International Geology Review, Vol. 44, 2002, p. 686–701.

Copyright © 2002 by V. H. Winston & Son, Inc. All rights reserved.

What Is the “Calc-alkaline Rock Series”?

HETU C. SHETH,1 IGNACIO S. TORRES-ALVARADO,2 AND SURENDRA P. VERMA
Centro de Investigación en Energía, Universidad Nacional Autónoma de México, Priv. Xochicalco s/n, Col. Centro, A. P. 34,
Temixco, Morelos 62580, Mexico

Abstract

The “calc-alkaline” series of rocks was originally defined in the early 1930s on the basis of the
“alkali-lime index” on a combined SiO2 versus (Na2O + K2O) and SiO2 versus CaO plot. The usage
of the term has evolved considerably since, and today it is used variably for the subalkalic basalt-
andesite-dacite-rhyolite suite, or any rock suite containing andesite, or island-arc rocks, or rocks
with high ratios of large-ion-lithophile elements (LILE) to high-field-strength elements (HFSE), or
simply rocks with negative HFSE anomalies (e.g., Nb-Ta) in primitive mantle–normalized multiele-
ment diagrams. Although such variable usage is normal in science, the use of certain geochemical
variation diagrams to define and depict the calc-alkaline series is not strictly appropriate. Two of
these widely used diagrams are the total alkalies-silica (TAS) diagram and the (Na2O + K2O)–FeO*–
MgO (AFM) triangular diagram, neither of which has calcium as one of the plotting parameters. The
TAS diagram can be used to depict “alkaline,” “subalkaline,” and probably “transitional” rocks, but
not “calc-alkaline” or “high-alumina” rocks. Care must be taken while using such diagrams for rock
classification, inasmuch as some of them are inherently unsuitable and several together may classify
even a single rock into widely different associations. “Association” or “suite” are probably better
terms than “series,” because they imply neither comagmatic relationships nor linear trends. The
calc-alkaline suite of rocks is abundant along destructive plate margins, but calc-alkaline geochem-
istry is not a 100% foolproof indicator of subduction processes, inasmuch as calc-alkaline rocks are
also known from regions undergoing extension, such as the Basin and Range province and the Gulf
of California. Therefore, caution must be exercised in interpreting ancient terrains with complicated
geology and calc-alkaline rocks as former subduction zones. Not all orogenic andesites are calc-
alkaline, and not all calc-alkaline andesites are orogenic.

... we cannot improve the language of any science without at the same time improving the science itself;
neither can we, on the other hand, improve a science, without improving the language or nomenclature
which belongs to it.
—Abbé de Condillac (cited in Anderson, 1999)

Introduction of the calc-alkalic rock association. Most petrolo-

“CALC-ALKALINE” (syn. “calc-alkalic”) is a very
well known and widely used term in igneous petrol-
ogy today, although its usage is not consistent, the
term being used in widely different senses by vari-
ous workers. As Middlemost (1985, p. 118) noted,
“There is no generally accepted succinct definition
1Present address: Department of Geology and Geophysics,
School of Ocean and Earth Science and Technology (SOEST),
University of Hawaii at Manoa, Honolulu, HI 96822. Address
after November 1, 2002: Homi Bhabha Centre for Science
Education (HBCSE), Tata Institute of Fundamental Research
(TIFR), V. N. Purav Marg, Mankhurd, Bombay, 400 088 India.
2Corresponding author: Fax: +52-55-5622-9791; Phone: +52-
55-5622-9726; e-mail: ita@cie.unam.mx
gists would, however, agree that the volcanic rocks
of this association consist of a comagmatic suite of
subalkalic silica-oversaturated rocks, and that: (a)
they tend to contain more Al2O3 than the normal
rocks of the tholeiitic association; (b) their interme-
diate members do not normally develop any signifi-
cant enrichment in iron; and (c) orogenic andesite is
the most characteristic member of the association.”
However, even this “agreement” is difficult to
implement in actual case studies. An examination of
the petrological literature, including research
papers and textbooks, shows many case studies in
which the use of the term is not justified: the term
has often been incorrectly used for particular rock
suites on the basis of their geochemical parameters

0020-6814/02/610/686-16 $10.00 686

 CALC-ALKALINE ROCK SERIES
FIG. 1. Total alkalies-silica (TAS) plot (Harker, 1909)
showing classification of igneous rocks into the “alkaline” and
“sub-alkaline” or “tholeiitic” series. Boundary lines proposed
by Macdonald and Katsura (1964) and Irvine and Baragar
(1971) are shown.
that have no bearing on the nomenclature. Also,
rocks belonging to this association are identified,
often without sufficient rationalization, with a par-
ticular tectonic setting (subduction). We discuss
below the progressive evolution of the term through
time, the various geochemical parameters that have
been routinely used to identify rocks as calc-alka-
line, and the problems arising from the use of some
of these parameters.
Alkaline, Subalkaline
and Calc-alkaline Rocks
The TAS diagram: Alkaline and subalkaline rocks
The total alkalies-silica (TAS) diagram (Harker,
1909; Le Maitre, 1984), in which the wt% Na2O +
K2O contents of volcanic rocks are plotted against
their wt% SiO2 contents, enables the assignment of
volcanic rock names (e.g., Cox et al., 1979;
Kremenetskiy et al., 1980; Middlemost, 1980; Le
Maitre, 1984; Le Bas et al., 1986; Rickwood, 1989)
and also distinguishes two rock series—the “alka-
line” (“alkalic”) and “subalkaline” (“subalkalic”)
(Fig. 1). Various investigators (Macdonald and Kat-
sura, 1964; Macdonald, 1968; Irvine and Baragar,
1971; Miyashiro, 1978) have proposed somewhat
different coordinates for the dividing line between
the two series (see Rickwood, 1989 for numerical
values). The dividing line by Macdonald and Kat-
sura (1964), for example, is the one that best divides
Hawaiian lavas into “alkaline” and “tholeiitic”
687
FIG. 2. The “basalt tetrahedron” Di-Fo-Ne-Qz (Yoder and
Tilley, 1962), with the “critical plane of silica undersatura-
tion” (Fo-Di-Ab) and “critical plane of silica saturation” (En-
Di-Ab), where Di is diopside, Fo is forsterite, Ne is nepheline,
Qz is quartz, Ab is albite, and En is enstatite. This is helpful
in classifying basalts based on their normative mineral compo-
sitions. Quartz tholeiites have normative quartz, olivine tholei-
ites have normative hypersthene and olivine, and alkali
basalts have normative olivine and nepheline (Tatsumi and
Eggins, 1995).
groups, as identified based on their normative min-
eral assemblage (Kuno et al., 1957). Rocks that fall
roughly on the dividing line itself, i.e., are neither
strongly alkaline nor subalkaline, could be called
“transitional” (Fig. 1).
