Mineralogy and Petrology (1990) 41:163-183

Mineralogy
ano
Petrology
© by Springer-Verlag 1990

Mineralogical Evidence for the Derivation

of Metaluminous, Potassic Rocks
from Peralkaline Precursors:
The Cordon Syenite Complex (Philippines)*
U. Knittel and A. Cundari

Department of Geology, University of Melbourne, Parkville, Victoria, Australia

With 6 Figures

Received October 10, 1989;

accepted February 16, 1990

Summary
Rocks from the Cordon Syenite Complex, located in the Philippine island arc, corre-
spond to miaskitic (metaluminous) potassic lavas from the Roman Region and the
Indonesian arc in terms of bulk rock chemistry. However, the mineral chemistry in-
dicates a complex history of multiple equilibrations with liquids of different nature. T-site
(Si + A1) occupancy in some clinopyroxenes and Ca contents of alkali feldspar pheno-
crysts indicate that these phases crystallized under the temperature-pressure subvolcanic
regime from host liquids with progressively decreasing (Na + K)/A1 ratio. In con-
trast to current views on the genesis of potassic rocks, it is suggested that differentiated
leucite tephrite suites may be derived from peralkaline liquids by alkali loss. Magmas
with affinities to lamproites may occur in the Philippine island arc, but a direct
genetic relationship between subduction and alkaline/peralkaline magmatism remains
questionable.

Zusammenfassung
Mineralogische H inweise auf die Entstehung subalkalischer, K-reicher gesteine aus peral-
kalischen Vorliiufern: Der Syenit Komplex yon Cordon (Philippinen)
Die Magmatite des im philippinischen Inselbogen gelegenen Syenitkomplexes von Cor-
don entsprechen in ihrem Gesamtgesteinschemismus den miaskitischen, K-reichen Vul-

* Paper presented at the General Assembly of the International Association of Volcano-

logy and Chemistry of the Earth Interior, Santa Fe, New Mexico, 1989.
164 U. Knittel and A. Cundari

kaniten der Romanischen Provinz und des indonesischen Inselbogens. Die chemische
Zusammensetzung einzelner Mineralphasen deutet auf eine komplexere Genese unter
Beteiligung von Magmen unterschiedlicher Alkalinit~it hin. Die Variation in der Beset-
zung der T-Position (Si + A1)in Klinopyroxenen und der Ca-Gehalte in Alkalifeldsp/~ten
wird dahingehend interpretiert, dab diese Phasen unter subvulkanischen Bedingungen
aus Schmelzen mit abnehmenden (Na + K)/A1-Verhfiltnissenkristallisierten. Im Gegen-
satz zu g/ingigen Auffassungen wird daher angenommen, dab differenzierte Leucit-
Tephrite aus mild-peralkalischen Magman hervorgehen k6nnen. Obwohl die K-reichen
Magmatite des Syenitkomplexes von Cordon in einem Inselbogen gebildet wurden, ist
ein direkter Zusammenhang mit Anreicherungsvorg/ingen im Bereich der Subduktions-
zone fraglich.

Introduction
K-rich alkaline rocks are a volumetrically insignificant group of igneous rocks on
a worldwide basis, but are the dominant rock type in some igneous provinces such
as the Roman Comagmatic Region, henceforth refered to as Roman Region, and
the West African Rift. On the basis of their mineralogy and major element chemistry
potassic igneous rocks may be subdivided into three groups, viz. (1) lamproites
('Leucite Hills type magmas' of Barton, 1979; group I of Foley et al., 1987), (2) leucite
tephrites and related rocks (the "high-K series" (HKS) of the Roman Region of Apple-
ton, 1972; 'Roman Province type magmas' of Barton, 1979; group III of Foley et
al., 1987), and (3) kamafugites ('Toro-Ankole type magmas' of Barton, 1979; group
II of Foley et al., 1987). These groups are not clearly separated petrologically and
transitional types bridge the gap between the more extreme compositions (Barton,
1979; Foley et al., 1987). The genetic relationships between these rock types are not
well understood. Roman Region type magmas appear to be restricted to volcanic
arcs at destructive plate boundaries (Whitford, 1975; Varne and Foden, 1986). Lam-
proites and related rocks occur almost exclusively in cratonic areas, suggesting that
their generation may be related to intra-plate tectonic processes (Bergman, 1987),
though some lamproites have been found in the Northwestern Italian Alps (Ventur-
elli, 1984). Kamafugites are clearly related to extensional tectonics.
In a comparative study, Barton (1979; see also Cundari and Ferguson, 1982 and
Ferguson and Cundari, 1982) has outlined the mineralogical characteristics of lavas
representative of the three types of potassic rocks as defined above. In lamproites
leucite and alkali feldspar are Fe3+-rich, leucite contains significant amounts of
excess silica, and clinopyroxenes and other ferro-magnesian minerals are Al-poor
and contain insufficient Si and A1 to fill the tetrahedral sites. In Roman Region
type lavas, leucite and alkali feldspars are Fe3+-poor, alkali feldspar is Ca-rich
and associated with plagioclase. Clinopyroxene and other ferro-magnesian minerals
have variable, occasionally high A1, and contain more Si and A1 than is required
to fill the tetrahedral sites. Toro-Ankole type lavas do not contain feldspars, leucite
compositions are close to stochiometry, and clinopyroxenes are Al-rich with (Si +
A1) which may or may not be sufficient to fill the tetrahedral sites. Subsequent
detailed studies have confirmed these trends (e.g., Carmichael, 1967; Cundari, 1979;
Sheraton and Cundari, 1980).
Foley et al. (1987) summarized the geochemical features of potassic rocks and
argued that their chemical characteristics reflect the evolution of their mantle
sources. 'Roman Province type magmas; characterized by moderate SiO2 (45-48
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 165

