Sedimentary evolution of the Mesozoic continental redbeds using geochemical and mineralogical tools: the case of Upper Triassic to Lowermost Jurassic Monte di Gioiosa mudrocks (Sicily,

ORIGINAL PAPER

Sedimentary evolution of the Mesozoic continental redbeds usinggeochemical and mineralogical tools: the case of Upper Triassicto Lowermost Jurassic Monte di Gioiosa mudrocks(Sicily, southern Italy)

Francesco Perri • Salvatore Critelli •

Giovanni Mongelli • Robert L. Cullers

Received: 16 December 2009 / Accepted: 19 September 2010

� Springer-Verlag 2010

Abstract The continental redbeds from the Internal

Domains of the central-western Mediterranean Chains have

an important role in the palaeogeographic and palaeotec-

tonic reconstructions of the Alpine circum-Mediterranean

orogen evolution since these redbeds mark the Triassic-

Jurassic rift-valley stage of Tethyan rifting. The composi-

tion and the sedimentary evolution of the Middle Triassic

to Lowermost Jurassic continental redbeds of the San

Marco d’Alunzio Unit (Peloritani Mountains, Southern

Italy), based on mineralogical and chemical analyses,

suggests that the studied mudrock sediments share common

features with continental redbeds that constitute the Inter-

nal Domains of the Alpine Mediterranean Chains. Phyllo-

silicates are the main components in the mudrocks. The

10 A-minerals (illite and micas), the I–S mixed layers,

and kaolinite are the most abundant phyllosilicates. The

amount of illitic layers in I–S mixed layers coupled with

the illite crystallinity values (IC) are typical of high degree

of diagenesis, corresponding to a lithostatic/tectonic load-

ing of about 4–5 km. The mineralogical assemblage cou-

pled with the A-CN-K plot suggest post-depositional

K-enrichments. Palaeoweathering proxies (PIA and CIW)

record intense weathering at the source area. Further, the

studied sediments are affected by reworking and recycling

processes and, as consequence, it is likely these proxies

monitor cumulative effect of weathering. The climate in

the early Jurassic favoured recycling and weathering

occurred under hot, episodically humid climate with a

prolonged dry season. The source-area is the low-grade

Paleozoic metasedimentary basement. Mafic supply is

minor but not negligible as suggested by provenance

proxies.

Keywords Mesozoic continental redbeds � Mudrocks �Provenance � Source-area weathering � Southern Italy �Recycling

Introduction

After the Hercynian orogeny, and starting from the Trias-

sic, the western Mediterranean region was fragmented by

rifting and transform faulting, giving rise to the western

Tethyan Ocean, and several new lithospheric plates (Biju-

Duval et al. 1977). One of these lithospheric plates was the

Mesomediterranean Microplate (Guerrera et al. 1993),

comprising the internal zones of the Betic–Rif, Tellian,

Kabylian, Calabria–Peloritani and Southern Apennine

chains, built up after the alpine compressive Tertiary phase

related to the Mediterranean opening. The continental rift-

valley phase and the proto-oceanic phase of the Tethyan

rifting in the western-central Mediterranean region play an

important role for the deposition of the continental redbeds,

which mark the base of the Meso-Cenozoic sedimentary

covers. In fact, in many internal units of the Betic (Spain),

Rif (Morocco), Tell (Algeria), and Apenninic (Italy) chains,

the onset of Mesozoic-to-Cenozoic sedimentation was

marked by deposition of these continental clastic sediments.

F. Perri (&) � S. Critelli

Dipartimento di Scienze della Terra, Universita degli Studi della

Calabria, 87036 Arcavacata di Rende, CS, Italy

e-mail: [email protected]

G. Mongelli

Dipartimento di Chimica, Universita degli Studi della Basilicata,

Campus di Macchia Romana, 85100 Potenza, Italy

R. L. Cullers

Department of Geology, Kansas State University,

108 Thompson Hall, Manhattan, KS 66506-3201, USA

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DOI 10.1007/s00531-010-0602-6

Int J Earth Sci (Geol Rundsch) (2011) 100:1569–1587

/ Published online: 19 October 2010

The domain of depositional environments where these

redbeds were deposited was located around small mountain

areas, from which alluvial depositional systems provided

siliciclastic supply to neighbouring nascent continental

sedimentary basins formed during Triassic rifting (Perrone

et al. 2006).

The distribution of major and trace elements related to

the mineralogical composition of mudrocks is a pivotal

factor to reconstruct the palaeogeography and the palae-

otectonics of sedimentary basins. These determinations

are based on the different behaviour of the elements

during erosion and sedimentation, in order to preserve the

characteristic trace-element distribution of the source

rocks. However, a number of studies have shown that

weathering, hydraulic sorting, and diagenetic processes

can affect both the source rock signature and the tectonic

memory of the sediments in certain situations, question-

ing the validity of this assumption (Crichton and Condie

1993; Condie et al. 1992, 2001; Bauluz et al. 2000).

These modifications are dependent on the minerals in

which these trace elements are hosted. In this respect, it is

generally assumed that clay minerals are the phases

which contain most trace elements in fine-grained sedi-

ments (Taylor and McLennan 1985). By combining the

information deduced from the evolution of the X-ray

diffraction (XRD) patterns after thermo-chemical treat-

ments (heating and ethylene glycol treatments) and the

elemental analyses for major and trace elements concen-

trations obtained by X-ray fluorescence spectrometry

(XRF), it is possible to explain and predict the sedi-

mentary evolution and geological processes affecting fine

grained sediments and, thus, the relationship developed

between source area and sedimentary basin.

The studied mudrocks characterize the Mesozoic sedi-

mentary cover of the San Marco d’Aulunzo Unit outcrop-

ping in the Monte di Gioiosa (hereafter M.te di Gioiosa)

area, located in the northern sector of the Peloritani

Mountains (northeastern Sicily) of the Calabria-Peloritani

Terrane (southern Italy). The Peloritani Mountains repre-

sent the westward termination of the Calabria-Peloritani

Terrane, an orogenic segment connecting the dominantly

sedimentary thrust systems of the Apennines and the

Maghrebides of the central Mediterranean region. The

Calabrian microplate is one of the fragments of continental

crust of the western Mediterranean that rifted off the

southern margin of the Iberian plate and drifted south-

eastward to collide with the Adria plate (e.g., Critelli 1999

and reference therein).

We decided to focus our attention on the M.te di Gioiosa

section because it shows well preserved stratigraphic suc-

cession and it is one of the continuous and particularly

thick succession within the Mediterranean Mesozoic sedi-

mentary cover.

The aim of this study is to detail paleoweatheing con-

ditions, sedimentary recycling processes, source-area

provenance and diagenetic significance of Upper Triassic

to Lower Jurassic continental mudrocks from the San

Marco d’Aulunzo Unit (M.te di Gioiosa area, Peloritani

Mountains) in the context of the Triassic rifting of Pangea

during the early Mesozoic evolution of the westernmost

Mediterranean Alpine regions.

Geological and stratigraphic settings

The Calabria–Peloritani Terrane (CPT) is a fault-bounded

terrane including Calabria (the region at the southern tip of

the Italian peninsula) and the Peloritani Mountains of

northeastern Sicily (Fig. 1a) (Bonardi et al. 2001). The

CPT is composed of pre-Mesozoic crystalline basement

and shows evidence of pre-Neogene tectonism and meta-

morphism, in marked contrast with the geology of the

adjacent orogenic chains. The southern Apennines to the

north and the Maghrebides of northern Sicily are made of

thin-skinned thrust sheets that were emplaced during

Neogene time and lack any evidence of metamorphism

(Cavazza and Ingersoll 2005 and references therein).

The Peloritani Mountains represent the Sicilian portion

of the Calabria-Peloritani metamorphic massif, which is a

fragment of the Hercynian belt that has been thrust over the

sedimentary units of the Apenninic domains during early

Miocene (Amodio Morelli et al. 1976). In late-Hercynian

time the basement was widely intruded by granitoid bodies

(Del Moro et al. 1982; Rottura et al. 1990). High pressure

Tertiary metamorphism is present in northern Calabria,

whereas in Aspromonte (Platt and Compagnoni 1990) and

in the North-Peloritani (Messina et al. 1992) sectors the

overprint is very variable or totally absent.

