Clay Minerals, (2010) 45, 115–130

Use of T max as a thermal maturity indicator

in orogenic successions and comparison
with clay mineral evolution
F. DELLISANTI1,*, G. A. PINI1 AND F. BAUDIN2
1
Dipartimento di Scienze della Terra e Geo-Ambientali, Università di Bologna P. Porta S. Donato, 1 I-40126, Bologna,
Italy, 2 UPMC ! Université de Paris 06, CNRS-UMR 7193, ISTEP, Equipe Evolution et Modélisation des Bassins
Sédimentaires, case 117, 4 place Jussieu 75252 Paris Cedex 05, France

(Received ; revised )

AB ST R ACT : The relationship between three parameters, the Tmax given by Rock-Eval pyrolysis,
the illite content in illite-smectite mixed layers (I-S) and the Kübler Index (KI) has been investigated
in the Cretaceous!Neogene, sedimentary syn-orogenic successions in the Northern Apennines
(Italy). A strong relation was found between maturity stages of kerogen, illite content in I-S and KI.
The oil formation zone for continental organic matter (Type III), delimited by Tmax between 434 and
465ºC, corresponded to rocks with short-range ordering R1, I-S with illite content between 60 and
85% and KI values in the range 0.85!0.65 (ºD2y). Over-mature rocks were characterized by Tmax
>465ºC, a long-range ordered I-S with an illite content >85% and KI in the range 0.65!0.45 (ºD2y).
The relationship permits use of both mineralogical parameters and T max to estimate
palaeotemperatures in sedimentary successions and it can be exploited in hydrocarbon research to
evaluate the petroleum potential.

KEYWORDS: Rock-Eval pyrolysis, Tmax, Kübler Index, illite!smectite, thermal maturity, palaeotemperatures,
petroleum potential.

Tmax is defined as the pyrolysis temperature at
which the maximum amount of hydrocarbon is
released by kerogen (Espitalié et al., 1977). As a
general rule, Tmax increases linearly with the
maturation degree of the organic matter (Barker,
1974; Espitalié et al., 1977), thus giving a rapid
estimate of the thermal maturity of sedimentary
basins. Tmax is dependent on the cracking kinetics
of the organic matter and is correlated with the type
of organic matter: lacustrine (Type I), marine
(Type II) and continental (Type III). The relation-
ship between Tmax and different stages of oil and
* E-mail: f.dellisanti@unibo.it
DOI: 10.1180/claymin.2010.045.1.115
gas formation zones varies with the type of organic
matter; however Type III is the most reliable in
estimating the maturation degree (Espitalié, 1986).
The variation of Tmax with the organic matter
maturity has been compared to the change in
vitrinite reflectance (%Ro) (Teichmüller &
Durand, 1983; Espitalié et al., 1984) and, for the
kerogen of Type III, the beginning of the oil
formation is characterized by Ro of 0.5% and Tmax
in the range 430!435ºC, whereas the transition oil-
gas zone is fixed at Ro of 1.35% and Tmax ~465ºC
(Espitalié, 1986).
The progressive conversion of smectite to illite
and the ordering of the illite structure, indicated by
the Kübler Index (‘illite crystallinity’) (Kübler,
1967; Guggenheim et al., 2002), are a function of
the burial temperature (see Kisch, 1983; Frey, 1987;
Frey & Robinson, 1999). The illitization reaction