wt. ~ in the more mafic members), variable, usually high A1103 (12-18 wt. ~), CaO
(12-14 wt. ~) contents, and (Na + K)/A1 < 1 (atomic ratio), are considered to be
derived from relatively fertile mantle peridotite, selectively enriched in incompatible
elements. On the other hand, lamproites, characterized by variable, usually high
SiO2 (>51 wt. ~), low to very low AlzO 3 (< 10 wt. ~), N a / O ( < 2 wt. ~o), and CaO
(< 6 wt. ~) contents, and (Na + K)/A1 > 1, are believed to be derived from sources
that have lost A1, Ca, and Na during one or more earlier melting events and to have
been subsequently enriched in incompatible trace elements. Kamafugites, which are
characterized by very low SiO2 (< 42 wt. ~) and high CaO (> 12 wt. ~o), appear to
be derived from sources that were initially depleted (similar to lamproite sources),
but subsequently enriched not only in trace elements, but also in CaO (by carbonati-
tic melts?).
Within the Cordon Syenite Complex, which is located in the Philippine island
arc and clearly belongs to the Roman Region type with respect to bulk-rock
geochemistry, some rocks contain clinopyroxenes and alkali feldspar phenocrysts,
which closely resemble the respective minerals from mildly peralkaline, transitional
lamproites, while the bulk of the complex contains minerals with appropriate
compositions for Roman Region-type lavas. This suggests that the two different
magma types (Roman Region type and lamproites) may be related in terms of
differences in magma evolution, viz. evolution in open vs. closed systems, rather
than differences in source compositions. Furthermore, the data presented in this
paper indicate that peralkaline magmas with affinities to lamproites may occur in
oceanic island arcs.

Regional Setting and Field Relationships

The Cordon Syenite Complex (CSC) is located at the margin of the Cagayan Basin,
an asymmetrical graben structure in the central part of North Luzon (Christian,
1964), the northernmost island of the Philippine arc (Fig. 1). It is composed of
shallow level multiple intrusions, associated with comagmatic volcanic rocks. Rb-Sr
whole-rock and biotite age determinations indicate that the CSC was emplaced at
25 _ 1 Ma (Knittel, 1983). A second alkaline complex, the Palali Intrusion, was
emplaced at about the same time southwest of the CSC and consists exclusively of
highly differentiated syenites and nepheline syenites and their extrusive analogues
(Albrecht and Knittel, in press). The oldest sediments found in the Cagayan Basin
are of early Miocene age (Christian, 1964) indicating that the emplacement of
potassic magmas and the initial graben subsidence occurred contemporaneously.
The extrusion of potassic lavas and formation of the Cagayan Basin followed a
period of extensive subalkaline volcanism and plutonism lasting about 27-50 Ma
with possibly a period of magmatic quiescence at 33-42 Ma (Wolfe, 1981; Knittel,
1983). Magmatism in this period is generally believed to have been related to
westward-directed subduction below the Philippine arc (e.g., Karig, 1973; Knittel,
1986).
The dominant volcanic rock type is analcime-tephritic phonolite (ATP), which
forms the hills east of the intrusive complex and locally overlies a sequence of folded
tufts west of the intrusion. The folded sequence is not exposed east of the intrusion,
suggesting that the magma intruded a fault zone along which the eastern block was
downfaulted. The present thickness of the volcanic deposits, comprising essentially
166 U. Knittel and A. Cundari

1 8 °-

16 °

Fig. 1. Map of northern Luzon, showing the location of the Cordon Syenite Complex (CSC)
and the Palali Intrusion (PI). Potassic igneous complexes are shown in black; subalkaline
batholiths of Oligocene age are stippled. Paleogene volcanic sequences and sediments are
ruled. The Lingayen-Dingalan Fault forms the southern boundary of northern Luzon

ash-flow tufts with few intercalated lavas, is at least 300 m, which may be considered
as a minimum depth for the intrusive complex.
The intrusive complex consists of several large bodies of syenitic rocks, which
may be distinguished by their porphyritic vs. non-porphyritic structure. These large
bodies are intruded by several small stocks and dykes of monzonite and lusitanite
(marie alkali syenite; Streckeisen, 1976).
The pseudoleucite phonolites (pseudoleucite-bearing syenites of Knittel, 1983,
1987) underlie an area about 300 x 1000 m wide, close to the eastern margin of the
intrusive complex. Lack of adequate outcrops has so far prevented the establishment
of the nature of the contact between the intrusive complex and these rocks. Previous-
ly the pseudoleucite phonolites were considered as chilled margin (Knittel, 1983,
1987). A re-examination of their field and textural relationships suggests that they
are lavas which form part of the roof of the intrusion or were rafted into their present
position by the upwelling of the intrusive magma.

Petrography and Geochemistry

ATP contains large clinopyroxene phenocrysts (up to 1 cm long), which may be
associated with variable amounts of analcime (0-30 vol. %, up to 1.5 cm in diameter).
Some samples contain also small amounts of albitized feldspar (formerly plagio-
clase?), apatite, biotite, and Fe-Ti oxides (Knittel, 1987). The glassy matrix contains
microcrystalline analcime crystals. The composition of the glass closely approx-
imates alkali feldspar composition. The analcime crystals are considered to be
leucite pseudomorphs (Knittel, 1983, 1987; Wilkinson, 1977).
The intrusive rocks (syenites, alkali syenites and monzonites), which differ from
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 167
Table 1. Major and trace element data for selected samples of the Cordon Syenite
Complex

Sample KN17 KN13 Q43 KN1 Q51 KN18

rock type tephritic syenite syenite psleucite monzonite amph.
phonolite syenite syenite

Major elements (wt. per cent)

SiO2 50.8 52.9 53.9 52.4 55.5 55.4
-I-iO2 0.58 0.51 0.49 0.52 0.48 0.37
AI203 13.5 15.9 17.2 16.7 18.4 17.5
Fe203 8.6 8.4 6.5 6.3 5.8 5.2
MnO 0.16 0.12 0.16 0.13 0.13 0.1
MgO 6.0 4.6 3.4 3.1 2.1 1.9
CaO 8.7 7.4 7.3 7.7 5.8 6.4
Na20 2.5 3.5 3.7 1.5 4.0 4.3
K20 6.1 4.5 5.7 7.7 5.2 6.6
P205 0.59 0.49 0.63 0.50 0.57 0.32
LOI 2.2 1.9 1.3 3.9 2.1 1.9

total 99.7 100.2 100.3 100.4 100.0 100.0

Trace elements (p.p.m.)

