Precambrian Research 113 (2002) 269– 291

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Petrogenesis of metaluminous A-type rhyolites from the

St Francois Mountains, Missouri and the Mesoproterozoic
evolution of the southern Laurentian margin
Julian F. Menuge a,*, Timothy S. Brewer b, Cheryl M. Seeger c
a
Geology Department, Uni6ersity College Dublin, Belfield, Dublin 4, Ireland
b
Geology Department, Uni6ersity of Leicester, Leicester LE1 7RH, UK
c
Di6ision of Geology & Land Sur6ey, Department of Natural Resources, Rolla, MO 65401, USA

Received 28 July 2000; accepted 8 August 2001

Abstract

Predominantly acid volcanic and intrusive rocks of the approximately 1.48 Ga Eastern Granite– Rhyolite Province
are exposed only in the St Francois Mountains inlier, Missouri. Combined Nd isotopic, major and trace element
analyses are presented for the predominantly acid volcanic rocks of the St Francois Mountains. They are
metaluminous to mildly peraluminous, A-type compositions with positive initial mNd values of 3.1– 5.0. They are
interpreted to be the result of crystal fractionation of partially melted calc-alkaline igneous rocks formed at a recently
active subduction zone. The likelihood of a juvenile, calc-alkaline, subduction-generated protolith for the St Francois
Mountains rhyolites leads to a hypothesis in which dacitic parental magmas resulted from partial melting in a
continental ‘back-arc’ setting. Basaltic magmatism due to decompression melting of the mantle resulted from
lithospheric extension and thinning and provided the heat source for melting in the middle or lower crust.
Penecontemporaneous magmatism elsewhere in Laurentia included subduction related calc-alkaline rocks in the
Pinware Terrane of Labrador; some felsic igneous rocks of uncertain plate tectonic setting within the Grenville
Province also have 1.5–1.6 Ga TDM ages. These are interpreted as magmatic products of approximately 1.5 Ga
northward dipping subduction beneath much of the length of the southern margin of Laurentia. The Eastern Granite
Rhyolite Province is consequently seen as an integral inboard expression of this subduction related igneous activity.
Petrogenetic models involving a mantle plume or the development of a continental rift are not required to explain this
granite–rhyolite terrane and evidence against their involvement is discussed. © 2002 Elsevier Science B.V. All rights
reserved.

Keywords: Mesoproterozoic; Granite–rhyolite; A-type magmatism; Laurentia; Geochemistry

* Corresponding author. Tel.: + 353-1-7162141; fax: + 353-1-2837733.

E-mail addresses: j.f.menuge@ucd.ie (J.F. Menuge), tsb5@le.ac.uk (T.S. Brewer), nseegc@mail.dnr.state.mo.us (C.M. Seeger).

0301-9268/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0301-9268(01)00211-X
270 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
1. Introduction
Early Mesoproterozoic crustal development in
North America involved the production of rela-
tively large volumes of A-type felsic rocks, form-
ing a number of granite– rhyolite provinces. Some
authors have regarded these rocks as forming in
an anorogenic tectonic setting (Anderson, 1983;
Kisvarsanyi and Kisvarsanyi, 1990). This conclu-
sion was reached because they are largely unde-
formed and unmetamorphosed and also because
A-type geochemistry has tended to be equated
with anorogenic petrogenesis. This in part relates
to some confusion in the use of the term ‘A-type’.
Young A-type felsic rocks elsewhere whose tec-
tonic setting can be determined with confidence
did not all form in a strictly anorogenic setting
(e.g. Eby, 1992). Peraluminous to metaluminous
A-type rocks frequently occur in post-orogenic,
extensional settings (Eby, 1992). The petrogenesis
of the North American Mesoproterozoic granite –
rhyolite provinces, whose felsic rocks are predom-
inantly metaluminous to peraluminous, may be
related to orogenic processes (Rivers, 1997). Con-
sequently, unravelling the petrogenesis of these
felsic rocks provides a means to constrain their
tectonic setting and the nature and development
of the approximately 1.5 – 1.4 Ga Laurentian
margin.
This paper presents comprehensive major, trace
and rare earth element and Nd isotopic data for
early Mesoproterozoic rhyolitic volcanic rocks
from the St Francois Mountains of southeast
Missouri. The data constrain models for the pet-
rogenesis of the voluminous rhyolites, and hence
contribute to the debate on the origin of alumi-
nous A-type felsic rocks. Constraints are provided
on the tectonic setting of the St Francois Moun-
tains and the Eastern Granite – Rhyolite Province
of which they form a part. The conclusions
reached may be applicable to other Mesoprotero-
zoic granite –rhyolite provinces.
2. Geological background
The St Francois Mountains of southeast Mis-
souri contain the only exposure of the early Meso-
proterozoic Eastern Granite –Rhyolite Province,
whose geology has been summarised by
Kisvarsanyi and Kisvarsanyi (1990), Sims (1990).
Palaeozoic sedimentary rocks cover most of this
province but it outcrops as a 2500 km2 inlier in
the St Francois Mountains in a structural and
topographic high. The inlier consists of volcanic
rocks, almost entirely of rhyolitic composition,
which are intruded by granites and minor basic
and intermediate bodies (Fig. 1). Geochemical
and geochronological data from drill core samples
suggest that the Eastern Granite –Rhyolite
Province has an aerial extent of at least 60000
km2 (Kisvarsanyi, 1981; Van Schmus et al., 1996;
Lidiak, 1996).
The rhyolitic rocks, which are the focus of this
paper, are mostly welded, ash flow tuffs with
occasional air fall and water lain tuffs and rhy-
olitic lavas. Eruption of the tuffs has in some
cases been linked to caldera collapse structures
(Sides et al., 1981). Published major element data
for the acid volcanic rocks indicate that they are
high SiO2, subalkaline rhyolites with high K/Na
and Fe/Mg ratios and low CaO concentrations
(Kisvarsanyi, 1972; Bickford et al., 1981a; Sides et
al., 1981). They are characterised by perthite phe-
nocrysts and Fe-rich mafic minerals including fay-
alite, ferrosilite and ferrohastingsite (Kisvarsanyi
and Kisvarsanyi, 1990). Limited trace element
data indicate an A-type signature (Cullers et al.,
1981).
The granites have been subdivided into subvol-
canic massifs, ring intrusions and central plutons
(Kisvarsanyi, 1980, 1981; Kisvarsanyi and
Kisvarsanyi, 1990). The subvolcanic massifs are
biotite alkali granites, comagmatic with the rhyo-
lites, ranging in texture from granophyric to ra-
pakivi with increasing depth. Both the felsic
volcanic rocks and most of the granites which
intrude them have yielded igneous crystallisation
ages of 1.45 –1.50 Ga by the U–Pb zircon discor-
dia method; similar ages from drill core allow the
boundaries of the Eastern Granite –Rhyolite
Province to be defined (Bickford and Mose, 1975;
Bickford, 1976; Bickford et al., 1981b; Van
Schmus et al., 1996). The most precise age deter-
minations suggest that most volcanism occurred
at 1.48 Ga (Van Schmus et al., 1996).
 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291 271

