Paleoclimatic conditions and paleoweathering processes on Mesozoic continental redbeds from Western-Central Mediterranean Alpine Chains

Palaeogeography, Palaeoclimatology, Palaeoecology 395 (2014) 144–157

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Paleoclimatic conditions and paleoweathering processes on Mesozoic continental redbeds from Western-Central Mediterranean Alpine Chains Francesco Perri a,⁎, Tohru Ohta b a b

Dipartimento di Biologia, Ecologia e Scienze della Terra, Università degli Studi della Calabria, Via P. Bucci, 87036 Arcavacata di Rende, CS, Italy Department of Earth Sciences, Faculty of Education and Integrated Arts and Sciences, Waseda University, 1-6-1, Nishiwaseda, Shinjuku-ku, Tokyo 169-8050, Japan

a r t i c l e

i n f o

Article history: Received 19 September 2013 Received in revised form 9 December 2013 Accepted 19 December 2013 Available online 29 December 2013 Keywords: Continental redbeds Paleoweathering processes Paleoclimatic conditions Chemical composition Mesozoic Mesomediterranean microplate

a b s t r a c t Chemical and mineralogical analyses of the Triassic to lowermost Jurassic mudstones from continental redbeds outcropping in the Internal Domains of the Betic–Rifian and Calabria–Peloritani chains have been used to infer the relationships between paleoclimatic conditions and paleoweathering processes during rifting of a continental crust block that finally detached from adjoining western Tethyan realms to form an independent microplate (Mesomediterranean Microplate) from Jurassic to lower Miocene time. The studied mudstone samples come from Middle Triassic and Upper Triassic beds of the Saladilla Formation (both in the Betic Cordillera and in the Rif), whereas the Calabria–Peloritani Arc studied mudstones come from Upper Triassic to lowermost Jurassic beds (both in the Sila and Longi Taormina Units). Major and trace element concentrations, based on the massbalance calculation relative to the upper continental crust, show negative values both in Gibraltar and Calabria–Peloritani Arcs, implying that mudstone formation in the Early Mesozoic involved moderate to intense continental paleoweathering of the crust. In particular, CaO, Na2O, MgO, Sr, Ba, Fe2O3, MnO and transition metal elements (V, Cr, Co and Ni) are more depleted in the Triassic to Upper Jurassic samples of the Calabria–Peloritani samples than in the Middle to Upper Triassic Betic–Rifian samples, and suggest an increase of continental paleoweathering in the Mediterranean region from the Triassic to the Jurassic. In addition enrichment in SiO2, TiO2, Al2O3, K2O and incompatible elements in the Calabria–Peloritani Arc mudstones indicates sediment recycling effects that gradually increase from the Triassic to Jurassic time. The hinterland paleoweathering and sediment recycling effects have been mathematically distinguished using principal component analysis (PC1 is a measure of paleoweathering rate mainly due to humidity (positive values) against aridity (negative values), whereas PC2 corresponds to the extent of sediment recycling). The results strongly indicate that humidity had increased from the Triassic to the Jurassic and that the depositional environments in Calabria–Peloritani Arc were probably more suitable for sediment recycling. These seasonal climate alternations corresponding to an increase in paleoclimatic humidity that favored paleoweathering conditions and recycling processes. These results are also confirmed by the mineralogical data, which show a higher abundance of kaolinite, typical of warm–humid conditions, in the Calabria-Peloritani mudstones than in those of the Betic Cordillera and the Rif. Furthermore, the comparison among geochemical weathering index values of the studied samples and of recent soils from different climatic zones likely suggests a tropical rainforest climate in the studied area during the Triassic to the lowermost Jurassic. © 2013 Elsevier B.V. All rights reserved.

1. Introduction Continental redbeds are important indicators of paleogeographic, paleotectonic and paleoclimatic conditions in the sedimentary basins and their source areas, preferentially when they develop in relation to early stages of continental rifting (e.g., Perrone et al., 2006; Critelli et al., 2008; Perri et al., 2008b, 2011a; Perri et al., 2013 and references therein). In particular, Triassic to lowermost Jurassic continental redbeds that characterize the base of the Alpine cycle in many internal units of the Western-Central Mediterranean Alpine Chains represent ⁎ Corresponding author. Tel.: +39 0984 493550. E-mail addresses: [email protected] (F. Perri), [email protected] (T. Ohta). 0031-0182/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.palaeo.2013.12.029

important stratigraphic markers to reconstruct environmental and sedimentary characteristics of the basins in which they were deposited during the coeval breakup of the Pangea supercontinent (e.g., Guerrera et al., 1993; Martín-Algarra et al., 1995; Guerrera et al., 2005; Perri et al., 2005a, 2005b; Mongelli et al., 2006; Perrone et al., 2006; Aldinucci et al., 2008; Critelli et al., 2008; Perri, 2008; Perri et al., 2008a, 2008b; Zaghloul et al., 2010; Perri et al., 2011a, 2011b, 2012, 2013). Perrone et al. (2006) showed that the Mesozoic continental redbeds outcropping in the Internal Domains of the Western-Central Mediterranean Alpine Chains were paleogeographically and paleotectonically independent of the European–African Germano-Andalusian Triassic redbeds outcropping in the External Domains of the same chains and in their forelands. In addition, the same authors recognized: i) that

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two redbed subdomains, with ‘Verrucano-type’ and ‘Pseudoverrucanotype’ successions, also characterized by a different post-Triassic paleogeographic and tectonometamorphic evolution, can be differentiated in these internal Domains; ii) that both subdomains record the geodynamic evolution of the westermost Tethyan regions during the Triassic and Jurassic continental rift stage of Pangea; iii) that the source area of their continental Triassic and lowermost Jurassic redbeds was a small, isolated continental block rifted from the future European, African and Apulian plates, which provided clastic supply to its surroundings regions; and iv) that this continental blocks was finally detached to form an independent plate (Mesomediterranean Microplate) during the opening of the Western Tethyan and Central Atlantic oceanic basins. By comparing climate and weathering proxy signals from polar to equatorial regions, important insight into the global paleoclimate variations can be obtained (Ohta et al., 2011b). Furthermore, information about provenance, paleoclimate and sedimentary environment can only be achieved by combining a variety of geochemical records coupled to mineralogical data. As a result, previous studies have determined the spatial and temporal variations of the paleoclimate, paleoweathering and sediment recycling effects in the Verrucano/Pseuoverrucano-type redbeds using clastic petrofacies analysis of sandstones and conglomerates, as well as mineralogical and geochemical analyses of the associated fine-grained sediments (e.g., Mongelli et al., 2006; Critelli et al., 2008; Perri et al., 2008b, 2011a, 2013). However, since proxy signals can be overprinted by various diagenetic (and even metamorphic) effects, a full quantification of the change in paleoclimate and paleoweathering or extent of recycling has not been accomplished in this region. This is mainly due to the difficulties in separating the signatures of the paleoclimate change and sediment recycling effect. Furthermore, diagenesis is typically a process that bridges between weathering and metamorphism in the rock cycle (Keller, 1962). Sujkowski (1958) notes that there is no sharp boundary between diagenesis and weathering (Keller, 1962). Few studies permit utilization of compositional data to infer paleoclimate from ancient siliciclastic sediments (Dott, 1978). More recently, studies on ancient siliciclastic sediments have provided some basis for quantitative documentation of climate's role and control on composition of both modern (e.g., James et al., 1981; Suttner et al., 1981) and ancient sediments (e.g., Ridgway et al., 1999). Moreover, Suttner and Dutta (1986), have shown that the climatic imprint and, thus, the weathering processes on framework mineralogy remains rather indelible in spite of diagenesis, especially in case of alluvial sediments deposited and buried close to its source. In addition, previous works demonstrated that the extent and degree of geochemical modification induced by diagenesis are quite similar between Middle Triassic and lowermost Jurassic mudstone redbeds of the Western-Central Mediterranean Alpine Chains, since these sediments show a similar diagenetic evolution (e.g., Mongelli et al., 2006; Perri, 2008; Perri et al., 2008a; Zaghloul et al., 2010; Perri et al., 2011a, 2011b, 2013). Therefore, the relative geochemical variations may be induced by other geological factors, such as, paleoweathering and sediment recycling. This study focuses on the application of principal component analysis (multivariate statistics) in order to extract orthogonal latent variables. Previous studies have revealed that sediment geochemistry in the Mesomediterranean Microplate was largely governed by the change in paleoclimate and/or extent of sediment recycling (e.g., Mongelli et al., 2006; Critelli et al., 2008; Perri et al., 2008b, 2011a, 2013). If so, it is expected that extracted principal components will represent geochemical variations induced by the paleoclimate change and extent of sediment recycling. Mathematically, these principal components should be independent of each other, meaning that change in paleoclimate and extent of sediment recycling can be discussed individually. By the use of this technique, this study is aim to provide full quantification of the paleoclimatic evolution and of its

