EPA/625/R-96/01 Ob
Compendium of Methods
for the Determination of
Toxic Organic Compounds
in Ambient Air
Second Edition
Compendium Method TO-9A
Determination Of Polychlorinated,
Polybrominated And
Brominated/Chlorinated
Dibenzo-p-Dioxins And Dibenzofurans In
Ambient Air
Center for Environmental Research Information
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
January 1999

-------
Method TO-9A
Acknowledgements
This Method was prepared for publication in the Compendium of Methods for the Determination of Toxic
Organic Compounds in Ambient Air, Second Edition (EPA/625/R-96/010b), which was prepared under Contract
No. 68-C3-0315, WA No. 3-10, by Midwest Research Institute (MRI), as a subcontractor to Eastern Research
Group, Inc. (ERG), and under the sponsorship of the U.S. Environmental Protection Agency (EPA). Justice A.
Manning, John Burckle, and Scott Hedges, Center for Environmental Research Information (CERI), and Frank
F. McElroy, National Exposure Research Laboratory (NERL), all in the EPA Office of Research and
Development, were responsible for overseeing the preparation of this method. Additional support was provided
by other members of the Compendia Workgroup, which include:
•	John O. Burckle, U.S. EPA, ORD, Cincinnati, OH
James L. Cheney, Corps of Engineers, Omaha, NB
Michael Davis, U.S. EPA, Region 7, KC, KS
•	Joseph B. Elkins Jr., U.S. EPA, OAQPS, RTP, NC
Robert G. Lewis, U.S. EPA, NERL, RTP, NC
Justice A. Manning, U.S. EPA, ORD, Cincinnati, OH
•	William A. McClenny, U.S. EPA, NERL, RTP, NC
Frank F. McElroy, U.S. EPA, NERL, RTP, NC
•	Heidi Schultz, ERG, Lexington, MA
William T. "Jerry" Winberry, Jr., EnviroTech Solutions, Cary, NC
Method TO-9 was originally published in March of 1989 as one of a series of peer reviewed methods in the
second supplement to "Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Air, " EPA 600/4-89-018. In an effort to keep these methods consistent with current technology,
Method TO-9 has been revised and updated as Method TO-9A in this Compendium to incorporate new or
improved sampling and analytical technologies.
This Method is the result of the efforts of many individuals. Gratitude goes to each person involved in the
preparation and review of this methodology.
Author(s)
Bob Harless, U. S. EPA, NERL, RTP, NC
William T. "Jerry" Winberry, Jr., EnviroTech Solutions, Cary, NC
Gil Radolovich, Midwest Research Institute, KC, MO
Mark Horrigan, Midwest Research Institute, KC, MO
Peer Reviewers
Audrey E. Dupuy, U.S. EPA, NSTL Station, MS
Greg Jungclaus, Midwest Research Institute, KC, MO
•	Stan Sleva, TRC, RTP, NC
Robert G. Lewis, U.S. EPA, NERL, RTP, NC
•	Lauren Drees, U.S. EPA, NRMRL, Cincinnati, OH
Finally, recognition is given to Frances Beyer, Lynn Kaufman, Debbie Bond, Cathy Whitaker, and Kathy Johnson
of Midwest Research Institute's Administrative Services staff whose dedication and persistence during the
development of this manuscript has enabled it's production.
DISCLAIMER
This Compendium has been subjected to the Agency's peer and administrative review, and it has been
approved for publication as an EPA document. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
li

-------
Method TO-9A
Determination Of Polychlorinated, Polybrominated And Brominated/Chlorinated
Dibenzo-p-Dioxins And Dibenzofurans In Ambient Air
TABLE OF CONTENTS
Page
1.	Scope		9A-1
2.	Summary of Method		9A-2
3.	Significance		9A-3
4.	Safety 		9A-3
5.	Applicable Documents		9A-4
5.1	ASTM Standards 		9A-4
5.2	EPA Documents		9A-4
5.3	Other Documents		9A-5
6.	Definitions 		9A-5
7.	Interferences And Contamination		9A-9
8.	Apparatus		9A-9
8.1	High-Volume Sampler		9A-9
8.2	High-Volume Sampler Calibrator 		9A-9
8.3	High Resolution Gas Chromatograph-High Resolution Mass Spectrometer-Data
System (HRGC-HRMS-DS)		9A-10
9.	Equipment And Materials 		9A-10
9.1	Materials for Sample Collection 		9A-10
9.2	Laboratory Equipment		9A-11
9.3	Reagents and Other Materials 		9A-11
9.4	Calibration Solutions and Solutions of Standards Used in the Method 		9A-12
10.	Preparation Of PUF Sampling Cartridge		9A-12
10.1	Summary of Method		9A-12
10.2	Preparation of Sampling Cartridge 		9A-13
10.3	Procedure for Certification of PUF Cartridge Assembly		9A-13
10.4	Deployment of Cartridges for Field Sampling		9A-14
11.	Assembly, Calibration And Collection Using Sampling System		9A-14
11.1	Description of Sampling Apparatus		9A-14
11.2	Calibration of Sampling System 		9A-15
11.3	Sample Collection 		9A-21
in

-------
TABLE OF CONTENTS (continued)
Page
12.	Sample Preparation		9A-23
12.1	Extraction Procedure for Quartz Fiber Filters and PUF Plugs 		9A-23
12.2	Cleanup Procedures 		9A-23
12.3	Glassware Cleanup Procedures 		9A-25
13.	HRGC-HRMS System Performance 		9A-25
13.1	Operation of HRGC-HRMS 		9A-25
13.2	Colum Performance 		9A-26
13.3	SIM Cycle Time		9A-26
13.4	Peak Separation 		9A-26
13.5	Initial Calibration		9A-26
13.6	Criteria Required for Initial Calibration 		9A-27
13.7	Continuing Calibration		9A-28
14.	HRGC-HRMS Analysis And Operating Parameters		9A-28
14.1	Sample Analysis		9A-28
14.2	Identication Criteria		9A-29
14.3	Quantification		9A-29
14.4	Calculations 		9A-30
14.5	Method Detection Limits (MDLs)		9A-31
14.6	2,3,7,8-TCDD Toxic Equivalents 		9A-31
15.	Quality Assurance/Quality Control (QA/QC)		9A-32
16.	Report Format		9A-33
17.	References		9A-34
IV

-------
METHOD TO-9A
Determination Of Polychlorinated, Polybrominated And
Brominated/Chlorinated Dibenzo-p-Dioxins
And Dibenzofurans In Ambient Air
1. Scope
1.1	This document describes a sampling and analysis method for the quantitative determination of
polyhalogenated dibenzo-p-dioxins and dibenzofurans (PHDDs/PHDFs) in ambient air, which include the
polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), polybrominated dibenzo-p-dioxins and
dibenzofurans (PBDDs/PBDFs), and bromo/chloro dibenzo-p-dioxins and dibenzofurans (BCDDs/BCDFs). The
method uses a high volume air sampler equipped with a quartz-fiber filter and polyurethane foam (PUF)
adsorbent for sampling 325 to 400 m3 ambient air in a 24-hour sampling period. Analytical procedures based
on high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS) are used for analysis
of the sample.
1.2	The sampling and analysis method was evaluated using mixtures of PHDDs and PHDFs, including the
2,3,7,8-substituted congeners (1,2). It has been used extensively in the U.S. Environmental Protection Agency
(EPA) ambient air monitoring studies (3,4) for determination of PCDDs and PCDFs.
1.3	The method provides accurate quantitative data for tetra- through octa-PCDDs/PCDFs (total concentrations
for each isomeric series).
1.4	Specificity is attained for quantitative determination of the seventeen 2,3,7,8-substituted PCDDs/PCDFs and
specific 2,3,7,8-substituted PBDD/PBDF and BCDD/BCDF congeners.
1.5	Minimum detection limits (MDLs) in the range of 0.01 to 0.2 picograms/meter3 (pg/m3) can be achieved for
these compounds in ambient air.
1.6	Concentrations as low as 0.2 pg/m3 can be accurately quantified.
1.7	The method incorporates quality assurance/quality control (QA/QC) measures in sampling, analysis, and
evaluation of data.
1.8	The analytical procedures also have been used for the quantitative determination of these types of compounds
in sample matrices such as stack gas emissions, fly ash, soil, sediments, water, and fish and human tissue (5-9).
1.9	The method is similar to methods used by other EPA, industry, commercial, and academic laboratories for
determining PCDDs and PCDFs in various sample matrices (10-25). This method is an update of the original
EPA Compendium Method TO-9, originally published in 1989 (26).
1.10	The method does not separately quantify gaseous PHDDs and PHDFs and particulate-associated PHDDs
and PHDFs because some of the compounds volatilize from the filter and are collected by the PUF adsorbent.
For example, most of the OCDD is collected by the filter and most of the TCDDs are collected by the PUF during
sampling. PCDDs/PCDFs may be distributed between the gaseous and particle-adsorbed phases in ambient air.
Therefore, the filter and PUF are combined for extraction in this method.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-1

-------
Method TO-9A
Dioxins and Furans
1.11 The sampling and analysis method is very versatile and can be used to determine other brominated and
brominated/chlorinated dioxins and furans in the future when more analytical standards become available for use
in the method. A recent modification of the sample preparation procedure provides the capability required to
determine PCDDs, PCDFs, PCBs, and PAHs in the same sample (27).
2. Summary of Method
2.1	Quartz-fiber filters and glass adsorbent cartridges are pre-cleaned with appropriate solvents and dried in a
clean atmosphere. The PUF adsorbent plugs are subjected to 4-hour Soxhlet extraction using an oversized
extractor to prevent distortion of the PUF plug. The PUF plugs are then air dried in a clean atmosphere and
installed in the glass cartridges. A 50 microliter (pL) aliquot of a 16 picogram/microliter (pg/uL) solution of
37Cl4-2,3,7,8-TCDD is spiked to the PUF in the laboratory prior to field deployment. (Different amounts and
additional 13C12-labeled standards such as 13C12-l,2,3,6,7,8-HxCDF may also be used if desired.) The cartridges
are then wrapped in aluminum foil to protect from light, capped with Teflon® end caps, placed in a cleaned
labeled shipping container, and tightly sealed with Teflon® tap until needed.
2.2	For sampling, the quartz-fiber filter and glass cartridge containing the PUF are installed in the high-volume
air sampler.
2.3	The high-volume sampler is then immediately put into operation, usually for 24 hours, to sample 325 to
400 m3 ambient air.
[Note: Significant losses were not detected when duplicate samplers were operated 7 days and sampled 2660
m3 ambient air (1-4).]
2.4	The amount of ambient air sampled is recorded at the end of the sampling session. Sample recovery involves
placing the filter on top of the PUF. The glass cartridge is then wrapped with the original aluminum foil, capped
with Teflon® end caps, placed back into the original shipping container, identified, and shipped to the analytical
laboratory for sample processing.
2.5	Sample preparation typically is performed on a "set" of 12 samples, which consists of 9 test samples, a field
blank, a method blank, and a matrix spike.
2.6	The filter and PUF are combined for sample preparation, spiked with 9 13C12-labeled PCDD/PCDF and 4
PBDD/PBDF internal standards (28), and Soxhlet extracted for 16 hours. The extract is subjected to an acid/base
clean-up procedure followed by clean-up on micro columns of silica gel, alumina, and carbon. The extract is then
spiked with 0.5 ng 13C12-1,2,3,4-TCDD (to determine extraction efficiencies achieved for the" Q -labeled
internal standards) and then concentrated to 10 /aL for HRGC-HRMS analysis in a 1 mL conical reactivial.
2.7	The set of sample extracts is subjected to HRGC-HRMS selected ion monitoring (SIM) analysis using a 60-
m DB-5 or 60-m SP-2331 fused silica capillary column to determine the sampler efficiency, extraction efficiency,
and the concentrations or the MDLs achieved for the PHDDs/PHDFs (28). Defined identification criteria and
QA/QC criteria and requirements are used in evaluating the analytical data. The analytical results along with the
volume of air sampled are used to calculate the concentrations of the respective tetra- through octa-isomers, the
concentrations of the 2,3,7,8-chlorine or -bromine substituted isomers, or the MDLs. The concentrations and/or
Page 9A-2
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
MDLs are reported in pg/m3. The EPA toxicity equivalence factors (TEFs) can be used to calculate the 2,3,7,8-
TCDD toxicity equivalents (TEQs) concentrations, if desired (18).
3.	Significance
3.1	The PHDDs and PHDFs may enter the environment by two routes: (1) manufacture, use and disposal of
specific chemical products and by-products and (2) the emissions from combustion and incineration processes.
Atmospheric transport is considered to be a major route for widespread dispersal of these compounds in stack
gas emissions throughout the environment. The PCDDs/PCDFs are found as complex mixtures of all isomers
in emissions from combustion sources. The isomer profiles of PCDDs/PCDFs found in ambient air are similar
to those found in combustion sources. Isomer profiles of PCDDs/PCDFs related to chemical products and by-
products are quite different in that only a few specific and characteristic isomers are detectable, which clearly
indicate they are not from a combustion source.
3.2	The 2,3,7,8-substituted PCDDs/PCDFs are considered to be the most toxic isomers. Fortunately, they
account for the smallest percentage of the total PCDD/PCDF concentrations found in stack gas emissions from
combustion sources and in ambient air. The 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), 1 of 22 TCDD
isomers and the most toxic member of PCDDs/PCDFs, is usually found as a very minor component in stack gas
emissions (0.5 to 10 percent of total TCDD concentration) and is seldom found in ambient air samples. All of
the 2,3,7,8-substituted PCDDs/PCDFs are retained in tissue of life-forms such as humans, fish, and wildlife, and
the non 2,3,7,8-substituted PCDDs/PCDFs are rapidly metabolized and/or excreted.
3.3	Attention has been focused on determining PHDDs/PHDFs in ambient air only in recent years. The analyses
are time-consuming, complex, difficult, and expensive. Extremely sensitive, specific, and efficient analytical
procedures are required because the analysis must be performed for very low concentrations in the pg/m3 and sub
pg/m3 range. The MDLs, likewise, must be in the range of 0.01 to 0.2 pg/m3 for the results to have significant
meaning for ambient air monitoring purposes. The background level of total PCDDs/PCDFs detected in ambient
air is usually in the range of 0.5 to 3 pg/m3, and the PBDFs is in the range of 0.1 to 0.2 pg/m3 (2,3,14). Because
PCDDs/PCDFs, PBDDs/PBDFs, and BCDDs/BCDFs can be formed by thermal reactions, there has been an
increasing interest in ambient air monitoring, especially in the vicinities of combustion and incineration processes
such as municipal waste combustors and resource recovery facilities (19,20). PBDDs/PBDFs can be created
thermally (22,23), and they may also be formed in certain chemical processes (21). BCDDs/BCDFs have been
detected in ash from combustion/incineration processes (9). The sampling and analysis method described here
can be used in monitoring studies to accurately determine the presence or absence of pg/m3 and sub pg/m3 levels
of these compounds in ambient air (26,27).
4.	Safety
4.1 The 2,3,7,8-TCDD and other 2,3,7,8-chlorine or bromine substituted isomers are toxic and can pose health
hazards if handled improperly. Techniques for handling radioactive and infectious materials are applicable to
2,3,7,8-TCDD and the other PHDDs and PHDFs. Only highly trained individuals who are thoroughly versed in
appropriate laboratory procedures and familiar with the hazards of 2,3,7,8-TCDD should handle these substances.
A good laboratory practice involves routine physical examinations and blood checks of employees working with
2,3,7,8-TCDD. It is the responsibility of the laboratory personnel to ensure that safe handling procedures are
employed.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-3

-------
Method TO-9A
Dioxins and Furans
4.2	The toxicity or carcinogenicity of the other penta-, hexa-, hepta-, and octa-PHDDs/PHDFs with chlorine or
bromine atoms in positions 2,3,7,8 are known to have similar, but lower, toxicities. However, each compound
should be treated as a potential health hazard and exposure to these compounds must be minimized.
4.3	While the procedure specifies benzene as the extraction solution, many laboratories have substituted toluene
for benzene (28). This is due to the carcinogenic nature of benzene. The EPA is presently studying the
replacement of benzene with toluene.
4.4	A laboratory should develop a strict safety program for working with these compounds, which would include
safety and health protocols; work performed in well ventilated and controlled access laboratory; maintenance of
current awareness file of OSHA regulations regarding the safe handling of chemicals specified in the method;
protective equipment; safety training; isolated work area; waste handling and disposal procedures;
decontamination procedures; and laboratory wipe tests. Other safety practices as described in EPA Method 613,
Section 4, July 1982 version, EPA Method 1613 Revision A, April 1990, Office of Water and elsewhere (29,30).
5. Applicable Documents
5.1	ASTM Standards
•	Method D1365 Definitions of Terms Relating to Atmospheric Sampling and Analysis.
•	Method E260 Recommended Practice for General Gas Chromatography Procedures.
•	Method E355 Practice for Gas Chromatography Terms and Relationships.
5.2	EPA Documents
•	Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II, U. S. Environmental
Protection Agency, EPA 600/R-94-03 8b, May 1994.
•	Protocol for the Analysis of 2,3,7,8-Tetrachlorodibenzo-p-Dioxin by High Resolution Gas
Chromatography-High Resolution Mass Spectrometry, U. S. Environmental Protection Agency,
EPA 600/40-86-004, January 1986.
•	"Evaluation of an EPA High Volume Air Sampler for Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans," undated report by Battelle under Contract No. 68-02-4127, Project Officers
Robert G. Lewis and Nancy K. Wilson, U. S. Environmental Protection Agency, Research Triangle Park,
North Carolina.
•	Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air:
Method TO-9, Second Supplement, U. S. Environmental Protection Agency, EPA 600/4-89-018,
March 1989.
•	Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient
Air, U. S. Environmental Protection Agency, EPA 600/4-83-027, June 1983.
•	"Analytical Procedures and Quality Assurance for Multimedia Analysis of Polychlorinated Dibenzo-p-
Dioxins and Dibenzofurans by High Resolution Gas Chromatography - Low Resolution Mass Spectrometry,"
U. S. Environmental Protection Agency/OSW, SW-846, RCRA 8280 HRGC-LRMS, January 1987.
•	"Analytical Procedures and Quality Assurance for Multimedia Analysis of Polychlorinated Dibenzo-p-
Dioxins and Dibenzofurans by High Resolution Gas Chromatography - High Resolution Mass Spectrometry,"
U. S. Environmental Protection Agency/O SW, SW-846, RCRA 8290 HRGC-HRMS, June 1987.
Page 9A-4
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
•	Harless, R., "Analytical Procedures and Quality Assurance Plan for the Determination of PCDDs and
PCDFs Ambient Air near the Rutland, Vermont Municipal Incinerator," Final Report, U. S. Environmental
Protection Agency, AREAL, RTP, NC, 1988.
•	Feasibility of Environmental Monitoring and Exposure Assessment for a Municipal Waste Combustor:
Rutland, Vermont Pilot Study, U. S. Environmental Protection Agency, EPA 600/8-91/007, March 1991.
•	"Method 23, Determination of Polychlorinated Dibenzo-p-Dioxins (PCDDs) and Dibenzofurans (PCDFs)
from Stationary Sources." Federal Register, Vol. 56, No. 30, February 13, 1991.
•	Method 1613 Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRdC-HRMS.
U. S. Environmental Protection Agency, Office of Solid Waste, Washington, DC, April 1990.
5.3 Other Documents
•	"Operating Procedures for Model PS-1 Sampler," Graseby/General Metal Works, Inc., Village of Cleves,
OH 45002 (800-543-7412).
•	"Chicago Air Quality: PCB Air Monitoring Plan, Phase 2," IEAP/APC/86-011, Illinois Environmental
Protection Agency, Division of Air Pollution Control, April 1986.
•	"Operating Procedures for the Thermo Environmental Semi-volatile Sampler," Thermo Environmental
Instruments, Inc. (formerly Wedding and Associates), 8 West Forge Parkway, Franklin, MA 02038 (508-520-
0430).
6. Definitions
[Note: Definitions used in this document and any user-prepared Standard Operating Procedures (SOPs)
should be consistent with those used in ASTM D1356. All abbreviations and symbols are defined within this
document at the point of first use.]
6.1	Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs)—compounds
that contain from 1 to 8 chlorine atoms, resulting in a total of 75 PCDDs and 135 PCDFs. The structures are
shown in Figure 1. The numbers of isomers at different chlorination levels are shown in T able 1. The seventeen
2,3,7,8-substituted PCDDs/PCDFs are shown in Table 2.
6.2	Polybrominated dibenzo-p-dioxins (PBDDs) and polybrominated dibenzofurans (PBDFs)—compounds
that have the same structure and contain from 1 to 8 bromine atoms, resulting in a total of 75 PBDDs and 135
PBDFs. The structures and isomers are the same as those of the PCDDs/PCDFs shown in Figure 1 and Tables 1
and 2.
6.3	Brominated/chlorinated dibenzo-p-dioxins (BCDDs) and brominated/chlorinated dibenzofurans
(BCDFs)—compounds with the same structures and may contain from 1 to 8 chlorine and bromine atoms,
resulting in 1550 BCDD congeners and 3050 BCDF congeners.
6.4	Polyhalogenated dibenzo-p-dioxins (PHDDs) and polyhalogenated dibenzofurans (PHDFs)—dibenzo-
p-dioxins and dibenzofurans substituted with 1 or more halogen atoms.
6.5	Isomer—compounds having the sample number and type of halogen atoms, but substituted in different
positions. For example, 2,3,7,8-TCDD and 1,2,3,4-TCDD are isomers. Additionally, there are 22 isomers that
constitute the homologues of TCDDs.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-5