Fig. 1. (a) Simplified geological map of the Mesoproterozoic rocks of the St Francois Mountains after Kisvarsanyi and Kisvarsanyi
(1990) with inset showing position within state of Missouri and showing area of Fig. 1(b). The map shows only generalised
Mesoproterozoic rock types and represents both outcrop controlled surface features and subsurface features inferred from
geophysical evidence, (b) simplified geological map of Arcadia region after Berry (1976) showing sampling localities.
272 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
The frequently porphyritic ring intrusions were
emplaced in ring fractures related to caldera
collapse and include amphibole granite, biotite–
hornblende granite, hornblende– biotite adamel-
lite and syenite. The Silver Mine Granite
biotite–amphibole granite ring pluton has been
dated at 1.48 Ga (Bickford and Mose, 1975). Like
the felsic volcanic rocks, both the subvolcanic
granites and those of the ring intrusions are pre-
dominantly metaluminous to peraluminous and
have A-type chemical characteristics (Bickford et
al., 1981a; Cullers et al., 1981). The alkaline,
A-type chemistry of the 1.48 Ga suite and the lack
of both metamorphism and deformation have led
to this event being described as anorogenic (An-
derson, 1983; Kisvarsanyi and Kisvarsanyi, 1990).
The central plutons are typically high-SiO2,
muscovite– biotite alkali granites of circular to
oval plan. They are enriched in Sn, W, Nb, Y, Be,
Li, Rb, Ba, U, Th and F which reside in a suite of
accessory minerals characteristic of Phanerozoic
granites associated with Sn– W mineralisation. On
the basis of crosscutting relationships at least
some are younger than the other two classes of
granite in the St Francois Mountains and U– Pb
zircon dating of the Graniteville Granite has
yielded an age of 1.38 Ga (Bickford et al., 1986).
The central plutons are regarded as outlying in-
trusions of the adjacent 1.34– 1.40 Ga old South-
ern Granite–Rhyolite Province of southwestern
Missouri, southern Kansas, Oklahoma and the
Texas panhandle (Thomas et al., 1984; Bickford
and Van Schmus, 1985; Van Schmus et al.,
1993a,b).
Fe-rich intermediate rocks, often called mag-
netite trachytes, form minor ring intrusions and
dykes and it has been suggested that some also
occur as lava flows intercalated with the rhyolitic
volcanics (Kisvarsanyi, 1981; Kisvarsanyi and
Kisvarsanyi, 1990). The latter would have to be ca
1.48 Ga old, but the intrusive members of the
suite may be part of the 1.38 Ga magmatic event
which produced the central plutons. There are no
published isotopic age determinations for any of
the intermediate igneous rocks.
Basic rocks have been divided into two groups
on the basis of their mineralogy and chemical
composition (Sylvester, 1984). The older Silver
Mine Mafic Group is olivine-free, exhibits granitic
xenocrysts and occurs as small aphanophyric
dykes (Sylvester, 1984); a basaltic flow (Blades
and Bickford, 1976) of similar composition is
known and hence this group of rocks are all
believed to be ca 1.48 Ga old (Sylvester, 1984).
Sm–Nd isotopic analysis of two subsurface gab-
bro plutons has yielded mineral-whole rock
isochron ages indistinguishable from 1.48 Ga,
though this technique leads to relatively large age
uncertainties (Van Schmus et al., 1996), and these
are probably part of the same magmatic event. A
study of mafic enclaves in the 1.48 Ga Silvermine
Granite (Lowell and Young, 1999) also implies
that basic and felsic magmas were at least in part
coeval. The occurrence of 1.48 Ga basic igneous
rocks has led some workers to describe the suite
as bimodal (e.g. Kisvarsanyi and Kisvarsanyi,
1990). However, the proportion of approximately
1.48 Ga old rock which is basic is much less than
5% at the present level of erosion, though the
possibility cannot be discounted that volumetri-
cally significant basaltic flows, since eroded,
erupted after the rhyolitic volcanics as part of the
same 1.48 Ga magmatic event. A second group of
basic rocks, the Skrainka Mafic Group, comprises
olivine-bearing, xenocryst-free basalt and dolerite
and occurs as dykes and irregular bodies intrud-
ing both the volcanic rocks and the granites
(Sylvester, 1984). U–Pb mineral dating yields ages
of ca 1.33 Ga for this suite (Rämö et al., 1994).
Subsurface samples of felsic igneous rocks from
the supposed extension of the Eastern Granite–
Rhyolite Province northeastwards from the St
Francois Mountains have been the subject of a
geochemical study. Although, these rocks are un-
dated, they have similar chemical signatures to the
St Francois Mountains rocks and suggest a com-
mon origin for the igneous rocks of the Eastern
Granite–Rhyolite Province (Lidiak, 1996). Whilst
rare in outcrop, Precambrian sedimentary rocks
are known from subsurface samples from the
Eastern Granite–Rhyolite Province, though none
are known in the St Francois Mountains inlier.
The Middle Run Formation of southwestern
Ohio, comprises sandstone, siltstone, shale and
conglomerate (Shrake et al., 1990, 1991). Some of
these rocks contain rhyolitic detritus and are no
 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
older than the granite– rhyolite complex (Lidiak,
1996), but Hauser (1993) has pointed out that it is
not known whether they are younger, or of the
same age, as the rhyolitic volcanics.
At least two major hydrothermal events have
affected the igneous rocks of the St Francois
Mountains. The earlier event is associated with a
number of Fe oxide deposits, some of which are
also enriched in Cu and REE (Kisvarsanyi and
Kisvarsanyi, 1990). At the Pea Ridge magnetite
mine, a U –Pb xenotime age of 14669 4 Ma has
confirmed that Fe oxide-REE mineralisation is
essentially coeval with volcanism, dated by U– Pb
zircon analysis of rhyolite from Pea Ridge at
147393 Ma (Van Schmus et al., 1996). This
mineralising event is an important consideration
in studies of the magmagenesis of the host igneous
rocks. The presence of associated REE minerali-
sation implies high REE carrying capacity by
hydrothermal fluids and demands caution in the
use of REE concentrations and initial Nd isotopic
ratios to determine the petrogenesis of the St
Francois Mountains igneous rocks.
A later hydrothermal event is probably associ-
ated with intrusion of later Mesoproterozoic, ap-
proximately 1.38 Ga old central plutons. It is
characterised by fluorite, and sometimes Sn and
W mineralisation and wallrock greisenisation
(Kisvarsanyi and Kisvarsanyi, 1990). Since this
high temperature style of mineralisation has been
shown elsewhere to both accompany and closely
follow granite intrusion, for example in Cornwall,
SW England (Chesley et al., 1993), this hydrother-
mal event probably accompanied 1.38 Ga magma-
tism and, therefore, post-dated rhyolitic
volcanism in the St Francois Mountains by about
100 Ma.
All the volcanic rocks of the St Francois Moun-
tains inlier have been hydrothermally altered but
the extent to which the two hydrothermal events
described were responsible is not known. Mose
and Bickford (1972) demonstrated a positive cor-
relation between apparent Rb– Sr ages of volcanic
rock samples and their Sr concentrations and
deduced that their Rb– Sr ages have been lowered
by Sr loss. Their Rb – Sr model ages cluster
around 1300 Ma, suggesting that the hydrother-
mal event associated with intrusion of the central
273
plutons may have been responsible. Alternatively,
the possibility of one or more additional, as yet
unrecognised, hydrothermal events cannot be
discounted.
The basement through, and on to which, the
volcanics were erupted is not exposed in the St
Francois Mountains. Younger sedimentary rocks
cover all of the contacts between the Eastern
Granite– Rhyolite Province and other parts of the
Precambrian basement. The position and nature
of the southeastern boundary is very poorly con-
strained. To the northwest, borehole data reveal
metamorphosed igneous and sedimentary rocks of
the Central Plains Orogen (Sims and Peterman,
1986; Bickford et al., 1986). This comprises a
northern belt of 1800–1700 Ma old rocks and a
southern belt of 1690–1630 Ma old rocks. These
may, respectively, represent arc accretion and
continental arc magmatism (Van Schmus et al.,
1993a). Lower Palaeozoic sedimentary rocks
cover the boundary with the Eastern Granite-
Rhyolite Province but the existence of ca 1.47 Ga
granitic rocks intruding the Central Plains Orogen
strongly suggests that the latter is at least locally
the basement to the Eastern Granite–Rhyolite
Province (Sims et al., 1987).
Sm– Nd isotopic studies (Nelson and DePaolo,
1985; Nelson, 1990; Bowring et al., 1991; Van
Schmus et al., 1996) have revealed that all the
acid rocks of the Eastern Granite–Rhyolite
Province have depleted mantle model ages (TDM)
not much greater than the igneous crystallisation
ages of the rocks. Van Schmus et al. (1996) have
additionally proposed that a relatively sharp NE-
SW boundary runs through Missouri separating
rocks of TDM \ 1550 Ma to the northwest from
rocks of TDM B 1550 Ma to the southeast.
3. Sample collection and petrography
Localities from which samples of rhyolitic vol-
canic rocks were collected are shown in Fig. 1.
Samples were collected primarily from two areas
where local relationships between volcanic units
are well exposed and have been mapped in detail.
The first comprises a well-exposed area of outcrop
in the Taum Sauk-Arcadia region of Iron County
274 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
(Fig. 1(b)), in the centre of the St Francois
Mountains, where the acid volcanics have been
mapped to a number of formations and their
petrography described (Berry, 1970, 1976; Berry
and Bickford, 1972). The second is the Pea
Ridge magnetite mine (Fig. 1(a)), which lies
northwest of the St Francois Mountains beneath
Lower Palaeozoic sandstones and dolomites. A
single sample was collected from Crane Lookout
Tower, Iron County. Lithologies, formation
names and map references for all samples are
given in Appendix A.
Examination of both outcrops and thin sec-
tions confirms that the acid volcanics are mostly
ash flow tuffs, as described by Berry (1970,
1976), Berry and Bickford (1972). Evidence
comes from the presence of fiammé, the occa-
sional presence of glass shards, now devitrified,
and the absence of grading features that would
be expected in air fall tuffs or volcaniclastic sed-
iments. Their matrixes consist mainly or entirely
of devitrified glass.
The ash flow tuffs generally comprise a ma-
roon to grey devitrified glassy matrix enclosing a
phenocryst population consisting of variable
proportions of K-feldspar, which is usually
perthitic, plagioclase and quartz. Total phe-
nocryst abundance varies from 5 to 50% and in
some cases alignment of long axes parallel to
flow is seen. Rounded and embayed quartz and
perthite phenocryst surfaces in some samples
suggest their partial resorption prior to eruption.
However, it should be noted that embayed phe-
nocrysts may represent highly localised resorp-
tion due to convection around gas bubbles, or
may represent a growth phenomenon (Don-
aldson and Henderson, 1988). No mafic phe-
nocrysts have been detected but occasionally
fine-grained opaques pick out the outlines of
stumpy prismatic crystals, suggesting the prior
existence of phenocrysts of Fe-rich olivine, py-
roxene or amphibole. All samples contain
equant opaque grains scattered through the de-
vitrified groundmass. Accessory phases include
apatite and zircon. The groundmass has in all
cases devitrified to a fine-grained mixture of
quartz and K-feldspar formed mainly or entirely
by devitrification of glass. The style of devitrifi-
cation crystallisation is in some cases radial, of-
ten centred on phenocrysts. In other cases
centimetre scale domains, elongated parallel to
flow, consist mainly of intergrown optically con-
tinuous quartz and K-feldspar. In yet others
there is no visible preferred devitrification crys-
tal orientation.
Two of the acid volcanic samples are not ash
flow tuffs. ARC5/96-1 exhibits flow banding,
with alternating red and white bands a few mil-
limetres wide. It is interpreted to be a rhyolite
flow. ARC5/96-4 contains abundant angular
lithic fragments of devitrified ash flow tuff up to
at least 1 cm in diameter. The groundmass ap-
pears to have a clastic texture. It exhibits vari-
able grain size and comprises quartz, K-feldspar
and equant opaques, the latter defining layering
which may be bedding. The rock is interpreted
as an agglomerate, but most if not all of its
constituents are pre-existing ash-flow tuffs.
Effects ascribed to hydrothermal alteration are
seen in all acid volcanic samples. There is ubiq-
uitous slight to sometimes moderate sericitisa-
tion of both phenocryst and groundmass
feldspars. The red to maroon colour displayed
to varying degree by all samples in hand speci-
men is seen to be due to hematitisation of the
groundmass; in samples ARC5/96-10, PEA10/
95-13, PEA10/95-15 and PEA10/95-17 hematite
has also invaded cracks in feldspar phenocrysts
and coated their surfaces. Occasional patches of
secondary calcite occur in most samples and
there is chloritisation of both feldspar phe-
nocrysts and of the groundmass in a few sam-
ples. Epidotisation of feldspars is common in
the samples from Pea Ridge mine but rare in
the Arcadia samples.
Several samples contain oval to elongate
patches a few millimetres long, with their long
axes parallel to flow, rimmed by tiny inward
growing euhedral prisms of feldspar (probably
K-feldspar) coated with hematite. The remainder
of the structure is filled with quartz. In most
samples these are isolated features but in ARC5/
96-1 and ARC5/96-10 they are abundant and
interconnected. Recrystallisation of the enclosing
groundmass makes it difficult to decide whether
these structures are vesicles or result from later
dissolution.
Table 1
Major and trace element data, acid volcanic rocks

