From: David Word [ mailto: d_ word@ src ncasi. org] Sent: Wednesday, February 04, 2004 9: 46 AM To: Becky ( Rebecca) Nicholson Cc: Ric Law; John Pinkerton Subject: NCASI 99.02 Becky:

As John Pinkerton was reviewing 99.02 for inclusion in our sampling manual, he found an error in Figure 1. The T14 GC/ FID analysis should be MSD GC/ MSD. I have attached a corrected version.

If you can still make a change, then good. If not, that's OK. The correction is not critical, and should have little, if any, effect.

Thanks,

DW DRAFT REVISED METHOD IM/ CAN/ WP 99.02 March 2003 ii 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 i 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 140th Terrace 402 SW 140th 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 140th 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. ii Disclaimer THE MENTION OF TRADE NAMES OR COMMERCIAL PRODUCTS DOES NOT CONSTITUTE ENDORSEMENT OR RECOMMENDATION FOR USE. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 1 NCASI METHOD IM/ CAN/ WP 99.02 IMPINGER/ CANISTER SOURCE SAMPLE METHOD FOR SELECTED COMPOUNDS AT WOOD PRODUCTS FACILITIES 1.0 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: The action, activity, or procedural step is    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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 2 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.

2.0 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. 2.1 This method has been structured to allow for the determination of only the desired compounds of interest. While Table 2.1 provide 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 3 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 3.0 Principle and Methodology 3.1 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 4 3.2 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 than 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.

3.2.1 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.

3.2.2 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.

3.2.3 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).

3.2.4 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 5 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.

<IP_ADDRESS> [ AQU] Method Detection Limit   This method will require that a method detection limit ( MDL) be establish for each compound detected by the [ AQU] analytical procedure. MDLs must be established as defined by EPA1, 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 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 <IP_ADDRESS> [ 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 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" NCASI METHOD IM/ CAN/ WP 99.02 January 2004 6 NCASI established that the MDL for formaldehyde in the source gas tested ( based on 75 mL volume of aqueous impinger sample and 400 mL/ min sample rate) was 0.13 ppmv.

<IP_ADDRESS> [ 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.

<IP_ADDRESS> [ 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.

4.0 Apparatus 4.1 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).

4.1.1 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 7 4.1.2 Heated Filter Box  The heated probe is directly connected to a heated box containing a Teflon filter. The filter housing and connections are made of stainless steel. A thermocouple connected to or within the filter housing is used to record the filter temperature which must be maintained at 250 ± 25 ° F.

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

4.1.4 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.

4.1.5 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.

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

4.1.7 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.

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

4.1.9 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.

4.1.10 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.

4.1.11 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 8 4.1.12 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.

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

4.1.14 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.

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

4.2 [ AQU] GC/ FID analysis 4.2.1 Laboratory glassware  Volumetric pipets, volumetric flasks, 2.0 mL autosampler vials, and syringes necessary for standards preparation and analysis.

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

4.2.3 Column  30 m x 0.53 mm x 3 µ m 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.

4.2.4 GC detector  Flame ionization detector with appropriate data acquisition system.

4.3 [ FOR] Formaldehyde analysis 4.3.1 Laboratory glassware   Borosilicate test tubes ( 5 to 10 mL) with TFEfluorocarbon lined screw caps, 50 mL buret, volumetric pipets, volumetric flasks, syringes, and cuvettes necessary for standards preparation and analysis. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 9 4.3.2 Spectrophotometer  A spectrophotometer capable of measuring absorbance at a 412 nm wavelength.

4.3.3 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.

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

4.3.5 Centrifuge with capped tubes.

4.3.6 Magnetic stirrer and stir bars.

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

4.4 [ MSD] GC/ MSD analysis 4.4.1 Laboratory glassware  Volumetric pipets, volumetric flasks, and syringes necessary for standards preparation and analysis.

4.4.2 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.

4.4.3 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.

