GMW 15634

WORLDWIDE ENGINEERING STANDARDS

Test Procedure Materials

GMW15634

Determination of Volatile and Semi-Volatile Organic Compounds from Vehicle Interior Materials

Note: Nothing in this standard supersedes applicable laws and regulations. Note: In the event of conflict between the English and domestic language, the English language shall take precedence. 1.1 Purpose. This Test Procedure is used for the qualitative and semi-quantitative determination of Volatile Organic Compound (VOC) and SemiVolatile Organic Compound (SVOC) emissions in vehicle Interior Materials (IM) utilizing TenaxTA adsorbent media and Thermal Desorption - Gas Chromatography / Mass Selective Detector (TDGC/MSD). 1.1.1 Individual VOC and SVOC emissions in different vehicle interior materials can be identified, semi-quantified, and compared. 1.1.2 VOC emissions in the boiling point range ≤ 345°C or chromatographic elution range from n-pentane (n-C5) to n-eicosane (n-C20) can be detected by this method (VOC value). It is assumed that these substances can be detected from an analysis of the vehicle interior air. 1.1.3 Emissions that condense on a vehicle surface (e.g., glass, plastic lens, etc.) at ambient temperature are classified as Semi-volatile Organic Compounds (SVOC) or FOG components. SVOCs are in the boiling point range ≥ 280°C or chromatographic elution range from n-hexadecane (n-C16) to n-dotriacontane (n-C32) and can also be detected by this method (FOG Value). 1.1.4 The limits for the VOC and SVOC have been established by convention. 1.2 Foreword. Determination of VOCs and SVOCs in vehicle interior air is essential to meet customer requirements and regulatory requirements in some global markets. Emissions from the vehicle interior materials can be the source of the emissions in the vehicle interior air. Concentrations are in the parts per million (ppm) range, which warrants accurate analytical measurements. 1.3 Applicability. All materials than can contribute to emissions in the vehicle interior must be tested. Examples include emissions from textiles, carpets,

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1 Scope

adhesives, sealants, foams, plastic components, films, leather, interior paints and composite materials. 1.3.1 In relation to emissions, the relevant vehicle interior area comprises all areas that are linked to the passenger compartment either directly or by air contact. Therefore it also includes the luggage compartment, Heating, Ventilation and Air Conditioning (HVAC) systems, etc. 1.3.2 The results will provide complementary information to interpret findings in GMW3205, GMW3235 and GMW3059. The analytical instrument described herein can also be used in GMW15654 to determine the concentration of VOC and SVOC in vehicle interior air. 1.3.3 Suppliers must submit the TD-GC/MSD analysis results together with the corresponding material samples. 1.3.4 This test procedure compliments VDA-278 and results may be compared to the American Industrial Hygiene Association (AIHA) health standards.

2 References Note: Only the latest approved standards are applicable unless otherwise specified. 2.1 External Standards/Specifications. DIN 55531

ISO/IEC 17025

2.2 GM Standards/Specifications. GMW3059 GMW3235

GMW3205 GMW15654

2.3 Additional References. 

Thermal Desorption Analysis of Organic Emissions to Characterize Non-Metallic Automotive Materials. German Association of the Automotive Industry. English Translation, Sep. 2002, Verband der Automobilindustrie VDA-278 Recommendation. Method may be examined at www.vda.de/index_en.html



Odor thresholds for chemicals with established occupational health standards, American Industrial Hygiene Association. May be purchased at www.aiha.org.

© Copyright 2008 General Motors Corporation All Rights Reserved

January 2008

Copyright GM Worldwide Provided by IHS under license with GMW No reproduction or networking permitted without license from IHS

Originating Department: North American Engineering Standards

Sold to:ESPUMLATEX S A, W0743786 Not for Resale,2009/8/26 19:47:27 GMT

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GMW15634

GM WORLDWIDE ENGINEERING STANDARDS

3 Resources 3.1 Facilities. Lab testing is to be performed by a laboratory that conforms (see Note) to ISO/IEC 17025 and should be or is acceptable to the customer (GM). Test reports must conform to Sections 5.10.2 and 5.10.3 of ISO/IEC 17025 with a letter of compliance. Note: Meets requirements, may not be formally recognized by a third party. 3.2 Equipment. This test procedure utilizes commonly available sampling equipment and analytical instrumentation. Specific instrumentation and test conditions are given in Appendix A. 3.2.1 Balance with a sensitivity of 0.01 mg. 3.2.2 Directly Coupled Thermal Desorption-Gas Chromatography System with Cryofocusing and Split System. This instrumentation may be purchased at www.gerstelus.com. 3.2.3 Gas Chromatograph (GC) with massselective detector, software and mass spectra library. This instrumentation may be purchased at www.agilent.com. 3.2.4 GC Capillary Columns. GC Capillary Guard Column is used to prevent thermal shock to increase capillary column longevity. A low-Bleed Gas Chromatograph Mass Spectrometer (GC/MS) Capillary Column, Stationary Phase: (5%-phenyl)methylpolysiloxane is used (e.g., 60 m x 0.32 mm x 0.50 μm DB-5MS capillary column Agilent P/N 1235566, see Appendix A). 3.2.5 Sample Tubes with deactivated glass surface. 3.2.5.1 TenaxTA Glass Thermal Desorption Tubes (GTDT), compatible with the specific corresponding thermal desorption system. (See Figure G1). The tubes may be purchased at www.supelco.com. 3.2.5.2 Empty Glass Tubes compatible with the specific corresponding thermal desorption system. Empty glass tubes with ~3 cm end-packed deactivated quartz wool or with glass frits at one end of the tube can be used. These are designated as an Interior Material Glass Thermal Desorption Tube (IM GTDT) (see Figure G1). 3.2.6 Tube-Spiking Adapter for spiking liquid standards onto Tenax tubes and evaporating the solvent. For example see Figure G2 for details. Other apparatus can also be used. 3.2.7 Carrier Gas. Grade ≥ 5.0 Helium and a corresponding in-line purifier trap is used for the GC carrier gas, the TenaxTA Glass Thermal Desorption Tubes (GTDTs) conditioning purge gas and the Tube-Spiking Adapter gas.

