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2008 Frost and Frost
2008 Frost and Frost
1093/petrology/egn054
In this paper we classify the range of feldspathic igneous rocks three compositional variables, FeO/(FeO þMgO) (or
using five geochemical variables: the FeO/(FeO þMgO) ratio or Fe-index), Na2O þ K2O ^ CaO (or the modified alkali^
Fe-index, the modified alkali^lime index, the aluminum-saturation lime index, MALI), and the aluminum-saturation index
index, the alkalinity index, and the feldspathoid silica-saturation [ASI; molecular Al/(Ca ^ 167P þ Na þ K)]. The scheme
index.The Fe-index distinguishes between melts that have undergone has achieved wide use but several issues remain unad-
extensive iron enrichment during differentiation from those that have dressed. One is whether the ferroan^magnesian boundary
not. The transition from tholeiite to ferrobasalt allows us to extend can be extended to intermediate and basic rocks. Another
this boundary to silica values as low as 48 wt %. We introduce the is the petrological significance of the alkalic, alkali^calcic,
feldspathoid silica-saturation index, which, coupled with the alkali- calc-alkalic and calcic boundaries in the MALI diagrams.
nity index, allows us to extend the geochemical classification to In addition to addressing these questions, we extend
alkaline rocks. We show that most alkaline rocks are ferroan and our classification scheme by introducing two additional
that this probably reflects extensive fractional crystallization of indices: the alkalinity index (AI) and feldspathoid silica-
olivine and pyroxene with minimal participation of Fe^Ti oxides. saturation index (FSSI). These indices allow for the discri-
The expanded classification allows us to illustrate the geochemical mination of metaluminous from peralkaline rocks and
and petrogenetic relationship of the plutonic rocks from ferroan gran- silica-saturated from silica-undersaturated rocks, and
ites to nepheline syenites that commonly occur in intracratonic envir- thereby allow the geochemical classification scheme of
onments. It also allows us to distinguish four families of feldspathic Frost et al. (2001) to be extended to alkaline rocks. The
rocks: (1) magnesian rocks, which are exemplified by Caledonian enlarged classification scheme can be applied to the whole
and Cordilleran batholiths and are characterized by differentiation range of feldspathic rocks; that is, rocks in which feldspars
under oxidizing and relatively hydrous conditions; (2) ferroan rocks, ( quartz or feldspathoids) are the dominant minerals.
which include fayalite granites, alkali granites, and nepheline sye-
nites and are characterized by differentiation under reducing and
relatively dry conditions; (3) leucogranites, which commonly form R EV I SIONS TO T H E
by crustal melting; (4) potassic and ultrapotassic rocks, which origi- G E O C H E M I C A L C L A S S I F I C AT I O N
nate from mantle that has been enriched in K2O.
OF GR A N I T ES
Fe-index: the boundary between ferroan
KEY WORDS: granite; rhyolite; geochemistry; classification; nepheline and magnesian rocks
syenite; alkaline rocks; phonolite The FeO/(FeO þMgO) ratio of rocks is an important
indication of the fractionation history of a suite of rocks.
If the rocks are reduced [FMQ (fayalite^magnetite^
I N T RO D U C T I O N quartz) or below, Frost & Lindsley, 1992] fractional crystal-
Several years ago we introduced a geochemical classifica- lization results in iron enrichment, whereas if the rocks are
tion for granitic rocks (Frost et al., 2001). In that scheme relatively oxidized (FMQ þ 2 or more, Frost & Lindsley,
we suggested that granitic rocks could be classified using 1992) the crystallization of magnetite inhibits iron
1956
FROST & FROST FELDSPATHIC IGNEOUS ROCK CLASSIFICATION
12
nepheline alkali feldspar granite
20 alkali feldspar
Kspar
granite
average alkali feldspar 8
megacryst albite
10 an10 a granodiorite
an20 a-c
biotite c-a trondjhemite
c 4
MALI
0
MALI
an40 a
quartz tonalite
an60 0 a-c
−10 q diorite
hornblende
an80 c-a diorite
−4 c
−20 anorthite
augite
−8
−30 50 60 70 80
30 40 50 60 70 80 SiO2
SiO2
Fig. 3. MALI as a function of SiO2, showing where the model
Fig. 2. The location of various igneous minerals on plot of MALI granitoids listed in Table 1 plot. Abbreviations as in Fig. 2.
against SiO2. a, alkalic; a-c, alkali^calcic; c-a, calc-alkalic; c, calcic;
boundaries after Frost et al. (2001). Data from Deer et al. (1962, 1963)
and Vernon (1986).
