Experimental Atmospheric Chemistry
(12.335/12.835)
Section 3, Lecture 3:
Karin Ardon-Dryer & Sarvesh Garimella
Tuesday, Nov 25, 2014
1
Today
• Atmospheric Particles
• Atmospheric Clouds
2
Remainder of Today
This image has been removed due to copyright restrictions.
Please see: Figure 2.15 of the book Atmospheric Chemistry and Physics:
From Air Pollution to Climate Change. ISBN: 9780471720188.
3
Seinfeld and Pandis
Aerosol Abundance
This image has been removed due to copyright restrictions.
Please see: Table 2.20 of the book Atmospheric Chemistry and Physics:
From Air Pollution to Climate Change. ISBN: 9780471720188.
4
Unless otherwise specified figures from Seinfeld and Pandis
Aerosol Composition Before 1994
• So, what’s the problem(s)
here?
•Courtesy / adapted from J.
Jimenez
5
Thermal Desorption
Aerosol Mass Spectrometer
This image has been removed due to copyright restrictions.
Please see: http://cires1.colorado.edu/jimenez/amsanimation.gif.
This image has been removed due to copyright restrictions.
Please see: http://www.airmonitor.cn/upload/editorfiles/
2008.12.3_13.43.7_7015.JPG.
This image has been removed due to copyright restrictions.
Please see: http://www.tropos.de/fileadmin/_processed_/
csm_Aerosol_chemicalKK_20131212_c10452182e.jpg.
https://www.tropos.de/en/research/projects-infrastructures-technology/technology-at-tropos/chemical-analytics/
aerosol-mass-spectrometry-techniques/
6
Single Particle Mass Spectrometry
PALMS
Particle Analysis by Laser Mass Spectrometry
Particle
Inlet
start
stop
+
300
µs
100
200
Particle
Sizing
Particle
Composition
-
Intensity
Intensity
+
0
m / z µ t2
m / z µ t2
Image courtesy of Deborah Gross. Used with permission.
Courtesy of D. Gross
7
10
Na
ion current (mA)
1
+
Al
+
+
K
Fe
Ca
0.1
+
+
SO
Li
0.01
Mineral Dust particle
+
Cu
Apr 07 16:06
8.5 km 237 K
Da = 1.3 m
+
+
+C
Rb
+
Ba
+
Pb
+
0.001
0
10
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
m/z
+
ion current (mA)
C
Sulfate-Organic particle
+
1
CO +
+
C NO
0.1
C3
2
+
+
SO
+
HSO2
0.01
+
HSO3
+
H3SO4
Pb
+
0.001
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
m/z
8
adapted from D. Cziczo
Influential Results
Detector Signal (mA)
A
19980507 #6672
19 km: 31oN
θ=437 K
HSO4-
0.3
0.2
H
HSO3-
0.1
O-
OH-
SO3-
S-
SO4-
H34SO4-
0.0
0
20
40
60
80
100
120
B
Detector Signal (mA)
0.4
CN- & C2H2-
0.3
0.2
OHH-
0.1
C2-
HSO4-
CHO2C2H2O-
O-
Cl-
35
19980501 #1120
14.6 km: 22oN
θ=360 K
C2H5CO2CH3CO2-
CH2OHSO3-
SO3-
HSO3- H34SO 4
Br-
79
SO4-
l-
0.0
0
20
40
60
80
100
120
most
many common some
rare
maybe
He
Li Be
B
C
N
O
F Ne
Na Mg
Al Si
P
S Cl Ar
V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
K Ca
Sc
Ti
Rb Sr
Y
Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te
I
Xe
Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Cs Ba
Fr Ra
La
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac
Th Pa U
Figure by MIT OpenCourseWare.
Ion mass/charge
Figure by MIT OpenCourseWare.
Murphy et al. Science 1998
9
Free Tropospheric
• Biomass Burning
Altitude (km)
Tropopause
• Sulfate-Organic
mixtures dominate in
UTLS
• Mineral Dust: 10-30%
• Little Sea Salt in UT
• Meteoric particles in
stratosphere
• Acidic sulfate mainly in
stratosphere
Number Fraction
Image courtesy of Karl Froyd. Used with permission.
K. Froyd, unpublished
10
This image has been removed due to copyright restrictions.