4.4.4 Column  60 m x 0.32 mm x 0.25 µ m 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.

4.4.5 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.

4.5 [ TER] GC/ FID analysis 4.5.1 Laboratory glassware  Volumetric pipets, volumetric flasks, and syringes necessary for standards preparation and analysis. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 10 4.5.2 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.

4.5.3 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.

4.5.4 Column  30 m x 0.32 mm x 0.25 µ m 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.

4.5.5 GC detector  Flame ionization detector with appropriate data acquisition system.

5.0 Reagents 5.1 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.

5.2 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.

5.3 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.

5.4 [ 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 11 Table 5.1. Reagents for the [ AQU] Primary Stock Solution Compound Amount ( µ L) 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 5.5 [ 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.

5.6 [ 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.

5.6.1 [ 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.

5.6.2 [ 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.

5.7 [ 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 12 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.

5.8 [ 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.

5.9 [ 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.

5.10 [ 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.

5.11 [ 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.

5.11.1 [ 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 13 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 ( µ L) 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 µ L of this aqueous stock solution into a clean evacuated canister ( below 1.0 in Hga) along with 170 µ L 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.

5.11.2 [ 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.

5.11.3 [ 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 14 Number 1 or other approved certified level.

5.11.4 [ 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.

5.12 [ 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.

5.13 [ 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. Then, inject 100 µ L 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 ( µ L) to Add to 10 mL Volumetric Flask p mentha 1,5 diene 810 3 carene 786 cumene 694 p cymene 780 limonene 811   pinene 795   pinene 793 camphene ( solid) 809 mg NCASI METHOD IM/ CAN/ WP 99.02 January 2004 15 5.14 [ 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.

5.15 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.

5.15.1 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.

5.15.2 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 16 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.

5.16 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.

6.0 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.

6.1 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.

6.2 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.

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

6.4 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 17 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.

6.5 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.

6.5.1 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.

6.5.2 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 18 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.

6.6 Pre Sample Run Procedures   6.6.1 Verify that the probe and filter housing are at operating temperature. Place crushed ice and water around the impingers.

6.6.2 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.

6.6.3 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 O2 and CO2.

6.6.4 Insert probe into test port and align perpendicular to source gas flow. Recheck the operating temperature. Close the on/ off valve at the slipstream 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.

6.7 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.

6.7.1 Start the impinger sample pump. Record start time and flow rate at the flow meter. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 19 6.7.2 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.

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

6.7.4 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.

6.8 Post Sample Run Procedures   6.8.1 Remove probe from test port.

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

6.8.3 Verify that the difference between pre and post average flow rate measurements are within 20%.

6.8.4 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.

6.9 Sample Recovery   6.9.1 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.

6.9.2 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.

6.9.3 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 20 6.9.4 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.

6.10 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.

6.10.1 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.

6.10.2 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.

6.10.3 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.

<IP_ADDRESS> 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 21 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.

<IP_ADDRESS> 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 determined by one sample train minus the dry source concentration determined by the other sample train divided by the average dry source concentration determined from both trains ( Equation 6.1).

( ) ( ) 100 , % ×   =

SD SN SD SN C C Average C C ABS difference ( Equation 6.1)

CSN = dry source gas concentration determined by the normal train, ppmvd CSD = 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.

<IP_ADDRESS> Source Gas Concentration  The source gas concentration reported for duplicate sample runs will be based on the average of the dry source gas concentrations determined by each collection train even if the QA criteria is not met.

6.10.4 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 22 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.

<IP_ADDRESS> 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.

<IP_ADDRESS> 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 23 <IP_ADDRESS> 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.

<IP_ADDRESS> 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.

100 mass mass %

) i ( ) i ( ) i ( × =

FS recovered Recovery ( Equation 6.2)

massrecovered( i) = mass of analyte ( i) recovered by the spiked collection train massFS( 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.

6.10.5 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 24 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. 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.

