1、 WORLDWIDE ENGINEERING STANDARDS Test Procedure GMW15600 Determination of Aldehyde and Ketone Emissions in Vehicle Interior Cabin Air Copyright 2013 General Motors Company All Rights Reserved November 2013 Page 1 of 9 1 Scope Note: Nothing in this standard supercedes applicable laws and regulations.
2、 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 quantitative determination of aldehyde and ketone emissions in vehicle interior cabin air, utilizing a coated solid adsorbent follow
3、ed by High Performance Liquid Chromatography (HPLC) with ultraviolet (UV) detection. 1.2 Foreword. The determination of aldehydes and ketones in vehicle cabin air is essential to meet customer and regulatory requirements in global automotive markets. Concentrations are in the parts per million (ppm)
4、 ranges, which warrant accurate, analytical measurements. This test procedure is based on test method EPA T0-11A. It has been updated to reflect new technology in air sampling and analytical instrumentation. Note: There is no direct correlation between the limits on material, component, and vehicle
5、level due to the high complexity of chemical interactions, unpredictable influence of different part sizes and addition, interaction and elimination of their emissions. 1.3 Applicability. This test procedure can be used for all air samples for the determination of aldehyde and ketone emissions, incl
6、uding cabin air inside vehicles in a stationary or dynamic mode. The results will provide complementary information to interpret findings in GMW16818 and GMW15635 2 References Note: Only the latest approved standards are applicable unless otherwise specified. 2.1 External Standards/Specifications. E
7、PA T0-11A ISO 12219-1 MOLIT 2013-549 HJ/T400 JASO Z125 2.2 GM Standards/Specifications. GMW15635 GMW16818 2.3 Additional References. 3 Resources 3.1 Facilities. The cabin air samples shall be collected inside a vehicle in a garage or in a stable environment with low background levels of aldehydes
8、. If data is acquired for regulatory purposes, the use of a vehicle sampling chamber may be required. The test chamber requirements and sampling protocol may differ for different regulations. 3.1.1 Calibration. The test facilities and equipment shall be in good working order and shall have a valid c
9、alibration label. 3.1.2 Alternatives. Alternative test facilities and equipment may also be used. However, all measuring variables as specified in this standard shall be determined correctly with respect to their physical definition. Copyright General Motors Company Provided by IHS under license wit
10、h General Motors CompanyNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15600 Copyright 2013 General Motors Company All Rights Reserved November 2013 Page 2 of 9 3.2 Equipment. This test procedure utilizes commonly available eq
11、uipment and instrumentation. Specific instrumentation and test conditions are noted in all the tables and figures in Appendix A through Appendix C. Other equipment can also be used when compatibility has been shown. 3.2.1 Test Apparatus. 3.2.1.1 High performance liquid chromatograph with (binary) pu
12、mp, solvent degasser, heated column compartment, auto sampler (optional), variable wavelength, or diode array detector, and computer based controller and data evaluation. System must be capable of gradient operation to 3.5 mL/minute and 350 bar (maximum), and ultraviolet (UV) detection at 360 Nm to
13、365 Nm. 3.2.1.2 HPLC column capable of separating the 2, 4-Dinitrophenylhydrazine (DNPH) derivatives of the specified aldehydes/ketones using gradient elution conditions. The column is critical for this procedure. 3.2.2 Sample Pump. Portable sampling pump with a minimum flow range between 50 mL/minu
14、te to 1000 mL/minute (e.g., Mine Safety Appliance Number 49772 or SKC AirCheck 2000). 3.2.3 Flow Calibrator. Appropriate flow calibrator (e.g., DC-1 flow calibrator, ) should be used to calibrate the sampling pumps prior to sampling. 3.2.4 Sample cartridges filled with 2, 4-DNPH on silica gel. Cartr
15、idges should have a capacity of 70 g of formaldehyde and blank values of formaldehyde 24 h is expected before analysis. 4.1.2 HPLC Determination of the Concentration of Aldehydes and Ketones. 4.1.2.1 Calibration Standards and Chromatograms. Calibration standard solutions of the aldehydes and ketones
16、 have to be prepared in concentrations of 0.1 g/mL to 15 g/mL (related to the corresponding carbonyl compound) in acetonitrile. 4.1.2.1.1 Calibration curves are created by measuring the calibration solutions by HPLC according to the test conditions in the tables and figures in Appendix A through App
17、endix C. For example: If using a Restek Ultra C18 column, use the HPLC instrument and solvent conditions in Appendix A, Table A1 and Table A2. See Appendix A, Figure A1 for chromatogram example. If using a Restek Allure AK 5 column, use the HPLC instrument and solvent conditions in Appendix B, Table
18、 B1 and Table B2. See example of chromatogram in Appendix B, Figure B1. If using a Phenomenex Synergi 4 m maximum column, use the HPLC instrument and solvent conditions in Appendix C, Table C1 and Table C2. See example of chromatogram in Appendix C, Figure C1. 4.1.2.1.2 Each measuring sequence shoul
19、d start with pure solvent. Afterward, calibration standards are measured with increasing carbonyl content (e.g., 0.1, 0.3, 0.5, 1.0, 3.0 and 15 g/mL). 4.1.2.1.3 Individual peaks in the samples are identified by their retention times and quantitated by evaluation of their peak areas. 4.2 Conditions.
