21.

12 MULTIDIMENSIONAL TRANSPORT AND REACTION 549

A D

Metabasalt

Inc

E Selvage
B
Hb

Czo
Bt-bearing
Hb-bearing

Ky

Hb
Selvage

F
C

Glc + Omph + Ep
Selvage

Metacarbonate

Fig. 21.34 Photographs of cut rock slabs illustrating vein–selvage relations. (A) Vein and alteration selvage cutting Ankerite–albite zone
metacarbonate rock, south-central Connecticut. Dashed line denotes geochemical profiles shown in Figure 21.35 and discussed in Section 21.13.
Width of field is 12.5 cm. (B) Vein and selvage cutting Amphibole zone metacarbonate rock, south-central Connecticut. Vein, at left, contains coarse
hornblende (Hb) and clinozoisite. Moving to the right, there is a clinozoisite-rich zone directly adjacent to the vein (Czo), then a zone where biotite has
reacted to form amphibole, then finally the less reacted biotite-bearing rock (Bt). Infiltrating fluid had lower XCO2 than that in equilibrium with biotite-
bearing assemblage, and therefore drove decarbonation producing amphibole (reaction (21.87)). Width of field is 9.5 cm. (C) Glaucophane (Glc) and
omphacite (Omph) in vein and selvage along top half of photo. Note “fingers” of glaucophane-rich alteration extending away from vein zone (arrows).
Metacarbonate rock, Cycladic subduction complex, Tinos, Greece. Width of field is 17 cm. (D) Greenschist facies metabasalt which still contains relict
igneous plagioclase phenocrysts at right, cut by vein and plagioclase + chlorite selvage at left. Vein contains inclusion of selvage (Inc) dislodged from
the vein margin. Width of field is 12 cm. (E) Amphibolite facies vein and kyanite + staurolite + biotite-rich selvage cutting metapelitic rock, south-central
Connecticut. Kyanite (Ky) appears as light gray crystals in photo. Note large grain size of kyanite along vein margin. Width of field is 11 cm.
(F) Amphibolite facies quartz–garnet–kyanite–biotite–carbonate vein cutting granulite facies plagioclase + pyroxene mafic gneiss, northeastern
Connecticut. Note large garnet mass growing in vein (G). Width of field is 15 cm.
550 Material transport during metamorphism
(e.g. Palin, 1992; Young and Rumble, 1993; Abart, 1995; van
Haren et al., 1996). In these cases, the total timescale of vein
activity could have been longer if the fluid flow occurred in
multiple pulses separated by quiescent periods.
The mass precipitated in veins is derived from through-
going fluids, the local wall rocks, or some combination.
Study of amphibolite facies veins in southern Connecticut
(Ague, 1994b) indicates that about 30 volume percent of the
mass was derived from external fluids, and about 70 volume
percent from the local wall rocks. The volume of externally
derived quartz would have required an average time-
integrated fluid flux, qTI, of about 3 × 105 m3 m−2 (Eq.
(21.67)). This result was later tested by examination of geo-
chemical fronts (Ague, 2003a). It turns out that where large
amounts of fluid flowed along cracks from metapelitic rocks
into metacarbonate layers, Al was transported from metape-
lite to metacarbonate (Fig. 21.34(B)). Kv can be estimated
using fluid and rock concentration values for metapelite.
Taking an Al concentration of 10−3 molal (Manning, 2001,
2007), and a typical Al2O3 concentration in the rock of 25 wt
% (Ague, 2003a), the resulting Kv is about 7 × 10−5. The
distance of Al metasomatism along the cracks varies but is
generally in the range of 1 to 10 m. The corresponding qTI
values are 104 to 105 m3 m−2 (Eq. (21.60)). These values are
compatible with the estimate obtained independently from
quartz vein precipitation, and confirm that some veins were
conduits for very large fluid fluxes.
The sequence of vein-forming events in these Connecticut
rocks is envisioned as follows. First, fracturing opened up
channel-ways through which regionally migrating fluids
moved. Some quartz was precipitated as the fluids ascended
and cooled. In addition, the migrating fluids interacted chemi-
cally and isotopically with the surrounding wall rocks to pro-
duce alteration selvages (Fig. 21.34(A), (B), (E)). The exchange
was probably dominated by diffusion, but some flow through
the wall rock margins may have occurred as well. Silica also
diffused down pressure gradients to the fractures in order to
help seal them. In this way, both externally derived and inter-
