Chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100°C to 550°C: Case study in the Liassic black shale formation of Central Swiss Alps

Hydrocarbon distributions and stable isotope ratios of carbonates (δ¹³C_car, δ¹⁸O_car), kerogen (δ¹³C_ker), extractable organic matter (δ¹³C_EOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C_<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C₁₂ and C₁₃n-alkanes, C₁₄, C₁₆ and C₁₈n-alkylcyclopentanes and to a lesser extend C₁₅, C₁₇ and C₂₁n-alkylcyclohexanes. The progressive ¹³C-enrichment (up to 3.9‰) with metamorphism of the C_>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C_<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C₁ and C₂ radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C_>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C₂₉ to C₃₁ range and 5α(H),14α(H),17α(H)-20R C₂₇, C₂₉ steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C₂₉Ts) vs. 17α(H),21β(H)-30-norhopane [C₂₉Ts/(C₂₉Ts + C₂₉)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.     

Planetary elements for 10 000 000 years

In 1950 Brouwer and van Woerkom published a secular theory of the variations of the planetary elements in analytical form. In the present paper we provide a graphical representation of this theory in the form of element plots for a time span of ten million years.     

A proposal for the theoretical analysis of the interactive coupled effects between urbanization and the eco-environment in mega-urban agglomerations

Mega-urban agglomerations are strategic core areas for national economic development and the main regions of new urbanization. They also have important roles in shifting the global economic center of gravity to China. However, the development of mega-urban agglomerations has triggered the interactive coercion between resources and the eco-environment. The interactive coupled effects between urbanization and the eco-environment in mega-urban agglomerations represent frontier and high-priority research topics in the field of Earth system science over the next decade. In this paper, we carried out systematic theoretical analysis of the interactive coupling mechanisms and coercing effects between urbanization and the eco-environment in mega-urban agglomerations. In detail, we analyzed the nonlinear-coupled relationships and the coupling characteristics between natural and human elements in mega-urban agglomerations. We also investigated the interactive coercion intensities between internal and external elements, and the mechanisms and patterns of local couplings and telecouplings in mega-urban agglomeration systems, which are affected by key internal and external control elements. In addition, we proposed the interactive coupling theory on urbanization and the eco-environment in mega-urban agglomerations. Furthermore, we established a spatiotemporal dynamic coupling model with multi-element, multi-scale, multi-scenario, multi-module and multi-agent integrations, which can be used to develop an intelligent decision support system for sustainable development of mega-urban agglomerations. In general, our research may provide theoretical guidance and method support to solve problems related to mega-urban agglomerations and maintain their sustainable development.     

Impact of Sea-level Rise and Storm Surges on a Coastal Community

A technique to evaluate the risk of storm tides (the combination of a storm surge and tide) under present and enhanced greenhouse conditions has been applied to Cairns on the north-eastern Australian coast. The technique combines a statistical model for cyclone occurrence with a state-of-the-art storm surge inundation model and involves the random generation of a large number of storm tide simulations. The set of simulations constitutes a synthetic record of extreme sea-level events that can be analysed to produce storm tide return periods. The use of a dynamic storm surge model with overland flooding capability means that the spatial extent of flooding is also implicitly modelled. The technique has the advantage that it can readily be modified to include projected changes to cyclone behaviour due to the enhanced greenhouse effect. Sea-level heights in the current climate for return periods of 50, 100, 500 and 1000 years have been determined to be 2.0 m, 2.3 m, 3.0 m and 3.4 m respectively. In an enhanced greenhouse climate (around 2050), projected increases in cyclone intensity and mean sea-level see these heights increase to 2.4 m, 2.8 m, 3.8 m and 4.2 m respectively. The average area inundated by events with a return period greater than 100 years is found to more than double under enhanced greenhouse conditions.     

Palaeomagnetism of the teschenitic rocks (Lower Cretaceous) in the Outer Western Carpathians of Poland: constraints for tectonic rotations in the Silesian unit

Results of palaeomagnetic investigations of the Lower Cretaceous teschenitic rocks in the Silesian unit of the Outer Western Carpathians in Poland bring evidence for pre-folding magnetization of these rocks. The mixed-polarity component reveals inclinations, between 56° and 69°, which might be either of Cretaceous or Tertiary age. Apparently positive results of fold and contact tests in some localities and presence of pyrhotite in the contact aureole suggest that magnetization is primary, although a Neogene or earlier remagnetization cannot be totally excluded since inclination-only test between localities gives 'syn-folding' results. Higher palaeoinclinations (66°–69°) correlate with a younger variety of teschenitic rocks dated for 122–120 Ma, while lower inclinations (56°–60°) with an older variety (138–133 Ma). This would support relatively high palaeolatitudes for the southern margin of the Eurasian plate in the late part of the Early Cretaceous and relatively quick northward drift of the plate in this epoch, together with the Silesian basin at its southern margin. Declinations are similar to the Cretaceous–Tertiary palaeodeclinations of stable Europe in the eastern part of the studied area but rotated ca. 14°–70° counter-clockwise in the western part. This indicates, together with older results from Czech and Slovakian sectors of the Silesian unit, a change in the rotation pattern from counter-clockwise to clockwise at the meridian of 19°E. The rotations took place before the final collision of the Outer Carpathians nappe stack with the European foreland.