Method 0023A: Sampling Method for Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofuran Emissions from Stationary Sources, part of Test Methods for Evaluating Solid Waste, Physical/Chemical Methods

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METHOD 0023A
SAMPLING METHOD FOR POLYCHLORINATED DIBENZO-
p-DIOXINS 
AND POLYCHLORINATED DIBENZOFURAN EMISSIONS
FROM STATIONARY SOURCES
1.0
SCOPE AND APPLICATION
1.1
This method describes the sampling procedure to be used for determining stack
emissions of polychlorinated dibenzo-
p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs)
from stationary sources. The air sample is collected and analyzed by the determinative portion of
Methods 8280 or 8290. This method describes the procedures for sampling and calculating results.
This method may be modified to allow simultaneous sampling and analysis for polychlorinated
biphenyls (PCBs), polynuclear aromatic hydrocarbons (PAHs), or semivolatile organic compounds
(SVOCs). However, specific approval is required for this modification, and detailed modification of
the methodology is required.
1.1.1
This method is a revision of Method 23 (see Ref. 10).
1.1.2
The surrogates and recovery standards include the standards listed in Methods
8280 and 8290.
1.1.3
The method refers to specific techniques described in Methods 1, 2 and 5 (see
Ref. 10). Analysts should obtain copies of those methods prior to sampling.
1.2
This method is restricted to use by or under the supervision of analysts experienced in
the use of air sampling methods and the analysis of PCDDs, PCDFs, PCBs, PAHs, and SVOCs from
the components of Method 0010 trains. Each analyst must demonstrate the ability to generate
acceptable results with this method.
1.3
Safety - The laboratory should develop a strict safety program for the handling of PCDDs
and/or PCDFs.
1.3.1
2,3,7,8-TCDD has been found to be acnegenic, carcinogenic, and teratogenic in
laboratory animal studies. Other PCDDs and PCDFs containing chlorine atoms in positions
2,3,7,8 are known to have toxicities comparable to that of 2,3,7,8-TCDD. The analyst must be
aware of the potential for inhalation and ingestion. It is recommended that such samples be
processed in a confined environment, such as a hood or a glove box. Personnel handling
these types of samples should wear masks fitted with charcoal filters to prevent the inhalation
of airborne particulates.
1.3.2
The toxicity or carcinogenicity of each reagent used in this method is not precisely
defined. However, each chemical should be treated as a potential health hazard, and
exposure to these chemicals kept to a minimum. The laboratory is responsible for maintaining
a current awareness file of OSHA regulations regarding the safe handling of the chemicals
specified in this method. A reference file of material safety data sheets should be made
available to all personnel involved in the sampling and chemical analysis of samples suspected
to contain PCDDs/PCDFs. Method 8290 and References 7, 8, and 9 give additional
information on laboratory safety.

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2.0
SUMMARY OF METHOD
2.1
Gaseous and particulate PCDDs/PCDFs are isokinetically withdrawn from an emission
source and collected in a multicomponent sampling train. The collection components consist of the
front half glassware surfaces (nozzle, probe, and front half filter holder), the glass fiber filter, the back
half glassware surfaces (back half filter holder and condenser coil) and the solid sorbent (XAD-2®)
module.
2.2
Following sampling the glass collection components are rinsed. The PCDD/PCDF are
then extracted from the front half rinses and filter and another separate extraction is performed on
the XAD-2® and back half rinses.
2.3
The filter and XAD-2® extracts are then analyzed separately. Surrogate recoveries are
determined for both fractions. The analysis is performed using high resolution gas chromatography
(HRGC) and high resolution mass spectrometry (HRMS), using the procedures of Method 8290.
3.0
INTERFERENCES
3.1
The use, in this method, of high resolution mass spectrometry with high resolution
capillary gas chromatography avoids the interference from polychlorinated biphenlys and
polychlorinated diphenyl ethers which could be serious with lower resolution techniques. 
3.2
Very high amounts of other organic compounds in the matrix will interfere with the
analysis. Extensive column-chromatographic cleanup has been introduced into typical HRGC/HRMS
analytical methodology to minimize matrix effects due to high concentrations of organic compounds.
3.3
Method interferences may be caused by contaminants in solvents, reagents, glassware,
and other sample processing hardware. All of these materials must be routinely demonstrated to
be free from interferences under the conditions of the analysis by preparing and analyzing laboratory
method blanks.
Glassware must be cleaned thoroughly before using. A procedure which has been found to
be effective is given in Sec. 6.1.4, but any protocol which consistently results in contamination-free
glassware is acceptable.
3.3.1
The use of high purity reagents and solvents helps to minimize interference
problems in sample analysis.
4.0
APPARATUS AND MATERIALS
The following section describes all the sampling equipment and the associated performance
specifications necessary to collect a gas sample from a stationary source according to Method 0023.
4.1
Sampling train - A schematic diagram of the sampling train is shown in Figure 1. This
train configuration has been adapted from Method 5 (Reference 10) with the addition of condenser,
XAD-2® trap and filtration-coil connecting glassware. Sealing greases must not be used in
assembling the train. Complete sampling systems are commercially available that have been
developed to meet all the EPA equipment design specifications. The following equipment is
required.

