530SW86032
SEPA
                SIMM
            Environmental Protection
            Agency
                Office of
                Solid Warn *nd
                Emergency ftesponte
DIRECTIVE NUMBER:   9*86.00-2

TITLE:  Permit Guidance Manual on Hazardous Waste Land
       Treatment Demonstrations
             APPROVAL DATE:  July 1986

             EFFECTIVE DATE:  July 1986

             ORIGINATING OFFICE:  office of solid waste

             S FINAL

             D DRAFT
                        •

               STATUS: '
                 ]
A- Pending OMB approval
B- Pending AA-OSWER approval

     reView 4/or con»ent
               I  ]
[                   ^^      	— » —• •.WMiuldll
                 J  D- In development or circulating

REFERENCE (other documents):        headquarters
 DIRECTIVE    DIRECTIVE     D

-------
                                                                       '  I
   v>EPA
                                  * •  ?..   —
                      Washington. fJC 20460
 Name of Contact Person
     Jon Perry
      OSWER Directive Initiation  Request
                         Qngmatof Information
                             Branch
                                                                                 9486.00-2
 Lead Office

    D OERR
    00SW
D OUST
LJ OWPE
U AA-OSWER
 Title
                                                Telepnone*Numoer
                                                	382-4662
                        Approved for Review
ignature of Office Director
                                            Date
    Permit Guidance Manual on Hazardous Waste Land Treatment Demonstrations
 Summary of Directive
    In  response to RCRA,  EPA issues permits for hazardous  vaste land treatment facilities
    RCRA standards require  that the owner  or operator of a hazardous waste land treatment
    facility demonstrate, prior to application of the waste,  that hazardous within
    the  treatment zone, and that human health and the environment are protected by
    the  design and operation strategy.used for the waste at the site.   Successful
    performance of the land treatment demonstration is required in order  to obtain a
    permit under 40 CFR Parts 264 and 270.

    This document was prepared to give the  applicant and the  regulatory agency guidance
    on the information necessary to assist  in choosing and implementing the land
    treatment  demonstration approach.  The  technical approach presented in this manual
    for both evaluating site,  soil, and waste characteristics, and assessing waste
    treatment  processes within the treatment zone soil.
Key Words:

    Treatment,  Soil,  Degradation
                                                                                 -~&<
                                                                                 .''-' -li"
 ype of Directive iMenuel. Policy Directive. Announcement, etc.f
                           e

   -Guidance Manual
                                              ' Status
                                              !    Doreft
                                              !    0 Fin.1
                                                D
                                                LJ Revision
Does this Directive Supersede Previous Directive!*;'   Q Yes
f "Yes" to Either Question. What Directive (number, title!
                              No   Does It Supplement Previous Directives)?   |~1 Yes
                                D OECM

                                D OGC

                                D OPPE
   Request Meets OSWER Directives System Format
            Office Directives Officer
                                                                            (Date
               rectives Officer
                                                                            Date

-------
            UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

                        WASHINGTON, D.C. 20460
                                 I 7 1986
                                    ^^^                 OFFICE OF
                                                          EMERGENCY RESPONSE
                                                          ,
MEMORANDUM
SUBJECT:  Permitting of Land Treatment Uni.ts:   EPA  Policy,
          and XJuidance, Manual on  Land Treatment Demonstration
nd XJuid
 ^X^-v
. Winst
FROM:     J. Winston Porter
          Assistant Administrator

TO:       Hazardous Waste Management Division  Directors
          Regions I-X


     As you know, we must work toward the  1988 RCRA permitting
deadline for land disposal permits, while  concurrently developing
the land disposal restriction ("ban") regulations.  While  these
activities have significant  interactions,  the  land ban regu-
lations are somewhat behind  the permitting decisions.

     The issues of land disposal permits and the  land ban  are of
particular relevance to the  case of land treatment of hazardous
wastes.  Land treatment units are, based on statutory language,
a form of land disposal.  Thus, for this type  of  waste disposal
we must be cognizant of both permitting requirements and the
effects of the upcoming land ban regulations.

     In this memo I will first describe some potential effects
of the land ban restrictions, followed by a discussion of  the
permitting of land treatment units.  Finally,  this memo also
transmits the land treatment guidance and discusses the treatment
demonstration required of land treatment units seeking an  operating
permit.

POTENTIAL EFFECTS OF LAND DISPOSAL RESTRICTIONS

     Most of the current land treated wastes will be affected by
promulgation of land ban regulations in July 1987 (as part of the
"California List"),  or August 1988 (as part of the "first  third").
The Hazardous and Solid Waste Amendments of 1984  (HSWA) indicate
that such land banned wastes should be treated prior to disposal,
unless the owner/operator can show by petition that there  will
be no migration for as long as the wastes remain  hazardous.

-------
                               -2-
                                            OSWER POLICY DIRECTIVE NO.

                                          9486.0032
     The following additional statements apply to the case of
land treatment of hazardous wastes:

     o  In the land ban context, land treatment itself apparently
        does not "count" as a form of treatment, since HSWA
        defines land treatment as a form of land disposal.

     o  Thus, before placing wastes in a land treatment unit it
        will likely be necessary to pretreat the wastes to a
        level to be determined in future land ban regulations; or
        to present a petition showing that there will be no
        migration for as long as the wastes remain hazardous.

     Of particular interest to the land treatment situation is
the issue of air emissions.  As required by 3004(n) of HSWA, we
are developing air emission regulations for treatment, storage
and disposal units.  In addition, we are developing a toxicity
characteristic that will take into account the air emission
potential of waste streams.

     Based on the above, I would like to present the following
strategy for handling land treatment permit applications with
respect to the 1988 permitting deadline, and the potential
impact of the land bans.

POLICY ON PERMITTING OF LAND TREATMENT UNITS

     Given the uncertain and potentially short life of certain
land treatment units, what is the Agency's policy on RCRA permits
for such units?  We must, on one hand, respond to the permit
applications of those facilities which choose to apply for an
operating or demonstration permit.   On the other hand, we should
make sure that facilities understand the potentially short
operating life of land treatment as it is practiced today, and
consider the option of closing or modifying their land treatment
units by the effective date of the relevant land ban provisions.

     Therefore, Regional Offices and States should take the
following actions:

     First, they should inform owners and operators of land
treatment units as soon as possible of the points made in this
policy statement, and determine if the owner/operator wishes to
continue with the permitting process.  Facilities should also be
encouraged to consider reducing the volume of land treated
hazardous wastes through recycling and other activities.

-------
                                              03WER POLICY DIRECTIVE KO.

                                .3-          9486  . 00-2    '
     Second, the Region and State should vigorously pursue permit
processing for those units which opt to remain in the permit — ! -
   ^m-  This means carefully considering the merits and requirements
   tKe various permit options (i.e., short-term permits, "Phase I"
                                   .,                   ,    ase
 permits, and final operating permits) discussed in the final Permit
 Guidance Manual on Hazardous Waste Land Treatment Demons trationT -

 J f.  This also means responding quickly and appropriately to Part B
 deficiencies.  Facilities should be able to submit a complete
 application after only one Notice of Deficiency (NOD), following
 the issuance of the final Demonstration Guidance.  Those facilities
 which do not correct deficiencies after that final NOD should be
 placed in the path for permit denial.  The Region or State should
 issue a draft notice of intent to deny a permit,  pursuant to the
 permitting procedures of 40 CFR Part 124,  due to  failure to
 correct deficiencies in the application (§124.3 (d)).   (The
 applicant may submit the required information during the public
 comment period on the draft notice,  and the Region or  State may
 change their decision and prepare a  draft  permit; see  § §124.13
 and 124.14.)   The Region or State should note in  any permit denials
 that  the denial applies only to the  unit's operating life,  not  to
 the unit s post-closure care period.   Regions and States should,
 in  most cases,  continue to pursue the portion of  the unit's permit
 applicable to post-closure care under §270.1 (c) due to the
 corrective action authorities that a  permit can provide.

      Third,  for those facilities  which choose to  discontinue  the
 permit process  with  respect to  the operation or demonstration
 phase  of the  permit,  the  Region or States  should  obtain the
 owner/operator's  written  agreement to submit a  closure plan no
 later  than 180  days  prior to the  statutory date of  the relevant
 land  disposal  restriction rule.   This  agreement should be specified
 in  the  unit's  closure plan under  §265.112.   The Region or State
 should  proceed  at  this  time to  review the  technical  and procedural
 adequacy  of the closure plan, so  that  they will be  prepared  to
 approve,  modify,  or  disapprove  the plan  expeditiously  when  the
 agreed  closure  date  arrives.  Units which  agree to  close as
 outlined  above will  not require further  processing  of  applications
 for the operation  or demonstration phase of  their permits,  but
may require a permit  for  post-closure  care.

     I  realize  that  a number of issues remain regarding the
 closure/post-closure of land treatment units under  Part 265
 Subparts G and M.  In order  to address these issues, the Office
of Solid Waste is preparing a brief guidance on the closure of
 land treatment units.  I  intend to issue this guidance by December 31,
1 y 86 .

-------
                                                  OSiVEfs POLICY DIRECTIVE f.'G.

                               -4-
                                                9 4 8 t> ,  {;•; - :>
LAND TREATMENT DEMONSTRATION GUIDANCE
     To assist permit writers and owner/operators of those land
treatment units that wish to continue pursuit of a land-treatment
facility permit, we are issuing the final version of the', afore-
mentioned Permit Guidance Manual on Hazardous Waste Land Treatment
Demonstration.  A copy of the manual is attached.  This manual
provides guidance on the conduct of land treatment demonstrations
in compliance with Section 264.272.  The manual contains specific
laboratory and field test methods that may be used to complete
the demonstration and describes alternative technical approaches
and permitting procedures to accommodate the treatment demonstra-
tion.  This final guidance manual was prepared based on comments
received on the December 1984 draft (EPA/530-SW84-015).

     I want to emphasize that the methods described in the Land
Treatment Demonstration Manual are for guidance only and are
neither requirements nor regulations.  An applicant may use
alternative methods, provided that these methods comply with the
applicable regulatory requirements.  We believe that methods
which are equivalent to or more comprehensive than those described
in the manual will meet the regulatory requirements.  While we
believe that the specifications provided for each of the described
test methods are a reasonable estimate for a complete treatment
demonstration in compliance with Section 264.272, the permit
writer may modify these specifications as necessary.

     Finally, I want to highlight that completion of a successful
land treatment demonstration or issuance of a land treatment
operating permit does not necessarily constitute a demonstration
of "no migration for as long as the waste remains hazardous"
for purposes of exemptions from land disposal restrictions.  The
demonstration for an exemption will need to address factors
related to longer timeframes for migration to surface and ground
water than are addressed in the permit demonstrations.  It may
also need to address migration to air—a consideration not currently
part of the permit demonstrations.

Attachment

cc:  RCRA Branch Chiefs, Regions I-X
     Permit Section Chiefs, Region I-X
     Marcia Williams
     Bruce Weddle
     Jack Lehman
     Eileen Claussen

-------
                                           OSWER POLICY DIRECTIVE NO.

                                         9486..00s2  fl
          PERMIT GUIDANCE MANUAL ON

HAZARDOUS WASTE LAND TREATMENT DEMONSTRATIONS





                FINAL VERSION
             Office of Solid Waste
     U.S. Environmental Protection Agency
            Washington, D.C.  20460
                  July 1986

-------
                                           OSWEK POLICY DIRECTIVE NO.

                                         9486 • 00-2   *
This  guidance document was prepared  for the

    U.S.  EPA, Office of Solid Waste  by:
      Utah  Water Research Laboratory
         Utah State University
         Logan, Utah 84322 - 8200

-------
                                                          OSWER POLICY DIRECTIVE NO.

                                                         9486  .00-2   «
                               ACKNOWLEDGMENTS


     The  toxic  and  hazardous  waste management group  (THWMG)  at  Utah  State
University  would  like  to  acknowledge  the  leadership,  guidance,  and
contributions provided by Jon Perry, Office of  Solid Waste, and John Matthews,
Robert  S.  Kerr  Environmental Research Laboratory,, with  regard  to planning,
organizing, and executing the tasks  involved in producing this manual.   Mike
Gansecki,  U.S.  EPA  Region   VIII,  provided  much of  the  technical   input  and
administrative guidance  that has been incorporated  into  this draft  manual.
Also, K.  W.  Brown and  Associates,  Inc.,  and  Michael Flynn, Office of  Solid
Waste,  are  acknowledged for  providing  the  groundwork for  conducting   Land
Treatment Demonstrations in  the  Draft Manual published in  1984  (EPA/530-SW-84-
015).  Gordon Evans,  of K.  W. Brown and Associates, Inc.,. 1s acknowledged for
his  comments  and  input  concerning  problems  and approaches taken in the  1984
Draft Manual.   Finally, the members of  the  Land  Treatment  Coordinating
Committee  are acknowledged, including the Subcommittee,  for providing  the
framework for developing this manual  and for providing feedback throughout the
development of this document.
                                  ii

-------
PREFACE
                                                               OS'.'.'EA eOLiCY OIRiCilVi ,.J.

                                                              94S6.00-.2  a
     Subtitle C of the Resource Conservation and Recovery Act (RCRAr)  requires ----
the U.S. Environmental Protection Agency  (U.S.  EPA) to  establish  a  federal
hazardous waste management program.  This program must ensure that  hazardous
wastes are handled safely  from generation to final disposition.  The U.S. EPA
issued a series  of hazardous waste regulations  under Subtitle C of RCRA,
published in 40 Code  of  Federal  Regulations  (CFR) Parts 260 through 265, 270
and 124.

     Parts 264 and 265 of 40 CFR contain standards  applicable to  owners and
operators of all facilities that treat, store, or dispose of hazardous wastes.
Wastes are identified or listed as hazardous under 40 CFR Part 261.   The Part
264 standards are implemented through  permits  issued by authorized States or
the EPA  in accordance with  40  CFR  Part  124  and  Part  270 regulations.  Land
treatment, storage, and  disposal  (LTSD) regulations in 40 CFR  Part 264 issued
on July  26,  1982,  establish  performance  standards  for  hazardous  waste
landfills, surface  impoundments, land  treatment units,  and waste  piles.

     This final  manual  provides  guidance on  land  treatment  demonstrations
required under  Section 264.272 for all  owners/operators  of  hazardous waste
land treatment  units.   The  manual  contains specific laboratory  and field
test methods that  may be  used  to complete  the  demonstration and  describes
alternative technical approaches and  permitting procedures  to  accommodate
the treatment demonstration.  This guidance does not supersede the
regulations promulgated under  RCRA and  published  in the. Code of  Federal
Regulations, and  is  not  intended to  suggest that other  approaches  to the
demonstration of  land treatment might  not  also satisfy  the  regulatory
standards.

     This final  guidance  manual  was  prepared  based  on  comments  received
concerning the December 1984 draft document (EPA/530-SW-84-015),  titled Draft
Permit Guidance Manual on Hazardous Waste Land Treatment Demonstrations:  For
Public Comment.              ~~                ~~~
                                      ill

-------
                                                                          . vll IL. i.U.
                              EXECUTIVE SUMMARY


     Hazardous waste  land  treatment  (HWLT)  can be considered as the  intimate
mixing or dispersion  of  wastes  into  the  upper  zone of  a  soil  system, with the
objectives of  degradation,  transformation,  and/or immobilization,  leading to
an environmentally acceptable assimilation of the waste.  The overall goal is
the  simultaneous  ultimate  disposal  and treatment of  hazardous  wastes,  while
ensuring protection of public health and  the environment.

     The U.S.  Environmental  Protection Agency  (U.S.  EPA)  issued standards in
July 1982, required by the Resource Conservation and  Recovery Act (RCRA), that
are used for permitting a hazardous waste land  treatment  (HWLT)  facility.  The
regulations define the principal elements of a  HWLT program  as:  a) the wastes
to be  applied, b) the design  and  operating measures necessary  to maximize
degradation,  transformation,   and  immobilization  of the  hazardous  waste
constituents, and c)  an unsaturated zone  monitoring program.

     A  land  treatment demonstration  (LTD)  addresses the requirement  in  the
regulations  that the owner  or  operator  of   a  land  treatment  unit must
demonstrate, prior to application of the  waste,  that  hazardous constituents in
the  waste  can be  completely degraded,  transformed,  or immobilized in  the
treatment zone.   An  LTD is  also required to establish the  protectiveness of
human health and the  environment  for the design and  management strategy used
for a waste at a site.

     Successful  performance  of the  land  treatment demonstration  (LTD)  is
required in order to  obtain a final  permit under 40 CFR Parts 264 and 270  for
a hazardous waste land treatment  unit.   In  consideration of  the complexity of
the  demonstration  requirements,  this  document  was prepared to  give  the
applicant and  regulatory agency guidance  on the information needed  to assist
in choosing and implementing the LTD approach.

     Permit  options   for  land  treatment  differ from  those  of other  land
disposal technologies.   The  LTD, much  like  the  trial  burn  for incinerators,
may require a  permit  to  allow for trial  performance.  A trial performance  may
be conducted  under a  short-term  demonstration   permit or  a  two-phase permit.
It is also possible to apply directly for a  full  scale permit.   The applicable
permitting scenario depends in part on  1)  whether  the unit is  new or existing,
2) the conditions of  the site, and 3) past,  present,  and planned operations.

     The technical approach  to  accomplishing the goal of  demonstrating  land
treatment  is  to  provide a  methodology for  evaluating site,  soil,  and  waste
characteristics  and  for assessing  waste  treatment  processes  within  the
treatment zone soil.   The methodology is  used to determine the potential  for a
soil  to  assimilate a  candidate  hazardous  waste (soil  site  assimilative
                                   iv

-------
capacity; SSAC) so that there  is  no  statistically  significant release to the
environment  from the  treatment  zone.

     While much  of  the information preliminary to  the  LTD should .have been
supplied  as  part of  other  permit application requirements,  this  document
provides supplementary  guidance  on  some  aspects  of  these  application
requirements.  Of particular importance for existing units (ISS)  is  guidance
on  a reconnaissance  survey  of soil   and  hazardous  constituent  sampling and
analysis.   Data from  this  investigation  are  used to  define  the  spatial
distribution of hazardous  constituents across  HWLT  units and to  formulate the
permit and treatment  demonstration  approach.

     The  logic  and flow of information for making  decisions in choosing the
permit  approach  and  the technical elements  in  the LTD  involve  answering   a
series  of  questions.   The  questions  ask  1) whether  the  unit  is new or
existing, 2) whether  hazardous  constituent data have been collected along with
other Part  B  information,  3)  whether  the unit  1s operating effectively to
treat wastes,  4) whether  past  activities  can  be  adequately documented from
literature,  past records,  and operating data,  and  5) whether major design and
operation changes  are  planned.   The  answers  to  these questions,  and the
judgment  of  the  regulatory  agency, determine which  of the  LTD  scenarios will
be employed.

     Technical methods  for  performing each  step  of the LTD are presented  in
this  manual.    Methods  discussed  include reconnaissance surveys,  laboratory
analyses, mathematical  modeling,  and  field  plot  studies.   These  methods  are
not  necessarily  listed  in  order of performance nor are they all  required  in
any  given case.   A technical approach section discusses issues  common  to  all
methods,  such as statistical and analytical aspects of an LTD.

     Volatilization  will   not  be directly measured  in the LTD  methodology
presented in  this  guidance manual.   The  Office of Air Quality  Programs  and
Standards (OAQPS), U.S. EPA,  is currently developing  air  emission  rules  for
all  RCRA facilities.   Also,  the Robert S.  Kerr Environmental   Research
Laboratory  (RSKERL),  U.S. EPA,  is  currently evaluating methodologies  for
assessing volatilization specifically for  land treatment facilities.  However,
to   impose  guidelines or  requirements  at  the  present  time  is considered
premature  and may be confusing,   since  no  standard methods are currently
available  for  measuring  volatile  emissions.   Where  obvious  air  emission
problems  are identified on a  case-by-case basis,  permit writers  may address
volatilization  under the omnibus provision of  HSWA  Section 3005(c)(3).

      A  mathematical  model  based  on  the  model developed by  the  U.S. EPA
(RSKERL)  for use in  banning specific hazardous wastes from land treatment  is
presented in this  guidance manual  for integrating  the treatment processes  of
biodegradation  and  Immobilization.   A mathematical description  of  the  land
treatment  system provides a unifying  framework for  the evaluation  of
laboratory screening  and  field  data.   Specifically,  the model  provides  a
framework for determining  the  effects of (1)  design and operating parameters
(loading  rate,  loading  frequency,  irrigation, amendments  to  Increase
degradation;  (2)  site characteristics  (soil  type,  soil  horizons,  soil
permeability);  and  (3) environmental  parameters  (season,  precipitation)  on

-------
treatment  performance.   Also,  the model  can  be  used  for comparison  of  the
effectiveness of treatment  using  different design and  operating  practices  in
order  to  maximize  treatment,  and  for  the  selection  of  principal  hazardous
constituents for monitoring waste performance.

     Results of  field analysis, where  field studies are  selected  based  on a
laboratory assessment using the model,  will  be  useful  for verification of the
model and for providing information for modifying the model.  Also where site,
soil,  and  degradation  kinetic  information  can be  developed  based on field
sampling, minimal laboratory analyses are required (determination of partition
coefficients) for using the model.
                                   vi

-------
                                                                   POLICY DIRECTIVE KO,

                                                                «6  .00-2   «
                                  CONTENTS

Acknowledgments  	    ii
Preface	iii
Executive Summary   	    ix
Figures    	     x
Tables	xi

   1  Introduction and Administrative Approach to the Performance
      of a land treatment demonstration  	      1
          1.1  Introduction  	      1
          1.2  Basic LTD Concepts	      2
               1.2.1  Toxicity of the waste  to the soil  treatment
                      medium 	      2
               1.2.2  Degradation of hazardous constituents   ....      4
               1.2.3  Transformation/detoxification of hazardous
                      constituents 	      4
               1.2.4  Immobilization of hazardous constituents    ...      4
          1.3  Regulatory Requirements   	      5
          1.4  Administration Options for  Land Treatment
               Demonstrations   	     10
          1.5  Criteria for Choosing a Land  Treatment Demonstration
               Scenario	     15
          1.6  Implications of the Hazardous and  Solid Waste
               Amendments of 1984 (HSWA) for Land Treatment
               Demonstrations and Facilities   	     24
   2  Technical Approach to the Performance  of an LTD   	     26
          2.1  Evaluation of Treatment Process 	     26
          2.2  Determination of the  Site/Soil  Assimilative
               Capacity (SSAC) for a Candidate Waste 	     29
               2.2.1  The toxicity component of the SSAC	     29
               2.2.2  The immobilization component of the SSAC    ...     30
               2.2.3  The biodegradation component of the SSAC    ...     31
               2.2.4  The transformation/detoxification  component
                      of the SSAC	     31
               2.2.5  Calculation of the SSAC	     32
               2.2.6  Principal hazardous  constituents (PHCs)  ....     32
               2.2.7  Use of the SSAC for  design  and management   ...     32
          2.3  Design and Management Parameters   	     33
               2.3.1  Loading rate	     33
               2.3.2  Waste application frequency 	     34
               2.3.3  Waste application method 	     34
               2.3.4  Operation and  management factors  	     34
               2.3.5  Evaluation of  the effect of design and
                      management parameters  on SSAC values  .   .   .   .  '.     35
          2.4  Field Verification Study 	     35
                                  vii

-------
                          CONTENTS  (CONTINUED)

       2.5  Analytical Aspects of Conducting an LTD	    35
       2.6  Analytical Costs	    43
3  Procedures for Collecting Field Information for Reconnaissance
   Survey and Field Verification Studies	-  . "  .    45
       3.1  Introduction	   .    45
       3.2  Waste Characterization	    46
            3.2.1  Sampling and sample collection 	    47
            3.2.2  Sample handling and storaqe 	    48
            3.2.3  Analysis of waste characteristics 	    48
       3.3  Waste Management Records for an Existing Site  ....    49
       3.4  Soil Characterization	    49
            3.4.1  Soil survey	    49
            3.4.2  Characterization of distribution of hazardous
                   constituents in soil (existing sites only)  ...    53
       3.5  Groundwater Monitoring 	    57
       3.6  Data Interpretation and Presentation	    59
4  Predictive Tool for Land Treatment Demonstrations 	    61
       4.1  Introduction	    61
       4.2  Model Description	    62
            4.2.1  Definition of terms	    62
            4.2.2  Model construct	    63
            4.2.3  Immobilization/transport 	    63
            4.2.4  Constituent degradation  	    66
            4.2.5  Input  .  .	    66
            4.2.6  Output	    66
       4.3  Model Application	,	    69
       4.4  Examples	    70
5  Laboratory Analyses and Studies for Selecting Design and
   Operation Conditions   	  .....    74
       5.1  Introduction	    74
       5.2  Waste Characterization 	    74
       5.3  Soil Characterization	    75
       5.4  Toxicity of Waste to the Soil Treatment Medium ....    75
            5.4.1  Possible assays	    75
            5.4.2  Preparation of waste soil mixtures for
                   bioassays	    85
            5.4.3  Determination of loading rates 	    86
            5.4.4  Data interpretation	    88
       5.5  Transformation/Detoxification of the Waste:Soil
            Moisture	    89
       5.6  Immobilization of Waste Constituents in the Soil
            Treatment Medium 	    90
            5.6.1  Experimental apparatus for determination of
                   partitioning between oil phase and aqueous
                   phase  (Ko)	    92
            5.6.2  Experimental procedure for determination of Ko.   .    94
            5.6.3  Experimental apparatus for determination of
                   partitioning between soil phase and aqueous
                   phase  (Kd)	-.    95
            5.6.4  Experimental procedure for determination of Kd.   .    95
                                  viii

-------
                            CONTENTS  (CONTINUED)

               5.6.5  Partitioning between aqueous phase and air
                      phase (Kh)	    96
               5.6.6  Experimental procedure for determination of Kh.  .    96
               5.6.7  Three phase partitioning method for Ko and
                      Kh determination	  .    97
               5.6.8  Experimental procedure for the combined
                      contamination of Ko and Kh	    97
               5.6.9  Data handling	    99
          5.7  Degradation of Waste Constituents in the Soil
               Treatment Medium 	 .....    99
               5.7.1  Hazardous constituent reduction evaluation
                      techniques	    99
   6  Monitoring Treatment Performance in the Field  	   108
          6.1  Purpose of Field Verification Study for New
               and ISS Facilities	108
          6.2  Field Verification Study Alternatives 	   109
          6.3  Selection of Design and Management Parameters  ....   110
          6.4  Analytical Aspects of Field Verification 	   Ill
          6.5  Plot Preparation	Ill
          6.6  Waste Application   	   113
          6.7  Field Verification Study Monitoring   	   113
               6.7.1  Collection  and analysis for soil core and
                      soil pore liquid samplers	114
               6.7.2  Groundwater monitoring   	   118
               6.7.3  Data interpretation	118
   7  Quality Assurance Program for Conducting an LTD   	   119

References	122
Appendices

   A  Summary of Treatment Demonstration Permit Application
      Information Requirements  	   131
   B  Statistical Considerations  for the Performance of an LTD   ...   138
   C  Information Concerning the  HWLT Mathematical Model    	   147
   D  Target Detection Limits in  Water for Constituents of
      Petroleum Refining Wastes ....   	   169
   E  Target Detection Limits for Selected Organic Compounds in
      Water	171
   F  Extended Ritz Model Fortran Listing    	   175
   G  Example of a Monitoring Schedule for a Field Plot
      Demonstration 	   198
                                   ix

-------
                                   FIGURES                         .  -
Number                                                                    Page
 1.1  Treatment processes and monitoring techniques for a land
        treatment unit	     3
 1.2  LTD guidance for selection of appropriate scenario 	    16
 1.3  Specific guidance and information requirements for LTD
        meeting the definition for Scenario 2	22
 1.4  Specific guidance and information requirements for LTD
        meeting of the definition for Scenario 3	23
 4.1  Conceptual description of land treatment system used in
        extended RITZ model formulation   	    64
 4.2  Transport and partitioning relationships within soil control
        volumes used in modified RITZ model	65
 4.3  Sample constituent total soil concentration profile at
        selected time periods after initial waste application  ....    68
 4.4  Time distributions of naphthalene concentration in the plow
        zone and depth distributions at specific times in the lower
        treatment zone	73
 5.1  Sample preparation and analysis scheme for the determination
        of Kh, Kd, and Ko	93
 5.2  Apparatus for three-phase partitioning coefficient
        determinations  	    98
 5.3  Laboratory flask apparatus used for mass balance measurements  .   .   101
 5.4  Laboratory microcosm apparatus used in laboratory AERR model
        validation studies   	  	   106
C2.1  Sample input data file	153
C2.2  Sample output file	156
C2.3  Sample supplementary output file for graphic displays 	   162
C3.1  Enhanced RITZ model structure	   164

-------
                                    TABLES

Table                                                                      Page
1.1       Summary of Specific Part B  Information Requirements for
          Land Treatment Facilities  	    6
1.2       Standards Given  in 40 CFR Section 264.272 - Treatment
          Demonstration	    8
1.3       Standards Given  in 40 CFR Section 264.271 Related to Section
          264.272 - Treatment Program   	    8
1.4       Standards Given  in 40 CFR Section 264.273 Related to Part
          264.272 - Design  and Operating Requirements 	    9
1.5       Land Treatment Permit Elements   	    11
1.6       Permit Application Content for Each Permit Element   ....    12
1.7       Information Required to Assess Planned Changes in Design and
          Operation and to  Assess the Suitability of the Use of
          Scenario 2	    20
2.1       Monitoring and Evaluation Strategies to Assess Treatment
          Processes in a Land Treatment Demonstration 	    27
2.2       Design and Operation Parameters for LTDs    	29
2.3       Suggested Analytical Information for an LTD	37
2.4       Summary of Suggested Maximum Metal Accumulations Where
          Materials Will be Left in Place at Closure	42
2.5       Suggested Metal  Loadings for Metals with Less Well-Defined
          Information	43
2.6       Estimates of Analytical Costs for Type I, II, and III Analyses.    44
3.1       Useful Waste Management Data and Records 	    50
3.2       Soil Physical and Chemical Properties To Be Determined in Soil
          Survey	52

-------
                              TABLES  (CONTINUED)


Table                                                                     Page

3.3       Suggested Uses of Field Information	60

4.1       Design/Operational Variables Required for Use in the Extended
          RITZ Model	67

4.2       Variables Required from Laboratory Analyses, Prediction
          Methods, Etc., for Use in the Extended RITZ Model	67

4.3       Physical Properties of the Soil Columns Used for Examples 1
          Through 4     	70

4.4       Operating Parameters and Waste Characteristics for Examples
          1 Through 4	71

4.5       Summary of Results for Sample Runs	73

5.1       Toxicity Screening Bioassays Useful in Evaluating Hazardous
          Waste Applications to Soil	76

6.1       Comparison of Field Verification Alternatives  	  110

B.I       Frequency Distribution of Soil Properties   	  140

B.2       Examples of Number of Samples Required to Achieve a Specified
          Analytical Precision and Level of Confidence, Based on Expected
          Variability of Sample Concentrations, as Determined in an
          Exploratory Study   	   .144

D.I       Constituents of Petroleum Refining Wastes   	  169

E.I       Target Detection Limits for Organic Compounds  	  171

6.1       Example of -a Monitoring Schedule for a Field Plot Study  ...  200
                                    xn

-------
                                                         OSWER POLICY DIRECTIVE NO.

                                                       9486 • 00-2  «*
                                  CHAPTER  1

         INTRODUCTION AND ADMINISTRATIVE APPROACH TO THE PERFORMANCE
                      OF A LAND TREATMENT  DEMONSTRATION
1.1  INTRODUCTION

     Under  the  authority  of  Subtitle  C of  the Resource  Conservation  and
Recovery  Act  (RCRA), the  U.S.  Environmental  Protection  Agency  (U.S.  EPA)
promulgated regulations for the treatment, storage, and disposal of hazardous
waste 1n land treatment  units (40 CFR Part 264).  These regulations require a
permit  for  the  operation  of a  hazardous  waste land  treatment  (HWLT) unit.
Section 264.272  stipulates that the first step  in  obtaining  such  a permit is
to complete a land treatment demonstration  (LTD).

     The land treatment demonstration is  used  by the permitting authority to
define  two elements  of  the  land treatment program.  First, the demonstration
establishes what  wastes may be  managed  at  the unit.    Wastes that  will  be
applied must be  subject to  degradation, transformation, and/or  immobilization
processes in the soil  such that  hazardous  constituents are not  expected to
migrate from  the defined treatment  zone.    Second,  results  of the treatment
demonstration will  be   used  to define the  initial  set  of waste  management
practices,   including  loading  rates,  that  will  be   Incorporated  Into  the
facility permit.

     The treatment  demonstration  can be  completed  using  information derived
from published literature,  laboratory studies, field  studies,  and/or actual
facility operating experience.  However,  the U.S. EPA generally believes that
an inadequate data base  exists in the published  literature at the present time
to  predict  unit-specific  waste-soil  interactions.   Consequently, most  land
treatment permit  applicants must use laboratory studies, field studies, actual
facility operating experience,  or  a  combination of these  approaches  to
complete the treatment  demonstration.

     One  criterion  for  whether  an LTD permit  is needed  is 1f  field  or
laboratory data  will be collected.   The  regulations assume that  any form of
disposal, even in a small-scale laboratory situation, requires a permit.

     The purpose of this manual  is to provide guidance on specific approaches,
Including laboratory and field test methods, that may be used to complete the
treatment demonstration  as required  under  Section 264.272  for  owners  and
operators of  hazardous waste  land treatment  units.   The  manual  addresses
policy  and technical aspects  of the demonstration, and describes alternative
permitting approaches.

-------
     This  manual  expands the  general  guidance on  treatment  demonstrations
already provided in the following documents:

          Permit  Applicants'   Guidance  Manual  for Hazardous  Waste  Land
          Treatment, Storage,  and Disposal Facilities (U.S. EHA, I964a);

          RCRA Guidance Document:   Land Treatment Units (U.S. EPA, 1983b).

     The U.S.  EPA  wishes  to  emphasize that  the methods described  in  this
manual  are  for  guidance only and  are not regulations.  An  applicant may use
alternative methods, provided that  these  methods comply with  the  applicable
regulatory requirements.  EPA believes that methods which are equivalent to or
more  comprehensive  than those  described  herein  will  meet the  regulatory
requirements.   While the U.S.  EPA believes that  the  specifications  provided
for  each  of the  described test methods  are  a  reasonable  estimate  for  a
complete  treatment demonstration  in compliance  with  Section 264.272,  the
permit writer may modify these specifications as necessary.

1.2  BASIC LTD CONCEPTS

     The land  treatment demonstration  Is  designed to evaluate  the  principal
processes  involved  in  the treatment of  hazardous wastes applied  to  a  land
treatment   unit.    These  processes  include  degradation,  transformation,  and
immobilization.   Figure  1.1 shows  a conceptual  diagram  for  a  land  treatment
demonstration  site,  illustrating  a  mass  balance  approach.   Leaching  and
volatilization  are inversely related  to the process of immobilization, and are
Included  for  the  purpose of  illustrating a mass  balance around  the  soil
treatment  zone  for each  hazardous  constituent.    For  many  wastes,  only  a
fraction  of  the  applied material  is considered  hazardous  under  the  RCRA
definition.   Emphasis  is  therefore-placed on  Identifying  and evaluating  RCRA
Appendix  VIII  compounds (defined as  hazardous  constituents  in  the  RCRA
regulations, 40 CFR 261).

     Figure  1.1  also  illustrates  the  principal  monitoring  techniques for  a
field verification  study  as part of  a  land  treatment demonstration--analysis
of wastes, soil cores  in  and below the treatment zone,  soil-pore liquid below
the treatment zone, and groundwater monitoring where appropriate.

1.2.1  Toxicity of the  Waste to  the  Soil Treatment Medium

     The  decomposition  of  hazardous   wastes  and  the  detoxification
(transformation)  of  PHCs in  the  soil  depend  primarily  on  the  enzymatic
activities of soil microorganisms.   The evaluation of the  impact of  hazardous
wastes  on  indigenous soil  microbial  populations  is  important,  especially for
those wastes  containing  hazardous  constituents  specifically designed  to
Inhibit biological  activity, e.g.,  wood  preserving  wastes,  pesticide wastes,
etc.  The toxicity of  a waste  can  be evaluated using one or more  short-term
bloassay testing procedures.  The choice of a particular assay or a battery of
assays  to  be used  must be made based on the ability of selected  tests  to
protect a  wide range  of metabolic  capabilities  of decomposers  and  -nutrient
cycling soil organisms.  The  purpose 1n using  bioassays  is to ensure  that the
biological  pathways for assimilating  a  hazardous waste are operative.

-------
                 MASS BAUNCE APPROACH
                                                                              MONITORING TECHNIQUES
           VOLATILIZATION/
           PHOTOOEGRADATION
Treatment
Zone
(TZ)
Below
Treatment
Zone (BTZ)
Groundwaler
                                                    Waste Analyses
                                                                                                                     Weds
   Figure 1.1.   Treatment  processes and monitoring  techniques  for a  land treatment unit.

-------
     Hazardous wastes,  applied  in  too  high of  a concentration  in  the soil
(loading rate), may reduce the microbial population and/or microbial  activity
and  the concomitant  process of  biodecomposition.   Under  these conditions,
toxic constituents may leach from the zone of incorporation (ZOI) through the
treatment   zone  and  may  migrate  from  the bottom  of the  treatment zone.
Bioassays   may be  used  to help  establish waste  application  rates  and
frequencies that will not  appreciably reduce microbial  function in the soil.
Bioassays may  also  be used  to follow the transformation (detoxification)  of
the waste as biodegradation products are formed in the soil, since a candidate
waste should not  be  applied to  land unless  it is rendered  nonhazardous as a
result of treatment.

1.2.2  Degradation of Hazardous Constituents

     Degradation of waste and waste constituents  describes the loss of  parent
compounds   through  chemical and  biological  reactions within  the soil/waste
matrix.  Complete degradation is  the term used to  describe the process  whereby
waste  constituents  are mineralized  to inorganic  end  products,  generally
Including carbon  dioxide,  water,  and   inorganic   species,  such  as nitrogen,
phosphorus,  and  sulfur.   The   rate   of  degradation  may be  established  by
measuring the loss of the parent  compound with time.

     The biodegradation potential of hazardous constituents in waste(s) to be
applied at  the proposed land treatment  facility is critical as biodegradation
usually represents the  primary removal  mechanism  for organic constituents in
waste(s)'   Hazardous constituent  degradation  rates  may be determined from
appropriate literature  data and/or from experimental  procedures described in
Chapter 5 of this manual.

1.2.3  Transformation/Detoxification of  Hazardous  Constituents

     The chemical  and/or  biological conversion of hazardous  constituents to
less toxic  intermediates within the land treatment unit  should be evaluated in
a determination of hazardous waste land treatability.   Transformation may be
addressed  along  with degradation  based on  parent and   intermediate  compound
characterization procedures.  Chemical  and bioassay  analyses are recommended
to  ensure  that  transformation/detoxification processes  are  active  in  the
soil/waste mixture.

1.2.4  Immobilization of Hazardous Constituents

     Immobilization  refers to the  affinity of  a chemical  for  particulate
surfaces in the soil treatment  zone.   Chemicals  that adsorb tightly  to soil
may  be less  subject to  environmental  transport  in  the solution (leachate)
phase and/or in the gaseous  (volatile)  phase.

     Leaching  refers  to the movement of materials through the  treatment zone
to deeper  soils  and/or  to groundwater.    An  LTD for a properly  operating land
treatment site should show the absence of hazardous constituent  migration.

-------
      Volatilization refers to the  process by which applied materials are lost
to the  atmosphere.  Volatilization will  not  be directly measured  in  the LTD
methodology  presented  in this  guidance  manual.    The  Office of  Air  Quality
Programs and Standards (OAQPS), U.S.  EPA, is  currently  developing air emission
rules  for  all  RCRA facilities.   Also,  the  Robert  S.  Kerr  Environmental
Research  Laboratory,  U.S.  EPA,  is currently evaluating  methodologies for
assessing  volatilization specifically for land  treatment facilities.  However,
to  Impose  guidelines/requirements  at the present time  1s considered premature
and  may be confusing since  no  standard  methods are currently  available for
measuring  volatile emissions.  Where obvious  air emissions are identified on a
case-by-case  basis,  permit  writers  may address   volatilization  under  the
omnibus provision of RCRA.

      Subsequent  chapters  in  this manual will  explain  how these treatment
processes  are  measured  and  assessed through the use  of operating  data,
reconnaissance  surveys,  literature  information,   mathematical  modeling,  and
field plot studies.

1.3  REGULATORY REQUIREMENTS

     The  approach for land  treatment  demonstrations  (LTDs) is  organized  to
address  the  hazardous waste land treatment  (HWLT)  regulations  promulgated
under  the  Resource Conservation  and Recovery  Act, Subtitle C  in  40  Code  of
Federal  Regulations  (CFR),   Section 264.272, titled  Treatment  Demonstration.
The  treatment  demonstration  is  conducted  in  order  to obtain a  permit  to land
treat hazardous wastes under the  hazardous  waste  permit  program  as specified
In 40 CFR  Part 270.  Specifically, 40 CFR Section 270.20 addresses information
requirements for  a Part  B  permit for  operating a  hazardous  waste  land
treatment  facility.   These  information requirements  are  listed  in  Table 1.1.
The  Part B permit  information requirements presented  in 40 CFR  Section 270.20
reflect the  standards  promulgated in 40 CFR Part  264, and  are  necessary for
EPA  to determine compliance with Part 264 standards.

     Section 270.20  (a)  (3)  requires that the Part  B  permit  application for
land treatment units outlines a treatment demonstration plan as required under
Section 264.272  (Table 1.2).  This treatment  demonstration  plan  must  include
characteristics of the waste(s) to be  land  treated and a description  of the
unit  that  will  be  simulated  in  the demonstration,  including  waste
characteristics,  treatment  zone characteristics,  climatic conditions  and
operating  practices.   Additional  permit  requirements  of this  treatment
demonstration plan are presented in detail  in the  Permit  Applicants' Guidance
Manual  for Hazardous  Waste  Land  Treatment, Storage, and  Disposal  Facilities
(U.S. EPA 1984a) and are  summarized in Appendix A of this manual.

     A description of a land  treatment program to be used at a new or existing
facility is specified  in  Section  270.20(b) as  required under Section  264.271
(Table  1.3)  and  must  be  submitted  with  the   plans  for  the  treatment
demonstration.   The land treatment program must be updated  as necessary based
on results of the completed land treatment demonstration.   Table 1.1 indicates
general  information  requirements  of the  land  treatment  program  including:
waste(s) to be land treated,  design measures to maximize treatment,  procedures
for  unsaturated  zone monitoring,  list  of  hazardous  constituents  in the

-------
Table 1.1  Summary of Specific Part B Information Requirements  for Land
           Treatment Facilities (40 CFR 270.20)


270.20 (*a).  Treatment demonstration plan (as required  under 264.272),
     including:
     (1)  Waste and waste characterization
     (2)  Data sources to be used in the demonstration
     (3)  Laboratory or field tests
            (i) test type (column leaching, degradation,  etc.);
           (ii) materials and methods, including analytical  procedures;
          (iii) time schedule;
           (iv) characteristics of the unit that will  be  simulated in
                the demonstration (treatment zone,  climate,  operating
                practices);

270.20 (b).  Land treatment  program (as required under 264.271),  including:

    *(1)  Wastes to be land  treated
    *(2)  Design measures and operating practices necessary  to  maximize
          treatment in accordance with 264.273(a) including:
            (i) waste application method;
           (ii) waste application rate;
          (iii) measures to  control soil pH;
           (iv) enhancement  of microbial or enhancement  of chemical
                reactions;
            (v) .control of soil moisture content;
     (3)  Procedures for .unsaturated zone monitoring including:
            (i) sampling equipment, procedures,  and frequency;
           (ii) procedures for selecting sampling locations;
          (iii) analytical procedures;
           (iv) chain of custody control;
            (v) procedures for establishing background values;
           (vi) statistical  methods for interpreting results;
          (vii) justification for any hazardous  constituents
                recommended for selection as principal hazardous  consti-
                tuents (in accordance with criteria for  such selection in
                264.278(a));
     (4)  A list of hazardous constituents reasonably expected  to be in,
          or derived from, the wastes to be land treated based  on waste
          analysis performed pursuant to 264.13
     (5)  The  proposed dimensions of the treatment zone
270.20 (*c).   Design and operation Information (as required  under 264.273),
     including:
     (1)  Control of run-on
     (2)  Collection and control of run-off
     (3)  Minimization of run-off of hazardous constituents  from  the
          treatment zone
     (4)  Management of collection and holding facilities associated
          with run-on  and run-off control systems
     (5)  Periodic  inspection of the unit (270.14(b)(5))
     (6)  Control of wind dispersal of particulate matter, if applicable

-------
Table 1.1.  Continued
270.20 (d).  Food-chain crops considerations  (264.276(a))  (if grown  in/on
     treatment zone)
     (1)  Crop characterization
     (2)  Characteristics of waste,  treatment  zone,  and  waste application
          method and rate
     (3)  Procedures for crop growth,  sample  collection  and  analysis
          and data evaluation
     (4)  Characteristics of comparison crop

270.20 (e).  Food-chain crops and cadmium  considerations (264.276(b))

270.20 (f).  Closure considerations,  including vegetative  cover  (refer to
     264.28(a)(8), 264.280(c)(2), and  270.14(5)(13))

270.20 (g).  Ignitable or reactive waste considerations  (requirements in
     264.281)

270.20 (h).  Incompatible wastes and materials considerations (requirements
     in 264.282)

     [48 FR 14228, April, 1983
      48 FR 30114, June 30,  1983J
     *Information developed in or related  specifically  to Section 264.272.

-------
Table 1.2 Standards Given in 40 CFR Section 264.272 - Treatment  Demonstration


264.272 (a).  Hazardous constitutents in a waste to be land  treated  must  be
     demonstrated to be completely degraded, transformed,  or immobilized  in
     the treatment zone

264.272 (b).  Information sources for LTD include:
     (1)  Field tests
     (2)  Laboratory analyses
     (3)  Available data
     (4)  Operating data from existing units

264.272 (c).  Requirements when using field test and laboratory  analyses
     (1)  Simulate characteristics and operating conditions  for  proposed
          unit including
            (i) characteristics of the waste;
           (ii) climate in the area;
          (iii) topography of the surrounding area;
           (iv) characteristics of the soil in the  treatment zone (includ-
                ing depth);
            (v) operating practices to be used at the unit;
     (2)  Show that hazardous constituents in the waste will be  complete-
          ly degraded, transformed, or immobilized  in the  treatment  zone
     (3)  Conducted in a manner that protects human health and the
          environment considering:
            (i) characteristics of the waste to be  tested;
           (ii) operating and monitoring measures taken during the course
                of the test;
          (iii) duration of the test;
           (iv) volume of waste used in the test;
            (v) for field tests, the potential for  migration of  hazardous
                constituents to groundwater or surface water;
Table 1.3  Standards Given in 40 CFR Section 264.271 Related to Section
           264.272 - Treatment Program


264.271  (a).  Facility permit specifications include:
     (1)  Wastes capable of treatment at the unit based on 264.272
     (2)  Design measures and operating practices necessary to maximize
          the success of degradation, transformation, and immobilization
          processes in the treatment zone in accordance with 264.273(a)

264.271  (c)
     (2)  The maximum depth of the treatment zone may be no more than 5
          feet  (1.5 m) below the soil surface and no less than 3 feet (1 m)
          above the seasonal high water table.

-------
waste(s) to be land treated and the proposed dimensions of the treatment  zone.
Facility design, construction  and  operation and maintenance  information must
also  be provided  to  the U.S.  EPA as required  under  Section 264.273  (Table
1.4).   The reader is  referred  to  the Permit Applicants' Guidance Manual fgr
Hazardous Waste  Land Treatment,   Storage  and   Disposal  Facilities  U.S. ETA"
(l984a) Section  7.4,  Land Treatment  Program, and  Section 7.11, Checklist of
Permit Application Requirements for Land  Treatment  Units.


Table 1.4  Standards Given in 40 CFR Section 264.273 Related  to Part 264.272
           - Design and Operating Requirements
264.273(a).  Maximize treatment
     Use  conditions  established in  264.272  (design and operating  conditions
     used in 264.272) as a basis for facility permit specifications  (minimum):
     (1)  Rate and method of waste application
     (2)  Measures to control soil pH
     (3)  Measures to enhance microbial  or chemical  reactions
     (4)  Measures to control the moisture content of the treatment  zone

264.273(f).   If  the treatment  zone  contains  particulate  matter which may be
     subject to wind dispersal, the owner or operator must manage the unit to
     control wind dispersal.
     Standards promulgated in 40  CFR  Section  264.272  (a)  and (c)  (2)  specify
that to obtain a full-scale  permit, a  demonstration must be  performed  to'show
that any hazardous constituents contained in the waste to be  land  applied must
be  completely degraded,  transformed, or  immobilized in  the  soil  treatment
zone.   (The  treatment zone  is  defined  in  Section 264.271 as  no  more than 5
feet (1.5 m)  depth  from the initial  soil surface, and more than 3 feet (1 m)
above the seasonal  high water  table.)   If the  applicant  is  required to use
field or  laboratory analyses or  tests  to  conduct an  LTD,  these tests, which
involve the treatment  and  disposal of  hazardous waste, can only be  performed
under a treatment demonstration permit.

     The preamble to  the Part 264  regulations  (Federal Register, 47,  No. 143,
pp. 32326-7, July 26, 1982) explains  land treatment requirements more fully:

     The basic criterion used in  evaluating  a  treatment demonstration  is
     that  it  must  be  possible  to  achieve  complete  degradation,
     transformation or  Immobilization of the hazardous constituents  in a
     waste if that waste is to be applied at the unit. Within  the  limits
     of the  tests  used  in  the demonstration, this  is  a  standard  that
     requires 100* treatment.  EPA believes that land  treatment should  be
     limited to  wastes  for  which  complete  treatment  is  possible:
     therefore, the "10056 treatment" criterion  is most appropriate.  -EPA
     recognizes that it  will  not always  be  possible to  achieve  100*
     treatment at an operating unit because of variations in  climatic and

-------
     other  conditions not  fully  under  the  control  of the  owner or
     operator.   Thus, the  failure  to achieve 100%  treatment  at an
     operating  unit  does  not necessarily  constitute  a permit violation
     but rather will often be grounds  for modifying permit conditions to
     maximize the success  of treatment  at the  unit.                -  -

     The  regulations also  recognize the  probabilistic  nature  of  the
demonstration in Section  264.272  (c)  (2)  1n requiring  that an LTD "be likely
to  show"  complete  degradation,  transformation  or  immobilization.    Any
demonstration cannot guarantee  complete treatment beyond the conditions of the
test.   The  regulations also  suggest  that  statistical  testing  of significance
may be necessary to evaluate  a  treatment situation.

     Other sections of Section  264 Subpart  M standards  for land treatment are
relevant to the  performance  of  an LTD.  Part 264.278 presents a protocol for
unsaturated zone monitoring  at  a  full-scale facility.   The  unsaturated zone
monitoring information from  a reconnaissance  survey or  from  an LTD utilizing
field testing should be comparable to data generated in full-scale operation.
If food chain crops  are to  be  grown  on a  land treatment area, the LTD should
be designed to include considerations given in Section  264.276.  Treatment of
Ignitable or  reactive wastes  in  an LTD  must meet  the criteria  in Section
264.281.  The LTD  should  approximate the  design and operational  requirements
for full-scale operation of  a land treatment facility under Section 264.273.

1.4  ADMINISTRATIVE OPTIONS  FOR  LAND TREATMENT DEMONSTRATIONS

     Administrative procedures  allow  applicants  to  choose  one  of  three permit
approaches:                                 :

     (1)  an immediate full-scale  facility permit

     (2)  a short-term treatment demonstration permit followed by a full  scale
facility permit; or

     (3)  a two-phase permit.

     Full-scale, short-term, and  two-phase  permits are described  in 40  CFR
Section 270.63.  Table  1.5   outlines the  essential  elements of  these  permit
approaches,  and  the content  of  applications for each of these types of permits
is described in  Table 1.6.

     An applicant  with  an  existing  interim  status  land  treatment  unit  may
apply directly for  a full-scale facility permit 1f  complete treatment  can be
demonstrated  based on available  literature data,  additional  reconnaissance
data,  and/or  existing operating  data.   This  approach  requires documented
historical  records  and  intensive  historical  soil   and  waste characterization
data that  allow  reliable  retrospective  extrapolations and  conclusions
regarding the  treatment  of  Individual  hazardous  constituents.   Because  ISS
facilities are  "treated  as  though  they have  been issued permits" (while
awaiting completion of the Part 264  permitting  process),  field monitoring on
hazardous wastes already  applied at the facilities may  be  conducted  (i.e.,  a
reconnaissance survey of  existing  conditions).  However, these tests  must not


                                   10

-------
Table 1.5  Land Treatment Permit Elements (U.S. EPA 1984a)

Full-Scale Facility Permit

-  Used when complete data have been collected to satisfy the treatment
   demonstration requirement (i.e., using available literature data* oper-
   ating data, and/or lab or field test results).

-  Contains provisions necessary to meet all the Subpart M, Part 264 require-
   ments and all other applicable Part 264 standards.

-  Requires a 45-day public comment period and hearing if requested or
   required under state regulations.

Short-Term Treatment Demonstration Permit

-  Involves small-scale lab or field experiments to demonstrate that hazard-
   ous constituents in a candidate waste can be treated in the land treatment
   unit.

-  Used when insufficient treatment information exists to satisfy treatment
   demonstration requirements for full-scale facility permits or to establish
   preliminary Phase 2 (full-scale) conditions for a two-phase permit.

-  Contains provisions necessary to meet the general performance standards in
   Section 264.272(c).

-  Requires a 45-day public comment period and hearing if requested or
   required under state regulations.

Two-Phase Permit

-  Combination of above two permits when Phase 1 is for the treatment
   demonstration and Phase 2 is for the full-scale facility design and
   operation.

-  Used when substantial  but incomplete "treatment"  data exists and when
   sufficient data are not available to completely satisfy a treatment  demon-
   stration, but are available to determine  the preliminary set of full-scale
   facility permit conditions.

-  Used when Phase 1 and  2 permits are based on substantial  but incomplete
   information; Phase 2 permit is modified to incorporate the results of
   Phase 1.                                              .           •

-  Avoids the burden of two separate permitting procedures (e.g.,  only
   one public comment and hearing is necessary rather  than two)  unless  a
   major permit modification is required (Part 124 and 47 FR 32335).

-  Contains provisions necessary to meet treatment demonstration (Phase.
   1); contains provisions to meet all  applicable  Part 264 standards  (Phase
   2).
                                    11

-------
Table 1.6  Permit Application Content for Each Permit  Element  (U.S.  EPA
           1984a)
Full-Scale Facility Permit

-  Information addressing the general  standards  applicable  to  all  facili-
   ties - Part 270.14, "General  Information Requirements."

-  Information requirements of Part 270.20 addressing  the Subpart  M,  Part
   264 requirements

   — Treatment Demonstration Plan and Results
   — Land Treatment Program
   — Design and Operating Requirements
   -- Food Chain Crops
   — Closure and Post-Closure Care
   — Ignitable and Reactive Waste
   -- Incompatible Wastes

-  Information addressing the groundwater protection requirements  in  Subpart
   F, Part 264.

Short-Term Treatment Demonstration Permit

-  Treatment demonstration plan  including provisions to  meet the Part
   264.272(c) performance standard:  any field or  laboratory test  conducted
   must

   — simulate characteristics of the  proposed land treatment  unit,  Including
      waste, climate, topography, treatment zone soil, and  operating  prac-
      tices to be used at the unit;

   -- be likely to show that hazardous constituents will be completely
      degraded, transformed, or  immobilized in the treatment zone;  and

   -- be conducted in a manner that protects human health and  the  environment
      considering waste characteristics, operating and monitoring  measures,
      test duration, waste volume used in the test, and, in the case  of  field
      tests, the potential for migration of hazardous  constituents to grouad-
      water or surface water.

-  Certification of completion of LTD  and results  submitted to the appro-
   priate regulatory agency(ies) at end of study and as  part of full-scale
   facility permit application.

Two-Phase Permit

-  Same as full-scale facility permit  except that  the  results  of the  short-
   term treatment demonstration  are submitted (Phase 1).               '
                                    12

-------
be carried out in a manner that will lead to violation  of  the  Part 265 interim
status standards.  If the testing involves new application of  wastes, a permit
(short-term or two phase) must be obtained.

      If  literature data  are  to be useful  and supportive  of an  LTD  at  an ISS
facility,  the data  should  have  been  generated under  conditions  similar  to
those  at the  proposed  unit.   The literature  information  should  include
specific  data on  the  fate  and movement of  hazardous  constituents  (i.e.,
compounds  listed  in  Appendix VIII  of  40 CFR Part 261) present  in  the  waste
under conditions representative of  the  site  (soil,  temperature,  moisture,
hydraulic  conductivity, etc.)  proposed  to be used.   Although literature data
may  assist  in the design of the  laboratory and  field tests, these data alone
are  not  expected  to  fully  satisfy the  requirements  of  a treatment
demonstration.  As the data  base  improves  with  continued  research, literature
data may become more useful.

