The atmospheric compartment
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The atmospheric compartment. How much does it weigh? Temperature and pressure Circulation and mixing Where did Oxygen come from Particle emissions Emissions of other pollutants.

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The atmospheric compartment
The atmospheric compartment

  • How much does it weigh?

  • Temperature and pressure

  • Circulation and mixing

  • Where did Oxygen come from

  • Particle emissions

  • Emissions of other pollutants


The total atmosphere weights5.13x1018 kg Assume that an average car weighs 1000 kg or one metric tonnehow many cars are equal to the weight of the atmosphere?if you could cover the earth in cars how high would the stack be? Assume the average car has a “foot print” of 4x2 meters and is 2 meters high?


T wo important features the atmospheric compartment are temperature and pressure
Two important features the atmosphericCompartment aretemperature and pressure


The atmosphere is usually divided into the following
The atmosphere is usually divided into the following:

  • Troposphere 0-10 km

  • tropopause ~10km

  • Stratosphere 10-50km

  • stratopause ~50 km

  • mesosphere 50-80kn

  • Thermosphere 80 + km


These divisions come about because of temperature differences as one increases in altitude:


  • The troposphere contains about 80% of the atmospheric mass.

  • Air cools with altitude in the troposphere. The top; 10-15 km is at ~-60oC; which means very little water vapor.

  • In the stratosphere, temp. increases with height because O3 absorbs uv radiation.

  • Thermal mixing of air (heat) is responsible for global circulation in the lower atmosphere.


The atmosphere is held to earth s surface
The atmosphere is held to earth’s surface

  • by the gravitational attraction of the earth

  • At a given altitude the downward force (F) is related to the mass (M) of the atmosphere above that point. F= M (g); where g is the gravitational acceleration constant


The pressure or force per unit area
The pressure or force per unit area

  • decreases with increasing altitude

  • The decline in pressure (P) with altitude is approximately = to log P= - 0.06 (z); where z is the altitude in km and P is bars


How thin is the air at the top of mt everest
How thin is the air at the top of Mt. Everest?

  • Mt. Everest is 8882 meters high or 8.88 km high

  • log P = -0.06 x 8.88

  • P = 10-0.06x 8.88 = 0. 293 bars

  • Assume there are 1.01bars/atm.

  • This means there is < 1/3 of the air


  • Where does log p = - 0.06 (z) come from;

  • Force = mass x accelerationacceleration =g

  • The mass of air over a surface,A,equals height x A x mass/volume; the mass / volume = density, r;

  • So Force = -z x A xrxg

  • The change in force at any altitude

  • dF = -dz x A xrxg; F/A = pressure, p

    So the change in pressure with height isdp= -dz xrxg


  • dp = -dz xrxg

  • What is the ideal gas law

  • pV = nRT

  • Show that r = Mw xp/RT

  • Substituting for r in dp = -dz xrxg

  • dp = -dz xMw xp/RTxg

  • Sodp/p = -dz xMw /RTxg

  • Integrating

  • So p = po exp {-Mw g z/RT}


  • p = po exp {-Mw g z/RT}

  • If we set H = (Mw g/RT)-1 it has the units of length

  • and we get a simple expressionp= po exp {-z/H}

  • Solving for H at 290K; R = 8.3 joules/(K mole) one joule = 1kg meter2/sec2average Mw of air = 28.9 g/moleg = 9.8 meter/sec2

  • H = 8.5 km; people actually find that 7km works best; when 7 km is used we end up with

  • log p = - 0.06 (z);


Is it possible in the troposphere to calculate the rate that temperature of the air decreases with altitude?


To do this we need to start with simple thermodynamics

  • The first law of thermo says that the change internal energy of a system is the sum of its changes in heat content and work that is done.

