Catena 171 (2018) 299–315

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Catena
journal homepage: www.elsevier.com/locate/catena

Role of weathering of pillow basalt, pyroclastic input and geomorphic T

processes on the genesis of the Monte Cerviero upland soils (Calabria, Italy)
⁎
Anna Chiara Tangaria, , Fabio Scarcigliab, Eugenio Pilusob, Lucia Marinangelia,
Loredana Pompilioa
a
Dipartimento di Scienze Psicologiche, della Salute e del Territorio (DiSPUTer), Università di Chieti-Pescara, 66013 Chieti, Italy
b
Dipartimento di Biologia, Ecologia e Scienze della Terra (DiBEST), Università della Calabria, Via P. Bucci – Cubo 15B, 87036 Arcavacata di Rende, CS, Italy

A R T I C LE I N FO A B S T R A C T

Keywords: In this paper we present new data on weathering and soil formation processes affecting alkaline pillow basalts on
Pillow basalts the summit of Mt. Cerviero (Calabria, southern Italy). We investigated two representative soil profiles using an
Weathering integrated approach, including pedological, petrographic, mineralogical and geochemical investigations. We
Soil genesis distinguished the main features inherited from the hydrothermal alteration of the pillow basalts in a submarine
Pyroclastic input
environment from the chemical weathering processes under meteoric conditions. Irregular geochemical patterns
Erosion
and chemical index of alteration values across the soil profiles indicate a lithological discontinuity between the
Central Mediterranean
bedrock and the upper soil horizons, as a response to soil rejuvenation, in turn controlled by erosive processes
and an allochthonous pyroclastic input. The soil profiles display poor horizonation and an incipient to inter-
mediate degree of weathering, in line with the clay mineralogy (chlorite or hydroxy-interlayered vermiculite,
illite, kaolinite and varying mixed-layers). The degeneration microtextures of clay and iron-manganese coatings
in one soil profile suggest their relict genesis, with an emplacement under warm-humid conditions during the
last interglacial. A Late Pleistocene to Holocene age of soil development is supported by the trachytic compo-
sition of volcanic micropumices, correlated to explosive eruptions from the Campania Province or the Aeolian
Islands, in both soil profiles. Geochemical indices obtained from selective extractions of pedogenetic Al, Fe and
Si pools point to poor andic properties with humus-Al-complexes prevailing over short-range order minerals.
Nonetheless, the latter are consistent with the presence of volcanic glass, an optically isotropic pedogenic matrix
and the Andosol-like field features of the soil profiles, even if they developed in a non-volcanic area. This should
lead to a partial reassessment of the volcanic versus non-volcanic origin of certain Andosols worldwide and
claims a good field work as a basis for choosing the best-suited laboratory methods to fill the gap between
ordinary lab and field results.

1. Introduction Previous studies focused on basalt soils in the peri-Mediterranean

Studies of weathering and soil-forming processes on basaltic rocks
have been approached with a large variety of investigation methods, at
different scales and in several environments, as documented in the
current literature. The published studies provide information on the
morphological textures produced by chemical and physical weathering
processes, weathering of primary minerals, mineralogy of neoformed
products, rock and soil geochemistry, including isotopes. Other topics
are the degree and rates of the weathering processes and soil devel-
opment, relationships with relief features and landscape evolution,
paleoweathering and climatic signature (e.g., Prudêncio et al., 2002;
Sayyed, 2014; Conceição et al., 2015; Taboada et al., 2016).
area are mainly localized to the southeastern (Singer, 2007; Lucke
et al., 2014), southwestern (Hamidi et al., 1999; Dekayir and El
Maâtaoui, 2000) regions, and insular Italy (Egli et al., 2008; Vacca
et al., 2009; Vingiani et al., 2010). The knowledge of weathering and
pedogenetic processes occurring on basaltic parent rocks in mountai-
nous environments of the central Mediterranean area is quite poor.
These sites are characterized by significantly more humid climate
compared to the Mediterranean coastal areas. In addition, only few
papers focus on the weathering and soil formation processes affecting
pillow basalts (e.g., Polat et al., 2012; Žigová and Štastný, 2014), which
are very peculiar rocks in terms of genesis and corresponding primary
features.

⁎
Corresponding author.
E-mail address: a.tangari@unich.it (A.C. Tangari).

https://doi.org/10.1016/j.catena.2018.07.015
Received 23 November 2017; Received in revised form 12 July 2018; Accepted 13 July 2018
0341-8162/ © 2018 Elsevier B.V. All rights reserved.
A.C. Tangari et al. Catena 171 (2018) 299–315

In this paper, we present new data on the weathering and soil for-
mation processes involving basaltic pillow lavas which outcrop in the
Monte Cerviero area (Calabria, southern Italy). Although pillow basalts
have a tholeiitic geochemical affinity and form in mid-oceanic ridge
settings, the pillow basalts of the study area show an alkaline geo-
chemical affinity and were intruded in a submarine environment within
Meso-Cenozoic carbonatic sequences. These features represent an in-
triguing case study in order to assess soil formation processes on al-
kaline basalts.
We analyzed the weathering products which formed on the basalts
which were emplaced in a submarine environment and subsequently
emerged and exposed to subaerial, meteoric conditions. We tried to
distinguish the main features inherited from hydrothermal alteration
from those diagnostic of weathering processes under environmental
conditions. We also explored the potential contribution of fine volcanic
ash (not easily visible, either to naked eyes or under the optical mi-
croscope) on soil formation processes, which is usually poorly in-
vestigated in basalt-derived soils (Rasmussen et al., 2010; Taboada
et al., 2016). Since in recent years soils with andic properties were
largely described worldwide in non-volcanic ecosystems, spanning a
wide range of parent materials and climatic conditions (Bäumler et al.,
2005; Dümig et al., 2008; Mileti et al., 2013), our work is relevant to
test the hypothesis that the Andosol-like field appearance of the pedons,
along with corresponding andic properties estimated in the lab, could
be considered as proxies of cryptotephras even in non-volcanic areas.
This would have important implications on tephrostratigraphy, geo-
chronology and reconstruction of Quaternary landscape evolution
(Scarciglia et al., 2008; Pelle et al., 2013; Vingiani et al., 2014), as well
as help the assessment of fertility and susceptibility to land degradation
of andic soils, which are particularly fragile ecosystems subject to soil
erosion and landslides (Terribile et al., 2007; Arnalds, 2013; Henry
et al., 2013).

2. Geology, geomorphology and climate of the study area

Mount Cerviero is part of the mountainous group of the Pollino
Massif, located at the Calabria-Lucania boundary of the southern
Apennine fold-and-thrust belt (southern Italy). It consists of an isolated
relief, reaching an altitude of 1443 m a.s.l. (Fig. 1A). Mt. Cerviero
emerges from a flat to gently rolling landscape, which consists of old
planation surfaces (paleosurfaces), shaped during the Late Pliocene-
Early Pleistocene and uplifted at different elevations above
1100 m a.s.l. (Schiattarella et al., 2013, 2017). The whole area is
dominated by a wide exposure of the Middle Trias to Early Miocene
limestone-dolostone sequence (Amodio Morelli et al., 1976;
Grandjaquet and Grandjaquet, 1962; Iannace et al., 2005), exhumed
during Miocene age (Iannace et al., 2007) and strongly affected by ty-
pical karst processes. Sheet wash, soil creep and colluvial dynamics also
occur, especially on bare to sparsely vegetated surfaces, with local
gravity-driven phenomena, such as falls, topples, translational slides
and debris flows/avalanches along steeper slopes. Alkaline basalt in-
trusions within the carbonatic rocks outcrop at places (Pierattini et al.,
1975; Macciotta et al., 1986; Matrangolo, 2013).
From bottom to top, the calcareous-dolomitic sequence includes
(Fig. 1A): Late Triassic black and white dolomite; Jurassic-Cretaceous
limestone and metalimestone with cherts; Paleocene to Early Miocene
(?) calcirudites and calcarenites with nummulites, and limestone
breccias (Ghisetti and Vezzani, 1983; Iannace et al., 2004).
The mafic rocks consist of pillow lava basalts cross-cutting the
Triassic-Paleocene sequence. The age of the basalts is still debated.
Proposed emplacement ages vary between Middle Eocene (Quitzow,
1935) to Early Miocene (Grandjaquet and Grandjaquet, 1962), al-
though more recently Iannace et al. (2007) placed the basaltic mag-
matism in the Cerviero area within the Jurassic period. K/Ar geochro-
nological dating of the basaltic intrusions yields an Early Miocene age,
which was also attributed to the greenschist metamorphism, well
Fig. 1. (A) Geological-structural sketch of the sampling area (modified after
CASMEZ, 1954; Servizio Geologico d'Italia, 1971; Ghisetti and Vezzani, 1983;
Iannace et al., 2004; Brozzetti et al., 2017): 1 = Late Pleistocene-Holocene al-
luvial fans, colluvium and slope debris; 2 = Middle to Late Pleistocene fill of the
basin (mainly lacustrine); 3 = Paleocene to Early Miocene(?) calcirudites and
calcarenites with nummulites, and limestone breccias; 4 = pillow basalts;
5 = Upper Jurassic to Early Cretaceous weakly schistose argillites and slates
with intercalations of quartzites and calc-schists; 6 = Jurassic-Cretaceous
limestone and metalimestone with cherts; 7 = Late Triassic black and white
metadolomite; 8 = Late Pleistocene to Holocene west-dipping normal fault;
9 = Early-Middle Pleistocene west-dipping normal fault; 10 = Early to Middle
Pleistocene south-dipping normal fault; 11 = sample site. (B) Slope map of the
study area. The circles indicate the location of the soil profiles.
documented in the carbonatic rocks (Pierattini et al., 1975).
Mt. Cerviero is characterized by temperate humid climatic condi-
tions typical of Mediterranean upland climate, with mean annual pre-
cipitation around 1600 mm and mean annual temperature around 8 °C,
with udic and mesic moisture and temperature regimes (ARSSA, 2003).
3. Materials and methods
Based on the major soil types described in the summit landscape of
Mt. Cerviero, where shallow to moderately deep Cambisols, Regosols
and Phaeozems or Umbrisols (cf. ARSSA, 2003) occur, and basaltic
rocks outcrop for only 1 km2, we accomplished a field soil survey and
selected two representative soil profiles (MC1 and MC2) developed on
top of the pillow basalts. Both the soil profiles were sampled on gentle
slopes of the Plio-Pleistocene planation surfaces at an elevation of about
1330 m a.s.l. (Fig. 1B). The field study focused on a detailed morpho-
logical description of the major soil features, such as depth, color,