3.2.8 Conditioning TenaxTA Glass Thermal Desorption Tubes (GTDTs). Tenax filled tubes will be cleaned thermally with an apparatus designed for that purpose, such as the Dynatherm Model 9600 six-tube conditioner, or equivalent. Set the helium purge gas flow rate to 30 to 40 mL/minute for each port. Conditioning consists of heating TenaxTA GTDTs at 320°C continuously for 3 h ± 10 minutes. TenaxTA GTDTs must be conditioned before use. The conditioning apparatus may be purchased at www.cdsanalytical.com. 3.2.8.1 For empty tubes, use an appropriate detergent for the cleaning of the empty glass tubes. After cleaning with the detergent the tubes have to be cleaned with distilled water and then heated in a drying oven at 105°C for 45 minutes. 3.2.8.2 After the cleaning (thermally and/or with detergent) the tubes should be packed airtight in aluminum foil or special Teflon tubes to prevent contamination. 3.2.9 Syringes for Spiking Tubes: 10 L, 5 L, and 1 L syringes. 3.2.10 Solvents for Standard Dilutions. 

Methanol (MeOH), HPLC grade.

 Methylene Chloride (MeCl2), HPLC grade. 3.2.11 Standards and Dilutions. All standards and dilutions are to be kept in sealed containers and refrigerated ≤ 8C when not in use. 3.2.11.1 Standards of desired VOC and SVOC components at ≥ 98% purity (or equivalent). Standards can be purchased at www.sigmaaldrich.com. 3.2.11.2 Check standard containing a mixture of 18 individual components, 110 ± 10 g/mL each in MeOH. (See Appendix B, B1.) 3.2.11.3 Calibration standard consisting of toluene and n-hexadecane, 500 ± 50 g/mL each in MeOH. (See Appendix B, B2). 3.2.11.4 n-Alkane Standard containing n-C5 to nC32 of 28 individual n-alkane components, 2000 g/mL each in MeCl2. The n-Alkane standard can be custom blended and purchased at www.spexcsp.com. 3.2.11.5 Aromatic Standard containing aromatic hydrocarbons, 14 individual components, 2000 g/mL each in MeOH. The aromatic standard (AK-101AA-ARO-PAK) can be purchased at www.accustandard.com. 3.2.11.6 Grob-Test Mix for testing the GC-column performance. This test mix can be purchased at www.sigma-aldrich.com.


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Calendar time:

1 day

Test hours:

8 hours

Coordination hours:

4 hours

3.5 Test Required Information. 3.5.1 For Parts. Part number and drawing and circa dimensions of the part in the interior. 3.5.2 For all Samples. Manufacturing date and sampling date has to be declared. 3.6 Personnel/Skills. Proper training is required to operate the instrumentation in this procedure. Professional degrees in chemistry, chemical engineering, or the health sciences are preferred.

4 Procedure 4.1 Preparation. For each sample, two tubes are loaded with the weighed amount specified for the material (see Appendix C). 

Tube A: First VOC analysis run.



Tube B: Second analysis run for VOC followed by SVOC or FOG run. 4.1.1 From the material, 2 samples should be taken originating from 3 different places at the sample. For each sample, 3 small strips are cut off with a scalpel and weighed into one glass tube (weight 10 to 30 mg). (Figure G6 for sample scheme.) 4.1.2 In order to insert as large a sample as possible, maximum use should first be made of the width of the sample tube when cutting the sample to size. The maximum sample width is generally around 3 mm. The dimensions of the cut sample should be documented in the report. 4.1.3 Some suggested interior material masses are given in Appendix C. The required accuracy for weighing is ± 0.1 mg. 4.1.4 For Thick Samples: height, more than 3 mm, or sandwich samples, cores of 3 mm diameter are stamped out. These cores are cut into halves. For analysis two different halves are weighed into one tube. 4.1.5 For Multi-Layer Sandwich Samples: with individual layers relatively thick, more than 0.5 mm, the material in each layer should be analyzed separately. This also helps to allocate the emitted substances accordingly, and to target problem materials. 4.1.6 For Paint Films: 2 samples, 30 x 3 mm are weighed into a glass tube. The weight of the aluminum foil has to be subtracted. 4.1.7 Samples with a High Water Content: e.g., leather could lead to a freezing of the cold trap. This leads to lower values or the run is aborted. To prevent this, reduce the weight of these samples.


