Water uptake of atmospheric particles:

From the Millikan Oil Droplet Experiment

to a Blue Sky
Chak K. Chan
Division of Environment
Department of Chemical and Biomolecular Engineering
HKUST

http://ihome.ust.hk/~keckchan
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Air Pollution in HK

2
 We have a
severe PM
pollution
problem.

WHO PM10
Air Quality Guideline
(2006)

Source: EPD 3
 Source: EPD

WHO NO2
Air Quality Guideline
(2006)

We also have
a serious
NO2 pollution
problem.
4
 Health Costs of Air Pollution in Hong Kong
Five avoidable numbers to remember
Daily Air pollutant concentrations are now 200% higher than the
200% World Health Organization Guidelines (2006) 24 hr Levels (Should not
be exceeded more than 2 or 3 times annually)

6,800,000 Family doctor visits each year for respiratory problems.

Hospital bed-days a year, mostly for heart, lung and blood vessel
64,000 diseases.

Deaths a year, mostly from heart attacks, stroke, pneumonia and

1,600 other lung diseases.

Value of the direct benefits of air quality improvement would be

20 billion more than $20 billion a year.

(HKU, CUHK, HKUST, Civic Exchange Report, 2006)

*The above does not include indirect costs (Tourism, Business, Talent and long-
term competitiveness) which are several times larger!
 If We Can’t Breathe,
Nothing Else Matters.
(American Lung Association)

6
 Two distinct Outdoor air quality problems

@Tung Chung: Visibility 1.5km

PM10: 342 g/m3 (WHO AQG: 50)
PM2.5: 295 g/m3 (WHO AQG: 25)

Webcam: Hong Kong Tourist Association

Regional Haze / Smog Local, Urban and Roadside

(Secondary Pollutants: PM, O3) (PM, NOx, Black Carbon, SO2)

Similar problems for all major Chinese cities

7
 Urban Air Pollution

Oxidant Secondary Higher Conc.

PM, O3
(O3, OH) PM PM, O3

In-flow hv Out-flow
SO2, NOx Primary PM
HC、NOx

Deposition
Biogenic
Anthropogenic Flux

Atmosphere as a giant chemical reactor

•Transport
•Physical/Chemical Transformation
•Secondary Pollution Xiaoyan Tang, 2006
 •regional problem
•potent oxidant
•VOC/NOx/light
•AVOC & BVOC

VOC =
Volatile Organic
Compounds

揮發性有機物
From: http://www.globalchange.umich.edu/gctext/Inquiries/Inquiries_by_Unit/Unit_9.htm
9
 Particulate Matter

From http://www.sbcapcd.org/sbc/pollut.htm

Poschl , 2005
• Size: from molecule clusters (10-9 m) to fast-settling sand (10-4 m).

• Shape: as weird as you can imagine; depends strongly on composition

and formation processes.
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 Section 1

Visibility degradation by atmospheric pollutants

http://www.epa.gov/air/visibility/what.html
13
 Visibility degradation
– the most visible impact of air pollution

1st, Jul., 2008, RSP: 20-40 µg/m3 28th, Jul., 2008, RSP: 50-250 µg/m3

RSP: respiratory suspended particles;

RSP conc. from ENVF website, HKUST 14
Visibility is not how far a person can see, but
rather the ability of an observer to clearly see
and appreciate the many and varied scenic
elements in each vista.

15
Ansel Adams (1902 -1984)

16
 Prevention of Significant Deterioration

Yosemite National Park

California, USA
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 Factors involved in seeing an object
(Malm)

http://www.epa.gov/air/visibility/what.html 18
 Air pollutants
Gases
• SO2 (二氧化硫)
• NOX/NO2/NO (氮氧化合物)
• O3 (臭氧)
• CO, CH4, VOCs (有機物)
Particulates
• Dust, Black Carbon (灰塵, 黑煙)
• Aerosols (氣溶膠/懸浮粒子)

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 Size of Atmospheric
Particulate Pollutants (Aerosols)
PM2.5

Sea Salt

Urban particles

Viruses Bacteria Fungi

Dust storms

Tobacco Smoke Sand storms

Volcanic plumes

Atmospheric Aerosols
Forest fires

5 orders of magnitude in size

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Light interacts with a particle
Fig.2.2(a) Rayleigh scattering:
If the particles are small (such as
the air molecules themselves),
the amount of light scattered in the
forward and backward directions
are nearly the same.

