r/EPA
United States
Environmental Protection
Agency
Municipal Environmental Research EPA-600/2-78-080
Laboratory. June 1978
Cincinnati OH 45268
Research and Development
Microwave Plasma
Detoxification
Process for
Hazardous Wastes
Phase II. Systems
Application
Evaluation
.
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-78-080
June 1978
MICROWAVE PLASMA DETOXIFICATION
PROCESS FOR HAZARDOUS WASTES
Phase II. Systems Application Evaluation
by
L. J. Bailin
Lockheed Palo Alto Research Laboratory
LOCKHEED MISSILES & SPACE COMPANY, INC.
Palo Alto, California 94304
Contract No. 68-03-2190
Project Officer
Donald A. Oberacker
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and policies
of the U.S. Environmental Protection Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
ii
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FOREWORD
The Environmental Protection Agency was created because of increasing public
and government concern about the dangers of pollution to the health and welfare of the
American people. Noxious air, foul water, and spoiled land are tragic testimony to
the deterioration of our natural environment. The complexity of that environment and
the interplay between its components require a concentrated and integrated attack on
the problem.
Research and development is that necessary first step in problem solution and
it involves defining the problem, measuring its impact, and searching for solutions.
The Municipal Environmental Research Laboratory develops new and improved
technology and systems for the prevention, treatment, and management of wastewater
and solid and hazardous waste pollutant discharges from municipal and community
sources, for the preservation and treatment of public drinking water supplies, and to
minimize the adverse economic, social, health, and aesthetic effects of pollution.
This publication is one of the products of that research; a most vital communications
link between the researcher and the user community.
This report summarizes a broad spectrum of applications for microwave plasma
processing of hazardous and highly toxic wastes. Technical discussions at U.S. EPA
Headquarters, regional offices, national conferences on toxic waste disposal, and at
other government and industrial facilities contributed to the information on the diverse
substances which could be disposed of by treatment with this new method.
Francis T. Mayo
Director
Municipal Environmental Research
Laboratory
iii
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ABSTRACT
This preliminary survey has revealed new information on several highly toxic
substances which exist within the continental U.S. for which there is no satisfactory
means of disposal. They exist in multiple ton quantities, as well as small centigram
batches at a multitude of locations. They are, specifically, materials in search of a
disposal method, such as the microwave plasma detoxification process (MWP). These
materials which have been surveyed for suitability in the MWP include the following
exceedingly dangerous compounds and mixtures:
• Cancer-causing nitrosamines, vinyl and vinylidene chlorides, dioxin-
containing organohalogens, and aromatic amine compounds which heretofore
have been considered only as oddities, or as being present only in small
quantities.
• Acute-toxicity organometallic compounds and heavy metal complexes, such
as mercury, arsenic, cadmium, and lead compounds, derived from industrial
processes and pesticides.
• Nerve-poisons from military sources, which include organophosphorus
chemicals stock-piled above ground, and from pesticide wastes which are
only slightly less hazardous.
Identification of these materials and sources is abstracted in Table A.
This information was obtained to identify real-world industrial requirements
and applications for microwave plasma detoxification of high-toxicity waste streams
and chemicals. To obtain the data, technical discussions were held at six U.S. EPA
regional offices, U.S. EPA Office of Solid Waste, Washington, DC, plus other govern-
ment and industrial facilities. Two national conferences on toxic waste disposal were
also attended.
With respect to identities, techniques, and locations of hazardous wastes, the
U. S. EPA regional offices, although highly cooperative, did not have a good "handle"
on the exact quantities of materials. The national conferences also left many questions
unanswered on this problem. It was indeed surprising to learn after much time spent
how poor the data were on quantities as related to specific locations. Only estimates,
at best, could be made. And for military-type materials, it may be stated unequivocally,
that a more extensive survey will be needed for their identification and location. It
was frustrating to know that the materials were "out there," but not be able to learn
anything beyond that point.
Positive information of a type, however, was expressed at the national meetings
which dealt with the philosophy of safe disposal. One group or faction spoke of in-
cineration as the only genuine means for decomposition or destruction. Landfill,
however, was loudly promulgated by those who regarded incineration as too difficult
IV
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to control for highly toxic materials, and thus too costly, dangerous, etc. The
incineration partisans described the storage and landfill alternative as only a temporary
answer; in this instance, the substances are covered up underground and left for
future generations to be troubled with.
If one wishes to consider, therefore, the applicability of the microwave plasma
technique as an ultimate disposal procedure, the materials cited in the table meet
the process requirements eminently well. The process to date detoxifies low poundage
quantities, depending on apparatus size, i.e., 1-10 lbs/hr in the original 5 kW unit,
and 10 - 30 lbs/hr in the 15 kW unit which is undergoing tests now. Pending continued
development, units of 50 - 100 IbsAr are envisioned. Several of these in parallel
should have sufficient capacity to satisfy all but very high volume throughput levels.
Predicted costs per pound based on three 15 kW systems operating continuously is
$0.20-0.25. Dilute toxic waste water streams are not suggested, only because the
energy of the plasma would be wasted in producing a stream or water plasma rather
than producing the chemical reactions which are necessary for total detoxification.
However, concentration of these streams can be accomplished, and these would then
be candidates for the microwave plasma process. Thus, the MWP appears as an
important adjunct, or the only method in many instances, for the detoxification of
hazardous wastes, which, because of their "too-hot-to-handle" reputations, cannot be
buried in landfill, or moved across statelines for detoxification or disposal.