     Evidence of the  use  of operation  and/or management  practices  that
maximize treatment performance,  as  required in  40  CFR  Section  264.273,  must
also be  presented  with  an  interim  status land  treatment  facility  permit
application.   If  no  operation  and/or  management practices have been utilized
for  treatment maximization laboratory or  field  investigations may be required
at the discretion of the permit writer.

     The short-term treatment demonstration permit,  usually applied for by new
units, existing units with contamination, or existing units that are planning
to  treat  new wastes or  implement   major design  and  operational  changes,
authorizes  field  testing or  small-scale laboratory testing,  and  contains
provisions necessary to  meet the  general  performance standards  in  Section
264.272  (c)  (see  Table  1.6).   The  applicant only  submits  a treatment
demonstration plan in the  permit  application.   An applicant should apply for
this  permit  when  Insufficient  treatment Information   exists  (1)  to fully
satisfy the treatment demonstration  for a full-scale  permit without additional
testing or  investigation;  or (2) to establish  preliminary permit conditions
for  the  full-scale  facility  in a two-phase  permit.   A 45-day public  comment
period is  required prior  to permit  issuance.    The public  may  request  a
hearing,  if  they  desire.   After  the  laboratory or  field  tests are completed
and are found acceptable, the applicant should  apply  for a full-scale facility
permit.  The  full-scale permit is used  when complete data have been collected
to satisfy the treatment demonstration.  The applicant  should  submit both the
treatment  demonstration  plan  and results,  as  well   as  all  other information
described in Table 1.6,  for application for a full-scale facility permit.

     The  two-phase permit 1s a combination of the short-term permit and  full-
scale  facility  permit.   Phase  1  of the  permit includes  conditions for  the
short-term treatment demonstration, while Phase 2 includes provisions  for the
full-scale facility design  and operation.   This permit should  be  used  when
substantial but incomplete data exist to  satisfy the treatment demonstration,
but  sufficient  data are  available  to  determine the preliminary full-scale
facility conditions.   For the two-phase facility permit, the applicant submits
the  same information as  for  the  full-scale facility permit,  except that  the
results of the short-term treatment  demonstration (Phase 1) are submitted  at  a
later date.   Thus,  the permitting  official  first  writes  a draft permit  for


                                    t3

-------
 Phases  1  and  2,  and  then  after the results of the treatment demon-strati on are
 submitted, modifies the Phase 2 permit as. required.   The primary advantage of
 the  two-phase  permit is  the elimination  of the  need  for two  separate
 permitting procedures, i.e., one for  the  treatment  demonstration  and  another
 for the full-scale facility permit.


     After the two-phase  permit  is  issued,  Phase  1 is effective  during  the
 period  of the treatment  demonstration.   Phase  1  of  the  permit  is only
 applicable to laboratory and  field  studies, and the  interim status  of  the
 remainder of the HWLT unit is unaffected.   The owner/operator  may  continue to
 operate under  interim status on this remaining area  during the demonstration.
 The owner/operator  is  subject  to enforcement action  if   interim   status
 violations occur in the remaining area.


     The  owner/operator should  submit  the  following  to  the   permitting
 authority after  completion  of  the  tests:   (1)  a  certification that the  LTD
 tests have been  performed in accordance with Phase  1 of  the  permit; and  (2)
 all of  the data collected  during  the  LTD,  along  with  interpretations  and
 suggestions for  adjustments in the  final design,  operation,  and  management
 plans that will be incorporated in the full-scale facility permit.


     The  permitting  authority  will  evaluate  the results  and  will modify as
required the  second phase  of the permit to incorporate the LTD results.   Phase
 2 of the  permit  (i.e.,  full  scale  operation) will become  effective after  any
 and all  minor modifications  are completed.


     Guidance for minor modifications  are  given  1n Section 270.42(m)'and (n),
which states  that minor modifications may  only:


     (m)  Change any  conditions  specified in  the  permit  for  land
     treatment units  to  reflect the results  of  the  field  tests or
     laboratory analyses  used  in  making  a  treatment demonstration  in
     accordance with Part  270.63, provided that the change is minor;


     (n)  allow a second  treatment demonstration for land treatment to be
     conducted when the results of the first demonstration have not shown
     the  conditions under  which  the  waste or wastes  can  be treated
     completely  as  required by Section 264.272(a),  provided  that the
     conditions  for  the  second demonstration are substantially the same
     as the conditions for the first demonstration.
     If the Information from the  LTD necessitates major changes 1n the Phase 2
permit, the permit may be  modified  or revoked and reissued  ^nder guidelines
given  in  Section 270.41.   If  a  determination  1s  made  that the  permitted

                                    14

-------
activity »ndangers human health or  the  environment, the  pe'rmit  may be
terminated Sect ion 270.43).
1.5  CRITERIA FOR CHOOSING A LAND TREATMENT DEMONSTRATION SCENARIO

     The choice of an appropriate LTD  approach involves organizing information
and comparing that information with several  criteria (Figure  1.2).   The  first
question to address is whether the  land treatment unit is new or existing.  An
existing  unit  is  one where  waste has been  previously applied.    For the
purposes of conducting an  LTD, the  unit is considered "new" only if  it has not
had previous waste application.
1.5.1  Evaluation of Adequacy of  Part B  Information for Definition
       of LTD Plan (Existing  Sites)


     By  November  8, 1985 existing  sites under  interim  status should  have
submitted a Part B application for a permit or have indicated  their  intention
to  close.   The  Part B  permit  application should  provide  a description  of
procedures that  will  be  used  to demonstrate  complete degradation,
transformation,  and Immobilization  of hazardous  constituents  in  the  land
treatment unit (see Appendix  A).   As part of this description, the collection
of the following information  is recommended:


          Waste  characterization,  including  organic  and inorganic, Appendix
          VIII hazardous  constituents,  and other waste  constituents and
          properties that may affect the  performance  of the land  treatment
          unit
          Past waste management  activities

          Site and soil  survey information

          Waste distribution  in  the  soil

          Soil-pore liquid monitoring

          Groundwater monitoring,  Including data  collected  during Part 265
          Subpart F  monitoring  program and  if applicable,  data  collected
          according to the regulations given  in Section 270.14(c)(4)
     If any  or  all of  this  Information is not  available,  the applicant  in
conjunction with the permit writer should design and conduct-a reconnaissance
survey to  obtain the  missing  data, according  to the  guidelines  given  in

                                     15

-------
                        LAND TREATMENT
                               UNIT
                                SITE
                              EXISTING
                              OR NEW?
      PARTB
   APPLICATION
  PARTB
APPLICATION
          IS
       PART B
     INFORMATION
     ADEQUATE TO
      DEFINE LTD
       PLAN?
                                                       IS
                                                   SITE, SOIL
                                                   and WASTE
                                                CHARACTERIZATION
                                                  ADEQUATE TO
                                                   DEFINE LTD
                                                     PLAN?
                   SITE, SOIL and WASTE
                    RECONNAISSANCE
                   CHARACTERIZATION
RECONNAISSANCE
   SURVEY
                                                    SCENARIO 3
                                                    SHORT-TERM
                                                DEMONSTRATION PERMIT
       IS
      THERE
  CONTAMINATION
  EVIDENT IN SOIL
     AND/OR
GROUND WATER BELOW
    THE LOWER
    TREATMENT
      ZONE?
                                  IS
                              HWLT UNIT
                            RESPONSIBLE FOR
                            CONTAMINATION?
                       ARE
                  COMPREHENSIVE
                   LTD STUDIES
                    REQUIRED?
                                                                       SCENARIO 2
                                                                    TWO-PHASE PERMIT
                                ARE
                              MAJOR
                             LTD PLAN
                             CHANGES
                             REQUIRED?
                                                  ARE
                                                 DATA
                                              SUFFICIENT TO
                                              DEMONSTRATE
                                              TREATMENT AT
                                                 HWLT
                                                 UNIT?
      MAJOR
   DESIGN *nd/or
   OPERATIONAL
     CHANCES
     PLANNED?
                                              SCENARIO 1
                                               FULL-SCALE
                                            PART 264 PERMIT
Figure 1.2   LTD guidance for selection of appropriate  scenario.
                                        16

-------
Chapter 3  concerning  the  suggested  types  of information  and  procedures  for
data collection.

     Part 265 regulations do not require  data to be collected on Appendix VIII
hazardous  constituents.    However,  the  analysis of  these constituents  are
required for the LTD under Parts 270 and  264 for wastes, soil-cores, soil-pore
liquid  in  the  treatment  and  below treatment  zones  (if available)  and
groundwater and should be provided  for the  LTD review.

1.5.2  Contamination Below the Treatment  Zone or in the
       Groundwater beneath the HWLT Unit

     If the  information  presented   for definition  of the  LTD  plan indicates
contamination  with  hazardous  constituents  below  the  treatment  zone,  as
compared to a  background area further evaluation of the site are necessary to
determine required modifications to the LTD plan.

     Indicators  of contamination  may  include:    (1)  The  unsaturated  zone
monitoring data (including soil core  and soil-pore  liquid  data) collected
during interim  status and  included  in the operating record, as required under
Section 265.73, which should demonstrate  no significant migration of hazardous
constituents below the treatment zone;  (2)  Data provided for the Part B permit
application, i.e., data collected according to  Part 265 Subpart F and Section
270.14(c)(4) guidance, which  should be  evaluated  and  compared  to background
data,  using  appropriate  statistical  techniques  according  to  U.S.  EPA
groundwater sampling guidance; and  (3) reconnaissance sampling data (including
soil core  and   soil-pore  liquid  data and  results of groundwater monitoring,
which  should  demonstrate  no  significant increase of  hazardous  constituents
(Appendix  VIII) below the  proposed  treatment zone,  within the  active portion
of the site, compared to  background levels.

     If the soil below the treatment zone or the groundwater is determined to
be  contaminated,  an evaluation  should be  made  whether the  contamination  is
reasonably expected to come from the LT  unit.   If  the LT unit is suspected as
the contaminant source,  further studies  should  be conducted.   These studies
may include deeper soil  core sampling, either at specified  intervals below the
treatment  zone  to the top  of  the aquifer,  or samples composited through depth
increments to  the  top  of the  aquifer.    ISS  sites may show  groundwater
contamination  below land  treatment  units  due  to  either   regulated  or  solid
waste management units not associated with  the land treatment units.

     Analytical  problems may  occur due  to  different  detection  limits  for
hazardous constituents in the different sampling media, e.g., detection limits
may be  lower  in  soil-pore  liquid  than  in  soil  core samples, thus indicating
contamination  that  may  not even be detected  in the  soil core samples.   An
organic environmental chemist should be consulted  if such  analytical  problems
are suspected.

     If the groundwater  is contaminated due to the HWLT unit, major revisions
to the LTD plan will likely be necessary.  Revisions may also be necessary if
only  the  soil  below  the  treatment  zone  is   contaminated.    If minor
contamination is found in the below treatment  zone soil  (e.g.,  only in one or

                                   17

-------
a few sample locations, or only minor contamination  levels  are  found), the LTD
may possibly  be  conducted on  the  uncontaminated  portions of  the HWLT  unit.
Changes  in  loading  rate, frequency of  application,  or method of  application
may be evaluated in the LTD to enhance treatment.                    -  -

     If  the  site  is  highly contaminated  beneath  the treatment  zone, the
performance of  an LTD  field  study may  not  be technically feasible.    Prior
contamination of  the  site would likely  be  difficult to distinguish from new
applications of the waste, unless radioactive tracers were  used.

     The  regulatory  agency  may pursue  legal  action  based  on  demonstrated
groundwater contamination at an ISS HWLT unit.  The HWLT unit may be required
to  cease  operations in  the  contaminated area  if necessary  to protect  human
health and  the  environment.   The facility may decide  not  to  proceed  with an
LTD or may decide on a more comprehensive LTD design.   However,  at the present
time  RCRA regulations  do  not require  prior clean-up  of  a site  before LTD
studies can be conducted.

     For  sites  requiring only minor  modifications  to  the LTD design  due to
below treatment zone  soil  contamination,  there  is  a possibility that further
laboratory or field studies may not be required.

1.5.3  Major Design and Operational  Changes  in the HWLT Unit

     For an existing HWLT unit to be permitted on the  basis of current design
and management, the planned  future  activities under  a  Part 264 permit should
Involve  similar  wastes, -similar  waste  application  rates  and  methods  of
application, similar management practices, and should continue  to  use the same
soil as the treatment medium.   If  current and proposed future activities are
not similar, the planned changes should  lead  to more conservative  application
rates, better  waste  quality  (i.e., lower  concentrations of  hazardous  or
pertinent  nonhazardous  constituents),  or better management  practices or
design.   In  addition,  for permitting  on the  basis of current  design and
management  practices, the  soils  presently used  cannot  be replaced by others.
To demonstrate future consistency of operation, the  permit application should
address planned unit  processes,  waste  application  rates, and  use of the site
soil.  If major design  and operational changes are planned, the LTD should be
more comprehensive and conducted according to Scenario  2 or 3.

1.5.3.1  Planned Unit  Processes--
     Major  changes  in the  unit processes  generating  the  wastes are of concern
1f the changes result in the introduction or increase of measurable  amounts of
hazardous constituents  in  the waste or the production of  a new waste stream.
New. constituents  introduced after  a  treatment  demonstration  would  not  have
been  tested in  the treatment  demonstration,  and therefore their behavior in
the HWLT unit would not be definitively known.  Later  changes  in  unit process
design and/or operation may or may not warrant a new  LTD, depending on whether
changes  may be anticipated  to adversely affect  the  performance of a  land
treatment unit.

     The  relative  abundance of  various  waste constituents in  even  a single
waste stream may be expected to vary due  to  seasonal effects,  fluctuations in
feed  stocks,  relative  market  demand for  the various  products  of the  waste

                                       18

-------
generator,  and   intermittent  batch  generation  of  certain wastes.   These
variations may  be  accounted  for  in  reconnaissance  waste characterization.
However, the on-going waste monitoring program should be capable of detecting
substantial  long-term  changes  in  waste  quality.   For the  LTD, anticipated
changes that  could  affect  waste  quality should be  identified..   If these
changes may be anticipated or are shown to  adversely affect the performance of
a land treatment unit, Scenario 2 or 3 should  be  used.

1.5.3.2  Planned Waste Application Rates—
     The applicant may wish to investigate  waste  application rates higher than
currently  used  in  practice  due  to  forecasted  increases  in  the  rate  of
production for one  or several waste  streams or a  change in the composition of
the waste stream due to operational changes (e.g., application of a dewatered
waste  stream  will  result  in  an  increased application rate  of  hazardous
constituents compared to the same application  of  the waste stream that has not
been dewatered;  however, dewatered sludge may  be  applied to the land treatment
unit  at  a  lower  loading rate so  that  the  concentration  of hazardous
constituents in the soil  remains the  same  as  the  concentration resulting from
the application of  nondewatered  sludge).    Planned  application rates should be
expressed  in terms of  the concentrations  and application rates of  limiting
constituents, or constituents that are nearly  limiting, as well as in terms of
less descriptive parameters, such as oil  content.

     Scenario 2  or 3  should be  followed  if increases  in  the  application
rate(s) are  anticipated for the future.

1.5.3.3  Planned Use of Soils—
     The use of a different soil for the  land  treatment unit may  significantly
affect the behavior and fate  of  waste  constituents within the treatment zone.
Due to differences  among  the  physical, chemical,  and biological properties of
soils, treatability of waste  within different soils likewise varies (U.S. EPA
1983a).  An  expansion  of the HWLT unit onto  a different soil series would be
considered a change in treatment medium and would  require the performance of a
more rigorous LTD,  i.e.,  the use of  Scenario 2  or 3.   Likewise, removal and
replacement  of  soil present  on  an  existing  active  area  with  soil  from  a
different  series  is also  regarded  as  a  change  of treatment  medium and would
indicate the use of Scenario 2 or 3.

     Finally,  a  proposed major  disruption of the treatment  zone would
significantly alter soil  conditions.   While normal operations are expected to
disrupt  only surface soils  in  the  zone  of  incorporation,  major disruption
Involves one of the following:   deep tillage  (e.g.,  greater  than 18 inches),
an  activity  which mixes  the  lower  portion of the soil  profile that normally
would remain undisturbed  during HWLT  operations,  or the  artificial  drainage
and  lowering of  a  seasonal  high water  table that had previously encroached
Into the treatment zone in order to meet  the separation requirements of 40 CFR
Section 264.271  (c)  (2).   These types of  activities  would require the use of
Scenario 2 or 3 for the LTD.

1.5.3.4  Guidance on Planned Design and Operation-
     Management personnel  of the  facility should be consulted  to  determine
possible near-term modifications to the waste streams or land treatment unit.


                                   19

-------
Table  1.7  lists information needed to  assess  planned design and  operational
changes  and  presents  guidance  in  interpreting this  information.   For
anticipated future changes, a decision must be  made whether  to conduct  the LTD
for  the  revised  unit  at  the  present or  at a  later time.   If  design  and
operational changes  will  occur, HWLT unit  permitting  as  per Scenario 2 or 3
may be used.


Table 1.7  Information Required to Assess Planned  Changes  in  Design and
           Operation and to Assess the Suitability of  the  Use of  Scenario 2
     Category                           Confirmation  of  No  Design
                                         and  Operational  Changes


Unit Processes                No anticipated  measurable  quantities of addi-
                              tional  hazardous  constituents that are not
                              presently in  the  waste.  No new wastes proposed
                              for treatment.

Waste Application Rates       No significant  increase  in  the quantities of
                              hazardous constituents  applied per unit area per
                              unit time (kg/ha/yr).

Soil                    .      No expansion  onto new soil  series; no importa-
                              tion of different soils  for use as the treat-
                              ment medium;  no major disruption of existing
                              soils.
1.5.4  Evaluation of Whether Information  is  Sufficient
       to Demonstrate Treatment at  the  HWLT  Unit
     If only literature, reconnaissance, and existing operating data form the
basis  for  a full-scale  facility permit,  the  applicant is  limited  to waste
application rates  and  frequencies  used during past  operations  in succeeding
full-scale operations  (i.e.,  the applicant may  not have  the  opportunity to
evaluate higher  loadings or  frequencies  on a  full-scale operating  basis).
Also,   because  this  approach  1s  a retrospective  analysis,  sufficient
Information on  the relative mobility and degradation  of  hazardous constituents
based on monitoring data will  likely not be available for determination of the
"principal  hazardous  constituents"   (PHCs)  that  may serve  as Indicators  in
unsaturated zone  monitoring  (UZM)  during  full-scale operation.   A  number of
parameter  estimation  methods  are  available  that  provide  an  estimate  of
constituent properties based  on  fundamental chemical and physical/structural
characteristics (structure  activity  relationships  (SAR),  UNIFAC, correlation
equations,  etc.)  (Lyman  et  al.  1982).   These  methods are limited in 'terms of
breadth of application and extent  of verification  and  their use  should be
supported with  some confirmatory data for  the complex waste mixture to be land


                                   20

-------
treated.  In most cases, additional  studies  are required to provide sufficient
data for the selection of appropriate PHCs.   Therefore,  an  applicant  with  an
ISS facility who  uses  laboratory  studies  or field investigations  to  complete
the treatment demonstrati on  should apply for  an LTD permit (i.e., a short-term
treatment demonstration followed  by a full-scale facility permit, or  a  two-
phase permit).

     If  information  from  ISS operating  experience,  literature data,  and
reconnaissance  survey  is  not  sufficient  to  demonstrate treatment, the
performance of an  LTD  under an  LTD permit is appropriate, i.e., requires the
use of Scenario 2 or 3.

1.5.5  Further  Information Requirements for  Demonstrating Treatments

     If the Part B  information  is  judged  "substantial but  incomplete"  by the
permit  writer, the  applicant  may  conduct  the  LTD  according  to   Scenario 2
(Figure  1.3),  using a  two-phase   permit.   Depending  on  the quality and
completeness  of  information  presented,  the  LTD  may  include only the
quantitative presentation  of complete, comprehensive reconnaissance data,  past
operating  data,  and  estimated  or laboratory  determined  waste  constituent
parameter data, and the evaluation of such data  using the LTD model described
in  Chapter  4.    If  these  data  are  still  considered  insufficient,  additional
laboratory  analyses,  and  laboratory  and  field  verification studies  may  be
necessary.   The  permit writer  and  the  applicant should  determine the  exact
scope of  the treatment demonstration using  available operating,  monitoring,
and performance data in a  pre-application meeting.

     When there  is not  enough  information  to establish  Subpart M  permit
conditions,  Scenario 3 (Figure  1.4)  should  be  followed, using a  short-term
demonstration permit.    The  technical  approach to the  performance  of  an  LTD
according to Scenario  3 involves the comprehensive assessment of the potential
for migration of hazardous constituents,  the potential  for their degradation,
immobilization,  transformation,  and  detoxification,  as  well   as the
determination of  loading  rates and management  practices  for  performance
maximization at the land treatment unit.   These  endpoints are accomplished  by
the use  of  a  combination  of  literature data,  laboratory analyses, and
laboratory and  field verification  studies.

     A redesigned ISS  unit with major design and  operational  changes  planned,
should follow  Scenario 3 to obtain  a permit.  Major design  and  operational
changes considered under Scenario  3  include:  new wastes (wastes that  have not
been  applied previously at  the unit),  changes  in  waste application  rates,
replacement  or  addition of soil  for waste  treatment at the unit, and/or major
disturbance of  the  soil  at   the  unit.   Also, units  that have exhibited
contamination below the treatment  zone are  eligible  for  an LTD permit  under
Scenario 3.

1.5.6  LTD Approach for New  Sites

     Prior to beginning the  LTD, the applicant with  a new site should-perform
a  site/soil  survey to determine  if the  proposed site is  suitable for  land
treatment, and  a complete waste  characterization  to determine  the  presence  of


                                   21

-------
       SCENARIO 2
        PHASE 1
     OF TWO-PHASE
     PART B PERMIT
       EFFECTIVE
    EVALUATION OF
      EXISTING
TREATMENT PRACTICES
                                                  ASSESSMENT OF:
                                                   MIGRATION POTENTIAL »nd
                                                   DETOXIFICATION of PREVIOUSLY APPLIED
                                                   WASTES, «nd OPTIMIZATION of
                                                   TREATMENT PERFORMANCE by USE of
                                                   RECONNAISSANCE INFORMATION end
                                                   ADDITIONAL LABORATORY ANALYSES
                                                   for USE in PREDICTIVE MODEL
                             PHASE 2
                         PERMIT EFFECTIVE
                                   INFORMATION
                                   SUFFICIENT TO
                              DEMONSTRATE DEGRADATION,
                           TRANSFORMATION *n
-------
                                     SCENARIO 3
                               WASTE CHARACTERIZATION
                                      SHORT TERM
                              TREATMENT DEMONSTRATION
                                   PERMIT EFFECTIVE
                            DETERMINATION OF:
                              LOADING RATES,
                              MANAGEMENT PRACTICES,
                              MIGRATION POTENTIAL,and
                              POTENTIAL FOR TREATMENT and
                                DETOXIFICATION of WASTE
                                CONSTITUENTS by USE OF
                                LABORATORY ANALYSES,
                                LABORATORY STUDIES, and
                                FIELD VERIFICATION STUDIES
          SITE NOT
        PERMITTABLE
         FOR LTD AT
        PRESENT TIME
         INFORMATION
        SUFFICENT TO
   DEMONSTRATE DEGRADATION,
TRANSFORMATION and IMMOBILIZATION,
  DETOXIFICATION, and TREATMENT
        OPTIMIZATION?
                                      FULL SCALE
                                     PART B PERMIT
                                       EFFECTIVE
Figure 1.4.  Specific guidance and information requirements for LTD meeting of
           the definition for Scenario 3.
                                 23

-------
hazardous constituents  and  other  pertinent  constituents  that  may affect  land
treatment.  Guidelines   for   assessing   the  suitability  of  a  site  for  land
treatment are  given in  the   Permit   Writers' Guidance Manual  for the location
of  Hazardous  Waste  Land   Treatment  Facilities:  .Criteria   for  Location
Acceptability and Existing applicable Regulation?   fOm  ETA"19855).  TRe
applicant then obtains  a  short-term  demonstration  permit  according to  Scenario
3 that  incorporates the  provisions  necessary  to meet  the general  performance
standards in  Section 264.272(c).   A 45-day  public  comment  period is  required
prior to  permit   issuance.   The public  may  request  a  hearing  if they  desire.
Once this permit  is obtained,  the LTD  may  begin.   Once  the LTD  is  completed,
a certification   of  completion   and   a   final   Part   B  permit   application
incorporating the  LTD  results  should  be  prepared.    A   full-scale  Part  264
facility permit  is   issued  after  appropriate  administrative  steps  are  taken,
Including a second period for public comment and a public hearing.

1.6  IMPLICATIONS OF THE HAZARDOUS AM) SOLD WASTE AMENDMENTS OF
     1984 (HSWA) FOR LAND TREATMENT DEMONSTRATIONS AND  FACILITIES

     Although  land  treatment   demonstrations   are  presently  regulated  under
existing RCRA  regulations  (Section  264.271   et  seq.),  the  recent  HSWA  have
changed the  regulatory  approach  to  land  disposal  in  general,  and  directly
impact land treatment facilities and the performance  of LTDs.

     As Section  1002(b)  (7) of  the  HSWA  indicates,   the  U.S.  Congress  felt
that certain  classes of  Land  disposal  facilities  could  not   assure  long-term
containment  of  certain  hazardous  wastes.   While   landfills   and surface
impoundments were the  primary  motivation  for  the  amendments, land  treatment
was also defined  as  "land disposal"  under  Section 3004(k) and  is   subject  to
many of  the  stringent  provisions  of the  HSWA.   Some  of  the HSWA  provisions
that  may   relate  to  the   performance  of  land  treatment demonstrations  are
summarized here.

     Sections 3004(d),  (e),  and  (g)  prohibit  the  land disposal  of  all  hazardous
waste unless  (1)  the  waste  is  treated  prior to "land  disposal"   in  compliance
with a  treatment  standard  promulgated   underSection3004(m)   or  (2)  if  an
interested  party   demonstrates,    to a  reasonable degree  of  certainty,  that
there will  be no migration  of  hazardous   constituents  from the  disposal  unit
or injection  zone  for  as  Tong  as the  waste  remains  hazardous.   Sections  3004
(d), (e), and (g),   as  well as  a  schedule published  by the EPA   (51 FR  19300,
May 28,  1986),   establish   a   schedule   for  implementing the   land  disposal
prohibitions for hazardous wastes.

     Section 3004(n)   requires   that   the  U.S.   EPA promulgate  regulations
concerning air  emissions  from land  disposal   facilities.   Currently  U.S.  EPA
1s conducting  studies   to  evaluate  the  potential  level   of hazardous  volatile
organics released from  land  disposal facilities.   However, this  LTD  Guidance
Manual does  not  address  the collection  of site-specific  information for  this
evaluation since air standards have not been promulgated at this time.
                                    24

-------
     Section 3004(o) requires new land treatment units to have EPA-approved
leak detection  systems.   Although  this  requirement  does  not  take  effect
until the  regulations  are   issued,  the  performance  of  LTDs  may  provide
opportunities to evaluate the  suitability  of unsaturated  zone sampling and
analysis techniques to meet this requirement.

     Section 3004(u) requires corrective action for all  releases of hazardous
waste or constituents  from  any solid waste management unit at a treatment,
storage, or disposal  facility  seeking  a  permit, regardless of  the  time at
which the  waste  was placed  in the  unit.   The Agency  has  determined that
Section 3004(u)  should not   apply  to land treatment  demonstration  permits
Issued pursuant to Section 270.63(a)(2),  because these permits generally act
as an extension of the application process by providing  information for the
final permit.  The requirements of  Section  3004(u) must be incorporated into
the final Part B permit for  such facilities.  Similarly, the requirements of
Section 3004(u) must be addressed in the  second phase of a two-phase permit
Issued under Section 270.63(a)(l).

     Section 3004(v)  requires   cleanup   beyond  the property  boundary  for
permitted facilities.  The U.S. EPA has required that corrective actions be
undertaken as  soon  as  possible.    If  groundwater  monitoring  Indicates
contamination at  a land treatment  site  performing  an  LTD,  some form  of
corrective action  may  also  be  required.   From a technical  standpoint, this
manual recommends  that  such corrective  actions be taken before a facility
defines an LTD on an ISS land treatment site.   A facility applying for a Part
B permit and having groundwater contamination may be required  to concurrently
plan for corrective  action   responses as  well as  fulfilling  other  Part  B
requirements.
                                    25

-------
                                                          OSV.cn POLICY DIRECTIVE NO.

                                                        9486 . 00-2   a<
                                  CHAPTER 2

               TECHNICAL APPROACH TO THE PERFORMANCE  OF AN LTD


 2.1  EVALUATION OF TREATMENT PROCESS

     For  each  candidate  waste  that  will be applied at a land treatment unit,
 the  owner or  operator  must demonstrate  that  hazardous constituents  in  the
 waste can be completely degraded, transformed, or  immobilized in the treatment
 zone.   The  technical  approach  to  the demonstration of  land  treatment  is
 organized  to  address  the  evaluation of degradation,  transformation,  and
 immobilization  processes  within the  context  of  each  scenario  presented  in
 Chapter 1 of this manual.

     Table 2.1 identifies specific measurements  used to evaluate the principal
 processes involved in land treatment that  were identified above.  For example,
 measuring the  concentrations of hazardous  constituents  in  the  treatment zone
 soil through  time may  be used  to  assess the  degradation  potential  of  the
 waste.   Similarly, leaching potential  may be observed by comparing the mass of
 hazardous constituents in the soil-core with the mass 1n the soil-pore liquid,
 either .in  the  laboratory  or  in the  field.   Leaching  potential may  also  be
 evaluated  through  measuring   and  comparing  concentrations  of  hazardous
 constituents  in  field  plots  below the treatment  zone  with background
 concentrations.   Toxicity  testing  can  be  used  1n laboratory  and  field
 experiments to  assess the  transformation  of hazardous  constituents  through
measuring relative detoxification with time.   Table 2.1  also  identifies  the
 sources of information for evaluating each treatment process, type  of sample,
 and analytical methods for  evaluation of each treatment process.   Tests  for
 identifying the statistical  significance  for  each of the treatment  processes
based on literature,  laboratory, and field  generated data are appropriate,  and
 are presented in Appendix B of  this  guidance manual.

     As indicated in  Table  2.1, the requirement  for  demonstrating  treatment,
 i.e., degradation, transformation, and  immobilization,  can be addressed using
 several approaches.   Information concerning  each treatment process  can  be
obtained  from  several  sources Including  literature  data,  field  tests,
 laboratory  studies,  laboratory analyses,  theoretical  parameter  estimation
methods,  or  in the  case  of existing  units,  operating  data (40 CFR  Section
264.272) as indicated in  Table  2.1.

     Literature data  used to  support the LTD should be clearly documented with
respect to waste type, waste  toxicity, soil characteristics, and environmental
variables including  temperature.  Theoretical parameter estimation methods  for
determination of degradation and  Immobilization  Information  (partitioning  in
the soil/waste mixture)  also  should  be clearly documented and justified as  the

                                   26

-------
     Table 2.1   Monitoring and  Evaluation Strategies to Assess Treatment Processes in a  Land Treatment
                 Demonstration
ro

Treatment
Processes
Degradation


Transformation

I (mobilization



Monitoring and Evaluation Measurement
Change In concentration of principal organic
hazardous constituents over time in the
treatment lone soil (TZ)
Change In concentration of Indicatory param-
eters over time (e.g., oil content, benzene
extractables)
Potential for degradation/leaching
Concentration of hazardous metabolites or
chemical breakdown products
Change In tox Icily over time
Decrease In pollutant velocity relative to
soil-pore liquid velocity or air velocity,
measured by comparing soil core with soil-
pore liquid concentrations of hazardous
constituents
Buildup In concentration of metals over time
Concentration of Appendix VIII compounds
below the treatment zone (BTZ) (leaching)
Potential for leaching/degradation
Sources of Information
Laboratory Kinetic Study
Field Plot Study
Literature Values
Laboratory Kinetic Study
Field Plot Study
1SS Operating Data
Literature Values
Mathematical Model
Field Plot Study
Reconnaissance Study
Laboratory Study
Field Plot Study
Laboratory Analysis
Field Plot Study
Reconnaissance Study
Field Plot Study
Reconnaissance Study
1SS Data
Field Plot Study
Reconnaissance Study
Mathematical Model
Type of Sample
Waste 1 TZ* Soil -core
Haste t TZ Soli-core
Waste & TZ Soil -core
Waste 1 TZ Soil -core
Waste !> TZ Soil -core
Waste 1 TZ Soil -core
Waste I TZ Soil -core
Waste It TZ Soil -core
Waste & TZ Soil -core
TZ Soli-core, Waste, & ,
Soil-Pore Liquid
TZ Soli Cores 1. Soil-pore Liquid
TZ Soil Cores & Soil-pore Liquid
Waste t TZ Soil -core
Waste i TZ Soil -core
Waste I TZ Soil -core
BTZ4 Soli Cores, Soil-pore Liquid
I Groundwater
Waste & TZ So 11 -core
Analytical
Methods
Type 11
Type II
Type I
Type 1
Type I

Type III
Type III
Type III
Toxlclty Tests
Toxiclty Tests
Type III
Type III
Type II
Type II
Type 11
Type III
Type III

       *TZ  • Treatment zone.
       +BTZ « Below treatment zone.

-------
 approach  selected.   Also,  an assessment of the quality of the data should be
 given.  Quality of literature data may be assessed  based on criteria including
 statistical  approach,  results  of statistical  analyses  (confidence  limits,
 coefficient of  variation,  precision,  etc.),  and  rigorousness of experimental
 design.   The U.S.  EPA considers the use  of  literature  information  alone as
 Insufficient to support an LTD at the present  time.

     Field  tests  may Include sampling of  the  treatment  zone soil, soil-core
 and  soil-pore liquid  below the treatment  zone, and  groundwater  sampling.   A
 statistical approach to field sampling and  evaluation of analytical results is
 recommended.  Information concerning statistical approaches and techniques are
 included  in Appendix B of this guidance  manual.  Also Chapters 3 and 6 of this
 manual  provide  detailed information  concerning  reconnaissance  and  field
 verification  studies,  respectively,  as  sources of  information  for assessing
 treatment  (degradation,  transformation,  and  immobilization).   Chemical  and
 bioassay  techniques  are discussed  in this chapter  and in Chapter 5.   Field
 verification  studies  may  be  based on  results  of the  mathematical  model
 assessment of design and management parameters.

     Laboratory studies, laboratory analyses,  and soil/waste characterization
 also  provide  information  concerning  treatment  effectiveness for  design  and
management  combinations,  and are  identified  in  the  scenarios  presented  in
 Chapter 1.  A laboratory study involves  the use of controlled and experimental
 treatments  where  treatment results  are compared  in  order to  select  the
design/management combination that maximizes treatment, i.e., the best set of
SSACs for all  hazardous constituents in  the waste.  Laboratory analyses within
the context of the scenarios refers to the determination of degradation rates
 and  partition  coefficients for  input into the  land treatment mathematical
model.    Waste   and  soil  characterization refer  to any bioassay(s)  and/or
chemical  procedure(s)  or  test(s)  that  are used  to determine the treatment
 status of a specific sample.  Laboratory studies therefore include laboratory
analyses  and  waste/soil  characterization  in  the  format  of  an  experimental
matrix for evaluating the effectiveness  of  design/management combinations, and
for selecting  the design/management combination that maximizes treatment.  The
design/management  combination  chosen  may then  be  used  in  the  field
verification study part of  the  LTD.

     For existing units where operating  data are  used to support,  the  LTD the
quality and amount  of the data  presented  are  important.   Also, the  planned
future  use of  the  LTD  unit  compared  with historical  design/management
practices need to be  evaluated.   It is  the philosophy of this manual  that  a
combination of  data  sources  should  be  utilized,  e.g.,   literature  data,
laboratory  analyses,  laboratory studies and  field  verification  tests,  to
strengthen confirmation of  hazardous constituent treatment demonstration.  The
availability and completeness of existing  operating and literature data will
 influence the  need for collection of further performance data.

     Evaluation  of these  treatment processes  may  be  integrated through  the
definition and  the  determination  of  the soil/site  assimilative capacity
 (SSAC).    The SSAC  is  defined  as the amount of waste that may be  appTied  per
unit  of  site-soil  per unit  of  time,  based on  the Individual  hazardous
constituents present.  The  SSAC  is developed  for a  specific  candidate  waste

                                   28

-------
and  a  specific  design  and  operation combination.   Therefore,  the  SSAC
represents a  combination  of loading rate  and  loading frequency that  allows
complete degradation,  transformation,  and  immobilization  of  hazardous
constituents to be accomplished  within the defined treatment zone.

     Prior  to  the determination  of  the  SSAC,  a waste characterization  is
conducted in  order  to identify and quantify hazardous constituents that  are
present in the waste.

2.2  DETERMINATION OF  THE  SITE/SOIL ASSIMILATIVE
     CAPACITY (SSAC) FOR A CANDIDATE WASTE

     Determination of  the  SSAC  for  a  hazardous  waste  land  treatment
demonstration involves addressing the  factors  identified  in 40  CFR 264.272  in
an integrated manner:

     (1)  extent of immobilization;

     (2)  rate of biodegradation;  and

     (3)  transformation/detoxification  potential  (effects  on the soil
treatment medium and potential  public health aspects).

The toxicity  of  the waste  or  waste constituents  to  the  treatment medium  must
alsolfe evaluated to ensure that the biodegradation pathway is not eliminated.

     Through the evaluation of the factors  listed above.  Information  required
by  RCRA for  conducting an LTD,   i.e.,  design  and  operation  and management
characteristics presented  in Table 2.2,  will  be obtained  and  an assessment  of
the land treatability of a waste can be made.


Table 2.2  Design and  Operation  Parameters for LTDs
          Design parameters                 Operation and management
          Waste application method           Soil moisture
          Waste application rate(s)          Microbial activity
          Waste application frequency        Chemical activity
                                            Soil pH
2.2.1  The Toxlclty Component  of the  SSAC

     The following  list  of  bioassays identify those tests commonly  cited  in
the professional  literature  to assess the  impact  of a waste on soil  microbial
activity:

                                   29

-------
      1.   Microtox toxicity assay
      2.   Carbon dioxide evaluation
      3.   Dehydrogenase activity
      4.   Nitrification
      5.   Microorganism plate count

      Descriptions of each bioassay listed above and additional  bioassays,  and
 procedures,  methods,  and guidance on  data handling  and  interpretation  are
 detailed  in  Chapter  5 of this  guidance  manual.   The bioassay or battery of
 bioassays selected for  use  in the LTD may  be  negotiated  between the  permit
 applicant and  the permit writer  and  agreed  in writing  at the  initiation of
 negotiations.   Regardless  of which assays  are chosen,  due  to the  inherent
 variability  of  biological  testing  procedures and  the lack of  a  single  assay
 which shows waste toxicity to all microbial  functions, it  is  suggested that a
 battery of  two  or more  assays  be  used to  more confidently  identify  critical
 toxic loading rates.

 2.2.2  The Immobilization Component of the SSAC

     Evaluation of loading rates also  Involves  an  investigation of the  extent
 of migration of  hazardous constituents.  The approach taken  in this  guidance
manual is to recommend that  the maximum  loading  rate that does not  prohibit
microbial  degradation  of readily  biodegradable organic  constituents in  the
 waste.be established  and,  using this maximum  loading   rate,  that  the
 immobilization  of hazardous  waste  constituents by the  site/soil  at that
 loading rate be  evaluated.   Thus, the amount  of  waste  on  a given   area  per
 application  is  limited either  by the acute toxicity to the  treatment medium or
by the mobility of waste  constituents.

     Mobility includes the downward transport, or leaching  potential,  of  waste
constituents.   Several  approaches  for the  evaluation of  the  mobility of a
waste  and  specific  hazardous  waste  constituents are listed  below.   These
 include:

     1.    predictive mathematical models
     2.    laboratory  isotherm  analyses
     3.    laboratory column  studies
     4.    laboratory  analyses  for soil thin layer chromatography
     5.    field  plot  studies
     6.    barrel  lysimeter studies
     7.    parameter  estimation  methods  including  structure-activity
relationships,  etc.

  •   The  downward transport,  or  leaching  potential,  of the waste  is evaluated
to ensure  that  waste constituents do not migrate out of the treatment  zone.

     Laboratory analyses  and/or  other  methods may be used to determine
partition  coefficients,  which  are  directly  related  to  constituent
immobilization.   These constituent-specific partition coefficients can then be
used as input parameters  for  the  land treatment  mathematical  model  (Chapter
4),  along  with biodegradation  data, for estimating breakthrough concentrations
and  breakthrough times  of  hazardous  constituents in  the  wastes.    The

                                   30

-------
 collection  and  use of this immobilization data for identification of principal
 hazardous  constituents   (PHCs)  and  for  field  verification study  design  is
 described  later  in  this chapter  and  in Chapter  5  "Laboratory Analyses and
 Laboratory  Studies for Selecting Design and  Operating Conditions."

 2.2.3   The  Biodegradation Component of the SSAC

     The basis  for  biodegradation  coefficient  measurements  is  the
 determination  of specific constituent  soil  concentrations as  a  function  of
 time.    One  critical  aspect  of biodegradation measurements that  should  be
 emphasized  is  the  deficiency in  the  measurement of  biodegradation  as the
 "apparent  loss"  of  hazardous constituents over time.    A  biodegradation
 correction  factor  is   required  to  adjust  "apparent  loss"  rates that are
 appropriate  to  biodegradation.  Experimental methods for the determination of
 a biodegradation  rate for hazardous waste constituents are  provided in Chapter
 5  of this  guidance  manual.    Corrected coefficients for  biodegradation may
 represent a  more accurate description of true  biodegradation occurring within
 the  land treatment unit, and  may provide an Improved estimate of the relative
 effect  of  different  design/management  options on constituent degradation and
 transport expected on a full-scale unit when they are used  in conjunction with
 the  land treatment mathematical model.

 2.2.4   The Transformation/Detoxification Component of the SSAC

     Information  concerning the decrease  in acute toxicity of  the  waste/soil
 mixture  to  soil  microorganisms with  time  can be evaluated using  short-term
 bioassay procedures for 'toxicity  determination.   The relative detoxification
 (transformation)  of the  waste by  the  treatment medium may be correlated with
 parent  compound degradation   to ensure  protection of the  public health (CFR
 Section 264.272(3) and soil  microbial  activity in  the  land  treatment unit.

     If  parent  constituents  in a  waste to be  land  applied are  Identified  as
 having  mutagenic or  carcinogenic  characteristics,  it  is  recommended  that  a
 test be used to  indicate the mutagenic  potential  of the  leachate at the bottom
 of the  treatment zone.   A list of  short-term bioassay that have been  used to
 screen mutagenic characteristics of soil/waste  mixtures  include:

     1.   Salmonella typhimurium mammalian microsome mutagenicity assay (Ames
 assay);

     2.   Bacillus subtilis;  and

     3.   Aspergillus nidulans

     These assays have been  used  by K. W. Brown  (1984)  for assessment of the
mutagenic potential  and mutagenic  detoxification of  hazardous  waste-soil
mixtures.  The  Ames assay has also  been  used by  Sims  (1984) in laboratory and
field  treatabiHty  studies  for assessment  of   deactlvation  of  mutagenic
characteristics  for hazardous  waste-soil  mixtures.   As  with the  toxicity
 assays, however,  the  above  list is not  comprehensive,  and other methods for
 Indicating  detoxification may be used  1f their  methodology,  validity,  etc.,
 are substantiated for the LTD permit writer.

                                    31

-------
 2.2.5  Calculation of the SSAC

      The site/soil   assimilative  capacity  is calculated  as  the  integrated
 effects of degradation and immobilization of hazardous constituents'present  in
 the  candidate  waste,  where treatment  is  not  limited  by toxicity  and/or
 transformation/detoxification  potential.   In  order  to integrate  information
 concerning degradation and immobilization, a mathematical  model may be  used  to
 evaluate the SSAC and the effects of operation and management practices  on the
 SSAC.   A proposed land treatment model is described  in detail in  Chapter 4 and
 in  Appendix  C  of this manual.  The  model  is  based  on the model developed  by
 Dr.  Thomas  Short,  Robert  S.  Kerr  Environmental  Research  Laboratory, U.S.
 Environmental  Protection Agency,  for  use  in determining  which  hazardous
 substances  should  be banned  from  land treatment.   The model  allows for the
 evaluation  of  degradation  and  leaching  potential  of waste constituents   in
 accordance with  40  CFR  Section 264.272  in order  to meet  the requirements  of
 Sections 264.271 and 264.273.

 2.2.6   Principal Hazardous Constituents (PHCs)

     The approach  to demonstrating  complete  degradation,  transformation,   or
 immobilization of  hazardous  constituents  in  the  waste within  the  treatment
 zone  (Section  264.272(c)(2))  is  to  identify  a  subset  of  these  hazardous
 constituents in  the  waste,  labeled  principal  hazardous constituents  (PHCs-),
 that  can be used for  evaluating  land treatment performance.   According to  40
 CFR Section 264.278, PHCs are defined  as  "hazardous  constituents contained -in
 the wastes to  be applied at  the  unit that are the  most  difficult to treat,
 considering the combined  effects of  degradation, transformation,  and
 Immobilization"  (40  CFR  Section  264.278).   PHCs are, by  definition, those
 hazardous constituents having the  lowest  SSACs, and therefore  may be used  to
 Indicate the success  of treatment in laboratory studies and field verification
 studies for land treatment demonstrations, and  may be used to monitor the long
 term performance of a full-scale  land treatment facility.

     PHCs may be identified based  on  degradation  and  immobilization  estimates
 using a land treatment  mathematical  model  that is described in  Chapter 4  of
this guidance manual.  The model  integrates the combined effects of biological
degradation and  leaching for  predicting   levels  of  constituent( s)  in  the
 leachate at  breakthrough.   The  model  is useful  for selection  of  PHCs  for
establishing priorities with respect to constituents that  are predicted to  be
transported the fastest  (most difficult to treat)  compared with all hazardous
constituents identified in the waste.

2.2.7  Use  of the SSAC for Design  and Management

     Through the  integration of  the combined effects of  degradation  and
 Immobilization, hazardous constituent  movement toward the critical region  of
the land treatment system, the bottom of the defined  treatment  zone,  can  be
evaluated.   The  two  primary output  parameters of the model  used to evaluate
treatment are:    (1)  the  concentration of a constituent at the bottom- of the
treatment zone  (defined  as "breakthrough"), Cb, and   (2) the time required for
a constituent  to  travel  a distance  equal to  the treatment  zone  (Tb).   The

                                   32

-------
 ratio Cb/Tb  defines the  integrated  relationship between  degradation  and
 immobilization  and  therefore  defines  the SSAC.   The smaller the  ratio,  the
 greater  is  the  SSAC for a  hazardous  constituent.   Constituent-specific
 degradation  and mobility  coefficients  obtained  from various  sources  (i.e.,
 literature  data,  theoretical  parameter estimation  methods,  laboratory  data,
 field  data,  etc.,) for  various  design  and operation and  management  options
 given  in  Table 2.2 can  be  used  in the land  treatment model  to  develop SSAC
 (Cb/Tb)  values for each design/management  combination  investigated.    These
 SSAC  values  can then  be compared  and used  to  evaluate the  following  for  the
 LTD:

      1.   Most appropriate  design/management   combination  for  field
 verification  for  a specific  waste/soil  mixture  (lowest  SSAC  values  for
 hazardous constituents).

      2.   Principal hazardous constituents  (PHCs)  that  will  be  monitored  to
 ensure  effective  treatment or  to indicate the  need for design/management
 modification of the full-scale operation (set of constituents with the  highest
 SSAC  values for the best  design/management combination).


 After the most  appropriate design/management option  is  selected,  based  on  the
 results  of  the ranking  described above, PHC  selection,  degradation,  and
 mobility  estimates  for  hazardous  constituents of the  waste may  be  verified
 through field  monitoring  activities  (Chapter  6)  at  the full  scale treatment
 site.

 2.3  DESIGN AND MANAGEMENT PARAMETERS

 2.3.1  Loading Rate

     The  loading  rate (mass/area/application)  is the first  design parameter
that  should be determined based  on  the amount of  waste  that can safely  be
 applied in a single application.   The  loading rate is expected to be different
 for nonacclimated  and  acclimated  soils,  and  therefore different methods may be
 used  to establish  the  loading rate depending  upon  the  waste-impacted  history
 of the soil.

     Waste application rates (mass/area/application) have  been established  at
many of the land treatment facilities  currently operating under interim status
 permits.  For existing facilities operating in compliance  with interim status
 permits,  these  established  rates may be  used for  the LTD.   For  facilities
following Scenario  3, a  method  must be  used to determine  acceptable  site-
 specific application rates for the wastes to be land treated.  The use  of an
 appropriate battery of acute  toxicity screening  tests  provides  an acceptable
method  for  estimating the  initial  waste application  rates  to  be  used  in
 subsequent LTD  studies.    However, the  final  acceptable  rate of application
must  be  established by  the  rate  of leaching  versus  degradation  and
 immobilization in  the  treatment  zone.

     This  initial  loading  rate,  which may be  determined from  toxicity
screening, therefore  should  be  evaluated  in  terms of  predicted mobility

                                   33

-------
  potential  based  on  results  of  the  land  treatment  model.   Site,  soil  and  waste
  specific  data  along with predicted and/or measured partition and degradation
  parameters  are  used  as  model  input  parameters  to  estimate  the  fate of
  hazardous  constituents within the treatment zone at the design loading, rate(s)
  evaluated.                                                        -        ^  '

  2.3.2  Waste Application Frequency

      The  limit  of  how much  waste  may be  applied  in  a  single application
  combined with  the  frequency of application yields an estimate  of the annual
  waste  loading  rate  (mass/area/yr)  feasible at  the  site.   The design initial
  loading  rate(s)  can  be  tested at  several  frequencies.    The test  data  on
  degradation rates  and mobility for the  specific hazardous constituents  found
  in the waste can then  be evaluated for determining the SSAC.  The timing for
  waste  reapplication  may  be  determined using  a soil-based  bioassay  that
  indicates  detoxification of  the  waste/soil  mixture, or may be  based upon  a
 historical predetermined schedule of application of the waste at  the initial
 loading rate(s).

      Regardless of the approach used to  determine frequency and  rate  of  waste
 application,  effective treatment must be demonstrated, as  required in 40 CFR
 Part  264.   This  includes  demonstration of  detoxification (transformation)
 using bioassay  procedures, and  demonstration of degradation and immobilization
 of hazardous  constituents  in  the waste.

 2.3.3  Waste  Application  Method

      The  selected method  of  waste application should be demonstrated  to result
 in effective treatment.   The  SSAC for a  particular  waste may be  a  function of
 the waste  application  method.   If the SSAC established for  a given waste  and a
 given soil  is unsatisfactory, then modifying the method of waste  application
 may increase  the SSAC  to  an  acceptable  level.   For example, a change in  the
 method  of  application  from surface  soil  application to waste incorporation  on
 subsurface injection may  be  effective  in  increasing  the  SSAC for  waste
 constituents.

      Changing the  method of  application  may also decrease  the SSAC for  other
 constituents, however,  by limiting soil   aeration  capacity,  etc.   Therefore,
 any modification should be carefully evaluated to determine the overall effect
 of  the method on the SSAC.

      If historical operating  data suggest  that changes to  current  application
 methods would  not improve waste  land treatability, then  evaluation  of  this
 design option may not be necessary.

 2.3.4  Operation and Management Factors

     Operation  and  management  factors,  addressed   1n 40 CFR Section 264.272
 include those listed  in Table 1.2.   The effect  of  these factors on  the  SSAC
may  be  determined  in  laboratory  and/or  field  experimental  studies.
 Information from the  experiments is  used  to optimize waste treatment in  land
treatment  facilities  in accordance with  the  standards identified  in  40 CFR

                                   34

-------
 Section 264.273.  The operation and management  factors  included in the LTD may
 be  based  on  current  practices,  if  any,  as  well   as  waste/soil/site
 characteristics which  suggest  possible improved treatment performance if such
 management practices are initiated.

     Microbial  and/or  chemical activity may  be  enhanced  through  waste/soil
 Incorporation,  soil  aeration,  microbial  inoculation,  fertilizer  application,
 and establishment of vegetation.   If a soil has poor aeration, tilling may be
 investigated.  Fertilizer application should be investigated if soil and waste
 nutrient  levels  are low compared  with available  carbon  levels in  the waste.
 Waste/soil  incorporation  and  microbial  inoculation  may be  investigated  if
 Indigenous  microbial  populations are  low.    Measures  for  control   of  soil
 moisture may  include methods for both irrigation and drainage, the  evaluation
 of  which  would  depend  upon  the water  balance  at  the site,  groundwater
 elevation,  concerns for constituent mobility,  and soil  moisture  content
 required  for optimal   biodegradation.   Soil   pH  control  measures  should  be
 Investigated  if  existing  soil  pH  conditions prevent adequate  soil microbial
 activity  or  produce soil solution  conditions  that  favor  inorganic hazardous
 constituent migration (for example, low soil pH values).

 2.3.5  Evaluation of the Effect of  Design and Management
       Parameters on SSAC Values

     Information  obtained  from laboratory  studies concerning "volatilizatiSn
 corrected" biodegradation rates, immobilization (partitioning) volatilization
 rates,  initial  toxicity,  and  detoxification rates  as  a function  of loading
 rates  and  frequencies, application  methods,  and  operation  and  maintenance
 options are used  to formulate  input to the land treatment model.   These input
 data reflect the combined mobility/degradation  effects that allow selection of
 PHCs for  field  verification..  In  addition,  the mathematical  model  provides a
 tool for:

     1.   Evaluation of  the  effects of  site  characteristics,  including  soil
 type, soil horizons, and topography/runon-runoff,  on treatment performance;

     2.   Determination  of  the  effects  of  design  (loading rate,  loading
 frequency), and operation parameters (e.g.,  irrigation, amendments to  increase
 degradation) on treatment performance;

     3.   Evaluation of the effects of environmental parameters (e.g., season,
 precipitation) on treatment  performance;  and

     4.   Comparison of the effectiveness of treatment  using  different design
 and operating practices in order to maximize treatment.

 2.4  FIELD VERIFICATION STUDY

     The most appropriate combination(s)  of operation and management  options,
 loading rate,  and frequency is  (are)  selected and  may be  used  in   a  field
verification study depending  upon the choice of the LTD scenario.  The use of
 laboratory  experiments  to  select  options  for  evaluation  1n  a  field
verification  study may reduce   high  costs  associated  with  field  scale

                                   35

-------
 investigations,  and  may  allow  for more detailed  evaluation  of  field
 performances under a limited range of treatment variables.

     A short-term (one year) field study should be used to assess the ability
 of  the  land treatment unit to  prevent  hazardous  constituents  from migrating
 rapidly out of the treatment zone.   Therefore, soil-pore liquid and soil core
 sampling  and  analysis for  toxicity (toxicity bioassays),  soil-pore  liquid
 analyses  for  mutagenicity potential,  and soil-pore  liquid  and  soil  core
 analyses  for  specific PHCs are  considered  extremely important  to  determine
 migration  of  hazardous constituents  in  the field demonstration.   Long-term
 monitoring  and  continued  use  of  the land  treatment  model  for  the  land
 treatment  unit during full-scale operation under  the  Part B permit will  allow
 continued  evaluation of treatment effectiveness or for modification to be made
 in design  and management  practices to maintain effective treatment.

     A one-year field  plot  study,  including  waste  application  and monitoring
 for  treatment  effectiveness,  is  recommended.   However,  a shorter  field
 verification study  (e.g.,  6 months)  may  be conducted  1f  laboratory  results
 indicate rapid treatment of waste  constituents.   The length  of time required
 for field  scale verification may be extended if  Insufficient  data  have been
 obtained, or  if  waste  application  or  operating practices  are  not
 representative of the full-scale  facility.   Other  factors,  including  unusual
 weather  patterns  (e.g.,  extremely  wet  or dry  season) and  inconsistent  or
 contradictory data may be used  at the discretion of  the  permit writer  for
 extension of the time required  for the  field plot study.

 2.5  ANALYTICAL ASPECTS OF  CONDUCTING AN LTD

     The specific constituents  to be  measured  in wastes,  soils, waste/soil
mixtures,  soil-pore liquid, and  groundwater during the  performance  of an LTD
 include constituents  that  may  affect  the functioning  of  a  land treatment
 system (Type  I analyses),  constituents  that may  affect the  performance  of
other analytical procedures (Type  I  analyses), and hazardous  constituents as
defined in  Appendix VIII of 40 CFR Part  261  (Type II and Type III analyses).
 A listing  of the three types of  analyses, as well as the media to be  sampled
for each type are presented  in  Table  2.3.

     All  procedures used to measure  constituents  included  in  Type I analyses
 should be  those  approved  by the U.S. EPA or  should be recognized  standard
methods.   Most  of the required  methods  for these constituents are described in
 Tes_ M(?5hod!__for Evaluating Solid Waste, Physical/Chemical  Methods.  SW-846
 [U.S. EPA  1982b).  In  the  Guidance for the  Analysis  of  Refinery  Wastes (U.S.
EPA 1985a),  1n  Standard  Methods for the  Examination  of Water and Wastewater
 (AfHA  1985),  in Methods  for  Organic   Chemical  Analysis of Municipal  anJ
 Industrial  Wastewater  (U.S.  EPA  1982a).  1n  Methods  of Chemical  Analysis  of
 Water and Haste (UTSTEPA  1979), in Methods of Soil Analysis, Part 1: Physical
 Properties  (Black 1965) and in  Methods of Soil  Analysis, Part  2:  Chemical and"
Microbiological  Properties   (Page  1982).   AT!analytical   data  should  be
 reported based  on  the wet  weight of  the  sample  unless otherwise specified.
 For samples containing water (other  than  aqueous  samples), the percent water
 should  be  determined  on  a  representative  subsample so  that constituent
concentrations can be determined on a dry  weight basis,  if required.