300
A.C. Tangari et al.
structure, dry consistence, texture, skeletal fraction and other pedo-
features (FAO, 2006) as well as description of the underlying bedrock.
A pedological, petrological and mineralogical study of fresh, un-
weathered up to intensely weathered bedrock samples and proper soil
horizons was then accomplished with laboratory analyses.
The fine-earth fraction (< 2 mm) of the bulk soil samples from each
soil horizon was characterized for particle size distribution, organic
matter and total carbonate contents, pH (H2O) and cation exchange
capacity (CEC), performed according to standard laboratory procedures
(van Reeuwijk, 2002; Burt, 2004).
The petrography of the bedrock was studied in thin section using a
polarizing optical microscope. Also, the main micromorphological
features of pedogenetic A and Bt horizons and a patina covering the
outer surface of the pillow basalts were described in thin section (ob-
tained from undisturbed soil samples collected with aluminum Kubiena
boxes), following the guidelines of FitzPatrick (1984).
Mineralogical analyses were carried out using X-ray diffraction
(XRD) both on powdered bedrocks samples and parallel oriented spe-
cimens of the clay fraction (< 2 μm) extracted from each soil horizon,
in order to assess the primary mineral assemblage and neoformed clay
minerals. A Rigaku Miniflex II diffractometer operating with Cu-Kα
radiation at 50 kV and 1 mA was used. The clay fraction was separated
through sieving and centrifugation, after organic matter removal with
H2O2 reaction. The oriented specimens on glass slides were analyzed
after the following treatments: air-dried; ethylene-glycol (EG) solvation,
K-saturation and heating treatments at 105, 335 and 550 °C. X-ray
diffraction patterns were interpreted according to Moore and Reynolds
(1997).
The amounts of Al, Fe and Si extracted with acid ammonium oxalate
(Schwertmann, 1964) and sodium pyrophosphate (Bascomb, 1968)
were measured using atomic absorption spectroscopy (AAS) of the fine-
earth fraction (< 2 mm). These data allowed us to calculate some
pedogenetic indices, such as Alo + 0.5 Feo (ICOMAND, 1988),
(Alo − Alp)/Sio and Alp/Alo (Parfitt and Wilson, 1985), as proxies of
andic properties (IUSS Working Group WRB, 2014; Soil Survey Staff,
2014) and an estimate of the potential occurrence of short-range order
minerals (SROM), such as allophane, imogolite and proto-imogolite.
The total chemical composition of major (as % wt oxides) and trace
elements (as mg kg−1), both in the bedrock and soil horizons was
measured with an X-ray fluorescence spectrometer (XRF) Bruker S8
Tiger.
The geochemical behavior of these elements across the soil profiles
was evaluated to trace their degree of weathering and identify the main
pedogenetic processes (e.g., Nesbitt, 1979; Caspari et al., 2006;
Scarciglia et al., 2016). The chemical index of alteration (CIA) proposed
by Nesbitt and Young (1982) was also calculated, both in soil horizons
and bedrock, as the ratio Al2O3/(Al2O3 + CaO + Na2O + K2O) × 100,
where CaO represents the amount of calcium in silicate minerals.
Therefore, the CaO content was recalculated after subtracting the ex-
cess of CaO included in carbonate minerals, in turn obtained from the
total carbonate content.
Scanning electron microscopy coupled with energy dispersive
spectroscopy (SEM-EDS) analyses were carried out on the outer rim of
the basaltic bedrock to identify neoformed phyllosilicate clay groups,
based on the major element composition and the Si/Al ratio. A FEI/
Philips scanning electron microscope, equipped with a Si/Li crystal
microprobe detector (GENESIS-4000, EDAX, Philips Electronics) was
used. The possible occurrence and chemical composition of volcanic
glass in some soil samples with Andosol-like field appearance was also
investigated. EDS distribution maps of some chemical elements were
also obtained in selected areas of the basalt bedrock at the transition
with the outer patina.
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Catena 171 (2018) 299–315
Fig. 2. The pillow basalt bedrock from Mount Cerviero related to soil profile
MC2.
4. Results
4.1. Bedrock features and nature
The pillow lava basalts cropping out in the study area preserve the
original pillow structure at the mesoscopic scale (Fig. 2). Along their
borders, where the pillow basalts are in contact with the limestones,
they have a brecciated aspect. The pillows are sub-spherical in shape
with diameters in the order of few decimeters to meters. Generally,
each pillow exhibits a greenish gray massive core surrounded by a
coriaceous outer shell as a surface crust. The pillow core has a por-
phyritic texture, while the outer vesicular glassy crust includes vacuolar
microcavities, spherical in shape. The weathering pattern develops
concentrically around the pillows, thus forming one or more, cen-
timeter to millimeter thick, micro-cracked, weathered rinds, which are
locally affected by flaking, spalling and detachment of small blocks,
which are peeled off at places (Fig. 2). Occasionally, it is possible to
observe a patina covering the concentric weathering rinds, which
consists of reddish yellow to black Fe-Mn oxides/hydroxides and brown
clay coatings of illuvial origin. Generally, this patina overlays the outer
surface of the pillows and occurs in the sub-parallel, concentric cracks,
and is less developed in the bedrock underlying soil profile MC2 than
MC1. In places, very small tree roots, lichens and/or mosses appear to
grow within cracks or colonize small patches of the rock surface.
The petrographic analysis of the unweathered bedrock under the
optical microscope showed phenochrysts of plagioclase, clinopyroxene
and opaque minerals surrounded by an intersertal groundmass made of
plagioclase, clinopyroxene, opaque and glass. Euhedral phenocrysts of
plagioclase have turbid aspect due to their retrogression in epidote and
white mica. Clusters of calcite, epidote and sericite are also present.
Clinopyroxenes occur both as idiomorphous phenocrysts and glomer-
oporphyres and appear strongly transformed into chlorite. The opaque
minerals show a subhedral to anhedral habitus. Subordinate phases
such as pumpellyite, prehnite, chlorite, epidote, zeolite and calcite were
detected. Conversely, the cryptocrystalline groundmass displays clear
evidence of devitrification processes (Fig. 3).
4.2. Field soil features
The two representative soil profiles (MC1 and MC2) developed on
A.C. Tangari et al.
Fig. 3. The basalt microstructure with vacuolar microcavities of spherical shape filled by chlorite and zeolite. (A) MC1R sample plane polarized light; (B) MC2R
sample plane polarized light.
intensely weathered pillow lava basalts display different pedogenetic
horizonation under a very thin surface litter (Fig. 4). Their main mor-
phological features are listed in Table 1. Soil profile MC1 (Fig. 4A)
varies in color from pale to weak red; its pedogenic structure ranges
from granular and subangular blocky in the A horizon to angular blocky
in the Bt horizon, with very weak to hard dry consistence. Texture
ranges from sandy loam to loam. Frequent to abundant, strongly
weathered, angular clasts of basalt, from few centimeters to half a
meter in size, occur especially in the subsoil, suggesting a partly col-
luvial origin of the soil profile. The Bt horizon displays an amount of
clay coatings around 30–35%. A Cr/R layer with whitish skeletal clasts
of carbonate origin underlies the soil profile.
Soil profile MC2 (Fig. 4B) is less differentiated into soil horizons
than MC1 and shows different colors, ranging from brown at the top (A
horizon) to reddish brown at the bottom (AB horizon). The pedogenic
structure changes from granular and subangular blocky in the A horizon
to angular blocky in the AB horizon. Similarly, to MC1, soil profile MC2
has a very weak to hard consistence, sandy loam texture, and includes
an abundant, coarse skeletal fraction, consisting of angular basalt
fragments, in turn exhibiting frequent illuvial clay coatings.
The upper soil horizons of both profiles exhibit field features similar
to those formed on volcanic ash soils with andic properties, such as dark
moist colors, powdery appearance when dry, fluffy, friable and
Fig. 4. Soil profile MC1 (A); soil profile MC2 (B). Each red and white line of the tape measure corresponds to 10 cm. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
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Catena 171 (2018) 299–315
sometimes smeary consistence, low bulk density, and a certain thixo-
tropy (cf. Shoji et al., 1993; Baumgarten et al., 2013; IUSS Working
Group WRB, 2014).
The field test with a 10% HCl solution gave a null effervescence
reaction for each pedon in proper pedogenetic horizons, whereas a
strong reaction in Cr and R layers.
4.3. Chemical and physical properties
Chemical and physical features of the soil profiles MC1 and MC2 are
listed in Table 2. Particle size distribution indicates prevalent loamy
textures, although it is well-known that the clay fraction in volcanic ash
soils is often poorly dispersible (Velescu et al., 2010) and therefore
underestimated. In MC1 soil samples, a clear increase of clay fraction
with depth was detected, whereas textural changes in soil profile MC2
are not relevant. Slightly to moderately acidic pH conditions char-
acterize all the soil horizons except the Cr layer of soil profile MC1
which is moderately alkaline. The organic matter content ranges from
about 6% to 1%. Cation exchange capacity shows generally high values,
except for the Cr horizon (soil profile MC1) where it is very low. The
two soil profiles show a null content of total CaCO3 except in the Cr
horizon of soil profile MC1, where it reaches up to 19.6%. The CaCO3
content is in good agreement with the HCl solution field test.
A.C. Tangari et al. Catena 171 (2018) 299–315

