United States
Environmental Protection
Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S2-87/069 Nov. 1987
<>EPA Project Summary
Reference Manual of
Counter measures for Hazardous
Substance Releases
Walter Unterberg, Robert W. Melvold, Scott L Davis, Frank J. Stephens,
and Pitzhugh G. Bush III
When a release of hazardous sub-
stances has occurred or threatens to
occur, federal, state, local government,
or industrial personnel may have to
assume responsibility for immediate and
planned removal, which is the principal
cleanup and treatment phase. They
must select treatment and disposal
processes, or countermeasures, which
are effective for the particular hazardous
substances and circumstances of the
The manual described in this Project
Summary contains procedures to assist
response personnel in selecting optimum
countermeasures. The procedures make
up a rational methodology which con-
sist of four decision-making steps in
series, starting with identification df
the substance(s) involved and site-
specific parameters, and ending with
an optimization of technically feasible
counter-measures in the light of eco-
nomic, logistic, and other criteria. The
methodology uses comprehensive
tables, or matrices, which provide
technical guidance for almost 700
hazardous substances designated by the
Comprehensive Environmental Re-
sponse, Compensation and Liability Act
of 1980, otherwise known as CERCLA
or Superfund (PL96-510). Remedial
action of a long-term nature, which
follows removal, is not addressed here.
The manual is designed as a reference
for use in field or office and stands
alone. It is based on available, some-
times incomplete, sources. Its purpose
is to provide persons with a limited
background a fast, workable guide to
plausible removal countermeasures.
given a reasonable amount of know-
ledge about the release. The user should
be cognizant of federal, state and local
regulations that may impact the decision
to select specific countermeasures, and
of the fact that these regulations may
be amended from time to time. An
example of the application of the manual
to a real situation is included.
This Project Summary was developed
by EPA's Hazardous Waste Engineering
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).
Objectives and Background
The manual described in this Project
Summary is designed to assist federal,
state, and local government and industry
personnel who may find it necessary to
respond to a release (or threat of a release)
of hazardous substances designated in
the Comprehensive Environmental Re-
sponse, Compensation and Liability Act
of 1980 (CERCLA). Approximately 700
hazardous substances have been
designated pursuant to CERCLA Section
101(14). The manual applies to many
types of releases, including transportation
and non-transportation related ones as
well as those from hazardous waste sites.
The manual guides the responder
through a series of decisions and actions
to be taken at the site of the release or
potential release. Actions such as these
are mandated by the National Contin-
-------
gency Plan (NCP) (40 CFR Part 300).
Note that regulations may be amended
from time to time, as may lists of regulated
chemicals. Check to see that your in-
formation is up-to-date.
Manual Contents
The entire manual is summarized in
Figure 1, which shows how Sections 2 to
5 are used in the selection of counter-
measures for a given release situation.
Section 2 of the manual provides
guidelines for situation assessment. This
provides for the identification of the
hazardous substance and determination
of the proper response procedures
dependent on the medium (atmosphere,
surface water, ground) receiving the
release. Discussions on site assessment,
guidelines for protective clothing selec-
tion, and equipment decontamination at
the affected sites are offered in Ap-
pendices A, B, and C.
Section 3 addresses the selection of
countermeasures. The information gen-
erated in Section 2 is utilized in three
steps: The "A" Tables disclose the physical
nature of the hazardous substances in-
volved and the associated hazards; the
"B" tables establish various technically
feasible countermeasures based on Tables
A; and the "C" Tables give the optimal
countermeasures in light of applicable
criteria and parameters. Samples of all
three tables are provided in this Project
Summary. Note that the number-letter
combination identifying each table is
based both on the nature of the spilled
substance and on the type of receiving
medium. The term countermeasure in-
cludes physical, chemical, and biological
cleanup; treatment; and disposal pro-
cesses to be carried out on-site or off-
site. Countermeasure selection criteria
include considerations of the degree of
cleanup achievable, environmental fac-
tors, logistics, safety, and cost. One
possible alternative is to take no immedi-
ate action and rely on isolation alone
until such time as the hazards have
lessened and suitable countermeasures
can be applied.
