ASTM D7339-18

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D7339 − 12 D7339 − 18
Standard Test Method for
Determination of Volatile Organic Compounds Emitted from
Carpet using a Specific Sorbent Tube and Thermal
Desorption / Gas Chromatography
This standard is issued under the fixed designation D7339; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This test method describes an analytical procedure for identifying and quantifying the masses of individual volatile organic
compounds (individual VOCs or IVOCs) that are emitted into a flow of air from carpet specimens and collected on sorbent
sampling tubes during emissions testing.
1.2 This test method will be used in conjunction with a standard practice for sampling and preparing carpet specimens for
emissions testing. If a specific chamber practice is not available for the carpet specimens, this standard test method should be used
in conjunction with approved standard practices for emissions testing and sample preparation.
1.3 When used in conjunction with standard practices for carpet specimen preparation and collection of vapor-phase emissions
, this test method will provide a standardized means of determining the levels of IVOC in the exhaust stream of the emissions test
chamber/cell. If this test method is used with a reliable practice for emissions testing, these IVOC levels can be used to determine
the emission rate from a unit quantity (usually surface area) of the sample material under test.
1.4 VOCs in the exhaust stream of an emissions test device are collected on thermal desorption tubes packed with a specific
combination of sorbents using active (pumped) sampling. (See Practice D6196 for a more general description of vapor collection
using pumped sampling onto sorbent tubes).tubes.) The samples are analyzed by thermal desorption (TD) with gas chromatography
and mass spectrometry detection (GC/MS) and/or flame ionization detection (FID) depending upon the requirements of the specific
materials emissions testing/certification protocol.
1.5 This test method can be used for the measurement of most GC-compatible organic vapors ranging from the approximate
-4
volatility from n-hexane to n-hexadecane (that is, compounds with vapor pressures ranging from 16 kPa to 4 × 10 kPa at 25°C).
Properties other than a compound’s vapor pressure such as affinity for the sorbent may need to be taken into account. Compounds
with vapor pressures outside this range may or may not be quantifiable by this test method. However, qualitative data concerning
the identity of a compound(s), outside the stated volatility range for quantitation, may still be useful to the user. The This test
3 3
method can be applied to analytes over a wide concentration range—typically 1 μg/m to 1 mg/m concentration of vapor in the
exhaust air from the emission cell or chamber.
1.6 This test method is not capable of quantifying all compounds which are emitted from carpets. See the appropriate test
practices/methods for determining other compounds that are not amenable to analysis by gas chromatography (that is, Test Method
D5197 for the determination of aldehydes).
1.7 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
standard.
1.8 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use.
1.9 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
This test method is under the jurisdiction of ASTM Committee D22 on Air Quality and is the direct responsibility of Subcommittee D22.05 on Indoor Air.
Current edition approved Oct. 15, 2012March 1, 2018. Published November 2012March 2018. Originally approved in 2007. Last previous edition approved in 20072012
as D7339 – 07. DOI:10.1520/D7339-12.12. DOI:10.1520/D7339-18.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7339 − 18
2. Referenced Documents
2.1 ASTM Standards:
D1356 Terminology Relating to Sampling and Analysis of Atmospheres
D3686 Practice for Sampling Atmospheres to Collect Organic Compound Vapors (Activated Charcoal Tube Adsorption Method)
D5116 Guide for Small-Scale Environmental Chamber Determinations of Organic Emissions from Indoor Materials/Products
D5197 Test Method for Determination of Formaldehyde and Other Carbonyl Compounds in Air (Active Sampler Methodology)
D5337 Practice for Flow Rate Adjustment of Personal Sampling Pumps
D6196 Practice for Choosing Sorbents, Sampling Parameters and Thermal Desorption Analytical Conditions for Monitoring
Volatile Organic Chemicals in Air
