At 10:03 AM 01/10/2001 -0400, Frank Spear wrote:
>Dugald and others,
>I can't resist weighing in on this discussion.
>Dugald started off with an elegant equilibrium discussion of how to
>view buffering, but ended with a kinetic argument...
...that rests on the same strong foundation as an elegant technique of
determining a P-T path from a garnet zoning profile (Spear & Selverstone
1983 CMP 83,348-357) - the postulation that diffusion within garnet is
>A useful quantity to calculate for your s-buffer assemblage in the
>KFMASH-O2 system for the assemblage Grt+Bt+Mu+Mt+Qtz+aqueous vapor
>phase is the partial derivative (¸Xalm/¸f(O2))P,T. This will provide
>an equilibrium view of the sensitivity of the garnet Fe/Mg to changes
>in f(O2). Another useful quantity is (¸Mgrt/¸f(O2))T,P (where M is
>the amount of the phase), which will provide a measure of the amount
>of garnet (or any other phase) that will be consumed/produced as a
>function of f(O2). It is also useful to quantify the amount of oxygen
>required, in which case a useful derivative is (¸Mgrt/¸M(O2))T,P.
How about the partial derivative (dM(O2)/df(O2))T,P),normalized to 100
oxygens in the less oxidized assemblage? This could be used to compare the
limited equilibrium mass-transfer capacity of various s-buffer reactions to
the unlimited mass transfer of any r-buffer reaction. But none of the
above will ease my suspicion that many assemblages with F>2 are former
divariant assemblages that ran out of r-buffering capacity due to the
relatively fast rate of equilibration of divariant assemblages.
Mass-transfer of oxygen would not be necessary; loss or gain of _any
component_ would lead to complete consumption of one mineral and hence loss
of r-buffering for all components of the assemblage (including oxygen).
>Since most minerals are dominantly oxygen, I suspect one would find
>that most metamorphic assemblages are pretty effective s-buffers.
>That is, the value of f(O2) is pretty nearly totally controlled by
>the internal equilibrium.
Most minerals being dominantly oxygen is not sufficient; f(O2) buffers must
be able to produce or consume O2 and this depends on altervalent cations
(principally Fe). But for sure the equilibrium f(O2)-buffering capacity of
crustal rocks is huge. In a 1948 paper in J Geol, Tom Barth showed that
lateritic weathering of average continental crust to a depth of ~240m would
consume virtually all the oxygen in the atmosphere.
>I know of no examples where major changes
>in f(O2) have been documented in regionally metamorphosed rocks as a
>result of infiltration.
Me neither. My intersecting isograds in southern Ontario (1970 J Petrol)
were cited by Rice and Ferry (1982 Reviews in Mineralogy 10) as evidence of
km-scale "infiltration and the external control of fluid composition", yet
sillimanite-zone metapelites containing either graphite or abundant
magnetite occur within a few meters of each other, reflecting a steep
gradient of f(O2) that evidently was not much flattened during the
It looks as if Rice and Ferry fuzzified "buffering" quite deliberately:
"Following the treatment of buffers in the chemical literature, we adopt
the more general concept of buffering phenomena. Buffers are considered as
those equilibria that _resist changes_ in certain intensive variables that
are imposed on the system under consideration. The conventional petrologic
definition of buffers -- equilibria that _fix_ intensive variables -- is
then simply a special case of this more general definition of buffers." (op
Dugald M Carmichael Phone/V-mail: 613-533-6182
Dept of Geological Sciences and Geological Engineering
Queen's University FAX: 613-533-6592
Kingston ON K7L3N6 E-mail: [log in to unmask]