor
damage by washing  soil  up around the base  of the trees.
Some trees had as much as 13 centimeters of soil piled up
around them.  Most of the trees adjusted to the change in
soil  level  by  putting  out  adventitious   roots.   Excess
soil  was removed  with   a  shovel from  around the  trees
without  disturbing the  roots.  Soil  was  washed around
trees  in  area  C as well  as  areas A and B;  however, the
damage was not as extensive.  Rainfall data for the study
period appears in Appendix E.
     Weeds  were a  problem in area C  during the  rainy
period because  they  grew to twice  the  size  of  the tree
seedlings and  were in • competition  with them for nutri-
ents .   A  weedeater and  lawnmower  were  used  to  cut back
these  weeds.   One  hackberry seedling was  accidently cut
and killed  along with  the  weeds and  one  red cedar was
shortened.
     There were  marked  changes in  the appearance of the
trees  during the summer months.   The data  in Table 10.2
indicate  that  while  the  number  of trees   in  the control
area  stayed nearly  constant,  those in  areas  A  and  B
decreased for all species.  All of the trees were dead in
area B at the conclusion of the  study  with  the  excep-
                          106

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tion of  one  red cedar.  The trees in  area  C  rapidly in-
creased in size throughout  the  summer.   All of the trees
on the land  treatment  site  grew slowly and were severely
stunted.
     The temperature  on  the dark  colored  land treatment
site was higher than that for the  control  site.   Some of
the trees  in areas A and B showed signs of heat stress.
Composted  cotton  mulch seed and  hull was  spread  around
the base of  each tree in  all  three  areas  to  lessen the
effects of reflected heat.  In  addition  to  the high tem-
peratures  which  the plants had  to cope with  during the
summer,  there  was an  increase  in  the volatility  of the
oily waste.   On hot days the  oily waste  was  especially
odorous  and  vapors could be seen  rising above  the soil
surface.  Daily  air temperature  data appears  in Appendix
E.
     Leaves  which  grew 14  centimeters or more above the
soil in  areas A  and  B  were  lost early in the summer.
This leaf  loss was  noted for all  of  the species with the
exception of red cedar.  The trees developed new buds and
then new  leaves within two to  five  weeks  after initial
loss.   Trees  in  area  B grew back  their  leaves only once
before they  succumbed.  The trees in  area A lost and grew
back their leaves anywhere from one to three times.  This
cycle of leaf loss and regrowth ended in early September.
The trees which survived in area A had new basal branches
and leaves which  were  close to  the ground.  Osage orange
and russian  olive  trees  had the most  cycles of  loss and
regrowth of  leaves  and the largest amount  of  new growth
from the rootstalk.
     The cycles of leaf loss and regrowth could have been
due to water stress brought about  by  the presence of the
oily waste in  the soil.  Volatile  compounds and heat may
also have had an affect on the  leaves.
                          107

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     Soil samples were collected  to  determine  if oil was
migrating horizontally to  the tree  roots.   Samples  were
collected from 8 centimeters  out  around  the base of  dead
trees  in  areas A  and B.   The samples  were taken  to  a
depth  of 25  centimeters  from  the   soil   surface.   The
averaged values for percent oil  content  are listed below
in Table

  TABLE 10.3  % OIL CONTENT 8 CENTIMETERS FROM TREE BASE
Date
3/26/82
6/29/82
11/25/82
Area A
0.00
0.51
0.89
% Oil Content
Area B
0.00
3.65
4.33
     It  is  apparent from data  in Table  10.3  that there
was  some migration  of  oil.  Casual  observation  of  the
roots  of dead trees reveals  that there  were  few branch
roots  present.   The values for  percent  oil  content  in
Table  10.1  indicate that the top  25  centimeters of soil
contained more  oil  than did the  25-51  centimeter depth.
The  concentration  of   oil  may  have  affected  the  root
development.
     In  the control area  all of  the species  grew well
with the  exception  of the  hackberry tree.  The hackberry
seedlings were very small  in  size from  the start of this
study and remained  small throughout.  The seedlings' size
could explain the poor growth of this species.
     Two  russian olive trees faired exceptionally well in
area A.   The final  height  and  width of  these two trees
were not significantly  different  from  the  russian olive
trees in  the control area.  These  two russian  olive trees
were  unique  in  that   they  were  the  only  species  not
                          108

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significantly different from the controls.
     Four black locust trees survived in area A, but they
were  severely  stunted  compared  to  the control  trees.
Five of  the  nine  red cedar trees planted in  area  A were
also alive.    In addition  to  stunted growth,  they were
pale in  color and many of  the  needles had turned red and
dry.   Five  osage orange  trees showed  signs  of  life  in
area A.  Most of the  osage  orange  trees  were  so severely
stunted  that their  height  and  width could not be measur-
ed.  The parts of the osage orange trees which were alive
and green  were  young shoots  and  leaves which  grew from
the root stalks.
     The  trees  growing in  area A  were  unusual  in that
they were green  and had  most of their leaves  as late  as
November 25, 1982.  The trees  in  the control  had already
undergone leaf  abscission  and  were dormant by  the first
of November,  These effects were probably a result of the
high soil  and air  temperatures  in the  area  due  to  the
dark colored soil absorbing heat.
Grasses
     The long duration  of  rain in  the spring forced the
planting of  grass  to  be  delayed until late June.   Three
weeks  after  the grass was  planted  none  of the  seed had
germinated.  The seedbed for the  grass dried  out quickly
between waterings.   The plots were reseeded in late July.
     The straw mulch  used  for  the  second attempt  to es-
tablish grass on the plots helped to hold moisture in the
seedbed.  The soil was not  tilled as  deeply  for the sec-
ond seeding  as  it  had been for the first.   Shallow til-
ling depth prior to tilling allowed for  more  seeds to  be
kept on the soil surface.
     After one month only crabgrass and bermudagrass were
growing successfully on the land  treatment  site.  A cou-
ple of  small isolated lovegrass seedlings were located.

                          109

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A third  unexpected grass was  found  to be doing  well  on
the plots in areas A and B.  This third grass species was
barnyardgrass   (Echinochloa   crusgalli).    Barnyardgrass
seed had  apparently been mixed  in with the  wheat  straw
used as  mulch.   Barnyardgrass is  a weed  commonly  found
near the study location.
     Barnyardgrass  and  other weeds were  responsible for
taking over  area  C.   The presence  of additional  water
stimulated weed  growth  and most of the seeds planted  in
the study plots were outcompeted.  Crabgrass and bermuda-
grass,  however, fared well in area C.
     Poor germination results for many of  the seeds  under
study  was  attributed  to a  number of  factors.  One  of
these factors was the delay in planting time.  The spring
months would  have  been  the  best  time for  seeding  pur-
poses.   Another  factor  was  the thickness  of  the  straw
mulch placed  over  the seedbeds.   Wind action piled  much
of  the  straw up making  germination  impossible  in  some
sections of  the study  plots.   A  factor  which accounted
for seed  loss was damage  caused by a flock  of guineas.
Since  guineas can  fly  they were  able to  fly over our
control fences and  fences over the  top of  the plots  were
beyond the scope of this project.
     Soil was tested  to  ensure that there  were no nutri-
ent deficiencies which  might  affect  the  health of the
plants.  Fertilizer had  been applied  in the early spring
     •
prior  to  planting  of  the trees  and  grass.   Table  10.4
provides the  results  of the  nutrient analysis.   Since
nitrogen was  found to be  low  in all  three  study areas,
ammonium nitrate fertilizer was  applied at  a rate of 227
kg/hectare in early September.
     The bermudagrass  sod which was  growing  in  areas  A
and B was not as lush and thick,  nor as green as compared
to area C.   Bermudagrass sod on the  land  treatment  site

                          110

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showed a definite edge effect in that all of the edges of
the sod which were in contact with the oily sod which

    TABLE 10.4  NUTRIENT ANALYSIS FOR FIELD SITES

                                 Kilograms per Hectare
Area
A
B
C
pH
6.9
6.9
6.6
Available
(P2o5)
180
75
83
Available
(K20)
395
395
163
Magnesium
1055
907
1361
Calcium
6010
4990
2944
NO N
19
16
12
were  in  contact with  the  oily soil  surface  were yellow
and curling.  The  center of the sod  plots  was green and
healthy.  The sod  growing  in area B was  not  as green as
the sod  in  area A.   The bermudagrass sod  in  area C did
not have an edge effect  and  many  runners were spread out
from  the  sodded plot.   No  runners were  observed on the
plots in the land treatment areas.
     A few sprigs of bermudagrass were growing in the un-
contaminated soil around the base of the  trees in areas A
and B.   These  sprigs  sent  out one to  two  foot  runners.
These  runners  were  abnormal because  they  were  not at-
tached to the  soil surface.   Normally  the  runners would
have  roots  at  each  node to secure the  plant.   Instead,
the runners spanning across the soil in areas A and B had
only the shriveled up  remains of roots at the nodes.
     The depth  of  root penetration was measured on Octo-
ber  19,  1982 for  crabgrass, bermudagrass  and barnyard-
grass to  see if root  growth was  inhibited by the  oily
waste.  Compared with  the roots of plants growing  in area
C there was no  difference  in the  length of roots  for any

                          111

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of the  species  growing in areas A  and  B.   Crabgrass and
bermudagrass had  roots which penetrated 18  to  20 centi-
meters  into the soil.   The  barnyardgrass had roots which
were between 20 and 26 centimeters long.
     Where the  grasses were growing, the  top  6.1 centi-
meters  of  soil,  in areas  A  and B was  fairly dry.  Below
this  top dry  layer  the  soil  was  very  wet and soggy.
Table 10.5 lists the percent oil content for soil samples
which were  taken to  a depth  of • 15  centimeters.  These
samples were collected in October from the grass plots.
         TABLE 10.5  OIL CONTENT OF GRASS PLOTS
Grass Type
Seeded Grasses
(Composite of plots)
Bermudagrass Sod
Area A
4.50%
6.24%
Area B
12.25%
13.22%
     In  addition  to  the  grasses  growing  on  the  plots,
three  new  plant species  were  discovered on  an untilled
section of the  land  treatment  site.   The first plant was
growing in soil which had an oil content of 3.67%.  This
plant  was  identified as  either Aster  exilius Ell.  or
Aster  subulatus  Michx.   var.  ligulatus  Shinners.  The
plant  stood  about  100  centimeters  tall  and  had roots
which  penetrated  30  centimeters  into  the   soil.   The
flowers were unusually small for this species.
     The  other plants  which  were  growing  in  the  land
treatment  area  were  grasses.   One  of these  grasses was
Setaria  glauca (=§_•  lutescens).  The  roots  of Setaria
glauca penetrated  down to  18  centimeters  in  soil which
had an oil content  of 4.6%.   The second  grass was unable
to -be  identified  and was most likely  an introduced spe-
cies.  The roots  of  this grass  were  13  centimeters long
and the oil  content of the soil  in which  it was growing
                          112

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was 1.75%.
     Measurements  were not  taken for  the  above  ground
height  of  the  grasses  in  this  study  because in  late
September  they  were  eaten.   A  large  steer  had  escaped
from  a  nearby ranch  and  jumped  over our  5  foot  control
fence  and was observed eating the grass.
Environmental Chamber Studies
     The  soil used for study in  the environmental cham-
bers was  taken  from areas A, B and  C.   An evaluation of
the available nutrients, pH, and oi-1 content of this soil
appears in Table 10.6.
     Water  was  added  to  the soil prior to  planting  to
provide  adequate  moisture  for  the  seeds  and  sod.   The
water could  not  be sprayed directly on  the  soil  surface
because  it  tended  to  run  off  and drain  through  without
wetting the soil.  The soil was wet by mixing water in