                                   36

-------
Table 2.3  Suggested Analytical  Information for an LTD
Type of
Analysis



Type 1



























Purpose



1. To provide infor-
mation concerninq
the land treat-
ability of a
waste

2. To optimize other
analytical pro-
cedures



















Constituents



Water content
Total residue
Total volatile
residue
Oil and grease
Total organic
carbon
Extractable
hydrocarbons*
Specific gravity
(1 iquid) or
bulk density
(solids)
Total dissolved
sol ids or
electrical
conductivity
(EC)
PH
Nutrients (nitro-
gen, phosphorus,
potassium)
F luoride*
Cyanides*
Sulfides*
Total organic
hal ides




Waste
X
X

X
X

X

X


X





X
X


X
X
X
X
x

Media to be Sampled
Soil
Treatment Zone Below
Zone nf Below Zone of Treatment
Incorporation Incorporation Zone




X X X

X X X

XXX








X XX
X XX


X
X
X
X




Soil-
Pore
Liquid








X








X
X



X
X
X
x




Ground -
Water




X

X

X








X
X



X
X
X
x


-------
Table 2.3  Continued
Type of
Analysis
Type II
Purpose Constituents
To detect, monitor. Appendix VIII
and quantify selected metals**
Appendix VIII con-
stituents Appendix VIII
Media to be Sampled
Soil
Treatment Zone Below
Zone of Below Zone of Treatment
Waste Incorporation Incorporation Zone
xx xx

Soil-
Pore
Liquid
X

Ground -
Water
X
                                     organic  con-
                                     stituents that
                                     are reasonably
                                     expected to be
                                     in, or derived
                                     from waste
                                     placed in or  on
                                     the treatment
                                     zone of  a land
                                     treatment unit

                                   Principal  hazard-
                                     ous constituents
                                     (PHCs),  which
                                     are hazardous
                                     constituents
                                     contained in  the
                                     wastes to be
                                     applied  at the
                                     units  that are
                                     most difficult
                                     to  treat,  con-
                                     sidering  the
                                     combined  effects
                                     of  degradation,
                                     transformation,
                                     and  immobi 1iza-
                                     tion (40  CFR
                                     261.278)

-------
       Table 2.3   Continued
Type of
Analysis



Type II!



Purpose



To identify and
quantify Appendix
VIII organic con-
stituents
Media to be
Constituents Soil
Treatment Zone
Zone of Below Zone of
Waste Incorporation Incorporation
Appendix VIII
organic con-
stituents XX X

Sampled

Below Soil-
Treatment Pore Ground-
Zone Liquid Water


X XX

       **
*If used as  an  indicator of amount of  wastes  applied,
*lf expected to be present in the waste.
"Total  concentrations and not EP toxicity data.
CO
ID

-------
      If approved  by the  permit writer, the hazardous constituents (Type II  and
 Type III  analyses)  for  wastes  handled  at  a  facility that  are  from  an
 identified process (e.g.,  petroleum refinery processes)  for  which  analysis  is
 required may include only those constituents that  are reasonably  expected  to
 be  in,  or derived from  waste placed  in  or on the treatment zone  of  the  land
 treatment unit (40  CFR  270.20).    U.S.  EPA  has developed  such  a subset  for
 wastes  from  petroleum  refineries  (i.e.,   the  "Skinner List").   The  list
 approved as  of  October 1985  is included in Table D.I in Appendix  D.

      For facilities other  than  petroleum refineries,  guidance  for  determining
 constituents for  which  a  facility  should  test could  follow  the  guidelines
 given to facilities for preparation  of  petitions  to delist hazardous  wastes
 (U.S. EPA 1985).    Two  general  procedures  are  given:    the facility  should
 submit  either  (1)  a complete listing  of  raw  materials,  intermediate  products,
 by-products, and final products; or (2) representative analytical data  for  all
 constituents listed  in Appendix VIII of Part  261 that are likely  to be  present
 in the  waste at significant  levels, as well as the basis  for  not  analyzing  for
 the  other Appendix  VIII hazardous  constituents.   Chapter 6 of the  document,
 Petitions to Delist  Hazardous  Wastes;   A  Guidance  Manual  (U.S.  EPA  1985c)
 shouldbe consultedFora  thorough  discussion of  theseapproaches.   The
 applicant and  permit writer  should  agree  in  writing  on the  specific  subset  of
 Appendix  VIII constituents at the initiation  of negotiations.

      Hazardous  constituents  must  be  identified and  quantified  according -to
 procedures  and  technology approved  by the  U.S.  EPA,  i.e.,  Test  Methodst  for
 Evaluating  Solid  Waste, Physical/Chemical Methods,  SW-846   (U.S.  EPA  1982b).
 Additional information on analysis  of  Appendix  VIII constituents may be found
 in Characterization  of  Hazardous  Waste  Sites, A  Methods Manual.-  Volume  3:
 Available  Laboratory Analytical  Methods (Plumb 1984).

      Methods for  analysis  of hazardous  constituents  are complex  and  require
 the  services of  an  analytical  chemist  with experience  in  hazardous waste
 analysis.   Analytical  difficulties  often  occur  when  the  sample matrix  is
 chemically  similar to the  analyte,  and  thus  potential  interferences may  be
 present  in  amounts  that overwhelm the  analytical technique.    To deal with
 severe  interferences and yet achieve  useful  detection  limits  is  a  difficult
task  for the  analyst.   Interferences may  have marked  effects  on  detection
 limits.

      Detection  limits  of analytes as  a  function  of analytical method, media
 sampled,  and sample  size should be calculated and  reported.   The U.S.  EPA  has
defined detection limit in  40 CFR 136.2(f):

      'Detection  limit1  means the  minimum concentration  of  an  analyte
      (substance) that can be measured  and reported with  a 99%  confidence
      that the analyte concentration is greater than zero  as determined  by
      the  procedures set forth in Appendix B of this Part.

Regulations  outlining  this   procedure, as  well  as  information on estimating
precision,  recovery and   other   quality  assurance  and   quality  control
considerations may be found  in The Federal  Register (Vol.  49, No. 209,  October
25,  1984, pp. 43234-43442).


                                   40

-------
      At  this  time,  U.S.  EPA has not provided definitive guidance on  acceptable
 detection  limits  for Appendix  VIII  constituents  in different  types  of
 environmental  samples.  The  applicant  should  discuss  with the  permit writer
 acceptable  detection  limits  for  waste  and  waste/soil  samples. .  Target
 detection  limits in water samples as reported by  a  commercial  laboratory and
 by the U.S. EPA are presented  in Table E.I of Appendix  E for  selected Appendix
 VIII  organic  constituents and in Table C.I of Appendix  C  for constituents of
 petroleum  refinery  wastes.    Sample  results  should  be  reported for  all
 hazardous constituents as positive values or as below detection  limits (BDL).

      Clean-up procedures should  be  used  as  required  to  reduce analytical
 interferences and provide reasonable detection limits.   U.S.  EPA has developed
 a  document,  Guidance for the Analysis of  Refinery Wastes  (U.S.  EPA 1985a)  to
 describe  and  direct modifications applied to samples from  petroleum refining
 waste streams.  Samples containing oil  are especially difficult to analyze.
 Care  should be taken not to over-dilute extracts  to minimize  interferences due
 to oil,  which  may result  in detection  limits  which are  unacceptable.   A
 possible solution to the problem of analyzing samples containing oil might  be
 to use analytical methodologies that are more sensitive to  the constituents  of
 Interest  (e.g.,  6C/PID  for  aromatics  and  6C/FID  for  hydrocarbons).
 Verification  of  alternative methods should be accomplished  by analysis of 5-10
 percent of the samples with GC/MS.  When reporting  results  of organic analyses
 of samples  containing  oil, the  amount  of oil  present  and  the  cleanup
 procedures  used should  be  reported.    Any modifications  made  to  U.S.  IPK-
 approved standard methods should be documented  by the laboratory.

      Type II  analyses  are  designed to detect  and  monitor  levels of Appendix
 VIII  volatile  and  semi-volatile organic constituents on  a  routine basis using
 sample extraction   preparation techniques  and  GC  and  HPLC  for  detection  of
 organic  constituents.    These  analyses  are  used   for  known  hazardous
 constituents  such   as  those  listed in  an approved  subset of   Appendix  VIII
 constituents  for a  specific  waste type or those designated as  PHCs.  The use
 of  Type  II analyses allows for the  processing  of large numbers  of samples  at
 lower costs than Type  III analyses.

      Type II  analyses  also  include the detection of metals in  the  soil/waste
 treatment system by the  use  of ICP or AA.   Accumulation of  metals  are  often
 the factor  that controls the  total  amount of waste that  may be treated per
 unit  area.    Suggested maximum concentrations  of  metals that  may  be  safely
 added  to  soils (U.S.  EPA 1983a)  are  shown  in  Table  2.4.  The  concentrations
 based on current literature and experience were developed  using microbial  and
 plant toxicity limits, animal  health considerations, and soil chemistry which
 reflects the ability of the soil to immobilize the metal elements.  Table 2.5
 presents suggested  acceptable  levels  of metals  for  which   less data  are
 available (U.S.  EPA 1983a).   These  levels  are  based on  only a limited
 understanding of the behavior of these  metals  in  soils  and  should be used as  a
 preliminary guide.    If  a waste  to be  land  treated  contains  these  metals,
 laboratory or field  tests  should  be  conducted  to  supplement  the  limited
 information  in the  literature.

     Type III  analyses are designed  to  Identify  and  quantify  Appendix  VIII
organic constituents using sample clean-up and  extraction techniques and GC/MS

                                   41

-------
Table 2.4  Summary of  Suggested Maximum  Metal  Accumulations
           Will Be Left in Place at Closure* (U.S.  EPA 1983a)
Where Materials
                                                                   Soil
                                                             Concentrations
                                                             Based  on  Current
Sewage Sludge
Loading Rates*
Element (mg/kg soil)
As
Be
Cd 10
Co
Cr
Cu 250
Li
Mn
Mo
Ni 100
Pb 1000
Se
V
Zn 500
Calculated Acceptable
Soil Concentrations*
(mg/kg soil) (kg/15 cm-ha)
500
50
3
500
1000
250
250
1000
3
100
1000
3
500
500
1100
110
7
1100
2200
560
560
2200
7
220
2200
7
1100
1100
Literature and
Experience**
(mg/kg)
300
50
3
200
1000
250
250
1000
5
100
1000
5
500
500

 *If materials will  be removed  at  closure  and plants will not be  used  as  a
  part of the operational  management  plan, metals may be  allowed  to  accumulate
  above these levels as long  as treatability tests  show that metals  will  be
  immobilized at  higher levels  and that other treatment processes will not be
  adversely affected.

 *Dowdy et al. (1976); for use  only when soil CEO15 meq/100 g, pH>6.5.

 ^National Academy of  Science and  National Academy  of Engineering (1972)  for
  20 years irrigation  application.

**If metal tolerant plants will  be used to establish a vegetative cover at
  closure, higher levels may  be acceptable if treatability tests  support  a
  higher level.
                                   42

-------
Table 2.5  Suggested  Metal Loadings for Metals with Less Well-Defined Informa-
           tion (U.S.  EPA 1983a)
                      Total Loading                     Total Loading
        Element       (kg/ha-30 cm)       Element       (kg/ha-30 on)
Ag
Au
Ba
Bi
Cs
Fr
Ge
Hf
Hg
Ir
In
La
Nb
Os
Pd
Pt
Rb
400
4,000
2,000
2,000
4,000
4,000
2,000
4,000
40
40
2,000
2,000
2,000
40
2,000
4,000
1,000
Re
Rh
Ru
Sb
Sc
Si
Sn
Sr
Ta
Tc
Te
Th
Ti
Tl
W
Y
Zr
4,000
2,000
4,000
1,000
2,000
4,000
4,000
40
4,000
4,000
2,000
2,000
4,000
1,000
40
2,000
4,000
for identification and quantification.   These  analyses  are performed when the
identity and levels of hazardous  constituents  are  not  known, such as in waste
characterization and in degradation  studies.   They are  also used periodically
in  conjunction  with Type  II  analyses to  confirm  the accuracy of  Type  II
techniques.

2.6  ANALYTICAL COSTS

     With the  emphasis  on measurement of  Appendix  VIII  constituents  in  the
performance of  an  LTD,  the costs  of   analytical   measurements  may  be
significant.   Table 2.6  presents  costs estimates  for  Type  I, II,  and  III
analyses.   The  cost  estimates  were  prepared by  Michael  Gansecki  of U.S.  EPA
Region VIII after discussion with commercial  laboratories.  The higher costs
quoted   are  for  samples  that  require  more  extensive  clean-up  and
extraction/digestion  procedures,  such as  soil  samples.   Although Type  III
analyses  are  more expensive than  Type II, they  may  provide  more thorough
Information on  identification of organic constituents than Type II  analyses.
Because  of  the  potentially  high costs  of  analytical services,  careful design
1s  required  in  developing  the LTD plan  to obtain the most  useful  and
representative information at  a reasonable  cost.


                                   43

-------
Table 2.6   Estimates of Analytical Costs for Type I, II, and III analyses
            (Gansecki 1986)
Type of Analysis
 Cost per Sample
Type I

Type II
     Selected Appendix VIII organic constituents
     (e.g., HPLC analysis of polynuclear aromatic
     compounds)

     Metals

Type III
     Appendix VIII organic constituents
          Volatiles by GC/MS
          Base/neutral fraction by GC/MS
          Acid fraction by GC/MS
          Volatiles, base/neutral  and acid
            fraction by GC/MS
$20-30/constituent
$200-300/sample
$ll-15/metal
$250-350/sample
$350-450/sample
$250-350/sample

$900-1500
                                   44

-------
                                                          OSWER POLICY DIRECTIVE NO.

                                                             6 6  • 00-2   *
                                  CHAPTER 3

        PROCEDURES  FOR  COLLECTING FIELD INFORMATION FOR RECONNAISSANCE
                    SURVEY AND FIELD VERIFICATION STUDIES


3.1  INTRODUCTION

     Field  information  at  an HWLT  unit may  be required for  the  following
reasons:

     (1)  to  determine  whether  the  site/soil/waste  system  at  a  new site
appears to be appropriate for land  treatment;

     (2)  to  identify "uniform  areas," and  to determine the  variation  in
important  soil  properties that  affect   waste  treatment  within  the  "uniform
areas";

     (3)  to  determine whether  there is  migration  of hazardous constituents
from the bottom of the treatment  zone at  an  ISS land  treatment  unit;

     (4)  to determine whether groundwater beneath an ISS land treatment unit
is contaminated  and  whether  the contamination  is due to  the  land  treatment
unit;

     (5)  to evaluate past waste  management  activities at  an ISS  unit by means
of past waste management records  and present  waste distribution  in  the soil;

     (6)  to  identify any  "hot spots"  in  the  ISS treatment  area,  and  to
determine whether wastes in these "hot spots"  are being  adequately  treated;

     (7)  to determine the level  of  accumulation of Appendix VIII metals;

     (8)  to  determine the  representativeness  of a  field  verification test
area compared to the conditions  of  the full-scale unit;

     (9)  to  determine the background conditions for the field verification
study,  including the levels  of hazardous constituents  in the  soil  treatment
zone; and

    (10)  to monitor treatment in a field verification study.

     Much of this  information may  already have been  gathered  to fulfill Part
270 requirements for the  Part B  application.   In particular, an  in-depth soil
characterization and mapping should  have been  conducted.    Waste  analyses
should  also  have  been  performed   to  characterize  the  waste  streams (both


                                    45

-------
hazardous  and  nonhazardous)  that  will  be land treated  and  used  in the  land
treatment  demonstration.   For  existing  units, the reconnaissance  information
should include chemical characterization of both  the  waste/soil mixture  in the
treatment  zone of the  unit and waste management practices (existing and past)
at the land treatment unit.                                        -

     This  chapter  summarizes  the Part  270 data  requirements  applicable to
treatment  demonstration  planning  and  provides additional  guidance  to  the
applicant.   This discussion  supplements the  guidance  provided  in the  Permit
Applicants Guidance Manual for HWLTSD Facilities  (PAGM)  (U.S. EPA  1984b), with
specifics  on how to gather the information suggested  by the PAGM.   Statistical
considerations  for  the  performance of  an LTD,  including  a reconnaissance
investigation are presented in Appendix  B.

3.2  WASTE CHARACTERIZATION

     A demonstration of the land  treatability of  a  waste must first begin with
waste characterization.   Only  after  thorough characterization  of  a waste has
been completed can  an  appropriate  LTD be conducted,  since comprehensive waste
analyses are required  to  identify and  quantify the hazardous constituents in
the waste.  If significant concentrations of hazardous  constituents other than
those for which the waste was listed  are present, analytical measurements used
in the  LTD should be  more extensive  (i.e., analyses for many of the 40 CFR
261, Appendix  VIII  compounds vs.  parameters  such  as  total  oil  and grease-).
The converse may also be true:   thorough characterization may allow for the
elimination of  certain analytical procedures  during the performance  of the
LTD.   Waste characterization  will  also provide a preliminary assessment of
whether special requirements  exist (e.g., site life of  the land treatment unit
may be determined by total allowable  accumulation of  metals).

     The general Part B  information  requirements  specified  under  Part
270.14(b)  require the submittal  of 1)  chemical  and  physical  analyses on the
hazardous  wastes  that will  be  handled  at  the facility, including  all data
required to  properly treat,  store,  or  dispose of wastes  in accordance with
Part 264,  and 2) a copy of the waste  analysis plan.  In  addition,  the specific
information  requirements   under Section  270.20(b)   (4)  require that  an
owner/operator of any facility that includes a land treatment unit submits "a
list of hazardous constituents reasonably expected  to be in, or derived from,
the wastes to be  land  treated, based  on waste analyses performed  pursuant to
Part 264.13."   Part  270.20  (a)  also stipulates that  the  description  of the
treatment  demonstration plan must  also  include a list  of potential hazardous
constituents in the waste.

     The program of routine, broad scale  waste characterization conducted for
the Part B application only  partially fulfills LTD data needs.   For the LTD,
representative  waste  batches must  be  obtained  and  characterized in detail,
especially  if  an experimental  (i.e.,   laboratory  or  field  verification)
demonstration  1s  planned.    If the waste for the  LTD  can  be obtained  at the
time of sampling  for  general  waste characterization, one set of  analyses may
serve both purposes.
                                   46

-------
     Although an  LTD is  not required  for  land treatment  of  a nonhazardous
waste, its presence within the same treatment  zone may affect the treatment of
the hazardous waste, and vice versa.  When nonhazardous wastes  are treated in
the same  treatment  zone as  hazardous wastes,  a detailed  characterization of
the nonhazardous  waste  (including  Appendix  VIII hazardous constituents) must
also  be  provided.   The  applicant  does have  the  option  of  segregating  the
hazardous and nonhazardous  wastes  at the land  treatment  unit,  and therefore
avoid characterization of the nonhazardous waste.

     The  waste  characterization  phase is  also  important  for  identifying
possible capacity limiting  constituents  (CLC)  (e.g.,  metals)  and  application
limiting  constituents  (ALC).  The  limiting  levels for the  CLCs will  depend
partially on  the closure method employed at  the  HWLT unit.  For  a thorough
discussion  of  CLCs  and  ALCs,  the  applicant should refer  to   Chapter 7  of
Hazardous Waste  Land Treatment (U.S.  EPA 1983a).

3.2.1  Sampling  and Sample Collection

     Sampling of waste  should be conducted in  accordance with good scientific
methods to ensure that accurate,  representative samples  are  obtained.  Because
waste uniformity  and  variability  always  present  a problem in treatment
demonstrations,  all samples should  be collected using  appropriate sampling and
compositing  procedures.   Multi-phase  samples  should be homogenized before the
sample is aliquoted  so  that  the  aliquot taken is  representative of the total
sample.   Test Methods for Evaluating Solid Waste.  Physical/Chemical Methods,
SW-846  (U.S.  EPA 1982b) presents  general sample  collection requirements  and
statistical  considerations  for solid  waste  samples and  should be consulted
concerning these protocols.  "Specific  amounts needed  for  analysis and use in
the  laboratory  and field  plot  studies depend  upon  the  type of treatment
demonstration chosen and on whether an  existing  site  is being used  for
demonstration of  treatability of  a waste.   The applicant should refer to the
appropriate  sections of  this  document  when  estimating  amounts of  wastes
required to perform the respective treatment  demonstration  approaches.

      In  some complex waste generating  situations  (e.g.,  intermittent waste
generation or seasonal  variability),  sampling may need to be  performed  over  a
period of months to  produce  a representative  set of samples.  To decrease the
analytical burden,  the  quantity of  waste that will be used in  the treatment
demonstration could in  some cases  be  collected  and  stored  at  the  time of
sampling  and used  for  overall  waste characterization.   The  waste should be
representative of the mixture of waste  streams that are land applied,  if  such
a mixture  is  used.   If  wastes from different  sources  are  applied to different
locations, samples of each waste should be analyzed.

      All   sampling  equipment  should be  thoroughly  clean  and free of
contamination both   prior  to use  and between  samples.   Storage  containers
should be similarly  free of  contamination.  While only plastic  or Teflon1" may
be  used  for samples  intended for inorganic analysis,  glass,  Teflon1" or
stainless steel  may  be  used  for samples intended  for  organic  analysis.  Zero-
headspace  containers should  be  used for  samples  collected  for  analysis of
volatile  waste constituents.  Care should be taken that both the  samples  and
storage container materials  are not reactive with the waste.  If the sample  is


                                     47

-------
to  be  frozen for storage,  ample  room for expansion must  be provided in the
sample container.

3.2.2  Sample Handling and Storage

     After  a sample has been collected,  it  must be preserved to protect the
chemical and physical integrity of the sample prior to analysis.  The type of
sample  preservation  required  will vary according  to  the sample type and the
parameter to be  measured.   Appropriate preservation and storage requirements
for  different  analytical  methods  are  described  in SW-846  (U.S.  EPA 19825).
The  applicant should make prior arrangements with  the receiving laboratory to
ensure  sample  integrity until  the time of  analysis.    The  Guidance for the
Analysis of  Refinery Wastes (1985a)  presents guidelines for  sample  handling,
preservation and holding times for petroleum  refinery  wastes.

     For wastes  that  will be  used 1n the LTD, samples  may be tightly sealed
and  preserved at 4°C,  or  frozen when organic constituents are expected  to be
lost through volatilization.    Freezing may  cause multi-phase  samples to
separate, which  are then difficult or  impossible to homogenize  after  thawing.
Freezing may be  accomplished by packaging sealed sample  containers in dry ice
directly after  collection  if  other refrigeration methods are not  immediately
available.    For  wastes  collected  for the LTD,  preservation  methods that may
bias the LTD results  should be  avoided.   Since  storage  of  large,waste volumes
for  the  LTD may present  problems in  terms  of  qualitative   and quantitative
waste integrity, the applicant should strive  to minimize storage time.

     At some facilities,  wastes  that will  be land  treated may be stored for
periods of time before being land applied.  This  pattern of holding  could also
be  followed  for  the performance of the LTD.   For  wastes that are being  held
for  use in the  LTD,  a set of  representative  constituents and waste  properties
could be monitored in order  to document changes  in  waste quality.

3.2.3  Analysis of Waste Characteristics

     At the  reconnaissance  level  of  investigation,  the  waste characterization
should be as thorough as possible, including Types  I  and III  analyses.   Since
GC/MS analyses  (Type III  analyses)  will  most  likely be the  detection method
used for characterization  of organic  waste  constituents, additional  library
searches for  identification of  compounds  detected  in GC/MS  analyses, but not
Included  in  the  EPA-approved  subset of  Appendix   VIII  constituents for the
particular industry (e.g., the "Skinner List" for the  petroleum industry), are
recommended  and  should not  add  significantly to  the cost  of the  analyses.
Another alternative may be  to identify the  ten  most  prominent  GC/MS peaks  in
each waste  fraction (i.e.,  volatiles,  base  neutral  semi-volatiles, and  acid
semi-volatiles)  not otherwise identified as  part of the EPA-approved  subset.

     Quality control  procedures must be included  as  an integral  part of the
analytical   scheme  so as to provide  a means  of  determining  and  improving the
quality of   Information presented.    (See  Chapter  7  of this  manual  for  a
discussion of Quality Assurance/Quality Control.)
                                    48

-------
3.3  WASTE MANAGEMENT RECORDS FOR  AN  EXISTING SITE

     An  existing  site  should  provide,  as  part  of  its recannaissance
Investigation results, information concerning past waste management practices
that clearly document the  conditions  under which  hazardous  waste  was managed
at  the  site.    Table 3.1 lists important waste management  data  and records.
These records  should include  available  history  of waste  application  (i.e.,
application rates,  timing,  and location)  and  available  history  of  waste
quality (i.e.,  waste analysis (especially Appendix  VIII constituents) and unit
process  data.   These  requirements are  more  comprehensive  than  those  under
Interim status  standards (ISS), and complete  information may not be available.
Acceptability  of  partial  information  is  at  the  discretion  of  the  permit
writer.

     These  data  will  be  used  by  the permit  writer 1n  conjunction  with
treatment zone  soil  core and soil- pore liquid monitoring  data  to determine
uniform  areas  (which are based on waste loading  as well as soil  properties),
to evaluate the performance of present operating and management practices, and
to make  modifications  as required (i.e., changes  which  can  be  tested  in the
LTD and implemented  in the  operation  of the full-scale facility).

3.4  SOIL CHARACTERIZATION

     A basic understanding  of the potential  for degradation, transformation,
or  immobilization  of a  waste involves  an  understanding  of the  physical,
chemical, and  biological properties  of the  land  treatment  site.   Critical to
the treatment  demonstration  is a  thorough  understanding of  the  specific  soil
that will  act  as  the treatment medium for the waste.  Therefore, an in-depth
study of the site and soil  is necessary.  Much of the site  information (e.g.,
hydrogeology, topography, climate, and  water budget, including precipitation,
runoff,  runon,  evaporation,  and   infiltration)  should  already have  been
determined  to  fulfill  the  Part  270  requirements  for  Part  B of  the permit
application.   The  site  and  soil   analysis will  identify limiting conditions
that may restrict  the  use of the site  as  an  HWLT unit and, at  an existing
site, will  provide  an indication  of  whether waste constituents  are building
up, are  leaching  out of the  treatment  zone, or  whether "hot spots" of  waste
accumulation exist.  The analysis  will  also  provide  information for  selecting
field  plot  sites   if  field  verification  studies  are  required.    The   major
components  of  interest   in  the soil   system  are  the variations  in  physical,
chemical, and biological properties of the  soil  (U.S. EPA 9183a) and  the  area!
and vertical distribution of waste constituents  in  the  soil.

3.4.1  Soil Survey

     A  soil survey should  already have  been   conducted  for  the  permit
application, according   to  PAGM  guidance.   Many areas have  already  been
"broadly"  surveyed  by the U..S. Soil  Conservation  Service.   If  such a  survey
exists for a given  site, it may be used as   a guide.   However, an  existing SCS
survey,  unless  done specifically  for  the site, cannot be used as  a substitute
for  a  detailed site-specific  survey and sampling  program  because  the  scale
used to  conduct the SCS surveys  is too small,  analyses  are  too  few,  and  often


                                   49

-------
Table 3.1  Useful Waste Management Data and  Records.
  Category
  Item
        Specific Information
History of Waste
 Application
History of Waste
 Quality
Years in
service and
annual quan-
tity of
waste land
treated

Placement of
wastes on
land treat-
ment plots

Estimated
annual quan-
tity of
waste land
treated

Approximate
placement of
wastes
Waste
Analyses
                       Unit
                       Processes
Records of measured annual waste
quantity (dry weight) treated over
the life of the HWLT unit.  In-
clude all wastes, both hazardous
and nonhazardous, that are managed
on the same unit.

Records of quantity (dry weight),
date, and location of each waste
application for each land-treated
waste over the life of the LT unit,

Estimated annual  waste quantity
(dry weight) treated during the
life of the unit.
Approximate quantity (dry weight),
timing, and location of each waste
application during the life of the
unit.

Periodic analyses of each land-
treated hazardous waste.  (Non-
hazardous waste analyses are also
necessary if these wastes are land
treated in same plot as hazardous
wastes.)  Parameters should include
those listed as Type I analyses and
Appendix VIII hazardous constitu-
ents, as available.

History of unit processes employed
in the generation and treatment of
the land treated wastes (i.e.,
wastewater treatment) for the entire
un i t 1 i f e.
                                    50

-------
the  surveys  do  not  include  all  the  necessary parameters.    If  an  acceptable
soil survey by a qualified soil  scientist  has  not been done,  a soil  scientist
should be retained to conduct the soil survey.  The characterization .of waste
distribution in the soils will require an  even  more  detailed,  extensive,  and
carefully controlled sampling program  than is required for  the  soil  survey.
Guidance for conducting a soil survey is given in the National Soils Handbook
(SCS 1983).

3.4.1.1  Conducting the Soil  Survey-                       .
     In a soil survey, the soil  series present at a given site are identified
and sampled.  Soil series are differentiated on the basis of both physical  and
chemical  characteristics.   The  number  of  samples required  to  adequately
identify the  soil series  present  at  a  site  and  to characterize  the  soils
should be  determined  by the  soil scientist.  Sampling  depth will  also vary,
depending upon the soils present  at the site,  but  should extend at least to 30
cm  below  the  treatment  zone.    The  geological  and  hydrogeological
characteristics of the  site  should  already have  been  conducted  according to
guidance given  in the  Permit Writer's  Guidance  Manual  for   the  Location of
Hazardous   Waste  Land  Treatment   Paci nties;   criteria  for  Location
Acceptability and Lxisting Applicable  Regulations  (U.S. EPA I98bbj.

     The soil survey information  should include:

     (1)  Soil profile descriptions

     (2)  Mineralogy

   '  (3)  Use and vegetation

          (a)  Permeability
          (b)  Flood frequency and  duration
          (c)  Frost action potential

     (4)  Estimates of erodibility of the soil (used  to  design erosion control
structures)

     (5)  Depth   and  texture of surface  horizons  and  subsoils  (used to
determine  if  the  soil  is suitable for contaminant  degradation  and  to design
berms and lined runoff retention ponds)

     (6)  Depths  to  seasonally high water  table  and  zones, such  as  fragipans,
that may limit vertical water movement.

     The soil survey of a proposed or existing site will  be used  to  define the
"uniform  areas"   of  the treatment unit  as well  as  identify any  potential
problem areas such as inclusions of sandy materials with high permeability.   A
uniform  area is  defined  as   an   area  of  the  active  portion  of  an  HWLT  unit
composed of  soils of  the  same soil  series to  which similar wastes  are  applied
at  similar  rates.   If two  or more  areas  are  otherwise  similar but  receive
different amounts of similar wastes, the heavier loaded area  may be  considered
representative of the other(s).   Two different  soil  series may  be  included  in
a  given  uniform area  if  a qualified  soil  scientist  determines that  the


                           !        51

-------
characteristics  that  differentiate the particular soil series in  question  do
not affect the success of land treatment of the particular wastes at the site.
The soil scientist may also determine that a single soil  series may.be divided
into  two or more  uniform areas 'if  those soil  properties  that  affect  waste
treatment vary  significantly  within  the original proposed uniform  area.   The
soil  scientist,  therefore, should  be  familiar  with those  soil  properties that
affect  treatability of  different  types  of  wastes or  should  consult with  a
person  knowledgeable  in  waste/soil  interactions.   A list  of  selected  soil
properties which are  important in  waste treatment and may be  included  in  the
soil  survey is presented  in Table 3.2.
Table 3.2
Soil  Physical
Survey
and Chemical  Properties  To  Be Determined  in Soil
Soil Physical Properties
                                  Soil  Chemical Properties
Soil texture
Bulk density
Available water capacity
Porosity (saturated water content)
Saturated hydraulic conductivity
Particle density
Soil temperature
Aeration status (saturated or unsaturated)
                                 Cation exchange capacity
                                 Total organic carbon or organic
                                    matter content
                                 Nutrients (in ZOI only)
                                 Electrical conductivity
                                 PH
                                 Total organic carbon
                                 Buffering capacity
                                 Type of clay
     For  new units,  the  soil within  the boundaries  of the  proposed land
treatment  unit  (i.e., within   the  boundaries defined  by the  runon/runoff
control  structures)  should  be  surveyed  along  with background  soils   (i.e.,
untreated  soils  outside the  boundaries).   While  the  same  process should  be
followed for existing units,  difficulties are often encountered  as  the  result
of waste additions and soil disturbances, which  may have significantly altered
active  area  soil  properties.  If a definable native  soil  still exists,  the
soil survey  must  emphasize deeper sampling  and  a  greater use of test pits  to
identify the soil series present, their  boundaries, and  their continuity with
background  areas.   In  some cases,  no native  soil  will  be  present  or
Identifiable.   Nevertheless,  the  soil  scientist should conduct  a  soil  survey
to identify "uniform areas."

3.4.1.2  Analysis of Soil  Samples Obtained—
     Soil  samples  should  be characterized  for their  chemical   and  physical
properties.   The values  obtained  may  be  used  for  management of . a land
treatment  unit  and  in predictive modeling to evaluate  treatment.   For  an  in-
depth discussion of these properties and their relationship  to  land treatment,
the applicant should  refer  to Hazardous  Waste Land Treatment  (U.S.  EPA  1983a)
and Review of  In Place Treatment Techniques  for  Contaminated Surface  Soils,
                                   52

-------
Volume 2:   Background  Information for In Situ Treatment (Sims et al.  1984).
Analytical  procedures for these characteristics may  not  be  widely  employed by
typical water, waste, and  sediment  laboratories.  Such  methods are, .however,
standard soil  procedures  used  by soil  laboratories and are recommended  for use
to  ensure  reliable results.   Complete discussion  of  these  procedures are
presented  in  Methods of Soil  Analysis.  Part  1:   Physical  Properties  (Black
1965)  and  Methods of  Soil  Analysis.  Part  2:   Chemical and  Microbiological
Properties (Page 1JHK).

     The number of samples  required  to  characterize the soil may be determined
by  the soil  scientist  using  the  statistical  method  similar  to  those  in
Appendix  B.    Enough  samples  should be  analyzed  initially to  determine
representative sample variance.  If the variance  is  large,  additional  samples
may need to be analyzed  to  establish reliable estimates of variability.   Mason
(1983)  and  Barth and Mason  (1984)  present  guidance on  sample analysis and
determination of variance.

     3.4.1.2.1   Soil  Physical  Properties—Soil physical  properties  are  those
characteristics, processes, or reactions of  a  soil  caused by physical  forces.
Measurements of  physical properties  that should be  included  in a  soil  survey
are listed in Table 3.2.

     3.4.1.2.2   Soil   Chemical  Properties—Chemical  reactions  that  occur
between waste constituents and  the  soil must be considered  in  land  treatment
demonstrations.   Large numbers  of  complex  chemical  reactions and
transformations,  including  exchange reactions,  sorption,  precipitation, and
complexing,  occur  in  the  soil.   Understanding  the  fundamentals of  soil
chemistry  and  the  soil  components that control  these  reactions  makes  it
possible to  predict the fate  of a  particular waste in the soil.   Chemical
properties that need to be evaluated are listed in Table 3.2.

     3.4.1.2.3   Soil   Biological  Properties—The  soil  provides  $ suitable
habitat for a diverse range of  organisms that render a  waste  less hazardous.
The types  and numbers of decomposer  organisms present in a waste-amended soil
depend  on  soil  moisture  content, oxygen status  of  the soil,  nutrient
composition, and  soil pH.  Organisms  important in the decomposition  of wastes
have  diverse enzymatic  capabilities  and include bacteria,   fungi, and
actinomycetes.    Although  enumeration of  species  and  numbers of  microbial
organisms  is not necessary in  the characterization of a  land treatment site,  a
recognition of  the  importance of these organisms  and their role  in  the waste
treatment  process  is critical.   Management  of the  unit  should  be  designed  to
manipulate  environmental  factors to enhance the  activity of these decomposer
organisms.   A discussion of  soil  organisms is  given in Introduction  to Soil
Microbiology (Alexander 1977).

3.4.2  Characterization of Distribution of Hazardous
       Constituents  in Soil (Existing Sites  Only)

     Characterization of  the  distribution  of  hazardous constituents' in  the
soil at  an  ISS  unit  may  be used to evaluate the performance of the  site.  The
data may be used to  determine:   (1) if hazardous  constituents  are present  in
the groundwater  below the  treatment  zone (see groundwater monitoring);  (2)  if


                                    53

-------
hazardous constituents  have migrated  below the  treatment  zone; and  (3)  if
degradation,  immobilization,  and/or  transformation are occurring  within the
treatment zone.                                                   .  -

3.4.2.1  Soil Core Sampling-
     Waste constituents may move  slowly  through  the soil  profile for  several
reasons,  such  as:   (1)  lack  of sufficient soil moisture  to  leach the
constituents through the system,  (2) a natural or  artificial  layer or  horizon
of low  hydraulics conductivity, or  (3)  waste  constituents  that exhibit  only
low to  moderate mobility  relative  to  soil  water.   Soil  core monitoring can
identify  any one  or  a combination  of these  effects.    The  intent of  such
monitoring  is  to demonstrate  whether  significantly higher  concentrations of
hazardous constituents are present below  the treatment  zone  than  in background
soils.  The applicant should refer to the guidance on  soil sampling procedures
and  equipment recommended  in  the Guidance Manual  on  Unsaturated   Zone
Monitoring  for Hazardous  Waste Land Treatment Units  jU.S.  EPA 1964).SoTT
samples collected  foranalysis of volatile  hazardous  constituents  should be
collected in zero-headspace containers.

     Background should be considered for the area  just outside  the HWLT  unit,
and not necessarily an  undisturbed,  pristine area.  The background should be
representative of  the  treatment  area,  except for  past  waste  applications.
Samples should represent the conditions of this background area  and  should not
be selected  in  a  biased manner that  would  lead to unreal istically  low  or high
concentrations of hazardous constituents.  If high concentrations of  hazardous
constituents are  found  in  the background soils,  that fact  should be reported
to the permitting official.

     3.4.2.1.1   Depth  of Sampling—Soil  cores should  reach a depth of  30  cm
below  the treatment zone.   After  samples  of the  zone  of  Incorporation  are
taken, that  zone  should  be removed  to avoid contamination  of  lower  horizons.
A  soil  core sampler may  be  used  which extends  to the base  of  the  treatment
zone.  To minimize  contamination, the  center of  the soil  core may be  removed
for analysis.   The  soil  cores  may be segmented with depth according  to visual
changes  in  soil properties (e.g.,  texture,  color, structure).   The  zone  of
incorporation  should comprise the first sample.  All soil  core segments should
be analyzed  separately.  As much  of  each  soil  core segment  should  be analyzed
as  possible,  within  the  limits  of the  extraction/digestion  and  analytical
procedures,  to ensure that waste constituents present will be detected.

     Alternate methods of  soil  sampling  through  depth  may also  be  used.   Each
soJl  core boring may be  segmented  according to  the  following  scheme:   ZOI,
ZOI-45  on,  45-90 cm,  90-150 on,  and 150-180 an.   Another method is  to divide
the soil core  into four segments:  ZOI, an upper treatment zone (TR1),  a  lower
treatment zone that extends to the  bottom  of  the 1.5  m  treatment  zone (TR2),
and  a below treatment  zone  that extends  to 30  cm below the  treatment zone
(BTZ).   Since  the depth  of the ZOI  may vary from  site to site, depending upon
soil conditions  and operating  practices,  TR1 and TR2 are each  defined as 1/2
of (B-ZOI),  where B is  the total  depth of the treatment zone.  Alternatively,
intermediate sampling depths  (TR1 and TR2) may be chosen to represent distinct
soil  horizons within the  treatment zone,  if  they are present.   Within each
zone,  samples  should be taken  consistently at the  same depths in each of these


                     ':               54

-------
two  zones  throughout  the  reconnaissance  investigation  and in  the  field
verification studies.  The amount of soil  analyzed  from each zone should be as
large as possible to ensure detection of waste constituents.

     3.4.2.1.2   Area!  Distribution of  Sampling—While the  uniform  area
delineates  the  domain of  each  set  of  soil  samples,  the location of  each
sampling point  within  each soil  series is  determined  randomly (see Appendix
B).  In addition to the random sampling points,  locations  which represent "hot
spots"  within  an  HWLT  unit  should  also  be  sampled  and should  be analyzed
separately.  These "hot spots" may include the following  locations:

     (1)  toe  slope  landscape  positions,  where  runoff may  have deposited
contaminated soil

     (2)  soils with a hydraulically restrictive lower horizon that may cause
lateral movement of soil-pore liquid, with subsequent accumulation  at the base
of the slope

     (3)  saturated areas, such as swales  or soils  with perched water tables

     (4)  soils below isolated areas of high permeability

     (5)  areas where  greater than  planned amounts of waste accumulate, such
as waste unloading locations next to roadways

     (6)  areas  where degradation  may  have  been  limited due  to  inadequate
nutrients, lack of sufficient soil moisture, or  inappropriate pH levels.

The soil scientist  should  note any unusual soil conditions that may indicate
the presence of "hot spots,"  such  as discolorations  or  the  presence  of oil
through depth.   If  a  "hot spot" is  found  during  a site investigation, more
intensive, repeat sampling of the "hot spot" may be required to determine the
potential  for leaching of  hazardous  constituents below the treatment zone and
to  define  possible  management  options  to  minimize migration.    Details  on
location of sampling sites are discussed  in Appendix B  and in Mason (1983) and
Barth and Mason (1984).

     3.4.2.1.3   Number  of Samples—A statistical  procedure incorporating the
estimated  variability of  the  levels  of   waste  constituents  at  the  site  is
recommended in determining the  number of  samples required.   Such  a procedure
1s  described   in  Appendix  B,  in  Preparation  of Soil Sampling Protocol:
Techniques and Strategies  (Mason 1983).  and in Soil Sampling Quality Assurance
User's Guide (Barth and Mason 1984).  Alternatively, guidance on the number or
samples given in the Permit Guidance Manual on Unsaturated Zone Monitoring for
Hazardous Waste  Land Treatment Units (U.S. EPA 1984b) may be  used.However,
caution should be used in compositing samples for analysis.

     3.4.2.1.4   Analysis  of  Soil  Core  Samples—Soil   core  samples should be
characterized  for  Appendix VI11  constituents,  or a subset  of Appendix VIII
constituents that  have been  approved by  the  U.S.  EPA,  using  Type  II or Type
III analyses, depending on the  use  of the data.   These  analyses  are required
to provide information about both organic  and inorganic  hazardous  constituents

                                    55

-------
that may be present at the site and should  be monitored throughout the life of
the HWLT  unit.   This  analysis  is  also required to determine  whether  an ISS
unit  is  meeting  treatment  performance  standards.   Analysis of.  soil  core
samples is also required during the performance  of  a field verification study.
The hazardous constituents monitored may be  those present at the time of waste
application  or  degradation products  not  originally  in  the waste.   Because
analysis  of  Appendix  VIII constituents is  not  required  under  interim status
standards  (40  CFR 265),  the  application  does  not  usually  possess  data
concerning all  possible hazardous  constituents.  The extent of accumulation of
metals  in the  treatment  zone of  the soil may be compared  with regulatory
limits.

     Detection limits  for  waste constituents in the  soil  should be reported.
If oily  wastes  are present, these  detection limits  should  be  reported  as  a
function of oil content of the  sample.  Sample  results should be reported for
all hazardous constituents as  positive values or below detection limits (BDL).

     The  following  approach  should  be  used   for  analysis to  preserve the
Integrity of the data:

     (1)  Each sample increment in  each soil core in the active  zone should be
analyzed separately so that data on "hot  spots" and other  possible anomali.es
will  not be lost.  Compositing should not be used for  these  samples.

     (2)  After background  samples have been  analyzed and  show no hazardous
organics,  or  analyses  are  begun  to  determine the  mean  and  variance  of
hazardous constituents  in  the  background  samples,  active  area samples may be
analyzed.   Concentrations determined  should  be compared  to the  background
levels.

     The  permit  writer may,  at his/her discretion,  allow the  applicant  to
analyze the  treatment  unit  samples first.   If  no  hazardous constituents are
found  in  the  groundwater  and/or  below the  treatment zone,  the background
levels may be assumed to be below  detection, and the background  soils need not
be analyzed separately.

     3.4.2.1.5  Interpretation of  Soil Core Sample  Data—A land  treatment unit
should be designed and operated such  that no vertical movement  of significant
quantities of hazardous constituents  occurs below the treatment zone.  In the
analysis of  the  data  collected, sound statistical  principles should be  used.
The  key  to  valid comparisons  between background  levels  and  levels  1n the
treatment  zone  is  the  choice  of sample size (number of replications) and the
use of random sampling.  Guidelines for statistical  interpretation of data are
presented  1n  Appendix B  and  the   Permit Guidance  Manual  on Unsaturated Zone
Monitoring for  Hazardous Waste Land Treatment  Units  (U.S.  EPA 1984) and "in
Preparation  of  Soil  Sampling Protocol:   Technique's and  Strategies (Mason
mrr.	

     Data on  "hot  spots" should  be carefully  evaluated  to  determine the
potential for migration from these areas below  the  treatment zone.
                                     56

-------
3.4.2.2  Soil-Pore Liquid Sampling--                        ...
     Percolating water added to the soil  by precipitation,  irrigation or waste
applications may pass through the treatment zone and rapidly transport mobile
waste constituents or degradation products  through the unsaturated.zone to the
groundwater.   Soil-pore  liquid monitoring  is intended to  detect  these rapid
pulses of  contaminants that occur immediately after significant additions of
liquids.   Therefore, the timing  (seasonally) of soil-pore liquid sampling is
essential to the usefulness of this technique  (i.e., scheduled sampling cannot
be planned  on a  pre-set  date,  but  must be  coordinated  with  precipitation,
irrigation, etc.).   Soil  tensiometers or neutron probes may be installed with
the soil-pore  liquid  samplers  to indicate  when  sampling  should  be conducted.
Soil  tensiometers or neutron probes also  may be  used to indicate if sufficient
soil  moisture  is present for  sampling.   The use of  soil-pore liquid samplers
may be restricted to HWLT units located  in  wetter climates.

     Since  interim status standards require the Installation and use of soil-
pore  liquid  sampling  equipment, data  concerning  the quality  of  soil-pore
liquid below the treatment zone may already exist.   However, if these data do
not  include  all  the constituents of  concern for the  LTD and for  future
management  and monitoring,  an  applicant with  presently  operating  soil-pore
liquid samplers should begin collecting  samples for analysis of Appendix VIII
constituents  using  Type   II  (metals) and  Type  III  (organic  constituents)
methodology.   For sites  without soil-pore liquid   samplers  or  with samplers
that are not  functioning,  the  reconnaissance  evaluation may be  based on  soil
core  and  groundwater  data only.   If  soil-pore  liquid   samplers  have been
installed  but have  not  been  functioning  effectively,  possible  reasons  for
their failure  (e.g.,  improper  installation, mechanical failures,  installation
in a soil horizon which has  a  low hydraulic conductivity,  such as a fragipan)
should be investigated and corrected, perhaps by changing  the type of sampler.
To provide minimum  volumes required for  analyses, liquid samples  may be
composited  from two  or more samples.  The  locations of the composited  samples
should be  identified  and reported.   The  samplers should preferably be  located
near  one  another.    However,  if  sufficient  volumes  of  sample  for required
analyses cannot be collected, a  possible priority scheme of analysis may be in
the order:   volatile organics,  semi-volatile  organics, and other  constituents
of interest.   Other difficulties that may occur  with soil-pore liquid sampling
equipment  include  the potential  for absorption of  hazardous constituents in
the  samplers, the potential  for release  of  hazardous  contaminants  from the
samplers  and  pumps,  and  volatilization  of hazardous  constituents during the
sampling process.  The applicant  should note that lack  of  compliance with  Part
265  soil-pore liquid  monitoring may affect  whether  the  performance  of the
facility  is considered  acceptable and  may expose  the operator  to possible
enforcement action.   The  use of several  types of soil-pore liquid samplers is
recommended to enhance the likelihood  of obtaining  samples.  A more detailed
discussion  of soil-pore  liquid  sampling is presented  in   the Permit Guidance
Manual On Unsaturated Zone  Monitoring for Hazardous  Waste  Land Treatment units
(U.S. EPA 1984) and  in Chapter 6  of this manual.'

3.5  GROUNDWATER MONITORING

     Groundwater  monitoring  data  can  be  an  essential   part  of the
reconnaissance  investigation  and may  also  be  used  in  field  verification


                                    57

-------
studies.  For  some  facilities, groundwater monitoring may be the only source
of  information concerning  hazardous constituents  in  liquids  below  the
treatment zone, if soil-pore liquid  samplers  are  inoperative.  New. facilities
will be required to  implement  a groundwater monitoring program according to 40
CFR  264 Subpart  F.   For  existing  sites, a  groundwater  monitoring program
should have been implemented as  specified  in  40 CFR Sections 265.90-94.   The
monitoring  system  should  consist  of  (40  CFR 265.91):    (1)  at  least  one
monitoring  well installed hydraulically upgradient from the limit of the waste
management  area, which yields groundwater samples that are representative of
background  water quality  in  the  uppermost  aquifer near the facility and which
is  not  affected by the  facility;  and  (2)  at least  three  monitoring  wells
installed hydraulically downgradient  at  the  limit  of the waste  management
area, which are  located  such  that  they immediately detect any statistically
significant  amounts of hazardous waste constituents  that  migrate from  the
waste management area  to the uppermost aquifer.

     However,  for  facilities  consisting  of  several  waste  management
components,  i.e.,  more  than  one  surface   impoundment, landfill,  or  land
treatment area, the ISS groundwater monitoring program may not be sufficient
for  determining  if hazardous waste  constituents  are migrating  out  of  the
bottom of the  land  treatment  unit.    ISS  do  not  require  separate monitoring
systems for  each waste management component.   If  hazardous waste constituents
are  found  in   the groundwater  from  a  multi-component  waste  facility,  the
owner/operator  should  install  separate  monitoring  wells  immediately
downgradient  from the  land treatment unit  to determine if it is the source of
the hazardous  constituents.

     Also,  ISS do not  specifically require that the  groundwater analysis plan
include all  Appendix VIII constituents or those reasonably expected to be in
or  derived  from the wastes (including inorganic  analyses).    If those
constituents  have not  been  analyzed,  the owner/operator  should  arrange  for
their  analysis  as part of  the reconnaissance   investigation,  in  order to
provide  information concerning  the  effectiveness of  treatment  in the  HWLT
unit.    Similarly  for analyses performed  for  waste characterization,  the
compounds analyzed may, on the approval of the permit  writer,  consist of an
EPA-approved  subset of  Appendix  VIII  constituents (e.g.,  the "Skinner List"
for the petroleum industry)  and  the  additional ten most prevalent  peaks of  a
GC/MS  scan  for volatiles,  base/neutrals,  and  acid waste  fractions.   The
presence of  any oils or oily sheens on water samples should be noted.

     Complete  Appendix  VIII  constituent  testing may  be required  if  it is
established  that  groundwater  contamination  exists  at  the facility.   Under
Section  270.14(c)(4), the  applicant  is required to  provide  in  the  Part   B
permit  application  "a description of  any plume  of  contamination that  has
entered  the  groundwater  from  a regulated  unit."   This description should
Identify "the concentration  of each Appendix VIII...constituent throughout the
plume,"  or  identify the  "maximum  concentration  of  each Appendix   VIII
constituents in the  plume."   If  evidence of contamination  is  inconclusive, the
regulatory agency may require that  only an approved  subset of Appendix  VIII
compounds be  measured (e.g., the  "Skinner   List"  for  petroleum  refinery
wastes).
                                   58

-------
3.6  DATA INTERPRETATION AND PRESENTATION

     Reconnaissance  information  concerning the  presence  or  absence  of
hazardous constituents in groundwater  or below the treatment zone will be used
by the  permit  writer and the  applicant for  developing the LTD plan  and  for
deciding the required comprehensiveness of the laboratory analyses and studies
and field verification studies.   At  new sites, the information will be used to
determine the characteristics of the wastes and the site/soil system that will
be used  at  the land treatment unit and the  suitability of  the  site  for land
treatment.

     The  applicant  should present  to  EPA the  analytical  data  from  the
following activities:
     (1)  waste characterization
     (2)  past waste management activities (existing  sites)
     (3)  soil survey
     (4)  waste distribution in soil  (existing  sites)
     (5)  soil-pore liquid monitoring (existing sites)
     (6)  groundwater monitoring (existing sites)
     A  map of  the  land  treatment  unit should  be  developed,  including  t-he
location of the  background  areas,  uniform  treatment areas, field verification
study  areas,  "hot  spots" of  hazardous  constituents  (at  existing sites), and
sampling locations  for  groundwater,  soil  cores,  and soil-pore liquids.  Data
collected  for use in modeling of the land treatment  system  should be  presented
in summary form, as well as results of the modeling.

     At  existing sites,  to assess  past  treatment  performance, statistical
analysis  of  soil  core,  soil-pore  liquid,  and groundwater  data  should be
conducted  by  comparing  the  concentrations of hazardous constituents  in the
soil  cores,  the soil-pore  liquids,  and the  groundwater  below the  treatment
zone  with  background  levels.    A  significant  difference  would  indicate
unacceptable  hazardous  constituent mobility unless other  circumstances could
account  for   any such  differences  (e.g.,  pockets of  buried materials  not
associated with  the land treatment operation or  land  treatment  unit built on
former  waste  disposal site).

     A  summary of possible  statistical  approaches and  use of  field  information
is given in Table 3.3.

     The  results of statistical  interpretation  of  data  will   help to  provide
the  basis  for a decision on the choice of the  appropriate scenario  described
in  Figure  1.1 (Chapter  1).   Specifically  these  data  assist the permit writer
1n deciding whether the  design  and operation of the site are  acceptable.
                                    59

-------
     Table  3.3  Suggested  Uses of Field Information
      Type  of  Information
        Statistical  Approach
             Use of Information
      Waste  analysis
      Treatment  zone
       soil-core analysis
o\
o
      Below treatment zone
       soil-core analysis
      Soil-pore liquid
       analysis at bottom
       of treatment zone
      Groundwater
Mean and variance estimates;  confidence
 intervals
Mean and variance estimates; confidence
 intervals
Comparison of individual  values with
 background treatment zone soil core
 samples at similar depths; tolerance
 1imits
Comparison of mean values within a
 uniform area through time; t-test or
 ANOVA with multiple comparison between
 means tests

Mean and variance estimates; confidence
 intervals
Comparison of individual  values with
 background below treatment zone
 samples; tolerance limits
Comparison of mean values within a
 uniform area through time; t-test or
 ANOVA with multiple comparison between
 means tests

Mean and variance estimates; confidence
 intervals
Comparison of Individual  values with
 background soil-pore liquid samples  at
 same depth; tolerance limits
Comparison of mean values within a
 uniform area through time; t-test or
 ANOVA with multiple comparison between
 means tests

Mean and variance estimates; confidence
 intervals
Comparison of individual  values with
 background groundwater samples
Definition of hazardous constituents and
 constituents that may affect land treat-
 ment

Distribution and accumulation of
 hazardous organic constituents
 through depth (degradation immobili-
 zation)
Accumulation of metals/comparison with
 regulatory 1imits
Measurement of degradation products
 (transformation)
Definition of all "hot spots"
Evaluation of treatment through time

Assessment of migration of hazardous
 constituents below the treatment zone
 (immobilization)
Definition of "hot spots"
Evaluation of treatment through time
Assessment of migration of hazardous
 constituents below the treatment zone
 (immobilization)
Definition of "hot spots"
Evaluation of treatment through time
Assessment of migration of hazardous
 constituents below the treatment zone

-------
                                                         05WER POUCY DIRECTIVE NO.

                                                       94«6 • 00-2   «
                                 CHAPTER 4

              PREDICTIVE TOOL FOR LAND TREATMENT  DEMONSTRATIONS
4.1  INTRODUCTION

     Mathematical  models  can  be  utilized  to  provide  a  rational  approach
for obtaining, organizing,  and  evaluating  specific  information  required  to
conduct an LTD.   A relevant model  for an LTD  can  be considered as a tool  for
integrating data concerning contaminant transformation, immobilization,  and
degradation for  assessing  the relative treatment effectiveness of alternative
design/ management combinations.   The multiple  factors  involved  in  deter-
mining  the success of  land treatment  are generally  complex and make  it
difficult to evaluate  the effect of  each factor on  the total treatment
process without  a tool for  interrelating these individual  factors.   A model
also can be used to guide the  design  of specific  experiments and the col lee-
ion of  specific data  that directly  address 40 CFR Part 264.  Specifically,
the effects  of  design and  operating  alternatives on  the SSAC may  be pre-
dicted, and  the  influence of  waste  type and soil type on treatment  may be
assessed prior to verification in field or laboratory studies.-

     A  mathematical  description of  the land  treatment   system  provides  a
unifying  framework  for  the evaluation of laboratory screening  and field
data that  is  useful  for the selection  of  PHCs and for determination of  the
SSAC for  a  waste.  While  current models cannot be relied  upon for long-term
predictions of absolute  contaminant concentrations due  to the  lack  of
an  understanding  of  the  biological,  physical, and  chemical  complexity
of  the  soil/waste  environment,  they represent a  powerful  tool  for ranking
design, operation, and  maintenance  alternatives  for  an LTD  as  well  as  for
the design of performance  monitoring programs.

