Journal of South American Earth Sciences 28 (2009) 1424

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Journal of South American Earth Sciences

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Geochemical and thermal effects of a basic sill on black shales

and limestones of the Permian Irati Formation
Roberto Ventura Santos *, Elton Luis Dantas, Claudinei Gouveia de Oliveira, Carlos Jos Souza de Alvarenga,
Camila Wense Dias dos Anjos, Edi Mendes Guimares, Frederico Bedran Oliveira
Universidade de Brasilia, Instituto de Geocincias, Campus Darcy Ribeiro, Asa Norte, 70910-900 Braslia, DF Brazil

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

Article history: Intrusive rocks are an important heat source for the maturation of organic matter contained in sediments
Received 13 August 2007 from the Paran Basin, South America. In this study, we have investigated the geochemical effects
Accepted 31 December 2008 induced by the thermal effect of a 13-m thick basic sill intruded on carbonates and black shales of the
Permian Irati Formation, which constitutes one of the most important oil source horizons in the Paran
Basin.
Keywords: Detailed sampling was performed on the sedimentary host rocks located in the upper and lower con-
Sill
tacts. XRD mineralogical examination of the host rocks reveals major mineralogical changes induced by
Trace element
Nd isotopes
the basic intrusion that led to the formation of talc, serpentine and pyroxene. Trace elements and neo-
Carbon isotopes dymium (Nd) isotopes across the contact indicate that geochemical interaction between the basic magma
Oxygen isotopes and the sedimentary rocks was not signicant, suggesting that heat was transferred predominantly by
Permian diffusion. The data also reveal that: (i) the sedimentary rocks located below the sill are more enriched
Paran Basin in hydrous minerals than those in the upper part, suggesting that the sill behaved as a hydraulic barrier
Oil to uid percolation; and (ii) carbonate samples show a systematic decrease in carbon (C) and oxygen (O)
isotope values towards the contact, indicating release of CO2 from carbonate consumption during meta-
morphic reactions.
Thermal effects are also observed on spores present in black shales. They show coloration index (SCI)
values up to 10 for distances below 1.65 m from the lower contact with the basic sill. Beyond this point,
the spore coloration index drops to 44.5 at 12 m from the contact, which is the deepest point from
which samples could be collected.
Assuming that heat was transported by diffusion, we modeled the variation of temperature near the
contact using a one-dimensional transfer model of a one-dimensional innite slab. Modeled temperature
across the contact is, however, not compatible with the SCI values, which indicate a narrow thermally
affected zone. We argue that heat was absorbed by mineral dehydration, pore water volatilization,
organic matter maturation and decarbonization reactions.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Maturation of organic matter contained in black shales is one of
the main sources of hydrocarbons. Maturation is induced by heat,
among other factors, related either to the local thermal gradient or
to igneous intrusions (Cooper et al., 2007; Golab et al., 2007; Gurba
and Weber, 2001; Finkelman et al., 1998; Galushikin, 1997). The
thermal effect of an igneous intrusion depends on a variety of dif-
ferent factors, including intrusion and host rock temperatures, nat-
ure of the magma and of the host rocks, geometry and depth of the
intrusion, mechanism of heat transfer, and other parameters
(Galushikin, 1997). Most studies that have addressed the thermal
* Corresponding author. Tel./fax: +55 61 33071113.
E-mail address: rventura@unb.br (R.V. Santos).
effect of igneous intrusions on coals and black shales have concen-
trated on the transformations of the organic matter (e.g. Cooper et
al., 2007; Amijaya and Littke, 2006; Gurba and Weber, 2001; Flores
and Bader, 1999; Meyers and Simoneit, 1999) and on the extent of
the thermal maturation (Galushikin, 1997). For instance, modeling
calculations suggest that intrusion can affect host rock organic
matter maturity up to a distance corresponding to 11.5 times
its thickness, implying that it may play an important role in hydro-
carbon generation, depending on its dimension and extent.
The presence of gas in the Paran Basin is well-known. It is
related to the thermal decomposition of organic matter within
rocks from the Irati and the Ponta Grossa Formations. In addition
to the thermal effects of burial, another important heat source
may have been Cretaceous basaltic magmatism that extended over
a large area of the basin. Although these organic-rich rocks provide

