Hydrogeochemical models locating sulfate-methane transition zone in marine sediments overlying black shales: A new tool to locate biogenic methane?

Precise hydrogeochemical modeling of early diagenesis is a key in the reconstruction of sedimentary basin models. This determines the mineralogical evolution of the sediment and consequently the porosity of the rock. During early diagenesis also part of the initial organic matter is converted into biogenic gas: CH₄ CO₂, and H₂S. These processes are part of complex reaction chains during sedimentation, and biogeochemical reactions leave different signals that can be observed today. In this work, we reproduce the early diagenetic processes as integrated signals over geological times in sediments of the Demerara Rise by applying chemical thermodynamics using the PHREEQC (version 2) computer code. The investigated sediments are characterized by the presence of black shales in 410–490 mbsf and by a diagenetic barite layer above in 300–350 mbsf at depth of sulfate-methane transition (SMT). We determine the parameters that influence the location of diagenetic barite peaks in sediments overlying black shales by means of a novel modeling approach. Crucial parameters are the amount of bacterial organic matter mineralization, sedimentation rates and bottom water sulfate concentrations. All parameters are intertwining and influence the sulfate-methane cycle. They affect the location of the SMT visualized by diagenetic barite peaks. However, our model approach opens a wide field in exploring early diagenetic reactions, processes and products (such as biogenic methane) over geological times mirrored by diagenetic minerals and pore water concentration profiles that can be detected in present-day sediments.     

Multiple controls on the paleoenvironment of the Early Cambrian marine black shales in the Sichuan Basin,SW China: Geochemical and organic carbon isotopic evidence

In order to understand the paleoenvironment of the Early Cambrian black shale deposition in the western part of the Yangtze Block, geochemical and organic carbon isotopic studies have been performed on two wells that have drilled through the Qiongzhusi Formation in the central and southeastern parts of Sichuan Basin. It shows that the lowest part of the Qiongzhusi Formation has high TOC abundance, while the middle and upper parts display relative low TOC content. Redox-sensitive element (Mo) and trace elemental redox indices (e.g., Ni/Co, V/Cr, U/Th and V/(V + Ni)) suggest that the high-TOC layers were deposited under anoxic conditions, whereas the low-TOC layers under relatively dysoxic/oxic conditions. The relationship of the enrichment factors of Mo and U further shows a transition from suboxic low-TOC layers to euxinic high-TOC layers. On the basis of the Mo-TOC relationship, the Qiongzhusi Formation black shales were deposited in a basin under moderately restricted conditions. Organic carbon isotopes display temporal variations in the Qiongzhusi Formation, with a positive excursion of δ¹³C_org values in the lower part and a continuous positive shift in the middle and upper parts. All these geochemical and isotopic criteria indicate a paleoenvironmental change from bottom anoxic to middle and upper dysoxic/oxic conditions for the Qiongzhusi Formation black shales. The correlation of organic carbon isotopic data for the Lower Cambrian black shales in different regions of the Yangtze Block shows consistent positive excursion of δ¹³C_org values in the lower part for each section. This excursion can be ascribed to the widespread Early Cambrian transgression in the Yangtze Block, under which black shales were deposited.     

Diagenetic evolution of the upper Cretaceous limestone and sandstone exhumed reservoirs in the western Basque–Cantabrian Basin,North Spain

The Basque–Cantabrian Basin (NE Spain) has been considered one of the most interesting areas for hydrocarbon exploration in the Iberian Peninsula since the 60th to 70th of last century. This basin is characterized by the presence of numerous outcrops of tar sands closely associated with fractures and Triassic diapirs. The aims of this work is to establish the diagenetic evolution of the Upper Cretaceous reservoir rocks with special emphasis in the emplacement of oil and their impact on reservoir quality. The studied rocks are constituted of carbonates and sandstones that contain massive quantities of bitumen filling vugs and fractures.Petrographic results indicate that the carbonate rocks from Maestu outcrops are bioclastic grainstones and wackestones, whereas the tar sandstones from Atauri and Loza outcrops are dominated by quartzarenites and subordinated subarkoses. The paragenetic sequence of the main diagenetic phases and processes include, pyrite, bladed and drusy calcite cement, calcite overgrowths, silicification of bioclasts and microcrystalline rhombic dolomite cement, and first stage of oil emplacement, blocky calcite cement, coarse crystalline calcite cement, calcitized dolomite, calcite veins, saddle dolomite and stylolites filled by the second phase of oil entrance. Together with the above mentioned diagenetic alterations, the arenites are affected by early kaolinitization of feldspars and the scarce formation of clay rim and epimatrix of illite. All sandstones and dolomitized carbonate rocks show high intercrystalline and intergranular porosity which is full by biodegraded hydrocarbons (solid bitumen). The biodegradation affects alkanes, isoprenoids and partially hopanes and steranes saturated hydrocarbons. Aromatics hydrocarbons, like naphthalenes, phenanthrenes, dibenzothiophenes and triaromatics are also affected by biodegradation. Results indicate that the first HC emplacement corresponds to early stage of calcite and dolomite cementation, and the second and more important emplacement is related to fracturation processes resulting in the formation of excellent reservoirs.     

