"What s inside your car?

Transcription

1 "What s inside your car? Car interior emissions testing using Thermal desorption GC/MS analysis Inge de Dobbeleer EU GCMS specialist ThermoFisher Lara Kelly Sales Manager Markes

2 Thermal desorption

3 The Thermal Desorption Process On-line Electrically-cooled focusing trap Direct desorption of materials Canisters Sorbent Tubes Headspace 1-2 µl injection of vapour into GC(MS) 3 Water and volatile interferences may be purged to vent

4 What can be analysed by TD? VOC / SVOC Yes C 2 to n-c 4 (b.p. <5 C), GC analysis Matrix compatible with high temperatures required No Compounds which are not compatible with standard gas chromatography CH 4 > n-c 4 (non-volatiles) Special GC analysis, e.g. on-column injection Most inorganic (permanent) gases (O 2, O 3, CO 2, SO 2, NO 2, etc. Exceptions include H 2 S, N 2 O & SF 6 ) 4

5 Thermal desorption (TD) instruments TD sampling accessories/consumables 5

6 Autosampler and Sample tubes DiffLok - Caps Sample Tubes (Glass) Standard- Tubes (Tenax) 6

7 Electrically-cooled focusing trap Gas flow during focusing Sorbents Weak Medium Strong Narrow-bore inlet/outlet end Gas flow during trap desorption Collar for easy trap withdrawal and installation Inert and high thermal conductivity Maximum trapping efficiency: -3ºC & 4 sorbents Simultaneous VOC & SVOC analysis Maximum sensitivity Reduces analytical interference 7

8 Stage 1: Primary (tube) desorption with optional (inlet) split Intensity Heated valve To GC Time 8

9 Stage 2: Secondary (trap) desorption with optional (outlet) split Intensity Heated valve To GC Time 9

10 Advantages of Markes TD All applications on one platform C 2 to n-c 4 AND reactive compounds plus high and low concentrations - means versatility Cryogen-free cooling reliability and low running costs Capacity and versatility up to 1 tubes plus up to 8 cans or online means high capacity and fast return on investment SecureTD-Q as standard for repeat analysis and validation ECC and optional electronic mass flow control of TD split/desorb flows Splitless operation with high res. capillary for optimum sensitivity Optional tube tagging for enhanced tube and sample tracability Uniquely effective tube seals for TD automation offering simple/robust automation Standard method compliant: leak test, purge to vent, backflush trap.. 1

11 ISQ

12 The ISQ: single quad MS Heated source: ion volume, repellor, lenses, RF prefilter Solid, highly inert material ensures reliable performance in all ionization modes, including EI and CI Dual filament cartridge Two filaments in same magnetic orientation Filament lens assures that both filaments will remain protected, for longer life even with redundancy The S-Shaped Ion Guide Reduces neutral noise created by excited helium neutrals striking the detector, resulting in lower detection limits and better selectivity Autotune: Complete and standardized autotune algorithm for excellent day to day variability 12

13 Maintenance without venting and without wires Step 1. Insert removal tool Step 2. Remove source Step 3. Hot source is held in tool Step 4. Push source out of tool 13

14 Relative Abundance The ISQ: True Fast scanning Theoretical (scan/sec) Actual (scans/sec) d:\training\fs282 28/2/21 11:33:35 new 1pgOFN, at scan rate 25 amu/s, factory spec RT: SM: 5B NL: 1.79E4 m/z= MS fs282 NL: 2.4E4 m/z= MS fs283 NL: 2.28E4 m/z= MS fs286a NL: 2.4E4 m/z= MS fsre Time (min) 14