0895-9811/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jsames.2008.12.002
 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424
one of the most important gas source horizons in the basin, only
limited data exist concerning their thermal evolution and its rela-
tionship to the basaltic magmatism.
In the northwestern part of the basin, close to Perolndia city,
Gois (GO), limestone quarries expose sedimentary rocks from
the Irati Formation that are affected by basic sill intrusions, allow-
ing a detailed study of the thermal effects of the magmatism on the
sedimentary host rocks (Fig. 1). In this report, we have used trace
elements and stable (C and O) and Nd isotopes to perform a de-
tailed study across the contact between the intrusive and the sed-
imentary host rocks in order to better understand their thermal
and geochemical interactions and the effects on organic matter
maturation. We also address the heat transfer mechanism (advec-
tion or diffusion) across the contact and possible uid-rock
interactions.
2. Geology of northwestern Gois state area
The intracratonic Paran Basin extends over most of the south-
ern part of South America and has a maximum thickness of 8 km.
Six Supersequences are represented in this basin, ranging from
Late Ordovician to Late Cretaceous (Milani et al., 1994; Milani
and Zaln, 1999) (Fig. 2): Rio Iva (Rio Iva Group of Ordovician
Silurian age), Paran (Paran Group, Devonian), Gondwana I (Tu-
baro and Passa Dois Groups, Carboniferous-Permian), Gondwana
Fig. 1. Geologic map showing the main sequences of the Paran basin and the location of the Perolndia quarry.
15
II (Triassic units), Gondwana III (So Bento Group, Jurassic-Creta-
ceous) and Bauru (Cretaceous) Supersequences.
The Irati Formation, which is well-known for its oil-bearing
rocks and fossils, is part of the Permian Passa Dois Group and ex-
tends throughout most of the basin (Fig. 1). This unit is divided into
the lower Taquaral Member, composed of siltstones and gray clay-
stones, and the upper Assistncia Member, formed from organic-
rich claystones intercalated with limestone lenses. The organic-
rich rocks are black laminated claystones in which the total organic
carbon content can be as high as 16.3% (Arajo, 2001). Rocks of the
Passa Dois Group are cut by Cretaceous basic intrusions, which
represented an important heat source for the maturation of organic
matter in the claystones. This unit is stratigraphically located at the
base of the Passa Dois Group, which represents the regressive
phase within the major Upper Paleozoic transgressiveregressive
cycle of the Gondwana I Supersequence (Milani and Zaln, 1999).
The paleoenvironmental reconstruction of the Irati Formation
and its depositional setting are still controversial and are thought
to be either a succession deposited in an epicontinental sea or a
continental sequence formed in a lagoon or gulf with variable
salinity (Arajo, 2001). This unit has an average thickness of
40 m and extends over an area of 4 million km2 (South America
and Africa). This formation was previously estimated as Late Perm-
ian (Daemon and Quadros, 1970; Schneider et al., 1974; Milani
et al., 1994). Recent dating of volcanic ash layers have indicated,
16 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424
Fig. 2. Stratigraphic column of the Gondwana I Supersequence (Upper Carboniferous Upper Permian) of the Paran basin. The Irati Formation, which belongs to the Passa
Dois Group, is placed stratigraphically above the Rio Bonito Formation.
however, an age of 278 My for this unit, placing it in the Artinskian
(Early Permian, Santos et al., 2006).
Pre-Cretaceous units of the Paran Basin are crosscut by igneous
intrusions dated between 138 and 127 Ma caused by the Serra Ger-
al Magmatism (Gomes, 1959). Previous studies have shown that
the heat generated by sills caused synchronous generation and
migration of hydrocarbons associated with the Irati Formation
rocks, characterized by an atypical petroleum system (Arajo
et al., 2000). Specically in the north part of the basin, where the
low degree of burial did not favor thermal maturity, the presence
of sills was even more important as a local heat source.
In the Perolndia Quarry area, located in the northwestern part
of the Paran Basin, the Irati Formation consists of a lower Taquaral
and an upper Assistncia Member with thicknesses of 10 m and
30 m, respectively (Costa et al., 1981; Rodrigues, 2001). The Taqua-
ral Member consists of a basal conglomerate that is followed by
white to white-gray ne sandstones, siltstones and claystones with
chert intercalations (Rodrigues, 2001). The lower contact with
Aquidauana Formation is marked by an erosional unconformity.
The Assistncia Member consists of alternating centimeter-sized
beds of dark gray to black shales and dolomite (Figs. 3E and F). Also
found are smaller amounts of gray to black claystones, marls and
oolitic beds, and a few beds of green to greenish-gray claystones
and siltstones. In the upper portion, the Assistncia Member has
a conformity contact with the Corumbata Formation.
The sedimentary rocks of the Irati Formation in Perolncia are
intruded by a 13-m thick basic sill that imprints thermal effects
on the host sedimentary rocks (Figs. 3A and B). The basic sill has
a porphyritic texture with phenocrysts of plagioclase (0.5
1.5 mm) and olivine (0.21 mm). The aphanitic matrix is composed
mainly of plagioclase and augite. Pyrite and ilmenite occur as
accessory minerals. Near the contact, the basic rock displays a
glassy texture and a large number of millimeter- to centimeter-
sized amygdales that are usually lled with carbonaceous material,
carbonate, talc, or trioctahedral smectite (Fig. 3C). Smectite has a
brous to lamellae habit and usually covers the walls of the
amygdales.
Macroscopic evidence of the thermal effect includes the pres-
ence of pyrite-bearing stylolites and stylolitic surfaces in the lime-
stone (Fig. 3D) and pyrite-bearing nodules in the organic-rich
claystone. Pyrite-bearing stylolites and nodules are found less than
5 m from the contact, are lled with euhedral pyrite crystals, and
are usually enveloped by a high-reectance organic matter lm.
A detailed optical microscopy, X-ray diffraction and electronic
microprobe study to be published separately was performed by
Anjos (2003). This study revealed major mineralogical changes in
the sedimentary rocks that were induced by the basic intrusion.
While limestones far from the contact are characterized by dolo-
mite and minor amounts of quartz, illite, feldspar, trioctahedral
smectite and kaolinite, the same rocks near the contact are charac-
terized by calcite and minor amounts of talc and serpentine. In the
pelitic rocks, the mineralogical changes are even more remarkable.
While the unaffected rocks are made of smectite and minor
amounts of quartz, dolomite, illite, kaolinite and zeolite, the ther-
mally affected rocks contain magnesium-bearing metamorphic
minerals with calcite as the dominant carbonate mineral. The main
mineralogical changes noted by Anjos (2003) are: (i) the host rocks
preserve the sedimentary lamination even close to the contact; (ii)
far from the sill, the pelitic rocks are formed mainly by saponite
and quartz, while the carbonate rocks are dominated by dolomite;
(iii) within 5.5 m from the upper and lower contacts, Mg-rich clay
minerals such as saponite, talc and lizardite are dominant; and (iv)
pyroxene crystals are found up to 1 m from the upper contact.
These observations indicate a systematic substitution of dolomite
by calcite towards the contact, leading Anjos (2003) to propose
reactions such as:
3CaMgCO3 2 4SiO2 H2 O > Mg3 Si4 O10 OH2 3CaCO3 3CO3 :
3. Sampling and method
Samples were collected across the upper and lower contact be-
tween the basic sill and the sedimentary rocks and up to 20 m from
the contact. After being crushed, the samples were analyzed for C
and O isotopes, trace element geochemistry and Nd isotopes.
For whole-rock chemical analysis, the samples were weighted
into Teon Savillex beakers and combined with concentrated
HNO3 and HF solution. The mixture was heated on a hot plate until
completely dry. After repeating the procedure once, the residue
 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424 17