 TABLE 10.6  ENVIRONMENTAL CHAMBER SOIL CHARACTERISTICS
Kilograms per Hectare
Area
A
B
C
Oil
Content
8.7%
13.5%
0.0%
pH
6.8
6.8
4.6*
Available (P 0 )
Phosphorous
75
37
37
Available (KO)
Potassium
299
381
245
Mn
740
646
1701
Ca
4649
4763
3515
NO N
**
86
22
66
*   pH adjusted to 6.9
**  Values increased to 227 kg/hectare with NO.N addition

with a spoon and stirring vigorously.  Once the soil con-
taining the oily waste was wet,  it retained moisture for
a long period of time.
     The  germination  of  crabgrass  seed planted  in soil
from areas A  and  B was delayed by  7-10  days as compared
                          113

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to seed planted in soil from area C.  The crabgrass seed-
lings growing in  the  oily  soil  appeared to be normal the
first 10  days  after germination.  Thirty  days  after the
seed was planted, crabgrass plants in the soil from areas
A and B were discolored and severely stunted.  The leaves
were curled and  pale.   Some  of  the crabgrass plants were
starting  to yellow  and  the tips  of  leaves were  red.
Plants grown in  the soil from area C were all  green and
healthy.
     The  crabgrass  grown  in  soil from  areas  A  and B had
renewed growth 50 days after planting.  After most of the
leaves  appeared  to  undergo  senescence  the leaf  color
improved and new tillers were produced.   Table 10.7 lists
the mean height values for the plants 40 days and 70 days
after they were planted.
     In general  the  crabgrass grown in  the environmental
chamber,  in soil  from  areas A  and B,  did not  look  as
vigorous  as that which  grew   at  the  field site.   The
difference  in  appearance could  have  been  the  result  of
exposure  to volatile  compounds.  Wind activity  in the
field would decrease the amount of exposure that plants
would have to volatiles.
        TABLE 10.7  MEAN HEIGHT VALUES  FOR GRASS
Height (cm) after Planting
Area of Soil Origin
Crabgrass
A
B
C
Bermudagrass runners
A
B
C
Bermudagrass sod
" A
B
C
40 days

3.6
1.5
18.0

59.8
48.4
95.2

20.7
15.9
46.7
70 days
•
3.7
2.6
26.9

80.0
70.6
116.9

23.0
21.0
38.0
                          114

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     Bermudagrass sod was clipped the  day  it was planted
such that  the height  of  the  sod was  7 centimeters  and
equal for all pans.  The runners which grew  over the  top
of the pans were measured along with the thick growth in
the center of  the  sod.  Height measurements  are located
in Table 10.8.
     Throughout the study the  bermudagrass which grew in
the pans containing soil from  areas A  and  B  were pale in
color and grew slowly  as  compared to  the  sod  growing in
the soil from area C.   The  above  ground  biomass was cal-
culated on a dry weight basis for  all  of the  grass seven-
ty days after planting.  Total biomass  was not calculated
because oil adhering to the  roots  would introduce a large
error.   The biomass values are listed  in Table 10.8.

       TABLE 10.8   ABOVE GROUND BIOMASS OF GRASS

Area of Soil Origin        Dry wt  (g)        % of Control

Crabgrass
    A                         0.46               2.55
    B                         0.43               2.39
    C                        18.01             100.00
Bermudagrass
    A                        56.47        •      21.76
    B                        32.31              38.03
    C                       148.49             100.00
DISCUSSION
     The revegetation of a land treatment site containing
large amounts of oil, although possible, is not desirable
until much of the oil has been degraded.  Soil containing
high concentrations of oily waste is more toxic to plants
than is soil with low concentrations.  Highly oiled soils
should be cultivated  by  tilling,  fertilizing,  and liming
as needed to degrade  waste  products.  The biodegradation
                          115

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of oily waste  may actually be slowed with  a plant cover
present because  the  soil could not  be  cultivated.  Fre-
quent fertilizer  additions  necessary to degrade a highly
oiled soil may cause injury to plants.
     Once  the  oil has  been  sufficiently  degraded on  a
land treatment site,  revegetation efforts  should begin.
Vegetation on  a  land treatment site  would  serve  to pro-
tect the  soil  by intercepting and dampening the  effects
of  rainfall  and  wind  activity.   The  main purpose  for
growing vegetation  on  these  sites  would  be  to  protect
against erosion  and  off-site transport of soil  and  or
waste material.   Plants  can also  be used to dry  out  wet
areas and help improve aeration.   A vegetative cover crop
could  also be used  to  help  monitor the  toxicity of  a
closed land treatment site.
     The  selection of suitable plant species  to  be used
on a  land treatment  site is  difficult.  There is little
data available on the revegetation  of  these sites.  In-
formation  on the  uptake  of  hazardous materials by plants
is limited at  this time to the  uptake  of  metals and to
the effects of selected pesticides.   Generally speaking,
it is  important  to plant species,  subspecies or ecotypes
in an  environment similar  to those  on which  they occur
natively.
     Plants which are  selected for revegetation purposes
should be  adapted to  the soil and  climatic conditions in
the  area   in which  they  will be  used.  Any  first hand
knowledge  gained  about  plants growing  in  specific geo-
graphic areas  is  helpful.   A  knowledge  of  the attributes
of plants  is helpful to  select the most suitable ones for
revegetation purposes.   Consequently,  the  experience of
others furnishes a good  beginning.
     All of the plants used in this  study were subject to
adverse environmental conditions which  represent  some of

                          116

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the  unavoidable  risks that  occur when  conducting  field
studies  of  this type.   Based upon  the  results  of  this
study, hardy  species  which are  fairly  drought resistant
should be used  for site revegetation.   Despite  the  fact
that adequate water was  provided for the plants, many of
the trees exhibited signs  of  dehydration.   The red  cedar
tree  which  is  very  drought  resistant  fared the  best.
Drought resistant  species  were better  suited  to  the  soil
at  the  study  site because of the high  temperatures  and
altered soil-water relations associated with the presence
of oil in soil.
     Care must  be  taken when watering  vegetation  on  a
land treatment site because once wet,  the soil will  hold
moisture and  increase the  chances  of the  soil  becoming
anaerobic.   Soil  moisture  must  be  adequate to  not  only
meet  the  needs  of  plants, but  also to  support optimum
conditions  for   the  microorganisms  degrading   the  oily
waste.
     It is critical to monitor the soil nutrients.  These
nutrients supply  the  microorganisms  as  well  as plants.
In a competition for  nutrients between plants and micro-
organisms ,  Meyers  and Huddleston (1979)  concluded  that
lower  nitrogen  content   in  wheat  was  the  result  of
assimilation by  microorganisms  degrading  the  waste  oil.
The use  of  nitrogen fixing plants  for  revegetation  pur-
poses may help to alleviate this  competition for nitrogen
which is often  a limiting factor to  oil degradation and
plant growth.
     Grasses are the best  choice  for initial revegetation
of a land treatment site.   Grasses  provide a quick  cover
and  have  root systems which  can hold  the top  layer of
soil in place.  If grass is to be planted as seed prepa-
rations are needed to assure good germination and healthy
growth.  A layer of composted materials such as manure or

                           117

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possibly treated sewage  sludge,  should  be  tilled in with
the  surface  soil  and  used  as  a  seed  bed.  This  would
buffer  the  vulnerable  seeds  from  the hot  soil  surface,
help retain moisture and  cause  less  injury to seeds from
volatile  compounds  and  dissolved  constituents  during
germination and  early  growth.  Our  study  indicated that
approximately a  2.5 cm  layer of  composted  material  was
beneficial.
     Viable seed from native species are often  difficult
to obtain; therefore, good commercial seed should be used
for  the  revegetation  of  closed  land   treatment  sites.
Grasses may also be planted  on  a site as sod.  If sod is
used it should  be  thick  and healthy.   Large sod blocks
are  desirable to limit  the  edge effects associated with
growing sod on this type of  soil surface.
     The  survivability  of trees on  land treatment  sites
depends on a number of  factors.  The most  important fac-
tors are  the  concentration  of  the oil  and  the  depth of
penetration of that oil in the soil.   Tree growth and de-
velopment is affected  by the amount  of  available water,
nutrients, and toxic constituents in the oily waste.
     Until a  tree  has  recovered  from the  initial  shock
that planting causes  its root  system,   it  should not be
exposed to the oil contaminated soil.  In order to buffer
the  roots from the  treated  soil  a  large hole about  twice
the  size  normally  used  to plant the  tree  should be used
and  filled  in with uncontaminated soil.   This  will give
the  tree  time  to establish  itself before  the roots come
in contact with the oily soil.
     The  grasses  which  yielded  the   best  growth  and
appeared to be the most resistant to the presence of oily
residues  in this study were crabgrass  and bermudagrass.
The  red cedar had  the  highest survival  rate in  the test
plots  followed by  russian olive,  black  locust  and  osage

                          118

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orange.  The grasses and trees selected in general proved
to be  good choices  for  the field conditions  which were
present.
     The revegetation of land should be an important part
of the  site  closure procedures for  land  treatment sites
which contain oil  refinery  waste.  A revegetated site is
functionally and aesthetically appealing but, until suit-
able plants  which  can  adapt  to  the  unique environment
created by  a land  treatment  system are  identified,  the
revegetation of closed sites  remains as much an art as a
science.
                          119

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                       SECTION 11
                       DISCUSSION

     The current regulations  governing  land  treatment of
hazardous wastes were published  on  Monday, July 26,  1982
in Vol. 47, No. 143 of the Federal Register.   A number of
the regulations listed were evaluated on the  basis of the
results of this project.
     The treatment zone is defined as the region from the
soil surface down to a depth of 1.5 meters (5 feet),  with
the proviso that the bottom of the  zone must be at least
1  meter  (3 feet)  above the  seasonal high  water  table.
The results of this experimental work  suggest  that  this
minimum depth above the water table may be too shallow to
prevent  salts  and  solubilized metals from  reaching  the
ground water.   The  lysimeters were installed at  a depth
of 4 feet and  elevated  levels  of chloride, barium, zinc,
iron,   manganese,  and  TOC  were  found  in  the  soil  pore
water.  In addition, the metal concentrations in the soil
below  50  cm at the  sites  were  not  statistically  higher
than background levels.  This means  that once metals are
solubilized, and  migrate below  the  top  50  cm  of soil,
they remain in  solution  and migrate  with the pore water.
Furthermore, it appears that oil which migrates below the
aerobic  zone  (top 20-25 cm) ,  while  immobilized,  is  not
degraded and may  act as a source  of  contaminated leach-
ate.
     Unpublished work by the authors on land treatment of
oily sludges,   shows that migration  of oil  below the till

                          120

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zone is  possible  even at low  (3-5%)  loading  rates.   The
exact mechanism  by which this  migration occurs  has  not
been determined,  but the movement of  infiltrated  water
caused by heavy rain  may be  the driving force.   Movement
of oil below  the  till zone  is  difficult  to control  even
at well managed sites with low loading rates.
     Closure requirements include:
(1)  The continuation of all operations required to maxi-
     mize the  degradation/  transformation or  immobiliza-
     tion of hazardous  constituents  within  the  treatment
     zone.
(2)  Control of run-off and run-on.
(3)  Continuation of  unsaturated  zone monitoring, except
     for soil pore liquid monitoring which may be termin-
     ated 90 days  after  the  last  application  of waste to
     the treatment zone.
(4)  The  establishment  of a vegetative cover,  when  the
     cover will not interfere with the continued treat-
ment of the waste.
     The  results  of  this research project,  support  the
need for all of the requirements listed.  However, it ap-
pears that  at  sites with high  loading rates, fulfilling
requirement number  1  may take  a  considerable  period of
time.  In addition, the results suggest that both organic
and inorganic pollutants can move through the unsaturated
zone in  pore  water  for longer than  90  days  after  the
wastes have been  applied.  The presence  of  organics at
site 2,  six  years after closure, even  though  only in
trace amounts, supports  the  need  for extended monitoring
of pollutants  in  the unsaturated  zone in  pore  water as
well as  soil  cores.   However, it  must  be noted that the
rate at which oil is applied to the site, and the rate at
which it  is degraded will  determine the length  of   time
for which  monitoring  the soil  pore water  must  be main-
                         121

