-------
5.4 DIOXIN/FURAN EMISSIONS DATA
Emissions concentration and emissions rate data measured at the exhaust
stack sampling location are shown in Tables 5-10 and 5-11 for the 2378 TCDD,
total PCDD, and total PCDF species. The data include dioxin and furan
captured by the entire MM5 train, including the filter, primary XAD sorbent
trap, back-up XAD sorbent trap, impingers, and sample train clean-up rinses.
Average as-measured emissions concentrations of the 2378 TCDD, total
PCDD, and PCDF species were 10.6 ng/dscm 2378 TCDD, 558 ng/dscm total PCDD,
and 2,820 ng/dscm total PCDF. When corrected to 3% 02 using the Radian CEM
oxygen concentration data, these values correspond to 232 ng/dscm @ 3% 02,
11,900 ng/dscm 9 3%02, and 60,700 ng/dscm 9 3% 02, respectively. Average
emission rates for the three species were 0.005 g/hr 2378 TCDD, 0.28 g/hr
total PCDD, and 1.42 g/hr total PCDF. Emissions of 2378 TCDD varied by about
a factor of 3 between runs, while total PCDD and total PCDF emissions showed
less variability. The maximum deviations of the total PCDD and total PCDF
emission concentrations for any individual run from the average values for all
runs were 40 percent and 22 percent, respectively.
Isomer- and homologue-specific emission concentration data are summarized
in Tables 5-12 and 5-13 for the three test runs. Run-specific data tables
showing homologue emission concentrations in both ng/dscm and
part-per-trillion units and homologue emission rates in ug/hr units are
included in Appendix 0. Detectable quantities of each targeted dioxin and
furan species were found in the flue gas samples.
Figure 5-9 is a histogram that shows the relative distributions of the
2378 TCDD/TCDF isomers and the tetra-through octa PCDD/PCDF homologues in the
exhaust stack emissions (mole basis). The distribution of dioxin species was
relatively uniform among the various homologues. The 2378 TCDD isomer
accounted for 1 to 4 percent of the total dioxins analyzed for, which
corresponded to roughly 10 to 20 percent of the tetra-homologue total for
Surrogate recoveries could not be determined for Runs 02 and 04 dioxin/furan
samples because of the large quantities of native CDD and CDF species
present; therefore, no measure of extraction method efficiency was available.
All three runs gave similar results, tending to lend credibility to the
validity of the estimated values for the Runs 02 and 04 samples. See
Section 8.3.1.2 for more details.
5-23
*
-------
TABLE 5-10.
OVERVIEW OF DIOXIN AND FURAN EMISSIONS CONCENTRATION
DATA FOR SITE MET-A (STACK LOCATION)
Run Number
ng/dscm (as-measured)
Run 02
Run 03
Run 04
Average
Emissions
2378 TCDD •
17.5
8.5
5.8
10.6
Concentration.
Total PCDD
436
781
456
558
nq/dscm
Total PCDF
2,190
3,270
3,000
2,820
no/dscm @ 3%
Run 02
Run 03
Run 04
Average
395
170
130
232
9,800
15,600
10,300
11,900
49,200
65,300
67,400
60,700
Flue gas concentration data corrected to 3% 0
data in Table 5-8.
using the average Radian CEM
Surrogate recoveries could not be determined for Runs 02 and 04 dioxin/furan
samples because of the large quantities of native CDD and CDF species
present; therefore, no measure of extraction method efficiency was
available. All three runs gave similar results, tending to lend credibility
to the validity of the estimated values for the Runs 02 and 04 samples. See
Section 8.3.1.2 for more details.
5-24
-------
TABLE 5-11. SUMMARY OF DIOXIN AND FURAN EMISSION RATE
DATA FOR SITE MET-A (STACK LOCATION)
Run Number
Run 01
Run 02
Run 03
Average*
Dioxin/Furan
2378 TCDD
8,830
4,430
2,810
5,360
Emission Rate.
Total PCDD
219,000
408,000
222,000
283,000
ua/hr
Total PCDF
1,110,000
1,700,000
1,460,000
1,420,000
Surrogate recoveries could not be determined for Runs 02 and 04 dioxin/furan
samples because of the large quantities of native CDD and CDF species
present; therefore, no measure of extraction method efficiency was available
All three runs gave similar results, tending to lend credibility to the
validity of the estimated values for the Runs 02 and 04 samples. See
Section 8.3.1.2 for more details.
5-25
-------
TABLE 5-12 SUMMARY OF DIOXIN/FURAN EMISSIONS CONCENTRATION
DATA FOR SITE MET-A (AS-MEASURED CONCENTRATIONS)
Dioxin/Furan
Isomer
Isomer Concentration in Flue Gas
(ng/dscm)
Run 02 Run 03 Run 04
Avg.c
DIOXINS-
2378 TCDD
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
»
1.75E+01
3.53E+01
6.28E+01
1.45E+02
1.09E+02
6.51E+01
4.36E+02
1.86E+02
6.28E+02
5.59E+02
5.10E+02
1.81E+02
1.23E+02
2.19E+03
8.50E+00
7.01E+01
1.16E+02
1.08E+02
2.93E+02
1.85E+02
7.81E+02
2.53E+02
8.90E+02
9.27E+02
3.0'4E+02
5.32E+02
3.60E+02
3.27E+03
5.77E+00
5.40E+01
7.45E+01
6.76E+01
1.48E+02
1.06E+02
4.56E+02
2.65E+02
1.33E+03
7.65E+02
2.58E+02
1.97E+02
1.85E+02
3.00E+03
1.06E+01
5.31E+01
8.46E+01
1.07E+02
1.84E+02
1.19E+02
5.58E+02
2.35E+02
9.48E+02
7.50E+02
3.57E+02
3.03E+02
2.22E+02
2.82E+03
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section 8.3.1.2 for discussion of
analytical surrogate recovery results.
b. Surrogate recoveries could not be determined for Runs 02 and 04
dioxin/furan samples because of the large quantities of native CDD and CDF
S???;*Jherefore' no measure of extraction method efficiency was
J *Jhree runs gave similar results, tending to lend
to the validity of the estimated values for the Runs 02 and 04
samples. See Section 8.3.1.2 for more details.
NOTE: Concentrations shown are at as-measured oxygen conditions.
ng - 1.0E-09g
5-26
-------
TABLE 5-13 SUMMARY OF DIOXIN/FURAN EMISSIONS CONCENTRATION
DATA FOR SITE MET-A
(CONCENTRATIONS CORRECTED TO 3% OXYGEN)
Dioxin/Furan
Isomer
Isomer Concentration in Flue Gas
(ng/dscm @ 3% oxygen)
Run 02 Run 03 Run 04
Avg.c
DIOXINS
2378 TCDD
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
3.95E+02
7.93E+02
1.41E+03
3.27E+03
2.46E+03
1.47E+03
9.80E+03
4.18E+03
1.41E+04
1.26E+04
1.15E+04
4.06E+03
2.76E+03
4.92E+04
1.70E+02
1.40E+03
2.33E+03
2.15E+03
5.86E+03
3.70E+03
. 1.56E+04
5.06E+03
1.78E+04
1.85E+04
6.08E+03
1.06E+04
7.20E+03
6.53E+04
1.30E+02
1.22E+03
1.68E+03
1.52E+03
3.34E+03
2.39E+03
1.03E+04
5.97E+03
2.99E+04
1.72E+04
5.81E+03
4.44E+03
4.15E+03
6.74E+04
2.32E+02
1.14E+03
1.81E+03
2.32E+03
3.89E+03
2.52E+03
1.19E+04
5.07E+03
2.06E+04
1.61E+04
7.79E+03
6.38E+03
4.70E+03
6.07E+04
a. Data reported in this table represent lower bounds on the actual
dioxin/furan emissions from Site MET-A. See Section 8.3.1.2 for
discussion of analytical surrogate recovery results.
b. Surrogate recoveries could not be determined for Runs 02 and 04
dioxin/furan samples because of the large quantities of native CDD and CDF
species present; therefore, no measure of extraction method efficiency was
available. All three runs gave similar results, tending to lend
credibility to the validity of the estimated values for the Runs 02 and 04
samples. See Section 8.3.1.2 for more details.
NOTE: Concentrations shown are corrected to 3% oxygen using the Radian
CEM data.
ng » 1.0 E-09g
5-27
-------
1
u
FU RAN
0.9
o.a
O.7 -
o.a -
o.s -
O.4. -
0.3 -
0.2 -
O.I -
0-
•
X^
x'\
y \/ ^ /// V~
jC^fe ^2^1
2?
i
sys
1
%
$li n
Y^\% y nq
^^^ ^\^
-------
individual test runs. The contributions of the tetra- through
octa-chlorinated dioxin homologues to the total PCDD emissions were: tetra,
13-16%; 'penta, 12-18%; hexa, 21-23%; hepta, 29-32%; and octa, 17-23%. The
furan species were less uniformly distributed than the dioxin species, with
the tetrachlorinated homologue being the largest single contributor to the
total PCDF emissions. The contributions of the tetra- through
octa-chlorinated furan homologues to the total PCDF were: tetra, 45-52%;
penta, 21-23%; hexa, 7-13%; hepta, 5-9%; and octa, 4-6%.
Emission factors for the various dioxin and furan homologues were
reasonably consistent between test runs. Emission factors based on the
coke-free cupola furnace feed rates are shown in Table 5-14. Average*
emission factors for 2378 TCDD, total PCDD, and total PCDF were 0.13 ug 2378
TCDD emitted per kg coke-free feed; 6.4 ug total PCDD emitted per kg coke-free
feed; and 32.5 ug total PCDF emitted per kg coke-free feed. The coke-free
feed rate basis was chosen for the emission factors because it is the basis
used by the host plant to determine the cupola furnace feed rate.
5.5 ADDITIONAL DIOXIN/FURAN EMISSIONS DATA FROM SITE MET-A
Approximately one year after Site MET-A was sampled for dioxin/furans
under the Tier 4 study, Radian Corporation, under contract to Site MET-A,
performed additional dioxin/furan emission testing. Flue gas samples at the
outlet stack were collected during four 60-minute test runs performed on
April 15, 1986 and April 18, 1986 (two on each day). For the four tests, an
average of 445 ng/dscm of PCDD and 3968 ng/dscm of PCDF were detected in the
flue gas. On an emission rate basis, 274 mg/hr of PCDD and 2450 mg/hr of PCDF
were measured. (These results are not blank or surrogate-corrected.) The
concentration of each target dioxin and furan homologue are summarized in
Table 5-15. The homologue distribution for the April 1986 test is shown in
Surrogate recoveries could not be determined for Runs 02 and 04 dioxin/furan
samples because of the large quantities of native CDD and CDF species
present; therefore, no measure of extraction method efficiency was available.
All three runs gave similar results, tending to lend credibility to the
validity of the estimated values for the Runs 02 and 04 samples. See
Section 8.3.1.2 for more details.
5-29
-------
TABLE 5-14 DIOXIN/FURAN EMISSION FACTORS FOR SITE MET-A
Dioxin/Furan
Isomer
DIOXINS
2378 TCDD
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
Dioxin/Furan Emission Factors (ug/kg)
Run 02 Run 03 Run 04
2.22E-01
4.46E-01
7.94E-01
1.84E+00
1.38E+00
8.23E-01
5.51E+00
2.35E+00
7.94E+00
7.07E+00
6.45E+00
2.28E+00
1.55E+00
2.76E+01
9.05E-02
7.47E-01
1.24E+00
1.15E+00
3.12E+00
1.97E+00
8.32E+00
2.70E+00
9.48E+00
9.88E+00
3.24E+00
5.67E+00
3.83E+00
3.48E+01
6.76E-02
6.33E-01
8.73E-01
7.92E-01
1.74E+00
1.24E+00
5.35E+00
3.11E+00
1.56E+01
8.96E+00
3.03E+00
2.31E+00
2.16E+00
3.51E+01
Avg.b
1.27E-01
6.09E-01
9.70E-01
1.26E+00
2.08E+00
1.35E+00
6.39E+00
2.72E+00
1.10E+01
8.64E+00
4.24E+00
3.42E+00
2.52E+00
3.25E+01
a. Data reported in this table represent lower bounds on the actual
-SeCt1°n 8'3'1-2 f°r «'«"
b. Surrogate recoveries could not be determined for Runs 02 and 04
dioxin/furan samples because of the large quantities of native CDD and CDF
fE!?11?MpresS??;+Jherefore' no measure of extraction method efficiency was
l^le. All three runs gave similar results, tending to lend
^IP< LoVh?.Valldl1:? frthe estimated values for the Runs 02 and 04
samples. See Section 8.3.1.2 for more details.
NOTE: Emission factors are defined as the ug of dioxin/furan emitted per kq
of coke-free feed to the cupola furnace.
ug - 1.0E-06g
kg - 1.0E+03g
5-30
-------
TABLE 5-15. DIOXIN/FURAN HOMOLOGUE RESULTS FOR APRIL 1986 TEST
Homo! ogue
Dioxins
2378-TCDD3
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
Furans
2378-TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
Run 01
ND (0.004)
39.9
61.8
77.3
71.9
131
382
174
631
410
307
561
1100
3180
Concentration
Run 02
ND (0.008)
51.0
85.7
28.9
116
132
413
227
637
504
501
828
1490
4190
(ng/dscm,
Run 03
2.48
29.6
31.2
82.1
154
242
542
85.5
393
439
806
1260
2090
5080
as -measured)
Run 04
—
1.50
25.4
43.2
74.3
116
• 182
442
71.6
277
331
539
631
1570
3420
Average
1.0
36.5
55.5
65.7
114
172
445
140
485
421
538
820
1563
4000
Minimum detection limit indicated in parenthesis.
5-31
-------
Figure 5-10. The higher chlorinated homologues appear to be more prevalent
compared to the Tier 4 test (Figure 5-9).
For comparison, the average mass emission rates and the average
concentration measured during the Tier 4 test (May 1985) and the April 1986
test are presented in Table 5-16. The CEM results for each test are included
in Table 5-17. During the April 1986 test, oxygen and carbon monoxide were
lower than during the Tier 4 test. Carbon monoxide was higher. Total
hydrocarbons are not comparable since the Tier 4 results were measured on a
wet basis, and the April 1986 results were measured on a non-condensible (less
than 40°F) basis. The emission rates for 2378-TCDD and 2378-TCDF were lower
during the April 1986 test. However, considering that the analytical results
are precise to + 50 percent, total PCDD and PCDF emissions for both tests are
not significantly different.
5.6 HC1 TRAIN CHLORIDE EMISSIONS DATA
Table 5-18 summarizes HC1 train chloride emissions data measured at the
exhaust stack sampling location. The data are reported as "front-half,"
"back- half", and "train-total" chloride emissions. The front-half emissions
represent chlorides captured in the probe rinse/filter fraction of the HC1
train, which may include metal chlorides contained in the particulate matter.
The back-half emissions represent chlorides captured in the HC1 sample train
impingers, which would include HC1 and any metal chlorides that pass through
the sample train filter. The train-total emissions represent the sum of the
front-half and back-half emissions.
As shown in Table 5-18, the average as-measured train-total chloride
emissions concentration was approximately 2.4 mg/dscm (0.001 gr/dscf).
Corrected to 3% 02 using-the Radian CEM data, this corresponds to
approximately 60 mg/dscm @ 3% 02 (0.026 gr/dscf 9 3% 0,,). The train-total
chloride mass emission rate from the baghouse exhaust stack was about 1.2
kg/hr (2.6 Ib/hr). Chloride emissions were approximately equally distributed
between the front-half and back-half of the HC1 sample train.
5-32
-------
FURAN HOMOLOGUES
1
0.9
0.8
0.7
O.6
0.9
0.4
0.3
0.2-
0.1 -
2378 TCOF Other TCOF P«nta—CDF H«xa—CDF H«pta—CDF Octo—CDF
I7"71 RUN 01
FURAN HC
1777* RUN O2 |
JLOGUES
a RUN O3
RUN 04
DIOXIN HOMOLOGUES
i •
0.8
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
2378 TCDD Oth«r TCDD P«nta-CDO H«xa-COD H«pta—COD Octa-CDO
DIOXIN HOMOLOCUES
DTI RUN 01 1777* RUN O2 KX RUN O3 ESS RUN O4
Figure 5-10.
Dioxin/furan homologue distribution for Site MET-A
outlet emissions, April 1986 Test
5-33
-------
TABLE 5-16. COMPARISON OF DIOXIN/FURAN RESULTS FROM
APRIL 1986 TEST TO TIER 4 (MAY 1985) RESULTS
Dioxin/furan
Homologues
Dioxins
2378-TCDD
Other TCDO
Penta-TCDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
Fur an s
2378-TCDF
Other TCDF
Penta-TCDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
Average
Rate
Tier 4
May 1985
5.36
26.9
42.9
54.1
93.4
60.3
283
118
475
379
181
155
113
1420
Emissions
(ma/hr)
April 1986
0.59
22.9
35.0
40.3
70.1
105
274
88
306
262
328
504
1277
2450
Average Concentration
na/dscm @ 3% 0_
Tier 4
May '1985
232
1140
1810
2320
3890
2520
11900
5070
20600
16100
7790
6380
4700
60700
c Percent
April 1986 Change
13
399
591
744
1337
2010
5093
1489
5273
4730
6388
9758
18205
46850
-94
-65
-67
-68
-66
-20
-57
-71
-74
-71
-18
+53
+287
-23.
5-34
-------
TABLE 5-17. COMPARISON OF APRIL 1986 TEST CEM RESULTS
TO TIER 4 (MAY 1985) RESULTS
Parameter
02 (% vol)a
CO (ppmv)a
C02 (% vol)a
THC (ppmv) as propane
Averaae
Tier 4
May 1985
20.2
1220
1.8
15. Ob
Concentrations
April 1986
19.1
1060
2.3
7.5C
Concentrations are on a dry basis.
Measured on a wet basis.
Only non-condensible hydrocarbons.
5-35
-------
TABLE 5-18. HC1 TRAIN CHLORIDE EMISSIONS DATA FOR SITE MET-A
Sample Test
Component Run
Train Total Run 02
Run 03
Run 04
Average
Front Half Run 02
Run 03
Run 04
Average
Back Half Run 02
Run 03
Run 04
Average
Emissions Concentration
mg/dscm
3.05
2.38
1.86
2.43
1.70
1.49
0.93
1.37
1.35
0.89
0.93
1.06
ppmva
2.1
1.6
1.3
1.6
1.2
1.0
0.6
0.9
0.9
0.6
0.6
0.7
mg/dscmu
@ 3% 02D
78.1
53.3
47.6
59.7
43.5
33.4
23.8
33.6
34.6
19.9
23.8
26.1
Emissions Rate
(kg/hr)
1.53
1.24
0.90
1.22
0.86
0.78
0.45
0.70
0.68
0.46
0.45
0.53 -
ppmv - parts per million chloride by volume, dry basis at actual stack
02 concentration
Concentration corrected to 3% 02 using the equation:
[Cl~] @ 3% 02 - [Cl~], as measured x (20.9 - 3)/(20.9 - % 09)
where: % 02 - oxygen concentration in stack gas as measured by the Radian
CEM system (See Table 5-8)
5-36
-------
5.7 DIOXIN/FURAN ANALYSIS OF BAGHOUSE DUST SAMPLES
Table 5-19 shows the mean dioxin/furan contents of Baghouse No. 1 and
Baghouse No. 2 dust catch samples for the three test runs, and Table 5-20
shows the run-specific data.