Fig. 3. (A) Picture of the upper part of the Perolndia sill. (B) Picture of the lower part of the sill showing the sedimentary sections across which the samples were collected.
(C) Basic rocks from near the contact showing voids and amygdales. (D) Limestone from the contact zone that exhibits a stylitic surface lled with pyrite. (E) Sedimentary
rocks placed below the sill. The upper section is dominated by limestone intercalated with black shales, while the lower part of the section is made of massive limestone. (F)
Massive limestone from the lower part of the section.

was dissolved with dilute HNO3 and the resulting solution was
used to determine the trace elements using a Finnigan Element
ICP-MS at the Geoscience Institute of the University of Braslia.
Sample dissolution for Sm and Nd isotopes was carried out in
Teon Savillex beakers or Parr-type Teon bombs. Sm and Nd
extraction from whole-rock powders followed the technique of
Richard et al. (1976) and Gioia and Pimentel (2000), in which the
separation of the rare earth elements (REE) as a group using cat-
ion-exchange columns precedes reversed-phase chromatography
for the separation of Sm and Nd using columns loaded with HDEHP
(di-2-ethylhexeyl phosphoric acid) supported on Teon powder.
We have also used the REE-Spec and Ln-Spec resins for REE and
SmNd separation. A mixed 149Sm150Nd spike was used. Sm and
Nd samples were loaded onto Re evaporation laments of a double
lament assembly. Sm and Nd isotopic analyses were carried out
using a Finningan MAT-262 mass spectrometer. Uncertainties on
Sm/Nd and 143Nd/144Nd ratios are considered to be less than 0.1%
(1r) and 0.000001 (1r), respectively, based on repeated analyses
of international rock standards BCR-1 and BHVO-1. 143Nd/144Nd ra-
tios were normalized to a 146Nd/144Nd ratio of 0.7129. Nd proce-
dure blanks were smaller than 100 pg.
C and O isotope ratios were obtained after reacting the samples
with 100% H3PO4 at 25oC for at least 12 h for calcite and for over
three days for dolomite (MacCrea, 1950). The released CO2 was
analyzed in a Europa mass spectrometer at the University of So
Paulo.
4. Results
The REE data from the igneous and sedimentary rocks are given
in Table 1 and are shown as chondrite-normalized patterns in
Fig. 4. The basic igneous rocks show higher concentrations of REE
(RREE of 129.7 and 211.4 ppm) and a higher RLREE/RHREE ratio
than the sedimentary rocks. All sedimentary rocks show slightly
negative Eu anomalies and enrichment in LREE relative to HREE.
Relative to average crustal values from Taylor and McLennan
(RREE = 143 ppm; 1985), they all show much lower RREE, ranging
from 3.6 to 59.3 ppm. Normalized trace element variations from
the sedimentary and igneous rocks are presented in Table 2 and
Fig. 5.
Nd isotopic compositions across the contact between the sill
and the host rock are shown in Table 3 and Fig. 6. While the basic
18 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424

Table 1
Trace element geochemistry of Perolndia samples.

