comparative study of two methods for olfactory measurement ○ saeko amano, hiroyuki ueno tokyo...
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Comparative Study of Two Comparative Study of Two Methods for Olfactory Methods for Olfactory
MeasurementMeasurement
○ Saeko Amano , Hiroyuki Ueno Tokyo Metropolitan Research Institute for Environmental Protection
Triangle Odor Bag MethodTriangle Odor Bag Method and Dynamic Olfactometryand Dynamic Olfactometry
Outline of this presentation Outline of this presentation
1.1. Dilution accuracy between the European methoDilution accuracy between the European method and the Japanese method using GC and HPLd and the Japanese method using GC and HPLCC
2.2. Difference of odour threshold between the EuroDifference of odour threshold between the European method and the Japanese method pean method and the Japanese method
3.3. Difference among 3 method Difference among 3 method ththee European method, the Japanese method and European method, the Japanese method and European-like Japanese methodEuropean-like Japanese method
Outline of this presentation Outline of this presentation
1. Dilution accuracy between the Europ1. Dilution accuracy between the European method and the Japanese methean method and the Japanese method using GC and HPLCod using GC and HPLC
2. Difference of odour threshold between the Euro2. Difference of odour threshold between the European method and the Japanese method pean method and the Japanese method
3. Difference among 3 method 3. Difference among 3 method tthehe European method, the Japanese method anEuropean method, the Japanese method and European-like Japanese methodd European-like Japanese method
Differences between the Japanese Differences between the Japanese method and the European methodmethod and the European method
The Japanese method
The European method
Dilution Bag &
Syringe
Flow controller,
Needle valve, etc.
Presentation DescendingAscending random
Step factor 3 2
Sniffing condition
Air in the bag
Air emanated from port
Panel Selection
5 standard solutions
n-Butanol
1. Dilution accuracy between the European method and the 1. Dilution accuracy between the European method and the Japanese methodJapanese method
Sample Dilution factorThe European The European
methodmethodThe Japanese The Japanese
methodmethod
NoNoDilutionDilution
factorfactorDilutionDilution
factorfactor
44 3333 303055 6565
10010066 136136
77 266266 30030088 560560
1000100099 10321032
Sample, Dilution factor
Hydrogen Sulfide
Hexanal
Propion aldehyde
1. Dilution accuracy between the European method and the 1. Dilution accuracy between the European method and the Japanese methodJapanese method
Analytical method Make the original
gas
Dilute with odor-free air according to European method or Japanese method
Adsorb gas to cartridge
( SUPELCO DNPH)
Elute with acetnitrile
HPLC-UV
Trap gas to cold concentration tube
Heat tube and inject to GC
GC-FPD
Aldehyde Hydrogen Sulfide
1. Dilution accuracy between the European method and the 1. Dilution accuracy between the European method and the Japanese methodJapanese method
50
75
100
125
150
10 100 1000 10000
Result of dilution test -1Result of dilution test -1 ( Hydrogen Sulfide) ( Hydrogen Sulfide)
Hydrogen Sulfide is hardly adsorbed
during the test .
Recovery
(%
)
Dilution Factor
◆ Dynamic Olfactometer( The European method)
■ Triangle Odor Bag Method( The Japanese method)
1. Dilution accuracy between the European method and the 1. Dilution accuracy between the European method and the Japanese methodJapanese method
0
50
100
150
200
10 100 1000 10000
Result of dilution test -2Result of dilution test -2 ( Hexanal) ( Hexanal)
The Japanese method have nice recovery when dilution factor is more than 300. The European method nearly get good recovery of each dilution factor.
Recovery
(%
)
Dilution Factor
1. Dilution accuracy between the European method and the 1. Dilution accuracy between the European method and the Japanese methodJapanese method
◆ Dynamic Olfactometer( The European method)
■ Triangle Odor Bag Method( The Japanese method)
0
50
100
150
10 100 1000 10000
Result of dilution test -3Result of dilution test -3 ( Propion aldehyde) ( Propion aldehyde)
The result is as same as that of hexanal .
Recovery
(%
)
Dilution Factor
1. Dilution accuracy between the European method and the 1. Dilution accuracy between the European method and the Japanese methodJapanese method
◆ Dynamic Olfactometer( The European method)
■ Triangle Odor Bag Method( The Japanese method)
Conclusion of dilution accuracy Conclusion of dilution accuracy testtest
The difference of dilution accuracy between the European method and the Japanese method was shown by using Hydrogen Sulfide, hexanal and propionaldehyde as samples.Concerning hydrogen sulfide, both method could get almost 100% recovery.About aldehyde containing hexanal and propionaldehyde, recovery varied a little widely at the European method ,however, the European method nearly got good recovery . On the other hand, the Japanese method didn’t get good result when their dilution value was lower. But when dilution factor was more than 300, the Japanese method had good recovery as to the European method.
