Geography 140
Introduction to Physical Geography

Lecture: Gaseous Composition of the Atmosphere

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  I. In this lecture, I introduce a completely new major section of the 
     course:  the earth's atmosphere.
     A. Basic definition:  The earth's atmosphere is a mixture of various 
        gases and other "stuff," which is held to it by gravity.
     B. It is about 10,000 km thick (~6,000 mi. or so), but it is densest at 
        sea level (well, denser yet at spots below sea level, such as Badwater 
        in Death Valley, the Salton Sea, and the Dead Sea) and thins out very 
        quickly as you move upwards.
        1. Some 97 percent of it is found in the first 30 km of the earth's 
           surface.
        2. The remaining 3 percent of it thins out from there to the top of 
           the atmosphere.
        3. There's no sharp and definite boundary to the planet's atmosphere:  
           By the time you get to 10,000 km "out there," the density of 
           hydrogen atoms per unit of volume drops to the level of 
           interplanetary space.

 II. The chemical composition of the lower atmosphere (out to about 100 km, 
     the homosphere) is relatively uniform.
     A. Gaseous constituents of the homosphere:
        1. The overwhelming bulk of the atmosphere's constituent chemicals 
           exist in a gaseous state, as "air." Almost all of it is nitrogen 
           and oxygen, with a teensy amount of trace gases.
        2. Nitrogen is far and away the most common gas in our atmosphere.  It 
           makes up 78.1 percent of clean (as IF), dry air by volume  (since 
           nitrogen is a fairly light molecule, it makes up about 75.5 percent 
           of the mass of the atmosphere).
           a. Atmospheric nitrogen exists in the form, N2, or molecular nitrogen.
           b. This particular molecule is very stable:  It does not easily 
              unite with other chemicals because two nitrogen atoms form a 
              powerful covalent bond, sharing three electron pairs between 
              them.  
                i. Geotrivia for you.  Nitrogen will combine with other 
                   elements only when strongly heated.  Nitrogen atoms in 
                   other compounds are very unstable, explosively dropping 
                   their bonds with the other atoms in order to pair up in 
                   their favorite match: one another, to form nitrogen gas. 
                   This is why nitrogen atoms are found in explosives, such as 
                   NITROglycerin and triNITROtoluene (TNT).
               ii. But, when nitrogen is happily pair-bonded as nitrogen gas, 
                   it is very stable.  As such, it is neutral filler stuff in 
                   the atmosphere (kind of like soy powder in hot dogs?).
              iii. Actually, the nitrogen gas in the atmosphere serves to 
                   limit the combustibility of many substances in the presence 
                   of oxygen (the second most abundant gas in the atmosphere):  
                   If there were more oxygen gas in the atmosphere, forest 
                   fires and other combustion events would be even more, 
                   pardon the pun, explosive. 
           c. An interesting irony: Plants and animals need nitrogen in order 
              to make proteins and nucleic acids (such as the four in DNA).  
              Unfortunately, nitrogen in its happiest state, N2, is 
              too stable for most living creatures to use, so nutrient 
              nitrogen is a scarce and limiting resource for life, even though 
              we're sitting at the bottom of an atmosphere filled with 
              nitrogen!  Plants and, ultimately, animals depend on bacteria to 
              "fix" nitrogen into a useful form, nitrate (NO3 that 
              they can absorb and use.   
        3. Oxygen in the form of O2 is the second most common gas 
           in clean (ha!), dry air.  It makes up 21.0 percent of the 
           homosphere by volume  (because oxygen is a somewhat heavier 
           molecule than nitrogen, it makes up 23.1 percent of the mass of the 
           atmosphere).
           a. Superficially, oxygen gas resembles nitrogen gas in that they 
              both consist of two atoms of their respective elements.
           b. That's where the resemblance ends:  Oxygen gas is HIGHLY 
              reactive, highly prone to combine with many other chemicals in a 
              general process called "oxidation."  The stuff is downright 
              promiscuous!
           c. Familiar forms of oxidation (which entails a loss of electrons 
              from the oxidized substance and the release of energy) include:
                i. Respiration.  Animals and plants take in oxygen and use it 
                   to oxidize sugar into carbon dioxide and water, releasing 
                   energy for movement (animals), growth, repair, heat, what 
                   have you.
               ii. Combustion is the rapid oxidation of compounds, such as the 
                   cellulose in wood producing fire.
              iii. Some kinds of mineral weathering represent very slow 
                   oxidative processes, such as rust of iron compounds in 
                   rocks.
        4. The remaining 1 percent of clean, dry air by volume is made up of a 
           variety of trace gases.
           a. Argon, A, an inactive, neutral gas, makes up about 0.93 percent 
              (or 1.3 percent by mass), which just about takes care of that 
              last piddling one percent.  You might think that there's nothing 
              else worth discussing in the remaining 0.06 percent.  Guess 
              again!
           b. Carbon dioxide gas, CO2, makes up only about 0.03 
              percent of clean, dry air by volume.  This vanishingly small 
              amount is very important to the earth's radiation balance and is 
              the subject of much controversy today. 