     A  mathematical  description of  land  treatment  systems,  based  upon  a
conceptual model of  land treatment  that incorporates  specific requirements
of  40  CFR Part 264.272 as specified  in  264.271 and  264.273,  provides a
framework for:

     (1)  Evaluation of  literature and/or experimental  data for the selection
of PHCs;

     (2)   Evaluation  of  the  effects of site  characteristics  on treatment
performance (soil  type,  soil horizons, soil  permeability);

     (3)   Determination  of the effects of design and operating  parameters
(loading  rate,  loading  frequency, irrigation,  amendments  to  increase  degra-
dation), on treatment  performance;

                                   61

-------
     (4)    Evaluation of  the effects  of  environmental  parameters  (season,
precipitation)  on treatment  performance; and

     (5)   Comparison  of  the  effectiveness of treatment using different design
and operating practices  in order to maximize treatment.

4.2  MODEL DESCRIPTION

     The effectiveness of  a site  for land treatment  will depend on its
ability to  immobilize  and/or degrade  hazardous  waste  constituents.  There
are many  mechanisms  influencing  these  two  phenomena,  and although certain
characteristics can be  identified and  quantified  independently for  specific
substances,  it is necessary to express  the mechanisms in mathematical terms
to evaluate the overall  performance  of  an  LTD.   The mathematical  formulation
also facilitates  the transfer of  knowledge  optained at one  site to other
similar sites.

     Short  (1985) presented a model   (the  Regulatory  and  Investigative
Treatment  Zone  model; RITZ)  for use  in banning specific  hazardous  wastes from
land treatment.  The model  is based  on  the approach by Jury  (1983) for
simulating the  fate of pesticides in soils.  The RITZ model  has  been  expanded
at  Utah State University for this manual to  incorporate features which.
increase  its utility  for the planning and evaluation of LTDs.

     The extended version of the model  is programmed for the computer in such
a way that  additional enhancements  (such  as unsteady flow  and  time  variable
decay transport/partition coefficients) may be incorporated into the  model  in
the future  with  a minimum  of reprogramming.   A detailed description of the
model  equations  and  a  FORTRAN listing  of the  source  code are  included  in
Appendices C&F.summary description of the model is provided below.

4.2.1  Definition of  Terms

     There  is  no terminology which  has been  universally  accepted  for de-
scribing   soil  environments  used  for  land treatment  of   hazardous  wastes.
Consequently, several important  terms  are  defined here  and  used consistently
throughout the remainder of  the discussion.

     "Constituent" is the  term used  for  the hazardous substance being tracked
by  the  model.    It   is  a  substance  exhibiting (or  which  can  be  assumed  to
exhibit)  homogeneous chemical properties,  i.e., its environmental character-
istics may be  quantified by a specific  isotherm, degradation rate, etc.  The
constituent may  be  a pure compound or  it  may be  a mixture of several  com-
pounds as  long as their  behavior  can   be  adequately described  by composite
constituent parameters.

     A "phase" is a physical  component of  the soil environment.  In this ap-
plication of the model, the following phases are defined:   soil grains,  pore
water, pore oil, and pore  air (unsaturated  pore space).  The relative amounts
of  the phases  may change  with time and depth  in  the  soil.  The constituent
resides in  (on)  the phases,  and  the  sum  of  the  constituent  masses  in  all
phases equals the total  mass of the  constituent  at  any particular time.


                                    62

-------
     The constituent may exist  in  several  "states"  within the soil environ-
ment or  even within  a phase.   The  principal  state of  a  constituent will
normally depend  on the type of  phase  in which  (or on which)  it resides.  For
example,  it  may be  dissolved  in  the water  phase  or  adsorbed  on'the soil
grains.  The constituent will  tend  to  shift from  one  state to another at some
rate of transition until  equilibrium is reached.

4.2.2  Model Construct

     The model  describes  a soil column 1  meter  square with depth specified
by  the  user (usually 1.5  m).   The column  consists  of  a plow zone (Zone of
Incorporation, ZOI) and a  Lower Treatment  Zone (LTZ) as  shown  in  Figure 4.1.
The  soil  environment within  the  column  is made up of  four  phases:   soil
grains, pore water, pore air, and  pore oil.   It  is  important that all  phases
and  constituent  states  be  included  in order  to accurately simulate  inter-
actions and  maintain a mass  balance   in the  model.   Characteristics of the
soil environment may change with depth and/or  time.  The waste  is applied to
the plow zone at loading rates and  frequencies specified  by  the  user.

     The constituent is acted on by the transport and  degradation mechanisms
in the model, and its "life history" is calculated  at intervals  determined by
the  user.   The  constituent may migrate from  one phase to another during the
course  of  the model simulation.   Breakthrough occurs  when  a  pre-determined
concentration level  is  exceeded at the bottom of  the lower treatment zone_.
The  average  Soil Retention Time (SRT)  and  Treatment  Efficiency  are estimated
from the model results.

4.2.3   Immobilization/Transport

     Once applied to the land and mixed into the plow zone,  a constituent may
be  mobilized by three  mechanisms:   migration between/among phases,  disper-
sion, and advection.

4.2.3.1  Migration--
     When  two or more  phases are  in  contact,  the  constituent will  tend to
migrate  between/among them.    This  mechanism  is  modeled  by -assuming  that
constituent  concentrations reach  equilibrium immediately  between/among  all
phases  which are  in contact.   This  equilibrium  condition  is  described by
partition  coefficients determined  from literature data, laboratory  experi-
ments,  field sampling, and/or appropriate  parameter estimation methods.

     Figure  4.2  depicts  this  relationship  in the soil  column.  The plow zone
contains  all  four  phases  and  the  constituents migrate  among them to maintain
equilibrium.  In addition, the  oil phase is  assumed to decay with first-order
kinetics  and releases  its  contents to the other three phases.  It is assumed
that the  oil phase does not penetrate significantly into the lower treatment
zone,  as  indicated  in Figure  4.2.

4.2.3.2  Dispersion--
     Concentration  gradients  drive transport  within a  phase from regions of
high  concentration  to  regions of  low concentration.    Dispersive transport
 is  caused  by molecular  diffusion  and turbulence  within the phase.   In  the


                                      63

-------
       LUaste Loading
                   ^•••H

                    oil
    Variable Depth
 (Normally 15-20 em)
   Variable Depth
(Bottom of Treatment
   Zone i  1 .5 m
Below Ground Surface)
         Plow Zone
soil* oil s?
                                   t
          Lower
        Treatment
           Zone
    SOU ^
Degradation, u
Partitioning  «
          y>
 Degradation,
              Model Assumptions:
                 Periodic Application of Waste
                 Oil is Completely Mixed in Plow Zone
                 Plug Flow of Water in Plow Zone and Treatment Zone
                 Dispersion of Constituent in Unsaturated Pore Space
                    in Plow Zone and Treatment Zone
                 Soil Pore Velocity /(site  infiltration rate, soil type)

Figure 4.1.  Conceptual  description of land  treatment  system  used in  extended
             RITZ model  formulation.
                                     64

-------
  Fate of Constituent(s):
    1. Decay
   2. Leached when in water moving
     past bottom of Treatment Zone
  Action within Control Volume:
   1. Decay of Constituent in all
     Phases
   2. Transfer of Constituent among
     Phases until Equilibrium reached
      PLOW ZONE
      LOIDER TREflTMENT ZONE
 Action between Control Volumes:
  1. Downward movement of
    Constituent with Water
  2. Upward and Downward
    movement of Constituent in pore
    space driven by concentration
    gradient and properties of
    Constituent
Figure 4.2.  Transport and  partitioning  relationships within soil control
             volumes used in modified  RITZ  model.
                                      65

-------
model,  dispersion  is the primary transport mechanism for  the  volatile  frac-
 tion  of the constituent  in  the air  phase.   This mechanism is included in  the
model  because  of its importance in distributing the mass  of the  constituent
 in  the  vapor phase throughout  the soil column.

4.2.3.3 Advection--
      If a phase moves  through the  soil column,  it  will transport the con-
stituent along with  it.  In the model, the water phase  and its  dissolved con-
stituents  are  advected at the  average soil  pore water  velocity.   This veloc-
 ity is  calculated from the site infiltration rate and the site  soil  type.

     The  movement  of the constituent is retarded via  adsorption/desorption
by  the  other phases that it comes  in contact with as  it passes  through  the
soil column.

4.2.4   Constituent Degradation

     The  constituent may be  decomposed by biochemical  processes which  are
represented in  the model  by  first-order  rate kinetics.  Different  rate
coefficient  values  may  be  assigned  to different  phases and  to  different
depths  within the soil column.

4.2.5   Input

     Table  4.1  indicates the  design/operation  information  that  is used  for
input to the model.   Table 4.2  shows specific  input parameters  characterizing"
the waste  constituents.   These  parameters  may  be obtained  from  laboratory
experiments, literature  data,  and/or  parameter  estimation  techniques  used  in
conjunct'ion with field and laboratory observations.

4.2.6  Output

     The user  may  select the  level  of  detail  for the  output  of the model
results.  The output may include the constituent concentrations  in  each phase
at  selected  depths  in the soil column,  and at times specified by the user.
Output  also  includes  the  time  to  breakthrough of  the  constituent  at   the
bottom  of  the  designated  treatment  zone  at  leachate   concentrations  at  or
above constituent detection  limits.

     Figure  4.3  demonstrates  the   type  of  output  information that  can  be
obtained from the model.  Initially (t  = 0),  the waste  is  applied  and plowed
into the  zone  of  incorporation (ZOI)  as  depicted  in  Figure 4.3(a).   The
concentration of the constituent in the water  phase  is  shown to the right of
the' figure.  The advective velocity  of the water is indicated by the downward
movement of the  shaded areas  in Figure 4.3(b),(c)  and  (d).  The movement of
the constituent!s)  is  retarded via  adsorption/desorption by other phases as
shown  by the concentration distributions in these  figures that indicate peak
concentrations  remaining  in  the vicinity of  the ZOI.  Figure  4.3(d)  shows  the
condition when the advected water phase reaches the bottom of the  treatment
zone.    Breakthrough may occur  at this time  if a detectable  concentration of
the constituents)  is present  in the  water phase.  Breakthrough may occur  at
a later  time  if the constituent  is sufficiently mobilized but not degraded
during  its movement  through  the upper  soil column.


                                    66

-------
Table 4.1  Design/Operational Variables Required for Use in the Extended RITZ
           Model

Soil Properties

     soil texture
     saturated water content of the soil
     saturated hydraulic conductivity of the soil
     soil bulk density
     soil organic carbon fraction
     soil particle density
     soil particle effective size

Waste Properties

     concentration of constituents) in the applied waste
     mass fraction of oil in the applied waste
     mass fraction of water in the applied waste
     density of oil
     viscosity of oil
     detection limit in aqueous median of constituent(s) in waste

Environmental Properties

     site recharge rate on monthly or seasonal  basis
     site temperature on monthly or seasonal basis

Operational  Factors

     plow zone depth (zone of incorporation:  ZOI)
     treatment zone depth
     application rate of the waste
     application frequency of the waste
     tilling frequency of ZOI
Table 4.2  Variables Required from Laboratory Analyses,  Prediction Methods,
           Etc., for Use in the Extended RITZ Model

Biodegradation information (for each soil zone as appropriate):
     Half- life (ti/g) for each constituent of concern, corrected
     for volatil ization
     Half-life (tjyg) of oil  in the applied waste;
Immobilization information (for each soil  zone as appropriate):
     Ko = partitioning of constituents between water and oil  phases
     Kd * partitioning of constituents between water and soil phases
     Kh = partitioning of constituents between water and air  phases
                                    67

-------
      ZOI
Treatment
  Zone
                       Constituent
                     Concentration
                           Co
2221
      Initial Condition, t=0
               (o)
ZOI
                  Treatment
                     Zone
                                         Constituent
                                        Concentration
                                              Co
                            t= one time period11
                                     (b)

Tree
Zo
ZOI
tment
ne




















c
Cc
Constituent
ncentration
1 Co
f
i
A
/\
^
*
c
:
|
1
         t= ten time periods*
                 (c)
                                               ZOI
                                         Treatment
                                            Zone
                                                               Constituent
                                                              Concentration
                                                                    Co

                         t= fourteen time periods*
                                  (d)
     One time period = Time of travel of water through one control volume
      ilillli!!!!!  = Theoretical constituent/water plug of dimension=ZOI
      n.i«*ia*iii!i:w!i::*i        advecting via plug flow through Treatment Zone
Figure 4.3.   Sample constituent total soil  concentration profile at selected
             time periods after initial  waste  application.
                                   68

-------
 4.3   MODEL  APPLICATION

      The  results of  the model,  representing  an  integration  of  laboratory,
 literature,  and/or  calculated  input  data,  are  described  for each  design/
 management  combination  selected  for field  evaluation.   The  model  outputs for
 each  of the design/management combinations include:

      1.   Maximum residence  time of each  constituent  in the  zone  of  incor-
 poration  (ZOI);

      2.   Maximum residence time of constituent in the treatment zone;

      3.   Treatment  zone breakthrough time, Tb,  for constituent concentration
 at or above the detection limit if available;

      4.   Concentration of the constituent in  the leachate  at breakthrough,
 Co, 2. detection limit if available;

      5.   Retardation  factor  in  the  lower  treatment   zone,  below the  ZOI;
 and

      6.   Velocity of  the  pollutant in  the  lower treatment zone,  below  the
 ZOI.

     Two  output  parameters  are  used for making decisions  concerning  treat--
 ment,  as described previously.  The parameters  include:   1)  the concentration
 of a  constituent  at  the bottom of  the  treatment  zone,  Cb,  >_ detection  limit
 if available, and 2) the time required for a constituent to  travel  a distance
 equal  to  the  treatment zone depth,  Tb.   The ratio  Cb/Tb defines  the  inte-
 grated relationship  between  degradation and leaching (immobilization).   The
 smaller the ratio,  the more  "successful"  is  the assessed  treatment  of  a
 constituent.  This simple ratio can  be  used  to  evaluate and rank  the factors
 identified  above  with  regard to principal hazardous  constituents (PHCs),
 design/management options,  and the effects of environmental  parameter changes
 on treatment as indicated by this Cb/Tb ratio.

     PHCs, as  defined  in Part 264.278,  are  hazardous constituents  contained
 in the applied wastes  that   are the most difficult to treat,  considering  the
 combined  effects  of degradation,  transformation,  and  immobilization.    The
model  integrates the combined  effects  of treatment,  as discussed above,  for
 predicting  times  and  concentrations at  "breakthrough."    For selection of
 PHCs,  the model  is  useful,  not   in  terms  of quantitative determinations of
 constituent  concentrations   in  the  leachate,   but rather  for establishing
 priorities with respect to constituents  that are predicted  to  be  transported
 the fastest compared  to all other  hazardous constituents identified  in  the
 applied waste.

     The model output,  summarized as Cb/Tb  for each constituent for  each  com-
bination of design/management and environmental characteristics, can then be
used   to select  one or  more optimum  design/management  combination(s)  to be
evaluated  in  a field  verification   study.   The monitoring  program for  the
field verification study may be  based  primarily on the  PHCs  identified  from

                                    69

-------
 laboratory,  literature, and/or estimated input data used in the extended  RITZ
 model.   However,  it  is  suggested as described  in  Chapter 6 of  this  manual
 that for 5-10  percent  of field  samples taken,  a complete analysis for  all
 hazardous  constituents  be conducted  to evaluate the  accuracy of the model
 predictions.   This approach will  also  allow field monitoring of  any  trans-
 formation  products not predictable  by  the model.   Using  this approach  for
 field verification saves costs, while at the same time allows  verification of
 laboratory  data  and  model  description without  compromising  protection of
 public  health during the LTD.

 4.4  EXAMPLES

     Examples are  illustrated for two types of model  applications:

     1.  The recovery of a hypothetical  site receiving one  waste application.

     2.  A land treatment site receiving periodic waste applications.

 Examples 1  through 3  fall into the  first  type and  Example 4 falls into  the
 second.   Physical  properties of  the  soil  columns used for all examples  are
 shown in Table 4.3.

     Table  4.4  shows  the  operating parameters  and  waste characteristics -
 assumed for the four example runs.

     The first three columns in Table 4.5  show the results of  the  model runs
 for  Examples  1  through  3.   None  of these compounds  significantly penetrate
 the LTZ in detectable  levels.  The last  column in Table 4.5  shows  the results
 of repeated  land  application  of   a  waste  constituent.   In order  to yield
 naphthalene penetration  into  the  LTZ,  its decay  coefficient  in  the LTZ  was
 reduced to  1/20 of the value  in  the plow zone  (see  Table 4.4).   Even then
 naphthalene only penetrated approximately half way into the  LTZ.

     The upper  portion  of Figure 4.4 shows  the  "saw  tooth" distribution of
 the naphthalene concentration in the plow zone.   Concentration  pe-aks occur at
 each 90-day application event and then  decay  between events.  The  lower por-
 tion of the figure indicates  the  approximate  concentration distributions with-
 in the  treatment  zone  at the  times  indicated.   The penetration  and attenu-
 ation of the naphthalene peaks  in  the LTZ are clearly  seen  in the  figure.


 Table 4.3  Physical  Properties  of  the Soil  Columns  Used  for  Examples 1
           Through 4

 Depth of treatment zone  (m)                             1.5
 Soil  moisture coefficient                               4.9
 Soil  porosity (cc/cc)                                   0.435
 Soil  bulk  density (cc/cc)                               1.4
Temperature in the plow  zone  ("C)                      20 (constant)
Temperature in the lower treatment zone  ("C)           20 (constant)
Dispersion  coefficient  in  air                          0


                                     70

-------
Table 4.4  Operating Parameters  and Waste Characteristics  for  Examples  1 Through 4

Depth of the zone of incorporation (m)
Waste application rate (g waste/ 100 g soil)
Constituent concentration in the waste (ppm)
Weight fraction oil in the waste (Kg/Kg)
Weight fraction water in the waste (Kg/Kg)
Density of oil (g/cc)
Length of application period within year (days)
Application frequency within period (days)
Infiltration rate (m/day)
Initial oil content in the plow zone (m-Vm3)
Degradation rate of oil (per day)
Initial concentration in water, plow zone (g/m3)
Initial concentration in water, LTZ (g/m^)
Initial concentration in oil, plow zone (g/m3)
Initial concentration in oil, LTZ (g/m3)
Initial concentration in air, plow zone (g/m3)
Initial concentration in air, LTZ (g/m3)
Initial concentration on soil, plow zone (g/m3)
Initial concentration on soil, LTZ (g/m3)
Water to oil partition coefficient, plow zone
Water to oil partition coefficient, LTZ
(g/m3 per g/m3)
Water to air partition coefficient, plow zone
Water to air partition coefficient, LTZ
(g/m3 per g/m3)
Water to soil partition coefficient, plow zone
Water to soil partition coefficient, LTZ
(g/m3 per g/m3)
Constituent decay rate In water, PZ (per day)
Constituent decay rate in water, LTZ (per day)
Example 1
Phenanthrene
0.15
0
0
0
0
0.80
0
0
0.0024
0.0125
0.0231
0
0
60
0
0
0
0
0
23,000
23,000

0.006
0.006

0.0575
0.0575

0.026
0.026
Example 2
Benzo(a)pyrene
0.15
0
0
0
0
0.80
0
0
0.0024
0.0125
0.0231
0
0
42
0
0
0
0
0
4,037,000
4,037,000

0.0
0.0

1.69
1.69

0.0075
0.0075
Example 3
Naphthalene
0.15
0
0
0
0
0.80
0
0
0.0024
0.0125
0.0231
0
0
100
0
0
0
0
0
1,349
1,349

0.017
0.017

0.004
0.004

0.69
0.69
Example 4
Naphthalene
0.15
0.06
2,000
0.40
0.40
0.80
366
91.3
0.0012
0.0
0.0231
0
0
0
0
0
0
0
0
1,349
1,349

0.017
0.017

0.004
0.004

0.345
0.0172

-------
Table 4.4  Continued

Example 1
Example 2 Example 3
Example 4
Phenanthrene Benzo(a)pyrene Naphthalene Naphthalene
Constituent decay rate in oil, PZ (per day)
Constituent decay rate in oil, LTZ (per day)
Constituent decay rate In air, PZ (per day)
Constituent decay rate in air, LTZ (per day)
Constituent decay rate on soil, PZ (per day)
Constituent decay rate on soil, LTZ (per day)
0.026
0.026
0.0
0.0
0.026
0.026
0.0075
0.0075
0.0
0.0
0.0075
0.0075
0.69
0.69
0.0
0.0
0.69
0.69
0 345
0.0172
0 0
0.0
0.345
0.0172

-------
Table 4.5  Summary of Results  from  Sample  Runs
                  Example 1
                 Phenanthrene
              Example 2
            Benzo(a)pyrene
                Example 3      Example 4
               Naphthalene    Naphthalene
                              Applled Four
                             Times per Year
Maximum depth
of detectable
concentration

Concentration
at maximum
depth (g/m3)

Time to maxi-
mum depth
0.36 m
0.0010
65 days
plow zone
plow zone
initial
plow zone
plow zone
3 days
0.84 m
0.0014
154 days
  Plev Zone
  Plou> Zone
   Lover
  Treatment
    Zone
  C(llg/m3)
                    90
                                                  T-*1	1	r—|	1	r
                                    270      360      450      S40      (30

                                                                    Time (days)
C
1 t t










0
•










Co
^^"P
ZJ

,


!


i
:
1
1 	 Co
!

^


t




i Co



-^



k

:
1 C

""•'
»


fc




O

~








i C

-«*
^


^




                              210  244
                                              390
                                           S70  Tim* (days)
 Figure 4.4.  Time distributions of  naphthalene  concentration in the plow zone
              (upper curves) and depth  distributions  at specific times in the
              lower treatment zone  (lower  curves).
                                     73

-------
                                                            05>«tR rGLlCY DIRECTIVE NO.

                                                          9486  .00-2   «
                                  CHAPTER 5

                LABORATORY ANALYSES AND STUDIES  FOR  SELECTING

                       DESIGN AND OPERATION  CONDITIONS


 5.1   INTRODUCTION

      Procedures  for  measuring  degradation,  transformation/detoxification,
 and   immobilization,   and  for  organizing,  collecting,  and processing  data
 are  presented  in  this chapter.   Use  of data  obtained  for calculating SSACs
 and  for  making  decisions  concerning  treatment  effectiveness  and  design/
 management options is discussed in Chapters  2  and 4  of this manual.

      Evaluation of  degradation and  immobilization  is  generally recommended
 for  the  zone of  incorporation and  the  lower  treatment  zone.   However,  this-
 decision  should  be  based on  observed and measured  differences  between  the
 properties of  the  zone of  incorporation and  the lower  treatment  zone  with.
 respect to specific  factors  that  influence  waste  treatment as  identified in
 Chapter 3 of this manual  (Table 3.5).

     Analysis of hazardous constituents for determination of degradation  and
 immobilization may be  conducted  using identification techniques (GC/MS)  and
monitoring techniques (GC,  HPLC, etc.).  Identification  techniques  are
 recommended for initial and  final  constituent  determinations and confirmation
of Appendix VIII  constituents (or  the  subset of Appendix VIII constituents in
the waste/soil  mixture) in aqueous/soil,  aqueous/oil, and aqueous/air phases.
Monitoring techniques may be used for obtaining  specific data points between
 initial and final determinations for  establishing the mathematical  relation-
ships required for calculations of the extent  of contaminant degradation  and
 immobilization.  Monitoring techniques for determinating data points between
 initial and  final values  represents a cost-effective approach  for obtaining
sufficient information to evaluate  design/management options  for describing
degradation and immobilization of  hazardous constituents  in  the land treat-
ment system.

5.2  WASTE CHARACTERIZATION

     The waste characterization performed for the reconnaissance investiga-
tion of existing sites may  be used for the short-term  land treatment demon-
stration.    For new  sites,  waste  characterization should  also  be  conducted
according   to   the  guidelines  and  procedures  given for  the  reconnaissance
investigation,  as described  in Section 3 of  this manual.   Waste character-
ization  includes analysis of physical  and  chemical  characteristics  and
constituents  of the waste (necessary to optimize other  analytical procedures


                                    74

-------
or  to  provide information concerning  the  land treatability of  the  wastes)
(Table 3.3)  and  analysis of  Appendix VIII  (or an appropriate subset  of
Appendix VIII) hazardous constituents.

5.3  SOIL CHARACTERIZATION

     A thorough characterization of soils  present at an existing site should
have been conducted for the reconnaissance  investigation.  At new sites, soil
characterization  should  also be  conducted  according to the guidelines  and
procedures given for the reconnaissance  investigation,  as  described  in
Section  3  of  this manual.   Information concerning  soils may also  have been
collected  as  part of  initial  site investigation of the suitability of  the
site  as  a hazardous  waste land treatment  facility  (U.S.  EPA  1985).   Soil
characteristics that  should be  described  and/or measured   are  discussed  in
Section  3.5.1 (soil  survey  information),  in  Table  3.5 (soil   physical  and
chemical properties),  and  in  Section  3.5.2 (distribution of hazardous  waste
constituents  in the soil).

5.4  TOXICITY OF WASTE TO THE SOIL  TREATMENT MEDIUM

     Determination  of  acceptable waste application  rates   (mass/area/appli-
cation)  is  an  important  step  in  conducting  an LTD.   Many land  treatment
facilities  currently  operating  under  interim  status  may   have  established
acceptable loading rates for  their site  which may be used  for the LTD.
However, for  interim  status  facilities  with unacceptable loading rates,  for
newly planned facilities, or for new waste addition to an existing facility,
a method  to  determine initial  waste application rates  is  needed.  Since the
decomposition of  hazardous wastes  and detoxification of organic waste con-
stituents in  the  soil  depends.to a large  extent on biological  activities of
soil microorganisms, it is  important  that waste application  rates be based on
impacts  of the waste for indigenous soil microbial  populations.   These
impacts can be measured using a battery of  short-term bioassays  that measure
acute toxicity.

5.4.1  Possible Assays

     Appropriate bioassays  should reflect the  activity and/or survival of the
soil microbial  population.   This  information  may  indicate effects on  the
microbes responsible  for  waste degradation.   The  tests selected  should  be
sensitive enough  to indicate adverse  impacts  of a candidate waste  for  the
soil microbial  population,  which  is directly related  to  the   assimilative
capacity of the soil.   The  objective  is to  predict initial loading rates that
allow detoxification  of  hazardous  constituents to occur within  the  defined
waste treatment soil as a result of normal soil biotransformation processes.

     The toxicity screening tests  should  be  easily performed, rapid,  and
inexpensive.   They  should  also be validated  for the ability  to demonstrate
responses to toxic environments.

     Table 5.1 contains a list  of suggested  toxicity screening bioassay-s with
activities measured and the references for the performance  of the bioassays.
More detailed descriptions  of  several  of  the  bioassays,  along with pro-
cedures,  methods,  data handling,  and  interpretation are provided  below.


                                     75

-------
Table 5.1  Toxicity Screening  Bioassays  Useful  in  Evaluating  Hazardous  Waste
           Applications to  Soil
Organism   Test
 Type     Medium
    Test
     Activity
     Measured
  References
Decom-    Soil
poser
          Soil




          Soil


          Soil




          Soil




          Soil
         Soil


         Soil


         Soil
 Viable Counts
 Soil  respiration
Organic matter
decomposition
Dehydrogenase
activity
Enzyme activities
 Viability
Organic matter
utilization
 Biomass reduction    Growth
Decomposition
Microbial electron
transport activity
Biochemical
processes
Microcalorimetry
ATP or Adenylate
charge

Nitrogen cycling
processes; fixation
mineralization,
nitrification,
denitrif ication
Metabolic heat
production

Cellular
energetics

Nutrient cycling;
specific
heterotrophic
and autotrophic
metabolism
Greaves  et  al.
  (1976)
Atlas et  al.
  (1978)
Greaves  et  al.
  (1981)

Atlas et  al.
  (1978)
Greaves et  al.
  (1981)

Anderson  et al.
  (1981)

Greaves et  al.
  (1976)
Malkomes  (1980)
Porcella  (1983)

Atlas et  al.
  (1978)
Greaves et  al.
  (1981)

Greaves et  al.
  (1976)
Burns (1978)
Atlas et  al.
  (1978)
Swisher &
 Carroll  (1980)

Greaves et  al.
(1976)
Atlas &
 (1981)
Bartha
Greaves et al
 (1976)
Atlas et al.
 (1978)
Greaves et al
 (1981)
                                    76

-------
Table 5.1  Continued
Organism Test
Type Medium
Test
Activity
Measured
References
Plant
Inverte-
brate
          Soil
Water
extract
of soil

Solvent
extract
of soil
water

Soil
water
extract

Soil
leachate

Soil
          Sulfur oxidation
                    Microtox"
                    Ames Test
Root elongation
                    Selenastrum
Earthworm
                     Nutrient  cycling;
                     autotrophic
                     metabolism

                     Bacterial
                     luminescence
Genetic toxicity




Growth



Growth


Lethality
                    Atlas et al
                     (1978)
Beckman
 Instruments
 (1982)

Maron and Ames
 (1983)
Porcella (1983)
                                         Porcella  (1983)
Neuhauser et al
 (1983)

Verte-
brate
Soil
leachate
Soil
leachate
Daphnids
Fathead minnow
Lethality
Lethality
Porcella (1983)
Porcella (1983)
5.4.1.1  Microtox"--
     The  Microtox"  system  is  a  simple  standardized toxicity  test  system
which utilizes  a  suspension of marine luminescent bacteria  (Photobacterium
phosphoreum)  as bioassay  organisms.   The  system  measures acute toxicity  in
aqueous samples.  An  instrumental  approach is used in which  bioassay  organ-
Isms are handled much like chemical  reagents.   Suspensions with  approximately
1,000,000 bioluminescent  organisms  in each are  "challenged"  by addition  of
serial  dilutions of an aqueous sample.  A  temperature controlled photometric
device  quantitatively  measures the  light  output  in  each suspension  before
and  after  addition of  the sample.   A reduction of  light  output  reflects
physiological  inhibition,  thereby indicating  the  presence of  toxic  constitu-
ents in the  sample.
                                    77

-------
      For purposes  of the  LTD,  acute  toxicity tests  are conducted using
 the water  soluble fraction (WSF) extracted from  appropriate  samples of
 waste,  soil  and/or a  series  of  waste-soil  mixtures.   An  EC50  (effective
 concentration  causing  a  50  percent decrease  in bacterial bioluminescence) is
 calculated  for each WSF extracted.  Results are used to calculate the range
 of  loading  rates around  a "toxic floor" which will  not produce an  unfavorable
 impact on the  soil microbial detoxification potential.

      The Microtox"  System (Microbics Corporation, Carlsbad, CA)  described in
 this  chapter  has been evaluated using  a  large  number  of pure compounds and
 complex  industrial  wastewaters  and  sludges.   This  procedure,  as  with  any
 other toxicity screening test which might be used,  offers potential  advan-
 tages and disadvantages.

      The small  volume  of sample  required  (as little as 10  ml) and the rapid-
 ity in which  results can  be obtained (less than one  hour for the assay
 itself)  are  highly desirable features  of  a screening  procedure.   It is
 also  reported effective in  determining relative acute  toxicity  of complex
 effluents containing toxic  organic  constituents (Qureshi et al. 1982, Vasseur
 et  al.  1984,   Burks  et al.   1982;  Casseri  et al. 1983;  and  Indorato  et  al.
 1984).   In  each of  these studies,  Microtox" results were compared with those
 from  several other  assays and were found  to provide a reliable indication of
 the  presence  of toxic organics.   Both Qureshi  et  al.  and Vasseur  et  al..
 reported Microtox" to be more sensitive to complex organic  effluents than the"
 other  assays  tested.   King  (1984)  reported  that the production  of light by
 the  luminescent  bacteria in the Microtox" reagent is  very sensitive  to the
 presence of inhibitory chemicals.

      Strosher  (1984) reported  the  assay to be a viable  method  of screening
 for  apparent  toxicity  in complex  waste drilling fluids.   Microtox" results
 were  found  to  correlate closely  with  those  from  rainbow  trout  bioassays.
 Strosher recommended  that   this  assay  be  utilized as  a tool  in  evaluating
 effects of  drilling fluids  on soils.   In  an  earlier paper,  Strosher  et al.
 (1980) reported that  small  changes  in concentrations  of  toxic  components
 could be detected using  the  Microtox" procedure.   Matthews and Bulich (1985)
 and  Matthews  and Hastings   (1985)  presented  results  from toxicity screening
 and toxicity reduction tests conducted  using  the WSF extracted from different
 types of waste-soil  mixtures.

     There are two  potential  disadvantages to consider.  First, the Microtox"
 test organism is a  photoluminescent bacterium of marine origin, which may not
 accurately represent the response  of soil microbes.    In addition,  the test
 procedure is designed  to measure the  toxicity of water soluble  constituents
 and may  underestimate  the  toxicity of  hydrophobic  compounds.   Reported re-
 sults  from  developmental work  and evaluation involving different  types of
 waste-soil  mixtures  tend to discount  either  disadvantage  as a  severe hin-
 drance for  using the  test   for  general  screening  purposes  (Matthews 1983;
Matthews and Bulich  1984; Sims 1985;  and Matthews and Hastings 1985).  Micro-
 tox"  toxicity screening  test results have been  used  by these researchers to
establish a range of  initial waste application  rates  that did not result in
undesirable impacts on the  soil  system with  respect  to treatment potential,
thereby allowing detoxification  of hazardous  organic  constituents to occur.


                                    78

-------
     King  (1984)  reported  Microtox1"  to be more sensitive  to  inhibitory
chemicals than activated sludge organisms.  Slattery  (1984) found  that  when
the influent EC50  for Microtox" became less than 10 percent, activated  sludge
organisms  became  completely inactive.   The Micrptox"  test  can  .be  useful
for  predicting  initial  waste  application rates  if  a similar  relationship
exists between the inhibition of Microtox" bioluminescence and  soil  microbial
activity can be further  substantiated.

     5.4.1.1.1    Experimental Apparatus—Two major  pieces  of  experimental
apparatus  are  needed to conduct  the toxicity  screening  test procedure as
described  in  this section.   A  tumbler,  wrist-action  or platform  shaker is
used to extract the  WSF from each  sample.   Following  extraction, the  Micro-
tox"  system  is used to determine  the  relative residual acute  toxicity
in each WSF sample.

     5.4.1.1.2    Water Soluble Fraction Extraction Procedure—A  distilled,
deionized  water   (DDW)extractionprocedureasdescribedEy Matthews and
Hastings (1985) is  used to generate WSF  samples.   The following  steps are
used to prepare these samples for toxicity testing:

     a.  Place a  100 g  sample of each  of  the background soil, waste, and
selected soil-waste mixtures into  an  extraction vessel,  i.e., 500 ml  glass
flask or bottle.   If  the waste  has a high water content,  a thoroughly mixed
sample  can be centrifuged to obtain  the WSF  for  toxicity  testing, thus
eliminating the need  for the extraction step.

     b.  Add 400  ml  of  DDW  (4:1  vol/wt  extraction ratio)  to each vessel and
seal tightly.

     c.  Use a tumbler shaker for mixing.  If a wrist-action shaker is used,
place the  vessels on the shaker  at  a  180"  angle;  if a platform  shaker is
used, place the vessels  on  their side.   In all  cases,  the extraction vessels
must be sealed tightly.

     d.  Allow the extraction vessels to shake for 20^4 hrs at  approximate-
ly 30  rpm  in the  tumbler shaker or  60  rpm  on   the wrist-action or platform
shaker.

     e.  Following the specified mixing period,  remove  flasks from the  shaker
and allow  them  to sit for 30 minutes.   Decant the supernatants into high-
speed centrifuge tubes.   Add 0.4 g of NaCl  for  each 20 ml  of  sample;  shake;
then centrifuge at 2,500 rpm for 10 minutes.

     f.  Prepare  a  sample from each  test unit  for  Microtox"  testing by
pipetting 20  ml  of elutriate from each  centrifuge tube into  a clean glass
container,  sealing and storing at 4"C.  Take care to ensure that  any floating
material is  not transferred.   As  soon  as  all  samples  are prepared, begin
Microtox" testing; conduct all tests the same day that  they are prepared.

     g.  Follow the test procedure outlined in the Microtox* System  Operation
Manual (Beckman Instruments, Inc. 1982).
                                   79

-------
      5.4.1.1.3    Test System Operation—The   Microtox"   toxicity  analyzer
 associated reagents,  ana  detailed operating Instructions  can be obtained from
 Microbics Corporation,  Carlsbad, CA.  The test involves:

 ic-r *^   AdJust1n9  the  instrument to  the  desired  test temperature,  i.e.,
 A3 U •

      (b)  Adding 0.01  ml  of rehydrated cell  suspension  to  serial  dilutions
 prepared  by mixing  the  previously extracted WSF  samples in  appropriate
 dilution water.

      (c)  Taking readings of light outputs at time zero and  after the desired
 reaction time, i.e.,  5 minutes for most applications.

     (d)  Using  blank readings to correct for time-dependent drift in  liaht
 output.                                                                  '

     (e)  Calculating relative acute  toxicity (EC50  values  along with  upper
 and  lower 95 percent  confidence limits) for the WSF extract.  This involves
 preparing  a log-log plot of concentration versus  gamma  (the ratio of  light
 loss to light remaining)  corrected  for effects of  lightdrift  based  on the
 blank response.  The  concentration of the sample corresponding to a gamma of
 1  is termed  the  EC50 (t.T),  meaning  at this concentration a  50 percent
 decrease in light output occurs for an  exposure time  (t)  and  test  temperature
 '  '_•

 5.4.1.2  Soil Respiration--
     Soil  respiration is generally accepted  as a measure   of  overall  soil
 microbial  activity  (Hersman  and Temple 1979)  and has  been  used  as an  indi-
 cator of the toxicity or of the utilization of  organic compounds  added to the
 soil environment (Pramer  and Bartha 1972).   Respiration may also act  as an
 indicator  for  microbial  biomass in soil because the  transformations  of the
 important organic elements (C,N,P,  and  S) occur through the biomass (Franken-
 berger and  Dick 1983).   Measurement of  C02  evolution from soil  samples  is  a
 commonly  used indicator  of soil  respiration, although  measurement  of  0?
 uptake using  a Warburg-type  respirometer is  a  viable alternative for  short-
 term respiration.   Evolution  of  C02 can be  measured  in  flow-through or
 enclosed systems.   Flow-through systems  involve passing a stream of C02-free
 air  through  incubation chambers and  then  capturing   C0£ from the  effluent
 gas  stream in alkali  traps  (Atlas and  Bartha 1972).   The Biometer  flask
 described by  Bartha and Pramer  (1965)  is  an  example  of the  enclosed  system.
 It consists of an  Erlenmeyer flask modified with  a  side-arm addition  which
 serves as  an  alkali reservoir  for trapping 0)3.   A  septum  in  the  side-arm
 allows  for removing samples  of  the  alkali.   The flask  itself is  fitted  with
 an ascarite trap for  maintenance of C02-free  aerobic  conditions  within the
container.  The carbon dioxide  produced by microbial respiration is quanti-
 tated by titration of  the  alkaline  solution with  an  acid of known normality
or by determination of total  inorganic  carbon  in the  solution through  use of
a carbon analyzer.

     Determination of  soil  respiration  through  C02 evolution is an in-
expensive  and  simple  method  for indicating  general  soil   microbial  activity


                                   80

-------
and acute  effects  of added  substrates  on that  activity.   The  use  of  soil
respiration in the  literature  is  widespread,  indicating  the general  accept-
ance of respiration as an  indicator  of soil microbial activity.  Soil  respir-
ation  is  limited  in  that results  will  not  necessarily reflect  changes  in
specific types and/or groups  of microorganisms.

     5.4.1.2.1  Experimental  Apparatus—Each  experimental  unit consists  of a
500 ml Erlenmeyer flask having a single-hole  stopper fitted with an ascarite
trap.  A  stiff wire,  bent to an 'I' shape at  the  bottom,  is  suspended  from
the stopper.   A  scintillation vial  attached  to the wire with  a rubber  band
contains 0.5 N KOH  for capturing C0£ released from the soil.

     5.4.1.2.2   Experimental  Procedure—The  method  recommended  below  is
modified from the procedure described by  Bartha and Pramer (1965).

     a.   Distribute  50 g of each of  the background soil,  waste,  and  soil:
waste mixtures to 500 ml  flasks, using triplicates for each loading.  Include
three  empty  flasks as blanks  and  treat  blanks  in  an  identical manner  to
samples throughout  the testing  period.

     b.  Place a scintillation vial  filled with 15 ml of a 0.5 N solution  of
KOH into each flask and  secure  the stoppers.

     c.  Incubate the flasks  at room temperature (22+_l°C).

     d.  Monitor the  evolution of C02  for a  24-hour period.  For determina-
tions  of  detoxification  potential, C02  evolution should  be  monitored  at
specific time intervals.

     e.  The  alkali  traps  are  changed by removing  the vial  of KOH from  each
flask,  capping  it,  and  replacing  the vial with  one freshly filled  with
alkali.

     f.   Determine  the  amount of C02 in  each  trap using a carbon  analyzer
and testing  for  total  inorganic  carbon.  Where a  carbon  analyzer  is not
available, the  amount  of C02  evolved   can  be  determined  titrimetrically.
Add an excess of BaCl2 to the alkaline solution to precipitate the carbonate
as  insoluble BaCOs-   With phenolphthalein as  an indicator, titrate the
unreacted KOH with  0.6 N  HC1.   Calculate evolved carbon  expressed as C02-C,
using the following formula (Stotzky 1965):

         mg C02-C = [(ml  of HC1 to  titrate blanks)  - (ml of  HC1  to  titrate
                    sample)]  x normality  of  HC1  x  equivalent  weight; equi-
                    valent weight =  6 if data expressed in terms of carbon.

     g.   Subtract  the mean amount  of C02-C  found  in the blank  flasks  from
the mean  of  the  results  from the other  flasks.   This accounts  for  the C02
which enters  the flasks  when samples  are taken  and the  flasks are  aerated.

     h.   Check the moisture  content of  each unit  once  a week.   The avail-
ability of water  has a large  effect  on microbial activity.
                                   81

-------
 5.4.1.3  Dehydrogenase Activity--
     Dehydrogenation  is the general  pathway  of biological  oxidation  of
 organic  compounds.    Dehydrogenases  catalyze  the  oxidation  of  substrates
 which  produce  electrons able to  enter  the electron transport  system  (ETS)
 of  a cell.  Measurement of  dehydrogenase  activity  in soils has  been  recom-
 mended  as  an  indicator  of  general  metabolic  activity of  soil  microorganisms
 (Frankenberger  and  Dick 1983;  Skujins  1973; Casida 1968).   Free  dehydro-
 genases  in  soil  are  not expected because  cofactors  such  as  NAD  and  NADH  are
 required,  linking dehydrogenase activity to living organisms (Skujins  1978).
 The  type and quantity of carbon  substrates, both present  and introduced, will
 influence dehydrogenase activity (Ladd 1978; Casida 1977).

     The  soil  dehydrogenase assay  involves the incubation of soil with
 2,3,5-triphenyltetrazolium chloride (TTC) either with or without added
 electron-donating substrates.   The water-soluble, colorless TTC  intercepts
 the  flow of electrons  produced  by microbial  dehydrogenase  activity and  is
 reduced  to  the  water-insoluble,  red  2,3,5-triphenyltetrazolium  formazan
 (TTC-formazan).  The  TTC-formazan  is  extracted  from the soil  with  methanol
 and quantified colorimetrically.

     The soil  dehydrogenase  activity assay is  simple  and efficient.  It  is
 also  a  convenient test to  run  since  the only major  pieces of equipment
 required are  a spectrophotometer,  a  centrifuge,  and,  depending  on  selected
 test conditions, an  incubator.   However,  since  the assay indicates general
 activity of  the  major portion of  the soil microbial  community,  it may not
 reflect effects of an  added substrate or toxicant on specific segments of the
 commun i ty.

     5.4.1.3.1    Experimental Apparatus and Procedure—The method for deter-
mination of dehydrogenase activity  is based on Klein et al.  (1971).   Activity
both with  and without  glucose   addition  is  determined.   Work  by  Sorensen
 (1982)  found that increased soil dehydrogenase activity due  to  glucose
 addition can be more sensitive to  stress  than the  activity  without  glucose.

     Triplicate test  units  are  prepared  for  each of the  background  soil,
waste,  and  soil .-waste  mixtures.   Color correction  is  accomplished  by pre-
paring one  additional tube for each combination  of soil:waste mixture with or
without glucose that does not include TTC.

     For each sample:

     a.   Weigh  2  g soil  into  each of two  16 x  150 mm culture  tubes.

     b.  Add 0.4  ml of a 4 percent (w/v)  solution of TTC to each tube.

     c.   Into one tube add  1  ml  deionized  water.   To the  other tube  add 1 ml
of 0.5 percent  glucose.

     d.   Mix the tubes  on  a  vortex mixer, place stoppers in the tubes,  and
 incubate at 35"C  for 22 +_ 2 hours.

                                   82

-------
     e.  Add  10 ml  methanol to each tube.  Shake  the  tubes  vigorously  for  1
min  to extract  the  TTC-formazan.    Allow  the tubes to  sit overnight,  then
shake  again for 1 min and centrifuge at 600 x  g for 10  min.

     f.  Read the absorbance of the supernatant  from  each  sample at 485 nm
using  a 1 cm light path with methanol as a blank.

     g.  Determine dehydrogenase activity from a  standard curve derived  from
TTC-formazan  standards  of  1, 2, 5,  10,  and 20 mg/1 in methanol.  Calculate
color-corrected results by subtracting the absorbance value  obtained for  each
sample  having no  TTC  from  corresponding TTC-containing samples.   Express
results as  g formazan produced per gram dry weight of  soil  in  24  hours.

5.4.1.4  Nitrification--
     Oxidation of  ammonium-nitrogen  to nitrite and then to  nitrate nitrogen
is  called  nitrification.   The chemoautotrophic  bacteria  that derive  their
energy for growth from  the oxidation of  ammonium  ion (e.g.,  Nitrosomonas) or
nitrite ion (Nitrobacter) are  sensitive to environmental  stress and are not
different from their heterotrophic  microbial neighbors  in  the soil  in many of
their  requirements  for metabolic  activity and  growth  (Focht  and  Verstraete
1977).   Coupled with  the fact  that  the  energy  yielding  substrates and/or
oxidized products  of nitrification  are  easily extracted from the soil and
measured, the process  of nitrification can be used as an excellent bioassay
of  microbial  toxicity  in the  soil.   Nitrification is a process which in-
fluences soil fertility -since  the nitrate anion  is very mobile in soil and
easily leached  while the ammonium cation  is  strongly  absorbed.   Therefore,
information about the nitrification process helps  in understanding  the status
of nitrogen cycling in the soil.

     A possible  disadvantage of using nitrification as a toxicity indicator
is the high sensitivity of the  bacteria involved.   This is especially true of
Nitrobacter (Focht and Verstraete  1977).  Heterotrophic microbes may be more
resistant  and  resilient  and as  they are  the organisms involved  in  waste
stabilization, this  assay may overestimate the general  toxicity potential of
the waste.

     5.4.1.4.1   Experimental Apparatus  and Procedure—The  methods outlined
below  were  used  by Sorensen (1982)  as adapted  from Belser  and Mays (1980).
The intent of the assay  is to measure  the  potential  activity of the ammonium
or nitrite oxidizing bacteria  in  the soil  over a relatively short period of
time,  and not to measure the ability of the soil  to support growth of these
organisms over an extended period.   Substrate concentrations are kept low to
avoid toxic effects, and to  avoid  the  necessity of  dilution  prior  to nitrite
analysis.

     Initial Potential  Nfy*  Oxidation Activity Procedure--

     For each sample:

     a.  Weigh 6 g  of soil  into  a  125 ml  Erlenmeyer  flask.

                                    83

-------
      b.   Add  25  ml  of ammonium-phosphate buffer solution containing 167 ma
 K2HP04/1,  3 mg KH2P04/1,  and 66 mg  (NH4)2S04/1.   The  pH of this  solution
 should be 8.0  +_ 0.2.  Note:  A buffer close to the  test  soil  pH may be desir-
 able.                                                              -

      c.   Add  0.25  ml of  1  M NaClOa to  each flask to block N02-oxidation.

      d.  Cover the flask with aluminum foil and shake  on  an orbital shaker at
 200 rpm  for  22 +_  2 h  at 24 +_ 2"C.

     e.   Clarify the slurry or  a  portion of  the  slurry by centrifuqation
 or  filtration.                                                        3

 1000 f*   Ana1^ze the filtrate  or centrate  for N02-N  (Kenney and  Nelson
 1982;  APHA  1985).   Each  batch of  ammonium-phosphate buffer  should  also be
 analyzed  for  N02-N  and the  concentration subtracted from  sample  results.

     Initial Potential N02-0xidation Activity  Procedure--

     a.  Weigh 6 g of soil  into a 125  ml Erlenmeyer  flask.

     b.   Add  25  ml  of nitrite-phosphate   buffer solution  containing  167 mq
 K2HP04/1, 3 mg KH2P04/1, and 4.5 mg NaN02/l.  The pH of this solution should
 be 8.0 _+ 0.2.  Note:   A buffer  close to  the test soil pH may be desirable.

     c.  Add 5   1 of a "20 percent  solution  of nitropyrin (2-chloro-6-(tri-
 chloromethyl)  pyridine)  in dimethyl  sulfoxide  to   each  flask  to block  the
 oxidation of indigenous NH4+  to N02- (Shattuck and Alexander 1963).

     d.  Process  each flask and its contents as described for NH4+ oxidation
 described above in Steps d through  f.   In this case the N02-N concentration
 in the nitrite-phosphate buffer is the initial substrate concentration.

 5.4.1.5  Soil Plate  Counts--
     Total  counts  of major  microbial groups in the  soil  are intended  to  show
 the  viability of the soil microbial community.   Comparison  counts made
 before and  after  waste addition  provide   an  indication  of  acute microbial
 toxicity to the  specific  microbial  groups  and show the effect  of waste
 addition on  the community  as a whole.  Dominant species may be  suppressed,
 allowing for an increase in the predominance of less common groups.

     Ideally, the  plate count procedures should create optimal conditions  for
 the' microorganisms to be enumerated,  therefore, medium  composition,  incuba-
 tion conditions  and   length  of incubation are  important considerations  in
 plate  count assays.   It  is improbable that  all  types of microorganisms
 present  in  the soil  will  be detected  using  agar   plates, since all media
 types are  selective  to a  certain extent   (Greaves  et al. 1976).    Another
disadvantage of the  plate count assay  is that  comparisons  made among  enumer-
 ations performed  at  different times  will be accurate only if  test conditions
for each set of counts are  identical.  In addition,  the plate  count method  is
not conducive to counting numbers of filamentous organisms or  those producing
 large quantities of  spores.  Also,  there  is not necessarily  any  correlation

                                    84

-------
between numbers of microorganisms  and measured metabolic activities (Greaves
et  al.  1976).   The microbial  life forms  suggested  for  enumeration, i.e.,
total bacteria, actinomycetes  and  fungi,  are the most important soil  organ-
isms effecting  biological  degradation  and transformation  of hazardous waste
constituents.

     5.4.1.5.1  Media Preparation—The following three media are recommended
for determining viable  counts  of  the selected microbial  types:  tryptic soy
agar for  bacteria,  Martin's rose bengal  media for fungi,  and starch-casein
agar for  actinomycetes.   Details  on preparation  of these  media can be found
in Wollum (1982).

     5.4.1.5.2  Experimental Procedure--

     a.  Prepare a sufficient quantity of  plates  of each media  type.

     b.  Prepare dilutions of the  control  soil  and  each soilrwaste mixture in
triplicate according to  section 4.2.2 of  Wollum  (1982).   Three dilutions of
each replicate  are  plated on each type of media.   For bacteria and actino-
mycetes  10'6,  10~5,  and 10~4  dilutions  are  recommended.   For fungi,  the
suggested dilutions  are  10~5,  10'4, and 10~3.    The  dilutions  to be  used
should encompass the optimum  number  of  organisms for counting, i.e.,  30-300
colonies for bacterial  and  actinomycete plates and 10-20  for fungal plates.
All dilutions shoul be  prepared  in the  same manner since  comparisons  across
treatments are to  be made.

     c.  Prepare spread  plates  according  to section 5.2.2 of Wollum (1982).

     d.   Incubate the plates  at a controlled temperature,  generally between
24  and  28*C.   The  period  of  incubation  depends on  temperature  and  growth
conditions.   For bacteria and fungi, 4 to 7  days should be sufficient, while
actinomycete plates may have  to  be incubated  10 to  14  days  for  adequate
results.

     e.   Average  the  number of  colonies per plate  for  each  dilution  and
determine the number  of colony-forming units  per  gram dry  weight  of soil.
Significant  differences  in  numbers  of colony-forming  units  from the control
can be  determined  using statistical  tests.    A significant  reduction  in  the
number  of colony-forming  units  found in  the soil treated with waste as
compared  to control  soil  indicates the degree of acute  toxicity  of  the
complex waste mixture.

5.4.2  Preparation  of  Waste Soil Mixtures  for Bioassays

     If air-dried soil  is used,  it should be  brought up to the desired
moisture content (minimum  60 percent of  the water-holding  capacity  of  the
soil, preferably a moisture content that  will prove  typical  for field  con-
ditions).  The soil  is  acclimated  for 7 to 10 days  to allow for proliferation
of soil microorganisms.   After  the acclimation period,  waste which  has  been
thoroughly mixed  is added  to the  soil  at   the  previously  selected loading
rates.   When small percent  loadings  are to be tested, i.e., £10 percent, it
may be difficult to evenly disperse  the waste material in  the soil.   The use


                                     85

-------
 of an organic  solvent  as  a dispersal  agent  may not  be feasible in all cases
 since some solvents have toxic  effects on microbial processes.  The following
 method  (Utah  State University  1986) has  proved successful  for  providing  a
 fairly  uniform distribution of small  quantities of waste in soil."  A soil-
 waste mixture at a concentration much higher  than  the upper loading  rate is
 prepared using air-dried  soil.   The waste  is  incorporated  into  the  soil  by
 mixing on a rotary tumbler  for 12  hours  at  30 rpm.   This soil:waste  concen-
 trate can  be  "diluted" with  additional  acclimated  soil  so that the  final
 concentration  of  waste  is  equal to  the desired loading rate.

      After the waste has been  added to  the soil and thoroughly incorporated,
 the soilrwaste mixture  is  allowed to incubate  22+2 hours.   This incubation
 allows for acute  effects  of the waste on  soil  microbiota to  be  expressed
 After the incubation period, the  selected  toxicity assays  are begun.   Except
 for soil  plate counts,  the assays described  in this chapter  require 24
 hours for incubation or extraction.

 5.4.3 Detennination of Loading Rates

 5.4.3.1   Preliminary Loading Rate Investigation--
      In  order  to use any of  the previously described  acute toxicity tests for
 determining an appropriate range of  waste  application  rates,  a set  of  initial
 rates  to test  should be chosen.

      5-4.3.1.1    Microtox—Matthews and  Hastings (1985)  have  described  a
 method  using  the Microtox  assay  to determine  an  initial  range of waste
 application rates.   The following steps  are involved:

      a.   Obtain a  5 kg sample of  the site soil  and a 1 kg  sample  of the
 waste  to be applied.    Follow  the  sample collection procedures  referenced
 in  this  manual  to  insure that characteristics  of  soil  and  waste   samples
 are representative of those anticipated  at  the  site.

     b.   Weigh out two 100 g  aliquots of  air-dried  soil  which has  been
 crushed  and  sieved  to 2 mm  for soil  toxicity  determinations;  weigh  out two
 100 g  aliquots of waste  which has  been  thoroughly mixed.

     c.   Prepare WSF  samples   for  toxicity  testing  by  extracting aliquots
 of the duplicate waste and  soil  samples as  described in the Microtox" methods
 section.

     d.   Conduct  Microtox" tests on each  WSF  sample  prepared  as previously
 described.  Experience suggests  that if the EC50  for the WSF of a given waste
 as defined by  the  Microtox"  system  exceeds  25  percent,  the EC50 for  the WSF
 of any waste-soil  combination will exceed 20  percent and toxicity as measured
 by  the Microtox"  system  will   not  be a  significant  factor  in determining
 loading rate.  This  does not preclude use of the  test system to determine if
 toxicity reduction  of  hazardous organic  constituents  within  the  waste-soil
matrix is occurring  over time.

     e.   If  the soil WSF  is non-toxic, i.e.,  the full  strength DDW  extract
effects <_ 25 percent decrease in  bacterial bioluminescence,  the soil  has  no

                                    86

-------
apparent residual  toxicity.    If  soil  residual toxicity  is  indicated (> 25
percent decrease  in light  output in the  full strength DW extract),  the
cause of this toxicity should be determined  prior to  further  testing.

     f.   Determine  four loading  rates  to  be used  in  subsequent toxicity
screening tests according to the following criteria:

     1)  Calculate the  EC50  and 95 percent  confidence limits  for the waste
         WSF.

