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○ Ryosuke Yoshiki , 1 Yuki Haga, 1 ChisatoMatsumura, 1

Investigation for Analysis and Concentration of Benzotriazole UV Stabilizers in Water Environment of Hyogo (Japan). ○ Ryosuke Yoshiki , 1 Yuki Haga, 1 ChisatoMatsumura, 1 Kazuo Fujimori, 1 and Takeshi Nakano 1,2,3.

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○ Ryosuke Yoshiki , 1 Yuki Haga, 1 ChisatoMatsumura, 1

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  1. Investigation for Analysis and Concentration of Benzotriazole UVStabilizers in Water Environment of Hyogo (Japan) ○Ryosuke Yoshiki,1 Yuki Haga,1 ChisatoMatsumura,1 Kazuo Fujimori, 1 and Takeshi Nakano1,2,3 1Hyogo Prefectural Institute of Environmental Sciences, Kobe, Hyogo 654-0037, Japan 2Osaka University, Center for Advanced Science and Innovation, Suita, Osaka 565-0871, Japan Hyogo Prefectural Institute of Environmental Sciences

  2. Japan Area: 380,000km2 Population: 127,000,000 Prefecture:47 Belgrade～Tokyo 9,000km Time difference：7h

  3. Hyogo Prefecture Russia Area:8,400km2 Population :5,528,562 Cities:29 Towns:12 Japan North Korea China Hyogo South Korea ・Saitama ・Tokyo ・ ・Kyoto ・ Kobe Osaka Kobe Himeji Pacific Ocaan Nishinomiya Nishinomiya city Himeji city (castle) (HANSHIN KOSHIEN STADIUM ) Kobe city

  4. Outline • About Benzotriazole UVStabilizers (BUVSs) • AnalyticalMethod for BUVSs • Surveysof BUVSsin Hyogo

  5. Sun blocking agents • Feature －Absorb and change the energy of the UV rays • Use －Personal care products －polymeric materials －automobile components －paints

  6. Benzotriazole UVStabilizers (BUVSs) BUVSs･･･Typical ultraviolet light absorber Property ・ Stability ・ Bioaccumulative Contamination source ・ Recreation activities ・ Wastewater treatment plants The situation when investigating ・ Few cases of an environmental survey

  7. Benzotriazole UVStabilizers (BUVSs) UV-320: 2-(2H-1,2,3-Benzotriazol-2-yl) -4,6-di-tert-butylphenol C20H25N3O1 MW：323.44 CAS No:3846-71-7 MP:152-154℃ LogKow:7.22 UV-326: 2-(tert-butyl)-4-mehtyl-6-(4-chloro -2H-1,2,3-Benzotriazole-2-yl)phenol C17H18NCl1N3O1 MW：315.8 CAS No:3896-11-5 MP:144-147℃ LogKow:6.58

  8. Benzotriazole UVStabilizers (BUVSs) UV-327: 2,4-di-tert-butyl-6-(5-chloro-2H -1,2,3-Benzotriazol-2-yl) phenol C20H24Cl1N3O1 MW：357.88 CAS No:3864-99-1 MP:150-153℃ LogKow:7.81 UV-328: 2- (2H-1,2,3-Benzotriazol-2-yl) -4,6-di-tert-phenylphenol C22H29N3O1 MW：351.49 CAS No:25973-55-1 MP:80-83℃ LogKow:8.28

  9. Cl Cl Benzotriazole UVStabilizers (BUVSs) • BCF(BCF:Bioconcentration Factor) BCF:33,300 UV-327 BCF:3,250 Dolphin (4.0ng/g) Fish (0.39ng/g) Sea water (0.12ng/L) BCF of POPs(Sea water - Dolphin) ・PCB :13,000,000 ・DDT :37,000,000 ・HCH :37,000 Similar to HCH ※Nakata,H.et.al, Occurrence and concentration of benzotriazole UV stabilizers in marine organisms and sediments from the Ariake Sea,Japan,Enviromental Science and Technology,43,6920-6926(2009)

  10. Outline • About Benzotriazole UVStabilizers (BUVSs) • AnalyticalMethod for BUVSs • Surveysof BUVSsin Hyogo

  11. BUVSs analysis(LC/MS/MS condition) LC-MS/MS

  12. Chromatograms of Standards 0.5ppb 10ppb UV320 UV320 UV326 UV326 UV327 UV327 UV328 UV328

  13. Chromatograms of Standards

  14. BUVSs analysis in water Watersample, 200mL Liq./Lid, Extraction Concentration 0.6-HCl 4mL NaCl 6g Dichloromethane 30mL×2 Nitrogenstream Resolve in methanol LC/MS/MS SRM ESI(-) ※5ng(n=2)

  15. BUVSs analysis in sediment Sampling Air-drying (in draft) Shifting (under 2mm) LC/MS/MS Analysis Drying loss (110℃,40min) Ignition loss (600℃,2h)

  16. BUVSs analysis in sediment ※100ng(n=2)

  17. BUVSs analysis Liquid-Liquid Extraction(LLE) (Water sample) Solid Phase Extraction(SPE) (Sediment sample)

  18. Outline • About Benzotriazole UVStabilizers (BUVSs) • AnalyticalMethod for BUVSs • Surveysof BUVSsin Hyogo

  19. Survey of Hyogo Russia North Korea Sea of Japan China South Korea Hyogo ・Tokyo ・Kyoto ・Osaka ・ Kobe Pacific Osean

  20. Survey of Hyogo in 2015 Sampling Points Water ＆ Sediment Water 1 1

  21. Results of Water Samples in 2015 Conc.(ng/L) 1 2 3 6 7-1 7-2 7-3 8 9 10 Sampling point in Summer Conc.(ng/L) Concentrations of BUVSs in the most points : N.D. or <10 ng/L 1 2 3 4 5 6 7-1 7-2 7-3 8 9 10 Sampling point in Winter Concentration of BUVSs in Water (2015)

  22. Results of Sediment Samples in 2015 Conc.(ng/g-dry) 1 2 3 6 7-1 7-2 7-3 8 9 10 Sampling point in Summer Conc.(ng/g-dry) High concentration in Point 6 , 7 4 5 6 7-1 7-2 7-3 8 11 12 13 14 15 16 17 18 19 Sampling point in Winter Concentration of BUVSs in Sediment (2015)

  23. Results of Sediment Samples in 2015 神崎橋 HBCD Only in Point6, UV-327 was detected most Summer right left center 神崎橋 Winter 6 6 6 7 5 4 6 5 4 5 4 7 7 7 right center left Compared with Point6, Point4and5 are very low concentration Source in the upper stream more than Point6

  24. Results of Sediment Samples in 2015 High concentration BUVSs in sediment which exceeds the survey result in other areas

  25. Results of Sediment Samples in 2015 Concentration(ng/g-dry) Ignition Loss of the mass(%) Concentration of BUVSs in sediment samples vs. ignition loss of mass

  26. Sediment in a high concentration point Sediment sample

  27. Conclusions • Any samples in water had low BUVSs concentration than methodical quantification limit, but it was detected in all points in sediment. • The high lipophilic character of BUVSs resulted in a strong trend to remain sorbed on sediment. • High concentration BUVSs was detected in sediment in 2 points in Kanzaki-gawa-river. These results exceed the other survey of whole country.

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