passive air sampling for ozone by solid phase ... air sampling for ozone by solid phase...
TRANSCRIPT
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Passive Air Sampling for Ozone by Solid Phase Microextraction
I-Su Lee and Shih-Wei Tsai
Institute of Environmental Health, College of Public Health, National Taiwan University, Taipei, [email protected]
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Outline
IntroductionPurposeMaterials and methodsResultsConclusions
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Introduction
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Ozone
One of the major air pollutants
Ground level is produced by reaction between NO2, organic gas and sunlight
Exposures might cause severe health effects
4Source, U.S. EPASource, U.S. EPA
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Methods of Sampling and Analysis
Direct instrumentUV-light absorption…...
Personal samplerActivePassive
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Active VS. Passive
Active Passive
Advantage High accuracyShort term monitoring
LightHigh accuracyOperation easinessLong term monitoring
Disadvantage Need pumpHeavyNot reusable
Low sensitivity Sample storage hardNot reusable
6source, http://www.tva.gov/environment/air/ontheair/outdoor.htm
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The advantages of SPME
Integration of sampling、extraction、concentration、sample injectionReduce and simplify the extraction proceduresSolvent-freeGood detection and quantitation limitReusable
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Purpose
Develop a passive sampler for ozone based on the technique of SPME
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Expected reaction
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N C C N N CO
HDPE
ozone+ other product
F
F
F
CH 2
FFO NH 2
N CO
H
F F
CH 2
FF
FO N C
H
NF F
F CH 2
FFO N C
H
N
PFBHA
+
+
Pyridin-4-aldehyde-PFBHA
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Materials and methods
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Materials
1,2-Di-(4-pyridyl)ethylene(DPE)Pyridin-4-aldehydePFBHAOzoneOximeExposure systemSPME diffusion sampler
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Chromatogram of oxime
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CH2O N
FF
F
FFC
H
N
CH2O N
FF
F
FFC
H
N
Synthesize oxime
Aldehyde and PFBHA form
oxime on SPME
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Reaction time between PFBHA and pyridin-4-aldehyde
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Materials
1,2-Di-(4-pyridyl)ethylene(DPE)Pyridin-4-aldehydePFBHAOzoneOximeExposure systemSPME diffusion sampler
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Exposure system
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Passive sampler
Hood
Mixing chamber
Exposure chamber
Continuous analyzer
Ozone generator
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Materials
1,2-Di-(4-pyridyl)ethylene(DPE)Pyridin-4-aldehydePFBHAOzoneOximeExposure systemSPME diffusion sampler
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SPME diffusion sampler
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Perspective view of the passive sampler: (a) SPME fiber assembly,
(b) PTFE septum, (c) PTFE tubing, and (d) cap/PTFE tape.
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Fiber selection
fiberarea
Oxime* DPE**
PDMS 455475 -
PDMS/DVB 1125855 8852208
CAR/PDMS nd -
CW/DVB 110338 -
DVB/CAR/PDMS 1168172 872430*pyridin-4-aldehyde extract 5min and PFBHA extract 2min,
GC inject port temperature 250 ºC, desorption time 2min**DPE extract 30min, GC inject port temperature 250 ºC, desorption time 5min
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Desorption efficiency of oxime
desorption time(min)#
areadessoption
efficiency*(%)first second
1 16671.055 797.887 95.43%
2 15390.997 468.4785 97.05%
5 15269.862 398.117 97.46%
7 14746.4935 0 100.00%
# aldehyde adsorption 1 min, PFBHA react 20min, temperature of GC inject port 270 ºC*first area/(first area + second area)
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Methods
Fiber PDMS/DVB
DPE loaded method Direct extraction 30sec
GC inject port temperature 270 ºC
Desorption time 7min
PFBHA reaction time 20min
GC temperature program 150 ºC 250 ºC(15min)
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10 ºC/min
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Results
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Test on real sample
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Ozone concentration : 400ppbExpose 4hr
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Fick’s First Law : nf = Dg(A/Z) ∫Cg(t)dt
nf and Q is the sampling mass of the analyte
Sampling Rate = Dg(A/Z)
Dg : Binary diffusion coefficient of analyte in air, cm2min−1
A : Surface area of the needle opening, cm2
Z : Retracted fiber path length, cm
Fick’s First Law
Q=RCT*source: Jacek A.K. and Inman N.. Sampling and sample-preparation strategies based on solid-phase
microextraction for analysis of indoor air. Trends in Analytical Chemistry, 21 (12); 840-850 (2002)
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Fiber condition
Coating DPE
React with
PFBHA
GC analyse
Fiber condition
Coating DPE
Coating PFBHA
GC analyse
method 1
method 2
sampling Wait 20min
sampling
Sampling method
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ozone concentration × exposure time vs. oxime mass
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Pyridin-4-aldehyde storage
Day* Area
0 2998.857
1 2477.574
4 2160.433
*aldehyde adsorption 1min, storage in 4 ºC, PFBHA react 20min
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Compare with other samplerSampling reagent Instrument Detection limit
1,2-di(4-pyridyl)ethylene(DPE) GC-ECDMethod 1, 120 ppb-hrMethod 2, 30 ppb-hr
1,2-di(4-pyridyl)ethylene(DPE) Spectrophotometry(422nm) 3 ug/m3 for a one week exposure
indigo carmine Spectrophotometry(408nm) 0.7 ppm-hr, 50 ppb for 8 hr
potassium iodideSpectrophotometry(575nm)
ion chromatography(IC)
3-methyl-2-benzothiazolinone acetone azine (MBTH ) Spectrophotometer(504nm) 0.09 ppm-hr,
4 ppb for 24 hr
p-acetamidophenol(p-ATP) Spectrofluorimeter
nitrite ion ion chromatography(IC)201 ppb-hr,
17 ppb for 12 hr, 8 ppb for 24 hr
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Conclusions
More sensitiveReusableSolvent-freeBackground noiseCoated fiber should be prepared before samplingInterferenceField test
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AcknowledgementNSC 95-2314-B-002-329, Taiwan
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