THE CHEMISTRY OF THE ATMOSPHERE
Of a very particular interest is the question of the atmosphere of
the planets. The great problem of habitability of the latter is most
intimately connected therewith. Primitive fancy, very early, populated
the stellar bodies, especially the stars and the Sun, with beings
similar to those on Earth. Gradually, however, the insight awoke that
these bodies are incandescent and therefore unfit to shelter life of
the kind with which we are familiar. Attention then turned to the
planets, as they and the Earth belonged to the same order of heavenly
bodies. Perhaps they furnished abodes for our kin. And the stars, suns
like our Sun, should not they be surrounded each with its throng of
planets, gravitating around their central source of light and heat?
This beautiful thought vied with the conception of Earth as the centre
of the universe and as wholly set apart from the other stellar bodies,
whose prime object it were merely to furnish light and to indicate time
for the inhabitants of the Earth. Much to be regretted, it was the
latter far less attractive theory which gained firm hold on the Church,
although a few of its unbiased men, like the renowned Cardinal Nicolaus
Cusanus (1401–1464), declared in favour of the contrary opinion, and
did so unmolested. But times grew harder, ironclad orthodoxy triumphed,
and Giordano Bruno, whose defence was that he simply accepted the
theory of the great Cusanus, was burned at the stake to expiate his
fearless assertion that other worlds, no less than ours, might be
blessed with the presence of living beings.
Undoubtedly, other planets are upbuilt of the same material which
enters into the composition of the Earth--as held already by Leonardo
da Vinci. Spectral analysis teaches us that the same constituents
form all the suns, including our own. If we agree that the suns have
furnished the original substance of the planets revolving around them
it is a natural conclusion that this matter should combine into similar
chemical compounds on planets equally advanced in their evolutionary,
that is cooling, process. And we know, indeed, that the same elements
compose the Sun and the Earth, and that the samples brought to us from
other worlds, _i. e._ the meteors, are of a composition which strongly
reminds us of the rocks in the interior of the Earth. We seek in vain
only for indications of the action of water, which substance has left
such obvious traces on the surface of our globe and in the immediate
strata below. But it should be remembered that the water, in the form
of vapour, as previously set forth, has left all the minor stellar
bodies, and the meteorites manifestly belong to the small or smallest
among the wanderers of the heavens.
There is then no reason to doubt that the material of which the
planets are built essentially is the same throughout the universe.
Their interior should, like that of our Earth, consist of the heavy
metals, principally iron,--strongly prevalent also in the Sun and in
the meteors,--and this metallic nucleus should be clothed with the
silicates, oxides, carbonates, sulphides, and hydrates of all metals,
particularly aluminum, and among the metals we may also count hydrogen.
The melting points of these exterior and lighter substances lies above
1000° C (1800° F.). No life could exist in such a molten mass, so
that not until a solid crust had been formed through cooling was the
possibility of life at hand.
Life is, at least on Earth, tied to certain so-called compounds, in
which carbon is the essential common element, while hydrogen, nitrogen,
and oxygen together with sulphur, phosphorus, iron, magnesium, and a
few other less important elements also enter therein. No substance but
carbon possesses this quality of being a prerequisite of life. Silica
is a close kin to carbon and a substitute in certain organic compounds,
but protoplasm, the main constituent of the living cell, cannot be
built without carbon. In the inorganic world, however, silica by
virtue of its affinity, which is kindred to that of carbon, plays a
rôle somewhat similar to the latter in the almost infinitely variably
silicates. Protoplasm cannot endure in a temperature above 60° C.
(140° F.) or thereabout--certain algæ, it is sometimes stated, thrive
in hot springs up to 80° to 90° C. (176° to 194° F.) but certainly not
over 100° C. (212° F.). At these temperatures--strictly speaking at
all temperatures between O° C. (32° F.) and 365° C. (689° F.)--water
can exist in fluid state and this too is a prerequisite of life. We
may say therefore that life is confined to a small temperature range
between the freezing and boiling points of water. But wherever water
occurs, except in a vessel which it completely fills, there exists also
in the adjacent space, if unoccupied by fluids or solids, water vapour
of at least 4.6 mm. (.18 inches) pressure. There is, therefore, always
an atmosphere of aqueous vapour on any planet whose surface is partly
covered by water.