  • dU = dq - dw

  • A change in work can only occur if a force moves through a distance; dw = d (fxz) = d (pV) for work there must be movement

  • Hence dw = Vdpand dU = dq - Vdp

  • Another form of energy is call enthalpy (H) which is the sum of the internal energy and pV from pV=nRT

  • so H = U + PV or dH = dq –Vdp+ Vdp +pdV = Vdp(dq is assumed to be zero for a process that does not have a heat loss)

  • The change in the heat of a mass, per change in a degree centigrade, is called its specific heat Cp and Cp = dH/dT


  • we said the enthalpy dH= Vdp

  • specific heat capacity; Cp = dH/dT

  • So Cp dT= dH = Vdp

  • Before we said that the change in pressure with height, z was dp= -dz x r x g

  • So substituting for dp we get

  • Cp dT= - V xdz x r x g

  • So the change in temp with height is dT/dz = - V x r x g/ Cp

  • Density r is mass/V; so for an air mass of one gram, r = 1/V

  • This puts Cp in units of energy gram-1 deg-1; for dry air this is 0.24 cal gram-1 o K-1 and we will call it cp

  • So - dT/dz = g/ cp where g = 9.8 m sec-2

  • 1 cal = 4.1 joules so cp= ~1 joule gram-1 o K-1

  • One joule = 1 kg m2sec-2

  • So - dT/dz = g/ cp = 0.0098 oK/meter or 9.8 oK/kilometer


  • The fact that - dT/dz = g/ cp = 9.8 oK/kilometer is constant is consistent with observations

  • And this is called the dry adiabatic lapse rate so that - dT/dz = d

  • When - dT/dz > d the atmosphere will be unstable and air will move (convection) to re-establish a stability


The quantity dis called the dry adiabatic lapse rate

  • Air that contains water is not as heavy and has a smaller lapse rate and this will vary with the amount of water

  • If the air is saturated with water the lapse rate is often called s

  • Near the surface sis ~ -4 oK/km and at 6 km and –5oK/km it is ~-6K/km at 7km high


Sun-down earth cools

more cooling at surface at night

midday

altitude

altitude

altitude

}

Inversion layer

temp

temp

temp

At midday, there is generally a reasonably well-mixed layer lying above the surface layer into which the direct emissions are injected.

As the sun goes down, radiative cooling results in the formation of a stable nocturnal boundary layer, corresponding to a radiation inversion.


What happens to the material above the inversion layer??

more cooling at surface at night

}

residual layer

altitude

}

Inversion layer

temp

These materials are in a residual layer that contains the species that were well-mixed in the boundary layer during the daytime. These species are trapped above and do not mix rapidly during the night with either the inversion boundary layer below or the free troposphere above.


more cooling at surface at night

Heating at surface during the next day

altitude

altitude

}

Inversion layer

}

Inversion layer

temp

temp

When the sun comes up the next day it heats the earth an the air close to the earth.

During the next day heating of the earth's surface results in mixing of the contents of the nocturnal boundary layer and the residual layer above it


Mixing height in the morning
Mixing height in the morning

  • We will start with the balloon temperature curve that is taken at the airport each morning.

  • In the morning the temperature usually increases with height for a few hundred meters and then starts to decrease with height (see the green curve) according to the temperature sensor on the balloon

  • The the break in the curve usually defines the inversion height in the early morning


Mixing height in the morning1

Balloon temperature

}

Inversion height

Mixing height in the morning

height in kilometers

Temp in oC


Mixing height in the morning2
Mixing height in the morning

  • There are another set of lines called the dry adiabatic lines, which are thermodynamically calculated, and represent the ideal decrease in temperature with height for dry air starting from the ground.

  • In the morning, the mixing height is estimated by taking the lowest temperature just before sunrise and adding 5oC to it, and then moving up the dry adiabatic line at that temperature until it intersects the balloon temperature line or the green curve.

  • Let’s say the lowest temperature just before sunrise was 20oC. We would add 5oC to it and get 25oC. We then move up the 25oC dry adiabatic line. We then go straight across to the right, to the height in kilometers and get a morning mixing height of ~350 meters (0.35 km). This is illustrated in the next slide. It is animated so you can see it more easily


Mixing height in the morning3

Balloon temperature

1.5

1.1

height in kilometers

Dry adiabatic

lines

0.4

0.3

0.2

0.1

0.0

20

25

30

35

Temp in oC

Mixing height in the morning


Mixing height in the afternoon
Mixing height in the afternoon

  • To get the mixing height in the afternoon, you just take the highest temperature between 12:00pm and 15:00 pm

  • Do not add anything to it, but as before run up the dry adiabatic curve and intersect the morning balloon temperature curve.

  • Let say the highest afternoon temperature is 35oC, we would estimate an afternoon mixing height of ~1.67 km


Afternoon mixing height

Balloon temperature

1.5

1.1

height in kilometers

Dry adiabatic

lines

0.4

0.3

0.2

0.1

0.0

20

25

30

35

Temp in oC

Afternoon Mixing height


How does air circulate

  • At the equator air is heated and rises and water is evaporated.

