Method NCASI 99.01 (1999)

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NCASI METHOD IM/CAN/WP-99.01
IMPINGER/CANISTER SOURCE SAMPLING METHOD FOR

SELECTED HAPS AT WOOD PRODUCTS FACILITIES
NCASI SOUTHERN REGIONAL CENTER
JANUARY 1999
Acknowledgements
This method was prepared by Dr. MaryAnn Gunshefski, Senior Research Scientist, Dr. David
Word, Program Manager, Jim Stainfield, Research Associate, and Steve Cloutier, Research
Associate, at the NCASI Southern Regional Center. Other assistance was provided by Terry
Bousquet, Senior Research Scientist, with the NCASI West Coast Regional Center.
For more information about this method, contact:
Dr. David Word Dr. MaryAnn Gunshefski

NCASI NCASI
PO Box 141020 PO Box 141020
Gainesville, FL 32614 Gainesville, FL 32614
(352) 377-4708 ext. 241 (352) 377-4708 ext. 244
FAX (352) 371-6557 FAX (352) 371-6557
email D_Word@src-ncasi.org email M_Gunshefski@src-ncasi.org
For more information about NCASI publications, contact:
Publications Coordinator
NCASI
PO Box 13318
Research Triangle Park, NC 27709-3318
(919) 558-1987
National Council of the Paper Industry for Air and Stream Improvement, Inc. (NCASI). 1999.
Methods Manual, Impinger/Canister Source Sampling Method for Selected HAPs at Wood
Products Facilities, Research Triangle Park, N.C.: National Council of the Paper Industry for Air
and Stream Improvement, Inc.
 2000 by the National Council of the Paper Industry for Air and Stream Improvement, Inc.
NCASI’s Mission
To serve the forest products industry as a center of excellence for providing technical
information and scientific research needed to achieve the industry’s environmental goals.
i
Disclaimer
The mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
ii
IM/CAN/WP-99.01, Impinger/Canister Method for Selected HAPs
at Wood Products Facilities
NCASI METHOD IM/CAN/WP-99.01
IMPINGER/CANISTER SOURCE SAMPLING METHOD FOR

SELECTED HAPS AT WOOD PRODUCTS FACILITIES
1.0 Introduction
1.1 This method is intended for the sampling of selected hazardous air pollutant (HAP)
concentrations in stationary source emissions at wood products mills or panel plants. The
analysis of the impinger contents is performed by gas chromatography/flame ionization
detection (GC/FID), and a colorimetric method. The analysis of the canister contents is
performed by gas chromatography/mass selective detection (GC/MSD) and gas
chromatography/flame ionization detection (GC/FID). This method has been written to
conform with the contents and format of EPA Air Methods.
2.0 Method Description

2.1 Principle, applicability, interferences, and stability
2.1.1 Principle - A sample of the source gas is drawn through three midget
impingers, each containing chilled organic free water. A Teflon-head pump and a
critical orifice are used to maintain the flow through the impingers of
approximately 400 mL/min. A portion of the gas exiting the pump is drawn into
an evacuated stainless steel canister for an analysis of the compounds not trapped
in the aqueous impingers. The water from the impingers is analyzed by direct
injection into a gas chromatograph equipped with a flame ionization detector
(GC/FID). The formaldehyde concentration in the impinger solution is determined
by the acetylacetone procedure. This procedure involves the reaction of
acetylacetone with formaldehyde to produce a colored derivative which is
measured by colorimetric analysis.
For analysis of the canister contents, a sample is drawn from the canister and is
analyzed by cryogenic preconcentration followed by injection into a gas
chromatograph equipped with a mass selective detector (GC/MSD). For the
analysis of terpene concentrations collected in the canister, a second sample is
drawn from the canister and is analyzed by injection into a gas chromatograph
equipped with a flame ionization detector (GC/FID). In both analyses, the
retention times of each of the compounds are compared with those of known
standards containing the same compounds. Concentrations of the analytes are
calculated from calibration curves obtained from analysis of standard solutions.
A diagram summarizing these analyses and the corresponding analytes is given in

Figure 1. The three character designations given in this diagram for the individual
analyses will be used throughout the method to distinguish them. EPA Methods
1 January 1999
1-4, or equivalent methods, must be performed in order to obtain mass emission

rates. These methods are not described in this document.
2.1.2 Applicability - The method has been evaluated though the use of train spikes and
run spikes performed during an extensive field sampling effort. This method was
found to be applicable for the measurement of these selected HAPs found in
emission vents at wood products facilities. This method is not applicable if the
moisture content of the source gas is greater than approximately 60% (by
volume).
2.1.3 Interferences - Compounds present in the source gas can coelute with the analytes
of interest during the chromatographic analysis. These types of interferences can
be reduced by appropriate choice of GC columns, chromatographic conditions,
and detectors. Method interferences may also be caused by contaminants in
solvents, reagents, glassware and other sample processing hardware.
2.1.4 Stability – A formal stability study has not been performed, but laboratory tests
show that the impinger catch was stable for approximately 2 weeks if kept
refrigerated, at which time acrolein begins to degrade. At room temperature, the
acrolein in the impinger catch degrades in a matter of hours. The canister catch,
in general, was stable for over 3 weeks.
2.1.5 Validation – This method is designed to be a self-validating method. This is

accomplished through the use of spikes during the sampling events. It has not
been evaluated using the United States Environmental Protection Agency (EPA)
Method 301, Field Validation of Emission Concentrations from Stationary
Sources (Appendix A to CFR 63).
2.2 Apparatus
2.2.1 Sampling apparatus - A diagram of the sampling train is shown in Figure 2.
2.2.1.1 Heated Sampling Probe - The sampling probe is constructed of 1/2

inch OD stainless steel tubing. For wood products sources, the
probe is maintained at 250 ± 25°F. The probe inlet is placed near
the center of the stack or duct.
2.2.1.2 Heated Filter Box - The heated probe is directly connected to a

heated box containing a Teflon filter. The filter housing and
connections are made of stainless steel. A thermocouple connected
to or within the filter housing is used to record the filter
temperature which should be maintained at 250 ± 25°F. An
unheated Teflon line is used to convey the sample from the back of
the heated filter box to the first impinger.
2 January 1999
2.2.1.3 Midget Impingers - Three midget impingers are connected in series

