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