1. Dilution accuracy between the European method and the 1. Dilution accuracy between the European method and the Japanese methodJapanese method
Outline of this presentation Outline of this presentation
1. Dilution accuracy between the European metho1. Dilution accuracy between the European method and the Japanese method using GC and HPLd and the Japanese method using GC and HPLCC
2. Difference of odour threshold betwee2. Difference of odour threshold between the European method and the Japan the European method and the Japanese methodnese method
3. Difference among 3 method 3. Difference among 3 method tthehe European method, the Japanese method anEuropean method, the Japanese method and European-like Japanese methodd European-like Japanese method
odoranodorantt
n-butanoln-butanol
HexanalHexanal
Hydrogen SulfideHydrogen Sulfide
TrimethylamineTrimethylamine
Isobutyric acidIsobutyric acid
Ethyl AcetateEthyl Acetate
Standard odourants of the European method
2.Difference of odour threshold between two method for olfactory measurement2.Difference of odour threshold between two method for olfactory measurement
Standard odourants of the Japanese methos
Odour quality
smell of stinking socks, smell of natto
Smell of rotten fish
Smell of rotten egg
Smell of cutting grass
Smell of thinner
Olfactory Olfactory measurementmeasurement
Measurements by both method for each odourant were performed in a same day using same panel members
Number of Measurement : 3~
2.Difference of odour threshold between two method for olfactory measurement2.Difference of odour threshold between two method for olfactory measurement
Result of odour threshold measuremenResult of odour threshold measurementt
2.Difference of odour threshold between European method and Japanese method2.Difference of odour threshold between European method and Japanese method
Except for isobutyric acid, threshold of the European method are higher than that of the Japanese method
log Threshold (ppt )
DynamicOlfactmetry
Triangle odorbag method
n-butanol 4.8 4.1Hexanal 3.4 2.4
Ethyl Acetate 3.1 2.6Hydrogen Sulfide 3.1 2.5Trimethyl amine 3.1 2.7Isobutyric acid 3.6 4.0
Result of odour threshold measuremenResult of odour threshold measurementt
2.Difference of odour threshold between European method and Japanese method2.Difference of odour threshold between European method and Japanese method
Concentrations of threshold measured by the European method are about 3-9 times higher than that measured by the Japanese method except for butyric acid.Dynamic
Olfactmetry(A)
Triangle odorbag method
(B)
Proportion(A/B)
n-butanol 75 14 5.3Hexanal 2.9 0.3 9.0
Ethyl Acetate 1389 384 3.6Hydrogen Sulfide 1.5 0.3 4.5Trimethyl amine 1.7 0.5 3.2Isobutyric acid 4 11 0.4
Threshold (ppb )
Standard deviation of odour thresholdStandard deviation of odour threshold
Standard division of each sample is also same between two method.
2.Difference of odour threshold between two method for olfactory measurement2.Difference of odour threshold between two method for olfactory measurement
DynamicOlfactmetry
Triangle odorbag method
n-butanol 0.1 0.3Hexanal 0.2 0.1
Ethyl Acetate 0.2 0.2Hydrogen Sulfide 0.4 0.2Trimethyl amine 0.2 0.1Isobutyric acid 0.2 0.1
Standard deviation
Summary of odour threshold’s differencSummary of odour threshold’s differencee
Olfactory measurement was done using 6 odour Olfactory measurement was done using 6 odour substances.substances.Except for isobutyric acid, concentrations of threshold measured by the European method are about 3-9 times higher than that measured by the Japanese method.Standard division are also same between two methods.
2.Difference of odour threshold between two method for olfactory measurement2.Difference of odour threshold between two method for olfactory measurement
Outline of this presentation Outline of this presentation 1.1. Dilution accuracy between the European method aDilution accuracy between the European method a
nd the Japanese method using GC and HPLCnd the Japanese method using GC and HPLC
2.2. Difference of odour threshold between the EuropeDifference of odour threshold between the European method and the Japanese method an method and the Japanese method
3. Difference among 3 method 3. Difference among 3 method thethe European method, the Japanese methoEuropean method, the Japanese method and European-like Japanese methodd and European-like Japanese method
Differences between Japanese Differences between Japanese method and European methodmethod and European method
The Japanese method
The European method
Dilution Bag & Syringe
Flow controller, Needle valve, etc.