Section 4 lists all countermeasures
in Section 3. The countermea-
sures are categorized and defined in terms
of their characteristics, advantages, and
disadvantages. Having been presented at
the conclusion of Section 3 with at least
one optimal countermeasure, the re-
sponder may make the final choices by
referring to this listing. An important use
of the listing occurs when a release con-
sists of two or more hazardous sub-
stances. It is crucial that synergistic ef-
fects be considered. The application of
different countermeasures in parallel or
in series must then be closely examined.
Section 5 lists the bibliography which
underlies the entire manual. A total of
285 sources were accessed; of these,
235 were reviewed and 203 distinct
sources extracted. The cut-off publication
date for bibliography sources was 1983.
The bibliography is categorized with major
headings similar to those used in Sections
3 and 4 and arranged alphabetically by
author within each category. Section 4
references the original sources so that
the responder may obtain more detailed
information, if desired. The final subsec-
tion, "General Sources," contains a list
of references, each of which may address
a number of different countermeasures.
Three appendices conclude the manual.
All three are devoted to safety aspects
necessary in the approach, entry, and
decontamination of a hazardous spill or
waste site. Appendix A presents sug-
gested guidelines for site assessment,
entry, and control. Appendix B provides
Scenario
Chemical & Physical
Data
Countermeasure
Selection
Countermeasure
Description
Solid or Liquid
Spill in Water
Liquid Spill on
Land
Solid Spill on
Land
Table 1A
^- Table 2A
Table 3A
Gases
Table 4A
Table 1B 1C
Table 2B «-2C
Table 3B -3C
Table 4B - 4C
Table SB * 5C
Table 6B 6C
*- Table 7B «- 7C
Table # of Pages Table # of Pages Table # of Pages Table # of Pages Table # of Pages
1A
2A
3A
4A
40
14
23
2
IB
2B
3B
4B
2
2
1
1
SB
6B
78
2
2
1
1C
2C
3C
4C
4
4
5
5
5C
6C
7C
4
3
1
Figure 1. Pathways in the use of the manual.
2
-------
details on suggested guidelines for selec-
tion of chemical resistant clothing.
Appendix C discusses decontamination
protocols in terms of work zones, safety
clothing, and equipment.
Use of the Manual
Brief Overview
The selection of countermeasures for a
given release situation is illustrated in
Figure 1. Briefly, four steps are carried
out in series:
1. The Spill Scenario is obtained from
Section 2:
The Hazardous Substance and its
state (liquid, solid, gas); and
the medium (water, land, atmo-
sphere) into which it is released.
2. Chemical and Physical Data of the
released substance are obtained from
the "A" Tables in Section 3:
Releases in water Table 1A;
Liquids released on land Table
2A; Particulate solids released on
land Table 3A; Compressed
gases released into air Table
4A.
3. Technically Feasible Countermea-
sures are obtained from the "B" Tables in
Section 3:
Spills on water: Insoluble sinkers
Table 1B; Soluble sinkers
Table 2B; Insoluble floaters
Table 3B; Soluble floaters Table
4B; Liquid spills on land Table
5B; Paniculate solid spills on land
Table 6B; Compressed gases
released into air Table 7B.
4. Optimum Countermeasures are
selected from among the Technically
Feasible Countermeasures by using the
"C" Tables in Section 3 (Tables 1C through
7C correspond to Tables 1B through 7B).
For more details about items 1 to 4
above, the manual presents:
Descriptions of the Counter-
measures and their characteris-
tics (for better understanding of
the Optimum Countermeasures)
in Section 4, and a
Listing of the Original Sources
from which Descriptions of the
Countermeasures were taken
(including both specific and
general references) in Section
5.
The preceding decision-making
methodology has related to one hazardous
substance release into one environmental
medium. The correlating parameter in
steps 2 and 3 is the chemical class to
which the substance of interest has been
assigned. The countermeasures then
depend on the chemical class. Actual
spill situations may involve (a) hazardous
substance(s) belonging to more than one
chemical class and (b) scenarios of more
than one hazardous substance being re-
leased into more than one environmental
medium.
