mutagenic effects of emissions from old and new technology
TRANSCRIPT
Mutagenic Effects of Emissions from Old and New
Technology Diesel Engines Combusting Biogenic
and Fossil Fuel Qualities
Bünger J1,4, Munack A2,4, Schröder O3, Krahl J3,4
1 Institute for Prevention and Occupational Medicine of the German Social Accident Insurance (IPA),
Ruhr-University Bochum, Germany
2 Thünen Institute of Agricultural Technology, Braunschweig, Germany
3 Coburg University of Applied Sciences and Arts, Coburg, Germany
4 Fuels Joint Research Group, www.fuels-jrg.de
Introduction
Fuels, Engines, Methods
Results
Summary and Conclusions
Outline
2
Introduction
Fuels, Engines, Methods
Results
Summary and Conclusions
Outline
3
Components of Diesel Engine Emissions (DEE)
DEE consist of a complex mixture of compounds.
Several can be hazardous to human health:
• Carbon monoxide (CO)
• Carbon dioxide (CO2)
• Sulfur dioxide (SO2)
• Nitrogen oxides (NOX)
• Hydrocarbons (HC), thereof ca. 2-5%
• Polycyclic aromatic Hydrocarbons (PAH)
• Particles
Source: HEI 1995
Carcinogenicity of DEE
Diesel engine emissions (DEE) are considered to be
carcinogenic on the basis of numerous scientific data:
1. Strong mutagenicity of particle extracts of DEE in the Ames-test
(Huisingh et al. 1978)
2. Lung tumors in rats after inhalation of DEE (Heinrich et al. 1986)
3. Increased lung cancer risk in occupationally DEE-exposed subjects
(IARC 2012)
“In conclusion, the Working Group classified diesel engine exhaust
as “carcinogenic to humans” (Group 1).”
Genotoxicity of diesel engine particles
6
(PAH)
Modified according to HEI 1995
Direct genotoxic mechanism:
Indirect genotoxic mechanism:
PAH: Modes-of-Action
DNA
DNA-Strand Breaks
Mutations
H O
O H
O
B [ a ] P - 7 , 8 - d i h y d r o d i o l - 9 , 1 0 - e p o x i de
Reactive Oxygen Species (ROS)
DNA-Oxidation
Mutations H O
O H
B [ a ] P - 7 , 8 - d i h y d r o d i o l
O
O
B [ a ] P - 7 , 8 - d i o ne
Non substituted PAH
indirectly mutagenic
Substituted PAH
especially Nitro-PAH
directly mutagenic
Carcinogenic Components of DEE
Benzo[a]pyrene
Nitro-benzo[a]pyrene
Often much stronger mutagenic !
Introduction
Fuels, Engines, Methods
Results
Summary and Conclusions
Outline
Data Base
Projects: 23 studies from 1993 until 2012
Engines: 6 passenger cars, Euro 2 - 6;
7 truck engines, Euro 0 – VI;
2 one-cyl.-test engines (Euro 0)
Fuels: DF from gas stations used as reference in all studies
11 fossil (sulfur <2 - 500 ppm, aromates <1 - 37%)
14 biogenic (sulfur <2 ppm, aromates <1%)
Aftertreatment: Diesel Oxidation Catalyst (DOC)
Diesel Particle Filter (DPF)
Selective Catalytic Reduction (SCR)
Emission Test Stand
Sampling Setup for Mutagenicity Testing
(according to VDI-guideline 3872, page 1)
Preparation of Test Solutions
Particle phase
Soxhlet extraction of filters
Dichloromethane (150 mL)
Reduction by evaporation
Drying under a stream of nitrogen.
Condensates
Reduction by evaporation.
Drying under a stream of nitrogen.
Re-dissolution of residues in 4 mL
dimethyl sulfoxide (DMSO)
Bacterial Reverse Mutation Test = Ames-Test (OECD-Guideline 471) Standard test protocol of Maron and Ames (1983) Mutat Res 113: 173-215
Tester strains TA98 and TA100 with and without metabolic
activation by a microsomal rat liver enzyme fraction (S9)
4 concentrations; controls: DMSO (neg.) 3-NBA, 2-AF, MMS (pos.)