Sample PEA10/95- PEA10/95- PEA10/95- PEA10/95- PEA10/95- PEA10/95- ARC5/96-1 ARC5/96-2 ARC5/96-3 ARC5/96-4 ARC5/96-5 ARC5/96-6 ARC5/96-7 ARC5/96-8 ARC5/96-9 ARC5/96-1
35 13 14 15 16 17 0
Lithology Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow Rhyolite Ash-flow Air-fall Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow
tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff

SiO2 70.04 72.08 71.11 77.06 74.61 75.84 76.70 78.07 73.95 70.73 77.93 70.31 74.62 71.35 68.96 76.91
TiO2 0.65 0.39 0.40 0.15 0.75 0.19 0.10 0.11 0.10 0.39 0.10 0.58 0.15 0.38 0.43 0.13
Al2O3 13.56 14.03 14.28 11.42 10.29 11.49 11.02 11.32 11.87 13.62 10.94 13.18 13.31 15.01 15.39 11.15
Fe2O3 5.10 2.76 2.90 2.37 5.24 2.39 3.12 2.49 2.83 4.72 2.20 4.75 2.44 3.63 3.81 2.88
MnO 0.09 0.04 0.05 0.02 0.02 0.01 0.08 0.05 0.18 0.17 0.05 0.03 0.03 0.03 0.07 0.03
MgO 0.13 0.57 0.37 0.17 1.01 0.18 B0.01 B0.01 B0.01 0.12 B0.01 B0.01 0.01 0.32 0.53 B0.01
CaO 1.68 0.52 2.07 0.27 1.03 0.62 B0.01 0.21 0.99 1.48 0.11 0.63 0.24 0.44 0.80 B0.01

J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291

Na2O 3.98 3.66 3.50 3.06 1.86 2.51 0.57 2.32 1.21 3.66 2.30 2.98 4.15 7.51 4.47 0.39
K2O 4.38 5.25 4.90 5.09 4.40 6.02 7.71 5.78 7.87 3.57 5.24 6.58 4.73 0.22 4.95 7.83
P2O5 0.17 0.07 0.06 0.02 0.13 0.03 0.01 B0.01 0.01 0.13 0.01 0.15 0.03 0.13 0.16 0.01
LOI 0.32 0.73 0.40 0.36 0.72 0.73 0.56 0.15 1.21 1.83 0.44 0.23 0.32 0.57 0.61 0.67
Total 100.10 100.09 100.05 99.99 100.06 100.00 99.81 100.42 100.13 100.43 99.29 99.41 100.03 99.58 100.16 99.95
Ba 969 1076 1027 409 1010 743 564 155 180 705 543 1346 780 54 1250 519
Co 4 5 4 4 8 4 B3 3 4 5 5 5 3 5 5 B3
Cr B3 B3 5 B3 7 8 8 5 5 B3 5 B3 5 10 10 81
Cu 1 15 6 4 7 3 29 2 6 11 2 6 6 6 2 5
Ga 18 17 19 19 13 19 17 19 21 19 17 15 20 20 17 20
Nb 15 17 16 23 19 19 16 16 16 13 16 13 13 10 9 16
Ni 8 8 14 8 8 11 6 3 5 3 4 4 2 0 4 6
Pb 23 5 19 6 5 3 58 16 13 7 6 6 6 7 6 9
Rb 148 164 192 204 187 213 309 230 305 132 172 142 96 5 155 308
S 10 70 148 43 11 465 71 26 19 30 37 67 44 35 22 58
Sc 10 5 4 B1 13 3 4 5 6 13 2 10 5 10 3 7
Sr 131 84 178 52 79 33 28 23 37 50 45 28 23 38 114 15
Th 10 20 20 27 13 16 12 12 17 11 8 12 12 3 8 10
U 3 6 7 3 3 5 4 2 8 3 3 6 5 4 1 B1
V 26 18 18 5 41 7 7 8 5 19 6 41 10 40 40 9
Y 71 59 54 42 59 69 46 69 68 48 62 39 65 37 16 52
Zn 92 22 47 8 19 6 28 39 59 57 33 18 11 29 38 24
Zr 372 335 365 303 400 354 413 412 456 269 358 307 330 226 244 394
La 39.50 46.36 46.36 42.47 41.91 39.50 6.77 54.06 57.66 35.76 45.68 48.22 26.05 33.13 32.11 5.75
Ce 84.27 99.07 99.07 86.38 88.93 84.27 20.94 115.77 118.63 80.31 97.20 106.02 56.59 82.05 63.90 18.04
Pr 10.12 12.01 12.01 9.45 10.42 10.12 2.75 15.19 13.70 10.14 12.10 10.76 7.33 10.02 7.20 2.38
Nd 42.23 46.33 46.33 37.86 37.92 42.23 10.88 59.62 54.04 42.85 52.66 37.52 31.15 36.57 25.84 12.04
Sm 9.48 10.04 10.04 5.71 7.63 9.48 3.19 12.67 10.38 8.82 10.68 6.04 6.66 6.57 4.83 3.30
Eu 1.67 2.23 2.23 0.74 1.30 1.67 0.17 0.47 0.42 1.60 0.63 1.44 0.92 1.25 1.05 0.30
Gd 9.54 10.34 10.34 6.71 8.98 9.54 3.87 10.01 9.63 7.50 8.87 6.59 7.19 4.94 4.59 3.87
Dy 10.24 10.80 10.80 7.56 9.64 10.24 6.90 11.34 11.28 8.03 9.82 7.59 9.02 4.79 4.47 7.82
Er 6.90 6.80 6.80 5.26 6.25 6.90 5.21 7.66 8.09 4.76 6.19 4.40 6.74 2.88 2.47 5.51
Yb 6.43 5.97 5.97 5.63 6.23 6.43 6.27 8.81 7.94 4.01 6.06 4.90 6.50 2.23 2.49 6.94
Lu 1.03 0.92 0.92 0.86 0.91 1.03 1.04 1.41 1.24 0.61 0.94 0.83 1.01 0.35 0.39 1.19
LaN 107.66 126.35 126.35 115.74 114.22 107.66 18.46 147.34 157.15 97.47 124.51 131.43 70.99 90.28 87.51 15.66
CeN 88.07 103.54 103.54 90.27 92.93 88.07 21.88 120.98 123.97 83.93 101.58 110.80 59.13 85.75 66.78 18.86
PrN 73.85 87.66 87.66 68.97 76.04 73.85 20.05 110.89 100.01 73.99 88.32 78.57 53.48 73.15 52.55 17.34
NdN 59.41 65.18 65.18 53.27 53.36 59.41 15.31 83.89 76.03 60.29 74.10 52.79 43.83 51.45 36.36 16.94
SmN 41.03 43.47 43.47 24.72 33.03 41.03 13.82 54.86 44.95 38.18 46.22 26.14 28.84 28.46 20.91 14.29
EuN 19.19 25.67 25.67 8.53 14.89 19.19 1.97 5.39 4.82 18.35 7.25 16.58 10.61 14.35 12.09 3.48

