April 1985
    DIOXIN EMISSIONS FROM
INDUSTRIAL BOILERS BURNING
     HAZARDOUS MATERIALS
                     by
                  C. Castaldini
                Acurex Corporation
            Energy & Environmental Division
                555 Clyde Avenue
                 P.O. Box 7555
            Mountain View, California 94039
             EPA Contract No. 68-03-3241
                 Project Officer:
                Robert A. Olexsey
             Research Program Manager
            Alternative Technologies Division
      Hazardous Waste Engineering Research Laboratory
               Cincinnati, Ohio 45268
                     for

      Hazardous Waste Engineering Research Laboratory
       US. ENVIRONMENTAL PROTECTION AGENCY
          Office of Research and Development
               Cincinnati, OH 45268

-------
April 1985
DIOXIN EMISSIONS FROM INDUSTRIAL BOILERS
BURNING HAZARDOUS MATERIALS
by
C. Castaldini
Acurex Corporation
Energy & Environmental Division
555 Clyde Avenue
P.O. Box 7555
Mountain View, CA 94039
EPA Contract No. 68—03—3241
Project Officer:
Robert A. Olexsey
Research Program Manager
Alternative Technologies Division
Hazardous Waste Engineering Research Laboratory
Cincinnati, Ohio 45268
for
Hazardous Waste Engineering Research Laboratory
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Cincinnati, Ohio 45268

-------
NOT ICE
This document has been reviewed In accordance with U.S. Environmental
Protection Agency policy and approved for publication. Mention of trade
names or comercial products does not constitute endorsement or
recomendation for use.

-------
FOREWORD
Today’s rapidly developing and changing technologies and industrial
products and practices frequently carry with them the increased generation of
solid and hazardous wastes. These materials, if improperly dealt with, can
threaten both public health and the environment. Abandoned waste sites and
accidental releases of toxic and hazardous substances to the environment also
have important environmental and public health implications. The Hazardous
Waste Engineering Research Laboratory assists in providing an authoritative
and defensible engineering basis for assessing and solving these problems.
Its products support the policies, programs, and regulations of the
Environmental Protection Agency, the permitting and other responsibilities of
State and local governments and the need of both large and small businesses
in handling their wastes responsibly and economically.
This report describes the results obtained from laboratory analyses of
flue gas samples from industrial boilers burning hazardous waste materials.
The purpose of the analyses was to determine if detectable quantities of
polychlorinated dibenzo—p—dioxlns (PCDD) and polychiorinated dibenzo—furans
(PCDF) are emitted from such boilers when hazardous waste materials are
burned. This information will be useful to regulatory officials who are
responsible for setting standards, to permitting officials who may encounter
questions about dioxin emissions during a permitting process and to members
of the technical community who are seeking safe methods for hazardous waste
disposal. For further information, please contact the Alternative
Technologies Division of the Hazardous Waste Engineering Research
Laboratory.
David G. Stephan, Director
Hazardous Waste Engineering Research Laboratory
iii

-------
ABSTRACT
Laboratory analyses for polychiorinated dibenzo—p—diOXiflS (PCDD) and
polychlorinated dibenzo—furans (PCDF) were performed on waste fuels and stack
gas emission samples from five Industrial boiler test sites cofiring liquid
hazardous waste fuels. Analytical results Indicate that, apart from creosote
sludge, chlorinated wastes were void of PCDD and PCDF homologs at detection
limits in the range of 0.045 to 4.7 ppb. Creosote sludge cofired with wood
waste In a stoker boiler was found to contain 7.4 ppm of total dioxins,
primarily hepta and octa homologs. Stack gas concentrations of PCDD were
highest for the creosote wood-fired stoker at about 75 ng/m 3 . Other PCDD
results indicate concentrations ranging from below detection levels
(0.0022 to 0.019 ng/m 3 ) to a maximum of 1.1 ng/m 3 . PCDF concentrations were
generally higher with total furan levels up to 5.5 nglm 3 . No
2,3,7,8 —tetrachlorodibeflZOi,diOXin was detected in any waste fuel. While
the 2,37,8—TCDD isomer was detected in the flue gas emissions from one
boiler, the measured value for the emissions of 23,7,8—TCDD was equal to the
detection limit for the compound in the particular flue gas (0.002 ng/m 3 ).
Iv

-------
Forward . . . . . . . . . . . . . . . .
Abstract . . . . . . . .
Tables . . . . . . . . . . . . .
Introduction . . . . . .
1.1 Program Objective
Test Program Description
2.1 Test Description . . . . . . . .
2.2 Analysis Protocol
Results
Interpretation and Conclusion . . . .
References . . . . . . . . .
Appendix A —— Battelle Columbus Laboratory
Analytical Report . . .
• . . . • . . I I 1I
iv
• I I I I • • • I vi
• . I I 1
• 1
. 6
• . . . . . . • • 6
8
10
16
19
. • . . 20
CONTENTS
1
2
3
4
V

-------
TABLES
Number Page
1 Summary of Test Site Boilers . . 2
2 Summary of Test With Waste Fuel Firing 3
3 Summary of Test Average DRE’s for Volatile POHC’s 4
4 Test Sites Selected for PCDD and PCDF Analyses . . . . . . . 7
5 Dioxins Concentrations in Waste Fuels . . 11
6 Furan Concentrations in Waste Fuels . . . . . 12
7 Flue Gas Concentrations —— Dioxins . . . . . . . . 13
8 Flue Gas Concentrations —— Furans 14
9 QA/QC Results for Flue Gas Sample Extracts . . 15
10 Site A Dioxin DRE’s . . . 17
11 Mass Flow Rates of Total Dioxins and Furans . 18
vi

-------
SECTION 1
INTRODUCTION
In 1982, the EPA ’s Hazardous Waste Engineering Research Laboratory in
Cincinnati initiated a series of field test programs on industrial boilers
cofiring hazardous wastes. A principal objective of these tests was to
develop a data base on the destruction and removal efficiencies (DRE) of
industrial boilers co—firing hazardous organic components in waste fuels.
This data base was required by the EPA’s Office of Solid Waste and Emergency
Response to evaluate hazards and potential control measures in preparation
for recommending regulations controlling ongoing industry cofire practices.
Eleven boilers were tested under typical industrial operating
conditions. The boiler specifications for these 11 tests are listed in
Table 1. Waste specifications and additional boiler specifications are
listed in Table 2. The majority of the tests were on gas— and oil—fired
watertube boilers which correspond to the predominant cofiring application in
industry. The wastes at Sites E through K were spiked with carbon
tetrachloride and, usually, chlorobenzene and trichloroethylene. This was
done to extend the range of volatile POHC’s to be monitored and to provide a
common basis for intra—boiler comparisons.
Table 3 summarizes the ORE results for volatile principal organic
hazardous compounds (POHC’s). With the exception of Site F, site—average
ORE’s exceeded 99.99 percent. The mass—weighted volatile organics DRE for
all test sites was 99.998 percent. Additional results for the Site A stoker,
however, indicated DRE’s lower than 99.99 percent for several semivolatile
POHC’s including pentachlorophenol and polynuclear aromatics in the creosote
sludge. Generally, lower DRE’s were attributed to nonsteady or transient
combustion conditions.
Recently, additional tests were performed to measure volatile POHC ORE’s
and volatile PlC emissions during nonsteady and transient boiler operations
typical for these combustion devices. These tests, documented in the Site L
report (Ref. 2), indicate generally good destruction efficiency (ORE
average 99.998 percent) under most nonsteady and off—specification combustion
conditions investigated.
1.1 PROGRAM OBJECTIVE
The objective of this program was to perform laboratory analyses of
boiler flue gas samples to determine concentrations of polychlorinated
I