Fig2.2(b) As the particle

increases in size, more light
tends to scatter in the forward
direction. If the particle is large
(greater than 10 microns), most
of the incident light is scattered
in the forward direction.
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Fig.2.1 Large particle light scattering and absorption.

(a) Diffraction (b) Refraction

(c) Phase Shift (d) Absorption

http://www.epa.gov/air/visibility/what.html
22
 Aerosol (Particle) Size Distribution

Fig. 2.4 shows the

relative amounts of small
and large particles found
in the atmosphere.
The blue line shows the
relative amount of mass
typically found in a given
particle size range.
The orange line shows the
relative amount of particle
scattering associated with
that mass.

Note: Even though most of the

mass is associated with coarse
particles (>2.5 µm), it is the fine particles (<2.5 µm) that are primarily
responsible for scattering light, causing visibility impacts. 23
 Summary 1

 Visibility degradation is mainly caused by

particulate pollutants.

 SIZE matters! Smaller (PM2.5) particles

are more efficient in scattering light.

 There is NO PM2.5 standard in HK. We

only have PM10 (or RSP, respirable
suspended particulate) standards.

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 Section 2

Chemical Characteristics of Particulate

Pollutants

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 PM2.5 in Hong Kong

elemental
carbon

26
Louie et al. (2005), Atmospheric Environment 39, 1695.
 Fig.4.8 schematically shows the five particle types that make up nearly all of the fine
particle mass found in the atmosphere. They are, in order of their relative contribution
to visibility impairment, sulfates, organics, soil, elemental carbon, and nitrates (in
selected US National Parks).
 Importance of sulfate to visibility

18 18

16 16

Visibility (km)
Visibility (km)

14 14

12 12

10 10

8 8

20 40 60 803 100 4 8 12 3
16
Total RSP (ug/m ) Sulfate in RSP (ug/m )

Data shown are 19 daily measurements made in the period

of December 1996 to Jan 1997. Zhuang et al. (1999a)
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 Visibility

Visual range (x) is related to the

extinction coefficient (bext) via the
Koschmeider equation,

x = 3.912 / bext.

where bext = bscat + babs.

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 Visibility

bscat = A1 F1(RH) [Sulfate] + A2 F2(RH) [Nitrate]

+ A3 F3(RH) [Organic Carbon]
+ A4 F4(RH) [Soil] +…

RH= relative humidity

Analogously, the absorption coefficient,

babs = B1[NO2] + B2[Elemental Carbon]

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 Activate to
Aerosol Hygroscopicity form cloud
droplets
Increased light
scattering degrades
visibility

hn
Hygroscopic
Growth
Growth Factor

Water Saturation
Crystallization Deliquescence
100%
Relative Humidity 31
 Observation of Phase Transition
Example : Pure Ammonium Sulfate particles upon a humidity cycle
10 μm
• Crystallization : 63% 37.5%

• From spherical droplets to Evap. Growth

irregular and opaque solids
• CRH : Range of RH in which all
observed particles crystallize
42% 78%
• 37.5 – 39.5% RH

• Deliquescence :
• From irregular and opaque
solids to spherical droplets
39.5% 80%
• DRH : RH at which all particles
completely dissolve
• 80% RH

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Climate Effect of Aerosols

33
References : Penner et al. 2001; Ramanathan et al. 2001; Forster et al. 2007
Importance of hygroscopic growth of aerosols
to visibility

“Some inorganic salts, such as

ammonium sulfate and nitrate, undergo
sudden phase transitions from solid
particles to solution droplets when the
relative humidity (RH) rises above a
threshold level.
Thus, under higher RH (>70%) levels,
these salts become disproportionately
responsible for visibility impairment as
compared with other particles that do not
uptake water molecules.”

