real-time detection of vocs for viaq and shed measurements
TRANSCRIPT
Real-Time Detection of VOCs for
VIAQ and SHED Measurements
Presented by Barbara Marshik, PhD
MKS Instruments, Inc.
2016 APMP TCMQ Meeting
Ulaanbaatar, Mongolia
July 27, 2016
Vehicle Interior Air Quality
(VIAQ)
“New Car” smell – Monitored for health and safety of
the occupants
– PVC, paint thinner, polyurethane,
foam, carpets, adhesives etc.
– Smell loved in US, EU but not as
much in Asia
Measure VOC outgassing in
vehicle interior as well as
interior trim materials and
components
MKS 1
Sealed Housing Evaporative
Determination (SHED)
Looking at emissions NOT from the engine exhaust – Tank leaks and filter breakthrough
– Permeation of HC through the fuel lines
– Diurnal emissions and tank venting due to heating
Others can contribute as well – tire, paint, adhesives and vinyl
emissions
Three Main Tests – Running Losses
– Hot Soaks
– Diurnal Emissions
– Looking for Hydrocarbons and Ethanol mainly
MKS 2
MKS Solutions
AIRGARD® Analyzer – VIAQ – Short Term Solution
Process analyzer to spot vehicles with high emissions immediately
FTIR which requires Zero gas only Analysis using 1 – 10 minute sample times Alcohols, Acetaldehyde, Formaldehyde and high levels of BTEX
– SHED Solution Sealed Housing Evaporative Determination Ethanol and other alcohols, Acetaldehyde, Formaldehyde
PRISM MAX™ Analyzer – Long Term Solution for VIAQ – Combination of GC and MKS FTIR technologies
– Analysis within 30 – 60 minutes on site
– Extremely low levels of BTEX
– Configurations for Acetaldehyde and Formaldehyde as well at low ppb
MKS 3
Standard VIAQ VOCs Measured
Compound Health Hazard Potential Source
Benzene Carcinogen Plastics and solvents
Formaldehyde Carcinogen Adhesives, foam, fiberboard,
textile treatment
Ethyl benzene Possible Carcinogen Used to produce Styrene
Styrene Possible Carcinogen Plastics, resins and
synthetic rubbers
Toluene Reproductive Toxin Fuel Additive, paints,
varnish, glues
Xylenes Liver and Kidney damage Paints, inks, leathers,
plastics
Acetaldehyde Symptoms similar to
alcoholism and respiratory
effects
Solvent for rubber, leather
tanning, polyester resins
and dyes
MKS 4
VOC VIAQ
Maximum Allowable Limits (µg/m3)
Component
China
GB/T 27630- 2011 Korea Japan MHLW
2011 Proposed
2016
Benzene 110 50 30 NA
Formaldehyde 100 80 250 100
Toluene 1100 1000 1000 260
Xylene
(o-,m-,p-) 1500 500 870 870
Ethyl Benzene 1500 500 1600 3800
Acetaldehyde 50 200 NA 50
Styrene 260 260 300 220
Acrolein 50 50 NA NA
MKS 5
VIAQ Vehicle Process
Each Country is different – Age of vehicle (generally
14-28 days)
– Windows open (X hrs) then closed (2, 8, 16 hrs)
– Test procedures, analysis methods, VOCs and limits
All include a Standard Mode
– Vehicle not moving or on
– At 23°C or 75°F
May include – Parking Mode - External
heating may be on
– Driving Mode – AC or fan on
ISO is working on global harmonization of testing
– ISO TC 146/SC 6/TC22 Joint WG 13
MKS 6
Test Procedures
Example of VIAQ Testing
Vehicle acclimates at 75oF (~23oC) – Open window for 30 minutes
– Close doors for 8 hours then collect sample Plastic tube at drivers seating
area attached to a pump
Current Analyses – Samples collected using DNPH,
Tenax tubes (30 min each)
– DNPH uses HPLC and Tenax uses GC – MS
– ~3 cars per day at $2K each tube ~$6K per day
– ~$1.5M per station
MKS 7
AIRGARD® Analyzer VIAQ FTIR
MeOH Toluene Formaldehyde
MKS 8
PP
M
Time (generic)
AIRGARD® Analyzer - VIAQ