-------
Method TO-9A
Dioxins and Furans
6.6	Isomeric group—a group of dibenzo-p-dioxins or dibenzofurans having the same number of halogen atoms.
For example, the tetra-chlorinated dibenzo-p-dioxins.
6.7	Internal Standard—is an isotopically-labeled analog that is added to all samples, including method blanks
(process and field) and quality control samples, before extraction. They are used along with response factors to
measure the concentration of the analytes. Nine PCDD/PCDF and 4 PBDD/PBDF internal standards are used
in this method. There is one for each of the chlorinated dioxin and foran isomeric groups with a degree of
halogenation ranging from four to eight, with the exception of OCDF.
6.8	High-Resolution Calibration Solutions (see Table 3)—solutions in tridecane containing known amounts
of 17 selected PCDDs and PCDFs, 9 internal standards (13C12-labeled PCDDs/PCDFs), 2 field standards, 4
surrogate standards, and 1 recovery standard. The set of 5 solutions is used to determine the instrument response
of the unlabeled analytes relative to the 13C12-labeled internal standards and of the 13C12-labeled internal standards
relative to the surrogate, field and recovery standards. Different concentrations and other standards may be used,
if desired. Criteria for acceptable calibration as outlined in Section 13.5 should be met in order to use the analyte
relative response factors.
6.9	Sample Fortification Solutions (see Table 4)—solutions (in isooctane) containing the 13C12-labeled internal
standards that are used to spike all samples, field blanks, and process blanks before extraction. Brominated
standards used only when desired.
6.10	Recovery Standard Solution (see Table 5)—Recovery Standard Solution (see Table 5)—an isooctane
solution containing the 13C12-1,2,3,4-TCDD (13C12-2,3,7,8,9-HxDD optional) recovery standards that are added
to the extract before final concentration for HRGC-HRMS analysis to determine the recovery efficiencies
achieved for the 13C12-labeled internal standards.
6.11	Air Sampler Field Fortification Solution (see Table 6)—an isooctane solution containing the 37C14-
2,3,7,8-TCDD standard that is spiked to the PUF plugs prior to shipping them to the field for air sampling.
6.12	Surrogate Standard Solution (see Table 7)—an isooctane solution containing 4 13C12-labeled standards
that may be spiked to the filter or PUF prior to air sampling, to the sample prior to extraction, or to the sample
extract before cleanup or before HRGC-HRMS analysis to determine sampler efficiency method efficiency or
for identification purposes (28). Other standards and different concentrations may be used, if desired.
6.13	Matrix Spike and Method Spike Solutions (see Table 8)—isooctane solutions of native (non-labeled)
PCDDs and PCDFs and PBDDs and PBDFs that are spiked to a clean PUF prior to extraction.
6.14	Sample Set—consists of nine test samples, field blank, method blank, and matrix spiked with native
PHDDs/PHDFs. Sample preparation, HRGC-HRMS analysis, and evaluation of data is performed on a sample
set.
6.15	Lab Control Spike—standard that is prepared during sample preparation and that contains exactly the
same amounts of all of the labeled and unlabeled standards that were used in extraction and cleanup of the sample
set for HRGC-HRMS analysis.
Page 9A-6
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
6.16	Field Blank—consists of a sample cartridge containing PUF and filter that is spiked with the filed
fortification solution, shipped to the field, installed on the sampler, and passively exposed at the sampling area
(the sampler is not operated). It is then sealed and returned to the laboratory for extraction, cleanup, and
HRGC-HRMS analysis. It is treated in exactly the same manner as a test sample. A field blank is processed with
each sampling episode. The field blank represents the background contributions from passive exposure to
ambient air, PUF, quartz fiber filter, glassware, and solvents.
6.17	Laboratory Method Blank—represents the background contributions from glassware, extraction and
cleanup solvents. A Soxhlet extractor is spiked with a solution of 13C12-labeled internal standards, extracted,
cleaned up, and analyzed by HRGC-HRMS in exactly the same manner as the test samples.
6.18	Solvent Blank—an aliquot of solvent (the amount used in the method) that is spiked with the 13C12-labeled
internal standards and concentrated to 60 uL for HRGC-HRMS analysis. The analysis provides the background
contributions from the specific solvent.
6.19	GC Column Performance Evaluation Solution (see Table 9)—a solution containing a mixture of
selected PCDD/PCDF isomers, including the first and last chromatographic eluters for each isomeric group. Used
to demonstrate continued acceptable performance of the capillary column and to define the PCDD/PCDF
retention time windows. Also includes a mixture of tetradioxin isomers that elute closest to 2,3,7,8-TCDD.
6.20	QA/QC Audit Samples—samples of PUF that contain known amounts of unlabeled PCDDS and PCDFs.
These samples are submitted as "blind" test samples to the analytical laboratory. The analytical results can then
be used to determine and validate the laboratory's accuracy, precision and overall analytical capabilities for
determination of PCDDs/PCDFs.
6.21	Relative Response Factor—response of the mass spectrometer to a known amount of an analyte relative
to a known amount of a labeled internal standard.
6.22	Method Blank Contamination—the method blank should be free of interferences that affect the
identification and quantification of PHDDs and PHDFs. A valid method blank is an analysis in which all internal
standard signals are characterized by S/N ratio greater than 10:1 and the MDLs are adequate for the study. The
set of samples must be extracted and analyzed again if a valid method blank cannot be achieved.
6.23	Sample Rerun—additional cleanup of the extract and reanalysis of the extract.
6.24	Extract Reanalysis—analysis by HRGC-HRMS of another aliquot of the final extract.
6.25	Mass Resolution Check—a standard method used to demonstrate a static HRMS resolving power of
10,000 or greater (10 percent valley definition).
6.26	Method Calibration Limits (MCLs)—for a given sample size, a final extract volume, and the lowest and
highest calibration solutions, the lower and upper MCLs delineate the region of quantitation for which the
HRGC-HRMS system was calibrated with standard solutions.
6.27	HRGC-HRMS Solvent Blank—a 1 or 2 ,uL aliquot of solvent that is analyzed for tetra- through octa-
PCDDs and PCDFs following the analysis of a sample that contains high concentrations of these compounds.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-7

-------
Method TO-9A
Dioxins and Furans
An acceptable solvent blank analysis (free of PHDDs/PHDFs) should be achieved before continuing with analysis
of the test samples.
6.28	Sampler Spike (SS)—a sampler that is spiked with known amounts of the air sampler field fortification
solution (see Table 6) and the matrix spike solutions (see Table 8) prior to operating the sampler for 24 hours
to sample 325-400 std m3 ambient air. The results achieved for this sample can be used to determine the
efficiency, accuracy and overall capabilities of the sampling device and analytical method.
6.29	Collocated Samplers (CS)—two samplers installed close together at the same site that can be spiked with
known amounts of the air sampler field fortification solution (see Table 6) prior to operating the samplers for 24
hours to sample 325-400 std m3 ambient air. The analytical results for these two samples can be used to
determine and evaluate efficiency, accuracy, precision, and overall capabilities of the sampling device and
analytical method.
6.30	Congener—a term which refers to any one particular member of the same chemical family. As an example,
there are 75 congeners of chlorinated dibenzo-p-dioxins. A specific congener is denoted by unique chemical
notations. For example, 2,4,8,9-tetrachlorodibenzofuran is referred to as 2,4,8,9-TCDF.
6.31	Homologue—a term which refers to a group of structurally related chemicals that have the same degree
of chlorination. For example, there are eight homologues of CDDs, monochlorinated through octochlorinated.
Notation for homologous classes is as follows:
(lass Auoiimii
Dibenzo-p-dioxin
D

Dibenzofuran
F

\o ol'haloLvns
Acioin in
l\ani|"ik'
1
M

2
D
2,4-DCDD
3
Tr

4
T
1,4,7,8-TCDD
5
Pe

6
Hx

7
Hp

8
O

1 through 8
CDDs and CDFs

7. Interferences And Contamination
7.1 Any compound having a similar mass and mass/charge (m/z) ratio eluting from the HRGC column within
± 2 seconds of the PHDD/PHDF of interest is a potential interference. Also, any compound eluting from the
HRGC column in a very high concentration will decrease sensitivity in the retention time frame. Some commonly
encountered interferences are compounds that are extracted along with the PCDDs and PCDFs or other
PHDDs/PHDFs, e.g., polychlorinated biphenyls (PCBs), methoxybiphenyls, polychlorinated diphenylethers,
polychlorinated naphthalenes, DDE, DDT, etc. The cleanup procedures are designed to eliminate the majority
of these substances. The capillary column resolution and mass spectrometer resolving power are extremely
helpful in segregating any remaining interferences from PCDDs and PCDFs. The severity of an interference
Page 9A-8
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
problem is usually dependent on the concentrations and the mass spectrometer and chromatographic resolutions.
However, polychlorinated diphenylethers are extremely difficult to resolve from PCDFs because they elute in
retention time windows of PCDFs, and their fragment ion resulting from the loss of 2 chlorine atoms is identical
to that of the respective PCDF. For example, the molecular ions of hexachlorodiphenylethers must be monitored
to confirm their presence or absence in the analysis for TCDFs. This requirement also applies to the other PCDFs
and PBDFs.
7.2 Since very low levels of PCDDs and PCDFs must be determined, the elimination of interferences is essential.
High purity reagents and solvents must be used, and all equipment must be scrupulously cleaned. All materials,
such as PUF, filter solvents, etc., used in the procedures are monitored and analyzed frequently to ensure the
absence of contamination. Cleanup procedures must be optimized and performed carefully to minimize the loss
of analyte compounds during attempts to increase their concentrations relative to other sample components. The
analytical results achieved for the field blank, method blank, and method spike in a "set" of samples is extremely
important in evaluating and validating the analytical data achieved for the test samples.
8. Apparatus
[Note: This method was developed using the PS-1 semi-volatile sampler provided by General Metal Works,
Village of Cleves, OH as a guideline. EPA has experience in use of this equipment during various field
monitoring programs over the last several years. Other manufacturers' equipment should work as well.
However, modifications to these procedures may be necessary if another commercially available sampler is
selected.]
8.1	High-Volume Sampler (see Figure 2). Capable of pulling ambient air through the filter/adsorbent cartridge
at a flow rate of approximately 8 standard cubic feet per minute (scftn) (0.225 std m3\min) to obtain a total
sample volume of greater than 325 scm over a 24-hour period. Major manufacturers are:
Tisch Environmental, Village of Cleves, OH
-	Andersen Instruments Inc., 500 Technology Ct., Smyrna, GA
Thermo Environmental Instruments, Inc., 8 West Forge Parkway, Franklin, MA
8.2	High-Volume Sampler Calibrator. Capable of providing multipoint resistance for the high-volume
sampler. Major manufacturers are:
Tisch Environmental, Village of Cleves, OH
-	Andersen Instruments Inc., 500 Technology Ct., Smyrna, GA
Thermo Environmental Instruments, Inc., 8 West Forge Parkway, Franklin, MA
8.3	High Resolution Gas Chromatograph-High Resolution Mass Spectrometer-Data System
(HRGC-HRMS-DS)
8.3.1 The GC should be equipped for temperature programming and all of the required accessories, such as
gases and syringes, should be available. The GC injection port should be designed for capillary columns.
Splitless injection technique, on-column injections, or moving needle injectors may be used. It is important to
use the same technique and injection volume at all times.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-9

-------
Method TO-9A
Dioxins and Furans
8.3.2	The HRGC-HRMS interface, if used, should be constructed of fused silica tubing or all glass or glass
lined stainless steel and should be able to withstand temperatures up to 3400 C. The interface should not degrade
the separation of PHDD/PHDF isomers achieved by the capillary column. Active sites or cold spots in the
interface can cause peak broadening and peak tailing. The capillary column should be fitted directly into the
HRMS ion source to avoid these types of problems. Graphite ferrules can adsorb PHDDs/PHDFs and cause
problems. Therefore, Vespel® or equivalent ferrules are recommended.
8.3.3	The HRMS system should be operated in the electron impact ionization mode. The static resolving
power of the instrument should be maintained at 10,000 or greater (10% valley definition). The HRMS should
be operated in the selected ion monitoring (SIM) mode with a total cycle time of one second or less. At a
minimum, the ions listed in Tables 10, 11, and 12 for each of the select ion monitoring (SIM) descriptors should
be monitored. It is important to use the same set of ions for both calibration and sample analysis.
8.3.4	The data system should provide for control of mass spectrometer, data acquisition, and data processing.
The data system should have the capability to control and switch to different sets of ions (descriptors/mass menus
shown in Tables 10, 11, and 12) at different times during the HRGC-HRMS SIM analysis. The SIM
traces/displays of ion signals being monitored can be displayed on the terminal in real time and sorted for
processing. Quantifications are reported based on computer generated peak areas. The data system should be
able to provide hard copies of individual ion chromatograms for selected SIM time intervals, and it should have
the capability to allow measurement of noise on the baseline. It should also have the capability to acquire mass-
spectral peak profiles and provide hard copies of the peak profiles to demonstrate the required mass resolution.
8.3.5	HRGC columns, such as the DB-5 (28) and SP-2331 fused silica capillary columns, and the operating
parameters known to produce acceptable results are shown in Tables 13 and 14. Other types of capillary columns
may also be used as long as the performance requirements can be successfully demonstrated.
9. Equipment And Materials
9.1 Materials for Sample Collection (see Figure 3a)
9.1.1	Quartz fiber filter. 102 millimeter bindless quartz microfiber filter, Whatman International Ltd,
QMA-4.
9.1.2	Polyurethane foam (PUF) plugs. 3-inch thick sheet stock polyurethane type (density 0.022 g/cm3).
The PUF should be of the polyether type used for furniture upholstery, pillows, and mattresses. The PUF
cylinders (plugs) should be slightly larger in diameter than the internal diameter of the cartridge. Sources of
equipment are Tisch Environmental, Village of Cleves, OH; University Research Glassware, 116 S. Merritt Mill
Road, Chapel Hill, NC; Thermo Environmental Instruments, Inc., 8 West Forge Parkway, Franklin, MA; Supelco,
Supelco Park, Bellefonte, PA; and SKC Inc., 334 Valley View Road, Eighty Four, PA (see Figure 3b).
9.1.3	Teflon® end caps. For sample cartridge. Sources of equipment are Tisch Environmental, Village of
Cleves, OH; and University Research Glassware, 116 S. Merritt Mill Road, Chapel Hill, NC (see Figure 3b).
9.1.4	Sample cartridge aluminum shipping containers. For sample cartridge shipping. Sources of
equipment are Tisch Environmental, Village of Cleves, OH; and University Research Glassware, 116 S. Merritt
Mill Road, Chapel Hill, NC (see Figure 3b).
9.1.5	Glass sample cartridge. For sample collection. Sources of equipment are Tisch Environmental,
Village of Cleves, OH; Thermo Environmental Instruments, Inc., 8 West Forge, Parkway, Franklin, MA; and
University Research Glassware, 116 S. Merritt Mill Road, Chapel Hill, NC (see Figure 3b).
Page 9A-10
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
9.2	Laboratory Equipment
9.2.1	Laboratory hoods.
9.2.2	Drying oven.
9.2.3	Rotary evaporator. With temperature-controlled water bath.
9.2.4	Balances.
9.2.5	Nitrogen evaporation apparatus.
9.2.6	Pipettes. Disposal Pasteur, 150-mmlongx5-mmi.d.
9.2.7	Soxhlet apparatus. 500-mL.
9.2.8	Glass funnels.
9.2.9	Desiccator.
9.2.10	Solvent reservoir. 125-mL, Kontes, 12.35-cm diameter.
9.2.11	Stainless steel spoons and spatulas.
9.2.12	Glass wool. Extracted with methylene chloride, stored in clean jar.
9.2.13	Laboratory refrigerator.
9.2.14	Chromatographic columns.
9.2.15	Perfluorokerosenes.
9.3	Reagents and Other Materials
9.3.1	Sulfuric acid. Ultrapure, ACS grade, specific gravity 1.84, acid silica.
9.3.2	Sodium hydroxide. Potassium hydroxide, reagent grade, base silica.
9.3.3	Sodium sulfate.
9.3.4	Anhydrous, reagent grade.
9.3.5	Glass wool. Silanized, extracted with methylene chloride and hexane, and dried.
9.3.6	Diethyl ether. High purity, glass distilled.
9.3.7	Isooctane. Burdick and Jackson, glass-distilled.
9.3.8	Hexane. Burdick and Jackson, glass-distilled.
9.3.9	Toluene. Burdick and Jackson, glass-distilled, or equivalent.
9.3.10	Methylene chloride. Burdock and Jackson, chromatographic grade, glass distilled.
9.3.11	Acetone. Burdick and Jackson, high purity, glass distilled.
9.3.12	Tridecane. Aldrich, high purity, glass distilled.
9.3.13	Isooctane. Burdick and Jackson, high purity, glass distilled.
9.3.14	Alumina. Acid, pre-extracted (16-21 hours) and activated.
9.3.15	Silica gel. High purity grade, type 60, 70-230 mesh; extracted in a Soxhlet apparatus with methylene
chloride (see Section 8.18) for 16-24 hours (minimum of 3 cycles per hour) and activated by heating in a foil-
covered glass container for 8 hours at 130°C.
9.3.16	18 percent Carbopack C/Celite 545.
9.3.17	Methanol. Burdick and Jackson, high purity, glass distilled.
9.3.18	Nonane. Aldrich, high purity, glass distilled.
9.3.19	Benzene. High purity, glass distilled.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-11