to the end of the Teflon line exiting the heated filter box. The first
impinger has a frit on the end of the stem to improve gas/liquid
contact. The following two impingers have regular tapered stems.
All impinger train connectors should be glass and/or Teflon.
2.2.1.4 Filter - A second Teflon filter can be used after the impingers to
prevent any fiber, debris, or water from accidentally being drawn
into the sample pump system.
2.2.1.5 Variable Area Flow Meter - A flow meter should be placed in line
after the impingers for a flow check during sampling.
2.2.1.6 Flow Control Device - A 400 ± 50 mL/min critical orifice should

be used for flow control.
2.2.1.7 Teflon Head Vacuum pump - The critical orifice is followed by a

pump, with a Teflon head, capable of providing a vacuum of about
18 inches of Hg. (Pump capacity should be sufficient to obtain and
maintain critical conditions at the orifice.)
2.2.1.8 Variable Area Flow Meter - A flow meter should be placed in line
before the canister for a flow check during sampling.
2.2.1.9 Needle valve - A needle valve is placed before the canister to

regulate the sample flow.
2.2.1.10 Canisters - 6 L SUMMA™ polished canister or 6 L SilcoSteel™

canister is used to collect a portion of the sample gas.
2.2.1.11 Thermometer - An accurate thermometer is used to measure the

canister and ambient temperature.
2.2.1.12 Pressure Gauge - A pressure or vacuum gauge capable of

indicating ± 0.1 in Hga (absolute) is placed after the impingers and
before the canister. The gauge is used to indicate the canister
pressure before and after the sample run as well as during the leak
check procedure. The gauge can also be used to determine
barometric pressure.
2.2.1.13 Sample storage bottles - Glass (i.e., 40 mL VOA vials) or

polyethylene bottles can be used to store the impinger catch sample
after stack sampling is complete.
3 January 1999
2.2.2 GC/FID analysis apparatus (impinger analysis) [AQU]
2.2.2.1 Laboratory glassware - Volumetric pipets, volumetric flasks,

autosampler vials, syringes, and cuvettes necessary for standards
preparation and analysis.
2.2.2.2 Gas chromatography system - Gas chromatography analytical

system complete with a temperature-programmable gas
chromatograph suitable for splitless injection and all required
accessories including syringes, analytical columns and gases.
2.2.2.3 Column - 30 m x 0.32 mm x 0.25 µm bonded phase DB-WAX

fused silica capillary column (J&W Scientific or equivalent), or 30
m x 0.53 mm x 3 µm bonded phase DB-624 fused silica capillary
column (J&W Scientific or equivalent), or other column shown to
be capable of separating the analytes of interest.
2.2.2.4 GC detector - Flame ionization detector with appropriate data

system.
2.2.3 Formaldehyde analysis apparatus (impinger analysis) [FOR]
2.2.3.1 Spectrophotometer - A spectrophotometer capable of measuring

absorbance at 412 nm.
2.2.4 Cryogenic preconcentration/GC/MSD analysis apparatus (canister analysis) [T14]

2.2.4.2 Cryogenic concentration system - A cryogenic preconcentrator is

required to concentrate the sample and to introduce it to the
GC/MSD system.

2.2.4.4 Column - 60 m x 0.32 mm x 0.25 µm bonded phase DB-624 fused

silica capillary column (J&W Scientific or equivalent), or other
column shown to be capable of separating the required analytes.
2.2.4.5 Mass selective detector – A mass selective detector capable of

scanning from 29 to 300 amus every 2 seconds or less using 70
4 January 1999
volts electron energy in the electron impact ionization mode, and

appropriate data system.
2.2.5 GC/FID analysis apparatus (canister analysis) [TER/THC]

2.2.5.2 Sample loop injection system - A system capable of extracting a

sample from the canister and into a sample loop which can then
inject the sample onto the GC/FID system.

2.2.5.4 Column - 30 m x 0.32 mm x 0.25 µm bonded phase DB-1 fused

silica capillary column (J&W Scientific or equivalent), or other
column shown to be capable of separating the terpenes of interest.
2.2.5.5 GC detector - Flame ionization detector with appropriate data

system.
2.2.6 Combustion gas analysis [COx]
2.2.6.1 Bacharach gas analyzer.
2.3 Reagents
2.3.1 Water - Deionized water is to be used as the impinger collection liquid, and in the
preparation of all standard and spike solutions.
2.3.2 Pure compounds - Reagent grade acetaldehyde, acrolein, propionaldehyde,

methyl ethyl ketone, methyl isobutyl ketone, methanol, phenol, 37%
formaldehyde solution (formalin), camphene, p-mentha-1,5-diene, 3-carene,
cumene, p-cymene, limonene, α-pinene, β-pinene, and ethyl ether for preparation
of standard and spike solutions.
2.3.3 GC/FID calibration primary stock solution (impinger analysis) [AQU] - Prepare
stock solution by diluting an aliquot of the pure compounds in a 100 mL
volumetric flask according to the following table.
5 January 1999
Amount to Add to 100 mL

Compound Volumetric Flask (µL)
acetaldehyde 128
acrolein 119
methanol 126
methyl ethyl ketone 124
methyl isobutyl ketone 125
propionaldehyde 124
phenol* 100 mg
*solid
2.3.4 GC/FID calibration and matrix spike solutions (impinger analysis) [AQU] -
Prepare standard solutions by serial dilutions of the stock solution. The
recommended calibration range is 0.5 to 1000 mg/L. Prepare matrix spike
solutions by calculating the concentration of analytes desired, and diluting the
primary stock solution.
2.3.5 GC/FID internal standard primary spiking solution (impinger analysis) [AQU] -
For calibration standard analysis, prepare primary stock solution by adding 0.312
mL cyclohexanol and diluting to 100 mL with DI water in a 100 mL volumetric
flask (3 mg/mL cyclohexanol). For impinger analysis, prepare stock solution by
adding 3.12 mL cyclohexanol and diluting to 2 L with DI water in a 2 L
volumetric flask (1.5 mg/mL cyclohexanol).
2.3.6 Acetylacetone reagent (impinger analysis) [FOR] - Prepare by dissolving 15.4 g of

ammonium acetate in about 50 mL of DI water in a 100 mL volumetric flask.
Add 0.20 mL of acetylacetone to this solution, along with 0.30 mL of glacial
acetic acid. Mix thoroughly and dilute to 100 mL with DI water. Store reagent in
a brown glass bottle in the refrigerator. Reagent is stable for at least two weeks.
2.3.7 Formaldehyde analysis primary stock solution (impinger analysis) [FOR] -

