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Transcript of Coburg University of Applied Sciences and Arts .Coburg University of Applied Sciences and Arts

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Picture: EXPO Aust, Bamberg

Coburg University of Applied Sciences and Arts

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Jrgen Krahl Olaf Schrder Axel Munack Barbara Fey

Lasse Schmidt Kevin Schaper Jrgen Bnger

Emission and Health Effects from Biofuels

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

www.fuels-jrg.de

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Introduction

Fuels, Engines, Methods

Results

Summary and Conclusions

Outline

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Introduction

Fuels, Engines, Methods

Results

Summary and Conclusions

Outline

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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3001000 h

ECE R49

ESC

FTP-75

HWY

JC08

ECE R83

UDDS

C1 Cycle

CFR T40 P86 SpN

JE05

JMEC

MVEG-A

NEDC

TMG2

TMG5

[%] relative to DF

HC CO NOx PM

Regulated Emissions from Biodiesel versus DF

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Including different species of biodiesel * -50

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HC CO NOx PMNOx

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Regulated Emissions from Biodiesel versus DF

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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Em

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NOx HC

CO

Farymann engine with catalytic converter, 5-mode test

NOx, HC und CO emissions of a single cylinder engine

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Regulated Emissions from Fischer-Tropsch Fuels and Blends versus DF

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400 13-modeARTEMISCBDCEC ModeESCETCFTPFTP-75FTP Cold StartFTP Hot StartHFETHWYISO 8710JC08JE05JMECLight-duty european test cycleNEDCTMG2TMG5US06WVU-5

HC CO NOx PM

[%] relative to DF

including different blends with diesel fuel *

* GtL-blends with diesel fuel (5 80 vol%)

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Regulated Emissions from Fischer-Tropsch Fuels and Blends versus DF

-35

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HC CO NOx PMNOx

[%] relative to DF

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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).

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Genotoxicity of diesel engine particles

(PAH)

Modified according to HEI 1995

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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!

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Introduction

Fuels, Engines, Methods

Results

Summary and Conclusions

Outline

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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 and reference diesel fuel:

11 fossil (sulfur 2 - 500 ppm, aromatics 1 - 37%) 14 biogenic (sulfur

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Cartridge KI-

Engine and Emission Laboratory

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Sampling Setup for Mutagenicity Testing (according to VDI-guideline 3872, page 1)

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Zeit [min]

Dre

hzah

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min

], D

rehm

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t [N

m]

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tung

[kW

]

Drehmoment Bremse Drehzahl Motor Leistung

Torque brake Revolutions engine Power

Time [min]

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W]

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Sampling during the ESC Test

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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ue [N

m] 3000

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Torque brake Revolutions engine Power

Time [min] 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

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Sampling Conditions for Mutagenicity Testing

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Sampling Setup for Mutagenicity Testing (according to VDI-guideline 3872, page 1)

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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)

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

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

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Introduction

Fuels, Engines, Methods

Results

Summary and Conclusions

Outline

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Mutagenicity from VO, RME, and high sulfur DF Deutz Tractor, EURO < 0

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Mut

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late

TA98 -S9

TA98 +S91994

Workshop on Sprays and Biodiesel, Brunel University, 21.11. 2013

Mutagenicity of DF with high sulfur and optimization of RME combustion (Euro III)

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idling 25% load rated power max. torque

Mut

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