Comparative Study of Two Methods for Olfactory Measurement

1. Comparative Study of Two Methods for Olfactory Measurement Triangle Odor Bag Method and Dynamic Olfactometry ○ SaekoAmano,Hiroyuki Ueno Tokyo Metropolitan Research Institute for Environmental Protection

2. Outline of this presentation • Dilution accuracy between the European method and the Japanese method using GC and HPLC • Difference of odour threshold between the European method and the Japanese method • Difference among 3 method theEuropean method, the Japanese method and European-like Japanese method

3. Outline of this presentation 1. Dilution accuracy between the European method and the Japanese method using GC and HPLC 2. Difference of odour threshold between the European method and the Japanese method 3. Difference among 3 method theEuropean method, the Japanese method and European-like Japanese method

4. 1. Dilution accuracy between the European method and the Japanese method Differences between the Japanese method and the European method

5. 1. Dilution accuracy between the European method and the Japanese method Sample, Dilution factor Dilution factor Sample • Hydrogen Sulfide • Hexanal • Propion aldehyde

6. 1. Dilution accuracy between the European method and the Japanese method Analytical method Make the original gas Dilute with odor-free air according to European method or Japanese method Adsorb gas to cartridge （SUPELCODNPH) Trap gas to cold concentration tube Heat tube and inject to GC Elute with acetnitrile HPLC－UV GC-FPD Aldehyde Hydrogen Sulfide

7. 1. Dilution accuracy between the European method and the Japanese method Result of dilution test -1 ( Hydrogen Sulfide) Hydrogen Sulfide is hardly adsorbed during the test . ◆Dynamic Olfactometer （The European method) ■Triangle Odor Bag Method （The Japanese method) Recovery (%) Dilution Factor

8. 1. Dilution accuracy between the European method and the Japanese method Result of dilution test -2 ( 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. ◆Dynamic Olfactometer （The European method) ■Triangle Odor Bag Method （The Japanese method) Recovery (%) Dilution Factor

9. 1. Dilution accuracy between the European method and the Japanese method Result of dilution test -3 ( Propion aldehyde) The result is as same as that of hexanal . ◆Dynamic Olfactometer （The European method) ■Triangle Odor Bag Method （The Japanese method) Recovery (%) Dilution Factor

10. 1. Dilution accuracy between the European method and the Japanese method Conclusion of dilution accuracy test • 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.

11. Outline of this presentation 1. Dilution accuracy between the European method and the Japanese method using GC and HPLC 2. Difference of odour threshold between the European method and the Japanese method 3. Difference among 3 method theEuropean method, the Japanese method and European-like Japanese method

12. 2.Difference of odour threshold between two method for olfactory measurement Standard odourants of the European method Odour quality Smell of cutting grass Smell of rotten egg Smell of rotten fish smell of stinking socks, smell of natto Smell of thinner Standard odourants of the Japanese methos odorant • n-butanol • Hexanal • Hydrogen Sulfide • Trimethylamine • Isobutyric acid • Ethyl Acetate

13. 2.Difference of odour threshold between two method for olfactory measurement Olfactory measurement Measurements by both method for each odourant were performed in a same day using same panel members Number of Measurement : 3~

14. 2.Difference of odour threshold between European method and Japanese method Result of odour threshold measurement Except for isobutyric acid, threshold of the European method are higher than that of the Japanese method log Threshold (ppｔ)

15. 2.Difference of odour threshold between European method and Japanese method Result of odour threshold measurement 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. Threshold (ppｂ)

16. 2.Difference of odour threshold between two method for olfactory measurement Standard deviation of odour threshold Standard division of each sample is also same between two method. Standard deviation

17. 2.Difference of odour threshold between two method for olfactory measurement Summary of odour threshold’s difference • Olfactory measurement was done using 6 odour 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.