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3.3 Test Vehicle/Test Piece. This Test Procedure is used to test vehicle interior materials that are contributing emissions. Materials should be obtained from suppliers as soon as possible after production. The sample should be taken within 7 days after production. Manufacturing date and sampling date should be documented. Care should be taken to prevent material out-gassing before analysis (package, refrigerate). 3.3.1 For the analysis, a representative sample of the material is taken (for larger parts, small samples are cut, ca. sample size 10 cm x 15 cm). The sample should not be touched with bare fingers. The cutting has to be done with an oil-free tool. The sample should be packed into aluminum composite films (e.g., VACUPAC, or any other material according to DIN 55531.) In the exceptional case, the sample can be packed twice into thick silicone-free aluminum foil (clean with npentane), the edges should be folded multiple times to prevent contamination and to ensure a gastight packing. The aluminum foil packed sample should then be packed additionally into a polyethylene bag. The bag should be labeled with drawing number; final sample name (can not be changed afterwards), manufacturing date and date of sampling. Note: If this information is missing the sample will not be analyzed. 3.3.2 Paints are sprayed on aluminum foil 30 µm maximum foil thickness, to a dried film thickness of 50 ± 5 µm. For multilayer paints, the thickness of the film should be the same as the thickness on the painted part. If necessary each layer will be analyzed separately. The paint process guidelines of the paint supplier including coating, thickness and drying requirements shall be followed. After drying, the samples are vented at room temperature for 7 days. After venting, packaging is done as described above for the other materials. 3.3.3 After receipt in the laboratory, samples should be refrigerated -18°C until analysis. 3.3.4 Prior to analysis, the sample should be taken from the refrigerator and stored open at room temperature for 2 h to prevent condensation. From manufacturing to analysis, it should be assured that the sample has been stored open at room temperature for 7 days. 3.4 Test Time.

GMW15634

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GMW15634


4.2 Conditions. 4.2.1 Environmental Conditions. Not applicable. 4.2.2 Test Conditions. Deviations from the requirements of this standard shall have been agreed upon. Such requirements shall be specified on component drawings, test certificates, reports, etc. 4.2.2.1 Samples of vehicle interior material are heated to either 90°C (VOC) for 30 minutes or 120°C (SVOC or FOG) for 60 minutes and the evolved gases are trapped in a cold injection system. At the end of the thermal evolution phase, these gases are then thermally desorbed at 280°C into the GC/MSD system for qualitative and semiquantitative analysis. 4.2.2.2 The VOC value is measured twice, from each of the two prepared samples. Following the VOC analysis, the FOG value is determined by leaving the second sample in the desorption tube, and heating it under the FOG conditions to 120°C for 60 minutes. 4.2.2.3 A semi-quantitative determination of the emissions expressed as mass parts per million (ppm) can be obtained by calibration with reference substances; toluene is used as a reference substance for VOC and n-hexadecane as reference substance for the FOG value. Unknown substances can be identified from the mass spectra and the retention time. 4.3 Instructions. The instrument conditions for the VOC and FOG analysis are given in Appendix D. 4.3.1 Spiked Standard(s). The known standard solutions (g/L) of sought compounds are spiked on separate preconditioned TenaxTA tubes. This is accomplished by using an apparatus as described in 3.2.6 and Figure A3. Use a 0.7 ± 0.3 L/minute helium flow rate for 3 to 4 minutes to achieve a 2.5 to 3.0 L total helium volume. 4.3.1.1 Check Standard. Perform a TD-GC/MSD run on a TenaxTA GTDT spiked with 4 L of Check Standard (see 3.2.11.2) in SCAN mode to acquire standard VOC and SVOC compounds. The retention times of the components in this mixture are suitable as reference points to determine the retention time indices of unknown substances, and in this way can be used as an additional check of MSD identification during test runs. Keep a running record of the individual components response and retention times as a method monitor. 4.3.1.1.1 A calibration curve is prepared by spiking a number of TenaxTA GTDT with different volumes of the check standard solution (range 0.01 to 6 µg per substance per injection).

4.3.1.2 Calibration Standard. Perform a TD-GC/MSD run on a TenaxTA GTDT spiked with 4 L of Calibration Standard (see 3.2.11.3) in SCAN mode to acquire toluene equivalent data for VOCs and hexadecane equivalent data for SVOCs (this calibration is used for compounds beyond the specific sought substances). 4.3.1.3 n-Alkane and Aromatics Standards. Perform a TD-GC/MSD run on a TenaxTA GTDT spiked with 1 L of n-Alkane Standard (see 3.2.11.4) or 1 µL Aromatics Standard (see 3.2.11.5) in SCAN mode with VOC and SVOC conditions. The retention times of the components in these mixtures are suitable as reference points to determine the retention time indices of unknown substances (see Figures G3 and G4), and in this way can be used for an additional check of MSD identification during test runs. Keep a running record of the individual components response and retention times as a method monitor. 4.3.2 Testing the TD-GC/MSD system. The function of the instrument system is tested by analyzing a check standard during the analysis sequence. 4.3.2.1 This check standard contains non-polar, polar, basic and acid components that would display noticeable peak tailing even with low adsorption effects. Peaks occurring in close succession can be used to check the separation efficiency of the chromatographic column. 4.3.2.2 The performance of the mass spectrometric detector is verified by means of mass and sensitivity tuning and the specification required by the manufacturer must be achieved. An air/water check has to be done to check the integrity of the entire system. 4.3.2.3 All substances in the check standard must be clearly identified from the mass spectra library during the search run. 4.3.2.4 The thermal desorption system must also be checked for possible memory effects by performing a “blank” run with an empty desorption tube at least before every sample series. 4.3.3 Test Procedure. Prior to the analysis of interior material samples a calibration has to be done and the following limits of detection have to be reached: 

toluene < 0.04 µg,



n-hexadecane (n-C16) < 0.05 µg,



n-eicosane conditions)



n-dotriacontane (n-C32) < 0.2 µg, (at SVOC conditions)

