1、 WORLDWIDE ENGINEERING STANDARDS Test Procedure GMW15654 Determination of Volatile and Semi-Volatile Organic Compounds from Vehicle Interior Air Copyright 2013 General Motors Company All Rights Reserved December 2013 Page 1 of 21 1 Scope Note: Nothing in this standard supercedes applicable laws and
2、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 quantitative determination of Volatile Organic Compound (VOC) and Semi-Volatile Organic Compound (SVOC)
3、emissions in vehicle interior air utilizing Tenax TA adsorbent media and Thermal Desorption - Gas Chromatography/Mass Selective Detection (TD-GC/MSD). 1.1.1 Individual VOC and SVOC emissions in different vehicle interior air samples can be identified, quantified, and compared. 1.1.2 In combination w
4、ith GMW15634 the sources of VOCs and SVOCs in vehicle air can be identified. 1.1.3 VOC emissions are in the boiling point range 345 C or chromatographic elution range from n-pentane (n-C5) to n-eicosane (n-C20), and SVOC emissions are in the boiling range 280 C or chromatographic elution range from
5、n-hexadecane (n-C16) to n-dotriacontane (n-C32). This procedure can determine all of these components in vehicle interior air. 1.2 Foreword. The determination of VOCs and SVOCs in vehicle interior air is essential to meet customer and regulatory requirements in global markets. Concentrations are in
6、the micrograms per cubic meter (g/m3) range which warrants accurate analytical measurements. Note: There is no direct correlation between the limits on material, component and vehicle level due to the high complexity of chemical interactions, unpredictable influence of different part sizes and addit
7、ion, interaction and elimination of their emissions. 1.3 Applicability. This test procedure can be used for all air samples for the determination of VOC and SVOC emissions including cabin air inside vehicles in a stationary or dynamic mode. The results will provide complementary information to inter
8、pret findings in GMW3205, GMW3059 and GMW15634. The test procedure can be used to pursue customer complaints regarding odor. The analytical instrumentation described herein is also applicable for GMW15634 to determine the sources of VOCs and SVOCs in interior materials. 1.3.1 This test procedure was
9、 modified from EPA TO-17. 1.3.2 This test procedure complements GMW15600. 2 References Note: Only the latest approved standards are applicable unless otherwise specified. 2.1 External Standards/Specifications. EPA TO-17 ISO 12219-1 JASO Z125 MOLIT 2013-549 HJ/T400 2.2 GM Standards/Specifications. GM
10、W3059 GMW15600 GMW15634 GMW16818 GMW3205 Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15654 Copyright 2013 General Motors Company All
11、Rights Reserved December 2013 Page 2 of 21 3 Resources 3.1 Facilities. The air samples shall be collected inside a vehicle in a garage or in a stable environment with low background levels. If data is acquired for regulatory purposes, the use of a vehicle sampling chamber is required. The test chamb
12、er requirements and sampling protocol may differ for different government regulations. 3.1.1 Calibration. The test facilities and equipment shall be in good working order and shall have a valid calibration label. 3.1.2 Alternatives. Alternative test facilities and equipment may also be used. However
13、, all measuring variables as specified in this standard shall be determined correctly with respect to their physical definition. 3.2 Equipment. This test procedure utilizes commonly available equipment and instrumentation. Equivalent instrumentation and test conditions are suggested in Appendix A, T
14、able A1. 3.2.1 Balance with a sensitivity of 0.01 mg. 3.2.2 Directly Coupled Thermodesorption Gas Chromatography System with Trapping and Split System. 3.2.3 Gas Chromatograph (GC) with mass-selective detector, software and mass spectra libraries. 3.2.4 Gas Chromatograph Capillary Columns. GC Capill