<IP_ADDRESS> 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.

<IP_ADDRESS> 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 <IP_ADDRESS>). 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.

<IP_ADDRESS> 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 25 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.

<IP_ADDRESS> 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.

100 mass mass Recovery %

FS( i) ST( i) ( i) × = ( Equation 6.3)

massST( i) = mass of analyte ( i) recovered by the spiked collection train massFS( 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.

7.0 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.

7.1 Sample Preparation   7.1.0 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.

7.1.1 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 26 7.2 [ 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.

7.2.1 [ 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 µ L 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 250oC, the oven to over 200oC, and the detector to 275oC for several hours.

7.2.2 [ 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 µ L of the [ AQU] internal standard stock ( Section 5.6) into each vial. Then fill each vial with a different [ AQU] calibration standard. The NCASI METHOD IM/ CAN/ WP 99.02 January 2004 27 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 ( RRFM). The RRFM is calculated by Equation 7.1 using a relationship between the responses obtained for the internal standard and analyte.

M IS IS M M C C x A A RRF = ( Equation 7.1)

RRFM = Relative response factor for an analyte AM = area of analyte peak AIS = area of internal standard peak CM = concentration of analyte injected ( mg/ L) CIS = concentration of internal standard injected ( mg/ L)

A calibration curve will be acceptable when the relative standard deviation of the RRFMs are less than 20%. The average RRFM will then be used to calculate the concentration of an analyte in an aqueous sample by Equation 7.2.

M IS IS averageRRF x A C x S S A C = ( Equation 7.2)

CS = Concentration of the analyte in the sample, mg/ L AS = Area of the analyte peak in the sample CIS = Concentration of the internal standard, mg/ L AIS = Area of the internal standard peak in the sample averageRRFM = 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.

7.2.3 [ 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 28 <IP_ADDRESS> 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.

<IP_ADDRESS> 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 <IP_ADDRESS>).

<IP_ADDRESS> 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.

<IP_ADDRESS> 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.

<IP_ADDRESS> 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 29 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.

7.2.4 [ 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.

7.3 [ 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.

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

7.3.2 [ 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 60oC. 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 30 7.3.3 [ FOR] Formaldehyde Laboratory QA Requirements   The formaldehyde analysis includes both mandatory and recommended laboratory QA procedures.

<IP_ADDRESS> 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.

<IP_ADDRESS> 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 <IP_ADDRESS>).

<IP_ADDRESS> 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.

<IP_ADDRESS> 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.

7.3.4 [ 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 31 Add 2.0 mL of the acetylacetone reagent and mix thoroughly. Place test tube in a water bath for 10 minutes at 60oC. 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.

7.4 [ 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.

7.4.1 [ 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 32 7.4.2 [ 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 RRFMs obtained for each analyte of interest. Refer to Equation 7.1 ( Section 7.2.2) to calculate the RRFM for each calibration point along a calibration curve. A calibration curve will be acceptable when the relative standard deviation of the RRFMs are less than 20%. Use the average RRFM 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.

7.4.3 [ 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.

<IP_ADDRESS> 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.

<IP_ADDRESS> 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 <IP_ADDRESS>).

<IP_ADDRESS> 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 33 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.

<IP_ADDRESS> 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.

<IP_ADDRESS> 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.

7.4.4 [ MSD] GC/ MSD Source Sample Analysis   <IP_ADDRESS> Record the temperature and pressure of each canister at laboratory conditions.

<IP_ADDRESS> 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.

<IP_ADDRESS> Using a preconcentrator, inject a sample from each canister into the GC/ MSD. The concentration of the samples analyzed must be NCASI METHOD IM/ CAN/ WP 99.02 January 2004 34 determined from the calibration curves developed for this procedure.

7.5 [ 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.

7.5.1 [ 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.

7.5.2 [ 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 35 correlation coefficient. If that evaluation also fails, then prepare new calibration standards and/ or perform instrument maintenance.