This report fulfills Phase II of Contract No. 60-03-2190 by the Lockheed Palo
Alto Research Laboratory, Lockheed Missiles & Space Company, Inc., under the
sponsorship of the U.S. Environmental Protection Agency. The period covered was
February - July 1977.
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TABLE A. IDENTITIES AND KNOWN SOURCES OF
Toxic Material
Classification
Organophosphorus Compounds:
• Nerve gases or G-agents
(phosphonofluoridate s)
Flame retardant (e.g., "Tris")
Pesticides (phosphonates, thiophosphonates)
Anticholinesterase nerve toxin
Carcinogen
Anticholine sterase
Organometallic Compounds:
• Arsenical pesticides
• Mercurials pesticides
• Lead (tetraethyl lead)
• Metal cyanides
• Nickel carbonyl, Zn, Cd, Mn, Se, V,
Misc. Heavy metal compounds
Llpoid toxin
Primary organ toxins in humans
Primary organ toxins
Halogenated Compounds:
• Hexachlorobenzene (containing dioxin)
PCBs, Kepone, Mlrex, etc.
• DBCP (dibromochloropropane)
• Vinyl and vinylldene chlorides
Carcinogens
Male sterility in humans
Carcinogens
Organonltrogen Compounds:
• Nitrosamines (e. g., dimethyl nitrosamine)
• Aromatic amines (e.g., benzidines)
• Polyaromatic hydrocarbons, PAH (dyes,
pigments)
Carcinogens, teratogens, mutagens
(a) LD50 < 100 (oral lethal dose 50% test animals, < 100 rag/1 kg body weight).
(b) Temporary method: Materials have not been rendered chemically or biologically safe.
vi
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HIGHLY TOXIC*a) AND HAZARDOUS SUBSTANCES WITHIN CONTINENTAL U. S.
Source of Material
Quantities and Location,
Where Known
Disposal Method
Military: Stored pure agents. Stored waste
streams. Stored neutralization products
Manufacturer
Commercial, Industrial, Agricultural:
Pesticide manufacturing wastes
Outdated supplies
Unlabeled, unknown supplies
Thousands of gallons
Several thousand Ib
(Colorado, Utah, Maryland)
Probable 1000's of Ib (California)
1 to 10,000 Ib in various locations
Storage* ' above ground
IT II
Unknown
Chemical disposal sites,
incineration
Commercial, Industrial, Agricultural:
Solids
Holding ponds (Alexandria, Va. area)
New Mexico)
Solids, solutions
Process wastes
Plating wastes, solids
Petroleum catalysts, pesticides,
experimental complexes
100's of Ib
100 to 1000 gallons
100's of Ib, gallons
1000's of Ib (East and West Coast)
1 to 100 Ib, a few 1000's of Ib
(Texas, California, New Jersey)
Storage underground
Storage above ground
Storage underground
Storage above ground
Storage above and underground
Wet oxidation, UV, ozonolysis
Storage above and underground
Commercial, Agricultural
Fumigant/agrlcultural chemicals
Industrial waste streams and process bottoms
1000's of Ib
Estimated 1000's of Ib (California)
Estimated 1000's of Ib
Storage above and underground.
Incineration
Unknown
Storage and incineration
Industrial, Hospitals, Universities, Cancer
Centers. (Note: Expect larger quantities to
be identified at university laboratories from
greater awareness at these sources)
U.S. Navy smokes, flares, etc.
1 to 10 Ib (throughout U.S.)
100's of Ib
100's of Ib
Storage above and below ground
Unknown
vii
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CONTENTS
Foreword . iii
Abstract v
Figures x
Tables x
Acknowledgments ' x*
1. Introduction 1
2. SAE Program Criteria 3
3. U. S. EPA Regional Office Interviews 4
Region I, Northeast 4
Region III, Middle Atlantic 7
Region V, Midwest 7
Region VI, Southwest 7
Region VII, Midwest 8
Region EX, West 8
4. National Meetings on Toxic Waste Disposal 1°
1. National Conference About Hazardous Waste Management 10
2. National Conference on Treatment and Disposal of Industrial
Wastewaters and Residues H
5. Other Government and Industrial Interviews 12
1. California State Department of Health 12
2. California State Department of Health 12
3. Arthur D. Little, Inc. 15
6. Forum on Microwave Plasma Process U. S. EPA, Washington, D. C. 16
7. Conclusions and Recommendations 17
Appendix
Estimated Operating Costs for 15-kW Microwave Plasma System 19
ix
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Number
FIGURES
U. S. Environmental Protection Agency Regions and regional
interview locations
Extremely hazardous waste Class I disposal sites in State of
California
13
Number
TABLES
Identities and Known Sources of Highly Toxic and Hazardous
Substances Within Continental U.S.
Highly Toxic and Hazardous Waste Materials — U. S. EPA
Regions I, III, IV
Highly Toxic and Hazardous Waste Materials — U. S. EPA
Regions VI, VII, IX
Types of Extremely Hazardous Wastes Sent to California Class I
Landfill Sites - 1975 - 1977
14
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ACKNOWLEDGMENTS
This report was prepared by the Lockheed Palo Alto Research Laboratory,
Lockheed Missiles & Space Company, Inc., under U.S. EPA Contract No. 68-03-2190.
The work was performed in the Department of Chemistry, Dr. Ernest L. Littauer,
Manager. Dr. Lionel Bailin was Principal Investigator.