According to Tatsumi and Eggins (1995), the
strength of the alkaline-subalkaline divisory
scheme is that the alkaline and subalkaline magma
series tend to remain separated during differentia-
tion, since the early crystallization of olivine, cli-
nopyroxene, and plagioclase from basaltic magmas
drives derivative magmas farther away from the
“critical plane of silica undersaturation” (Fo-Di-
Ab) that divides the two magma series in the
“basalt tetrahedron” (Yoder and Tilley, 1962) (Fig.
2). Also, alkaline magmas have normative olivine
and feldspathoids (e.g., nepheline), and subalka-
line magmas have normative orthopyroxene and
plagioclase, and can be further divided into oliv-
ine- and quartz-normative types (Tatsumi and
Eggins, 1995). Middlemost (1975) has proposed
688 SHETH ET AL.
FIG. 3. wt% K2O-SiO2 (A) and Na2O-SiO2 (B) plots (Mid-
dlemost, 1975) showing classification of igneous rocks into
“alkalic” and “sub-alkalic” (including “normal sub-alkalic”
and “low-K subalkalic”) series.
separate diagrams of wt% K2O versus wt% SiO2
and of wt% Na2O vs. wt% SiO2 to classify basalts
into alkaline and subalkaline types, and the subal-
kaline basalts are themselves further divided into
“normal” subalkaline basalts and “low-K subalka-
line” basalts (Fig. 3).
Calc-alkaline rocks: Definitions through time
Peacock (1931) and Kennedy (1933) first
divided the subalkaline series into “tholeiitic” and
“calc-alkaline” magma types (see discussion in Tat-
sumi and Eggins, 1995, pp. 54–55). Kennedy
(1933) proposed the existence of two different pri-
mary magma series: (1) the “olivine-basalt magma
type,” comprising olivine basalts containing phe-
nocrysts of olivine, augite, plagioclase, and magne-
tite, and differentiating to silica-undersaturated
alkaline rocks; and (2) the “tholeiitic magma type,”
containing phenocrysts of pyroxene, plagioclase,
and magnetite, and differentiating to silica-satu-
rated and silica-oversaturated rocks.
FIG. 4. Peacock’s (1931) diagram showing how the “alkali-
lime index” is defined. The continuous line marked “lime”
shows the variation of lime with silica, and the broken line
marked “alkalies” shows the variation of alkalies with silica,
for the given rock suite. The silica value at which these two
lines intersect is the alkali-lime index. If it is between 56 and
61% SiO2, the concerned rock suite is designated “calc-alka-
line.”
Peacock (1931) provided a quantitative defini-
tion of four rock series, including the calc-alkaline
series, by superimposing two Harker plots (SiO2 ver-
sus Na2O + K2O, and SiO2 versus CaO) on the same
graph (i.e., using the same scale). The critical
parameter for the division was the “alkali-lime
index,” which is the SiO2 value at which the best-fit
curves through the two trends for the given rock
suite intersected (Fig. 4). His four rock series were
“alkalic” (with alkali-lime index <51 wt%), “alkali-
calcic” (alkali-lime index between 51 and 56 wt%),
“calc-alkalic” (alkali-lime index between 56 and 61
wt%), and “calcic” (alkali-lime index >61 wt%)
(Fig. 4). This scheme designates series with low
alkali contents as calcic, and those with high alkali
contents as alkalic. The point of intersection of the
two best-fit curves in Peacock’s graph, which
decides the critical SiO2 value (the alkali-lime
index), is related more to changes in alkalies than to
changes in CaO, because the CaO curves of most
rock series are roughly similar, but the alkali con-
tents and alkali curves of various rock series can be
highly variable (Ragland, 1989, p. 322). Tatsumi
and Eggins (1995) felt that this scheme has become
largely redundant. In any case, with the availability
of large data sets today and inherent spread on these
diagrams, the use of Peacock’s definition of the calc-
alkaline series will depend largely on the correct
type of regression method to be used for estimating
 CALC-ALKALINE ROCK SERIES
the “alkali-lime index” (e.g., Baumann and Wätzig,
1997; Drapper and Smith, 1998).
Nockolds and Allen (1953, 1954, 1956) sug-
gested the use of the terms “tholeiitic” and “calc-
alkaline” for magma series with and without iron
enrichment during progressive differentiation
(increasing SiO2 contents), respectively. Miyashiro
(1974) quantitatively defined the two series, propos-
ing that the calc-alkaline and tholeiitic rock series
show steeper and gentler slopes, respectively, than
the straight line
SiO2 (wt%) = 6.4 × FeO*/MgO + 42.8.
He also suggested that if the magmas are differenti-
ated to intermediate degrees (such that 2.0 < FeO*/
MgO < 5.0), the calc-alkaline series would lie above
the line, and the tholeiitic below it. According to
Tatsumi and Eggins (1995), Miyashiro’s discrimi-
nant line is often misused and applied as a single
compositional discriminant outside this composi-
tional range, rather than as a “trend-slope” compar-
ison for which it was primarily intended. Again,
appropriate regression methods and ANOVA-type
statistical tests may have to be used for this purpose.
