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

Seinfeld and Pandis

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

Aerosol Abundance

Unless otherwise specified figures from Seinfeld and Pandis

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

Aerosol Composition Before 1994

• So, what’s the problem(s) here? •Courtesy / adapted from J. Jimenez

5

Thermal Desorption Aerosol Mass Spectrometer

https://www.tropos.de/en/research/projects-infrastructures-technology/technology-at-tropos/chemical-analytics/aerosol-mass-spectrometry-techniques/

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.

6

Single Particle Mass Spectrometry

Particle Inlet

Particle Sizing

Particle Composition

+ -+ -

2/ tzm µ

Inte

nsity

2/ tzm µ

Inte

nsity

start 0

200

100300µsstop

0

200

100300µs

0

200

100300µs

Courtesy of D. Gross

PALMS Particle Analysis by Laser Mass Spectrometry

Image courtesy of Deborah Gross. Used with permission.7

0.001

0.01

0.1

1

10

ion

cu

rre

nt

(mA

)

2202102001901801701601501401301201101009080706050403020100m/z

C+

C2+

SO+

CO+

Pb+

NO+

C3+

HSO3+HSO2

+

H3SO4+

0.001

0.01

0.1

1

10

ion

cu

rre

nt

(mA

)

2202102001901801701601501401301201101009080706050403020100m/z

Apr 07 16:068.5 km 237 KDa = 1.3 m

C+

Na+

SO+

Al+

Fe+

Ca+

Ba+

Cu+

Li+

K+

Pb+

Rb+

Mineral Dust particle

Sulfate-Organic particle

adapted from D. Cziczo

8

Influential Results

Murphy et al. Science 1998 9

0.3

0.2

0.1

0.0

0.3

0.4

0.2

0.1

0.0

0 20 40 60 80 100 120

0 20 40 60 80 100 120

O-S-

HSO4-

HSO3-

SO3- SO4

-H34SO4

-OH-

OH-C2

-

CHO2-

C2H2O-O-H-

C2H5CO2-

CH3CO2- SO4

-79Br-35Cl-

A

B

19980507 #667219 km: 31oNθ=437 K

19980501 #112014.6 km: 22oNθ=360 K

Det

ecto

r Sig

nal (

mA)

Det

ecto

r Sig

nal (

mA)

Ion mass/charge

CN- & C2H2-

SO3-

HSO3-

HSO4-

l-

CH2OHSO3-

H34SO4-

La

Ac Th Pa U

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

H

Li Be

Na Mg

K

Rb

Cs

Fr

Ba

Ra

Sr

Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br

Ru Rh Pd Ag Cd In Sn Sb Te ITc

Re Os Ir Pt Au Hg Tl Pb Bi Po At

Mo

W

Nb

TaHf

ZrY

most many common some rare maybeHe

NeB C N O F

Al Si P S Cl Ar

Kr

Xe

Rn

Figure by MIT OpenCourseWare.

Figure by MIT OpenCourseWare.

Free Tropospheric

K. Froyd, unpublished

• Biomass Burning

• Sulfate-Organicmixtures dominate in UTLS

• Mineral Dust: 10-30%

• Little Sea Salt in UT

• Meteoric particles in stratosphere

• Acidic sulfate mainly in stratosphere

Tropopause

Number Fraction

m)

(k

tud

eA

lti

Image courtesy of Karl Froyd. Used with permission.10

Murphy et al. JGR 2006

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

Influential Results

Zhang et al. GRL2007

This image has been removed due to copyright restrictions.Please see: http://eloquentscience.com/wp-content/uploads/2013/03/img_global.jpg.

12

What Forms Clouds?

Seinfeld and Pandis, 2006

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.

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.

13

Cloud Formation Basics

"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

http://jennyse7en.blogspot.com/

This image has been removed due to copyright restrictions.Please see: http://www.harding.edu/lmurray/113_files/html/d2_earth%20revised/img037.jpg.

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 © sources unknown. All rights reserved. This content is excludedfrom our Creative Commons license. For more information, seehttp://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

• Contrail clouds •Ship track •Mammatus clouds • Orographic clouds

Classification of Clouds

Other Cloud Types:

Temperatures

By their shape and heights

18

0˚C 0˚C 0˚C

Mixed Phase cloud

Glaciated cloud

Warm cloud

Water drop Ice crystal

19

Stratiform High-Level Clouds Mid-Level Clouds Low-Level Clouds

Clouds Classification

Convective

Clouds with Vertical Development

Stratiform Convective

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20

Contrails

Other Cloud Types

Image courtesy of NASA.