12
Table 1: Modes and compositions used for model rocks Lofoten Ballachulish
8
Rock % Plag % Kspar % Q
4
Diorite 100 (An45) 0 0
MALI
−8
50 60 70 80
SiO2
parallel to the boundary between the calcic and calc-alka-
lic fields. In contrast, those granitoids that have increasing Fig. 4. Plot of MALI against SiO2 showing the composition ranges of
proportions of K-feldspar to plagioclase lie at progressively the Peninsular Ranges, Tuolumne, Ballachulish, and Lofoten batho-
liths. Abbreviations as in Fig. 2. Data from Larsen (1948), Malm
higher MALI values. Our simple calculations suggest that & Ormaasen (1978), Bateman & Chappell (1979), and Weiss &
the shape of the boundaries in the MALI diagram reflects Troll (1989).
the increases in the abundance of Kspar and in the albite
component of plagioclase with increasing silica in plutonic
rocks. For volcanic suites, the trend reflects the changes in Lofoten (Malm & Ormaasen, 1973) batholiths (Fig. 4).
normative abundances of these two feldspar end-members. A plot of the modal data for the four plutons from Fig. 4
To further emphasize the role of feldspars in the alkali^ on a QAP diagram (Le Maitre, 1989; Fig. 5) illustrates
lime index we have plotted the modes of some of the suites how differences in the MALI reflect differences in the feld-
that we used to define the MALI boundaries. Because spar composition. The rocks of the Peninsular Ranges
modal mineralogy data are sparse for the Sherman bath- batholith, which is a calcic series, follow a trend from
olith (Frost et al., 1999) and Bjerkreim^Sokndal intrusion diorite to quartz diorite to tonalite to granodiorite. In con-
(Duchesne & Wilmart, 1997), our type alkali^calcic and trast, the granitic rocks of Lofoten, an alkalic granitoid,
alkalic granitioids, we have plotted instead data from the follow the trend monzonite to quartz syenite to alkali feld-
alkali^calcic Ballachulish (Weiss & Troll, 1989) and alkalic spar granite (Fig. 5).
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JOURNAL OF PETROLOGY VOLUME 49 NUMBER 11 NOVEMBER 2008
Q (a)
16
alkali
feldspar
12
sodic
8 plagioclase
c-a
−4
Tuolumne c
−8
50 60 70 80
Ballachulish
SiO2
Lofoten
(b) 12
A P
Fig. 5. QAP diagram showing the trends in modal mineralogy of
rocks from the Peninsular Ranges, Tuolumne, Ballachulish, and 8 Sybille
Lofoten batholiths. Sources of data as in Fig. 4.
metaluminous
The aluminum-saturation index (ASI)
0.7
The third variable Frost et al. (2001) used in the classifica-
50 60 70 80
tion of granites is the aluminum-saturation index (ASI),
SiO2
which was defined as molecular Al/(Ca167P þ Na þ K)
(Shand, 1947; Zen, 1988), which separates rocks into meta- Fig. 6. Effects of feldspar accumulation and mixing on granitic com-
position indices. (a) MALI diagram showing how alkali feldspar
luminous and peraluminous varieties. Peraluminous vari- accumulation (arrows) can drive a plutonic rock to compositions
eties (ASI41) have more Al than is necessary to make more alkalic than the magma from which it crystallized. (b) MALI
feldspars. We noted (Frost et al., 2001) that rocks with diagram showing how the assimilation of calc-alkalic country-rock
ASI51 are metaluminous when molecular Na þ K5Al, gneiss made the more silica-rich portions of the Sybille monzosyenite
more calcic (c) Plot of ASI vs silica showing how the assimilation of
and are peralkaline when molecular Na þ K4Al. In this country-rock gneiss made the more silica-rich portions of the Sybille
paper we introduce an additional classification diagram monzosyenite more aluminous (data from Scoates et al., 1996).