# 2010 The Mineralogical Society

116 F. Dellisanti et al.
and the illite Kübler Index are widely used as
thermal indicators in sedimentary successions of
low- and very low-grade metamorphism and,
associated with the vitrinite reflectance, are used
to determine a scale of palaeotemperatures
(Jaboyedoff & Thelin, 1996; Merriman & Frey,
1999). However, the relationship between clay
minerals and Tmax evolution is not well defined.
Burtner & Warner (1986), in a preliminary study
using selected samples from wells, reported a
correlation for the oil window, indicating Tmax
values in the range 435!460ºC and an illite content
in illite-smectite mixed layers (I-S) between 60 and
90%, although they did not find a linear relation-
ship. On the contrary, a poor correlation between
the illite content in I-S and kerogen maturity was
found by Scotchman (1987), who pointed out that
the illitization reaction was strongly influenced by
either the pore-water chemistry or K+ availability,
suggesting the need to adopt extreme caution in
using the clay mineral evolution as an indicator of
the thermal maturity of sedimentary basins when
the chemical factors are not well constrained.
Velde & Espitalié (1989) have found regular
trends between the illite content in I-S and Tmax
values in wells from six sedimentary basins,
suggesting a range of correlation between the two
parameters. However, the relationship between the
kerogen maturity and clay transformation applied
only to sediments at the end of the illitization
reaction (about 90% of illite content in I-S)
whereas, between immature kerogen and more
smectitic I-S mixed layers, the correlation was not
clear or failed because of the different reaction
kinetics. Furthermore, the data analysed in previous
work corresponded only to late Tertiary and older
sequences, while the kerogen maturity and clay
mineral evolution could also be dependent on the
age of the rocks (Velde & Espitalié, 1989).
A well defined correlation between Tmax and
mineralogical data can be useful both to enable the
use of Tmax as a geothermometer and to support
petroleum research in calculating maturity organic
parameters. Thus, to overcome the uncertainty
mentioned above, the present work reports a study
of the relationship between Tmax and clay mineral
evolution, examining sedimentary syn-orogenic
successions covering a wide timespan from the
early Cretaceous up to the late Pliocene. In
addition, as a novel approach, the correlation
between Tmax and the Kübler Index in the same
sedimentary successions is also reported.
GEOLOGICAL SETTING
The Northern Apennines of Italy are an orogenic,
northeast-verging wedge composed of stacked
nappes and thrust-bounded units (Elter, 1975;
Barchi et al., 2001; Carmignani et al., 2001;
2004; Cerrina Feroni et al., 2004). The more
extensive and distant allochthonous nappe, the
Ligurian nappe, consists of several structural units,
which can in turn be grouped into the Ligurian and
Subligurian units (Bortolotti et al., 2001; Cerrina
Feroni et al., 2004, and references therein) (Fig. 1).
The Ligurian units derive from the middle
Jurassic to late Cretaceous-Eocene sedimentary
cover and basement of the Ligurian ocean, a part
of the oceanic seaways of the Neo-Tethys, and from
the thinned margin of a conterminous, easterly-
placed, continental domain (African promontory,
Channell et al., 1979, or Adria microplate, Dercourt
et al., 1986). The so-called Internal Ligurian units
actually display complete sequences of oceanic
crust beneath the sedimentary cover (Bortolotti et
al., 2001; Marroni & Pandolfi, 2001). The oceanic
crust is only present as blocks and slabs in mass
wasting deposits at the stratigraphic base of the
external Ligurian units, together with fragments of
continental crust (Marroni et al., 2001). The
Subligurian units are considered to represent the
sedimentary cover of the Adria microplate origin-
ally positioned to the East of the Ligurian units
(Bortolotti et al., 2001).
The Ligurian units, or part of these, participated
in a late Cretaceous-Eocene accretionary wedge
(e.g. Vai & Castellarin, 1993; Pini, 1999, Vescovi
et al., 1999; Daniele and Plesi, 2000; Marroni &
Pandolfi, 2001), mainly related to the subduction of
oceanic crust, which was part of a single Alpine
orogen (e.g. Laubscher et al., 1992; Doglioni et al.,
1999; Castellarin, 2001; Mantovani et al., 2008),
together with the Alpine units of Corsica (Molli,
2008, and references therein). The diverse structural
units experienced different burial depths during this
phases of deformation (hereafter defined as ‘Alpine
phases’), with the Internal units that were stacked
westward by thrust faults and, in turn, overthrust by
the External units (see Antola unit in Fig. 1) (e.g.
Marroni, 1994; Marroni et al., 1999, 2001; Levi et
al., 2006). The estimated palaeotemperatures for the
Internal Ligurian units increase gradually from E to
W, until reaching the metamorphic condition of the
Cravasco-Voltaggio unit and the Western Alps
(Reutter et al., 1980, 1983; Leoni et al., 1996,
 Relationship between Tmax and clay minerals 117

FIG. 1. Structural-geological map of the Northern Apennines and location of the sampling sites.

1998; Ducci et al., 1995; Ellero et al., 2001; Leoni,
2001). Deformation also occurred in the External
Ligurian units during this stage, possibly related to
retrovedge kinematics, changes of subduction
direction or to transpressions (Marroni & Treves,
1998; Marroni et al., 2001; Molli, 2008, and
references therein).
The Ligurian nappe as a whole has been
subsequently involved in the Oligocene-Plio/
Pleistocene intracontinental deformations on the
western margin of the Adria microplate
(Apenninic phases: Castellarin et al., 1992;
Cerrina Feroni et al., 2004). During these phases,
the Ligurian nappe always maintained the highest
position on top of the stack of nappes and units,
since it progressively moved NE above the Adria
margin (Boccaletti et al., 1990, and reference
therein; Castellarin et al., 1992). The age of
emplacement of the Ligurian nappe above the
sediments of the Adria microplate progressively
changes from early Oligocene on the western side
(close to the Tyrrhenian Sea), to early-middle
Miocene along the Apennines main divide, to the
middle-upper Miocene and Pliocene towards the NE
border of the chain (Ricci Lucchi, 1986; Boccaletti
et al., 1990; Lucente & Pini, 2008, and references
therein). The translation of the nappe mainly
occurred in submarine conditions, so that middle-
late Eocene to Pliocene sedimentary successions
deposited in satellite basins were deposited on top
of the Ligurian nappe (Epiligurian basins: Ori &
Friend, 1984; Ricci Lucchi, 1986).
Deformation related to this stage also occurred
inside the nappe, reactivating and/or offsetting the
118 F. Dellisanti et al.