The palæontologists have agreed that all life commenced in the water.
The manifold living beings which now inhabit the solid crust of the
Earth all descend from ancestors which floated in the waves of the
ocean, the cradle of all organisms. It is not absolutely certain
that oxygen is necessary to all living beings but many biologists
hold that opinion. Certain bacteria are able to draw the oxygen they
require for their development from compounds in which oxygen is bound
sometimes in a very intimate manner, as in sulphates. But these
bacteria are considered degenerate plants, and free oxygen is certainly
indispensable to the existence of the animals and probably also to the
plants with the exception just mentioned. As we shall see later, free
oxygen cannot be present on the planets until a solid crust has been
formed. We may therefore state that the conditions for the existence of
life on a planet are fulfilled when a true atmosphere containing oxygen
and water surround its body.
If we are to understand these conditions, we must study the processes
whereby oxygen is supplied to the atmosphere. As the planets are
segregations from the Sun, they should originally have the composition
of the Sun, particularly that of its outer layers. Here metals occur in
greatest abundance, but there are also a few oxides, especially those
of titanium and magnesium (according to Fowler), hydrogen in great
quantities, oxygen, carbon, cyanogen, and carbon monoxide. It may seem
strange that free oxygen exists side by side with a surplus of hydrogen
and sodium, strong so-called reducing substances which bind oxygen.
But at the high temperatures prevailing on the Sun compounds of oxygen
and the reducing substances, for instance hydrogen, _i. e._ water, are
largely dissociated into their constituents. But, if the temperature
should drop to about 1200° C. (2200° F.), at which point crust building
does not yet take place, the oxygen would be entirely absorbed in the
formation of the compounds mentioned. The compound substances of the
Earth, like those of the Sun, are also strongly reducing, so that we
must infer that free oxygen did not enter into the gas covering of
the Earth at the time when its solid crust was formed. We may gain
a conception of the gases which then existed in the outmost layers
of the Earth by studying the gases on the Sun and on other stellar
bodies, particularly the comets, and also by investigating the gases
absorbed by the molten interior of the Earth. Previous to the crust
formation, the entire mass of the Earth except the gases in its outmost
layers were of the same character as possessed by its molten interior
now. This molten mass, or magma, when in contact with the surrounding
gases partly imbibed them through the process called absorption. An
investigation of the gases present in the magma will therefore give
us an idea of those existing in the original vapours surrounding the
Earth. The magma occasionally comes into view in volcanic eruptions,
and the confined gases are then partly given up into the air, but they
are also partly retained in the solidifying lava, or volcanic rocks,
whence they may be driven off by high temperature and subsequently
analyzed. The direct gas emanations from the craters may also be
gathered and analyzed. Such investigations have been carried out on
a large scale by Albert Brun, Frenchman, Arthur Day, American, and
his co-labourers Shepherd and Perret. Brun reached the surprising
conclusion that water vapour, hitherto considered the most important of
the volcanic gases, in reality was not one of them but originated in
the crust of the earth. This theory, however, was completely refuted
through the investigations by Day and his associates. As an example,
we give the analysis (the mean of several determinations) of volcanic
gases from the crater Halemaumau on the volcano Kilauea in Hawaii:
_May, 1912_
_Per cent. of Volume_
Carbon dioxide 55.4
Carbon monoxide 4.3
Hydrogen 7.7
Nitrogen 29.6
Sulphurous acid 2.9
_December, 1912_
_Per cent. of Weight_
Carbon dioxide 42.9
Nitrogen 25.8
Water 27.5
Sulphurous acid 3.7
In the latter case, it has been shown that air had gained entrance to
the volcanic gases, which air might have carried a quantity of water.
But this quantity could not have been large judging by the amount of
nitrogen present which corresponds to not quite 3 per cent. water by
weight. In the former case water was not included in the analysis. At
any event, a high percentage of water has frequently been observed in
volcanic gases.
When the gases were left in contact with water a considerable part was
absorbed thereby, particularly compounds of chlorine and fluorine and
also ammonia and sulphurous acid. An analysis of such water showed 10
per cent. more fluorine than sulphurous acid and two fifths as much
chlorine as fluorine. The ammonia amounted only to half of one per
cent. of the chlorine. None of the rare air gases were present, which
indicates that the nitrogen originated entirely from the magma and not
from the air.