  • As the air rises it cools producing large amounts of precipitation in equatorial regions.

  • Having lost its moisture the air mass moves north and south.

  • It then sinks and compresses (~30oN and S latitude) causing deserts


Circulation currents
Circulation currents

30oN

Hadleycell

equator



Circulation currents1
Circulation currents and flows south (in the northern hemisphere.

Hadleycell

indirectcells

30oN

Hadleycell

equator



Circulation currents2
Circulation currents and at the poles, counter current or indirect cells are set up.

Hadleycell

indirectcell

30oN

Hadleycell

equator


  • The air in each hemisphere mixes with a time constant , and at the poles, counter current or indirect cells are set up.t, of a few months.

  • The air between the north and south hemispheres completely mix on the order of one year.

  • Air mixes into the stratosphere from rising Hadley cells in the tropics, storms and eddy diffusion.

  • exchange between the troposphere and the stratosphere can be thought of in terms of mean residence times (MRT)


  • The mean residence time ( and at the poles, counter current or indirect cells are set up.MRT) can be expressed as: MRT = mass / flux where flux is mass/time

  • If 75% of the mass/year in the stratosphere comes from the troposphere

  • 1 MRT = ----------------- = 1.3 years

    • 0.75/year


  • Mt. Pinatubo in the Philippines erupted in June 1991, and added a huge amount of SO2 and particulate matter the stratosphere. After one year how much SO2was left?

  • For a 1st order process C= Coe-1 year/ MRT

  • C/Co= e -1 year/ MRT = e -1/1.3= 0.47 or ~ 50%

  • in 4 years, C/Co= e -4 years/1.3 years = ~5%



Atmospheric Composition eruption

  • Three gases, O2, N2, and argon make up 99% of the atmosphere mass of 5.14x1021 g

  • These gases are relatively un-reactive and their mean residence times are much longer than the rate of atmospheric mixing. Hence the conc. of N2, O2, and the Nobel gases (He, Ne, Ar, Kr, and Xe) are relatively uniform.


Atmospheric Composition eruption

  • N2 78.084% 3.87x1021 grams

  • O2 20.946 1.19x1021

  • Ar 0.934 6.59x1021

  • CO2 0.036 2.80x1018

  • Ne 18.2 ppm 6.49x1016

  • H2 510 ppb 1.82x1014

  • CFC 11 280 ppt 6.79x1012

  • MeBr 11 ppt 1.84x1011


Where does oxygen come from in our atmosphere
Where does eruptionoxygencome from in our atmosphere?

  • ~3.8 billion years ago the earliest bacteria were able to take acetic acid and metabolize it to CO2 and water.

  • CH3COOH ->CO2+ H2O

  • A later form of bacteria could obtain energy from the reduction of H2S to S


  • CO eruption2 +2H2S->CH2 O+ 2S + H2O

  • As supplies of H2S were consumed in the oceans other energy generating metabolic processes became more competitive

  • one was photosynthesis

  • H2O +CO2 -> CH2O + O2


A good summary of the rise of life on earth
A good summary of the “Rise of Life on Earth” eruption

  • is given in National Geographic, vol 193, p 54, March 1998

  • Experiments in the early 1950’s (Dr. Stanley Miller, U. Cal. San Diego) showed that is is possible to generate amino acidsin an atmosphere of CH4, NH3 and H2 over a pool of water with an electrical discharge


This gave rise to the theory that life could have originated in warm tidal pools of the oceans
This gave rise to the theory that eruption“life” could have originated in warm tidal pools of the oceans,

  • since amino acids are the building blocks of “life”.

  • It is now thought that the atmosphere 4-3.5 billion years ago consisted of CO2 and N2

  • sparking CO2 and N2does not generate large amounts of organics


A more recent theory is that eruption“life” could have originated in deep hot pools of water heated by volcanic rock.

  • Some of the most primitive live forms, called thermophil bacteria, can live at 190oC and consume iron and sulfur (3.8 billion years ago).

  • Another theory involves ice. Trapped H2C=O, NH3, HCN and water--->glycine (amino acid) followed by meteorite impact


  • Photosynthetic cyanobacteria (blue green algae) may go back 3.46 billion years. They were recently found in a rock from NW Australia.