The Alpine Peloritani belt consists of a series of

southward-verging continental-derived tectonic slices over-

lying the Apennine–Maghrebian domain (Lentini et al. 2000;

Bonardi et al. 2001). The geological mapping of this

area is described in detail in Lentini et al. (2000) and

Messina et al. (2004), and it will be summarized here. The

tectonic edifice is structurally arranged in a reverse-order

metamorphic stack, with the highest-grade metamorphic

rocks above the lowest-grade ones below. The main tec-

tonic units (Fig. 1 and Fig. 2) are, from top to bottom: the

Aspromonte unit, the Mela unit, the Mandanici unit, the Alı

unit, the Fondachelli unit, the San Marco d’Alunzio unit,

the Longi-Taormina unit and the Capo Sant’Andrea unit

(Vignaroli et al. 2008). The Aspromonte unit is made of

Hercynian high grade metamorphic and intrusive rocks

locally showing an Alpine metamorphic overprinting

equilibrated in the greenschist facies (Messina et al. 1990;

Bonardi et al. 1992). The Mela unit consists of Hercynian

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medium-grade gneisses, micaschists, and amphibolites

with eclogite relicts (Messina et al. 1997). The Mandanici

unit consists of a Paleozoic basement (low-grade meta-

clastic rocks involving lenses of quartzites and metaba-

sites) and a Mesozoic sedimentary cover (e.g. Bonardi

et al. 2001). The Alı unit consists of a Paleozoic arena-

ceous–conglomeratic basement covered by a Lower

Jurassic–Cretaceous sequence, affected by a very low-

grade metamorphic overprint (Bonardi et al. 1976; Cirrin-

cione and Pezzino 1991, 1994; Somma et al. 2005). The

Fondachelli unit is characterized by a Paleozoic sequence

(phyllites, metarenites, quartzites, metalimestones and

minor metabasites) with a Variscan, low-P, polyphase and

monofacial metamorphism, typical of chlorite zone of

greenschist facies, covered by a Mesozoic calcareous

deposits (Messina et al. 2004). The whole Peloritani tec-

tonic edifice is unconformably covered by the late-orogenic

sedimentary sequence of the Stilo–Capo d’Orlando For-

mation, which is Burdigalian in age (Bonardi et al. 2002).

Some Peloritanian nappes (Fig. 1a) consist only of pre-

Alpine crystalline basement (Mela and Aspromonte Units);

the lowermost tectonic units (i.e. the San Marco d’Alunzio,

the Longi–Taormina and the Capo Sant’Andrea units)

show a similar stratigraphic succession, made of a Devo-

nian polymetamorphic basement with a Mesozoic–Ceno-

zoic sedimentary cover. Only pre-Alpine (Variscan in age)

metamorphism has been reported from these units (e.g.

Bonardi et al. 2001 and references therein).

The studied area focuses on the San Marco d’Alunzio

Unit (Fig. 1a) that constitutes the lowermost nappe in the

Peloritanian nappe stack and is arranged in three imbri-

cated subunits, cropping out along a WNW-ESE oriented

belt. The San Marco d’Alunzio Unit is arranged with a

thick pre-Alpine crystalline basement and a narrow

Mesozoic to Cenozoic sedimentary cover. The basement

consists of low-grade metamorphic rocks (phyllite, metar-

enite, metalimestone and metavolcanic rocks) of Paleozoic

age (Messina et al. 1996, among others) on which sedi-

mentary successions rest unconformably (Lentini 1975;

Lentini and Vezzani 1975; Bonardi et al. 1976).

In the M.te di Gioiosa section the continental sediments

are particularly thick (over 100 m) and they are well

exposed. The sedimentary succession is characterized by

Upper Triassic lenticular conglomerate and sandstone

strata, representing fluvial channel-fill, interbedded with

thin clay layers (Fig. 3). The main lithofacies are fine

grained, represented by massive and laminated sandy

mudstones and siltstone beds, associated with stratified,

graded or rarely massive sandstone stratal-sets (Fig. 3a and

b); their internal structures are normal grading, parallel

laminae, sinusoidal ripples and cross-laminae. The silici-

clastic deposits show small-scale cross lamination and

small channels, characterized by variations in grain size

with quartz-grain commonly rounded that indicates

reworking. Decimetre-thick to metre-thick, sheet-like

massive sandstones are frequently alternated with thin-

bedded mudstones and siltstones (Fig. 3c). Palaeocurrents

indicate a dominant terrigenous clastic rocks supply

derived from rapid erosion of highland area located to the

north, northwestern and western of the present-day

Fig. 1 a Geological sketch map of the Peloritani Thrust Belt

(Southern Sector of the Calabria-Peloritani Arc—CPA). Legend: 1Etna volcanics (Pleistocene-Holocene). 2 Alluvial and coastal

deposits (Holocene) and Pleistocene-Miocene deposits. 3 Calcarenitidi Floresta Fm. (Serravallian-Langhian) and ‘‘Antisicilide Variegated

Clays’’ (upper Cretaceous-Paleogene). 4 Aspromonte Unit (Paleo-

zoic). 5 Mela Unit (Paleozoic). 6 Mandanici Unit (Mesozoic

sedimentary cover and Paleozoic basement). 7 Alı Unit (Mesozoic

sedimentary cover and Paleozoic basement). 8 Fondachelli Unit(Mesozoic sedimentary cover and Paleozoic basement). 9 Epimeta-

morphic units and their Meso-Cenozoic sedimentary cover (SanMarco d’Alunzio, Longi-Taormina and Capo Sant’Andrea Units). 10Sampling area. 11 Stratigraphic contact. 12 Tectonic contact.

Modified after Messina et al. 2004. b Detailed geological map of

M.te di Gioiosa area and location of the studied samples (San Marco

d’Alunzio Unit). Modified after Lentini et al. (2000)

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outcrops of the Calabria-Peloritani Arc realms, with main

transport directions oriented northwest (e.g., Mongelli et al.

2006; Critelli et al. 2008; Perri et al. 2008a, b). Generally

the sandstone and conglomerate beds show erosional bases,

and it is commonly difficult view the passage from fine-

grained lithofacies (mudstones and siltstones) to medium to

coarse grained stratified sandstones alternating with centi-

metre thick layers of mudrocks (Fig. 3d). The studied

sedimentary succession can be interpreted as a part of

braided river, showing a thin sequence of mudrocks with

thin planar and parallel sandstone beds, interpreted as

floodplain deposits. The contact between the metamorphic

basement and the sedimentary successions is not visible.

Sampling and methods

A set of 34 mudrock samples (from FP148 to FP181), from

beds interlayered between the quartzarenite and conglom-

erate strata (Fig. 4), were collected along the M.te di

Gioiosa section within the San Marco d’Alunzio Unit

cropping out in the Tyrrhenian area of the Peloritani

Mountains at Capo Calava and at the west of the Patti

village, between Saliceto and Sorrentini villages (Fig. 1b).

Samples were cleaned for geochemical analyses.

Weathered coats and veined surfaces were cut off. The

rocks were crushed and milled in agate mill to a very fine

powder.

The powder were placed in an ultrasonic bath at low

power for a few minutes for disaggregation; the \2 lm

grain-size fraction was then separated by settling in dis-

tilled water.

The mineralogy of whole-rock powder and clay frac-

tions (\2 lm) has been obtained by X-ray diffraction

(XRD) using a Siemens D5000 diffractometer (CuKa

radiation, graphite secondary monochromator, sample

spinner; step size 0.02; speed 3 s for step) at the Universita

di Catania (Italy). In order to distinguish chlorite from

kaolinite, the samples were heated to 550�C for 1 h. The

heating causes that the intensity of the chlorite {001}

reflection to increase greatly, shifting it to about

6.3–6.4�2h. Kaolinite becomes amorphous to X-rays dur-

ing this heating, and its diffraction pattern disappears

(Moore and Reynolds 1997). X-ray diffraction analyses

were also carried out on air-dried specimens, glycolated at

60�C for 8 h, and heated at 375�C for 1 h (Moore and

Reynolds 1997).

Semiquantitative mineralogical analysis of the bulk rock

was carried out on random powders measuring peak areas

using the WINFIT computer program (Krumm 1996). The

strongest reflection of each mineral was considered, except

for quartz for which the line at 4.26 A was used instead of

the peak at 3.34 A because of its superimposition with

10 A-minerals and I–S mixed layer series. The amount of

phyllosilicates was estimated measuring the 4.5 A peak

area. The percentage of phyllosilicates in the bulk rock was

split on the diffraction profile of the random powder,

according to the following peak areas: 10–15 A (illite–

smectite mixed layers), 10 A (illite ? micas), and 7 A

(kaolinite ? chlorite) minerals.

