United States
Environmental Protection
Agency
Municipal Environmental Research
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S2-83-118 Jan. 1984
SERA Project Summary
Treatment of Reactive Wastes at
Hazardous Waste Landfills
Douglas Shooter, Joo Hooi Ong, Alan Preston, and John R. Ehrenfeld
A study was undertaken-to provide
information for personnel who must
make decisions about the disposition of
reactive hazardous wastes (Federal and
State personnel, employees accepting
hazardous wastes at existing disposal
sites, and coordinators performing
remedial action at uncontrolled waste
sites). These wastes generally display
one or more acute physical or chemical
hazards and form an immediate threat
to human health or the environment.
Though Federal regulations place
reactive wastes in a special category,
they do not identify applicable treat-
ment methods.
In response to the need for better
information, this report identified
problem wastes, treatment alterna-
tives, and data gaps. Emphasis is placed
on simple treatment and disposal
schemes that are likely to be the most
cost effective. The measures described
are either already in use or they are
promising techniques that require little
further development and have a high
probability of success. Information is
provided on the possible hazards and
the appropriate safety precautions to
protect personnel and property.
This Project Summary was developed
by EPA's Municipal Environmental
Research Laboratory. Cincinnati. OH.
to announce key findings of the
research project that is fully
documented in a separate report of the
same title (see Project Report ordering
information at back).
Introduction
Though reactive hazardous wastes
constitute only about 5% of all hazardous
waste, extreme caution must be used
during their transportation, handling,
storage, treatment, and disposal. These
wastes generally display one or more
acute physical or chemical hazards and
form an immediate threat to human
health or the environment (fire or
explosion, for example). The Resource
Conservation and Recovery Act (RCRA)
provides a special classification for
reactive wastes and prohibits certain
treatment and disposal methods for
them, but the regulations do not specify
treatment methods that are applicable.
Thus adequate information on handling
reactive wastes is very much needed, but
it is difficult to provide because of the
wide variety of chemical behavior that
can be expected from materials in this
category.
This report provides an information
base for personnel who must make
decisions about the disposition of
reactive wastes—Federal or State
personnel, employees accepting
hazardous wastes at existing disposal
sites, or coordinators performing
remedial action at uncontrolled waste
sites. Emphasis is placed on simple
treatment and disposal schemes that are
likely to be the most cost effective. The
measures described are either already in
use or they are promising techniques that
require little further development and
have high probability of success.
Information is provided on the hazards to
be anticipated and the appropriate safety
precautions needed to protect personnel
and property and to prevent any further
environmental damage. Appendices in
the full report list representative samples
of chemical compounds or species that
can be classified as reactive hazardous
wastes, and they present alternative
treatment technologies identified from
the literature.
Methods
Three methods were used to obtain the
data in this report: A review of extensive
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inhouse background information on the
characteristics of reactive hazardous
wastes, a review of the recent literature
(particularly information on the handling
and treatment of hazardous chemicals),
and direct comment and information from
operators of hazardous waste disposal
sites (including those specializing in
reactive wastes).
Identification of
Problem Wastes
Classification Scheme
The initial classification scheme
adopted in this work appears in Table 1
and was originally published as part of
the RCRA regulations. Two broad
categories of reactive wastes exist--
explosive and nonexplosive. The wastes
are further divided into the eight
categories listed in Table 1. In practice,
reactive wastes have a wide range of
chemical behavior and many do not fall
exclusively into a single category. The
following hierarchy is proposed for
classifying reactive chemicals based on
their potential for causing acute physical
damage (fire and explosion) and exposure
to toxic gases:
VII < Vl< VIII < l< IV < IIK IK V
Some of these classes are further subdi-
vided, with each subcategory having
somewhat different reactive effects,
consequent hazards, and necessary
safety precautions.
The full report describes the properties
of reactive wastes in each class, cites
representative examples, defines the
hazards associated with that type of
reactive material, and outlines the
necessary safety precautions.
Safety Precautions
Reactive wastes can cause acute
adverse effects to human health and thus
must be stored, handled, treated, and
destroyed by experienced operators.
Three types of acute effects can be distin-
guished: Explosion, fire, and exposure to
toxic gases. For many wastes, at least two
of these effects may occur simultane-
ously. Materials that may detonate must
be treated with extreme caution.
Transportation of many reactive
wastes is extensively covered by DOT
regulations. Expert help may be needed to
treat or dispose of wastes when they are
dangerous or unacceptable for transport
because of aging, lack of inhibitors, or
deterioration of the container. Reactive
wastes should be handled according to
the harmful effects of the most hazardous
member of a particular class, since
reactivity can vary considerably depend-
ing on many factors.
The full report provides general
guidance as to safety precautions for
each class of reactive waste. But more
detailed information and experienced
personnel are required to permit actual
Table 1.
