Organic matter accumulation,redox, and diagenetic history of the Marcellus Formation,southwestern Pennsylvania,Appalachian basin

Variations in the concentration of redox sensitive elements combined with pyrite framboid size data documented from a Marcellus Formation (Middle Devonian) core recovered from southwestern Pennsylvania elucidate the redox, organic matter accumulation, and diagenetic history of these deposits in this region of the basin. Uranium and Mo enrichment and Fe/Al display sharp increases coincident with diminishing Th/U upward through the initial 3rd order trangressive systems tract (lower Union Springs Member). These data as well as abundant small (<6 μm) pyrite framboids record establishment of strongly reducing benthic conditions, perhaps related to the expansion of an oxygen minimum zone induced by increased surface productivity. Strongly anoxic, even euxinic, conditions were interrupted by episodes of dysoxia, perhaps seasonal or longer term. Overlying regressive systems tract (RST) deposits record modestly improved redox conditions, likely a reflection of a receding oxygen minimum zone as base level dropped. A subsequent 3rd order base level rise and renewed expansion of the oxygen minimum zone triggered by increased surface productivity resulted in the accumulation of the organic-rich lower Oatka Creek Member. Still, the mix of abundant small and subordinate large (>10 μm) framboids preserves the record of oxygen deficient to sulfidic bottom conditions frequently interrupted by episodes of (dys)oxia. Improving redox conditions through the overlying RST were accompanied by a two-fold increase in Al and consequent dilution of the organic matter flux and authigenic trace metal uptake at the sediment–water interface. The upper half of the Oatka Creek comprises a depositional sequence not obvious from core inspection or gamma-ray signature but revealed by Mo enrichment and Al concentration profiles. Diagenetic modification of the Marcellus includes several horizons of authigenic calcium carbonate concretions and marked Ba enrichment. Both features reflect the effects of non-steady state microbial diagenesis within a methane-rich sedimentary column.     

Characterisation and preliminary quantification of the methane reservoir in a coastal sedimentary source: San Simón Bay,Ría de Vigo,NW Spain

Ría de Vigo is a river valley flooded by the sea, with a bay (San Simón Bay) at its innermost part. The accumulation of Holocene sediment in San Simón Bay has been studied by the integration of 1) large scale high resolution seismic data, and 2) detailed geochemical analysis of a gravity core. In San Simón Bay the majority of the seismic records are obscured by acoustic turbidity which represents gassy sediments, but on records from Rande Strait it is possible to distinguish two Quaternary seismic sequences; an Upper Pleistocene sequence (SQ1) and a Holocene sequence (SQ2). Only SQ2 is recognized in San Simón Bay where it is comprised of two seismic units; the upper unit represents the HST sediment, i.e. the period of highest sea level. A gravity core taken within the gassy zone at 10 m water depth provided 3.55 m of fine-grained sediments (muds) from the youngest seismic unit (4 m thick). Geochemical analysis show high values (4 to 10%) of TOC. Sediment and porewater analyses indicate a distinct sulphate–methane transition zone (SMTZ) between 60 and 80 cm where sulphate is depleted (to <1.7 mM) and methane increases (to >0.4 mM). The top of the acoustic turbidity (the gas front) at 80 cm corresponds to the lower limit of the SMTZ. The methane cannot have been derived from the underlying metamorphic and granitic rocks, but was probably derived by microbial degradation of the organic matter in the Holocene sediments. We estimate that the sediments of the Bay contain approximately 1.8 × 10⁶ m³ of organic carbon and 275 ton of methane.     

Jurassic source rocks in the Vienna Basin (Austria): Assessment of conventional and unconventional petroleum potential

The Upper Jurassic marlstones (Mikulov Fm.) and marly limestones (Falkenstein Fm.) are the main source rocks for conventional hydrocarbons in the Vienna Basin in Austria. In addition, the Mikulov Formation has been considered a potential shale gas play. In this paper, organic geochemical, petrographical and mineralogical data from both formations in borehole Staatz 1 are used to determine the source potential and its vertical variability. Additional samples from other boreholes are used to evaluate lateral trends. Deltaic sediments (Lower Quarzarenite Member) and prodelta shales (Lower Shale Member) of the Middle Jurassic Gresten Formation have been discussed as secondary sources for hydrocarbons in the Vienna Basin area and are therefore included in the present study.The Falkenstein and Mikulov formations in Staatz 1 contain up to 2.5 wt%TOC. The organic matter is dominated by algal material. Nevertheless, HI values are relative low (<400 mgHC/gTOC), a result of organic matter degradation in a dysoxic environment. Both formations hold a fair to good petroleum potential. Because of its great thickness (∼1500 m), the source potential index of the Upper Jurrasic interval is high (7.5 tHC/m²). Within the oil window, the Falkenstein and Mikulov formations will produce paraffinic-naphtenic-aromatic low wax oil with low sulfur content. Whereas vertical variations are minor, limited data from the deep overmature samples suggest that original TOC contents may have increased basinwards. Based on TOC contents (typically <2.0 wt%) and the very deep position of the maturity cut-off values for shale oil/gas production (∼4000 and 5000 m, respectively), the potential for economic recovery of unconventional petroleum is limited. The Lower Quarzarenite Member of the Middle Jurassic Gresten Formation hosts a moderate oil potential, while the Lower Shale Member is are poor source rock.     