Prepare stock solution by diluting 2.7 mL of formalin in 1000 mL volumetric
flask with DI water. (1000 mg/L formaldehyde)
2.3.8 Formaldehyde analysis calibration standard solution (impinger analysis) [FOR] -

Prepare standard solution by diluting 1.0 mL of primary stock solution in 100 mL
volumetric flask with DI water. (10 mg/L formaldehyde)
2.3.9 Formaldehyde analysis calibration solutions (impinger analysis) [FOR] - A series

of calibration standards are made from the standard solution by adding 0, 0.1, 0.2,
0.4, 1.0 and 1.5 mL of the standard solution to individual screw-capped vials. The
volume in each vial is adjusted to 2.0 mL with DI water. This corresponds to 0,
0.5, 1, 2, 5, 7.5 mg/L calibration solutions. To each vial, 2.0 mL of the
6 January 1999
acetylacetone reagent is added and the procedure described in Section 2.4.4.3 is

then followed.
2.3.10 GC/MSD calibration primary stock gas cylinder [T14 analytes] (canister analysis)
[T14] - Obtain a cylinder containing the compounds of interest at a level of
1 ppmv. Refer to EPA Compendium Method TO-14 for possible compound list.
2.3.11 GC/MSD calibration and matrix spike gas canisters [T14 analytes] (canister
analysis) [T14] - Prepare standard canisters by serial dilutions of the stock
cylinder. The recommended calibration range is 50 to 500 ppbv.
2.3.12 GC/MSD calibration primary stock gas canister [aqueous analytes] (canister
analysis) [T14] – Prepare a primary stock gas canister by first preparing a stock
solution by diluting an aliquot of the pure compounds in a 100 mL volumetric
flask according to the following table.

acetaldehyde 281
acetone 369
acrolein 334
methanol 202
methyl ethyl ketone (2-butanone) 448
methyl isobutyl ketone 628
propionaldehyde 360
phenol (solid) 439
Inject 10 µL of this stock solution into an evacuated canister along with 140 µL of
water. Fill canister with N2 to 60 in Hga. This will result in a canister
concentration of 1000 ppbv for these compounds.
2.3.13 GC/MSD calibration and matrix spike gas canisters [aqueous analytes] (canister
analysis) [T14] - Prepare standard canisters by serial dilutions of the stock
canister. The recommended calibration range is 50 to 500 ppbv.
2.3.14 GC/MSD internal standard cylinder (canister analysis) [T14] - Obtain a cylinder
containing internal standard compounds for the GC/MSD analysis.
Bromochloromethane, 1,-4-difluorobenzene, and d5-chlorobenzene are commonly
used. Refer to EPA Compendium Method TO-14 for additional guidance.
2.3.15 GC/FID calibration primary stock gas canister (canister analysis) [TER] – Prepare
a primary stock gas canister by first preparing a solution containing the analytes in
ethyl ether using the following table:
7 January 1999
camphene 809
p-mentha-1,5-diene 810
3-carene 786
cumene 694
p-cymene 780
limonene 811
α-pinene 795
β-pinene 793
Inject 100 µL of this solution into a evacuated canister and fill to 60 in Hga. This
will result in terpene concentrations of 100 ppmv.
2.3.16 GC/FID calibration canisters (canister analysis) [TER] – Prepare calibration

canisters by serial dilutions of the stock canister. The recommended calibration
range is 1 to 300 ppmv.
2.3.17 GC/FID calibration primary stock gas canister (canister analysis) [THC] - Obtain
a cylinder containing propane at a level of 900 ppmv.
2.3.18 GC/FID calibration and matrix spike gas canisters (canister analysis) [THC] -
Prepare standard canisters by serial dilutions of the stock cylinder. The
recommended calibration range is 15 to 2700 ppmv as C (3 to 900 ppmv as
propane).
2.4 Procedure
2.4.1 Sample Bottle Preparation - Determine the number of samples bottles required for
the sampling trip. Weigh each bottle and record the pre-sampling weight on the
bottle. To each bottle add 1 mL of the 1.5 mg/mL cyclohexanol internal standard
stock solution (see section 2.3.5) and 75 mL DI H2O.
2.4.2 Sampling - A sample field data sheet is shown in Figure 3.
2.4.2.1 Measure and record ambient temperature and barometric pressure.

Source gas flow rate is determined by EPA methods 1-4 or
equivalent methods.
2.4.2.2 Preparation of collection train - The sampling train consists of: a