nally derived silica was deposited in the fractures.
This “crack–flow–seal” sequence of events was repeated
many times in order to produce a typical amphibolite facies
vein. Selvages in metapelitic rocks are depleted in silica
because it was repeatedly transferred to the adjacent veins
in order to seal them. Mass transfer of alkalis in selvages
helped the aluminous index minerals staurolite and kyanite
to grow at the expense of alkali-rich minerals like muscovite
(Fig. 21.34(E)). The infiltration of fluids derived from meta-
pelitic or igneous rocks drove decarbonation reactions
around veins cutting metacarbonate layers (Figs. 21.27,
21.34(B)). The presence of fluids also facilitated diffusion
and the growth of large crystals in and around the veins
(Fig. 21.34(E)). Some vein kyanite crystals reached ~5 cm
in length, as opposed to the grain sizes of all minerals out-
side selvage margins which are usually <0.5 cm. We can
conclude that fluid flow through veins may exert consider-
able controls on both rock composition and grain size in
metamorphic belts.
21.13 DETERMINING CHANGES IN COMPOSITION AND VOLUME
USING MASS BALANCE
This chapter has been concerned with mass transfer and
changes in rock composition. The expression for the time-
integrated fluid flux based on Na metasomatism, for example,
requires that we know how much Na the rock gained or lost
(Eq. (21.71)). But we have not yet addressed the question
of how the magnitudes of such changes can be determined
in real rocks. The equations needed to assess metasomatic
changes are straightforward to derive and are firmly based
on mass balance principles. Mass balance, in turn, follows
directly from the first law of thermodynamics. The following
treatment is based largely on the work of Gresens (1967),
Grant (1986), Brimhall et al. (1988), Ague (1994a), and Ague
and van Haren (1996); the reader is referred to these papers
for further details.
In order to determine compositional changes, one must
first have a chemical analysis of the altered rock, as well as an
analysis of the precursor rock from which the altered rock
was derived. In practice, identification of the precursor can be
a difficult task, particularly if metasomatism has been exten-
sive. Misidentification of precursors renders a mass balance
analysis invalid, so the utmost care must be exercised at this
stage. One setting in which precursor uncertainties are mini-
mized is alteration selvages adjacent to veins that cut across a
metasedimentary layer. Relatively little original sedimentary
variation would be expected within a single layer, although
graded bedding and other sedimentary features can introduce
compositional heterogeneity and must be identified prior to
geochemical sampling. Sedimentary variations tend to be
most pronounced across layers (top to bottom) rather than
along them, so profiles that stay within a single horizon
parallel to layering generally have the smallest precursor
uncertainties. For such profiles, the amount of metasomatism
can be monitored progressively from little-altered wall rock
precursor outside the selvage margins, to more strongly
altered rock in vein selvages.
Figure 21.34(A) shows a synmetamorphic quartz–albite–
calcite–ankerite vein cutting across a greenschist facies meta-
carbonate layer in the Wepawaug Schist, Connecticut (Ague,
2003a). In the alteration selvage adjacent to the vein, musco-
vite was destroyed and albite precipitated. Finely dissemi-
nated organic matter and pyrite in the matrix organized into
larger “clumps” in the selvages, lending a bleached and
spotted appearance to the selvage areas. Xenotime, a phos-
phate mineral that is normally rich in rare earth elements
(particularly the heavy rare earths) precipitated in and around
the vein. The vein represents a channelway for fluids that
migrated through the metamorphic sequence, and the selvage
records chemical and isotopic alteration that occurred due to
reactions between these fluids and their wall rocks.
Geochemical profiles across the wall rock and vein are
shown in Figure 21.35. These data were obtained using X-ray
fluorescence and inductively coupled mass spectrometry
techniques carried out on aliquots of rock cut from the sample
at regular intervals. Take, for example, the plot illustrating the
 21.13 COMPOSITION–VOLUME CHANGES FROM MASS BALANCE