The No. 1 Baghouse dust samples contained higher levels of each of the
dioxin and furan homologues than the No. 2 Baghouse dust samples. The
analytical values for the No. 1 Baghouse dust were consistently about 50
percent higher than those for the No. 2 Baghouse dust. There is no simple
explanation for this fact, although the No. 1 Baghouse does handle exhaust
gases from sources other than the cupola furnace, while the No. 2 baghouse
does not. As discussed'in Section 3.3, ventilation gases from the arc furnace
ladles, settler tap holes, settler ladles, and silo bin vent account for about
18 vol% of the No. 1 Baghouse gas, with cupola furnace exhaust (20 vol%),
cupola furnace charge floor ventilation gas (14%) and ambient dilution air (48
vol%) accounting for the remainder. Another difference between the two
baghouses was that the mean inlet gas temperature to the No. 1 Baghouse during
the test runs was 142°C (288°F), while the mean inlet temperature'to the No. 2
Baghouse was 130°C (266°F). Also, there are physical differences, (e.g.
length, diameter) in the ductwork leading to the two baghouses.
The distribution of tetra through octa dioxin and furan homologues in the
baghouse dust samples does not mirror that of the baghouse emissions. On a
relative basis, the higher chlorinated species tend to be more prevalent in
the baghouse dust samples than in the emissions. This may be due to a
condensation phenomenon that preferentially concentrates the less volatile,
more highly chlorinated species in the baghouse dusts.
5.8 CUPOLA FURNACE FEED SAMPLE ANALYSES
As discussed in Section 6.2.1, four cupola furnace feed material
categories were sampled at Site MET-A. These were: (1) electronic switching
gear internals and associated light gauge coated wire; (2) circuit boards; (3)"
miscellaneous plastic parts, heavy gauge wire, and telephone receiver parts;
and (4) coke. These samples were analyzed for chlorinated benzenes,
5-37
-------
TABLE 5-19.
AVERAGE DIOXIN/FURAN CONTENT OF BAGHOUSE
DUST SAMPLES FROM SITE MET-A
Isomer/Homologue
Dloxins
2378 TCDD
Other TCDD
Penta CDD '
Hexa CDD
Hepta CDD
Octa CDD
Total PCDD
Fur an s
2378 TCDF
Other TCDF
Penta CDF
Hexa CDF
Hepta CDF
Octa CDF
Total PCDF
Average Dioxin/Furan Homologue
Contents. Parts oer Rill inn fnnM
No. 1 Baghouse
Dust
0.17
2.8
5.6
20.7
44.3
53.5
127.1
10.8
92.1
96.1
140.8
154.2
207.2
700.0
No. 2 Baghouse
Dust
0.12
1.8
4.4
11.3
27.7
40.4
85.7
•
6.9
58.1
55.0
52.3
94.7
158.8
425.7
Overall
Average
_/
0.15
2.3
5.0
16.0
36.0
47.0
106.4
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5-38
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chlorinated biphenyls, and chlorinated phenols. In addition, a composite of
the circuit board samples and the electrical switching gear samples was
analyzed for total organic halide (TOX).
Table 5-21 summarizes the results of the compound-specific precursor
analyses. The electronic switching gear sample and the miscellaneous plastic
parts/heavy gauge wire/telephone receiver parts sample were found to contain
small quantities (<300 ppb) of chlorinated biphenyls, but chlorinated benzenes
and chlorinated phenols were not detected. None of the precursor compounds
analyzed for were found in the coke and circuit board samples.
A composite of the circuit board sample and the electrical switching gear
samples from Site MET-A was analyzed using the TOX procedures. The circuit
board/electrical switching gear composite sample contained approximately 4,300
ppm total TOX. Thus, although the specific precursors analyzed for (i.e.,
chlorobenzenes, chlorinated biphenyls, and chlorophenols) were either not
detected or were found in only small quantities, there were significant
quantities of halogenated species present. This suggests that either (1) the
specific precursors analyzed'for were present in the samples but were not
easily detected using the GC/MS procedure due to the complexity of the sample
matrix, or (2) halogenated species other than the specific precursors analyzed
for were present in the samples. Potential sources of these "other"
halogenated species include polyvinyl chloride, halogenated plasticizers,
etc., that may have been present in the plastic-bearing feed components.
5.9 AMBIENT XAD TRAIN DATA
Dioxin and furan concentration data for ambient air samples taken near
the baghouse dilution air intake point are shown in Table 5-22. Small but
detectable quantities were found of all species analyzed for except 2378-TCDD
and penta-CDD, which were not detected. Measured ambient air concentrations
of total PCDD and total PCDF were 0.15 ng/dscm and 1.1 ng/dscm, respectively.
5.10 SOIL SAMPLING DATA
The soil sample was archived pending evaluation of analytical data.
5-40
-------
TABLE 5-21. SUMMARY OF DIOXIN PRECURSOR DATA FOR SITE MET-A FEED SAMPLES
Precursor categories
Precursor Concentration, ug/g (ppm)
Coke far^Kre "carts
Gear
Total Chlorinated Benzenes
Total Chlorinated Biphenyls
Total Chlorinated Phenols
Total Organic Halide (TOX)
NO
NO
ND
NA
ND
0.004a
ND
NA
NDb
NDb
ND
4,300d
ND
0.26C
ND
4,300d
Was the On1y Polychlorlnated biphenyl homologue
detected in the telephone parts and wire sample.
b' 5l2!iIIUKal ?Urr°9at^rec?Yer1es were very low for the circuit board
foTlhf JhiUabJeA8)' Wh1ch ^ 1J|d1cat« low niethod efficiencies
for the chlorinated benzenes and biphenyls.
o^;i He?ta:> ai?d Octa- polychlorinated biphenyls were all
detected in the electronic switching gear samples.
d. TOX analysis was performed on a composite circuit board/electronic
switching gear sample only.
ND = not detected
NA = not analyzed
5-41
-------
TABLE 5-22. DIOXIN/FURAN AMBIENT CONCENTRATION DATA FOR SITE MET-A
Isomer/Homologue Concentration
(ng/dscm)
Dioxins
2378 TCDD ND
Other TCDD 3.9 x 10~2
Penta CDD ND
Hexa CDD 3.1 x 10"2
Hepta CDD 3.1 x 10"2
Octa CDD 5.4 x 10"2
Total PCDD 1.5 x 10"*
Furans
2378 TCDF 4.6 x id'2
Other TCDF 4.6 x 10"1
Penta CDF 1.1 x 10"1
Hexa CDF 2.3 x 10"1
Hepta CDF 1.3 x 10"1
Octa CDF 1.2 x 10"l
Total PCDF 1.1 x 10°
ND - Not detected.
5-42
-------
6.0 SAMPLING LOCATIONS AND PROCEDURES
This section details the sampling locations and procedures listed in
Table 4.1 of Section 4.0. Gaseous sampling is considered in section 6.1, and
solids sampling is considered in Section 6.2.
6.1 GASEOUS SAMPLING
Four types of gaseous samples were taken during this test program:
Modified Method 5 dioxin/furan (MM5), Modified Method 5 HC1 (HC1), EPA Method
3, and continuous emissions monitoring (CEM). The sampling locations and
methods are listed in Table 6-1 and are further discussed in this section.
6.1.1 Gaseous Sampling Locations
6-1.1.1 Cupola furnace baahouse system exhaust stack. The exhaust stack
sampling location of the cupola furnace baghouse system is shown as Point A in
Figure 4rl. This location was used for dioxin/furan sampling and HC1
sampling, according to MM5 procedures described in section 6.2.2. EPA Methods
2, 3, and 4 were performed to determine the volumetric flowrate, molecular
weight and moisture content of the exhaust gas, respectively.
The sample port locations and dimensions are shown in Figure 6-1. The
outside diameter of the stack is 12 feet. Four MM5 sample ports are located
approximately 160 feet from the base of the stack. The MM5 sample ports have
3 inch diameters and are spaced 90° apart. The MM5 sample ports are 80 ft
(6-7 equivalent duct diameters) downstream of the breeching where the baghouse
exhaust gases enter the stack and 90 ft (7-8 equivalent duct diameters)
upstream of the top of the stack. According to EPA Method 1, a total of 12
traverse points are required. A layout of the traverse points is shown in
Figure 6-2. the railings of the platform limit the effective length of the
sample probe to four feet, which requires the use of all four ports to
complete a sampling traverse.
6-1
-------
TABLE 6-1. SUMMARY OF GAS SAMPLING METHODS FOR SITE MET-A
'Sample Location
Sample Type
or Parameter
Sample
Collection Method
Blast Furnace
Baghouse System
Exhaust Stack
Breeching toe
Exhaust Stack
Dioxin/furan
Volumetric flow
Molecular weight
Moisture
HC1
CO, C0?, 0-, NOY,
S02, and THC x
monitoring.
Modified EPA Method 5
EPA Method 2
EPA Method 3
EPA Method 4
HC1 train
Continuous Monitors
Ambient dilution
Air Sampling
Dioxin/furan
Dioxin precursors
Ambient XAD trai.n
Ambient XAD train
6-2
-------
Discharge to Atmosphere
Sample Point A:
Pour 3" Ports
90° Apart
Platforms
Sample Point B:
GEM Port
Exhaust Gas
from Baghouse No
and Baghouse No
»as r
: $ Q
Breeching
Exhaust Stack
i i i
•*- 12 ft
O.O.
90 ft
80 ft
80 ft
Figure 6-1. Sample port locations and flow dimensions.
6-3
-------
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6-4
-------
6.1.1.2 Cupola furnace baohouse system breeching to exhaust stack. The
sample ports used by Radian and the host plant for continuous monitoring are
located in the breeching to the exhaust stack, as shown in Figure 6-1. The
exhaust gases from baghouse No. 1 and baghouse No. 2 are combined before they
reach the sampling location.
6.1.1.3 Ambient dilution air sampling. The baghouse ambient dilution
air was sampled for dioxin/furan and dioxin precursors near the air dilution
intake point, which is shown as Point C in Figure 4-1. Samples were collected
using the ambient XAD train, which is described in Section 6.2.2.3.
Two separate ambient XAD trains were run simultaneously during the time
periods that the MM5 samples were collected. The same two ambient XAD trains
were used during all three MM5 test runs, providing composite dilution air
samples for the site. One ambient XAD train was analyzed for dioxin/furan and
the other for dioxin/furan precursors.
6.1.2 Gaseous Sampling Procedures
Gaseous sampling procedures used during this program are discussed in
detail in the Tier 4 QAPP.(1> A brief description of each method is provided
in the following sections.
6-1-2.1 Modified Method 5 (MM5K Gas sampling for dioxins and furans
was based-on the October 1984 draft of the ASME chlorinated organic compound
sampling protocol. This sampling method is a modified version of EPA Method 5
that includes a solid sorbent module (i.e., XAD-2 resin) for trapping vapor
phase organics. The only differences in the sampling protocol which were not
discussed in the Tier 4 QAPP are as follows:
(1) Benzene was substituted for hexane or toluene as both the cleanup
and extractant solvent for the MM5 filters and the XAD-2 resin.
This was caused by a discrepancy between the draft ASME sampling
protocol and the draft ASME analytical protocol. (November 16, 1985)
(2) Methylene chloride was substituted for hexane as the final field
rinse solvent for the MM5 train. Methylene chloride was also
substituted for hexane in the glassware cleaning procedure. This
6-5
-------
substitution was instituted to improve the field recovery of dioxins
and furans from the MM5 train.
(3) A backup XAD sorbent module was used at this test site to ensure
high capture efficiencies for dioxins and furans.
The MM5 samples were collected isokinetically over a 4 hour sampling
period at the exhaust stack location. The minimum sample volume for any test
run was 3.3 dscm (116 dscf). The MM5 sampling rate was approximately 0.016
dscmm (0.56 dscfm).
Following sample recovery, the various components of the sample (filter,
solvent rinses, XAD module, etc.) were sent to the EPA's Troika laboratories
to quantify 2378 TCDD, the tetra- through octa-PCDD homologues, and the tetra-
through octa-PCDF homologues present in the samples.
A schematic diagram of the MM5 sampling train used at Site MET-A is shown
in Figure 6-3. Flue gas is pulled from the stack through a nozzle and a
glass-lined probe. Particulate matter is removed from the gas stream by means
of a glass fiber filter housed in a teflon-sealed glass filter holder
maintained at 248+25°F. The gas passes through a sorbent trap similar to that
illustrated in Figure 6-4 for removal of organic constituents. The trap
consists of separate sections for (1) cooling the gas stream, and (2)
adsorbing the organic compounds on Amber!ite XAD-2R resin (XAD). A backup XAD
resin trap was used at this test site to ensure high capture efficiencies for
dioxins and furans. A chilled impinger train following the sorbent trap is
Used to remove water from the flue gas, and a dry gas meter is used to measure
the sample gas flow.
6-1-2.2 HC1 Determination. HC1 concentrations in the outlet exhaust
stack were determined using another modification of EPA Method 5. The sample
train components and operation are identical to those of Method 5 with the
following exceptions:
1. Water in the first two impingers was replaced with 0.1 m NaOH.
2. Sampling was single point isokinetic, with the nozzle placed at
points in the stack with approximate average velocity.
3. The moisture/NaOH in the impingers was saved for laboratory analysis
by ion chromatography.
6-6
-------
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Trap '
Coar«« Frit
28/12
Figure 6-4. Condenser Coil and XAD-2 Resin Trap
6-3
-------
Recovery of the HC1 train provided a sample consisting of three components:
probe rinse, filter, and back-half rinse/impinger catch. These components
were shipped from the field to Radian's Austin, Texas laboratory for analysis
by ion chromatography.
6.1.2.3 Ambient Air Sampling. A schematic diagram of the ambient XAD
sample train is shown in Figure 6-5. The ambient train consists of a short
glass probe, sorbent tube, knockout impinger (optional), silica gel impinger,
umbilical line, pump, and dry gas meter. Ambient air is drawn into the
sorbent module, where it is cooled to 20°C (68°F) or lower, and the organic
constituents are adsorbed by the XAD resin. The gas is then dried with the
silica gel, and the sample volume is measured by the dry gas meter.
The entire ambient XAD sample train is leak tested before and after each
test run at 10 inches H20 to ensure that the leak rate is less than 0.02 cfra.
Dry gas meter readings are recorded twice daily (i.e., at the beginning and
end of each test period). The dry gas meter temperature, ice bath
temperatures, pressure, and volume are recorded once per hour during the
sampling periods.
Recovery of the ambient XAD sample train is similar to that of the MM5
train. The probe is rinsed with acetone and methylene chloride three times
each, and this rinse is stored in a single sample container. The XAD sorbent
module is capped with ground glass caps. If the optional knockout impinger is
used, the impinger is rinsed with acetone and methylene chloride, and the
condensate and rinse are combined in a single container.
6.1.2.4 Volumetric Gas Flow Rate Determination. The volumetric gas flow
rate was determined using EPA Method 2. Based on this method, the volumetric
gas flow rate is determined by measuring the average velocity of the flue gas
and the cross-sectional area of the duct. The average flue gas velocity is
calculated from the average gas velocity pressure (AP) across an S-type pi tot
tube, the average flue gas temperature, the wet molecular weight, and the
absolute static pressure.
6-9
-------
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6-10
-------
6-l-2.5 Flue Gas Moisture Determination. The moisture content of the
flue gas was determined using EPA Method 4. Based on this method, a known
volume of particulate-free gas is pulled through a chilled impinger train.
The quantity of condensed water is determined gravimetrically and then related
to the volume of gas sampled to determine the moisture content^—
6.1.2.6 Flue Gas Molecular Weight Determination. The integrated
sampling technique described in EPA Method 3 was used to obtain a composite
flue gas sample for fixed gas analysis (02, C02, N2). The fixed gas analysis
was used to determine the molecular weight of the gas stream. A small
diaphragm pump and a stainless steel probe were used to extract single point
flue gas samples. The samples were collected at the MM5 sampling ports using
Tedlar bags. Moisture was removed from the gas sample by a water-cooled
condenser so that the fixed gas analysis is on a dry basis.
The composition of the gas sample was determined using a Shimadzu Model
3BT analyzer instead of the Fyrite or Orsat analyzer prescribed in Method 3.
The Shimadzu instrument employs a gas chromatograph and a thermal conductivity
detector to determine the fixed gas composition of the sample.
6.1.2.7 Continuous Emissions Monitoring. Continuous emissions
monitoring was performed in the breeching leading to the exhaust stack for 0
C02, CO, NOX, S02, and THC throughout the 3 to 5-hour period that dioxin
sampling was conducted each test day. Sample acquisition was accomplished
using an in-stack filter probe and a TeflonR sample line connected to a mobile
laboratory. The heat-traced sample line was maintained at a temperature of at
least 120°C (248°F) to prevent condensation in the sample line. The stack gas
sample was drawn through the filter and sample line using pumps located in the
mobile laboratory. Sample gas to be analyzed for CO, C02, 02, S02, and NO
was pumped through a sample gas conditioner, which consists of an ice bath and
knockout trap. The sample gas conditioner removes moisture and thus provides
a dry gas stream for analysis. A separate unconditioned gas stream was
supplied to the THC analyzer for analysis on a wet basis.
An Anarad Model 412 nondispersive infrared analyzer was used to measure
CO and C02; a Beckman Model 755 paramagnetic analyzer was used to measure 02;
and a Beckman Model 402 flame ionization analyzer was used to measure THC.
6-11
-------
6.2 SOLID SAMPLES
Samples of the cupola furnace feed materials, the No. 1 and No. 2 baghouse
dusts, and plant soils were taken at Site MET-A. The sampling locations and
methods are discussed in the following sections.
6-2.1 Cupola Furnace Feed
The telephone scrap component of the charge bed and the metallurgical
coke used to fire the blast furnace were the only feed materials with the
potential to contain dioxin/furan precursors. These materials were sampled
.once during the test program and analyzed by the Radian/RTP laboratory for
dioxin/furan precursor content.
Telephone scrap sampling consisted of taking grab samples of one or more
large pieces of each clearly distinguishable plastic-bearing telephone scrap
material in the charge bed. The large grab samples so obtained were size
reduced, composited and analyzed by the Radian/RTP laboratory. Due to the
heterogeneity of the charge bed, it was beyond the scope of the Tier 4 project
to obtain truly representative samples. The feed sampling effort was consid-
ered representative only in the sense that each major plastic-bearing material
was sampled.