(n-C20)

< 0.06 µg,

(at

VOC


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GM WORLDWIDE ENGINEERING STANDARDS 4.3.3.1 Recovery rate of the individual substances of the check standards under VOC conditions should be between 60 to 140%, with the exception of toluene which should be between 80 to 120%. 4.3.3.2 For a complete analytical run, the following measurements have to be done: 4.3.3.2.1 Blank sample under VOC and SVOC conditions, to check the cleanliness of the TD-GC/MSD system. 4.3.3.2.2 Check standard mix spiked on a TenaxTA tube for testing the TD-GC/MSD system 4.3.3.2.3 Calibration standard (toluene and n-hexadecane), 4 µL of the standard solution spiked on a TenaxTA GTDT, as described in 4.3.1.2 for the semi-quantitative determination of the substances. 4.3.3.2.4 Analysis of the interior material, at VOC and SVOC conditions. 4.3.3.3 After every change of the TD-GC/MSD system, (e.g., cleaning, changing the column, etc.) the Grob-Test Mix, n-alkane standard and aromatic standard must be analyzed to determine the retention time of the analytes for quality assurance.

5 Data

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5.1 Calculations 5.1.1 Qualitative Analysis. During this procedure identification of individual VOC and SVOC components is accomplished by operating the mass filter in SCAN mode. Several sought compounds may be semi-quantitatively determined with an extracted ion chromatogram, e.g., when there are overlapping peaks or an explicit determination is impossible. Usually the molecule’s base ion (highest m/z abundance) or the + molecule’s parent ion (if available: m/z = M ) serves as the target ion (quantitative m/z). A known corresponding fragment ion serves as a qualifier ion (m/z). With this information and the retention time of each analyte, an exact determination is possible. If a substance cannot be clearly identified, a possible identification (marked with a question mark) or a reference to the substance class can be given, provided that the appropriate reference points (e.g. typical mass fragments) permit such conclusions to be drawn. (See Appendix E for notation examples). 5.1.2 Semi-Quantitative Analysis. 5.1.2.1 Total Amount of VOCs and SVOCs. The total area of all of the substance peaks occurring in the chromatogram (excluding artifacts) is determined first. The integration parameters for the chromatography software must be set so that peaks with a concentration of ≥ 1 ppm are detected

GMW15634

reliably. For the total amount of VOCs, all peaks in the corresponding chromatogram have to be integrated, including peaks beyond the retention time of the n-C20 alkane as well as peaks with a concentration lower than 1 ppm. 5.1.2.2 If the chromatogram includes so-called “oil-mountains”, consisting of unresolved species, these are integrated as one peak, in which the baseline is laid from the start to the end of the “oil-mountain”. If clearly identified peaks of other substance occur in this zone, they must be integrated and specified separately. 5.1.2.3 The calculation for the individual peaks can be found in Appendix F. 5.1.2.3.1 The total amount of VOCs is calculated as toluene equivalent, and the total amount of SVOCs as n-hexadecane (n-C16) equivalent by comparison of the peak areas to the peak area of the individual calibration standard. For the VOC, only the peak areas from n-pentane (n-C5) to neicosane (n-C20) will be calculated. For the SVOC, only the peak areas from n-hexadecane (n-C16) to n-dotriacontane (n-C32) will be calculated. 5.1.2.3.2 If the VOC results deviate by more than 20% relative to the mean value, a repeat analysis, including a SVOC run, must be performed. Both VOC values must be stated in the test report, but the analysis with the higher value is used for evaluation. 5.1.3 Individual Amounts of VOCs and SVOCs. 5.1.3.1 Each analyte with a concentration > 1 ppm has to be identified and its concentration has to be calculated. At a minimum, the concentrations of the analytes that are mentioned in the individual regulation have to be calculated. 5.1.3.2 The individual VOCs and SVOCs are quantified by comparing the SCAN quantitative ion peak area amounts to those of known standard solutions (external standard calibration). 5.1.3.3 If there are individual peaks in the “oil-mountains” they have to be integrated manually at the height sticking out the “oil-mountain”. 5.1.4 Calculated Result Disclaimer. The calculated semi-quantitative results obtained are from individual organic compounds thermally stripped and detected under these particular methods and corresponding sampling conditions. This semi-quantitative method should not be compared to other semi-quantitative or quantitative methods. 5.2 Interpretation of Results. Some VOCs and SVOCs are frequently cited as odorous compounds and may require additional testing in


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GMW15634


accordance with GMW3205. Those VOCs and SVOCs listed as restricted and reportable substances should meet the requirements specified under GMW3059. 5.3 Test Documentation. The results are displayed in a report. See Appendix G for details. In addition, the chromatograms for the VOC/SVOC determination and associated substance lists must be attached to the results report. The full set of analytical data must be supplied electronically. It should include: 5.3.1 Microsoft Excel files containing the detailed results of the VOC/SVOC analysis and the chromatogram of the appropriate sample. 5.3.2 Information on the TD-GC/MSD equipment used for the measurement. 5.3.3 Information on the calculation of the results.

