SEDGEO-04926; No of Pages 13

Sedimentary Geology xxx (2015) xxx–xxx

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Sedimentary Geology

journal homepage: www.elsevier.com/locate/sedgeo

Sediment generation in humid Mediterranean setting: Grain-size and

source-rock control on sediment geochemistry and mineralogy
(Sila Massif, Calabria)
Hilmar von Eynatten a,⁎, Raimon Tolosana-Delgado b, Volker Karius a, Kai Bachmann b, Luca Caracciolo c
a
Geowissenschaftliches Zentrum der Georg-August-Universität Göttingen, Abteilung Sedimentologie/Umweltgeologie, Göttingen, Germany
b
Helmholtz Institute Freiberg for Resource Technology, Freiberg, Germany
c
Chemostrat Ltd., Welshpool, UK

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

Article history: Grain-size control on sediment composition is investigated in modern proximal sediment from the Sila Massif,
Received 3 July 2015 where basic to felsic intrusive rocks are exposed in a Mediterranean humid–temperate upland climate. Samples
Received in revised form 15 October 2015 were taken from small creeks and weathering profiles from three areas reflecting different bed rock compositions.
Accepted 19 October 2015
Samples were separated into eleven grain size fractions from very coarse sand to clay and analyzed by (i) X-ray
Available online xxxx
fluorescence for chemical composition and (ii) X-ray diffraction and Mineral Liberation Analysis for mineralogical
Keywords:
composition. The chemical composition vs. grain size relations were modeled by compositional linear regression.
Geochemistry Mineralogical composition of selected samples is used to substantiate the interpretations based on geochemistry.
Mineralogy Results: reveal a high degree of chemical weathering with chemical index of alteration (CIA) up to 92. High CIA
Chemical weathering values are restricted to the fine-grained fractions, while sand-sized sediment average at low to moderate CIA values
Comminution (~60). Although strongly weathered, the three sample suites reflecting basic to felsic plutonic bed rock can be ef-
Provenance fectively discriminated across all grain-size classes using trace elements such as V, Rb, and Sr. Linear trend model-
Compositional linear regression ing and mineralogical data reflect similar patterns for all sample suites implying similar processes independent of
source rock composition. This includes overall decrease of quartz and K-feldspar over the full grain-size range from
very coarse sand to clay, which is contrasted by overall increase of sheet silicates from coarse to fine. Among the
latter, increase of clay minerals strongly outpaces the increase of micas in silt to clay fractions. A more complex
behavior is shown by plagioclase, which is most abundant in intermediate grain-size fractions for all sample suites.
This is likely caused by initial hydrolysis along cleavage and twinning planes and subsequent breakage of plagioclase
crystals into smaller fragments. Towards finer grain size, intense hydrolysis has destroyed most feldspars.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction as specific methodological constraints (e.g., microscopic determination

The chemical and mineralogical compositions of sediments and sed-
imentary rocks are strongly controlled by grain size (e.g. Blatt et al.,
1972; Basu, 1976). Other factors include source rock composition,
weathering, and physical as well as chemical processes that modify the
sediment while being transported from source to sink (e.g. Johnsson,
1993). The effect of grain size is generally thought to exceed the impact
of all other control factors on the variability of sediment composition
(e.g. Garzanti et al., 2011; Bloemsma et al., 2012). Nevertheless, many
studies inferring geologic or paleoclimatic conditions from sediment
characteristics do not consider grain size influence adequately.
The high relevance of grain-size for analyzing sediment composition
is contrasted by the fact that analyzing the entire grain-size spectrum is
often impossible, due to limitations of the accessible rock record as well
⁎ Corresponding author.
E-mail address: hilmar.von.eynatten@geo.uni-goettingen.de (H. von Eynatten).
of framework grains or heavy minerals is restricted to certain grain-
size ranges). Therefore, classic approaches to infer geological conditions
from sediment composition typically rely on data obtained from a given
narrow grain size range (e.g. Basu et al., 1975; Ingersoll et al., 1984;
Morton and Hallsworth, 1994). The shortcomings of such approaches
have been recently outlined by, for instance, Garzanti et al. (2009).
Therefore, comparing data obtained from different grain size fractions
or from sediment samples with contrasting grain size distributions inev-
itably requires an understanding of the compositional relations across
grain size grades. If these relations are controlled by purely physical pro-
cesses such as hydrodynamics or mechanical comminution, relatively
simple empirical or numerical models can be used to correct for the
grain-size dependent control on composition (e.g. Garzanti et al., 2009;
von Eynatten et al., 2012). For complex interactions of chemical and
physical processes, which must be considered the rule rather than the
exception in natural systems, Bloemsma et al. (2012) developed a statis-
tical method to separate the grain-size dependent part of compositional

http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
0037-0738/© 2015 Elsevier B.V. All rights reserved.

Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
2 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx
variation from a residual part, which reflects other controlling factors
such as provenance or diagenesis. Application of this tool revealed that
trends of grain size vs. composition strongly depend on the specific geo-
logical setting, implying that more empirical studies and models are
needed to better understand individual settings.
The aim of the paper is to describe and quantify the effects of grain
size and source-rock lithology on geochemical and mineralogical
compositions of sediments in a specific case study. The samples were
taken from three areas of the humid–temperate Sila Massif, southern
Italy, composed of contrasting basic to felsic plutonic source rocks. A
broad grain size spectrum covering more than three orders of magni-
tude from very coarse sand to clay is considered. Previous studies
have documented significant chemical weathering of soils and sediment
in the Sila Massif (e.g. Scarciglia et al., 2007). In a first step, weathering
and provenance effects on sediment composition, as well as their varia-
tions across the grain size grades from coarse to fine are evaluated. In a
second step, the results are compared to a previous study (von Eynatten
et al., 2012) from a highly contrasting climatic setting where chemical
weathering is negligible and thus mechanical comminution controls
sediment composition across grain-size grades.
The study is essentially based on geochemical data because they can
be obtained easily and precisely for the full grain size spectrum from
very coarse sand to clay, which covers N 95% of the global clastic sedi-
ment budget given that conglomerates and breccias comprise only a
few percent of the total clastic sediment record (e.g. Pettijohn, 1975).
Mineralogical composition is obtained by X-ray diffraction for selected
samples and grain-size fractions to verify interpretations based on geo-
chemical data. Moreover, Mineral Liberation Analysis (MLA) has been
tested on some samples because it potentially provides a tool to analyze
mineral composition over a large grain size range.
2. Study area and sampling strategy
The study area is located in the uplands of the Sila Massif in northern
Calabria (southern Italy) at altitudes between approx. 1150 and
1600 masl, characterized by a smooth topography with gentle hills
and slightly incised streams in between. It has a typical Mediterranean
humid–temperate upland climate, characterized by mean annual pre-
cipitation of 1400 to 1800 mm and mean annual temperature of
10–12 °C, with mean monthly temperatures ranging between − 1 °C
and 18 °C (cf. Scarciglia et al., 2012). The climatic and geomorphological
conditions have caused deep and intense weathering of the respective
bed rocks, which has been investigated in numerous weathering pro-
files (e.g. Le Pera and Sorriso-Valvo, 2000; Scarciglia et al., 2007), and
is reflected in the sediments exported from the Sila Massif through the
main drainage systems, i.e. the Crati and Neto River basins (e.g. Le
Pera et al., 2001).
The Calabrian Massif constitutes an allochthonous crustal segment
of the western Variscan belt in Europe, exposed in a structurally high
position between the Alpine Mesozoic to Cenozoic sedimentary nappe
piles of the Apennines to the North and the Maghrebides in Sicily to
the Southwest (Ayuso et al., 1994; Graessner et al., 2000). The Sila
Massif forms the northern part of the Calabrian Massif and is mainly
composed of high-grade (granulite facies) metapelites in the West
and Southwest, low to medium-grade metasedimentary rocks in the
East, and the Sila Batholith comprising most of the central part of the
Sila Massif (Fig. 1). Peak metamorphism is dated at around 300 Ma,
roughly coeval to the Late Variscan intrusion ages of the batholith
(Graessner et al., 2000). The Sila Batholith is a complex intrusive body
composed of variable plutonic rocks that range from granites and grano-
diorites to tonalite, diorite, and even gabbroic rocks (Messina et al.,
1991; Ayuso et al., 1994; Caggianelli et al., 1994). After intrusion the
plutons cooled and were exhumed to mid-crustal levels in Permian to
Triassic time (Ayuso et al., 1994; Graessner et al., 2000). Final exhuma-
tion of the Sila Massif is constrained by zircon and apatite fission-track
analysis to Oligocene to Mid-Miocene time (35 to 15 Ma; Thomson,
Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
1994). Late Pleistocene to Holocene catchment-averaged erosion rates
for the flat uplands are low, scattering around 0.1 mm/a as inferred
from cosmogenic nuclide data (Olivetti et al., 2012).
The samples were collected in June 2010 (RT3) and September 2013
(RT4). They derive from three different areas of the Sila Massif, which
were selected to represent the diverse range of the Sila Batholith from
felsic to basic plutonic rocks. From north to south, the first area is locat-
ed to the northeast of Lago Cecita and exposes felsic rocks of granodio-
rite to monzogranite composition (i.e. cordierite-bearing biotite–
muscovite granodiorite to monzogranite according to Messina et al.,
1991; peraluminous granite according to Graessner et al., 2000). These
rocks range in SiO2 content from 68 to 74 wt.% (Ayuso et al., 1994)
and constitute the most felsic sample suite, termed F2 (Fig. 1). The sec-
ond area is located around Carlo Magno and Silvana Mansio north of
Lago Arvo. It belongs to the widely exposed hornblende and biotite-
bearing tonalites to granodiorites, which range in SiO2 content from
60 to 71 wt.% (Messina et al., 1991; Ayuso et al., 1994). The selected
area constitutes the felsic to intermediate sample suite, termed F1
(Fig. 1). Some bedrock samples of this area indicate a dominant compo-
sition of F1 bedrocks in the less felsic part of the tonalites to granodio-
rites with SiO2 content around 61 to 62%. The third area is located
directly northeast of Lago Arvo around the village of Rovale and exposes
basic to intermediate rocks of the so-called Rovale Zone or Complex.
This small area (~15 km2) consists of gabbroic rocks (norites, amphibole
gabbros; 42–49 wt.% SiO2, 18–26 wt.% Al2O3) in its western part close to
Rovale, while in its eastern part plagioclase and amphibole-rich diorites
and tonalites prevail (52–57 wt.% SiO2, 17–18 wt.% Al2O3), with small
local gabbroic bodies (Caggianelli et al., 1994). This area constitutes
the basic to intermediate sampling area of the study, termed B (Fig. 1).
Two types of samples have been collected: modern sediment from
small proximal creeks (Sed, N = 10) as well as material from
weathering profiles or grus exposed in roadcuts (WP, N = 6). Small
creek means channel width less than 2 m. Sampling was intended to
cover a broad grain-size spectrum from very coarse sand to clay from
each sampling site. Therefore, Sed-samples may represent a mixture
of up to three subsamples taken from a small area of no more than
approx. 20 m2. Grus samples were taken from the debris cones devel-
oped along roadcuts through deeply disintegrated granitoid bed rock.
While sample suites F1 and F2 comprise both Sed and WP samples
(altogether seven samples for each suite), only two sediment samples
are available from sampling suite B (Table 1).
3. Methods
Samples were separated in up to eleven grain-size fractions ranging
from very coarse sand (1 to 2 mm, −1 b Φ b 0) to clay (b 2 μm, Φ N 9),
with Φ being the negative logarithm of the grain diameter d to the basis
of 2 (Φ = −log2 d). Grain size separation was achieved in one-Φ-unit
steps by wet sieving of the sand-sized fractions (− 1 b Φ b 4), and by
gravity settling for all finer fractions (Φ N 4). Each separation step of
the fine-grained fractions in Atterberg-cylinders was repeated 8 to 14
times until quantitative separation of the respective grain-size fraction
was achieved. The remaining suspension was vacuum-filtered through
0.2 μm cellulose acetate filters. Therefore, the finest fraction actually
represents the grain size fraction 9 b Φ b 12.
Each sediment grain-size fraction was powdered, fused using
lithium metaborate, and subsequently analyzed by X-ray fluorescence
(XRF) method using a PANalytical AXIOS Advanced sequential X-ray
spectrometer at the Geoscience Center Göttingen. All samples and
grain size fractions were analyzed for ten major element oxides (SiO2,
Al2O3, TiO2, Fe2Otot
3 = total iron calculated as Fe2O3, MnO, MgO, CaO,
Na2O, K2O, P2O5), the loss on ignition (LOI), and 16 trace elements
(Ba, Co, Cr, Cu, Ga, Nb, Nd, Ni, Pb, Rb, Sc, Sr, V, Y, Zn, Zr). The RT4 samples
were additionally analyzed for Ce, Hf, La, Mo, Sm, Th, U, and Yb. The
elemental concentrations of all samples and grain-size fractions are
available in the Supplementary data file.
 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx 3

Fig. 1. Simplified geological map of the study area, modified from Messina et al. (1991) and Borelli et al. (2014).