Calc-alkaline rocks: Current usage of the term
Today, the term “calc-alkaline” is applied vari-
ably to island-arc or subduction-zone rocks ranging
from basalt to rhyolite (e.g., Basaltic Volcanism
Study Project, 1981), or to a magma series interme-
diate between the low-K and high-K series (e.g.,
Wilson, 1996). Some petrologists use the term to
represent the subalkalic basalt-andesite-dacite-rhy-
olite suite and their intrusive equivalents, whereas
others use the term to describe any series of rocks or
magmas that contain andesite or its intrusive equiv-
alent (see Middlemost, 1985, p. 117). Some con-
sider high ratios of the large-ion-lithophile elements
(LILE) to the high-field-strength elements (HFSE)
(e.g., high Ba/Nb, high Rb/Ti) as an important char-
acteristic of calc-alkaline rocks. For example,
Hooper (1994) stated that high LILE/HFSE ratios
are characteristic of the calc-alkaline suite of rocks
directly associated with subduction. The Encyclope-
dia of the Solid Earth Sciences (Kearey, 1993, p. 78)
described calc-alkaline rocks as “characterized by
higher concentrations of CaO in relation to alkalies
in comparison with alkaline igneous rocks” and
therefore as rocks “in which the dominant feldspar
is plagioclase rather than alkali feldspar.” Notably,
none of these characteristics are in any way related
689
to how the suite was originally defined by Peacock
(1931). Middlemost (1985, p. 117) has made the
interesting observation that if one determines the
alkali-lime index of a typical suite of rocks that con-
tain orogenic andesites, one discovers that they usu-
ally belong to the calcic series of Peacock, not calc-
alkalic. On the contrary, Middlemost (p. 118) found
that rocks of the “tholeiitic” basalt-icelandite suite
usually plot within the “calc-alkalic” field on Pea-
cock’s diagram. To some extent, the varible usage of
the term “calc-alkaline” is natural, and the term
may continue to be used meaningfully and without
ambiguity as long as each worker specifies his basis
for using it. However, a matter of more concern
arises in cases where a calc-alkaline series may be
defined with, and depicted on, an inappropriate
multielement-chemical variation diagram, and then
used as unequivocal evidence for tectonic setting.
Both issues are discussed below.
Identification of ‘Calc-alkaline’ Trends
on Geochemical Diagrams
The TAS diagram
Wilkinson (1968, p. 171) included both the
“tholeiitic” and “calc-alkaline” series under the
heading “subalkaline.” This has been followed by
many. For example, Wilson (1996, p. 9) stated that,
in general, the “subalkaline” magma series can be
subdivided into a “high-alumina” or “calc-alkaline”
series, and a “low-K tholeiitic” series, correspond-
ing to the “subalkaline” and “low-K subalkaline”
fields of Middlemost (1975). However, the represen-
tation of the high-alumina or calc-alkaline series on
the total alkalies-silica (TAS) diagram is somewhat
puzzling, as the diagram has neither Al2O3 nor CaO
as one of its plotting parameters.
Kuno (1960, 1966) described basalts from the
Far East (Japan, Manchuria, and Korea), and classi-
fied them into “tholeiitic” (with low Al2O3 and alka-
lies), “alkaline” (with variable Al2O3 and higher
alkalies), and “high-alumina” (with higher Al2O3
and intermediate alkalies) series, on a TAS diagram
(Fig. 5). However, Kuno’s (1960, 1966) high-alu-
mina series has significance, as far as the TAS dia-
gram is concerned, only as the one intermediate
between the other two in terms of alkali contents, in
his study area. The critical point is this: Kuno plot-
ted his high-alumina rocks in the TAS diagram
because they had intermediate alkali contents
between his tholeiitic and alkaline rocks. A suite of
samples from another region, with the same interme-
690 SHETH ET AL.
FIG. 5. Total alkalies-silica plot (Kuno, 1966) showing the
fields for his “tholeiitic” (TH), “high-alumina” (HI-AL), and
“alkalic” (ALK) series, into which he divided basalts from
eastern Asia.
diate alkali contents, and plotted on that diagram,
does not deserve the name high-alumina—and the
TAS diagram cannot anyway depict alumina con-
tents. The appropriate term for these rocks, if they
were represented on the TAS diagram, would be sub-
alkaline—inasmuch as the classifying power of the
TAS diagram is inherently limited to “alkaline,”
“subalkaline,” and probably “transitional” rocks.
Let us assume that we have a suite of samples
from an intraplate ocean island, or an intraplate
continental flood basalt province, and we plot the
relevant data for these on a TAS diagram using
Kuno’s (1966) classification so that some samples
plot in the “tholeiitic” field, others in the “high-alu-
mina” field, and the rest in the “alkalic” field.
Would this be sufficient to enable us to interpret,
without any hesitation, the tholeiitic and high-alu-
mina lavas as marking a volcanic arc and the alkalic
lavas an associated backarc? We are aware, of
course, that no petrologist would do this, but that is
only because the tectonic setting of the rocks in
question is known. What do we do when we are deal-
ing with ancient rocks exposed in deformed terrains
of complex geology and dubious tectonic setting?
How can we be more confident with ancient rocks
than with modern rocks?
In fact, Kuno (1966) also used the terms “high-
alumina” and “calc-alkaline” differently, stating
that the calc-alkaline rock series could be derived
from the tholeiitic, alkalic, or high-alumina series
by fractionation under high oxygen pressure. He
also used an AFM (Na2O + K2O–FeO*–MgO) dia-
gram, Fe/Mg ratio, and phenocryst assemblage to
distinguish the calc-alkaline series from the tholei-
itic series (see Ragland, 1989, p. 323). Primary
high-alumina basalts can be produced at depths
intermediate between tholeiitic and alkaline mag-
mas (e.g., Green et al., 1967; Tatsumi et al., 1983).
Recently the term has been applied loosely to por-
phyritic magmas, in particular to subduction zone
magmas rich in plagioclase phenocrysts (Tatsumi
and Eggins, 1995). Workers like Brophy and Marsh
(1986) and Brophy (1987) considered these magmas
to be the product of melting of subducting oceanic
crust, but Crawford et al. (1987) demonstrated
that they are derived by the differentiation of
more magnesian parent basalts with plagioclase
accumulation.