6 Safety This standard may involve hazardous materials, operations, and equipment. This standard does not propose to address all the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

7 Notes 7.1 Glossary. Not applicable. 7.2 Acronyms, Abbreviations, and Symbols. CAS# Chemical Abstract Service Number CIS Cooled Injection System FOG Same as SVOC GC Gas Chromatograph GC/MS Gas Chromatograph/Mass Selective Detector GTDT Glass Thermal Desorption Tube He Helium

HVAC ID IM IM GTDT MS MSD ppm RT SCAN SIM SLH STBY STD SVOC TD TD-GC/MSD

TDS TIC VDA VIAQ VOC

Heating, Ventilation and Air Conditioning Internal Diameter Interior Materials Interior Material Glass Thermal Desorption Tube Mass Spectrometer Mass Selective Detector parts per million Retention Time Scan over specified mass range Selective Ion Monitoring Septumless Head Standby Standard Semi-Volatile Organic Compound Thermal Desorption Thermal Desorption Gas Chromatography / Mass Selective Detection Thermal Desorption System Total Ion Chromatogram Verband der Automobilindustrie Vehicle Interior Air Quality Volatile Organic Compound

8 Coding System This standard shall be referenced in other documents, drawings, etc., as follows: Test to GMW15634

9 Release and Revisions 9.1 Release. This standard originated in July 2007, replacing GMW8081. It was first approved by the GM Global VIAQ Team in December 2007. It was first published in January 2008.

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GMW15634

Appendix A Table A1: Instruments Usable for the Measurements Described Herein Instrument Part Thermal Desorption System Gas Chromatograph

Example Combination 1

Example Combination 2

Gerstel TDS2

Gerstel TDS3

Agilent 6890N + ChemStation PC software

Agilent 6890N + ChemStation PC software Gerstel CIS 4 including a deactivated quartz wool liner (#007519-010-00), silver seal (#002841-005-0), GP-2M silver adapter (#007259-045-00), GP2M slotted nut (#001268-005-0), GP2M 0.32 mm ID ferrule (#001805-04500) and MASter PC software for system control

Mass Selective Detector and Spectra Library

5973N Agilent Mass Selective Detector + NIST and Wiley mass spectra libraries

5975N Agilent Mass Selective Detector + NIST05 mass spectra library

GC-Column with Stationary Phase (5% phenyl)methylpolysiloxane

Agilent ~15 cm x 0.32 mm capillary guard column #160-2325-1, glass union #705-0825, polyamide sealing resin #500 to 1200 is connected to the beginning of the preferred capillary column. + Agilent Technologies 60 m x 0.32 mm x 0.50 µm DB-5MS capillary column (#123-5566).

HP Ultra 2: 50 m x 0.32 mm x 0.52 µm

Gerstel configuration for the Gerstel system (Supelco, #28287-U) or with frits (Supelco 28286-U)

Gerstel configuration for the Gerstel system (Supelco, #28287-U) or with frits for Gerstel TDS-System (Supelco 28286-U)

Gerstel configuration for the Gerstel System (Supelco #28281-U)

Gerstel configuration for the Gerstel System (Supelco #28281-U)

Apparatus for Spiking the TenaxTA Tubes

Gerstel Septumless Head (SLH) Adapter (#008871-004-00), with a He flow meter connected upstream, and a gas meter connected downstream.

Gerstel Septumless Head (SLH) Adapter (#008871-004-00), with a He flow meter connected upstream

Apparatus for Conditioning the Tubes

Dynatherm Model 9600 Six-Tube Conditioner

Syringes

Agilent: 10 µL syringe (#5181-1267, 5 µL syringe (# 5181-1273) and 1 µL syringe (5188-5247).

Desorber Tubes with an Internal Diameter (ID) 4 to 5mm with Deactivated Glass Surface Desorber Tubes Internal Diameter (ID) 4 to 5mm with Deactivated Glass Surface Filled with TenaxTA

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Temperature Programmable Cryotrap with Split

Gerstel CIS 4 including a deactivated quartz wool liner (#007519-010-00), silver seal (#002841-005-0), GP-2M silver adapter (#007259-045-00), GP-2M slotted nut (#001268-005-0), GP-2M 0.32 mm ID ferrule (#001805-045-00) and MASter PC software for system control

Gerstel: 10 µL Syringe (# 009996-05900)


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Appendix B B1 Check Standard Carefully weigh out 220 ± 20 mg of each component (below) into a 5 mL roll-edged vial to an accuracy of 0.1 mg. Take approximately 100 mg of this mixture and transfer it to a 50 mL volumetric flask and weigh to an accuracy ± 0.1 mg. MeOH is then added to just below the calibration mark the measuring flask, the flask is closed and carefully shaken until all the solvent droplets have fully dissolved in the MeOH. The volumetric flask is then filled up again to the line. Table B1: Check Standard Components benzene

2-ethylhexanol

n- heptane

n-undecane

n- octane

n-dodecane

n- butyl acetate

n-tridecane

p- xylene

n-tetradecane

o- xylene

dicylohexylamine

n- nonane

n-pentadecane

n- decane

n-hexadecane

Note: The n-butyl acetate normally hydrolyzes in MeOH noticeably in a few days. This creates an additional butanol and acetic acid peaks within the chromatogram. The n-butyl acetate peak also decreases in intensity as a direct function of decreased concentration. Note: This mixture serves as an example; additional substances for this standard also can be used.