15、ary 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., 50 m 0.52 mm 0.32 m Ultra 2 capillary column). 3.2.5 Tenax TA or equival
16、ent, Glass Thermal Desorption Tubes (GTDT). Compatible with the specific corresponding thermal desorption system. (See Appendix H, Figure H1.). 3.2.6 Tube-Spiking Adapter for loading liquid standards onto Tenax TA tubes and evaporating the solvent. See Appendix H, Figure H2 for details. Other tube-s
17、piking apparatus can 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 conditioning purge gas, and the Tube-Spiking Adapter gas. 3.2.8 Conditioning Tenax TA Glass Thermal Desorption Tubes
18、. Tenax TA tubes must be conditioned thermally with an apparatus designed for that purpose. Set the helium or nitrogen purge gas flow rate to 30 mL/minute to 40 mL/minute for each port. Conditioning consists of heating Tenax TA GTDTs at 320 C continuously for 3 h 10 minutes. After thermal conditioni
19、ng, the sorbent tubes should be packed airtight in aluminum foil or protective end caps to prevent contamination. 3.2.9 Syringes for Spiking Tubes. Ten (10) L, 5 L, and 1 L syringes. 3.2.10 Solvents for Standard Dilutions. Methanol (MeOH), High Pressure Liquid Chromatography (HPLC) grade Dichloromet
20、hane (MeCl2), HPLC grade 3.2.11 Standards and Dilutions. All standards and dilutions are to be kept in sealed containers and refrigerated at 8 C when not in use. 3.2.11.1 Standards of desired VOC and SVOC components at 98% purity (or equivalent). 3.2.11.2 Check standard containing a mixture of 18 in
21、dividual components, 110 G/mL 10 g/mL each in MeOH. (See Appendix B, Section B1.) 3.2.11.3 Calibration standard consisting of toluene, 500 g/mL 50 g/mL in MeOH. See Appendix B, Section B2. 3.2.11.4 Retention Time Lock Standard. The n-Alkane Standard containing n-C5 to n-C32 of 28 individual n-Alkane
22、 components, 2000 g/mL each in MeCl2. 3.2.11.5 Aromatic Performance Standard. Aromatic Standard containing aromatic hydrocarbons, e.g., 14 individual components, 2000 g/mL each in MeOH. 3.2.11.6 Grob-Test Mix for testing the GC column performance. 3.2.12 Sampling Pump. Portable sampling pumps with a
23、 flow calibrator and a minimum flow range between 50 mL/minute to 1000 mL/minute and an appropriate flow calibrator (e.g., type DC-1 flow calibrator BIOS International No. DC-MC-1). Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproductio
24、n or networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15654 Copyright 2013 General Motors Company All Rights Reserved December 2013 Page 3 of 21 3.3 Test Vehicle/Test Piece. The vehicle to be tested is determined by the test director. The actual age of the vehi
25、cle may vary according to the purpose of the test. It may be a used vehicle with a customer complaint or a new vehicle less than 28 days after production as required by sampling protocols. 3.3.1 The nominal temperature in the test vehicle interior air can range from 10 C to 65 C. However, at tempera
26、tures above 30 C, the sampling tube should be placed outside the vehicle to ensure quantitative collection of the VOC and SVOC species. Vehicles may be preconditioned as required, and details should be documented. 3.4 Test Time. A preconditioning procedure (e.g., addressing time, temperature, humidi
27、ty, etc.,) as specified within an individual government regulation must be followed. Calendar time: Up to 2 days Test hours: 6 hours Coordination hours: 4 hours 3.5 Test Required Information. The Vehicle Identification Number (VIN), vehicle build date and the odometer reading shall be recorded, incl
28、uding remarks on the condition of the vehicle and a brief history. 3.6 Personnel/Skills. Proper training is required to operate the instrumentation in this procedure. A professional degree in chemistry, chemical engineering, industrial hygiene or the health sciences is a prerequisite. 4 Procedure 4.
