Dioxin Testing and Analysis


Method 0010/Method 0023A

Method for Determining Dioxins and Furans in Stack Gas

Sampling and Field Procedure for Dioxins/Furans in Stack Gases

Sample Name:

Modified Method 5 (Method 0010/Method 0023A)

  • Dioxins/Furans
Sampler:

Stack Sampling Engineer

Process Sample Location:

Stack Sampling Platform

Sampling & Health & Safety Equipment:

Sampling and safety equipment is as follows:

  • Method 0010/Method 0023A Sampling Train
  • Organic-free DI water
  • Aluminum foil
  • 250 mL amber Boston Round - acetone probe rinse, the methylene chloride probe rinse, and toluene probe rinse
  • Glass Petri Dish - particulate filter
  • XAD-2 Resin Tube
  • 250 mL amber Boston Round - backhalf rinse of the filter holder behind the particulate filter, coil condenser and connecting glassware with acetone, methylene chloride, and toluene
  • Squirt bottles for acetone, methylene chloride and toluene
  • Graduated cylinder
  • Safety glasses or face shield
Gloves and other safety equipment as required

 

Sample Collection Frequency:

Continuously for approximately 4 hours until at least 3 m3 of stack sample is collected for each run; sampling rate will be ≤ 0.75 m3 per hour.  Three runs will constitute a test.

Sampling Procedures:

XAD-2 Tube Preparation - The laboratory will prepare the XAD-2 resin tubes and deliver them to the sampling team for use during the project.  During the resin preparation, the five (5) Method 0023A sampling surrogates will be spiked onto the XAD-2.  These labeled spikes will serve as sampling surrogates to indicate analyte loss due to the sampling process. The procedures for preparing, handling, storing, and analyzing the tubes are those described in the U.S. EPA SW-846 Methods referenced below.  Pre-cleaned XAD-2 resin is commercially available (Supelco®) and will be used to prepare the resin tubes.  Two XAD-2 resin tubes using the purchased resin will be spiked with surrogates and isotope dilution internal standards and analyzed as laboratory resin blanks (Spiked Resin Blanks) to confirm that the resin is free from significant background contamination and to assess the recovery capabilities of the analytes from the resin batch.

For storage and transport to the field, the resin tubes will have their ends sealed with Teflon® tape, wrapped in aluminum foil, sealed in Ziploc® bags, and packed in a clean sample cooler.  In the field, the cooler will be stored in the sample recovery trailer and resin tubes are removed only when ready for labeling and installation in the sampling train.

Before each sampling run, the Sampling Coordinator will supply a XAD-2 resin tube and a field blank tube to the Stack Sampling Engineer who will direct the operation of the MM-5 train.  At the end of each run, the Sample Coordinator will recover from the Stack Sampling Engineer the resin tubes and other train components and complete the preparation of the sample documentation.  The MM-5 stack samples will be stored on ice at approximately 4oC in insulated coolers in a storage area away from sources of fugitive contamination.

MM-5 Train Operation - The MM-5 train components will be provided by the Stack Sampling team.  With the exception of the necessary modification for installing and recovering the resin tubes, the sampling procedures will be as specified in U.S. EPA Methods 1 and 2 for stack flow measurements, and Method 4 and 5 for moisture content and particulate.  An initial traverse is made with a pitot tube at each sample point following U.S. EPA Methods 1 and 2 to establish the stack velocity profile, temperature, and flow rate, and to check for cyclonic air flow.  Sample point location will be in accordance with U.S. EPA Method 1. The sampling team will record the data as recommended in Method 5.

The sampling equipment will be calibrated before and after the test.  The pretest calibrations will be available for agency review before testing commences.

The first impinger (Impinger #1) will be an empty condensate knockout impinger.  The MM-5 train will be charged with 100 ml of organic-free DI water in the second (Impinger #2) and third (Impinger #3) impingers. The fourth impinger will contain indicating silica gel which is tare weighed to the nearest 0.5 gram.

The sampling train will be leak tested according to U.S. EPA Method 5 protocols.  A Teflon® plug or a sampler's thumb covered with Teflon® tape will be placed over the end of the nozzle to ensure that no contaminants are transferred to the train during nozzle leak checks.

MM-5 Train Sample Recovery - The eight (8) sample fractions that will be separately recovered from the MM-5 train are as follows:

  • Particulate Filter - Will be removed from its holder and carefully placed in its original, labeled Petri dish, sealed with Teflon® tape, and sealed in a Ziploc® plastic bag for shipment to the laboratory.

 

  • Solvent Probe Rinse - The nozzle, probe, the front-half of the filter holder will be brushed and rinsed three times with acetone followed by brushing and rinsing three times with methylene chloride.  The rinses will be combined and placed in a 250 mL amber labeled Boston Round sample collection bottle with a Teflon®-lined lid.
  • Toluene Probe Rinse - As a separate rinse following the acetone and methylene chloride, the nozzle, probe, the front-half of the filter holder will be brushed and rinsed three times with toluene.  The rinses will be placed into a separate 250 mL amber labeled Boston Round sample collection bottle with a Teflon®-lined lid only when other analyte types are being measured such as SVOCs or PAHs.  Do not combine this toluene rinse with the acetone/methylene chloride solvent rinses under combined train conditions.  These samples are to be handled separately in the laboratory preparation when combined trains are conducted.

