© 2006 iarc environmental competences: viaq training day dr. g.j.williams, dr.m.w.pharaoh,...
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© 2006 IARC
Environmental Competences:
VIAQ Training Day
Dr. G.J.Williams, Dr.M.W.Pharaoh, P.Madden,
Warwick Manufacturing Group, University of Warwick
M.Griffin
JLR
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© 2006 IARC
ContentContent
Programme background and objectives
Definitions and standards
Sampling techniques
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© 2006 IARC
Environmental Competence Project Environmental Competence Project - Primary Objectives- Primary Objectives
Understand the issues and provide clear direction for the project partners to ensure an effective response to the Integrated Product Policy (IPP).
Develop capability within the supply base to satisfy the emerging requirements for vehicle interior air quality (VIAQ)
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PARD Programme backgroundPARD Programme background
• The Premium Automotive Research and Development (PARD) Programme consists of a portfolio of research and development projects.
• Programme set up in 2003, project activity to be completed by end 2006 and deliverables achieved by 2010
• It is aimed at enhancing the manufacturing and design capabilities of automotive supplier companies, particularly in the West Midlands.
• The programme is supported by the Regional Development Agency, Advantage West Midlands together with numerous partner companies, including a lead partner, Jaguar & Land Rover.
• The International Automotive Research Centre was set up in the University’s Warwick Manufacturing Group to host the programme
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Supplier InteractionSupplier Interaction
Headliner
carpets
facia
trim
Components
(component testing)
Materials
(micro chamber)
Adhesives
Sealants
Assistance to suppliers
Tests, reports, training, material choices
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JAMA Guidelines Overview Substances emitted from vehicle interior may be harmful
Japan (JAMA) are the first country to have released voluntary vehicle interior air quality guidelines– seen as potential future legislation. FULL LIST IN HANDOUTS.
Guideline limits are for 9 compounds including formaldehyde, acetaldehyde and toluene tested at 40°C
SubstanceConcentration guidelines
µg/m3 Issue
Formaldehyde 100 Potential carcinogen, irritant
Acetaldehyde 48 Irritant
Toluene 260 Headaches, fatigue
Xylene 870 Harmful irritant
Ethylbenzene 3800 Toxic agent
Styrene 220 Harmful irritant
Di-n-butyl phthalate 220 Phthalates linked to cancer
Di-n-ethylhexyl phthalate 120 and hormone imbalance
Tetradecane 330
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VOC: VOC:
Sum of VVOC and VOC which easily evaporate from sample Sum of VVOC and VOC which easily evaporate from sample at test-temperature 25 << 100 at test-temperature 25 << 100 ºC/1barr and with in-car ºC/1barr and with in-car concentration at least > 2 times higher than outsideconcentration at least > 2 times higher than outside
FOG (Windscreen Fogging): FOG (Windscreen Fogging):
Sum of VOC and SVOC which evaporate from sample at test-Sum of VOC and SVOC which evaporate from sample at test-temperature > 90 temperature > 90 ºC/1barrºC/1barr
Odour compounds (OC’s):Odour compounds (OC’s):
Organic chemicals with very high vapour pressure and Organic chemicals with very high vapour pressure and readily evaporating at normal pressures and temperatures readily evaporating at normal pressures and temperatures and quite often not detected as VOC’sand quite often not detected as VOC’s
Definitions: In car air quality – what exactly do Definitions: In car air quality – what exactly do the terms mean ?the terms mean ?
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Boiling pointBoiling point TermTerm ExamplesExamples
< 50 < 50 ºCºC Very Volatile Organic Very Volatile Organic Compounds (VVOC)Compounds (VVOC)
Formaldehyde (- 21 Formaldehyde (- 21 ºC)ºC)
Acetaldehyde (20 ºC)Acetaldehyde (20 ºC)
> 50 > 50 ºCºC
< 260 ºC< 260 ºC
Volatile Organic Compounds Volatile Organic Compounds (VOC)(VOC)
Benzene (80 Benzene (80 ºC)ºC)
Toluene (110 ºC)Toluene (110 ºC)
Styrene (145 ºC)Styrene (145 ºC)
Dabco (175 ºC) Dabco (175 ºC)
> 260 > 260 ºCºC
< 400 ºC< 400 ºC
Semivolatile Organic Semivolatile Organic Compounds (SVOC)Compounds (SVOC)
Di-n-butyl phthalate (340 Di-n-butyl phthalate (340 ºC)ºC)
Di-n-ethylhexyl phthalate (390 ºC)Di-n-ethylhexyl phthalate (390 ºC)
> 400 ºC> 400 ºC Particulate Organic Matter Particulate Organic Matter (POM)(POM)
PCBPCB
Definitions: VOC Classification by the WHODefinitions: VOC Classification by the WHO
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Which VOC substances monitored ?Which VOC substances monitored ?