Rb 109 87 100 157 92 125

Sr 1519 1133 1508 2335 2136 1996
Ba 850 568 716 861 924 723
Zr 56 74 n.d. n.d. n.d. 131
Y 14 13 n.d. n.d. n.d. 16
Nb 4 5 n.d. n.d. n.d. 7
Ta 0.11 0.14 n.d. n.d. n.d. 0.32
Hf 1.19 1.67 n.d. n.d. n.d. 3.02
Th 1.40 2.05 n.d. n.d. n.d. 4.00
Ni 32 31 n.d. 14 11 10
Cr 99 48 n.d. 20 36 12

n.d. = not determined

Major elements and all trace elements except Ta, Hf, and Th were determined by XRF
methods on fused discs (major elements) and powder pellets (trace elements) and Ta, Hf, and
Th were determined by INNA.

each other in the relative proportions of alkali feldspar, plagioclase, and mafic
minerals as well as in their porphyritic to equigranular textures (Knittel, 1987), are
close variants of the ATP in that their matrix is composed of coarse K-feldspar.
Analcime was not detected, possibly due to reaction of leucite, magnetite, and
clinopyroxene with the melt to form phlogopite (Knittel, 1987). Lusitanite contain-
ing K-feldspar pseudomorphs after leucite is considered as a clinopyroxene-leucite
cumulate emplaced while partially consolidated (Knittel, 1987).
With respect to major element chemistry (selected analyses are given in Table
1; for additional data see Knittel, 1987), the potassic rocks of the CSC closely
resemble the HKS rocks of the Roman Region and the Indonesian arc. This
relationship is illustrated in Fig. 2, where compositions are plotted in S i O 2 vs.
(Na + K)/A1 and CaO vs. A1z 0 3 diagrams, respectively, (based on Barton, 1979 and
Foley et al., 1987) and are compared with typical Roman Region, lamproite, and
kamafugite compositions.
With regard to minor and trace element compositions, the CSC rocks are
characterized by similar K2 O, TiO2, and Sr, and lower Ba and Rb concentrations
168 U. Knittel and A. Cundari

65

60

55
Si02
50

45

40
0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4
(Na + K) / AI

14

12

10

8
CaO
6

0
6 8 10 12 14 16 18 20 22
AI 2° 3

Fig. 2a, b. Bulk-rock compositions of the Cordon Syenite Complex (circles)compared with
typical lamproites, kamafugites, and Roman Region HKS lavas (after Barton, 1979; Foley
et al., 1987)

compared with the leucite tephrites of the Roman Region (Knittel, 1987). They have
typical "arc-signatures', i.e. low Ti, Nb, Ta, Zr, Hf (Table 1). Initial 87Sr/86Sr ratios
of 8 samples scatter in the range of 0.70350-0.70364 (Knittel and Defant, 1988), which
are virtually identical, within the analytical error (Knittel, 1983). A pyroxenite had
a slightly higher STSr/S6Sr ratio (0.70388), confirmed by a duplicate analysis. These
ratios are low compared with those reported of similar rocks from Indonesia
(0.7039-0.7071; Whitford et al., 1978; Varne and Foden, 1986), HKS magmas from
the Roman Region (0.7053-0.7110; e.g., Hawkesworth and Vollmer, 1979), lamproi-
tes (0.7053-0.7201; Vollmer et al., 1984; McCulloch et al., 1983) and kamafugites
(0.7037-0.7061; Bell and Powell, 1969). One ATP sample was included in a regional
study of the Sr-Nd isotopic variation of Mid-Tertiary igneous rocks in northern
Luzon and yielded lgaNd/lggNd = 0.51296 -t- 0.00002 (Knittel et al., 1988). This
value is higher than values found for Roman Region HKS (0.51218-0.51260; Haw-
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 169

kesworth and Vollmer, 1979) and lamproites ( < 0.51220; Fraser et al., 1985). In the
143Nd/144Nd vs. 875r/86Sr plot, the sample from the CSC and two samples from
the Palali Intrusion plot in the same field as the Oligocene non-alkaline plutonic
rocks, forming the large batholiths of North Luzon (Knittel et al., 1988).

Sample Selection and Analytical Methods

15 out of about 150 samples were selected for microprobe analysis after detailed
thin section studies and bulk rock chemical analyses. The specimens whose composi-
tions are considered in Figs. 3 through 6 are identified in the appendix; sample
locations are given in Knittel (1982). Mineral compositions were obtained by means
of an automated JEOL JXA-5A electron microprobe operated at 15 kV accelerating
voltage and 0.02-0.03 #A specimen current. The operational mode was described
by Ferguson and Sewell (1980). The results were corrected following the method of
Mason et al. (1969) and are considered to be accurate within 2-3% for major
elements and better than 9% for minor elements.

Mineral Chemistry
In view of the similarities in bulk rock geochemistry between CSC and Roman
Region HKS type lavas, it was expected that the corresponding mineral composi-
tions would also be similar. However, the results of this study show that this is not
true for several representative samples.

Clinopyroxene
Clinopyroxene is an ubiquitous phase in the CSC. Typical analyses and structural
formulae are given in Table 2. Calculation of structural formulae on the basis of 4
cations and 6 oxygens in no case resulted in the conversion of the total Fe, expressed
as Fe 2+, into Fe 3*, in contrast to observations by Barton and van Beroen (1981).
The pseudoleucite phonolites contain three optically distinct clinopyroxene types
(Table 2a). Type 1 is rare and is characterized by a colourless core and a green rim,
usually separated from each other by a very narrow zone with transitional colour
and composition. Type 2 is greenish, appears to be either optically homogeneous or
faintly zoned and corresponds in composition to the rims of type 1 clinopyroxenes.
The frequent occurrence of type 2 clinopyroxenes indicates that they are not merely
rim sections of type 1 clinopyroxenes. Type 3 has brownish cores overgrown by
greenish rims and is very rare.
The colourless cores of type 1 clinopyroxenes are diopside, while their green
rims, as well as type 2 and type 3 clinopyroxenes are salites (Fig. 3). The diopside
cores are compositionally variable, while their salite rims and type 2 salites all
yielded very similar compositions. This indicates that the diopsides are either
xenocrysts or they may represent early stages of magma evolution, while the green
salites represent the clinopyroxene in equilibrium with the host magma. The brown
cores of type 3 salites are generally the most Fe-rich clinopyroxenes found in the
CSC. They contain slightly more Na and distinctly less A1 than the green salites and
in their rim compositions approach the main field of the green salites, suggesting
that they may be xenocrystals with rims equilibrated with the host magma.
170 U. Knittel and A. Cundari

