172 Interpretation of Metamorphic Phase Diagrams
a phase diagram or an isograd on a geologic map. Most V W
of the time, however, rocks contain assemblages of higher
variance. It is important to find ways to treat multivari-
ant assemblages so it is possible to visualize the pressure,
temperature, or fluid compositions that control them.
Divariant assemblages are easy to understand in a sys-
tem with one component, such as the system Al2SiO5, for
these assemblages consist of only one phase (Figure 2.1).
In systems with more components, however, it becomes
progressively more difficult to recognize divariant assem-
blages merely through inspection. In complex systems,
chemographic projections make it possible to recognize
divariant assemblages and to find their stability fields in
a phase diagram. In chemographic projections, mineral
compositions are expressed graphically and the graphical
relationship between minerals determines whether they
are in a reaction relationship.
12.3.1 Chemographic Projections in a Two-
Component System
Consider a hypothetical two-component system consist-
ing of the components a – b and the phases V = a, W =
a2b, Y = ab2, and Z = b (Figure 12.1; note the convention
that components are written in lower case letters, whereas
phases are written in capitals). With a little bit of work
with pencil and paper, you can show that this system con-
tains the following univariant reactions:
2V + Z = W (12.1)
V + 2Z = Y (12.2)
3V + Y = 2W (12.3)
3Z + W = 2Y (12.4)
These reactions could potentially intersect at an invari-
ant point, as in Figure 12.2. The diagram in Figure 12.2 is
called a topology. It shows the arrangement of reactions
around an invariant point but does not locate the reac-
tions in P-T space.
Even with a quick glance at Figure 12.2 one can deter-
mine where three-phase assemblages such as W-V-Z are
stable, since each three-phase assemblage is marked by
one of the reactions listed previously. The problem comes
when one has a divariant assemblage or suite of divari-
ant assemblages. For example, where would the assem-
blages WY and YV be stable? This question is answered
by locating chemographic diagrams for this system (i.e.,
Figure 12.1) in each of the divariant fields. Realize that
Y Z
a b
Figure 12.1 Chemography for the two-component system a-b
with phases V, W, Y, Z. The topology for this system is shown
in Figures 12.2 and 12.3.
(12.2)
P
V
+
T
2Z
Y
2V + Z
(12.1)
W
Y
+ 3Z
3V 2W 2Y +
W
(12.3)
(12.4)
Figure 12.2 Topology for the hypothetical two-component
system a-b shown in Figure 12.1.
each reaction is an expression of a change in chemogra-
phy: two phases react to form one phase (or one phase
breaks down to form two others; chemographically they
are equivalent). The chemographic expression of a reac-
tion is the appearance (or disappearance) of the prod-
uct phase on the segment of line that lies between the
two reactant phases. For example, consider the reaction
(12.1) in Figure 12.2. On the high-pressure side of this
reaction, phases V + Z are stable; this means there is a
line running from V to Z with no intervening phases. On
the low-pressure side of this reaction, W has appeared.
Chemographically this means that on this side of the
reaction point, W lies between V and Z. Consequently
the stable two-phase assemblages in this field are VW
and WZ. This is shown in Figure 12.3. Using this rule
it is possible to fill in all the rest of the divariant fields
in Figure 12.3 with chemographic projections that indi-
cate what two-phase assemblage is stable in each field.
With this information added to Figure 12.3, it becomes
straightforward to answer the question raised earlier
about where WY and YV are stable.
 12.3 Use of Chemographic Projections 173

(12.2) z
P
V T
+
2 C
Y Z V Z
B

V Y Z 2V + Z E
(12.1)
W A D
x y
3V + Y V W Z A = x, B = Xz, C=yz2, D = y, E = x2yz
3Z
Figure 12.4 Chemographic diagram for a hypothetical three-
2W 2Y +
W component system x-y-z.
(12.3) V W Y Z
(12.7)
(12.4)

A+
(12.8)

B
Figure 12.3 Topology for the hypothetical two-component E

+D
system a-b shown in Figure 12.1., with divariant assemblages B
D+ C
identified using chemographic projections. A+
B+D
(12.6)
E+C
12.3.2 Chemographic Projections in a Three-
Component System A P
B+E
Now consider a hypothetical three-phase system x, y, z A+C +
T
containing the phases: A = x, B = xz, C = yz2, D = y, and E E C
(12.5) +
= x2yz. Again, after a little work with a pencil and paper it D
is possible to balance the following reactions: (12.9)