Sample Rock Distance from ppm

contact (m)
Co Ni Cr V Sr Rb Ba Pb Zr Yb Nb Hf Th U
SUC I-16B Black shale 2.32.7 19.16 6.47 16.09 23.21 33.52 1.10 49.83 2.73 9.47 0.14 0.81 0.28 0.08 0.04
SUC I-15 Black shale 2.32.7 7.23 9.57 17.15 26.20 411.65 1.81 25.02 2.80 17.15 0.49 2.34 0.48 0.29 0.25
SUC I -13C Limestone 2.1 6.65 10.83 16.30 23.15 603.64 0.17 101.16 2.46 16.56 0.32 1.10 0.47 0.17 0.14
SUC I -13B Limestone 2.05 6.64 10.59 15.74 22.91 575.61 0.18 72.55 2.04 14.33 0.27 0.99 0.42 0.21 0.10
SUC I -13A Limestone 2 8.50 10.33 18.09 27.99 598.63 1.89 138.70 2.48 27.00 0.79 2.20 0.73 0.45 0.33
SUC I-12 Black shale 0.61.5 10.67 12.52 24.04 37.08 77.63 8.48 43.25 7.13 48.19 0.84 5.01 1.36 2.26 0.80
SUC I-9 Stolitic limestone 0.4 7.24 10.91 14.93 22.47 534.68 0.10 106.09 1.72 10.51 0.24 0.84 0.32 0.16 0.11
SUC I AB 8 Limestone 0.35340 2.55 5.40 12.97 20.26 26.95 0.09 4.83 1.53 8.80 0.13 0.65 0.27 0.05 0.02
SUC I-7 Black shale 0.20.3 10.06 8.11 19.59 28.98 77.10 8.33 24.54 1.69 24.57 0.38 2.72 0.66 0.91 0.39
SUC I-6B Black shale 0.20.3 8.14 7.35 16.57 26.95 63.23 14.26 26.75 4.56 18.05 0.30 1.66 0.47 0.46 0.34
SUC I-6A Black shale 0.20.3 10.85 6.16 14.70 21.40 43.06 0.62 9.23 2.20 10.73 0.27 0.83 0.31 0.12 0.09
SUC l-5 Black shale 0.10.2 7.93 9.05 19.06 31.89 105.80 7.62 49.23 2.02 23.60 0.41 2.41 0.67 0.99 0.49
SUC l-4 Black shale 0.10.2 3.87 6.99 13.50 31.53 46.05 0.78 25.84 2.52 24.85 0.21 1.02 0.41 0.12 0.13
SUC l-3 31.37 32.48 38.42 287.71 286.09 15.94 339.48 5.59 191.03 1.66 13.08 4.48 1.47 0.54
SUC ll-1 34.82 25.57 50.67 379.09 452.50 40.75 507.86 7.83 279.60 2.93 26.91 6.53 3.01 0.71
SUC ll-2 10.31 15.32 20.56 55.82 66.50 4.35 148.74 2.73 23.73 0.69 2.65 0.65 1.00 0.60
SUC l l-4.a Black shale 0.3 36.23 6.49 14.97 23.32 32.04 1.05 20.78 0.94 17.32 0.17 1.08 0.40 0.32 0.17
SUC l l-4.b Black shale 0.3 14.97 10.48 25.47 31.95 120.51 10.02 45.83 6.47 34.97 0.50 3.81 0.96 1.91 0.44
SUC II-5A Limestone 0.45 7.94 8.79 15.51 23.76 307.40 0.70 21.07 0.82 10.85 0.19 1.03 0.34 0.13 0.20
SUC II-5B Limestone 0.65 12.23 12.48 23.35 34.58 169.68 10.21 73.91 4.12 33.25 0.62 3.58 0.91 1.70 1.40
SUC II 6B Limestone 0.8 7.53 9.55 15.31 24.58 345.59 0.57 24.89 0.83 11.08 0.31 1.05 0.34 0.05 0.20
SUC II 9 A,B Limestone 1.2 5.63 7.56 14.10 22.06 280.00 0.31 35.15 0.58 9.86 0.19 0.80 0.30 0.13 0.09
SUC II-10A Limestone 1.3 4.32 7.74 14.14 112.15 26.88 0.39 9.48 4.08 12.39 0.13 0.78 0.30 0.18 1.12
SUC II 10 C Limestone 1.45 5.71 7.73 13.98 23.48 205.67 0.75 16.39 0.74 10.03 0.21 0.97 0.31 0.07 0.12
SUC ll-13 Black shale 4 8.71 9.47 19.03 27.31 129.35 4.35 88.66 2.65 21.98 0.81 2.84 0.66 1.43 0.37
SUC II- 32 Dolostone 18 6.67 8.12 14.78 29.34 352.66 2.10 18.60 1.16 8.69 0.19 1.02 0.27 0.04 0.59

1000

Limestone
100
chondrite
sample

10

0.1
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Fig. 4. REE patterns of the basic sill and of sediments from the Irati Formation.

sill has TDM model ages around 1.2 Ga and eNd (t) values of 2, the
sedimentary host rock has TDM model ages ranging from 1.45 to
1.87 Ga and strongly negative eNd (t = 278 Ma) values (8 to
12). Even samples of black shale located a few centimeters from
the sill show no signs of interaction with the basic magmatism.
C and O isotopes from carbonates across the lower contact be-
tween the sill and the sedimentary host rocks are presented in Ta-
ble 3 and Fig. 7. Samples from the upper part of the proles have
oxygen isotope values around to 8, while samples from the
lower part of the proles have values around 5. The differences
in the oxygen isotopic composition seem to be related to the prox-
imity to the sill as discussed below.
In contrast to the oxygen isotopes, the carbon isotopes display
signicant variation with values ranging from 7.0 to +12.7.
The samples with high carbon isotope values, which are found
mainly in the middle part of the lower prole, are characterized
 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424 19

Table 2
REE geochemistry of Perolndia samples.

