Chemical Geology 265 (2009) 468–487

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Chemical Geology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c h e m g e o

Adakite-like magmas from fractional crystallization and melting-assimilation of

mafic lower crust (Eocene Macuchi arc, Western Cordillera, Ecuador)
Massimo Chiaradia ⁎
Department of Mineralogy, University of Geneva, Rue des Maraichers 13, 1205 Geneva, Switzerland

a r t i c l e i n f o a b s t r a c t

Article history: The basement of the Western Cordillera of Ecuador consists of a fragment of oceanic plateau crust
Received 24 September 2008 (Pallatanga) accreted to the continental margin during the Late Cretaceous. Magmatic arcs were formed upon
Received in revised form 2 April 2009 the oceanic plateau before (Rio Cala arc, Maastrichtian) and after (Silante, Upper Maastrichtian–Paleocene,
Accepted 8 May 2009
and Macuchi, Paleocene?–Eocene) accretion, during westward and eastward subductions respectively. Both
Editor: B. Bourdon arc sequences display isotopic and geochemical evidence of involvement of different source reservoirs in the
petrogenesis of their rocks. Rio Cala arc basaltic rocks can be interpreted as the result of mixing between
Keywords: variably evolved magmas derived from different mantle domains or of melting and assimilation of oceanic
Ecuador plateau crust by mantle-derived magmas. Crustal thickening through the build-up of previous magmatic arcs
Andes and, possibly, increased coupling between subducting and overriding plates favoured the interaction of
Western Cordillera mantle-derived melts with the lower to mid-levels of the thickened and modified mafic crust of the accreted
Macuchi oceanic plateau during the subsequent eastward subduction event (Macuchi arc). Adakite-like signatures
Rio Cala
were developed in andesitic to dacitic magmas of the Macuchi arc in response to the evolution of mantle-
Arc magmatism
derived melts within the lower to mid-parts of the thickened juvenile crust. This adakite-like magmatism
Adakite
Radiogenic isotopes marked the onset of a long-lived period of adakite-like magmatism in the Western Cordillera, which,
although interrupted by several periods of normal calc-alkaline magmatism, continues still nowadays in the
active frontal volcanoes of Ecuador.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
Arc magmatism at convergent margins is believed to originate from
partial melting of the peridotitic mantle wedge induced by fluxing of
fluids released from the subducting slab (e.g., Davies and Stevenson,
1992) and possibly by pressure release (e.g., Sisson and Bronto, 1998).
As an additional mechanism to generate magmas at convergent
margins, the occurrence of andesitic to dacitic arc rocks with high Sr/Y
(N40) and low HREE (Yb b 1.8 ppm) has been considered to indicate
direct melting of the downgoing slab (so called adakite by Defant and
Drummond, 1990; e.g., Kay, 1978; Kay et al., 1993; Yogodzinski et al.,
1995; Stern and Kilian, 1996). Such adakite melts might rise more or
less unmodified to the surface or react to various extent, sometimes
until complete consumption, with the peridotitic mantle wedge (e.g.,
Rapp et al., 1999; see also the review of Martin et al., 2005). However,
other studies have suggested that the same geochemical signatures of
adakite can be produced by fractional crystallization and assimilation
processes and/or partial melting of mafic lithologies of the lower
crust in the stability field of clinopyroxene, amphibole ± garnet (e.g.,
⁎ Tel.: +41 22 379 66 34; fax: +41 22 379 32 10.
E-mail address: Massimo.Chiaradia@unige.ch.
Atherton and Petford, 1993; Castillo et al., 1999; Müntener et al., 2001;
Garrison and Davidson, 2003; Macpherson et al., 2006; Davidson et al.,
2007; Rodríguez et al., 2007; Alonso-Perez et al., 2009; Chiaradia et al.,
2009). The correct interpretation of arc rocks with adakite-like
signatures is important to understand the processes that lead to the
formation of andesitic to dacitic magmas at convergent margins and
also for the potential association of adakite-like magmas with giant
porphyry-type deposits (e.g., Thiéblemont et al., 1997).
This study presents new geochemical and isotopic (Pb, Sr, Nd) data
on arc rocks of the Eocene Macuchi arc in the Western Cordillera of
Ecuador. The Western Cordillera of Ecuador consists of a basement of
oceanic plateau crust, accreted to the continental margin during the
Late Cretaceous (Vallejo et al., 2006), and overlying arcs formed
intermittently from the Late Cretaceous to the Quaternary. Rocks with
adakite-like features were known so far to occur in the Quaternary
(e.g., Bourdon et al., 2003; Bryant et al., 2006; Chiaradia et al., 2009)
and Miocene (Chiaradia et al., 2004a; Somers et al., 2005; Schütte
et al., 2007) arcs of the Western Cordillera and have been interpreted
either as the result of slab melts and slab melt–mantle interactions
(e.g., Samaniego et al., 2002; Bourdon et al., 2002; Bourdon et al.,
2003) or of lower crustal magmatic evolution processes (e.g., Garrison
and Davidson, 2003; Garrison et al., 2006; Chiaradia et al., 2009). The
present study shows that the Eocene Macuchi arc also contains

0009-2541/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2009.05.014
 M. Chiaradia / Chemical Geology 265 (2009) 468–487 469

Fig. 1. Simplified geological map of the Western Cordillera of Ecuador between latitudes 1°N and 1°S (modified from BGS and CODIGEM, 1999, 2001) with location of the investigated
samples. Top left: map of South America showing the location of Ecuador and main oceanic topographic features (CR = Cocos ridge; CGR = Carnegie ridge; NR = Nazca ridge; JFR =
Juan Fernandez ridge; Chile rise).