Thus, “calc-alkaline” and “high-alumina” are
not synonymous, but Middlemost (1985, p. 95), Wil-
son (1996) and Philpotts (1990) have considered the
high-alumina and calc-alkaline series as essentially
the same. These are undoubtedly very complex
rocks petrogenetically. In any case, our main argu-
ment stands—that neither a high-alumina nor a
calc-alkaline series can be defined, or even repre-
sented accurately, on a TAS diagram.
The Alkali Index versus wt% Al2O3 plot
Wilson (1996) found a plot of Alkali Index (A.I.)
vs. wt% Al2O3 (Middlemost, 1975) useful in distin-
guishing tholeiitic basalts from calc-alkaline basalts
(Fig. 6). She reported that very few low-K basalts
plot in the high-alumina field in this diagram, but
opined that this is usually readily explained in terms
of accumulation of plagioclase crystals. The major
chemical difference between the more mafic mem-
bers of the typical tholeiitic and calc-alkaline
series, Wilson stated, is in their Al2O3 content: calc-
alkaline basalts and andesites contain 16–20%
Al2O3, whereas tholeiitic ones contained only 12–
16% (also Philpotts, 1990, p. 100). However, the
calc-alkaline rocks themselves may owe their high
Al2O3 to phenocryst accumulation, because “a char-
acteristic feature of island arc volcanics is their
highly porphyritic nature, magmas of the tholeiitic
series being in general the least porphyritic” (Wil-
son, 1996, p. 9) and plagioclase being the most com-
mon phenocryst phase (Ewart, 1982; Wilson, 1996,
p. 169–170). This could mean that this plot may not
be very useful in distinguishing tholeiitic basalts
from calc-alkaline basalts.
The AFM diagram
Following Irvine and Baragar (1971), several
workers have used the AFM diagram to divide the
 CALC-ALKALINE ROCK SERIES
FIG. 6. Plot of Alkali Index (A.I.) vs. wt% Al2O3 separating
tholeiitic basalts from high-alumina and calc-alkaline basalts
(Middlemost, 1975).
subalkaline rocks into calc-alkaline and tholeiitic
series on the basis of their iron contents, where A =
Na2O + K2O, F = total Fe expressed as FeO, and M =
MgO (all in wt%). F approximately equals FeO +
0.8998 Fe2O3 (Irvine and Baragar, 1971; Johnson et
al., 1985). Authors like Pearce et al. (1975) did not
recalculate Fe2O3 as FeO but designated F = (wt%
FeO + wt% Fe2O3) taken as such. Rickwood (1989)
noted that this practice is unlikely to result in seri-
ous misplotting, with which we do not agree because
of error “amplification” in ternary diagrams (see,
e.g., Butler, 1979). The proponents of the discrimi-
nant lines did intend that the iron adjustment should
be done to compensate for oxidation. Also, all oxides
are calculated to 100% on an H2O- and CO2-free
basis (e.g., Ewart, 1982), although this anhydrous
adjustment would not matter significantly.
In the AFM diagram, tholeiitic suites commonly
show a strong trend of iron enrichment in the early
stages of differentiation, whereas calc-alkaline
suites do not undergo iron enrichment due to the
early crystallization of Fe-Ti oxides and trend
straight across the diagram toward alkali enrich-
ment (Fig. 7). The tholeiitic trend is exhibited by
lavas of Thingmuli volcano in Iceland, and the calc-
alkaline trend by the Cascades lavas (Carmichael,
1964). The former are the so-called icelandites—
andesites poorer in alumina and richer in iron than
691
F IG . 7. The AFM diagram, showing the boundaries
between the “tholeiitic” (TH) and “calc-alkaline” (CA) fields
(heavy lines) as proposed by Kuno (1968) and Irvine and
Baragar (1971). Kuno’s boundary is based on Japanese rocks,
and Irvine and Baragar’s boundary on rocks from many loca-
tions worldwide. Kuno’s boundary yields a smaller area for the
tholeiite suite than Irvine and Baragar’s. Also shown are the
typical tholeiitic trend for lavas of Thingmuli volcano, Iceland
(Carmichael, 1964) and the typical calc-alkaline trend exhib-
ited by the average compositions of Cascades lavas (Car-
michael, 1964). Abbreviations: A = (Na2O + K2O) wt%; M =
MgO wt%. For both Kuno and Irvine and Baragar plots, F is
calculated as (FeO) + (Fe2O3 expressed as FeO) in wt%. The
coordinates for Kuno’s boundary are A,F,M: 72.0, 24.0, 4.0;
50.0, 39.5, 10.5; 34.5, 50.0, 15.5; 21.5, 57.0, 21.5; 16.5, 58.0,
25.5; 12.5, 55.5, 32.0; and 9.5, 50.5, 40.0. The coordinates for
Irvine and Baragar’s boundary are A, F, M: 58.8, 36.2, 5.0;
47.6, 42.4, 10.0; 29.6, 52.6, 17.8; 25.4, 54.6, 20.0; 21.4, 54.6,
24.0; 19.4, 52.8, 27.8; 18.9, 51.1, 30.0; 16.6, 43.4, 40.4; and
15.0, 35.0, 50.0 (from Rickwood, 1989; Rollinson, 1993).
the typical orogenic andesites (see Middlemost,
1985, p. 121). The following problems exist,
however.
1. The AFM diagram involves neither calcium
nor alumina. A calc-alkaline or high-alumina series
of rocks, so defined by other appropriate criteria,
may be plotted on it, but the diagram cannot be used
to define a rock series as calc-alkaline. Of course, it
is the lack of iron enrichment during fractionation
that is characteristic of the calc-alkaline series, and
it is because of this lack of iron enrichment that a
calc-alkaline series is usually shown trending
straight down across the AFM diagram. But what the
diagram is really showing is the lack of iron enrich-
ment, not calc-alkalinity.
