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Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 1
Determination of Ambient VOCs using Passive-Canister-Preconcentrator-GC/MS
W. Laowagul, S. Sooktawee, S. Boonyapitak, S. Rattanapiboon,
H. Garivait and S. Watanabe
Contents of Presentation
ObjectivesQA/QC on sampling QA/QC on analysisPreliminary study
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 2
Objectives
I. To develop an appropriate methodology for ambient VOC monitoring
II. To determine the prevailing VOC in ambient air in Thailand using canister-preconcentrator-GC/MS
77 Target VOCs are focused
40 compounds are included in the 189 hazardous air pollutants (HAPs) listed in Title III of the clean Air Act Amendment of 199015 compounds are included in the Photochemical Assessment Monitoring Station (PAM)39 compounds are in the lists of Compendium Method TO-1436 compounds are in the lists of Compendium Method TO-15
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 3
QA/QC on Sampling
Testing cleanliness of canisterand sampling train
Leak test 50 mtorrRough pump 1 psiHigh vacuum 225 mtorrpumpNitrogen gas fill 25 psiCycle 10-20Final rough pump 1 psiFinal H. V. pump 50 mtorr
225
30
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 4
Assembling frit filter and orificeIn a clean environment, assemble the sampling train components as shown in Figure 1. It is imperative that you leak test the assembled train. If the sampling train leaks during sampling, the final partial pressure in the canister will not be the desired final partial pressure, making the sample invalid. The most common reason for invalid samples is leaks within the sampling train.How to check leak1. Cap the inlet (A), attach the sampling train to an evacuated canister, open the valve on the canister and evacuate the sampling train.2. Close the valve and monitor any pressure change in the static sampling train. Leaks of less than 0.1 mL/min. can be detected in 10-20 minutes.3. Make sure no-leak by monitor any pressure change when opening the valve.
(A)
Checking the leak of canister and sampling train
Repeating assembling a canister to a pre-concentrator, a canister cleaner, or a STD gas diluter, this nut may become lose
At first, these connections to be checked when leak is observed
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 5
Checked Flow Controller
Ambient Air Sampling 24 hrs
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 6
Sampling record sheet
QA/QC on Analysis
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 7
GC-MS chromatogram of a standard sample containing 77 volatile organic compounds
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 8
Quality Assurance and Quality Control
GC/MS performance check using BFBLaboratory blank checkMulti-point calibration Daily calibration check(mid-level calibration standard)Field blank checkDuplicate sampling
Constructed the calibration curve
R2 >0.99%Difference of each concentration in calibration curve less than + 20%%RSD for the relative response factor for each compound in the calibration curve less than + 30%
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 9
Determination Blank LevelCriteria acceptance of EPA < 0.20ppbv
Instrument Detection Limit
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 10
20: Japanese EQS/100.2030.061Tetrachloroethylene
20: Japanese EQS/100.0840.025Trichloroethylene
0.3: Japanese EQS/10; 0.128: equivalent to USEPA 10-5 unit risk/10; 0.225: the lowest UK EQS
0.1070.032Benzene
0.043: equivalent to USEPA 10-5 unit risk/10 0.0460.014Chloroform
15: Japanese guideline/10; 0.2: equivalent to USEPA 10-5 unit risk/10
0.3180.095Dichloromethane
0.03: equivalent to USEPA 10-5 unit risk/10; 0.225: UK EQS/100.0270.00801,3-Butadiene
1: Japanese guideline/100.0340.0103Vinyl chloride
Freon 22 is still used in some spray cans. 0.1800.0539Freon 22
RemarksMQL (ug/m3)
MDL (ug/m3)Compounds
Repeatability Test
0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
0 4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72 76
Peak number
%R
SD
Acetonitrile
Technical acceptance criteria <25%
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 11