Organic geochemistry of the Silurian Tanezzuft Formation and crude oils,NC115 Concession,Murzuq Basin,southwest Libya

Thirty-six Silurian core and cuttings samples and 10 crude oil samples from Ordovician reservoirs in the NC115 Concession, Murzuq Basin, southwest Libya were studied by organic geochemical methods to determine source rock organic facies, conditions of deposition, thermal maturity and genetic relationships. The Lower Silurian Hot Shale at the base of the Tanezzuft Formation is a high-quality oil/gas-prone source rock that is currently within the early oil maturity window. The overall average TOC content of the Hot Shale is 7.2 wt% with a maximum recorded value of 20.9 wt%. By contrast, the overlying deposits of the Tanezzuft Formation have an average TOC of 0.6 wt% and a maximum value of 1.1 wt%. The organic matter in the Hot Shale consists predominantly of mixed algal and terrigenous Type-II/III kerogen, whereas the rest of the formation is dominated by terrigenous Type-III organic matter with some Type II/III kerogen. Oils from the A-, B- and H-oil fields in the NC115 Concession were almost certainly derived from marine shale source rocks that contained mixed algal and terrigenous organic input reflecting deposition under suboxic to anoxic conditions. The oils are light and sweet, and despite being similar, were almost certainly derived from different facies and maturation levels within mature source rocks. The B-oils were generated from slightly less mature source rocks than the others. Based on hierarchical cluster analysis (HCA), principal component analysis (PCA), selected source-related biomarkers and stable carbon isotope ratios, the NC115 oils can be divided into two genetic families: Family-I oils from Ordovician Mamuniyat reservoirs were probably derived from older Palaeozoic source rocks, whereas Family-II oils from Ordovician Mamuniyat–Hawaz reservoirs were probably charged from a younger Palaeozoic source of relatively high maturity. A third family appears to be a mixture of the two, but is most similar to Family-II oils. These oil families were derived from one proven mature source rock, the Early Silurian, Rhuddanian Hot Shale. There is a good correlation between the Family-II and -III oils and the Hot Shale based on carbon isotope compositions. Saturated and aromatic maturity parameters indicate that these oils were generated from a source rock of considerably higher maturity than the examined rock samples. The results imply that the oils originated from more mature source rocks outside the NC115 Concession and migrated to their current positions after generation.     

Thermal maturity of Miocene organic matter from the Carpathian Foredeep in the Czech Republic: 1D and 3D models

A three-dimensional reconstruction of burial and palaeogeothermal conditions is presented for Miocene sediments of the Carpathian Foredeep beneath the Outer Western Carpathians fold and trust belt in the eastern part of the Czech Republic. The sedimentary units involved include autochthonous Paleozoic sequences, Miocene deposits of the Carpathian Foredeep and of the Western Carpathian nappe system. Reservoir rocks with economic oil and gas accumulations occur in the fractured crystalline basement and in the Neogene Carpathian Foredeep. The studied Vizovice area, is characterized by rocks representing both Variscan and Carpathian orogenic cycles. The 3D thermal maturity and subsidence model presented allows the significance of both tectonic events to be evaluated. The model, calibrated by vitrinite reflectance from eight boreholes proved that eroded units related to the Variscan orogeny approach, in amount, those eroded during the Carpathian orogeny. The thickness of the eroded rocks does not exceed 300 m in either case. Vitrinite reflectance data from representative core samples of the Miocene organic matter show that R_r values increase with depth from 0.36 to 0.58%. A re-evaluation of archival data on the quantity and quality of organic matter shows that total organic carbon ranges from 0.20 to 2.92 wt%, and residual hydrocarbons (S₂) from 0.04 to 8.48 mg HC/g rock. These results lead to the conclusion that Neogene Unit II that was interpreted as coastline-through to shallow-marine deposition environment within the Carpathian Foredeep in the Czech Republic is potential source rock for hydrocarbon accumulations.     