275
 276
J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
Table 1 (Continued)

Sample PEA10/95- PEA10/95- PEA10/95- PEA10/95- PEA10/95- PEA10/95- ARC5/96-1 ARC5/96-2 ARC5/96-3 ARC5/96-4 ARC5/96-5 ARC5/96-6 ARC5/96-7 ARC5/96-8 ARC5/96-9 ARC5/96-1
35 13 14 15 16 17 0
Lithology Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow Rhyolite Ash-flow Air-fall Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow Ash-flow
tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff tuff

GdN 31.11 33.73 33.73 21.89 29.29 31.11 12.64 32.67 31.42 24.48 28.94 21.49 23.45 16.11 14.98 12.61
DyN 26.85 28.32 28.32 19.83 25.29 26.85 18.11 29.75 29.60 21.06 25.75 19.92 23.67 12.56 11.72 20.51
ErN 27.70 27.30 27.30 21.13 25.10 27.70 20.94 30.78 32.47 19.12 24.85 17.66 27.07 11.55 9.90 22.13
YbN 25.95 24.12 24.12 22.73 25.17 25.95 25.32 35.57 32.07 16.20 24.47 19.80 26.23 9.01 10.04 28.00
LuN 27.02 24.15 24.15 22.66 23.88 27.02 27.36 37.04 32.66 16.03 24.80 21.77 26.44 9.18 10.26 31.21
Ce/Ce* 0.99 0.98 0.98 1.01 1.00 0.99 1.14 0.95 0.99 0.99 0.97 1.09 0.96 1.06 0.98 1.14
Eu/Eu* 0.54 0.67 0.67 0.37 0.48 0.54 0.15 0.13 0.13 0.60 0.20 0.70 0.41 0.67 0.68 0.26
(La/Yb)N 4.15 5.24 5.24 5.09 4.54 4.15 0.73 4.14 4.90 6.02 5.09 6.64 2.71 10.03 8.71 0.56
TZr (°C) 842 858 847 849 856 886 878 832 878 833 857 818
Zircon* Subhedral subhedral anhedral None anhedral subhedral euhedral anhedral subhedral anhedral subhedral subhedral
 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291 277

4. Analytical techniques (1996), Mansley et al., in preparation give full

All samples were jaw-crushed and then pow-
dered in an agate mill. 6– 8 g of this powder was
used to make pressed powder pellets with the
addition of a few mils of PVP-methylcellulose
binder. Glass fusion beads were made by
combining 1.0 g of rock powder with 5.0 g of Li
metaborate–Li tetraborate (80:20 mix) flux, using
the methods described by Harvey et al. (1996).
The major and trace elements were determined by
X-ray fluorescence spectrometry at Leicester Uni-
versity following the procedures of Harvey (1989).
Analyses of international reference materials indi-
cate that accuracy and precision is better than
0.5% for the major elements and better than 3%
for the trace elements.
REE analysis was carried out by inductively
coupled plasma atomic emission spectrometry
(ICP-OES) at Leicester University. In order to
ensure full dissolution of accessory phases sam-
ples were fused to a glass with c.1 g lithium
metaborate. The cooled glass was then dissolved
in a concentrated HF+ HNO3 mixture on an
open hot plate, thereby removing B by volatilisa-
tion. In all cases, the REE were then quantita-
tively separated on conventional cation exchange
columns in HCl. REE fractions were dissolved in
HNO3 for storage and analysis. Harvey et al.
details of the techniques with analyses of interna-
tional reference standards.
143
Nd/144Nd ratios, Sm and Nd concentrations
were determined by isotope dilution mass spec-
trometry at University College Dublin following
the methods described by Menuge (1988), with
minor modifications. All samples were isotopically
spiked with a mixed Sm–Nd tracer solutions and
were dissolved in pressurised digestion vessels in a
5:1 mixture of 40% HF and 70% HNO3. Repro-
ducibility of Sm and Nd concentrations is 92%
and of 147Sm/144Nd ratios is 9 0.2%. 143Nd/144Nd
ratios were normalised to 146Nd/144Nd = 0.7219
and are quoted relative to a 143Nd/144Nd ratio of
0.511845 for the La Jolla Nd standard. Within-
run precision of 143Nd/144Nd ratios is given in
Table 2; reproducibility of 143Nd /144Nd ratios is
9 0.00002. All errors are quoted at the 2|m level.
Sm and Nd spike solutions were calibrated
against the CIT mixed normal Sm–Nd solution
(Wasserburg et al. 1981). mNd values were calcu-
lated using present day values for CHUR of
143
Nd /144Nd = 0.512638 and 147Sm /144Nd =
0.1966, both renormalised from Jacobsen and
Wasserburg (1980). All the rocks are assigned an
age of 1.48 Ga for the purposes of calculating
their initial mNd values. TDM ages are calculated
relative to the depleted mantle model of DePaolo