D6670 Practice for Full-Scale Chamber Determination of Volatile Organic Emissions from Indoor Materials/Products
D7143 Practice for Emission Cells for the Determination of Volatile Organic Emissions from Indoor Materials/Products
D7706 Practice for Rapid Screening of VOC Emissions from Products Using Micro-Scale Chambers
E355 Practice for Gas Chromatography Terms and Relationships
2.2 ISO Standards:
ISO 10580 Resilient, textile and laminate floor coverings—Test method for volatile organic compound (VOC) emissions
ISO 16000-6 Determination of volatile organic compounds in indoor and test chamber air by active sampling on Tenax TA
sorbent, thermal desorption and gas chromatography using MS/FID
ISO 16000-9 Indoor Air—Part 9: Determination of the emission of volatile organic compounds from building products and
furnishings—Emission test chamber method
ISO 16000-10 Indoor Air—Part 10: Determination of the emission of volatile organic compounds from building products and
furnishings—Emission test cell method
ISO 16000-11 Indoor Air—Part 11: Determination of the emission of volatile organic compounds from building products and
furnishings—Sampling, storage of samples and preparation of test specimens
2.3 US EPA Methods:
TO-15 Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specially-Prepared Canisters and Analyzed
by Gas Chromatography/Mass Spectrometry (GC/MS)
TO-17 —Determination of Volatile Organic Compounds in Ambient Air Using Active Sampling onto Sorbent Tubes
3. Terminology
3.1 Definitions—Refer to Terminology D1356 and Practice E355 for definitions of terms used in this test method.
4. Summary of Test Method
4.1 A sample of the VOCs emitted from a carpet specimen is collected following the preparation and collection guidelines
provided in ISO 10580 or the appropriate chamber/emission cell practices/guides. See, for example, Guide D5116 (small chamber),
Practice D6670 (full-scale chamber), Practice D7706 (micro-scale chamber), Practice D7143 (emission cells), ISO 16000-9 (small
chambers), ISO 16000-10 (emission cells), and ISO 16000-11 (sample preparation).
4.2 Organic vapors in the exhaust stream of an emission test chamber or cell are pumped onto standard thermal desorption tubes
(see Practice D6196) containing ~200 mg of a polyphenylene oxide resin-based (PPOR-B) sorbent W-PP (weak porous polymer
sorbent) with a short bed (1-2(1–2 mm) of quartz wool, a glass frit, or stainless steel screen (singly or combined) at each end of
the ~200 mg of PPOR-BW-PP sorbent. The pump flow rate and sampling time must be controlled (see Practice D6196). The
sorbent tubes are then thermally desorbed, in a reverse flow of carrier gas, using an appropriate two-stage desorption apparatus,
(Seeapparatus (see Practice D6196)), such that volatile organic compounds are transferred (injected) efficiently into the capillary
GC column for analysis.
4.3 GC-compatible organic compounds which are retained by the PPOR-BW-PP sorbent or quartz/PPOR-Bquartz/W-PP sorbent
tube during vapor collection and which elute between n-C and n-C on a 100 %, polydimethylsiloxane (PDMS) fused silica
6 16
capillary column are identified and quantified by gas chromatography/mass spectrometry (see Section 11). Selective ion
monitoring, ion extraction or spectral de-convolution shall be used to quantify specific volatile organic compounds. Individual
components of interest are quantified using authentic standards of that particular compound. Other compounds are quantified using
toluene as the surrogate standard reference material (see 11.7.2).
NOTE 1—The procedure is similar to that outlined in ISO 16000-6.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http://www.ansi.org.
Found in “Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air,” 2nd Ed., 1999, US. Environmental Protection
Agency/625/R-96/010b. Available from United States Environmental Protection Association (EPA), Ariel Rios Agency (EPA), William Jefferson Clinton Bldg., 1200
Pennsylvania Ave., NW, Washington, DC 20460, http://www.epa.gov.
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5. Significance and Use
5.1 Manufacturers of carpet need to monitor emissions of VOCs to assess the environmental impact of their products indoors.
These results are also used to demonstrate compliance with VOC emission limits for individual VOCs.
5.2 These data are also used to understand which VOCs are emitted from a product or material and to measure the magnitude
of those emissions.