heated probe, heated filter box, three midget impingers in series
immersed in an ice bath, a critical orifice, a rotameter, a Teflon-
head sample pump, and an evacuated canister with a needle valve
flow controller, rotameter, and a pressure gauge. For each emission
8 January 1999
source tested the sample probe and filter housing should be cleaned
with organic-free water and the filter replaced. The three
impingers each contain approximately 25 mL of organic free water.
For sources with very high amounts of moisture (>40%), a fourth
dry impinger, used as the first train impinger, may be necessary as
a water dropout. A clean evacuated canister is attached to the
sample pump exhaust vent. This part of the system includes the
vacuum/pressure gauge, rotameter, needle valve, and canister
temperature indicator. The critical orifice should allow collection
of about 400 mL/min of dry air. A sample collection time of one
hour is used.
2.4.2.3 Leak and flow check procedure - The sample system must be
checked for leaks prior to sampling. How the leak check is
performed is dependent on the configuration of the train as
designed by the manufacturer. In general, a leak test of the probe ,
impingers, and pump would be performed by drawing a vacuum on
the system and testing for a change in pressure with an inline
gauge. The canister sampling portion can be combined with the
impinger section or treated separately. This would also require a
vacuum or pressure gauge. The canister valve is kept closed until
after any leak check is performed. The leak check procedure shall
be conducted when all of the measurement system's components
have reached their appropriate operating temperatures.
For a vacuum leak check, plug the sampling probe inlet tip and
turn on the pump to draw a vacuum. When the vacuum reading is
approximately 15 inches of Hg, isolate the test section with the
on/off valve. Note the beginning and ending readings on the
vacuum gauge over a two minute period. An acceptable leak rate
must be less that 1.0 inch of Hg / 2 min. A leak may be indicated
by a flow of bubbles in the impinger (leak ahead of the impingers),
liquid being drawn into the stem of the impinger (leak in an
impinger or behind the impingers), or a loss of vacuum. If a leak is
present, tighten fittings, connections, and impingers and restart
leak check procedure. Slowly and carefully remove the plug from
the end of the probe to prevent the filter from dislodging from the
backing plate or water from reversing through the impinger stems.
After the system has been proved to be leak free or has an
acceptable leak rate, the canister and gauge must be isolated and
the vacuum pressure of the evacuated canister be checked by
opening the canister valve. A pressure of less than 1.0 in Hga is
required to assure that the canister can withdraw enough sample
without diluting the sample unnecessarily or that any
contamination has been introduced since the cleaning of the
9 January 1999
canister. After verifying that the canister has the correct vacuum
pressure close the canister valve.
Next, check the flow rate at the probe inlet with a bubble
flowmeter. The flow rate should be comparable to the flow rate of
the critical orifice with the impingers off-line. Record five
measurements of the flow rate and turn off the pump.
2.4.2.4 Sample collection - Insert the probe into the stack perpendicular to
the flow and secure it. Start the pump, recording the time and the
flow reading on the rotameter. One minute after starting the sample
run open the canister valve and adjust the flow rate to the canister
with the needle valve. This is done to insure that the canister is
sampling stack gas and not clean air from the train system volume.
At the end of the sample run turn off the pump and record the
canister temperature and pressure, then close the canister valve. A
normal sample run is 60 minutes. Record the stop time and
remove the probe from the vent. Turn on the pump and recheck the
sample flow rate at the probe inlet and turn off the pump. If the
flow rate has changed significantly, redo sampling with fresh
capture water. A slight variation (<10%) in flow can be averaged.
Disconnect the Teflon tubing at the back of the heated box. Rinse
the line into the impingers by adding about 10 mL of deionized
water into the tubing. Use the sample pump to "pull" the rinse
water into the first impinger.
2.4.3 Sample Recovery - Transfer the contents of the impingers into appropriate labeled
and pre-weighed sample storage bottle. The contents of the three impingers can
be combined into one bottle. If a large amount of water was collected in the
dropout impinger, 2 bottles can be used. Store sample bottles in a cooler with ice,
or refrigerated at approximately 4oC until they can be stored in a laboratory
refrigerator. Place cap on canister valve and ship to the laboratory.
2.4.4 Sample analysis
2.4.4.1 Preparation of impinger samples [AQU] - Remove bottles from

refrigerator. Weigh the sample bottles and record weights on the
bottle. Transcribe initial and final bottle weight to sample field
data sheet. Bottles do not need to be at room temperature before
weighing.
2.4.4.2 GC/FID impinger analysis [AQU] - Analysis is performed by

direct aqueous injection into the GC/FID. Place an aliquot of the
impinger catch in an autosampler vial and analyze. Representative
10 January 1999
conditions for the GC/FID analysis are given in Tables 1 and 2.

Other chromatographic columns and conditions may be used if it
has been established that the compounds are separated and quality
control parameters are met. Some possible interfering compounds
include ethanol, methyl mercaptan, dimethyl sulfide, and dimethyl
disulfide. Once the GC/FID system is optimized for analytical
separation and sensitivity, the sample operating conditions must be
used to analyze all samples, blanks, calibration standards and
quality assurance samples. Note that constant injections of aqueous
samples can cause water to buildup in the system. This will cause
the retention times to shift, and the peaks to broaden. It is
recommended that after approximately 50 injections a bakeout of
the system be performed. This should consist of heating the
injector to 250oC, the oven to over 2000C and the detector to 275oC
for several hours.
2.4.4.3 Formaldehyde sample analysis [FOR] - Remove a 2.0 mL aliquot

of the impinger sample and transfer to a screw-capped vial. Add
2.0 mL of the acetylacetone reagent and mix thoroughly. Place vial
in a water bath at 60oC for 10 minutes. Allow vials to cool to room
temperature. Transfer solution to cuvette and measure the
absorbance at 412 nm. If the sample concentration is above the
calibration curve, dilute original sample solution and repeat entire
procedure. Do not dilute colored (derivatized) samples.
2.4.4.4 Preparation of canisters – Record pressure of canisters when

returned to the lab. Add humidified nitrogen gas (N2) to each
canister to increase the pressure in the canister to approximately 40
in Hga. Record final pressure.
2.4.4.5 GC/MS canister analysis [T14] – Analysis is performed by

removing a sample from the canister and using cryogenic
preconcentration to remove the moisture, air, and to concentrate
the sample. This is followed by a gas chromatograph with a mass
selective detector. Representative conditions for the concentration
and GC/MSD analysis are given in Table 3.
2.4.4.6 GC/FID canister analysis [TER/THC] – Analysis is performed by

using a gas sample loop injection port for introduction of the
sample into the GC/FID. Representative conditions for the
GC/FID analysis are given in Table 4.
2.4.4.7 Bacharach gas analysis [COx] – A sample of the canister contents

is analyzed using the Bacharach gas analyzer for CO, O2 and CO2.
Record readings.
11 January 1999
2.4.5 Quality Assurance/Quality Control - Each field sampling program or laboratory

that uses this method is required to operate a formal quality assurance program.
Laboratory or field performance is compared to established criteria to determine if
the results of analyses meet the performance criteria of the method.
2.4.5.1 Field blank samples - A field blank sample of water must be