20、4.2.1 Environmental Conditions. The environmental conditions are described in the respective sampling protocols that are 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,
21、 test certificates, reports, etc. 4.2.3 Instrument. Set up the HPLC instrument with the conditions given in Appendices A, B, C, or equivalent. 4.2.4 Analysis. Each measurement should start with pure solvent followed by a standard solution. 4.2.4.1 Vials containing the derivatized carbonyl samples ca
22、n be placed after the standard, starting with the blank solution. Run the analysis sequence, injecting an aliquot from each vial using the HPLC conditions previously developed. Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproduction or
23、networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15600 Copyright 2013 General Motors Company All Rights Reserved November 2013 Page 4 of 9 4.3 Instructions. The operating parameters for the HPLC instrument are given in the tables and figures of Appendix A throu
24、gh Appendix C with three (3) different acceptable columns. 4.3.1 Air sample cartridge (exposed cartridge or blank cartridge) will be attached to a 10 mL or 20 mL polyethylene syringe filled with acetonitrile. The cartridge should be attached so that the acetonitrile flows through it in the opposite
25、direction as the air sample flowed through it. Elute the cartridge slowly approximately 2.5 mL/minute into a 5 mL volumetric flask and bring the liquid to the mark. Cap the volumetric flask, mix, and label it. Transfer an aliquot of the eluate to the HPLC. 5 Data 5.1 Calculations. Calculation of ald
26、ehyde and ketone concentrations is done by first identifying the individual peaks in the samples by their retention times and quantitating the peak areas against the calibration curves (external standard calibration). To determine the concentration of individual aldehydes and ketones in the interior
27、 air of the vehicle, the following formula is used: C1 x V1 Cald_ket = _ x 1000 V2 Where: Cald_ket = concentration of aldehyde or ketone g/m3 in vehicle interior air C1 = concentration of aldehyde or ketone by HPLC g/mL V1 = total volume solution of the derivatized reaction (5.0 mL) V2 = volume of i
28、nterior air sampled in liters 1000 = conversion from liters to m3 The values obtained from the HPLC (in g/mL) are multiplied by the volume used to elute the sampling cartridge (5 mL) and divided by the volume of cabin air sampled in liters to give final results in g/L. Results are converted to g/m3
29、by multiplying by 1000 L/m3. 5.2 Interpretation of Results. The concentrations of the aldehydes and ketones are a measure of the amount of carbonyls in the cabin air of the vehicle in question. Assessment as to the air quality of the cabin air depends on the standards established by the regulatory a
30、gencies in the various global markets. 5.3 Test Documentation. The results are displayed in a report from the data system. (Appendix A, Figure A1, Appendix B, Figure B1, and Appendix C, Figure C1). 5.4 Report. A report documenting all of the vehicle conditions and results shall be prepared according
31、 to the template in Appendix D, Table D1. 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 safet
32、y 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. DNPH Dinitrophenylhydrazine EPA Environmental Protection Agency HPLC High Performance Liquid Chromatography ISO International
33、 Organization for Standardization ppm parts per million RP Reversed Phase 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 GMW15600 Copyright
34、 2013 General Motors Company All Rights Reserved November 2013 Page 5 of 9 UV Ultraviolet VIAQ Vehicle Interior Air Quality VIN Vehicle Identification Number 8 Coding System This standard shall be referenced in other documents, drawings, etc., as follows: Test to GMW15600 9 Release and Revisions Thi
35、s standard was originated in April 2007. It was first approved by the Global Vehicle Interior Air Quality Team in November 2007. It was first published in January 2008. Issue Publication Date Description (Organization) 1 JAN 2008 Initial publication. 2 NOV 2013 Updated to current template. (Interior
36、 Air Quality/Volatile Organic Compound Global Subsystem Leadership Team) 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 GMW15600 Copyright
37、2013 General Motors Company All Rights Reserved November 2013 Page 6 of 9 Appendix A Figure A1: Method A, HPLC Chromatogram of Aldehyde and Ketone DNPH Derivative Standards. Table A1: Method A, HPLC Instrument Conditions Column Restek Ultra C18 5 m 150 mm 4.6 mm Temperature 40 C Detector 365 Nm, 20
38、Nm bandpass Injection Volume 20 L Pump Flow Rate 1.5 L/minute Solvent A HPLC-Grade Water/HPLC-Grade Tetrahydrofuran (70/30) Solvent B HPLC-Grade Acetonitrile Table A2: Method A, HPLC Solvent Gradient Conditions Time (Minutes) Solvent B (Percent %) 0 25 12 50 13 50 13.1 25 Note: Run Time: 16 minutes.