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4.1.1
Nozzle - The nozzle should be made of quartz or borosilicate glass. Stainless
steel nozzles should not be used. The taper angle should be 
# 30E, with taper on the outside
to preserve a constant inside diameter (ID). The nozzle ID should be determined in order to
sample isokinetically at a rate that allows collection of an adequate sample volume. The
minimum sample volume should be determined to allow appropriate detection limits to be
achieved (see Sec. 6.2.3).
4.1.2
Probe liner - The sampling probe liner should be constructed of borosilicate or
quartz glass tubing. The typical outside diameter (OD) used by sampling equipment
manufacturers is about 16 mm, encased in a stainless steel sheath with an OD of 25.4 mm.
Either borosilicate or quartz glass liners may be used for stack temperatures up to about
480
EC, but quartz glass liners should be used at higher stack temperature [480 to 900EC].
4.1.3
Probe sheath and heating system - A stainless steel or equivalent probe sheath
should be used to house the probe liner and heating system. The probe heating system should
be capable of maintaining probe gas temperatures at the probe exit of 120
EC ± 14EC during
sampling. This temperature should be verified by placing a thermocouple temperature sensor
against the outer surface of the probe liner at least 2 feet upstream of the filter oven.
Temperature readings should be recorded during sampling.
4.1.4
Glass cyclone - A glass cyclone may be used between the probe and filter holder
for high particulate concentrations. A cyclone, if used, should be rinsed and recovered with
the front half of the train.
4.1.5
Filter holder - A filter holder of borosilicate glass with a Teflon® frit filter support
should be used. The holder design should provide a positive seal against leakage from the
outside or around the filter. The holder should be durable, easy to load, leak-free in normal
applications, and is positioned immediately following the probe (or cyclone, if used) with the
filter placed toward the flow.
4.1.6
Filter heating system - Any heating system may be used which is capable of
maintaining the filter holder at 120
EC ± 14EC during sampling. Other temperatures may be
specified by a subpart of the regulations or approved for a particular application. A gauge
capable of measuring temperatures to within 3
EC should be provided to monitor the
temperature around the filter during sampling.
4.1.7
Sample transfer lines - A sample transfer line may be used if needed to direct
sample flow from the probe to the filter or from the filter to the condenser. The probe-to-filter
line should be insulated and heated so that gas exit temperatures are 120
EC ± 14EC. The
filter-to-condenser line should be insulated and oriented with the downstream end lower than
the upstream end so that any condensate will flow away from the filter and into the condenser.
These lines should be constructed of Teflon® or glass and should be recovered with their
respective rinse fractions (front half or back half).
4.1.8
Condenser - A multi-coil water-cooled glass condenser should be used to cool
the sample gas prior to entry into the sorbent module. The orientation of the condenser should
be vertical.
4.1.9
Sorbent module - The glass water-cooled container configured to hold the solid
sorbent (XAD-2®) should contain a minimum of 20 g of XAD-2® and may contain as much as
40 g. A schematic diagram is shown in Figure 2. A single piece condenser-trap can be used
if desired. The sorbent trap configuration should be vertical so that condensate drains from