     2)  Choose the upper limit of the 95 percent confidence interval as the
         highest loading  rate  to be used.   For example,  if the  WSF  of  the
         waste  has  an  average  EC50 of  10  percent  and  upper  and  lower  95
         percent confidence  limits of  12 percent and 8 percent,  the highest
         loading rate would be 12 g of  waste  per 100  g of  soil.

     3)  Use  1/4,  1/2,  and  3/4 of the  upper  limit as the  remaining three
         loading rates (in percent wet weight waste per dry weight soil)  for
         testing.

     g.    Weigh out  four 300  g  samples of prepared soil.   Add prescribed
amount of waste and mix thoroughly to  achieve  the four loading rates (wt/wt)
described above.   Let the waste:soil  mixtures  incubate  at  room  temperature
(22 +_ 2"C)  for 22 +_ 2 hours before proceeding.

     h.  From each  of the four waste:soil samples,  remove three 100 g (dry
wt) subsamples  and  place in a  flask or  bottle for  extraction.   Discard  the
remainder of the sample.

     i.  Extract  each of the  12  subsamples  with  DDW according  to  the pro-
cedure described in Section  5.2.1  and  conduct  the  Microtox"  test on the  WSF
constituents.

     j.  Calculate the EC50  and 95 percent confidence limits for each waste-
soil  WSF.  Average  triplicate values to obtain  EC50 and 95 percent confidence
limits for each loading rate extracted.  Transpose each EC50 value to toxic-
ity units (TU) in soil  using  the following equation:
     k.  Prepare  a  log-log plot of toxicity  units  versus  loading  rates  for
use in estimating an  acceptable  initial  loading  rate  window.   The intercep-
tion point for  20 soil  TUs is  the  lower loading limit  for the window;  the
upper limit is defined as  twice  the  lower limit.  Experimental  data generated
to date suggest that  this  is a reasonable window for initial loading.

     This procedure was  developed based on experience with several classes of
hazardous wastes being evaluated for land treatment  in experiments conducted
at  the  U.S.  EPA  Robert S. Kerr  Environmental  Research Laboratory  at  Ada,
Oklahoma,  and  the Utah Water  Research  Laboratory, Utah  State University,
Logan,  Utah.

                                    87

-------
      5.4.3.1.2    Other Assays—When using  assays  other  than Microtox"  for
 preliminary initial  application rate estimation,  the following procedure may
 be useful:                                                                  J

      a.   Choose three or  four  loading  rates  that cover the range "from  0 to
 the maximum rate  likely  to be  used  based  on mobility, soil  hydraulic  con-
 ductivity effects, anticipated degradation rates,  or other criteria.  Concen-
 trations used  should  vary  by a  factor of 10 (e.g., 0, 0.1, 1, and 10 percent
 by weight).

      b.   Perform the selected acute toxicity bioassays on each  of  the  soil-
 waste mixtures.

      c.   Beginning  at the  concentration  showing little  or  no   toxicity  in
 step  b  above,  prepare a series  of  loadings that  encompass the concentration
 tfiere activity  is  reduced  approximately  50 percent relative to the  untreated
 control.  Smaller  increments in concentration should be used  than  in step  a
 above.

      d.  Again,  perform the  accute  toxicity bioassays.  The results of  these
 assays should identify a range  of loading rates that  are  not  highly toxic to
 the  soil  biota, and  that  can be used in laboratory  detoxification  studies.

 5.4.3.2  Selecting Waste Loading Rates--
      Giving greater weight to the level  of toxicity indicated  by  assays which
 indicate activity among a broader spectrum of  the microbial population (e.g.,
 respiration  and dehydrogenase)  or  indicating  general toxicity  (Microtox"),
 but considering  all  assay  results,  select a range of loading  rates  which  is
 not likely  to  inhibit decomposition but  will  use  the apparent  assimilative
 capacity of the soil.

 5.4.4  Data Interpretation

     No single  assay  is  likely  to  indicate the activity or viability of  the
 broad spectrum  of  soil  microorganisms or their functions.   Measurements of
 respiration may  represent  the  activity of the broadest community of micro-
 organisms,  but  high rates  of respiration by organisms with narrow metabolic
 capabilities, when  appropriate  growth substrate is  available, may  mask the
 reduction in activity of a  larger spectrum of  organisms.  When  information on
 the toxicity  of a  waste   or  its degradation  or  transformation  products is
 available from more than one assay, decisions on acceptable levels of toxic-
 ity for loading  rate  determinations or determination of detoxification  will
 be more reliable.  Broad  spectrum assays, (e.g., respiration or  dehydrogenase)
 and general  toxicity  (Micrptox")  are recommended,  but assays  relating  to
 specific subgroups of the  microbial community (e.g., nitrification, nitrogen
 fixation,  or cellulose decomposition) may also be considered.

     Assays  measuring  universal  metabolic activities (e.g.,  carbon dioxide
 evolution)  or general toxicity  (e.g., Microtox1") may be weighted highest in
decision making, but if other assays indicate severe toxicity, lower loading
rates should be  investigated.
                                    88

-------
5.5  TRANSFORMATION/DETOXIFICATION OF THE WASTE:SOIL MIXTURE

     Transformation/detoxification data are used to evaluate rates of detoxi-
fication  relative  to  the mobility of PHCs  in  the  soil.   Compounds  with high
mobility  in the soil must be degraded or detoxified rapidly.

     Changes in toxicity of the waste/soil mixture to soil microbial activity
can be monitored using  the  short  term bioassay procedures described in Table
5.1 for  the  determination of acute toxicity and  initial  loading  rates.   The
assays  are performed through  incubation  time  and  the results are compared
to  those  obtained  from  a control  soil.  For  organic  wastes,  stimulation  of
activity  in  assays,  for example respiration and dehydrogenase which  rely  on
heterotrophic  metabolism, may be  observed  as  microbial  communities  develop
the capacity to degrade part or all of the waste.   Assays should  be  continued
for  two  or  more  weeks after  activity has apparently  returned  to  control
levels  in assays  where  stimulation was observed  to assure that  toxicity  is
not expressed  after the  stimulatory  substrate has  been exhausted.   An  in-
crease  followed  by a decrease  in  toxicity of the soil/waste mixture  may  be
observed.  Initially, assays may need to  be performed  weekly.  The  frequency
of analysis using  assays may be based on  the  rate of change of toxicity with
soil incubation time.   Decreasing toxicity of the soil/waste mixture may  be
observed  over  a period of  time  until  the toxicity  is   at a  level  that  is
statistically indistinguishable from that  in the control  soil.

     Toxicity in the water  soluble fraction (WSF)  of  a soil/waste mixture  or
1n  the  leachate is  especially important  from a  public health  standpoint.
Water leaching from the  treatment  zone  should  be  free  of toxicity,  including
genotoxicity.   The Microtox"  assay  appears  suitable  for determining  water
soluble toxicity in the waste,  the waste/soil  mixture,  and the  transformation
or degradation  products of  the treatment  process.   Other assays,  including
higher  organism  assays,  may also  be  considered  (Table 5.1).   Tests  with
higher plants  and  animals have the potential  of showing the  integration  of
physiological  effects  of toxicants   on  the whole  organism,  although  these
tests are more expensive and  more difficult  to  perform than the  microbial
assays described above.

     Mutagenicity of the WSF should also be evaluated  periodically throughout
the study.   The  accumulation  of water  soluble mutagens  in  laboratory treat-
ability studies may  limit loading  rates.   Mutagenicity of the WSF  should  be
evaluated  before each  waste reapplication  event.    In  field  studies, muta-
genicity  of the soil-pore liquid  at  the bottom of the treatment  zone  may  be
evaluated  periodically.  The Ames  Salmonella typhimurium mammalian  microsome
(Maron and Ames  1983),  the Bacillus  subtil is  (Kada  et al. 1978) and/or the
Aspergillus nidulans  (Scott et  al.   1982,  Kafer  et  al.  1982) mutagenicity
assays are recommended for mutagenicity testing of soil-pore liquid based  on
the previous use of these assays  in hazardous  waste  land  treatment  research.
Other assays may  be used  if  their applicability  can  be demonstrated.  The
separatory funnel  liquid-liquid (method  3510) extraction  procedure  of the
U.S. EPA  (1982) is  recommended  for use in  mutagenicity  assays.

     Loading rates used in  the field  verification  study should  be  adjusted
based on the detoxification  rates  observed in  the  laboratory studies.

                                    89

-------
 5.6   IMMOBILIZATION  OF WASTE CONSTITUENTS
      IN THE SOIL  TREATMENT MEDIUM

      The affinity of a  chemical  substance  for  solid  surfaces  is  an."important
 factor  affecting  its  environmental  movement  and  ultimate  fate.  Chemicals
 that  adsorb tightly to  soil  are less subject to environmental  transport in
 the gaseous (volatile) or solution (leachate) phases.

      A  number of  laboratory  tests  consider the effects  of soil  adsorption
 on mobility.   Tests most  frequently  used include adsorption isotherms
 soil  thin  layer  chromatography  (TLC),  and soil columns.   Two  tests recom-
 mended  for use in the  Federal  Register  (Volume  44,  No.  53, March 16, 1979)
 are  the  isotherm and TLC  Methods.  These tests were  selected  for their
 relatively low cost, uncomplicated  test procedures,  wide usage  and  accept-
 ance, and  low  labor requirements.  Procedures for conducting isotherm  and TLC
 analyses,  data manipulation,  and calculations  are  given  in  the reference to
 the Federal Register cited above.  Both  tests are also recommended  for use by
 the Pesticide  Guidelines  (U.S. EPA,  1978)  for  obtaining information concern-
 Ing the mobility  of  chemicals in soil systems.  The use of isotherm and TLC
 procedures  also supports the standards identified in  Part  264.272(3)(iv).

     Although  soil  columns have also been  used to   assess the  mobility of
 chemicals  in  the  environment,  the following cautions were identified  in the
 Federal  Register  (Volume 44, No.  53,  March  15, 1979):  (a)  the difficulty of
 standardizing  column packing, (b)  the  large  amounts of  soil  and chemical
 required,  and  (c)  the excessive  time  and labor requirements.   If soil column
 studies  are used  as  part of an  LTD,  these cautions should be recognized and
 addressed  at  the  beginning of the  study.   The uniformity of  column packing
 anong a set of experimental columns may be  evaluated  using tracer  studies to
 determine hydraulic detention  time and extent of  dispersion or deviation from
 plug-flow  conditions.    Procedures  for  evaluating  flow characteristics  for
 column  reactors  are included in standard environmental  engineering  and
 chemical engineering textbooks.

     When column studies are used for evaluating  treatment, it  is recommended
 that  a  mass balance  for each  column be conducted that includes mobility and
 decay of  hazardous constituents  within the soil matrix.   Constituent concen-
 tration through depth of each  column  and the time interval required to reach
 the measured depth should be recorded.  Results may be expressed in terms of
 the relative transport of hazardous constituents for  all  columns  in order to
 select  design/management  options that  maximize treatment  (minimize  trans-
 port),  and  for determination of  PHCs  for each design/management combination.
 Using this  procedure and procedures for determining toxicity of the waste to
 the treatment  soil allows calculation of the soil/site assimilative capacity
 (SSAC) for each design management option evaluated.

     A  specific  type of column  study for  land  treatment evaluation  is  the
 barrel  lysimeter  (U.S.  EPA 1984).   A barrel  lysimeter  is a  large,  undis-
 turbed  soil monolith enclosed  by a water tight, waste compatible  casing,  and
 equipped with leachate collection devices.

     Because of  the requirement  for partitioning  data in  the mathematical
model  proposed for  conducting  LTDs, the  procedures for  conducting soil


                                    90

-------
isotherms for determining  partitioning coefficients using laboratory analyses
are discussed here, and are based on the procedures discussed in the Federal
Register (Volume 44, No.  53,  March  16,  1979).   Although not described here,
TLC  and soil column testing may also  be used  for the  determination  of
partitioning data for land treatment  demonstrations.  The specific procedures
and  approaches  for obtaining mobility information using TLC,  soil  columns,
estimation methods, etc.,  should  be  chosen in coordination  with  the  permit
writer  in order to determine  how the information can best be used in support
of the land treatment demonstration.

     Partitioning information, which  is expressed in terms of relative
concentrations  of  constituents in  oil,  air,  and soil  phases relative  to
the aqueous phase, is used to evaluate the:

     1.   effect of the three phases (soil, air,  and  oil)  on the concentra-
tion of hazardous constituent(s)  in the leachate;

     2.  effect  of waste and soil  type on immobilization;

     3.  effect  of soil  horizons  (depth) on  immobilization, and;

     4.  effect  of design  and operation parameters on immobilization.

     The partition coefficients required  for the model include:  Ko - parti-
tioning of constituents between oil  and  aqueous  (waste)  phases; Kd = parti-
tioning of constituents between soil  and aqueous phases; and Kh = partition-
ing of constituents between air and  aqueous  phases.

     It  is  recommended  that  these  partition  coefficients  be obtained  in
laboratory  analyses using  the  actual site  soil and  candidate waste(s).
This  approach  supports  the  standards  stated  in Part  264.272(c)(l)(i  and
iv).    Individual  constituents  that  have  been  identified  in  the candidate
waste(s) may  also  be  used as pure compounds in these analyses to obtain the
necessary  information.   The  use  of  the  site soil, however,  is required  in
order to support Part 264.272(c)(iv).

     Separate plots  of the  concentration  of  constituent(s)  in  each  phase
versus  the concentration  of constituent(s)  in  the aqueous  phase at equilib-
rium conditions and at constant temperature provides a means for calculating
each partition  coefficient  required.   The  partition  coefficients  are calcu-
lated as the slope of the  line for each plot, as follows:

        s   constituent(s) concentration  in oil phase
      0 = constituent(s) concentration  in  aqueous  phase


        _  constituent(s)  concentration  in  soil phase
      a = constituent(s) concentration  in  aqueous  phase


     ... _   constituent(s) concentration  in air  phase
        " constituent(s) concentration  in  aqueous  phase


                                    91

-------
     The  partitioning between  oil  (waste) and  aqueous  phases is evaluated
 using  a procedure  developed  by  McKown  et  al.  (1981)  for  assessing  the poten-
 tial  for mobility  (leaching)  of purgeable  and  semi-volatile organic  priority
 pollutants  from  waste materials.  The  general  approach is  similar  to that of
 the  U.S.  EPA  Extraction  Procedure (EP)  and the proposed American Society for
 Testing  and  Materials  (ASTM)  leaching  tests.  Samples of waste  and the
 leaching  medium (distilled  water)  are  mixed.   The aqueous  layer  is  then
 separated and analyzed.   The  partitioning  between  the  oil  (waste)  phase
 and  the  aqueous phase  can  be  determined  by  comparing  the concentration of
 constituents  in  the waste with the concentration of  the same constitutents in
 the  aqueous phase.

     The  partitioning between soil  and  aqueous  phases is obtained by  conduct-
 ing  a  soil  isotherm  analysis  using the  treatment demonstration site  soil and
 the  aqueous phase  obtained in the oil  (waste)raqueous partitioning analysis.
 A  typical method  of conducting an  isotherm  determination is  described  iii
 Weber  (1971).  The Pesticides Guidelines (U.S.  EPA 1978) also list references
 to procedures for adsorption  evaluations.   The  protocol described in  this LTD
 Guidance  Manual  is  based  on the method  described   in the  Federal   Register
 (Volume  44,  No.  53,  March  16,  1979),   and on  the Environmental  Engineering
 Unit Operations and Unit Processes Laboratory Manual  (1975).

     The  partitioning  between  water  and air phases may be evaluated by
 conducting  an equilibrium  partitioning  analysis  using  the   aqueous  phase
 generated in the determination of Ko.  Use of  this aqueous phase permits the
 evaluation of  air:water  partitioning coefficients,  Kh, as they may be
 affected  by  interactions  of  waste-specific   contaminants  existing  in  the
 extract.   Such  partitioning  experiments  should be  conducted  via  headspace
 analysis  equipment  or simpler controlled volume, sealed  sample  vials main-
 tained  at constant  temperature  for  a  time  period   during  which  liquid/gas
 phase  equilibrium  is  reached.   Following equilibrium, both phases are  ana-
 lyzed  for specific constituents of interest and  partition  coefficients  are
 determined based  on the  ratio of constituent concentrations in the liquid and
 gas phases.  A flow chart of a  typical   analyses scheme for partition  coeffi-
 cient determinations is  shown  in Figure  5.1.

     Alternatively, partition coefficients obtained  from  standard references
 for  simple  water:chemical  mixtures  may be used  for  Ko,  Kd, and Kh  values.
 However, this approach does not take into account the potential  interactions
 of waste  specific  contaminants occurring  in   the  complex hazardous waste
matrix.

 5.6.1  Experimental Aparatus  for Determination of Partitioning
       Between Oil  Phase  and  Aqueous Phase (Ko)

     Each experimental  unit  consists  of  a glass  reactor containing waste
 as it  will  be applied  to the  site  soil.  Liners  for screw  cap  reactors
 should  be Teflon*.   Distilled  water  is  used  for the  leaching  medium  for
 simulating natural   conditions.   The unit  is  sealed  and  placed on a rotary
mixer  (tumbler) of  the National Bureau of Standards (NBS)  design type.
 Samples are tumbled  at  approximately 30  rpm  for 22  hours  +  2 hours.    Ex-
 tracted samples  are  allowed to  settle  for  30 minutes and  the  supernatant  is


                                   92

-------
                                                Analyze by
                                                GC or HPLC
                                               Extract with
                                                  CH2C12
    Analyze by
Purge and Trap GC
Volatile Fraction
Methenol Extract
   Analyze by
   GC or HPLC
      Extractable
    Fraction
                                                   Soil
II
                                          Waste ^=i Water ;=s Air
                                               Sample with
                                            Gaslight Syringe
                                 Analyze by Direct
                                   Injection GC
                                 Volatile
                                 Fraction
                                      CH2C12 Extracteble
                                          Fraction
                               Analyze by
                            Purge and Trap GC
                                         Analyze by
                                         GC or HPLC
Figure  5.1.  Sample preparation and analysis  scheme for the determination  of Kh, Kd,  and  Ko.

-------
 centrifuged  prior  to analysis.   Test units are set  up  in  duplicate  for each
 candidate waste.

 5.6.2  Experimental  Procedure for Determination of Ko              .  •

     1.   Prepare glass reactors by  adding  waste (wet weight)  and distilled
 water  (volume)  to  each duplicate  reactor  making  sure that  no  head  space
 results upon sealing.  An example schedule is  presented  below.   The amount of
 waste  used  can  be  varied,  however,  the  suggested  ratio  of  waste  to  water
 should be appropriate for most determinations.


             Reactor Number         Waste                Water

                   1                1000 g            1000 ml
                   2                1000 g            1000 ml
                   3                1000 g            1000 ml
                   4                1000 g            1000 ml
                   5                1000 g            1000 ml
                   6                1000 g            1000 ml
                   7                 500 g            1500 ml
                   8                 500 g            1500 ml
                   9                 100 g            1900 ml
                  10                 100 g            1900 ml


     2.  Tumble  test units at  approximately  30  rpm for 22 hours +  2 hours
 at room temperature (22*C  +  2*C).

     3.  Remove the test unit  and allow  to settle  for 30 minutes.

     4.  Centrifuge the supernatant for each reactor at high speed (at least
 20,000 g)  for 10 minutes.  The  aqueous  equilibrium solution should be stored
 at or below  4*C.

     5.  Reserve Reactors  1 through  4  for  analyses to determine Kd  and Kh
values.

     6.  Analyze for  concentrations  of constituents of concern  in  the
supernatant  for Reactors 5 through  10  for  determination of Ko.

     7.  Refer to data  handling section (Section  5.6.7)  for calculations of
Ko values.

     8.  Use the  supernatant from Reactors 1 and 2 for conducting analyses to
obtain  the  partitioning  between soil and water,  i.e.,  Kd.  This is  accom-
plished by conducting isotherm  analyses using  the site  soil  and the  complex
waste aqueous extract supernatant.

     9.  Use the  supernatant from Reactors 3 and 4 for conducting analyses to
obtain  the  partitioning  between  air and  water,  i.e., Kh, as per Experimental
Procedures for  Determination of  Kh presented below.


                                    94

-------
5.6.3  Experimental Apparatus for Determination of Partitioning
       "Between Soil Phase and Aqueous  Phase  (Kd)

     Scalable  glass  reactors  should  be  used.    Screw  cap  reactors "should
use Teflon™  liners.   Reactors are sealed and placed on  a  shaker  or tumbler
for mixing  at 22"C +_ 2"C.   Soils should be sieved with a  100 mesh  stain-
less steel or brass screen before testing.

5.6.4  Experimental Procedure for Determination of Kd

     1.   Use four  aqueous  subsamples of  each  supernatant obtained  from
Reactors 1 and 2 for determination of Kd  (approximately 250 ml),  for a total
of  eight  samples  (four  duplicates).    The  following  schedule is  suggested
although other combinations  may be considered:


                  Sample         Aqueous Phase          Soil

                    1                250 ml             0.5 g
                    2                250 ml             0.5 g
                    3                250 ml             1.0 g
                    4                250 ml             1.0 g
                    5                250 ml             2.0 g
                    6                250 ml             2.0 g
                    7                250 ml            10.0 g
                    8                250 ml            10.0 g


     2.   Immediately after  addition of  the  solution, assuring  that  no  head-
space  exists,  the containers  should  be  vigorously agitated with  a  vortex
mixer or similar  device.   The containers should be equilibrated in  the  rotary
tumbler for 22 +_  2 hours.

     3.   After equilibration,  the suspensions  should be  centrifuged   at  a
high speed  (at least  20,000 g)  for  10  minutes.   The  aqueous  equilibrium
solutions  should  be stored at or  below 4"C.

     4.  The  chemical  adsorbed  on the  soil  surface  should  be extracted  with
an  organic  solvent in  which the  test  chemical(s)  is  soluble,  and a  mass
balance should be performed.   A volume of organic  solvent  equal to the
original  volume of aqueous  solution  (used to attain equilibrium)  should be
added  to  the adsorbent so  that no  headspace exists, and  the containers
shaken vigorously for  10 minutes.  The mixture should  then  be centrifuged at
a minimum of  20,000  g for 10 minutes.  This extraction  procedure should be
performed  three times.

     5.  The  aqueous  phase  and  the organic solvent extracts should be  ana-
lyzed for the  constituents  of  concern.    If the mass of constituents in the
aqueous and/or the solvent  phases are too  low, concentration of each-phase
must be carried out  using standard techniques,  i.e.,  K.D.,  purge and  trap,
etc.
                                   95

-------
 5-6.5  Partitioning  Between Aqueous Phase and Air Phase (Kh)

      Glass  reactors with  scalable Teflon1"  septum  caps  should  be used.   A
 known amount of aqueous extract solution is  added  to provide a variable air
 phase volume  in  the  reactors. The reactors are maintained at constant temper-
 ature of  22-C  +_  2"C  for 22 + 2 hours to ensure equilibrium is reached.

 5.6.6  Experimental  Procedure for Determination of Kh

      1.  Use  four aqueous  subsamples  of  each  supernatant  obtained  from
 Reactors  3  and 4 for determination of Kh, for a total  of eight samples   Four
 volumes of  supernatant should  be used to provide a variable  gas  volume  over
 the  liquid   that  allows  the  determination   of  true  equilibrium  within  the
 samples.  The  following schedule is suggested although other combinations mav
 be considered :                                                              J


             Sample           Aqueous Phase            Gas  Phase

                1                50 ml                  75  ml
                2                50 ml                  75  ml
                3                62.5 ml                62.5  ml
                4                62.5 ml                62.5  ml
                5                75 ml                  50  ml
                6                75 ml                  50  ml
                7                85 ml                  40  ml
                8                85 ml                  40  ml


     2.   Immediately after addition of  the  solution  to the unit, the upper
Teflon1"-lined cap  should  be  sealed and the  unit  should be  placed in a  con-
stant temperature environment for a 22  +_  2 hour  incubation time.

     3.   Upon  completion of incubation,  the gas phase is  sampled (1-4 ml)
with a gas-tight  syringe and  analyzed by  direct  injection  gas chromatography.
Duplicate  samples should be taken for GC  analysis, and  efforts  should be made
to minimize  volume  taken for each sample  to prevent a  significant vacuum  from
occurring  within  the sample vial.

     4.   The  aqueous phase should be  analyzed  immediately  for contaminants
of concern following solvent extraction and/or concentration (purge and trap,
KD concentration, etc.) if the concentrations of  contaminants in  that phase
are too low for  accurate quantification  following equilibrium partitioning.

     5.   A  mass  balance can then  be  performed using  data  from  the aqueous
and air phases  to indicate  the accuracy of the method.

     6.   If the  concentrations  of  constituents in either of  the  two phases
are too low after  equilibrium  to obtain accurate results larger  air/liquid
partitioning vessels (500 to 1000  ml)  could be used  to provide  large phase
volumes for  the concentration step prior to quantification.
                                    96

-------
5.6.7  Three Phase Partitioning Method for Ko and Kh Determination

     An  alternative  to  separate phase partitioning experiments using  waste,
aqueous,  and  air phases  is  possible if  equilibrium  concentrations of con-
taminants  of  interest  are  readily  quantifiable  without  significant  phase
concentration.  This method utilizes glass crimp  top vials  with  Teflon1"-lined
septa, as  described  above,  for the equilibration of the waste, aqueous, and
air phases as shown in Figure 5.2.

5.6.8  Experimental Procedure for the Combined
       Contamination of Ko and Kh

     1.   Prepare glass  serum  bottles by  adding  the approximate  waste (wet
weight)  and distilled water  (volume)  to  each duplicate reactor according to
the following suggested schedule for each  candidate waste:

              Sample               Aqueous              Waste

                1                   75 ml                 0.5
                2                   75 ml                 0.5
                3                   75 ml                 1
                4                   75 ml                 1
                5                   75 ml                 5
                6                   75 ml                 5
                7                   75 ml                10
                8                   75 ml                10

     2.   Immediately  after  addition  of  the waste and distilled water to the
bottles, the  Teflon^-lined  cap  should be sealed  and  the  bottles  should be
tumbled for 22 +_ 2 hours in  a rotary mixer at approximately 30 rpm.

     3.   After  tumbling,  the bottles are centrifuged at 2000 rpm  for  30
minutes.

     4.  Upon completion of centrifugation the gas phase is sampled (1-4 ml)
using a  gas tight  syringe.   Duplicate samples should be taken for GC analy-
sis, and efforts should  be  made to  minimize volume taken for each  sample
to prevent a sigificant  vacuum from forming within  the  serum bottle.

     5.  Aliquots of the  aqueous phase are taken immediately after headspace
sampling.   Duplicate  analyses  for  volatile constituents should be conducted
using  purge  and  trap   procedures,  while  solvent extraction/concentration
procedures should be conducted  for  nonvolatile constituents of interest using
the balance of the aqueous phase.

     6.   Finally, aliquots  of  the  waste phase  should be taken,  following
aqueous  phase  sampling,  for use in  volatile and/or nonvolatile constituent
quantification in the equilibrated  waste phase.

     7.  A Kd can be evaluated from  the equilibrated aqueous phase generated
from this  procedure  if  a larger initial  aqueous  phase volume  ( 400  ml)  is
utilized.   This  aqueous phase  is used  to  determine  Kd  according  to the
procedures described in  Section 5.6.4.


                                    97

-------
                Aluminum Ring
                      Waste
Teflon™ Lined Rubber Septa
                                                 Glass Bottle
                                               Aqueous Phase
Figure 5.2.   Apparatus for three-phase partitioning coefficient determina-
              tions.
                                    98

-------
 5.6.9  Data Handling

     For each partition coefficient, Ko, Kd, and Kh,  the determination  of  the
 value of the coefficient  is  determined  from a plot of the concentration of a
 constituent  in  the aqueous  phase  (x-axis) versus the concentration of  the
 constituent  in  the  relevant  phase (y-axis).  Three  plots  will  be  generated,
 one  plot  for determination  of each partition  coefficient.   Each  partition
 coefficient is calculated as the slope of the line.   Values for  the partition
 coefficients for each hazardous constituent serve as  input  to the  LTD  mathe-
 matical model presented and discussed in Chapter 4 of this manual.

 5.7  DEGRADATION OF WASTE CONSTITUENTS
     IN THE SOIL TREATMENT MEDIUM

     Loss rates are generally  based  on  first  order kinetic  constants derived
 from  laboratory or field  studies.   Methods and  procedures  for  laboratory
 studies  that can  provide data  for the  calculation of  rate  constants  are
 presented below.

     A plot of the disappearance of  a constituent, originally present  in  the
 waste  and  in  the waste/soil  mixture  immediately after  waste  application,
 versus treatment time provides the following information:

     (1)   The  reaction order  of the degradation  process (generally  either
 zero order or first order);

     (2)  The reaction rate constant, u  (mass constituent/mass  soil-time  for
 zero order reactions or I/time for first order reactions);

     (3) The half-life (t]_-/2, time) of each constituent of  concern.

     Degradation information  should be collected  at constant temperature,  and
 through at  least  one complete cycle of  application  and  treatment prior to
 reapplication.   Biodegradation rates for each constituent of concern must be
 calculated, as  well  as  the  biodegradation  rate  for  the  oil   phase of   the
 waste.  Degradation rates are  converted into  half-lives for constituents  and
 for the oil phase.

     Degradation  information,  which  is normally  reported  as  half-life
 in the soil,  is used  to  evaluate:

     (1)  Effect of degradation  on the  attenuation of constituent transport
 through the treatment  zone; and

     (2)  Effect of design and operation parameters  on constituent degrada-
 tion and attenuation of  resultant  constituent  transport  through  the treatment
 zone (including loading  rate, loading  frequency, control  of  soil  moisture,
 amendments  to maximize degradation, etc.).

 5.7.1  Hazardous Constituent  Reduction Evaluation Techniques

 5.7.1.1  General Experimental  Approach—
     Hazardous  constituent  reduction  experiments using methods accounting for
contaminant vapor  loss from  the  soil  are  recommended if significant amounts


                                    99

-------
of volatile constituents exist  in  the  waste to be evaluated for land treat-
ment.  A complete experimental  set-up might  include, for example, degradation
units consisting of  600 ml glass  beakers containing  200  g  of prepared soil
(air-dry weight),  along  with  air emission  flask  units  consisting  of 500 ml
ground glass  stoppered  Erlenmeyer flasks in  which  up to 200  g  of prepared
soil  is  added.  The units are arranged in  sample  sets for sacrifice at
selected intervals during the duration of the experiment (126 days).  Waste-
soil in the sacrificed  units  is extracted and analyzed for  TOC and specific
organic constituents to  evaluate PHC  reduction with time.

     Test units are  routinely  set-up in  triplicate  for each of three levels
of waste loading plus a  blank  for each  sampling interval (triplicates for the
air emission  samples  for each  waste  loading only).   The units are typically
incubated at room temperature (22"C + 2"C)  in the dark.  Four sample sets of
the degradation  units are prepared Tor  sacrifice,  extraction  and  analysis,
and data calculation  at selected test intervals,  while only  a portion of the
air emission units are sacrificed at  42 days with  the balanced dismantled and
evaluated at the end of  the study.

5.7.1.2  Evaluation of Biodegradation--
     5.7.1.2.1   Experimental  Apparatus—Each  experimental   degradation  unit
consists of a 600 ml  glass beaker containing 200  g of prepared soil (air-dry
weight).   Following an initial acclimation period, each unit is charged with
one of the selected loadings of waste.  The  units  are  arranged in sample sets
for sacrifice  at  selected  intervals during the  duration of  the experiment
(126 days).   Waste-soil in  the sacrificed units  are analyzed for  TOC  and
specific  organic constituents  to evaluate  apparent degradation potential.

     The experimental  apparatus for air  emission measurements  is  shown  in
Figure 5.3.  The system consists of the 500 to 1000 ml Erlenmeyer flask with
a fitted glass  aeration cap through  which high  quality breathing air enters
the flask through  Teflon™  tubing.   The purge air flows over  the surface of
the soil-waste mixture contained within the  flask and exits  the aeration cap
through an effluent  tube close  to  the  top of the flask.  The  flow path  and
configuration  of the  flask ensures effective mixing  over  the  surface of the
soil.  Effluent purge gas containing  volatile  constituents from  the  soil-
waste mixture leaves the flask through Teflon1" tubing, passes  a glass T used
for split stream sampling, and  is  then conducted via tygon  tubing  to a vent
for discharge  away  from the  experimental  area.   Split stream  sampling  is
conducted through  the glass  T's in the flask effluent line by  using  a con-
stant volume  sample pump  in  conjunction  with sorbent tubes,  sample bulbs,
etc., connected to  the  pump via  a balanced capillary flow  controlled  glass
and Teflon" sampling manifold.

     5.7.1.2.2     Experimental  Procedure  for Apparent Degradation Measure-
ments--

     a.   Prepare  experimental  units  for  each  design/management  combina-
tion.

     b.  Adjust the  soil moisture content in each unit to 70 percent (except
where soil  moisture is evaluated as a management option); record unit weight.

                                    100

-------
               Influent
               Purge Gas
                        »Effluent Purge Gas

                                   I
/•;:•;:•;':•;':•;:•;
$$•:
$%&&
                            Soil/Waste
                              Mixture
                                               Capillary Flow     I
                                                  Control         n
Constant
Flow
Sample
Pump
                                     Effluent Purge Gas
                                                                 '•SL*,ct*
Figure 5.3.   Laboratory  flask apparatus used for mass balance measurements.
                                  101

-------
     c.   Place  test  units  in  dark  at  room temperature  and  allow to acclimate
 for 10 days while maintaining favorable moisture content.

     d.    Following  acclimation,  charge  each   test  unit  with  its" selected
 loading  (wt.  X) of  waste  and  mix  thoroughly (36 units will  receive  1 of 3
 selected waste charges and 12 will  receive no waste charge).

     e.   Arrange  the test units  in  6 sample sets consisting of 2  units
 for each charge and 2 control  soil  blanks  (8  test  units).

     f.   Place  5  sample  sets in  the dark at room temperature to  begin
 the  test;  sacrifice  the  Day  0 sample set for organics extraction and  TOC
 analysis.

     g.   Check  the moisture content of each  unit weekly  and adjust  to
 70 percent water-holding capacity by adding deionized water.

     h.   Aerate each unit by  mixing  the  total  contents  thoroughly  every  14
 days.

     i.   Sacrifice sample sets so  that  a minimum of  6 points are used  to
 generate the  degradation plot.  Sampling  on  days  7,  21,  42,  84,  and 126  may
 allow completion of the experiment.   If results  indicate sufficient data have
 been generated, the PHC experiment  can be terminated  following data  calcula-
 tions for any sample set.

     5.7.1.2.3   Experimental  Procedure for Volatilization Corrected  Degrada-
 tion Rates--                              ~               "	!	

     a.  An experimental run  is initiated by first placing  an amount of  the
 actual  field soil  within 12 flask units, the magnitude and procedure  of  which
 is dependent upon the application  method,  i.e.,  surface or subsurface,  being
 simulated  during  the run.   If subsurface  application  is to  be  simulated,
 approximately 200 g of soil is placed  in the flask,  waste is added following
 the 10 day acclimation period  as described  for the degradation studies above,
 acclimated soil of  70. percent moisture content is  then  immediately placed
 above the waste application point to a  depth simulating  the actual  subsurface
 injection depth to  be used in the  field, and  the  flask units are quickly
capped.  If surface application is  simulated, waste  is  added  to the  200 g  of
 soil  in the flask, is quickly mixed, and the flask units are quickly capped.

     b.   Once capped,  the purge  gas  should be  initiated  at a  controlled
rate of 200 ml/min, and initial emission measurements are  begun by drawing a
constant volume sample of flask effluent gas through  the sampling/collection
system via a constant  volume sample  pump and  a balanced,  capillary flow
controlled, four-place sampling manifold (three  samples plus  a blank).  This
procedure  allows  the concurrent  sampling  of all flask  units for the same
period  of time  and during  the  same  time period  over  the  volatilization run.

     c.  Sample pump rate  and purge gas flow rate are measured before each
sampling  event via a  bubble tube flow  meter  and the  duration  of  the sorbent
tube sampling  is recorded for  accurate  soil loss rate  calculations.

                                    102

-------
     d.   Upon completion of the sampling event, sampling tubes,  bulbs,  etc.,
should be stored  as  recommended by EPA prior  to  analysis  via  standard pro-
cedures   appropriate  for  the  specific  sampling/concentration  method  used.

     e.    The sampling and  analysis  procedure  is repeated  at  selected time
intervals following waste addition  corresponding to the anticipated log  decay
in soil  loss rates.  A recommended  sampling schedule is as follows:

     0,  15  min,  1 hour,  2.5 hours,  10 hours,  1  day,  10 days, 21  days,  80
     days, and 126 days

If results indicate undetectable air release rates after 10 days of sampling,
this portion of the study may be terminated.    If blank soils show insignifi-
cant levels within the first  day of  sampling,  their  use may also  be discon-
tinued.   Appropriate blanks  and  spikes  must  be used  throughout  the sampling
period,  however,  to maintain QA/QC  procedures for the method.

     f.    The moisture content  of  these units  should be checked  weekly  and
adjusted to 70 percent water holding capacity by adding deionized water.

     g.    One flask  from each  loading  rate  should be  sacrificed following
the  21  day  sampling  event  to allow correlation  with  degradation  studies
regarding residual soil  mass  levels of contaminants  in the applied  waste.

5.7.1.3   Data Calculations--
     For each of  the  selected operating/management and  waste loading  condi-
tions evaluated, the  degradation  kinetic  parameters,  and half-life (tj/2 in
days) for first order kinetics or the rate of transformation (r in mg/kg/day)
for zero order kinetics,  are calculated from  specific  constituent and  gross
parameter  data  after  being  corrected  for  volatilization  losses  measured
during the  study.   Mean concentrations for the duplicate  units are used in
all calculations.

     For  each PHC,  a  plot of  cumulative mass  collected  in  the  emission
flask effluent gas versus  time  is made.   These cumulative mass  values  are
calculated  from  the  measured  soil release data  (mass/area/time),  the soil
surface  area  exposed  to the  purge air, the  fraction of  purge  air actually
sampled, and  the  cumulative time  during effluent sampling.  The  cumulative
mass values  are  then  used  to correct  degradation  data for volatile emission
losses by subtracting  them  from the  total  PHC  mass change as indicated from
beaker degradation studies.

    For  each  PHC, a  plot  of mean  volatilization-corrected  concentration
versus  time  is  made.   If  a  straight  line  plot  results,  then  zero-order
kinetics are indicated and the rate of degradation is computed from the slope
of the straight line.

     f = GI - C2/t2 - ti                                               (5.1)

where:

     Ci  » the volatilization-corrected concentration coordinate of point i on
          the straight line in mg/kg

                                    103

-------
     t-j  =  the  time coordinate of point i on the straight  line, days

     If  zero order kinetics do not fit the data, plot the ratio of the mean
 volatilization-corrected concentration at day t to the mean concentration at
 day  0  versus  time on  semi-log  paper  (time  is plotted on the linear scale)
 If a straight  line results from a plot of this type,  first-order kinetics are
 indicated,  and the  slope  of  the  relationship of the natural  logarithm of
 contaminant  concentration at time, t,  divided  by contaminant concentration at
 time zero  versus  time represents  the  first  order degradation  rate for that
 constituent  with units of I/time.

     The  half-life  coefficient, ti/2  (time), represents  the length  of time
 required for a constituent,  C,  to decay to one-half of its original  concen-
 tration, C0:
                                                                       (5.2)


where:

     C0   = the initial concentration  of  a constituent in soil (mg/kg)

     C    = the volatilization-corrected  concentration of constituent in soil
            at time t (mg/kg)

     tl/2 = half-life of the constituent  in  soil (time)

Because the  above relationship is  not  a linear function, there  is  no con-
venient relationship  between  the  half- life  and the zero order  rate  coeffi-
cients; however,  the  half-life may be calculated from  the  first  order rate
coefficient by the following formula:

     ti/2 = In (0.5)/(-yi)  « 0.693/yi                                   (5.3)

where:

     tj/2 = half-life of waste constituent in soil (time)

     wi   = first order  volatilization-corrected degradation rate, slope  of
            plot of logarithm  of  concentration  versus treatment time (semi-
            logarithm plot)  with units of I/time

     For those  cases  in which  neither  zero order nor  first order  kinetics
apply,  the plot  of   volatilization-corrected concentration  versus   time  is
simply reported.

     Effects of design and  operation parameters on contaminant degradation  is
evaluated from  degradation  rate and tj/2 data  from degradation experiments
conducted  under  various design  and  operation conditions.  For example,
evaluation  of the effect of moisture  content on corrected waste degradation
at a design application rate can be determined by conducting  laboratory scale
degradation studies  at three  soil moisture contents.  Optimal moisture


                                   104

-------
conditions for such an experiment can be determined  from  analysis of reaction
rate  constants  and/or tj/2  values  measured  at each condition  investigated.
The  moisture content  producing  a  maximum  corrected  degradation .rate  and
minimal  tj/2 for the  PHCs  in the  waste would then be  selected  for  use in
field verification studies.

     Similar  laboratory  experiments can  also be conducted  for determining
conditions for nutrient  addition, organic amendment,  soil  pH control, etc.,
that result  in maximizing of land treatment activities.

5.7.1.4  Evaluation Using Laboratory Scale Microcosm Systems—
     5.7.1.4.1   Introduction—Laboratory data may be collected using column
or microcosm  systems if  it  is desired  that  laboratory equilibrium partition-
ing data and  model prediction information be  evaluated on a  laboratory scale
prior to actual  field  plot  studies.   It  should be recognized, however, that
while  column studies  do provide  a means  of investigating  land  treatment
system  dynamics,  results should  be expected  to  be highly  variable  due to
variability  in  packing methods, soil  uniformity, etc.,  as  discussed  above.
Results often preclude rigorous quantification of transport and degradation
phenomenon, but do allow semi-quantitative evaluation of  the  scale of various
interaction  pathways  expected to  affect waste constituents  applied  to  the
actual land  treatment  site.   The cost and complexity of column or microcosm
systems  should  be weighed  against  the  value of data  collected  in  such  a
laboratory system that may be collectable at  an experimental  field site.

     5.7.1.4.2   Experimental  Apparatus--Air  emission monitoring  and quanti-
fication as  a function of operating  and management  procedures is conducted
in a controlled laboratory setting  using modular, 7.62 cm I.D., beaded glass
process  pipe microcosm  systems,  with solid  sorbent tubes,  sampling  bulbs,
etc., for sample collection  and/or concentration.  Figure 5.4 shows a typical
microcosm unit  consisting of  two   15.25  cm  long body sections,  along with
removable bottom  and  top cap sections  for  ease  of unit assembly  and dis-
assembly for cleaning.   Sections of  each unit  are  connected via Teflon^-lined
pipe clamps  to provide an air and water tight seal  at all  joints.   The  top
cap section has four glass  inlet tubes  to  provide inlet  and  outlet ports for
purge gas flow,  a port  for  connection  to  a  Magnehelic or manometer  for  cap
pressure determinations,  and  a port  for  head  space temperature and  gas
composition determinations.   Brass Swedgelock1" fittings with  Teflon™ ferrules
are used at  all connections, with Teflon1" tubing  used for all transfer lines
to the point  of  split  stream sampling.  Tygon" tubing  is used downstream of
the split stream  point for purge gas  venting, with  venting  conducted  to an
enclosed hood for discharge  from the experimental  area.

     High quality  breathing air is  utilized  as  purge gas  to  eliminate  the
possibility of  oxygen  limitations  that may occur to microbial process
carried out during the volatilization runs.  A series of four microcosms  are
connected to  a  single purge gas source via  balanced glass Ys,  with  flow
balance checked  via Magnehelic or manometer readings to ensure equal  flow to
each microcosm unit.   Microcosm units  are  placed in  a constant temperature
water bath  or within  a  constant temperature room  to  eliminate temperature
variation during  a given run.
                                    105

-------
    Influent
    Purge Gas
 Magnehelic
                          Effluent Purge Gas

                                   1
           Microcosm Unit
                             Soil
Tenax Sorbent
    Tubes
                                               Capillary Flow
                                                   Control
Constant
Flow
Sample
Pump
                                      Effluent Purge Gas
Figure 5.4.   Laboratory microcosm apparatus used in  laboratory AERR model
             validation studies.
                                 106

-------
     5.7.1.4.3  Experimental  Procedure for  Microcosm Studies--

     a.  An  experimental  run  is initiated  by first placing a given depth of
soil within  a microcosm unit, dependent upon  the  application  method,  i.e.,
surface or subsurface, being  simulated during  the run.  A maximum application
of depth of  approximately 15.24 cm is  possible with the two piece body shown
in Figure  5.4 with deeper application depths  possible with  additional  body
units connected in series.

     b.  Soil  depth  and mass readings are  taken for bulk density determina-
tions.

     c.  Waste is then applied  to  the units in as uniform  a fashion  as
possible.    The  application  rates used are  based on a weight percent  of
waste  with  respect to  the top 6  inches of  the soil  material   the  waste  is
applied  to.    If  subsurface   injection  is  to be  simulated,  the appropriate
amount of soil  is added to  the unit  to provide the desired soil depth  above
the application point.

     d.  The units  are then  capped, sealed air tight,  and  purge gas  is
initiated and maintained constant  at  300 ml/min/microcosm during the volatil-
ization experiments.

     e.   Microcosm  gas sampling  is conducted at  selected  time  intervals
following waste application  as described  above for volatilization-corrected
degradation rate flask studies (5.7.1.2.3 b through d).

     f.  Data related to the  physical  conditions of the microcosm systems  are
collected at each  sampling time  and  include  air and water  bath temperature,
height of the capillary rise  observed above the injection point, and depth of
the waste wetting front below the  soil  surface.

     g.  When used in conjunction  with  degradation and leaching  rate measure-
ments, columns must be sacrificed at  selected intervals,  as described  above,
to allow soil extraction for mass  balance determinations.
                                    107

-------
                                                         OSWER POLICY DIRECTIVE NO.

                                                          4«6  .  00-2   »
                                  CHAPTER 6

                MONITORING TREATMENT PERFORMANCE  IN THE  FIELD
6.1  PURPOSE OF FIELD VERIFICATION STUDY FOR
     NEW AND ISS FACILITIES

     The purpose of a field plot study is to verify the  effectiveness of waste
treatment under field conditions for selected design and management option(s).
Field  verification  studies are  appropriate  for  sites  using  Scenario  2  or 3
(Chapter 1)  for obtaining  a Part  B permit.   The  design  and management
option(s) may  have been  selected  based on  the  result  of laboratory studies
(Chapter 5)  and/or model  results  (Chapter 4).    Alternatively,  for  ISS
facilities, previous field  scale  practices  that  have not  been evaluated with
respect to  the specific criteria given in Part 264 may be selected.  However,
for  ISS  facilities,  if the applicant selects a design/management combination
that is different from  previous  practice(s),  with  respect  to changes in unit
processes,  application rates, or  use of soils,  the use of laboratory studies
and/or model  estimation  is  strongly encouraged  for  evaluation  of potential
treatment effectiveness  before  conducting  a field verification  study.   The
field  evaluation is  based on monitoring  soil  cores  and  soil-pore  liquid  to
detect losses.   The use  of the PHCs identified  through  laboratory  or other
studies may also be verified in  the field studies.

     The field plot study has the following  components:

     Design parameters                        - application rate(s)
                                             - application frequency
                                             - application method(s)

     Management options                      - controlling soil pH
                                             - enhancing microbial activity
                                             - enhancing chemical reactions
                                             - controlling soil moisture

     Site selection                          - site  location
                                             - number  of sites needed

     Monitoring                              - soil  core
                                             - soil  pore liquid
                                             - waste analysis
                                             - groundwater (optional)

     Data interpretation


                                   108

-------
     The  field  verification  study is  intended  to  provide  the following
specific information:

     a)  The effectiveness of design parameters and  management options for the
degradation, transformation,  and  immobilization  of  hazardous constituents by
monitoring soil cores and soil-pore liquid.

     b)   Whether  significant concentrations of  hazardous constituents  occur
below the treatment zone and in groundwater.

     c)  If current ISS site loading rates and  frequencies are compatible with
local site conditions.

     d)   If  current  ISS  management practices  are suitable for  local  site
conditions.

     e)  A data base  for evaluating  transferability of  information concerning
effectiveness of  waste  treatment  from one  site  to  another  using  the mathe-
matical model proposed, or  a similar model,  to  integrate site, soil, and waste
information.

6.2  FIELD VERIFICATION STUDY
     ALTERNATIVES


     Field verification  studies may  be  conducted  using  one of  the  methods
Identified  in  Table 6.1.    The  table contains a  comparison  of  field
verification  alternatives  for  factors  including  representativeness,
effectiveness,  and  implementation  aspects.    Other  methods  may be used  for
field verification studies, and would need the  approval  of the permit writer.

     As indicated in Table 6.1, field verification  studies are categorized by
the size of  the  field plot.   Box plots and barrel  lysimeters are small  scale
reactors containing experimental units that  are physically separated  from  the
surrounding site/soil.  Typically a 5'  x  5' wooden box plot is used.  A barrel
lysimeter is a  cylindrical  reactor containing an undisturbed  soil  monolith.
Information concerning  the collection and  installation of barrel  lysimeters
is presented in Brown et al.  (1985).

     A  larger  field  scale  plot may  also  be  used.  Generally,  a  field  scale
plot may be  used  on an existing  ISS site or new site  with  runon/runoff  and
other field  conditions  controlled.   Usually  approximately 12  ft x 48  ft  in
size, field scale plots  allow routine full  scale management practices  to  be
applied.

     It  is  also  possible to  collect  and  evaluate  data from  a  full-field
treatment area  for  ISS  sites.    However,  as  indicated  in  Table  6:1, the
effectiveness in  accurately  evaluating treatment  processes is  generally low.
This is due  to  the difficulty  in  accounting  for and controlling  sources  of
variation in  sampling and treatment  in full field evaluations.


                                   109

-------
Table 6.1.  Comparison of Field Verification Alternatives.
                                     Field Verification  Alternatives
                              Barrel  Lysimeter   Held  Scale       Full
Factor                           or Box Plot         Plot         Field
                                            comparison  Scale
Representativeness

     Simulation of climate,   Moderate            Moderate         High
       soils, and operations

Effectiveness in Evaluating
Treatment Processes

     Degradation              Moderate            Moderate         Low
     Transformation           Moderate            Moderate         Low
     Immobilization           Moderate            Moderate  '       Moderate
     Toxicity                 High                High             Low
     Integrated Effects       Moderate            Moderate-High    Low

Implementation Aspects

     Variability control       High                Moderate         Low
     Reproducibility          Moderate            Moderate         Low
     Cost                     Moderate            Moderate         High
     Design/management
       problems               Moderate            Low              High
6.3  SELECTION OF DESIGN AND MANAGEMENT  PARAMETERS


     Acceptable  design  parameters  (loading rates,  loading frequencies  and
application  methods),  and  operation  and management  options  have  been
established at many of the land  treatment  facilities currently operating under
Interim status.   These  established design and  management  options can be used
for the LTD.   If a  new  facility is planned, methods  discussed  in this manual
(Chapters 2 and  5)  may  be used  to determine acceptable design parameters and
operation and management options.   Loading rates  in field verification studies
should not result  in  concentrations  of  metals  in the soil  greater than those
recommended by the U.S.  EPA (1983a),  as  discussed in Section 2.5.

     The field  test should  accurately  simulate  the  site  characteristics and
operating conditions, including  waste,  climate,  topography,  soils, treatment
zone  characteristics  and  likely  operating  practices.   Results  from the
laboratory studies  and  model predictions,  summarized as  Cb/Tb  for  each

                                   110

-------
constituent (Section 4.3), may be  used to  select one waste  application design
(loading rate, loading frequency and application method) and field management
scheme  (soil  pH,  soil  moisture,  chemical  reaction,  nutrients  and mi.crobial
activity)  that  will  be  evaluated   in the   field.    More  .than  one
design/management combination may  also be evaluated  at  the discretion of the
permit  writer.    The  purpose  of  the  field  plot  study  is to  verify  the
effectiveness  of  the  selected  design  and  management options  under  field
conditions.  Replication of each waste  application  and field management scheme
to be  tested  is  highly recommended.  The field study should be conducted for
at least one  seasonal  cycle for ISS units  and 1-2 years for  a  new facility,
depending  on  recommendations of the  permit writer and results  of the  first
year study.  The study should be conducted until a  50 percent reduction in the
initial concentration  is  experimentally  observed  for  a  majority of hazardous
constituents.    Special  attention  should be  given to  short-term leaching
effects  (generally  one week  to three months  after waste  application,  with
sampling closely following precipitation  events).

6.4  ANALYTICAL ASPECTS OF FIELD VERIFICATION

     The design  plan  should  identify  proposed  statistical  testing approaches
for the field  verification  study.   The analytical  approach to the monitoring
and analyses  of  field  samples  involves  the  use  of Type  III  Identification
technology  (GC/MS)  and  Type  II  monitoring technology  (GC,  HPLC).   Type III
analyses should  be  conducted  at  the beginning, middle,  and end  of the  field
verification  study.   Metals  analyses  should  also be conducted  to determine
accumulation of metals in the soil  profile.  After initial  waste application,
at least 5  percent of  each  sampling media analyzed  with  type II methodology
should also  be  analyzed  with  Type  III technology  to  verify that  the
identification  and  monitoring  results  agree  with respect to constituent
Identification.  The PHCs selected  should be monitored through time with Type
II technologies.

     Monitoring  analyses should  also include  toxicity testing of the  zone of
incorporation (ZOI) and below  treament zone (BTZ)  samples  using the Microtox
assay  or other  appropriate  bioassays  (see  Chapter 5).   Bioassays  of  the ZOI
will  be used to evaluate the relative detoxification of  the soil-waste mixture
with time.   Bioassay of BTZ  samples will  be used  as an  indicator of hazardous
constituents  leaving  the  treatment zone.   If carcinogenicity is  of  concern
with the PHCs  present in a  waste, the mutagenic  potential  of the soil-waste
mixture should  be  monitored  using  a  mutagenic  assay  such   as  the  Ames
Salmonella  microsome assay (Chapter 5).

     Analytical costs for the  field verification  study  may be estimated from
Table  2.6.   Results of  the  field  verification study should  be  evaluated  and
Interpreted using the  statistical  methods discussed in Appendix B.

6.5  PLOT PREPARATION

     "Uniform area" has been defined  as  an area  of the active  portion  of  a
HWLT unit composed of soils of the  same  soils  series  to which similar wastes
are applied at  similar  rates (Chapter 3).  A  rigorous  soil  survey will  have
been conducted as part of  the reconnaissance study  for the HWLT unit such that

                                      111

-------
those soil  properties  that affect  treatability  of  waste  types have  been
identified and those areas with similar treatability characteristics have been
classified  as uniform.   The  number  of  field  plots  should  be based  on  the
number of uniform areas.  Replication of field plots is recommended especially
for  barrel  lysimeter  or  box  plot  studies.   Soil monoliths  for  barrel
lysimeters and  sites for box  plots  should be chosen  from uniform areas  for
field  scale  plots.   Locations of field  scale plots  are also determined  by
choosing  uniform areas based  on  the site  soil  survey.   Ease of  access  and
isolation from  existing  waste  treatment  facilities should  be  considered.
•Plots should be  chosen to represent slope and drainage conditions.

     The  size  of a box plot,  barrel  lysimeter, of  field  scale plot may vary.
Box plots are generally 5x5  feet to allow for easy application of wastes.   A
barrel  lysimeter  is  usually constructed  from  a  55  gallon  drum.   Details
concerning the collection of barrel  sized undisturbed  soil lysimeters  may  be
found  in  Brown  et  al.  (1985).  The smaller  the  plot, the more  difficult  it
will be to evaluate leaching using soil-pore liquid  samplers.

     The  size  and  location of field  scale plots  should, however,  reflect  full
scale field operation  application methods and equipment usage.  The  size  and
shape of  a field scale plot  may  vary.   For example, if a tractor  with a 10  ft
manure spreader  is  to  be  used for  waste application,  a plot  that is  10 ft  or
20 ft  wide  would  accommodate  the method  of application.   The  total  areas  of
the  plot  should  be at  least 550 ft2.   Experimental  field  plots should  be
isolated   from  existing  waste treatment areas  using  berms  around  plots  to
eliminate cross-contamination  and runon/runoff.   Berms need to be  high  enough
to contain or  eliminate  specified  storm-water flow events, as required  under
Section 264.273(c).  It is not necessary to physically separate plots  intended
to receive the same waste loading and frequency.   Similar considerations would
apply for box plots, which should be  protected from  runon/runoff.

     Barrel  lysimeters  should be sheltered  from  normal  precipitation  (e.g.,
with  an open-sided  pole  barn); water should  be applied in specified  amounts.
The site water budget may be  useful in  terms  of water  added via other sources
(e.g.;  irrigation).    After  calculated  losses due to  runoff/evaporation  have
been subtracted, appropriate  amounts of water may be  applied  according  to the
precipitation record.