prepared to assure that the water being used in the impingers is not
contaminated. It is made in the field by filling a 40 mL VOA vial
or polyethylene bottle with the same water being used to fill the
impingers.
2.4.5.2 Field duplicate samples - Duplicate samples should be collected

and are then analyzed as separate samples. One duplicate is
collected per mill or per every ten sample runs conducted at a mill,
whichever is more stringent. For the duplicate, dual impinger
trains and pumps may be connected to a single probe and filter
box. The average of the duplicate values are reported for the run
value. Results of the duplicate sample analysis are reported with
the sample results. There are no acceptance criteria for the
analytical results of the field duplicates (see Figure 4).
2.4.5.3 Field train spike sample- A field train spike recovery run should be
conducted for each mill tested. This spike recovery test should be
conducted on the full sample train, that is the spike solution should
be introduced into the tip of the sampling system (into the heated
probe). The sample train is then operated outside or independent
of the source(s) tested. The field spike solution should contain all
compounds that are to be sampled for and reported. Sample flow
rate and sample time should be identical or very close to the actual
sample runs. Care must be taken to prevent introduction of any
ambient organic contaminants during this procedure. If a single
spike is used, the mass of each analyte introduced should be
targeted to be ± 50% of the mass expected to be captured in an
actual sample run. Alternatively, both "low" and "high" spike
solutions can be used on two separate spike recovery runs to
bracket the expected capture from the source. Field spike recovery
results should be reported. A criterion for field spike recovery of
70% to 130% is used to determine the validity of the sampling
effort. This type of spiking provides a check of the complete field
sampling procedure, sample storage, and sample analysis.
2.4.5.4 Field run spike sample – A field run spike should be conducted for
each mill tested. Duplicate sample trains are set up to sample the
source, then the first impinger of one of these two trains is spiked.
The two sample trains are then run as a typical source sample.
12 January 1999
Spike recovery is determined by subtracting the source

concentration obtained from the non-spiked-train from the total-
spike-plus-source concentration determined from the spiked train.
Targets and criteria are as specified in the paragraph above (see
Figure 4).
2.4.5.5 Laboratory blank sample - A laboratory blank sample should be

analyzed with each batch of samples. A batch is considered no
more than 20 samples of similar matrix type.
2.4.5.6 Laboratory duplicates - A replicate injection of one sample in the

analytical batch should be performed. The results of the duplicate
analysis should be within 10% of the mean of the original and
duplicate sample analysis.
2.4.5.7 Laboratory matrix spike samples - A laboratory matrix spike

sample may be prepared with each group of similar matrix type.
Using the mean concentration determined by the replicate analyses,
or the background level determined from a single measurement,
determine the spiking level which will give one to four times the
background. If the background sample does not have detectable
levels of analytes, spike the sample at approximately five times the
lowest calibration level of the instrument. Spike the sample with
the determined amount of the calibration standard/matrix spike
solution and proceed to analyze the sample in the normal manner.
The results can be considered acceptable if the calculated spike
recovery is 80 to 120%. In cases where multiple analytes are
present, the analyte with the highest concentration should govern
the acceptance criteria.
2.5 GC calibration
2.5.1 Internal standard calibration [AQU, T14]
2.5.1.1 For [AQU] analysis, place 10 µL of the internal standard solution

into an autosampler vial. Fill the autosampler vial with a high
level calibration standard. The internal standard concentration will
be 15 mg/L. For [T14] analysis, inject a high level calibration
standard along with the internal standards. Determine the retention
time of the analytes relative to the internal standard. Each analyst
should optimize the temperature program or instrument conditions,
as necessary, to establish distinct separate peaks.
2.5.1.2 Calculate the relative response factor for the analytes (RRFM) using
Equation 1. If the average of the relative response factor for the
13 January 1999
analytes is constant, i.e., exhibits a coefficient of variation less that

20%, the calibration is acceptable and the average RRFM can be
used in all subsequent calculations; otherwise, the calibration curve
solutions must be reanalyzed and reevaluated. It may be necessary
to perform instrument maintenance prior to reanalysis. If
reanalysis also fails to produce a linear curve, new calibration
standards must be prepared and analyzed.
2.5.1.3 Analyze and calculate the percent recovery of a mid-range

calibration standard, daily, prior to each sample set, using Equation
2 to verify the calibration. The percent recovery should be between
80-120%. If it is not, either prepare a new standard or perform
instrument maintenance. If necessary, re-calibrate the instrument.
______________________________________________________________________________
Equation 1
AM C IS
RRFM = x
AIS C M
AM = area of analyte peak

AIS = area of internal standard peak
CM = concentration of analyte injected (mg/L)
CIS = concentration of internal standard injected (mg/L)
______________________________________________________________________________
______________________________________________________________________________
Equation 2
AS x C IS
Conc (mg/L) =
AIS x RRFM
As = Area of the analyte peak in the sample

CIS = Concentration of the internal standard (mg/L)
AIS = Area of the internal standard peak
RRFM = Relative response factor of analyte (Section 2.5)
______________________________________________________________________________
2.5.2 External standard calibration [TER, THC]
2.5.2.1 Inject a high level calibration standard and determine the retention
time of each analyte. Each analyst should optimize the temperature
program or instrument conditions, as necessary, to establish
distinct separate peaks.
14 January 1999
2.5.2.2 Measure and plot the response of each analyte vs. concentration. If
the correlation coefficient of the graph is greater than 0.99, the
calibration is acceptable and the equation of the line can be used in
all subsequent calculations; otherwise, the calibration curve
solutions must be reanalyzed and reevaluated. It may be necessary
to perform instrument maintenance prior to reanalysis. If
reanalysis also fails to produce a linear curve, new calibration
standards must be prepared and analyzed.
2.5.2.3 Analyze and calculate the concentration of a mid-range calibration

