Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents. 13 th ETH-Conference on Combustion Generated Nanoparticles

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2 Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents 3 th ETH-Conference on Combustion Generated anoparticles Zürich, June

3 Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents 3 th ETH-Conference on Combustion Generated anoparticles Zürich, June

4 Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents What are the products of soot combustion and what are their health effects? Trojan horse, Harbour of Canakkale, Turkey

5 Diesel nanoparticles Trojan horses for genotoxic compounds Problems: anoparticles penetrate cell membranes (alveoli, blood cells) acting as Trojan horses Diesel exhaust contains dozens of carcinogenic, mutagenic, and hormone-like compounds Toxic nitrogen oxide emissions Do DPFs detoxify diesel exhaust? Trojan horse, Harbour of Canakkale, Turkey

6 Secondary pollutants of catalytic converter systems What else can a converter produce besides C 2, H 2, and 2? Toxic secondary pollutants - relevant examples

7 Secondary pollutants of catalytic converter systems What else can a converter produce besides C 2, H 2, and 2? Toxic secondary pollutants - relevant examples TWC-induced formation of ammonia TWCs the most efficient Dex systems on road Formation of 2 in diesel oxidation catalysts From a reducing to an oxidizing exhaust Formation of PAHs in diesel particulate filters? Carcinogenic PAHs from soot combustion? itration of PAHs in particulate traps? From harmless precursors to mutagenic itro-pahs? Formation of PCDD/Fs in particulate traps? The DPF- an ideal reactor

8 The VERT approach ne engine, one test cycle, 4 DPFs, 4 years of work

9 The x problem Do DPFs affect nitrogen oxide emissions? itrogen oxides ( x,, 2 )

10 The x problem itrogen oxides ( x,, 2 ) o effects with respect to engine and vehicle legislation!

11 The x problem itrogen oxides ( x,, 2 ) With respect to nitric oxide?

12 The x problem itrogen oxides ( x,, 2 ) With respect to nitric oxide?

13 The x problem itrogen oxides ( x,, 2 ) With respect to nitrogen dioxide?

14 The x problem itrogen oxides ( x,, 2 ) We have 2 filter families, one converts 2 the other forms 2!

15 Low- / high-oxidation potential DPFs Carbon monoxide, hydrocarbons, fuel We have 2 filter families, one converts C the other doesn t!

16 Low- / high-oxidation potential DPFs Carbon monoxide, hydrocarbons, fuel We have 2 filter families, one converts C the other doesn t!

17 Low- / high-oxidation potential DPFs Carbon monoxide, hydrocarbons, fuel Both filter families convert HCs

18 Low- / high-oxidation potential DPFs Carbon monoxide, hydrocarbons, fuel Both filter families convert HCs

19 Low- / high-oxidation potential DPFs Carbon monoxide, hydrocarbons, fuel o significant effects on fuel consumption

20 Low- / high-oxidation potential DPFs High-ox filters, convert C and forming 2, lox-dpfs don t! Carbon monoxide, hydrocarbons, fuel

21 Secondary pollutants of catalytic converter systems What else can a converter produce besides C 2, H 2, and 2? Toxic secondary pollutants - relevant examples TWC-induced formation of ammonia TWCs the most efficient Dex systems on road Formation of 2 in diesel oxidation catalysts From a reducing exhaust to an oxidizing exhaust Formation of PAHs in diesel particulate filters? Carcinogenic PAHs from soot combustion? itration of PAHs in particulate traps? From harmless precursors to mutagenic itro-pahs? Formation of PCDD/Fs in particulate traps? The DPF- an ideal reactor

22 Genotoxic polycyclic aromatic hydrocarbons Carcinogenic PAH Genotoxic PAHs in diesel exhaust Pyrene Fluoranthene 2 Chrysene 3 Benz(a)anthracene Benzo[k]- 7 Benzo[a]- 8 fluoranthene pyrene Benzo[b]- fluoranthene Indeno(,2,3-cd)- pyrene

23 Genotoxic polycyclic aromatic hydrocarbons Six PAHs are carcinogenic according to the WH Carcinogenic PAH Pyrene Fluoranthene 2 Chrysene 3 Benz(a)anthracene Benzo[k]- 7 Benzo[a]- 8 fluoranthene pyrene Benzo[b]- fluoranthene Indeno(,2,3-cd)- pyrene

24 Genotoxic polycyclic aromatic hydrocarbons Two are precursors for mutagenic nitro-pahs Carcinogenic PAH Pyrene Fluoranthene 2 Chrysene 3 Benz(a)anthracene Benzo[k]- 7 Benzo[a]- 8 fluoranthene pyrene Benzo[b]- fluoranthene Indeno(,2,3-cd)- pyrene

25 Carcinogenesis from benzo(a)pyrene xidative metabolic activation of benzo(a)pyrene by cytochrome P450 enzymes 8 7 Benzo(a)pyrene (BP) (+/-) 7,8 BP-oxide 0 9 H 8 7 H 8 7 H H (+) anti 7R,8S,9S,0R-BPdihydrodiol-epoxide (+/-) 7,8 BP-dihydrodiol

26 Carcinogenesis from benzo(a)pyrene Stereoselective formation of benzo(a)pyrene-da-adducts H DA H H 2 0 H 9 0 DA H 9 H 0 H 8 7 H (+) anti 7R,8S,9S,0R-BPdihydrodiol-epoxide H 8 7 H (-) 0R trans-anti-[bp]-triol- 2-deoxy-guanosine-adduct