                i. It is very important in weather processes, because it traps 
                   radiant energy from the sun and reradiated energy from the 
                   earth in certain infrared wavelengths.  By so doing, it 
                   delays the departure of energy from the earth system into 
                   outer space, and this delay permits the lower atmosphere to 
                   maintain a reasonably stable and warm temperature.
               ii. If the earth were a chunk of black rock with no atmosphere, 
                   its blackbody temperature would average about -18° C: 
                   the temperature set by the intensity of incoming solar 
                   radiation, if that radiation were instantly reradiated into 
                   outer space.
              iii. The earth's average temperature (the Sahara and Antartica 
                   averaged in together) is actually about 15° C, some 
                   33° above its blackbody temperature:  The difference 
                   reflects the absorption of roughly half the infrared energy 
                   being reradiated by Earth, energy that is, therefore, held 
                   up in its departure.  
               iv. The tiny amount of carbon dioxide gas is a major player in 
                   absorbing this reradiated energy.  Carbon dioxide is an 
                   important part of the earth's thermostat, if you will:  Its 
                   absorbtion capacity times its abundance means that carbon 
                   dioxide accounts for about 54 percent of the greenhouse 
                   effect that keeps Earth 33° C warmer than blackbody 
                   levels.
                v. Plot complication:  The amount of carbon dioxide is 
                   increasing.
                   a. At the present, it is increasing about 0.4 percent a 
                      year.
                   b. This increase is associated with human activities, with 
                      combustion, such as combustion of petroleum fuels in 
                      vehicles, residential furnaces, power plants, industrial 
                      processes, and in human-set fires.
                   c. Even perfect, clean, non-polluting combustion releases 
                      water vapor and carbon dioxide as its byproducts.
                   d. Whether clean or dirty, human-induced combustion has 
                      been accelerating over the last couple of centuries, as 
                      we are releasing hydrocarbon fossil fuels (that took 
                      millions of years to accumulate) in a geological 
                      "instant."
                   e. Deforestation, especially in the tropics, is often done 
                      through torching (slash and burn agriculture), which 
                      then combusts plant material and adds to the atmospheric 
                      carbon dioxide.  The death of all these plants 
                      drastically reduces photosynthesis, by which carbon 
                      dioxide is combined with water to create sugar and 
                      oxygen (thereby removing carbon dioxide gas from the 
                      atmosphere).  
                   f. Carbon dioxide levels in the earth's atmosphere have 
                      about doubled in the last century, going up about 15 
                      percent just in the last 40 years.
               vi. The reason this is of concern is that one consequence of 
                   the build up of carbon dioxide gas is global warming, as 
                   the carbon dioxide raises the earth's thermostat.
                   a. Global average temperatures have risen about 0.5° C 
                      in the last century (~1° F), coïnciding with 
                      the increase in carbon dioxide. 
                   b. They are predicted to rise another 3° C (~6° F) 
                      over the course of the next century.
                   c. This may have a variety of unpleasant side effects:
                      1. Accelerated melting of polar ice, which could raise 
                         sea levels and flood coastal plains and cities (where 
                         a large fraction of the human population lives and 
                         works).
                      2. The increased energy lingering in the earth system 
                         could result in more storms (such as hurricanes) and 
                         more violent storms at that.
                      3. Increased warming could exaggerate temperature 
                         extremes, floods, and droughts.
                      4. Migration of plant and animal species poleward, 
                         including tropical diseases moving into the mid-
                         latitudes (e.g., dengue, West Nile virus in New York 
                         City).
                   d. It may have a few nicer effects, including accelerated 
                      photosynthesis and crop productivity.
             viii. The picture isn't as simple as a direct, linear 
                   relationship between carbon dioxide levels and global 
                   temperatures, however.
                   a. Increased temperatures of ocean water promotes the 
                      accelerated dissolution of atmopheric carbon dioxide 
                      into carbonic acid, which can then combine with other 
                      elements and precipitate to the ocean floor as carbonate 
                      rock (e.g., limestone).  This ocean sump for carbon 
                      dioxide will slow the build up of carbon dioxide, but it 
                      is not known with how much efficiency.
                   b. Tropical forest combustion builds up carbon dioxide in 
                      the short run (a byproduct of combustion is carbon 
                      dioxide and the loss of photosynthesis prevents the 
                      reuptake of carbon dioxide), but it may cause an 
                      intermediate-term increase in photosynthesis:  The 