Fig. 21.35 Geochemical profiles Vein
across traverse shown in Figure 2300
21.34(A). See text for discussion. 2200
(Modified from Ague, 2003a;
2100 Si/Zr
published by permission of the
American Journal of Science.)
2000
3800
Ca/Zr
3400
3000
60
Ti/Zr
40
20
0
450
400
Mg/Zr
350
0 5
X (cm)
increase in the Na/K ratio in the alteration selvage and vein
area. While this may seem like a simple relationship, there are
actually six different ways to interpret it! First, the precursor
rock that the altered selvages were derived from could have
been different from the wall rock outside the selvages. This
kind of precursor uncertainty can be ruled out given that we
are examining a profile across a vein that cuts a single,
homogeneous metasedimentary layer. Consequently, we can
be confident that the Na/K ratio did in fact increase due to
fluid infiltration and chemical reaction. This, in and of itself,
is very valuable information. But we can go further and
investigate what kind of mass changes caused the ratio to
increase. A second possibility, then, for interpreting the pro-
file is that Na was added to the rock, and K was lost. At first
glance, this would seem to be the primary possibility, but
there are several more to consider. Thus, a third possibility
is that Na was added, but K was immobile and did not leave
the rock. Fourth, Na may have been immobile, but K was lost.
Fifth, Na and K may both have been added to the rock, but
more Na was added than K. Finally, Na and K may both have
been lost from the rock, but more K was lost than Na.
To assess these possibilities, we need to define a reference
frame. One might conclude that all one has to do is plot up the
weight percents of Na and K by themselves to determine what
mass changes occurred. Unfortunately, it turns out that
weight percents, in and of themselves, are not suitable for
assessing such mass changes because they are, by definition,
normalized to sum to 100 weight percent. Consider the fol-
lowing hypothetical example from Ague and van Haren
(1996). A quartzite contains quartz, rutile, and zircon, and
has a bulk composition of 99.2 wt% SiO2, 0.72 wt% TiO2,
and 0.08 wt% ZrO2. Suppose that metasomatism caused
by fluid flow in a direction of increasing temperature
551
Vein
16
12 Na/K (moles)
8
4
0
0.50
Y/Zr
0.25
0.3
Yb/La
0.2
0.1
18
16 Sr/Zr
Fe/Zr
14
12
10 0 5 10
X (cm)
(Eq. (21.67)) dissolves a substantial amount of quartz from
the rock, such that 100 kg of precursor loses 20 kg of SiO2
and the mass of SiO2 is now 79.2 kg. Ti and Zr are assumed,
for this example, to have remained inert. Normalization of the
altered rock chemistry to weight percents yields: 99.0 wt%
SiO2, 0.90 wt% TiO2, and 0.10 wt% ZrO2. So even though
20 kg silica per 100 kg rock were lost, the weight percentage
of SiO2 has barely changed! Comparison of SiO2 weight
percents alone, therefore, would not reveal any substantial
mass transfer.
Three different kinds of reference frame can be used to
better assess mass changes. One is a constant volume refer-
ence frame, which assumes that the volume of the altered
rock is the same as the precursor. A second is a constant rock
mass reference frame, which stipulates that even though the
chemical composition of the altered rock may have changed,
the bulk rock mass didn’t. Thus, 100 kg of precursor would
yield 100 kg of altered rock. Mass transfer produces changes
in rock composition and, hence, volume, so both of these
reference frames are rather special cases. Pseudomorphs that
preserve recognizable shapes of the replaced grains are some-
times taken as evidence for constant volume replacement.
However, a potential pitfall here is that the pseudomorphs
could have retained the general shape of the original crystals,
but not the size (and thus volume) of the originals.
The third reference frame can treat all mass transfer sce-
narios, including constant mass or volume. It is based on
identification of an immobile element or suite of elements.
In nature, of course, no element is truly immobile. However,
some have far lower concentrations in solution than others
and can be used as good approximations for the geochemical
reference frame. Elements most commonly used as reference
species in this regard are the high field strength elements
552 Material transport during metamorphism

