\-\-\-\--Original Message\-\-\-\--\
**From:** David Word \[mailto:d_word@src-ncasi.org\]\
**Sent:** Tuesday, June 22, 2004 6:41 PM\
**To:** Gary McAlister (Gary McAlister); Katie Hanks; Becky (Rebecca)
Nicholson\
**Cc:** Tim Hunt; Mary Tom Kissell (Mary Tom Kissell); John Pinkerton
(John Pinkerton)\
**Subject:** Benzene and Impinger Canister

Gary, Katie, and Becky:

 

The AF&PA Wood Products Environmental Issues Task Group has proposed
using the NCASI impinger/canister sampling system (NCASI
IM/CAN/WP-99.02) for benzene.  I volunteered to send you our QA data for
benzene.  Open mouth -- insert foot.  I forgot that toluene was our QA
target, not benzene.  We spiked toluene, methylene chloride, and
1,2-dichloroethane into the sample train probe tips for train spikes,
and directly into the canisters prior to field sampling for the run
spikes.  So we have toluene spike recovery data, not benzene.

 

However, benzene and toluene are similar compounds, both considered
slightly soluble and both can be purged from water.  Toluene is a
benzene ring (C6H6) with a single carbon side chain (C7H8).

 

I have attached an excerpt from NCASI Technical Bulletin 774 regarding
spike recovery of toluene (toluene.pdf).  Our toluene spike recovery
averaged high -- 133% for train spikes and 147% for run spikes.  There
is a little discussion of this on page 15 of the attached file
(underlined).

 

When we re-wrote the impinger canister method we added fairly stringent
quality control criteria.  We require that the compounds of interest
(benzene in this case) be spiked into the sample train probe tip for
train spikes and into the canister or first impinger for run spikes. 
The spike recovery is acceptable if it is 70% to 130%.  So, this builds
in a self-validation component and requires that the samplers prove they
can spike and recover benzene.  Embarrassingly, we are asking sampling
companies to provide better spike recoveries than we obtained, on
average, for the compounds we spiked as a gas. 

 

Please contact me if you have questions.

 

Thanks,

 

DW    

 

David Word, Ph.D.

402 SW 140th Terrace

Newberry, Fl 32669

\(352\) 331 - 1745 x 241

Fax (352) 331 -  1766

D_Word@src-ncasi.org

 

**NCASI METHOD IM/CAN/WP-99.02**

**IMPINGER/CANISTER SOURCE SAMPLING METHOD**

**FOR SELECTED HAPS AND OTHER COMPOUNDS AT**

**WOOD PRODUCTS FACILITIES**

**NCASI SOUTHERN REGIONAL CENTER**

**JANUARY 2004**

#### 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 and
Richard Law, Project Engineer, with the NCASI Southern Research Center.

**For more information about this method, contact:**

Dr. David Word Richard W. Law

NCASI NCASI

402 SW 140^th^ Terrace 402 SW 140^th^ Terrace

Newberry, FL 32669 Newberry, FL 32669

\(352\) 331-1745 ext. 241 (352) 331-1745, ext. 254

FAX (352) 331-1766 FAX (352) 331-1766

e-mail: dword@src-ncasi.org email: rlaw@src-ncasi.org

Jim Stainfield

NCASI

402 SW 140^th^ Terrace

Newberry, FL 32669

\(352\) 331-1745, ext. 249

FAX (352) 331-1766

e-mail: jstainfield@src-ncasi.org

**For more information about NCASI publications, contact:**

Publications Coordinator

NCASI

PO Box 13318

Research Triangle Park, NC 27709-3318

\(919\) 941-6411

National Council for Air and Stream Improvement, Inc. (NCASI). 2003.
Methods Manual, *Impinger/Canister Source Sampling Method for Selected
HAPs at Wood Products Facilities*, Research Triangle Park, N.C.:
National Council for Air and Stream Improvement, Inc.

 2004 by the National Council 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.*

**Disclaimer**

**The mention of trade names or commercial products does not constitute
endorsement or recommendation for use.**

NCASI Method IM/CAN/WP-99.02

**IMPINGER/CANISTER SOURCE SAMPLE METHOD**

**FOR SELECTED COMPOUNDS AT**

**WOOD PRODUCTS FACILITIES**

1.  **Introduction**\
    \
    This test method is intended to measure a select group of organic
    compounds that may be present in air emissions from stationary
    sources at wood products facilities. The organic compounds are
    captured in water filled impingers and an evacuated air sample
    canister. The analysis of the impinger contents is performed by gas
    chromatography/flame ionization detection and a colorimetric method.
    The analysis of the air sample canisters is performed by gas
    chromatography/mass selective detection as well as gas
    chromatography/flame ionization detection.

> Procedural steps outlined by this method range from optional to
> mandated. Actions that are not to be performed are also specified. The
> following terms will be used within the text of this method in order
> to clarify these activities:

[Term:]{.underline} [The action, activity, or procedural step
is...]{.underline}

...must not.... Prohibited

...may... Optional

...should... Suggested

...must... Required

> This NCASI impinger/canister sampling system is capable of accurately
> measuring a large number and wide variety of organic compounds in
> forest products industry source exhausts. Development of this wide
> applicability, however, resulted in a complicated field sampling
> system, lab analyses, and source concentration calculations. This
> revision to the method incorporates numerous quality control and
> quality assurance procedures intended to provide mills, sampling
> contractors, and laboratories clear feedback on the quality of
> sampling conducted.
>
> NCASI strongly suggests that sampling contractors and laboratories
> conduct spiked train sample runs and conduct full trial runs of all
> sample train configurations prior to use of this method in the field.
> Failure to do so will greatly increase the probability that mandated
> quality assurance criteria will not be achieved and the sample results
> will not be acceptable.
>
> NCASI recommends that mills, sampling contractors, and laboratories
> carefully review this method and all quality assurance procedures and
> criteria prior to source sampling. Since spikes will be used as one of
> the quality assurance procedures, evaluation of source concentration
> for the analytes of interest needs to be carefully undertaken prior to
> manufacture of the spike solutions. If multiple and varied sources
> (for example, inlets and outlets of control systems) are to be
> sampled, multiple spike solutions or varied spike volumes will likely
> be necessary to meet spiking criteria.
>
> This method shall be considered conducted only if all quality
> assurance procedures have been performed and the results clearly
> reported in the sampling report.

0.  **Applicability**\
    \
    This method is applicable to determining the concentration of a
    select group of organic compounds from stationary air emission
    sources at wood products facilities. The select group of organic
    compounds listed in Table 2.1 include hazardous air pollutants
    (HAPs), terpene compounds, acetone, and cis-1,2-dichloroethylene.

1.  **This method has been structured to allow for the determination of
    only the desired compounds of interest.** While Table 2.1 provides a
    complete list of the compounds that are applicable, this method can
    be utilized for smaller sets of compounds such as for "Total HAPs"
    (acetaldehyde, acrolein, formaldehyde, methanol, phenol and
    propionaldehyde) as defined by the Environmental Protection Agency
    (EPA) for the wood products industry. For this case, only three of
    the four analytical procedures included in this method will be
    required to obtain the concentration of total HAPs in the source gas
    being tested.\
    \
    This method is not applicable for any emission source that has a
    moisture content greater than 60%-by volume.

+-----------------------------------+-----------------+---------------+
| **Table 2.1.** Target HAP and     |                 |               |
| Non-HAP Analytes                  |                 |               |
|                                   |                 |               |
| Analysis Techniques               |                 |               |
+-----------------------------------+-----------------+---------------+
|                                   |                 |               |
+-----------------------------------+-----------------+---------------+
|                                   | Impinger        | Canister      |
+-----------------------------------+-----------------+---------------+
|                                   | Analysis        | Analysis      |
+-----------------------------------+-----------------+---------------+
| Analytes of Interest: HAPs        | Technique       | Technique     |
+-----------------------------------+-----------------+---------------+
|                                   |                 |               |
+-----------------------------------+-----------------+---------------+
| acetaldehyde                      | \[AQU\] GC/FID  | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| acrolein                          | \[AQU\] GC/FID  | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| benzene                           |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| bromomethane                      |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| chloroethane                      |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| chloroethene                      |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| 1,2-dichloroethane                |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| formaldehyde                      | \[FOR\]         |               |
|                                   | Colorimetric    |               |
+-----------------------------------+-----------------+---------------+
| methanol                          | \[AQU\] GC/FID  | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| methyl ethyl ketone               | \[AQU\] GC/FID  | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| methyl isobutyl ketone            | \[AQU\] GC/FID  | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| methylene chloride                |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| phenol                            | \[AQU\] GC/FID  | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| propionaldehyde                   | \[AQU\] GC/FID  | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| styrene                           |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| toluene                           |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| 1,2,4-trichlorobenzene            |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| m,p-xylene                        |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| o-xylene                          |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| Analytes of Interest: Terpenes    |                 |               |
+-----------------------------------+-----------------+---------------+
| cumene                            |                 | \[TER\]       |
|                                   |                 | GC/FID        |
+-----------------------------------+-----------------+---------------+
| camphene                          |                 | \[TER\]       |
|                                   |                 | GC/FID        |
+-----------------------------------+-----------------+---------------+
| 3-carene                          |                 | \[TER\]       |
|                                   |                 | GC/FID        |
+-----------------------------------+-----------------+---------------+
| p-cymene                          |                 | \[TER\]       |
|                                   |                 | GC/FID        |
+-----------------------------------+-----------------+---------------+
| limonene                          |                 | \[TER\]       |
|                                   |                 | GC/FID        |
+-----------------------------------+-----------------+---------------+
| p-mentha-1,5-diene                |                 | \[TER\]       |
|                                   |                 | GC/FID        |
+-----------------------------------+-----------------+---------------+
| alpha-pinene                      |                 | \[TER\]       |
|                                   |                 | GC/FID        |
+-----------------------------------+-----------------+---------------+
| beta-pinene                       |                 | \[TER\]       |
|                                   |                 | GC/FID        |
+-----------------------------------+-----------------+---------------+
| Other Organic Analytes of         |                 |               |
| Interest:                         |                 |               |
+-----------------------------------+-----------------+---------------+
|                                   |                 |               |
+-----------------------------------+-----------------+---------------+
| acetone                           | \[AQU\] GC/FID  | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
| cis-1,2-dichloroethylene          |                 | \[MSD\]       |
|                                   |                 | GC/MSD        |
+-----------------------------------+-----------------+---------------+
|                                   |                 |               |
+-----------------------------------+-----------------+---------------+

2.  **Principle and Methodology**

    1.  Principle. A sample of source gas is drawn through three midget
        impingers, each containing chilled organic free water. A
        Teflon-heated pump and a critical orifice are used to maintain a
        constant flow through the impingers. A portion of the gas
        exiting the impingers is drawn into an evacuated stainless steel
        canister to capture the compounds not trapped in the aqueous
        impingers.

    2.  Methodology. The water from the impingers is analyzed by direct
        injection into a gas chromatograph equipped with a flame
        ionization detector (GC/FID), referenced as \[AQU\] in this
        method.\
        \
        The formaldehyde concentration in the impinger solution is
        determined by the acetylacetone procedure, referenced as \[FOR\]
        in this method. This procedure involves the reaction of
        formaldehyde with acetylacetone to produce a colored derivative
        which is measured by colorimetric analysis.\
        \
        Terpenes in the canister are measured by a separate procedure
        from the one used for the non-terpene analytes captured in the
        canister. The terpene concentration is determined by drawing a
        sample from the canister into a gas loop. The sample is then
        directly injected into a GC/FID, referenced by \[TER\] in this
        method. The concentration of the remaining organic compounds is
        obtained by drawing another sample from the canister for
        pre-treatment by a cryogenic preconcentrator. The sample is then
        injected into a gas chromatograph equipped with a mass selective
        detector (GC/MSD), referenced as \[MSD\] in this method.\
        \
        Figure 1 provides a flow diagram of the four analytical
        procedures covered by this method.

        1.  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.  Stability -- A formal stability study has not been
            performed, but laboratory tests show that the impinger catch
            is 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, is stable for 3
            weeks.