Duplicate Sampling
Reproducibility test (Duplicate sampling)
0.00
10.00
20.0030.00
40.00
50.00
60.0070.00
80.00
90.00
0 4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72
Peak number
%R
SD
Propene
2-Propenal
1-Butanol
Pentanal
Hexanal%RSD < 30%
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 12
Preliminary study
Sampling sites
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 13
(1) Aliphatic Hydrocarbons
0.00 10.00 20.00 30.00 40.00 50.00
1,3-Butadiene
Pentane
Isoprene
Hexane
Com
poun
dsConc. (µg/m3)
Klongjun
Sahakorn
Dindang
(2) Aromatic Hydrocarbons
0.00 50.00 100.00 150.00 200.00
Benzene
Toluene
Ethylbenzene
m/p-Xylene
o-Xylene
Styrene
1,3,5-Trimethylbenzene
1,2,4-Trimethylbenzene
1,2,3-Trimethylbenzene
Com
poun
ds
Conc. (µg/m3)
Klongjun
Sahakorn
Dindang
0.52 - 3.2Freon 113
3.51.2 - 3.8Freon 11
Estimated world average conc. (1993-1995) (µg/m3)
Conc. range in Kawasaki city, Japan (1997 -2002)* (µg/m3)
Compounds
(3) CFC
0.00 2.00 4.00 6.00 8.00
Freon 12
HCFC22
Freon 11
Freon113
Com
poun
ds
Conc. (µg/m3)
Klongjun
Sahakorn
Dindang
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 14
(5) Aromatic Halogenated Hydrocarbons
0.00 2.00 4.00 6.00 8.00 10.00
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
1,2,4-Trichlorobenzene
Com
poun
ds
Conc.(µg/m 3)
Klongjun
Sahakorn
Dindang
(4) Low M.W Halogenated Hydrocarbons
0.00 1.00 2.00 3.00 4.00 5.00
Chloromethane
Methylene chloride
Trichloroethylene
1,2-Dichloropropane
Bromodichloromethane
Com
poun
ds
Conc.(µg/m 3))
Klongjun
Sahakorn
Dindang
(6) Oxygenated Hydrocarbons
0.00 2.00 4.00 6.00 8.00 10.00 12.00
2-PropenalPropanal
MTBEMethacrolein
Methyl vinyl ketonePentanal
MIBKBromoform
Com
poun
ds
Conc.(µg/m 3)
Klongjun
Sahakorn
Dindang
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 15
Comparison of ambient VOCs
1.335.44.3111,3,5-Trimethylbenzene0.443.21.95.3Styrene3.234.74.412o-Xylene9.19119.995m/p-Xylene3.065.04.611Ethylbenzene16.935434170Toluene0.203.23.33.0Pentanal
0.74-1.600.142.42.90.76Trichloroethylene1.90-3.404.765.44.112Benzene2.40-4.100.102.32.01.4Methylene chloride
0.513.73.56.2Propanal6.288.85.440Pentane
0.31-0.431.41.22.71,3-Butadiene1998-20031996-1997
Japan Germany KlongjunSahakornDindangConcentration (µg/m3)Compounds
WHO Guideline Value7673.21.95.3Styrene
WHO Guideline Value79005434170Toluene
Maine7002.62.52.8MIBK
Japanese EQS2002.42.90.8Trichloroethylene
The lowest UK EQS2.25
Equivalent to USEPA 10-5 unit risk1.28
Japanese EQS35.44.112Benzene
Equivalent to USEPA 10-5 unit risk2
Japanese Guideline1502.32.01.4Methylene chloride
UK EQS2.25
Equivalent to USEPA 10-5 unit risk0.331.41.22.71,3-Butadiene
Guideline/EQSKlongjunSahakornDindang
Concentration (µg/m3)Compounds
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 16
Tree Diagram for 35 CasesWard`s method
1-Pearson r
0 1 2 3 4 5 6
Linkage Distance
1,3,5-Trimethylbenzene1,2,4-Trimethylbenzene
m/p-Xyleneo-Xylene
EthylbenzeneBenzene
1,2,3-TrimethylbenzeneStyrene
1,2,4-Trichlorobenzene1,4-Dichlorobenzene1,2-Dichlorobenzene
BromoformBromodichloromethane
MIBKPentanal
1,3-DichlorobenzeneMethacrolein
Methyl vinyl ketonePropanal
2-PropenalToluene
Isoprene1,2-Dichloropropane
HexanePentane
1,3-ButadieneTrichloroethylene
MTBEFreon113
Vinyl chlorideMethylene chloride
DifluorochloromethaneChloromethane
Freon 11Freon 12
Cluster analysis of ambient VOCs measured at Dindang in April 24-30,2006
Acknowledgement
Seminar on Development of Environmental and Emission Standards of VOCs 15 September 2006, Bangkok, Thailand 17
This project was supported by Japanese International Cooperation Agency (JICA). The support of JICA is gratefully acknowledged. We gratefully acknowledge Prof. Kunio Yoshizumi, Kyoritsu Women’ university, Japan for his advise on cluster analysis and Mr. Yoshiharu Shirane, Mr. Munihiro Fukuda, Sowa Consultants INC. for his advice on data evaluation.
We would like to thank the Pollution Control Department staffs for their assistance and allowing us to set up the VOCs sampling site.
We also gratefully acknowledge the staffs at Environmental Research and Development on Air Pollution section, ERTC for their assistance to collect the samples.
Thank You