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Passive Sampling of Nitrogen Dioxide and Sulfur Dioxide in Ambient Air of Chiang Mai. Shakya, K.M. 1 , P. Thavornyutikarn 1 , S. Chantara 1 , W. Saipunkaew 1 , H. Mosbaek 2. 7 December 2004. Environmental Science Program, Faculty of Science, Chiang Mai University, Thailand
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Passive Sampling of Nitrogen Dioxide and Sulfur Dioxide in Ambient Air of Chiang Mai Shakya, K.M.1, P. Thavornyutikarn1, S. Chantara1, W. Saipunkaew1, H. Mosbaek2 7 December 2004 • Environmental Science Program, Faculty of Science, Chiang Mai University, Thailand • Technical University of Denmark, Denmark
1. Introduction Passive Sampling • First described by Palmes et al. (1976) in occupational hygiene for measuring NO2 in indoor air • Based on diffusion principle • Collection of gas on sampling medium soaked with absorbent by chemical absorption (Krupa and Legge, 2000) • Sampling medium – filter papers or steel meshes • Absorbent – depends on gas of interest
Advantages Disadvantages • Long sampling time • No standard procedures • Inability to obtain short-term peaks • Possibility of interferences from meteorology • Doubts on reliability • Light, cheap, robust, easy to operate • Small, soundless and reusable • On-site power and pumping of air not required • Do not require attention during sampling • Supports “green analytical chemistry“ • Favors to have many sampling sites • Very appropriate for large scale monitoring
Objectives of this research • To determine the accuracy of passive samplers by comparing with active samplers, • To compare the results among different kinds of passive samplers, • To compare the results of NO2 concentrations from spectrophotometer and ion chromatograph, and • To determine the levels of NO2 and SO2 concentrations in ambient air using passive samplers in Chiang Mai city
2. Experimental Preparation of diffusion tubes • diffusion tubes – polystyrene (ps), polyethylene (pe), and “Gradko” tubes • Sampling medium - Whatman no. 40 filter paper • Absorbents for NO2 – TEA and NaOH plus NaI • Absorbents for SO2 – TEA, Na2CO3, and NaOH • Installation of diffusion tubes inside the polyethylene box at 1.5 m above ground level • 3-9 sampling sites • Sampling period – October 2003 to February 2004
Diagram of diffusion tube TEA coated filter paper 5.4 cm 5.4 cm 1.2 cm 1.3 cm Polyethylene cap Polystyrene tube Polyethylene tube
Analysis of NO2- by spectrophotometer • Extraction with DI water • Color formation with reagent mixture (Sulfanilamide + N-1 naphthyl ethylene diamine hydrochloride solution) • Measured at 540 nm on PerkinElmer Lambda 25 Spectrophotometer Analysis of NO2- and SO42- by Ion Chromatograph • Extraction with Milli-Q water • Oxidation with 0.15% H2O2 • eluent: 1.80 mM Na2CO3/ 1.70 mM NaHCO3 • 1.5 ml/min eluent flow rate • 3 s background conductivity • 25 l sample loop volume • BDS, Barspec Data System
3. Results & Discussion PE tubes - 14.22% > PS tubes Correlation between NO2 measurements by PS and PE tubes (Analysis by Spectrophotometer)
PE tubes - 1.95% > PS tubes Correlation between SO2 measurements from 4 weeks exposure of PS and PE tubes
PS tubes - 1. 62% > PE tubes Correlation between SO2 measurements from 2 weeks exposure of PS and PE tubes
Underestimation:54.13% PS tubes and 15.39% PE tubes Correlation between NO2 measurements from active and passive sampling for 2 weeks period
Detection limits for instrument • Spectrophotometer • 0.09 g/ml NO2- • Ion Chromatograph • DL: 0.04 g/ml NO2- and 0.02 g/ml SO42- • Minimum Detectable Quantity: 0.48 g.sec NO2- and 0.36 g.sec SO42- Detection limits for passive sampling method • NO2: 1.6 g/m3 for PS and 3.9 g/m3 for PE tubes • SO2 (2 weeks): 1.9 g/m3 for PS and 1.7 g/m3 for PE tubes • SO2 (4 weeks): 1.4 g/m3 for PS and 2.1 g/m3 for PE tubes
4. Conclusion • Diffusion tubes (ps and pe) showed good trends of NO2 and SO2 concentrations • Good correlation between ps and pe tubes • Good correlation between active and passive sampling measurements for NO2 but variable for SO2 • Underestimation for NO2 and overestimation for SO2 by diffusion tubes compared to active sampling; also supported by “Gradko” tubes • Variations in blank measurements • Precision - 18.12% for NO2 and 16.36% for SO2
Errors can be reduced for diffusion tubes : • Use of protective shelters • Keeping tubes in an airtight containers during transit • Storage of tubes in a refrigerator and not storing for very long time • Diffusion tubes with separate cap and body parts • Use of a porous membrane at mouth of the tube • Good laboratory practice