Please see Figure 6 on page: https://cloud1.arc.nasa.gov/
intex-na/publications/articles/2006JD007340.pdf.
11
Murphy et al. JGR 2006
Influential Results
This image has been removed due to copyright restrictions.
Please see: http://eloquentscience.com/wp-content/uploads/2013/03/img_global.jpg.
12
Zhang et al. GRL2007
What Forms Clouds?
This image has been removed due to copyright restrictions.
Please see: Figure 17.6 of the book Atmospheric Chemistry and Physics:
From Air Pollution to Climate Change. ISBN: 9780471720188.
This image has been removed due to copyright restrictions.
Please see: Figure 2.15 of the book Atmospheric Chemistry and Physics:
From Air Pollution to Climate Change. ISBN: 9780471720188.
13
Seinfeld and Pandis, 2006
Cloud Formation Basics
This image has been removed due to copyright restrictions.
Please see: http://www.harding.edu/lmurray/113_files/html/d2_earth%20revised/img037.jpg.
http://jennyse7en.blogspot.com/
"The Atmosphere", Lutgens and
Tarbuck, 10th Edition Reference Texts
on Reserve in EPSc Library:
"Understanding
Our
Atmospheric
Environment", Neiburger
et al.
"Meteorology
Today",
Ahrens
http://epsc.wustl.edu/courses/epsc105a/,
W. H. Smith
14
Cloud Development
Clouds form as air rises,
expands and cools
Most clouds form by:
a. Surface heating and
free convection
b. Lifting of air over
topography
c. Widespread air lifting
due
to
surface
convergence
d. Lifting along weather
fronts
.
http://www.sir-ray.com/cloudformation2.jpg
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from our Creative Commons license. For more information, see
http://ocw.mit.edu/help/faq-fair-use/.
15
A Few Words About ALL Clouds
16
This image has been removed due to copyright restrictions.
Please see the image on page: http://scied.ucar.edu/webweather/clouds/cloud-types.
17
Classification of Clouds
Temperatures
By their shape and heights
Other Cloud Types:
• Contrail clouds
•Ship track
•Mammatus clouds
• Orographic clouds
18
Water drop
Ice crystal
Warm cloud
0˚C
Glaciated cloud
0˚C
0˚C
Mixed Phase cloud
19
Clouds Classification
Stratiform
Stratiform
Convective
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 High-Level Clouds Convective
 Mid-Level Clouds Clouds with Vertical Development
 Low-Level Clouds 
20
Other Cloud Types
Contrails
Image courtesy of NASA.
http://commons.wikimedia.org/wiki/File:Sfc.contrail.1.26.01.JPG.
Image courtesy of NASA.
© Aviationstirling. Some rights reserved. License:
CC BY-SA. This content is excluded from our
Creative Commons license. For more information,
see http://ocw.mit.edu/help/faq-fair-use/.
This image has been removed due to copyright restrictions.
Please see the image on page: http://www.rainbowskill.
com/wp-content/uploads/2009/07/a132.jpg.
This image has been removed due to copyright restrictions.
Please see the image on page: https://s-media-cacheak0.pinimg.com/736x/76/e3/63/76e363ed61675f5de64f68a
1608197ad.jpg.
21
Continental and Maritime clouds
Clouds with high concentrations of cloud drops
are referred to as continental clouds. These are
more often found over land.
Clouds with low concentrations of cloud drops
are called maritime clouds and they are often
found in clean regions and over water.
Maritime clouds
Continental clouds
22
Warm M-P
Cold or Ice
Clouds
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Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.
Lamb and Verlinde
23
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Please see the image on page:
http://teachertech.rice.edu/Participants/louviere/Images/profile.gif.
© Mirisa56. Some rights reserved. License: CC BY-SA. This content is
excluded from our Creative Commons license. For more information,
see http://ocw.mit.edu/help/faq-fair-use/.
Tropopau
se
winds
Cloud anvil
Troposphere
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24
Heterogeneous Droplet Activation : ~101%RH
Condensation Nucleus
Droplet
Homogeneous Nucleation :
~400% RH!