29、1 Preparation. If necessary, the vehicle shall be prepared as it is mentioned in the respective test recommendations (2.1). For global testing, prepare the vehicle according to ISO 12219-1 and use HJ/T400 for vehicles exported to China, JASO Z125 for vehicles exported to Japan, and MOLIT 2013-549 fo
30、r vehicles exported to South Korea. A known volume of vehicle interior air is drawn through preconditioned Tenax TA GTDT sampling tubes at a sampling rate of 100 mL/minute to 200 mL/minute for a period 30 minutes to 1 h. After sampling, the samples and field blanks are capped, labeled, and returned
31、to the laboratory where they are analyzed by TD-GC/MSD to determine the identity and the quantitative amounts of substances in the vehicle interior air. If necessary, an air sample can be drawn 0.5 m outside of the vehicle for background VOC correction. 4.1.1 Vehicle. The vehicle has to be condition
32、ed according to the respective test procedure. 4.1.2 Tube Conditioning. The Tenax TA GTDTs are thermally conditioned before sampling (3.2.8). 4.1.3 Air Sampling. Calibrate the sampling pump, and record the sampling rate. The sampling has to be done on two (2) tubes in parallel. Place the sample pump
33、s and Tenax TA GTDTs in the car with the pumps on the seat and the Tenax TA GTDTs at driver breath level (use the headrest to hold the Tenax TA GTDTs). Assemble the Tenax TA GTDTs and sampling pumps so that the flow direction is that indicated by the labeled arrow on the tube. Use a sampling rate of
34、 100 mL/minute to 200 mL/minute for a period 30 minutes to 1 h. Start the sampling pumps and record the time. Close the vehicle doors and windows. After an appropriate sampling time, open the vehicle doors and stop the sampling pumps, noting the elapsed sampling time. Remove the Tenax TA GTDT air sa
35、mple(s), cap it and label it with the details VIN, sampling time, and flow rate, etc., of the test. Refrigerate the Tenax TA GTDT samples at 8 C if a delay of 24 h is expected before analysis. 4.2 Conditions. 4.2.1 Environmental Conditions. The environmental conditions are described in the respectiv
36、e method used for testing. 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. 4.3 Instructions. The operating parameters for the TD-GC/MCD instrumentation a
37、re given in Appendix C. Table C1 includes the instrument conditions for the Gerstel Thermal Desorption System (TDS) system. Table C2 shows the conditions of the Gerstel Cooled Injection System (CIS) system. Table C3 describes the Agilent GC inlet conditions. Copyright General Motors Company Provided
38、 by IHS under license with General Motors CompanyNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15654 Copyright 2013 General Motors Company All Rights Reserved December 2013 Page 4 of 21 Table C4 shows the split ratio. Table C
39、5 includes the analytical column conditions. Table C6 shows the GC oven conditions and Table C7 the Agilent MSD conditions. Table C8 shows the conditions if a Markes Thermodesorption unit is used. 4.3.1 Spiked Standards. The known standard solutions (g/mL) of sought compounds are spiked on separate
40、preconditioned Tenax TA GTDT tubes. This is accomplished by using an apparatus as described in 3.2.6 and Appendix H, Figure H2. Use a 0.7 L/minute 0.3 L/minute helium flow rate for 3 minutes to 4 minutes to achieve a 2.5 L to 3.0 L total helium volume. Other apparatus can also be used. Create a quan
41、titative calibration curve by spiking preconditioned Tenax TA GTDTs with, 200 ng, 400 ng, 800 ng, 1200 ng, and 1600 ng of sought VOC or SVOC standard(s) depending on the requirements. Record calibration concentrations. 4.3.1.1 Check Standard. Perform a TD-GC/MSD run on a Tenax TA GTDT spiked with 4
42、L per 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 duri
43、ng test runs. Keep a running record of the individual components response and retention times as a method monitor. 4.3.1.1.1 From time to time, a calibration curve is prepared by spiking a number of Tenax TA GTDT with different volumes of the check standard solution (range 0.016 g to 6 g per substan
44、ce 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 (3.2.11.3) in SCAN mode to acquire toluene equivalent data for VOCs and SVOCs (this calibration is used for compounds beyond the specific sought substances). 4.3.1.3 N-
45、Alkane and Aromatics Standards. Perform a TD-GC/MSD run on a Tenax TA GTDT spiked with 1 L of n-Alkane Standard (3.2.11.4) or 1 L of Aromatics Standard (3.2.11.5) in SCAN mode. The retention times of the components in these mixtures are suitable as reference points to determine the retention time in
46、dices of unknown substances (Appendix H, Figure H3 and Table H1), and in this way can be used for an additional check of Mass Selective Detector (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 t
47、he 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 occurri
48、ng in close succession can be used to check the separation efficiency of the chromatographic column. 4.3.2.2 The performance of the mass selective 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
49、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 vehicle interior air
