United States
Environmental Protection
Agency
Industrial Environmental
Research Laboratory
Research Triangle Park NC 27711
N k"/
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Research and Development
EPA-600/S2-84-159 Dec. 1984
Project Summary
Hot Flue Gas Spiking and
Recovery Study for
Tetrachlorodibenzodioxins
(TCDD) Using Modified Method
5 and SASS Sampling with a
Simulated Incinerator
Marcus Cooke, Fred DeRoos, and Bruce Rising
i\
This study was initiated to evaluate
the sampling and analysis of ultratrace
levels of dibenzodioxins using EPA's
recommended source sampling
procedures (Modified Method 5 (MM5)
train and the Source Assessment
Sampling System-SASS). A gas-fired
combustion system was used to
simulate incineration flue gas, and a
precision liquid injection system was
designed for the program. The precision
liquid injector was used to administer
dilute solutions of 1.2,3,4-tetrachloro-
dibenzo-p-dioxin (1,2,3,4-TCDD) di-
rectly into a hot-260°C (500°F)-flue
gas stream. Injections occurred contin-
uously during a sampling episode so
that very low gas-phase concentrations
of 1,2,3,4-TCDD were continuously
mixed with flue gases.
Recoveries were measured for eight
burn experiments. For all but one, the
recoveries could be considered quanti-
tative, demonstrating efficient
collection by the EPA sampling
systems. In one study, the components
and connecting lines from a sampling
device were analyzed separately to show
where the 1,2,3.4- TCDD deposited in
the train.
This Project Summary was developed
by EPA's Industrial Environmental
Research Laboratory. Research
Triangle Park. JVC, to announce key
findings of the research project that is
fully documented in a separate report of
the same title (see Project Report
ordering information at back).
Introduction
To test the collection efficiency of the
recommended EPA sampling trains for
TCDD isomers, a stack sampling program
was carried out. A simulated incinerator
flue gas was generated using a laboratory
scale furnace. The flue gases from this
furnace were spiked with a small quantity
of 1,2,3,4-TCDD and then sampled to
determine collection efficiency of the
TCDD sampling system. Sampling rates
and conditions were maintained at levels
typical of those used with the Method 5 or
SASS sampling devices.
Figure 1 shows the experimental setup:
natural gas combustor outlet, hot gas
spike injection, sampling train, charcoal
safety filter, and gas moving system.
Combustion and
Sampling Systems
In this study, two sampling systems
(the Source Assessment Sampling
System (SASS) and a modification of the
Method 5 (MM5) sampling train) were
used. In this program, the SASS
equipment was operated in accordance
with procedures outlined in the EPA Level
1 manual. Because a relatively clean fuel
(natural gas) was used to produce the flue
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Furnace
Outlet
Air
Pump
| Sampling (J 3 Atmosphere
Train f* •A
Spike Injection
System
To
Charcoal
Filler
consistency and high recoveries for each I
experiment, except Test 10, where a
229% recovery was observed.
These experiments demonstrated the
ability of two EPA source sampling trains
to collect and stabilize TCDDs for
subsequent analysis. The model
compound used, 1,2,3,4-TCDD, is
probably a good representative of all the
tetrachlorinated dibenzo-p-dioxins, and
the other isomeric members of this class
of compounds can probably be analyzed
by the techniques used in this study.
Figure 1. TCDD injection and sampling apparatus.
Table 1. 1,2,3,4-TCDD Recoveries from Tests 1-10
Test
Number
1 (Blank)
2 (Dry Air)
3
4
5
6
7
8
9
JO
Samp/ing
System
SASS
SASS
SASS
SASS
SASS
SASS
MM5
MM5
MM5
MM5
Liquid
Spike
Volume (ml)
50
49
51
42
50
51
47
47
49
47
1.2.3,4-TCDD
Liquid
Concentration
(pg/ml)
0
500
500
50
5
5
15
12
8
8
Expected
Concentration
(ngl
....
25
21
2.5
0.25
7.1
0.56
0.39
0.38
Calculated
Concentration
(ng)
—
....
18
17
2.9
0.28
8.0
0.57
0.47
0.87
Percent
Recovery
0
="92
73
83
117
113
113
101
120
229
gas stream sampled.some modifications
were made to the standard SASS
apparatus. The normal stack sampling
probe and cyclones were replaced with
borosilicate glass connecting tubing. The
stainless steel cyclones were removed to
simplify equipment turnaround. The
solutions that would normally be con-
tained in impingers 1 and 2 were
eliminated, although the impingers were
left in the system as condensate traps.
A development of this study was a gas-
phase spiking system that could inject
liquid solutions of the test material into
the hot flue gas'stream. A fused silica
capillary line was used to transfer the
dioxin solution from a precision metering
pump to the flu'e gas stream.
Results
A series of 10 experiments were
performed. The first experiment (Test 1)
was a system blank in which the SASS
train and combustion system were
operated normally using the solvent
delivery system to generate a blank
injection. No 1,2,3,4-TCDD was observed
in the blank run. Test 2 was a heated air
run in which the 1,2,3,4-TCDD spike was
tested on heated room air.The air stream
was dry, not containing the high moisture
observed in many combustion gas
streams. Tests 2-10 involved spiking the
combustion flue gas with variable dioxin
levels, using both SASS and MM5 trains
for collection of gas-phase emissions.
Tests 3-10 were designed to challenge
both the SASS and MM5 sampling sys-
tems at gas-phase concentrations that
were expected to cover a range from high
levels to the minimum levels detectable
by available analytical methodology.
Resu Its of Tests 1 -10 are given in Table 1.
These data show good internal
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M. Cooke, F. DeRoos, andB. Rising are with Battelle-Columbus Laboratories, 505
KingAve., Columbus, OH43201.
Merrill D. Jackson is the EPA Project Officer (see below).
The complete report, entitled "Hot Flue Gas Spiking and Recovery Study for
Tetrachlorodibenzodioxins fTCDD) Using Modified Method 5 and SASS
Sampling with a Simulated Incinerator," (Order No. PB 85-115 145; Cost:
$8.50, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
U S GOVERNMENT PRINTING OFFICE, 1984 — 559-016/7857
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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