United States
             Environmental Protection
             Agency
             Office of Air Quality
             Planning and Standards
             Research Triangle Park NC 27711
EPA-450/4-79-023
September 1979
             Air
&EPA
Detonation of Explosives;
An AP-42 Update

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                                  EPA-450/4-79-023
Detonation  of Explosives;
      An  AP-42 Update
         Pacific Environmental Services, Inc.
               1930 14th Street
          Santa Monica, California 90404
            Contract No. 68-02-2583
       EPA Project Officer: Audrey McBath
     U.S. ENVIRONMENTAL PROTECTION AGENCY
         Office of Air, Noise, and Radiation
     Office of Air Quality Planning and Standards
     Research Triangle Park, North Carolina 27711

              September 1979

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This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers. Copies are
available free of charge to Federal employees, current contractors and
grantees, and nonprofit organizations - in limited quantities - from the
Library Services Office (MD-35), U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina 27711; or for a nominal fee,
from the National Technical Information  Service, 5285 Port Royal Road,
Springfield,Virginia 22161.
This report was furnished to the Environmental Protection Agency by
Pacific Environmental Services, Inc. ,  1930 14th Street, Santa Monica,
CA 90404, in fulfillment of Contract No. 68-02-2583. The contents of
this report are reproduced herein as received from Pacific Environ-
mental Services, Inc.  The opinions, findings, and conclusions expressed
are those of the author and not necessarily those  of the Environmental
Protection Agency.  Mention of company or product names is not to be
considered as an endorsement by the Environmental Protection Agency.
                   Publication No. EPA-450/4-79-023
                                   11

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                         TABLE OF CONTENTS
                                                          Page
FIGURES	   i v
TABLES	   i v
INTRODUCTION	   1
DETONATION OF EXPLOSIVES	   2
11.3.1  General	   2
11.3.2  Emissions and Controls	   3
REFERENCES FOR SECTION 11.3	   7
BACKGROUND DOCUMENT	   8

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                              FIGURES





Number                                                       Page



11.3-1    Two-, three-, and four-step explosive trains	     4
                              TABLES





Number                                                       Page



11.3-1    Emission factors for detonation of explosives	    6
                                IV

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                            INTRODUCTION

   As the title indicates, this report was written for inclusion
in EPA Publication No. AP-42, Compilation of Air Pollutant Emission
Factors.  The work was performed under Work Assignment No. 12 of
EPA Contract No. 68-02-2583.
                                 -1-

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 11.3   DETONATION  OF  EXPLOSIVES                           Audrey  McBath

 11.3.1   General1'5

   This  section deals mainly with  pollutants resulting from the
 detonation of  industrial explosives and small arms firing.  Mili-
 tary applications are excluded  from this discussion.  Emissions
 associated with the  manufacture of explosives are treated in
 Section  5.6, Explosives.

   An explosive is a chemical material that is capable of extremely
 rapid combustion  resulting in an explosion or detonation.  Since
 an adequate supply of oxygen cannot be drawn from the air, a source
 of oxygen must be incorporated  into the explosive mixture.  Some
 explosives, such as  trinitrotoluene (TNT), are single chemical
 species, but most explosives are mixtures of several ingredients.
 "Low explosive" and  "high explosive" classifications are based on
 the velocity of explosion, which,  in turn, is directly related to
 the type of work the explosive  can perform.  There appears to be
 no direct relationship between  the velocity of explosions and the
 end products of explosive reactions.  The end products are primarily
 determined by the oxygen balance of the explosive.  As in other
 combustion reactions, a deficiency of oxygen favors the formation
 of carbon monoxide and unburned organic compounds and produces
 little,  if any, nitrogen oxides.   An excess of oxygen causes more
 nitrogen oxides and  less carbon monoxide and other unburned organics.
 For ammonium nitrate and fuel oil  mixtures (ANFO), a fuel oil con-
 tent of more than 5.5 percent creates a deficiency of oxygen.

