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OCR for page 191
Degassing
JAMES C. G. WALKER
The University of Michigan
ABSTRACT
Measurements of the concentrations of rare gases and trace elements
in oceanic basalts have provided new information concerning the structure
of the Earth's mantle and its evolution. This review is based principally
on papers by Allegre, Staudacher, Sarda, O'Nions, Oxburgh, and Jacobsen.
Approximately 35% of the mantle lost more than 99% of its rare gas
content in the first 100 million years of solar system history. A comparable
volume of the mantle has also been depleted in radioactive and other
large ion lithophile elements, the depleted elements being concentrated in
continental crust. But depletion was a much slower process than degassing.
The average age of continental crust is 1.8 billion years, but the average age
of the rare gas atmosphere is 4.4 billion years. There has been very little
mixing of material between the degassed and depleted portion (presumably
the upper mantle) and the undegassed and relatively undepleted portion
(presumably the lower mantle).
Gas fluxes from the mantle indicate that degassing today is inefficient,
affecting only the top few hundred meters of oceanic crust. It is not likely
that sea floor spreading processes like those now operating could have
degassed the entire upper mantle within a 100 million years, even given
large initial heat fluxes. At the same time, it is not likely that sea floor
spreading processes could have dissipated the initial heat of a nearly molten
Earth. Lava flooding could have removed initial heat efficiently and at the
same time degassed the upper mantle rapidly.
Rare gases do not make an atmosphere, of course. There is new
information concerning the release of carbon dioxide from the mantle. As
191
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PLANETARY SCIENCES
pointed out most forcefully by Marty and Jambon, the exogenic system
(atmosphere, ocean, and sedimentary rocks) is deficient in carbon by a
factor of 100 relative to rare gases when present amounts are compared
with present fluxes from the mantle. It appears that carbon dioxide did
not participate in the initial rapid degassing that released rare gases from
the upper mantle. Instead, carbon has been modestly concentrated into
the continental crust like other incompatible, but not atmophile, elements.
Less than 10% of upper mantle carbon has been transferred to the crust,
and the total mantle amount may be 40 times the amount in the exogenic
system.
INTRODUCTION
Important new information has become available in recent years con-
cerning the release of gases from the interior of the Earth. The most fruitful
source of information has been the measurement of rare gas concentrations
in sea floor basalts. The results set important constraints that need to be
incorporated into any comprehensive understanding of the early history
of the planets. In my review here, I will describe some of the highlights
of these results and give an indication of how they are derived. I cannot
provide a complete description of all of the evidence that is used to reach
the conclusions presented.
RESERVOIRS
Measurements on sea floor basalts have provided clear indications of
two major reservoirs within the mantle. The larger reservoir, constituting
about 65% of the mantle, is undegassed and relatively undepleted in
incompatible elements. The remaining 35% of the mantle was degassed
very early in Earth history (within 100 million years of the beginning), and
more than 99% of the initial gas content of this reservoir was released.
Throughout the whole of Earth history there has been very little mixing
between these reservoirs (O'Nions 1987; Anderson 1989~.
These conclusions are based on measurements of the concentrations in
sea floor basalts of the radioactive parent elements shown in Figure 1, along
with their radiogenic daughter isotopes and non-radiogenic cousin isotopes
also shown in the figure (Allegre e' al. 1983~. The important feature of
these isotope systems is that the ratio of daughter/cousin increases through
time as a result of the radioactive decay of the parent, and that there are
no other processes that will cause the ratio of daughter/cousin to change
because they are chemically and physically almost identical.
Figure 2 shows how the ratio of daughter/cousin, called ALPHA,
increases at a rate that depends on the ratio of parent/cousin, called MU.
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AMERICAN AND SOVIET RESEARCH
P are nt D laughter ~ outran
K40 Ar40 Ar36
U,Th He4 He3
Il29 Xel29 Xel30
193
· ALPHA (=DAUGHTER/COUSIN) increased by
decay
· MU (=PARENT/COUSIN) determines rate of
1ncre ase
FIGURE 1 Isotope taxonomy.