15 Relative Abundance Relative Abundance FS and SIM simultaneous RT: FullScan 1.53 SM: 5G Selected 8 ion 49 in FS S/N 33 8 SIM mode m/z49 6 S/N RT: RT: 11.6 SN: 33RMS SM: 5G RT: 11.6 SN: 26758RMS RT: SN: 546RMS Time (min) 2 Simultaneous FullScan and SIM: One NL: 4.49E6 injection only TIC F: with + c Full ms [35.-3.] MS a83 screening of unknowns quantitation of known compounds at very low level RT: 11.6 SN: 33RMS RT: 11.6 SN: 26758RMS NL: 5.5E4 m/z= F: + c Full ms [35.-3.] MS ICIS a83 Datapoints In SIM: approx 2 In FS: approx 2 NL: 7.48E4 m/z= F: + c SIM ms [ , , , , ] MS ICIS a83 RT: SN: 546RMS Time (min) NL: 5.5E4 m/z= F: + c Full ms [35.-3.] MS ICIS a83 NL: 7.48E4 m/z= F: + c SIM ms [ , , , , ] MS ICIS a83 15

16 Rules and regulations

17 German regulations Voluntary program (at the moment) for Auto manufacturers as set up by the German automotive industry (VDA) Cabin air quality must adhere to quality guidelines VDA 27 - Odour VDA Formaldehyde VDA VOC, s-voc Test Chamber VDA VOC Headspace VDA VOC, s-voc Direct desorption The list of target compounds and specified concentration limits defined by TÜV (Technischer Überwachungs-Verein Nord) 17

18 Japanese regulations JAMA s Japanese Automotive Manufacturers Association: New models of passenger cars to be sold from fiscal 27 must satisfy the indoor concentration guidelines established for 13 VOCs by the Ministry of Health, Labour and Welfare. Each carmaker must continuously strive to reduce VOC concentration in passenger compartments. Vehicles covered by the guidelines are passenger cars manufactured and sold domestically. 18

19 JAMA and TÜV Guidelines 19

20 American regulations Manufacturer specific Joint ventures between some manufactures Limit of compounds taken from California s OEHHA list Test chambers 2

21 21 Chronic Reference Exposure Level (REL)s

22 Harmonisation: Regulations and Methods ISO Indoor Air of Road Vehicles ISO Whole vehicle test chamber -Specification and method for the determination method for the determination of volatile organic compounds in car interiors ISO Determination of the emissions of volatile organic compounds from car trim components Bag method (Screening method) ISO Determination of the emissions of volatile organic compounds from car trim components Micro-chamber method ISO Determination of the emissions of volatile organic compounds from car trim components Small chamber method 22

23 Methods External - Certification VOC emission profiles under real-use conditions are best obtained using test chambers or cells with sorbent tube sampling and TD-GC(-MS) analysis. Internal QC - Prevention Direct thermal desorption / thermal extraction of materials - Measures VOC content as an indication of emission potential 23

24 ISO Determination of the emissions of volatile organic compounds from car trim components Micro-chamber method Surface-only or bulk emissions testing 4 or 6 samples/hour Sorbent tubes ((S)VOC) or DNPH cartridges (H 2 CO) Parameters: 65 C equilibrate for 2 minutes. * UK patent application ml/min (VOCs) or 25 ml/min (H 2 CO) Collect vapour for 15 minutes (VOC) or for 2-4 hours (H 2 CO) 24

25 Using the microchamber for bulk/content testing Sample tube Bulk Emissions Ambient/elevated temperature Dynamic Headspace Homogenous sample Air space Sample Heated air stream 25 Proprietary flow control device no pump required

26 Surface emissions Heated lid: The collar projecting from lid defines area for surfaceonly emission testing and minimises ingress of edge emissions Sample tube Air space Sample Spacers to present sample at correct height Heated air stream 26 Proprietary flow control device no pump required Micro-chamber data has been shown to correlate with results from

27 Correlation Studies Small chamber - Days Tedlar bag- Hours Microcham ber- Minutes 27 Micro-chamber emission screening methods are now being standardised

28 The new car smell

29 29 Trace ISQ and Markes TD-1

30 Analysis Goal The analysis procedure serves to indentify the emissions from non-metallic materials that are used in Automobiles. For example: Textile Carpets Adhesives Sealants Foams Leather Plastics Transparancies Paint Combination Materials 3

