A laboratory study on capillary sealing efficiency of Iranian shale and anhydrite caprocks

Caprock has the most important role in the long term safety of formation gas storage. The caprocks trap fluid accumulated beneath, contribute to lateral migration of this fluid and impede its upward migration. The rapid upward passage of invasive plumes due to buoyancy pressure is prevented by capillary pressure within these seal rocks. In the present study, two main seal rocks, from the Zagros basin in the southwest of Iran, a shale core sample of Asmari formation and an anhydrite core sample of Gachsaran formation, were provided. Absolute permeabilities of shale and anhydrite cores, considering the Klinkenberg effect, were measured as 6.09 × 10⁻¹⁸ and 0.89 × 10⁻¹⁸ m², respectively. Capillary sealing efficiency of the cores was investigated using gas breakthrough experiments. To do so, two distinct techniques including step by step and residual capillary pressure approaches were performed, using carbon dioxide, nitrogen and methane gases at temperatures of 70 and 90 °C, under confining pressures in the range 24.13–37.92 MPa. In the first technique, it was found that capillary breakthrough pressure of the cores varies in the range from 2.76 to 34.34 MPa. Moreover, the measurements indicated that after capillary breakthrough, gas effective permeabilities lie in range 1.85 × 10⁻²¹ – 1.66 × 10⁻¹⁹ m². In the second technique, the minimum capillary displacement pressure of shale varied from 0.66 to 1.45 MPa with the maximum effective permeability around 7.76 × 10⁻²¹ – 6.69 × 10⁻²⁰ m². The results indicate that anhydrite caprock of the Gachsaran formation provides proper capillary sealing efficacy, suitable for long term storage of the injected CO₂ plumes, due to its higher capillary breakthrough pressure and lower gas effective permeability.     

Prediction of diagenetic facies using well logs – A case study from the upper Triassic Yanchang Formation,Ordos Basin,China

Understanding diagenetic heterogeneity in tight sandstone reservoirs is vital for hydrocarbon exploration. As a typical tight sandstone reservoir, the seventh unit of the Upper Triassic Yanchang Formation in the Ordos Basin (Chang 7 unit), central China, is an important oil-producing interval. Results of helium porosity and permeability and petrographic assessment from thin sections, X-ray diffraction, scanning electron microscopy and cathodoluminescence analysis demonstrate that the sandstones have encountered various diagenetic processes encompassing mechanical and chemical compaction, cementation by carbonate, quartz, clay minerals, and dissolution of feldspar and lithic fragments. The sandstones comprise silt-to medium-grained lithic arkoses to feldspathic litharenites and litharenites, which have low porosity (0.5%–13.6%, with an average of 6.8%) and low permeability (0.009 × 10⁻³ μm² to 1.818 × 10⁻³ μm², with an average of 0.106 × 10⁻³ μm²).This study suggests that diagenetic facies identified from petrographic observations can be up-scaled by correlation with wire-line log responses, which can facilitate prediction of reservoir quality at a field-scale. Four diagenetic facies are determined based on petrographic features including intensity of compaction, cement types and amounts, and degree of dissolution. Unstable and labile components of sandstones can be identified by low bulk density and low gamma ray log values, and those sandstones show the highest reservoir quality. Tightly compacted sandstones/siltstones, which tend to have high gamma ray readings and relatively high bulk density values, show the poorest reservoir quality. A model based on principal component analysis (PCA) is built and show better prediction of diagenetic facies than biplots of well logs. The model is validated by blind testing log-predicted diagenetic facies against petrographic features from core samples of the Upper Triassic Yanchang Formation in the Ordos Basin, which indicates it is a helpful predictive model.     

Nano-scale pore structure and fractal dimension of organic-rich Wufeng-Longmaxi shale from Jiaoshiba area,Sichuan Basin: Investigations using FE-SEM,gas adsorption and helium pycnometry