Table 1
Summary of morphological features of the Cerviero soil profiles.
Soil profile Elevation (m a.s.l.) Horizon Depth (cm) Color Redness rating Structurea Consistenceb Clay coatings (%)

MC1 1338 O 0–3/5 – – – –

A 3/5–10/20 10R 6/2-10R 5/3 0 GR-SB vw-m
Bt 10/20–45/50 10R 5/3 0 AB m 30–35
Bt/R 45/50–95 – – – –
Cr/R 95–125/130 – – – –
MC2 1334 O 0–1 – – – –
A 1–6/12 cm 7.5YR 5/4-5YR 4-3 2.0–3.75 SB vw –
AB/R 6/12–48/72 5YR 5/4-7.5YR 5/4 4.0–2.0 SB-AB vw-m –
R 48/72–200 – – – –

a
Structures: GR = granular; SB = subangular blocky; AB = angular blocky.
b
Consistence: vw = very weak; m = moderate.

4.4. Mineralogy 4.5. Geochemistry

The XRD patterns of the weathered bedrock display diagnostic
peaks of quartz, plagioclase, chlorite, micas and pumpellyite. These
data are in good agreement with the mineral assemblage identified
from petrographic analyses on the unweathered (“fresh”) bedrock. X-
ray diffraction analysis of the Cr horizon from soil profile MC1 exhibits
a great abundance of dolomite.
The X-ray diffraction patterns of the clay fraction obtained from the
soil horizons allow the main clay mineral signatures to be identified
(Fig. 5; Table 2). In soil profile MC1 illite is the most abundant phyl-
losilicate clay, with minor amounts of kaolinite/smectite mixed-layers
(K/Sm), hydroxy-interlayered vermiculite (HIV) and traces of chlorite/
vermiculite (Chl/V) or chlorite/smectite (Chl/Sm) interlayers (Fig. 5A).
In soil profile MC2 chlorite and kaolinite are the most abundant phyl-
losilicate clays, followed by illite and traces of Chl/Sm and Chl/V
mixed-layers (Fig. 5B). The persistence of the basal reflection at
10.00–10.22 Å and secondary reflections at 4.95–4.99 Å and
3.30–3.35 Å, after any treatment, allowed illite to be identified in both
samples. Reflections at 7.10–7.12 Å and 3.58 Å persisted after almost all
the treatments and collapsed at 550 °C. These pattern and behavior are
diagnostic of kaolinite, which exhibits sharper and more intense peaks
in soil profile MC2 than MC1. Conversely, MC1 diffraction patterns
show broad, asymmetrical and composite diffraction peaks of kaolinite,
indicating possible 2:1 clay mineral interlayers. In particular, the shift
of the basal reflection to 7.56–8.04 Å after glycolation suggests that
these components consist of kaolinite/smectite mixed-layers. XRD
patterns of all the air-dried samples exhibit also a diffraction peak at
14.26–14.42 Å. In soil profile MC1, the above peak around 14 Å which
largely contracts to ca. 10 Å after heating at 335 °C indicates the oc-
currence of hydroxy-interlayered vermiculite. In the MC2 soil horizons,
the basal reflection at 14 Å was stable after any treatment, suggesting
the presence of chlorite, further confirmed by the peaks at 4.78–4.68
and 3.54 Å. The samples of both profiles occasionally showed a very
weak diffraction peak centered at 12.4–12.6 Å, which can be inter-
preted as the scarce occurrence of mixed-layer clay minerals of the
chlorite group, interlayered with 2:1 phyllosilicates such as vermiculite
or smectite.
XRF data of the soil horizons and the parent rock are listed in Tables
3 and 4. In addition, we considered the mean chemical composition of
five basalt samples outcropping in the same study area (Matrangolo,
2013), which are characterized by relatively low values of loss on ig-
nition (3.5 ≤ LOI ≤ 5.0%). The average value of the five samples was
assumed as a reference composition of the relatively unweathered
(“fresh”) bedrock (Tables 5 and 6). All the bedrock samples show
transitional affinity from alkaline to sub-alkaline basalts, ranging from
trachy-basalt to basalts and picrobasalts, as classified according to the
TAS (total alkali versus silica) diagram (Le Bas et al., 1986).
Irregular geochemical patterns are observed across the soil profiles,
as a number of chemical species (both major and trace elements) ex-
hibit strong variations in their abundance in the Cr/R and R layers of
profiles MC1 and MC2, compared to the underlying/overlying horizons.
Apart from these discontinuities, from the bedrock to the topsoil hor-
izons, our data show an increase of Al2O3, K2O and MnO content. SiO2,
CaO and MgO progressively decrease from the bottom to the topsoil.
Fe2O3 content is generally slightly higher in soil profile MC1 than MC2.
P2O5 content exhibits an opposite behavior, showing usually higher
values in MC2 than in MC1, as well as NaO. Irregular patterns of major
and trace elements are also observed in the Cr horizon (soil profile
MC1), where calcium and magnesium oxides dominate. The behavior of
major and trace elements in the soil profiles is shown by the molar ratio
between elements with different mobility (Figs. 6, 7). The patterns of
some trace elements, such as Ce and La, versus Ti generally show an
increase from the bedrock to the topsoil in both soil profiles. The CIA
index depicts an intermediate (to incipient) chemical weathering (cf.
Fedo et al., 1995) in the two soil profiles (Fig. 6A), where it generally
increases abruptly from the bedrock to the topsoil.
4.6. Selective extractions
Data obtained from selective extractions and related geochemical
indices are shown in Table 7. The Alo + 0.5 Feo index is low for all the
samples and comprised between 0.3 and 1.2% with higher values in soil

Table 2
Main physical-chemical properties and clay minerals of the studied soil profiles.
Soil profile Horizon Particle size distribution CaCO3% pH (H2O) OM % CEC cmol(+) kg−1 Clay minerals

Sand % Silt % Clay %

MC1 A 54 35 11 0 6.51 2.90 29.2 I, HIV, K/S, Chl/V, (Chl/S)

Bt 28 45 27 0 6.36 0.97 42.6 I, HIV, K/S, Chl/V, (Chl/S)
Cr Not determined 19.6 8.20 1.39 3.42 Not determined
MC2 A 48 44 8 0 6.04 6.30 45.2 I, K, Chl, I/S, Chl/V, (Chl/S)
AB 45 47 8 0 6.24 4.05 39.9 I, K, Chl, I/S, Chl/V, (Chl/S)

OM = organic matter; CEC = cation exchange capacity; HIV = hydroxyl-interlayered vermiculite; I = illite; K = kaolinite; Chl = chlorite; S = smectite; slash in-
dicates mixed layers clay minerals.