        3.  Validation -- This method is designed to be a
            self-validating method. The quality assurance procedures
            outlined in this method are designed to validate the
            performance of the measurement system by the introduction of
            spike solutions and checking calibrations using standard
            solutions. This procedure 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).

        4.  Analytical Sensitivity -- The sensitivity of each analytical
            instrument will tend to vary depending on characteristics of
            the laboratory equipment, analysis procedure, and compound
            being analyzed. This method, therefore, has not established
            one overall level of sensitivity for the analytes present in
            both the impinger and canister samples. Instead, different
            sensitivity requirements have been established for the
            \[AQU\], \[FOR\], \[MSD\], and \[TER\] analytical
            procedures.

            1.  \[AQU\] Method Detection Limit -- This method will
                require that a method detection limit (MDL) be
                established for each compound detected by the \[AQU\]
                analytical procedure. MDLs must be established as
                defined by EPA[^1], and the documentation should be kept
                on file for reference. The MDL determined for each
                compound must be clearly reported for this method in
                terms of the laboratory concentration obtained in the
                aqueous sample (milligrams per Liter, mg/L).\
                \
                As an example, NCASI conducted a formal detection limit
                study to establish the \[AQU\] method detection limits
                in the [source gas]{.underline} tested (based on 75 mL
                volume of aqueous impinger sample and 400 mL/min sample
                rate) for the compounds shown in Table 2.1 and listed
                below in Table 3.2.

> **Table 3.2.** Example of MDLs

  ------------------------------------------ ----------------------------
  Analyte                                    NCASI Method Detection Limit
                                             (ppmv)

                                             

  Acetaldehyde                               0.26

  Acrolein                                   0.16

  Methanol                                   0.35

  Methyl Ethyl Ketone                        0.16

  Methyl Isobutyl Ketone                     0.09

  Phenol                                     0.21

  Propionaldehyde                            0.18

  Acetone                                    0.18

                                             
  ------------------------------------------ ----------------------------

2.  \[FOR\] Method Detection Level -- The laboratory sensitivity level
    for formaldehyde analysis will be determined in a similar manner as
    the procedure used to determine the \[AQU\] MDLs. The\
    formaldehyde MDL must be clearly reported in terms of mg/L in the
    aqueous sample.\
    \
    As an example, the formal detection limit study conducted by NCASI
    established that the MDL for formaldehyde in the [source
    gas]{.underline} tested (based on 75 mL volume of aqueous impinger
    sample and 400 mL/min sample rate) was 0.13 ppmv.

3.  \[MSD\] Measurement Level -- A formal detection limit study will not
    be required to establish the level of sensitivity for the compounds
    determined by the \[MSD\] analytical procedure. Instead, the
    measurement level (ML) established for these compounds will be set
    at 50 parts per billion by volume (ppbv) in the canister. This ML
    will be verified by the lowest calibration standard. If the analyte
    of interest is detected by the GC/MSD below the ML, report the
    concentration as \<50 ppbv.\
    \
    Note that the canister sample may or may not require dilution prior
    to the \[MSD\] analytical procedure. If the canister sample is
    diluted, then the actual source gas concentration will have to be
    adjusted for dilution. Clearly report the ML, the dilution factor
    (if applicable), and the source gas detection level.\
    \
    NCASI used approximately a 2:1 dilution ratio for the canister
    analysis. Using the 50 ppbv as the ML for the diluted result, the
    actual detection level for the analytes in the source gas was
    approximately 100 ppbv.

4.  \[TER\] Measurement Level -- The laboratory sensitivity level for
    terpene analysis will be based on the measurement level of the
    lowest calibration standard or 1000 ppbv. If the analyte of interest
    is detected by the GC/FID below the ML, report the concentration as
    \<1000 ppbv. The terpene samples are generally diluted, therefore
    the ML of the canister sample will have to be adjusted for dilution.
    Clearly report the ML, the dilution factor (if applicable), and the
    source gas detection level.

```{=html}
<!-- -->
```
3.  **Apparatus**

    1.  Sampling - A diagram of the sample collection train is shown in
        Figure 2. Alternative configurations for the collection train
        may be used if approved. Obtain approval prior to sample
        collection by demonstrating that the alternative collection
        train is capable of meeting the QA sampling criteria set forth
        by this method (Section 6.9).

        1.  Heated Sample Probe - The sample probe is constructed of 1/2
            inch OD stainless steel tubing or equivalent. 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.  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 must be
            maintained at 250 ± 25°F.

        3.  Sample Line - An unheated Teflon line is used to convey the
            sample from the back of the heated filter box to the first
            impinger.

        4.  Midget Impingers -- The sample line is connected to three
            midget impingers in series. The first impinger is equipped
            with a stem that has a frit on the end to improve gas/liquid
            contact. The following two impingers have regular tapered
            stems. All impinger train connectors must be glass and/or
            Teflon.

        5.  Filter - A second Teflon filter may be used after the
            impingers to prevent any fiber, debris, or water from
            accidentally being drawn into the critical orifice.

        6.  Variable Area Flow Meter - A flow meter should be placed in
            line after the impingers for a flow check during sampling.

        7.  Flow Control Device - A critical orifice or other approved
            device must be used to maintain a steady flow rate through
            the collection train. The flow rate must be 400 ± 100
            mL/min.

        8.  Vacuum Gauges -- Two vacuum gauges placed on each side of
            the critical orifice capable of reading 25 inches of mercury
            gauge (in Hg).

        9.  Teflon Head Pump - The critical orifice is followed by a
            pump, with a Teflon head, capable of providing a vacuum of
            about 18 in Hg. Pump capacity must be sufficient to obtain
            and maintain critical conditions at the orifice. The Teflon
            diaphragms used in the pump must be cleaned or replaced
            prior to each mill test effort.

        10. Canister Sample Pickup Point -- A tee with an on/off valve
            must be placed inline between the sample pump exhaust and
            the excess source gas vent for the pump. The canister will
            draw a slip-stream of source gas at this location.

        11. Variable Area Flow Meter with a Flow Controller - A flow
            meter should be placed in line before the canister as a
            visual aid for maintaining the sample delivery rate to the
            canister during sampling. The flow to the canister will
            require adjustment periodically during sampling to ensure
            that the canister is filled at a constant rate over the
            sample run. The flow controller can be a needle valve.

        12. Canisters - 6 L SUMMA™ polished canister or 6 L SilcoSteel™
            canister is used to collect a portion of the sample gas.
            Other types of canisters can be used if the canisters are
            shown to have similar non-reactive properties.

        13. Thermometer - An accurate thermometer is used to measure the
            ambient and canister temperatures.

        14. Canister Gauge -- An absolute pressure gauge or a vacuum
            gauge capable of indicating ± 0.1 in. Hg is placed after the
            canister sample pickup point and before the canister. This
            gauge will indicate the canister pressure before and after
            the sample run as well as during the leak check procedure.
            If an absolute pressure gauge is used, then the barometric
            pressure can be obtained before and after each sample run.

        15. Sample storage bottles - Glass (i.e., 40 mL or larger VOA
            vials) or polyethylene bottles can be used to store the
            aqueous impinger samples.

    2.  \[AQU\] GC/FID analysis

        1.  Laboratory glassware - Volumetric pipets, volumetric flasks,
            2.0 mL autosampler vials, and syringes necessary for
            standards preparation and analysis.

        2.  Gas chromatography system - Gas chromatography analytical
            system complete with a temperature-programmable gas
            chromatograph suitable for splitless injection and all
            required accessories including an autosampler, syringes,
            analytical columns and gases. **The autosampler must be
            capable of maintaining the samples at 4°C to prevent
            degradation of acrolein.**

        3.  Column - 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.

        4.  GC detector - Flame ionization detector with appropriate
            data acquisition system.

    3.  \[FOR\] Formaldehyde analysis

        1.  Laboratory glassware -- Borosilicate test tubes (5- to
            10-mL) with TFE-fluorocarbon-lined screw caps, 50-mL buret,
            volumetric pipets, volumetric flasks, syringes, and cuvettes
            necessary for standards preparation and analysis.

        2.  Spectrophotometer - A spectrophotometer capable of measuring
            absorbance at a 412 nm wavelength.

        3.  Absorption Cell -- The absorption cell must have a minimum
            path length of 1.0 cm. Longer paths may be used to improve
            the sensitivity of the photometer.

        4.  Heating Block -- Heating block or water bath that can be
            regulated to maintain 60°±3°C for the test tubes.

        5.  Centrifuge with capped tubes.

        6.  Magnetic stirrer and stir bars.

        7.  pH Meter conforming to the requirements of ASTM Test Method
            D 1293.

    4.  \[MSD\] GC/MSD analysis

        1.  Laboratory glassware - Volumetric pipets, volumetric flasks,
            and syringes necessary for standards preparation and
            analysis.

        2.  Cryogenic concentration system - A cryogenic preconcentrator
            **capable of trapping polar compounds** is required to
            concentrate the sample prior to introduction into the GC/MSD
            system.

        3.  Gas chromatography system - Gas chromatography analytical
            system complete with a temperature-programmable gas
            chromatograph suitable for split/splitless injection and all
            required accessories including syringes, analytical columns
            and gases.

        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.

        5.  Mass selective detector -- A mass selective detector capable
            of scanning from 29amu to 300 amu every 2 seconds or less
            using 70 volts electron energy in the electron impact
            ionization mode, and appropriate data system.

    5.  \[TER\] GC/FID analysis

        1.  Laboratory glassware - Volumetric pipets, volumetric flasks,
            and syringes necessary for standards preparation and
            analysis.

        2.  Sample loop injection system - A system capable of
            extracting a sample from the canister into a sample loop.
            The sample is then directly injected into GC/FID system.

        3.  Gas chromatography system - Gas chromatography analytical
            system complete with a temperature-programmable gas
            chromatograph suitable for split/splitless injection and all
            required accessories including syringes, analytical columns
            and gases.

        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.

        5.  GC detector - Flame ionization detector with appropriate
            data acquisition system.

**5.0 Reagents**

1.  DI Water -- Organic free or deionized (DI) water, is used in the
    impingers as a capture solution, for rinsing the sample line and
    impingers at the end of the sample run, and for preparation of all
    aqueous calibration standards and spike solutions.

2.  Nitrogen gas -- Pure nitrogen gas (99.999%) must be used for
    cleaning the canisters and as the dilution gas for gas calibration
    standards and spike solutions. When preparing the gas calibration
    standards and spike solutions, the nitrogen gas must be humidified
    by bubbling through DI water prior to being added to a canister.

3.  Purity of Reagents -- Reagent grade chemicals shall be used for all
    tests. The reagents required by this method shall conform to the
    specifications established by the Committee on Analytical Reagents
    of the American Chemical Society, where such specifications are
    available; otherwise, use the highest purity grade available.

4.  \[AQU\] Primary Stock Solution --Reagent grade chemicals must be
    used in the preparation of the aqueous primary stock solution for
    the \[AQU\] GC/FID analysis portion of this method. Prepare the
    \[AQU\] Primary Stock Solution by combining aliquots of the
    compounds of interest listed in Table 5.1 in a 100 mL volumetric
    flask. Dilute to 100 mL with DI water. This stock solution will be
    used to prepare the \[AQU\] Calibration Standards and the \[AQU\]
    Spike Solution. The resulting \[AQU\] Primary Stock Solution will
    have a concentration of 1000 mg/L.

**Table 5.1.** Reagents for the \[AQU\] Primary Stock Solution

+----------------------------------+-----------------------------------+
| Compound                         | Amount (μL) to Add to             |
|                                  |                                   |
|                                  | 100 mL Volumetric Flask           |
+----------------------------------+-----------------------------------+
|                                  |                                   |
+----------------------------------+-----------------------------------+
| acetaldehyde                     | 128                               |
+----------------------------------+-----------------------------------+
| acetone                          | 128                               |
+----------------------------------+-----------------------------------+
| acrolein                         | 119                               |
+----------------------------------+-----------------------------------+
| methanol                         | 126                               |
+----------------------------------+-----------------------------------+
| methyl ethyl ketone              | 124                               |
+----------------------------------+-----------------------------------+
| methyl isobutyl ketone           | 125                               |
+----------------------------------+-----------------------------------+
| propionaldehyde                  | 124                               |
+----------------------------------+-----------------------------------+
| phenol (solid)                   | 100 mg                            |
+----------------------------------+-----------------------------------+
|                                  |                                   |
+----------------------------------+-----------------------------------+

5.  \[AQU\] Calibration Standards -- Prepare a series of aqueous
    calibration standards from the \[AQU\] Primary Stock Solution to
    develop a calibration curve for each compound of interest. The lower
    limit \[AQU\] Calibration Standard must be 0.5 mg/L. The upper limit
    of the aqueous calibration standards should be 1000 mg/L.

