past and future issues in exhaust particle measurement and control david b. kittelson center for...
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Past and Future Issues in Exhaust Particle Measurement and Control
David B. Kittelson
Center for Diesel Research
University of Minnesota
Aristotle University
Thessaloniki, Greece
23 July 2003
Acknowledgements
• We have had help from many collaborators– In the Center for Diesel Research
» Feng Cao, Marcus Drayton, Jason Johnson, Hee Jung Jung, Duane Paulsen, Winthrop Watts, Robert Waytulonis, Qiang Wei, Darrick Zarling
– In the Particle Technology Lab» Peter McMurry, Kihong Park, Hiromu Sakurai
– At UC Riverside» Herbert Tobias, Paul Ziemann
– At Paul Scherrer Institute» Nick Bukowiecki, Urs Baltensperger
• And many sponsors– Coordinating Research Council, U.S. Office of Heavy Vehicle
Technologies, Engine Manufacturers Association, Southcoast Air Quality Management District, California Air Resources Board, Cummins, Caterpillar, Perkins, Volkswagen, and Volvo.
• In recent years many concerns have been raised about extremely tiny particles, smaller than 50 to 100 nm in diameter, that are emitted by engines and other combustion sources. This presentation considers issues associated with the formation and measurement of these particles from current and future low emission Diesel engines
Outline
• Introduction• On-road measurements• Structure and Composition• How they form• Formation downstream of aftertreatment devices• Alternatives to mass measurements• Conclusions
Outline
• Introduction• On-road measurements• Structure and Composition• How they form• Formation downstream of aftertreatment devices• Alternatives to mass measurements• Conclusions
Typical Diesel Particle Size Distributions, Number, Surface Area, and Mass Weightings Are Shown
0
0.05
0.1
0.15
0.2
0.25
1 10 100 1,000 10,000
Diameter (nm)
No
rmal
ized
Co
nce
ntr
atio
n (
1/C
tota
l)dC
/dlo
gD
p
Number Surface Mass
Fine ParticlesDp < 2.5 m
Ultrafine ParticlesDp < 100 nm
NanoparticlesDp < 50 nm
Nuclei Mode - Usually forms from volatile precursors as exhaust dilutes and cools
Accumulation Mode - Usually consists of carbonaceous agglomerates and adsorbed material
Coarse Mode - Usually consists of reentrained accumulation mode particles, crankcase fumes
PM10Dp < 10 m
In some cases this mode may consist of very small particles below the range of conventional instruments, Dp < 10 nm
Heavy-Duty Engine Emission Standards
• It was thought that the 1994 standards would lead to the use of exhaust filters - but high performance electronically controlled engines met standards without them
• The combination of 90% PM reduction and 95% NOx reduction in 2007 makes aftertreatment virtually certain
• Recent concern about global warming by elemental carbon particles makes particle control by filtration even more attractive
Year Particulate Matter (g/kW-hr)
NOx (g/kW-hr)
1988 0.80 8.0 1991 0.34 6.7 1994 0.13 6.7 1998 0.13 5.4 2007 0.013 0.27
Emissions of Ultrafine and Nanoparticles from Engines• Current emission standards are based on filter mass. Recently
interest in other measures, i.e, size, number, surface, has increased.
• Concerns about particle size– New ambient standards on fine particles– Special concerns about ultrafine and nanoparticles – number or surface area may be
a better measure of biological response than mass– Indications that reductions in mass emissions sometimes increase number emissions
• Difficulties associated with measurement of ultrafine and nanoparticles
– Typically, with current engines more than 90% of particle number and more than 35% of particle mass are formed from volatile precursors during exhaust dilution.