Zr, Ti, Th, and the rare earth elements (REE). However, even The bulk density of the rock, ρ, is reduced as the volume of
these elements can be mobile under appropriate pressure, void space increases. Thus, bulk density and porosity are
temperature, and fluid composition conditions (Bröcker and related by
Enders, 2001). Particular caution should be exercised when ρ
working with rocks which have undergone partial melting,
¼1 (21:95)
ρg
because most elements can be mobilized to some degree in
silicate melts. where ρg is the density of the mineral grains themselves, and
Once the precursor and reference frame are identified, it is porosity is understood to be, in this case, the volume of void
straightforward to derive the necessary mass balance equa- space (not fluid) per unit volume of rock. Substitution for the
tions. For a reference species i, the basic statement of mass density terms in (21.94) gives
balance is

0  0 !

c ρg 1 
0
V 0 ρ0 c0i ¼ V 0 ρ0 c0i (21:90) "i ¼ i0 1 (21:96)
ci ρ0g 1 
0
where V is rock volume, ρ is bulk rock density, ci is the
concentration of the reference species i, and the superscripts This expression reveals that volume change is the product of
0
and / refer to precursor and altered rock, respectively. three factors. The concentration ratio term accounts for vol-
Equation (21.90) simply states that the mass of i in the altered ume losses or gains resulting from mass losses or gains. The
rock and in the precursor are the same (because i is inert). The second ratio accounts for changes in volume due to changes
total rock mass is given by the product of volume and density. in density. For example, the density of calcite is 2720 kg m−3,
Thus, the change in total rock mass, Tmass, can be written as and that of aragonite is 2950 kg m−3. Therefore, transforma-
tion of calcite to aragonite produces a nearly 8% volume
V 0 ρ0  V 0 ρ0 decrease. The third term describes volume changes due to
Tmass ¼ (21:91)
V 0 ρ0 porosity changes. If the precursor and altered rocks had small
porosities, or if they had similar porosities, then this term is
From Eq. (21.90), we can write approximately unity and can be ignored.
In addition to the total change in rock mass, we can also
c0i
V 0 ρ0 ¼ V 0 ρ0 define the change in mass for any individual mobile species j
c0i
V 0 ρ0 c0j  V 0 ρ0 c0j
Substitution of this expression into (21.91) and rearranging τj ¼ (21:96)
yields (Ague, 1994a) V 0 ρ0 c0j

c0 where τj is the fractional change in mass for species j. To

Tmass;i ¼ i0  1 (21:92) eliminate the volume terms, we make use of the fact that
ci
V0
where Tmass,i is the total rock mass change calculated based ¼ "i þ 1 (21:97)
V0
on reference species i. This value is a fraction; the percentage
mass change can be found by multiplying by 100. The units so as to obtain
of concentration, such as weight percent or parts per million, !

j c0j ρ0
don’t matter as long as they are the same for both numerator τi ¼ ð"i þ 1Þ  1 (21:98)
0
cj ρ0
and denominator. If rock mass has been lost, the concentra-
tion of i in the altered rock will be greater than that in the
precursor, and vice versa. If no rock mass change occurred, Equation (21.98) is very useful because it relates changes in
then the concentration ratio will be unity. Experience has composition, density, and volume. It can be simplified, how-
shown that total rock mass changes in excess of ±35% are ever, by substituting (21.94) for the volume strain to yield
unusual in metamorphic rocks, unless they have undergone
0 0 !
j c cj
partial melting. τ i ¼ i0 1 (21:99)
Volume changes can also be assessed based on Equation ci c0j
(21.90). The volume change (strain, ε) can be defined as
Taken together, Equations (21.92), (21.96), and (21.99) pro-
0 0 vide quantitative expressions for evaluation of rock mass
V V
"¼ (21:93) change, volume strain, and changes in the masses of individ-
V0
ual elements, provided that the precursor and geochemical
Substitution of (21.91) into this expression yields, after some reference frame are identified correctly. Note that all these
rearrangement expressions are cast in terms of concentration ratios. The use

0 
0  of ratios cancels out the 100% normalization inherent in all
c ρ weight percent data. If we return to our quartzite example,
"i ¼ i0 1 (21:94)
ci ρ0 using Zr or Ti as the reference frame we obtain the correct