Sedimentary and residual gas geochemical characteristics of the Lower Cambrian organic-rich shales in Southeastern Chongqing,China

To study the sedimentary environment of the Lower Cambrian organic-rich shales and isotopic geochemical characteristics of the residual shale gas, 20 black shale samples from the Niutitang Formation were collected from the Youyang section, located in southeastern Chongqing, China. A combination of geochemical, mineralogical, and trace element studies has been performed on the shale samples from the Lower Cambrian Niutitang Formation, and the results were used to determine the paleoceanic sedimentary environment of this organic-rich shale. The relationships between total organic carbon (TOC) and total sulfur (TS) content, carbon isotope value (δ¹³C_org), trace element enrichment, and mineral composition suggest that the high-TOC Niutitang shale was deposited in an anoxic environment and that the organic matter was well preserved after burial. Stable carbon isotopes and biomarkers both indicate that the organic matter in the Niutitang black shales was mainly derived from both lower aquatic organisms and algaes and belong to type I kerogen. The oil-prone Niutitang black shales have limited residual hydrocarbons, with low values of S₂, I_H, and bitumen A. The carbon isotopic distribution of the residual gas indicate that the shale gas stored in the Niutitang black shale was mostly generated from the cracking of residual bitumen and wet gas during a stage of significantly high maturity. One of the more significant observations in this work involves the carbon isotope compositions of the residual gas (C₁, C₂, and C₃) released by rock crushing. A conventional δ¹³C₁–δ¹³C₂ trend was observed, and most δ¹³C₂ values of the residual gases are heavier than those of the organic matter (OM) in the corresponding samples, indicating the splitting of ethane bonds and the release of smaller molecules, leading to ¹³C enrichment in the residual ethane.     

Pore structure and fractal characteristics of organic-rich shales: A case study of the lower Silurian Longmaxi shales in the Sichuan Basin,SW China

Shales from the Lower Silurian Longmaxi Formation in the Sichuan Basin are among the most important shale gas reservoirs in China, and have been investigated because of their great shale gas potential. To understand the pore structure and fractal characteristics of the shales, a series of experiments was conducted on core samples from the Lower Silurian Longmaxi Formation in the Sichuan Basin of China, including X-ray diffraction (XRD), total organic carbon (TOC) content and vitrinite reflectance (Ro) analysis, field emission-environmental scanning electron microscope (FE-ESEM) observation, and low-pressure N₂ adsorption-desorption experiments. Frenkel-Halsey-Hill (FHH) method was applied to calculate fractal dimensions. In addition, the pore genesis, the relationships between composition and thermal maturity, the pore structure parameters, and the fractal dimensions are discussed. FE-ESEM observation results show that the Longmaxi Formation shales are dominated by organic-matter (OM) pores along with interparticle (interP) pores, intraparticle (intraP) pores and fracture pores. This study identified the fractal dimensions at relative pressures of 0–0.45 and 0.45–1 as D₁ and D₂ respectively. D₁ ranged from 2.60 to 2.71 and D₂ ranged from 2.71 to 2.82. D₁ was typically smaller than D₂, indicating that the smaller pores in shales were more homogeneous than the larger ones. The formation of these OM pores is owing to kerogen deformation during the thermal maturation, which results in a large number of nanopores. The pore structure of the Longmaxi Formation shales is primarily controlled by TOC content and thermal maturity. TOC content is a controlling factor on the fractal dimensions as it exhibited positive correlations with D₁ and D₂. Fractal dimensions are useful for the characterization of the pore structures complexity of the Longmaxi Formation shales because D₁ and D₂ correlate well with pore structure parameters as they both increase with the increase of surface area and the decrease of average pore diameter.     

Thermal maturity,source rock potential and kinetics of hydrocarbon generation in Permian shales from the Damodar Valley basin,Eastern India