– These fractions will be even higher with future ultra low emission engines– Particle formation during sampling and dilution is highly nonlinear and extremely
sensitive to conditions
Background - Historical Perspective
• A HEI study published in 1996 showed dramatic increase in nanoparticle emissions for a prototype 1991 Diesel engine compared to 1988 engine
– This raised concerns that low mass emission engines might increase number emissions
– It was suggested that these emissions were tiny carbon particles that might constitute a new health threat
• Further investigation has alleviated some of those concerns– The recent CRC E-43 study (2002) showed for typical modern Diesel engines
» Nanoparticles mostly volatile rather than solid» Both reduced mass and number emissions are reduced
• In any case, high nanoparticle emissions are not a new development!
– Roadside measurements made starting in the 60’s nearly always show a large nuclei (nanoparticle) mode
– Both Diesel and spark ignition sources
Outline
• Introduction• On-road measurements• Structure and Composition• How they form• Formation downstream of aftertreatment devices• Alternatives to mass measurements• Conclusions
U of M Mobile Laboratory built to study formation of nanoparticles in the atmosphere for the CRC E-43 project
• Instruments (primary instruments highlighted in blue)
– SMPS to size particles in 9 to 300 nm size range
– ELPI to size particles in 30 to 2500 nm size range
– CPC to count all particles larger than 3 nm
– Diffusion Charger to measure total submicron particle surface area
– Epiphaniometer to measure total submicron particle surface area
– PAS to measure total submicron surface bound PAH equivalent
– CO2 , CO, and NO analyzers for gas and dilution ratio determinations
During the DOE / CRC E-43 program particles from modern Diesel engines were measured on road and in the laboratory
Here we have a 1999 highway tractor with its plume being characterized by the University of Minnesota Mobile Emission Laboratory
Comparison with previous studies: Nuclei mode particles from newer engines are at lower concentrations and somewhat smaller in diameter
0.0E+00
5.0E+08
1.0E+09
1.5E+09
2.0E+09
2.5E+09
3.0E+09
1 10 100 1000
Particle Diameter (nm)
dN
/d(l
og
(Dp
)) (
par
t./c
m3 )
HEI Composite (1991)
AP2 chase (1979)
Engine 1 chase (2000)
Engine 2 chase (1999)Engine 3 chase (1999)
Corrected for dilution ratioNot corrected for particle losses
All data except HEI are for standard on-highway EPA/Federal fuels. HEI fuel lower S ~ 100 ppm
Nuclei Mode Particles Exist in Large Concentrations over Roadways
• Measurements made with University of Minnesota Mobile Laboratory
• Large concentrations observed in presence of both Diesel and spark ignition traffic
• The nuclei mode forms rapidly in the diluting plumes of vehicles – time scale seconds
• Nuclei mode decays rapidly downwind of roadway – time scale minutes
• The focus here is on nucleation in diluting exhaust plumes, nucleation also occurs in the atmosphere as a result formation of low vapor species by atmospheric chemistry but usually on a longer time scale
Typical Roadway Number Concentrations from Several Instruments and Road Speed
Dp > 3 nm
Dp > 29 nm
Dp > 9 nm
On-highway measurements made on urban freeways in Minnesota show a large nuclei mode even in the absence of significant Diesel traffic
• Traffic speed has at least as much influence on the size of the nuclei mode as the presence of Diesel traffic
• Particle number increases and size decreases as traffic speed increases• Particle volume (mass) is higher under low speed congested conditions• It appears that slow moving congested traffic leads to storage of volatile materials
in the exhaust system• As vehicles speed up the exhaust system heats leading to the release of the
materials which subsequently form nanoparticles
0
100000
200000
300000
400000
500000
1 10 100 1000
Midpoint Diameter (nm)
dN
/dlo
gDp
(p
art.
