Carrasco et al., 2023

LITHOS 462-463 (2023) 107400
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LITHOS
journal homepage: www.elsevier.com/locate/lithos
Geochronological, geochemical and isotopic characterisation of the Early

Cretaceous Andean margin within Ecuador: The Alao Arc
Hugo Carrasco a, *, Richard Spikings a, Massimo Chiaradia a, Alexey Ulianov b, Paul Buenaño c,
Andrés Zambrano c, Cristian Vallejo c, Bernardo Beate c
a
Department of Earth Sciences, University of Geneva, 1205 Geneva, Switzerland
b
Institute of Earth Sciences, Université de Lausanne, 1015 Lausanne, Switzerland
c
Departamento de Geología, Facultad de Ingeniería en Geología y Petróleos, Escuela Politécnica Nacional, Quito 170517, Ecuador
A R T I C L E I N F O A B S T R A C T
Keywords: Tectonic models of the Early Cretaceous Andean margin in Ecuador are hindered by a paucity of accurate
Geochronology crystallisation ages of igneous rocks. The Alao Arc, situated on the western flank of the Cordillera Real in
Isotopes Ecuador, is mainly composed of submarine altered basalts to andesites, and the most deformed areas are
Geochemistry
frequently modified by greenschist metamorphism. To improve our knowledge of the evolution of the northern
Active margins
Andes prior to the accretion of the Caribbean Large Igneous Province we attempt to constrain the tectonic origin
Andes
Ecuador and crystallisation age of the arc’s volcanic rocks, using whole-rock geochemistry and isotopic tracing, combined
with 40Ar/39Ar geochronology. Major oxides and trace element abundances and Sr-Nd-Pb compositions show
that the Alao Arc comprises two separate assemblages, namely, typical arc-like volcanic rocks and E-MORB-like
basalts. These have been interpreted to have formed in a continental arc above thinned continental crust in an
extensional setting, and the E-MORB-type basalts are considered to have formed in an intra-arc rift. As the Alao
Arc’s volcanic rocks are devoid of zircon and baddeleyite we attempted to date the time of their crystallisation
using 40Ar/39Ar analyses of whole-rock groundmass and plagioclase. However, as the igneous rocks are modified
by varying degrees of alteration with the formation of secondary K- and Ca-bearing phases, none of the ~75 Ma
to ~16 Ma 40Ar/39Ar dates record the age of their crystallisation. The plateau and weighted mean 40Ar/39Ar date
populations define peaks at ~75–60 Ma and ~ 45–30 Ma that coincide with previously recognised tectonic
events that drove fluid circulation, modifying the Ar isotopic compositions. Based on the maximum depositional
ages of intercalated sedimentary rocks, the degree of deformation, geochemical and isotopic trends of the
Jurassic arc in Ecuador, and correlations with the Early Cretaceous Quebradagrande Arc of Colombia, we pro
pose that the Alao Arc formed during ~140–110 Ma.
1. Introduction to the Alao Arc, suggesting the arc sequence may extend for at least
1000 km along strike (e.g., Spikings et al., 2005; Fig. 1). Therefore, here
The Andean mountains formed via the long-lived (>500 Ma) inter we complement previous work and constrain the tectonic origin of the
action between oceanic lithosphere of the eastern Pacific and conti arc by combining field observations with petrology, whole rock
nental lithosphere of South America. Consequently, a majority of the geochemistry and isotopic tracing (Sr, Nd and Pb). The dominantly
Andean mountains consist of arc crust. Rock exposure along the western mafic character of the volcanic units has precluded accurate geochro
flanks of the Eastern Cordillera of Ecuador is dominated by mafic vol nology using Th- and U-bearing accessory minerals (i.e., zircon), which
canic rocks that yield geochemical characteristics of an arc, and have has severely hindered tectonic models for the Andes of Ecuador and
been mapped as the Alao Arc (Litherland et al., 1994; Spikings et al., Colombia. A major aim of this study is thus to attempt to constrain the
2015). Similarly, a series of mafic volcanic rocks also crop out along- time of crystallisation of the igneous rocks of the Alao Arc in Ecuador
strike in Colombia (i.e., the Quebradagrande Complex; Villagómez with the 40Ar/39Ar technique. This is challenging given the low-K, high-
et al., 2011; Spikings et al., 2015), which are considered to be equivalent Ca nature of the rocks, and the significant secondary chemical and
* Corresponding author.
E-mail address: [email protected] (H. Carrasco).
https://doi.org/10.1016/j.lithos.2023.107400
Received 17 April 2023; Received in revised form 18 October 2023; Accepted 20 October 2023
Available online 30 October 2023
0024-4937/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
H. Carrasco et al. LITHOS 462-463 (2023) 107400
78°W 77°W
SOUTH
AMERICAN PLATE 125.3±0.9
CAF Chinguál COLOMBIA