adakite-like rocks, implying that adakite-like magmatism has lasted,
although interrupted by variably long periods of normal calc-alkaline
magmatism, for the last ∼40 My in the Western Cordillera of Ecuador.
The geochemical and isotopic evolution of the Macuchi arc rocks is
investigated in the frame of the geodynamic evolution of the Western
Cordillera during Late Cretaceous to Eocene times and compared to
the magmatic evolution of rocks of an older arc of the Western
Cordillera, the Late Cretaceous intraoceanic Rio Cala arc, for which
conditions were apparently not suitable to develop adakite-like
signatures.
470 M. Chiaradia / Chemical Geology 265 (2009) 468–487
2. Geodynamic setting
The Western Cordillera of Ecuador consists of a basement of
allochthonous oceanic terranes (Figs. 1 and 2) accreted to the South
American margin during the Late Cretaceous (Feininger, 1987; Megard,
1989; Wallrabe-Adams,1990; Jaillard et al., 1990, 1997; Kerr et al.,1997;
Reynaud et al., 1999; Hughes and Pilatasig, 2002; Mamberti et al.,
2003; Kerr and Tarney, 2005; Vallejo et al., 2006). Gravimetric data
(Feininger and Seguin, 1983) indicate that the Western Cordillera
consists of 25–30 km thick oceanic crust, and an even thicker (40–
50 km) crust has been suggested based on the depth of seismic activity
(Guillier et al., 2001). Various geochemical and isotopic studies (e.g.,
Cosma et al., 1998; Reynaud et al., 1999; Lapierre et al., 2000; Kerr et al.,
2002; Mamberti et al., 2003) have highlighted the oceanic plateau
nature of the accreted terranes, but much debate still remains on the
age, provenance and accretion time of these oceanic plateau terranes.
Arc sequences have been emplaced on top of the oceanic plateaus
(Figs. 1 and 2), but divergence exists on whether they formed before or
after the accretion of the plateau basement (e.g., Henderson, 1979;
Fig. 2. Simplified stratigraphic column of the Western Cordillera of Ecuador (modified
from Vallejo, 2007 and Vallejo et al., 2009).
Aguirre and Atherton, 1987; van Thournout et al., 1992; Hughes and
Pilatasig, 2002; Kerr et al., 2002; Vallejo et al., 2009).
This study uses the geodynamic model recently proposed by
Vallejo et al. (2009), which is the most up-to-date with available
geochronologic, stratigraphic, paleomagnetic and geochemical data
(Fig. 3). Nonetheless, the interpretation of the data here presented
does not depend uniquely on this model and is equally applicable to
previous geodynamic scenarios, as it will become clear from the
following discussion.
According to data of Vallejo et al. (2009) the thick (ca 20 km)
oceanic plateau known as Pallatanga terrane, now forming the
basement of the Western Cordillera (Fig. 2), was extruded mainly
between 88 and 84 Ma (see also Luzieux et al., 2006) and was accreted
to the Ecuadorian margin during the Campanian–Maastrichtian (73–
70 Ma) (see also Vallejo et al., 2006). It has therefore chronological
affinity with the Late Cretaceous Colombian/Caribbean oceanic
plateau (CCOP). Older oceanic plateau crust fragments (e.g., San
Juan Unit: Sm–Nd isochron age of 123 Ma: Lapierre et al., 2000) could
have been accreted previously to the Ecuadorian margin (Fig. 2).
According to the model of Vallejo et al. (2009) an intraoceanic island
arc (Rio Cala island arc: Figs. 1 and 3) was formed prior to accretion
upon the Pallatanga oceanic plateau between 85 and 72 Ma as a result
of westward subduction (Fig. 3A). This model contrasts with that of
Kerr et al. (2002) according to which Rio Cala was an autochthonous
arc formed during eastward subduction. In the model of Vallejo et al.
(2009) collision between the eastern leading edge of the Pallatanga
terrane and the Ecuadorian margin caused the shut off of westward
subduction (Fig. 3B). Subduction resumed oceanward of the accreted
Pallatanga terrane, this time dipping eastward (Fig. 3C). The eastward
subduction resulted in the formation of the subaerial Silante arc
during the latest Maastrichtian (ca 65 Ma) in the eastern part of the
Western Cordillera and of its temporal continuation, the submarine
Macuchi arc, in the western part of the Western Cordillera during the
(Paleocene?–)Eocene (Figs. 2 and 3). The interpretation of Macuchi as
an autochthonous arc, emplaced upon the already accreted Pallatanga
oceanic plateau and, at least partly, the overlying Rio Cala and Silante
arcs (Fig. 3C), contrasts with the model of Hughes and Pilatasig (2002)
that Macuchi was an intraoceanic island arc formed upon the
Pallatanga oceanic plateau and accreted to the Ecuadorian margin,
together with the latter, during the late Eocene.
After the Macuchi arc, the Western Cordillera of Ecuador was the
locus of more or less continuous subduction-related magmatic activity
throughout the Cenozoic (BGS and CODIGEM, 1999, 2001; Somers
et al., 2005; Schütte et al., 2007) until the formation of the Quaternary
frontal arc volcanoes. Major geodynamic rearrangements of the
subducting plate in terms of its age, angle of subduction and obliquity
at the trench (e.g., Noblet et al., 1996) occurred at 25 Ma when the
Farallon plate was split into the Cocos and Nazca plates and with the
debated arrival of the aseismic Carnegie ridge at the trench from as
early as 9–15 My (Spikings et al., 2001) to as late as 1 My ago
(Lonsdale and Klitgord, 1978; Gutscher et al., 1999).
3. Lithologic units
This study investigates magmatic rocks associated with both west-
(Rio Cala arc) and east-dipping subduction (Macuchi arc). A short
description of the lithologies forming the two arc sequences (Figs. 1
and 2) is provided below, based mostly on previous studies and partly
on the author's observations.
3.1. Rio Cala arc
In this study the Rio Cala arc includes the Campanian–Maastrichtian
Rio Cala Group, situated east of the Toachi fault, and parts of the Naranjal
Unit and Colorado Formation, situated west of the Toachi fault (Fig. 1).
The Campanian–Maastrichtian (85–72 Ma) Rio Cala Group (including
 M. Chiaradia / Chemical Geology 265 (2009) 468–487
Fig. 3. Geodynamic evolution of the Western Cordillera of Ecuador (modified from
Vallejo et al., 2009). For discussion refer to text.
the La Portada, Mulaute, Pilatón, Natividad and Rio Cala Formations)
represents a volcanic and sedimentary intraoceanic island arc sequence
deposited above the 88–84 My old Pallatanga oceanic plateau. The
Campanian Naranjal Unit consists of pillow basalts characterized by
geochemical features typical of both oceanic plateau and primitive
island arc (Kerr et al., 2002).
Available geochemical data of volcanic rocks belonging to the Rio
Cala arc (Vallejo, 2007; Allibon et al., 2008) indicate a subduction-
related fingerprint and primitive, tholeiitic island arc geochemical
features.
3.2. Macuchi arc
In this study the Macuchi arc includes the Macuchi Unit and the
Tortugo Formation (Fig. 1). The Macuchi Unit crops out along the
western portion of the central Western Cordillera. It consists of basaltic
to andesitic pillow lavas with a subduction-related fingerprint and
tholeiitic to calc-alkaline affinity (e.g., Chiaradia and Fontboté, 2001;
Hughes and Pilatasig, 2002; Kerr et al., 2002), lithic tuffs, breccias, high-
level intrusions of andesitic (rarely dacitic) composition, as well as
resedimented turbiditic volcanic material and cherts representing
altogether a submarine volcanic arc sequence (BGS and CODIGEM,
1999). The occurrence of silicic ash-flow tuffs in the sequence (Egüez,
1986) possibly indicates that subaerial conditions were reached during
the build-up of the Macuchi arc (Hughes and Pilatasig, 2002).
Table 1
Summary of the analyses carried out in previous and in the present study.
Samples Major elements (XRF) Trace elements (XRF)a
Series E09 Chiaradia and Fontboté (2001) Chiaradia and Fontboté (2001)
Series TRI Chiaradia et al. (2008) Chiaradia et al. (2008)
a
Zn, Cu, Cr, Ni, V, Sc.
b
Co, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Hf, Ta, Pb, Th, U.
471
Foraminifera in sedimentary rocks intercalated within andesites
and tuffs of the Macuchi Unit are of Late Eocene age (Egüez, 1986).
High-level intrusions of andesitic composition have been dated (K–Ar)
at ∼42–36 Ma (Egüez, 1986) and andesitic lava flows yielded 40Ar/39Ar
plateau ages of 42.62 ± 1.3 Ma (2σ) and 35.12 ± 1.66 Ma (2σ) Ma
(Vallejo, 2007). These data suggest that the Macuchi Unit erupted
during the early to late Eocene and perhaps as early as the Paleocene
(Fig. 2).
BGS and CODIGEM (1999) mapped lenses of pillow basalt and
pillow andesite occurring in the lower stratigraphic part of the
Macuchi Unit as a separate, geochemically more primitive subunit,
representing either an early arc stage or an oceanic crust basement to
the Macuchi arc. Chiaradia and Fontboté (2001) recognized that these
sequences of pillow basalts and andesites (that they called Basal
Macuchi) were primitive subduction-related rocks geochemically
different from the subduction-related basaltic to dacitic rocks of the
Macuchi Unit sensu strictu (termed Main Macuchi by Chiaradia and
Fontboté, 2001) and attributed them to an earlier subduction event
(see below).
The Eocene Tortugo Formation, cropping out in the northern part
of the Western Cordillera, consists of volcanosedimentary deposits
directly overlying the Naranjal Unit of the Rio Cala Group, in a
stratigraphic position similar to that of the Macuchi Unit.
4. Sampling and nomenclature
The present study investigates rocks that were collected and
analyzed for major and some trace elements and partly for Pb isotopes
by Chiaradia and Fontboté (2001) (series E09: Table 1) and Chiaradia
et al. (2008) (series TRI: Table 1). Table 1 shows the repartition
between the analyses done in the previous studies (Chiaradia and
Fontboté, 2001; Chiaradia et al., 2008) and those carried out in this
study. In the light of new radiometric data (Spikings et al., 2005) and
the new map of the Western Cordillera between 0° and 1°N (BGS and
CODIGEM, 2001), it is now possible to relocate samples of those
studies within more appropriate lithologic units as explained below.
4.1. Samples of the Rio Cala arc sequence
All samples that were attributed to the Basal Macuchi by Chiaradia
and Fontboté (2001) are now included in the Rio Cala arc sequence. In
fact, relocation of three Basal Macuchi samples (E99237, E99122,
E94016: Fig. 1) of Chiaradia and Fontboté (2001) within the new map
of the Western Cordillera between latitudes 0° and 1°N (BGS and
CODIGEM, 2001) shows that samples E99237 and E99122 were
collected within the Naranjal Unit and sample E94016 was collected
from the Pilatón Unit close to Nanegalito (Fig. 2), both these Units
being part of the Rio Cala arc (see above).
Samples E99103, 109, 110, 121, 193 and 204 were collected in
proximity of Alluriquín and Santo Domingo and on the road Quevedo–
Latacunga within what is mapped as the pillow basalt and pillow
andesite subunit of the Macuchi Unit by BGS and CODIGEM (1999)
and was named Basal Macuchi by Chiaradia and Fontboté (2001)
(Fig. 1). However, Spikings et al. (2005) have recently obtained a
zircon fission track age of ∼ 67.5 ± 10.7 (1σ) Ma on a basaltic andesite
close to the town of Alluriquín, which represents a typical outcrop of
the Basal Macuchi from where also Chiaradia and Fontboté (2001) had
Trace elements (ICP)b Pb isotopes Sr isotopes Nd isotopes
This study Chiaradia and Fontboté (2001) This study This study
This study This study This study This study
472 M. Chiaradia / Chemical Geology 265 (2009) 468–487

Table 2
Geochemical and isotopic data of the investigated rocks.

Sample E94016 E99099 E99103 E99109 E99110 E99121 E99122 E99204 E99237 TRI 001 TRI 007
Lithology Basalt Basalt Basalt Basalt Basalt Basalt Basaltic Basalt Basalt Basalt Basalt
andesite
Subdivision Rio Cala arc Rio Cala arc Rio Cala arc Rio Cala arc Rio Cala arc Rio Cala arc Rio Cala arc Rio Cala arc Rio Cala arc Dolerite dyke Dolerite dyke
SiO2 50.47 50.33 47.68 51.01 48.47 49.17 55.16 48.32 49.2 46.01 47.79
TiO2 0.69 0.86 0.64 0.62 0.81 0.67 0.69 1.24 0.74 0.76 1.12
Al2O3 18.33 15.58 14.21 14.17 14.6 16.35 13.71 15.9 17.15 15.14 16.05
CaO 5.81 9.88 9.85 9.02 11.5 8.42 6.47 8.61 6.81 11.77 10.54
Na2O 4.12 2.13 1.72 1.95 2.32 4.45 4.01 2.96 5.01 1.18 2.15
K2O 0.31 0 0.48 0.48 0.79 0.13 1.07 0.27 0.09 0.29 0.4
MnO 0.13 0.17 0.17 0.11 0.14 0.15 0.19 0.13 0.14 0.16 0.16
MgO 7.23 3.74 12.32 8.48 8.22 8.21 4.27 9.01 4.82 10.95 8.49
Fe2O3 8.02 13.1 8.61 7.69 8.82 8.97 12.42 8.65 12.91 8.54 9.19
P2O5 0.14 0.13 0.11 0.12 0.17 0.1 0.14 0.18 0.58 0.09 0.16
LOI 4.14 3.94 4.37 6.6 4.28 3.61 2.31 3.75 2.53 4.4 2.71
Total 99.42 99.88 100.3 100.39 100.18 100.31 100.43 99.19 100.06 99.39 98.84
Rb 3.7 0.2 7.3 8.2 10.6 1.8 24.2 3.0 1.1 5.0 3.4
Sr 302 179 148 235 173 62 90 214 175 152 230
Y 21 15 14 16 16 16 22 21 33 12 20
Zr 61 29 34 59 45 38 46 85 40 38 72
Nb 1.2 0.4 0.9 1.7 5.8 0.7 0.6 5.3 0.9 1.3 3.2
Hf 1.5 0.9 1.0 1.6 1.1 1.0 1.4 2.0 1.2 1.1 1.9
Pb 2.0 1.7 1.0 1.0 1.2 0.9 1.1 3.4 0.9 2.8 1.1
Th 0.6 0.2 0.3 1.5 0.8 0.4 0.4 0.7 0.3 0.4 0.8
U 0.3 0.1 0.1 0.5 0.2 0.1 0.2 0.2 0.3 0.2 0.3
Ba 86 11 63 94 128 26 147 66 31 61 138
Zn 61 90 68 112 71 72 63 53 117 65 67
Cu 27 26 42 58 44 7 16 42 17 20 50
Cr 193 5 550 571 244 325 20 287 61 554 424
Ni 78 3 351 257 109 156 10 156 37 238 160
Sc 42 41 40 43 42 28 29 51 43 45 46
V 249 420 222 218 265 292 439 253 319 191 257
La 6.2 2.3 2.5 6.8 5.9 3.3 4.6 6.1 7.2 4.6 6.6
Ce 14.1 5.7 6.7 15.3 13.4 8.1 10.9 15.4 9.4 7.1 13.0
Pr 2.1 0.9 1.1 2.2 1.9 1.2 1.7 2.3 1.9 1.0 1.9
Nd 10.3 4.4 5.1 10.4 9.5 6.5 8.7 10.7 9.2 5.6 9.7
Sm 2.5 1.5 1.5 2.5 2.4 1.8 2.2 2.9 2.8 1.6 2.7
Eu 0.9 0.7 0.6 0.8 0.8 0.7 0.8 1.1 0.9 0.6 1.0
Gd 2.9 1.9 2.3 2.6 2.7 2.4 2.7 4.0 3.5 2.0 3.3
Tb 0.5 0.3 0.4 0.4 0.4 0.4 0.4 0.6 0.6 0.3 0.5
Dy 3.6 2.1 2.3 2.6 2.8 2.6 2.8 3.7 4.0 2.4 3.7
Ho 0.7 0.5 0.5 0.6 0.6 0.6 0.6 0.8 1.0 0.4 0.7
Er 2.3 1.6 1.5 1.6 1.7 1.7 1.7 2.3 3.1 1.4 2.1
Tm 0.3 0.3 0.2 0.2 0.2 0.2 0.2 0.3 0.5 0.2 0.3
Yb 2.2 1.7 1.5 1.5 1.5 1.6 1.7 2.2 3.1 1.4 2.1
Lu 0.3 0.2 0.2 0.2 0.2 0.3 0.3 0.3 0.5 0.2 0.3
Mg# 0.6 0.4 0.7 0.7 0.7 0.6 0.4 0.67 0.43 0.72 0.65
143
Nd/144Nd 0.513021 0.513012 0.513075 0.512946 0.512971 0.513040 0.513043 0.513071 0.512940 0.513066 0.513044
143
Nd/144Ndi 0.512946 0.51291 0.512985 0.512874 0.512894 0.512956 0.512967 0.512988 0.512850 0.513026 0.513005
εNd(0)a 7.5 7.3 8.5 6 6.5 7.8 7.9 8.4 5.9 8.4 7.9
87
Sr/86Sr 0.704040 0.704143 0.703660 0.703217 0.703956 0.703599 0.704155 0.703129 0.704804 0.703911 0.703401
87
Sr/86Sri 0.704001 0.704139 0.703503 0.703106 0.703761 0.703508 0.703302 0.703084 0.704783 0.703863 0.70338
206
Pb/204Pb 18.803 18.662 18.781 18.814 18.773 18.793 18.72 18.866 18.734 18.952 18.753
207
Pb/204Pb 15.563 15.537 15.586 15.585 15.571 15.598 15.551 15.578 15.55 15.613 15.589
208
Pb/204Pb 38.291 38.217 38.386 38.463 38.403 38.526 38.243 38.455 38.304 38.627 38.382