Analytical precision is typically in the range of 1% for major elements of our samples. The only exception is Zr: although all four reference
and 5% for trace elements. Accuracy of measurements was tested materials have comparable Zr concentrations (96–180 ppm), the de-
against internationally certified reference materials with values for JB- viations for JA-2, JB-3 and JR-1 are only 2% and thus strongly contrast
3, JA-2, and JR-1 taken from Imai et al. (1995) and values for JG-2 the high deviation for JG-2.
taken from Guevara et al. (2001). Accuracy is better than 3% for all Selected samples were analyzed by X-ray diffraction (XRD) for identi-
major oxides except for TiO2 (JG-2, 6%), MnO (JA-2, 4%, JG-2, 14%), fication and quantification of mineral phases. Individual grain size frac-
MgO (JA-2, 4%, JR-1, 8%), P2O5 (JA-2, 5%, JG-2, 46%, JR-1, 14%) and tions were wet milled with a McCrone micronising mill in distilled
Fe2Otot
3 (JG-2, 7%), and better than 8% for all trace elements except water, evaporated to dryness at 60 °C, and pulverized using agate mortar.
for Ba (JR-1, 15%), Ce (JB-3, 12%), Ga (JR-1, 12%), Nb (JG-2, 31%), Rb 10% ZnO was admixed as internal standard. X-ray diffraction analyses
(JB-3, 14%), Sr (JG-2, 75%), Zn (JB-3, 9%) and Zr (JG-2, 45%). Observed were performed on a Philips X'Pert MPD, equipped with a PW3050
deviations higher than 10% are mostly related to concentrations near Goniometer, and CuKα radiation. Qualitative phase analysis was achieved
the detection limit and/or below or at the lower end of the data range using a search match routine of the program X'Pert Highscore (Version
2.2a) (Panalytical B.V., 2006). Quantitative phase analysis was performed
with Rietveld refinements based on the diffraction data using the pro-
gram AutoQuan (Version 2.80) (GE Inspection Technologies, 2014).
Table 1 All Mineral Liberation Analysis (MLA) measurements were run on a
List of samples including bed rock suite, sample type, coordinates and approximate eleva- scanning electron microscope FEI Quanta 650F equipped with two
tion (Sed = sediment from small creeks; WP = weathering profile or grus from roadcuts).
Bruker Quantax X-Flash 5030 Silicon Drift Detectors (SDD) and the spe-
Sample Suite Type N–coordinates–E Elevation cific software MLA Suite 3.1.4 for automated data acquisition. The MLA
RT3-1 F1 WP 39°16′06.17″ 16°32′01.42″ ~1480 masl measurements were carried out at the Geometallurgy Laboratory at
RT3-2 F1 Sed 39°16′06.61″ 16°31′59.36″ ~1480 masl the Helmholtz Institute Freiberg. More detailed information about the
RT3-3A F1 WP 39°16′49.60″ 16°32′18.91″ ~1570 masl functionality of the MLA system can be found in Fandrich et al. (2007).
RT3-3B F1 WP 39°16′49.60″ 16°32′18.91″ ~1570 masl The operating conditions used for this study are listed in Table 2. All
RT3-5A F2 Sed 39°23′14.85″ 16°33′12.04″ ~1170 masl
RT3-6 F2 Sed 39°22′12.59″ 16°31′30.34″ ~1150 masl
measured datasets were processed with the MLA Image Processing soft-
RT4-3 F1 Sed 39°16′48.28″ 16°34′36.48″ ~1580 masl ware, version 3.1.4. A coincidence threshold of 90% with the standard
RT4-4 F1 Sed 39°17′34.23″ 16°31′16.66″ ~1530 masl spectra was used for the classification of the measurements.
RT4-5 F1 Sed 39°17′36.39″ 16°31′23.51″ ~1520 masl The statistical techniques applied are fundamentally based on the
RT4-6 B Sed 39°15′10.33″ 16°32′10.70″ ~1330 masl
log-ratio approach to compositional data, as introduced by Aitchison
RT4-7 B Sed 39°15′17.02″ 16°33′39.36″ ~1380 masl
RT4-10 F2 WP 39°23′21.79″ 16°33′44.29″ ~1270 masl (1986). This includes the evaluation of the covariance structure via
RT4-11 F2 Sed 39°24′17.18″ 16°36′26.30″ ~1430 masl biplot analysis, the calculation of geometric means and predictive re-
RT4-12 F2 Sed 39°23′03.87″ 16°36′51.97″ ~1390 masl gions, and the linear regression model. All this is performed on trans-
RT4-13 F2 WP 39°23′42.77″ 16°36′03.80″ ~1320 masl formed data, i.e. the data are transferred from the constrained
RT4-15 F2 WP 39°23′22.18″ 16°33′43.33″ ~1270 masl
compositional space to the Euclidean space by centered log-ratio

Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
4 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx

Table 2 4. Results
Summary of MLA parameters for samples RT4-3, RT4-4, and RT4-7.

SEM parameters MLA parameters 4.1. Major and trace element concentrations and patterns
Mode GXMAP Scan speed 16
Voltage (kV) 25 Resolution (pixels) 500 × 500 The variability of the major element oxide concentrations for the
Working dist. (mm) 12 Pixel size (μm/px) 1.6 three sample suites B, F1, and F2 against the eleven separated grain-
Probe current (nA) 10 Acq. time (ms) 6 size fractions from very coarse sand to clay is illustrated in Fig. 2. Con-
Spot size 5.84 Min. EDX-count 2000
trasts between the three suites are clearly visible for some elements
HFW (μm) 800 Step size (px) 6×6
Brightness 83.5 GXMAP trigger 25–255 (e.g. Si, Ca, K, Fe) but typically converge or even disappear towards
Contrast 26.2 Min. particle size (px) 10 finer grain size. Some major element oxides show general trends such
BSE calib. Au 252 Min. grain size (px) 4 as overall decrease of SiO2 and increase of Al2O3 and loss on ignition
(LOI) with decreasing grain size. Other elements display specific pat-
terns for individual parts of the grain size spectrum for some or all of
the three sample suites (e.g. Na, Ca, P, Ti, Fe). For instance, CaO displays
transformation (clr; Aitchison, 1986). The transformation frees the data a more or less pronounced increase in the coarser fractions from very
from the constant-sum constraint implying, for instance, that incremen- coarse sand to very fine sand and a decrease in the fine fractions from
tal changes in concentrations in clr-scale are independent of the respec- very coarse silt to clay. The latter is very pronounced for suites B and
tive level of concentration, i.e. the clr-scale provides a translation- F1. Maximum CaO concentrations are thus measured in the very fine
invariant measure of the degree of change (e.g. von Eynatten et al., sand to very coarse silt fractions (3 b Φ b 5) for all sample suites
2003a). For linear regression, the transformation is followed by standard (Fig. 2). A similar observation is made for Na2O but is restricted to the
multiple regression techniques to estimate the coefficients of the compo- intermediate to felsic sample suites F1 and F2. In the basic sample
sitional linear trend. The trend may include steps if distinct breaks are ob- suite Fe2O3, TiO2, and MnO are peaking in the fine to very fine sand
served at certain grain-size thresholds. Methodological details are range (2 b Φ b 4), accompanied by a small trough in SiO2 and MgO in
described elsewhere (Tolosana-Delgado and von Eynatten, 2009; this range. P2O5 is peaking in very coarse silt (4 b Φ b 5) for all sample
Tolosana-Delgado and van den Boogart, 2011; von Eynatten et al., 2012; suites, decreases in the coarse to fine silt fractions and then again nota-
and references therein). bly increases in the clay fraction (Φ N 9) (Fig. 2). Upon visual inspection

Fig. 2. Major element raw data concentrations in oxide wt.% for all three sample suites of the Sila Massif (blue = B, gabbro to diorite; red = F1, tonalites to granodiorites; brown = F2,
granodiorite to monzogranite) versus grain size in Φ-grades from very coarse sand (−1 b Φ b 0) to clay (Φ N 9). The variability of individual samples of a grain-size class is illustrated
in box plots for suites F1 and F2 (N = 7 each), while sample suite B (N = 2) is represented by stippled lines with solid line reflecting the mean. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)

Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx 5

of the raw percentage data K2O appears to discriminate best between all
suites across the full grain size range, while MgO separates best the basic
suite B from the rest, and CaO separates best F1 from F2.
Trace element concentrations typically vary by an order of magni-
tude across sample suites and grain-size range (Fig. 3). Some elements
show general increase with decreasing grain size for all sample suites
(Th, Pb, U, Ga) while three more elements show this trend for F1 and
F2 only (Zn, Cr, Nb). Zr and Hf peak in the very coarse silt fraction for
all sample suites and Zr/Hf ratios scatter around 40 without grain-size
dependence. Y and the light (LREE: La, Ce) and middle rare earth ele-
ments (MREE: Sm, Nd) all peak in the very fine sand to very coarse
silt fractions (3 b Φ b 5) for all sample suites, however, in F2 the concen-
trations of these elements stay high over the entire fine range (Fig. 3). V
and Nb peak at 3 b Φ b 5 in the basic sample suite only. Upon visual in-
spection Th, U, and Rb appear to discriminate best between the three
sample suites across the full grain size range. V nicely separates the
basic suite from the rest, while Sr and Ba nicely separate F1 from F2
across the full grain size range (Fig. 3).
4.2. Covariance structure
Evaluation of the covariance structure of the dataset is performed
using compositional biplots, which provide a 2D-representation of
multivariate compositional data based on principal components (e.g.
Aitchison, 1990; von Eynatten et al., 2003b). The data set has been
transformed using centered log-ratio transformation (clr) to account
for the specific compositional nature of geochemical data (Aitchison,
1986). This implies that the center of the biplot corresponds to the geo-
metric mean of the dataset.
The major element biplot of the entire data set (Fig. 4A) reveals a
strong grouping depending on sample suite and grain size. The first
principal component (PC1, x-axis) captures ~49% of the total variability
and is characterized by strong positive loadings of K and Na and nega-
tive loadings of Mg, Ti, Fe, P, Ca, and LOI. The second principal
component (PC2, y-axis) captures ~ 22% of the total variability and is
characterized by strong positive loading of LOI and strong negative load-
ing of CaO. PC1 effectively separates sediments from basic source rocks
from intermediate to felsic ones (i.e. sample suites B vs. F1 vs. F2;
Fig. 4A). This, however, holds only for grain size fractions coarser than
medium silt (i.e. Φ ≤ 6). Towards finer grain size the contrast between
the sample suites decreases with decreasing scores of PC1 and increas-
ing scores of PC2. PC2 groups the very coarse silt to sand fractions for
each sample suite, and effectively orders the finer grain size fractions
by increasing PC2 scores (brown arrows in Fig. 4).
The mixed biplot of major elements and selected trace elements
(Fig. 4B) reveals a roughly similar picture. While V behaves like the
mafic elements Mg and Ti (strong negative loading on PC1), Rb, Y and
Zr have positive loadings on PC1. Zr also has strong negative loading
on PC2. Zn appears to be strongly related to the high LOI of the finest
fractions (positive loading on PC2). The separation of the three sample
suites appears even more pronounced in the mixed biplot. Moreover,
grain size separation is enhanced. Fine-grained fractions still have the
highest scores on PC2, while the coarser fractions are now better differ-
entiated by PC2 (Fig. 4B): the lowest scores in each suite are restricted to
very fine sand and very coarse silt (3 ≤ Φ b 5), while the coarser sand
fractions yield intermediate scores on PC2.
Comparing only the two granitoid suites F1 and F2 allows for focus-
ing the biplot analysis on features controlled by parameters other than
source rock, such as grain-size and/or sample type. A threefold structure
becomes visible that is predominantly controlled by grain size (Fig. 5):
(i) very coarse to medium sand (Φ ≤ 2) is mainly characterized by pos-
itive scores on PC1 and negative scores on PC2 and PC3 translating to
high proportions of Si, Na, K, and Rb, (ii) very fine sand and very coarse
silt (3 ≤ Φ b 5) is mainly characterized by positive scores on PC1, PC2
and PC3 translating to high proportions of Ca, Zr, Y and P, and (iii)
medium silt to clay (Φ N 6) characterized by negative scores on PC1
while PC2 and PC3 are rather unspecific. The latter translates to
high proportions of Zn, V, Ti, Mg, Fe, and P. In contrast, the sample

Fig. 3. Trace element raw data concentrations in ppm (note log-scale) for all three sample suites of the Sila Massif (blue = B, gabbro to diorite; red = F1, tonalites to granodiorites;
brown = F2, granodiorite to monzogranite) versus grain size in Φ-grades from very coarse sand (−1 b Φ b 0) to clay (Φ N 9). The variability of individual samples of a grain-size class
is illustrated in box plots for suites F1 and F2 (N = 7 each), while sample suite B (N = 2) is represented by stippled lines with solid line reflecting the mean. For key to box plots see
Fig. 2. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
6 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx

Fig. 4. Compositional biplots of the clr-transformed geochemical data (Aitchison, 1990). Symbols reflect sample suite (B, F1, F2) and sample type (Sed = sediment, WP = weathering
profile), color coding refers to grain size class in Φ-units from very coarse sand (yellow; −1 ≤ Φ b 0) to clay (black; Φ N 9). A given value x thus represents the grain-size class of
x ≤ Φ b x + 1. Both biplots indicate sample position in the two dimensional projection based on the first (x-axis, PC-1) and second (y-axis, PC-2) principal components, as well as the var-
iables and their loadings on the respective principal component. Left side (A) shows the major element oxide data including loss on ignition (LOI). Right side (B) shows the same major
elements along with selected trace elements (Rb, Sr, V, Y, Zn, Zr). Numbers in italics refer to percentages of the total variability explained by PC1 and PC2. (For interpretation of the ref-
erences to color in this figure legend, the reader is referred to the web version of this article.)

type (i.e. sediment from creek vs. weathering profile) does not reveal
systematic differences in the biplots. However, the fine-grained
fractions from the weathering profile of suite F2 (WP, triangles
upside down) appear to be separated from their sediment equivalents
(Sed, rhombs) by high proportions of Y relative to e.g. Ca. This contrast
Fig. 5. Compositional biplots of major element oxides (excluding LOI) and selected trace
elements (Rb, Sr, V, Y, Zn, Zr) for the intermediate to felsic suites F1 and F2. The composi-
tional contrast that still exists between F1 and F2 has been minimized by matching the
means of each suite (i.e. by perturbing one data set by the inverse geometric mean of
the other). Panel (A) shows the first (x-axis) vs. second (y-axis) principal components,
(B) shows the first (x-axis) vs. third (y-axis) principal components. Numbers in italics
refer to percentages of the total variability explained by PC1 and PC2 (A) or by PC1 and
PC3 (B). For key to symbols and colors see Fig. 4. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)
explains the high variance for F2 samples regarding Y and REE concen-
trations (Fig. 3, third row).
4.3. Linear regression model
The modeling has been restricted to the major elements (including
LOI) and the intermediate to felsic suites F1 and F2, as only these pro-
vide reasonable numbers of samples. Constraints on the linear regres-
sion model like (i) similar slope over the full grain-size range and (ii)
distinct steps at Φ = 4 and Φ = 8, as applied in a previous study (von
Eynatten et al., 2012), resulted in a poor fitting of the data especially
for Ca, Na, P as well as Si and K. The raw data already point at such misfit
because some elements show distinct breaks in increase/decrease pat-
terns at around Φ = 4 (Fig. 2). Moreover, the three-pole structure
governed by grain size as revealed in Fig. 5A calls for modifications
from a simple uniform linear trend over the full grain-size range. We,
therefore, chose model constraints which account for the observed
breaks in slope, i.e. the slopes are allowed to be different for the sand
fraction (Φ b 4) compared to the silt-clay fraction (Φ N 4). Further, a
possible step has been allocated at Φ = 4 but no further steps appear
necessary. The regressions are calculated separately for F1 and F2 with
intercepts as well as the step at Φ = 4 being independent, while the
slopes are forced to be equal for F1 and F2.
The resulting linear trend indicates a reasonable fit to the composi-
tional range of sample suites F1 and F2 for all major elements except
for P2O5 (Fig. 6). The relatively poor linear fit for P is due to its double
peaking in very coarse silt and clay with a significant trough in between.
Well adjusted negative slopes for the full grain-size range (i.e. decreas-
ing relative concentration with decreasing grain size) are obtained for
Si, Na, and K, while general positive slopes are obtained for Fe, Mg, Ti,
and LOI (Fig. 7). In contrast, Ca and Al reveal opposing slopes for sand
and silt-clay: Ca shows distinct increase from coarse sand to very fine
sand and very coarse silt, and then markedly decreases towards clay,
while Al behaves vice versa (Fig. 6). However, Al exhibits very small
slopes in both parts of the grain-size spectrum implying relatively
small changes over the full grain-size spectrum.
4.4. Mineralogical composition
The XRD analysis of three selected samples covers the grain-size
spectrum from coarse sand to clay as well as all three sample suites B,
F1, and F2. Inferred mineral compositions include quartz, K-feldspar
(orthoclase, microcline), plagioclase (almost pure albite to Ca-rich vari-
eties), amphibole (hornblende), pyroxene (enstatite, augite), Ti-phases

Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx 7

Fig. 6. Linear regression model (solid lines) adjusted for the F1 (red) and F2 (brown) sample suites against grain size classes, displayed in clr-scale for each of the 10 variables included in
the model (9 major elements plus LOI) separately. For key to box plots see Fig. 2. (For interpretation of the references to color in this figure legend, the reader is referred to the web version
of this article.)

(ilmenite, rutile), muscovite, biotite, chlorite, clay minerals (illite, smec-
tite, kaolinite), and gibbsite. Quantitative phase models are well adjust-
ed if the quality parameter 1–ρ of the Rietveld refinement is approx. 1%.
This criterion is reasonably fulfilled for the sample suites F1 and F2 (1–ρ:
0.8%–3.5%) but less well for sample suite B (1–ρ: 2.5%–6.6%). For this
sample qualitative analysis revealed a Mg-rich amphibole phase (e.g.
cummingtonite) which could not be quantified by AutoQuan due to
the lack of an appropriate structural model. As a consequence, the amor-
phous content in this sample is calculated to ~10% within the sand and
coarse silt fractions which is likely related to the missing amphibole
phase. Because structural phase models do not necessarily reflect the
real structure of the mineral in the sample, especially in the case of high-
ly weathered materials, quantitative Rietveld modeling delivered partly
ambiguous results for these highly weathered materials, especially in
the finer-grained fractions. We therefore present, besides quartz, quan-
titative data for the summed values of the clearly determined and quan-
tified phase groups, i.e. quartz, total K-feldspar, total plagioclase, total
Fig. 7. Graphical representation of the model parameters slope in the sand fraction (Φ b 4)
vs. slope in the silt to clay fraction (Φ N 4). Dotted line reflects 1:1 relation of the slopes.
chain silicates, total mica including chlorite, and total clay minerals
(Fig. 8). Moreover, gibbsite and Ti-phases are listed, if appropriate.
In general, mineral proportions are highly variable with respect to
both sample suites and grain size. As expected, clay minerals and mica
increase from coarse sand to clay. Increase of clay minerals is strongest
in the finest fraction (~60–75%). Only in the F2 samples micas (mainly
muscovite) decrease relatively from fine silt to clay, which is, however,
more than compensated by the strong increase of clay minerals (~60%)
and gibbsite (~10%). Quartz content decreases continuously from coarse
(~ 22% in B, ~ 40% in F1, F2) to fine (b 5%). The same is observed for
K-feldspar, starting from ~ 20%, except for the B-sample where
K-feldspar is pretty low. Plagioclase content is highest (~ 20–30%) in
the very fine sand and/or coarse silt fractions for all samples, and then
decreases dramatically towards finer fractions. Amphibole and
pyroxene decrease strongly from coarse (~ 25%) to fine (b 5%) for the
B-sample, are relatively low in F1 (max. ~5%, mostly hornblende) and
almost lacking in F2. Ti-phases are significant in the B-sample only
(max. ~5%), and peak in very fine sand (Fig. 8).
Results for Mineral Liberation Analysis (MLA) are restricted to the
sand-sized fractions of samples RT4-3 and RT4-4 (F1) as well as RT4-7
(B). The mineral phases (or groups) identified and quantified include
quartz, K-feldspar, albite, plagioclase, amphibole (mainly hornblende),
pyroxene (augite, pigeonite), biotite, chlorite, muscovite, clay minerals,
Ti-minerals (e.g. ilmenite, titanite, TiO2-polymorphs), apatite, zircon,
and other accessories (e.g. monazite, magnetite, carbonate). The miner-
al concentrations for each sample and the trends from coarse sand to
very fine sand are listed in Table 3. Separation between suites B and
F1 is straightforward due to strongly contrasting proportions of quartz,
K-feldspar, and chain silicates (amphiboles + pyroxenes). Very good
discrimination within the sand fractions is thus obtained by the quartz
to chain silicates and K-feldspar to plagioclase ratios (Table 3). Very
fine sand typically shows decrease of quartz and K-feldspar and increase
of plagioclase and amphibole compared to coarse sand. Heavy minerals
such as apatite, zircon, and Ti-minerals increase by factors of ~2 to 17 in
very fine sand compared to coarse sand.
Comparison of XRD vs. MLA data for samples RT4-3 (suite F1) and
RT4-7 (suite B), for which both methods were applied on two grain-
size fractions each, yields an overall good agreement of the respective
mineral phases (Fig. 9). RT4-3 yields good agreement for all phases ex-
cept for muscovite, which yields lower values with MLA. RT4-7 yields
very good agreement for quartz, amphibole, K-feldspar, and clay min-
erals, good agreement for plagioclase, biotite + chlorite, and muscovite,

Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
8 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx

Fig. 8. Quantitative X-ray diffraction (XRD) results of three samples, one from each of the sample suites B (RT4-7), F1 (RT4-3), and F2 (RT4-11). For each sample five grain-size fractions
from coarse sand (0 b Φ b 1) to clay (Φ N 9) were analyzed and quantified. Mica includes biotite, muscovite, and chlorite; claymin includes illite, smectite, and kaolinite; gib = gibbsite;
ti-phases include ilmenite and rutile. Error bars include 3 sigma errors of Rietveld refinements. Note different scale for concentrations N32%.

but some contrast in the case of pyroxene and Ti-minerals (especially
for coarse sand; Fig. 9). The higher values for pyroxene in the MLA
dataset may derive from some problems in discriminating Al-poor am-
phiboles from pyroxene with this technique. Alternatively, Mg-rich
chain silicates have been observed in the XRD-spectra but could
not be quantified and may be as high as ~ 10% (see above). Taken
together, the data indicate reasonable consistency between the two
methods.
5. Discussion
5.1. Chemical weathering
Chemical weathering of silicate minerals such as feldspar or chain
silicates leads to exchange of cations of alkaline and alkaline earth ele-
ments for H+ via hydrolysis (e.g. Bahlburg and Dobrzinski, 2011). Min-
eralogically, this process is characterized by the transformation of the
original minerals into clay minerals, with kaolinite commonly reflecting
intense weathering and complete removal of mobile elements including
potassium. Chemical weathering may also mobilize silica, including
desilicification of clay minerals and formation of gibbsite (Vazques,
1981). Among the vast number of proxies for chemical weathering the
chemical index of alteration (CIA; Nesbitt and Young, 1982) is by far
the most popular. It essentially describes the degree of removal of
Ca2+, Na+, and K+, normalized to Al, through transformation of feld-
spars to clay minerals. Unweathered source rocks typically have CIA of
40–50 while extremely weathered materials entirely composed of, for
instance, kaolinite, gibbsite, and Fe-(hydr)oxides have CIA close to
100. Average pelitic rocks that typically experienced significant
weathering yield CIA of ~ 70 (e.g. CIA 70 for post-Archean Australian
shale, Taylor and McLennan, 1985; CIA 69 for Phanerozoic average cra-
tonic shale, Condie, 1993). It must be noted that CIA values or other
weathering indices do not exclusively depend on the degree of chemical
weathering. Other factors such as initial source rock composition

Table 3
Results of MLA analysis.

