Investigation of the pyrolytic liberation of molecular nitrogen from Palaeozoic sedimentary rocks

Open-system non-isothermal pyrolysis up to 1,200°C in combination with elemental analysis was used to study the thermal liberation of molecular nitrogen (N₂) from sedimentary rocks and kerogen concentrates of Palaeozoic age from the Central European Basin system and an Eocene shale (Liaohe Basin, China) with a high content (36%) of ammonium feldspar (buddingtonite). The N/C_org (atomic) ratios of the kerogen concentrates ranged from 0.005 to 0.014, which represents the range commonly observed for coals. Bulk N/C_org ratios of the Palaeozoic shales extended from 0.035 to 0.108, indicating the presence of significant amounts of inorganic nitrogen. Namurian A and A-B (CnA; CnA-B) samples typically exhibited the earliest onset of N₂ generation with intense, characteristic peaks around 600°C. N₂ liberation from the buddingtonite-rich sample occurred at higher temperatures, with a broad peak around 700°C. Pyrograms of the kerogen concentrates showed no or strongly reduced N₂ generation in the 500–700°C range. On-line isotope-specific analysis of the pyrolytically liberated N₂ on one sample revealed a variability of ∼10‰ in the δ¹⁵N values and a steady increase in δ¹⁵N with temperature during the main phase of N₂ generation.     

Organic matter maturation under the influence of a deep intrusive heat source: A natural experiment for quantitation of hydrocarbon generation and expulsion from a petroleum source rock (Toarcian shale, northern Germany)

Four shallow boreholes were drilled in the Hils syncline, northern Germany, in order to determine quantitatively the amount of hydrocarbons generated and expelled during maturation of a typical kerogen-type-II-bearing source rock. The holes penetrated the carbonceous Lias shales (Posidonia shale, Lower Toarcian) and part of the adjacent Dogger α and Lias δ mudstones. The maturity of the organic matter in the cores recovered ranges from immature (0.48% R̄₀) to overmature 1.45% R̄₀) due to location of the Hils syncline in the vicinity of the Vlotho Massif, which is deep-seated intrusive body. Facies variations of the Lias within the short geographical distances in the study area are negligible.Organic matter mass balance calculations were based on detailed organic geochemical analyses of residual material in the Lias shales (kerogen, bitumen etc.) and on the evidence of a uniform initial composition of these sediments in the study area. Dead carbon determinations supported this latter criterion but were not used as a parameter in the calculations.About 50% of the initial kerogen was transformed into oil, gas and inorganic compounds during the vitrinite reflectance increase from 0.48 to 0.88% R̄_o and only marginally more during the maturity increase from 0.88 to 1.45% R̄_o. Only a small portion of the generated material remained in the source rock even at a relatively early stage of generation (0.68% R̄_o). Expulsion efficiency of oil plus gas reached a value of 86% at the end of the main generation stage (0.88% R̄_o).     

Numerical modelling of burial and temperature history as an approach for an alternative interpretation of the Bramsche anomaly, Lower Saxony Basin

The Lower Saxony Basin, Germany, is one of the several sedimentary basins within the Central European Basin system. In its southwestern part, anomalously high maturity of organic matter has been observed to reach 4.5% VRr in Upper Jurassic and Lower Cretaceous sedimentary rocks in an area which coincides with a magnetic and a positive gravimetric anomaly. This anomaly was often interpreted as the consequence of a deep-seated igneous intrusion, the so-called Bramsche Massif. However, results obtained from calibrated numerical modelling are not in accordance with this scenario. Instead, a burial by approximately 4 km of now-eroded Cretaceous rocks was revealed to be the probable cause for the anomaly. Data and modelling results from six boreholes and two pseudo-wells support this view.     