The Project Officer for the Environmental Protection Agency was Mr. Donald
A. Oberacker, Solid and Hazardous Waste Research Division, Municipal Environ-
mental Research Laboratory, Cincinnati. His guidance and support are sincerely
acknowledged.
Appreciation is also expressed to personnel from U.S. EPA Headquarters and
regional offices mentioned in this report who contributed time and effort in aid of
this program.
xi
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SECTION 1
INTRODUCTION
Of the approximately 10 million tons of toxic and hazardous wastes which are
generated yearly in the United States, it has been estimated that 10 to 20% will need
special methods for disposal. These materials are made up in large part from pesti-
cides which have been withdrawn from use, obsolete or below-specification toxic
substances, industrial wastes from chemicals, explosives, etc., and biological
residues, carcinogens, mutagens, and related materials. (*•>
For compounds of nominal toxicity, such as diluted DDT or other pesticides
mixed with solvent or municipal sludges, on the order of LDso's of 500 or higher,^)
notable achievements have been accomplished in thermal destruction, chemical and
biological detoxification, and special landfill methods. However, with the exception
of incinerator processing, relatively little new technology has been developed within the
last 10 years for the disposal of highly toxic, refractory, and extremely persistent
wastes in the form of concentrates, pure chemicals, or nondiluted process wastes.
The technique of deomposition of hazardous, concentrated organic compounds
by passage through a microwave discharge began at the Lockheed Palo Alto Research
Laboratory in 1967. In a U.S. Army supported program conducted during 1970 - 1972,
the decomposition of toxic gas simulants was carried out in which nearly 100% de-
composition of selected organophosphonate materials was performed in a laboratory-
size plasma system.(3) In 1975 - 1976, the U.S. EPA, Solid and Hazardous Waste
Research Division, Municipal Environmental Research Laboratory, Cincinnati, Ohio,
approved a feasibility study to test the process on several pesticides and toxic wastes.
As the consequence of several highly successful evaluations, the construction of an
expanded scale system followed, which resulted in an increase in throughput from 1 - 5
g/hr for the laboratory unit to 450 - 3200 g ( 1 to 7 Ib) per hr in the larger system.(3)
Consequently, the further design and construction of pilot equipment was authorized
by the U.S. EPA for expansion to a portable unit of 5 to 14 kg (10 to 30 Ib) per hr.
(1) Report to Congress, Disposal of Hazardous Wastes, U.S. Environmental
Protection Agency, Publication SW-115, 1974
(2) Lethal dose for 50% of test animals in mgAg of body weight
(3) Bailin, L. J., M. E. Sibert, L. A. Jonas, and A. T. Bell, "Microwave Detoxifi-
cation of Toxic Vapor Simulants," Environmental Science & Technology. 9(3),
254-58, 1975
(4) Bailin, L. J. and Barry L. Hertzler, "Development of Microwave Plasma De-
toxification Process for Hazardous Wastes," Phase I, U.S. EPA-600/2-77-030,
Apr 1977
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Preliminary to the construction and testing of the new unit, it was considered
essential to perform an intensive short-term survey to identify current industrial
requirements and potential applications for the process for application to real-world
highly toxic hazardous chemicals and waste streams. Those materials which might
be detoxified and yield valuable by-products, such as organometallics, would also
identified and proposed for additional development work. This report summarizes
the information which was obtained in this study.
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SECTION 2
SAE PROGRAM CRITERIA
To perform the systems application evaluation (SAE), specific tasks were
prescribed, as follows:
1. Identify existing industrial requirements and potential applications for
microwave plasma processing of real-world, highly toxic, hazardous
chemicals and waste streams. Municipal, agricultural, and ordinary
chemical wastes were not included.
2. Collect and publish the information and provide to U.S. EPA and related
personnel who are directly concerned with toxic and hazardous waste
management.
The method by which the information was obtained involved visits and technical
interviews with cognizant personnel at U.S. EPA Headquarters and regional offices;
attendance, participation, and discussion at two national conferences on toxic wastes;
and additional discussions at local government and industrial facilities. Details of
visits, interviews, presentations, etc. are given in the sections which follow.
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SECTION 3
U.S. EPA REGIONAL OFFICE INTERVIEWS
Of the ten U.S. EPA regional offices, interviews were conducted with personnel
from six locations.
Region Location
I Boston, MA
III Philadelphia, PA
V Chicago, IL
VI Dallas, TX
VII Kansas City, MO
IX San Francisco, CA
The regions in which the 60 percent sampling was performed are shown on the
map in Figure 1.
Preliminary to discussions of toxic problem wastes, a description of the micro-
wave plasma system was presented by the interviewer using visual aids, including an
8-minute color-sound 16-mm movie. The information was concerned with current and
projected process size, capacity, costs, and the anticipated schedule for scale-up.
In this way, the applicability of the process to regional problems and specific hazardous
substances could be estimated more readily.
REGION I, NORTHEAST
Boston, MA
Contact: Richard R. Keppler, (Acting) Director, Office of Research and Development
The materials of high toxicity to be disposed of were, principally, PCB's in
the sludge bottoms of several Massachusetts rivers, and waste pesticides. The
pesticides were estimated to be 200 tons at various locations throughout the region.
The PCB's are present at 40 — 50 ppm in the river sludges; if the contaminant is not
removed, the problem was estimated to remain approximately 50 years. See Table 1.
Toxic waste disposal is carried out mainly by means of storage and specialized
incineration. Until better methods become available, these are the only procedures
acceptable.