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tained.
     The results  of  this study suggest  that  grasses are
the best choice for initial revegetation of a land treat-
ment  site.   Results also  indicated that  oil  concentra-
tions of  4-5%  were sufficiently low  to  allow successful
revegetation with grass.  However,  the  growth of grasses
was inhibited, and establishing a grass cover undesirable
because  the rate  of  further  oil  degradation  would  be
inhibited, since tilling of the site would have to cease.
The authors therefore recommend that revegetation of land
treatment sites not  be  implemented  until the degradation
rate has decreased to some low constant value.
                          122

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Fuller, W.H.,  "Movement of Selected Metals, Asbestos and
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Giddens, J., "Spent Motor Oil Effects on Soil and Crops",
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Gould, Frank W., Common Texas Grasses, Texas A & M Univ.
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                          124

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Grove, G.W., "Use Landfarming for Oily Waste Disposal",
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                         125

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                          126

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                          128

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                       APPENDIX A
                   ANALYTICAL METHODS
Oil Content
     Two procedures were used  for  oil  content determina-
tions.  The  oil content of  the sludges and  soil  sludge
mixtures was determined by  extraction  with dichlorometh-
ane, using the procedure of McGill and Rowell (1980) .   In
this procedure, 10 grams of the sample were extracted for
4 hours using  a Soxhlet extraction  apparatus.   Prior to
extraction,  the  soil was  ground so  that  it could  pass
through a 40 mesh sieve, and then quartered to obtain the
desired sample size.   The  extract  was then evaporated
down to a  volume  of 15 to 20  ml  on  a  steam bath,  trans-
ferred to a  preweighed  aluminum dish,  and  allowed  to air
dry in a fume hood overnight.  The sample was then purged
with nitrogen  gas,  by  directing a steam at  the  gas  onto
the  surface  of the  residue in the  aluminum dish.   The
purging was  necessary  to drive off  any remaining dich-
loromethane.   The residue  and  aluminum  dish were  then
weighed, and the  weight of  oil determined.  The thimbles
plus soil were oven dried at 103°C, and the weight of dry
soil obtained.  The  oil content was then  expressed  as a
dry weight.
     The oil content of  the  aqueous  samples was  deter-
mined  gravimetrically,  using  method  413.1  from  test
"Methods for Chemical Analysis of Water and Wastes"  pub-
lished by the Environmental Protection Agency (March
1979) .
Fractionation Analysis of Oil
     Fractionation analysis on the oil extracts from the
site soils  was carried out using  ASTM Method D-2007-73.
Ini-tial analyses were performed on standard oils obtained
from the Agronomy Department  at Texas  A  & M University,
to verify the method.
                          129

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Metal Analysis
     Heavy metal  analyses were  carried out  on  sludges,
site  soil,  and soil  pore water.   The sludges  and  site
soil  samples  were analyzed  using a  digestion  procedure
obtained  from  the   Environmental   Protection  Agency's
Robert S. Kerr Environmental Research Laboratory (RSKERL)
in Ada,  Oklahoma.   In this procedure,  between 0.2  and 1
gram  of  sample  was accurately weighed  in  an acid-washed
beaker,  10 mis  of concentrated nitric  acid  added  to the
beaker,  and  the  mixture just evaporated to  dryness.  10
more  mis  of  acid  were then added to  the beaker,  and the
beaker was  covered a'nd  allowed to  reflux gently  for a
minimum  of 2  hours.   When ashing of  the sample  was com-
plete, indicated by the absence of vigorous reaction, the
beaker was cooled, 1  ml  of 30%  H_02 added  and the diges-
tion  was continued.   Additional  1  ml portions  of  ^2°2
were  added up to  a maximum  of 10 mis, until ashing was
complete.  This  stage was denoted by  no  further changes
in the color  of the  sample.  The cover was  then removed
from  the beaker,  and the  sample evaporated  until  just
dry.   3  mis  of nitric acid  were then  added,  the beaker
heated  to solubilize  the residue,  and then  25 mis  of
water were added.   The beaker was  then covered,  and the
contents  allowed  to digest  for  1 hour.   The  sample was
then  transferred to a  100 ml volumetric flask, diluted to
volume,  and analyzed by AA.
      The  aqueous samples were prepared  for analysis  using
methods  3010  or  3020  from "Test Methods  for Evaluating
Solid  Waste-Physical/Chemical  Methods" published  by  the
Environmental Protection Agency.
      All  samples  were analyzed on  a  IL Model 551 Atomic
Absorption Spectrophotometer,  equipped with  a  Model  655
furnace.
                          130

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Chloride Analysis
     The method  used  for chloride analysis  of  soils was
taken  from  "Methods of  Soil  Analysis" published  by the
American Agronomy Society (Black et al., 1979).   Both 1:5
and 1:1 ratios of soil to water  were  used.   The chloride
ion concentration in the soil spore water samples was de-
termined using method  325.3  - titritmetric  determination
with mercuric nitrate - taken from the EPA manual Methods
for Chemical Analysis of water and wastes.
pH Determination
     The pH determination for soils was done according to
the procedure outlined in Methods of Soil Analysis (Black
et al., 1979).
     The soil sample was diluted 1:1 with water  and mixed
for 30 minutes.  The mixture was allowed to stand for one
hour to settle, and then the pH was determined using an
Orion Model 401 pH meter.
Nitrate
                              i
     Soil nitrate determinations were  carried  out using
the phenoldisulfonic  acid method described  in  part  2 of
Methods  of  Soil  Analysis   published  by  the   American
Agronomy Society (Black et  al., 1965).  This  procedure
involves the development of  a yellow  color  with phenold-
isulfonic acid by the nitrate ion in an aqueous  extract
of the soil.
Available Phosphorus - Bray's Method
     The method  used, determined  the phosphorus  in the
soil  soluble  in NH F/HC1 solution.   The procedure  used
was taken from Methods of Soil Analysis, edited  by Black
et al.
Total Organic Carbon
     The total organic carbon content of aqueous samples
was determined using  a Beckmann Model  915  Total Organic
                         131

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Carbon Analyzer  with an  infra  red detector.   The  total
organic carbon content of the soil samples was determined
in two ways.   The first set of  determinations  were car-
ried  out  using  the  Walkley-Black  Method with  external
heat  as described in Methods of  Soil  Analysis  edited by
Black et al.  In this method, the carbon is oxidized with
potassium  dichromate at  a  temperature of  150°C.   Later
determinations were performed on a Leco Total Organic
Carbon Analyzer.
Priority Pollutant Analysis
     The soil  samples were  extracted  for  priority pollu-
tant  analysis  by  using  a combination  of Methods 3540 and
3530  in the EPA Manual  Test Methods for evaluating solid
waste.  In the  first  part  of  the procedure,  the  solid
sample was subjected to  Soxhlet extraction  using  dich-
loromethane,  as  described  in  Method   3540.   The extract
from  this  procedure  was  concentrated  to about  2.5 mis,
and 0.5 mis removed  for analysis for  volatiles.  The re-
mainder was  then  extracted by  Method 3530,  yielding  a
base/neutral and phenolics  fraction.  The three  fractions
were  then  analyzed by GC/MS.  The  instrument  used  was a
Hewlett-Packard Model 5985B GC/MS.  The GC was fitted
with  a DB-5 30 meter, fused silica, capillary column.
Cation Exchange Capacity
      The  cation exchange  capacity of  the  soil  at each
site  was determined  using the ammonium  saturation method.
This  procedure was taken from "Methods of Soil  Analysis"
edited by  Black et al.  The procedure  entailed saturation
of the air-dried  soil with  neutral  IN  NH.OAC,  followed by
removal of the  absorbed NH,   by passing  air  through a
suspension of  the  NH.   saturated  soil  in Na-CO,  solution.
The displaced  NH.  ions were then passed  into a  container
with  H_SO..   By  determining  how much  acid reacted with

                          132
                          V

-------
the NH.+ ion, the concentration of  NH.   ion could be  de-
termined, and hence  the  cation exchange capacity  of  the
soil.
                          133

-------
                       APPENDIX B




                     SITE SOIL DATA




            TABLE B-l.  TOTAL ORGANIC CARBON




Site 1
Location

Bkg T
Bkg B
IT
IB
2T
2B
3T
5T
6T









TOC %
11/10/81
2.0
1.3"
10.0
0.9
10.2
2.1
13.4
13.6
4.9









Site 2
Location

Bkg T
Bkg B
IT
IB
2T
2B
3T
3B
4T
4B
5T
5B
6T
6B

7/21/81
1.1
0.5
4.2
3.9
4.1
1.3
4.1
1.8
6.7
7.2
1.7
1.0
0.7
0.6
TOC. %














11/12/81
0.8
0.3
4.8
0.1
4.0
0.2
5.3
0.3
5.5
1.3
6.9
1.9
4.6
1.3
 (continued)
                          134

-------
                 TABLE B-l. (continued)

Site 3


       Location                   TOC. %


                                 11/17/81

       Bkg T                        1.4
       Bkg B                        0.3
       IT                           7.6
       IB                           1.4
       2T                           1.7
       2B                           1.1
       3T                          14.6
       3B                           8.8
       4T                          13.6
       4B                          11.7
       5T                          18.4
       5B                          10.7
                          135

-------
      TABLE B-2.  CHLORIDE ION CONCENTRATION  (mg/kg)
Site 1
Date
6/30/82













Location
Bkg T
Bkg B
IT
IB
2T
2B
3T
3B
4T
4B
5T
5B
6T
6B
Concentration (mg/kg)
(1:5 ratio)*
17.6
15.4
167.0
136.1
161.5
112.1
68.1
70.4
108.8
87.4
106.6
130.5
105.5
83.5
(1:1 ratio)*
5.5
-
-
103.9
-
93.5
-
58.0
-
85.7
-
109.9
-
69.8
     *  Ratio of soil to water
Site 2
Date
7/8/82













Location
Bkg T
Bkg B
ITU
1BU
2TU
2BU
3TU
3BU
4TU
4BU
5TU
5BU
6TU
6BU
Concentration (mg/kg)
(1:1 ratio)*
13.7
2.9
24.9
28.1
24.9
45.1
19.0
-
28.2
23.9
34.3
35.4
36.9
-
(1:5 ratio)*
47.8
17.6
52.7
-
19.8
-
22.8
-
33.9
-
37.5
-
24.2
-
       Ratio of soil to water
                            136

-------
              TABLE B-2.   (continued)
Site 3
Date

11/4/82







Location

Bkg T
Bkg B
2T
4T
4B
5T
5B
'6T
Concentration (mg/kg)
(1:5 ratio)*
19.8
7.3
48.5
125.1
150.4
71.7
52.5
44.9

(1:1 ratio)*
15.4
4.1
17.2
99.6
141.7
51.1
49.2
52.1
*  Ratio of soil to water
                       137

-------
                   TABLE B-3.  SOIL pH
Site 1
Location

Bkg T
Bkg B
IT
IB
2T
2B
3T
3B
4T
4B
5T
5B
6T
6B
pH
11/10/81 12/1/82
7.4
7.5
7.2 7.1
' 7.5
7.6 7.0
7.5
7.4 7.2
7.3
7.1
7.3
7.2 7.0
7.5
7.5 7.1
7.2
Site 2
Location

Bkg T
Bkg B
IT
IB
2T
2B
3T
3B
4T
4B
5T
5B
6T
6B

7/21/81
6.8
6.8
6.9
7.9
6.2
5.8
6.2
5.8
6.7
7.3
6.1
6.2
6.4
6.3
PH
11/12/81
7.0
7.0
-
7.1
—
7.3
—
7.3
-
7.2
-
7.4
—

11/19/82
7.2
7.8
7.0
7.2
7.4
7.3
7.3
7.6
7.3
7.4
7.2
6.8
7.1
7.2
(continued)
                          138

-------
                 TABLE  B-3.   (continued)

 Site  3


 Location                           pH

                   7/16/81       11/17/81       3/26/82

 Bkg T               5.8           7.2
 IT                   7.5           7.4           7.7
 IB                   7.2
 2T                   7.4           7.4           7.1
 2B                   6.6
 3T                   7.2           -            7.5
 3B                   6.8
 4T                   7.6           7.3           7.3
 4B                   6.0
'5T                   7.3           7.4           7.6
 5B                   7.3
 6T                    -                          7.6
 6B                    -
                          139