(Grey = Soluble Particles take up
water
or Insoluble)
Heterogeneous Ice Nucleation : ~120% RH
Ice Nucleus (IN)
Ice Crystal
Nucleation Mode
(Black = Solid)
Contact Freezing
Deposition Freezing
Homogeneous Ice Nucleation: ~160% RH
Homogeneous Freezing Nucleus (HFN)
Higher Temperature, Lower Humidity
Lower Temperature, Higher Humidity
25
Homogeneously Formed Clouds
Droplets-and
Almost all particles nucleate ice
~ -38° C
Ice Crystals
- Many small ice crystals
Contact
- Longer lifetime
Freezing
- Higher altitude clouds
Ice
Only
Homogeneous
Freezing
Supersaturation (With Respect to Ice)
1.6
Deliquesced
Aerosol and
Ice
Condensation
Freezing
Deliquescence
Deliquescence
Heterogeneously Formed Clouds:
Droplet
-Few but large ice crystals
Activation
-Shorter lifetime due to crystal size
Deposition
-Clouds possible at lower altitude (higher
T, lower RH)
Freezing
Aerosol and Ice
1.0
0
Figure 3.
Temperature (°C)
-50
26
Cloud Measurement
Cloud Droplet Probe (CDP-2)
This image has been removed due to copyright restrictions.
Please see the "Cloud Droplet Probe" image on page:
http://dev.dropletmeasurement.com/products/airborne.
This image has been removed due to copyright restrictions.
Please see the "Cloud Imaging Probe" image on page:
http://dev.dropletmeasurement.com/products/airborne.
Cloud Imaging Probe (CIP)
This image has been removed due to
copyright restrictions.
Please see the "Ultra-High Sensitivity Aerosol
Spectrometer" image on page: http://dev.
dropletmeasurement.com/products/airborne.
Passive Cavity Aerosol Spectrometer Probe
(PCASP-100X)
This image has been removed due
to copyright restrictions.
Please see the "Passive Cavity Aerosol" image
on page: http://dev.dropletmeasurement.
com/products/airborne.
27
DMT, Boulder, CO
PCVI - Pumped Counter flow Virtual Impactor
pump
This image has been removed due to copyright restrictions.
Please see Figure 3 on page:
http://www.tandfonline.com/doi/pdf/10.1080/02786826.2010.539291.
add
Fluid flow velocity characteristics during passage through the PCVI
This image has been removed due to copyright restrictions.
Please see Figure 4 on page:
http://www.tandfonline.com/doi/pdf/10.1080/02786826.2010.539291.
28
Kulkarni et al AST 2011
Analysis of Cloud Residuals
Single particle size and composition (0.2 – 3 mm)
Offline – SEM + EDS
This image has been removed due to copyright restrictions.
Please see Figure 1 on page: http://www.sciencemag.org/content/340/6138/1320.full.
Size, morphology, and composition
Online - PALMS
focus particles
detect a particle & meas size
vaporize & ionize
193 nm
+ +–
+
–
– +
Time-of-flight
MS
analyze ions
Size and composition
Cziczo et al. 2013
29
This images has been removed due to copyright restrictions.
Please see Figure 2 on page: http://www.sciencemag.org/content/340/6138/1320.full.
30
Cziczo et al. 2013
Unclassified
SulfateOrganic
Biomass Burning
EC
Sea Salt
Mineral
Dust &
Metallic
This image has been removed due to copyright restrictions.
Please see Figure 1 on page:
http://www.sciencemag.org/content/340/6138/1320.full.
31
Cziczo et al. 2013
Making Clouds in the lab
Spectrometer for Ice Nuclei (SPIN)
Commercially available from DMT, Boulder, CO
Based on Zurich Ice Nucleation Chamber (Stetzer. Lohmann)
• Parallel plates
• Ice on walls
– Ice saturation
• Linear temp and vapor gradient
• Nonlinear saturation ratio
– Clausius-Clayperon Relation
This image has been removed due
to copyright restrictions.
Please see: http://www.dropletmeasurement.com/
sites/default/files/pictures/Products/SPIN/SPIN_2.gif.
1
0
Detector
© sources unknown. All rights reserved. This content is excluded
from our Creative Commons license. For more information, see
http://ocw.mit.edu/help/faq-fair-use/.
Sarvesh Garimella PhD work
32
Drop freezing technique
CCD
Camer
a
Cold metal plate
130 drops
(1µl; 0.8mm diameter)
33
MIT OpenCourseWare
http://ocw.mit.edu
12.335 / 12.835 Experimental Atmospheric Chemistry
Fall 2014
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