For the purpose of the Tier 4 project, the telephone scrap was considered
to consist of the following materials: (i) switching gear internals and
associated narrow gauge coated wire; (ii) circuit boards; and (iii) miscellane-
ous plastic parts, heavy gauge wire, and telephone receiver parts. No attempt
was made to estimate the relative contributions of these types of materials to
the telephone scrap category.
6.2.2 Baohouse Dust Samples
Separate samples of the No. 1 and No. 2 baghouse dusts were taken twice
per MM5 test run, once at the beginning and once at the end of each run. The
individual samples were taken from a capped spout installed by plant personnel
on the baghouse screw conveyors. A composite sample of dust from each baghouse
was prepared at the end of each run and sent to Troika for dioxin/furan
analysis.
6-12
-------
6.2.3 Soil Sampling
A single composite soil sample comprised of 10 individual soil core
samples was prepared for Site MET-A. Soil sampling protocol for Tiers 3, 5,
6, and 7 of the National Dioxin Study are specified in the documents, "Sampling
Guidance Manual for the National Dioxin Study." A similar protocol was used
for soil sampling at Site MET-A. Soil samples were collected by forcing a
bulb planter into the soil to a depth of 3 inches. The soil samples were
composited in a clean stainless steel bucket. A portion of the composite was
shipped to .Troika for potential dioxin/furan analysis.
A total of 10 soil sampling locations were selected around the periphery
of the plant site. These locations are shown in Figure 6-6. It should be
noted that the plant site consists mainly of fill dirt; thus, natural soils
for the area were not available.
6-13
-------
fl-TT.T -SS?.-^^_..:. . T^rr- r -r^irsr-
..— -.4, • S> —
ST-^i^ v'
\
Figure 6-6. Soil Sampling Locations for Site MET-A
6-14
-------
7.0 ANALYTICAL PROCEDURES
Laboratory procedures used to quantify dioxins/furans and dioxin/furan
precursors in the Tier 4 samples are described in this section. Samples
analyzed by EPA's Troika laboratories for dioxin/furan content included MM5
train samples, back-up XAD traps, baghouse dust samples, and ambient XAD train
samples. Procedures used for the dioxin/furan analyses are described in
detail in the Analytical Procedures and QA Plan for the Analysis of Tetra
through Octa CDD's and CDF's in Samples from Tier 4 Combustion and
Incineration Processes. These procedures are summarized in Section 7.1.
Cupola furnace feed samples were analyzed by Radian to determine
concentrations of chlorinated phenols (CP), chlorobenzenes (CB),
polychlorinated biphenyls (PCBs), and total organic halogen (TOX). Procedures
used for these analyses are detailed in Section 7.2.
7.1 DIOXINS/FURANS
The analytical procedures summarized in this section were used by Troika
for dioxin/furan analysis of MM5 train samples, back-up XAD traps, baghouse
dust samples, and ambient XAD train samples from Site MET-A. A separate
document detailing these procedures has been prepared.
Samples consisting of organic solvents, aqueous solutions, and solids
were prepared for analysis using slightly different procedures. The organic
solvent samples consisted of rinses from the MM5 probe, nozzle, filter housing
and condenser coil. Aqueous samples consisted of impinger catch solutions,
and solid samples included filters, XAD resin, and baghouse dust.
Isotopically-labeled surrogate compounds were added to all samples prior to
extraction to allow determination of method efficiency and for quantification
purposes.
Organic liquid samples (e.g., acetone and methylene chloride-based MM5
train rinses) were concentrated using a nitrogen blowdown apparatus. The
Analytical Procedures and Quality Assurance Plan for the Analysis of Tetra
Through Octa Chlorinated Dibenzo-p-Dioxins and Dibenzofurans in Samples
from Tier 4 Incineration Processes. Addendum to: "Analytical Procedures
and Quality Assurance Plan for the Analysis of 2378-TCDD in Tier 3-7
Samples of the U.S. Environmental Protection Agency National Dioxin
Strategy." EPA/600/3-85-019, April 1985.
7-1
-------
residue, which contained participate matter from the MM5 train probe and
nozzle, was combined with the filter and handled as a solid sample. Solid
samples were extracted with benzene .in a Soxhlet apparatus for a period of at
least 16 hours. The extract was concentrated by nitrogen blowdown and
subjected to chromatographic cleanup procedures.
Aqueous solutions (e.g., MM5 train impinger samples) were extracted with
hexane by vigorous shaking for a three hour period. This extraction procedure
was repeated three times, with the organic fractions ultimately being combined
and concentrated for chromatographic cleanup.
The cleanup procedure involved using liquid chromatographic columns to
separate the compounds of interest from other compounds present in the
samples. Four different types of columns were used: a combination acid and
base modified silica gel column, a basic alumina column, a PX-21 carbon/eelite
545 column and a silica/diol micro column. These were used in successive
steps, with the last two being used only if necessary.
The cleaned samples were analyzed using high resolution gas
chromatography/high resolution mass spectrometry (GC/MS). Conditions for the
analyses were as follows:
Gas Chromatoaraph - Injector configured for capillary column, splitless
injection; injector temperature 280°C; helium carrier gas at 1.2 ml/min;
initial column temperature 100°C: final column temperature 240°C; interface
temperature 270°C.
Mass Spectrometer - Varian/MAT Model 311A; electron energy 70ev; filament
emission IMA; mass resolution 8000 to 10,000; ion source temperature 270°C.
7.2 DIOXIN/FURAN PRECURSORS
Feed samples for Site MET-A were analyzed by Radian/RTP for chlorophenols
(CP), chlorobenzenes (CB) and polychlorinated biphenyls (PCBs) by GC/MS; total
organic ha!ides (TOX) by GC/Hall detector. Analytical procedures are
discussed in the following sections.
7-2
-------
7.2.1 GC/MS Analyses
The analytical procedures used for determining CP, CB, and PCB
concentrations in feed samples are modified versions of procedures typically
used for the analysis, of MM5 train components. These procedures involve
initial extraction of the sample with an appropriate solvent, preliminary
separation of the compounds of interest by solvent partitioning and liquid
chromatography, and analysis of the processed fractions. Solutions containing
CB and PCB are injected directly into the GC/MS, and solutions containing CP
are derivatized prior to injection. Details on the procedures used for Site
MET-A samples are provided in the sections below.
7.2.1.1 Sample Preparation
A flow chart for the sample preparation procedure used for Site MET-A
feed samples is shown in Figure 7-1. The first step in the procedure involved
adding labeled surrogate compounds to provide a measure of extraction method
efficiency. The next step involved adding a mixture of 0.5 N NaOH and MeCl?
to the sample and sonicating the sample for 30 minutes. The NaOH and MeCl2
mixture converts the acid compounds to their salts and collects base/neutrals
in the organic solvent. The sonicated sample was filtered and rinsed with 0.5
N NaOH. The filtrate was extracted three times in a separatory funnel with
MeCl2 and the aqueous and organic fractions were saved for derivatization
and/or further cleanup. The aqueous fraction (or acids portion) was acidified
to pH2 with HC1 and then extracted three times with MeClg. The MeCl2 from
this extraction was dried with anhydrous Na2S04, exchanged to benzene, and
concentrated using a nitrogen blowdown apparatus. Acetylation of any CP
present in the sample involved the following steps:
1. 2.0 mL isooctane, 2.0 ml acetonitrile, 50 uL pyridine, and 20 uL
acetic anhydride were added to the extract. The test tube
containing the extract was placed in a 60°C water bath for 15
minutes and was shaken 30 seconds every 2 minutes.
7-3
-------
flOg Sample
1.0ml. Baae/Neutral Surrogates
1.0mL Acid Surrogates
Sonlcat* with 25OmL
0.5 M NaOH and 1SmL M«CI2
Flltar thru Buchner and
Rinse with 0.8 H NaOH
Extract 3x with MeClj
In Separatory Funnel
Aqueous
Organic
Adjust to pH2 with HCI;
Extract 3x with MeC>a
Discard Aqueous
Filter with N«23O4
Discard All
AcM/H2O Layers
Add 30mL Cone. H2SO4:
Shake 4 mln; Atternate
with 30ml. distilled H2O;
Repeat until acid Is clear.
Add lOmL Benzene
Concentrate to 1mL
Filter wtth
To 1mL Benzene add:
2.0ml. Iso octane
2.0ml. Acetonltrlle
SOmt Pyridme
20mL Acetic Anlydrlde
Add 10mL Hexanes;
Concentrate to 1mL
Pre-wet Column
wtth 20mL Hexanes
Chromatography column wtth:
1.0o Silica
2.0o 33% NaOH Silica
2.0« Silica
Put In 80 C iyj bath
for 15 minutes, Shaking
3O seconds every 2 minutes.
Bute with QOmL Hexanes;
Concentrate to 1mL
Add 6mL of O.O1 N
H3PO4; Shake 2 minutes.
Mml-cokimn with
1.0g Alumina
Ehrte with 2OmL SO/SO
MeClg/Hexanes
Add Quantltatlon Standards;
Concentrate to ImL
GC/MS Analysis
Figure 7-1. Sample Preparation Flow Diagram for
Site MET-A Precursor Analyses.
7-4
-------
2. 6 ml of 0.01 N_ H3P04 were added to the test tube,-and the sample
was agitated for 2 minutes on a wrist action shaker.
3. The organic layer was removed and the quantisation standard was
added. The sample was concentrated in a Reacti-Vial at room
temperature (using prepurified N2) to 1 ml prior to GC/MS analysis.
Cleanup of the organic (or base/neutrals) layer from the first MeCK
extraction involved successively washing the extract with concentrated H2SO.
and double-distilled water. The acid or water was added in a 30 ml portion
and the sample was shaken for two minutes. After the aqueous (or acid) and
organic layers were completely separated, the aqueous (or acid) layer was
discarded. The acid washing procedure was repeated until the acid layer was
colorless. The organic fraction from the final wash was dried with anhydrous
Na2$04, exchanged to hexane and concentrated. Final cleanup of the sample by
column chromatography involved the following procedure.
A glass macro-column, 20 mm o.d. x 230 mm in length, tapered to 6 mm o.d.
on one end was prepared. The column was packed with a plug of silanized glass
wool, followed successively by 1.0 g silica, 2.0 g silica containing 33% (w/w)
1 N NaOH, and 2.0 g silica. The concentrated extract was quantitatively
transferred to the column and eluted with 90 ml hexane. The entire eluate was
collected and concentrated to a volume of 1 ml in a centrifuge tube.
A disposable liquid chromatography mini-column was constructed by cutting
off a 5-mL Pyrex disposable pipette at the 2.0 ml mark and packing the lower
portion of the tube with a small plug of silanized glass wool, followed by 1 g
of Woehlm basic alumina. The alumina had been previously activated for at
least 16 hours at 600°C in a muffle furnace and cooled in a desiccator for 30
minutes just before use. The concentrated eluate from above was
quantitatively transferred onto the liquid chromatography column. The
centrifuge tube was rinsed consecutively with two 0.3-mI"portions of a 3
percent MeCl2: hexane solution, and the rinses were transferred to the liquid
chromatography column.
The liquid chromatography column was eluted with 20 ml of a 50 percent
(v/v) MeCl2:hexane solution, and the eluate was concentrated to a volume of
approximately 1 ml by heating the tubes in a water bath while passing a stream
7-5
-------
of prepurified N2 over the solutions. The quantitation standard was added and
the final volume was adjusted to 1.0 ml prior to GC/MS analysis.
7.2.1.2 Analysis
Analyses for CP, CB and PCBs present in the feed sample extracts were
performed with a Finnigan Model 5100 mass spectrometer using selected ion
monitoring. A fused silica capillary column was used for chromatographic
separation of the compounds of interest. Analytical conditions for the GC/MS
analysis are shown in Table 7-1.
Tuning of the GC/MS was performed daily as specified in the Tier 4 QA
Project Plan. An internal-standard calibration procedure was used for sample
quantitation. Compounds of interest were calibrated against a fixed
concentration of either d12-chrysene (for CP) or dg-naphthalene (for CB, PCB).
Components of the calibration solution are shown in Table 7-2. For
multi-point calibrations, this solution was injected at levels of 10, 50, 100,
and 150 ng/ml.
Compound identification was confirmed by comparison of chromatograph.ic
retention times and mass spectra of unknowns with retention times and mass
spectra of reference compounds. Since the selected ion monitoring technique
was necessary for the samples analyzed, care was taken to monitor a
sufficiently wide mass region to avoid the potential for reporting false
positives.
The instrument detection limit for the analytes of interest (i.e., CP,
CB, and PCB) was estimated to be approximately 500 pg on column. For a 50 g
sample and 100 percent recovery of the analyte, this corresponds to a feed
sample detection limit of 10 ppb.
7.3 TOX ANALYSIS
Cupola furnace feed samples were analyzed for total organic halide (TOX)
by short-column GC and a Hall detector (GC/Hall). Solid samples were
extracted with benzene for at least 16 hours in a Soxhlet apparatus. The
7-6
-------
TABLE 7-1. INSTRUMENT CONDITIONS FOR GC/MS PRECURSOR ANALYSES
Column
Injector Temperature
Separator Oven Temperature
Column Head Pressure
He flow rate
GC program
Emission Current
Electron Energy
Injection Mode .
Mode
Chlorobenzenes/
Polychlorinated biphenyls
30 m WB DB-5 (1.0 u film
thickness) fused silica
capillary
290°C
290°C
9 psi
1 mL/min
40(4)-290°C,
min & hold
0.50 ma
70 ev
Chlorophenols
290°C
290°C
9 psi
1 mL/min
40(1)-290°C,
12°/min & hold
0.50 ma
70 ev
Splitless 0.6 min, then 10:1 split
Electron ionization, Selected Ion
Monitoring
7-7
-------
TABLE 7-2. COMPONENTS OF THE CALIBRATION SOLUTION
Base/Neutrals
4-chlorobiphenyl
3,3'-di chlorobi phenyl
2,4',5-trichlorobiphenyl
3,3'4,4'-tetrachlorobiphenyl
2,2',6,6»-tetrachlorobi phenyl
2,2,4,5,6-pentachlorobiphenyl
2,2',4,4',5,5'-hexachlorobiphenyl
2,2',3,4,4',5',6-heptachlorobiphenyl
2,2',3,3',4,4',5,5'-octachlorobiphenyl
2,2',3,3',4,4',5,6,6'-nonachlorobiphenyl
decachlorobi phenyl
p-dichlorobenzene
1,2,4-tri chlorobenzene
1,2,3,5-tetrachlorobenzene
pentachlorobenzene
hexachlorobenzene
d^-l,4-dichlorobenzene (SS)1
3-bromobiphenyl (SS)
2,2',5,5'-tetrabromobiphenyl (SS)
2,2',4,4',6,6'-hexabromobiphenyl (SS)
octachloronaphthalene (QS)2
d10-phenanthrene (QS)
djg-chrysene (QS)
Acids
2,5-dichlorophenol
2,3-dichlorophenol
2,6-dichlorophenol
3,5-dichlorophenol
3,4-dichlorophenol
2,3,5-trichlorophenol
2,3,6-trichlorophenol
3,4,5-trichlorophenol
2,4,5-trichlorophenol
2,3,4-trichlorophenol
2,3,i5,6-tetrachlorophenol
pentachlorophenol
dg-phenol (SS)
d.-2-chlorophenol (SS)
C6~pentachlorophenol (SS)
dg-naphthalene (QS)
2,4,(3-tribromophenol (QS)
d10-phenanthrene (QS)
d12chrysene (QS)
1
Surrogate standard.
"Quantitation standard.
7-8
-------
extracts were washed three times with 100 ml portions of reagent-grade water
concentrated to 10 mL.
An attempt to use a fused silica capillary column to separate surrogates
from target compounds was unsuccessful due to the complexity of the sample
constituents. Determinations for TOX were therefore performed on samples
without surrogates and no measure of extraction efficiency is available.
Instrument conditions are shown in Table 7-3. Sample quantitation was
based on an average response factor developed from a mixture of chlorinated
benzenes and brominated biphenyls. Individual CP, CB and PCBs were also
injected at. various concentrations to develop a calibration curve for
comparison to the mixture response factors.
7-9
-------
TABLE 7-3. ANALYTICAL CONDITIONS FOR TOX ANALYSIS
Hall Detector Conditions
Reactor temperature - 850°C
Solvent - n-propanol
Hydrogen flow rate - 35 mL/min
6C Conditions (Varian 37001
Injection volume (1 - 5 uL)
Helium carrier gas flow rate - 60 mL/min
Column - 3-ft packed column with 1 in 10% 0V 101
Column temperature - 200°C isothermal
7-10
-------
8.0 QUALITY ASSURANCE/QUALITY CONTROL (QA/QC)
This section summarizes the results of the quality assurance and quality
control (QA/QC) activities for Site MET-A. The flue gas dioxin/furan
surrogate recovery data for Run 03 was within the QC specifications presented
in the Tier 4 QAPP. The surrogate recoveries for Runs 02 and 04 were not
within the specifications. The surrogate recoveries could not be determined
because of the large amounts of native CDDs and CDFs which were present in the
samples. The surrogate recoveries for the back-up XAD modules ranged from 82
to 96 percent. The surrogate recoveries for the baghouse dust samples and
ambient XAD train samples were all within the specifications designated in the
QAPP. The results of the analysis of the fortified laboratory QC sample were
all within 32 percent of true value except for 2378 TCDF, which was 100
percent higher than the true value. This should not affect the data quality
since the true value was so near the detection limit. The specifications for
the fortified sample were + 50 percent. The laboratory fortified QC sample
for baghouse dust was also within 32 percent of the true value. Generally,
the reported analytical results for the flue gas samples should be considered
lower bounds on the true values while the baghouse dust and ambient results
should be considered reasonable estimates.
The dioxin/furan precursor analysis of the feed samples was not as
accurate as the dioxin/furan homologue analysis. Surrogate recoveries of the
base neutrals fractions were generally within the specified QC limits of
+ 50 percent; however, the surrogate acid fractions were generally below the
specified limits. In spite of the low recoveries of the acid fraction, the
dioxin/furan precursor results are considered a reasonable approximation of
the true precursor concentration in the feed samples.
The following sections summarize the results of all Site MET-A QA/QC
activities. Manual gas sampling methods are considered in Section 8.1 and
continuous emission monitoring and molecular weight determinations are
considered in Section 8.2." The laboratory analyses QA/QC activities are
summarized in Section 8.3.