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A.C. Tangari et al. Catena 171 (2018) 299–315

Fig. 5. Selected XRD patterns of clay minerals: (A) horizon Bt of soil profile MC1; (B) horizon AB of soil profile MC2. Chl: chlorite; HIV: hydroxy-interlayered
vermiculite; I: illite; K: kaolinite; S: smectite.

Table 3
Content of major elements in weight percentage of oxides and CIA index in the Cerviero soil profiles (weathered bedrock included) obtained using X-ray fluorescence
spectroscopy.
Soil profile Horizon SiO2% Al2O3% MgO% Fe2O3% CaO% Na2O% K2O% P2O5% TiO2% MnO% LOI % CIA%

MC1 A 43.24 17.03 4.63 14.33 1.69 0.35 5.04 0.19 2.17 0.12 11.19 70.63
Bt 48.66 17.49 4.58 12.35 1.41 0.52 4.63 0.22 2.14 0.17 7.16 71.8
Cr 2.83 1.04 19.74 1.05 33.57 0.00 0.33 0.03 0.16 0.01 41.24 3.87
R 50.84 13.43 10.18 9.88 6.27 0.12 2.21 0.29 2.22 0.09 4.47 33.33
MC2 A 40.04 15.65 5.43 12.95 2.34 0.55 2.67 0.44 2.11 0.34 17.48 73.79
AB 40.64 16.42 5.99 13.46 2.39 0.46 2.69 0.41 2.25 0.34 14.93 74.77
R 44.34 13.65 12.02 12.75 8.27 0.00 0.00 0.26 2.26 0.18 6.27 37.72

profile MC2. The ratio Alp/Alo is always < 1, whereas the ratio
(Alo − Alp)/Sio is ≤0.3. The latter is an estimation of the Al/Si molar
ratio in the short-range order minerals, after correction of the alu-
minum forms bound to soil organic matter (Parfitt and Wilson, 1985).
4.7. Micromorphology
The A horizon includes both weathered basalt and carbonate rock
fragments as skeletal fraction. It exhibits a highly porous, single grain
structure coupled with crumbs and rare subangular blocky micro-
aggregates. The pedogenic matrix is mainly isotropic with some ani-
sotropic domains when viewed in cross-polarized light. No glass frag-
ment was identified under the optical microscope in each soil horizon.
Occasional black charcoal fragments with a typical cellular structure
were identified. The Bt horizon of soil profile MC1 exhibits a skeletal
fraction including all the primary minerals of the bedrock, affected by
severe weathering. Abundant faunal passages and occasional planar
pores represent the main porosity. The soil matrix generally appears as
moderately anisotropic in cross-polarized light. It includes frequent il-
luvial clay, silt and silty-clay coatings within pores and in places sur-
rounding chlorite grains or filling their cleavage planes (Fig. 8A, B),
where chlorite flakes with a fibrous habitus and a recurrent fan-like
assemblage are splitted apart. The clay coatings range from yellow to
yellowish red (where iron-stained) in color and are often alternated
with brownish yellow to (reddish) brown, silt and silty-clay dusty
coatings (Fig. 8A). They are often fragmented and microlaminated with

304
A.C. Tangari et al. Catena 171 (2018) 299–315

concentric patterns (Fig. 8C), and exhibit grainy to smooth-banded

(mg kg−1)
extinction patterns, up to sharp extinction bands in cross-polarized light

24.00
18.00
(Fig. 8D). Occasionally, sub-rounded to irregular Fe-Mn segregations
7.00
4.00
4.00
0.00

3.00
Pb

can be observed, often fragmented and surrounded by clay coatings

(Fig. 8C–G).
(mg kg−1)

Micromorphological features partly similar to those identified in the

119.00
112.00
97.00
87.00
12.00

51.00
2.00
Bt horizon can be observed at the interface between the bedrock and
Rb

the surface patina. The patina developed on the surface of the MC2
bedrock includes weathered flakes of chlorite crystals at places, or coats
(mg kg−1)

the outer boundary of concentric, poorly regular layers, where chlorite

14.00
12.00

18.00
0.00
0.00

9.00
6.00

phenocrysts are concentrated and alternated with other concentric, Fe-

As

Mn-coated zones. Yellowish patches of neoformed clay were observed

(mg kg−1)

on the patina (Fig. 8F). In addition, the patina coating the MC2 bedrock
181.97
191.50

100.79
201.69
202.21
132.29
28.92

shows abundant clay illuviation in pits and large voids, along with Fe-
Zn

Mn oxide segregations.
The Fe-Mn oxide segregations are more frequent in the patina
(mg kg−1)

overlaying the bedrock of MC1 than MC2. In general terms, the MC1
85.29
86.94

79.57
58.21
55.95
81.62

bedrock exhibits more extensive weathering, since argillification and in

7.30
Cu

situ oxidation (Fig. 8G, H) are much more widespread than in MC2
specimens. Furthermore, polycrystalline quartz with tectonic fabric
(mg kg−1)

filling amygdaloid structures was often identified in association with

206.00
190.00

167.00
218.00
217.00
167.00
31.00

chlorite, epidote and pumpellyite structures in the MC2 bedrock. Single

Zr

grains of calcite also occur.

(mg kg−1)

133.00

127.00
253.00
254.00
235.00
113.00
20.00

4.8. SEM-EDS analysis

Sr
(mg kg−1)

SEM analysis was carried out in order to better constrain the mor-
phological features of the patina at the surface of the basalt parent rock
20.00
25.00

25.00
23.00
25.00
25.00
1.00

(Fig. 9A). The irregular, thin submillimetric patina shows a different

Y
Content of trace elements in mg kg−1 in the Cerviero soil profiles (weathered bedrock included) obtained using XRF.

morphology of the constituent particles, ranging from sheet to granular-

(mg kg−1)

globular shapes in the top and bottom sides (Fig. 9B–D). We also used
34.00
30.00
15.00
29.00
37.00
35.00
28.00

the EDS spectra to analyze the composition of primary and neogenic

Nb

mineral phases at the bedrock-patina transition. In particular, clay

mineral assemblages in the patina were estimated using major element
(mg kg−1)

contents and the Si/Al molar ratio (e.g., Mulyanto et al., 1999;
222.00
170.00

181.00
458.00
428.00
51.00
0.00

Scarciglia et al., 2011; Perri et al., 2015). This ratio throughout the
Ba

patina ranges between 1 and 2. These values together with the high
content of K2O suggest the dominance of illite components. On the
(mg kg−1)

other hand, the same range of molar ratio values, coupled with a
65.67
65.75

52.61
66.90
67.70
66.55
0.00

variable amount of Mg, Fe, Ca and minor Na, points out the occurrence
Co

of other clay minerals such as chlorite, vermiculite and traces of

(mg kg−1)

smectite.
43.00
33.00
14.00
34.00
66.00
64.00
33.00

The patina developed inside the subparallel and concentric rinds of

Ce

the altered pillow basalts shows abundant particles with spherical

shapes, usually a few microns in size (Fig. 9D). High iron (from 28.0%
(mg kg−1)

up to 72.0 wt%) and manganese (from 3.0% up to 21.0 wt%) contents

10.00
7.00
0.00
7.00
9.00
7.00
0.00

are consistent with iron and/or manganese oxy-hydroxides. Molar ra-

La

tios of Si/Al close to 1 of extensive clay coatings and platelets allow us

to infer the dominance of kaolinite or halloysite.
(mg kg−1)

207.00
200.00

228.00
225.00
227.00
228.00

The different distribution of the major elements in the bedrock and

72.00

the patina (Fig. 10A) indicates a relative decrease of SiO2, MgO, CaO
V

and increase of Al2O3 from the former to the latter (Fig. 10B–E). Al-
(mg kg−1)

kaline elements follow an enrichment trend from the bedrock to the

412.00
429.00

441.00
376.00
388.00
432.00

patina. Iron and titanium increase from the bedrock to the patina
0.00
Cr

(Fig. 10F–G). Although completely absent in the bedrock, Mn reaches

high concentrations in the upper-intermediate, concentric rinds of the
(mg kg−1)

patina developed on the MC2 sample (Fig. 10G). In addition, nitrogen

174.72
202.15

261.28
218.72
225.98
295.53
21.71

and phosphorus, diagnostic of organic matter, increase (up to 2.8 and

Ni

1 wt% respectively) from the bedrock to the patina.