Table 2a. Typicalchemicalcompositionsand structuralformulae of clinopyr-

oxenesfrom sample KN1

No. 65 274 62 275 113 112 118 120

ooloudesswith green vim green brown

%wt. core core rim rim core rim core rim

SiO2 52.49 52.73 49.66 47.53 50.50 48.38 48.97 48.47

TiO2 0.27 0.16 0.46 0.91 0.67 0.94 0.69 0.75
AI203 0.95 1.29 3.36 4.65 2.51 4.25 2.17 3.57
Fe203 * 3.32 3.65 6.29 7.35 6.05 6.65 7.38 6.73
FeO* 1.39 1.36 2.01 2.84 2.90 3.95 4.13 3.68
MnO 0.11 0.07 0.16 0.31 0.25 0.35 0.39 0.32
MgO 16.20 16.43 13.94 12.06 13.26 11.86 11.67 11.79
CaO 24.21 24.44 24.30 23.55 23.80 23.24 22.70 22.97
Na20 0.35 0.25 0.32 0.61 0.80 0.75 1.02 0.81
Cr203 0.04 0.05 0.08 0.06 0.04 0.00 0.03 0.03

99.32 100.44 100.60 99.87 100.77 100,37 99.13 99.36

Cations on the basis o f 4 cations and 6 oxygens

Si 1.938 1.926 1.837 1.788 1.871 1.813 1.864 1.833

AI IV 0.041 0.056 0.147 0.206 0.109 0.187 0.098 0.159
-13 0.007 0.005 0.013 0.006 0.019 0.000 0.020 0.008
Fe3+ 0.014 0.013 0,001 0.000 0.001 0.000 0.018 0.000
,~ 2.000 2.000 2.000 2.000 2,000 2.000 2.000 2.000

AI vl 0.000 0,000 0.000 0.000 0.000 0.001 0.000 0.000

13 0.000 0.000 0.000 0.020 0.000 0.027 0.000 0.013
Mg 0.891 0.895 0.768 0.677 0.732 0.662 0,662 0.677
Fe 2+ 0,043 0,042 0.062 0.089 0.090 0.124 0.132 0.116
Fe3+ 0.078 0.087 0,174 0.208 0.168 0,188 0.193 0.192
Cr 0.001 0.001 0.002 0.002 0.001 0.000 0.000 0,001
Ca 0.958 0.956 0.963 0.950 0.945 0.933 0.926 0.931
Na 0.025 0.018 0.023 0.044 0.057 0,055 0.075 0.060
Mn 0.004 0.002 0.005 0.010 0.008 0.011 0.013 0.010
Y, 2.000 2.000 2.000 2.000 2.000 2.000 2.000 2.000

* partitioned on the basis of 4.00 cations and 6.00 oxygens

The diopsides are characterized by high SiO 2 (usually > 52 wt. ~o) and low A1z 0 3
contents (usually < 2 wt. ~). Salites have lower SiOz (usually < 51 wt. ~ ) and higher
A I 2 0 3 contents (usually > 3 wt. ~o). In general, the A1 and N a contents of CSC
clinopyroxenes increase with decreasing m9 [ = Mg/(Mg + Fe z+ + Fe 3+ + Mn)].
However, the correlation between A1 and mg is restricted to the range mg = 0.91 -
0.70. At lower values (mg = 0.70 - 0.66) AI increases without further decrease in rag.
The lack of a similar N a enrichment indicates that N a is essential to maintaining
charge balance, rather than reflecting the N a concentrations of the liquid (cf. Dal
Negro et al., 1984). The limited Fe-enrichment is a typical feature of clinopyroxenes
from m a n y other potassic and calc-alkaline suites (e.g., Joplin et al., 1972; Cundari,
1975, 1979; Holm, 1982) and appears to reflect the lack of significant Fe-enrichment
in these rocks.
The most interesting feature of the clinopyroxenes in pseudoleucite phonolite is
that, except for a few Al-rich salites, they consistently contain insufficient (Si + A1)
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 171
--colourless cores / green &brown cores

/tl/amproite Jl~i"g~l~ " _-A ~ ~0 0~' 0

• /o/ ..'..-" i" • • •
• u~ I~lo1.,,/ [] O
'Y "i ,vow
\ j "" / • []

45 / / / /
5 l0 15 20
• KN1 AKN7 *KN13 "B37

(~ ® ~ o oO
D 0

45 / / i / / / Fe, Mn
5 10 15 20
nCA1 o051 -KN18
/ / /

• •0 • 0

45 / / / /
5 10 15 20
• KN17 *MAG4 AQ43 "JG6
Fig. 3. Clinopyroxenes from the Cordon Syenite Complex plotted in terms of Ca-Mg-
Z(Fe + Mn), atoms on the basis of 4.00 cations and 6.00 oxygens. Closed symbols, cores;
open symbols, rims; circles with dot: brown cores; for key to specimen see Appendix. Circled
symbols (KN 18) in Fig. 3b indicate xenocrysts with (Si + AI) < 2. The fields for lamproite
clinopyroxene compositions, based on data from West Kimberley (Jaques et al., 1984),
Leucite Hills (Carmichael, 1967; Kuehner et al., 1981), and Gaussberg (Sheraton and Cundari,
1980), and clinopyroxenes in the New South Wales leucitites (Cundari, 1973), are shown for
comparison

to fill the tetrahedral sites to the stoichiometric value of T = 2 (Fig. 4a), similar to
clinopyroxenes from peralkaline rocks (Barton, 1979; Cundari and Ferguson, 1982).
Furthermore, the majority ofdiopsides does not contain sufficient Ti to compensate
for the (Si + A1) deficiency, and Fe 3+ possibly enters the tetrahedral sites. On the
other hand, the salites usually contain enough Ti to fill the T-sites with (Si + A1 +
Ti). Because of the lack of A1 in the Ml-site, the charge deficiencies, resulting from
the incorporation of A1 in the T-site and of Na in M2, have to be balanced by Fe 3+
in M1, resulting in high Fe 3+ contents of these clinopyroxenes. The A12 03 contents
of diopsides and salites are high, compared with diopsides from typical peralkaline
rocks, but are comparable to those in clinopyroxenes from the New South Wales
leucitites (Fig. 4a), which are alkaline to slightly peralkaline ([Na + K]/A1 = 0.85 -
1.25; Cundari, 1973).
Clinopyroxenes sharing the characteristic features of type 1 diopsides have been
found also in the amphibole-bearing syenite KN18, where their association with
clinopyroxenes with (Si + A1) > 2 and with plagioclase provides clear evidence for
172 U. Knittel and A. Cundari