1958
FROST & FROST FELDSPATHIC IGNEOUS ROCK CLASSIFICATION
A GEOC H EM ICA L
C L A S S I F I C AT I O N O F A L K A L I N E Hy, Ol-
1959
JOURNAL OF PETROLOGY VOLUME 49 NUMBER 11 NOVEMBER 2008
silica-undersaturated silica-saturated value (Fig. 9d). One suite that shows no increase in
Fe-index with increasing silica is the lamproites of the
Leucite Hills (Fig. 9d), which have been interpreted to
Al-adequate or excessive
metaluminous (rarely metaluminous and
record different degrees of melting or derivation by melting
peraluminous) peraluminous of different assemblages in the mantle (Mirnejad &
Bell, 2006).
+
feldspathoid-bearing quartz-bearing
minous granites (Fig. 10a and b). Those suites with the
lowest silica activity, such as Shonkin Sag or Nyambeni,
peralkaline tend to have the steepest slopes whereas those that are
Al-deficient
peralkaline quartz-
silica-saturated, such as Boina, tend to follow a slope close
feldspathoid-bearing
−
1960
FROST & FROST FELDSPATHIC IGNEOUS ROCK CLASSIFICATION
Ilimaussaq
0.8 0.8
Red Hill
Brome
Fe*
Fe*
0.4 0.4
40 50 60 70 80 40 50 60 70 80
SiO2 SiO2
Pantelleria Afar
0.6 0.6 Nandewar
Boina
0.4 0.4
Leucite Hills
40 50 60 70 80 40 50 60 70 80
SiO2 SiO2
Fig. 9. Variation of Fe in alkaline rocks; boundary as in Fig. 1. (a) Nepheline-bearing plutonic rocks; (b) ultrapotassic alkaline plutonic rocks
and plutonic suites, portions of which contain quartz; (c) volcanic rocks that formed by fractional crystallization; (d) volcanic rocks that evolved
by processes other than (or in addition to) fractional crystallization. Ferroan^magnesian boundary as in Fig. 1. Data from Jacobson et al. (1958),
Carmichael (1967), Abbott (1969), Nash et al. (1969), Ferguson (1970), Nash & Wilkinson (1970, 1971), Valiquette & Archambault (1970), Barberi
et al. (1974, 1975), Ewart et al. (1977), Brotzu et al. (1983), Eby (1985), Stoltz (1985), Currie et al. (1986), Orajaka (1986), Czygan & Goldenberg (1989),
Henderson et al. (1989), Le Roex et al. (1990), Civetta et al. (1998), Krishna Reddy et al. (1998), Bailey et al. (2001), Mirnejad & Bell (2006),
Di Renzo et al. (2007), Kumar et al. (2007) and Riishuus et al. (2008).
The trends shown in Fig. 11 reflect two processes that (FSSI50) to silica-saturated (FSSI40) as in the
accompany differentiation of igneous rocks, as follows. Kangerlussuaq intrusion (Riishuus et al., 2008), but there
(1) Melts generally evolve away from the thermal divide is no known closed-system process that could drive
(AI ¼ 00) towards minima (and under some conditions saturated melts into the undersaturated field.