   There are hundreds of different explosives, with no universally
accepted system for classifying them.   The classification used in
Table 11.3-1  is based on the chemical  composition of the explosives,
                                 -2-

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without regard to other properties, such as rate of detonation,
which relate to the applications of explosives but not to the
specific end products.   Most explosives are used in two-, three-,
or four-step trains that are shown schematically in Figure 11.3-1.
To illustrate, the simple removal  of a tree stump from the ground
might be done with a two-step train made up of an electric blasting
cap and a stick of dynamite.  The  detonation wave from the blasting
cap would cause detonation of the  dynamite.  On the other hand, to
make a large hole in the earth, an inexpensive explosive such as
ammonium nitrate and fuel oil (ANFO) might be used.  In this case,
the detonation wave from the blasting cap is not powerful enough
to cause detonation, so a booster  must be used in a three- or four-
step train.  Emissions  from the blasting caps and safety fuses
used in these trains are usually small compared to those from the
main charge, because the emissions are roughly proportional to the
weight of explosive used, and the  main charge makes up most of the
total weight.  No factors are given in the next section for comput-
ing emissions from blasting caps or fuses, because these have not
been measured and because the uncertainties are so great in esti-
mating emissions from the main and booster charges that a precise
estimate of all emissions is not practical.

11.3.2  Emissions and Controls2'4'5'6

   Carbon monoxide is the pollutant produced in greatest quantity
from explosives detonation.  TNT,  an oxygen-deficient explosive,
produces more CO than most dynamites, which are oxygen-balanced, but
all explosives produce measurable  amounts of CO.  Particulates are
produced as well, but such large quantities of particulate are gen-
erated by the shattering of the rock and earth which the explosive
is used to move that the  quantity of particulates from the explosive
charge cannot be distinguished.  Nitrogen oxides (both NO and N02)
                                 -3-

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                                          2. DYNAMIT;
                         1. ELECTRIC
                          BLASTING CAP
                       PRIMARY
                       HIGH EXPLOSIVE
                                         SECONDARY HIGH EXPLOSIVE
                     a.   Two-step explosive train
                                              3 DYNAMITE
             1. SAFETY FUSE
                          2. NONELECTRIC
                            BLASTING CAP
                LOW EXPLOSIVE    PRIMARY
                (BLACK POWDER)   HIGH
                              EXPLOSIVE
                                        SECONDARY HIGH EXPLOSIVE
                     b.  Three-step  explosive train
                                                   4. ANFO
NELECTRIC
1ST ING CAP
| i


3. DYNAMITE
BOOSTER

i
I
I

\x

               LOW       PRIMARY           V-'
               EXPLOSIVE   HIGH EXPLOSIVE  SECONDARY HIGH EXPLOSIVE
                      c.    Four-step explosive train
Figure 11.3-1.   Two-, three-,  and  four-step  explosive trains

                                   -4-

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are formed, but only limited data are available  on  these  emissions.
Oxygen-deficient explosives are said to produce  little  or no  nitro-
gen oxides, but there is only a small body of data  to confirm this.
Unburned hydrocarbons also result from explosions,  but  in most
instances methane is the only hydrocarbon species that  has been
reported.

   Hydrogen sulfide, hydrogen cyanide and ammonia have  all been
reported as products of explosives use.  Lead is emitted  from small
arms ammunition when lead projectiles and/or lead primers are fired,
however the explosive charge does not contribute lead to  the  emissions

   The emissions from explosives detonation are  influenced by many
factors, such as explosive composition, product  expansion, method
of priming, length of charge, and confinement.   These factors are
difficult to measure and control in the field and are almost
impossible to duplicate in a laboratory test facility.  With  the
exception of a few studies in underground mines, most studies have
been performed in laboratory test chambers that  differ  substantially
from the actual environment.  Any estimates of emissions  from
explosives use must be regarded as order of magnitude approximations
that cannot be made more precise, because explosives are  not  used
in a precise, reproducible manner.

   To a certain extent, emissions can be altered by changing  the
composition of the explosive mixture.  This has  been practiced for
many years to safeguard miners who must use explosives  in under-
ground mines.  The U.S. Bureau of Mines has a continuing  program
to study the products from explosives and to identify those explo-
sives that can be used safely in underground mines.  Lead emissions
from small arms use can be controlled by using jacketed soft  point
projecticles and special leadfree primers.

   Emission factors are given in Table 11.3-1.