692 SHETH ET AL.
2. The AFM plot distinguishes intermediate
members of the series very well, but considerable
overlap exists at the mafic and felsic ends. At the
extreme felsic end there is no satisfactory way of
distinguishing calc-alkalic and tholeiitic members,
and all granitic rocks are simply assigned to the
calc-alkaline series (Philpotts, 1990, p. 100), rea-
sons for which are not clear.
3. Miyashiro (1974) observed that the calc-alka-
line and tholeiite series do not represent two dis-
crete trends of magmatic evolution but are two
artificially defined divisions of continuously vari-
able and diverse trends; he felt that the use of alkali
elements in the distinction could be misleading.
Jensen (1976) found that the AFM diagram was
sometimes misleading in discerning rock chemical
trends.
4. The A-F-M parameters make up less than
50% of the oxide weight percentages and therefore
cannot fully represent the rock chemistry (Rollin-
son, 1993).
5. Only four components (Na + K, Fe, and Mg) of
the whole rock are rounded up to 100%, leading to
distortion of actual trends, and unequal distortion for
rock suites having members ranging from felsic to
mafic. For example, if the volcanic rock series var-
ies in composition from basalt to dacite, about 40%
of the basalt is used when plotting onto an AFM
diagram, whereas only about 15% of the dacite is
used (Rollinson, 1993).
6. The problem of closure or constant sum effect
results in forced correlations (Chayes, 1960; Skala,
1979; Butler, 1986; Ragland, 1989; Rollinson,
1993), such that an unknown amount of the exhib-
ited variability is an artifact of closure.
7. Because of percentage formation, the subcom-
positions do not reflect the variations present in the
overall dataset (Aitchison, 1986; Rollinson, 1993),
inasmuch as percentage formation may drastically
change the statistical properties of the data (the rank
order of the means, variances, and correlation coef-
ficients may change or reverse). This results in at
least part of any trend being artificial (Butler, 1979).
8. A “series,” according to widespread conven-
tion, is not restricted to rocks related by simple frac-
tional crystallization, or melting. Many petrologists
would use the term “series” for magmas having
undergone variable fractionation and mixing and
contamination. In fact, Rollinson (1993, p. 66)
argued that most trends on variation diagrams are
the result of mixing. However, trends can also exist
between completely unrelated rocks, and it is there-
fore preferable to use the terms “association” or
“suite” over “series.”
9. Fractionation under reducing conditions gen-
erally suppresses magnetite crystallization, which
leads to iron enrichment in the early stages. This
generates the tholeiitic trend. Under oxidizing con-
ditions, however, magnetite crystallizes from the
outset, and quickly depletes the residual liquids in
iron, which generates the calc-alkaline trend
(Osborn, 1962; Miyashiro, 1974). These trends are
therefore probably more closely related to differing
activities of oxygen and water during high-level
fractionation than to any fundamental differences in
the chemistry of the parent magmas (Wilson, 1996,
p. 173).
The Calc-alkaline Suite:
Tectonic Connotations
A note is in order concerning the tectonic conno-
tations of the calc-alkaline suite. This suite of rocks
is widespread in island arcs and active continental
margins, with tholeiitic lavas dominating the volca-
nic front, and alkaline lavas dominating the backarc
regions. This has sometimes led to the identification
of ancient terrains with calc-alkaline rocks as
former subduction zones. However, there are several
regions undergoing extension and rifting where
calc-alkaline lavas have been erupted. These
include the Basin and Range province in the west-
ern United States (Gans et al., 1989; Hawkesworth
et al., 1995), the Gulf of California (Martin-Barajas
et al., 1995; Paz Moreno and Demant, 1999), and
the Rio Grande rift (McMillan and Dungan, 1986).
For this reason, caution needs to be exercised in
interpreting ancient terrains with calc-alkaline
rocks as former subduction zones. We discuss below
a specific instructive modern case study from the
Mexican Volcanic Belt (MVB).
The MVB is a 1000 km long, E-W–trending belt
between Puerto Vallarta and Veracruz (Fig. 8). It
comprises more than 8000 individual structures
(Robin, 1982), including towering stratovolcanoes,
calderas, domes, and monogenetic cone fields (Fig.
8). Several of its large stratovolcanoes are presently
active (Colima, Popocatépetl), or have been histori-
cally active (Ceboruco, Citlaltépetl). The Sierra
Chichinautzin (SCN) is a volcanic field of Pleis-
tocene to Recent age (<40,000 years; e.g., Márquez
et al., 1999b), situated south of Mexico City in the
central part of the Mexican Volcanic Belt (Fig. 8)
and close to the volcanic front. It comprises over
 CALC-ALKALINE ROCK SERIES 693

FIG. 8. The Mexican Volcanic Belt (MVB) (shaded region) and other important geological provinces of Mexico.
Abbreviations: SMO = Sierra Madre Occidental; SMOr = Sierra Madre Oriental; SMS = Sierra Madre del Sur. Major MVB
volcanoes (filled triangles) shown are: C = Colima; Ce = Ceboruco; P = Paricutín; NV = Nevado de Toluca; Po = Popoc-
atépetl; Iz = Iztaccíhuatl; Ci = Citlaltépetl (Pico de Orizaba). Black box just south of Mexico City is the Sierra Chich-
inautzin monogenetic volcanic field. Modified after Verma (1999).

220 Quaternary monogenetic volcanic centers
(Márquez et al., 1999b and references therein).