6.  \[AQU\] Internal Standards -- The aqueous internal standard is added
    to every standard, blank, matrix spike, and sample before analysis
    to compensate for variations in sample size and is used in
    determining relative response factors for the target compounds
    analyzed by the \[AQU\] GC/FID procedure used in this method. The
    recommended \[AQU\] internal standard for this method is
    cyclohexanol. Another internal standard that may be used in place of
    cyclohexanol is 2,2,2-triflouroethanol.

    1.  \[AQU\] Internal Standard Stock -- This internal standard will
        be added to each laboratory blank and quality control sample and
        calibration standard. If cyclohexanol is to be added to
        autosampler vials, prepare the aqueous internal standard stock
        solution by using 0.312 mL of pure cyclohexanol and diluting to
        100 mL with DI water in a 100 mL volumetric flask. The resulting
        concentration of this stock solution will be 3000 mg/L
        cyclohexanol.

    2.  \[AQU\] Intermediate Internal Standard -- This internal standard
        will be added to each field sample bottle along with a known
        volume of DI water in the laboratory prior to sampling. If using
        cyclohexanol, prepare this intermediate internal standard by
        using 3.12 mL of pure cyclohexanol and diluting to 2.0 L with DI
        water in a 2.0 L volumetric flask. The resulting concentration
        of this internal standard will be 1500 mg/L cyclohexanol.

7.  \[FOR\] Primary Stock Solution -- For this method, the preparation
    of the primary stock solution for formaldehyde will be based on the
    ASTM Method D 6303-98, "Standard Test Method for Formaldehyde in
    Water." The formalin solution called for by the ASTM method contains
    37% formaldehyde by weight or 40g formaldehyde/100 mL formalin
    solution. Note that formalin solutions contain methanol.\
    \
    The \[FOR\] Primary Stock Solution is made by placing a 2.7 mL
    aliquot of formalin solution (37% formaldehyde by weight) in a 1000
    mL volumetric flask and dilute to 1000 mL with DI water. The
    formalin solution must be standardized per the ASTM method to verify
    the formaldehyde content. The primary stock solution should be
    stored at room temperature, in the dark, and must be standardized
    every six months. The solution appears to be reasonably stable.

8.  \[FOR\] Intermediate Stock Solution - The intermediate stock
    solution must be prepared from the \[FOR\] primary stock solution
    each time the calibration standards are prepared. Prepare the
    \[FOR\] intermediate stock solution by placing a 1.0 mL aliquot of
    the \[FOR\] primary stock solution in a 100 mL volumetric flask and
    dilute to 100 mL with DI water. The resulting \[FOR\] intermediate
    stock solution will have a formaldehyde concentration of 10 mg/L.

9.  \[FOR\] Calibration Standards -- The spectrophotometer used in the
    colorimetric analysis procedure must be calibrated using six
    different formaldehyde concentrations. The calibration standards
    will be prepared in six screw capped test tubes. Leave the first
    test tube empty and place 0.1, 0.2, 0.4, 1.0, and 1.5 mL of the
    \[FOR\] secondary stock solution in the second through sixth test
    tubes, respectively. Fill all six test tubes to 2.0 mL with DI
    water. The resulting concentration in the test tubes will be 0.0,
    0.5, 1.0, 2.0, 5.0, and 7.5 mg/L formaldehyde, respectively.

10. \[FOR\] Acetylacetone Reagent -- Prepare by dissolving 15.4 g of
    ammonium acetate in 50 mL of DI water in a 100 mL volumetric flask.
    To this solution, add 0.20 mL of pure acetylacetone and 0.30 mL of
    aldehyde-free glacial acetic acid (specific gravity 1.05). Mix
    thoroughly and dilute to 100 mL with DI water. This reagent must be
    stored in a brown glass bottle and refrigerated. This reagent is
    stable for a maximum of two weeks.

11. \[MSD\] Primary Stock Gas Mixtures and Calibration Standards -- The
    compounds that are analyzed by the GC/MSD technique are either
    partially purged from, or not captured in, the aqueous impinger
    sample. As a consequence, two separate primary stock mixtures will
    be required to prepare the calibration standards for the GC/MSD
    analytical technique. In either case, the primary stock mixtures
    shall consist of the compounds of interest that will be captured in
    the canister.

    1.  \[MSD\] Aqueous Analyte Primary Stock Gas Mixture -- This
        primary stock gas mixture shall consist of the compounds of
        interest that have the potential to be purged from the aqueous
        impinger sample. These compounds are analyzed by both the
        \[AQU\] and \[MSD\] procedures. This primary stock gas mixture
        is made in two steps, first an aqueous solution is prepared and
        then an aliquot of the aqueous solution is converted to a gas
        mixture.\
        \
        The aqueous solution is prepared by adding the aliquot for each
        compound of interest shown in Table 5.2 into a 100 mL volumetric
        flask. Dilute this solution to 100 mL with DI water.

> **Table 5.2.** Reagents for the \[MSD\] Aqueous Analyte
>
> Primary Stock Solution (gas phase)

+------------------------------------+---------------------------------+
| Compound                           | Amount (μL) to Add to           |
|                                    |                                 |
|                                    | 100 mL Volumetric Flask         |
+------------------------------------+---------------------------------+
|                                    |                                 |
+------------------------------------+---------------------------------+
| acetaldehyde                       | 281                             |
+------------------------------------+---------------------------------+
| acetone                            | 369                             |
+------------------------------------+---------------------------------+
| acrolein                           | 334                             |
+------------------------------------+---------------------------------+
| methanol                           | 202                             |
+------------------------------------+---------------------------------+
| methyl ethyl ketone (2-butanone)   | 448                             |
+------------------------------------+---------------------------------+
| methyl isobutyl ketone             | 628                             |
+------------------------------------+---------------------------------+
| propionaldehyde                    | 360                             |
+------------------------------------+---------------------------------+
| phenol (solid)                     | 439 mg                          |
+------------------------------------+---------------------------------+
|                                    |                                 |
+------------------------------------+---------------------------------+

> Then inject 10 μL of this aqueous stock solution into a clean
> evacuated canister (below 1.0 in Hga) along with 170 μL of DI water.
> Fill the canister to 60 in Hga with a nitrogen gas. The resulting
> concentration for each compound in the \[MSD\] aqueous analyte primary
> stock solution will be 1000 ppbv in the canister.

2.  \[MSD\] Aqueous Analyte Calibration Standards - Prepare a series of
    gas calibration standards for the \[MSD\] analysis technique. The
    lower limit of the gas calibration standards must be 50 ppbv. The
    upper limit of the gas calibration standards should be 500 ppbv. The
    concentration of each calibration standard shall be prepared by
    adding the appropriate amount of \[MSD\] aqueous analyte primary
    stock gas mixture to a clean evacuated (\<1.0 in Hga) canister and
    dilute with nitrogen gas to 40 in Hga or above.

3.  \[MSD\] Gas Analyte Primary Stock Gas Mixture -- This primary stock
    gas mixture shall consist of the compounds in Table 2.1 that are not
    captured in the aqueous impinger sample as indicated by the \[MSD\]
    analysis technique only. The compounds of interest can be obtained
    in gas phase directly. Refer to EPA Compendium Method TO-14 for
    possible list of available compounds.\
    \
    \
    \
    The concentration of each compound should be 1000 ppbv at a
    certified level of Environmental Protection Agency (EPA)
    Traceability Protocol Number 1 or other approved certified level.

4.  \[MSD\] Gas Analyte Calibration Standards -- Prepare a series of gas
    calibration standards for the \[MSD\] analysis technique. The lower
    limit of the gas calibration standards must be 50 ppbv. The upper
    limit of the gas calibration standards should be 500 ppbv. The
    concentration of each calibration standard shall be prepared by
    adding the appropriate amount of \[MSD\] gas analyte primary stock
    gas mixture to a clean evacuated (\<1.0 in Hga) canister and dilute
    with nitrogen gas to 40 in Hga or above.

```{=html}
<!-- -->
```
12. \[MSD\] Internal Standard -- An internal standard must be added to
    the gas samples analyzed by the GC/MSD technique. The commonly used
    internal standards are bromochloromethane, 1,4-diflourobenzene, and
    d5-chlorobenzene. For additional guidance, refer to EPA Compendium
    Method TO-14.\
    \
    The gas concentration of the \[MSD\] internal standard will be at an
    appropriate level as determined by the laboratory conducting the
    analysis with a recommended concentration range between 100 and 300
    ppbv.

13. \[TER\] Primary Stock Gas Mixture -- The primary stock gas solution
    for the terpene compounds will be used to make calibration standards
    for the \[TER\] GC/FID analysis technique in this method. This stock
    solution is prepared in two steps, first add the amount of each
    terpene compound of interest shown in Table 5.3 into a 10 mL
    volumetric flask and dilute to 10 mL with reagent grade [ethyl
    ether]{.underline}. Then, inject 100 μL of the terpene/ethyl ether
    solution into a clean evacuated canister (below 1.0 in Hga). Fill
    the canister to 60 in Hga with nitrogen gas. The resulting \[TER\]
    primary stock solution will have a canister concentration of 100
    ppmv for each terpene compound.

**Table 5.3.** Reagents for the \[TER\] Primary Stock Solution

+----------------------------------+-----------------------------------+
| Compound                         | Amount (μL) to Add to             |
|                                  |                                   |
|                                  | 10 mL Volumetric Flask            |
+----------------------------------+-----------------------------------+
|                                  |                                   |
+----------------------------------+-----------------------------------+
| p-mentha-1,5-diene               | 810                               |
+----------------------------------+-----------------------------------+
| 3-carene                         | 786                               |
+----------------------------------+-----------------------------------+
| cumene                           | 694                               |
+----------------------------------+-----------------------------------+
| p-cymene                         | 780                               |
+----------------------------------+-----------------------------------+
| limonene                         | 811                               |
+----------------------------------+-----------------------------------+
| α-pinene                         | 795                               |
+----------------------------------+-----------------------------------+
| β-pinene                         | 793                               |
+----------------------------------+-----------------------------------+
| camphene (solid)                 | 809 mg                            |
+----------------------------------+-----------------------------------+
|                                  |                                   |
+----------------------------------+-----------------------------------+

14. \[TER\] Calibration Standards - Prepare a series of calibration
    standards from the \[TER\] Primary Stock Solution. The calibration
    standards will be used to develop a calibration curve for each
    terpene compound of interest. The lowest calibration standard must
    have a concentration of 1.0 ppmv. The highest calibration standard
    should be 300 ppmv. For each concentration, the appropriate amount
    of \[TER\] Primary Stock Solution shall be added to a clean
    evacuated gas cylinder (below 1.0 in Hga) and diluted with nitrogen
    gas to 60 in Hga.

15. Spike Solutions -- This method requires that quality assurance
    procedures be carried out to ensure that the measurement system is
    capable of capturing the compounds of interest from the emission
    source and preserving those compounds until analysis can be
    conducted. Spike solutions are used to introduce a known quantity of
    reagent(s) into the measurement system operating under normal
    sampling conditions. The spike samples are collected and analyzed
    along with the source samples collected by the measurement system.

    1.  Aqueous Spike Solution - The aqueous spike solution shall have
        the appropriate concentration for each compound of interest that
        is equivalent to ±50% of the expected source gas concentration.
        The expected source gas concentration can be obtained from
        historical test results, test results from similar emission
        sources, or published emission factors. Alternatively, both
        \"low\" and \"high\" spike solutions can be used. In this case,
        the two spike solutions are intended to bracket the expected
        source gas concentration.