31 Description of the method- VOC The samples are thermally extracted and the emissions analyzed using GC/MS There are two half-quantitative summation values determined that determine the emission levels for volatile organic compounds (VOC-Value) and The portion of condensable substances (Fogging-Value) The VOC value according to VDA 278 is the sum of high to medium volatile substances and is reported as toluene equivalent results. Substances with vapor point or retention times for substances up to Eicosan (C2) are determined and reported. The sample is analyzed for 3 minutes at 9 C 31

32 Description of the method determination- Fogging The Fog value is the sum of the heavy volatile substances that occur after the elution time for n-hexadecane. This will be reported as the Hexadecane equivalents. These are the substances in vapor pressure range from n-alcanes C16 up to C32 are reported These substances can condensate at slightly warmer than room temperatures and can be seen as Fog Film on the inside portion of windshields 32

33 33 Sample Preparation TDS

34 Instrument parameters Trace GC Column: TR 5 ms, 3m x.25m x.25 µm Oven: 4 C 2min 3 C/min 92 C min- 5 C/min 16 C min- 1 C/min 28 C 1min Carrier: 1.5 ml/min He, const. Flow ISQ MS EI-Scan: m/z w. 2ms / Scan TDS 1 Flow Path: 2 C Desorption: 3 min at 9 C (VOC) 6 min at 12 C (FOG) Split (high): Desorption: 4,2:1; Injektion: 27:1; Gesamt: 113:1 Split (low): Desorption: 2,1:1; Injektion: 15,6:1; Gesamt: 32,8:1 Trap: 2-stage graphitised carbon Trap low Temp: -3 C; Trap high Temp: 3 C for 3 minutes 34

35 Standard Loading Rig Direct injection of liquid standard C-SLR From: Markes Technical Presentation C-SLR injection of liquid standard in a flow of inert gas 35

36 Standards used in this application QC standard Component Amount injected Ret.time C7.32 µg abs C8.31 µg abs C9.34 µg abs C1.31 µg abs. 9.2 C11.3 µg abs C12.34 µg abs C13.34 µg abs C14.35 µg abs C16.36 µg abs Benzene.34 µg abs Toluene.35 µg abs. 4.3 o-xylene.33 µg abs p-xylene.35 µg abs Ethylhexanole.35 µg abs Diethyladipate.37 µg abs Calibration standard Component Conc. Ret.time Toluol.5 µg/µl 4.3 C16.5 µg/µl µL Std in MeOH are used 36

37 QC standard RT: RT: RT: 2.95 RT: 4.3 RT: 5.29 RT: 6.97 RT: 7.59 RT: 9.2 RT: 1.47 RT: RT: RT: RT: NL: 2.93E8 m/z= MS Genesis 15KompMix_3 ng_1 TIC C9 RT: Ethylhexanol RT: 9.2 C1 RT: 1.47 C11 RT: C12 RT: RT: RT: C13 C14 C16 NL: 6.55E7 m/z= MS Genesis 15KompMix_3 ng_1 m/z= C7 RT: 2.95 C8 RT: 5.29 RT: RT: 2.49 Benzol NL: 3.76E7 m/z= MS Genesis 15KompMix_3 ng_1 m/z= RT: Toluol RT: 4.3 RT: 7.43 RT: 6.97 o-xylol p-xylol NL: 6.13E7 m/z= MS Genesis 15KompMix_3 ng_1 m/z= Diethylhexyladipat RT: 2.38 NL: 4.25E7 m/z= MS Genesis 15KompMix_3 ng_1 m/z= Time (min)

38 Relative Abundance Calibration standard: Toluene + C16: 1µg each c:\xcalibur\...\tds files\std_mix_vda_1 Toluol+C16 je 1ug, Tube /28/21 9:38:24 AM RT: Toluene C16 RT: NL: 7.16E8 m/z= MS Genesis std_mix_vd a_1 4 3 RT: RT: NL: 1.63E8 m/z= MS Genesis std_mix_vd a_ RT: Time (min) NL: 1.17E8 m/z= MS Genesis std_mix_vd a_1 38