北冰洋门捷列夫海岭富锰棕色层稀土元素组成特征与来源初步分析

北冰洋深海广泛分布的富锰棕色沉积层(棕色层)是海冰、洋流、物源供给等多种因素共同作用的结果,本文基于西北冰洋门捷列夫海岭ARC07-E25岩芯沉积物稀土元素与微量元素含量、颜色反射率参数、粗颗粒组分和无机碳含量的变化特征,对该类沉积层中稀土元素的组成特征、形成机制和物质来源进行了综合分析。结果显示,沉积物稀土元素总含量(∑REE)在122.37×10?6～231.94×10?6之间变化,北美页岩标准化配分模式显示出轻微的中稀土(MREE)富集以及由La、Ce、Nd主导的较强的轻稀土(LREE)优势。沉积物中∑REE随着粗组分颗粒(如冰筏碎屑)的增多而呈现降低趋势,表明门捷列夫海脊沉积物中的稀土元素主要富集在细粒沉积物中。根据∑REE在沉积物中的变化特征将E25岩芯沉积物划分为4种地层,反映出了冰期/间冰期的气候转变过程中温暖条件下形成的棕色层与寒冷条件下形成的浅灰绿色沉积层(灰色层)的岩性旋回中稀土元素组成的差异,由于两种沉积层在形成时受到不同的底层水氧化还原环境的控制,导致了铈(Ce)元素在氧化水体中会由Ce3+氧化为Ce4+并发生沉降,而在还原水体中则由Ce4+还原为Ce3+发生溶解,这一特性使LREE含量产生较大波动,进而影响到∑REE,使之趋于在代表氧化条件的棕色层中升高而在代表还原条件的灰色层中降低。R型因子分析和物质来源判别结果显示,E25岩芯沉积物中稀土元素与亲碎屑元素(Nb、U、Th)有较好的相关性,主要来源于东西伯利亚海和新西伯利亚群岛的近岸侵蚀物质以及勒拿河物质的输入。     

2015年春季长江口表层沉积物生源要素分布和来源

根据2015年5月对长江口及其邻近海域的生态环境调查资料, 探讨长江口春季表层沉积物总有机碳(TOC)、总氮(TN)、总磷(TP)和生源硅(BSi)4类生源要素的空间分布和来源。结果表明: 2015年春季长江口表层沉积物TOC、TN、TP和BSi平均含量分别为0.315%、0.041%、0.066%和0.450%, 其中, 沉积物中TOC、TN受到陆源输入和海洋自生输入双重影响, 且海洋自生组分的贡献较大, 二者空间分布均呈现南部分布最高并沿西北方向递减趋势; TP分布主要受陆源输入影响, 并呈西北向东南递减趋势; BSi来源于生物沉积, 总体呈现南部高、北部低的分布趋势。与2007年相比, 长江口表层沉积物有机碳、氮含量降低, 东南外海区域替代浑浊区域成为表层沉积物生源要素含量最高区域, 且陆源输入对长江口表层沉积物生源要素的贡献趋于减弱。     

Total hydrolysable amino acid mineralisation in sediments across the northeastern Atlantic continental slope (Goban Spur)

Total hydrolysable amino acids (THAA), individual amino acid distributions, total organic carbon (TOC) and total nitrogen (TN) were measured in sediments across the Goban Spur continental slope at water depths of 651, 1296 and 3650 m. Objectives were to examine (1) differences in organic matter (OM) degradation state in surface sediments across the slope from sedimentary amino acid compositions, and (2) whether these differences are related to particle size distributions. Application of a ‘reaction–diffusion’ model to the sediment concentration profiles showed that TOC and THAA degradation rate constants decreased with increasing water depth. Ratios of degradation rate constants of THAA over TOC indicated that THAA turn over faster than TOC at 651 and 1296 m water depth only. From estimates of degradation rate constants of individual amino acids, it was concluded that with increasing water depth fewer amino acids contribute to overall THAA degradation. The contribution of THAA to TOC mineralisation decreased from the upper to the lower slope. Since at all three sampling stations the amino acids with the highest relative contribution to THAA had a higher abundance in sediments with reduced THAA mineralisation rates, we conclude that the overall amino acid reactivity decreases with increasing water column depth. A principal component analyses, carried out on normalised amino acid mole percentages, established significant shifts in amino acid compositions and confirmed that (1) OM degradation state increased from 651 to 3650 m and (2) that OM in the finest fraction at the shallowest station appeared to be considerably less degraded than in the coarser fractions or any size fractions at the deeper stations. Therefore, we conclude that downslope transport, sorting and accumulation of fine particles with continuous mineralisation of OM attached to the particles during vertical and lateral transport results in an increasing organic matter degradation state from the upper slope to the abyssal plain.     