基于傅里叶变换质谱的烃源岩成熟度评价方法及地质意义

<正>伴随非常规油气资源的勘探开发,油气资源开采的广度和深度进一步扩大,一定程度上缓解了我国油气供需矛盾、保障了我国能源安全,同时有力推动了能源结构战略转型。但同时也对能源地质研究工作提出了新的挑战。有机质成熟度是油气评价的重要参数之一,不同成熟阶段的有机质会对应产出不同成因、不同性质、不同质量的油气,如何准确评价沉积有机质成熟度是当前油气资源勘探开发工作的关键问题之一。前人在科研实践工作中从光学、化学、谱学等角度提出了适用条件各异的成熟度评价方法,在部分地质环境中获得了良好的应用效果,但已有的成熟度指标多受测定方法原理的制约导致其适用性不同程度受限(肖贤明等,2020),制约了油气资源的高质量勘探开发。     

Alteration of five organic compounds by glow discharge plasma and UV light under simulated Mars conditions

The Viking missions to Mars failed to detect any organic material in regolith samples. Since then, several removal mechanisms of organic material have been proposed. Two of these proposed methods are removal due to exposure to plasmas created in dust devils and exposure to UV irradiation. The experiments presented here were performed to identify similarities between the two potential removal mechanisms and to identify any compounds produced from these mechanisms that would have been difficult for the Viking instruments to detect. Five organic compounds, phenanthrene, octadecane, octadecanoic acid, decanophenone and benzoic acid, were exposed to a glow discharge plasma created in simulated martian atmospheres as might be present in dust devils, and to UV irradiation similar to that found at the surface of Mars. Glow discharge exposure was carried out in a chamber with 6.9 mbar pressure of a Mars like gas composed mostly of carbon dioxide. The plasma was characterized using emission spectroscopy and found to contain cations and excited neutral species including carbon dioxide, carbon monoxide, and nitrogen. UV irradiation experiments were performed in a Mars chamber which simulates the temperature, pressure, atmospheric composition, and UV fluence rates of equatorial Mars. The non-volatile residues left after each exposure were characterized by mass loss, infrared spectroscopy and high resolution mass spectrometry. Oxidized, higher molecular weight versions of the parent compounds containing carbonyl, hydroxyl and alkenyl functional groups were identified. The presence of these oxidized compounds suggests that searches for organic material in soils on Mars use instrumentation suitable for detection of compounds which contain the above functional groups. Discussions of possible reaction mechanisms are given.     

Titan trace gaseous composition from CIRS at the end of the Cassini-Huygens prime mission

This paper reports on the results from an extensive study of all nadir-looking spectra acquired by Cassini/CIRS during the 44 flybys performed in the course of the nominal mission (2004-2008). With respect to the previous study (Coustenis, A., and 24 colleagues [2007]. Icarus 189, 35-62, on flybys TB-T10) we present here a significantly richer dataset with, in particular, more data at high northern and southern latitudes so that the abundances inferred here at these regions are more reliable. Our enhanced high-resolution dataset allows us to infer more precisely the chemical composition of Titan all over the disk. We also include improved spectroscopic data for some molecules and updated temperature profiles. The latitudinal distributions of all of the gaseous species are inferred. We furthermore test vertical distributions essentially for acetylene (C₂H₂) from CIRS limb-inferred data and from current General Circulation Models for Titan and compare our results on all the gaseous abundances with predictions from 1-D photochemical-radiative models to check the reliability of the chemical reactions and pathways.     