SEM analyses also revealed the presence of few volcanic glass shards
Horizon

and vesiculated micropumices (< 1%) within the matrix of the A hor-
Cr/R

AB
Bt

izon of soil profile MC1 (Fig. 11). These fragments are micrometric in
A

A
R

size (~10 μm) and have a trachytic composition according to the TAS
Table 4

profile

MC1

MC2
Soil

diagram (mean value of SiO2 = 60%; standard deviation = 0.54; mean

value of Na2O + K2O = 12%; standard deviation = 0.95).

305
A.C. Tangari et al. Catena 171 (2018) 299–315

Table 5
Chemical composition of major elements (as wt% of oxides) of unweathered (“fresh”) bedrock obtained using XRF.
Unweathered bedrock SiO2% Al2O3% MgO% Fe2O3% CaO% Na2O% K2O% P2O5% TiO2% MnO% L.O.I.%

AB4 49.16 11.87 9.52 12.19 11.26 2.96 0.58 0.25 2.38 0.15 5.00
AB15 50.21 13.35 10.16 11.26 8.16 2.62 0.08 0.35 2.20 0.12 4.00
AB33 48.92 16.01 7.97 15.54 2.93 4.97 0.39 0.42 2.95 0.14 5.00
AB35 52.27 12.98 9.1 12.77 6.85 3.12 0.07 0.34 2.20 0.14 3.50
AB40 47.97 12.33 9.85 13.38 10.39 3.11 0.07 0.3 2.4 0.14 4.50
Mean value 49.71 13.31 9.32 13.03 7.92 3.36 0.24 0.33 2.43 0.14 4.40
Standard deviation 1.64 1.62 0.85 1.61 3.29 0.92 0.24 0.06 0.31 0.01 0.65

5. Discussion quartz is a well-known product of basalt–seawater interaction, which

Because of the emplacement of pillow basalts in a submarine en-
vironment, a better understanding of the main soil formation processes
requires a discrimination between features produced by hydrothermal
alteration (herein after referred to as “alteration”) and those related to
chemical transformation processes in the subaerial continental en-
vironment (meteoric “weathering”).
5.1. Pillow morphology, mineral assemblage and weathering features
Pillow basalts are igneous rocks and generally occur in mid-oceanic
ridge settings, as a result of the interaction between basaltic magma and
seawater (Schubert et al., 2001; Hefferan and O'Brien, 2010). Although
they often have a tholeiitic affinity, the pillow basalts outcropping in
the Mt. Cerviero area show an alkaline geochemical affinity. Their ty-
pical spheroidal shape with an outer vesicular glassy shell, is consistent
with the instantaneous quenching and faster cooling of their surface
than the inner core after their emplacement in cold seawater, at rela-
tively low effusion rates (e.g., Hefferan and O'Brien, 2010). The wide-
spread vacuolar microcavities within the crust support an emplacement
in a shallow marine environment (Grandjaquet and Grandjaquet,
1962). The concentric, onion-like distribution of the weathering rinds
observed on the pillows, suggests a clear control of physical breakage
patterns under subaerial conditions (related to surface flaking and
spalling; e.g., Bourke and Viles, 2007) by the spherical shape of their
core and the hydrothermally formed, layered surface crust. Due to the
climatic conditions of the study area, mechanical weathering is prob-
ably triggered by thermoclastic and cryoclastic processes, coupled with
local bioturbation by small tree roots and/or lichen and moss coloni-
zation, as described in other mountainous settings of Calabria (cf.
Scarciglia et al., 2007, 2012).
This mineral assemblage (pumpellyite, prehnite, chlorite, epidote
and zeolite) of the pillow core can be interpreted as the result of an
early stage alteration, presumably related to hydrothermal fluids,
which affected the fresh bedrock originally composed of plagioclase,
clinopyroxene and opaque minerals, with an intersertal groundmass
made of plagioclase, clinopyroxene, opaque and glass. In particular: (i)
pumpellyite, prehnite and zeolite are common alteration products of
plagioclase (Escuder Viruete et al., 2009; Kiss et al., 2016); (ii) epidote
and chlorite may derive from the hydrothermal alteration of plagioclase
and clinopyroxene, respectively (Humphris and Thompson, 1978); (iii)
the alteration of glass appears an important factor in the formation of
the zeolites (Keith and Staples, 1985; Chipera and Apps, 2001). The
identification of chlorite crystals in the outer part of the basalt core at
the interface with the overlying patina supports the role of circulating
hydrothermal fluids in the alteration of pillows.
The identification of K-mica in XRD patterns is probably related to
the sericitization of plagioclase, which is in good agreement with high-
temperature conditions and hydrothermal alteration. The formation of
quartz can be explained as related to seafloor metamorphism, triggered
by the circulation of hydrothermal fluids. Si-enriched hydrothermal
fluids could have been responsible of the precipitation and later crys-
tallization of silica. Nevertheless, according to Polat et al. (2012),
possibly occurred during the brecciation of pillow rinds. In addition,
quartz could have an external provenance, being included within the
cherty limestone breccias overlapping the pillow basalts. After the
emplacement, the pillows were exhumed and involved in the Apenninic
orogenesis (Iannace et al., 2007), in accordance with the microtectonic
fabrics.
5.2. Soil formation processes and (paleo)environments
The poor differentiation into shallow depth soil horizons, dominant
sandy loam textures, abundance of very coarse skeletal fraction, at least
partly related to colluvial processes, and incipient to intermediate de-
gree of weathering indicated by CIA values (Fedo et al., 1995) show
that both profiles MC1 and MC2 still preserve a relevant imprint from
the parent material. In addition, the very shallow A horizons in both
profiles, the lack of Bt horizon in soil profile MC2 and its shallow depth
in profile MC1, suggest that severe erosive processes and soil truncation
affect(ed) the soil profiles (cf. Scarciglia et al., 2011) and the sur-
rounding area, where even bare bedrock widely outcrops both on gentle
landforms and steep slopes. Erosion processes are enhanced by the high
local relief generated by the Pleistocene tectonic uplift that displaced
the summit paleosurfaces (Martino et al., 2009; Schiattarella et al.,
2006, 2017), as also recorded in the Sila Massif, located at about 70 km
southeast of Mt. Cerviero (Molin et al., 2012; Olivetti et al., 2012;
Scarciglia, 2015). A rejuvenation of the weathering/pedogenetic front
as a consequence of erosion is also supported by the irregular trends of
some elemental ratios and abrupt changes of CIA values within both soil
profiles, which probably mark a pedological discontinuity between the
bedrock and the overlying soil horizons, along with an increase of or-
ganic matter in the Cr layer of profile MC1 with respect to the overlying
Bt horizon. The effects of soil rejuvenation can also explain the ap-
parent discrepancy between the overall incipient to intermediate de-
gree of weathering (which could be related to late Pleistocene to Ho-
locene soil development; see below in this section and Section 5.4) and
the much older ages of emplacement (Jurassic) and later exhumation
(Miocene) of the pillow basalts after which they were exposed to sub-
aerial weathering and pedogenesis. The young pedogenetic develop-
ment of the Cerviero soils is in good agreement with their clay
mineralogy, characterized by chlorite, illite, hydroxy-interlayered ver-
miculite, kaolinite and different mixed-layer clay minerals including
smectite, coupled with some amounts of short-range order minerals.
The inherited hydrothermal origin of chlorite from the parent material,
and its identification in the MC1 skeleton and MC2 clay fraction, sup-
ports that weathering processes haven't yet affected largely some pri-
mary minerals. This is also in line with the presence of some vermi-
culite, which is a common product of early stage weathering of chlorite
and tends to increase in soils (Perri et al., 2015; Scarciglia et al., 2016).
Also, illite, kaolinite and the interstratified phyllosilicate clay minerals
can derive from chlorite, as well as from micas, feldspars and/or pyr-
oxenes, through weathering processes (e.g., Bétard et al., 2009;
Rasmussen et al., 2010; Vingiani et al., 2010).
The whole phyllosilicate mineral assemblage identified in the pillow
patina (illite, chlorite, vermiculite and smectite in traces) depicts an

306
A.C. Tangari et al. Catena 171 (2018) 299–315

overall early stage of weathering of the basalt parent rock. The presence
(mg kg−1)
of kaolinite (or halloysite) covering the inter-rind portions of the pa-
tina, likely of illuvial origin, is in line with its eluviation from topsoil
bdl
bdl
bdl
bdl
bdl
bdl
bdl
Pb

horizons and translocation downprofile into the bedrock cracks.

