Burial diagenetic reactions of di- and trioctahedral clay minerals were compared in Brazilian offshore, basinal sediment sequences of Cretaceous age. Originally dioctahedral smectite-rich shales of three basins—Potiguar,Ceara, and Ilha de Santana—exhibited the classical smectite-to-illite burial pattern. Trioctahedral clay-rich shales and trioctahedral clay-mineral cements in sandstones, however, showed a burial sequence of saponite to mixed-layer chlorite/saponite with progressive increase in the percentage of chlorite layers with increasing burial depth.

The change from disordered to ordered interstratifications of chlorite/saponite occurred in the temperature range 60°-70°C at a vitrinite reflectance value of about 0.65. These values are lower than those found for the ordering of illite/smectite clays. Increasing substitution of Al for Si in tetrahedral sites, followed by fixation of interlayer hydroxide sheets was found to be the major chemical change promoting transformation of saponite to chlorite via corrensite.

The correlation between illite/smectite (I/S) diagenesis and mean vitrinite reflectance (Ro) data is examined in mudrocks from a hydrocarbon exploration well (geothermal gradient 35°C km−1) from the Great Hungarian Plain of the Pannonian Basin System. The expandability of I/S decreases with depth and there is a change from random to ordered mixed-layering at about 2500 m depth. At this depth Ro is about 0.6%. Comparison of the correlation of expandability and Ro from this study to published data for the Vienna Basin and the Transcarpathian Basin, sub-basins of the Pannonian Basin System, shows that the correlation is systematically different for each sub-basin, according to their thermal histories. In the Vienna Basin (geothermal gradient 25°C km−1), for any given value of Ro, the expandability of I/S is less than in the Transcarpathian Basin (geothermal gradient 55°C km−1) and the sediments are older and more deeply buried. Data from the present study are intermediate. This variation is believed to be due to the effect of time on the smectite-to-illite reaction. Results of an optimization procedure to calculate the kinetics of the smectite-to-illite reaction, using as input the expandability depth profiles, and thermal histories constrained by comparison of observed and calculated Ro data, showed that I/S diagenesis in the Pannonian Basin System can be modelled by a single first order rate equation:

$-dS/dt=e^{log(A)-E/RT}\cdot S$

The <0.5-μm fraction of 120 samples from a lithologically complex Permian sedimentary sequence, underlying dolerite intrusive sheets, has been characterized by means of X-ray diffraction to establish I/S compositions as a function of temperature, lithology and time duration. Illitization has been active over the entire 210 m depth range and the clay data reflect both the local pattern of contact metamorphism and the more regional trend of heat flow during burial. A continuum exists in the illite proportions of the illite/smectite interstratifications with increasing distance from the intrusive sheet ranging from R = 3 with less than 5% smectite via R = 2 and R = 1 to R = 0 with up to 70% smectite. In the mixed-lithology section, individual component layers in the I/S within similar distance levels, but between contrasting lithologies, appear to vary only within a very restricted compositional range. In the massive mudstone strata, however, more silty parts contain I/S of a higher degree of ordering and lower expandability. Calcite contents are reflected in a higher rate of chlorite formation, but not in the I/S composition. A satisfactory inverse correlation was found between percent smectite in I/S and vitrinite reflectance in the lithologically complex section. R = 1 interstratifications are associated with a maximum vitrinite reflectance of 1.07–1.29 and R > 1 phases with 1.93–2.7, indicating that time duration is not a controlling factor in the illitization process in this facies. R = 0 interstratifications are present in a massive mudstone/siltstone sequence situated furthest from the igneous intrusives, and display vitrinite reflectance values of 1.42–1.52. No satisfactory explanations for this finding can be offered.

Chlorite and corrensite are common clay minerals in lacustrine mudrocks from the Devonian Orcadian Basin, Scotland. The relationship of their occurrence to vitrinite reflectance data demonstrate that they are authigenic minerals, formed during burial diagenesis/metamorphism at temperatures of ≥120°C. Whole rock mineralogical and chemical analyses show that chlorite authigenesis occurred by reactions between the detrital dioctahedral clay mineral assemblage and dolomite that was formed under early evaporitic conditions in the lacustrine environment.