8-1
-------
8.1 MANUAL GAS SAMPLING
Manual gas sampling methods at Site MET-A included Modified Method 5
(MM5), EPA Methods 1 through 4, and HC1 train sampling. These methods are
discussed in Section 6.0. Quality assurance and quality control (QA/QC)
activities for the manual sampling methods centered around (1) equipment
calibration, (2) glassware pre-cleaning, (3) procedural QC checks, and (4)
sample custody procedures. Key activities and QC results in each of these
areas are discussed in this section. Also discussed are problems encountered
that may have affected data quality.
8.1.1 Equipment Calibration and Glassware Preparation
Pre-test calibrations or inspections were conducted on pitot tubes,
sampling nozzles, temperature sensors and analytical balances. Both pre-test
and post-test calibrations were performed on the dry gas meters. All of the
field test equipment met the calibration criteria specified in the Tier 4
Qual.ity.Assurance Project Plan (QAPP). Differences in the pre-test and
post-test dry gas meter calibrations were less than 2 percent (%).
An extensive pre-cleaning procedures was used for all sample train
glassware and sample containers. This cleaning procedure, which is outlined
in Table 8-1, was implemented to minimize the potential for sample
contamination with substances that could interfere with the dioxin/furan
analysis. A blank MM5 train that had been pre-cleaned using this procedure
(i.e., proof train blank) was recovered with acetone and methylene chloride
rinses according to the usual MM5 recovery procedure. The rinses and other
MM5 train components of the proof train blank (i.e., filter, XAD trap, and
impinger solution) were submitted to Troika for dioxin/furan analysis.
To minimize the potential for contamination in the field, all sample
train glassware was capped with foil prior to use. Sample train field
recovery was performed in an industrial hygiene laboratory at the host plant.
This laboratory was performing low-level metals analysis using nitric,
sulfuric, and hydrochloric acids. No organic solvents were in use. A blank
MM5 train that had been previously used and field-recovered at least once at
8-2
-------
Table 8-1. GLASSWARE PRECLEANING PROCEDURE
NOTE; USE DISPOSABLE GLOVES AND ADEQUATE VENTILATION
1. Soak all glassware 1n hot soapy water (AlconoxR) 50°C or higher.
2. Distil1ed/de1onized H20 rinse (X3).a
o
3. Chromerge rinse 1f glass, otherwise skip to 6.
4. High purity liquid chromatography grade H_0 rinse (X3).
5. Acetone rinse (X3)» (pesticide grade).
6. Methylene chloride rinse (X3), (pesticide grade).
7. Cap glassware with clean glass plugs or methylene chloride rinsed
aluminum foils.
a(X3) = three times.
8-3
-------
Site MET-A (i.e., field recovery train blank) was assembled and recovered
according to the usual HM5 recovery procedures. The rinses and other
components of the field recovery train blank (i.e., filter, XAD trap, and
impinger solution) were submitted to Troika for dioxin/furan analysis.
Analytical results for the proof train blank and field recovery train blank
are presented in section 8.3.1.3.
8.1.2 Procedural PC Activities/Manual Gas Sampling
Procedural QC activities during the manual gas sampling for dioxin/furan
and HC1 focused on:
visual equipment inspections,
*
utilization of sample train blanks,
ensuring the proper location and number of traverse points,
conducting pre-test and post-test sample train leak checks,
maintaining proper temperatures at the filter housing,
sorbent trap and impinger train,
maintaining isokinetic sampling rates, and
recording all data on Preformatted field data sheets.
Unusual circumstances noted while carrying out the procedural QC activities
are discussed below.
As noted earlier, the first test run, Run 01, (5/21/85) was aborted after
about 30 minutes of on-line sampling because the MM5 sample train filter
•housing was incorrectly assembled. Insufficient time and inclement weather
prohibited the sampling team from beginning another test run on 5/21/85. As a
result, two test runs (Runs 02 and 03) were performed on 5/22/85. The final
test run (Run.04) was performed on 5/23/85. Both the MM5/dioxin and MM5/HC1
sampling proceeded without incident during Runs 02, 03, and 04.
Results of the average isokinetics calculations for the three valid MM5
test runs are shown in Table 8-2. The QA objective of 100 +10 percent was met
for all test runs. Initial, final, and port change leak checks for the MM5
and HC1 sample trains also achieved the QA objectives for all test runs. The
leak check dataware noted on the MM5 field data sheets.
8-4
-------
TABLE 8-2. SUMMARY OF ISOKINETIC RESULTS FOR MM5 AND HC1 SAMPLING
AT SITE MET-A
Run
.... , .MM5 Outlet
Isokinetics Meets QC
Objective?
HC1 Outlet
Isokinetics Meets QC
Objective?
02
107.1
YES
97.5
YES
03
102.2
YES
104.8
YES
04
105.7
YES
103.2
YES
The quality assurance objective for MM5 and HC1 sampling was isokinetics of
100 +10 percent.
8-5
-------
8.1.3 Sample Custody
Sample custody procedures used during this program emphasized careful
documentation of the samples collected and the use of chain-of-custody records
for samples transported to the laboratory for analysis. Steps taken to
identify and document samples collected included labeling each sample with a
unique alphanumeric code and logging the sample in a master logbook. All
samples shipped to Troika or returned to Radian-RTP were also logged on
chain-of-custody records that were signed by the field sample custodian upon
shipment and also signed upon receipt at the laboratory. Each sample
container lid was individually sealed to ensure that samples were not tampered
with. No evidence of loss of sample integrity was reported for samples
collected at this site.
8.2 CONTINUOUS MONITORING/MOLECULAR WEIGHT DETERMINATION
Flue gas concentrations measured continuously at the stack breeching
location included 02, CO, C02, THC, NOX, and SOg. Concentrations of 02,
C02and N2 were also determined for integrated bag samples of the flue gas.
Quality control results for these analyses are discussed in this section.
Drift check results for the continuously monitored flue gas parameters
are summarized in Table 8-3. Data reduction was performed by assuming a
linear drift of the instrument response over the test day based on drift
checks at the beginning and end of the day. The drift check results met the
QC criteria of ±10 percent daily drift for all species except for S02, which
showed nearly 32 percent drift during Run 04.
The quality control gases for this program consisted of mid-range
concentration standards different than those used for daily calibration. The
QC gases were analyzed immediately after calibration each day to provide data
on instrument variability. The acceptance criteria for the analysis of each
QC standard was agreement within -+/-10 percent (%) of the running mean value.
Since there were only two test days, this consisted of a comparison of QC
output data from 5/22/85 (Runs 02, 03) and 5/23/85 (Run 04). The QC output
data for 02, CO, C02, NOX, and THC each agreed within less than 4 percent,
8-6
-------
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8-7
-------
thus achieving the QC objective. There is no QC output data for S02 because
the S02 gas cylinder originally intended for QC purposes was used for
instrument calibration.
8.3 LABORATORY ANALYSES
QA/QC activities were carried out for dioxin/furan, precursor, and total
chloride analyses performed on Site MET-A samples. The dioxin/furan analyses
of MM5 train samples, baghouse dust samples and ambient XAD train samples
performed by Troika are considered in Section 8.3.1; the precursor analyses of
cupola furnace feed samples performed by Radian/RTP are considered in Section
8.3.2; and the total chloride analyses of HC1 train samples performed by
Radian/Austin are considered in Section 8.3.3.
8.3.1 Dioxin/Furan Analyses
Three individual topics related to the dioxin/furan analyses at Site
MET-A are discussed >n this section. The contribution of the back-up XAD trap
to the train-total MM5 dioxin/furan catch is presented in Section 8.3.1.1.
Analytical recoveries of labeled surrogate compounds spiked onto MM5 train
samples, baghouse dust samples, and ambient XAD train samples prior to
extraction are reported in Section 8.3.1.2. Sample blank data are reported in
Section 8.3.1.3.
8.3.1.1 Back-Up XAD Trap Data
As noted in Section 6.1.2.1, a back-up XAD trap was added to the MM5
trains used at Site MET-A (See Figure 6-3). The back-up traps were analyzed
separately from the "primary" MM5 train samples. Table 8-4 summarizes the
contribution of the back-up XAD trap to the total amount of each dioxin and
furan species measured on the entire train (i.e., primary MM5 train plus
back-up XAD trap). In general, the back-up XAD trap accounted for a fairly
small portion of the train-total catch. As a rule, the higher the degree of
chlorination for both dioxin and furan species, the lower was the amount of
8-8
-------
TABLE 8-4. PERCENTAGE CONTRIBUTION OF BACK-UP XAD MODULE TO
TOTAL MM5 TRAIN CATCH OF DIOXIN/FURAN HOMOLOGUES
Range of Back-up XAD
Isomer/Homologue Module Percentage Contribution
to Total MM5 Train Catcha
Dioxins
2378 TCDD
Other TCDD
Penta CDD
Hexa CDD
Hepta CDD
Octa CDD
0 '
0.5
0
0
0
0.03
- 0.8
-13.5
- 1.9
- 0.4
- 0.2
-0.1
Furans
2378 TCDF
Other TCDF
Penta CDF
Hexa CDF
Hepta CDF
Octa CDF
0.3
1.1
0.1
0
0
0
- 3.2
-11.5
- 1.8
- 0.6
- 0.5
- 0.3
a. Run 02 showed the highest percentage back-up XAD module contribution for
all isomers/homologues except Octa CDD. Run 04 showed the highest
percentage back-up XAD contribution for Octa CDD.
8-9
-------
the species that escaped capture by the first XAD trap. The maximum
percentage contributions of the back-up trap to the train-total catch ranged
from 0.1 percent for the octa-CDDs to 13.5 percent for other-TCDDs.
8.3.1.2 Surrogate Recoveries of the Test Samples
Table 8-5 presents the analytical recovery data reported by Troika for
four isotopically labeled surrogate compounds spiked onto the primary MM5
train samples, back-up XAD trap samples, baghouse dust, and ambient XAD train
samples. Those samples consisting solely of solid components (i.e., back-up
XAD traps, baghouse dusts, and ambient train XAD. traps) were spiked with the
13 13
C12"TCDD and Ci2~0cta CDD surrogates. Samples consisting solely of liquid
components (i.e., the aqueous portion of the ambient train samples) were
spiked with the 37C14~TCDD and 37Cl4-Hepta CDD surrogates. Samples that
consisted of both solid and liquid components (i.e., the primary MM5 train
samples) were spiked with all four of the surrogates.
Surrogate recoveries for the back-up XAD trap samples, baghouse dust
samples, and ambient XAD train samples were all within the target ranges of 50
to 120 percent for the"labeled TCDDs and 40 to 120 percent for the labeled
hepta- and octa- CDDs. Recoveries for the primary MM5 train samples could not
be determined for all four surrogate compounds because of the relatively large
quantities of native CDD and CDF species present in the samples. Since no
measure of extraction method efficiency is available for the MM5 samples, it
should be noted that the reported analytical results for native compounds may
actually represent lower bounds on the true values.
8.3.1.3 Sample Blanks
Table 8-6 summarizes the analytical results reported by Troika for
internal laboratory blanks, laboratory fortified quality control (QC) samples,
proof blank MM5 train samples, and field recovery blank MM5 train samples. In
general, the data show good surrogate recoveries, with values ranging from 80
to 100 percent. Comparison of the measured and spiked values for the
8-10
-------
TABLE 8-5. PERCENT SURROGATE RECOVERIES FOR
SITE MET-A DIOXIN/FURAN ANALYSES
37ci,
4
Sampl e TCDD
MM5 Train Samples
Run 02 Primary MM5 NR
Run 02 Back-up XAD
Run 03 Primary MM5 NR
Run 03 Back-up XAD
Run 04 Primary MM5 NR
Run 04 Back-up XAD
Baqhouse Dust Samples
Run 02 #1 BH Dust
Run 02 #2 BH Dust
Run 03 #1 BH Dust
Run 03 #2 BH Dust
Run 04 #1 BH Dust
Run 04 #2 BH Dust
13C
12
TCDD
NR
96
120
96
NR
94
100
102
104
90
96
68
37ci, 13c
4 L12
Hepta-CDD Octa CDD
NR NR
82
NR 58
93
NR 33
87
73
56
63
64
64
45
Ambient XAD Train Samples
Ambient XAD • 86 - 87
Ambient Aqueous 88 - H2
Note: NR indicates that surrogate recovery data were not reported for
this compound. In some cases, valid surrogate recoveries could not be
determined for the primary MM5 train because of the large amounts of
native CDDs and CDFs present in the samples.
Dash (-) indicates that the surrogate compound of interest was not
spiked onto this sample.
8-11
-------
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8-12
-------
laboratory fortified QC samples showed agreement to within +30 percent for all
target species except the 2378 TCDF isomer. The measured values for the 2378
TCDF isomer were about twice as high as the spiked values. Small but
detectable quantities of several dioxin and furan species were found in the
proof blank MM5 train samples, and detectable quantities of all targeted
dioxin and furan species were found in the field blank MM5 train. Table 8-7
gives a comparison of the dioxin/furan analytical results for the field blank
MM5 train and the test run MMS trains. In no case did the field blank value
correspond to more than 10 percent of the minimum test run value, which
indicates that there were no significant blanking problems at Site MET-A.
Thus, the field clean-up procedures were found to be adequate for this test
site. Emissions data reported in Section 5.4 are not blank-corrected.
8.3.2 Precursor Analyses
Table 8-8 presents analytical recovery efficiencies for six isotopically
labeled compounds used as surrogates for the target precursor analytes in the
Site MET-A feed samples. The surrogate recovery values in Table 8-8 vary
considerably by sample type and by specific surrogate species. The overall
ranges of surrogate recoveries for the different types of feed samples were: 7
to 84% for coke, 28 to 89% for telephone parts and wire, 0 to 15% for circuit
boards and 11 to 64% for electronic switching gear. These values are below
the 50 percent objective stated in the Tier 4 QA Project Plan and are below
those generally considered achievable when analyzing for similar compounds in
water or from MMS train components. There are no directly comparable
surrogate recovery values reported in the literature for samples similar to
the Site MET-A feed materials.
There are several reasons for the comparatively low surrogate recoveries
reported in the Tier 4 study for samples such as the Site MET-A circuit
boards. First, the complex nature of the samples required extensive clean-up
procedures prior to GC/MS analysis, which increased the potential for losses
of the surrogate compounds (and analytes) during sample preparation. Second,
large sample sizes (25 to 50 g) were required to increase method sensitivity
for the target analytes and to ensure that representative portions of the
8-13
-------
TABLE 8-7. FIELD BLANK DIOXIN/FURAN DATA
FOR SITE MET-A MM5 SAMPLES
Amount Detected, Nanograms per Train
Isomer/Homologue
Dioxins
2378 TCDD
Other TCDD
Penta CDD
Hexa CDD
Hepta CDD
Octa CDD
Furans
2378 TCDF
Other TCDF
Penta CDF
Hexa CDF
Hepta CDF
Octa CDF
Field
Blank
Value
0.1
2.0
0.3
7.5
7.3
6.3
2.6
29.2
21.0
40.0
16.1
43.1
Minimum
Test Run
Value
19
134
238
223
415
247
705
2380
2119
852
652
465
Percentage3
0.5
1.5
0.1
3.4
1.8
2.6
0.4
1.2
1.0
4.7
• 2.5
9.3
a. Percentage shown is the ratio of the field blank value to the minimum test
run value, expressed as a percentage.
8-14
-------
TABLE 8-8. PERCENT SURROGATE RECOVERIES FOR SITE MET-A FEED SAMPLES
Surrogate
Compound
o d4-dichlorobenzene
o bromobiphenyl
o2', 5, 5' tetra
bromobiphenyl
o d4-2-chlorophenol
Q 13C -pentachlorophenol
6
o dg-phenol
Feed
, Telephone
Coke* Parts, Wire
26, 31 51
80, 68 89
84, 78 67
49, 45 28
24, 7 72
22, 18 22
Materials
Circuit
Boards3
3, trace
5,1
3, ND
' 3, 2
14,15
ND, 1
Electronic
Switching
Gear
11
21
20
50
64
43
a. Duplicate analyses were run on the coke and circuit board samples.
8-15
-------
samples were analyzed. Due to the high cost of labeled surrogates, It was not
desirable to spike the large sample sizes with surrogates in proportion to
that normally used for smaller samples. Supplemental in-house laboratory
studies showed that when sample size was restricted to 1 g and the amount of
surrogate spiked was held fixed, surrogate recoveries improved and were
directly comparable to those reported in previous studies.1 Surrogate
recoveries for Tier 4 samples and the results for small sample sizes are
further discussed in the Tier 4 Engineering Analysis Report.
In spite of the relatively low surrogate recovery values for some of the
feed samples, the resulting analytical sensitivity for the target analytes was
considered acceptable for the purpose of this study. The instrumental
detection limit ranged from about 100 to 500 picograms on-column for the 1
micro!iter of final extract injected into the GC/MS. At a method recovery
efficiency of 100 percent for a 50 gram solid sample cleaned up to a final
extract volume of 1 mill 11iter, the overall analytical sensitivity would be
approximately 2 to 10 ppb in the solid sample. For samples such as the
circuit boards with surrogate recoveries as low as 1 percent, the overall
analytical sensitivity of the method would still be 200 to 1000 ppb, or 0.2 to
1.0 ppm. Thus, even in a worst-case situation the analytical procedures used
provide information on the precursor content of the feed samples down to the
ppm level.
8.3.3 Total Chloride Analysis
Total chloride analyses were performed by Radian/Austin on the HC1
train samples. QA/QC activities included total chloride analysis of field
recovery blank HC1 train samples, total chloride analysis of an aliquot of the
NaOH solution used in the sample train impingers, and duplicate total chloride
M.L. Taylor, T.O. Tiernan, J.H. Garrett, G.F. Van Ness, J.G. Solch.
Assessments of Incineration Processes as Sources of Supertoxic Chlorinated
Hydrocarbons: Concentrations of Polychlorinated Dibenzo-p-dioxins/Dibenzo-
furans and Possible Precursor Compounds in Incinerator Effluents in
Chlorinated Dioxins and Dibenzofurans in the Total Environment, G. Choudhary,
L.H. Keith, and C. Rappe, eds., Butterworth Publishers, Boston,
Massachusetts, 1983.
8-16
-------
analyses of two individual samples. Chlorides were not detected in either the
field recovery blank train samples or the aliquot of NaOH solution analyzed.
Duplicate ion chromatograph analyses of the probe rinse/filter fraction of the
HC1 train from Run 03 were in exact agreement. Duplicate analyses of the
impinger fraction of the HC1 train from Run 03 showed non-detectable leveJs of
total chlorides in both cases.