-------
                                          TABLE  B-4.    OIL  CONTENT DATA %
•£>•
O
Site 1 Location
9/3/81
BGT 0 . 8
ITU 2 . 3
1BU 3.8
2TU
2BU
3TU 1 . 5
3BU 1.0
4TT 2.5
4BT 0.1
5TT 3.4
5BT
6TT 3 . 1
6BT 0 . 2
BGB

11/10/81
0.1
2.5
0.1
. 1.7
0.1
1.2
0.3
-
-
1.2
-
1.2
0.4
0.0

4/8/82
0.3
4.4
0.7
7.1
0.8
3.4
-
4.0
0.4
6.5
1.1
4.0
0.2
0.1
Date
6/14/82
0.5
6.6
1.9
-
-
2.5
0.1
-
-
8.0
-
4.0
0.1
0.1

6/30/82
_
-
0.7
-
8.0
3.6
0.3
5.5
0.1
-
-
6.2
0.1
"

8/4/82
-
-
-
5.8
1.0
2.3
0.2
-
-
7.1
1.5
-
-


12/1/82
0.5
6.9
1.5
7.7
1.2
2.9
0.6
4.7
0.7
8.3
3.0
3.2
4.1
0.2

1/18/83
1.0
5.9
-
8.2
-
-
-
-
-
7.9
-
5.8
-

          (continued)

-------
                                TABLE B-4.   (continued)
Site 2 Location

BGT
BGB
ITT
1BT
ITU
1BU
2TT
2BT
2TU
2BU
3TT
3BT
3TU
3BU
4TT
4BT
4TU
4BU
5TT
5BT
5TU
5BU
6TT
6BT
6TU
6BU
11/12/81
0.0
0.0
1.7
0.3
0.8
0.2
-
-
1.5
0.3
-
0.2
1.4
0.1
0.2
0.0
1.9
0.3
-
-
1.0
0.4
—
-
1.0
0.2
4/6/82
0.3
0.1
2.8
1.4
3.8
-
2.5
0.5
2.5
-
1.6
0.6
3.3
-
1.7
0.4
2.8
0.5
4.2
1.0
2.9
-
3.0
0.8
2.4
0.5
Date
7/8/82
3.7
0.5
2.4
1.1
3.1
1.6
3.0
1.5
4.8
1.0
1.7
0.6
2.9
1.9
1.8
1.0
0.4
1.1
4.0
1.2
3.7
1.2
-
-
0.7
0.2
11/19/82 6/16/82
0.4 3.1
0.4 0.3
3.3
— _
3.1
1.0
2.1
1.3
0.1
0.1
1.8 .5
0.1 0.1
1.1
0.2
1.2
0.3
3.7
2.8
4.7
3.0
3.6
2.1
4.5 0.2
2.6 0.1
4.3 1.3
0.3 0.2
2/16/83
0.6
—
3.0
_
—
—
2.6
-
-
-
1.7
—
—
-
0.7
-
-
-
5.1
—
-
-
4.7
1.7
-
-
(continued)

-------
                                                TABLE  B-4.   (continued)
K)
Site *3 Location

BGT
BGB
IT
IB
2T
2B
3T
3B
4T
4B
5TT
5BT
6T
6B

11/17/81
0.2
0.1
3.0
-
2.0
0.9
8.6
3.5
4.9
6.1
4.6
2.4
-
—

3/26/82
0.1
0.1
5.3
0.1
5.6
0.2
10.5
0.2
8.4
2.3
9.6
10.7
12.8
-
Date
7/29/82
_
• -
-
-
-
-
—
1 -
13.2
2.4
17.3
6.2
12.5
8.7

10/19/82 11/4/82
0.5
0.1
-
- -
5.2
— —
- -
- _
13.9
17.9
13.1 13.4
5.9
11.9
- -

3/8/83 6/7/83
1.1 2.3
0.1
4.0
0.5
5.7
0.9
11.0 9.3
1.4
15.3 14.1
8.6
20.8 15.6
9.9
12.0 9.4
9.5

-------
              TABLE B-5   SOIL METALS  DATA
SITE  1

SI TECUOE
10

1(3-6)
I (6-12)
2(0-6)
2(6-9)
3< 0-e)
4(0-dJ
             0-l4»
                   cu

               183.00
               129.00
               274.00
               141 .00
               246.00
                ta. oo
               310.00
               240.30

                   P9
                 15.00
                   .
                   .
                 13.00

                 24.00

                 30.00
    (continued)
                                a*
                                            SE
                    CO
                               2N
97.00
65.00
1S1 .00
83.00
291 .00
93. wi.
10.00
137.00
95.00
323.00
243.00
514.00
1 7u.OO
554.OO
SSo.OO
5ft. 00
saj.oo
O6O.OO
                                      29300.JO
                                           •
                                      21360.00
                                      3lo50.00
                                      2021J.00
                                                        AS
                                             Nl

<1*P"
I.CO
< '.00
O.PD
O.ffl
0 .00
<1.00
1 m 00

22.00
.
.
23. JO
.
22.00
16.1)3
26.00

•
314.00
29.00
42.00
75.00
4J.OO
137.00
79.00
82.00

37.00
                                             c«

                                         126.40
                                          aa.oo
                                         2e3.00
                                         I 07.00
                                         232.30
                                         317.00
                                           7.40
                                         350.00
                                         360.00
                                               F£
                    Reproduced from
                    best available  copy.
                               143

-------
                  TABLE B-5  (continued)
SITE  1
I 070^81S
10

aGoio-oj
BOB
        CO

     Jtt.OO
     11*00

        PB

     23.00
     27.00

        Avi

      • .00
      1.00
                               BA
                               CO

                            o.oo
                             «.oo

                               ZN

                            10.00
                            20.00
   cu

le. 00
 7.00

  Ai.
                                     20bob.00
                                                       AS
   Ml

I 17.00
 IV.00

   CP
                                                    J7.00
    (continued)
                      Reproduced from
                      best available  copy.
                              144

-------
                   TABLE  B-5  (continued)
SITE 1
strecuoc
in
10

ib
IB
IT
2b
26
2T
31
5T
OT
                                 SE
    AS

400.00
270*00
440.60
3*0.00
370.00
270.00
340.JO
4OU.OO
270.JO
                                CO
                 21.00
                100.00
                 42.00
                 JJ. 00
                143.OC
                IS*.00
                167.00
                 So. 00

Inn
* uu
«.. 00
O.OO
• .00
1.00
a. ao
*.oo
1.00
S. 00
7*00

13.00
7.00
10. 40
7.00
1 7.00
7.00
10.00
7.00
23.00

20.00
44.30
27.00
33.00
231.00
57. JO
44 .00
2S.OO
                                2.H
                                                         CR
43.00
43. Ob
137.00
33.00
47.00
93. OU
ioo.au
1*3.00
37.00
4«.00
61. 30
4A9.UO
73.OO
65.00
*7<>.OO
272.00
443. OC
IVb.uO
23160. 00
1 0600. 00
10710. OO
24220.00
2*140.00
18230.00
128di>.uJ
13170.00
iaa*u.oo
                                                      270.00
                                                      110.00
                                                      157.00
                                                      no. no
                                                       90.30
                                  MN
                   2.00
                   J.OJ
                  17.00
                   S.OO
                   S.OO
                  17.00
                  lo.OO
                  |7.uO
    (continued)
                        Reproduced from
                        besl  available copy.
                               145

-------
                   TABLE B-5  (continued)
SITE  1

SITECOOfe

1061402S
10

BCT
            IT
            ia
            3T
            3B
            6T
            60
            IT
                    Ctl
                    PB
                     A6

                   3.00
                   3.00
                  17.03
                   • .00
                   3.00
                   7.00
                   3.00
                  la. oo
    BA

 «e*00
 9«.t>0
 41 .00
101*00
174.00
 94.00
122*00
 to.bu
6JU.OO

    CO
13.00
9.00
202.00
76.00
6«. 00
13.00
1*0.00
14.00
215*00

o.oo
o.oo
o.oo
o.oo
O .1)0
0.00
0.00
.
o.oo
3d. 00
17.00
112.40
36.00
• 7S.OO
20. 00
79.tiO
10.0(1
120.00
121.00
64.00
»2J*00
307. utf
207.00
tQl.tiO
«31.00
6*.OO
73d. 00
                                             CO
                                              NI

                                           19.00
                                           16.00
                                           2J.OO
                                           »».00
                                           28.00
                                           2*. 00
                                           32.00
                                           17.00
                                           31.00

                                              CA

                                           3a*ao
                                           J3.00
                                          24».00
                                          141.00
                                           70.00
                                           38.00
                                          337.00
                                           45.00
                                          263.00
    (continued)
                           Reproduced from
                           best available copy.
                                146

-------
SITE 2
sartcooa
20721615
                   TABLE B-5 (continued)
10
            1(6-12)
            t (12 + )
            210- B)
            2(0*1
            3(0-0)
                   QJ
                   pa
                    AC.

                  7.UO
                  5.UO
                  3.00
                  u.Ub
                  6.Ob
                  • »tt 0
                  *.oo
                 10 .4,0
                  7.00
                               CO
                                           CO
                                            Nl
76.00
17. 7i)

23.30
99.70
33.00
243.00
23.30
Aft. 70
23.70

< 1 . 0 0
ci.no

1*3-)
C1.00
O.SO
<1.00
0.00

23.70
*4.JO
60.00
30.00

46.00
S6.00
0*.UO
44.00
A*. JO
57.00
•6.00
                                                       CR
113. UO
50.00
2J.OO
9J.OO
3.1.00
• 7.00
27. UC
197.00
133.00
2oa.oo
65.00
19.00
89.00
67.00
7*. 00
•4.00
37T.OO
I6U.OO
2J1«U.OO
20700.00
U6ab. 00
3*370.00
•W.J30.00
*&27b.OO
2V«bU.OO
3UOOO. OO
20390.00
27U.OO
127 .dU
73.00
1*U.OO
137.00
77.00
87 .JO
46O.MO
223.00
                                 •N
    (continued)
                      Reproduced from
                      best available copy.
                                147

-------
                    TABLE  B-5  (continued)
SITE  2
SITECLOE

2072161S
13
            610-8)
            616+)
            B67
                 22.30
                 11.70
                 IS. 00
                 la* 70
                 18. JO
                    Ptt
                 20.00
                 10. OU
                 23. 00
                 *O.OG
                 17.00

                     AC

                   5.00
                   4.00
                   1 cOO
                   b.OW
                   *.OU
                                 CO
                   <1.00
                   <1.00
                   <1.00
                   <1.03

                   o.oo
                  73.nn
                  22.00
                  o. 13
                   9.00
                  '9.09
                  12.00
      CO

   29.70
   29.30
   21.40
   22.30
   14.00
   17.410
25210.00
3097U.00
1*000.00
1*710.00
13760.00
13VBO.OO
104.00
 29.00
 41.00
 3S.OO
 ftO.OO

    CR

 73.00
 70.00
 S3.00
 73.00
 27.00
 43.00
                      MN
    (continued)
                        Reproduced  from
                        best  available  copy.
                                  148

-------
                   TABLE  B-5  (continued)
SITE  2

S1TECODE

21112819
10

10T
JTT
ittu
ITW
IBT
2TU
            3BU
            3TU
                     CU

                  10.00
                  24.00
                  14. 00
                  36.00
                  11 .00
                  22.00
                   9.00
                   6.00
                  35.00

                     Po
                     8A
                     CO

                   o.oo
                   <1.00
                   <1.00
                   0.00
                   o.oo
                   0.00
                   o.oo
                   o.oo
                   0.00
                                  ZN
  CO

10.00
o.oo
 7.00
10.00
 7.00
 3.00
10. 00
10.00
 7.00
                                               AS
33.00

-------
                    TABLE  B-5   (continued)
SITE  2

SlTEwOOe

21112815
10

*ar
*TT
4T7
            4-ru
            9TU
            d6B
            BUT
                               AS
                                                           <0.01
                                              