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incidence in sediment recycling and paleoweathering that allowed deposition of the Early Mesozoic Verrucano/Pseuoverrucano-type redbeds that characterize the Western Mediterranean Alpine regions. 2. Geological background The Central-Western Mediterranean area is limited by the Betic Cordillera, the Maghrebian Chain (Rif, Tell and Sicily), and the Apennines. They are linked by the Gibraltar Arc to the west and the Calabria–Peloritani Arc to the east, two main tectonic features that demonstrate the connection between different chains and that reveal a gradual change of convergence from one chain to another (e.g., Guerrera et al., 1993). The Gibraltar and the Calabria–Peloritani Arcs were shaped by Cretaceous to Miocene convergence during the Alpine orogeny and by late- to post-orogenic extensional tectonics (e.g., Guerrera et al., 1993; Doglioni et al., 1997; Gueguen et al., 1998; Guerrera et al., 2005 and many others). The Mesozoic and Cenozoic terranes involved in these chains were deposited in the Internal Domain, ‘Flysch’ Domain and External Domain (Guerrera et al., 1993). This paper focuses on the continental redbeds (Pseudoverrucano-type; Perrone et al., 2006) from the Mesozoic covers of the Internal Domains (Fig. 1). These redbeds, which represent the onset of Mesozoic sedimentation during the rift-valley stage of the Pangea breakup, were deposited on Variscan continental crust (Fig. 2) (e.g., Perri et al., 2013 and references therein). 2.1. The Gibraltar Arc (Betic Cordillera and Rifian Maghrebids) The Gibraltar Arc has two arms represented by the Betic Cordillera of southern Spain and the Rifian Maghrebids (“Rif” in Fig. 1) of northern Morocco, which land-locked the Alboran Basin situated in the internal part of the Arc (Fig. 1). The inner portion of the Betic Cordillera consists of an imbricate system of thrust slices at its front (Frontal Units) plus an antiformal stack of nappe complexes named, in ascending tectonic order, Nevado– Filabride, Alpujarride and Malaguide complexes. These complexes have been defined on the basis of their lithostratigraphic characteristics and metamorphic signatures. In particular, the Malaguide Complex constitutes the highest tectonic element of the Betic Internal Domain and consists of a Paleozoic basement unconformably covered by a Mesozoic and Cenozoic sedimentary cover that starts with welldeveloped Triassic continental redbeds (Pseudoverrucano-type; Perrone et al., 2006). The Malaguide Triassic continental facies belt changed laterally to marine carbonate sediments with Alpine lithofacies of the Alpujarride Complex and of the Frontal Units. The Malaguide Triassic redbeds have been formally grouped into the Saladilla Formation (Roep, 1972; Martín-Algarra et al., 1995). This formation is generally made of quartzose conglomerates, overlain by sandstones and mudstones (siltstones and claystones) with red colors and sometimes includes conglomerate with carbonate clasts, calcareous sandstone, dolostone, limestone, marl and gypsum (Fig. 3) (Soediono, 1971; Geel, 1973; Martín-Algarra, 1987). The thickness of the whole formation changes notably between different outcrops but, in most areas, it varies from some tens of meters up to a few hundred of meters. The Internal Nappes of the Rifian Maghrebids are characterized, from bottom to top, by structural complexes, named ‘Dorsale Calcaire’, Sebtide and Ghomaride Complexes, which are identical, respectively, to the Betic Frontal Units, to the tectonically highest Alpujarride units and to the Malaguide Complex (Fallot, 1937; Didon et al., 1973; Suter, 1980). The most internal tectonic unit of the ‘Dorsale Calcaire’ Complex are characterized by Meso-Cenozoic successions showing a tectonosedimentary evolution similar to that of the Ghomaride Complex, into which the ‘Dorsale Calcaire’ realm passed laterally (e.g., Maate and Martín-Algarra, 1992; Maate, 1996). The Ghomaride Complex is organized into four nappes, structurally superposed during upper Oligocene to lowermost Miocene times (Martín-Algarra et al., 2000). All these

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Fig. 1. Sketch map of the Alpine Chains in the Central-Western Mediterranean region (after Perrone et al., 2006; Critelli et al., 2008) and location of the studied area.

nappes are made up of an unmetamorphosed or slightly metamorphosed pre-Alpine basement, deformed by the Variscan orogenesis (e.g., Michard et al., 2002 and references therein) and consisting of Paleozoic slates, phyllites, metarenites and metalimestones, ranging in age from Ordovician to Carboniferous. The basement rocks support a thin Alpine Meso-Cenozoic cover, severely reduced by erosion. Here, continental redbeds (Pseudoverrucano-type; Perrone et al., 2006) are followed by Lower Jurassic, shallow-marine white massive limestones (Fig. 3) (El Kadiri, 1991; Maate et al., 1991; Maate, 1996). These continental redbeds also belong to the Saladilla Formation (Martín-Algarra et al., 1995; Maate, 1996). The age of the Pseudoverrucano-type redbeds (Saladilla Formation) both in the Betic Cordillera and in the Rif has been paleontologically dated as Anisian to Rhaetian (although the presence of older Triassic and upper Permian beds cannot completely excluded) (e.g., Milliard, 1959; Simon and Kozur, 1977; Baudelot et al., 1984; Martín-Algarra, 1987; Martín-Algarra et al., 1995; Maate, 1996; Perrone et al., 2006 and references therein). The studied mudstone samples mainly come from Middle Triassic beds; few samples are from Upper Triassic beds (Fig. 2) (e.g., Zaghloul et al., 2010; Perri et al., 2013).

2.2. The Calabria–Peloritani Arc (north Calabria and north-western Sicily, southern Italy) The Calabria–Peloritani Arc represents a fault-bounded exotic terrane connecting the southern Apennines to the north with the Sicilian Maghrebides to the south (Bonardi et al., 2001 and references therein). The Paleozoic metamorphic and plutonic rocks of the Calabria–Peloritani Arc represent the remnants of Caledonian, Hercynian and Alpine orogens accreted over the Adria–Africa lithosphere during the Miocene Alpine continental collision (Bonardi et al., 2001 and references therein). The northern sector of the Calabria–Peloritani Arc is composed of uppermost tectonic units, consisting of thrust sheets formed by Paleozoic igneous and metamorphic rocks (Bagni, Castagna and Sila units) unconformably covered by Mesozoic to Cenozoic sediments. The Sila Unit is the northernmost extended portion of the Calabria– Peloritani Arc, and it consists of a pre-Alpine crystalline basement characterized by low-to-high grade Variscan metamorphic rocks intruded by intermediate to felsic late Variscan plutonic rocks (Sila Batholith). The Sila Unit is overlain by a Mesozoic sedimentary

Fig. 2. Middle Triassic and Upper Triassic paleogeographic sketch maps of the westernmost Tethys area (modified and redrawn after Vera, 2004; Critelli et al., 2008; Perri et al., 2013).

