------------------------------------------------

CHAPTER

NINE
-- MIXED WASTES

9.1 INTRODUCTION

Mixed wastes contain both radioactive and hazardous wastes. Therefore, a dual regulatory
framework exists for mixed wastes, with the U.S. Environmental Protection Agency
(EPA) or authorized states regulating the hazardous wastes using the Resource Conser-
vation and Recovery Act (RCRA) and the U.S. Nuclear Regulatory Commission (NRC),
NRC agreement states, or the U.S. Department of Energy (DOE) regulating the ra-
dioactive waste using the Atomic Energy Act (AEA). NRC generally regulates com-
mercial and non-DOE federal facilities. DOE is currently self-regulating and its orders
apply to DOE sites and contractors. The requirements of RCRA and AEA are generally
consistent and compatible. However RCRA takes precedence over AEA in the event
provisions or requirements of the two are inconsistent.
Almost all of the commercially generated (non-DOE) mixed waste is composed of
low-Ievel radioactive waste (LLRW) and hazardous waste and is called low-level
mixed waste (LLMW) or sometimes, mixed low-Ievel waste (MLLW). Cornmercially
generated LLMW is produced in all 50 states at industrial, hospital, and nuclear power
Plant facilities. Radioactive and hazardous materials are used in a number of processes
sUch as medical diagnostic testing and research, pharmaceutical and biotechnology de-
velopment, and pesticide research, as well as nuclear power plant operations. Under
the 1984 Amendments to RCRA, Land Disposal Restrictions (LDR) regulations pro-
hibit disposal of most mixed waste including LLMW until it meets specific treatment
Standards. Most 01' the commercial mixed waste can be treated to meet the LDRs by
cornmercially available technologies. Commercial mixed waste volumes are very small
(approximately 2%) cornpared to the volume of mixed waste being generated or stored

291
292 MIXED WASTES 9.5 WASTE MINIMIZATlON METHODOLOGIES 293

Table 9.1 Summary of estimated total MLLW inventories and FY1996 generatiolJ. 'fable 9.2 Total volume (nr') of inventory and generation of DOE RCRA
----
Category

OOE sites
Total inventory
Volume (m")
----
FY 1996 generation" --
and RCRA PCB MLLW, by physical forma

MPC Cúrrent Actual

Volume (rrr')

FY projections
RCRA and RCRA PCB MLLW
Non-RCRA PCB MLLW
OOE MLLW total
Major commercial sites"
Other commercial sites''
71,710b
4,530b
76,240
2,116
31,014
608
73
681
3,949
O
-
JVlPCname

Liquids
AqueouS liquids/
slurries
code

LOOOO
L1000
inventory

148.34
4,903.52

1,311.53
1996

12.15
4.67
1997

19.27
255.18
1998-2006

545.96
6,705.85

1,440.56
2007-2030

107.10
1,232.45

Organic liquids L2000 69.36 140.06 2,935.09

SOOOO 490.52 40.93 62.78 1,842.79 361.18
Solids
"Exccpt where indicated. S3000 21.51 0.86 9.77 54.98 59.89
J-Iomogeneous solids
b Based on ref. 2. The currentness of these data for the various OOE sites ranges from September 1995
Inorganic homogeneous S3100 49,991.40 89.98 148.60 11,279.31 7,999.89
to July 1997.
solids
"Reported for calendar year 1990. S3200 501.68 0.33 1.87 13.49 25.48
Organic homogeneous
dWastes from commercial- and government-sponsored (OOE, EPA, 000) activities that are disposed of
solids
at other commercially operated disposal facilities. S4000 1,459.34 21.43 63.36 7,737.51 2,638.25
Soil/gravel
24.32
• Debris waste
1norganic debris
S5000
S5100
784.43
1,353.16 105.93
0.25
218.95
2.29
16,671.29
6.10
36,146.50
Organic debris S5300 2,257.89 67.10 96.96 3,238.62 2,834.41
by the Department of Energy (DOE). There are three main types of mixed waste Heterogeneous debris S5400 6,146.02 110.56 325.31 13,672.19 8,702.63
being produced or stored at DOE facilities, low-Ievel, high-level, and transuranic. Unknownlother matrix U9999 331.56 0.79 1.30 35.46 6.96
Lab packs X6000 527.13 13.57 39.82 2,558.53 923.98
Table 9.11 provides a summary of the estimated total inventories for the commercial-
Special waste X7000 5.70 1.83
and DOE-generated mixed wastes. Elemental mercury X7100 8.11 0.51 0.49 1.39 1.07
Elemental hazardous X7200 870.41 33.52 56.52 2,713.79 1,126.41
metals
9.2 HISTORICAL BACKGROUND Beryllium dust X7300 5.25
Batteries X7400 26.05 0.42 1.29 3.95 .21.04
Reactive metals X7500 394.63 0.00 0.20 1.80 1.20
The Resource Conservation and Recovery Act was promulgated in 1976 and required Explosives/propellants X7600 15.79 9.37 7.19 30.94 40.07
the EPA to regulate hazardous wastes from cradle to grave. However, RCRA specifical!y Compressed gases/aerosols X7700 9.89 0.00 - 0.14 0.03
excludes source, special nuclear, and by-product materials as defined by the Atomic Immobilized forms ZIOOO 145.75 0.00 14.00 97.53 1,067.63
Energy Act of 1954. In 1984 the court mandated that RCRA would apply to DOE's Decontaminated solids Z2000 0.00 - 293.98 134.64

