Folie 1Vortrag > Autor > Dokumentname > Datum
Combustion Generated Nanoparticles (Soot Precursors): Underrated Species with Potentially High Health Risk
Horst-Henning Grotheer, Tania Gonzalez Baquet, Joachim Happold,Institute of Combustion Technology, DLR Stuttgart
Antonio Borghese, Luciano Speranza, Instituto Motori, CNR, Naples
Christa Baumstark-Khan, Christine E. Hellweg, Institute of Aerospace Medicine, DLR Cologne
Vortrag > Autor > Dokumentname > Datum
Folie 2
road dusttyre attrition
10-4 10-3 10-2 10-1 1 10
0,1 1 10 100 1000 10.000
µm
nm
gas molecules
oil smoke
soot
viruses bacterias
visible light
cement dust
fly ash
particle diameter, Dp
adapted from GSF,Umweltmed. Forsch. Prax. 7, 2002
Matter presently found in the Atmosphere
range of
nanoparticles
Range of PM 10
Vortrag > Autor > Dokumentname > Datum
Folie 3
Nanoparticles – species between gas phase molecules and soot
primarysoot
some PAH exhaustgas components
nano-particles
restructuringrequires t,T
Critical stepin case ofengines
Emission of nanoparticles in addition to soot
Vortrag > Autor > Dokumentname > Datum
Folie 4
Two types of limiting structures
• already in moderately rich flamesΦ ~ 1.1 or larger
• very slow growthemitted in large numbers
• environmental aspect
• only in sooting flamesΦ ~ 2 or larger
• rapid growthrapidly decreasing numbers
• important for soot formation
Giant molecules Molecular crystallites
Vortrag > Autor > Dokumentname > Datum
Folie 5
Mobile setup for flame and engine measurements (Stuttgart)
TOF- mass spectrometer
pump
pump
MCP
reflectron
5x10-6
molecular beam
sampling line
timing electronicsIon optics
data handling
1x10-7
mbarskimmer
pulsed valve
pump pump
quartz tube
photo-ionisation
MS
Inlet system
ArF excimer laser193nm; P < 8mJ/pulse Δt = 10ns; f. = 200 cps
Vortrag > Autor > Dokumentname > Datum
Folie 6
Flame generated particles,C2H2 low pressure flame
Polymer like spectra
Average Δm between hills= mass of single layerΔ = 450u – 500u
Average mass of first„hill“ 900 – 1000u→ double layer.
Interpretation as stacksrather than chains
Note: this type of nanoparticles is found only under sooting conditions
Vortrag > Autor > Dokumentname > Datum
Folie 7
Measurements of combustion generated nanoparticles (<5 nm) behind commercial engines
500 1000 1500 2000 2500 30000
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
18_08_04 Mess 10-12
Rollermessungen IIMit LinseWarm
1400 rpm2500 rpm4000 rpm
Sig
nal (
coun
ts)
Mass (amu)
1300 1350 1400 1450 15000
1000
2000
3000
4000
5000
18_08_04 Mess 10-12
Sign
al (c
ount
s)
Mass (amu)
strong dependence on (idle) engine speed
Common result of TOC analysis:
Some 1012 particles /Ncm3
at the end of the exhaust pipe, very high relative to soot
Investigated:
2 stroke motor scooter4 stroke motor bike (2)gasoline DI research engine (industries)gasoline 4 stroke power generator (2)Diesel power generator
Result of DLR-ME:Toxicity, see below
Scooter
Vortrag > Autor > Dokumentname > Datum