The main differences of the pedological features observed in the
(mg kg−1)

field between the two soil profiles (their color, thickness and hor-
17.00

16.00
11.00

12.00
9.00

8.00

4.00
izonation) could be related to different lengths of exposure to soil for-
Rb

mation processes, climate conditions and erosion rates. In particular,

the rubification (i.e., the reddening of the matrix due to the highly
(mg kg−1)

pigmenting power of hematite; Torrent et al., 1983), which is well

bdl
bdl
bdl
bdl
bdl
bdl
bdl

developed in the Bt horizon of soil profile MC1, indicates longer time of

As

pedogenesis and/or warmer and moister (pedo)climatic conditions with

(mg kg−1)

free drainage and marked seasonal water deficit (Schwertmann and

Taylor, 1989; Huang and Wang, 1997; Scarciglia et al., 2011) than soil
bdl
bdl
bdl
bdl
bdl
bdl
bdl
Zn

profile MC2. This hypothesis is consistent with the extent of clay illu-
viation, which is not detected in the soil horizons of profile MC2. He-
(mg kg−1)

matite segregation, among other iron-oxides/hydroxides, could have

been enhanced by the higher pH (Schwertmann and Taylor, 1989), in
bdl
bdl
bdl
bdl
bdl
bdl
bdl
Cu

turn related to higher amounts of carbonate (dolomite) in the skeletal

fraction. In particular, the occurrence of dolomite is likely related to the
(mg kg−1)

“contamination” from the carbonatic sequence within which the basalts

157.00
162.00
149.00
149.00
162.00
156.00
7.00

are intruded. Matrix rubification represents a common pedogenetic

Zr

process of past Pleistocene interglacial periods in the Mediterranean

area, under temperate or warm, humid climate characterized by sea-
(mg kg−1)

sonally contrasted moisture availability (Carboni et al., 2006; Scarciglia

184.00
193.00
179.00
122.00
176.00
171.00
28.00

et al., 2011). During the same time intervals, intense clay illuviation
Sr

also took place in the Mediterranean area (Catt, 1989; Fedoroff, 1997).
(mg kg−1)

The upper pedostratigraphic position of soil profile MC1 and the age
estimated for the volcanic ash input in the overlying A horizon (see
20.00
22.00
30.00
27.00
22.00
24.00
4.00

Section 5.4) suggest that both rubification and accumulation of illuvial

Y

clay could be mainly related to the last interglacial (cf. Scarciglia et al.,
(mg kg−1)

2008). In particular, the microlamination of clay coatings indicates a

32.00
32.00
36.00
31.00
32.00
33.00

cyclical repetition of the illuvial process, which is consistent with long

Chemical composition of trace elements (as mg kg−1) of unweathered (“fresh”) bedrock obtained using XRF.

2.00
Nb

interglacial time spans. Their color variations, mainly due to variable

extent of the Fe-oxide staining, as well as the occasional Fe-Mn segre-
(mg kg−1)

gations, are consistent with variations of moisture availability and/or

730.00

300.00
245.00
290.00
37.00
87.00
72.00

drainage conditions. The fragmentation and peculiar extinction pat-

Ba

terns of the clay pedofeatures indicates that they are affected by de-
generation processes (FitzPatrick, 1984) and suggest an old emplace-
(mg kg−1)

ment, related to paleoclimatic and/or paleoenvironmental conditions

45.00
53.00
70.00
53.00
52.00
55.00
9.00

different from nowadays, even though a reorientation of clay particles

Co

by present-day root acids cannot be ruled out. Among the most common
(mg kg−1)

processes that could have been responsible of the degeneration of the

clay coatings, swelling and shrinkage of clays as a result of wetting-
34.00
38.00
61.00
50.00
27.00
42.00
14.00
Ce

drying cycles (argilloturbation) and bioturbation are very likely.

Cryoturbation, due to freeze-thaw cycles, cannot be ruled out, in line
(mg kg−1)

with the typical mountainous environment of the study area, where

27.00
17.00
30.00
21.00
26.00
24.00

temperature oscillations around 0 °C are quite common during winter,

5.00
La

and could have largely occurred during Pleistocene glacial stages, as

testified by the identification of relict glacial cirques and moraines in
(mg kg−1)

the nearby central-eastern part of the Pollino Massif (Palmentola et al.,

227.00
226.00
260.00
205.00
233.00
230.00
20.00

1990; Giraudi, 1998). Similar climatic conditions, along with active and
V

relict cryogenic processes, are well documented in the Sila Massif up-
(mg kg−1)

land (Scarciglia et al., 2007; Dimase, 2006), located at about 70 km

386.00
353.00
472.00
374.00
419.00
400.00
46.00

southeast of Mt. Cerviero. The alternation of pure clay with silt and
Cr

silty-clay coatings could be the result of such present-day and past

seasonal soil freezing and cryonival processes (possibly enhanced
(mg kg−1)

bdl = below detection limits.

during the last glacial period), where freeze-thaw cycles promote coarse
235.00
174.00
343.00
320.00
278.00
270.00
68.00

particle detachment from soil aggregates and rock, and seasonal ice/
Ni

snow melting facilitates their translocation downprofile (Kemp, 1998;

Standard deviation

Scarciglia et al., 2011). The lack of other diagnostic microfeatures re-

lated to freeze/thawing processes, especially those typical of surface
Unweathered

Mean value

horizons such as lenticular or platy structures, could be explained by

bedrock

the severe erosion which affected the soil profiles. However, we cannot
Table 6

AB15
AB33
AB35
AB40
AB4

exclude stages of exposure of a bare soil to rainfall effects (splash

erosion) together with other dry-wet cycles and subsequent water

307
A.C. Tangari et al. Catena 171 (2018) 299–315

Fig. 6. Bar diagrams showing selected geochemical patterns from fresh bedrock (RF) to weathered bedrock (R) and soil horizons. Soil horizons in profiles MC1 (Cr,
Bt, A) and MC2 (AB, A) are indicated with red and blue color, respectively. CIA values (A); molar ratios between some major elements and titanium (B–H, L); trace
element ratio Rb/Sr (I). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
308
A.C. Tangari et al. Catena 171 (2018) 299–315

Fig. 7. Geochemical patterns of some ratios between pairs of trace elements from the bottom to the top of both MC1 and MC2 soil profiles, indicated with red and
blue bars respectively (A–F). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

infiltration, just reflecting different intensities of water availability, to
explain these pedofeatures.
Similarly, to what observed in the Bt horizon of soil profile MC1,
clay and iron-manganese coatings in the pillow patina and the basalt
cracks, suggest a pedogenetic origin of this patina with migration of
illuviation processes downprofile.
Sheet morphologies of the fine particles in the upper part of the
patina, as identified with SEM analyses, are a clear evidence of a pre-
valent clayey composition of this patina. In addition, the main changes
in its chemical composition detected using EDS analysis, are consistent
with the formation of clay minerals as weathering products of the pri-
mary minerals present in the bedrock. The major elements chemistry
indicates a relative decrease of SiO2, MgO, CaO and an increase of
Al2O3 from the bedrock to the patina, which suggest a progressive
desilication and leaching of basic cations, coupled with Al bonding in
the lattice of neoformed phyllosilicate minerals. The relative depletion
of Mg and Ca indicates both the release and leaching of these elements
from the weathering of primary minerals (plagioclase, clinopyroxene,
pumpellyite), and their partial fixation as interlayer or lattice cations in
clay minerals, such as vermiculite and smectite. Manganese, more than
the other species, exhibits an anomalous behavior, showing higher
contents in some concentric, upper-intermediate rinds of the patina
(where globular, micron-sized, Fe-Mn oxide particles were also identi-
fied in places) compared to the bedrock groundmass, where it was not
detected in EDS maps. Conversely, Mn was detected in some primary
minerals of the bedrock, containing Fe as well, such as chlorite, pum-
pellyite and zeolite. This distribution of manganese is more consistent
with its enrichment in the patina through illuvial processes rather than

Table 7
Data of selective extractions and related geochemical indices in the Cerviero soils. Alo, Feo, Sio, indicate the ammonium oxalate extracted aluminum, iron and silica
content, respectively; Alp indicates the sodium pyrophosphate extracted aluminum content.
Soil profile Horizon Alo% Alp% Feo% Sio% Alo + 0.5 Feo % (Alo − Alp)/Sio Alp/Alo