Data are from this study, Chiaradia and Fontboté (2001) and Chiaradia et al. (2008) according to the scheme reported in Table 1.
a
Referred to CHUR.

taken a sample (E99099). This Late Cretaceous (to Early Paleocene?)
age, although the large error, is permissible for a correlation of the
pillow basalts and andesites of the Basal Macuchi with rocks of the
Late Cretaceous Rio Cala Group. As it will be shown below (and was
shown already by Chiaradia and Fontboté, 2001) geochemical and
isotopic consistency of this group of Basal Macuchi samples (E99103,
109, 110, 121, 193 and 204) with the above three samples (E99237,
E99122, E94016) that, after publication of the new map of the Western
Cordillera between latitudes 0° and 1°N (BGS and CODIGEM, 2001),
are known to have been collected within the Rio Cala arc, supports this
interpretation. This suggests that the Rio Cala arc sequence underlies
immediately the Macuchi arc sequence between latitudes 0° and 1°S
(see Figs. 1 and 2).
Finally, sample E09099 was collected on the old road Quito-Sto
Domingo, close to Guarumal, from an area mapped as Silante Unit by
BGS and CODIGEM (1999) (Fig. 1). However, the geochemical and
isotopic features of this sample (see below) indicate that it belongs to
the Rio Cala arc. The occurrence of several slivers of the Pilatón Unit
(Rio Cala Group) in tectonic contact with the Silante Unit (BGS and
CODIGEM, 1999, 2001) makes it possible that this basalt sample was
collected from a small sliver of the Pilatón Unit (Rio Cala Group).
4.2. Samples of the Macuchi arc sequence
In this study the Macuchi arc includes all lava and high-level
intrusive samples of the Main Macuchi sequence of Chiaradia and
 M. Chiaradia / Chemical Geology 265 (2009) 468–487 473

Table 2
Geochemical and isotopic data of the investigated rocks.

TRI 039 TRI 040 TRI 054 TRI 069 E94015 E99113 E99114 E99156 E99161 E99174 E99176 E99182
Basalt Basalt Basalt Basalt Basaltic Andesite Dacite Basaltic Basalt Basalt Dacite Basaltic
andesite intrusion intrusion andesite intrusion andesite
Dolerite dyke Dolerite dyke Dolerite dyke Dolerite dyke Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc
49.22 51.71 49.26 47.82 58.31 62.85 69.02 53.52 49.61 50.73 66.99 54.34
1.16 1.7 1.34 0.71 0.55 0.27 0.22 0.68 0.88 0.75 0.38 0.82
16.11 15.43 15.93 17 16.91 17.3 16.5 17.84 15.98 15.19 14.17 16.57
7.08 6.65 7.96 11.16 5.36 4.65 3.6 3.93 6.32 6.55 2.92 5.92
4.28 5.47 4.64 1.99 4.77 4.28 4.7 4.11 4.86 5.16 4.16 6.08
0.08 0.14 0.11 0.63 0.1 1.27 1.25 1 0.1 0.05 1.38 0.23
0.17 0.18 0.16 0.16 0.13 0.09 0.05 0.23 0.14 0.15 0.11 0.16
8.46 5 5.16 8.11 3.58 2.17 0.77 4.51 6.47 6.82 1.93 3.21
9.09 10.69 9.45 9.16 7.18 4.26 1.93 7.99 11.54 10.81 3.85 9.36
0.14 0.19 0.18 0.08 0.15 0.08 0.09 0.17 0.14 0.14 0.16 0.18
3.85 2.51 3.13 2.37 3.05 2.67 1.34 4.9 3.43 2.74 3.61 2.55
99.7 99.68 97.33 99.21 99.55 99.89 99.47 98.89 99.49 99.11 99.65 99.42
1.2 1.7 1.5 5.6 1.9 15.4 25.8 19.9 1.8 1.1 25.8 2.7
165 92 207 212 298 445 627 255 118 144 207 162
19 27 24 13 19 6 6 20 17 15 10 21
60 92 75 33 64 48 63 50 41 36 63 67
2.4 3.4 2.8 0.9 1.1 0.8 1.7 1.0 1.0 0.9 2.4 2.0
1.6 2.4 2.0 0.9 1.6 1.4 1.9 1.6 1.3 1.0 2.0 1.9
3.2 2.8 1.8 1.0 3.6 2.3 4.8 3.0 5.2 14.0 9.9 6.0
0.8 1.0 0.8 0.4 0.8 1.0 0.8 1.3 1.7 1.5 2.5 1.7
0.3 0.3 0.3 0.2 0.3 0.4 0.5 0.5 0.5 0.4 1.0 0.5
64 58 47 75 63 273 504 442 73 106 369 39
90 74 66 54 67 48 39 77 89 144 68 79
49 39 25 60 31 40 5 56 100 55 9 51
277 40 62 61 30 8 23 57 87 139 19 19
108 25 36 42 12 11 3 22 22 32 6 6
49 35 42 46 38 6 5 48 64 49 8 25
292 418 348 222 203 105 36 321 417 398 81 264
6.1 7.6 6.9 4.6 6.5 5.1 4.3 6.7 7.0 7.3 10.4 7.7
11.5 16.4 13.9 6.3 14.5 10.2 9.3 14.7 15.0 13.9 21.7 17.9
1.8 2.5 2.0 1.0 2.1 1.4 1.2 2.3 2.1 1.9 2.8 2.5
8.9 12.7 10.7 5.3 8.9 6.0 5.3 11.0 9.8 8.9 11.9 12.3
2.6 3.8 3.1 1.7 2.6 1.1 1.1 2.9 2.4 2.3 2.0 3.1
0.9 1.3 1.2 0.6 0.9 0.4 0.4 0.9 0.8 0.7 0.5 1.0
3.1 4.4 4.0 2.0 2.8 1.0 1.0 3.4 2.7 2.1 1.9 3.1
0.5 0.7 0.6 0.3 0.4 0.1 0.1 0.5 0.4 0.4 0.3 0.5
3.4 5.0 4.4 2.3 3.0 1.0 0.7 3.6 2.9 2.5 1.7 3.6
0.7 1.1 0.9 0.5 0.6 0.2 0.1 0.7 0.6 0.6 0.4 0.8
2.0 2.9 2.5 1.4 2.0 0.5 0.3 2.3 1.7 1.6 1.0 2.4
0.3 0.4 0.3 0.2 0.3 0.1 0.1 0.3 0.3 0.3 0.2 0.3
1.9 2.9 2.5 1.3 2.1 0.6 0.3 2.4 1.7 1.9 1.0 2.2
0.3 0.4 0.4 0.2 0.3 0.1 0.1 0.4 0.3 0.3 0.2 0.3
0.65 0.48 0.52 0.64 0.5 0.5 0.44 0.53 0.53 0.56 0.5 0.4
0.513029 0.513052 0.513060 0.513046 0.512997 0.512989 0.512993 0.512937 0.512853 0.512662 0.512976 0.512911
0.513044 0.513011 0.51302 0.513001 0.512949 0.512958 0.512957 0.512894 0.512813 0.51262 0.512949 0.512870
7.6 8.1 8.2 8 7 6.8 6.9 5.8 4.2 0.5 6.6 5.3
0.704647 0.703572 0.703661 0.703441 0.703973 0.703515 0.703372 0.704101 0.704600 0.707740 0.703882 0.704043
0.704637 0.703545 0.70365 0.703403 0.703962 0.703455 0.703301 0.703966 0.704574 0.707726 0.703667 0.704014
19.041 19.089 19.036 18.911 18.826 18.752 18.824 18.9 19.087 19.059 18.907 18.992
15.652 15.639 15.666 15.629 15.586 15.57 15.569 15.614 15.648 15.667 15.602 15.633
38.775 38.795 38.831 38.609 38.405 38.34 38.385 38.57 38.873 38.874 38.547 38.729
(continued on next page)

Fontboté (2001) plus 4 lava samples and 6 dolerite dyke samples
collected in the La Plata mine area and investigated by Chiaradia et al.
(2008).
All lava and high-level intrusive samples were collected within the
Macuchi Unit as mapped by BGS and CODIGEM (1999) (Fig. 1) and
show geochemical and isotopic consistency (see below), as opposed to
the dolerite dyke samples which are geochemically and isotopically
distinct. The only exceptions are sample E94015, collected within the
Silante Unit, and sample E99236, collected within the Tortugo
Formation, which also belongs to the Macuchi arc sequence (see
above and Fig. 1). Because the Macuchi arc is considered to be the
temporal continuation of the Silante arc (Vallejo et al., 2009; see also
Figs. 2 and 3) sample E94015 would be, among the investigated
samples, the earliest expression of the eastward subduction-related
autochthonous arc magmatism in the Western Cordillera. Both above
samples have petrographic and, as it will be shown below,
geochemical and isotopic affinity with samples of the Macuchi Unit.
5. Analytical techniques
Besides petrographic studies of the thin sections, all rock samples
were investigated by X-ray fluorescence (XRF) for major and some
trace elements (Tables 1 and 2) by Chiaradia and Fontboté (2001) and
Chiaradia et al. (2008) at the Institute of Mineralogy and Geochem-
istry, University of Lausanne (Tables 1 and 2) using a Philips PW 2400
spectrometer. The BHVO-1, NIMN and GA basaltic and rhyolitic
474 M. Chiaradia / Chemical Geology 265 (2009) 468–487