Fig. 2 Stratigraphic scheme of

the tectono-metamorphic units

(from bottom to top) of the

Peloritani Mountains (modified

from De Gregorio et al. 2003;

Messina et al. 2004)

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The percentage of illite (%I) and stacking order (Re-

ichweite; R) of the illite–smectite (I–S) mixed layer was

determined on the spectrum of the glycolated specimens

according to the method of Moore and Reynolds (1997).

The 2h peak position was determined by decomposition of

the x-ray pattern using asymmetric and symmetric func-

tions at low and high angles, respectively (Battaglia et al.

2004). Experimental x-ray profiles were compared with

theoretical patterns calculated with the NEWMOD�computer program (Reynolds 1985). The percentage of

illite in I–S mixed layers, and the illite crystallinity value

(IC) are techniques used to determine the degree of post-

sedimentary processes possibly affecting the redbed sam-

ples studied and the range of temperature they experienced.

The determination of illite crystallinity values (IC) is based

on the method that measures the full width at half-maxi-

mum (FWHM) of the first 10 A basal reflection of illite-

muscovite (Arkai et al. 2000).

Elemental analyses for major and some trace elements

(Nb, Zr, Y, Sr, Rb, Ba, Ni, Co, Cr, V) concentrations

were obtained by X-ray fluorescence spectrometry (Phi-

lips PW 1480) at the Universita della Calabria (Italy), on

pressed powder disks of whole-rock samples (prepared by

milling to a fine grained powder in a agate mill) and

compared to international standard rock analyses of the

United States Geological Survey. X-ray counts were

converted into concentrations 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 3 h at 900�C. Instrumental Neu-

tron Activation Analysis (INAA) at the Activation Lab-

oratories (Ancaster, Canada) was used to determine the

abundance of the rare earth elements (La, Ce, Nd, Sm,

Eu, Tb, Yb and Lu) and Sc, Zn, Cs, Th, and U. The

estimated precision and accuracy for trace element

determinations are better than 5%, except for those ele-

ments having a concentration of 10 ppm or less

(10–15%).

The chemical composition (e.g., some trace and rare-

earth elements, Th and Sc) of sediments is best suited for

provenance and tectonic setting determination studies,

because of their relatively low mobility during sedimentary

processes (e.g., McLennan et al. 1993; Cullers 2000;

Cullers and Podkovyrov 2002; Corcoran 2005; Mahjoor

et al. 2009 and references therein). The relative distribution

of the immobile elements that differ in concentration in

felsic and basic rocks such as La and Th (enriched in felsic

rocks) and Sc, Cr, and Co (enriched in basic rocks relative

to felsic rocks) has been used to infer the relative contri-

bution of felsic and basic sources in shales from different

tectonic environments (e.g., Wronkiewicz and Condie

1990). The REE pattern of fine grained siliciclastic sedi-

ments and some elemental ratios, especially Eu/Eu*, are

assumed to reflect the exposed crustal abundances in the

source area (McLennan et al. 1993; Mongelli et al. 1996;

Fig. 3 Field photos of the M.te

di Gioiosa section. a Decimetre-

thick to metre-thick, sheet-like

massive sandstones are

frequently alternated with thin-

bedded mudstones and

siltstones (tape measure 45 cm).

b View the passage from fine-

grained lithofacies (mudstones

and siltstones) to medium to

coarse grained stratified

sandstones alternating with

centimetre thick layers of

mudrocks (tape measure

25 cm). c Ungraded pebbly

sandstones sharply overlain by

graded medium to coarse-

grained sandstone bed,

reflecting superimposition of

two or more different flows

(tape measure 1 m). d Particular

of decimetre-thick massive

sandstones alternated with

coarse grained sandstone and

conglomerate beds with erosive

bases

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Fedo et al. 1996; Hassan et al. 1999; Bauluz et al. 2000;

Cullers 2000; Condie et al. 2001; Mongelli 2004, among

others). Mobile elements such as Na and Ca can be used to

evaluate the degree of chemical weathering, characterizing

paleoclimates in source regions at the time of deposition

(Nesbitt and Young 1982; Corcoran 2005; Mahjoor et al.

2009). Further the mineralogical features of fine grained

siliciclastic sediments may be used to record some post-

depositional changes, including diagenesis and incipient

metamorphism (Chamley 1995).

Mineralogy

The results of whole rock XRD analyses are shown in

Table 1. The mudrock samples are mainly composed by

phyllosilicates (mostly illite, illite/smectite mixed layers

and negligible amounts of kaolinite and chlorite) prevail

over quartz, hematite and minor amounts of feldspars.

Phyllosilicates are the main mineralogical components of

the mudrock, comprising 55–69% of the total abundances.

Quartz (ranging from 18 to 38%) is the most abundant

phase among the non-phyllosilicate minerals. Hematite is

relatively abundant with an average value of 8%, whereas

feldspars have an average value of 2%.

The \2 lm grain-size fraction is composed by illite

prevailing on illite/smectite mixed layers, kaolinite and

negligible amounts of chlorite. The distribution of illite and

I/S mixed layers along the studied succession is charac-

terized by a noticeable increase of illite in samples col-

lected along the lower part of the stratigraphic succession,

whereas, samples of the upper part have higher amounts of

the I/S mixed layers. The IC value ranges between 0.61�and 0.71� D 2h; the average illite crystallinity value is

0.65� D 2h (±0.1� D 2h), but the modal illite crystallinity

value is 0.67� D 2h. These are typical values of a high

diagenetic zone (Merriman and Frey 1999).

The percent of illitic layers in I–S mixed layers, esti-

mated following Moore and Reynolds (1997), is in the

range of 70–90% (R [ 1 ordering, Reickeweite number).

The percent of illitic layers in I–S mixed layers is better

defined in samples collected along the lower part of the

stratigraphic succession, that are characterized by illite with

higher crystallinity values. The high ordering of the mixed

layers and the high % of illitic layer in the I–S mixed layers

are also consistent with high diagenetic conditions.

Whole-rock geochemistry

Major element geochemistry

Major element geochemistry is a helpful tool when con-

templating certain trends in the general composition of

rocks, and to decipher the weathering profile of rocks (e.g.,

Nesbitt and Young 1982; Nesbitt et al. 1996; Zimmermann

and Spalletti 2009).

The elemental concentrations, some selected elemental

ratios, and the palaeoweathering indices CIA, CIW and

PIA (see below) of samples are given in Table 2. The

major and trace elemental distributions normalized to

upper continental crust averages (after McLennan et al.

2006; diagram after Floyd et al. 1989) are shown in Fig. 5.

The mudrocks are characterized by compositional ran-

ges for SiO2, TiO2, Al2O3, Fe2O3, and K2O close to those

Fig. 4 Stratigraphic column of the continental redbeds at the M.te di

Gioiosa section (San Marco d’Alunzio Unit; Peloritani Mountains,

Sicily) with location of the studied mudrock samples (FP148–FP181)

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of UCC (McLennan et al. 2006), although many samples

are weakly enriched in TiO2, Al2O3, Fe2O3, and K2O

(Fig. 5). On the contrary CaO, Na2O, P2O5 and, in a lesser

extent, MgO and MnO are strongly depleted relatively to

the UCC. Manganese concentrations are in most of the

samples well below to the UCC value. The MnO depletion

may be due to a sum of effects likely including source-area

composition and redox chemistry of the element promoting

Mn solubility as Mn2? under surface conditions (e.g.,

Mongelli et al. 2006). Aluminium is positively correlated

with TiO2 (r = 0.49) and Fe2O3 (r = 0.70), but it is neg-

atively correlated with SiO2 (r = 0.92). In fine grained

sediments Al2O3 monitors clays and this factor may thus

account for the competition between mica-like clay min-

erals and quartz (Crichton and Condie 1993). In the studied

samples Al2O3 is good correlated to the phyllosilicate

percentage (r = 0.9) testifying that this element monitors

the clay minerals in fine grained sediments. Furthermore,

the good correlation between Fe2O3 and hematite abun-

dance (r = 0.9) shows that high Fe2O3 values are related to

the presence of Fe-oxides (hematite), that gives the red

color to the studied sediments (‘redbeds’).

