1.

MEASURES OF ATMOSPHERIC COMPOSITION

 The atmosphere seen from space

WHAT IS THE ATMOSPHERE?

Gaesous envelope surrounding the Earth

Mixture of gases, also contains suspended solid and liquid particles

(aerosols)
Aerosol = dispersed condensed phase suspended in a gas

Aerosols are the visible components of the atmosphere

California fire plumes Pollution off U.S. east coast Dust off West Africa
 WHAT ABOUT CLOUDS?

Clouds are made up of water droplets or ice crystals

(1-100 mm), much larger than typical aerosols (0.01-
10 mm). They are technically aerosols but have
unique properties and are in practice considered
separately.
 1.1 Mixing ratio or mole fraction CX [mol mol-1]
# moles of X remains constant when air density changes
CX
mole of air e robust measure of atmospheric composition

SPECIES MIXING RATIO

(dry air) Air also contains variable H2O
[mol mol-1]
vapor (10-6-10-2 mol mol-1) and
aerosol particles
Nitrogen (N2) 0.78
Oxygen (O2) 0.21
Argon (Ar) 0.0093
Carbon dioxide (CO2) 380x10-6
Neon (Ne) 18x10-6
Trace Ozone (O3) (0.01-10)x10-6
gases Helium (He) 5.2x10-6 Hindenburg disaster movie
Methane (CH4) 1.7x10-6
Krypton (Kr) 1.1x10-6

Trace gas concentration units:

1 ppmv = 1 mol mol-1 = 1x10-6 mol mol-1
1 ppbv = 1 nmol mol-1 = 1x10-9 mol mol-1
1 pptv = 1 pmol mol-1 = 1x10-12 mol mol-1
Atmospheric gases are visible too if you look in UV or IR
Vis
UV 0.4-0.7 m IR

% radiation
absorbed by
atmospheric
gases
Nitrogen dioxide (NO2 ) observed by satellite in the UV
ATMOSPHERIC CO2 INCREASE OVER PAST 50 YEARS

Intergovernmental Panel on Climate Change (IPCC), 2014

Concentration units: parts per million (ppm)

number of CO2 molecules per 106 molecules of air

CO2 CONCENTRATION IS MEASURED AS MIXING RATIO

 EPA SURFACE OZONE AIR QUALITY STANDARD
8-hour average of 0.08 ppmv not to be exceeded more than 3x/year

EPA air quality standard for surface ozone is 0.075 ppm or 75 ppb
 1.2 Number density nX [molecules cm-3]

Proper measure for

# molecules of X
nX reaction rates
unit volume of air optical properties of atmosphere

Column concentration X = nX ( z )dz Proper measure for absorption or
0 scattering of radiation by atmosphere

nX and CX are related by the ideal gas law: na = air density

Av = Avogadros number
Av P
n X naC X CX P = pressure
RT R = Gas constant
T = temperature
Also define the mass concentration (g cm-3): MX= molecular mass of X

mass of X M n
X X X
unit volume of air Av
 THIS WEEKS STRATOSPHERIC OZONE LAYER
http://ozoneaq.gsfc.nasa.gov

Method: UV solar backscatter

l1 l2
Ozone layer

Scattering by
Earth surface
and atmosphere

Ozone
1 Dobson Unit (DU) = 0.01 mm ozone at STP absorption
= 2.69x1016 molecules cm-2 spectrum
THICKNESS OF OZONE LAYER IS MEASURED
AS A COLUMN CONCENTRATION
l1 l2
US AREAS EXCEEDING THE PARTICULATE MATTER (PM2.5)
EPA AIR QUALITY STANDARD (2010)

PM2.5 concentration of aerosol particles < 2.5 mm diameter)

U.S. air quality standard:

PM2.5 = 15 mg m-3
(annual mean)
SPECIFIC ISSUES FOR AEROSOL CONCENTRATIONS
A given aerosol particle is characterized by its size, shape, phase, and
chemical composition large number of variables!