Table 2
Geochemical and isotopic data of the investigated rocks.
Table 2 (continued)
Sample E99183 E99184 E99185 E99190 E99236 TRI 010 TRI 051 TRI 055 TRI 096
Lithology Andesite Andesite Dacite Basalt Basaltic andesite Basalt Basalt Andesite Andesite
intrusion intrusion
Subdivision Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc Macuchi arc
SiO2 60.93 52.81 64.49 52.01 53.44 51.84 52.21 59.79 57.86
TiO2 0.69 0.68 0.27 0.91 0.77 0.71 0.8 0.66 0.66
Al2O3 16.54 16.37 16.97 18.17 17.89 15.4 17.62 13.69 12.89
CaO 6.25 4.12 5.12 6.28 9.97 9.38 9.32 6.5 6.2
Na2O 4.6 5.56 4.22 3.62 2.23 3.87 1.91 2.95 4.66
K2O 1.08 0.48 0.63 0.64 0.32 0.03 0.27 0.07 0.07
MnO 0.05 0.22 0.06 0.17 0.16 0.18 0.15 0.14 0.28
MgO 1.48 6.39 0.99 2.49 4.64 4.83 5.35 3.44 5.16
Fe2O3 4.99 9.79 3.23 9.76 9.68 10.59 8.72 9.36 9.95
P2O5 0.17 0.11 0.16 0.15 0.1 0.14 0.19 0.11 0.1
LOI 2.4 3.34 3.05 4.52 0.7 2.67 2.5 2.49 1.27
Total 99.19 99.89 99.19 98.72 99.92 99.65 99.06 99.2 99.12
Rb 14.4 5.7 12.7 9.6 4.8 0.6 5.9 1.4 1.3
Sr 558 207 466 365 193 141 431 105 236
Y 8 15 10 25 19 15 16 13 11
Zr 81 36 79 58 42 36 43 33 29
Nb 2.0 0.8 2.8 1.2 1.0 0.9 2.3 1.0 0.8
Hf 2.3 1.1 2.1 1.8 1.2 1.1 1.2 1.0 0.9
Pb 4.9 3.4 11.0 3.1 1.3 3.7 2.2 3.8 5.3
Th 1.2 0.6 1.7 1.3 0.4 1.5 1.1 1.4 1.2
U 0.5 0.3 0.7 0.7 0.2 0.4 0.4 0.4 0.3
Ba 359 81 184 213 45 19 79 41 108
Zn 78 102 38 104 76 76 65 71 70
Cu 36 29 6 71 146 14 89 76 117
Cr 26 73 6 10 59 73 84 25 109
Ni 9 36 1 13 35 24 40 9 23
Sc 10 56 9 35 35 40 44 36 43
V 142 312 25 391 307 387 331 297 356
La 8.7 3.6 8.6 6.9 3.1 8.6 9.1 6.5 7.2
Ce 19.3 8.6 19.0 15.6 7.9 13.7 15.5 11.5 10.8
Pr 2.6 1.3 2.5 2.4 1.3 1.9 2.3 1.7 1.5
Nd 12.1 6.2 11.4 11.8 6.9 8.3 10.3 7.9 7.0
Sm 2.8 1.8 2.4 3.5 1.9 2.3 2.8 2.2 1.8
Eu 0.8 0.7 0.6 1.0 0.7 0.7 0.9 0.7 0.5
Gd 2.4 2.1 1.8 3.6 2.4 2.3 3.0 2.1 2.0
Tb 0.3 0.4 0.2 0.5 0.4 0.4 0.5 0.4 0.3
Dy 1.4 2.7 1.4 3.8 3.3 2.5 3.0 2.3 2.0
Ho 0.2 0.5 0.3 0.8 0.7 0.5 0.6 0.5 0.4
Er 0.6 1.6 0.8 2.5 2.1 1.5 1.8 1.4 1.2
Tm 0.1 0.3 0.2 0.3 0.3 0.2 0.2 0.2 0.2
Yb 0.5 1.6 1.0 2.2 2.0 1.5 1.7 1.4 1.2
Lu 0.1 0.2 0.1 0.4 0.3 0.3 0.3 0.2 0.2
Mg# 0.37 0.56 0.38 0.34 0.49 0.47 0.55 0.42 0.51
143
Nd/144Nd 0.512918 0.512973 0.512999 0.512960 0.513036 0.512852 0.512981 0.512851 0.512851
143
Nd/144Ndi 0.512880 0.512924 0.512964 0.512911 0.512990 0.512807 0.512937 0.512806 0.512809
εNd(0)a 5.5 6.5 7 6.3 7.8 4.2 6.7 4.2 4.2
87
Sr/86Sr 0.703839 0.705248 0.703562 0.703844 0.703627 0.704409 0.703254 0.704338 0.704907
87
Sr/86Sri 0.703794 0.705201 0.703515 0.703799 0.703584 0.704402 0.703230 0.704314 0.704898
206
Pb/204Pb 18.870 19.087 18.893 19.029 18.910 19.073 18.94 19.06 19.01
207
Pb/204Pb 15.583 15.657 15.581 15.640 15.619 15.669 15.611 15.653 15.636
208
Pb/204Pb 38.498 38.881 38.479 38.773 38.573 38.868 38.602 38.811 38.725

standards were used for quality control. The 2σ uncertainties based on
repeated measurements of these standards are b1% for all major
elements and b5% for trace elements. Concentrations of rare earth
elements (REE) and other trace elements (Tables 1 and 2) were
determined in the present work by LA-ICP-MS on glass beads (used for
major element XRF analyses) at the Institute of Mineralogy and
Geochemistry, University of Lausanne, using a 193 nm Excimer Laser
System (Geolas®) associated with an ICP-MS Perkin-Elmer ELAN 6100
DRC. Operating conditions of the laser were: 10 Hz frequency, 160 mJ
energy, 120 µm spot size. The measurement time for blank correction
was about 90 s after which the laser was switched on and the signal
was measured for about 40 s. For each sample 3 to 4 points were
measured and results were then averaged. Uncertainties between
results of repeat points of the same sample were b10% for REE and b5%
for the other trace elements analyzed (Table 2). CaO contents
previously determined by XRF on the glass beads were used for
internal standardization by reference to an SRM612 NIST external
standard. Raw data were reduced off-line using the LAMTRACE
(Jackson et al., 1992; Longerich et al., 1996) and SILLS (Guillong
et al., 2008) softwares.
Rocks were analyzed for Pb, Sr and Nd isotopic compositions
(Tables 1 and 2) at the Department of Mineralogy of Geneva. Samples
of the series TRI were analyzed for Pb isotopes following the same
procedure (Chiaradia and Fontboté, 2003) used for samples of the
series E09, which were already analyzed by Chiaradia and Fontboté
(2001) for Pb isotopes, i.e., by first leaching the rock powder for 36 h at
 M. Chiaradia / Chemical Geology 265 (2009) 468–487 475

180 °C in screw-sealed 20 ml Teflon vials using a mixture of 3.5 ml of the basaltic lava flows and the high-level andesitic to dacitic
7 M HCl and 1.5 ml of 14 M HNO3 and then analyzing only the residue porphyritic magmas. The dolerite dykes cutting the lava sequence at
(for details see Chiaradia and Fontboté, 2001, 2003). La Plata mine are holocrystalline and consist of sub-equidimensional
For samples of the series E09 that were not previously investigated plagioclase and clinopyroxene crystals defining a subophitic texture.
for Sr and Nd isotopes as well as for samples of the series TRI, between Both Rio Cala and Macuchi basaltic to andesitic rocks underwent
100 and 150 mg of powdered rock fractions (b70 µm) were leached an oceanic hydrothermal and burial metamorphism, more or less
overnight at room temperature with 3 M HCl to remove secondary contemporaneous with the arc build-up process, which has pro-
soluble mineral phases (e.g., calcite). The leachate was discarded and duced zeolite facies assemblages overprinting the original primary
the residue, after being rinsed twice with deionized water centrifuged mineralogy (Aguirre and Atherton, 1987; Chiaradia and Fontboté,
and separated from the supernatant, was dissolved on a hot plate at 2001; Tripodi, 2002; Vallejo, 2007; Chiaradia et al., 2008). Whereas
140 °C in closed Teflon vials during 7 days with a mixture of 4 ml conc. plagioclase and clinopyroxene are relatively well preserved in the
HF and 1 ml HNO3 15 M. The sample was then dried on a hot plate, and majority of the investigated samples, in the most altered samples
redissolved in 3 ml of 15 M HNO3 in closed Teflon vials at 140 °C and olivine is replaced by serpentine ± calcite ± quartz, plagioclase is
dried down again. Sr and Nd separation was carried out using cascade albitized and clinopyroxene as well as amphibole are replaced by
columns with Sr-spec, TRU-spec and Ln-spec resins following a chlorite, pumpellyite and Fe-oxides. The amygdales occurring in
modified method after Pin et al. (1994). the basaltic lithologies are filled with quartz, calcite, chlorite and
Pb, Sr and Nd isotope ratios were measured on a Thermo TRITON zeolites.
mass spectrometer on Faraday cups in static mode. Pb was loaded on The burial-hydrothermal metamorphism of the investigated rocks
Re filaments using the silica gel technique and all samples (and results in fairly to very high volatile contents (loss on ignition
standards) were measured at a pyrometer controlled temperature of LOI = 0.5–6.5 wt.%), which are overall higher in the more mafic rocks
1220 °C. Pb isotope ratios were corrected for instrumental fractionation of the Rio Cala arc due to the occurrence of amygdales. Macuchi rocks
by a factor of 0.07% per amu based on more than 90 measurements of have lower LOI values (b3.6 wt.%) except for two basaltic rocks, which
the SRM981 standard and using the standard values of Todt et al. have LOI values at 4.5 and 4.9 wt.% (Table 2). Under these
(1996). External reproducibilities (2σ) of the standard ratios are 0.05% metamorphic conditions some large ion lithophile elements (LILE)
for 206Pb/204Pb, 0.08% for 207Pb/204Pb and 0.10% for 208Pb/204Pb. may be mobile, whereas the high concentrations of major elements
Sr was loaded on single Re filaments with a Ta oxide solution and
measured at a pyrometer-controlled temperature of 1490 °C. 87Sr/86Sr
values were internally corrected for fractionation using a 88Sr/86Sr
value of 8.375209. Raw values were further corrected for external
fractionation by a value of + 0.03‰, determined by repeated mea-
surements of the SRM987 standard (87Sr/86Sr = 0.710250). External
reproducibility (2σ) of the SRM987 standard is 7 ppm. Nd was loaded
on double filaments with 1 M HNO3. 143Nd/144Nd values were
internally corrected for fractionation using a 146Nd/144Nd value of
0.7219 and the 144Sm interference on 144Nd was monitored on the
mass 147Sm and corrected by using a 144Sm/147Sm value of 0.206700.
External reproducibility (2σ) of the JNdi-1 standard (Tanaka et al.,
2000) is 4 ppm.
87
Sr/86Sr and 143Nd/144Nd whole rock compositions were cor-
rected for time-integrated decay of 87Rb and 147Sm using Rb, Sr, Sm
and Nd concentrations determined by LA-ICP-MS on whole rocks and
ages of 77 Ma, 42 Ma and 35 Ma for the Rio Cala arc lavas, Macuchi arc
lavas and high-level intrusions and Macuchi dolerite dykes respec-
tively. The resulting time-integrated corrections are small (less to
much less than 300 pm for 87Sr/86Sr and less to much less than
200 pm for 143Nd/144Nd: see Table 2).