-------
Method TO-9A
Dioxins and Furans
9.4 Calibration Solutions and Solutions of Standards Used in the Method
9.4.1	HRGC-HRMS Calibration Solutions (see Table 3). Solutions containing 13C12-labeled and
unlabeled PCDDs and PCDFs at known concentrations are used to calibrate the instrument. These standards can
be obtained from various commercial sources such as Cambridge Isotope Laboratories, 50 Frontage Road,
Andover, MA 01810, 508-749-8000.
9.4.2	Sample Fortification Solutions (see Table 4). An isooctane solution (or nonane solution) containing
the 13C12-labeled PCDD/PCDF and PBDD/PBDF internal standards at the listed concentrations. The internal
standards are spiked to all samples prior to extraction and are used to measure the concentration of the unlabeled
native analytes and to determine MDLs.
9.4.3	Recovery Standard Spiking Solution (see Table 5). An isooctane solution containing 13C12-1,2,3,4-
TCDD at a concentration of 10 pgA iL. Additional recovery standards may be used if desired.
9.4.4	Sampler Field Fortification Solution (see Table 6). An isooctane solution containing 10 pg/. iL
37Cl4-2,3,7,8-TCDD.
9.4.5	Surrogate Standards Solution (see Table 7). An isooctane solution containing the four 13C12-labeled
standards at a concentration of 100 pg/. iL.
9.4.6	Matrix/Method Spike Solution (see Table 8). An isooctane solution containing the unlabeled
PCDDs/PCDFs and PBDDs/PBDFs at the concentrations listed.
[Note: All PHDD/PHDF solutions listed above should be stored in a refrigerator at less than or equal to 4° C
in the dark. Exposure of the solutions to light should be minimized.]
9.4.7	Column Performance Evaluation Solutions (see Table 9). Isooctane solutions of first and last
chromatographic eluting isomers for each isomeric group of tetra- through octa-CDDs/CDFs. Also includes a
mixture of tetradioxin isomers that elute closest to 2,3,7,8-TCDD.
10. Preparation Of PUF Sampling Cartridge
10.1	Summary of Method
10.1.1	This part of the procedure discusses pertinent information regarding the preparation and cleaning of
the filter, adsorbents, and filter/adsorbent cartridge assembly. The separate batches of filters and adsorbents are
extracted with the appropriate solvent.
10.1.2	At least one PUF cartridge assembly and one filter from each batch, or 10 percent of the batch,
whichever is greater, should be tested and certified before the batch is considered for field use.
10.1.3	Prior to sampling, the cartridges are spiked with surrogate compounds.
10.2	Preparation of Sampling Cartridge
10.2.1	Bake the quartz filters at 400°C for 5 hours before use.
10.2.2	Set aside the filters in a clean container for shipment to the field or prior to combining with the PUF
glass cartridge assembly for certification prior to field deployment.
10.2.3	The PUF plugs are 6.0-cm diameter cylindrical plugs cut from 3-inch sheet stock and should fit, with
slight compression, in the glass cartridge, supported by the wire screen (see Figure 2). During cutting, rotate the
die at high speed (e.g., in a drill press) and continuously lubricate with deionized or distilled water. Pre-cleaned
PUF plugs can be obtained from commercial sources (see Section 9.1.2).
Page 9A-12
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
10.2.4	For initial cleanup, place the PUF plugs in a Soxhlet apparatus and extract with acetone for 16 hours
at approximately 4 cycles per hour. When cartridges are reused, use diethyl ether/hexane (5 to 10 percent
volume/volume [v/v]) as the cleanup solvent.
[Note: A modified PUF cleanup procedure can be used to remove unknown interference components of the
PUF blank. This method consists of rinsing 50 times with toluene, acetone, and diethyl ether/hexane (5 to
10 percent v/v), followed by Soxhlet extraction. The extracted PUF is placed in a vacuum oven connected to
a water aspirator and dried at room temperature for approximately 2 to 4 hours (until no solvent odor is
detected). The extract from the Soxhlet extraction procedure from each batch may be analyzed to determine
initial cleanliness prior to certification.]
10.2.5	Fit a nickel or stainless steel screen (mesh size 200/200) to the bottom of a hexane-rinsed glass
sampling cartridge to retain the PUF adsorbents, as illustrated in Figure 2. Place the Soxhlet-extracted, vacuum-
dried PUF (2.5-cm thick by 6.5-cm diameter) on top of the screen in the glass sampling cartridge using polyester
gloves.
10.2.6	Wrap the sampling cartridge with hexane-rinsed aluminum foil, cap with the Teflon® end caps, place
in a cleaned labeled aluminum shipping container, and seal with Teflon® tape. Analyze at least 1 PUF plug from
each batch of PUF plugs using the procedures described in Section 10.3, before the batch is considered acceptable
for field use. A level of 2 to 20 pg for tetra-,penta-, and hexa- and 40 to 150 pg for hepta- and octa-CDDs similar
to that occasionally detected in the method blank (background contamination) is considered to be acceptable.
Background levels can be reduced further, if necessary. Cartridges are considered clean for up to 30 days from
date of certification when stored in their sealed containers.
10.3 Procedure for Certification of PUF Cartridge Assembly
10.3.1	Extract 1 filter and PUF adsorbent cartridge by Soxhlet extraction and concentrate using a Kuderna-
Danish (K-D) evaporator for each lot of filters and cartridges sent to the field.
10.3.2	Assemble the Soxhlet apparatus. Charge the Soxhlet apparatus with 300 mL of the extraction solvent
(10 percent v/v diethyl ether/hexane) and reflux for 2 hours. Let the apparatus cool, disassemble it, and discard
the used extraction solvent. Transfer the filter and PUF glass cartridge to the Soxhlet apparatus (the use of an
extraction thimble is optional).
[Note: The filter and adsorbent assembly are tested together in order to reach detection limits, to minimize
cost and to prevent misinterpretation of the data. Separate analyses of the filter and PUF would not yield
useful information about the physical state of most of the PHDDs and PHDFs at the time of sampling due to
evaporative losses from the filter during sampling.]
10.3.3	Add 300 mL of diethyl ether/hexane (10 percent v/v) to the Soxhlet apparatus. Reflux the sample
for 18 hours at a rate of at least 3 cycles per hour. Allow to cool; then disassemble the apparatus.
10.3.4	Assemble a K-D concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask.
10.3.5	Transfer the extract by pouring it through a drying column containing about 10 cm of anhydrous
granular sodium sulfate and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column
with 20 to 30 mL of 10 percent diethylether/hexane to complete the quantitative transfer.
10.3.6	Add 1 or 2 clean boiling chips and attach a 3-ball Snyder column to the evaporative flask. Pre-wet
the Snyder column by adding about 1 mL of the extraction solvent to the top of the column. Place the K-D
apparatus on a hot water bath (50 °C) so that the concentrator tube is partially immersed in the hot water, and the
entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-13

-------
Method TO-9A
Dioxins and Furans
and the water temperature as required to complete the concentration in one hour. At the proper rate of distillation,
the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the
apparent volume of liquid reaches approximately 5 mL, remove the K-D apparatus from the water bath and allow
it to drain and cool for at least 5 minutes. Remove the Snyder column and rinse the flask and its lower joint into
the concentrator tube with 5 mL of hexane. A 5-mL syringe is recommended for this operation.
10.3.7	Concentrate the extract to 1 mL, cleanup the extract (see Section 12.2.2), and analyze the final extract
using HRGC-HRMS.
10.3.8	The level of target compounds must be less than or equal to 2 to 20 pg for tetra-, penta-, and hexa-
and 40 to 150 pg for hepta- and octa-CDDs for each pair of filter and adsorbent assembly analyzed is considered
to be acceptable.
10.4 Deployment of Cartridges for Field Sampling
10.4.1	Prior to field deployment, add surrogate compounds (i.e., chemically inert compounds not expected
to occur in an environmental sample) to the center bed of the PUF cartridge, using a microsyringe. The surrogate
compounds (see Table 3) must be added to each cartridge assembly.
10.4.2	Use the recoveries of the surrogate compounds to monitor for unusual matrix effects and gross
sampling processing errors. Evaluate surrogate recovery for acceptance by determining whether the measured
concentration falls within the acceptance limits.
11. Assembly, Calibration And Collection Using Sampling System
[Note: This method was developed using the PS-1 semi-volatile sampler provided by General Metal Works,
Village of Cleves, OH as a guideline. EPA has experience in use of this equipment during various field
monitoring programs over the last several years. Other manufacturers' equipment should work as well.
However, modifications to these procedures may be necessary if another commercially available sampler is
selected.]
11.1	Description of Sampling Apparatus
The entire sampling system is diagrammed in Figure 1. This apparatus was developed to operate at a rate of 4
to 10 scfm (0.114 to 0.285 std m3/min) and is used by EPA for high-volume sampling of ambient air. The
method write-up presents the use of this device.
The sampling module (see Figure 2) consists of a filter and a glass sampling cartridge containing the PUF utilized
to concentrate dioxins/furans from the air. A field portable unit has been developed by EPA (see Figure 4).
11.2	Calibration of Sampling System
Each sampler should be calibrated (1) when new, (2) after major repairs or maintenance, (3) whenever any audit
point deviates from the calibration curve by more than 7 percent, (4) before/after each sampling event, and
(5) when a different sample collection media, other than that which the sampler was originally calibrated to, will
be used for sampling.
11.2.1 Calibration of Orifice Transfer Standard. Calibrate the modified high volume air sampler in the
field using a calibrated orifice flow rate transfer standard. Certify the orifice transfer standard in the laboratory
against a positive displacement rootsmeter (see Figure 5). Once certified, the recertification is performed rather
Page 9A-14
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
infrequently if the orifice is protected from damage. Recertify the orifice transfer standard performed once per
year utilizing a set of five multiple resistance plates.
[Note: The set of five multihole resistance plates are used to change the flow through the orifice so that
several points can be obtained for the orifice calibration curve. The following procedure outlines the steps
to calibrate the orifice transfer standard in the laboratory.]
11.2.1.1	Record the room temperature (Tj in °C) and barometric pressure (Pb in mm Hg) on the Orifice
Calibration Data Sheet (see Figure 6). Calculate the room temperature in K (absolute temperature) and record
on Orifice Calibration Data Sheet.
T\ in K = 273° + T\ in °C
11.2.1.2	Set up laboratory orifice calibration equipment as illustrated in Figure 5. Check the oil level of
the rootsmeter prior to starting. There are 3 oil level indicators, 1 at the clear plastic end and 2 site glasses, 1 at
each end of the measuring chamber.
11.2.1.3	Check for leaks by clamping both manometer lines, blocking the orifice with cellophane tape,
turning on the high volume motor, and noting any change in the rootsmeter's reading. If the rootsmeter's reading
changes, there is a leak in the system. Eliminate the leak before proceeding. If the rootsmeter's reading remains
constant, turn off the hi-vol motor, remove the cellophane tape, and unclamp both manometer lines.
11.2.1.4	Install the 5-hole resistance plate between the orifice and the filter adapter.
11.2.1.5	Turn manometer tubing connectors 1 turn counter-clockwise. Make sure all connectors are open.
11.2.1.6	Adjust both manometer midpoints by sliding their movable scales until the zero point corresponds
with the meniscus. Gently shake or tap to remove any air bubbles and/or liquid remaining on tubing connectors.
(If additional liquid is required for the water manometer, remove tubing connector and add clean water.)
11.2.1.7	Turn on the high volume motor and let it run for 5 minutes to set the motor brushes. Turn the
motor off. Insure manometers are set to zero. Turn the high volume motor on.
11.2.1.8	Record the time, in minutes, required to pass a known volume of air (approximately 200 to 300 ft3
of air for each resistance plate) through the rootsmeter by using the rootsmeter's digital volume dial and a
stopwatch.
11.2.1.9	Record both manometer readings-orifice water manometer (aH) and rootsmeter mercury
manometer (aP) on Orifice Calibration Data Sheet (see Figure 6).
[Note: aH is the sum of the difference from zero (0) of the two column heights.]
11.2.1.10	Turn off the high volume motor.
11.2.1.11	Replace the 5-hole resistance plate with the 7-hole resistance plate.
11.2.1.12	Repeat Sections 11.2.1.3 through 11.2.1.11.
11.2.1.13	Repeat for each resistance plate. Note results on Orifice Calibration Data Sheet (see Figure 6).
Only a minute is needed for warm-up of the motor. Be sure to tighten the orifice enough to eliminate any leaks.
Also check the gaskets for cracks.
[Note: The placement of the orifice prior to the rootsmeter causes the pressure at the inlet of the rootsmeter
to be reduced below atmospheric conditions, thus causing the measured volume to be incorrect. The volume
measured by the rootsmeter must be corrected.]
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-15

-------
Method TO-9A
Dioxins and Furans
11.2.1.14	Correct the measured volumes on the Orifice Calibration Data Sheet:
P - aP T ,
Vstd = Vm (-L-	)(^L)
std	1 a
where:
Vstd = standard volume, std m3
Vm = actual volume measured by the rootsmeter, m3
Pa = barometric pressure during calibration, mm Hg
aP = differential pressure at inlet to volume meter, mm Hg
Pstd = 760 mm Hg
Ta = ambient temperature during calibration, K.
11.2.1.15	Record standard volume on Orifice Calibration Data Sheet.
11.2.1.16	The standard flow rate as measured by the rootsmeter can now be calculated using the following
formula:
O = —
td 0
where:
Qstd = standard volumetric flow rate, std m3/min
0 = elapsed time, min
11.2.1.17	Record the standard flow rates to the nearest 0.01 std m3/min.
11.2.1.18	Calculate and record ^/aH (P|/Pstd)(298/T|) value for each standard flow rate.
11.2.1.19Ploteach ^aH (P|/Psld)(298/T|) value (y-axis) versus its associated standard flow rate (x-
axis) on arithmetic graph paper and draw a line of best fit between the individual plotted points.
[Note: This graph will be used in the field to determine standard flow rate.]
11.2.2 Calibration of the High Volume Sampling System Utilizing Calibrated Orifice Transfer
Standard
For this calibration procedure, the following conditions are assumed in the field:
•	The sampler is equipped with an valve to control sample flow rate.
•	The sample flow rate is determined by measuring the orifice pressure differential, using a magnehelic
gauge.
•	The sampler is designed to operate at a standardized volumetric flow rate of 8 ft3/min (0.225 m3/min), with
an acceptable flow rate range within 10 percent of this value.
•	The transfer standard for the flow rate calibration is an orifice device. The flow rate through the orifice
is determined by the pressure drop caused by the orifice and is measured using a "U" tube water
manometer or equivalent.
•	The sampler and the orifice transfer standard are calibrated to standard volumetric flow rate units (scfm
or scmm).
Page 9A-16
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
•	An orifice transfer standard with calibration traceable to NIST is used.
•	A "U" tube water manometer or equivalent, with a 0- to 16-inch range and a maximum scale division of
0.1 inch, will be used to measure the pressure in the orifice transfer standard.
•	A magnehelic gauge or equivalent, with a 9- to 100-inch range and a minimum scale division of 2 inches
for measurements of the differential pressure across the sampler's orifice is used.
•	A thermometer capable of measuring temperature over the range of 32° to 122°F (0° to 50°C) to ±2°F
(±1 °C) and referenced annually to a calibrated mercury thermometer is used.
•	A portable aneroid barometer (or equivalent) capable of measuring ambient barometric pressure between
500 and 800 mm Hg (19.5 and 31.5 in. Hg) to the nearest mm Hg and referenced annually to a barometer
of known accuracy is used.
•	Miscellaneous handtools, calibration data sheets or station log book, and wide duct tape are available.
11.2.2.1	Monitor the airflow through the sampling system with a venturi/Magnehelic assembly, as
illustrated in Figure 7. Set up the calibration system as illustrated in Figure 7. Audit the field sampling system
once per quarter using a flow rate transfer standard, as described in the EPA High Volume-Sampling Method,
40 CVR 50, Appendix B. Perform a single-point calibration before and after each sample collection, using the
procedures described in Section 11.2.3.
11.2.2.2	Prior to initial multi-point calibration, place an empty glass cartridge in the sampling head and
activate the sampling motor. Fully open the flow control valve and adjust the voltage variator so that a sample
flow rate corresponding to 110 percent of the desired flow rate (typically 0.20 to 0.28 m3/min) is indicated on the
Magnehelic gauge (based on the previously obtained multipoint calibration curve). Allow the motor to warm up
for 10 minutes and then adjust the flow control valve to achieve the desire flow rate. Turn off the sampler.
Record the ambient temperature and barometric pressure on the Field Calibration Data Sheet (see Figure 8).
11.2.2.3	Place the orifice transfer standard on the sampling head and attach a manometer to the tap on
the transfer standard, as illustrated in Figure 7. Properly align the retaining rings with the filter holder and secure
by tightening the three screw clamps. Connect the orifice transfer standard by way of the pressure tap to a
manometer using a length of tubing. Set the zero level of the manometer or magnehelic. Attach the magnehelic
gauge to the sampler venturi quick release connections. Adjust the zero (if needed) using the zero adjust screw
on face of the gauge.
11.2.2.4	To leak test, block the orifice with a rubber stopper, wide duct tape, or other suitable means. Seal
the pressure port with a rubber cap or similar device. Turn on the sampler.
Caution: Avoid running the sampler from too long a time with the orifice blocked. This precaution will
reduce the chance that the motor will be overheated due to the lack of cooling air. Such overheating can
shorten the life of the motor.
11.2.2.5	Gently rock the orifice transfer standard and listen for a whistling sound that would indicate a
leak in the system. A leak-free system will not produce an upscale response on the sampler's magnehelic. Leaks
are usually caused either by damaged or missing gaskets by cross-threading and/or not screwing sample cartridge
together tightly. All leaks must be eliminated before proceeding with the calibration. When the sample is
determined to be leak-free, turn off the sampler and unblock the orifice. Now remove the rubber stopper or plug
from the calibrator orifice.
11.2.2.6	Turn the flow control valve to the fully open position and turn the sampler on. Adjust the flow
control valve until a Magnehelic reading of approximately 70 in. is obtained. Allow the Magnehelic and
manometer readings to stabilize and record these values on the Field Calibration Data Sheet (see Figure 8).
11.2.2.7	Record the manometer reading under Y1 and the Magnehelic reading under Y2 on the Field
Calibration Data Sheet. For the first reading, the Magnehelic should still be at 70 inches as set above.
11.2.2.8	Set the magnehelic to 60 inches by using the sampler's flow control valve. Record the manometer
(Yl) and Magnehelic (Y2) readings on the Field Calibration Data Sheet.
11.2.2.9	Repeat the above steps using Magnehelic settings of 50, 40, 30, 20, and 10 inches.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-17