Class
Reactive Waste C/asses*
Reactivity Characteristic
I The waste is normally unstable and readily undergoes violent change without detonating.
II The waste reacts violently with water.
Ill The waste forms potentially explosive mixtures with water.
IV When mixed with water, the waste generates toxic gases, vapors or fumes in a quantity
sufficient to present a danger to human health or the environment.
V The waste 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.
VI The waste is capable of detonating or exploding if it is subjected to a strong initiating
source or if heated under confinement
VII The waste is readily capable of detonation or explosive decomposition or reaction at
standard temperature and pressure.
VIII The waste 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 in 49 CFR 173.88.
"Source: Federal Register, Vol. 45, No. 98, p 33122, May 19, 1980.
2
handling of reactive wastes. In addition,
specific requirements may be imposed by
local codes and ordinances.
Identification of
Treatment Alternatives
Defining Alternatives
To define alternative treatment
technologies, background data were
assessed and the literature was searched
for specific examples using commonly
recognized chemicals or waste materials
from each reactivity class. Next, each
treatment technology was classified
either as "isolation and containment" or
as "destruction." Each technology was
then assessed according to the following
criteria: Technical feasibility, applicabil-
ity, chemicals and equipment required,
operator requirements, residual
production, advantages and disadvan-
tages, and relative cost.
Isolation and Containment
Eight isolation and containment tech-
niques are broadly applicable to a number
of reactive waste classes. The degree to
which each technique is applicable to
these eight classes is indicated in Table 2.
No technique is applicable to all eight
classes of reactive wastes, but two
procedures stand out as generally
applicable: (1) dilution with excess solids
and sealing in a dry container (applicable
to Classes I through V) and (2) mixing with
water and excess inert or absorbent solids
(applicable to Classes VI, VII, and VIII).
Destruction
Seven techniques for hazard destruc-
tion are broadly applicable to a number
of reactive waste classes (Table 3).
These techniques are not as broadly
applicable to a group of waste classes as
are those for containment and isolation
because destruction requires more
specific technology. Mixing with an inert
solid followed by open burning may be the
most broadly applicable technique,
though it is not applicable to Class V
(cyanides and sulfides).
Data Gaps and Research Needs
A number of data gaps have been iden-
tified by this preliminary study. Some of
the most important needs are listed here:
1. A comprehensive listing of
hazardous wastes detailing reactive
properties, hazards, and necessary
safety precautions. A useful body of
data does exist (the Oil and
Hazardous Materials Technical
-------
Assistance Data System), but many
fairly common examples of reactive
wastes are not included.
1. A directory of EPA-registered
hazardous waste transporters and
treatment, storage and disposal
facility (TSDF) operators who are
qualified and willing to accept
specific classes of reactive wastes.
3. Guidance on the maximum
quantities of a waste that can be
handled by simple procedures.
4. Inventory data indicating the types
and quantities of reactive wastes
entering the market for treatment
and disposal.
5. Development, testing, and docu-
mentation of simple techniques for
destroying reactive wastes.
Results and Conclusions
Classification of Reactive
Wastes
Reactive wastes can be broadly classi-
fied as explosive and nonexplosive. They
are further divided into eight classes
listed in the Federal Register (Vol. 45, No.
98, p. 33122, May 19, 1980). These eight
classes account for the chemical diversity
of reactive wastes quite well, but a
further subdivision of Classes I and II is
proposed to allow for a better definition of
materials that are pyrophoric, polymer-
izable, or oxidizers.
Safety Precautions
Reactive wastes pose acute hazards to
personnel and property and they may also
create longer-term environmental
hazards. Blast protection, protective fire-
resistant clothing, and breathing
apparatus may have to be used, as appro-
priate. Materials that may explode
(particularly wastes that are not well
characterized) should not be moved but
should be isolated from other wastes,
property, and personnel. Wastes that are
not explosive should be moved to a safer
location to isolate them from other
wastes, property, and personnel. Further
containment, handling, and treatment
requirements can then be determined.