3A C= B E (12.5) Figure 12.5 Topology for the hypothetical three-component

4B 3D= 2E C (12.6) system x-y-z.
E= A+ B D (12.7)
2A C 2B D (12.8) (12.7)
22E= 4A+ C D (12.9)
A+

(12.8)
B+

C E
The divariant assemblages for a three-component system B
D

B
are expressed chemographically using an equilateral trian- A
E
D D+
C
gle that has one component at each apex. The chemogra- A+
B+D
phy for the three-component system in question is shown (12.6)
E+C
in Figure 12.4. (For rules governing the construction of
this figure, see Section 2.3) E A
B+ C +
Figure 12.5 presents a topology showing how these +
A C
reactions could be related. The four-phase assemblages E
+ P
make up the five univariant reactions in this system. (12.5) D
T
Chemographic projections are used to determine where (12.9)
three-phase or two-phase assemblages are stable in this
system. The chemographic representation of a divariant Figure 12.6 Topology for the hypothetical three-component
assemblage in a three-component system is a triangle system x-y-z, with divariant assemblages identified using
that has as its apices the three stable phases. Figure 12.6 chemographic projections.
174 Interpretation of Metamorphic Phase Diagrams

provides an illustration of how a topology of a three-phase (12.7)

system is interpreted using chemographic projections.

A+
Consider the field outlined by reactions (12.5) and (12.8)

B
E

(12.6) in Figure 12.6. From reaction (12.6) (4B+3D = 2E
+ C) one can see that the tie line E-C is stable, and from
reaction (12.5) (3A + C = B+E) it is evident that the tie
line B-E is stable. Having established two tie lines, how
does one fill in the rest of the triangle? Note that if reac-
tion (12.6) operated on a bulk assemblage with abun-
dant D and small amounts of B, B would be consumed
by this reaction, leaving some D remaining along with
the products of E + C. This implies that in the divariant
field between reactions (12.5) and (12.6) there must be a
tie line from E to D. Similar reasoning concerning reac-
tion (12.5) implies that there must be a tie line from E to
A. Thus the divariant field between reactions (12.5) and
(12.6) contains the following assemblages: B-C-E, C-E-D,
A-B-E, and A-E-D.
Once one has determined the divariant assemblages
present in one field, the relations in other fields are deter-
mined by performing the operation implied by each uni-
variant reaction. For example, in crossing reaction (12.6),
the tie line from E to C is broken and a tie line from B to
D forms instead. This leads to the chemography shown
in the divariant field between reactions (12.6) and (12.7).
Note that all the other tie lines shown in the field between
reactions (12.5) and (12.6) are unchanged. What hap-
pens when one goes from the field bounded by reactions
(12.6) and (12.7) to that bounded by (12.7) and (12.8)?
Reaction (12.7) says that E reacts out to form A + B +
D. Chemographically, that means E disappears within the
triangle A-B-D. Since E has disappeared, the tie lines from
E to A, B, and D disappear also (Figure 12.6).
A careful study of Figure 12.6 reveals two types of reac-
tions. One type has two or more phases on each side of a
reaction. The chemographic representation of this reac-
tion is a quadrilateral in which two tie lines have an inte-
rior intersection (e.g., reaction (12.6) in Figure 12.6). This
type of reaction is known as a tie line flip reaction. When a
reaction such as this occurs, all the phases remain intrinsi-
cally stable; it is merely the stable assemblages that change.
The second type of reaction occurs when only one phase
occurs on either side of the reaction. The chemographic
representation of this type of reaction is a triangle with
an interior phase (e.g., reaction {(12.7)} in Figure 12.6).
A reaction such as this is called a terminal reaction. In
+D
C
B
B
E D+
A D
A+
C
B+D
(12.6)
E+C
p
q
A
B +E +
C
A+ E
C
+ P
(12.5) D
T
(12.9)
Figure 12.7 Same topology as Figure 12.6 showing the
assemblages found in two hypothetical bulk compositions, p
and q.
crossing a terminal reaction, a phase destabilizes in all
bulk compositions.
Rarely are minerals consumed by terminal reactions.
Most of the time, metamorphic reactions involve tie
line flip reactions. As an example, consider the stability
of chlorite. Chlorite is a common mineral in low-grade
metamorphism of most protoliths; it disappears with
increasing metamorphic grade. However, chlorite is not
restricted to low metamorphic temperatures. Chlorite
disappears because, with increasing temperatures, tie line
flip reactions restrict its occurrence to increasingly lim-
ited bulk compositions. The terminal reaction for chlorite
(chlorite = olivine + orthopyroxene + spinel) occurs at
temperatures around 700°C, which means that in ultra-
mafic rocks chlorite may be stable up to very high grade
metamorphism.
In addition to indicating the stable phases in a given
divariant field, chemographic projections also show the
assemblage present in a rock of a given bulk composition.
To understand this concept, consider Figure 12.7, which
shows the same topology as that given in Figure 12.6 along
with the chemographic diagrams for the compositions of
two hypothetical rocks, p and q. Rock p has a composition
very close to mineral B, whereas rock q has a composi-
tion that lies close to the A-D tie line. In the divariant field
bounded by reactions (12.7) and (12.8), both bulk com-
positions will have the same assemblage: A-B-D. Rock p
will have a lot of B and only a small amount of A and D,