For eventualities (a) and (b), the fol-
lowing procedure is suggested. The
responder should carry out steps 2, 3,
and 4 for all alternative chemical classes,
hazardous substances, and media per-
taining to the incident. The result will be
a multiplicity of feasible and optimum
Sample page from "A" Table:
Table 1A. Releases in Water
countermeasures, usually a choice of
several for any one set of inputs. The
responder should select countermeasures
which are common to the chemical
classes and substances released into each
medium. Also, a judgment must be made
about the cleanup priority of each
medium, e.g., should countermeasures
for different media be performed in series
or in parallel, or in some other time
relationship? To help the user with such
decisions, the material in Sections 4 and
5 emphasizes logistics, speed of deploy-
ment, cost of different countermeasures,
etc.
Hazardous
Substance
Acenaphthene
Acenaphthylene
Acetaldehyde
Acetic acid
Acetic anhydride
Acetone
Chemical Class/
CAS No.
Aromatics
CAS 83-32-9
Aromatics
CAS 208-96-8
Aldehydes
CAS 75-07-0
Acidic compounds.
organic
CAS 64-19-7
Acidic compounds,
organic
CAS 108-24-7
Ketones
CAS 67 -64-1
Hazardfs)
In Addition
To Toxicity
Combustible
Combustible
Flammable
Polymerizable
Combustible
Corrosive
Combustible
Corrosive
Flammable
* "B" Table Reference
* Behavior in Water
IB Insoluble Sinker
3B Insoluble Floater
4B Soluble
2B Soluble
2B Soluble, decomposes
4B Soluble
Acetone cyanohydrin Cyanides and nitrites
CAS 75-86-5
Acetonitrile
Acetophenone
Acetyl bromide
Acetyl chloride
2-Acetylamino
fluorene
Cyanides and nitriles
CAS 75-05-8
Ketones
CAS 98-86-2
Aliphatics,
halogenated
CAS 506-96-7
Combustible w/toxic
products
Poison
Flammable w/toxic
products
Combustible
Aliphatics,
halogenated
CAS 75-36-5
Amines, aryl
CAS 53-96-3
Flammable w/toxic
products
Corrosive
Reactive
Flammable w/toxic
products
Corrosive
Reactive
Potential carcinogen
1 -Acetyl-2-thiourea Ureas
CAS 591-0802
4B Soluble
4B Soluble
1B Insoluble Sinker
2B Decomposes (Sinker)
2B Decomposes (Sinker)
IB Insoluble Sinker
2B Soluble
-------
Countemneasure Considerations
The many techniques for containment,
treatment, and disposal (listed in Table 8
of the manual) need to be considered in
their basic, practical aspects. Depending
on the location of the treatment and any
interference with the environment, three
types of countermeasures are possible:
1. In Situ: The spill site is not significantly
disturbed by the treatment method
carried out on the site, e.g., radio-
frequency heating of ground surface
using implanted electrodes (removed
after treatment) to distill off organic
pollutants.
2. On Site: The spill site is disturbed by
the treatment method which is carried
out on the site, e.g., contaminated soil
is excavated, incinerated on the site in
mobile incinerators, and the clean soil
is replaced on the site.
3. Off Site: The spill site is disturbed, and
the contaminated material transported
off the site is either (a) treated in a
Table IB. Insoluble Sinkers in Water
Containment
Applicable
Countermeasures
Chemical Class
Acidic compounds, organic
Aliphatics, halogenated
Amides, anilides and imides
Amines, alky!