> All of the compounds of interest, except formaldehyde, can be obtained
> from diluting the \[AQU\] primary stock solution. The formaldehyde
> portion of the Aqueous Spike Solution will come from a dilution of the
> \[FOR\] primary stock solution. Note that the liquid volume
> contributed by the \[FOR\] primary stock solution will contain
> methanol, therefore, the resulting methanol concentration will be
> higher than expected from just methanol in the \[AQU\] primary stock
> solution.\
> \
> It is recommended that the volume of the aqueous spike introduced into
> the spiked sample run (Section 6.9.3) and spiked train sample run
> (Section 6.9.4) be 1.0 mL.

2.  Prepare Gas Spike Solution - The gas spike solution shall have the
    appropriate concentration of each compound of interest that is
    equivalent to ±50% of the expected concentration for the source gas
    being tested. The expected source gas concentration can be obtained
    from historical test results, test results from similar emission
    sources, or published emission factors.

> The gas spike solution can be prepared by diluting the \[MSD\] gas
> analyte primary stock gas mixture, the \[TER\] primary stock gas
> mixture, or purchasing a cylinder with the compounds of interest at
> the desired concentration. The gas mixtures can then be diluted or
> stored undiluted in a cleaned canister that is pressurized between 40
> and 60 in Hga that will be used as a spike transfer container.

16. Reference Standards -- A reference standard is used to validate each
    calibration curve developed for the analytical procedures in this
    method. The reference standard can be certified or from a secondary
    source. A second source reference standard is purchased from a
    different vendor than was used to purchase the reagent used to make
    the primary stock solution.\
    \
    The concentration for each reference standard shall be equivalent to
    the midpoint of the reagent's calibration curve. Note that an
    aliquot of internal standard solution must be added to the reference
    standard prior to analysis.

```{=html}
<!-- -->
```
6.  **Sample Procedure**\
    \
    Reliable emission data can be obtained through properly configuring
    and operating the sample collection train. Quality assurance
    measures provide verification that appropriate sampling techniques
    were utilized. This section will describe the assembly and operation
    of the sample collection train and the quality assurance
    requirements.

    1.  Preparation of the Sample Bottles -- Add 1.0 mL \[AQU\]
        intermediate internal standard stock to each sample bottle and
        dilute with 74 mL of DI water. Record the pre-sample weight of
        each bottle.

    2.  Sample Run -- A sample collection period preceded and followed
        by quality assurance checks as specified in this method. It is
        recommended that the duration of each sample run be one hour.
        Sampling or source specific conditions may\
        require, however, that the collection time be adjusted to a
        shorter or longer\
        interval.\
        \
        For source types with multiple vents such as press vents, a
        sample run shall refer to all collection trains that operate
        simultaneously. Control device inlets and outlets are considered
        separate sources.

    3.  Sampling Event -- Three consecutive sample runs conducted at one
        source type.

    4.  Preparation of the Collection Train -- Prior to testing each new
        emission source, clean the probe and filter housing with DI
        water and replace the filter. Use one pre-weighed sample bottle
        for each impinger set. Record the ID of the sample bottle and
        divide the contents between the three midget impingers so that
        each contains approximately 25 mL of the aqueous solution.\
        \
        Assemble the impinger/canister collection train as shown in
        Figure 2. For sources that are expected to have very high
        amounts of moisture (40% to 60%-by volume), a fritless empty
        impinger can be used as the first impinger (for a total of four
        impingers) to act as a water drop out. Keep both the impingers
        and canister out of direct sunlight. Attach a thermocouple to
        the outside of the canister and keep the canister valve closed.

    5.  Leak-Check Procedure -- An optional leak check can be conducted
        when the collection train is first assembled before the system
        is brought up to operating temperature. A leak check prior to
        starting the sample run is mandatory with the collection train
        at operating temperature.\
        \
        The method used for leak checking the collection train will be
        dependent on the configuration of the train. The collection
        train shown in Figure 2, for instance, has two sections to leak
        check; the probe/impinger section and the canister section. The
        probe/impinger section includes components from the probe to the
        pump. The canister section is from the canister sample pickup
        point to the canister.\
        \
        The probe/impinger section and the canister section will have an
        acceptable leak check when the loss of vacuum is not greater
        than 1.0 in Hg over a 2.0 minute period.

        1.  Probe/Impinger Section Leak Check - The leak check procedure
            shall be conducted when all of the heated components have
            reached operating temperature (250°F ± 25°F). The probe and
            impinger section of the collection train is leak checked by
            turning on the sample pump, plugging the probe tip, and
            drawing a vacuum of at least 15 in. Hg. After 15 in. Hg has
            been reached, close the inlet side of the sample pump and
            turn the sample pump off. After the pressure reading has
            stabilized, note the beginning and ending pressure on the
            vacuum gauge over a two minute period.\
            \
            Leak Check Troubleshooting: presence of bubbles in the first
            impinger indicates a leak located between the probe and the
            first impinger: a leak between the impingers or behind the
            impingers will be indicated by\
            aqueous solution being drawn up one of the impinger stems
            (flow direction is backwards through the system).\
            \
            When this section of the collection train has passed the
            leak check, ***slowly*** remove the plug at the probe tip.
            Bringing this section up to ambient pressure slowly will
            ensure that the aqueous solution remains distributed evenly
            between the impingers.

        2.  Canister Section Leak Check -- Close the on/off valve at the
            canister sample pickup point. Open the needle valve of the
            flow meter to the canister. Open the canister valve and
            allow the canister to bring this section under vacuum. After
            the pressure reading in this section equalizes, note the
            beginning and ending pressure readings on the canister
            vacuum gauge over a two minute period. An alternative
            procedure might include a second evacuated canister that
            could be used to draw a vacuum on this section. This will
            alleviate the necessity for using the sample canister for
            leak checking.\
            \
            If this section passes the leak check, close the canister
            valve and slowly open the on/off valve. There should be very
            little loss of vacuum (less than 0.5 in Hga) in the canister
            since the air volume in this section of the collection train
            is minimal.

    6.  Pre-Sample Run Procedures --

        1.  Verify that the probe and filter housing are at operating
            temperature. Place crushed ice and water around the
            impingers.

        2.  Obtain the average of five flow rate readings taken at the
            probe tip of the collection train. The average flow rate
            should be 400 ± 100 mL/min. Record the ambient temperature
            and pressure at this measurement location.

        3.  Obtain the flow rate of the source gas at the test port
            using appropriate stack measurement methods. Other source
            gas parameters required must include stack gas temperature,
            moisture content, static pressure, and percent O~2~ and
            CO~2~.

        4.  Insert probe into test port and align perpendicular to
            source gas flow. Recheck the operating temperature. Close
            the on/off valve at the slip-stream pickup point for the
            canister sample, open the canister valve to verify that the
            canister pressure is less than 1.0 in Hga, and adjust the
            canister flow meter so that it is just barely open (this
            will prevent excessive flow to the canister at the start of
            the sample run). Record the beginning canister pressure and
            temperature.

    7.  Sample Collection -- Prior to the start of each sample run,
        coordinate with process operators to verify that the production
        unit and source gas being tested are under steady state
        conditions.\
        \
        The collection train will be started in two steps. The first
        step will involve purging ambient air from the collection train
        by drawing sample gas through the impingers. The second step
        will then establish sample flow to the canister.

        1.  Start the impinger sample pump. Record start time and flow
            rate at the flow meter.

        2.  After one minute, open the on/off valve at the canister
            sample pickup point and adjust the flow rate to the
            canister. An appropriate flow rate will deliver a constant
            amount of sample gas over the entire sample run. For the 6-L
            canisters and a 1-hour sample run, it is recommended that
            the flow rate be 100 ml/min.

        3.  At various intervals during the sample run, record the
            impinger flow rate, canister flow rate, and the canister
            pressure and temperature.

        4.  At the end of the sample run, turn off both the slip-stream
            valve and impinger sample pump. Record ending canister
            pressure and temperature. [Close the canister
            valve.]{.underline}

    8.  Post-Sample Run Procedures --

        1.  Remove probe from test port.

        2.  Turn on the sample pump only long enough to obtain the
            average of five flow rate measurements at the probe tip.

        3.  Verify that the differences between pre- and post-average
            flow rate measurements are within 20%.

        4.  If the difference is greater than 20% then examine the
            collection train and determine if the sample run is valid. A
            post-sample run leak check may be conducted in order to
            examine flow rate differences.

    9.  Sample Recovery --

        1.  Disconnect the sample line at the exit to the heated filter
            box. Rinse the sample line with a small amount of DI water
            (approximately 10 mL). Operate the sample pump long enough
            to draw the rinse into the first impinger.

        2.  Transfer the contents of the impingers into the original
            sample bottle. Label the sample bottle appropriately, mark
            water level, and obtain the post-sample weight of the
            bottle. For high moisture sources, two sample bottles can be
            used.

        3.  The sample bottles must be stored on ice or in a
            refrigerator set at approximately 4°C. If the water samples
            are required to be shipped to the laboratory for analysis,
            pack the sample bottles in ice, do not use frozen packs.

        4.  Disconnect the canister sample line from the canister and
            place the protection cap on the canister valve. Label the
            canister appropriately. Ship the canisters in a container
            that will keep the canister valve protected.

    10. Quality Assurance Procedures for the Collection Train -- The
        quality assurance (QA) measures used to verify the performance
        of the collection train(s) include conducting duplicate sample
        runs and spiked sample runs. A QA sample run will be conducted
        at the same time as the normal sample run.

        1.  Field blank sample -- There should be at least one field
            blank sample per source tested. The first field blank will
            be one of the pre-weighed sample bottles containing 75 mL of
            solution (DI water and internal standard). The field blank
            must be analyzed along with the other aqueous samples
            collected by this method.

        2.  Equipment blank sample -- A 75 mL sample of the DI water
            must be used for rinsing the collection train components in
            the field. Note that the internal standard will need to be
            added to the equipment blank at the laboratory prior to
            analysis. The equipment blanks must be analyzed along with
            the other aqueous samples collected by this method.

        3.  Duplicate Sample Run - One duplicate sample run must be
            conducted per mill visit or per sampling event for each
            source type at a mill, whichever is more stringent. The
            optimal sampling configuration used to conduct a duplicate
            sample will be to connect two separate collection trains to
            a single probe and filter box as shown in Figure 3.
            Alternative configurations for conducting a duplicate sample
            run can be used if shown to meet the QA criteria. Duplicate
            sample trains must be configured such\
            that independent leak checks and flow rate measurements can
            be conducted.\
            \
            For source types with multiple emission points being tested
            simultaneously such as press vents, this method requires
            that a duplicate sample run be conducted at only one of the
            emission points. To provide additional QA, however, it is
            recommended that duplicate samples be collected at more than
            one emission point during a sampling event. Control device
            inlets and outlets are considered separate sources.

            1.  Duplicate Sample Run Procedure - Prepare both collection
                trains as per Section 6.3. To leak check the duplicate
                train shown in Figure 3, disconnect one of the trains
                from the outlet of the heated filter box. Cap that
                connection and follow Section 6.4 to conduct the leak
                check procedure for the probe, filter box, and
                impinger/canister assembly for one train. For the
                disconnected\
                impinger/canister train, again follow Section 6.4 but
                disregard the probe and filter portion of the leak check
                procedure.\
                Follow Section 6.5 through Section 6.8 to complete a
                duplicate sample run making sure that both collection
                trains are started simultaneously and operate in a
                similar manner.\
                \
                The normal and duplicate samples are separate samples
                whereby the duplicate is collected, labeled, and
                analyzed separately from the normal sample.