The solid line in the top panel of the figure shows the evolution of the
amount of radiogenic 40Ar resulting from the decay of radioactive 40K
The bottom panel shows the evolution of the ratio of 40Ar/36Ar, ALPHA
The effect of a degassing episode fairly early in Earth history is indicated
by the left hand arrow labeled Degas 50%. The degassing episode reduces
the concentration of 40Ar by a factor of two, as shown in the top panel.
Because 36Ar concentration is also reduced by a factor of two there is
initially no change in ALPHA The rate of increase of ALPHA with time
is larger after the degassing episode, however, because there is less 36Ar
in the denominator of the ALPHA ratio. This evolution is shown by the
dashed line in the figure. The effect of a second degassing event at -1 billion
years is also shown in the figure. The impact of the second degassing event
on the evolution of ALPHA is smaller because, later in Earth history,
there is less radioactive 40K left to decay. Thus, early degassing leads to
large increases in ALPHA; late degassing has a smaller effect. The event
in the middle of Figure 2 shows the effect of a depletion by 50% in the
concentration of radioactive 40K Depletion reduces the rate of increase
of ALPHA in the manner indicated by the dashed line. In this way it is
possible to deduce the history of MU from measurements of ALPHA
The basic data concerning mantle degassing appear in Figure 3. They
are ALPHA values measured for He, Ar, and Xe in mid-ocean ridge
basalts and in ocean island basalts. The mid-ocean ridge basalts appear to
sample the upper mantle, whereas the ocean island basalts are assumed
OCR for page 194
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PLANETARY SCIENCES
_ 1.5
·_.
A:
0 a.)
P
C: 0 5
i_
5-
o
400
ID
~ 200
lo
Degas
/~,.~-
/6'
1
Deplete
50% j
Degas 50%
, -, , 1
- . ~~ - ''
-
-73 -1
BILLION YEARS
FIGURE 2 Measure ALPHA to deduce history of MU.
1
to sample plumes of material rising from the lower mantle. There is a
range of compositions of ocean island basalts representing various degrees
of mixing between lower mantle material and upper mantle material. As
representative of the least contaminated material I show results for Loihi
sea mount in Hawaii. The point is that ALPHA is larger in MORB than in
Loihi material, which indicates that MORB material is more degassed. The
enhancement in ALPHA has been large for He and Ar. From data such
as these it is now possible to derive important results concerning mantle
reservoirs.
First, the bulk Earth concentration of K gives the 40AT concentration in
undegassed mantle material. The ALPHA value observed in Loihi basalts
gives the 36Ar concentration in undegassed mantle material. The mass of
36Ar in the atmosphere then gives the mass of the mantle that has been
degassed. From a comprehensive study of rare gas isotope systematics
Allegre et al. (1987) deduce that 46% of the mantle has been degassed.
To increase the ALPHA value of Ar from the Loihi value to the MORB
value it is necessary that no more than 390/25000 = 1.6% of the initial 36Ar
complement be retained in degassed mantle material. This value would
apply in the case of early degassing from undepleted material. Delayed
degassing or prior depletion of 40K would reduce the permitted degree of
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AMERICAN AND SOVIET RESEARCH
He
ALP HA
Ar
,
Xe
MORB 86~000
Loihi 25,000
195
25~000 6.95
390 6.48
MORB samples degassed reservoir
(upper mantle ~
Loihi samples undegassed flower
mantle ~
FIGURE 3 Data that constrain degassing (AIlegre et al. 197.
retention. The conclusion is that degassing has been very thorough indeed.
At the same time, because the difference between ALPHA values in Loihi
and MORB is so great, it is possible to conclude that just 2% contamination
of MORB material by Loihi material would reduce the ALPHA value of
the degassed mantle by a factor of two. There is therefore evidence for
strong isolation of the mantle reservoirs from one another.