-------
TABLE 1. SUMMARY OF TEST SITE BOILERS (Source: Ref. 1)
9
Coe , 0rt,d ,0tsrbe
0 bdi?l ,l psct. d
71,,
U 9 1.14 ..cbd
,eo oetl.llp flood
30 t o r tubS
I PucospI 30br
1 3 1101 17_I 1613) 1% (1.141)
1.1 (0.07 I I (317 SO (53)
20 (230) 3 ? ? 11 1.030) (70 (.530)
11.6 (10) St ((.130) I SO (1.110)
i cO . .oub iIud . 61usd wIth o.od
I lIlpi 30u b , I I , utowltid
oil qus
• P$seolic ousou be or be lbs.
.towIz.d bso.iu
I btbo.1 sod be of Ifs
bI , 0 , 0 30085 i. O.U 18 ,0
p11 11 chiusiusUd .1.11.4 borO...
orgs .lcl
I bthyl tbcrpIsb TO. ibem obeIrW
bpp ,.dwct usuthe ouib ‘l to
borus, tIwo.t
I Pilot solusosti L ? lbs•
stowliod oil
burus ’
I IIØlp t61 .rI30Ud Sooflubl• S I,
.1.1 red oil
11 co.l. boWl susbW be or be
6 oIl ,0Ibu fu,l 58 .1164 eli
0 bIll.. ouub hiqb ((If.. o.r or
1. sitrul, 8q i .l(i io. It,..
•to. 18d berth?
— I ll?lci.I3p ArsHibi . oil
bb,. d foul. berow,
Uo 6 .51 1 Sl,. d oust, slib hoed with bus,,
light oil .51
Opolt. 131 (97 ip.,.iIo.
bliicyclouw !l.cbstI..q 1 3 04$. c $tIua
ii , end .0,18 75,4
Low boll.. bowl b. 1 oulbu
firs rub .9 4? .1!. (40 qpef
fsr to. loud sills reduo.d .r 66
bsusro. Ul ii •IC4$ l sir.
bus. bout 00 D5v’9wt C40.cit7 with
3 or I b ,r .s ,u I. , 0r.lc,
be. Port loud .45* .1 7 10 .7?,
(240 qph) o.ib 91.1.., rut, for
10 54$ sbe30 SO
busu Purl loud with ) 130 . 1 1 1
(I S O 30h) usut, fioln Pit, Is.’
losdo show. SO porc , .t
ier s.u P. I l d 018 ,8P 30
I. 05555$ Oso.11 IIi. 1097 cClo?l , 0
to 00 ...cowt o ouu8 7,07.
SOP St boll. ’ tspscltp with o..i
460 .1/, (410 ,ehl oult, firing
‘It,
bus SIaqed c u,tlo. for I. 10,
with . ,f (JO •th ((20 qoh)
slut, flow
Yvette? , .i •Ir of
I? or,’c,.t
bus Typici I 70110 porcoot buo ,p sad
llqht oIl .1. .
318 bilIetyp.
£ btu’tub . slob.,
I Puctipud fire
S ft.ld-.r.ctid
. 5 8 ,1.6 ,
o Fl.id.i,cb4
cusoortod ou#r
itat. ,
£ PIC6 Ip.d .u bes
Obi.
0gb
copucity.
1IO 1Sf’,’)
Forest, .gl .
. (ft )
.“ if
F 5,us9 b,o.It b.p ’us.rl
iy’fucq. Ilniocti . .
. ‘ IIt I Priusry lou) ports)
7751141 3018
fouls
IsiJ ocito .
outbuoto.
bed oust,
btm’.l pus
b8,Sl U I
or oil
50. 6 oil
7.1 (60 ) 31 (3.310) 130
I I 6 IllS) 67 (1.450) 664 (7.160) 30. 6 oil
11. 1001 So. 6 .13.
or
7,305,0
0.0 (*0) 6.1 (tIll 20 (270) Utuse
3? (3001 020 1 1 5 .4th) 011
7.5 1571
J Pichipud Pl , , .
I Puctapud 308?bes
1.030) P ,lw.,i,,d
to sI
3510) b8..1 pus
Ii (1.630) 76
1.3 (IC) 7.0 II I) LI (PIP
3.6 (60) 60 (2.270) 67 13301