                                 -5-

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                       Table  11.3-1.   EMISSION  FACTORS FOR  DETONATION  OF  EXPLOSIVES
                                                   (EMISSION  FACTOR RATING:    D)
Explosive
Black powder?
Smokeless
Powder2
Dynaml te ,
Straight2
Dynamite,
Ammonia'
Dynamite.
Gelatin2
ANFO*-5
TNT2
RDX3
PITN!
Composition
75/15/10; potassium (sodium)
nitrate/charcoal/sulfur
nitrocellulose (sometimes
with other materials)
20-601 nitroglycerine/
sodium nitrate/wood pulp/
calcium carbonate
20-601 nitroglycerine/
ammonium nitrate/sodium
nitrate/wood pulp
20-100% nitroglycerine
ammonium nitrate with
5.R-Rt fuel oil
trinitrotoluene
(CH?)3N3(NO?)3
eye lotr imethy!enetr1n1troam1ne
CfCH^NO,),)
pentaprythn tol tetranitrate
Uses
delay fuses
sma 1 1 a rms
propel) ant
rarely used
quarry work
stump blasting
demol 1t1on,
construction
work, blasting
in mines
construction
work, blasting
in mines
main charge 1n
art 11 lery pro-
jectiles,
mortar rounds,
etc.
booster
booster
Carbon Monoxide3
kg/HT
85
(38-120)
38
(34-42)
141
(44-262)
32
(23-64)
52
(13-110)
34
398
(324-472)
98d
(2.8-277)
149
(130-160)
Ib/ton
170
(76-240)
77
t«8-84)
281
(87-524)
63
(46-128)
104
(26-220)
67
796
(647-944)
196d
(5.6-554)
297
(276-319)
Nitrogen Oxides3
kg/MT
unk
unk
unk
unk
26
(4-59)
8
unk
unk
unk
Ib/ton
unk
unk
unk
unk
53
(8-119)
17
unk
unk
unk
Methane6
kg/MT
2.1
(0.3-4.9)
0.6
(0.4-0.6)
1.3
(0.3-2.8)
0.7
(0.3-1.1)
0.3
(0.1-0.8)
unk
7.2
(6.6-7.7)
unk
unk
Ib/ton
4.2
(0.6-9.7)
1.1
(0.7-1.5)
2.5
(0.6-5.6)
1.3
(0.6-2.1)
0.7
(0.3-1.7)
unk
14.3
(13.2-15.4)
unk
unk
Other*
Pollu-
tant
H2S
H2S
Pb
H2S
H2S
H2S
SO?
S02
NH3
HCN
C2H2
C?«6
NH3
NH3
kg/MT
12
(0-37)
10
(10-11)
c
3
(0-7)
16
(9-19)
2
(0-3)
1
(0-8)
1
(0-2)
14
(14-15)
13
(11-16)
61
0.5
22d
(12-61)
1.3
(0-25)
Ib/ton
24
(0-73)
21
(20-21)
c
6
(0-15)
31
(19-37)
4
(0-6)
1
(1-16)
2
(1-3)
29
27-30)
27
22-32)
121
1.1
44d
24-122)
2.5
(0-5)
a Based on experiments carried out  prior to 1930 except in the case of ANFO, TNT and PF.TN

I- The factors apply  to the chemical specie1;, methane.  They do not represent total VOC  expressed as methane.
  year-, a TO.

f f,rpit.tr than 6 q per 158 grain projectile (0.6 kg/MT, 1.2 Ib/ton).

d Thp-.c fa> tors arp  derived from theorectlcal calculations—not from experimental data.
Studies were carried out more than 40

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References for Section 11.3
1.  C.  R. Newhouser, Introduction to Explosives,  National  Bomb Data
    Center, International  Association of Chiefs of Police, Gaithersburg,
    MD (undated).

2.  Roy V. Carter, "Emissions from the Open Burning or Detonation of
    Explosives", Presented at the 71st Annual  Meeting of the Air
    Pollution Control  Association, Houston, TX, June 1978.

3.  Melvin A. Cook, The Science of High Explosives. Reinhold Publishing
    Corp., New York, 1958..

4.  R.  F. Chaiken, et  al., Toxic Fumes from Explosives:  Ammonium
    Nitrate Fuel Oil Mixtures.  U. S. Bureau of Mines Report of
    Investigations 7867,  1974.

5.  Sheridan J.  Rogers, Analysis of Noncoal Mine  Atmospheres:  Toxic
    Fumes from Explosives, Bureau of Mines, U.S.  Department of
    Interior, Washington,  D.C., May 1976.