Presentation Descending Ascending random
Step factor 3 2Forced choice 3 2Sniffing condition
Air in the bag
Air emanated from port
Panel Selection
5 standard solutions
n-Butanol
3. Difference among three methods 3. Difference among three methods
Condition of experimentCondition of experimentThe
European method
The Japanese method
European-like Japanse method
Dilution
Flow controller, Needle valve, etc.
Bag & Syringe
Bag & Syringe
Presentation
Ascending random
DescendingAscending random
Step factor 2 3 2Forced choice 2 3 2
Sniffing condition
Air emanated from port
Air in the bag
Air in the bag
3. Difference among three methods 3. Difference among three methods
The European method
The Japanese method
European-like Japanse method
Dilution
Flow controller, Needle valve, etc.
Bag & Syringe
Bag & Syringe
Presentation
Ascending random
DescendingAscending random
Step factor 2 3 2Forced choice 2 3 2
Sniffing condition
Air emanated from port
Air in the bag
Air in the bag
Condition of experimentCondition of experiment3. Difference among three methods 3. Difference among three methods
Samples and PanelsSamples and PanelsSamplesSamples
n-butanol n-butanol Source sample of offset printing Source sample of offset printing
(mixture of odour)(mixture of odour)
Panel membersPanel members12 person12 personss
(divide 2 groups and 6 members each)(divide 2 groups and 6 members each)
MeasurementsMeasurementsEach measurement was done one time in a day anEach measurement was done one time in a day and repeated four daysd repeated four days
3. Difference among three methods 3. Difference among three methods
20
30
40
50
1 2 3
Differences among 3 methodsDifferences among 3 methods((offset printing smelloffset printing smell))
The Europea
n method
The Japanese method
European-like Japanese method
10 x
log
Odo
ur c
once
ntr
atio
nEuropean-like Japanese method had same log odour conc. as the European method and lower than the Japanese method.
Low
←
Sen
sit
ivit
y →
Hig
h
3. Difference among three methods 3. Difference among three methods
Differences among 3 methodsDifferences among 3 methods(n-butanol)(n-butanol)
0
1
2
31 2 3
log
Th
resh
old
(p
pb
)Sensitivity of European-like Japanese method is lower than the Japanese method.
The Europea
n method
The Japanese method
European-like Japanese methodL
ow
←
Sen
sit
ivit
y →
Hig
h
3. Difference among three methods 3. Difference among three methods
Results of odour threshold in this year’s Results of odour threshold in this year’s ( n-butanol)( n-butanol)
0
1
2
3
1 2 3 4
log
Th
resh
old
(p
pb
)
◆The European method ■ The Japanese method
First time Second time
Sensitivity by Japanese method are higher than that by European method. This result show same trend as that of offset printing
Low
←
Sen
sit
ivit
y →
Hig
h
3. Difference among three methods 3. Difference among three methods
Summary of difference among 3 Summary of difference among 3 methodmethod
European-like Japanese European-like Japanese method( ascending presentation method( ascending presentation and two forced choice mode)and two forced choice mode) was was compared with the European compared with the European method and the Japanese method.method and the Japanese method.
Sensitivity of European-like Sensitivity of European-like Japanese method is lower than the Japanese method is lower than the Japanese methodJapanese method
3. Difference among three methods 3. Difference among three methods
Conclusion(1/2)Conclusion(1/2)
Dilution accuracy of hydrogen sulfide and alDilution accuracy of hydrogen sulfide and aldehyde is good on both method when dilutiodehyde is good on both method when dilution factor is more than 300. n factor is more than 300. Concentrations of threshold measured by the European method are 3-9 times higher than that measured by the Japanese methodEuropean-like Japanese method European-like Japanese method had same threshold as the European method.
Conclusion(2/2)Conclusion(2/2)These results shows that deference between Japanese and European methods is mainly caused by the definition of the threshold, not by dilution method or materials.
Main reason may be as follows: Answer of panelist is recognized as “true” when “correct and certain” is observed in the European method while the Japanese method recognize the answer as “true” whenever it is correct.