Quebradagrande Arc Pluton
PF Ecuador
157.9±7.3 Rosa Florida
Alao Arc Batholith
Huancabamba LF ECUADOR 0°
Deflection PF 182.4±0.6
Q
244.6±2.4
U-Pb zircon,
CF 169.8±1.1
LA-ICPMS
Azafrán 173.0±1.3
U-Pb zircon, Batholith
277.3±3.0
ID-TIMS
Abitagua
U-Pb zircon, 79°W Batholith
LA-ICPMS 1°
(youngest 140.7±1.7 174.0±1.2
233.7±4.8
detrital zircons)
metasedimentary
143.5±1.3 Amazon
rocks Foreland
40Ar/39Ar Chaucha B Basin
plateau date Block Study area
213.7±0.9 hornblende, 168.8±2.2
muscovite, 155.0±6.1
phengite,
plagioclase 163.7±1.6 2°
244.6±2.4 Lu-Hf isochron
Cretaceous (Early)
Ultramafic - mafic H-MP/LT
Peltetec metabasalts, metagabbros.
134.7±0.9 Raspas, Peltetec complexes
134.3±13 Alao Metalluminous volcanic rocks
80°W Arc ALAO ARC
143.3±9.9
3°S Metalluminous granitoids
Raspas Continental arc intrusions
126.4±4.0 PF Azafrán Batholith
129.9±5.6 Chinguál Pluton
121.0±0.8 Upano Unit (basalts, turbidites)
BF CF
SALADO ARC
Jurassic - latest Triassic
178.1±1.4
Slates, quartzites
Guamote Sequence
CHAUCHA BLOCK
145.4±0.2
Raspas 4°S Metalluminous granitoids
123.9±1.4 Continental arc intrusions
L 153.8±1.5
129.3±1.3 Permian and Triassic
132±5 160.5±1.7 Peraluminous granitoids
and migmatites
Zamora Continental rift.
Batholith e.g.Tres Lagunas Granite.
Palaeozoic
131.6±1.1
Undifferentiated
5°S
Fig. 1. Simplified geological map of the Eastern Cordillera of Ecuador, after Litherland et al. (1994). The major geological features are shown, including the
unfoliated, continental Jurassic Arc (in red), the foliated, latest Jurassic continental Salado Arc (in blue), the Early Cretaceous Alao Arc (in green) and sedimentary
Jurassic rocks of the Chaucha Block (in brown; all defined in the geological model of Spikings et al., 2015). Some geochronological data are shown, which are
summarised in Spikings et al. (2015, 2019). Major faults: BF: Baños Fault, CAF: Cauca-Almaguer Fault, CF: Cosanga Fault, LF: Llanganates Fault, PF: Peltetec Fault.
Towns: B: Baños, L: Loja, Q: Quito.
2
mineral transformations during fluid alteration and greenschist-facies metamorphosed, submarine sedimentary rocks of the Maguazo Unit to
metamorphism. Additionally, two volcanic rocks from the Salado Arc the west, and metamorphosed, graphitic volcano-sedimentary rocks of
were sampled and analysed using the same analytical methods to the El Pan Unit to the east, which were considered to be the fore- and
compare them with data acquired from the Alao Arc, given that the back-arc sequences of the Alao Arc by Litherland et al. (1994; Fig. 2),
Salado Arc is located to the east of the Alao Arc, and may be coeval respectively. The igneous rocks have undergone variable degrees of
(Fig. 1). greenschist metamorphism and post-depositional alteration processes
The two prevailing and contrasting models for the origin for the Alao that have modified their primary mineralogy to various degrees. The
Arc are i) the accretion of an intra-oceanic arc during the beginning of dense mineral assemblages of the sedimentary units, detrital zircon age
the Cretaceous during the so-called Peltetec event (Aspden and Lither spectra, and whole rock geochemical and isotopic (Sr, Nd) compositions
land, 1992; Litherland et al., 1994), and ii) the in-situ development of a of the igneous units were used by Spikings et al. (2015) to suggest the
continental arc on highly attenuated continental crust in an extensional Alao Arc formed on thin continental crust.
tectonic setting during the Early Cretaceous (Spikings et al., 2015, The few geochronological estimates of the time of crystallisation of
2019). Dense mineral assemblages and U-Pb concordia ages of detrital the igneous rocks of the Alao-Paute Unit include i) K/Ar dates of the
zircons support a continental origin for the arc (Cochrane et al., 2011, volcanic (hornblende) and metasedimentary rocks (whole rock and
2014), although its age has been determined by comparisons with the muscovite), which span between ~142–61 Ma (Table 1; Herbert and
Quebradagrande Arc of Colombia (U-Pb zircon dates of 112.9 ± 0.8 Ma Pichler, 1983; Kennerley, 1980; Litherland et al., 1994), and ii) U-Pb
and 114.3 ± 3.8 Ma; Villagómez et al., 2011; Cochrane et al., 2014). On analyses of detrital zircons using LA–ICP–MS, which yield a maximum
a local scale, our results will provide a better understanding of how the depositional age of 163.7 ± 1.6 Ma (i.e., Maguazo Unit; Table 1;
northwestern South American margin evolved during the Cretaceous, Cochrane et al., 2014; Spikings et al., 2015). Apatite and zircon fission
prior to the collision of the Caribbean Large Igneous Province, and may track dates from the Eastern Cordillera of Ecuador vary between ~65–8
provide insights into the origin of several mineralized deposits that are Ma (Spikings et al., 2000, 2001), and are not considered to record the
associated with the arc. At a larger scale, our data will provide a better age of the arc. Consequently, no accurate dates for the time of crystal
understanding of how new continental crust forms at active margins, lisation of the arc rocks have been generated. Volumetrically minor
either by accretion of oceanic terranes or by extension and hyperex mafic-ultramafic intrusive rocks of the Tampanchi Complex occur
tension of the existing margin and the addition of new juvenile crust. within the Alao-Paute Unit (Litherland et al., 1994) and yield U-Pb
(SHRIMP) crystallisation ages of ~75 Ma (Table 1; Villares et al., 2022).
2. Geological setting and previous work Additionally, paleontological studies indicate Jurassic – Lower Creta
ceous pollen, spores and acritarchs from phyllites in the Maguazo Unit,
A continental arc formed on the metamorphic Palaeozoic-Triassic constraining the maximum age of the Alao Arc to be Upper Bathonian to
basement of the Eastern Cordillera of Ecuador between the late Early Albian (~166–100 Ma; Molyneux, 1988; Riding, 1989; Litherland et al.,
and Late Jurassic (Fig. 1; ~182–145 Ma; Cochrane et al., 2014; Lither 1994).
land et al., 1994; Spikings et al., 2015), although the same phase of The western margin of the Alao Arc is defined by the 1–2 km wide
trench-parallel subduction commenced in Colombia as early as ~209 Ma dextral Peltetec fault zone (Fig. 1), which hosts steeply dipping, anas
(Spikings et al., 2015; Van der Lelij et al., 2016). Within Ecuador, these tomosed blocks of peridotite, olivine gabbros, spilitizied dolerites, basalt
I-type calk-alkaline and mainly granodioritic batholiths (the Rosa Flor and volcanoclastic rocks. Spikings et al. (2015, 2021) show that the
ida, Abitagua and Zamora batholiths) are located along the eastern flank mafic units formed during Neoproterozoic (40Ar/39Ar plagioclase dates
of the Eastern Cordillera (Figs. 1 and 2), and are usually undeformed of 565.5 ± 34.4 Ma, 581.8 ± 41.1 Ma, and 585.5 ± 14.1 Ma; Fig. 2;
(Litherland et al., 1994; Spikings et al., 2015). Traversing oceanward Table 1) and Lower Cretaceous (40Ar/39Ar groundmass dates of 134.3 ±
(westward) from the Jurassic batholiths and crossing the mylonities and 12.8 Ma and 134.7 ± 0.9 Ma; Fig. 2; Table 1), while some doleritic
ultramylonites of the Cosanga Fault in Ecuador, the deformed Salado slivers yield Triassic U-Pb zircon concordia ages (228.1 ± 1.7 Ma; Vil
Arc (Figs. 1 and 2) within the Eastern Cordillera is characterised by lares et al., 2020; Fig. 2; Table 1), indicating that these units do not
interbedded Upper Jurassic - Lower Cretaceous turbiditic metasedi define a coherent series of rocks that formed in a common tectonic
mentary rocks and mafic lavas (Upano Unit). U-Pb concordia ages of setting. Pratt et al. (2005) describe a stratigraphic transition from the
detrital zircons extracted from a sedimentary rock of the Upano Unit greenschists of the Alao Arc into metasedimentary rocks (the Guamote
yield maximum stratigraphic ages of 143.3 ± 9.9 Ma, and zircons sequence) located west of the Peltetec Fault, and thus they rule out the
extracted from a greenschist yield a U-Pb concordia age of 121.0 ± 0.8 Peltetec Fault as a terrane boundary. The Guamote sequence consists of
Ma. (Table 1; Cochrane et al., 2014). The Upano sequence is in faulted or a series of gently dipping slates and quartzites, which are exposed in
unconformable contact with the foliated, I-type calc-alkaline Azafrán isolated inliers, and host Jurassic – Early Cretaceous ammonites. Pratt
Batholith (U-Pb zircon ~145–140 Ma; Fig. 1; Table 1; Cochrane et al., et al. (2005) and Spikings et al. (2015) suggest they are autochthonous
2014; Spikings et al., 2015), which forms the intrusive component of the to South America and may have a stratigraphic transition upwards into
Salado Arc. Further north, near the Colombian border, the Chingual the Alao Arc. U-Pb ages of detrital zircons extracted from metasedi
Pluton is considered to be the youngest intrusive record of the Salado mentary turbidites of the Guamote sequence yield maximum strati
Arc, with a U-Pb zircon age of 125.3 ± 0.9 Ma (Fig. 1; Table 1; Cochrane graphic ages of ~163 Ma (Table 1; Cochrane et al., 2014; Spikings et al.,
et al., 2014; Spikings et al., 2015). Further west, these sequences are 2015).
placed against greenschist grade para-graphitic schists, and submarine
meta-andesites and meta-agglomerates of the Alao Arc, across the Baños 3. Methodology
Fault (Fig. 1), which is the focus of this study.
The rocks of the Alao Arc were deposited in a submarine setting and 3.1. Rock sampling