-------
                  TABLE B-5  (continued)
SITE  2

SJTCCOOt

2U12dlS
            BST
            odJ
            6TO
                    cu

                 21.00
                  9.00
                 I*. 00
                 33*00
                 13.00
                 23.00
                 3U.Oi>
                113.00

                    AA
    8A
    CO

  <1.00
  <1.00
   1.00
  <1.03

    2M

 60.00
 »l .00
 Sfr.OO
162.JO
                SE
      CO

    7.OO
    7.00
    7.00
    A. 00
 8610.00
19460.00
17060.00
                             AS
  
-------
                   TABLE  B-5   (continued)
 SITE 2

SITE (.JOE

2001 obi*:»
10

b&T
BuB
37
3b
6TU
6BU
6TT
WT
3T
                    cu

                  7.00
                  •.00
                  9.00
                  O. 00
                 30.00
                 10.00
                 13. t)u
                 13.00
                 10. 00
 9.00
 3.50
 8.00
 0.00
10.00
 8.00
18.50
13. SO
 9.00

   CO
                   <1.00
                   <1.00
                   
-------
               TABLE  B-5  (continued)
SITE  3

S1TECOOE

31117BIS
        IU
        IB
        U
        28
        2T
        3d
        3T
        40
        4T
               CU

             IS. 00
             18.00
             28.40
             11.00
              8.00
             32.00
             S3. 00
             58.00
             44.00

               PB
               4 .00
               4.03
               4.JO
               2 .00
               3.0w
               o.OO
               7.wO
               a.oo
               O .Ol>
(continued)
                           bA
                           CO
                                        CO
   AS

331.nn
2ft7.00
 <8.01
133,00
ifi7.no
 
-------
                  TABLE B-5  (continued)
SITE  3

S1TCC09E

31117*14
10

S3
5T
           aer
                  cu
    (continued)
BA
            SE
                              CO
                                          CO
                       4S

                     <0.91
                    1*7.00
                     <0.01
                     
-------
                   TABLE  B-5  (continued)
SITE  3
siitcooe
10

IT
IB
«T
•a
2T
26
.»!
3B
4T
                    OJ

                 ib.oo
                 10.00
                 • 3. 00
                 IS. 00
                 lo. 00
                  6*00
                 JO. 00
                 12.00
                 43.00

                    Ptt
    bA

 59.00
 6T.OO
133.00
 So.OC
 89.00
121.00
213.00
 42.00
214.UO

    CO
                   0.00
                   O.OO
                   0.90
                   o.oo
                   <1.00
                   0
20.00

   CA

36.00
44.00
67.00
71.00
46.00
33.00
bd.OO
37.00
 00.00
                                                 fS.
                    O.OO
                    o.oo
                    0.00
                    0.00
                    0.00
                    o.oo
                    0.00
                    0.00
                    o.oo
      (continued)
                        Reproduced (rom
                        best available copy.
                              155

-------
            TABLE  B-6    DEEP CORES  METALS  DATA
SITE  1

 S1IECOOE

 112J031S
ID

2(45-30)
2 ( 50-60 J
3(J2-*d>
             6(45-SOJ
             b£^( 30-42J
             B00(3o-o2 )
                 123.00
                 sa.oo
                    CJ

                 14*00
                  6*00
                  3.00
                  8. JO
                  9.00
                 24.^0
                  O.OU
                 14.00
                    CO
                  <1.00
                  o.on
                  o.oo
                  <1.00
                   3.00
                   3.00
                                 cu
                  MI

                38.00
                27.00
                27.00
                3o.OO
                44.00
                4O.OO
                22 .00
                 13.00
                 £0.00
                 13.00
                 23.06
                 20.Ou
                 17.06
                 18.00
                 17.00
                    ZN

                 40 .00
                 43. UO
                 40. CO
                 J7.00
                 33.00
                 Sw.OO
                 44. OC
                 • 6.00
                                                          CR
31170.00
3*000.00
27670.00
27560.00
               26.00
               29.00
        (continued)
                                                ff.
                   S.uO
                   1.00
                   2.CO
                   I .00
                   4.00
                   7.00
                   3.00
                   4.00
                       Reproduced  from
                       best available  copy.
                                 156

-------
                    TABLE  B-6  (continued)
.SITE  1
S1TCUOE

I 063042S
10

d«D(3J-«2)
0»D( 56-62)
1 134-36 I
1(50-55)
ot 30-35)
    •A

I2J.30
 sa.oo
            t( 44-36)
                              54.00
                              63.00
                              44.00
                             165.00
                    cu

                  8.00
                 14.00
                  9.00
                  9.00
                  9.00
                  9.00
                  9.00
                     CO
                  O. 00
                  o. no
                  
-------
                     TABLE  B-6  (continued)
 SITE 2
SITECOOE

2122101
ID

4(26-30)
3C30-36J
M 36*40 )
             9( 36-491
             S(*W-oOI
             0(26-32 i
             6(32-49)
             6 ( 49-50 j
                     cu

                  16.00
                   6.00
                   5.00
                  14.00
                  IS. 00
                  21.CO
                  1C. 00
                  14.00
                  21.00
                     CO

                     1.00
                    <3.00
                     1.00
                    <3.00
                     3.00
                    <1.00
                    :1.SO
                    ;:. 90
                    <3.00
                                   SE
                                                AS
                                               CO
   hi

2*.00
25.00
 9.00
61.00
14.00
7tt.UO
17.04
39.00
35.00

   CD
20.00
17.03
17.00
20.00
10.00
«0. 00
<2. c:
13.00
3.00

33.00
1 .00
1 7.00
43.00
33.00
00.00
67.00
20.00
33.00
                                         13330.00
                                          0670.00
                                          70JU.OO
                                         10500.00
                                         17670.00
                                         1IOOO.OO
                                          6676.00
                                         21000.00
                                    MN
                     2.00
                     1.03
                     1.00
                     1.00
                     1 .00
                     2.00
                     3.00
                    <1.00
                     5.00
         (continued)
                       Reproduced from
                       best available copy.
                                 158

-------
                    TABLE B-6  (continued)
SITE  2
   *
10

6iO(.*0—»i>)

4(33-37)
            4( 34-40)
            4 (50-54).
            2(33-37)
                    CJ

                   .00
                   .00
                   .00
                   .00
                   .00
                   .wO
                   . 00
                   .00
                   .00

                    PL
                 16.30
                 7.00
                 13.00
                 9. OC.
                 7.00
                 6.00
                 b. Ob
                 7.00
                 6.00
    SA

104.00
 7S.OO
 16*00
 37.00
112.00
 14*04
 le .00
 30.00
 S3.00

    CO
                    c.co

                    u.oo

                   O. JO

                   < ;•. 30


                     ZN

                  33.00
                  lu.GO
                  2J.OO
                  26.00
                  25.00
                  IS.00
                  IV.00
                   4.00
                  19.00
                                              SE
                                                           AS
                 Ct
                              Ml

                           22.00
                            8.30
                           14.00
                            0.00
                            7.00
                            4.00
                           15.00
                            2.00
                            7.00

                              CR

                           18.00
                           10.00
                           U.JO
                           84.00
                           19*00
                            9.00
                           I to. 90
                            4.UO
                           10.00
                  <3.03
                  <3.00
                  O.OO
                  <3.00
                  0.00
                  (3.00
                  O.03
                  <3.00
                  <3.00
         (continued)
                        Reproduced from
                        best available copy.
                                  159

-------
                    TABLE B-6  (continued)
SITE  2

SITECOOE

21221UI
10
            B6O( 30-35)
            dCO(S6-o2>

                   CJ

                16.00
                 b.OO
                 3.60

                   PB

                10.00
                18.00
                 7.00
                    BA
                102.00
                 75.00

                    CO

                 <3.00
                 0.00
                  f..OO
                 37.00
                 33.00
                 1ft. 00
                                se
>*00u.00
               39.00
               22.00
                a. oo

                  Cfi
               ta.oo
               10. JO
                  2.00
                  i.OO
                  3.00
        (continued)
                      Reproduced from
                      best available copy.
                               160

-------
           TABLE B-6  (continued)
SITE  3

SI TECJOE

3122881
    10

    1 (30- JO)
    1 ( A«-*8>
    l(Ad-S2>
    1 I »2 -Sol
    21 32-36)
    3(27-30)
    3(39-J»l
    3(A5-A8J
           cu

          2.00
         20.00
         60.00
         17.00
         37.00
         29. UO
         62.00
         5o.OO
         90.00

           pa
                        UA
                                cu
                               0.00
                               <3. 00
                               <3. 00
                               o.oo
                               o.oo
                               o.oo
                               O.OO
                               O.OO
                                ZN

                             30.00
                             AO .00
                             o7 .00
                             9J.OO
                             OA .00
                            120.0O
                             A7.00
                             bO .00
                                    SE
                                     CO
    Nl

 34.30
 22.00
 38.00
 «9.0U
141.00
 55.0O
 AS .00
 •2.00
 3«.00
                               16170.00
                               1*070.00
                               20830.00
                               2JOJO. I>O
                               29l7g.<»0
                               2«670.OO
                               20000.00
                               21670.00
                                       FE
           2.00
          O.OO
           J.OC
           6.00
           1 .00
           *.00
           1 .00
           1 .00
           1.00
(continued)
              Reproduced From
              best available  copy.
                       161

-------
                    TABLE B-6  (continued)
S.ITE 3
snecuoe
            10
                   cu

                9*. 00
                 a. uo
                11*00

                    A6

                  3.00
    bA

107.00
 frt.OO

    CO

 O.OO
 <1.00

    2N

 •O.OO
 33.00
CC
                                                       AS
          9.00
         10*90
         It. 00
         19.00
        (continued)
                          Reproduced from
                          best available copy.
                                 162

-------
                     TABLE B-6  (continued)
SITE  3

SITECJOE

3002*625
ID

•63IJO-3SJ
             e(S2-»e>
             4*7
   cu

9«.00
 a.oo
 6.0U
17.00

20.00
13.00
 a. Ob

   P6

27.00
11.00
33.00
J6.00
 7.00

30.00
23.00
    bA

107.00
 »*.uo
 JW.OO
 M.OO
 61 .00
                                  CO
                               <1. 00
                               o.oo
                               
-------
                           APPENDIX C

 CONCENTRATIONS  OF ORGANIC COMPOUNDS FOUND IN SITE SOIL


   Table  C-l   Compounds Present in Backgound Samples
Compound               Concentration in Background Sample (mg/kg)
                               Top (0-25 cm)      Bottom (25-51 cm)
Site 1

Chrysene                           <.001
Bis(2-ethylhexyl)phthalate          0.538            0.520
                                                     .077
Benzo(b)fluoranthene                                 0.721
Benzo(k)fluoranthene                0.220            0.721
Benzo(a)anthracene                  <.001
Phenol                                              <.001

Site 2

1,2-Diphenylhydrazine               <.001            <.001
Butylbenzylphthalate                                 <.001
Bis(2-ethylhexyl)phthalate          <.001
Chrysene                            .008
Benzo(a)anthracene                   .008
2-Nitrophenol                                       0.102
4-Nitrophenol                                        .006

Site 3

Ethylbenzene                                         .003
Bis(2-ethylhexyl)phthalate          <.001            0.801
                                  16.57
Naphthalene                         .002
Isophorone                         <.001
Pyrene                              .001
Chrysene                           <.001
Benzo(a)anthracene                  <.001
Toluene                            4.92
                              164

-------
                  Table C-2   Organic Compounds in Soil at Site 1
Compound

Benzo (b) f luoranthene

Benzo (k) f luoranthene

Benzo (a) anthracene




Phenanthrene




Fluoranthene




11/10/81
Top Bottom
<.001

<.001

78.80 <.001
1.976 <.001
26.60
17.08 x 103
874.00
.006 <.001
.003
.001 <.001
.012 <.001
<.091
.012 <.001
.193
14.700
.002
Concentration mg/kg
6/14/82
Top Bottom
t