The MVB has traditionally been considered as a
“complex” arc resulting from the subduction of the
Cocos plate under the North American plate (e.g.,
Molnar and Sykes, 1969; Thorpe, 1977; Menard,
1978; Negendank et al., 1985). The reason it has
been described as “complex” is that numerous geo-
logical, geophysical, and geochemical anomalies in
the subduction scenario exist. For example, the
MVB is not parallel to the Middle America trench
but makes an angle of ~20° to it (Molnar and Sykes,
1969). The Wadati-Benioff zone beneath the belt is
seismically very poorly defined, and is completely
absent beneath the central MVB (Singh and Pardo,
1993; Pardo and Suárez, 1995). The seismicity
throughout the MVB is shallower than 60 km, with
most earthquake foci less than 20 km deep and
extensional (Suter et al., 1992; Singh and Pardo,
1993). A pronounced gravity low is observed all
over the MVB, and especially over its central part,
which suggests a low-density, low-seismic-velocity
anomalous mantle layer at the base of the crust (~40
km depth) (Molina-Garza and Urrutia-Fucugauchi,
1993; Campos-Enríquez and Sánchez-Zamora,
2000). The Sierra Chichinautzin monogenetic volca-
nic field is located precisely in this area. Such geo-
physical characteristics of the MVB as a whole are
in marked contrast to what are observed along
Benioff zones like the Japan, Aleutian, Philippine,
or Central American (Gill, 1981). There is also no
geochemical evidence for any role of the subducting
Cocos plate in the petrogenesis of either the mafic
magmas or the evolved magmas at the volcanic front
in the central part of the MVB (Verma, 1999, 2000a;
Velasco-Tapia and Verma, 2001), or in the Los
Humeros caldera in the eastern part of the MVB
(Verma, 1983, 2000b). It is due to these observa-
tions contrary to the subduction explanation that
several workers have interpreted the MVB not as an
arc but as a rift-like structure undergoing extension
(see Sheth et al., 2000; Márquez et al., 2001, and
references therein).
Verma (2000a) analyzed major and trace ele-
ments (including the rare-earth elements) and radio-
genic isotopes in basalt and sediment samples from
the Cocos plate and the accretionary wedge.
Besides, Verma (1999) and Velasco-Tapia and
Verma (2001) have provided a complete geochemi-
cal and Nd-Sr isotopic data set for mafic rocks from
694 SHETH ET AL.
FIG. 9. A. TAS diagram showing the positions of lavas from
the Sierra Chichinautzin volcanic field (Mexican Volcanic
Belt). Thick continuous line is the boundary between the alka-
line and tholeiitic fields of Macdonald and Katsura (1964).
The two thick broken lines are Kuno’s (1966) boundaries sep-
arating alkaline (ALK), high-alumina (HI-AL), and tholeiitic
(TH) fields. Boundary lines and fields for the common volca-
nic rocks, proposed by the IUGS (e.g. Le Bas et al., 1986), are
also shown in the background. B. Plot of Alkali Index versus
wt% Al2O3. Alkali Index is defined as [wt% (Na2O + K2O)]
divided by [(wt% SiO2 – 43) × 0.17]. Data sources for both
plots are Verma (1999, 2000a), 21 samples. All analyses have
been recalculated to 100% on a volatile-free basis, following,
for example, Ewart (1982) and iron oxidation ratios calculated
following Middlemost (1989), using SINCLAS (Verma et al.,
2002).
the SCN. The most important geochemical charac-
teristics of the SCN rocks according to Verma (1999)
are: (1) the evolved (andesitic and dacitic) rocks
generally have lower REE concentrations than the
mafic rocks; (2) the evolved and mafic rocks have
similar Pb isotopic compositions, but the evolved
rocks have slightly higher 87Sr/86Sr and somewhat
lower 143Nd/144Nd than the mafic rocks; and (3) the
evolved rocks have lower Nb concentrations and
higher Ba/Nb ratios than the mafic ones. Verma
(1999) modeled the petrogenesis of the evolved
rocks and found that they could not be explained by
partial melting of the subducted slab, simple differ-
entiation of mafic magmas (which would lead to, for
example, isotopic ratios being the same for both
groups of rocks, and the REE contents being higher
in the evolved rocks than the mafic rocks, the oppo-
site of what is observed), or melting of the mantle in
the presence of fluids released by the subducted
slab. Verma (1999) found that the partial melting of
lower continental crust and magma mixing were the
only plausible mechanisms. His main conclusions
are as follows: (1) the SCN mafic magmas were pro-
duced by partial melting of a heterogeneous upper
mantle; (2) the SCN evolved magmas were generated
by melting of a more heterogeneous lower continen-
tal crust; and (3) mixing of mantle-derived basaltic
magmas and lower crust-derived andesitic and dac-
itic magmas, prior to eruption, can explain SCN
lavas of intermediate compositions. Based on a par-
tial melting inversion model, Velasco-Tapia and
Verma (2001) concluded that SCN mafic magmatism
was derived from partial melting of an enriched
lithospheric mantle in an extensional tectonic set-
ting. They found a mantle source comparable to that
inferred from mantle xenoliths of central Mexico,
with a range of 7 to 16% partial melting.
If the SCN evolved and mafic magmas are plot-
ted together on a TAS diagram using Kuno’s (1966)
classification (“tholeiitic,” “high-alumina,” and
“alkalic”) (Fig. 9), some of them would be desig-
nated high-alumina. On an Alkali Index versus wt%
Al2O3 diagram, however, only two of the samples
plot in the high-alumina/calc-alkaline basalt field,
with all the rest lying in the tholeiitic basalt field. In
the AFM diagram (Fig. 10), however, the data for
these rocks define a typical calc-alkaline trend (cf.
the Cascades trend in Fig. 7). But does this calc-
alkaline trend indicate a subduction origin of the
SCN and thereby the MVB? Any unrelated mafic
and evolved samples plotted together may form a
linear trend simply by virtue of their compositions.
The dominant calc-alkaline chemistry of the MVB
magmas (e.g., Verma and Aguilar-Y-Vargas, 1988)
usually has been cited as strong evidence for their
origin from subduction (e.g., Negendank et al.,
1985; Nixon et al., 1987; Suter et al., 1995). For
 CALC-ALKALINE ROCK SERIES
example, Delgado et al. (1998) studied basalts from
Xitle volcano in the Sierra Chichinautzin volcanic
field, found that these rocks plotted in the calc-alka-
line field on the AFM diagram, and thereby con-
cluded that “Xitle volcano lavas show calc-alkaline
affinity characteristic of subduction-related envi-
ronments,” and that “the data… do not support
Verma’s (2000a) suggestion for a rifting process to
explain the origin of Xitle volcano basalts due to
their calc-alkaline affinity” (Delgado et al., 1998, p.