Sample Rock Distance from ppm

contact (m)
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm
Above the sill SUC I-16B Black shale 2.32.7 0.66 1.42 0.19 0.81 0.21 0.06 0.23 0.04 0.18 0.05 0.12 0.02
SUC I-15 Black shale 2.32.7 8.49 11.10 1.40 5.50 1.13 0.27 1.30 0.19 1.01 0.22 0.57 0.08
SUC I -13C Limestone 2.1 5.98 7.24 0.85 3.20 0.58 0.16 0.65 0.09 0.49 0.12 0.32 0.05
SUC I -13B Limestone 2.05 4.09 4.83 0.56 2.17 0.42 0.12 0.47 0.07 0.38 0.09 0.26 0.04
SUC I -13A Limestone 2 9.56 11.26 1.33 5.08 0.99 0.25 1.12 0.18 1.02 0.25 0.73 0.12
SUC I-12 Black shale 0.61.5 11.30 19.40 2.62 10.08 2.00 0.40 2.05 0.29 1.55 0.33 0.86 0.13
SUC I-9 Stolitic Limestone 0.4 4.49 4.62 0.53 2.06 0.38 0.11 0.44 0.06 0.33 0.08 0.23 0.04
SUC I AB 8 Limestone 0.35340 0.54 1.28 0.16 0.70 0.19 0.05 0.21 0.04 0.17 0.04 0.11 0.02
SUC I-7 Black shale 0.20.3 5.16 9.96 1.36 5.19 1.05 0.20 0.96 0.14 0.76 0.15 0.39 0.06
SUC I-6B Black shale 0.20.3 3.07 5.65 0.76 3.03 0.62 0.15 0.65 0.10 0.50 0.11 0.29 0.05
SUC I-6A Black shale 0.20.3 3.08 4.16 0.50 2.02 0.41 0.12 0.48 0.07 0.40 0.10 0.27 0.04
SUC l-5 Black shale 0.10.2 5.40 8.83 1.26 4.95 1.02 0.25 1.04 0.15 0.80 0.17 0.44 0.07
SUC l-4 Black shale 0.10.2 2.72 4.30 0.61 2.43 0.53 0.15 0.53 0.08 0.40 0.09 0.22 0.03
Si ll SUC l-3 19.49 54.35 6.33 26.17 5.90 1.86 5.54 0.82 4.29 0.80 1.95 0.27
SUC ll-1 35.89 78.36 11.10 45.66 10.16 3.04 9.68 1.43 7.48 1.38 3.34 0.46
SUC ll-2 8.29 15.68 2.00 8.02 1.70 0.45 1.90 0.28 1.49 0.31 0.80 0.11
SUC l l-4.a Black shale 0.3 1.57 2.27 0.35 1.33 0.30 0.07 0.31 0.05 0.24 0.06 0.15 0.03
SUC l l-4.b Black shale 0.3 5.78 11.09 1.52 5.95 1.20 0.23 1.13 0.17 0.88 0.19 0.49 0.08
Below thesil SUC II-5A Limestone 0.45 1.70 2.47 0.32 1.33 0.31 0.09 0.35 0.05 0.28 0.07 0.18 0.03
SUC II-5B Limestone 0.65 8.32 15.80 2.04 8.03 1.69 0.32 1.69 0.25 1.29 0.26 0.68 0.10
SUC II 6B Limestone 0.8 4.02 5.19 0.66 2.72 0.58 0.15 0.68 0.10 0.53 0.13 0.34 0.05
SUC II 9 A,B Limestone 1.2 1.57 2.30 0.30 1.27 0.30 0.08 0.35 0.06 0.26 0.07 0.18 0.03
SUC II-10A Limestone 1.3 0.48 1.26 0.17 0.72 0.21 0.06 0.23 0.04 0.17 0.05 0.11 0.02
SUC II 10.05C Limestone 1.45 2.23 3.12 0.42 1.71 0.40 0.11 0.46 0.07 0.36 0.09 0.23 0.04
SUC ll-13 Black shale 4 15.30 21.25 2.72 10.86 2.07 0.48 2.31 0.33 1.63 0.37 0.94 0.13
SUC II- 32 Dolostone 18 3.68 4.45 0.90 4.14 0.79 0.17 0.81 0.10 0.46 0.10 0.25 0.03

1000 Limestone In the Perolndia Quarry area, thermal effects on the host rock
black shale include the formation of stylolite, pyrite nodules and mineralog-
basicrock ical transformations (Fig. 3D). The presence of organic matter
100
lms associated with the stylolites and pyrite nodules at loca-
tions up to 5 m from the lower contact suggests that organic mat-
ppm

10 ter was remobilized to various extents. A particular feature of the

1
0 citepyroxene, while in the lower part, the association is smec-
Co Ni Cr V Sr Rb Ba Pb Zr Yb Nb
Fig. 5. Average trace element variations of the basic igneous rock, limestones and
black shales.
by centimeter-size dolomite layers intercalated with organic-rich
shalestones.
5. Discussion
High temperatures are essential to the generation of oil and gas
by organic matter maturation. In the Paran Basin, Cretaceous ba-
sic intrusions are known to have been an important source of heat
for the maturation of organic matter bearing rocks from the Irati
and Ponta Grossa Formations (Arajo et al., 2000). The data pre-
sented here allow us to address questions concerning the interac-
tion between the basic magma and the host rocks, including
understanding how this interaction affected organic matter matu-
ration. Specically, we hope to answer the following questions:
How far from the contact are thermal features observed, and
how do they affect mineralogical and textural changes in the host
rock? Did chemical interaction occur between the magma and the
host, and if so how did this interaction depend on the type of mag-
ma? What was the main heat transfer mechanism: thermal diffu-
sion or advection? Heat transfer induced by mass is far more
efcient and is expected to affect a much larger host rock volume.
mineralogical transformations pointed out by Anjos (2003) re-
veals that the thermal effects are different for the host rocks lo-
cated on the upper versus the lower part of the sill. In the
upper part, the mineral association is smectiteserpentinecal-
Hf Th U titetalcserpentinecalcite. The presence of pyroxene in the
upper host rocks indicates a higher temperature mineralogical
association, suggesting more anhydrous conditions compared to
the rocks below the sill. This difference implies that the sill
may have affected uid dynamics in the area, behaving as a
hydraulic barrier to upward uid migration. In that case, the
presence of uid in the lower rocks made possible local retro-
metamorphic effects, which resulted in the replacement of pyrox-
enes by lower temperature minerals.
The geochemical interactions between the intrusive and the
host rocks were investigated using trace element and isotope geo-
chemistry (Fig. 7). In particular, REE analyses have been used pri-
marily to study the magmatic evolution of igneous rocks in
terms of fractionation and contamination by the host rock. Such
analyses have also been applied to understand the source areas
of sediments, giving further support to the Nd isotope interpreta-
tions. In the present study, we used REE analysis to evaluate possi-
ble geochemical interactions between the sill and the sedimentary
host rocks. Fig. 4 shows that there is a signicant difference
between the REE patterns of the basic sill and those of the sedi-
mentary rocks. Although the basic rocks have higher REE concen-
trations, there is no sign of interaction with the sedimentary
rocks even a few centimeters from the contact (Fig. 7). The REE
concentrations of the limestones and black shales are variable
and are not dependent on the distance from the contact as shown
in Table 1. Variations of REE and other trace elements seem not to
20 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424