-------
TABLE 2. SUMMARY OF TEST WITH WASTE FUEL FIRING (Source: Ref. 1)
CA)
Site
Ilunt er of
waste—fuel—
fired tests
Volumetric heat
release rate,
kW/m 3
(10 Btu/hr—ft 3 )
Surface heat
release rate,
kW/m 2
(10 Btu/hr—ft 2 )
Bulk
furnacea
temperature,
C ( F)
Bulk
furnacea
residence
time, sec
Waste fuel
heatinq
value, NJ/kg
(10 Btu/lb)
Waste heat
input,
percent of
total
POHC’s of interest
A
4
300 (29)
48 (16)
1.370 (2,500)
1.2
39 (17)
40
Phenol, pentachlorophenol, naphthalene
fluorene. 2-4-Dirnethyiphenol
B
3
745 (72)
106 (34)
1.320 (2.400)
0.8
0.03-0.18
(0.013—0.017)
(1
Toluene
C
3
78 (1.5)
150 (48)
1.320 (2.400)
2.0
39 (17)
38
Phenol
0
3
400 (39)
180 (57)
1,430 (2,600)
1.1
21 (8.8)
18
Tetrachloroethylene
3
230 (22)
100 (33)
1.370 (2.500)
1.3
42 (18)
48
BIs(2—chloroethyl)ether, toluene
1
580 (55)
37 (11)
1,550 (2,800)
0.7
27 (12)
22
Piethylmethacrylate, ohydroxy methyl
I sobuty-ra to and a-hydroxy I sobutyrate
methyl ether
6
380—710
(37—14)
24—49
(7.6—15)
1,480-1.590
(2,700—2.900)
0.5—1.0
25-27 (11—12)
19—43
Above plus carbon tetrachioride,
chlorobenzene and trichloroethylene
1
420 (40)
26 (8.1)
1,480 (2,700)
1.1
37 (16)
56
Toluene, methylmethacrylate
F
3
114 (11)
104 (34)
1,370 (2.500)
2.0
33 (14)
9.0
Carbon tetrachloride, chlorobenzene,
trichloroethylene, toluene
G
3
820 (79)
262 (81)
1.350 (2.450)
0.4
21 (9.0)
100
Carbon tetrachioride, epichiorohydrin,
bi s( 2-chiorol sopropyl )ether
H
3
180 (17)
183 (58)
1,310 (2,500)
2.0
17 (7.0)
2.4—4.3
Carbon tetrachloride, chlorobenzene.
1 • 1, 1—Trichioroethane
I
2
340 (33)
180 (57)
1,430 (2,600)
1.8
25 (11)
8.2
Carbon tetrachloride, chlorobenzene,
trichloroethylene, toluene, aniline,
benzene. ni trobenzene
J
6
690—1.750
(65—170)
118-300
(37-95)
1.310-1.370
(2,400-2,500)
0.3—0.7
42 (18)
100
Carbon tetrochloride, chlorobenzene,
trichloroethylene, toluene
K
1
270 (26)
370 (120)
1,370 (2,500)
1.8
40 (17)
65
Carbon tetrachloride, chlorobenzene.
trichloroethylene, toluene, benzene
5 Not measured values. Estinmtes
approsimate.
of bulk gas temperature in the furnace were used to calculate bulk furnace residence time. Values to be considered

-------
TABLE 3. SUMMARY OF TEST AVERAGE DRE t S FOR VOLATILE POHC’sa
(Source: Ref. 1)
---- - m - -
Weigti ted
POHC Site B Site 0 Site E Site F Site G Site H Site I Site J Site K Range average
Carbon tetrachiorlde 99.9990— 99.98— 99.995- 99.97— 99.9990— 99.997— 99.91— 99.9992
99.9998 99.9990 99.9990 99.9994 99.9993 99.9998 99.9998
(99.9996)b (99.995) (99.998) (99.98) (99.9993) (99.9990) 99.9998
Tr1ch oroethy1ene 99.994— 99.98- 99.99990- 99.998— 99.98 99.9994
99.9995 99.998 99.99992 99.99993 99.99993
(99.998) (99.996) (99.99991) (99.9996) 99.99990
1 1,1—TrIch1oroethane 99.97— 99.97 99.994
99.9996 99.9996
(99.994)
Chlorobenzene 99.995- 99.96— 99.990- 99.997 99.8- 99.9 99.992
99.99990 99.992 99.997 99.9990 99.97 99.99992
(99.998) (99.98) (99.992) (99.990) (99.95) 99.99992
Benzene 99.91— 99.91— 99.990
99.98 99.996
(99.97) 99.996
Toluene 99.9992— 99.90— 99.9990— 99.90— 99.998
99.99990 99.97 99.9997 99.99996
99.991 (99.9996) 99.997 199.95) 99.998 (99.9990) 99.99996
Tetrachioroethylene 99.994- 99.994— 99.998
99.9992 99.9992
(99.998)
Methylmethacrylate 99.95— 99.95— 99.991
99.997 99.995
(99.991)
Mass weighted average 99.991 99.994— 99.95— 99.90— 99.995- 99.97— 99.97— 99.8- 99.996- 99.8— 99.998
99.99990 99.99990 99.9990 99.9990 99.9996 99.99992 99.99993 99.99996 99.99996
(99.9993) (99.995) (99.98) (99.998) (99.991) (99.998) (99.9990) (99.9991)
aEach test average DRE Is general )y based on the weighted average of tr (p 1cate measurements.
bNu,,ters In parentheses represent the site—specifIc POHC average ORE.

-------
dibenzo—p—dioxins (PCDD) and polychiorinated dibenzo—furans (PCDF) including
the 2,3,7,8 tetra isomer for selected boiler sites. In addition, analyses of
waste fuels cofired at these selected test sites were also performed to
determine whether PCDD and PCDF emissions could be attributed to waste fuels
or to products of combustion of waste fuels.
5

-------
SECTION 2
TEST PROGRAM DESCRIPTION
2.1 TEST DESCRIPTION
Table 4 lIsts test sites selected for PCDD and PCDF analyses. At
Site A, four cofire tests were performed by burning a mixture of wood waste
(chips, bark, and sawdust) with creosote sludge. The sludge contained
phenolic coupounds including pentachiorophenol, generally identified as a
precursor to dioxin emissions during combustion. Heat Input attributed to
the creosote sludge was estimated at 40 percent for these tests. Operation
of the stoker at Site A was erratic with large and frequent fluctuations in
excess air and CO emissions. This operation is typical of batch—feed
wood—fired stokers.
Two test series were performed at Site D, each consisting of three
cofired tests. A methanol waste stream containing tetrachloroethylene was
burned with residual oil in a multiburner boiler. Heat input contribution
due to the methanol waste ranged between 18 and 30 percent. A toluene waste
stream containing bis(2—chloroethyl)ether was cofired in the second test
series contributing about 47 percent of the total heat input to the boiler.
Boiler operation during the initial test series (Dl) was characterized by
several burner upsets caused by waste feed problems. Boiler heat input, and
thus) furnace temperature, was higher for Dl tests than for the D2 test
series.
A nethylmethacrylate waste stream containing spiked amounts of carbon
tetrachioride, chlorobenzene and trichloroethylene was cofired at Site E
during a test series involving six individual cofire tests. With the
exception of one, all tests were conducted with residual oil as the primary
fuel. Natural gas was substituted for residual oil during one of the tests.
Three different boiler heat input rates were Investigated. The waste stream
contributed from 20 to 43 percent of the total heat input. Boiler operation
was relatively steady for each test condition.
The pulverized coal—fired boiler at Site H was cofired with methyl
acetate waste spiked with carbon tetrachioride, chlorobenzene and
l1,1—trichloroethane. The boiler was fired at capacity with the waste
contributing only 2.4 to 4.3 percent of the total heat input. Boiler
operation was steady during all three cofired tests.
6