XRD and electron microprobe analyses indicate that phases intermediate between corrensite and chlorite are probably mixed-layer chlorite/corrensite with a tendency towards segregation of layer types. Chemically, the conversion of corrensite to chlorite involves an increase in Al for Si substitution in tetrahedral sites, but there is no change in the Fe/Mg ratio of octahedral cations. There is also no relationship of mixed-layer proportions to paleotemperature; only a general paleotemperature interval of approximately 120° to 260°C in which a range of phases between corrensite and chlorite occurs. Chlorite polytypes are exclusively IIb, indicating the formation of this polytype at diagenetic temperatures.

The occurrence of corrensite and Mg-rich chlorite in evaporite and carbonate successions is probably a reliable indicator of diagenetic alteration at temperatures of ≥ 100°C. Burial diagenetic reactions between dioctahedral clay minerals and Mg-rich carbonates may possibly explain many occurrences of corrensite and Mg-rich chlorite in such rocks.

Clay mineralogy (including illite crystallinity) was studied in Pennsylvanian synorogenic sediments (Atoka Formation) in the subsurface of the Arkoma Basin and the adjacent Ouachita thrust belt. Vitrinite reflectance values range from ≥0.8% at the surface up to as high as 4.7% Ro at the base of the Atoka Formation. The mineralogy of the <2 µm fraction of the mudrocks is fairly monotonous and composed of illite (<10% interstratified smectite), Fe-chlorite, kaolinite, quartz, and traces of feldspars. Kaolinite is common at shallow levels and “disappears” in most wells at a thermal maturity of 1.9–2.1% Ro, suggesting its possible use as an independent paleothermal indicator in this basin. Illite crystallinity (IC) values are fairly high (0.3–0.5° 2θ) and show little variation throughout the entire maturity range. In addition, no relation was observed between vitrinite reflectance and illite crystallinity, indicating that IC is not a useful paleothermal indicator in these rocks. Illite is almost exclusively of the 2M1 polytype, suggesting a predominantly detrital origin. Incipient metamorphic and low-grade metamorphic mudrocks in the Ouachita thrust belt to the east of the Arkoma Basin are regarded as the source rocks for the clays of the Atoka Formation. Rapid transportation and deposition by turbidity currents probably played a key role in protecting these unweathered micas from pervasive alteration in the terrestrial environment.

Results are presented of a diagenetic study from the 1300 m thick Oligocene Molasse deposits penetrated by the Thônex geothermal exploration well (Geneva, Switzerland). The x-ray diffraction (XRD) studies of fine-grained rocks indicate the following diagenetic changes: a decrease of illite/smectite (US) expandability from approximately 90% to 30% with depth, a decrease of the amount of US in the clay mineral fraction, and the appearance of corrensite at depths >750 m. The transition from random US to ordered I/S occurs at the base of the Thônex well (1200 to 1300 m) and is associated with a coal rank of about 0.7% Rr (mean random vitrinite reflectance) corresponding to paleotemperatures of 110 to 115 °C Corrensite appears at a vitrinite reflectance value of 0.6% Rr and a corresponding paleotemperature of 100 °C. The amount of post-Molasse erosion is estimated to be approximately 2 km. Thermal history modeling of the Thônex well suggests maximum paleotemperatures of 80 to 115°C and an average paleogeothermal gradient of 27 °C/km during Late Miocene maximum burial conditions.

Temperature-dependent clay mineral assemblages and vitrinite reflectance data have been used to investigate levels of diagenesis from the Messinian Laga Basin in the Central Apennines developed at the footwall of the Sibillini Mts. and the Gran Sasso Massif. Data are from stratigraphic units forming the main siliciclastic basin fill up to Middle Messinian gypsum-arenites and its pre-orogenic substratum. Specifically, the largest Rom% values and percentages of illite layers in illite-smectie (I-S) are found in the basin depocenter and at the footwall of the main carbonate thrust sheets. Smaller Rom% values, and percentage of illite layers in I-S characterize less subsided sectors surrounding the depocenter.

The X-ray diffraction data were treated using decomposition methods and the peaks identified were rationalized in terms of discrete and/or mixed-layer phases. Complex clay mineral assemblages were found in the Laga Fm. including three sub-populations of illitic material corresponding to authigenic and detrital components. I-S mixed layers record the maximum paleotemperature the Laga Fm. experienced, which is directly related to its burial history. Kübler index (KI) data, however, suggest higher temperatures related to detrital K-micas inherited from the uplift of the Alpine-Apennines chain.