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Figure 1. U.S. Environmental Protection Agency Regions and regional
interview locations.
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TABLE 1. HIGHLY TOXIC AND HAZARDOUS WASTE MATERIALS - U.S. EPA REGIONS L HI, IV
Source of Information
U.S. EPA Region I (New England)
ME, VT, NH, MA, HI. CT
U.S. EPA Region HI (Middle Atlantic)
PA, MD, DE, VA, WV
U.S. EPA Region V (Midwest)
NM, WI, IL, IN, OH, MI
Location of Toxicants
Massachusetts:
Acushnet River
New Bedford Harbor
Housatonic River
Entire region
Hopewell, VA
James River, VA
Arlington
(Washington, D.C.)
Entire region
Belle, WV
Various locations
New Albany , IN
Entire region
Minneapolis, MN
Entire region
Michigan
Substance
PCB's
Various pesticides
Kepone
Kepone
Arsenical pesticide
Cyanide and ferric
cyanide from plating
baths
Nitrosamines
Vinyl chloride
Vinylidene chloride
Hexachlorobenzene
PCB's
Hexachloro-
naphthalene in fuel
oil
Organophosphonate
pesticide
Unlabeled chemical
wastes
Form
River and bay
sludge bottoms
All forms
Powder, etc.
River sludge
Solids
Holding ponds
Solution
Solids
Water solution
Liquid
Liquid
Liquid
Liquids
Solids
Quantities
40-50 ppm
High tonnages
> 200 tons
Estimated: 50 tons
High tonnages
Estimated: 100 's of Ib
100 's of gal
Estimated: 100'sofgal
100 's of Ib
Estimated: 100 's of gal
Estimated: tonnage quantity
Estimated: 100 's of gal
Estimated: > 100's of Ib
Estimated: > 1000 gal
Estlmat3d: >100'soflb
Several thousand
55-gal drums
Means
of
Disposal
Storage;
specialized
incineration
Storage
None
High-
temperature
incineration
Unknown
_
_
-
Storage
Storage and
incineration
Storage
Storage
Storage
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REGION IE, MIDDLE ATLANTIC
Philadelphia, PA
Contact: Albert Montague, Director, Office of Research & Monitoring
The following materials known to exist within the region were described as
needing special disposal methods:
Organic arsenical pesticides, Arlington, Virginia (Washington, D.C. area).
No disposal method exists other than chemical landfill.
Nitrosamines (carcinogens) present in cutting fluids were found in Belle, West
Virginia, as a water contaminant, and in Baltimore, Maryland, as an air contaminant.
Cyanide effluents from plating baths, especially ferric cyanide, are problem
areas. The latter is not oxidized readily by ozone or hypochlorite. Location is
nonspecific, i.e., they occur wherever cyanide baths are used.
Vinylidene chloride and vinyl chloride wastes in several-ton quantities were
located at one manufacturer's site.
Kepone and Kepone sludges at Hopewell, Virginia, are notorious problem
materials. Contaminated sludge is present in high multiple ton quantities in the
James River area. For Kepone pesticide solids stored in drums, a 50-ton figure was
estimated. See Table 1.
REGION V, MIDWEST
Chicago, IL
Contact: Karl Bremer, Toxic Substance Coordinator
Discussion indicated that significant quantities of hexachlorobenzene, PCB's,
hexachloronaphthalene in fuel oil, still-bottoms, organophosphonate pesticides,
research chemicals, and several thousand 55-gallon drums of unlabelled chemical
wastes are either being sent to landfills, or are being stored "outside" and "just
rusting." See Table 1. It was agreed that some means must be found for final disposal
since the landfills are only storage areas for these highly toxic substances. '
REGION VI, SOUTHWEST
Dallas, TX
Contact: Ms. Mildred Smith, Special Assistant for R&D Surveillance and Analysis
Several problems were discussed, principally those involving organometallic
compounds In Texas and New Mexico, several hundred pounds of arsenicals are
being stored in warehouses for want of a better means of disposal. Experimental
quantities of organometallic compounds in the 1 - 100 Ib range which contain Gd In etc
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have also been reported by petroleum companies to be in storage at their chemistry
and catalyst laboratories. Nickel carbonyl, lead compounds, zinc and manganese salts
are known toxic substances used by oil companies which need to be disposed of cor-
rectly. See Table 2.
It was reported that an inventory of toxic and highly toxic materials is being
collected at this time by Region VI from industrial and other sources. It was estimated
that data from this survey will be available on or about the latter part of 1978.
REGION VH, MIDWEST
Kansas City, MO
Contact: Morris Tucker, Chief, Solid Waste Programs
The principal hazardous materials of concern include:
Hexachlorobenzene mixed with oil, 4600 gallons, contaminated with 100 - 1000 ppm
of p-dioxin (2, 3, 7, 8-tetrachlorodibenzo-p-dioxin), in a tank stored near St. Joseph,
Missouri. No safe detoxification method exists.
PCB's and PCB-contaminated soil over a large area at relatively dilute con-
centrations are located in the St Louis, Missouri, area.
Pesticides in a fire-damaged warehouse in which the materials were partially
destroyed, or consist of unlabelled containers, are being retained above ground
in the St. Louis area. See Table 2.