The increase in the ALPHA value for Xe between Loihi and MORB,
although modest, demonstrates that degassing took place very early in
Earth history. For ALPHA to have changed, degassing must have occurred
before all of the parent i29I had decayed away. But the half life of t29I
is only 17 million years. Therefore, the division of the mantle into two
reservoirs, the very thorough degassing of one of these reservoirs, and the
nearly total isolation of the two reservoirs all took place very early in Earth
history. At this time it is not clear to me how to reconcile these surprising
conclusions with our current understanding of the growth of the Earth by
planetesimal impact, in which planetesimals were vaporized and degassed,
at least during the later stages of accretion. Neither is it clear how to
reconcile with these data the current thinking concerning the formation
of the Moon by a giant impact event occurring near the end of Earth
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PLANETARY SCIENCES
accretion. It appears likely that such an impact would have completely
remixed and homogenized the mantle. On the other hand, it is not clear
that such an impact event would have led to complete degassing of the
mantle or to complete removal from the Earth of any atmosphere released
during the course of previous accretion. Also unclear is what physical
process causes the separation of the mantle into two distinct reservoirs. In
my further analysis I shall assume that degassing of the upper mantle was
a consequence of mantle convection, possibly driven by accretional energy,
but that most of the impacts, and in particular the giant Moon-forming
impact had already occurred before the processes that brought about the
presently observable state had begun.
In this interpretation then, degassing should be related to continental
growth and the depletion of the upper mantle in incompatible elements.
Studies of continental growth and depletion are based on precisely the same
kind of isotopic arguments as the studies of degassing already described.
The only difference in depletion is that the daughter and cousin isotopes
are concentrated in the continents instead of in the atmosphere. Analyses
of Sm-Nd, Lu-Hf, and Rb-Sr isotopes in sea floor basalts, summarized in
Figure 4, indicate that 30% of the mantle has been depleted to form the
continents (Jacobsen 1988~. The average age of the continents is 1.8 Ga.
Allegre e! al. (1983, 1988), in a similar analysis, conclude that 35% of the
mantle has been depleted while 47% of it has been degassed (Sarda et
al. 1985~. The average age of the rare gas atmosphere deduced in their
analysis is 4.4 Ga. My tentative conclusion is that the degassed and depleted
reservoirs are probably the same, but that degassing occurred much earlier
than depletion.
FLUXES
Fluxes of gases from the mantle to the atmosphere can be deduced
from the measured flux of 3He and the concentration ratios in sea floor
basalts. These fluxes lead to the very interesting conclusion that heat is
released much more readily from the mantle than are the rare gasses
(O'Nions and Oxburgh 1983; Oxburgh and O'Nions 1987~. Further it can
be argued that degassing today is inefficient. Processes now operating could
not have degassed the upper mantle rapidly and thoroughly. A comparison
of the fluxes of heat, helium, and argon is presented in Figure 5. The
sources are mainly concentrated in the lower mantle because the upper
mantle is depleted in radioactive incompatible elements. The heat flux
through the surface of the Earth exceeds the sum of upper and lower
mantle sources because the interior of the Earth is cooling down. This fact
is reflected in the Urey ratio of source/flux. For heat this ratio has a value
of about 0.6 (Pollack 19&0~. For 4He the Urey ratio is 6.8, indicating that
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AMERICAN AND SOVIET RESEARCH
He3
Ar36
Xel30
He4
Ar40
Xel29
U238
Th232
K40
HEAT Q
DE GASSED
DEPLETED
DEPLETED
Ndl44
Hfl77
Sr86
/////////////////////~
A////////////
a///////// IW/////~
///////////////////1~\\\~
,///////////\
///////////AK//////~
//////////////~V//////////~
//////'E~///////////~
//////////////~IY///////////
_
///////////////~////////////
//////////
//////////////~\\\\\\\\\\\\~
,///////////////~\\\\\\\\\~
///////////////~\\\\\\~/////
, . . . . . . . . . . , . . , . . ~ . . ..