tectonic contacts inherited by the Alpine phases.
The main structures have been referred to thrust
faults propagating from the base of the nappe
(Castellarin & Pini, 1989), normal faults (Bertotti et
al., 1997; Capozzi & Picotti, 2002) and/or diapiric-
like reactivation of stratally-disrupted units
(mélanges) from the base/lower part of the nappe
(Castellarin & Pini, 1989; Borgia et al., 2006; Festa
et al., 2010).
The translation of the Ligurian nappe and of the
overlying Epiligurian basins coincides with the
onset of thrust-bounded structural units from the
successions of the western margin of Adria, such as
Tuscan metamorphic units, the Tuscan nappe, the
Cervarola-Falterona unit and the Umbria-Romagna-
Marche fold-and-thrust belt (Fig. 1). Deformation
of the Adria-related successions occurred at the
front and below the lip of the advancing Ligurian
nappe. The more recent sediments of the Adria-
related successions are thick, turbiditic sequences
considered to be the infill of a migrating foredeep
(the Macigno, Mt. Falterona, Mt. Cervarola and
Marnoso-arenacea Formations) and finer-grained,
slope deposits (‘draping muds’; Ricci Lucchi,
1986). Tectono-sedimentary mélanges due to the
deformation of coalescent bodies from submarine
landslides and debris flows are interbedded between
the top of the foredeep successions and the base of
the Ligurian nappe (Lucente & Pini, 2008;
Vannucchi et al., 2008; Camerlenghi & Pini, 2009).
The maximum thickness of the Ligurian nappe,
containing the Epiligurian sediments and the sub-
nappe mélanges, is 4!4.5 km, inferred from
industrial wells and shown in some recent
reconstructions (Cerrina Feroni et al., 2002;
Boccaletti et al., 2004).
MATERIALS AND METHODS
Sampling
A suite of 71 samples was collected from the
Epiligurian, External and Internal Ligurian,
Subligurian and Cervarola-Falterona structural
units cropping out in the Italian Northern
Apennines (Fig. 1, Table 1). The units studied

TABLE 1. Mineralogical parameters (KI and % illite in I-S), total organic carbon (%TOC), Tmax and hydrogen
index data, and vitrinite reflectance data (%Ro) for different structural units. (Tmax) indicates anomalously low
values due to oil impregnation.

Sample Kubler Index Illite in I-S Ordering Tmax Hydrogen Index TOC Ro
(~º2y) (%) I-S (ºC) (mgHC/gTOC) (%) (%)

Internal Ligurian (early Cretaceous–early Paleocene)

T184 0.65 100 R3 569 15 0.97 n.m.
T220 0.55 90 R3 !362 54 0.21
T157 0.46 100 R3 !351 45 0.34 n.m.
T223 0.54 100 R3 !358 57 0.66
T151 0.48 100 R3 !331 21 0.58
T155 0.39 100 R3 !362 22 0.47 n.m.
T225 0.48 100 R3 !353 56 0.59
Subligurian (middle Eocene)
T189 0.8 77 R1 476 60 0.21
Epiligurian (late Eocenelate Pliocene
T180 0.7 85 R1 465 45 0.29
T192 0.47 100 R3 438 38 0.55
T178 0.54 100 R3 468 20 0.54 0.91
T160A 0.54 100 R3 456 106 0.65 1.68
T193A 0.48 100 R3 499 17 0.64 1.57
T176 0.54 100 R3 563 22 2.22 0.73
T191 0.39 100 R3 !327 63 0.36 n.m.
T195 0.69 88 R3 !358 51 0.24
T162 0.54 100 R3 !361 193 0.14
T145 0.53 100 R3 !353 112 0.16
Slr28 n.m. 22 R0 419 80 0.30 0.3
Slr5pt n.m. 22 R0 420 80 0.31
 Relationship between Tmax and clay minerals 119

TABLE 1. (contd.)