Estimated Detection Limits
MKS 9
Name
Estimated
Detectable Limit 10 min. scan
(ug/m3)
Proposed
GBT 27630-
2016 China
(ug/m3)
Acetaldehyde 100 200
Formaldehyde 10 80
Toluene 600 1000
Ethyl benzene 700 500
Xylenes 500 500
Styrene 200 260
Benzene ND 50
Acrolein ND 50
Methanol 20 NA
Ethanol 100 NA
Acetone 50 NA
AIRGARD® Analyzer VIAQ
Rapid screening for Aldehydes and high levels of
BTEX
Provides insight into other unexpected
components – Alcohols that may present
– Compounds that may be converted or missed using the
thermal desorption tube process
Process screening tool
Better fit for SHED
MKS Confidential 10
MKS SHED Solution
AIRGARD® Analyzer
AIRGARD® Analyzer – Ethanol DL is 100 ppb
and Methanol is 40 ppb
– Oxygenated HCs at ppb
– No MeOH interference
Current Technology – LumaSense Innova
– IR, filter wheel with photo-acoustic detector
– Interference from MeOH
MKS 11
5 ppm EtOH 0.35 ppm EtOH
New On Site VIAQ Solution
MAX™ Analyzer New Technology
Current Technology - SYFT Technology’s SIFT – MS – Selected Ion Flow Tube Mass Spectrometry
– Typical DLs are ppbv to pptv
– Daily validation of a multicomponent certified standard required
– Carrier gas required Dilutes the sample Requires pptv detection for low ppb components
– Very high capital cost ~$250,000 USD
MKS / PRISM Analytical Technology’s on site solution – MAX Analyzer
Novel combination of GC and FTIR technologies Thermal desorption tube concentrator
– Many types available GC separates out the components coming of TDT
– Restek column with VICI resistive heating Performs gas analysis using FTIR
– MKS 2030 FTIR Gas Analyzer – no LN2 required – Can also run FTIR alone
– Fixed Calibrations for FTIR & GC-FTIR Applied together – measures % to ppbv (mg to ng)
MKS 12
MAX Sampling System
MKS 13
Dual adsorption tubes for
spike recovery or
different species matrix
MAX TDT Desorber / GC /
FTIR Gas Cell
MKS Confidential 14
MAX™ MKS FTIR
gas cell
GC
Column
How Does the MAX Analyzer
Work?
Sample injected into chromatographic column (A)
GC separates components, which enter/fill FTIR gas cell (B)
Infrared beam passes through gas sample multiple times (C)
MAX™ software integrates and measures each fully eluted compound
MKS 15
A B C
MAX Analysis Software
(Mass versus Time)
MKS 16
Page 16
● ●
●
Real Benzene Example
MKS 17
MAX™ Peak
BKG SPC
● ● ● ●
●
Time
Actual conc
Mass (ng)
Sample vs Calibration 120 ng at 5L = 24 ugm-3
near DL
FT
IR A
bs
orb
an
ce
Wavenumber (cm-1)
Benzene
Library SPC
Compound is eluting
from column here
MAX Analyzer
VIAQ Detection Limits
MKS 18
Name
Estimated
Detectable Limit 5000 mL
sample (ug/m3)
Proposed
GBT 27630-
2016 China
(ug/m3)
Benzene 25 50
Toluene 25 1000
Ethyl benzene 25 500
m-Xylene 25
500 p-Xylene 25
o-Xylene 25
Styrene 25 260
Acetaldehyde 25 200
Formaldehyde 10 80
MKS Solutions for
Vehicle Material Emissions
AIRGARD® Analyzer VIAQ – Rapid screening tool for high BTEX
– Validation of Acetaldehyde, Formaldehyde
– Ethanol, Methanol and other unknowns can be determined
AIRGARD® Analyzer SHED – Instant Validation tool
– Validation of Ethanol, Methanol, Acetaldehyde, Formaldehyde and other alcohols and aldehydes
PRISM MAX Analyzer – Low cost option to SYFT SIFT-MS
– On site analyzer replaces laboratory analyzer for real time results
– Validation of BTEX, Ethanol, Methanol, Acetaldehyde, Formaldehyde and other alcohols and aldehydes
– Detection limits well below proposed China Limits for most BTEX and Aldehyde components
MKS 19