-------
TABLE 4. TEST SITES SELECTED FOR PCDD AND PCDF ANALYSES
Site PriiMry Waste fuel POHCs
I i) Boiler type fuel Waste fuel concentration (mg/el) Nun er of tests
A Watertube stoker Wood chips Creosote sludge Phenol 0.6 to 1.3 Four cofire tests •
sawdust Pentachlorophenol 2.2 to 6.0 •
Naphthalene 5.4 to 19 a
Fluorene 4.4 to 7.6
2.4 Din thy1phenol 0.3 to 1.3
D l Field erected Ho. 6 fuel Methanol waste Tetrochloroethylene 46 to 310
converted oil
watertube stoker
D2 No. 6 fuel Toluene waste Bis(2—chloroethyl)ether 39 to 42
oil Toluene 950
E Packaged watertube No. 6 fuel Methylmethacrylate Methylmethacrylate 33 to 52
olla waste artificially Carbon tetrachloride 27 to 34
spiked Chlorobenzene 16 to 20
Trichloroethy lene 27 to 32
Pulverized Methyl acetate Carbon tetrachloride 24 to 51
coal waste artificially Chlorobenzene 26 to 53
spiked 1.1.1—Trichloroethane 20 to 41
Natural Methylinethacrylate Carbon tetrachloride 6.8
gas waste artificially Chlorobenzene 15
spiked
aone of the six tests was performed with natural gas as the primery fuel
H
Field erected
watertube
I
Packaged
watertube
Streams analyzed for
PCDO and PCOF
Creosote waste
Flue gas
Flyash from najiticlone
Bottom ash
Waste fuel
Flue gas
Waste fuel
Flue gas
Waste fuel
Flue gas
Three cof Ire tests
Three cofire tests
Six cofire tests
.
.
.
.
.
Three cofire
tests S Waste
• Flue
fuel
gas
One test
• Waste
• Fluegas
fuel

-------
Sampling for semivolatile and nonvolatile organics at Site L was
performed only during one cofire test. Carbon tetrachloride and
ctilorobenzene spiked methylmethacrylate waste was burned with natural gas.
Heat input from the waste was approximately 30 percent with steady boiler
operations. Although several other nonsteady tests were performed at Site L,
none of the measurements included protocols for sernivolatile and nonvolatile
organic compounds.
2.2 ANALYSIS PROTOCOL
Analysis for PCDD and PCDF including the isomers 2 ,3 ,7,8—TCDD and —TCDF
were performed by Battelle Columbus Laboratory (BCL) on both waste fuels and
flue gas samples corresponding to the test series listed in Table 4. The
analytical method by BCL was based on high—resolution gas chromatographyf
high—resolution mass spectrometry (HRGC/HRMS). Detection limits were on the
order of 0.04 to 0.13 ng/ml (ppb) for tetra isomers and 1 to 4 ppb for octa
isomers in the waste fuels. Detection limits for flue gas samples ranged
between 0.005 to 0.08 ngfm 3 of gas (about 0.0003 to 0.0005 ppt(v)).
Quality assurance procedures Included recovery analysis of spiked
internal standards and analytical method blanks. Appendix A details the
analytical procedures and results obtained. Soxhlet extraction of flue gas
samples collected using the modified EPA Method 5 train were performed by the
Acurex Laboratory using the procedure depicted In Figure 1. These extract
samples were in turn cornposited and analyzed by BCL.
Analyses focused on both waste fuels and flue gas samples. However, for
Site A, selected ash samples collected from the stoker bottom hopper and from
the nulticlone hopper were also analyzed. PCDD analysis results of ash
streams documented In Reference 3 are not reported here. for each of the
Site D, E, and H test series listed in Table 4, waste fuels were coniposited
into one sample and analyzed. Similarly, organic extracts of flue gas
samples for each test series were coniposited and analyzed.
8

-------
8302-034
8302-0 34
r Probe
and
nozzle wash
SC/MS as BNA’s
Semivolatile PP’s and
other predominant
chromatograPhic peaks
(—10 non-PP peaks)
Report results in jg/train
Back half
rinse and
impinger contents
Figure 1.
Flow scheme for extraction and analysis of organic samples
from MM5 trains.
8302-031
XAD
resin
8302 -040
r Filter
Soxhiet
extract
Parti cul ate
we 1 ght
Dry
and weigh
Combine solids
as
Extract
BNA s
Measure
vol u
Part, cul ate
weight
Combine all extracts
Combine all extracts
Soxhlet
extract
Fluorene-d 10 Terphenyl-d 14
(2-nItrophenol—d4)
d 5 -ni trobenzene)
9

-------
SECTION 3
RESULTS
Tables 5 and 6 summarize dioxins and furans concentrations,
respectively, in the waste fuels at each of the test sites selected for these
analyses. Site A results are based on an individual sample of the creosote
collected during test 2. As indicated, all waste fuels, with the exception
of Site A, were void of PCDD’s or PCDF’s at detection limits indicated in the
tables’ footnotes. Site A creosote contained about 7.4 ppm total PCDD’s,
primarily hepta and octa isomers. No PCDF analysis was performed on the
Site A creosote sludge since the sample was exhausted in the PCDD analysis.
The highly toxic 2,3,7,8-TCDD was not detected in any of the waste fuels.
Tables 7 and 8 summarize flue gas concentrations of PCDD and PCDF
homologs, respectively. Site A emissions measured during two tests showed
total PCDD of about 75 ng/m 3 , by far the highest level of any of the other
test sites. Total PCDD at Site 0 measured 0.80 and 0.64 ng/m 3 for the two
test series, respectively. Minute levels of 2,3,7,8—TCDD were detected in
the sample for the 02 test series when cofiring with toluene and
bis(2—chloroethyl)ether. However, the concentration was at the detection
limit. Both Site E and H emissions Indicate no PCDD emissions. However,
flue gas samples obtained at Site L showed 1.1 ng/m 3 total PCOD, primarily
tetra isomers.
PCDF emissions were generally higher than PCDD emissions. Emissions
were lowest for the test series at Site E and highest for the test series Dl
and 1. No PCDF data are available for Site A.
In general. flue gas concentrations of total PCDD and PCDF compounds
ranged between non—detected (below 0.08 ng/m 3 ) to 5.5 ng/m 3 with the
exception of the wood/creosote stoker. These concentrations correspond to a
maximum of about 0.3 ppt(v).
Table 9 summarizes the results of XAD—2 sorbent analytical blank
extracts and the results of analysis of a field XAD blank from the Site L
test program. Results indicate below—detection levels of PCDD and PCDF
homologs In all samples except the Site L field blank which showed 3.77 ny of
TCDD. This compound was tentatively identified as a l2,3,4—TCDD isomer.
The presence of the l,2,3,4—TCDD in the field blank sample could not be
explained and thus is to be considered an artifact of the analytical
procedure.
10