Measures of aerosol concentrations must be given in some integral

form, by summing over all particles present in a given air volume that
have a certain property

The aerosol size distribution is a continuous function

URBAN
Typical U.S. aerosol
size distributions
by volume
RURAL
 1.3 Partial pressure Px [Pa]

Daltons law: PX C X P Proper measure for phase change

(such as condensation of water vapor)

Evaporation of liquid water from a pan:

No lid: water molecules escape from pan to

atmosphere (evaporation)

Add a lid:
escaping water molecules collide on lid and
return to surface; collision rate measures PH2O

eventually, flux escaping = flux returning :

saturation (PH2O,SAT)

cloud formation in atmoshere requires

PH2O > PH2O,SAT

Tk e PH2O,SAT k
CLAUSIUS-CLAPEYRON EQUATION: PH2O, SAT = f(T)
1 1 A = 6.11 hPa
PH 2O , SAT A exp[ B( )] B = - 5310 K
PH2O,SAT (hPa) T To To = 273 K

T (K)
 Phase rule of physical chemistry

The number n of independent variables determining the equilibrium partitioning

of c species between p phases is given by

n=c+2-p
 Questions

1. Oxygen has a fixed mixing ratio in the atmosphere. How would you
expect its number density measured in surface air to vary between day and
night? How would you expect its partial pressure measured in surface air to
vary between day and night?

2. Give a rough order of magnitude for the number of molecules present in a

typical 1 micrometer aerosol particle.

3. In an atmosphere with fixed mixing ratio of water vapor, what two

processes can cause an increase in relative humidity?

4. We saw that a cloud in the atmosphere can remain liquid at temperatures

below freezing. At a given temperature below freezing, and for a given total
amount of water in an air parcel, will a cloud contain more condensed water
if it is liquid or solid?
 PHASE DIAGRAM FOR WATER

http://weather.unisys.com

triple
gas-liquid point
metastable
equilibrium

Relative humidity (%) = 100(PH2O/PH2O,SAT)

Dew point: Temperature Td such that PH2O = PH2O,SAT(Td)

 RUNAWAY GREENHOUSE EFFECT ON VENUS
due to accumulation of water vapor from volcanic outgassing early in its history
did not happen on Earth because farther from Sun; as water accumulated it
reached saturation and precipitated, forming the oceans

EARTH VENUS
 WHY CAN YOU SEE YOUR BREATH ON COLD MORNINGS?
Draw mixing lines (dashed) to describe dilution of your breath plume w/outside air

PH2O is plotted on linear

scale to draw the mixing
lines

LIQ
Your breath
37oC, 100%RH

ICE cloud!
no cloud

warm outside air

cold outside air GAS
 AIR POLLUTION HAZE

Views of Acadia National Park

http://www.hazecam.net/

clean day moderately polluted day

Visibility is limited by high concentrations of aerosol particles that have swollen

to large sizes due to high (but <100%) relative humidity
 RAOULTS LAW

Po
H 2O , SAT PH 2O,SAT x o
P
H 2O H 2O, SAT

solute
molecules
in green
water saturation vapor pressure water saturation vapor pressure
over pure liquid water surface over aqueous solution of water
mixing ratio xH2O

An atmosphere of relative humidity RH can contain at equilibrium

aqueous solution particles of water mixing ratio PH 2O , SAT RH
xH 2O
PHo 2O , SAT 100
 HOWEVER, AEROSOL PARTICLES MUST ALSO
SATISFY SOLUBILITY EQUILIBRIA

Consider an aqueous sea salt (NaCl) particle: it must satisfy

xNa xCl K s (solubility equilibrium)

xNa xCl (electroneutrality)
xNa xCl xH 2O 1 (closure)

This requires:
1
RH 100(1 2 K s ) "deliquescence RH"
2

At lower RH, the particle is dry.

UPTAKE OF WATER BY AEROSOLS: HAZE

NaCl/H2O

Deliquescence RH;
depends on particle
composition