This study investigates the source rock characteristics of Permian shales from the Jharia sub-basin of Damodar Valley in Eastern India. Borehole shales from the Raniganj, Barren Measure and Barakar Formations were subjected to bulk and quantitative pyrolysis, carbon isotope measurements, mineral identification and organic petrography. The results obtained were used to predict the abundance, source and maturity of kerogen, along with kinetic parameters for its thermal breakdown into simpler hydrocarbons.The shales are characterized by a high TOC (>3.4%), mature to post-mature, heterogeneous Type II–III kerogen. Raniganj and Barren Measure shales are in mature, late oil generation stage (Rr%_Raniganj = 0.99–1.22; Rr%_{Barren Measure} = 1.1–1.41). Vitrinite is the dominant maceral in these shales. Barakar shows a post-mature kerogen in gas generation stage (Rr%_Barakar = 1.11–2.0) and consist mainly of inertinite and vitrinite. The δ¹³C_org value of kerogen concentrate from Barren Measure shale indicates a lacustrine/marine origin (−24.6–−30.84‰ vs. VPDB) and that of Raniganj and Barakar (−22.72–−25.03‰ vs. VPDB) show the organic provenance to be continental. The δ¹³C ratio of thermo-labile hydrocarbons (C₁–C₃) in Barren Measure suggests a thermogenic source.Discrete bulk kinetic parameters indicate that Raniganj has lower activation energies (ΔE = 42–62 kcal/mol) compared to Barren Measure and Barakar (ΔE = 44–68 kcal/mol). Temperature for onset (10%), middle (50%) and end (90%) of kerogen transformation is least for Raniganj, followed by Barren Measure and Barakar. Mineral content is dominated by quartz (42–63%), siderite (9–15%) and clay (14–29%). Permian shales, in particular the Barren Measure, as inferred from the results of our study, demonstrate excellent properties of a potential shale gas system.     

Evaluation of burial history, thermal maturity and source-rock assessment of the Upper Paleozoic succession of the eastern Taurus region, southern Turkey

The regional burial history pattern, thermal maturity variations and source rock assessment of the sedimentary succession in the eastern Taurus region, in the southern part of Turkey, have been studied on surface samples collected from the six different sections which represent the entire region. Organic petrography (Thermal Alteration Index) and geochemical data (TOC content, T_max and HI values) were obtained from transmitted-light microscopy and Rock-Eval pyrolysis.The Lower Paleozoic (Cambrian, Ordovician and Silurian) strata were not investigated and modeled in terms of the maturity and hydrocarbon source rock potential, because of their poor organic matter content and their over maturity resulting from great burial depth (more than 7630 m). Other Paleozoic strata, except the Lower Devonian Ayitepesi Formation, generally have the values of more than 0.5% TOC. Organic matter of the Middle Devonian Safaktepesi sediments are composed of highly terrestrial organic material (type III kerogen), while samples from other three formations (Gumusali, Ziyarettepe and Yigilitepe Formations), while samples from other organic matter (type II and type III kerogen). The average TAI values are as high as 3.4 (equivalent to 1.42 of R₀%) for Ayitepesi and as low as 2.75 (equivalent to 0.77 of R₀%) for Yigilitepe Formations. Time-temperature index values (TTI) indicate that Ziyarettepe and Yigilitepe sediments are marginally mature to mature, while the Devonian strata are overmature. There are minor discrepancies between ΣTTI values and geochemical data in terms of the organic maturity for Devonian strata. In contrast, the e is a consistency between those values for the Ziyarettepe and the Yigilitepe Formations. The onset of oil generation time in the region was initiated from as early as the Norian (216 Ma) to as late as the Lutetian (45 Ma).Regional variations in the level of thermal and source-rock maturities of the Upper Paleozoic sediments in the eastern Taurus region largely depend on burial depth.     

Origin of organic matter and paleoenvironment conditions of the Late Jurassic organic-rich shales from shabwah sub-basin (western Yemen): Constraints from petrology and biological markers

Late Jurassic organic-rich shales from Shabwah sub-basin of western Yemen were analysed based on a combined investigations of organic geochemistry and petrology to define the origin, type of organic matter and the paleoenvironment conditions during deposition. The organic-rich shales have high total sulphur content values in the range of 1.49–4.92 wt. %, and excellent source rock potential is expected based on the high values of TOC (>7%), high extractable organic matter content and hydrocarbon yield exceeding 7000 ppm. The high total sulphur content and its relation with high organic carbon content indicate that the Late Jurassic organic-rich shales of the Shabwah sub-basin were deposited in a marine environment under suboxic-anoxic conditions. This has been evidenced from kerogen microscopy and their biomarker distributions. The kerogen microscopy investigation indicated that the Late Jurassic organic-rich shales contain an abundant liptinitic organic matter (i.e., alginite, structureless (amorphous organic matters)). The presence of alginite with morphology similar to the lamalginite alga and amorphous organic matter in these shale samples, further suggests a marine origin. The biomarker distributions also provide evidence for a major contribution by aquatic algae and microorganisms with a minor terrigenous organic matter input. The biomarkers are characterized by unimodal distribution of n-alkanes, low acyclic isoprenoids compared to normal alkanes, relatively high tricyclic terpanes compared to tetracyclic terpanes, and high proportion of C₂₇ and C₂₉ regular steranes compared to C₂₈ regular sterane. Moreover, the suboxic to anoxic bottom water conditions as evidenced in these Late Jurassic shales is also supported based on relatively low pristane/phytane (Pr/Ph) ratios in the range of 0.80–1.14. Therefore, it is envisaged here that the high content of organic matter (TOC > 7 wt.%) in the analysed Late Jurassic shales is attributed to good organic matter (OM) preservation under suboxic to anoxic bottom water conditions during deposition.     