-------
TABLE 5. DIOXIN CONCENTRATIONS IN WASTE FUELS (ppb)
Site
identification
Sample description
Tetra
Penta
Hexa
Hepta
Octa
Total
PCDD
2,3,78—TCDD
A
Test 2 creosote sludge
ND
2.1
360
3.600
3,400
7,400
ND
Dl
Composited of methanol/
PCE for tests 2, 3,
and 4
ND
ND
ND
ND
ND
ND
ND
D2
Composited of toluene/
BCEE for tests 5, 6,
and 7
ND
ND
ND
ND
ND
tID
ND
E
Composited of MMA CC1 4 ,
TCE, and Cl for
tests 3, 4, 5, 6, 7,
and 8
ND
ND
ND
ND
ND
ND
ND
H
Composited of methyl
acetate, Cd 4 , C14
and 1,l,1—TCA for
tests 2, 3, and 4
ND
ND
ND
ND
ND
ND
ND
L
Test 2 MMA, Cd 4 and
Cl q
ND
ND
ND
ND
ND
ND
ND
Analytical method blank
ND
ND
ND
ND
ND
ND
ND
Note
ND —— Not detected. Below detection limits. Detection limits fn the range of 0.045 to
4.17 ppb. Detection limits are summarized in Appendix A, Table 4, Page 30

-------
TABLE 6. FURAN CONCENTRATIONS IN WASTE FUELS (ppb)
Site
identification
Sample description
Tetra
Penta
Kexa
Hepta
Octa
Total
PCDF
2,37,8—TCDF
Dl
Composites of methanol!
PCE for tests 2, 3.
and 4
ND
ND
lID
ND
ND
ND
ND
02
ComposItes of toluenef
BCEE for tests 5, 6,
and 7
ND
ND
HO
ND
ND
ND
ND
E
Composited of MMA, CC1 4
TCE and CL$ for
tests 3, 4, 5, 6, 7,
and 8
lID
ND
ND
ND
ND
lID
ND
H
Composited of methyl
acetate Cd 4 , CI and
1,ll-TCA for
tests 2, 3, and 4
ND
ND
ND
ND
MD
NO
lID
1
Test 2 MMA, CC1 4 and
CI
ND
NO
NO
ND
ND
ND
ND
Analytical blank
ND
ND
lID
lID
ND
ND
ND
Note
ND —- Not detected. Below detection limits. Detection limits in the range of 0.045 to 2.0 ppb.
Detection limits are summarized in Appendix A, Table 3, Page 29

-------
Site
identification
Sample description
Flue gas
sample (m 3 )
Tetra
Penta
Ilexa
Hepta
Octa
Total
PCDD
23,7,8—TCDD
A
Test 2 FINS extract
2.34
43
14
7.5
5.5
4.6
75
ND
Test 4 MM5 extract
2.50
38
24
12
1.6
0.8
76
ND
D l
Cornposited of FINS
extracts for
test 2, 3, and 4
27.8a
0.12
0.074
0.10
0.25
0.26
0.80
ND
02
Composited of rIMS
extracts for
tests 5, 6, and 7
18.4
0.027
0.032
0.052
0.12
0.41
0.64
0.002b
E
Composited of rIMS
extracts for
tests 3. 4, 5, 6,
7, and 8
51.5a
ND
ND
ND
ND
ND
ND
ND
H
Composited of FINS
extracts for
tests 2, 3, and 4
26.Oa
ND
ND
ND
ND
ND
ND
ND
I
Test 2 FINS extract
8.7
0.57
0.010
0.066
0.12
0.29
1.1
ND
acompositod sample volumes
bMeasured value was equal to the detection limit
Note
TlF — Not detected. Detection limit 0.005 to 0.08 ng/m 3
To convert ng/m 3 to ppt multiply table entries by 0.068 for tetra, 0.062 for penta, 0.056 for hexa, 0.052 for
hepta and 0.048 for octa
TABLE 7. FLUE GAS CONCENTRATIONS -- DIOXINS (ng/m 3 )
I - .

-------
TABLE 8. FLUE GAS CONCENTRATIONS —— FURANS (ng/m 3 )
— --—————.——————- —
Site Flue gas Total
identification Sample description sample (m 3 ) Tetra Penta Hexa }lepta Octa PCDF 2 ,3 ,7 ,8-TCDF
D l Con osited of FQ45 27.8 2.1 1.4 0.77 0.94 0.27 5.5 0.24
extracts for
tests 2, 3, and 4
02 Composited of MM5 18.4a 0.10 0.035 ND 0.034 0.07 0.24 0.13
extracts for
tests 5, 6, and 7
E Composited of ? l5 51.5a 0.12 0.019 ND ND ND 0.14 0.014
extracts for
tests 3, 4, 5, 6,
1, and 8
H Composited of 1’ 4S 26.Oa ND 0.14 0.39 0.071 0.20 0.81 MD
extracts for
tests 2, 3, and 4
L Test 2 I l5 extract 8.7 0.61 0.53 0.62 0.38 0.34 2.5 0.033
aComposi ted sample voluees
Note
N1T — Not detected. Detection limit 0.005 to 0.037 ng/m 3
To convert nglm 3 to ppt , tiultiply table entries by 0.072 for tetra, 0.065 for penta,0.059 for hexa, 0.054 for
hepta, and 0.050 for octa

-------
TABLE 9. QA/QC RESULTS FOR FLUE GAS SAMPLE EXTRACTS (ng)
Tetra Penta Hexa Hepta Octa 23,7,8—Tetra
Method blank PCDD ND ND ND ND ND ND
PCDF ND ND ND ND ND ND
Site L field PCDD 3.77 ND ND ND ND ND
blank
PCDF ND ND ND ND ND ND
Note
ND —— Not detected; detection limit In the range of 0.040 to 1.50 ng
in each extract sample
15

-------
SECTION 4
INTERPRETATION AND CONCLUSION
Site A creosote sludge was the only waste fuel found to contain dioxins
tn detectable quantities. Table 10 summarizes the DRE of each dioxin homolog
and for the 2,3 ,7,8—TCDD at Site A. In the creosote waste, dioxin tended to
predominate in the higher homologs —— hepta and octa. In the flue gas, the
reverse is evident; dioxin concentrations tended toward the lower
homologs —— tetra and penta. A plausible Interpretation is that during
combustion the higher homologs In the waste were reduced to lower homologs
which were emitted in the flue gas. This would account for the low DRE
(negative in the case of tetra—CDD) for the lower homologs.
Table 11 summarizes the mass flow rates for total dioxins and total
furans for the test series Dl, 02, E, H, and 1. The calculated input rates
are based on the combined waste firing rate for the test series and the sums
of the detection limits for total PCDD and total PCDF. The flue gas emission
rate was calculated using the combined flue gas emission rate for each test
series since sample extracts were composited and analyzed as one sample. The
table indicates that Input rates of dioxins and furans were not necessarily
below the measured flue gas emission rate. Therefore, although no dioxins
and furans were detected in each waste stream, it cannot be stated with
certainty that measured dioxins and furans in the flue gas were products of
combustion.
16