8-17
-------
-------
APPENDIX A
FIELD SAMPLING DATA
A-l Modified Method 5 and EPA Methods 1-4
Field Results
A-2 Continuous Emissions Monitoring Results
A-3 HC1 Train Results
A-4 Ambient XAD Train Results
A-5 Modified Method 5 Sample Calculations
-------
-------
APPENDIX A-l
Modified Method 5 and EPA Methods 1-4
Field Results
A-l
-------
-------
RADIAN SOURCE TEST
EPA METHOD 2-5
(RAW DATA)
PLANT DIOXIN SITE #10
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
BAGHOUSE EXHAUST
10-MM5-02
5/22/85
0750-1240
PARAMETER
VALUE
Sampling time (min.) 240
Barometric Pressure (in.Hg) 29.87
Sampling nozzle diameter (in.) .183
Meter Volume (cu.ft.) 137.566
Meter Pressure (in.H20) .95
Meter Temperature (F) 82.15
Stack dimension (sq.in.) 14957.16
Stack Static Pressure (in.H20) -.26
Stack Moisture Collected (gm) 195.1
Absolute stack pressure(in Hg) 29.85088
Average stack temperature (F) 214
Percent C02 1.98
Percent 02 20.4
Percent N2 77.6
Delps Subroutine result 26.352
DGM Factor .9978
Pitot Constant .84
A-3
-------
IAN
RAD
EPA
FINAL
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
SOURCE TEST
METHODS 2-5
RESULTS
DIOXIN SITE #10
BAGHOUSE EXHAUST
10-MM5-02
5/22/85
0750-1240
PARAMETER
RESULT
Vm(dscf)
Vm(dscm)
Vw gas(scf)
Vw gas (sera)
% moisture
Md
MWd
MW
Vs(fpm)
Vs (mpm)
Flow(acfm)
Flow(acmm)
Flow(dscfm)
Flow(dscmm)
Z I
Z EA
133 .7695
3.788352
9.198965
.2605147
6.434263
.9356573
29.1272
28.41125
3898.842
1188.671
404969.5
11468.74
296148
8386.91
107 .0902
23611 .36
Program Revision:I/16/84
A-4
-------
RADIAN SOURCE
EPA METHOD 2 -
( R A W DATA)
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
TEST
DIOXIN SITE #10
BAGHOUSE EXHAUST
10-MM5-03
5/22/85
1440-1910
PARAMETER
VALUE
Sampling time (min.) 240
Barometric Pressure (in.Hg) 29.87
Sampling nozzle diameter (in.) .184
Meter Volume (cu.ft.) 140.937
Meter Pressure (in.H20) 1.02
Meter Temperature (F) 95.2
Stack dimension (sq.in.) 14957.16
Stack Static Pressure (in.H20) -.26
Stack Moisture Collected (gm) 190.4
Absolute stack pressure(in Hg) 29.85088
Average stack temperature (F) 221.5
Percent C02 1.78
Percent 02 20.4
Percent N2 77.8
Delps Subroutine result 27.5893
DGM Factor .9978
Pitot Constant .84
A-5
-------
TEST
5
DIOXIN SITE #10
RADIAN SOURCE
EPA METHODS 2 -
FINAL RESULTS
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
BAGHOUSE EXHAUST
10-MM5-03
5/22/85
1440-1910
PARAMETER
RESULT
VmCdscf)
Vm(dscm)
Vw gas(scf)
Vw gas (scm)
% moisture
Md
MWd
MW
Vs(fpm)
Vs (mpm)
Flow(acfm)
Flow(acmm)
Flow(dscfm)
Flow(dscmm)
Z I
Z EA
133.8492
3.790609
8.97736
.2542388
6.285499
.937145
29.0952
28.39781
4082.87
1244.777
424084.3
12010.07
307201
8699.932
102.1788
14655.15
Program Revision:I/16/84
A-6
-------
RADIAN SOURCE
EPA METHOD 2 -
W
TEST
DAT
( R A
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
A )
DIOXIN SITE #10
BAGHOUSE EXHAUST
10-MM5-04
05/23/85
1215-1646
PARAMETER
VALUE
Sampling time (min.) 240
Barometric Pressure (in.Hg) 29.87
Sampling nozzle diameter (in.) .175
Meter Volume (cu.ft.) 120.014
Meter Pressure (in.H20) .72
Meter Temperature (F) 82.1
Stack dimension (sq.in.) 14957.16
Stack Static Pressure (in.H20) -.26
Stack Moisture Collected (gm) 167.6
Absolute stack pressure(in Hg) 29.85088
Average stack temperature (F) 213.4
Percent C02 1.48 •
Percent 02 20.7
Percent N2 77.8
Delps Subroutine result 25.3921
DGM Factor .9978
Pitot Constant .84
A-7
-------
RADIAN
SOURCE
TEST
— c
EPA METHODS 2
FINAL RESULTS
DIOXIN.SITE #10
PLANT
PLANT SITE
SAMPLING LOCATION
TEST f
DATE
TEST PERIOD
BAGHOUSE EXHAUST
10-MM5-Q4
05/23/85
1215-1646
PARAMETER
RESULT
Vm(dscf)
Vm(dscm)
Vw gas(scf)
Vw gas (scm)
% moisture
Md
MWd
MW
Vs(fpm)
Vs (mpm)
Flow(acfm)
Flow(acmm)
Flow(dscfm)
Flow(dscmm)
% I
% EA
116.6468
3.303436
7.902341
.2237943
6.34476
.9365524
29.0592
28.35752
3760.38
1146.457
390587 .6
11061 .44
286158.7
8104.013
105.6801
-12873.06
Program Revision:I/16/84
A-8
-------
APPENDIX A-2
Continuous Emissions Monitoring Results
A-9
-------
-------
CEMS DATA - SITE 10 - TEST 2
:ME
=====
750
755
81210
SOS
810
815
320
825
830
335
840
845
850
855
900
905
910
913
920
925
930
935
940
945
955
1000
1005
1010
1015
1132(3
1025
1030
1035
1040
1045
1050
1055
1100
1105
1110 •
1113
1120
1125
1130
1135
1140
1145
1150
02
C/.V)
3==;==;==
21. 1
20. 1
19.9
21. 1
19.9
20.0
20.9
19.8
20.0
21. 1
20.1
20.2
21.0
20.0
20.2
21.0
20.0
19.8
20.3 •
19.9
19.9
21. 1
19.8
19.7
19.7
19.9
21.0
19.8
19.8
20.9
19.9
20. 1
21.2
20.0
19.9
21. 1
19.9
19.9
21. 1
19.7
19.7
20.9
19.5
19.4
21.2
19.6
19.6
21.0
CO
(PPMV)
=:—===:==:
1302.6
455.3
1564.3
654.8
766.2
3035.6
904.2
373.1
2377. 1
309.7
2066.4
1210.0
430.6
913.7
1025.8
53.0
3575. 1
191.6
1430.9
580.5
1088.7
1190.6
635. 9
3713.4
2256.3
3409.9
136.1
1257.0
1139. 1
393.0
1447.0
110.7
2512.4
1684.7
1248. 1
3254. 1
1663.9
3718.0
1853.8
497.6
2987.2
551.2
530.4
1439.3
557.3
198.4
1649.8
712.3
C02
<7.V>
1.5
1.8
1.6
1.8
1.7
1.7
1.8
1.8
1.7
1.8
1.5
1.7
1.7
1.6
1.6
1.6
1.5
1.6
1.7
1.3
1.3
1.3
1.9
1.6
1.3
1.9
1.9
1.9
1.8
1.3
1.6
1.5
1.6
1.6
1.7
1.3
1.8
1.7
2.0
2. 1
2.0
1.9
2. 1
2.0
2.0
2.0
2. 1
2.0
502
(PPMV)
182.7
221.7 •
236.6
239.4
304.0
336.3
284.3
255.8
252.7
200.5
181.3
201.2
178.1
158.8
182.8
150.4
209.2
185.5
141.7
172.7
206.2
193.5
206.5
226.4
173.7
208.8
146. 1
146.9
149.6
151. 1
135.3
117.8
154.4
186.2
224.3
240.5
225.7
180.8
165.9
178.3
195.7
139-. 4
139.5
147.5
174.3
137.3
137, 1
185.9
NOX
-------
GEMS DATA - SITE 10 - TEST 3
TIME
1440
1445
1430
1455
1500
1305
1510
1515
1320
1525
1530
1535
1540
1545
1550
1555
1600
1605
1610
1615
1620
1625
1630
1635
1640
1645
1650
1655
• 1700
1705
1710
1715
1720
1725
1730
1735
1740
1745
1750
1755
1830
1S05
1810
1815
1820
1825
1830
1835
02
C/.V)
21.3
19.9
20.0
19.7
20.1
19.8
19.9
19.7
19.9
19.6
19.7
19.9
20.3
19.9
19.9
19.7
19.8
19.9
20.0
20.1
20.0
20.0
20.0
20.0
20.5
20.2
20.2
20.0
20.3
20.0
20.0
19.5
19.6
19.8
19.9
20.0
20.5
20. 0
19.8
20. 1
20.0
20.1
20.1
20.2
20.4
20.3
20.3
20.4
CO
(PPMV)
683.9
463.4
3547.8
848.9
1856.8
1447.8
2938.3
369.4
487.2
146.8
1211.3
905.7
702.4
995.8
1177.8
587.4
2450.6
795. 1
3626.2
1499.8
1289.4
1868.4
915.5
1073.2
927.4
204.3
594.0
453.0
2227. 1
427.5
3072. 9
292. 1
1048.2
426.9
98.9
346.9
24.5
146.7
55.7
92.5
51. 1
100.2
36.4
164.3
136.4
243.9
337. 2
1436.7
C02
C7.V)
1.7
1.7
1.4
1.6
1.8
1.6
1.8
1.7
1.9
1.8
l.S
1.5
1.7
1.8
1.7
1.8
1.7
1.6
1.5
1.7
1.3
1.6
1.6
1.6
1.5
1.5
1.7
1.6
1.6
1.8
1.7
2. 1
1.9
1.6
l.S
1.9
1.7
1.8
1.8
1.6
i.a
1.6
1.6
1.5
1.5
l.S
1.5
1.5
S02
(PPMV)
150.2
188.5
188.4
144.5
163.2
159.0
139.0
126.0
90.6
115.5
130.1
91.3
95.3
169.8
196.9
148. 1
1S0.2
186.0
185.4
154.1
115.4
174.9
159.9
179.0
120.2
115.2
174.3
147.1
211.6
278.4
309. 1
323. 3
345. 5
265.2
260. 1
283.5
205.9
215.2
184.8
130.3
136.7
163.6
161.5
151.8
155.0
198.7
200.4
193.5
NOX
(PPMV)
33.4
34. a
25.7
44.4
35. I
26.7
36.3
42. 1
29. 1
35. 21
30.9
35. 1
46.9
34.7
32.3
43.2
32. 8
48.2
23. 1
43.3
27.2
32. 9
52.5
42.4
56.3
43.6
33.2
46.9
24. 1
45.9
28.4
59.8
36.8
42. 1
30. 1
33. 1
57. 1
33.2
42.9
36.9
65.3
48.5
34.7
54. 1
53. a
37.6
42.6
47.3
THC
(PPMV)
7. 1
5. 7
43.0
g. 7
19. 5
16.9
41. 9
7.8
6.5
4.8
10.3
12. 1
5.8
7.8
11.2
3.5
31.5
12.5
44. 4
30.3
18. 4
26.6
11.8
16.2
21.2
7.3
8. 8
5.8
28.5
7.2
42.6
10. 1
a. 4
8.5
4. 1
4. 5
4.0
4. 2
2.8
2.9
2.9
3.3
2.4
3. 6
3. 3
3. 7
3.3
13.7
CEMS DATA - SITE 10 - TEST 3
1S40
1845
1850
1855
1900
1905
1910
1915
1920
NO. PTS.
MEAN
STD. DEV.
20.6
20.2
20.2
20.3
20.2
20.5
20.4
20.3
21.2
57
20. 1
0.3
251.3
206.4
111.5
166.2
135.5
291.3
851.5
371.8
56
843.6
390.3
1.4
1.6
1.6
1.5
1.5
1.4
1.5
1.6
56
1.6
0.2
149.8
180.0
151.6
114.3
142.6
160. a
163.5
185.0
56
175.6
34.7
36.9
43.6
42.5
42.4
49.1
37.5
42.7
52.4
36
40.9
9.4
4.6
4.2
3.2
2.8
3.6
5.7
11.2
8.2
36
11.7
11.2
A-12
-------
CEMS DATA - SITE 10 - TEST 4
TIME
1215
12213
1225
1230
1235
1240
J245
125B
1255
1300
1305
1310
1315
1320
1325
1330
1335
1340
1345
1350
1355
1400
1405
1410
1415
1420
1425
1430
1435
1440
1445
1450
1455
1500
1505
1510
1515
1520
1325
1530
1535
1540
1545
1550
1555
1600
1605
1610
02
C/.V)
20.5
20.3
20.2
21. 1
20.3
20.2
21.1
20.0
20. 1
21.2
20.0
19.8
20.5
19.8
19. 3
21.2
19.6
20.0
21. 1
19.8
19. 8
21.1
19.9
19.8
20.5
' 19.8
19.8
21.2
19.3
19.4
21.1
19.5
19.5
21.1
19.4
19.4
20.4
19.8
19.6
21. 1
19.5
19.7
21.0
19.7
19.8
21. 1
CO
6BS.7
1206.0
1303.4
1348.2
2073.4
1729.9
2030.3
1616.4
1438.2
1231.4
2664.2
2099. 4
3425.0
2530. 2
723.8
2521.2
866.3
2118.3
1091.4
2683.9
2478.0
624.7
1154.7
2885.9
1435.7
3631.5
2568.8
1499.5
3072.2
843.0
376.6
1854.0
566.8
131.9
534.9
1811.0
1006.5
729.4
1536.7
S54.5
821.6
646.8
1276.4
443.3
295.1
620.7
1887.3
1484. 1
C02
1.5
1.5
1.5
1.4
1.4
1.5
1.5
1.6
1.4
1.7
1.7
1.7
1.7
1.8
1.8
1.8
2.0
1.8
2.0
1.8
1.9
2. 1
2.0
1.9
2.0
2.0
2.2
. 2.0
2.0
2.2
2.3
2. 2
2.0
2. 1
2.0
2.2
1.9
2.0
2.0
2.0
2. 1
1.9
1.6
2.0
2.0
1.3
2.0
2.0
S02
(PPMV)
213.4
231.1
282.7
233.9
225.2
254.0
235.0
248.2
226.0
266.9
275.2
276.9
241.9
292.2
257.1
245.0
250.5
206. 1
229.9
252.0
319. 1
309. 1
234.2
219.4
217.4
243.4
298.2
165.3
226.8
275.9
270.0
309.0
260.1
147.0
168.7
198.3
121. 1
135.9
'"•''"* A "*"
301. 1
326.2
253.6
207. 1
250.8
201.6
177.4
335.5
305.3
NOX
(PPMV)
39.7
46.7
49.6
36.5
35.6
46.3
34.9
39.0
32. 1
34.2
28.5
33.9
26.8
45. 1
43.5 ,
38.3
42.4
38.4
44.0
36.6
43.2
45.4
44. 1
34.2
27.2
23.6
28.3
30.4
23.8
27.8
33.7
28.6
28.4
28.2
30.5
30.9
-29.7
37.3
-0.9
33.6
34.5
34. 6
26.6
31.7
32.7
29.5
31.2
35.7
THC
8. 1
12.5
20. 1
19.4
28.5
24. 4
19.7
29.9
24.7
19.9
31.5
27.7
41.3
36.4
9.6
27.6
16. 9
18.7
16.0
27.0
27.8
5.9
13. 1
30. 1
16.5
35.2
32.5
21.9
48.3
14. 4
4. 1
14.2
6. 3
3.4
2.8
19.9
4.8
4.3
16. 1
6.2
6.7
4.5
15. 1
3. 4
3.0
27.4
12. 1
CEMS DATA - SITE 10 - TEST 4
1615
1620
1625
1630
1635
1640
1645
1650
NO. PTS.
MEAN
STD. DEV.
19.7
19.7
20.4
19.3
19.8
21.1
19.5
19.9
54
20.2
0.6
714.1
1633.9
753.5
1662.7
436.0
3266.5
=======»=
54
1499.7
871.3
1.3
1.9
2.0
1.9
2. 1
1.9
54
1.9
0.2
172.9
253.0
223.0
234.4
189.9
189.3
54
239.5
47.5
33. 1
32.7
34.5
42.4
34.5
30. 1
54
34.8
6. 1
9.7
23.0
3.8
51.5
10.3
26.2
54
18.5
11.9
A-13
-------
-------
APPENDIX A-3
HC1 Train Results
A-15
-------
-------
RADIAN SOURCE TEST
EPA METHOD 2-5
(RAW DATA)
PLANT DIOXIN SITE #10
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
BAGHOUSE EXHAUST
10-HCL-02
5/22/85
0753-0953
PARAMETER
VALUE
Sampling time (min.) 120
Barometric Pressure (in.Hg) 29.87
Sampling nozzle diameter (in.) .189
Meter Volume (cu.ft.) 61.288
Meter Pressure (in.H20) .8
Meter Temperature (F) 81
Stack dimension (sq.in.) 14957.16
Stack Static Pressure (in.H20) -.26
Stack Moisture Collected (gm) 91.6
Absolute stack pressure(in Hg) 29.85088
Average stack temperature (F) 207.4
Percent C02 1.98
Percent 02 •• 20 .4
Percent N2 77.6
Delps Subroutine result 24.2253
DGM Factor 1 .0053
Pitot Constant .84
A-17
-------
DIOXIN SITE #10
RADIAN SOURCE
EPA METHODS 2 -
FINAL RESULTS
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
T E
5
S T
BAGHOUSE EXHAUST
10-HCL-02
5/22/85
0753-0953
PARAMETER
RESULT
Vm(dscf)
Vm(dscm)
Vw gas(scf)
Vw gas (scm)
% moisture
Md
MWd
MW
Vs(fpm)
Vs (mpm)
Flow(acfm)
Flow(acmm)
•Flow(dscfm)
Flow(dscmm)
Z I
% EA
60.15003
1.703449
4.31894
.1223124
6.699254
.9330074
29.1272
28.38176
3586.054
1093.309
372480.5
10548.65
274303.9
7768.285
97.47961
23611 .36
Program Revision:I/16/84
A-18
-------
RADIAN SOURCE
EPA METHOD 2 -
( R A W DATA)
TEST
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
DIOXIN SITE #10
BAGHOUSE EXHAUST
10-HCL-03
05/22/85
1452-1652
PARAMETER
VALUE
Sampling time (min.) 120
Barometric Pressure (in.Hg) 29.87
Sampling nozzle diameter (in.) .185
Meter Volume (cu.ft.) 62.935
Meter Pressure (in.H20) .78
Meter Temperature (F) 104.2
Stack dimension (sq.in.) 14957.16
Stack Static Pressure (in.H20) -.26
Stack Moisture Collected (gm) 87.7
Absolute stack pressure(in Hg) 29.85088
Average stack temperature (F) 220.7
Percent C02 1.78
Percent 02 20.4
Percent N2 77.8
Delps Subroutine result 23.5768
DGM Factor 1 .0053
Pitot Constant .84
A-19
-------
RADIAN SOURCE
EPA METHODS 2 -
FINAL RESULTS
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
TEST
5
DIOXIN SITE #10
BAGHOUSE EXHAUST
10-HCL-03
05/22/85
1452-1652
PARAMETER
RESULT
Vm(dscf)
Vm(dscm)
Vw gas(scf)
Vw gas (scm)
% moisture
Md
MWd
MW
Vs(fpm)
Vs (mpm)
Flow(acfm)
Flow(acmm)
Flow(dscfm)
Flow(dscmm)
% I
% EA
59.2237
1 .677215
4.135055
.1171048
6.526415
.9347359
29.0952
28.37108
3490.714
1064.242
362577.6
10268,2
262279.1
7427 .743
104.7663
146 5 5 ., 15
Program Revision:1/16/84
A-20
-------
RADIAN SOURCE
EPA METHOD 2 -
(RAW DATA)
TEST
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
DIOXIN SITE #10
BAGHOUSE EXHAUST
10-HCL-04
05/23/85
1218-1418
PARAMETER
VALUE
Sampling time (min.) 120
Barometric Pressure (in.Hg) 29.87
Sampling nozzle diameter (in.) .185
Meter Volume (cu.ft.) 58.644
Meter Pressure (in.H20) .73
Meter Temperature (F) 87.8
Stack dimension (sq.in.) 14957.16
Stack Static Pressure (in.H20) -.26
Stack Moisture Collected Cgm) 85.4
Absolute stack pressureCin Hg) 29.85088
Average stack temperature (F) 208.3
Percent C02 . 1.48
Percent 02 20.7
Percent N2 77.8
Delps Subroutine result . 22.5451
DGM Factor 1 .0053
Pitot Constant .84
A-21
-------
RADIAN SOURCE TEST
EPA METHODS 2-5
FINAL RESULTS
DIOXIN SITE #10
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
BAGHOUSE EXHAUST
10-HCL-04
05/23/85
1218-1418
PARAMETER
RESULT
Vm(dscf)
Vm(dscm)
Vw gas(scf)
Vw gas (scm)
% moisture
Md
MWd
MW
Vs(fpm)
Vs (mpm)
Fl'ow(acfm)
Flow(acmm)
Flow(dscfm)
Flow(dscmm)
% I
% EA
56.83091
1.609451
4.02661
.1140336
6 .616455
.9338354
29.0592
28.32747
3340.53
1018.454
346978.1
9826.42
255405.7
7233.088
103 .2391
-12873.06
Program Revision:1/16/84
A-22
-------
APPENDIX A-4
Ambient XAD Train Results
A-23
-------
-------
RADIAN
EPA MET
(RAW DA
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
S (
H (
T t
) U R C E
) D 2 -
i )
DIOXIN S
AMBIENT
AMBIENT
05/21-23
(1350-13
TEST
5
ITE #10 -
SAMPLING LOCATION
"A" TRAIN
/85
52) (0755-1900) (1
235-1740)
PARAMETER
VALUE
Sampling time (min.)