Folie 8
Transmitter TX
Receiver RXRetro-reflector
Open-Path Ultra-Violet Spectrophotometry, Naples
Optical Extinction of the Atmosphere
1. Confined O2+N22. Ambient AIR
Vortrag > Autor > Dokumentname > Datum
Folie 9
O2 21%O3 102 µg/m3
NO2 130 µg/m3
EC 70 µg/m3
Nitrate 60 µg/m3
Extinction spectrum measured 1m above ground
Vortrag > Autor > Dokumentname > Datum
Folie 10
0
2
4
6
8
10
12
14
200 220 240 260 280 300 320 340 360 380 400
wavelength , nm
Ke
xt
, 1
/k
m <---- Experimental
<------- Built from Known Species
O2
O3EC
nitrate
NOC
Reconstruction of the Atmospheric Extinction Spectrumincluding the Contribution of NOC = 30 μg / m3
dp= 2 nm ⇒ Number Concentration Np> 109 / cm3
Vortrag > Autor > Dokumentname > Datum
Folie 11
Verdünnungsfaktor
10-4 10-3 10-2 10-1 100
Rel
. Lum
ines
zenz
(Lux
i/Lux
0)
0.0
1.0
2.0
3.0
4.0
5.0
BMW
Rel
. Flu
ores
zenz
(Flu
x/Flu
0)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Verdünnungsfaktor
10-4 10-3 10-2 10-1 100
Rel
. Lum
ines
zenz
(Lux
i/Lux
0)
0.0
1.0
2.0
3.0
4.0
5.0Vespa
Rel
. Flu
ores
zenz
(Flu
x/Flu
0)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
BMW4 stroke engineno catalytic converter
Vespa2 stroke engine
Nanoparticle Samples from Motor BikesSWITCH-Test of DLR-ME using Salmonellae bacterias
In both cases:50% of the bacterias survive@ 2E10 particles/scm(mass of 3000 u assumed)
Vortrag > Autor > Dokumentname > Datum
Folie 12Verdünnungsfaktor10-4 10-3 10-2 10-1 100
Rel
ativ
es Z
ellw
achs
tum
0.0
0.2
0.4
0.6
0.8
1.0Menschliche Lungenzellen A549
Inkubationszeit
30 m
in 1 h
2 h
4 h
24h
30 m
in 1 h
2 h
4 h
24h
30 m
in 1 h
2 h
4 h
24h
Rel
ativ
e G
enex
pres
sion
no
rmal
isie
rt a
uf B
2M-E
xpre
ssio
n
-6
-4
-2
2
4
6
* *1/-1
Inkubationszeit
1 h 2 h 4 h 1 h 2 h 4 h 1 h 2 h 4 h
Rel
ativ
e G
enex
pres
sion
nor
mal
isie
rt a
uf B
2M-E
xpre
ssio
n
-6
-4
-2
2
4
6
* *
** *
-1/1
GADD45beta CDKN1A IL-6 Significance*
Nanoparticle samples from a Propane (C3H8) flameGene expression in human lung cell solutions (DLR-ME)
Inkubationszeit
30 m
in 1 h
2 h
4 h
24h
30 m
in 1 h
2 h
4 h
24h
30 m
in 1 h
2 h
4 h
24h
Rel
ativ
e G
enex
pres
sion
no
rmal
isie
rt a
uf B
2M-E
xpre
ssio
n
-6
-4
-2
2
4
6
*
1/-1
Inkubationszeit
30 m
in1 h2 h4 h30
min1 h2 h4 h
30 m
in1 h2 h4 h
Rel
ativ
e G
enex
pres
sion
norm
alis
iert
auf
B2M
-Exp
ress
ion
-6
-4
-2
2
4
6
**
** *
*
*
*
*
-1/1
Vortrag > Autor > Dokumentname > Datum
Folie 13
Conclusion
Nanoparticles are species between polyaromatics and soot.They can be measured by a variety of methods such as optical UV extinction, mass spectrometry and others.They are predominantly emitted from instationary combustion sources(engines)According to UV extinction measurements they are present in theatmosphere in high numbersExperiments using bacterias and human lung cells indicate a high toxicity(cytotoxicity as well as genotoxicity)In the current EU regulation on PM10 the particle mass is measured. This grossly underrates nanoparticles due to their small masses.