            2.  Duplicate QA Criteria - Calculate the difference between
                the source gas concentration as determined by the normal
                and duplicate trains. This difference is calculated by
                the absolute value of the [dry source
                concentration]{.underline} determined by one sample
                train minus the [dry source concentration]{.underline}
                determined by the other sample train divided by the
                average [dry source concentration]{.underline}
                determined from both trains (Equation 6.1).\
                \
                $\text{\%}\text{difference} = \text{ABS}\left| \frac{\left( C_{\text{SN}} - C_{\text{SD}} \right)}{\text{Average}\left( C_{\text{SN}},C_{\text{SD}} \right)} \right| \times \text{100}$
                (Equation 6.1)\
                \
                C~SN~ = dry source gas concentration determined by the
                normal train, ppmvd\
                C~SD~ = dry source gas concentration determined by the
                duplicate train, ppmvd\
                \
                The result is expressed as a percent difference for each
                analyte and should be less than 40%. The percent
                difference should not be calculated if the concentration
                of the analyte determined by the normal train or
                duplicate train has been detected below the method
                detection limit.\
                \
                Results of the duplicate sample analysis must be clearly
                calculated and reported for each analyte. Identify each
                analyte that did not meet the 40 percent acceptance
                criteria.

            3.  Source Gas Concentration - The source gas concentration
                reported for duplicate sample runs will be based on the
                average of the [dry source gas
                concentrations]{.underline} determined by each
                collection train even if the QA criteria is not met.

        4.  Spiked Sample Run and Field Spike Samples -- One spiked
            sample run must be conducted per mill visit or per sampling
            event for each source type at a mill, whichever is more
            stringent. For the spiked sample run, a known spike solution
            is introduced into one of the two collection trains to
            determine the percent recovery of the spike. The optimal
            sampling configuration used to conduct a spiked sample run
            will be to connect two separate collection trains to a
            single probe/filter box as shown in Figure 3. One of the
            collection trains will be equipped with: (1) a spike tee at
            the inlet to the first impinger and (2) an evacuated spiked
            canister. The two sampling trains must be configured such
            that independent leak checks and flow rate measurements can
            be conducted.\
            \
            For source types with multiple emission points being tested
            simultaneously such as press vents, this method requires
            that a spiked sample run be conducted at only one of the
            emission points. To provide additional QA, however, it is
            recommended that a spiked sample run be collected at more
            than one emission point during a sampling event. Control
            device inlets and outlets are considered separate sources.\
            \
            ***If the analytes of interest are limited to acetaldehyde,
            acrolein, acetone, formaldehyde, methanol, phenol, methyl
            ethyl ketone, methyl isobutyl ketone, and propionaldehyde,
            then substitute an unspiked evacuated canister for the
            spiked canister.***\
            \
            Alternative configurations for conducting a spike sample run
            can be used if shown to meet the QA criteria.

            1.  Aqueous Field Spike -- For each spiked sample run,
                prepare an aqueous field spike by injecting an aliquot
                (1.0 mL) of aqueous spike solution (Section 5.14.1) into
                one of the sample bottles containing DI water and
                \[AQU\] Internal Standard. Clearly label the aqueous
                field spike and analyze with the corresponding aqueous
                sample from the spiked sample run. Results of the
                aqueous field spike must be clearly reported.

            2.  Spiked Canisters and Gas Field Spike -- Prior to going
                to the field, prepare two spiked canisters for each
                spiked sample run. A spiked canister is prepared by
                injecting an aliquot, for example 25 mL at ambient
                pressure, of the gas spike solution (Section 5.14.2)
                into a clean evacuated canister. The gas spike solution
                can be transferred to each spike canister using a gas
                syringe with a valve. It is very important to use a
                consistent gas spike volume or record the volume of
                spike (both at ambient conditions) that is injected into
                each canister. Clearly label each spike canister.\
                \
                A gas field spike will be required for each spiked
                sample run. Choose one of the spiked canisters to be the
                gas field spike and label it as such. The gas field
                spike will be analyzed along with the spiked canister
                used for the spiked sample run. Results of the gas field
                spike must be clearly reported.

            3.  Spiked Sample Run Procedure -- Prepare both collection
                trains as per Section 6.3 choosing one as the spiked
                train. To leak check the collection trains shown in
                Figure 3, disconnect one of the trains from the outlet
                of the heated filter box. Cap that connection and follow
                Section 6.4 to conduct the leak check procedure for the
                probe, filter box, and impinger/canister assembly for
                one train. For the disconnected impinger/canister train,
                follow Section 6.4 but disregard the probe and filter
                portion of the leak check procedure.\
                \
                Follow Section 6.5 through Section 6.8 to complete a
                spiked sample run making sure that both collection
                trains start simultaneously and operate in a similar
                manner.\
                \
                After the start of the run, inject an aliquot of the
                aqueous spike solution (Section 5.14.1) into the first
                impinger of the spiked train. Note that the canister has
                already been pre-spiked. The normal and spiked samples
                are separate samples whereby the spiked sample is
                collected, labeled, and analyzed separately from the
                normal sample.

            4.  Spike Recovery QA Criteria -- The percent recovery of
                the aqueous spike and the gaseous spike will be based on
                the mass recovered in the spiked train (after
                subtraction of the source gas contribution as shown in
                Figure 4) divided by the mass obtained from the field
                spikes (Equation 6.2). The method used to calculate the
                percent recovery for Equation 6.2 is outlined in Figure
                4**.**\
                \
                Account for all laboratory and field dilutions in the
                computation of the mass.\
                \
                $\text{\%}\ \text{Recovery}_{(i)} = \frac{\text{mass}_{\text{recovered}(i)}}{\text{mass}_{\text{FS}(i)}} \times \text{100}$
                (Equation 6.2)\
                \
                *mass*~recovered*(i)*~ *=* mass of analyte (*i*)
                recovered by the spiked collection train\
                *mass*~FS*(i)*~ *=* mass of analyte (*i*) in the aqueous
                and gas field spike\
                \
                The spike recovery is acceptable if the percent recovery
                is between 70% and 130%. Results of the spiked sample
                run must be clearly calculated and reported for each
                analyte. If the 70 to 130 % percent recovery criteria
                are not met, the analyte(s) failing the criteria must be
                listed and the results clearly stated in the report.

        5.  Spiked Train Sample Run -- One spiked train sample run must
            be conducted for each mill visit. This QA procedure can be
            conducted prior to source testing, while in the field, or
            after source testing.\
            \
            \
            **If the analytes of interest are limited to acetaldehyde,
            acrolein, acetone, formaldehyde, methanol, phenol, methyl
            ethyl ketone, methyl isobutyl ketone, and propionaldehyde
            the gas spike, gas field spike, and spiked canister
            discussed in this section are not needed.**\
            \
            The spiked train sample run will be conducted using only one
            collection train attached to the heated probe and filter box
            as shown in Figure 3. [Use an unspiked evacuated
            canister.]{.underline} This collection train will be
            operated outside or independent of the source(s) tested. For
            the spiked train sample run, both an aqueous spike and a gas
            spike, if applicable, are injected into the probe tip of the
            collection train to determine the percent recovery of the
            spikes. Care must be taken to prevent introduction of any
            ambient organic contaminants during this procedure;
            activated charcoal tubes may be used for this purpose.

            1.  Aqueous Field Spike -- Prepare an aqueous field spike by
                injecting an aliquot (1.0 mL) of aqueous spike solution
                (Section 5.14.1) into one of the sample bottles
                containing DI water and \[AQU\] Internal Standard.
                Clearly label the aqueous field spike and analyze with
                the corresponding aqueous sample from the spiked sample
                run.

            2.  Spiked Canisters and Gas Field Spike -- Prior to going
                to the field, prepare one spiked canister for the spiked
                train sample run unless the analytes are limited to the
                list provided above in bold. A spiked canister is
                prepared by injecting an aliquot, for example 25 mL at
                ambient pressure, of the gas spike solution (Section
                5.14.2) into a cleaned evacuated (\<1.0 in Hga)
                canister. The gas spike solution can be transferred to
                the canister using a gas syringe with a valve. Use the
                same gas spike volume as injected into the spiked
                canisters prepared for the spiked sample run (Section
                6.9.3.2). Clearly label this spike canister.\
                \
                The gas field spike will be injected into the probe tip
                of the collection train using a gas syringe with a
                valve. Use the same gas spike volume that was injected
                into the spiked canister.

            3.  Spiked Train Sample Run Procedure -- Prepare the
                collection train as per Sections 6.3 and 6.4. Then
                follow Section 6.5 through Section 6.8 to complete the
                spiked train sample run. The sample flow rate and
                duration should be similar to the sample runs conducted
                at the source.\
                \
                Note that two spikes will be injected into the probe tip
                of this collection train unless the analytes are limited
                to the list provided above in bold. After the start of
                the run, inject the gas spike first over a period of at
                least 5 minutes. Then follow with the injection of the
                aqueous spike over a period of at least 10 minutes. It
                is recommended that the aqueous spike be injected
                ***slowly*** into the heated probe tip over the duration
                of the remaining sample run. Prepare the aqueous and gas
                field spikes.

            4.  Spike Recovery QA Criteria -- The percent recovery of
                the aqueous spike and the gaseous spike will be based on
                the mass recovered in the spiked train divided by the
                mass obtained from the field spikes (Equation 6.3). The
                method used to calculate the percent recovery is
                outlined in Figure 5. Account for all laboratory and
                field dilutions in the computation of the mass.

> $\text{\%}\ \text{Recovery}_{(i)} = \frac{\text{mass}_{\text{ST}(i)}}{\text{mass}_{\text{FS}(i)}} \times \text{100}$
> (Equation 6.3)\
> \
> *mass~ST(i)~ =* mass of analyte (*i*) recovered by the spiked
> collection train\
> *mass~FS(i)~ =* mass of analyte (*i*) in the aqueous and gas field
> spike\
> \
> The spike recovery is acceptable if the percent recovery is between
> 70% and 130%. Results of the spiked train sample run must be clearly
> calculated and reported for each analyte. If the 70 to 130 % criteria
> are not met, the analyte(s) failing the criteria must be listed and
> the results clearly stated in the report.

0.  **Sample Analysis**\
    \
    Complete analysis of the impinger and canister samples will require
    four analytical techniques. If a select group of compounds are to be
    determined, then only use the analytical techniques that are
    required to obtain the desired concentrations in the aqueous and gas
    samples.

```{=html}
<!-- -->
```
1.  Sample Preparation --

    0.  Aqueous Impinger Samples - Record the laboratory weight and
        verify water level mark for each sample bottle prior to
        analysis. Note any differences. The sample bottles do not need
        to be at room temperature before weighing and must remain cold.

    1.  Gas Canister Samples - Record the pressure of each canister when
        delivered to the lab. If the canister samples require dilution,
        add nitrogen gas and record the final pressure of the canister.

2.  \[AQU\] GC/FID Analysis -- Perform the analysis of the compounds of
    interest in the aqueous impinger samples by direct aqueous injection
    into a GC/FID.

    1.  \[AQU\] GC/FID Operating Parameters -- Table 1 lists the
        recommended operating parameters for the GC/FID analysis of the
        aqueous samples. Other chromatographic columns and conditions
        may be used if it has been established that the compounds are
        adequately separated, quality control parameters are met, and no
        other interferences are present. Once the GC/FID system has been
        optimized for analytical separation and sensitivity, the
        operating conditions must remain constant for the analysis of
        all samples, blanks, calibration standards and quality assurance
        samples.\
        \
        Optimal GC/FID operating conditions will produce distinct
        separate peaks for each analyte at established retention times.
        Verification of the GC/FID performance is recommended by running
        an analysis of a solution containing a high level \[AQU\]
        calibration standard and the \[AQU\] internal standard stock.
        Determine the retention time of each analyte relative to the
        internal standard. If using the recommended \[AQU\] internal
        standard stock solution (Section 5.6), place 10 μL into a 2.0 mL
        autosampler vial and fill the vial with a high concentration
        \[AQU\] calibration standard. The resulting concentration of the
        \[AQU\] internal standard in the autosampler vial will be 15
        mg/L.\
        \
        Compare the results with previously established retention times
        for the GC/FID instrument. If the retention times are
        significantly different, then adjust the \[AQU\] GC/FID
        operating parameters to return the retention times to the
        established values.\
        \
        Troubleshooting tips: **The temperature of the samples in the
        autosampler must be kept at 4°C to inhibit the degradation of
        acrolein.** Some possible interfering compounds include ethanol,
        methyl mercaptan, dimethyl sulfide, and dimethyl disulfide. Also
        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
        250^o^C, the oven to over 200^o^C, and the detector to 275^o^C
        for several hours.