Barometric Pressure (in.Hg)
Sampling nozzle diameter (in.)
Meter Volume (cu.ft.)
Meter Pressure (in.H20)
Meter Temperature (F)
Stack dimension (sq.in.)
Stack Static Pressure (in.H20)
Stack Moisture Collected (gin)
Absolute stack pressure(in Hg)
Average stack temperature (F)
Percent C02
Percent 02
Percent N2
Delps Subroutine result
DGM Factor
Pitot Constant
972
30
0
496
.85
116.4
0
0
65.5
30
0
.001
21
79
0
1 .003
0
45
A-25
-------
RADIAN SOURCE
EPA METHODS 2
FINAL RESULTS
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
TEST
- 5
DIOXIN SITE #10
AMBIENT SAMPLING LOCATION
AMBIENT "A" TRAIN
05/21-23/85
(1350-1352) (0755-1900) (1235-1740)
PARAMETER
RESULT
Vm(dscf)
Vm(dscm)
Vw gas(scf)
Vw gas (scm)
Z moisture
Md
MWd
MW
Vs(fpm)
Vs (mpm)
Flow(acfm)
Flow(acmm)
Flow(dscfm)
Flow(dscmm)
Z I
% EA
458.3001
12.97906
3.088325
8.746136E-02
.6693547
.9933064
28.84044
28.76788
0
0
0
0
0
0
0
0
Program Revision:I/16/84
A-26
-------
RADIAN SOURCE
EPA METHOD 2-5
(RAW DATA)
TEST
PLANT
-PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
DIOXIN SITE #10
AMBIENT SAMPLING LOCATION
AMBIENT "B" TRAIN
05/21-23/85
(1345-1350) (0800-1900) (1238-1740)
PARAMETER
VALUE
Sampling time (min.)
Barometric Pressure (in.Hg)
Sampling nozzle diameter (in.)
Meter Volume (cu.ft.)
Meter Pressure (in.H20)
Meter Temperature (F)
Stack dimension (sq.in.)
Stack Static Pressure (in.H20)
Stack Moisture Collected (gm)
Absolute stack pressureCin Hg)
Average stack temperature (F)
Percent C02
Percent 02
Percent N2
Delps Subroutine result
DGM Factor
Pitot Constant
967
30
0
508
.85
109.2
0
0
63.7
30
0
.001
21
79
0
1 .004
0
53
A-27
-------
TEST
5
.DIOXIN SITE #10
RADIAN SOURCE
EPA METHODS 2 -
FINAL RESULTS
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
AMBIENT SAMPLING LOCATION
AMBIENT "B" TRAIN
05/21-23/85
(1345-1350) (0800-1900) (1238-1740)
PARAMETER
RESULT
Vm(dscf)
Vm(dscm)
Vw gas(scf)
Vw gas (scm)
Z moisture
Md
MWd
MW
Vs(fpm)
Vs (mpm)
Flow(acfm)
Flow(acmm)
Flow(dscfm)
Flow(dscmm)
Z I
Z EA
475.8639
13.47647
3.003455
8.505785E-02
.6271998
.9937281
28.84044
28.77245
0
0
0
0
0
0
0
0
Program Revision:1/16/84
A-28
-------
RADIAN SOURCE TEST
EPA METHOD 2-5
SAMPLE CALCULATION
PLANT
PLANT SITE
SAMPLING LOCATION
TEST #
DATE
TEST PERIOD
DIOXIN SITE #10
AMBIENT SAMPLING LOCATION
AMBIENT "B" TRAIN
05/21-23/85
(1345-1350) (0800-1900) (1238-1740)
1) Volume of dry gas sampled at standard conditions (68 deg-F ,29.92 in. Hg)
Y x Vm x [T(std) + 460] x [Pb +(Pm/13.6)]
Vm(std) =
P(std) x (Tm + 460)
1.004 x 508.53 x 528 x [ 30 + ( .85 /13.6)]
Vm(std) =
29.92 x ( 109.2 + 460)
Vm(std) = 475.864dscf
2) Volume of water vapor at standard conditions:
Vw(gas) = 0.04715 cf/gm x W(l) gm
Vw(gas) » 0.04715 x 63.7 = 3.003 scf
3) Percent Moisture in stack gas :
100 x Vw(gas)
%M = .
Vm(std) + Vw(gas)
100 x 3 .003
%M = » 0.63 %
475.864 + 3.003
4) Mole fraction of dry stack gas :
100 - %M 100 - 0.63
Md = = = .9937281
100 100
A-29
-------
-------
APPENDIX A-5
Modified Method 5 Sample Calculations
A-31
-------
-------
PARAMETER
RADIAN SOURCE TES-T
EPA METHODS 2-5
DEFINITION OF TERMS
DEFINITION
Tt(min.)
Dn(in .)
Ps(in.H20)
Vm(cu.ft .)
VwCgm.)
Pm(in.H20)
Tm(F)
Pbdn.Hg.)
% C02
% 02
% N2
SQR(DELPS)
As(sq.in . )
Ts(F)
Vm(dscf)
Vm(dscm)
Vw gas(scf)
% moisture
Md
MWd
MW
Vs(fpm)
Flow(acfm)
Flow(acmm)
Flow(dscfm)
Flow(dsc mm)
% I
% EA
DGM
Y
Pg
Cp
dH
dP
*** EPA
STANDARD
CONDITIONS
TOTAL SAMPLING TIME
SAMPLING NOZZLE DIAMETER
ABSOLUTE STACK STATIC GAS PRESSURE
ABSOLUTE VOLUME OF GAS SAMPLE MEASURED BY DGM
TOTAL STACK MOISTURE COLLECTED
AVERAGE STATIC PRESSURE OF DGM
AVERAGE TEMPERATURE OF DGM
BAROMETRIC PRESSURE
CARBON DIOXIDE CONTENT OF STACK GAS
OXYGEN CONTENT OF STACK GAS
NITROGEN CONTENT OF STACK GAS
AVE. SQ. ROOT OF S-PITOT DIFF . PRESSURE-TEMP. PRODUCTS
CROSS-SECTIONAL AREA OF STACK(DUCT)
TEMPERATURE OF STACK
STANDARD VOLUME OF GAS SAMPLED ,Vm(std),AS DRY STD. CF
STANDARD VOLUME OF GAS SAMPLED,Vm(std),AS DRY STD. CM
VOLUME OF WATER VAPOR IN GAS SAMPLE,STD
WATER VAPOR COMPOSITION OF STACK GAS
PROPORTION, BY VOLUME,OF DRY GAS IN GAS SAMPLE'
MOLECULAR WEIGHT OF STACK GAS,DRY BASIS LB/LB-MOLE
MOLECULAR WEIGHT OF STACK GAS,WET BASIC LB/LB-MOLE
AVERAGE STACK GAS VELOCITY
AVERAGE STACK GAS FLOW RATE(ACTUAL STACK COND.)
AVERAGE STACK GAS FLOW RATE(ACTUAL STACK COND.)
AVERAGE STACK GAS VOLUMETRIC FLOW RATE(DRY BASIS)
AVERAGE STACK GAS VOLUMETRIC FLOW RATE(DRY BASIS)
PERCENT ISOKINETIC
PERCENT EXCESS AIR IN STACK GAS
DRY GAS METER
DRY GAS METER CORRECTION FACTOR
STACK STATIC GAS PRESSURE
PITOT COEFFICIENT
ORIFICE PLATE DIFF. PRESS. VALUE
PITOT DIFF. PRESS. VALUE
Temperature = 68 deg-F (528 deg-R)
Pressure « 29.92 in. Hg.
A-33
-------
RADIAN SOURCE TEST
EPA METHOD 2-5
SAMPLE CALCULATION
PLANT
PLANT SITE
SAMPLING LOCATION
TEST f
DATE"
TEST PERIOD
DIOXIN SITE #10
BAGHOUSE EXHAUST
10-MM5-02
5/22/85
0750-1240
1) Volume of dry gas sampled at standard conditions (68 deg-F ,29.92 in. Hg)
Y x Vm x [T(std) + 460] x [Pb +(Pm/13.6)]
Vm(std) *
P(std) x (Tm + 460)
.9978 x 137.566 x 528 x [ 29.87 + ( .95 /13.6)]
Vm(std) * — _-__—____—„ ____„______ „
29.92 x ( 82.15 + 460)
Vm(std) - 133.769dscf
2) Volume of water vapor at standard conditions:
Vw(gas) - 0.04715 cf/gm x W(l) gm
Vw(gas) - 0.04715 x 195.1 = 9.199 scf
3) Percent Moisture in stack gas :
100 x Vw(gas)
ZM . „
Vm(std) ' + Vw(gas)
100 x 9.199
%M = 6.43 %
133.769 + 9.199
4) Mole fraction of dry stack gas :
100 - %M 100 - 6.43
Md * = 3 .9356573 "
100 100
A-34
-------
SAMPLE CALCULATION
PAGE TWO
5)Average Molecular Weight of DRY stack gas :
MWd = (.44 x %C02) + (.32 x %02) + (.28 x %N2)
MWd = (.44 x 1.98 ) + (.32 x 20.4 ) + (.28 x 77.6 ) - 29.1272
6)Average Molecular Weight of wet stack gas :
MW = MWd x Md + 18(1 - Md)
MW = 29.1272 x .9356573 + 18(1 - .9356573 ) = 28.41125
7) Stack gas velocity in f eet-per-minute (fpm) at stack conditions :
Vs = KpxCp x [SQRT (dP)]§avet x SQRT [Ts §avgt] x SQRT [l/(PsxMW)] x 60sec/min
Vs - 85.49 x .84 x 60 x 26.352 x SQRT[l/( 29.85088 X 28.41125 )]
Vs = 3898.842 FPM
8) Average stack gas dry volumetric flow rate (DSCFM) :
Vs x As x Md x T(std) x Ps
= --- - -------------------------------------
144 cu.in./cu.ft . x (Ts +460) x P(std)
3898.842 x 14957.16 x .9356573 x528x 29.85088
Qsd = --- .
144 x 674 x 29.92
Qsd = 296148 dscfm
A-35
-------
SAMPLE CALCULATION
PAGE THREE
9)Isokinetic sampling rate (%) :
Dimensional Constant C = K4 x 60 x 144 x [1 / (Pi /4)]
K4 - .0945 FOR ENGLISH UNITS
IZ
IZ
C x Vm(std) x (Ts + 460)
Vs x Tt x Ps x Md x (Dn)*2
1039.574 s 133.7695 x 674
3898.842 x 240 x 29.85088 x .9356573 x( .183 )°2
IZ - 107.0902
10) Excess air (Z) :
100 x Z02 100 x 20.4
EA « »
(.264 x ZN2) - Z02 (.264 x 77.6 ) - 20.4
EA = 23611.36
11) Particulate Concentration :
Cs » ( grams part.) / Vm(std) = 0 / 133.7695
Cs -
Ca -
Ca »
*
Ca -
LBS/HR
LBS/HR
LBS/HR
0.0000000 Grams/DSCF
T(std) x Md x Ps x Cs
P(std) x Ts
528 x .9356573 x 29.85088 x 0.0000000
29.92 x 674
0.0000000 Grams/ACF
Cs x 0.002205 x Qsd x 60
O.OOOOOOOx 0.002205 x296148.0 x 60
Program Revision:I/16/84
A-36
-------
APPENDIX B
Sample Shipment Letters
B-l
-------
-------
May 24, 1935
U.S. EPA ECC Toxicant Analysis Center
Building 11O5
Bay St. Louis, MS 39529
Attention: Danny McDaniel
f Subject: Tier 4 - Analysis Instructions
Dear Sir:
The objective o-f this letter is to clarify instructions and
priorities -for individual samples -from specific Tier 4 combustion sites.
This instruction letter is No. 12 and pertains to EPA Site No. 1O (MET-A) .
The Episode No. is 2646, and SCC numbers assianed to this site were
numbers DQOO2OOO through DQOO2O99.
SCC numbers DQOO2OO1 through DQOO20O6 have been assigned to Troika
•for QA/QC purposes- SCC numbers DQOO2OO7 through DQOO2O25 have been
assigned to samples included in this shipment. SCC numbers DQOO2O26
through DQOO2O2S have been assigned to samples being archived at Radian.
All remaining SCC numbers are unused.
The sample shipment for EPA Site No. 1O (MET-A) consists of 3 boxes
Containing 42 samples in 43 containers. The boxes were shipped under
Federal Express, Airbi-11 Nos. 769751765, 76^751776 and 7697517SO.
Instructions for extraction and analysis follow™
1. Priority 4*1 samples include the sample train components, the
baghouse dust, the lab proof blank, and the reagent blanks. These
samples require i_mmed_i ate.__ex tract i.on and analysis.
MM5 TRAIN SAMPLES
Radian Run # 1O-MM5-O1 was an aborted run with no samples.
Radian Run # 1O-MM5-O2 (Total of 6 train components)
iCQ._tlS-
DQOO20O8 1 Filter
DQ002008 2 Probe, Rinse
DQ002008 3 Back Half /Coil Rinse
DS002003 4 Condensate
DQ002008 5 Impinger Solution
DQ002003 6 XAD Module
B-3
-------
U. S. EPA ECC Toxicant Analysis Center
Paq© two
May 24, 1985
Radian Run # 1O-MM5-O3 (Total of 6 train components)
ECl.cti.on '
DQ002012 1 Filter
DQO02O12 ' 2 * Probe Rinse
DQ002012 3 Back Hal -f /Coil Rinse
DQ002012 4 Con den sate
DQOO2O12 5 Ifnpinger Solution
DQOO2O12 6 XAD Module
* indicates two containers
Radian Run # 1O-MM5-O4 (Total of 6 train components)
DQ002021 1 Filter
DQO02021" 2 Probe Rinse
DQ002021 3 Back Half /Coil Rinse
DQ002021 4 Condensate
DQOO2O21 5 Impinger Solution
DQ002021 6 XAD Module
Radian Run # 1O-MM5-FBL (Total of & train components)
DQOO2O23 1 Filter
DQ002023 2 Probe Rinse
DQO02023 3 . Back Half /Coil Rinse
DQOO2O23 4 Condensate
DQOO2O23 5 Tmpinqer Solution
DQOO2023 6 XAD Module
BACK UP XAD*
S£Q_N°- ' SAMPLE
DQOO2OO9 MM5 Run 1O-MM5-O2
DQOO2O13 MM5 Run 1O-MM5-O3
DQOO2O22 MM5 Run 1O-MM5-O4
DQOO2O16 Blank XAD
*Back up XAD used at Site 1C to verify organic collection.
AMBIENT XAD TRAIN
Radian Run 4* 1O-AMB-A (Total of 2 train components)
SCQ_No.
DQ002020 1 .XAD Module
DQOO2O2O 2 Probe Rinse
B-4
-------
U. S. EPA ECC Toxicant Analysis Center
Page three *.
May 24, 19S5
LABORATORY . PROOF BLANK
DQOO2OO7
DQOO2OO7
DQOO2OO7
i
2
Fraction
Filter
Probe Rinse,
Back Hal-F/Coil Rinse,
and Impi nger Solut i on
XAD Module
REAGENT BLANKS
e
Baghouse Dust, Run O2
Baghouse Dust, Run O3
Baghouse Dust, Run O4
DQOO2O17 HPLC grade water blank
DQOO2O18 Acetone blank
DQ002019. Methylene chloride blank
NO. 1 BAGHOUSE DUST
SCC._No.
DQOO2O1O
D13OO2014
DQOO2O24
NO. 2 BAGHOUSE DUST
IQQ...NO-
DQ002011 Baghouse Dust, Run O2
DQO02015 . Baghouse Dust, Run O3
DQ002025 - Baghouse Dust, Run O4
The priority #2 samples are the plastic bearing -Furnace -Feed samples
and the coke samples. These samples will be held at Radian -For
analysis pending the results o-F Priority #1 samples analysis.
COKE - PROCESS SAMPLE
SCC # DQOO2O2& Sample: composite o-F coke -For entire test.