5.3 Emission data may be used to compare different lots of carpet of the same materials of construction, or carpets composed
of different materials of construction, in order to develop products with lower emissions and lower potential environmental impact.
5.4 This test method should be used in conjunction with practices/guidelines for emissions testing such as Guide D5116,
Practice D7143, Practice D7706, ISO 16000-9, and ISO 16000-10. These detail how to select and prepare samples and how and
when to carry out emissions tests such that the concentration and profile of vapors in the exhaust air of the emission chamber/cell
are representative of the product under test. This standardtest method covers the sampling and analysis of volatile organic
compounds in the exhaust gas from the chamber/cell using thermal desorption—compatible sorbent tubes and will provide the
necessary analytical consistency to ensure that reproducible data is obtained for the analysis of identical vapor samples by different
laboratories.
6. Interferences
6.1 Organic compounds that have the same or nearly the same retention times as the analyte of interest can interfere during gas
chromatographic analysis. High resolution capillary columns are required to minimize these issues. Artifacts can be generated
during sampling and analysis. Interferences can be minimized by proper selection of gas chromatographic columns and conditions,
and by stringent conditioning of both the sorbent tubes and the analytical system before use. Artifacts may be formed during
storage of blank sorbent tubes. This is minimized by correctly sealing and storing blank and sampled tubes (see 7.3 and 10.1). The
effectiveness of these methods for controlling the potential interferences can be demonstrated by proper quality assurance
procedures including the use of blanks and spiked sampling tubes.
NOTE 2—Note that The inherent artifact levels will vary from sorbent to sorbent but are generally at sub-nanogram levels for quartz wool, PPOR-B
and for carbon-black W-PP and for MS-GCB (medium to strong graphitized carbon black) type sorbent (see Practice D6196).
6.2 Compounds of interest that co-elute chromatographically, are not distinguishable when using an FID. Identification and
quantification shall be done using a mass spectrometer in the selected ion monitoring (SIM) mode, or in SCAN mode in
combination with post-run processing using spectral deconvolution, or ion extraction, or both.
6.3 Even if mass spectroscopy is employed, it may not be possible to uniquely identify individual compounds when similar
compounds co-elute exactly (co-maximize) under the analytical conditions selected.
6.4 The This test method is suitable for sampling and analyzing vapor samples ranging up to 95 % relative humidity for all
hydrophobic sorbents such as quartz wool, PPOR-B and graphitized carbon blacks. W-PP and MS-GCB. When less hydrophobic,
strong sorbents such as carbonized CMS (carbonized molecular sievessieves) are used in a secondary (back-up) tube,tube (see Note
3 and Note 87)), care mustshould be taken to reduce the mass of water retained from humid samples (see Practice D6196).
7. Apparatus
7.1 Sorbent Tubes for Pumped Sampling—Sample tubes (see Practice D6196) packed with 200 mg of PPOR-BW-PP sorbent
or with a combination of 1 or 2 mm of loosely packed quartz wool, glass frit, or stainless steel screens bracketing 200 mg of
PPOR-BW-PP sorbent should be used for collection of the volatile organic vapors in the exhaust gas from the emission
chamber/cell. Analyses of glass or stainless steel spiked tubes indicates that similar results are obtained using either glass wool,
or stainless steel frits, as long as the sorbent is in the heated zone of the thermal desorber (see 12.2).
NOTE 3—Note that The use of a secondary back-up tube can serve as a useful check on the breakthrough volume of the primary PPOR-BW-PP or
quartz/PPOR-Bquartz/W-PP tubes. Breakthrough should be determined using two sorbent tubes containing the same sorbent and placed in series. Tube
performance should be addressed by individual laboratory QC programs, see EPA Method TO-17 for guidance.
7.2 Sorbent Tube End Caps for Long-termLong-Term Storage—Blank and sampled tubes should be sealed with metal screw-cap
fittings with combined (one-piece) PTFE ferrules for storage and transportation. If alternate fittings are used, the laboratory should
determine that they meet storage and transportation stability requirements.