Trace element composition and rare earth elements

(REEs)

Most trace element concentrations overlap the PAAS

composition (Taylor and McLennan 1985) and the UCC

(McLennan et al. 2006) except for Ba and Sr that, similarly

to CaO, are depleted with respect to UCC (Fig. 5). Cesium

and rubidium, which behave similarly to potassium, are

enriched to the UCC and show a positive correlation with

K2O (r = 0.66 and r = 0.88, respectively) suggesting that

these elements are mostly controlled by the dioctahedral

mica-like clay minerals.

Zirconium and hafnium concentrations are slightly

higher than the UCC values (McLennan et al. 2006) tes-

tifying that mudrocks are reworked. These two elements

(Zr and Hf) are positively correlated (r = 0.91) since, in

sediments, these elements are likely controlled by zircon.

Due to a combination of its resistance to weathering and of

its high specific gravity, this mineral suffers a sorting

related fractionation that, in turn, means that Zr and Hf are

affected by gravitative fractionation (e.g. Taylor and

McLennan 1985). In a similar way, Nb and Ti show a

positive correlation (r = 0.48) because, in clastic sedi-

ments, they are usually hosted by resistate minerals (for

instance rutile; Zimmermann and Spalletti 2009) that may

follow the fate of the clay minerals. As for Ti, many

samples are weakly enriched in Nb and Sc (Fig. 5).

The concentrations of the transition elements are close

to or slightly lower than those of UCC (Fig. 5). The tran-

sition metals as Sc, V and Cr show a positive correlation

with Al2O3 (r = 0.73, r = 0.84 and r = 0.77, respec-

tively), suggesting these trace elements are mostly hosted

by mica-like clay minerals.

High field strength trace elements (HFSE) and the light

rare earth elements (LREE) show concentrations close to

those of UCC, although some samples are weakly enriched

relative to the UCC (Fig. 5). The chondrite-normalized REE

patterns (Fig. 6) have a PAAS-like shape characterized by

Table 1 Mineralogical composition of the bulk rock (weight percent)

SampleP

Phyllo Feld Qtz Hem

FP181 58.4 2.7 30.0 9.0

FP180 58.0 2.0 33.2 6.8

FP179 61.9 2.3 28.3 7.5

FP178 59.2 2.3 31.1 7.4

FP177 61.8 2.7 27.4 8.1

FP176 63.3 3.1 25.5 8.2

FP175 61.5 1.5 26.8 10.2

FP174 63.2 1.5 26.1 9.2

FP173 60.7 1.4 30.6 7.3

FP172 54.9 1.2 38.3 5.6

FP171 60.7 1.3 29.6 8.4

FP170 58.7 1.2 32.9 7.3

FP169 60.8 1.3 29.3 8.6

FP168 57.5 1.2 35.6 5.7

FP167 67.3 2.6 21.1 9.1

FP166 61.3 2.4 28.4 8.0

FP165 59.3 2.2 31.1 7.4

FP164 61.3 3.0 28.4 7.3

FP163 61.5 1.9 29.2 7.4

FP162 59.1 2.4 31.9 6.7

FP161 60.8 1.5 30.5 7.2

FP160 63.2 1.8 25.6 9.4

FP159 59.2 1.6 32.7 6.5

FP158 59.1 1.6 32.2 7.1

FP157 57.7 2.3 33.7 6.3

FP156 57.5 1.8 34.1 6.6

FP155 55.5 2.3 36.3 5.9

FP154 60.1 2.6 28.9 8.4

FP153 57.9 1.1 32.7 8.3

FP152 59.4 2.5 29.7 8.4

FP151 58.9 1.6 31.2 8.3

FP150 57.0 1.2 35.0 6.7

FP149 56.7 1.2 37.0 5.1

FP148 68.5 2.2 17.8 11.5

Min 54.9 1.1 17.8 5.1

Max 68.5 3.1 38.3 11.5

SD 2.9 0.6 4.3 1.3

Average 60.1 1.9 30.4 7.7

Qtz quartz, Feld feldspars (k-feldspars ? plagioclase), Hem hematite,PPhy sum of phyllosilicates

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Int J Earth Sci (Geol Rundsch) (2011) 100:1569–1587 1575

Table 2 Major, trace element and ratios distribution in studied samples

Samples no. FP148 FP149 FP150 FP151 FP152 FP153 FP154 FP155 FP156

Oxides (wt%)

SiO2 50.99 70.74 67.09 64.71 61.10 62.85 60.51 68.22 66.29

TiO2 0.94 0.49 0.63 0.78 0.77 0.80 0.77 0.83 0.74

Al2O3 24.12 16.16 17.20 18.04 19.17 17.81 19.74 15.98 17.40

Fe2O3 10.35 3.74 5.35 5.99 6.91 6.57 6.88 4.51 5.29

MnO 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.08 0.01

MgO 1.28 0.92 1.16 1.13 1.83 1.77 1.63 1.35 1.29

CaO 0.05 0.04 0.04 0.04 0.10 0.04 0.20 0.18 0.04

Na2O 0.26 0.17 0.18 0.20 0.26 0.14 0.23 0.21 0.30

K2O 6.99 4.56 4.86 5.27 5.90 5.62 5.88 4.48 4.37

P2O5 0.09 0.05 0.05 0.05 0.08 0.04 0.07 0.06 0.06

LOI 4.91 3.11 3.43 3.76 3.86 4.34 4.07 4.07 4.20

Total 99.99 99.99 99.99 99.98 99.99 99.99 99.99 99.97 99.99

Trace elements (ppm)

Nb 28.00 12.00 14.00 19.00 20.00 19.00 23.00 22.00 18.00

Zr 211.00 185.00 228.00 187.00 202.00 203.00 153.00 312.00 281.00

Y 55.00 30.00 41.00 52.00 84.00 26.00 30.00 60.00 37.00

Sr 158.00 85.00 160.00 148.00 65.00 55.00 77.00 83.00 104.00

Rb 307.00 171.00 187.00 227.00 265.00 260.00 259.00 194.00 180.00

Ba 572.00 233.00 325.00 368.00 358.00 291.00 419.00 321.00 330.00

Ni 22.00 13.00 21.00 16.00 33.00 31.00 33.00 29.00 24.00

Co 23.00 10.00 14.00 14.00 20.00 19.00 20.00 13.00 17.00

Cr 137.00 48.00 72.00 107.00 85.00 82.00 97.00 66.00 61.00

V 183.00 66.00 93.00 103.00 102.00 85.00 135.00 72.00 88.00

Cs 32.90 18.40 31.10 32.00 32.00 24.50 36.10 21.70 22.10

Hf 4.10 4.80 6.00 7.00 5.40 5.00 4.00 7.60 6.20

Sc 22.00 10.60 12.60 12.00 16.50 15.50 19.00 12.90 11.50

Th 17.30 12.40 13.50 13.10 14.80 15.70 16.30 15.20 14.40

U 4.90 2.60 2.80 2.50 2.90 2.80 2.50 3.50 2.70

La 84.60 43.80 60.30 62.00 46.20 45.20 39.30 52.20 44.10

Ce 105.00 59.00 78.00 75.00 72.00 69.00 57.00 75.00 69.00

Nd 53.00 26.00 39.00 41.00 31.00 29.00 23.00 35.00 31.00

Sm 12.70 5.60 8.80 8.40 9.60 6.30 6.00 8.70 7.60

Eu 2.40 0.90 1.70 2.00 2.30 1.00 1.00 1.50 1.50

Tb 1.20 0.60 0.80 0.70 1.90 0.60 0.60 1.10 0.90

Yb 4.60 2.90 3.60 3.40 5.90 3.00 3.10 4.50 3.50

Lu 0.69 0.44 0.54 0.58 0.89 0.45 0.46 0.67 0.53

Ratios

CIA 67.79 68.64 68.52 67.89 66.45 66.36 66.96 68.01 70.49

CIW 98.26 98.24 98.26 98.20 97.48 98.62 97.11 96.76 97.36

PIA 96.84 96.90 96.92 96.74 95.27 97.31 94.74 94.37 95.72

Eu/Eu* 0.66 0.55 0.65 0.68 0.69 0.55 0.57 0.56 0.65

LaN/YbN 12.43 10.21 11.12 11.32 5.29 10.18 8.57 7.84 8.51

La/Sc 3.85 4.13 4.79 5.17 2.80 2.92 2.07 4.05 3.83

Th/Sc 0.79 1.17 1.07 1.09 0.90 1.01 0.86 1.18 1.25

La/Co 3.68 4.38 4.31 4.43 2.31 2.38 1.97 4.02 2.59

Th/Co 0.75 1.24 0.96 0.94 0.74 0.83 0.82 1.17 0.85

La/Cr 0.62 0.91 0.84 0.58 0.54 0.55 0.41 0.79 0.72

Th/Cr 0.13 0.26 0.19 0.12 0.17 0.19 0.17 0.23 0.24

Cr/Th 7.92 3.87 5.33 8.17 5.74 5.22 5.95 4.34 4.24

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Table 2 continued

Samples no. FP157 FP158 FP159 FP160 FP161 FP162 FP163 FP164 FP165

Oxides (wt%)