6. Results

6.1. Petrography and alteration

Lavas of the Rio Cala and Macuchi arc are basaltic and basaltic to
andesitic in composition, respectively, and consist of phenocrysts of
plagioclase, clinopyroxene ± amphibole and relict olivine in a matrix
of plagioclase, clino- and orthopyroxene and glass with accessory Fe–
Ti-oxides. Basaltic and andesitic lavas of the Rio Cala and Macuchi
arc have been erupted in a submarine setting as suggested by the
occurrence in both arc sequences of pillow structures, hyaloclastite,
and perlitic textures (Tripodi, 2002; Vallejo, 2007; Chiaradia et al.,
2008). Several basaltic lava samples contain abundant vesicles now
filled with alteration minerals (amygdales: see below). High-level
subvolcanic intrusions occur in the Macuchi arc and consist of
amphibole and/or plagioclase-bearing porphyritic rocks of andesitic
to dacitic composition (Table 2). In some samples, andesitic to dacitic Fig. 4. (A) TAS diagram (LeBas et al., 1986) and (B) Zr/TiO2 versus Nb/Y plot
porphyritic blebs (millimetric to centimetric in size) are intermingled (Winchester and Floyd, 1977) for the classification of the magmatic rocks of the Rio Cala
with host basaltic lavas indicating a broad contemporaneity between and Macuchi arcs.
476 M. Chiaradia / Chemical Geology 265 (2009) 468–487
such as Fe2O3 and MgO as well as concentrations of high-field strength
elements (HFSE: e.g., Zr, Ti, Y, V, Sc, Th) and rare earth elements (REE),
usually considered as fluid-immobile, are unlikely to be significantly
affected. Additionally, although usually considered a fluid-mobile
element, also Sr displays correlations with the above-defined
immobile elements (see below) suggesting that its concentrations
were not, in general, significantly altered. Pb and Sr (as well as Nd)
isotope analyses were carried out on leached fractions of the whole
rocks (see above) to remove Pb and Sr contained in secondary
minerals. The correlations shown by these isotope systems (see
below) with the above “immobile” elements suggest that the removal
of alteration-related Pb, Nd and Sr, if present, was successful to a good
extent.
6.2. Geochemistry of Rio Cala arc rocks
The investigated Rio Cala arc magmatic rocks are basaltic in
composition (Fig. 4A and B), with possibly one sample being a basaltic
andesite (Fig. 4A: caution is necessary due to the possible presence of
quartz-filled amygdales). Although straddling the boundary between
tholeiitic and calc-alkaline fields, they display evolutionary trends
towards the tholeiitic series in the AFM and FeOtot/MgO versus SiO2
plots (Fig. 5). Fe2O3 (TiO2, V) increases, Sc remains almost unchanged
whereas Ni and Cr strongly decrease with decreasing MgO (Fig. 6).
Incompatible elements such as Sr, Y, and Nb (not shown) do not
correlate with MgO decrease. In contrast, HFSE and REE ratios (e.g., Zr/
Sm, Zr/Hf) and, to some extent, Zr and Hf (not shown) display a
decrease with MgO (Fig. 6), except for the MgO-richest sample
(E99103).
In the Y–Cr diagram for basalt discrimination (Fig. 7A), Rio Cala
basalts plot in the field of arc basalts (e.g., Fig. 7). However, in other
basalt discrimination plots (e.g., Ti–Zr, Zr–Ti/100-Sr/2: not shown),
some samples extend into the MORB field (see also Fig. 7B). In the
Fig. 5. (A) Na2O + K2O–FeOtot–MgO (AFM) (Kuno, 1968) and (B) FeOtot/MgO versus
SiO2 (Miyashiro, 1974) plots for the discrimination of tholeiitic and calc-alkaline
magmatic series. For discussion refer to text.
NMORB-normalized spider-diagram (Fig. 8) of Sun and McDonough
(1989) all samples display variably deep Nb negative anomalies,
typical of subduction-related magmas, and variable enrichments in
LILE (although concentrations of the latter may have been affected
by metamorphism). The REE spectra are almost flat with a very
slight enrichment in LREE and are typical of tholeiitic arc basalts
(Fig. 8).
The Rio Cala arc rocks are characterized by primitive 143Nd/144Ndi
between 0.51285 and 0.51230, by 87Sr/86Sri values between 0.703
and 0.705 and by 207Pb/204Pb values between 15.53 and 15.60. In Pb
versus Pb and Nd versus Pb isotope diagrams (Figs. 9 and 10A) rocks of
the Rio Cala arc display compositions largely overlapping the fields of
the main oceanic reservoirs of the region, namely East Pacific Rise,
Galapagos Spreading Center, Galapagos Islands, and Pallatanga
oceanic plateau terrane, but also defining a trend towards the EM2
end-member of Zindler and Hart (1986). In Nd versus Sr and Pb versus
Sr isotope plots (Fig. 10B and C) they define trends pointing towards a
radiogenic Sr reservoir, which could be either the EM2 end-member of
Zindler and Hart (1986) or seawater-altered oceanic crust. It is
important to note that the radiogenic Sr compositions are unlikely the
result of seawater alteration (e.g., due to the precipitation of
secondary carbonate minerals) because rocks were leached before
isotopic analyses (see above). If they contain a component of
seawater-altered oceanic crust this has been acquired during primary
magmatic processes (see below).
Pb isotope ratios correlate with compatible elements such as MgO,
Fe2O3, Ni and Cr, but also with HFSE like Hf and Zr and their ratio
(Fig. 11), whereas 87Sr/86Sr and 143Nd/144Nd values correlate with
ratios of incompatible HFSE and REE like Zr/Sm, Zr/Y, Ce/Sm, but not
with compatible elements. The consistent correlations of both Sr and
Nd isotopes with HFSE and REE further supports that the radiogenic
Sr isotopic compositions of the Rio Cala rocks have petrogenetic
significance.
6.3. Geochemistry of the Macuchi arc rocks
Lava flows and associated high-level intrusive porphyritic rocks of
the Macuchi Unit (plus the two lava samples from the Silante Unit and
Tortugo Formation: see above) range in composition from basaltic to
dacitic, with lava flows being basaltic to andesitic and porphyritic
intrusive rocks being andesitic to dacitic (Table 2 and Fig. 4). Dolerite
dykes cutting lava flows in the La Plata area are consistently basaltic
(Fig. 4).
In the AFM and FeOtot/MgO versus SiO2 plots, the Macuchi arc
lavas and associated intrusive rocks define trends starting in the
tholeiitic field but evolving into the calc-alkaline field, whereas the
dolerite dykes follow rather a tholeiitic trend (Fig. 5). A calc-alkaline
affinity for the Macuchi arc lavas and associated intrusive rocks is
supported by the fact that Fe2O3, and V (plus TiO2: not shown)
decrease with chemical evolution (Fig. 6). In contrast, the dolerite
dykes (like Rio Cala arc rocks) are characterized by increasing values
of Fe2O3 and V (plus TiO2: not shown) with chemical evolution
(Fig. 6), in agreement with their tholeiitic affinity.
Compared to Rio Cala arc lavas and Macuchi dolerite dykes,
Macuchi arc lavas and high-level intrusive rocks are characterized by
lower MgO as well as Ni and Cr concentrations (Fig. 6). For decreasing
MgO contents they show a consistent decrease (besides Fe2O3, TiO2,
V) of Ni, Cr, Sc, and Y and a continuous increase in Sr and Zr/Sm (plus
Zr, U, and also, not shown, Th, Rb, Hf and other incompatible elements:
Fig. 6). The Macuchi dolerite dykes display identical trends as the Rio
Cala arc rocks in the plots of Fig. 6, except for a trend of increasing Zr
with decreasing MgO as opposed to the trend of decreasing Zr with
decreasing MgO of the Rio Cala arc rocks.
In basalt discrimination diagrams (Fig. 7), all Macuchi arc lavas and
high-level intrusive rocks plot in the island arc field whereas the
dolerite dykes show mixed arc and MORB affinities (confirmed also by
 M. Chiaradia / Chemical Geology 265 (2009) 468–487 477

Fig. 6. Major and trace elements versus MgO plots for the magmatic rocks of the Rio Cala and Macuchi arcs. For discussion refer to text.

various other basalt discrimination plots not shown here). In the
NMORB-normalized spider-diagram of Sun and McDonough (1989)
(Fig. 8), all Macuchi arc rocks (including the dolerite dykes) display
the typical fingerprint of subduction-related magmas, with variably
deep Nb negative anomalies and variable enrichment in LILE
(although the latter could have been mobile during the low grade
metamorphism of the arc sequence). REE spectra of Macuchi arc lavas
and high-level intrusive rocks are characterized by slightly enriched
light REE (LREE) values compared to Macuchi dolerite dykes and Rio
Cala arc lavas and especially by moderately to strongly depleted heavy
REE (HREE) in the high-level intrusive rocks (Fig. 8).
The Macuchi arc lavas and high-level intrusive rocks display
altogether strongly increasing Sr/Y and La/Yb with decreasing MgO
and the porphyritic intrusive rocks (i.e., the most evolved of the
series) fall in the adakite field in the Sr/Y versus Y plot, but not in the
La/Yb versus Yb plot (Fig. 12). The andesitic to dacitic high-level
478 M. Chiaradia / Chemical Geology 265 (2009) 468–487
Fig. 7. (A) Cr/Y (Pearce, 1982) and (B) V–Ti/1000 (Shervais, 1982) geotectonic discrimination diagrams for basaltic rocks of the Rio Cala and Macuchi arcs. For discussion refer to text.
intrusive rocks might appear to form a cluster at variably high Sr/Y
and La/Yb values (Fig. 12) as well as at low Y, Fe2O3 and V contents
(Fig. 6) as they were forming a separate group with respect to basaltic
to andesitic lavas of the Macuchi arc, but more samples would be
needed to check this.
The Macuchi lavas and associated intrusive rocks are characterized
by slightly more variable and crustal Sr and Nd isotopic compositions
than Rio Cala lavas (143Nd/144Ndi = 0.51280–0.51230; 87Sr/86Sri =
0.7030–0.7052) and by significantly more variable and crustal Pb
isotope compositions (207Pb/204Pb = 15.56–15.67). In contrast, Macu-
chi dolerite dykes have homogeneous 143Nd/144Ndi values around
0.5130, 87Sr/86Sri between 0.7035 and 0.7045, and 207Pb/204Pb
between 15.59 and 15.67.
In Pb versus Pb, Sr versus Nd, Sr versus Pb and Nd versus Pb
isotopic plots (Figs. 9 and 10) rocks of the Macuchi arc define trends
between the Pallatanga terrane (but also East Pacific Rise, Galapagos
Spreading Center, Galapagos Islands) and the EM2 end-member. Also
in this case, like for Rio Cala arc rocks, the radiogenic Sr isotopic
compositions are unlikely due to seawater alteration because rocks
were leached before isotopic analyses.
Macuchi lavas and associated intrusive rocks display consistent
correlations of Pb and Sr isotopes (and, less evident, Nd isotopes) with
evolution indices such as MgO, Fe2O3, Sr, Y, Zr, Yb, Sr/Y, Zr/Hf (Fig. 11
reports only some of the best correlations). These correlations
reinforce the idea that radiogenic isotopes obtained on leached
fractions have petrogenetic significance. In particular the correlation
between decreasing 87Sr/86Sr and increasing Sr concentrations
(Fig. 11J) makes it unlikely the possibility of seawater alteration as
responsible for these trends. In fact in such a case the opposite
correlation should be expected, although some scatter in the Sr–87Sr/
86
Sr trend might indeed result from secondary seawater alteration
having changed Sr concentrations in the rocks (87Sr/86Sr ratios are
more likely to reflect “magmatic” values because obtained on leached
fractions). The Macuchi dolerite dykes, probably due to the limited
sample number, do not show clear trends in the isotope versus
element spaces (not shown).
7. Discussion
The rocks of the Western Cordillera of Ecuador here investigated
belong to three magmatic events (Rio Cala arc, Macuchi arc, dolerite
dykes cutting the lavas of the Macuchi arc) that differ for their
geochemical and isotopic characteristics. The model of Vallejo et al.
(2009), schematically represented in Fig. 3, allows the geochemical
evolution of these rocks, in particular the transition from non-adakitic
rocks of the Rio Cala arc to the adakite-like signatures of the high-level
intrusions of the Macuchi arc, to be placed in a suitable geodynamic
context.
7.1. Source and evolution of the Rio Cala arc magmas
Magmatic rocks of the Rio Cala island arc are associated with Late
Cretaceous westward subduction of oceanic crust under a fragment of
the CCOP (Pallatanga terrane: Fig. 3), according to the model of Vallejo
et al. (2009). A subduction-related fingerprint for Rio Cala arc rocks is
indicated by their variably deep Nb negative anomalies (Fig. 8). The
least evolved rocks of the Rio Cala arc have high MgO (N8 wt.%,
Mg# ≥ 0.65), Ni (N150 ppm) and Cr (≥200 ppm) contents, which are
close to those of primitive arc basalts of other island arc settings (e.g.,
Lesser Antilles: Pichavant and MacDonald, 2003, 2007). The high Ni
and Cr contents of the MgO-rich basalts of the Rio Cala arc indicate
that they were most reasonably derived from partial melting of a
spinel-bearing peridotitic mantle (see also Pichavant and McDonald,
2003). Different degrees of partial melting of such a mantle and/or
melting of compositionally different mantle domains are possible in
view of the variable contents of Nb and other HFSE of some of the most
primitive (MgO N 8 wt.%) rocks of the Rio Cala arc (e.g., samples
E99103 and E99204: see Table 2 and Fig. 6). More data would be
needed to explore this aspect in detail.
Correlations of Pb isotopes with compatible (Ni, Cr, MgO) and
incompatible (Zr, Hf) elements and with HFSE ratios (e.g., Zr/Y, Zr/Hf)
indicate that the most primitive (MgO- and Ni-richest) rocks (which,
excluding sample E99103, are the richest in HFSE like Zr and Hf and
have the highest Zr/Sm and Zr/Hf values: Fig. 6) are the most
radiogenic ones in terms of Pb isotopes (207Pb/204Pb up to ∼ 15.60 and
206
Pb/204Pb up to ∼ 18.90: Fig. 11). At the same time, the correlations
of Zr/Sm (but also, not shown Zr/Y, Ce/Sm) with Sr and Nd isotopes
(Fig. 11) suggest that the most primitive rocks (highest in Zr/Sm) are
the least evolved in terms of Sr and Nd isotopes (i.e., lower 87Sr/86Sr
and higher 143Nd/144Nd). Therefore, the isotopic compositions of the
most primitive magmas of the Rio Cala arc (radiogenic Pb and Nd and
non-radiogenic Sr) are compatible with those of an EPR-type mantle
slightly enriched by subducted sediments-derived radiogenic lead
(EM2 end-member in Figs. 9 and 10). Because Pb is more mobile than
Sr and especially Nd in the fluid phase and because the ratio of [Pb
concentration in subducted sediments]/[Pb concentrations in
depleted mantle] is much higher (N1000) than corresponding ratios
of Sr and Nd (both ∼40), it is reasonable that the Pb fingerprint of the
fluid phase released by the subducted slab and metasomatising the
mantle wedge is more marked than that of Sr and Nd.
Since Rio Cala rocks were collected tens to hundreds of km apart
along the arc (Fig. 1) and therefore are not cogenetic, the correlations
of geochemical indices with geochemical indices and radiogenic
isotopes (Figs. 6 and 11) probably indicate the occurrence of a similar
magmatic process along the arc involving two main magma sources,
which are compositionally and isotopically rather uniform. Under this
point of view, the scatter of some samples around the trends could
 M. Chiaradia / Chemical Geology 265 (2009) 468–487 479