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Fig. 3. Schematic stratigraphic columns of the Gibraltar Arc (Betic Cordillera — Malaguide Unit; Rifian Maghrebids — Ghomaride Unit) and the Calabria–Peloritani Arc (Calabria — Sila Unit; Sicily — Longi-aormina Unit) showing significant Middle Triassic and Lower Jurassic redbed successions, with location of the studied samples (modified and redrawn after Perrone et al., 2006; Zaghloul et al., 2010; Perri et al., 2013).

succession (Longobucco Group), made at the base, of continental redbeds (Pseudoverrucano-type; Perrone et al., 2006), that pass upward into shallow to deep water carbonates and, the, to turbidites (Fig. 3) (e.g., Zuffa et al., 1980; Young et al., 1986). The southern sector of the Calabria–Peloritani Arc is constituted by tectono-stratigraphic units, with Africa ward convergence, involving both Variscan and older crystalline rocks and unconformable Mesozoic– Cenozoic deposits (e.g., Bonardi et al., 2001; Messina et al., 2004). The Peloritani Mountains consists of seven Alpine tectonic units, which are, geometrically, from top to bottom, and geographically outcropping from north to south: the Aspromonte, Mela, Mandanici, AlìMontagnareale, Fondachelli and Longi-Taormina units (e.g., Messina et al., 2004). The three Longi-Taormina subunits show a similar stratigraphic succession, made of a Paleozoic polymetamorphic basement with a Mesozoic–Cenozoic sedimentary cover. The base of these Mesozoic sedimentary successions is composed by continental redbeds (Pseudoverrucano-type; Perrone et al., 2006) particularly thick (over 100 m) and well exposed, that pass upward into a Jurassic carbonate facies (Fig. 3) (e.g., Mongelli et al., 2006; Perri et al., 2008b, 2011a and references therein). The Pseudoverrucano-type redbeds both in Calabria (Sila Unit) and in Sicily (Longi Taormina Unit) have been paleontologically dated as Upper Triassic (Norian and Rhaetian) and lowermost Jurassic (Hettangian) (e.g., Young et al., 1986; Baudelot et al., 1988; de Capoa et al., 1997; Cecca et al., 2002; Perrone et al., 2006 and references therein); the studied mudstone samples come from Upper Triassic to lowermost Jurassic beds (Fig. 2) (e.g., Mongelli et al., 2006; Perri et al., 2008b, 2011a). 3. Sampling and methods A set of 119 mudstone samples was collected for chemical and mineralogical studies from the Mediterranean units above mentioned

(Fig. 3). Samples were cleaned for geochemical analyses and weathered coats and veined surfaces were cut off. The rocks were crushed and milled in an agate mill to a very fine powder for X-ray diffraction (XRD) and other analytical studies. For XRD studies, randomly-oriented whole rock powders were run in the 2–70 °2θ interval, at a scan speed of 1 °2θ/min, with a step size of 0.05 °2θ and a counting time of 3 s per step, using a Scintag X1 apparatus equipped with a solid-state Si (Li) detector. The tube current and the voltage were 30 mA and 40 kV, respectively. The intensities and diffraction angles of the identified minerals were compared to the database of the International Center for Diffraction Data (ICDD). The mineralogical composition of the b 2 μm grain-size was determined by a thin highly oriented aggregate; oriented air-dried samples were scanned from 1 to 48 °2θ at a scan speed of 0.75 °2θ/min with a step size of 0.05 °2θ and a counting time of 4 s per step. The occurrence of expandable clays was determined after treatment with ethylene glycol (EG) at 25 °C for 15 h. Glycolated samples were scanned at the same conditions used for the air-dried aggregates in the 1–30 °2θ interval. Expandability measurements (percent of illite in illite/EG-smectite) were determined according to Moore and Reynolds (1997) using the delta two-theta method after decomposing the composite peak between 9–10 °2θ and 16–17 °2θ using the Scintag X1 software program with a split Pearson VII function and calculating the quantity Δ°2θ (Moore and Reynolds, 1997). The Pearson VII function was used in the quantitative analysis for decomposition of overlapping reflections (e.g., Perri, 2008). Elemental analyses for major and some trace elements (Nb, Zr, Y, Sr, Rb, Ba, Ni, Co, Cr, V, La, Ce) concentrations were obtained by X-ray fluorescence (XRF) spectrometry (Philips PW 1480) at the Università della Calabria (Italy), on pressed powder disks of whole-rock samples and compared to international standard rock analyses of the United States Geological Survey. X-ray counts were converted into concentrations

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by a computer program based on the matrix correction method according to Franzini et al. (1972, 1975) and Leoni and Saitta (1976). Total loss on ignition (L.O.I.) was determined after heating the samples for three hours at 900 °C. The estimated precision and accuracy for trace element determinations are better than 5%, except for those elements having a concentration of 10 ppm or less (10–15%). The elemental concentrations are given in Table 1. To determine absolute mass fluctuation of each element during continental paleoweathering, a mass-balance calculation have been conducted in this work (see Brimhall et al., 1988; Chadwick et al., 1990; Sheldon and Tabor, 2009). The composition of the upper continental crust (UCC; McLennan et al., 2006) has been used as a representative host rock composition before paleoweathering. Mudstone sample compositions were regarded as weathered derivatives of UCC. The mass-balance approach is a powerful calculation that can determine absolute mass gain or loss but, in performing the calculation, a standardization of the data using an element that had actually been unchanged during the paleoweathering processes is required. Normally, it is difficult to evaluate, solely from the compositional data, which element had been unchanged. In order to overcome this problem, Ohta et al. (2011a) proposed statistical tests to determine the unchanging component in the given compositional dataset. According to the tests of Ohta et al. (2011a), Lanthanum (La) has been selected as the most invariant component in the dataset of this work. Therefore, La has been chosen as a reference frame to calculate mass-balance of elements during paleoweathering of the UCC (McLennan et al., 2006). In this study the principal component analysis (PCA) has been used; PCA is a technique to combine numerous variables into several latent variables that underlie the multivariate data. In undertaking the PCA, the compositional data are first transformed into centered log ratios (CLR: Aitchison, 1986). Then the PCA calculation was performed using a singular value decomposition. All statistical calculations were conducted on “R” (http://www.R-project.org), a free environment for statistical computing. 4. Results and discussion 4.1. Paleoclimate variations and paleoweathering indices Chemical data from redbed mudstones provide information about paleoclimate, source area composition, paleoweathering, sorting and recycling. Climate and recycling effects exert the major control on weathering processes affecting the upper continental crust. Paleoweathering processes in source areas have been generally characterized using the Chemical Index of Alteration (CIA; Nesbitt and Young, 1982), the Chemical Index of Weathering (CIW; Harnois, 1988) and the Plagioclase Index of Alteration (PIA; Fedo et al., 1995). The CIA values for all redbed samples are quite similar, with an average values of about 71, suggesting moderate source-area paleoweathering. Furthermore, the studied redbeds have very high and uniform CIW and PIA values, ranging from about 97 (CIW) and 95 (PIA) for the Calabria–Peloritani Arc samples to about 94 (CIW) and 91 (PIA) for the Gibraltar Arc samples, suggesting intense paleoweathering under steady-state conditions typical of tectonically quiescent or cratonic environments (e.g., Nesbitt et al., 1997). The W index is a geochemical weathering index that was developed from a statistical analysis of element behavior during the course of igneous rock weathering (Ohta and Arai, 2007). The W values of recent soils developed in a variety of climatic zones (Ohta et al., 2011b) and those of the Mesozoic Mediterranean mudstones are given in Fig. 4. The W values obtained for the Gibraltar and Calabria–Peloritrani Arcs samples are equivalent to those of recent soils developed in tropical rainforest climate. Since the mudstones of this study are not always paleosols, it is problematic to directly compare the W values of the studied mudstone samples with those of recent soils. However, the W values of the Mesozoic Mediterranean mudstones are distinctly