/cm
3)
Diesel=Y, MPH >=0 <=10 Diesel=Y, MPH >10 <50 Diesel=Y, MPH >=50
Diesel=N, MPH >=0 <=10 Diesel=N, MPH >10 <50 Diesel=N, MPH >=50
0.0E+00
1.0E+04
2.0E+04
3.0E+04
4.0E+04
5.0E+04
6.0E+04
0 10 20 30 40 50 60
Speed, mph
N/V
(pa
rt./ m
3 )
0
6
12
18
24
30
36
DG
N (
nm)
N/V
DGN
N/V of 1 part./m3 =1012 part./gm for spherical unit density particles
Diesel
No Diesel
Nuclei Mode Decays Rapidly Downwind of Roadways
• Modeling (Capaldo and Pandis, 2001) indicates
– For typical urban conditions, characteristic times and transit distances for 90 % reduction of ultrafine concentrations are on the order of a few minutes and 100-1000 m, respectively.
– For a given wind speed, ultrafine particles are expected to survive and travel a factor of ten greater distances in a rural flat area as compared to an urban downtown location.
• Mobile particle sources will influence the aerosol particle number concentrations mainly near roadways.
Outline
• Introduction• On-road measurements• Structure and Composition• How they form• Formation downstream of aftertreatment devices• Alternatives to mass measurements• Conclusions
Some of the instruments used to determine composition and structure of Diesel particles
Particle Technology Laboratory
NanoMOUDI
TDPBMS measures the volatility and mass spectra of the volatile fraction of all the particles in selected size ranges between 15 and 300 nm - Summary Results
• Engines– Deere 4045T medium-duty
– Caterpillar C12 heavy-duty
– Cummins ISM
• Fuels– Federal pump fuel, 360 ppm S
– California pump fuels, 50 and 96 ppm S
– Fischer-Tropsch, < 1 ppm S
• Test conditions– Light and medium load
• Composition of volatile fraction– Organic component of total
diesel particles and nanoparticles appears to be mainly unburned lubricating oil
– Major organic compound classes are alkanes, cycloalkanes, and aromatics
– Low-volatility oxidation products and PAHs have been found in previous GC-MS analyses, but are only a minor component of the organic mass
– Nanoparticles formed with higher S Federal pump fuel contain small amounts of sulfuric acid but those formed with the lower S fuels show no evidence for sulfuric acid
OC/EC analysis of nano-MOUDI Samples, gives results generally consistent with TDPBMSAnalysis performed by Barbara Zielinska, Desert Research Institute
0
100
200
300
400
500
600
700
800
0.001 0.01 0.1 1 10
Dp (m)
dm
/dlo
gD
p ( g
/m3 )
OC EC mass EC + OC
Not corrected for dilution ratio Not corrected for particle losses
Aluminum substrates
EPA fuel, 330 ppm S
0
100
200
300
400
500
600
700
800
0.001 0.01 0.1 1 10
Dp (m)
dm
/dlo
gD
p ( g
/m3 )
OC EC mass EC + OC
Not corrected for dilution ratio Not corrected for particle losses
Aluminum substrates
CA fuel, 50 ppm S
There is nearly no EC in nuclei mode
The nuclei mode is smaller with lower S fuel, but it is still nearly all OC
Typical Composition and Structure of Diesel Particulate Matter
• Solid particles are typically carbonaceous chain agglomerates and ash and usually comprise most of the particle mass
• Volatile or semi-volatile matter (sulfur compounds and organics (SOF)) typically constitutes 35% (5-90%) of the particle mass, 90% (30-99%) of the particle number
• Carbon and sulfur compounds derive mainly from fuel
• SOF and ash derive mainly from oil• Most of the volatile and semi-
volatile materials undergo gas-to-particle conversion as exhaust cools and dilutes
60%
5%
10%
20%5% Carbon
Ash
Sulfate and Water
Lube Oil SOF
Fuel SOF
Outline
• Introduction• On-road measurements• Structure and Composition• How they form• Formation downstream of aftertreatment devices• Alternatives to mass measurements• Conclusions
Nature of particles emitted by Diesel engines
• Diesel engines produce a bimodal size distribution in the submicron range
• With current engines– The nuclei mode is in the 3-30 nm diameter range and contains most of
the particle number
– The accumulation mode is in the 30-500 nm range and contains most of the particle mass
• These modes form by different mechanisms• The nuclei mode may contain the majority of both the mass
and the number emitted by future technology engines
A dilution ratio of 1000 may be reached in 1 - 2 s
Atmospheric dilution leads to nucleation, absorption, and adsorption - in excess of 90 % of the particle number may form as the exhaust dilutes
Carbon formation/oxidationt = 2 ms, p = 150 atm.,
T = 2500 K
Ash Condensationt = 10 ms, p = 20 atm.,
T = 1500 K
Exit Tailpipet = 0.5 s, p = 1 atm.,
T = 600 KSulfate/SOF
Nucleation and Growtht = 0.6 s, p = 1 atm.,D = 10, T = 330 K
Fresh Aerosol overRoadway–Inhalation/Aging
t = 2 s, p = 1 atm.,D = 1000 T = 300 K
IncreasingTime
Formation
Atmospheric AgingExposure
Particle formation history – most volatile nanoparticles form during dilution
University of Minnesota
This is where most of the volatile nanoparticles emitted by
engines usually form.