hazardous wastes. It was not until October 6, 1992 that Congress passed the Federal Total 71,709.82 607.61 1,463.17 68,942.36 66,377.99

Facility Compliance Act, which required DOE and other federal facilities to comply
with EPA and state hazardous waste regulations and sanctions. Since that time DOE, "Based on Ref. 2.
NRC, and EPA have jointly worked to clarify the mies and regulations for handling,
packaging, and disposal of mixed wastes. 9.4 REGULATIONS AND STANDARDS FOR MIXED WASTES

Table 9.4 gives a chronologicallist of regulatory activities with regard to mixed wastes.
9.3 SOURCES, CLASSIFICATION, AND INVENTORIES

Mixed wastes are generated in every state in the United States, at al! federal facilities
working with nuclear materials, and at many hospitals, universities, and private
facilities. The largest portion by far is produced at DOE sites. The wastes produced
at DOE sites include MLLW, HLW, and transuranic waste (TRU). Tables 9.2 and
9.31 pro vide the combined total volume inventories (at al! DOE sites) by waste
formo
9.5 WASTE MINIMIZATION METHODOLOGIES
There are many technologies being developed by industry and within the National Labo-
ratory system. However, there are only a few that have been adequately demonstrated
~nd approved by NRC and EPA. The Chemical Technology Division at Oak Ridge Na-
lIona] Labs has been working on developing processes for separating the radioactive
294 MIXEO WASTES 9.6 WASTE PACKAGING ANO OISPOSAL 295

Table 9.3 Total volume (nr') of inventory and generation of DOE non-RCRA 'fable 9.4 Regulations and standards for mixed wastes
PCB MLLW, by physical forma
~ The Resource Conservation and Recovery Act (RCRA) is promulgated giving EPA the authority
Volume (rrr') to regulate hazardous waste from cradle to grave
NRC recognizes joint regulation for mixed waste rulemaking

