EPA/600/R-94/149
May 1993
CHARACTERIZING CONTAINERIZED
MIXED LOW-LEVEL WASTE
FOR TREATMENT
A Workshop Proceedings
May 25-27,1993
EDITOR:
Gretchen L. Rupp
University of Nevada - Las Vegas
PROJECT OFFICERS:
S.P. (John) Mathur, U.S. DOE
Kenneth W. Brown, U.S. EPA
Cooperative Agreement No. CR818526
Harry Reid Center for Environmental Studies
University of Nevada - Las Vegas
Las Vegas, Nevada
Environmental Monitoring Systems Laboratory
i Office of Research and Development
? U.S. Environmental Protection Agency
Las Vegas, Nevada '
Printed on Recycled Paper
t»
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NOTICE
The information in this document was developed with partial funding by the U.S.
Environmental Protection Agency under an Interagency Agreement with the U.S. Department of
Energy. Although it has been peer and administratively reviewed and approved for publication as
an EPA document, the observations and recommendations of the workgroup members do not
necessarily represent the position and policy of the U.S. Environmental Protection Agency or the
U.S. Department of Energy, and as such no endorsement is implied by publication of this material.
«**,
11
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EXECUTIVE SUMMARY
This report is the product of a technical workshop held in May 1993 in Las Vegas, Nevada.
The workshop was conducted by the Environmental Protection Agency (EPA) and the Department
of Energy (DOE). Its purpose was to define the waste characterization that would be required to
operate a mixed low-level waste treatment facility applying robust treatment methods to broad
categories of waste. Evaluation of these characterization needs, and comparison with the needs
defined under current programs, may allow DOE to realize savings in both its waste characterization
and treatment efforts.
Mixed waste contains both hazardous components regulated under the Resource
Conservation and Recovery Act (RCRA) and radioactive components regulated by DOE Orders.
There are conflicts between the two sets of requirements. Moreover, the RCRA delisting of mixed
wastes following treatment has not been generally approved by regulatory agencies, and treatment
of mixed waste under the RCRA Debris Rule has not been demonstrated. Wastes generated and
disposed on National Priorities List (NPL) sites are subject to further regulation under the
Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). In
formulating plans to treat its mixed waste, DOE is now on a schedule imposed by the Federal
Facility Compliance Act of 1992. This Act requires that site treatment plans be in place by October
1995, and grants states approval authority over the plans.
This report concerns DOE's mixed low-level waste (MLLW). Within the DOE complex,
MLLW is generated by dsfense-related activities, research programs, facility decontamination and
decommissioning activities, and environmental restoration. Uranium, plutonium, fission products,
and other radionuclides may be present. The wastes may contain up to 100 nCi/g of transuranic
alpha activity. Lead, mercury, or other hazardous contaminants are present. DOE currently has
custody of roughly 250,000 cubic meters of MLLW, and it is estimated that 3-4 times this amount
will be added to the inventory over the next 5 years.
To address handing of its MLLW stockpile, DOE has initiated the Mixed Waste Treatment
Project (MWTP). Its purpose is to identify promising technologies and strategies for MLLW
characterization and treatment that can be applied to containerized waste throughout the DOE
complex. /The approach of the MWTP is to classify all MLLW waste streams into several very
broad treatability groups,, and treat these groups in an integrated facility relying on very robust
(mostly thermal) treatment technologies (a minimum waste characterization/maximum treatment
approach). The MWTP has generated a conceptual design for such an integrated facility. That
facility may never be constructed; its value is as a model, a general framework for the definition of
efficient waste characterization/treatment strategies. :
The Las Vegas workshop attendees addressed what waste characterization would be required
to operate the MWTP facility. The 75 workshop attendees, consisting predominantly of DOE
contractors (see Acknowledgements), divided into three groups and considered the characterization
needs in three stages: evaluating containerized wastes to route them to the proper treatment train;
monitoring the pretreataent and treatment processes and their effluents; and characterizing final
waste forms for disposal.For each stage, they identified the properties to be measured, data quality
objectives, applicable m
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In an integrated MLLW treatment facility, the three purposes of up-front waste
characterization are: to identify containers of transuranic waste mistakenly sent to the facility; to
identify containers with mercury, lead, compressed gases, or other materials that will require special
treatment; and to characterize the physical and chemical properties of the waste so that each
container can be routed to the proper treatment line. The six waste properties that must be
evaluated are:
specific alpha activity
physical properties, including debris content
solids content, or pumpability
organic constituents (qualitative and quantitative)
hazardous elements or special materials
radionuclides
An enormous number of waste containers must be evaluated, and the container contents are often
heterogeneous. Consequently, measurement methods that assess the bulk properties of a container
of waste are strongly preferred over those that require characterization at several points within the
container. In practical terms, non-intrusive methods are given priority over intrusive methods,
which in turn are favored over methods requiring full sampling. This hierarchy will enhance the
safety, representativeness, and efficiency of initial waste characterization.
Several dozen methods were identified for evaluating the six properties in incoming wastes.
Most are in some stage of research or development, but multiple "existing" methods were cited as
potentially applicable for each property. Few of these can be considered "off-the-shelf;" nearly all
would require some degree of testing and adaptation to this application. No existing non-intrusive
methods were identified for organics or special hazardous materials. In a facility accepting varied
waste streams, most of the six properties would have to be evaluated using a suite of techniques
rather than one single method. The extent to which full sampling would be required cannot be
specified at this time. That will depend on quantitative data quality objectives. Full sampling and
analysis are most likely to be required for organic constituents and special hazardous materials
should their acceptable thresholds be low. '
The workshop attendees identified a need for the documentation, verification, and use of
process knowledge in formulating a waste characterization strategy. Methods research is particularly
needed for assessing organics and special hazardous materials in a non- or minimally-intrusive way
Gamma neutron activation analysis and pulsed fast neutron analysis were identified as long-term
research possibilities. In the near term, advances in intrusive methods utilizing fiber optic systems
appear most promising.
Within the treatment facility, material streams will be monitored at a great many points in
the pretreatment and treatment lines, as well as the offgas systems. The workshop group handling
process monitoring noted that a careful scheme to batch and process like wastes together would
lessen the need for in-plant characterization. The group identified existing methods for all of the
in-plant monitoring needs, although some methods may require considerable development for this
application. Offgas monitoring methods should receive the highest research priority Real-time
techniques for monitoring metals and radionuclides in offgases would be a major attribute for any
treatment facility. Mercury detectors for solid matrices and improved in-plant radiation detectors
also warrant research, as do screening methods for chemically heterogeneous matrices and
IV
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contaminant-specific detectors. The development of national performance standards for the non-
standard (particularly radiation) methods is desirable. There is a need for a thorough evaluation
by a multidisciplinary team on the relative benefits of up-front characterization versus versatile
process design versus extensive process monitoring and control.
This report contains a discussion of the plasma arc vitrification process for waste treatment
and the associated characterization needs. Plasma arc is not universally applicable to DOE's
MLLW streams, and it is not one of the treatment technologies in the MWTP conceptual design.
It is employed here as an example: if the minimum characterization/maximum treatment concept
is taken to the extreme, what are the characterization needs? Feed drums with containerized
liquids or compressed gases must be identified, so that they can be routed away from the plasma
arc unit. Significant amounts of lead in the feed must also be detected, since lead will not be
recoverable from the glass. Organics in the feed should not require identification or quantitation,
since they will be completely destroyed (as demonstrated by trial burns). Some degree of
confirmatory offgas monitoring for organics may be required. Mercury is a serious problem for
plasma arc units, as for all thermal treatment techniques. Identification and re-routing of mercury-
laden wastes is desirable. Furthermore, public acceptance of the plasma arc would be greatly
facilitated by continuous, real-time monitoring for mercury (as well as radionuclides and other
metals) in the stack gases. In sum, it appears that characterization needs are somewhat lessened
in a plasma arc system. However, plasma arc shares with other thermal technologies the major
characterization difficulties: identifying mercury in the feed containers and monitoring offgases in
real time. .
The MWTP facility will produce nine solid waste forms and materials for recycle:
cement grouts (cement and organic-cement conglomerate)
crystalline ceramic
glass . .
polymers (sulfur polymer and macroencapsulation)
elemental lead
elemental mercury
ferrous metal alloys :
Testing of these materials will be driven chiefly by regulation, although shipping requirements,
treatment unit process control, and health and safety considerations will also apply. Twenty
properties or parameters were identified for assessment in these materials (not all tests will be
required for all materials). Additional waste acceptance criteria specific to the disposal site would
apply, but these cannot be anticipated at present. In general, measurement methods for the final
waste forms are well established. Many of the test protocols are established by regulation (the
RCRA Characteristic Tests, for example). Most of the questions regarding final waste form testing
relate to the interpretation of test results and regulatory uncertainty.
Appropriate sampling designs, and the statistical characteristics of individual batches of
waste forms, must be established. This will be straightforward with the more uniform waste forms,
but some, like polymer-encapsulated forms, will present a challenge. Polymer forms will require
methods development to assay radionuclides and alpha activity, and to quantify gas generation.
Whether neutron and gamma methods are sensitive enough ito assess radionuclides in any of the
waste forms is in question. There is an effective lack of methods for evaluating long-term physical
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integrity and leaching properties of waste forms, in that prescribed methods are of questionable
applicability. The creation of sulfur polymer waste forms needs further thought; it may be
impossible to make these so they are not "reactive" — and hence hazardous — under RCRA.
A number of non-technical concerns related to waste characterization were voiced during
the workshop. Waste characterization and treatment strategies must be developed in concert. The
facility design team cannot first specify the treatment scheme and then plug in off-the-shelf
measurement methods, since method shortcomings may constrain treatment design. They may also
dictate operating mode: batch instead of continuous, uniform instead of varied batches. On the
other hand, a careful batching scheme may obviate the need for sophisticated measuring devices
at some points. Because of the complexity of the treatment facility, a state-of-the-art expert system
integrating process monitors and controllers is called for. Some methods development for
characterization may be driven by the need for public acceptance of the treatment facility. This
appears to be especially true for characterizing process offgas streams.
The possibility exists that regulators may require full RCRA testing of all waste forms exiting
an integrated treatment facility, regardless of the treatment technology. This would require an
enormous characterization program, and would render moot the concept of 'minimum
characterization followed by maximum treatment.' On the other hand, the 1992 RCRA Debris
Rule and its amendments may substantially diminish the characterization requirements for large
portions of the stored MLLW.
VI
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CONTENTS
NOTICE .....: ii
EXECUTIVE SUMMARY , ,. .... " ft
LIST OF FIGURES viii
LIST OF TABLES .. ,'. . . . . .... . ... .^..'.'.'.]' yiii
ABBREVIATIONS AND ACRONYMS . ., ; ix
ACKNOWLEDGEMENTS . . ., . . . . xiii
Chapter 1 Introduction - Gretchen Rupp . '........... 1
The Regulatory Situation .... . .,., ..... 1
Status of Waste Characterization and Treatment 2
The Mixed Waste Treatment Project ,, 3
Related Programs and Initiatives 5
Report Purpose and Scope , .......... 7
Organization of the Report .... . . .... '„•'... ....... 9
References ; . .... 11
Chapter 2 Characterization Before Treatment - Isabel Anderson, George Eccleston and
Mark Pickrell : . . . . ... 12
Introduction . [ 12
Measurement Points and Techniques ; 13
Conclusions and Recommendations t 34
References ; 3g
Chapter 3 Process Monitoring and Control - Ray Geimer, Gary Leatherman
and Ellen Stallings , , 3g
Introduction , 38
The Mixed Waste Treatment Project Integrated Treatment Facility 38
Measurement Requirements for Process Control 39
Generic Monitoring and Controls Required for Operation of Thermal Units
for the Treatment of Mixed Low-level Waste 59
The Minimum Characterization/Maximum Treatment Concept .65
Conclusions and Recommendations 73
Chapter 4 Final Waste Form Characterization - Peter Lindahl, Srini Venkatesh,
M. John Plodinec, SJ. Amir, Mark Pickrell and Rich Van Konynenburg 75
Introduction 75
Parameters and Tests . ! ' 77
Conclusions and Recommendations 101
References 102
Vll
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CONTENTS (Continued)
Chapter 5 Conclusions and Recommendations - Gretchen Rupp, Ellen Stallings
and John Koutsandreas ............................................... 103
Identified Research, Development, and Demonstration Needs ................. 103
Waste Treatment and Institutional Issues ................................. 106
Continuing Work ...................................... ' 109
Reference
109
Appendix A - The Five Waste Streams ..................................... A-l
Appendix B - MWTP Process Flow Diagrams ............... . . . . ................. B-l
Appendix C - Method Descriptions for Characterization of Incoming Waste ........... ! C-l
Appendix D - Advanced Technologies for Process Monitoring and Control ........... . . D-l
Appendix E - Instrumentation for Waste Form Characterization .................. '.'.'. E-l
Appendix F - Bibliography for Characterization of Low-Level Waste . . ....... '.'.'.'.'.'.'.'.'. F-l
LIST OF FIGURES
Number
1-1. Schematic diagram of the MWTP facility ........ .... ................... g
3-1. Plasma furnace system schematic ............................ ..... gg
C-l. Fiber optic system for drum examination .............................. ..... C-9
C-2. Ion Mobility Spectrometer ..................................... ° ......... Q.H
Number
Table 2-1.
Table 4-1.
Table 4-2.
Table 4-3.
Table 4-4.
Table 4-5.
Table 4-6.
Table 4-7.
Table 4-8.
Table 4-9.
Table 4-10.
Table 4-11.
LIST OF TABLES
Measurement Methods for Containerized Waste ig
Parameters Tested in Final Waste Forms 78
Characterization of Glass Waste Forms '.'.'.'.'.'.'.'.'.'.'. 79
Characterization of Ceramic Waste Forms 80
Characterization of Cement (organic) Waste Forms 81
Characterization of Cement (inorganic) Waste Forms 82
Characterization of Inorganic/Sulfur Polymer Waste Forms '.'.'.'.'.'. 83
Characterization of Organic Polymer Waste Forms . .... 84
Characterization of Ferrous Metal Waste Forms 85
Characterization of Elemental Lead Waste Forms 86
Characterization of Elemental Mercury Waste Forms '.'.'.'.'.'.'.'. 87
Removable External Radioactive Contamination Wipe Limits. 91
VJUl
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ABBREVIATIONS AND ACRONYMS
AAS
ACS
AE
AEA
AED
ALARA
AMU
ANS
ANSI
APCD
ARAR
ASTM
BACT
BAT
BDAT
BG
bm
BPT
BTU
CAA
CAM
CEM
CERCLA
CFC
cfm
CFR
cfs
CHCs
CN
COLIWASA
CPAC
cpm
CTEN
CWA
D&D
D-T
DDT
DBA
DMCP
DOE
DOT
DQO
DRE
DTA
atomic absorption spectrophotometry :
American Chemical Society Act :
atomic emission :
Atomic Energy Agency
atomic emission detection
as low as reasonably achievable
atomic mass unit
American Nuclear Society
American National Standards Institute '
air pollution control device
Applicable or Relevant and Appropriate Requirement
American Society for Testing and Materials
Best Available Control Technology
Best Available Technology (Economically Achievable)
Best Demonstated Available Technology
background ;
benchmark glass
Best Practicable (Control) Technology or Treatment
British Thermal Unit ;
Clean Air Act
continuous air monitor j
continuous emission monitoring
Comprehensive Environmental Response, Compensation, and Liability Act
chlorofluorocarbon
cubic feet per minute
Code of Federal Regulations
cubic feet per second
chlorinated hydrocarbons
cyanide
colorimetric liquid waste sampler
Center for Process Analytical Chemistry (University of Washington)
counts per minute ;
combined thermal - epithermal neutron
Clean Water Act
decommissioning and decontamination
deuterium-tritium
differential die-away technique ;
Drug Enforcement Agency
DOE Methods Compendium Program
U.S. Department of Energy
U.S. Department of Transportation ,
data quality objective ,
destruction removal efficiency
differential thermal analysis '•
IX
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ABBREVIATIONS AND ACRONYMS (Continued)
EDX
eH
EM
EMSL-LV
EP
EPA
EPRI
eV
F&OR
FA
FBI
FFCA-92
FPXRF
FUR
g
GC
GC/MS
H&S-
HAP
HEPA
HPGe
HLW
HMTA
HOC
HP
HPLC
HQ
HSWA
HVAC
1C
ICP
ICP/MS
INEL
IR
kw
kwh
LAER
LANL
LDR
LIBS
LIPS
LLNL
LLW
LOQ
electron diffractive x-ray
redox potential
Office of Environmental Management within DOE
Environmental Monitoring Systems Laboratory-Las Vegas
Extraction Procedure
U.S. Environmental Protection Agency
Electric Power Research Institute
electron volts
functional and operational requirements
flow injection analysis
fluidized bed incinerator
Federal Facilities Compliance Act of 1992
field-portable X-ray diffraction
Fourier transform infrared spectroscopy
grams
gas chromatography
gas chromatograph/mass spectrometry
health and safety
hazardous air pollutant
high-efficiency particulate air
high-purity germanium detector
high-level waste
Hazardous Materials Transportation Act
halogenated organic carbon
Health Physics
high performance liquid chromatography
headquarters
Hazardous and Solid Waste Amendment of 1984/RCRA
heating, ventilation, and air conditioning (system)
ion chromatography
inductively coupled plasma
inductively coupled plasma/mass spectrometry
Idaho National Engineering Laboratory
infrared spectroscopy
kilowatt
kilowatt hour
lowest achievable emissions rate
Los Alamos National Laboratory
land disposal restrictions (of RCRA)
laser-induced breakdown spectroscopy
laser-induced plasma spectroscopy
Lawrence Livermore National Laboratory
low-level waste
level of quantitation
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ABBREVIATIONS AND ACRONYMS (Continued)
LSC
MACT
MAER
MATC
mCi
meV
MLLW
MSDS
MWIP
MWTP
NACE
nCi
NDE
NFPA
NPDES
NPL
NRC
ORIA-LV
ORNL
OSWER
OTD
P&T
PAH
PARCC
PCS
pCi
PCT
PFA
PFD
PFNA
PGNAA
PIC
PNA
PNL
POHC
ppb
ppm
ppt
PQM
QA/QC
RadCon
RCRA
Rem
RTR
liquid scintillation counting I
maximum achievable control technology
maximum allowable emission rate
maximum allowable toxicant concentration
milliCuries
millielectron volts
Mixed low-level waste ' ' , .
Material Safety Data Sheet
Mixed Waste Integrated Program
Mixed Waste Treatment Project
National Association of Corrosion Engineers
nanoCuries
non-destructive evaluation
National Fire Protection Association
National Pollutant Discharge Elimination System
National Priorities List
Nuclear Regulatory Commission
Office of Radiation and Indoor Air (EPA), Las Vegas
Oak Ridge National Laboratory
Office of Solid Waste & Emergency Response (EPA)
Office of Technology Development of DOE
purge and trap
polyaromatic hydrocarbon
precision, accuracy, representativeness, completeness, and comparability
polychlorinated biphenyl ,
picoCuries
product consistency test
polyfluoroacetate
process flow diagram
pulsed fast neutron analysis
prompt gamma neutron activation analysis
products of incomplete combustion
polynuclear aromatics
Pacific Northwest Laboratory ;
principal organic hazardous constituents
parts per billion
parts per million
parts per trillion
piezoelectric quartz microbalance
quality assurance/quality control
radiological control
Resource Conservation and Recovery Act of 1976
Roentgen equivalent man • . ,
real-time radiography
XI
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ABBREVIATIONS AND ACRONYMS (Continued)
SAW
SCFE
scfm
SEM
SERS
SGS
SIMS
SOA
SVOC
TAP
TBD
TBP
TC
TCLP
TLD
TOC
TOX
TRU
TSCA
TSD
TSDF
TSG
UHV
UV/Vis
VOA
VOCs
W.C.
surface acoustic wave (sensor)
supercritical fluid extraction
standard cubic feet per minute
scanning electron microscopy
surface-enhanced Raman spectroscopy
segmented gamma scanner
secondary ion mass spectrometry
state-of-the-art
semivolatile organic compounds
toxic air pollutant
to be determined
tributylphosphate
Toxicity Characteristic
Toxicity Characteristic Leaching Procedure
thermoluminescent dosimeter
total organic carbon
total organic halogens
transuranic
Toxic Substances Control Act
treatment, storage or disposal
treatment, storage, and disposal facility
Technology Support Group
ultrahigh vacuum
ultraviolet/visible (spectrum)
volatile organics analysis
volatile organic compounds
water column
xu
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ACKNOWLEDGEMENTS
This document is the product of a workshop sponsored by the U.S. Department of Energy
(DOE) and the U.S. Environmental Protection Agency (EPA) in May 1993. Project Officers were
Ken Brown of EPA's Environmental Monitoring Systems Laboratory-Las Vegas (EMSL-LV) and
John Mathur of DOE's Office of Environmental Management. The Harry Reid Center for
Environmental Studies of the University of Nevada-Las Vegas (UNLV) conducted the project under
Cooperative Agreement No. CR8526-02-0. The UNLV project manager was Kathy Lauckner.
Three workgroups convened:
1. Waste Characterization before Treatment
a) Chemical Aspects - Chair, Isabel Anderson.
b) Radiation - Chair, George Eccleston. ,
2. Process Monitoring - Co-Chairs, Ray Geimer and Gary Leatherman.
3. Final Waste Forms -Co-Chairs, Peter Lindahl, and Srini Venkatesh.
The group chairs were the principal authors of this report. 'The following additional individuals
'served on a steering committee for the project. The names of those who made contributions of text
to the project report or served as principal reviewers are denoted with an asterisk.
* Gretchen Rupp (chair)
* Clare Gerlach (vice chair)
* Ellen Stallings (vice chair)
Janine Arvizu
Chuck Baldwin
* Jerry Stakebake
Barbara Broomfield
Tom Clements
Nancy David
Barry Lesnick
* SamPillay
Robert Holloway
Roy R. Jones, Sr.
* John Koutsandreas
Milo Larsen
Betsy McGrath
Colleen Petullo
Bob Sanders
Jeff Williams
Ben Hull
University of Nevada-Las Vegas
Lockheed Environmental Systems & Technologies
Los Alamos National Laboratory
Consolidated Technical Services'
EG&G Rocky Flats
EG&G Rocky Flats
Westinghouse Hanford
EG&G Idaho, Inc.
ERIM
EPA, Office of Solid Wastes •.
Los Alamos National Laboratory
EPA, EMSL-LV '
EPA Region 10
University of Nevada - Las Vegas
Science Applications International Corp., Idaho
University of Washington, CPAC
EPA Office of Radiation and Indoor Air
Lehigh University
DOE, Office of Waste Management
EPA, Office of Radiation & Indoor Air
A participant list foEows. We have made every effort to include the names of all participants, and
sincerely hope we have not overlooked any names.
xui
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Characterization for Treatment of Containerized Mixed Low-Level Wastes
Workshop
May 25-27, 1993
Groups:
1} - Waste Characterization 2} - Process Monitoring 3} - Final Waste Forms
a. chemical aspects
b. radiation
lb} Dr. Ishwar D. Aggarwal
Naval Research Labs
*3} Mr. S. J. Amir
Westinghouse Hanford Co.
*la}Ms. Isabel Anderson
EG&G Idaho
la} Dr. Pat Beauieu
Los Alamos National Laboratory
2} Mr. Tony J. Bengelsdijk
Los Alamos National Laboratory
2} Dr. Chris Bjork
Los Alamos National Laboratory
Mr. Kenneth Brown
U.S. EPA, EMSL-LV
lb} Dr. E. (Bud) J.T. Burns
Lawrence Livermore National Laboratory
Dr. Tom Chiang
Lockheed Environmental Systems & Tech.
la} Dr. Susan D. Carson
Sandia National Laboratory
la} Dr. Bart Draper
Bechtel Environmental Inc.
2} Mr. James Dyke
Los Alamos National Laboratory
*lb}Mr. George W. Eccleston
Los Alamos National Laboratory
*la} Mr. Richard Ediger
Perkin-Elmer Corp.
2} Dr. Nina Bergen French
Lawrence Livermore National Laboratory
*2} Mr. Robert J. Gehrke
EG&G, Idaho, Inc.
*2} Mr. Ray Geimer
Science Applications International Corp.
*!} Dr. Robert W. Gerlach
Lockheed Environmental Systems & Tech.
* Ms. Clare Gerlach
Lockheed Environmental Systems & Tech.
1} Mr. Bud Gibson
ATI
1} Mr. Keith V. Gilbert
Lawrence Livermore National Laboratory
la} Dr. Wayne H. Griest
Oak Ridge National Laboratory
lb} Mr. William J. Haas
CMST-IP
2} Dr. Ronald A. Harlan
EG&G Rocky Flats, Inc.
2} Mr. Steven D. Hartenstein
Idaho National Engineering Laboratory
*lb} Dr. Robert C. Hochel
Savannah River Technology Center
xiv
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2} Dr. Robert Holloway
U.S. EPA, EMSL-LV
lb} Dr. J. Paul Hurley
Special Technologies Laboratory
2} Dr. David E. Hyatt
ADA Technologies Inc.
1} Mr. David E. James
UNLV Civil & Mechanical Engineering
3} Mr. Roy R. Jones
U.S. EPA
2} Mr. Patrick Kelly
Sanford Cohen & Assoc.
*lb}Mr. John D. Koutsandreas
UNLV Harry Reid Center
2} Mr. Milo Larsen
Science Applications International Corp.
Ms. Kathy Lauckner
UNLV Harry Reid Center
*2} Mr. Gary Leatherman
Science Applications International Corp.
la} Dr. Leroy Lewis
Westinghouse Idaho Nuclear Co.
*3} Mr. Peter Lindahl
Argonne National Laboratory
*3} Mr. Mike Maskarinec
Oak Ridge National Laboratory
3} Mr. John Mathur
U.S. DOE
la} Mr. David Maxwell
U.S. EPA
lb} Mr. Richard Mayer
U.S. EPA
lb} Mr. Ed McCrea
EG&G
3} Mr. Clay D. McCurley
Bechtel Environmental Inc.
2} Dr, Jerry N. McKamy
EG&G Rocky Flats Inc.
lb} Mr. Steve Mech
Westinghouse Hanford Co.
la} Mr. Steve Merrill
Lockheed - Austin Division
2} Dr. Bob Newberry
U.S. DOE
Dr. Dale L. Perry
Lawrence Berkeley Laboratory
2} Dr. Thomas L. Pettit
*3} Dr.,MarkPickrell
Los Alamos National Laboratory
*3}, Mr, MJ. Plodinec
Westinghouse Savannah River
la} Dr.1 Edward J. Poziomek
UNLV Harry Reid Center
1} Mr. Antonio J. Ricco
Sandia National Laboratory
2} Mr. Julio G. Rodriguez
EG&G Idaho
*lb} Mr.TimRoney
EG&G Idaho
2} Dr. Jeffrey J. Rosentreter
Idaho State University
3} Mr.; Wayne Ross
Battelle Pacific Northwest Laboratory
xv
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*3} Ms. Gretchen Rupp
UNLV Harry Reid Center
la} Mr. Randall Ryti
Neptune and Co.
lb} Mr. James Schaffer
EG&G Idaho, Inc.
la} Mr. Gary M. Seidel
Westinghouse Hanford Company
la} Ms. Doris L. Simmons
Westinghouse Savannah River Co.
la} Dr. Anita Singh
Lockheed Environmental Systems & Tech.
2} Dr. Ashok Singh
UNLV Mathematical Sciences
3} Mr. Chris Smith
Martin Marietta
*2} Ms. Ellen Stallings
Los Alamos National Laboratory
lb} Mr. Russel Stimmel
Lockheed Analytical Services
la} Mr. Phillip J. Swanson
Concord Associates, Inc.
2} Mr. Bob Swoboda
*lb} Mr.AlTardiff
U.S. DOE
* 3} Mr. Srini Venkatesh
Westinghouse Savannah River Co.
*2} Mr. Art Verardo
Sandia National Laboratory
*3} Mr. Rich Van Konynenburg
LawrenceLivermore NationalLaboratory
1} Mr. (Wei-Tao) Paul Wang
*lb} Mr. Jeff Williams
U.S. DOE
2} Mr. Wayne Winkelman
Characterization Methods & Devices
3/2} Mr. Stanley Wolf
U.S. DOE
lb/3} Mr. Matt Zenowich
U.S. DOE
Contributed to the project report as a writer or reviewer.
xvi
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Chapter 1
Introduction
Gretchen Rupp
Radioactive wastes that are generated in the nation's nuclear weapons program are
stored at a number of facilities that are under the jurisdiction of the Department of Energy
(DOE). These include substantial volumes of mixed low-level waste (i.e., low-level
radioactive waste that is also hazardous under the Resource Conservation and Recovery Act
(RCRA)). Over 1300 types of mixed low-level waste (MLLW) have been identified. There
are more than a million containers of MLLW in storage at DOE sites.
Characterization of these wastes for treatment, storage and disposal currently requires
enormous resources. Under the aegis of its Mixed Waste Treatment Project (MWTP), DOE
is exploring a strategy to expedite treatment and minimize characterization requirements.
In this approach, wastes would be classed into broad treatability groups and processed and
treated by robust methods. Because of the robustness of the treatment, the need for initial
waste characterization would be lessened. \
DOE's Office of Technology Development ! (EM-50) has called on EPA's
Environmental Monitoring Systems Laboratory at Las Vegas (EMSL-LV) to support the
characterize-to-treat portion of this strategy. This report is the product of a technical
workshop conducted by EMSL-LV in May, 1993, co-sponsored by DOE and EPA Its
purpose is to define the characterization that would be required at each stage for operation
of a MLLW treatment facility applying robust treatment methods to broad categories of
MLLW. Evaluation of these characterization needs, and comparison with current needs,
may allow DOE to realize savings in both its waste characterization and treatment efforts.
The Regulatory Situation
The following discussion is adapted from reference 1.
Mixed waste contains hazardous contaminants that are governed by RCRA and
radioactive contaminants that are governed by DOE Orders. Requirements specified under
these regulations conflict, in some instances. Generally, RCRA regulations are designed to
cover both general and site-specific situations, while DOE orders require interpretation in
specific situations.
Disposal criteria have not been established for mixed waste. There are several
difficulties with finalizing such criteria. First, the selection of disposal sites and waste
disposal criteria will be based on performance assessments. However, performance
assessments for radioactive waste disposal do not account for the form of the waste.
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Furthermore, the RCRA delisting of mixed waste after treatment has not been generally
accepted or approved by the regulatory agencies. The treatment of mixed waste under the
"Debris Rule" has not been demonstrated or approved, and development of the RCRA
Rules for soil and debris is ongoing. The RCRA Hazardous Waste Identification Rule, that
will address the "mixture" and "derived from" rules, is also still in development. The risk
to _ the public and workers due to storage of legacy waste is not well defined; therefore,
priorities cannot be established on a risk-based cleanup strategy. Finally, many treated
DOE wastes will be disposed on NPL sites, where CERCLA cleanup standards, potentially
very stringent, will apply.
Congress recognized the problems associated with mixed waste management and
enacted the Federal Facility Compliance Act of 1992 (FFCA-1992). The Act waives
sovereign immunity for Federal facilities, thereby allowing DOE to be subject to fines and
penalties for failure to manage mixed waste according to RCRA This congressional
mandate for DOE to treat its mixed waste establishes a 3-year timetable (ending in October
1995) for development of site treatment plans, during which time the waiver is delayed. The
Act gives states approval authority over the site treatment plans. Differing state
requirements for the treatment plans are anticipated. After plans have been reviewed, it
is further anticipated that equity brokering between states will occur regarding treatment
storage and disposal facility location. '
Status of Waste Characterization and Treatment
Low-level waste is defined by DOE' Order 5820.2A as all radioactive waste not
classified as high level waste, transuranic waste, spent fuel, or by-product materials (uranium
mill taihngs, for example). Within the DOE complex, mixed low-level waste is generated
by defense-related activities, research programs, facility decontamination and
decommissioning activities (D&D), and environmental restoration. The principal radioactive
components are uranium and plutonium, but many other radionuclides, including other
transuranic elements, can be present. The wastes can contain up to 100 nCi/gram of
transuranic alpha activity. Both contact- and remote-handled wastes are included Mercury
lead, or other hazardous materials are present in all MLLW. MLLW takes many forms'
Wastewaters, salts and sludges contribute a great deal to the waste volume, but cleaning
materials, miscellaneous laboratory wastes, building and demolition debris, soil, spent filters
tools and discarded equipment are also included. '
The most comprehensive survey of DOE mixed wastes is the April 1993 Draft Mixed
Waste Inventory Report prepared by DOE to comply with FFCA-92 (2). According to the
Sr^nn17 f?™*' MLLW comPrises 42% of VOE's mixed wastes, and currently totals
247,000 cubic meters. The report estimates that an additional 280,000 m3 of MLLW will be
generated in the next five years of operations across the DOE complex. A rough estimate
of the 5-year volume of MLLW that will be created by environmental restoration activities
-------
«
is 620,000 m3. In addition, a considerable - and unknown - portion of the currently stored
TRU wastes are expected to be examined and reclassified as MLLW. More than four fifths
of the MLLW is generated at five sites: the Hanford Reservation, the Idaho National
Engineering Laboratory, Oak Ridge K-25 Plant, Oak Ridge Y-12 Plant, and Rocky Flats
Plant. However, almost all DOE sites generate some MLLW. There are wastes stored at
48 sites in 22 states. !
The Draft Mixed Waste Inventory Report includes a tabulation of approximately 1300
individual waste streams of mixed low-level waste. Of these, roughly 60% have been
characterized using process knowledge, while the remaining 40% have been sampled. There
are a number of existing and planned facilities for treatment of specific waste streams, but
these facilities are generally not adaptable to treat a broader array of wastes (2). In
addition, the Draft Inventory Report identifies "...an acute shortage of treatment capacity
for treating alpha MLLW," that is, MLLW with transuranic alpha levels greater than 10
nCi/g, such that containment is of special concern.
Under the current approach to waste characterization and treatment, ea.ch DOE
facility is involved in rigorous efforts to identify and describe mixed low-level wastes
generated or stored at that facility. Characterization is needed to safeguard the environment
and worker health and safety; to design, protect and optimize the treatment processes; to
meet environmental regulations and to satisfy the waste acceptance criteria of the disposal
sites. Many types of characterization technologies are needed, including some technologies
that are now in development. The projected characterization costs for extensive, site-by-site
waste analysis are 30-45 billion dollars over the next 30 years (3). Each DOE site that
generates or stores MLLW would require waste characterization laboratories, waste handling
facilities, and other resources. This approach embodies considerable potential for
duplication of effort across the DOE complex.
The Mixed Waste Treatment Project
As a more efficacious alternative, DOE is exploring a strategy in which
characterization would be performed just prior to and during waste treatment, to support
the treatment needs. In its Mixed Waste Treatment Project (MWTP), DOE's Office of
Waste Management (EM-30) has divided MLLW into 5 broad treatability groups
(hereinafter called "the five waste streams"): ;
• aqueous liquids
• organic liquids : ,
• wet solids
• homogeneous dry solids
• heterogeneous dry solids (also called debris). :
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Pre-conceptual waste segregation and treatment trains have been devised for each
of these waste streams, and the functional and operational requirements (F&ORs) of a
prototype treatment facility have been specified (4). The baseline treatment technologies
are Best Demonstrated Available Technologies (BDATs) derived from RCRA treatment
requirements, but alternative technologies have also been identified. It should be noted
that design of the MWTP facility is an ongoing process. The design used as a baseline
herein, the corresponding F&ORs, and the waste stream classifications are those of late
1992. They do not take into acccount the RCRA "Debris Rule" promulgated at that time.
This will influence both facility design and characterization strategy (see concluding chapter
for further discussion).
The MWTP is highly conceptual in nature and will not likely ever be constructed
Its purpose is to guide the selection of waste treatment and characterization methods that
may be needed at actual facilities.
The Five Waste Streams
The five waste streams are defined on the basis of their physical and chemical
properties, which dictate pre-treatment processing requirements and appropriate treatment
technologies. The properties of the waste streams are described in detail in Appendix A
They are summarized below. All of the waste streams include both incoming wastes and
internal transfer streams from within the treatment facility. Note that these waste streams
include only MLLW that is contained in drums or boxes. The Hanford tank wastes (and
those at other sites) will be treated by other processes.
Aqueous liquids These liquids contain less than 1 percent organic carbon. They may
contain up to 35 or 40 percent solids, as long as they are pumpable. The average density
ot this waste stream (including drums) is 1049 kg/m3.
Organic liquids These liquids may have as low as 1 percent organic content. They
include miscellaneous organic liquids, scintillation cocktails, solvents, sludges PCBs and
mercury-contaminated organics. Their average density is 882 kg/m3.
_ Wet solids These are wet wastes that are not pumpable. The solids may be mixed
with either water or organic liquids. Components of this stream include sludges, absorbed
liquids, resins and cemented sludges. The average density, including drums, is 1276 kg/m3.
Homogeneous dry solids These solids have a particle size of less than 2 inches The
major component pf this waste stream is soil from site remediation activities. The average
density is 1181 kg/m3. °
Heterogeneous Dry Solids Demolition debris and lead forms are major components
of this waste stream. The average density is 1234 kg/m3.
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Waste Handling and Treatment
In the preconceptual design of the MWTP prototype treatment facility, handling and
treatment of the wastes have been specified according to the applicable DOE orders and
guidelines (5,6,7), as well as the .requirements of RCRA. The facility operates in batch
mode, and is able to handle PCB-containing wastes under a Toxic Substances Control Act
(TSCA) permit. Appendix B is a complete collection of the flow diagrams for the facility.
The overall scheme is depicted in Figure 1.1. Each of the five waste treatment paths, herein
referred to as "lines," begins with several waste handling and preparation operations, such
as organics removal, suspended solids removal, size segregation, or removal of ferrous
metals. Several internal transfer streams are generated at this pretreatment stage. In some
cases, a waste stream is split into components of different density or particle size. The
concentrated waste streams are then treated. Organics are destroyed by wet air oxidation
or one of several thermal methods. Inorganic contaminants are stabilized within solid waste
forms. Reusable materials are recovered in pure form. The final products of the facility
are:
clean water
treated offgas
ferrous metals
elemental lead ,
elemental mercury
reusable containers
compacted waste forms
glass, ceramic, polymer or grout waste forms.
For planning and design purposes, it is assumed by DOE that roughly ten such
treatment plants would be required across the DOE complex. Since each would accept only
a limited number of the 1300 waste streams, there would probably be differences in the
waste characterization and handling protocols among the plants. At least some of the plants
would handle wastes about which very little a priori knowledge exists.
Related Programs and Initiatives
The Mixed Waste Integrated Program within the Office of Technology Development
supports the MWTP by developing and demonstrating innovative and emerging technologies
for the treatment and management of the DOE MLLW (8). As the treatment flowsheets
evolve due to technology development, the characterization needs will be re-examined and
updated.
A related activity within the Office of Environmental Management is the
development of the Programmatic Environmental Impact Statement (PEIS) for management
of DOE's waste streams. This document will evaluate options for treatment facility config-
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participating in the discussions. The draft PEIS will be released in the spring of 1994.
The National Governors' Association is providing a forum for states, EPA and DOE
to discuss FFCA-92 implementation. The Western Governors' Association is actively
seeking industry involvement in technology development. It has formed the Development
of On-site Innovative Technologies Committee to foster technology development for-mixed
waste management (9).
Report Purpose and Scope
This report may serve as an accessory to the F&OR document and flow diagrams
describing the treatment processes of the integrated MWTP facility. Its purpose is to
identify and describe the characterization needed at each stage for the operation of an
integrated MLLW treatment facility. As Site Treatment Plans are developed in compliance
with FFCA-92, the report can be consulted as a description of a "baseline" characterization-
for-treatment scenario.
Three general topical areas are covered:
• characterizing containerized MLLW prior to treatment, including
characterization to direct the waste to the appropriate treatment train and to
distinguish between LLW and transurank waste - Chapter 2
i ^'
• treatment process monitoring, and evaluation of sidestreams, including offgases -
Chapter 3 ,
• characterization of the final solid waste forms - Chapter 4.
The report is based on two technical workshops held in 1993. In January 1993, a
preliminary characterization needs assessment was carried out by a working group in
Albuquerque. That assessment showed the locations in the generalized treatment trains
where measurements are needed, and compiled a preliminary list of the parameters to be
measured. On that basis, a larger workshop of technical experts was convened in Las Vegas
in May 1993. This workshop was sponsored by EMSL-LV and the DOE. On the basis of
their areas of expertise, the participants were divided into three workgroups. Each group
developed a rough sampling/analysis plan for its respective portion of the treatment facility.