Amines, aryl
Aromatics
Aromatics, halogenated
Asbestos
Azo compounds
Basic compounds
Chromates
Cyanates
Cyanides and nitrites
Epoxides
Esters
Ethers
Halides, alkyl
Halides, inorganic
Heavy metals
Ketones
Nitro compounds
Nitroso compounds
Olefins
Organometallics
Organophosphates
Oxides
Peroxides
Phenols and cresols
Phosphorous and compounds
Phosphates and phosphonates
Strychnine and salts
Sulfates
Sulfides and mercaptans
SuHites
Sulfones, sulfoxides. & sulfonates
Ureas
8
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^/V Use during dredging operations
(2) Mechanical dredging applicable to particulates only
(3) Reduce contaminant levels below toxic level through flow augmentation and mechanical mixing. Applicable to small spills in remote areas only!
(4) Treat with dilute and/or removable acids
(5) Treat with sodium hypochlorite or calcium hypochlorite
(6) Treat with hydrogen peroxide or ozone
(7) Potentially biodegradable
-------
Tab/0 1C.
Counter-
measures
Curtain
Barriers
Dams, Berms,
Dikes
Stream
Diversion
Synthetic
Membrane
Cover
Trenches
Dispersion
Dredging
Pumping
Activated
Carbon
Column
Biological
Treatment
Insoluble Sinkers
I
5 «.
S.I
a|
(Q
*.' 0)
S*
1 °
S Potential
§ Extent of
<> Mode Cleanup
C In-situ NA
C In-situ NA
C In-situ NA
C In-situ NA
C In-situ NA
D In-situ Gross
D In-situ Gross
D In-situ NA
T On-site Moder-
ate
Polish
T Off-Site Moder-
ate
Polish
Limitations Requirements
Environmental
« S §" S
§ 5 t 1
'*" w ^
5J Q) a*
o 1 c * §
X *« « & I 1§ "
cq)'*-!JS>^i9' § **
^ ^ ^ o '^ E> Oj -^ *** fe
S « S Jj ^ -8 "J -g 3 co i
Depen- t>:|S.£all-l»^lB I
Form dent J$|^5Sc§.IJ:fcS ^
ofHS Time So-'-Ss^ScoQ.SOco *
Neat <1 day X X XX X TEC
Diss
Neat varies X X X X X HEO
Diss CE
Neat varies X X X XX
Diss HEO
CE
Neat varies X XXX X
Diss TEC
PRO
Neat varies X X X X X X
Diss HEO
CE
Neat >1 day X
Diss
Neat >1 day XXX X
TEC
CE
Neat varies XX X
Diss TEC
Diss >1 day X X X X X
TEC
PRO
Neat Varies X
Diss STE
.^
a Q>
1 *
£ Unit £
Cost Comments
$200- 1.1.3.2 Max. current
300/ft 1-2 knots
Max. depth
2-5 feet
Max. waves
6 feet
$4/cuyd 1.1.1 Earth moving
equipment may
require special
access
1.1.5 Earth moving
equipment may
require special
access. Power
required for
pumps. Mobile
unit available.
3-4C/sq. 1.2.3 Material must be
ft. chemically
11972) compatible with
hazardous
substance
Navigable water
only
1.1.2 Underwater
trenches may
require special
equipment
X 1.3.5 Bad weather and
rough water may
enhance
dispersion. Type of
HS dictates
whether
dispersion usable
in populated
acreas
X $5-15/yrf 1.3.1 Par/meter of spill
must be known.
Requires large
boat/barge
$50-60/hr 1.3.4 -32' height limit
for vacuum
pumping. May
need corrosion/
explosion proof
pumps.
2-23C/gal 2,1.1 Spent carbon
50-55C/lb must be
regenerated or
disposed of.
X 4.0 May require
special bacteria.
-------
Table 1C.
