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Chemistry-based assessment of combustion exhausts
Norbert Heeb Empa, Überlandstrasse 129 Lab for Advanced Analytical Technologies CH-8600 Dübendorf Phone +41-58-765 42 57 Fax +41-58-765 40 41 e-mail [email protected] Internet http://www.empa.ch
Focus Event: Effect- and toxicity-based assessment of exhausts Empa, March 16, 2018
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Road vehicles on earth
From 0.1 to 1 billion in 60 years
(3 vehicles/s) 90 million new vehicles/y
(3800 as I spoke, 86’000 today)
Kyoto (in force 2005)
From 3 to 8 billion in 60 years (3 x)
Kyoto (in force 2005)
(10 x)
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Road vehicles on earth
From 0.1 to 1 billion in 60 years
(3 vehicles/s) 90 million new vehicles/y
(3800 as I spoke, 37’000 this morning)
Kyoto (in force 2005)
From 300 to 400 ppm in 60 years
Kyoto (in force 2005)
(10 x)
(1.6 ppm CO2/y) 12.5 Gt CO2/y
109 vehicles x 104 km/y x 200 g CO2/km = additional 2 Gt CO2/y
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Chemistry-based assessment of combustion exhausts
Mass spectrometry is the tool for HAP identification and quantification
The sooting problem (Soot is bad news at the nanometer scale)
Combustion exhaust, ia a toxic cocktail (Many ways for intoxication)
The chemistry of fuels
Combustion of fossil fuels is pure chemistry
(What you feed is what you get!)
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The chemistry of fuels
What you feed is what you get, not one atom is lost!
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If you burn fossil fuels you get lots of CO2 and water in the best case
- Alkanes (CxH2x+2) are major fuel constituents of CNG, LPG, gasoline, jet fuel, diesel fuel, heating oil. - Alkyl benzenes (C6+xH6+2x) important constituents of gasoline
Combustion of fossil fuels
Fossil fuels are complex mixtures of >1000 compounds (except CNG & LPG)
The chemistry of fuels
- Alkyl naphthalenes (C10+xH8+2x) constituents of gasoline, jet & diesel fuels
- Alkyl PAHs constitutents of jet & diesel fuels
- Carbon contents 85-87% (850’000-870’000ppm)
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Energy consumption of Swiss traffic
Energy consumption traffic (TJ)
Consumption of gasoline, diesel and jetfuel?
Traffic accounts for 34% of total Swiss energy consumption(2010)
96% based on fossil fuel!
gasoline diesel jet fuel electricity
(incl. railway & public transport)
<1% CNG, and all future concepts
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If you burn fossil fuels you get lots of CO2 and water, but stoichiometry matters
Stoichiometric combustion of alkanes:
The chemistry of fuels
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Stoichiometric combustion of alkyl benzenes:
The chemistry of fuels
If you burn fossil fuels you get lots of CO2 and water, but stoichiometry matters
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Stoichiometric combustion of alkyl naphthalenes:
The chemistry of fuels
If you burn fossil fuels you get lots of CO2 and water, but stoichiometry matters
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- alkanes are combusted as mixtures (exception CNG)
- The global biofuel market is growing, weather we like it or not
Oxygen to carbon ratio (O/C):
Are biofuels part of a sustainable society?
The chemistry of fuels
CNG LPG Gasoline Diesel Jet fuel 4.0
3.6
3.2
2.8
2.4
2.0
If you burn mixtures, stoichiometric combustion is difficult to maintain!
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- alkanes are combusted as mixtures (exception CNG)
- The global biofuel market is growing, weather we like it or not
Oxygen to carbon ratio (O/C):
Are biofuels part of a sustainable society?
The chemistry of fuels
CNG LPG Gasoline Diesel Jet fuel 4.0
3.6
3.2
2.8
2.4
2.0
Sub-stoichiometric combustion results in sooting!
