Fighting both toxic exhaust and climate gas emissions from

bio-blended diesel– Assessment of strategies.

Seminar Sogndal 25 Feb 2011

Strategies:
Biodiesel fuel pre-treatment
Through high gauss magnetic beam, i.e. aligning the fuel molecules to
increase the electron spin (magnetohydrodynamics)
Adding water to form emulsified fuel
Additives and liquid catalysts
Various types of additives and liquid catalysts
New exhaust filter technologies
What properties should they have?
How to develop them?
The potential of Molecular Dynamics Simulations in designing exhaust
filters
Carbon nanotubes (CNTs) as functional material in filters
The problematics of
bioblending
Western Norway Research
Institute
Sogndal
 Means and standard deviations of triplicate mutagenicity tests
of particle extracts of DF, RME, Ult, B20 Ult, V-P, and B20 V-P
using tester strain TA98 with (+S9) and without (-S9)
metabolic activation by rat liver enzymes; OM 906; ESC

Munack, A., Krahl, J., Bünger, J., Ruschel, Y., Schröder, O. (2008): Exhaust Gas Emissions and Mutagenic Effects of Modern Diesel Fuels, GTL, Biodiesel, and
Biodiesel Blends. CIGR - International Conference of Agricultural Engineering XXXVII Congresso Brasileiro de Engenharia Agrícola. Brazil, August 31 to
September 4, 2008.
 Means and standard deviations of triplicate mutagenicity tests
of particle extracts of DF, RME, B20, GTL1, and GTL2 using
tester strain TA98 with (+S9) and without (-S9) metabolic
activation by rat liver enzymes; OM 906; ESC

Munack, A., Krahl, J., Bünger, J., Ruschel, Y., Schröder, O. (2008): Exhaust Gas Emissions and Mutagenic Effects of Modern Diesel Fuels, GTL, Biodiesel, and
Biodiesel Blends. CIGR - International Conference of Agricultural Engineering XXXVII Congresso Brasileiro de Engenharia Agrícola. Brazil, August 31 to
September 4, 2008.
 Means and standard deviations of triplicate mutagenicity tests
of particle extracts of DF, RME, B20, GTL1, and GTL2 using
tester strain TA98 with (+S9) and without (-S9) metabolic
activation by rat liver enzymes; OM 906; ESC

Munack, A., Krahl, J., Bünger, J., Ruschel, Y., Schröder, O. (2008): Exhaust Gas Emissions and Mutagenic Effects of Modern Diesel Fuels, GTL, Biodiesel, and
Biodiesel Blends. CIGR - International Conference of Agricultural Engineering XXXVII Congresso Brasileiro de Engenharia Agrícola. Brazil, August 31 to
September 4, 2008.
 Means and standard deviations of quadruple mutagenicity
tests of particle extracts of DF, B5, B10, B20, B50, and RME
using tester strain TA98 with (+S9) and without (-S9)
metabolic activation by rat liver enzymes; AVL 502.019; rated
power

Munack, A., Krahl, J., Bünger, J., Ruschel, Y., Schröder, O. (2008): Exhaust Gas Emissions and Mutagenic Effects of Modern Diesel Fuels, GTL, Biodiesel, and
Biodiesel Blends. CIGR - International Conference of Agricultural Engineering XXXVII Congresso Brasileiro de Engenharia Agrícola. Brazil, August 31 to
September 4, 2008.
 Means and standard deviations of quadruple mutagenicity
tests of particle ex-tracts using tester strain TA98 with (+S9)
and without (-S9) metabolic activation by rat liver enzymes;
engine: MAN D08; Test: ETC

Munack, A., Krahl, J., Schröder, O., Bünger, J. (2010): Potentials of Biofuels. XVIIth World Congress of the International Commission of Agricultural
and Biosystems Engineering (CIGR). Hosted by the Canadian Society for Bioengineering (CSBE/SCGAB) Québec City, Canada June 13-17, 2010.
 Deposition measured by
Munack et al (2010)

Munack, A., Krahl, J., Schröder, O., Bünger, J. (2010): Potentials of Biofuels. XVIIth World Congress of the International Commission of Agricultural
and Biosystems Engineering (CIGR). Hosted by the Canadian Society for Bioengineering (CSBE/SCGAB) Québec City, Canada June 13-17, 2010.
 Hypothesis for the B20-
effect
Mutagenicity correlates with the tendency of blends to form
sediments, particularly if aged (partly oxidized) biodiesel
is used.
The mutagenicity is therefore hypothesized to be caused
when carotenoids in the aged biofuel lose their anti-
oxidative effect in the biodiesel fraction, forming
oligomers and thereby sediments.