The photochemical products of benzene in Titan’s upper atmosphere

The Cassini spacecraft detected benzene high in Titan’s atmosphere as well as the presence of large mass positive and negative ions. Previous work has suggested that these large mass ions could be composed of fused-ring polycyclic aromatic hydrocarbon compounds. These fused-ring PAHs, such as naphthalene and anthracene, are usually the result of high temperature processes that may not occur in Titan’s thin, cold, upper thermosphere. Here we suggest that a different class of aromatic compounds, polyphenyls, may be a better explanation of the data. Polyphenyls can grow to be large polymeric structures and could condense to form the aerosols seen in Titan’s cloud and hazes. They have similar properties to fused-ring PAHs (for example, electron affinity, ionization potential) and could be the negative ion species seen in the CAPS instrument data from the Cassini spacecraft.     

Urbanised beaches of the Ligurian coastal area (NW Mediterranean): A classification based on organic-matter characteristics and hydrolytic enzymatic activities

The beaches of Liguria have been intensively affected by human activities for over a century, transforming nearly the entire coastline from natural to urbanised and significantly upsetting beach ecological properties. The present study aims to investigate 9 Ligurian beaches characterised by different degree of urbanisation, to test if and to what extent the organic-matter (OM) recycling processes can be linked to the human activity. Swash zone sediment, sampled during the spring–summer–autumn period, when the anthropogenic influence is at its maximum due to tourism, was analysed for OM features and recycling processes. Multivariate statistical analyses showed that huge amounts of detrital OM accumulated in the more urbanised sites, where the anthropogenic influence was at its peak, deriving from higher inhabitant number and density, from the presence of crowded roads very near to the swash zone and sewage treatment plants. The presence of torrent outlets on the beaches provided further OM accumulation. Lipids, carbohydrates and degraded autotrophic pigments were the OM fractions mainly responsible of the differentiation, and rather constant, high labile phosphorus contents were found in the more urbanised sites. The high activity values of the hydrolytic enzymes indicate the response of the microbial system to the OM accumulation in the urban sites. However, a decoupling of the trends of some enzymatic activities (namely glucosidase and lipase) and their target OM was observed in the highly urbanised conditions.     

Kinematic wave solutions for pollutant transport over an infiltrating plane with finite‐period mixing and mixing zone

Kinematic wave solutions are derived for transport of a conservative non‐point‐source pollutant during a rainfall‐runoff event over an infiltrating plane for two cases: (i) finite‐period mixing and (ii) soil‐mixing zone. Rainfall is assumed to be steady, uniform and finite in duration, and it is assumed to have zero concentration of pollutants. Infiltration is assumed constant in time and space. Prior to the start of rainfall, the pollutant is distributed uniformly over the plane. In the first case, when rainfall occurs, the mixing of pollutant in the runoff water occurs in a finite period of time. In the second case, the chemical concentration is assumed to be a linearly decreasing function of rainfall intensity and overland flow. The solute concentration and discharge are found to depend on the flow characteristics as well as the solute concentration parameters. The characteristics of solute concentration and discharge graphs seem to be similar to those reported in the literature and observed in laboratory experiments. Copyright © 2002 John Wiley & Sons, Ltd.     

Organic carbon concentrations and transport in small mountain rivers,Panama

Tropical small mountainous rivers (SMRs) are increasingly recognized for their role in the global export of dissolved organic carbon (DOC) to the oceans. Here we utilize the Isthmus of Panama as an ideal place to provide first-order estimates of DOC yields across a wide assemblage of bedrock lithologies and land cover practices. Samples for dissolved organic carbon (DOC) analysis were collected across Panama along an E–W transect from the central Panama area to the Costa Rican border for 24 mainstem rivers, 3 large tributary rivers, and one headwater stream. Sampling occurred during both the wet and the dry seasons. DOC concentrations during the wet season are higher than during the dry season in all but three of the rivers. Concentrations vary greatly from river to river and from season to season, with values as low as 0.64 mg l⁻¹ to greater than >25 mg l⁻¹ with the highest concentrations observed for the rivers draining Tertiary marine sedimentary rocks in the Burica and Azuero peninsulas. DOC yields from Panamanian rivers (2.29–7.97 tons/km²/y) are similar to or slightly lower than those determined for other tropical SMR systems. Areas underlain by Tertiary aged sediments exhibited significantly higher mean DOC yields compared to their igneous counterparts, despite maintaining substantially lower aboveground carbon densities, suggesting the important influence of lithology. Finally, regression analyses between DOC yields and select watershed parameters revealed a negative and statistically significant relationship with maximum and mean gradient suggesting lower soil retention times may be linked to lower DOC yields.