/////~//////////1~\~\\\\~/~
0 0.5 t.O
197
`~79 LOWER
`~ MANTLE
MANTLE
CONTINENTS
ATMOSPHERE
Allegre et al.
"Jacobsen
FIGURE 4 Comparison of deductions concerning degassing and depletion (Allegre et al.
1983, 1987; Jacobsen 19883. Ibe team indicate what fraction of the terrestrial complement
of each isotope is in the indicated reservoir. HEAT Q refers to heat source.
most radiogenic helium is retained within the Earth and that the flux from
mantle to atmosphere is much less than the production within the Earth.
However, the flux does exceed upper mantle production. Helium must be
flowing from the lower mantle to the upper mantle at a significant rate.
For 40Ar, on the other hand, the flux is less than the upper mantle source.
There is no evidence of flow from lower mantle to upper mantle; the Urey
ratio is 23, and 40Ar is accumulating even in the depleted upper mantle.
These observations provide strong support for the notion of a two-layer
convective structure in the mantle.
It is entirely reasonable to suppose that heat is more mobile than
helium which is in turn more mobile than argon. The argon flux from the
mantle is 6.2 x 106 molely. The 40Ar concentration in the upper mantle
is 3 x 10-~° mole/g. Therefore, the rate at which upper mantle material
is degassed, calculated from the ratio of these two numbers, is 2 x 10~6
g/y. Since the mass of the upper mantle (35% of the total mantle) is 1.4
X 1027 g, it would take 70 Ga to degas the upper mantle at this rate. But
the xenon isotope data indicate that the upper mantle was degassed in less
than .1 Ga. Therefore, the present rate of degassing is too slow to explain
the observations by a factor of 1000.
Furthermore, degassing today is inefficient, in the sense illustrated in
Figure 6. Ocean crust is formed by the partial melting of upper-mantle
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PLANETARY SCIENCES
UREY RATIO 0.6
SOURCE/FLUX
FLUX: 3.6E15}
Heat He4
6.8
9.6E7 ~
Ar40
~ .62E7 ~
Upper mantle
SOURCE: .09E 1 5 4E7
watt
mole/y
~ 5.~7 ~
1E7
tower mantle
SOURCE: 1.4E15 63E7 13E7
FIGURE 5 Fluxes of heat and gases and ratios of sources to fluxes.
material. The degree of partial melting can be deduced from the con-
centrations of the completely incompatible element potassium. Potassium
concentration is enhanced in ocean crust by a factor of 10, more or less,
so we have approximately a 10% partial melt of 60 kilometers of upper
mantle material to produce six kilometers of ocean crust. About the same
increase by a factor of 10 can be expected in the concentration of 40Al,
also presumably a completely incompatible element. New ocean crust is
generated at the rate of 3 km2 per year. 1b produce the 40Ar degassing flux
of 6.2 x 106 mole per year it would be necessary to extract 40Ar from just
the top 250 meters of ocean crust. This extraction presumably occurs by in-
teraction between sea water and the ocean crust. The 40Ar does not diffuse
directly out of the crust or bubble out of the magma. It must be extracted
by leaching at relatively shallow depths in the crust. During the lifetime of
the sea floor before subduction, heat will be extracted from a lithospheric
layer approximately 60 kilometers thick, but Ar will be extracted only from
250 meters of ocean crust. This thickness of crust is equivalent, before
partial melting, to Z5 kilometers of upper mantle, so the release of Ar is
about 25 times less efficient than the release of heat. The flux data indicate
that radiogenic rare gases are accumulating in the mantle. The degassing
process now operating is inefficient and slow. It seems that the process
that originally degassed the upper mantle completely and rapidly must have
been markedly different from the process now operating.