their lithofacies reveal a variety of volcanic and sedimentary environ
ments. The entire sequence is regionally deformed with steeply (almost The freshest and least deformed igneous rocks of the Alao Arc (27
vertical) dipping cleavage or schistosity (Litherland et al., 1994; Pratt samples) and the Salado Arc (2 samples) were sampled in several regions
et al., 2005). The igneous rocks (Fig. 1) are entirely volcanic to sub- (between 1◦ 15′S and 3◦ 15′S; Fig. 2) along the western flank of the
volcanic, including massive lavas, amygdaloidal lavas, agglomerates, Eastern Cordillera of Ecuador. These are, from north to south, i) close to
tuffs, pillow basalts and minor doleritic dykes (Litherland et al., 1994; the town of Baños, ii) close to the town of Penipe, iii) the Huarguallá
Pratt et al., 2005), which were referred to as the Alao-Paute Unit by valley, iv) the road spanning between the towns of Guamote and Macas,
Litherland et al. (1994). The Alao-Paute Unit is faulted against v) the Taday section (area west of the Tampanchi mafic-ultramafic
3
40
Fig. 2. Geological Map of the Eastern Cordillera of Ecuador between 01◦ 15′S and 03◦ 15′S, showing Ar/39Ar dates and previous radiometric dates of the area
summarised in Table 2. The map is modified from Litherland et al. (1994).
4
Table 1
Summary of published dates obtained from the Salado Arc, Alao Arc, Peltetec Unit and the Guamote sequence.
Sample Unit Lithology Longitude W Latitude S Age (Ma) Method Reference
206 238
09RC57 Azafrán (Salado Arc) Granodiorite 78◦
16′ 38” W 1 24′ 21” S
◦
143.5 ± 1.3* Pb/ U zircon Cochrane et al. (2014)
206 238
09RC59 Azafrán (Salado Arc) Monzogranite 78◦ 15′ 45” W 1◦ 24′ 34” S 140.7 ± 0.7* Pb/ U zircon Cochrane et al. (2014)
206 238
09RC63 Chingual (Salado Arc) Monzogranite 77◦ 29′ 26” W 00◦ 38′ 6” N 125.3 ± 0.9 Pb/ U zircon Cochrane et al. (2014)
206 238
11RC13 Upano (Salado Arc) Greenschist 78◦ 41′ 39” W 03◦ 14′ 54” S 121.0 ± 0.8* Pb/ U zircon Cochrane et al. (2014)
206 238
11RC23 Upano (Salado Arc) Sandstone 78◦ 12′ 04” W 02◦ 15′ 0” S 143.3 ± 9.9 (max) Pb/ U zircon Cochrane et al. (2014)
*
22 Maguazo (Alao Phyllite 78◦ 50′ 15” W 2◦ 50′ 50” S 92 ± 3 K/Ar whole rock Kennerley (1980)
forearc)
23 Maguazo (Alao Phyllite 78 50′ 15” W
◦
2 50′ 50” S
◦
88 ± 2 K/Ar whole rock Kennerley (1980)
forearc)
Alao-Paute (Alao Arc) Chl-ms schist 61 ± 2 K/Ar muscovite Herbert and Pichler
(1983)
CCR-E87- Alao-Paute (Alao Arc) Andesite 78◦ 42′ 6.8” W 2◦ 57′ 21.7” S 99 ± 10; 115 ± 12 K/Ar hornblende Litherland et al. (1994)
15A
CCR-E87- Alao-Paute (Alao Arc) Andesite 78◦ 42′ 6.8” W 2◦ 57′ 21.7” S 142 ± 36 K/Ar hornblende Litherland et al. (1994)
15B
206 238
09RC12 Maguazo (Alao Sandstone 78 36′ 40” W
◦
02 03′ 26” S
◦
163.7 ± 1.6 (max) Pb/ U zircon Cochrane et al. (2014)
forearc) *
33 Tampanchi Hornblendite 78◦ 33′ 00” W 2◦ 14′ 30” S 85 ± 3 K/Ar hornblende Kennerley (1980)
CRSH-89- Tampanchi Hornblende 78◦ 38′ 20.9” W 2◦ 38′ 22.3” S 66 ± 3 K/Ar hornblende Litherland et al. (1994)
17A gabbro
CRSH-89- Tampanchi Hornblendite 78◦ 38′ 20.9” W 2◦ 38′ 22.3” S 61 ± 4 K/Ar hornblende Litherland et al. (1994)
17B
CRSH-89- Tampanchi Basalt 78 38′ 20.9” W
◦
2 38′ 22.3” S
◦
61 ± 10 K/Ar hornblende Litherland et al. (1994)
17C
206 238
AR-31B Tampanchi Clinopyroxe-nite UTM 17S 9707855 75.8 ± 0.7* Pb/ U zircon Villares et al. (2022)
761480
206 238
AR-07 Tampanchi Hornblende UTM 17S 9707284 76.0 ± 0.4* Pb/ U zircon Villares et al. (2022)
gabbro 762684
206 238
AR-34 Tampanchi Leucodiorite UTM 17S 9707476 75.5 ± 0.3* Pb/ U zircon Villares et al. (2022)
762047
206 238
AR-15 Tampanchi Granite UTM 17S 9707799 75.1 ± 0.2* Pb/ U zircon Villares et al. (2022)
761638
40
04PR47 Peltetec Metabasalt 78◦ 33′ 41.3” W 1◦ 52′ 40.2” S 134.3 ± 12.8 Ar/39Ar Spikings et al. (2015)
plagioclase
40
04PR48 Peltetec Gabbro 78◦ 33′ 41.3” W 1◦ 52′ 40.2” S 134.7 ± 0.9 Ar/39Ar Spikings et al. (2015)
plagioclase
206
P-23 Peltetec Metadiabase 78 33′ 39.1” W
◦
1 53′ 8.3” S
◦
228.1 ± 1.7 Pb/ 238U zircon Villares et al. (2020)
40
04PR68 Peltetec Metagabbro 78◦ 33′ 45.3” W 1◦ 52′ 35.8” S 581.8 ± 41.1 Ar/39Ar Spikings and Popov
plagioclase (2021)
40
04PR98 Peltetec Metagabbro 78◦ 33′ 30.2” W 1◦ 51′ 19.3” S 565.5 ± 34.4 Ar/39Ar Spikings and Popov
plagioclase (2021)
40
04PR116 Peltetec Peridotite 78◦ 33′ 30.2” W 1◦ 51′ 19.3” S 585.5 ± 14.1 Ar/39Ar Spikings et al. (2021)
plagioclase
206
11RC05 Guamote Quartzite 78 00′ 09” W
◦
0 26′ 43” N
◦
157.9 ± 7.3 (max) Pb/ 238U zircon Cochrane et al. (2014)
206
09RC13 Guamote Graywacke 78◦ 41′ 51” W 1◦ 57′ 20” S 168.8 ± 2.2 (max) Pb/ 238U zircon Cochrane et al. (2014)
*
206 238
09RC17 Guamote Sandstone 78◦ 41′ 51” W 1◦ 57′ 20” S 155 ± 6.1 (max)* Pb/ U zircon Cochrane et al. (2014)
206 238
max: maximum depositional age defined by the youngest concordant U-Pb zircon date; *: Pb/ U zircon ages shown in Fig. 2.
complex), vi) the Paute section, and vii) close to the town of Gualaceo. Uncertainties of the three measurements per sample were < 5% for rare
Sample locations and lithologies are presented in Tables 2 and 3. earth elements (REE) and < 10% for the rest of the trace elements.
3.2. Whole rock geochemistry 3.3. Sr–Nd–Pd isotopes
Twenty-three volcanic and volcanoclastic rocks of the Alao Arc and Sixteen volcanic rocks were selected for whole rock Sr–Pb–Nd iso
two volcanic rocks of the Salado Arc were selected for whole rock topic analyses (Table 2). Approximately 150 mg of whole rock powder
chemical analyses (Table 2). Representative whole rock powders were was dissolved in 4 ml of concentrated HF and 1 ml of 15 M HNO3 in
prepared with an agate mill. Major and trace elements were measured closed Teflon vials at 140 ◦ C for seven days. The samples were dried
using a Philips PW2400 X-Ray Fluorescence (XRF) spectrometer at the down and re-dissolved in 3 ml of 15 M HNO3 before being dried down
University the Lausanne in glass fused disks and pressed pellets. Sub again. Sr–Nd–Pb chemical separation was achieved following the
sequently, the glass fused disks were fragmented and mounted for methods in Chiaradia et al. (2011) and Pin and Zalduegui (1997). Pb, Sr
additional analyses of trace and rare earth elements (REE). Measure and Nd isotope ratios were measured on a Thermo TRITON mass spec
ments were made using a Sector-field spectrometer Element XR ICP–MS trometer housed at the University of Geneva, Switzerland. Pb was
using NIST SRM 612 and BCR-2G as external standards. The laser set loaded on Re filaments using the silica gel technique (Gerstenberger and
tings used for analyses were 10 Hz frequency, 6 Jcm− 2 energy and 100 Haase, 1997) and all samples (and standards) were measured with
μm spot size. Background intensities were measured for ~90 s, followed Faraday cups in static mode at a pyrometer-controlled temperature of
by three ablations of ~30 s for raw data acquisition. The CaO compo 1220 ◦ C. Pb isotope ratios were corrected for instrumental fractionation
sition, previously determined by XRF, was used as an internal standard. by a factor of 0.07% per amu based on >90 measurements of the
Data reduction was done offline with LAMTRACE (Jackson, 2008). SRM981 standard, and using the standard values of Baker et al. (2004).
5
Table 2
Geochemical and isotopic data of the studied rocks of the Alao and Salado Arcs.
Samples PB02 PB04 PB05 PB07 PB14 PB15 AZ12 AZ13 AZ14 AZ16 PB17
Unit Alao- Alao-Paute Alao-Paute Alao-Paute Alao-Paute Alao-Paute Alao-Paute Alao-Paute Alao-Paute Maguazo Upano
Paute
Lithology Basalt Basaltic Basaltic- Basalt Basalt Basaltic- Basalt Basalt Tuff Tuff Dolerite
tuff andesite Andesite (resedimented) (resedimented)
Latitude S 2◦ 51′ 2◦ 52′ 2◦ 52′ 34.9” 2◦ 53′ 2◦ 45′ 2◦ 46′ 13.9” 2◦ 12′ 2◦ 11′ 11.7” 2◦ 11′ 4.9” 2◦ 7′ 5.6” 2◦ 16′ 20.7”
27.8” 13.7” 43.3” 47.3” 15.04”
Longitude W 78◦ 8′ 78◦ 46′ 78◦ 45′ 50.9” 78◦ 46′ 78◦ 43′ 78◦ 45′ 6.8” 78◦ 28′ 78◦ 29′ 78◦ 30′ 54.7” 78◦ 35′ 1.1” 78◦ 11′
50.3” 15.4” 10.9” 22.3” 18.5” 22.02” 29.01”
SiO2 41.67 49.24 49.60 44.79 46.12 52.35 47.03 43.50 59.72 59.88 48.13
TiO2 0.49 0.98 0.82 1.12 0.72 0.99 2.24 2.32 0.58 0.82 1.09
Al2O3 16.19 18.11 17.61 19.36 14.35 16.96 15.32 15.28 14.56 16.30 19.60
Fe2O3 8.68 9.45 7.75 10.62 8.95 8.87 11.55 12.34 5.37 7.55 10.86
MnO 0.13 0.06 0.12 0.15 0.15 0.13 0.17 0.26 0.14 0.17 0.15
MgO 7.86 6.89 4.92 7.22 8.31 6.86 7.86 6.79 2.06 3.30 4.36
CaO 11.31 7.97 10.80 8.65 12.68 4.82 8.64 7.77 4.64 3.98 8.02
Na2O 1.94 2.34 1.88 1.58 3.33 1.81 3.00 3.98 2.41 4.02 3.12
K2O 0.68 0.05 0.64 0.97 0.19 1.92 0.84 0.12 1.65 1.43 0.86
P2O5 0.05 0.25 0.28 0.16 0.08 0.25 0.33 0.32 0.17 0.17 0.39
Cr2O3 0.01 0.02 0.02 0.01 0.07 0.03 0.02 0.01 0.01 0.02 0.00
NiO 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00
LOI 10.14 5.25 5.18 4.80 5.94 4.76 2.90 7.19 7.88 3.01 3.14
Total 99.16 100.61 99.65 99.45 100.90 99.75 99.92 99.90 99.18 100.65 99.73
Sc 40.78 28.13 27.69 36.21 39.84 34.55 38.23 37.08 14.29 25.37 22.60
V 224.56 275.10 243.39 366.22 239.88 237.53 301.73 346.28 126.48 208.06 264.41
Co 38.21 29.30 28.12 31.19 36.43 44.64 41.20 35.73 11.14 33.74 29.91
Ni 45.86 52.09 45.11 48.24 85.80 63.01 76.24 47.43 19.55 37.18 20.52
Zn 89.55 84.28 87.13 76.63 62.00 78.56 83.32 105.98 58.15 183.05 60.15
Rb 14.54 1.00 16.02 27.79 2.30 38.51 10.29 2.23 53.61 40.53 29.40
Sr 131.00 138.40 255.97 328.31 73.20 215.87 316.30 81.22 292.36 296.74 640.51
Y 10.81 20.65 19.34 19.83 14.65 17.47 29.17 38.81 13.82 19.80 22.94