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.     

Geochemical evolution of organic-rich shales with increasing maturity: A STXM and TEM study of the Posidonia Shale (Lower Toarcian,northern Germany)

Hydrocarbon generation and retention processes occurring within gas shales as a response to increases in thermal maturation are still poorly constrained. While efforts have been directed at unravelling the resource potential, composition and textures of these economically important unconventional systems, their spatial variability in chemistry and structure is still poorly documented at the sub-micrometer scale. Here, we have characterized samples of the Lower Toarcian Posidonia Shale samples from northern Germany at varying stages of thermal maturation using a combination of compositional organic geochemistry and spectromicroscopy techniques, including synchrotron-based scanning transmission X-ray microscopy (STXM). We document geochemical and mineralogical heterogeneities down to the nanometer scale within the investigated samples as a function of their level of thermal maturity. In particular, authigenic albite crystals containing nanometric halite inclusions have been documented within the investigated mature and overmature samples. The presence of such tracers of palaeobrine–carbonate interactions supports a maturation scenario for the Lower Toarcian Posidonia Shale intimately related to ascending brine fluids rather than a maturation scenario solely resulting from high heat flows. In addition, various types of asphaltene- and NSO-rich bitumen have been detected within the same samples, very likely genetically derived from thermally degraded organic precursors. Furthermore, the formation of nanoporous pyrobitumen has been inferred for samples of gas window maturity, likely resulting from the formation of gaseous hydrocarbons. By providing in-situ insights into the fate of bitumen and pyrobitumen as a response to the thermal evolution of the macromolecular structure of kerogen, the results reported here constitute an important step towards better constraining hydrocarbon generation processes during natural shale gas maturation.     

Depositional environment and geochemical characteristics of the Lower Carboniferous source rocks in the Marsel area,Chu-Sarysu Basin,Southern Kazakhstan

There are two sets of carbonate source rocks in the Lower Carboniferous layers in Marsel: the Visean (C₁v) and Serpukhovian (C₁sr). However, their geochemical and geological characteristics have not been studied systematically. To assess the source rocks and reveal the hydrocarbon generation potential, the depositional paleoenvironment and distribution of C₁v and C₁sr source rocks were studied using total organic carbon (TOC) content, Rock-Eval pyrolysis and vitrinite reflectance (Ro) data, stable carbon isotope data, gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) analysis data. The data were then compared with well logging data to understand the distribution of high-quality source rocks. The data were also incorporated into basin models to reveal the burial and thermal histories and timing of hydrocarbon generation. The results illustrated that the average residual TOC contents of C₁v and C₁sr were 0.79% and 0.5%, respectively, which were higher than the threshold of effective carbonate source rocks. Dominated by type-III kerogen, the C₁v and C₁sr source rocks tended to be gas-bearing. The two source rocks were generally mature to highly mature; the average Ro was 1.51% and 1.23% in C₁v and C₁sr, respectively. The source rocks were deposited in strongly reducing to weakly oxidizing marine–terrigenous environments, with most organic material originating from higher terrigenous plants and a few aquatic organisms. During the Permian, the deep burial depth and high heat flow caused a quick and high maturation of the source rocks, which were subsequently uplifted and eroded, stopping the generation and expulsion of hydrocarbons in the C₁v and C₁sr source rocks. The initial TOC fitted by the △logR method was recovered, and it suggests that high-quality source rocks (TOC ≥ 1%) are mainly distributed in the northern and central local structural belt.     

Puerulus and juvenile abundance in the rock lobster Jasus edwardsii at Stewart Island,New Zealand (Note)

Settlement of puerulus‐stage New Zealand red rock lobsters (Jasus edwardsii) and abundance of the first three juvenile cohorts were measured from 1981 to 1989 near Halfmoon Bay, Stewart Island. Puerulus settlement on subtidal collectors shows great annual variation. Juvenile abundance, estimated from the number caught in annual diver collections, shows less variation. One‐year‐olds appear less vulnerable to diver sampling than older juveniles. Abundance of 2‐ and 3‐year‐olds is highly correlated with puerulus settlement 2 and 3 years previously. Survival between puerulus and 1+ stages appears to be density‐dependent, but survival of older juveniles does not. Size is inversely related to abundance in 3+ females but not in the other cohorts, suggesting density‐dependent growth between ages 2 and 3. Puerulus settlement rates and processes on shallow inshore reefs appear to be important in determining recruitment strength in this species.     