Sample Kubler Index Illite in I-S Ordering Tmax Hydrogen Index TOC Ro
(~º2y) (%) I-S (ºC) (mgHC/gTOC) (%) (%)

Slr5apt n.m. 22 R0 420 73 0.79

Slr6 n.m. 25 R0 420 78 0.40
Af1c n.m. 44 R0 420 70 0.32
Slr5asp n.m. 31 R0 422 70 0.41
Slr43pt n.m. 33 R0 422 87 0.29
Slr28sp n.m. 20 R0 423 33 0.59
Slr25pt n.m. 24 R0 425 73 0.30
Slr6sp n.m. 25 R0 425 110 0.20
Slr39sp n.m. 30 R0 425 100 0.20
Slr27pt n.m. 35 R0 425 93 0.32
Slr39pt n.m. 45 R0 425 68 0.61
Slr48pt n.m. 50 R0 429 90 0.39
Af1ept n.m. 39 R0 430 103 0.30
Slr41pt n.m. 33 R0 431 83 0.31
Slr27sp n.m. 19 R0 432 100 0.20
T209 n.m. n.m n.m 424 67 0.42
External Ligurian (early Cretaceous–middle Eocene)
T88 n.m. 54 R0 424 68 0.37
T113 n.m. 60 R0 428 61 1.24 0.47
T1pt n.m. 26 R0 430 95 0.18 0.49
T122 n.m. 60 R0 430 80 3.42 0.42
T110 n.m. 38 R0 431 76 0.84
T111 n.m. 60 R0 431 90 0.37
T29 0.77 76 R1 433 170 0.20 1
T114 n.m. 47 R0 434 48 2.10
T116 n.m. 51 R0 434 38 0.73 0.83
T168 0.87 67 R1 435 111 0.63 0.39
T92 0.78 84 R1 436 20 0.85
T133 n.m. 46 R0 437 42 0.81
T85 0.72 82 R1 437 166 0.50
T62in 0.82 69 R1 438 137 0.31
T66df 0.69 85 R1 440 160 0.13
T36 0.68 81 R1 443 2 1.98 1.11
T127 0.78 70 R1 457 73 0.41
T136 0.64 90 R3 466 54 0.77
T137 0.67 92 R3 496 18 0.56 0.69
T138 0.64 82 R1 502 37 1.08
T124 n.m. 54 R0 512 11 0.92
T213 0.66 89 R3 477 58 0.33
T221 0.65 86 R3 483 47 1.15 1.48
T205 0.68 86 R3 520 13 0.96
T204 0.59 92 R3 532 11 1.20 n.m.
T143 0.78 84 R1 !330 59 0.29
T144 0.63 91 R3 !353 56 0.35
T146 0.6 92 R3 !359 35 0.32 0.76
T159 0.7 91 R3 !354 49 0.27
T172 0.51 90 R3 !363 126 0.36
T187 0.68 84 R1 !338 142 0.25
T201 0.74 83 R1 !349 86 0.26
T219 0.63 90 R3 !359 114 0.50
T222 0.59 90 R3 !361 91 0.45
T106 n.m. n.m n.m 418 68 0.36 0.39