 

  • XAD-2 Resin Tube - The XAD-2 resin tube will be removed from the sampling train, its ends capped or sealed with Teflon® tape, wrapped in aluminum foil, sealed in a Ziploc® bag, and stored on ice for shipment to the laboratory.
  • Back Half of the Filter Holder and Coil Condenser solvent glassware rinses - The back half of the filter holder, coil condenser, and connecting glassware will be rinsed three times with acetone and methylene chloride.  The rinses will be combined and placed in a 250 mL amber Boston Round sample bottle with Teflon®-lined lid.

 

  • Toluene Back Half of the Filter Holder and Coil Condenser glassware rinses - The back half of the filter holder, coil condenser, and connecting glassware will then be rinsed three times with toluene. The rinses will be placed in a separate 250 mL amber Boston Round sample bottle with Teflon®-lined lid only when other analyte types are being measured such as SVOCs or PAHs. Do not combine this toluene rinse with the acetone/methylene chloride solvent rinses under combined train conditions.  These samples are to be handled separately in the laboratory preparation when combined trains are conducted.
  • Condensate (Impinger #1) and Impinger Contents of Impingers #2 and #3 - The aqueous contents of each individual impinger (1-3) will be volumetrically measured to the nearest milliliter, recorded separately for moisture calculations.

 

  • Silica Gel - The silica gel impinger will be reweighed to the nearest 0.5 gram and the weight gain is calculated as moisture gain in the train.

All of the MM-5 sample components will be assigned unique sample tracking numbers and labeled with date and test run number.  The samples will be recovered by the Sample Coordinator and the Stack Sampling Engineer and the sample collection documentation will be recorded.  The Sample Coordinator will record the appropriate data in the field log book and pack the samples on ice in a storage cooler. 

 

Quality Assurance:

A complete MM-5 blank train will be prepared once during the test burn series, set up near the base of the stack in a manner similar to the actual MM-5 sampling train and applying an equivalent number of associated leak checks.  It is required that the blank train be set up during one of the actual dioxin and furan runs.  The train will remain sealed with the filter holder and probe heated to their standard operating temperature at that location for a time period equivalent to one test run.  The blank train samples will be recovered using the same procedures described above for the actual train samples.

                                                An XAD-2 resin field blank will be opened at the location of train assembly one time during the test.  The XAD-2 should remain open for the duration of actual train assembly.   An XAD-2 trip blank should accompany each Method 0010/0023A shipment of samples to the laboratory.

                                                Two spiked resin blanks of the XAD-2 resin are to be prepared at the time or resin tube preparation and analyzed with the field samples.

Liquid samples will have the liquid levels clearly marked on the sample bottles to display the final sample contents level.

Sample Preservation:

The holding time for dioxins and furans is 30 days to extraction from the time of collection.  All samples should be preserved on ice at approximately 4oC.

Method References:

Method 0023A - "Sampling Method for Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofuran Emissions from Stationary Sources". Taken from Test Methods for Evaluating Solid Waste, Physical/Chemical Methods.  SW-846, Third Edition, September 1986.   Final Update I (July 1992), Final Update IIA (August 1993), Final Update II (September 1994), Final Update IIB (January 1995), Final Update III (December 1996), and Final Update IIIA (April 1998).  USEPA, OSWER, Washington, D.C. 20460.

Method 0010 - "Modified Method 5 Sampling Train". Taken from Test Methods for Evaluating Solid Waste, Physical/Chemical Methods.  SW-846, Third Edition, September 1986.   Final Update I (July 1992), Final Update IIA (August 1993), Final Update II (September 1994), Final Update IIB (January 1995), Final Update III (December 1996), and Final Update IIIA (April 1998).  USEPA, OSWER, Washington, D.C. 20460.

Method 5, Appendix A, Test Methods and Procedures, New Source Performance Standards, 40 CFR 60.

Analysis of Dioxins/Furans in Method 0023A Train Samples

Sample Name:

MM-5 Train for the collection of Dioxins and Furans

The actual sample names given to fractions derived from the Method 0023A Train are:

  • Front Half Composite - Particulate filter and the front half of the filter holder, probe and nozzle solvent rinses (Figure 2)
  • Back Half Composite - XAD-2 resin tube and the back half of the filter holder and coil condenser solvent rinses (Figure 3)

Sample Holding Time:

Extract within 14 days of sample collection, and analyze within 40 days from extraction date.

Analysis Procedures:

Front Half Composite
Place solvent probe and nozzle rinse, particulate filter and front half of the filter holder rinses into a Soxhlet extractor.  Add semivolatile surrogate compounds and isotopically labeled dioxin/furan and PCB internal standards onto the filter portion prior to extraction.  Extract for 18 hours using methylene chloride.