-------
Method TO-9A
Dioxins and Furans
11.2.2.10	Turn the voltage variator to maximum power, open the flow control valve, and confirm that the
Magnehelic reads at least 100 inches. Turn off the sampler and confirm that the magnehelic reads zero.
11.2.2.11	Read and record the following parameters on the Field Calibration Data Sheet. Record the
following on the calibration data sheet:
Data, job number, and operator's signature;
•	Sampler serial number;
•	Ambient barometric pressure; and
•	Ambient temperature.
11.2.2.12	Remove the "dummy" cartridge and replace with a sample cartridge.
11.2.2.13	Obtain the Manufacturer High Volume Orifice Calibration Certificate.
11.2.2.14	If not performed by the manufacturer, calculate values for each calibrator orifice static pressure
(Column 6, inches of water) on the manufacturer's calibration certificate using the following equation:
^/AH(Pa/760)(298/[Ta + 273])
where:
Pa = the barometric pressure (mm Hg) at time of manufacturer calibration, mm Hg
Ta = temperature at time of calibration, °C
11.2.2.15	Perform a linear regression analysis using the values in Column 7 of the manufacturer High
Volume Orifice Calibration Certificate for flow rate (QSTD) as the "X" values and the calculated values as the Y
values. From this relationship, determine the correlation (CC1), intercept (Bl), and slope (Ml) for the Orifice
Transfer Standard.
11.2.2.16	Record these values on the Field Calibration Data Sheet (see Figure 8).
11.2.2.17	Using the Field Calibration Data Sheet values (see Figure 8), calculate the Orifice Manometer
Calculated Values (Y3) for each orifice manometer reading using the following equation:
Y3 Calculation
Y3 = [Yl(Pa/760)(298/{Ta + 273})f
11.2.2.18	Record the values obtained in Column Y3 on the Field Calibration Data Sheet (see Figure 8).
11.2.2.19	Calculate the Sampler Magnehelic Calculate Values (Y4) using the following equation:
Y4 Calculation
Y4 = [Y2(Pa/760)(298/{Ta + 273})]1/1
11.2.2.20 Record the value obtained in Column Y4 on the Field Calibration Data Sheet (see Figure 8).
11.2.2.21 Calculate the Orifice Flow Rate (XI) in scm, using the following equation:
XI Calculation
xi = Y3 - B1
Ml
Page 9A-18
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
11.2.2.22	Record the values obtained in Column XI, on the Field Calibration Data Sheet (see Figure 8).
11.2.2.23	Perform a linear regression of the values in Column XI (as X) and the values in Column Y4 (as
Y). Record the relationship for correlation (CC2), intercept (B2), and slope (M2) on the Field Calibration Data
Sheet.
11.2.2.24	Using the following equation, calculate a set point (SP) for the manometer to represent a desired
flow rate:
Set point (SP) = [(Expected Pa)/(Expected Ta)(Tstd/Pstd)] [M2 (Desired flow rate) + B2]2
where:
Pa = Expected atmospheric pressure (Pj, mm Hg
Ta = Expected atmospheric temperature (Ta), °C
M2 = Slope of developed relationship
B2 = Intercept of developed relationship
Tstd = Temperature standard, 25 °C
Pstd = Pressure standard, 760 mm Hg
11.2.2.25 During monitoring, calculate a flow rate from the observed Magnehelic reading using the
following equations:
Y5 = [Average Magnehelic Reading (aH) (Pa/Ta)(Tstd/Pstd)]'/2
X2 = Y5 - B2
M2
where:
Y5 = Corrected Magnehelic reading
X2 = Instant calculated flow rate, scm
11.2.2.26 The relationship in calibration of a sampling system between Orifice Transfer Standard and
flow rate through the sampler is illustrated in Figure 9.
11.2.3 Single-Point Audit of the High Volume Sampling System Utilizing Calibrated Orifice Transfer
Standard
Single point calibration checks are required as follows:
•	Prior to the start of each 24-hour test period.
•	After each 24-hour test period. The post-test calibration check may serve as the pre-test calibration check
for the next sampling period if the sampler is not moved.
•	Prior to sampling after a sample is moved.
For samplers, perform a calibration check for the operational flow rate before each 24-hour sampling event and
when required as outlined in the user quality assurance program. The purpose of this check is to track the
sampler's calibration stability. Maintain a control chart presenting the percentage difference between a sampler's
indicated and measured flow rates. This chart provides a quick reference of sampler flow-rate drift problems and
is useful for tracking the performance of the sampler. Either the sampler log book or a data sheet will be used
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-19

-------
Method TO-9A
Dioxins and Furans
to document flowcheck information. This information includes, but is not limited to, sampler and orifice transfer
standard serial number, ambient temperature, pressure conditions, and collected flow-check data.
In this subsection, the following is assumed:
•	The flow rate through a sampler is indicated by the orifice differential pressure;
•	Samplers are designed to operate at an actual flow rate of 8 scfm, with a maximum acceptable flow-rate
fluctuation range of ± 10 percent of this value;
•	The transfer standard will be an orifice device equipped with a pressure tap. The pressure is measured
using a manometer; and
•	The orifice transfer standard's calibration relationship is in terms of standard volumetric flow rate (Qstd).
11.2.3.1	Perform a single point flow audit check before and after each sampling period utilizing the
Calibrated Orifice Transfer Standard (see Section 11.2.1).
11.2.3.2	Prior to single point audit, place a "dummy" glass cartridge in the sampling head and activate the
sampling motor. Fully open the flow control valve and adjust the voltage variator so that a sample flow rate
corresponding to 110 percent of the desired flow rate (typically 0.19 to 0.28 m3/min) is indicated on the
Magnehelic gauge (based on the previously obtained multipoint calibration curve). Allow the motor to warm up
for 10 minutes and then adjust the flow control valve to achieve the desired flow rate. Turn off the sampler.
Record the ambient temperature and barometric pressure on a Field Test Data Sheet (see Figure 10).
11.2.3.3	Place the flow rate transfer standard on the sampling head.
11.2.3.4	Properly align the retaining rings with the filter holder and secure by tightening the 3 screw
clamps. Connect the flow rate transfer standard to the manometer using a length of tubing.
11.2.3.5	Using tubing, attach 1 manometer connector to the pressure tap of the transfer standard. Leave
the other connector open to the atmosphere.
11.2.3.6	Adjust the manometer midpoint by sliding the movable scale until the zero point corresponds with
the water meniscus. Gently shake or tap to remove any air bubbles and/or liquid remaining on tubing connectors.
(If additional liquid is required, remove tubing connector and add clean water.)
11.2.3.7	Turn on high-volume motor and let run for 5 minutes.
11.2.3.8	Record the pressure differential indicated, aH, in inches of water, on the Field Test Data Sheet.
Be sure stable aH has been established.
11.2.3.9	Record the observed Magnahelic gauge reading, in inches of water, on the Field Test Data Sheet.
Be sure stable aM has been established.
11.2.3.10	Using previous established Orifice Transfer Standard curve, calculate Qxs (see
Section 11.2.2.23).
11.2.3.11	This flow should be within ±10 percent of the sampler set point, normally, 8 ft3. If not, perform
a new multipoint calibration of the sampler.
11.2.3.12	Remove Flow Rate Transfer Standard and dummy adsorbent cartridge.
11.3 Sample Collection
11.3.1 General Requirements
11.3.1.1	The sampler should be located in an unobstructed area, at least 2 meters from any obstacle to air
flow. The exhaust hose should be stretched out in the downwind direction to prevent recycling of air into the
sample head.
11.3.1.2	All cleaning and sample module loading and unloading should be conducted in a controlled
environment, to minimize any chance of potential contamination.
Page 9A-20
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
11.3.1.3 When new or when using the sampler at a different location, all sample contact areas need to be
cleared. Use triple rinses of reagent grade hexane or methylene chloride contained in Teflon® rinse bottles.
Allow the solvents to evaporate before loading the PUF modules.
11.3.2	Preparing Cartridge for Sampling
11.3.2.1	Detach the lower chamber of the cleaned sample head. While wearing disposable, clean, lint-free
nylon, or powder-free surgical gloves, remove a clean glass adsorbent module from its shipping container.
Remove the Teflon® end caps. Replace the end caps in the sample container to be reused after the sample has
been collected.
11.3.2.2	Insert the glass module into the lower chamber and tightly reattach the lower chambers to the
module.
11.3.2.3	Using clean rinsed (with hexane) Teflon-tipped forceps, carefully place a clean conditioned fiber
filter atop the filter holder and secure in place by clamping the filter holder ring over the filter. Place the
aluminum protective cover on top of the cartridge head. Tighten the 3 screw clamps. Ensure that all module
connections are tightly assembled. Place a small piece of aluminum foil on the ball-joint of the sample cartridge
to protect from back-diffusion of semi-volatile into the cartridge during transporting to the site.
[Note: Failure to do so could result in air flow leaks at poorly sealed locations which could affect sample
representativeness.]
11.3.2.4	Place in a carrying bag to take to the sampler.
11.3.3	Collection
11.3.3.1	After the sampling system has been assembled, perform a single point flow check as described
in Sections 11.2.3.
11.3.3.2	With the empty sample module removed from the sampler, rinse all sample contact areas using
reagent grade hexane in a Teflon® squeeze bottle. Allow the hexane to evaporate from the module before loading
the samples.
11.3.3.3	With the sample cartridge removed from the sampler and the flow control valve fully open, turn
the pump on and allow it to warm-up for approximately 5 minutes.
11.3.3.4	Attach a "dummy" sampling cartridge loaded with the exact same type of filter and PUF media
to be used for sample collection.
11.3.3.5	Turn the sampler on and adjust the flow control valve to the desired flow as indicated by the
Magnehelic gauge reading determined in Section 11.2.2.24. Once the flow is properly adjusted, take extreme care
not to inadvertently alter its setting.
11.3.3.6	Turn the sampler off and remove both the "dummy" module. The sampler is now ready for field
use.
11.3.3.7	Check the zero reading of the sampler Magnehelic. Record the ambient temperature, barometric
pressure, elapsed time meter setting, sampler serial number, filter number, and PUF cartridge number on the Field
Test Data Sheet (see Figure 10). Attach the loaded sampler cartridge to the sampler.
11.3.3.8	Place the voltage variator and flow control valve at the settings used in Section 11.3.2, and the
power switch. Activate the elapsed time meter and record the start time. Adjust the flow (Magnehelic setting),
if necessary, using the flow control valve.
11.3.3.9	Record the Magnehelic reading every 6 hours during the sampling period. Use the calibration
factors (see Section 11.2.2.23) to calculate the desired flow rate. Record the ambient temperature, barometric
pressure, and Magnehelic reading at the beginning and during sampling period.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-21

-------
Method TO-9A
Dioxins and Furans
11.3.4 Sample Recovery
11.3.4.1	At the end of the desired sampling period, turn the power off. Carefully remove the sampling
head containing the filter and adsorbent cartridge to a clean area.
11.3.4.2	While wearing disposable lint free nylon or surgical gloves, remove the PUF cartridge from the
lower module chamber and lay it on the retained aluminum foil in which the sample was originally wrapped.
11.3.4.3	Carefully remove the glass fiber filter from the upper chamber using clean Teflon®-tipped
forceps.
11.3.4.4	Fold the filter in half twice (sample side inward) and place it in the glass cartridge atop the PUF.
11.3.4.5	Wrap the combined samples in the original hexane rinsed aluminum foil, attached Teflon® end
caps and place them in their original aluminum sample container. Complete a sample label and affix it to the
aluminum shipping container.
11.3.4.6	Chain-of-custody should be maintained for all samples. Store the containers at <4°C and protect
from light to prevent possibly photo-decomposition of collected analytes. If the time span between sample
collection and laboratory analysis is to exceed 24 hours, refrigerate sample.
11.3.4.7	Perform a final calculated sample flow check using the calibration orifice, as described in
Section 11.3.2. If calibration deviates by more than 10 percent from the initial reading, mark the flow data for
that sample as suspect and inspect and/or remove from service.
11.3.4.8	Return at least 1 field filter/PUF blank to the laboratory with each group of samples. Treat a field
blank exactly as the sample except that no air is drawn through the filter/adsorbent cartridge assembly.
11.3.4.9	Ship and store samples under ice (<4°C) until receipt at the analytical laboratory, after which it
should be refrigerated at less than or equal to 4°C. Extraction must be performed within seven days of sampling
and analysis within 40 days after extraction.
12. Sample Preparation
12.1 Extraction Procedure for Quartz Fiber Filters and PUF Plugs
12.1.1	Take the glass sample cartridge containing the PUF plug and quartz fiber filter out of the shipping
container and place it in a 43-mm x 123-mm Soxhlet extractor. Add 10 »«L of 13C12-labeled sample fortification
solution (see Table 4) to the sample. Put the thimble into a 50 mm Soxhlet extractor fitted with a 500 mL boiling
flask containing 275 mL of benzene.
[Note: While the procedure specifies benzene as the extraction solution, many laboratories have substituted
toluene for benzene because of the carcinogenic nature of benzene (28). The EPA is presently studying the
replacement of benzene with toluene.]
12.1.2	Place a small funnel in the top of the Soxhlet extractor, making sure that the top of the funnel is inside
the thimble. Rinse the inside of the corresponding glass cylinder into the thimble using approximately 25 mL
of benzene. Place the extractor on a heating mantel. Adjust the heat until the benzene drips at a rate of 2 drops
per second and allow to flow for 16 hours. Allow the apparatus to cool.
12.1.3	Remove the extractor and place a 3-bulb Snyder column onto the flask containing the benzene extract.
Place on a heating mantel and concentrate the benzene to 25 mL (do not let go to dryness). Add 100 ml of hexane
and again concentrate to 25 mL. Add a second 100 mL portion of hexane and again concentrate to 25 mL.
12.1.4	Let cool and add 25 mL hexane. The extract is ready for acid/base cleanup at this point.
Page 9A-22
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
12.2 Cleanup Procedures
12.2.1	Acid/Base Cleanup. Transfer the hexane extract to a 250 mL separatory funnel with two 25-mL
portions of hexane. Wash the combined hexane with 30 ml of 2 N potassium hydroxide. Allow layers to separate
and discard the aqueous layer. Repeat until no color is visible in the aqueous layer, up to a maximum of 4
washes. Partition the extract against 50 ml of 5% sodium chloride solution. Discard the aqueous layer. Carefully
add 50 mL of concentrated sulfuric acid. Shake vigorously for 1 minute, allow layers to separate, and discard
the acid layer. Repeat the acid wash until no color is visible in the aqueous layer, up to a maximum of 4 washes.
Partition the extract against 50 ml of 5% sodium chloride solution. Discard the aqueous layer. Transfer the
hexane through a 42-mm x 160-mm filter funnel containing a plug of glass wool and 3-cm of sodium sulfate into
a 250-mL Kuderna-Danish (KD) concentrator fitter with a 15-mL catch tube. Rinse the filter funnel with two
25 mL portions of hexane. Place a 3-bulb Snyder column on the KD concentrator and concentrate on a steam
bath to 1-2 mL. The extract is ready for the alumina column cleanup at this point, but it can be sealed and stored
in the dark, if necessary. An extract that contains obvious contamination, such as yellow or brown color, is
subjected to the silica column cleanup prior to the alumina cleanup.
12.2.2	Silica Column Preparation. Gently tamp a plug of glass wool into the bottom of a 5.75-inch (14.6
cm) disposable Pasteur pipette. Pour prewashed 100-200 mesh Bio-Sil®A (silica gel) into the pipette until a
height of 3.0 cm of silica gel is packed into the column. Top the silica gel with 0.5 cm of anhydrous granular
sodium sulfate. Place columns in an oven set at 220°C. Store columns in the oven until ready for use, at least
overnight. Remove only the columns needed and place them in a desiccator until they have equilibrated to room
temperature. Use immediately.
12.2.3	Silica Column Cleanup. Position the silica column over the alumina column so the eluent will drip
onto the alumina column. Transfer the 2 mL hexane extract from the Acid/Base Cleanup onto the silica column
with two separate 0.5-mL portions of hexane. Elute the silica column with an additional 4.0 mL of hexane.
Discard the silica column and proceed with the alumina column cleanup at the point where the column is washed
with 6.0 mL of carbon tetrachloride.
12.2.4	Alumina Column Preparation. Gently tamp a plug of glass wool into the bottom of a 5.75-inch
(14.6 cm) disposable Pasteur pipette. Pour WOELM neutral alumina into the pipette while tapping the column
with a pencil or wooden dowel until a height of 4.5 cm of alumina is packed into the column. Top the alumina
with a 0.5 cm of anhydrous granular sodium sulfate. Prewash the column with 3 mL dichloromethane. Allow
the dichloromethane to drain from the column; then force the remaining dichloromethane from the column with
a stream of dry nitrogen. Place prepared columns in an oven set at 2250 C. Store columns in the oven until ready
for use, at least overnight. Remove only columns needed and place them in a desiccator over anhydrous calcium
sulfate until they have equilibrated to room temperature. Use immediately.
12.2.5	Alumina Column Cleanup. Prewet the alumina column with 1 mL of hexane. Transfer the 2 mL
hexane extract from acid/base cleanup into the column. Elute the column with 6.0 mL of carbon tetrachloride
and archive. Elute the column with 4.0 mL of dichloromethane and catch the eluate in a 12- mL distillation
receiver. Add 3 »«L tetradecane, place a micro-Snyder column on the receiver and evaporate the dichloromethane
just to dryness by means of a hot water bath. Add 2 mL of hexane to the receiver and evaporate just to dryness.
Add another 2-mL portion of hexane and evaporate to 0.5 mL. The extract is ready for the carbon column
cleanup at this point.
12.2.6	Carbon Column Preparation. Weigh 9.5 g of Bio-Sil®A (100-200 mesh) silica gel, which has been
previously heated to 225 °C for 24 hours, into a 50-mL screw cap container. Weigh 0.50 g of Amoco PX-21
carbon onto the silica gel cap and shake vigorously for 1 hour. Just before use, rotate the container by hand for
at least 1 minute. Break a glass graduated 2.0-mL disposal pipette at the 1.8 mL mark and fire polish the end.
Place a small plug of glass wool in the pipette and pack it at the 0.0 mL mark using two small solid glass rods.
Add 0.1 mL of Bio-Sil®A 100-200 mesh silica gel. If more than 1 column is to be made at a time, it is best to
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-23

-------
Method TO-9A
Dioxins and Furans
add the silica gel to all the columns and then add the carbon-silica gel mixture to all columns. Add 0.40 mL of
the carbon silica gel mixture to the column; the top of the mixture will be at the 0.55-mL mark on the pipette.
Top the column with a small plug of glass wool.
12.2.7 Carbon Column Cleanup. Place the column in a suitable clamp with the silica gel plug up. Add
approximately 0.5 mL of 50 percent benzene-methylene chloride (v/v) to the top of the column. Fit a 10 mL
disposable pipette on the top of the carbon column with a short piece of extruded teflon tubing. Add an additional
9.5 mL of the 50 percent benzene-methylene chloride. When approximately 0.5 mL of this solvent remains, add
10 mL of toluene. After all the toluene has gone into the column, remove the 10-mL reservoir and add at least
2.0 mL of hexane to the column. When approximately 0.1 mL of the hexane is left on the top of the column,
transfer the sample extract onto the column with a Pasteur pipette. Rinse the distillation receiver column that
contained the extract with two separate 0.2 mL portions of hexane and transfer each rinse onto the column. Allow
the top of each transfer layer to enter the glass wool before adding the next one. When the last of the transfer
solvent enters the glass wool, add 0.5 mL of methylene chloride, replace the 10-mL reservoir, and add 4.5 mL
of methylene chloride to it. When approximately 0.5 mL of this solvent remains, add 10 mL of 50 percent
benzene-methylene chloride. When all this solvent has gone onto the column, remove the reservoir, take the
column out of the holder and rinse each end with toluene, turn the column over, and put it back in the holder. All
previous elution solvents are archived. Place a suitable receiver tube under the column and add 0.5 mL of toluene
to the top of the column. Fit the 10 mL reservoir on the column and add 9.5 mL of toluene to it. When all toluene
has eluted through the column and has been collected in the receiving tube, add 5 mL of tetradecane and
concentrate to 0.5 mL using a stream of nitrogen and water bath maintained at 600 C. Transfer the toluene extract
to a 2.0 mL graduated Chromoflex® tube with two 0.5-mL portions of benzene. Add 0.5 ng of 13C12-1,2,3,4-
TCDD and store the extracts in the dark at room temperature. Concentrate the extract to 30 uL using a stream
of nitrogen at room temperature just prior to analysis or shipping. Transfer the extracts that are to be shipped
to a 2 mm i.d. x 75 mm glass tube that has been fire sealed on one end with enough benzene to bring the total
volume of the extract to 100 ,uL. Then fire seal other end of the tube.
12.3 Glassware Cleanup Procedures
In this procedure, take each piece of glassware through the cleaning separately except in the oven baking process.
Wash the 100-mL round bottom flasks, the 250 mL separatory funnels, the KD concentrators, etc., that were used
in the extraction procedures three times with hot tap water, two times with acetone and two times with hexane.
Then bake this glassware in a forced air oven that is vented to the outside for 16 hours at 450 °C. Clean the PFTE
stopcocks as above except for the oven baking step. Rinse all glassware with acetone and hexane immediately
before use.
13. HRGC-HRMS System Performance
13.1 Operation of HRGC-HRMS
Operate the HRMS in the electron impact (EI) ionization mode using the selected ion monitoring (SIM) detection
technique. Achieve a static mass resolution of 10,000 (10% valley) before analysis of a set of samples is begun.
Check the mass resolution at the beginning and at the end of each day. (Corrective actions should be implemented
whenever the resolving power does not meet the requirement.) Chromatography time required for PCDDs and
PCDFs may exceed the long-term stability of the mass spectrometer because the instrument is operated in the
high-resolution mode and the mass drifts of a few ppm (e.g., 5 ppm in mass) can have adverse effects on the
analytical results. Therefore, a mass-drift correction may be required. Use a lock-mass ion for the reference
Page 9A-24
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
compound perfluorokerosene (PFK) to tune the mass spectrometer. The selection of the SIM lock-mass ions of
PFK shown in the descriptors (see Tables 10, 11 and 12) is dependent on the masses of the ions monitored within
each descriptor. An acceptable lock-mass ion at any mass between the lightest and heaviest ion in each descriptor
can be used to monitor and correct mass drifts. Adjust the level of the reference compound (PFK) metered inside
the ion chamber during HRGC-HRMS analyses so that the amplitude of the most intense selected lock-mass ion
signal is kept to a minimum. Under those conditions, sensitivity changes can be more effectively monitored.
Excessive use of PFK or any reference substance will cause high background signals and contamination of the
ion source, which will result in an increase in "downtime" required for instrument maintenance.
Tune the instrument to a mass resolution of 10,000 (10% valley) at m/z 292.9825 (PFK). By using the peak
matching unit (manual or computer simulated) and the PFK reference peak, verify that the exact m/z 392.9761
(PFK) is within 3 parts per million (ppm) of the required value.
Document the instrument resolving power by recording the peak profile of the high mass reference signal (m/z
392.9761) obtained during the above peak matching calibration experiment by using the low mass PFK ion at
m/z 292.9825 as a reference. The minimum resolving power of 10,000 should be demonstrated on the high mass
ion while it is transmitted at a lower accelerating voltage than the low mass reference ion, which is transmitted
at full voltage and full sensitivity. There will be little, if any, loss in sensitivity on the high mass ion if the source
parameters are properly tuned and optimized. The format of the peak profile representation should allow for
computer calculated and manual determination of the resolution, i.e., the horizontal axis should be a calibrated
mass scale (amu or ppm per division). Detailed descriptions for mass resolution adjustments are usually found
in the instrument operators manual or instructions.
13.2	Column Performance
After the HRMS parameters are optimized, analyze an aliquot of a column performance solution containing the
first and last eluting compounds (see Table 9), or a solution containing all congeners, to determine and confirm
SIM parameters, retention time windows, and HRGC resolution of the compounds. Adjustments can be made
at this point, if necessary. Some PeCDFs elute in the TCDD retention time window when using the 60 m DB-5
column. The PeCDF masses can be included with the TCDD/TCDF masses in Descriptor 1. Include the
PeCDD/PeCDF masses with the TCDD/TCDF masses when using the 60 m SP-2331 polar column. The HRGC-
HRMS SIM parameters and retention time windows can be rapidly and efficiently determined and optimized by
analysis of a window defining solution of PCDDs/PCDFs using one mass for each isomer for the complete
analysis of tetra- through octa- compounds, as illustrated in Figure 11.
13.3	SIM Cycle Time
The total time for each SIM cycle should be 1 second or less for data acquisition, which includes the sum of the
mass ion dwell times and ESA voltage reset times.
13.4	Peak Separation
Chromatographic peak separation between 2,3,7,8-TCDD and the co-eluting isomers should be resolved with
a valley of 25% or more (see Figure 12).
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-25