NOTE 4—As a quick test that long term storage caps have been fitted correctly, check the length of the capped tube to make sure the seals are seated
as far down the tube as possible and check that the caps cannot be pulled off the tubes by hand using reasonable force.
7.3 Syringes—A precision 10–μL10-μL liquid syringe readable to 0.1 μL.
7.4 Soap Bubble Meter—A soap bubble flow meter or another suitable calibrated device is required for calibrating pump,
desorption, and split flows. Follow the manufacturer’s recommended procedure and or the participating laboratory QC program.
See Practice D3686 for further guidance.
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7.5 Thermal Desorption Apparatus—A two-stage apparatus is required for thermally desorbing VOCs retained on the sorbent
tubes and transferring/injecting them into a gas chromatograph (GC) in a flow of inert carrier gas. A typical apparatus contains a
mechanism for holding the tubes to be desorbed while they are heated and purged simultaneously with inert carrier gas. The sample
flow path through the thermal desorber must be constructed entirely of inert materials (that is, quartz, fused silica, silica-coated
steel, PTFE, etc.), including all valve components which may come into contact with sample vapors. The desorption temperature
and time should be adjustable, as should the carrier gas flow rate. Air must be purged from the sample tube and analytical system
before heat is applied to prevent sorbent and analyte oxidation. None of the purged air should be allowed to reach the GC column
or detector. The apparatus should incorporate a stringent leak test of every sample (see Note 5) to check flow path integrity before
sample desorption/analysis. The secondary focusing (cold) trap should contain appropriate sorbents and be of sufficient internal
diameter to prevent ice from blocking the flow path during the focusing of humid samples. It should be desorbed in back-flush
direction (that is, with carrier gas flowing in the reverse direction to that used during the trapping stage) to ensure compatibility
with components over the widest possible volatility range. The option for sample splitting should be available during primary
(tube) desorption, secondary (trap) desorption or both. Tubes on automated thermal desorption systems must be sealed, both before
and after desorption, to protect the integrity of sampled and desorbed (blank) tubes. The sample should be desorbed rapidly from
the secondary focusing trap to ensure efficient transfer to the capillary GC column and optimum sensitivity. The sample is routed
to the gas chromatograph by way of a heated capillary-lined, or silica-lined stainless steel, transfer line. The option of internal
standard addition, whereby gas phase internal standard is automatically introduced onto the sampling end of sorbent tubes post leak
test and before analytical desorption, should also be considered as a tool for checking system stability/performance over time (see
11.7.3).
NOTE 5—Note that leak Leak testing should be carried out under no-flow conditions, at low temperature, and at carrier gas column head pressure such
that it is suitably stringent, but does not compromise sample integrity. Tubes that fail the leak test should not be analyzed but resealed to await user
intervention.
7.6 Gas Chromatographic (GC) Apparatus:
7.6.1 Gas Chromatograph—Fitted with a mass spectrometric (MS) detector and with a flame ionization detector (FID) if the
latter is required (see 4.3). The gas chromatograph should be capable of split/splitless injections. The MS detector should be
capable of scanning between mass ion 25 and 450.
7.6.2 Gas Chromatographic Column—A100 % polydimethylsiloxane (PDMS) fused silica capillary column should be used.
Typical dimensions: 50 – 60-m long with 0.32-mm I.D. and a 1.0-μm film thickness. Higher speed alternatives with similar phase
ratio (narrower I.D. and thinner film) can also be used. If a more polar column (for example, cyanopropyl-phenyl-
polymethylsiloxane) is used for these analyses, the testing laboratory must demonstrate that they obtain recoveries and precision
that meet the guidelines outlined in 12.1 and 12.2.
7.6.3 Effluent Splitting—If both FID and MS detection are required by the relevant emissions test protocol, the outlet of the
capillary column should be connected to both the FID and MS detector using a conventional, zero or low-dead-volume, capillary
effluent splitting device. Connections from each respective detector to the capillary effluent splitter should ensure that sufficient
effluent from the capillary analytical column is directed to the FID and to the MS detector to achieve the desired detection limits,
taking into account the fact that the MS detector operates at vacuum.