    2.  \[AQU\] GC/FID Calibration Curves -- The calibration curves will
        be based on the analysis of the \[AQU\] calibration standards
        prepared in Section 5.5. Obtain a 2.0 mL autosampler vial for
        each calibration standard and place 10 μL of the \[AQU\]
        internal standard stock (Section 5.6) into each vial. Then fill
        each vial with a different \[AQU\] calibration standard. The\
        \
        resulting concentration of the internal standard in the vials
        will be 15 mg/L.\
        \
        Most analytical software will automatically generate calibration
        curves and verify the accuracy of each curve. Verification of a
        calibration curve shall be based on the determination of the
        relative standard deviation of the relative response factors
        obtained for each analyte of interest. Each point on a
        calibration curve will have a relative response factor (RRF~M~).
        The RRF~M~ is calculated by Equation 7.1 using a relationship
        between the responses obtained for the internal standard and
        analyte.\
        \
        \
        $\text{RRF}_{M}\  = \ \frac{A_{M}}{A_{\text{IS}}}\ x\ \frac{C_{\text{IS}}}{C_{M}}$
        (Equation 7.1)\
        \
        RRF~M~ = Relative response factor for an analyte\
        A~M~ = area of analyte peak\
        A~IS~ = area of internal standard peak\
        C~M~ = concentration of analyte injected (mg/L)\
        C~IS~ = concentration of internal standard injected (mg/L)\
        \
        A calibration curve will be acceptable when the relative
        standard deviation of the RRF~M~s are less than 20%. The average
        RRF~M~ will then be used to calculate the concentration of an
        analyte in an aqueous sample by Equation 7.2.\
        \
        $C_{S}\  = \ \frac{A_{S}\ x\ C_{\text{IS}}}{A_{\text{IS}}\ x\ \text{averageRRF}_{M}}$
        (Equation 7.2)\
        \
        C~S~ = Concentration of the analyte in the sample, mg/L\
        A~S~ = Area of the analyte peak in the sample\
        C~IS~ = Concentration of the internal standard, mg/L\
        A~IS~ = Area of the internal standard peak in the sample\
        averageRRF~M~ = Relative response factor of analyte\
        \
        If the calibration curve is not acceptable, then reanalyze the
        calibration solutions by developing another calibration curve
        and evaluating the relative standard deviation. If that
        evaluation also fails, then prepare new calibration standards
        and/or perform instrument maintenance.

    3.  \[AQU\] GC/FID QA Requirements -- The GC/FID aqueous analytical
        technique includes both mandatory and recommended laboratory QA\
        procedures. Laboratories must report the appropriate QA results
        along with the source sample results.

        1.  Laboratory Blank Sample - A laboratory blank sample must be
            analyzed prior to analysis. Additional laboratory blanks
            must be included for every 20 source samples analyzed. Blank
            samples are prepared from the DI water used to prepare the
            internal and calibration standards. Blank samples must
            include the appropriate internal standard.

        2.  Laboratory Duplicates -- One laboratory duplicate of a
            source sample will be required. Additional laboratory
            duplicates will be required for every 10 source samples
            analyzed. Duplicates are a replicate injection of the same
            source sample. Note that these samples already contain the
            internal standard.\
            \
            The percent difference of the duplicate concentrations
            should be within 10% (Section 6.9.2.2).

        3.  Calibration Verification Standard -- The calibration
            verification standard shall be the mid-range \[AQU\]
            calibration standard. This calibration check must be
            performed prior to analysis, after every 10 source samples
            analyzed, and at the end of the analysis.\
            \
            Compare the concentration reported by the instrument with
            the known concentration of the standard to verify instrument
            calibration. The percent recovery of the concentrations must
            be within 80% and 120%. If it is not, either prepare a new
            standard or perform instrument maintenance. If necessary,
            re-calibrate the instrument.

        4.  Reference Standard -- Analysis of a reference standard
            (Section 5.15) is required for each analyte following the
            initial analysis of the calibration verification standard.
            The reference standard should match the results obtained for
            the calibration verification standard to demonstrate optimum
            analytical performance.\
            \
            Compare the concentration of the reference standard with the
            concentration of the calibration verification standard. The
            percent recovery of the concentrations must be within 80%
            and 120%. If it is not, either prepare a new standard or
            perform instrument maintenance. If necessary, re-calibrate
            the instrument.

        5.  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 are 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.

    4.  \[AQU\] GC/FID Source Sample Analysis -- The concentration of
        the source samples must be determined from the calibration
        curves derived for the \[AQU\] GC/FID analytical technique. Note
        that the internal standard has already been added to the source
        samples.

```{=html}
<!-- -->
```
2.  \[FOR\] Acetylacetone Colorimetric Procedure -- This analytical
    procedure will determine the concentration of formaldehyde in the
    aqueous samples. It is based on the ASTM Method D 6303-98. Note that
    this procedure does not require the use of an internal standard.
    Laboratories must report the appropriate QA results along with the
    source sample results.

    1.  Spectrophotometer Operating Parameters -- The spectrophotometer
        must be capable of measuring absorbance at 412 nanometer
        wavelength.

    2.  \[FOR\] Calibration Curve -- Prepare the six \[FOR\] Calibration
        Standards as described in Section 5.8. Add 2.0 mL of the
        acetylacetone reagent to each test tube and mix thoroughly.
        Place test tubes containing the calibration\
        standards in the water bath for 10 minutes at 60^o^C. Then allow
        the test tubes to cool to room temperature.\
        \
        The same spectrophotometer absorption cell will be used to
        analyze the six \[FOR\] calibration standards. The six
        concentrations will represent 0.0, 0.5, 1.0, 2.0, 5.0, and 7.5
        mg/L formaldehyde, respectively. Follow the spectrophotometer
        manufacturer's instructions for calibrating the instrument by
        measuring the absorbance, at 412 nm, for each calibration
        standard.\
        \
        The calibration curve should yield a linear plot of the
        absorbance value versus the corresponding formaldehyde
        concentration. The linear plot must have a correlation
        coefficient that is greater than 0.995. Determine the slope and
        y-intercept of the curve to develop a linear equation that must
        be used to determine the concentration of formaldehyde in the
        source samples.\
        \
        Verification of the formaldehyde calibration curve is not
        required because the titration process to determine the
        formaldehyde content of the formalin solution, called for by the
        ASTM method, is a primary standard.

    3.  \[FOR\] Formaldehyde Laboratory QA Requirements -- The
        formaldehyde analysis includes both mandatory and recommended
        laboratory QA procedures.

        1.  Laboratory Blank Sample - A laboratory blank sample must be
            analyzed prior to analysis. Additional laboratory blanks
            must be included for every 20 source samples analyzed. Blank
            samples are prepared from the DI water used to prepare the
            internal and calibration standards. Note that the blank
            samples for this analytical technique do not contain an
            internal standard.

        2.  Laboratory Duplicates -- One laboratory duplicate of a
            source sample will be required. Additional laboratory
            duplicates will be required for every 10 source samples
            analyzed. Duplicates are a replicate analysis of the same
            source sample.\
            \
            The percent difference of the duplicate concentrations
            should be within 10% (Section 6.9.2.2).

        3.  Calibration Verification Standard -- The calibration
            verification standard shall be the mid-range \[FOR\]
            calibration standard. This calibration check must be
            performed prior to analysis, after every 10 source samples
            analyzed, and at the end of the analysis.\
            \
            Compare the concentration reported by the instrument with
            the known concentration of the standard to verify instrument
            calibration. The percent recovery of the concentrations must
            be within 80% and 120%. If it is not, either prepare a new
            standard or perform instrument maintenance. If necessary,
            re-calibrate the instrument.

        4.  Reference Standard -- Analysis of a reference standard
            (Section 5.15) is required following the initial analysis of
            the calibration verification standard. The reference
            standard should match the results obtained for the
            calibration verification standard to demonstrate optimum
            analytical performance.\
            \
            Compare the concentration of the reference standard with the
            concentration of the calibration verification standard. The
            percent recovery of the concentrations must be within 80%
            and 120%. If it is not, either prepare a new standard or
            perform instrument maintenance. If necessary, re-calibrate
            the instrument.

    4.  \[FOR\] Formaldehyde Source Sample Analysis -- Refer to the ASTM
        Method 06303-98 for complete details. In summary, remove a 2.0
        mL aliquot of the impinger sample and transfer to a screw-capped
        test tube. Add 2.0 mL of the acetylacetone reagent and mix
        thoroughly. Place test tube in a water bath for 10 minutes at
        60^o^C. Allow test tubes to cool to room temperature. Transfer
        the cooled solution to an absorption cell and place in the
        spectrophotometer to measure the absorbance at 412 nm.\
        \
        Use the absorbance value obtained for each source sample to
        calculate the formaldehyde concentration from the calibration
        curve developed by this procedure.\
        \
        If the concentration of a sample is above 7.5 mg/L after the
        initial analysis, remove an aliquot of the original aqueous
        sample and dilute accordingly. Start the procedure over by using
        the diluted source sample. Confirm that this concentration is
        within the operating range of the instrument. Always dilute the
        aliquot of original source sample instead of diluting the
        colored (derivatized) solutions.

3.  \[MSD\] GC/MSD Analysis -- Perform the analysis of the canister
    samples by using a cryogenic preconcentrator to concentrate the
    sample for injection into a gas chromatograph followed by a mass
    selective detector. The delivery of the \[MSD\] Internal Standard
    should be automated by the preconcentrator. The lab must insure that
    that pretreatment of the gas sample does not remove the polar
    compounds of interest.

    1.  \[MSD\] GC/MSD Operating Parameters -- Table 2 lists the
        recommended operating parameters for the preconcentrator and the
        GC/MSD instrument. Other chromatographic columns and conditions
        may be used if it has been established that the compounds are
        adequately separated, quality control parameters are met, and no
        other interferences are present. Once the \[MSD\] GC/MSD system
        has been optimized for analytical separation and sensitivity,
        the operating conditions must remain constant for the analysis
        of all samples, blanks, calibration standards and quality
        assurance samples.\
        \
        Optimal \[MSD\] GC/MSD operating conditions will produce
        distinct separate peaks for each analyte at established
        retention times. Verification of the \[MSD\] GC/MSD performance
        is recommended by running an analysis of a solution containing a
        high level \[MSD\] Calibration Standard and the \[MSD\] Internal
        Standard. Determine the retention time of each analyte relative
        to the internal standard.\
        \
        Compare the results with previously established retention times
        for the \[MSD\] GC/MSD instrument. If the retention times are
        significantly different, then adjust the \[MSD\] GC/MSD
        operating parameters to return the retention times to the
        established values.

    2.  \[MSD\] GC/MSD Calibration Curves -- Develop a separate
        calibration curve for each compound being analyzed by the GC/MSD
        technique. The calibration curves will be based on the analysis
        of the \[MSD\] Calibration Standards prepared in Section 5.11.
        The delivery of the \[MSD\] Internal Standard should be
        automated by the preconcentrator for all samples and QA
        requirements. Most analytical software will automatically
        generate calibration curves and verify the accuracy of each
        curve.\
        \
        Verification of a calibration curve shall be based on the
        determination of the relative standard deviation of the RRF~M~s
        obtained for each analyte of interest. Refer to Equation 7.1
        (Section 7.2.2) to calculate the RRF~M~ for each calibration
        point along a calibration curve. A calibration curve will be
        acceptable when the relative standard deviation of the RRF~M~s
        are less than 20%. Use the average RRF~M~ to calculate the
        concentration of an analyte in a gas sample by Equation 7.2
        (Section 7.2.2).\
        \
        If the calibration curve is not acceptable, then reanalyze the
        calibration solutions by developing another calibration curve
        and evaluating the relative standard deviation. If that
        evaluation also fails, then prepare new calibration standards
        and/or perform instrument maintenance.