Table 3
Nd, carbon and oxygen isotopes for samples of the basic sill and sedimentary host rocks from the Perolndia Quarry.
147
Sample Rock Distance from Sm(ppm) Nd(ppm) Sm/144Nd 143
Nd/144Nd e Nd (o) TDM d 18o d 13C
contact (m) ( 1s) ( 1r) (Ma) (PDB) (PDB)
Above SUC I-18 Limestone 3.1 1.644 8.022 0.1239 0.512063 10 11,22 1,64
the sill SUC I-16B Limestone 2.32.7 1.601 7.968 0.1215 0.511980 05 12,83 1,74
SUC I-13C Limestone 2.1 5.87 4.72
SUC I-13B Limestone 2.05 6.60 6.60
SUC I-13A Limestone with 2 1.2234 6.759 0.1104 0.512050 14 11.48 1,45 6.43 6.53
SUC I-12 Black shale 0.61.5 1.964 10.268 0.1156 0.512050 07 11,47 1,53
SUCI-10 Black shale 0.61.5 1.704 8.942 0.1152 0.512003 07 12,38 1,59
SUC I-9 Stolitic limestone 0.4 6.36 6.51
SUC I AB 8-9 Limestone 0.40.45 6.34 4.66
SUC I AB 8 Limestone 0.350.40 0,391 2.235 0,1058 0,512094 10 10,61 1,33 8.64 5.16
SUC I-7 Black shale 0.20.3 0.778 5.888 0.0799 0.512218 07 8.19 0,93
SUC I-6B Black shale 0.20.3 1.000 5.106 0.1184 0.512102 07 10.46 1,49
SUC I-6A Black shale 0.20.3
SUC l-5 Black shale 0.10.2
SUC I-3B Limestone 0.05 7.46 4.24
SUC I-3A Limestone 0 8.93 4.92
Sill SUC I-3 9.56 43.06 0.1342 0.512401 07 4.62 1,22
SUC I-2 9.768 44.03 0.1341 0.512398 07 4.68 1,22
SUC I-1 9.492 42.827 0.134 0.512403 07 4.59 1,21
Below the SUC II-3 Limestone 0.15 11.81 0.68
sill SUC ll-4.a Limestone 0.3 0.148 0.798 0.1121 0.511708 05 18.13 1,98
SUC ll-4.b Black shale 0.3
SUC II-5A Limestone 0.45 10.40 0.62
SUC II-5B Limestone 0.65 0.526 2.812 0.113 0.512066 10 11.16 1,46 10.51 2.02
SUC II-6B Limestone 0.8 8.92 5.32
SUC II-7 Limestone 0.9 0.398 2.42 0.0996 0.511911 09 14.18 1,50 9.13 4.58
SUC II-7A Limestone 0.9 0.39 2.001 0.1177 0.512064 07 11.19 1.54
SUC II-9 A,B Limestone 1.2 7.79 6.33
SUC II-10A Limestone 1.3 10.51 1.48
SUC II-10C Limestone 1.45 9.53 2.05
SUC II-10E Limestone with 1.65 8.99 1.07
SUC II-10F Limestone 1.7 7.68 3.95
SUC II-13 Black shale 4 1.795 8.974 0.1209 0.512030 12 11.85 1,64
SUC II-15A Black shale 6 2.093 9.926 0.1275 0.512088 06 10.73 1,67
SUC II-16 Limestone 7 4.06 10.99
SUC II-17 Limestone 8 4.72 12.10
SUC II-18 Limestone 9 4.16 12.27
SUC II-19 Limestone 10 5.26 12.75
SUC II-20 Limestone 11 4.73 11.36
SUC II-21 Limestone 12 4.80 7.29
SUC II-22 Dolostone 13 4.43 2.37
SUC II-36 Dolostone 14 4.36 2.05
SUC II-35 Dolostone 15 5.76 2.28
SUC II-34 Dolostone 16 4.97 0.40
SUC II-33 Dolostone 17 4.78 0.94
SUC II-32 Dolostone 18 2.159 10.292 0.1268 0.511968 10 13.07 1,87 3.91 2.44
SUC II-31 Dolostone 19 4.45 7.00
SUC II-30 Dolostone 20 5.11 3.90