Fig. 8. NMORB-normalized trace element (Sun and McDonough, 1989) and chondrite-normalized REE (Sun and McDonough, 1989) spider-diagrams for rocks of the Rio Cala and
Macuchi arcs. For discussion refer to text.

reflect, besides analytical uncertainties and alteration, changes in the
compositions of the sources and/or of the magmatic process along the
arc. Taking into account the geodynamic setting in which the Rio Cala
arc was formed, at least three different processes could explain the
correlations between isotopes and geochemical indices for rocks of
the Rio Cala arc: (i) mixing between melts derived from composi-
tionally and isotopically different mantle domains; (ii) fractionation of
mantle-derived melts with concomitant assimilation of the host
oceanic plateau crust (AFC); (iii) mixing between mantle-derived
melts and partial melts of the host oceanic plateau crust.
Concerning process (i) above, the low MgO and very low Ni and Cr
contents of the most evolved rocks of the Rio Cala arc (Fig. 6) suggest
that they must have undergone significant fractionation. Mixing
between a MgO-rich mantle-derived melt and a melt derived from a
compositionally and isotopically different mantle domain that has
subsequently undergone olivine and spinel fractionation might
explain the trends of Pb isotopes with strongly decreasing compatible
elements but not those of MgO and radiogenic isotopes with Hf, Zr or
HFSE ratios (Figs. 6 and 11). In fact, the fractionated end-member
should have higher HFSE contents than the MgO-rich melt (resulting
in opposite trends of Zr, Hf, Zr/Hf and Zr/Sm with MgO and radiogenic
isotopes), unless partial melting of an extremely depleted mantle has
occurred. Alternatively, the evolved end-member of the Rio Cala trend
might derive from partial melting of eclogite- or pyroxenite-rich
480 M. Chiaradia / Chemical Geology 265 (2009) 468–487

melts and magmas derived from melting of clinopyroxene-rich

(ankaramitic) oceanic plateau crust.
Whereas the mixing trends towards non-radiogenic Pb and
radiogenic Nd isotopes (Fig. 11) are consistent with assimilation of
partial melts of ankaramitic rocks of the Pallatanga terrane (Fig. 10),

Fig. 9. 208Pb/204Pb and 207Pb/204Pb versus 206Pb/204Pb plots for rocks of the Rio Cala
and Macuchi arcs compared with fields of the Pallatanga terrane (Mamberti et al.,
2003), East Pacific Rise, Galapagos spreading center and Galapagos islands (data from
White et al., 1993), Paleozoic–Triassic basement rocks of Ecuador (Chiaradia et al.,
2004b), EM2 (Zindler and Hart, 1986) and global subducted sediments (GLOSS: Plank
and Langmuir, 1998). Upper crust (UC) and orogen (OR) evolution curves are from
Zartman and Doe (1981). For discussion refer to text.

portions of the mantle, which would have low Ni contents (Ishiwatari

et al., 2008) and low (subchondritic) Zr/Sm values (e.g., Rapp et al.,
2003). For the same reasoning, process (ii) above cannot explain
decreasing Zr and Hf contents as well as decreasing Zr/Sm and Zr/Hf
with decreasing MgO and their correlations with radiogenic isotopes
(Figs. 6 and 11), even if fractional crystallization was accompanied by
extensive assimilation of very low HFSE material.
Another possibility is that primitive MgO-rich melts have mixed
with partial melts of the oceanic plateau crust of the Pallatanga
terrane (process (iii) above). In particular, crustal melting of
clinopyroxene-rich (ankaramitic) lithologies of the Pallatanga oceanic
terrane (see also Mamberti et al., 2003), perhaps followed by some
fractionation, might account for the very low Ni contents of the most
evolved rocks of the Rio Cala arc (see also Ishiwatari et al., 2008) as
well as for their low Zr and Hf contents and low Zr/Hf and Zr/Sm
values, clinopyroxene being characterized by DZr b DSm and DZr b DHf.
Fig. 10. 143Nd/144Nd versus 206Pb/204Pb (A), 143Nd/144Nd versus 87Sr/86Sr (B) and 87Sr/
Such a possibility, already proposed by Allibon et al. (2008), is 86
Sr versus 206Pb/204Pb (C) plots for rocks of the Rio Cala and Macuchi arcs compared
consistent with the Pb and Nd isotope compositions of the Pallatanga with fields of the Pallatanga terrane (Mamberti et al., 2003) and East Pacific Rise (EPR),
oceanic plateau terrane, which are less radiogenic than those of the Galapagos Spreading Center (GSC) and Galapagos islands (GIs) (data from White et al.,
least evolved rocks of the Rio Cala arc (Figs. 9 and 10), and would 1993). The DMM (Depleted MORB Mantle), BSE (Bulk Silicate Earth), HIMU (high µ),
EM1 (Enriched Mantle 1) and EM2 (Enriched Mantle 2) end-members are from Zindler
explain the correlation trends between decreasing 143Nd/144Nd and and Hart (1986). For discussion refer to text. The field of seawater-altered Pallatanga
decreasing Zr/Sm and between decreasing 206Pb/204Pb and decreas- oceanic crust is drawn based on the 87Sr/86Sr composition of Late Cretaceous seawater
ing Zr/Hf (Fig. 11) as the result of mixing between mantle-derived (∼ 0.7075: McArthur et al., 2001).
 M. Chiaradia / Chemical Geology 265 (2009) 468–487 481

Fig. 11. Correlations between various geochemical evolution and adakitic indices with Pb, Sr and Nd isotope values for rocks of the Rio Cala and Macuchi arcs. For discussion refer to
text. AFC and mixing models based on the equations of DePaolo (1981) and simple mixing equations for rocks of the Macuchi arc in the Sr/Y versus 207Pb/204Pb (Fig. 11H). Table 4
reports boundary conditions used for modelling. For discussion refer to text and Table 4.

the trend towards more radiogenic Sr isotopes indicated by the tions of the Pallatanga oceanic plateau underlying the Western
correlation between 87Sr/86Sr and Zr/Sm (Fig. 11) suggests assimila- Cordillera of Ecuador (Mamberti et al., 2003; Fig. 10). It might suggest
tion of radiogenic Sr, which is not compatible with known composi- an insufficient isotopic characterization of rocks of the Pallatanga
482 M. Chiaradia / Chemical Geology 265 (2009) 468–487

Fig. 12. Sr/Y versus Y, Sr/Y versus MgO, La/Yb versus Yb and La/Yb versus MgO plots for rocks of the Rio Cala and Macuchi arcs. For discussion refer to text.

terrane or a preferential melting and subsequent assimilation of
seawater-altered Pallatanga oceanic plateau crust (Fig. 10). This latter
possibility would be consistent with fluid dynamic calculations
(Huppert and Sparks, 1988) and experimental results (Campbell and
Turner, 1987) on crustal magmatic assimilation processes and has
been also proposed for the petrogenesis of tholeiitic rocks of the
Eastern Galapagos Spreading Center (Perfit et al., 1999).
7.2. Source of the Macuchi arc lavas
The Macuchi arc, according to the model of Vallejo et al. (2009), is an
autochthonous arc formed during eastward subduction upon the
Pallatanga oceanic plateau, after accretion of the latter in the Late
Cretaceous (Fig. 3). All rocks of the Macuchi arc have typical subduction-
related features such as Nb negative anomalies and LILE enrichment
(although the latter might be affected by the metamorphism).
Compared to the most primitive rocks of the Rio Cala arc, those of the
Macuchi arc are poorer in MgO (7 wt.%), Ni (40 ppm) and Cr (140 ppm)
and have slightly higher SiO2 contents (Fig. 6). The low Ni contents
suggest that the least evolved rocks of the Macuchi arc underwent
significant olivine fractionation or, alternatively, were derived from
elements is that, during the Eocene eastward subduction leading to the
formation of the Macuchi arc magmatism, sediments were transferred to
the mantle wedge through partial melting or mechanical incorpora-
tion (see also Gerya and Stockhert, 2006; Klimm et al., 2008).
However, whereas these processes can account for the non-radio-
genic Nd and radiogenic Sr and Pb isotopic composition of the least
evolved magmas of the Macuchi arc, the high Th/Nb and Th/La values
of the latter cannot be explained neither by bulk sediment transfer
nor by sediment partial melting (Fig. 13 and Table 3). In contrast, they
can be explained by a sediment-derived supercritical (?) fluid com-
ponent (Fig. 13 and Table 3). As highlighted by other studies (e.g.,
Hochstaedter et al., 2001) this seems to imply Th and Nd mobility in a
supercritical (?) fluid phase released from the subducted slab.
Table 3
Compositions of potential reservoirs for the Rio Cala and Macuchi arc magmas.
143
Th Nb La Pb Zr Nd/144Nd References/
(ppm) (ppm) (ppm) (ppm) (ppm) notes