REGION IX, WEST
San Francisco, CA
Contact: Charles T. Bourns, Chief, Solid & Hazardous Waste Management Program
Discussion revealed, principally, the problems in disposal of PCB's present
in waste transformer oils and old or discarded capacitors, Kepone and similar
pesticides, and miscellaneous organometallics. See Table 2. For details on quantities,
referral was made to the California State Department of Health for information from
their toxic substances list. These materials are identified in Section 5.
Inspection of both tables show the large numbers and varied types of toxic and
hazardous wastes scattered across the continental United States. They cover all types
of compounds, mixtures, etc., in all forms of matter. Based on the program scope, the
search indeed identified many materials which need treatment as soon as possible. It
is also quite certain that many more substances will be located under more intensive
scrutiny - which is strongly suggested for future investigations.
8
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TABLE 2. HIGHLY TOXIC AND HAZARDOUS WASTE MATERIALS - U. S. EPA REGIONS VL. VII, DC
Source of Information
U.S. EPA Region VI
(Southwest)
AR, LA, NM,
OK, TX
U.S. EPA Region VH
(Midwest)
10, KS, MO, NE
U.S. EPA Region IX
(West)
CA, NV, AZ
Location of
Toxicants
Victoria, TX
New Mexico
Houston, TX
Texas
St. Joseph, MO
St. Louis, MO
St. Louis, MO
Entire region
Entire region
Entire region
Entire region
Substance
Arsenlcals
Arsenlcals
Nickel carbonyls
Lead compounds
Gd, In, Zn, Mn,
Pb compounds
Waste stream mix-
tures of organo-
metallics
Hexachlorobenzene
in oil
(100—1000 ppm
p-dioxin)
PCB's
Pesticides
Kepone
Pesticides
Organometallics
PCB's
Form
Solids
Solids
All forms
Liquid,
Slurries
Liquid
Liquid
All Forms
Solids
All Forms
All forms
Liquid,
Capacitors
Quantities
Several hundred
pounds
Several hundred
pounds
1 -100 Ib each
Estimated:
1000's of gal
5000 gal
> 100 gal
> 1000 Ib
Multipounds
> 1000 Ib
> 100 Ib
Multigallons
Disposal
Landfill or
storage
Landfill or
storage
Landfill or
storage
Storage
Storage
Storage
Storage
Landfill
(Class I sites)
Landfill
Landfill
Landfill
Landfill
to
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SECTION 4
NATIONAL MEETINGS ON TOXIC WASTE DISPOSAL
Two conferences were attended during the SAE program. At the first, an EPA-
Lockheed coauthored paper was presented on the initial phase of microwave plasma
process development. At the second, solutions to difficult residue disposal problems
were presented by varied speakers. The primary objective of attendance by the
writer was to develop a high degree of familiarity with the real issues of hazardous
materials disposal and detoxification. In this regard, the goal was well met. There
were, however, a number of presentations at the second conference which were,
unfortunately, repetitions from the first.
1. NATIONAL CONFERENCE ABOUT HAZARDOUS WASTE MANAGEMENT
San Francisco, CA, February 1-4, 1977
Chairman: Dr. Harvey F. Collins, California State Department of Health
This meeting was sponsored by the U.S. EPA, California State Department of
Health, and Governmental Refuse Collection and Disposal Association.
The EPA-Lockheed coauthored paper, "Developments in the Low Temperature
Microwave Plasma Process for Hazardous Waste Disposal and Recovery" reported
data obtained during the EPA, Cincinnati, supported program on the successful scale-
up of the microwave plasma process. Additional relevant topics included
• Definitions of terms, such as hazardous, extrahazardous, highly toxic wastes,
etc., in several independent contributions.
• Development of the California hazardous waste transportation manifest, its
complexity and requirements, or "Getting Hazardous Waste From Here to There."
• Visits to two Northern California Class I (Chemical Disposal) Sites for the
disposal of hazardous/toxic material: Pacific Reclamation and Disposal, Inc.,
Benecia, and Sierra Reclamation and Disposal, Inc., Martinez, CA. There
were varied opinions on what highly toxic materials would be acceptable for
disposal underground. For example, no military wastes, politically "hot"
or related materials are accepted at Class I sites in California. Since
incineration is extremely limited within the state, landfill appears to be the only
acceptable means for disposal.
• With regard to landfill, encapsulation, etc., in the keynote address to the
conference, Senator John F. Dunlap, Member of the California Legislature
and author of California's 1972 Hazardous Waste Control Legislation, called
for additional emphasis on recycling and recovery of energy values. Senator
10
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Dunlap stated that toxic material burial, although acceptable now, may become
a serious problem later. Paraphrasing his further remarks, he said, the
undesirable storage of these substancesumderground may require guards-with-
guns to watch over them -forever.
2. NATIONAL CONFERENCE ON TREATMENT AND DISPOSAL OF INDUSTRIAL
WASTEWATERS AND RESIDUES
Houston, TX, April 26 - 28, 1977
This symposium, sponsored by AIChE (South Texas Section); Gulf Coast Waste '
Disposal Authority; U.S. EPA; University of Houston; and Information Transfer. Inc..
dealt with, principally, the treatment of industrial wastewaters and residues with
regard to solutions to difficult disposal problems, ultimate disposal (so-called
encapsulation) treatment processes, costs of alternative methods, area-wide manage-
ment, and new concepts.
