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Quantification of Aerosol Species
with AMS and ACSM:
Presented by: Manjula Canagaratna
2021 Virtual AMS/ACSM User Meeting
Jan 19-22, 2021
3.0
2.5
2.0
1.5
1.0
0.5
0.0
Nitra
te E
quiv
ale
nt
Ma
ss C
once
ntr
atio
n (
µg
m-3
)
16014012010080604020
m/z (Daltons)
Ammonium 4.8 ug/m3Nitrate 5.8Sulphate 9.4Organics 13.4Chloride 0.15
Mexico City 2/2002
Overview
Ion
In
ten
sity (
Hz)
1) How do we convert AMS ion signal to species mass
concentrations in AMS and ACSM?
2) Interferences/ Biases observed with thermal vaporizer
Aerosol Mass Concentrations
Avogadro’s Number (NA), Flow (Q), Molecular weight (MW)
Ionization Efficiency (IENO3 ) – primary calibrant
Collection Efficiency (CES)
Relative Ionization Efficiency (RIES)
(Calibrations and empirical parameterizations)
See Usr mtg talks: Leah Williams, Ben Nault
Apportion ion
intensities to
species
(Frag Table)
Collection Efficiency
Lens TransmissionOverlap between particle
beam and vaporizer
Particle
Bounce on
oven
Huffman et al.
Efficiency with which particles are transmitted to and collected at vaporizer
Collection Efficiency: EL
Standard Lens: Liu et al. (2007)
EL: Size dependent Transmission through lens
AMS, ACSM, SP-AMS: All use same Lens, same CEL effects
PM2.5 Lens: Xu et al. (2017)
See usr mtg Talk: Ben Nault, Day2 AM
• The lens cutoffs should to be taken into
account when comparing AMS with other
instruments
How de we account for this in AMS concentration
calcs?
• Since the curve for each lens is slightly different
from these curves, we do not directly apply these
curves to correct the AMS measurements.
Collection Efficiency: Es
Most particles (even aspherical soot particles) are collected with
greater that 95% efficiency.
Huffman et al. AS&T. 2005
Es: Overlap
between particle
beam and
Vaporizer
Use Es =1 for most situations
Standard Vaporizer: Eb is dominant contribution to CE.
Bounce depends on particle phaseReferences: Matthew et al.,AS&T, 2018.
Quinn et al., JGR, 2006. Allan et al., JGR, 2004,Drewnick et al, AS&T, 2004. Docherty, AS&T, 2013, Middlebrook et al.,
AS&T, 2011
Collection Efficiency: Eb
Eb < 1 (solids), Eb =1 (Liquids)
1) Nitrate content
2) Acidity
3) Relative humidity in sampling line
Ambient
CE≈ 0.5 (internally mixed SO4)
Empirical parameterization for ambient
particles (Middlebrook et al.)
• Included in analysis programs
Lab Eb values are highly variable.
Calibrate CE OR use SMPS for
concentrations
Capture Vaporizer to increase Eb
AMS and ACSM: SV
CE dominated by Eb = f(composition,phase, size)– Ambient- Empirical parameterization
– Lab – Measure explicitly
AMS and ACSM: CV
Eb = 1
Fragmentation patterns of CV different from SV
Need to account for these changes in frag patterns
when quantifying species
Eb: Correction
factor for particle
bounce off
vaporizer
CV: Capture
SV: Bounce
Xu et al., AS&T, 2017
SV: Flash Vap
Hu et al., AS&T,2017
Ambient Aerosol
during SOAS
field campaign
Collection Efficiency: SP-AMS
Onasch et al., AS&T, 2015
SP2 Module: 1064 nm laser
Lens TransmissionOverlap between particle beam
and laser beam (ES <1)
Particle
Bounce
AMS Mass Quantification
Converting AMS ion signal to species mass
Collection Efficiency (CE)
Relative Ionization Efficiency (RIES)
- Measure of (ions/unit mass)s / (ions/unit mass)NO3
NOTE: if you use RIES=1, then mass concentration is
expressed as NITRATE EQUIVALENT MASS
RIE (Relative Ionization Efficiency)Inorganic Species
Early lab calibrations on inorganics by Frank Drewnick, Ann Middlebrook
RIENO3 accounts for fact that NO3 mass loading is calculated from additional ions besides m/z 30 and 46 used in NO3 IE calibration
Other inorganic RIEs are variable and should be calibrated
RIENH4 - 3-5
RIE SO4 - 1.2 (0.5-2)
RIE Cl - 1.3 (1.6-2.5)
RIE (organic species, OA)
Ambient OA is made up of thousands of individual
organic species. What do we use as a calibrant?
Ambient Measurements:
- RIEOA = 1.4 is based on
laboratory work
(Jimenez et al., AS&T, 2016)
Dependence of RIEOA on OSc
Lab RIEOA = 1.7 for Osc > -1.5 (within 20% of 1.4 used for ambient)
Should we use different RIE for ambient POA and SOA components?
Xu et al. AS&T,(2018)
See Usr mtg talks: Day 1, PM
Offsetting of RIE by CE differences?
RIE (POA) > RIE (SOA)
CE (POA) < CE (SOA)
RIEOA of POA and SOA
Jimenez et al. AS&T, 2017
Large biases not observed for
ambient OA mass calculated with
constant RIE =1.4 (even for high
POA content)
More ambient measurements needed to
derive variable RIE parameterizations
Organic Nitrates (ON) and Sulfates (OS)
1) Investigate fragment ion
ratios
ON: 30 (NO+)/m/z 46 (NO2+)
typically ranges from 5-10
IN: typically 2-3(Fry et al., ACP, 2009, Bruns et al., ES&T, 2010. Farmer et al., PNAS, 2010, Boyd et al., ACP, 2015,Kiendler-Scharr, GRL, 2016, Ng et al., ACP, 2017)
OS: SOX+ ratios
(Phinney et al., Deep Sea Res, 2006. Ge et al., Environ. Chem., 2012., Gilardoni, PNAS, 2016.
Song., ACP, 2019. Chen et al., ES&T, 2019)
2) Lab Calibrations
3) Combined PMF (organic
and inorganic)
See Usr mtg talks: Day 3, AM
Kiendler-Scharr, GRL, 2016.
Chen et al., ES&T, 2019
C-S or C-N containing fragments are minor
Quantification of semi-refractory species
• Slow vaporization- Monitor open &closed signal
- Ions have different vaporization
timescales.
- Pick fragment ions with
faster response for quantification
(e.g. NaCl+, HCl+)
• Pb, NaCl, metal halides (e.g., chlorides,
bromides or iodides of Al, Ba, Cd, Cu, Fe, Hg,
K, Na, Pb, Sr, Zn)
• Reactions on
vaporizer
Salcedo et al., AS&T, 2010. Ovadnevaite et
al., JGR, 2012. Drewnick et al., AMT, 2015.
Drewnick et al., AMT, 2015.
Ambient Cl : Tobler et al., AMT, 2020.
See Usr mtg talks: Day 3, AM
“Pieber” Effect
Pieber et al. ES&T, 2016.
Multiple ACSM instruments at ACMCC(Freney et al., AS&T, 2019)-Application of lab calibrations of Pieber effect for pure
NH4NO3 can overcorrect ambient data-Pieber effect is a function of NO3_MF
-In ambient, NO3_MF < 50% most of the time So, Pieber effect small, but should be aware of it
(test mixtures of (NH4)2NO3 and
(NH4)2SO4)
The End
Thank you for your attention!
Happy to take questions now or at end of
session.
Questions : [email protected]