Si

tarnproii'e"', ~A "~
1.9- I~,~. ~'~.
NSW"-',• " , \ ~
"e, ",~ \ o \

°xo \Vico \

0.1 0.2 0,3 AI

1.75- ~ ~ -

!.70-

I I I I i
0.05 0,10 0.15 0.20 0.25 0.30 A l
Fig. 4. Evolution of the clinopyroxenes from the Cordon Syenite Complex, showing the
evolution from a) compositions with (Si + A1) < 2, through b) compositions with (Si +
A1) ,,~ 2 to c) compositions with (Si + A1) > 2. Analyses in Figs. a, b, c, correspond to the
analyses in Fig. 2, respectively. Symbols as in Fig. 2. Generalized fields for clinopyroxenes
from lamproites (Carmichael, 1967; Sheraton and Cundari, 1980; Kuehner et al., 1981; Jaques
et al., 1984), clinopyroxenes from the New South Wales leucitites (Cundari, 1973), and
clinopyroxenes from the Vico, Vulsini, and Sabatini lavas, Roman Region (Cundari, 1975;
Holm, 1982, Dal Negro et al., 1985) are shown for comparison. Note that for all clinopyroxene
suites from the Cordon Syenite Complex (Si + A1) increases with increasing AI.
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 173

i I I I 1 I I
Si
m

1.9-

1.8-

L I I I I I
0.1 0.2 0.] AI
Fig. 4

Table 2b. Typical chemical compositions and structural formulae of

clinopyroxenes from samples KN17 and KN18

Sample KN18 KN18 KN18 KN18 KN17 KN17 KN17

No. 187 188 191 190 112 114 113

core rim core dm core outer core rim

SiO2 48.32 50.11 47.78 49.42 51.79 51.81 48.23

TiO2 0.62 0.82 0.54 0.57 0.48 0.49 0.80
AI203 4.69 3.17 5.11 3.45 2.79 3.09 5.51
Fe203 * 7.29 5.21 7.33 5.99 2.73 1.89 5.60
FeO* 2.81 4.58 3.13 2.76 2.53 3.75 2.98
MnO 0.21 0.49 0.30 0.36 0.13 0.17 0.20
MgO 12.45 12.29 12.10 13.04 16.21 15.55 13.52
CaO 23.80 23.13 23.63 23.67 23.22 23.04 23.07
Na20 0.57 0.87 0.50 0.63 0.23 0.26 0.33
Cr203 0.07 0.00 0.00 0.00 0.26 0.28 0.06
100.83 100.67 100.42 99.89 100.36 100.33 100.31

Cations on the basis of 4 cations and 6 oxygens

Si 1.797 1.866 1.787 1.847 1.894 1.899 1.790
AI Iv 0.203 0.134 0.213 0.152 0.106 0.101 0.210
"13 0.000 0.000 0.000 0.001 0.000 0.000 0.000
2.000 2.000 2.000 2.000 2.000 2.000 2.000

AI VI 0.003 0.005 0.004 0.000 0.014 0.032 0.031

"li 0.017 0~023 0.015 0.015 0.013 0.013 0.022
Mg 0.690 0.683 0.675 0.726 0.884 0.850 0.748
Fe2+ 0.087 0.143 0.098 0.086 0.077 0.115 0.093
Fe 3+ 0.204 0.146 0.206 0.169 0.075 0.052 0.156
Cr 0.002 0.000 0.000 0.000 0.008 0.008 0.002
Ca 0.948 0.923 0.947 0.948 0.910 0.905 0.917
Na 0.041 0.063 0.037 0.045 0.016 0.019 0.024
Mn 0.007 0.015 0.010 0.011 0.004 0.005 0.006
2.000 2.000 2.000 2.000 2.000 2.000 2.000

* partitioned on the basis of 4.00 cations and 6.00 oxygens

174 U. Knittel and A. Cundari

their xenocrystal nature. Type 2 salites are the only clinopyroxene in syenite KN13
associated with plagioclase.
Clinopyroxene crystals from tephritic phonolites, pyroxenites, lusitanites, sye-
hires, alkali syenites and monzonites (Table 2b) are usually euhedral to subhedral and
faintly green in colour. Zoning and sector zoning is visible in many specimens.
Compositionally, they are salites with limited Ca- and Fe-enrichment in a Ca-Mg-
E(Fe + Mn) quadrilateral (Fig. 3). In contrast to the clinopyroxenes from the pseu-
doleucite phonolites, they contain (Si + A1) > 2. If all available data are plotted in
terms of A1 vs. Si, atoms per formula unit, (Fig. 4a-c), a complete gradation is found
from samples containing T-site deficient clinopyroxenes to samples containing only
clinopyroxenes with (Si + A1) > 2. The T-site deficient clinopyroxenes are in general
more Mg-rich than those containing (Si + AI) > 2, consistent with similar T-site
deficient clinopyroxenes from the Roman Region (Cundari and Salviulo, 1987).

Phlogopite
Within individual samples phlogopite compositions are very uniform, consistent
with textural relationships between phlogopite and coexisting minerals, which in-
dicate that phlogopite formed at a late stage (phlogopite is subhedral where it is
intergrown with minerals other than K-feldspar, but is usually euhedral where
enclosed only by K-feldspar). Phlogopite generally contains just enough A1 to
balance the Si-deficiencies and thus corresponds to phlogopite from the potassic
lavas of the Roman Region with regard to its A1 and Si contents (Fig. 5). No

At I I L I t I I J
3.0 _]