MPCname

Liquids
MPC
code

LOOOO
Current
inventory

20.75
Actual
1996 1997
FY projections

1998-2006 --
2007-2030
1981
1984
1984
In LEAF vs. Hodell, the Court mandated that RCRA be applied to DOE hazardous waste,
Hazardous Solid Waste Amendments to RCRA increase the stringency of hazardous waste
requirements
EPA publishes notice c1arifying RCRA jurisdiction
Aqueous liquids/slurries L1000 5.73 1986
Land disposal restrictions for California are promulgated by EPA
Organic liquids L2000 59.99 0.00 0.00 0.00 0.00 1986
NRC and EPA publish draft guidance on the definition and identification ofLLMW.
Solids SOOOO 316.48 70.16 0.79 2.03 3.97 1987
NRC and EPA publish joint guidance on siting guidelines
Inorganic homogeneous S3100 20.12 0.60 0.97 5.51 2.31 1987
EPA promulgates LDR standards for solvents and dioxins
solids 1987
DOE c1arifies its position on by-product materials
Organic homogeneous S3200 1.37 1987
DOE Order 5400.3, Hazardous and Radioactive Mixed Waste Programs, establishes policy
solids 1987
guidelines and minimum requirements
Soil/gravel S4000 2,667.38
DOE Order 5820-2A, Management of Defense LLW, establishes policies for handling LLW
Debris waste S5000 8.06 0.41 11.11 69.85 34.80 1988
EPA publishes a notice which c1arifies requirements for facilities that treat, store, or dispose of
Inorganic debris S5100 1,102.63 1.00 1.80 1.00 0.50 1988
radioactive mixed wastes
O¡ganic debris S5300 82.54 0.56 1.44 7.46 19.90
1988 EPA publishes hazardous waste injection restrictions including mixed wastes
Heterogeneous debris S5400 228.01 0.07 0.07 0.63 1.68
1990 A conditionallO-year no-migration variance for limited amounts of untreated waste for the
Unknown/other matrix U9999 5.28 0.00 0.40 0.10 0.10
purpose oftesting and experimentation is granted to the DOE WIPP facility
Lab packs X6000 11.55
1992 EPA issues a policy of giving a reduced priority to civil enforcement of the RCRA storage
Total 4,529.89 72.80 16.58 86.59 63.26 prohibition
1992 Congress passes the Federal Facilities Compliance Act, which defines mixed waste and requires
DOE and other federal facilities to comply with RCRA
a Based on Ref. 2.
1994 EPA extends its policy of giving a reduced priority to civil enforcement of the RCRA storage
prohibition for 2 years
components from the nonradioactive wastes. These same engineers are also working on 1995 EPNNRC publishes Draft Guidance on the Storage of LLMW
1996 EPA announces a Iimited extension of its policy of prohibition of storage of mixed waste until
soil washing techniques and other technologies for in situ soil decontamination. These
April 20, 1998
technologies are not suficiently developed yet to be approved by the regulators. NRC and EPA jointly publish final guidance on the testing requirements for mixed wastes
1997
The following technologies have been approved by the regulators for use in treating
mixed wastes.

Pulsed plasma supercritical organics treatment This technology is available frorn
Solar Wind Environmental, located in Mountain View, California (information available
at http://www.techknow.org).This system uses an underwater plasma discharge, which
creates an electrical, shaped pulse in the water. The result is a violent supercritical elec-
trachemical reaction releasing hundreds of millions of electrons into the water. An
intense continuous reaction occurs from the pulse corona f1ow. Organic molecules are
split into their basic parts. For example, air and water separate into oxygen peroxy and
hydroxyl radicals.
Reduction O/ SOx/NOx and particulates This system is available from Specialty Chemical
Consultants, Inc., !ocated in New Berlin, Wisconsin (information available from
http://www.techknow.org). The treatment system utilizes combustion catalyst additives for
heavy/mazut or bunker C oil-fired utilities for reduction of unburned carbon particulates,
sulfur oxides, and nitrogen oxides. It improves the thermal and heat transfer efficiency of
boiler operation and saves on fue! consumption. It also reduces sulfur corrosion and low-
temperature corrosion in the system. This technology reduces ash load factors to 60% of that
achieved by magnesium hydroxide/oxide slurry-based products currently used by utilities.

Matrix enhanced treatment system This system is available from Earthworks Environ-
mental Inc. (information available from http://www.techknow.org). The matrix enhanced
treatment system is an ex situ treatment methodology to treat organic and inorganic
soil contamination in a single throughput of the unit. The treatment unit is mobile and
it is logistically very easy to mobilize and treat soils at the source. Treatment costs are
claimed to be less than 65% of the cost for landfilling while providing a permanent
solution.
9.6 WASTE PACKAGING AND DISPOSAL
lbe National Laboratories a!ong with other organizations are continuing to develop method-
Ologies to encapsulate and package mixed wastes for ultimate disposal. Brookhaven
National Laboratories (BNL) has done a lot of work in this area (information available
from http://www.dne.bnl.gov). Examples of their efforts follow.
 REFERENCES 297
296 MIXED WASTES