7.5.3 [ 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.

<IP_ADDRESS> 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.

<IP_ADDRESS> 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 <IP_ADDRESS>).

<IP_ADDRESS> 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.

7.5.4 [ 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.

<IP_ADDRESS> Record the temperature and pressure of each canister at laboratory conditions.

<IP_ADDRESS> 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 36 <IP_ADDRESS> 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.

8.0 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.

8.1 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.

8.1.1 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.

<IP_ADDRESS> 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:

aqueous f, HCOH aqueous HCOH, V x mass C =

massHCOH, aqueous = mass of formaldehyde in the aqueous sample, µ g CHCOH = concentration of formaldehyde in aqueous sample, µ g/ mL Vf, aqueous = final volume of aqueous sample, mL NCASI METHOD IM/ CAN/ WP 99.02 January 2004 37 <IP_ADDRESS> 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: mL 100 x mass [ AQU] aqueous [ AQU], C =

mass[ AQU], aqueous = mass of [ AQU] analyte in the aqueous sample,

µ g C[ AQU] = concentration of analytei in the aqueous sample, µ g/ 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.

8.1.2 Mass Collected in the Canister   The collection train only captures a slipstream 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.

<IP_ADDRESS> 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:

      = Hg in 92 . 29 R 528 L 0 . 6 V std GS, GS GS P T

VGS, std = wet standard volume of gas sample at standard conditions, wsL TGS = temperature of gas sample ( equivalent to canister temperature) at laboratory conditions, ° R PGS = pressure of the gas sample prior to analysis, in Hga <IP_ADDRESS> Mass of [ MSD] or [ TER] Compounds in Canister Sample   Obtain the concentration of the compounds of interest in the canister gas NCASI METHOD IM/ CAN/ WP 99.02 January 2004 38 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:

( ) ( )

      = g g 10 MW L 24.055 gmole 1 V 10 C mass 6 ( i) , G 9 [ TER] or [ MSD] i, canister i, µ std S massi, canister = mass of analyte( i) in the canister, µ g Ci, [ MSD] or [ TER] = concentration of [ MSD] or [ TER] analyte in wet canister sample gas, ppbvw VGS, std = wet standard volume of gas sample at standard conditions, wsL ( one atmosphere and 68 ° F) MW( i) = molecular weight of analytei, g/ gmole 8.1.3 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.

<IP_ADDRESS> 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:

        =

meas vap bar meas probe drystd probe T R Hg in P P Q Q

528 92 . 29 , ,

Qprobe, drystd = dry standard flow rate measured at the probe tip of the sample collection train, dsL/ min Qprobe, meas = actual flow rate measured at the probe tip of the sample collection train, L/ min Pbar = barometric pressure at flow rate measurement site, in Hga Pvap = water vapor pressure in the gas stream being measured, assumed to be saturated at ambient dry temperature, in Hga. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 39 Tmeas = 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:

t Q Q drystd probe f drystd probe i drystd sourcegas ×

      + = 2 V , ) ( , ) ( ,

Vsourcegas, 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 <IP_ADDRESS> 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:

      × =

can o can o drystd s canisterga o T R Hg in P L , , , ) ( 528 92 . 29 0 . 6 V

V( o) canistergas, drystd = dry standard canister gas volume, dsL, at start of sample run Po, can = pressure of the canister, in Hga, at start of sample run To, can = temperature of canister gas sample, ° R, at start of sample run Equation 8:

        × =

can f F vap can f drystd s canisterga f T R Hg in P P L , 38 @ ,

, ) ( 528 92 . 29 0 . 6 V

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 Pvap@ 38 ° F = moisture correction for water vapor in canister equivalent to 0.2292 in Hga; gas stream assumed saturated leaving NCASI METHOD IM/ CAN/ WP 99.02 January 2004 40 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:

drystd s canisterga o drystd s canisterga f drystd ple anistersam , ) ( , ) ( , c V V V   =