Image courtesy of NASA.http://commons.wikimedia.org/wiki/File:Sfc.contrail.1.26.01.JPG.

© Aviationstirling. Some rights reserved. License:CC BY-SA. This content is excluded from ourCreative 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-cache-ak0.pinimg.com/736x/76/e3/63/76e363ed61675f5de64f68a1608197ad.jpg.

21

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.

Continental and Maritime clouds

clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. Continental clouds

clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. clean regions and over water. Maritime clouds

22

Clouds

Lamb and Verlinde

o

r Ic

ed

C

ol

P

-M

arm

W

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Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.23

Troposphere

Tropopause

Cloud anvil

winds

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24

Higher Temperature, Lower Humidity Lower Temperature, Higher Humidity

Condensation Nucleus

(Grey = Soluble or Insoluble)

(Black = Solid)

Droplet

Ice Crystal

Heterogeneous Droplet Activation : ~101%RH

Heterogeneous Ice Nucleation : ~120% RH Ice Nucleus (IN)

od

e Contact Freezing

Mon

itael

Nuc

Deposition Freezing

Homogeneous Ice Nucleation: ~160% RH Homogeneous Freezing Nucleus (HFN)

Particles take up water

Homogeneous Nucleation : ~400% RH!

25

Supe

rsat

urat

ion

(With

Res

pect

to Ic

e)

Temperature (°C) 0 -50 1.0

1.6

Droplets and Ice Crystals ~ -38° C

Droplet Activation

Contact Freezing

Deliquescence

Hom

ogen

eous

Fr

eezi

ng

Free

zing

Fr

eezi

ng

Ice Only

Figure 3.

Aerosol and Ice

Condensation Freezing

Condensation Condensation

Deliquescence

Deliquesced Aerosol and

Ice

Deposition Freezing

Heterogeneously Formed Clouds: -Few but large ice crystals -Shorter lifetime due to crystal size -Clouds possible at lower altitude (higher T, lower RH)

Homogeneously Formed Clouds - Almost all particles nucleate ice - Many small ice crystals - Longer lifetime - Higher altitude clouds

26

Cloud Measurement

DMT, Boulder, CO

Cloud Imaging Probe (CIP)

Passive Cavity Aerosol Spectrometer Probe (PCASP-100X)

This image has been removed due to copyright restrictions.

Please see the "Cloud Droplet Probe" image on page:http://dev.dropletmeasurement.com/products/airborne.

Cloud Droplet Probe (CDP-2)

This image has been removed due to copyright restrictions.Please see the "Cloud Imaging Probe" image on page:http://dev.dropletmeasurement.com/products/airborne.

This image has been removed due tocopyright restrictions.Please see the "Ultra-High Sensitivity Aerosol

Spectrometer" image on page: http://dev.

dropletmeasurement.com/products/airborne.

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

PCVI - Pumped Counter flow Virtual Impactor

add

pump

Fluid flow velocity characteristics during passage through the PCVI

Kulkarni et al AST 2011

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.

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

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

detect a particle & meas size

focus particles vaporize & ionize – + + Time-of-flight + MS

–+ – 19

3

analyze ions

nm

Size and composition

29

Cziczo et al. 2013 29

Cziczo et al. 2013

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

Sulfate-

Organic Biomass Burning

Mineral

Dust &

Metallic

Sea Salt

Unclassified

EC

Cziczo et al. 2013

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

0 1

• Parallel plates • Ice on walls

– Ice saturation • Linear temp and vapor gradient • Nonlinear saturation ratio

Detector – Clausius-Clayperon Relation

Sarvesh Garimella PhD work

Making Clouds in the lab Spectrometer for Ice Nuclei (SPIN) Commercially available from DMT, Boulder, CO Based on Zurich Ice Nucleation Chamber (Stetzer. Lohmann)

This image has been removed dueto copyright restrictions.Please see: http://www.dropletmeasurement.com/sites/default/files/pictures/Products/SPIN/SPIN_2.gif.

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Drop freezing technique

Cold metal plate

CCD Camer

a

130 drops (1µl; 0.8mm diameter)

33

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12.335 / 12.835 Experimental Atmospheric ChemistryFall 2014

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