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the condenser through the sorbent and so that channeling of the gas flow does not occur. The
connecting fittings should form leak-free, vacuum tight seals. Sealant greases should not be
used in the sampling train. A coarse glass or Teflon® frit along with glass wool plugs is
included to retain the sorbent. The tester may engrave a unique identification number for
inventory and sample tracking.
4.1.10 Impinger trains - Four impingers should be connected in series with leak-free
ground-glass fittings or any similar noncontaminating fittings. The first impinger should be a
short stem (knock out) version. The second impinger should be a Greenburg-Smith impinger
with the standard tip and plate. The third and fourth impingers should be the Greenburg-Smith
design modified so that the glass tube has an unconstricted 13 mm ID and extends to within
13 mm of the flask bottom. The fourth impinger outlet connection should allow insertion of a
thermometer capable of measuring ± 1
EC of true value in the range of 0 to 25EC.
4.1.11 Water circulating bath - A bath and pump circulating system which is capable of
providing chilled water flow to the condenser and sorbent trap water jackets should be used.
Typically a submersible pump is placed in the impinger ice water bath so that the ice water
contained there can be used. The function of this system should be verified by measuring
sorbent trap gas entrance temperature 
#20EC.
4.1.12 Pitot tube - The pitot tube, preferably of Type S design, shall meet the
requirements of Method 2. The pitot tube is attached to the probe as shown in Figure 1. The
proper pitot tube-sampling nozzle configuration for prevention of aerodynamic interference is
shown in Figures 2.6 and 2.7 of Method 2. The Type S pitot tube assembly shall have a known
coefficient, determined as outlined in Sec. 4 of Method 2.
4.1.13 Differential pressure gauge - The differential pressure gauge should be an
inclined manometer or the equivalent as described in Method 2. Two gauges are required:
one gauge to monitor the stack velocity pressure ()P), and the other to measure the orifice
pressure differential ()H).
4.1.14 Metering system - The metering system should consist of a dry gas meter with
2% accuracy, a vacuum pump, a vacuum gauge, orifice meter, thermometers or
thermocouples capable of measuring ± 3
EC of true value in the range of 0 to 90EC; and related
equipment as shown in Figure 1. Thermocouples should be used to monitor the temperature
at the following sampling train locations:
@
stack gas
@
probe liner
@
filter holder
@
sorbent trap entrance
@
silica gel impinger exit
@
dry gas meter inlet and
@
dry gas meter outlet.
Other metering systems capable of maintaining isokinetic sampling rates within 10% and
determining sample volumes to within 2% may be used if approved. Sampling trains with
metering systems designed for sampling rates higher than those described in APTD-0581 and
APTD-0576 (Air Pollution Technical Document, see references) may be used if the above
specifications can be met. When the metering system is used with a pitot tube, the system
should permit verification of an isokinetic sampling rate through the use of a nomograph or by
calculation.

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4.1.15 Barometer - A mercury (Hg), aneroid, or other barometer capable of measuring
atmospheric pressure to within ± 2.5 mm Hg is needed. A preliminary check of a new
barometer should be made against a mercury-in-glass barometer or the equivalent. The
absolute barometric pressure may be obtained from a nearby weather service station and
adjusted for elevation difference between the station and the sampling point. Either subtract
2.5 mm Hg from the station value for every 30 m elevation increase or add the same for an
elevation decrease. If the barometer cannot be adjusted to agree within 0.1 in. Hg of the
reference barometric pressure, it should be repaired or discarded.
4.1.16 Gas density determination equipment - The equipment necessary for conducting
Methods 2 - 4 for determining stack gas flow, molecular weight and moisture content,
respectively, should be used. Required measurements include stack gas velocity and static
pressure; gas temperature; concentrations of O , CO , and N (by difference), metered gas
2
2
2
volumes and meter temperatures and pressure; and condensate weight gain collected by the
impinger train. All equipment should meet Methods 2 through 4 requirements.
4.2
Sample recovery equipment
4.2.1
Fitting caps - Ground glass or cleaned aluminum foil to cap the exposed sections
of the train.
4.2.2
Wash bottles -Teflon® .
4.2.3
Probe-liner, probe-nozzle, and filter-holder brushes - These should be constructed
with nylon or Teflon® bristles with precleaned stainless steel or Teflon® handles. The probe
brush should have extensions of stainless steel or Teflon® at least as long as the probe. The
brushes should be properly sized and shaped to brush out the nozzle, probe liner, and front
half filter holder.
4.2.4
Filter storage container - Typically a glass petri dish sealed with Teflon® tape is
used. Petri dishes should be cleaned according to glassware cleaning procedures listed in this
method (Sec. 6.1.4).
4.2.5
Balance - This balance is used for measuring weight gain of the impingers and
sample bottle weights as well. Typically a 0 to 2000-g balance is used. The balance should
be accurate to within 0.5 g, verified with ASTM Class 1 (Class S) weights.
4.2.6
Aluminum foil - Heavy duty cleaned by rinsing three times with methylene chloride
and once with toluene, stored in pre-cleaned glass petri dish or glass jar.
4.2.7
Graduated cylinder - Glass, 250-mL, with ± 1 mL resolution (this cylinder can be
used for impinger volume determinations in place of the balance).
4.2.8
Glass sample storage container - Amber glass bottle for sample glassware
washes, 500- or 1000-mL, with leak-free Teflon® -lined caps. The bottles should be either
purchased as precleaned or cleaned according to glassware cleaning procedures listed in this
method (Sec. 6.1.4).