The presentation included technical and administrative problems, which in the
main, were concerned with sludge, pretreatment methods, and similar broad-based
applications. Although toxic or highly toxic substances were discussed as part of a
number of presentations, no new toxic materials not previously covered in other
papers or publications were revealed. Important contributions were, however, made
during several presentations and discussions, as condensed below:
• Dr. Stephen J. Gage, Deputy Assistant Administrator for Energy, Minerals
and Industry, U.S. EPA, Washington, D. C. In the keynote address, he
emphasized recovery and re-use. For example, metallic zinc was listed
as an "endangered" material. He said that only 20 years of production remain
within the U.S., and, therefore, diligent resource recovery should be
practiced.
• Mr. George S. Thompson, Jr., Chief, Metals and Inorganic Chemicals Branch,
IERL, Cincinnati, discussed the need for recovery of metals, especially toxic
species, such as Hg, Cu, Pb, Cd, As, Se, and V from industrial sludges,
incinerator discharges, etc.
No single method for disposal of toxic wastes was considered applicable for all
types of materials. Indeed, there were several interesting informal discussions during
and after the meeting "in the halls" regarding the difficulties associated with even the
major disposal techniques. For example, incineration was stated as the only real method
for decomposition or destruction. However, landfill was promulgated by those who re-
garded incineration as too difficult to control (for highly toxic materials), costly, dangerous
etc. Incinerator partisans described the storage and landfill alternatives as only a tem-
porary answer in which the substances are covered up underground and left for future
generations to be troubled with.
The information gathered at both meetings supported the proposal that organo-
metallics, chlorinated hydrocarbons, and carcinogens are strong candidates for micro- '
wave plasma processing, but, of course, these toxins had been known previously. Support
for the use of the plasma process was derived from the estimated quantities of the materials
to be detoxified, although the exact numbers were not known with confidence by any of the
meeting personnel contacted.
11
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SECTION 5
OTHER GOVERNMENT AND INDUSTRIAL INTERVIEWS
Referral of the interviewer to the California Department of Health (CDH),
Berkeley, by EPA Region IX; a return visit by a CDH waste management specialist
to Lockheed Palo Alto Research Laboratory (LPARL); and a visit to Arthur D. Little,
Inc. (ADL), Cambridge, MA, comprise the interviews listed in this section.
1. CALIFORNIA STATE DEPARTMENT OF HEALTH
Berkeley, CA
Contact: Warren Manchester, Associate Industrial Hygienist, Waste Management
Division
A visit to the Waste Management Division yielded maximum information on the
toxic materials which the State of California classifies as extremely hazardous, i.e.,
those with an oral, rat LDso (lethal dose, 50% fatalities) of less than 50_ (< 50 mg
toxicant/1 kg body weight of test animal). A briefing on these materials indicated
that literally hundreds of highly toxic materials, in quantities from 1 - 10 g to
thousands of gallons, are being sent to Class I chemical disposal sites. The location
of these sites in California is shown in Figure 2. These included PCB's, pesticides,
carcinogens, organometallics, cyanides, antibiotics, rocket fuels, hydrofluoric acid,
and rejected or distressed substances. These are part of one-time laboratory clean-
outs, monthly industrial waste inputs to the sites, hospital biological wastes, and
local, city government disposals from their pesticide and rodenticide storage. A
summary tabulation of materials deposited at the sites since 1975 is listed in Table 3.
During the visit, the applicability of the microwave plasma detoxification process to
these wastes was discussed, particularly since Class I landfill has been the only answer
for disposal of many of these highly toxic materials within the state.
All the items in Table 3 are candidates for detoxification by the microwave
plasma process.
2. CALIFORNIA STATE DEPARTMENT OF HEALTH
Berkeley, CA
Contact: Carl G. Schwarzer, Waste Management Specialist, Vector & Waste
Management Section
As the result of the discussion at Berkeley on the applicability of the microwave
plasma process to many of the toxic wastes now being sent to Class I sites, a return
visit by a CDH specialist to the Lockheed Palo Alto Research Laboratory was arranged.
The purpose was to discuss in greater detail the start-up date of the 15-kW plasma
12
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1. PACIFIC RECLAMATION &
DISPOSAL
2. SIERRA RECLAMATION &
DISPOSAL. NO LONGER
OPERATING.
3. RICHMOND SANITARY SERVICE
4. HOLLISTER DISPOSAL SITE
5. SIMI VALLEY LANDFILL
6. CALABASAS LANDFILL
7. PALO VERDES LANDFILL
8. WESTCOVINA LANDFILL
9. STRINGFELLOW QUARRY
COMPANY. NOW CLOSED.
10. OMAR RENDERING COMPANY
11. OTAY LANDFILL
^CLASSIFIED AS ACCEPTABLE
FOR DISPOSAL OF GROUP I
WASTES BY THE CALIFORNIA
REGIONAL WATER QUALITY
CONTROL BOARDS.
Figure 2. Extremely hazardous waste Class I disposal sites in State of California.