MC1 A 0.15 0.10 0.28 0.22 0.29 0.23 0.67

Bt 0.16 0.06 0.53 0.35 0.42 0.29 0.37
MC2 A 0.61 0.41 0.61 0.61 0.91 0.33 0.67
AB 0.79 0.60 0.83 0.81 1.20 0.23 0.76

309
A.C. Tangari et al.
in situ weathering of parent rock components. The large extent of il-
luvial Mn and clay in the cracks of the pillows, along with their low
contents in the soil horizons, confirm the above soil truncation, and the
relict significance of clay and manganese illuviation processes.
5.3. Chemical element distribution from bedrock to soil
Geochemical data reflect to variable extent the effects of the che-
mical weathering of primary minerals (and possibly amorphous com-
ponents), but also point out relevant changes of parent rocks across the
soil profiles. The CIA index displayed a clear but abrupt increase from
the basaltic rock to the topsoil horizons in both soil profiles. This is in
line with a progressive increase of weathering intensity from the bed-
rock upward. Furthermore, the high discrepancy of the CIA values from
the bottom to the topsoil horizon, especially in the Cr horizon of soil
profile MC1, corroborates the hypothesis of a rejuvenation of the
310
Catena 171 (2018) 299–315
Fig. 8. Microphotograph to the optical micro-
scope of: illuvial clay and clay-silty coatings
range from yellow to yellowish red (where iron-
stained) in color alternated with brownish
yellow to (red arrow) brown (yellow arrow)
surrounded by chlorite grains (red arrow) in the
Bt horizon, plane polarized light-PPL (A) crossed
polarized light-XPL (B); Degeneration of micro-
laminated clay coatings surrounded by Fe-Mn
segregations (red arrow) in the Bt horizon, PPL
(C) grainy to smooth-banded extinction patterns
of clay coatings XPL (D); Fragmented segrega-
tions of iron-manganese oxy-hydroxides (red
arrow), PPL (E) Neoformed clay in the patina
(red arrow), XPL (MC2 pillow basalt) (F); bed-
rock-patina transition developed on the MC1
pillow basalt. The patina shows abundant Fe-Mn
oxy-hydroxides (yellow arrow) and extensive
argillification (red arrow), PPL (G) and XPL (H).
(For interpretation of the references to color in
this figure legend, the reader is referred to the
web version of this article.)
pedogenetic front caused by erosive processes (more marked in soil
profile MC1) (see Section 5.2) and a pyroclastic input (see Section 5.4).
The irregular geochemical patterns marked by several major (e.g.,
CaO and MgO) and trace elements, which showed much higher or much
lower contents in the Cr/R layer of soil profile MC1 and in the R layer of
MC2 compared to the underlying and/or overlying soil horizons (Fig. 6,
Section 4.5) suggest the presence of lithological discontinuities along
both soil profiles. This finding is consistent with the high amount of
dolomite in the Cr layer, derived from the carbonatic rocks in contact
with the basaltic pillows, and the mixed nature (dolomite and basalt) of
the rock fragments identified both in the field and in thin section in
both soil profiles. Apart from this behavior, the main trends through the
other soil horizons of each soil profile, show more even patterns. For
this reason, hereinafter we will mainly focus on the major vertical
trends in soil profiles, without accounting for the behavior of these
trends in the above Cr layer. The decrease of SiO2 from the bottom
A.C. Tangari et al.
Fig. 9. SEM images of the patina: overall morphology of the patina covering the pillow basalt bedrock (A); sheet clay platelets on the top of the patina (B); particles of
iron and/or manganese oxy-hydroxides, with typical spherical shapes (C); granular to sheet morphology of the illuvial clay particles (D).
(bedrock) to the topsoil clearly indicates a progressive desilication
process linked to the weathering of the primary aluminosilicate mi-
nerals (plagioclase, pyroxene, chlorite, pumpellyite, etc.) and glass. The
SiO2 depletion, together with an Al2O3 increase, indicates the fixation
of aluminum in neoformed clay minerals, as clearly confirmed by the
Al2O3/SiO2 ratio (Scarciglia et al., 2016) (Fig. 6B). The same behavior
is confirmed by both Al2O3 and SiO2 ratioed with TiO2 (Fig. 6C–D)
showing an increase and a decrease, respectively. The overall decrease
of Na2O, CaO and MgO (as well as of the ratios of the same oxides
versus TiO2) towards the topsoil of both profiles (Fig. 6E–G) indicates
that the basic cations, especially Na, are intensely leached. Nonetheless,
according to the medium-high values of CEC, they are partly adsorbed
by the reactive (negatively charged) sites of organic matter and clay
minerals (including short-range order components), and/or enter the
interlayer and crystal lattice of the phyllosilicates, especially smectite
or vermiculite components. The greater amount of sodium in the bed-
rock could also be related to the presence of zeolite minerals and glass
particles. The increase of K2O (and its ratio to TiO2) from the parent
rocks to topsoils in both profiles (Fig. 6H), is an evidence that potassium
is fixed in the illite interlayer after its release from primary minerals
such as feldspar and micas. This behavior is more evident in profile
MC1 than MC2, in line with a prevalence of illite among phyllosilicate
clay minerals in the first profile. Also, the Rb pattern is consistent with
these findings, because Rb preferentially replaces K in K-hosting mi-
nerals (Reimann et al., 2003; Kabata-Pendias, 2011) and is more easily
released during weathering processes, but may be adsorbed or in-
corporated, and therefore enriched, into neogenic clay minerals
(Reimann et al., 2003; Wennrich et al., 2014). A similar behavior is
observed with the Rb/Sr pattern as Rb is selectively less leached than Sr
(Wennrich et al., 2014) (Fig. 6I). As a whole, the increase of Fe2O3 (and
the Fe2O3/TiO2 ratio) from parent rocks to overlying soil horizons in
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Catena 171 (2018) 299–315
both profiles (Fig. 6L) can be related to the Fe content fixed in iron
oxides/hydroxides (especially in the rubified MC1 profile) or linked to
the organic pool (according to the high values in both A and AB hor-
izons). A partly similar (but more irregular behavior in soil profile MC1)
is shown by Mn, mainly sourced by primary chlorite and pumpellyite
and locally concentrated in oxy-hydroxide coatings. Phosphorous is
strictly related to the organic matter retention properties of soils, as
suggested by its usually higher content in A and AB horizons of soil
profile MC2, and their andic behavior characterized by particularly
high phosphate retention (IUSS Working Group WRB, 2014). Ba, as well
as Sr in soil profile MC1, exhibits opposite behavior compared to Ca
(Fig. 7A, B). Sr is more mobile and often selectively leached than Ba,
which tends to be enriched in secondary minerals (Wan et al., 2010).
Both these species commonly replace calcium and potassium in Ca- and
K-bearing minerals (Reimann et al., 2003). Based on their behavior,
their ratios versus titanium appear rather irregular across each soil
profile. However, the great amount of Ba in A horizons of both soil
profiles and in the AB horizon of profile MC2 suggests that it is mainly
adsorbed by organic matter and partly by Fe-oxy-hydroxides in the Bt
horizon of profile MC1 (cf. Reimann et al., 2003). The patterns of Ce
and La versus Ti indicate an enrichment from the bedrock to the topsoil
horizons (Fig. 7C, D). This enrichment trend is likely controlled by rare
earth fractionation during weathering processes (e.g. Mongelli, 1993;
Mongelli et al., 1998) and adsorption onto organic compounds, clay
minerals and Fe-Mn oxides (Laveuf and Cornu, 2009; Scarciglia et al.,
2011), despite the common low mobility of these lanthanides in the
secondary environment (Reimann et al., 2003). The higher content of
lanthanides in the unweathered rocks than the soils is likely related to
plagioclase, pyroxene and the glass fraction present in the bedrock. A
quite homogeneous distribution of titanium, ranging between 2.4 and
2.6% in both soil profiles (except the very low values of Ti in the Cr
A.C. Tangari et al. Catena 171 (2018) 299–315