Munack, A., Krahl, J., Schröder, O., Bünger, J. (2010): Potentials of Biofuels. XVIIth World Congress of the International Commission of Agricultural
and Biosystems Engineering (CIGR). Hosted by the Canadian Society for Bioengineering (CSBE/SCGAB) Québec City, Canada June 13-17, 2010.
 Size distribution – bus, 1400 rpm,
full load

Mayer, A., Czerwiński, J., Wyser, M., Heitzer, A. (2010): Particle Emissions of Diesel Busses with
RME/Diesel Blends. Euro Oil & Fuel 2010. Prace naukowe INiG 172. PL ISSN 0209-0724.
Scanning Mobility Particle Size (SMPS)
measurements

Heikkilä, J. Virtanen, A., Rönkkö, T., Keskinen, J., Aakko-Saksa, P., Murtonen, T. (2009): Nanoparticle Emissions
from a Heavy-Duty Engine Running on Alternative Diesel Fuels. Environ. Sci. Technol. 43, 9501-9506.
 Background (1)
• Exhaust toxicology effects of blending biodiesel
into fossil diesel.
– FAME-PAH nanoagglomerates from
biodiesel/fossil diesel blends using molecular
simulation: studies of nanoagglomerate
formation and toxic membrane- crossing
effects.
In collaboration with:
University of Uppsala, Bio-Medical Center, Supercomputing Group.
Laboratory of Exhaust Emissions Control, Hochschule für Technik
und Informatik, Biel.
Oil and Gas Institute Krakow
 Background (3)
• Biodiesel is mainly composed of methyl esters deriving from the trans-esterification
of plant oils such as soya bean oil (generating soya-bean methyl esters - SME) and
rapeseed oil for the production of rapeseed methyl esters (RME), which are both
classified as fatty acid methyl esters (FAME).

• Fossil diesel on the other hand, is quite rich in combustion products of stronger
toxic degrees. The majority of chemical compounds from the soluble organic
fraction (SOF) of fossil diesel arranges in agglomerates which contain unburned
hydrocarbons, semi-oxidized hydrocarbons and PAHs.

• The level of PAHs in fossil diesel has been documented to be quite high, reaching
as much as 7 times higher concentrations than in biodiesel and their carcinogenic
potential is well known.

• The combination of biodiesel and fossil diesel introduces therefore new

toxicological aspects given the mixtures of two different chemistries, giving rise to
potentially “toxic partnerships” between biodiesel components and fossil diesel
components, and given the suggestions in previous studies, the biodiesel exhaust
component of interest for a toxicological assessment is uncombusted FAME.
 Preliminary results -
Electrostatic Potential (ESP)
mapping
 Preliminary results -
OME cooling simulation

Video
OME cooling simulation –
cluster size vs time
 Nanoagglomerate
simulations

A lipid layer in contact with a nanoparticle. The nanoparticles ability

to cross the layer is assessed using molecular simulations in order
to label a potential toxicological degree.
Membrane simulation

Membrane MDS
 Methods
•
Molecular dynamics simulations on supercomputer
•
Factors to be assessed for interaction with
PAH-FAME:
• Membranes
•
Proteins at blood barriers and the
pleural cavity (e.g. SNARE proteins)
•
Golgi apparatus transporter proteins
(e.g. CARGO proteins)
•
DNA (e.g. unspecific DNA fragments
crystallized with genetic regulators)
• Lysosomes and phagocytic components
 Methods
•
Physiochemical analysis of exhaust
• Separation and detection using field-flow
fractionation and fluorescence as well as UV
spectrophotometry to determine particle size
distributions.
• The fractions will be analysed by FTIR and
NMR to confirm the presence of FAME
 Methods
•
Toxicology studies of exhaust
•
Cell exposure to different ratios of bioblended diesel
will provide answers to the crucial queation: Does
blending increase the toxicity? And if so, how large is
the effect?
•
Cellular toxic effects of exhaust will be studied with
cells from human epithelial tissue being exposed to
exhaust in exposure chambers. After exposure of
modeled human respiratory tract to the exhaust the
cells will be examined for:
•
Cytotoxicity (percentage of dead cells)
•
Inflammatory reactions
•
Oxidative stress
 Methods
•
Studies of interaction between PAH/FAME and cells
• PAH-FAME complex will be studied by
exposing cells, to obain dose response curves,
for:
•
The major type of FAMEs in biodiesel
from rape, sunflower, soya and palm oil
(methyl esters of C16:0, C18:1, C18:2),
•
blended with PAH, nitro-PAH, and oxy-
PAH, in various ratios, and exposed to
cells.