The emphasis of the workshop discussions was on the potentially applicable measurement
methods: their strengths and drawbacks for the proposed uses, and any associated research
or development needs.
The scope of this report is limited to those activities that take place within the
treatment facility. Characterization needs for excavated wastes are not included, nor are the
needs associated with waste transportation. The report covers process monitoring needs that
-------
are special to these treatment trains; testing that is standard in process engineering (flow
meters, level monitors, etc.) is covered only insofar as special requirements have been
identified. Likewise, characterization for worker safety in such a facility is not dealt with
explicitly, although special issues, such as waste criticality, are covered. There is a discussion
of all effluent streams as they exit the facility, but out-of-plant, ambient environmental
monitoring is not discussed. The five principal waste treatment trains are addressed, and
the measurement needs for each of the baseline treatment technologies are defined.
Only characterization needs are dealt with in this report. Review and discussion of
the generalized treatment trains for the five waste streams was not within the scope of the
workshop. Workshop discussions did, however, identify several duplicative measurements
that could be consolidated, and some instances where additional measurement points were
needed. Points where the lack of satisfactory characterization technology could constrain
the treatment design were identified.
Regulatory requirements can be expected to change over time, regardless of what
characterization strategy is adopted by DOE. This report does not attempt to define
characterization needs to meet a speculated future regulatory scenario. Instead, pertinent
current regulations are assumed as the baseline operating environment.
Quality assurance and quality control are not discussed at length in this report. In
the workshop discussions, QA/QC principally arose in the context of specific measurement
technologies. The report reflects these discussions, with QA discussions centering on the
data quality objectives for particular measurements, and the level of QA achievable with the
recommended characterization methods. In some cases, particularly characterization of the
final waste forms, the level of effort for quality assurance will be specified by regulatory
requirements. In other cases, the work group leaders agreed that QA/QC activities should
be assumed for planning purposes to represent 10-20% of total sampling and analysis efforts.
The workshop participants felt that the preconceptual design represented by the
F&ORs was not specific enough to allow actual characterization sampling plans to be
devised. For example, for many of the waste pre-treatment and treatment operations, it is
not yet settled what constitutes a batch. Consequently, numbers of required samples per
volume of waste handled cannot be specified. Where they could, the work groups specified
numbers of measurements per sample or per batch.
Because a complete sampling plan cannot be devised for the treatment facility,
comprehensive characterization costs cannot be estimated. In this report, the only cost
figures given are the costs of the principal instruments needed for the onsite laboratory, and
for on-line process monitoring.
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Organization of the Report
Within this report, the technical discussion of characterization needs is concentrated
in Chapters 2, 3, and 4. These correspond to the topical areas covered by the three
workgroups at the Las Vegas workshop. Each of these chapters is centered on an analysis
table, and each includes discussion of the characterization technologies recommended for
each measurement. The chapters differ considerably in format, as befits their different
topics. For example, characterization for process monitoring and control occurs at dozens
of points in the facility, while characterization of final waste forms occurs at one point- a
solid waste form about to exit the plant. '
Chapter 2: Preliminary Waste Characterization
f A dom*in.of this chapter begins Svhen the drums get to the dock' at the front end
ot the facility. It includes the waste pre-screening and screening stages, and any other
operations preparatory to assigning the wastes to a treatment train and beginning ore-
treatment. •&&?**
The major activities covered by this chapter are:
• identifying any containerized TRU wastes mistakenly routed to the MLLW
treatment facility
• physical/chemical characterization of containerized wastes to route them to the
appropriate treatment train
• identifying hazardous or special materials within the containers so that they can
be handled separately ; • J
• performing a radionuclide inventory on a container of waste.
The chapter's emphasis is on real-time or near-real-time, non-intrusive or minimally
methodS' Measurements requiring complete sampling are also
Chapter 3: Process Monitoring and Control
in i ,.ThischaP?f coverscharacterization techniques for the treatment trains themselves
including any solids, gases or liquids that are recirculated within the facility Both the ore-
treatment and treatment operations are covered.
of the Tv-f'n f!ret glveS a brief Summary of the five treatment lines
of the MWTP This is followed with a listing of the points where measurements are needed
specification of those measurements, and recommended methods. Next, there is a discussion
of the generic monitoring and controls needed for thermal treatment of MLLW; this section
applies to several of the treatment units specified for the MWTP. As a detailed example
there is a description of the measurement needs for operation of a plasma hearth furnace'
-------
The example is followed by a discussion of the tradeoff between rigor of characterization
and robustness of treatment technology, with reflections on how this balance affects facility
design. Finally, the observations and research recommendations of the process monitoring
workgroup are summarized.
Chapter 4: Final Waste Forms
This chapter discusses the characterization of the solid wastes that exit the facility:
glass, ceramic and grout waste forms; plus ferrous metals and elemental lead and mercury
that are destined for re-use. It is focused on the properties of the solid waste forms
requiring measurement, and the associated measurement parameters. The text concentrates
on the test methods, which are usually established by regulatory requirements.
Concluding Chapter
The final chapter contains a comprehensive list of the research, development and
demonstration priorities identified during the workshop. This is followed by a discussion of
waste treatment strategy as influenced by characterization needs and shortfalls. Pertinent
regulatory and institutional issues are summarized, and further work to define
characterization needs is discussed.
Appendices
The text is augmented by six appendices:
• Appendix A - detailed waste stream descriptions showing the points where
measurements are made.
• Appendix B - the 41 flow diagrams for the MWTP integrated facility.
• Appendix C - descriptions of the principal measurement methods identified for
up-front waste characterization. Many of these methods are also cited in the
chapters concerning process monitoring and final waste forms characterization.
• Appendix D - brief discussions of developing methods that may be of great utility
in process monitoring.
• Appendix E - technology summary sheets for the analytical methods used on the
final waste form samples.
• Appendix F - a bibliography of LLW characterization references.
10
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References
1.
2.
3.
4.
5.
6.
7.
8.
9.
U.S. Dept. of Energy. December 1993. Call for Technical Task Plans, FY95. Office
of Environmental Restoration and Waste Management, Office of Technology
Development.
U.S. Dept. of Energy. April 1993. U.S. DOE Interim Mixed Waste Inventory
Report: Waste Streams, Treatment Capacities and Technologies. Vol I
DOE/NBM-1100. ,
S. Wolf. 1993, Plenary session presentation to the Workshop on Characterization
of Containerized Mixed Low-level Waste. U.S. DOE, Las Vegas, NV. May 25,1993.
T.K. Thompson. 1992. Mixed Waste Treatment Project: Functional & Operational
Requirements for an Integrated Facility. Prepared for Los Alamos National
Laboratory, subcontract 9-XY2-Y9590-1.
U.S. Dept. of Energy. Undated. DOE Order 5400.3: Hazardous and Radioactive
Mixed Waste Management Program.
U.S. Dept. of Energy. Undated. DOE Order 5820.2A: Radioactive Waste
Management.
°Uideline for i
of DOE Order
ff Mixed W^te Integrated Program Technology
Summary. Office of Technology Development, Office of Research and Development.
Western Governors' Association. November 1993. Mixed Waste Working Group
TeThnLies ^^^ Committee to Devel°P On-site Innovative
11
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Chapter 2
Characterization Before Treatment
Isabel Anderson, George Eccleston and
Mark Pickrell
Introduction
Prescreening, characterization and sorting of wastes for assignment to treatment
trains will be accomplished as containers are received at the treatment facility. This chapter
identifies measurement methods and instrumentation appropriate to screening and
characterization of wastes contained in drams or boxes.
The number of containers and the range of wastes to be received at the facility
suggest that a building separate from the treatment plant should be considered to receive
containers where they can be characterized and accumulated into batches of similar wastes
prior to sending to treatment trains. This building would house the characterization
instrumentation, calibration standards, and the chemical laboratory. It would include areas
to hold received containers prior to characterization, and to store batches of characterized
containers with similar waste components that are awaiting treatment. A special storage
area would also be needed to properly store containers that were mistakenly shipped to the
MWTP facility and are awaiting return to the sender. A separate storage area may be
needed for difficult-to-characterize containers that will require special handling and intrusive
sampling. Some sampled containers may need to be set aside awaiting results from chemical
analysis.
Containers should be visually checked for damage when received at the loading dock.
Leaking containers should be set aside and must be repackaged before being moved into
the characterization building, otherwise contamination of characterization instrumentation
could occur.
The characterization strategy for waste containers consists of:
• identifying drums containing TRU wastes; these cannot be handled at the facility
• determining the radionuclides contained in drums, by quantity and isotope
• identifying hazardous and special materials that require separate handling of
containers and processing outside the five primary treatment trains
12
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determining the physical and chemical properties of the wastes to enable
assignment of the container to one of the five treatment trains.
Measurement Points and Techniques
Sample Points
A r 7?16 Rasterization requirements are expressed as "sample points." These are
defined in the F&OR document for the treatment facility (1) and the points of measurement
are shown on the flowsheets (Appendix B). For pretreatment characterization, all of the
sample points are shown on flow diagram PFD 010. Each "sample point" requires the
determination of a specific waste component in a container. For example, Sample Point
010 1 calls for the determination of the specific alpha activity to assure that containers with
1RU wastes are identified and not sent to the treatment trains.
Although the F&ORs and the sample points establish a framework for evaluating the
measurement technology, some specifics are lacking. For example, the accuracy bias or
precision necessary for a successful measurement have not been specified in the highly
conceptual MWTP design. In many instances, several measurement technologies address
a sample point requirement. Choosing the optimum method balances cost effort
measurement time, and whatever accuracy is necessary. The workgroup chose to address
each sample point with a range of possible measurement methqds rather than to specify an
optimum measurement technique. . •
Another issue that is not settled is the waste processing mode. For example it is
possible that the characterization prior to treatment and container segregation Would be
fn«\T°n!iT y ^ concurrently with Processing of the waste drums. Conversely, it is
possible that waste drums would be segregated into the different categories and then
processing mode ais° affects
Sample points appropriate to preliminary waste characterization consist of:
Point
010.1
Sample Parameter to be Characterized
Specific alpha activity (<> 100 nCi/gram).
This sample point rejects containers having alpha activity that exceeds 100 nCi/e
to assure that TRU wastes are not sent to the; treatment trains.
13
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010.2 Physical Properties
This sample point determines whether the container contents are liquid, wet or
dry solids, homogeneous solids, or heterogeneous solids.
010.3 Particulate content, or Pumpability
For containers of liquids or wet solids, determine whether the contents are
pumpable or contain large particles (assumed to be particles with a diameter of
eight inches or greater).
010.4 Qualitative and Quantitative Organics
This sample point determines the types and amounts of organic compounds in
the container, to enable proper assignment to a treatment train.
010.5 Hazardous Elements or Special Materials
This measurement is made for safety and to determine unique processing
requirements. For example, both lead and mercury require special processing,
as do high-clorine wastes. Other materials might present a hazard either to
personnel in the plant or to equipment.
010.6 Radionuclides
Both for safety and to assure land disposal requirements are met, the
radionuclide content of containers must be determined.
100.12 Total organic carbon
This sample point applies to a treatment train and is equivalent to sample point
010.4. Sample point 100.12 can be satisfied during characterization before
treatment and should not need to be repeated within the treatment train.
100.15 Particulate content
This measurement applies to liquids and wet solids, and determines whether the
material is pumpable. It is equivalent to sample points 010.2 and 010.3. Sample
point 100.15 can be satisfied during characterization before treatment and should
not need to be repeated at the treatment train.
200.22 Mercury content
Mercury is a hazardous material and must be treated in a unique manner,
outside the primary treatment trains.
300.11 Size of large solids ( >8 inches)
This measurement also applies to liquids and wet solids and determines whether
the material is pumpable. It is identical to sample point 010.3, and need not be
repeated within the treatment train.
14
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Measurement Techniques
Table 2.1 is a listing of measurement methods that are potentially applicable to
characterizing the incoming wastes. The table entries are organized according to sample
point. For each point, a number of techniques are listed. Those denoted by an asterisk
were discussed in the workshop. Non-starred entries were added later, and should be
considered less favorable choices. No specific "preferred method" is indicated for each
measurement; instead, a full suite of potentially applicable methods is listed.
In the table, measurement methods are classified by their physical nature: non-
intrusive (N), intrusive (I) such as headspace analysis, ot full sampling (S). For reasons of
safety, representativeness, and efficacy of container processing, non-intrusive methods are
preferable to intrusive methods or sampling. For each sample point, they are listed first.
Method sensitivity, precision and accuracy are also noted, where the information is
readily available. Many of these methods have been developed and applied in very different
operating environments than the MWTP integrated facility. Sensitivity, precision and
accuracy achievable within that facility may be very different than published values. The
entry "TBD" in these columns denotes "to be determined," meaning information on these
parameters was not readily available. Parameters clearly not applicable to the measurement
are so noted.
The listed methods are also classified as to whether they are established techniques
(E) or will require development (D) for this application.: Where methods were recognized
to need research, development or .demonstration, an estimate of the number of months
required is given. This estimate is very rough; it simply represents the "best judgement" of
the workgroup members. It must be stressed that most of the "established" methods would
also require adaptation and demonstration for this application.
Further details on the principal recommended methods are found in Appendix C
In the appendix, each individual technique is described and its capabilities and limitations
are defined. Specific research that is necessary to bring the method to its full potential is
also discussed.
In assembling information on the listed methods, a number of technical references
were consulted. The primary references, many method-specific, are 2 through 7. Secondary
references of a more general nature, including textbooks of analytical chemistry are 8
through 16.
The charge made to the workshop attendees was to determine applicable tech-
nologies for waste characterization; however, quantitative data quality objectives have not
been established. Although the techniques listed provide the type of information required
by the F&OR guidelines, they may not provide these: measurements at the required
precision and accuracy. The facility designer has several alternatives for resolving this
problem. 6
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Limitations in the specific characterization techniques can be accommodated by
additional and more complete waste treatment; multiple instruments with complementary
capabilities can be used in concert to achieve improved data quality; and additional research
and development can be done to augment the existing instrumentation capabilities.
Several factors account for the limitations of characterization technologies. In some
cases the available technologies were developed for other applications. These applications
probably have different data quality objectives and different operating conditions. Although
the underlying principals are similar, the specific application engineering may be quite
different. Some measurement techniques may require only modest re-engineering to adapt
them to this specific application. Other techniques may have been developed for less
demanding applications and may require significant scientific development to sufficiently
raise their capabilities.
Different instruments have different, and sometimes complementary capabilities.
Few instruments can accurately measure a quantity under all circumstances. For example,
gamma-ray spectroscopy is limited by the attenuation from high-Z (high atomic number)
materials (e.g., metals). Drums with large amounts of metals cannot be effectively measured
using garnma rays. Conversely, neutron-based measurements are largely unaffected by high-
Z materials, but are strongly affected by low-Z materials (e.g., the hydrogen in plastics).
These complementary limitations can be somewhat offset by properly combining individual
instruments. !
There is a significant problem with discrete sampling of heterogeneous waste. It is
effectively impossible to sample drums of heterogeneous waste in a manner that assures the
samples are representative of the entire container (18). Indeed, the need to circumvent this
problem is one of the principal forces driving the development of a MLLW treatment
facility based on very robust techniques. Discrete samples measure only a small portion of
the containerized waste. It is possible to develop sophisticated sampling plans to assure that
the ensemble of sample locations within the container is representative of the entire
container. However, these strategies require significant knowledge of the material
distribution in advance, which largely defeats the minimum-characterization approach. If the
drum contents are initially unknown, it is not possible to sample a drum and assure that the
samples are representative. Therefore, bulk measurements that measure the dram in its
entirety should be used whenever possible, even if thesei methods have significantly higher
bias errors. The important distinction is that the bias errors of bulk methods, such as
radiation-based methods, are well known. Without knowing the rnaterial distribution in
advance, the uncertainties from sampling are completely unknown. Therefore, it is
essentially impossible to assign specific data quality objectives for sampling methods because
the uncertainties cannot be quantified.
When a final measurement strategy is constructed from the required data quality
objectives, these limitations must be considered. An optimum measurement strategy may
use suites of measurement instruments for a single sample point in order to balance the
33
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strengths and weaknesses of the individual techniques. Additional, perhaps significant,
development may be necessary to improve some techniques to the required level of
performance. In some cases insufficient measurement capability may compel yet more
robust waste treatment methods. The measurement strategy designer must balance the costs
and benefits of these various options.
Conclusions and Recommendations
At the receiving area of the treatment facility, some real-time and near-real-time
measurements will be made on-line. However, for some containers, full sampling, with
sample submittal to an analytical laboratory at the MWTP, will be necessary. This lab will
measure both qualitative and quantitative attributes. A specific example of this need is the
quantification of organics in drums whose contents are heterogeneous or are not well known
a priori. The work group concluded that if organic content must be known to 1% it will be
necessary to open many drums and conduct physical sampling.
A corollary of this is that a large storage area will be needed to stage containers
while awaiting test results from the laboratory, for those containers requiring full sampling.
The size of the staging area depends on the plant throughput and the analysis turnaround
time. On-line, near-real-time (or better) measurements are not subject to this limitation.
The work group favored in situ measurements of the waste containers, even if those
could not be made in real time. Improvements in field-portable instrumentation far outpace
improvements in laboratory technologies. It is expected that the next ten years will see
growing regulatory acceptance of in situ methods, continued refinement of existing methods,
innovative application of new methods, and the need for fewer confirmatory analyses by
traditional methods. As an example, -the X-ray fluorescence instrument (XRF) can
determine heavy metals in a soil matrix in minutes as compared to nearly a day for analysis
by the atomic absorption spectrophotometer (AAS). Cost savings for field-portable XRF
over traditional AAS are approximately a factor of ten. The more samples analyzed in the
field, the greater the savings. Similar savings can be realized when "sniffers" are used for
volatile organic compounds (VOCs). In the case of VOCs, an additional benefit is seen in
the integrity of samples that, when shipped or handled, are destined to lose (preferentially)
highly volatile compounds.
There were considerable differences of opinion within the work group on the proper
role of process knowledge, and several experiences with seriously inaccurate container
manifests were related by group members. There was agreement that the treatment facility
should definitely use process knowledge and container manifests to the extent that they
could be trusted. The current practice is to place little or no trust in process knowledge,
particularly for wastes generated before the land disposal restrictions were put in place.
One strategy that has been used is to verify process knowledge and identify sub-populations
34
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within a waste stream using a screening technique such as real-time radiography. The group
felt strongly that workers within the DOE complex need more guidance from DOE on the
use of process knowledge. ;
I • , ' ''-•''.'
One way to get around insufficient process knowledge is to encourage or require
waste characterization at the shipping site if containers came from off-site. Many of the
techniques cited are applicable at the point of waste generation. Unfortunately, this doesn't
really diminish the .characterization requirements - it just moves them to another location
and time. \
E
The next round of design for the MWTP integrated facility should include
characterization experts as well as facility engineers. This goes for design of any treatment
facility that is at this stage. The treatment design and the measurement design are
intimately related. Field sampling experts should also attend.
No one technique can acquire all the needed information for diverse waste streams,
especially for radiation measurements. A facility accepting a wide range of waste streams
will need pairs or suites of methods, to cover the different waste types and configurations.
These may be able to be narrowed down for each specific facility, where there is a limited
range of incoming waste streams. • i
I
The group identified several indirect (non-intrusive) methods to assess pumpability
of containerized materials. For each of these, some method has to be worked out to infer
from an image - usually a radiographic image - whether the materials will pass through a
pump. ;
Almost all the existing methods for evaluating' the organic content of a closed
container require sampling or intrusive sensing. PGNAA warrants continued development
as a potential non-intrusive method. A related method, PFNA, also shows promise for non-
intrusive characterization. Also important will be development of intrusive methods
combined with fiber-optic systems for headspace sensing or submersion in containerized
liquids. Sensing methods include immunoassay, FTIR, U(V fluorescence, and others. These
systems would likely require hardening for this application.
A very similar situation exists with respect to assessing special materials in containers.
Many of the parameters of concern are currently difficult or impossible to sense or quantify
non-intrusively. Here too, development of PGNAA, PFI^A, and minimally intrusive sensing
techniques hold the most promise for avoiding the need to sample.
i
Several of the measurement technologies which cpuld be used in the characterization
of containerized MLLW were developed for very different applications. In some cases all
that is needed is to adapt the technology for the MLLW application, which should require
only a modest development effort. In other instances the existing technology is insufficient
35
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for this application and must be extended, which might require significant research and
development.
In this work group, there was some difficulty in selecting methods because needed
data accuracy and precision (or DQOs more generally) are not well defined at this point.
When the group tried to address this matter, they found it thoroughly tangled with the issue
of representative sampling - not easy in many of the waste streams, which may be very
complicated matrices. In some of these waste streams it seems unlikely that rigorous
quantitative DQOs can ever be met. Designers of the up-front characterization program
need more information from the facility design engineers on how much uncertainty the
initial waste processing .operations can tolerate.
A significant technological issue is whether to use discrete sampling or bulk
measurement. Discrete sampling suffers from the limitation that it may not represent
heterogeneous matrices properly. There is no a priori method for insuring that discrete
sampling completely characterizes a container. Bulk measurements are not subject to this
limitation, and are thus favored, where they can meet requirements of the measurement.
References
1.
2.
3.
4.
5.
T.K. Thompson. 1992. Mixed Waste Treatment Project: Functional & Operational
Requirements for an Integrated Facility. Prepared for Los Alamos National
Laboratory, subcontract 9-XY2-Y9590-1.
Air and Waste Management Assoc. 1993. Field Screening Methods for Hazardous
Wastes and Toxic Chemicals. Proceedings of the 1993 U.S. EPA/A&WMA
International Symposium, Las Vegas, NV, February 1993, UIP-33.
U.S. Environmental Protection Agency. 1988. Field Screening Methods Catalogue,
User's Guide. EPA/540/2-88/005. Office of Emergency and Remedial Response,
Washington, DC.
L.H. Keith (editor). 1991. Compilation of EPA's Sampling and Analysis Methods,
W. Moeller and D.L. Smith, compilers. CRC Press, Boca Raton, FL.
M.C. O'Brien, R.H. Merservey, M. Little, J.S. Ferguson, and M.C. Gilmore. 1993.
Idaho National Engineering Laboratory Waste Area Groups 1-7 and 10 Technology
Logic Diagram, Volumes I, II, and III. EG&G Idaho, Inc., Idaho Falls, ID. EGG-
WTD-10784.
36
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6. Pacific Northwest Laboratory. 1993. DOE Methods for Evaluating Environmental
and Waste Management Samples. DOE/EM-OQ89T, Rev. 1. PNL, Richland, WA.
7. L.D. Koeppen, RJ. Gehrke, J.W. Rogers, C.L. Rdwsell, and C. Casey. 1989. Quality
Assurance/Quality Control Program of the Radiation Measurements Laboratory for
Gamma Spectroscopy and Direct Cross Alpha/Beta Counting. Internal Technical
Report ST-CS-013-89. EG&G Idaho, Inc., Idaho Falls, ID.
8. D.C. Harris. 1987. Quantitative Chemical Analysis, 2nd edition. W.H. Freeman &
Co., San Francisco, CA.
9. J.G. Grasselli, M.K. Snavely, and B.J. Bulkih. ! 1981. Chemical Applications of
Raman Spectroscopy. J. Wiley & Sons, New York.
10. R.M. Smith (editor). 1988; Supercritical Fluid Chromatography. The Royal Society
of Chemistry, London. ' \
11. T. Kuwana (editor). 1978. Physical Methods in Modern Chemical Analysis.
Volumes I and II. Academic Press, New York. '-,
12. R.W. Frei and O. Hutzinger (editors). 1975. Analytical Aspects of Mercury and
other Heavy Metals in the Environment. Gorden and Breach Science Publishers,
London. i
13. T. Handi (editor). 1982. Handbook of Chromajtography, Volume I: Phenols and
Organic Acids. CRC Press, Boca Raton, FL. '
14. Instrument Society of America. 1986. Analysis Instrumentation, Vol. 22.
Proceedings of the 32nd Annual ISA Analysis Instrumentation Symposium.
Instrument Society of America. Research Triangle Park, NC.
.)
15. D.A. Collnick. 1986. Basic Radiation Protection Technology. Pacific Radiation
Corporation, Altadena, CA. j
16. J.K. Taylor. 1987. Quality Assurance of Chemical Measurements. Lewis Publishers,
Chelsea, MI. i
i
17. D. Duffey, A. El-Kady and F.E. Fenelt. 1970. Analytical.sensitivities and energies
of thermal-neutron-capture gamma rays. Nuclear! Inst. and Methods, Vol. 80, p. 149.
I
18. G. Rupp and R. Jones, Jr., editors. 1992. Characterizing heterogeneous hazardous
wastes: Methods and recommendations. EPA/600/R-92/033. U.S. Environmental
Protection Agency Office of Research and Development, Environmental Monitoring
Systems Laboratory, Las Vegas, NV. j
37
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Chapter 3
Process Monitoring and Control
Ray Geimer, Gary Leatherman and Ellen Stallings
Introduction
This chapter discusses waste processing characterization/sensor needs for the
treatment of mixed low-level waste. The MWTP flow diagrams and F&ORs have been used
as the framework within which to discuss the nature of characterization and sensor needs
and the availability and status of characterization/sensor technology to meet those needs.
This chapter is divided into several parts: a brief description of the MWTP
flowsheet; a description of measurement points in the MWTP flowsheet where
characterization is required with the suggested measurement techniques listed with
information about each technique; an examination of the generic monitoring and controls
required for operation of thermal treatment units for the treatment of low-level mixed waste
(since the MWTP flowsheet relies heavily upon thermal treatment); as a detailed example,
a description of the characterization/sensor requirements for the plasma hearth process (a
technology which has the potential to be omnivorous thereby minimizing characterization
and sorting requirements); and recommendations for technology development to meet the
characterization needs identified by the workshop. The use of existing automation hardware
and software for monitoring the processing of the mixed low-level waste is discussed in
Appendix D. "Smart sensor" process monitoring control applications have been introduced
by industry recently and will be used for the characterization of MLLW; see Appendix D
for further details.
The Mixed Waste Treatment Project Integrated Treatment Facility
The MWTP facility (see Appendix B for flow diagrams) consists of five processing
lines for treatment of incoming waste: aqueous liquids, organic liquids, wet solids,
homogeneous dry solids, and heterogeneous solids. The types of wastes encompassed by
these categories are described in detail in Appendix A. Incoming waste is sorted and
assigned to one of these process lines. The basic working assumptions of this discussion are
that incoming waste will be assigned to the correct treatment process line during initial
characterization (as discussed in Chapter 2), and that characterization of the final waste
38
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forms will take place after treatment is complete (see Chapter 4). Monitoring of process
offgases is discussed in this chapter. i
The aqueous treatment line is basically a standard! waste water treatment process line.
It contains unit operations for neutralization of acidic or caustic liquids, removal of
suspended solids, separation of large quantities of organic compounds, destruction of
residual organics by wet air oxidation, and final polishing of effluent water.
1 • '
{ •
The organic liquids process line is more complicated, but primarily involves
separating the incoming organic waste into dilute organics, concentrated organics, and heavy
organics. After appropriate pretreatment such as solids removal, the dilute organics are
treated in a controlled air incinerator, the concentrated organics in a rotary kiln incinerator,
and the heavy organics in a car-bottom furnace. !
• i . » .
The wet solids line consists primarily of a size reduction unit operation to insure
pumpability of the incoming wet solids and a low tempjerature drying unit to dewater the
sludges. The resulting dry solids are then assigned to the appropriate portion of the
homogeneous solids processing line. !
The homogeneous dry solids line sorts the incoming waste into organics, inorganics,
nonferrous metals, and ferrous metals. Bakeout of liquids and mercury occurs if necessary.
The organics are incinerated in a controlled-air furnace. The inorganics are vitrified in a
joule melter and the metals melted in an electrically heiated batch melter. The slag from
the metal melters is tapped off separately and may with the addition of appropriate additives
be processed in a joule melter to produce the final waste form.
- i -
The heterogeneous solids line includes size sorting and size reduction, then separates
the waste into the above-listed categories of organics, inorganic solids, ferrous metals, and
nonferrous metals. (It should be noted that, with the promulgation of the RCRA Debris
Rule, most MLLW treatment facilities will have complete, separate treatment trains for
wastes that can be classified as "debris" under that rule.)
The flowsheet also includes appropriate offgas systems for the thermal units, holding
tanks, and transfer lines/valves etc. to enable the integrated operation of the facility.
Measurement Requirements for Process Control
The characterization requirements for the five treatment lines (flow diagrams 100-
500) are listed below according to measurement numbers that match measurement points
on the flow diagrams. The suggested measurement techniques are listed with limited
information about each technique. Potential .offgas: monitoring instrumentation and
radiometric research or development needs are also included. ;
39
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Aqueous Liquids Treatment (flow diagrams MWTP-PFD-100)
The purpose of this process is to treat aqueous streams from both external newly
generated and stored aqueous liquid waste and internal transfers from within the facility to
produce a clean effluent water. The process has a feed preparation area, filtration units,
pretreatment tanks, a primary carbon bed treatment unit, special feed treatment units, and
a unit for feed containing organics. The feed must have < 1% organic content and must
be pumpable (defined as <40% particulate).
The waste containers will be opened and the contents screened before the waste is
introduced into the processing lines to prevent mixing of incompatible materials, and to
verify that the feed is appropriate for the treatment line.
Preliminary Measurement Requirements (MWTP-PFD-100-n
100.11 pH
Purpose: safety: ensure that highly acidic or caustic solutions are not mixed; to
prevent a violent reaction in the tanks.
Matrix: solutions containing <1% organic content, <40% particulate (may contain
heavy metals, radionuclides, salts, etc.)
Accuracy required: 1 pH unit
Precision: 10-20%
Time Frame: 5-15 minutes
Suggested Measurement Technique: pH probe, automated titration - Existing
Technology
100.12 Total Organic Carbon
Purpose: protection of process line from out-of-specification feeds; verify solutions
are < 1% total organic content
Matrix: same
Detection Omit: percent
Range: < 1% or > 1%
Accuracy: 50%
40
-------
Precision: 10-20% j
'I.
Time Frame: 5-15 minutes ;
Potential Measurement Technique: Total Organic Carbon Analyzer - Existing
Technology j
r
' • . " I
100.13 Compatibility |.
i
Purpose: safety; verify that a violent reaction will not occur as a result of mixing
incompatible feeds i
i - .
Matrix: same i.
Time Frame: < 15 minutes !
Potential Measurement Technique: Differential Thermal Analysis (DTA) with offgas
sampling. Existing technology. "\
I
I
Other: DTA generally requires one to several hours.
Assign Treatment
A processing decision must be made to assign the feed to the special feed tank, main
feed tank, or to the organics feed tank. ;
!
! '-
100.14 Quantitative Total Organics
' ! '•" -
Purpose: If organics are present, the solution will be routed to the wet air oxidation
feed tank for organic destruction. i
Matrix: Large particulates (>3mm) are removedlfrom the aqueous stream.
i
Detection Limit: 10 ppm !
Range: 10-10,000 ppm j
, - i
Accuracy: 10 ppm s
Precision: 10-20% j
i
Time Frame: < 15 minutes
i • .
Potential Measurement Technique: Total Organic Carbon Analyzer - Existing
Technology j
41
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100.15 Particulates
Purpose: If gross levels of particulates are present, the feed will be routed to the
Special Treatment Line.
Matrix: same
Range: Determine if particulate content is > 1% or < 1%
Time frame: minutes
Potential Measurement Techniques; Conductivity, Acoustical Sensor - Existing
Technology
»
100.16 Heavy Metals
Purpose: Gross amounts of heavy metals that would foul the carbon adsorption beds
in the Primary Treatment Line will be removed in the Special Treatment Line.
Matrix: same
Range: ppb-ppm, depending on metallic species
Time frame: minutes
Potential Measurement Techniques: • LIBS, ICP/MS, XRF, 1C, UV-Fluorescence,
Voltammetric Measurements, FA/Flow Probe, Capillary Zone Electrophoresis
LIBS (Laser Induced Breakdown Spectroscopy)
Constituents Measured: Most of the periodic table
Detection Limits: ppm - percent
Time for Measurement: Real-time
Instrument Cost: 80-100K
Technology Status: R&D; 3-4 years for development
Other: Non-invasive measurements possible for most of the periodic table in any
matrix
42
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ICP/MS (Inductively Coupled Plasma/Mass Spectroscopy)
i
Constituents Measured: 80% of the periodic table
Detection Limits: ppt - ppm j
Time for Measurement: Real-time i
i
i
Instrument Cost: 250 - 300K ' •
Technology Status: Commercially available, needs adaptation to application
i
Other: Provides isotopic information; cost is high; instrument may not be rugged
enough to survive processing floor conditions I
i
XRF (X-ray Fluorescence) j
i • •' . ,
i
Constituents Measured: Elements higher than aluminum in the periodic table
Detection Limits: high ppm - percent i
Time for Measurement: Real-time !
t
Instrument Cost: 75-90K I
Technology Status: Commercially available
Other: Provides a penetrating analysis (not just surface)
1C (Ion Chromatography) ;
Constituents Measured: metals, anions \
Detection Limits: ppm ;
Time for Measurement: 10's of minutes . i '
Instrument Cost: 50-70K i
i
Technology Status: Commercially available '
i •-.
Other: Not optimal technology for metals in complex matrices
' - ' . 1
i
UV-Fluorescence !
Constituents Measured: U, Actinides, specific metals
i
43 ;
-------
Detection Limits: ppm - percent
Time for Measurement: Real-time
Instrument Cost: 25-35K
Technology Status: R&D; 3-4 years to develop for this application (currently a
laboratory technique)
Other: May be a low cost option
Voltammetric Measurements
Constituents Measured: U, Fe, Cu, V, heavy metals
Detection Limits: ppb
Time for Measurement: Minutes
Instrument Cost: 25-35K
Technology Status: Commercially available, needs adaptation to application
Other: May be a low cost option; technique has good selectivity for some hard-to-
measure elements
FA (Flow Injection Analysis)/Flow Probe
Constituents Measured: heavy metals
Detection Limits: ppm - percent
Time for Measurement: Minutes
Instrument Cost: 5-25K
Technology Status: Some applications are developed, others would require R&D
Other: Inexpensive sensors for specific constituents may be practical for some
applications
CZE (Capillary Zone Electrophoresis)
Constituents Measured: Heavy metals detection limits; ppt - ppm
Time for Measurement: Real-time
44
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Instrument Cost: 50-70K
Technology Status: Commercially available, needs adaptation to application
Other: This multi-element technique uses small sample volumes
100.17 pH ! .
Purpose: Feeds requiring neutralization will be routed to the Special Treatment
Line.
Matrix: same :
Accuracy: 1 pH unit
Precision: 10-20%
Time frame: minutes '•
Potential Measurement Techniques: pH Probe, Titration, Acid Sensor - Existing
Technology
100.18 Other problematic compounds (cyanide, chelating agents, nitrates, etc.)
Purpose: Determine if other compounds are present that may interfere with down-
line processes, or affect final waste form integrity.
Measurement parameters cannot be specified.
Potential Measurement Techniques: 1C (see 100,16), ISE
ISE (Ion Specific Electrodes)
Constituents1 Measured: Anions, cations
Detection Limits: ppm
Time for Measurement: Minutes
Instrument Cost: 15-20K ;
Status of Technology: Commercially available
Other: Interferences are major problems in many cases; technique is rugged- some
chemistry is required
45
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Special Treatment (MWTP-PFD-100-2^
The special treatment unit of the aqueous line will remove gross concentrations of
heavy metals, salts, radionuclides, etc., that may foul the main activated carbon beds in the
primary treatment unit. The treatment may include manual addition of chemical additives
for precipitation, neutralization, valence adjustment, etc., or may contain specialized ion
exchange resins to remove specific contaminants.
Measurement Requirements
100.21 Contaminant Concentration (heavy metals, radionuclides, etc.)
Purpose: Determine when treatment is complete (for example, continuously monitor
the effluent exiting ion exchange columns to determine effectiveness of treatment)
Matrix: Aqueous solutions with most particulate material removed, may range from
dilute solutions to solutions that contain substantial dissolved solids
Detection Limit: ppm range
Range: ppm - percent
Accuracy: ppm
Precision: ppm
Time frame: Real-time or near reaMime
Potential Measurement Techniques: Ion Specific Sensors or Electrodes,
spectroscopy,' alpha, beta, gamma detectors, etc.
- These measurements are highly dependent on the treatment technology
100.22 Oxidation State
Purpose: Some specialized treatments (such as ion exchange) may require oxidation
state adjustment to feed.
Matrix: same as above
Detection Limit: ppm range
Range: ppm - percent
Accuracy: ppm range
Precision: 10-20%
46
-------
Time frame: real-time or near real-time
i
Potential Measurement Technique: Spectroscopy
- Specialized treatment diagnostic instrumentation is highly dependent pn the
process; some measurement techniques may be required that measure process
characteristics rather than specific constituents and some spectroscopic techniques
(Near Infrared Spectroscopy) may be useful.
100.23 pH or Acid Concentration
i
Purpose: Determine when feed neutralization is complete
Matrix: same
Accuracy: 1 pH unit
Precision: 10-20%
Time frame: minutes
Potential Measurement Techniques: pH Probe, Titration - Existing Technology
100.24 Ionic Strength or Conductivity
Purpose: High salt content can affect treatment
Matrix: same
Detection Limit: percent range
Time frame: minutes
Potential Measurement Techniques: Conductivity Meter - Existing Technology
Organic Separation and Wet Air Oxidation nVIWTP-PFD-100-3)
Organics are oxidized to carbon dioxide and water in the organics oxidation unit that is
based on the wet air oxidation process. The oxidizing agent is high pressure plant air.
Measurement Requirements
100.31 Organic content
Purpose: verify effectiveness of treatment (determine if feed should be routed to
primary treatment or final polishing)
47
-------
Matrix: Aqueous solutions will still contain inorganic contaminants, but the organics
should have been destroyed.
Detection limit, Accuracy, and Precision: Regulatory levels (ppb-ppm) that will
apply downstream. Must meet EPA standards for Quality Assurance.
Time frame: minutes
Potential Measurement Technique: GC/MS
GC/MS (Gas Chromatography/Mass Spectroscopy)
Constituents Measured: Volatile and Semi-volatile organics
Detection Limits: ppb - ppm
Tune for Measurement: 10's of minutes
Instrument Cost: 100 - 120K
Status of Technology: Commercially available
Other: This measurement will probably be made in the facility's support laboratory
rather than at the process line
Primary Treatment (MWTP-PFD-100-4')
Once all appropriate pretreatment is completed, the dissolved (and some suspended)
inorganics are removed in the activated carbon beds in the Primary Treatment Unit.
Measurement Requirements
100.41 pH
Purpose: Neutralization of feed, if necessary, before introduction to the carbon beds.
Matrix: same
Accuracy: 1 pH unit
Precision: 10-20%
Time frame: minutes
Potential Measurement Techniques: pH Probe, Titration
48
-------
Second Stage Polishing (MWTP-PFD-100-5) :
This unit removes all remaining inorganic ions from the clean water stream. This is
accomplished using ion specific technologies such as media beds or membranes.
Measurement Requirements
100.51 Condensate quality (NPDES requirements)
Purpose: Determine if condensate meets specifications for release to the
environment, or recycle. These will be established under a facility-specific NPDES
permit.
Matrix: evaporator condensate (clean water)
Detection Limit, Accuracy, Precision: As per NPDES requirements set forth by EPA
or the State.
Potential Measurement Techniques: EPA-specified methods
- Existing Technologies
Solids Concentration/Dewatering Treatment fMWTP-PFD-100-6)
The purpose of the solids concentration/dewatering unit is to evaporate the water associated
with the separated solids.
Measurement Requirements
100.61 Evaporator Bottoms Moisture Content
Purpose: Determine when dewatering is complete
Matrix: Sludge in evaporator
Detection Limit: percent
Accuracy: percent
Precision: 10-20%
Time frame: real-time, continuous
Potential Measurement Techniques: TBD
- Workshop participants did not think this measurement will be necessary
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100.62 Radionuclide concentration potential
Purpose: Safety; verify that radionuclide concentration doesn't build up in the
evaporator.
Matrix: Sludge in the evaporator
Time frame: real-time, continuous monitor
Potential Measurement Techniques: On-line Alpha, Gamma, Beta, Neutron
Monitors
- Should meet DOE/NRC Quality Assurance standards for criticality control
- Workshop participants determined that radionuclide content in the evaporator
would be controlled by measuring what goes in, so the evaporator itself will not need
to be monitored.