Brun has analyzed lavas from different volcanoes. The gases extracted
therefrom naturally do not give as reliable information about the
original atmosphere of the Earth as do the gases directly emanating
from the volcanoes. As examples we quote the composition of the vapours
in lavas ejected March 4, 1901, from Stromboli, and from Vesuvius in
the well-known eruption of 1906. They show in percentages of volume:
_Stromboli_ _Vesuvius_
Free chlorine 12.8 0
Hydrate of chlorine 2.0 6.6
Sulphurous acid 4.5 12.0
Carbon dioxide 60.2 73.8
Carbon monoxide 11.5 traces
Hydrogen 0.5 7.6
Nitrogen 6.9 traces
Marsh-gas 1.6 0
----- ------
100.0 100.0
It will be noticed that the composition varies considerably. Free
chlorine cannot very well be primigenial as it, like oxygen, combines
with reducing substances. Chlorine may be produced by heating chloride
of calcium with silica and ferro-silicates which are present in the
magma. At all events, carbon dioxide constitutes the bulk. Next
in importance are sulphurous acid and hydrate of chlorine. Carbon
monoxide, hydrogen, and nitrogen may occur in quite considerable
quantities but are sometimes almost wholly absent.
Day and Shepherd reached the conclusion that the gases emitted by the
hot lava in the Halemaumau crater are nitrogen, water, carbon dioxide,
carbon monoxide, sulphurous acid, hydrogen, sulphur vapour, also
small quantities of chlorides, fluorides, and possibly ammonia. Such,
at least approximately, should also the original composition of the
Earth’s atmosphere have been when the crust was newly formed. Nitrogen,
water, and carbon dioxide were the most important ingredients; in
the high strata hydrogen was present. Oxygen was totally lacking and
reducing gases such as hydrogen, sulphurous acid, and carbon monoxide
abounded instead. If we further note the composition of comets and
meteorites we find that cyanogen, carbohydrates, and carbon monoxide
also are present in the former, argon and helium in the latter. It
is therefore probable that these substances, although absent in the
emanations from Kilauea, yet belonged to the primary atmospheres of the
planets. The rare gases of the air especially should originally have
come from the exterior parts of the sun, as did the nitrogen.
An atmosphere of such a composition would be utterly unendurable to
living beings. It must, if organisms are going to thrive therein,
be purified from such poisons as carbon dioxide, gaseous sulphur,
cyanogen, and sulphurous acid. We know that such a process has taken
place and that the sunlight has been the great chemist who produced
oxygen and carbon from the carbon dioxide. The just mentioned poisonous
gases were subsequently oxidized through electrical discharges. We
all know that the plants up-build their framework under the influence
of sunlight, consuming in the meantime carbon dioxide, water, and a
little ammonia. In the process, oxygen is formed, as are also starch,
cellulose, sugars, and albuminous substances with the aid of the
green colouring matter in plants, chlorophyll, which considerably
accelerates the action. Subsequently these new substances, which all
(except the albuminous ones) belong to the carbohydrate group, are
converted into principally carbon and water. The final result is that
carbon dioxide through the agency of sunlight is split into its two
constituents, carbon and oxygen. This process, which is comparatively
rapid in the presence of chlorophyll, should also, although more
slowly, take place without that medium; and in recent trials the
chemists--particularly Daniel Berthelot--have, indeed succeeded in
imitating without chlorophyll this important function of the plants
through the application of light of a short wave length. In the course
of the many millions of years which geology has proved necessary
for the evolution of our planet, the carbon dioxide in the air was
gradually converted into oxygen and carbon. As long as reducing gases,
such as the poisonous ones mentioned, or any considerable quantities
of carbohydrates and hydrogen yet remained in the atmosphere, the
oxygen was consumed in their combustion. If a solid crust had not
existed to prevent the oxygen from entering into the interior molten
mass, it would also have found its way there and would have oxidized
the reducing substances in the magma. The separation of the interior
from the surrounding gas shell is therefore a necessary requisite for
the existence of free oxygen in the air. Another condition is that the
combustible gases escaping from the volcanoes must be added to the air
at a sufficiently slow rate not to consume all of the simultaneously
formed oxygen. A third requirement is that the liberated carbon should
not in a renewed process of oxidation bind the oxygen just recovered.