Vcanistersample, 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 <IP_ADDRESS> 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:

drystd ple anistersam drystd sourcegas , c ,

V V CF=

CF = canister mass correction factor Vsourcegas, drystd = Total dry standard volume of source gas sampled by the collection train, dsL Vcanistersample, drystd = dry standard volume of canister sample collected, dsL 8.1.4 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:

( ) CF x mass mass canister i aqueous i , , total , i mass + =

massi, total = total mass of analyte( i) captured by the collection train, µ g massi, aqueous = mass of analyte( i) in the aqueous sample, µ g massi, canister = mass of analyte( i) in the canister sample, µ g NCASI METHOD IM/ CAN/ WP 99.02 January 2004 41 CF = canister mass correction factor 8.2 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.

8.3 Equation 12:

drystd sourcegas i L L , 6 6 total i,

gas source i, V 10 gmole L 055 . 24 MW 1 g 10 g mass C

      × = µ µ Ci, sourcegas = concentration of analyte( i) in the source gas, ppmvd massi, total = total mass of analyte( i) captured by the collection train, µ g MW( i) = molecular weight of analytei, g/ gmole Vsourcegas, drystd = Total dry standard volume of source gas sampled by the collection train, dsL 9.0 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. NCASI METHOD IM/ CAN/ WP 99.02 January 2004 42 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 µ L Injection Liner Size: 2 mm id ( no packing) Syringe Rinse 10 rinses with VOC free DI water FID Detector Temperature: 275 ° C H2 Flow Rate: Approx. 50 mL/ min Air Flow Rate: Approx. 500 mL/ min Makeup Gas: Helium Makeup Gas Flow Rate: Approx. 25 mL/ min Carrier Gas: Helium Carrier Gas Flow Rate: Constant pressure mode to give 6 mL/ min at room temperature Column: J& W DB 624, 30 m x 0.53 mm id x 3 micron fused silica capillary column with 10 m deactivated fused silica guard column Cryogenics: On Temperature Program ° C: Initial: 0 ° C for 3 min Ramp 1: 5 ° C/ min to 50 ° C for 0 minutes 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 43 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:  150oC Module 1 Desorb Temperature: 20oC Module 2 Trap Temperature:  10oC Module 2 Desorb Temperature: 180oC Module 3 Trap Temperature:  170oC Module 3 Inject Temperature: 100oC Transfer Line Temperature: 100oC Gas Chromatograph/ Mass Selective Detector Inlet Temperature: 180oC Carrier Gas: Helium Carrier Gas Flow Rate: Constant flow mode at 2.0 mL/ min 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 NCASI METHOD IM/ CAN/ WP 99.02 January 2004 44 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 H2 Flow Rate: 40 mL/ min Air Flow Rate: 450 mL/ min Makeup Gas: Helium Makeup Gas Flow Rate: 45 mL/ min Carrier Gas: Helium Carrier Gas Flow Rate: Ramped pressure mode. Initial pressure 14.0 psi. Ramp 7 psi/ min to 9.3. Initial flow 3.2 mL/ min. 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,   pinene, camphene,   pinene, p mentha 1,5 diene, 3 carene, p cymene, limonene NCASI METHOD IM/ CAN/ WP 99.02 January 2004 45 Figure 1. Schematic of Sample Analyses and Analytes [ MSD] GC/ MSD Analysis Canister Analysis Sampling Train [ TER] GC/ FID For Terpenes [ FOR] Acetylacetone Procedure [ AQU] GC/ FID Analysis Impinger Analysis NCASI METHOD IM/ CAN/ WP 99.02 January 2004 46 Figure 2. Chilled Impinger/ Canister Sample Collection Trains Heated Probe ( 250 F) Ice Water Bath Heated Filter Box ( 250 F) Filter Optional Variable Area Flow Meter Critical Orifice 400 mL/ min Teflon Head Pump Variable Area Flow Meter Needle Valve 6L Canister Excess Sample Gas Stream Canister Sample On/ Off Valve NCASI METHOD IM/ CAN/ WP 99.02 January 2004 47 Figure 3. Quality Assurance Sample Collection Trains Heated Probe Filter Box F Pump/ Control Box Aqueous Impingers SUMMA Canister N Spiked Train Sample Run Heated Probe Filter Box F Pump/ Control Box Aqueous Impingers D Run Duplicate Duplicate Sample Run F Pump/ Control Box Aqueous Impingers N Run Normal Heated Probe Filter Box F Pump/ Control Box Spike Tee ( for introduction of liquid spike solution)