                      secondary successional vegetation that moves into a 
                      fired area is often hyperactive in its photosynthetic 
                      activities (sun-loving, fast-growing plants 
                      photosynthesize like crazy).  Again, we don't have the 
                      data to predict how much offset to global warming this 
                      provides.
                   c. On top of all else, the earth's climate is not stable:  
                      There are centuries-long trends in temperature that are 
                      independent of human activity (e.g., the Little Ice Age 
                      of the 18th century, from which we may still be 
                      warming).  Again, big surprise, we are not sure how much 
                      of the global warming is anthropogenic (human-created) 
                      and how much reflects secular (centuries-long) trends in 
                      the planet's climate.
               ix. The growing consensus in the scientific community is that 
                   anthropogenic increases in carbon dioxide are a serious 
                   concern and may account for at least part of the global 
                   warming of the last couple of centuries and that it would 
                   be better to err on the side of caution and do everything 
                   we can to reduce carbon dioxide emissions.
                x. The costs of doing so, however, may be extremely high and a 
                   lot of people (not just oil companies) are worried about 
                   the opportunity costs of responding to the carbon dioxide 
                   and global warming problem with insufficient data.  They 
                   would prefer to err on the side of continuing economic 
                   growth pending the resolution of every single scientific 
                   question.
               xi. The dilemma for decision-makers is, of course, that, if 
                   carbon dioxide buildup is creating global warming, waiting 
                   for all the scientific dotting of the i's and crossing of 
                   the t's may mean we respond when it's way too late to 
                   prevent ecological catastrophe (and the attendant economic 
                   costs).
              xii. This is an area that can use as many new scientists as our 
                   educational institutions can pump out, scientists in 
                   disciplines as diverse as geography, geology, oceanography, 
                   meteorology, biology, public health and medicine, and 
                   economics.  Hopefully, some of you might be among them?  
                   There is so much we don't know, and there are such huge 
                   stakes involved.  
           c. Ozone (O3 is a special form of oxygen.  Instead of 
              being made up of two oxygen atoms, it's made up of three.  
                i. Two of the atoms have a double covalent bond, while the 
                   third bonds to one of them with a single bond.
               ii. It is created by the action of ultraviolet radiation from 
                   lightning and from the sun (high energy radiation with 
                   wavelengths shorter than visible light, i.e., from 0.4 
                   microns to 0.04 microns).  Really shortwave UV (UV-C, 0.04-
                   0.29 microns, and UV-B, 0.29-0.32 microns) has the energy 
                   to pop the double covalent bonds of O2 when it 
                   is absorbed by them. The freed oxygen radicals (O) then 
                   quickly bond to other O2 to form ozone 
                   (O3).  
              iii. This absorbtion blocks the UV radiation from making it all 
                   the way through the earth's atmosphere to the surface, and 
                   a good thing, too, since UV is quite hostile to life, 
                   penetrating tissues and dinging DNA:
                   a. Skin cancer is one expression of too much exposure to 
                      UV.
                   b. A sunburn is a kinder and gentler expression.
                   c. A suntan is your skin's statement that it has been 
                      injured by the penetration of UV:  Melanin granules 
                      absorb a lot of it and darken, producing the bronzed 
                      look.  The more melanin you have, the more UV can be 
                      absorbed, and the darkened melanin granules confer a bit 
                      of protection from the further penetration of 
                      ultraviolet rays.  Most of the damage is done in the 
                      process of acquiring the tan.  The darker you are 
                      naturally, the better off you are in coping with UV 
                      penetration.  The lighter you are, the more vulnerable 
                      you are to skin cancer. 
               iv. A secondary process of ozone construction entails the 
                   knocking off of the third oxygen atom from the ozone 
                   molecule:  The single bond is weaker than the double bond 
                   in regular oxygen and in one pair of the ozone molecule.  
                   The weaker bond can be broken by less energetic rays, by 
                   UV-A, with wavelengths from 0.32-0.40 microns.  The freed 
                   oxygen radical then finds another oxygen molecule to look 
                   for a place to bond, again absorbing some UV radiation and 
                   keeping it from making it to the earth's surface.
                v. Ozone is a teensy component of the homosphere overall:  
                   0.001 percent by volume, varying from 0 to 12 parts per 
                   million, depending on elevation, latitude, and time.
               vi. Ozone is not evenly distributed in the earth's atmosphere:  
                   About 90 percent of it is concentrated about 20 to 50 km up 
                   (roughly 12 to 30 mi. up). 