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- alkanes are combusted as mixtures (exception CNG)
- The global biofuel market is growing, weather we like it or not
Oxygen to carbon ratio (O/C):
Are biofuels part of a sustainable society?
The chemistry of fuels
CNG LPG Gasoline Diesel Jet fuel 4.0
3.6
3.2
2.8
2.4
2.0
If you burn mixtures, stoichiometric combustion is difficult to maintain!
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The sooting problem
The result of too low oxygen level, temperature or too short combustion time
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The sooting problem of diesel engines
The result of too low oxygen level, temperature or too short combustion time
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GDI fleet properties: Mean GDI fleet (n=7) GDI-1: Mitsubishi Carisma (1.8 L) GDI-2: VW Golf (1.4 L) GDI-3: Opel Insignia (1.6) GDI-4: Volvo V60 T4F (1.6 L) GDI-5: Opel Zafira (1.6 L) GDI-6: Citroën C4 Cactus (1.2 L) GDI-7: VW Golf VII (1.4 L) Diesel benchmark (with DOC+DPF, EGR) DI: Peugeot 4008 (1.6 L)
Euro-6 Euro-6
Euro-3
Euro-5 Euro-5
Euro-4 Euro-5
Euro-5
The sooting problem of GDI vehicles
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Each transient induces the release of nanoparticles
The sooting problem of GDI vehicles
Euro-5 GDI (Volvo V60, 1.6 L)
WLTC
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GDI particles indeed are nanoparticles of 10-200 nm
Nanoparticle emissions of GDI vehicles
Millions of new «sooting stars» are born every year now!
- GDI particles are nano!
- Maxima at 20 & 80nm
- Bimodal distribution
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Europe is flooded with soot nanoparticles of GDI vehicles
GDI vehicles on the rise
- 30% of the EU fleet will be GDI in 2020 - 53 mio GDI vehicles in Europe (2010-2020)
GDI vehicles, on average, release: 700 x more nanoparticles and 17 x more genotoxic PAHs than a Euro-5 diesel vehicle with DPF!
Before you buy a GDI vehicle, please read the GASOMEP report (https://www.empa.ch/web/s604/soot-particles-from-gdi)
Nanoparticle emissions of GDI vehicles
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Combustion exhausts are toxic cocktails
Many ways to get intoxicated, mostly chronic diseases, only CO kills quickly
How toxic are combustion exhausts, what can chemical analysis tell us?
Acute toxicity: - CO, reactive nitrogen compounds (RNCs)
Chronic toxicity: - oxidative stress - inflammation - chronic obstructive pulmonary disease
Genotoxicity: - mutations - cancer
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Adverse health effects of combustion exhausts
Problem: Acute toxicity
The simple oxidation of methane can lead several toxic intermediates
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tive
(per
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Adverse health effects of combustion exhausts
Problem: CO intoxication
CO limit 1000 mg/km for gasoline vehicles results in ~1300 mg/m3 exhaust
- headache, dizziness in 6-8 h 35 (44)
ppm (mg/m3)
100 (125) - headache, dizziness in 2-3 h
- headache, dizziness in 2-3 h, loss of judgment 200 (250)
400 (500)
800 (1000)
1600 (2000)
3200 (4000)
6400 (8000)
12800 (16000)
- dizziness, nausea in <10 min, death <30 min
- dizziness, convulsion, respiratory arrest, death <20 min
- unconsciousness after 3 breath, death <3 min
- frontal headache, in 1-2 h
- dizziness, nausea, convulsion in 45 min in 6 h
- dizziness, nausea in 20 min, death <2h
Euro-4,-5,-6 1000 mg/km Euro-2 2200 mg/km
2x
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Adverse health effects of combustion exhausts
Benzene, carcinogenic fuel and exhaust constitutent
Problem: benzene toxicity
Ambient air EU limit Jan. 1st, 2010, 1 µg benzene/m3
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Adverse health effects of combustion exhausts
Metabolic activation leads to several toxic and reactive intermediates
Hang B. J. Nucleic Acids. 2010, 1-29, doi:10.4061/2010/709521
Benzene activation with human myeloperoxidase (MPO):
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Adverse health effects of combustion exhausts
Metabolic activation leads to reactive intermediates and DNA adducts
DNA adducts from activated benzene metabolites:
t,t-muconic acid
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Adverse health effects of combustion exhausts
Metabolic activation leads to reactive intermediates and DNA adducts
DNA adducts from activated benzene metabolites:
o-benzoquinone
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Adverse health effects of combustion exhausts
Metabolic activation leads to reactive intermediates and DNA adducts
DNA adducts from activated benzene metabolites:
p-benzoquinone
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Adverse health effects of combustion exhausts
1 precursor, 3 reactive metabolites, 9 DNA adducts
DNA adducts from activated benzene metabolites:
1 precursor
3 metabolites
9 DNA adducts to be repaired
mutagenesis
leukemia
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Adverse health effects of combustion exhausts
The good thing about benzene - it is volatile, you might be able to exhale it!