Concentrate extract to 10 ml.  Divide the extract into three equal portions:  a 3.3 ml portion for semivolatile PIC analyses, a 3.3 ml portion for dioxin/furan analysis, and a 3.3 ml portion for PCB congeners and coplanars.

Add the toluene probe rinse portion of the sample to the Soxhlet extractor.  Extract the Front Half Composite a second time using toluene, for 18 hours.  Concentrate the extract down to 10 mLs.  Remove a 3.3 mL portion of the extract and combine it with the methylene chloride extract portion designated for dioxins and furans.

Add semivolatile internal standards and dioxin/furan and PCB recovery standards to the appropriate extract portions, and analyze by Methods 8270, 8290, and 1668 for semivolatile PICs, dioxins/furans, and PCBs.


Back Half Composite
Place XAD-2 Resin Tube and the Backhalf of the Filter Holder and Coil Condenser Solvent Rinses into a Soxhlet extractor.  Add semivolatile surrogate compounds and isotopically labeled dioxin/furan and PCB internal standards onto the filter portion prior to extraction.  Extract for 18 hours using methylene chloride.

Concentrate extract to 10 ml.  Divide the extract into three equal portions: a 3.3 ml portion for semivolatile PIC analyses, a 3.3 ml portion for dioxin/furan analysis, and a 3.3 ml portion for PCB congeners and coplanars.

Add the toluene probe rinse portion of the sample to the Soxhlet extractor.  Extract the Back Half Composite a second time using toluene, for 18 hours.  Concentrate the extract down to 10 mLs.  Remove a 3.3 mL portion of the extract and combine it with the methylene chloride extract portion designated for dioxins and furans.

Add semivolatile internal standards and dioxin/furan and PCB recovery standards to the appropriate extract portions, and analyze by Methods 8270, 8290, and 1668 for semivolatile PICs, dioxins/furans, and PCBs.

Condensate Composite
Place a one liter portion of the sample in a separatory funnel and add semivolatile surrogate compounds and PCB isotope dilution internal standards onto the sample.  Perform a liquid-liquid extraction using Method 3510.  Concentrate extract to 10 mL followed by a splitting of the sample 50:50 for semivolatiles and PCBs. Add semivolatile internal standards and the PCB recovery standards to the appropriate extract and analyze by Methods 8270 and 1668 for semivolatile PICs and PCBs, respectively.

 

Method References:

Method 3510 - "Separatory Funnel Liquid-Liquid Extraction". Taken from Test Methods for Evaluating Solid Waste, Physical/Chemical Methods.  SW-846, Third Edition, September 1986.   Final Update I (July 1992), Final Update IIA (August 1993), Final Update II (September 1994), Final Update IIB (January 1995), Final Update III (December 1996), and Final Update IIIA (April 1998).  USEPA, OSWER, Washington, D.C. 20460.

                                                Method 3540 - "Soxhlet Extraction". Taken from Test Methods for Evaluating Solid Waste, Physical/Chemical Methods.  SW-846, Third Edition, September 1986.   Final Update I (July 1992), Final Update IIA (August 1993), Final Update II (September 1994), Final Update IIB (January 1995), Final Update III (December 1996), and Final Update IIIA (April 1998).  USEPA, OSWER, Washington, D.C. 20460.

                                                Method 3542 - "Extraction of Semivolatile Analytes Collected Using Method 0010 (Modified Method 5 Sampling Train)". Taken from Test Methods for Evaluating Solid Waste, Physical/Chemical Methods.  SW-846, Third Edition, September 1986.   Final Update I (July 1992), Final Update IIA (August 1993), Final Update II (September 1994), Final Update IIB (January 1995), Final Update III (December 1996), and Final Update IIIA (April 1998).  USEPA, OSWER, Washington, D.C. 20460.

                                                Method 8290 - "Polychlorinated Dibenzodioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) by High Resolution Gas Chromatography/High-Resolution Mass Spectrometry (HRGC/HRMS)". Taken from Test Methods for Evaluating Solid Waste, Physical/Chemical Methods.  SW-846, Third Edition, September 1986.   Final Update I (July 1992), Final Update IIA (August 1993), Final Update II (September 1994), Final Update IIB (January 1995), Final Update III (December 1996), and Final Update IIIA (April 1998).  USEPA, OSWER, Washington, D.C. 20460.

                                                Method 0023A - "Sampling Method for Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofuran Emissions from Stationary Sources" Taken from Test Methods for Evaluating Solid Waste, Physical/Chemical Methods.  SW-846, Third Edition, September 1986.   Final Update I (July 1992), Final Update IIA (August 1993), Final Update II (September 1994), Final Update IIB (January 1995), Final Update III (December 1996), and Final Update IIIA (April 1998).  USEPA, OSWER, Washington, D.C. 20460.

 

MM5 Train Sample Handling and Extract Splitting Scheme for the XAD-2
Resin Tube and the Back Half of the Filter Holder and Coil Condenser Solvent Rinses (Dioxins and Furans)

  Method-0023A-Sampling_Analysis-Procedures-8.jpg
View as PDF: Method 0023A Sampling_Analysis Procedures.pdf