Hydrothermal indications of Early Cretaceous red beds in lacustrine successions,North Yellow Sea Basin,eastern China

Controversies over the origin of globally distributed Cretaceous red beds have mainly focused on climate vs. weathering with potential hydrothermal influence. In comparison to Cretaceous Oceanic Red Beds, Cretaceous lacustrine red beds exhibit chronological inconsistencies and their diverse tectonic settings suggest differing genetic mechanisms. In this paper, Early Cretaceous red beds in the North Yellow Sea Basin, one of Mesozoic rift basins in eastern China that are associated with multi-phase magmatic activities, was chosen to document potential hydrothermal impact. Geological and geochemical analyses show that these red beds were syndepositional products developed in shallow to moderately deep lacustrine environments and that they were influenced by hydrothermal activity. Major and trace elements, including enhanced Al₂O₃-normalized Fe₂O₃ and Fe₂O₃ (total) values, Al/(Al + Fe + Mn) and (Fe + Mn)/Ti ratios, Ni-Co-Zn and Fe-Mn-(Ni + Co + Cu)*10, ∑REE-La/Yb, the concentrations of hydrothermally-related ions, invalid redox indicators of trace elements, abnormally high Fe₂O₃ (total) content, positive Eu anomaly, correlation of Fe₂O₃ (total) and Eu anomaly, and vitrinite reflectance (Ro) vs. total organic carbon (TOC), all show strong hydrothermal fluid influence and heating effects. By integrating and comparing data from previous studies, we propose a hydrothermally affected sedimentation model for Cretaceous red beds and associated sediments in magma-activated lacustrine basins, and conclude that the enriched metallic ions introduced by the hydrothermal fluids may be the most significant reason for the deposition of the red beds, and the flushed ferric ions, accompanied by hydrothermal fluid, are the main ions that are hosted inside hematite causing the red sediment. This model can be applied to similar lacustrine basins that experience strong magmatic activity.     

Paleo-redox depositional conditions inferred from trace metal accumulation in two Cretaceous-Paleocene organic-rich sequences from Central Egypt

Cretaceous-Paleocene organic-rich sediments in Egypt occur as an east-west trending belt extending from the Quseir-Safaga district (Red Sea) to the Kharga-Dakhla (Western Desert) region. They are associated with the Duwi Formation (phosphate-bearing) and the overlying Dakhla Formation (deeper epicontinental shale/marl). This study aims to reconstruct the paleo-redox conditions during deposition of these thermally immature organic-rich sediments using carbon-sulfur-iron systematics and trace metal proxies in two cores, one each from the Quseir and Abu Tartur areas. Paleoproductivity, based on P content, seems to have been higher in the Quseir section than in the Abu Tartur section. The Quseir section also records a relatively greater occurrence of anoxic conditions during the accumulation of these sediments than the Abu Tartur section. This difference is indicated by its markedly higher total organic carbon (TOC) content as well as higher contributions of redox-sensitive and sulfide-forming metals (Mo, U, Ni, V, and Co). A weak correlation exists between S and TOC, and a positive S intercept (>1) was observed in most of the rock units of the study sections. A high consistency between the TOC-S-Fe relations and trace metals findings was found. The uppermost Duwi and the lowermost Dakhla strata, which have the highest TOC and represent a maximum sea transgression during the Late Cretaceous, have the highest contents of redox-sensitive trace metals. The carbonate-dominated transgressive Baris and Beida members of the Dakhla Formation record relatively stronger oxygen-depleted conditions during their accumulation than others, which led to relatively higher TOC contents and redox-sensitive metal accumulations. A scenario for the environmental conditions that existed during the deposition of these organic-rich successions, based on compiled trace metals and TOC-S-Fe implications, is reconstructed here.     