BNL has developed a low-density polyethylene encapsulation process for low,
level radioactive, hazardous, and mixed wastes that provides greater long-term stabil_
ity than products from conventional solidification technologies. Polyethylene is an
inert, low-permeability, thermoplastic material that is highly resistant to chemical
attack, microbial degradation, and radiation damage. This process can be used for ei-
ther microencapsulation or macroencapsulation. The microencapsulation process in-
vol ves heating the polyethylene above its melting point and combining it with the dry
waste to form a homogeneous mixture that is allowed to cool into a monolithic solid
waste form in which small particles are interspersed within the polymer matrix.
Macroencapsulation involves pouring molten polyethylene into a waste container in
which large pieces ofwaste have been suspended or supported. Upon cooling, the polv,
ethylene forms a solid layer sorrounding the waste.
Sulfur polymer cement, developed by the U.S. Bureau of Mines in 1972, is a ther,
moplastic material that is easily melted to a low-viscosity liquid at 120°C. BNL has
developed an encapsulation process that can be used to solidify fly ash in sulfur polymer
cement. The process involves using a dual-action mixer to simultaneously heat the waste
~nd binder with several additives to form a homogeneous mixture which simply cools
into a solid monolith waste form without the need for chemical reactions. As much as
2.5 times more incinerator fly ash can be solidified in sulfur polymer cement than in
hydraulic cement and with improved compressive and tensile properties.
The Environmental and Waste Management Group at BNL has been developing
and characterizing innovative thermosetting polymers for waste management use for
many decades. BNL has developed and characterized thermosetting polymers for
encapsulation of hazardous, mixed, and radioactive waste and for container materials.
These materials cover broad ranges of chemical and physical durability, performance,
viscosity, and cost. The polymers selected are innovative materials with desirable prop-
erties in both their fluid and solid states. This makes them suitable for applications
where impermeability, chemical resistivity, high strength, and long-term durability are
required.
BNL has proposed using new low-temperature glasses and glass-ceramics based on
advanced phosphate formulations for the treatment of low-Ievel and mixed wastes. The
high temperature (l200-1500°C) required for vitrification using borosilicate glass is a
major drawback because volatization of certain isotopes and heavy metals can occur.
Alternative glass compositions have been prepared with melt temperatures between
450°C and 900°C and with improved durability.
CAN. Canister model systems analysis. This package provides a computer simula-
ion of a system for packaging nuclear waste in canisters. The canister model calculates
t veral! programatic cost, number 01' canisters, and waste inventaries.
o COMRADEX4. Accidental release radiologic dose. This code was developed to
valuate potential radiologic doses in the near environment of radioactive releases,
e . I
especially postulated accident re eases.
PATU. Gamma dose calculations and shielding analysis. This code is a highly
flexible shielding code utilizing the common point-kernel integration technique.
GTIPS. Greater than Class C (GTCC) tracking, inventory and projection system.
This code was developed as part of the National Low Level Waste Management
Program's effort to characterize GTCC wastes.
RANCUMD. Radionuclide migration geologic media. This code is a one-
dimensional transport code for transport oí' radionuclide chains through layered geologic
media, taking into account longitudinal dispersion, convection, and retention.
WAPPA. Waste package performance assessment. This code is intended to serve as
a tool for evaluating both the relative and the absolute performance of waste package
design concepts.
9.8 DISCUSSION QUESTION
1. Which regulatory agency rules are applicable in the event of disagreement be-
tween the requirements of RCRA and AEA?
REFERENCES
1. Integrated Data Base Report-1996, U.S. Spent Nuclear Fuel and Radioactive Waste Inventaries, Projec-
tions, and Characteristics, DOEIRW-0006, Rev. 13, December 1997.
2. U.S. Department of Energy, Office of Environrnental Restoration, Office ofWaste Management, Techni-
callnformation Collection Data Base. Updated through October 30, 1997.

9.7 COMPUTER CODES

There are several computer codes used to address issues associated with mixed wastes-
Some of these codes are listed here, but this is not intended to be a complete list. The
following codes were obtained from a software catalog that is maintained by the U.S.
Department of Energy, Office of Scientific and Technical Information, Energy Science
and Technology Software Center, P.O. Box 11020, Oak Ridge, Tenn. 37831. Several
other computer codes are provided elsewhere in this book.