Fig. 10. Results from scanning electron microscope analyses in thin section. Backscattered electron (BSE) image of MC1 R sample (A), showing the transition in the
bedrock from pillow core to the surrounding rinds (separated by continuum line) in turn separated from the patina (dashed red line). Elemental maps (EDS) for
sample MC1 R, displaying the spatial distribution of three major elements from bedrock to patina: superimposition of the three layers (combined color map) (B); red:
Al (C); green: Mg (D); blue: Si (E). BSE image of MC2 R pillow basalt (F) with a zoom of the patina (black rectangle) shown in G, indicating the spatial distribution of
Ti (red), Fe (green) and Mn (blue). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

layer in soil profile MC1), is consistent with its relatively immobile
behavior. Nevertheless, its maximum content in AB and Bt horizons
shows a weak tendency to concentrate in the fine fraction, where it is
probably stable as Ti-oxide, as long as weathering and pedogenetic
processes proceed (Tyler, 2004; Scarciglia et al., 2016).
The marked lithological discontinuity in soil profile MC1 is clearly
confirmed by the Si/Zr and Ti/Zr ratios, which decrease in correspon-
dence of the Cr/R layer between the bedrock and the overlying soil
horizons (Fig. 7E, F). Actually, since these ratios involve all relative
immobile elements, they are often used as indicators of the parent
material heterogeneity (e.g., Sauer et al., 2007; Scarciglia et al., 2016).
The Ti/Zr pattern marks better such separation between the basalt
bedrock and the upper soil, which can be also supposed for soil profile
MC2, possibly controlled by changes in geochemistry and mineralogy
related to an allochthonous pyroclastic input during pedogenesis (see
next Section 5.4).
5.4. Pyroclastic input
The typical andic-like morphological features described in the field
for the two soil profiles are consistent with (i) the prevalent optically
isotropic pedogenic matrix of the A horizons, suggesting that poorly
crystalline or amorphous components are present (e.g., Scarciglia et al.,
2008; Vingiani et al., 2014); (ii) the identification of micrometric glass
shards and vesiculated micropumices in the same soil matrix; and (iii)
the results of the selective extraction analysis. The latter data show that
the Alo + 0.5 Feo index is always lower than 2%, which is the minimum
required to enter the Andisol group according to the WRB criteria for
andic properties (IUSS Working Group WRB, 2014). Nonetheless, for
almost all the soil horizons, this index is ≥0.4%, which is a low-level
proxy for andic properties according to the USDA Soil Taxonomy, along
with a volcanic glass content ≥ 5% (Soil Survey Staff, 2014), whereas it
is an indicator of vitric properties in the WRB classification system
(IUSS Working Group WRB, 2014). The overall low (Alo − Alp)/Sio
ratio, together with Alp/Alo values close to 0.7 (except for horizon Bt of
soil profile MC1), indicate that Al can be assumed to form mainly
complexes with organic matter, thus limiting the formation of short-
range order aluminosilicates (Nanzyo et al., 1993; García-Rodeja et al.,
2007). Therefore, as a whole both soil profiles show weak andic
properties, although some apparent features of Andosols were observed
in the field. A low but relatively higher amount of poorly crystalline
mineral components can be supposed for soil profile MC2 than MC1,
because of its higher Alo + 0.5 Feo values and Sio content. Based on
their properties, profile MC1 can be classified as a Humic Aluandic

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A.C. Tangari et al. Catena 171 (2018) 299–315

and a windblown pyroclastic input, with further contribution of dolo-

mitic limestone in soil profile MC1.

6. Conclusions

This study provides a comprehensive understanding of the genesis,

evolution and geochronology of two representative soil profiles devel-
oped on alkaline pillow basalts in the Mt. Cerviero area (Calabria,
southern Italy) and allowed to discriminate the main diagnostic fea-
tures of submarine hydrothermal alteration from those related to
weathering and pedogenesis in subaerial conditions. The hydrothermal
alteration of the basalt produced chlorite, pumpellyite, prehnite, epi-
dote, zeolite and sericite mica minerals whereas, the chemical weath-
ering led to the formation of clay minerals (illite, hydroxy-interlayered
vermiculite, kaolinite, different mixed-layers including smectite, and
short-range order minerals) in both a patina coating the pillow core and
the soils.
The observed features suggest an important imprint of the parent
material in the soils. The presence of a lithological discontinuity be-
Fig. 11. SEM image of glass shards (red arrows) in the A horizon of soil profile tween the bedrock and the upper soil horizons indicates a rejuvenation
MC1. (For interpretation of the references to color in this figure legend, the of the weathering/pedogenetic front as consequence of erosive pro-
reader is referred to the web version of this article.) cesses triggered by the Pleistocene tectonic uplift of the study area. This
is also supported by the large extent of Mn and clay illuviation in the
pillow cracks, despite the generally poor Mn and clay contents in the
Luvisol and profile MC2 as a Mollic Protoandic Umbrisol according to
overlying soil horizons. These illuvial pedofeatures, their relict sig-
the WRB.
nificance and the concurrent matrix rubification point to temperate or
The coexistence of poor SROM components with phyllosilicate mi-
warm and humid climatic conditions, characterized by seasonally
nerals suggests that part of the silica available in the soil system is also
contrasted moisture availability, possibly occurred during the last in-
incorporated into the lattices of crystalline clays along with aluminum
terglacial. Soil rejuvenation can be partly related to an input of al-
(in line with the clay mineralogy; see Sections 4.4, 4.8 and 5.2) and thus
lochthonous pyroclastic material, as indicated by the presence of glass
further contributes to inhibit the formation of short-range order alu-
particles and changes in the geochemical features from the basaltic
minosilicates. A certain amount of Si is likely leached out of the soil
bedrock to the topsoil.
profiles, in accordance with the desilication evidenced by geochemical
The Late Pleistocene age estimated for both soils is supported by the
data (see Sections 5.2 and 5.3), and with the very humid climatic
trachytic composition of the volcanic glass fragments, which is con-
conditions and high precipitation rates of the Cerviero area. As a high
sistent with putative explosive eruptions from the Campania province
moisture availability promotes the neogenesis of SROM components
(Vesuvius and Campi Flegrei) or the Aeolian Arch (mainly Lipari and
over the phyllosilicates (e.g., Rasmussen et al., 2010), some changes in
Volcano Islands), occurred during the Pleistocene-Holocene epochs.
the main climatic conditions could have occurred at the study sites,
Finally, this work demonstrates that the Andosol-like field appear-
possibly with episodes of higher seasonality during the late Pleistocene
ance can be used as a potential indicator of cryptotephras, even when
and the Holocene (cf. Section 5.2), also documented in other sites of
andic properties are not well-developed. This finding suggests that a
southern Italy (e.g., Scarciglia et al., 2008, 2014; Pelle et al., 2013).
possible contribution of fine volcanic ash (invisible to the naked eye
Moreover, phyllosilicate and poorly crystalline clay minerals could be
and optical microscopy) to soil formation in soils of non-volcanic areas
partly linked to the mixed nature (basalt rock and volcanic ash) of the
should be investigated in more detail, especially at the submicroscopic
soil parent material.
level, when andic properties or at least andic-like field features occur.
The trachytic composition of the volcanic glass in the Cerviero soils
This should lead to a partial reassessment of the volcanic versus non-
is consistent with a provenance from the Late Pleistocene and Holocene
volcanic origin of certain Andosols worldwide and claims a good field
volcanic eruptions of the Campania Province (Vesuvius and Campi
work with detailed description of soil properties as a basis for choosing
Flegrei) or part of the Aeolian Arch (mainly Lipari and Volcano Islands)
the best-suited laboratory methods, to fill the gap between ordinary lab
during the last 50–60 ka (Paterne et al., 1988; Vingiani et al., 2014;
and field results.
Albert et al., 2017; Raab et al., 2017). Both of these volcanic districts
are about 180–190 km far from Mt. Cerviero and coherent with a distal
Acknowledgements
deposition of the very fine size of glass particles found in the studied
soils. However, in another soil profile (MOR) sampled in the Pollino
The authors thank M. Davoli and G. Niceforo (University of
Massif upland, just 1 km southeast of profiles MC1 and MC2, Vingiani
Calabria) for their help during SEM-EDS and X-ray fluorescence ana-
et al. (2014) identified rhyolitic micropumices dispersed in the pedo-
lyses, respectively. We wish to thank D. Cirillo (University of Chieti-
genic matrix, whose provenance is more likely from the Aeolian Islands
Pescara) for his help with the use of ArcGIS software package. We thank
volcanism. This apparent inconsistency could be explained by different
M. Bocci (University of Calabria) and S. Toro (University of Chieti-
volcanic sources or more likely by some changes in glass geochemistry
Pescara) for the total carbonate content analysis. This study was part of
(mainly loss of mobile alkalis or desilication by leaching processes)
the PhD thesis of A.C. Tangari at the University G. d'Annunzio Chieti-
during soil formation, probably due to local environmental conditions
Pescara. We are grateful to three anonymous reviewers for their con-
(e.g., different moisture availability and drainage, time of interaction of
structive comments and suggestions that helped to increase the quality
glass fragments with soil solution). This behavior could have led to a
of our manuscript.
varying and therefore uncertain compositional signature.
The above volcanic ash very likely contributes to explain the li-
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