128). However, we find various anomalies in the
subduction scenario sufficiently compelling, and
would instead continue to argue that calc-alkalinity
is not evidence for subduction. As noted, there are
several regions undergoing crustal extension where
calc-alkaline lavas have erupted. In fact, calc-alka-
linity may not be a suitable indicator of tectonic set-
ting at all, but may instead reflect the mantle
sources and petrogenetic processes. Recently, Sheth
et al. (2000) have interpreted the calc-alkaline
chemistry of the MVB magmas as simply reflecting
the process of crustal contamination experienced by
mantle-derived magmas, and their fractionation
mechanisms, rather than subduction (see also Mor-
ris et al., 2000). Melting of the continental crust,
crustal contamination of mafic magmas, and mixing
between mafic and evolved magmas are common
processes throughout the MVB (e.g., Nixon, 1988;
Luhr, 1997; Verma, 1999, 2000b, 2001; Verma and
Nelson, 1989; Verma et al., 1991; Márquez et al.,
1999b). A volcanic suite cannot be characterized as
subduction-related merely because it has calc-alka-
line characteristics or because it includes andesites
or dacites (Márquez et al., 1999a; Morris et al., 2000).
Ferrari and Rosas-Elguera (1999) and Ferrari et
al. (2000) have defined MVB lavas with negative Nb
anomalies in mantle-normalized incompatible-ele-
ment diagrams as calc-alkaline, and in turn as sub-
duction related. We opine that the negative Nb
anomalies, like calc-alkaline geochemistry, reflect
contamination of mantle-derived magmas by gra-
nitic or granulitic continental crust depleted in Nb
and similar high-field-strength elements (e.g., Ta,
Ti), as shown by Verma (1999, 2000a, 2000b, 2001)
for several areas of the MVB. Negative Nb anoma-
lies are widespread in lavas contaminated by conti-
nental crust, and are shown not only by arc lavas but
also by continental flood basalt lavas, such as those
of the Deccan Traps, India (e.g., Mahoney et al.,
2000) and the Central Atlantic Magmatic Province
comprising parts of South America, North America,
Africa, and Europe (Marzoli et al., 1999).
695
FIG. 10. The AFM diagram with Irvine and Baragar’s
(1971) boundary between the tholeiitic (TH) and calc-alkaline
(CA) fields, with data for lavas of the Sierra Chichinautzin vol-
canic field (Mexican Volcanic Belt). Data sources are the same
as for Figure 9. All analyses recalculated to 100% on an H2O-
and CO2-free basis. Abbreviations: A = (Na2O + K2O); F =
FeO* = total Fe as FeO; and M = MgO, all in wt%. Total Fe as
FeO = FeO + 0.8998 Fe2O3 (following Irvine and Baragar,
1971; Johnson et al., 1985; see Ragland, 1989; Rickwood,
1989).
Calc-alkaline and High-Alumina Rocks
on the TAS Diagram
We return to problems related to the depiction of
calc-alkaline rocks on geochemical variation dia-
grams. Ragland (1989) discussed the current con-
fused state of nomenclature of igneous rock series.
Discussing various classification schemes, which
tend to classify the same rock as belonging to wholly
different series, he asked (p. 326), “Must a rock ful-
fill all these various criteria to be classified as being
in a particular series? If this were true, a consider-
able number of rocks could never be placed in any
series.” As an example, Morrison (1980) found that
shoshonitic rocks usually plot in the “alkaline” field
on the TAS diagram but in the “calc-alkaline” field
on the AFM diagram.
Macdonald and Katsura (1964), who used the
TAS diagram to classify basaltic rocks in Hawaii,
proposed only two suites, “tholeiitic” and “alkalic.”
As Ragland (1989, p. 323) noted, the boundary
between Kuno’s “high-alumina” and “alkaline”
basalts is quite close to the boundary between Mac-
donald and Katsura’s “tholeiitic” and “alkaline”
basalts, which results in mafic rocks of a certain
696 SHETH ET AL.
composition being classified as tholeiitic by Mac-
donald and Katsura’s diagram, but as high-alumina
by Kuno’s diagram. Ragland asked which of these
two is correct, answering that Kuno’s scheme is pref-
erable if one is working on subduction-related
basaltic rocks at a convergent margin, but Mac-
donald and Katsura’s scheme is preferable if one is
working on intraplate or ocean-ridge basalts.
We ask, therefore, which scheme should be used
when one is studying ancient rocks whose tectonic
setting is unknown? Or modern rocks in a complex
tectonic setting? The use of one diagram or the other
in that case would lead to widely varying terminol-
ogy, and if the objective were to infer the tectonic
setting based on the geochemical characteristics,
two tectonic settings not even remotely resembling
each other would be inferred for the same rock: the
tholeiitic classification might lead to the inference
of an ocean-ridge or marginal-basin setting, and the
high-alumina classification for the same rock would
lead to the inference of an island-arc setting. Which
of these two would be correct? For that matter, the
Bushveld Layered Complex of South Africa and
some other igneous masses contain some rocks that
show a trend towards iron enrichment, and others
that do not (Middlemost, 1985, p. 118)—what would
be the tectonic setting of the Bushveld Complex
based on this? As noted earlier, subalkalic basaltic
magmas might be identified on the basis of either of
these trends to be a result of, for example, local dif-
ferences in oxygen fugacity of the parent magma
(Middlemost, 1985, p. 118) and different fraction-
ation assemblages (Rogers and Hawkesworth,
1999).
The above confusion is completely unwarranted,
and the solution is as follows. The Macdonald and
Katsura classification is the correct one in this case,
and the depiction of the “high-alumina” series on
the TAS diagram, following Kuno (1966), is incor-
rect in the first place, so his classification should not
be used, and there is no paradox regarding whether
these mafic rocks are tholeiitic or high-alumina.