Organic Liquids and Slurries Treatment (MWTP-PFD-200)
The function of this line is to process dilute organic liquids, concentrated organic
liquids, and organic sludges to produce waste forms that can be further processed in other
treatment lines.
Segregation (MWTP-PFD-200-1^
Organic waste is segregated into four categories: category 1 (concentrated organic liquids);
category 2 (concentrated organic sludges and slurries), category 3 (concentrated organic
liquids containing solids); and category 4 (dilute organics), according to the shipping
manifest. Aqueous liquids may be present at up to 99% in category 4 wastes. The
concentrated organic wastes have no discrete aqueous layer present.
Assign Treatment rMWTP-PFD-200-2^
The function of the assign treatment process is to verify drum content and route the waste
to the proper downstream process.
Measurement Requirements
200.21 Pumpable or sludge?
Potential Measurement Techniques: Real-time-radiography
- Existing Technology
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200.22 Mercury
Purpose: Organics contaminated with mercury will be treated separately
Matrix: Organic liquids and sludges
Detection Limit: low ppm range
Range: low ppm - low % .
Accuracy: 50%
Precision: 10-20%
Time frame: minutes
Potential Measurement Techniques: PGNAA, Hg Vapor Analysis, Immunoassay,
Jermone Mercury Analyzer
PGNAA (Prompt Gamma Neutron Activation Analysis)
Constituents Measured: Heavy metals, chlorides
Detection Limits: High ppm - percent
Time for Measurement: Real-time
i. ,'
Instrument Cost: 100 - 120K
Status of Technology: Commercially available, need to demonstrate usefulness to
this application
Mercury Vapor Analysis
Constituents Measured: Mercury
Detection Limits: ppb-ppm
Time for Measurement: Real-time
Instrument Cost: 25-30K
Status of Technology: Commercially available, needs adaptation to application
Other: Very specific for elemental mercury
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Immunoassay
Constituents Measured: Mercury
Detection Limits: ppb - ppm
Time Measurement: Real-time
Instrument Cost: information not available
Status of Technology: In demonstration by EPA Superfund Office
Other: Highly sensitive and specific, non-renewable (one-time use of sensor)
Jermone Mercury Analyzer
Constituents Measured: Mercury
Detection Limits: ppb - ppm
Instrument Cost: 10-15K
Status of Technology: Commercially available, some adaptation to application
Other: Non-reversible, accumulative
200.23 Dilute or concentrated organics? (How much water is present?)
Purpose: Routing decision
Range: < 10% or > 10%
Time frame: minutes
Potential Measurement Technique: Karl Fisher
Dilute and Concentrated Organics Separation (MWTP-PFD-200-4^1
The dilute organic fraction from the continuous decanter is routed to the wet air oxidation
treatment unit, and the heavy organics will be burned in the car bottom furnace.
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Measurement Requirements
200.41 Organic content of dilute fraction
1 >
Purpose: Ensure the wet air oxidation unit can treat the level of organics present
(same as measurement 100.14)
Wet Solids Treatment (MWTP-PFD-300)
Wet solids are size reduced, if necessary, and then dried in preparation for treatment
in the Thermal Treatment Line.
Feed Preparation (MWTP-PFD-3QO-1)
Measurement Requirements
300.11 Does drum contain large aggregate solids (>8 inches in the largest dimension)?
Purpose: Drums that contain large aggregates are directly routed to size reduction.
Time frame: minutes
Potential Measurement Techniques: NDE, such as X-ray
Feed Tankage (MWTP-PFD-300-3^
Sludge coming from the grit screen is pumped either to special feed tank or main feed
tanks, depending on the properties of the sludge. Main process feed is wet solid material
that can be fed to the main feed dryer that operates at about 200 degrees centigrade without
deleterious effects. The specialized feed may include nitrated wet solids, ion exchange
resins, organics as cellulosic adsorbents, spent activated carbon, mercury contaminated wet
solids, chlorine salts, etc. Each of these has unique properties that require a low
temperature rotary vacuum type dryer. These materials can be thermally sensitive, have
higher than normal radioactivity levels, or produce harmful vapors if subjected to the higher
temperature in the primary dryer. :
Measurement Requirements
300.31 Screening for high nitrate, mercury, lead, chloride
Purpose: Determine if sludge will be routed to the high temperature dryer or the
low temperature dryer.
Detection Limit: low ppm
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Range: low ppm - low %
Accuracy: 50%
Precision: 10-20%
Time frame: minutes
Potential Measurement Techniques: (see 100.16, 100.18, and 200.22)
300.32 pH or Acid Content
Purpose: Highly acidic or alkaline sludge will be neutralized.
Matrix: Sludge
Accuracy: IpHunit
Precision: 10-20%
Time frame: minutes
Potential Measurement Techniques: may require a combination of high acid sensors,
high caustic sensors, and pH probes.
Homogeneous Dry Solids Treatment (MWTP-PFD-400)
This process consists of separating the homogeneous dry mixed waste into combustible,
ferrous metal, non-ferrous metal and inert streams for further processing in the melt/slag
and thermal treatment lines.
Preliminary Sorting (MWTP-PFD-400-2)
Measurement Requirements
400.21 Mercury
Purpose: Mercury contaminated dry solids will be processed separately.
Range: ppm - low %
Accuracy: < 10 ppm or > 10 ppm
Time frame: Real-time continuous monitoring
Potential Measurement Techniques: (See 200.22)
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400.22 Lead
Purpose: Lead contaminated dry solids will be processed separately.
Range: ppm - low%
Accuracy: < 10 ppm or > 10 ppm
Time frame: Real-time continuous monitoring
Potential Measurement Techniques: (See 100.16) ,
Magnetic Separation Treatment rMWTP-PFD-400-5^
Ferrous metals are removed from the homogeneous dry solids stream by a magnetic
separator. The non-magnetic ferrous alloys and non-ferrous metals must be sorted for
treatment in separate melters.
Measurement Requirements
400.51 Separation of non-magnetic ferrous alloys from non-ferrous metals
Purpose: Separation of incompatible metals for melting, as these materials will be
processed to final waste forms in separate melters.
Potential Measurement Techniques: Alloy detectors
Heterogeneous Dry Solids (MWTP-PFD-500)
This process consists of separating, and size reducing if necessary, the heterogeneous
dry mixed waste into combustible, ferrous metal, nonferrous metal and inert streams that
are further processed separately.
'•'"'.'. • • • ~
The measurements are the same as those for homogeneous dry solids (see above).
On the flowsheets they are numbered 500.21 through 500.51.
Radiamettic Measurements for Process Control
The work group felt that measurement of radionuclides during waste treatment
deserved special attention. The group's general observations on this topic are:
1. Tracking the radionuclides throughout the process is probably essential.
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2. Neutron and photon (X-ray and gamma-ray) detection and pulse processing is an
advanced technology. Its use on-line in DOE processing facilities has been
demonstrated. These detectors should be employed often throughout the process
streams.
3. Ash from thermal treatment is the best physical form for radionuclide assay. It
should be batched into containers (within glovebox containment) and measured with
segmented Gamma-Ray Scanner (SGS) and Passive/Active Neutron Counter
(coincidence counting and active interrogation). This combined assay will provide
the best data on Pu and U (and other radibisotopes) before final waste form
processing.
4. A large component of the development of a system is assurance of data quality. This
includes proper calibration technique, continuous measurement control, and on-line
data analysis. Computer control employing real-time continuous, unattended
operation has-been demonstrated.
In addition, several research and development needs and priorities for tracking
radionuclides were identified during the workshop. These are:
1. Room temperature, solid state detectors (photons) with resolution better than Nal,
such as CdTe, HgI2 (see EG & G, Santa Barbara work), pin diodes, photodiodes, and
other silicon technologies are needed. These would be applicable to many harsh
environments, especially where liquid nitrogen, refrigeration, and the presence of
maintenance personnel are precluded. Operational saving are possible; however,
continuing expensive development is required.
2. Radioactive tracer nuclei may be beneficial for sensitive determination of
breakthrough in an ion exchange resin (for example, photon systems).
3. Development of real-time, continuous, unattended monitoring including measurement
control for QA after initial calibration (neutron and photon systems) should be
continued.
4. Neutron detector development (perhaps coated solid state) would be useful.
Efficiency is important: polyethylene moderators with imbedded He3 tubes are good,
but expensive (approximately $800/tube and 1 tube/3 inches coverage is required).
5. Pulse-processing developments for neutron counting should continue to maximize the
available information (e.g., multiplicity and, perhaps, crude imaging).
6. Development of radionuclide monitoring techniques for stack gases must continue.
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Potential Offgas Monitoring Instrumentation (MWTP-PFD-1001)
GC/MS (Gas Chromatography/Mass Spectrometry) ; '
Constituents Measured: Volatile and semi-volatile organics
Detection Limits: ppb - ppm
Time Measurement: lO's of minutes
Instrument Cost: 100 - 125K
' ! . . • ' . ! "'""„'-'
Status of Technology: Commercially available; some adaptation for this application
Other: Complex instrumentation that may not be appropriate for stack gas
monitoring
MS (Mass Spectrometry)
Constituents Measured: PICs (Products of Incomplete Combustion)
Detection Limits: ppb - ppm
Time for Measurement: Real-time
Instrument Cost: 100-.125K
Status of Technology: R&D required for this application
Other: Limited selectivity, may not be appropriate for a stack gas monitor
FTIR (Fourier Transform Infra-Red Analysis)
Constituents Measured: Organics, nitrate
Detection Limits: ppm - percent
Time for Measurement: Real-time
Instrument Cost: 60 - 80K
Status of Technology: Commercially available
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TOC (Total Organic Carbon Analyzer)
Constituents Measured: Organics
Detection Limits: ppm - percent
Time for Measurement: 10's of minutes
Instrument Cost: 40 - 60K
Status of Technology: Commercially available
Other: Rugged and process proven
CARS (Coherent Antistokes Raman Spectroscopy)
Constituents Measured: Organics and temperature .
Detection Limits: percent
Time for Measurement: Real-time
Status of Technology: R&D
Other: Need more information on this technique
PGNAA (Prompt Gamma Neutron Activation Analysis)
Constituents Measured: Heavy metals, chloride
Detection Limits: High ppm - percent
Time for Measurement: Real-time
Instrumentation Cost: 100 - 125K
Status of Technology: Commercially available, needs demonstration for this
application
Other: Matrix dependant
Laser Induced Fluorescence Spectroscopy (LIFS)
Constituent Measured: Heavy metals, volatile and semi-volatile organics
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Detection Limits: ppb.-ppm
Time for Measurement: Real-time
Status of Technology: R&D; 2 years needed to develop
Other: Good sensitivity
Specific compound sensors ;
Constituents Measured: Developed for specific constituents
Status of Technology: R&D; 3 years to develop
Generic Monitoring and Controls Required
for Operation of Thermal Units
for the Treatment of Mixed Low-level Waste
These requirements relate to the thermal treatment units shown in flow diagrams
801-808, and 1001 (see Appendix B). Most are measured in the offgas from the secondary
combustion chamber (flowsheet 808) or at the stack (flowsheet 1001).
Major Species Requiring Characterization
Continuous monitoring of oxygen (O2) is required by regulations to correct carbon
monoxide concentrations in the unit to a standard basis of 7% oxygen by volume. Oxygen
continuous monitoring is also necessary for control purposes and will be tied into the
thermal treatment unit control system. Regulations allow the O2 monitor to be located
anywhere in the offgas system from the secondary combustion chamber (SCC) exit to the
stack, though preferably as close as possible to the SCC exit. For combustion control
purposes, the O2 monitor should be located at the SCC exit. Monitoring conditions are as
follows: O2 range from 0 to 25% (air is 21% oxygen by volume but the expanded range
covers oxygen enrichment processes); temperature range from ambient to 2200°F;
depending on monitor location and offgas equipment, normal operating pressure could range
from about -100 in. W.C. to atmospheric pressure (some positive pressure surges from upset
conditions in the thermal treatment device are expected); offgas environment is generally
oxidized with "puffs" of a reducing environment expected; offgas will contain acid gases such
as HC1, HF, SO2, SO3, and nitrogen oxides (NOX) at levels generally below a few hundred
parts per million (ppm) but could be as high as 10% for certain wastes and certain thermal
treatment devices; particulate in the form of inorganic oxides, inorganic salts, carbon (soot),
and elemental species will be present at loadings that can exceed a concentration of 5 grains
per dry standard cubic foot (5 gr/dscf). The current state-of-the-art for oxygen monitors is
analysis of an extractive sample or the use of a probe for an in situ analysis. Because of the
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harsh conditions in the offgas at the SCC exit, monitors at this location are subject to
frequent maintenance and calibration.
Carbon monoxide (CO): continuous monitoring is required by regulations to
determine the amount of CO emitted and as an indication of the combustion efficiency of
hydrocarbons. Although the CO monitor is not normally tied into the thermal treatment
unit control logic, it is frequently used by operators as an indicator of changes that need to
be made or how well changes that have been made affect operations. As with the O2
monitor, the CO monitor can be located anywhere in the offgas system but near the SCC
exit is desirable from both a regulatory and an operational standpoint. . Monitoring
conditions are as follows: CO content ranges from essentially 0 CO to over 1000 ppm with
normal operating range between 40 -100 ppm. The EPA requires a dual range CO monitor
with ranges from 0 - 200 ppm and 0 - 3000 ppm. All other conditions are the same as those
for the O2 monitor.
Carbon dioxide (CO2) monitoring is required when burning polychlorinated biphenyl
(PCB) liquids or waste contaminated with PCB liquids. The CO2 monitoring is not required
to be continuous but must provide a data point at least every 15 minutes. The CO2
concentration is required to be determined so that a combustion efficiency can be
calculated. As with the CO and O2 monitor, the CO2 monitor can be located anywhere in
the offgas tram. The conditions encountered in the offgas system would depend on the
location of the monitor, ranging from the harsh conditions at the SCC exit to the
significantly milder, but potentially wet, conditions at the stack. Normally when burning
PCB waste, the CO2 content can vary from essentially 0% to approximately 20%. If,
however, the waste matrix is nearly pure carbon, such as contaminated charcoal or graphite,
and the oxidant is pure oxygen rather than air, then the CO2 content in the offgas would
approach 100%.
Radionuclide monitoring at the stack is required for regulatory purposes. Current
regulations do not require real-time monitoring, but the offgas must be continuously
sampled. However, continuous real-time monitor would be desirable. One of the important
improvements that could be made in radionuclide monitoring is the development of
monitors that can detect radionuclides that are converted to gases when thermally treated
(e.g., tritium or radioiodine). Current methods to detect these nuclides rely on absorption
or adsorption with media that also collect other combustion products and are therefore
rapidly saturated.
At a minimum, nuclide monitoring should include a beta/gamma scan down to
picocurie levels. Depending on the .type of waste and local/regional regulatory
requirements, it may be necessary to monitor for alpha and difficult-to»control nuclides such
as tritium, carbon-14, radioiodine, and noble gases. Since alpha-emitting radionuclides are
usually attached to particulate matter, real-time continuous alpha monitoring would probably
be performed between HEPA filters in series and serve essentially as an upset or filter
breakthrough monitor. The downstream HEPA filter(s) would provide additional protection
should an upstream filter fail. Conditions in the stack will be substantially milder than at
the SCC exit: temperature will range from about 150 - 500 °F; system pressure will be
slightly below or above atmospheric; acid gases will be 100 ppm or less downstream of a
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scrubber; paniculate loadings will be below 0.015 gr/dscf (significantly lower than this figure
downstream of HEPA filters); the offgas may be saturated with moisture depending on the
type of air pollution control equipment used.
Hydrochloric acid (HC1): Continuous emissions monitoring at the stack is not usually
required by regulatory agencies but is recommended for process control purposes,
particularly in dry and semi- dry offgas treatment systems to control alkali reagent addition.
Conditions will be the same as for radionuclide monitoring.
For SOX and NOX continuous monitoring at the stack may be required if Prevention
of Significant Deterioration (PSD) concerns exist. Low sulfur levels in the waste will likely
preclude the need for SOX continuous emission monitoring (CEM). A NOX CEM is likely
due to the high levels of nitrogen in some waste feed streams and may also be needed due
to the thermal NOX generated by the thermal treatment device. Where waste with a high
nitrogen content is being treated, a NOX abatement technology is required and installed.
Monitors should be able to monitor levels as high as 10,000 ppm in an abatement
equipment failure situation. The conditions in the stack will be the same as listed above for
radionuclides.
Particulate monitoring in real-time is not likely required because of the use of
redundant HEPA filters. Stack particulate sampling, including that for radionuclides
attached to particulate, should be conducted at isokinetic conditions. Under normal
operation, strictly from a technical standpoint, isokinetic sampling downstream of HEPA
filters would not be required. However, should the HEPA filters fail, allowing larger
particulate to be emitted, then isokinetic sampling would be required to measure the actual
particulate emission.
Heavy (toxic) metals monitoring is not currently a standard requirement, but some
EPA regions have required it of certain facilities (such as when the waste stream is known
to have a high quantity of heavy metals or if public pressure persuades the EPA). Ideally,
heavy metals monitoring would be done on a continuous real-time (or near real-time) basis,
but continuous extractive sampling, followed by analysis in a laboratory, is currently an
accepted method. For a future mixed waste treatment facility, continuous real-time
monitoring for mercury, because of its high volatility, may be desirable both for emissions
performance and internal process control. Development of a continuous monitor for
emissions of the toxic metals regulated by the EPA is considered a high priority. Monitoring
for metal levels down to a mass emission rate of a few grams per hour will be necessary.
Conditions at the stack will be the same as for radionuclide monitoring.
Organics monitoring is currently required by the Boiler and Industrial Furnace (BIF)
Regulations for total hydrocarbons (THCs) depending on the demonstrated CO levels in the
offgas. THC monitoring is usually performed in the high temperature zone of the thermal
treatment unit, such as at the SCC exit. Real-time continuous monitoring for a variety of
organics in the offgas such as principal organic hazardous constituents (POHCs) and
products of incomplete combustion (PICs) is currently not required, but improvements and
developments in CEMs for organics would be beneficial. As such monitoring
instrumentation at the required detection limits becomes available, its use should be
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encouraged to help future mixed waste treatment processes become more acceptable to the
public.
Trial burn monitoring requires measurements of particulate and, in most cases, HC1
and heavy metals emissions at the stack. A determination of the destruction and removal
efficiency (DRE) of the POHCs will be required and measurement of the emissions levels
of PICs may also be required. There are standard EPA methods for measurement of these
species.
Temperature: The temperature .of the offgas should be measured at various points
throughout the offgas system starting at the thermal treatment unit. Conditions will vary
from about 2200 °F with high levels of primary pollutants .(acid gas, NOX, particulate, heavy
metals, radionuclides) to nearly ambient conditions at the stack with the majority of the
pollutants removed. Depending on the type of offgas system, the offgas at the stack could
be near water saturation. The temperature of the gas at each combustion chamber exit
must be measured to verify that the operating conditions stay within the operating envelope
established during the trial burn in order to ensure that the required organics destruction
is achieved. In general, the inlet temperature to air pollution control devices (APCDs) must
be monitored if the APCD is required to meet permit conditions and if the APCD hasxa
temperature limit for proper operation. For example, in offgas systems having a baghouse
for particulate removal, the baghouse inlet temperature must be monitored to ensure that
the bags are not damaged by high temperatures. In addition to monitoring temperatures
for regulatory purposes, temperatures at various locations in the offgas system should also
be monitored to ensure proper operation, which in turn can have a direct effect on meeting
permit conditions. For example, the quencher exit temperature is a monitored variable in
a wet offgas system to verify that the offgas is being adequately cooled to maintain the
integrity of downstream process equipment including HEPA filters. Likewise, where offgas
reheaters are required to raise the offgas above the dew point prior to HEPA filtration,
temperature differential across the reheater unit is a necessary control variable to ensure
the HEPA filters are not damaged by moisture.
Pressure and Differential Pressure: Absolute pressure and differential pressures
must^be monitored and controlled at various points throughout the offgas system. Process
conditions will be the same as described for temperature measurements. Control of the
thermal treatment unit's internal pressure, slightly below atmospheric, will be required for
operational safety purposes. Differential pressures across specific APCDs must be
controlled to stay within the operating envelope established during the trial burn and to
maintain high particulate removal efficiencies. The pressure of the liquid flow to the
scrubber must also be monitored. For other APCDs such as packed tower scrubbers, the
differential pressure must be monitored to avoid upset conditions such as flooding.
Baghouses typically require monitoring of differential pressure to monitor for bag filter
failure. For HEPA filters, a measurable minimum pressure drop indicates the integrity of
the filter; a maximum aUowable particulate loading is indicated by high pressure drop and
the subsequent need to change filters.
Gas Flowrates: Flowrate measurements for both input gas streams into the thermal
treatment unit and for the offgas at selected points in the offgas train including the stack
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are important. Input gas streams are essentially air but Can contain contaminants, such as
in chemical venting operations. The gas may be wet, contain relatively high concentrations
of organics, and have a relatively high dust loading. Input gas flow pressures will be slightly
negative with respect to atmospheric, and temperatures will be near ambient. The SCC exit
offgas flowrate must either be monitored directly or readily determined through calculation
to determine the average gas residence time in the SCC. Final stack offgas flowrate
monitoring is useful for material balance purposes and required in order to calculate mass
emission rates of monitored pollutant species as well as for isokinetic particulate sampling.
Conditions at the stack are the same as those described above for radionuclide monitoring.
Liquid Flowrates: For wet or semi-wet offgas systems, the flowrate of circulating
scrubber liquid at various points in the system is an important process control parameter.
For example, the flowrate of scrubber liquid to many APCDs such as particulate and acid
gas scrubbers, affects the removal efficiency of these pollutants and must be monitored to
verify that flowrates are reflective of operating conditions used during the trial burn. The
proper.flowrate of liquid to an offgas quencher is the variable that controls the quencher
exit temperature. Emergency water addition to a wet offgas system may also be controlled
by scrubber liquid flowrate. For regulatory purposes, monitoring of the scrubber liquid
blowdown flowrate is almost always required and is useful for overall process material
balance closure. Scrubber liquid conditions are generally as follows: slightly caustic (pH
of 8 - 9 optimally, but periodically higher or lower), slightly elevated temperature (80 -
180°F). The aqueous liquids normally contain dissolved solids (salts such as NaCl, NaF, and
Na2SO4) and suspended solids (primarily flyash consisting of soot, metal oxides, and
inorganics in elemental form).
•.',... • • - . .! . •
pH of Scrubbier Liquid: The pH of scrubber liquid is an important system control
variable and also happens to be one of the most difficult process parameters to control
satisfactorily. The pH must be controlled within a prescribed range, typically 8 to 9, to
maintain acid gas removal efficiency, avoid precipitation of gelatinous metal hydroxides, and
meet scrubber blowdown pH discharge requirements. The scrubber liquid pH is the
measured variable that controls caustic addition. Conditions are the same as those
described for flowrates.
Power and voltage monitoring is required for certain APCDs that rely on electrical
input to create electrostatic forces for the collection of particulate. These monitors are used
to ensure that the particulate removal equipment is operated under the same conditions as
those used during the trial burn so that the particulate removal efficiency will be nearly the
same as that obtained during the trial burn. The primary APCDs that will be required to
monitor these variables are: electrostatic precipitators (ESPs), wet electrostatic precipitators
(WESPs), and ionizing wet scrubbers (IWS). Obviously, these monitors will not be in
contact with the offgas and will not be subjected to the extreme conditions associated with
the offgas.
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General Monitoring Needs for Control Purposes
Density and/or Conductivity of Scrubber Liquid: Continuous monitoring and control
of density or electrical conductivity is a means of controlling dissolved solids concentration
of the recirculating scrubber liquid. Slowdown of scrubber liquid is normally based on
controlling either or both of these two parameters at a specified setpoint. The liquid blown
down is replaced with fresh makeup water to maintain a constant inventory of liquid in the
system. Conditions are the same as those described above for liquid flowrates.
Liquid Level: The level of scrubber liquid in APCD sumps and surge tanks must be
controlled to avoid dry pump suction and the loss of flow of liquid to APCDs. Level control
is also required to avoid overflow of process vessels.
Fissile Material Monitoring: For avoidance of criticality concerns, especially in wet
offgas systems processing waste with fissile materials, a means of monitoring key process
areas that could expect holdup of material should be provided. Such areas include APCD
sumps and scrubber liquid recirculation tanks.
Vibration Monitoring of Rotating Equipment: Key rotating machinery in an offgas
system includes induced draft blowers and liquid pumps. To maintain safe operating
conditions, monitoring for vibration should be considered at a minimum for induced draft
blower performance to anticipate maintenance requirements and avoid failure of equipment
during operations.
Monitoring of Chemical Species in Selected Gas Streams
For various gas streams within the MWTP facility, additional monitoring may be
indicated for control purposes. Following are species that would likely require monitoring
for process control:
• Organics - Measurement of the organics content of input gas streams to the
thermal treatment unit, though not critical, can provide information
concerning heat input into the thermal treatment unit. Conditions will be
similar to those described above for flowrate measurement of input gas
streams. -
• Acid Gas - Acid gas (primarily HC1 and SOX) content of stack gases may need
to be measured if a dry or semi-dry offgas system is used. This measurement
would be used for feed forward control of the addition of alkali reagent for
acid gas scrubbing in such a system.
• Chlorine Gas - Chlorine (C12) gas monitoring in the exhaust from chlorine gas
scrubbing is needed for control purposes. Gas temperature will be slightly
above ambient (120 - 160°F). . The gas will be fairly clean but will be
saturated with moisture.
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Mercury - Mercury monitoring in the offgajs from a mercury cleanup scrubber
and from the activated carbon bed absorber downstream of the mercury
vacuum still is needed for control purposes and may be beneficial hi
demonstrating regulatory compliance. Such monitors would indicate proper
operation of the scrubber and approach to breakthrough of the carbon bed.
The Minimum Characterization/Maximum Treatment Concept
Overview
The approach to mixed waste treatment embodied in the MWTP is more efficient
than an exhaustive, waste stream-by-waste stream characterization and treatment effort.
However, it still begins with an extensive characterization of the waste materials, followed
by a rigorous screening, segregation and sorting step. Characterized, segregated waste
streams then undergo treatment in a variety of treatment processes specifically designed for
individual waste stream treatment applications. This approach satisfies treatment
requirements, but may result in a significant cost in conducting the characterization needed,
as well as in the multiple pre-treatment steps required. Some reduction in characterization
needs may be gained through development and use of some of the analytical and process
monitoring techniques discussed in previous sections of this chapter.
An alternative approach would be to employ a mixed waste treatment technology that
is sufficiently robust to treat a very wide range of differing waste classifications and physical
types. This approach combines three basic strategies in designing a waste treatment facility
to attain the goal of minimizing the costs for characterization: robust primary .treatment,
complete gaseous products cleanup, and in-process monitoring. These three elements, when
used in concert, should allow the design and operation of a mixed waste treatment facility
that can be operated with a minimum need for precharacterization of current inventories
of mixed waste, as well as future mixed waste volumes.
The basis of this strategy is that the primary treatment step must be sufficiently
robust that a wide array of waste types can be effectively treated by the process, minimizing
the need for waste segregation and multiple treatment technologies. Hazardous organic
components of the waste must be fully destroyed in the primary treatment step. Treatment
residuals must be sufficiently stabilized such that inorganic hazardous components will not
leach from the solid matrix. Treatment residuals must be much more homogeneous than
the untreated waste so that characterization of the residual solid product is simplified.
Secondly, a complete gaseous-phase cleanup system must be employed to treat
gaseous discharge from the primary treatment process such that facility stack discharge will
be fully compliant with regulatory discharge requirements. The gas cleanup system must
take into account a wide range of contaminants that must be removed, and it must be
flexible enough to operate over a wide range of operating conditions and pollutant
concentrations.
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Thirdly, in-process monitoring and characterization technologies can be employed to
ensure proper operation of the treatment process, thus ensuring that treatment system
performance is as required.
Plasma arc vitrification is an example of one developing technology that has the
potential for application over a wide spectrum of wastes. Plasma arc vitrification processes
have been demonstrated in the treatment of waste materials such as bulk combustible waste
items (e.g., rubber gloves, clothing, paper, wood), high-metal-content wastes (steel,
aluminum, copper), organic and inorganic sludges, soils and other remediation-derived
wastes, construction and/or facility decontamination and decommissioning (D&D) wastes,
and mixtures of these contained in a single matrix. Plasma arc vitrification technology may
be able to replace the need for multiple waste-specific technologies in a waste treatment
facility, potentially reducing the degree of characterization and pretreatment needed, and
thereby significantly reducing facility operating costs. Plasma arc vitrification processes have
demonstrated destruction of a range of organic contaminants. The technique produces a
very stable, homogeneous, glassy treatment residual which inhibits leaching of elements in
the matrix. This technology is also very amenable to the use of current state-of-the-art offgas
control technologies for offgas cleanup. For these reasons, a plasma arc vitrification process
may represent a good option as a primary treatment technology that would minimize pre-
characterization requirements for many DOE wastes.
This section provides a preliminary evaluation of how a plasma arc vitrification
process could.be employed in a mixed waste treatment facility as a primary treatment
process in the context of the alternative treatment process described above, and what in-
process monitoring techniques may be useful or necessary in order to complete the strategy.1
Plasma Arc Vitrification Process Description
A plasma arc vitrification process, converts electrical energy into intense heat within
a primary waste treatment chamber. The plasma arc vitrification process uses a "plasma
arc torch" to generate the plasma in the chamber. The plasma is created by initiating and
maintaining a gaseous electrical current conductor, the plasma arc column, between the
plasma arc torch and a molten pool of waste materials. Waste materials are fed into the
primary chamber, where they are melted by the plasma torch, and are incorporated into the
molten pool. The molten material is then removed from the chamber and cooled to form
a very stable, glassy final product. Glass forming materials can be added to the molten slag,
if needed, to optimize the properties of the slag. Some of the potential advantages of
plasma treatment include:
1 This discussion should not be viewed as an endorsement of plasma arc vitrification for the
treatment of MLLW. There are many waste streams for which it would not be suitable. But this
technology can serve as a useful model when considering the characterization needs for a very
robust waste treatment process and its effluents, in the same way that the (highly conceptual)
MWTP serves as a model for denning the general needs of a treatment facility.
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• efficient destruction of organics,
• a high-integrity, vitrified final waste form with encapsulation of heavy metals
and radionuclides,
• maximum volume reduction,
• a one-step treatment process (no pre- or post-treatment required), and
• capability to process many waste types.
In the high temperature zone of the primary process chamber, essentially all organics
in the waste are destroyed. A secondary combustion chamber is often used to ensure the
complete destruction of organics, and thus to achieve the required destruction and removal
efficiency (DRE) for hazardous organics in the waste. The remaining inert materials form
a molten, vitreous slag which, when removed from the furnace, cools and solidifies into a
stable final waste form. Most of the hazardous heavy metals in the waste remain in the
molten slag and are sufficiently bound that the vitrified final product will consistently pass
EPA Toxicity Characteristic Leaching Procedure (TCLP) tests for heavy metal leachability.
Radionuclides will also be bound in the non-leaching slag.
! • '
Plasma arc vitrification systems have been developed that accept whole, unopened
drums of waste material into the primary chamber for processing. This eliminates some of
the concern raised in treatment scenarios that require mixing of potentially incompatible
materials in pre-treatment operations. It also serves to reduce the potential for exposure
of facility personnel.
A state-of-the-art offgas cleanup system is installed on the outlet of the plasma arc
vitrification process to provide conditioning of the process offgas prior to release. Offgas
conditioning requirements are dictated by EPA regulations governing release of hazardous
components that may be part of the process offgas. Offgas conditioning will be required to
remove participate material entrained in the offgas, treat and remove acid gas components
(e.g. HC1), remove volatile heavy metals from the offgas stream (e.g. lead, mercury), and
possibly to reduce high concentrations of oxides of nitrogen generated in the process. A
schematic representation of a complete plasma arc vitrification process, including offgas
equipment, is provided in Figure 3-1.
Characterization Needs in a Plasma Arc Vitrification Facility
While the plasma arc vitrification concept provides many advantages in minimizing
precharacterization requirements, there are still a number of limitations that must be
considered in developing precharacterization and in-process monitoring requirements. In
the end, there will remain some degree of characterization. With thoughtful use of existing
techniques and technologies, combined with development of promising characterization
concepts, the cost for characterization within the waste treatment facility can be rninimized.
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I
00
oo
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Hazardous Heavy Metals
The EPA currently, regulates the quantity of hazardous heavy metal constituents that
can be released from a waste treatment process. The regulation is a risk-based approach
that relies on a complex evaluation strategy that takes into account factors such as facility
location relative to population, local geographical and 'climatological characteristics, and
concentrations of specific heavy metals in the stack release. Compliance with the regulation
requires a balance of control of the materials introduced into the treatment process and the
use of offgas control technologies that remove volatile heavy metals from the offgas prior
to release at the stack.
In any high-temperature process, certain heavy metal contaminants are volatilized
into the offgas stream in varying percentages. This is particularly of concern for lead and
mercury, two components present in a large quantity of DOE mixed waste. Thus, capture
and control of these volatile heavy metals in the offgas cleanup system will be a high
priority. ; i
In this concept, the primary method that is used to address the volatile heavy metal
at Savannah River). The metal-laden particulate may then be collected and recycled to the
primary chamber, where they can eventually be captured in the vitrified residual. However,
there will most likely be a need to couple this primary approach with some degree of
precharacterization and in-process monitoring.
It would be desirable to characterize the offgases after offgas cleanup to ensure heavy
; metal concentrations are below permit limitations. The current state-of-the-art to
accomplish this is a complex sampling and analysis procedure adopted by the EPA, which
requires significant operator involvement in collecting the sample and conducting the
analysis using wet chemistry methods. This is a very labor intensive and costly process that
only provides an "instant-in-time" assessment of the process performance., Some hazardous
waste treatment facilities have been forced to adopt this concept, taking these samples on
a daily basis.
An alternative would be to provide a real-time analysis of the offgas stream in the
stack, which would give the facility operator a continuous assessment of the concentration
of heavy metals in the offgas. However, current technology is not sufficiently developed for
full-scale application in this area. Several technologies (as discussed in previous sections)
are being developed, and if successful, would provide an optimum strategy when combined
with the use of a robust offgas cleanup system.
The final, and least favorable way to address this issue is to provide for an analysis
of the feed material to the process to ascertain where high concentrations of heavy metals
may be encountered. This is least favorable because it would require a major allocation of
resources for sampling and analysis of heterogeneous wastes. Perhaps the one area of
development that could prove beneficial in this regard would be the development of a
technology that could ascertain the presence of relatively large quantities of mercury and/or
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lead in a drum. Thus, with minimal prescreening (e.g. a head space analysis for mercury,
NDE examination for large lead objects), potential problem waste drums could be routed
to areas for removal of the offending objects prior to feed to the plasma arc process, or to
separate, specialized treatment lines (e.g. mercury recovery).
Hazardous Organics and Products of Incomplete Combustion
One of the primary purposes of the thermal treatment process is to provide an
environment that will effect the complete destruction of hazardous organic materials in the
waste by converting the organic molecules to principally carbon dioxide and water vapor.
Some organic materials are relatively easy to destroy, while other compounds are much
more difficult. In addition, especially for the more difficult to destroy constituents, it is
possible that some organic materials may be converted through incomplete chemical
reaction to form different organic compounds, some of which may be more hazardous than
the original compound. These compounds are known as Products of Incomplete
Combustion (PICs). Both the release of unaltered Principal Hazardous Organic
Constituents (POHCs) and PICs are regulated by the EPA.
It would be helpful to know, prior to processing, which individual hazardous organics
are present in a given waste container. Often the EPA requires a detailed listing of the
organics in a particular waste stream. This would present a very difficult challenge to DOE,
given that much of its waste has been in storage for long periods of time, and records that
might identify contaminants present are incomplete. Sampling and analysis of these
heterogeneous matrices will also be difficult and expensive, will lead to exposure of workers,
and may not be accurate or representative in many cases.
In the minimum characterization scenario, the principal means of assuring proper
destruction of organics and minimal formation of PICs is vested in the primary and
secondary thermal treatment devices, or in this example, the plasma chamber and a close-
coupled secondary combustion chamber. The approach relies on the fact that the plasma
process has a very high efficacy of destruction of organic material, due to the intense heat
and controlled reaction environment in the primary plasma chamber. The secondary
destruction chamber is designed in accordance with EPA criteria, including sufficient
temperature, adequate residence time in the chamber, and sufficient heat in the presence
of copious quantities of oxygen (air) to ensure that any PIC or unconverted organic that did
pass from the primary chamber would be destroyed in the secondary chamber. This is
proven in a "trial burn" test conducted on the treatment process, where known amounts of
materials are introduced to the process, and extensive sampling and analysis is conducted
on the offgas to ensure proper destruction is being attained. The trial burn is conducted
using the most difficult-to-destroy organic materials as feed compounds, permitting the
inference that other compounds would be more readily destroyed. This is consistent with
current EPA approaches to thermal treatment of organic wastes.
Having demonstrated that the primary process can treat essentially any organic in the
waste, the second component is to provide some form of monitoring that will ensure
destruction will be attained on a routine, continuing basis. -Hie main way this is
accomplished is by monitoring the operating parameters of the thermal treatment process
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and maintaining them within the bounds of the operating parameters of the trial burn. This
is commonly done on currently permitted thermal treatment devices and is augmented by
some minimal form of monitoring of various constituents in the offgas. Carbon monoxide
is monitored on a real-time basis as a measure of completion of the combustion reactions,
and must be maintained below 100 ppm on average. Oxygen content is measured to assure
a certain excess is available in the process to complete the conversion. Sometimes total
hydrocarbon (THC) concentrations are measured to assure a very low concentration of both
the original compound and PICs are contained in the stack gas.
Some thermal treatment facilities, mainly in Europe, have installed offgas equipment
beyond the secondary chamber for the purpose of removing trace quantities of PICs and
POHCs from the offgas stream, further ensuring a minimal release. One example is use of
an activated carbon bed. Such a strategy should be considered under this scenario,
especially since the residual material could be reintroduced to the feed to the plasma
process to ultimately provide the complete destruction required.
These strategies have been allowed for operation of a permitted waste treatment
facility in the past, and should continue to be allowed in the future. Thus, it should not be
necessary to fully characterize organic concentration and type prior to treatment. No
advanced characterization technology or process monitor should have to be developed in this
case; the current state-of-the-art is sufficiently advanced to implement the strategy as
outlined. It may be beneficial to develop a continuous, real-time monitor that can identify
specific PIC or POHC concentrations as a means of further assurance; however this is a
lower priority development.
Feed containing containerized liquids or compressed gases
Several of the DOE waste streams are likely to include liquids inside of closed
containers and/or compressed gas cylinders. These sealed vessels, when introduced into the
high temperature plasma processing chamber, will heat up along with their contents
increase in pressure, and will cause small explosions within the chamber when the container
is ultimately breached. This is of particular concern when the containerized fluid is
flammable material. Therefore, containerized liquids and compressed gas cylinders are
restricted from feed into a plasma process.
Some form of screening is needed to determine if liquid containers or gas cylinders
are present within a given drum. This would be best accomplished using a non-destructive
means of assay, where drums, containing these materials could be routed aside for opening
and removal of the restricted items in a controlled environment. The state-of-the-art is
advancing in this area, with some real-time radiography techniques being able to detect this
type of waste component. Further development to better automate such a process which
now relies on operator interpretation, may prove beneficial.
!
Feed of large quantities of lead
The DOE has used and disposed of copious quantities of lead in its operations over
the years. Most often, the lead takes the form of drum liners or bricks of lead that have
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become contaminated. Aside from the potential for lead emissions discussed above, it may
be beneficial for the DOE to provide for the decontamination and recycle of these bulk
quantities of lead for future use. In the plasma process, the majority of the lead will likely
be unrecoverable as a resource if introduced into the primary chamber with the other waste
materials, and will instead be incorporated into the residual for disposal. A prescreening
step, using a technique such as real-time radiography, could allow for segregation of drums
containing large lead items, so that those drums could be handled separately and the lead
removed.
Radionuclides
Stack emissions of radionuclides are regulated by both the EPA through the Clean
Air Act and the DOE through the DOE Orders. Radionuclide releases are evaluated using
a procedure similar to that discussed for heavy metal emissions. A complex computer model
is developed to simulate the anticipated transport of radionuclides after release. Releases
are limited to a value that would result in less than a certain level of exposure to a
theoretical maximally exposed individual living nearest the release site.
Some prescreening of radionuclide concentration is possible by a variety of gross and
isotope-specific measurement techniques. However, since releases are often controlled on
an isotope-by-isotope basis, it is often difficult to provide sufficiently accurate measurements
for all radionuclides of concern. A gross radiation screening method will undoubtedly be
used in the type of operation being considered here.