eutectics) involving either feldspars þ feldspathoids or (2) There is a tendency for fractional crystallization of
feldspars þ quartz. Extraction of low-silica phases such as plagioclase and alkali feldspar to enrich the melt in
olivine and hornblende enriches a hypersthene-normative sodium while depleting it in alumina. As a result, many of
melt in silica, whereas crystallization of high-silica phases the suites cross from metaluminous to peralkaline with
such as aegirine and feldspars drives nepheline-normative increasing differentiation. In Fig. 11c we plot the location
melts away from the silica saturation boundary. Fractional of plagioclase of various compositions. Fractional crystalli-
crystallization of low-silica phases such as Fe^Ti oxides and zation of calcium-bearing plagioclase (with An as low as
Na-amphiboles can cause some alkali basalts to evolve to An40) extracts alumina in preference to Na, thus decreas-
silica-saturated rhyolites (e.g. Red Hill, Henderson et al., ing the AI of the magma. This phenomenon, known as the
1989; Pantelleria, Civetta et al., 1998). Crustal assimilation ‘plagioclase effect’ (Bowen, 1945), can cause a primary melt
may cause the transition of magmas from undersaturated in which molecular Ca is greater than Al to evolve toward
1961
JOURNAL OF PETROLOGY VOLUME 49 NUMBER 11 NOVEMBER 2008
6 a 6 a
a-c Red Hill a-c
MALI
MALI
c-a c-a
c
−18 −18
40 50 60 70 80 40 50 60 70 80
SiO2 SiO2
(c) (d)
Suswa 2 Nandewar
14 Suswa 1 14 Vesuvius Afar
−2 −2
Leucite Hills
Pantelleria
−10 −10 Afar
Boina
−18 −18
40 50 60 70 80 40 50 60 70 80
SiO2 SiO2
Fig. 10. Variations of MALI vs SiO2 (wt %) in alkaline rocks. (a) Nepheline-bearing plutonic rocks; (b) ultrapotassic alkaline plutonic rocks
and plutonic suites, portions of which contain quartz; (c) volcanic rocks that formed by fractional crystallization; (d) volcanic rocks that evolved
by processes other than (or in addition to) fractional crystallization. Abbreviations as in Fig. 2; sources of data as in Fig. 9.
alkaline differentiates. For some suites (such as Nyabeni granitoids; (3) metaluminous feldspathoid-bearing
and Boina) the transition to peralkaline compositions is syenites; (4) peralkaline feldspathoid-bearing syenites
simply a manifestation of the plagioclase effect (Barberi (Table 2).
et al., 1975; Brotzu et al., 1983). In addition to the plagioclase Frost et al. (2001, table 1) categorized the varieties of
effect, alkaline rocks commonly evolve Na-rich fluids granitoids on the basis of the Fe-index, MALI, and ASI.
and addition of such fluids can increase the alkalinity of The alkaline rocks fall into the alkalic (or rarely alkali^
magmas (Bailey, 1974). Such a process has been postulated calcic) peralkaline category in that table. With the
for the volcanic centers marginal to the Afar rift (Barberi addition of the AI and FSSI indices, we can expand the
et al., 1974) and in the peralkaline nepheline syenites of classification of alkaline rocks. This expanded classification
Ilimaussaq (Schoenenberger et al., 2006). is presented in Table 2, where the peralkaline granites
are included along with other alkaline rocks. Of all the
A classification of feldspathic rocks alkaline rock suites that we compiled, only Shonkin Sag,
Frost et al. (2001) based their granitoid classification on the phonotephrites of Vesuvius, and Leucite Hills are
three indices: Fe-index, MALI and ASI. In this paper we magnesian; all the others are ferroan.
have introduced the alkalinity index (AI) and the feld-
spathoid silica-saturation index (FSSI). These additional Nature of intraplate magmatism
indices extend the original classification to encompass The fact that nearly all alkaline rocks are ferroan
alkaline rocks. As is evident from Fig. 8, the AI and FSSI suggests that they most probably formed through extreme
indices divide feldspathic rocks into four broad categories differentiation or partial melting of tholeiitic to alkalic
of plutonic rocks (and their volcanic equivalents): (1) meta- mafic magmas, similar to other ferroan granites (Loiselle
luminous and peraluminous granitoids; (2) peralkaline & Wones, 1979; Frost & Frost, 1997). It has long been
1962
FROST & FROST FELDSPATHIC IGNEOUS ROCK CLASSIFICATION
(a) (b)
0.14 0.14
0.10 0.10
AI
AI
Nyambeni
AI
0.02 0.02
−0.02 −0.02
Suswa 2 Ab,Or
−0.06 Suswa 1 −0.06 Tweed
Leucite Hills
−0.10 −0.10
−1.2 −0.8 −0.4 0.0 0.4 −1.2 −0.8 −0.4 0.0 0.4
FSSI FSSI
Fig. 11. FSSI vs AI plots for alkaline rocks. (a) Nepheline-bearing plutonic rocks; (b) ultrapotassic alkaline plutonic rocks and plutonic suites,
portions of which contain quartz; (c) volcanic rocks that formed by fractional crystallization; (d) volcanic rocks that evolved by processes other
than (or in addition to) fractional crystallization. Sources of data as in Fig. 9.