7.7 Injection Facility for Preparing Standards Purpose-Built—Injection ports are available for introducing standards to the
sampling end of sorbent tubes in the vapor-phase in a stream of carrier gas. A conventional gas chromatographic injection port may
also be used. Injection port temperatures between 75°C and 140°C have been shown to give reliable results in preparing samples
(see 12.2 and Table 1). This can be left in-situ, or it can be mounted separately. The carrier gas line to the injector should be
retained. The back of the injection port should be adapted if necessary to fit the sampling end of a sorbent tube. This can be done
conveniently by means of a ⁄4-in. compression coupling with a PTFE or graphitized vespel ferrule. Alternatively, commercially
prepared standards may be used.
7.8 Use ordinary laboratory apparatus (for example, volumetric flasks for preparing standard solutions) as needed.
8. Reagents and Materials
8.1 Unless otherwise stated, all reagents shall conform to the specifications of the committee on Analytical Reagents of the
American Chemical Society, where such specifications are available. Other grades may be used, provided that it is ascertained that
use of the reagent does not lessen the accuracy of the practice.
TABLE 1 Average Recoveries for GC/MS Analysis of Six IVOCs spiked into Glass and Stainless Steel Thermal Desorption Tubes
Average % Average % Average % Average % Average % Average %
Recovery Recovery Recovery Recovery Recovery Recovery
Toluene Benzene 4-PCH Styrene 2-EHA Caprolactam
Glass Tube (Glass Wool) 102 97 98 99 120 70
Glass Tube (Glass Frit) 101 94 99 97 119 72
A
Stainless Steel (1) 94 92 89 86 109 66
A
Stainless Steel (2) 98 98 97 93 127 73
A
(1) and (2) refer to 75°C and 140°C preparation temperatures for the spiked tubes. The glass tubes were prepared at 75°C.
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8.2 Reagents:
8.2.1 Volatile Organic Compounds—To be prepared as liquid standards for calibration. These would ideally be within the
volatility range of n-hexane to n-hexadecane (see 1.5) and should reflect the compounds of interest. Toluene must be included.
8.2.2 Methanol Dilution Solvent—To be used as the solvent for preparation of liquid standards of toluene and the volatile
organic compounds of interest. The methanol used should be of chromatographic quality, free from compounds co-eluting with the
compound or compounds of interest (see 8.2.1). Alternative dilution solvents, for example, ethyl acetate or cyclohexane can be
used, particularly if there is a possibility of reaction or chromatographic co-elution.
8.3 Sorbents—Sorbent tubes, pre-packed with weighed amounts of sorbent, are available commercially. Empty industry-
standard sized tubes can also be packed by the user. In this case 200 mg of PPOR-BW-PP sorbent ranging in particle-size from
35 to 80 mesh should be weighed into standard sample tubes that are either empty or contain 1-2 mm of loosely packed, clean and
non-friable quartz wool, glass frits, or stainless steel screens at the sampling end. New commercial or self-packed PPOR-BW-PP
sorbent or quartz-PPOR-Bquartz-W-PP sorbent tubes should be stringently conditioned before initial use. Example conditions for
cleaning the sorbent tubes are as follows: 320°C under a flow of >100 mL/min of pure inert gas (helium or nitrogen) for >2 hours,
followed by a further 30 minutes at 335°C (see Practice D6196). Cleaning procedures specified by the tube supplier or
manufacturer should always be followed.
NOTE 6—Note that much less Less stringent conditions are required for cleaning used tubes (for example 10 minutes at a temperature ~20°C higher
than that to be used for analysis), provided this doesn’t exceed the maximum safe temperature for PPOR-BW-PP sorbent. Practically, the analytical
desorption temperature should not be greater that 300°C because higher temperatures may lead to the production of trace amounts of benzene. Tubes used
for trace level monitoring (individual VOC levels below 20 ng/L) can often be re-used immediately after analysis,analysis (that is, without further
cleaning).