Radionuclides will not be destroyed at all in any treatment process. Most
radionuclides will be retained within the primary chamber of the plasma process, and
contained within the molten residual. However, some radionuclides will evolve from the
process as gases, vapors or as small particulate entrained in the offgas stream. Thus, the
primary strategy to be relied upon will be a carefully designed process for removal of
radionuclides from the offgas stream prior to release.
Radionuclides evolved as vapors will be condensed into solid particulate material in
the initial quenching section of the offgas treatment train. This condensed particulate, as
well as particulate carried over as solid material, will be readily removed from the offgas
by current state-of-the-art technologies for particulate removal. Removal efficiencies as high
as 99.97% are possible using a baghouse/HEPA filter combination.
Radioactive isotopes evolved as gases in the process chamber will be more difficult
to control. Fortunately, they represent .a relatively small portion of the overall DOE
radionuclide inventory. Two notable exceptions are carbon-14 and tritium, which are
responsible for significant quantities of mixed waste. However, neither of these
radionuclides is of great concern from an exposure standpoint, and very high release limits
are allowed for these items. Some up-front screening will have to be done, as a minimum
to identify drums that may contain significant quantities of gaseous radionuclides so that
potential release problems can be identified and controlled processing initiated where
necessary (e.g., blending with other waste drums to lower the release potential).
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Current techniques for radioactive material measurements in the stack emission of
thermal treatment processes are limited to sampling and laboratory analysis. The sampling
involves a collection of particulate in a stream of the stack gas by use of a fine filter. This
requires a sample drawn over a long period of time in order to provide a sufficient
concentration for analytical detection. It can provide an indication of breakdown of
efficiency in the offgas cleanup system, but several days'may pass before routine analysis is
conducted and the problem is discovered. It also provides no method to detect gaseous
radionuclides, which would pass through the filter undetected.
An advance that would greatly enhance the operation of a plasma system, or any
other thermal treatment device, would be the development of real-time monitoring
capability for radionuclides in an offgas effluent stream. This would serve a number of
useful functions. First and foremost, regulatory authorities would have the ability to ensure
that stack releases were indeed within the bounds permitted. Facility operators would have
a real-time indication of a potential problem in the offgas treatment equipment, and would
be able to make immediate adjustments in the process to correct the problem. In addition
if gaseous radionuclides were discovered, drums from the rest of that particular batch could
be more carefully screened to ensure annual release rates would not be exceeded.
Summary
The use of a plasma arc vitrification system, or other robust treatment technology
when combined with a comprehensive offgas cleanup system and a degree of in-process
monitoring, should result in an approach that will allow DOE to conduct only minimum and
in most cases non-intrusive, characterization of waste inventories. This approach would be
fostered by the development of a number of novel concepts for in-process monitoring as
well as some screening level pre-characterization techniques. Overall, this approach has the
potential to significantly reduce the cost for waste characterization currently facing the DOE
as well as improve the safety of operations by minimizing exposure of workers to hazardous
materials during sampling operations.
The approach is not without costs, however. It replaces the need for extensive waste
characterization with a requirement for very rigorous offgas treatment and monitoring A
facility accepting a wide range of wastes would need a very elaborate system for offgas
handling. Establishing the adequacy (and cost-effectiveness) of the system for monitoring
and controlling a variety of potential problem species would require a great deal of work
DOE Idaho's current trial burn program, which is setting the standard for such work, has
achieved promising results in offgas monitoring and cleanup.
Conclusions and Recommendations
The general consensus of the workshop group felt that the following research needs
were of the highest priority:
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1. Public acceptance of any thermal treatment technology for mixed waste demands the
development'of continuous emission monitors for metals and radionuclides in
gaseous effluents. These monitors must be capable of operating in a hostile
environment and should be simple to operate, reliable, and not cost-prohibitive. This
is probably the most promising area for technology development relating to process
monitoring or control.
2. Cost-effective sample extraction techniques for containerized heterogeneous waste
need to be developed. In addition cost-effective, simple measurement calibration
techniques are required.
3. Mercury is an extremely troublesome species with regard to thermal treatment.
Detection technology for mercury in solid matrices is a real need.
4. The heterogeneous nature of much of the waste and the potential presence of
multiple troublesome species requires the development of screening methods for
heterogeneous matrices and specific detectors for specific constituents.
5. Improvement in radiation detection is also required, particularly for real-time gas-
phase monitoring of process effluents. Two particularly promising areas are neutron
detector development and room temperature solid state detectors with resolution
superior to Nal-based detectors.
In the course of the discussions that produced the detailed information on process
monitoring technologies, several overarching issues concerning the strategy for mixed waste
treatment were identified:
1. A thorough evaluation by a multi-disciplinary team is required on the relative
benefits of up-front characterization versus versatile process design versus in-process
monitoring/control. The optimum solution to mixed waste treatment will most likely
be some combination of all three strategies.
2. There may be an inappropriate tendency to, "high tech" the approach to process
monitoring/control of the treatment of mixed waste. For instance, real-time analysis
technologies may not really be required when an on-site dedicated laboratory can
provide quick turn-around. In addition, standard process control measurements can
often be used to indirectly assess more difficult-to-measure properties.
3. It is almost impossible when bulking/staging dissimilar waste materials to ensure
compatibility (i.e. the prevention of chemical reactions which may at best adversely
affect treatment or at worst create potentially hazardous situations). Batching by
waste stream or drum by drum processing may be more cost-effective approaches.
4. There is a need for the establishment of national performance standards for many
of the cited measurement techniques.
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Chapter 4
Final Waste Form Characterization
Peter Lindahl, Srini Venkatesh, M. John Plodinec, S.J. Amir,
Mark Pickrell and Rich Van Konynenburg
Introduction
The principal force determining characterization requirements for final waste forms
is regulation The waste forms created by the MWTP facility will be regulated under the
EPA s Land Disposal Restrictions and must be disposed in compliance with applicable state
and federal requirements. In general, treatment requirements include elimination of organic
hazardous constituents and stabilization of inorganic hazardous constituents In addition
the long-term stability and safety of the waste forms must be assessed. Final waste forms
must meet both EPA leach testing and DOE disposal acceptance criteria. In addition to the
EPA and DOE criteria, final waste form characterization may be required by the Nuclear
Regulatory Commission (NRC), Department of Transportation (DOT), disposal site waste
acceptance criteria (WAC), accepting states, and for process control and health and slfery
the EpA re
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parameters for each waste analysis plan are determined on an individual basis as part of the
permit application review process.
NRC regulations do not describe specific testing requirements for wastes to
determine if a waste is radioactive. However, both NRC and Department of Transportation
regulations contain requirements applicable to characterizing the radioactive content of the
wSeSresMpmen? For example, NRCs regulations in 10 CFR 20.311 (20.2006 of the
Revised Part 20) require that the manifest include, as completely as practicable, the
radionuclide identity and quantity, and the total radioactivity. NRC regulations also require
that generators determine the disposal class of the radioactive waste and outline waste form
requirements that must be met before the waste is suitable for land disposal. These
regulations are referenced in 10 CFR 20.311 (20.2006 of the Revised Part 20) and are
outlined in detail at 10 CFR Part 61.55 and 61.56. Mixed waste generators such as the
MWTP must satisfy both RCRA and NRC waste testing and waste form requirements.
All of the RCRA strategies allowing hazardous waste to be land-disposed will be
employed at the MWTP facility. Where LDR requirements must be met, it is planned that
(a) specific treatment technologies (BDATs) will be used for some of the wastes, (b) final
waste forms will not exceed the maximum concentration level designated for some regulated
constituents, and (c) other waste forms will be created so as not to exceed the concentration
limit established by a leach test procedure. In some cases, RCRA delisting of final waste
forms will allow their on-site disposal. Key to satisfying disposal requirements is the
implementation of appropriate treatment for individual hazardous wastes. The objective of
treatment standards is either (a) the removal/destruction of the hazardous characteristic or
constituent or (b) the stabilization/immobilization of toxic materials ma durable matrix
The assumption is that waste residue thus treated can be placed safely in a land disposal
facility. Therefore, final waste forms must be produced that meet the requirements for
* control of inorganic and organic constituents and radionuclides. Process control
requirements for each final waste form should be assessed and defined in a formal process
control program.
Because of concern about the inherent safety and health hazards of sampling and
analyzing mixed waste materials, and in particular, the potential risk to workers from
exposure'to radiation and hazardous chemicals posed by duplicative testing of mixed wastes,
redundant testing should be avoided. In addition, waste analysis plans should include
provisions to keep radiation exposures as low as reasonably achievable (ALARA) and
incorporate relevant Atomic Energy Agency requirements and regulations. Further, testing
should be conducted in laboratories licensed by NRC or the appropriate NRC Agreement
State authority. In this case, it is assumed that the testing will be performed in a dedicated
laboratory at the MWTP facility.
The final waste forms and recyclable materials expected to be products of the MWTP
facility are listed below, along with the sample points at which they are characterized:
• cement grouts (cement and organic-cement conglomerate); sample point
1002.10.
• crystalline ceramic; sp 803.10
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• glass; sp 901.10
• polymers (sulfur polymer and polyethylene macroencapsulation); sp 902.2
lead; sp 902.10
• mercury; sp 905.10
• ferrous alloys; sp 804.10.
The workgroup identified the general suite of final waste form properties or
parameters that should be evaluated, and recommended their applicability to each of the
final waste form types. Priority was given to glass and ceramic waste forms, and recyclable
metals. The applicable tests were assessed as to when these tests were needed and the
frequency at which they should be applied. Three levels of frequency were specified: one-
time, at process start-up; once per batch of waste forms; and every waste form. Assigning
testing frequency was difficult in some cases, because of uncertainty as to what would
constitute a batch, i.e., whether it would have uniform feed or not. The process flow
diagrams that correspond to the discussion of this chapter are 901, 902, 903, 904 and 905
(see Appendix B).
The chief sources drawn on for waste form testing were:
RCRA requirements - 40 CFR 260 et seq.
NRC requirements - 10 CFR 61 et seq. It should be noted that these
requirements are not currently binding on DOE wastes.
DOT regulations
general process control practices for creation of waste forms
customary health and safety guidelines for handling LLW, as set forth in DOE
Orders and Guidelines
The Waste Acceptance Criteria for the Waste Isolation Pilot Plant (WIPP)
and the Nevada Test Site (NTS) waste repository.
Parameters and Tests
The workgroup identified 21 parameters/properties to be assessed for characterizing
final waste forms. These are listed in Table 4-1, along with the regulation or purpose
driving the measurement. Several additional properties require testing in materials to be
recycled. Each final waste form does not require determination of the full suite of
parameters/properties. Tables 4-2 through 4-10 list the properties to be measured the
recommended measurement frequency, some data quality objectives, and recommended test
methods for each of the waste forms or materials for recycle. As many of the testing
requirements are established by regulation, the tables often simply cite the pertinent
regulation for test method or data quality objective. The properties and test methods are
described below. Summaries of some of the most important analytical instruments used in
final waste form characterization are given in Appendix E.
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Table 4-1. Parameters Tested in Final Waste Forms.
Property/Parameter
Leach. Resistance
Free Liquids
Radionuclides
Transferable Contamination
Specific Alpha Activity
Dose Rate
Weight/Size
Labeling Requirements
Hardness Test
Drum Weight
Major Matrix Elements
Toxicity Characteristic
Jgnitability
Corrosivity
Reactivity
Waste Acceptance Criteria
Land Disposal Restriction Tests
Void Volume
Gas Generation
Compressive Strength
Set Time
Purpose or Regulatory Requirement
NRC regulations
RCRA
NRC, DOT,
Risk/Performance Assessment
DOT, DOE Rad Con
TRU-LLW Distinction, gas gen.
H&S, DOT
process control
DOT, DOE Orders
process control
WAC, DOT
process control, WAC
RCRA (define hazardous waste)
RCRA (define hazardous waste)
RCRA (define hazardous waste)
RCRA (define hazardous waste)
site specific requirements
RCRA
minimize post-burial settling (WAC)
risk to container integrity
process control, leachability
process control
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Table 4-2. Characterization of Glass Waste Forms
Property
Leach
Resistance
Free Liquids
Radionuclides
Transferable
Contamination
Specific a
Activity
Dose Rate
Weight/Size
Other Labeling
Requirement
Hardness Test
Weight of Drum
Major Matrix
Elements
Toxicity
Ignitability
1 Corrosivity
r • —
Reactivity
LDR
. .
Void Volume
-
Gas Generation |
Compressive
Strength
Sampling •
Frequency
Every batch
Every
Container
Every
Container
Every
Contahier
Every batch
Every
Container
Every batch
Every
Container
Every batch
Every
Container
Every Batch
Every Batch
NR
MR
NR
Every Batch
Every
Container
NR
NR
Requirements
<0.5% by Vol. (RCRA)
For discussion assume
10 CFR 61
220 dpm/dm2 a
2200 dpm/dm2 ft, y
<100 nCi/g
200 mrem/hr @ surface
Site specific
DOT
<12001b(on-site)
800 Ib (DOT)
elem present @ > 1 wt %
limits in RCRA
40 CFR 261
+
banned by waste J
< 10% I
— J-
Methods
PCT, ANS 16.1
Inspection
EPA 9095
SGS for drum
HPGe for pellet
neutron method for
a
a Chamber
P. y counter
neutron method for
a
Count rate meters
Balance optical
comparator
"truck" scale
XRF; ICPMS;
ICP; NAA
TCLP-Method 1311
— . . — L
.
TCLP - SW-846
\-
calculation 1
Detection
Limits
4— —
95% coinf. that
better than
blank
no visible
moisture
10 CFR 61 II
3a/BG< limit
3ff/BG
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Table 4-3. Characterization of Ceramic Waste Forms.
Transferable
Contamination
Other Labeling
Requirement
Major Matrix
Elements
Requirements
Methods
Detection
Limits
needed
<0.5% by Vol. (RCRA)
Inspection
EPA 9095
no visible
moisture
For discussion assume
10 CFR 61
SGS for drum
HPGe for pellet
neutron method for
10 CFR 61
a
220 dpm/dm2 a
2200 dpm/dm2 y3,-y
a, Chamber
p.y counter
3a/BG< limit
<100 nCi/g
neutron method for
a
3<7/BG1 wt %
XRF; ICPMS;
ICP; NAA
10 rel % at 1
abs wt % if
possible
limits in RCRA
40 CFR 261
TCLP-Method 1311
SW-846
banned by waste
TCLP SW-846
< 10%
calculation
40 CFR 265
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Table 4-4. Characterization of Cement (organic) Waste Forms
Property
Leach
Resistance
Free Liquids
Radionuclides
Transferable
Contamination
Specific a
Activity
Dose Rate
Weight/Size
Other Labeling
Requirement
Hardness Test
Weight of Drum
Major Matrix
Elements
Toxicity
Ignitability
Corrosivity
Reactivity
LDR
Void Volume
Gas Generation
Compressive
Strength
Set Time
Sampling
Frequency
Every _Batch
Every Drum
Every Batch
Every Drum
Every Batch
Every Drum
NR
Every Drum
NR
Every Drum
Every Batch
Every Batch
NR
NR
NR
Every Batch
Every Drum
Every Batch
Every Batch
Every Batch
Requirements
<0.5% by Vol.
For discussion assume
10CFR61
220 dpm/dm2 a
2200 dpm/dm2 /3, 7
s 100 nCi/g
200 mrem/hr @ surface
Site specific
DOT
<1200 Ib (on-site)
800 Ib (DOT)
elem present @ > 1 wt %
limits in RCRA
40CFR261
banned by waste
< 10%
Methods
ANSI 16.1
Inspection
EPA 9095
Dissolve rep sample
andHPGe
a chamber
8, 7 counter
neutron method
count rate meter
XRF; ICPMS;
ICP; NAA
org - IR, Raman
TCLP-Method 1311
TCLP SW-846
calculation
calculation
ASTM C-39,
D-1633
ASTM C-403
Detection
Limits
no visible
moisture
10 CFR 61
3cr/BG< limit
3a/BG< limit
3
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Table 4-5. Characterization of Cement (inorganic) Waste Forms
Property
Leach
Resistance
Free Liquids
Radionuclides
Transferable
Contamination
Specific a
Activity
Dose Rate
Weight/Size
Other Labeling
Requirement
Hardness Test
Weight of Drum
Major Matrix
Elements
Toxicity
Ignitability
Corrosivity
Reactivity
LDR
Void Volume
Gas Generation
Compressive
strength
Set Time
Sampling
Frequency
Every Batch
Every Drum
Every Batch
Every Drum
Every Batch
Every Drum
NR
Every Drum
NR
Every Drum
Every Batch
Every Batch
NR
Every Batch
If needed
every batch
Every Batch
Every Drum
Every Batch
Every Batch
Every Batch
Requirements
<0.5% by Vol.
For discussion assume
10 CFR 61
220 dpm/dm2 a
2200 dpm/dm2 /9, 7
£ 100 nCi/g
200 mrem/hr @ surface
Site specific
DOT
<1200 Ib (on-site)
800 Ib (DOT)
elem present @ > 1 wt %
limits in RCRA
40 CFR 261
banned by waste
Methods
ANSI 16.1
EPA 9095
Disolve rep. sample
and HPGe
a Chamber
y9. 7 counter
neutron method
count rate meter
"truck" scale
XRF; ICPMS;
ICP; NAA
TCLP-Method 1311
9040; 9041; 1110
SW-846
SW-846
calculation
ASTM C-39,
D-1633
ASTM C-403
Detection
Limits
no visible
moisture
10 CFR 61
I
3a/BG< limit
3a/BG< limit
3or/BG< limit
± 10 Ibs
10rel%atl
abs wt % if
possible
SW-846
82
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Table 4-6. Characterization of Inorganic/Sulfur Polymer Waste Forms
Property
Leach
Resistance
Free Liquids
Radionuclides
. Transferable
Contamination
Specific a
Activity
Dose Rate
Weight/Size
Other Labeling
Requirement
Hardness Test
Weight of Drum
Major Matrix
Elements
Toxicity
Ignitability
Corrosivity
Reactivity
LDR
Void Volume
Gas Generation
Compressive
Strength
Set Time
Sampling
Frequency
NR
Every
Container
Every
Container
Every
Container
Every Rep
Every
Container
NR
Every
Container
NR
Every
Container
Every Batch
Every Batch
NR
Every batch
Every batch
Every Batch
Every
Container
Every batch
Every batch
Every batch
Requirements
<0.5% by Vol.
For discussion assume
10 CFR 61
220dpm/dm2a
2200 dpm/dm2 0, 7
s 100 nCi/g
200 mrem/hr @ surface
<12001b (on-site)
800 Ib (DOT)
elem present @ > 1 wt %
limits in RCRA
40 CFR 261
banned by waste
Methods
Inspection after
cooling
TBD
TBD
count rate meter
,
same as before
TCLP - Method
1311
EPA 9040, 9041;
NACE 1110
For sulfide-Ch7,
SW-846
calculation
calculation
TBD
TBD
Detection
Limits
No visible
moisture
3a/BG < limit
3a/BG < limit
±101bs
SW-846
83
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Table 4-7. Characterization of Organic Polymer Waste Forms
Property
Leach
Resistance
Free Liquids
.Radionuclides
Transferable
Contamination
Specific a
Activity
Dose Rate
Weight/Size
Other Labeling
Requirement
Hardness Test
Weight of Drum
Major Matrix
Elements
TCLP
Ignitability
Corrosivity
Reactivity
LDR
Void Volume
Gas Generation
Compressiye
Strength
Set Time
Sampling
Frequency
NR
Every
Container
Every
Container
Every
Container
Every Rep
Every
Container
NR
Every
Container
NR
Every
Container
Every Batch
Every Batch
NR
NR
NR
Every Batch
Every
Container
Every batch
Every batch
Every batch
Requirements
<0.5% by Vol.
For discussion assume
10 CFR 61
220 dpm/dm2 a
2200 dpm/dm2 ft, y
< 100 nCi/g
200 mrem/hr @ surface
Site specific
DOT
<1200 Ib (on-site)
800 Ib (DOT)
elem present @ > 1 wt %
limits in RCRA
40 CFR 261
banned by waste
Methods
Inspection
Tomographic scan
a Chamber
/3.f counter
Process knowledge
count rate meters
"truck" scale
same as before
TCLP-Method 1311
calculation
calculation
TBD
TBD
Detection
Limits
-•
No visible
moisture
3cr/BG < limit
3or/BG < limit
± 10 Ibs
SW-846
84
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Table 4-8. Characterization of Ferrous Metal Waste Forms
Property
Purity
Radionuclides
Dose Rate
Specific a
activity
Labeling
Transferable
Contamination
Sampling
Frequency
Per item
Every Batch
Every item
Per item
Per item
Every Batch
Requirements
For discussion
assume 10 CFR 61
200 mrem/hr @
surface
DOT, NFPA,
WAC
220/2200
dpm/dm2
Methods
Alloy analyzer
TGS/SGS
dosimeters; count
rate meters »
Passive & active
neutron counts
MSDS
Smear, PAN
Detection
Limits
10 CFR 61
3a/background
< limit
3a/BG < limit
85
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Table 4-9. Characterization of Elemental Lead Waste Forms
Property
Purity
Radionuclides
Dose Rate
Specific a
activity
Labeling
Transferable
Contamination
Sampling
Frequency
Per item
Every Batch
Every item
Per item
Every item
Every Batch
Requirements
98%
For discussion
assume
10 CFR 6i
200 mrem/hr @
surface
DOT, NFPA
220/2200
dpm/dm2
Methods
Spectro-
photometric
HPGe on sample
dosimeters; count
rate meters
Sampled long
range
MSDS
Smear, PAN
Detection
Limits
3a/BG
< limit
3cr/BG < limit
86
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Table 4-10. Characterization of Elemental Mercury Waste Forms
Property
Purity
Radiomiclides
Dose Rate
Specific a activity
Labeling
Transferable
Contamination
Sampling
Frequency
Per item
Every Batch
Every item
Per item
Per item
Every Batch
Requirements
100%
For discussion
assume 10 CFR 61
200 mrem/hr @
surface
220/2200
dpm/dm2
Methods
Process knowledge
HPGe on sample
dosimeters; count
rate meters
as before
49 CFR 172.101
Smear container
Detection
Limits
3ff/BG < limit
3a/BG < limit
87
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Leach Resistance
Several tests have been applied to evaluate the chemical durability of final waste
forms. These tests are designed to determine the rates of release of various chemical
species from a crushed final waste form sample to a test solution. Commonly applied tests
include product consistency tests (PCTs), the Toxicity Characteristic Leaching Procedure
(TCLP), and the ANSI/ANS 16.1 leachability test (1). The TCLP is described in a separate
section below.
The PCT Methods These methods were developed within DOE's High-Level Waste
Program. Test Methods A and B have been used to evaluate the chemical durability of
homogeneous and devitrified glasses (2,3,4). The evaluation is performed by measuring the
concentrations of the chemical species released from a crushed glass to a test solution and
comparing them to the results for a "benchmark" glass.
Test Method A was developed specifically to test the durability of radioactive waste
glasses during production. It can also be used to test simulated waste glasses. The method
is easily reproducible, can be performed remotely on highly radioactive samples and can
yield results rapidly. The glass does not need to be annealed prior to testing. In this
method the glass is crushed and sieved to -100 to +200 mesh. The particles are cleaned of
adhering fines, and an amount of sized and cleaned glass that is greater than or equal to 1
gram is placed in a 304L stainless steel vessel. An amount of ASTM Type 1 water equal
to 10 tunes the sample mass is added and the vessel is sealed. The vessel is placed in a
convection oven at 90 °C. After 7 days the vessel is removed from the oven and cooled to
room temperature. The pH is measured on an aliquot of the leachate and the temperature
of the aliquot at the time of the pH measurement is recorded as well. The remaining
leachate is filtered and sent for analysis.
Test Method B was developed to test the durability of radioactive, mixed, or
simulated waste glasses. The method is similar to Test Method A except for the following
differences: (a) In this method the glass is crushed and sieved to -100 to +200 mesh pi to
the size range of interest as long as the glass particles are <40 mesh, (b) The particles are
cleaned of adhering fines (note: devitrified glasses containing soluble secondary phases
require special handling procedures), and an amount of sized and cleaned glass greater than
or equal to 1 gram is placed in either a 304L stainless steel vessel or a Teflon\ vessel.
Sample mass-to-volume of solution (S/V) ratios other than 1:10 are allowed and other
leachants than ASTM Type 1 water are allowed, (d) The vessel is placed in a convection
oven, generally at 90 °C but other test temperatures are allowed. After 7 days, or other
optional test durations, the vessel is removed from the oven and cooled to room
temperature. The pH is measured on an aliquot of the leachate and the temperature of the
aliquot at the time of the pH measurement is recorded as we'll. The remaining leachate is
filtered and sent for analysis.
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The ANS 16.1 Test This is a sequential-batch test in which small coupons of cemented
waste are extracted in distilled water. This test was developed for grouted waste forms
containing radionuclides. From the concentrations that leach into the successive leaching
solutions, an effective diffusivity and logarithmic leachability index are calculated for each
nuclide of interest. If leaching can be assumed to be diffusion-controlled, these parameters
have value in predicting cumulative leaching over time, and relative leachability of various
waste/grout formulations.
Free Liquids
EPA Method 9095, "Paint Filter Liquids Test," is used to determine the presence of
free liquids in a representative sample of waste and is specified as the method to be used
to determine compliance with 40 CFR 264.314 and 265.314. In the test a predetermined
amount of material is placed in a paint filter. If any portion of the material passes through
and drops from the filter within the 5-minute test period, the material is deemed to contain
free liquids.
Radionuclide Content
A specific inventory for all radionuclides is a difficult measurement because of all the
possible nuclides that must be measured independently. For the common isotopes of
plutonium and uranium, the neutron measurements discussed in the section for specific
alpha activity (below) are the most effective. Neutron multiplicity counting can also identify
americium and curium in some samples, but not with high sensitivity.
The standard method for identifying elemental constituents in a sample is gamma-ray
analysis. Passive gamma ray analysis will identify radioactive nuclides that decay by
spontaneous gamma ray emission. Gamma ray spectroscopy is a standard nuclear chemistry
technique. Passive gamma ray instruments for laboratory use are available from several
commercial sources as standard laboratory instrumentation.
Another approach to passive gamma-ray spectroscopy is the segmented gamma
scanner (SGS). The SGS instrument makes chordal measurements of the sample drum to
determine qualitatively the nuclear material distribution. It also has the ability to do a
transmission correction using a gamma ray source of known strength. Two measurements
are made, one with the source to determine the chordal attenuation and one to make the
isotopic determination. The passive measurement is corrected using the attenuation results.
Recently, the SGS system has been extended to a full tomographic system, modeled
somewhat after the medical imaging technology. In this case, the spatial distribution of both
attenuating medium and gamma-ray emission is determined by inverting chordal
measurements at many different angles and heights of the sample drum. A complete matrix
of linear attenuation is constructed from the data which is used to correct the passive
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gamma ray measurement. Both the SGS and the tomographic scanner are designed to
measure the more prominent gamma ray lines of spontaneously decaying radionuclides.
For those nuclides that decay by processes other than spontaneous gamma ray
emission, or for fissile material which does not have a high decay rate, active gamma ray
assay is necessary. The active techniques typically use a neutron source to induce the n-
gamma or the n-prime-gamma reactions. (The n-gamma reaction is a thermal neutron
capture process; the n-prime-gamma reaction is a neutron inelastic scattering process.)
These instruments use either a neutron source such as californium or a neutron generator.
Typical neutron generators electrostatically collide deuterium and tritium ions to excite the
D-T fusion reaction. Several manufacturers produce commercially available neutron
sources. Laboratory and industrial instruments for elemental identification are also
commercially available.
Transferable Contamination
The NRC has established limits of removable external radioactive contamination, i.e.,
transferable contamination as part of the requirements described in 10 CFR 71 on
Packaging and Transportation of Radioactive Material. The level of non-fixed (removable)
radioactive contamination on the external surfaces of each package offered for shipment
must be as low as reasonably achievable. The level of non-fixed radioactive contamination
may be determined by wiping an area of 300 square centimeters of the surface concerned
with an absorbent material, using moderate pressure, and measuring the activity on the
wiping material. Sufficient measurements must be taken in the most appropriate locations
to yield a representative assessment of the non-fixed contamination levels. Except as
provided under the next paragraph of this section, the amount of radioactivity measured on
any single wiping material when averaged over the surface wiped, must not exceed the limits
given below at any time during transport. Other methods of assessment of equal or greater
efficiency may be used. When other methods are-used, the detection efficiency of the
method used must be taken into account and in no case may the non-fixed contamination
on the external surfaces of the package exceed ten times the limits listed in Table 4-11
below.
In the case of packages transported as exclusive-use shipments by rail or highway
only, the non-fixed radioactive contamination at any time during transport must not exceed
ten times the levels prescribed in the first paragraph of this section. The levels at the
beginning of transport must not exceed the levels prescribed in the first paragraph of this
section.
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Table 4-11. Removable External Radioactive Contamination Wipe Limits.
Nuclides
Beta-gamma emitting
radionuclides; with half-
lives less than ten days.
All other alpha emitting
radionuclides.
Maximum Permissible Limits
/iCi/cm2 dpm/cm2
lO'5
ID"*
22
2.2
Specific Alpha Activity
Measurement methods for specific alpha activity are discussed in detail in Appendix
C. The following paragraphs summarize that discussion.,
Specific alpha activity is the rate of alpha particle emission per weight, measured in
curies per gram. The present limit for distinguishing low-level waste (LLW) from
transuranic waste (TRU) is 100 nanocuries per gram. Specific alpha activity is important
for two reasons. First, it directly affects the generation of gas by radiolysis. Gas generation
can affect the physical integrity of the container. Also,, alpha activity is typically associated
with a certain class of radionuclides which have a severe environmental impact. The most
notable are the isotopes of plutonium. Leaching of these isotopes out of the waste form
container could cause a significant environmental impact.
Because of the short mean free path of alpha particles, alpha activity is usually
measured indirectly. The most common approach is to exploit the alpha-neutron reaction:
an alpha interacts with a moderate atomic number (Z) material which then gives off a
neutron. Inferring the alpha activity from the neutron emission is a common and effective
technique. In the case of LLW waste assay, it is particularly reliable because the
presumption is that small quantities of waste are involved, so that the plutonium (or other
alpha emitting material) is naturally oxidized.
Passive Totals Counting Passive neutron totals counting is used to determine
specific alpha activity from the induced neutron emission. Typical instruments are the
passive counting aspect of the californium shuffler, and the passive add-a-source counter.
The passive-active neutron differential die-away counter can also make this passive neutron
measurement. This technique is typically used as a "screening" measurement; it determines
the upper bound of the alpha activity rate rather than a precise measurement.
Passive Coincidence Counting A more accurate but somewhat less sensitive method
is passive coincidence counting. Passive coincidence counting counts the number of
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simultaneous neutron pairs. Neutron pairs are a specific signature of a nuclear fission, so
this measurement determines the amount of fissionable material. Because the fissionable
isotopes are also typically those that decay by alpha emission, the alpha activity can also be
inferred. Passive coincidence counting systems for 55 gallon drums can operate down to the
10 nanocuries per gram level in well-shielded environments (the sensitivity depends on the
background count rates).
The passive coincidence measurement can be extended to neutron multiplicity
counting. Multiplicity counting counts simultaneous neutron events consisting of multiple
neutrons, extending the coincidence concept of counting neutron pair events. This technique
can reduce many of the uncertainties from matrix effects, additional isotopes such as curium,
and detector efficiencies.
Another extension of the passive coincidence measurement is the add-a-source
technique. The add-a-source technique provides a correction to a passive multiplicity or
coincidence counting for matrix-induced errors. The passive measurement is significantly
less sensitive to matrix effects than active measurements, but the induced bias error can be
reduced further. The add-a-source method introduces a known source with a neutron
spectrum similar to fission neutrons, and measures the effect of the waste drum matrix on
the source neutrons.
Active Interrogation The third principle measurement of specific alpha activity is
done by active neutron interrogation. The active measurement interrogates the sample with
a neutron source. Typically, a neutron generator is used in the case of the passive active
neutron, differential die-away (PAN/DDA) system and a californium source is used in the
PAN/californium shuffler. In both cases fissions are induced in the sample material and the
resulting fission neutrons are measured. The PAN/DDA system measures prompt fission
neutrons and the shuffler measures delayed neutrons. The isotopes that are specific to this
measurement are the odd isotopes of plutonium (239Pu, M1Pu predominantly) and ^U.
An important variant of the PAN/DDA system is the combined thermal-epithermal
neutron system (CTEN). The CTEN system now under development addresses one of the
important limitations of the PAN/DDA system, namely that the interrogation is done with
thermal neutrons. The penetration of thermal neutrons is very small, roughly a few hundred
microns in metallic plutonium. If significant quantities of plutonium are present in a
sample, it is possible that the active PAN/DDA system will significantly underestimate the
quantity. The CTEN .directly addresses this problem.
Because the active assay instruments can also make a passive measurement,
occasionally the active interrogation is combined with a passive multiplicity or coincidence
measurement. The most common instruments are the passive multiplicity counter with add-
a-source matrix correction, the californium shuffler, and the differential die-away system.
92
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Method Selection The choice of which system to use for final waste form certification
depends somewhat on the anticipated application. If the waste drum must be characterized
for low-level waste disposal only, then the passive multiplicity with add-a-source is the most
robust measurement. If a highly sensitive measurement is required, such as for Department
of Transportation regulations, then the PAN/DDA system has the required sensitivity. If
uranium is anticipated in the waste form, then the PAN shuffler measurement is perhaps
the most appropriate. Other active and passive neutron-based instruments are also under
development which may alleviate some of the problems discussed^ here.
Dose Rate
The Department of Transportation (DOT) has estabh'shed radiation level limitations,
i.e., dose rate, for radioactive materials offered for transportation. Each package shall be
designed and prepared for shipment so that under conditions normally incident to
transportation the radiation level does not exceed 200 millirem per hour at any point on the
external surface of the package, and the transport index does not exceed 10. If a package
exceeds the radiation level limits specified in the first paragraph, it shall be transported by
exclusive-use shipment only, and the radiation levels for such shipment must not exceed the
following during transportation: .
(1) 200 millirem per hour (2 millisievert per hour) on the external surface of the
package unless the following conditions are met, in which case the limit is
1000 millirem per hour (10 millisievert per hour). The shipment is made in
a closed transport vehicle; the package is secured within the vehicle so that
its position remains fixed during transportation; and there are no loading or
unloading operations between the beginning and end of the transportation.
(2) 200 millirem per hour (2 millisievert per 'hour) at any point on the outer
surfaces of the vehicle, including the top and underside of the vehicle; or in
the case of a flat-bed style vehicle, at any point on the vertical planes
projected from the outer edges of the vehicle, on the upper surface of the
load (enclosure is used), and on the lower external surface of the vehicle.
(3) 10 millirem per hour (0.1 millisievert per hour) at any point 2 meters (6.6
feet) from the outer lateral surfaces of the vehicle (excluding the top and
underside of the vehicle); or in the case of a flat-bed style vehicle, at any
point 2 meters (6.6 feet) from the vertical planes projected by the outer edges
of the vehicle (excluding the top and underside of the vehicle.
(4) 2 millirem per hour (0.02 millisievert per hour) in any normally occupied
space, except that this provision does not apply to private carriers if exposed
personnel under their control wear radiation dosimetry devices and operate
under .provisions of a State or Federally regulated radiation protection
program.
93
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Various commercially-available dosimeters and scanners can be used to measure the
dose rate. These include thermoluminescent dosimeters (TLDs), thermoluminescent
neutron dosimeters and critical neutron dosimeters.
Weight/Size
The weight and size measurements are expected to be part of the process control
scheme for those processes that produce pellets as the final waste forms, e.g., crystalline
ceramic waste forms. Current thinking is to weigh and measure the size of the pellets
occasionally during operation to determine density, as a quality control measure. The
pellets will be weighed with an electronic balance and measured with calipers.
labeling Requirements
General labeling and marking criteria include the following:
• Shall meet the labeling/marking requirements of DOT.
• Labels and markings shall be permanently applied with paint or other
materials that have a predicted 20-year life expectancy in the expected storage
environment and are compatible with the container and protective coating.
Epoxy-polyamide paint or Electromark plastic stickers are examples of 20-year
labeling and marking.
• All labels and markings shall be in clear, legible English in a color contrasting
with the background. Stencils (for paint-applied markings) or adhesive labels
shall be used for all markings.
• All labels and markings shall be nonfading and nonsmearing.
• Drums being banded to pallets shall be positioned to permit visual inspection
of the labels and markings!
Hardness Test
Hardness testing is expected to be part of the process control scheme for those
processes that produced pellets as a final waste form, e.g., crystalline ceramic waste forms.
Currently, hardness testing is not being conducted.
Weight of Drum
For waste forms from the MWTP that are transported off that site for disposal, the
DOT requires that individual drums not exceed 800 Ibs. For on-site disposal, higher weights
may be permitted (at the Nevada Test Site the limit is 1200 Ibs). In either case, the
measurement can be made using a truck scale.
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Major Matrix Elements
Major matrix element components and chemical composition contained in the final
waste form can be determined by a number of instrumental techniques, including atomic
absorption spectrophotometry, inductively coupled plasma-atomic emission spectroscopy, and
X-ray fluorescence spectrometry. Depending on the approach preferred by the facility or
on the requirements in the WAC for these measurements, all of the aforementioned
techniques can perform the necessary measurements, either individually or in some
complementary combination. For example, XRF may be chosen for frequent nieasurements,
backed up by periodic ICP/AES measurements. For those techniques requiring dissolution
of the final waste form material prior to assay, solubilization techniques and methods are
readily available.
Toxidty Characteristic
Each batch of waste forms produced by the treatment facility that was not created
in a BDAT process will have to be tested for the Toxicity Characteristic. The TC will be
shown if the TCLP extract from a subsample of the waste contains any of the contaminants
listed in 40 GFR §261.24 at a concentration greater than or equal to the respective value
given.
The Toxicity Characteristic Leaching Procedure is designed to simulate the leaching
a waste will undergo if disposed of in a sanitary landfill. The extraction fluid employed is
a function of the alkalinity of the solid phase of the waste. A subsample of a waste is
extracted with a buffered acetic acid solution for 18 ±2 hours. The extract obtained from
the TCLP (the "TCLP extract") is then analyzed to determine if any of the thresholds
established for the 40 Toxicity Characteristic constituents have been exceeded. If the TCLP
extract contains any one of the TC constituents in an amount equal to or exceeding the
concentrations specified in 40 CFR §261.24, the waste possesses the characteristic of toxicity
and is a hazardous waste. Both the leaching and extract analysis methods are specified by
RCRA.
Ignitability
The objective of the ignitability characteristic is to identify wastes that either present
fire hazards under routine storage, disposal, and transportation or are capable of severely
exacerbating a fire once started. The following definitions that apply to solid final waste
forms have been taken nearly verbatim from the RCRA regulations (40 CFR §261.21) and
the DOT regulations (49 CFR §§ 173.300 and 173.151). They specify the required tests.
A solid waste exhibits the characteristic of ignitability if a representative sample of
the waste has any of the following properties:
95
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(1) It is a liquid, other than an aqueous solution, containing <24% alcohol by
volume, and it has a flashpoint <60°C (140°F), as determined by a Pensky-
Martens Closed Cup Tester, using the test method specified in ASTM
Standard D-93-79 or D-93-80, or a Setaflash Closed Cup Tester, using the test
method specified in ASTM standard D-3278-78, or as determined by an
equivalent test method approved by the Administrator under the procedures
set forth in Sections 260.20 and 260.21. (ASTM standards are available from
ASTM, 1916 Race Street, Philadelphia, PA 19103.)
(2) It is not a liquid and is capable, under standard temperature and pressure, of
causing fire through friction, absorption of moisture, or spontaneous chemical
changes and, when ignited, burns so vigorously and persistently that it creates
a hazard.
(3) It is an oxidizer, as defined in 49 CRF §173.151.
For the purpose of the regulation, an oxidizer is any material that yields oxygen
readily to stimulate the combustion of organic matter (e.g., chlorate, permanganate,
inorganic peroxide, or a nitrate).
Corrosivity
The corrosivity characteristic, as defined in 40 CFR §261.22, is designed to identify
wastes that might pose a hazard to human health or the environment due to their ability to:
(1) Mobilize toxic metals if discharged into a landfill environment.
(2) Corrode handling, storage, transportation, and management equipment.