standard, daily, prior to each sample set to verify the calibration.
The percent recovery should be between 80 and 120%. If it is not,
either prepare a new standard or perform instrument maintenance.
If necessary, re-calibrate the instrument.
2.6 Analytical range and minimum calibration level
2.6.1 Demonstrate that the calibration curve is linear (relative response factors exhibit a
coefficient of variation less than 20%, or correlation coefficient greater than 0.99)
throughout the range of the calibration curve.
2.6.2 Demonstrate that the analytes are detectable at the minimum levels using the
lowest level calibration curve standard.
2.7 Calculations
To determine the stack concentration of each analyte, three factors must be calculated:
the mass of the analyte in the impinger, the mass of the analyte in the canister, and the
total volume of gas sampled. The calculations to determine these factors are given in the
following sections.
2.7.1 Determination of dry volume of gas sampled:
• Convert pre- and post-flow rates to STP (Eq. 3)
• Calculate water vapor flow rate at STP (Eq. 4)
• Calculate dry flow rate at STP (Eq. 5)
• Calculate dry volume sampled at STP (Eq. 6)
15 January 1999
Equation 3
 Pi , f   TSTP 
Qi , f ( STP ) = Qi , f  x 
P  T 
 ( STP )   i , f 
Qi,f (STP) = initial or final flow rate at STP (L/min)

Qi,f = initial or final measured flow rate (L/min)
Pi.f = initial or final measured barometric pressure (in Hg)
P(STP) = pressure at STP = 29.2 in Hg
Ti,f = initial or final temperature (°R)
T(STP) = temperature @STP = 68°F = 528°R
____________________________________________________________________________
____________________________________________________________________________
Equation 4
 Pwi,wf   TSTP 
Q wi,wf (STP ) = Q i ,f (STP )  x 
P   T 
 (STP )   i ,f 
Qwi, wf (STP) = initial or final flow rate of water vapor at STP (L/min)
Pwi, wf = initial or final water vapor pressure (in Hg) [look up in H2O Vapor
Table based on Temperature]
____________________________________________________________________________
____________________________________________________________________________
Equation 5
Q i,f(STP) (Dry) = Q i,f (STP) − Q wi, wf (STP)
Q (STP) =
(Q i (STP) ) (
− Q wi (STP) + Q f (STP) − Q wf (STP) ) L/min
2
___________________________________________________________________________
16 January 1999
Equation 6
 L 
V probe, dry (L) = Q (STP)   x total sample time (min)
 min 
V probe, dry (L) = Total dry sample volume at standard temperature and pressure
____________________________________________________________________________
2.7.2 Determination of mass collected in impingers (Eq. 7)
Equation 7
mass analyte impinger ( µg) = reported conc. from lab (mg/L) x Vimp (L) x (10 3 )
Vimp = assumed volume of water in impinger = 0.100 L
Since we are adding the internal standard before sampling, and are using an
internal standard calibration curve for the [AQU] analysis, this volume is set at
0.100 L. For the calculation of the [FOR] mass, the actual volume collected in the
impinger catch must be used.
__________________________________________________________________________
2.7.3 Determination of mass collected in canister:
• Calculate volume of wet sample collected in canister (Eq. 8 and 9)
• Calculate volume of H2O vapor collected in canister (Eq. 10)
• Calculate volume of dry sample collected in canister (Eq. 11)
• Calculate correction factor (required because only a portion of total sample drawn
through probe is collected in the canister) (Eq. 12)
• Calculate total volume in canister after lab dilution (Eq. 13)
• Calculate mass collected in canister (Eq. 14)
17 January 1999
Equation 8
 T(STP)   Pi , f ( CAN ) 
Vi, f (CAN)(STP) = 6.0 L   
T  P 
 i, f (CAN)  ( STP ) 
Vi,f (CAN) (STP) = initial or final volume of canister @STP (L)

Ti,f (CAN) = initial or final temperature of canister (°R)
Pi.f (CAN) = initial or final temperature of canister (in Hga)
____________________________________________________________________________
Equation 9
Vf -i ( CAN ) (STP) = Vf ( CAN ) (STP ) − Vi ( CAN ) (STP )
Vf-i (CAN) (STP) = Volume of wet sample collected in canister @STP (L)
_____________________________________________________________________________
Equation 10
 T(STP )   P38° F (SAT ) 

VH 2 O @ 38° F (STP) ( L) = Vf − i ( CAN ) (STP ) ( L)   
T  P 
 ( 38° F )   (STP ) 
T38°F = It is assumed the temperature of the air sample leaving the 3rd impinger is
38°F = 498°R
P38°F (SAT) = vapor pressure of H2O @38°F = 0.2319 in Hga
_____________________________________________________________________________
Equation 11
V(CAN) (dry) ( L) = Vf − i ( CAN ) (STP ) ( L) − VH 2 O @ 38° F (STP ) ( L)
____________________________________________________________________________
18 January 1999
Equation 12
Vprobe (dry) ( L)
CF =
V(CAN) (dry) ( L)
CF = canister mass correction factor
____________________________________________________________________________
Equation 13
 T(STP )   Pf ( LAB) 
V f (LAB) (STP) ( L) = 6.0 L   
 Tf ( LAB)   P(STP ) 
  
Vf (LAB) (STP) = final volume of canister in laboratory (L)

Tf (LAB) = final temperature of canister in laboratory (°R)
Pf (LAB) = final pressure of canister in laboratory (in Hga)
____________________________________________________________________________
Equation 14
(  1 mole 
)
massanalyte canister (µg) = ( ppbv(wet) ) V f (LAB)(STP) ( L)  (
 (mwanalyte ) 10 −3 )
 24.0 L 
ppbv(wet) = measured conc. in lab

mwanalyte = molecular weight of analyte (g/mole)
___________________________________________________________________________
2.7.4 Calculation of source concentration
• Calculate total mass of analyte collected in sample train (Eq. 15)
• Calculate total volume of analyte collected (Eq. 16)
• Calculate source concentration (Eq. 17)
19 January 1999
Equation 15
(
mass analyte total (µg) = mass analyte impinger (µg) + massanalyte canister (µg ) x CF )
____________________________________________________________________________
Equation 16
( ) ( )  1   24.0 L 
volumeanalyte total ( L) = massanalyte total (µg) 10 -6    
 mw   1 mole 
____________________________________________________________________________
Equation 17
volumeanalyte total
ppmv (dry) = x 10 6
volumeprobe (dry)
___________________________________________________________________________
2.8 Alternative procedures - Not applicable to this method.
2.9 References
Wight, Gregory D. 1994. Fundamentals of Air Sampling, Lewis Publishers, Boca Raton,
FL.
EPA Compendium Method TO-14, “Determination of Volatile Organic Compounds