-------
TABLE 10. SITE A DIOXIN DRE’S
1 -lomol og/
Isomer
Flowrates ( i
g/sec)
Creosote
Flue gas
DRE
(percent)
2 ,3,7,8—TCDD
ND
ND
NA
Tetra—CDD
ND
0.14
Penta—CDD
0.1
0.044
56.0
Hexa—CDD
18
0.024
99.87
Hepta—CDD
180
0.017
99.99
Octa—CDD
170
0.014
99.99
Total—CDD
370
0.24
99.94
Note
NA —— not applicable, DRE cannot be computed
because concentration in both input and flue gas
streams were below the detection limit
ND —— not detected; below the detection limits of
0.0032 for creosote and 0.0047 for the flue gas
17

-------
TABLE 11. MASS FLOW RATES OF TOTAL DIOXINS AND FURANS
Total
PCDD
Total
PCDF
Site
Input ratea
(ng/s)
Emission ratea
(ng/s)
Input ratea
(rig/s)
Emission ratea
(ng/s)
D 1
ND (2,400)
22
ND (2,500)
150
02
ND (3,600)
12
ND (1,800)
44
E
ND (5,100)
ND (4.2)
ND (3,300)
7.4
H
ND ( 20)
ND (2.7)
ND ( 17)
27
L
ND ( 560)
7.4
ND C 570)
17
aBased on firing rate of waste and sum of detection limits for
total PCDD and total PCDF listed in Appendix A, Table 3 and 4.
18

-------
REFERENCES
1. Castaldinl, et al., “Engineering Assessment Report Hazardous Waste
Cofiring in Industrial Boilers,” Acurex Technical Report TR—84—159/EED,
June 1984.
2. DeRosier, R., et al., “Emission Testing of Industrial Boilers Cofiring
Hazardous Wastes —— Site L,” Acurex Technical Report, December 1984.
3. Castaldinl, C., et al., “Emission Testing of Industrial Boilers Cofiring
Hazardous Wastes —— Site A,” Acurex Technical Report TR—83—112/EED,
January 1983.
19

-------
APPENDIX A
BATTELLE COLUMBUS LABORATORY
ANALYTICAL REPORT
20

-------
0 BalteIle
Ci ,Iumbus L. h r li rie
r() King Avtnw
CoIurnhu , Oliii, 4 32( I 26
TItphcinc ( 14 424 -h4 24
TiIcx 24-c4 4
January 25, 1985
Mr. Carlo Castaldini
Project Engineer
Acurex Corporation
555 Clyde Avenue
P.O. Box 7555
Mountain View, CA 94039
Dear Mr. Castaldini:
We have completed the analyses of the fuel oils and XAD—2 resin extract
samples. I am enclosing a description of the analytical methodology,
the instrumentation, and the quality assurance measures that we employed.
Copies of the computer generated selected ion chromatograms are included
in the appendix. Please contact me at (614) 424—4247 if you have any
questions.
Si ncerely,
( a Q- .
Fred 1. DeRoos, Ph.D.
Principal Research Scientist
Analytical Chemistry Section
FLD/bsf
21

-------
Analytical Methodology
Introduction
This report describes the analytical procedures used to determine
the levels of polychiorinated dibenzo-p-dioxins (PCDD) and polychlorinated
dibenzofurans (PCDF) in eleven composite samples from Acurex Corporation,
Mountain View, California. The samples, consisting of fuel oils and
XAD-2 extracts, were received by Battelle on December 14, 1984.
Extraction
The composited fuel oil samples were prepared by combining
5 ml of each of the fuel samples specified in your letter dated December
7, 1984. One milliliter of the composite fuel sample was removed for
sample extraction and was spiked with three isotopically labelled internal
standards. The internal standard spikes were 25 ng of 2,3,7,8—tetrachioro-
dibenzofuran- 13 C 12 (2,3,7,8-TCDF- 13 C 12 ), 25 ng of 2,3,7,8-tetrachlorodi-
benzo-p-dioxin- 13 C 12 (2,3,7,B-TCDD— 13 C 12 ), and 25 ng of octachlorodibenzo-
-p-dioxin- 13 C 12 (OCDD- 13 C 12 ). The samples were diluted with 30 ml
of hexane and washed multiple times with concentrated sulfuric acid.
The hexane solution was then concentrated to 10 ml and eluted through
a 5 g basic alumina column using 25 ml of hexane, 25 ml of 3% methylene
chioride/hexarie, and 25 ml of 50% methylene chloride/hexane. The 50%
methylene chioride/hexane fraction was collected, concentrated and
exchanged into hexane. The sample was then passed through a multilayer
silica gel column containing 1 g silica gel, 2 g 33% NaOH on silica
gel, 1 g silica gel, 4 g 44% H 2 S0 4 on silica gel and 2 g silica gel.
The eluate was collected, concentrated, solvent exchanged into hexane,
and passed through a 1 g basic alumina column. The eluting solvents
were 5 ml of hexane, 5 ml of 3% cnethylene chioride/hexane and 22 ml
22

-------
of 50% methylene chloride/hexane. The 50% methylene chioride/hexane
fraction wa collected, concentrated to dryness and diluted with 20
i l of decane.
Composite samples of the XAD-2 extracts were prepared by
combining all of the specified samples. One of the 6 sets of samples
that were combined, XE38, was prepared with methylene chloride since
the samples to combine were dry. The composite XAD—2 samples were
spiked with 25 ng 2,3,7,8-TCDF— 13 C 12 , 25 ng 2,3,7,8-TCDD- 13 C 12 and
25 ng OCDD- 13 C 12 and eluted through two silica gel columns. The first
column contained 10 g of 44% concentrated H 2 S0 4 on silica gel and the
second was a multilayer silica gel column as described above. The
eluate was collected, concentrated to 5 ml, and passed through a 1
g basic alumina column. The elution solvents were 5 ml of hexane,
5 ml of 3% methylene chloride/hexane, and 22 ml of 50% methylene chloride/hexane.
The 50% methylene chloride/hexane fraction was collected, concentrated
to dryness and diluted with 20 l of decane.
Analysis
The extracts were analyzed and quantified for PCDD/PCDF using
combined capillary column gas chromatography/high resolution mass spectrometry
(HRGC/HRMS). The HRGC/HRMS consisted of a Carlo Erba Model 4160 gas
chromatograph interfaced directly into the ion source of a VG Model
7070 mass spectrometer. The primary chromatographic column was a 3DM
DB-5 fused silica column using helium carrier gas at a flow velocity
of 25 cm/sec. The mass spectrometer was operated in the electron impact
(El) ionization mode at a mass resolution of 9000-12000 (M/ M, 10%
valley definition). The operating parameters of the HRGC/HRMS are
sumarized in Table 1. The primary analyses, determination of total
level of each PCDD/PCDF class, were carried out using two separate
HRGC/HRMS runs. This approach was necessary due to chromatographic
23