13
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TABLE 3 TYPES OF EXTREMELY HAZARDOUS WASTES SENT TO CALIFORNIA
CLASS I LANDFILL SITES - 1975 - 1977
Materials
Alkali Cyanide
PCB's
Nickel Cyanide
Sodium Cyanide
Tetraethyl Lead
Aflatoxin
Arsine Mixed With
Nitrogen
Benzidine
Hydrochloride
Strichnine
Rocket Fuels/
Propellants/
Miscellaneous
a -Naphthylamine
Methyl Yellow
Agricultural
Chemicals. Outdated:
Organophosphonates ,
Chlorinated
Hydrocarbons ,
and Carbomates
Antibiotics ,
Miscellaneous
Source
Plating company
Transformer
manufacturer
Plating company
Plating company
Petroleum
company
USDA
Semiconductor
company
Hospital
Plant nursery
Chemistry
laboratory
Hospital
Supply house
Hospital
Form
Solution, 1 Ib/gal
Liquid, transformer
oil
Liquids
Solution, 12 oz/gal
Solution, 12 oz/gal
Sludge
Contaminated peanut
butter, 1000 ppm
Gas , 5000 ppm
Solid
Solid, gopher
poison, 3% agent
Solids
Solid
Solid
Solids, dispersions
Solids, dispersions
Quantities
2000 gal/yr
62 x 55 gal
drums
40 x 55 gal/yr
3000 gal/yr
800 gal/yr
1000 gal
2 x 55 gal
drums
Bottles under
pressure
225 g
350 Ib
10-lb batches
100 g
20 g
500-1000 g
Ib quantities
—
14
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unit, the estimated costs, and, specifically, the potential for handling chemical
carcinogens, such as benzidine, nitrosamines, etc. Part of Mr. Schwarzer's
responsibility is to reduce as far as possible the influx of these and related toxic
materials to the Class I sites. A second visit is scheduled when the 15-kW system
becomes operational.
3. ARTHUR D. LITTLE, INC.
Cambridge, MA
Contact: Dr. Joan Berkowitz
In 1975 - 76, A. D. Little, Inc. (ADL) performed a survey study for U.S. EPA,
Office of Solid Waste, Washington, D.C., under EPA Contract 68-01-3554, to
evaluate new disposal methods for toxic wastes. A visit to ADL was made in order
to correct what Lockheed believed to be a misunderstanding on ADL's part concerning
the engineering aspects of the microwave plasma process. Personnel at ADL had had
previous experience with these plasmas, but were not familiar with the recently
developed, EPA, Cincinnati, supported Lockheed microwave scale-up program.
In this context, several subjects were discussed, which included: microwave plasma
chemistry and its engineering potential as applied to hazardous wastes, the background
of the LPARL plasma process scale-up, and the application of an oxygen plasma as the
principal reactor medium. By the completion of the discussions, the misunderstandings
were cleared-up, such that the projected Lockheed scale-up plans for the near future
were understood readily by the meeting participants. Potential toxic materials dis-
cussed for MWP treatment were nitrosamines, carcinogens, organophosphonate nerve
poisons, chlorinated hydrocarbons, and organometallic compounds.
15
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SECTION 6
FORUM ON MICROWAVE PLASMA PROCESS
U.S. EPA, WASHINGTON, B.C.
The purpose of the forum was to present to interested individuals within
the Government environmental community the most recent developments in microwave
plasma technology for the disposal of very hazardous wastes. The attendees repre-
sented EPA, NIH, Army, Air Force, Navy, and the Frederick Cancer Research
Center. The presentation was held March 1977 at the Office of Solid Waste (OSW),
Waterside Mall Headquarters. Mr. Donald A. Oberacker, Solid and Hazardous
Waste Research Division, Cincinnati, presided as EPA meeting chairman. Dr. L. J.
Bailin, Lockheed principal investigator, presented the technical data.
As the result of a broad line of questions posed and answered during a well-
attended and lengthy session, several conclusions were reached, which may be
summarized, principally, as follows.
• OSW appeared convinced with regard to the workability and usefulness of such
a device, particularly portable units.
• Agencies other than EPA, such as NIH, the Army, and Air Force showed
an appreciation for small, but highly toxic waste streams which need a
disposal process, such as the microwave plasma, but for which costs are
of secondary importance.
• A number of materials were brought forward which would be amenable to this
treatment. These included organometallics (mercury, arsenic compounds),
organophosphonates (anticholinesterase toxins), polyaromatic dyes and
polyaromatic hydrocarbons (carcinogens). These were mentioned at various
times as materials in search of a disposal method.
This meeting served, therefore, as a focal point for questions which had accum-
ulated for more than a year since the inception of the program in April 1975. It served
as a forum since various needs were expressed for the process, even though a complete
cost analysis for a portable system was not available then. It emphasized that, although
costs were without doubt important, there were materials which needed to be detoxified
now for which no satisfactory means for disposal existed at "ten times the price. "(5)
Thus, as a result of the information exchange, important new information and needs
were'determined for microwave plasma processing within the governmental sphere.
As an example, one agency requested that it be permitted to support the program in
a related study during the continuing developmental phases. All the information
obtained in the meeting was therefore scheduled for follow-up, since the requirement
was immediate for the agency which stated this request.
(5) See Appendix for estimation of operating costs.
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SECTION 7
CONCLUSIONS AND RECOMMENDATIONS
As the result of a Systems Application Evaluation, it has been shown that, without
doubt, there are a large number of compounds, wastes, mixtures, and problem
materials which need safe, efficient, and cost-effective means for disposal. Current
methods have been almost exclusively underground landfill, or above-ground ware-
house or exposed drum storage. This is not a true disposal, but a "hiding" action,
in that the materials are still there, in place, waiting for a disposal method which
will carry out the detoxification eventually.
The highly toxic and hazardous wastes which have been found applicable for
microwave plasma processing, as determined on this program, include gases, pure
liquids, solutions, slurries, pure solids, and solids mixed with inorganic components.