There is potential to form solid nanoparticles here if the ratio of
ash to carbon is high.
Particles formed by Diesel combustion carry a strong bipolar charge
Nuclei mode
• Nuclei mode particles form mainly from volatile precursors– The nuclei mode typically consists mainly of heavy hydrocarbons, mainly from
lubricating oil, and sulfates
– Although although the mode is mainly hydrocarbon, its formation is facilitated by sulfur in the fuel
– Its formation is very dependent on dilution conditions, especially dilution rate and dilution air temperature
– Its formation is favored by low solid carbon and high precursor concentration
– It may be all that is left when carbon is removed by exhaust filtration
• Solid nuclei mode particles may form from metals in the lube oil or fuel– Formed from oil under engine conditions that lead to little solid carbon
formation.
– Formed from fuel when metallic additives or high metal fuels are used.
Accumulation mode
• The accumulation mode is where most “soot” or “smoke” resides• It consists primarily of carbonaceous agglomerates and adsorbed hydrocarbons• Particles in this mode are strongly light absorbing• Most of the lubricating oil ash is found in this mode• The density of accumulation mode particles decreases with increasing size
– Fractal like behavior– Low densities cause size to be underestimated by some methods
• Accumulation mode particles carry a significant bipolar electrical charge that is produced during the basic combustion process
– Offers potential for particle sensing– Could influence filtration
• Accumulation mode particles are not strongly influenced by dilution conditions
• Accumulation mode particles have been reduced sharply by better engine technology
Studies of Diesel Nanoparticle Formation Using a Variable Residence Time Dilution System
Engine
CPC
PrimaryEjectorPump
Insulated Variable Residence Time
section
Diluted NOx
SMPS
OverflowBypass
Three Way Valve
SecondaryOrifice
SecondaryEjector Pump
OverflowBypass
PressureGauge
PrimaryOrifice
ExhaustPipe
Tygon Flexible
Tube
Air InletThermocouple
Humidity and temperature
Sensor
PressureGauge
Emission Rack, CO2,
NOx
Three Way Valve
SamplingProbe
Thermo-couple
Retractable tubing
Heated or Cooled Compressed Air Compressed
Air
Influence of Residence Time and Temperature on Number Weighted Size Distributions
• Medium-duty Diesel engine running at medium speed and load• Increasing residence time in the primary dilution chamber from 230 ms to
1 s increases the size of the nuclei mode by two orders of magnitude• Decreasing the temperature in the primary dilution chamber from 66 to 32
°C increases the size of the nuclei mode by about one and one half orders of magnitude
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
1.00E+10
1 10 100 1000
Dp (nm)
DN
/DL
og
Dp
(P
art
./c
m³)
Residence time = 1000 ms 100 ms 230 ms
Tdilution = 32 °C, Primary DR ~ 12
1600 rpm, 50% load
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
1.00E+10
1 10 100 1000
Dp (nm)
DN
/DL
og
Dp
(P
art.