-------
overlap of adjacent isomer classes and hardware limitations to the
number of masses that could be sequentially monitored. The first run
provided data for the PCDD and PCDF isomers having an odd number of
chlorine substituents, while the second run determined the levels of
the isomers containing an even number of chiorines. Although the DB-5
capillary column is excellent for PCDD/PCDF isomer class determinations,
it does not provide the isomer specificity of the more polar phase
columns. Since 2,3,7,8—TCDD and 2,3,7,8-TCDF are the most toxic PCDD/PCDF
isomers, all samples that were found to contain these isomers, using
the DB-5 column, were reanalyzed using 50M CP Sil-88 fused silica capillary
column which resolves 2,3,7,8-TCDD from the other 21 TCDD isomers. While
this column does not provide complete separation of 2,3,7,8-TCDF, the
level of confidence is far greater than with the DB-5 column and is
considered to be state of the art. All HRGC/HRMS data were acquired
by multiple-ion—detection using a VG Model 2035 Data System. The exact
masses that were monitored are shown in Table 2.
Quality Assurance
The operation of the HRGC/HRMS was evaluated each day by
analyzing standard mixtures of PCDD/PCDF isomers. These consisted
of 2,3,7,8-TCDF, 2,3,7,8-TCDD, 2,3,7,8-TCDF-’ 3 C12, and 2,3,7,8—TCDD- 13 C 12
mixtures to evaluate accuracy of quantification, mixtures of selected
PCDD/PCDF isomers to evaluate the stability of the chromatographic
elution windows, and TCDD isomer mixtures to evaluate isomer resolution.
The mass accuracy of the MID unit was evaluated at least every four
hours by focusing selected ion masses from perfluorokerosoene (PFK)
and correcting the slope to account for minor variations. Mass focus
stability was assured by the use of a reference PFK “lock mass” to
correct for any mass focus drift.
24

-------
Quanti fi cation
The PCDF/PCDD isomers were quantified by comparing the sum
of the two ions monitored for each class to the sum of the two ions
monitored for the corresponding internal standard. The 2,3,7,8-TCDF- 13 C 12
was used to quantify the TCDF isomers, the 2,3,7,8-TCDD— 13 C 12 was used
to quantify the TCDD and the pentachioro through hexachloro isomers
and the OCDD-’ 3 C 12 used for the heptachioro through octachioro isomers.
Experimental relative response factors were obtained by analyzing a
test mix which contained representatives of the tetra- through octa-dioxin
classes. These response factors were included in all calculations
used to quantify the data. The response factors for the furans were
assumed to be the same as those for the corresponding dioxin class.
The response factors were calculated using the sum of the two ions
monitored for each class of isomers compared to the sum of the two
ions monitored for the corresponding internal standard. The experimental
response factors were:
Tetra-COF 0.980
Tetra-CDD 1.001
Penta 0.672
Hexa 0.570
Hepta 2.498
Octa 1.132
The formula used for quantifying the isomers was:
Conc ( / = Areas of Quant. Masses Quant. of Internal Standard
g g Areas of mt. Std. Masses Resp. Factor x 1 g (for fuel oils)
25

-------
In the case.of the XAD-2 samples the level of PCDF/PCDD is reported
in nanograms per total XAD-2 extract.
The criteria that were used to identify PCDD and PCDF Isomers
were:
(1) Simultaneous responses at both masses
(2) Isotope ratio within ± 15% of theoretical value
(3) Retention times within windows determined by analyses
of standards
(4) Signal to noise ratio equal to or greater than 2.5 to
1
The 2,3,7,8-TCDF/TCDD isomers included the additional criterion
that they coeluted within ± 1 second of their isotopically labelled
analogs. A limit of detection was calculated for samples in which
a particular chlorination class was not detected. The formula used
was:
Limit of Detection (n / ) = Hts. of Quant. Masses Quantity of mt. Std. x 2.5
g Rts. of mt. Stnd. Masses Wesp. Factor x 1 g (for fuel oils )
In the case of the XAD-2 samples the limit of detection is reported
in nanograms per total XAD-2 extract.
Re s u 1 t s
The results from the PCDF/PCDD analyses are summarized In
Tables 3 and 4 respectivelY. A detection limit is listed in parentheses
for samples in which a particular chlorination class was not detected.
The selected ion current traces for the sample and standard analyses
are included in the appendix.
26

-------
TABLE 1. HRGC/HRMS OPERATING PARAMETERS
Mass Resolution
Electron Energy
Accelerating Voltage
Source Temperature
Preamplifier Gain
Electron Multiplier Gain
Transfer Line Temperature
Col urnn
Injector Temperature
Column Temp — Initial (3 mm)
Column Temp - Program
Column Temp - Final
Carrier Gas
Flow Velocity
Injection Mode
Injection Volume
9000-12000 (M/AM, 10% valley definition
70 eV
6000 volts
200°C
volts/amp
i 06
280°C
DB—5 30M
CP Sil-88 50M
300° C
160°C
30°C/mi n
250°C (CP Si1-88)
290°C (DB-5)
Heli urn
25 cm/sec
Spl itless
2 iti
27

-------
TABLE 2. EXACT MASSES USED FOR THE DETERMINATION OF PCDD AND PCDF
Accurate
Compound Mass 1
Mass
Mass 2
Theoretical
Mass
Isotope Ratio
1/Mass 2
Monoch lorodibenzo-p-dioxins 218.0134 220.0105 3.09
Monochlorodlbenzofurans 202.0185 204.0156 3.09
Trichlorodiphenyl ethers 271.9562 273.9533 1.03
DicPilorodlbenzo—p—dioxlns 251.9745 253.9715 1.54
Dichlorod lbenzofurans 235.9796 237.9766 1.54
TetrachIorodiphenyl ethers 305.9173 307.9143 0.77
Trichlorodibenzo—p—dioxins 285.9355 287.9325 1.03
Trichlorodibenzofurans 269.9406 271 .9376 1.03
Pentachiorodiphenyl ethers 341.8753 343.8724 1.54
Tetrach lorodibenzo—p—dioxins 319.8965 321 .8936 0.77
Tetrachlorodibenzofurans 303.9016 305.8987 0.77
Hexachiorodiphenyl ethers 375.8364 377.8334 1.23
Pentach lodibenzo-p—diox lns 355.8546 357.8517 1.54
Pentach lorodibenzofurans 339.8597 341 .8567 1.54
Heptachlorodiphenyl ethers 409.7974 411.7944 1.03
Hexachlorodibenzo-p-diox lns 389.8156 391 .8127 1.23
Hexach lorodibenzofurans 373.8207 375.8178 1.23
Octachlorodiphenyl ethers 443.7584 445.7555 0.88
Heptach lorodibenzo-p-dioxins 423.7766 425.7737 1.03
I4 otach1orodibenzofurans 407.7817 409.7788 1.03
Nonachlorodiphenyl ethers 477.7194 479.7165 0.77
Octachlorodibenzo-p-dioxin 457.7377 459.7347 0.88
OctachIorodibenzofuran 441 .7428 443.7398 0.88
Decachlorodiphenyl ether 511.6805 513.6775 0.69
28