.036

.003 <.001
.003



<.001 <.001
<.001



<.001 <.001
.001



12/1/82
Top Bottom
.010 .036
62.400
.010 .036
68.400
3.686 12.810













(continued)

-------
                              Table C-2(continued)
Compound
Concentration mg/kg
11/10/81 6/14/82 12/1/82
Top Bottom Top Bottom Top Bottom
Butylbenzylphthalate
Benzo (a)pyrene
Dibenzo (a,L) anthracene
Benzo (g, h, i) perylene
Anthracene
Naphthalene
.009 <.001 <.001 <.001
<.001 <.001 <.001
.104
.002
<.001
4482.00 .026
.332 7.24
<.001 .019
135.90
.002 0.200
229.10
.006 <.001 <.001 <.001
.001 <.001 <.001 <.001
.002
.009
<.001
.053 <.001 <.001
<.001
(continued)

-------
Table C-2(continued)
Compound
Concentration mg/kg
11/10/81 6/14/82 12/1/82
Top Bottom Top Bottom Top Bottom
Benzene
Pyrene
Toluene
Ethylbenzene
Di-n-butylphthalate
Chyrsene
Bis (2-ethyhexyl)phthalate
Isophorone
.021
<.001
<.001
<.001
3.142 <.001 <.001 .001
.358 <.001 <.001
9.594
14.924
<.001
.002
.011
<.001
<.001
<.001

<.001 <.001 <.001 <.001
<.001 .003
.073 <.001 <.001 <.001 <.001 <.001
.006 <.001
<.001
(continued)

-------
                                  Table C-2  .(-continued)
CTi
00
Compound

Phenol
Pentachlorophenol

11/10/81
Top Bottom
<.001 <.001
.031
<.001
<.001
<.001
<.001
<.001
Concentration mg/kg
6/14/82
Top Bottom
.0234 .1170
1.863
.0141


12/
Top
8.957
5.770
42.980
30.700


1/82
Bottom
.1073
129.0


-------
                    Table C-3  Organic Compounds in Soil at Site 3
VO
Compound

Chrysene
Benzo (a) anthracene
Bis (2-ethylhexyl) phthalate
Isophorone
2 , 6-Dinitrotoluene
Concentration mg/kg
11/17/81
Top Bottom


.196
.167

.806 1.586
4.53 .005
.038 .023
.052
6/29/82 10/19/82
Top Bottom Top Bottom
<.001
<.001
<.001 .002 .002
.0002 1.421
<.001 .012
<.001
<.001
<.001
<.001
<.001
   N-Nitrosodiphenylamine

   Dibenzo(a,h)anthracene



   Benzo(a)pyrene
<.001
                      <.001
                       .005
                       .016

                       .095
<.001
   (continued)

-------
                              Table C-3 (continued)
Compound
                Concentration mg/kg
                             11/17/81
                          Top       Bottom
                      6/29/82
                   Top       Bottom
                                   10/19/82
                                Top     Bottom
Fluoranthene


Phenol


Benzene
Bromoform


Toluene


Ethylbenzene
 .091
 .024
 .034
<.001
<.001
 .005

<.001
                           1.079
                           5.790

                           <.001
                            .006
2.059
<.001
<.001
<.001

 .653
          .003
          .001
                                         0.220
                                         0.058
                                         .288

-------
                 Table C-4 Organic Compounds in Soil at Site  2
Compound
Concentration mg/kg
9//81 or 11/12/81 6/16/82 11/19/82
Top Bottom Top Bottom Top Bottom
Anthracene
Benzene
Naphthalene
Phenanthrene
1 , 2-Diphenylhydrazine
Isophorone
.3.18 <.001 0.018
6.520
<.001
.578
11.772
<.001 <.001
<.001
<.001
<.001
.264 3.378
9.480 <.001
.425
.318 <.001
6.520 13.630
0.578
11.772
<.001
.011 .001
0.448
.090 .040
.222
(continued)

-------
                                Table  C-4  (continued)
Compound

Bis (2-ethylhexyl) phthalate
Pyrene
Butylbenzylphthalate
Phenol
4-Nitrophenol
Pentachlorophenol
Concentration mg/kg
9//81 or 11/12/81 6/16/82
Top Bottom Top Bottom
<.001 <.001
.062 .131
.072
<.001 <.001
<.001 .001 .027
<.001 <.001
<.001
<.001

.260 <.001
<.001

11/19/82
Top Bottom
4.068

*

.0013
.2814
2-Nitrophenol
.849

-------
   Table C-5 Organics Present in the  Unsaturated Zone.



              at  Site 1






Deep  Soil Cores
Compound Concentration (mg/kg)
Top Bottom
1,2-Diphenyl-
hydrazine .001 <.001
Acenaphthene <.001
2,4-Dinitrotoluene <.001 <.001
Soil Pore Water

Compound Concentration (mg/1)
Phenol .122
.067
.052
Bis (2-ethylhexyl) -
phthalate 120.80
55.64
# of +ve
Observations
3
1
2

# of +ve
Observations
3


2
Di-n-butylphthalate




Butylbenzylphthalate




Chrysene
.031




.036




.631
1




1




1
                             173

-------
  Table C-6  Organics Present in the  Unsaturated  Zone



             at  Site 2



Deep Soil Cores
Compound
1 , 2-Diphenylhydrazine
Anthracene
Bis(2-ethylhexyl)-
phthalate
Isophorone
Acenaphthylene
Fluorene
Diethylphthalate
Butylbenzylphthalate
2-Nitrophenol
4-Nitrophenol
2 , 4-Dichlorophenol
Phenol
Soil Pore Water

Compound
Concentration (mg/kg)
Top Bottom
.010 .010
.056
<.001
<.001
.008
<.001
<.001
<.001 <.001
<.001
<.001
0.676
0.384
0.010
0.089 0.138

Concentration (mg/1)
# of +ve
Observations
3
1
2
1
1
2
1
1
1
1
1
2

No. of +ve
Observations
Phenol




4-Nitrophenol




Pentachlorophenol
<.001




<.001




<.001
1




1




1
                             174

-------
  Table C-7   Organics Present in  the  Unsaturated Zone



              at Site 3



Deep Soil Cores

Compound
Anthracene
Phenanthrene
Pyrene
Di-n-butylphthalate
Butylbenzylphthalate
Chrysene
Bis (2-ethylhexyl)
phthalate
Benzo(a) anthracene
Benzo(b) fluoranthene
Benzo(k) fluoranthene
Benzo(a) pyrene
2 , 4-Dichlorophenol
2 , 6-Dinitrotoluene
Soil Pore Water
Concentration (mg/kg)
Top Bottom
1.28
1.32 16.90
1.17 13.16
.352
4.76
12.02 80.80
650.90
0.284 3.49
6.19 8.87
140.5
0.396 3.76
.056
.044
0.394
0.069
0.515

# of +ve
Observations
1
2
2
2
3
2
3
2
1
1
1
1
1

Phenol                 < .001
                           175

-------
   Table c-8 Organic Compounds Found in the Background

             Samples of the Unsaturated Zone
Compound                         Concentrations (mg/kg)
                                 Top             Bottom
Site 1

I,2-Diphenylhydrazine            0.040

Site 2

1,2-Diphenylhydrazine              -               .001

Anthracene                                        <.001

Bis(2-ethylhexyl)phthalate                       . <.001

2-Nitrophenol                    1.166

4-Nitrophenol                    0.662             .097

Site 3

Phenol                             -              0.273
                          176

-------
Quality Control/Quality Assurance
     A QC/QA program was  implemented  at  the  beginning of
the project.   This  program had  two  main parts.   Part  1
involved sample  collection,  transportation  and  storage/
and Part 2  involved the determination of  blanks,  repli-
cates and spikes.
     Each sample collected was  assigned  an identifying
code, which  contained  information on the  site,  date  and
type of sample collected.  Samples were placed in a cool-
er immediately upon collection,  to keep them  cool until
they could be refrigerated.  The samples were stored in a
refrigerator  dedicated  to  project  samples, until  they
were  analyzed.   Soil  samples were  collected in  ziploc
plastic  bags and aqueous  samples in  borosilicate glass
bottles with teflon-faced  screw  caps.   A log book of all
site visits  and  samples  collected was maintained.   Aque-
ous samples to be analyzed for metals were adjusted to pH
<2 with  nitric acid as soon as  they  arrived at  the lab-
oratory.   pH  and   COD  analyses  were  performed  on  the
samples within 24 hours of collection.  Soil samples were
refrigerated at  4°C until they  were  analyzed.   All sam-
ples for priority pollutant analysis were extracted with-
in one week  of collection,  and analyzed within one month
of extraction in most cases.
     Glassware used for priority  pollutant  analysis was
solvent washed,  detergent  washed,  rinsed with tap water,
                          177

-------
distilled water and oven-dried.  The  K-D  flasks  and con-



centrators were also soaked in chromic acid prior to each



set of extractions.  After each batch of samples from one



site was  run,  the  glassware was also fired  in  a furnace



of 400°C after the cleaning sequence described above.



     Glassware for metals analysis was washed with deter-



gent, and then acid-rinsed with nitric  and hydrochloric



acids.   After a  final  rinse  with  distilled water/  the



glassware  was  oven-dried.   Glassware  used  for  other



analyses  were cleaned  using  standard  laboratory  proce-



dures.



     The  quality control procedures used in the determin-



ation of  organics centered mainly on the determination of



blanks  and the  use of  duplicate  determinations.   Some



spikes were also  determined,  particularly on the aqueous



samples.   No   studies were done  on recoveries  from the



different  soil matrices,  because  of time  and  money re-



strictions.



     Duplicates,  spikes  and blanks were  also  run on the



samples  analyzed  for metals.   The  duplicate determina-



tions are included  in the  raw data  for metals in Appendix



B.



     Procedural blanks were run with every  set of Extrac-



tion  Procedure Toxicity determinations.   Ultrex  nitric



acid from J.T. Baker Chemical Co.,  was used  in the  diges-



tion  of  the  extract for  metal analysis.   These  blanks



                           178

-------
served as  controls  for the level  of  metal contamination



introduced  by  the  extraction and  filtration  steps,  as



well as the digestion step.



     In all cases,  the  concentrations of the blanks were



subtracted  before  the  final  metal  concentrations  were



calculated.  Table  C-9  lists  blanks for soil pore water,



E.P. Toxicity and soil core samples.
                          179

-------
TABLE C-9   BLANK CONCENTRATIONS  mg/1

Soil Pore Water
Blank #1
Blank #2
E.P. Toxicity
Blank #1 <
Blank #2
oo Blank #3
o
Blank #4
Soil Samples
Blank ftl <
Blank #2
Cu
.02 .
.03
.002
.02
.01
.01
.002
.01
Ni
<.008
<.008
<.008
.130
.015
.010
<.008
.010
Zn
.46
.04
.31
.10
.19
.16
.01
.03
Ba Cr
.26 <.01
<.02 .05
.29 <.01
.20 .01
.28 .02
.08
.11 <.01
.15 .08
Al Pb
.20 .15
.10 <.02
.22 <.02
.35 .10
.29 <.02
.20 .03
<.02
.03
As Cd Fe Mn Ag
.108 <.01 .049 .007 .006
.090 .010 .014
- .02 - - .03
- .01 - - <.002
<.01 - - .011
<.01 - - .010
<.01 - - .013
<.01 - - .010

-------
                      APPENDIX D

                  Field Data for Trees
SPECIES
TREE  AREA   DATE
HEIGHT   UIDTu  DEATH
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
bt - ~l. 1 	 ,.. _.u
XC4WI\ X
-------
                      Field Data  for Trees
SPECIES
TREE  AREA   DATE
HEIGHT   WID'iM  LEATIJ
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
5
A
A
A
A
A
A
A
" A
A
A
A
A
A
A
A
A
A
A
A
A
A'
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
APR07C2
JUL2782
SEPOR82
APR0782
JUL27S2
SEPOGC2
APR0732
JUL2782
SEP0832
APR0782
JUL27S2
SEP0832
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEPCC82
APR0782
JUL2782
SEP03S2
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0832
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEPC882
APR0782
JUL2702
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
                                     29.80
                                     51.00
                                     52.00
                                     22.90
                                     21.50