Chlorophyll a in Arctic sediments implies long persistence of algal pigments

Sediment cores were collected from the shelf, slope, and basin of the Bering, Chukchi, and Beaufort Seas during May–June (under ice cover) and July–August (largely ice-free) 2004. Measurements of chlorophyll a (chl a), total organic carbon (TOC), and C/N ratios were made in surface and some subsurface core increments. Surface sediment chl a decreased with increasing water depth. Significant positive correlations were found between chl a and TOC and chl a and C/N ratios in the basin (>2000 m), but there were significant negative correlations between chl a and C/N ratios on the shelf (⩽200 m). Chl a values generally declined in down-core profiles, but in some deeper slope and basin cores, measurable inventories of subsurface chl a were present at depth. In some cases, these subsurface chlorophyll inventories coincident with peak activities of the anthropogenic radionuclide ¹³⁷Cs were detected, which had maximal deposition following the atmospheric nuclear weapons testing era in the 1960s. A sedimentation rate independently determined for one of these cores using ²¹⁰Pb was consistent with the depths of subsurface ¹³⁷Cs peaks in slope sediments reflecting steady, relatively undisturbed deposition over a several-decade period. The depth of penetration of ¹³⁷Cs in some continental slope sediments, together with detectable chl a, suggests that chl a can be buried in some of these deeper-water sediments under cold conditions for decadal periods in the absence of deposit feeders. Because organic deposition from the water column is episodic at high latitudes and concentrated following the spring bloom, these buried sources of organic materials, whether on the shelf or in deeper basin sediments, may ultimately be important for benthic invertebrates that could utilize this food source during times of the year when primary production flux from the overlying water column is reduced.     

BIB-SEM characterization of pore space morphology and distribution in postmature to overmature samples from the Haynesville and Bossier Shales

Four Haynesville Shale and four Bossier Shale samples were investigated using a combination of Scanning Electron Microscopy (SEM) and Broad Ion Beam (BIB) polishing. This approach enables the microstructure and porosity to be studied down to the mesopore size (<50 nm) in representative areas at the scale of the BIB cross-sections. The samples vary in mineralogy, grain size and TOC and the maturity ranges from 2.42 to 2.58 VR_r in the Haynesville Shale to 1.79–2.26 VR_r in the Bossier Shale. This variety within the samples enabled us to study controls on the porosity distribution in these shales. Visible pores exist as intraparticle pores mainly in carbonate grains and pyrite framboids and as interparticle pores, mainly in the clay-rich matrix. Pores in organic matter show a characteristic porosity with respect to the type of organic matter, which mainly consists of mixtures of amorphous organic matter and minerals, organic laminae and discrete macerals. A clear positive trend of organic-matter porosity with maturity was found. Pore sizes are power law distributed in the range of 4.4 μm to at least 36 nm in equivalent diameter. The differences in power law exponents suggest that a more grain supported, coarse-grained matrix may prevent pores from mechanical compaction. Porosities measured in the BIB cross-sections were significantly lower in comparison to porosities obtained by Mercury Intrusion Porosimetry (MIP). This difference is mainly attributed to the different resolution achieved with BIB-SEM and MIP and type of pore network. Extrapolation of pore size distributions (PSDs) enables the BIB-SEM porosity to be estimated down to the resolution of the MIP and thus to upscale microstructural observation at the confined space of the BIB-SEM method to bulk porosity measurement. These inferred porosities are in good agreement with the MIP determined porosities, which underpins the assumption that pores segmented in BIB-SEM mosaics are representative of the MIP methodology.     

Mineralogical and chemical distribution of the Es3L oil shale in the Jiyang Depression,Bohai Bay Basin (E China): Implications for paleoenvironmental reconstruction and organic matter accumulation

The Es₃^L (lower sub-member of the third member of the Eocene Shahejie Formation) shale in the Jiyang Depression is a set of relatively thick and widely deposited lacustrine sediments with elevated organic carbon, and is considered to be one of the most important source rocks in East China. We can determine the mineralogy, organic and inorganic geochemistry of the Es₃^L shale and calculate paleoclimate indexes by using multiple geochemical proxies based on organic chemistry (total organic carbon [TOC] and Rock-Eval pyrolysis), major and trace elements, X-Ray diffraction, and carbon and oxygen isotope data from key wells alongside ECS (Elemental Capture Spectroscopy) well log data. These indicators can be used to analyze the evolution of the paleoenvironment and provide a mechanism of organic matter (OM) accumulation. The Es₃^L oil shale has high TOC abundance (most samples >3.0%) and is dominated by Type I kerogens. Additionally, the organic-rich shale is rich in CaO and enrichment in some trace metals is present, such as Sr, Ba and U. The positive δ¹³C and negative δ¹⁸O values, high Sr/Ba, B/Ga and Ca/Ca + Fe ratios and low C/S ratios indicate that the Es₃^L shales were mainly deposited in a semi-closed freshwater-brackish water lacustrine environment. The consistently low Ti/Al and Si/Al ratios reflect a restricted but rather homogeneous nature for the detrital supply. Many redox indicators, including the Th/U, V/(V + Ni), and δU ratios, pyrite morphology and TOC-TS-Fe diagrams suggest deposition under dysoxic to suboxic conditions. Subsequently, the brackish saline bottom water evolved into an anoxic water body under a relatively arid environment, during which organic-lean marls were deposited in the early stage. Later, an enhanced warm-humid climate provided an abundant mineral nutrient supply and promoted the accumulation of algal material. OM input from algal blooms reached a maximum during the deposition of the organic-rich calcareous shale with seasonal laminations. High P/Ti ratios and a strongly positive relationship between the P and TOC contents indicate that OM accumulation in the oil shale was mainly controlled by the high primary productivity of surface waters with help from a less stratified water column. Factors such as the physical protection of clay minerals and the dilution of detrital influx show less influence on OM enrichment.     