/cm
³)
Tdil (32 °C) Tdil (48 °C) Tdil (65 °C)
Residence Time ~ 400 ms, Primary DR ~ 12Humidity Ratio ~ 0.0016
1600 rpm, 50% load
Influence of residence time and temperature on total number concentrations – nearly all in nuclei mode
3350
65
90
400
900
0.00E+00
1.00E+08
2.00E+08
3.00E+08
4.00E+08
5.00E+08
6.00E+08
7.00E+08
Number Concentrations
(Part./cm³)
Dilution Temperature (°C)
Residence Time (ms)
Heavy-Duty DieselMedium Load and Speed
Primary Dilution Ratio = 12
A 2-stage, porous tube/ejector dilutor could simulate on-road nuclei mode formation under summer highway conditions
• Results shown are composite of loaded and unloaded highway cruise for a modern heavy-duty Diesel engine with full electronic engine management
• The relative sizes of the two modes are more significant than the absolute levels – due to uncertainty in on-road dilution ratios
• In general the CA fuel produced a smaller nuclei mode than EPA fuel
• These results show that it is possible to simulate carefully defined on-road conditions
• At present, it is unclear which on-road conditions should be simulated. There are many variables including
– Temperature– Previous operating history– Road speed– Exhaust system design– Others ….
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
1 10 100 1000
Dp (nm)
dN
/dlo
gDp
, p
art/
cm3
Cat Chassis Dyno 3406E, EPA Fuel
Cat Chase 3406E, EPA Fuel
Corrected for DRNot corrected for particle losses
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
1 10 100 1000
Dp (nm)
dN
/dlo
gDp
, p
art/
cm3
Cat Chassis Dyno 3406E, CA Fuel
Cat Chase 3406E, CA Fuel
Corrected for DRNot corrected for particle losses
Lab
On-road
Lab
On-road
EPA fuel
CA fuel
Outline
• Introduction• On-road measurements• Structure and Composition• How they form• Formation downstream of aftertreatment devices• Alternatives to mass measurements• Conclusions
Influence of an uncatalyzed exhaust filter on particle size and concentration
• Filters remove accumulation mode particles very effectively• Nuclei mode particles may form downstream of filters, especially at longer residence times• These particles form from volatile materials that are in the gas phase in the filter and are
thus not collected
1.00E+03
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
1 10 100 1000
Dp (nm)
DN
/DL
og
Dp
(P
art.
/cm
³)
Upstream, Res. 40 ms Upstream, Res. 6000 ms
Downstream, Res. 40 ms Downstream, Res. 6000 ms
Mode 6
Upstream
Downstream
Figure 11
1.00E+03
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
1 10 100 1000
Dp (nm)
DN
/DLo
g D
p (P
art./
cm³)
Upstream, Res. 40 ms Upstream, Res. 6000 ms
Dow nstream, Res. 40 ms Dow nstream, Res. 6000 ms
Mode 4Peak power speed25% load
RatedTorque
Formation of a volatile nuclei mode downstream of a catalyzed Diesel particulate filter (DPF)
• The results shown are for tests of a catalyzed DPF on a modern Cummins engine
• DPF very efficient for solid particles
• May form a very large nuclei mode downstream of DPF at high load conditions
• Size of mode increases with sulfur content of fuel, but still observed with near zero sulfur fuel
• Sulfuric acid likely major component
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1.0E+08
1.0E+09
1.0E+10
1 10 100 1000
Dp (nm)
dN
/dlo
gD
p, p
art
/cm
3
No CDPF, No TDCDPF No TDCDPF With TD