  • It is felt these types of bacteria invaded other cells and their chloroplasts“stayed” there.

  • Some bacteria were also invaded by mitochondria which burn sugar


  • These photosynthetic cells gave off huge amounts of oxygen. 3.46 billion years. They were recently found in a rock from NW Australia.

  • Oxygen did not really start to build up in the earth's atmosphere until ~2 billion years ago. Why??

  • The oceans contained much dissolved iron. It had to be oxidized before O2 could persist in the atmosphere.


Aerosols 3.46 billion years. They were recently found in a rock from NW Australia.

  • The atmosphere contains particles which are known as aerosols. These come from a number of different sources

  • Soil minerals are dispersed by wind erosion from arid (dry) and semi-arid regions

  • Particles with a diameter of 1.0 mm (the smallest we can see is 20 mm) are held aloft by turbulent motion and can be transported long distances


  • It is estimated that 1x10 3.46 billion years. They were recently found in a rock from NW Australia.15grams/year of soil particles enter the atmosphere and 20% are involved in long range transport.

  • Dust from the deserts of central Asia falls on the Pacific ocean where it contributes much of the iron (Fe) needed by oceanic phytoplankton

  • Dust from the Sahara desert supplies nutrients to phytoplankton in the Atlantic ocean and phosphorous to the Amazon rain forest.


  • The oceans create bubbles which burst and provide a huge quantity of large and small aerosols.

  • About 200x1012 grams of sea salt are carried to land each year

  • Forest fires in the Amazon are thought to produce 1x1013 grams of fine aerosols.

  • These aerosols affect regional rain fall patterns and influence global warming


  • Volcanoes emit particles into the atmosphere which contribute to soil development down wind of major eruptions.

  • Small particles are also produced by reactions of gases in the atmosphere SO2 ----> H2SO4 H2SO4 + NH3 --> [NH4]2SO4 aerosols

  • These aerosols and others from the sea (dimethylsulfoxide) influence global warming


Natural sources contribute to soil development down wind of major eruptions.

  • Primary aerosolsSoil dust 1500x 1012 g/yearsea salt 1300volcanic dust 33organic particles 50

  • Secondary aerosolssulfates from organics 90sulfates from SO2 12organic condensates 55nitrates from NOx 22

  • sum of natural sources 3070 x1012g/year


Anthropogenic sources contribute to soil development down wind of major eruptions.

  • Primary aerosolIndustrial particles 100x 1012 g/yearsoot 20forest fires 80

  • Secondary aerosolssulfates from SO2 140organic condensates 10nitrates from NOx 36

  • sum of Anthropogenic 390 x1012g/year

  • sum of natural sources 3070 x1012g/year


If more particles are emitted from natural sources, why are we worried about man made or anthropogenic sources; they are 10 times less????

  • sum of Anthropogenic 390 x1012g/year

  • sum of natural sources 3070 x1012g/year


Primary pollutants emitted into the atmosphere sources
Primary pollutants emitted into the atmosphere- sources we worried about man made or anthropogenic sources;

Oxides of nitrogen (NOx = NO + NO2)

Sulfur dioxide (SO2)

Carbon monoxide (CO)

Volatile hydrocarbonds (VOCs)


  • Approximately 72 Tg (1Tg = 1x10 we worried about man made or anthropogenic sources;12grams ) of NOx emitted into the atmosphere

  • The US emits ~30% of this

  • On the next slide we will look at global trends in emissions of NOx


NOx Emissions Trends we worried about man made or anthropogenic sources;


NOx we worried about man made or anthropogenic sources;

dilution aloft

NOx emitted near the ground

  • Much of the NOx comes from

    • Cars

    • Power plans

    • Off the road vehicles

  • The same emitted mass of NOx from different sources can have different atmospheric chemistry effects.


NOx Emissions in the US we worried about man made or anthropogenic sources;


SO2 Emissions trends we worried about man made or anthropogenic sources;


SO we worried about man made or anthropogenic sources;2 Emissions in the US


VOC Emissions in the US we worried about man made or anthropogenic sources;


CO Emissions in the US we worried about man made or anthropogenic sources;


Lead Emissions in the US we worried about man made or anthropogenic sources;


Lead Emissions in the US we worried about man made or anthropogenic sources;


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