Docherty et al. Green Chem., 2006, 8, 560
Introduction
Fuels, Engines, Sampling Methods
Results
Summary and Conclusions
Outline
Mutagenicity of DEP from VO, RME, and high sulfur DF
(Deutz Tractor, EURO 0)
0
250
500
750
1000
1250
1500
DF VO RME
Mu
tati
on
s p
er
Pla
te
TA98 -S9
TA98 +S9
1994
Mutagenicity of DF with high sulfur
and optimization of RME combustion
0
100
200
300
400
500
600
idling 25% load rated power max. torque
Mu
tati
on
s p
er
pla
te
DF without S9
DF with S9
RME without S9
RME with S9
RME opt. without S9
RME opt. with S9
2000
DF RME GTL 1 GTL 20
25
50
75
100
125
150
175
200
225
250
Fuels
Mu
tati
on
s p
er
pla
teMutagenicity of LSDF, RME and Gas to Liquid Fuels (GTL)
2004
0
50
100
150
200
DF JME NExBTL RME
Muta
tions [
-]
-S9
+S9
0
50
100
150
200
DF JME NExBTL RME
Muta
tions [
-]
Mutagenicity of PM-Extracts (left) and Condensates (right)
2008
-10
-5
0
5
10
15
20
25
Mu
tati
on
s p
er
pla
te
DF cold
DF
warm
HVOB7 cold
HVOB7 warm
DF cold
DF warm
HVOB7 cold
HVOB7 warm
DF cold
DF warm
HVOB7 cold
HVOB7 warm
2011
Euro 6 Euro 5 Euro 3
DF RME B 20 GTL 1 GTL 20
25
50
75
100
125
150
175
200
225
250
Fuels
Mu
tati
on
s p
er
pla
te
2004
Mutagenicity of B20 from LSDF and RME
DF RME ULT V-P B20 ULT B20 V-P
0
50
100
150
200
250
300
Fuels
Mu
tati
on
s p
er
pla
teMutagenicity of B20 from Ultimate / V-Power DF and RME
2006
DF B 5 B 10 B 20 B 50 RME 0
10
20
30
40
50
60
70
80
90
100
Fuels
Mu
tati
on
s p
er
pla
teMutagenicity of a Series of Blends from DF and RME
2008
24
Mutagenicity of rapeseed oil (Mercedes Benz OM 906 LA, Euro III, ESC)
DF GTL RME VO 0
200
400
600
TA98-S9
TA98+S9
Mu
tati
on
s
2007
25
VO_mod. DF GTL RME VO
Mu
tati
on
s
0
200
400
600
800
1000
1200
1400
1600
TA98-S9
TA98+S9
Mutagenicity of rapeseed oil with preheating (Mercedes Benz OM 906 LA, Euro III, ESC)
2007
Introduction
Fuels, Engines, Methods
Results
Summary and Conclusions
Outline
Mutagenicity – Reduction in the last 20 years
No significant mutagenicity :
• Cars with Euro 5-standard
• Cars with Euro 6-standard
• Trucks with Euro VI-standard
1993
-199
7
1998
-200
2
2003
-200
7
2008
-201
2
1993
-199
7
1998
-200
2
2003
-200
7
2008
-201
2
0
100
200
300
400
500
Fossil fuels Biogenic fuels
Mu
tati
on
s p
er
L E
xh
au
st
Conclusions
Measuring only regulated compounds is not
sufficient for the estimation of health effects
from diesel engine emissions.
Independent fuel and emission research is needed
for a reliable consumer and worker protection.
Mutagenicity of DEE was lowered to non significant
levels in the last 20 years using the Ames test.
Jürgen Bünger Prof. Dr. Jürgen Bünger, MD
Endowed Chair Experimental Occupational Medicine
Institute for Prevention and Occupational Medicine of the German Social Accident Insurance (IPA)
Institute of the Ruhr-University Bochum
Buerkle-de-la-Camp-Platz 1, 44789 Bochum, Germany
Tel.: 0049 234 3024556
Fax: 0049 234 3024505
http://www.ipa.ruhr-uni-bochum.de/
email: [email protected]
Thank you for listening !
Questions ?
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