B-5
-------
U. S. EPA ECC Toxicant Analysis Center
Paqe four
May 24, 1985
PLASTIC-BEARING FEED MATERIALS - PROCESS SAMPLE
SCC ^ DQOO2O28 Samples lO-Scrap
3. The soil sample is the only Priority #3 sample. It will be held at.
Radian for analysis pending the results of Priority #1 and Priority
#2 samples. The SCC number -for the soil sample is DQOO2O27.
"• " I
If any questions arise concerning this sample shipment, please
contact either Larry Keller or James McReynolds at Radian Corporation at
(919) 541-9100.
Sincerel y ,
TEST TEAM LEADER
ccs E. Hanks/EPA/AMTB
A. Miles/Radian
Radian Field File - RTP/PPK
B-6
-------
CORPORATION
November 11, 1985
U.S. EPA ECC Toxicant Analysts Center
Building 1105
Bay St. Louis, MS 39529
Attention: Danny McDanlel
Subject: Tier 4-Analysis Instructions
Dear Sir:
Enclosed 1s the soil sample for Tier 4 Site No. 10 (MET-A) that has been
archived at Radian. The Episode No. 1s 2646, and the SCC number of the sample
1s DQ-002027. This sample 1s to be extracted for dloxln / furan analysis.
If any questions arise concerning this sample shipment, please contact
Larry Keller or Andrew Miles at Radian Corporation at (919) 541-9100.
Sincerely,
Larry Keller
Staff Chemical Engineer
cc: E. Hanks/EPA/ AMTB
A. Miles/Radian
Radian Field FUe-RTP/PPK
B-7
Progress Center/3200 E. Chapel Hill Rd./Nelson Hwy./P.O. Box 13000/Research Triangle Park, N.C. 27709/(919)541-9100
-------
-------
APPENDIX C
DIOXIN/FURAN ANALYTICAL DATA
FOR GASEOUS SAMPLES
C-l Modified Method 5 Trains
C-2 Ambient XAD Train
C-l
-------
-------
TABLE C-l. DIOXIN/FURAN ANALYTICAL DATA FOR MM5 TRAINS
Isomer/Homologue
Furans
2378 TCDF
Other TCDF
Penta CDF
Hexa CDF
Hepta CDF
Octa CDF
Total PCDF
Amount Detected, Picograms Per Sample Train'
Run 02
704,900
2,380,300
2,119,000
1,933,500
684,100
464,600
8,286,400
Run 03
959,100
3,372,400
3,513,400
1,151,500
2,018,030
1,364,000
12,378,430
Run 04
Dioxins
2378 TCDD
Other TCOD
Penta COD
Hexa CDD
Hepta CDD
Octa CDD
Total PCDD
66,500
133,600
238,100
551,200
415,000
246,800
1,651,200
32,200
265,700
441,500
408,300
1,111,300
701,000
2,960,000
19,050
178,350
246,000
223,000
489,800
350,200
1,506,400
875,100
4,380,300
2,524,300
852,000
651,700
609,000
9,892,400
a.
Includes back-up XAD trap. See Section 8.3.2 for a discussion of quality
assurance/quality control results for these analyses.
C-3
-------
TABLE C-2. DIOXIN/FURAN ANALYTICAL DATA FOR AMBIENT XAD TRA-IN
Isomer/Homologue
Amount" Detected
Picograms per Train
Dioxins
2378 TCDD
Other TCDD
Penta CDD
Hexa CDD
Hepta CDD
Octa CDD
Total PCDD
ND(40)
500
ND(200)
400
400
700
2,000
Furans
2378 TCDF
Other TCDF
Penta CDF
Hexa CDF
Hepta CDF
Octa CDF
Total PCDF
600
6,000
1,400
3,000
1,700
1,600
14,300
ND » not detected
See Section 8.3.2 for a discussion of quality assurance/quality control
results for these analyses.
C-4
-------
APPENDIX D
RUN-SPECIFIC DIOXIN/FURAN EMISSIONS DATA
D-l Run-Specific Dioxin/Furan Emissions Data
(As-Measured Concentrations)
D-2 Run-Specific Dioxin/Furan Emissions Data
(Concentrations Corrected to 3 Percent Oxygen)
-------
-------
APPENDIX D-l
Run-Specific Dioxin/Furan Emissions Data
(As-Measured Concentrations)
D-l
-------
-------
TABLE D-l. DIOXIN/FURAN EMISSIONS DATA FOR RUN 2, SITE MET-A*
(AS-MEASURED CONCENTRATIONS)
Dioxin/Furan
Isomer
Isomer Concentration Isomer
In Flue Gas In
(ng/dscm)
Concentration
Flue Gas
(ppt)
Isomer Hourly
Emissions Rate
(ug/hr)
DIOXINS
2378 TCDD
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
1.75E+01(
3.53E+01(
6.28E+01(
1.45E+02(
1.09E+02(
6.51E+01(
4.36E+02
1.86E+02(
6.28E+02(
5.59E+02(
5.10E+02(
1.81E+02(
1.23E+02(
2.19E+03
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
1.31E+00(
2.63E+00(
4.25E+00(
8.95E+00(
6.20E+00(
3.41E+00(
2.67E+01
1,
4,
3,
3,
1,
6.
46E+01(
94E+01(
96E+01(
27E+01(
06E+01(
64E+00(
1.54E+02
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
8.83E+03
1
3
7
5,
3,
9,
3,
2.
2.
9,
6.
77E+04
16E+04
32E+04
51E+04
28E+04
2.19E+05
36E+04
16E+05
81E+05
57E+05
08E+04
17E+04
1.10E+06
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section 8.3.1.2 for discussion of
analytical surrogate recovery results.
NOTE: Isomer concentrations shown are at as-measured oxygen conditions
N/A = Not applicable. QA samples indicate the method capabilities and
minimum limits of detection when values are positive
ng = 1.0E-09g
ug = 1.0E-06g
ppt = parts per trillion, dry volume basis
D-3
-------
TABLE D-2. DIOXIN/FURAN EMISSIONS DATA FOR RUN 3, SITE MET-A*
(AS-MEASURED CONCENTRATIONS)
Dioxin/Furan
Isomer
Isomer Concentration
In Flue Gas
(ng/dscm)
Isomer Concentration
In Flue Gas
(ppt)
Isomer Hourly
Emissions Rate
(ug/hr)
DIOXINS
2378 TCDD
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
"Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF •
Total PCDF
8.50E+00(
7.01E+OH
1.16E+02(
1.08E+02(
2.93E+02(
1.85E+02(
7.81E+02
2.53E+02(
8.90E+OZ(
9.27E+02(
3.04E+02(
5.32E+02(
3.60E+02(
3.27E+03
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
)
)
)
)
)
)
6.35E-01(
5.24E+00(
7.87E+00(
6.63E+00(
1.66E+01(
9.67E+00(
4.66E+01
1.99E+01(
7.00E+01(
6.56E+01(
1.95E+01(
3.13E+01(
1.95E+01(
2.26E+02
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
)
)
)
)
)
i
4.43E+03
3.66E+04
6.08E+04
5.62E+04
1.53E+05
9.65E+04
4.08E+05
1.32E+05
4.64E+05
4.84E+05
1.59E+05
2.78E+05
1.88E+05
1.70E+06
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section S.3.,1.2 for discussion of
analytical surrogate recovery results.
M/IE: IM°'?er Concentrat1ons shown are at as-measured oxygen conditions.
N/A
ng
ug
PPt
Not applicable. QA samples indicate the method capabilities and
minimum limits of detection when values are positive.
1.0E-09g
1.0E-06g
parts per trillion, dry volume basis
D-4
-------
TABLE D-3. DIOXIN/FURAN EMISSIONS DATA FOR RUN 4, SITE MET-A*
(AS-MEASURED CONCENTRATIONS)
Dioxin/Furan
Isomer
Isomer Concentration
In Flue Gas
(ng/dscm)
Isomer Concentration
In Flue Gas
(ppt)
Isomer Hourly
Emissions Rate
(ug/hr)
DIOXINS
2378 TCDD
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
5.77E+00(
5.40E+01(
7.45E+01(
6.76E+01(
48E+02(
06E+02(
4.56E+02
2.65E+02(
1.33E+03(
7,
2,
1.
1,
65E+02(
58E+02(
97E+02(
85E+02(
3.00E+03
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
4.31E-01(
4.04E+00(
5.04E+00(
4.16E+00(
8.40E+00(
5.55E+00(
2.76E+01
08E+01(
04E+02(
41E+01(
66E+01(
16E+01(
OOE+01(
2.17E+02
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
2.81E+03
2,
3,
3.
7.
5.
63E+04
62E+04
29E+04
22E+04
16E+04
2.22E+05
1.29E+05
6.45E+05
3.72E+05
1.26E+05
9.60E+04
8.97E+04
1.46E+06
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section 8.3.1.2 for discussion of
analytical surrogate recovery results.
NOTE: Isomer concentrations shown are at'as-measured oxygen conditions.
N/A = Not applicable. QA samples indicate the method capabilities and
minimum limits of detection when values are positive.
ng = 1.0E-09g
ug = 1.0E-06g
ppt = parts per trillion, dry volume basis
D-5
-------
-------
APPENDIX D-2
Run-Specific Dioxin/Furan Emissions Data
(Concentrations Corrected to 3 Percent Oxygen)
0-7
-------
-------
TABLE D-4
DIOXIN/FURAN EMISSIONS DATA FOR RUN 2, SITE MET-Aa
(CONCENTRATIONS CORRECTED TO 3% OXYGEN)
Dioxin/Furan
Isomer
Isomer Concentration
In Flue Gas
(ng/dscm @ 3% oxygen)
Isomer Concentration
In Flue Gas
(ppt @ 3% oxygen)
Isomer Hourly
Emissions Rate
(ug/hr)
DIOXINS
2378 TCDD
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
3.95E+02(
7.93E+02(
1.41E+03(
3.27E+03(
2.46E+03(
1.47E+03(
9.80E+03
4.18E+03(
1.41E+04(
1.26E+04(
15E+04(
4.06E+03(
2.76E+03(
1
4.92E+04
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
2.
5,
9,
2,
1,
7.
95E+01(
93E+01(
55E+01(
01E+02(
39E+02(
66E+01(
6.02E+02
3.29E+02(
) 8.90E+02(
.36E+02(
2.39E+02(
1.49E+02(
3.45E+03
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
8.83E+03
1.77E+04
16E+04
32E+04
51E+04
28E+04
2.19E+05
9.36E+04
3.16E+05
2.81E+05
.57E+05
.08E+04
.17E+04
2.
9.
6.
1.10E+06
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section 8.3.1.2 for discussion of
analytical surrogate recovery results.
NOTE: Isomer concentrations shown are corrected to 3% oxygen.
N/A = Not applicable. QA samples indicate the method capabilities and
minimum limits of detection when values are positive.
ng = 1.0E-09g
ug = 1.0E-06g
ppt = parts per trillion, dry volume basis
D-9
-------
TABLE D-5 DIOXIN/FURAN EMISSIONS DATA FOR RUN 3, SITE MET-A*
(CONCENTRATIONS CORRECTED TO 3% OXYGEN)
Dioxin/Furan
Isomer
Isomer Concentration Isomer Concentration
In Flue Gas In Flue Gas
(ng/dscm @ 3% oxygen) (ppt @ 3% oxygen)
Isomer Hourly
CTrtr*** D •% + /•*
.> I \s I 1 *J IVUUC
(ug/hr)
DIOXINS
2378 TCDD
Other TCDD
•Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
1.70E+02(
-1.40E+03(
2.33E+03(
2.15E+03(
5.86E+03(
3.70E+03(
1.56E+04
5.06E+03(
l'.78E+04(
1.85E+04(
6.08E+03.(
1.06E+04(
7.20E+03(
6.53E+04
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
}
!
1
)
)
)
1.27E+01(
1.05E+02(
1.57E+02(
1.33E+02(
3.32E+02(
1.93E+02(
9.33E+02
3.98E+02(
1.40E+03(
1.31E+03(
3.90E+02(
6.26E+02(
3.90E+02(
4.51E+03
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
)
)
)
)
)
)
4.43E+03
3.66E+04
6.08E+04
5.62E+04
1.53E+05
9.65E+04
4.08E+05
1.32E+05
4.64E+05
4.84E+05
1.59E+05
2.78E+05
1.88E+05
1.70E+06
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section 8.3.1.2 for discussion of
analytical surrogate recovery results.
NOTE: Isomer concentrations shown are corrected to 3% oxygen.
N/A - Not applicable. QA samples indicate the method capabilities and
minimum limits of detection when values are positive
ng = 1.0E-09g
ug =* 1.0E-06g
ppt - parts per trillion, dry volume basis
D-10
-------
TABLE D-6 DIOXIN/FURAN EMISSIONS DATA FOR RUN 4, SITE MET-A'
(CONCENTRATIONS CORRECTED TO 3% OXYGEN)
Dioxin/Furan
Isomer
Isomer Concentration
In Flue Gas
(ng/dscm @ 3% oxygen)
Isomer Concentration
In Flue Gas
(ppt @ 3% oxygen)
Isomer Hourly
Emissions Rate
(ug/hr)
DIOXINS
2378 TCDD
Other TCDD
Penta-CDD
Hexa-CDD
Hepta-CDD
Octa-CDD
Total PCDD
FURANS
2378 TCDF
Other TCDF
Penta-CDF
Hexa-CDF
Hepta-CDF
Octa-CDF
Total PCDF
1.30E+02
1.22E+03
1.68E+03
1.52E+03
3.34E+03
2.39E+03
1.03E+04
5.97E+03
2.99E+04
1.72E+04
5.81E+03
4.44E+03
4.15E+03
6.74E+04
; N/A
N/A
N/A
N/A
[ N/A
[ N/A
( N/A
( N/A
; N/A
( N/A
( N/A
( N/A
,
)
)
)
)
,
)
)
)
)
9.70E+00(
9.08E+01(
1.13E+02(
9.35E+01(
1.89E+02(
1.25E+02(
6.21E+02
4.69E+02(
2.35E+03(
1.22E+03(
3.73E+02(
2.61E+02(
2.25E+02(
4.89E+03
N/A )
N/A )
N/A )
N/A )
N/A )
N/A )
N/A )
N/A )
N/A )
N/A )
N/A )
N/A )
2.81E+03
2.63E+04
3.62E+04
3.29E+04
7.22E+04
5.16E+04
2.22E+05
1.29E+05
6.45E+05
3.72E+05
1.26E+05
9.60E+04
8.97E+04
1.46E+06
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section 8.3.1.2 for discussion of
analytical surrogate recovery results.
NOTE: Isomer concentrations shown are corrected to 3% oxygen.
N/A = Not applicable. QA samples indicate the method Capabilities and
minimum limits of detection when values are positive.
ng = 1.0E-09g
ug = 1.0E-06g
ppt = parts per trillion, dry volume basis
D-ll
-------
-------
APPENDIX E
RUN-SPECIFIC RISK MODELING INPUT DATA
E-l
-------
-------
TABLE E-l. RISK MODELING PARAMETERS FOR RUN 2, SITE MET-AC
Latitude = 40 Degrees , 33 Minutes , 48 Seconds
Longitude = 74 Degrees , 13 Minutes , 05 Seconds
Stack Height (From Grade Level) = 76.2 m
Stack Diameter (ID) = 3.5 m
Flue Gas Flow Rate (Dry Standard) = 8386.9 dscmm
Flue Gas Exit Temperature = 374.3 Degrees K
Flue Gas Exit Velocity (Actual) = 19.8 mps
Dioxin/Furan
Isomer
2378 TCDD
Other TCDD
2378 TCDF
Other TCDF
Penta-CDD
Penta-CDF
Hexa-CDD
Hexa-CDF
Hepta-CDD
Hepta-CDF
Octa-CDD
Octa-CDF
Isomer
Concentration
In Flue Gas
(ng/dscm)
1.75E+01
3.53E+01
1.86E+02
6.28E+02
6.28E+01
5.59E+02
1.45E+02
5.10E+02
1.09E+02
1.81E+02
6.51E+01
1.23E+02
Isomer Hourly
Emissions
Rate
(ug/hr)
8.83E+03
1.77E+04
9.36E+04
3.16E+05
3.16E+04
2.81E+05
7.32E+04
2.57E+05
5.51E+04
9.08E+04
3.28E+04
6.17E+04
Relative
Potency
Factor
1.000
.010
.100
.001
.500
.100
.040
.010
.001
.001
.000
.000
2,3,7,8 - TCDD
Equivalent
Emissions
(mg/yr)
7.20E+04
1.45E+03
7.64E+04
2.58E+03
1.29E+05
2.30E+05
2.39E+04
2.09E+04
4.50E+02
7.41E+02
.OOE+00
.OOE+00
Net 2378 TCDD Equivalent Atmospheric Loading
5.57E+05
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section 8.3.1.2 for discussion of
analytical surrogate recovery results.
ng = 1.0E-09g
ug = 1.0E-06g
mg = 1.0E-03g
Standard conditions: 293 K (20 C) temperature and 1 atmosphere pressure.
8160 operating hours per year
E-3
-------
TABLE E-2. RISK MODELING PARAMETERS FOR RUN 3, SITE MET-A*
Latitude - 40 Degrees , 33 Minutes , 48 Seconds
Longitude - 74 Degrees , 13 Minutes , 05 Seconds
Stack Height (From Grade Level) = 76.2 m
Stack Diameter (ID) - 3.5 m
Flue Gas Flow Rate (Dry Standard) - 8699.9 dscmm
Flue Gas Exit Temperature = 378.4 Degrees K
Flue Gas Exit Velocity (Actual) =20.7 mps
Dioxin/Furan
Isomer
2378 TCDD
Other TCDD
2378 TCDF
Other TCDF
Penta-CDD
Penta-CDF
Hexa-CDD
Hexa-CDF
Hepta-CDD
Hepta-CDF
Octa-CDD
Octa-CDF
Isomer
Concentration
In Flue Gas
(ng/dscm)
8.50E+00
7.01E+01
2.53E+02
8.90E+02
1.16E+02
9.27E+02
1.08E+02
3.04E+02
2.93E+02
5.32E+02
1.85E+02
3.60E+02
Isomer Hourly
Emissions
Rate
(ug/hr)
4.43E+03
3.66E+04
1.32E+05
4.64E+05
6.08E+04
4.84E+05
5.62E+04
1.59E+05
1.53E+05
2.78E+05
9.65E+04
1.88E+05
Relative
Potency
Factor
1.000
.010
.100
.001
.500
.100
.040
.010
• .001
.001
.000
.000
2,3,7,8 - TCDD
Equivalent
Emissions
(mg/yr)
3.62E+04
2.99E+03
1.08E+05
3.79E+03
2.48E+05
3.95E+05
1.84E+04
1.29E+04
1.25E+03
2.27E+03
.OOE+00
.OOE+00
Net 2378 TCDD Equivalent Atmospheric Loading 8.29E+05
a. Data reported in this table represent lower bounds'on'the'actuardioyin/
furan emissions from Site MET-A. See Section 8.3.1 2 for discussion of
analytical surrogate recovery results. aiscussion or
ng
ug
mg
1.0E-09g
1.0E-06g
1.0E-03g
C)
"..ph.™ pressure.