1963
JOURNAL OF PETROLOGY VOLUME 49 NUMBER 11 NOVEMBER 2008
Plutonic rocks
alkaline rocks
Application to mafic rocks
ferroan granites Although in this paper we have plotted suites of rocks
ferroan granites
that contain samples with silica contents as low as 40%,
layered mafic peralkaline nepheline syenite
intrusions and syenites granite our classification scheme does not distinguish well various
types of basaltic rocks: basanite, alkali basalt, oceanic tho-
low-P
anorthosite leiites, mid-ocean ridge basalts (MORB), and arc basalts
differentiation all plot in the same area on MALI diagrams (Fig. 14a).
high-P Therefore, although MALI diagrams may depict the
differentiation
evolution of alkalis in mafic rocks, we suggest that the
tholeiite transitional basalt alkali basalt basanite alkalic alkali calcic calc-alkalic calcic boundaries
Fig. 13. Schematic diagram showing the relationships between intra-
on the MALI diagrams are not usefully applied to rocks
plate feldspathic rocks and their inferred parental basalts. that have silica contents lower than 52%. We have chosen
this silica value for two reasons. First, it marks the bound-
the melt in equilibrium with Plag^Ol^Cpx will be alumi- ary between intermediate and mafic rocks (Le Maitre,
nous and when it is emplaced into shallow levels it would 1989) and is a logical place to make a break. Second, the
lie in the primary crystallization field for plagioclase MALI diagram distinguishes suites of rocks dominated by
(Longhi et al., 1993). Both these processes could lead to the feldspars (or feldspathoids) and mafic rocks are dominated
formation of massif anorthosites (Fig. 13). instead by pyroxenes or amphiboles.
The residual magmas from anorthosites or from high-P Because we have defined the Fe-index using ferrobasalts,
differentiation of tholeiitic magmas may form potassic this index can be used for rock suites with silica values
ferroan granites (Anderson et al., 2003; Whitaker et al., as low as 48% (Fig. 14b). As noted above, it is helpful in
2008). Extreme fractional crystallization or partial melting distinguishing those suites that have undergone extensive
of basalts that are transitional between tholeiite and alkali differentiation under low oxygen fugacities from those
basalt could lead to the formation of peralkaline granites that have not. The ferroan^magnesian boundary as we
(Barberi et al., 1975; Loiselle & Wones, 1979), although have defined it is fundamentally different from that of
peralkaline granites may also form by assimilation of Miyashiro (1974). Our boundary distinguishes rocks that
siliceous crust by phonolitic magmas (e.g. Kangerlussuaq; have undergone extensive iron enrichment from those
Riishuus et al., 2008). Finally, differentiation of alkali that have not, whereas Miyashiro’s boundary distinguishes
basalts and basanites will lead to the formation of suites that have undergone even moderate amounts of
nepheline syenites (Fig. 13). These syenites are likely to be Fe enrichment (his ‘tholeiitic’ trend) from those that have
metaluminous, unless the original magma had rather undergone some Si enrichment (his ‘calc-alkalic’ trend).
low abundances of normative An, in which case the plagi- It is important to note that, at low silica, his boundary
oclase effect could cause these nepheline syenites to be does not distinguish between tholeiitic and calc-alkalic
peralkaline (Bowen, 1945). rocks senso stricto: for example, basalts from Giant Crater,
1964
FROST & FROST FELDSPATHIC IGNEOUS ROCK CLASSIFICATION
Hawaii alkali basalts Our new classification scheme, when added to that of Frost
et al. (2001), establishes that feldspathic igneous rocks fit
Magnesian Rocks that follow a rela- Tonalites, granodiorites, Arc or post-collisional Tuolumne Etive (Bateman & Chappell,
tively oxidizing differentia- granites and their volcanic magmas or melts derived 1979) (Frost & O’Nions,
tion trend with minor Fe equivalents from earlier arc magmas 1985)
enrichment
Ferroan Fe-rich rocks that have Ferroan granites, alkali Evolved magmas from Bjerkreim–Sokndal (Duchesne & Wilmart,
undergone extensive frac- granites, nepheline syenites intraplate environments Ilimaussaq 1997) (Ferguson, 1970)
tionation at low oxygen and volcanic equivalents
fugacity
Leucogranite High-silica granitoids that Peraluminous and metalu- Crustal melts found in Manaslu Tetons (La Fort, 1981) (Frost et al.,
are commonly minous leucogranite compressional tectonic 2006)
peraluminous environments
Potassic K-rich and ultra-K-rich Lamproites and high-K Rare, found in both intra- Leucite Hills Roman (Carmichael, 1967; Mirnejad
mafic and felsic magmas shoshonites, plate and arc settings Province & Bell, 2006) (Avanzinelli
phonotephrites et al., 2008)
1965
JOURNAL OF PETROLOGY VOLUME 49 NUMBER 11 NOVEMBER 2008
although a few are peraluminous (Collins et al., 1982; crystallization is required to enrich the melt in alkalis
King et al., 2001). They form in intraplate settings, mostly (Bowen, 1945), potassic rocks emerge from the mantle
on continents, although evolved magmas from ocean already enriched in alkalis, hence their magnesian nature.
