United States
Environmental Protection
Agency
Municipal Environmental
Research Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S2-84-057 Apr. 1984
&ER& Project Summary
Design and Development of a
Hazardous Waste Reactivity
Testing Protocol
C.D. Wolbach, R.R. Whitney, and U.B. Spannagel
A project was conducted to develop a
test scheme (protocol) to determine the
gross chemical composition of waste
materials in the field. Such a test
scheme is needed during remedial
actions at hazardous waste disposal
sites, where it is necessary to predict
the potential consequences of mixing
wastes from separate sources. Earlier
procedures have assumed a prior
knowledge of the chemical composition
of the wastes. Information obtained
from these tests is used to classify
wastes into reactivity groups and thus
predict compatibility.
The test scheme developed here
includes a field test kit, a series of flow
diagrams, and a manual for using the
flow diagrams and test procedures.
Because small-scale mixing is needed
as a safeguard before large-scale
mixing takes place (even when the
chemical composition of two wastes
indicates compatibility), a simple device
is included for observing the effects of
mixing two hazardous materials.
The protocol was challenged with
more than 60 compounds and mixtures
of compounds in the laboratory and 29
waste samples in the field. Of 755
laboratory observations, 15 were false
positives and 2 were false negatives
(including replicate tests). All but one of
the field samples were classified into
the correct reactivity group based on
the bulk chemical composition listed in
the suppliers' manifest. The one incor-
rectly identified sample was found to be
incorrectly labeled by the supplier and
was correctly classified according to its
actual composition.
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
With funds allocated by the regulations
to the Comprehensive Environmental
Response, Compensation, and Liability
Act (CERCLA), numerous locations have
been identified as containing large
quantities of hazardous wastes. Uncon-
trolled or abandoned hazardous waste
sites may present long-term danger to the
local environment and possible immediate
danger to personnel involved in cleanup
activities. A major effort in any cleanup is
the bulk recontainerization of materials
residing in leaking drums or tanks, or
stored in holding ponds. This task is
usually performed for shipment to inter-
mediate storage or ultimate disposal.
Many materials are incompatible with
each other and, when mixed, can result in
immediate catastrophic reactions or
intermediate-term reactions that can
cause dangerous results.
Presently, some work is underway to
identify the types of materials that have
compatibility problems and the potential
results of their mixing. These efforts are
primarily theoretical studies incorporating
the chemistry of pure compounds. One
study (Hatayama, H.K., et al., "A Method
of Determining the Compatibility of
Hazardous Wastes," EPA-600/2-80-
076, U.S. Environmental Protection
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Agency, Cincinnati, OH, 1980)* has
classified materials into several reactivity
groups, identified potential problems
with mixing the different groups, and
specified a logical series of procedures to
avoid mixing incompatible materials. The
procedures require that the user have at
least a minimal knowledge of thechemical
nature of the materials in question. Other
work has been directed toward field tests
for one or two specific reaction hazards or
chemical characteristics. These efforts
address only the most immediate and
catastrophic effects of incompatibility.
Cleanup personnel are left with no way of
estimating the short-term (minutes to
hours) or long-term (days to weeks)
effects of mixing and recontainerizing
unknown materials.
The purposes of this project were (1) to
identify any field-usable procedures for
classifying wastes into the reactivity
groups developed by Hatayama et al., (2)
to test identified procedures against
representatives of their respective reac-
tivity groups, (3) to establish a protocol for
the use of the procedures, and (4) to
assemble a field test kit. Tests were
needed for 41 reactivity groups, which
are numbered 1 through 34 and 101
through 107. These are called the
reactivity group numbers, or RGN's. The
tests used to classify a sample waste into
the correct RGN had to be simple enough
so that users with minimum training
could apply them. The associated protocol
had to be logical and contain a minimum
of complex decisions. The test kit itself
had to be as self-contained as possible
and require no field laboratory. That is, it
was to be transportable in a car or van and
to require an absolute minimum of
utilities.
The project was divided into six phases:
• Literature search to identify RGN
tests
• Testing of the identified procedures
against representative compounds
• Establishing the testing sequence or
protocol
• Verification of the reproducibility of
the protocol and test procedures
• Assembly of the field test kit
• Field verification of the complete
system using actual wastes
The project was successfully concluded
with the preparation of a hazardous
waste reactivity test protocol and asso-
•This EPA report is no longer available from EPA or
NTIS. An updated version of this report entitled "A
Proposed Guide for Estimating the Incompatibility of
Selected Hazardous Wastes Based on Binary
Chemical Reactions" is scheduled to be published in
1984 by the American Society for Testing and
Materials(ASTM)D34Committeeon Waste Disposal.
ciated field kit that allowed the correct
RGN classification of 29 wastes for which
there was no prior chemical knowledge.
Procedures
Because identifying the RGN for a
waste sample is a qualitative assessment,
the literature search concentrated on
qualitative analysis methods. Of particular
interest were color spot tests and other
wet chemical tests requiring only a few
milligrams of material. Reference and
text books for college-level qualitative
analysis courses (both organic and
inorganic) were reviewed along with
literature on spot testing. Some 59
compounds were selected from the RGN
lists of Hatayama et al. to provide the
broadest possible coverage on the
various groups. These compounds were
then subjected to the identified procedures
to verify that the tests gave unequivocal
results and correctly identified the RGN to
which the compound belonged.
