Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

Reconstructing the response of C3 and C4 plants to decadal-scale climate change during the late Pleistocene in southern Illinois using isotopic analyses of calcified rootlets

The δ¹³C and δ¹⁸O values of well-preserved carbonate rhizoliths (CRs) provide detailed insights into changes in the abundance of C₃ and C₄ plants in response to approximately decadal-scale changes in growing-season climate. We performed stable isotope analyses on 35-40 CRs sampled at 1-cm intervals from an 18-cm-thick paleosol formed in southern Illinois during Wisconsin interstadial 2. Minimum δ¹³C values show little variation with depth, whereas maximum values vary dramatically, and average values show noticeable variability; maximum δ¹⁸O values vary less than the minimum δ¹⁸O values. These findings indicate that a diverse and stable C₃ flora with a limited number of C₄ grass species prevailed during this interval, and suggest that the maximum growing-season temperatures were relatively stable, but minimum growing-season temperatures varied considerably. Two general patterns characterize the relationships between the δ¹³C and δ¹⁸O values obtained from the 1-cm samples. In some cases, low δ¹³C values correspond to low δ¹⁸O values and high δ¹³C values correspond to high δ¹⁸O values, suggesting that cooler growing-season temperatures favored C₃ and warmer growing-season temperatures favored C₄ plants. In other cases, low δ¹³C values correspond to high δ¹⁸O values, likely suggesting that wetter growing-season conditions were favorable to C₃ plants. The high density of well-preserved CRs in this paleosol provides a unique opportunity to study detailed ecological responses to high-resolution variability in growing-season climate.     

湖泊沉积物C4植物含量重建方法的讨论——以新生代柴达木盆地大红沟剖面为例

当前气候变暖是一个全球面临的重大问题,它对人类赖以生存的植被生态系统造成的影响已经在全球各地逐步显现出来。为了深入了解植物生态系统对环境和气候变化的响应机制,我们需要更好地借鉴地质历史时期气候环境和植物协同演化的重要事件。C₄植物作为陆地生产力较强的植物,在植物生态演化中占举足轻重的地位。目前研究表明C₄植物可能最晚起源于始新世-渐新世之交,但从它早期起源到随后在生态系统中的大规模扩张时间间隔长达20多个百万年。是什么因素导致了C₄植物的起源和扩张是一个悬而未决的重要问题,需要开展大量的调查研究来评估和重建C₄植物在过去生态系统中的相对生物量变化。重建C₄植物的含量目前主要的方法是建立在C₃/C₄植物碳同位素和植物内部结构形态差异基础之上。最常运用的研究材料包括(古)土壤有机质、成壤碳酸盐、陆地食草动物体组织、沉积物生物标志物、孢粉、植硅体等。这些方法在重建现代以及地质历史时期C₄植物相对生物量变化的研究中发挥了重要作用,但同时也存在很多无法避免的问题。本文介绍了C₄植物起源和扩张机制的主流观点以及不同研究材料的碳同位素所推算C₄植物生物量的基本原理,并以柴达木盆地大红沟剖面为例,针对新生代湖泊沉积物中陆生高等植物的长链正构烷烃特征和单体烃碳同位素的研究结果,详细讨论C₄植物含量重建的方法与缺点,为探讨C₄植物起源、演化及控制因素提供参考。我们通过分析前人研究的大红沟剖面长链正构烷烃及单体烃 δ¹³C_alk 值特征,推测在30~24 Ma、20~17 Ma和13~7 Ma期间δ¹³C_alk值显示相对正偏的原因,可能是干旱和C₄植物在当地生态系统中出现的双重因素叠加造成的。但这一推断还需要借助于新的研究方法,即单颗粒孢粉碳同位素的方法来提供C₄植物的确凿证据。     

Comparison of binding abilities of fulvic and humic acids extracted from recent marine sediments with UO2

Potentiometric titrations were used to measure conditional stability constants of UO₂²⁺-fulvic acid and UO₂²⁺-humic acid complexes. Both 2:1 and 1:1 COO^-:UO₂²⁺ binding were observed. With decreasing metal concentration (2.5·10⁻⁴-6.25·10⁻⁵ M) increasing amounts of UO₂²⁺ were in the form of 1:1 humate complexes and 2:1 fulvate complexes. Despite the high nitrogen content and the low acidic OH group content, the successive stability constant values were similar to those determined for divalent cations associated with fulvic and humic compounds isolated from soils. Stability constant values increase simultaneously with increasing ionization of the humic (or fulvic) acid polyelectrolytes and with decreasing metal concentration.     

Experimental identification of CO2–water–rock interactions caused by sequestration of CO2 in Westphalian and Buntsandstein sandstones of the Campine Basin (NE-Belgium)

Geological sequestration of CO₂ is one of the options studied to reduce greenhouse gas emissions. Although the feasibility of this concept is proven, apart from literature data on modelling still little is known about the CO₂–water–rock interactions induced by CO₂-injection.To evaluate the effect of CO₂–water–rock interactions on three sandstone aquifers in NE-Belgium an experimental setup was built. Eighteen experiments were performed in which sandstones were exposed to supercritical CO₂. CO₂–water–rock interactions were deduced from the evolution of aqueous concentrations of 25 species and a thorough characterisation of the sandstones before and after treatment. The results show that dissolution of ankerite/dolomite and Al-silicates could enhance porosity/permeability. The observed precipitation of end-member carbonates could increase storage capacity if it exceeds carbonate dissolution. Precipitation of the latter and of K-rich clays as observed, however, can hamper the injection.