    3.  \[MSD\] GC/MSD QA Requirements -- The GC/MSD technique includes
        both mandatory and recommended laboratory QA procedures.
        Laboratories must report the appropriate QA results along with
        the source sample results.

        1.  Laboratory Blank Sample - A laboratory blank sample must be
            analyzed prior to analysis. Additional laboratory blanks
            must be included for every 20 source samples analyzed. Blank
            samples are prepared from the nitrogen gas used to prepare
            the calibration standards.

        2.  Laboratory Duplicates -- One laboratory duplicate of a
            source sample will be required. Additional laboratory
            duplicates will be required for every 10 source samples
            analyzed. Duplicates are a replicate injection of the same
            source sample.

> The percent difference of the duplicate concentrations should be
> within 10% (Section 6.9.2.2).

3.  Calibration Verification Standard -- The calibration verification
    standard shall be the appropriate mid-range \[MSD\] calibration
    standard. This calibration check must be performed prior to
    analysis, after every 10 source samples analyzed, and at the end of
    the analysis.\
    \
    Compare the concentration reported by the instrument with the known
    concentration of the standard to verify instrument calibration. The
    percent recovery of the concentrations must be within 80% and 120%.
    If it is not, either prepare a new standard or perform instrument
    maintenance. If necessary, re-calibrate the instrument.

4.  Reference Standard -- Analysis of a reference standard (Section
    5.15) is required for each analyte following the initial analysis of
    the calibration verification standard. The reference standard should
    match the results obtained for the calibration verification standard
    to demonstrate optimum analytical performance.\
    \
    Compare the concentration of the reference standard with the
    concentration of the calibration verification standard. The percent
    recovery of the concentrations must be within 80% and 120%. If it is
    not, either prepare a new standard or perform instrument
    maintenance. If necessary, re-calibrate the instrument.

5.  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 are 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.

```{=html}
<!-- -->
```
4.  \[MSD\] GC/MSD Source Sample Analysis --

    1.  Record the temperature and pressure of each canister at
        laboratory conditions.

    2.  If dilution of a canister sample is required for analysis, then
        fill the appropriate canisters to 40 in Hga or above with
        nitrogen gas. Record the final pressure and temperature of each
        diluted canister.

    3.  Using a preconcentrator, inject a sample from each canister into
        the GC/MSD. The concentration of the samples analyzed must be
        determined from the calibration curves developed for this
        procedure.

```{=html}
<!-- -->
```
4.  \[TER\] GC/FID Analysis -- Perform the analysis of the terpene
    compounds collected in the canister by using a gas sample loop to
    introduce the gas sample into the GC/FID. Note that there is no
    internal standard for terpene analysis.

    1.  \[TER\] GC/FID Operating Parameters -- Table 3 lists the
        recommended operating parameters for the GC/FID analysis for
        terpene compounds. Other chromatographic columns and conditions
        may be used if it has been established that the compounds are
        adequately separated, quality control parameters are met, and no
        other interferences are present. Once the \[TER\] GC/FID system
        has been optimized for analytical separation and sensitivity,
        the operating conditions must remain constant for the analysis
        of all samples, blanks, calibration standards and quality
        assurance samples.\
        \
        Optimal \[TER\] GC/FID operating conditions will produce
        distinct separate peaks for each analyte at established
        retention times. Verification of the \[TER\] GC/FID performance
        is recommended by running an analysis of a solution containing a
        high level \[TER\] calibration standard. Determine the retention
        time of each terpene compound. Note that there is no internal
        standard used in the terpene analysis.\
        \
        Compare the results with previously established retention times
        for the \[TER\] GC/FID instrument. If the retention times are
        significantly\
        \
        different, then adjust the \[TER\] GC/FID operating parameters
        to return the retention times to the established values.

    2.  \[TER\] GC/FID Calibration Curves -- Develop a separate
        calibration curve for each compound being analyzed by the
        \[TER\] GC/FID technique. The calibration curves will be based
        on the analysis of the \[TER\] calibration standards prepared in
        Section 5.14. Most analytical software will automatically
        generate the calibration curves and verify the accuracy of each
        curve.\
        \
        Verification of a calibration curve shall be based on the linear
        plot of the terpene concentration versus corresponding GC/FID
        area count. Calibration will be acceptable if the correlation
        coefficient for the curve is greater than 0.995. Determine the
        slope and y-intercept of the curve to develop a linear equation
        that must be used to determine the concentration of terpenes in
        the source samples.\
        \
        If the calibration curve is not acceptable, then reanalyze the
        calibration gas mixtures by developing another calibration curve
        and evaluating the correlation coefficient. If that evaluation
        also fails, then prepare new calibration standards and/or
        perform instrument maintenance.

    3.  \[TER\] GC/FID QA Requirements -- The \[TER\] GC/FID procedure
        includes both mandatory and recommended laboratory QA
        procedures. Laboratories must report the appropriate QA results
        along with the source sample results.

        1.  Laboratory Blank Sample - A laboratory blank sample must be
            analyzed prior to analysis. Additional laboratory blanks
            must be included for every 20 source samples analyzed. Blank
            samples are prepared from the nitrogen gas used to prepare
            the calibration standards.

        2.  Laboratory Duplicates -- One laboratory duplicate of a
            source sample will be required. Additional laboratory
            duplicates will be required for every 10 source samples
            analyzed. Duplicates are a replicate injection of the same
            source sample.\
            \
            The percent difference of the duplicate concentrations
            should be within 10% (Section 6.9.2.2).

        3.  Calibration Verification Standard -- The calibration
            verification standard shall be the appropriate mid-range
            \[TER\] calibration standard. This calibration check must be
            performed prior to analysis, after every 10 source samples
            analyzed, and at the end of the analysis.\
            \
            Compare the concentration reported by the instrument with
            the known concentration of the standard to verify instrument
            calibration. The percent recovery of the concentrations must
            be within 80% and 120%. If it is not, either prepare a new
            standard or perform instrument maintenance. If necessary,
            re-calibrate the instrument.

    4.  \[TER\] GC/FID Source Sample Analysis - Obtain a gas sample from
        each canister and analyze using the GC/FID. The concentration of
        the samples analyzed must be determined from the calibration
        curves developed for this procedure.

        1.  Record the temperature and pressure of each canister at
            laboratory conditions.

        2.  If dilution of a canister sample is required for analysis,
            then fill the appropriate canisters to 40 in Hga or above
            with nitrogen gas. Record the final pressure and temperature
            of each diluted canister.

        3.  Inject a sample from each canister into the GC/FID. The
            concentration of the samples analyzed must be determined
            from the calibration curves developed for this procedure.

```{=html}
<!-- -->
```
7.  **Calculations\
    \
    **The stack gas concentration of each analyte will be determined by
    combining the data collected from the sample train and laboratory
    analyses. The following calculation procedure has been provided as
    guidance. Other calculation methods may be used if shown to be
    valid.\
    \
    This method has been developed to determine the emission source gas
    concentration of the compounds listed in Tables 2.1 and 2.2. Some of
    these compounds will be captured in the aqueous impinger sample,
    some will be collected in both the aqueous and canister sample, and
    the rest will be collected in the canister. The calculations
    provided determine the mass of each compound captured in the
    impinger and canister samples and the corresponding source gas
    concentration.

    1.  Total Mass Captured by the Collection Train\
        \
        The total mass of a compound is determined by combining the mass
        captured in the aqueous sample with the corrected mass captured
        in the canister sample. The procedure used to calculate the
        total mass can also be used to determine the mass for the
        percent recovery calculations required by the QA procedures in
        this method.

        1.  Mass Collected in the Aqueous Sample -- The mass of an
            analyte in the aqueous sample is determined by multiplying
            the aqueous concentration of the analyte by the volume of
            the aqueous sample.

            1.  Mass of Formaldehyde - The formaldehyde concentration is
                determined by a different analytical procedure than the
                other compounds of interest in the aqueous sample.
                Therefore, the mass of formaldehyde in Equation 1 is
                calculated using the final volume of the aqueous sample
                obtained by the collection train (sample plus rinse).\
                \
                Equation 1:\
                $\text{mass}_{\text{HCOH, aqueous}}\  = \ C_{\text{HCOH}}\ x\ V_{\text{f,aqueous}}\ $\
                \
                mass~HCOH,aqueous~ = mass of formaldehyde in the aqueous
                sample, μg\
                C~HCOH~ = concentration of formaldehyde in aqueous
                sample, μg/mL\
                V~f,aqueous~ = final volume of aqueous sample, mL

            2.  Mass of \[AQU\] Compounds - The determination of the
                mass for the remaining compounds in the aqueous sample
                is based on a fixed sample volume, 100 mL, and the
                concentration (Equation 2).\
                \
                Equation 2:\
                $\text{mass}_{\lbrack\text{AQU}\rbrack\text{,aqueous}}\  = \ C_{\lbrack\text{AQU}\rbrack}\ x\ \text{100}\ \text{mL}\ $\
                \
                mass~\[AQU\],aqueous~ = mass of \[AQU\] analyte in the
                aqueous sample, μg\
                C~\[AQU\]~ = concentration of analyte~i~ in the aqueous
                sample, μg/mL\
                \
                The final volume of the \[AQU\] samples are fixed at 100
                mL because both the \[AQU\] internal standard and the
                \[AQU\] primary stock solution were prepared in 100 mL.

        2.  Mass Collected in the Canister -- The collection train only
            captures a slip-stream of the source gas in the canister
            while the total sample of the source gas passes through the
            impingers. Because of this, the resulting mass collected in
            the canister will have to be adjusted by a correction
            factor.\
            \
            First, however, the mass of each compound captured in the
            canister is determined by multiplying the volume of the
            sample gas at standard conditions by the concentration as
            determined by the \[MSD\] GC/MSD or \[TER\] GC/FID
            analytical procedures. Note that the dry concentration in
            the canister will only be equivalent to the dry
            concentration in the source gas for those compounds that are
            not partially captured in the aqueous sample and for
            canister samples that have not been diluted prior to
            laboratory analysis.

            1.  Volume of Gas Sample in Canister -- The interior volume
                of the canister used in this method is 6.0 Liters.
                Equation 3 calculates the volume of the gas sample in
                the canister at standard conditions.\
                \
                Equation 3:\
                $\ V_{\text{GS, std}}\  = 6\text{.}0\ L\ \left( \frac{\text{528}^{\circ}R}{T_{\text{GS}\ }} \right)\ \left( \frac{P_{\text{GS}\ }}{\text{29}\text{.}\text{92}\ \text{in Hg}} \right)$\
                \
                V~GS,\ std~ = wet standard volume of gas sample at
                standard conditions, wsL\
                T~GS~ = temperature of gas sample (equivalent to
                canister temperature) at laboratory conditions, °R\
                P~GS~ = pressure of the gas sample prior to analysis, in
                Hga

            2.  Mass of \[MSD\] or \[TER\] Compounds in Canister Sample
                -- Obtain the concentration of the compounds of interest
                in the canister gas sample by the \[MSD\] GC/MSD or
                \[TER\] GC/FID analytical procedures. Then combine the
                concentration with the standard sample gas volume to
                calculate the mass of analyte~(i)~ in the canister using
                in Equation 4.\
                \
                Equation 4:
                $\ \text{mass}_{\text{i, canister}}\  = \ \left( \frac{C_{\text{i, }\lbrack\text{MSD}\rbrack\text{ or }\lbrack\text{TER}\rbrack}}{\text{10}^{9}} \right)\ \left( V_{GS\ ,\text{std}} \right)\ \left( \frac{1\ \text{gmole}}{\text{24}\text{.}\text{055}\ L} \right)\ \left( \text{MW}_{(i)} \right)\ \left( \frac{\text{10}^{6}\mu g}{g} \right)$\
                \
                mass~i,canister~ = mass of analyte~(i)~ in the canister,
                μg\
                C~i,\ \[MSD\]\ or\ \[TER\]~ = concentration of \[MSD\]
                or \[TER\] analyte in wet canister sample gas, ppbvw\
                V~GS,std~ = wet standard volume of gas sample at
                standard conditions, wsL (one atmosphere and 68°F)\
                MW~(i)~ = molecular weight of analyte~i~, g/gmole

        3.  Canister Mass Correction Factor -- A mass correction factor
            is used to adjust the mass collected in the canister. This
            correction factor is based the ratio of the total dry volume
            of source gas sampled through the\
            collection train to the dry volume of the sample collected
            in the canister at the end of the sample run.