                   [ ozone concentration in atmosphere, courtesy of 
NASA-Goddard ]

                   a. This is the famous ozone layer in the stratosphere.
                   b. It's just as well ozone hangs out in the stratosphere, 
                      absorbing UV radiation for us down here, since ozone 
                      down here is a rather nasty corrosive pollutant (a 
                      component of smog and, like carbon monoxide, the product 
                      of faulty combustion), which attacks plastics, rubber, 
                      and living tissue (skin and lungs) with great gusto.
              vii. It varies in concentration horizontally, too, particularly 
                   when we examine it through time.
                   a. To get at this, we need to imagine all the ozone 
                      molecules in a column of air stretching from the ground 
                      to the top of the atmosphere.  If we took all the ozone 
                      molecules and pushed them to the very bottom of the 
                      atmosphere (someplace at sea level, calibrating the 
                      temperature to 0° C), we would create a thin layer 
                      of "nuthin' but us ozone molecules."  Every millimeter 
                      of thickness is called 100 Dobson Units.  1 mm = 100 DU 
                      (a millimeter, by the way, is one thousandth of a meter, 
                      which is a tad more than a yard, so a millimeter is a 
                      teense more than one thousandth of a yardstick).  Now, 
                      let us visualize the horizontal distribution of ozone in 
                      Dobson Units all over the Earth at one point in time, 
                      let's say about now:

               [ NASA TOMS image of today's ozone distribution ]

                   b. For an explanation of the map, click here
                   c. So, ozone levels are the lowest over Antarctica, 
                      particularly in Antarctica's spring.  
                   d. Very disturbingly, there has been a substantial decline 
                      in minimum ozone levels over Antarctica over the last 
                      couple of decades and the area covered by less than 220 
                      DU has been increasing through that time (the ozone hole 
                      is defined as any area with less than 220 DU).
                   e. You can see for yourself in this lab, 
                      in which you will make two X-Y graphs showing, first, 
                      the trends in ozone minima through time and, then, the 
                      trends in size of the ozone hole through time.
             viii. The depletion of the ozone layer is an artifact of human 
                   activity. 
                   a. One element that is extremely effective in breaking up 
                      ozone molecules is chlorine. 
                      1. Chlorine often enters the stratosphere in 
                         chlorofluorocarbons, molecules combining carbon, 
                         fluorine, and chlorine (CFCs).  CFCs are very stable, 
                         inert compounds that, because of their benign impacts 
                         on the environment here at the surface, were and are 
                         widely manufactured for all sorts of purposes, 
                         including air conditioning and refrigeration.
                      2. Very sadly, while stable down here, they may become 
                         very unstable and reactive under the special 
                         circumstances of the stratosphere over Antarctica.
                      3. Released down here, they join the air in the 
                         atmosphere and, mixed in thoroughly, they get carried 
                         eventually into the tropics, where the heat lifts air 
                         (including the CFCs) way above ground.  Up there, 
                         some of them drift into the stratosphere and, when 
                         some of these wander into the Antarctic region, the 
                         extreme cold and unique stratospheric clouds of 
                         Antarctica cause the chlorine atoms to dissociate 
                         from the rest of the CFC molecules.  Then, when the 
                         Antarctic spring begins, sunlight lets the chlorine 
                         atoms disrupt ozone molecules to create regular 
                         oxygen and ClO, which can combine with NO to create 
                         ClONO, which can then break into NO2 and 
                         Cl (which can then repeat the cycle).  ClO can also 
                         interact with O3 to form two O2 
                         and .... another independent Cl atom, which can 
                         repeat the cycle ad infinitum.  Because Cl 
                         atoms can repeatedly go through chemical cycles that 
                         break up an ozone molecule, it is estimated that one 
                         measly chlorine atom in the stratosphere over 
                         Antarctica in the spring can destroy 100,000 ozone 
                         molecules before it drifts out of the region or gets 
                         bound up in some other, less reactive compound.  
                         Nasty stuff.
                   b. Another nasty beast is bromine.
                      1. Bromine is found in the form of bromocarbons 
                         (commonly used in fumigants, such as methyl bromide, 
                         and fire extinguishers).
                      2. They, too, get carried to the Antarctican 
                         stratosphere in the winter.
                      3. Unlike chlorine, they don't readily form inert 
                         compounds that can be carried out of Antarctica, so 
                         they recycle longer and are estimated to take out 
                         from 1 million to 10 million ozone molecules.    
                   c. CFCs and bromocarbons are being phased out by 
                      international agreement:  We can't replace the ozone, 
                      but we can gradually reduce the key elements that attack 
                      the ozone.
               ix. In the meanwhile, the depletion of stratospheric ozone and 
                   the spatial extension of the Antarctican (and a smaller 
                   Arctic) ozone hole means that more ultraviolet radiation, 
                   especially UV-B, is making it to the surface of the planet.  
                   a. For humans, this translates into a greater risk for skin 
                      cancer and sunburn:  We have seen a doubling of skin 
                      cancer reports in the last two decades!
                   b. Interestingly, even people with loads of melanin in 
                      their skins are reporting sunburns!  
                   c. This may reflect:
                      1. Ozone depletion.
                      2. Culture: More people run around in nearly nothing 