As long as the air still was reducing, this last condition was no doubt
fulfilled for that very reason. At all events, the crust once formed
and the original violent volcanic activity somewhat abated, the time
finally arrived when free oxygen existed in the air. The previously
present reducing gases were, except for small fractions, burned into
water, carbon dioxide, and sulphuric acid and the nitrogen compounds
had no doubt yielded free nitrogen to the stores of that gas already
a part of the atmosphere. The time was now ripe for the first plants,
probably low forms of algæ, which, in the oceans, commenced life on our
planet. The carbon dioxide and hydrochloric acid of the air as well as
the newly formed sulphuric acid were absorbed by the running water and
caused a rapid disintegration producing silica and acid silicates. As
plant life developed and extended the formation of oxygen increased.
Falling vegetable matter was imbedded in slime which prevented the
access of oxygen during decay and in this manner the fossil fuels were
deposited. Koene of Brussels first pointed out that the carbon and the
sulphuric compounds accumulated in the Earth would suffice to bind the
oxygen of the air. Later investigations lead to the conclusion that the
carbon alone is sufficient for the purpose. It would therefore appear
that all the oxygen of the air is derived from carbon dioxide belonging
to the original atmosphere or contributed thereto by the volcanoes.
The reason why carbon dioxide and water continuously are liberated from
the magma is undoubtedly that the acid silicates are lighter than the
basic and therefore accumulate in the exterior parts of the magma. A
great surplus of silica exists there. Compounds containing water and
carbon dioxide, _i. e._ hydrates and carbonates, are also light and
should therefore congregate to the same strata where silica abounds,
there partly to be dissolved by the free silica and thus setting
water and carbonic acid free. The latter are, in contrast to silica,
volatile and evaporate therefore into the air leaving the silica
behind. This process is yet in evidence wherever the magma emerges as
through the volcanoes. But also a few other acids in the magma are
highly volatile, as sulphurous, thiosulphuric, and hydrochloric acids.
These also belong to the volcanic gases, are dissolved by the water,
and partake in the processes of disintegration. The carbon dioxide
and hydrochloric acid form carbonates and chlorides. The former are
extracted from the sea water by crustacea, sometimes also by plants,
and form part of our sedimentary strata; the latter are soluble and
remain in the water, chiefly as sodium chloride or common salt. The
thiosulphuric acid, probably a product of ferrous sulphide and acids in
the magma, has entered into numerous insoluble metallic sulphides found
in the Earth. Partly, it has also been oxidized, like the sulphurous
acid, into sulphuric acid and has then assisted in the processes
of disintegration, forming gypsum which has been deposited in the
sedimentary rocks.
The geologists believed formerly that the Earth gradually and
continuously has grown cooler. This theory, however, struggled with
the difficulty that certain cold time intervals, ice periods, were
succeeded by warmer epochs. To begin with efforts were made to
surmount this obstacle by assuming that an ice period on the north
hemisphere was counterbalanced by a warm period on the south hemisphere
and vice versa. In this manner, the mean temperature for the entire
surface of the globe might possibly have been continuously decreasing
although fluctuations had occurred on the two hemispheres. But this
view has proved untenable, because the ice period has left traces also
within the tropics, near the equator, as on Kilimanjaro, in New Guinea,
and so on. It is now practically agreed that the last great ice period
was characterized by a temperature between 4° to 5° C. (7° to 9° F.)
below the present all over the surface of the Earth. This determination
has been accomplished by measuring the difference in height between the
terminals of the glaciers at present and the lowest points where their
grinding action has left obvious traces. The ice coverings of North
Europe, North-East America, South America, along the coast of Chile
and in Argentina, as well as on the southern island of New Zealand,
all appear to have existed simultaneously. Also during earlier eras,
for instance during the Algonkian and the Permian epochs, ice periods
have occurred. The latter, which was felt in Australia, India, and
South Africa, is called the Gondwana-time. This period was formerly
supposed not to have caused any temperature drop except in the tracts
mentioned. Later investigations lead us to believe, as asserted by
Holland in his presidential address to the geological section of the
British Association at its 1914 meeting, that also this ice period
simultaneously embraced the entire globe.