Table 2
Sm–Nd isotopic data and initial Nd values

Sample Lithology 143

Nd/144Nd 2|m Sm Nd Sm/144Nd
147
Initial mNd TDM

PEA10/95-35 Ash-flow tuff 0.512235 0.000018 9.680 43.631 0.1341 4.0 1538
PEA10/95-13 Ash-flow tuff 0.512067 0.000014 9.393 46.887 0.1211 3.2 1598
PEA10/95-14 Ash-flow tuff 0.512062 0.000012 9.188 45.791 0.1213 3.1 1609
PEA10/95-15 Ash-flow tuff 0.511990 0.000018 7.061 39.603 0.1078 4.2 1508
PEA10/95-16 Ash-flow tuff 0.512086 0.000012 8.889 42.142 0.1275 2.3 1683
ARC5/96-1 Rhyolite lava 0.512354 0.000012 3.120 10.257 0.1839 −3.1
ARC5/96-2 Ash-flow tuff 0.512067 0.000014 12.601 63.566 0.1198 3.4 1576
ARC5/96-3 Air-fall tuff 0.512120 0.000014 10.534 53.462 0.1191 4.6 1480
ARC5/96-4 Ash-flow tuff 0.512145 0.000012 8.280 40.176 0.1246 4.1 1527
ARC5/96-5 Ash-flow tuff 0.512101 0.000012 10.150 49.377 0.1243 3.3 1596
ARC5/96-6 Ash-flow tuff 0.512039 0.000010 6.777 37.711 0.1086 5.0 1450
ARC5/96-7 Ash-flow tuff 0.512257 0.000012 6.581 29.953 0.1328 4.7 1473
ARC5/96-8 Ash-flow tuff 0.511955 0.000014 6.298 36.182 0.1052 4.0 1521
ARC5/96-9 Ash-flow tuff 0.512061 0.000016 5.159 27.601 0.1130 4.6 1479
ARC5/96-10 Ash-flow tuff 0.512398 0.000012 2.997 9.933 0.1824 −2.0
278 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
(1981) but have not been calculated for two sam-
ples (ARC5/96-1 and ARC5/96-10) with near
chondritic 147Sm/144Nd ratios.
5. Geochemical effects of hydrothermal alteration
All of the samples analysed have suffered at
least minor hydrothermal alteration, as has been
documented by previous workers (e.g. Brown,
1989; Lowell 1991). The most important effects
are noted briefly here because they must be re-
solved from magmatic effects in order to under-
stand the petrogenesis of the volcanics.
Sr isotopic data for the same sample suite indi-
cate that Rb/Sr ratios have been increased by up
to about 25% from magmatic values, presumably
by hydrothermal alteration (Menuge, unpubl.
data). There is no mineralogical evidence for sig-
nificant loss of Ca, and hence Sr, from acid
volcanics as sericitisation and other alteration of
feldspars is generally slight. Minor secondary cal-
cite is a common constituent, indicating mobility
of Ca and Sr, but it is not known whether this
reflects input from outside the volcanic pile or
purely internal chemical redistribution. Assuming
that the change in Rb/Sr ratio is entirely due to
increases of up to 25% in Rb concentration, these
concentrations must be treated with caution but
will have only a modest effect on geochemical
variation diagrams in which they are displayed on
a logarithmic scale. K/Ca ratios were presumably
increased in the same event as Rb/Sr ratios, so
that the acid volcanics were less potassic at the
time of their eruption than they are now.
As discussed in the next section, all of the acid
volcanics appear to display metaluminous to pera-
luminous characteristics using the Shand index. It
has been suggested that replacement of Na by K
can increase the Shand index (Kisvarsanyi, 1981)
and destroy original peralkaline characteristics. If
metasomatism was an important process, veining
(fluid pathways) and K-bearing secondary alter-
ation minerals, e.g. micas, should be more abun-
dant, whereas they are scarce in the majority of
samples, though some alteration by pore-filling
solutions during devitrification may have taken
place without leaving an obvious petrographic
signature. Secondly, K-metasomatism would not
only change the K content of the rock, but would
also produce significant changes in trace element
contents. However, K and Rb vary coherently
with LREE and HFSE, suggesting that large-scale
chemical changes were not induced during hy-
drothermal alteration. Neither is there any corre-
lation between K/Na ratio and the Shand index.
The lack of petrographic and geochemical evi-
dence to support K-metasomatism suggests that
this process did not produce a substantial effect
for most samples and that their major element
concentrations approximate magmatic values.
The REE patterns, and hence Sm–Nd isotopic
systems, of the volcanics give no indication of
hydrothermal alteration with the exception of two
samples, ARC5/96-1 and ARC 5/96-10. These
have much lower apparent initial mNd values (−
2.0 and −3.1) than the other samples (2.4–5.0).
Their flat REE patterns contrast with the moder-
ate LREE enrichment of the other samples. Most
notably they also have positive Ce anomalies,
implying that the event responsible was highly
oxidising compared with magmatic oxygen fugac-
ity but readily explained by the action of an
oxidising hydrothermal fluid. Since similar effects
are not seen in samples of acid volcanics from the
Pea Ridge mine, this effect is tentatively ascribed
to hydrothermal alteration accompanying later
granite intrusion.
Hematitisation of the groundmass occurs to a
greater or lesser extent in all samples. It is not
clear whether this reflects essentially redistribution
of iron on a small scale or movement over greater
distance. The possibility of large-scale movement
is suggested by the coating of hematite on sec-
ondary K-feldspar that is most extensively devel-
oped in amygdales or dissolution features in
ARC5/96-1 and ARC5/96-10, the samples that
have experienced the greatest changes to their
composition through hydrothermal alteration.
The consequences of the deductions regarding
hydrothermal alteration are that alkali, and possi-
bly alkaline earth element, concentrations must be
treated with caution for all samples, but have not
been altered so greatly as to preclude their use in
understanding magmatic processes. The excep-
tions are ARC5/96-1 and ARC 5/96-10, which
 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
Fig. 2. (a) Total alkali – silica plot, (b) molar Al2O3/(Na2O+
K2O) plotted against molar Al2O3/(CaO+ Na2O+ K2O).
display not only very large changes in their Rb/Sr
ratios but also major changes to their REE pat-
terns including Ce/Ce* \ 1.1; ARC5/96-8, which
has experienced Na metasomatism; and PEA10/
95-16, which contains significant Fe oxide veining.
Consequently, these four samples will be excluded
from consideration in the remainder of this paper.
Two other samples, ARC5/96-2 and ARC5/96-3,
have K/Na ratios higher than expected for mag-
matic values, but in other respects their chemical
compositions are coherent with the other samples.
6. Results
Major, trace and rare earth element data are
given in Table 1. Data are plotted on the total
alkali–silica plot (Fig. 2(a)) and are strongly clus-
tered in the rhyolite field. For brevity, the vol-
canics will be referred to as rhyolites in the
remainder of this paper. The samples analysed
279
range from metaluminous to mildly peralumi-
nous, with a few samples being more strongly
peraluminous (Fig. 2(b)). Similar trends are ap-
parent in previously published data (Kisvarsanyi,
1972; Bickford et al., 1981a), although these also
range marginally into the peralkaline field. Pub-
lished analyses of St Francois Mountains granite
samples (Kisvarsanyi, 1972; Bickford et al.,
1981a) encompass the range exhibited by the rhy-
olites but cover a wider range of compositions in
both the metaluminous and peraluminous fields.
This may in part be due to the greater number of
samples analysed.
All samples have negative Eu anomalies with
Eu/Eu* = 0.1–0.7 and all show moderate LREE
enrichment and flat HREE patterns, with the size
of the Eu anomaly tending to be greater where the
concentrations of the other REE are higher. Other
than differences in Eu anomaly, REE patterns are
subparallel for all samples (Fig. 3(a)). Similar
partial REE patterns were obtained by Cullers et
al. (1981) for the 1.48 Ga intrusive suite and are
typical of A-type acid magmatism globally. A plot
of Eu/Eu* against Zr shows a broad negative
correlation (Fig. 3(b)). No published full REE
analyses of granites are available for comparison.
A similar negative correlation can be seen on a
plot of Eu/Eu* against SiO2 concentration (Fig.
3(c)). These correlations are consistent with
greater feldspar fractionation in the more evolved
compositions. A logarithmic plot of Ba against Sr,
designed to discriminate between plagioclase and
potassium feldspar crystallisation, shows a moder-
ate correlation with a fairly steep slope, suggesting
that potassium feldspar crystallisation was pre-
dominant over plagioclase crystallisation (Fig.
3(d)). The possibility of the introduction of
Palaeozoic hydrothermal Ba must be borne in
mind when interpreting this diagram, though the
extreme Ba/Sr ratios expected of such fluids
should produce vertical trends.
Magmatic temperatures may be estimated by
assuming that the rhyolites are saturated in zirco-
nium, using the approach of Watson and Har-
rison (1983). The calculated temperatures range
from 818 to 886 °C (Table 1). U–Pb zircon dates
consistent with geological constraints on the age
of volcanism have been obtained from euhedral
280 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
zircons separated from the Royal Gorge Rhyolite
(Van Schmus et al., 1996), indicating that at least
some of the rhyolitic magmas were saturated
with respect to Zr. However, Zr concentration is
not, as would be expected, inversely correlated
with Zr saturation temperature, suggesting Zr
undersaturation of the less fractionated rhyolitic
magmas. Consequently the zircon saturation tem-
peratures of the most fractionated samples, taken
to be those with Eu/Eu* no greater than 0.2, are
probably the closest to true magmatic tempera-
tures. These three samples yield temperatures of
886 °C (ARC5/96-2), 878 °C (ARC5/95-3) and
878 °C (ARC5/96-5). Some support for this hy-
pothesis comes from microscopic examination of
the rhyolites. Of the three samples yielding the
highest zircon saturation temperatures, one con-
tains euhedral prismatic zircons and the other
two contain subhedral prisms. Euhedral zircons
were not detected in any of the other samples,
many of which contain anhedral zircons sugges-
Fig. 3. (a) REE concentrations, chondrite-normalised after Evensen et al. (1978), (b) Eu/Eu* versus Zr, (c) Eu/Eu* versus SiO2, (d)
Ba versus Sr.
tive of resorption, or no visible zircon at all
(Table 1). The high apparent magmatic tempera-
tures calculated are typical of A-type felsic mag-
mas world-wide.
Sm–Nd isotopic data are given in Table 2 and
initial mNd values are plotted on Fig. 4. An age of
1480 Ma is assumed for all samples. Initial mNd
values range from 3.1 up to 5.0, i.e. from just
below to approximately equal to the value of 4.6
expected for the depleted mantle 1480 Ma ago
(DePaolo, 1981). Expressed as TDM ages, the rhy-
olites range from 1450 to 1680 Ma. It is notewor-
thy that the samples from the Pea Ridge mine
have higher mean TDM age than the other sam-
ples. Pea Ridge lies close to the TDM boundary
proposed by Van Schmus et al. (1996), which
they suggested was relatively sharp. Consider-
ation of the data presented by Van Schmus et al.
(1996) and in the present work suggests a gradual
change over perhaps 100–200 km in TDM ages of
rhyolitic and granitic rocks.
 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291 281