Corrected for DRNot corrected for particle losses
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1.0E+08
1.0E+09
1.0E+10
1 10 100 1000
Dp (nm)
dN
/dlo
gD
p, p
art
/cm
3
No CDPF, No TDCDPF No TDCDPF With TD
Corrected for DRNot corrected for particle losses
26 ppm S fuel
1 ppm S fuel
Filter performance is best evaluated under sampling conditions that minimize nuclei mode formation
• Results shown are for a VW TDI with an uncatalyzed DPF• Here we are investigating how trap loading influences filtration
performance• Concentrations are shown on the left, penetrations on the right
0.00
0.03
0.06
0.09
0.12
0.15
1 10 100 1000
Dp (nm)
Par
tic
le P
ene
trat
ion
Time = 5 min Time = 10 min Time = 15 min
Tunnel Temperature = 60 CPDR = 40, TDR = 140
Low Sulfur Fuel ~ 360 ppm
1.00E+03
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
1 10 100 1000
Dp (nm)
dN
/d(L
og
Dp
) (p
art./
cm3)
Upstream Downstream: T= 5 min Downstream: T= 10 min Downstream: T = 15 min
Tunnel Temperature = 60 CPDR ~ 40, TDR ~ 140
Low Sulfur Fuel ~ 360 ppm
Increasing time
Increasing time
On road characterization of aftertreatment devices– we sniff our own exhaust plume
Driver side sample point
Passenger side sample point
Background sample point
Stacks
Stacks
Plume sampling points on MEL
1.0E+02
1.0E+03
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1 10 100 1000
Dp, nm
dN/d
logD
p, p
art/
cm3
On road tests of particle filtration device
All tests done with 15 ppm S fuel (post 2006) with standard or low sulfur lubricant
Engine out with low S oil
On road tests of particle filtration device
1.0E+02
1.0E+03
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1 10 100 1000
Dp, nm
dN/d
logD
p, p
art/
cm3
Engine out with low S oil
Filter with low S oil, August
All tests done with 15 ppm S fuel (post 2006) with standard or low sulfur lubricant
On road tests of particle filtration device
1.0E+02
1.0E+03
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1 10 100 1000
Dp, nm
dN/d
logD
p, p
art/
cm3
Engine out with low S oilFilter with standard oil, August
Filter with low S oil, August
All tests done with 15 ppm S fuel (post 2006) with standard or low sulfur lubricant
1.0E+02
1.0E+03
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1 10 100 1000
Dp, nm
dN/d
logD
p, p
art/
cm3
On road tests of particle filtration device
Engine out with low S oilFilter with standard oil, August
Filter with standard oil, October
Filter with low S oil, August
All tests done with 15 ppm S fuel (post 2006) with standard or low sulfur lubricant
On road tests of particle filtration device – volume (mass) distributions
0.0E+00
5.0E+00
1.0E+01
1.5E+01
2.0E+01
2.5E+01
3.0E+01
3.5E+01
4.0E+01
1 10 100 1000
Dp, nm
dVdl
ogD
p,
m3 /c
m3
Engine out with low S oil
Filter with standard oil, August
Filter with standard oil, October
Filter with low S oil, August
All tests done with 15 ppm S fuel (post 2006) with standard or low sulfur lubricant
Particles from future engines
• Solid particles in both the nuclei and accumulation modes may be nearly completely eliminated by filtration
• Filters cannot directly remove the gas phase precursors that lead to the formation of nuclei mode particles– Precursors may be removed by adsorption on collected particles
followed by..