partial melting of olivine-poor portions of the mantle, for instance N-MORB 0.12 2.33 2.5 0.3 74 0.513150 1, 2
AOCa 0.07 1.22 1.84 0.7 66.5 0.513077 3, 4, 5
dominated by pyroxenite or eclogite (e.g., Ishiwatari et al., 2008).
AOC fluid 0.166 0.364 0.126 23.49 0.848 0.513077 6
The least evolved rocks of the Macuchi arc are characterized by the Sediment 6.91 8.94 28.8 19.9 130 0.512180 7
most radiogenic Pb (207Pb/204Pb up to 15.67) and, opposite to Rio Cala arc Sediment melt 7.4 7.94 23.9 17.0 130 0.512180 8
rocks, also by the most radiogenic Sr (87Sr/86Sri up to 0.7052) and by the Sediment fluid 16.39 2.67 1.97 668 1.66 0.512180 9
least radiogenic Nd signatures (143Nd/144Ndi down to 0.5128: Fig. 11). References: 1 = Sun and McDonough (1989); 2 = Klein (2004); 3 = Staudigel et al. (1996);
Excluding seawater alteration (see above), the isotopic signatures of the 4 = Hochstaedter et al. (2001); 5 = GERM web page (http://earthref.org/GERM); 6 =
most primitive lavas of the Macuchi arc (MgO=7.0 wt.%; Mg#=0.55) are calculated from AOC following the method of Hochstaedter et al. (2001): fluid released by AOC
dehydrating during subduction, assuming 2% of fluid in equilibrium with AOC and fluid/solid
significantly more crustal than those of the most primitive rocks of the Rio
partition coefficients (gar:cpx:rut=59.5:39.5:1) from Brenan et al. (1995a,b); 7 = global
Cala arc (207Pb/204Pb=15.60; 87Sr/86Sri ∼0.703; 143Nd/144Ndi ∼0.5130) subducting sediment (GLOSS) of Plank and Langmuir (1998); 8 = calculated from Sediment
and suggest derivation from a mantle enriched not only by subducted following the method of Hochstaedter et al. (2001), i.e., assuming 40% melt in equilibrium
sediments-derived Pb but also Sr and Nd (EM2-type mantle in Fig. 10), with Sediment and melt/solid partition coefficients from Johnson and Plank (1999); 9 =
compared to that from which originated the most primitive rocks of the calculated from Sediment following the method of Hochstaedter et al. (2001): fluid released
by Sediment dehydrating during subduction, assuming 2% of fluid in equilibrium with
Rio Cala arc which was slightly enriched only in Pb. Sediment and fluid/solid partition coefficients (gar:cpx:rut=59.5:39.5:1) from Brenan et al.
A possible explanation of the enrichment of the mantle both by very (1995a,b).
fluid-mobile (Pb), relatively fluid-mobile (Sr) and fluid-immobile (Nd) a
AOC = altered oceanic crust.
 M. Chiaradia / Chemical Geology 265 (2009) 468–487 483

Fig. 13. 143Nd/144Nd versus Th/Nb and Th/La versus Th/Nb plots for the investigated rocks. The Macuchi arc lavas show a higher sediment fluid component than rocks of the Rio Cala
arc and the dolerite dykes of the Macuchi arc. Note that the isotopic and geochemical compositions of the Macuchi arc lavas cannot be explained neither by sediment melting or bulk
incorporation into a N-MORB-type mantle wedge nor by a slab fluid released uniquely from the subducted Altered Oceanic Crust (AOC). Compositions of the potential reservoirs are
detailed in Table 3.