Fig. 4. mNd versus time, showing the Nd isotopic evolution

(Nelson and DePaolo, 1985) of two 1.64 Ga old rocks from
the Southern Central Plains Orogen (Van Schmus et al., 1996)
and the model depleted mantle (DePaolo, 1981) for compari-
son.

The rhyolites have marked depletions in Nb, Sr,

P, Eu and Ti, are strongly enriched in highly
incompatible trace elements and have near flat
concentration profiles of the high field strength
elements (HFSE) (Fig. 5). Variations in most of
these elements amongst the rhyolites are likely to
be due mainly to crustal crystal fractionation, e.g.
Sr and Eu control by feldspar fractionation and P
control by apatite fractionation. However, all
samples are Nb depleted and this feature is likely
to be inherited from the source rocks melted to
produce the acid magmas. The alternative expla-
nation of control by crystallisation of ilmenite or

Fig. 6. (a) Nb versus Y (Pearce et al. 1984), (b) Rb-Y + Nb

(Pearce et al. 1984) and (c) Zr versus 10000. Ga/Al (Whalen et
al. 1987) tectonic discrimination diagrams.

titanite is unlikely because these minerals were not

Fig. 5. Incompatible element variation, normalised to primi-
tive mantle (Sun and McDonough, 1989).
found in thin section and because there is no
correlation between Nb and Ti concentrations in
the samples analysed.
In granitoid discrimination diagrams, the rhyo-
lites typically plot in the A-type and the within-
plate fields (Fig. 6). Further subdivision of the
282 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
A-type signatures suggests that they are typical of
magmas generated by the partial melting of calc-
alkaline rocks. For example, on the plot of Nb
against Y, the data plot in the A2 field of Eby
(1992). They also plot in this field in the triangu-
lar Y–Nb –3Ga and Y – Nb – Ce diagrams (not
illustrated) (Eby 1992). However, it must be em-
phasised that these diagrams do not provide
unique solutions (Förster et al., 1997). The posi-
tion of the St Francois rhyolite data is typical of
felsic rocks produced by either fractionation from
I-type granitoids (cf. King et al., 1997), or those
generated in continental back-arc settings (cf.
Förster et al., 1997).
7. Geochemical constraints on rhyolite
petrogenesis
The chemical compositions of the rhyolites are
consistent with their formation by fractional crys-
tallisation, primarily of plagioclase and K-
feldspar, from a dacitic or less siliceous melt (Fig.
3). However, the parental magma was probably
not much less siliceous than dacite because there
are no 1.48 Ga igneous rocks less siliceous than
67% SiO2 (Fig. 2(a)), except for very minor
basaltic and intermediate lavas and intrusions.
Derivation of acid magma by fractional crystalli-
sation of a basaltic or even intermediate melt is,
therefore, unlikely. Consequently, although a sub-
ordinate mantle derived component cannot be
ruled out, the acid magmas must have formed
primarily by partial melting of pre-existing crustal
rocks. A similar conclusion was reached by
Cullers et al. (1981) on the basis of geochemical
and isotopic analysis of plutonic rocks believed to
be broadly comagmatic with the rhyolites. The
high initial mNd values of the rhyolites imply that
the crustal rocks melted were no more than about
50 Ma older than the volcanics themselves. A
similar conclusion was reached by other authors
mainly on the basis of Nd isotopic analysis of
granites (Nelson and DePaolo, 1985; Nelson,
1990; Bowring et al., 1991; Van Schmus et al.,
1996).
The REE and HFSE in particular identify the
rhyolites as A-type (Fig. 5). Following the subdi-
vision of A-type granitic rocks proposed by Eby
(1992), the St Francois Mountains rhyolites are
A2-type. Eby (1992) argued that, unlike the
mainly peralkaline A1-type granitic rocks, A2-
type magmas are produced by partial melting of
pre-existing crustal rocks. In particular, their trace
element signatures are consistent with derivation
by partial melting of calc-alkaline igneous rocks.
Taken together with their metaluminous to mildly
peraluminous compositions, high initial mNd values
and lack of metamorphism and deformation,
these characteristics suggest that the St Francois
Mountains rhyolites formed by partial melting of
almost contemporaneous calc-alkaline rocks. As-
suming the latter formed in a destructive margin
tectonic setting, the rhyolites may have formed in
an extensional setting within the continental plate
overlying an active, or recently active, subduction
zone.
The scarcity of 1.48 Ga old basaltic rocks in the
St Francois Mountains, and the absence of high
temperature basic rocks such as picrites, suggest
that a mantle plume was not involved in the
formation of any of the St Francois Mountains
igneous rocks. The only dated basic rocks of
likely ca 1.48 Ga age are plutons with positive
initial mNd values similar to those of the 1.48 Ga
rhyolites, interpreted by Van Schmus et al. (1996)
as resulting from the partial melting of litho-
spheric mantle; a chondritic or isotopically en-
riched mantle plume source is not required to
explain their compositions. In order for plumes to
form at the core–mantle boundary, the tempera-
ture anomaly required is such that voluminous
production of basaltic melts is expected when the
plume reaches the top of the mantle (Griffiths and
Campbell, 1990), even though there may be some
delay, accompanied by continuing uplift, if the
lithosphere is thick enough for plume incubation
(Watson and McKenzie, 1989; Kent et al., 1992).
The thermal anomaly associated with a plume
originating at the boundary between upper and
lower mantle would be no more than 300 km in
diameter (Griffiths and Campbell, 1990) and,
therefore, too small to account for the Eastern
Granite–Rhyolite Province. There is also no evi-
dence for doming of the crust immediately prior
to magmatism as would be expected if a mantle
 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
plume impinged on the lithosphere, for example
approximately 1.5 Ga clastic sedimentary rocks
are not known in adjoining parts of Laurentia.
If instead the Eastern Granite– Rhyolite
Province was situated in a continental back-arc
region (Rivers, 1997) in which back-arc extension
was the mechanism for generating the basaltic
melts, the rate of generation of basaltic magmas
by decompression could be very much less than in
the case of a mantle plume impinging on the base
of the lithosphere. In such a scenario it is possible
that large volumes of basic material would not be
erupted, but rather stored at the base of the crust
or in lower crustal magma chambers. These mag-
mas would then have provided the heat source to
cause extensive crustal melting of the fertile juve-
nile calc-alkaline crust, so producing the relatively
large volumes of metaluminous to peraluminous
A-type felsic volcanics. Furthermore, the produc-
tion of relatively large volumes of felsic magma by
crustal melting could well have acted as a barrier
to the ascent of mafic magmas, leading to essen-
tially a silicic large igneous province (cf.
Pankhurst et al., 1998). Magmatism in this case is
not anorogenic, but directly linked to subduction
zone processes.
8. Experimental constraints on rhyolite
petrogenesis
The overwhelming preponderance of acid, rela-
tive to basic and intermediate, magmatism is
strong evidence against petrogenesis of rhyolites
and comagmatic granites by simple crystal frac-
tionation of mantle derived magmas. Lowell and
Young (1999) presented evidence for localised
mixing and mingling of mafic and felsic magmas
within the Silvermine granite. Nevertheless, it is
difficult to reconcile models involving major
magma hybridisation or coupled assimilation and
fractional crystallisation with the overall distribu-
tion of rock types. Also, the presence of a major
component of basaltic magma would be expected
to increase the MgO, Ni and Cr concentrations
above the values seen and could only be plausible
if the least evolved rhyolites had themselves un-
dergone substantial subsequent fractional crys-
283
tallisation. Nevertheless, the high Zr saturation
temperatures suggest the involvement of basaltic
magmas as a heat source at some deeper level
within the crust.
We, therefore, start from the assumption that
the St Francois Mountains acid magmas were
melts of pre-existing crustal rocks and that they
contain no more than a minor component of
juvenile, mantle-derived magma. The problems
then are to constrain the nature of the crustal
protolith(s), the conditions under which melts
were extracted and the extent of subsequent frac-
tional crystallisation. Quantitative geochemical
modelling of the origin of the rhyolitic magmas is
beyond the scope of this paper. Here we discuss
the likely range of possible source rocks given the
geological setting and the constraints of experi-
mental petrology.
Of the rhyolites analysed in this study and
previously by Kisvarsanyi (1972), Bickford et al.
(1981a), SiO2 concentrations range upwards from
about 67%; below is a large compositional break.
It cannot be ruled out that some of the variation
in rhyolite composition reflects different degrees
of partial melting of their source rocks, or indeed
variation in source rock composition. However,
the ubiquitous presence of K-feldspar and plagio-
clase phenocrysts in the rhyolites leads us to the
assumption that variation in chemistry amongst
the rhyolites primarily reflects fractional crystalli-
sation and that the parental magma was no more
siliceous than 67% SiO2. The least siliceous sam-
ples are, therefore, the best guide to parental
magma composition. Like the rhyolites as a
whole, they are metaluminous to mildly peralumi-