     Run-off  collection  can  be  accomplished at  field scale  plots  in  small
sumps or  impoundments at the low slope  position of each plot.   The size  of the
collection area  is  calculated based on  the water balance  computed  for the
site.  Run-off collection ponds should  be designed to  contain  run-off  from the
24 hr/25 yr storm.  The LTD plan should address managment of excess runoff.

     The  use  of control  plots on previously treated  soil for  ISS  sites  is
recommended to  allow estimation of  longer term  degradation,  transformation,
and immobilization of  hazardous constituents  already  in the soil.  A control
plot  is  not  necessary for  a new site,  since background  conditions can  be
defined adequately from the test plot receiving wastes.
                                   112

-------
 6.6  WASTE APPLICATION

     Waste  application  practices used  or planned for  use on the  full-scale
 land treatment  unit  should  be  used  for field   verification" studies.
 Incorporation  of  waste  should  be accomplished with the  same type  of equipment
 used on  the land treatment units,  and  corresponding  tilling  practices  should
 be used.

     To  apply waste to  a  barrel  lysimeter  or  box  plot, the  zone  of
 incorporation  should first  be removed  and  carefully  homogenized with  the
 applied waste.  A plastic barrier can be laid around  the edge of the casing or
 box  to prevent side  channel flow.   The  soil-waste mixture  is  then  replaced in
 5  cm or small lifts, tamping  each successive layer   if necessary,  to achieve
 field bulk density.

     Normal  tillage  and deposition  practices  do not  ensure  a  uniform
 distribution in field scale  plots.   Variability in the waste distribution in
 the  ZOI for  field scale  plots  may be reduced by either  of two methods.  A pug
 mill or cement mixer  could be used to mix the ZOI soil  and  waste,  followed by
 careful application  to  the  soil.  Care must be taken in  using tilling, since
 large discontinuous blocks of soil containing little  or  no waste may be raised
 to the soil surface.  Alternatively, applied  wastes could  be tilled  repeatedly
 until a desired  uniformity  is achieved.   Random  sampling should  be  excluded
 from areas near the edge of the plot on all  sides.

 6.7  FIELD VERIFICATION STUDY MONITORING

     A hazardous  organic  constituent of  a waste  may be volatilized,  sorbed,
 degraded, or leached  in  the soil system.   The  goal   of  land  treatment  is  to
maximize  sprption and degradation  processes while minimizing volatilization
 and migration losses.  Field verification plot monitoring  consists  of:

     - soil-core  sampling, for monitoring degradation, immobilization, and
       transformation of hazardous constituents  in  soils with  depth;

     - soil-pore  liquid  sampling, for monitoring  losses  of  hazardous
constituents in soil-water below the treatment zone;

     - groundwater sampling,  for monitoring contamination  of groundwater.

     Volatilization is not specifically  addressed  in  field verification plot
monitoring, because of the lack of guidance in 40  CFR  Part  264.

     Evaluation of results should be  conducted  during the performance of the
LTD to allow for any necessary modifications  of the monitoring schedule.

     An example of a  sampling schedule for a hypothetical land treatment unit
is given in Appendix 6.
                                   113

-------
 6.7.1      Collection  and  Analysis  for  Soil Core
           and  Soil  Pore Liquid  Sample??

 6.7.1.1   Soil  Core-
     Analysis  of soil  cores is necessary to  monitor the behavior of hazardous
 constituents  present  in  the treatment  zone, to  identify  possible degradation
 products,  and to  detect  slowly  migrating  hazardous  constituents  below  the
 treatment  zone.

     For  barrel   sized  lysimeters, Dr.  K.  W.  Brown  of Texas  A&M  University
 should be  contacted for details on monitoring treatment in the lysimeters.

     For  field scale  plots, soil  cores may be divided  into four sections:   1)
 the  zone of  incorporation  (ZOI); 2) an upper  treatment  zone  (TR1);  3)  a lower
 treatment  zone  (TR2);  and  4)  below  treatment  zone  (BTZ),  as  described  in
 Chapter  3.  Soil  survey  information  may  indicate  other  subdivisions  of  the
 soil  core based  on soil  properties  relevant  to  waste treatment.   Zone  of
 incorporation  (ZOI) soil  samples and  soil  cores  should  be  collected  at  random
 on each  plot  with  the  appropriate sampling  device.   Details  concerning  soil
 sampling  are  discussed  in Section 3.4.2.   U.S.  EPA (1984)  provides  guidance
 for  selection  of the appropriate devices for specific soil  types.

     The  monitoring schedule  should  be designed  to  sample  soil   cores  at
 frequent  enough  intervals to determine  whether  a  waste is  being treated  and
 whether  hazardous constituents  are  passing  below  the treatment zone.    To
 determine  initial concentrations of hazardous constituents  in the zone,  a  soil
 sample should  be  taken  immediately  after the  initial  waste  application  and
 incorporation  and following  each  application thereafter.   The  frequency  of
 core  sampling  should be  based  initially  on mobility  and degradation rates
 determined  in  the  laboratory studies  and predicted  for  field conditions using
 the  proposed  or  similar model.   This periodic evaluation of  the soil cores
 between  the   ZOI  and BTZ  is  made  to  determine  the  extent  of mobility  of
 hazardous  constituents  within  the treatment zone.   At  specific times,  the
 entire soil  core to some  point below  the treatment zone (e.g.,  30  cm)  should
 be analyzed to determine  if  any hazardous  constituents, including degradation
 products have migrated down the soil  profile.   Once a data  base is established
 on the  mobility  and  degradation of  hazardous  constituents  under  field
 conditions,  the  sampling  schedule should  be re-evaluated  and  modified,   if
 necessary.   If  hazardous  constituents  are  evident at  greater depth than
 predicted, sampling should  be done more frequently.  If there  is no  evidence
of movement, sampling may be performed less frequently.

     The  number  of samples  to  be collected  for analysis from  each plot  is
dependent on the expected  variability in soil-waste treatment within  each plot
 and  on the margin of  error  that is acceptable for the study,  as  discussed  in
 Appendix B and in Mason (1983).   Information  from the reconnaissance  study and
 past analysis of ISS units can be used to help judge the representativeness  of
 field verification plot data.  It is  estimated  that a minimum of  three t.o five
 samples  per  plot  will  be  required.    Separate sample  cores  should  not   be
composited before analysis.  Composited core  samples may not  only show a lower
 variability, but  also the  true  frequency distribution  of  the raw data  may  be
distorted.  Much  information may be lost by compositing  samples.

                                       114

-------
      The  practice of  averaging  data within a  plot  may also lead  to  loss  of
 essential  information.    Within  a plot,  where  there  has  been improper
 application  of waste or misjudgment of variability within the plot; averaging
 results may  mask  the presence  of "hot  spots."   Data may be presented by using
 histograms,  or any method  which  illustrates sampling point variance.

 6.7.1.2  Soil-Pore Liquid  Sample Collection and Analysis-
      Percolating  water added  to  the soil  by  precipitation,  irrigation,  snow-
 melt, or  waste applications may pass  through  the treatment  zone  and  rapidly
 transport  some mobile  waste constituents  or degradation  products  through  the
 unsaturated  zone  to  the groundwater.  Soil-pore liquid monitoring  is intended
 to  detect  these pulses of contaminants since  they may not be observed  through
 the analysis of soil  cores.

      By monitoring  soil-pore  liquid,  the rate  and  extent of  waste movement
 through the  soil  can be determined.  If waste is migrating out of the treat-
 ment  zone, the waste  application should  be modified  and  corrective measures
 taken.

      A discussion of types of  samplers, installation procedures,  and cautions
 for use are  given in the Permit  Guidance Manual on Unsaturated Zone Monitoring
 for Hazardous  Waste  Land Treatment  Units (U.S.  EPA 1984b).

 6.7.1.3  Soil  Pore Liquid  Sampler:   Vacuum Type--
    ' Vacuum  soil-pore Itquid  samples may be divided  into  two types (U.S.  EPA
 1984b):    (1)  vacuum  operated  soil-water  samplers;  and  (2) vacuum-pressure
 samplers.   Soil-pore  liquid  samplers  generally  consist of  a ceramic  cup
 mounted on the end  of a small-diameter PVC tube,  similar to  a  tensiometer.
 The upper  end  of the PVC tubing projects  above  the soil surface.  A rubber
 stopper and  outlet tubing  are  inserted  into the  upper  end.   Vacuum  is  applied
 to  the  system  and  soil water moves into the  cup.    To  extract  a sample,  a
 small-diameter  tube  is inserted  within the outlet tubing  and extended to  the
 base of  the  cup.   The  small-diameter  tubing  is  connected  to  a  sample-
 collection flask.  A vacuum is applied via a hand vacuum-pressure  pump  and the
 sample is  sucked  into  the collection flask.  These units are  generally  used to
 sample to  depths  up  to 6 feet  from the land surface,   consequently, they  are
 used  primarily to monitor  the near-surface movement  of  pollutants from the
 HWLT.

     To extract  samples from  depths greater  than  the suction lift of  water
 (about 25  feet),  a vacuum-pressure  lysimeter  may be  used.   These  units were
 developed by  Parizek  and Lane  (1970)   for  sampling the  deep  movement of
 pollutants from a land  disposal project.  The  body tube of the unit  is  about  2
 feet  long, holding  about  1 liter  of  sample.   Two  copper  lines   are forced
through a  two-hole rubber  stopper  sealed  into a body  tube.   One copper line
 extends to the base of the ceramic cup as shown  and the other terminates  a
 short distance below the rubber stopper.  The  longer line  connects to a sample
bottle and the  shorter  line connects to a vacuum-pressure  pump.  All Tines and
connections  are sealed.  In operation,  a vacuum  is applied to the system (the
 longer  tube to  the  sample  bottle  is  clamped shut  at this time).   When
sufficient time  has  been  allowed  for  the unit  to fill  with  solution, the


                                  115

-------
vacuum  is  released and the clamp on the outlet  line  is  opened.   Air pressure
is then  applied  to the system, forcing the sample  into  the  collection  flask.
A basic  problem  with this unit  is that when  air  pressure  is applied,  some  of
the  solution  in  the  cup  may  be  forced  back  through  the  cup  into the
surrounding  pore-water system.   Consequently, this  type  of  pressure-vacuum
system is recommended for depths only  up to about 50  feet  below  land surface.
A modification of this type of  sampler utilizes  a  check valve to  prevent the
liquid being forced out of the cup during application  of pressure.

     Factors  such as rate of  water  extraction,  plugging of the pores of the
samplers, and sorption and screening effects by ions can produce  as much  as  60
percent range  in sample  concentrations in  vacuum type  soil  pore liquid
samplers (Hansen  and Harris 1975).   Many of these problems may be  reduced  or
eliminated  by  proper installing  of samplers,  selection  of  appropriate
samplers, type of  vacuum  used, and proper sealing of  all connections (Parizek
and  Lane  1970;  U.S.  EPA 1984b).    Vacuum  type samplers  have been  used
extensively for  studies of the movement of major  inorganic cations  and anions
through the soil  profile.   The literature is lacking information  in  the use  of
vacuum type  samplers  for  organic constituents in soil.  Unanswered  questions
concerning their use include:   are organic  compounds sampled  by these types  of
devices; are they sorbed  or screened by the  porous materials;  is plugging a
problem  with  oily wastes;  and  how can volatile  organics  be sampled without
loss  in  a  vacuum system?   The  Permit  Guidance  Manual on  Unsaturated  Zone
Monitoring for Hazardous Waste Lan? Treatment  Units  (U.S. EPA 1984b)  discusses
these problems and proposes solutions.       '.

     Timing of sampling is critical  with  these sampling devices,  requiring the
use  of  soil moisture  measurement devices,  such  as  tensiometers  or neutron
probes.  As the water front moves through the  soil profile, the tensiometer  or
probe will  indicate  when  the wetting  front  is at  the  depth of  the sampler.
Samples should be  collected at this  time to ensure that the sample  is of the
water  and  waste  constituents  moving through  the  soil  profile  and is  not
stagnant soil-pore water.

6.7.1.4  Pan-Type Soil  Pore Liquid  Sampler--
     Vacuum-type   soil  liquid  samplers, as  discussed  above,  are  made of fine
porous materials  that  form  a  continuum with small  soil pores.   If water and
associated  hazardous  constituents  move uniformly through  the  small  pores  of
soil  matrix as they infiltrate, the movement of hazardous constituents may be
readily  evaluated  using  these  types of samplers.    Water  soluble  hazardous
constituents percolating through soil  may,  however, bypass much  of the total
soil  mass and thereby would not be  collected by porous samplers.  The movement
of water  through  large  pores, bypassing the smaller  pore  system  has  been
reported by  Kissel et  al.  (1973),  Tyler and  Thomas  (1977), Quisenberry and
Phillips (1976, 1978),  Thomas  et  al.  (1978)  and Shuford et  al.  (1977).

     The mechanism visualized  for water movement  through  soil  is  that  of  a
dual-pore soil  system.   The first set of pores are  a continuum of small pores
while the  second  set,  often  termed macropores,  may   appear 1n  the "form  of
cracks in  shrink-swell  clays,  as  earthworm  and old root holes,  or  as
interaggregate pores and interpedal voids (Wagenet et  al. 1983; Shaffer et al.
1979).   Macropores may be responsible for bulk water  and associated  hazardous

                       i            116

-------
constituents  moving  through  distinct  isolated  areas of  soil  with  little
interaction with  the water  inside  of  small  pores.   Simpson and  Cunningham
(1982) have shown that rapid  flow of  wastewater  through interpedal  cracks  may
lessen the renovating capacity of the soil because of reduced surface area  and
contact time.  Similarly,  because of  the  rapid  flushing of pollutants through
large interconnected  pores,  the movement  of such pollutants  into finer  pores
of the  soil  may be  limited.   An opposite  consequence of macropore  flow,  as
suggested by Thomas and Phillips (1979), is that hazardous constituents in  the
small pores of surface soil  will  be bypassed  by rapidly moving water and will
remain at or near the soil surface.

     Macropore flow  1s  of particular  importance  in well-drained  shrink-swell
soils with  large  pores and  cracks  at high water  content.    This  phenomenon,
however,  is  not  limited  to  such soils but can  occur at  interfaces  between
adjacent soil peds (Richie et al. 1972; Thomas and Phillips 1979)  and at  water
contents  well  below  field  capacity (Aubertin  1971: Quisenberry  and  Phillips
1976).   At present,  there is  not  sufficient  information  in the  literature
defining  the  soil  properties and  water  regimes where macro-pore  flow will
occur to the extent  that  predictions  of waste-soil  interaction and  flow  rates
based on  Dare 1 an  theory  are grossly  incorrect.   For  this  reason,  macropore
sampling devices should be included in field verification studies.

     Macropore sampling devices,  consisting of  various types of pan samplers,
have been  described  by Shafer et al.  (1979),  Parizek  and  Lane  (1970),  Tyler
and Thomas (1977), and U.S. EPA (1984b).  The reason for using pan samplers is
to confirm whether large quantities of leachate are flowing through structural
macropores and possibly bypassing much of the  treatment capacity of the soil.
Pan  samplers  collect  rapidly moving  water because  the  sampler  acts  as  a
textural  discontinuity in  the  soil  profile,  forming  a  perched water  table
above the  pan  surface.   Water then  flows  through holes in  the top  surface to
be collected  and  stored  in  the collection area.   This type  of  flow usually
only lasts  a  few  minutes to  a  few  hours  after irrigation  or a precipitation
event occurs (Thomas  and Phillips 1979), so samples should be removed within a
limited time period  (less than 24 hr) to prevent sample quality changes within
the  pan.   The  Permit  Guidance Manual  on  Unsaturated  Zone  Monitoring  for
Hazardous  Waste Land  Treatment  Units  (U.S.  EPA 1984b) should be consulted  tor
details  on pan-type  samplers andinstallation  procedures.   The U.S.  EPA is
presently  investigating several new designs of pan  samplers.

     The  number  of each  type of sampler  needed for each  field  scale plot is
dependent  on  the  expected  variance  in soil-waste  treatment  within  each plot
and  on  the margin of error that  is  acceptable  for  the study (Mason 1983).  A
discussion of  this technique  1s  presented  in Appendix B.   A minimum of  two
each of  vacuum-type  and  pan-type soil pore liquid samplers is recommended  for
each field plot.

     Barrel lysimeters should have  a  soil-pore liquid  sampler installed at  the
base  of each  barrel monolith.   Leachate  should  first  be generated  in  the
barrel   lysimeters  to  define background  leachate  quality.   A  tracer  study
should  be conducted  to  evaluate  possible sidewall  flow  and short-circuiting
that may bias  subsequent  soil-pore  liquid analysis  (Brown et  al. 1985).
                                    117

-------
6.7.2  Groundwater Monitoring

     The use of ground water monitoring is not explicitly required in a land
treatment  demonstration.   However,  Section 264.272(c)(3)(v)  requires
consideration of the potential  for migration to ground or surface water.  At
the discretion  of  the  regulatory agency,  it  may  be  appropriate  to  include
ground water monitoring  in the field verification study design.  At a new site
without ground water monitoring  protection, temporary monitoring wells may be
installed adjacent  to the field plot area.

6.7.3  Data Interpretation

     Field  plot studies  should  be designed  to monitor  hazardous  waste  land
treatment performance.   Data collected from  soil  core, soil-pore  liquid, and
groundwater sampling for monitoring  purposes may be compared  with results of
model  evaluations.   Because of the complex nature of  field  plot  studies and
the  extreme variance   in  environmental factors,  such as  temperature,
precipitation, soil properties,  etc.,  quantification  of  degradation,
transformation, and immobilization for  prediction  of  field  performance  is
difficult  at  the  present time.   Results  of  field  plot monitoring   should
demonstrate no movement  of hazardous constituents  out  of the treatment zone.
If losses  are noted, treatment  practices should be modified  to  prevent
continued migration.

     Since metal  loading  limits  in  soils   have been  established,  the
accumulation  of  metals in the field verification plots  should be monitored and
compared to  those  limits shown  in Tables  2.4  and  2.5, in  order to determine
site life based  on  metal loading rate.
                                  118

-------
                                                            0SWER POLICY DIRECTIVE MO.
                                  CHAPTER 7

               QUALITY ASSURANCE PROGRAM FOR CONDUCTING AN LTD


     An  integral  part of an  LTD  design is a quality  assurance (QA) program
 to  ensure that  data collected can  be evaluated  and  interpreted  with con-
 fidence.   An  adequate  QA program requires that  all  sources of error asso-
 ciated  with  each step of the experimental  study or monitoring and sampling
 program  be  identified and quantified.   The most highly developed aspects of
 QA  programs  are for  laboratory analytical  procedures.   However,  in an LTD,
 the treatment medium, i.e.,  the soil, may be extremely  non-homogeneous.  Soil
 samples  taken  only several  feet apart my  exhibit different  soil characteris-
 tics  or may differ  in chemical  pollutant concentrations by an  order of
 magnitude.  Therefore QA  on analytical  results  is  a necessary but not suffi-
 cient condition for  assessing  total  sample  variability within a soil that is
 being sampled  or  used in a laboratory  investigation.   The  analytical errors
 may account for  only a small portion of the total variance  (Barth and Mason
 1984).  High quality soil sampling is required  to minimize total variance.

     A  complete QA  program  should  include  sample site  selection,  sample
 collection, sample  handling,  and  analysis and  interpretation  of  resulting
 data.   Quality of results  obtained  are assured in two ways:   1)  providing
 control   of various  steps  in  the sampling  and analytical  processes,  from
 sample  collection  to data  interpretation;  and  2)  providing adequate repli-
 cation for statistically determining  and quantifying the sources of variation
 or error in the sampling and analytical  processes.

     A  QA  program  consists  of a  system of documented  checks which validate
 the reliability of a  data set.  It is  implemented  as a set  of basic sampling
 and measurement procedures  and corresponding quality control checks.  Neces-
 sary elements of a QA program include:

     1.    Adherence  to  documented,  proven analytical methodology and  QC
 procedures;

     2.    Performance of sampling and  analytical  activities by  qualified,
 trained  individuals;

     3.    Maintenance of  laboratory  physical facilities and sampling  equip-
ment;

     4.   Data recording,  handling,  storage,  and  retrieval, including sampling
 analytical performance parameters,  in a  scientifically  sound manner.

     A high  quality  set  of data  should  include the  following measures  of
 sampling and analytical  performance:

           '                        119

-------
      1.  Accuracy - measure of closeness of a measurement  to  the true value;

      2.   Precision  -  measure of  the probability that  a measurement  will
 fall  within certain confidence limits;

      3.   Sensitivity  -  a) determination of the method detection  limit,
 which is the  lowest concentration  of a particular  chemical constituent
 that  can be measured  reliably  in  a sample, and b)  determination  of  the
 limit  of detection, which  is the  lowest  concentration  level that  can  be
 determined to be statistically different from a blank;

      4.   Representativeness - assurance  that the sample being analyzed
 is a  subset of a set and  has  the average characteristics of the set;

      5.  Completeness -  a  data recovery level which will adequately charac-
 terize the existing  condition  that is being monitored.

     The QA  program for an  LTD should include procedures  which address
 the reconnaissance investigation,  laboratory analyses  and studies,  and
 field plots.   If literature  data  and/or  information are used  as part of  an
 LTD,  an  assessment of the  representativeness and  quality  of the  information
 is recommended.  Specifically,  the QA plan  should address:

     1.  A  detailed flow  scheme of  the  work to be  performed  during the
 LTD program;  individuals  responsible  for each specific  test  procedure,
 including chemical  analysis  and  data  interpretation;  approximate  dates  of
 sampling and analysis.

     2.  Detailed procedures -to ensure the collection of representative soil
 or  waste samples;   procedures  for  a sample  receipt  log  that will  include
 Information  on  storage conditions, sample  distribution, and  sample  identi-
 fication.

     3.   A master  schedule for tracking  all  samples  through  the analytical
 program. This schedule  should  include  the test performed,  individual respon-
 sible, and dates of  initiation and completion.

     4.   Standard operating procedures (SOPs) which outline specific details
of each test  procedure and associated  QA/QC  requirements.

     5.   A plan for  data handling  and  interpretation, including data obtained
from literature and  from laboratory and/or field experiments.

     6.   A  report  for each waste  used  in  the LTD that includes  the study
protocol, a  complete set of raw data for  each  test  procedure, the individ-
ual (s) generating the data,  and the data  generating dates.

     Information concerning QA/QC  procedures  and  guidance for the prepara-
tion of a QA  program may be obtained from the  following documents:

     1-   Soil  Sampling Quality Assurance User's Guide  (Barth and  Mason
1984).	


                                   120             !

-------
     2.      Methods  of  Soil Analysis.   Part 1:   Physical  and Mineralogical
Properties  (Black  1965).~

     3.      Handbook for Analytical Quality Control  in  Water and Wastewater
Laboratories  (U.S.  EPA 1979a).

     4.   Test  Methods for Evaluating Solid Waste,  SW-846  (U.S.  EPA 1982b).

     5.   Methods for Chemical Analysis of Water and Wastes (U.S.  EPA 1979b).

     6.   "Guidelines for  Data  Acquisition  and  Data  Quality Evaluation
in Environmental Chemistry" (ACS 1980).

     7.    "Elements  of  a  Laboratory  Quality Assurance  Program"   (Dressman
1982).

     8.      Guidelines  for  Quality  Assurance/Qua!ity Control  Program   (U.S.
EPA 1980).

     9.   User's Guide to the Contract Laboratory  Program  (U.S. EPA 1984c).
                                   121

-------
                                  REFERENCES


APHA.   1985.   Standard methods for the examination of water and wastewater.
     Sixteenth edition.  American  Public Health Association, Washington, DC!

ACS.   1980.   Guidelines  for  data acquisition and  data quality evaluation
     in  environmental  chemistry.   American  Chemical  Society  Committee  on
     Environmental Improvement.  Analytical  Chemistry 52:2242-2249.

Alexander,  M.   1977.   Introduction to soil  microbiology.   Second Edition
     John Wiley and Sons, New York, NY.

Anderson, J.  P.  E., R.  A. Armstrong, and  S.  N.  Smith.   1981.   Methods  to
     evaluate pesticide damage to  the biomass of  the soil  microflora.  Soil
     Biol. Biochem. 13:149-153.

Atlas,  R. M., and R.  Bartha.   1972.  Degradation and mineralization  of
     petroleum by  two bacteria  isolated  from  coastal  water.   Biotechnol.
     Bioeng. 14:297-308.

Atlas,  R.  M., and  R.  Bartha.    1981.   Microbial  ecology,  fundamentals and
     applications.   Addison-Wesley, Reading, MA.

Atlas,  R.  M., D.  Pramer,  and R.  Bartha.    1978.   Assessment  of  pesticide
     effects on non-target soil microorganisms.   Soil Biol.  Biochem. 10-231-
     239.

Aubertin, G. M.   1971.   Nature and extent  of macropores  in  forest  soils and
     their influence on subsurface  water movement.  USDA For. Serv.  Res. Pap.
     NE-192.  Northeast.  For. Exp.  Stn., Upper Darby, PA.  33 p.

Barth,  D.  S., and  B.  J. Mason.   1984.  Soil  sampling quality assurance
     user's  guide.   EPA-600/4-84-043,  Environmental Monitoring Systems Labor-
     atory,  U.S.  Environmental  Protection Agency, Las Vegas,  NV.

Bartha,  R.,  and D.  Pramer.   1965.   Features of a flask  and method  for mea-
     suring  the  persistence and   biological  effects  of  pesticides.    Soil
     Sci. 100:68-70.

Beckman  Instruments,  Inc.  1982.   Microtox*  system operating manual.  Micro-
     bics Corp.,  Carlsbad,  CA.

Belser,  L. W., and E. L.  Mays.   1980.  Specific inhibition of nitrite oxida-
     tion by  chlorate  and  its use in assessing nitrification  in  soils and
     sediments.   Appl.  Environ. Microbiol. 39:505-510.

     !                               122

-------
Black, C.  A.  (Ed.).   1965.   Methods  of soil analysis,  Part  1:    Physical
     and  mineralogical  properties,  including  statistics of measurement and
     sampling.    Monograph #9,  American  Society of  Agronomy,  Madison, WI.

Brown, K.  W., and  K.  C. Donnelly.   1984.  Mutagenic activity of runoff and
     leachate  water from  hazardous  waste land treatment.   Environ. Pollut.
     (Series A),  35:229.

Brown, K.  W., J.  C.  Thomas,  and M.  W.  Aurelius.   1985.  Collecting and
     testing barrel  sized undisturbed soil  monoliths.    Soil  Sci.  J.  Am.
     49:1067-1069.

Burks, S.  L.,  M. Amalon,  E.  F. Stebler, J.  Harmon,  F. Leach,  M.  Sanborn,
     and  J. Matthews.    1982.   Comparison of  acute  response  of Microtox1",
     Daphnia  magna,  and  fathead   minnows to  oil refinery wastewaters.
     Progress  Report  to  Oil  Refiners'  Waste  Control   Council  by  Oklahoma
     State  University,  Water  Quality  Research Laboratory, Stlllwater,
     OK.

Burns, R. G. (ed.).  1978.   Soil enzymes.   Academic  Press,  London, England.

Carnahan,  8.,  H.  A.  Luther,  and  J.  0.  Wilkes.    1969.   Applied numerical
     methods.  John Wiley  &  Sons, New York, NY.  604 p.

Casida,  L. E.,  Jr.   1968.  Methods  for the isolation and estimation of
     activity  of  soil  bacteria,  p. 97-122.  In_J.  R.  G. Grey and D. Parkinson
     (Eds.).  The  ecology of  soil  bacteria.   Liverpool  Univ. Press, Liver-
     pool,  England.

Casida, L.  E., Jr.  1977.   Microbial  metabolic activity in soil as  measured
    by dehydrogenase determinations.   Appl.  Environ.  Microbiol. 34:630-636.

Casseri, N. A., W. Ying, and  S. A.  Soiyka.  1983.   Use of a rapid  bio-
     assay  for assessment of  industrial  wastewater  treatment effectiveness,
     p. 867-878.   In J.  M. Bell (Ed.).  Proceedings  of the 38th Indus-
     trial  Waste Co~nTerence,  Purdue  University,  Ann  Arbor Science, Boston,
     MA.

Clapp, R.  B.,  and  G.  Hornberger.   1978.   Empirical  equations  for some  soil
     hydraulic properties.   Water Resources Research  14:601-604.

Dressman, R. C.   1982.   Elements of a laboratory quality  assurance  program.
     p. 69-75.   Proc.  of AWWA Water Quality Technology Conference, Nashville,
     TN,  Dec.  5-8,  American Water Works Assoc., Denver, CO.

Focht, D.  D., and  W.  Verstraete.   1977.   Biochemical  ecology of nitrifica-
     tion and  denitrification.   Adv.  Microbial  Ecol.  1:135-214.

Frankenberger,  W.  T.,  Jr., and W.  A. Dick.    1983.   Relationships between
     enzyme activities  and  microbial  growth and activity  indices  in  soil.
     Soil Sci. Soc.  Am.  J. 47:945-951.
                                   123

-------
 Gano  K. A.,  D  W.  Carlile, and  L.  E. Rogers.   1985.   A  harvester ant

      b^/V^n °r*assessing nazard°us chemical  waste sites.   PNL-5434
      Battelle Pacific Northwest  Laboratory, Richland, WA.



 Gansecki,  M.    1986.   Personal   communication.   Region VIII,  U.S   Environ
      mental Protection Agency, Denver, CO.                           tnviron-
       wMMH           -ie*' J' A'  P<  Marsh'  and 6' '• Wlngfleld.  1976
      Herbicides and  soil  microorganisms.   CRC Crit.  Reviews  Microbiol.





      fh "'  PV "•  A.  Davles. J.  A.  P.  Marsh,  and G.  I  Wingfield.   1981

      Effects of pesticides on  soil microflora using  Dalapon  as  an example'
      Arch.  Environm. Contam. Toxicol.  10:437-449.                    example.
      rAnl'/;Vand A'  R' Harr1s'   1975'    Val^ity  of  soil-water samples
      collected  by porous ceramic cups.  Soil  Sci.  Soc.  Am. J. 39:528-536.



      lS^  .fn'nc'   <19-i9R-  1Variati°nD of four  P^sphorus properties  in  wood-
      land  soils.   Soil Biology and Biochemistry  11:393-403.
      nt   iE"  3nd  *,'  L' T.empl.e'   1979'    Comparison  of  ATP phosphatase,
      pectinolase,  and respiration  as  indicators  of microbial activity

      in  reclaimed coal strip mine spoils.  Soil Sci. 127:70-73.


 Hindin,  E., D  S. May, and G.  H.  Dunston.  1966.  Distribution of insecticide

      sprayed by  airplane  on  an  irrigated  corn plot.   p.  132-145.   Chapt   11

      in  Organic  Pesticides  in the  Environment.   A. A.  Rosen  and  H.  F.  Kray-

            e  I' h-  *ancenr1n  Chemistr*  Ser1'es  #60.  American Chemical
               wasmngton, DC.
 Indorato, A. M.  L. B. Snyder, and P. J. Usinowicz.  1984.  Toxicity screen-

      ng  using  Microtox"  analyzer, p.  37-53.   In  D.  L.  Lui and B.  J.  Dutka

     n ?u'}' wvToxlc1ty Screenin9  procedures  usTFTg  bacterial  systems. Marcel
             NT*
Jury, W   A.   W  F. Spencer, and  W.  J.  Farmer.   1983.   Behavior  assessment

     model for  trace  organics  in  soil:   I. Model description.  J. Environ.

     Qua! . 12(4): 558-564.



Kada, T.,  K. Hirano,  and  Y.  Shirasu.   1978.   Screening  of environmental

     chemical mutagens by the REC assay systems with Bacillus subtil is.  In

     v  I  Jv a           J'    Chemical  mutagens,  Vol.  ^   Plenum  Press, New
     T Oi K 9 Ml*



Kafer, E., B.  R.  Scott, G.  L.  Dorn, and  R.  Stafford.   1982.  Aspergillus

     mdulans:   Systems  and results of  tests for chemical induction  of

     mitotic  segregation  and mutation.    I.  Diploid  and  duplication  assay

     systems.   A Report  of the  United States Environmental  Protection

     Agency Gene-Tox Program.  Mutation Research  98:1-48.



Kenney,  D. R.,  and  D.  W.  Nelson.   1982.  Nitrogen-inorganic  forms,  p.  643-

     698.  _In A. L. Page  (Ed.).   Methods of  soil  analysis, Part  2.   Second

     edition. Am. Soc. Agronomy, Inc., Madison,  WI.




                                     124

-------
King,  E.  F.   1984.   A comparative study of  methods  assessing  the toxicity
     to  bacteria  of  single  chemicals  and  mixtures, p.  175-194.   _In_  D.  L.
     Lui  and  B.  J. Dutka  (Eds.).   Toxicity screening  procedures  using bac-
     terial systems.  Marcel  Dekker, NY.

Kissel, D.  E.,  J.  T.  Ritchie, and  E. Burnett.   1973.   Chloride movement  in
     undisturbed swelling clay soil. Soil Sci. Soc. Am. J. 37:21-24.

Klein,  D.  A., T.   C.  Loh,  and R. L. Golding.   1971.   A  rapid  procedure  to
     evaluate the  dehydrogenase  activity  in soils  low  in  organic  matter.
     Soil Biol.  Biochem. 3:385-387.

Ladd,  J.  N.   1978.  Origin  and  range of enzymes  in  soil, p.  51-96.    In  R.
     G. Burns (Eds.).   Soil  enzymes.   Academic Press, London, England.

Lyman,  W.  J., W.  F. Rechl,  and  D.  H. Rosenblatt.   1982.   Chemical  property
     estimation  methods.  McGraw-Hill, New York.

Malkomes, H.-P.   1980.   Stohrotteversuche zur erfassurg von  herbizid-
     nebenwirkungen ant den  strohumsatz  im  boden.  Pedobiologia 20:417-427.

Maron,  D.  M., and  B.  N.  Ames.   1983.   Revised methods  for  the  Salmonella
     mutagenicity  test.  Mutation Research 113:173-215.

Mason,  B.  J.   1983.    Preparation  of soil  sampling  protocol:    Techniques
     and  strategies.    EPA-600/4-83-020,  Environmental   Monitoring  Systems
     Laboratory, U.S.  Environmental  Protection Agency, Las Vegas, NV.

Mathur, S.  P.,  and R.  B. Sanderson.   1978.   Relationships  between  copper
     contents,  rates  of soil respiration and  phosphatase activities  of
     some  histosols  in  an   area  of southwestern Quebec  in  the  summer and
     the fall.  Canadian J. of Soil  Science  58(5):125-134.

Matthews,  J.  E.    1983.   Toxicity  reduction  screening  procedure  for  deter-
     mining  land treatability of hazardous  wastes.   lr\_  Abstracts  from the
     SETAC  Annual   Meeting,   Multidisciplinary Approaches to  Environmental
     Problems.  Arlington,  VA.  November.

Matthews, J.  E., and  A.  A.  Bulich.   1985.   A toxicity reduction test  system
     to assist  in  predicting land treatability of hazardous  organic  wastes.
     In Proceedings 4th ASTM Hazardous  and Industrial  Waste  Testing  Sympo-
     TTum, Arlington,  VA.   American Society of  Testing  and Materials.
     Philadelphia,  PA.

Matthews, J.  E., and  L.  L. Hastings.   1985.  Evaluation  of  a toxicity test
     procedure for  use  in  screening land treatability  potential.   Presented
     at the  Second International Symposium on  Toxicity Testing  Using Bac-
     teria.  Banff, Alberta,  Canada.  May 6-10.

Mausbach,   J.  J.,  B.  R.  Brasher, R. D.  Yeck, and W.  D.  Nettleton.   1980.
     Variability of measured properties  in morphologically matched  pedons.
     Soil  Science  Society of  America J. 44(2):358-363.

                                    125

-------
 McKown, M.  M.f  J.  U.  Warner,  R.  M.  Rlggin,  M.  P.  Medley,  P.  E. Heffelfinger,
      B. C.  Garrett, G. A. Jungclaus, and T.  A.  Bishop.   1981.  Development of
     methodology for the evaluation of solid wastes,  Volume  I.  Final Report
     EPA  Contract  No.  68-03-2552,  U.S. EPA,  Effluent  Guidelines  Division'
     117 p.

 Neuhauser,  E.,  R.  Loehr,  and J. Martin.   1983.   The  effect  of industrial
     wastes on soil biota.  Final Report to  U.S. EPA, Robert S. Kerr Environ-
     mental Research Laboratory,  Cooperative Agreement (R-809285-01).

 Parizek, R.  R.,  and B.  E.  Lane.  1970.  Soil-water  sampling  using pan  and
     deep pressure-vacuum lysimeters.   J. Hydrol.  11:1-21.

 Page,  A.  L. (Ed.).   1982.   Methods  of soil  analysis.   Part 2:   Chemical
     and microbiological properties.  American Society of Agronomy,  Madison,
     W A •

 Plumb, R.  H., Jr.   1984.  Characterization  of  hazardous  waste sites--a
     methods manual:   Volume  III.   Available laboratory analytical  methods.
     EPA-600/4-84-038,  Environmental  Monitoring  Systems  Laboratory,   U.S.
     Environmental  Protection  Agency,  Las Vegas, NV.

 Porcella,  D. B.  1983.   Protocol for bioassessment of hazardous waste sites.
     EPA-600/2-83-054.   Corvallis  Environmental  Research Laboratory,  Cor-
     vallis, OR.

 Pramer, D., and R.  Bartha.   1972. Preparation  and processing of soil samples
     for biodegradation studies.   Envir. Lett.  2:217-224.

 Provost,  L. P.   1984.   Statistical methods  in environmental  sampling.
     p. 79-96.   In Environmental  Sampling for  Hazardous  Wastes.  G.  E.
     Schweitzer aful  J.  A.  Santolucito  (eds.).   ACS  Sympsoim  Series 267,
     American Chemical  Society, Washington, DC.

 Quisenberry, V. L.,  and R.  E.  Phillips.    1976.  Percolation  of surface
     applied water  in  the field.   Soil Sci. Soc. Am. J.  40:484-489.

 Qjisenberry, V.  L.,  and R.  E.  Phillips.  1978.  Displacement  of soil  water  by
     simulated  rainfall.   Soil Sci. Soc. Am.  J. 42:675-679.

 Qureshi,  A. A., K.  W. Flood,  S.  R.  Thomson,  S.  M. Janhurst, C. S.  Inniss,
     and  D.  A.  Rokosh.  1982.   Comparison  of a  luminescent bacterial  test
     with  other  bioassays  for determining  toxicity of  pure compounds  and
     complex effluents, p.  179-195.   ln_ J. G. Pearson,  R.  B. Foster,  and
     M. E.  Bishop (Eds.).  Aquatic Toxicology  and  Hazard  Assessment:  Fifth
     Conference.  ASTM STP 766.   American Society  for Testing  and Materials.

Rao,  P. V.,  P.  S.  C.  Rao, J. M.  Davison,  and L. C. Hammond.   1979.   Use
     of goodness-of-fit tests  for characterizing  the spatial variability  of
     soil properties.   Soil Science Society of America J.  43(2):274-278".

Ritchie,  J.  T.,  D. E.  Kissel,  and E.  Burnett.   1972.   Water movement  in
     undisturbed swelling clay soil.  Soil Sci.  Soc. Am.  Proc.  36:874-879.

                                   126

-------
Scott, B.  R.,  G. L.  Dorn,  E. Kafer,  and  R.  Stafford.   1982.   Aspergill us
     nidulans:   Systems and  results of  tests  for induction  of mi to tic
     segregation and  mutation.   II. Haploid assay  systems  and overall
     response of all  systems.   A Report of the  United States Environmental
     Protection Agency Gene-Tox Program.  Mutation Research 98:49-94.


Shaffer,  K. A., D.  D. Fritton,  and D.  E. Baker.   1979.   Drainage water
     sampling in a wet, dual-pore soil system.   J. Environ.  Qua!. 8:241-246.


Shattuck,  G. E., and M. Alexander.  1963.   A  differential  inhibitor of
     nitrifying microorganisms.   Soil  Sci. Soc. Am. Proc. 27:600-601.


Short, T.  E.   1985.   Mathematical   modeling  of  land   treatment  processes.
     Invited paper  presented  at  the  National  Specialty Conference on Land
     Treatment,  University of  Texas at Austin,  Austin, TX, April  16-18.


Short, T.  E.  1986.   Modeling  of  processes  in  the unsaturated zone, p.
     211-240.  _l£ R. C. Loehr and J.  F. Malina, Jr.  (Eds.).   Land treatment:
     A hazardous waste management  alternative.   Water Resources Symposium  No.
     13,  Center for Research  in  Water Resources,  The Universoty  of Texas at
     Austin, Austin,  TX conference.


Shuford,  J.  W.,  D.  D.  Fritton,  and   D. E.  Baker.   1977.   Nitrate-nitrogen
     and  chloride  movement  through   undisturbed   field  soil.   J. Environ.
     Qua!.  6:736-739.


Simpson,  T. W.,  and  R.  L.  Cunningham.  1982.  The occurrence  of flow channels
     in soils.   J. Environ.  Qua!.  11:29-30.


Sims, R. C.   Loading  rates  and  frequencies for   land treatment  systems,  p.
     151-170.  J_n_ R. C. Loehr and J.  F. Malina, Jr.  (Eds.).   Land treatment:
     A hazardous  waste management  alternative.   Water Resources Symposium  No.
     13,  Center for Research  in Water Resources,  The University  of Texas at
     Austin, Austin,  TX,  April  16-18.


Sims, R.  C., D. L.  Sorensen, J. L. Sims,  J. E. McLean,  R. Mahmood,  and R. R.
     Dupont.  1984.   Review  of  In  Place Treatment Techniques  for  Contaminated
     Surface Soils.   Volume  2:  Background Information for In Situ Treatment.
     EPA-540/2-84-003b.    Municipal  Environmental  Research Laboratory, U.S.
     Environmental Protection Agency,  Cincinnati,  OH.


Skujins,  J.   1973.    Dehydrogenase:   An  indicator of biological  activities
     in arid soils.   Bull. Ecol. Res.  Commun. (Stockholm) 17:235-241.


Skujins,  J.   1978.   History of  abiotic soil  enzyme  research, p.  1-49.   J[n_
     R. G.  Burns (Ed.).   Soil enzymes.    Academic  Press, London, England.


                                    127

-------
 Slattery,  G.  H.   1984.   Effects of toxic  influent  on PATAPSCO  wastewater
     treatment  plant  operations.   Presented  at the Annual  Conference of  the
     Water Pollution Control  Federation,  New Orleans,  LA, October 1-4.

 Soil  Conservation Service.   1983.   National  soil  handbook.   430-VI-NSH.
     U.S.  Department of Agriculture, Washington,  DC.

 Sorensen,  D.  L.   1982.    Biochemical  activities  in  soil  overlying Paraho
     processed  oil  shale.    PhD  Dissertation,  Colorado  State  University
     Fort  Collins, CO.

 Stotzky,  G.   1965.   Microbial  respiration, p.  1550-1572.   In  C. A. Black
     et  al.  (Eds.).   Methods of  soil analysis,  Part 2.  Am.36c.  of Agron-
     omy  Inc., Madison, WI.

 Strosher,  M.  T.   1984.   A  comparison of biological testing methods in  as-
     sociation with chemical analysis to evaluate toxicity of waste drilling
     fluids  in  Alberta,  Vol.   I.    Canadian  Petroleum  Association  Report,
     Calgary, Alberta, Canada.

 Strosher, M. T., W. E.  Younkin, and  D. L. Johnson.  1980.  Environmental  as-
     sessment of the terrestrial disposal of waste drilling muds in Alberta.
     Canadian Petroleum Association,  Calgary, Alberta, Canada.

 Swisher, R., and  G.  C.  Carroll.  1980.   Fluorescein diacetate hydrolysis as
     an  estimation of  microbial  biomass on  coniferous  needle  surfaces
     Microbial  Ecology 6:217-226.

Thomas, G.  W.,  and R.  E. Phillips.   1979.   Consequences  of  water movement
     1n macropores.  J.  Environ. Qual. 8:149-152.

Thomas, G. W.,  R.  E.  Phillips,  and V.  L. Quisenberry.   1978.   Characteriza-
     tion of water displacement  in soils  using  simple chromatoqraphic theory.
     J. Soil Sci.  29:32-37.

Tyler,  D.  D.,  and G.  W.  Thomas.   1977.   Lysimeter measurements of  nitrate
     and chloride  losses  from   soil  under conventional  and  no-tillage  corn.
     J. Environ. Qual.  6:63-66.

U.S. EPA.   1979a.   Handbook for analytical   quality  control  in  water  and
     wastewater   laboratories.     EPA-600/4-79-19,  Environmental   Monitoring
     and Support Laboratory,  Cincinnati,  OH.

U.S. EPA.   1979b.  Methods  for  chemical  analysis of water  and  wastes.   EPA-
     600/4-79-020.    Environmental  Monitoring  and  Support  Laboratory,  U.S.
     Environmental  Protection Agency, Cincinnati, OH.

U.S. EPA.  1980.  Guidelines for quality assurance/quality  control  prograns.
     QAMS-005-80,  Environmental  Monitoring  Systems  Laboratory,  U.S. Environ-
     mental Protection Agency, Las  Vegas, NV.
                                    128

-------
U.S.  EPA.   1982a.   Methods for  organic  chemical  analysis  of municipal  and
      industrial  wastewater.   EPA-600/4-82-057,  Environmental  Monitoring  and
      Support  Laboratory,  U.S.   Environmental  Protection  Agency, Ci/icinnati,
      OH.

U.S.  EPA.  1982b.  Test methods for evaluating  solid waste:   Physical/
      chemical methods.   Second  Edition.   SW-846.   Office of Solid Waste and
      Emergency  Response,  U.S.   Environmental  Protection  Agency, Washington,
      DC.

U.S.  EPA.  1983a.  Hazardous waste land  treatment.   Revised Edition.  SW-874.
      Office of Solid Waste and  Emergency  Response,  U.S. Environmental Protec-
      tion Agency, Washington, DC.

U.S.  EPA.  1983b.   RCRA  guidance  document:   Land  treatment units.  Office of
      Solid Waste, U.S. Environmental  Protection Agency, Washington, DC.

U.S.  EPA.   1984a.   Permit  applicants'   guidance  manual  for  hazardous waste
      land  treatment,  storage,   and disposal  facilities.   EPA-530/SW-84-004.
     Office of Solid Waste and  Emergency  Response,  U.S. Environmental Protec-
      tion Agency, Washington, DC.

U.S.  EPA.  1984b.   Permit guidance manual on  unsaturated zone monitoring  for
      hazardous waste land treatment units (draft).   EPA/530-SW-84-016, Office
     of  Solid  Waste  and. Emergency  Response, U.S.  Environmental  Protection
     Agency,  Washington,  DC.
U.S.
U.S.
EPA.   1984c.   User's guide
of  Emergency  and  Remedial
Agency, Washington, DC.
to the contract laboratory program.   Office
 Response.'   U.S.   Environmental  Protection
EPA.   1985a.   Guidance for the analysis of refinery wastes.   Office of
Solid  Waste and  Emergency  Response,  U.S.  Environmental Protection
Agency, Washington, DC.
U.S.  EPA.   1985b.   Permit writers' guidance  manual for  the location  of
     hazardous  waste  land treatment facilities:   Criteria for location
     acceptability  and  existing  applicable  regulations.    Office of  Solid
     Waste, U.S. Environmental  Protection Agency, Washington, DC.
U.S. EPA.  1985c.  Petitions to
     Office of  Solid  Waste and
     tection Agency,  Washington,
                           delist hazardous wastes:
                           Emergency  Response,  U.S.
                           DC.
                         A guidance manual.
                         Environmental  Pro-
Vasseur, P.,  J.  F. Ferod,  C.  Rost, and  6.  Larbaight.   1984.   Luminescent
     marine bacteria  in ecotoxicity screening  tests  of complex  effluents.
     p. 23-37.   Jin D.  L.  Lui  and  B.  J.  Dutka (Eds.).  Toxicity screening
     procedures using  bacterial systems.   Marcel Dekker, NY.

Wagenet, R. J.   1983.  Principles  of  salt  movement 1n soils,   p.  123-140.
     In_ D.  W. Nelson,  D. E. Elrick, and K. K. Tanji (eds.).  Chemical  Mobil-
     ity and Reactivity in  Soil Systems.   Spec. Pub. 11, Soil Science Society
     of America,  Madison, WI.
                                     129

-------
Weber, J.  8.    1971.    Interactions of  organic  pesticides with participate
     matter in aquatic  and  soil  systems, p.  55-120.   In R. F. Gould (Ed )
     Fate of  organic  pesticides  in aquatic  environmerff.   Am.  Chem  Sor
     Washington,  DC.                                                 '  JUl"'

White, G.  C.,  and T.  E.  Hakonson.   1979.   Statistical  considerations  and
     survey of  plutonium concentration variability  in  some terrestrial
     ecosystem components.  J. of Environmental Quality  8(2):176-182.

Wollum,  A. G.,  II.    1982.    Cultural methods  for soil microorganisms   D
     781-802.  j£ A. L.  Page (Ed.).   Methods  of soil analysis,  Part  2
     Second edition.  Am. Soc. of Agronomy,  Inc., Madison, WI.
                                  130

-------
                                 Appendix A

             SUMMARY OF TREATMENT DEMONSTRATION PERMIT APPLICATION

                   INFORMATION REQUIREMENTS (U.S. EPA 1984a)


I.   Treatment Demonstration Plan

    A.  Wastes for  treatment demonstration plan

       1.  List  of all  wastes (hazardous and nonhazardous)  included  in  the
           treatment demonstration

           a.  Common name and EPA hazardous waste ID number
           b.  Generating process
           c.  Expected monthly quantity
           d.  Form of waste and approximate moisture content

       2.  List  all  potentially hazardous constituents (Appendix  VIII)  and
           pertinent nonhazardous constituents in wastes listed in I.A.

       3.  Quantitative analysis of each waste listed in I.A.

           a.  Concentration  of  each hazardous  constituent listed in  I.B.
               based  on  boiling  point  ranges  (25"C,  25  to  105"C,  105  to
               250'C, and > 250VC)
           b.  Percent water content
           c.  Specific gravity or bulk density
           d.  pH
           e.  Electrical conductivity
           f.  Total acidity or alkalinity
           g.  Total organic carbon

    B.  Data  sources of treatment demonstration

       1.  Identify  information  sources for  data  used in  treatment  demon-
           stration

       2.  Description of data from each  source  and  how data are to  be  used
           in  treatment demonstration

    C.  Laboratory  and field test design

       1.  Laboratory tests

           a.  Name of test
           b.  Objective of test
                                   131

-------
             c.  Step-by-step materials and methods
             d.  Schedule of completion
             e.  List of full scale operating characteristics  that  are or are
                 not simulated in test
             f.  List of data to be obtained in  test  along  with  final form of
                 of data presentation

         2.  Field tests

             a.  Objective of test
             b.  Scale drawing showing location  of  test plots  with respect to
                 proposed land treatment  unit
             c.  Number and size of test  plots
             d.  Horizontal and vertical  dimensions of the  treatment zone
             e.  Statistical  design of test
             f.   Preparation  activities for test plot(s)
             g.  Waste application rate on  each  plot
             h.   Irrigation method and scheduling
             i    Methods  for establishing  and maintaining  vegetation  if
                 applicable
             j.   Methods for  monitoring  and recording daily  meteorological
                 data
             k.   Monitoring procedures for:  soil,  soil-pore liquid, surface
                 runoff, vegetation,  groundwater, and air as applicable
             1.   Daily schedule of events and activities
             m.   Rationale for design  and  management of field tests to  pre-
                 clude hazardous constituent migration to  ground  or surface
                 waters
             n.   List of data to be obtained  in test along with final form  of
                 data presentation
             o.   Clean-up procedures  upon completion of field tests

II.   Treatment Demonstration  Results

     A.  Wastes  and waste composition

             Information regarding wastes different from those  specified  in
        Treatment  Demonstration Plan using criteria  of I.A. above.   Include
        pretreatment or mixing  activities utilized.

     B.  Degradation/transformation

             Information on rate and extent of degradation/transformation of
        specific hazardous constituents  as well as bulk organic fraction of
        waste(s).

        1.   Existing literature data

             a.  Brief written review of  scientific  literature  and  previous
                studies
             b.  Documentation  of  sources of information in text and  biblio-
                graphy


                                   132

-------
         c.  Description of test procedures and results as per II.B.3 or
             II.B.4 as appropriate

     2.  Operating  data

         a.  Description of existing  facility,  operating  records,  waste
             composition,  waste  application  rate(s),   and  data  demon-
             strating degradation of  hazardous  constituents  and/or  bulk
             organics
         b.  At  minimum provide  analytical results of  soil  sampling for
             hazardous  constituents  and  plot  percent degradation  or
             transformation  as a function  of time for  each  waste  appli-
             cation treatment

     3.   Laboratory test results

         a.   Name of test
         b.   Test procedures including laboratory apparatus,  experimental
             design,  waste  application rate(s),  preparation  and  handling
             of  soil  and  waste(s),  analytical  methods,  sampling  pro-
             cedures,  and all  test conditions
         c.   Test results  including  tables  and/or graphs specific  to the
             test  method  utilized, along with  the  half-life  of  each
             organic  hazardous constituent calculated  from  experimental
             data
         d.   Discussion  and interpretation of results

    4.   Field test results

         a.   Field  test objectives
        b.   Field  test  procedures  used  including physical plot charac-
            teristics,  soil and  waste properties, etc., and any and  all
            changes  from  procedures described  in  the  Treatment  Demon-
             stration Plan
        c.  Field  test  results  in  form of tables  and  graphs to demon-
            strate  degradation  or  transformation  of  organic hazardous
            constituents.    Include  analytical  results, plot of percent
            degradation/transformation versus  time, half-life of hazard-
            ous constituents in  the  treatment  zone, and application rate
            providing optimal  treatment  performance.

C.  Immobilization

        Information  on  potential for organic  and  inorganic  hazardous
    constituents to migrate  from  treatment  zone  under  typical  waste
    application rates and  operating  conditions.

    1.  Existing literature  data

        a.  Brief  written review of scientific  literature and previous
            studies
                               133

-------
         b.   Documentation of  sources  of  information  in  text  and  biblio-
             graphy
         c.   Description  of  test  procedures  and results  as  per -II.c.3
             below

     2.   Operating data

         a.   Description  of  existing facility, operating records, waste
             composition, waste  application rate(s),  and data reflecting
             the mobility of hazardous constituents
         b.   Sampling  procedures and  analytical  methods  should  be  in-
             cluded  with  monitoring data  presented  in detail described
             in II.C.4 below

     3.   Laboratory test results

         a.   Name of test
         b.   Test objectives
         c.   Test procedures  including laboratory apparatus, experimental
             design,  waste application rate(s), preparation and handling
             of  soil   and  waste(s),  analytical  methods,  sampling  pro-
             cedures, and all  test  conditions
         d.   Test results including tables and/or graphs specific to the
             test method utilized
         e.   Discussion and  interpretation  of results

    4.   Field test results

        a.  Field test objectives
        b.  Field test procedures  including  physical  plot characteris-
            tics, soil  and waste properties,  etc.,  and any and  all
            modifications from  procedures described  in  the  Treatment
            Demonstration Plan
        c.  Field test  results in the form  of tables and  graphs  to
            demonstrate  the  rate   and  extent  of hazardous  constituent
            migration  during  the field test

D.  Volatilization

        Information  on  potential  for volatilization of hazardous  con-
    stituents from the treatment  zone which  is  not  considered  degrada-
    tion, transformation  nor  immobilization.    Extensive  quantitative
    information is not required If•It can be  shown  that volatilization
    will  not be a  significant release mechanism for the  hazardous
    constituent of concern.

    1.  Existing  literature data

        a.  Brief written review of  scientific  literature  and  previous
            studies
                               134

-------
        b.  Present results  as  vapor  pressure  (mm Hg),  and  estimated
            flux  (mass/area)  versus time,  along  with  other  pertinent
            values as appropriate
        c.  Document sources  of  information  in text and bibliography

    2.  Operating data

        a.  Description of existing  facility, operating  records,  waste
            composition,  waste application rate(s),  and data reflecting
            volatilization potential  of hazardous constituents
        b.  Description of  sampling  procedures  and analytical  methods
            along with monitoring data

    3.  Laboratory test results

        a.  Name of test
        b.  Test procedures including laboratory apparatus, experimental
            design,  waste application rate(s),  analytical  methods,
            sampling procedures, and  all test conditions
        c.  Test results including graph  showing mass  of hazardous
            constituent volatilized  per unit area  as a function  of time
           .for various application rates
        d.  Discussion and interpretation of results

    4.  Field test results

        a.  Field test objectives
        b.  Field test procedures including  physical  plot characteris-
            tics, soil  and waste  properties,  etc.,  and any and  all
            modifications  from  procedures  described  in  the  Treatment
            Demonstration  Plan
        c.  Field test results  in form of tables  and   graphs  to  demon-
            strate the flux of  hazardous  constituents  (mass/area)  as  a
            function of time for various application rates

E.  Microbial toxicity

        Information  on toxicity  of  applied waste to soil  microorganisms
    to ensure maintenance  of biodegradation within the  treatment  zone.