7.3. Magmatic evolution of the Macuchi arc lavas and associated pH2O was high enough to stabilize clinopyroxene, amphibole, and
intrusions garnet but not plagioclase. Magmatic garnet crystallization (Müntener
et al., 2001; Macpherson et al., 2006; Rodríguez et al., 2007; Alonso-
The rocks of the Macuchi arc show a broad compositional range, Perez et al., 2009) in hydrous basaltic magmas occurs at pressures of
from basaltic to dacitic, which is characterized by systematic 1.5–2.0 GPa, or, under high pH2O and temperatures below 1100 °C, as
geochemical and isotopic correlations. The increasing Sr contents low as 1.2 GPa (Müntener et al., 2001) or even 0.8 GPa (Alonso-Perez
and Sr/Y values with decreasing MgO (Fig. 6) are compatible with et al., 2009). The thickness of the crust in the Western Cordillera of
suppression of plagioclase fractionation, at least in the most evolved Ecuador (at least 40 km) is consistent with the possibility that garnet
andesitic to dacitic magmas, where Sr enrichment is greatest. At the was stable in magmas evolving at the base of such a crust or even
same time lower contents of middle REE (MREE: e.g., Tb) and Y as well within its lower levels, although there is no direct evidence of the
as strongly increasing Zr/Sm values in the high-level intrusive rocks occurrence of magmatic garnet in the Macuchi rocks. Alternatively,
(Figs. 6, 8, 12) suggest extensive fractionation of clinopyroxene and garnet could be a restitic phase from partial melting of a lower mafic
amphibole (for both of which DZr b DSm). The possibility of clinopyr- crust (e.g., Atherton and Petford, 1993).
oxene and amphibole fractionation is supported by their occurrence as Nonetheless, the correlations of Pb and Sr (and to some extent Nd)
phenocrysts in the andesitic to dacitic porphyritic high-level intru- isotopes with various evolution indices (Figs. 11) indicate that
sions. The strongly depleted HREE contents (Tm, Yb, Lu) of the fractional crystallization is not the only responsible for petrogenesis
andesitic-dacitic porphyritic intrusions (Fig. 8) require fractionation of the Macuchi arc rocks and imply open system processes such as AFC
of a few percent (up to 6–8%) of garnet estimated by modelling REE and/or mixing. In reality, because true AFC or mixing processes are
patterns of these samples as the result of fractional crystallization of incompatible with the geographic spread of the Macuchi samples, the
various possible basaltic parent magmas chosen among the least above correlations rather indicate, like for Rio Cala arc rocks, the
evolved rocks of both the Macuchi and Rio Cala arc. Therefore, involvement of relatively homogeneous magma sources and of
andesitic to dacitic magmas of the high-level intrusions are likely to broadly similar magmatic processes along the arc as responsible for
have reached their compositions at lower to mid-crustal levels where the petrogenesis of the Macuchi rocks.
The correlations of adakitic indices with geochemical evolution
and radiogenic isotopes (Figs. 6, 11, 12) are difficult to reconcile with
the slab melting hypothesis. A more likely scenario explaining them is
that of a deep crustal hot zone (e.g., Annen et al., 2006, but see also
Table 4 Petford and Gallagher, 2001; Dufek and Bergantz, 2005). In the deep
Parameters used for modelling AFC and mixing trends for the Macuchi rocks. crustal hot zone model, mantle-derived basaltic magmas injected into
207
Pb/204Pb Pb Sr Y the lower to mid-crust, fractionate, partially melt and assimilate the
Parenta 15.67 0.7 ppm 200 ppm 22 ppm surrounding crust, yielding hybrid intermediate to felsic magmas with
Assimilantb 15.56 4 ppm 80 ppm 22 ppm adakite-like signatures due to magmatic evolution at high pressures
Mixc 15.57 6 ppm 400 ppm 2 ppm (see also Chiaradia et al., 2009). These hybrid magmas, which acquire
D (for AFC)d 0 0 3 a distinct isotopic signature with respect to their parents because of
AFC model curves were derived using the equations of DePaolo (1981), whereas mixing interaction with the lower/mid- crust, subsequently rise to shallower
model curves were derived from simple two end-member mixing equations. levels where they undergo further fractionation and mix with other
a
Pb and Sr concentrations falling within the range of oceanic island arc basalts (Kelemen
magmas, some of which might have short-circuited the deep crustal
et al., 2004) that yield the best fit to the observed data. The 207Pb/204Pb value is that of
the most radiogenic Macuchi sample (E99174). evolution (e.g., basaltic rocks of the Macuchi arc), yielding the
b
Hypothetical compositions of a refined CCOP crust that provide the best fit to the correlation trends between geochemical and isotopic indices observed
observed data. The Sr value falls within the range of the CCOP crust whereas Pb contents for the Macuchi rocks. The occurrence of mingling textures between
are higher than typical CCOP values (according to data in Mamberti et al., 2003 and Kerr, basaltic and andesitic-dacitic magmas in lavas of the Macuchi arc
2004).
c
Compositions of a hypothetical end-member required to fit the observed trend for a
supports the possibility of magma mixing as a petrogenetic process.
model of two-end member mixing. Alternatively, the observed correlation trends might indicate a
d
See text for explanations. temporal evolution from initial basaltic magmatism, rising and
484 M. Chiaradia / Chemical Geology 265 (2009) 468–487
evolving at shallow crustal levels, to late andesitic-dacitic magmatism
evolving in the deep crustal hot zone before rising to shallower levels.
This hypothesis could be consistent with the fact that adakite-like
rocks occur as high-level intrusions cutting most of the lava sequence
of the arc and therefore might be late magmatic episodes. The lack of
systematic geochronology on both lavas and intrusive rocks of the
Macuchi arc precludes at the moment the possibility to test further
these two scenarios.
Both the thick oceanic plateau crust of the Pallatanga terrane, the
Rio Cala arc rocks (as underplated material at the base of the
Pallatanga terrane), or the Pallatanga oceanic crust modified through
interaction with magmas of the older Rio Cala and Silante arcs are
isotopically consistent with being the non-radiogenic isotopic end-
member of the Macuchi rock trends (Figs. 9–11). However, due to the
deep crustal evolution of the most evolved magmas of the Macuchi
series discussed above and the evidence of subudction-related
geochemical signatures in all rocks of the Macuchi arc (e.g., Nb
negative anomalies), it is likely that the assimilant was underplated
mafic material related to the build-up of the earlier Rio Cala and
Silante arcs (or even the early stages of Macuchi itself) or an oceanic
plateau crust “modified” by the continuous interaction with subduc-
tion-related mantle-derived melts (see also Lee et al., 2006; Chiaradia
et al., 2009). The pristine oceanic plateau crust of the Pallatanga
terrane in fact does not have subduction geochemical hallmarks like
Nb negative anomalies (see Mamberti et al., 2003).
7.4. Geodynamic significance of the adakite-like rocks of the Macuchi arc
The lower to mid-crust depth suggested by geochemical signatures
for the magmatic evolution of the andesitic to dacitic magmas of the
Eocene Macuchi arc could be the consequence of two factors:
i) Thickening of the crust upon which the Macuchi arc was formed,
due to the building of subsequent magmatic arcs (Rio Cala, Silante,
Macuchi itself) in the same crustal section through distinct
subduction episodes (see Fig. 3);
ii) Increased coupling between subducting and overriding plate
during eastward subduction due to the arrival at the trench of
small oceanic plateau fragments carried on top of the oceanic
plate as a swarm behind the main Pallatanga accreted fragment.
The ensuing increased compression (see also Graindorge et al.,
2004 for a similar situation in present-day Ecuador) would slow
down magma ascent to shallower levels and compel magmas to
evolve at deep levels for variably long periods (Chiaradia et al.,
2009).
The data above indicate that the Eocene Macuchi arc sequence
contains the oldest evidence (≤∼ 40 Ma, taking into account the
available ages of andesitic high-level intrusions: see above) of adakite-
like magmatism in the Western Cordillera of Ecuador. Works of
Chiaradia et al. (2004a), Somers et al. (2005), and Schütte et al. (2007)
suggest that rocks with adakite-like features occur in the Western
Cordillera of Ecuador also throughout the Miocene intercalated with
periods of normal calc-alkaline magmatism, and that their genesis,
like that of the Quaternary equivalents (e.g., Chiaradia et al., 2009), is
most reasonably related to deep crustal fractionation processes
accompanied by partial melting and assimilation of a mafic lower
crust. Given an appropriate crustal thickness, such a long-lived,
recurrent adakite-like magmatism intercalated with periods of
normal calc-alkaline magmatism requires periods of compression,
with consequent sealing of crustal transfer structures and forced
evolution of mantle-derived magmas at lower to mid-crustal levels,
intercalated with periods of relaxation favouring magma ascent to
shallow crustal levels and development of normal calc-alkaline
magmas. As discussed above, it can be speculated that several small
fragments of buoyant oceanic plateau crust were carried on top of the
Farallon plate first and the Nazca plate after 25 My ago as a swarm
behind the large oceanic plateau fragment accreted during the
Cretaceous or originating from the Galapagos hotspot in more recent
times. When arriving at the trench of northwestern South America,
they were responsible for the transient increased coupling between
subducting and overriding plates (see also Ego et al., 1996; Graindorge
et al., 2004; Pedoja et al., 2006 for the present-day Carnegie ridge
impact at the subduction zone), increased compression and con-
sequent episodic development of adakite-like geochemistry of the
magmas through their forced evolution within the lower to mid-crust
throughout the Tertiary. Additional geodynamic changes at the
subduction zone, like convergence rate and obliquity (Noblet et al.,
1996), could have also played a role in modulating the extensional and
compressional stress on the overriding plate.
7.5. Source and evolution of the Macuchi arc dolerite dykes
The MORB-type dolerite dykes cutting the Macuchi arc lavas
correspond to a magmatic episode post-dating the Macuchi arc lavas.
Their primitive Sr and Nd isotopic signatures (but evolved Pb isotopic
signatures and moderate Nb negative anomalies) suggest derivation
from a mantle only slightly modified by subduction-related fluids,
whereas the restricted compositional range suggests again, like for Rio
Cala, a geodynamic setting unfavourable to significant magma
maturation within the crust. Pressure-release melting of a MORB-
type mantle modified by slab fluids, perhaps associated with an intra-
arc rift episode, could be responsible for this magmatic event, but
more data are necessary to test this hypothesis.
7.6. Modelling magmatic evolution of rocks of the Macuchi arc
The correlations of geochemical indices with radiogenic isotopes
are suitable, in principle, to carry out modelling of the magmatic
evolution of the Macuchi rocks through AFC or mixing processes.
Nonetheless, it has been discussed above that these correlation
trends may be the result of multiple processes such as AFC at high
pressure accompanied by partial melting and mixing with lower
crustal melts and, possibly, subsequent mixing at shallower levels
with mafic magmas that have themselves previously fractionated. It
is difficult to reliably model the complex combination of these
processes using simple AFC and mixing equations (e.g., DePaolo,
1981) even if a fit between observed trends and model curves can
be obtained (see also Roberts and Clemens, 1995). The simple AFC
and mixing models here presented are, therefore, an oversimplifica-
tion, yet they can be used as a loose test to the reservoirs and mag-
matic processes discussed above as responsible for the petrogenesis
of the Macuchi rocks.
Modelling of AFC and mixing processes is shown for simplicity only
in the 207Pb/204Pb versus Sr/Y space. The boundary conditions of
parent magmas and assimilant/mixed end-members are reported in
Table 3. As it is customary with modelling, more or less large
uncertainties reside in the choice of isotopic and geochemical
compositions of the end-members, especially of the assimilant in
AFC processes. The latter is not easily constrainable for the Macuchi
arc rocks, which have partially evolved at depth through interaction
with underplated material of the Rio Cala arc or a refined oceanic crust
material (see above). Additionally, small changes in the element
concentration and/or isotopic compositions of the assimilant result in
significant changes of the modelling results. Therefore, not too much
significance should be attached to the values of assimilation and
fractionation obtained for the AFC model. In contrast, R values
(R = mass of the assimilant/mass of crystallized magma) as well as
element partition coefficients control the shape of the model AFC
curve, which is independent from the choice of the end-member
compositions, and therefore provide more reliable estimates on the
fractionating assemblage and on the ratio of crystallized melt to
assimilated material. Whereas in the AFC model the observed trends
 M. Chiaradia / Chemical Geology 265 (2009) 468–487
can be reproduced by various combinations of end-member composi-
tions, R and partition coefficient values, in the mixing model, once
determined the composition of one of the two end-members (e.g., the
most primitive one) the composition of the other is forcedly fixed to
threshold values above or below which the observed trend is not
reproduced by a model mixing line. The salient outcomes of modelling
of the Macuchi arc rocks are the following:
(i) Mixing reproduces the observed trend only for an assimilant
characterized by very low Y (≤2 ppm), high Sr (≥400 ppm)
and high Pb (≥6 ppm) contents. These compositions are
consistent with those of a partial melt of a basaltic protolith in
the stability field of clinopyroxene, amphibole and garnet but
not in that of plagioclase, which is consistent with the model of
the deep crustal hot zone.
(ii) AFC best reproduces the observed trends for elevated R values
(between 0.6 and 0.8) assuming an end-member composition
of a modified Pallatanga oceanic plateau crust (Table 4). To
obtain Sr and Y model concentrations that are internally
consistent with those of the most evolved rock of the Macuchi
series (i.e., Sr ∼630 ppm and Y ∼ 6 ppm), DY must be 3 and DSr
must be 0. A DSr of 0 (or close to zero) is required to comply
with the Sr increase (Fig. 6) through evolution, a consequence
of the fact that plagioclase was not fractionating in agreement
with the high pressure pH2O evolution of the Macuchi magmas.
A DY = 3 implies significant fractionation of mineral phases
such as amphibole and garnet, which are a receptacle of this
element and are also stable at high pH2O, and is consistent with
the low Y contents of the high-level intrusive rocks (Fig. 6). The
same trend can also be reproduced assuming lower DY but in
this case other parameters of the modelling have to be changed
accordingly (R, composition of the assimilant) and model Sr
and Y concentrations of the most evolved rocks will be
significantly higher than the true values thus violating the
internal consistency of the model. The high R values (N0.6)
suggest that if AFC is the process responsible for the correlation,
it must have occurred under a hot thermal regime such as that
present in the mid- or lower crust (see also DePaolo, 1981)
heated by repeated magma injections, which is again consistent
with the deep crustal hot zone model. In the AFC modelling the
most evolved term of the Macuchi series (a dacite with 69 wt.%
SiO2) requires assimilation of up to ∼40% of lower mafic crust
for a corresponding ∼45% crystallization of the parent magma
for R = 0.8 (Fig. 11). In view of the above discussion these latter
estimates have to be considered only as indicative.
8. Conclusions
The geochemical and isotopic evolutions of rocks from two distinct
Late Cretaceous and (Paleocene?–)Eocene magmatic arcs of the
Western Cordillera of Ecuador have been presented. The Late
Cretaceous intraoceanic Rio Cala island arc formed upon the
Pallatanga oceanic plateau crust during westward subduction before
accretion of the Pallatanga terrane onto the Ecuadorian margin. This
arc consists of basaltic flows with tholeiitic affinity characterized by
strongly decreasing MgO, Ni and Cr contents correlated with
decreasing Pb isotope ratios and by decreasing HFSE contents
correlated with Pb, Sr and Nd isotopes. The geochemical signatures
of the Rio Cala arc can be explained by different magmatic processes,
including mixing between variably evolved melts derived from
compositionally different mantle domains and AFC/mixing processes
in which a rather homogeneous mantle-derived melt assimilates
oceanic plateau crust of the Pallatanga terrane or mixes with its partial
melts through a broadly similar process along the arc.
After accretion of the Pallatanga terrane and overlying Rio Cala arc
onto the Ecuadorian margin, subduction resumed oceanward of the
485
accreted plateau dipping eastward. This new subduction event
produced the subaerial Silante arc first and the subaqueous Macuchi
arc later, superposed onto the Rio Cala arc and the underlying accreted
Pallatanga terrane. The most primitive rocks of the Macuchi arc have
crustal Pb, Sr and Nd isotope compositions and elevated Th/Nb and
Th/La values that are best explained by a subducted sediment-derived
supercritical (?) fluid metasomatism of the mantle wedge. The
basaltic rocks of the Macuchi arc are MgO-poorer than those of the
Rio Cala arc and have low Ni contents (b40 ppm) suggesting
significant olivine fractionation or derivation from melting of an
olivine-poor mantle domain, e.g., dominated by pyroxenite or eclogite.
The most evolved rocks of the Macuchi arc are andesitic to dacitic
high-level intrusions characterized by adakite-like signatures (high Sr,
low Y, low HREE). They derive most likely from hybrid intermediate to
felsic magmas that have evolved in a deep crustal hot zone. The
geochemical and isotopic variability of the Macuchi arc series could
thus be the result of mixing between the low-Ni mantle-derived
basaltic magmas and the hybrid intermediate to felsic magmas formed
in the deep parts of the thickened mafic crust of the Western
Cordillera of Ecuador. This model is consistent with the occurrence of
mingling textures between the mafic and intermediate/felsic magmas
in basaltic lavas of the Macuchi arc. Alternatively, there could be a
temporal evolution of magmatic processes characterized initially by
basaltic magmas rising to shallow crustal levels and evolving through
low-pressure fractionation of olivine and spinel followed by magmas
evolving at deep crustal levels and yielding adakite-like signatures.
The lack of systematic geochronology on lava flows and high-level
intrusions of the Macuchi arc prevents at this time to test which one of
these hypotheses is the more likely.
The increased crustal thickness, resulting from the formation of the
Rio Cala and Silante arcs and underplated material associated with
them, as well as from an increased coupling between subducting and
overriding plates, perhaps resulting from the arrival at the trench of
fragments of buoyant oceanic plateau crust, could have been
responsible for the deep crustal evolution of the andesitic to dacitic
Macuchi arc magmas. The Macuchi arc contains thus the oldest
episode of adakite-like magmatism in the Western Cordillera of
Ecuador, which has since continued, intercalated with periods of
normal calc-alkaline magmatism, until the present day. The arrival of
several discrete topographic highs (e.g., oceanic plateau fragments,
aseismic ridges as a swarm of the main oceanic plateau accreted in the
Late Cretaceous first and as a result of the Galapagos hotspot activity
later) could have been responsible for the transient increases of
coupling between subducting and overriding plates, resulting in
evolution of magmas at deeper crustal levels with development of
transient adakite-like signatures.
Acknowledgements
This work was greatly improved by the constructive reviews of Jon
Blundy and an anonymous reviewer. I am grateful to R. Spikings
(University of Geneva) for stimulating discussions about the geology
of the Western Cordillera of Ecuador. A. Ulianov (University of
Lausanne), M. Senn and F. Capponi (University of Geneva) are thanked
for technical assistance in sample preparation and analysis. This work
has been funded by the Swiss National Science Foundation (SNF
Project N. 200020-117616).
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