-------
Method TO-9A
Dioxins and Furans
13.5 Initial Calibration
After the HRGC-HRMS SIM operating conditions are optimized, perform an initial calibration using the 5
calibration solutions shown in Table 3. The quantification relationships of labeled and unlabeled standards are
illustrated in Tables 15, 16, 17, and 18. Figures 13 through 22 represent the extracted ion current profiles (EICP)
for specific masses for 2,3,7,8-TCDF, 2,3,7,8-TCDD and other 2,3,7,8-substituted PCDF/PCDD (along with
their labeled standards) through OCDF and OCDD respectively.
[Note: Other solutions containing fewer or different congeners and at different concentrations may also be
used for calibration purposes.]
Referring to Tables 10, 11, or 12, calculate (1) the relative response factors (RRFs) for each unlabeled
PCDD/PCDF and PBDD/PBDF [RRF (I)] relative to their corresponding 13C12-labeled internal standard and (2)
the RRFs for the 13C12-labeled PCDD/PCDF and PBDD/PBDF internal standards [RRF (II)] relative to37Cl4-
2,3,7,8-TCDD recovery standard using the following formulae:
(A xQ.)
RRF(I) = x 1S
(Q x A.)
1S^
(A xQ )
RRF(II) =
(Q x A )
rs^
where:
Ax = the sum of the integrated ion abundances of the quantitation ions (see Tables 10,
11 or 12) for unlabeled PCDDs/PCDFs, and PBDDs/PBDFs and BCDDs/BCDFs.
A1S = the sum of the integrated ion abundances of the quantitation ions for the
13C12-labeled internal standards (see Table 10, 11 or 12).
[Note: Other 13Cu-labeled analytes may also be used as the recovery standard(s)]
Ars = the integrated ion abundance for the quantitation ion of the 37Q -2,3,7,8-TCDD
recovery standard.
Q1S = the quantity of the 13C12-labeled internal standard injected, pg.
Qx = the quantity of the unlabeled PCDD/PCDF analyte injected, pg.
Qrs = the quantity of the 37Cl4-2,3,7,8-TCDD injected, pg.
RRF(I) and RRF(II) = dimensionless quantities. The units used to express Q1S and Qx must be the same.
[Note: 13CI2-1,2,3,7,8-PeBDF is used to determine the response factor for the unlabeled 2,3,7,8-substituted,
PeBDD, HxBDF and HxBDD.]
Page 9A-26
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
Calculate the average RRFs for the 5 concentration levels of unlabeled and 13C12-labeled PCDDs/PCDFs and
PBDDs/PBDFs for the initial calibration using the following equation:
7777^ RRF1 + RRF2 +RRF3 + RRF4 +RRF5
RRF =	
5
13.6	Criteria Required for Initial Calibration
The analytical data must satisfy certain criteria for acceptable calibration. The isotopic ratios must be within the
acceptable range (see Tables 19 and 20). The percent relative standard deviation for the response factors should
be less than the values presented in Table 21. The signal-to-noise ratio for the 13C12-labeled standards must be
10:1 or more and 5:1 or more for the unlabeled standards.
13.7	Continuing Calibration
Conduct an analysis at the beginning of each day to check and confirm the calibration using an aliquot of the
calibration solution. This analysis should meet the isotopic ratios and signal to noise ratios of the criteria stated
in Section 13.6 (see Table 21 for daily calibration percent difference criteria). It is good practice to confirm the
calibration at the end of the day also. Calculate the daily calibration percent difference using the following
equation.
RRF -RRF
%RRF =		x 100
RRF
RRFCC = the relative response factor for a specific analyte in the continuing calibration standard.
14. HRGC-HRMS Analysis And Operating Parameters
14.1 Sample Analysis
Sample Analysis. An aliquot of the sample extract is analyzed with the HRGC-HRMS system using the
instrument parameters illustrated in Tables 13 and 14 and the SIM descriptors and masses shown in Tables 10,
11, and 12. A 30-m SE-54 fused silica capillary column is used to determine the concentrations of total tetra-,
penta-, hexa-, hepta- and octa-CDDs/CDFs and/or to determine the minimum limits of detections (MLDs) for
the compounds. If the tetra-, penta-, and hexa-CDDs/CDFs were detected in a sample and isomer specific
analyses are required, then an aliquot of the sample extract is analyzed using the 60 m SP-2331 fused silica
capillary column to provide a concentration for each 2,3,7,8-substituted PCDD/PCDF and concentrations for total
PCDDs and PCDFs also.
[Note: Other capillary columns such as the DB-5, SE-30, and DB-225 may be used if the performance
satisfies the specifications for resolution of PCDDs/PCDFs. The SE-54 column resolves the four HpCDF
isomers, two HpCDD isomers, OCDF and OCDD for isomer specific analysis. It does not resolve the tetra-,
penta-, and hexa-2,3,7,8-substituted isomers. The SE-54 column is used for the analysis ofPBDDs and
PBDFs.J
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-27

-------
Method TO-9A
Dioxins and Furans
Isomer specificity for all 2,3,7,8-substituted PCDDs/PCDFs cannot be achieved on a single HRGC capillary
column at this time. However, many types of HRGC capillary columns are available and can be used for these
analyses after their resolution capabilities are confirmed to be adequate using appropriate standards.
Two HRGC columns shown in Table 13 have been used successfully since 1984 (27, 28). The 60-m DB-5
provides an efficient analysis for total concentrations of PCDDs/PCDFs, specific isomers (total tetra-, penta-,
hexa-CDDs/CDFs, four HpCDF isomers, two HpCDD isomers, OCDD and OCDF), PBDDs/PBDFs, and/or
determination of MDLs. The 60 m SP-2331 column provides demonstrated and confirmed resolution of 2,3,7,8-
substituted tetra-, penta-, and hexa-PCDDs/PCDFs (14). The descriptors and masses shown in Tables 10, 11
and 12 must be modified to take into account the elution of some of the PeCDDs and PeCDFs in the tetra
retention time window using the SP-233 lcolumn.
14.2	Identication Criteria
Criteria used for identification of PCDDs and PCDFs in samples are as follows:
•	The integrated ion abundance ratio M/(M+2) or (M+2)/(M+4) shall be within 15 percent of the theoretical
value. The acceptable ion abundance ranges are shown in Tables 19 and 20.
•	The ions monitored for a given analyte, shown in Tables 10, 11, and 12, shall reach their maximum within
2 seconds of each other.
•	The retention time for the 2,3,7,8-substituted analytes must be within 3 seconds of the corresponding 13C12-
labeled internal standard, surrogate, or alternate standard.
•	The identification of 2,3,7,8-substituted isomers that do not have corresponding 13C12-labeled standards
is done by comparison to the analysis of a standard that contains the specific congeners. Comparison of
the relative retention time (RRT) of the analyte to the nearest internal standard with reference (i.e., within
0.005 RRT time units to the comparable RRTs found in the continuing calibration or literature).
•	The signal-to-noise ratio for the monitored ions must be greater than 2.5.
•	The analysis shall show the absence of polychlorinated diphenyl- ethers (PCDPEs). Any PCDPEs that co-
elute (± 2 seconds) with peaks in the PCDF channels indicates a positive interference, especially if the
intensity of the PCDPE peak is 10 percent or more of the PCDF.
Use the identification criteria in Section 14.2 to identify and quantify the PCDDs and PCDFs in the sample.
Figure 23 illustrates a reconstructed EICP for an environmental sample, identifying the presence of
2,3,7,8-TCDF as referenced to the labeled standard.
14.3	Quantification
The peak areas of ions monitored for 13C12-labeled PCDDs/PCDFs and7 CI -^,3,7,8-TCDD, unlabeled
PCDDs/PCDFs, and respective relative response factors are used for quantification. The 37Cl4-2,3,7,8-TCDD,
spiked to extract prior to final concentration, and respective response factors are used to determine the sample
extraction efficiencies achieved for the nine 13C12-labeled internal standards, which are spiked to the sample prior
to extraction (% recovery). The 13C12-labeled PCDD/PCDF internal standards and response factors are used for
quantification of unlabeled PCDDs/PCDFs and for determination of the minimum limits of detection with but
one exception: 13C12-OCDD is used for OCDF. Each 13C12-labeled internal standard is used to quantify all of
the PCDDs/PCDFs in its isomeric group. For example, 13C12-2,3,7,8-TCDD and the 2,3,7,8-TCDD response
factor are used to quantify all of the 22 tetra-chlorinated isomers. The quantification relationships of these
standards are shown in Tables 15, 16, 17, and 18. The 37Cl4-2,3,7,8-TCDD spiked to the filter of the sampler
Page 9A-28
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
prior to sample collection is used to determine the sampler retention efficiency, which also indicates the collection
efficiency for the sampling period.
14.4 Calculations
14.4.1 Extraction Efficiency. Calculate the extraction efficiencies (percent recovery) of the 9 13C12-labeled
PCDD/PCDF or the 3 13C12-labeled PBDD/PBDF internal standards measured in the extract using the formula:
[A. xQ xlOOl
L is	J
%R =¦
18 [QisxArsxRRF(II)]
where:
%Ris = percent recovery (extraction efficiency).
A1S = the sum of the integrated ion abundances of the quantitation ions (see Tables 10, 11 or 12) for
the 13C12-labeled internal standard.
Ars = the sum of the integrated ion abundances of the quantitation ions (see Table 10, 11 or 12) for
the 37C14- or 13C12-labeled recovery standard; the selection of the recovery standard(s) depends
on the type of homologues.
Q1S = quantity of the 13C12-labeled internal standard added to the sample before extraction, pg.
Qrs = quantity of the ' CI, - or13 Q2 -labeled recovery standard added to the sample extract before
HRGC-HRMS analysis, pg.
RRF(II) = calculated mean relative response factor for the labeled internal standard relative to the
appropriate labeled recovery standard.
14.4.2 Calculation of Concentration. Calculate the concentration of each 2,3,7,8-substituted PCDD/PCDF,
other isomers or PBDD/PBDF that have met the criteria described in Sections 14.2 using the following formula:
c	[AxxQls]
X [AisxVstdxRRF(I)]
where:
Cx = concentration of unlabeled PCDD/PCDF, PBDD/PBDF or BCDD/BCDF congener(s), pg/m3.
Ax = the sum of the integrated ion abundances of the quantitation ions (see Table 11, 12 or 13) for the
unlabeled PCDDs/PCDFs, or PBDDs/PBDFs or BCDFs.
A1S = the sum of the integrated ion abundances of the quantitation ions (see Table 11, 12 or 13) for the
respective 13C12-labeled internal standard.
Q1S = quantity of the 13C12-labeled internal standard added to the sample before extraction, pg.
Vstd = standard volume of air, std m3.
RRF(I) = calculated mean relative response factor for an unlabeled 2,3,7,8-substituted PCDD/PCDF
obtained in Section 13.4.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-29

-------
Method TO-9A
Dioxins and Furans
14.5 Method Detection Limits (MDLs)
The ambient background levels of total PCDDs/PCDFs are usually found in the range of 0.3 to 2.9 pg/m3.
Therefore, the MDLs required to generate meaningful data for ambient air should be in the range of 0.02 to 0.15
pg/m3 for tetra-, penta-, and hexa-CDDs/CDFs. Trace levels, 0.05 to 0.25 pg/m3, of HpCDDs and OCDD are
usually detected in the method blank (background contamination).
An MDL is defined as the amount of an analyte required to produce a signal with a peak area at least 2.5 x the
area of the background signal level measured at the retention time of interest. MDLs are calculated for total
PHDDs/PHDFs and for each 2,3,7,8-substituted congener. The calculation method used is dependent upon the
type of signal responses present in the analysis. For example:
•	Absence of response signals of one or both quantitation ion signals at the retention time of the 2,3,7,8-
substituted isomer or at the retention time of non 2,3,7,8-substituted isomers. The instrument noise level
is measured at the analyte's expected retention time and multiplied by 2.5, inserted into the formula below
and calculated and reported as not detected (ND) at the specific MDL.
•	Response signals at the same retention time as the 2,3,7,8-substituted isomers or the other isomers that
have a S/N ratio in excess of 2.5:1 but that do not satisfy the identification criteria described in 14.2 are
calculated and reported as ND at the elevated MDL and discussed in the narrative that accompanies the
analytical results. Calculate the MDLs using the following formula:
[2.5 x A x Q ]
MDL = —	-———
[A1S x Vstd x RRF]
where:
MDL =
Ax =
A1S -
Q» =
vstd =
RRF =
concentration of unlabeled PHDD/PHDF, pg/m3.
sum of integrated ion abundances of the quantitation ions (see Table 10, 11 or 12) for the
unlabeled PHDDs/PHDFs which do not meet the identification criteria or 2.5 x area of noise
level at the analyte's retention time.
sum of the integrated ion abundances of the quantitation ions (see Table 10, 11, or 12) for the
13C12-labeled internal standards.
quantity of the 13C12-labeled internal standard spiked to the sample prior to extraction, pg.
standard volume of ambient air sampled, std m3.
mean relative response factor for the unlabeled PHDD/PHDF.
14.6 2,3,7,8-TCDD Toxic Equivalents
Calculate the 2,3,7,8-TCDD toxic equivalents of PCDDs and PCDFs present in a sample according to the method
recommended by EPA and the Center for Disease Control (18). This method assigns a 2,3,7,8-TCDD toxicity
equivalency factor (TEF) for each of the seventeen 2,3,7,8-substituted PCDDs/PCDFs (see Table 22). The
2,3,7,8-TCDD equivalent of the PCDDs and PCDFs present in the sample is calculated by the respective TEF
factors times their concentration for each of the compounds listed in Table 22. The exclusion of the other isomeric
groupings (mono-, di-, and tri-chlorinated dibenzodioxins and dibenzofurans) does not mean that they are non-
toxic. Their toxicity, as known at this time, is much less than the toxicity of the compounds listed in Table 22.
The above procedure for calculating the 2,3,7,8-TCDD toxic equivalents is not claimed to be based on a
Page 9A-30
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
thoroughly established scientific foundation. The procedure, rather, represents a "consensus recommendation
on science policy." Similar methods are used throughout the world.
15. Quality Assurance/Quality Control (QA/QC)
15.1	Certified analytical standards were obtained from Cambridge Isotope Laboratories, 50 Frontage Road,
Andover, MA 01810, 508-749-8000.
15.2	Criteria used for HRGC-HRMS initial and continuing calibration are defined in Sections 13.5 and 13.6.
15.3	Analytical criteria used for identification purposes are defined in Section 14.2.
15.4	All test samples, method blanks, field blanks, and laboratory control samples are spiked with 13C12-labeled
internal standards prior to extraction.
15.5	Sample preparation and analysis and evaluation of data are performed on a set of 12 samples, which may
consist of 9 test samples, field blank, method blank, fortified method blank, or a laboratory control sample.
15.6	Method evaluation studies were performed to determine and evaluate the overall method capabilities (1,
2).
15.7	The 13C12-1,2,3,4-TCDD solution is spiked to filters of all samplers, including field blanks, immediately
prior to operation or is spiked to all PUF plugs prior to shipping them to the field for sampling to determine and
document the sampling efficiency.
15.8	Minimum equipment calibration and accuracy requirements achieved are illustrated in Table 23.
15.9	QA/QC requirements for data:
Criteria
The data shall satisfy all indicated identification criteria
Method efficiency achieved for 13C12-labeled tetra-, penta-, hexa-
CDDs/CDFs and PBDDs/PBDFs
Method efficiency achieved for 13C12-labeled HpCDD and OCDD
Accuracy achieved for PHDDs and PHDFs
in method spike at 0.25 to 2.0 pg/m3
concentration range
Precision achieved for duplicate method spikes or QA samples
Sampler efficiency achieved for 13C12-1,2,3,4-TCDD
Method blank contamination
Method detection limit range
for method blank and field blank (individual isomers)
January 1999	Compendium of Methods for Toxic Organic Air Pollutants	Page 9A-31
Requirements
Discussed in Section 14.2
50 to 120%
40 to 120%
70 to 130%
± 30%
50 to 120%
Free of contamination that would
interfere with test sample results.
0.02 to 0.25 pg/m3