different from soils developed in arctic, boreal, temperate and arid climates (Fig. 4). The W values of mudstones more likely suggest that Mediterranean region was in a tropical rainforest climate during the Triassic to lowermost Jurassic time. The W values of the Gibraltar Arc samples are about 80 and those of the Calabria–Peloritani Arc samples are about 85 (Fig. 4). The Calabria– Peloritani Arc samples experienced a somewhat higher degree of paleoweathering than Gibraltar Arc samples. The increase in chemical weathering intensity rapidly leaches Sr compared to Rb (Nesbitt and Young, 1982); therefore, the Rb/Sr ratio rises with weathering increase. Rb has been considered to be primarily fixed in weathered residues and is less reactive than Ca, Na, and Sr (e.g., Nesbitt and Young, 1989). The Rb/Sr ratios of sediments and sedimentary rocks can thus be used to monitor the degree of source rock paleoweathering (McLennan et al., 1993). High Rb/Sr ratios suggest a derivation from intensively weathered rocks such as phyllite and argillite (mean Rb/Sr ratios 1.48 and 1.71; Selvaraj and Chen, 2006), which are dominant among the basement rocks of the studied mudstones. The Calabria–Peloritani Arc samples show higher values of Rb/Sr ratio (mean values 2.21) than Gibraltar Arc samples (both in the Betic Cordillera – mean 1.49 – and in the Rif – mean 1.69) suggesting variations in paleoweathering conditions from the Triassic to the Jurassic. This further indicates somewhat higher degree of paleoweathering in the Calabria–Peloritani Arc than in the Gibraltar Arc as also shown by statistical studies. 4.2. Mass-balance calculation Fig. 5 shows the result of mass-balance calculation showing mass gain or loss of mudstone samples relative to the UCC. For example, a value of − 0.5 indicates a half of the molecular element within the eroded UCC in western-central Mediterranean Alpine chains during the Late Mesozoic was lost due to paleoweathering and formation of mudstones, whereas the value of −1 indicates that a relevant element has been completely lost. Similarly, if the value in Fig. 5 is positive, it indicates addition of absolute abundance of the element compared to the UCC. For instance, a value of 1 indicates that the absolute abundance of an element is doubled when compared to its original abundance in the UCC. In Fig. 5, most elements show negative values both in the Gibraltar and the Calabria–Peloritani Arcs, implying that mudstone formation in the Early Mesozoic involved a moderate to intense continental crust paleoweathering. In particular, CaO, Na2O, Sr and Ba are highly depleted. This indicates intense dissolution of plagioclase as these elements mainly reside in plagioclase. Mudstones of the Calabria–Peloritani Arc tend to be more depleted in these elements than the Gibraltar Arc. Similarly, compared to Gibraltar samples, the Calabria–Peloritani samples have smaller amounts of MgO, Fe2O3 and MnO as well as of transition metal elements, such as V, Cr, Co and Ni (Fig. 5). This relationship suggests that continental paleoweathering condition in the Mediterranean region intensified from Triassic to Jurassic time. The Calabria–Peloritani Arc mudstones are in contrast enriched in SiO2, TiO2, Al2O3, K2O, Y, Zr, Nb and U (Fig. 5) when compared to Gibraltar Arc mudstones. These are typical incompatible elements consisting of chemically stable minerals such as quartz, K-feldspar and zircon, which are commonly concentrated in geochemically mature sediments (e.g., Talyor and McLennan, 1985; Bauluz et al., 2000; Khudoley et al., 2001; Ohta, 2004). This result indicates that the Calabria–Peloritani Arc area probably experienced more intensified sediment recycling than the Gibraltar Arc area. As suggested by previous studies (Garcia et al., 1991; Mongelli et al., 2006; Perri, 2008; and Perri et al., 2008a, 2008b, 2011a, 2011b, 2013), mass-balance calculations also support a gradual advancement in sediment recycling effect from the Triassic to the Jurassic time. Therefore, both hinterland paleoweathering and sediment recycling have been important factors controlling the sediment geochemistry of

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Table 1 Major and trace element distribution in the studied samples. Samples Calabria–Peloritani arc

SiO2

TiO2

Al2O3

Southern sector (Sicily — Longi-Taormina unit) VL1 650.86 0.62 16.30 VL2 72.05 0.66 14.23 VL3 61.19 0.59 18.05 VL4 70.15 0.74 15.38 VL5 64.79 0.71 16.48 VL6 61.48 0.66 17.24 VL7 63.40 0.78 16.98 VL8 63.55 0.79 17.43 VL9 70.43 0.74 14.53 VL10 60.21 0.83 19.36 VL11 66.83 0.70 16.69 VL12 61.26 0.81 18.88 VL13 59.70 0.82 19.46 VL14 59.80 0.84 19.58 VL15 62.73 0.82 18.41 VL16 66.81 0.79 16.50 VL17 67.97 0.68 14.77 VL18 65.09 0.78 17.71 VL19 66.23 0.78 17.85 FP148 50.99 0.94 24.12 FP149 70.74 0.49 16.16 FP150 67.09 0.63 17.20 FP151 64.71 0.78 18.04 FP152 61.10 0.77 19.17 FP153 62.85 0.80 17.81 FP154 60.51 0.77 19.74 FP155 68.22 0.83 15.98 FP156 66.29 0.74 17.40 FP157 65.90 0.74 17.61 FP158 63.68 0.81 18.18 FP159 63.81 0.80 18.55 FP160 56.85 0.74 21.78 FP161 61.88 0.85 19.48 FP162 62.97 0.79 19.46 FP163 61.59 0.77 20.15 FP164 60.96 0.82 20.29 FP165 64.17 0.85 18.52 FP166 60.45 0.98 20.92 FP167 54.65 1.08 23.90 FP168 69.15 0.63 16.46 FP169 60.28 0.80 19.56 FP170 63.83 0.75 18.07 FP171 60.12 0.76 19.32 FP172 72.34 0.78 14.09 FP173 61.67 0.78 19.50 FP174 57.35 0.87 21.52 FP175 58.03 0.89 20.56 FP176 58.43 1.03 21.99 FP177 59.37 0.90 20.91 FP178 64.39 0.81 18.77 FP179 60.17 0.87 21.40 FP180 67.90 0.87 17.99 FP181 62.30 0.86 18.86 Northern sector (Calabria — Sila unit) FP88 60.68 0.94 19.84 FP89 62.69 0.88 19.31 FP90 65.87 0.86 17.24 FP91 61.79 1.02 21.57 FP92 61.72 1.10 20.60 FP93 66.46 0.87 16.65 FP94 66.13 1.05 16.62 FP95 60.94 0.98 19.26 FP96 58.60 0.99 19.95 FP97 58.89 0.95 19.76 FP98 58.96 0.97 19.75 FP99 61.94 0.95 18.49 FP100 67.05 1.02 17.52 FP101 62.93 1.01 18.25 FP102 60.28 1.05 20.56 FP103 71.62 0.89 15.84 FP104 69.32 0.83 13.43 FP105 54.30 0.88 19.53 FP106 67.33 1.00 18.54 FP107 67.91 0.94 17.43

Fe2O3

MnO

MgO

CaO

Na2O

K2O

P2O5

L.O.I.

Total

6.01 3.76 7.47 4.26 6.86 7.28 6.91 7.47 5.80 8.11 7.06 8.13 8.12 7.91 6.60 6.48 5.58 3.66 2.93 10.35 3.74 5.35 5.99 6.91 6.57 6.88 4.51 5.29 5.30 6.21 5.79 8.17 5.95 5.51 6.34 6.41 6.46 7.04 7.96 4.50 7.38 6.22 7.19 4.37 6.09 8.00 8.96 7.09 6.75 6.42 6.78 5.88 8.17

0.20 0.11 0.03 0.01 0.14 0.19 0.06 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.06 0.01 0.04 0.02 0.05 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.08 0.01 0.01 0.04 0.00 0.01 0.01 0.01 0.01 0.03 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.17

1.68 1.55 1.83 1.23 1.65 1.84 1.64 1.60 1.10 1.68 1.21 1.38 1.47 1.45 1.43 1.20 1.89 1.53 1.70 1.28 0.92 1.16 1.13 1.83 1.77 1.63 1.35 1.29 1.21 1.75 1.18 1.25 1.31 1.29 1.31 1.46 1.46 1.46 1.31 1.30 1.72 1.50 1.66 1.16 1.54 1.35 1.30 1.79 2.56 1.62 1.77 0.87 1.57

0.20 0.13 0.22 0.13 0.15 0.37 0.18 0.22 0.15 0.21 0.12 0.08 0.17 0.11 0.26 0.21 0.89 0.22 0.38 0.05 0.04 0.04 0.04 0.10 0.04 0.20 0.18 0.04 0.10 0.05 0.02 0.02 0.02 0.15 0.05 0.13 0.02 0.02 0.02 0.02 0.02 0.01 0.01 0.02 0.03 0.04 0.03 0.03 0.02 0.02 0.03 0.03 0.17

0.18 0.15 0.14 0.19 0.21 0.16 0.19 0.18 0.22 0.21 0.15 0.15 0.17 0.16 0.20 0.15 0.15 0.17 0.20 0.26 0.17 0.18 0.20 0.26 0.14 0.23 0.21 0.30 0.30 0.23 0.25 0.27 0.20 0.26 0.29 0.42 0.37 0.40 0.45 0.14 0.19 0.18 0.18 0.14 0.19 0.21 0.21 0.58 0.38 0.37 0.43 0.38 0.36