Sample RT4-3 RT4-4 RT4-7

Grain-size cs–vfsa cs–vfsa cs–vfsa

Quartz 40.5–20.2 38.2–19.2 22.7–11.3

K-feldspar 23.3–14.1 13.7–17.4 4.3–2.4
Albite 7.4–9.2 6.8–10.6 4.5–3.2
Plagioclase 5.1–11.9 9.6–16.1 (6.6)b 5.3–16.1
Amphibole 0.4–5.1 0.03–6.0 21.2–21.7 (26.3)b
Pyroxene 0.0–0.0 0.0–0.0 14.9–9.9
Biotite 7.4–11.4 10.8–7.1 (12.4)b 8.2–6.9
Chlorite 0.5–1.7 0.6–1.3 1.6–8.1
Muscovite 1.4–1.6 (2.4)b 2.5–1.7 2.8–1.7
Clay minerals 13.6–23.7 17.1–17.4 (14.1)b 11.6–13.5
Ti-minerals 0.10–0.39 0.25–0.86 2.2–4.5 (5.9)b
Apatite 0.14–0.29 0.20–1.25 0.44–0.63
Zircon 0.05–0.12 (0.03)b 0.03–0.54 0.02–0.06
Quartz/Σ feldspar 1.1–0.6 1.3–0.8 1.6–0.5
K-feldspar/plagioclasec 1.9–0.7 0.8–0.7 0.4–0.1
Quartz/chain silicatesd ~100–4.0 N100–3.2 0.6–0.4
Quartz/clay minerals 3.0–0.9 2.2–1.1 2.0–0.8
a
The values [wt.%] describe the trend from coarse sand (cs) to very fine sand (vfs).
b
Values in brackets refer to exceptions from the trend observed in medium or fine sand.
c
Albite included in plagioclase.
d
Chain silicates = amphibole + pyroxene.

Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx
Fig. 9. Comparison of results on mineral composition from X-ray diffraction (XRD) vs. Min-
eral Liberation Analysis (MLA) for two samples from suite F1 (RT4-3) and suite B (RT4-7).
Two grain-size fractions from each sample are available for comparison (qtz = quartz,
pla = plagioclase incl. albite, kf = K-feldspar, am = amphibole, px = pyroxene, bio = bi-
otite, chl = chlorite, clm = Σ clay minerals). For explanation see text.
(Nesbitt and Young, 1984), grain size (von Eynatten et al., 2012), or
provenance settings including e.g. sheet-silicate rich units or sediment
recycling (Garzanti and Resentini, 2015) are prone to add significant
variation to the calculated CIA values.
Fig. 10. Chemical index of alteration (CIA) for each grain-size fraction and each sample
suite B, F1, and F2. The variability of individual samples of a grain-size class is illustrated
in box plots for suites F1 and F2 (N = 7 each), while sample suite B (N = 2) is represented
by stippled lines with solid line reflecting the mean. For key to box plots see Fig. 2.
Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
9
Calculated CIA values for the Sila samples show a very wide range
from 55 to 92, i.e. from almost “fresh” to heavily weathered materials
(Fig. 10). There is no clear distinction between the three sample suites.
Nevertheless, the most felsic suite F2 tends to slightly lower CIA at the
coarse and fine tails of the grain-size range and the basic suite shows
slightly higher CIA from coarse silt to very fine silt (5 b Φ b 9; Fig. 10).
In general, CIA values show a pronounced increase with decreasing
grain size. However, within the sand fraction there is only little increase
from CIA 55–61 for very coarse sand to CIA 56–68 for very fine sand. The
average CIA for all sand fractions from all samples is 60. Very coarse silt
(4 b Φ b 5) is still relatively low in CIA (57–68; medians still around 60)
while all finer fractions mark a continuous increase up to the clay
fraction, which range in CIA from 77 to 92 with mean values between
84 and 88 for the three suites (Fig. 10). Average CIA for all the fine frac-
tions from coarse silt to clay (Φ N 5) is 75.4, which is higher than average
shale (see above).
The strong chemical weathering in the Sila Massif has long been
known and is described elsewhere. It is characterized by the develop-
ment of deep weathering profiles on granitoid bedrock (e.g. Le Pera
and Sorriso-Valvo, 2000), dissolution microtextures including intensely
etched quartz grains (e.g. Scarciglia et al., 2007), and the occurrence of
various neo-formed clay minerals such as illite–smectite mixed layers,
kaolinite, and halloysite (e.g. Borelli et al., 2014). Our data support this
through (i) high CIA up to 92 and (ii) high proportions of minerals indi-
cating strong chemical weathering such as kaolinite and gibbsite in the
finest sediment fractions.
Grain size dependence of chemical weathering indices was de-
scribed earlier, but has been typically restricted to broader categories
such as sand(stone) vs. mud(stone) (e.g. Ohta, 2008). The detailed
grain-size resolution obtained here fully confirms that comparing
weathering proxies from samples with different grain size distributions
is likely to produce biased results. The effect appears less relevant for
different grades of sand(stone) but highly relevant for comparison of
sand vs. mud and for comparison of different grades and mixtures of
silt to clay. For the latter, our data suggest strong contrast in CIA al-
though the source area is similar in terms of both bedrock type (for
each sample suite) and weathering conditions. This statement is crucial
given that many case studies have based their interpretations on rela-
tive subtle changes in weathering proxies like, for instance, 5 to
15 units in CIA (e.g. Nesbitt and Young, 1982; Passchier and Krissek,
2008; Bahlburg and Dobrzinski, 2011).
5.2. Source-rock discrimination
The three sample suites B, F1 and F2 reflect marked contrasts in bed-
rock mineralogy and geochemistry. The question is whether the sedi-
ments reflect these contrasts across the full grain size range despite
intense chemical alteration? Raw data concentrations and covariance
structure suggest high discriminative potential for K2O, MgO, and CaO,
as well as Rb, Th, U, V, Sc, Co, Ba, and Sr (Figs. 2 to 5). Because some of
these elements are sensitive to chemical weathering (e.g. Ca, Sr, Rb, K,
U), this observation implies that chemical weathering was not extreme
enough to fully destroy source rock signatures. Typical element ratios
used to discriminate sediments derived from basic vs. sediments de-
rived from felsic rocks such as Ba/Co, La/Co, La/Sc, or Th/Sc (e.g. Bhatia
and Crook, 1986; Cullers et al., 1988) almost completely separate sam-
ple suite B from the more felsic suites, like does Rb/Sc and Rb/Co. The
best separation between suite B and all other samples based on single
ratios is obtained by Rb/V. All these ratios, however, do not sufficiently
separate F1 from F2 across all grain size grades. This can be achieved
by using Rb/Sr as additional discriminator (Fig. 5A).
Consequently, a very good discrimination of the three sample suites
is achieved in the ternary diagram with trace elements Rb, Sr and V,
where relative V concentration effectively discriminates sample
suite B from all the other samples (probability N90%) and Rb/Sr ratio
is the main discriminator between F1 and F2 (Fig. 11). The latter
10 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx
Fig. 11. V–Rb–Sr ternary diagram for discrimination of the three sample suites B, F1, and
F2. Fields represent predictive regions for each suite with 67% (solid line) and 90%
(stippled line) probability.
discrimination is less strict due to minor overlap between F1 and F2,
which mainly derive from the finer fractions (Φ N 5) of one single sam-
ple at the western boundary of suite F2 (RT3-6) that shows relatively
low Rb/Sr ratios compared to the rest of F2. Replacing the trace elements
Rb, Sr and V by the major element oxides K2O, CaO, and MgO, respec-
tively, leads to almost the same level of discrimination.
5.3. Grain-size control on composition
Biplot analysis of major and trace elements as well as the linear re-
gression model reveals strong grain size control on sediment composi-
tion. In mineralogical terms the general trend from coarse to fine is
accompanied by the increase of sheet silicates at the expense of quartz
and the silicates. The increase of sheet silicates is twofold: (i) newly
formed clay minerals are preferentially concentrated in the finest frac-
tions due to intense chemical weathering of feldspars and other sili-
cates, and (ii) micas are enriched in the finer fractions due to enhanced
chemical alteration and mechanical comminution along cleavage planes,
as well as hydrodynamic sorting. This is reflected in the ratios of quartz
and feldspar over both micas and clay minerals, which strongly decrease
from sand to silt-clay (Fig. 12). Decrease of the quartz/clay ratio from
coarse sand to clay may exceed two orders of magnitude. In the finest
Fig. 12. Selected mineral ratios from coarse sand to clay for all three sample suites based on
X-ray diffraction data. Note logarithmic scale implying that, for instance, quartz to clay
mineral ratio (qtz/clay) decreases by more than two orders of magnitude from coarse
sand to clay.
Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
fractions, clay minerals even increase relative to mica (i.e. stronger de-
crease of quartz/clay compared to quartz/mica; Fig. 12).
Chemically, sheet silicate enrichment is reflected by an overall de-
crease of SiO2 and increase of Al2O3 and LOI from very coarse sand to
clay (Fig. 2). All other major elements have a more complex pattern, es-
pecially in relative terms (clr-scale, Fig. 6) where even Al increases in
the Φ N 4 fractions only. Considering the sand-fractions separately, the
main trend is controlled by strong depletion of SiO2 and K2O while
CaO and P2O5 increase. All other major elements show only minor
changes (slopes b 0.05) except for LOI showing moderate increase
(Fig. 7). This pattern mostly reflects depletion of quartz and K-feldspar
and increase of plagioclase (and partly amphibole, RT4-3) in (very)
fine sand compared to (very) coarse sand, as corroborated by XRD
data (Fig. 8). Chemical weathering of feldspar grains preferentially
evolves at the surfaces as well as along cleavage and twinning planes,
the latter in turn accelerate mechanical comminution of mineral grains
(e.g. Berner and Holdren, 1979; Banfield and Eggleton, 1990). Among
the feldspars, plagioclase weathers much faster than K-feldspar (e.g.
White et al., 2001), implying that comminution of plagioclase is more
effective than K-feldspar at the initial stages of feldspar weathering.
Therefore, plagioclase is enriched over K-feldspar in fine sand to coarse
silt fractions, where Ca peaks in both raw data and the linear model
(Figs. 2, 6). This decrease in K-feldspar/plagioclase ratio from (very)
coarse to very fine sand is strongly corroborated by both XRD data
(Fig. 12) and MLA data (Table 3). P2O5 reflects enrichment of apatite
and/or other phosphate minerals such as monazite in very fine sand/
very coarse silt, consistent with general enrichment of heavy mineral
in these size fractions (e.g. zircon, Ti-minerals; Table 3).
In the silt to clay range, the linear model is characterized by strong
increase in LOI and strong decrease of CaO and especially Na2O. More-
over, a moderate increase of Fe2O3, and MgO (slopes around 0.1) is ob-
served, and only minor changes for TiO2, P2O5, Al2O3, SiO2 and K2O
(slopes at around ±0.03–0.07, Fig. 7). This observation reflects strong
increase of clay minerals and mica compared to all other minerals
(Figs. 8, 12) and is well in line with the strong increase of CIA obtained
for Φ N 5 (Fig. 10). Because some of these sheet silicates still keep potas-
sium (illite, biotite, muscovite), the decrease of K2O is only minor com-
pared to CaO and Na2O, although most K-feldspar and plagioclase have
disappeared in the finest fractions (Fig. 8). Relative increase of Fe2O3
and MgO also reflects increase of the respective sheet silicates (biotite,
chlorite, smectite). Fe-(hydr-)oxides appear negligible because Fe2O3
and MgO are strongly coupled (Fig. 7).
Interestingly, the least changes in the linear regression model over
the full grain size range (i.e. smallest slopes regardless of sign; Fig. 7)
refer to Al2O3 (Figs. 6, 7). Obviously, Al increase in raw data concentra-
tions towards fine fractions (Fig. 2) but has low overall variability
(Figs. 4, 5) and only small (F1) or almost no (F2) increase from coarse
to fine in relative clr-scale (Fig. 6). Because Al is largely immobile during
weathering processes and is commonly enriched in most clay minerals,
Al typically increases towards fine fractions, even in clr-scale (e.g.
Bloemsma et al., 2012). This effect is quite small here, likely because
we included the loss on ignition (reflecting mainly the water content
of the sheet silicates), which captures most of the relative increase to-
wards the fine grain-size classes.
Regarding trace elements, the Zr/Zn ratio provides a straightforward
proxy for grain size, as already observed for basic and granitoid rocks in
glacial setting (von Eynatten et al., 2012). The new data corroborate this
finding, and extend its use to intensely weathered settings, where Zn is
similarly enriched in the finest fractions, regardless of source-rock li-
thology (Fig. 13). The source rocks, i.e. basic versus more felsic lithology,
are best discriminated by the Rb/V ratio (Figs. 3, 11, 13).
5.4. Comparison to non-weathered sediments
In an analogous study, von Eynatten et al. (2012) investigated the in-
fluence of grain size and source rocks on sediment composition in
 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx 11

model constraints as for the Sila Massif, except for the step at Φ = 8
which is obviously necessary to describe the Aar Massif data set (von
Eynatten et al., 2012).
The comparison shows striking contrasts in the modeled linear re-
gression trends of the major elements against grain size (Fig. 14). The
main observations on contrasting trends for the Sila case vs. the Aar
case include (i) strong decrease of SiO2 already in the sand fraction
from very coarse to very fine sand, (ii) strong increase of CaO in the
sand fraction from coarse to fine, (iii) continuous and pronounced de-
crease for CaO and Na2O in the silt-clay fraction, (iv) continuous in-
crease of Al2O3 and Fe2O3 for the silt-clay fraction (i.e. no significant
steps at Φ = 8), and (v) no increase of K (i.e. no step) for the finest frac-
tions at Φ N 8. These observations mainly reflect the following processes,
which are prominent in the Sila case compared to the Aar case:

(1) Initial plagioclase weathering through hydrolysis along cleavage

Fig. 13. Rb/V vs. Zr/Zn diagram showing all samples and all grain-size fractions. For expla-
nation see text.
glacial settings where chemical weathering is negligible and mechanical
comminution is the main process that governs the separation of mineral
phases and, hence, their distribution in different grain-size fractions.
Study area was granitic bedrock of the Aar Massif in the Central Alps
and basic amphibolites from the Silvretta Massif in the eastern Alps.
The Aar example is quite similar in bedrock composition to sample
suite F2 from the Sila Massif. Given the similar starting point (i.e. gran-
itoid bedrock composition) the comparison of the two cases is actually a
comparison of the effects of strong vs. negligible chemical weathering.
For a reasonable comparison of the linear regression, we recalculated
the model adjusted to the Aar Massif case study, applying the same
and/or twinning planes causes breakage and preferential enrich-
ment of plagioclase over quartz and K-feldspar from coarse sand
to very fine sand, as reflected in Ca increase (observation ii) and
some Si decrease (observation i). The effect may be supported by
initial amphibole weathering in the case of F1.
(2) Intense chemical weathering mainly through hydrolysis leads to
the almost complete removal of feldspar and chain silicates from
the intermediate grain sizes (3 b Φ b 6) to the finest fractions
(observation iii).
(3) Enrichment of various Al- and/or Fe-rich sheet silicates (biotite,
chlorite, smectite, illite, kaolinite) towards the finer and finest
fractions as a consequence of process no. 2 (observation iv).
(4) Enrichment of K-poor clay minerals (kaolinite, smectite) relative
to micas in the finest fractions (observation v). This reflects ongo-
ing removal of potassium, which is essential to obtain the high
CIA values.
The combination of processes (1) and (2) causes the smoothed Ca
(Figs. 2, 6) and plagioclase (Fig. 8) peaks in the Sila case instead of the
abrupt break (i.e. step) in Ca concentration of the glacial Aar case
(Fig. 14), which is caused by mechanical comminution in combination
with inherited mineral-specific grain size distributions (von Eynatten

Fig. 14. Comparison of the adjusted linear regression trends for the weathered case (Sila Massif, sample suites F1 and F2) against the glacial case (Aar Massif) for the most important major
elements. Minor differences in F1 and F2 values compared to Fig. 6 are caused by excluding loss on ignition (LOI) because these data are not available for the Aar Massif data set.

Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
12 H. von Eynatten et al. / Sedimentary Geology xxx (2015) xxx–xxx
et al., 2012). The latter combination was also found to be responsible for
quartz concentrations peaking in fine to very fine sand in the glacial case
study (2 b Φ b 4), which is not the case in the Sila example. There, SiO2
continuously decreases over the full grain-size range from coarse to fine
(observation i), which is caused by intense hydrolysis supported by
quartz leaching (Scarciglia et al., 2007) and, finally, desilicification of
clay minerals and formation of gibbsite as observed in some samples
(Fig. 8). Despite all these differences between the highly weathered
and the glacial case study, some elements converge towards the finest
fractions to very similar relative concentrations independent of similar
(e.g. SiO2) or contrasting starting points (e.g. Fe2O3).
For the fine fractions, the elements showing most contrast between
the highly weathered and the glacial case study are Al2O3 and Na2O
(Fig. 14), suggesting that the ratio of these two elements represents a
simple and straightforward proxy for chemical weathering, which
avoids potential bias through K-metasomatism (Fedo et al., 1995)
and/or the need for corrections for Ca associated with non-silicate
phases (von Eynatten et al., 2003a).
6. Conclusions
Analysis and modeling of composition vs. grain size relations of
proximal sediments in a highly weathered Mediterranean setting (Sila
Massif) and its comparison to a previous study in glacial settings in
the European Alps (von Eynatten et al., 2012) reveal the following
main conclusions:
(1) The chemical index of alteration (CIA) corroborates strong chem-
ical weathering by individual values as high as 92 and average
values of 84 to 88 for the finest fractions. Fractions coarser than
coarse silt (i.e. Φ b 5), however, reveal low to moderate values
in CIA (55 to 68) and an average of 60 for all sand fractions
from all sample suites. The CIA value of a specific sample thus
strongly depends on its grain-size distribution.
(2) Although strongly weathered, the three sample suites reflecting
basic to intermediate (B), intermediate to felsic (F1), and felsic
(F2) plutonic bed rock can be effectively discriminated across
all grain-size classes using trace elements such as V, Rb, and Sr.
At least in the coarser fractions, major elements Mg, Ca, and K
do so, too.
(3) The chemical composition vs. grain-size relations can be accu-
rately modeled by linear regression only if different slopes are
allowed for the sand (Φ b 4) and the silt to clay (Φ N 4) fractions.
Similar slopes in the respective grain-size range for different
sample suites (i.e. intermediate and felsic source rocks F1 and
F2, respectively) underline similar processes independent of
source rock composition.
(4) The mineralogy behind the geochemical data reflects overall (i.e.
valid for all three sample suites) decrease of quartz and K-
feldspar over the full grain-size range from coarse to fine. This
is compensated by overall increase of sheet silicates from coarse
to fine, where the increase of clay minerals strongly outpaces the
increase of micas in the silt to clay fractions (i.e. Φ N 5). A more
complex behavior is shown by plagioclase, which peaks in inter-
mediate grain-size fractions (i.e. 3 b Φ b 6) in all sample suites.
The latter is caused by initial hydrolysis along cleavage planes
and subsequent breakage of plagioclase crystals into smaller
fragments, preferentially in the 125 μm to 16 μm range.
(5) Mechanical comminution, mineral durability, and inherited
grain-size distribution were found to be relevant parameters in
the glacial case study, responsible for peaking of, for instance,
quartz and total SiO2 concentration in fine to very fine sand
(2 b Φ b 4). This is not observed in the highly weathered Sila
case. Instead, both quartz and total SiO2 concentrations continu-
ously decrease from coarse to fine, reflecting the cumulative ef-
fects of minor mechanical forces, quartz leaching, and hydrolysis.
Please cite this article as: von Eynatten, H., et al., Sediment generation in humid Mediterranean setting: Grain-size and source-rock control on
sediment geochemistry and mineralogy (Sila Massif, Calabria), Sedimentary Geology (2015), http://dx.doi.org/10.1016/j.sedgeo.2015.10.008
(6) Given the constantly contrasting behavior of SiO2 and Al2O3 the
ratio Si/Al provides a reasonable proxy for grain size in the Sila
case. This is not valid for the glacial case (Fig. 14). However, Zr/
Zn provides a good proxy for grain size valid for both settings:
high ratios indicate zircon concentration in the intermediate frac-
tions (mostly 3 b Φ b 5) while low ratios indicate sheet silicate en-
richment in the fine fractions (e.g. Φ N 7).
The application of Mineral Liberation Analysis (MLA) yields some
encouraging results, namely (i) the apparent compatibility with X-ray
diffraction data for the main source-rock forming minerals quartz,
K-feldspar, plagioclase, amphibole, and most sheet silicates, and (ii)
the abundance and grain-size distribution of certain heavy minerals.
The potential of the method with respect to the fine grain size ranges
and especially highly weathered materials needs further exploration.
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.sedgeo.2015.10.008.
Acknowledgments
Salvatore Critelli greatly supported us during field work in the Sila
Massif and subsequent discussions. Sample preparation and grain-size
fractionation were performed by Cornelia Friedrich. Journal reviewers
Abhijit Basu and Gert Jan Weltje and guest editor Eduardo Garzanti
are thanked for their careful and constructive handling of the
manuscript.
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