depend on distance from the basic igneous rocks and are probably
related to primary variations in the sedimentary rocks.
Isotopic variations across the prole are shown in Fig. 7. While
changes in Nd isotopes are limited to the transition zone, there are
major variations in C and O isotopes across the prole. As discussed
below, these variations are related to both sedimentary processes
and thermal effects caused by the basic sill.
Nd isotopes are very sensitive to small-scale geochemical inter-
actions, as shown in the isotopic values across the contact between
the sill and the host rock (Fig. 7). The basic sill TDM model ages
(1.2 Ga) and eNd (t) values (2) indicate a Neoproterozoic mantle
source; whereas, the sedimentary host rocks TDM model ages
(1.451.87 Ga) indicate older source regions. The eNd (t) values were
calculated at 278 Ma based on Santos et al. (2006) SHRIMP zircon
dating of bentonic layers intercalated with the Irati Formation rocks.
Fig. 7 shows that Nd and Sm concentrations, as well as TDM model
ages, show a marked change across the basic sillhost rock contact,
suggesting minor chemical and isotopic interactions between the
intrusion and the host rocks. It should be noted that no signs of
interaction were observed, even at a centimeter scale (Fig. 7).
Detailed C and O isotope analyses performed across the contact
with the basic sill show large variations in the isotopic ratios
(Fig. 7). Based on previous studies, at least part of this large stable
isotope variation seems to be related to sedimentary processes
rather than to the thermal effect of the basic sill. For instance,
the anomalous high positive d13CPDB values were also observed in
other parts of the basin (Arajo, 2001; Giovani et al., 1974). Giovani
et al. (1974) do not mention the presence of basic intrusions but
report that an 11 m thick sequence of Irati Formation carbonates
intercalated with bituminous shales from a stone quarry along
the Rio ClaroPiracicaba highway had C isotope values ranging
from 8.6 to 14.9. According to the authors, these rocks contain
rare vertebrate fossils (Mesosauros brasiliensis) and, as in the pres-
ent study, are located above a massive dolomitic sequence. Simi-
larly, Arajo (2001) performed a systematic study of drill cores
along the Paran Basin and showed that carbonates with anoma-
lous positive C isotopes are commonly found in Irati sedimentary
rocks from the southwestern portion of the basin. Hence, these
anomalous C isotope values seem to be related to stratigraphic
variations and are beyond the scope of the present study.
 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424 21

10 (modeled assuming the isotopic fractionation follows a Rayleigh

law) of a carbonate rock that released CO2 during metamorphism
assuming an initial carbonate rock with 70% calcite and initial
Basic d13CPDB and d18OPDB values of +6.0 and 7.0, respectively.
TDM
intrusive The initial isotopic values were based on average values, while
rocks the amount of calcite represents the best t to the data.
0 The isotopic variation is more signicant for those samples be-
low the sill, a result that seems to be related to more hydrous con-
ditions that may have favored metamorphic reactions.
Nd (0)

sedimentary 5.1. Thermal effects on organic matter

-10 rocks
-20
0 1.0 2.0
T (Ga)
Fig. 6. Evolution of Nd isotopes in the sill and the host from the Perolncia quarry.
A close look at the C and O isotope values, particularly those
from samples located less than 2.5 m from the contact, reveals that
the thermal effect imprinted signicant isotopic variations on the
carbonates. Fig. 8 shows d13C plotted versus d18O. The group of
samples located less than 2.5 m from the contact display a regular
decrease in isotopic ratios. A similar result has been described for
carbonate-bearing rocks intruded by igneous rocks and has been
attributed to CO2 devolatilization induced by metamorphic reac-
tions (Valley, 1986). Under these circumstances, the released CO2
is enriched in 13C and 18O relative to the residual carbonate, thus
decreasing the isotopic composition of the residual carbonate (Val-
ley, 1986). Fig. 8 shows the expected variation of C and O isotopes
The heating of organic matter-rich sedimentary rocks by intru-
sive rocks may be an important mechanism for the generation of
gas and oil in many sedimentary basins (Galushikin, 1997; Meyers
and Simoneit, 1999; Gurba and Weber, 2001; Cooper et al., 2007,
among others). In general, the thermal effect of igneous bodies in-
truded into sedimentary rocks is expected to be evident for dis-
3.0
tances up to one to two times the thickness of the intrusion
(Dow, 1977; Galushikin, 1997). However, other studies have
shown that the extent of the thermal effect also depends on other
factors, including thermal conductivity, volume of pore water,
development of a convection cell, time, and maturation of the or-
ganic matter (Barker et al., 1998; Suchy et al., 2004). These factors
may explain why in some instances the extent of the thermal effect
is much thinner than that expected based on the thickness of the
sill or the dyke. Previous studies have also reported signicant dif-
ferences between thermal effects induced by a dyke and those in-
duced by a sill. While the former generates methane (CH4), which
is released by fractures and changes in the residual organic matter
carbon isotopic composition, the latter tends to trap the CH4, which
is later converted to pyrolite (Cooper et al., 2007).
The absence of signicant mass exchange between the sill and
the sedimentary host rocks from Perolndia suggests that the
mechanism of heat transfer from the basic intrusion to the sedi-

Fig. 7. TDM, eNd, carbon and oxygen isotopes, and SCI across the basic sillsedimentary host rocks contact. The SCI are from Souza et al. (2005).
22 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424

Fig. 8. Carbon versus oxygen isotopic composition of Irati carbonates for samples below the contact with the basic intrusive sill. The curve in the diagram refers to carbon and
oxygen isotopic variations of a carbonate rock that released CO2 during metamorphism following a Rayleigh process. The curve was made for an initial carbonate rock with
70% calcite and initial d13CPDB and d18OPDB values of +6.0 and 7.8, respectively.

mentary host rock was mainly controlled by thermal diffusion. Nd
isotopes and trace element geochemistry suggest that the mineral-
ogical changes in the host rock induced by the thermal effect prob-
ably occurred under closed system conditions, except for the CO2
released by the decarbonization reactions. This assumption allows
us to model the temperature variations across the intrusivesedi-
mentary interface with a one-dimensional innite slab diffusion
heat transfer model (Jaeger, 1959, 1964; Wickham and Oxburgh,
1987; Stewart et al., 2005). This model assumes that the slab has
a constant thickness of 13 m along the z direction and an innite

1200
0.13
1.34
2.68
1000 6.70
13.40
26.79
66.99
800
Tmax
Temperature (C)

SCI

600

10
Spore coloration index

400

5
200

0 0
0 5 10 15 20 25 30
Distance (m)