4.37 4.04 4.48 3.95 4.53 4.49 4.62 4.54 3.32 4.90 3.84 4.49 4.76 5.00 4.16 3.68 3.92 4.80 4.73 6.99 4.56 4.86 5.27 5.90 5.62 5.88 4.48 4.37 4.58 5.08 4.90 6.04 5.00 5.32 4.99 5.09 4.21 4.87 5.76 4.76 5.74 5.32 5.76 3.98 5.62 6.39 5.92 4.53 4.10 4.03 4.59 2.74 3.48

0.06 0.03 0.03 0.05 0.05 0.04 0.07 0.07 0.07 0.09 0.07 0.05 0.07 0.05 0.04 0.04 0.02 0.02 0.03 0.09 0.05 0.05 0.05 0.08 0.04 0.07 0.06 0.06 0.05 0.05 0.03 0.06 0.05 0.06 0.06 0.06 0.02 0.02 0.03 0.02 0.02 0.02 0.03 0.02 0.03 0.06 0.07 0.02 0.03 0.02 0.02 0.04 0.05

4.41 3.15 5.74 3.89 4.44 6.27 5.05 4.02 3.54 4.12 3.15 4.61 5.12 5.01 5.05 4.08 4.01 5.01 5.13 4.89 3.02 3.21 3.54 3.59 4.12 4.01 4.04 4.10 4.15 3.74 4.41 4.74 5.15 4.11 4.12 4.22 3.75 3.74 4.65 3.00 4.25 4.01 4.21 3.01 4.24 4.09 4.01 4.25 4.65 3.23 3.54 3.15 3.95

99.89 99.86 99.77 99.98 100.01 100.02 99.88 99.89 99.92 99.74 99.84 99.86 99.88 99.93 99.76 99.95 99.92 99.01 100.01 99.97 99.90 99.77 99.76 99.72 99.77 99.93 99.94 99.89 99.95 99.82 99.74 99.93 99.90 99.93 99.68 99.89 99.84 99.91 99.82 99.99 99.98 99.92 99.26 99.92 99.70 99.89 99.99 99.75 99.68 99.69 99.61 99.86 99.94

7.00 5.51 6.09 3.00 4.04 6.32 6.18 6.17 7.45 7.24 6.65 7.27 2.25 6.14 4.45 2.39 5.25 6.83 2.10 2.21

0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.03 0.01 0.02 0.01 0.01 0.18 0.04 0.01 0.01 0.17 0.01 0.01

1.30 1.39 1.31 1.25 1.32 1.04 1.06 1.49 1.56 1.67 1.83 1.26 1.32 1.46 1.75 1.20 1.38 1.97 1.37 1.40

0.21 0.23 0.19 0.25 0.24 0.41 0.21 0.55 0.35 0.31 0.26 0.25 1.42 0.31 0.44 0.37 1.48 2.77 0.43 0.52

0.13 0.20 0.22 0.17 0.26 0.21 0.26 0.32 0.31 0.30 0.28 0.15 0.21 0.26 0.37 0.47 0.34 0.18 0.36 0.35

4.34 4.47 4.00 4.71 4.59 3.34 3.32 4.02 4.25 4.43 4.60 3.87 3.74 4.10 4.84 2.79 3.40 4.73 3.45 3.22

0.02 0.02 0.02 0.01 0.02 0.01 0.01 0.02 0.02 0.02 0.02 0.02 0.03 0.02 0.02 0.03 0.02 0.03 0.02 0.02

5.23 5.12 4.11 6.12 6.01 4.15 5.02 6.04 6.12 6.14 6.24 5.42 5.13 5.18 6.07 4.19 4.36 9.25 5.23 6.00

99.70 99.83 99.92 99.90 99.91 99.47 99.87 99.81 99.63 99.72 99.58 99.63 99.70 99.84 99.87 99.80 99.82 100.64 99.84 100.01

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Table 1 (continued) Samples Calabria–Peloritani arc

Sc

Th

V

Cr

Southern sector (Sicily — Longi-Taormina unit) VL1 16 11 100 60 VL2 10 10 81 75 VL3 19 13 127 75 VL4 13 12 110 73 VL5 14 11 106 68 VL6 17 12 112 73 VL7 14 12 111 79 VL8 14 11 113 73 VL9 12 12 98 62 VL10 16 13 126 84 VL11 12 10 104 60 VL12 15 12 128 81 VL13 16 12 136 83 VL14 18 13 132 85 VL15 15 11 130 78 VL16 13 13 125 70 VL17 10 10 99 57 VL18 14 12 112 75 VL19 14 11 110 83 FP148 22 17 183 137 FP149 11 12 66 48 FP150 13 14 93 72 FP151 12 13 103 107 FP152 17 15 102 85 FP153 16 16 85 82 FP154 19 16 135 97 FP155 13 15 72 66 FP156 12 14 88 61 FP157 13 14 91 62 FP158 18 16 104 74 FP159 11 13 96 85 FP160 23 13 152 101 FP161 16 12 111 90 FP162 14 12 122 77 FP163 13 12 104 78 FP164 14 12 112 87 FP165 15 12 129 80 FP166 16 12 136 96 FP167 22 12 157 119 FP168 11 10 60 49 FP169 16 12 110 85 FP170 14 11 106 73 FP171 17 12 124 83 FP172 8 10 57 46 FP173 16 12 114 78 FP174 19 13 125 104 FP175 19 13 122 98 FP176 18 14 141 100 FP177 18 10 132 92 FP178 14 11 113 77 FP179 17 11 129 93 FP180 14 12 95 84 FP181 16 12 133 90 Northern sector (Calabria — Sila unit) FP88 23 10 138 101 FP89 19 10 127 89 FP90 20 8 108 76 FP91 20 10 115 103 FP92 24 13 138 108 FP93 22 11 124 78 FP94 21 8 115 80 FP95 19 9 127 91 FP96 21 8 133 99 FP97 15 9 133 97 FP98 16 10 135 99 FP99 20 12 119 82 FP100 29 13 102 72 FP101 19 15 111 76 FP102 23 16 129 95 FP103 19 15 96 60 FP104 21 12 82 53 FP105 16 15 133 95 FP106 15 13 111 73 FP107 18 12 102 65

Co

Ni

Zn

Rb

Sr

Y

Zr

Nb

Ba

La

Ce

22 12 27 10 18 23 19 20 15 19 16 20 20 24 20 17 14 15 12 23 10 14 14 20 19 20 13 17 14 19 12 18 15 13 16 17 17 18 19 11 18 17 18 11 15 19 20 21 22 19 21 17 29

37 25 42 25 36 55 34 38 26 39 25 32 39 43 41 32 29 30 31 22 13 21 16 33 31 33 29 24 23 39 23 31 34 26 26 32 44 49 48 21 27 23 23 15 23 25 24 55 42 38 51 33 59

97 59 98 62 76 110 80 100 80 90 77 74 75 99 64 80 51 96 66 72 40 59 58 65 86 86 65 51 57 84 42 38 39 43 50 59 58 58 52 50 68 75 53 39 37 52 52 75 86 51 56 40 78

146 131 181 142 166 188 178 187 142 216 147 190 206 228 185 153 158 225 232 307 171 187 227 265 260 259 194 180 184 199 227 258 245 222 196 213 170 193 246 180 268 224 262 157 238 277 253 191 191 172 215 138 162

91 79 94 157 105 113 150 125 108 157 110 138 157 163 111 111 100 99 93 158 85 160 148 65 55 77 83 104 106 97 97 171 145 81 101 97 158 103 126 73 82 87 117 75 111 137 118 178 119 158 148 140 113

40 34 37 37 38 74 40 36 41 41 31 39 40 43 41 41 31 38 38 55 30 41 52 84 26 30 60 37 33 41 30 56 38 35 41 34 35 41 42 34 15 37 27 33 37 46 51 33 39 39 36 47 62

236 284 174 342 270 205 269 235 339 215 226 250 228 218 242 339 285 260 223 211 185 228 187 202 203 153 312 281 257 263 257 164 237 207 253 226 283 308 212 312 160 242 166 734 205 195 221 335 237 243 231 346 278