A tentative calculation of paleotemperatures from selected data of organic and inorganic parameters is also proposed and compared with recent sedimentological, stratigraphic and structural data. We conclude that the Laga Basin fill never experienced temperatures of >100–110°C, generally due to variable sedimentary loading, whereas localized anomalous heating is due to the effect of the tectonic emplacement and subsequent local erosion of the Sibillini and Gran Sasso thrust sheets.

The ‘Fischschiefer formation’ has been identified as the likely source rock for petroleum in the western Molasse Basin of Austria. The investigated cores originate from different depths (1242 m to 4294 m) of the Fischschiefer horizon. The illitization observed in the <0.2 μm fraction proceeds slowly, probably because of the low geothermal gradient (3°C/100 m) in the Molasse Basin. The illite content in illite-smectite ranges from 30% (randomly ordered) for the shallowest sample to 65% (R0+R1 ordering) for the deepest sample. The oxygen index (OI) vs. hydrogen index (HI) plot implies type I to II kerogen for the organic matter. Vitrinite reflectance and Rock Eval parameters indicate an immature stage in the diagenesis of kerogen. Only the deepest sample (4294 m, 0.6% Rr) reaches the early oil window. There is a good correlation of the illitization trend of the mixed-layer mineral I-S and the organic maturity parameters.

Miocene pelitic sedimentary rocks from six wells in the Sava Depression (sub-basin in the south-western part of the Pannonian Basin System) were investigated in order to determine the degrees of diagenetic alteration.Qualitative and semiquantitative mineral compositions of samples and the content of smectite in illite-smectite (I-S) were determined by X-ray powder diffraction (XRD).Vitrinite reflectance and thermal alteration index (TAI) were measured in order to estimate the palaeotemperatures.Carbonate minerals, clay minerals and quartz are the main constituents of the pelitic sediments.Feldspars (albite), pyrite, opal-CT and hematite are present as minor constituents in some rocks. The mineral composition of the rocks, apart from previously known differences caused by various depositional environments and clastic material provenance, is dependent on the degree of diagenetic processes. At elevated temperatures and large burial depths the minerals formed by alteration processes or precipitated at the surface; smectite, kaolinite and calcite were gradually replaced by minerals formed by diagenetic processes, i.e. by illite-smectite, illite, chlorite, Ca-excess dolomite/ankerite and albite. Based on XRD data for smectite, I-S and illite, three stages of diagenetic development have been established. The early stage was characteristic of samples at depths <1.8 km containing smectite, I-S of the random R0 type and detrital illite.The middle stage begins with the appearance of the ordered R1 type of I-S at the depths >1.8 km and temperature above 80°C. At depths >4.6 km with corresponding temperatures >190ºC, the late stage began, characterized by the presence of R>1 I-S with <10% smectite.

The Mississippian volcano-sedimentary complex in the Toca da Moura – Cabrela areas represents remnants of intra-volcanic marine sedimentary basins, formed during the collision between the Ossa Morena Zone with the South Portuguese Zone. These rock units are unconformably overlain by the Pennsylvanian intramontane coal-bearing Santa Susana Basin. Vitrinite reflectance determinations from rocks of these two basins indicate two episodes of thermal maturation. During the first episode, the Toca da Moura – Cabrela volcano-sedimentary complexes attained high maturation levels, equivalent to anthracite coal rank (3.0–3.5% Roran), which pre-dates the middle Moscovian Santa Susana Basin. The Santa Susana Basin attained moderate maturation levels equivalent to bituminous coal rank (1.35–1.5% Roran) recording a second episode of thermal maturation. Here, peak thermal conditions did not overprint the first maturation episode. The observed effects of magmatic intrusion on the thermal maturity and the lack of any increase in vitrinite reflectance with depth through c. 400 m of section in borehole SDJ-1 indicate high geothermal gradients during the first maturation episode. A contemporaneous magmatic event associated with the c. 335–320 Ma Cuba-Alvito Gabbros/Diorites of the Beja Massif was the possible cause for the high geothermal gradients postulated for the first maturation episode. Burial under a post-upper Moscovian sedimentary cover was the most likely process to account for the maturation levels determined for the Santa Susana Basin and for the second episode of thermal maturation.