Spatial and vertical distributions of elements in sediments of the Colorado River delta and Upper Gulf of California

The abundance of major components (Fe, Ca, K, and organic carbon) and trace elements was analyzed in surface sediments and core samples from the Colorado River delta (CRD) and the Upper Gulf of California (UGC) using instrumental neutron activation analysis.The spatial distribution patterns of the elements studied are consistent with the model of sedimentary dynamics proposed for this area [Mar. Geol. 158 (1999) 125]: intense tidal resuspension of sediments in the delta with subsequent transport of suspended particulate matter in a southerly direction, followed by sedimentation of fine-grained material in a depocenter near the southwestern margin of the UGC. Concentrations of most of the elements are higher in the surface sediments of this depocenter. The gradual mixing of terrigenous and marine biogenic materials, normally expected for the estuarine sediments, was not detected in the CRD–UGC system because of homogenization of the sediments by tides and wind.Vertical profiles of element contents in samples of the sediment core collected in the depocenter area revealed (i) almost no anthropogenic contamination of the area by environmentally important trace elements such as Cr, Co, Sb, and As; (ii) a twofold decrease of Fe, Sc, Cr, and Co in upper core sediments; and (iii) the enrichment of the sediments at 60–62 cm depth in the core, in calcium carbonate, Ca, Sr, and the Eu_n/Sm_n shale-normalized ratio along with a depletion in this layer of Fe, Sc, Cr, Co, light rare-earth elements (REEs), and some other elements of terrigenous origin, presumably caused by the dilution of fluvial terrigenous material by biogenic carbonates, which were probably introduced at this level in the sediments by the action of a strong episodic winter storm, followed by the advective transport of shell fragments from the coastal clam banks or as a result of strong planktonic bloom.     

Rapid lateral particle transport in the Argentine Basin: Molecular 14C and 230Thxs evidence

Recent studies have revealed that lateral transport and focusing of particles strongly influences the depositional patterns of organic matter in marine sediments. Transport can occur in the water column prior to initial deposition or following sediment re-suspension. In both cases, fine-grained particles and organic-rich aggregates are more susceptible to lateral transport than coarse-grained particles (e.g., foraminiferal tests) because of the slower sinking velocities of the former. This may lead to spatial and, in the case of redistribution of re-suspended sediments, temporal decoupling of organic matter from coarser sediment constituents. Prior studies from the Argentine Basin have yielded evidence that suspended particles are displaced significant distances (100–1000 km) northward and downslope by strong surface and/or bottom currents. These transport processes result in anomalously cold alkenone-derived sea-surface temperature (SST) estimates (up to 6 °C colder than measured SST) and in the presence of frustules of Antarctic diatom species in surface sediments from this area. Here we examine advective transport processes through combined measurements of compound-specific radiocarbon ages of marine phytoplankton-derived biomarkers (alkenones) from core tops and excess ²³⁰Th (²³⁰Th_xs)-derived focusing factors for late Holocene sediments from the Argentine Basin. On the continental slope, we observe ²³⁰Th_xs-based focusing factors of 1.4–3.2 at sites where alkenone-based SST estimates were 4–6 °C colder than measured values. In contrast, alkenone radiocarbon data suggest coeval deposition of marine biomarkers and planktic foraminifera, as alkenones in core tops were younger than, or similar in age to, foraminifera. We therefore infer that the transport processes leading to the lateral displacement of these sediment components are rapid, and hence probably occur in the upper water column (<1500 m).     