Zr 19.44 67.69 51.11 44.54 30.53 59.13 167.82 157.73 103.59 119.71 62.57
Nb 0.26 6.24 4.08 3.27 0.96 4.75 19.60 11.88 4.94 4.66 6.61
Mo 0.29 0.83 1.08 0.32 0.23 0.44 0.67 1.14 0.46 0.76 0.72
Cs 0.47 0.22 0.66 1.60 0.07 2.38 0.19 0.21 3.09 3.31 1.60
Ba 320.63 73.13 446.71 452.30 79.25 1121.16 202.21 110.79 562.98 684.17 446.79
La 2.29 17.39 16.39 9.71 2.21 13.56 13.14 11.02 17.71 15.72 16.17
Ce 3.85 37.86 32.56 21.48 5.36 28.73 29.51 26.54 32.40 31.99 34.56
Pr 0.66 4.96 4.28 3.29 0.86 3.89 3.99 3.82 3.87 4.04 4.75
Nd 3.56 20.81 17.85 15.11 4.52 16.48 18.23 18.72 15.25 16.52 21.52
Sm 1.12 4.63 4.04 3.71 1.49 3.64 4.67 5.29 3.11 3.75 5.09
Eu 0.66 1.14 1.13 1.09 0.63 0.94 1.59 1.81 0.85 0.99 1.49
Gd 1.58 4.13 3.47 3.65 1.99 3.29 5.10 6.08 2.66 3.40 4.50
Tb 0.27 0.60 0.52 0.57 0.36 0.50 0.83 1.00 0.37 0.53 0.67
Dy 1.76 3.78 3.17 3.61 2.39 3.08 5.16 6.46 2.29 3.36 4.16
Ho 0.38 0.79 0.68 0.76 0.52 0.66 1.05 1.38 0.47 0.71 0.80
Er 1.10 2.21 1.96 2.18 1.57 1.90 3.04 4.00 1.33 2.03 2.33
Tm 0.16 0.31 0.27 0.31 0.23 0.28 0.43 0.54 0.18 0.28 0.33
Yb 1.07 2.13 1.87 2.00 1.49 1.80 2.75 3.64 1.33 1.97 2.26
Lu 0.16 0.32 0.29 0.31 0.23 0.28 0.42 0.54 0.21 0.30 0.32
Hf 0.61 1.84 1.35 1.32 0.87 1.62 3.76 3.75 2.64 3.11 1.69
Ta 0.02 0.32 0.20 0.17 0.05 0.24 1.09 0.65 0.32 0.26 0.33
W 0.18 0.53 0.45 0.18 0.13 0.34 0.18 0.33 0.68 0.71 0.21
Pb 2.38 1.78 2.60 2.04 1.27 2.30 3.62 1.75 9.94 108.43 3.28
Th 0.12 4.77 3.69 2.15 0.34 4.58 1.15 1.03 7.04 4.32 2.32
U 0.22 1.31 1.01 0.69 0.27 1.21 0.39 0.43 1.92 1.31 0.58
86
Sr/87Sruncorr 0.70559 0.70423 0.70431 0.70423 0.70492 0.70551 0.70378 0.70487 0.70409
143
Nd/144Nduncorr 0.51286 0.51262 0.51262 0.51272 0.51297 0.51255 0.51301 0.51300 0.51280
εNduncorr 4.32 − 0.39 − 0.33 1.55 6.44 − 1.70 7.34 7.06 3.10
86
Sr/87Sri(120 Ma) 0.70505 0.70419 0.70400 0.70381 0.70477 0.70462 0.70362 0.70474 0.70386
143
Nd/144Ndi(120Ma) 0.51271 0.51251 0.51251 0.51260 0.51281 0.51245 0.51289 0.51287 0.51269
εNd(120 Ma) 4.43 0.57 0.60 2.30 6.43 − 0.72 8.00 7.47 3.94
86
Sr/87Sri(75 Ma) 0.70525 0.70420 0.70412 0.70397 0.70483 0.70496 0.70368 0.70479 0.70395
143
Nd/144Ndi(75Ma) 0.51277 0.51255 0.51255 0.51264 0.51287 0.51249 0.51294 0.51292 0.51273
εNd(75 Ma) 3.30 − 0.56 − 0.53 1.17 5.30 − 1.85 6.86 6.34 2.81
206
Pb/204Pbuncorr 19.151 19.586 19.200 19.090 19.286 19.285 19.030 19.481 19.033
207
Pb/204Pbuncorr 15.723 15.702 15.675 15.652 15.691 15.689 15.628 15.713 15.656
208
Pb/204Pbuncorr 38.963 39.487 39.043 38.843 38.875 39.202 38.684 39.095 38.914
206
Pb/204Pbi(120 Ma) 19.037 18.682 18.727 18.678 19.030 18.646 18.899 19.178 18.819
207
Pb/204Pbi(120 Ma) 15.717 15.658 15.652 15.632 15.678 15.659 15.621 15.698 15.645
208
Pb/204Pbi(120 Ma) 38.943 38.407 38.479 38.425 38.770 38.406 38.558 38.859 38.633
206
Pb/204Pbi(75Ma) 19.080 19.023 18.905 18.834 19.126 18.887 18.949 19.292 18.900
207
Pb/204Pbi(75Ma) 15.719 15.675 15.661 15.639 15.683 15.671 15.624 15.704 15.649
208
Pb/204Pbi(75Ma) 38.951 38.813 38.691 38.582 38.810 38.705 38.605 38.948 38.739
6
PB19 AZ17 AZ18 AZ19 AZ21 AZ22 PB23 PB25 BB04 BB05 BB06 BB07
Upano Alao-Paute Alao-Paute Maguazo Maguazo Maguazo Maguazo Alao-Paute Peltetec Peltetec Peltetec Peltetec
Basalt Amygdaloid Basaltic- Andesitic Basaltic- Tuff Basaltic Greenschist Basaltic- Basaltic- Basaltic- Basaltic-
basalt andesitic tuff tuff Andesite (resedimented) tuff Andesite Andesite Andesite Andesite
2◦ 14′ 1◦ 40′ 21.4” 1◦ 40′ 55.6” 1◦ 39′ 1◦ 36′ 40.6” 1◦ 36′ 12.6” 1◦ 21′ 1◦ 24′ 16.4” 1◦ 53′ 30.8” 1◦ 53′ 23.9” 1◦ 53′ 17.0” 1◦ 52′ 54.8”
53.5” 38.05” 36.8”
78◦ 12′ 78◦ 30′ 30.8” 78◦ 30′ 4.3” 78◦ 30′ 78◦ 30′ 78◦ 31′ 11.1” 78◦ 29′ 78◦ 28′ 78◦ 33′ 78◦ 33′ 78◦ 33′ 78◦ 33′
24.8” 59.4” 45.07” 23.4” 17.09” 13.8” 25.1” 30.6” 53.1”
48.88 59.13 52.38 57.39 51.77 65.93 44.74 53.56 49.91 51.72 51.69 53.01
0.90 0.84 1.15 0.71 1.60 0.66 0.86 0.94 0.79 0.63 0.58 0.76
16.07 15.68 15.34 15.97 15.11 13.74 18.14 15.38 17.89 15.20 17.51 14.07
11.45 6.82 11.64 6.61 12.31 6.47 9.33 10.09 9.02 8.43 6.58 7.93
0.16 0.12 0.26 0.08 0.22 0.12 0.09 0.18 0.10 0.12 0.11 0.14
3.83 2.85 3.51 3.87 4.57 2.03 6.51 5.91 6.95 6.73 4.84 7.75
7.31 10.09 9.12 6.92 6.16 4.20 11.75 6.88 5.10 9.13 6.45 6.76
1.95 1.18 1.43 2.95 5.21 2.39 1.91 4.65 4.78 2.21 1.28 2.69
4.36 0.15 0.54 1.20 0.45 1.32 0.08 1.05 0.19 0.03 2.34 1.35
0.45 0.11 0.17 0.11 0.45 0.15 0.10 0.24 0.09 0.09 0.11 0.17
0.00 0.03 0.02 0.02 0.00 0.01 0.01 0.02 0.02 0.06 0.02 0.06
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01
3.13 3.90 4.77 3.86 2.25 3.58 6.31 1.87 5.17 5.76 9.23 4.95
98.49 100.88 100.33 99.69 100.09 100.61 99.84 100.77 100.01 100.13 100.74 99.64
18.09 26.39 41.42 26.08 35.45 24.06 43.68 31.07 27.48 31.14 22.28 29.14
216.28 108.93 307.63 173.18 295.53 186.19 307.04 225.23 187.66 205.34 166.09 190.83
6.58 18.18 26.14 18.64 27.57 17.94 29.65 26.04 21.34 26.96 16.12 31.61
9.18 17.38 17.25 40.66 12.91 18.84 26.17 54.48 27.31 82.24 22.35 76.03
73.22 67.27 128.52 66.46 92.54 104.09 73.74 95.70 91.43 61.79 69.86 75.59
125.62 3.27 7.87 27.90 7.38 27.94 2.29 21.61 2.89 1.09 84.83 28.63
538.94 54.31 180.08 124.85 140.38 124.83 165.22 163.27 74.81 81.92 96.43 460.80
19.21 19.51 26.04 18.76 22.92 24.41 16.79 26.06 13.66 14.26 16.96 15.27
70.46 99.38 57.70 124.20 41.62 83.93 53.88 76.02 53.88 74.60 84.01 72.58
5.51 4.12 1.18 3.73 1.17 2.10 1.65 2.53 1.46 2.20 2.41 3.78
0.82 1.63 1.81 0.32 0.36 5.67 0.30 0.41 0.33 1.04 0.46 0.34
3.36 0.17 0.74 1.47 0.43 1.54 0.18 0.57 1.34 1.27 3.72 0.70
1172.93 112.71 862.43 334.96 240.65 841.55 18.33 546.33 289.06 20.26 283.31 693.63
15.53 12.33 4.97 12.70 6.61 10.20 3.81 9.33 4.32 9.62 10.12 7.73
31.36 25.79 11.72 26.18 15.01 20.02 9.28 20.49 10.10 20.50 21.58 17.22
4.16 3.25 1.83 3.24 2.29 2.71 1.36 2.89 1.45 2.64 2.73 2.45
18.17 13.41 9.32 13.63 11.26 11.99 6.61 13.32 6.53 11.44 11.65 10.85
4.09 3.20 3.03 3.10 3.27 3.08 2.07 3.59 1.86 2.73 2.75 2.61
1.47 0.88 1.02 0.89 1.24 0.94 0.74 1.17 0.64 0.78 0.75 0.79
3.73 3.15 3.55 2.97 3.87 3.54 2.54 3.93 2.16 2.61 2.70 2.66
0.56 0.53 0.64 0.49 0.62 0.59 0.45 0.67 0.36 0.40 0.43 0.41
3.30 3.27 4.24 3.17 4.04 3.97 2.97 4.33 2.26 2.46 2.74 2.52
0.66 0.69 0.90 0.65 0.85 0.86 0.63 0.93 0.49 0.53 0.59 0.53
1.93 1.99 2.64 1.95 2.38 2.54 1.76 2.76 1.43 1.46 1.68 1.50
0.27 0.29 0.37 0.28 0.33 0.38 0.26 0.39 0.20 0.22 0.26 0.21
1.76 1.94 2.57 1.91 2.30 2.60 1.66 2.69 1.43 1.48 1.73 1.42
0.28 0.30 0.40 0.29 0.34 0.40 0.24 0.40 0.21 0.23 0.26 0.23
1.73 2.54 1.68 3.17 1.23 2.43 1.50 2.08 1.43 2.07 2.12 1.85
0.29 0.24 0.06 0.24 0.06 0.14 0.11 0.14 0.09 0.14 0.15 0.22
2.88 0.82 0.77 0.29 0.18 0.58 0.72 0.23 0.16 0.33 0.18 0.17
11.12 5.23 4.56 4.02 2.20 11.67 2.60 3.82 10.51 1.93 5.43 2.16
3.07 2.72 0.75 3.39 1.62 3.77 1.11 2.72 0.85 2.02 1.93 1.46
0.92 0.68 0.57 0.88 0.46 1.61 0.86 0.73 0.33 0.68 0.55 0.46
0.70521 0.70665 0.70615 0.70519 0.70551 0.70547 0.70412
0.51278 0.51248 0.51265 0.51274 0.51276 0.51278 0.51284
2.75 − 3.09 0.24 1.94 2.44 2.81 3.97
0.70406 0.70635 0.70504 0.70493 0.70532 0.70540 0.70381
0.51267 0.51237 0.51254 0.51260 0.51263 0.51267 0.51273
3.69 − 2.27 1.15 2.28 2.82 3.62 4.77
0.70450 0.70646 0.70546 0.70503 0.70539 0.70543 0.70393
0.51271 0.51241 0.51258 0.51265 0.51268 0.51271 0.51277
2.56 − 3.40 0.02 1.15 1.69 2.49 3.64
19.008 19.181 19.213 19.255 19.106 19.213 19.007
15.690 15.714 15.705 15.673 15.704 15.654 15.678
38.965 39.104 39.107 39.042 39.004 38.928 38.891
18.908 19.023 18.945 19.001 19.067 18.787 18.749
15.685 15.707 15.692 15.661 15.702 15.633 15.665
38.855 38.897 38.771 38.749 38.972 38.511 38.624
18.945 19.083 19.046 19.097 19.082 18.947 18.846
15.687 15.710 15.697 15.665 15.703 15.641 15.670
38.896 38.975 38.897 38.859 38.984 38.668 38.725
7
H. Carrasco et al.
Table 3
40
Summary Ar/39Ar data from the mafic rocks from the Alao Arc and Salado Arc, Eastern Cordillera of Ecuador.
39
Lithology Sample Main alteration Latitude (N) Longitud Step Heating MSWD Ar% # K/Ca ± 2σ Inv. Isochron MSWD (40Ar/36Ar)i ± 2σInitial Total Fusion
phasephase (W) released steps ± 2σ
Date ± 2σ Date ± 2σ Date ± 2σ
(Ma) (Ma) (Ma)
Plateau dates
Tuff 20AZ22- Clay 78◦ 31′ 1◦ 36′ 12.6” 65.10 ± 1.36 68.71 5 464 ± 394 61.82 ± 4.82 1.04 366.95 ± 99.84 60.24 ±
Gm 11.1” 0.81 0.79
Basaltic andesite 20BB04- Clay 78◦ 33′ 1 53′ 30.8”
◦
20.60 ± 0.64 90.76 6 1.86 ± 0.20 37.84 ± 0.36 271.51 ± 37.41 21.49 ±
Gm 13.8” 3.22 21.64 3.00
Basaltic andesite 20BB06- Sericite 78◦ 33′ 1◦ 53′ 17.0” 51.11 ± 0.64 72.63 8 28 ± 10 55.86 ± 8.07 0.55 281.66 ± 28.43 53.90 ±
Gm 30.6” 2.10 2.55
Basaltic andesite 20BB07- Clay 78◦ 33′ 1◦ 52′ 54.8” 32.84 ± 0.85 87.01 10 1.02 ± 0.09 32.36 ± 2.02 0.93 310.26 ± 49.22 32.35 ±
Gm 53.1” 0.38 0.48
Tuff 20AZ16- Clay 78◦ 35′ 1.1” 2◦ 7′ 5.6” 35.24 ± 0.68 100 11 50 ± 19 35.45 ± 7.20 0.76 297.78 ± 29.45 35.14 ±
Gm 1.12 1.17
Basalt 20PB19- Clay 78 12′
◦
2 14′ 53.5”
◦
31.84 ± 1.78 59.22 5 83 ± 8 31.28 ± 0.70 1.07 371.35 ± 76.71 32.99 ±
Gm 24.8” 0.38 0.37
Tuff 20AZ01- Sericite 78◦ 41′ 2◦ 36′ 72.64 ± 1.89 61.2 7 594 ± 173 70.59 ± 5.36 2.09 504.38 ± 356.67 72.03 ±
Gm 12.4” 45.04” 0.81 0.75
Basaltic tuff 20PB04- Clay 78◦ 46′ 2◦ 52′ 13.7” 54.33 ± 0.59 58.26 5 1.41 ± 1.12 62.07 ± 0.75 293.45 ± 31.51 75.22 ±
Gm 15.4” 8.89 40.09 7.65
Basalt 20PB07- Chlorite 78◦ 46′ 2◦ 53′ 43.3” 39.59 ± 0.73 51.71 7 1.02 ± 0.20 37.04 ± 3.83 0.48 321.31 ± 33.70 40.54 ±
Gm 10.9” 0.76 0.77
Meta basalt 20PB09- Sericite 78◦ 45′ 2 53′ 53.5” 69.71 1.39 76.93 5 83 ± 33 69.97 ± 0.96 1.44 288.25 ± 21.52 71.03 ±
8
◦
±
Gm 41.8” 0.80 0.76
Weighted mean dates