Lipid biomarkers have been extensively applied for tracing organisms and evolutionary processes through Earth's history. They have become especially important for the reconstruction of early life on Earth and, potentially, for the detection of life in the extraterrestrial realm. However, it is not always clear how exactly biomarkers reflect a paleoecosystem as their preservation may be influenced by increasing temperatures (T) and pressures (P) during burial. While a number of biomarker indices reflecting thermal maturity have been established, it is often less well constrained to which extent biomarker ratios used for paleoreconstruction are compromised by T and P processes. In this study we conducted hydrous pyrolysis of Green River Shale (GRS) kerogen in gold capsules for 2–2400 h at 300°C to assess the maturation behaviour of several compounds used as life tracers and for the reconstruction of paleoenvironments (n-alkanes, pristane, phytane, gammacerane, steranes, hopanes and cheilanthanes). Lignite samples were maturated in parallel with the GRS kerogen to obtain exact vitrinite reflectance data at every sampling point. Our experiment confirms the applicability of biomarker-based indices and ratios as maturity indicators (e.g. total cheilanthanes/hopanes ratio; sterane and hopane isomerization indices). However, several biomarker ratios that are commonly used for paleoreconstructions (e.g. pristane/phytane, pristane/n-C17, phytane/n-C18 and total steranes/hopanes) were considerably affected by differences in the thermal degradation behaviour of the respective compounds. Short-term experiments (48 h) performed at 400°C also revealed that biomarkers >C15 (especially steranes and hopanes) and ‘biological’ chain length preferences for n-alkanes are vanished at a vitrinite reflectance between 1.38 and 1.83% RO. Our data highlight that ‘thermal taphonomy’ effects have to be carefully considered in the interpretation of biomarkers in ancient rocks and, potentially, extraterrestrial materials.

Thermal history and evolution of the Palaeozoic petroleum system of the western Lower Saxony Basin as well as charge history of the Apeldorn gas field was reconstructed using 2-D forward basin modelling software. The Apeldorn gas field is located on an inverted western rim of the Lower Saxony Basin (LSB) and belongs with its relatively anomalous nitrogen content of 73.9 vol. % to one of the most unique gas accumulations in North Germany. Based on thermal calibration studies utilising both, vitrinite reflectance and corrected bottom hole temperatures as calibration parameters, a shallow burial model and an anomalous event of Coniacian high heat flow of 80 to 120 mW/m2 was derived. As result, Lower Triassic and younger successions became subjected to slight changes in thermal maturity as opposed to Carboniferous and Permian successions, which show no assessable impact of the high heat flow event on the coalification pattern. The deep burial model in contrary to the shallow burial model is not supported by the structural reconstruction and backstripping in this more marginal setting. According to the modelling results, the key charge of the present Apeldorn gas field began in Tithonian (late Upper Jurassic) during the major phase of rifting in the Lower Saxony Basin. The present Westphalian coal-derived gas accumulations of the Lower Triassic Buntsandstein reservoir were sourced directly from modelled methane pools at top Rotliegend level. The hydrocarbon potential of the Westphalian source rocks became exhausted in Oxfordian (early Upper Jurassic). Reduction of the hydrostatic pressure during the Coniacian high heat flow event together with uplift during the Coniacian-Santonian inversion led to an extensive free gas exsolution. The resulting gas mixture between the exsolved free gas and the Westphalian coal-derived gas reached and saturated Buntsandstein reservoir. The structural trap became destroyed in course of the inversion leading to a sharp decrease of methane and nitrogen saturation.

Devonian miospores have been discovered in the previously poorly dated Old Red Sandstone volcanic sequence of Papa Stour. They occur at two sites in minor sedimentary deposits between the lavas, and fossil fish remains are also present. The age range of the miospores is mid Eifelian to early Givetian, probably more specifically late Eifelian and from a position close to the Achanarras horizon. This allows a correlation of the Papa Stour volcanic sequence with that of the Upper Stromness Flags of Orkney and not the tuffaceous horizons in the Eday Sandstones. The good preservation and composition of the miospores indicate a close similarity to other Orcadian Basin sediments and support the view that the Old Red Sandstone sequences W of the Melby Fault have affinities with the Orkney and Caithness successions rather than with Shetland. The age of the volcanic sequence also provides a valuable datum point for plate tectonic models based on the geochemistry of Old Red Sandstone lavas.