n.m.: not measurable

120 F. Dellisanti et al.
covered a wide range of thermal maturity, from a
shallow diagenetic zone up to anchizone (Leoni et
al., 1996; Botti et al., 2004; Dellisanti & Pini,
2007; Dellisanti et al., 2008). Since geothermal
anomalies or short periods of intense heating due to
magmatic intrusions were not present, a mean
geothermal gradient of about 30ºC km!1 was
assumed for the last, Oligocene-Pliocene to recent
stages of intracontinental deformation (Reutter et
al., 1980; Ventura et al., 2001; Zattin et al., 2002).
High-pressure, low- temperature conditions
(20!25ºC km !1 ) should be expected for the
Cretaceous-Eocene accretionary wedge (Marroni,
1994; Molli, 2008). All the samples were analysed
by Rock-Eval pyrolysis and by X-ray powder
diffraction (XRD); in a few samples the vitrinite
reflectance was also determined.
Analytical methods
Rock-Eval pyrolysis is used to determine the
petroleum potential and the thermal maturity of the
kerogen occurring in a rock, as proposed by Espitalié
et al. (1977; 1985a,b). The procedure consists of
progressive heating (25ºC min!1) of the whole rock
from 25ºC to 650ºC by using the Rock-Eval 6
analyser (VINCI Technologies) which measures the
hydrocarbons released during the heating over the
temperature range 300!650ºC. The amount of
hydrocarbon compounds (HC) given in mg g!1 of
dry rock (S2 parameter) indicates the oil not yet
released from the rock by natural processes and
represents the residual petroleum potential. The
temperature at which the maximum amount of HC
is generated is indicated as Tmax (culmination of S2
peak) and is used as an indicator of the thermal
maturity of the rock (Espitalié, 1986). The total
organic carbon (TOC) can also be determined using
the Rock-Eval 6 apparatus. The hydrogen index (HI)
has been obtained from the ratio of S2/TOC. Because
the pyrolysis of coals and kerogens of various origins
has shown a good correlation between HI and the
elemental composition of organic matter (Espitalié et
al. 1985a), the correlation with Tmax permits
determination of the type of organic matter in the
rocks. Standard samples (IFP 160000 and FB 2330)
and a blank were used as reference materials to
calibrate the Tmax data. Only samples with S2
>0.1 mgHC g!1 were considered reliable in esti-
mating the Tmax values (Espitalié et al. 1985a,b).
Mineralogical and crystallographic data were
determined on <2 mm grain-size fractions by
powder XRD. Following Kisch (1991), the <2 mm
fraction was obtained by differential settling after
disintegration by shaking in demineralized water and
ultrasonic disaggregation for up to 15 min. Both air-
dried and ethylene-glycol solvated samples (50ºC
overnight) were analysed using a Philips PW 1710
diffractometer (Philips PW 1710, Cu-Ka radiation;
40 kV/30 mA power supply; graphite secondary
monochromator, 1º divergence and scatter slits,
0.1 mm receiving slit; 0.02º2y step size; counting
time of 2 s/step). Smeared oriented mounts were
prepared for each sample ensuring that the amount
of clay on the glass slide was >3 mg cm!2
(Lezzerini et al., 1995). Mineralogical parameters
were determined by processing the XRD patterns by
the WINFIT program (Krumm, 1996) using an
asymmetrical Pearson VII function (Stern et al.,
1991; Warr & Rice, 1994). The occurrence of mixed
layer illite-smectite (I-S) and the concentration of
illite in I-S was confirmed in the XRD patterns by
applying the NEWMOD# simulation program
(Reynolds, 1985). The identification of mixed-layer
I-S was based on d spacings of the 001 peak; the
concentration of illite in I-S was determined based
on peak positions of I-S in the range 16!17.7º2y
(glycolated specimen). Following the criteria
reported by Moore & Reynolds (1989), a disordered
R0-type I-S with illite content <60%, a short-range
ordered R1-type I-S with illite content between 60
and 85% and a long-range ordered R3-type I-S with
illite content >85% (Reynolds, 1980) were recog-
nized. The Kübler Index (KI) (Kübler, 1967;
Guggenheim et al., 2002) was only calculated in
the samples in which R1 or R3-type I-S occurred. KI
data were calibrated against the CIS scale (Warr &
Rice, 1994) using the following regression equation:
KI(CIS) = 0.93 KI(Bologna) + 0.09 (R2 = 0.95)
(Dellisanti et al., 2008).
The vitrinite reflectance method has been widely
used in determining the thermal maturity of the
organic matter in sedimentary rocks. Vitrinite is an
important maceral product showing a progressive
ordering of the structure as a consequence of
increasing thermal maturity of a rock (Tissot &
Welte, 1984). Vitrinite random reflectance (%Ro)
measures the reflection capacity in incident light in
relation to the incr ease of the palaeotemperature
(Teichmüller, 1958; Stach et al., 1982) and is
reliable only when at least 20 unaltered vitrinite
particles can be measured. Among the 21 samples
analysed in the present work, only 16 have provided
reliable data for vitrinite reflectance measurements.
 Relationship between Tmax and clay minerals 121

RESULTS samples contained kerogen with different stages of

Tmax by Rock-Eval pyrolysis
A group of 19 rocks showed faint S2 peaks over a
very low temperature range (327!363ºC) (Table 1,
Fig. 2), indicating the presence of free heavy
hydrocarbons already generated by the source rock
but not yet expelled. These rocks were not reliable
for maturity determination because the measure-
ment of the S2 peak has been made on the oil
fraction and not on the autochthonous organic
matter (kerogen). In the rocks with reliable S2
parameters, the Tmax values ranged from 418 to
569ºC (Table 1). Fig. 2 reports the relationship
between Tmax and the hydrogen index (HI) and
permits determination of the type of organic matter
in the rocks. In particular, the analysed samples
contained organic matter of continental origin
related to Type III (Espitalié et al., 1985a).
However, small values of HI, associated with a
relatively low TOC content, that in most of the
samples was lower than 1% (Table 1), indicated the
presence of organic matter dispersed in the mineral
matrix rather than in coal layers. For Type III
organic matter, as proposed by Espitalié et al.,
(1985a), a Tmax of 434ºC was adopted as the
boundary between immature and mature kerogen
(oil production zone) and a Tmax of 465ºC as the
boundary between mature and over-mature kerogen
(gas-production zone). Figure 2 shows that the
thermal maturity, i.e. immature, oil-window, gas-
window and over-mature.
In shallow diagenetic areas, samples of the
Epiligurian units were collected from both fault
rocks and non-deformed rocks to evaluate the
possible influence of the tectonic strain on Tmax.
However, the results indicated very similar Tmax
values, suggesting that the temperature of digenetic
alteration was not significantly influenced by
tectonic deformation (Dellisanti et al., 2008).
Mineralogical data
The KI values and the illite content in I-S are
given in Table 1. Since the KI is reliable only when
the smectite-illite reaction reaches an equilibrium
stage, it was calculated only for the samples
containing ordered R1 or R3-type with illite
content in I-S >60%. In samples from shallow
diagenetic zones, characterized by the presence of a
disordered R0-type I-S (illite content <60%), the
detrital illite was predominant with respect to that
from authigenic zones and could influence the
measurement of the KI. However, in order to
present data from these rocks, a nominal value of
1.50 (ºD2y) for KI was adopted. In a few samples,
I-S was lacking because the illitization of I-S was
complete; then a value of 100% of illite in I-S was
considered.