-------
Method TO-9A
Dioxins and Furans
16. Report Format
The analytical results achieved for a set of 12 samples should be presented in a table such as the one shown in
Table 24. The analytical results, analysis, QA/QC criteria, and requirements used to evaluate data are discussed
in an accompanying analytical report. The validity of the data in regard to the data quality requirements and any
qualification that may apply is explained in a clear and concise manner for the user's information.
Page 9A-32
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
17. References
1.	Harless, R. L. et al., "Evaluation of Methodology for Determination of Polyhalogenated Dibenzo-p-Dioxins
and Dibenzofurans in Ambient Air," in Proceedings of the 1991 EPA/A&WMA International Symposium on
Measurement of Toxic and Related Air Pollutants, U. S. Environmental Protection Agency, Research Triangle
Park, NC 27711, EPA-600/9-91-018, May 1991.
2.	Harless, R. L., et al., "Evaluation of a Sampling and Analysis Method for Determination of Polyhalogenated
Dibenzo-p-Dioxins and Dibenzofurans in Ambient Air," in Proceedings of the 11th International Symposium
on Chlorinated Dioxins and Related Compounds, U. S. Environmental Protection Agency, Research Triangle
Park, NC 27711, EPA-600/D-91-106; Chemosphere, Vol. 25, (7-10): 1317-1322, Oct-Nov 1992.
3.	Smith-Mullen, C., et al., Feasibility of Environmental Monitoring and Exposure Assessment for a Municipal
Waste Combustor, Rutland, Vermont Pilot Study, U. S. Environmental Protection Agency, Research Triangle
Park, NC 27711, EPA-600/8-91-007, March 1991.
4.	Harless, R. L., et al., Sampling and Analysis for Poly chlorinated Dibenzo-p-Dioxins and Dibenzofurans
in Ambient Air, U. S. Environmental Protection Agency, Research Triangle Park, NC 27711, EPA-600/D-9-172,
May 1990.
5.	Harless, R L. et al., Analytical Procedures and Quality Assurance Plan for the Analysis of 2,3,7,8-TCDD
in Tier 3-7 Samples of the U. S. EPA National Dioxin Study, U. S. Environmental Protection Agency, Research
Triangle Park, NC 27711, EPA-600/3-85-019, May 1986.
6.	Harless, R. L. et al., Analytical Procedures and Quality Assurance Plan for the Analysis ofTetra Through
Octa Chlorinated Dibenzo-p-Dioxins and Dibenzofurans in Tier 4 Combustion and Incineration Processes,
U. S. Environmental Protection Agency, Research Triangle Park, NC 27711, Addendum to EPA-600/3-85-019,
May 1986.
7.	Albro, P.W., et al., "Methods for the Quantitative Determination of Multiple Specific Polychlorinated
Dibenzo-p-Dioxins and Dibenzofuran Isomers in Human Adipose Tissue in the Parts-Per-Trillion Range. An
Interlaboratory Study," Anal. Chem., Vol.57:2717-2725, 1985.
8.	O'Keefe, P. W., et al., "Interlaboratory Validation of PCDD and PCDF Concentrations Found in Municipal
Incinerator Emissions," Chemosphere, Vol. 18:185-192, 1989.
9.	Harless, R. L., et al., "Identification of Bromo/Chloro Dibenzo-p-Dioxins and Dibenzofurans in Ash
Samples," Chemosphere, Vol. 18:201-208, 1989.
10.	Lafleur, L.E., and Dodo, G. H., "An Interlaboratory Comparison of Analytical Procedures for the
Measurement ofPCDDs/PCDFs in Pulp and Paper Industry Solid Wastes," Chemosphere, Nol. 18:77-84, 1989.
11.	Patterson, D. G. et al., "Levels of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans in Workers
Exposed to 2,3,7,8-TCDD," American Journal of Industrial Medicine, Vol. 16:135-146, 1989.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-33

-------
Method TO-9A
Dioxins and Furans
12.	Lamparski, L. L. andNestrick, T. J. "Determination of Tetra-, Hexa-, Hepta-and Octa-chlorodibenzo-p-
dioxin isomers in Particulate Samples at Parts-Per-Trillion Levels," Anal. Chem., Vol. 52:2045-2054, 1980.
13.	Rappe, C., "Analysis of Polychlorinated Dioxins and Furans," Environ. Sci. Technol., Vol. 18:78A-90A,
1984.
14.	Rappe, C., et al., "Identification of PCDDs and PCDFs in Urban Air," Chemosphere, Vol. 17:3-20, 1988.
15.	Tondeur, Y., et al., "Method 8290: An Analytical Protocol for the Multimedia Characterization of
Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans by High Resolution Gas Chromatography/High
Resolution Mass Spectrometry," Chemosphere, Vol. 18:119-131, 1989.
16.	"Method 23, Method for Measurement of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from
Stationary Sources," Federal Register, Vol. 56(30):5758-5770, February 13, 1991.
17.	"Method 1613: Tetra- through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC-HRMS,"
Federal Register, Vol. 56(26:)5098-5122, February 7, 1991.
18.	Interim Procedures for Estimating Risks Associated with Exposures to Mixtures of Chlorinated Dibenzo-
p-Dioxins and Dibenzofurans (CDDs/CDFs), U. S. Environmental Protection Agency, Research Triangle Park,
NC 27711, EPA-625/3-89-016, March 1989.
19.	Tiernan, T., et al., "PCDD/PCDF in the Ambient Air of a Metropolitan Area in the U.S.," Chemosphere,
Vol. 19:541-546, 1989.
20.	Hunt, G., "Measurement of PCDDs/PCDFs in Ambient Air," J. Air Pollut. Control Assoc., Vol. 39:330-
331, 1989.
21.	"40 CFR Parts 707 and 766, Polyhalogenated Dibenzo-p-Dioxins and Dibenzofurans: Testing and Reporting
Requirements: Final Rule," Federal Register, Vol. 52 (108):21412-21452, June 5, 1987.
22.	Buser, H., "Polybrominated Dibenzo-p-Dioxins and Dibenzofurans: Thermal reaction products of
polybrominated diphenyl ether flame retardants," Environ. Sci. Technol., Vol. 20:404-408, 1988.
23.	Sovocol, G. W., et al., "Analysis of Municipal Incinerator Fly Ash for Bromo and Bromo/Chloro Dioxins,
Dibenzofurans, and Related Compounds," Chemosphere, Vol. 18:193-200, 1989.
24.	Lewis, R. G., et al., Modification and Evaluation of a High-Volume Air Sampler for Pesticides and
Semivolatile Industrial Organic Chemicals," Anal. Chem., Vol. 54:592-594, 1982.
25.	Lewis, R G., et al., "Evaluation of Polyurethane Foam for Sampling Pesticides, Polychlorinated Biphenyls
and Polychlorinated Naphthalenes in Ambient Air," Anal. Chem., Vol. 49:1668-1672, 1977.
26.	Winberry, W. T., Jr., et al., Compendium of Methods for the Determination of Toxic Organic Compounds
in Ambient Air, Second Supplement, Method TO-9, U. S. Environmental Protection Agency, Research Triangle
Park, NC 27711, EPA 600/4-89-018, March 1989.
Page 9A-34
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
27.	"Analysis of Air Samples for PCDDs, PCDFs, PCBs, and PAHs in Support of the Great Lakes Deposition
Project," Draft Report, Midwest Research Institute, 425 Volker Boulevard, Kansas City, MO, MRI Project
No. 3103-A, April 1990.
28.	Boggess, K.E., "Analysis of Air Samples for PCDDs, PCDFs, PCBs and PAHs in Support of the Great
Lakes Deposition Project," Final Report, Midwest Research Institute, 425 Volker Boulevard, Kansas City, MO,
MRI Project No. 3103-A, April 1993.
29.	"Working with Carcinogens," NIOSH, Publication 77-206, August 1977.
30.	"Safety in the Academic Chemistry Laboratories," ACS Committee on Chemical Safety, 1979.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-35

-------
Method TO-9A
Dioxins and Furans
TABLE 1. NUMBER OF POLY CHLORINATED DIBENZO-P-DIOXIN AND
DIBENZOFURAN (PCDD/PCDF) CONGENERS
\o ol'( hlorine Alums
\o dI" l'( 1)1) Isomers
\o oN'CDI- Isomers
1
2
4
2
10
16
3
14
28
4
22
38
5
14
28
6
10
16
7
2
4
8
1
1
Total
75
135
[Note: This also applies for the polybrominated dibenzo-p-dioxins and dibenzofurans
(PBDDs/PBDFs).]
TABLE 2. LIST OF 2,3,7,8-CHLORINE
SUBSTITUTED PCDD/PCDF CONGENERS
I'CDDs
P( 1)1 s
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF

2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDD
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDD
1,2,3,7,8,9-HxCDF

2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF

1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDD
1,2,3,4,6,7,8,9-OCDF
Page 9A-36
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 3. COMPOSITIONS OF THE INITIAL CALIBRATION SOLUTIONS OF
LABELED AND UNLABELED PCDDS AND PCDFS
Compound Solution No.
Concentrations (p» .1.)
1
2
,¦>
4
5
Unlabeled Analytes
2,3,7,8-TCDD
0.5
1
5
50
100
2,3,7,8- TCDF
0.5
1
5
50
100
1,2,3,7,8-PeCDD
2.5
5
25
250
500
1,2,3,7,8-PeCDF
2.5
5
25
250
500
2,3,4,7,8-PeCDF
2.5
5
25
250
500
1,2,3,4,7,8-HxCDD
2.5
5
25
250
500
1,2,3,6,7,8-HxCDD
2.5
5
25
250
500
1,2,3,7,8,9-HxCDD
2.5
5
25
250
500
1,2,3,4,7,8-HxCDF
2.5
5
25
250
500
1,2,3,6,7,8-HxCDF
2.5
5
25
250
500
1,2,3,7,8,9-HxCDF
2.5
5
25
250
500
2,3,4,6,7,8-HxCDD
2.5
5
25
250
500
1,2,3,4,6,7,8-HpCDD
2.5
5
25
250
500
1,2,3,4,6,7,8-HpCDF
2.5
5
25
250
500
1,2,3,4,7,8,9-HpCDF
2.5
5
25
250
500
OCDD
5.0
10
50
500
1000
OCDF
5.0
10
50
500
1000
Internal Standards
13C,,-2,3,7,8-TCDD
100
100
100
100
100
13C„-1,2,3,7,8-PeCDD
100
100
100
100
100
"C„- 1,2,3,6,7,8-HxCDD
100
100
100
100
100
13C„-1,2,3,4,6,7,8-HpCDD
100
100
100
100
100
13C„-OCDD
200
200
200
200
200
13C,,-2,3,7,8-TCDF
100
100
100
100
100
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-37

-------
Method TO-9A
Dioxins and Furans
TABLE 3. (continued)
Compound Solution No.
Concentrations (p» .1.)
1
2
,¦>
4
5
13C,1,2,3,7,8-PeCDF
100
100
100
100
100
13C„-l,2,3,4,7,8-HxCDF
100
100
100
100
100
13C„-l,2,3,4,6,7,8-HpCDF
100
100
100
100
100
Surrogate Standards
13C„-2,3,4,7,8-PeCDF
60
80
100
120
140
13C„-l,2,3,4,7,8-HxCD
60
80
100
120
140
13C,1,2,3,6,7,8-FtxCDF
60
80
100
120
140
13C„-l,2,3,6,7,8,9-HpCD
60
80
100
120
140
Field Standards
37Cl4-2,3,7,8-TCDD
100
100
100
100
100
13C„-1,2,3,7,8,9-HxCDD
100
100
100
100
100
Recovery Standard
13C12-1,2,3,4-TCDD
50
50
50
50
50
[Note: Standards specified in EPA Method 1613 can also be used in this method.]
Page 9A-38
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 4. COMPOSITION OF THE SAMPLE
FORTIFICATION SOLUTIONS
An;il\ le
( DiKcnlKiluin (|"iL- l.i
Chlorinated Internal Standards
13C12-2,3,7,8-TCDD
100
13C12-l,2,3,7,8-PeCDD
100
13C12-1,2,3,6,7,8-HxCDD
100
13C12-l,2,3,4,6,7,8-HpCDD
100
13c12-ocdd
100
13C12-2,3,7,8-TCDF
100
13C12-l,2,3,7,8-PeCDF
100
13C12-1,2,3,4,7,8-HxCDF
100
13C12-l,2,3,4,6,7,8-HpCDF
100
Brominated Internal Standards
13Cl12-2,3,7,8-TBDD
0.86
13C12-2,3,7,8-TBDF
0.86
13C12-l,2,3,7,8-PeBDF
0.86
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-39

-------
Method TO-9A
Dioxins and Furans
TABLE 5. COMPOSITION OF RECOVERY
STANDARD SOLUTION
AiniK le
( oiKvnli';ilion (py l.i
Recovery Standard
13C12-1,2,3,4-TCDD
10
TABLE 6. COMPOSITION OF AIR SAMPLER FIELD
FORTIFICATION STANDARD SOLUTION
AiniK it-
( oiKvnli';ilion (py l.i
Field Fortification Standard
37Cl4-2,3,7,8-TCDD
10
TABLE 7. COMPOSITION OF SURROGATE STANDARD SOLUTION
AiniK it-
( DiK\.-nli';iluin (|il- l.i
Surrogate Standards
13C12-1,2,3,4,7,8-HxCDD
100
13C12-2,3,4,7,8-PeCDF
100
13C12-1,2,3,6,7,8-HxCDF
100
13C12-l,2,3,4,7,8,9-HpCDF
100
Page 9A-40
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 8. COMPOSITION OF MATRIX AND METHOD SPIKE AND METHOD
SPIKE SOLUTIONS OF PCDDS/PCDFS AND PBDDS/PBDFS3
AnaK le
( oiKvnli'alion
( |1L' 1 . 1
AnaK It-
( oiKvnlialion
( |1L' 1 . 1
Native PCDDs and PCDFs
Native PBDDs and PBDFs
2,3,7,8-TCDD
1
2,3,7,8-TBDD
1
2,3,7,8-TCDF
1
2,3,7,8-TBDF
1
1,2,3,7,8-PeCDD
5
1,2,3,7,8-PeBDD
5
1,2,3,7,8-PeCDF
5
1,2,3,7,8-PeBDF
5
2,3,4,7,8-PeCDF
5
1,2,3,4,7,8-HxBDD
5
1,2,3,4,7,8-HxCDD
5
1,2,3,4,7,8-HxBDF
5
1,2,3,6,7,8-HxCDD
5


1,2,3,7,8,9-HxCDD
5


1,2,3,4,7,8-HxCDF
5


1,2,3,6,7,8-HxCDF
5


1,2,3,7,8,9-HxCDF
5


2,3,4,6,7,8-HxCDF
5


1,2,3,4,6,7,8-HpCDD
5


1,2,3,4,6,7,8-HpCDF
5


1,2,3,4,7,8,9-HpCDF
5


OCDD
10


OCDF
10


Solutions at different concentrations and those containing different congeners may also be used.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-41

-------
Method TO-9A
Dioxins and Furans
TABLE 9. HRGC-HRMS COLUMN PERFORMANCE EVALUATION SOLUTIONS
( oiiLvner
l iisl l!luk\l
l.;isl LIuled
SE-54 Column GC Retention Time Window Defining Standard3
TCDF
1,3,6,8-
1,2,8,9-
TCDD
1,3,6,8-
1,2,8,9-
PeCDF
1,3,4,6,8-
1,2,3,8,9-
PeCDD
1,2,4,7,9-
1,2,3,8,9-
HxCDF
1,2,3,4,6,8-
1,2,3,4,8,9-
HxCDD
1,2,4,6,7,9-
1,2,3,4,6,7-
HpCDF
1,2,3,4,6,7,8-
1,2,3,4,7,8,9-
HpCDD
1,2,3,4,6,7,9-
1,2,3,4,6,7,8-
OCDF
OCDF

OCDD
OCDD

SE-54 TCDD Isomer Specificity Test Standard13

1,2,3,4-TCDD


1,4,7,8-TCDD
2,3,7,8-TCDD
SP-2331 Column TCDF Isomer Specificity Test Standard0

2,3,4,7-TCDF


2,3,7,8-TCDF


1,2,3,9-TCDF

aA solution containing these congeners and the seventeen 2,3,7,8-substituted congeners may also be used for these
purposes.
bA solution containing the 1,2,3,4,-TCDD and 2,3,7,8-TCDD may also be used for this purpose.
°Solution containing all tetra- through octa-congeners may also be used for these purposes.
Page 9A-42
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 10. DESCRIPTORS, MASSES, M/Z TYPES, AND ELEMENTAL COMPOSITIONS
OF THE PCDDS AND PCDFS
Descriptor
Number
Accurate
Mass
ill / Type
Elemental Composition
Compound2
Primary
111 /
1
292.9825
Lock
c7fu
PFK


303.9016
M
c12 h4 35ci4 o
TCDF
Yes

305.8987
M+2
c12 h4 35ci3 37ci o
TCDF


315.9419
M
13c12 h4 35ci4 o
TCDF3
Yes

317.9389
M+2
13c12 h4 35ci3 37ci o
TCDF3


319.8965
M
c12 h4 35ci4 o2
TCDD
Yes

321.8936
M+2
c12 h4 35ci3 37ci o2
TCDD


327.8847
M
c12 h4 37ci4 o2
TCDD4


330.9792
QC
C7F13
PFK


331.9368
M
13c12 h4 35ci4 o2
TCDD3
Yes

333.9339
M+2
13c12 h4 35ci3 37ci o2
TCDD3


375.8364
M+2
c12 h4 35ci5 37ci o
HxCDPE

2
339.8597
M+2
c12 h3 35ci4 37ci o
PeCDF
Yes

341.8567
M+4
c12h3 35ci3 37C12 o
PeCDF


351.9000
M+2
13c12 h3 35ci4 37ci o
PeCDF3
Yes

353.8970
M+4
13c12 h3 35C13 37C12 o
PeCDF3


354.9792
Lock
c9f13
PFK


355.8546
M+2
c12 h3 35ci4 37ci o2
PeCDD
Yes

357.8516
M+4
c12 h3 35ci3 37ci2o2
PeCDD


367.8949
M+2
13c12 h3 35ci4 37ci o2
PeCDD4
Yes

369.8919
M+4
13c12 h3 35ci3 37ci2o2
PeCDD4


409.7974
M+2
C12 H3 35C16 37ci o
HpCDPE

January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-43

-------
Method TO-9A
Dioxins and Furans
TABLE 10. (continued)
Descriptor
Number
Accurate
Mass
in / Type
Elemental Composition
Compound2
Primary
111 /
3
373.8208
M+2
c12 h2 35ci5 37C1 o
HxCDF
Yes

375.8178
M+4
c12 h2 35ci4 37ci2 o
HxCDF


383.8639
M
13c12 h2 35ci6 o
HxCDF3
Yes

385.8610
M+2
13c12 h2 35ci5 37C1 o
HxCDF3


389.8157
M+2
c12 h2 35ci5 37ci o2
HxCDD
Yes

391.8127
M+4
c12 h2 35ci4 37ci2 o2
HxCDD


392.9760
Lock
c9f15
PFK


401.8559
M+2
13c12 h2 35ci5 37ci o2
HxCDD3
Yes

403.8529
M+4
13c12 h2 35ci4 37ci2 o2
HxCDD3


430.9729
QC
c9f13
PFK


445.7555
M+4
c12 h2 35ci6 37ci2 o
OCDPE

4
407.7818
M+2
c12h35ci6 37ci o
HpCDF
Yes

409.7789
M+4
C12 H 35C15 37C12 O
HpCDF


417.8253
M
13c12 h 35ci7 o
HpCDF3
Yes

419.8220
M+2
13c12 h 35ci6 37ci o
HpCDF3


423.7766
M+2
C12 H 35C16 37C1 02
HpCDD
Yes

425.7737
M+4
C12 H 35C15 37C12 02
HpCDD


430.9729
Lock
c9f17
PFK


435.8169
M+2
13c12 h 35ci6 37ci o2
HpCDD3
Yes

437.8140
M+4
13c12 h 35ci5 37ci2 o2
HpCDD3


479.7165
M+4
C12 H 35C17 37C12 O
NCDPE

Page 9A-44
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 10. (continued)
Descriptor
Accurate



l'rimarv
Number
Mass
m / Type
Elemental Composition
Compound2
111 /
5
441.7428
M+2
C12 35C17 37C1 o
OCDF
Yes