Isolation and Containment
Techniques
No universally applicable technique
exists for isolating and containing all
reactive wastes. Hazards in transpor-
Table 2. Isolation and Containment Techniques
Applicability to Reactive Waste Class*
Procedure
Mix with excess inert solid material
and seal in a dry container
Mix with excess solid absorbent
and seal in a dry container
Mix with excess solid absorbent
in a vented container
Mix with water and excess inert
A
X
a
X
X
1
B
X
D
X
X
c
D
n
D
n
A
n
D
n
X
II
B
n
D
X
X
III
n
n
n
X
IV
X
n
X
X
V
X
n
X
X
VI
X
X
X
D
VII
X
X
X
n
VIII
X
X
X
n
solid material
Immerse in alcohol/water mixture
Immerse in alkaline solution
Immerse in kerosene
Encapsulate in a cement matrix
X X X X X
X X X X X
X X X X X
X X a X X
X
X
D
X
X
X
*
X
X
a
X
if
D
X
X
a
D
X
X
n
Table 3. Destruction Techniques
Procedure
A B C A B
vent gases
Mix with weak alkali
React with calcium hypoch/orite
React with ferrous chloride
solution (reducing agent)
Mix with alcohol/water and burn
Mix with solid (vermiculite)
and burn
D X D D D
X X X X X
X X n X *
a X X X X
D D X X D
*
X
*
X
D
n
a
X
X
n
a
a
X
X
X
X
X
*
n
*
X
X
*
tation, handling, and storage of water-
reactive wastes can be reduced by
diluting the material with an inert solid or
absorbent (vermiculite, sand, etc.) and
protecting it from moisture. Explosive
materials should be kept in a wet state,
however, as they are much more shock-
and friction-sensitive when dry. For some
explosive wastes, any handling or
transport can be extremely hazardous.
These wastes may have to be destroyed
onsite.
D
X
X
D
' X = not applicable, D = applicable, * = applicable only to some members of the class.
Applicability to Reactive Waste Class*
II III IV V VI VII VIII
Mix with excess water
Mix with excess water and
X
D
X
*
D
D
D
D
a
D
a
a
X
n
X
X
X
X
X
X
X
X
X
X
X
n
*
X - not applicable, D = applicable, + = applicable only to some members of the class
Destruction Techniques
Two destruction techniques are more
broadly applicable than the others-open
burning and reaction with water. Open
burning may apply to most or all reactive
materials except cyanides and oxidizers.
This method has been applied to various
types of water-reactive materials (e.g.,
alkaline metals) and avoids some of the
complex equipment required for other
-------
destruction techniques. Open burning
has also been applied to the destruction
of explosives and is still a permitted use
for them when they cannot be safely
incinerated. Local permit requirements
may limit open burning except as an
emergency response.
Reaction with water (for Classes I
through IV) has more complex
requirements than open burning, but
energy needs are low. Destruction of
water-reactive wastes in aqueous media
may lead to the production of explosive
or toxic gases that must be vented or
scrubbed from the atmosphere. The use
of open burning for these wastes pro-
duces different reactions that generally
avoid the formation of explosive or toxic
gases. Explosive wastes are stable m
water, but some can be destroyed by
alkaline solution.
Reaction with calcium hypochlorite (or
other similar chlorine-containing com-
pounds) is a well-developed and widely
practiced technique for the destruction of
inorganic cyanides. Though other
techniques are available, little advantage
appears to exist in supplanting this tech-
nique with any other. Sulfides can be
oxidized by the same technique. Organic
sulfides and cyanides can be destroyed by
combustion.
Field Interviews
The field interviews covered three
major companies in hazardous waste
management and three companies
specializing in management of reactive
wastes. Each company has its own
procedures for managing reactive wastes
and is selective about the type of wastes
it will accept. The major companies tend
to be conservative and refer very danger-
ous wastes to specialist companies. All
the companies stressed the importance
of obtaining expert advice about the
specific waste and its location before
attempting to handle it.
Recommendations
1. Work should be done to expand the
documentation of reactive hazard-
ous wastes listed in the appendices
to the full report. An expanded field
interview program should be
conducted to assess information
available from the literature and
from industry. The data should be
documented to make them more
accessible to TSDF operators. For
wastes that have no data available,
conservative estimates should be
made based on expected chemical
properties.
2. Simple techniques and equipment
should be developed for destroying
wastes in water and aqueous
media. Information is needed on
appropriate feed rates, venting or
scrubbing of off-gases, and treat-
ment and disposal of spent reaction
and scrubber solutions.
3. A program should be instituted to
further develop the techniques and
equipment for the open burning of
reactive wastes. The program
should define the following
parameters: Maximum quantities of
waste to be treated, potential
hazards, necessary safety precau-
tions for personnel and equipment,
requirements for auxiliary fuel, and
disposal of residuals.
4. Estimates should be developed to
compare the costs of destroying
reactive wastes with the costs of
alternative technologies, particu-
larly long-term containment or
landfill.
The full report was submitted in fulfill-
ment of Contract No. 68-01-5949 by
Arthur D. Little, Inc., under the sponsor-
ship of the U.S. Environmental Protection
Agency.
Douglas Shooter, Joo Hooi Ong, Alan Preston. John R. Ehrenfeld are with Arthur
D. Little, Inc., Cambridge, MA 02140.
Robert Landreth is the EPA Project Officer (see below).
The complete report, entitled "Treatment of Reactive Wastes at Hazardous Waste
Landfills," (Order No. PB 84-124 833; Cost: $10.00, subject to change) will be
available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Municipal Environmental Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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