Analysis of undisturbed layers of a waste deposit landfill – Insights into the transformation and transport of organic contaminants

Comprehensive GC/MS analysis was applied to both the mobile liquid phase (seepage water) and the immobile solid matter of discrete layers derived from a waste deposit landfill. The vertical distribution of organic compounds supports information on the transport, transfer and transformation processes with depth and, consequently, with time.Numerous low molecular weight organic contaminants of natural and xenobiotic origin were identified and partially quantified. Several were selected to act as molecular indicators for different processes. Interpretation of their occurrence and concentration profiles (considering possible waste sources) and their molecular properties allowed us to (i) differentiate immobile and mobile fractions, (ii) reveal restrictions in the vertical transport by transfer processes between particulate and water phase, (iii) identify dynamic accumulations of individual contaminants and (iv) estimate approximate residence times. In addition, intensive degradation processes were pointed out for the natural fraction of the organic matter by way of determination of specific transformation products. Besides the transformation of natural components, transformation of numerous xenobiotics was recognised. In particular, with respect to an important group of contaminants, the phthalate-based plasticisers, a detailed view of (i) the influence of transfer and transport phenomena on transformation processes as well as (ii) the consecutive appearance of different degradation steps in both seepage water and solid waste was pointed out. The information provides a valuable base for the prediction of the long term behaviour of organic contaminants in waste deposit landfills.     

Maturity modelling integrated with apatite fission-track dating: Implications for the thermal history of the Mid-Polish Trough (Poland)

The Mid-Polish Trough (MPT) is situated in the easternmost part of the Central European Basin System (CEBS) and stretches NW–SE across the Polish Basin. It was characterised by pronounced subsidence and thick sediment accumulation between the Permian and the Late Cretaceous. Late Cretaceous–early Paleogene basin inversion led to the formation of the Mid-Polish Swell (MPS). The study area is located within the Pomeranian segment of the MPT/MPS (NW Poland) and experienced up to 7 km Permian-Mesozoic subsidence. PetroMod 1-D modelling was performed on several well-sections in order to study Permian to recent burial-uplift evolution. The modelling was calibrated with new vitrinite reflectance (VR_r) data and allowed to constrain the magnitude of uplift and related erosion as well as provided a first overview of the temperature history. The base of the studied Permian–Mesozoic successions attained maximum burial depths of 4800–5400 m before the onset of the inversion, less than in the axial trough area. The thickness of pre- and most probably also syn-inversion Upper Cretaceous deposits is estimated as 300 m. Erosion associated with inversion processes removed between 900 and 1400 m of the Mesozoic sediments, i.e. 1000–1500 m less than in the most inverted central part of the trough. VR_r data suggest constant Permian–Mesozoic heat flows corresponding to present-day values (40–45 mW/m²). Apatite fission-track (AFT) ages modelled with the PetroMod module PetroTracks show a good fit with AFT ages directly measured on well samples, and further support the assumption of steady heat flow in the range 40–45 mW/m². Palaeotemperatures appear to have decreased towards the East European Craton margin, which is compatible with the present day distribution of heat flow. Thermal history modelling shows a relatively simple Permian–Mesozoic heat flow pattern in the Pomeranian segment of the MPT. Such a scenario implies that the present-day heat flow distribution has not changed essentially since Mesozoic times.     

Microfacies and depositional environment of Tertiary Tanjung Enim low rank coal, South Sumatra Basin, Indonesia

The South Sumatra basin is among the most important coal producing basins in Indonesia. Results of an organic petrography study on coals from Tanjung Enim, South Sumatra Basin are reported. The studied low rank coals have a mean random huminite reflectance between 0.35% and 0.46% and are dominated by huminite (34.6–94.6 vol.%). Less abundant are liptinite (4.0–61.4 vol.%) and inertinite (0.2–43.9 vol.%). Minerals are found only in small amounts (0–2 vol.%); mostly as iron sulfide.Based on maceral assemblages, the coals can be grouped into five classes: (1) humotelinite-rich group, (2) humodetrinite-rich group, (3) humocollinite-rich group, (4) inertinite-rich group and (5) humodetrinite–liptinite-rich group. Comparing the distribution of maceral assemblages to the maceral or pre-maceral assemblages in modern tropical domed peat in Indonesia reveals many similarities. The basal section of the studied coal seams is represented typically by the humodetrinite–liptinite-rich group. This section might be derived from sapric or fine hemic peat often occurring at the base of modern peats. The middle section of the seams is characterized by humotelinite-rich and humocollinite-rich groups. The precursors of these groups were hemic and fine hemic peats. The top section of the coal seams is typically represented by the humodetrinite-rich or inertinite-rich group. These groups are the counterparts of fibric peat at the top of the modern peats. The sequence of maceral assemblages thus represents the change of topogenous to ombrogenous peat and the development of a raised peat bog.A comparison between the result of detailed maceral assemblage analysis and the paleodepositional environment as established from coal maceral ratio calculation indicates that the use of coal maceral ratio diagrams developed for other coal deposits fails to deduce paleo-peat development for these young tropical coals. In particular, mineral distribution and composition should not be neglected in coal facies interpretations.     