These are stored in drums, cannisters, bottles, in dispersion, and in settled-out
form, both pumpable and nonpumpable in consistency and, therefore, cover the gamut
of materials handling technologies. The materials are listed by classification
below. l
• Organometallic compounds and waste pesticides, containing mercury,
arsenic, cadmium, nickel, zinc, and other metals
• Organophosphorus compounds and wastes, such as chemical warfare agents
and similarly constituted pesticides.
• Organic nitrogen compounds and wastes which have been shown to manifest
significant carcinogenic, teratogenic, and mutagenic tendencies in test animals.
• Halogen-containing hydrocarbons and related impurities, which include many
compounds of recent notoriety, such as PCB's, Kepone, p-dioxin, DBCP, etc.
All of these are problem materials which give great concern to those who are
responsible for their safe disposal. This is so even for compounds which are present in
gram or pound excesses, as well as for the hundreds of gallons/thousands of pounds
of toxic chemicals.
Therefore, an important place as a true-disposal mechanism may be readily
claimed for the microwave plasma process. The method is important, since it can
be made portable for use in areas where the materials to be treated cannot be
transported or moved because of local or federal ordinanaces regarding the handling
of these substances. Also, the recovery of by-product metal values from the
organometallic wastes would serve national needs by way of recycling, as described by
EPA guidelines.
17
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Therefore, recommendations concerning further process development from the
point of view of need are positive. It should be noted, however, that although hundreds
and thousands of pounds of these highly toxic materials have been listed, we did dis-
cover that the details on their many specific locations were woefully poor. It was
indeed surprising to learn after much time spent how poor these data were, "was
frustrating to know that the materials were "out there" but not be able to learn anything
beyond that point. And for military-type toxic and hazardous materials, it.may-be
stated unequivocally that a more extensive survey will be needed for their identifi-
cation and location.
18
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APPENDIX
ESTIMATED OPERATING COSTS FOR 15-kW MICROWAVE PLASMA SYSTEM
The costs for treating approximately 1 ton of Kepone solids/day are detailed
below.
Equipment costs are based on current figures for microwave plasma hardware
and predicted needs for ancillary parts. The trailer and truck are estimated
separately.
Electrical usage, 1.6 kWh,* for operating the plasma system on a per pound
treated basis, is estimated to be constant for all organic materials, since the maximum
microwave power available from the power sources is used for generation of the plasmas.
Oxygen consumption for Kepone is 5.58 SCF/lb calculated, based on formation of
chlorine, and equimolar quantities of CO and CO.
4
A 330-day/yr, 24 hr operation is used, in which three units treat 90 Ib/hr of
Kepone solids. Throughput is 2,160 Ib/day, or 712, 800 Ib/yr.
Labor costs are based on one-man operation of three automated units.
EQUIPMENT AND OPERATING COSTS
1. Microwave hardware, including vacuum pump, materials feed, $ 85, 000
recovery system, and on-board analyzer, per unit
2. Cab and trailer, one per 3 MWP units 25, 000
3. Electricity, industrial usage $0.015/kWh
4. Oxygen, large volume usage $0. 005/SCF
Add $3, 000/yr storage costs
5. Labor $9/hr
The calculated process costs based on these data are tabulated as follows:
*Development of Microwave Plasma Detoxification Process, Phase I, EPA Report
600/2-77-030, April 1977, p. 30.
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VARIABLE COSTS (YEARLY BASIS)
Operating labor, 7920 hr x $9/hr $ 71, 280
Maintenance, 4% of equipment, including cab and trailer 11, 200
Oxygen, 712, 800 Ib x 5. 58 SCF/lb x oxygen cost 22, 887
Electricity, 712, 800 Ib x i. 6 kWh/lb x electricity cost 17.107
A. Total Variable Costs $122,474
FIXED COSTS
Capital Recovery (10 yr - 7%)* 39> 872
Taxes and Insurance (2%/yr) 5> 60°
B. Total Fixed Costs $ 45, 472
Total Annual Costs, A + B $167, 946
Treatment Cost per Pound $ 0.23
*Compound interest factor, uniform series capital recovery, 0.1424, from D. G.
Newman, Engineering Economic Analysis, Engineering Press, San Jose, 1976.
20
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1.JBEP.OBTNO.
EPA-600/2-78-080
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
MICROWAVE PLASMA DETOXIFICATION PROCESS
FOR HAZARDOUS WASTES
Phase II. Systems Application Evaluation
5. REPORT DATE
June 1978 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
L. J. Bail in
8. PERFORMING ORGANIZATION REPORT NO.
. PERFORMING ORGANIZATION NAME AND ADDRESS
Lockheed Palo Alto Research Laboratory
Lockheed Missiles and Space Company, Inc.
Palo Alto, California 94304
10. PROGRAM ELEMENT NO.
1DC618
11. CONTRACT/GRANT NO.
Contract No. 68-03-2190
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory--Cin.,OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final for Phase II - 2/77-7/77
14. SPONSORING AGENCY CODE
EPA/600/14
is.SUPPLEMENTARY NOTES Project Officer:Donald A. Oberacker
This contract is continuing and currently in Phase III.
See also EPA-600/2-77-030 and EPA-600/2-78-081.
513/684-7881
16. ABSTRACT . •
mis preliminary survey has revealed new information on several highly toxic substances
ich exist within the continental U.S. for which there is no satisfactory means of
Jisposal. They exist in multiple ton quantities, as well as small centigram batches at
i multitude of locations. They are, specifically, materials in search of a disposal
nethod, such as the microwave plasma detoxification process (MWP). These materials
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