Petroleum generation characteristics of heterogeneous source rock from Chia Gara formation in the Kurdistan region,northern Iraq as inferred by bulk and quantitative pyrolysis techniques

This study is the first attempt which provides information regarding the bulk and quantitative pyrolysis results of the Chia Gara Formation from the Kurdistan region, northern Iraq. Ten representative early-mature to mature samples from the Chia Gara Formation were investigated for TOC contents, Rock Eval pyrolysis, pyrolysis-GC and bulk kinetic parameters. These analyses were used to characterize the petroleum generated during thermal maturation of the Chia Gara source rock and to clarify the quantity of the organic matter and its effect on the timing of petroleum generation.Pyrolysis HI data identified two organic facies with different petroleum generation characteristics; Type II–III kerogen with HI values of >250 mg HC/g TOC, and Type III kerogen with HI values < 100 mg HC/g TOC. These types of kerogen can generate liquid HCs and gas. This is supported by the products of pyrolysis–gas chromatography (Py–GC) analysis of the extracted rock samples. Pyrolysis products show a dominance of a marine organic matter with variable contributions from terrestrial organic matter (Types II–III and III kerogen), and produces mainly paraffinic-naphthenic-aromatic low wax oils with condensate and gas.Bulk kinetic analysis of the Chia Gara source rock indicates a heterogeneous organic matter assemblage, typical of restricted marine environments in general. The activation energy distributions reveal relatively broad and high values, ranging from 40 to 64 kcal/mol with pre-exponential factors varying from 2.2835 E+12/sec to 4.0920 E+13/sec. The predicted petroleum formation temperature of onset (TR 10%) temperatures ranges from 110 to 135 °C, and peak generation temperatures (geological T_max) between 137 °C and 152 °C. The peak generation temperatures reach a transformation ratio in the range of 42–50% TR, thus the Chia Gara source rock could have generated and expelled significant quantities of petroleum hydrocarbons in the Kurdistan of Iraq.     

Food web and fish stock changes in central Chile: comparing the roles of jumbo squid (Dosidicus gigas) predation,the environment,and fisheries

We analyzed recent food web and fish stock changes in the central Chile marine ecosystem, comparing the roles of jumbo squid (Dosidicus gigas) as predator, the environment, and fishing. To accomplish this we used food web modeling and the Ecopath with Ecosim software (EwE). The principal fish stocks have experienced wide decadal fluctuations in the past 30 years, including stock collapses of horse mackerel (Trachurus murphyi) and hake (Merluccius gayi), and there was a large influx of jumbo squid during the mid-2000s. We used two EwE models representing the food web off central Chile to test the hypothesis that predation by jumbo squid has been significant in explaining the dynamics of the main fishing resources and other species in the study area. Results indicate that predation by jumbo squid on fish stocks is lower than that of other predators (e.g. hake) and the fishery. Long-term fluctuations (1978–2004) in the biomass of the main fish stocks (as well as other components of the food web) seem to be related to fishing and to variation in primary production, rather than to predation by jumbo squid alone. Jumbo squid seems to play a role as predator rather than prey in the system, but its impacts are low when compared with the impacts of other predators and fishing. Therefore, we conclude that jumbo squid predation on its prey was not the primary force behind the collapse of important fish stocks off central Chile. Future efforts should be directed to better understanding factors that trigger sudden increases in jumbo squid abundance off central Chile, as well as modeling its trophic impacts.     

Sedimentology and depositional architecture of tidal compound dunes on a carbonate ramp: The lower Miocene deposits of the central Apennine (Latium,Italy)