ESIS: R-phrases ECB IARC EC Nr CAS Nr1 Formaldehyde 23 24 25 34 40 43 Carc. Cat 3 200-001-8 50-00-02 Acetaldehyde 12 36 37 40 Carc. Cat 4 200-836-8 75-07-03 Propionaldehyde 11 36 37 38 204-623-0 123-38-6
4 Benzene 23 24 25 36 38 45 46 48 65Carc. Cat. 1 Mut. Cat 2
200-753-7 71-43-2
5 Toluene 11 20 38 48 63 65 67 Repr. Cat 3 203-625-9 108-88-36 Xylene 10 20 21 38 215-535-7 1330-20-77 Ethylbenzene 11 20 202-849-4 100-41-48 Styrene 10 20 36 38 202-851-5 100-42-59 Chlorobenzene 10 20 51 53 203-628-5 108-90-710 Paradichlorobenzene 36 40 50 53 Carc. Cat 3 Carc. Cat 2B 203-400-5 106-46-711 Dichlorobenzene 246-837-7 25321-22-612 Bromobenzene 203-623-8 108-86-113 Parabromochlorobenzene 203-392-3 106-39-814 Bromochlorobenzene 249-303-1 28906-38-9
15 Nitrobenzene 23 24 25 40 48 51 53 62Carc. Cat 2 Repr. Cat.3
Carc. Cat 2B 202-716-0 98-95-3
16 Phenol 20 21 22 23 24 25 34 48 68 Mut. Cat 3 203-632-7 108-95-217 Benzylchloride 20 51 53 246-698-2 25168-05-218 Dimethylamine 12 20 22 34 Carc. Cat 3 204-697-4 124-40-319 Tetrachloormethane 23 24 25 40 52 53 59 200-262-8 56-23-520 Nitrosodimethylamine 26 27 28 45 6121 Dimethylformamide 20 21 36 61 Repr. Cat 2 200-679-5 68-12-222 Di-n-butyl-phtalate 50 61 62 Repr. Cat 2 & 3 201-557-4 84-74-223 Di-n-ethyl- hexyl- phtalate 60 61 Repr. Cat 2 204-211-0 117-81-7
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Which VOC substances monitored? R-phrasesWhich VOC substances monitored? R-phrases
10 Flammable11 Highly flammable12 Extremely flammable20 Harmful by inhalation21 Harmful in contact with skin22 Harmful if swallowed23 Toxic by inhalation 24 Toxic in contact with skin25 Toxic if swallowed26 Very toxic by inhalation27 Very toxic in contact with skin28 Very toxic if swallowed29 Contact with water liberates toxic gas34 Causes burns 36 Irritating to the eyes37 Irritating to the respiratory system 38 Irritating to skin40 Limited evidence of a carcinogenic effect 41 Risk of serious damage to the eyes43 May cause sensitization by skin contact45 May cause cancer 48 Danger of serious damage to health by prolonged exposure50 Very toxic to aquatic organisms51 Toxic to aquatic organisms52 Harmful to aquatic organisms53 May cause long-term adverse effects in the aquatic environment59 Dangerous to the ozon layer60 May impair fertility61 May cause harm to the unborn child62 Risk of impaired fertility63 Possible risk of harm to the unborn child65 Harmful: may cause lung damage if swallowed67 Vapours may cause drowsiness and dizziness
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Evaluation strategy - Equipment and facilitiesEvaluation strategy - Equipment and facilities
Vehicle Testing: performed at Gaydon
Volumetric test: ug/m3
1m3 chamber testing
Volumetric test: ug/m3
Micro-chamber testing
Emission rate test: ug/m2/hr
Thermal desorption – GC/MS
HPLC – being installed later this week
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Evaluation strategy - Test programmeEvaluation strategy - Test programme
Vehicle testing: - Complete vehicle testing performed in line with Japanese Automotive Manufacturers Association (JAMA) voluntary guidelines on a range of new vehicles
Component testing: - Complete car set being tested in chamber - Correlation tests being done to VDA 276
Material testing being done using micro-chamber: - production material - component material
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Test configuration / sampling processTest configuration / sampling process
Air flow rate / sampling time very closely
controlled to give consistency of results.
Results in micrograms per m3
These must be below values given in regulations.
Will effect: health toxicity, odour and fogging.
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Sampling and test protocolSampling and test protocol
Air sampling conditions - Components
Chamber temp.: 40 0C
Heating time : 4.5hr
Heatercase
Chamber
Fill the heated air
Schematic of 4m3 chamber
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U-cte testing set-upU-cte testing set-up
IARC emission lab set-up:
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Single µ- CTE Chamber Assembly
Sample tube
Flow controlling device•10 – 500 ml/min
Air/gas manifold supplying all 6 μ-Chambers
Heated block•Temps. up to 120°C
Micro-chamber•Diameter 45 mm•Depth 28 mm•Volume ~45 cm3
Heated air/gas supply
• The µ-CTE contains 6 Chambers in Total
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Evaluation strategy - Equipment and facilitiesEvaluation strategy - Equipment and facilities
Micro-chamber benefits:
Can collect air samples from up to 6 material samples simultaneously
Highly repeatable and controllable
Can carry out sampling from ambient to 120 degs C
Need only small quantities of sample material (~∅40mm discs)
Rapid sample turnaround (based on 30mins sampling time)
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Sampling and test protocolSampling and test protocol
Materials sampling conditions
Microchamber Parameters:
Micro-cell mode (planar sample, Ø40mm disc)
VOC-free compressed air
40 0C
30 minutes
21 ml/min flow rate
TENAX TA packed steel tubes (200mg)
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1m3 Chamber for VDA276 Testing1m3 Chamber for VDA276 Testing
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1m3 – VDA276 Chamber Specifications1m3 – VDA276 Chamber Specifications
Treated stainless steel for best cleanliness.