I I i I I I 1
5.2 5.6 6.0 6.4 Si

Fig. 5. Phlogopite from the Cordon Syenite Complex, compared with phlogopite from New
South Wales leucitites, Leucite Hills lamproites, Vico and Vulsini complexes, in terms of A1
vs. Si [-atoms per formula unit on the basis of 22.00 oxygen and 4(OH + C1 + F)]. Data
sources as for Fig. 4. Circles with dot indicate phlogopite from samples containing clinopyr-
oxene with (Si + A1) < 2
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 175
Table 3. Representative chemical analyses for phlogopite, amphibole, alkali feldspar
and plagioclase (see Appendix for key to specimen)

mineral phlogopite amphibole alkali feldspar plagioclase

sample KN1 KN18 B37 B37 KN1 Q43 Q43 Q43
No. 412 319 328 329 361 516 364 368

SiO2 36.12 40.05 37.89 37.68 62.88 63.70 54.29 59.24

TiO2 3.51 0.89 1.77 1.36 n.d. n.d. n.d.
n.d.
A1203 14.77 10.98 13.06 13.12 18.23 19.30 27.29 23.87
Fe203 5.881 4.421 5 . 3 4 1 0 . 3 2 2 0 . 1 0 2 0.312 0.352
FeO 13.393 11.191 15.951 14.381
MnO 0.56 0.69 0.55 0.47 n.d. n.d. n.d. n.d.
MgO 16.36 11.17 8.13 8.59 n.d. n.d. n.d. n.d.
CaO 0.00 11.53 11.76 12.02 0.00 0.47 10.57 5.53
Na20 0.34 2.60 1.75 1.60 1.90 3.51 5.46 7.94
K20 10.08 1.87 2.67 2.85 14.08 11.04 0.30 1.08
SrO n.d. n.d. n.d. n.d. 0.84 0.19 0.64 0.27
BaO n.d. n.d. n.d. n.d. 0.41 0.23 0.08 0.14
F 2.12 0.99 0.32 0.30
OH (calc.) 3.01 1.53 1.81 1.81
T, 100.27 99.38 100.08 99.52 98.69 98.52 98.94 98.42

Structural formulae on the basis of 22 oxygen (mica), 23 oxygen (amphibole) and 8 oxygen
(feldspar) respectively
Si 5.426 6.132 5.870 5.851 2.961 2.967 2.491 2.699
AI IV 2.574 1.868 2.130 2.149 1.012 1.013 1.475 1.282
AIvl 0.042 0.114 0.255 0.253
li 0.397 0.102 0.207 0.159
Fe3+ 0.678 0.515 0.624 0.011 0.003 0.011 0.012
Fe2+ 1.682 1.432 2.066 1.868
Mn 0.072 0.090 0.072 0.062
Mg 3.663 2.549 1.878 1.989
Ca 0.000 0.0314 0.0074 0.0464 0.006 0.024 0.520 0.270
Ca(M4) 1.861 1.945 1.954
Na 0.098 0.773 0.527 0.482 0.174 0.316 0.486 0.701
K 1.932 0.366 0.528 0.564 0.846 0.652 0.018 0.063
Sr 0.023 0.005 0.017 0.007
Ba 0.006 0.004 0.001 0.002
F 1.009 0.478 0.156 0.154

n.d. = not determined

CI in biotite and amphibole below detection limit (<0.1%)
1 iron partitioned on the basis of 16 cations and 23 oxygens per formula unit
2 total iron as Fe203
3 total iron as FeO
4Cain M1, M2, M3.

systematic variation was observed in phlogopite compositions from samples that

contain clinopyroxene with (Si + A1) < 2 and those that contain clinopyroxenes
with (Si + A1) > 2 (Table 3).

Amphibole
Only two of the samples selected for mineralogical studies contain amphibole, in
contrast to the Palali intrusion, where amphibole is a common rock-forming phase
(Albrecht, 1986; Albrecht and Knittel, in press). The investigated amphibole is a
176 U. Knittel and A. Cundari

K-rich, Mg-hastingsite (Leake, 1978). All analyzed amphibole crystals contain en-
ough A1 to balance the Si-deficiency in the T-site. In the highly evolved amphibole-
bearing syenites, represented by sample KN18, amphibole forms large crystals,
poikilitically enclosing other minerals. This texture indicates that it was the last
phase to crystallize. However, in sample B37 amphibole forms euhedral, prismatic,
distinctly bluish-green microphenocrysts, which are characterized by K > Na
(atoms). Selected analyses in Table 3 illustrate the compositional differences between
amphiboles in highly evolved syenites and B37.
An interesting feature of these amphiboles is that from the microprobe data no
structural formula may be calculated which simultaneously satisfies the following
constraints:
1. all positions, except the A-position to be completely filled,
2. the sum of cations (relative to 23 oxygens) to be less than or equal to 16,
3. Ca to be restricted to the M4-site.
This is due to the high alkali content of these amphiboles. Formulae on the basis
of (Ca + Na + K) = 3 violate constraint (1), formulae on the basis "sum of cations
excluding Ca, Na, and K equal 13" violate constraint (2), and formulae on the basis
of "sum of cations equal 16" violate constraint (3) (Table 3). The same observation
applies to amphiboles from the Palali Intrusion (Albrecht and Knittel, in press), the
Roman Region (Cundari, 1979), and the potassic volcanics of Mt. Muriah, Indonesia
(Whitford, 1975). This suggests that Ca-amphiboles from alkaline rocks, similar to
some alkali amphiboles (Hawthorne, 1976), may accommodate limited amounts of
Ca in other than the M4-site and are, therefore, an important paragenetic indicator.

Feldspar
Alkali feldspar is an ubiquitous phase in the subvolcanic rocks of the CSC. In general,
it becomes more sodic in successively more evolved rocks (syenite-monzonite-
amphibole-bearing syenite). The pseudoleucite phonolites contain the most potassic
alkali feldspars (Or80.92) which are distinguished from the alkali feldspars of the
syenite-monzonite-amphibole syenite suite (Or56.75) also by low contents in Ca
(Table 3). In this respect they resemble alkali feldspar from peralkaline rocks.
However, they differ from the latter by their lack of high Fe contents (Fig. 6). On the
other hand, they resemble alkali feldspar compositions from the New South Wales
leucitites. Notably, the alkali feldspars of CSC samples with clinopyroxenes that
contain A1Iv delineate a trend from the field of the NSW leucitite feldspars to that
of Roman Region feldspars (Fig. 6).
Plagioclase is present only in syenites, some alkali syenties and monzonite. It
was not observed in pseudoleucite phonolites and lusitanites. It might have been
present in ATP, as indicated by habit of albite pseudomorphs. Its compositional
variation in syenites, alkali syenites and monzonite may be considerable within an
individual sample, e.g. An3o.so in monzonite Q51. Most analyses are in the range
An4o-An55. Compared to plagioclase from several volcanoes of the Roman Region
(An70.85; Cundari, 1975, 1979; Luhr and Giannetti, 1987), the CSC plagioclase is
distinctly more sodic. Despite this, CSC plagioclase is too calcic, relative to the
co-existing alkali feldspar, for two-feldspar thermometers to be applied (see discus-
sion in Luhr and Giannetti, 1987 and references therein).
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 177