E-4
-------
TABLE E-3. RISK MODELING PARAMETERS FOR RUN 4, SITE MET-AC
Latitude - 40 Degrees , 33 Minutes , 48 Seconds
Longitude » 74 Degrees , 13 Minutes , 05 Seconds
Stack Height (From Grade Level) * 76.2 m
Stack Diameter (ID) = 3.5 m
Flue Gas Flow Rate (Dry Standard) = 8104.0 dscmm
Flue Gas Exit Temperature =373.9 Degrees K
Flue Gas Exit Velocity (Actual) = 19.1 mps
Dioxin/Furan
Isomer
2378 TCDD
Other TCDD
2378 TCDF
Other TCDF
Penta-CDD
Penta-CDF
Hexa-CDD
Hexa-CDF
Hepta-CDD
Hepta-CDF
Octa-CDD
Octa-CDF
Isomer
Concentration
In Flue Gas
(ng/dscm)
5.77E+00
5.40E+01
2.65E+02
1.33E+03
7.45E+01
7.65E+02
6.76E+01
2.58E+02
1.48E+02
1.97E+02
1.06E+02
1.85E+02
Isomer Hourly
Emissions
Rate
(ug/hr)
2.81E+03
2.63E+04
1.29E+05
6.45E+05
3.62E+04
3.72E+05
3.29E+04
1.26E+05
7.22E+04
9.60E+04
5.16E+04
8.97E+04
Relative
Potency
Factor
1.000
.010
.100
.001
.500
.100
.040
.010
.001
.001
.000
.000
2,3,7,8 - TCDD
Equivalent
Emissions
(mg/yr)
2.29E+04
2.14E+03
1.05E+05
5.27E+03
1.48E+05
3.04E+05
1.07E+04
1.02E+04
5.89E+02
7.84E+02
.OOE+00
.OOE+00
Net 2378 TCDD Equivalent Atmospheric Loading
6.09E+05
a. Data reported in this table represent lower bounds on the actual dioxin/
furan emissions from Site MET-A. See Section 8.3.1.2 for discussion of
analytical surrogate recovery results.
ng = 1.0E-09g
ug = 1.0E-06g
mg = 1.0E-03g
Standard conditions: 293 K (20 C) temperature and 1 atmosphere pressure.
8160 operating hours per year
E-5
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-------
APPENDIX F
COMPOUND-SPECIFIC PRECURSOR RESULTS
F-l
-------
-------
TABLE F-l. COMPOUND-SPECIFIC DIOXIN PRECURSOR CONCENTRATIONS
FOR SITE MET-A FEED SAMPLES
Precursor Concentration, ug/g (ppm)
Precursor Telephone Circuit Electronic
Compounds Coke Parts,Wire Boards Switching
Gear
Base Neutrals Fraction
Chlorinated Benzenes:
Dichlorobenzenes
Tri chl orobenzenes
Tetrachl orobenzenes
Pentachl orobenzenes
Hexachl orobenzenes
Total Chlorinated Benzenes
Chlorinated Biphenvls:
Chlorobiohenvls
Dichlorobiohenvls
Trichlorobiohenvls
Tetrachl orobi ohenvl s
Pentachl orobi ohenvl s
Hexachl orobi ohenvl s
Heotachl orobi ohenvl s
Octachl orobi ohenvl s
Nonachlorobiohenvls
Decachl orobi phenvl s
Total Chlorinated Biohenvls
ND,
Nl),
NU,
Nl),
Nl),
Nf)
NO,
Nl),
Nil,
Nl),
NO,
Nl),
NU,
NU,
NO.
Nl)
Nl),
ND
ND
ND
ND
NU
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.004
ND
ND
ND
ND
ND
0.004
ND.
ND.
ND.
ND.
ND.
ND
ND.
ND.
ND.
ND.
ND.
ND.
ND.
ND.
ND.
ND.
ND.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
0.003
0.100
0.140
0.016
ND
ND
0.26
Acids Fraction
Chlorinated Phenols:
Dichlorophenols ND. ND ND ND ND ND
Trichlorophenols ND. ND ND ND ND ND
Tetrachloroohenols ND. ND ND ND ND ND
Pentachloroohenols ND. ND ND ND ND ND
Total Chlorinated Phenols ND. ND ND ND ND ~ND
ND = not detected ~~ : ;
See Section 8.3.2 for a discussion of quality assurance/quality control
results for these analyses.
F-3
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-------
APPENDIX G
RESEARCH TRIANGLE INSTITUTE (RTI)
SYSTEMS AUDIT
G-l
-------
RESEARCH TRIANGLE INSTITUTE
QUALITY ASSURANCE AUDIT FOR TIER 4 OF THE NATIONAL DIOXIN STUDY:
SECONDARY COPPER RECOVERY BLAST FURNACE. SITE MET-A
By
Richard V. Crime
Robert S. Wright
EPA Contract No. 63-02-3149
Work Assignment 10-1
RTI Project No. 472U-250Q-48
EPA Technical Project Monitor,
D. Qberacker
Prepared for
William 3. K.'jykendal, Air Management Technology Branch
Monitoring and Data Analysis Division
Offica of Air Quality Planning and Standards
Environmental Protection Agency
Research Triangle Park, NC 27711
November 1935
POST OFFICE BOX 12194 RESEARCH TRIANGLE PARK, NORTH CAROLINA 27709
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TABLE OF CONTENTS
Section Page
1.0 INTRODUCTION -. 1
2.0 AUDIT RESULTS , 4
2.1 Continuous Emission Monitoring System 4
' 2.2 Modified Method 5 Sampling Train 5
2.3 Additional Observations 9
3.0 CONCLUSIONS .- 10
4.0 APPENDIX 11
4.1 Section From Internal Radian Audit Report
Describing Audit of Continuous Emission
Monitoring System 11
G-2
-------
LIST OF TABLES
Table Page
1 List of Persons Present During Site MET-A Audit 2
2 Radian Calibration Standards 6
3 On-Hand Cylinder Certificates (AIRCO) 7
LIST OF FIGURES
Figure Page
1 Configuration of Primary and Back-Up Sorbent
Modules in Modified Method 5 Sampling Train 8
6-3
-------
1.0 INTRODUCTION
On May 30, 1985, Research Triangle Institute (RTI) performed a
quality assurance (QA) audit of an emission test program underway at a
secondary copper recovery blast furnace (Site MET-A). The emission
test program was one of a series of tests performed by Radian Corpora-
tion for the U.S. Environmental Protection Agency (EPA). The data
collected during these tests will be added to the data base supporting
Tier 4 of EPA's National Dioxin Study. The primary objective of Tier 4
is to determine if various combustion facilities are sources of dioxin
emissions. If any of the combustion facilities are found to emit
dioxins, the secondary objectives of Tier 4 are to quantify these
dioxin emissions and, if possible, to relate the emissions to
combustion device operating conditions. The audit was performed by
RTI's Richard V. Crume and Robert S. Wright. The EPA Project Officer
was William B. Kuykendal of the Office of Air Quality Planning and
Standards, Research Triangle Park, North Carolina. A list of persons
present during the audit, including a number of observers from the
States of New York and New Jersey, is presented in Table 1.
At EPA's request, RTI's audit focused on the continuous emission
monitoring system and on modifications made to the Modified Method 5
sampling train. Additionally, RTI examined other sampling systems and
reviewed in-house audit data provided by Radian. In preparing for the
audit, RTI reviewed the following two documents:
o Site Specific Test Plan, Secondary Copper Recovery Blast Furn-
ace, Test Number Ten, Site MET-A. Radian Corporation. April
8, 1985.
o Radian Corporation's Response to Comments Submitted by the
State of New York. No Date.
1
G-4
-------
TABLE I. LIST OF PERSONS PRESENT DURING
THE SITE MET-A AUDIT
U.S. Environmental Protection Agency
William Lamason
Radian Corporation
Deborah Benson, Assistant
Lee Garcia, MM5 Operator
Gary Henry, MM5 Operator
Larry Keller, Engineer
Jill Myerson, Assistant
Jim Reynolds, Sample Team Leader
"Dave Savia, CEM Operator
Research Triangle Institute
Richard Crume
Robert Wright
State of New York
Michael Bryce
Al Columbus
Louise Halper
Steven Ohrwaschel
Michael Osual
Michael Surgan
State of New Jersey
Ezikpe Akuma
Edward Chromaiski
Scott Hawthorne
David Lowie, Jr.
Rich Oaniak
Frank Papp
Bryon Sullivan
2
G-5
-------
The results of this audit are also reported in a letter to the EPA
Project Officer, William B. Kuykendal1.
1 Grume, R.V. Letter to William 8. Kuykendal discussing results of
Site MET-A audit. Research Triangle Institute, Research Triangle
Park, North Carolina. August 1, 1985.
G-6
-------
-------
2.0 AUDIT RESULTS
2.1 Continuous Emission Monitoring System
The continuous emission monitoring system was of particular
interest to EPA because a new set-up, which had not been used during
previous Tier 4 tests, was in use during the MET-A tests. Although
the new set-up consisted of the same equipment that had previously been
used, the equipment had been moved to a newly outfitted truck. The
auditors carefully examined the new set-up and concluded that it was
satisfactory, although several minor problems were detected. It is
recommended that these problems, which are summarized below, be
addressed prior to any future testing.
o 0? Monitor. Although the Og monitor was operating cor-
rectly, a problem with the signal conditioning box prevented
the signal from reaching the data acquisition system. Instead,
5-minute averages were taken by hand.
o SO? Calibration and QC Gases. The S02 concentrations found
in the stack (about 250 ppm) were much higher than expected.
As a consequence, the concentrations of the calibration and QC
gases (83.5 and 19.6 ppm, respectively) were too low to be
effective. (The instrument scale was 500 ppm rather than the
100 ppm scale anticipated prior to the testing.)
o Verification of Calibration Gas. The calibration gas certifi-
cations had not been verified. However, Radian felt that the _+
20% accuracy QA objective would coyer any possible certifica-
tion inaccuracy. (Nevertheless, prior KTI audits of commercial
"certified" calibration standards found that their certified
values could be in error by greater than 20 percent. Errors of
this magnitude would leave little room for other instrumental
errors).
o Calibration Gas Certification. Several of the calibration
standards had not been analyzed or re-analyzed within 6 months
of the test. (It should be noted, however, that Radian's QA
project plan does not call for periodic re-analysis of the
calibration standards.)
4
G-7
-------
o Calibrations Standards vs. Certificates. The gas producers'
calibration standards on-hand in the Radian mobile facility did
not match producers' certificates on-hand. This problem is
illustrated in Tables 2 and 3.
o NOy Monitor. The NOX monitor drift, at _+ 5 to 10%, exceed-
ed that observed for the other monitors.'" Although at this time
the drift is still within the acceptance limit of ± 20% for the
single point response factor test, the monitor should be close-
ly watched to prevent a worsening of drift during future
tests.
In addition to evaluating Radian's on-site continuous emission
monitoring system, RTI asked Radian to provide the results of any in-
house continuous monitor performance auditing relevant to the Tier 4
tests. The materials Radian provided are contained in the Appendix.
Note that although most performance test data for the'continuous
emission monitors fall within the +_ 20% objectives, the relative errors
for the CO and NOX instruments exceeded this objective in several
cases.
2.2 Modified Method 5 Sampling Train
The Modified Method 5 sampling train in use at Test Site MET-A was
unique in that a second XAD resin cartridge was added to the system
just after the first impinger, as illustrated in Figure 1. This
configuration, which was requested by EPA, was designed to mitigate
concerns regarding the horizontal position of the XAD condenser.
(Although the horizontal mounting of the condenser had been approved by
EPA during previous Tier 4 tests, officials from the State of New York
remained concerned about an increased potential for organic compounds
breaking through the resin.)
The set-up and operation of the second XAD resin cartridge
appeared to be acceptable. Furthermore, with one exception, operation
of the entire train appeared normal. The one exception involved the
formation of a yellow precipitate in the condenser, between the filter
and the first XAD resin cartridge. The nature of this precipitate is
unknown, although its color suggests that it may be chloride. Radian
reported that the precipitate was easily removed: with acetone.
5
G-8
-------
TABLE 2. RADIAN CALIBRATION STANDARDS
Cylinder
1.0.
CC-18556
CC-541
CC-1904
CC -18428
CC-17528
CC-9688
CC-1S595
CC-15903
Contents
Propane
Air
Propane
Air
CO
CO 2
02
N2
CO
CO 2
02
N2
NO
N2
NO
N2
S02
N2
S02
N2
Concentrations
• 19.7 ppm
90.0 ppm
5530 ppm
18.05
21. IS
2000 ppm
13. OS
9.3S
84.6 ppm
20.8 ppm
83.1 ppm
19.5 ppm
Cyl inder
Analysis
Date
10/84
10/84
4/85
Not
Found
4/85
9/84
Not
Found
Not ,
Found
Comments
None.
None.
None.
None.
No tag. Value read
from cylinder wall.
None.
No tag. Value read
from cylinder wall.
No tag. Value read
from cylinder wall.
6
G-9
-------
TABLE 3. ON-HAND CYLINDER CERTIFICATES (AIRCO)
Cylinder
I.D.
N-249706
C-18428
CC-16600
CC-17350
CC-2320
CC-15819
CC-18059
CC-180064
CC-17573
Contents
H2
N2 '
CO
CO 2
02
N2
S02
02
CO
C02
02
N2
NO
NO 2
NO
N02
N2
02
NO
Concentrations
40.12
2000 ppm
13.02
9.32
2005 ppm
10.22
5175 ppm
18.52
21.02
285 ppm
< 2 ppm
1042
< 10 ppm
17.82
155 ppm
< 2.0 ppm
7
G-10
-------
Condenser
(Yellow Precipitate)
From Filter
Primary
Sorbent
Module
Glass Wool
XAD
FRIT
Ice Bath
To Second Impinger
Back-Up
Sorbent
Module
Figure 1. Configuration of primary and back-up sorbent modules
in modified Method 5 sampling train.
8
G-ll
-------
2.3 Additional Observations
Several other problems occurred during the test program, as
summarized below:
o Analytical Laboratory. Radian's mobile analytical laboratory
was damaged en route to the test site and had to be left
behind. Most of the laboratory equipment was salvaged and
transferred to a temporary laboratory set-up at the plant. The
temporary laboratory was inspected by RTI and appeared to be
satisfactory.
o Filter Placement. On the first day of testing the Modified
Method 5 sample train filters were placed backwards, thereby
invalidating the test results. These tests were consequently
repeated.
. i
o Electrical Problems. Power supply problems'forced testing to
be delayed during the morning of the second day. However,
•these problems were solved by noon and did not seriously
interfere with the test schedule.
9
6-12
-------
3.0 CONCLUSIONS
Operation of the continuous emission monitoring system and the
Modified Method 5 sampling train was found to be satisfactory.
Although several problems with the monitoring system were detected,
these problems did not appear to significantly interfere with testing
or to compromise test results." Nevertheless, if these problems are not
corrected, more serious problems could develop during any future
testing. In particular, it is recommended that the following actions
be taken:
o Repair the signal conditioning box so that the Q£ signals can
reach the data acquisition system.
o Calibration and QC gas concentrations should be selected to
fall within the operating range of the continuous emission
monitors.
o Calibration and QC gases for the most critical measurements
should be verified.
o Gas cylinder calibrations should be kept up to date.
o Calibration standards should match the gas producers'
certificates on-hand.
o The NOX monitor drift problem should be corrected.
o The relative errors associated with the CO and NOX monitors
should be examined.
10
G-13
-------
-------
4.0 APPENDIX
4.1 Section From Internal Radian Audit Report Describing Audit of
Continuous- Emission Monitoring System
11
G-14
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/4-84-014s
2.
3. REORIENTS ACCESSION NO.
4. TITUS AND SUBTITLE
National Dioxin Study Tier 4 - Combustion Sources
Final Test Report - Site 10
Secondary Copper Recovery Cupola Furnace MET - A
5. REPORT DATE
April 1987
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Lawrence E. Keller, James R. McReynolds
Deborah J. Benson
8. PERFORMING ORGANIZATION REPORT NO.
87-231-056-12-44
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
Post Office Box 13000
Research Triangle Park, NC 27709
1O. PROGRAM ELEMENT NO.
11, CONTRACT/GRANT NO.
68-03-3148
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency, OAQPS
Research Triangle Park, NC 27711
Office of Research and Development
Washington, DC 20460
13, TYPE OF REPORT AND PERIOD COVERED
Final
14, SPONSORING AGENCY CODE
IS. SUPPLEMENTARY NOTES
EPA Project Officers: Donald Oberacker, ORD
William B. Kuykendal, OAQPS
10. ABSTRACT ' —~ —•"——————————^^^^—
This report summarizes the results of a dioxin/furan emissions test of a secondary
copper recovery cupola furnace equipped with an afterburner for hydrocarbon emissions
control and two baghouses for particulate emissions control. The cupola furnace is used
for recovery of copper from telephone scrap and other copper-bearing materials. The
test was, the 10 in a series of dioxin/furan emissions tests conducted under Tier 4
of the National Dioxin Study. The primary objective of Tier 4 is to determine if
various combustion sources are sources of dioxin/or furati emissions. If any of the
combustion sources are found to emit dioxin or furan, the secondary objective of Tier 4
is to quantify these emissions.
Secondary copper recovery cupola furnaces are one of 8 combustion source categories
that have been tested in the Tier 4 program. The tested cupola furnace, hereafter
referred to as cupola furnace MET-A, was selected for this test after an initial infor-
mation screening and a one-day pretest survey visit. Cupola furnace MET-A is a large
secondary copper recovery cupola furnace relative to others in the United States. The
furnace feed includes plastic-bearing materials of various types, some of which may con-
tain chlorinated organic compounds.
Data presented in the report include dioxin (tera through octa homologue +2378
TCDD) and furan (tetra through octa homologue +2378 TCDF) results for both stack samples
and ash samples. In addition, process data collected during sampling are also
-presented.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATl Field/Group
Air Emissions
Combustion Sources
Dioxin
Furans
2,3,7,8 Tetrachlorodibenzo-p-dioxin
Secondary Copper Recovery Cupola Furnace
Secondary Metals
Air Pollution Emissions
Data
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report I
Unclassified
21. NO. OF PAGES
210
20. SECURITY CLASS (Thispage/
Unclassified
22. PRICE
EPA F*tm 2220—1 (R«v. 4—77) PREVIOUS COITION is OBSOLETE
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