– Hydrocarbon precursors may be destroyed in catalyzed systems to the extent allowed by kinetics (mainly mass transfer) but sulfuric acid may be formed
• If filters remove nearly all of the solid particles the only thing left will be volatile particles in the nuclei mode, with all the sampling problems associated with this mode
Outline
• Introduction• On-road measurements• Structure and Composition• How they form• Formation downstream of aftertreatment devices• Alternatives to mass measurements• Conclusions
Filter mass measurements with low emission engines - issues
• Very difficult to accurately measure filter mass at low levels• For volatile particles, filter mass does not adequately represent suspended
mass (what we breathe)– DPF performance measured with filters is very different from that measured with
instruments that measure suspended particles (VERT (Switzerland), SWRI,..)– Absolute suspended mass measurements made with a new instrument developed at of U of
M (Park, et al., 2003) show that filters may significantly overstate the mass of volatile particles
– Sampling and dilution may strongly influence results
• Other measures may better predict environmental impact– Number– Surface area– Black carbon
• The European Union is expected to institute a solid particle number or surface area standard to supplement filter mass standard
• Fast response, low cost instruments needed for engine diagnostics, conventional smokemeters inadequate
An instrument suite that would offer an attractive alternative to filter mass
• A sampling and dilution system that adequately simulates atmospheric dilution conditions
• A device to remove volatile particles• Condensation particle counter• An active surface area instrument• A black carbon instrument
• For more fundamental work one of the new fast response sizing instruments
Outline
• Introduction• On-road measurements• Structure and Composition• How they form• Formation downstream of aftertreatment devices• Alternatives to mass measurements• Conclusions
Conclusions
• The particulate mass emitted by future Diesel engines will be very low and difficult to measure accurately.– This would be true even if all the material were solid
– Unfortunately much of the material will consist of volatile nuclei mode particles that form during exhaust dilution
– Volatile particles sampled on a filter may be very different from those that we breathe
• Instruments that directly measure suspended particles rather than collecting them on a filter avoid these difficulties
Future Issues
• Both the fuel and lubricating oil properties will play an important role in the performance of aftertreament devices– Sulfur and phosphorus– Metallic ash
• Many low emission engine concepts without traps have potential to for significant nanoparticle emissions mainly associated with the lubricating oil – Spark ignition engines – especially older worn engines– Gaseous fuel engines– Homogeneous charge compression ignition engines (HCCI)
• Recent measurements on a Boeing 757 gave number emissions in the same range or higher than current Diesel engines
• Certain roadways, on ramps, airports, etc. are likely nanoparticle “hotspots”
Alternatives to filter mass – dilution and sampling, sample conditioning
• System used for dilution and sampling of exhaust must adequately simulate nuclei mode formation under representative atmospheric conditions
• The system must be designed to minimize particle losses that may be very large for sub 10 nm particles
• A system to differentiate between solid and volatile particles should be included– Thermal denuder, Dekati, Matter
– Catalytic Stripper, U of M, SWRI
Alternatives to filter mass - particle sizing of suspended particles
• Current– Scanning Mobility Particle Sizer, size range 3 to 700 nm, TSI
» Commonly used» Not suitable for transient measurements
– Electrical Low Pressure Impactor, size range ~10 to 2500 nm, Dekati» Widely used in Europe, Japan» Poor response to nuclei mode
• New– Electrical Diffusion Battery, size range ~10 to 200 nm, Matter
» Fast response» Poor size resolution
– Differential Mobility Spectrometer, size range 5 to 500 nm, Cambustion» Fast response, < 1 s» Expensive
– Real Time Mobility Particle Sizer, size range 5 to 500 nm, new from TSI » Fast response, < 1 s» Expensive
Alternatives to filter mass - fast response integral measures of suspended particles
• Total number– Condensation Particle Counter, size range > 3 to 11 nm, TSI
» Time resolution, 1 – 13 s» Extremely sensitive
• Active surface area– Diffusion Charger, size range > 10 nm, (Matter, Dekati)
» Inexpensive» Dp1.4
» Time resolution, 1 s
– Electrical Aerosol Detector (TSI)» Inexpensive» Dp1.1
» Time resolution, 1 s
Alternatives to filter mass - fast response integral measures
• Black carbon mass– Laser induced incandescence, Sandia
» Expensive» Time resolution, < ms
– Photo acoustic, DRI» Expensive» Time resolution, ~1 s
– Aethalometer, Magee Scientific» Particles collected on filter, not an issue for solid particles» Inexpensive» Time resolution, ~1 s – 1 min
• Total mass (particles collected subject to artifacts similar to filters)– Tapered Element Oscillating Microbalance, Rupprecht & Patashnick
» Time resolution, ~1 s
– Quartz Crystal Microbalance, Booker» Time resolution, ~1 s