William C. Malm
National Park Service, USA 34
 Summary 2

• Visibility degradation is mainly caused by

particulate pollutants
• SIZE matters! Smaller (PM2.5) particles are
more efficient in scattering light.
• Chemical composition matters!
• Water matters! Relative humidity matters!

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 Section 3

Laboratory determination of water contents

(or hygroscopic properties) of atmospheric particles
by
Single Particle Levitation

36
 Measurement Techniques of
Hygroscopic Properties of Aerosols
Single Particle Levitation Method
1. Electrodynamic Balance (EDB)

Aerosol Flow Through System

1. Tandem Differential Mobility Analyzer
2. Aerosol Flow Tube - Fourier Transform Infrared System
3. Controlled Relative Humidity Nephelometry
4. Aerosol Size Spectrometer

Other Methods
1. Filter-Based Analysis - Gravitational Measurement
2. Water Activity Measurement of Bulk Aqueous Solutions
3. Microscope System

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Robert A. Millikan (1868-1953)
• Nobel Physicist (1923)
• Founder of Caltech
(1921)
• Determined the value of
the electron charge, e
(1910)

• Developed the “Millikan

Oil Droplet Experiment”

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 Electrodynamic balance for
single particle levitation
Metal
Gas inlet
Electrostatic force

AC
0-1000V
DC
30-100kHz
0-99V
AC

Gas outlet
Insulator
Gravitational force
Particle is stationary if:
Electrostatic force = Gravitational force
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 Electrodynamic balance

A particle oscillates vertically A particle is levitated stationary

when its weight is not balanced by an electric field in an EDB.
by the electrostatic field.

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 Hygroscopic measurements
In static environment (i.e. no relative motion between the particle
and the ambient gas)

Gravitational force co q Electrostatic force

mg  Vbal
of the particle zo of the particle

The relative mass change of a particle as a result of evaporation/

condensation of water can be determined by Vbal, the DC voltage
required to balance the particle stationary.

A picogram (10-12 g) level balance for measuring the water content

of an individual particle as a function of relative humidity and
composition.
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 Single Particle Raman Spectroscopy
Slit width
Convex lens (f 6.9) ~50mm
Gas inlet

Electrodynamic
balance
Notch
filter
Gas outlet

Monochromator with
Argon Laser
CCD detector
514.5 nm
connected to computer
42
 Series of Raman spectra for an AS/GA particle
undergoing evaporation
GA Solid GA Aq GA Solid GA
~940 ~1676 ~1707 ~2928, 2951
(5) RH=35%
m/m0=1.0, crystal

(4) RH=39%
m/m0=1.2, aqueous
Intensity (a.u.)

(3) RH=54%
m/m0=1.4, aqueous

(2) RH=78%
m/m0=1.9, aqueous

(1) RH=86%
m/m0=2.3, aqueous

AS AS
~462, 623 ~980 H2O, ~3500

300 800 1300 1800 2300 2800 3300 3800

Raman Shift (cm-1) 43
Monet’s London visit (1899-1901)

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Monet’s London visit (1899-1901)

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 Monet’s London visit (1899-1901)

Monet’s Love for London’s Fog

“I love London…I adore London. But what I love

more than anything..is the fog”
“The Thames was all gold. God it was so
beautiful…I began to work in a frenzy”
“I can’t begin to describe a day as wonderful as
this. One marvel after another, each lasting less
than five minutes…”
Thornes and Baker, 2006
46
 Monet’s London visit (1899-1901)

‘For me, a landscape does not exist in its

own right, since its appearance changes at
every moment; but the surrounding
atmosphere brings it to life, the air and the
light, which vary continually…For me, it is
only the surrounding atmosphere that gives
subjects their true value.’

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