As the Algonkian time belongs to the oldest epochs of geological
history it appears that the temperature on the Earth as long as life
has existed on our planet on the whole has been nearly constant,
with important alternations, however, of warm and cold periods. For
an explanation of these fluctuations, our well-nigh only recourse is
the assumption that the heat-conserving quality of the atmosphere has
changed by virtue of a varying composition. Warm periods occurred when
carbon dioxide was abundant in the atmosphere due to volcanic activity,
cold periods again accompanied a paucity of carbon dioxide. With rising
temperature, the percentage of water vapour in the air also increased,
affording further protection against radiation loss of heat.
Thus, it would seem as if the mean temperature of the Earth’s surface
hardly had changed to any extent worth mentioning during immense spans
of time estimated to about 500 million years. Nevertheless, a slow
process of cooling proceeding toward the centre of the planet probably
takes place. Ever growing quantities of matter are transported from the
interior of the earth through volcanic action. Sedimentary deposits
increase continuously while the interior becomes hollow. As a result
the crust must gradually settle, causing large cracks in the process.
For these weakened places the volcanic products show a special liking
and the craters are strung out in lines along such fissures. In other
places, where volcanic action is less pronounced, hot springs appear
instead, generally emitting carbon dioxide in abundance, occasionally
also sulphurous acid and sulphuretted hydrogen. The dislocations in the
crust also take place along these cracks accompanied by earthquakes.
The study of these various phenomena has enabled us to map out the
fissures, which generally radiate in nearly straight lines from one
point, the so-called centre of collapse, as the cracks in a pane of
glass issue from the point of breakage caused by a swift blow. We shall
later see that such breakage lines and centres of collapse are common
on all stellar bodies which possess a solid crust and are observable
from the Earth.
We may now easily form an idea of the general trend in the development
of the atmosphere. The gases originally present were all, except the
hydrogen, the nitrogen, and the rare gases, strongly absorbent of light
and in particular of heat. It is, therefore, natural that the planets
which have not formed a solid crust possess a strongly absorbing
vapour-shell, as indeed is the case with the large planets (compare
Fig. 13). The crust once formed and the air gradually purged of these
gases, thanks to the sunlight, so that mainly nitrogen and oxygen,
small quantities of the rare gases, and carbon dioxide besides water
remained, the temperature fell rather rapidly. Carbon dioxide formed
the last effective heat-conserving ingredient. As the crust grew
thicker, the supply of this gas diminished and was further used up
in the processes of disintegration. As a consequence the temperature
slowly decreased, although decided fluctuations occurred with the
changing volcanic activity during different periods. Supply and
consumption of carbon dioxide fairly balanced as disintegration ran
parallel with the proportion of this gas in the air. But evolution on
the whole can only proceed in one direction toward a final cooling of
the Earth. This must occur if for no other reason because the store of
energy in the Sun and therefore its radiation must slowly decrease.
With deepening crust and disappearing carbon dioxide vegetation must
ebb, and with it the production of oxygen. This gas also partakes in
the general disintegration through oxidation of iron protoxides in the
mineral rocks. The oxygen portion of the air must therefore finally
reach its maximum and start on the decline. Calculations point to the
conclusion that the carbon dioxide of the air would be consumed in a
few tens of thousand years if new supplies were not furnished from the
interior. Water is also absorbed in the processes of decay as hydrated
compounds are formed, increasing in quantity with falling temperature.
As the amount of water in the ocean is immensely larger (about 50,000
times) than the stores of carbon dioxide in the air and in the seas
the lack of the latter will undoubtedly first become serious. But a
slow desiccation of the planet must subsequently take place, and will
proceed at an accelerated rate with the continued cooling of the Earth.
Then the vapour in the air and consequently precipitation will wane.
Then, as during the ice periods, mighty ice caps will cover the poles
and impound a large portion of the water in the ocean. Finally, the
entire planet, perhaps after having harboured life during trillions
of years, becomes an ice waste with a few cracks in its hard crust
through which warm and acid vapours rise and create small melted areas
characterized by a darker colour than the desert and ice-landscape in
general. Organic life lacks the conditions for existence and ceases
therefore to cheer the planet with its interesting variations. The
planet is dead but continues in obedience to gravitation to describe
its orbit in space.