B2 Calibration Standard


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Carefully weight 20 to 30 mg of toluene and n-hexadecane (both pesticide grade) into a 50 mL volumetric flask to an accuracy of ± 0.1 mg. Then add methanol or pentane exactly up to the line, close the flask and carefully shake it.


GMW15634

Appendix C Interior Material Sample Weights. Unless otherwise specified, weigh out 10 to 30 mg solid sample that has been cut to fit the Internal Diameter (ID) of an IM GTDT. The IM cuts should maximize the surface area exposed to thermal heating. The following is a suggested mass of different interior materials: Table C1: Interior Material Sample Weights Material

Weight

Comments

Foam

15 ± 2 mg

Pack loosely, take sample from the surface, because of the influence of the release agent

Composite fiber

60 ± 20 mg

Thick plates must to be divided

Film-type

30 ± 5 mg

Single strips

Leather

10 ± 2 mg

Remove most of the backside meaty texture, more important are the paints on the front side

Paints

Film 50 ± 5 µm (strips 30 mm x 3 mm)

Adhesives

30 ± 5 mg


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Film in application size

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Appendix Conditions


D:

Instruments

and

Thermal Desorption System (TDS) Instrument Conditions for VOC/SVOC Standards. Set up the Gerstel TDS2/3 instrument with the conditions in Table D1. For other instruments the parameters have to be adapted. Table D1: TDS Instrument Conditions for VOC/SVOC Standards Mode: STD or STBY Cool Flow Mode: Splitless Purge Time: 0 minutes Standby Temp: 20C Transfer Temp: 300C Valve Temp: 20C Purge Time: 0 minutes Calibration Run: 0

Initial Temp: 20C Initial Time: 0 minutes Delay Time: 1 minutes st 1 Rate: 60C/minutes st 1 Final Temp: 300C st 1 Final Time: 7.5 minutes nd 2 Rate: 0C/minutes nd 2 Final Temp: 0C nd 2 Final Time: 0 minutes

TDS Instrument Conditions for VOCs in interior Material Samples. Set up the Gerstel TDS2/3 instrument with the conditions in Table D2. For other instruments the parameters have to be adapted. Table D2: TDS Instrument Conditions for VOCs in interior Material Samples Mode: Sample Remove Flow Mode: Splitless Purge Time: 0 minutes Standby Temp: 20C Transfer Temp: 280C Valve Temp: 20C Purge Time: 0 minutes Calibration Run: 0

Initial Temp: 20C Initial Time: 0 minutes Delay Time: 1 minutes st 1 Rate: 60C/minutes st 1 Final Temp: 90C st 1 Final Time: 30 minutes nd 2 Rate: 0C/minutes nd 2 Final Temp: 0C nd 2 Final Time: 0 minutes

TDS Instrument Conditions for SVOCs in IM Samples. Thermal Desorption System Instrument Conditions for SVOC Emission Analysis. Set up the Gerstel TDS2 instrument with the conditions in Table D3. For other instruments the parameters have to be adapted.

Table D3: TDS Instrument Conditions for SVOCs in IM Samples. Mode: Sample Remove Flow Mode: Splitless Purge Time: 0 minutes Standby Temp: 20C Transfer Temp: 300C Valve Temp: 20C Purge Time: 0 minutes Calibration Run: 0

Initial Temp: 50C Initial Time: 0 minutes Delay Time: 1 minute st 1 Rate: 60C/minutes st 1 Final Temp: 120C st 1 Final Time: 60 minutes nd 2 Rate: 0C/minute nd 2 Final Temp: 0C nd 2 Final Time: 0 minutes

Cooled Injection System (CIS) Instrument Conditions. Set up the Gerstel CIS4 instrument with the conditions in Table D4. For other instruments the parameters have to be adapted. Table D4: CIS Instrument Conditions. Run Time: 60 minutes Split Mode: Split Initial Temp: -150C Initial Time: 0.1 minute st 1 Rate: 12C/s st 1 Final Temp: 300C st 1 Final Time: 5 minute

Cryo Cooling: On Splitless Time: 0 minute Purge Time: 0 minute Equilib. Time: 0.4 minute nd 2 Rate: 0C/s nd 2 Final Temp: 0C nd 2 Final Time: 0 minute

GC Inlet Conditions for Standards and Material Samples. Set up the 6890N GC inlet for a desired capillary column with the conditions in Tables D5, D6 and D7. Tor other instruments the parameters must be adapted. Table D5: GC Inlet Conditions Inlet Mode: Solvent Vent

Constant Flow: 1.3 mL/minute

Vent Flow: 50 mL/minute

Vent Time: 0 minute

Purge Flow to Split

Vent Time: 0.1 minute

Gas Saver: On

Saver Flow: 30 mL/minute

Saver Time: 3 minute

Outlet: MSD

Outlet Pressure: Vacuum


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GM WORLDWIDE ENGINEERING STANDARDS Table D6: Alternate Split Ration Table Split Ratio Note 1

30:1 40:1 50:1 60:1 80:1 100:1

Purge Flow to Split Vent (mL/minute) Note 1 38.7 51.6 64.6 77.5 103 129

Table D8: GC Oven and MSD Conditions for VOCs in Standards and IM Samples.