Natural sealed fractures in mudrocks: A case study tied to burial history from the Barnett Shale,Fort Worth Basin,Texas, USA

The Mississippian Barnett Shale (Texas, USA), consisting of organic-rich shales and limestones, hosts the largest gas fields of North America. This study examines sealed fractures from core and outcrop samples of the Barnett Shale of the Fort Worth Basin and aims to: 1) characterize the phases occurring in the fractures from samples having experienced different burial histories; 2) establish a paragenetic sequence to relate the timing of fracture origin and sealing with the burial history of the basin; and 3) contribute to the understanding of the mechanisms of fracture formation in shales, including overpressure origin.Four fracture generations were distinguished in the most deeply buried core samples by characterizing the sealing minerals petrographically and geochemically. The generations were inserted into the framework of a reconstructed burial history for the Fort Worth Basin, which allowed a time sequence for fracture development to be established. This in turn allowed inference of conditions of fracture development, and consideration of fracture mechanisms as well as the origin of the parent fluids of sealing minerals.Type 1 fractures formed during early mechanical compaction (at a few 10 s to 100 m of depth) of still not fully cemented sediments. Type 2 fractures formed during moderate burial (∼2 km), from slightly modified seawater. Their timing is consistent with overpressure generated during rapid deposition and differential compaction of Pennsylvanian lithologies during the onset of the Ouachita compressional event. Type 3 fractures formed during deep burial (>3 km) from silica-rich basinal brines possibly derived from clay diagenesis. Type 4 fractures formed at very deep burial (>4 km), from hot and ¹⁸O-rich fluids, carrying light oil (20-30 API) and record the opening of the fluid system after hydrocarbon migration.Differences are highlighted between the timing and thermal regimes under which fractures formed in Barnett lithologies from different areas of the basin, this suggesting that extrapolation of outcrop observations to subsurface must be used with due care.     

Origins and maturity of organic matter in mid-Cretaceous black shales from ODP Site 1138 on the Kerguelen Plateau

We have conducted elemental, isotopic, and Rock-Eval analyses of Cenomanian–Santonian sediment samples from ODP Site 1138 in the southern Indian Ocean to assess the origin and thermal maturity of organic matter in mid-Cretaceous black shales found at this high-latitude location. Total organic carbon (TOC) concentrations range between 1 and 20 wt% in black to medium-gray sediments deposited around the Cenomanian–Turonian boundary. Results of Rock-Eval pyrolysis indicate that the organic matter is algal Type II material that has experienced modest alteration. Important contributions of nitrogen-fixing bacteria to the amplified production of organic matter implied by the high TOC concentrations is recorded in δ¹⁵N values between −5 and 1‰, and the existence of a near-surface intensified oxygen minimum zone that favored organic carbon preservation is implied by TOC/TN ratios between 20 and 40. In contrast to the marine nature of the organic matter in the Cenomanian–Turonian boundary section, deeper sediments at Site 1138 contain evidence of contributions land-derived organic matter that implies the former presence of forests on the Kerguelen Plateau until the earliest Cenomanian.     

Using sediment geochemistry to infer temporal variation of methane flux at a cold seep in the South China Sea

Release of methane from the seafloor throughout the world's oceans and the biogeochemical processes involved may have significant effects on the marine sedimentary environment. Identification of such methane release events in marine sediment records can hence provide a window into the magnitude of ancient seeps. Here, we report on analysis of the geochemical composition of samples in a 12.3 m long sediment core (DH-5) collected from a seep site in the South China Sea (SCS). Our aim has been to investigate whether the evidence for the presence of methane release event within sediments is discernible from solid-phase sediment geochemistry. We show that sedimentary total sulfur (TS), δ³⁴S values of chromium reducible sulfur (δ³⁴S_CRS) along with total organic carbon (TOC) and total inorganic carbon (TIC) content can be used to infer the presence of methane release events in cold seep settings. At least three methane release events were identified in the studied core (Unit I at 400–550 cm, Unit II at 740–820 cm, and Unit III at 1000–1150 cm). According to the characteristic of redox-sensitive elements (eg., Mo, U and Mn), we suggest that methane flux has been changed from relatively high (Unit I) to low (Unit II and III) rates. This inference is supported by the coupled occurrence of ³⁴S-enriched sulfides in Unit II and III. AMS ¹⁴C dates from planktonic foraminifera in Unit I suggest that high methane flux event occurred at ∼15.4–24.8 kyr BP, which probably resulted in locally-focused aerobic methane oxidation. Overall, our results suggest that TS, TOC, TIC and δ³⁴S_CRS have potential for identifying present and fossil methane release events in marine sediments.     