The procedures were organized into a
sequence or protocol. Two technicians
were then assigned to subject the
(unmarked) compounds and mixtures of
compounds to the protocol. This procedure
was carried out to ensure that the
protocol would correctly classify the
compounds into their respective RGN's.
After successful completion of this
phase, the field kit was assembled. As
part of the kit, a field-mixing device was
also constructed. This device was a
simplification of previously developed
devices in that it did not require utilities or
a laboratory setting. The device itself is
used in the last step of the protocol to
verify that two materials will not generate
immediate catastrophic results when
mixed.
The final phase of the project was to
take the assembled kit to the field (the
EPA Combustion Research Facility at
Jefferson, Arkansas) and attempt to
identify and classify actual wastes. Much
of the testing was conducted indepen-
dently and in duplicate to assure that
different operators would achieve the
same results.
Results and Discussion
The literature search resulted in
identification of appropriate tests for all
but two of the listed RGN's — RGN 25
(nitrides) and RGN 103 (polymerizable
compounds). Tests for nitrides were not
sought because compounds were not
commercially available; synthesis of
nitrides is very dangerous, and the
authors felt that working with such
compounds offered too high a risk. In
addition to the two RGN's for which tests
were not found, no qualitative test could
be located for epoxides (RGN 34).
During verification of the 35 test
procedures, 755 individual observations
were made, including duplicate and
triplicate observations by a single techni-
cian and repeated run-throughs of the
protocol by two other analysts. Of the 755
observations, only 15 were false positives
and 2 were false negatives (including
duplicates).
Field testing was conducted on 25
wastes. Since 4 wastes contained 2
phases, a total of 29 samples was tested.
The waste descriptions in the suppliers'
manifests identified 39 materials classi-
fiable into RGN categories. The test
protocol identified 33 of these and also
found 15 additional RGN's that were not
predicted from the manifest information.
Indeed, one sample identified on the
manifest as a waste solvent was classified
by the protocol as RGN 106 (water and
mixtures containing water). On further
investigation, the sample was found to be
the water layer of a two-phase system
that had been mislabeled during sampling.
Two of the RGN's missed by the test pro-
cedure were manifested as being at low
levels. The levels were not specified. The
remainder of the unidentified RGN's
were organics dissolved in water, a
classification not in the current RGN list.
Analysis time averaged 1.3 hr per phase.
The sensitivities of the tests to their
respective RGN's is important because it
is not known at what levels the danger
from the reactivity of a particular RGN
may become significant. For example, an
oil identified as having high levels of
polychlorinated biphenyls (PCB's) was
found to contain chlorinated aromatic
organics (a correct identification); but two
oils said to have low PCB levels gave
negative responses to the chloride test.
The difference in the PCB levels of these
oils is not known, but they would require
significantly different decisions about
handling and disposal procedures. Also,
some materials had a positive nitrogen
test, but no nitrogen-containing RGN's
could be identified.
Conclusions and
Recommendations
Actual wastes were classified into
correct RGN's, and a hazardous waste
reactivity test protocol was developed
that can classify wastes into the 41
reactivity groups defined by Hatayama et
al. The equipment and materials needed
to carry out the protocol can be packaged
and transported to the field in a car or M
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small van. The tests can be conducted in
the field without utilities. The classifica-
tion time per waste phase (1.3 hr) is
reasonable.
Weaknesses in the field application of
the kit include the need for a working
surface of about 1.8 m2 (20 ft2) and
difficulties in performing the tests under
adverse weather conditions. Specifically,
wind, temperature below about 5°C
(40°F), or precipitation makes testing
difficult. Atemperature above 33°C(90°F)
will also have adverse effects on test
results. One potential problem area with
the RGN classification system is RGN 106
(water and materials dissolved in water).
The system does not classify water
phases heavily laden with dissolved
organics into the organic RGN's. A few
cases of compounds classified into the
wrong RGN by Hatayama et al. were also
noted.
Recommendations arising from the
results and conclusions of this project are
as follows:
• Efforts should be initiated to establish
the detection limits of the various
RGN tests.
• A review of the original (Hatayama
et al.) classification scheme should
be conducted to verify the accuracy
of the RGN listings.
• The predicted compatibilities of the
Hatayama et al. compatibility chart
should be verified in the laboratory.
• RGN 106 in Hatayama et al. should
be reviewed to determine whether it
is appropriately defined or should be
further broken down.
• Procedures should be developed to
identify organics in water phases
and the RGN's to which they belong.
• The protocol should be expanded to
include schemes for more accurate
identification of specific compounds
or classes of compounds.
• The protocol should be expanded to
include procedures to identify spe-
cific generic wastes streams.
• The protocol should be challenged
by an expanded variety of wastes.
A full report was submitted in fulfill-
ment of Contract No. 68-02-3176-38 by
Acurex Corporation under the sponsor-
ship of the U.S. Environmental Protection
Agency.
C. Dean Wolbach, Richard R. Whitney, and Ursula Spannagel are with Acurex
Corporation, Mountain View, CA 94042.
Naomi P. Barklay is the EPA Project Officer (see below).
The complete report, entitled "Design and Development of a Hazardous Waste
Reactivity Testing Protocol, "(Order No. PB84-158 807; Cost: $ 16.00, 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
6 U.S. GOVERNMENT PRINTING OFFICE: 1865-55941027069
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