(3) Destroy human or animal tissue in the event of inadvertent contact.
To identify such potentially hazardous materials, EPA has selected two properties
upon which to base the definition of a corrosive waste. These properties are pH and
corrosivity toward Type SAE 2020 steel.
The procedures for measuring pH of aqueous wastes are detailed in EPA Method
9040, Chapter Six. EPA Method 1110 describes how to determine whether a waste is
corrosive to steel. Use EPA Method 9095, "Paint Liquids Test," to determine free liquid.
According to the RCRA regulations, a solid waste exhibits the characteristic of
corrosivity if a representative sample of the waste has either of the following properties:
1. It is aqueous and has a pH <2 or >12.5, as determined by a pH meter using
either the test method specified in this manual (Method 9040) or an
96
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equivalent test method approved by the Administrator under the procedures
set forth in Sections 260.20 and 260.21.
It is a liquid and corrodes steel (SAE 1020) at a rate >6.35 mm (0.250 in.)
per year at a test temperature of 55 °C (130 °F), as determined by the test
method specified the National Association of Corrosion Engineers (NACE),
Standard TM-01-69, as standardized by EPA Method 1110 or an equivalent
test method approved by the Administrator under the procedures set forth in
Sections 260.20 and 260.21.
Reactivity
The regulation in 40 CFR §261.23 defines reactive wastes to include wastes that have
any of the following properties.
(1) Readily undergo violent chemical change.
(2) React violently or form potentially explosive mixtures with water.
(3) Generate toxic fumes when mixed with water or, in the case of cyanide- or
sulfur-bearing wastes, when exposed to mild acidic or basic conditions.
(4) Explode when subjected to a strong initiating force.
(5) Explode at normal temperatures and pressures.
(6) Fit within the Department of Transportation's forbidden explosives, Class A
explosives, or Class B explosives classifications.
This definition is intended to identify wastes that, because of their extreme instability and
tendency to react violently or explode, pose a problem at all stages of the waste
management process. The definition is to a large extent a paraphrase of the narrative
definition employed by the National Fire Protection Association.
A solid waste exhibits the characteristic of reactivity if a representative sample of the
waste has any of the following properties:
(1) It is normally unstable and readily undergoes violent change without
detonating.
(2) It reacts violently with water.
(3) It forms potentially explosive mixtures with water.
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(4) When mixed with water, it generates toxic gases, vapors, or fumes in a
quantity sufficient to present a danger to human health or the environment.
(5) It is a cyanide- or sulfide-bearing waste which, when exposed to pH conditions
between 2 and 12.5, can generate toxic gases, vapors, or fumes in a quantity
sufficient to present a danger to human health or the environment.
(6) It is capable of detonation or explosive reaction if it is subjected to a strong
initiating source or if heated under confinement.
(7) It is readily capable of detonation or explosive decomposition or reaction at
standard temperature and pressure.
(8) It is a forbidden explosive, as defined in 49 CFR §173.51, or a Class A
explosive, as defined in 49 CFR §173.53, or a Class B explosive, as defined hi
49 CFR §173.88.
Land Disposed Restrictions (LDR)
Most or all of the waste streams that enter the treatment facility will be subject to
the RCRA Land Disposal Restrictions. Each waste stream may contain one or many
RCRA-listed wastes. For many of these waste streams, the Land Disposal Restrictions will
be satisfied by treatment that uses the Best Demonstrated Available Technology (BDAT).
But for others, testing will be necessary to verify that the final waste forms can be disposed
on land. The required test will be one of two types, as specified in 40 CFR 268: either an
assay of total concentrations of the constituents of concern in the waste form, or
measurement of these constituents in an extract of the waste form created using the TCLP.
As an example, consider a waste stream comprised of a hundred drums of
contaminated soil, that was created in the course of site remediation. Attached to this waste
stream is the waste code F039, defined as "leachate (liquids that have percolated through
land disposed wastes) resulting from the disposal of more than one restricted waste classified
as hazardous..." There is no BDAT defined for F039 wastes. In the facility, this waste
stream is treated by drying it and stabilizing the dried soils into inorganic grout waste forms.
To assure that these waste forms meet LDR limits, representative samples of each batch
must be collected (perhaps in the form of small grouted coupons cast specifically for
testing). They must be ground and extracted via the TCLP. The extract must be analyzed
for a suite of ten metals using methods listed in SW-846 (5). If the extract does not exceed
the limits listed in 40 CFR 268.41 for any of the ten metals, the waste forms satisfy this part
of the RCRA requirements (RCRA characteristic testing, as for corrosivity, may also be
required).
Because of the RCRA "mixing rule," it may be necessary to test every batch of waste
forms for the constituents of concern from every listed waste that had previously passed
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through the treatment facility, for which treatment was not by a BDAT. After many waste
streams were processed, this could require very extensive testing of final waste forms to
satisfy the Land Disposal Restrictions. Alternatively, the operator could demonstrate to the
regulator that the treatment technologies used are equal in effectiveness to the BDATs
(where those exist); this would obviate the need for RCRA testing of waste forms derived
from that waste stream. Such a demonstration program would be worthwhile for larger
waste streams, but for the many waste streams that are comprised of only a few containers,
the need for RCRA testing of the final waste forms can be anticipated.
Void Volume
Void volume, internal void spaces in LLW packages intended for disposal, shall be
minimized to the maximum extent practical; 10 percent is suggested as a maximum. This
requirement is likely to be among the WACs at the disposal site. It is intended to prevent
subsidence of the burial ground final cover after package deterioration.
The internal void space of any LLW package disposed at the TSD facilities shall not
exceed 10% of the total internal volume of the waste package! This requirement is based
on a similar requirement for hazardous waste disposal in 40 CFR §265.315. For the
purposes of this requirement, the internal void space shall include any opening within the
waste matrix that exceeds 5 cm (2 in.) in diameter. Spaces smaller than 5 cm (2 in.) such
as small horizontal planar spaces (e.g., the space between a waste package and its overpack)
need not be included in the void calculation. Spaces larger than 5 cm (2 in.) must be
eliminated either by vacuum compression, compaction of the waste, or by filling with an
approved void space filler.
Gas Generation
Packages of MLLW with the potential for gas generation or to reach explosive
concentrations of hydrogen and oxygen or other explosive gases (e.g., methane, volatile
organic compounds) may require vents or catalyst packs to deplete free oxygen and prevent
explosive concentrations. Packages with potential of H2 generation should be analyzed by
standard calculation methods such as developed by C. P. Delkate of EPRI, or if required,
.the use of catalysts or vents will be applicable. Liners other than plastic bags shall be
provided with positive gas communication to the outer container.
Compressive Strength
The 28-day compressive strength is a property often measured for quality control in
creating grout waste forms. It is also widely used to assess the long-term physical integrity
of the waste forms, although interpretation of the data in this context is not without
ambiguity. The tests that are used are unconfined, triaxial tests such as those specified in
ASTM standards C-39 and D-1633.
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Set Time
Set time is a process control variable evaluated in the creation of grout waste forms.
It should be tested at the beginning of each batch, using a penetration resistance procedure
such as ASTM standard €-403.
Waste Acceptance Criteria
Any disposal site that accepts final waste forms from the MWTP facility for disposal
will require that they satisfy .a particular set of waste acceptance criteria. These WACs,
specific to .the disposal site, will include various measures of radioactivity, material integrity,
chemical composition, labelling and physical properties. In all likelihood, they will include
many of the tests discussed in this chapter, or similar tests.
Many waste forms will be disposed on NPL sites. In these cases, CERCLA
requirements will be among the waste acceptance criteria. The site-specific Applicable or
Relevant and Appropriate Requirements (ARARs) may be much more stringent than
corresponding RCRA requirements.
Envirocare, Utah is now a permitted disposal site for MLLW from the DOE complex.
That site's operating plan may be consulted for an example set of waste acceptance criteria.
Additional Properties
The MWTP facility will produce lead, mercury and ferrous metals as well as waste
forms. Since these materials will be returned to use rather than disposed, they will be
subject to a different testing regimen than the waste forms. It is not now known whether
the distribution of these materials will be restricted in any way. If not, they will have to be
tested to assure the standards of the General Services Administration (GSA) are met. If
recycle is confined to the site itself, a more limited set of tests, shown in Tables 4-8 through
4-10, will suffice. Material purity and labelling requirements will differ from those already
discussed.
Material Purity The needed purity will depend on the intended use of the material.
It is assumed that all will be relatively pure upon exit of the plant. An alloy analyzer or
XRF can be used to evaluate the ferrous metals; the lead can be assessed by
spectrophotometry, and the mercury by process knowledge.
Labelling/DOT The materials for recycle are to be accompanied by Material Safety
Data Sheets. They are to be handled according to DOT regulations and have NFPA labels.
Radionuclides In lead, these will have to be measured by creating special samples.
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Conclusions and Recommendations
The insufficiency of analytical testing methods was judged by the workshop
participants to be not nearly so pronounced for final waste forms as upstream in the process.
There are several reasons for this. In general, the matrix tested is much more uniiLorm, so
representative sampling is not so difficult. The need for real-time or near-real-time testing
is not so great as within the waste treatment trains. The testing environment is not harsh,
compared to the environments monitored during processing. And%finally, many of the tests
are done by older, established methods or methods that are required by regulation. Several
method development needs were identified at the workshop, but the principal problems and
outstanding questions identified relate to interpretation of test results and regulatory
impediments.
Further effort must be devoted to clarifying sampling issues for final waste forms.
Questions to be addressed include:
• should destructive sampling use cores or separate coupons cast specifically for
testing?
• What constitutes representative sampling in the different waste forms and
materials for recycle? For the more uniform materials this will not be a
difficult issue to resolve, but what is a representative sample of a polymer-
encapsulated waste form?
how uniform are individual batches of waste forms?
influence the sampling/analysis design.
This will profoundly
The work group noted several research needs specific to testing of the organic
polymer waste forms. Methods development is needed here for assaying radionuclides, for
monitoring specific alpha, activity and for quantifying gas generation.
Within the work group, there was serious disagreement as to whether neutron and
gamma methods can achieve the desired detection limit of 3 a over background in
quantifying radionuclides. One recent study (6) suggested that they cannot. More work,
with actual waste forms, is needed.
There is insufficient guidance and consensus at present concerning waste form leach
resistance. What are the appropriate attributes for a test of leach resistance, and how can
test results be interpreted - and- extrapolated - correctly? The work group identified a
paucity of trustworthy tests for leaching behavior in LLW repositories. Performance
assessment methods and the use of TCLP results in particular were noted as potentially
inappropriate.
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It was pointed out that a sulfur polymer waste form will probably itself qualify as
reactive under RCRA. Without careful pilot testing, the treatment facility may itself create
new hazardous waste. There are a number of outstanding questions concerning measuring
the properties of this waste form, as well.
A major concern is the effect the RCRA "Mixing Rule" could have on characterizing
final waste forms. The rule could be - and recently has been - interpreted by regulators to
require testing for the full suite of RCRA characteristics in every waste form and recyclable
material, once a listed waste has passed through the plant. Treatment that occurs by
BDATs can be judged irrelevant. If such a requirement were imposed on an integrated
MLLW treatment faculty, waste form testing would call for an enormous resource allocation.
The balance between maximum treatment and minimum characterization would be broken..
1.
2.
3.
4.
5.
6.
References
American Nuclear Society. 1986. Measurement of the teachability of solidified low-
level radioactive wastes by a short-term test procedure. An American National
Standard. American Nuclear Society, LaGrange Park, IL.
Bibler, N.E, and Jantzen, C.M. 1989. The Product Consistency Test and its role in
the waste acceptance process. Waste Management 89 Proceedings I, pp. 743-749.
Jantzen, CM., RE. Bibler, D.C. Beam, W.G. Ramsey, and BJ. Waters. 1991.
Nuclear waste glass Product Consistency Test (PCT) method - Version 5.0. U.S. DOE
Report WSRC-TR-90-539, Rev. 2.
Jantzen, CM., N.E. Bibler, D.C. Beam and M.A. Pickett. 1993. Defense Waste
Processing Facility (DWPF) Environmental Assessment glass standard reference
material. U.S. DOE Report WSRC-TR-92-346 Rev. 1.
U.S. Environmental Protection Agency. 1986. Test methods for evaluating solid
waste. SW-846, 3rd edition and revisions. Office of Solid Waste and Emergency
Response, Washington, D.C,
SJ. Amir. 1993. Parametric study of radionuclide characterization - Low-level waste.
Prepared for the US DOE Office of Environmental Restoration and Waste
Management. Westinghouse Hanford Co., Richland, WA. WHC-EP-0655.
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Chapter 5
Conclusions and Recommendations
Gretchen Rupp, Ellen Stallings and John Koutsandreas
Identified Research, Development, and Demonstration Needs
At the workshop, each of the three workgroups identified needed research,
development, and demonstration efforts for characterization methods. The importance of
technology development was viewed differently by the three groups. In the area of
preliminary waste characterization, the conclusion reached was that efficient characterization
for the parameters of concern will depend on improved technology. Technology advances
are also needed for process monitoring and control, but basic facility design and public
perception issues will be equally important in establishing the characterization protocol.
Improvement of measurement methods is of less importance for final waste forms. The
outstanding questions relating to waste forms are the degree of testing that will be required
by regulators and what constitutes valid surrogate tests of long-term waste form properties.
Measurement-specific research, development and ; demonstration needs are listed
below. Larger unresolved characterization issues are discussed in later sections of this
chapter.
Pretreatment Waste Characterization
The baseline treatment scheme embodied in the MWTP will require a great deal of
characterization, especially at the upstream end of the facility. The difficulty of
representative characterization of heterogeneous waste is acute. This leads to two general
recommendations for RD&D. First, development of methods for bulk measurement of
waste properties should be emphasized over those for' measurement of small samples.
Second, where heterogeneous waste streams (that cannot be classified as debris) must be
treated, very robust treatment technologies that can accommodate a variety of waste
matrices (such as plasma furnace treatment units) should be considered. While treatment
process selection is technically outside of waste characterization, the balance between
treatment technique and characterization protocol cannot be avoided when considering
either. , 6
The general consensus of the work group felt that the following research needs were
of the highest priority for pretreatment characterization:
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1. Determine the reliability of process knowledge as an indicator of waste properties.
A standardized guidance for preparation of shipping manifests and describing and
verifying process knowledge should be developed.
2. Development of non-intrusive technologies to differentiate between organic/aqueous
or liquid/liquid phases in the near real time is a very high priority. Some
technologies such as neutron radiography are in the research stage and may have this
capability.
3. Non-intrusive methods to pinpoint radiation hot spots within containers in a timely
fashion require development for this application.
4. No known method for non-intrusively measuring the organic content of containerized
wastes appears to be commercially available. The non-intrusive technique prompt
gamma-neutron activation analysis (PGNAA) is being developed to help determine
organic content through the measurement of elemental composition, but it is still in
the research stage. Another promising method, still in development, is pulsed fast
neutron analysis (PFNA). Consequently, minimally-intrusive technologies should be
developed. These technologies would most likely utilize the fiber optic cable and
sensor systems that are being developed for vadose-zone and groundwater
measurements. The instrumentation would have to be hardened to overcome the
harsh environment within the containers.
5. There are similar limitations in the available methods for measuring special materials
in closed containers. At the workshop, only PGNAA was identified to make these
measurements non-intrusively, and it is not certain how many of the contaminants of
concern can be detected by this method. Here too, intrusive methods that test the
headspace or contained liquids deserve development.
6. Many existing methods were identified as potentially useful for measurement of
incoming wastes. However, very few of these can be considered "off-the-shelf"
technologies. Almost all will require adaptation and demonstration for this
application. In many cases, pilot- and full-scale evaluation using test bed facilities
will be needed. The resource requirements for this adaptation will not be trivial.
Process Monitoring and Control
Increased public awareness of safety, health, and environmental concerns has
generated a regulatory environment that places greater demands on the operation of
chemical process facilities. The DOE complex waste clean-up efforts will require facilities
that are operating chemical processes, which makes them a target for even more stringent
regulations because of the nature of the waste materials requiring processing. Considering
the present and future regulatory climate, the processes must be optimized to minimize
generation of secondary waste streams, limit worker exposure to hazardous and radioactive
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materials, and be capable of producing a final waste form for disposal that is both
chemically inert and resistant to physical degradation. One method for achieving process
optimization is to develop operating methods with process control based on near-real-time
chemical analyses. Achieving better control requires increased knowledge of the chemical
and radiological parameters that affect the process operations.
Characterization of waste during processing and treatment is needed to (1) identify
chemical and physical components that interfere with the formation of a stable final waste
lorm, (2) optimize/control reagent addition, (3) minimize secondary waste streams and (4)
provide process control based on real-time or near-real-time measurements
instrumentation and sensors must be rugged enough to operate in a processing environment
and must provide accurate quantitative determinations of contaminants at levels of interest
in a usable time frame for process control purposes.
f u general consensus of the work group felt that the following research needs were
of the highest priority:
There is a lack of real-time instrumentation to monitor the releases of heavy metals
radionuclides, and various hydrocarbon species from offgas systems. Development
ol this instrumentation is vital for public acceptance of treatment facilities.,
C rSt??eCtlve' Simple measurement calibration techniques are needed to insure the
reliability of m-lme measurements. As instrumentation is placed into the process
environment, innovative calibration techniques must be developed
1,
2.
3.
4.
5.
7.
Detection technology for mercury in solid matrices needs improvement.
The heterogeneous nature of much of the waste and the potential presence of
multiple troublesome species requires the development of screening methods for
heterogeneous matrices and specific detectors for specific constituents. Examples are
heavy metals and concentrated salts. y«»
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(neural network, electrical analog, etc.) for modelling the facilities. This would be
adapted to be site-specific. Its principal utility would be in facility design, testing,
and troubleshooting a malfunction in the operating facility.
Thermal treatment is likely to be the cornerstone of MLLW treatment across the
DOE complex. Many of the most difficult.treatment issues, technical and otherwise,
concern the offgases from thermal units. Those developing Site Treatment Plans would be
greatly aided by a concise compendium of methods for the monitoring of process gases.
Such a report should handle gases influent to the treatment unit, upstream of the offgas
cleanup units, and at the stack. A document that includes a narrative description of each
method (as in Appendix C herein) and summarize its capabilities and status (as in Table 2-
1) should be developed. An expanded report could include case histories, descriptions of
protocols for testing the methods, and discussion of the trade-off between up-front waste
characterization and segregation, and extensive, costly off-gas controls and monitoring.
Final Waste Forms
Research and development projects should target the following:
1. Methods for reliably quantifying radionuclides in final waste forms need
demonstration. In particular, the sensitivity, precision and accuracy of neutron and
gamma methods for this application need to be established.
2. Appropriate methods for sampling final waste forms should be standardized. The
protocols should specify where samples should be collected when destructive
sampling is required. Sampling schemes that guarantee representativeness must be
established.
3. Further background work is needed to develop these' representative sampling
protocols. The thermal treatment engineers need to establish the variation in the
characteristics of waste forms derived from each treatment technology. These
"population parameters" may have to be established in preliminary or pilot tests.
4. Methods for sampling organic polymer waste forms and measuring their properties
should be standardized. Especially needed are methods to quantify gas generation,
specific alpha.activity and the radionuclide content of these waste forms.
Waste Treatment and Institutional Issues
Effective waste characterization for treatment cannot be assured simply by
intensifying methods development. Many of the impediments to developing a
characterization plan are institutional or regulatory in nature, or relate to the design and
operation of the facility itself. These "larger issues," that were of considerable concern to
workshop participants, are discussed briefly in this section.
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Facility Design and Operation
Facility design cannot precede characterization plan development. Those who are
experts in the various measurement methods are essential members of the design team
Process design engineers cannot assume there will be off-the-shelf measurement techniques'
available to equip a facility treating mixed wastes. The lack of adequate measurement
methods may constrain process design; conversely, without explicit data quality objectives
measurement experts cannot select appropriate characterization techniques.
A vivid example of this treatment/characterization balance is the need to quantify
orgamcs in incoming waste containers. At the workshop, it was assumed that the plant
operators must know whether any container's contents are more than one percent organic
In many cases this can be determined semi-intrusively using some type of headspace analysis
But for heterogeneous materials like lab packs, full sampling would be required. Based on
the types of incoming waste streams, a choice must be made: should there be a set of
processing and treatment operations that will require this high level of preliminary waste
characterization, or should the facility incorporate more robust unit operations, avoiding the
need to quantify organics in every container? If these unit operations are not BDATs
demonstrating them to the satisfaction of the regulatory agency may be a lengthy process'
cancelling out the health benefits and savings realized by not measuring orgamcs.
A similar balance exists between characterization and facility operation. Workshop
participants warned that ensuring compatibility of wastes processed together is crucial but
the needed methods have not been assembled. DOE could develop a suite of methods to
meet this need, and perform the tests at the head of each treatment train. Alternatively
careful consideration of waste container batching, staging and processing may avoid the need
for such rigorous compatibility testing.
The characterization will employ a host of in-situ sensors to provide near-real-time
data on the treatment process. It is recommended that waste characterization and process
monitoring within the treatment facility incorporate a state-of-the-art expert system to assure
optimal operation levels and to assist in the analysis of the sub-systems during down time
This would involve the development of an off-line model which would evolve into an on-line
application that ^infers in real time. The analysis and modeling would involve the
n™^TntH T ? rt^^-"*** togic, symptoms, interactions, and patterns of plant
operating behavior. Based on tendencies, pattern matching and measured data, the expert
system would assure optimal operations and could forcast an operating deviation as much
!!ili» £ ? T' C°ntinuous use °f the expert system would allow the operators to
enhance their understanding of the treatment process.
An in-plant analytical laboratory will be needed at each facility. This laboratory will
perform all the physical and chemical tests required for the final waste forms. It will be
used to calibrate on-line instrumentation. Waste samples may also be analyzed there
depending on the final characterization strategy y '
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Regulatory and Institutional Issues
Workshop participants repeatedly expressed a need for explicit guidance from DOE
on the use of process knowledge to characterize wastes. The effort devoted to up-front
waste testing could be decreased greatly if many containers could be ^b\^ara^e^d
by process knowledge. The benefits would be especially pronounced for heterogeneous
wastes.
Workshop participants also stressed the need to develop consensus on tests to
evaluate the long-term properties of final waste forms. Tests of leaching and material
rrltegrity, in particular, need work. TCLP leachability is a property that will certainty be
required in facility WACs, but it only has validity in the environment of a sanitary landfill.
Long-term performance assessments of glass or ceramic waste forms are subject to
considerable controversy among materials scientists. This issue has technical regulatory
and public perception aspects. Reaching agreement on these tests is vital for the approval
of site-specific waste treatment plans.
A similar type of issue is the need for national performance standards for many of
the measurement methods. The well-established methods have agreed-upon performance
standards. Examples are the codification of many chemical techniques in ASTM standards
or EPA's SW-846 (1). But many nuclear methods discussed herein have no such standards;
measurement results are subject to varying interpretation. This variation will impede public
acceptance of facilities relying on these methods.
The issue of public acceptance arose throughout the workshop, but particularly in
discussions of the thermal treatment units. Public concern over these processes must be
accomodated by methods development for sensing/controlling system upsets and tor
monitoring offgases.
The RCRA Debris Rule may have a dramatic effect on the characterization and
treatment requirements for many mixed waste streams. If the specified BOAT is used to
treat the contaminated debris, the initial characterization requirements are significantly
reduced. Also, the requirement to verify that the final waste form meets the LDRs is
waived To date, all work that has been conducted toward evaluation of debris technologies
(extraction, destruction, and immobilization) has focused on hazardous waste. DOE's Mixed
Waste Integrated Program is pursuing projects to demonstrate, test, and evaluate debris
treatment technologies for mixed waste debris. As mixed waste streams are reclassified as
debris, the flowsheets for treatment could change significantly. To be eligible for the LDR
verification waiver for debris, treatment facilities will need a separate treatment line for
mixed waste debris.
A •final regulatory issue raises the concern that extensive characterization may be
required, no matter how carefully the treatment facility is designed and operated. A
regulatory agency could interpret the RCRA mixing rule to require exhaustive
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characterization of every solid waste form, regardless of whether treatment was by a BDAT.
There are no direct technical answers to this concern. However, reaching consensus on test
protocols, developing national performance standards, and involving regulators in developing
the waste characterization protocol may help diminish the likelihood of this outcome.
Continuing Work
This report describes a baseline characterize-to-treat strategy for mixed low-level
waste. Further technical work will be of two kinds:
technology research, development or demonstration to enhance
characterization capabilities, and
• development of individual Site Treatment Plans.
The technology RD&D efforts will be led by DOE headquarters offices. At each
site, the waste characterization strategy (really, the treatment-characterization strategy) will
be tailored to that site, and will be based on a risk-benefit analysis. It is recommended that
the strategy be developed by process design engineers and characterization technology
experts working together, along with field sampling experts, if necessary. Insofar as possible
explicit data quality objectives should form the basis for technology selection For some
measurements, a suite of complementary technologies will be needed; this will be site-
specific and will depend on the incoming waste streams. In general, the more varied the
waste streams, the greater the range in needed measurement options. The process planners
will need to allow for 10 - 20% added characterization costs for quality assurance and
quality control measurements.
In addition, public stakeholders should be involved at each stage, to lower non-
technical hurdles. Successful treatment of DOE's MLLW stockpile is a goal shared by all
interested parties. ', •
1.
Reference
U.S. Environmental Protection Agency. 1986. Test methods for evaluating solid
waste. SW-846. 3rd edition and revisions. Office of Solid Waste and Emergency
Response, Washington, D.C. y
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APPENDIX A
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Appendix A
The Five Waste Streams
John Koutsandreas
The five general waste streams correspond to the five treatment trains of the Mixed
Waste Treatment Project. The descriptions of their characteristics are drawn from
References 1 through 4. This classification dates from late 1992; more recent treatabihty
groupings differ somewhat from this. The word "debris" as used here is not equivalent to
the "debris" described in the RCRA Debris Rule. The current (spring 1994) methodology
for assigning waste streams to treatability groups is laid out in Reference 5.
Aqueous Liquids
Aqueous liquids consist of aqueous solutions and slurries. The total organic carbon
(TOC) is less than 1%. Some aqueous liquids are waste waters but not all will meet the
EPA definition of waste water under RCRA because they contain greater than 1% total
suspended solids. Non-wastewaters may contain suspended solids up to the pumpable limit
(30-40%) of the mass. Waste streams may exhibit multiple hazardous characteristics.
Streams may contain some of the following: As, Cd, Cr, Pb, Hg, Ag, and organics. Ignitable
and reactive characteristics could be exhibited by the following: benzene; solvents;
electroplating sludges, cyanides, and tetrachloroethylene. Corrosive characteristics could be
exhibited by sodium azide; chloroform; formaldehyde; formic acid; hydrofluoric acid; and
pyridine. Many different waste streams could exhibit the toxicity characteristic.
Acidic aqueous liquids include liquids with a pH of less than 6.0. Neutral aqueous
liquids include liquids with a pH between 6.0 and 8.0. Basic aqueous liquids include liquids
with a pH in excess of 8.0.
Homogeneous Solids
1. Wastes with matrices that are at least 90% homogeneous solids, including particulate
materials that do not meet the LDR criteria for classification as debris. The
homogeneous solids are further classified as particulates or cemented solids. Liquids,
if present, contain less than 1% TOC. The subcategory definitions follow.
A. Inorganic Particulates
Waste with matrices that are at least 90% inorganic particulates, including
residual or minimal absorbed water.
A-2
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3.
A.1 Ash
Waste with matrices that are at least 90% ash including incinerator
bottom and fly ash.
A,2 Sand Blasting Media
Waste with matrices that are at least 90% unused or spent surface
cleaning or decontamination paniculate material including coarse sand
or glass beads.
A3 Inorganic Bulk Chemicals
Waste with matrices that are at least 90% inorganic particulate
absorbent materials such as clay, vermiculite or diatomaceous earth.
B. Inorganic Cemented Solids
Inorganic homogeneous solids that have been immobilized with cement, or
other inorganic stabilization agents, and cured into a solidified form.
Waste with matrices that are at least 90% homogeneous solids may be mixtures of
organic and inorganic materials. Liquids, if present, may contain at least 1% TOC
or more. Included are particulates, cemented solids and hardened paint waste. The
subcategory definitions follow.
A. Inorganic/Organic Particulates
Wastes with matrices that are at least 90% inorganic particulate absorbent
materials with absorbed organic liquids; such as clay, vermiculite, or
diatomaceous earth with absorbed solvents.
*
A.1 Inorganic Particulate Absorbents w/Absorbed Organic Liquids
Waste with matrices that are at least 90% a mixture of
inorganic and organic particulates such as organic liquids
absorbed onto inorganic particulate absorbents.
This category includes waste with matrices that are immobilized solids containing
both inorganic and organic homogeneous materials that have properly cured into a
solidified form but do not meet disposal criteria. An example of waste that might
be included in this category is organic liquids solidified with an inorganic stabilization
agent. The subcategories follow.
A. Paint Chips/Solids
Waste with matrices that are at least 90% solid such as dried paint chips or
containers filled with dried paint.
A-3
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4.
This category includes waste with matrices that are least 90% homogeneous solids.
On a dry basis, the homogeneous solids are organic. Organic homogeneous solids
are further classified as particulates.
A. Organic Particulates
Waste with matrices that are at least 90% organic particulates including
residual or absorbed liquids.
A.1 Activated Carbon
Waste with matrices that are at least 90% spent or unused activated
carbon used for removal of organic materials from off-gas streams or
waste water operations.
A.2 Organic Resins
Waste with matrices that are at least 90% spent or unused organic
based resins, other than activated carbon.
A.3 Organic Particulate Absorbents
Waste with matrices that are at least 90% organic particulate
absorbent materials, including any absorbed aqueous liquids, such as
sawdust or ground corn cobs.
A.4 Organic Bulk Chemicals
Waste with matrices that are at least 90% solid, unused organic
chemicals packaged in bulk form that are either being excessed or have
expired.
This category includes waste with matrices that are at least 90% a mixture of
homogeneous solids and debris with the homogeneous solids fraction comprising at
least 50%, but no more than 90%, of the matrix.
A. Inorganic Homogeneous Solids (50%-90%)/Debris
Waste with matrices that are at least 90% a mixture of homogeneous solids
and debris with inorganic homogeneous solids comprising at least 50%, but
no more than 90%, of the matrix such as scrap iron (35%) and incinerator ash
(65%).
B. Inorganic/Organic Homogeneous Solids (50%-90%)/Debris
Waste with matrices that are at least 90% a mixture of homogeneous solids
and debris with homogeneous solids comprising at least 50%, but no more
than 90% of the matrix. The homogeneous solids are a mixture of inorganic
and organic materials with neither fraction contributing 50%, or more, to the
matrix.
A-4
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7.
C. Organic Homogeneous Solids (50%-90%)/Debris
Waste with matrices that are at least 90% a mixture of homogeneous solids
and debris with organic homogenous solids comprising at least 50%,, but no
more than 90%, of the matrix such as 65% organic particulate absorbents and
35% rags.
This category includes waste with matrices that are greater than 50% soil. Following
are the subcategory definitions.
A. Soil (>90%)
This category includes waste that is at least 90% soil.
B. Soil (50%-90)/Debris
This category includes waste with matrices that are at least 90% a mixture of
soil and debris with soil comprising at least 50%, but no more than 90%, of
the mixture.
This category includes debris (> 50%) materials that meet the LDR criteria for
classification as debris. The definitions for debris subcategories follow.
A. Metal Debris (> =90%)
This category includes inorganic debris that is at least 90% metal. Metal
debris are further subdivided below according to lead or cadmium content.
A.1 Metal Debris (w/o Pb or Cd)
Waste that is at least 90% metal debris and does not contain any bulk
lead or cadmium.
A.2 Lead-Containing Metal Debris
Waste that is at least 90% metal debris and contains separable or
bonded lead as part of the matrix such as glovebox parts containing
lead clad in stainless steel.
A.3 Cadmium-Containing Metal Debris
This category includes waste for which the entire matrix (e.g., > = 90%)
is essentially elemental cadmium. An example of waste in this
category is cadmium sheets.
A.4 Uranium Chips/Turnings
This category includes waste that is at least 90% uranium metal
components. An example of waste that might by included in this
category is uranium lathe turnings. The waste can be contained in
particulate materials to reduce their reactivity.
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A.5 Reactive Metals/Equipment Containing Reactive Metals
This category includes waste with matrices that are essentially bulk
reactive metals. Retired equipment containing reactive metals such as
pumps and pipe sections from handling reactive metals are included.
Typically these waste are sodium metal or sodium metal alloys, but
they can also include particulate fines of aluminum, magnesium
zirconium, or other pyrophoric materials. These are defined as waste
meeting the criteria for classification as water reactive or ignitable
reactive per the Third LDR rule.
B. Metal/Nonmetal Debris
Inorganic debris that is a mixture of metal and inorganic, nonmetal debris
with each fraction comprising less than 90% of the matrix including bulk,
separable or bonded, lead.
B.I Metal (> =50%)/Nonmetal Inorganic Debris
Inorganic debris that is a mixture of metal and inorganic nonmetal
debris with the metal fraction comprising at least 50% of the matrix
such as a drum contain 65% scrap iron and 35% concrete.
B.2 Metal/Nonmetal (> =50%) Inorganic Debris
Inorganic debris that is a mixture of metal and inorganic, nonmetal
debris with the nonmetal fraction comprising at least 50% of the
matrix such as 65% concrete and 35% scrap iron.
C. Inorganic Nonmetal Debris
Inorganic debris that is at least 90% inorganic, nonmetal materials
C.1 Concrete
Inorganic, nonmetal debris that is at least 90% concrete such as
concrete chunks and blocks.
C.2 Glass
Inorganic, nonmetal debris that is at least 90% glass such as leaded
glass windows, bottles, or light bulbs. Crushed glass is included if it
meets the LDR particle size criteria for classification as debris.
C.3 Ceramic/Brick
Inorganic, nonmetal debris that is at least 90% ceramic or brick
materials such as bricks, ceramic crucibles, or ceramic refractories.
C.4 Rock
A-6
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C.5 Asbestos
Waste that is at least 90% asbestos or asbestos based materials
requiring special handling based on content such as gloves, fire hoses,
aprons, flooring tiles, pipe insulation, boiler jackets, laboratory table
tops, and concrete.
D. Organic Debris
This category includes organic debris that is at least 90% plastic and/or
rubber materials including plastic or rubber sheeting, containers, gloves,
gaskets, and components of benelex or plexiglass. Also included are wood,
paper/cloth and graphite based solid materials of at least 90%, and animal
carcasses.
D.I Leaded Gloves/Aprons
This category includes plastic rubber organic debris that is at least 90%
leaded glbvebox gloves or aprons.
D.2 Halogenated Plastic/Rubber
This category includes plastic/rubber organic debris with halogenated
plastic, such as PVC.
D.3 Nonhalogenated Plastic/Rubber
This category includes plastic/rubber debris excluding leaded gloves
and aprons, which do not include halogenated plastics, such as PVC.
D.4 Wood
Includes organic debris that is at least 90% wood or wood products
other than paper such as structural timbers, boxes, or pallets..
D.5 Paper/Cloth :
Includes organic debris that is at least 90% paper or cloth such as
protective clothing, rags or wipes.
D.6 Graphite
Includes organic debris that is at least 90% graphite based solid
materials such as crucibles, graphite components, or pure graphite.
D.7 Biological
Includes organic debris that is at least 90% biological material such as
biological samples and animal carcasses.
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8. Hazardous Materials (> =90%)
This category includes waste in which the entire matrix is hazardous such as
elemental lead, reactive metals and liquid mercury, or wastes for which the waste
form is regulated. The subcategories follow.
A. Nonactivated Elemental Lead (> =90%)
This category includes waste consisting of elemental lead that is surface
contaminated with radionuclides.
B. Activated Elemental Lead (> =90%)
This category includes waste consisting of elemental lead that has bulk
radioactive contamination or has been contaminated through induction.
C. Beryllium Dust (>=90%)
This category includes waste that is essentially beryllium dust or chips and
fines that may contain beryllium dust. This category does not include debris
waste that is contaminated with beryllium dust.
D. Explosives
Includes wastes consisting of substances which undergo rapid chemical
transformations which produce large amounts of gases and heat and
explosions such as liquid nitroglycerine and TNT.
E. Compressed Gases/Aerosols
Includes waste meeting the criteria for classification as ignitable compressed
gases for the Third LDR rule such as pressurized gas cylinders or potent
aerosol cans.
F. Reactive metals
Typically these wastes are sodium metal or sodium metal alloys, but they can
also include particulate fines of aluminum, magnesium, zirconium, or other
pyrophoric materials. These are defined as waste meeting the criteria for
classification as water reactive or ignitable reactive per the Third LDR rule.
F.I Bulk Reactive Metals
Includes waste with matrices that are essentially bulk reactive metals.
F.2 Equipment Containing Reactive Metals
- Includes retired equipment waste that contains reactive metals such as
pumps and pipe section for handling reactive metals.
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G. Liquid Mercury
This category includes waste containing bulk quantities of pour able liquid
mercury. The liquid mercury may be also packaged in small containers within
a larger container holding other materials '(e.g., labpack configuration).
5.
Organic Liquids
Non-Halogenated Organics
These are solvents free of F, Cl, Br, e.g., oils, hexane, methanol. Streams may
contain Cd, Cr, Pb, Hg, and Se as trace contaminants. Ignitable characteristics and
corrosive characteristics could be exhibited by Cd, Gr, Pb, Hg, Se, benzene, carbon
tetrachloride, 1-2-dichloroethane, 1-1-dichloroethylene, tetrachloroethylene,
trichloroethylene, degreasing solvents, methanol, toluene, xylene, and benzene.
Halogenated Organics ,...,-.
These are solvents containing F, Cl, Br, etc. They include all PCB contaminated
organic streams. Streams may contain Cd, Cr, Pb, Hg, and Ag as trace
contamination. Ignitable characteristics, corrosive characteristics and reactive
characteristics may be exhibited by Cd, Cr, Pb, Hg, Ag, benzene, carbon
tetrachloride, chlorobenzene, chloroform, 1-2-dichloroethane, 1-2-dichloroethylene,
tetrachloroethylene, trichloroethylene, and solvents.
Scintillation Cocktails
These are solutions used for scintillation counting. Solutions are most often in the
original glass or plastic analysis bottles. Streams may contain Cd, Cr, and Pb as trace
contamination. Ignitable characteristics and corrosive characteristics may be
exhibited by Cd, Cr, Pb, chloroform, degreasing solvents and other solvents.
Low TOC Organic Liquids contain at least 1%, but less than 10% TOC. This
includes:
A. Halogenated low TOC organic liquids containing at least 1% (10,000 ppm)
halogenated organic compounds (HOC).
B. Non-halogenated low TOC organic liquids containing less than 1% (10,000
ppm) HOC.
Moderate TOC Organic Liquids contain at least 10%, but less than 90% TOC. This
includes:
A. Halogenated moderate TOC organic liquids containing at least 1% (10 000
ppm) HOC.
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B. Non-Halogenated moderate TOC organic liquids containing less than 1%
(10,000 ppm) HOC.
High TOC Organic Liquids includes liquids for which the TOC is at least 90%. This
includes:
A. Halogenated high TOC organic liquids containing at least 1% (10,000 ppm)
HOC.
B. Non-halogenated high TOC organic liquids containing less than 1% (10,000
ppm) HOC.
Heterogeneous Solids
Heterogeneous Debris (Inorganic > =50%)
This category includes heterogeneous debris that is at least 50% inorganic debris
material including a mixture of 65% scrap metal with 35% rags, or a mixture of 75%
concrete with 25% plastic.
A. Heterogeneous Debris (Metal > =50%)
Includes heterogeneous debris that is at least 50% metal debris material such
as 65% scrap metal with 10% concrete and 25% rags, or a mixture of 75%
glove box sections with 15% empty glass bottles and 10% paper wipes.
B. Heterogeneous Debris (Nonmetal> =50%)
Includes heterogeneous debris that is at least 50% inorganic, nonmetal debris
material such as a mixture of 65% brick with 35% rags, or a mixture of 75%
concrete with 25% plastic.
Heterogeneous Debris (Organic > =50%)
This category includes heterogeneous debris that is at least 50% organic debris
material such as a mixture of 65% rags with 35% scrap metal, or a mixture of 75%
plastic with 25% concrete.
Asphalt
This category includes waste that is at least 90% asphalt or other bituminous
materials such as roadways, shingles, bituminous cement or other materials
containing both tar and gravel.
Debris (50-90%)
This category includes waste with matrices that are at least 90% a mixture of
homogeneous solids and debris, with the debris fraction comprising at least 50%, but
no more than 90%, of the matrix. Also included are mixtures of soils and debris with
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the debris fraction comprising at least 50%, but no more than 90%, of the matrix.