SiO2 65.90 63.68 63.81 56.85 61.88 62.97 61.59 60.96 64.17

TiO2 0.74 0.81 0.80 0.74 0.85 0.79 0.77 0.82 0.85

Al2O3 17.61 18.18 18.55 21.78 19.48 19.46 20.15 20.29 18.52

Fe2O3 5.30 6.21 5.79 8.17 5.95 5.51 6.34 6.41 6.46

MnO 0.01 0.04 0.00 0.01 0.01 0.01 0.01 0.03 0.01

MgO 1.21 1.75 1.18 1.25 1.31 1.29 1.31 1.46 1.46

CaO 0.10 0.05 0.02 0.02 0.02 0.15 0.05 0.13 0.02

Na2O 0.30 0.23 0.25 0.27 0.20 0.26 0.29 0.42 0.37

K2O 4.58 5.08 4.90 6.04 5.00 5.32 4.99 5.09 4.21

P2O5 0.05 0.05 0.03 0.06 0.05 0.06 0.06 0.06 0.02

LOI 4.18 3.90 4.66 4.80 5.21 4.15 4.32 4.32 3.90

Total 99.98 99.98 99.99 99.99 99.96 99.97 99.88 99.99 99.99

Trace elements (ppm)

Nb 18.00 20.00 23.00 22.00 27.00 24.00 23.00 26.00 19.00

Zr 257.00 263.00 257.00 164.00 237.00 207.00 253.00 226.00 283.00

Y 33.00 41.00 30.00 56.00 38.00 35.00 41.00 34.00 35.00

Sr 106.00 97.00 97.00 171.00 145.00 81.00 101.00 97.00 158.00

Rb 184.00 199.00 227.00 258.00 245.00 222.00 196.00 213.00 170.00

Ba 339.00 282.00 295.00 423.00 309.00 430.00 385.00 401.00 387.00

Ni 23.00 39.00 23.00 31.00 34.00 26.00 26.00 32.00 44.00

Co 14.00 19.00 12.00 18.00 15.00 13.00 16.00 17.00 17.00

Cr 62.00 74.00 85.00 101.00 90.00 77.00 78.00 87.00 80.00

V 91.00 104.00 96.00 152.00 111.00 122.00 104.00 112.00 129.00

Cs 21.60 12.70 20.10 28.30 24.20 29.90 18.70 22.40 18.90

Hf 6.20 6.90 6.60 3.70 6.60 5.80 7.10 6.70 8.20

Sc 12.50 17.80 11.20 23.30 15.90 14.10 13.20 14.30 15.30

Th 14.30 16.20 13.30 13.20 12.10 12.00 11.50 11.90 11.90

U 2.70 2.90 2.70 2.70 2.30 3.00 2.90 2.60 2.50

La 45.10 48.60 38.90 47.30 48.00 44.90 51.40 52.70 55.40

Ce 73.00 71.00 74.00 87.00 94.00 80.00 99.00 109.00 109.00

Nd 31.00 38.00 30.00 48.00 43.00 30.00 41.00 39.00 44.00

Sm 7.00 8.70 5.10 9.80 8.00 6.10 7.60 7.30 8.40

Eu 1.20 1.60 1.00 2.50 1.60 1.40 1.60 1.50 1.70

Tb 0.70 0.90 0.60 1.40 0.60 0.60 0.70 0.60 0.80

Yb 3.30 4.20 3.30 4.40 3.70 3.30 3.70 3.40 3.50

Lu 0.50 0.63 0.50 0.65 0.57 0.51 0.55 0.52 0.53

Ratios

CIA 69.52 68.59 69.82 68.82 70.35 68.60 70.45 70.12 72.32

CIW 96.96 97.91 98.01 98.17 98.45 97.18 97.71 96.39 97.15

PIA 94.97 96.34 96.66 96.81 97.44 95.18 96.32 94.19 95.64

Eu/Eu* 0.59 0.63 0.91 0.81 0.92 1.06 0.74 0.95 0.71

LaN/YbN 9.24 7.82 7.97 7.26 8.77 9.19 9.39 10.47 10.70

La/Sc 3.61 2.73 3.47 2.03 3.02 3.18 3.89 3.69 3.62

Th/Sc 1.14 0.91 1.19 0.57 0.76 0.85 0.87 0.83 0.78

La/Co 3.22 2.56 3.24 2.63 3.20 3.45 3.21 3.10 3.26

Th/Co 1.02 0.85 1.11 0.73 0.81 0.92 0.72 0.70 0.70

La/Cr 0.73 0.66 0.46 0.47 0.53 0.58 0.66 0.61 0.69

Th/Cr 0.23 0.22 0.16 0.13 0.13 0.16 0.15 0.14 0.15

Cr/Th 4.34 4.57 6.39 7.65 7.44 6.42 6.78 7.31 6.72

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Table 2 continued

Samples no. FP166 FP167 FP168 FP169 FP170 FP171 FP172 FP173 FP174

Oxides (wt%)

SiO2 60.45 54.65 69.15 60.28 63.83 60.12 72.34 61.67 57.35

TiO2 0.98 1.08 0.63 0.80 0.75 0.76 0.78 0.78 0.87

Al2O3 20.92 23.90 16.46 19.56 18.07 19.32 14.09 19.50 21.52

Fe2O3 7.04 7.96 4.50 7.38 6.22 7.19 4.37 6.09 8.00

MnO 0.01 0.01 0.01 0.02 0.01 0.02 0.01 0.01 0.01

MgO 1.46 1.31 1.30 1.72 1.50 1.66 1.16 1.54 1.35

CaO 0.02 0.02 0.02 0.02 0.01 0.01 0.02 0.03 0.04

Na2O 0.40 0.45 0.14 0.19 0.18 0.18 0.14 0.19 0.21

K2O 4.87 5.76 4.76 5.74 5.32 5.76 3.98 5.62 6.39

P2O5 0.02 0.03 0.02 0.02 0.02 0.03 0.02 0.03 0.06

LOI 3.81 4.82 3.00 4.25 4.07 4.94 3.08 4.52 4.19

Total 99.98 99.99 99.99 99.98 99.98 99.99 99.99 99.98 99.99

Trace elements (ppm)