442.9728
Lock
ClO Fl7
PFK


443.7399
M+4
c12 35ci6 37ci2 o
OCDF


457.7377
M+2
c12 35ci7 37ci o2
OCDD
Yes

459.7348
M+4
c12 35ci6 37ci2 o2
OCDD


469.7779
M+2
13c12 35ci7 37ci o2
OCDD3
Yes

471.7750
M+4
13c12 35ci6 37ci2 o2
OCDD3


513.6775
M+4
c12 35ci8 37ci2 o
DCDPE

'Nuclidic masses used:
H= 1.007825 C = 12.00000 13C = 13.003355 F = 18.9984
0= 15.994915 35C1 = 34.968853 37C1 = 36.965903
2Compound abbreviations:
Polvchlorinated dibenzo-p-dioxins
TCDD = Tetrachlorodibenzo-p-dioxin
PeCDD = Pentachlorodibenzo-p-dioxin
HxCDD = Hexachlorodibenzo-p-dioxin
HpCDD = Heptachlorodibenzo-p-dioxin
OCDD = Oetaehlorodibenzo-p-dioxin
Polvchlorinated dibenzofurans
TCDF = Tetraehlorodibenzofuran
PeCDF = Pentachlorodibenzofuran
HxCDF = Hexachlorodibenzofuran
HpCDF = Heptachlorodibenzofuran
Polvchlorinated diphenvl ethers
HxCDPE = Hexachlorodiphenyl ether
HpCDPE = Heptachlorodiphenyl ether
OCDPE = Octachlorodiphenyl ether
NCDPE = Nonachlorodiphenyl ether
DCDPE = Decachlorodiphenyl ether
Lock mass and OC compound
PFK = Perfluorokerosene
'Labeled compound
4There is only one m/z for 37Cl4-2,3,7,8-TCDD (recovery standard).
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-45

-------
Method TO-9A
Dioxins and Furans
TABLE 11. DESCRIPTORS, M/Z TYPES, EXACT MASSES AND ELEMENTAL

c
OMPOSITION
S OF THE PBDDS AND PBDFS

Descriptor
Number
Accurate
Mass1
Ion Type
1 Elemental
Composition
Compound2
1
327.8847
M
c12 h4 37ci4 o2
TCDD4
330.9792
QC
C7F13
PFK
331.9368
M
c12 h4 35ci4 o2
TCDD3
333.9339
M+2
c12 h4 35ci3 37ci o2
TCDD3
2
417.825
M
13c12 h 35ci7 o
HpCDF3
419.822
M+2
13c12 h 35ci6 37ci o
HpCDF3
466.973
QC
PFK
481.698
M+2
C12 H4 79Br3 81BrO
TBDF
483.696
M+4
C12 H4 79Br2 81Br2 O
TBDF
485.694
M+6
C12 H4 79Br 81Br3 O
TBDF
492.970
LOCK MASS
PFK
493.738
M+2
13C12 H4 79Br3 81Br O
TBDF3
495.736
M+4
13C12 H4 79Br2 81Br2 O
TBDD3
497.692
M+2
C12 H4 79Br3 81Br 02
TBDD
499.690
M+4
C12 H4 79Br2 81Br2 02
TBDD
501.689
M+6
C12 H4 79Br 81Br3 O
TBDD
509.733
M+2
13C12 H4 79Br3 81Br02
TBDD3
511.731
M+4
13C12 H4 79Br2 81Br2 02
TBDD3
565.620
M+6
C12H5 79Br281Br30
PeBDPO
643.530
M+6
C12 H4 79Br3 81Br3 O
HxBDPO
Page 9A-46
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 11. (continued)
Descriptor
Number
Accurate
Mass1
Ion Type
1 elemental
Composition
Compound2
3
469.778
M+2
13c12 35ci7 37ci o2
OCDD3

471.775
M+4
13c12 35ci6 37ci o2
OCDD3

559.608
M+2
C12 H3 79Br4 81Br O
PeBDF

561.606
M+4
C12H3 79Br381Br20
PeBDF

563.604
M+6
C12 H3 79Br2 81Br3 O
PeBDF

566.966
LOCK MASS
PFK

573.646
M+4
13C12 H3 79Br3 81Br2 O
PeBDF3

575.644
M+6
13C12H3 79Br281Br30
PeBDF3

575.603
M+2
C12 H3 79Br4 81Br 02
PeBDD

577.601
M+4
C12H3 79Br3 37Br202
PeBDD

579.599
M+6
C12H3 79Br281Br302
PeBDD

589.641
M+4
13C12H3 79Br3 37Br202
PeBDD3

591.639
M+6
13C12H3 79Br381Br202
PeBDD3

616.963
QC
PFK
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-47

-------
Method TO-9A
Dioxins and Furans
TABLE 11. (continued)
Descriptor
Number
Accurate
Mass1
Ion Type
1 elemental
Composition
Compound2
4
643.530
M+6
C12 H4 79Br3 81Br3 O
HxBDPO

721.441
M+6
C12 H3 79Br4 81Br3 O
HpBDPO

616.963
QC

PFK

639.517
M+4
C12 H2 79Br4 81Br2 O
HxBDF

641.514
M+6
C12H2 79Br381Br30
HxBDF

643.512
M+8
C12 H2 79Br2 81Br4 O
HxBDF

655.511
M+4
C12 H2 79Br„ 81Br2 02
HxBDD

657.509
M+6
C12H2 79Br381Br302
HxBDD

659.507
M+8
C12 H2 79Br2 81Br4 02
HxBDD

666.960
LOCK
MASS

PFK

721.441
M+6
C12 H3 79Br4 81Br3 O
HpBDPO

801.349
M+8
C12 H2 79Br4 81Br4 O
OBDPO
Page 9A-48
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 11. (continued)
Descriptor
Accurate

Elemental

Number
Mass1
Ion Type
Composition
Compound2
5
717.427
M+4
C12 H 79Br5 81Br2 O
FtpBDF

719.425
M+6
C12 H 79Br4 81Br3 O
FtpBDF

721.423
M+8
C12 H 79Br3 81Br4 O
FtpBDF

733.422
M+4
C12 H 79Br5 81Br2 02
HpBDD

735.420
M+6
C12 H 79Br4 81Br3 02
HpBDD

737.418
M+4
C12 H 79Br3 81Br4 02
HpBDD

754.954
QC
PFK

770.960
LOCK MASS ALTERNATE
HpTriazine

801.349
M+8
C12 H2 79Br4 81Br4 O
OBDPO

816.951
LOCK MASS
PFK

879.260
M+8
C12 H 79Br5 81Br4 O
NBDPO

865.958
QC ALTERNATE
HpTriazine
'Nuclidic masses used:
H = 1.007825
0= 15.994915
19F = 18.9984
C = 12.000000 13C = 13.003355
79Br = 78.91834 81Br = 80.91629
2Compound abbreviations:
Polvbromoinated dibenzo-p-dioxins
TBDD = Tetrabromodibenzo-p-dioxin
PeBDD = Pentabromodibenzo-p-dioxin
HxBDD = Hexabromodibenzo-p-dioxin
HpBDD = Heptabromodibenzo-p-dioxin
OBDD = Oetabromodibenzo-p-dioxin
Polvbromoinated dibenzofurans
TBDF = Tetrabromodibenzofuran
PeBDF = Pentabromodibenzofuran
HxBDF = Hexabromodibenzofuran
HpBDF = Heptabromodibenzofuran
OBDF = Oetabromodibenzofuran
'Labeled Compound
4There is only one m/z for 37Cl4-2378-TCDD (recovery standard).
Polvbromoinated diphenvl ethers
FtxBDPE = Hexabromodiphenyl ether
HpBDPE = Heptabromodiphenyl ether
OBDPE = Octabromodiphenyl ether
NBDPE = Nonabromodiphenyl ether
DBDPE = Decabromodiphenyl ether
PFK = Perfluorokerosene
HpTriazine = Tris-(perfluoroheptyl)-s-Triazine
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-49

-------
Method TO-9A
Dioxins and Furans
TABLE 12. DESCRIPTORS, MASSES, M/Z TYPES, AND ELEMENTAL COMPOSITIONS
OF THE BCDDS AND BCDFS
Descriptor
Accurate



Primary
Number
mass1
m / Type
Hlemenlal Composition
Compound2
m /
1
315.942
M
13c12 h4 35ci4 o
TCDF4


317.939
M+2
C12 h4 35ci3 37C1 o
TCDF4
Yes

327.885
M
c12 h4 35ci4 o2
TCDD3
Yes

330.979
Lock
C7F13
PFK


331.937
M
13c12 h4 35ci4 o2
TCDD4


333.934
M+2
13c12 h4 35ci3 37ci o2
TCDD4
Yes

347.851
M
C12 H4 35C13 79Br 0
Br Cl3 DF


349.849
M+2
C12 H4 35C12 37C179Br O
Br Cl3 DF
Yes

363.846
M
C12 H4 35C13 79Br 02
Br Cl3 DD


365.844
M+2
C12 H4 35C12 37C179Br 02
Br Cl3 DD
Yes
Page 9A-50
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 12. (continued)
Descriptor
Accurate



Primary
Number
mass1
m / Type
Hlemenlal Composition
Compound2
m /
2
351.900
M+2
13c12 h3 35C15 o
PeCDF4


353.897
M+4
13c12 h3 35ci4 37C1 0
PeCDF4


354.979
Lock
C9F3
PFK


367.895
M+2
13c12 h3 35ci5 o2
PeCDD4
Yes

369.892
M+4
13c12 h3 35ci4 37ci o2
PeCDD4


381.812
M
C12 H3 35C14 79Br O
Br Cl4 DF


383.809
M+2
C12 H3 35C13 37C179Br O
Br Cl4 DF
Yes

397.807
M
C12 H3 35C14 79Br 02
Br Cl4 DD


399.804
M+2
C12 H3 35C13 37C179Br 02
Br Cl4 DD
Yes
'Nuclidic masses used:
H= 1.007825	C= 12.00000
0= 15.994915	35C1 = 34.968853
F = 18.9984	79Br = 78.91834
2Compound abbreviations:
Polvchlorinated dibenzo-p-dioxins
TCDD = Tetrachlorodibenzo-p-dioxin
PeCDD = Pentachlorodibenzo-p-dioxin
HxCDD = Hexachlorodibenzo-p-dioxin
HpCDD = Heptachlorodibenzo-p-dioxin
OCDD = Oetaehlorodibenzo-p-dioxin
Polvchlorinated dibenzofurans		
TCDF = Tetrachlorodibenzofuran
PeCDF = Pentaehlorodibenzofuran
HxCDF = Hexachlorodibenzofuran
HpCDF = Heptachlorodibenzofuran
3There is only one m/z for 37Cl4-2,3,7,8-TCDD (recovery
4Labeled compound
13C = 13.003355
37C1 = 36.965903
81Br = 80.91629
Brominated/Chlorinated
dibenzo-p-dioxins and dibenzofurans
BrCl3DD = Bromotrichloro dibenzo-p-dioxin
BrCl4DD = Bromotetrachloro dibenzo-p-dioxin
BrCl3DF = Bromotrichloro dibenzofuran
BrCl4DF = Bromotetrachloro dibenzofuran
Lock mass and OC compound	
PFK = Perfluorokerosene
standard).
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-51

-------
Method TO-9A
Dioxins and Furans
TABLE 13. HRGC OPERATING CONDITIONS
( olumn T\ |v
DB-5
SE-54
Sl'-:33l
Length (m)
60
30
60
i.d. (mm)
0.25
0.25
0.25
Film Thickness Cum)
0.25
0.25
0.20
Carrier Gas
Helium
Helium
Helium
Carrier Gas Flow (mL/min)
1-2
1-2
1-2
Injector temperature (°C)
290
308
308
Injection Mode
Splitless
<— Moving needle —>
Initial Temperature (°C)
200
170.0
150.0
Initial Time (min)
2
7.0
7.0
Rate 1 (°C/min)
5
8.0
10.0
Temperature (°C)
220


Hold Time (min)
16


Rate 2 (deg. C/min)
5


Temperature (°C)
235


Hold Time (min)
7


Rate 2 (deg. C/min)
5


Final Temperature (°C)
330
300.0
250.0
Hold Time (min)
5


TABLE 14. HRMS OPERATING CONDITIONS
Electron impact ionization
25-70 eV
Mass resolution
>10,000 (10% Valley Definition)
Analysis
Selected ion monitoring (SIM)
Exact masses monitored
Masses shown in Tables 10, 11, 12
Page 9A-52
Compendium of Methods for Toxic Organic Air Pollutants
January 1999

-------
Dioxins and Furans
Method TO-9A
TABLE 15. UNLABELED AND LABELED
ANALYTE QUANTIFICATION RELATIONSHIPS
An
-------
Method TO-9A
Dioxins and Furans
TABLE 16. INTERNAL STANDARDS QUANTIFICATION
	RELATIONSHIPS	
Ink-null Slandaid
Standard I sod Duiiiil' IVkviH
Reon cry IX'leinnnalmn
13C12-2,3,7,8-TCDD
13C12-1,2,3,4-TCDD
13C12-l,2,3,7,8-PeCDD
13C12-1,2,3,4-TCDD
13C12-1,2,3,6,7,8-HxCDD
13C12-1,2,3,7,8,9-HxCDD
13C12-l,2,3,4,6,7,8-HpCDD
13C12-1,2,3,7,8,9-HxCDD
13c12-ocdd
13C12-1,2,3,7,8,9-HxCDD
13C12-2,3,7,8-TCDF
13C12-1,2,3,4-TCDD
13C12-l,2,3,7,8-PeCDF
13C12-1,2,3,4-TCDD
13C12-1,2,3,4,7,8-HxCDF
13C12-1,2,3,7,8,9-HxCDD
13C12-l,2,3,4,6,7,8-HpCDF
13C12-1,2,3,7,8,9-HxCDD
aSurrogate standards shown in Table 7 may also be used.
TABLE 17. SURROGATE/ALTERNATE STANDARDS
QUANTIFICATION RELATIONSHIPS
SuiTOL'jk' Slandaid
Siandard I sod Duiiiil' IVrcvnl
Reon cry Delermmalion
13C12-2,3,4,7,8-PeCDF
13C12-l,2,3,7,8-PeCDF
13C12-1,2,3,4,7,8-HxCDD
13C12-1,2,3,6,7,8-HxCDD
13C12-1,2,3,6,7,8-HxCDF
13C12-1,2,3,4,7,8-HxCDF
13C12-l,2,3,4,7,8,9-HpCDF
13C12-l,2,3,4,6,7,8-HpCDF
[Note: Other surrogate standards may be used instead]
Page 9A-54
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
TABLE 18. QUANTIFICATION RELATIONSHIPS OF THE
CARBON-LABELED STANDARDS AND THE ANALYTES
Analyles
Quantification Standard
2,3,7,8-TBDD
13C12-2,3,7,8-TBDD
2,3,7,8-TBDF
13C12-2,3,7,8-TBDF
1,2,3,7,8-PeBDD
13C12-1,2,3,7,8-PeBDD
1,2,3,7,8-PeBDF
13C12-1,2,3,7,8-PeBDF
2,3,4,7,8-PeBDF
13C12-1,2,3,7,8-PeBDF
1,2,3,4,7,8-HxBDD
13C12-1,2,3,7,8-PeBDD
0.5 ng 37Cl4-2,3,7,8-TCDD spiked to the extract prior to final concentration
to 60 /J.L was used to determine the method efficiency (% recovery of the
nCI2-labeled PBDDs/PBDFs).
•	Additional 2,3,7,8-substitutedPBDDs/PBDFs are now commercially
available.
•	Retention Index for the PBDDs/PBDFs were published by Sovocool,
etal., Chemosvhere 16. 221-114, 1987; and Donnelly, etal.,
Biomedical Environmental Mass Spectrometry. 14, pp. 465-472,
1987. J
THEORETICAL ION ABUNDANCE RATIOS AND CONTROL

LIMIT!:
5 FOR PCDDSAND
PCDFS
No. of Chlorine
Atoms
m /.'s Forming
Ratio
Theoretical
Ratio
Control
l.ower
Limits'
I Jpper
42
M/M+2
0.77
0.65
0.89
5
M+2/M+4
1.55
1.32
1.78
6
M+2/M+4
1.24
1.05
1.43
63
M/M+2
0.51
0.43
0.59
7
M+2/M+4
1.04
0.88
1.20
74
M/M+2
0.44
0.37
0.51
8
M+2/M+4
0.89
0.76
1.02
[Note:
TABLE 19.
'Represent ± 15% windows around the theoretical ion abundance ratios.
2Does not apply to 37Cl4-2,3,7,8-TCDD (cleanup standard).
3Used for 13C12-HxCDF only.
4Used for 13C12-HpCDF only.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-55
-------
Method TO-9A
Dioxins and Furans
TABLE 20. THEORETICAL ION ABUNDANCE RATIOS AND CONTROL
LIMITS FO
R PBDDS AND PBDFS
\umlvr nl"
Bromine Alums
Inn T\ |v
1 heoivlical
Ratio
( oilll'ol 1.Minis
Lower
I |l|Vr
4
M+2/M+4
0.68
0.54
0.82
4
M+4/M+6
1.52
1.22
1.82
5
M+2/M+4
0.51
0.41
0.61
5
M+4/M+6
1.02
0.82
1.22
6
M+4/M+6
0.77
0.62
0.92
6
M+6/M+8
1.36
1.09
1.63
7
M+4/M+6
0.61
0.49
0.73
7
M+6/M+8
1.02
0.82
1.22
Page 9A-56
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
TABLE 21. MINIMUM REQUIREMENTS FOR INITIAL AND DAILY CALIBRATION
RESPONSE FACTORS
Compound
Relative Response laetors
Initial Calibration RSI)
Daily Calibration "o Dillerenee
Unlabeled Analytes
2,3,7,8-TCDD
25
25
2,3,7,8- TCDF
25
25
1,2,3,7,8-PeCDD
25
25
1,2,3,7,8-PeCDF
25
25
2,3,4,7,8-PeCDF
25
25
1,2,4,5,7,8-HxCDD
25
25
1,2,3,6,7,8-HxCDD
25
25
1,2,3,7,8,9-HxCDD
25
25
1,2,3,4,7,8-HxCDF
25
25
1,2,3,6,7,8-HxCDF
25
25
1,2,3,7,8,9-HxCDF
25
25
2,3,4,6,7,8-HxCDF
25
25
1,2,3,4,6,7,8-HpCDD
25
25
1,2,3,4,6,7,8-HpCDF
25
25
OCDD
25
25
OCDF
30
30
Internal Standards
13C12-2,3,7,8-TCDD
25
25
13C12-1,2,3,7,8-PeCDD
30
30
13C12-1,2,3,6,7,8-HxCDD
25
25
13C12-1,2,3,4,6,7,8-HpCDD
30
30
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-57
-------
Method TO-9A
Dioxins and Furans
TABLE 21. (continued)
Compound
Relative Response l aelors
Initial Calibration RSI)
Daily Calibration % Dillerenee
13c12-ocdd
30
30
13C12-2,3,7,8-TCDF
30
30
13C12-1,2,3,7,8-PeCDF
30
30
13C12-1,2,3,4,7,8-HxCDF
30
30
13C12-1,2,3,4,6,7,8-HpCDF
30
30
Surrogate Standards
37Cl4-2,3,7,8-TCDD
25
25
13C12-2,3,4,7,8-PeCDF
25
25
13C12-1,2,3,4,7,8-HxCDD
25
25
13C12-1,2,3,4,7,8-HxCDF
25
25
13C12-1,2,3,4,7,8,9-FtpCDF
25
25
Page 9A-58
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
TABLE 22. 2,3,7,8-TCDD EQUIVALENT FACTORS (TEFS)1
FOR THE POLY CHLORINATED DIBENZODIOXINS
AND POLY CHLORINATED DIBENZOFURANS
\unilvr
( oni|"KHIIkl
11 :i
1
2,3,7,8-TCDD
1.00
2
1,2,3,7,8-PeCDD
0.50
3
1,2,3,4,7,8-HxCDD
0.1
4
1,2,3,6,7,8-HxCDD
0.1
5
1,2,3,7,8,9-HxCDD
0.1
6
1,2,3,4,6,7,8-HpCDD
0.01
7
OCDD
0.001
8
2,3,4,7,8-TCDF
0.10
9
1,2,3,7,8-PeCDF
0.05
10
2,3,4,7,8-PeCDF
0.5
11
1,2,3,4,7,8-HxCDF
0.1
12
1,2,3,6,7,8-HxCDF
0.1
13
1,2,3,7,8,9-HxCDF
0.1
14
2,3,4,6,7,8-HxCDF
0.1
15
1,2,3,4,6,7,8-HpCDF
0.01
16
1,2,3,4,7,8,9-HpCDF
0.01
17
OCDF
0.001
interim procedures for Estimating Risks associated with Exposures
to mixtures of Chlorinated Dibenzo-p-Dioxins and Dibenzofurans
(CDDs/CDFs), WPA-625/3-89-016, March 1989.
[Note: The same TEFs are assigned to the PBDDs/PBDFs and
BCDDs/BCDFs.J
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-59
-------
Method TO-9A
Dioxins and Furans
TABLE 23. MINIMUM SAMPLING EQUIPMENT CALIBRATION AND
	ACCURACY REQUIREMENTS	
L(.|ui|inicnl
Acceptance linnls
liei.|uenc\ and method of
measurement
Action if i'ei|uii'e-
ments are not met
Sampler
Indicated flow rate = true
flow rate ±10%.
Calibrate with certified
transfer standard on
receipt, after maintenance
on sampler, and any time
audits or flow checks
deviate more than ±10%
from the indicated flow
rate or +10% from the
design flow rate.
Recalibrate
Associated eauinment
Sampler on/off timer
±30 min/24 hour
Check at purchase and
routinely on sample-
recovery days
Adjust or replace
Elapsed-time meter
±30 min/24 hour
Compare with a standard
time-piece of known
accuracy at receipt and at
6-month intervals
Adjust or replace
Flowrate transfer
standard (orifice device)
Check at receipt for
visual damage
Recalibrate annually
against positive
displacement standard
volume meter
Adopt new calibration
curve
Page 9A-60
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
TABLE 24. FORMAT FOR TAB]
OF ANALYTICAL RESULTS
IDENTIFICATION