6.  A.  A. Juhasz,  "A Reduction of Airborne Lead in Indoor Firing
    Ranges by Using Modified Ammunition",  Special Publication 480-26
    Bureau of Standards,  U.  S.  Department  of Commerce, Washington, D.C.,
    November 1977.
                                 -7-

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                          BACKGROUND  DOCUMENT
                SECTION  11.3   DETONATION  OF  EXPLOSIVES
 1.0   INTRODUCTION

      The major  reference  document  for this section was Reference 2,
 a  literature  survey  prepared  by  R.V. Carter of the U.S. Army
 Environmental Hygiene Agency.  This document deals with military
 explosives  as well as those used by civilians.  Some explosives
 are used in military and  civilian  applications, but the majority
 of military explosives are different from civilian explosives.
 The material  in AP-42 Section 11.3 deals entirely with civilian
 explosives  since it  is believed  that there would be little use of
 this  document by the military.  Accordingly, much of the material
 in Reference  2  is not included in  Section 11.3 because it is not
 considered  useful.

 2.0   BLACK  POWDER, STRAIGHT DYNAMITE, AND AMMONIA DYNAMITE

      The factors for these explosives are taken from Table 4 in
 Reference 2 and were obtained, in  turn, from the following, both
 published prior to 1930:
     •  A. Marshall, Explosives, Their History, Manufacture.
        Properties and Tests, Vol. I, 2nd ed., P. Blakestons's Son
        and Co., 1917-
     •  N. A. Tolch and G. St. J. Perrott, Dynamites: Their Propulsive
        Strength, Rate of Detonation, and Poisonous Gases Evolved,
        U.S. Bureau of Mines Report of Investigation 2975, 1929.
These factors are based on measured emissions and do not include
any theoretically calculated emissions.  Ranges are also given for
each factor (from Table 4, Reference 2) to illustrate the variability
                                 -8-

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of the results.  Table 5 of Reference 2 also lists  calculated
emissions for ammonia from straight dynamite,  but these have not
been included in AP-42 because the agreement between measured and
calculated emissions from detonation of explosives  has frequently
been poor (or at least unpredictable).

3.0  SMOKELESS POWDER

     The factors for smokeless powder are taken from Table 4 in
Reference 2 and were obtained, in turn, from the sources below -
books that were published prior to World War II.
     •  Davis, T.L.   The Chemistry of Powder and Explosives,  Vol.  I,
        New York:   John Wiley and Sons,  1941.
     •  Faber, H.B.   Military Pyrotechnics,  Vol. 3,  Government
        Printing Office, 1919.
The comments in the previous paragraph also apply to smokeless
powder.  In addition, the information on lead emissions from small
arms firing was taken from Reference 6, which describes a modern study
(1977).  In Reference 6, no attempt was made to collect and measure
all the lead emitted during firing.  The gun was fired in an 80 liter
chamber and a 20 liter sample of the contents was passed through a
filter for subsequent lead determination.   The fraction of lead
sampled can be calculated as 1-e 20/80 or .22 if the contents of the
experimental chamber were well  mixed at all times.   Since this was
not the case, the factors are given as >6 mg per 158 grain projectile,
and the total amount per projectile is not estimated.

4.0  GELATIN DYNAMITE

     The factors for methane and F^S are taken from Table 4 in
Reference 2 and were obtained,  in turn, from the sources listed in
                                 -9-

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Section 2.0 above.  The factors for CO, S02, and nitrogen oxides
are taken from Reference 5, Table 9, and are computed by averaging
all values for nitroglycerine-based agents and water gels.   Table 9
lists NO and N02 separately, and these values were added together
and presented as NO  in Table 11.3-1.
                   A

5.0  AMMONIUM NITRATE/FUEL OIL (ANFO)

     The factors for ANFO were taken from Reference 5, Table 9
(5.8% fuel oil) and from Reference 4, Tables 3 and 4 (6% and 8«
fuel oil).  Reference 4 also contains data for mixtures containing
1, 2, 3, and 4 percent fuel oil, but these were not used because
it is believed that they do not represent mixtures that are com-
monly used.  The data in Reference 5 includes emissions from the
booster charge as well as the ANFO main charge.  In Reference 4,
the emissions from the booster charge (PETN) have been subtracted
out.  To derive the factors for Table 11.3-1, the emissions from
the booster charge were added back in to the emissions from ANFO
taken from Reference 4, using a weighting factor of 60 g booster
per 430 g of main charge.  These corrected emissions were then
averaged with the emissions from Reference 5 to obtain the final
factors.  References 4 and 5 list comparable emissions for CO, but
Reference 4 gives somewhat lower NOX emissions than does Reference
5.  S02 emissions are given only in Reference 5 and not in Reference
4.  The factors in Table 11.3-1 are straight averages of all rele-
vant data without any attempt to judge the quality of individual
data items and weigh some more heavily than others.