Fig. 9. Modeled thermal evolution of the country rock assuming an innite slab 13-m thick. The numbers at the bottom of the diagram represent the temperature in each year
and the maximum temperature. The model was performed using the following parameters: sill initial temperature = 1100 C; country rock initial temperature = 100; and
thermal diffusion coefcient = 1.0  106 m2/s.
 R.V. Santos et al. / Journal of South American Earth Sciences 28 (2009) 1424
length along the x and y directions. It also assumes that there are
no uid ow or heat-absorbing processes, such as decarbonization
or dehydration reactions. Organic geochemistry data from the Irati
Formation black shales reveal that these rocks have a maximum
depth of about 23 km (Arajo et al., 1996). Using a gradient of
30 C/km and a mean surface temperature of 20 C, Arajo et al.
(1996) estimated a burial temperature of 6080 C for the Irati For-
mation. A possible scenario from our model is presented in Fig. 9,
which shows the thermal evolution of the country rock across
the contact. Based on the characteristics of the basic magma and
the sedimentary rocks as well as the approximate intrusion depth,
the model was run using the following parameters: sill initial tem-
perature = 1100 C; country rock initial temperature = 100 C; and
thermal diffusion coefcient = 1.0  106 m2/s. According to the
model, the temperature of the sedimentary rocks reached 500 C
in the vicinity of the contact and then decreased to 200 C at a dis-
tance of 18 m from the contact.
Black shale petrographic results and spore coloration index
(SCI) values from Perolndia were studied by Souza et al. (2005).
They show that organic matter across the Perolndia section con-
sists mainly of yellow to black aggregates of amorphous material.
Lipidic organic matter is characterized by sporomorphs of Botryo-
coccus algae that exhibit colonies and internal structure. They re-
port SCI values varying between 4 (brown) and 10 (black) across
the same section studied here, revealing major temperature varia-
tions across the contact zone (Fig. 7). This index reaches a value of
10 within the rst 1.65 m from the lower contact and then levels
off to 4 at a distance of 12 m, which was the farthest sample that
could be collected across the prole. In other parts of the basin,
the SCI values may be as low as 2 (Arajo, 2001). Because the upper
contact was close to the surface, sedimentary samples above the
sill encompassed only a 3 m section. Based on these SCI data, sed-
iments beyond 1.65 m from the base of the sill were probably not
heated to temperatures above 200 C (Fig. 9), indicating a signi-
cant inconsistency with the thermal diffusion model presented
above.
This inconsistency is probably related to heat sink processes,
which were not accounted for in the heat transfer model. These
processes, such as mineral dehydration, pore water volatilization,
organic matter maturation and decarbonization reactions, con-
sumed most of the heat produced by the sill, thus limiting the in-
crease in temperature far from the contact. The rst three
processes have already been invoked as heat sink mechanisms in
similar studies, including the Paran Basin (Murchison and
Raymond, 1989; Barker et al., 1998; Arajo et al., 2000; Suchy
et al., 2004). Decarbonization, however, is a more restricted pro-
cess and occurs where intrusive rocks intrude carbonate-bearing
rocks. This process is not easily identied by mineralogical trans-
formations but may signicantly affect the C and O isotopic com-
positions of carbonates as shown above.
6. Conclusions
In the Perolndia quarry, a 13 m thick basic sill intrudes black
shales and limestones of the Permian Irati Formation, which is
one of the most important stratigraphic units for hydrocarbon
source rocks in the Paran Basin. A detailed investigation across
the contact between the igneous and the sedimentary rocks re-
vealed major mineralogical changes induced by thermal effects.
For instance, near the contact with the sill, talc and serpentine
formed in the limestone, while magnesium-bearing minerals such
as pyroxene formed in the black shales.
A detailed geochemical investigation based on variations in
trace elements, REE and Nd isotopes across the contact indicates
that the mineralogical changes were not accompanied by geo-
23
chemical interaction between the intrusive and host rocks. There
is no sign of interaction even a few centimeters from the contact,
indicating that heat was transported mainly by diffusion.
However, the C and O isotopes of the limestone near the contact
indicate that the system was not closed. A decrease in the C and O
isotopic compositions of carbonates towards the contact suggests
that the thermal metamorphism was accompanied by CO2 devola-
tilization. This interpretation is supported by calcsilicate meta-
morphic reactions involving carbonate consumption and the
formation of pyroxenes near the contact zones.
The thermal effects were also observed in organic matter pres-
ent in the black shales that were intercalated with the limestones.
Spores up to 1.65 m from the lower contact have SCI values of 10.
Beyond this distance, the SCI values decrease to 44.5 at 12 m from
the contact.
Assuming that the heat transfer across the basic sillhost rock
was dominated by diffusion, we have modeled the variation of
temperature across the contact zone using a one-dimensional
transfer model. The temperature obtained by the model, however,
is not consistent with the thermal effects observed in spores within
the black shales. Spores beyond 1.65 m from the lower contact pre-
sented SCI values below 10, corresponding to temperatures that
were probably below 200 C. Beyond 1.65 m, the SCI values de-
crease and reach values between 4 and 4.5 at a distance of 12 m
from the contact. These values imply that the thermally affected
zone in the sedimentary host rock is much narrower than that pre-
dicted by the model. The discrepancy is likely due to the fact that
the model does not take into account heat consumption by mineral
dehydration, pore water volatilization, organic matter maturation
or decarbonization reactions. We argue that these processes were
an important heat sink across the sillsedimentary rock contact.
Acknowledgment
The authors would like to thank CNPq Conselho Nacional de
Desenvolvimento Cientco e Tecnolgico (National Council for
Scientic and Technological Development) for nancial support
granted to RVS (CtPetro 471907/01-4).
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