-------
TABLE 3. LEVELS OF PCDF (DETECTION LIMIT)
WASTE FUELS (ppb) XAD—2 (ng/saniple)
Sample
2,378—
TCDF
Tetra—CDF Penta—CDF
Hexa—CDF
Hepta—CDF
Octa-CDF
Dia
(0.129)
(0.129)
(0.063)
(0.094)
(0.909)
(1.999)
02
(0.073)
(0.073)
(0.075)
(0.081)
(1.757)
(0.914)
E38
(0.066)
(0.081)
(0.055)
(0.080)
(0.881)
(1.113)
H
(0.050)
(0.050)
(0.074)
(0.146)
(0.667)
(0.881)
L2
(0.051)
(0.051)
(0.045)
(0.073)
(0.679)
(1.734)
MBb
(0.065)
(0.065)
(0.082)
(0.129)
(1.021)
(1.157)
XD1C
6.69
57.31
38.78
21.44
26.17
7.55
XD2
0.23
1.87
0.64
(0.333)
0.62
1.28
XE38
0.72
6.34
0.98
(0.260)
(2.586)
(2.198)
XH
(0.968)
(0.968)
3.56
10.24
1.99
5.25
XL2
0.29
5.34
4.36
5.43
3.26
2.98
XLB
(0.120)
(0.120)
(0.040)
(0.041)
(0.095)
(0.134)
MB
(0.182)
(0.182)
(0.087)
(0.186)
(0.389)
(1.497)
a 01 through L2 are waste fuel samples
bLaboratory Method Blank
CXD] through XLB are flue gas extract samples
29

-------
TABLE 4. LEVELS OF PCDF (DETECTION LIMIT)
WASTE FUELS (ppb) XAD—2 (ng/sample)
Sample
237,8—
TCDF
Tetra—CDF
Penta—CDF
Hexa—CDF
Hepta—CDF
Octa-CDF
D1
(0.076)
(0.076)
(0.057)
(0.076)
(0.693)
(2.063)
D2
(0.072)
(0.072)
(0.075)
(0.108)
(1.755)
(4.168)
E38
(0.070)
(0.068)
(0.066)
(0.094)
(1.032)
(2.106)
H
(0.075)
(0.075)
(0.084)
(0.089)
(0.702)
(1.145)
L2
(0.050)
(0.050)
(0.045)
(0.074)
(0.714)
(1.648)
MBb
(0.090)
(0.090)
(0.064)
(0.095)
(0.823)
(3.444)
XD1C
(0.106)
3.28
2.06
2.85
6.86
7.32
XD2
0.04
0.50
0.59
0.96
2.22
7.59
XE3B
(0.174)
(0.174)
(0.296)
(0.280)
(2.471)
(3.913)
XH
(0.0492
(0.492)
(0.401)
(0.898)
(1.442)
(3.024)
XL2
(0.045)
4.92
0.09
0.57
1.06
2.52
XLB
(0.064)
3.77
(0.046)
(0.052)
(0.108)
(0.220)
MB
(0.198)
(0.198)
(0.089)
(0.170)
(0.738)
(1.450)
aD] through L2 are waste fuel samples
bLaboratjjry Method Blank
CXD1 through XLB are flue gas extract samples
30

-------
TECHNICAL REPORT DATA
(Please read Inzrruc lions on the revene before completing)
I REPORT NO 12
3 RECIPIENTS ACCESSION NO
4 TITLE AND SUBTITLE
DIOXIN EMISSIONS FROM INDUSTRIAL BOILERS BURNING
HAZARDOUS MATERIALS
& REPORT DATE
April 1985
PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
C. Castaldini
3 PERFORMING ORGANIZATION REPORT NO
PERFORMING ORGANIZATION NAME AND ADDRESS
Acurex Corporation
555 Clyde Avenue
P. 0. Box 7555
Mountain View. California 94039
10 PROGRAM ELEMENT NO
DIO9
11 CONTRACT/GRANTNO
68—03—3241
12 SPONSORING AGENCY NAME AND ADDRESS
U. S. Environmental Protection Agency
Hazardous Waste Engineering Research Laboratory
26 West St. Clair Street
Cincinnati, OH 45268
13 TYPE OF REPORT AND PERIOD COVERED
14 SPONSORING AGENCY CODE
15 SUPPLEMENTARY NOTES
lb b IM
Laboratory analyses for polychiorinated dibenzo—p—dioxinS (PCDD) and polychlorinated
dibenzo-furans (PCDF) were performed on waste fuels and stack gas emission samples
from five industrial boiler test sites cofiring liquid hazardous wastes. Analytical
results indicate that, apart from creosote sludge, chlorinated wastes were void of
PCDD and PCDF compounds at detection limits in the range of 0.045 to 4.17 ppb.
Creosote sludge cofired with wood waste in a stoker boiler was found to contain 7.4 ppr
of total dioxins, primarily hepta and octa homologs. Stack gas concentrations of PCDD
were highest for the creosote wood-fired stoker at about 75 ng/m . Other PCDD results
indicate concentrations ranging from below detection levels (0.0022 ng/m 3 to
0.019 ng/m 3 ) to a maximum of 1.1 ng/m 3 . PCDF concentrations were generally higher
with total furan levels up to 5.5 ng/rn 3 . No 2,3,7,8_tetrachloro -dibenZO-P-diOXifl
(TCDD) was detected in any waste fuel. While the 2,3,7,8-TCDD isomer was detected
in flue gas emissions from one boiler, the measured value for the emissions of
2,3,7,8-TCDD was equal to the detection limit for the compound in the particular
flue gas (0.002 ng/m 3 ).
17 KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b IDENTIFIERS/OPEN ENDED TERMS
C COSATI Field/Group
Dioxin
Boilers
Hazardous Wastes
Furans
Hazardous Air Emissions
RCRA
Field Testing
Engineering
Chemistry
18 DISTRIBUTION STATEMENT
19 SECURITY CLASS (This Report)
Unclassified
21 NO OF PAGES
32
20 SECURITY CLASS (This page)
Unclassified
22 PRICE
EPA Form 2220—1 (R.v. 4—77) PREVIOUS EDITION II OBSOLETE
31

-------