6.0  TNT, RDX, AND PETN

     The factors for TNT are taken directly from Table 4 of Reference
2 which, in turn, were derived from the book by Marshall (listed
                                 -10-

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in Section 2.0 above) and the following:
     •  Ornellas, D.L.  The Heat and Products of Detonation of
        Cyclotetramethylenetetranitramine, 2, 4, 6 Trinitrotoluene,
        Nitromethane and Bis [2, 2-dinitro-2-fluoroethyl] formal.
        J. Physical Chemistry 72:2390-2394. July 1968.
The factors for PETN were also taken directly from Table 4 for
Reference 2 and were based on studies reported in the book by
Marshall and also the following:
     •  Ornellas, D.L., J.H. Carpinter, and S.R.  Gunn.   Detonation
        Calorimeter and Results Obtained with Pentaerythritol
        Tetranitrate (PETN).  Review of Scientific Instruments 37:
        907-912, July 1976.
Both of the Ornellas studies were done in a small  scale laboratory
facility that may not be representative of actual  use.   No factors
for RDX were given in Table 4 of Reference 2, so factors were taken
from Table 5 of that same reference.  Table 5 gives factors that
are calculated theoretically, using methods described in Reference
3.  The ranges given with each factor represent the results of
making reasonable assumptions of ranges for values as input for the
computations.

7.0  EMISSION FACTOR RATINGS

     The ratings were made in a completely subjective manner.  The
explosive process is not reproducible:  therefore there cannot be
a precise factor to describe an imprecise operation.  The values
are based on experimental measurements (except for RDX), but many
of the measurements were made more than 50 years ago using techniques
that are crude when compared with modern methods.   The  factors are
definitely better than mere guesses, but they are probably not high
quality.  Rather arbitrarily, they are rated D.
                                 -11-

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2. 3. RECIF
EPA-450/4-79-023
4. TITLE AND SUBTITLE 5. REPO
Detonation of Explosives: An Ar-4^ Update S.PERF
7. AUTHOR(S) 8. PERF
K. Wilson
9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PRO
Pacific Environmental Services, Inc. 2AA
1930 14th Street H.CON
Santa Monica, California 90404 68-
Wor
12. SPONSORING AGENCY NAME AND ADDRESS 13. TYP
Office of Air Quality Planning and Standards Final
U.S. Environmental Protection Agency i4.spoc
Research Triangle Park, North Carolina 27711
15. SUPPLEMENTARY NOTES
EPA Project Officer: Audrey McBath
16. ABSTRACT
This document contains the text of AP-42 (Compilation of
factors) Section 11.3. Detonation of Explosive?;. It. di<;ruc;<;p
resulting from the detonation of industrial explosives and sm
Included are a process description, explosive train diagram,
emissions. A background document which discusses, in some de
of emission quantification methodologies follows the section
17 KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS b. IDENTI F IE RS OPEN ENDE
Emission Factors
Air Pollution Control
Explosives
Ammunition
18 DISTRIBUTION STATEMENT 19 SE CURITY CLASS I This
Unclassified
Unlimited 20 SECURITY CLASS iThis
Unclassified
lENT'S ACCESSION NO
RT DATE
ember 1979
DRMING ORGANIZATION CODE
DRMING ORGANIZATION REPORT NO.
3RAM ELEMENT NO.
635
TRACT 'GRANT NO.
02-2583
k Assignment No. 12
EOF RE PORT AND PERIOD COVERED
; April to September 1979
MSORING AGENCY CODE

Air Pollutant Emission
5 air pollutants
all arms firing.
and a discussion of
^ai 1 , the derivation
itself.

.D TERMS i COSATI 1 idd.'GrOUp

17
pugf 22 PRICE
EPA Form 2220-1 (R»v. 4-77)    PREVIOUS  ECITIONISOBSOLETE

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