1.00, [monzonite

0.80

Region (Vico, Vulsini)

0.60

CaO

0.40

#honolite
0.20 Leucite Hills
:it i t e s .........a:.~~:~:#::~:::!
::i-iii#ii:~iiii@i

0.00 1.00 2.00 3.00 4.00 5.00

Fe203

Fig. 6. Alkali feldspars from the Cordon Syenite Complex (filled symbols, pslc-phonolite =
pseudoleucite phonolite) plotted in terms of CaO vs. Fe2 03 (%wt.). Data for alkali feldspar
from New South Wales leucities (squares; Cundari, 1973; Birch, 1978; Ferguson and Cundari,
1982), Leucite Hills lamproites (circles; Carmichael, 1967), and the Roman Region lavas
(triangles; Vico: Cundari, 1975; Vulsini: Holm, 1982) are shown for comparison

Spinel
Spinel from CSC rocks falls into two separate groups. Group I spinel is nearly pure
magnetite with TiO 2 < 0.45%, A1203 < 0.33%, and no detectable MgO and Cr203.
On the other hand, group II spinel contains TiO2 > 3.2%, A1203 > 6.1%, and
MgO > 3.8%. Group II spinel is the only oxide found in samples CA1 and MAG4,
while all other samples contain almost exclusively group I spinel (some of these
samples also contain 1 or more grains with transitional compositions). Spinels from
both groups contain about 0.4-0.6% V205.

Petrogenetie Interpretation
Clinopyroxenes and alkali feldspars from individual specimens from CSC, in partic-
ular from all pseudoleucite phonolites, show features characteristic of the corre-
sponding analogues from peralkaline rocks. The consistent T-site configuration of
clinopyroxenes from individual CSC specimens (i.e. constant Si + Al) strongly argues
for cognate clinopyroxene crystallization from individual magma batches rather
than a xenocrystal origin. The CSC clinopyroxenes and alkali feldspars evolved from
compositions characteristic of peralkaline rocks towards compositions found in
miaskitic rocks, e.g., Roman Region HKS-type lavas (Figs. 4a-c and 6). Rocks with
Roman Region-HKS type clinopyroxene and alkali feldspar contain plagioclase,
similar to Roman Region HKS lavas, while most samples containing clinopyroxene
with (Si + A1) < 2 lack plagioclase. The magmatic evolution trend of the CSC from
peralkaline to miaskitic liquids is evidenced by the composition of late crystallized
178 U. Knittel and A. Cundari

minerals, e.g. mica and amphibole. These minerals are always similar to those found
in the HKS series of the Roman Region (Fig. 5), consistent with the CSC bulk-rock
compositions (Fig. 2). Because the bulk of the intrusive rocks falls at one extreme of
the evolutionary trend, i.e. typical Roman Region HKS mineralogy and bulk-rock
compositions, we believe that the compositional variation is not the result of
magma-mixing, which would have produced intermediate compositions between
end-members. Disequilibrium textures like those documented for potassic lavas of
the Highwood Mountains, Montana, and interpreted as evidence for magma-mixing
(O'Brian, 1988), were not found in the CSC.
The parental magma may have been similar in composition to that of the New
South Wales leucitites (Cundari, 1973), and similar rocks from North Vietnam
(Wagner and Velde, 1986), and Kalimantan (Wagner, 1986), supported by similarities
in mineral composition between these suites and CSC rocks. These leucitites show
the essential mineralogical and geochemical features of lamproites, i.e. they contain
diopside, Ti-rich phlogopite, and K-richterite with insufficient (Si + A1) to com-
pletely fill the tetrahedral sites. Mafic variants (MgO > 12 wt. ~) are generally low
in A12O3 ( < 12 wt. ~o),CaO ( <_9 wt. ~), and Na 2 0 ( < 2 wt. ~), and closely resemble
madupite from the Leucite Hills with regard to their chemical composition (Car-
michael, 1967; Kuehner et al.,1981).
In the CSC rocks, the absence of several minerals, e.g. olivine, Ti-rich phlogopite,
and K-richterite, commonly found in lamproites and leucitite of the New South
Wales type does not invalidate the hypothesis that the CSC magmas are derived
from peralkaline precursors. Olivine in some lamproites is xenocrystic and not
in equilibrium in Q-normative lamproites and thus may not necessarily occur in
a differentiated suite. Phenocrystal phlogopite is usually unstable in lamproite
(Mitchell, 1985) and if present may have been destroyed by reaction in the paren-
tal magma of the CSC suite. Groundmass phlogopite and K-richterite are late-
crystallized phases in lamproites and in the New South Wales suite and may have
not preceded the transition to a metaluminous type magma.
The transition from a peralkaline to an alkaline, metaluminous magma may
have been the result of one or several of the following processes:
1. Fractionation of Al-free alkali-bearing phases [e.g., priderite (K, Ba) (Ti, Fe)8016,
wadeite ZrK/Si 309],
2. Contamination of the magma with Al-rich materials,
3. Loss of alkalies.
The first possibility appears to be unlikely, because priderite is only a minor
constituent even in extremely Ti- and Ba-rich rocks, e.g., the Western Australian
lamproites (Jaques et al., 1984) and wadeite is a late-crystallized phase (Mitchell,
1985). Furthermore, these phases do not occur in the New South Wales, North
Vietnam, and Kalimantan leucitites.
Partial melting of granite xenoliths in the Hills Pond lamproite, Kansas, USA,
(Franks et al., 1971) attests to the capability of mafic potassic magmas to raise the
temperature of country rock above its solidus temperature. Mixing between potassic
magma and partial melts derived from the country rock may alter the geochemical
character of the former. This possibility, while theoretically arguable, may not be
evaluated in the present case, because assimilation of Luzon basement rocks would
not necessarily affect the CSC isotopic compositions and trace element systematics,
as all these rocks have typical geochemical arc signatures.
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 179