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AMERICAN AND SOVIET RESEARCH
UPPER
MANTLE
K=42 ppm
Ar40-3E- 10
mole/g
60 km
199
3 km^2/y
OCEAN
(RIOT
~ 6km
/ K-500 ppm
/ Ar40=3E-9
/t 096 p artial melt
Ar40 degassing flux
= 6.2E6 mole/y
Leaching
250 m
DE GASSED
C RUST
FIGURE 6 Degassing is inefficient compared with the extraction of heat.
CARBON DIOXIDE
~ what extent can the rare gas results be applied to more important
constituents of the atmosphere? It turns out that there is significant infor-
mation concerning carbon dioxide (Des Marais 1985; Marty and Jambon
1987~. The data and results are summarized in Figure 7. The flux of carbon
dioxide from mantle to atmosphere today is 2 x 10~2 mole per year. The
flux of 36Ar is 250 mole per year, so the ratio of the fluxes is 8 x 109.
On the other hand, the ratio of the amounts in atmosphere, ocean, and
continental crust is 1.8 x 106. The ratio of fluxes is very much larger than
the ratio of amounts now present in the surface layers of the Earth. Carbon
is missing from the surface layers relative to argon.
This conclusion can be seen also in the accumulation times calculated
by dividing the flux into the amount. Carbon would accumulate at present
rates in 5 x 109 years, but it would take 2.2 x 10~3 years for the 36AT now
in the atmosphere to accumulate at the present flux The conclusion is that
while 36Ar was massively degassed earlier in Earth history, carbon did not
participate in this early degassing. If carbon was rapidly released from the
mantle early in Earth history it was just as rapidly returned to the mantle.
Carrying this analysis further it can be concluded that carbon is a
lithophile and not an atmophile element. From the flux ratio of carbon to
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Accumulation times: 5E9
AMOUNT/FLUX
PLANETARY SCIENCES
2.2E13 y
Amounts: lE22 5.6ElC mole
Ratio C/Ar = t.BE6
CRUST AND ~ ~
ATMOSPHERE C ~ T Arab
MANTLE
Fluxes: HE ~ 2 250 mole/y
Flux ratio C/Ar = BE9
FIGURE 7 Compared to argon, carbon is deficient in the crust and atmosphere.
36Ar and the concentration of 36Ar in the upper mantle we can calculate
the concentration of carbon in the upper mantle. The value is 1 x 10-4
mole/g. This calculation assumes that carbon is not more mobile than Ar,
surely a reasonable assumption. If carbon is less incompatible than Ar the
required upper mantle concentration of carbon would be larger. From the
concentration and the mass of the upper mantle I calculate that there are
1.4 x 1023 moles of carbon in the upper mantle. The amount in the crust
and atmosphere and ocean is only 1 x 1022 mole (Wilkinson and Walker
1989~. Therefore less than 10% of upper-mantle carbon has been degassed.
By way of contrast, more than 99% of upper mantle 36Ar has been degassed.
Continuing the analysis and assuming that the lower- mantle concentration
is given by the upper-mantle concentration augmented by crustal carbon
mixed back in, the total amount of carbon in the mantle is 4.2 x 1023
mole, which is 42 times the amount in crust, ocean, and atmosphere. It
seems that the fate of most carbon dioxide released from the mantle is
to be incorporated into oceanic crust in weathering reactions and to be
carried back into the mantle on subduction. Only a small fraction of the
carbon is captured in the exogenic system as cratonic carbonate rocks. The
average carbon concentration in continental crust is 5 x 104 mole/g. The
concentration in the upper mantle is 1 x 104 mole/g. Therefore, the crust
is only moderately enriched in carbon dioxide relative to the upper mantle
and, unlike the rare gases, carbon is a modestly incompatible element.
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AMERICAN AND SOVIET RESEARCH
21)1
CONCLUSION
The rare gas data indicate that there was early, thorough degassing
of the upper mantle, but that there remain large amounts of primordial
rare gases in the undegassed, lower mantle reservoir. The time scales
and rates of degassing and depletion are very different. Depletion and
continental growth occurred much later in Earth history than degassing.