Problem: benzene intoxication
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Adverse health effects of combustion exhausts
Problem: anthracene toxicity
The bad thing about PAHs - you can’t exhale them if they are bound to particles!
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Several PAHs are carcinogenic according to the WHO
1 2
5 6 7 8
1 1
111
1
3 4
11
Pyrene Fluoranthene Chrysene Benz(a)anthracene
Benzo[b]- fluoranthene
Benzo[k]- fluoranthene
Benzo[a]- pyrene
Indeno(1,2,3-cd)- pyrene
Genotoxic PAHs
Carcinogenic PAHs
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Carcinogenesis from benzo(a)pyrene
Oxidative metabolic activation of benzo(a)pyrene
Benzo(a)pyrene (BP) (+/-) 7,8 BP-oxide
O 78
(+/-) 7,8 BP-dihydrodiol
7
8HO
OH
(+) anti 7R,8S,9S,10R-BP- dihydrodiol-epoxide
78HO
OH
O
9
10
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Stereoselective formation of benzo(a)pyrene-DNA-adducts
(+) anti 7R,8S,9S,10R-BP- dihydrodiol-epoxide
78HO
OH
O
9
10
(-) 10R trans-anti-[BP]-triol-N2-deoxy-guanosine-adduct
78HO
OH
9
10NHN
HO
NH
O
N
N
DNA
10NHN
HO
NH
O
N
N
DNA2
Carcinogenesis from benzo(a)pyrene
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Carcinogenesis from benzo(a)pyrene
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Trojan horse, Harbour of Canakkale, Turkey
Problem: Trojan horse effect
Nanoparticles penetrate cell membranes (alveoli, placenta, blood cells) acting like a Trojan horse
Diesel and GDI nanoparticles act as Trojan horses for genotoxic compounds
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World Health Organization, IARC Diesel engine exhaust: A group 1 carcinogen
Diesel engine exhausts cause cancer in humans
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World Health Organization, IARC Diesel engine exhaust: A group 1 carcinogen
Group 1
Lung cancer in exposed workers
Diesel engine exhausts cause lung cancer in humans
only 125 years after Rudolf Diesels patent!
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World Health Organization, IARC Diesel engine exhaust: a group 1 carcinogen
Diesel engine exhaust cause cancer in humans
12315 workers, 198 lung cancer death (16 in 1000)
diesel exhaust exposure: a potential public health burden
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Swiss Clean Air Act (LRV): List of carcinogenic compounds
EU ambient air limit Dec. 31st, 2012, 1 ng benzo(a)pyrene/m3
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Mean annual NO2 levels: City of London
From a Swiss perspective, the Brexit did not solve the problem!
Swiss Limit 30 µg/m3
M4
M25
Heathrow Airport
M25 M1
M40
EU Limit Jan. 1st, 2010 40 µg/m3
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Impact of deNOx-technologies on RNC emissions?