An enhanced understanding of the Basinal Bowland shale in Lancashire (UK), through microtextural and mineralogical observations

Variability in the Lower Bowland shale microstructure is investigated here, for the first time, from the centimetre to the micrometre scale using optical and scanning electron microscopy (OM, SEM), X-Ray Diffraction (XRD) and Total Organic Carbon content (TOC) measurements. A significant range of microtextures, organic-matter particles and fracture styles was observed in rocks of the Lower Bowland shale, together with the underlying Pendleside Limestone and Worston Shale formations encountered the Preese Hall-1 Borehole, Lancashire, UK. Four micro-texture types were identified: unlaminated quartz-rich mudstone; interlaminated quartz- and pyrite-rich mudstone; laminated quartz and pyrite-rich mudstone; and weakly-interlaminated calcite-rich mudstone. Organic matter particles are classified into four types depending on their size, shape and location: multi-micrometre particles with and without macropores: micrometre-size particles in cement and between clay minerals; multi-micrometre layers; and organic matter in large pores. Fractures are categorized into carbonate-sealed fractures; bitumen-bearing fractures; resin-filled fractures; and empty fractures. We propose that during thermal maturation, horizontal bitumen-fractures were formed by overpressuring, stress relaxation, compaction and erosional offloading, whereas vertical bitumen-bearing, resin-filled and empty fractures may have been influenced by weak vertical joints generated during the previous period of veining. For the majority of samples, the high TOC (>2 wt%), low clay content (<20 wt%), high proportion of quartz (>50 wt%) and the presence of a multi-scale fracture network support the increasing interest in the Bowland Shale as a potentially exploitable oil and gas source. The microtextural observations made in this study highlight preliminary evidence of fluid passage or circulation in the Bowland Shale sequence during burial.     

Source rock characteristics and hydrocarbon generation modelling of Upper Cretaceous Mukalla Formation in the Jiza-Qamar Basin,Eastern Yemen

The Upper Cretaceous Mukalla coals and other organic-rich sediments which are widely exposed in the Jiza-Qamar Basin and believed to be a major source rocks, were analysed using organic geochemistry and petrology. The total organic carbon (TOC) contents of the Mukalla source rocks range from 0.72 to 79.90% with an average TOC value of 21.50%. The coals and coaly shale sediments are relatively higher in organic richness, consistent with source rocks generative potential. The samples analysed have vitrinite reflectance in the range of 0.84–1.10 %Ro and pyrolysis T_max in the range of 432–454 °C indicate that the Mukalla source rocks contain mature to late mature organic matter. Good oil-generating potential is anticipated from the coals and coaly shale sediments with high hydrogen indices (250–449 mg HC/g TOC). This is supported by their significant amounts of oil-liptinite macerals are present in these coals and coaly shale sediments and Py-GC (S₂) pyrograms with n-alkane/alkene doublets extending beyond nC₃₀. The shales are dominated by Type III kerogen (HI < 200 mg HC/g TOC), and are thus considered to be gas-prone.One-dimensional basin modelling was performed to analysis the hydrocarbon generation and expulsion history of the Mukalla source rocks in the Jiza-Qamar Basin based on the reconstruction of the burial/thermal maturity histories in order to improve our understanding of the of hydrocarbon generation potential of the Mukalla source rocks. Calibration of the model with measured vitrinite reflectance (Ro) and borehole temperature data indicates that the present-day heat flow in the Jiza-Qamar Basin varies from 45.0 mW/m² to 70.0 mW/m² and the paleo-heat flow increased from 80 Ma to 25 Ma, reached a peak heat-flow values of approximately 70.0 mW/m² at 25 Ma and then decreased exponentially from 25 Ma to present-day. The peak paleo-heat flow is explained by the Gulf of Aden and Red Sea Tertiary rifting during Oligocene-Middle Miocene, which has a considerable influence on the thermal maturity of the Mukalla source rocks. The source rocks of the Mukalla Formation are presently in a stage of oil and condensate generation with maturity from 0.50% to 1.10% Ro. Oil generation (0.5% Ro) in the Mukalla source rocks began from about 61 Ma to 54 Ma and the peak hydrocarbon generation (1.0% Ro) occurred approximately from 25 Ma to 20 Ma. The modelled hydrocarbon expulsion evolution suggested that the timing of hydrocarbon expulsion from the Mukalla source rocks began from 15 Ma to present-day.