(VOCs) in Ambient Air Using SUMMA® Passivated Canister Sampling and Gas
Chromatographic Analysis,” EPA/600/4-89/017, June 1988.
20 January 1999
2.10 Tables and diagrams
Table 1. GC/FID Operating Conditions for Selected HAPs Analysis in

Impingers – DB-624 Column [AQU]
Injection: Direct (Splitless)
Injector Temperature: 170°C
Injection Volume: 1 µL
Injection Liner Size: 2 mm id (no packing)
Syringe Rinse 10 rinses with VOC free DI water
FID Detector Temperature: 275°C
H2 Flow Rate: Approx. 50 mL/min
Air Flow Rate: Approx. 500 mL/min
Makeup Gas: Helium
Makeup Gas Flow Rate: Approx. 25 mL/min
Carrier Gas: Helium
Carrier Gas Flow Rate: Constant pressure mode to give 6
mL/min at room temperature
Column: J&W DB-624, 30 m x 0.53 mm id x
3 micron fused silica capillary
column with 10 m deactivated fused
silica guard column
Cryogenics: On
Temperature Program °C:
Initial: 0°C for 3 min
Ramp 1: 5°C/min to 50°C for 0 minutes
Retention Time Order: Acetaldehyde, Methanol, Acrolein,
Propionaldehyde, Methyl Ethyl
Ketone, Methyl Isobutyl Ketone,
Cyclohexanol, Phenol
21 January 1999
Table 2. GC/FID Operating Conditions for Selected HAPs Analysis in

Impingers – DB-WAX Column [AQU]
Injection: Direct (Splitless)
Injection Volume: 1 µL
Injection Liner Size: 2 mm id (no packing)
Syringe Rinse 10 rinses with VOC free DI water
H2 Flow Rate: Approx. 50 mL/min
Air Flow Rate: Approx. 500 mL/min
Makeup Gas: Helium
Makeup Gas Flow Rate: Approx. 25 mL/min
Carrier Gas: Helium
Carrier Gas Flow Rate: Constant pressure mode to give 3
mL/min at room temperature
Column: J&W DB-WAX, 30 m x 0.32 mm id
x 1.4 micron fused silica capillary
silica guard column
Cryogenics: On
Retention Time Order: Acetaldehyde, Propionaldehyde,
Acrolein, Methyl Ethyl Ketone,
Methanol, Methyl Isobutyl Ketone,
Cyclohexanol, Phenol
22 January 1999
Table 3. GC/MS Operating Conditions for Selected HAPs Analysis

in Canisters [T14]
Cryogenic Preconcentrator
Sample Volume for Calibration: 500 mL
Module 1 Trap Temperature: -150oC
Module 1 Desorb Temperature: 20oC
Module 2 Desorb Temperature: 180oC
Module 3 Inject Temperature: 100oC
Transfer Line Temperature: 100oC
Gas Chromatograph/Mass Selective Detector
Inlet Temperature: 180oC
Carrier Gas: Helium
Carrier Gas Flow Rate: Constant flow mode at 2.0 mL/min
1.4 micron fused silica capillary
silica guard column
Cryogenics: On
Total Run Time: 57 min
Mass Range Scan: 29-250 amu
23 January 1999
Table 4. GC/FID Operating Conditions for Terpene/THC Analysis in Canisters

– DB 624 Column [TER/THC]
Injection: Split
Injection Volume: 2 mL – sample loop
Split Ratio: 1.5:1
Split Flow: 4.8 mL/min
Total Flow: 9.8 mL/min
H2 Flow Rate: 40 mL/min
Air Flow Rate: 450 mL/min
Makeup Gas: Helium
Makeup Gas Flow Rate: 45 mL/min
Carrier Gas: Helium
Carrier Gas Flow Rate: Ramped pressure mode. Initial
pressure 14.0 psi. Ramp 7 psi/min
to 9.3. Initial flow 3.2 mL/min.
0.25 micron fused silica capillary
silica guard column
Cryogenics: Off
Retention Time Order: Cumene, α-pinene, camphene, β-
pinene, p-mentha-1,5-diene, 3-
carene, p-cymene, limonene
24 January 1999
Figure 1. Schematic of Sample Analyses and Analytes
Sampling Train
Impinger Canister
Analysis Analysis
[AQU] [FOR] [T14] [TER] [THC] GC/FID [COx]

GC/FID Acetylacetone GC/FID GC/FID Analysis for Total Bacharach Gas
Analysis Procedure Analysis for Terpenes Hydrocarbons Analyzer
Acetaldehyd Formaldehyd Acetaldehyd Camphen

Calibrated CO
with
Aceton 3- O2
Acrolei
Methano Acrolei p-
CO2
Methyl Ethyl Methano cis-1,2-dichloroethylene

Ketone
Methyl Ethyl
Methyl Limonen
Ketone
Ketone
Methyl
Propionaldehyde
Ketone p-mentha-1.5-diene
Phenol Phenol
Alpha-
Propionalde
Beta-
hyde
T14 Compound
25 January 1999
Figure 2. Chilled Impinger/Canister Sampling Train for Use at Wood Products Mills to Measure Selected HAPs
Filter Variable Area

Flow Meter
Heated Probe (250 F) Heated Filter

Box (250 F)
Critical Orifice
400 mL/min
Ice Water Bath
Teflon Head
Needle Variable Pump
Valve Area Flow
Meter
6L
Canister
Vent Gas
26 January 1999
Figure 3. Field Sampling Data Sheet