nous, but tend to have higher CaO concentrations
of 1–2% and smaller negative Eu anomalies (Fig.
3(c)).
Some potential magma sources can be ruled out
by the results of experimental petrology or by
qualitative assessment of the expected trace ele-
ment compositions based on published mineral/
melt partition coefficients. All source rocks
containing more than 67% SiO2 fall into this
category. Given the evidence against involvement
of a mantle plume, dry melting of basalt is also
highly unlikely because of the very high tempera-
tures required. Experimental evidence indicates
284 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
that the only felsic magmas which can be pro-
duced by partial melting of metabasites are
tonalitic or granodioritic (e.g. Wyllie, 1984). Melt-
ing of pelitic sediments at low pressure seems
always to yield strongly peraluminous composi-
tions and can probably be ruled out. Similarly,
Montel and Vielzeuf (1997) carried out fluid-ab-
sent melting experiments on quartz-rich, alumi-
nous greywacke at 1– 10 kbars and at
780–1025 °C. All melts produced were peralumi-
nous and leucocratic, with 68– 74 wt.% SiO2. No
metaluminous compositions were produced.
Granulite facies crust from which I-type mag-
mas have already been extracted has been pro-
posed as the source of some A-type magmas (e.g.
Whalen et al., 1987). Cullers et al. (1993) have
pointed out that the near minimum melt composi-
tions of many A-type magmas, which include the
St Francois Mountains rhyolites and granites,
require quartz and K-feldspar in the source. How-
ever, K-feldspar, and possibly quartz, should have
been removed from the source by the large
amount of melting required for I-type granitic
melt separation (Cullers et al., 1993). Partial melt-
ing of granulite facies metasedimentary rocks is
also an unlikely source. Stevens et al. (1997)
showed that fluid-absent partial melting of mag-
nesian metapelites and metagreywackes produced
under granulite facies conditions at 5 and 10
kbars were always strongly peraluminous.
McCarthy and Patiño Douce (1997) simulated
the intrusion of basaltic magma into anhydrous
high-Al olivine tholeiite and into metapelite in the
lower crust at 11 kbar. The melt fractions of the
basalt at 1100 °C are dacitic and contain too
much CaO to fractionate to metaluminous A-type
granite magma, but the melt of pelite is rhyolitic
and similar to the more primitive St Francois
Mountains rhyolites though with somewhat
higher Al2O3 and CaO concentrations. Neverthe-
less such a parental magma might generate the St
Francois Mountains rhyolites by plagioclase frac-
tionation. The main drawback of this model is the
requirement for voluminous and extensive lower
crustal pelitic rocks. This seems unlikely for prim-
itive crust and would rather be expected at sites of
continental collision, though the possibility that
the 1.5 Ga Laurentian margin included recently
collided arc terranes cannot be ruled out.
Patiño Douce (1997) reported the results of the
experimental dehydration melting of calc-alkaline
tonalite at 950 °C. The major and trace element
characteristics of metaluminous A-type magmas
were broadly reproduced by incongruent melting
at 4 kbars, with crystallisation of calcic plagio-
clase and orthopyroxene. All melts will have nega-
tive Eu anomalies because of removal of Eu into
calcic plagioclase. At higher pressures, more calcic
and aluminous magmas are produced than are
common amongst metaluminous A-type magmas
because clinopyroxene, rather than plagioclase
and orthopyroxene, is increasingly crystallised by
incongruent melting (Patiño Douce, 1997). How-
ever, such melts could evolve to typical metalumi-
nous A-type compositions by fractional
crystallisation, especially of feldspars, at shallower
crustal levels. Given the apparently high tempera-
tures of the St Francois Mountains rhyolitic mag-
mas indicated by Zr saturation calculations, a
high degree of partial melting of tonalite, or dior-
ite, might produce dacitic magmas and would
imply major intrusions of basaltic magma into the
middle or lower crust.
A possible example of such a scenario is the
1.44 Ga Oak Creek batholith, Colorado (Cullers
et al., 1993). This was emplaced at a depth of
11–14 km with a liquidus temperature of 8809
60 °C and might represent the way in which other
aluminous A-type magmas behave in the middle
crust. The origin of this predominantly peralumi-
nous A-type leucogranite was modelled by 20–
30% melting of calc-alkaline intermediate rocks
(andesite, tonalite or granodiorite), or composi-
tionally equivalent metagreywacke (Cullers et al.,
1993), followed by extensive fractional crystallisa-
tion, producing cumulates with as little as 55 wt.%
SiO2 and generating dacitic to rhyolitic residual
magmas.
Turning to a modern example, Encarnación
and Mukasa (1997) have shown that the post-oro-
genic metaluminous high-K calc-alkaline I-type
Capoas granite in the Philippines has inherited the
geochemical signature of its source rocks, which
were calc-alkaline magmatic arc and/or collisional
granites. The Capoas granite formed after rifting
of its host terrane and its origin is unrelated to
either subduction or collision. Widespread
 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
basaltic magmatism is the only known possible
heat source (Encarnación and Mukasa, 1997).
Roberts and Clemens (1993) reviewed experimen-
tal data on possible source rocks of high-K calc-
alkaline I-type granitic rocks and concluded that
hydrated, calc-alkaline and high-K calc-alkaline
andesites and basaltic andesites are the only possi-
bilities. The St Francois Mountains rhyolites dis-
play trends on, for example, the Nb versus Y and
Rb versus Y+Nb discrimination diagrams lead-
ing back to the volcanic arc field (Fig. 6), suggest-
ing that they might be formed by fractionation of
melts derived from calc-alkaline source rocks.
We conclude that whilst deep crustal melting of
pelitic rocks cannot be ruled out, the source rocks
most plausible on experimental grounds which are
likely to be widespread are intermediate calc-alka-
line igneous rocks or immature clastic sediments
with an intermediate calc-alkaline provenance.
Quantitative modelling of major and trace ele-
ment compositions is required to better delimit
the compositional range of possible source rocks
and the relative effects of fractional crystallisation
and variable extent of partial melting.
9. Conclusions
The comprehensive geochemical and Nd iso-
topic data presented in this paper, combined with
field evidence and constraints from experimental
petrology, strongly favour a basement to the St
Francois Mountains felsic volcanics comprising
juvenile calc-alkaline material formed in an active
margin setting, which had only been recently ac-
creted onto the continental margin. Previous pet-
rogenetic models, which have suggested a mantle
plume origin for the St Francois Mountains
rocks, have the problem of identifying a mecha-
nism to produce both very minor quantities of
erupted basic magmas and very extensive crustal
melting. We propose that, following accretion and
a jump southwards in the position of subduction,
the St Francois Mountains region was then lo-
cated in a continental back-arc setting founded
upon juvenile calc-alkaline crust. Extension asso-
ciated with the back-arc setting, perhaps accom-
panied by slab break off, allowed for the
285
generation of basic magmas. The majority of
these were stored either at the base of the crust or
in lower crustal magma chambers, which then
provided a major thermal input to the crust. This
thermal input may have partly aided crustal ex-
tension due to heat softening of the crust. A
similar explanation has been proposed for wide-
spread Mesozoic silicic magmatism, partially of
A-type chemistry, in Patagonia and West Antarc-
tica (Pankhurst et al., 1998).
The juvenile nature of the crust, probably a
mixture of calc-alkaline granitoids and low grade
metasedimentary rocks which were accreted and
deposited along the earlier Laurentian margin,
was critical to the formation of large volumes of
felsic volcanics. The lower parts of this juvenile
crust, when repeatedly injected by mafic magmas,
could have generated large volumes of silicic
melts. These would have tended to form density
traps to ascending basaltic melts (Pankhurst et al.,
1998), so leading to a large volcanic province
characterised by mainly metaluminous to mildly
peraluminous A-type felsic volcanics. Occasional
batches of basic magmas did break through these
regions, but represent a very small proportion of
the eruptive products. However, the basic magma-
tism is critical as the driving mechanism for the
melting of the deeper crust. Much of the felsic
magma appears to have been stored in upper
crustal magma chambers, where fractionation of
feldspars, quartz and minor ferromagnesian
phases occurred prior to eruption. The extent of
crustal contamination in such a setting is difficult
to assess because of the juvenile nature of the
pre-existing crust, whose Nd isotopic composi-
tions were similar to those of the evolving
magmas.
In this type of model it is evident that the felsic
volcanism is a distal expression of orogenic pro-
cesses, which support the view that the Meso-
proterozoic margin of North America was an
active continental margin involving terrain accre-
tion and outwardly stepping subduction zones.
Further to the northeast, early Mesoproterozoic
crustal evolution is recorded by events in the
Pinware terrain (Gower, 1996). This is an area of
essentially calc-alkaline magmatism generated by
subduction beneath Labradorian crust (Rivers,
286 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291