                                     21^60
                                     43.00

                                     24'.10
                                     27.20
                                     19.68
                                     10.30

                                     34.30
                                     30.20
                                     29.50
                                     17.80
                                     13.90
                                    16.30

                                    32!40
                                    21.00
                                0.95
                                1.25
                                1.13
                                0.64
                                1.06

                                0.32
                                0.71

                                0*.32
                                1.54
24.10
73.60
80.00
22.90
45.60
25.40
32.00
22.20
25.80
25.40
24.10
46.70
39.50
0.64
1.30
1.23
0.64
0.90
0.48
•
o!48
0.72
1.25
0.32
0.91
0.86
                               0.32
                               0.20

                               0.32
                               0.44
                               0.41
                               0.16
                               0.20
                               0.20
                               0.38
                  Y
                  Y
                  Y
                  Y
                  Y
                  Y

                  Y
                  Y
                          182

-------
    Field Data for Trees
 SPECIES

 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 hackberry
 osage orange
 osage orange
 osage cran~e
 osage orange
 ocage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
 osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
 red cedar
TREE  AREA   DATE
HEIGHT   17 ID?!!  DEATH
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
SEP0802
APR0782
JUL2782
SEPOC82
APP.0782
JUL27G2
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JrJL27S2
SEP0882
APR0782
JUL2782
SEP08G2
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEPOR82
APR0732
JUL2782
SEP0882
APR0782
JUL2702
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0802
APR0782
JUL2702
SEP0882
APR0782
.
26.00
18.40
9
38.10
34.30
.
27.90
20.40
fc
22.90
18.40
^
m
9
.
15*.50
29.10
27.90
15.20
17.30
15.00
26.70
34.00
9
16.50
17.60
14.80
24.10
15.10
.
25.40
15.80
14.20
17.10
15.30
7.50
27.70
23.80
20.20
26.70
16.20
9
m
9
m
33.60
t
0.32
0.30
9
0.32
0.36
m
0.48
0.34
*
0.32
0.40
t
<
.

l.'ll
0.64
9
1.27
0.5C
0.67
0.64
9
m
1.27
0.36
0.58
1.27
0.52
9
1.11
0.74
0.52
0.79
0.41
9
0.64
0.49
0.43
0.79
0.30
.
.
t
t
0.32
Y

Y
Y


Y


Y

Y
Y




Y
R


R

Y
Y


R

Y
Y




Y
R

Y
R

Y





           183

-------
                  Field Data for Trees
SPECIES

red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
reel cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
russian ol
TREE  AREA   DATE
HEIGHT   WIDTH  DEATH





























ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
G
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
JUL2782
SEPOC82
APP.0782
JUL27B2
SEPOG82
APR0782
JUL2782
SEP0802
APP.0782
JUL2782
SEP0882
APP.0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0832
APR0732
JUL2782
SEP0882
APR0782
JUL2732
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL27S2
SEP0882
31.00
20.20
30.50
32.20
26.50
27.90
33.90
29.00
35.20
- 42.10
36.00
34.90
34.90
32.50
29.20
3 2 . 2.0
30.00
34.30
35.00
33.80
30.50
32.40
31.00
29.20
31.60
30.50
•
*
•
15.20
16.90
•
22.80
20.50
•
20.30
26.90
•
14.60
•
•
22.90
26.50
•
38.10
36.00
29.00
0.51
1.05
0.64
0.67
0.68
0.95
1.90
1.09
0.95
1.49
1.02
0.95
1.10
0.65
0.64
0.76
0.78
0.64
0.65
0.67
Cf *
. \) «i
0.66
0.60
0.48
0.48
0.46
•
*
•
0.79
0.79
•
0.64
•
•
1.27
0.31
*
0.32
•
•
0.64
0.57
•
1.27
1.60
1.50
                                        Y
                                        Y

                                        Y
                                        Y

                                        Y
                                        Y

                                        Y
                                        Y
                          184

-------
SPECIES
    Field Data  for Trees

TREE  AREA   DATE     HEIGHT
                                     16.50
                                     26.60

                                     15*.20
                                     12.40

                                     16.50
                                     23.80
                                     13.50
                                     20.30
                                     28.00

                                     22*90
                                     17.00

                                     30.00
                                     19.30

                                     19*10
                                     21.00

                                     14*.00
                                     16.00

                                     21.60
                                    33.00
                                    22.50

                                    17*. 10
                                     22.90
                                     21.00

                                     14*.00
                                     24.30

                                     26.70
                                     28.00

                                     31.10
                                     29.50
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
hackberry
hackberry
hackberry
hackberry
hackberry
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
5
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
APR0782
JUL2702
SEP0882
APR0782
JUL27G2
SSP0882
APR07G2
JDL2782
SEPC382
APR0782
JUL2782
SEP03G2
APR0702
JUL2782
SEP0882
APR0782
JUL2702
SEP0882
APR0732
•JUL2732
SEFGS82
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP08S2
APR0782
JUL27 82
SEP0882
APR0782
JUL2782
SEP0882
APR07B2
JUL2782
SEP0082
APR0782
JUL2782
SEPOC82
APR0782
JUL7.782
SEP0882
APR0782
JUL2702
SEPOG82
APR0702
JUL2782
WIDTH  DEATH

 0.32
 0.43
                                0.64
                                0.50

                                0.64
                                0.54
                                0.61
                                0.32
                                1.01

                                0*.32
                                0.99

                                0*.32
                                0.97

                                o!l6
                                1.02

                                0*.32
                                0.94

                                0*32
                                0.32
                                0.71

                                0*.48
                                0.48
                                0.64

                                0*.32
                                0.74

                                0.32
                                0.20

                                0*32
                                0.29
         Y
         Y
         Y
                                                      Y
                                                      Y
                                                      Y
                                                      Y
                         185

-------
SPECIES

hackbcrry
hackbcrry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hacUbcrry
hackberry
hackberry
hackberry
hackberry
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
    Field Data for Trees

TREE  AREA   DATE     HEIGHT
UIDTII  DEATH
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
D
D
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
n
B
B
B
B
SEP0082
APR0732
JUL2782
SEP0882
APR0782
JUL27C2
SEP0882
APR0782
JUL2782
SEPOC82
APR0782
JUL27 82
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
TT1T IT DO
U WiJ^. / Oi.
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0832
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0832
APR0782
JUL2782
SEP0832
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
24.50
17.10
14.50
•
29.20
26.60
•
26.70
24.00
•
19.10
18.00
•
27.90
26.00
•
22.90
10.00
•
12.70
14.00
•
20.30
22.00
•
25.40
19.50
•
15.20
20.50
*
17.80
25.00
3.90
19.10
18.30
10.40
15.20
13.00
•
16.50
19.00
•
14.00
»
•
20.30
0.38
0.32
0.19
»
0.32
0.26
•
0.16
0.28
•
0.16
0.20
•
0.32
0.18
•
0.32
0.28
•
0.16
0.14
o
0.16
0.23
•
0.95
0.25
•
1.11
0.18
«
1.11
0.30
0.19
1.27
0.25
0.23
1.11
0.17
•
1.27
0.21
.
0.95
•
•
0.95



Y


Y


Y

Y
Y


Y

Y
Y


Y


Y


Y


Y








Y


Y

Y
Y

                          186

-------
SPECIES

osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
red cedar
red "cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
red cedar
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
    Field Data for Trees

TREE  AREA   DATS     HEIGHT
6
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
B
B
B
B
B
B
E
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP08B2
A?R07 32
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0082
APR0782
JDL2782
SEP0882
APR0782
JUL2732
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
•
•
17.80
25.00
•
20.30
13.00
•
28.60
28.70
21.80
29.80
34.00
29.50
34.90
37.00
33.00
34.30
35.00
29.80
34.90
36.00
23.10
36.80
38.00
31.00
39.40
35.00
28.50
34.90
29.00
25.90
28.60
33.00
23.20
29.80
32.00
24.00
38.10
19.50
•
22.90
20.00
•
19.70
23.00
•
•
•
0.64
0.35
•
0.95
0.19
•
0.64
0.44
0.57
0.64
0.79
0.62
0.95
O.S2
0.91
1.11
0.36
0.75
1.43
0.58
0.55
0.48
0.45
0.48
0.79
0.65
0.74
0.64
0.49
0.48
0.64
0.34
0.34
0.32
0.31
0.28
1.11
0.77
•
0.64
0.70
•
0.64
0.74
•
WIDTH  DEATH
         Y
         Y
                           187

-------
                  Field Data for Trees
SPECIES

rusEian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
russian olive
rucsiars olivs
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
black locust
TREE  AREA   DATE
HEIGHT   !7IDTH  DEATH




                  Y



                  Y


                  Y


                  Y
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
B
B
B
B
n
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B-
n
C
C
C
C
C
C
C
C
C
C
C
C
C .
C
C
C
C
C
C
C
C
C
C
C
C
C
APR0782
JUL2782
SEP0082
AFR0782
JUL2782
SEP0882
APR0782
JUI.,2782
SEP0882
APR0702
JUL2782
SEP0882
APR07 82
JUL2782
SEP0882
APR0782
JUL2782
SEP0832
APR0782
JUL2782
SEPOES2
APR07 82
JUL2782
SEP0882
APR07 82
JUL2782
SEPOS82
APR0782
JUL2782
SEP0882
APR07 82
JUL2782
SEP0882
APR0782
JUL2732
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2702
19.10
23.00
•
20.30
23.00
•
30.50
22.50
•
15.20
10.00
t
21.60
16.80
•
17.80
•
•
17.80
15.00
•
22.20
201
270
19.70
213
250
29.20
232
257
34.90
230.5
260
25.40
173
215
27.90
237.5
228
30.50
200.5
202
33.00
101.5
112
24.10
181
0.95
0.89
•
0.64
0.71
•
0.64
0.72
•
0.64
0.61
•
0.43
0.37
•
0.48
*
•
0.32
0.28
•
0.43
1.59
2.41
0.32
1.91
2.36
0.64
2.41
3.05
0.79
1.88
3.01
0.64
1.81
2. 1C
0.64
2.09
2.22
0.95
1.64
1.91
0.95
1.17
1.15
0.64
1.92
                                        Y
                                        Y
                          188

-------
SPECIES
    Field Data for Trees

TREE  AREA   DATE     HEIGHT
WIDTH  DEATH
black locust
black locust
black locust
black locust
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
hackberry
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4 .
4-
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
SEPOC82
APR0782
JUL2782
SEP0882
AFR0732
JUL2782
SEP0882
APR0782
JUL27 82
SEPC082
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL27 82
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP08-82
APR0782
JUL2782
SEP0382
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEPOG32
APR0782
JUL2782
SEP0882
APR07R2
185.5
27.90
165.5
199
24.10
40.00
40.00
15.20
52.50
8.50
33.00
40.00
41.00
21.60
36.00
34.50
33.00
36.00
32.00
27.90
27.50
25.50
43.20
.
11.50
33.00
17.50
17.50
22.90
.
.
33.00
24.50
24.60
14.00
66.50
98.50
17.80
75.50
95.50
16.50
77.00
102
19.10
87.00
125
27.90
1.99
0.48
1.82
2.99
0.32
0.35
0.46
0.16
0.37
0.38
0.47
0.47
0.47
0.32
0.48
0.37
0.31
0.31
0.32
0.32
0.30
0.30
0.48
.
0.38
0.32
0.38
0.31
0.32
.
.
0.48
0,38
0.36
0.95
0.85
1.01
1.11
0.93
1.06
1.43
0.73
1.06
0.95
0.83
0.95
1.27
                                                      Y
                                                      Y
                         189

-------
SPECIES

osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
osage orange
red cedar
red cedar
red cedar
red cedar
red cedar
                .-  Field Data for Trees