Basaltic tuff 20PB23- Clay 78◦ 29′ 1◦ 21′ 36.8” 16.57 ± 1.52 62.13 3 29.4 ± 4.5 33.21 ± 2.93 250.49 ± 391.70 35.67 ±
Gm 23.4” 3.09 45.37 2.05
Basaltic andesitic 20AZ18- Clay 78◦ 30′ 4.3” 1◦ 40′ 55.6” 40.15 ± 2.34 43.18 4 220 ± 36 36.91 ± 3.05 0.63 341.22 ± 39.42 39.84 ±
tuff Gm 0.91 1.38
Basalt 20AZ13-Pl No alt. 78◦ 29′ 2◦ 11′ 11.7” 86.83 ± 8.5 53.65 3 33.0 ± 10.4 76.12 ± 16.53 325.60 ± 248.72 220.40 ±
22.02” 12.33 73.95 8.12
Basalt 20AZ12- Chlorite 78◦ 28′ 2◦ 12′ 60.00 ± 0.59 46.59 5 0.337 ± 61.26 ± 2.78 0.52 246.85 ± 107.41 59.33 ±
Gm 18.5” 15.04” 0.66 0.038 0.62
Basalt 20PB14- Clay 78◦ 43′ 2◦ 45′ 47.3” 31.56 ± 0.8 40.56 5 0.0528 ± 38.85 ± 9.09 0.41 263.23 ± 44.82 34.54 ±
Gm 22.3” 1.31 0.0046 1.85
Basaltic andesite 20PB15- Clay 78◦ 45′ 6.8” 2◦ 46′ 13.9” 73.93 ± 2.09 43.93 5 0.76 ± 0.13 75.78 ± 3.05 1.87 220.29 ± 111.63 74.07 ±
Gm 0.88 0.77
Basaltic andesite 20PB05- Clay 78◦ 45′ 2◦ 52′ 34.9” 67.67 ± 2.22 67.3 4 0.375 ± 71.54 ± 2.95 0.34 205.65 ± 66.98 66.28 ±
Gm 50.9” 0.97 0.087 0.77
Basalt 20PB06- Clay 78◦ 46′ 9.3” 2 52′ 55.1”
◦
70.52 ± 0.69 57.13 3 1.99 ± 0.43 76.80 ± 0.27 165.19 ± 213.41 65.94 ±
Gm 0.88 10.61 0.79
LITHOS 462-463 (2023) 107400