FIG. 2. Hydrogen index!Tmax diagram. Bold and dotted curves delimit the evolution paths for pure organic matter
(coal) and dispersed in rocks for Type III (continental OM). 1, Immature!mature transition; 2, Mature!over-
mature transition; 3, for Type III kerogen, transition between wet gas and dry gas zone (Modified from Espitalié
et al., 1985a).
122 F. Dellisanti et al.
In 27 rocks a disordered R0-type I-S with an
illite content <60% was measured, indicating a
shallow diagenetic zone for these rocks (Table 1)
(Merriman & Frey, 1999; Arkai et al., 2002). The
rocks in shallow diagenetic conditions were related
to Epiligurian units (late Eocene-late Pliocene) and
to a few samples of the External Ligurian units
(early Cretaceous-middle Eocene) collected in the
eastern sector of the Apennines. A second group of
14 rocks, belonging to External Ligurian units
widely distributed in the Northern Apennines,
showed an ordered R1-type I-S with an illite
content between 67 and 85% and KI values from
0.87 to 0.64 (ºD2y) indicating for these a deep
diagenetic zone (Merriman & Frey, 1999; Arkai et
al., 2002). A third group of 28 rocks of the
Cervarola-Falterona unit (middle Miocene), Internal
Ligurian (early Cretaceous!early Paleocene) and
External Ligurian in the south western sector,
showed an ordered R3-type I-S with an illite
content between 86 and 100% and KI values from
0.68 to 0.39 (ºD2y), indicating metapelitic zones
from deep diagenesis up to the early anchizone
(Merriman & Frey, 1999; Arkai et al., 2002).
Vitrinite reflectance data
Vitrinite reflectance data (Table 1) showed the
presence of immature organic matter in six rocks
with Ro <0.5%; in seven rocks Ro values between
0.5 and 1.35 % were found, which are considered as
limits for oil formation; and in three rocks organic
FIG. 3. Relationship between Kübler Index and illite content in I-S. The samples with a disordered R0-type I-S
are not shown.
matter with Ro >1.35% are related to gas-formation
zones (Burnham & Sweeney, 1989; Horsfield &
Rüllkotter, 1994).
Comparison between kerogen maturity and
clay mineral evolution
Mineralogical parameters showed good agree-
ment with the linear relationship found between KI
and illite content in I-S and permitted evaluation of
the thermal maturity (Fig. 3). The illite content in
I-S increased with the Tmax data (Fig. 4) following
a logarithmic relationship, indicating a wide
variability of the illite content in I-S for a narrow
range of immature and mature kerogen, whereas for
over-mature kerogen the illite is less variable
because the illitization is in an equilibrium state.
However, taking into account the limits proposed
by Espitalié et al. (1985a,b) and Espitalié (1986),
all the rocks with immature kerogen (Tmax 4434ºC)
presented an illite content <60%, corresponding to a
disordered R0-type I-S (Fig. 4 and Table 1). The
rocks with Tmax within the oil window (Tmax in the
range 435!465ºC) generally showed illite contents
between 65 and 85% (R1-type), except for two
samples in which I-S was lacking and are reported
as 100% illite in I-S (samples T192 and T160). The
rocks with Tmax within the gas window (Tmax
>465ºC) showed the concentration of illite in I-S
between 82 and 100% (R1-type and R3-type),
except for two samples with contents of 77%
(sample T189) and 54% (sample T124) respectively
 Relationship between Tmax and clay minerals
FIG. 4. Relationship between Tmax and illite content in I-S. The samples with 100% illite indicate rocks in which
I-S was absent. 1, R0-R1 type I-S transition; 2, R1-R3 type I-S transition (Reynolds, 1980).
(Fig. 4). Sample T189 with a Tmax of 476ºC and
illite <80% can be considered to belong to an
intermediate zone, whereas the data of sample T124
can be attributed to the low value of the S2
parameter (0.1 mgHC g!1); here Tmax was not
reliable enough to determine the thermal maturity
(Espitalié et al., 1985a,b). The rocks with free
hydrocarbon (Tmax <365ºC) showed a large illite
content in I-S (83!100%) (Table 1).
A detailed comparison between the Tmax and KI
data showed significant relations between the two
parameters (Fig. 5). All the rocks with immature
kerogen (Tmax 4434ºC) corresponded to the
samples in which KI was not measurable because
of the early stage of the illitization reaction. The
rocks with Tmax within the oil window (Tmax in the
range 435!465ºC) showed KI values between 0.87
and 0.68 (ºD2y) (Fig. 5), except for samples T192
and T160 which have KI values <0.60 (ºD2y); these
are the two anomalous samples mentioned above
with an illite content of 100%. These samples
showed mineralogical features comparable with
those of other rocks belonging to the same
structural unit (Cervarola-Falterona). In this case
an underestimation of Tmax could be due to a
difference in evolution between kerogen and the
clay minerals. The disagreement between miner-
alogical and Tmax data in sample T192, besides
123
being related to a greater rate of reaction of the clay
minerals, could be also attributed to an over-
estimation of the KI due to the possible influence
of detrital illite in a silt-rich rock. The rocks
containing over-mature kerogen (Tmax >465ºC)
showed KI values between 0.65 and 0.48 (ºD2y)
(Fig. 5) apart from samples T189 and T124. As
already shown in the I-S data, these samples
showed similar mineralogical parameters. They
were also consistent with the structural setting of
the Northern Apennines that will be reported in a
forthcoming paper; thus the discrepancy can be
attributed to a small value of the S2 parameter for
sample T124 (0.1 mgHC g!1), whereas sample
T189 can be considered to have data bordering
between Tmax and the mineralogical parameters.
The rocks with free hydrocarbons showed a wide
range of KI data; however a significant group of
rocks showed KI values <0.60 (ºD2y) (Table 1).
DISCUSSION
The rocks with immature kerogen (Tmax in the
range 400!434ºC) can be clearly correlated with
the occurrence of a disordered I-S and delimited by
the transition R0-R1-type mixed-layer I-S (Fig. 4).
This behaviour indicates a shallow diagenetic zone
(Hoffman & Hower, 1979; Merriman & Frey,
124 F. Dellisanti et al.