Nb 22.00 29.00 14.00 23.00 23.00 22.00 20.00 24.00 27.00

Zr 308.00 212.00 312.00 160.00 242.00 166.00 734.00 205.00 195.00

Y 41.00 42.00 34.00 25.00 37.00 27.00 33.00 37.00 46.00

Sr 103.00 126.00 73.00 82.00 87.00 117.00 75.00 111.00 137.00

Rb 193.00 246.00 180.00 268.00 224.00 262.00 157.00 238.00 277.00

Ba 524.00 548.00 228.00 383.00 309.00 396.00 194.00 371.00 428.00

Ni 49.00 48.00 21.00 27.00 23.00 23.00 15.00 23.00 25.00

Co 18.00 19.00 11.00 18.00 17.00 18.00 11.00 15.00 19.00

Cr 96.00 119.00 49.00 85.00 73.00 83.00 46.00 78.00 104.00

V 136.00 157.00 60.00 110.00 106.00 124.00 57.00 114.00 125.00

Cs 24.30 24.80 18.50 36.10 29.70 36.40 13.90 28.40 40.10

Hf 8.20 6.20 8.60 5.30 7.20 5.10 17.50 7.20 5.70

Sc 16.40 21.50 10.50 15.80 13.80 16.60 7.90 15.50 19.10

Th 12.40 12.10 10.30 11.50 10.80 11.50 10.40 12.00 12.90

U 3.60 3.00 2.00 3.10 2.70 2.30 4.00 2.50 3.80

La 54.30 54.80 46.00 42.60 42.60 48.00 43.00 55.80 60.00

Ce 104.00 104.00 95.00 89.00 83.00 105.00 85.00 97.00 106.00

Nd 39.00 36.00 39.00 36.00 31.00 39.00 32.00 41.00 44.00

Sm 7.20 8.00 7.50 6.00 7.30 8.80 6.40 8.80 9.00

Eu 1.50 1.70 1.60 1.10 1.50 1.70 1.20 1.70 1.90

Tb 0.90 0.70 0.60 0.60 0.70 0.90 0.90 0.90 0.90

Yb 4.10 3.90 3.30 2.40 3.60 3.10 4.10 4.30 4.40

Lu 0.61 0.60 0.51 0.36 0.54 0.47 0.61 0.65 0.66

Ratios

CIA 71.85 71.20 72.01 67.85 67.79 67.54 68.63 68.18 67.58

CIW 97.28 97.33 98.67 98.53 98.56 98.65 98.45 98.46 98.41

PIA 95.78 95.78 97.88 97.31 97.35 97.49 97.25 97.22 97.08

Eu/Eu* 0.68 0.75 0.99 0.85 0.72 0.66 0.60 0.66 0.73

LaN/YbN 8.95 9.50 9.42 11.99 8.00 10.46 7.09 8.77 9.21

La/Sc 3.31 2.55 4.38 2.70 3.09 2.89 5.44 3.60 3.14

Th/Sc 0.76 0.56 0.98 0.73 0.78 0.69 1.32 0.77 0.68

La/Co 3.02 2.88 4.18 2.37 2.51 2.67 3.91 3.72 3.16

Th/Co 0.69 0.64 0.94 0.64 0.64 0.64 0.95 0.80 0.68

La/Cr 0.57 0.46 0.94 0.50 0.58 0.58 0.93 0.72 0.58

Th/Cr 0.13 0.10 0.21 0.14 0.15 0.14 0.23 0.15 0.12

Cr/Th 7.74 9.83 4.76 7.39 6.76 7.22 4.42 6.50 8.06

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Table 2 continued

Samples no. FP175 FP176 FP177 FP178 FP179 FP180 FP181

Oxides (wt%)

SiO2 58.03 58.43 59.37 64.39 60.17 67.90 62.30

TiO2 0.89 1.03 0.90 0.81 0.87 0.87 0.86

Al2O3 20.56 21.99 20.91 18.77 21.40 17.99 18.86

Fe2O3 8.96 7.09 6.75 6.42 6.78 5.88 8.17

MnO 0.01 0.01 0.01 0.01 0.01 0.01 0.07

MgO 1.30 1.79 2.56 1.62 1.77 0.87 1.57

CaO 0.03 0.03 0.02 0.02 0.03 0.03 0.17

Na2O 0.21 0.58 0.38 0.37 0.43 0.38 0.36

K2O 5.92 4.53 4.10 4.03 4.59 2.74 3.48

P2O5 0.07 0.02 0.03 0.02 0.02 0.04 0.05

LOI 4.01 4.48 4.96 3.53 3.91 3.26 4.00

Total 99.99 99.98 99.99 99.99 99.98 99.97 99.89

Trace elements (ppm)

Nb 26.00 22.00 20.00 18.00 20.00 20.00 20.00

Zr 221.00 335.00 237.00 243.00 231.00 346.00 278.00

Y 51.00 33.00 39.00 39.00 36.00 47.00 62.00

Sr 118.00 178.00 119.00 158.00 148.00 140.00 113.00

Rb 253.00 191.00 191.00 172.00 215.00 138.00 162.00

Ba 436.00 438.00 374.00 385.00 403.00 246.00 432.00

Ni 24.00 55.00 42.00 38.00 51.00 33.00 59.00

Co 20.00 21.00 22.00 19.00 21.00 17.00 29.00

Cr 98.00 100.00 92.00 77.00 93.00 84.00 90.00

V 122.00 141.00 132.00 113.00 129.00 95.00 133.00

Cs 39.00 18.70 18.50 20.30 29.60 10.40 11.80

Hf 6.40 9.20 6.50 6.50 6.20 9.00 7.80

Sc 19.00 18.30 17.50 14.10 16.70 14.40 16.40

Th 12.80 13.80 10.00 10.90 11.20 11.70 11.60

U 2.50 2.70 2.40 2.50 3.70 3.80 2.20

La 61.60 58.60 47.60 47.70 52.50 55.40 61.40

Ce 113.00 117.00 91.00 99.00 105.00 138.00 120.00

Nd 55.00 44.00 38.00 41.00 43.00 48.00 48.00

Sm 10.60 9.50 7.90 8.40 9.90 10.30 10.90

Eu 2.10 1.80 1.60 1.80 1.90 2.20 2.30

Tb 1.10 0.60 0.70 0.90 1.20 1.20 1.20

Yb 4.40 3.70 3.60 3.60 3.50 4.30 4.70

Lu 0.66 0.55 0.54 0.54 0.53 0.66 0.71

Ratios

CIA 68.23 73.55 75.05 73.32 73.19 80.22 75.34

CIW 98.40 96.28 97.41 97.19 97.08 96.92 96.27

PIA 97.13 94.61 96.31 95.82 95.67 96.11 94.83

Eu/Eu* 0.68 0.87 0.72 0.73 0.63 0.71 0.71

LaN/YbN 9.46 10.70 8.93 8.95 10.14 8.71 8.83

La/Sc 3.24 3.20 2.72 3.38 3.14 3.85 3.74

Th/Sc 0.67 0.75 0.57 0.77 0.67 0.81 0.71

La/Co 3.08 2.79 2.16 2.51 2.50 3.26 2.12

Th/Co 0.64 0.66 0.45 0.57 0.53 0.69 0.40

La/Cr 0.63 0.59 0.52 0.62 0.56 0.66 0.68

Th/Cr 0.13 0.14 0.11 0.14 0.12 0.14 0.13

Cr/Th 7.66 7.25 9.20 7.06 8.30 7.18 7.76

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LREE/HREE fractionation (average LaN/YbN = 9.27 ±

1.43) (where ‘‘N’’ expresses chondritic normalization) and

negative Eu-anomaly (average Eu/Eu* = 0.72 ± 0.13).

The average LaN/YbN ratio and the Eu anomaly sizes are the

same as those of the PAAS (LaN/YbN = 9.2; Eu/Eu*PAAS =

0.66). Rare earth elements and yttrium, which behave like

heavy rare earth elements (HREE), show no correlation

with Al2O3; this is consistent with the observation that in

fine grained sediments these elements may be hosted in

accessory phases (Mongelli et al. 1996, 2006).

Discussion

Source-area weathering, sorting and recycling

Variable degrees of weathering in source areas may have

an important influence on the abundances of alkali and

alkaline-earth elements in siliciclastic sediments. Rubidium

and barium are often fixed in weathering profiles, whereas,

cations with smaller ionic radii, such as Na, Ca and Sr, are

easily removed from weathering profiles (Nesbitt et al.

1980).

A common approach to quantifying the degree of

source-area weathering is to use the chemical index of

alteration (CIA; Nesbitt and Young 1982). The chemical

compositions of studied samples are plotted as molar pro-

portions within Al2O3, CaO*?Na2O, K2O (A-CN-K)

compositional space, where CaO* represents Ca in silicate-

bearing minerals only. The CIA values of analyzed mud-

rocks are homogeneous (average = 70.1 ± 3.1) and in the

A-CN-K triangular diagram the samples plot in a tight

group on the A-K join close to the muscovite-illite point

(Fig. 7). Illite and other illitic minerals (I/S mixed layers)

are the dominant clay minerals that characterize the studied

mudrocks. The weathering trend for Upper Archean crust,

predicted from kinetic leach rates (Nesbitt and Young

1984; Nesbitt 1992), is directed towards the processes of

illitization (Fig. 7 point 1; e.g., Fedo et al. 1995). The

studied mudrocks plot below this trend since many samples

contain considerable K2O because they may have under-

gone K metasomatism (Nesbitt 1992). Both the amount of

K enrichment and the palaeoweathering index prior to such

enrichment can be ascertained from the A-CN-K plot. As K

involves addition of K2O to aluminous clays, the studied

samples follow a path toward the K2O apex of the triangle,

and the line from the K apex through the mudrock samples

Fig. 5 Normalization of major and trace elements to upper conti-

nental crust averages (after McLennan et al. 2006; diagram after

Floyd et al. 1989). The plot of the Post-Archean Australian Shales

(PAAS; Taylor and McLennan 1985) is shown for comparison

Fig. 6 Rare earth element compositional ranges, chondrite-normal-

ized (Taylor and McLennan 1985). The plot of the Post-Archean

Australian Shales (PAAS) is shown for comparison

Fig. 7 A-CN-K diagram (Nesbitt and Young 1982) for studied

samples. Studied samples are probably related to a initial weathering

trend (point 1) and subsequent a metasomatic trend (arrow 3) to attain

their current position. Point 2 is the probably CIA of weathered

residues (before metasomatism). Note only top 60% of the triangle is

shown. Legend: A, Al2O3; C, CaO; N, Na2O; K, K2O; Gr granite; Msmuscovite; Il illite; Ka kaolinite; Ch chlorite; Gi gibbsite; Smsmectite; Bi biotite; Ks K-feldspar; Pl plagioclase. UC Upper Archean