islands also fall into this group (Haapala et al., 2005;
Bonin, 2007). The most Fe-rich of these rocks form by differ- Summary
entiation or partial melting of basaltic parents (Loiselle & Although distinctive examples exist for all these families
Wones, 1979; Frost & Frost, 1997).
1966
FROST & FROST FELDSPATHIC IGNEOUS ROCK CLASSIFICATION
potassic family includes magmas typically produced in Bonin, B. (2007). A-type granites and related rocks: evolution of a
small volumes by partial melting of potassium-enriched concept, problems and prospects. Lithos 97, 1^29.
Bowen, N. L. (1945). Phase equilibria bearing on the origin and differ-
mantle.
entiation of alkaline rocks. AmericanJournal of Science 243A, 75^89.
Brotzu, P., Morbidelli, L. & Piccirillo, E. M. (1983). The basanite
AC K N O W L E D G E M E N T S to peralkaline phonolite suite of the Plio-Quaternary Nyambeni
The authors would like to thank Gregor Markl, James multicenter volcanic range (East Kenya Plateau). Neues Jahrbuch
1967
JOURNAL OF PETROLOGY VOLUME 49 NUMBER 11 NOVEMBER 2008
Frost, C. D. & Frost, B. R. (1997). High-K, iron-enriched rapakivi-type MacDonald, G. A. (1968). Composition and origin of Hawaiian lavas.
granites: the tholeiite connection. Geology 25, 647^650. In: Coats, R. R., Hay, R. L. & Anderson, C. A. (eds)Studies in
Frost, C. D. & O’Nions, R. K. (1985). Caledonian magma genesis and Volcanology. A memoir in honor of Howell Williams. Geological Society of
crustal recycling. Journal of Petrology 26, 515^544. America Memoir 116, 477^522.
Frost, C. D., Frost, B. R., Chamberlain, K. R. & Edwards, B. R. Malm, O. A. & Ormaasen, D. E. (1978). Mangerite^charnockite
(1999). Petrogensis of the 143 Ga Sherman batholith, SE intrusives in the Lofoten^Vesterlen Area, North Norway:
Wyoming: a reduced rapakivi-type anorogenic granite. Journal of Petrography, chemistry, and petrology. Norges Geologiske Underso« kelse
1968
FROST & FROST FELDSPATHIC IGNEOUS ROCK CLASSIFICATION
Riishuus, M. S., Peate, D. W., Tegner, C., Wilson, J. R. & Brooks, C. K. Stoltz, A. J. (1985). The role of fractional crystallization in the evolu-
(2008). Petrogenesis of cogenetic silica-oversaturated and -undersa- tion of the Nandewar Volcano, north-eastern New South Wales,
turated syenites by periodic recharge in a crustally contaminated Australia. Journal of Petrology 26, 1002^1026.
magma chamber: the Kangerlussuaq Intrusion, East Greenland. Sutton, A. N., Blake, S., Wilson, C. J. N. & Charlier, B. L. A. (2000).
Journal of Petrology 49, 493^522. Late Quaternary evolution of a hyperactive rhyolite magmatic
Schoenenberger, J., Marks, M., Wagner, T. & Markl, G. (2006). Fluid^ system, Taupo Volcanic Center, new Zealand. Journal of the
rock interaction in autoliths of agpaitic nepheline syenites in the Geological Society, London 157, 537^557.
1969