The sedimentology and sequence stratigraphy of the central Apennine lower Miocene carbonate deposits (Guadagnolo Formation) are the goal of this paper. The Guadagnolo carbonate ramp deposits consist of a thick succession of three main lithofacies: marls, marly limestones and cross-bedded limestones. The lateral and vertical facies distribution, as well as the biota assemblages, suggests a deposition of these sediments along the middle-outer ramp sector of the Latium-Abruzzi carbonate platform. All the data suggest sedimentation under the influence of tidal currents that were responsible of bedforms generation as simple and compound dunes. These bodies are developed on metric and decametric scale, and are stacked one to other to form complex sedimentary bodies extending both in strike and dip section for several tens to hundred meters. The dune system developed in a semiclosed basin (the Paleoadriatic sea), open in the southern and closed in the northern sector respectively. Within this basin a probably amphidromic system developed. The flow sediment transport was dominantly westward, and was conditioned by the ramp paleotopography. From a sequence stratigraphic point of view several high and low rank depositional sequences that were differentiated basing on their relative physical scale (thickness of each unit) and on the lateral extension of the unconformities and the correlative conformities bounding them were recognized. The hierarchy of recognized sequence-stratigraphic units include, from the smallest to the largest: simple depositional sequences, low-rank composite depositional sequences and high-rank composite depositional sequences. In the Guadagnolo succession four high-rank composite depositional sequences having a duration variable from 0.9 to 1.6 Ma, and named Guadagnolo 1, 2, 3, and 4, were recognized. These high-rank composite sequences are internally constituted by a stacking of simple and low-rank composite depositional sequences, having a duration ranging from 40 ka to 200 ka. All these units constitute part of a higher-rank composite sequence developing between 21 and 14.80 Ma that we name “The Guadagnolo Depositional Sequence”. The wedge-shaped geometry, the thickness variation and the stacking pattern of the Guadagnolo succession are the response to eustasy and tectonic subsidence. The glacial eustasy mostly controlled the formation of the high-frequency depositional sequences, tectonic subsidence, related to the roll-back of the hinge west-directed subduction in turn connected to the advancement of the Apennine thrust modulated the accommodation space.     

Life strategies,energetics and growth characteristics of Calanoides carinatus (Copepoda) in the Angola-Benguela frontal region

Rates of daily egg production, moulting and egg hatching success, as well as total lipid content and composition of Calanoides carinatus, were measured in the region of the southern Angola Curre nt SAC), the Angola-Benguela Front (ABF) and the coastal upwelling area of the northern Benguela Current (NBC) system during February–March 2002. There were distinct differences in the vertical distribution, growth characteristics, lipid content and composition of populations in the SAC/ABF and NBC regions, indicative of different physiological states. Whereas in the NBC, C. carinatus was actively growing in response to elevated chlorophyll a levels associated with coastal upwelling, it comprised deep-living C5 copepodids with very large wax ester reseves (c. 40–50% dry mass) and extremely low metabolism in the SAC/ABF, suggesting diapause. This study provides the first data on lipid composition (lipid classes, fatty acids and alcohols) of this copepod in the region; in particular, the diapausing C5 contained high-levels of long-chain, mono-unsaturated fatty acids (23% of all fatty acids) and alcohols (69% of all fatty alcohols) in addition to trophic markers of diatoms, viz. 16:1(n-7) and 20:5(n-3). Based on total lipidcontent, the maximum survival time of the diapausal component of C. carinatus was estimated to be 149–192 days, whereas active surface-dwelling C5s and females could not survive for more than 10 days without feeding.     

The contribution of nano- and micro-planktonic assemblages in the surface layer (0-30 m) under different hydrographic conditions in the upwelling area off Concepción, central Chile

In the highly productive region off central Chile, the structure and temporal and spatial variability of planktonic assemblages, and the factors that determine changes in this structure are poorly understood. In the region, wind-driven upwelling, heating by solar radiation and freshwater inputs are highly seasonal processes, which, together with higher frequency events, can promote changes in the planktonic communities, especially in the upper layer. This study focuses on the structure of nano- through to micro-planktonic assemblages (2-200 μm) of unicellular organisms (protists) in surface waters (0-30 m) during different hydrographic conditions. Samples were taken from a fixed shelf station off Concepción (COPAS time series Station 18) on eight occasions between September 2003 and August 2004. The nano-plankton flagellate-dominated fraction was numerically important during the whole period. Maxima in flagellate abundance and biomass occurred during the upwelling period (November-April samplings) but these maxima appear to be unrelated to the degree of water column stratification. The micro-plankton diatom-dominated fraction was usually the largest component in terms of biomass during the study period and the diatoms made important numerical contributions during the upwelling period, with maxima in abundance and biomass when water column stability was lowest. The dominant genera and morphotypes in each functional group were found throughout the study period, with maxima in abundance and biomass co-occurring under similar environmental upwelling conditions. The mean macro-nutrient concentrations (nitrate and silicate) were relatively high in the top 30 m during both upwelling and non-upwelling periods, and did not explain the maxima in plankton or functional group replacements. The persistence of the dominant taxa in the planktonic assemblages suggests a high degree of flexibility, though probably not at the specific level, to withstand the highly variable environmental conditions in this upwelling area.