Crust (Condie 1993)

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Int J Earth Sci (Geol Rundsch) (2011) 100:1569–15871580

intersects the predicted weathering trend at a point repre-

senting its premetasomatized composition (Fig. 7, arrow 3

and point 2). The palaeoweathering index corrected for K

enrichment can then be determined by reading off the CIA

value, and the premetasomatized CIA value of 80 indicates

that the studied mudrocks have gained about 10% K2O

during metasomatism (e.g., Fedo et al. 1995).

Since the CIA index is not sensitive to the weathering

degree when K reintroduction occurs in the system, as in the

present case, alternative indices can be used to monitor

palaeoweathering at the source. Harnois (1988) proposed the

CIW index (Chemical Index of Weathering), which is not

sensitive to post-depositional K-enrichments. The CIW

similarly to the CIA, is a molecular immobile/mobile ratio

based on the assumption that Al remains in the system and

accumulates in the residue while Ca and Na are leached

away. The studied mudrocks show very uniform CIW values

(average = 97.7 ± 0.7). This indicates a source area with

intense weathering in steady-state conditions where material

removal rate matches the production of mineralogically

uniform weathering products generated in the upper zone of

soil development (Nesbitt et al. 1997). Furthermore, the

mudrocks show high PIA (Plagioclase Index of Alteration;

Fedo et al. 1995) values (average = 96.2 ± 1.1) that indi-

cate intense weathering at the source area and that most of

the plagioclase has been converted to clay minerals.

The presence of sorting-related fractionations is evalu-

ated when the Zr/Sc ratio (a useful index of sediment

recycling; e.g. Cox et al. 1995; Hassan et al. 1999), is

plotted against the Th/Sc ratio (indicator of chemical dif-

ferentiation; McLennan et al. 1993). The mudrocks are not

clustered along the primary compositional trend but fall

along a trend involving zircon addition and thus sediment

recycling (Fig. 8).

Constraints on provenance

The geochemical signatures of clastic sediments have

been used to find out provenance (Taylor and McLennan

1985; Condie et al. 1992; Cullers 1995; Madhavaraju

and Ramasamy 2002; Armstrong-Altrin et al. 2004).

Rare earth elements (REE) and Th, among the HFSE,

and some transition elements, including Sc and Cr, can

provide an insight into the provenance and are thus

useful to constrain the average source-area composition

(e.g., Taylor and McLennan 1985; Floyd et al. 1989;

McLennan et al. 1993; Fedo et al. 1996; Cullers and

Berendsen 1998). The abundance of Cr and Ni in silic-

iclastic sediments is considered as a useful indicator in

provenance studies. According to Wrafter and Graham

(1989) a low concentration of Cr indicates a felsic

provenance, whereas high contents of Cr and Ni are

mainly found in sediments derived from ultramafic rocks

(Armstrong-Altrin et al. 2004). The Cr/Ni ratios (aver-

age = 2.76) are low for the studied mudrocks. However,

the Th/Cr ratio (average = 0.16) is quite similar to the

PAAS (Th/Cr = 0.13; Taylor and McLennan 1985) and

to the UCC (Th/Cr = 0.13; McLennan et al. 2006).

Ratios such as La/Sc, Th/Sc, Th/Co, and Th/Cr are

significantly different in felsic and basic rocks and may

allow constraints on the average provenance composition

(Wronkiewicz and Condie 1990; Cox et al. 1995; Cullers

1995). The Th/Sc, Th/Co, Th/Cr, Cr/Th, and La/Sc ratios

of shales from this study are compared with those of

sediments derived from felsic and basic rocks as well as

to upper continental crust (UCC; McLennan et al. 2006)

and PAAS (Taylor and McLennan 1985) values

(Table 3). This comparison also suggests that these ratios

are within the range of felsic rocks. In addition, the La/

Sc and Th/Sc ratios are fairly constant in sedimentary

rocks (2.4 and 0.9, respectively; Taylor and McLennan

1985). The La/Sc and Th/Sc ratios of the studied mud-

rocks are close to those of the PAAS and UCC

(Table 3), suggesting a felsic nature of the source rocks.

This agrees with petrographic data obtained from the

sandstones interbedded between the studied mudrocks,

which are quartzarenite-to-quartzolithic in composition

(Critelli et al. 2008). They are characterized by abundant

monocrystalline and polycrystalline quartz, whereas feld-

spars are minor or absent. Sandstone suites plot within the

provenance fields for both continental blocks and recycled

orogens (Critelli et al. 2008).

Provenance proxies including triangular relationships

of Th-Sc-Zr and the Cr/V and Y/Ni ratios have been also

used to discriminate the source area composition and the

tectonic setting. The Th-Sc-Zr/10 diagram (Fig. 9) may be

used to discriminate sediments from felsic sources to

progressively more mafic sources (e.g., Bhatia and Crook

Fig. 8 Th/Sc vs. Zr/Sc plot (after McLennan et al. 1993). Samples

depart from the compositional trend indicating zircon addition

suggestive of a recycling effect. Rock average compositions (Rhy-

olite, Dacite and Andesite) are from Lacassie et al. (2006)

123

Int J Earth Sci (Geol Rundsch) (2011) 100:1569–1587 1581

1986; Cullers 1994). In this diagram the studied mudrocks

plot in the silicic rock field, close to the PAAS and UCC

point (Fig. 9). Moreover, the studied samples follow a

trend towards a continental environment, far from the

oceanic arc-related field suggesting a mainly felsic source.

The Cr/V ratio is an index of the enrichment of Cr over the

other ferromagnesian trace elements, whereas Y/Ni moni-

tors the general level of ferromagnesian trace elements (Ni)

compared to a proxy for HREE (Y). Mafic–ultramafic

sources tend to have high ferromagnesian abundances; such

a provenance would result in a decrease in Y/Ni (e.g.,

Hiscott 1984; McLennan et al. 1993). At the same time,

high values in Sc/Th are related to a mafic–ultramafic

supply. The Cr/V vs. Sc/Th and Cr/V vs. Y/Ni diagram

(Hiscott 1984) indicates the lack of a marked mafic–

ultramafic detritus input for the studied samples (Fig. 10).

The Eu/Eu*, a more conservative provenance proxy

(e.g. McLennan et al. 1993; Mongelli et al. 1998; Cullers

2000), vs. LaN/YbN plot add insights on the chemical

affinity when studied samples are compared to the base-

ment terranes (Messina et al. 2004). The mudrocks are

generally similar in composition to the felsic rocks of the

Paleozoic basement (Fig. 11) and only few have higher Eu/

Eu*. Moreover, a minor contribution from a mafic com-

ponent may be assumed in few samples, as deduced by the

amount of Sc and Nb. These values, however, are lower

than the Sc and Nb values of the amphibole-rich basement

terranes (Messina et al. 2004). Furthermore, the Eu

anomaly is not correlated with both the Sc and the Nb

values. Thus, the higher values of the Eu/Eu* proxy

observed in few samples, likely record a mixed source

including felsics and a definitely minor imput of mafic

detritus.