16 12 18 16 19 19 21 20 16 22 17 21 22 23 22 18 16 19 19 28 11 14 19 20 19 23 22 18 18 20 23 22 27 24 23 26 19 22 29 14 23 23 22 20 24 27 26 22 20 18 20 20 20

367 400 483 466 517 602 586 564 439 1395 541 671 729 634 655 500 471 893 579 572 233 325 368 358 291 419 321 330 339 282 295 423 309 430 385 401 387 524 548 228 383 309 396 194 371 428 436 438 374 385 403 246 432

42 38 37 48 43 50 45 41 48 44 38 46 47 48 47 49 40 43 43 85 44 60 62 46 45 39 52 44 45 49 39 47 48 45 51 53 55 54 55 46 43 43 48 43 56 60 62 59 48 48 53 55 61

79 79 82 86 82 85 89 82 89 86 68 84 89 92 90 93 72 80 82 105 59 78 75 72 69 57 75 69 73 71 74 87 94 80 99 109 109 104 104 95 89 83 105 85 97 106 113 117 91 99 105 138 120

31 18 16 9 11 14 13 20 23 19 20 16 11 18 23 15 10 16 10 10

41 24 21 21 26 28 28 41 43 39 41 26 21 28 37 23 17 34 17 23

60 45 36 40 39 35 33 45 69 40 50 31 45 60 50 52 75 66 51 56

240 225 207 293 265 174 186 207 233 223 236 188 158 176 215 113 155 231 156 148

62 64 58 54 75 39 43 58 67 72 72 74 83 75 75 72 64 104 86 79

36 30 26 36 47 30 40 40 41 40 40 40 38 44 43 23 32 35 30 34

264 267 282 244 276 262 289 253 232 229 227 281 440 400 321 327 326 240 305 304

20 20 20 24 26 19 23 23 22 23 23 22 23 23 24 21 19 20 24 24

645 554 454 611 617 473 439 535 568 597 579 427 381 488 620 397 269 965 651 418

59 50 49 42 69 45 49 45 77 50 55 63 47 59 51 49 51 53 50 45

121 91 75 77 114 74 89 91 128 83 99 112 100 98 100 88 99 97 83 75

(continued on next page)

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151

Table 1 (continued) Samples Gibraltar arc

Samples Gibraltar arc

SiO2

TiO2

Al2O3

Fe2O3

MnO

MgO

CaO

Na2O

K2O

P2O5

L.O.I.

Total

20.86 15.72 21.95 21.60 21.09 19.23 19.55 19.40 17.67 17.94 19.09 17.35 18.31 19.37 17.70 18.68 20.84 19.03 13.49 17.56 16.38 9.98 17.16

8.35 5.32 9.68 9.35 8.55 8.58 8.12 6.97 6.13 6.55 7.97 6.99 6.64 6.38 7.37 7.62 7.07 7.96 5.57 6.87 6.63 3.39 6.90

0.07 0.08 0.03 0.02 0.03 0.03 0.03 0.07 0.10 0.13 0.10 0.01 0.10 0.02 0.02 0.06 0.02 0.06 0.06 0.04 0.07 0.10 0.05

2.42 4.69 2.73 2.44 2.69 3.51 4.41 3.33 3.72 4.79 3.93 2.14 3.28 2.45 2.25 2.71 3.06 2.77 4.22 4.38 5.01 8.66 4.00

0.92 4.50 0.32 0.29 0.33 0.93 0.71 2.31 3.05 4.00 2.84 0.36 2.91 0.25 0.24 3.27 2.14 3.92 16.19 3.05 8.62 11.15 4.63

0.25 0.26 0.23 0.22 0.22 0.58 0.48 0.58 0.57 0.45 0.41 0.18 0.66 0.33 0.28 0.17 0.19 0.16 0.15 0.16 0.16 0.10 0.16

4.51 3.91 6.49 6.56 6.29 4.23 3.88 3.97 3.53 3.92 4.38 4.95 3.89 5.83 5.41 5.17 6.26 5.30 4.06 4.93 5.28 2.39 4.53

0.07 0.07 0.13 0.18 0.16 0.14 0.14 0.11 0.11 0.10 0.09 0.10 0.11 0.16 0.16 0.05 0.12 0.05 0.06 0.16 0.06 0.06 0.10

5.86 8.25 6.12 5.24 5.23 6.14 7.46 6.22 7.14 9.15 8.63 3.25 7.01 5.03 4.02 8.12 7.15 8.25 19.02 8.36 12.05 17.39 10.05

99.85 99.30 99.75 99.57 99.51 99.66 99.60 99.75 99.37 99.40 99.90 99.59 99.92 99.89 99.51 99.53 99.33 99.44 99.31 99.78 99.86 99.58 99.80

20.97 20.18 17.15 20.13 19.87 17.50 20.30 19.78 19.09 20.38 19.40 19.78 20.85 21.77 22.21 22.06 20.89 18.81 19.29 18.22 18.68 19.43 20.17

4.45 7.87 7.04 7.78 7.10 5.77 8.58 8.07 7.07 8.64 6.21 6.68 7.05 7.19 7.39 7.26 7.54 5.73 6.83 6.60 6.09 6.53 6.66

0.02 0.02 0.02 0.02 0.02 0.08 0.12 0.02 0.09 0.04 0.08 0.06 0.04 0.02 0.02 0.02 0.04 0.04 0.11 0.04 0.04 0.04 0.06

2.38 2.26 2.11 2.34 2.32 2.33 2.63 2.58 3.41 4.11 2.28 2.40 3.11 1.56 2.14 2.14 2.58 2.20 2.39 2.32 3.24 2.71 2.43

0.15 0.11 0.13 0.08 0.10 0.17 0.18 0.09 1.26 1.33 0.30 0.90 0.48 0.31 0.42 0.21 0.25 0.41 0.26 0.25 0.37 0.40 0.84

0.21 0.23 0.18 0.22 0.24 0.36 0.28 0.24 0.64 0.38 0.72 0.69 0.58 0.30 0.42 0.42 0.70 0.84 0.68 0.86 0.76 0.62 0.66

6.01 5.84 5.52 5.79 5.86 4.43 5.23 4.95 3.98 4.62 2.93 3.33 3.54 2.98 3.62 3.56 3.61 2.68 2.98 2.94 3.48 3.05 3.41

0.27 0.19 0.09 0.11 0.09 0.08 0.10 0.07 0.12 0.20 0.05 0.06 0.10 0.03 0.14 0.02 0.06 0.05 0.08 0.06 0.10 0.06 0.07

5.12 5.36 4.25 4.28 5.34 4.02 5.46 5.62 6.24 8.05 4.62 5.37 6.12 6.52 6.34 6.12 5.16 4.29 5.27 4.51 5.43 5.72 5.71

99.82 99.69 99.73 98.52 99.91 99.80 99.60 99.67 99.43 99.77 99.78 99.52 99.53 99.66 99.63 99.78 99.85 99.96 99.97 99.77 99.71 99.83 99.75

V

Cr

Co

Ni

Zn

Rb

Sr

Y

Zr

Nb

Ba

La

Ce

163 102 171 169 159 133 132 125 126 135 144 104 124 125 124 132 146 130 95 112 110 62 122

109 77 134 149 121 107 102 92 94 105 113 83 92 103 96 103 113 102 78 87 91 45 91

25 18 29 21 26 27 30 21 21 24 24 17 20 13 13 21 18 22 16 20 18 12 18

57 39 50 40 49 47 47 41 44 51 61 39 44 40 38 38 41 42 42 40 38 30 42

40 32 50 70 31 45 60 50 52 75 66 51 56 55 58 60 69 62 64 67 45 25 38

208 132 206 213 203 229 238 178 147 176 190 157 171 180 157 196 238 199 165 186 201 102 186

107 123 422 429 419 95 83 79 127 141 170 103 108 418 384 85 111 100 97 135 89 81 108

39 31 39 56 42 31 32 38 31 36 32 39 35 45 43 27 30 29 18 39 27 31 31

189 247 214 332 231 174 187 218 193 231 186 315 215 337 368 154 138 146 115 223 170 220 182

21 16 18 23 21 23 21 20 18 20 21 18 20 22 22 16 19 17 13 19 17 13 20

758 394 601 803 623 442 394 509 487 450 529 300 599 541 497 884 894 2318 6087 437 403 705 448