Lapilli 20PB08- Clay 78◦ 45′ 2◦ 53′ 55.7” 70.84 ± 3.51 47.07 3 6.3 ± 0.4 76.21 ± 5.12 1.48 202.66 ± 88.39 63.00 ±
(volcanoclastic) Gm 47.2” 1.27 0.74
Metabasalt 20PB09-Pl Sericite 78◦ 45′ 2◦ 53′ 53.5” 78.83 ± 10.55 52.63 3 136 ± 26 65.09 ± 8.13 0.01 493.96 ± 114.54 91.09 ±
41.8” 2.38 1.55
Step heating dates shown in bold are the preferred dates.

Fig. 3. Photographs of representative rocks of the Alao Arc in the Eastern Cordillera of Ecuador. a. Amygdaloidal basalt (20AZ17), b. Basaltic-andesitic lava
(20BB07), c. Aphanitic basaltic-andesite (20AZ21), d. Alkaline basalt (20AZ12), e. Volcanoclastic andesitic tuff (20AZ19), f. Volcanoclastic basaltic tuff (20PB04), g.
Volcanoclastic lapilli (20PB08), h. Greenschist (20PB25).
9
Fig. 4. Thin section photomicrographs of volcanic rocks of the Alao Arc. a. Basalt (20AZ13, XPL), b. Basaltic-andesite (20BB06, XPL), c. Basalt (20PB14, XPL), d.
Basaltic-andesite (20BB04, XPL), e. Dolerite (20PB17, XPL), f. Volcanoclastic lapilli (20PB08, XPL), g. Volcanoclastic tuff (20AZ01, XPL), h. Volcanoclastic tuff-
resedimented (20AZ16, XPL).
10
External reproducibility of the standard ratios are 0.08% for values were internally corrected for fractionation using a 146Nd/144Nd
206
Pb/204Pb, 0.12% for 207Pb/204Pb and 0.16% for 208Pb/204Pb. Sr was value of 0.7219 and the 144Sm interference on 144Nd was monitored on
loaded on single Re filaments with a Ta oxide solution and measured in the mass 147Sm and corrected by using a 144Sm/147Sm value of
static mode at a pyrometer-controlled temperature of 1480 ◦ C using the 0.206700. These values were further corrected for external fractionation
virtual amplifier design to cancel out biases in gain calibration among by a value of +0.03‰, determined by repeated measurements of the
amplifiers. 87Sr/86Sr values were internally corrected for fractionation JNdi-1 standard (143Nd/144Nd = 0.512115; Tanaka et al., 2000).
using a 88Sr/86Sr value of 8.375209. Raw values were further corrected External reproducibility of the JNdi-1 standard is <5 ppm.
for external fractionation by a value of +0.03‰, determined by repeated
measurements of the SRM987 standard (87Sr/86Sr = 0.710248). 40
3.4. Ar/39Ar analysis
External reproducibility of the 87Sr/86Sr ratio for the SRM987 standard
is 7 ppm. Nd was loaded on double Re filaments with 1 M HNO3 and
Groundmass and plagioclase concentrates were extracted from
measured in static mode with the virtual amplifier design. 143Nd/144Nd
twenty-six volcanic and volcanoclastic rocks from the Alao and Salado
a. b.
Alao Arc 12
This study Rhyolite Foidite Tephriphonolite
0.1 Cochrane et al. (2014) Trachyte
10
Litherland et al. (1994)
Na O + K O (wt%)
Phonotephrite Trachydacite
Rhyodacite Trachy-
Zr/TiO (ppm)
Salado Arc Dacite andesite

8 Basaltic
This Study trachy
Andesite Tephrite andesite
6 Basanite Tra-
0.01 RC19 chybasalt
Andesite,
Basalt 4
AZ12
Alkaline Andesite Dacite
Sub-alkaline basalt basalt 2 Picro-
basalt Basaltic
Quebradagrande Complex Basalt andesite
0.001 0
0.1 1 40 45 50 55 60 65 70
Nb/Y (ppm) SiO (wt%)
c. d.
8 100
High-K calc-alkaline
Metalluminous Peralluminous
6
10
Al/(Na+K)
Th (ppm)
4 BB06
PB15 Calc-alkaline
1
Bas esite,
dac nodiorit
and
Rhy ranite,
Bas
gra
altic
2
ite,
alt,
olite
-an iorite
g
Tholeiite
gab
des
,
0.1
e
br o
ite,
0
0.2 0.4 0.6 0.8 1.0 1.2 0 10 20 30 40 50
Al/(Ca+Na+K) Co (ppm)
e. f.
10000
Volcanic rocks - Alao Arc This study
1000 Cochrane et al. (2014)
10
EMORB-like signature basalts
100
Salado Arc - This study
10 1
0.1 0.1
N-MORB N-MORB
0.01
Cs Rb Ba Th U Nb Ta La Ce Pb Pr Sr Nd Zr Hf Sm Eu Ti Tb Y Tm Yb La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Yb Lu
Fig. 5. a. Nb/Y versus Zr/TiO2 plot (Winchester and Floyd, 1977), b. Total Alkali Silica diagram (corrected for volatile content; Le Bas et al., 1986), c. A/CNK vs A/
NK diagram, d. Co versus Th (Hastie et al., 2007), e. f. Whole-rock trace-element and REE concentrations normalized to N-MORB (Sun and McDonough, 1989). Data
of the Quebradagrande Arc is shown as grey fields on the plots (Cochrane et al., 2014; Nivia et al., 2006; Rodríguez and Zapata, 2013; Villagómez et al., 2011).
11
Arcs. Groundmass and plagioclase were separated from size fractions of in Cu foil, and stacked inside a silica-glass tube, along with Fish Canyon
500–300 μm and ≤ 300 μm, respectively. All crushed samples were Tuff sanidine (28.201 ± 0.046 Ma; Kuiper et al., 2008) that separated
cleaned using a Wilfley Table to thoroughly remove clays. Aliquots of every third sample. The tube was irradiated at the shielded cadmium-
groundmass were obtained using a Frantz magnetic separator at low lined in-core irradiation tube (CLICIT) position at the Oregon State
voltages (e.g., magnetic fraction <5 V, <10 V or < 15 V), while University TRIGA reactor for 18 h. The samples were pre-degassed at a
plagioclase aliquots (≤300 μm) were taken from the non-magnetic laser power of 0.56 W to remove extraneous Ar from the grain surfaces,
fraction with a current of >1.5 A. The plagioclase aliquots were using a 55 W, CO2-IR laser (Photon Machines Inc.). The samples were
further purified by hand-picking using a binocular microscope. Sixty subsequently step-heated with typically 12–18 individual degassing in
milligrams of both groundmass and plagioclase aliquots were wrapped crements. The liberated gas was cleaned via a cold finger held at
Fig. 6. a–n. Major, trace elements, and trace-element ratios against MgO for igneous rocks of the Alao and Salado Arcs, l. MgO versus Eu anomaly, the dashed field
represents the absence of an Eu anomaly where Eu*/Eu = 1 ± 0.1 (Eu/Eu* is Cl-chondrite-normalized; Sun and McDonough, 1989), m. Y versus Sr/Y plot.
12
− 130 ◦ C, and hot GP50 (ST101) and cold NP10 (ST101) getters. Ar and the pyroxenes are variably altered to chlorite ± epidote. The
isotopes were multi-collected in a single step using a Thermo Fisher groundmass consists of either fine tabular microlites of plagioclase ±
multi-collector Argus VI mass (40-37Ar were collected on Faradays pyroxene, or a formerly glassy matrix transformed into very fine-grained
equipped with 1E13 ohm resistors, and 36Ar was collected with the alteration assemblages. The degree of alteration of the matrix varies
CDD). Data were reduced using ArArCalc (Koppers, 2002), and baseline from moderate to intense, and the assemblages generally comprise clays
and blank corrected data are presented in Supplementary material 1 and + chlorite ± calcite ± epidote ± quartz ± actinolite ± pyrite. Nine out
2, along with data obtained from the Fish Canyon Tuff sanidine moni of fourteen lavas host amygdales that are usually infilled with secondary
tors. Mass discrimination and Faraday/CDD yields were continually minerals such as chlorite, calcite, prehnite, epidote, quartz and zeolites.
monitored and corrections were made as a function of gas intensity. Two rock samples of the Upano Unit (Fig. 2; Supplementary material
3), which form part of the Salado Arc (Spikings et al., 2015), are a
4. Results plagioclase-phyric dolerite (Fig. 4e) and a basalt. Both samples contain
euhedral plagioclase phenocrysts. The dolerite groundmass is composed
4.1. Petrography and secondary alteration of plagioclase and hornblende, which are slightly altered to sericite and
chlorite, respectively (Fig. 4e). The basalt is moderately altered with
Most of the volcanic rocks of the Alao Arc have basaltic to basaltic- secondary assemblages of clays + chlorite + calcite + quartz + actinolite
andesitic mineralogical compositions, with hypocrystalline aphanitic + epidote.
to porphyritic textures (Figs. 3a–d and 4a–d, Supplementary material 3). The sampled volcanoclastic rocks of the Alao Arc are tuffs, while one
These mineralogical definitions are consistent with the chemical com has a lapilli texture (Supplementary material 3; Figs. 3e–g and 4f–g), and
positions of the rocks (see Section 4.2). Phenocrysts are mainly plagio show basaltic to andesitic geochemical compositions (see Section 4.2).
clase, pyroxene ± olivine. The plagioclase phenocrysts are euhedral and These units are characterised by angular to subangular grains of
are variably altered to clay + sericite + calcite ± epidote ± quartz. The plagioclase, volcanic fragments, and a fine- to very fine-grained matrix,
olivine phenocrysts are slightly to moderately altered to serpentinite, while fiamme structures are replaced by chlorite. The alteration
a. seamounts
b.
ARC
0
1.6 500
AZ12
=2
RC19 MORB
/V
= 10
Ti
E-MORB BABB
400
Ti/V
1.2
AZ13
AZ13
V (ppm)
300 AZ12
Nb/La
0.8
RC19 = 50
200 Ti/V
MORB continental arc OIB
0.4 This study
100 Alao
Cochrane Arc
et al. (2014)
oceanic arc Salado Arc
0.0 0
0 1 2 3 0 5 10 15
(La/Sm)n Ti/1000 (ppm)
c. 10 d. 10
Basalt This study
y
Mariana Alao
ra
Basaltic- Cochrane
ar
Arc Crust Arc

c
andesite et al. (2014)

ar
ic
CC Andesite Salado Arc

an
IB
ay
O
lc
r
ar
RC19
vo
1
IB
O-
OIB array
RB
TiO /Yb
OIB
Th/Yb
(deep melting)
O
de
M
Magma-crust -rig on
me cti
interaction 1 AZ13 Pluntera
AZ13 i
AZ12
AZ12 RC19
B
R
0.1 MORB array