S Run Spike Spiked Sample Run F Pump/ Control Box Aqueous Impingers N Run Normal Previously spike SUMMA Canister D N S N N NCASI METHOD IM/ CAN/ WP 99.02 January 2004 48 Figure 4. Percent Recovery for the Spiked Sample Run Source Gas Impingers Aqueous Spike Spike Canister ppmvdST( i) Convert to Source Gas Concentration mg/ L( i) ppbvd( i) + Spike Train ( ST)

S Source Gas Impingers Non spiked Canister ppmvdNT( i) Convert to Source Gas Concentration mg/ L( i) ppbvd( i) + Normal Train ( NT)

N Mass Recovered by Spiked Train ppmvdrecovered( i) = ppmvdST( i) ppmvdNT( i)

ppmvdrecovered( i) Convert to Massrecovered( i)

Combine Field Spike Mass ( FS)

Sample Bottle Aqueous Field Spike mg/ LAFS( i) MassAFS( i) S ppbvdGFS( i) MassGFS( i) Gas Field Spike MassFS( i) = MassAFS( i) + MassGFS( i)

% Recovery( i) = Massrecovered( i)

MassFS( i) Calculate % Recovery NCASI METHOD IM/ CAN/ WP 99.02 January 2004 49 Figure 5. Percent Recovery for the Spiked Train Sample Run Convert to Gas Spike Concentration Impingers Non spiked Canister ppmvdST( i) mg/ L( i) ppbvd( i) + Spiked Train ( ST)

N Aqueous Spike Gas Spike Convert to ppmvdST( i) Mass ST( i)

Sample Bottle Aqueous Field Spike mg/ LAFS( i) MassAFS( i) S ppbvdGFS( i) MassGFS( i) Gas Field Spike MassFS( i) = MassAFS( i) + MassGFS( i) Combine Field Spike Mass ( FS)

% Recovery( i) = MassFS( i) MassST( i) Calculate % Recovery NCASI METHOD IM/ CAN/ WP 99.02 January 2004 50 EXAMPLE FIELD DATA COLLECTION SHEET SAMPLER DATE: CANISTER ID# CAN CODE:

SAMPLING CODE: FIELD SPKIE Y N gas____ mL aqueous_____ mL DESCRIPTION:

SECTION 1a SECTION 1b SECTION 2 SECTION 3 SECTION 4 SECTION 5 LEAK CHECK 1 2 3 4 5 AVG % DIFFERENCE % DIFFERENCE ° F in. Hga ° F in. Hga LEFT VAC. GA. VENT TIME FLOW ( mL/ min) ( in. Hga) TIME P ( in Hga) FLOW ( mL/ min) TEMP ° F FLOW ( mL/ min)

START 5 10 15 20 25 30 35 40 45 50 55 STOP COMMENTS: AMBIENT TEMPERATURE / PRESSURE IMPINGER CANISTER PRE RUN POST RUN PRE RUN POST RUN PRE RUN POST RUN FINAL DIFFERENCE PROBE SAMPLE FLOW RATES COMBINED TRAIN FLOW RATES PRESSURE INITIAL TRAIN SPIKE NCASI HAPS TRAIN FIELD DATA SHEET