68 45 70 88 69 54 45 61 57 44 57 36 48 65 55 54 45 55 40 49 43 30 47

112 89 138 183 145 82 89 92 86 88 102 74 93 106 104 86 92 88 54 79 83 63 82

Betic Cordillera (Malaguide unit) FP46 55.56 0.98 FP47 55.74 0.76 FP48 51.11 0.96 FP49 52.60 1.07 FP50 53.96 0.96 FP51 55.45 0.84 FP52 54.06 0.76 FP53 56.01 0.78 FP54 56.59 0.76 FP55 51.57 0.80 FP56 51.64 0.82 FP57 63.43 0.83 FP58 56.22 0.79 FP59 59.10 0.97 FP60 61.13 0.93 FP68 52.90 0.78 FP69 51.68 0.80 FP70 51.14 0.80 FP71 35.92 0.57 FP73 53.54 0.73 FP74 44.89 0.71 FP75 45.85 0.51 FP76 51.47 0.75 Rifian Maghrebids (Ghomaride unit) FP38a 59.16 1.08 FP38b 56.66 0.97 FP37 62.38 0.86 FP36 56.89 0.88 FP35a 58.07 0.90 FP35b 64.27 0.79 FP35c 55.80 0.92 FP34a 57.33 0.92 FP34b 56.73 0.80 FP34c 51.26 0.76 FP34d 62.31 0.88 FP33 59.35 0.90 FP32 56.81 0.85 FP30 58.11 0.87 FP29a 56.05 0.88 FP29b 57.05 0.92 FP28 58.01 1.01 FP27 64.07 0.84 FP26 61.17 0.91 FP25 63.05 0.92 FP24 60.72 0.80 FP23 60.40 0.87 FP22 58.84 0.90

Sc

Th

Betic Cordillera (Malaguide unit) FP46 16 14 FP47 13 14 FP48 18 12 FP49 25 6 FP50 22 10 FP51 19 9 FP52 18 8 FP53 18 8 FP54 14 9 FP55 17 8 FP56 14 7 FP57 16 8 FP58 12 7 FP59 16 6 FP60 18 6 FP68 15 6 FP69 20 8 FP70 17 8 FP71 10 5 FP73 15 5 FP74 14 7 FP75 10 6 FP76 15 7

(continued on next page)

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Table 1 (continued) Samples Gibraltar arc

Sc

Th

V

Rifian Maghrebids (Ghomaride unit) FP38a 23 5 117 FP38b 23 5 130 FP37 22 6 107 FP36 24 5 138 FP35a 23 7 131 FP35b 22 8 107 FP35c 21 9 146 FP34a 22 9 136 FP34b 21 10 132 FP34c 23 9 139 FP34d 22 10 110 FP33 21 8 127 FP32 23 7 136 FP30 22 6 144 FP29a 23 5 174 FP29b 23 6 157 FP28 22 8 143 FP27 21 11 104 FP26 19 13 120 FP25 21 15 120 FP24 16 14 137 FP23 15 14 117 FP22 18 11 127

Cr

Co

Ni

Zn

Rb

Sr

Y

Zr

Nb

Ba

La

Ce

101 119 79 114 103 76 102 111 98 110 79 97 102 111 122 110 109 75 94 83 78 85 96

13 18 18 20 20 17 37 27 23 27 20 23 24 22 26 26 29 20 25 24 20 23 23

30 31 37 46 44 75 67 52 45 47 36 45 46 44 54 56 52 35 56 41 37 42 44

64 64 75 96 90 80 65 77 77 77 77 74 81 78 82 82 75 64 70 84 65 62 59

192 190 160 187 183 132 176 177 173 255 140 166 207 174 221 217 184 123 146 150 170 163 168

444 552 308 370 269 111 157 113 112 89 73 97 85 72 76 70 91 73 87 88 65 78 97

58 54 38 38 37 40 51 56 39 34 37 37 36 29 46 34 42 36 42 40 40 41 38

454 262 252 221 212 246 242 215 227 162 254 215 197 176 187 209 207 280 247 268 286 235 220

26 22 19 20 20 19 23 22 20 21 20 20 20 22 23 22 24 18 22 20 20 20 20

929 1448 511 602 566 525 684 506 659 470 463 579 404 464 488 430 535 419 479 452 386 455 574

66 66 40 62 55 45 61 68 53 46 46 50 50 56 63 60 67 52 59 59 50 56 50

137 143 99 112 100 73 129 110 92 88 95 103 97 102 115 114 120 101 113 112 84 96 103

western-central Mediterranean Alpine chains during the Early Mesozoic. It is necessary to mathematically distinguish these two effects by PCA to determine the true degree of hinterland paleoweathering and of the sediment recycling effects.

4.3. Principal component analysis and chemical–mineralogical considerations The result of PCA is summarized in Table 2 and the biplot is illustrated in Fig. 6. The variance explained by the latent variables PC1 is 35.53% and that of PC2 is 11.88% (Table 2). Therefore, PC1 is the prominent variable controlling the geochemical differences among the studied mudstone samples. The cumulative proportion of PC1 and PC2 is in total 47.42%, indicating that these two latent variables can explain a half of the information inherited in the present dataset. Plots in the biplot show large scatter in PC1–PC2 space (Fig. 6). However, samples collected from Morocco, Spain and Italy generally have individual clusters.

Fig. 7 displays the loading of each element on PC1 and PC2. Elements that have strong negative loadings with PC1 are CaO, MgO and MnO. This element association indicates a contribution of carbonates such as calcite and dolomite, which are known to accumulate in arid environments (e.g., Schaetzl and Anderson, 2005). In contrast, elements that have positive loadings with PC1 include felsic major elements (SiO2, Al2O3, K2O) and incompatible trace elements (e.g., Sr, Y, Zr, La and others), as well as, mafic major elements (TiO2 and Fe2O3) and compatible trace elements (V, Cr and Co). Therefore, a positive value of PC1 indicates a contribution from siliciclastic rocks, regardless of mafic or felsic sources. As a total, PC1 can be interpreted as a latent variable that measures the influence of carbonates against silicates. Accordingly, mudstones deposited in an arid climate will have negative PC1 values and those deposited in a humid climate will tend to have positive PC1 values. Thompson et al. (1982) traced four major changes in precipitation in the northern Rocky Mountains during the Cenozoic era. They found that warm–humid climates are characterized by red, kaolinite-rich

Fig. 4. Comparison of the W values of recent soils developed under various climate regimes (Ohta et al., 2011b) and those of the Mesozoic Mediterranean mudstones. The degree of hinterland paleoweathering in the Gibraltar and Calabria–Peloritani Arcs are comparable to soils developed in tropical rainforest climate. The lower and upper limits of the box represent the first and third quartiles, respectively, and line within the box represents the second quartile. Whiskers represent the allowable range of the data and circles represent outliers. Notches on the side of boxes of recent soil indicate 95% confidence intervals of the median.

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Fig. 5. Results of mass-balance calculation for major (A) and minor elements (B). Negative values suggest net mass loss during continental crust weathering and positive values indicate net mass gain. Composition of La has been used as a reference frame to calculate mass-balance. Note that both Gibraltar and Calabria–Peloritani Arc sediments have lost significant amount of element masses during continental paleoweathering and mudstone formation.

Table 2 PCA loadings for PC1 and PC2.

SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 Sc V Cr Co Ni Zn Rb Sr Y Zr Nb Ba La Ce Nd Th U Eigen. values Proportion Cumulative proportion

PC1

PC2

PC3

0.74 0.86 0.92 0.26 −0.75 −0.77 −0.82 0.06 0.63 −0.47 0.55 0.58 0.52 0.04 −0.28 0.20 0.75 0.13 0.59 0.59 0.85 −0.23 0.76 0.70 0.61 0.65 0.13 90.59 350.53 350.53

−0.48 −0.19 0.16 0.70 −0.13 0.08 −0.23 −0.08 0.18 0.21 0.16 0.58 0.62 0.68 0.57 0.07 0.21 0.20 −0.17 −0.65 −0.07 0.14 −0.01 0.03 −0.09 −0.36 −00.22 30.21 110.88 470.42

0.23 −0.33 −0.05 0.32 0.23 −0.12 −0.33 −0.26 0.28 0.23 −0.50 −0.26 −0.39 0.20 0.07 0.51 0.03 0.25 0.30 0.06 −0.15 −0.15 −0.18 −0.19 0.57 0.36 −00.76 20.72 100.06 57.48

Fig. 6. Results of principal component analysis described as a compositional biplot. Arrows indicate loadings of elements.