O
M
(shallow melting)
E-
N E
Mariana Mariana Arc Crust
and Trough (BAB)
B
Trough
R
O
-M
(BAB)
N
0.01 0.1
0.1 1 10 100 0.1 1 10 100
Nb/Yb Nb/Yb
Fig. 7. a. (La/Sm)n versus Nb/La (John et al., 2003), b. Ti/1000 versus V (Shervais, 1982), c. Nb/Yb versus Th/Yb, and d. Nb/Yb versus TiO2/Yb (Pearce, 2008).
Mariana arc-basin system fields are taken from Pearce et al. (2005).
13
assemblages are dominated by clay + chlorite ± calcite ± epidote ± ignition LOI = 2.25–10.14 wt%; see Section 4.2) of the freshest and least
sericite ± quartz ± actinolite ± pyrite. Several volcanoclastic rocks deformed volcanic and volcanoclastic rocks suggest they experienced
show shear and strain shadow structures. Some fine-grained volcano alteration events by fluid-rock interaction, either by seafloor and/or
clastic rocks (tuffs) are highly reworked and show recognizable sedi magmatic-hydrothermal alteration, or by later fluid circulation.
mentary facies, with subangular to subrounded volcanic fragments, Field observations also show that the rocks of the Alao Arc are
grains of plagioclase and characteristic detrital quartz and zircon regionally deformed with a steeply (almost vertically) dipping cleavage
(Supplementary material 3; Fig. 4h). or schistosity, and the most intensely deformed zones have a greenschist
The secondary assemblages and the high volatile content (loss on metamorphic mineral assemblage (Litherland et al., 1994). Three
Fig. 8. Radiogenic Sr-Nd-Pb compositions for age corrected data from the Alao Arc, Salado Arc. a. 87Sr/86Sr versus 143Nd/144Nd, b. 206Pb/204Pb versus 143Nd/144Nd,
c. 206Pb/204Pb versus 208Pb/204Pb, d. 206Pb/204Pb versus 87Sr/86Sr plots, e. 206Pb/204Pb versus 207Pb/204Pb. Also shown are previous age corrected data the Alao Arc
of Cochrane et al. (2014), and age corrected field of lead isotopes of Triassic feldspars of Paul et al., 2018. Fields for the Galapagos islands (GIs; White et al., 1993),
East Pacific Rise (EPR), Depleted MORB Mantle (DMM), Bulk Silicate Earth (BSE), high μ (HIMU), Enriched Mantle 1 (EM1) and Enriched Mantle 2 (EM2) are also
shown (Zindler and Hart, 1986).
14
greenschists were sampled and have a schistose foliation with lepido plots without negative Nb, Ta and Ti anomalies, although their REE
blastic textures, with chlorite + epidote + actinolite + plagioclase concentrations are similar to those from all of the other sampled igneous
(albite?) + quartz ± hornblende ± muscovite ± calcite (Fig. 3h, Sup rocks of the Alao Arc (Fig. 5e, f).
plementary material 3). Most of the volcanic rocks of the Alao and Salado Arc plot in the
oceanic and continental arc fields when comparing (La/Sm)n and Nb/La
4.2. Whole rock geochemistry: Major oxide, trace element and REE (Fig. 7a; John et al., 2003), although three basalts (20AZ12, 20AZ13 and
09RC19) that are exposed between Guamote and Macas plot in the
The SiO2 content of the sampled igneous (basalts to andesites) and seamount field with Nb/La ratios higher than one, which is consistent
volcanoclastic rocks (tuffs and lapilli) of the Alao Arc, along with two with the N-MORB normalized multi-element plots. Tectonic discrimi
igneous rocks of the Salado Arc (a dolerite and a basalt), ranges between nation using V and Ti (Fig. 7b; Shervais, 1982) also suggests that the
46.8 and 62.21 wt% SiO2 (Table 2), while their MgO content spans igneous units of the Alao Arc formed in an arc setting that may have been
2.93–8.83 wt%. These igneous rocks range between the sub-alkaline undergoing extension.
basalt to basaltic to andesitic fields in the Zr/TiO2 versus Nb/Y classi The basaltic to andesitic rocks of the Alao and Salado Arcs with arc
fication diagram (Fig. 5; Winchester and Floyd, 1977), although two characteristics plot above the mantle array when comparing Nb/Yb with
basalts of the Alao Paute Unit (20AZ12 and 09RC19) fall into the alka Th/Nb (Fig. 7c; Pearce, 2008), perhaps due to magma interaction with
line field. Most of the volcanic rocks of the Alao Arc overlap with the continental crust (e.g., Mariana intra-oceanic arc, Pearce, 2008). On the
field defined by igneous rocks of the Quebradagrande Arc in the contrary basalts 20AZ12, 20AZ13 and 09RC19 lie in the mantle array
Cordillera Central of Colombia (Cochrane et al., 2014; Nivia et al., 2006; between E-MORB and OIB, corroborating their elevated Nb/La ratios
Rodríguez and Zapata, 2013; Villagómez et al., 2011). Despite the fact (Fig. 7a). Finally, a comparison of Nb/Yb and TiO2/Yb (Fig. 7d; Pearce,
that Na and K are among the most mobile elements in magmatic- 2008) shows that melting of the source of the arc-like rocks occurred at
hydrothermal processes, a comparison of Na2O + K2O and SiO2 shallower depths than basalts 20AZ12, 20AZ13 and 09RC19, which plot
(Fig. 5b; Le Bas et al., 1986) yields similar results to Zr/TiO2 versus Nb/ closer to Ocean Island Basalt compositions, suggesting a deeper melting
Y, and most of the rocks lie within the basalt, basaltic-andesite and zone.
andesite fields.
Basaltic to andesitic rocks of the Alao and Salado Arcs have a broad 4.3. Isotopic tracing of magma sources
range of metaluminous compositions with ASI (Aluminium Saturation
Index) values that range between 0.183 and 1.227 (Fig. 5c), which are Age-uncorrected, whole rock 143Nd/144Nd ratios of the igneous rocks
typical of Andean arcs (e.g., Spikings et al., 2015). A comparison of Th of the Alao and Salado Arcs range between 0.51248 and 0.51301 (εNd
and Co (Hastie et al., 2007; Fig. 5d) reveals a dominantly calc-alkaline values between − 3.09 and 7.34), 87Sr/86Sr between 0.70378 and
trend for both the Alao and Salado Arcs, while the Ternary AFM dia 0.70665, 206Pb/204Pb between 18.79 and 19.48, 207Pb/204Pb between
gram (not shown, Na2O + K2O – FeOtot – MgO; Kuno, 1968) reveals a 15.57 and 15.75, and 208Pb/204Pb values between 38.56 and 39.20
trend that straddles between the tholeiitic and calc-alkaline fields, (Table 2). In the absence of accurate estimates of their crystallisation
although this must be interpreted with caution because of the altered ages, these ratios have been age-corrected to initial values at 120 Ma and
nature of the volcanic rocks. 75 Ma (Fig. 8; Table 2), given previous estimates of their ages (see
With the exception of three basalts (20AZ12, 20AZ13 and 09RC19, Section 5.3) and U-Pb zircon dates of 114.3 ± 3.8 Ma and 112.9 ± 0.8
shown as dashed lines in Fig. 5e–f), N-MORB-normalized multi-element Ma obtained from the potentially equivalent Quebradagrande Arc in
plots (Fig. 5e; Sun and McDonough, 1989) of basaltic to andesitic rocks Colombia (Cochrane et al., 2014; Villagómez et al., 2011).
of the Alao Arc show negative Nb, Ta and Ti anomalies, positive Pb These scattered Nd and Sr isotopic compositions (Fig. 8a) range be
anomalies, positive and negative Sr anomalies and variably enriched tween bulk silicate earth and oceanic reservoirs that are proximal to
LILE relative to HFSE, although the LILE have probably been modified northwestern South America (e.g., East Pacific Rise and Galapagos
by secondary alteration processes. N-MORB-normalized REE plots Islands, White et al., 1993), while some rocks lie beyond the mantle
(Fig. 5f; Sun and McDonough, 1989) reveal a moderate enrichment in array towards the EM1 and EM2 end-members of Zindler and Hart
LREE compared to MREE and HREE. N-MORB normalized compositions (1986). Comparisons between Sr–Nd–206Pb isotopic compositions
of dolerite 20PB17 and basalt 20PB19 of the Salado Arc (Fig. 5e, f) are (Fig. 8b, c) reveal trends between the main oceanic reservoirs of the
indistinguishable from most of the igneous units of the Alao Arc. The region and the EM2 end-member of Zindler and Hart (1986), regardless
volcanic rocks of the Alao Arc show an increase in SiO2, Zr and Y with of whether the ratios are corrected to 120 or 75 Ma. Lead isotopic
decreasing MgO, and thus reveal magmatic differentiation (Fig. 6a–c). compositions (206Pb/204Pb vs 208Pb/204Pb and 206Pb/204Pb vs
207
The decrease of CaO, Ni and Sc with decreasing MgO is indicative of Pb/204Pb; Fig. 8d, e) range between the fields of Triassic K-feldspar
plagioclase, olivine, and pyroxene fractionation (Fig. 6d–f). Al2O3 in from the Eastern Cordillera of Ecuador (Paul et al., 2018), which crys
creases and then decreases, with decreasing MgO (Fig. 6g), revealing the tallised from peraluminous crustal melts, and the EM2 end-member
early fractionation of pyroxene and later crystallisation of plagioclase. (Zindler and Hart, 1986). The three basalts of the Alao-Paute Unit that
FeOT, TiO2 and V are very scattered and do not correlate with MgO are exposed along the Guamote-Macas traverse (basalts 20AZ12,
(Fig. 6h–j). The Dy/Yb ratio remains unchanged as MgO decreases, 20AZ13 and 09RC19) yield the most juvenile Nd isotopic composition
suggesting a lack of amphibole and garnet fractionation (Fig. 6k; e.g., (143Nd/144Nd around ~0.5129), although their Sr and Pb isotopic
Davidson et al., 2007). A subtle negative Eu anomaly is observed compositions are undistinguishable from the other igneous rocks of the
(Fig. 6l) and Eu/Eu* ranges from 0.76 to 1.07, except for basalts Alao Arc.
20PB02, 20PB14 and 09RC19, which show positive Eu anomalies
40
ranging from 1.12 up to 1.51. The Sr/Y ratio ranges between 2.09 and 4.4. Ar/39Ar data
30.17 and shows no correlations with MgO content (not shown),
although it reveals calk-alkaline trends (Fig. 6m) for the Alao and Salado Raw 40Ar/39Ar data are presented in Supplementary material 1,
Arc, which is consistent with the Th and Co compositions (Fig. 5d). while the sample locations and dates are shown in Fig. 2, and a summary
Basalts 20AZ12, 20AZ13 and 09RC19, sampled from the Alao-Paute of the data is presented in Table 3. 40Ar/39Ar, K/Ca and inverse isochron
Unit along the road between the towns of Guamote and Macas (shown in plots are provided in Supplementary material 2. Plateau dates are
red in Fig. 2), show geochemical differences to other igneous rocks of the defined when at least 50% of the 39Ar released is contained in at least
Alao Arc, with higher Zr, Y, TiO2 and Nb concentrations (Fig. 6b, c, i, n). five or more contiguous steps that yield individual dates that are
These three basalts also yield flatter N-MORB normalized multi-element indistinguishable at ±2σ (Schaen et al., 2021). Plateau dates are only
15
BAÑOS AND PENIPE

80
240 a. b. c.
Basaltic tuff 20PB23 Basaltic andesitic tuff 20AZ18
110
Groundmass - 15V 60 Groundmass - 5V
(Maguazo Unit) (Alao-Paute Unit)
Ar/39Ar date (Ma)

180
Ar/39Ar date (Ma)

Ar/39Ar date (Ma)
65.10±0.81 Ma
(plateau age) 80
40
120 40.15±0.91 Ma
(weighted mean age)
16.57±3.09 Ma 20 Tuff 20AZ22 50
40
40
40
60 (weighted mean age) Groundmass - 15V

(Maguazo Unit)
0 0 20
0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
39
39
Ar released (%) Ar released (%) 39
Ar released (%)
HUARGUALLÁ VALLEY
d. e. 35 f.
45 75
Basaltic andesite 20BB04 Basaltic andesite 20BB06
Groundmass -10V Groundmass - 15V
(Peltetec Unit)
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)

(Peltetec Unit)
30 60 32
32.84±0.38 Ma
(plateau age)
15 45 29
Basaltic andesite 20BB07
40
40
40
Groundmass - 5V
20.60±3.22 Ma (plateau age) 51.11±2.10 Ma (plateau age) (Peltetec Unit)
0 30 26
0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
39 39 39
Ar released (%) Ar released (%) Ar released (%)
GUAMOTE-MACAS ROAD
48 400 65
g. h. i.
Tuff 20AZ16 Basalt 20AZ13 60.00±0.66 Ma
Groundmass - 5V Plagioclase - 1.5A (weighted mean age)
42 300 62
(Maguazo Unit) (Alao-Paute Unit)
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)

Ar/39Ar date (Ma)
36 200 86.83±12.23 Ma 59
(weighted mean age)
30 100 56 Basalt 20AZ12

40
40
40
Groundmass - 15V
35.24±1.12 Ma
(Alao Paute Unit)
(plateau age)
24 0 53
0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
39 39
39
j. k. 38.28±0.51 Ma
70
Basalt 20PB19 38 Dolerite 20PB17
Groundmass - 5V Groundmass, mainly
(Upano Unit) hornblende - 5V
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)
55 34 (Upano Unit)
(staircase topology)
31.84±0.38 Ma
40 (plateau age) 30
40
40
27.76±0.44 Ma
25 26
0 20 40 60 80 100 0 20 40 60 80 100
39 39
Ar released (%) Ar released (%)
Fig. 9. 40Ar/39Ar spectra for groundmass and plagioclase extracted from mafic rocks of the Alao and Salado Arcs in the Eastern Cordillera of Ecuador. Box heights
represent uncertainty at 2σ.
16
TADAY AND PAUTE

80 90
l. m. n.
50 Basalt 20PB14 73.93±0.88 Ma
70 Groundmass - 15V 80 (weighted mean age)
(Alao-Paute Unit)
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)

72.64±0.81 Ma 40
60 (plateau age)
70
30
50
Tuff 20AZ01 60 Basaltic andesite 20PB15
40
40
40
Groundmass - 15V 31.56±1.31 Ma
Groundmass - 15V
40 20
(Alao-Paute Unit) (weighted mean age) (Alao-Paute Unit)
50
0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
39 39 39
GUALACEO
80
o. p. q.
180 72 67.67±0.97 Ma
Basaltic-tuff 20PB04
(weighted mean age)
Groundmass -10V
(Alao-Paute Unit)
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)

68 60
120 70.52±0.88 Ma
(weighted mean age)
64
40
60
Basaltic andesite 20PB05 Basalt 20PB06
40
40
40
60
Groundmass - 15V Groundmass - 15V
(Alao-Paute Unit) (Alao-Paute Unit)
54.33±8.89 Ma (plateau age)
0 56 20
0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
39 39 39
r. s.
48 75
39.59±0.76 Ma
(plateau age)
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)
70.84±1.27 Ma
42 60 (weighted mean age,
staircase topology)
36 45 Volcanoclastic
Basalt 20PB07 rock 20PB08
40
40
Groundmass - 5V Groundmass - 10V