1997; Gower, 1996), and the Pinwarian orogeny
was a high-grade orogenic event that affected
much of southern Laurentia (Krogh et al., 1996)
(Fig. 7). Magmatism in this region is typical of an
active continental margin, indicating that along
the length of this proto-North American margin
various terrains were being accreted at different
times, influencing the style and composition of
subsequent magmatism. In regions where juvenile
crust had been recently accreted and subduction
had stepped outwards, large volumes of alumi-
nous A-type volcanics and granitoids were gener-
ated in a continental back-arc setting, which
contrasts markedly with typical active continental
Laurentian margin. This type of model, therefore,
removes the necessity of invoking anorogenic
events, which are often difficult to apply with the
along strike variations observed on this proto-
North American margin.
An alternative mechanism for crustal extension
is continental rifting (e.g. Van Schmus et al.,
1996). Whilst fully developed continental rifting

Fig. 7. Geological map showing possible relationships of Laurentian Palaeoproterozoic and Mesoproterozoic terranes (modified
from Dickin and McNutt, 1990; Gower et al., 1990; Van Schmus et al., 1996). SF = St Francois Mountains, P = Pinware Terrane.
The solid bold line within the 1.51 –1.27 Ga granite –rhyolite terranes separates the older Eastern Granite – Rhyolite Province
(including the St Francois Mountains) from the younger Southern Granite – Rhyolite Province (Van Schmus et al., 1996); the dashed
bold line is the proposed boundary between rocks with TDM \1.55 Ga to the north and TDM B1.55 Ga to the south, after Van
Schmus et al. (1996). The lighter dashed line is the Laurentian margin about 1 Ga ago following the Grenville orogeny. The position
of the Laurentian margin at the time of Eastern Granite – Rhyolite Province igneous activity is poorly known due to the effects of
the Grenville orogeny and cover by younger sedimentary rocks.
 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291 287

would be expected to lead to significant basaltic
volcanism, incipient rifting is less easily dismissed.
Major NW – SE faults in the St Francois Moun-
tains, whose most recent movements have been
sinistral and approximately strike slip (Clendenin
et al., 1989), may be reactivated normal faults
(Marshak and Paulsen, 1996). The Missouri gravity
low (Guinness et al., 1982), which strikes NW– SE
beneath the St Francois Mountains, has been
interpreted as a possible buried rift. It appears to
be truncated to the NW and SE by the Neoprotero-
zoic NE – SW trending Midcontinent and Reelfoot
rifts, respectively. Using gravity and magnetic data,
the Missouri gravity low has been modelled as a
granitic batholith and arguments presented for an
age no greater than 1.38 Ga (Hildenbrand et al.,
1996). An age of no more than about 1.43 Ga for
the same structure was suggested by Gower and
Tucker (1994), who correlated it with development
of the Belt Supergroup. However, recent dating of
sills emplaced into wet sediments suggests that the
latter commenced as early as 1.47 Ga (Sears et al.,
1998), whilst Lowell and Harrison (2001) have
presented evidence for trans-tensional movement
on the Missouri gravity low at 1.47 Ga based on
U – Pb zircon dating of rhyolites in the Eminence-
Van Buren area.
We conclude that, whilst continental rifting can-
not be ruled out as the cause of magmatism, a
‘back-arc’, subduction-related tectonic setting is
favoured by comparison with Mesozoic silicic vol-
canism in Patagonia and West Antarctica (Kay et
al., 1989; Pankhurst et al., 1998) and by the unlikely
plate tectonic scenario of continental rifting devel-
oping within an overriding continental margin
above an active, or recently active, subduction
zone.
Acknowledgements
The authors thank the reviewers for Precambrian
Research, whose comments greatly improved an
earlier version of this paper. They also thank Dave
Ryckman for assistance with sample collection,
Emma Mansley for carrying out ICP REE analyses
and Frank McDermott for assistance with calcula-
tion of zircon saturation temperatures. J.F.
Menuge and Timothy S. Brewer acknowledge a
Forbairt-British Council exchange scheme grant,
which allowed efficient use of analytical facilities in
UCD and Leicester University and meetings to
discuss progress. J.F. Menuge acknowledges a
travel grant from the Jefferson Smurfit Fellowship
Program, which allowed him to visit the University
of Missouri-Rolla and the St Francois Mountains.
He thanks Dick Hagni and the faculty of the
Department of Geology and Geophysics, Univer-
sity of Missouri-Rolla, for their hospitality during
his sabbatical and other visits.

Appendix A. Sample localities, lithologies and formation names

Localities are all in Iron County, Missouri and are given using the US quadrangle grid reference system,
except for samples PEA-10/95-13, 14, 15, 16 and 17, which were all collected from Pea Ridge underground
magnetite mine, Washington County, Missouri (Fig. 1) on level 2275 on an approximately 160 m long
north-south traverse. Formation names after Nuelle et al. (1991) for samples from Pea Ridge mine and
after Berry (1976) for all other samples.

Sample Locality Lithology Formation

ARC5/96-1 T33N R3E, s 3, SE1/4, SE1/4 Rhyolite flow Royal Gorge Rhyolite
ARC5/96-2 T33N R3E, s 4, SE1/4, SW1/4 Ash-flow tuff Taum Sauk Rhyolite
ARC5/96-3 T33N R3E, s 4, SE1/4, SE1/4 Air-fall tuff Bell Mountain Rhyolite
ARC5/96-4 T33N R3E, s 3, SW1/4, SW1/4 Ash-flow tuff Russell Mountain Rhyolite
ARC5/96-5 T33N R3E, s 2, NW1/4, SW1/4 Ash-flow tuff Wildcat Mtn Rhyolite
ARC5/96-6 T34N R3E, s 30, SW1/4, SE1/4 Ash-flow tuff Shepherd Mtn Rhyolite
ARC5/96-7 T33N R3E, s 1, SE1/4, NE1/4 Ash-flow tuff Pond Ridge Rhyolite
288 J.F. Menuge et al. / Precambrian Research 113 (2002) 269–291
ARC5/96-8 T33N R3E, s 1, NE1/4, NW1/4
ARC5/96-9 T33N R3E, s 3, NE1/4, NE1/4
ARC5/96-10 T33N R3E, s 1, SW1/4, SW1/4
PEA10/95-35 T32N R4E, s 8, SE1/4 NE1/4
PEA10/95-13 Pea Ridge mine
PEA10/95-14 Pea Ridge mine
PEA10/95-15 Pea Ridge mine
PEA10/95-16 Pea Ridge mine
PEA10/95-17 Pea Ridge mine
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