    1.  Existing literature data

        a.  Brief written review of  scientific  literature  and previous
            studies
        b.  Document source of information in text  and  bibliography

    2.  Operating data

        a.  Description  of existing  facility, operating records,  waste
            composition,  waste  application  rate(s),   and  data  showing
            relative  microbial   activity  as a function of  time for
            various  concentrations of waste in the  soil


                              135

-------
    b.  Sampling  procedures
        monitoring  data

3.  Laboratory test results
                                   and  analytical  methods  along  with
    a,
    b,
            Name of test
            Test procedures including  laboratory apparatus, experimental
            design,  waste  application rate(s), analytical methods,
            sampling procedures,  and all test conditions
        c.  Test results  including tables or graphs  that  show relative
            microbial  activity as a function of time for various concen-
            trations of waste in  soil
        d.  Discussion and interpretation of results

    4.  Field test results

        a.  Field test objectives
        b.  Field test  procedures including physical  plot  characteris-
            tics, soil  and  waste properties,  etc., and  any and all
            modifications  from  procedures  described  in  the  Treatment
            Demonstration  Plan
        c.  Field test  results  in the form of  tables and graphs that
            demonstrate  relative  microbial  activity  as  a function of
            time at various  waste application  rates or operatinq con-
            ditions                                     .

F.  Phytotoxicity  "

        Information  on phytotoxicity of nonbiodegradable  hazardous
    constituents immobilized in the treatment zone or vegetative cover
    during the  operating  life of the  facility to  planned  cover crop
    following closure  of land treatment facility.

    1.   Existing literature data

        a.   Brief  written  review  of  scientific  literature and previous
            studies
        b.   Document source of information  in text  and  bibliography .
        c.   Include information such  as  plant species,  waste application
            rates, and test procedures

    2.   Operating data

        a.   Description  of  existing  facility, operating  records,  waste
            application  rate(s),  and data  showing the toxicity  of  the
            waste
        b.   Sampling   procedures  and  analytical  methods  along with
            monitoring data

    3.   Laboratory test results

        a.   Test  procedures  including  apparatus,  experimental  design,
            waste  application  rate(s), waste  application  schedule,  and
           plant varieties
                         136

-------
    b.  Test results should show the  concentration  of  waste  in the
        soil that causes  a  specified decrease in plant growth

4.  Field test results

    a.  Field test objectives
    b.  Field test  procedures  including  physical  plot  characteris-
        tics, soil  and  waste properties,  etc.,  and  any and all
        modifications  from  procedures described  in the  Treatment
        Demonstration Plan
    c.  Field test  results in  the  form  of  tables  or graphs  that
        demonstrate the concentration of waste  and  waste constitu-
        ents  that  cause a  specified  decrease  in  plant  growth  or
        survival
    d.  Discussion and  interpretation  of results
                           137

-------
                                   APPENDIXB

           STATISTICAL CONSIDERATIONS FOR THE  PERFORMANCE  OF  AN  LTD


 INTRODUCTION

     The  information  obtained  in aN LTD  should be  representative of  the  soil
 and soil/waste system  if it is to be useful, for the results may have  profound
 health  and  economic consequences.   The  sampling  designs used  should  provide
 information  of maximum  reliability and  minimum  cost.   Statistical  plans,
 Including  knowledge  of the  expected  variability  and  confidence  limits  of
 analytical  methods  used, sampling  designs  employed, and data  interpretation
 procedures  used, must  be  incorporated  into  the  LTD  from  the  beginning.  It  is
 highly  recommended  that  the applicant secure  the services of  a  statistician
 familiar  with  the  design  of  sampling and  monitoring  studies to prepare  the
 sampling design plan for the reconnaissance investigation.

     Statistics  are required  when  data  are  collected and  analyzed  to make
 judgments about  some  population  attribute.   Statistical   analyses may  be  used
 to estimate some overall property  (e.g.  mean  value  of  hydraulic  conductivity,
 concentration of a waste constituent, etc.), the pattern  of distribution  (e.g.
 soil pH distribution over  a  field), for  comparison purposes (e.g.,  testing
mean differences of treatment  versus background), and in experimental design
 (e.g.,  study  of  degradation rates  over time).    Two  critical  problems  in
 statistical  design  are the assurance  of the collection  of a  representative
 sample and the ability to make accurate inferences from the  sample data to the
 population.

 COLLECTION OF REPRESENTATIVE
 SAMPLES

     One of  the key characteristics of a  soil  system that  should be recognized
by the applicant is the  extreme  variability in soil properties (Mason 1983).
Mason summarizes available information on soil  variability as expressed by the
coefficient  of variation  in the following manner:

      Coefficients  of  variation  for soil  parameters have been reported
     ranging from as  low as 1 to  2 percent to as  high  as 850 percent.
     White  and  Hakonson  (1979),  for example,  noted  that the  CV for
     Plutonium in  the soils of  a number of  test sites  ranged  from 62
     percent  to  840  percent.   Mathur and  Sanderson   (1978)  reported
     coefficients for natural   soil  constituents  (i.e., part  of  the soil
     itself) varying from 5.6% to 75.2%.  Harrison  (1979) evaluated four
     phosphorus properties  of  soil  and  reported  CV values  ranging from 11


                                   138

-------
      percent  to  144 percent with the highest values being  for  available
      P.   Hindin  et al.  (1966)  reported  a  CV of  156% for  insecticide
      residue  concentrations  in  a square  block of  soil  that  was  30  .inches
      on  a side.

          Mausbach  et  al.  (1980)  reported on a  study conducted by the
      Soil  Conservation Service  (SCS)  laboratory in  Lincoln,  Nebraska.
      Matched  pairs of  samples  were collected from  areas  within a soil
      series.  The  samples were stratified by a number of factors  in order
      to  reduce the  variability.   The  samples  were  collected  from the
      modal  phase of the series  and  were collected  at distances  that
      ranged  from 2 to 32 km from  the  other members  of  the  pair.  The
      authors  note  that the literature indicates that  up  to half of the
      variability may occur  within a distance of one  meter.  (Studies are
      now  underway  at  Lincoln to determine variability  within  this  one
      meter  distance.)    Mausbach et  al.  (1980)  reported that  in  their
      study of the  variability within  a  soil type,  the CVs for  physical
      properties  ranged from 9  to  40% for loess, 23  to 35% for glacial
      drift, 33 to 47% for alluvium  and residuum, 18 to 32% for the A and
      B  horizons,  and  33  to  51% for  the  C  horizons.   The CVs  for the
      chemical properties tended  to  be higher, ranging from 12 to 50% for
      Alfisols, 4 to  71% for Aridisols,  6 to 61% for Entisols, 10 to 63%
      for Inceptisols,  9  to  46%  for  Mollisols,  16  to 132% for Spodosols,
      10 to 100% for Ultisols, and 8 to 46% for Vertisols.

      This soil variation must be taken into consideration during  the design of
a  sampling  and  surveying  plan.   A  single  sample or  a  single composite sample
will  not provide information on  the  types of  pollutants  present nor the routes
of  migration of  the   pollutants.   Compositing  assumes  that  the  soil  or
soil/waste system  being  investigated  is  virtually  homogeneous  and therefore
the  number  of  analyses required  and the  associated  costs can be  reduced.
Compositing obscures variability in a measurement, and information  about this
important property of  the  population  will  be lost.   Statistical  technologies
designed  to  account  for  variation  must  be   included  in  any  soil
characterization study.  The sample  arithmetic mean may be used as an estimate
of  central  tendency,  while  the variance  (or  its  square  root value,  the
standard deviation) may be used  to measure variability.

      In  situations  where  little  is known  about  the  distribution  of  a
population parameter,  nonparametric tests and  evaluations  are  used to  make
inferences.    If enough  1s known  about  a parameter to  Indicate  that  its
behavior can  be approximated by a parametric  model  such  as  a normal,  log
normal, or Poisson distribution, the  use of  parametric models  is preferable.
In particular, the  theoretical normal  distribution has been well described and
Its  properties  have been  extensively  tabulated.    Making   Inferences  is
relatively  straightforward  if  normality can  be  assumed.    Many naturally
occurring linear variables  are  well approximated  by this distribution.   For
many  other environmental variables, a transformation of  data  using  a.square-
root  or  logarithmic transformation,  will yield an  approximately  normal
distribution.  Examples of soil  parameters  following the normal and  log  normal
distribution are shown  in Table  B.I.
                                   139

-------
 Table  B.I    Frequency Distribution of Soil Properties (Rao et al.  1979,
             Barth  and Mason, 1984).
          Soil  Property
                                        Type of Frequency Distribution
 Bulk Density
 Organic Matter Content
 Clay Content
 Soil-Water Content at a Given Tension
 Air Permeability
 Saturated Hydraulic Conductivity
 Soil-Water Flux
 Pore-Water Velocity
 Solute Dispersion Coefficients
                                                  Normal
                                                  Normal
                                                  Normal
                                                  Normal
                                                  Log normal
                                                  Log normal
                                                  Log normal
                                                  Log normal
                                                  Log normal
     Even if a distribution is itself nonnormal,  the  sample  averages from such
a  population  are often  normally  distributed.    The  student-t  test relies on
this  basic  Central  Limit  theorem to  allow  comparison  of  mean  sample
differences  from  nonnormal  populations.    Finally,  the robustness  of tests
using the normal distribution can  handle moderate departures from normality.

     An important consideration is whether or not a given variable  under study
is  distributed  randomly or  nonrandomly.   Use of normal  approximations
presupposes a  random variable, that  is,  a variable whose  individual  sample
values are defined only by their probability of occurrence.  Individual sample
values are independent  of  one another.   By contrast, values from  a nonrandom
variable taken  close  together in  time  or space   will  exhibit  relatedness  or
covariation.    Many environmental  variables will contain  both a  random  and
nonrandom component.

SAMPLING DESIGNS
     Four  basic  statistical  sampling  designs  may be  used in  soil  studies:
simple random,  stratified  random,  systematic,  and  judgmental  sampling.
Complete explanations of each of these  designs  are presented in Preparation of
Soil Sampling Protocol;  Techniques and Strategies (Mason 1983).  The type of
sampling design chosen for the reconnaissance investigation should be reported
to the permit writer and included in  the permit application.
     A random sample is
equal  and  independent
Random samples are selected
factor of  selection.   In
selection of any particular
each  member  of  the  soil
                        any sample in  which  the probabilities of selection are
                        of  the other members  that comprise  the  population.
                            by some method that uses chance as the determining
                            simple  random  sampling of  soils,  the chances  of
                            segment of the soil system must be the same, i.e.,
                            population  must  have  an  equal  probability  for
selection.  A  random  location sampling  plan is  appropriate if  the  parameter
distribution is itself expected to be random.  Simple random sampling may not
                                  140

-------
give the  desired  precision  because  of  the large  statistical  variations
encountered  in  soil  sampling.   Therefore one of the other designs may be more
useful.                                                            -   -

     The  number of  samples necessary to  attain required  information may  be
reduced  by  the use of  stratified random  sampling.    The sampling  area  is
divided  into smaller,  more homogeneous  subareas called  strata.   These strata
 are defined by some  identifiable boundary that 1s based  on  topography,  soil
 chemical  or physical properties,  or  some stratigraphic  feature.   This is the
 technique  most  likely to be used in the analysis of waste distribution in the
 soils  at  a  land  treatment  unit, since the definition  of "uniform  areas"  is
 required  at the site for  further sampling efforts  and  study.   The use  of
 uniform areas should lead to increased  precision if the  subareas selected are
more homogeneous than the total  population.   Within  a uniform area, sampling
 is conducted as with the simple random sampling.

     The  systematic sampling plan  provides  better  coverage of the soil  study
 area than  does  the simple random  sample when  spatial variability is expected.
 Samples are collected in a regular pattern  (usually  a  grid or line transect)
over the  areas under  investigation.   The  starting point  is  located  by some
random  process, then all other  samples  are  collected  at regular  intervals  in
one or more directions.   The  orientation of  the  grid  lines  should  also  be
randomly selected.

     Judgmental  sampling  is  usually used in  conjunction  with  one  of  the  other
methods in order to include areas of  unusual  patterns,  (e.g.,  pollutant  "hot
spots").   However, when used by  itself,  this  approach, is subject  to  bias and
may  lead to  faulty conclusions.   If judgmental  sampling  is used,  duplicate  or
triplicate samples should be taken to  increase.the- level  of  precision.   Data
from judgmental  sampling  areas  should be identified.

NUMBER OF SAMPLES

     A  larger  number  of  samples usually  results  in  a better  estimate  of
properties of a population.   However,  the cost of  sampling and analysis  also
must be considered  in  sample design.   In the  performance of an LTD, which
requires sample measurements  for many constituents and  properties of  wastes,
soils,  soil-pore  liquid,  and  groundwater,  techniques  to  minimize sample
numbers should  be  employed.

     For many types of random variables, the  t-statistic  is  used  to  estimate
confidence levels  of the  true population mean  for  small  sample  sizes;  similar
techniques  are   used to  estimate  the  population variance.   In general, the
smaller the  sample, the wider is the confidence interval  in which  a population
mean 1s expected to lie for a given probable level  of confidence.   For  certain
comparisons  in  experimental studies, it  is necessary  to  reduce  the confidence
interval (i.e.,  increase confidence)  in order to evaluate  the  reliability  of
the results.  Generally,  the confidence  level  is controlled through choice  of
an appropriate  sample size.

     To determine  the number of samples required,  the  use of a  statistical
procedure incorporating the estimated  variability of concentrations or levels


                                    141

-------
 of soil or  waste  constituents of  interest, the desired  level of confidence of
 the data, and a specified level  of precision (or allowable margin of error to
 be met  by the results)  is  recommended.   One such  procedure  is  described in
 fr5.P.aratJon. of  .S°n  SamP11nq  Protocol;   Techniques  and  Strategies  (Mason
 1983).Further  information  on  the use of this technique as well  as tabu!ar
 solutions to required statistical  formulas are given in Soil Sampling Quality
 Assurance User's Guide (Barth and Mason  1984).
      Mason (1983) describes the statistical technique  in the following manner:

           If an estimate of the variance can be obtained from either
      a preliminary experiment,  a pilot  study, or from the literature,
      the number of samples required to obtain a given precision with
      a specific confidence  level  can  be obtained  from the following
      equation:
           n
      where  D  is  the  precision  given in  the  specifications of  the
      study,  s^ is  the sample variance,  and  t is the  two-tailed  t-
      value  obtained  from  the standard  statistical  tables  at  the a
      level  of significance  and (n-1)  degrees  of freedom.   D  is
      usually  expressed as  + or - a specified  number  of concentration
      units  (i.e., +  or - 5.00  ppm).  The equation can also be written
      in terms  of the coefficient of variation (CV) as follows:

          n =  (CV)2t2 a/p2

     where  CV is the coefficient of variation,  p  is the  allowable
     margin of error expressed as a  percentage  (D/y),  and y is  the
     mean of the samples.

          The  margin  of error  is  needed  in determining the  number  of
     samples required  to meet the precision specified.   This is often
     expressed  as the percentage  error that the scientist  is  willing
     to accept or  it may be the  difference that  he  hopes to detect
     via the  study.   The margin  of error  chosen  is combined  with the
     confidence level  to derive  an estimate of the number of  samples
     required.   The  smaller  the margin  of  error, the  larger  the
     number of samples required.
As  the  variability  increases in  a measurement,
differences in constituent concentration  decreases.
the  ability  to detect
     The  reliability  of data  is expressed by  the confidence  level,  which
states the  level  of  precision  of the results generated by the  study.   Mason
(1983) explains confidence levels as  follows:

     Three confidence levels are normally used by the scientific com- '
     munity.  These are usually expressed  as + or - 1 standard devi-
     ation, + or - 1.96 standard deviations,  and + or - 2.58 standard
     deviations, which covers  68X,  95%,  and 99X of  the  total
                                   142

-------
     population  respectively.   Another way to  state  this is to  say
     that  the probability  is  0.32  (or  1  in  3)  that  the  value  is
     outside  of  one standard deviation on  either  side of the mean;
     0.05  (or 1  in 20)  that  the value is  outside  of  1.96  standard
     deviations; or 0.01 (or  1 in 100) that the value  is outside  of
     2.58 standard deviations.

     The  first  step  in  the  use  of this  statistical  procedure  in  the
reconnaissance investigation is an initial determination of the variability of
concentrations or  levels of  hazardous waste  or soil  constituents.    Provost
(1984) recommends that for such an exploratory study,  6-15 samples  per  uniform
area should  be  sufficient.   Realizing that the cost of  analyses of hazardous
constituents may be quite high, a possible method to evaluate the  variance of
waste  distribution  in soil  is to use a  surrogate waste parameter  which is
easier and less  expensive to  analyze  than hazardous waste constituents (e.g.,
oil  and  grease  for  petroleum  refinery wastes).   A  large  variability in
concentrations of this surrogate  parameter  may mean that a  larger number of
samples  will  be  required  to  adequately  describe  the distribution  and
concentrations of wastes at the site.  Therefore, a well-managed and properly
designed  site that  has had  uniform  waste  application and  has  avoided  the
formation  of "hot  spots"  due to  uneven  waste application  or  runoff  will
require a fewer number of samples than a site that has been less well-managed.
The number of samples required during long-term  monitoring of an existing site
may  also  be affected  by the  variability  of  waste  distribution determined
during the reconnaissance  investigation.   Examples of  the number of  samples
required using this statistical  procedure  is given in Table B.2.

     The use of this  statistical  method assumes  that  the  measurements  are
Independent  of  one another  and are  distributed  normally  (Barth  and Mason
1984).    If one  or  the  other,  or  both,  of these  assumptions  is  not  valid,
undetermined  errors  may be  introduced.    If  the  normal distribution  is  not
valid, an assumption of  a log normal  distribution may  be considered.   Table
B.I listed those  soil  properties which are known to be usually normally or log
normally distributed.    In  general,   a variable whose  variance  increases  in
direct  proportion to   its  mean  value  (especially  over  a  few orders  of
magnitude),   is  best  described  by  a log  normal  distribution.    If  the
measurements  are dependent  on one  another,  it may  be possible  to  replace
classical   statistical  techniques  with kriging.   Examination  of the data
collected from the exploratory study  should enable the statistician to  decide
on an appropriate statistical  technique.

     The  distribution  pattern of  chemical  constituents  of soil  including
pollutants is truncated  at  zero.   This characteristic often  gives rise to  a
frequency curve  skewed to the  low end of  the concentration  scale.  When  this
situation 1s  encountered,  the data  can  usually be  transformed  to  a  normal
distribution by taking  the  log  of  the data.  Alternatively, a statistician  may
be consulted  for  preparation of a  procedure appropriate for determining  sample
numbers for constituents  which  have random,  log  normal distribution.  ..

     It is recognized  that  the cost of analysis for hazardous waste constitu-
ents in soil  cores divided  into  segments may be  extremely expensive.  The  more
                                   143

-------
 Table B.2   Examples of Number of Samples Required  to  Achieve a Specified
             Analytical  Precision  and  Level  of  Confidence,  Based on  Expected
             Variability of Sample Concentrations, as Determined in  an -Explor-
             atory Study
                                             Level of  Precision  (Specified)
 Coefficient of Variation   Confidence  Level     10?       5S?        lUOI	
      (measured)             (specified)       Number of  Samples  Required
1 95
90
70
50
4 95
90
70
50
10 95
90
70
50
50 95
90
70
50
100 95
90
70
50
2
1
1
1
3
2
. 1
1
6
5
2
1
99
70
28
12
385
271
115
47
1
1
1
1
1
1
1
1
2
2
1
1
6
5
2
1
18
13
6
3
1
1
1
1
1
1
1
1
2
1
1
1
3
2
1
1
6
3
2
1
important data from the  soil  cores are the concentrations of  constituents  at
and just below the bottom of the treatment zone (to determine if waste
constituents  are migrating out  of the  treatment  zone)  and  in  the zone  of
Incorporation  (ZOI)  (to determine  if  waste  constituents are  accumulating  in
the ZOI).  The permit writer may use discretion 1n allowing  the compositing  of
samples from  the same  depths  between  the ZOI  and  the bottom of the treatment
zone from soil cores within the  same  uniform area  If the variance  determined
by the analysis of the surrogate parameter is not too large.

     If the  variance  found during  the exploratory  study  is  so  great  as  to
require such  a large number of samples that  the  cost is prohibitive, or there
is a lack of  available laboratory capacity to  handle the analyses,  the  permit
writer  may  specify  a  lower level  of  confidence  and/or   a  lower  level  of


                                   144

-------
 precision  for  the  data.   The permit writer should use caution to  prevent cost
 from becoming  the  excuse  for failing  to  apply  statistical  criteria  in the
 design  of  the  reconnaissance  program.  Environmental  sampling usual]y-attempts
 to  attain  a level  of 95  percent  confidence.   However,  lower  levels  may be
 accepted  as long  as  the  level  is  known and  agreed  upon before the study is
 started.   Use  of the tables  given  in  Appendix A  of  the  Soil  Sampling Quality
 Assurance  User's Guide  (Barth  and Mason,  1984)  may be  used to estimate the
 number  of  samples  required using  different  specified levels  of  confidence and
 degrees of precision.  The data from the reconnaissance investigation are used
 to  determine whether additional  laboratory and/or field  studies are required
 to  complete the  LTD.  For such conclusions to be drawn, there  is a definite
 need to measure the  reliability  of the data.   In  general,  any approach for
 collecting LTD data without adequate quality assurance/quality control (QA/QC)
 and statistical  planning should  be  strongly discouraged  (Barth  and  Mason
 1984).

 STATISTICAL  INFERENCES

 Estimation

     All of the possible soil cores in  a land  treatment demonstration plot and
 all  of  the  soil pore water at the bottom of the treatment zone are examples of
 populations  from  which  samples  may be  drawn  in  a  hazardous  waste  land
 treatment  demonstration.   Given  analytical results  from  random samples  from
 such a  population, appropriate statistical  techniques should  be  used to report
 the  analyses  and provide  information  about the  data's representativeness  of
 the  population from which the samples were  drawn.

     In every case the sample mean (average) should be reported  along with the
 sample  variance,  standard  deviation,  or coefficient of  variation.   In  most
 situations, the mean is the best  single number to  represent the  population.   A
 confidence interval  for  the mean  should  be calculated  and reported.    The
 confidence  interval is a statement of  confidence  (e.g., 95 percent confident)
 by  the  person  reporting the  data that the population mean  lies  between  the
 upper and  lower  limits  of  the interval.   If the  population  data  is  normally
 distributed or the transformed data  is normally distributed (e.g.,  log  normal
 data),  the calculation of  the  confidence  interval  uses  the student's  t
 statistic.   Similar  confidence  intervals  for the variance of  a  normal
 population  are less frequently reported, but may be calculated using  the  chi-
 squared (x2)  statistic.    If  the population   data  are far  from  normally
distributed and  cannot  be  transformed   to be approximately  normal,  a
 statistician  familiar with  exact and  nonparametric  statistical  procedures
 should be consulted.

     In  situations  where  single  measurements may  need  to  be evaluated  as
 indications  of increasing  hazardous constituent  concentration,   the  upper
tolerance   limit for  the  background (existing)   concentration should  be
calculated.  The  tolerance  limit  is based on the mean value of the  constituent
 in  the  uniform area or plot  to  be used for demonstration.   Subsequent  data
from a  sample  that  exceeds  the  tolerance  limit  indicates  a  change in the
population  and  would  justify  a more  intense  investigation  if  the result
                                   145

-------
 occurred  at  a  critical  point  in  the  treatment scheme  (e.g.,  below the
 treatment  zone).

     Formulae  and  tabulated  statistical  values  for calculating all  the above
 statistics can be found in most introductory statistics  texts.

 Hypothesis Testing

     Statistics for determining the significance of changes in sample mean or
 variance values fall generally in the category  of  hypothesis  testing.   As an
 example, one might hypothesize that  the  population mean of a waste constituent
 1s  currently equal  to  the  mean  at  the last sampling  time.    The  alternate
 hypothesis would  be  that the means  are not  equal.   The alternate hypothesis
 could state that the mean has increased  or decreased.

     Where single pairs of means  from normal  populations  are being  compared,
the  use  of student's t-test  is recommended.   Care should be  taken  to  apply
either  the  two-tailed  or  one-tailed  test  appropriately,  depending on  the
nature of the hypotheses.

     Where more than  one comparison  of experimental treatment effects is to be
made, the  use of analysis of  variance (ANOVA) procedures  is  recommended.   If
ANOVA results  indicate significant  differences  exist  among  the  treatments,
tests for  multiple comparisons between means  such  as  Duncan's multiple  range
test  or Tukey's honestly  significant  difference test  should  be used  to
Identify means that  are significantly different from one another.

     Procedures for  performing  the above  tests  are  described  in  most
Introductory textbooks  and are available in many computer software statistical
packages.
                                   146

-------
                                                       9486.-OOs2
                                 APPENDIX C
             INFORMATION  CONCERNING THE HWLT MATHEMATICAL MODEL


 C.I   DETAILED DESCRIPTION OF MODEL EQUATIONS

 Basic  Equation

     A constituent of  Interest  may exist  simultaneously in more  than one
 phase.   The strategy  adopted  for  land  treatment  facility description  is to
 derive the  basic differential equation for  a single constituent in a single
 phase,  and then construct a system of equations as necessary  to describe more
 complex  relationships.   A mass balance must  include terms for the following
 mechanisms:
Rate change in mass\
 of constituent in
  control volume   j

        I
              /mass flux due to \
               dispersion within
              \    the phase    I

                       II
                            (mass flux due to
                              advection  to
                                the phase

                                   IV
                                /mass  flux  due  to\
                             +  I diffusion  within
                                \    the  phase   j

                                         III

                                   /mass  decay  rate\
                                         within
                                   \    the  phase
                           /mass supply rate\
                           I  into the  phase


                                   VI
                                          'mass transfer'
                                            rate among
                                              phases

                                                VII
                                                       (Cl.l)
For a phase partially filling a control  volume of dimension A by dz, the terms
in Equation Cl.l may be expressed  mathematically by:
     9C9Adz _ 30A
                 6
where:
dz
                 3 z
                                        9 z
          concentration,   g constituent

                            m3  phase
                                                - yCOAdz -H^SAdz +  Adz (C1.2)
     0 =

     A =

     z =

     t =
                                                phase
control volume phase content,! m3  „,...   ,   ,
               K            *y m-3  control volume

horizontal area of control  volume,

depth, positive downward,  (m),

time, (days),
                    147

-------
      6  *  dispersion coefficient related to movement the of phase,  (m2/day),
      ?  =  diffusion  coefficient  for  the  constituent  in quiescent  phase
           (mZ/day),                                               /
      V  =  vertical pore velocity of the phase in the soil,  (m/day),
      V  -  first order decay rate, (I/day),
      S  •  supply rate of the constituent into the control volume t(q/m3 control
           volume/day),
      ^  =  mass  adsorption rate into  the  control  volume,  (g/m2  control
           volume/day), and
    dz  B  depth of the control volume,  (m).
Equations  by Jury (1983). and Short  (1985)
Equation C1.2 may be simplified by  assuming:
      1.   © is constant with time.
      2.    A is set equal  to 1m2, i.e.,  applies to  a  1 m2 soil column, and
      3.   0, D, C, and V  are  constant  with depth.
this  results in:
where:
     D =  total dispersion coefficient  (m2/day), equal to 3 + £•
The following  additional  assumptions  were used  by Jury  et   al .   (1983)  and
Short (1985):
     1.   Only four phases  exist  1n  the soil environment:   water,  oil,  air,
          and soil  grains, and
     2.   The mass transfer rates  among  phases  are instantaneous  and  progress
          to the extent necessary to reach equilibrium.
These assumptions greatly reduce the complexity of the system equations because
the constituent states are in equilibrium at all times.  Because equilibrium is
assumed at  all times,   the mass  transfer rate,   ty may  be eliminated "from the
equations  by  introducing an  algebraic constraint  describing  isotherm
equilibrium partitioning.
     Applying  Equation  G1.3 to each of  the  four  phases  in  a  control  volume
(Figure 4.2) results  in:
                                   148

-------
                                          + Sw       (for water)    -  {C1.4a)


                                           $o         (for oil)      (C4.1b)
                   oZ

                                                       (for air)      (C4.1c)


                                                       (for soil)     (C4.1d)
where:
     w, o, a,  and  s=   subscripts  identifying water, oil, air, and soil grain
            •  phases, respectively,

     Cw=  concentration in water,  (g/m^  water),

     C0=  concentration in oily waste,  (g/m3 oil),

     Ca=  concentration in air, (g/m^  air),

     Cs=  adsorbed mass on soil grains,  (g constituent/g soil grains), and

      p=  bulk density of soil, (g soil  grains/m^ control volume).

The  sum  of the  masses  in  each phase  equals  the  total mass  in the  control
volume, CT, (g/m3 control volume), i.e.,

     CT = ewcw + GOCO +eaca +pcs                                   (ci.5)

     Summing equations  C1.4a through C1.4d  and substituting  Equation Cl.5
yields:
                                                           Sz        3z

                       - GaWaCa - pysCs + Sw + S0                     (C1
Based on assumptions made  above,  Cw,  C0,  Ca,  and  Cs are at  equilibrium  at  all
times, and the concentrations  in  all  phases can  be expressed in terms  of  the
concentration  in  one  of  the phases.    With the further assumption that
equilibrium conditions  can be  expressed  by linear  isotherms,  the following
relationships  between  phase concentrations results:


     r   =   K   r
     La     kaw'-w


and
                                   149

-------
      Cs   •   KSOC0

 and

      Cw   =   KwaCa
      Co   -   KoaCa
      Cs   -   *saCa

 and

      Cw   =   KWSCS
      Co   •   KSOCS
      Ca   •   KasCs

 It should be observed that only three of the coefficients  are  independent   For
 example:

      CQ * KOWCW * KoaCa s Koa(^awCw)»

      therefore,  Kow = KoaKaw.

      In  order  to  conform  with the  equation  developments presented  by Jury
 (1983) and  Short  (1985),  partitioning  coefficients  for  the dissolved state in
 water can be used as follows:

      CT = BWCW » B0C0 = BaCa = BSCS                                  (C1.7)

 where:

      Bw- 0W * 00Kow*0aKaw+PKsw
      B0 - (0W/KOW) + 00 + (0aKaw/Kow)  +(pKsw/Kow)
      Ba « (©w/Kaw + (0oKow/Kaw)  + ©a  +  
-------
           cT(z,t=o)  =0     L  <  z      for t  = o

     Boundary conditions

                     « 0
              aCr
          -DE — + vECT = -HECT     for z = o
where:
                                      11 the piow zone-<9/m3)-
     HE « upper boundary effective mass transfer coefficient.
                               151

-------
  C.2  USER  INFORMATION
         n
                            first
       Row 1.    Title  NAPHTHALENE, Application 4 t1n.es per year.

       "°W ?-      ™          °f treatment  zone'  <">• ««  » Depth of  Plow
       Row 3.     DETECT    DZ - Depth Increment, (m).
       Row 4.     TOTAL TIME . Length of run, (days). DT - Time Increment,  (days).
       Row 5.     TOI^. The time  (days)  Into  a run  that  a new output  Interval 1s
       Row 6.     DTOI - The new output Interval,  (days).
       Row 7.    Contains soil  characteristics
                                                .  PHI  =  son
      Row 8.    Contains water phase  characteristics
                RMUWPZ =  Constituent  Degradation Rate  within  water  in  Plow
                          w?thin ™tay)t-an?  UWLZTS  Const1t^nt  Degradation  Rate
                          within water  in Lower Treatment
                          Zone,  (I/day).
 The next  three  rows  contain partition coefficients.

      Row  9:     RKOWPZ  - Oil Water  Partition Coefficient  in Plow  Zone,   (g  in
                                  1 )f andTRKOWLZ •  Oil  Water  Partition   (9
                                        Treatment   Z°n*,  (9  1n  oil/m3/g 1n
     Row 10:   RKAWPZ x Air  Water  Partition  Coefficient  in  Plow Zone, (g in
               ciiff/A ln*Mt?r/f )f and RKAWLZ  "  A1r  Water Petition
               water/m3)e.ntS  1n Lower  Tr"tment  Zone,  (g  in  air/n,3/g  1n
     R°W U:   Si¥/i; S- " W,ate,r 3P,art1t1on Coefficients in Plow Zone,  (g in
               cSIffT/?pn?  Wf 6r;/m >f  arnd RKSWLZ * So11 Water Partition V9
               S"er/n&)!               Treatment  Zone,  (g  in  sovl/m3/g  1n

The next five rows contain oil  phase characterization
                                 152

-------
EXAMPLE RUN FOR COHPOUND NAPHTHALENE. APPLICATION 4 TIME PER YEAR
0TZON,DPZON,DZ 1.50 .150 .300E-01
DETECT .000
TOTAL TIHE, DT
TOI
90.0
.000
DTOI 1.00
SflLB, PHI, ROES 4.90
RHUMPZ, RHUMLZ
RKONPZ, RKOHLZ
RXAHPZ, RKAHLZ
RKSHPZ, RKSNLZ
MR.CONSMTFO
«TFH,ROE«,ROEOI
DTAC, DTAF
HO
RttUOPZ, RHUOLZ
DA, VA
RWMPZ, RHUALZ
RHUSPZ, RMUSLZ
ZX
CHZ
coz
CAZ
CS2
THETOX
TEHP FACTOR
TEMP IN PZ
TEHP IN LZ
VHPRINE
SHC
.345
.135E+04
.170E-01
.400E-02
.MOE-01
.400
366.
.231E-01
.345
.000
.000
.345
.000
.000
.000
.000
.000
.000
1.00
.500
6.00
15.0
.435
.172
.135E+04
.170E-01
.400E-02
.200E+04
.900
91.3

.173E-01
.000
.000
.172
.150
.000
.000
.000
.000
.000

40.0
60.0
1.40
-



.400
.BOO






220
000
000
000
000
000
20.0 20.0 20.0
20.0 20.0 20.0
.120E-02 .120E-02 .120E-02
1.00 1.00 1.00

.000
.000












.300
.000
.000
.000
.000
.000

.000
.000












.000
.000
.000
.000
.000
.000

.000
.000













.000
.000












.000 .000
.000 .000
.000 .000
.000 .000
.000 .000
.000 .000
20.0 20.0 20.0 20.0
20.0 20.0 20.0 20.0
•120E-02 .120E-02 .120E-02 .120E-02
1.00 1.00 • 1.00 1.00
20.0
20.0
.120E-02
1.00

.000
.000












.000
.000
.000
.000
.000
.000
20.0
20.0
.120E-02
1.00

.000.
.000












.000
.000
.000
.000
.000
.000
20.0
20.0
.120E-02
1.00

.000
• vw
.000












.000
.000
.000
.000
.000
.000
20.0
20.0
.120E-02
1.00
















20.0
20.0
.120E-02
1.00
Figure (2.1   Sample Input  Data  File
                                    153

-------
        Row 12:                                                   and
                  Fraction  of Oil  in  waste  (kq/kq)              f  and WTFO * Wei9ht
       Row 15:   Ho = decay rate of oil (I/day)
  The next two rows contain unsaturated  Pore  Space  Phase characteristics
                *«* Wth,,
 The next row contains the soil phase degradation characteristics-
 The next six rows contain initial  waste concentrations  within  the  soil  profile:
      Row 20:   ZX - Depths at which a new initial  condition  is set,  (m).
      R0" 21:   (9/m3)!nUial  C0nst1tuent concentration  In water at depth ZX,
      Row 22:   COZ  = Initial  concentration in Oil  at depth ZX,  (g/m3),
      Row 23:   CAZ  » Initial  concentration in Air  at depth ZX,  (g/m3),
      Row 24:   CSZ  - Initial  concentration in Soil at depth ZX, (g/m3),  and
      R0" ":    ZTXH!(£3X/^ft1al »" Content in Soil by Vol™ ,t depth

cTh,er,cteeXristf1cs.e  "" ""^   $Ue  """"....nt.l  and  soi 1  moisture
                           •  van't  Hoff-Arrhenius Coefficient, for"each month
     Row 27:    Temp in PZ  =  Temperature  during each month  in Plow Zone, CO,
                                 154

-------
  Row 28:
                        = Temperature dur1"9 "<=" "onth  in  Lower  Treatment
  Row 29
 Row.30:    SHC
Saturated Water Content,  during each  month,(cm3/Cm3).

 MASS DECAYED



 LEACHED WATER





 LEACHED OTHER  '•





 PERCENT TREATED^





ERROR
  Mass of constituent lost to decay,
                                    the
  soil
                                    atmosphere from the
   at  f^pnth°f,the,app]1ed constit^t mass which does
 not  leave the treatment zone, and



      departure  from true mass balance due to numerical
                             155

-------
EIAHPLE RUN FOR  COMPOUND NAPHTHALENE. APPLICATION 4  TIDE PER YEAR
DTZON,DPZON,DZ
DETECT
TOTAL THE, DT
TOI
OTOI
SHLB, PHI, ROES
muHPZ, miwLZ
RKONPZ, RKOMLZ
RKAHPZ, RKANLZ
RKSNPZ, RKSHLZ
HAR,CONSN,¥TFO
HTFH,ROEH,ROEOI
DTAC, DTAF
HO
RMUOPZ, RfflKJLZ
DA, VA
MUAPZ, RHUALZ
RHUSPZ, musLZ
zx
CMZ
coz
CAZ
csz
THETOI
TEHP FACTOR
1.50
.000
90.0
.000
1.00
4.90
.345
.135E+04
.170E-01
.400E-02
.600E-01
.400
366.
.231E-01
.345
.000
.000
.345
.000
.000
.000
.000
.000
.000
1.00
— —-••— •" • » •••te i MI i bnn
.150 .300E-01
.500
6.00 40.0
15.0 60.0
.435 1.40
.172
.135E+04
.170E-01
.400E-02
.200E+04 .400
.900 .800
91.3

.173E-01
.000
.000
.172
.150 .220
.000 .000
.000 .000
.000 .000
.000 .000
.000 .000
TENP IN PZ 20.0 20.0 20.0 .
TEHP IN LZ 20.0 20.0 20.0
WRIHE .120E-02 .120E-02 .120E-02
SHE 1.00 1.00 1.00
NCOUN INITIAL MASS 6 DT »
0 .0000
DEPTH CM
.00 .00000
.03 .00000
.06 .00000
.09 .00000
.12 .00000
.15 .00000
.18 .00000
.21 .00000
.24 .00000
.27 .00000
.30 .00000
.33 .00000
.36 .00000
.3? .00000
.42 .00000
.45 .00000
.48 .00000
.51 .00000
.54 .00000
.57 .00000
.60 .00000
.50
CO
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
^ 	 n _

CA
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000

.000
.000












.300
.000
.000
.000
.000
.000

.000
.000












.000
.000
.000
.000
.000
.000

.000 .000
.000 .000












.000 .000
.000 .000
.000 .000
.000 .000
.000 .000
.000 .000

•000 .000 - " .000
.000 .ooa .000












.000 .000 .000
.000 .000 .000
.000" .000 .000
.000 .000 .000
.000 .000 .000
.000 .000 .000
20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0
2.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 200
.120E-02 .120E-02 .120E-02 .120E-02 .120E-02 .120E-02 .120E-02 .120E-02 .120E-02
1.00 1.00 1.00 1.00 1.00 1.00 J.OO 1.00 1.00

CS
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000

THETAO
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000

THETAH
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722

THETAA
.00000
.17778
.17778
.17778
.17778
.17778
. 17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
                                                    156

-------
.63 .00000
.66 .00000
.00000
.00000
.00000
.00000
.69 .00000 .00000 .00000
.72 .00000 .00000 .00000
.75 .00000 .00000 .00000
.78 .00000 .00000 .00000
.81 .00000 .00000 .00000
.84 .00000 .00000 .00000
.87 .00000 .00000 .00000
.W .00000 .00000 .00000
.93 .00000 .00000 .00000
.96 .00000 .00000 .00000
.99 .00000 .00000 .00000
1.02 .00000 .00000 .00000
1.05 .00000 .00000 .00000
1.08 .00000 .00000 .00000
1.11 .00000 .00000 .00000
1.14 .00000 .00000 .00000
1.17 .00000 .00000 .00000
1.20 .00000 .00000 .00000
1.23 .00000 .00000 .00000
1.26 .00000 .00000 .00000
1.29 .00000 .00000 .00000
1.32 .00000 .00000 .00000
1.35 .00000 .00000 .00000
1.38 .00000 .00000 .00000
1.41 .00000 .00000 .00000
1.44 .00000 .00000 .00000
1.47 .00000 .00000 .00000
1.50 .00000 .00000 .00000
1.53 .00000 .00000 .00000
THE « 6.430 DT « 6.4304 MASS
DECAY « .22459 SADN = .00000 SOATOP
Co (g substance in oil)/(N3 control vol.)
DEPTH CH
.00 .00000
.03 .32627E-04
.06 .32627E-04
.09 .32627E-04
.12 .32627E-04
.15 .32627E-04
.18 .00000
.21 .00000
.24 .00000
.27 .00000
.30 .00000
.33 .00000
.36 .00000
.39 .00000
.42 .00000
.45 .00000
.48 .00000
.51 .00000
.54 .00000
Figure C2

CO
.00000
.15934E-04
.159.34E-04
.15934E-04
.15934E-04
.15934E-04
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.2. Conti

CA
.00000
.55466E-06
.55466E-06
.554WE-06
.5546&E-06
.55466E-06
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
nued.

.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
« .274UE-01
* .00000
.00000
.00000
.25722
.2572?
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
.00000 .25722
V« » .46653E-02
ERROR -.93132E-08 IMITIA
CS THETAO
.00000 .00000
.13051E-06 .36202E-03
.13051E-06 .36202E-03
-13051E-06 .36202E-03
.13051E-06 .36202E-03
.13051E-06 .36202E-03
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
.00000 .00000
157

THETAN
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722

.17778
.17778
• I / f t Q
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778 .
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
HASS * .25200
THETAA
1.0000
.17742
.17742
.17742
.17742
.17742
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778


-------
.57 .00000
.60 .00000
.63 .00000
.66 .00000
.69 .00000
.72 .00000
.75 .00000
.78 .00000
.81 .00000
.84 .00000
.87 .00000
.90 .00000
.93 .00000
.96 .00000
.99 .00000
1.02 .00000
1.05 .00000
1.08 .00000
. 1.11 .00000
1.14 .00000
1.17 .00000
1.20 .00000
1.23 .00000
1.26 .00000
1.29 .00000
1.32 .00000
1.35 .00000
1.38 .00000
1.41 .00000
1.44 .00000
1.47 .00000
1.50 .00000
1.53 .00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
TIHE = 19.291 DT = 6.
KCAY > .25168
Co (9 tubiUnce in
DEPTH CN
.00 .00000
.03 .38600E-06
.06 .3B604E-06
.09 .38604E-0&
.12 .38604E-06
.15 .38604E-06
.18 .71487E-10
.21 .24691E-14
.24 .00000
.27 .00000
.30 .00000
.33 .00000
.36 .00000
.39 .00000
.42 .00000
.45 .00000
.48 .00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000.
.00000
.00000
.00000
.00000
.00000
.00000
4304 HASS
SAW = .00000 SDATOP
oil)/(H3 control vol.)
CO
.00000
.14006E-06
.14007E-06
.14007E-0&
.14007E-06
.14007E-06
.00000
.00000
.00000
.00000
.00000
,00000
.00000
.00000
.00000
.00000
.00000
CA
.00000
.65620E-OB
. 6 56 26 E -08
.45626E-08
.65626E-OB
.65626E-08
.12153E-11
.41975E-16
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
* .32431E-03 VH * .46653E-02"
« .00000
cs
.00000
.15440E-08
.15442E-OB
.15442E-08
.15442E-08
.15442E-OB
.28595E-12
.9B765E-17
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
ERROR « .64785E-07 INITIA
THETAO
.00000
.26898E-03
.26B9BE-03
.26B98E-03
.2689BE-03
.2689BE-03
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
THETAN
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
. 17778
. 17778
.17778
.17778
.17778
.17778
. 17778
.17778
.17778
• • f f r if
. 17778
.17778
.17778
.17778
. 17778
. 17778
• ml f t D
. 17778
.17778
• 4 1 r / D
. 17778
• * f r r W
. 17778
. 17778
.17778
.17778
. 17778
. 17778
.17778
. 17778
.17778
.17778
.17778
. 17778
. 17778
.17778
.17778

HASS « .25200
THETAA
1.0000
.17751
.17751
.17751
.17751
.17751
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
Figure C2.2.  Continued.
                                    158

-------
     .51   .00000       .00000       .00000
     .54   .00000       .00000       .00000
     .57   .00000       .00000       .00000
  .  .60   .00000       .00000       .00000
     .63   .00000       .00000       .00000
     .66   .00000       .00000       .00000
     .69   .00000       .00000       .00000
     .72   .00000       .00000       .00000
    .75   .00000       .00000       .00000
    .78   .00000       .00000       .00000
    .81   .00000       .00000       .00000
    .84   .00000       .00000       .00000
    .87   .00000       .00000        .00000
    .90   .00000       .00000       .00000
    .93   .00000       .00000       .00000
    .96   .00000       .00000       .00000
    .99   .00000       .00000       .00000
  1.02   .00000        .00000       .00000
  1.05   .00000       .00000       .00000
  1.08   .00000       .00000       .00000
  1.11   .00000       .00000       .00000
  1.14   .00000       .00000       .00000
  1.17   .00000       .00000       .00000
  1.20   .00000       .00000       .00000
  1.23   .00000       .00000       .00000
  1.26   .00000       .00000       .00000
  1.29   .00000       .00000       .00000
  1.32   .00000       .00000       .00000
  1.35   .00000       .00000       .00000
  1.38   .00000       .00000       .00000
  1.41    .00000        .00000       .00000
  1.44    .00000        .00000       .00000
  1.47    .00000       .00000       .00000
  1.50    .00000       .00000       .00000
  1.53    .00000       .00000    ,  .00000
 THE *       32.152 DT «    4.4304     BASS =
DECAY =  .25200     SAM  =  .00000     SOATOP
Co (g substance in  oil)/(H3 control  vol.)
                                                 .00000       .00000       .25722
                                                 .00000       .00000       .25722
                                                 .00000       .00000       .25722
                                                 .00000       .00000       .25722
                                                 .00000       .00000       .25722
                                                 .00000       .00000       .25722
                                                 .00000       .00000       .25722
                                                 .00000       .00000       .25722
                                                .00000       .00000       .25722
                                                .00000       .00000        .25722
                                                .00000       .00000       .25722
                                                .00000       .00000       .25722
                                                .00000       .00000       .25722
                                                .00000       .00000       .25722
                                                .00000       .00000       .25722
                                                .00000      .00000       .25722
                                                .00000      .00000       .25722
                                                .00000       .00000       .25722
                                                .00000       .00000       .25722
                                                .00000       .00000       .25722
                                                .00000       .00000       .25722
                                                .00000       .00000       .25722
                                               .00000       .00000       .25722
                                               .00000       .00000       .25722
                                               .00000       .00000        .25722
                                               .00000       .00000       .25722
                                               .00000       .00000       .25722
                                               .00000       .00000       .25722
                                               .00000       .00000       .25722
                                               .00000       .00000       .25722
                                               .00000      .00000       .25722
                                               .00000       .00000       .25722
                                               .00000       .00000       .25722
                                               .00000       .00000       .25722
                                               .00000       .00000       .25722
                                                 .3B384E-05 VH *    .46653E-02
                                               .00000     ERROR «-.35949E-07 IKITIA
DEPTH
  .00
  .03
  .06
  .09
  .12
  .15
  .18
  .21
  .24
  .27
  .30
  .33
 .36
 .39
 .42
          CN
        .00000
        .45666E-08
        .4547SE-08
        .45675E-08
        .45675E-08
        .45675E-OB
        .B6209E-11
        .10120E-I4
        .41073E-19
        .56656E-24
       .00000
       .00000
       .00000
       .00000
       .00000
   CO
 .00000
 .12311E-08
 .12313E-08
 .12313E-08
 .12313E-08
 .12313E-08
 .00000
 .00000
 .00000
 .00000
 .00000
 .00000
.00000
.00000
.00000
   Figure  C2.2.    Continued.
   CA
 .00000
 .77633E-10
 .77647E-10
 .77647E-10
 .77647E-10
 .77647E-10
 .14655E-12
 .17204E-16
 .69B24E-21
 .96315E-26
 .00000
 .00000
 .00000
 .00000
.00000
   cs
 .00000
 .18247E-10
 .1B270E-10
 .18270E-10
 .18270E-10
 .18270E-10
 .34484E-13
 .404BOE-17
 .16429E-21
 .22662E-26
 .00000
 .00000
 .00000
.00000
.00000

       159
  THETAO
 .00000
 .199B4E-03
 .199B4E-03
 .19984E-03
 .199B4E-03
 .19984E-03
 .00000
 .00000
 .00000
 .00000
 .00000
.00000
.00000
.00000
.00000
  THETAN
 .25722
 .25722
 .25722
 .25722
 .25722
 .25722
 .25722
 .25722
 .25722
 .25722
 .25722
 .25722
 .25722
.25722
.25722
    .17778
    .17778
    .17778
    .17778
    .17778
    .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
   .17778
  .17778
  .17778
  .17778
  .17778
  .17778
  .17778
  .17778
  .17778
  .17778
  .17778
  .17778
  .17778
  .17778

HASS = .25200

  THETAA
 1.0000
 .17758
 .17758
 .17758
 .17758
 .17758
 .17778
 .17778
 .17778
 .17778
 .17778
 .17778
.17778
.17778
.17778

-------
     .45   .00000       .00000       .00000
     .48   .00000       .00000       .00000
     .51   .00000       .00000       .00000
     .54   .00000       .00000       .00000
     .57   .00000       ,00000       .00000
     .40   .00000       .00000       .00000
     .63   .00000       .00000       .00000
     .44   .00000        .00000       .00000
     .49   .00000       .00000       .00000
     .72   .00000       .00000       .00000
     .75   .00000       .00000       .00000
     .78   .00000       .00000       .00000
     .81   .00000       .00000       .00000
     .84   .00000       .00000       .00000
    .87   .00000       .00000      .00000
    .90   .00000       .00000      .00000
    .93   .00000       .00000       .00000
    .94   .00000       .00000       .00000
    .99   .00000       .00000       .00000
   1.02   .00000        .00000       .00000
   1.05   .00000       .00000       .00000
   1.08    .00000       .00000       .00000
   1.11   .00000       .00000       .00000
   1.14   .00000       .00000       .00000
   1.17   .00000       .00000       .00000
   1.20   .00000       .00000       .00000
   1.23   .00000       .00000       .00000 '
   1.24   .00000       .00000       .00000
  1.29   .00000       .00000      .00000
  1.32   .00000       .00000      .00000
  1.35   .00000       .00000       .00000
  1.38   .00000       .00000       .00000
  1.41    .00000       .00000       .00000
  1.44    .00000        .00000       .00000
  1.47    .00000       .00000       .00000
  1.50    .00000       .00000       .00000
  1.53    .00000       .00000       .00000
 TIHE *       51.443 DT =     4.4304      HASS
DECAY =  .25200     SADN *   .00000     SMTOP
Co (9 substance in  oil)/(H3 control vol.)
M^M*tl     _. .
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.17778
.17778
.17778
. 17778
.17778
. 17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
 .49903E-OB VK =   .46653E-02
.00000    ERROR '-.14402E-06 INITIfl
HASS = .25200
DEPTH
.00
.03
.06
.09
.12
.15
.18
.21
.24
.27
.30
.33
.36
CN
.00000
.58763E-11
.58782E-11
.58782E-11
.3B782E-11
.387B2E-11
.31279E-12
.79174E-16
.B4374E-20
.48303E-24
.15642E-2B
.27138E-33
.00000
CO
.00000
.10145E-11
.10149E-11
.10149E-11
.10149E-U
.10149E-11
.00000
.00000
.00000
.00000
.00000
.00000
.00000
CA
.00000
.99897E-13
.99929E-13
.99929E-13
.99929E-13
.99929E-13
.53175E-14
. 13460E-17
.14344E-21
.B2116E-26
.26591E-30
.46134E-35
.00000
CS
.00000
•23505E-13
.23513E-13
.23513E-13
.23513E-13
.23513E-13
.12512E-14
.31670E-1B
.33750E-22
.19321E-26
.6256BE-31
.10855E-35
.00000
THETAO
.00000
.12798E-03
.12798E-03
.I2798E-03
.1279BE-03
.12798E-03
.00000
.00000
.00000
.00000
.00000
.00000
.00000
THETAH
.25722
.25722
.25722
.25722
.25722
.25722
.23722
.25722
.25722
.25722
.25722
.25722
.25722
THETAA
1.0000
.17765
.17765
.17765
.17765
.17765
.17778
.17778
.17778
.17778
.17778
.17778
. 17778
                       Continued
                                                    160

-------
.39 .00000
.42 .00000
.45 .00000
.48 .00000
.51 .00000
.54 .00000
.57 .00000
.60 .00000
.43 .00000
.66 .00000
.69 .00000
.72 .00000
.75 .00000
.78 .00000
.81 .00000
.84 .00000
.87 .00000
.90 .00000
.93 .00000
.96 .00000
.99 .00000
1.02 .00000
1.05 .00000
1.08 .00000
1.11 .00000
1.14 .00000
1.17 .00000
1.20 .00000
1.23 .00000
1.26 .00000
1.29 .00000
1.32 .00000
1.35 .00000
1.38 .00000
1.41 .00000
1.44 .00000
1.47 .00000
1.50 .00000
1.53 .00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.23722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.25722
.17778
. 17778
.17778
.17778
.17778
.17778
.17778
. 17778
.17778
. 17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
.17778
Figure C2.2.   Continued.
                                  161

-------
Swple OUT2 fill, for plotting
TIKE HASS DECAYED LEACHED

6.43
12.86
19.29
25.72
32.15
38.58
45.01
51.44
57.87
64.30
70.73
77.17
83.60
90.03

.22458944
.24901854
.25167579
.25196471
.25199615
.25199959
.25199987
.25199987
.25199987
.25199987
.25199987
.25199987
.25199987
.25199987
MTbK
.000000
.000000
.000000
.000000
.000000
.000000
.000000
.000000
.000000
.000000
.000000
.000000
.000000
.000000
LEACHED PERCENT TREATED ERROR
OTHER
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000
.00000000000

100.000
100.000
100.000
100.000
100.000
100.000
100.000
100.000
100.000
100.000
100.000
100.000
100.000
100.000

-.931323E-OB
.384171E-07
.647851E-07
-.366017E-07
-.3594B7E-07
-.292068E-07
-.103457E-06
-.144021E-06
-.148457E-06
-.14B948E-06
-.149003E-06
-.149010E-06
-.149011E-06
-.149012E-06
Figure C2.3  Sample Supplementary Output  File for Graphic Displays
                                 162

-------
  C.3  FORTRAN PROGRAM DESCRIPTION
  MAIN

     ^""V1"1" ^ruyrdrn secnon reads  the  input file  and contrnU th
  of  the  following  subroutines:   INTFRP  mir   ci nn£r  urtl,-r,.   J>...ne calling
       y . ft * (VWPR IME )gX
                                                                         (C3.1)
 where:
              0
               W = water content,/       m3water
                                  m3 control volume
          TMC, .    _  u       .     ity, (cm3/cm3),
          IME i  = Recharge rate during month i  (m3/day/m2),
          SCH(i)  = Saturated^water  content, (cmVcm3),  during month i,
            SMLB = Soil  moisture coefficient,  and
               i = Month since start  of run.
     VW = VWPRIME/3W
     0-30 _ 0y
                                                                      (  3.3)
where:

     0a • air content,/      m3 air
                      tm3 control  volume.
                                163

-------
                                                      MAIN
Oh
             Figure  C3.1.  Enhanced RITZ Model Structure.

-------
 The  program  will  run with ©w equal  to zero, calculating  the  amount  decayed
 leached,  and  lost to  the  atmosphere.   The  user  should  be  warned  that  the
 amount  lost  to  the  atmosphere  will be  underestimated,  since  the  mass  of
 contaminant amount in  the  air is calculated  from the  mass in  the -water.   If
 the water content is zero or  close to zero,  the amount available for  tra'nsfer
 to the air is very small.


 INPUT

      Appendix C2  lists  and  describes  the  input  variables  read from the  input
 file.  The first line reads  the title  of the file.   The variables  are read  in
 the order given  in Appendix  C2.   The first  15  columns read  are made up of a
 character field followed by  up to 13  real  numbers.   All numbers  are separated
 by commas.


                                  Subroutines

 INTERC

      This subroutine  interpolates the  initial conditions,  input  by the user,
 onto  the DZ  grid.  Concentrations  are  calculated at points  midway between arid
 nodes.

 OUT

      This  subroutine  outputs initial  conditions for soil air,  water  and soil
 contaminant  concentration profiles along with initial  ©0,   ©w  and © a values
 and initial mass  levels  as input by the user.


 SLUDGE

      This  subroutine  adds sludge to the plow  zone every DTAF  days  during  the
 period DTAC each year.

 MONTH

     This  subroutine  calculates  the  rate  of  change  of  the  time-dependent
 variables  VW,  <=W, Temp  in  PZ, and Temp  in  LZ.  The  rates  of change  between
 months are used  in the main program to adjust these variables each time step
 to  avoid a large jump in these variables each month.