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Fig. 7. Bar plot of element loadings of PC1 and PC2. The element loadings indicate that PC1 measures the contribution of carbonates against silicates and PC2 measures the amount of recycled sediments. Therefore, PC1 can be interpreted as a latent variable of aridity against humidity and PC2 is a latent variable that measures the degree of sediment recycling.

paleosols. These saprolitic rocks are similar to many modern soils formed in the warm–humid tropics. Dry periods, which corresponded to times of sediment accumulation in the basins, are characterized by sediment types (i.e., evaporites) formed in arid to semiarid climates, and by a clay mineralogy that is enriched in smectite and illite–smectite mixed layers. The Calabria–Peloritani Arc samples show higher values of kaolinite than Gibraltar Arc samples, which are alternatively characterized by higher values of illite–smectite mixed layers than the Calabria– Peloritani Arc samples (e.g., Perri, 2008). Thus, the mineralogical composition of the studied samples (Perri, 2008) confirm the statistical consideration observed from the PC1 values testifying an alternation in climatic conditions with a more humid paleoenvironment for the Calabria–Peloritani Arc samples. As for PC2, elements that have negative loading are SiO2, TiO2, Zr, Th and U. These are representative felsic elements inherited in quartz, titanite and zircon. However, a negative PC2 value does not simply indicate a felsic source because elements that commonly reside in felsic plagioclase such as Na2O, Al2O3 and Ba do not have strong negative values; some of them even display positive values. Other elements that have positive PC2 values are elements such as Fe2O3, MgO, V, Cr and others, which mainly come from mafic minerals. Consequently, elements that have positive PC2 values are derived from more easily weathered minerals such as plagioclase, biotite, hornblende and pyroxene, while those with positive PC2 values are derived from chemically stable minerals like quartz, titanite and zircon. As a result, PC2 can be interpreted as a latent variable measuring the degree of sediment recycling. Consequently, PCA succeeded to extract independent indices that correspond to the degree of paleoweathering due to changes in humidity (PC1) and to the extent of sediment recycling (PC2). The geochemistry of the Pseudoverrucano-type redbed mudstones is governed principally by these two effects, verifying the previous interpretations made by Garcia et al. (1991), Mongelli et al. (2006), Perri (2008) and Perri et al. (2008a, 2008b, 2011a, 2011b, 2013). Furthermore, PC1 and PC2 are orthogonal coordinates and mathematically independent; this means that, in the present study, the degree of paleoweathering and sediment recycling can be evaluated independently, which had been a difficult task in previous studies. Histograms of PC1 scores and PC2 scores are plotted in Fig. 8. As mentioned above, PC1 can be interpreted as a paleoclimatic measure mainly due to humidity (positive values) against aridity (negative

values). PC1 scores have clear spatial and temporal differences (Fig. 8A). Gibraltar Arc sediments of Middle to Upper Triassic age have negative PC1 values, whereas, Calabria–Peloritani Arc sediments of Upper Triassic to lowermost Jurassic age have positive PC1 values. This result strongly indicates that humidity had increased from the Middle Triassic to the lowermost Jurassic in the Mediterranean. This explains why Calabria– Peloritani Arc sediments show slightly higher degree of hinterland paleoweathering compared to Gibraltar Arc sediments (Fig. 4). PC2 scores show no obvious differences between the studied areas (Fig. 8B). However, several samples of the Betic Cordillera, the LongiTaormina and Sila Units retain strong negative PC2 scores. This result indicates that the depositional environment in the Calabria–Peloritani Arc and in the Betic Cordillera was more suitable for sediment recycling than in the Rif. Cox et al. (1995) define the Index of Compositional Variability (ICV), which measures the abundance of alumina relative to the other major cations in a rock or mineral and may be applied to mudstones as a measure of compositional maturity. Compositionally immature mudstones have high values of the ICV index (ICV N 1), whereas compositionally mature mudstones have low values (ICV b 1). Furthermore, compositionally immature mudstones tend to be found in tectonically active settings and are first-cycle deposits, and compositionally mature mudstones are typical of tectonically quiescent or cratonic environments (Weaver, 1989) where sediment recycling is active, but may also be produced by intense chemical weathering of first-cycle material (Barshad, 1966). The studied samples show generally ICV values b 1 suggesting that these mudstones are compositionally mature and are related to environments where sediment recycling is active. In particular, Calabria–Peloritani Arc samples show lower ICV values rather than Gibraltar (both Betic Cordillera and Rifian Maghrebids) Arc samples testifying that the depositional environment for those mudstones was more suitable for sediment recycling, as also shown by the statistical (PC2 values) analysis. These sediment recycling processes have been also demonstrated before for both the Calabria–Peloritani Arc and the Gibraltar Arc samples using the Al2O3–TiO2–Zr plot and the Zr/Sc vs Th/Sc diagram where the redbeds fall along a trend involving zircon addition and thus support sediment recycling (e.g., Mongelli et al., 2006; Critelli et al., 2008; Perri et al., 2008b; Zaghloul et al., 2010; Perri et al., 2011a, 2013). These compositionally mature mudstones possibly support deposition in a tectonically quiescent or cratonic setting where recycling and associated weathering were active during

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Fig. 8. Histograms of the PCA1 (A) and PCA2 (B) scores of the Malaguide (Spain), Ghomaride (Morocco), Longi-Taormina and Sila units (Italy). Samples of Italy (Upper Triassic to lowermost Jurassic) have higher PC1 scores, indicating more humid paleoenvironment. Similarly, samples of Italy tend to have negative PC2 scores, indicating more recycled sedimentary provenance.

periods of tectonic quiescence (e.g., Akarish and El-Gohary, 2011). However, chemical weathering of first-cycle detritus can also produce mudstones as mature as those of the Mesozoic continental redbeds. 5. Concluding remarks The studied Mesozoic continental redbeds characterize a comparatively small depositional area that around a small microcontinent that sourced it. This microcontinent, and the surrounding rifted basins where the Pseudoverrucano-type redbeds were deposited, formed on a block of continental crust (previously deformed during the variscan Orogeny) that, since Middle Jurassic time, was completely detached from the Europe–Iberia, Africa and Adria–Apulia plates to form the Mesomediterranean Microplate in the Western Tethys. This microplate was successively destroyed during Alpine orogenesis to form the Internal Units of the Central-Western Mediterranean Alpine Belts. Major and trace element distribution of the studied mudstones suggests that the chemical and mineralogical composition of these Mesozoic continental redbeds is mainly influenced by distinctive paleoclimatic variations and paleoweathering and sediment recycling processes. In particular, the relationships among some geochemical proxies indicate an increase in continental paleoweathering conditions and sediment recycling effects from the Middle Triassic to the lowermost Jurassic. PCA analysis, based on PC1 and PC2 variables, allow an understanding of the paleoweathering and sediment recycling effects of the Early Mesozoic Mediterranean sediments. As noted, the degree of hinterland paleoweathering increased due to rising humidity. Also, the extent of sediment recycling intensified during the uppermost

Triassic to the lowermost Jurassic time, as mainly shown for the Calabria–Peloritani Arc samples. However, the contrast between the Middle to Upper Triassic Gibraltar Arc samples is not always obvious because several samples in the Betic Cordillera and Rifian Maghrebids are also affected by sediment recycling. Therefore, both paleoweathering and sediment recycling effects controlled the geochemistry of the sediments. The prime factor causing the spatial and temporal differences in the studied Early Mesozoic rocks was a shift in paleoclimatic conditions, especially a temporal increase in humidity. These seasonal climate alternations with an increase in paleoclimatic humidity that favored paleoweathering conditions and recycling processes are also confirmed by the mineralogical data showing higher abundance of kaolinite, typical of warm-humid conditions, in the Calabria–Peloritani Arc mudstones than in the Gibraltar Arc mudstones.

Acknowledgments The authors are indebted to Robert Cullers, Agustín Martín-Algarra and the editor Finn Surlyk for their reviews, discussions and suggestions on the manuscript.

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