An estimation of the composition of sedimentary rocks

can be showed using the ratios Nb/Y vs. Zr/Ti (after

Winchester and Floyd 1977; Fralick 2003; Zimmermann

and Spalletti 2009; Fig. 12) as these elements are strongly

immobile. Most of the studied samples fall in the rhyoda-

cite/dacite composition. They are partly enriched in Nb

over Y following a rhyolitic/dacitic trend, although some

samples seems to be influenced by a mafic input as showed

by the andesitic/basaltic trend (Fig. 12). This points to the

Table 3 Range of elemental ratios of studied samples compared to the ratios those of felsic and mafic rocks, upper continental crust (UCC;

McLennan et al. 2006), and Post-Archean Australian shale (PAAS; Taylor and McLennan 1985)

Elemental ratio Range of studied

mudrocks

Range of sedimentsa Upper continental crustb Post-Archean Australian

average shalec

Felsic rocks Mafic rocks

La/Sc 3.45 ± 0.77 2.5–16.3 0.43–0.86 2.21 2.4

Th/Sc 0.87 ± 0.20 0.84–20.5 0.05–0.22 0.79 0.9

Th/Co 0.78 ± 0.19 0.67–19.4 0.04–1.4 0.64 0.63

Th/Cr 0.16 ± 0.04 0.13–2.7 0.43–0.86 0.13 0.13

Cr/Th 6.63 ± 1.51 4.00–15 25–500 7.69 7.53

a Cullers (1994, 2000), Cullers and Podkovyrov (2000), bMcLennan et al. (2006), cTaylor and McLennan (1985)

Fig. 9 Th-Sc-Zr/10 diagram (after Bhatia and Crook 1986). The

mudrocks fall in a region close to the PAAS and the UCC point that

rules out important mafic supply

Fig. 10 Analysing the provenance by using relations of Cr/V vs. Sc/

Th and Cr/V vs. Y/Ni (after Hiscott 1984). Curve model mixing

between granite and ultramafic end-members. Ultramafic sources

have very low Y/Ni and high Cr/V and Sc/Th ratios. Arrows indicate

the direction of the mafic–ultramafic source end-members

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Int J Earth Sci (Geol Rundsch) (2011) 100:1569–15871582

mixing of a closely related volcanic detritus or mafic

component with a typical UCC (‘granitic’) source. The

source of the felsic-to-intermediate volcanic detritus is

might be related to some units that characterize the base-

ment rocks (e.g., metavolcanic rocks of the Mandanici,

Longi-Taormina, San Marco d’Alunzio and Capo San-

t’Andrea basements; Fig. 1 and Fig. 13). The felsic input is

explainable by the regional geology and the palaeogeo-

graphic evolution (Fig. 13) of the rocks that nowadays

characterize the paleozoic basement of the Internal

Domains of the Alpine central-western Mediterranean

Chains involved in the Meso-Cenozoic basin evolution

(e.g., Perrone et al. 2006; Mongelli et al. 2006; Critelli

et al. 2008; Perri 2008; Perri et al. 2008a, b).

Conclusions

The chemical and mineralogical composition of the studied

terrigenous sediments depends on the source-area compo-

sition, palaeoweathering, sorting and recycling processes

and in some cases, burial history. Thus, these processes

must be evaluated and hopefully minimized to monitor

provenance.

The geochemistry and mineralogy of Mesozoic conti-

nental mudrocks from the M.te di Gioiosa stratigraphic

section of the Peloritani Mountains suggest a complex

history. The mudrocks have concentrations very similar to

those of the UCC (McLennan et al. 2006) for Si, Ti, Al, Fe,

Mg, K, HFSE, and transition metals, whereas, Ca, Na, P,

Ba and Sr are strongly depleted. Cesium and rubidium are

enriched to the UCC and show a positive correlation with

potassium, suggesting these trace elements are mostly

hosted by dioctahedral mica-like clay minerals. This in turn

indicates that illite and illitic minerals (I/S mixed layers)

have played an important role in the distribution of ele-

ments in these rocks, since these minerals are abundant in

the studied samples. Furthermore, the mudrocks fall in a

tight group on the A-K join, in the A-CN-K triangular

diagram (Fig. 7), close to the muscovite-illite point, in

agreement with the mineralogical data.

The source area for the studied mudrocks should have

similar features to those of the pre-Mesozoic basements

of many Calabrian-Peloritanian tectonic units, which are

predominantly composed of felsic rocks with lesser

amounts of intermediate and mafic rocks (Fig. 13). Geo-

chemical proxies consistently suggest a felsic nature of the

source area, with a minor but not negligible supply from

mafic metavolcanic rocks.

As for palaeoweathering both the PIA and the CIW

proxies suggest intense weathering at the source area. The

studied sediments seems to be affected by reworking and

recycling processes and, as a consequence, it is likely these

proxies monitor cumulative effects of weathering (e.g.,

Mongelli et al. 2006; Critelli et al. 2008; Perri et al. 2008a,

2008b).

Wet-humid conditions favored the formation of stream

channels that eroded the soil profiles, whereas, the partially

Fig. 11 Eu/Eu* vs. (La/Yb)N plot (modified from Cullers and

Podkovyrov 2002) showing the composition fields of the Peloritani

Mt. basement rocks. PHYT Phyllosilicate-rich Types, QFT Quartz-

Feldspar-rich Types, AMPT Amphibole-rich Types (Messina et al.

2004)

Fig. 12 Zr/TiO2 vs. Nb/Y plot (after Winchester and Floyd 1977;

Fralick 2003; Zimmermann and Spalletti 2009) to reveal differences

in the whole-rock composition of the studied sediment

123

Int J Earth Sci (Geol Rundsch) (2011) 100:1569–1587 1583

dry season favored sedimentation; successively new wet-

humid conditions caused the erosion of the sediments

formed before (Perrone et al. 2006; Mongelli et al. 2006;

Critelli et al. 2008; Perri et al. 2008a; 2008b). The alter-

nation in the Late Triassic-Early Jurassic time of these

different climatic conditions likely favored recycling

process.

The chemical weathering of such rocks under hot, epi-

sodically humid climate with dry season, would produce

illitization of silicate minerals, oxidation of iron and con-

centration of quartz in thick soil profiles, that were later

denudated by fluvial erosion, producing relatively mature,

quartz-rich red deposits. Moreover, palaeocurrent analysis

clearly indicates that terrigenous clastic rocks derived from

rapid erosion of highlands located to the N, NW and W of

the present-day outcrops of the Calabria-Peloritani Arc

realms (Mongelli et al. 2006; Critelli et al. 2008; Perri et al.

2008a, b).

The reaction in which smectite is a reactant and illite a

product, recognized to occur over a predictable range of

depth in mudrocks, is here used as a comparative ‘‘geo-

thermometer’’ jointly with the illite crystallinity value

(IC). Usually, the smectite-to-illite reaction concerns the

diagenetic range of sample formation, and the illite

‘‘crystallinity’’ and the mica polytype 2M1 percentage

variation mainly applies to the early stages of metamor-

phism, i.e., very low (anchizone) and low (epizone)

grades (Chamley 1995). The basin maturity chart (BMC;

Merriman and Frey 1999), that shows correlation of

reaction progress in the smectite-I–S-illite series and IC

with temperature, was adopted to evaluate temperatures

based on clay mineral evolution in the M.te di Gioiosa

succession. Thus, the diagenetic grade and the estimated

temperature experienced by the mudrocks, obtained by

clay mineral geothermometers as the percentage of illitic

layers in I–S mixed layers and the illite crystallinity

values (BMC; Merriman and Frey 1999), is in the range

of 100–150�C. Starting from this temperature, and based

on geothermal gradient of 20–30�C Km-1 (Vignaroli

et al. 2008 and reference therein), the diagenetic/tectonic

evolution for the M.te di Gioiosa stratigraphic succession

should correspond to a lithostatic/tectonic loading of

about 4–5 km.

Acknowledgments This research has been carried out within the

MIUR-COFIN Project 2001.04.5835 ‘Age and characteristics of the

Verrucano-type deposits from the Northern Apennines to the Betic

Cordilleras: consequences for the palaeogeographic and structural

evolution of the central-western Mediterranean Alpine Chains’

(support to V. Perrone), MIUR-ex60% Projects (Palaeogeographic

and Palaeotectonic Evolution of the Circum-Mediterranean Orogenic

Belts, 2001–2005; and Relationships between Tectonic Accretion,

Volcanism and Clastic Sedimentation within the Circum-Mediterra-

nean Orogenic Belts, 2006; Resp. S. Critelli) and the 2006–2008

MIUR-PRIN Project 2006.04.8397 ‘The Cenozoic clastic sedimen-

tation within the circum-Mediterranean orogenic belts: implications

for palaeogeographic and palaeotectonic evolution’ (Resp. S. Critelli).

The authors are indebted to Udo Zimmermann, an anonymous ref-

eree, the Topic Editor Heinrich Bahlburg and the Editor in Chief

Wolf-Christian Dullo for their reviews and suggestions on the

manuscript.

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