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5.0
REAGENTS
5.1
Filters - Glass fiber filters, without organic binder, exhibiting at least 99.95% efficiency
(< 0.05% penetration) on 0.3 µm dioctyl phthalate smoke particles. One filter from each batch is
tested for contamination using the procedure in Sec. 5.1.2. If the filter fails the test, then all filters
must be cleaned and retested before their initial use according to the following procedures.
5.1.1
Precleaning - Place no more than 50 filters in a Soxhlet extraction apparatus.
Charge the Soxhlet with toluene and reflux for 16 hours. After extraction, allow the Soxhlet to
cool. Remove the filters and dry under a clean nitrogen (N ) stream. Store the filters in
2
cleaned glass petri dishes or amber glass bottles sealed with Teflon® tape or Teflon® -lined
caps prior to using them.
5.1.2
As a quality control check prior to the field test, take one precleaned filter and
perform Soxhlet extraction with toluene for 16 hours. Remove the toluene extract and analyze
according to Method 8290. No analytes may be observed above the detection limit.
5.1.3
Filter surrogate spike solution - As stated in Sec. 7.3.3, this method calls for both
the filter and the XAD-2® sorbent to be spiked with the same set of isotopically labeled
PCDD/PCDF standards. Surrogate spikes are added to the sorbent prior to sampling and to
the filter immediately before the sample extraction. The filter and XAD-2® fractions (including
the associated glassware rinses) are extracted separately and analyzed separately. The
surrogate standards listed in Table 1 should be used for both the filter spike and sorbent spike.
5.1.4
To ensure proper filter spiking, the isotopically-labeled standard solution, which
is normally at a concentration of 0.1 ng/µL, is diluted to 0.004 ng/µL with nonane, for a dilution
factor of 25. This spiking solution will be used to spike the surface of the filter as discussed
in Sec. 7.3.1.
5.2
Sorbent resin - Amberlite XAD-2® resin. XAD-2® may be purchased precleaned or
cleaned by the laboratory. If the sorbent has not been precleaned, a cleaning procedure capable
of producing resin meeting the quality control check in Sec. 5.2.1.8 shall be implemented. The
procedure given below has been found to produce excellent results.
5.2.1
Sorbent resin cleaning procedure
5.2.1.1
Place the sorbent resin in a clean beaker and rinse with reagent water.
Discard the rinse. Fill the beaker a second time with reagent water and allow the resin
to stand overnight. Discard this second rinse.
5.2.1.2
Place the sorbent resin in an all-glass thimble of a large Soxhlet
extractor. The sorbent resin will float when in contact with methylene chloride.
Therefore, add a glass wool plug on top of the resin in the thimble, and weight the glass
wool plug down with a stainless steel ring that fits inside the thimble.
5.2.1.3
Place the thimble filled with resin into the Soxhlet extractor, add organic-
free reagent water to the distilling flask, apply heat, and extract the resin for 8 hours.
5.2.1.4
Allow the Soxhlet extractor to cool, discard the water, and add methanol
to the extractor. Apply heat and extract for 22 hours.

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5.2.1.5
Again allowing the extractor to cool, drain off the methanol, replace it
with methylene chloride. Make sure that the stainless steel ring and glass wool plug are
still in place and extract for 22 hours.
5.2.1.6
Extract the resin a fourth time, using toluene as the extraction solvent,
for 22 hours.
5.2.1.7
Following the toluene extraction, the sorbent resin must be dried under
a stream of clean dry nitrogen or other inert gas. This may be accomplished by
transferring the resin to a large diameter glass column and flowing the gas through the
column. The gas may be heated to less than 40
EC, using a steam bath or other
appropriate heat source. Continue the inert gas flow through the resin until all the
residual solvent is removed. The flow rate should be sufficient to agitate the resin