With the correct classification, they are tholeiitic
and only tholeiitic. We emphasize once again, that
Kuno plotted his high-alumina series between the
alkalic and tholeiitic series because the high-alu-
mina series had intermediate alkali contents
between the other two. Although the real name for
this intermediate group of rocks would probably be
“transitional,” Kuno was led to call it “high-alu-
mina” because of their relatively high alumina con-
tents. The cause of the entire problem is obvious—
namely, the high-alumina series was depicted on,
and defined with, the TAS diagram, a diagram on
which it cannot strictly be defined or represented.
An example
Ragland (1989, p. 329) provided an example of
the current confusion. The basaltic rock with the fol-
lowing composition (his Table 1.1)—wt% SiO 2
48.70, TiO2 1.29, Al2O3 16.60, Fe2O3 2.05, FeO
8.29, MnO 0.16, MgO 6.63, CaO 10.70, Na2O 2.83,
K2O 0.47, H2O+ 0.81, H2O– 0.67, P2O5 0.20, CO2
0.09, and Total 99.49—is classified into different
rock series on the basis of different classifications,
as follows: high-alumina (TAS plot, Kuno, 1966),
tholeiitic (TAS plot, Irvine and Baragar, 1971),
tholeiitic (TAS plot, Macdonald and Katsura, 1964),
tholeiitic (K2O-SiO2 plot, Gill, 1970), calc-alkaline
(AFM plot, Kuno, 1968), tholeiitic (FeO*/MgO ver-
sus SiO2 plot, Miyashiro, 1978), subalkaline (a
molecular norm plot, Irvine and Baragar, 1971),
tholeiitic (Al2O3 versus plagioclase composition
plot, Irvine and Baragar, 1971), and tholeiitic (AFM
plot, Irvine and Baragar, 1971). Thus various
schemes classify this single rock sample variably,
and according to Ragland (1989), the rock would
have to be elected tholeiitic by a 6-2 vote. But this is
no solution; more diagrams with other classification
criteria, which would classify this rock as calc-alka-
line, could easily be constructed by “aficionados”
of that term. Thus, the rock could easily be made
tholeiitic or calc-alkaline by devotees of one classi-
fication scheme or the other.
We think that the aforementioned rock is indeed
tholeiitic, or rather subalkaline, for another, stron-
ger, simpler reason. The depiction of high-alumina
basalts being inappropriate on the TAS plot, the
classification of this rock as high-alumina based on
Kuno’s (1966) TAS plot is incorrect. Likewise, the
depiction of calc-alkaline basalts being inappropri-
ate on the AFM diagram, the classification of the
above-listed rock as calc-alkaline based on Kuno’s
AFM plot is also incorrect. The rest of the diagrams
are unanimous (“tholeiitic” is also “subalkaline”).
Therefore, we conclude that it is the use of inap-
propriate geochemical discrimination diagrams that
is the cause of particular rock suites, or even single
rocks, being classified into widely different associa-
tions. To avoid all the unwarranted confusion, we
suggest the use of simple rock names (basalt, andes-
ite, etc.) defined by the IUGS Subcommission on the
Systematics of Igneous Rocks (Le Maitre, 1984; Le
Bas et al., 1986; Le Bas, 1989; Le Bas, 2000) based
 CALC-ALKALINE ROCK SERIES
on the TAS diagram. An inherent feature of this
classification, attractive in the present context, is
that it is non-genetic. The classification is purely
descriptive, independent of field location or field
association, except that the rock in question is vol-
canic. To these rock names can be attached the
qualifier terms “alkalic” and “subalkalic” (e.g.,
alkalic basalt), but not “calc-alkaline” or “high-alu-
mina.” Verma et al. (2002) have developed a com-
puter program SINCLAS that classifies volcanic
rocks on the basis of their total alkalies-silica con-
tents and iron oxidation ratios, provides rock and
root names (following Le Bas et al., 1986; Le Bas,
1989, 2000), and also calculates CIPW norms.
Conclusions
Since originally defined in 1931, the term “calc-
alkaline” has come to mean various things to various
people. It is variably used for (1) island arc rocks,
(2) andesites, (3) rocks with high LILE/HFSE ratios,
(4) rocks with negative Nb anomalies, etc. This vari-
able usage may not be problematic as long as each
petrologist employing the term specifies his or her
basis for using it. However, calc-alkaline rocks must
be identified with, or depicted on, appropriate
geochemical variation diagrams, and neither the
TAS diagram nor the AFM diagram seem suitable
for this, although both have been used extensively
(the AFM particularly so). The TAS diagram can
classify rock suites into “alkaline,” “subalkaline,”
and “transitional,” but not “calc-alkaline” nor
“high-alumina.” The confused situation in which
even a single rock can be classified into completely
different series using different diagrams (Ragland,
1989, pp. 320–329), is largely due to some of these
diagrams being irrelevant and unsuitable for defin-
ing certain rock suites. “Association” and “suite”
are terms preferable to “series,” because they need
not imply comagmatic relationships, and need not
require linear trends on geochemical variation dia-
grams. A calc-alkaline suite of rocks, even when
identified with the right criteria, should have no tec-
tonic connotations. Not all orogenic andesites are
calc-alkaline, and not all calc-alkaline andesites are
orogenic.
Does the term “calc-alkaline” deserve expunge-
ment from the petrological literature? Perhaps it
does. Chayes (1964) gave pertinent reasons why the
term “tholeiite” should be expunged from the liter-
ature, and substituted by “subalkaline.” It is rele-
697
vant to recall that the IUGS Subcommission on
Systematics of Igneous Rocks (Le Bas et al., 1986;
Le Bas, 2000) has eliminated both the terms “calc-
alkaline” and “tholeiite,” and apparently replaced
them by “subalkaline.” Use of a computer program
such as SINCLAS (Verma et al., 2002) could facili-
tate automatic rock nomenclature, and thus reduce
the present confusion prevailing in geological
literature.
Acknowledgments
This work was partly supported by DGAPA-
UNAM project IN-106199. The manuscript was
written while H.C. Sheth was supported by a post-
doctoral fellowship from CIE-UNAM, and much
revised and improved while he was supported by a
SOEST Young Investigator award of the University
of Hawaii.
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