              TREE  AREA   DATE     HEIGHT
                                         T7IDTII  DEATI-1
rea
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
red
ceciar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
cedar
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
C
C
c
c
c
c
c
c
c
c
c
c
G
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
JUL2732
SEP0832
APR0782
JUL2782
SEP0832
APR0782
JUL2782
SEPOB82
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2702
SEP0882
APR0782
JUL27G2
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
. JUL2782
SEP0882
74.00
92.50
20.30
70.50
70.50
25.40
43.00
70.00
19.00
19.00
13.00
33.00
13.00
48.50
17.10
70.00
68.50
33.70
37.50
39.50
38.10
25.50
68.50
39.40
8.00
14.50
35.60
43.50
52.50
33.00
46.50
54.50
27.90
27.00
24.00
31.80
33.00
40.50
36.80
43.00
53.00
30.50
46.00
52.00
35.60
51.50
61.00
0.87
0.91
1.27
0.70
0.82
1.27
0.72
0.78
1.11
0.51
0.69
1.27
0.56
0.63
1.27
0.78
0.78
0.64
0.73
0.73
1.11
1.32
1.44
0.64
0.65
0.60
0.79
1.32
1.07
0.79
0.05
0.92
0.32
0.36
0.44
0.64
0.79
0.69
0.95
0.72
0.78
0.64
0.81
0.92
1.11
0.73
1.35
                         190

-------
                  Field Data for Trees
SPECIES
TREE
DAT?
HEIGHT   WIDTH  DEATH
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
russian
ol
ol
ol
ol
ol
ol
ol
ol
ol
ol
ol
ol
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
olive
ol
ol
ive
ive
olive
ol
ol
ive
ive
olive
ol
ol
ol
ol
ol
ol
ol
ol
ol
ol
ol
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
ive
1
1
1
2
2
2
3
3
3
4
4
4
5
5
5
6
6
6
7
7
7
8
8
8
9
9
9
10
10
10
C
C
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
f*
c
c
c
c
c
c
c
c
c
c
c
APR0782
JUL2782
SEPOG32
APR0782
JUL2782
SEPOS82
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0782
JUL2782
SEP0882
APR0732
JUL2782
SEP0882
APR0782
JUL2782
SEP0082
APR0782
JUL2782
SEP0882
APR07G2
JUL2782
SEP0882
21
53
67
24


27
44
44
21
20
17
19
36
36
20


17
27
31
32
30
24
20
56
56
22
67
70
.60
.00
.00
.10
9
.
.90
.50
.50
.60
.00
.00
.70
.00
.00
.30
.
,
.80
.00
.00
.40
.50
.00
.30
.50
.50
.90
.00
.50
0
0
0
0


0
0
0
0
0
0
0
0
0
0


0
0
0
0
0
0
0
0
0
c
0
1
.32
.72
.81
.32
m
.
.64
.59
.59
.64
.62
.55
.64
.53
.50
.32
.
*
. C "
'.52
.55
.64
.55
.53
.64
.66
.75
.64
.97
.05




Y
Y





Y




Y
Y





Y






                          191

-------
                    APPENDIX E

               CLIMATOLOGICAL  DATA

                                          1
          Table El   Daily Rainfall Record

DAY MARCH
1
2
3
4
5 .07
6
7
8
9
10
11
12
13 .80
14 .02
15
16 T
17 T
18
19
20 T
21
22
23
24
25
26 .40
27 .18
28
29 .06
30
31
Total 1.53
80 yr. 2.73
Avg.
APRIL

.30




.02


.32



T


.07
.18


T

.06
.02
.82

.07
.30

.22

2.38
4.13

MAY
.02
.20


2.45
.09




.04
3.55
.03


1.35
.03
.02
.28
.01
.18
.02
.80
1.50
.01
.42
1.50


.86

13.36
5.18

JUNE JULY AUGUST
.05

.22

.04
2.70
.10 .10
T

.46 .01
.26


T
.24 .03 T

.02
.12

.56
.04

.58
.82

T
.15 .04 .14
T

2.00
1.15
3.52 6.07 0.24
3.71 2.80 2.79

SEPT OCT NOV
.10
.50





.02

.30
.09 .22

.24
1.05
.09
T
T .01
.01
.03 T


.18 .03
T
.12
1.05
1.20
.08
1.25
.01


1.41 2.05 3.12
3.47 3.65 2.38

Measurements in inches, T = trace amount, data from
Noble Foundation headquarters farm.

                       192

-------
        Table E-2   Daily Temperature  Record  (°F)

Day

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Day

1
2
3
4
5
6
7
March
High
66
68
68
53
35
48
58
71
65
71
71
76
70
65
76
80
82
78
83
77
68
66
70
72
59
54
45
62
60
74
76































Low
33
45
48
35
32
28
30
40
43
43
56
53
49
48
49
48
50
64
64
52
48
42
38
46
47
36
37
40
42
58
51
April
High
78
82
76
70
64
60
50
62
58
60
68
82
88
82
80
89
73
58
82
64
64
71
71
59
75
79
77
67
78
64

August
High Low





91
92
92
94
97
101

90
71
71
72
72
71
71
72







Low
46
65
41
50
54
36
42
52
44
37
37
52
54
52
63
64
49
48
52
54
48
40
42
46
51
48
48
53
46
52

May
High
76
75
80
83
75
59
76
77
78
80
74
66
74
79
83
81
80
77
84 •
82
90
83
85
80
82
84
87
85
90
88
72
Sept
High
99
98
92
90
91
95
95
Low
74
71
69
58
61
56
59
Low
54
54
58
60
64
48
43
48
54
58
60
57
58
58
55
63
54
56
60
65
63
61
61
60
63
62
63
63
68
70
58
June
High
80
78
87
77
84
86
88
87
89
86
83
85
85
87
76
80
86
82
86
88
83
90
87
86
88
87
89
91
95
92

July
Low High
50
56
62
62
57
65
69
69
70
64
62
62
57
62
70
60
58
64
65
62
61
62
65
62
62
64
65
64
68
71

Oct
High
88
92
89
93
91
91
89
Low
61
64
63
64
64
67
62
90
91
92
93
91
88
87
92
94
93
91
92
94
92
92
93
93
94
96
96
99
101
99
97
95
97
97
95
92
87
79
Nov
LOW
70
72
72
74
76
67
66
65
70
71
66
69
68
66
67
72
74
75
72
70
72
71
72
70
68
70
69
72
74
72
68

High Low







81 64
70 55
58 46
64 36
64 33
69 42
70 54







(continued)
                              193

-------
Table E-2  (continued)

Day
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
August
High Low
92
94
94
94
96
98
99
100
100
91
90
94
96
97
99
99
98
96
98
102
92
96
100
98
70
68
70
71
71
73
73
71
70
71
70
66
65
66
68
71
74
70
71
74
68
70
70
72
Sept
High Low
92
93
94
94
97
89
95
79
88
95
85
73
77
74
80
88
84
81
76
86
88
87
87

62
60
65
66
68
70
70
64
64
64
64
61
60
50
46
56
60
54
48
61
66
66
68

Oct
High Low
86
76
73
75
68
79
79
80
85
77
86
82
63
49
72
74


74
77
68
76
75
81
70
53
51
47
51
52
45
48
48
53
56
63
41
43
49
41


60
38
54
42
52
66
Nov
High Low
66
73
70
70
54
54
52
55
59
50
60
77
78
77
79
53
42
39
40
39
59
67
74

51
55
58
60
45
28
36
26
40
44
47
57
55
40
56
32
29
32
36
38
32
34
42

           194

-------
                                           APPENDIX F


                                   X-RAY  DIFFRACTION SPECTRA
en
     CT70
     f» ID
     " TJ
       a.
      s.S
                 KENT  =  BT1340682S
                 CC!J:IT  TIHE=   1.0 SEC.
 RAHGE=   2.&9 -> 69.00     IHCR= 0.02
 ESTIMhTED TIME OF COUPLET I OH  IS 2?=  1
              INTENSITY US.. TWO-THETft
FULL SCALE =
1500.  COUNTS/S
EC.
               33.68
               (continued)

-------
                              APPENDIX F  (continued)
ID
ICEI-'T :  2T1040682S
co:ji!7 TII:E=   i  o «
                                   SEC.
               I'lTEMSlTV  US.  TWO-THETA
 RAHGE=   2.00 -> ee.eo     IUCF= o.a?
 ESTIMATED TIME OF COHPLET10M IS 24=12
FULL SCALE =
                                                1500. COUMTS/SEC.
               (continued)

-------
                               APPENDIX  F (continued)
                      TI"£=    10  SEC.
          RANGE=   2.00 -> 60.00     IHCP= 6.82
          ESTIMATED  TIME OF COUPLET IOH IS  1 22
             I TENSITY I'S.  TWO-THETA
         FULL SCALE  =
           1509. COUHTS/SEC.
10

                            24.60
                            39.60
              36 8C      36 60

               (continued)
42
48.00
54.80

-------
                               APPENDIX F  (continued)
10
GO
     crxi
      60.ee      IliCR=  8.02
                                 ESTIMATED TIME OF  COHPLETIOH  IS   2=34
0.80
                          .  TNO-THETA
                                 FULL  SCALE  =     1508.  COUHTS/SEC
                                                                                  c-J 00
               (continued)

-------
                                 APPENDIX  F (continued)
\o
vo
                 ICEJiT   2T3I01982S
                 C-CUMT TIME=   1.0 SEC.
                                2.09  ->  60.00      IMCR= 0.82
                       EiTIHATED TIME OF COKFLETIOU  IS  3=44
               U'TEi^ITY US. TUO-THETA
                      FULL SCftLE =    1500.  COUHTS/SEC.
                 0.00
6.
                3D.&0      36.


                (continued)
12.00
              12. 00
                                                             A^^WW^A-i^^
18.00
24.60
              43.

-------
                                APPENDIX F  (continued)
                I CENT =  5T3U0482S
                C-C-OfiT TIKE =   1 .8 SEC.
                                             RANGE=   2.63 -> 68.09     IHCR= 8.*2
                                             ESTIMATED TIME OF COMPLETION !S  •» 54
             IU7EM5ITY U5. TWO-THETA
                                            FULL SCALE =
1508.  COUNTS/SEC.
to
o
o
    CT70
    0) n
a ^

"I
o =
13
               8.68
              33.C8      36 08


               (continued)
                                   42.
48.
   54.00
60. CO

-------
                                 APPENDIX F  (continued)
to
o
    CT30
     -
                 IDr»!T =  BT2061682S
                 CO:JliT TIME=   1.0 SEC
                                              PAHGE=   2.00 -> 60.08      IHCP= 9.02
                                              ESTIMflTED TIME OF COMPLETION  IS 18=14
              INTENSITY US. TUO-THETA
                                             FULL SCALE  =     1560.  COUMTS/SEC.

-------
                                APPENDIX  F  (continued)
to
o
     CTXJ
      a
                ICEUT  : 3TT297882S
               .c-r-iuiT  TK;E=    i.e SEC
             INTENSITY US.  TWO-THETA
                        RAHCE=   2.69 -> 60.99     INCR= 9.92
                        ESTIHflTED TIME OF COMPLETION IS 19=26
                       FULL SCttLE =
1568.  COUNTS/SEC.
              33.68
36
               (continued)

-------
                                 APPENDIX F  (continued)
O
u>
£8.
a -
 o
o3
                 IC'EHT  = 4TT2070882S
                 C.ELHT  TIME-    1.0 SEC.
                                            RANCE=   2 00 -> 60.06     IHCR= 6.02
                                            ESTIMHTED TIME OF COMPLETION IS 20'38
              If.'TEMSITY  VS.  TMO-THETA
                                           FULL SCALE =
1506.  COUHTS/SEC.
               30, £'0      36.de


                (continued)
                                                48.de
   54.00
                                                                                  36.00
SO. 00

-------
                                 APPENDIX F  (continued)
to
o
     ID rc
      TJ




     1.
                 !rE!!T  :  5TT2D70882S
                 CC:."-:T  TIME=   i.o SEC

              IIITENSITY us. TWO-THETA
 PftNGE=   2 00 -> 60.90     INCP= 8.D2
 l&TfHftTED tlHE OF COMPLETION IS 2i=59
FULL SCALE =    1500. COUNTS/SEC.

-------