The subcategories follow.
A. Inorganic Debris (50%-90%)/Homogeneous Solids
Includes waste with matrices that are at least 90% a mixture of homogeneous
solids and debris, with inorganic debris comprising at least 50%, but no more
than 90%, of the matrix such as a combination of 65% scrap iron and 35%
incinerator ash.
B. Heterogeneous Debris (50%-90%)/Homogeneous Solids
Includes waste with matrices that are at least 90% a mixture of homogeneous
solids and debris, with debris comprising at least 50% but not more than 90%
of the matrix. The debris is a mixture of inorganic and organic materials with
neither fraction contributing 50% or more to the matrix. An example is a
combination of 35% concrete, 30% rags, and 35% sludge.
C. Organic Debris (50%-90%)/Homogeneous Solids
Includes waste with matrices that are at least 90% a mixture of homogeneous
solids and debris, with organic debris comprising at least 50%, but no more
than 90% of the matrix. An example might be a combination of 65% rags
and 35% sludge.
D. Inorganic Debris (50%-90%)/Soil
Includes waste with matrices that are at least 90% a mixture of soil and
debris, with inorganic debris comprising at least 50%, but no more than 90%,
of the matrix. An example is a combination of 65% concrete and 35 %
soil.
E. Heterogeneous Debris (50%-90%)/Soil
Includes waste with matrices that are at least 90% a mixture of soil and
debris, with debris comprising at least 50%, but no more than 90% of the
matrix. The debris is a mixture of inorganic and organic materials with
neither fraction contributing 50% or more. An example is a combination of
35% scrap iron, 30% rags, and 35% soil.
F. Organic Debris (50%-90%)/Soil
Includes waste with matrices that are at least 90% a mixture of soil and
debris, with organic debris comprising at least 50%, but no more than 90%
of the matrix. An example is a combination of 65% rags and 35% soil.
G. Batteries (> =90%)
This category includes waste consisting of batteries. The batteries may be
packaged with absorbent materials (e.g., particulates, rags, etc.)
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G.I Lead Acid Batteries
This category includes drained or undrained.lead acid batteries that
have been excessed or retired.
G.2 Cadmium Batteries
This category includes cadmium batteries that have been excessed or
retired.
G.3 Mercury Batteries
This category includes mercury batteries that have been excessed or
retired.
Wet Solids
1. Wastes with matrices that are at least 90% homogeneous wet solids include sludges
and salts. Liquids, if present, contain less than 1% TOC. The subcategory
definitions are listed below.
A. Inorganic Sludge
A.1 Waste Water Treatment Sludge
Waste with matrices that are at least 90% inorganic secondary sludge
or filter cakes.
A.2 Plating Waste Sludge
Waste with matrices that are at least 90% inorganic secondary sludge
or filter cakes.
A3 Pond Sludge
Waste with matrices that are at least 90% inorganic sludge from
remediation of surface impoundments, such as evaporation or
sedimentation basins.
A.4 Scrubber Sludge
Waste with matrices that are at least 90% inorganic sludge from wet
off-gas treatment systems.
A.5 Halogenated Inorganic Sludge
Waste with matrices that are at least 90% inorganic sludge containing
at least 1% HOC.
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D.
E.
A.6 Non-Halogenated Inorganic Sludge
Waste with matrices that are at least 90% inorganic sludge containing
less than 1% HOC.
B. Organic Sludge
B.I Halogenated Organic Sludge
Waste with matrices that are at least 90% organic sludge containing
greater than 1% HOC.
B.2 Non-Halogenated Organic Sludge
Waste with matrices that are at least 90% organic sludge containing
less than 1% HOC.
Salt Waste
C.1 Chloride/Sulfate Salt Waste
Waste with matrices that are at least 90% chloride and/or sulfate salts.
C.2 Nitrate Salt Waste
Waste with matrices that are at least 90% nitrate salts.
Paint Waste
This category includes waste with matrices that are at least 90% new, used or
removed paint.
D.I Paint Liquids/Sludge
Waste with matrices that are at least 90% pourable paint and Includes
paint that has partially dried to a sludge but can still be poured or
easily removed.
Inorganic Particulates
This category includes waste with matrices that are at least 90% inorganic
particulates including residual or absorbed water. There is lower water
content in the sludge with particulates.
E.I Inorganic Ion Exchange Resins
This category includes waste with matrices that are at least 90%
unused or spent inorganic exchange resins.
A-13
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F. Labpacked Organic Liquids
This category includes labpacked organic liquids.
F.I Labpacked Discarded Organic Liquid Chemicals.
This category includes labpacked organic liquid chemicals which are
either being excessed or have expired.
F.2 Labpacked Organic Scintillation Fluids
This category includes organic scintillation fluids contained in vials that
are packaged in a labpack configuration.
G. Labpacked Aqueous Liquids
This category includes labpacked aqueous liquids.
G.I Labpacked Discarded Aqueous Liquid Chemicals
This category includes labpacked aqueous chemicals which are either
being excessed or have expired.
G.2
Labpacked Aqueous Liquid Scintillation Fluids
This category includes aqueous scintillation fluids contained in vials
that are packaged in a labpack configuration.
References
1. U.S. Department of Energy. 1993. Draft Waste Treatability Group Guidance.
Matrix parameter categories. Office of Waste Management (EM-30). 7/14/93.
2. U.S. Department of Energy. 1993. Interim Mixed Waste Inventory Report: Waste
Streams, Treatment Capacities, and Technologies. Vol. 5.
3. W. Ross. 1993. Mixed Waste Matrix - Contaminant Treatment Matrix. Personal
communication (facsimile) to Stanley Wolf (EM-55). Pacific Northwest Laboratory.
6/22/93.
4. W. Ross. 1993. Waste Stream Characteristics - DOE's MLLW. Presentation to
MLLW Steering Committee, Albuquerque, NM, Jan. 1993. Pacific Northwest
Laboratory.
5. Kirkpatrick, T. and W. Ross. 1993. DOE Waste Treatability Groups Guidance. Final
Draft. Office of Waste Management, Office of Environmental Restoration and Waste
Management, U.S. Dept. Energy. September 1993.
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APPENDIX B
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Appendix B
MWTP Process Flow Diagrams
Drawing Title
Receiving and Segregation
Aqueous Liquids Treatment
Organic Liquids Treatment
Wet Solids Treatment
Homogeneous Dry Solids Treatment
Heterogeneous Dry Solids Treatment
Thermal Treatment-Heavy Organic
Thermal Treatment-Low Residue
Thermal Treatment-Non-Metallics
Thermal Treatment-Ferrous Metal
Thermal Treatment-Non-Ferrous Metal
Thermal Treatment-Hg Bakeout
Thermal Treatment-Hg Condensation
Thermal Treatment-Secondary Condensation and Off-
Gas
Final Forms Treatment-Glass Melter
Final Forms Treatment-Lead Treatment
Final Forms Treatment-Grouting
Final Forms Treatment-Super Compaction
Final Forms Treatment-Hg Distillation
and Polymer Solidification
Support Operations-Off-Gas Cleanup
Support Operations-Container Decon
MWTP
MWTP
MWTP
MWTP
MWTP
MWTP
MWTP
MWTP
MWTP-
MWTP-
MWTP-
MWTP-
MWTP-
-PFD-010
-PFD-100
•PFD-200
•PFD-300
-PFD-400
-PFD-500
•PFD-801
•PFD-802
•PFD-803
•PFD-804
•PFD-805
•PFD-806
•PFD-807
(6 sheets)
(5 sheets)
(3 sheets)
(5 sheets)
(6 sheets)
MWTP-PFD-808
MWTP-PFD-901
MWTP-PFD-902
MWTP-PFD-903
MWTP-PFD-904
MWTP-PFD-905
MWTP-PFD-1001
MWTP-PFD-1002
The sample points referred to in the text are shown on the diagrams by number. These
points may designate actual locations where on-line measurements are made, or they may
be points where material samples are collected for analysis elsewhere. Locations of some
of the points are not settled. For example, monitoring of the thermal treatment trains may
be done by measuring gaseous species at any of several points in the treatment train.
Source: Bechtel Environmental, Inc., September 1992. Mixed Waste Treatment Project
Process Systems and Facilities. Design Study and Cost Estimates. Prepared for Lawrence
Livermore National Laboratory.
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APPENDIX C
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Appendix C
Method Descriptions for
Characterization of Incoming Waste
This appendix is a compendium of descriptions for a number of the measurement
techniques cited in Chapter 2. The descriptions were submitted after the workshop by
members of the Characterization before Treatment workgroup. There is no attempt to offer
a comprehensive discussion of all the methods identified by this group. Many of these
methods may also be useful in process monitoring and final waste forms characterization.
Several of these techniques are undergoing development or demonstration in projects
funded by DOE.
High-Performance Liquid Chromatography (HPLC)
High-performance liquid chromatography (HPLC) is a chromatographic method in
which pumps capable of producing pressures in excess of 300 atmospheres are used to push
a liquid mobile phase through a column packed with stationary particles having an average
diameter of 20 jam or less. An organic component injected prior to the column is
partitioned between the mobile phase and the stationary phase, resulting in retention. The
most common type of detection is by ultraviolet/visible (UV/Vis) absorption. In UV/Vis
detection, the wavelength and quantity of light absorbed is characteristic of the type of
molecule (or ion) and its concentration. Other types of detectors used in HPLC include
fluorescence, electrochemical, and mass spectrometry.
HPLC has the ability to separate and detect a wide variety of organic compounds.
These include neutral, polar, and ionic organic species. Many species not amenable to gas
chromatography because they are thermally labile or non-volatile can be successfully
analyzed by HPLC. The chromatographer has a wide selection of mobile phases and
column types among which to choose for optimal results.
Gas Chromatography - Mass Spectrometry (GC/MS)
Gas chromatography/mass spectrometry (GC/MS) is a technique which provides
separation of volatile organic molecules by gas chromatography and detection by mass
spectrometry. In gas chromatography, a "carrier gas" (typically hydrogen or helium) flows
through a heated column which contains a stationary phase. Organic analytes injected into
the gas stream prior the column are vaporized and carried through the column. The organic
molecule's affinity for the stationary phase dictates the extent of retention. In electron
impact mass spectrometry, molecules are introduced into the ion source where they are
bombarded by 70 eV electrons. The interaction of the molecules with the electrons
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produces ions which are characteristic of the molecular weight of the analyte. After
formation the ions exit the ion source and are filtered (focused) into a detector such as an
electron multiplier. A computer then interprets the signal and produces a mass spectrum
that relates ionic abundance to the mass-to-charge ratio of the ion. The mass spectrum is
often considered a "fingerprint" of the molecule and is very useful for compound
identification.
The mass spectrometer is maintained at a high vacuum (10"6 Torr) and cannot
withstand much gas flow into the ion source. When GC/MS first emerged, the packed
columns used for GC had flow volumes too great for the mass spectrometer to handle and,
therefore, the sample had to be "split" resulting in less analyte reaching the mass
spectrometer's ion source. Modern GC/MS methods of analysis use small diameter (0.25
mm) fused silica capillary columns which can be introduced directly into the ion source of
the mass spectrometer with no splitting necessary. Not only does the capillary column
simplify the operation, it has greater resolution than the old packed columns.
X-ray Fluorescence (XRF)
X-ray fluorescence spectrometry uses x-ray photons produced from an x-ray tube or
radioactive source to bombard a sample to produce secondary fluorescent x-ray photons
which are characteristic of the elements and their quantities present in the sample. The
primary advantage of this method is that minimal sample preparation is required, making
the method suitable for field applications.
XRF is based on the principle that a percentage of the incident photons that impinge
on the electron shells in atoms of the sample are absorbed and their kinetic energy
transferred to inner shell electrons of the sample atoms. This process results in ejection of
an inner shell electron from the sample atoms and leaves the atom's electron configuration
in an excited state. The sample atom returns to a ground state electron configuration when
the vacant inner electron shell is filled with an electron from the outer shell. The outer
shell electron loses energy as an x-ray photon during the transfer in the process called x-ray
fluorescence.
There are two types of XRF spectrometers, energy dispersive (EXRF) and
wavelength dispersive (WXRF). The EXRF detects the quantity and number of x-ray
photons as a function of photon energies. The EXRF can simultaneously measure x-ray
photons from all elements heavier than fluorine in concentration ranges from a few parts
per million to 100%. WXRF uses diffraction to measure x-ray photons at each wavelength
but requires a specific detector at each wavelength. WXRF, while more sensitive than
EXRF, cannot easily perform different arrays of multi-element analyses. Both spectrometers
are more sensitive as the analytes of interest increase in atomic number.
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Inductively Coupled Plasma - Atomic Emission Spectrometry (ICP-AES)
Inductively coupled plasma (TCP) spectrometry uses an argon plasma which has been
excited by an inductively coupled radiofrequency field. This plasma is used to induce
emission from ions and atoms which have been injected into the plasma. At room
temperature, almost all of the atoms in a sample are in the ground state. Excitation of
electrons to higher orbitals is accomplished by the heat of the plasma. This excited state
lasts briefly and then the electron returns to the ground state. As the electron relaxes, a
characteristic quantum of radiation is emitted. This radiation can be used to identify and
quantify the inorganic analyte of interest.
Inductively Coupled Plasma - Mass Spectrometry (TCP-MS)
ICP-MS uses an argon plasma which has been produced by an inductively coupled
radiofrequency field as an ion source with a quadrupole mass spectrometer for the detection
and quantitation of ions of differing mass-to-charge ratios. The mass spectrometer is
capable of differentiating between masses which nominally differ by 1 atomic mass unit.
Detection of ions is performed by a channel electron multiplier, a faraday cup, or an active
film multiplier.
The ICP-MS is more sensitive than ICP-AES for many elements. More importantly,
ICP-MS allows for discrimination of isotopes of an element within a specified sample. If
the isotope ratios of an element found within a sample differ significantly from the naturally
occurring isotope ratios, the isotope ratio data can be used as a means of source
identification of a sample. The capability of ICP-MS to distinguish between isotopes of an
element makes it an extremely valuable tool for analysis of radioactive wastes. Radioactive
samples which are analyzed using counting techniques require extensive wet chemistry'
preparation prior to analysis due to the non-specificity of the detectors. The mass
spectrometer is a specific detector and ICP-MS, therefore, requires minimal sample
preparation prior to analysis. Consequently, turnaround times are greatly reduced.
Laser Ablation Inductively Coupled Plasma - Mass Spectrometry (LA ICP-MS)
Laser ablation ICP-MS uses a high energy Nd:YAG (Neodymium YAG) laser to
ablate or vaporize a solid sample prior to analysis. The laser is focused onto a small (tens
of microns) area of the sample of interest using a binocular microscope, and a series of laser
pulses is triggered to ablate the sample. The number of pulses fired can be varied and is
dependent on the concentration of analyte in the sample. Lower concentrations require
more pulses to provide sufficient vaporized sample for analysis. The ablated, or vaporized,
sample is then transported into the ICP plasma by means of an argon gas flow.
Data acquisition using the ICP-MS is rapid: scans taking in all elements can be
obtained in as little as 100 milliseconds, although scan times of 60 to 90 seconds are
necessary to obtain accurate concentration measurements. The capability of directly
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sampling a solid eliminates the need for sample dissolution which is necessary for analysis
using ICP-AES, ICP-MS and GFAAS. LA ICP-MS has been shown to be applicable to a
variety of solid matrices, including ceramics, glasses, whole rock and mineral samples,
semiconductor materials, metals and powders.
AtomicAbsorption Spectrometry (AAS) and Graphite Furnace Atomic Absorption Spectrometry
(GFAAS)
Atomic absorption Spectrometry (AAS) is useful in the determination of metal atoms.
For absorption of radiation by a metal atom to occur, the energy of the source radiation
must exactly match the energy difference between the ground state and one of the excited
states of the absorbing species. The decrease in the intensity of the source radiation due
to absorption by the analyte atoms can be related to the concentration of absorbing atoms
in the sample.
Graphite furnace atomic absorption Spectrometry (GFAAS) utilizes an electrical
current for vaporization of the sample prior to analysis. This is generally accomplished in
3 stages: 1) a drying stage during which the solvent is vaporized; 2) an ashing stage during
which any organic components present in the sample are burned off; and 3) an atomization
stage during which the analyte is atomized into a vapor. This vapor is subsequently analyzed
for the element(s) of interest. The method requires much smaller sample volumes (#L as
opposed to mL) and allows for lower absolute detection limits than conventional flame
AAS.
Gamma Ray Spectroscopy
The primary purpose of the measurement is to apply appropriate radiological safety
in processing drums. Here, a simple dose-rate measurement is sufficient. However, much
more qualitative and quantitative information can be obtained in reasonable times with a
variety of commercially available instruments. All rely on gamma-ray Spectroscopy using low
or high-resolution detectors. Either of two different methods may be used: whole-drum
counts (WCD) or segmented gamma scanning (SGS).
Whole-Drum Counter
In the WDC method, the drum is usually placed in a shielded enclosure viewed by
typically one to three detectorsi Detector selection depends on the complexity of the
measurement task. For waste containing only a few radionuclides, low resolution sodium
iodide, NaI(Tl), detectors may suffice. But for more variable or unknown wastes, high-
resolution high purity germanium (HPGe) detectors are a better choice.
The drum is rotated inside the enclosure as it is viewed by the detector(s). A
spectrum is required, stored in computer memory, and analyzed for the energies and
intensities of the detected gamma rays. If the drum contents are reasonably homogeneous
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and of low density, good corrections for attenuation of the gamma rays, as they pass through
the waste matrix, can be made. Most gamma-emitting nuclides can be measured at levels
of 1-10 pCi/g under ideal conditions with assays of 5-10%. As the waste becomes more
dense and/or heterogeneous, quantification accuracy decreases significantly. Howeyer,
qualitative information, as to the identity of nuclides present, is often still obtainable and
useful. . , ^
Segmented Gamma Scanner
The SGS represents a refinement of gamma counting which can overcome some of
the limitations of the WDC. ,It uses a single HPGe, since the method is aimed primarily at
high resolution measurements of enriched uranium or plutonium in waste.. Here, the
detector is shielded and collimated so as to view only a narrow vertical segment of the
drum. As before, the drum is rotated, but in addition, a beam of gamma rays from a
transmission source can be shone through the drum as a measure Of the waste's attenuation
of the nuclide of interest. Each segment is scanned sequentially and summed to provide an
assay of the entire drum. ,
SGS, under optimum conditions, can provide assays of a few percent for plutonium
at 100 nCi/g or more. This requires longer count times (30-60 min.) and more complex
hardware than for WDG. Also, SGS is generally set up to optimize measurement of a single
radionuclide like Pu-239 or U-235. While fission/activation products will also be detected,
their quantification is not as good, and they may interfere with the uranium or plutonium
determination.
Acoustic Monitoring
Acoustic monitoring probes have been installed on a mixer pump within tank 101-SY
on the Hanford site. There are two types of probes installed; one of them is applicable to
monitoring containerized wastes. These are "density monitors" which are 1/10 of a watt in
power and consist of a transmitter and a receiver. Currently particulate concentration data
obtained from these probes is converted to density information. The density information
tells operators the "degree of mobilization" of the waste. This information will aid during
the retrieval of double-shell tank waste by indicating when the sludge within a tank is
homogeneously mixed with the supernatant liquid inside it. Other possibilities include in-
line determination of particulate concentration. In-line particulate monitoring could be
utilized during single shell tank retrieval. Wastes are recirculated during sluicing operations.
This type of monitor would provide operators with information which would allow them to
switch from recirculation mode to transfer mode. Particulate concentrations of 30% are the
target for pumping the material out from the single shell tanks during sluicing operations.
Time to develop an acoustic probe system for in-drum application is approximately nine
months and $200K. The point of contact for this DOE demonstration project is Al Tardiffc
DOE-HQ, EM-542, (301) 903-7670.
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Laser-induced Plasma Spectroscopy
Laser-induced plasma spectroscopy (LIPS, also known as laser-induced breakdown
spectroscopy, LEBS) is an atomic spectroscopy technique for the determination of elements
directly in solids, liquids, and gases. Radiation from a laser is tightly focused to achieve an
energy density sufficient to form an atmospheric plasma. The portion of a sample brought
in contact with this plasma is vaporized and the resultant sample atoms emit spectra
characteristic of the consistent elements. The spectral emission is quantified using a
conventional grating spectrometer and detector.
Because the laser plasma generated by a LIPS system has a temperature of 25,000° C,
it is capable of vaporizing any solid, liquid, or gas. It is most readily usable for solids and
gases, but several methods are available for the direct analysis of aqueous and organic
liquids. It has seen application to bulk metals, soil, rubber, atmospheric particulates, process
solutions, and numerous other sample types.
Since the laser beam can be transmitted by fiber optics or by telescopic lenses, and
the resulting atomic emission can be returned to the spectrometer by the same means, LIPS
is applicable to samples in remote or hostile environments. Using relatively small laser and
spectrographic components, the system can be sufficiently reduced in size and weight to be
portable.
Detection limits for solids are in the 0.1 to 10 fig/g range for many elements. LIPS
has been shown to be sensitive to chlorine, bromine and several other elements that are
difficult to analyze by ICP-atomic emission methods. Its sensitivity for mercury is
substantially poorer than the cold vapor atomic absorption and atomic fluorescence methods
often used for this element.
LIPS is not commercially available at this time. However, development programs at
several of the national laboratories may result in the transfer of LIPS technology to the
commercial sector within the next several years. Los Alamos National Laboratory has
developed several real-time LIPS monitors for beryllium and lead in air, and is currently
configuring a portable system for several elements in soil. Sandia Laboratory at Livermore
is developing a multi-element LIPS system for the real-time determination of toxic metals
in the effluent of hazardous waste incinerators. A multi-element system is expected to cost
in the same range as current ICP-atomic emission systems.
Fiber Optic Chemical Sensors
The fiber optic chemical sensor includes a fiber optic core surrounded by a protective
cladding. Additional protection around the cladding for strengthening the cable is often
employed. The principle behind the fiber optic sensor is an alteration of the light being
transmitted in the core of the fiber optic cable. This is done either through an alteration
of the cladding around the core or else through an interaction of a medium that either
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replaces or is included in the cladding, which in either case produces a change in the light
parameter in the core. This change conveys the information from the sensor. A reagent
can be included in place of the cladding and upon interaction with the analyte (e.g.,
contaminant) changes in the optical properties of the core produce the information or
signal. The signal travels at light speeds, but information acquisition is usually near-real-
time due to the fact that additional processing of the information is required. The major
advantages of the fiber optic sensors are:
remote sensing is possible
no sampling is required
the sensor occupies a low volume
it is inert to most chemical environments
FOCS readily adapt to conventional optical spectroscopy.
For purposes of measuring chemical contaminants, fiber optic sensors can be
classified according to whether they exhibit intrinsic or extrinsic properties. In the intrinsic
sensor, the chemical contaminant interacts directly with the light in the fiber. The fiber
itself responds to the chemical parameter, and modulation of the optical signal occurs while
light is guided within the fiber. Intrinsic sensors with a modified fiber cladding can perform
immunoassays and are very promising as a way to measure very low concentrations of
chemicals in complex solutions. The modified cladding-to-fiber interface acts as the sensing
element by trapping specific chemicals in complex solutions.
With the extrinsic sensor, the fiber primarily acts as a conduit to and from an
external medium that alters the properties of the transmitted or reflected light The
combination of electrochemistry with surface-enhanced Raman spectroscopy (SERS) and
fluorescence spectroscopy make extrinsic sensors which provide a sensitive means to monitor
chlorinated hydrocarbon solvents, light aromatics, and other common contaminants in vapor
and liquid phases. Modular fiber-optic spectroelectrochemical probes serve several
important functions, including: generating reagents that react with select analytes to
produce fluorescent or Raman-active products with a laser diode excitation source-
absorbing and concentrating reaction products from solution for greater sensitivity and
providing a surface that enhances Raman spectroscopic signals up to a million-fold ' The
narrow Raman bands hold promise for simplifying the identification of individual
components in complex mixtures. Data analysis methods for real-time processing of Raman
signals of contaminants are forthcoming in the near future.
Fiber optic chemical sensors (FOCS), when used for process monitoring, can present
a great savings in money and time for making measurements. For process monitoring and
control m the pulp/paper, oil and gas, and chemical processing industries, fiber optic sensors
tend to be applied in difficult niches employing remote spectroscopy or Raman spectroscopy.
Ihough other types of conventional transducers are available, adopting optical multiplexme
in the process plant enables a single control device to monitor multiple stations in fiber
optic networks.
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Fiber Optic/Fourier-Transform Infrared Probe
A fiber optic/Fourier Transform Infrared probe has been tested for the identification
of organics in containerized waste. .This is a Small Business Innovative Research Project at
Brooks Air Force Base. This project has successfully completed the phase I portion of the
development work. Phase I of the project designed probes and demonstrated that mixtures
of organics could be accurately identified. Phase H of the program will be to design,
fabricate, test, and deliver to the Air Force an IR fiber optic sensor/FTIR measurement
system for the field screening of liquid hazardous wastes. This first system will be a
benchtop unit that can be readily transported and that will be suitable for use in sheltered
field environments. It will enable a trained technician to perform rapid on-site
screening/analysis of liquid wastes stored in drums or tanks. The proposed phase II system
will include a full-function FTIR spectrometer, personal computer, complete IR spectral
analysis software package (including calibration data for waste identification), color
printer/plotter and a supply of probes with connecting fiber optic cables (Figure C-l).
Computed Tomography
Computed tomography (CT) provides quantitative, nondestructive, and noninvasive
stationary views of liquids, solids, homogeneous, and heterogenous waste drums and provides
cross-sectional and full drum volume views of contents that include density and three
dimensional information. Cross-sections are stacked to present computer generated 3-D
volume views of drum content. A CT image is a computer generated density map of waste
that is approximately proportional to the CT grey or color scale. With CT, dimensional and
volume measurements are provided based on known boundary locations. CT is useful for
measuring a reduced drum wall thickness due to corrosion, the volume of liquids or solids,
and the density of a heavy metal such as Pb or Hg. In addition, CT has a wide dynamic
range and thus has contrast resolution which is useful in imaging dense waste matrices (i.e.,
cements or soils) or differentiating substances with similar densities both of which are
difficult for real-time radiography (RTR). As an example, CT can distinguish cement from
sand or wet sand from dry sand in a drum. CT can measure the volume or the difference
in volume between cured Portland cement and water in a drum. In addition, CT can
measure the volume of liquid surrounding cement as well as the amount of liquid inside
cement pores, cavities and inside a can within a drum. CT can identify water vs. oil volumes
from density differences. CT images are available in seconds to minutes per image
depending on the scanner model and imaging techniques used as compared to real-time
acquisition with RTR. As a result, CT drum throughput can be minutes to hours per drum.
CT can determine liquid motion with time sequenced views between drum movements.
Ranges of measurement limits for typical CT systems that can image 55 to 110 gallon waste
drums are defined below. All capabilities may not be available on a single CT system
simultaneously:
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SNAP-IN FIBER OPTIC
DISPOSABLE SENSOR
3/4" O.D. STAINLESS STEELTUBE
INJECTION
MOLDED
SENSOR
OLDER
STAINLESS STEEL
HANDLE
FIBER OPTIC
SENSOR END
FLEXIBLE FIBER OPTIC
CABLE 1-10 METERS LONG
PORTABLE FTIR SPECTROMETER
w/PC COMPUTER AND SPECTRAL
SEARCH SOFTWARE
FIBEROPTIC
DIP PROBE
FIBER OPTIC
CABLE
After 213-AFR-9699-2
Figure C-l. Fiber Optic System for Drum Examination.
G-9
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CT Parameters
Fields of view
Radiation voltages
Density differences measured
Dimensional accuracy
Volumes measured
Spatial resolutions
Resolvability range
Dynamic range
Typical CT Sensitivity
up to 1.5 meters diameter by 1.5 meters tall
320 kV to 9 MV
0.1% to 10.0%
50 microns to 125 microns
1 ml to over 100 ml
0.5 to 1.5 line pairs per mm at 10% contrast
50 to 100 microns at high contrast
16-bits (65,000 data values) to 20-bits
(1 million data values)
CT cannot image moving liquid surfaces in real-time or the boundaries of phases with
the same densities. CT spatial resolution can be equal to or less than RTR.
Ion Mobility Specfrometry
The ion mobility spectrometer (IMS) is not a chemical sensor as are piezoelectrical
devices or fiber optic sensors. However, it comprises a chemical sensor system, much as the
gas chromatograph (GC) and mass spectrometer (MS). Due to its portability, it has the
potential to be a useful device for quick looks at contaminated containers. In addition, it
has excellent sensitivity, in particular when paired with a GC. Most IMS systems can only
analyze vapors. However, particles can be analyzed using a sniffing technique, by collecting
contaminants of interest on a filter. The filter is then placed at the input to the IMS, where
it is heated with ranges up to 300 degrees centigrade. The resulting vapor is then analyzed
by the IMS. For explosives, heating to a temperature of 100 degrees centigrade or less is
satisfactory for the detection of 50 to 600 picograms of explosives.
A schematic diagram of the IMS is shown below, in Figure C-2. The instrument is
basically an electric-field drift tube comprising an ionizer and reactor coupled via an
electronic shutter grid to an ion drift region. The drift tube consists of a series of stacked
cylindrical guard rings which produce a uniform electric field along the axis of the cylinder.
The entire cell is at atmospheric pressure. The sample vapors enter the ion molecule
reaction region through a short quartz tube. lonization of the carrier gas results in the
formation of certain reactant ions. These efficiently ionize a large fraction of the trace
sample molecules in the carrier gas stream, accounting for the great sensitivity of the IMS.
All the ions thus formed move down the reaction region under the influence of the voltage
gradient until the shutter grid is encountered. This grid is repeatedly opened at brief
intervals, admitting pulses of mixed ions into the drift region. As they drift, the ions in any
particular pulse (i.e., due to grid opening and closing) separate into their individual chemical
species based upon their differing intrinsic mobilities. The arrival of the individual ion
pulses at the collector electrode produces a characteristic ion arrival time spectrum. Typical
drift times range from 10 to 20 milliseconds which provides the real-time monitoring capa-
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SAMPLE AND GAS FLOWS
ALL GAS
SAMPLE
U7ml
JP-"-»-»-«-fc*
mlVol
HEATED
CARRIER GAS
100-200 ml/min
I^HP^^i^-«_r-urm
1 IONIZER
1 Ni-63
ION-MOLECULE
"REACTION REGION'
100mlVol
SENSOR CELL HOUSING AND HEATER
a. Schematic of the unit.
FAST
ELECTROMETER
AMPLIFIER
'/ HEATED
' DRIFT GAS
500 - 700 ml/min
200-
150
100-
50-
10
15
i i
20 25
drift time [ms]
b. A typical IMS spectrum with a. reactant ion peak R and two product ion peaks Pl and P2
(e.g., contaminants).
Figure C-2. Ion mobility Spectrometer.
C-ll
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bility of the IMS. Since the shutter grid is repeatedly pulsed, a continuous spectrum can be
directly viewed or summed for enhanced signal-to-noise ratio.
Ultrahigh Vacuum Analytical Techniques
While there are a number of ultrahigh vacuum (UHV) instrumental techniques that
have ben adapted for analytical applications, perhaps the best known ones are x-ray
photoelectron (XPS) (sometimes also called electron spectroscopy for chemical analysis, or
ESCA) and Auger electron spectroscopy (AES).(1A3) These techniques work under vacuums
of 10'9 to 10"11 torr and are applicable to all solid samples involving toxic chemical elements
and species that are commonly encountered at DOE sites. The samples may be powders,
wafers, chips, films, or any other solid form that is amenable to the UHV conditions. With
instrumental modifications and low-temperature cells, liquid and wet samples can also be
analyzed; however, analyses of this kind are best performed using a dedicated instrument.
Both techniques mirror approximately the top 10-30 Angstroms of the surface of the sample
being studied.
as
X-ray photoelectron and Auger spectroscopy have a number of advantages
analytical techniques. First, both techniques can be used in the survey scan mode to give
a quick compilation of the elements that are present in a particular sample. Toxic heavy
metal samples such as copper, lead, and chromium are easily detected using the two
techniques. Equally spectroscopically visible are anionic polyatomic waste species such as
phosphates and nitrates, along with other waste non-metallic species such as iodides.
The second advantage of the two techniques is that they can be used not only to
detect the presence of an element but also to study its chemistry in detail when the spectra
are obtained in the high resolution mode, giving such information as the oxidation state of
the central element as well as the functional group that might contain it. There are several
examples of this, including the ability to distinguish cobalt(II) from cobalt(III),
chromium(III) from chromium(VI), and sulfur(-II) from sulfur(VI). In this last case, a
researcher can thus easily differentiate between a sulfide and a sulfate. Additionally, the
chemical and electronic state of other elements associated with the sulfur species can most
likely be determined.
The third advantage of the two techniques is that, using the appropriate instrumental
setup, they can complement one another to a very great degree. Specifically, using a
standard x-ray anode radiation source for soft x-rays that are typically used to perform the
normal x-ray photoelectron experiment, a researcher can also observe the Auger electron
spectrum that is concomitantly generated by the x-radiation; as a result, both the x-ray
photoelectron and Auger spectra are contained in the form of a combined spectrum. This
allows a direct comparison of the two spectra of a sample without worrying about
experimental aspects that might normally cause difficulty in the interpretation of the data,
one possibility being the problem of "charging." By being able to look at the x-ray
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photoelectron and Auger spectra in the same printout, this problem can be eliminated and
combined spectral parameters can be generated for a particular element of interest.
The fourth advantage of the two techniques is that they can be used to study samples
that are not homogeneous on the surface. As mentioned above, the techniques reflect the
near-surface of a sample that is being studied, thus allowing a researcher to study
contaminants that may have attached themselves to the original species. Both x-ray
photoelectron and Auger spectroscopy can be used to perform point analysis on samples,
meaning that locations of a few microns in area on a sample can be studied. This is most
easily accomplished using Auger spectroscopy under the conditions in which an electron
beam is used to generate the Auger spectrum; it is not so easily effected using x-ray
photoelectron spectroscopy, since the throughput of samples is reduced dramatically.
Finally, several drawbacks do exist for using UHV techniques for analysis. First,
there is the fact that samples are, practically speaking, restricted to solids. Second, the
establishment and breaking of vacuum is costly in time, restricting the number of samples
one can quickly run. Third, one must check to see if any radiation damage occurs as a
function of time; this can alter the interpretation of the data as they relate to chemical state
information such as oxidation state. Still, the UHV techniques provide a wealth of
knowledge about a wide variety of toxic elemental species.
Neutron Techniques for Specific Alpha Measurement
Specific alpha activity is the rate of alpha particle emission per weight, measured in
curies per gram. The present limit for distinguishing low-level waste (LLW) from
transuramc waste (TRU) is 100 nanocuries per gram. The difficulty with measuring the
specific alpha activity is that the mean free path of an alpha particle in almost any medium
is very short. In air, the mean free path is only a few centimeters. For drum-sized
containerized waste, essentially none of the emitted alpha particles would reach an alpha
detector. ^
Specific alpha activity is important for two reasons. First, it directly affects the
generation of gas by radiolysis. Gas generation is important because it can affect the
physical integrity of the container. Also, alpha activity is typically associated with a certain
class of radionuclides which have a severe environmental impact. The most notable are the
isotopes of plutonium. Leaching of these isotopes out of the waste container could cause
a significant environmental impact:
Because of the short mean free path of alpha particles, alpha activity is usually
measured indirectly. The most common approach is to exploit the alpha-neutron reaction-
an alpha interacts with a moderate atomic number (Z) material which then gives off a
neutron (4). This nuclear reaction is common for many oxidizing materials, such as oxygen
or fluorine. In most waste cases the nuclear material, such as plutonium, is in its oxidized
rather than metallic form (plutonium is a strong reducing agent). Therefore, inferring the
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alpha activity from the neutron emission is a common and effective technique. In the case
of LLW waste assay, it is particularly reliable because the presumption is that small
quantities of waste are involved, so that the plutonium (or other alpha emitting material)
is naturally oxidized.
The technique that is used to determine specific alpha activity from the induced
neutron emission is passive neutron totals counting (4,5,6). Typical instruments are the
passive counting aspect of the californium shuffler, and the passive add-a-source counter.
The passive-active neutron differential die-away counter can also make this passive neutron
measurement. Because there are other sources of neutrons besides the alpha-n reaction,
the total neutron counting technique generally provides only an upper bound to the alpha
activity rate. In addition, the reaction cross sections for alpha-n reactions vary for different
oxidizing materials. This technique is typically used as a "screening" measurement; it
determines the upper bound of the alpha activity rate rather than a precise measurement
(4,6).
A more accurate but somewhat less sensitive method is passive coincidence counting
(5,6). Passive coincidence counting counts the number of simultaneous neutron pairs.
Neutron pairs are a specific signature of a nuclear fission, so this measurement determines
the amount of fissionable material. Because the fissionable isotopes are also typically those
that decay by alpha emission, the alpha activity can also be inferred. For example, one of
the most common alpha emitters found in nuclear waste is plutonium, which also has a
significant spontaneous and induced fission component. By counting the neutron
coincidences, the fission rate can be determined. Knowing that plutonium is the dominant
source of alpha emission, the alpha rate can be inferred directly from the nuclear decay
properties of plutonium. Passive coincidence counting systems for 55 gallon drums can
operate down to the 10 nanocuries per gram level in well-shielded environments (the
sensitivity depends on the background count rates). This sensitivity is well below the 100
nanocurie per gram regulatory limit for distinguishing low level and TRU waste.
The passive coincidence measurement can be extended to neutron multiplicity
counting (6). Multiplicity counting counts simultaneous neutron events consisting of
multiple neutrons, extending the coincidence concept of counting neutron pair events. This
technique can reduce many of the uncertainties from matrix effects, additional isotopes such
as curium, and detector efficiencies.
Another extension of the passive coincidence measurement is the add-a-source
technique (5). The add-a-source technique provides a correction to a passive multiplicity
or coincidence counting for matrix induced errors. The passive measurement is significantly
less sensitive to matrix effects than active measurements, but the induced bias error can be
reduced further. The add-a-source method introduces a known source with a neutron
spectrum similar to fission neutrons, and measures the effect of the waste drum matrix on
the source neutrons. The effect on the source is assumed to be the same as the matrix
C-14
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effect on the sample. The passive measurement of the sample is corrected using the
measured effect on the added source.
The third principle measurement of specific alpha activity is done by active neutron
interrogation (7,8,9,10,11). The active measurement interrogates the sample with a neutron
source. Typically, a neutron generator is used in the case of the passive active neutron,
differential die-away (PAN/DDA) system and a californium source is used in the
PAN/californium shuffler. In both cases fissions are induced in the.sample material and the
resulting fission neutrons are measured. The PAN/DDA system measures prompt fission
neutrons and the shuffler measures delayed neutrons. In both instances the measured
neutrons are proportional to the amount of fissionable material in the sample. The isotopes
that are specific to this measurement are the odd isotopes of plutonium (^'Pu M1Pu
predominantly) and ^U. '
For the active neutron measurement two assumptions are made: the first is that the
alpha-emitting material is essentially all plutonium. For example, the measurement will be
in error if there are significant quantities of americium present, which decays by alpha
emission but does not have a significant induced fission cross section. Americium is
common to the plutonium production cycle. The second assumption is that the isotopic
distribution of the plutonium is known. (Typically, the isotopic distribution is assumed to
be weapons-grade material for DOE complex waste.) For certain samples with
noninterfering matrices, the isotopic distribution of plutonium can also be measured using
gamma-ray techniques, such as the segmented gamma scanner. Although active techniques
are more dependent on the underlying assumptions about the material distribution, they are
also the most sensitive. However, active techniques are considerably more sensitive to the
matrix material than passive techniques.
An important variant of the PAN/DDA system is the combined thermal-epithermal
neutron system (CTEN) (11). The CTEN system now under development addresses one of
the important limitations of the PAN/DDA system, namely that the interrogation is done
with thermal neutrons. The penetration of thermal neutrons is very small, roughly a few
hundred microns in metallic plutonium. If significant quantities of plutonium are present
in a sample, it is possible that the active PAN/DDA system will significantly underestimate
the quantity. The CTEN directly addresses this problem.
Because the active assay instruments can also make a passive measurement
occasionally the active interrogation is combined with a passive multiplicity or coincidence
measurement. The total neutron counts are also included in the coincidence or multiplicity
counting. The most common instruments are the passive multiplicity counter with add-a-
source matrix correction, the californium shuffler, and the differential die-away system.