Degassing today, by weathering of the sea floor, is a slow and inefficient
process and could hardly have provided the rapid and total early degassing
that apparently occurred. Carbon dioxide did not degas like the rare
gasses and is only modestly incompatible in the upper mantle. With the
example of carbon dioxide in mind, we must be cautious about deducing
degassing histories of other important atmospheric gases like nitrogen or
water from the rare gas data. In the absence of relevant observations it is
not immediately clear whether other atmospheric gases have behaved more
like argon or more like carbon dioxide. By analogy with the Earth, it does
seem likely that large amounts of both rare gases and carbon dioxide may
be retained within the interiors of Mars and Venus. This possibility must be
kept in mind in the study of the origin of planetary atmospheres. I do not
feel that we yet have a satisfactory description even in qualitative terms of
the origin of the Earth and the atmosphere. The challenge is to reconcile
the ideas of planetary growth by accretion, impact degassing during the
course of accretion, the origin of the Moon by a giant impact, and the data
described in this paper concerning the degassing history of the mantle.
ACKNOWLEDGEMENTS
This research was supported in part by the National Aeronautics and
Space Administration under Grant NAGW-176. I am grateful to Alex
Halliday and Richard Arculus for guidance and advice. During the course
of the conference my ideas were significantly influenced by discussions with
D. Weidenschilling, L. Mukhin, Jim Kasting, Dave Stevenson, and V.N.
Zharkov. I am grateful to all of them.
REFERENCES
Allegre, CJ., S.R. Hart, and J.-F. Minster. 1983. Chemical structure and evolution of
the mantle and continents determined by inversion of Nd and Sr isotopic data, II.
Numerical experiments and discussion. EZarth Planetary Sci. Letters 66:191-213.
Allegre, CJ., T. Staudacher, P. Sarda, and M. Kurd. 1983. Constraints on evolution of
Eanh's mantle from rare gas systematic Nature 303:762-766.
Allegre, CJ., 1: Staudacher, and P. Sarda. 1987. Rare gas systematics. formation of
the atmosphere, evolution and structure of the Earth's mantle. Earth Planetary Sci.
Letters 81:127-150.
Anderson, D.L. 1989. Composition of the Earth. Science 243: 367-370.
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202
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Des Marais, DJ. 1985. Carbon exchange between the mantle and the crust and its
effect upon the atmosphere: today compared to Archean time. Pages 602-611. In:
Sundquist, E.T., and W.S. Broecker (eds.~. Natural Variations in Carbon Dioxide and
the Carbon Cycle. American Geophysical Union, Washington, D. C.
Jacobsen, S.B. 1988. Isotopic and chemical constraints on mantle-crust evolution. Geochim.
Cosmochim. Acta 52 1341-1350.
Marty, B., and A. Jambon. 1987. C/3 He in volatile fluxes from the solid Earth: implications
for carbon geodynamics. Earth Planetary Sci. Letters 83:16-26.
Oxburgh, E.R., and R.K. O'Nion~ 1987. Helium loss, tectonics, and the terrestrial helium
budget. Science 237:1583-1588.
O'Nions, R.K, and E.R. Oxburgh. 1983. Relationships between chemical and convective
layering in the Earth. J. Geological Soc. London 144:259-274.
O'Nions, R.K, and E.R. Oxburgh. 1983. Heat and helium in the Earth. Nature 306:429431.
Pollack, H.N. 1980. The heat flow from the Earth: a review. Pages 183-192. In: Davies,
P.A., and S.K Runcorn (eds.~. Mechanisms of Continental Drift and Plate Tectonics.
Academic Press, New YorL
Sarda, P., T. Staudacher, and CJ. Allegre. 1985. 40Ari36Ar in MORB glasses: constraints
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W~lkinson, B.H., and J.CG. Walker. 1989. Phanerozoic cycling of sedimenta~y carbonate.
American J. Sci. 289:525-5413.
Representative terms from entire chapter:
rare gas