NCASI HAPS TRAIN FIELD DATA SHEET
SAMPLER DATE: CANISTER ID# CAN CODE: TRAIN SPIKE
SAMPLING CODE: FIELD SPKIE Y N gas____mL aqueous_____mL
DESCRIPTION:
PRESSURE SECTION 1a SECTION 1b SECTION 2 SECTION 3 SECTION 4 SECTION 5
LEAK INITIAL
CHECK FINAL
DIFFERENCE
PROBE SAMPLE FLOW RATES COMBINED TRAIN FLOW RATES
PRE-RUN POST-RUN PRE-RUN POST-RUN
AVG
% DIFFERENCE % DIFFERENCE
AMBIENT TEMPERATURE / PRESSURE
PRE-RUN POST-RUN
°F in. Hga °F in. Hga
IMPINGER LEFT VAC. GA. CANISTER VENT
TIME FLOW (mL/min) (in. Hga) TIME P (in Hga) FLOW (mL/min) TEMP °F FLOW (mL/min)
START
10
15
20
25
30
35
40
45
50
55
STOP
COMMENTS:
27 January 1999
Figure 4. Various Apparatus of Sampling Trains
Aqueous Impingers
N SUMMA Canister
Heated Pump/
Run 1 Probe Filter Control Run Normal
Box F Box
Aqueous Impingers
D
Pump/
Control Run Duplicate
F Box
Heated
Run 2 Probe Filter
Box Aqueous Impingers
N
Pump/
Control Run Normal
F Box
Spike Tee (for introduction of liquid spike solution)

Previously spike
S SUMMA Canister
Pump/
Control Run Spike
F Box
Heated
Run 3 Probe Filter
Box Aqueous Impingers
N
Pump/
Control Run Normal
F Box
28 January 1999

Method NCASI 99.01 (1999)

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NCASI METHOD IM/CAN/WP-99.01

IMPINGER/CANISTER SOURCE SAMPLING METHOD FOR

NCASI SOUTHERN REGIONAL CENTER

For more information about this method, contact:

Dr. David Word Dr. MaryAnn Gunshefski

For more information about NCASI publications, contact:

NCASI METHOD IM/CAN/WP-99.01

IMPINGER/CANISTER SOURCE SAMPLING METHOD FOR

2.0 Method Description

A diagram summarizing these analyses and the corresponding analytes is given in

1-4, or equivalent methods, must be performed in order to obtain mass emission

2.1.5 Validation – This method is designed to be a self-validating method. This is

2.2.1 Sampling apparatus - A diagram of the sampling train is shown in Figure 2.

2.2.1.1 Heated Sampling Probe - The sampling probe is constructed of 1/2

2.2.1.2 Heated Filter Box - The heated probe is directly connected to a

2.2.1.3 Midget Impingers - Three midget impingers are connected in series

2.2.1.6 Flow Control Device - A 400 ± 50 mL/min critical orifice should

2.2.1.7 Teflon Head Vacuum pump - The critical orifice is followed by a

2.2.1.9 Needle valve - A needle valve is placed before the canister to

2.2.1.10 Canisters - 6 L SUMMA™ polished canister or 6 L SilcoSteel™

2.2.1.11 Thermometer - An accurate thermometer is used to measure the

2.2.1.12 Pressure Gauge - A pressure or vacuum gauge capable of

2.2.1.13 Sample storage bottles - Glass (i.e., 40 mL VOA vials) or

2.2.2 GC/FID analysis apparatus (impinger analysis) [AQU]

2.2.2.1 Laboratory glassware - Volumetric pipets, volumetric flasks,

2.2.2.2 Gas chromatography system - Gas chromatography analytical

2.2.2.3 Column - 30 m x 0.32 mm x 0.25 µm bonded phase DB-WAX

2.2.2.4 GC detector - Flame ionization detector with appropriate data

2.2.3 Formaldehyde analysis apparatus (impinger analysis) [FOR]

2.2.3.1 Spectrophotometer - A spectrophotometer capable of measuring

2.2.4 Cryogenic preconcentration/GC/MSD analysis apparatus (canister analysis) [T14]

2.2.4.1 Laboratory glassware - Volumetric pipets, volumetric flasks,

2.2.4.2 Cryogenic concentration system - A cryogenic preconcentrator is

2.2.4.3 Gas chromatography system - Gas chromatography analytical

2.2.4.4 Column - 60 m x 0.32 mm x 0.25 µm bonded phase DB-624 fused

2.2.4.5 Mass selective detector – A mass selective detector capable of

volts electron energy in the electron impact ionization mode, and

2.2.5 GC/FID analysis apparatus (canister analysis) [TER/THC]

2.2.5.1 Laboratory glassware - Volumetric pipets, volumetric flasks,

2.2.5.2 Sample loop injection system - A system capable of extracting a

2.2.5.3 Gas chromatography system - Gas chromatography analytical

2.2.5.4 Column - 30 m x 0.32 mm x 0.25 µm bonded phase DB-1 fused

2.2.5.5 GC detector - Flame ionization detector with appropriate data

2.2.6 Combustion gas analysis [COx]

2.2.6.1 Bacharach gas analyzer.

2.3.2 Pure compounds - Reagent grade acetaldehyde, acrolein, propionaldehyde,

Amount to Add to 100 mL

2.3.6 Acetylacetone reagent (impinger analysis) [FOR] - Prepare by dissolving 15.4 g of

2.3.7 Formaldehyde analysis primary stock solution (impinger analysis) [FOR] -

2.3.8 Formaldehyde analysis calibration standard solution (impinger analysis) [FOR] -

2.3.9 Formaldehyde analysis calibration solutions (impinger analysis) [FOR] - A series

acetylacetone reagent is added and the procedure described in Section 2.4.4.3 is

Amount to Add to 100 mL

2.3.16 GC/FID calibration canisters (canister analysis) [TER] – Prepare calibration

2.4.2 Sampling - A sample field data sheet is shown in Figure 3.

2.4.2.1 Measure and record ambient temperature and barometric pressure.

2.4.2.2 Preparation of collection train - The sampling train consists of: a

2.4.4 Sample analysis

2.4.4.1 Preparation of impinger samples [AQU] - Remove bottles from

2.4.4.2 GC/FID impinger analysis [AQU] - Analysis is performed by

conditions for the GC/FID analysis are given in Tables 1 and 2.

2.4.4.3 Formaldehyde sample analysis [FOR] - Remove a 2.0 mL aliquot

SAMPLING CODE: FIELD SPKIE Y N gasmL aqueous_mL