The choice of which system to use depends somewhat on the anticipated application
If the waste drum must be characterized for the TRU/LLW distinction only, passive
multiplicity with add-a-source is the most robust measurement. If a highly sensitive
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measurement is required, then the PAN/DBA system has the required sensitivity. If
uranium is anticipated in the source stream, then the PAN shuffler measurement is perhaps
the most appropriate. Other active and passive neutron-based instruments are also under
development which may alleviate some of the problems discussed here.
Immunochemistry
Immunochemistry includes the techniques immunoaffinity, chromatography, and
immunoassay. Sample preparations based on immunoaffinity take advantage of the
attraction between an antibody and a specific analyte. The procedure has potential for
cleanup of complex samples like soils and sludges. By rinsing a sample over an antibody-
treated surface, chemists can isolate particular compounds that adhere to the antibody. The
isolated compound is then eluted from the immobilized antibody and is ready for analysis
by chromatography or by immunoassay. One common immunoassay is the enzyme-linked
immunosorbent assay (ELJSA). In this technique, the selectivity of the antibody for the
analyte and the resultant antibody-analyte complex is the basis for the specificity of
immunoassays.
Immunoassay techniques can be incorporated within fiber optic systems to facilitate
analysis of organic contaminants. Antibodies that specifically bind to the substance to be
detected are trapped on an optical fiber. The fiber is placed in a small column, where the
polluted sample is poured, and the pollutant binds to the trapper antibody. A second
antibody, tagged with a fluorescent compound, is put into the chamber to bind to the
pollutant, and light pulses measure the amount of reaction. The color intensity is related
to the sample analyte concentration. This technology has been developed to test for
contaminants in food, water, and soil, and on contaminated surfaces. Fiber optic
immunosensors have been developed to detect drugs and explosives at the ppb threshold.
Raman Spectroscopy
Raman spectroscopy detects the vibrational characteristics of molecules of a
contaminant after intense monochromatic excitation, typically provided by an ultraviolet
(UV), visible, or near-infrared (NIR) laser. The inelastic scattering caused by the
irradiation is representative of the induced polarization of bonding electrons due to
vibrational motion of the molecule (i.e. Raman effect). It has been used to detect VOCs
in soil and hi the vadose zone. Raman spectroscopy, combined with fiber optic techniques,
has been found to be particularly useful for detecting and monitoring VOCs hi groundwater
or remote locations. Fiber optic probes are used to perform surface-enhanced Raman
Spectroscopy (SERS) of analyte molecules absorbed on the surface of an electrode at the
end of the probe assembly. Real tune monitoring of carbon tetrachloride and TCE have
been demonstrated.
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Piezoelectric Sensors
Piezoelectricity is produced by applying pressure to a crystal of dielectric material.
The applied pressure deforms the crystal lattice causing a separation of charges which
results in an electrical potential. Application of an electrical potential (voltage) to the
crystal produces physical distortions and the crystal vibrates mechanically for short periods
until physical equilibrium is attained. Several types of piezoelectric sensors are available
including the surface acoustic wave (SAW) sensor. The SAW sensor is a mass sensitive
device and uses a shift in resonant frequencies as the indicating signal, through coatings that
chemically sorb analytes. The SAW is a microsensor and occupies a volume smaller than
one millionth of a liter. SAW sensors have found wide application because of their small
size, ruggedness, low cost, electronic output, sensitivity, and adaptability to a wide variety
of vapor phase analytical problems (e.g. VOCs).
i
Prompt Gamma Neutron Activation Analysis
This is a non-invasive method whereby interrogation of containerized waste is
possible through the interaction of neutrons directed at the sample (e.g. contaminant) being
analyzed. The PGNAA performs an elemental analysis of the sample. The neutron initiates
a nuclear reaction and there is an instantaneous gamma emission from the sample. The
high-energy gamma ray is the contaminant elemental signature. The energy levels give a
better signal-to-background ratio than conventional instrumental neutron activation analysis.
The per sample costs are lower than conventional laboratory analysis and the analysis results
are available in minutes. There is no sample collected for shipping and disposal. The
PGNAA is also configurable for a field survey vehicle. PGNAA is reported to be effective
throughout the periodic table. Elements such as U, Th, Cd, Cu, Pb, Hg, As, Ba, Cl and Cr
have been detected with PGNAA at sensitivities below the limiting regulatory requirement.
Electrochemical Sensors
Electrochemical sensors have been developed to measure ions and gases. They are
classified as potentiometric, amperometric, or conductimetric according to the influence of
the analyte in the electrochemical cell. To be detected, a gas must elicit an electrochemical
response. Most VOCs are electrochemically inactive and must be converted to electiroactive
reaction products (e.g. CO, C12, HC1, HF) using pyrolysis techniques prior to detection. The
electrochemical sensors are fast, sensitive, miniature, and inexpensive. Response and
recovery times are most often less than one minute and the interaction of the analyte and
surface is usually completely reversible. Detection levels range from 500 ppb to 1000 ppm
and are dependent on pre-detection operations.
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Pulsed Fast Neutron Analysis (PFNA)
PFNA is a non-intrusive system that uses a rapidly-pulsed beam of high-energy
neutrons to induce element-specific gamma-ray signatures of materials inside a sample. This
method will detect hazardous elements such as mercury and chlorine, and hazardous
compounds such as PCBs. Elemental maps are formed for nitrogen, oxygen, chlorine,
silicon, aluminum, iron, and other elements of interest. By combining these maps, it is
possible to screen for particular hazardous materials. PFNA has veiy broad applicability
in waste treatment and disposal where elemental composition and spatial distribution
influence operational decisions.
References
1.
2.
3.
4.
5.
6.
7.
8.
CD. Wagner, W.M. Riggs, L.E. Davis, J.F. Moulder, and G.K Mullenberg, editors.
1979. Handbook of x-ray photoelectric spectroscopy. Perkin-Elmer Corporation.
L.E. Davis, N.C. MacDonald, P.W. Palmberg, G.E. Riach, and R.E. Weber, editors.
1976. Handbook of Auger electron spectroscopy. Perkin-Elnier Corporation.
D.L. Perry. 1991. Application of combined x-ray photoelectron/Auger spectroscopy
to studies of inorganic materials. In: D.L. Perry, editor, Application of Analytical
Techniques to the Characterization of Materials. Plenum Press.
D. Reilly, N. Ensslin, H.A Smith Jr., and S. Kreiner, Editors. 1991. Passive
nondestructive assay of nuclear materials. NUREG/CR-5550. US Nuclear Regulatory
Commission, Washington, DC.
H.O. Menlove. 1992. Accurate plutonium waste measurements using the Cf-252
Add-a-Source technique for matrix corrections. LA-UR-92-2119. Los Alamos
National Laboratory, Los Alamos, NM.
M.S. Krick, S.C. Bourret, N. Ensslin, J.K. Halbig, W.C. Harker, D.G. Langer, H.O.
Menlove and J.E. Stewart. 1993. Passive thermal neutron multiplicity counting
developments at Los Alamos. LA-UR-93-1460. Los Alamos National Laboratory,
Los Alamos, NM.
NJ. Nicholas, K.L. Coop, and RJ. Estep. 1992. Capability and limitation study of
the DDT Passive-Active Neutron Waste Assay instrument. LA-12237-MS. Los
Alamos National Laboratory, Los Alamos, NM.
P.M. Rinard, E.L. Adams, H.O. Menlove, and J.K. Sprinkle, Jr. 1992. The
nondestructive assay of 55-gallon drums containing uranium and transuranic waste
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9.
10.
11.
using passive-active shufflers. LA-12446-MS. Los Alamos National Laboratory Los
Alamos, NM.
J.T. Caldwell, R.D. Hastings, G.C. Herrere, W.E. Kunz, and E.R. Shunk. 1986. The
Los Alamos second-generation system for passive and active neutron assays of drum-
size containers. LA-10774-MS. Los Alamos National Laboratory, Los Alamos, NM.
P.M. Rinard. 1991. Shuffler instruments for the nondestructive assay of fissile
materials. LA-12105. Los Alamos National Laboratory, Los Alamos, NM.
K.L. Coop. 1989. A combined thermal-epithermal neutron interrogation device to
assay fissile materials in large waste containers, in Proceedings of the llth Annual
ESARDA Symposium on Safeguards and Nuclear Material Management
Commission of the European Communities Report EUR 12193 EN, Luxembourg
C-19
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APPENDIX D
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Appendix D
Advanced Technologies for Process
Monitoring and Control
Gary Leatherman
Automating the Monitoring of the Waste Treatment Process
Adaptation of existing automation hardware and software for monitoring the
processing of the mixed low-level waste (MLLW) should be investigated. Waste water
treatment systems have been automated and some of this technology may be appropriate
for MLLW characterization for treatment. Typically, new sensors and controller hardware
are added to an existing distribution control system (DCS) of the waste treatment area (1).
An existing DCS could be modified to handle MLLW treatment requirements. In this
automation, operator display terminals can be placed where needed. A flexible system that
uses standard hardware and software components can be installed and maintained by in-
house personnel.
Personal computers (PC) could be the ideal engine for distributed control.
Connected to generic input and output devices wired directly to sensors and actuators, the
PC could provide a graphical display of process monitoring information, execute control
algorithms, and provide data logging and reporting. PCs can be linked together through low
cost networking technology enabling the transfer of information to each other.
The majority of PC-based automation software include the ability to acquire and
display real time data in a variety of formats: trend charts, bar charts, numerically, etc. The
monitoring instruments should use an interface standard so that linkage to the automated
system is easily accomplished.
D.ata reporting and archiving requirements in treatment of MLLW will require
specific information mainly because the format and contents of the reports are mandated
by regulatory agencies (e.g., EPA and state regulators). Monitoring data acquired from the
process needs to be sent directly to spreadsheets in real time, so that calculations are up to
the minute and reports show an instantaneous snapshot of the operating process. Modular
software is best because new features and functions can be purchased separately as
needed.
Laptop computers have become commonplace for the engineers called on to diagnose
and solve a variety of manufacturing or process related problems. Usually an external
device is needed that can digitize signals from sensors and store the data directly in the
D-l
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laptop's file. The use of these devices would help expedite the characterization for
processing of the MLLW and be more cost effective than a mainframe computer.
Smart Sensors
Smart sensors/transducers are defined as sensing devices with built-in intelligence.
This intelligence usually results in some form of digital signal processing. Smart sensor
design is evolving in several directions. These devices show promise for the monitoring of
MLLW treatment processes.
The initial focus was on digital processing of the sensor output signal to improve the
accuracy of temperature compensation and normalization. Later designs incorporated
enhanced digital features such as remote communication and addressability. The most
recent developments include the integration of a manufacturing test system interface that
allows batch mode fabrication of transducers. This advance significantly reduces
manufacturing cost and significantly improves the price/performance ratio (2).
Smart sensor process monitoring control applications have been introduced by
industry recently. In one application the process control transmitter used three monitoring
sensor input signals: differential pressure, temperature and static pressure. In addition to
basic signal conditioning functions, the software included the static pressure compensation
necessary for process control applications. The process control transmitter design
incorporated several key advanced digital features such as remote calibration over a 400:1
range, addressability and diagnostics.
The evolution of smart sensor and transducer design is bringing outstanding products
to market. While they represent a small market segment at present, it is expected that their
share will grow quite rapidly as they gradually replace classical analog designs. Several
factors confirm this trend. The growing demand for communication and networking
capabilities cannot be satisfied with analog transducer designs. Industrial applications of
single chip smart transducers can be expected in the current decade, with further
price/performance improvements; single chip smart sensor developments have already been
reported by research and academic centers. As a result of increasing volumes and levels of
integration for smart transducers, the conversion of a major sector of the existing low cost
sensor market can be expected.
References
1. R. Kok. Sept. 1993, PC-based Systems Aid Process Control. Env. Prot.
D-2
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2. N. Najafi. March 1993. A Multi-element Gas Analyzer utilized in a Smart Sensing
System. Proc. Sensors Expo West, San Jose, Ca.
D-3
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APPENDIX E
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Appendix E
Instrumentation for Waste Form Characterization
E-l
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Sampling and Sample Preparation
Description: Punch Cores
Application - Sampling technique for solid materials.
Summary - Solid materials such as final waste forms including sludges, concretes can be
sampled by collecting cores from core punching equipment.
Costs:
Instrument/Equipment.
Per Sample
or Operating Costs/yr
Capability and Limitations:
Advantages -
Commercial equipment is available.
Limitations -
May not be applicable to metallic final waste forms.
Accuracy routinely achieved/expected under these conditions
N/A
Status: Accepted technology
E-2
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Sampling and Sample Preparation
Description: Microwave Assisted Acid Digestion
Application - Solid matrix materials can rapidly digested for the determination of inorganic
elements.
Summary - A representative sample of a solid matrix material including final waste forms
such as sludge and concrete is digested with concentrated acid in a closed teflon vessel using
microwave heating with a suitable microwave unit.
Costs:
Instrument/Equipment S25-50K
Per Sample $25
or Operating Costs/yr
Capability and Limitations:
Advantages -
Effective in digesting and extracting trace elements from soils and complex matrices prior
to analysis. This is an emerging technology that shows much promise in reducing the
amount of work produced in sample analysis as well as increasing the quality of the data
obtained.
Limitations -
May not be applicable to the digestion of metallic final waste form samples.
Accuracy routinely achieved/expected under these conditions -
N/A
Status: Accepted technology
E-3
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Laboratory Characterization and Analysis
Description: Flame Atomic Absorption (FAA) Spectrophotometry
Application - A technique for the determination of metals and metalloids. Samples must
be subjected to an appropriate dissolution step prior to analysis.
Summary - Prior to analysis, samples must be solubilized or digested using appropriate
Sample Preparation Methods. Atomic absorption spectrophotometry is based on the
absorption of radiation from a line spectral source of the analyte being determined by
ground state analyte atoms. In FAA either a nitrous-oxide/acetylene or air acetylene flame
is used as an energy source for dissociating the aspirated sample into the free atomic state
making analyte atoms available for absorption of light. Absorbance is measured as a
function of analyte concentration.
Costs:
Instrument/Equipment $60K
Per Sample $25-50/determination
or Operating Costs/yr
Capability and Limitations:
Advantages -
It is a standard, well-accepted methodology for sensitive and selective determination of
single elements, metals and some metalloids.
Limitations -
Samples must be solubilized. If proper flame and analytical conditions are not used,
chemical and conization interference can occur.
Accuracy routinely achieved/expected under these conditions -
3-5%
Status: Accepted technology
E-4
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Sampling and Sample Preparation
Description: Sample Mixing and Homogenization
Application - Mixing and homogenization of final waste form samples.
Summary - Samples of the final waste materials are collected for characterization and
assessment of product material. Samples will need to be prepared for analysis.
Costs:
Instrument/Equipment S300K
Per Sample
or Operating Costs/yr
Capability and Limitations:
Advantages -
Equipment for mixing and homogenizing solid materials is available.
Limitations -
Equipment has not been specifically designed for use with radioactive samples.
Accuracy routinely achieved/expected under these conditions -
N/A
Status: Accepted technology
E-5
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Sampling and Sample Preparation
Description: Toxicity Characterization Leaching Procedure (TCLP)
Application - The TCLP is designed to determine the mobility of both organic and inorganic
analytes present in liquid, solid, and multiphasic wastes.
Summary - The particle size of the solid waste form is reduced, if necessary. The solid is
extracted with an amount of extraction fluid equal to 20 times the weight of the solid phase.
The extraction fluid employed is a function of the alkalinity of the solid phase of the waste.
Following extraction, the liquid extract is separated from the solid phase by filtration
through a 0.6 to 0.8 /im glass fiber filter. The extraction fluid is analyzed.
Costs:
Instrument/Equipment S2-3K
Per Sample
or Operating Costs/yr
Capability and Limitations:
Advantages -
"Satisfactory" test if this procedure is meaningful for the prescribed disposal conditions.
Limitations -
The test may not be meaningful for the prescribed disposal conditions. Potential
interferences may be encountered during analysis.
Accuracy routinely achieved/expected under these conditions -
N/A
Status: Accepted technology
E-6
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Laboratory Characterization and Analysis
Description: Cold Vapor Atomic Absorption (CVAA) Spectrophotometry
Application - A technique for the determination of mercury. Samples must be subjected to
an appropriate dissolution step prior to analysis.
Summary - Prior to analysis, solid or semi-solid samples must be prepared according to the
appropriate dissolution procedures. The CVAA technique is based on the absorption of
radiation at the 253.7-nm wavelength by the mercury vapor. The mercury is reduced to the
elemental state and aerated from solution in a closed system. The mercury vapor passes
through a cell positioned in the light path of an atomic absorption spectrdphotometer.
Absorbance (peak height) is measured as a function of mercury concentration.
Costs:
Instrument/Equipment S25-30K
Per Sample $50 -
or Operating Costs/yr
Capability and Limitations:
Advantages -
Highly sensitive and selective for mercury. In widespread routine use.
Limitations -
Limited to the determination of mercury. High concentrations of sulfide, copper, chloride
and certain volatile organic compounds may cause interferences.
Accuracy routinely achieved/expected under these conditions -
5-10%
Status: Accepted technology
E-7
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Laboratory Characterization and Analysis
Description: Graphite Furnace Atomic Absorption (GFAA) Spectrophotometry
Application - A technique for the determination of metals and metalloids. Samples must
be subjected to an appropriate dissolution step prior to analysis.
Summary - Prior to analysis, samples must be solubilized or digested using appropriate.
Sample Preparation Methods. Atomic absorption spectrophotometry is based on the
absorption of radiation from a line spectral source of the analyte being determined by
ground state analyte atoms. In GFAA an electrically heated graphite furnace is used as an
energy source to dissociate the sample into the free atomic state making atoms available for
absorption of light. Absorption, either peak height or peak area, is measured as a function
of the analyte concentration.
Costs:
Instrument/Equipment S75K
Per Sample $50-100/determination
or Operating Costs/yr
Capability and Limitations:
Advantages -
It is a standard, well-accepted methodology for sensitive and selective determination of
single elements, metals and some metalloids.
Limitations -
Samples must be solubilized. Because the technique is so sensitive, interferences can be a
problem.
Accuracy routinely achieved/expected under these conditions -
5-10%
Status: Accepted technology
E-8
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Laboratory Characterization and Analysis
Description: Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES)
Application - A technique for the determination of metals and metalloids. Samples must
be subjected to an appropriate digestion prior to analysis.
Summary - Prior to analysis, samples must be solubilized or digested using appropriate
Sample Preparation Methods. The technique measures element-emitted light by optical
spectrometry. Samples are nebulized and the resulting aerosol is transported to the plasma
torch. Element-specific atomic-line emission spectra are produced by a radio-frequency
inductively coupled plasma. The spectra are dispersed by a grating spectrometer, and the
intensities of the line are monitored by photomultiplier tubes. Depending on the instrument
analytes can be determined simultaneously or sequentially.
Costs:
Instrument/Equipment S150-200K
Per Sample $100-150
or Operating Costs/yr
Capability and Limitations:
Advantages -
It is a standard, well-accepted methodology. It allows multielement determinations.
Limitations -
Samples must be in solution. Background and spectral interferences can occur: appropriate
corrections must be made.
i
Accuracy routinely achieved/expected under these conditions -
3-5%
Status: Accepted technology
E-9
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MLLW Workshop - Final Waste Forms
Sampling Point: Final Waste Forms
Technique Name: Laboratory Characterization and Analysis
Description: Inductively Coupled Plasma - Mass Spectroscopy (ICP-MS)
Application - Inductively coupled plasma-mass spectrometry (ICP-MS) is a technique which
is applicable to flg/L, concentrations of a large number of elements in water and wastes after
appropriate sample preparation steps are taken.
Summary - Prior to analysis, samples which require total values must be digested using
appropriate sample preparation methods. The technique measures ions produced by a radio-
frequency inductively coupled plasma. Analyte species originating in a liquid are nebulized
and the resulting aerosol transported by argon gas into the plasma torch. The ions produced
are entrained in the plasma gas and introduced, by means of a water-cooled interface, into
a quadrupole mass spectrometer. The ions produced in the plasma are sorted according to
their mass-to-charge ratios and quantified with a channel electron multiplier.
Costs:
Instrument/Equipment S250-300K
Per Sample $100-200
or Operating Costs/yr
Capability and Limitations:
Advantages -
It has multielement capability. Isotopic analyses can be performed.
Limitations -
Solution samples should have low dissolved solids. Interferences for background ions from
the plasma gas, reagents, and sample matrix constituents must be corrected.
Accuracy routinely achieved/expected under these conditions -
0.2-0.5%
Status: Evolving technology
E-10
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APPENDIX F
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Appendix F
Bibliography for Characterization
of Low-Level Waste
Clare Gerlach
Introduction to Bibliography
A series of institutions were searched via INTERNET on-line computer catalogs to
establish this appendix. References listed here are from the libraries of the University of
Nevada, Las Vegas, the University of Texas, Austin, the University of Waterloo, Ontario,
the Massachusetts Institute of Technology, and the Dialog Database.
Each system has its own individual search software. Some can only search one word
at a time, others can use combinations of multiple one-word searches, and others can search
multiword phrases. For the present search tens of search combinations were employed using
allowable combinations of the one-word search terms: low-level, waste, radioactive
containerized, characterization, disposal, treatment, mixed, nuclear, medium-level, dumping'
and sludge. Thus, the references are not limited to mixed waste or low-level waste!
Nonetheless, the techniques described may be useful for MLLW.
This is by no means a comprehensive bibliography, but it should provide the
interested reader with a broad background in the topic and lead to identification of
additional references.
F-l
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Information Available Through the Government Documents Repositories
at the University of Nevada System
Current Sudoc = Library Call Number for the University of Nevada System
GPO Item No. = U.S. Government Printing Office Item Acquisition Number
MF = Microfiche
Current SuDoc: Y 3.N 88:25/4162
GPO Item No.: 1051-H-ll (MF)
Title: Survey of statistical and sampling needs for environmental monitoring of commercial
low-level radioactive waste disposal facilities / prepared by L.L. Eberhardt, J.M. Thomas.
Description: 1 v. (various pagings) : ill. ; 28 cm.
Author: Eberhardt, L. L. (Lester Lee)
Date: 1986
Current SuDoc: E 1.28:ICP-1187
GPO Item No.: 429-T-4 (MF)
Title: Methods evaluation for the continuous monitoring of carbon-14, krypton-85, and
iodine-129 in nuclear fuel reprocessing and waste solidification facility off-gas / SJ.
Fernandez et al.
Author: Idaho National Engineering Laboratory.
Description: v, 28 p. : ill. ; 28 cm.
Date: 1979
Location: UNR Government Publications
Current SuDoc: E 1.28:ICP-1174
GPO Item No.: 429-T-4 (MF)
Title: Methods evaluation and development for the monitoring of technetium-99 and
selenium-79 in nuclear fuel reprocessing and waste solidification facility off-gas / by S. J.
Fernandez, R. C. Girth; prepared for the Department of Energy, Idaho Operations Office
Author: Fernandez, S. J. (Steven Joseph)
Description: iii, 27 p. : ill., graphs ; 28 cm.
Date: 1978
Current SuDoc: EP 1.89/2:W 28/12
GPO Item No.: 431-L-12
Title: Securing containerized hazardous wastes with welded polyethylene encapsulates
Author: H.R. Lubowitz et al.
Description: 3, [1] p. : ill. ; 28 cm.
Date: 1981
F-2
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Current SuDoc: EP 6.10/7:77-3
GPO Item No.: 431-1-61
Title: Characterization of selected low-level radioactive waste generated by four commercial
light-water reactors.
Author: Dames & Moore.
Description: 77 p. in various pagings : ill. ; 28 cm.
Series: United States. Environmental Protection Agency. Office of Radiation Programs.
Technical note - Office of Radiation Programs; ORP/TAD-77-3.
Date: 1977
Current SuDoc: Y 3.N 88:25/5343
GPO Item No.: 1051-H-ll (MF)
Title: Radionuclide characterization of reactor decommissioning waste and spent fuel
assembly hardware: progress report
Author: D.E. Robertson et al.
Description: 1 v. (various pagings) : ill. ; 28 cm.
Date: 1991
Current SuDoc: GA 1.13:RCED-87-103 FS
GPO Item No.: 546-D (MF)
Title: Nuclear waste : status of DOE's nuclear waste site characterization activities : fact
sheet for the chairman, Subcommittee on Energy-and Power, Committee on Energy and
Commerce, House of Representatives / United States General Accounting Office.
Description: 41 p. : ill. ; 28 cm.
Date: 1987
Current SuDoc: E 1.28:DP-1483
GPO Item No.: 429-T-4 (MF)
Title: Chemical characterization of SRP waste tank sludges and supernates
Author: Gray, L. W. (Lucinda Wentworth), M. Y. Donnan, B. Y. Okamoto
Description: 140 p. : ill., graphs ; 27 cm.
Date: 1979
Current SuDoc: Y 3.N 88:25/5343
GPO Item No.: 1051-H-ll (MF)
Title: Radionuclide characterization of reactor decommissioning waste and spent fuel
assembly hardware: progress report
Author: D.E. Robertson et al.
Description: 1 v. (various pagings) : ill. ; 28 cm.
Date: 1991
F-3
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Current SuDoc: E 1.28/15:
GPO Item No.: 474-B-8
Title: Annual water quality data report for the Waste Isolation Pilot Plant.
Description: v. : ill., maps ; 28 cm.
Date: 1986
Current SuDoc: Y 3.N 88:25/4938
GPO Item No.: 1051-H-ll (MF)
Title: Occupational radiation exposures associated with alternative methods of low-level
waste disposal Author: Herrington, W. N., R. Harty, S.E. Merwin.
Description: 1 v. (various pagings) : ill. ; 28 cm.
Date: 1987
Current SuDoc: C 13.58:81-2409
GPO Item No.: 247-D (MF)
Title: Bibliography of literature on underground corrosion of metals and alloys considered
for use in the construction of containers for nuclear waste
Author: Sanderson, B. T., J. Kruger; prepared for U.S. Department of Energy.
Description: 43 p. ; 28 cm.
Series: NBSIR ; 81-2409
Date: 1982
Current SuDoc: Y 4.En 2:S.hrg. 100-293
GPO Item No.: 1040-A, 1040-B (MF)
Title: Civilian radioactive waste disposal : hearings before the Committee on Energy and
Natural Resources, United States Senate, One hundredth Congress, first session, on S. 1007
... S. 1141... S. 1211... S. 1266 ... S. 1428, July 16 and 17, 1987.
Author: United States. Congress. Senate. Committee on Energy and Natural Resources.
Description: iii, 618 p. : ill., maps ; 24 cm.
Series: United States. Congress. Senate. S. hrg. ; 100-293.
Date: 1987
Current SuDoc: Y 3.N 88:25/4519
GPO Item No.: 1051-H-ll (MF)
Title: Technology, safety, and costs of decommissioning reference nuclear fuel cycle facilities
: classification of decommissioning wastes
Author: Elder, H. K.
Description: 32 p. in various pagings : ill. ; 28 cm.
Date: 1986
F-4
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Current SuDoc: E 1.28:PNL-2690
GPO Item No.: 429-T-4 (MF) ;
Title: Conceptual design of a nuclear waste vitrification facility
Author: D. E. Larson et al. Pacific Northwest Laboratory.
Description: viii, 57 p. : ill. ; 28 cm.
Date: 1978
Current SuDoc: E 1.28:PNL-3129
GPO Item No.: 429-T-4 (MF)
Title: Environmental control aspects for fabrication, reprocessing, and waste disposal of
alternative LER and LMBR fuels
Author: Nolan, A. M., M. A, Lewallen, G. W. McNair.
Description: ca 100 p. in various pagihgs : ill. ; 28 cm.
Date: 1979
Current SuDoc: E 1.28:PNL-3038
GPO Item No.: 429-T-4 (MF)
Title: Technical summary, Nuclear waste vitrification project
Author: E. J. Wheelwright et al. Pacific Northwest Laboratory.
Description: viii, 67 p. : ill. (some col.) ; 28 cm.
Date: 1979
Current SuDoc: E 1.28:DP-1535
GPO Item No.: 429-T-4 (MF)
Title: Small-scale, joule-heated melting of Savannah River Plant waste glass
Author: Plodinec, M. J., P. H. Chismar.
Description: 30 p. : ill. ; 28 cm.
Date: 1979 ;
Current SuDoc: E 1.28:DP-1498
GPO Item No.: 429-T-4 (MF)
Title: Evaluation of glass as a matrix for solidifying Savannah River Plant waste : properties
of glasses containing Li40 ';-.,.-• « ,
Author: Plodinec, M. J., J. R. Wiley.
Description: 40 p. : ill., graphs ; 28 cm.
Date: 1979 ,
Current SuDoc: E 1.28:DP-1488
GPO Item No.: 429-T-4 (MF)
Title: Electrical resistivities of glass melts containing simulated SRP waste sludges
Author: Wiley, J. R. (John Robert), prepared for the U.S. Department of Energy
Description: 23 p. : ill., graphs ; 28 cm.
Date: 1978
F-5
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Current SuDoc: E 1.28:DP-1483
GPO Item No.: 429-T-4 (MF)
Title: Chemical characterization of SRP waste tank sludges and supernates
Author: Gray, L. W. (Lucinda Wentworth), M. Y. Donnan, B. Y. Okamoto; prepared for the
U.S. Department of Energy
Description: 140 p. : ill., graphs ; 27 cm.
Date: 1979
Current SuDoc: E 1.28:ORNL/TM:6350
GPO Item No.: 429-T-4 (MF)
Title: A literature survey : methods for the removal of iodine species from off-gases and
liquid waste streams of nuclear power and nuclear fuel reprocessing plants, with emphasis
on solid sorbents
Author: Holladay, D. W.
Description: vi, 165 p. : ill. ; 28 cm.
Date: 1979
Current SuDoc: E 1.18:0028/v.l-5
GPO Item No.: 429-P
Title: Technology for commercial radioactive waste management.
Author: United States. Dept. of Energy. Office of Nuclear Waste Management.
Description: 5 v.: ill. ; 28 cm.
Date: 1979
Current SuDoc: ER 1.11:CONF-770102
GPO Item No.: 1051-C
Title: Ceramic & glass radioactive waste forms
Author: Compiled & edited by D. W. Readey, C. R. Cooley
Description: 282 p. in various pagings : ill. ; 27 cm.
Date: 1977
F-6
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References from the University of Waterloo Library, Ontario, Canada
Title: Activities related to low - level radioactive waste management at AEGL
Author: Atomic Energy of Canada Limited.
Imprint: Pinawa, Man. : Whiteshell Nuclear Research Establishment, 1987.
Call Number: CA1 AE 685T360 v. 2
Title: Activities related to low - level radioactive waste management at AECL
Imprint: Chalk River, Ont. : Chalk River Nuclear Laboratories, 1987.
Author: Atomic Energy of Canada Limited.
Call Number: CA1 AE 685T360 v. 3
Title: Activities related to low-level radioactive waste management at AECL
Author: Atomic Energy of Canada Limited.
Imprint: Chalk River, Ont. : Chalk River Nuclear Laboratories, 1988.
Call Number: CA1 AE 685T360 v. 4
* " -•,-.'*
Title: Activities related to low-level radioactive waste management at AECL
Author: Atomic Energy of Canada Limited.
Imprint: Chalk River, Ont. : Chalk River Nuclear Laboratories, 1988.
Call Number: CA1 AE 685T360 v. 5
Title: Analytical source term for a low-level radioactive waste repository.
Author: Atomic Energy of Canada Limited.
Imprint: Chalk River, Ont. : Chalk River Laboratories, 1991.
Call Number: CA1 AE 690T510
Title: Stability of candidate buffer materials for a low-level radioactive waste repository.
Imprint: Pinawa, Man. : Whiteshell Nuclear Research Establishment, 1991.
Physical Description: 33 p.
Series: Atomic Energy of Canada Limited. Technical record TR ; 513
Associated Name(s): Torok, J.
Issuing Body: Atomic Energy of Canada Limited.
Title: A waste characterization monitor for low - level radioactive waste management.
Imprint: Chalk River, Ont. : Chalk River Nuclear Laboratories, 1985.
Physical Description: 6 p.
Series: Atomic Energy of Canada Limited. AECL, 0067-0367 ; 8851
Associated Name(s): Davey, E. C. Csullog, G. W. Kupca, S.
Issuing Body: Atomic Energy of Canada Limited.
F-7
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Title: Low - Level Radioactive Waste Management - Consultant Report.
Author: California. Energy Resources Conservation and Development Commission
Call Number: US2CAER 78L54
Title: Low-level radioactive waste : from cradle to grave
Author: Edward L. Gershey
Subject (s): Radioactive wastes. Low-level radiation - Environmental aspects. •
Imprint: New York : Van Nostrand Reinhold, c!990.
Notes: Bibliography: p. 177-180. Includes index.
ISBN: 0442239580
Title: The management and disposal of intermediate and low level radioactive waste. -
Subject(s): Radioactive waste disposal - Management.
Imprint: London : Mechanical Engineering Publications for the Institution of Mechanical
Engineers, 1987.
Notes: "Papers presented at a seminar organized by the Nuclear Energy Committee of the
Power Industries Division of the Institution of Mechanical Engineers and held at the
Institution of Mechanical Engineers on 19 March, 1987." Includes bibliographies.
ISBN: 0852986238 (pbk.)
Physical Description: 51 p. : ill. ; 30 cm.
Associated Name(s): Institution of Mechanical Engineers (Great Britain). Nuclear Energy
Committee.
Title: Safe disposal of radionuclides. in low-level radioactive-waste repository sites :
Low-Level Radioactive-Waste Disposal Workshop, U.S. Geological Survey, July 11-16,1987,
Big Bear Lake, Calif., proceedings.
Imprint: [United States : s.n.], 1990. .
Physical Description: ix, 125 p. : ill., maps.
Series: United States. Geological Survey. Circular ; 1036 ,
Associated Name(s): Bedinger, M. S. Stevens, Peter R. (Peter Ryan), United States.
Geological Survey.
Government Document Number: 119.4/2:1036
Title: A planner's guide to low-level radioactive waste disposal
Author: Smith, Thomas P.
Subject(s): Radioactive waste disposal - United States. Radioactive waste disposal - Law
and legislation - United States. Radioactive wastes - Transportation.
Imprint: Washington, D.C. : American Planning Association, 1982.
Notes: Cover title. Bibliography: p. 48-53.
Physical Description: 53 p. : ill. ; 28 cm.
Series: Report / American Planning Association. Planning Advisory Service ; no. 369
F-8
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Title: Radioactive dating and methods of low-level counting : proceedings Monaco, 2-10
March 1967.
imprint: Vienna, Austria : International Atomic Energy Agency, c!967.
Physical Description: 744 p. : ill.
Series: Proceedings series (International Atomic Energy Agency), 0074-1884
Associated Name(s): International Atomic Energy Agency. Joint Commission on Applied
Radioactivity.
Government Document Number: ST1/PUB/152
Title: Low-level radioactive waste : joint hearing [microform].
Imprint: Washington, D.C : USGPO, 1989.
Notes: Microfiche : [Bethesda, Md.] : Congressional Information Service, 1990 - 1
microfiche.
Physical Description: iv, 11 p.
Associated Name(s): United States. Congress. House. Committee on Interior and Insular
Affairs. Subcommittee on Energy and the Environment.
Issuing Body: United States. Congress. House. Committee on Energy and Commerce.
Subcommittee on Energy and Power.
Title: Specification and performance of on-site instrumentation for continuously monitoring
radioactivity in effluents.
Subject(s): Radioactive waste disposal. Radioactivity - Instruments - Standards - United
States. Nuclear facilities - Equipment and supplies - Standards - United States.
Imprint: New York, N.Y. : Institute of Electrical and Electronics Engineers, 1980, c!974.
Notes: Sponsors, Atomic Industrial Forum and Institute of Electrical and Electronics
Engineers. Approved September 19,1974, reaffirmed August 15,1980, American National
Standards Institute. "Formerly designated as ANSI N13.10-1974." Original designation
covered by label, includes bibliographical references.
Issuing Body: American National Standards Institute.
Title: Geochemical aspects of radioactive waste disposal
Author: Brookins, Douglas G.
Subject (s): Radioactive waste disposal. Geochemistry.
Imprint: New York : Springer-Verlag, c!984.
Notes: Bibliography: p. [307]-328. includes index.
ISBN: 0387909168 3540909168
Physical Description: xiii, 347 p. : ill. ; 25 cm.
F-9
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Title: Denitration of radioactive liquid waste / edited by L. Cecille and S. Halaszovich.
Subject(s): Radioactive waste disposal. Nitrification.
Imprint: London: Graham and Trotman for the Commission of the European Communities,
1986.
Notes: Conference proceedings. Includes bibliography.
ISBN: 0860108546 (pbk.)
Physical Description: viii, 180 p. : ill. ; 24 cm.
Related Work(s): Cecille, L. Halaszovich, S. Commission of the European Communities.
Title: Research and development on radioactive waste management and storage : second
annual progress report of the European Community Programme, 1980-1984.
Subject(s): Radioactive waste disposal.
Imprints: New York : Harwood Academic Publishers ; Brussels : For Commission of the
European Communities, c!982.
ISBN: 3718601486 (The Commission)
Physical Description: 310 p. : ill. ; 23 cm.
Series: Radioactive waste management (New York, N.Y.) ; v. 8.
Associated Name(s): Commission of the European Communities.
Title: Disposal of radioactive wastes / Zdenek Dlouhy ; contributions, Frantisek Cejnav et
al.
Author: Dlouhy, Zdenek
Subject(s): Radioactive waste disposal.
Imprint: Amsterdam : Elsevier Scientific Pub. Co., 1982.
Notes: Translated from the Czech. Includes bibliographical references and index.
ISBN: 0444997245
Physical Description: 264 p. : ill. ; 25 cm.
Series: Studies in environmental science ; 15
Title: Treatment, recovery, and disposal processes for radioactive wastes : recent advances
/ edited by J.I. Duffy.
Subject(s): Radioactive waste disposal.
Imprint: Park Ridge, N.J. : Noyes Data Corp., 1983.
Notes: Includes indexes.
ISBN: 0815509227
Physical Description: xii, 287 p. : ill. ; 25 cm.
Series: PoUution technology review, 0090-516X ; no. 95 Chemical technology review : no.
216.
F-10
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Title: Testing and evaluation of solidified high level radioactive waste / edited by A.R. Hall.
Subject(s): Radioactive waste disposal.
Imprint: London : Graham & Trotman for the Commission of the European Communities,
1987.
Notes: Includes bibliographies.
ISBN: 0860108937 0860109291 (Series)
Physical Description: 354 p. : ill. ; 24 cm.
Series: Radioactive waste management series
Title: Radioactive waste forms for the future / edited by Werner Lutze, Rodney C. Ewing.
Subject(s): Radioactive waste disposal.
Imprint: Amsterdam : North-Holland, 1988.
Notes: Includes bibliographies and indexes.
ISBN: 0444871047
Physical Description: xiii, 778 p. : ill. ; 25 cm.
Title: Radioactive waste technology / sponsored by the American Society of Mechanical
Engineers and American Nuclear Society ; edited by A. Alan Moghissi, Herschel W.
Godbee, Sue A. Hobart.
Subject(s): Radioactive waste disposal.
Imprint: New York, N.Y. : American Society of Mechanical Engineers, c!986.
Notes: Includes bibliographies.
Physical Description: x, 705 p. : ill. ; 27 cm.
Title: Understanding radioactive waste
Author: Murray, Raymond LeRoy
Subject(s): Radioactive wastes. Radioactive waste disposal.
Edition: 2nd ed.
Imprint: Columbus : Battelle Press, c!983.
ISBN: 0935470190 (pbk.)
Physical Description: ix, 117 p. : ill. ; 28 cm.
Title: Radioactive waste disposal.
Author: Roy, Rustum.
Subject(s): Radioactive waste disposal.
Imprint: New York : Pergamon Press, 1982
Notes: Includes bibliographical references.
Contents: v. 1. The waste package
ISBN: 0080275419 (v. 1)
Physical Description: v. : ill. ; 25 cm.
F-ll
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Title: Die Reinigung radioaktiv kontaminierter Abwasser durch Kontaktenthartung und
lonenaustausch. Mit 91 Abb., davon 60 Abb. auf 23 Taf., u. 67 Tab.
Author: Sachse, Gunter.
Subject(s): Radioactive waste disposal. Sewage - Purification -. Ion exchange process.
Water - Softening.
Imprint: Berlin, Akademie-Verl., 1971.
Notes: Bibliography: p. [130]-131.
Physical Description: 131 p. illus. 30 cm.