18. Outline of this presentation • Dilution accuracy between the European method and the Japanese method using GC and HPLC • Difference of odour threshold between the European method and the Japanese method 3. Difference among 3 method theEuropean method, the Japanese method and European-like Japanese method

19. 3. Difference among three methods Differences between Japanese method and European method

20. 3. Difference among three methods Condition of experiment

21. 3. Difference among three methods Condition of experiment

22. 3. Difference among three methods Samples and Panels Samples • n-butanol • Source sample of offset printing (mixture of odour) Panel members • 12 persons (divide 2 groups and 6 members each) Measurements • Each measurement was done one time in a day and repeated four days

23. 3. Difference among three methods Differences among 3 methods(offset printing smell) European-like Japanese method had same log odour conc. as the European method and lower than the Japanese method. 10 x log Odour concentration Low ←Sensitivity →High The European method The Japanese method European-like Japanese method

24. 3. Difference among three methods Differences among 3 methods(n-butanol) Sensitivity of European-like Japanese method is lower than the Japanese method. log Threshold (ppb) Low ←Sensitivity →High The European method The Japanese method European-like Japanese method

25. 3. Difference among three methods Results of odour threshold in this year’s ( n-butanol) Sensitivity by Japanese method are higher than that by European method. This result show same trend as that of offset printing Low ←Sensitivity →High log Threshold (ppb) First time Second time ◆The European method■The Japanese method

26. 3. Difference among three methods Summary of difference among 3 method • European-like Japanese method( ascending presentation and two forced choice mode) was compared with the European method and the Japanese method. • Sensitivity of European-like Japanese method is lower than the Japanese method

27. Conclusion(1/2) • Dilution accuracy of hydrogen sulfide and aldehyde is good on both method when dilution factor is more than 300. • Concentrations of threshold measured by the European method are 3-9 times higher than that measured by the Japanese method • European-like Japanese method had same threshold as the European method.

28. 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.

29. Future Plan • Study of difference in race. ( We take a test in Poland on and after tomorrow with your help, and compared with the result in Japanese) • research dilution accuracy of Isobutyric acid

30. Thank you for your attention END

31. Conclusion • Dilution accuracy of hydrogen sulfide is good on both method. Concerning hexanal, the European method is almost well and the Japanese method as same as that one which is limited dilution factor to more than 300. • Except for isobutyric acid, concentration s ofthreshold measured by the European method are about 3-9 times higher than that measured by the 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.

32. 2.Difference of odour thresold between European method and Japanese method Result of odour thresold-2 (winter) Except for isobutyric acid, thresold of Europian method are higher than that of Japanese method High ←Sensitivity of panel　　→　low Log Threshold (ppｔ) Isobutyric Acid Ethyl Acetate n-Butanol hexanal ◆Dynamic Olfactometer■Triangle Odor Bag Method

33. 2.Difference of odour thresold between European method and Japanese method Result of odour thresold-1 (summer) Thresold of Europian method are higher than that of Japanese method. But standard deviation are different. High ←Sensitivity of panel　　→　low Log Threshold (ppｔ) Hydrogen sulfide Trimethylamine n-Butanol hexanal ◆Dynamic Olfactometer■Triangle Odor Bag Method

34. 3. Study of difference among three method Main Points • 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MethodA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MethodAのみ高い閾値を示し、オルファクトとにおいは差がなかった。

35. 2点比較と3点比較

36. 3. Study of difference among three method Differences among 3 methods 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. High ←Sensitivity of panel　　→　Low Low ←log threshold (ppb)　 　→　High High ← log odor coc.　 　→　Low Caution!

37. 差異の要因の定量的検討 • 上昇法と下降法（閾値の定義（回答方法）の違い） • ２倍系列と３倍系列 • ３点比較と２点比較

38. 実験方法 • 上昇法・下降法等の測定条件を変えて同一臭気を同一パネルにより両手法によって測定 • オルファクトメーターはハードウェア・ソフトウェアの制約から条件の変更が難しいため、臭袋法の条件を変更 • 各条件で1日１回ずつ合計４日間測定