                         these days, exposing lots more skin than was the norm 
                         100 years ago.
                      3. Social geography: More people of northern and western 
                         European extraction are living in the Sunbelt, to 
                         which they are not evolutionarily adapted.  Type I 
                         (albino and near-albino) and II (pale skin and eyes 
                         and red or light blonde hair) skins were favored by 
                         natural selection at high latitudes to permit Vitamin 
                         D production in low sun-angle climates; they are not 
                         adapted to live half-nekkid in the Sunbelt, where 
                         Type III (light skin that tans fast and almost never 
                         burns), IV (olive or brown complexion), and V (very 
                         dark or black) skin is better adapted.  
                   d. "Slip, slap, slop," as they say in Australia (which is 
                      uncomfortably close to the Antarctican ozone hole):  
                      Slip into more clothes, slap on a hat, and slop on some 
                      SPF.
                      1. If you're a Type I or II, put on SPF 15+ each day.
                      2. If you're a Type III or IV, you might get along with 
                         SPF 8-10.
                      3. Even if you're a Type V, play it safe and use an SPF 
                         4-6.
                x. Ozone is a minor greenhouse gas, accounting for about 7 
                   percent of the warming of the earth above its expected 
                   blackbody temperature.
           d. Some more greenhouse gases:
                i. Methane: CH4
                   a. It makes up about 0.0002 percent of the atmosphere (2 
                      parts per million).
                   b. It accounts for about 12 percent of the greenhouse 
                      effect.
                   c. It is, however, much more efficient a greenhouse gas 
                      than carbon dioxide, about 40 times as effective in 
                      absorbing radiation.
                   d. It is created, among other ways, by agricultural 
                      production, such as rice production and, er, how to put 
                      this delicately, ummmmm, cattle flatulence and belching.
                   e. It is also increasing like crazy:  about 1 percent a 
                      year.
               ii. Nitrous oxide: N2O
                   a. It makes up about 0.00003 percent of the earth's 
                      atmosphere (300 parts per billion).
                   b. It's even more efficient a greenhouse gas than methane, 
                      about 200 to 310 times more absorbtive than carbon 
                      dioxide.
                   c. It currently accounts for about 6 percent of the 
                      greenhouse effect.
                   d. Yep, it's increasing, too, being produced by natural 
                      processes in soil and water AND by those pesky human 
                      activities, such as fossil fuel combustion, agricultural 
                      soil management, and animal manure production and 
                      management, about 0.02 percent a year, half the rate of 
                      increase in carbon dioxide.
              iii. CFCs (mentioned above in the section on ozone depletion) 
                   figure in here, too.
                   a. Currently they are about 0.0000003 percent of the 
                      atmosphere (3 parts per billion).
                   b. They are unbelievably efficient absorbers of radiation: 
                      20,000 times more efficient than carbon dioxide.
                   c. They presently account for about 21 percent of the 
                      greenhouse effect.
                   d. They are increasing at the rate of 5 percent a year, 
                      hopefully a rate being brought down by the international 
                      accords to reduce ozone depletion.     
               iv. The point of detailing these very minor trace gases is that 
                   many of them are increasing much faster than carbon dioxide 
                   and are much more efficient radiation absorbers.  This 
                   means that it is plausible that these may become much 
                   bigger culprits in global warming than carbon dioxide, when 
                   they are considered together.
           e. Other gases present:
                i. Hydrogen
               ii. Neon
              iii. Krypton (not to be confused with Superman's kryptonite ) 
               iv. Helium


Now, I don't expect you to memorize each of these gases and all of their 
characteristics and percentages.  What I want is for you to know the major 
players, why they're important  (nitrogen, oxygen, carbon dioxide, and ozone), 
and their relative abundances and for you to be aware that other, really minor 
gases may become more significant in the greenhouse effect through time.

In the next lecture, I'll summarize the solids in the atmosphere and the 
special case of atmospheric water.

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Document and © maintained by Dr. Rodrigue
First placed on web: 10/06/00
Last revised: 06/07/05

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