39 Relative Abundance VOC analysis in a Leather sample c:\xcalibur\...\p14886_voc_vda_1 1/27/21 7:47:32 PM High Split, 8.7mg, Tube RT: RT: NL: 7.4E8 m/z= MS Genesis p14886_voc _vda_ Sample weight: 8.7mg RT: RT: RT: RT: RT: Time (min) 39

40 Quantitative calculation according to VDA278 using Excel PEAK LIST Calibration std 2µL RT: Number of detected peaks: 2 Apex RT Area Smpl wt. RF Toluene µg.189 C µg.23 PEAK LIST Leather 1, 7.5mg RT: Number of detected peaks: 17 Apex RT Area Smpl wt. Emission µg.82 µg/g µg 1.61 µg/g µg 1.39 µg/g µg.82 µg/g µg.55 µg/g µg.82 µg/g µg µg/g µg.87 µg/g µg µg/g µg 1.38 µg/g µg 1.24 µg/g µg.6 µg/g µg 1.6 µg/g µg.94 µg/g µg 1.9 µg/g µg 4.53 µg/g µg.63 µg/g Sum 81.3 µg/g 4

41 Leather sample according to VDA 278, Weight: 8.7mg c:\xcalibur\...\p14886_voc_vda_1 High Split, 8.7mg, Tube /27/21 7:47:32 PM RT: RT: NL: 7.4E8 m/z= MS Genesis p14886_voc _vda_ VOC- Run RT: RT: RT: RT: RT: Time (min) 41

42 Leather 1: Identification of main components c:\xcalibur\...\p14886_voc_vda_2 High Split, 9.6 mg, Tube RT: /29/21 9:29:22 AM RT: AA: SN: 338 NL: 1.31E9 TIC MS Genesis p14886_voc _vda_ RT: AA: SN: Time (min) p14886_voc_vda_2 # RT: AV: 1 NL: 3.73E8 T: {,} + c EI Full ms [ ] m/z 42

43 Leather sample according to VDA 278, Weight: 8.7mg RT: RT: RT: RT: 4.59 NL: 9.8E8 m/z= MS Genesis P14886_FO G_VDA_ Fog- Run RT: 36.7 RT: RT: RT: RT: 1.45 RT: 31.2 RT: 2.95 RT: 14.2 RT: RT: RT: 44.8 NL: 1.32E7 m/z= MS Genesis P14886_FO G_VDA_4 6 RT: m/z= RT: RT: RT: Time (min) 43

44 PVC sample c:\xcalibur\...\p15191_voc_vda_2 High Split, 1.3 mg, Tube /29/21 12:2:1 PM RT: RT: 4.27 AA: SN: 55 RT: 7.22 AA: SN: 454 RT: AA: SN: 732 RT: AA: SN: 153 RT: AA: SN: 1538 RT: AA: SN: 1297 RT: AA: SN: 137 RT: NL: 7.51 AA: TIC - m/ SN: Genesis 15Komp RT: 14.4 AA: SN: 16 RT: AA: SN: 88 RT: 33.4 RT: 5.27 AA: AA: SN: SN: RT: AA: SN: Time (min) NL: 3.73 TIC - m/ Genesis p15191_ p15191_voc_vda_2 # RT: AV: 67 SB: NL: 3.6E6 T: {,} + c EI Full ms [ ] m/z 44

45 45 Artificial leather VOC

46 46 Artificial leather FOG

47 Conclusions Thermal desorption by Markes: Reliable; every tube is leak tested Controlable; repeat injections through recollection Completely controlled by software Enormously versatile GCMS by ThermoFisher : High robustness High productivity High reliability A powerful combination providing complete thermal desorption GCMS solutions for your lab info: go to and get access to all the applications And for more info on the ISQ and the applications 47