8.4 Calibration Solutions—Following guidance given in Practice D6196, prepare standard solutions of toluene and other VOCs
of interest (for example; styrene, caprolactam and 4-phenylcyclohexene) in methanol such that a 1 to 4 μL injection, via the
calibration solution loading apparatus (see 7.7), introduces 20 to 2500 ng of each compound, or an alternative mass range if more
appropriate to the samples being tested. In any event, the lowest and highest concentration standards must be prepared such that
the mass of the analyte introduced in the highest level standard is at least a factor of 20 higher than that introduced in the lowest
standard.
9. Tuning and Calibration of the TD-GC/MS(FID) Analytical System
9.1 Tuning and mass standardization is performed in accordance with the manufacturer’s instructions, generally using
perfluorotributylamine (FC-43) commonly known as PFTBA. This process may vary among instruments. Consult the tuning
instructions for the specific instrument being used for the appropriate tune conditions. The FC-43 is introduced directly into the
ion source through a molecular leak. Instrument parameters are adjusted to give acceptable relative ion abundances. An example
of the ranges for the relative ion abundances based on the NIST02 mass spectral database are given below.
Mass % Relative Abundance
69 100
131 25-55
131 25–55
219 45-75
219 45–75
502 3-7
502 3–7
The mass range scanned is 35 amu to 450 amu with an allowable scan rate >0.5 Hz. The mass spectrometer should be tuned
prior to an initial calibration, after vacuum is broken (column change, new source installed, etc.), and if the calibration check has
failed.
9.2 Standard calibration curves will be required for MS (and on FID, if required by the relevant materials emissions testing
protocol) for each compound of interest comprising at least five points within the range of 20 to 2500 ng of each compound. The
standard concentrations distribution should not be greater than five times the concentration of the next lower standard (for example
20, 100, 500, 1750, 2500 ng). See Fig. 1 for a typical example of an MS calibration curve (area response versus ng toluene loaded
on a thermal desorption tube). Prepare loaded tubes by injecting aliquots of standard solutions onto clean PPOR-BW-PP sorbent
or quartz-PPOR-Bquartz-W-PP sorbent tubes as follows: Fit the sampling end of the clean sorbent tube into the injection unit (see
7.7) through which inert purge gas is typically passing at 50-100 mL/min and introduce a 1 to 4 μL aliquot of an appropriate
standard solution injected through the septum. After 1 to 5 minutes, disconnect the tube and seal it using long term storage caps
(see 7.3). This multi-level calibration shall be carried out when the calibration check (see 9.4 and 9.5) falls outside the specified
range. The MS response factors shall agree within 20 % across all calibration levels or demonstrate an R value of >0.995.
9.3 The use of a linear regression of the standards for quantification is recommended. Use of a linear regression of the standard
responses does not eliminate the possibility of large systematic errors if the intercept value is large relative to the quantity being
measured. The analyst needs to be aware of unusually large intercepts which may bias the results. Typically observed intercept
values for toluene, benzene, styrene, 4PCH, caprolactam, and 4-ethylhexanoic acid have ranged from 5 to 50 nanograms.
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FIG. 1 Toluene MS Calibration Curve
9.4 Split or splitless injections can be used for these analyses. In either case, care must be taken to ensure that the calibration
standards do not exceed the capacity of the sorbent material, column, or the detector. Appendix X1 gives suggested split conditions,
however the analyst may need to adjust the split flow (or lack thereof) to accommodate the sensitivity needed, the breakthrough
volume of the compounds of interest, or the capacity of the column and/or detector.
9.5 If an FID is used, a single, mid-point calibration check of detector response will be carried out before and after the analysis
of a series of sorbent tubes collected during emissions testing of a single sample of carpet. The FID response factor shall agree
within 10 % to the average of that obtained from all five standards during the most recent multi-level calibration. If this is not the
case, the five-level calibration curves must be repeated before proceeding with the analysis.
9.6 A check on MS response for each target VOC will be carried out at the midpoint level of the
...