1. MEASURES OF ATMOSPHERIC COMPOSITION

WHAT IS THE ATMOSPHERE? The atmosphere seen from space 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.

Atmospheric gases are “visible” too… if you look in UV or IR % radiation absorbed by atmospheric gases Nitrogen dioxide (NO2 ) observed by satellite in the UV

1.1 Mixing ratio or mole fraction CX [mol mol-1] remains constant when air density changes e robust measure of atmospheric composition SPECIES MIXING RATIO (dry air) [mol mol-1] Nitrogen (N2) 0.78 Oxygen (O2) 0.21 Argon (Ar) 0.0093 Carbon dioxide (CO2) 380x10-6 Neon (Ne) 18x10-6 Ozone (O3) (0.01-10)x10-6 Helium (He) 5.2x10-6 Methane (CH4) 1.7x10-6 Krypton (Kr) 1.1x10-6 Air also contains variable H2O vapor (10-6-10-2 mol mol-1) and aerosol particles Trace gases Hindenburg disaster movie Trace gas concentration units: 1 ppmv = 1 µmol 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 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 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 reaction rates optical properties of atmosphere Proper measure for absorption or scattering of radiation by atmosphere nX and CX are related by the ideal gas law: na = air density Av = Avogadro’s number P = pressure R = Gas constant T = temperature MX= molecular mass of X Also define the mass concentration (g cm-3):

THIS WEEK’S STRATOSPHERIC OZONE LAYER http://ozoneaq.gsfc.nasa.gov Method: UV solar backscatter l1 l2 Ozone layer Scattering by Earth surface and atmosphere Ozone absorption spectrum 1 “Dobson Unit (DU)” = 0.01 mm ozone at STP = 2.69x1016 molecules cm-2 THICKNESS OF OZONE LAYER IS MEASURED AS A COLUMN CONCENTRATION l1 l2

U.S. air quality standard: 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] Dalton’s law: 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 T k e PH2O,SAT k

CLAUSIUS-CLAPEYRON EQUATION: PH2O, SAT = f(T) A = 6.11 hPa B = - 5310 K To = 273 K PH2O,SAT (hPa) DEMO: the freezing experiment. ask for student predictions. Explain about nucleation of the bubbles. Why are bubbles formed in the liquid and what are they made from? freezing: more energy in the ordered lattice, latent heat of "fusion" = 0.34 x 106 J/kg (less than evaporation, but still considerable). relate to boiling – what is boiling? condensation—as in a shower stall. Is heat released on condensation? To evaporate 1 kg of ice, 2.26 + .34 = 2.6 kJ/kg. Clausius-Clapeyron relationship— Psat = A exp [B( 1/273.15 – 1/T)] A=6.11 mbar, B= 5308K. A=water vap. pressure at 0C. 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 point gas-liquid 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 GAS cold outside air

Views of Acadia National Park 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

RAOULT’S LAW solute molecules in green water saturation vapor pressure over pure liquid water surface water saturation vapor pressure 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

HOWEVER, AEROSOL PARTICLES MUST ALSO SATISFY SOLUBILITY EQUILIBRIA Consider an aqueous sea salt (NaCl) particle: it must satisfy This requires: insert clapeyron eq At lower RH, the particle is dry.

UPTAKE OF WATER BY AEROSOLS: HAZE NaCl/H2O Deliquescence RH; depends on particle composition