AIR SAMPLER EFFICIENCY (% RECOVERY)
13C12-1,2,3,4,-TCDD





METHOD EFFICIENCY (% RECOVERY)
13C12-2,3,7,8-TCDF





13C12-2,3,7,8-TCDD





13C12-1,2,3,7,8-PeCDF





13C12-l,2,3/7,8-PeCDD





13C12-1,2,3,4,7,8-HxCDF





13C12-1,2,3,6,7,8-HxCDD





13C12-l,2,3,4,6,7,8-HpCDD





13C12-OCDD





CONCENTRATIONS DETECTED or MDL (pg/m3)
TCDDs (TOTAL)1





2,3,7,8-TCDD





PeCDDs (TOTAL)





1,2,3,7,8-PeCDD





HxCDDs (TOTAL)





1,2,3,4,7,8-HxCDD





1,2,3,6,7,8-HxCDD





1,2,3,7,8,9-HxCDD





HpCDDs (TOTAL)





1,2,3,4,6,7,8-HpCDD





January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-61
-------
Method TO-9A
Dioxins and Furans
TABLE 24. (continued)
IDENTIFICATION





OCDD





TCDFs (TOTAL)





2,3,7,8- TCDF





PeCDFs (TOTAL)





1,2,3,7,8-PeCDF





2,3,4,7,8-PeCDF





HxCDFs (TOTAL)





1,2,3,4,7,8-HxCDF





1,2,3,6,7,8-HxCDF





1,2,3,7,8,9-HxCDF





2,3,4,6,7,8-HxCDF





HpCDFs (TOTAL)





1,2,3,4,6,7,8-HpCDF





1,2,3,4,7,8,9-HpCDF





OCDF





'(TOTAL) = All congeners, including the 2,3,7,8-substituted congeners.
ND = Not detected at specified minimum detection limit (MDL).
[Note: Please refer to text for discussion and qualification that must accompany the results.]
Page 9A-62
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
Dibenzo-p-Dioxin
Dibenzofuran
January 1999
Figure 1. Dibenzo-p-dioxin and dibenzofuran structures.
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-63
-------
Method TO-9A
Dioxins and Furans
Sampling Head
(see Figure 3)
Pipe Fitting (1/2 in.;
Magnehlic Gauge
Venturi
Flow Control
Valve
Voltage Variator
Elapsed Time
Meter
Blower
Motor
Motor
Support
7-Day Timer
Exhaust Duct
(6 in. x 10 ft)
Base Plate
Figure 2. Typical dioxins/foran high volume air sampler.
Page 9A-64
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
Air Flow
Particle Fitter
Particle Filter
Support
Assembled
Sampling
Module
w

I -•I'VV-:'
, / / y
; i m v 4
/ / /

Air Flow
Exhaust
Filter Retaining Ring
Silicone Gasket
102-mm
Quartz-fiber
Filter
Filter Support Screen
Filter Holder (Part 2)
Silicone Gasket
Glass Cartridge
Retalnlna Screen
Sorbent
Retaining Screen
Silicone Gasket
Cartridge
Holder
(Part 1)
Figure 3a. Typical absorbent cartridge assembly for sampling dioxin/furans.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-65
-------
Method TO-9A
Dioxins and Furans
Glass PUF Sampler with
Stainless Steel Screens
,64mm O.D..


CM

O)

"51-

<3

LO

O)

•*-

.Glass
Cartridge
— End Cap
PUF Plug
"*H— End Cap
(1) Glass PUF cartridge, plug, and end caps.
Accessories
Teflon Sealing Caps
with O-rings for
capping PUF Sampler
PUF Insert
(2) PUF shipping container.
Aluminum Canister for Shipping
and Storage of the PUF Sampler
Figure 3b. Typical glass PUF cartridge (1) and shipping container
(2) for use with hi-vol sampling systems.
Page 9A-66
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
Venturi
Exhaust Hose
\
4" Diameter Pullflex
Filter and Support
PUF Adsorbent
Cartridge and Support
Quick Release Connections
for Module
Quick Release Connections
forMagnahelic Gage
Flow Control Valve
Elapsed Time Indicator
Figure 4. Portable high volume air sampler developed by EPA.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-67
-------
Method TO-9A
Dioxins and Furans
_ Woter
Manometer
Barometer
Mercury
Manometer
Air Flow
Thermometer
Orifice
Filter Adapter
y
Rootsmeter
High Volume Motor
OOff
PqO.
Resistance Plates
Figure 5. Positive displacement rootsmeter used to calibrate orifice transfer standard.
Page 9A-68
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
u
CO
§
P
§
o
H
p
o
w
P	PQ
p	a
z	<
m	o
&	w
53	u
9	E
o
I
32
03
P
O
!z
o S
Z 13
u3
•a
H PL, O
o
o
/—s
S"
r. as
1 % g
1 e? 1
>* eT
EC
<





x-Axis
Standard
Howrate.
Qsld ::
5.66
5.66
o
\Ti
00
8.50
o
00
VTN"
Iflllll
200
200
300
300
300
Resistance
Plants
(No. of
holes)

r-
o
t-H
cn
00
t-H
a3
a?
tc
.a
Tt;
•O



O
*C
o
.§>
E
I
Ph
CM
§
£
I
1
o
^	9
\o	o
ON	\o
ch	r-
CD
ll

II II
ii
"S
>
8
T3 Td
„ W «3
h eu
a

1

cs
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-69
-------
Method TO-9A
Dioxins and Furans
Stiutoff valves
Calibrated
orifice
Manometer
0- 18 in.
Sampling head
Pipe fitting (1/2 in.)
Magnehelic gauge
0-100 in.
Orifice
Row control
vaVe
EJapsed time
meter
Exhaust duct
7-day
timer
Motor
support
Figure 7. Field calibration configuration of the dioxin/furan sampler.
Page 9A-70
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
COMPENDIUM METHOD TO-9A
FIELD CALIBRATION DATA SHEET DIOXIN/FURAN SAMPLER CALIBRATION
Sampler ID:	Calibration Orifice ID:
Sampler Location:	Job No.:
High Volume Transfer Orifice Data:
Correlation Coefficient (CC1):	Slope (Ml):
(CC2):	(M2):
Intercept (B1):
(B2):
Time:
Calibration Date:	
Calibration Ambient Temperature: 	°F
Calibration Ambient Barometric Pressure:.
Calibration set point (SP): 	
C
CALIBRATOR'S SIGNATURE
."Hg	mm Hg
SA1
VIPLER CALIBRATION
Actual \ allies iVom calibration
( alibrateJ \ allies
On lice
manometer,
inches
iVI i
\lomlor
niagnehelic.
inches
(Y2)
On lice
manomeler
(Y.m
Monitor
nia-jnehehc
(Y4)
( alculaled \ aluc
orilice Mow. scm
(XI)

70




60




50




40




30




20




10



Y1 =	Calibration orifice reading, in. H20
Y2 =	Monitor magnehelic reading, in. H20
Pa =	Barometric pressure actual, mm Hg
B1 =	Manfacturer's Calibration orifice Intercept
Ml =	Manufacturer's Calibration orifice manometer
slope
Y3 =	Calculated value for orifice manometer
=	[Yl(Pa/760)(298/{Ta + 273})]1-4
Definitions
Y4
XI
Ta
T.t
= Calculated value for magnehelic
= [Y2(Pa/760)(298/{Ta + 273})]'/2
= Calculated value orifice flow, scm
Y3-B1
Ml
= Barometric pressure standard, 760 mm Hg
= Temperature actual, °C
= T emperature standard, 2 5 ° C
Figure 8. Orifice transfer field calibration data sheet.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-71
-------
Method TO-9A
Dioxins and Furans
stiuionusiVM
Vi
("H,Oid|.JJ
Y2

Sintplnj hood
Pipetting itrarnj

MagnfthnlG >gpu\fc
O-1 Win.
On 3g»
ROvri MrtCrd
va.Y»
SbWi1
rciDtar
i
Mafcir
StUMFl
VI
(¦K,OJ
MwiWMto1
0 - lanrt.
Bafi«iJ Whu
jnctef
eiihauM *;t
¦+ Linear regression of X1 (scmm) vs. Y4
i
VJ
' f HpO) adj.
Y.\
(Sanfflfl
Calculate B? and MS
I	YS - [avgF mag. i h (P^/T^J (298 / 760}]^
VS-02
X2 = 	-	
(scnirn)	ME
Figure 9. Relationship between orifice transfer standard and flow rate through sampler.
Page 9A-72
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
COMPENDIUM METHOD TO-9A
FIELD TEST DATA SHEET
GENERAL INFORMATION
Sampler I.D. No.:
Lab PUF Sample No.:
Sample location:
Operator:
Other:
PUF Cartridge Certification Date: 		Start Stop
Date/Time PUF Cartridge Installed: 		Barometric pressure ("Hg) 	 	
Elapsed Timer:			Ambient Temperature (°F) 	 	
Start		Rain	Yes	Yes	
Stop 		No	 No	
Diff.		Sampling time
Sampling	Start 	
Stop 	
Ml 	 B1 		Diff.	
M2 	 B2 	
Audit flow check within ±10 of set point
	Yes
No
II Ml.
1 IMP
ISAKOMI I KIC
I'KI.SSl Kl.
M \(.M.III I.IC
Kl A DIM.
CM.CI I.ATI.I)
1 l.(m KM 1.
(M'llllll)
KIM) l£^
























Avg.





Comments
Figure 10. Field test data sheet.
January 1999	Compendium of Methods for Toxic Organic Air Pollutants	Page 9A-73
-------
Method TO-9A
Dioxins and Furans
C->	r-i	r-	t-	">0 -rt
Ca]	ra	W	W	M M
n	¦qt	Hi>	r-
ct	«	t-I	I"
ar»	n-. n%	a-	O -
U	W H	P	W •
r-	o <1,"i	r-<	o
W M CI rl	^	4
Q
S
w
r-n 
-------
Dioxins and Furans
Method TO-9A
E S E E	E S S
¦—I	(-¦ ITi	MO
O ¦d	ft	pi 5
1 ¦ ¦ ¦ 1 ¦ ¦ ¦1 ¦ ¦ ¦ ^ ¦ I ¦ ¦ ¦
l£	!.£>	¦up	Li3	IB Ci -H
M	pq	pq	fi]	H H Eh
f%!	ih	1-	uT	fq a
lO	A>	p	*1 ~
&
~?
§'
£
dc"
00
«[
¦S' ' i! -i'
C QJ u fl
¦ o .	 —-
8
3
Sr-- r-- r--	r-- ®
p] cq u	hi ra h
D D O <3
ifl ^ n	H 9
!•¦¦¦!¦ ¦ ¦! ¦! i i ¦ l I ii i
¦O
9
C-
t-Tf
,M"L	* rirrfrFV
o o a- o -d —
O « ts- VP -Tfl
Iff
Q
O
C*
D_
d>
i-r
*
to
X
»
8
^ i.i ii ii i ii i, ¦
O C- & i -ii
O » "d? ^ f-J
u"j i.p Iaj 'u	Lri	a -h :
H pq rf W	W	Hj
H rV; irt Ifl	^	~
f*i -n r-l	W	Q
I ¦¦¦ I- ¦ ¦ '¦• ¦ ¦	¦ ¦'
in
¦ t
O
Ck
-------
Method TO-9A
Dioxins and Furans
f-L r-_ r-L c-_ r-_ o ,|q
a tt] p LJ [il w fn
¦CT r-l i"-"- LJ"i TO O
yj ii> "ia k0 Id
rsi PI H H W
<¦0 l/> "
IT" CO
—I...I
rl O
_llL
Q •
x
«6
	^ N
S3 S S £ S 3 e.
Tf	~ if f-. O
CO \D 1/1
hi
£
II
O
D
r^L
rii
¦rr
CO
«"
o' 0 a
¦£• -# w
Cl
D
S3
d?
h-'
<£¦'
oi
<3>
(D
II
y
?T3Td _
« ^ ^ ^ «
&
•"£¦ "¦£¦ «? "d? Ttf- O .^!
p] oq 00 Da ta pq (h
o iti ti- "=h rj o
i£y ^ rr> H O S
I ¦ ¦ -I ¦ ¦¦ I ¦ ¦ -I ¦ ¦!
dfl"l["T"l',,|-"l
000000
o «a « m
Page 9A-76
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
^ ^ -a •"
pq pq [A pel	ft H E*
(ft H ^ iTi	00 Q
|-- ITi -Pi	-*4 D 0
			
3
_ '-D TD "£l L/i O -H
p y W pa cu pa ^
—	k? a1! o
Ol «H
K
-pi-
r--,
S
y
..eS
o o o o
11 ¦ | ¦ I I £
o ft
e
_ C
r-- n r-- c-> r- O- -i€
na a ra ra m m (-
ft r- u"i n M O
-j
u
«j? «£¦ \0	"i? o
pq PQ pq H M W R
rl ft	l/> N C
y"i rt i-1"! N
I	I ¦ ¦ ¦ I
\£i
Q
O
£
hJ
*+
eJ

0
a
£
l-T
1
CJ
^ ^ a
L-Jd.Li.i.1' '.'J I i.iJ i 11
; c-
: C-
T3

=3
.g
"3
o
o
• c-
ft
tfl
in
M I 11 I ¦ I p I 11 11 I ] 1 11
Q ~ O O -to- ft
5 O [i- '¦!? "=H CN
rt
2

I ' I I 'I I
ft ft ft ft ft
W >sij t* ri
ft ft ft ft ft ft
fi -ii W ^ ri
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-77
-------
Method TO-9A
Dioxins and Furans
I I Id j L h —i¦I ¦ ¦ ¦ ¦ I¦¦ il

Page 9A-78	Compendium of Methods for Toxic Organic Air Pollutants	January 1999
-------
Dioxins and Furans
Method TO-9A
in
IXl
LA


¦ii
tl
U
CD
li]
¦u
M
M
ro
li1--
r--

hS
U
iT""i

iH
co
o
SP E G Q £ £

0-5
r--
r->
r--
r->
'J?
e> %-i
&
W E-:
oq
Q]
CU
EC
rci
¦n H
TO
O
r--
Cn,
-------
Method TO-9A
Dioxins and Furans





r-l
kTi

M1!
W
Ul
nk
in
111
nn e-i
W
W
W
MP
o
r-"i
u-;-
¦Si
on
u".

ri
¦Tfl
(-4
H

<5



S £
S G G
•¦£/ \C
. w w
CO f"1 H
O
G

!-¦¦ I - -l.-.l ¦¦ ¦!¦






'-£¦
W

£
[[]
O
Ph
rm
r->
n
W
M
H-
M
Q




1—1
.-I
IXl
a

Cp "¦£! -4J
£ t> -W	^ «
r> !
¦5 OT
Page 9A-80
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
If*
\0
LD
'¦jD
LTl
a-
W
W
w
H
y
CD
¦H


ij3
cri
o
U
nil
i i 1
i—1
1 • 1
ci
• .1
£
Itffr	H«>	u"l
dq nn pi k m
4J
s"
p3
£ G S £
r--
r^-
o -H
r->
r--
r--
r--
ifr
4
P
cu
m £h
Dj
m
linl
M
W
W
ri
c-l


r->
O

«•
<5
CM
rH
li


M
¦H
Ij2>
a
i i l-1-...i.Li ill ¦ 11
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-81
-------
Method TO-9A
Dioxins and Furans

¦J?


m
¦a
£
¦ rl
\0
"Xi
M3
in
Lt"?
o
DC
nn
W
W
M
F=l

w
cq
H
W
ill
[t]
tk
r-q
r-
¦H
"-?¦
¦a

oa

M
i—i
O
¦£j
t4
<¦¦¦1
¦H
T—1
in
~

rt
ri
l—1
r->
fj
d
w I
r-» \o "w- so
cq pfl Cfl pq
Q
~
<3
w
0_
CO
s
n
3
r- ^
fc
<*>
II
A
Ci
(J
—-
r- S
"I
ii
y L
^ o

"'I
o c
Page 9A-82
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
•|	i I | I ¦ I
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Method TO-9A
Dioxins and Furans
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------
Dioxins and Furans
Method TO-9A
January 1999	Compendium of Methods for Toxic Organic Air Pollutants	Page 9A-85
-------
Method TO-9A
Dioxins and Furans
¦U	-y	qi	ft
E	1	Is	e
U? i£- 'dj iri qTi o -h o vd u> in in a- -h r-> r-- r-> M? O t1- r-> f- "j?	'ri
Page 9A-86	Compendium of Methods for Toxic Organic Air Pollutants	January 1999
-------
Dioxins and Furans
Method TO-9A
January 1999	Compendium of Methods for Toxic Organic Air Pollutants	Page 9A-87
-------
Method TO-9A
Dioxins and Furans




ul
Q

¦lD
IQ
•ri

l;l
IM
W
w
W
W

W

W
w
•a
¦H

C?
«
o

ca
r-i.
r-
1—1
1
1111
1 1 l.>
1—1
LTV
o
o
o
Li
ro
. r 1 .
¦H
..I-
H
5 Q B S
Page 9A-88	Compendium of Methods for Toxic Organic Air Pollutants	January 1999
-------
Dioxins and Furans
Method TO-9A
fcVZ = 303,9010
JGflj
^,7^-TC[>F
j^mt JiJ/iW 3IJ00 iSfflfl 337 W	3ff--M JJfM
' Mfif=3 JJj-01? 33:QQ SiritO JSrlJC JffjOfl
'fj|tfFSi7Si^S64"
ra
CL



*iL„i .
in Iwu ii'
'J J I |jiI,\ L
- 1
liujl h j
Tflz^sfiaysr
I4G*

J7rtf0	M;BO	JiiHf M/fflt JJKTO J3J.-JN Jf;OS J3ijJ4
, ftEti
Figure 23. Extracted ion current profiles (EICP) for 2,3,7,8-TCDF and labeled standard in a
complex environmental sample showing presence of other TCDF isomers.
January 1999
Compendium of Methods for Toxic Organic Air Pollutants
Page 9A-89
-------
Method TO-9A	Dioxins and Furans
This Page Intentionally Left Blank
Page 9A-90
Compendium of Methods for Toxic Organic Air Pollutants
January 1999
-------