Cleaning protocol, plus air samples taken before each test to confirm cleanliness results.
Testing: Chamber conditioning phase 75C followed by sampling regime of 65C. VDA test is at 120mins after sample has been inserted.
Our testing takes air samples (15mins) immediately the test material is inserted and continues for 220mins.
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VDA276 expected concentration profile VDA276 expected concentration profile
Steady stateperiod
Nom
inal
cha
mbe
r co
ncen
trat
ion
Time during test
Sample conditioningperiod
VOC levels minusAir exchange
Oven conditioning
sampling
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Other MethodsOther Methods
Tedlar bag, used by Honda and Nissan
Component placed in a tedlar bag which is filled with clean air. Left in the bag for the duration of the test. Air sampled onto a tube at the end of the test period
Direct desorption techniques
Direct pyrolosis of the material in to the MS.
Heating the material in the thermal desorber which follows the usual GC/MS path.
We have been reluctant to do these are they can cause contamination and increase background levels.
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Surface Interactions Surface Interactions
Still air: surface boundary layer
- area / topography
Bulk Material:- Density- Surface area-VOC Molecular weights-Layered Structures
- foams- adhesives
Surface air flow
Bulk diffusion
Air Diffusion
Rapid Removalof VOCs
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Important criteriaImportant criteria
Selectivity
• Which VOCs can be identified and at which level
=> VOC list
Test capability
• How accurate => correctness / sensitivity (ppm, ppb,,.)
• How precise => repeatability (one lab, same conditions)
=> reproducibility (different labs, same conditions)
In house studies to study these parameters
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GC/MS - Analysis methodGC/MS - Analysis method
Run (Desorb & GC-MS):
1 blank (clean) VOC tube
1 pre-loaded calibration ‘standard’, contains 1ug each of target analytes (16 total)
Collected sample tubes
Process:
Calibrate detector response according to 1ug ‘standard’
Detect and integrate peaks from chromatogram
Analyse mass spectra within those detected peaks
Mass ratios within mass spectrum allow identification of compound
Quantified target compounds & qualitative unknowns
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GC/MS Analysis of ResultsGC/MS Analysis of Results
U-cte: run a minimum if 3 chambers, check flow at beginning and end of sampling.
Quantitative results: those compounds run in the standard can be quantified with respect to their response in the standard.
All others are determined with respect to toluene response in the standard using the relative areas; semi-quant results.
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Analytical process conditionsAnalytical process conditions
Parameter Value Flow rate (all) 20 ml/min Purge 1 min Tube desorption temperature/time 300 oC/8 mins Trap fire 310 oC/3 mins Total split ratio 46:1
Parameter Value
Column 60 m, 0.25 μm
GC oven (start) 40 oC
GC oven Ramp 1 110 oC @ 6 degs/min
GC oven Ramp 2 315 oC @ 15 degs/min
GC oven hold 315 oC for 10 mins
Total time 35.33 mins
Column flow control Constant velocity mode, 24 cm/sec
Ion source 200 oC
Interface 315 oC
m/z range 35 to 350
GC-MS Parameters:
Unity-Ultra Desorption Parameters:
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Effect of Temperature data: types of VOCEffect of Temperature data: types of VOC
No. of VOC vs Ret time
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30
Ret time
VO
C n
o.
60C
25C
40C
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Effect of Decay DataEffect of Decay Data
Normalised decay
0
20
40
60
80
100
120
1 6 11 16 21
day
no
rmal
ised
em
issi
on
rat
e
Acetone
Phenol
Dodecane
Isooctanal
acetone - start
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VDA276 normalised graphVDA276 normalised graph
Normalised Graph showing TVOC increase with time over test
y = -0.0433x2 + 11.803x - 38.49
0
100
200
300
400
500
600
700
800
900
0 20 40 60 80 100 120 140 160 180 200
time of test / mins
no
rma
lis
ed
TV
OC
Normalised data Poly. (Normalised data)
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VDA276 – Spectrum change with test.VDA276 – Spectrum change with test.
13.75 14.00 14.25 14.50 14.75 15.00 15.25 15.50 15.75
0.5
1.0
1.5
2.0
2.5
3.0
3.5
(x10,000,000)
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© 2006 IARC
© 2006 IARC
Environmental CompetenceEnvironmental Competence ProjectProject
Premium Automotive Premium Automotive
Research and Development ProgrammeResearch and Development Programme