            1.  Total Dry Volume of Source Gas Sampled -- This method
                assumes that the flow rate of the collection train is
                measured at the probe tip using a soap-bubble meter. The
                ambient air entering the bubble meter, however, becomes
                saturated from passing over the surface of the liquid
                reservoir. Therefore, the flow will have to be corrected
                to dry conditions assuming saturated conditions using
                the vapor pressure of water at the ambient temperature.
                Calculate the dry standard flow rate measured prior to
                and after the sample run using Equation 5.\
                \
                Equation 5:\
                $Q_{\text{probe},\text{drystd}} = Q_{\text{probe},\text{meas}}\left( \frac{P_{\text{bar}} - P_{\text{vap}}}{\text{29}\text{.}\text{92}\ \text{in}\ \text{Hg}} \right)\left( \frac{\text{528}^{\circ}R}{T_{\text{meas}}} \right)$\
                \
                Q~probe,\ drystd~ = dry standard flow rate measured at
                the probe tip of the sample collection train, dsL/min\
                Q~probe,\ meas~ = actual flow rate measured at the probe
                tip of the sample collection train, L/min\
                P~bar~ = barometric pressure at flow rate measurement
                site, in Hga\
                P~vap~ = water vapor pressure in the gas stream being
                measured, assumed to be saturated at ambient dry
                temperature, in Hga.\
                T~meas~ = ambient temperature at flow rate measurement
                site, °R\
                \
                \
                Then, calculate the total volume of source gas sampled
                by multiplying the average flow rate of the collection
                train by the duration of the sample run using Equation
                6.\
                \
                Equation 6:\
                $V_{\text{sourcegas},\text{drystd}} = \left( \frac{Q_{(i)\text{probe},\text{drystd}} + Q_{(f)\text{probe},\text{drystd}}}{2} \right) \times t$\
                \
                V~sourcegas,drystd~ = Total dry standard volume of
                source gas sampled by the collection train, dsL\
                Q~(i)probe,drystd~ = Pre-sample run dry standard flow
                rate measured at the probe tip of the sample collection
                train, dsL/min\
                Q~(f)probe,drystd~ = Post-sample run dry standard flow
                rate measured at the probe tip of the sample collection
                train, dsL/min\
                t = duration of sample run, minutes

            2.  Dry Volume of Canister Sample Collected -- This
                parameter represents the volume of the gas sample
                collected at the end of the sample run. Determine the
                volume of gas present in the canister at the start and
                end of the of the sample run using Equations 7 and 8. It
                is assumed that no moisture is present in the evacuated
                canisters.\
                \
                Equation 7:\
                $V_{(o)\text{canistergas},\text{drystd}} = 6\text{.}0L \times \left( \frac{P_{o,\text{can}}}{\text{29}\text{.}\text{92}\ \text{in}\ \text{Hg}} \right)\left( \frac{\text{528}^{\circ}R}{T_{o,\text{can}}} \right)$\
                \
                V~(o)canistergas,drystd~ = dry standard canister gas
                volume, dsL, at start of sample run\
                P~o,can~ = pressure of the canister, in Hga, at start of
                sample run\
                T~o,can~ = temperature of canister gas sample, °R, at
                start of sample run\
                \
                Equation 8:\
                $V_{(f)\text{canistergas},\text{drystd}} = 6\text{.}0L \times \left( \frac{P_{f,\text{can}} - P_{\text{vap}@\text{38}^{\circ}F}}{\text{29}\text{.}\text{92}\ \text{in}\ \text{Hg}} \right)\left( \frac{\text{528}^{\circ}R}{T_{f,\text{can}}} \right)$\
                \
                V~(f)canistergas,\ drystd~ = dry standard canister gas
                volume, dsL, at the end of the sample run\
                P~(f)can~ = Measured pressure of the canister, in Hga,
                at the end of the sample run\
                P~vap@38°F~ = moisture correction for water vapor in
                canister equivalent to 0.2292 in Hga; gas stream assumed
                saturated leaving the impinger train at 38°F\
                \
                T~(f)can~ = temperature of canister gas sample, °R, at
                the end of the sample run\
                \
                Then calculate the difference in the pre- and post-
                canister volumes using Equation 9.\
                \
                Equation 9:\
                $\ V_{c\text{anistersample},\text{drystd}} = \ V_{(f)\ \text{canistergas},\text{drystd}}\  - \ V_{(o)\ \text{canistergas},\text{drystd}}$\
                \
                V~canistersample,drystd~ = dry standard volume of
                canister sample collected, dsL\
                V~(f)canistergas,drystd~ = dry standard canister gas
                volume at the end of the sample run, dsL\
                V~(o)canistergas,drystd~ = dry standard canister gas
                volume at the start of the sample run, dsL

            3.  Canister Mass Correction Factor -- Since the volume of
                source gas sampled through the probe tip of the
                collection train is greater than the sample volume sent
                to the canister, the resulting mass of each analyte
                detected in the canister has to be corrected. This mass
                correction factor is calculated by Equation 10.\
                \
                Equation 10:

> **\
> **$\ \text{CF}\  = \ \frac{V_{\text{sourcegas},\text{drystd}}}{V_{c\text{anistersample},\text{drystd}}}$\
> \
> CF = canister mass correction factor\
> V~sourcegas,drystd~ = Total dry standard volume of source gas sampled
> by the collection train, dsL\
> V~canistersample,drystd~ = dry standard volume of canister sample
> collected, dsL

4.  Total Mass Captured by the Collection Train -- The mass of the
    compounds collected in the aqueous sample will be combined with the
    corrected mass collected in the canister sample using Equation 11.

> Equation 11:
>
> $\ \text{mass}_{i,\ \text{total}}\  = \ \text{mass}_{i,\text{aqueous}\ } + \ \left( \text{mass}_{i,\text{canister}}\ x\ \text{CF} \right)$\
> \
> mass~i,total~ = total mass of analyte~(i)~ captured by the collection
> train, μg\
> mass~i,aqueous~ = mass of analyte~(i)~ in the aqueous sample, μg\
> mass~i,canister~ = mass of analyte~(i)~ in the canister sample, μg\
> CF = canister mass correction factor

2.  Concentration in the Source Gas Sample\
    \
    The source gas concentration for each compound of interest can be
    determined by converting the total mass captured into a dry gas
    volume equivalent of the pure compound and then dividing by the
    total dry volume sampled by the collection train, as shown by
    Equation 12.

3.  Equation 12:\
    $C_{\text{i,source gas}} = \frac{\text{mass}_{\text{i,total}} \times \left( \frac{g}{\text{10}^{6}\mu g} \right)\left( \frac{1}{\text{MW}_{i}} \right)\left( \frac{\text{24}\text{.}\text{055}L}{\text{gmole}} \right)\left( \frac{\text{10}^{6}\mu L}{L} \right)}{V_{\text{sourcegas},\text{drystd}}}$\
    \
    C~i,sourcegas~ = concentration of analyte~(i)~ in the source gas,
    ppmvd\
    mass~i,total~ = total mass of analyte~(i)~ captured by the
    collection train, μg\
    MW~(i)~ = molecular weight of analyte~i~, g/gmole\
    V~sourcegas,drystd~ = Total dry standard volume of source gas
    sampled by the collection train, dsL

```{=html}
<!-- -->
```
8.  **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.

Federal Register, Part VIII, EPA,, 40 CRF Part 136, Rules and
Regulations, "Appendix B to Part 136-Definition and Procedure for the
Determination of the Method Detection Limit."

American Society For Testing and Materials, Designation: D 6303-98,
"Standard Test Method for Formaldehyde in Water," March 1999.

**Table 1.** Recommended Operating Conditions for the \[AQU\] GC/FID\
Analysis of the Impinger Samples

  ------------------------------------- ---------------------------------
                                        

  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

  H~2~ 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

  Ramp 2:                               70°C/min to 105°C for 17 minutes

  Ramp 3:                               70°C/min to 220°C for 3 minutes

  Retention Time Order:                 Acetaldehyde, Methanol, Acrolein,
                                        Propionaldehyde, Methyl Ethyl
                                        Ketone, Methyl Isobutyl Ketone,
                                        Cyclohexanol, Phenol

                                        
  ------------------------------------- ---------------------------------

**Table 2.** Recommended Operating Conditions for the

Preconcentrator and \[MSD\] GC/MS

Analysis of the Canister Samples

  ------------------------------------- ---------------------------------
  Cryogenic Preconcentrator             

                                        

  Sample Volume for Calibration:        500 mL

  Module 1 Trap Temperature:            -150^o^C

  Module 1 Desorb Temperature:          20^o^C

  Module 2 Trap Temperature:            -10^o^C

  Module 2 Desorb Temperature:          180^o^C

  Module 3 Trap Temperature:            -170^o^C

  Module 3 Inject Temperature:          100^o^C

  Transfer Line Temperature:            100^o^C

                                        

  Gas Chromatograph/Mass Selective      
  Detector                              

                                        

  Inlet Temperature:                    180^o^C

  Carrier Gas:                          Helium

  Carrier Gas Flow Rate:                Constant flow mode at 2.0 mL/min

  Column:                               J&W DB-624, 60 m x 0.25 mm id x
                                        1.4 micron fused silica capillary
                                        column with 10 m deactivated
                                        fused silica guard column

  Cryogenics:                           On

  Temperature Program °C:               

  Initial:                              20°C for 3 min

  Ramp 1:                               3°C/min to 100°C for 3 minutes

  Ramp 2:                               5°C/min to 140°C for 2 minutes

  Ramp 3:                               7°C/min to 240°C for 0 minutes

  Total Run Time:                       57 min

  Mass Range Scan:                      29-250 amu

                                        
  ------------------------------------- ---------------------------------

**Table 3.** Recommended Operating Conditions for the \[TER\] GC/FID

Analysis of the Canister Samples

  ------------------------------------- ---------------------------------
                                        

  Injection:                            Split

  Injector Temperature:                 180°C

  Injection Volume:                     2 mL -- sample loop

  Split Ratio:                          1.5:1

  Split Flow:                           4.8 mL/min

  Total Flow:                           9.8 mL/min

  FID Detector Temperature:             250°C

  H~2~ 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.

  Column:                               J&W DB-1, 30 m x 0.32 mm id x
                                        0.25 micron fused silica
                                        capillary column with 10 m
                                        deactivated fused silica guard
                                        column

  Cryogenics:                           Off

  Temperature Program °C:               

  Initial:                              55°C for 16 min

  Ramp 1:                               120°C/min to 240°C for 2 minutes

  Retention Time Order:                 Cumene, α-pinene, camphene,
                                        β-pinene, p-mentha-1,5-diene,
                                        3-carene, p-cymene, limonene

                                        
  ------------------------------------- ---------------------------------

**Figure 1.** Schematic of Sample Analyses and Analytes

![](media/image1.wmf){width="4.571527777777778in" height="2.925in"}

**Figure 2.** Chilled Impinger/Canister Sample Collection Trains

![](media/image2.wmf){width="7.993055555555555in"
height="5.048611111111111in"}

**Figure 3.** Quality Assurance Sample Collection Trains

![](media/image3.wmf){width="7.791666666666667in"
height="5.621527777777778in"}

![](media/image4.wmf)**Figure 4.** Percent Recovery for the Spiked
Sample Run

**Figure 5.** Percent Recovery for the Spiked Train Sample Run

![](media/image5.wmf)

EXAMPLE FIELD DATA COLLECTION SHEET

![](media/image6.wmf)

![](media/image7.wmf)

![](media/image8.png){width="6.708333333333333in"
height="10.131944444444445in"}

[^1]: Federal Register, Part VIII, EPA,, 40 CRF Part 136, Rules and
    Regulations, "Appendix B to Part 136-Definition and Procedure for
    the Determination of the Method Detection Limit"