FIG. 5. Relationship between Tmax and KI. The samples with KI of 1.5 (ºD2y) indicate rocks with a disordered
R0-type I-S and in which KI was not measurable.

1999). However, under shallow diagenesis, illitiza-
tion is not at an equilibrium stage and at low
temperatures the reaction rate of clay minerals is
greater than that of kerogen (Velde & Espitalié,
1989), confirming the variable illite content in I-S
with respect to the Tmax values and the poor linear
relationship between the two parameters (Fig. 4).
The transition R0-R1-type mixed-layer I-S in a
normal geothermal model corresponds to tempera-
tures of ~100!110ºC (Hoffman & Hower, 1979;
Merriman & Frey, 1999).
The rocks within the oil window (Tmax in the
range 435!465ºC) were correlated with an illite
content between 60 and 85% (Fig. 4), corre-
sponding to the conversion from a disordered I-S
to a short-range ordered R1-type (Reynolds, 1980).
However, the illitization kinetics resulted in a rather
variable situation with respect to the kerogen
evolution even though, except for several samples,
the presence of mature kerogen can be correlated
with the range between an R1and R3-type I-S.
According to the geothermal model proposed by
Hoffman & Hower (1979), this concentration range
corresponds to palaeotemperatures in the range
100!110ºC and 170!180ºC. KI data ranged from
0.85 to 0.65 (ºD2y) (Fig. 5), related to a deep
diagenetic zone and palaeotemperatures between
100 and 150ºC (Merriman & Frey, 1999; Arkai et
al., 2002).
Finally, the rocks with over-mature kerogen
showed variable Tmax values corresponding to
illite >85% and KI value in the range 0.65!0.45
(ºD2y) (Figs 4, 5). They are related to rocks in a
deep diagenetic zone up to the limit of the
anchizone and to palaeotemperatures between 150
and 200ºC (Merriman & Frey, 1999; Arkai et al.,
2002). Moreover, almost all the over-mature rocks
showed kerogen in the wet gas zone, confirming
palaeotemperatures 4200ºC (Hunt, 1995; Merriman
& Frey, 1999). The wider variability of the kerogen
evolution than that of the clay minerals can be due
to the equilibrium stage of the illitization reached
for these temperatures. Thus, the changes in the
illite content could be also driven by the K+ ion
 Relationship between Tmax and clay minerals
availability in the succession, as shown by the
different illite content of the External Ligurian units
(between 85 and 90%) and the Cervarola unit where
the illitization reaction is complete (Fig. 4).
Even though the presence of free hydrocarbons
prevented evaluation of the thermal maturity of the
source rocks by Tmax, the correlation with a large
illite content and small KI data (Figs 4, 5) suggests
that the kerogen reached the oil window, and
petroleum was produced even if it was not
completely expelled by the source rock.
The maturity stages of kerogen found by Tmax
data have been confirmed by vitrinite reflectance
(Fig. 6). Indeed, the rocks with mature kerogen
delimited by Tmax in the range 435!465ºC,
corresponded to the oil window defined by Ro
values 0.5 and 1.35% as already reported
(Teichmüller & Durand, 1983; Espitalié et al.,
1984). Similarly, the rocks with immature and over-
mature kerogen were correlated with immature and
overmature organic matter respectively, defined by
Ro values (Fig. 6), with the only exception being
sample T137 which showed a higher maturity with
respect to the vitrinite data. Finally, several samples
containing free hydrocarbons corresponded to Ro
values related to the oil window (Table 1),
confirming the hypothesis that mature kerogen
was already generating hydrocarbons but still
occurring in the source rock.
FIG. 6. Relationship between Tmax and vitrinite reflectance data. 1 and 2 show the limits of the oil window.
125
The structural setting of the Northern Apennines,
composed of stacked nappes and thrust-bounded
units, did not permit extrapolation to a general
correlation between clay mineral parameters and
Tmax. Thus, the estimated palaeotemperatures have
to be interpreted taking into account not only the