 DECAY

     This  subroutine carries out  first  order  decay  of the  oil  and the
 contaminant,  the rate of which can vary for  the contaminant  with  both  depth
 and medium.   The user  provides  decay  rates for the  plow zone and the  lower
 treatment zone.  Decay is calculated by the  following equation:

          Ci  = Ci*exp(-rateitZ*DT)                      (C3.4)
where:    C,  = concentration  in medium  i,  (g/m3),

                                  165

-------
     rate(i>2) - flr^orjter  teV rate for concentration ,„ med1OT , tt depth

            DT = time step (day).
  TRANS
  and cS'li "^                                     the water phase

  solution algorithm.   DT  is calculated* by the fonoling'eqSaHon:^  *"  "'^

       DT * DZ/VW
                                                                       (C3.5)
  where :


      DZ = depth of space element, (m).

  DT  is calculated by Equation C3.5 so that  VWJDT will  equal  1 to minimize

  numerical  error.  The boundary condition for  the water medium is:

      CM  (2=0, t=«) = o

 where:
      Cw = concentration in water,  (q/m3)
       z = depth, (m),  and          9   ''
       t = time,  (days).


 AIR










     The  boundry conditions assumed for the  solution  are  as  follows:

     CA  (l,t+l) = 0.0

     CA  (niz+2. t+1) = CA (niz+l,t)



                                            "
                            y

TRIDAG

                                 166

-------
  EQUIL

       This subroutine uses partition coefficients to calculate «•*«-,.„ *  •
  concentration in each medium using  the  foilowTng equations:    '    conta™nant

       MASSS • CS *  Y *  DZ                                             ,., ^
       MASSW = CW * ^ *  DZ                                             |«.6
       MASS0 = GO * e0 *  DZ                                              'a.?
       MASSA - CA * Ql *  DZ                                             JC3.8


  T°tC1 - TOTAS + MASSW + MASS° * MASSA                                 (C3 10)
           DZ                                                           (C3.ll)

      BW = ©w  4  0Q RKOW  + Qa *RKAW + Y *RKSW


      r°;
      CA !
      css

 where:

      TOTAL = Total mass  of  substance in  control  volume,  (g)
      RKOW   - ml   tconcent:aj!on  of  substance  in control volume, (g/m3).
      D£?U   " ?   W3ter Part1t10n  coefficient,  (g in oil/pm3/g in water/m
                                                                           and
                                        .   son "edfu"- (9/m3)-
     MASSW  = Mass of  substance in the water medium, (g)
                                                       - (9/m3)>
                           of        " 1n on
                                       ^_
                          m3 control volume

     MASSA = Mass of substance in air medium,  (g/m3),  and
        LA = Concentration of substance in air  medium,  (g/m3).

OUT2
                               167

-------
 OUTPUT
 .    This subroutine outputs concentration profiles at death ,t ,
 intervals.  The user controls the  frequency of outDut bv ^r^KiUSnTn^pecif
 time period of output frequency DTOI by TOI   A maximum of li H-~  OI a"d
 frequencies can be entered                      maximum of 10 different out
Note to users;
 J-lc             r,..e,Th'   °" "«
whenever a concentration value is less thaiTor MU?I  tnin^B    u",96  appears

                                                      '
                            168

-------
                                    APPENDIX  0
             TARGET DETECTION LIMITS IN WATER FOR CONSTITUENTS OF
                          PETROLEUM REFINING WASTES
  Table D-l  Constituents of Petroleum Refining  Wastes
                                             Target  Detection  Limits  in  Water
                                          banseeki lyotr   Commercial  Laboratory*
                                                                  (yg/1)
  1.   Metals

      Antimony
      Arsenic
      Barium
      Beryllium
      Cadmium
      Chromium
      Cobalt
      Lead
     Mercury
     Nickel
     Selenium
     Vanadium

 2.   Volatiles

     Benzene
     Carbon disulfide
     Chlorobenzene
     Chloroform
     1,2-Dichloroethane
     1,4-Dioxane
     Ethyl  benzene
     Ethylene dibromide
     Methyl ethyl ketone
     Styrene
     Toluene
     Xylene

3.   Semivolatile Base/Neutral
     Extractable Compound?

    Anthracene
    Benzo(a)anthracene
    Benzo(b)fluoranthene
    Benzo(k)f1uoranthene
    Benzo(a)pyrene
 10
 10
 10
 10
 10
 50
 10

 10
    5
    5
    5
    5
    5
 100
    5

  10
   5
   5
5-10
50
50

50
   5
   5

   5
   5
                                   169

-------
   Table D-l  Continued
                                             .-Target Detection Limits  in *.„„
                                             isecKIi  1986"  Ummercial -Laboratory*'
                                              (^ 9/1)              (ua/n      J
  3.  Semivolatile  Base/Neutral
      txtractable CompoundsTcohtinuprh
+6ansecki 1986.
      Bis(2-ethylhexyl) phthalate              in
      Butyl benzyl phthalate                   in
      Chrysene                                 £«
      Dibenz(a,h)acridine                    300
      Dibenz(a,h)anthracene                    50                       f
      Dichlorobenzenes                         in                       5
      Diethyl  phthalate                        in                       5
      ^  « A  ». •   . .  ..    .                        AW                     on
— •"-•i«.\ u ,n/an uiu av.eiie                    50                      _
Dichlorobenzenes                         in                      5
Diethyl phthalate                        JQ                     95
7,12-Dimethylbenz(a)anthracene           50                     20
nimafkul 1*1.4.1. .1 .j. .
       »—  — •"•v'^i*«wii&\«iyaiii>iif aweilc          SIJ
      Dimethyl  phthalate                      in
      Di(n)butyl  phthalate                                           20.
      Di(n)octyl  phthalate                    in                      5
      Fluoranthene                             1n
      Indene                                  1U
     Methyl chrysene           '                                       5
     1-Methyl  naphthalene'
     Naphthalene                              10                      5
     Phenanthrene
     Pyrene                                                           5
     Pyridine                                500                      5
     Quinoline                                                        5
                                                                     10

 4-   Semi volatile Acid-Extractable
     CompoundT

     Benzenethiol
     Cresols                                 10                      10
     2,4-Dimethylphenol                       10                      c
     2,4-Dinitrophenol                        on                      Cn
     4-Nitrophenol                            50                      c2
     Phenol                                   PC                      52
                                             '3                      5
                                    170

-------
                                     APPENDIX  E
          TARGET DETECTION  LIMITS  FQR SELECTED ORGANIC  COMPOUNDS  IN  WATER


  Table E.I  Target Detection Limits for Organic Compounds (Gansecki 1986)

  VOLATILE COMPOUNDS                                                           •-

  Parameter                                 ,,  ..,               Nominal Detection
  	                                 Un1ts                   Limit
  Benzene                                       /,
  Carbon tetrachloride                      Jja/i                       5
  Chlorobenzene                             J^/,                       5
  Chloroethane                                «/i                       5
  Chloroform                                 ^/                      10
  Cyclohexane                                JJ-J/j                      ,J
  1,1-Dichloroethane
  1,2-Dichloroethane
  1,1-Dichloroethylene                       ,,n/1
  Ethyl benzene                               ^/"                       5
  1,1,2,2-Tetrachloroethane                  !!a/l                       f
 Toluene                                    .My,.,                       _
 1,1,1-Trichloroethane
 1,1,2-Trichloroethane
 Trlchloroethylene
 m-Xylene
 o,p-Xylene

 BASE/NEUTRAL COMPOUNDS

 Acenaphthylene                             „/•,
 Anthracene                                 ua/1       '               ^
 Benzo( a) anthracene                         [Jg/T                      ^
 3,4-Benzofluoranthene                     ,,„/!                      ^
 Benzo(k)f1uoranthene
 Benzo(g,h,i)perylene
 Benzo(a)pyrene
 Chrysene
 Dibenzo(a.h) anthracene                     Ha/j                       f
 Fluorene                                   :,q/j                       5

Naphthalene0  Pyre"e                       [j9/J                       5
Phenanthrene                              [Jg^                       5

                                          vjg/i                       5
                                          ug/i                     10
                                    171

-------
Table E.I  Continued
   ACID COMPOUNDS

   Parameter

   0-Cresol
   m +  p-Cresol
   Phenol

   OTHER DETECTABLE QRRAMic

  Acenaphthene
  Acetone
  Acetonitrile
  Acrolein
  Acrylonitrile
  Aniline
  Azobenzene
  Benz(c)acridine
  Benzenethiol
  Benzidine
  Benzo(j)fluoranthene
  Benzoic  acid
  Benzyl alcohol
  Benzyl chloride
  Bis(2-chloroethoxy)methane
  Bis(2-chloroethyl)ether
  Bis(2-chloroisopropyl)ether
  Bis(chloromethyl)ether
 Bis(2-ethylhexylJphthalate
 Bromodichloromethane
 Bromoform
 Bromomethane
 4-Bromophenylphenyl ether
 2-Butanone
 Butyl benzylphthal ate
 Carbon disulfide
 4-Chloroaniline
 P-Chloro-m-cresol
 Ch 1 or od i b romome t h an e
 2-Ch 1 oroe thyl v i nyl ether
 Chioromethane
 2-Chloronaphthalene
 2-Chlorophenol
 4-Chlorophenylphenylether
 Crotonaldehyde
Oibenz(a,h)acridine
Dibenz(a,j)acridine
7H-Dibenzo(c,g)carbazole
                                          Units

                                          yg/l
                                          yg/l
                                          yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         U9/1
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                         yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                        yg/l
                                       yg/l
                                       yg/l
                                       yg/l
                                       yg/l
Nominal. Detection
      Limit

        5
        5
        5
       5
      10
     100
     100
     100
       5
       5
       5
      10
      50
       5
      25
      10
      5
      5
      5
      5
      5
      5
      5
      5
     10
      5
     10
      5
      5
      5
      5  .
      5
      5
     10
      5
      5
     5
     10
     5
     5
     5
                                 172

-------
  Table  E.I   Continued
  OTHER DETECTABLE ORGANIC COMPOUNDS  (Cont.)

  Parameter                                 „„,.«...             Nominal Detection
  	                                 Units                   Limit
  Dibenzofuran                              ..„/-,
  Dibenzo(a,e)pyrene                        Z                       5
  Dibenzo(a,h)pyrene                        ^n                      f
  D1benzo(a,1)pyrene                        ^a/1                      f
  1,2-Dlbromoethane                         ,,„/!                      5
  Di-n-butylphthalate                       ^/                       f
  1,2-Dichlorobenzene                       ,,a/l                      f
  1,3-Dichlorobenzene                       J^/j                      f
  1,4-Dlchlorobenzene                       .,0/1                      f
  3,3-Dichlorobenzidine                     ,,a/                      on
  Dlchlorodifluoromethane                   ,,a/                      ?S
  1,2-cis-Dlchloroethylene                  ua/                       2
  1.2-trans-Dichloroethylene                 ,,n/l                       ^
  Dichl orpmethane                            ,„/!                      ,
  1,1-Dichloropropane                        ^/i                      JJ
  1,2-Dlchloropropane                        .,0/1                       =
  1,3-Dichloropropane                        ^/l                       r
  2,2-Dichloropropane                        ^/                        f
  1,3-cis-Dichloropropene                    JIq/-I                       |
  1,3-trans-Dichl oropropene                 ,,a/l                       I
  2,4-Dichlorophenol                        ^/l                       f
  1,1-Dichloropropanol                      ya/1                       f .
  1,2-Dichloropropanol                      ,,«/!                      f
 1,3-Dichloropropanol                      fj/i                     • c
 2,2-Dichloropropanol                      ^/i                      5
 2,3-Dichloropropanol                      ,^/                       5
 3,3-Dichloropropanol                      ,Pa/                       f
 Diethylphthalate                           ,^/T                     J
 7 12-Dimethylbenz(a)anthracene            ^n/]                     2°
 2,4-Dimethylphenol                         y^/i                       5
 Dimethylphthalate                          y=/                       f
 4,6-Dinitro-o-cresol                       ,a/                      or
 2,4-Dinitrophenol                          "g/                      25
 2,4-Dinitrotoluene                         y^/                      5°
 2,6-Dinitrotoluene                         ,0/1                      !
 Di-n-octylphthalate                        ^/                      f
 1,4-Dioxane                                y2/J                    , 5
 Diphenylamine                              y3/                     10?
 Ethyl eneimine                              ^/J                      5
 Ethylene oxide                             y^/
 Ruoranthene                               y^/i                      "
 Formaldehyde                              y^/{                      5
Hexachlorobenzene                          a/i                      I  ..
Hexachlorobutadiene                          T
                                    173

-------
   Table E.I   Continued
   OTHER DETECTABLE ORGANIC COMPOUNDS fCont.)
                                                              Nominal. Detect ion
                                                                    Limit
  Hexachloroethane                            n
  Hexachlorocyclopentadiene                 f^/J                       5
  2-Hexanone                                y9''                       5
  Hydroquinone                              yg('                      10
  Indene                                    y9/                        5
  Isophorone                                yg/J                       5
  2-Methylaziridine                         y9^                       5
  Methylbenz(c)phenanthrene                 y9/
  3-Methylchloanthrene                       y?/                        5
  Methyl chrysene                             y9^                       5
  1-Methylnaphthalene                        y9>                        5
  2-Methylnaphthalene                        y9/                        5
  4-Methyl-2-pentanone                      y9(                        5
  Naphthyl amine                             n9/i                     10
  5-Nitroacenaphthene                       y9n              •        5
  2-Nitroaniline                            y9(]                      5
  3-Nitroaniline                            ^9<]                      5
 4-Nitroaniline                            y9(                      25
 Nitrobenzene                              y9;                       5
 2-Nitrophenol                             w\                       5
 4-Nitrophenol                             y9^                       5
 N-Nitrosodiethylarnne                      u^/                      10
 N-Nitrosodimethyl amine     ,               M2/                       5
 N-Nitroso-di-n-propyl amine                vl/\                       5
 Pentachlorophenol                          y9(                       5
 Quinoline                                  w\                       5
 Styrene                                    ^9/                        5
 Tetrachloroethylene                        pg/i                       5
 1,2,3-Trichlorobenzene                     U2/                       5
 1,2,4-Trichlorobenzene                     y9/   '                    5
 1,3,5-Trichlorobenzene                    u9n                      5
 Trichlorofluoromethane                     n/i                      5
 2,3,4-Trichlorophenol                     u9/                      10
 2,3,5-Trichlorophenol                     u2/i                      5
 2,3,6-Trichlorophenol                     y9/                       5
 2,4,5-Trichlorophenol                     Pa/i                      5
 2,4,6-Trichlorophenol                     y^/i                      5
 3,4,5-Trichlorophenol                     y9/i                      5
Trimethylbenz(a)anthracene                f,?/                       f
Vinyl  acetate                             y9n'                       5
Vinyl  chloride                            y9>                     10
                                                                  10
                                   174

-------
                                  < " t t_* 1U 1 A f                 w-'% t ••«' •	
                      EXTENDED RITZ MODEL FORTRAN LISTING
                                                                    00*2   1
  c
  c
  c                    USU LTD
  C
  C  Utah State University land Treatment Demonstration model.

  C  3£?f^ ^SiL5y^_te^wil^ ^enney
  C
  C  °SreS 2 SIS SSf^^? " -atr^ies, either
  C
  £ 2^fl^oansequent^
  v- urns program.
  C
  S****.^??^??^3^.2^18100 ^y 2,
                     //2)/RKDW(152)/RK^
      *                                ,         ,RKW5(152)
      *            ,K>,BMK)(152)
                               lIHEEAW/'IHErAA(152) ,

                               RMUEO(152) ,RKEWD(152) /QEOSO(152)

                         52) ,EEA(1S2) #XMDEIk(152) ,RKEWA(152)

 OCMON/CX3EEW/VEW(152) ,DEW(152) ,PMUEW(152) ,RKEOW(152) f RREW(152)
                   ,RKESW(152)
C*

       CHARACTER *32 FIIEI, FILED, PIIBl
       CHARACTER *80 TITLE
       CHARACTER *15 IDENT
     +  DIMENSION TOI(13) ,DIDI(13) ,TCHNG(13) ,TKM(13) ,TEaf(13) ,ZX(13)
           , (50(13) ,OOZ(13),CAZ(13),CSZ(13),VWE«M(13)
            _  »SHC(13)
       CHRRAC3ER  *40 ITEXT
C*

°*               813168 US8d to trad}c fate of Pollutant to zero
       SADW=0.0
       SDATOIM3.0
       NCOUN=0
                                175

-------
         WRITE (1,2000)
  2000       PORMAT(» ENTER FILENAME FOR INPUT
         READ (1,1000) FILEI
  1000       FORMAT (AO)
         WRITE (1,2002)
  2002
 c
        WRITE(1,2004)
 2004
        IF(ICWRIT(10,2/0,"ECHD.I»T"))GOrO 998
        WRITE (1,2030)
 2030       F3RMAT(1X, ''ENTER FOE Iim?imCATICN TEXT TOR PLOT ITIE

        HEAD ( 1 , 5004 ) nEXr
        WRITE (9 , 5005) ITEXT
 5005       F3RMAT(1X,AO)
 5004       KJRMAT(AO)

 C*
        NREAD=0
 5027       FORMAT (IX, 15)
       WRITE(1,5027)NREAD

       READ (7 , 1001) TITLE
1001       FORMAT (AO)
       WRITE (8 , 2010) TITLE
       WRITE ( 10 , 2010) TITLE
2010 .      FORMAT(1X,AO)

       NREAD-NREAD+1
       WRITE (1, 5027) NREAD
       READ (7 , 1002) IEENT, DTZCNE, DPZCNE, DZ
       WRITE (8 , 3002) IDEMT, DTZONE, DPZONE, DZ
       WRITE (10, 3002 ) IDENT, DTZCNE, OPZONE, DZ
       WRITE(1,5027)NREAD


                                  176

-------
        READ (7, 1002 )3XENT, DETECT
        WRITE(8,3002)IDENT,DErECr
        WRITE (10, 3002) IDENT, DETECT
 3002        FORMAT(1X,AO,11G10.3)
 1002        FC»!AT(A15,13FO.O)

        NREAD-NREADfl
        WRTTE (1, 5027) NREAD
        KE^(7,1002)IDENT,TOIALT, DT
        WRITE (8, 3002 )IDENT,TOTALT, DT
        WRITE(10,3002)IDENr,TOrALT, DT

        NREAD=NREADfl
        WRTTE(1,5027)NREAD
        HEAD(7, 1002) IDENT, TOI
        WRITE (8, 3002) IDENT, (TOI(I) ,1=1,10)
        WRITE (10, 3002) IDENT, (TOI(I) ,1=1,10)

        NREAD«NREADfl
        WRITE (1 , 5027) NREAD
        READ(7, 1002) IDENT,DTOI
        WRITE (8, 3002) IDENT, (DTOI(I) ,1=1,10)
       WRITE (10, 3 010)
         WRITE (8, 3010)
         WRITE (1,3010)
3010 ^     FORMATdx,/," **iNR7r ERROR** DIDI(l) must be greater

       IF(IOCLOS(7))GC3TO 992
       IF (10008(8)) GOTO 994
         STOP
       NREAD-NREADfl
       WRITE ( 1 , 5027 ) NREAD
       KEM>(7, 1002) IDENT, SMLB, EKE, FH3SI
       WRITE (8 , 3002) IDENT,SMLB, PHI ,RHOSI
       WRTTEdO, 3002) ZDENT,SMLB,EHI,F5JOSI
      BHOS-RHOSI*1.0E6

      NREAD-NFEADfl
      WRITE (1 , 5027) NREAD
      FEAD(7, 1002) IDEMr,RMDWPZ,RMUWLZ
      WRITE(8, 3002) IDENT, RMUWPZ,RMUWLZ
      WRITE (10, 3002) IDENT,RMUWPZ ,FMJWLZ

      NREAD=NREADfl

                                 177

-------
   WRITE (1, 5027) NREAD
   KEAD(7, 1002) H2ENr,RKDWPZ,RKDWLZ
                      ,/
   WRITE(10,3002)IDENr,RKDWPZ/RKiDWL2

   NREAD-NREADfl
   WRnE(l,5027)NREAD
         , 1002) IDEOT,RKAWFZ,RKAWLZ
                     ,,
   WRITE (10, 3002) IDENr,RKAWPZ ,RKAWLZ

   NREAD=41READfl
   WRITE (1 , 5027) NREAD
         , 1002) ZDENT,RKSWPZ/RKSWI2
          ,,,Z
  WRHE (10, 3002) IDENr,RKSWPZ/PKSWI2

  NREAD=NREADfl
  WRITE(1,5027)NREAD
                    /,/
          ,3002) mEOT,WAR,OCNSW/WITO
  WRTrE(10/3002)IDENr/WAR/CDNSW/wrro

  NREM>*IREAI>fl
  WRITE(1, 5027JNREAD
        , 1002) ZDENr,WrFWf K3EW,RDEOI
                    ,//
  WRITE(10/3002)IDENr/WrFW,RDEW,PDBOI
 WRITB(1,5027)NREAD
 READ(7 , 1002) JDENT, DTAC, DEAF
 WRITE (8 , 3002) IDENT, DIAC, DEAF
 WRITE (10, 3002) IDENr, DTAC, DEAF
 WRITE (1, 5027).NREAD
 READ (7 , 1002 ) IDENT, HO
 WRITE (8 , 3002) IDENTIC
 WRITE (10, 3002) 3UENr/HD

 NREAD-NREADfl
 WRITE (1, 5027)NREAD
 READ(7, 1002) ZDENT/RMUDPZ/RMUDLZ
 WraTEtS, 3002) ZDENT^BMUOPZ.RMtroia
 WRnE(10,3002)HSNT/ia*X>PZ,BMUOIZ

 NREAD-NREADfl
 WRTTE(1/5027)NREAD
 READ(7/ 1002) IDfHT, DA, VA
WRITE (8 , 3002) IDENT, DA, VA
WRITE (10, 3002) IDENT, DA, VA

                           178

-------
  NKEAD=NREADfl
  WRITE (1,5027)NREAD
  READ(7,1002)IDENr,RMLIAPZ,RM[IAIZ
  WRTIE(8,3002)IDENT,RMUAPZ,RMUAIZ
  WRITE (10,3002) IDEOT,RMUAPZ,KMUAI3

  NREAD=NREADfl
  WRITE (If5027) NREAD
  READ(7,1002) IDENr,RMUSPZ,RMUSI2
  WRITER, 3002) IDENr,RM[JSPZ,RMUSLZ
  WRrrE(10,3002)inENr,RM[JSPZ,RMUSI2

  NREAD=NREADfl
  WRTIE(1,5027)NREAD
  READ (7,1002) IEENT, ZX
  WRITE(8,3002)IDEOT, (ZX(I) ,1=1,10)
  WRITE(10,3002) IDENT, (ZX(I) ,1=1,10)

  NREAD=NREADfl
  WRITE(1,5027) NREAD
  READ(7,1002) IDENT,C5JZ
  WRITE(8,3002)IDEMT,(CWZ(I),1=1.10)
  WRITE(10,3002)IDENT,(CWZ(I),1=1,10)

  NREAD=NREADfl
  WRITE(1,5027) NREAD
  READ (7,1002) H2ENT, OOZ
  WRITE (8,3002)IDENT,(COZ(I),1=1,10)
 WRITE(10,3002)IDENT,(OOZ(I),1=1,10)

 NREAD-NREAEH-1
 WRITE (1,5027) NREAD
 READ(7,1002)IDENT,CAZ
 WRITE(8,3002)IDENT,(CAZ(I),1=1.10)
 WRITE (10,3002)IDENT,(CAZ(I),1=1,10)

 NREAD=NREADfl
 WRITE (1,5027)NREAD
 READ(7,1002)IDENT, GSZ
 WRITE (8,3002) IDEWT, (CSZ (I), 1=1,10)
 WRITE(10,3002)IDENT, (CSZ(I) ,1=1,10)

 NREAD=NREADfl
 WRITE(1,5027)NREAD
 READ(7,1002)IDEWT,THETQX
 WRITE(8,3002)IDENr, (THETOX(I) ,1=1,10)
 WRITE(10,3002)IDEMr, (THETOX(I) ,1=1,10)

NREAD=NREADfl
WRITE (1,5027) NREAD
READ(7,1002)IDENT, TFACT

                            179

-------
          WRITE ( 8 , 3 002 ) IDENT, TEACT
          WRITE (10, 3002) HJENT,TFACT

          NREAD=NREADfl
          WRITE(1,5027)NREAD
          READ(7,1002)IDENr, (TPZM(I) ,1=1,12)
          J®^(8,3006)H2ENT, (TPZM(I) ,1=
         NREAD=NREADfl
         WRITE (1,5027) NREAD
         JEA£(7,1002)IDENr, (TLZM(I) ,1=1,12)
         WRITE (8, 3006) H3ENT, (TIZM(I) 1=1 12)
         WRITE (10, 3006) IDENT, (TIZM(I) ,1=1,12)

         NREAD=NREADfl
         WRITE (1, 5027) NREAD
         JEAD(7,1002)IDENr, (VWIWl(I) ,1-1,12)
         WRTO 8, 3006) IDENT, (VWHttd) , 1-1,12)
         WRITE(10,3006)IDENr, (VWFRM(IJ 1,1=1,12)

         NREAIMIREADfl
         WRITE (1 , 5027) NREAD
         ^AD(7,1002)IDEOT, (SHC(I) ,1=1,12)
         WRITER, 3006) IDENT, (SHC(I) ,1=1,
 ^      WRITE (10, 3006) ffiENT, (SHC(I) ,1=1,

         IF(IOCLDS(10))GOTO 998

        JT-1
        JTP1=2
        NIZ-2+DTZONE/DZ
        KDZPZ=(0. 5+DPZONE/DZ)
 c              volcu in units of 103/102
                         G-SOZL/M3-OCNTROL VDIDME
                 WTPO  = R3-OIL/K3-WASTE
                 ROEOI = G-OIL/CC-OIL
 C* M3-OIL/M2=M*:M2* (G-SOIVM3) * (G-WASTE/100-G-SOIL)
 C*       * (KG-on/K3-WASTE) * (OC-On/G-OIL) * ( V10E6)
                                         *1.0E8)
C*       CMASSP - MASS OF CONSTITUENT IN PLOW ZONE
C*       RHOS   m G-SOIL/M3 OONIROL VOLUME
C*       DPZONE = M
C*       WAR      G-WASTE/100-<^-SOIL

                                  18D
                                                        100 G SOIL

-------
           CONSW  - OCNSTITUINr IN WASTE  KM; G-OONSnTUENT/106-O


                                       . OE8
                                                       OIL
         IF(VDIIX>.LT.l.E-12)GaiO 37
         CMASSP/(VDIIJD)
  37       OCNTINUE

  C*
         CALL IMIERC(ZX/CWZ/a*/JT,DZ,NIZ)
         CALL
                                 ff
         CALL IMIERC(ZX,CAZ/CA,JT,DZ/NIZ)
         CALL INIERC(ZX,CSZ/CS/JT/DZ/NIZ)
         CALL !NlERC(ZX,raElCK,TOEraO,JTfDZ,NIZ)

 C*
         DO 30 IZ-1,NDZPZ+1
          RKCW(IZ)-RK3WPZ
          RKAW(IZ)=RKAWPZ
          RKSW(IZ)*RKSWPZ
          RKW3(IZ)-RKWDPZ
          RKWA(IZ)*RKWAPZ
          RKWS(IZ)-RKWSPZ
 30         OCNITNUE
        DO 35 IZ>^DZPZ+2,NIZ
          RKAW(IZ)-RKAWLZ
          KKSW(IZ)-RKSWLZ
          RKWD(IZ)=PKWDLZ
          RKWA(IZ)-RKWALZ
          RKWS(IZ)«PKWSLZ
 35         CCNTINUE
 C*
        TIME=0
       TIMEXX)
       TLZ-TLZM(l)
       EX=1.0/(2*SMLBf3)
C******SB3RT"S EQUATION
       IF(mEIAW.Gr.0.05)GOTO 40
       VW=0
       GOTO 42
40
                                  181

-------
  42       CONTINUE
         DO 43 IZ=2,NIZ
           THETAA (12) =Hn-THETAW-THEIAO fIZ )
  43       CONTINUE
  C*
  C***ERINT INITIAL CCNDITIONS INCLUDING INITIAL MASS

         DO 48 IZ=2,NIZ-1
         SCONS=CS (IZ , JT) *RHOS
         SCONVKW (IZ , JT) *THETAW
         SOCNDM30(IZ,JT)*TflETAO(IZ)
         SOONA=CA(IZ, JT) *THBTAA(IZ)
  48        OCNTINUE
  C*        OCNVERT OCNCENTRATICN TO MASS
        SUMS=SUMS*DZ
  °*                                              SUM!
 C
 C       INITIALIZE OUTH7T CONTROL

        TIME=0.0
        ISTOPO=0
        IOUT=1
        TIMEO=DTOI (IOUT)


        CALL OUT (NOOUN,SUMI,JT/ DETECT)

 C       CALCULATE DT SO THAT VW*DT/D2-1
        IF (VW. GT . . 00015) DT-DZ/VW
50       CONTINUE
       TIME=TIME+DT
       IF(TIME.GE.TIMES) CALL SIDDGE(TIME,TIMES,DTA^DTAF^UJO,GO
     +                                SUMI)

       IF(TIME.GE.TIMEM) CALL MONTH (TIME, TTMEM/DT/VWERM,DELVW,DELIHW
                               , SMLB, FHI, TPZM, TLZM, DELTPZ, DELTLZ, SHC)

       THKTiyiHETAW
       THETDW^IHErAWfDELIHW
       VW^VWfDELVW

C       CALCULATE DT SO THAT VW*DT/DZ»1
C       DT=2
       IF(VW. GT..00015) DT-DZ/VW
       TPZ=TPZ+DELTFZ
       TLZ=TLZ+nELTLZ
                                  182

-------
          TFPZ=*TFACr** (TPZ-20)
          TFLZ=TFACT** (TLZ-20)
          DO 55 IZ=1,NDZPZ+1
            RMUW(IZ) •$MUWPZ*TFPZ
            RMUA(IZ) =£MUAPZ*TFPZ
            RMUS (IZ) =RMUSPZ*TFPZ
   55         CONTINUE
          DO 60 IZ«NDZFZ+2/NIZ
           I'MUO (IZ ) -FMUOIZ^rFXZ
           IMS (IZ) =PMUSI2*TFLZ
  60         CONTINUE
             EJ03IANGE AND DECAY
         CALL DECAY OIHHOT, SDECAY)
                 TRANSPORT MECHANISMS
                 ADVECTION IN WATER,
                  DIFFUSION IN AIR

         CALL TRANS (PH^SADW.SDAIDP)
         NOOUN=NaOUN+l
                RJJILIBRIUM OF SDBSTMJCE BB1WEEH MEDIDM
        IF (EW.GE.. 0001) CALL EQUIL (SUMS)
         CALOJIATE MASS AFTER TRANSPORT
        SUMS=0.0
        DO 49 IZ=2,NIZ-1
        SOONS=CS(IZ, JTP1)*RH3S
        SODN1*CW(IZ, JTP1) *THETAW
        SCCNX»(IZ, JTP1) *THEIAO(IZ)
        SOONA-CAflZ, JTP1) *THETAA(IZ)
           »
         CONTINUE
C*       CONVERT CONCENTRATION TO MASS
       SUMS-SUMS*DZ
C*              CALCULATE ERROR
                                183

-------
  C*              SAEW IS THE AO3JMUIATED LEACHATE
  C*              SUMS IS THE REMAINING MASS
  C*              ELEMENT NIZ IS BELOW THE LOWER
                  ^SP1 ZCNE' **** SUBSTANCE ENTERING ELEMENT NIZ
                  IS TREATED AS  LEACHATE AND IS ACCUMULATED IN
  C*               SADW

  C*       RMASS  IS THE REMAINING MASS
        BMASS=SUMI-SDEXa
        ERROR=SUMS-FMASS
        CALL CUI2(TIME,SI2X^/SADW,SUMI,ERRC(R,NCaJN,DETECT,SDATO

        IF (TIME. LT.TTMEO) GOTO 80
        CALL OUTPUT (TIME, SUMS,
      *             VW,SDBCAY, SADW, SDATOP, ERROR, SUM!, DETECT)

        IF(TOI(IOUTfl).LT.i.E-5)GOTO 85
        IF((TOI(IOUT) .LT.TIME) .AND. (TOI(IOUTfl) .GT.TIME))GOTO 85
        lOUA^IO^t^l                                     *
 85       CONTINUE
        TTMEO=TIMEOfDTOI (IOUT)

 80       CONTINUE

        JX=CT
        JT=JTP1
        JTP1«OX
        IF (TIME. LT.TOTALT) GOTO 50
        IF(IOCLOS(7))GOTO 992
        IF(IOCLOS(8))GOTO 994
        IF(lOCLOS(9))GOTO 993


       WRITE (1) "NORMAL TERMINATION11

       STOP

992       WRITE (1) "ERROR CLOSING INPUT FILE "
       IF(IOCLOS(8))GOTO 994
       IF(IOCLOS(9))GOTO 993
       STOP
994       WHITE (1)" ERROR CLOSING OUTPUT FILE"
       IF(IOCLOS(9))GOTO 993
       STOP
993       WRTTE(l)" ERROR CLOSING PLOT FILE "
       STOP

996       WRITE (1) "ERROR OPENING OUTPUT FILE "
       STOP
                                 184

-------
   997


   998



  999
   WRITE (1) "ERROR OPENING PLOT FILE"
STOP

   WRITE(1)» ERROR OPENING ECHO TTTF n
STOP


   WRITE (1) "ERROR OPENING INPUT FTTP n
STOP                         -   "^
END
  c
C

C
                SUBROUTINE ODI2
                                                    of
AS

DECAYS.
                 *• «» percent treated,  PC STORK AT 100 AND

                     OOOJRS.  OBNGE IN K SB3DU, DEORE^ M
        DOUBI£ PRECISION PC ,XIEACH, TOTAL
                   J^;|l'TIMEfl/6X,''MASS DECAYED" , 3X, "IEACHED"
      *         "LEACHED'-^X, "PERCENT TREATED", 4X "ERROR" /TY

                   ^111^^"'1^11011^")                     '
 1002
        TOTALrSUMI
        IF (TOTAL. LT.l.E-12) GOTO 70

 70       CONTINUE
        ODECAY=0.0

        IF(SDEQ^.GT.DE^ECT)ODECAY=SDECAy
        OSADW=0.0
        IF (SADW. GT. DETECT) OSADW=SADW
        QAIR=0.0
        IF (SDATOP. GT. DETECT) QAIR=SDATOP
1000


       END
                                185

-------
  c
  C              SUBROUTINE TRANS
  C       This subroutine adverts the substance in water
  C       hi/ *S^i^^?^^_?^:...,!Eran^rt to water is solved
C       The explicit method was choosen for water to reduce
c       gSS^ f^f ' J*" iaplicit Bethod
                     air to
  r         5^      ar to P*8761* negative values and reduce
        SDBROTTINE IRANS  (PH,SADW/SEftIOP)
                                  ,RKDW(152) ,RKAW(152)
      *             'S?^152* »"»»(15a) ,PKWA(152) ,RKWS(152)
      *             /HD,»03(152) /QO/nA/VA,EMUA(152)
                                    O, VD
        CW(1,JT)-0.0
        DO 10 IZ=2,NIZ-1
 C*              CAIOJIATION  PCR WATER. ADVECTICN CNIV
        CW(IZ/JTPl)
-------
   C       substance concentration in each medium.

         SUBROUTINE EQUIL (SIMS)
*
*
               » 0
         SIMCA-O.O
         SUMS=0.0
         DO 10 IZ-2,NIZ-1

 e      ffi OP      01*15 CT (152) ,RKWA(152) ,RKWS(152)
                                  ,QO,nA,VA,PMUA(152)
                                   '130'™
                                  IHEIAW/THEIAA(152) ,KHQS
        J£J?L?I3VM3 OIL)*(M3 OIIy^D OCNTROL VOL)
        SOONOCO(IZ,JTPl)*IHBrAO(IZ)
          (G IN AHVN3 AIR)*(M3 AHV/CONI3«)L)
        SOONA-CAdZ,,^1?!) *THEIAA(IZ)
        CT^OGNS+SOCNV^SOONO+SCONA

         CAIflJIAEE TOTAL OCNGENERAITCN IN SLICE
 c
        SUMS-SUMS+CT*DZ
                 KHOS*RKSW(IZ)


       CW(IZ,JTP1)»CT/BW
                          •OE•22>ro(IZ'™1)S!R^CI2)*a^(Iz
C       CHECK TO SEE IF MASS BALANCE IS MAINTAINED
C       SONS-OS (IZ,JTP1)*RBDS
C       SCCNW=CW(IZ,JTP1)*THEIAW
C       SCrNXX)(IZ,JTPl)*THETAO(IZ)
C       SCCNA»CA(IZ,JTP1)*THETAA(IZ)
                                  187

-------
  c
  C       SUMCA=SUMCA+Cr*DZ
  10       CONTINUE
         RETURN
         END
 C™
 C*               SUBROUTINE DECAY
 C*       This subroutine decays oil and calculates the new
 C*       substance concentration.
        SUBROUTINE  DECAY (TflHOT,SOECAY)
        a»*DN/VAR/CW(152,2) ,00(152,2) ,CA(152,2) ,08(152,2) ,JTP1
      *                 ,JT,DZ,DT,NIZ,NDZPZ

        CXMMCN/PAR/VW,DW,RMUW(152) ,KKDW(152) ,RKAW(152)
      *
                                 ,QO,DA/VA,FMUA(152)
      .             * 	 "      »   f f ^~ W ~™~/ w
      *             ,KMUS(152),HJI,DO,VO
        COM^*^/THETA/THETAO(152),THETAW/THETAA(152)  RHOS

 C*          DECAY OF THE OIL MEDIUM

        EX=EXP(-«5*DT)
        DO 10 IZ=2,NIZ-1
        IF (THETAO(IZ). IT. 0.00001) GOTO 10
        OMS=00 (IZ, JT) *THETAO (IZ)
        THETAO (IZ) «
-------
  14        CONTINUE

  C*          DECAY WITHIN MEDIA

        DO 30 IZ=2,NIZ-1
        CWDLD=CW(IZ,JT)
           CW(IZ, JT) -CWDID*EXP(-RMUW(IZ) *DT)
        SDECAY^DECAY+(CWOID-CW(IZ, JT)) *THETAW*DZ
        OOOUXD (IZ, JT)
           00(IZ,JT)=CCOID*EXP(-RMUO(IZ)*DT)
        SDECAY*SDECAY+ (COOID-OO (IZ, JT)) *THETAO f IZ) *DZ
        CAOU>CA(IZ,JT)
           CA(IZ/JT)-CADLD*EXP(-FMUA(IZ) *DT)
        SDECAY-SDECAY+fCAOID-CAflZ.JT))*THETAA(IZ) *DZ
        CSOID=CS(IZ/JT)
           CS (IZ, JT)-CSOID*EXP (-RMUS (IZ) *DT)
        SDECAY-SDECAY+ (CSOID-CS (IZ. JT)) *RHDS*DZ
 30         CONTINUE

        RETURN
 	END	
 (ihKKKh'KKKKKh M \-'\-V\..\,\hv.vi.vvv


 C*
 C*            SUBROUTINE INTERC
 C*            This subroutine  interpolates the initial conditions,
 c*            input by the user,  onto the DZ grid.  Concentrations
 c*            are calculated at points midway between  grid nodes.

       SUBROUTINE XNTERC(ZX,CX,C,JT,DZ,NIZ)
       DIMENSION  ZX(1),CX(1),C(1,1)

       DO  2  I«1,NIZ
       C(I,JT)=O.O
2       CONTINUE
       IF(ZX(l).Ur.l.OE-10)GOTO 1
       WRITE(8,2002)
2002       PORMATflX,/,"  ***WARNING INTERC*** Initial conditions do
not start"
     +             ," at  the surface.")

1       Z—DZ/2
       C(1,JT)-0.0
       CBAS-0
       11-0
       12-1
       DEHX).0
       DO 5 I=2/NIZ-1
                                189

-------
         1F(CX(I2).LT.1E-20)GOTO 4

           Z=Z+DZ
           IF(Z.LT.ZX(I2))GOTO 10
             12=12+1
             IF(ZX(I2).GT.1.0E-10)QOIO 15
  c*
              ZX(I2) =10000
             DELOO.O
             WRITE (8, 2000) CX(I1)
  2000^        FORMATd*,/, - ***WARNING iNTERc*** initial conditions
                                   °f ** trBatanent
 c*
                  »«r(«,/,ix, " **ERRQR INIERC** gp^ in initial
                           "
              STOP
                          '   npU  ""^ ** greater ^^an 2*DZ»)
 10        C(I,JT)=CBAS+DELC*(Z-ZXril))
 5         ODNTINUE    •
 4       CONTINUE
        C(I-1,JT)=0.0
        RETURN
        END
c*
C*              SUBROUTINE SLUDGE
                 Ada sludge to the plow zone every DTAF days
~               the period DTAC each year.
C*

C*               VOIDD : VOLUME OF OIL ADDED (M3/M2 SURFACE)
X               GO    : OCNCENTRATION IN THE OIL (G/M3)
C*               TIMES I TIME TO TRIGGER NEXT APPLICATION
       SUBROUTINE SLUDGE(TIME/.TIMES/DIM/DTAFfVOLUD/GO/SUMI)

                           ,00(152,2) ,CA(152f 2) ,05(152,2) ,JTP1
                       ,JT,DZ,DT,NIZ,NDZPZ
                               THErAW,TflETAA(152) ,

                              1,

C*
                                190

-------
   c*
   C*          ESTABUST THE TIME OF THE NEXT APPLICATION

         IF(DTAC.CT.0.01)GOro 5
   C*        Ino land application cycle
         TIMES=1.0E10

         RETURN
  C*

  5       I*EAR=(TIME+1.0E-6)/365
  C*       ITIME TO SUSPEND FOR THIS YEAR
         SUSP=IYEAR*3 65f DEAC
  C*       inext application this year
         TIMES==TIMES+DIAF
         IF(TIMES.I£.SUSP)OOTO 10
  C*       istart again next year
           TIMES=(IYEARf 1) *365
 C*        Ino oil was adied
 10        IF(VOUXXLr.l.OE-9) RETURN

        SUMVD=VOIDO
        SUMI=SUMH-SLIMMCO
        DO 20 IZ=2,NDZPZ+1


          SUMMCX>BSUMMCDfCO (IZ ,JT)*THETAO(IZ)*DZ
 20        CONTINUE                  ^^;  Ufi

        VOAVE=SUMVO/(NDZPZ*DZ)
        CMASAV^SUMMOO/ (NDZPZ*DZ)


        DO 30 IZ=2,NDZPZ-H
          THETAO(IZ)=VOAVE
          CT> (IZ, JT) "CMASAV/THETAO (IZ)
 30          OCNTINUE
 C*

       RETURN
       END
C*

C*              SUEROUTTNE MOTH
C*

       SUBRDUTINE M»raTIMET^

       DIMENSION VWPRM(l) /
       IVEAR= (TIMEMf 1) /365
       Il-l+( (TIMEMfl) -IYEAR*365)/30.416


                                 191

-------
         I2-I1+1
         IF (12. GT. 12) 12=1
         EX=1.0/(2*SMIBf3)
          SHC IS TOE SATURATED HYERAULIC OCNDUCITVIIIY SEE SHORT'S

         THET1=FHI*( (VWFKM(I1)/SHC(I1)) **EX)

         THET2=FHI* ((VWPHM(I2)/SHC(I2)) **EX)

         EEnmw=DT* (THET2-THET1)/30.416
 c*
         IF(THETl.GT.O.Ol) GOT02
         VTO^O.O
         GOTO 4
 2       VWl«^VWFRM(Il)/lHEri
 4       IF(THET2.GT.0.01)GOTO 6
        VW2-0.0
        GOTO 8
 6       VW2-*VWFBM(I2)/IHEr2
 8       EELVW«nr*(VW2-VWl)/30.416
 C*
 c*
 C*              TEMPERATURE CHANGE
 C*
        EEnTPZ=DT*(TPZM(I2) -TOZM(Il) )/30.416
 ^     EEIiri2=Dr*(TLZM(I2)-TL2M(Il))/30.416

        TIMEM=TIMEJf(-3 0.416
        RETURN
        EUD
     *
                SUBROUTINE OUTPUT
               ******************<
       SUBROUTINE OUTPUT (TIME, SUMS,
       ^n^r/,»«,           /
       OCMMDN/VAR/CW(152,2) ,CJO(152,2) ^(152,2) ,08(152,2) ,JTP1
     *                  fJT,DZ,DT,NI2/NDZPZ
       COM^/1HETA/THEIAD(152) ,THETAW/THETAA(152) ,KHOS
       CCWCN/CUTFUT/ TIMEOX,nM,ISTOFO,DIOIX
       DIMENSION TOI(l) ,0101(1)


30       ISTOFO-ISTOFOfl
       IF(ISTOFO.Iir.51) GOTO 31

         WRITE (8, 2000)
             PORMAT(1X,» **SUBROUTINE OUTPUT** output limited to 50



                                 192

-------
         WRITE (1) "EXCEDED CUTRTT UMIT"
           STOP

  31       CCNTINUE

  C*            OUTPUT VALUES


  35       OCNITNUE

        WRITE (8, 1000)  TIME, DT, Sure, W,SDECAY,SADW,SDATOP
       *    _        ,ERROR,SUMI

  1000  *   ,, v^cS:^ " II/F12-3'" ro • "'G13-5'
       *   "SDECAY'= "^GII.'S," SADW = "^GII.S," SDAIDP =»
       *   Gil. 5," ERRCR =",011.5," INITIA MASS ="       '
     \* /  °11-5'/'1X'"00 (9 substance in oil)/(M3 control
     ;  i/ tlXt
       *   "DEPTH", IX, 4X,"CW"
       *   /7X,4X,"00»/7X,4X,"CA",7X,
       *  4X, "CS" , 7X, 3X, "TOETAD" , 4X, 3X, 'THEEAW" , 4X, 3X, "3HEIAA")


        DO 10 IZ=1,NIZ

        OXUIXD (IZ , JTP1) *IHETAO (IZ)
        IF (CXJCUT. Iff. DETECT) OOOUT=0 . 0
                  r.DEIECT) CWDU1M). 0

        CACUr=CA(IZ,JTPl)
        IP (CACUT. IT. DETECT) CAOU1M) . 0
        iF(cscur.iir.DEiEcr) csou]>o. o

        DEPT=(IZ-1)*DZ
        WRITE (8 , 1050) DEPT, CWOUT, C30COT, CACOT,
      *               CSCOT,THEIAO(IZ)/IIHETAW,THETAA(IZ)
 10       OCNTINUE

 1050       IilO»MAT(lX/F5.2/2X,4(G11.5/2X),3(G11.5,2X))
       REIUFN

       END
                     iLtJLLi^KhiiKkhlkKt.'kkkkkt.t.'Vk'Vk^.kk'VVt.'b'u-vkkk't.'t.'t.'U'

C*
C*              SUBROUTINE dDSE

                                193

-------
 c*
        SUBROUTINE CDDSE
        WRITE(l)" TERMINATED DUE TO ERROR"
        WRITE(8,3000)
 3000       PORMAT(1X,/," PBOGRAM TERMINATED BEPCJRE COMPLETION")

        IF(IOCLOS(7))GOTO 992
        IF(IOCL0S(8))GOTO 994
        IF(IOCL0S(9))GOTO 993
 992       WRITE (1) "ERROR CLOSING INPUT FUE "
        IF(IOCLOS(8))GOTO 994
        IF(IOCXOS(9))GaiO 993
        STOP
 994       WRITE(l)" ERROR CLOSING OUTPUT FHE"
        IF(IOCIDS(9))QOTO 993
        STOP
 993       WRITE(l)" ERROR CLOSING PLOT TTTF H
        STOP
       END
C
C              SUBROUTINE OUT
C       This subroutine outputs the inital condition.
       SUBROUTINE OUT (NCOUN/SUMI,ICIUT, DETECT)
       OMCN/VAR/CW(152,2) ,00(152,2) ,CA(152,2) ,CS(152,2) ,JTP1
     *                 ,JT,DZ,DT,NIZ,NDZPZ
       CCM^lK/THErVTHE^AO(152) ,THETAW,THETAA(152) ,RHOS
       WRITE (8 , 2000) NOOUN, SUMI , DT
2000       FORMAT(IX,"NCOUN  INITIAL MASS G  DT =", / IX
     *   I5,G11.4,F5.2)                             '   '
     '  WRITE (8, 1000)
1000       FORMAT(1X,
     *      "DEPTH" , IX, 4X, "CW" , 7X, 4X, "CO" , 7X, 4X, "CA" , 7X,
     *   4X,MCSn,7X,3X,MTHETA^M/4X,3X,"THEI3^^4X,3X,"THE^AA")
       DO 10 IZ=1,NIZ
       COOU3XX) (IZ, JTP1) *THETAO (IZ)
       IF (COOUT. LT. DETECT) COOUT=0.0
                                 194

-------
                     , JTP1)
         IF (OKX7T. Iff. DETECT) CWDUT=0 . 0
                     , JTP1)
         IF (CACUT. Iff. DETECT) CftOUIK) . 0
         IF (CSCUT. Iff . DETECT) CSOUT=0 . 0

         nEFT=(IZ-l)*DZ
         WRiiE(8/io50)DEiT,cwa7r,aoou
                       CSCOT,1HEIAO(IZ) ,THEIAW,'mEIAA(IZ)

  10       C3CNTINCJE
        RETURN
        END
                 SUERCUTINE AIR TRANSKRT
            3 SUbrCUtlne "^ « ^l^it solution technique to
 C       transport of the substance in air.

       SOBRCT7EINE AIR (SEftTOP)
       OMCN/PAR/VW, EW,RMUW(152) ,RFCW(152) ,RKAW(152)

                    'S^SSUHfWD(152) '^^f152) ,
     *              'IC'RMUD(152)fQO,DA,VA/RM[]A(152)
C*              Uffi OHEaaA(l) R2R AIR ABOVE, IT WOUID BE FGR
       1HETAA(1)=1
       SHETAAfniz) =thetaa (niz-1)
      do 50 iz-2,niz-l

                                 195

-------
        xnassl?=xmassbKa(iz,jt)*dz*thetaa(iz)
 50       continue
 C*              SET ARRAYS A, B, AND C
        M-NIZ+1
        MPl=Mfl
        THA(1)=1.0
        1HA(2)-1.0
        DO 80 1-3,NIZ
        1HA(I)-!1HETAA(I-1)
 80       OCNTINUE
        THA(M)-fVARA
        B(I)=1.0+2.0*RATIO-VARA
2      . CONTINUE

C*              BOUNDARY AT JTP1
       T(l)=0.0
       T(MP1)=CA(NIZ,JT)
       DO 5 1=3,M
       D(I)=CA(I-1,JT)
5       CONTINUE
       D(2)-O.O+RATIO*T(1)
       D(M) -D(M) -(-RATIO*! (MP1)
       CALLTRIDAG (2,MfA,B,C,D,T)
       SDATOP=SDATOP4T (2) *DZ*1
        SDABCG>6DABOT4T(M) *DZ*THA(M)
       DO 15 IZ=2,NIZ
       GA(IZ,JrPl)«
-------
15
         OCNITNUE
c*
75
         calculate mass after transport
         -•isa=O.O
       do 75 iz=2,niz-l
       XMASSA=XMASSA+T(2) *DZ*1+T(M) *DZ*m(M)
       RBIUPN
       END
C
C
c
THEIR
C
OOEFFTCIENIS
C

              S°&~DIMONAL'
                                    , AND

                        dF,L,A,B,C,D,V)
                           ,,,,,,
      DIMENSION A(l) ,B(1, ,C(1, f D(l, ,V(1) f BE1A(154) ,
                                       BETA AND GAMMA. ..
     GAMMA (IF) -D (IF) /BETA (IF)
     IFP1=IF+1
     DO 1  I-IFP1,L

                          -1)/BETACI-1)
     IAST=L-IF
     DO 2
    END
                             197

-------
                             APPENDIX G
        EXAMPLE OF A MONITORING SCHEDULE FOR A FIELD PLOT DEMONSTRATION

  Into ^ V?.CT,it0id?IO??nrate h°W samPlin9 design principles may be integrated
  into  a field plot LTD, a hypothetical  field plot  samolina  schedule ««
  develoDpd    Tn Tahio r ^  if «_J\,« ».  j        ,   p'v«-  SOIH^I ui^  suneauie was
  ^.4,-.  t1^,^' i-i^.TiTr Thrr,?:,nhsu^'!e.iudji?.'s;i;rot?


  ^rL?isTfrs""e-^^^^^^
 S^fMr^,««^^

 ^I5£WS=*'SSTHSS^
        n of nrnnnHwatof / WaSte loadlng rate B at one  t1me Pfir year» and  waste
loadin rate A twice  per year.  Because the  groundwater is  extremely shallow
i^S'V °/- ^?h  Permeab111ty  ex1*t at the  site, a monitoring  well wa^
irprVnitlredlVelycd?WnEradient  of  each f1eld  Plot'   The annual  Iveragl
?I,«ihPi.  V°n- *•  5  lnC,heS' Su99ested that  so 11 -moisture  sampling  will be
feasible.   Existing groundwater  wells  will  be monitored  at six-month Intervals
In order to evaluate any changes in hazardous constituent concenVatioSs
m.nnn!        3 was  conducted at  two soil  sites  in the area of the
proposed field plots and showed no  Type III organic compounds above detection
                             198

-------
 limits at any  soil  depth.   Type  I  and III analyses were  performed  for  four
 samples  of each applied waste.   In the case of  the  two-time application,  two
 samples  were  evaluated  at each  application  after  careful  compositing.
 Groundwater  monitoring  results were  available for the ISS monitoring sites.  A
 one-time  sampling  of the  field plot  wells  showed no  detectable  Type  III
 constituents.   Metal concentrations  were  assumed to be  similar to  Part  265
 upgradient wells.

      The  Type  II  analysis  chosen  for evaluating  specific  hazardous
 constituents was SW-846  Method  8020  (U.S. EPA  1982b)  for  volatile  aromatic
 hydrocarbons,  since  these were  in the  highest concentrations  in  the  ISS  soil
 zones and below the  treatment  zone, and are expected  to be the most  mobile
 compounds.   Other hazardous constituents will be more  infrequently monitored
 with  Type  III  analysis.   It was not felt necessary to do further evaluation of
 metals.   Toxicity studies using  two bioassays  will  be conducted at  the  same
 frequency  as the Type II  analysis.

      Zone of  incorporation sampling is  scheduled  in  order  to evaluate  a
 presumed  first-order  kinetic rate degradation (i.e., a higher proportion  of
 sampling closest to  the time  of  waste application).   It was determined  from a
 small-scale  study that  5 Type II  samples would  be  required at each  sampling
 time.   Waste  would be  pre-mixed with  ZOI  soils   in  a pug  mill  to  reduce
 variability  of waste distribution  in the ZOI.   Five  or 6 ZOI samples over  time
 are expected to be sufficient to establish degradation rates.  Oil degradation
 will  also be measured with Type I  analysis.

      Type  III  core  samples  (ZOI  to  BTZ) will be  taken  at six  month intervals
 from  the  first application.   Three  replicate samples  within each treatment
 plot  will be analyzed for Type III compounds and  metals  at each depth.

      Soil-pore liquid monitoring was  established  on  a schedule  similar  to  the
 ZOI sampling.   Soil  mobility calculations  based  on  the  land  treatment model
 indicated that movement out  of  the treatment zone could  occur within one  to
 three months.  Two soil-pore  liquid   samplers were  located   in each treatment
 plot.   An effort will be made to time soil-pore  liquid  sampling  events  within
 the general schedule shown,  following significant precipitation events.

      The need  for  further analyses  will  be reviewed at  the end  of the year
 period.  Issues to be evaluated  are  whether or not high concentrations  of  the
 Appendix VIII  compounds would be  found in the  BTZ  soil and  whether or   not
 significant leaching could be identified.

      Evaluation of results may determine that  PHCs or other  compounds  have  not
degraded.  There  may be  a need  to establish a  consistent   sampling  schedule
 beyond the first year shown  in the example schedule.

     First-year results may also  indicate  some  compound movement  based  on
results of intermediate soil zone  sampling.  More intensive  sampling  in these
 zones  may be needed.   In general, it  is not  possible to  recommend  a  defined
schedule for  follow-up  studies.    Evaluation  of   results  should  be  conducted
during the  performance  of the  LTD to  allow  modification  of  the monitoring
schedule.

                                   199

-------
       o
          WL(A)
«£££•
      2/yr

-T?
s
Zl-,2  Z1.2  Z1.2
SP3   SP2   SP2

Z1.2  Z1.2  Zl,2
SP3          SP2
                                                              Z1.2    Z1.2
                                                                     SP3,C3
                        Z1.2
Z1.2    Z1.2    Zl,2    Z1.2
        SP3.C3          SP2
                                                                                                                 63
                                                                                                          SP3,C3,G3
        Z1.2
        SP3.C3.63

Z1.2    Z1.2
        SP3.C3.G3
          Definition of Terms
             Sample:   Z-  zone  of incorporation;  C-  soil  core samples from  ZOI  to BTZ;  SP-  soil-pore liquid- G-
          groundwater                                                                               r      M   •'

             Type of Analysis:  1- Type I;  2- Type  II; 3- Type  III

             Waste Loading and Frequency:   WL(A)- waste loading rate A; WL(B)- waste loading rate B; two  frequencies-
           i/yr and z/yr

-------