39、 m i n0 2 4 6 8 10 12m AU051015202530D AD 1 A, Si g = 3 6 5 , 2 0 R e f = 5 0 0 , 2 0 ( SJS T EST2 . D )0.8601.1811.2353.281-Formal4.052-Acetal4.938-Acetone5.346-Acrolein5.681-Propional6.666-Crotonal6.905-MEK7.180-Methacrolein7.500-Butyral8.049-Benzal9.632-Valeral9.929-Tolual11.999-HexanalCopyright
40、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 GMW15600 Copyright 2013 General Motors Company All Rights Reserved November 2013 Page 7 of 9 Appendix
41、B Figure B1: Method B, HPLC Chromatogram of Aldehyde and Ketone DNPH Derivative Standards Table B1: Method B, HPLC Instrument Conditions Column Restek Allure AK 5 m 200 mm 4.6 mm Temperature 40 C Detector 365 Nm, 20 Nm bandpass Injection volume 20 L Pump Flow rate 1.5 mL/minute Solvent A HPLC-Grade
42、Water Solvent B HPLC-Grade Acetonitrile Table B2: Method B, HPLC Solvent Gradient Conditions Time (Minute) Solvent B (Percent %) 0 60 8 65 10 90 12 90 12.1 60 Note: Run Time: 16 minutes. m i n0 2 4 6 8 10m A U05101520253035D A D 1 A , S i g = 3 6 5 , 2 0 R e f = 5 0 0 , 2 0 ( S J S S J S C A L 0 1 .
43、 D )4.359-Formal5.398-Acetal6.528-Acrolein6.778-Acetone7.037-Propional8.029-Crotonal8.478-Methacrolein8.778-Butyral9.044-MEK10.212-Benzal10.595-Valeral11.206-Tolual11.466-HexanalCopyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproduction or
44、 networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15600 Copyright 2013 General Motors Company All Rights Reserved November 2013 Page 8 of 9 Appendix C Figure C1: Method C, HPLC Chromatogram of Aldehyde and Ketone DNPH Derivative Standards Table C1: Method C, HP
45、LC Instrument Conditions Column Phenomenex Synergi 4 m Maximum Reversed Phase (RP) 80A, 150 mm 2 mm Temperature 25 C Detector 360 Nm, 20 Nm Bandpass Injection volume 10 L Pump Flow Rate 0.2 mL/minute Solvent A HPLC-Grade Water/HPLC-Grade Tetrahydrofuran (75/25) Solvent B HPLC-Grade Acetonitrile Tabl
46、e C2: Method C, HPLC Solvent Gradient Conditions Time (Minute) Solvent B (Percent %) 0 30 16 90 20 90 25 30 30 30 Note: Run Time: 16 minutes. -505101520253035404550550 2 4 6 8 10 12 14 16 18 20 22 24m i nm A U13.936Benzaldehyde7.044Formaldehyde8.689Acetaldehyde13.070Methacrolein12.485Crotonaldehydey
47、de11.318Propionaldehyde10.787Acrolein10.209Acetone13.498Butyraldehyde17.400Hexanaldehyde15.532ValeraldehydeD A D 1 A , S i g = 3 6 0 , 2 0 R e f = 4 0 0 , 1 0 0 ( A L D -K E T A L D 0 0 0 5 9 . D )Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for Resal
48、eNo reproduction or networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15600 Copyright 2013 General Motors Company All Rights Reserved November 2013 Page 9 of 9 Appendix D Table D1: Report Format Results from GMW15600 of Vehicle Interior Air Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-