Total Flow (mL/minute)

Initial Temp: 40C Initial Time: 2 minute Rate 1: 3 C/minute Rate 2: 5 C/minute Rate 3: 10 C/minute

Note 1

42.9 55.8 68.7 81.6 107 133

Post Temp: 0C Post Time: 0 minute Run Time: 63 minutes

Note 1: Preferred

Table D7: Desired Columns for VOC/SVOCs VOC Desired Capillary Column: Pressure: 4.84 psi Vent Pressure: 4.84 psi Desired Capillary Column: Pressure: 6.70 psi Vent Pressure: 6.70 psi SVOC Desired Capillary Column: Pressure: 5.36 psi Vent Pressure: 5.36 psi Desired Capillary Column: Pressure: 7.28 psi Vent Pressure: 7.28 psi

GMW15634

50 m x 0.32 mm x 0.52 m Avg. Velocity: 31.8 cm/second GC Oven Start: 40C 60 m x 0.32 mm x 0.5 m Avg. Velocity: 29.0 cm/second GC Oven Start: 40C

50 m x 0.32 mm x 0.52 m Avg. Velocity: 32.0 cm/second GC Oven Start: 50C 60 m x 0.32 mm x 0.5 m Avg. Velocity: 29.2 cm/s GC Oven Start: 50C

GC Oven Conditions for VOCs in Standards and IM Samples. Set up the 6890N GC oven with the conditions in Table D8. For other instruments the parameters have to be adapted.

Max Temp: 325C Equil. Time: 0.2 minute Final: 92C for 0 minute Final: 160C for 0 minute Final: 310C for 15.07 minute Cryo: Off Quick Cryo Cool: Off Ambient Temp: 25C

MSD Conditions for VOCs in Standards and IM Samples. Set up the 5973N MSD with the conditions in Table D9. For other instruments the parameters have to be adapted. Table D9: MSD Conditions for VOCs in Standards and IM Samples. Tune: standard spectra autotune Data Delay: 3.8 minute (60 m column) Scan Mode: 29 to 282 amu Transfer line: 280C Quadrupole: 150C

(GC oven at 100C)

Scan Rate: 3.1 scans/s Threshold: 100 Source: 230C

GC Oven and MSD Conditions for SVOCs in Standards and IM Samples. Set up the 6890N GC oven with the conditions in Table D10. For other instruments the parameters have to be adapted. Table D10: GC Oven for SVOCs in Standards and IM Samples. Initial Temp: 50C Initial Time: 2 minute Rate 1: 25 C/minute Rate 2: 10 C/minute Post Temp: 0C Post Time: 0 minute Run Time: 44 minutes

Max Temp: 325C Equilib. Time: 0.2 minute Final: 160C for 0 minute Final: 310C for 22.6 minutes Cryo: Of Quick Cryo Cool: Off Ambient Temp: 25C


January 2008

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MSD Conditions for SVOCs in Standards and IM Samples. Set up the 5973N MSD with the conditions in Table D11. For other instruments the parameters have to be adapted.

Table D11: MSD Conditions for SVOCs in Standards and IM Samples Tune: standard spectra autotune Data Delay: 13 minutes (60 m column) Scan Mode: 29 to 460 amu Transfer line: 280C Quadrupole: 150C

(GC oven @ 100C)

Scan Rate: 2.7 scans/s Threshold: 100 Source: 230C

Note: Proper training is required to operate the Gerstel TD instrument and the Agilent Technologies GC/MSD instruments.


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Appendix E Table E1: Description of the Substance Classification

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Example for Notation

Comment

toluene, methylbenzene

Mass spectra and retention time of referencing substance correspond (reliable identification).

? 1,1-bis(p-toloyl)ethane 210 195 179 104

Prefixed question mark, no reliable identification by mass spectra and retention time, but the given substance seems to be the correct one. Noticeable mass fragments are given.

? alcohol, 31 57 85

Prefixed question mark + substance class, typical mass fragments or known mass fragment pattern give a hint to substance class.

? 54 76 99 109

No conclusions on possible substance.

isomeric paraffinic fraction, boiling range “n-C16 to n-C26”

For oil-mountains the substance class and circa boiling range (acc. to n-alkanes) should be indicated. As retention time applies the retention time of the oil-mountain maximum.

cyclohexanone + ?

An identified peak is overlaid by one or more substances.

artifact

Peak which is not originated in the sample or is built in the system.


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Appendix F Calculation of the concentration in µg/g (ppm) toluene and hexadecane equivalents: Mass (S) Emission = ------------Area (S)

Area (P) x --------------Weight (P)

Mass (S): injected mass of the individual standard in µg (toluene for VOCs, n-hexadecane for SVOCs) Area (S): peak area in SCAN mode for the individual standard (counts) Area (P): peak area in SCAN mode for the individual analyte or the total peak area for the calculation of the total amount. Weight (P): weight of the sample in grams. The results for the total amount and the individual amount are given as toluene equivalents for the VOCs and hexadecane equivalents for the SVOCs.


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Appendix G Data Form G1: Example for Test Result Form for VOCs Results Single Substances GMW 15634 Vehicle Interior Material VOC Laboratory Order number (internal): Date of production:

Sample name:

Date of sampling: Part No.:

Total weight of the part in the car:

Supplier:

Total size of the part in the car:

Chromatogram No.: Data path:

Dimension of analysed sample:

Editor:

Weight of analysed sample:

sample 1

sample 2

Single Substance Area-%

Toluene Area-%

Date: Method:

total emission value (µg/g)

VOC

highest value

µg/g

second value

µg/g

Sum of the following identified substances in ppm (as toluene equivalent) Retention Time (min)

RI

substance name

CAS-No.

