what are the important parameters that need to be defined for a carbonaceous aerosol analysis ?
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Hélène CACHIER Laboratoire des Sciences du Climat et de l’Environnement. Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003. What are the important parameters that need to be defined for a carbonaceous aerosol analysis ?. - PowerPoint PPT PresentationTRANSCRIPT
What are the important parameters that need to
be defined for a carbonaceous aerosol
analysis ?
Hélène CACHIER
Laboratoire des Sciences du Climat et de l’Environnement
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
How should these be documented for
different analysis protocols ?
Carbonaceous Combustion Aerosols
Physical and chemical diversity: their own story
due to their origin source
due to the atmospheric environment
due to their age
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Carbonaceous Combustion Aerosolsmorphology
porous fly ash (carbonaceous)
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
diesel microsoots
Courtesy of A. Lefèvre
Carbonaceous Combustion Aerosolsmorphology
fresh diesel microsoots
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Biomass burning particles
Courtesy of A. Gaudichet
Carbonaceous Combustion Aerosols
Atmospheric aging
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Carbonaceous Combustion Aerosols
Chemical complexity of EC (BC) and OC
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
From D. Smith et al., 1989
Difficult to find a chemical separation
Difficult to find a thermal separation
Fate of attached VOC?
Carbonaceous Combustion Aerosols
Chemical complexity of the aerosol mix
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Biomass burning aerosols (savanna fires)
Carbonaceous Combustion AerosolsChemical complexity of the aerosol mix
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Weekly samples from Finokalia (Crete) nov 01-jun02
What type of method to be used?
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
2-step thermal method (Oxygen) : « blind » method
TOA under Oxygen : better
TOA under He and He/O2:
Pyrolysis vs Combustion: don’t mix
11TO
T
10TO
T
11bT
OT
12TO
T
12TO
T
11TO
T
10TO
T
11bT
OT
13TO
R
13TO
R
I
Interlaboratory comparisonsAre not consistent
Discrepancy is sample dependent
Schmid et al, 2001
What to avoid ?
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Interferences with other species: carbonates dusts salts (K)
Charring of the Organic Component
Overlap of the 2 EC and OC components:
Value of optical correction ?
Untimely removal of EC
TOA / Oxygen
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Charring minimized
Role of K (Na)
Carbonates : no problem? Temperature max?
Plateau temperature and duration ?
Negative role of concentration loading?
Temperature steps Optical (laser transmission) measurement
C peaks Calibration
Limit OC/EC
2 -step TOA example
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
OC1 OC2 OC3 OC4 OP EC
2- Step TOA He/He-Ox
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Peak (fraction) resolution BUT Important charring
role of plateau temperaturerole of plateau durationrole of concentration loadingrole of inorganic salt
Untimely departure of EC (negative artefact)
Refractory OC (positive artefact) temperature of the last OC plateau
Reflectance or Transmittance ? role of concentration loadingrole of filter matrix
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
From Chow et al.,2001
First type of 2-step TOA
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
From Chow et al.2001
Second type of 2-step TOA
Thermograms of levoglucosan in the (a) absence and in the (b) presence of ammonium
bisulfate using the UST-2 thermal method
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Thermal evolution of Organic species altered by inorganic species
Yu et al., 2002
!!! use of standard
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Yu et al., 2002
An important part of the charred OC(PEC) is from water soluble aerosol
Use aerosol water extract as PEC surrogate
Thermograms of a same aerosol water extract using (a) the NIOSH and (b) the
UST-3 thermal methods.
Prolonging the duration at each temperature step reduces charring
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Yu et al., 2002
Hypothetic thermograms of pure PEC, pure NEC, and a mixture of the two in a HeO2 atmosphere
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Charring corrections primarily rely on the hypothesis that charred carbon (PEC) evolves prior to EC (Native EC NEC)
Charred OC (PEC) does not evolve
prior to EC (NEC)b
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Thermograms of (a) an untreated aerosol sample and its water extract and (b) charcoal
Nor do PEC and NEC have
the same absorption coefficient
From Yang and Yu, 2002
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rans
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tive
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100% He 2% O2 + 98%He
OC1 OC2 OC3 OC4 EC1 EC2 EC3 EC4 EC50
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rans
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TempLaser TransFID
100% He 2% O2 + 98%He
OC1 OC2 OC3 OC4 EC1 EC2 EC3 EC4 EC5
Analysis of a « dust» sample by the Niosh method
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Whitening of the filter sample
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
RecommendationsReduce charring correction uncertainty:
reduce charring by increasing plateau durationreduce charring of the high temperature plateauincrease the resolution around the OC/EC split point
Avoid interactions with dusts (iron oxides)Proceed to removal of carbonates prior to analysis if necessary
Avoid untimely departure of EC during the He step
Need to find an experimental design to evaluate if OC remains on sample after the He step of the thermal procedure
Define an acceptable concentration range (gC/cm2)
charring cannot be predefined
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3,0
BC
, µgC
/m3
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nss-
SO
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g/m
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BC, Thermal methodnss-SO4
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25/07 30/07 04/08 09/08 14/08 19/08 24/08
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/m3
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nss-
K, µ
g/m
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BC, IMPROVE Tempprogramnss-K
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Analysis of Crete samples Minos experiment, Aug 2001
Why does the DRI-Improve mebbhod insensitive to «industrial» BC?
Why is it very sensitive to Biomass Burning BC?
From Sciare et al., 2003
Analysis of impactor samples
Heterogeneity of the depositConcentration of particles on small areas
Role of the substrate (quartz vs aluminium)
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Laboratoire des Sciences du Climat et de l ’Environnement Durando ECOC workshop, March 2003
Are you really wanting to change your own protocole??