The third process is supported by many observations, e.g. the development of

K-feldspar-biotite assemblages at the contact of the intrusive complex of the CSC.
In view of the extensive metasomatic aureoles (fenites) surrounding many stocks of
alkaline rocks, the observation that condensates of magmatic gases are invariably
rich in K and Na (e.g., Chevrier and Le Guern, 1982), and the alkaline nature of
thermal waters from active volcanic regions, Bailey (1976) argued that it would be
surprising to find a differentiated alkaline suite that had not experienced alkali losses.
For example, lamproite sills that have intruded shales at the Hills Pond Dome have
transformed the shales to buchite-like rocks, composed essentially of sanidine and
dark mica (Franks et al., 1971). These are enriched in K, Ba, and to a lesser extent
Rb and depleted in SiO2, compared to their original composition (Franks et al.,
1971; Cullers et al., 1985). It should be noted that the lamproite sills at Hills Pond
are only about 1-5 m, at the most 20 m thick; they were emplaced at very shallow
levels (a few 100 m) and, thus, solidified rapidly. Exchange reactions between marie
potassic magma and host rocks are expected to be more extensive in deeper seated,
larger magma bodies due to the higher temperatures and the slower cooling rate
of the magma. Most lamproites have escaped extensive alkali losses and/or A1-
contamination mainly because they rose very rapidly to the Earth's surface, as
suggested by the associated mantle xenoliths (Bergman, 1987; Foley et al., 1987;
Sheraton and Cundari, 1980). In contrast, the CSC magmas probably evolved in a
crustal reservoir as they were subsequently emplaced as a differentiated magma suite
(Knittel, 1987). On the basis of the evidence presented we suggest that the CSC
magma has lost considerable amounts of alkalies during its residence within the
crust.
Changes to the (K + Na)/A1 ratio may not be a unique feature of the CSC. HKS
volcanics from the Roman Region contain clinopyroxenes which recorded a com-
plex history of multiple equilibrations with liquids of different composition and
(Na + K)/A1 ratios (Cundari, 1975, 1979, 1982; Cundari and Salviulo, 1987). In
particular, leueititic ash-flow tuffs of the Roccamonfina Volcano contain clinopyr-
oxenes with diopside cores characterized by (Si + A1)< 2 (Luhr and Giannetti,
1987). Furthermore clinopyroxenes from pyroxenite ejecta and megacrysts from
Somma-Vesuvius, representing possible precursors of the associated lavas, clearly
indicate that some genetically related batches of the Roman Region HKS magmas
that crystallized at shallower depth (< 5 kb) are peralkaline (Cundari, 1982; Cundari
and Salviulo, 1987).
Mineralogical data for two potassic rock samples from Vietnam (Wagner and
Velde, 1986) indicate that suites with closer affinites to lamproites may have
undergone similar transitions. One of the samples contains clinopyroxene with
(Si + A1) < 2 phlogopite with (Si + A1)< 8, while the other sample contains
clinopyroxene with (Si + A1) > 2 and mica with higher (Si + A1) (7.909 vs. 7.707
respectively).

Conclusions

The mineralogical study of the CSC demonstrates that multi-stage histories of

evolved magmas, which would not be detected by whole-rock geochemistry, are
recorded by some of the constituent minerals. The results of this study suggest that
180 U. Knittel and A. Cundari

metaluminous magmas may have been derived from peralkaline precursors, imply-
ing that HKS-type and lamproitic magmas are not necessarily related to mantle
sources that differed in composition and evolution. In view of this interpretation, it
is interesting to note that all known occurrences of Roman Region type lavas are
located in orogenic areas (the Roman Region, the Indonesian arc systems, and the
American Cordillera in Alaska; Foley et al., 1987). This environment is notable for
its paucity of primitive magmas, i.e. some factors (so far little understood) favour
extensive differentiation of mantle-derived magmas at destructive plate boundaries
(e.g., Gill, 1981). It has been argued above that lamproites retain their chemical
characteristics because of their rapid ascent to the Earth's surface. Thus the paucity
of lamproites and related rocks at destructive plate boundaries could be a con-
sequence of the factors that favour differentiation in this tectonic setting.
The suggested occurrence of marie peralkaline magmas in the Philippine island
arc does not imply a direct genetic relationship between subduction and generation
of HKS-type and peralkaline magmas. Potassic magmatism in the Philippine arc
occurred at a time when a subduction zone east of the Philippine arc was deactivated
and subduction along the western margin of the arc was initiated (Knittel, 1983,
1987). Also, the K-rich complexes in the Philippine arc do not overlay the deepest
parts of the deactivated subduction zone, but occur approximately in the middle of
the Mid-Tertiary arc. Likewise, a direct genetic relationship between subduction
and potassic magmatism in the Roman Region and the Indonesian arc is question-
able (Cundari, 1980; Varne, 1985; Varne and Foden, 1986; Vollmer, 1989).

Acknowledgements
This study was carried out at the University of Melbourne while UK was the recipient of a
research grant of Deutsche Forschungsgesellschaft. We thank Professors A. Peccerillo and
R. N. Thompson and two anonymous referees for their comments.

Appendix
Key to Specimens
KN1 Pseudoleucite phonolite. Chemical analysis given in Table 1.
KN7 Pseudoleucite phonolite. Chemical analysis given in Knittel, 1987.
KN13 Syenite containing clinopyroxene poikilitically enclosing mica. Chemical analy-
sis given Table 1.
B37 Amphibole-bearing syenite with epidote xenocrysts. Not analyzed in bulk.
CA1 Analcime-rich tephritic phonolite. Chemical analysis given in Knittel, 1987
Q51 Monzonite. Chemical analysis given in Table 1.
KN18 Amphibole-bearing syenite. Chemical analysis given in Table 1.
KN17 Tephritic phonolite without analcime phenocrysts,. Chemical analysis given in
Table 1.
MAG4 Analcime-rich tephritic phonolite. Chemical analysis given in Knittel, 1982.
Q43 Equigranular syenite. Chemical analysis given in Table 1.
JG6 Equigranular syenite, with xenocrysts derived from partially disintegrated pyr-
oxenite xenoliths.
Not analyzed in bulk.
 Mineralogical Evidence for the Derivation of Metaluminous Rocks 181

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