Number of peaks

µg/g

Sum of the identified or dedicated substances

Comments for over all estimation

Instrumentation used Column used



Dimension of the whole part in the interior





Chromatogram number

Name of the sample





Date of analysis

Drawing number





Analysis method

Supplier





Total VOC and total FOG amount

Date of production/sampling date





List of identified analytes and amount

Weight of the sample analysed





Risk assessment of the results

Dimensions of the sample analyzed

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Note: The test result form includes the following information:


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Data Form G2: Example for Test Result Form for SVOCs Results Single Substances GMW 15634 Vehecle Interior Material SVOC Laboratory Order number (internal): Date of production:

Sample name:

Date of sampling: Part No.:

Total weight of the part in the car:

Supplier:

Total size of the part in the car:

Chromatogram No.: Data path:

Dimension of analysed sample:

Editor:

Weight of analysed sample:

sample 1

Date: Method:

SVOC

total emission value (µg/g)

highest value

µg/g

Sum of the following identified substances in ppm (as n-hexadecane equivalent) Retention Time (min)

RI

substance name

CAS-No.

Number of peaks

Substance %

Area- n-Hexadecane Area-%

µg/g

Sum of the identified or dedicated substances

Comments for over all estimation

Instrumentation used Column used

Note: The test result form includes the following information:



Dimension of the whole part in the interior





Chromatogram number

Name of the sample





Date of analysis

Drawing number





Analysis method

Supplier





Total VOC and total FOG amount

Date of production/sampling date





List of identified analytes and amount

Weight of the sample analysed





Risk assessment of the results

Dimensions of the sample analyzed


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SS Screen Glass Wool

Tenax TA

Tenax TA

Glass Wool

Glass Wool

15 mm

15 mm

TenaxTA GTDT

15 mm

Glass Frit

15 mm

Glass Frit

30 mm

30 mm

60 mm

Glass Wool

60 mm

SS Screen

GMW15634

133 mm

133 mm


IM GTDT

Figure G1: Side Profiles of a TenaxTA GlassThermal Desorption Tube (GTDT) and an Interior Materials Glass Thermal Desorption Tube (IM GTDT), Respectively (Not to Actual Scale)

Syringe

Standard Injection

He Flow SLH Adapter (1/2) Glass Frit

Flow Regulator

60 mm

Tenax TA

He Flow

Glass Wool SS Screen He Flow

Gas Meter

SLH Adapter (2/2) He Flow

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Figure G2: Side Profile of a Gerstel Tube Spiking Septumless Head (SLH) Adapter, with a Helium (He) Flow Meter Connected Upstream, and a Gas Meter Connected Downstream (Not to Actual Scale) © Copyright 2008 General Motors Corporation All Rights Reserved

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Figure G3: Merged Total Ion Chromatograms (TICs) of n-C5 to n-C16 VOCs Eluting w/60 m Column (Conditions of VOC run) Table G1: Corresponding Chromatogram (Figure G3) Retention Times (RT), Compound Names, and Chemical Abstract Services Number (CAS#). RT (minutes)

Compound

CAS#

4.59

n-C5

n-pentane

109-66-0

5.95

n-C6

n-hexane

110-54-3

8.54

n-C7

n-heptane

142-82-5

12.65

n-C8

n-octane

111-65-9

17.77

n-C9

n-nonane

111-84-2

22.91

n-C10

n-decane

124-18-5

27.15

n-C11

n-undecane

1120-21-4

30.74

n-C12

n-dodecane

112-40-3

33.85

n-C13

n-tridecane

629-50-5

36.25

n-C14

n-tetradecane

629-59-4

38.16

n-C15

n-pentadecane

629-62-9

39.76

n-C16

n-hexadecane

544-76-3


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Figure G4: TIC of n-C16 to n-C32 SVOCs Eluting w/60 m Column (Conditions of FOG Run, Solvent Delay at 13 Minutes) Table G2: Corresponding Chromatogram (Figure G4) Retention Times, Compound Names, and CAS# Compound

CAS#

14.05

n-C16

n-hexadecane

544-76-3

15.10

n-C17

n-hexadecane

629-78-7

16.14

n-C18

n-octadecane

593-45-3

17.15

n-C19

n-nonadecane

629-92-5

18.13

n-C20

n-eicosane

112-95-8

19.07

n-C21

n-heneicosane

629-94-7

19.99

n-C22

n-docosane

629-97-0

20.87

n-C23

n-tricosane

638-67-5

21.80

n-C24

n-tetracosane

646-31-1

22.82

n-C25

n-pentacosane

629-99-2

23.96

n-C26

n-hexacosane

630-01-3

25.28

n-C27

n-heptacosane

593-49-7

26.82

n-C28

n-octacosane

630-02-4

28.66

n-C29

n-nonacosane

630-03-5

30.87

n-C30

n-triacontane

638-68-6

33.57

n-C31

n-hentriacotane

630-04-6

36.85

n-C32

n-dotriacontane

544-85-4


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RT (minutes)

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1. sample

2. sample

1. 2. 3. 2 cm away from the border

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Figure G5: Scheme of Sample Preparation


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