Deformation mechanisms of deeply buried and surface-piercing Late Pre-Cambrian to Early Cambrian Ara Salt from interior Oman

We compared microstructures of Late Pre-Cambrian to Early Cambrian Ara Salt diapirs from the deep subsurface (3.5–5 km) of the South Oman Salt Basin and from surface-piercing salt domes of the Ghaba Salt Basin. Laterally, these basins are approximately 500 km apart but belong to the same tectono-sedimentary system. The excellent data situation from both wells and outcrops allows a unique quantification of formation and deformation mechanisms, spanning from sedimentation to deep burial, and via re-activated diapir rise to surface piercement. Microstructures of gamma-irradiated and etched thin sections indicate dislocation creep and fluid-assisted grain boundary migration as the main deformation mechanisms operating in the deep subsurface. Microstructures from the surface are characterised by large ‘old’ subgrain-rich crystals. These ‘old’ grains are partly replaced by ‘new’ subgrain-free and subgrain-poor crystals, which show gamma irradiation-decorated growth bands and fibrous microstructures, indicative of pressure solution creep and static recrystallisation, most likely due to surface piercement and exposure. Using subgrain size piezometry, the maximum differential stresses for the subsurface salt is 1.7 MPa and those for the surface-piercing salt is 3.4 MPa, the latter value displaying the high stress conditions in the diapir ‘stem’ as the salt rises on its way to the surface.     

Identification of specific organic contaminants for estimating the contribution of the Elbe river to the pollution of the German Bight

GC/MS analyses have been applied to sediment samples of the German Bight in order to document the state of organic contamination as well as to identify specific molecular markers that are appropriate to estimate the discharge of anthropogenic compounds derived from the Elbe river. Detailed screening analyses revealed a wide variety of organic lipophilic compounds of biogenic, petrogenic as well as anthropogenic origin. Potential marker compounds indicating the contribution of the Elbe river could be attributed mainly to the chlorinated aromatic contaminants. Specifically, these include tetra- to hexachlorobenzenes, mono- to dichloronaphthalenes, hexachlorobutadiene, tetrabutyl tin, alkylsulfonic acid phenylesters, 1,2,3,6,7,8-hexahydro-1,1,6,6-tetramethyl-4-isopropyl-as-indacene and 4,4′-dichlorodiphenylsulfide. These compounds are suitable to indicate the spatial distribution of Elbe river derived organic matter.     

Experimental investigation of the compositional variation of acyclic paraffins during expulsion from source rocks

Anhydrous non-isothermal heating experiments were conducted under controlled compressive stress on cylindrical plugs of six oil shales from Permian through Eocene age. The objective of this study was to compare the distribution of acyclic paraffins in initial, residual and expelled organic matter and to highlight causes of compositional differences resulting from expulsion. Pristane generation from kerogen is highest in the Eocene Messel shale and affects the pristane / phytane (pr / ph) ratio commonly used as a redox proxy. The isoprenoid to n-alkane ratios (pr / n-C₁₇, ph / n-C₁₈) decrease during generation and are lowest in the residual bitumen due to preferential generation and retention of n-alkanes. The n-alkane distribution shows that only lacustrine shales produce high wax oils. Evaporative fractionation leads to loss of n-alkanes up to n-C₂₀ with boiling points below 350 °C. This demonstrates that lacustrine and marine shales may lead to accumulation of low wax oils due to evaporative fractionation after expulsion.