27 Carcinogenesis from benzo(a)pyrene

28 Genotoxic PAHs For example benzo(a)pyrene? Carcinogenic PAHs

29 Genotoxic PAHs Efficient conversion of benzo(a)pyrene Carcinogenic PAHs

30 Genotoxic PAHs Conversion of all carcinogenic PAHs! Carcinogenic PAHs

31 Genotoxic PAHs Compound specific conversion? Carcinogenic PAHs 6.0 x 0-4 Pa

32 Genotoxic PAHs Compound specific conversion? Carcinogenic PAHs 6.0 x 0-4 Pa.2 x 0-3 Pa

33 Genotoxic PAHs Volatility and reactivity affect filtration efficiency! Carcinogenic PAHs 6.0 x 0-4 Pa.2 x 0-3 Pa 8.5 x 0-7 Pa 2.8 x 0-5 Pa

34 Secondary pollutants of catalytic converter systems What else can a converter produce besides C 2, H 2, and 2? Toxic secondary pollutants - relevant examples TWC-induced formation of ammonia TWCs the most efficient Dex systems on road Formation of 2 in diesel oxidation catalysts From a reducing exhaust to an oxidizing exhaust Formation of PAHs in diesel particulate filters? Carcinogenic PAHs from soot combustion? itration of PAHs in particulate traps? From harmless precursors to mutagenic itro-pahs? Formation of PCDD/Fs in particulate traps? The DPF- an ideal reactor

35 The DPF a chemical reactor Is nitration of PAHs in x-rich diesel exhaust an issue? itration of PAHs pyrene

36 The DPF a chemical reactor In one step from a harmless precursor to a mutagen? itration of PAHs pyrene -nitropyrene

37 Genotoxic itro-pahs DPF-induced nitration of PAHs Formation of -nitronaphthalene

38 Genotoxic itro-pahs Formation of -nitronaphthalene but conversion of 2-nitronaphthalene DPF-induced nitration of PAHs 3.2 x 0-2 Pa 2

39 Genotoxic itro-pahs Formation of -nitronaphthalene but conversion of 2-nitronaphthalene DPF-induced nitration of PAHs For comparison 3.2 x 0-2 Pa 2.2 x 0-3 Pa

40 Genotoxic itro-pahs DPF-induced nitration of PAHs What about 3-ring itro-pahs? 3

41 Genotoxic itro-pahs Formation of 9-nitrophenanthrene but some conversion of 3-nitrophenanthrene DPF-induced nitration of PAHs 3 9

42 Genotoxic itro-pahs itration is regioselective peri-positions are more reactive. DPF-induced nitration of PAHs 2 3 9

43 Genotoxic itro-pahs What about mutagenic itro-pahs? DPF-induced nitration of PAHs 3

44 Genotoxic itro-pahs What about less volatile itro-pahs? DPF-induced nitration of PAHs

45 Genotoxic itro-pahs Substantial variation among DPFs, but similar nitration chemistry DPF-induced nitration of PAHs 2 3 9

46 Genotoxic itro-pahs Formation and release of -nitronaphthalene and 9-nitrophenanthrene is frequent DPF-induced nitration of PAHs 2 3 9

47 Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents Do DPFs detoxify diesel exhaust? Trojan horse, Harbour of Canakkale, Turkey

48 Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents Its a long way from diesel soot to C 2 and H 2! Results: Wall-flow DPFs eliminate solid nanoparticles Some DPFs form 2, others convert it Current DPF technology lowers emissions of genotoxic compounds Some nitro-pahs are formed de novo, others are converted Conclusion: VERT -approved DPF are efficient sinks for soot nanoparticles and genotoxic compounds with moderate risks for secondary poisoning DPFs to not abate the x problem, some even enhance it!

49 Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents About 7 m 3 exhaust (3 min operation of a 3.0 L Euro-3 engine (00 kw)

50 Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents Today, wall-flow DPFs are best available technology to detoxify diesel exhaust. Are combined DPF-Dex systems the future?

51 Effects of low- and high-oxidation DPFs on genotoxic exhaust constituents Thanks: VERT team: Andreas Mayer, TTM, iederrohrdorf Jan Czerwinski, Sandro apoli, Tobias eubert, Thomas Hilfiker, Jean-Luc Petermann, Yan Zimmerli, Uni. Appl. Sci., Biel. Markus Kasper, Adrian Hess, Thomas Mosimann, Matter Engineering, Wohlen Hans Jaeckle, Urs Debrunner, liver Schumm, Intertek Caleb Brett, Schlieren. Empa colleagues: Brigitte Buchmann, Thomas Bührer, Anna-Maria Forss, Urs Gfeller, Maria Guecheva, Peter Graf, Roland Graf, Erika Guyer, Regula Haag, Peter Honnegger, Judith Kobler, Martin Kohler, Peter Lienemann, Alfred Mack, Peter Mattrel, Martin Mohr, Joachim Mohn, Christof Moor, Peter Schmid, Cornelia Seiler, Andreas Paul, Heinz Vonmont, Thomas Walter, Max Wolfensberger, Daniela Wenger, Adrian Wichser, Markus Zennegg, Kerstin Zeyer. Governement: Giovanni D Urbano, Max Wyser, Gerhard Leutert, Martin Schiess, Swiss Fed. ffice for Environment, Bern Filter- & catalyst manufacturers: >30 different diesel particulate filter systems Traugott Sandmeyer ( )

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