whereas rock q will have mostly D and A and only minor
amounts of B. As reaction (12.8) (D + B = A + C) pro-
ceeds, each assemblage behaves differently. Mineral D will
be depleted from rock p, which is dominated by mineral
B, whereas mineral B will be depleted first from rock q.
These relations are shown in the chemographic projection
in the field bounded by reactions (12.8) and (12.9), where
composition p lies in the triangle A-C-B, whereas compo-
sition q lies in the field A-C-D. The reader is encouraged
to determine the assemblages for these bulk compositions
in the other fields in Figure 12.7 as an exercise.
12.3.3 Chemographic Projections in Systems
with Four and More Components
In a system with four components, the phases can be
expressed using a three-dimensional tetrahedron, but in
systems of five or more components it is not possible to
display relations chemographically because it requires
more than three dimensions. There are two ways to han-
dle this problem. One way is to explore the system in
n-dimensional vector space using matrix algebra. In other
words, the problem is addressed mathematically rather
than graphically. This approach, while useful, will not be
addressed in this text. The other way is to use projections.
The extra dimensions of a complex system can be elimi-
nated by assuming that one or more phases are always
present in an assemblage. By projecting from the common
phases it is possible to reduce a multidimensional chemog-
raphy to a triangular chemographic projection. Such dia-
grams are called pseudoternary projections and are used
precisely like the chemographic diagrams described for a
three-component system. The difference is that these pro-
jections only depict reactions that contain the projecting
phases. Crossing a reaction that does not contain all the
projecting phases does not change the relations shown
on the projection. Pseudoternary projections have been
used previously in this text to discuss basalt melting and
the chemistry of MORB, where relations were projected
from plagioclase onto the olivine-clinopyroxene-quartz
triangle (Figures 5.5 and 6.5).
Figure 12.8 illustrates a projection from a triangu-
lar chemography to a binary one. Figure 12.8A shows
chemographic relations in the system MgO-SiO2-H2O.
If one assumes that H2O is always present during meta-
morphism of a serpentinite, we can show the same infor-
mation on a linear chemography projected from H2O
12.3 Use of Chemographic Projections 175
HO0.5
water
A
brucite
serpentine
talc
anthophyllite
MgO SiO2
forsterite enstatite quartz
B
b f s ea t q
MgO SiO2
Figure 12.8 A. Chemography for the system MgO-SiO2-H2O
showing projection from H2O to the MgO-SiO2 plane. Dark
points plot mineral compositions, gray points are projection
points. B. Pseudobinary projection from H2O for the same
system.
(Figure 12.8B). The coordinates used in the ternary pro-
jection are obtained by taking the ratio of each of the
three cations (Mg, Si, H) to the total number of cations
(Mg + Si + H). Similarly the coordinates used in the pro-
jection from H2O are obtained by taking the ratio of each
of two cations (Mg and Si) to the sum of these two ions
(Table 12.1). As long as H2O is involved in a reaction, the
binary and ternary chemographies show the same infor-
mation (Figure 12.8A), although all reactions will appear
as terminal reactions on the binary system. Indeed, they
are terminal if H2O is always in excess.
Ternary projections have strict rules in application to
topologies and phase diagrams. If the plot of an assem-
blage on a chemographic diagram produces crossing tie
lines or has a phase lying within a triangle outlined by
three other phases, then it is clear there is a reaction rela-
tionship among the phases. There is, however, another type
of projection that doesn’t have such a strict application,
but which is nevertheless very handy in understanding
mineral relations in chemically complex rocks. This is the
ACF projection of Eskola (1920). This is a projection from
quartz, plagioclase, and orthoclase onto a plane defined
by A = (Al2O3 + Fe2O3 – Na2O – K2O), C = CaO, and