Future PlanFuture Plan
Study of difference in race.Study of difference in race. ( We take a test in Poland on and after tomorrow with your h( We take a test in Poland on and after tomorrow with your h
elp, and compared with the result in Japanese)elp, and compared with the result in Japanese)
research dilution accuracy of Isobutyric acidresearch dilution accuracy of Isobutyric acid
ConclusionConclusionDilution accuracy of hydrogen sulfide is good on bDilution accuracy of hydrogen sulfide is good on both method. Concerning hexanal, the European meoth method. Concerning hexanal, the European method is almost well and the Japanese method as sthod is almost well and the Japanese method as same as that one which is limited ame as that one which is limited dilution factor to more than 300.Except for isobutyric acid, concentration s of threshold measured by the European method are about 3-9 times higher than that measured by the Japanese methodEuropean-like Japanese method European-like Japanese method had same log odour concentration as the European method in the case of using off-set printing, but difference that of using n-butanol.
12
345
67
n-butanol hexanal Isobutyric acid Ethyl acetate
Result of odour thresold-2 (winter)Result of odour thresold-2 (winter)H
igh
←
S
en
siti
vit
y o
f p
an
el
→
lo
wLog
Th
resh
old
(p
pt
)
n-Butanol hexanal
◆Dynamic Olfactometer ■ Triangle Odor Bag Method
IsobutyricAcid
EthylAcetate
2.Difference of odour thresold between European method and Japanese method2.Difference of odour thresold between European method and Japanese method
Except for isobutyric acid, thresold of Europian method are higher than that of Japanese method
2
3
4
5
n-butanol hexanal Hydrogen
sulfide
Trimethylamine
Result of odour thresold-1 (summer)Result of odour thresold-1 (summer)H
igh
←
S
en
siti
vit
y o
f p
an
el
→
lo
wLog
Th
resh
old
(p
pt
)
n-Butanol hexanal
Hydrogen sulfide
Trimethylamine
2.Difference of odour thresold between European method and Japanese method2.Difference of odour thresold between European method and Japanese method
Thresold of Europian method are higher than that of Japanese method. But standard deviation are different.
◆Dynamic Olfactometer ■ Triangle Odor Bag Method
Main PointsMain Points
におい袋を用いた、オルと同一の希釈倍におい袋を用いた、オルと同一の希釈倍数、サンプルの出し方の方法を数、サンプルの出し方の方法を MethodAMethodAとし、オル、におい袋法と比較した。とし、オル、におい袋法と比較した。オフセット印刷臭については、 Method Aと折るファクトメーターは同一の臭気濃度をしめした。ブタノールについてはブタノールについては MethodAMethodA のみ高いのみ高い閾値を示し、オルファクトとにおいは差閾値を示し、オルファクトとにおいは差がなかった。がなかった。
3. Study of difference among three 3. Study of difference among three method method
22 点比較と点比較と 33 点比較 点比較 臭袋法4臭袋法4
2倍系列上昇法 2倍系列上昇法臭袋法5臭袋法5
2倍系列上昇法 2倍系列上昇法
3点比較3点比較 2点比較2点比較n-n-ブタノールブタノール個人閾値の全平均個人閾値の全平均 (ppb(ppbの対数の対数))
2.02.0 2.02.0
標準偏差(個人間標準偏差(個人間)) 0.340.34 0.290.29
標準偏差(個人内標準偏差(個人内)) 0.270.27 0.250.25
オフセット印刷臭オフセット印刷臭個人閾値の全平均個人閾値の全平均 (希釈倍数の対数) (希釈倍数の対数) 3.33.3 3.33.3標準偏差(個人間標準偏差(個人間)) 0.320.32 0.260.26
標準偏差(個人内標準偏差(個人内)) 0.220.22 0.290.29
Differences among 3 Differences among 3 methodsmethods
European European methodmethod
Japanese Japanese methometho
ddMethodAMethodA
n-butanoln-butanolLog Threshold Log Threshold
(ppb)(ppb)1.61.6 1.61.6 2.02.0
Off-set printingOff-set printing
Log Odour Conc.Log Odour Conc. 3.23.2 3.83.8 3.33.3
Concering off-set printing, Method A had same log odour conc. as European method and be different from Japanese method. But as n-butanol, Log threshold of method A is high among 3 methods.
3. Study of difference among three 3. Study of difference among three method method
High ← Sensitivity of panel → LowLow ← log threshold (ppb) → HighHigh ← log odor coc. → Low
Caution!
差異の要因の定量的検討差異の要因の定量的検討上昇法と下降法(閾値の定義(回答方上昇法と下降法(閾値の定義(回答方法)の違い)法)の違い)2倍系列と3倍系列2倍系列と3倍系列3点比較と2点比較3点比較と2点比較