35.50±1.01 Ma
30 30
0 20 40 60 80 100 0 20 40 60 80 100
39 39
87 t. u.
Metabasalt 20PB09 130
Metabasalt 20PB09
Groundmass - 15V Plagioclase - 1.7A
Ar/39Ar date (Ma)
Ar/39Ar date (Ma)
110
78
90
69
40
40
70
69.71±0.80 Ma 78.83±2.38 Ma
(plateau age) (weighted mean age)
60 50
0 20 40 60 80 100 0 20 40 60 80 100
39 39
Fig. 9. (continued).
considered significant if they are indistinguishable from the corre isotopic measurements in this study limits the usefulness of this com
sponding inverse isochron dates, and where the (40Ar/36Ar)i is indis parison. Flat regions on age spectra that include 3 or more contiguous
tinguishable from the atmospheric value at 95% of the distribution steps but include <50% of 39Ar released are tentatively considered to be
(298.56 ± 0.31; Lee et al., 2006), although the imprecision of the Ar useful, and they are referred to as weighted mean dates, which are
17
means of the ages of the included steps weighted via their precision. the Alao-Paute Unit located north of Taday and ~5 km west of the ~75
Twenty-one out of twenty-nine igneous rock samples from the Alao Ma-old Tampanchi Complex (Villares et al., 2022), yielded a plateau
and Salado Arcs yielded plateau (~20 to ~72 Ma) and weighted mean date of 72.64 ± 0.81 Ma (61.20% 39Ar released) from a disturbed age
(~16 to ~86 Ma) dates, with no geographic trends. These dates overlap spectrum which shows Ar-loss in the lower temperature degassing steps.
with their inverse isochron dates with the exception of plagioclase from Further south, groundmass from basalt 20PB14 (Alao-Paute Unit) gave a
metabasalt 20PB09. Likewise, almost all initial 40Ar/36Ari overlap with disturbed age spectrum, although the higher temperature steps yield a
an atmospheric composition, except groundmass from basaltic andesitic weighted mean date of 31.56 ± 1.31 Ma (40.56% 39Ar released;
tuff 20AZ18 and basaltic andesite 20PB05, and plagioclase from meta Fig. 9m). The elevated dates of the lower temperature steps are probably
basalt 20PB09. caused by excess 40Ar, and 39Ar recoil is dismissed because K/Ca ratios
range is negligible. Groundmass from basaltic-andesite 20PB15 (Alao-
4.4.1. The north: Close to the towns of Baños and Penipe Paute Unit) yields a disturbed age spectrum, and its flattest part yields a
In the northernmost part of the study area, west of Baños town weighted mean date of 73.93 ± 0.88 Ma (43.93% 39Ar released; Fig. 9n).
(Fig. 2), groundmass from basaltic tuff 20PB23 (Fig. 9a) of the Maguazo The elevated date of the first heating step reveals the presence of excess
40
Unit yielded a young weighed mean date of 16.57 ± 3.09 Ma (62.13% Ar, and the discordance in the higher temperature steps is typical of 37,
39 39
Ar released; K/Ca ratio 29.4 ± 4.5) from a disturbed age spectrum Ar recoil.
which shows excess 40Ar in the lower temperature degassing steps and
37,39
Ar recoil in the higher temperature steps. Further south (south-east 4.4.5. The South: close to Gualaceo town
of Penipe town; Fig. 2), tuff 20AZ22 of the Maguazo Unit yielded an Plateau and weighted mean dates of groundmass extracted from four
older plateau date of 65.10 ± 0.81 Ma (68.71% 39Ar released; Fig. 9b) igneous rocks of the Alao-Paute Unit close to the town of Gualaceo range
and shows evidence for Ar-loss in the lower temperature heating steps. between 39.59 ± 0.76 Ma and 70.52 ± 0.88 Ma (Fig. 9o–r). Similar to
Basaltic andesitic tuff 20AZ18 of the Alao-Paute Unit, yielded a the igneous rocks of the Alao-Paute Unit further north, these age spectra
weighted mean date of 40.15 ± 0.91 Ma (43.18% 39Ar released; Fig. 9c), show either older ages in the lower-T steps due to the presence of excess
with evidence for excess 40Ar in the lower-T steps. 40
Ar (e.g., basaltic tuff 20PB04 and basalt 20PB07), and 39Ar recoil is
discarded on the basis of the K/Ca spectra, or younger dates that are a
4.4.2. The Huarguallá Valley result of several factors. These are either degassing secondary phases at
Three groundmass concentrates of basaltic andesites were dated, low temperature (see Section 4.1), or diffusive loss of Ar (e.g., basaltic
which are exposed within faulted slivers of the Peltetec Fault Zone in the andesite 20PB05 and basalt 20PB06). Groundmass of a mafic volcano
Huarguallá Valley located northeast of the town of Guamote (Fig. 2). clastic rock (20PB08) of the Alao-Paute Unit yields an age spectrum with
Groundmass from basaltic andesite 20BB04 yields a relatively young a staircase topology, where the step dates progressively increase from
and imprecise plateau date of 20.60 ± 3.22 Ma (90.76% 39Ar released; 35.50 ± 1.01 Ma to a flat region which has a weighted mean age of
Fig. 9d), with dates that increase to ~40 Ma in the higher-T steps. 70.84 ± 1.27 Ma (47.07% 39Ar released; Fig. 9s). The last four highest-T
Basaltic andesite 20BB06 gives an older plateau date of 51.11 ± 2.10 Ma steps give younger dates that is probably a consequence of 37,39Ar-recoil.
(72.63% 39Ar released; Fig. 9e), albeit from lower-temperature steps. Finally, groundmass from metabasalt 20PB09 (Alao-Paute Unit) yields a
Finally, groundmass from basaltic andesite 20BB07 yields a plateau date disturbed age spectra with a plateau date of 69.71 ± 0.80 Ma (76.93%
of 32.84 ± 0.38 Ma (87.01% 39Ar released; Fig. 9f). and shows Ar-loss in 39
Ar released; Fig. 9t). Plagioclase from the same sample yields a saddle-
the lowest-T heating step. shape age spectrum where the flattest part gives a weighted mean date
of 78.83 ± 2.38 Ma (52.63% 39Ar released; Fig. 9u), although an initial
40
4.4.3. The road between Guamote and Macas Ar/36Ari value of 494.0 ± 114.5 suggests it is affected by excess 40Ar.
Three samples from the Alao-Paute Unit exposed along the road
between the towns of Guamote and Macas (Fig. 2) yield plateau and 5. Interpretation
weighted mean dates. Groundmass from tuff 20AZ16 yields a plateau
date of 35.24 ± 1.12 Ma (100% 39Ar released; Fig. 9g). Further east 5.1. Tectonic origin and magmatic evolution of the Alao Arc
along the traverse, plagioclase from basalt 20AZ13 yields a saddle sha
ped spectrum that is generally indicative of excess 40Ar (Kelley, 2002), The volcanic rocks of the Alao Arc, along with two samples of the
although lower K/Ca compositions of the lowest temperature heating Salado Arc, have basaltic to andesitic compositions with a broad calc-
steps could also be attributed to 39Ar recoil (Supplementary material 2). alkaline and metaluminous signature, they show negative Nb, Ta, Zr,
The youngest part of the saddle gave a weighted mean date of 86.83 ± Hf and Ti anomalies, variable LILE enrichment relative to HFSE, and a
12.23 Ma (53.65% 39Ar released; Fig. 9h). Groundmass from basalt moderate enrichment in LREE compared to MREE and HREE (Fig. 5e, f),
20AZ12 has a weighted mean age of 60.00 ± 0.66 Ma (46.59% 39Ar which are characteristics of dehydration of a subducted slab in volcanic
released, K/Ca 0.337 ± 0.038; Fig. 9i) from the flattest part of the arc settings (Perfit et al., 1980; Schmidt and Jagoutz, 2017). Tectonic
otherwise highly disturbed age spectrum, which may reflect both the discrimination diagrams suggest these rocks formed in a continental to
presence of excess 40Ar and the effects of 37, 39Ar recoil. Two-samples oceanic arc environment in an extensional setting (Fig. 7a–b), with the
from the Upano Unit (usually assigned to the Salado Arc) were ana exception of basalts 20AZ12, 20AZ13 and 09RC19, which are discussed
lysed in the easternmost part of the road between Guamote and Macas. below. All of the volcanic rocks of the Alao and Salado Arcs yield Th/Yb
Groundmass from basalt 20PB19 yielded a plateau date of 31.84 ± 0.38 ratios that are higher than the mantle array, where some have compo
Ma (59.22% 39Ar released; Fig. 9j). In contrast, groundmass (which is sitions that are consistent with the continental crust (Fig. 7c, d; e.g., arc
mostly hornblende) from dolerite 20PB17 gave a disturbed spectrum magmas in the Mariana arc system; Pearce, 2008). This suggests that the
with a staircase topology where the step dates progressively increase primitive basaltic melts of the Alao and Salado Arc assimilated material
from 27.76 ± 0.44 Ma to 38.28 ± 0.51 Ma with increasing degassing that had a continental crust affinity (Fig. 7c; Pearce, 2008). This is
temperature (Fig. 9k). The staircase topology suggests the sample may consistent with the Sr–Nd–Pb isotopic systematic of the Alao and Salado
have experienced 40Ar loss due to thermally driven diffusion, although it Arcs (Fig. 8), that reveal source mixing by recycling of crustal terrige
is more likely that secondary phases were degassed at low temperatures nous sediments to the mantle wedge during subduction, showing trends
with contrasting K/Ca ratios (de Jong, 2009; Schaen et al., 2021). from mantle-like compositions of the region (East Pacific Rise and
Galápagos Islands) towards the EM2 reservoir (Fig. 8a–e). Furthermore,
4.4.4. Close to Taday and Paute Pb-isotopic compositions show that the Triassic basement of the Eastern
Groundmass from tuff 20AZ01 (Figs. 4g and 9l), which forms part of Cordillera (Spikings et al., 2019; Fig. 8d, e) could be one of the end-
18
39 39
a. ArK Plateau dates b. ArK Plateau dates
AZ22-Gm BB07-Gm PB19-Gm PB07-Gm
Group I BB04-Gm AZ16-Gm Group I AZ01-Gm PB09-Gm
BB06-Gm PB04-Gm
30 30
Group II Group II
0.6 =0
.6
C a= Ca
K/ .3 / .3
30 a=0 30 K a=0
Ma K/C 20 Ma K/C 20
45 M
a
45 M
a
75 Ma 10 10
75 Ma
40 20 40 60 80 37 40 20 40 60 80 37
Ar(r) ArCa*(f) Ar(r) ArCa*(f)
39
c. ArK Weighted mean dates d. Plateau and weighted mean dates (Groundmass)
PB23-Gm PB15-Gm 4 (n=18) 70.6 Main alteration
Group I AZ18-Gm PB05-Gm phase in
15 AZ12-Gm PB06-Gm groundmass:
M a PB14-Gm PB08-Gm 30 Clay
Group II 32.2
0.6 3 Chlorite
C a=
K/ .3 Sericite
30 a=0
Ma K/C 20
2
45 M
a
Group III 10
1
75 Ma
0
40 20 40 60 80 37
Ar(r) ArCa*(f) 0 10 20 30 40 50 60 70 80 90 100 Ma
Fig. 10. a, b, c. 40Ar(r), 39Ar(K) and 37Ar(Ca) ternary diagram comparing plateau and weighted mean dates (37Ar(Ca) is multiplied by f = 2.3255, with f being a constant
calculated from our dataset that allows the comparison of the acquired data with K/Ca ratios on the ternary diagram). d. Histogram and KDE from plateau and
weighted mean dates (histogram bars are coloured according with their main alteration phases).
member components that formed the isotopic compositions of the Alao with the interpretation of Spikings et al. (2015). Furthermore, the two
and Salado Arcs. A comparison of TiO2/Yb and Nb/Yb reveals source volcanic rocks of Salado Arc (Upano unit) are geochemically and
melting at shallow depths that supports mantle melting beneath a thin isotopically indistinguishable from the Alao Arc, and pending better
continental crust (Fig. 7d; Pearce, 2008). Sr/Y ratios (<30) and negative geochronological constrains, they are tentatively considered to have
Eu anomalies (Fig. 6m, n) suggest the magma evolved in shallow res formed within the same overall tectonic scenario.
ervoirs in the crust (Chiaradia, 2015) with fractionation of plagioclase,
olivine, and pyroxene, which is typical of calc-alkaline rocks and is 40
5.2. The significance of the Ar/39Ar dates
consistent with the petrography of the freshest samples. No evidence for
amphibole and garnet fractionation corroborates a thin arc crust.
The abundances of radiogenic 40Ar (40Ar(r)), 39Ar that formed from
Distinctly different geochemical characteristics were obtained from
reactions of 39K in the reactor (39ArK), and 37Ar that formed from re
basalts 20AZ12, 20AZ13 and 09RC19, which have been mapped as part
actions of 40Ca in the reactor (37ArCa) have been compared to assess the
of the Alao Arc sequence. These basalts have an E-MORB-like signature
degree of influence of Ca- and K-bearing secondary phases on the Ar
(Nb/La > 1; Fig. 2 and 7a) with elevated Nb/La values and flatter N-
isotopic compositions of the groundmass (Fig. 10a–c). Isochrons at 75,
MORB normalized multi-element plots without negative Nb, Ta, Zr, Hf
45 and 30 Ma (determined using a J-value of 0.0048682, which is the
and Ti anomalies. This suite also yields Th/Yb and Nb/Yb ratios that
mean value of all measured monitors) are drawn for reference. K/Ca
approximate mantle compositions without any influence of a subduction
isolines of 0.3 and 0.6 are also shown for reference, where K/Ca ratios
component (Fig. 7c; Pearce, 2008), corroborating their Nd isotopic
lower than 0.3 are an approximation of the range of primary mafic
compositions, which are the most juvenile among the studied rocks
compositions (basaltic-andesitic). The Ar isotopic compositions of in
(Fig. 8a). Thus, in the absence of robust geochronological data (see
dividual heating steps have been plotted ignoring those that reveal the
Section 4.3), we suggest that these E-MORB-type basalts represent a
presence of i) obvious 39,37Ar recoil (oscillating older and younger step
magmatic component of an intra-arc rift setting that formed in a highly
dates), and ii) excess 40Ar (according to elevated dates in the lower-T
attenuated, extending continental crust (Pearce, 2008; Pearce et al.,
steps and saddle shaped age spectra).
2005).
Data obtained from the groundmass aliquots do not reveal any sys
Summarising, the geochemical and isotopic data from the Alao Arc
tematic trend compared to the temperature of degassing in the plotted
supports a volcanic arc environment within continental crust in an
ternary space, however, they can be placed into three groups
extensional tectonic setting. This interpretation is entirely consistent
(Fig. 10a–c). Samples in Group I plot with high K/Ca ratios with almost
19
no 37ArCa, and resemble a mixing line between reservoirs of 39ArK and sedimentary intercalations of the Alao Arc (the Maguazo Unit) constrain
40
Ar(r). These are groundmass from tuffs (20PB23, 20AZ22, 20AZ18, the age of deposition between Upper Bathonian to Albian (~166–100;
20AZ16 and 20AZ01), basaltic to basaltic andesitic lavas (20BB06, Molyneux, 1988; Riding, 1989; Litherland et al., 1994) which partially
20PB19 and 20PB06), volcanoclastic rock (20PB08) and metabasalt overlaps the crystallisation age estimation for the igneous rocks of the
(20PB09). These groundmass compositions are best explained by the Alao Arc.
presence of a large volume component of K-alteration. Most of the vol Consequently, the Alao Arc formed at some time between ~149 and
canic and volcanoclastic rocks only show groundmass altered to clay and ~73 Ma, and we propose that the age is ~140–110 Ma, based on three
chlorite (e.g., basalt 20PB14 and volcanoclastic rock 20PB08; Fig. 4b, d, observations: i) The rocks of the Alao Arc have a dominant and near
f), although basaltic andesite 20BB06 and tuff 20AZ01 also include vertical foliation that is pervasive across most of the rocks of the Eastern
abundant sericite (Fig. 4b, g). This group yields plateau and weighted Cordillera (i.e., it also occurs within the Guamote sequence of the
mean dates that span between ~16–72 Ma, and given that even the Chaucha Block and the Upano Fm. of the Salado Arc; Figs. 1 and 2), and
highest-T heating steps yield unexpectedly high K/Ca ratios (>100; e.g., formed during strike-slip displacement under greenschist conditions
tuff 20AZ01) for mafic rocks, it is likely that none of these dates record (Pratt et al., 2005; Spikings et al., 2015, 2019). This deformation is not
the time of crystallisation. found in younger basement rocks that accreted to the west at ~75 Ma in
Samples in Group II have lower K/Ca values, although they are still the Western Cordillera of Ecuador (Spikings et al., 2005; Vallejo et al.,
higher than 0.3 and thus are elevated relative to andesitic and basaltic 2009). Therefore, we suggest that the dominant foliation within the
compositions (Fig. 10a–c). These samples are groundmass from basalts Eastern Cordillera pre-dates the collision event at ~75 Ma. ii) Late
and andesites (20BB04, 20BB07, 20AZ12, 20PB15, 20PB04, 20PB05 and Triassic (~209 Ma) to Lower Cretaceous (~112 Ma) arc units
20PB07), which have the same clay and chlorite alteration assemblage throughout the northern Andes (Colombia and Ecuador) young west
as the previous group (e.g., 20BB04; Fig. 4d), except basalt 20AZ12 wards (Fig. 1), while also becoming less silicic and more isotopically
which shows abundant chlorite as a secondary phase (Fig. 3d). The juvenile, revealing larger mantle-derived components in their source
lower K/Ca ratios compared to group I suggests they may contain a regions. The Alao Arc lies along the western flank of this prolonged arc
lower volume component of K-alteration phases, or more calcic alter sequence, and is the most isotopically juvenile, the least differentiated
ation phases, although this was not confirmed via optical petrography. and is dominated by volcanic units (Fig. 2;Cochrane et al., 2014; Spik
40
Ar/39Ar dates from this group span between ~20–73 Ma, and these are ings et al., 2015). Therefore, we suggest that the Alao Arc formed at or is
also not considered to be accurate estimates of the time of crystallisation younger than the eastern Salado Arc, which formed between ~145–121
of the primary igneous rock. Ma. iii) The Quebradagrande Complex of the Cordillera Central of
Finally, groundmass from basalt 20PB14 plots in a distinct region Colombia is exposed along-strike of the Alao Arc (Fig. 1) and has a
(group III; Fig. 10c) that yields a significant proportion of 37ArCa (K/Ca similar isotopic and geochemical composition, and thus it is considered
<0.1) with a relatively low amount of radiogenic 40Ar, and a weighted to be equivalent to the Alao Arc (Spikings et al., 2015). A tuff and a
mean 40Ar/39Ar date of 31.56 ± 1.31 Ma. This composition is more diorite of the Quebradagrande Complex yield U-Pb zircon dates of 112.9
characteristic of mafic rocks, although thin section analyses reveal the ± 0.8 Ma (Cochrane et al., 2014) and 114.3 ± 3.8 Ma (Villagómez et al.,
presence of secondary clay, chlorite and epidote (Fig. 4c), although 2011), respectively. Therefore, based on these arguments, we suggest
epidote could potentially account for its calcic composition. Therefore, the Alao Arc sequence formed at some time between ~140–110 Ma,
we are not confident that this date represents a crystallisation age. assuming it is equivalent to the Quebradagrande Arc.
In summary, all of the volcanic rocks of the Alao Arc have undergone
40
various degrees of alteration with the formation of secondary K- and Ca- 5.4. Ar/39Ar dates and geological events
bearing minerals, resulting in highly variably K/Ca ratios, and thus it is
extremely likely that the 40Ar/39Ar dates are not crystallisation ages. Although the 40Ar/39Ar groundmass dates do not record the crys
The oldest plateau 40Ar/39Ar date obtained from the Alao Arc is 72.64 ± tallisation ages of the Alao and Salado Arc, the plateau and weighted
0.81 Ma (tuff 20AZ01; Fig. 4g and 9m), which has abundant potassic mean dates show two peaks from a Kernel Density Plot (Fig. 10d) that
alteration phases (mainly sericite), and thus it is likely to be a minimum are late Cretaceous – Paleocene (~75–60 Ma) and Eocene – early
crystallisation age. Furthermore, three of the older 40Ar/39Ar dates were Oligocene (~45–30 Ma). These periods coincide with major tectonic
obtained from rocks with sericite as the main alteration phase (Fig. 10d). rearrangements within northwestern South America. The late Creta
ceous – Paleocene was dominated by the collision and accretion of a
5.3. The age of the Alao Arc large oceanic plateau and overlying intra-oceanic arc (the Caribbean
Large Igneous Province; the Pallatanga-Piñon terrane in Ecuador;Spik
The igneous rocks of the Alao Arc are mainly mafic and host neither ings et al., 2001, 2015; Vallejo et al., 2009). This accretion event drove
zircons nor baddeleyite. Furthermore, all of the Ar isotopic data ac significant cooling (≤300 ◦ C) and exhumation along the continental
quired from the mafic units has been modified by secondary K- and Ca- margin, which is recorded by U-Pb (apatite; Paul et al., 2018), 40Ar/39Ar
bearing minerals, and thus no accurate radiometric dates for the time of (white mica and biotite from Late Jurassic intrusions; Spikings et al.,
crystallisation of the arc rocks have been obtained. Previous K/Ar 2001), and fission track (apatite and zircon; Spikings et al., 2000, 2001,
hornblende dates of the volcanic rocks range between ~142 ± 36 and 2005, 2010) thermochronology of the Eastern Cordillera. The accretion
99 ± 10 Ma (Litherland et al., 1994; Table 1), although they are not and collision of the thickened crust, gave rise to the foreland basin
considered to be useful because the degree of Ar loss cannot be quan setting in the east, and may have promoted hydrothermal circulation
tified. Our 40Ar/39Ar geochronology of groundmass yielded dates that that altered the pre-existing assemblage of the buttressing South
lie between ~75–16 Ma and the oldest plateau 40Ar/39Ar date obtained American margin (i.e., the Alao Arc).
from the volcanic rocks of the Alao Arc in Ecuador of 72.64 ± 0.81 Ma is The Eocene – early Oligocene history of the Eastern Cordillera of
probably a minimum age for the arc. Sedimentary units that are Ecuador is also characterised by a phase of accelerated cooling and
considered to form part of the forearc of the Alao Arc in Ecuador exhumation (Spikings et al., 2001), as a result of increased convergence
(Maguazo Unit) host detrital zircons that yield a maximum U-Pb con rates between the Farallon and South American plates (e.g., Pardo-Casas
cordia date (LA–ICP–MS) of 163.7 ± 1.6 Ma, while the equivalent and Molnar, 1987), due to the opening of the southern Atlantic Ocean (e.
sedimentary unit in Colombia, within the Quebradagrande Arc, yields a g., Sébrier and Soler, 1991). Arc magmatism in the Eastern Cordillera
minimum zircon U-Pb age of 149.2 ± 6.1 Ma (Cochrane et al., 2014). formed some intrusive bodies that yield Eocene – Oligocene U-Pb zircon
These suggest that the arc rocks are younger than 149.2 ± 6.1 Ma, and crystallisation ages (41.44 ± 0.31 Ma, 39.40 ± 0.23 Ma and 33.78 ±
are older than 72.64 ± 0.81 Ma. Palaeontological data obtained from 0.31 Ma; Guerrero, 2020; Fig. 2). Consequently, heat flow perturbations
20
may have also influenced the Ar-isotopic system of the Alao Arc. Antoine provided assistance in the noble gas mass spectrometer
The 40Ar/39Ar dates may also be a function of thermally driven laboratory.
diffusive loss, where the rocks may have resided at temperatures hotter
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LITHOS 462-463 (2023) 107400

Contents lists available at ScienceDirect

Geochronological, geochemical and isotopic characterisation of the Early

CAF Chinguál COLOMBIA

3.2. Whole rock geochemistry 3.3. Sr–Nd–Pd isotopes

Weighted mean dates

LITHOS 462-463 (2023) 107400

Step heating dates shown in bold are the preferred dates.

Salado Arc Dacite andesite

Arc Crust Arc

andesite et al. (2014)

CC Andesite Salado Arc

0.1 MORB array

BAÑOS AND PENIPE

Ar/39Ar date (Ma)

Ar/39Ar date (Ma)

60 (weighted mean age) Groundmass - 15V

Ar/39Ar date (Ma)

Ar/39Ar date (Ma)

Ar/39Ar date (Ma)

30 100 56 Basalt 20AZ12

Ar/39Ar date (Ma)

TADAY AND PAUTE

Ar/39Ar date (Ma)

Ar/39Ar date (Ma)

Ar/39Ar date (Ma)

Ar/39Ar date (Ma)

Ar/39Ar date (Ma)

Groundmass - 5V Groundmass - 10V

Ar/39Ar date (Ma)

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