age and the thickness of the single stratigraphic
units, but rather their mutual structural position, the
maximum thickness of the structural units and the
burial time after the final tectonic events. The
lowest palaeotemperatures of the Epiligurian units
are coherent with their structural position on top of
the Ligurian nappe and, therefore, at the top of the
sequence of nappes of the Apennines. In the
Ligurian nappe, the increase of palaeotemperatures
from E to SW may be related to different burial
depths due to a west-verging thrusting of the
structural units in an accretionary wedge probably
during the Alpine phases (Cretaceous?-Eocene),
leading to a tectonic superposition of the External
units over the Internal units. An early pre-
Apenninic thermal event has been already recog-
nized by Reutter et al. (1983) for the Ligurian units.
Moreover, during the subsequent Apenninic
phases (from Oligocene onward), the Ligurian
nappe progressively moved NE, overthrusting the
Cervarola-Falterona unit (middle Miocene), which
was also deformed by thrusting and folding beneath
the Ligurian nappe (Castellarin & Pini, 1989; Botti
126 F. Dellisanti et al.
et al., 2004; Pini et al., 2004). Thus, the top of the
younger successions of the Cervarola-Falterona unit
underwent a burial of at least 5!6 km relative to
the emplacement of the Ligurian nappe, the
Epiligurian successions, and to its internal thrust-
stacking, leading to higher palaeotemperatures.
However, because the kinetics of kerogen
evolution is rather different than that of clay
minerals, the palaeotemperatures in the younger
successions could also be influenced by shorter
heating time, as found in some rocks of the
Cervarola-Falterona unit, where maturation of
kerogen is slower (oil window) than the reaction
of clay minerals which reached complete illitization
and is shown by their low KI values. These data
corroborate the correlations found by Velde &
Espitalié (1989) who did not find a clear relation-
ship between younger sediments and short heating
time.
CONCLUSIONS
The values of Tmax obtained by Rock-Eval analysis
permitted an estimation of the thermal maturity of
continental kerogen (Type III) dispersed in rocks of
sedimentary orogenic successions. Tmax was corre-
lated with the mineralogical parameters (illite in I-S
and Kübler Index) and the different maturity stages
of the kerogen related to well-defined values of
illite in I-S and KI. A significant relationship was
found between the clay minerals and the kerogen
thermal evolution. Tmax in the range of 434!465ºC
corresponded to the oil formation zone and was
correlated to a short-range ordered I-S with an illite
content between 60 and 85% and KI values
between 0.85 and 0.65 (ºD2y). Tmax >465ºC
corresponded to over-mature kerogen and was
correlated with a long-range ordered I-S with an
illite content >85% and KI values between 0.65 and
0.45 (ºD2y). The relationships are important in
supporting the palaeotemperature ranges obtained
from mineralogical parameters and act as a
preliminary geothermometer when mineralogical
data are not available. However, because of the
different kinetics of organic and inorganic mate-
rials, a correlation of general application would be
difficult to obtain. Moreover, in orogenic succes-
sions, the mineralogical parameters are essentially
influenced by the thickness of the structural units,
whereas kerogen evolution seems to be also
dependent on the heating time. Thus, further work
is required to shed light on the details of the
relationship between Tmax and illite in I-S and/or
the Kübler Index and to establish palaeotemperature
values.
ACKNOWLEDGMENTS
The final version of this paper has benefited from the
careful comments of two reviewers, C. Brime and H.
Hara. We are also indebted to S. Corrado for providing
the vitrinite reflectance data and to G. Valdrè for
helpful discussions. This paper has been produced
within the MIUR PRIN programme, contributions
2003-040755 and 2005-045211, granted to G.A. Pini.
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