Converter technologies strongly affect RNC levels, but not always to the better
Reactive nitrogen compounds in combustion exhausts
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pyrene 1-nitropyrene
In one step from a harmless precursor to a mutagen?
The DPF – a chemical reactor
Nitration of PAHs
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Regioselective nitration of pyrene
Nitration in alpha-position?
The DPF – a chemical reactor
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The DPF - a chemical reactor
or in beta-position?
Regioselective nitration of pyrene
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The DPF - a chemical reactor
or in gamma-position?
Regioselective nitration of pyrene
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The DPF - a chemical reactor
Two of the three isomers are mutagenic.
ON
O
O
NO
N
O
O
αγ
β
Regioselective nitration of pyrene
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The DPF - a chemical reactor
If nitration is possible ones, why not twice?
Nitration of nitropyrenes
ON
O
O
NO
N
O
O
αγ
β
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The DPF - a chemical reactor
From one precursor to 3 nitropyrenes to 15 dinitropyrenes?
ON
O
N
O
O
N
O
O
N
O
O
O
NO
NOO
N
O
O2,4
2,5
2,7
O
NO
O
NO
O
NO
O
NO
ON
O
O
NO
ON
O
4,5
4,9
4,10
γβ
β β
γ
γ
N
O
O
ON
O
ON
O
ON
O
N
O
O
1,7
1, 2
ON
O
ON
O
ON
O
NO
O
NOO
NO
O
1, 8
1, 6
1, 3
ON
O
ON
O
O
NO
NOO
1, 5
1, 4ON
O
ON
O
O
NO
NO O
1, 10
1, 9
β
α
α
α
αγ
αγ
β
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The DPF - a chemical reactor
The most potent direct-acting mutagens known are dinitropyrenes
ON
O
N
O
O
O
NO
O
NO
O
NO
O
NO
ON
O
O
NO
ON
O
4,5
4,9
4,10
γ
γ
N
O
O
ON
O
ON
O
ON
O
ON
O
ON
O
NO
O
NOO
NO
O
1, 8
1, 6
1, 3
NOO
α
ααγ
β
470
140‘000
180‘000
250‘000
2200 rev. nmol-1
Ames Salmonella typhimurium TA98 reversion assay
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Genotoxic Nitro-PAHs
Low oxidation potential DPF can support 1-nitro-pyrene formation!
1
ON
O
15
DPF-induced nitration of PAHs
Heeb et al. ES&T, 2008, 42, 3773-3779 Heeb et al. ES&T, 2010, 442, 1078-1084
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Chemistry-based assessment of combustion exhausts
Mass spectrometry is the tool for HAP identification and quantification
The sooting problem (Soot is bad news at the nanometer scale)
Combustion exhaust, ia a toxic cocktail (Many ways for intoxication)
The chemistry of fuels
Combustion of fossil fuels is pure chemistry
(What you feed is what you get!)
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Chemistry-based assessment of combustion exhausts by HRMS, a powerful tool
HR-MS is all we need for chemical hazard assessment of exhausts
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High resolutions mass spectrometry: Is all we need for quantitative analysis at the pg-level
GC-/ LC-HR-MS (Orbitrap)
Full scan mode – all in one run (shorter sampling times, less elaborate sample clean-up, better results )
Higher selectivity (chemical noise supression, 120’000 resolution)
High sensitivity (both EI and NCI mode)
HR-MS is the ideal tool for chemical hazard assessment of exhausts
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Chemistry-based assessment of combustion exhausts by HRMS, a powerful tool
Hazard assessment of combustion exhausts by chemical analysis
in vitro cell culture tests are helpful too
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Chemistry-based assessment of combustion exhausts
If we dare to expose miners to non-treated diesel exhausts for decades, we don’t need animial tests
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Chemistry-based assessment of combustion exhausts
?