Counter-
measures
Biological
Treatment
Coagulation/
Flocculation
Granular
Media
Filtration
Gravity
Separation
Incineration
Incineration
Ion Exchange
(Anionic/
Cationic)
Neutralization
(continued)
Limitations Requirements
Environmental
1 I 1 8
£ | ^ "^ 2
W. *« "Q *- tt) CQ
Q. 0) O "5 C x ?>
2 E x » « 1 I 5 *-
? f^a^-^Cb^"^- O*w
I* Sa5'SbS|.o,§-'|^
5 Potential Depen- "g52 & |
g Extent of Form dent i$||jji§.c§.!,§:s§. 5 * Unit
0 Mode Cleanup of HS Time sa-i-ssn^toQ-SOn * Cosr
T In-situ Moder- Diss >1 day XXX
ate STE
Polish
T On-Site Moder- Diss <'/zday XX X
ate CHE
CH
TEC
T On-Site Gross Neat >1 day XXX
STE
TEC
T On-Site Gross Neat <1 day XX TEC
On-Site Moder- Neat <1 day X XXX XXX PRO X
ate Diss
Polish
(Disposal)
Off-site Moder- Neat <1 day X X X X PRO X $395-
ate Diss 791 /ton
Polish solid $53-
(Disposal) 237/ton
111-
T On-site Moder- Diss >1 day X X X X X CHE
ate TEC
Polish
T On-site Moder- Diss >1 day X X X X X TEC
ate Neat CHE
Polish
j~
9
%
Cb
Comments
4.0 May require
special bacteria.
3.1 1 stage of
treatment process.
Usually followed
by filtration or
gravity separation.
23 1 stage of
treatment process.
Follows floccu-
lation/ coagulation
& precedes
polishing.
2.4 1 stage of
treatment process.
Follows floccu-
lation/ coagulation
& precedes
polishing. May
require special
equipment.
5.2 May require stack
monitoring. May
produce toxic
gases/ashes.
5.2 May require stack
monitoring. May
produce toxic
gases/ashes
3.4 Proper selection of
resin is very
important.
3.6 Neutralizer itself
may be hazardous.
May cause violent
exothermic
reaction.
-------
Table 1C.
Counter-
measures
Neutralization
Oxidation
Oxidation
Precipitation
Precipitation
Synthetic
Sorbents
Synthetic
Sorbent
Column
Wet Air
Oxidation
(continued)
Limitations
Environmental
I |
§.! 1
1 o .§ 5 § (o 5
5> Potential Depen- u § S. jjj jjj 5
§ Extent of Form dent £%.*,££'<:>.
T In-situ Moder- Neat <1 day X X XX
ate Diss
Polish
T On-site Moder- Diss >1 day X
ate
Polish
T In-situ Moder- Diss <1 day X X XX
ate
Polish
T On-site Gross Diss >1 day X
Polish
T In-situ Gross Diss <1 day X X XX
Polish
T In-situ Gross Neat <1 day X XX
T On-site Moder- Diss >1 day X
ate
Polish
T Off -site Moder- Diss <1 day
ate
Requirements
I | g
1 1 1
II | I 1 1 «,
3co
-------
Table 1C. (continued)
Counter-
measures
Landfill
ent. Dispersement
Treatment
c *"
Contain!
c
Limitations
Requirements
Environmental
(0
(0
1 ^
^> 4)
1 1 1
Potential
Extent of
Mode Cleanup
Off-site (Disposal)
Form
ofHS
Neat
Diss
JS (K 9) "^ ^ >
~ " "S J
Depen- tj § a fe « Q !
dent | S | | | & i
Time S a. K S S co :
Varies
S Uj i
i « < a
i M 1
5 co1
-------
the best combination of countermeasures
to apply.
The manual was submitted in partial
fulfillment of Contract No. 68-03-3014
by Combustion Engineering Corporation
under the sponsorship of the U.S. En-
vironmental Protection Agency. It covers
the period September, 1982 to July, 1984,
and work was completed as of December,
1984.
W. Unterberg, R. Melvold, S. Davis, and F. Bush are with Combustion
Engineering Environmental Monitoring Services, Inc. Newbury Park, CA
91320.
Leo T. McCarthy (deceased) was the EPA Project Officer {see below for present
contact).
The complete report, entitled "Reference Manual of Countermeasures for
Hazardous Substance Releases, "(Order No. PB87-232 252/AS; Cost: $24.95,
subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
For information John S. Farlow can be contacted at:
Releases Control Branch
Hazardous Waste Engineering Research LaboratoryCincinnati
U.S. Environmental Protection Agency
Edison, NJ 08837
-------
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