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
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' 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
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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.
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-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.
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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 .
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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
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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
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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
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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
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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
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. 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
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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
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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
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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
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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
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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
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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
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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
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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
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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.
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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.
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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.
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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.
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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
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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
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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.
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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.
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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
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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
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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).
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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). '
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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.
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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.
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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.
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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
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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.
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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
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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:
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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.
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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
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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.)
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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
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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.
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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
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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,
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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
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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
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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
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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.
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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
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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
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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
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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
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(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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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.
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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
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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.
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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.
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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).
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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
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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.
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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.
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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
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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
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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
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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
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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.
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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.
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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.
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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
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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
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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
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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.
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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.
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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.
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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.
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Aluminum Ring
Waste
Teflon™ Lined Rubber Septa
Glass Bottle
Aqueous Phase
Figure 5.2. Apparatus for three-phase partitioning coefficient determina-
tions.
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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
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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.
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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
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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.
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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
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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
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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.
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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.
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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.
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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
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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.
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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
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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
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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.
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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.
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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.
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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
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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
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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).
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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.
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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
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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 !
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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
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U.S. Department of Agriculture, Washington, DC.
Sorensen, D. L. 1982. Biochemical activities in soil overlying Paraho
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Fort Collins, CO.
Stotzky, G. 1965. Microbial respiration, p. 1550-1572. In C. A. Black
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Strosher, M. T. 1984. A comparison of biological testing methods in as-
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Calgary, Alberta, Canada.
Strosher, M. T., W. E. Younkin, and D. L. Johnson. 1980. Environmental as-
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128
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130
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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
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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
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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
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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
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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
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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
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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
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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
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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.
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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
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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
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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
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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
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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
------- |