Dr Peter Hughes Markes International Ltd Material Emissions Specialist Innovations to improve repeatability and reduce costs when testing (s)VOC emissions / content from car trim materials and In Vehicle Air Quality Dr Peter Hughes Markes International Ltd Material Emissions Specialist

Regulatory and Standard Method Developments for Materials Emissions Testing

ISO/CEN – ‘Horizontal’ standards Construction products (and furnishings..) (ISO TC 146, SC6 and CEN TC264 WG7) ISO 16000-6 – Tenax tube, TD-GCMS(/FID) analysis EN ISO 16000-9 – small chamber EN ISO 16000-10 – FLEC cell EN ISO 16000-11 – selection and preparation of samples ISO CD 16000-24 – sorptive building materials (Japan) Proposed new work item: method for SVOC emissions with high temp micro-chamber. Japanese draft submitted - currently being balloted Includes other parts on formaldehyde, tracer gas ventilation tests, etc Car cabin air quality and car trim emissions (new work item for ISO TC 146, SC6) ‘Garage-sized’ chamber test Chamber VOCs Chamber SVOCs Emissions screening method (indicative – would follow after above 3)

Regulatory and related drivers around the world Europe (and ROW) – Construction products directive Europe (and ROW) – REACH Germany – Flooring certification and the AgBB scheme US – California, Washington State, etc and the CHPS programme US EPA ‘Carpet Dialogue’, CRI and the US ‘Greenguard’ label Japanese labelling schemes for construction products Japanese regulation of 12-13 VOCs in car cabin air Koreans thinking of doing something similar (Dr Mangoo Kim) Chinese expect to implement controls on car cabin air quality from 2008

Japanese Automotive Manufacturers Association (JAMA) JAMA’s targets are as follows: “New models of passenger cars to be sold from fiscal 2007 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. An independent program to reduce VOC’s in commercial vehicles, including trucks and buses, is now being worked upon, and is expected to be announced within fiscal 2005.”

European Auto Industry Voluntary program (at the moment) for Auto manufacturers as set up by the European Automotive Industry (VDA) Similar to JAMA program in that in cabin air quality must adhere to quality guidelines The list of target compounds and specified concentration limits defined by TÜV (Technischer Überwachungs-Verein Nord)

JAMA and TÜV Guidelines Most European car manufacturers are interested in evaluating Vehicle Interior Air Quality (VIAQ) / Material emissions

Monitoring In Vehicle Air Quality (IVAQ) Sample air inside vehicle cabin – pumped sampling - retain compounds onto sorbent tube Tubes analysed using TD-GC/MS Sampling techniques available include JAMA and CSIRO technique Both techniques employ Thermal Desorption

VDA Techniques available for monitoring Material Emissions from vehicle trim components VOC’s Fogging S-VOC’s Odour VDA 270 – Odour VDA 275- Formaldehyde VDA 276- VOC, s-VOC Test Chamber VDA 277- VOC Headspace VDA 278- VOC, s-VOC Thermal Desorption

Analytical Options for Mat Em. Testing 1. Emission Chamber 2. Emission Cell External - Certification VOC emission profiles under ‘real-use’ conditions are best obtained using test chambers (VDA276) 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 (VDA 278) Create a barrier to prevent emissions contributing to environment- evaluate effectiveness / permeability of barrier 3. Micro-chamber Overview of the Typical approaches available for mat em testing can be broken up into 2 distinct areas Evaluating materials emissions under simulated real use conditions or by preventing potential hazourdous or toxic emission sby reducing their presence in the first place ie. reduce initial content or by employing suitable barriers to prevent emissions being released into the environment. All approaches require thermal desorption analysis 5. Barriers/ Permeation 4. Direct Desorption

VDA 276- Test Chamber Method Line Time [h:min] Temp. Target [oC] Air Change [1/h] Air-in humidity [oC/ %rh][1] Procedure Pre-conditioning 1 70 Maximum 10.4/4.0 2 -0:30 Prepare test chamber if needed Test 3 0:00 65 0.40 10.4/5.0 First conditioning phase 4 2:00 Start air sampling: BTXE/S-aromatics aldehydes and ketones survey analysis any other sampling 5 6 4:30 8:00 100 0.44 ? Second conditioning phase start fogging sampling end fogging sampling [1] dew point temperature or relative humidity at 65°C and 1.013 x 105 Pa

Direct Thermal Desorption-VDA 278 A number of voluntary labelling schemes which promote ‘Low VOC’ products actually rely on product content testing rather than emissions testing in order to comply with the scheme (e.g. using US EPA Method 311 for paint). The European automotive industry, adopts a similar approach to testing emissions from car trim components. Their Method VDA 278 specifies direct desorption of materials, at elevated temperatures, to assess both VOCs and SVOCs (fogging) components. Residual Solvent analysis- pharmaceutical companies

VDA 278 – VOC and sVOC content testing Direct Thermal Desorption Used to minimise the risk from emissions by ensuring that materials do not contain significant concentrations of toxic / odorous compounds in the first place. Small section of material placed inside of empty sorbent tube and content thermally extracted Desorbing for 30 minutes at 90°C - VOC’s up to n-C20 followed by 60 minutes at 120°C - SVOC n-C16 to n-C32

Internal QC- Direct Desorption (VDA 278) Valve Configuration 1- off line to GC Sample tube Heated To GC

Secondary Desorption (VDA 278) Valve Configuration 2- on line to GC GC/MS/FID To GC

Results- PVC Foam sheet VOC content analysis by VDA 278 Desorbing for 30 minutes at 90°C VOC’s up to n-C20 Compound toluene (C7H8) 2. 1-methoxy-2 propylacetate (C6H12O3) 3. 2-ethyl-1-hexanol (C8H18O) 4. 1-methyl-2-pyrrolidinone (C5H9NO) 5. 2-(butoxyethoxy)-ethanol (C10H20O4) 6. 1-decanol (C10H22O) 7. butylated hydroxytoluene (C15 H24 O)

Results- Artificial leather Fogging Compounds by VDA 278 Desorbing for 30 minutes at 90°C followed by 60 minutes at 120°C SVOC n-C16 to n-C32 Compound 2,6-di-tert-butyl-4-sec-butyl phenol (C16H350) 2. decanedioic acid, dimethyl ester (C12H2204) 3. 2-hexyl-1-decanol (C16H340) 4. bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (C25H56N204) 5. di-i-decyl phthalate (C28H4604) 6. di-n-decyl phthalate (C28H4604)

Direct Thermal Desorption for Troubleshooting (Example: Discoloration of Leather) White leather upholstery discoloured (turned yellow) in patches Direct desorption of the discoloured sample (top) showed high concentration of natural oils Direct desorption of a sample of white (control) leather (bottom) shows high concentrations of detergent. The leather upholstery had not been adequately treated with detergent Discoloured Portion Natural oil Detergent Control Portion

Direct Desorption (VDA 278) Summary Compatible with many materials Can be used for complete (quantitative) extraction Can provide a representative profile of the (S) VOC content of a material VOC/SVOC simultaneous analysis is readily achieved Limitations- small sample size might not be representative of the whole sample Direct correlation between conventional emissions testing difficult- due to bulk desorb’n rather than surface, elevated temps., and small sample size.