Series: Abhandlungen der Sachsischen Akademie der Wissenschaften zu Leipzig.
Mathematisch-naturwissenschaftliche Klasse, Bd. 50, Heft 4
Title: Radioactive waste: issues and answers / American Institute of Professional Geologists
; [Fred Schroyer, compiler].
Suhject(s): Radioactive waste disposal
Imprint: Arvada, Colo. : The Institute, 1985.
Notes: Cover title. Bibliography: p. 27.
Physical Description: 27 p. : col. ill. ; 28 cm.
Title: Radioactive waste management
Author: Tang, Y. S. (Yu S.), James H. Saling.
Subject(s): Radioactive waste disposal. Uranium mill tailings.
Imprint: New York : Hemisphere Pub. Corp., c!990.
Notes: Includes bibliographies and index.
ISBN: 0891166661
Physical Description: xi, 460 p. : ill. ; 24 cm.
Associated Name(s): Saling, James H.
References Available from Massachusetts Institute of Technology Library
Title: Conditioning of low- and intermediate-level radioactive wastes.
Edition: 1983.
Imprint: Vienna : International Atomic Energy Agency ; [New York
agent in the United States of America, UNIPUB],
Call Number: HD9698.Al.I61no.222
Exclusive sales
F-12
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Title: Geochemical behavior of disposed radioactive waste
Author: Barney, G.S., J.D. Navratil, W.W. Schultz
Imprint: Washington, D.C. : American Chemical Society, 1984.
Physical Features: ix, 413 p. : ill; 24 cm.
Series: ACS symposium series, 0097-6156 ; 246
Notes: Includes bibliographical references and indexes. "Based on a symposium jointly
sponsored by the Divisions of Nuclear Chemistry and Technology, Industrial and
Engineering Chemistry, and Geochemistry at the 185th Meeting of the American Chemical
Society, Seattle, Washington, March 20-25, 1983",
Title: Geological disposal of radioactive waste : research in the OECD area: national and
international research activities related to geological disposal of radioactive waste /
Coordinating Group on Geological Disposal of Radioactive Waste, Nuclear Energy Agency,
Organization for Economic Co-operation and Development.
Imprint: Paris : Nuclear Energy Agency, OECD, 1982.
Physical Features: 54 p. : ill., maps ; 24 cm.
Notes: Bibliography: p. 50-51.
Other Authors, etc: OECD Nuclear Energy Agency. Coordinating Group on Geological
Disposal of Radioactive Waste.
Subjects: Radioactive waste disposal in the ground.
Title: Proceedings of the Workshop on Geological Disposal of Radioactive Waste:: In Situ
Experiments in Granite. Stockholm, Sweden 25th-27th October 1982
Author: Workshop on Geological Disposal of Radioactive Waste: In Situ ExperL.
Edition: 1983.
Imprint:, Paris : Nuclear Energy Agency, Organization for Economic Cooperation and
Development
Call Number: TD898.W595 1982
Title: Design and instrumentation of in situ experiments in underground laboratories for
radioactive waste disposal: proceedings of a workshop jointly organized by the Commission
of the European Communities & OECD Nuclear Energy Agency, Brussels, 15-17 May 1984
Edition: 1985.
Imprint: Rotterdam ; Boston : Published for the Commission of the European
Communities by A.A. Balkema,
Call Number: TD898.D47 1985
F-13
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Title: A study of the lime-soda softening process as a method for decontaminating
radioactive waters / by Robert F. McCauley,
Author: McCauley, Robert F., Robert A. Lauderdale and Rolf Eliassen.
Imprint: Cambridge, Mass. : Sedgwick Laboratories of Sanitary Science, Massachusetts
Institute of Technology, 1953.
Physical Features: vi, 88 p. : ill. ; 28 cm.
Notes: Includes bibliographical references (p. 87-88). "NYO 4439."
Subjects: Radioactive pollution of water. Radioisotopes. Water — Purification —
Lime-soda ash process.
Title: Management of low-level radioactive waste / edited by Melvin W. Carter, A. Alan
Moghissi, Bernd Kahn.
Imprint: New York : Pergamon Press, c!979.
Physical Features: 2 v. (1214 p.) : ill. ; 24 cm.
Notes: Includes bibliographies and index. Based on papers presented at a symposium
sponsored by Georgia Institute of Technology, and others, held May 23-27,1977, in Atlanta.
Subjects: Radioactive waste disposal ~ Congresses. Nuclear facilities - Waste disposal ~
Congresses. LC Card: 78-27550
ISBN: 0080239072
Title: Partnerships under pressure : managing commercial low-level radioactive waste.
Imprint: Washington, DC : Congress of the U.S., Office of Technology Assessment: For
sale by the Supt. of Docs., U.S. G.P.O., 1989
Physical Features: vii, 153 p. : ill. ; 26 cm.
Notes: Include bibliographical references. Shipping list no.: 90-011-P. November 1989-P.
[4] of cover. "OTA-O-426"--P. [ 4] of cover.
Other Authors, etc: United States. Congress. Office of Technology Assessment.
Other Titles: Managing commercial low level radioactive waste.
Subjects: Radioactive waste disposal - United States ~ Management. Radioactive waste
disposal — Research ~ United States. Hazardous waste management industry - United
States.
LCCard: 89-600772
Government Document Number: Y 3.T 22/2: 2 P 25
Publisher's Number: Tech.Report no.: OTA-O-426
F-14
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Title: Proceedings of the Meeting on Low Level Radioactive Waste held at Incline Village,
Nevada, February 20-21, 1980 / Office of State Programs, U.S. Nuclear Regulatory
Commission [and] Department of Human Resources, State of Nevada.
Author: Meeting on Low Level Radioactive Waste (1980 : Incline Village, NV)
Imprint: Washington, D.C. : The Commission : Available from GPO Sales Program,
Division of Technical Information and Document Control, U.S. Nuclear Regulatory
Commission ; Springfield, Va. : National Technical Information Service, 1980.
Physical Features: vi, 96 p. : ill. : 28 cm.
Notes: Date published: July 1980.
Other Authors, etc: Nevada. Dept. of Human Resources. U.S. Nuclear Regulatory
Commission. Office of State Programs.
Title: Monitoring of radioactive contamination on surfaces; a manual prepared by R.F.
Clayton. Author: Clayton, R.F.
Imprint: Vienna, International Atomic Energy Agency, 1970.
Physical Features: 33 p. illus. 24 cm.
Series: Technical reports series, no. 120 International Atomic Energy Agency. Technical
reports series, no. 120 en
Notes: Bibliography: p. 30-33. "STI/DOC/120."
Subjects: Contamination (Technology). Radioactivity - Safety measures.
LCCard: 71-524940
Title: Proceedings of the Seminar on the Monitoring of Radioactive Effluents seminar
organized by the OECD Nuclear Energy Agency, in collaboration with the German
Ministry for Research and Technology and the Karlsruhe Nuclear Research Centre.
Author: Seminar on the Monitoring of Radioactive Effluents, Karlsruhe, 1974.
Imprint: Paris : OECD, 1974.
Physical Features: 446 p. : ill. ; 24 cm.
Notes: Includes bibliographical references. On cover: Monitoring of radioactive effluents.
English or French; summaries in English and French.
Other Authors, etc: Organization for Economic Cooperation and Development. Nuclear
Energy Agency.
Other Titles: Monitoring of radioactive effluents.
F-15
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Title: A planner's guide to low-level radioactive waste disposal.
Author: Smith, Thomas P.
Imprint: Chicago, IL (1313 E. 60th St., Chicago 60637) : American Planning Association,
1982. Physical Features: 53 p. : ill. ; 28 cm.
Series: Report / American Planning Association, Planning Advisory Service ; no. 369.
Notes: Bibliography: p. 48-53. Cover title.
Other Authors, etc: American Planning Association.
Subjects: Radioactive waste disposal in the ground, Handbooks, rnanuals, etc., Factory and
trade waste, Handbooks, manuals, etc.
LCCard: 83-105921//r83
Title: Radiation protection principles for the disposal of solid radioactive waste : a report
/ of Committee 4 of the International Commission on Radiological Protection.
Author: International Commission on Radiological Protection. Committee 4.
Edition: 1st ed.
Imprint: Oxford ; New York : published for the Commission by Pergamon Press, 1985.
Physical Features: v, 23 p. : ill. ; 25 cm.
Series: ICRP publication, 0146-6453 ; 46 Annals of the ICRP ; v. 15, no. 4
Notes: Bibliography: p. 23. At head of title: Radiation protection. "Adopted by the
Commission in July 1985."
Subjects: Radioactive waste disposal - Management. Radiation ~ Safety measures.
ISBN: 0080336663
Title: Principles of monitoring for the radiation protection of the population : a report
Author: International Commission on Radiological Protection. Committee 4.
Edition: 1st ed.
Imprint: Oxford ; New York : published for the Commission by Pergamon,
Call Number: RA1231.R2.I614 no.43
Title: Management of radioactive waste : the issues for local authorities : proceedings of
the conference organized by the National Steering Committee, Nuclear Free Local
Authorities, and held in Manchester on 12 February 1991 / edited by Stewart Kemp.
Imprint: London : Thomas Telford, 1991.
Physical Features: 177 p. : ill. ; 24 cm.
Notes: Includes bibliographical references.
Other Authors, etc: Kemp, Stewart. Nuclear Free Local Authorities (Great Britain).
National Steering Committee.
Subjects: Radioactive waste disposal - Great Britain - Congresses.
ISBN: 0727716441
F-16
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Title: Radioactive waste management.
Author: Berlin, Robert E., Catherine C. Stanton.
Imprint: New York : Wiley, c!989.
Physical Features: xvi, 444 p. : ill. ; 25 cm.
Notes: Includes bibliographies and index. "A Wiley-Interscience publication."
Other Authors, etc: Stanton, Catherine C.
Subjects: Radioactive waste disposal ~ United States. Radioactive waste .sites - United
States.
LC Card: 88-17359 . :
ISBN: 0471857920 ,
Title: Denitration of radioactive liquid waste / edited by L. Cecille and S. Halaszovich.
Imprint: London ; Norwell, Mass. : Graham and Trotman for the Commission of the
European Communities, 1986.
Physical Features: viii, 180 p. : ill. ; 24 cm.
Series: Radioactive waste management series
Notes: Includes bibliographies. "EUR 10650" Conference proceedings.
Other Authors, etc: Cecille, L. Halaszovich, S. Commission of the European Communities.
Subjects: Radioactive waste disposal. Nitrification.
LC Card: G.B. 86-27362
ISBN: 0860108546 (pbk) :
Publisher's Number: Tech.Report no.: EUR 10650
Title: Radioactive waste technology / sponsored by the American Society of Mechanical
Engineers and American Nuclear Society ; edited by A. Alan Moghissi, Herschel W.
Godbee, Sue A. Hobart. ,
Imprint: New York, N.Y. (345 E. 47th St., New York 10017) : American Society of
Mechanical Engineers, c!986. ,
Physical Features: x, 705 p. : ill. ; 27 cm.
Notes: Includes bibliographies.
Other Authors, etc: Moghissi, A. Alan. Godbee, H. W. Hobart, Sue A. American Society
of Mechanical Engineers. American Nuclear Society.
Subjects: Radioactive waste disposal. . :
LCCard: 86-151343
F-17
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Title: Radioactive waste management.
Author: Radioactive waste management (Chur, Switzerland : 1980)
Imprint: Chur [Switzerland] ; New York : Harwood Academic Publishers, cl980-c!982.
Physical Features: 2 v. : ill. ; 23 cm.
Notes: Quarterly (irregular) Indexed by Biological abstracts 0006-3169 Computer &
control abstracts 0036-8113 Sept. 198Q-June 1982 Electrical & electronics abstracts
0036-8105 Sept. 1980-June 1982 Physics abstracts. Science abstracts. Series A 0036-8091
Sept. 1980-June 1982 GeoRef 0197-7482 Title from cover. Continued by: Radioactive
waste management and the nuclear fuel cycle 0739-5876 (DLC) 83648101
(OCoLC)9052909
Other Titles: Abbreviated title: Radioact. waste manage. (Chur, Switz. 1980)
LCCard: 83-648100
ISBN: ISSN: 0142-2405
Title: Radioactive waste management.
Imprint: Oak Ridge, Tenn. : Technical Information Center, U.S. Bept. of Energy, 1981.
Physical Features: v.; 28 cm.
Notes: Semimonthly "A current awareness bulletin." Caption title. PB81-902914.
Other Authors, etc: United States. Dept. of Energy. Technical Information Center.
Other Titles: Abbreviated title: Radioact. waste manage. (Oak Ridge, Tenn.)
Subjects: Radioactive wastes - Abstracts - Periodicals. Radioactive waste disposal -
Abstracts — Periodicals.
LCCard: sn 81-476
ISBN: ISSN: 0275-3707
Title: The management of radioactive waste : a report by an international group of experts.
Imprint: London : Uranium Institute, 1991.
Physical Features: 70 p. : ill. ; 30 cm.
Notes: August 1991.
Other Authors, etc: Uranium Institute.
Subjects: Radioactive wastes - Management. Radioactive wastes - Management - Case
studies. Radioactive waste disposal. Radioactive waste disposal - Case studies.
LCCard: 91-217337
ISBN: 0946777217
F-18
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Title: Radioactive waste processing and disposal; an annotated bibliography of selected
literature.
Imprint: Oak Ridge, Tenn. : United States Atomic Energy Commission, Technical
Information Service etc.; Washington, D.C. : available from the Office of Technical
Services, Dept. of Commerce etc.
Series: 1958, 1964-80: TED; 3311 1960-62: TID; 3555 1980: NUREG 643-644 1981
: DpE/TIC3311
Other Authors, etc: Voress, Hugh E., Davis, Theodore F. United States. Atomic Energy
Commission.
Subjects: Radioactive wastes - Abstracts. Radioactive waste disposal - Abstracts. Reactor
fuel reprocessing — Abstracts.
Title: Radioactive waste management at the Savannah River Plant: a technical review /
Panel on Savannah River Waste, Board on Radioactive Waste Management, Commission
on Natural Resources, National Research Council.
Imprint: Washington, D.C. : National Academy Press, 1981.
Physical Features: xii, 68 p. : ill. ; 28 cm.
Notes: Bibliography: p. 58-68.
Other Authors, etc: National Research Council. (U.S.) Panel on Savannah River Wastes.
Subjects: Atomic power-plants -- South Carolina - Aiken ~ Waste disposal. Radioactive
waste disposal — South Carolina — Aiken.
LCCard: 81-85742 ,
ISBN: 030903227X
Title: Management of radioactive waste from U.S. light-water reactor operation.
Author: Losk, Richard Bryan.
Imprint: c!978.
Physical Features: 50 [i.e. 49] leaves : ill., charts ; 28 cm.
Series: Massachusetts Institute of Technology. Dept. of Nuclear Engineering. Thesis. 1978.
B.S. en
Notes: Thesis (B.S.)~M.I.T., Dept. of Nuclear Engineering, 1978. Includes bibliographical
references. Microfiche copy available in archives and science. Supervised by Irving Kaplan.
Subjects: Radioactive waste disposal. Reactor fuel reprocessing.
F-19
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Title; Testing, evaluation, and shallow land burial of low and medium radioactive waste
forms : proceedings of a seminar organized under the R & D Programme of the
Commission of the European Communities on Radioactive Waste Management and
Disposal, held at the Central Bureau for Nuclear Measurements, Geel, Belgium, 28-29
September 1983 / edited by W. Krischer and R. Simon.
Imprint: Chur, Switzerland ; New York, NY, U.S.A.: Hardwood Academic Publishers for
the Commission of the European Communities, c!984.
Physical Features: xi, 227 p. : ill. ; 23 cm.
Series: Radioactive waste management, 0275-7573 ; v. 13
Notes: Includes bibliographies.
Other Authors, etc: Krischer, W., Simon, R., R & D Programme of the Commission of the
European Communities on Radioactive Waste Management and Disposal.
Subjects: Radioactive waste disposal in the ground — Congresses.
Title: Radioactive wastes at the Hanford Reservation : a technical review / Panel on
Hanford Wastes, Committee on Radioactive Waste Management, Commission on Natural
Resources, National Research Council.
Author: National Research Council. Panel on Hanford Wastes.
Imprint: Washington : National Academy of Sciences, 1978.
Physical Features: xvi, 269 p. : ill. ; 28 cm.
Notes: Bibliography: p. 253-269.
Subjects: Hanford Engineer Works. Nuclear facilities - Washington (State) ~ Hanford --
Waste Disposal. Radioactive waste disposal.
LCCard: 78-52310
ISBN: 0309027454
Title: Radioactive wastes from the nuclear fuel cycle / R. E. Tomlinson, editor ; [3
contributors] P. Auchapt et al.
Imprint: New York : American Institute of Chemical Engineers, 1976.
Physical Features: vi, 178 p. : ill. ; 28 cm.
Series: AIChE symposium series ; no. 154, v. 72 American Institute of Chemical Engineers.
AIChE symposium series ; no. 154.
Notes: Includes bibliographical references. Papers from several symposia sponsored by the
Nuclear Engineering Division of the American Institute of Chemical Engineers in 1975.
Other Authors, etc: Tomlinson, R. E., Auchapt, P. American Institute of Chemical
Engineers. Nuclear Engineering Division.
Subjects: Atomic power-plants ~ Waste disposal ~ Addresses, essays, lectures. Reactor fuel
reprocessing — Waste disposal - Addresses, essays, lectures.
LCCard: 76-23229
F-20
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Title: Management of radioactive wastes from the nuclear fuel cycle : proceedings of a
symposium on the management of radioactive wastes from the nuclear fuel cycle / jointly
organized by the International Atomic Energy Agency and the OECD Nuclear Energy
Agency and held in Vienna, 22-26 March 1976.
Imprint: Vienna : International Atomic Energy Agency ; New York : sold by UNIPUB,
1976.
Physical Features: 2 v. : ill. ; 24 cm.
Series: Proceedings series - International Atomic Energy Agency
Notes: Includes bibliographical references. "STI/PUB/433." English, French, Russian, or
Spanish.
Title: Guide to the safe handling of radioactive wastes at nuclear power plants.
Imprint: Vienna: International Atomic Energy Agency, 1980.
Physical Features: 84 p. : ill. ; 24 cm.
Series: Technical reports series - International Atomic Energy Agency ; no. 198 Technical
reports series (International Atomic Energy Agency) ; no. 198.
Notes: Bibliography: p. 48; "STI/DOC/10/198." Supplements much of no. 28 in the IAEA
safety series, which was published under title: Management of radioactive wastes at nuclear
power plants.
Other Authors, etc: International Atomic Energy Agency.
Other Titles: Management of radioactive wastes at nuclear power plants.
Subjects: Atomic power-plants - Waste disposal. Radioactive waste disposal. Radioactivity
— Safety measures.
ISBN: 9201250800:
Title: American National Standard N542 : sealed radioactive sources, classification.
Author: American National Standards Institute. Subcommittee N43-3.3.
Imprint: Washington : Dept. of Commerce, National Bureau of Standards : for sale by
the Supt. of Docs., U.S. Govt. Print. Off., 1978.
Physical Features: vii, 20 p. ; 26 cm.
Series: NBS handbook; 126 United States. National Bureau of Standards. Handbook; 126.
Other Titles: Sealed radioactive sources, classification.
Subjects: Radioactive substances - Safety measures - Standards.
LCCar4: 83-601612
Government Document Number: C 13.11: 126
F-21
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Title: Table of radioactive isotopes / Edgardo Browne.
Author: Browne, Edgardo., Richard B. Firestone ; Virginia S. Shirley, editor.
Imprint: New York : Wiley, c!986.
Physical Features: xxiii, 29, [900] p. ; 29 cm.
Notes: Bibliography: p. xxii-xxiii. "A Wiley-Interscience publication."
Subjects: Radioisotopes — Tables.
LCCard: 86-9069
ISBN: 047184909X
Title: Table of radioactive isotopes and of their main decay characteristics.
Author: J. Blachot, C. Fiche.
Imprint: Paris ; New York : Masson, 1981.
Physical Features: 218 p. : ill. ; 26 cm.
Series: Annales de physique, 0003-4169 ; v. 6, (suppl.)
Notes: Bibliography: p.4. Cover title: Tableau des isotopes radioactifs et des principaux
rayonnements emis. "Numero special supplementaire." Chiefly tables. Includes indexes.
Other Titles: Tableau des isotopes radioactifs et des principaux rayonnements emis.
Subjects: Radioisotopes — Decay — Tables.
Title: The treatment and handling of radioactive wastes / edited by A.G. Blasewitz, J.M.
Davis, M.R. Smith.
Imprint: Columbus, [Ohio] : Battelle Press ; New York : Springer Verlag, c!982.
Physical Features: xiii, 658 p. : ill. ; 29 cm.
Notes: Includes bibliographical references and indexes. Selected papers presented at the
American Nuclear Society Topical Meeting on "The Treatment and Handling of Radioactive
Wastes" held Apr. 19-22, 1982, in Richland, Wash.
Subjects: Radioactive waste disposal ~ Congresses.
LCCard: 82-22695
"'Title: Treatment, recovery, and disposal processes for radioactive wastes : recent advances
/ edited by J.I. Duffy.
Imprint: Park Ridge, N.J. : Noyes Data Corp., 1983.
Physical Features: xii, 287 p. : ill. ; 25 cm.
Series: Pollution technology review, 0090-516X ; no. 95 Chemical technology review, no.
216 Chemical technology review ; no. 216. *
Notes: Includes indexes.
Subjects: Radioactive waste disposal.
LCCard: 82-22260
ISBN: 0815509227:
F-22
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References from the University of Texas at Austin Libraries
Title: Design validation final report/ U.S. Department of Energy. Waste Isolation Pilot
Plant.
Author: Waste Isolation Pilot Plant (N.M.)
Published: San Francisco, Calif. : Bechtel National, 1986.
Description: 2 v. (various pagings) : ill., maps ; 30 cm.
Notes: October 1986. Job 12484.
Title: Nuclear waste handling and storage : proceedings of a session / sponsored by
the Structural Division of the American Society of Civil Engineers in conjunction with
the ASCE National Convention, Boston, Massachusetts, October 31, 1986; edited by
Ralph A, Kohl.
Published: New York, N.Y. : ASCE, c!986.
Description: v, 70 p. : ill. ; 22 cm.
Notes: Includes bibliographies and indexes.
Subjects: Radioactive waste sites, design and construction, Congresses. Radioactive
wastes-Congresses.
ISBN: 0872625621 (pbk.)
OCLC Number: 14271182
Title: Use of the GENII computer code in a low-level radioactive waste disposal facility
performance assessment methodology /by Arnold Elaine Preece.
Author: Preece, Arnold Elaine
Published: 1993.
Description: x, 80 leaves : ill. ; 28 cm.
Notes: Vita.Thesis (M.S. in Engin.)--University of Texas at Austin, 1993. Includes
bibliographical references (leaves 76-80).
Subjects: Radioactive waste sites—Environmental aspects—Texas—Evaluation.Dept.:
Engineering, Mechanical.
OCLC Number: 28833960
F-23
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Title: Radwaste '86 : proceedings volume, Conference on the Treatment and
Containment of Radioactive Waste, and Its Disposal in Arid Environments, 7-12
September 1986, Cape Town, Republic of South Africa / sponsors, the Atomic Energy
Corporation of South Africa Limited, ESCOM ; compiled and edited by L.C. Ainslie.
Author: Conference on the Treatment and Containment of Radioactive Waste and Its
Disposal in Arid Environments (1986 : CapeTown, South Africa)
Published: Pretoria, Republic of South Africa : Atomic Energy Corporation of South
Africa Ltd., 1986.
Description: 1043 p. : ill. ; 30 cm.
Notes: Accompanied by map entitled: Geological map of the Vaalputs National
Radioactive Waste Disposal Facility, Northwestern Cape, South Africa. Includes
bibliographies. Radioactive waste disposal in the ground-Congresses. Arid
regions—Congresses. Radioactive waste sites—South Africa—Congresses.
ISBN: 0869608320
OCLC Number: 18342181
Title: Nuclear waste : quarterly report on DOE's nuclear waste program as of June 30,
1989 : report to Congressional requesters / United States General Accounting Office.
Published: Washington, D.C. : The Office, 1989.
Description: 27 p. ; 28 cm.
Notes: Cover title."December 1989"-Cover. "RCED-90-59""B-202377"~P. 1.
Subjects: United States. Dept. of Energy.Radioactive waste disposal—United States.
Radioactive waste disposal—Law and legislation—United States. Radioactive
pollution—United States. Radioactive pollution—Law and legislation-United States.
Hazardous waste sites—United States. Radioactive waste sites—United States.
Document Number: GA 1.13: RCED-90-59
OCLC Number: 21257756
Title: Quality assurance guidance for low-level radioactive waste disposal facility : final
report / C.L. Pittiglio, Jr.
Author: Pittiglio, C. L.
Published: Washington, DC : Division of Low-Level Waste Management and
Decommissioning, Office of Nuclear Material Safety and Safeguards, U.S. Nuclear
Regulatory Commission, 1989.
Description: 1 v. (various pagings) ; 28 cm.
Subjects: Radioactive waste sites-United States-Design and construction. Radioactive
waste disposal-United States.
U.S. Document Number: Y 3.N 88: 10/1293/989
OCLC Number: 23086340
F-24
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Title: Treatment of alpha bearing wastes.
Published: Vienna: International Atomic Energy Agency, 1988.
Description: 69 p. : ill. ; 24 cm.
Subjects: Radioactive wastes
Other Author(s): International Atomic Energy Agency
Series: Technical reports series (International Atomic Energy Agency)no. 287.
ISBN: 9201253885
OCLC Number: 18808633 T
Title: Treatment of low- and intermediate-level solid radioactive wastes.
Published: Vienna : International Atomic Energy Agency, 1983.
Description: 93 p. : ill. ; 24 cm.
Notes: "STI/DOC/10/223""... replaces the 1970 IAEA technical reports series no.
106,The Volume reduction of low-activity solid wastes."~Foreword. Bibliography: p.
83-90.
Subjects: Radioactive wastes Radioactive waste disposal
Series: Technical reports series (International Atomic Energy Agency)no. 223.
ISBN: 9201251831 :
OCLC Number: 9614148
Title: : Treatment of off-gas from radioactive waste incinerators.
Published: Vienna : International Atomic Energy Agency ; (Lanham, MD :
UNIPUB, distributor), 1989.
Description: 229 p. : ill. ; 24 cm.
Notes: "STI/DOC/10/302"-- T.p. verso. "October 1989."Bibliography: p. 219-225.
Subjects: Radioactive wastes Incinerators ,
Other Author(s): International Atomic Energy Agency
Series: Technical reports series (International Atomic Energy Agency)no. 302.
ISBN: 9201253893
OCLC Number: 20796480
Title: Data for radioactive waste management and nuclear applications.
Author: Stewart, Donald Charles
Published: New York : Wiley, c!985.
Description: x, 297 p. : ill. ; 24 cm.
Notes: A Wiley-Interscience publication. Includes index. Bibliography: p. 281-292.
Subjects: Radioactive wastes Ionizing radiation
ISBN: 0471886270:
OCLC Number: 11289332
F-25
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Title: Stabilization and solidification of hazardous, radioactive, and mixed wastes. 2nd
volume / T. Michael Gilliam and Carlton C. Wiles, (editors).
Published: Philadelphia, PA : ASTM, c!992.
Description: xii, 501 p. : ill. ; 24 cm.
Notes: "Contains papers presented at the Second International Symposium on
StabiMzation/Solidification of Hazardous,Radioactive, and Mixed Wastes, which was held
in Williamsburg, Virginia, 29 May to 1 June 1990."--Foreword. Includes index. Includes
bibliographical references.
Subjects: Hazardous wastes—Congresses. Radioactive wastes—Congresses.Sewage sludges
digestion-Congresses.Other Author(s): Gilliam, T. M.Wiles, Carlton C.
Author(s): International Symposium on Stabilization/Solidification of hazardous,
Radioactive, and Mixed Wastes (2nd : 1990 : Williamsburg, Va.)
Series: ASTM special technical publication. 1123.
ISBN: 0803114435
OCLC Number: 25276639
Title: Management of gaseous wastes from nuclear facilities : proceedings of an
International Symposium on Management of Gaseous Wastes from Nuclear Facilities /
jointly organized by the International Atomic Energy Agency and the Nuclear Energy
Agency of the OECD, and held hi Vienna, 18-22 February 1980.
Author: International Symposium on Management of Gaseous Wastes from Nuclear
FacUities (1980 : Vienna, Austria)
Published: Vienna: International Atomic Energy Agency ; (New York : exclusive
sales agent in United States of America, UNIPUB),1980.
Description: 699 p. : ill.; 24 cm.
Notes: "STI/PUB/561"English, French, or Russian with abstracts in the language of the
paper and English. Earlier work see under variant name: Symposium on Operating and
Developmental Experience in the Treatment of Airborne Radioactive Wastes.
Notes: Includes bibliographies and indexes.
Subjects: Radioactive wastes—Congresses. Radioactive pollution—Congresses. Nuclear
power plants—Waste disposal—Congresses. Air—Pollution—Congresses.
Series: Proceedings series (International Atomic Energy Agency) 1980
ISBN: 9200203809
OCLC Number: 76614003
F-26
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Title: Monitoring of radioactive effluents from nuclear facilities : proceedings of the
International Symposium on the Monitoring of Radioactive Airborne and Liquid
Releases from Nuclear Facilities, held by the International Atomic Energy Agency in
Portoroz, Yugoslavia, 5-9 September 1977.
Author: International Symposium oh the Monitoring of Radioactive Airborne and
Liquid Releases from Nuclear Facilities, Portoroz, 1977.
Published: Vienna : International Atomic Energy Agency, 1978
Description: 610 p. : ill. ; 24 cm.
Notes: "STI/PUB/466" In English, French or Russian. Includes bibliographical
references and index.
Subjects; Radioactivity-Measurement-Congresses. Radioactive wastes-Congresses
ISBN: 9200200788 &
OCLC Number: 4275885
Title: Treatment and conditioning of radioactive incinerator ashes / edited by L Cecille
and C. Kertesz. '
Published: London ; New York : Elsevier Applied Science, c!991.
Description: xii, 239 p. : ill. ; 25 cm.
Notes: "Proceedings of a technical seminar jointly organized by the Commission of the
European Communities, Directorate-General for Science, Research and Development
and the Commissariat a 1'energie Atomique, Direction du Cycle du Combustible
Departement Stockage Dechets, held in Aix-en-Provence, France, 12-15 June 1990"»Opp
t.p. Includes bibliographical references and index. .
Subjects: Radioactive wastes-Incineration-Congresses. Fly
ash-Purification-Congresses.
ISBN: 1851666559
OCLC Number: 23769476
Title: Waste drum fire propagation at the Waste Isolation Pilot Plant/ Prepared for the
U.S. Department of Energy by the Safety, Security and Environmental Protection
Department of the Management and Operating Contractor, Waste Isolation Pilot Plant
Published: Carlsbad, N.M. : Waste Isolation Pilot Plant, 1987
Description: (4p.) 45 p. : ill. ; 28 cm.
Subjects: Waste Isolation Pilot Plant (N.M.) Transuranium elements, Safety measures
radioactive wastes, packing
U.S. Document Number: E 1.28: WIPP-87-005
OCLC Number: 24101066
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Title: New separation chemistry techniques for radioactive waste and other specific
applications / edited by L. Cecffle, M. Casarci, and L. Pietrelli.
Published: London ; New York : Elsevier Applied Science, c!991.
Description: xiv, 307 p. : ill. ; 25 cm. .,,,_«•.• t ^
Notes: "Proceedings of a technical seminar jointly organized by the Commission ot tne
European Communities (CEC), Directorate-General for Science, Research, and
Development and by the Italian Commission for Nuclear and Alternative Energy Sources
(ENEA)" Includes bibliographical references and index.
Subjects: Radioactive wastes--Purification--Congresses. Sewage-Purification-Congresses.
Separation (Technology)--Congresses.
ISBM: 1851666567
OCLC Number: 23732085
Title: Radioactivity and its measurement.
Author: Mann, W. B., S.B. Garfinkel. • .
Published: Princeton, N.J., Published for the Commission on College Physics (by) Van
Nostrand (1966)
Description: 168 p. illus. 21 cm.
Notes: Bibliography: p. 161.
Subjects: Radioactivity
Series: Van Nostrand Momentum Books. No. 10
OCLC Number: 217974
Title: A Handbook of radioactivity measurements procedures : with nuclear data for
some biomedically important radionuclides, reevaluated between August 1983 and April
1984.
Edition: 2nd ed.
Published: Bethesda, Md. : National Council on Radiation Protection and
Measurements, c!985.
Description: xvi, 592 p. : ill. ; 24 cm.
Notes: "Recommendations of the National Council on Radiation Protection and
Measurements. February 1, 1985. Includes index. Bibliography: p. 517-564.
Subjects: Radioactivity Measurement Radioactivity Instruments
Series: NCRP report, no. 58
ISBN: 0913392715
OCLC Number: 11369895
.F-28
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Title: Recommended .instrumentation for uranium and thorium exploration.
Published: Vienna : International Atomic Energy Agency, 1974.
Description: 93 p. ; 24 cm.
Notes: Includes bibliographical references.
Subjects: Uranium ores thorium ores radioactivity-Instruments
Series: Technical reports series - International Atomic Energy Agency ; no. 158
International Atomic Energy Agency Technical reports series.no 158
OCLC Number: 1475763
Title: Radioisotope instruments. »
Author: Cameron, J. R, C. G. Clayton.
Edition: (1st ed.)
Published: Oxford, New York, Pergamon Press (1971)
Description: v. illus. 26 cm.
Notes: Includes bibliographical references.
Subjects: Radioactivity Instruments Radioisotopes-Iridustrial applications
Series: International series of monographs in nuclear energy v 107
ISBN: 0080158021 '
OCLC Number: 324336
Uniform Title: Apparatura dlia registratsii i issledovaniia ioniziruiushchikh izluchenii.
English Title: Handbook of recording instruments for ionizing radiation /compiled by
M. E. Egorov et al; edited by V. V. Matveev and B. I. Khazanov ; translated from
Russian (by J. Flancreich).
Author: Egorov, Ivan Maksimovich.
Published: Jerusalem : Israel Program for Scientific Translations; Springfield Va •
available from the U. S. Department of Commerce Clearinghouse for Federal Scientific
and Technical Information, 1967. .-. • -
Description: xiv, 455 p. : ill. ; 24 cm.
Subjects: Radioactivity-Instruments Radioactivity-Measurement
OCLC Number: 2506135
F-29
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References from Dialog Computer Databases
Title: Radioactive waste characterization.
Author: Amir, S.J., Westinghouse Hanford Co., Richland, WA.
Source: Govt Reports Announcements & Index (GRA&I), Issue 15, 1993
Spon. Agency: Department of Energy, Washington, DC.
Contract Number: WHC-SA-1756, CONF-921137-8, Contract AC06-87RL10930
Order Info.: NTIS/DE93004518, 12p
Title: Microwave separation of organic chemicals from mixed hazardous waste.
Author: Anderson, A.A.; Albano, R.K., EG & G Idaho, Inc., Idaho Falls.
Source: Govt Reports Announcements & Index (GRA&I), Issue 01, 1993
Spon. Agency: Department of Energy, Washington, DC.
Contract Number: EGG-M-92111, .CONF-920851-60, Contract AC07-76ID01570
Order Info.: NTIS/DE92017848, 5p
Title: Hanford Site high-level tank waste data specification process.
Author: Waters, R.D.; Babad, H., Westinghouse Hanford Co., Richland, WA.
Source: Govt Reports Announcements & Index (GRA&I), Issue 01, 1993
Spon. Agency: Department of Energy, Washington, DC.
Contract Number: WHC-SA-1492, CONF-920851-37, Contract AC06-87RL10930
Order Info.: NTIS/DE92015833, 16p
Title: Multivariate methods in nuclear waste remediation: Needs and applications.
Author: Pulsipher, B.A., Battelle Pacific Northwest Labs., Richland, WA.
Source: Govt Reports Announcements & Index (GRA&I), Issue 24, 1992
Spon. Agency: Department of Energy, Washington, DC.
Contract Number: PNL-SA-20486, CONF-9205174-1, Contract AC06-76RL01830
Order Info.: NTIS/DE92015094, 14p
Title: New mass spectroscopic methods for waste management.
Author: Chen, C.H.; Garrett, W.R.; Allman, S.L.; Phillips, R.C., Oak Ridge National
Lab., TN.
Source: Govt Reports Announcements & Index (GRA&I), Issue 23, 1992
Spon. Agency: Department of Energy, Washington, DC.
Contract Number: CONF-920851-23, Contract AC05-84OR21400
Order Info.: NTIS/DE92015080, 6p
F-30
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Title: Assessment of dome-fill technology and potential fill materials for the Hanford
single-shell tanks.
Author: Smyth, J.D.; Shade, J.W.; Somasundaram, S., Battelle Pacific Northwest Labs
Richland, WA. •>
Source: Govt Reports Announcements & Index (GRA&I), Issue 23, 1992
Spon. Agency: Department of Energy, Washington, DC
Contract Number: PNL-8014, Contract AC06-76RL01830
Order Info.: NTTS/DE92014599, 52p
Title: Medical waste: a minimal hazard
Author: Keene, J.H., Department of Biostatistics, School of Basic Health Sciences
Medical College of Virginia/Virginia Commonwealth University, Richmond.
Source: Infect Control Hosp Epidemiol; VOL 12, ISS 11, 1991 P682-5
ISSN: 0899-823X
Comment in Infect Control Hosp Epidemiol 1992 Feb;13(2):75-6
Document Type: Journal Article
Title: Management of mixed wastes from biomedical research.
Author: Linins, L; Klein, R.C.; Gershey, EX., Rockefeller University, New York, NY
Source: Health Phys; VOL 61, ISS 3, 1991, P421-6
ISSN: 0017-9078
Document Type: Journal Article
Title: Leach rate expressions for performance assessment of solidified low-level
radioactive waste.
' C" Dept Nuclear EnerSy» Brookhaven National Lab., Upton, New
Source: Waste Manage; 11 (4). 1991. 223-230.
Title: Proposed plan for vitrification demonstration of low-level radioactive wastes at the
Fernald Environmental Management Project.
Author: Gimpel, RF Westinghouse Environmental Management Co. of Cincinnati
Unio. Fernald Environmental Management Project. '
Source: Govt Reports Announcements & Index (GRA&I), Issue 05 1992
Spon. Agency: Department of Energy, Washington, DC
Contract Number: FMPC-2238, CONF-910981-14, Contract AC05-86OR21600
Order Info.: NTIS/DE91018817, 22p
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Title- Waste characterization plan for the Hanford Site single-shell tanks. Revision 1.
Author: Winters, W.I.; Jensen, L.; Sasaki, L.M.; Weiss, R.L.; Keller, J.F., Westinghouse
Hanford Co., Richland, WA,
Source: Govt Reports Announcements & Index (GRA&I), Issue 04, 1991
Spon. Agency: Department of Energy, Washington, DC.
Contract Number: WHC-EP-0210-Rev.l, Contract AC06-87RL10930
Order Info.: NTIS/DE91000296, 300p
Title: RCRA closure experience with radioactive mixed waste 183 H Solar Evaporation
Basins at the Hanford Site.
Author: Westinghouse Hanford Co., Richland, WA.
Source: Govt Reports Announcements & Index (GRA&I), Issue 14, 1990
Spon. Agency: Department of Energy, Washington, DC.
Contract Number: WHC-SA-0705, CONF-900210-45, Contract AC06-87RL10930
Order Info.: NTTS/DE90007212, Portions of this document are illegible in microfiche
products., 13p
Title: Bench-Scale Classification Test on Rocky Mountain Arsenal Basin F Material.
Author: Balasco, A.A.; Stevens, J.I.; Adams, J.W.; Brouns, R.; Cerundolo, D.L., Little
(Arthur D.), Inc., Cambridge, MA
Source: Govt Reports Announcements & Index (GRA&I), Issue 08, 1992
Spon. Agency: Army Toxic and Hazardous Materials Agency, Aberdeen Proving Ground,
MD. Technology Div.
Contract Number: Contract DAAK11-85-D-0008
Order Info.: NTIS/AD-A243 993/3, 62p
Title: Northwest Hazardous Waste Research, Development, and Demonstration Center:
Program Plan.
Author: Battelle Pacific Northwest Labs., Richland, WA.
Source: Govt Reports Announcements & Index (GRA&I), Issue 20, 1988
Spon. Agency: Department of Energy, Washington, DC.
Contract Number: PNL-6491-1, Contract AC06-76RL01830
Order Info.: NTIS/DE88007599, 156p
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