Much attention have been recently paid to the upper Ordovician Wufeng shale (O₃w) and lower Silurian Longmaxi shale (S₁l) in the Jiaoshiba area of Sichuan Basin, which is now the largest producing shale gas field in China. Field emission scanning electron microscopy (FE-SEM), low pressure gas (N₂ and CO₂) adsorption, helium pycnometry, X-ray diffraction and geochemical analyses were performed to investigate the pore structure and fractal dimension of the pores in O₃w-S₁l shale formation in the Jiaoshiba area. FE-SEM images show that organic matter (OM) pores are dominant in the organic-rich samples and these pores are often irregular, bubble-like, elliptical and faveolate in shape, while in organic-poor samples, limited and isolated interparticle (interP), intraparticle (intraP) and OM pores are observed. Reversed S-shaped isotherms obtained from nitrogen adsorption are type Ⅱ, and hysteresis loops indicate that the shape of micropore in the samples is slit-or plate-like. BET surface areas and total pore volume vary from 12.2 to 27.1 m²/g and from 1.8 × 10⁻² to 2.9 × 10⁻² cm³/g, with an average of 19.5 m²/g and 2.3 × 10⁻² cm³/g, respectively. Adsorption volume from both N₂ and CO₂ adsorption increases with respect to TOC contents. Porosities obtained from helium porosimetry are comparable with these from gas (CO₂ and N₂) adsorption in O₃w-S₁l shale. However, porosity determined by quantitative FE-SEM analysis is much smaller, which is mainly related to limited resolution and the small areas of investigation.Based on the Frenkel-Halsey-Hill (FHH) model of low-pressure N₂ adsorption, fractal dimensions of the pores varied from 2.737 to 2.823. Relationships between pore structure parameters and TOC content, mineral composition and fractal dimension reveal that the fractal dimension is mainly associated with micropores. Samples with higher TOC content, higher quartz content and lower clay content tend to contain more heterogeneous micropores, resulting in higher fractal dimensions and more complicated pore structure in shales. Therefore, fractal dimension is an effective parameter to reflect the complexity of pore structure and the degree of micropore development in O₃w-S₁l shale.     

Characteristics and petroleum origin of the Carboniferous volcanic rock reservoirs in the Shixi Bulge of Junggar Basin,western China

Shixi Bulge of the central Junggar Basin in western China is a unique region that provides insight into the geological and geochemical characteristics of large-scale petroleum reservoirs in volcanic rocks of the western Central Asian Orogenic Belt. Carboniferous volcanic rocks in the Shixi Bulge mainly consist of striped lava and agglomerate, as well as breccia lava and tight tuff. Volcanic rocks differ in porosity and permeability. Striped lava exhibits the highest porosity (average: 14.2%) but the lowest permeability (average: 0.67 × 10⁻¹⁵ m) among the rock types. Primary gas pores are widely developed and mostly filled. Secondary dissolution pores and fractures are two major reservoir storage spaces. Capillary pressure curves suggest the existence of four pore structure types of reservoir rocks. Several factors, namely, lithology, pore structure, and various diagenesis, govern the physical properties of volcanic rocks. The oil is characterized by a high concentration of tricyclic terpane, a terpane distribution of C₂₃ < C₂₁ > C₂₀, and sterane distributions of C₂₇ < C₂₈ < C₂₉ and C₂₇ > C₂₈ < C₂₉. Oil and gas geochemistry revealed that the oil is a mixture derived primarily from P₂w source rock and secondarily from P₁j source rock in the sag west of Pen-1 Well. The gases are likely gas mixtures of humic and sapropelic organic origins, with the sapropelic gas type dominant in the mixture. The gas mixture is most likely cracked from kerogen rather than oils. The Carboniferous volcanic reservoirs in Shixi Bulge share some unique characteristics that may provide useful insights into the various roles of different volcanic reservoir types in old volcanic provinces. The presence of these reservoirs will undoubtedly encourage future petroleum exploration in volcanic rocks up to the deep parts of sedimentary basins.     

Interhemispheric exchanges of mass and heat in the Atlantic Ocean in January–March 1993

Hydrographic, geochemical, and direct velocity measurements along two zonal (7.5°N and 4.5°S) and two meridional (35°W and 4°W) lines occupied in January–March, 1993 in the Atlantic are combined in an inverse model to estimate the circulation. At 4.5°S, the Warm Water (potential temperature θ>4.5°C) originating from the South Atlantic enters the equatorial Atlantic, principally at the western boundary, in the thermocline-intensified North Brazil Undercurrent (33±2.7×10⁶ m³ s⁻¹ northward) and in the surface-intensified South Equatorial Current (8×10⁶ m³ s⁻¹ northward) located to the east of the North Brazil Undercurrent. The Ekman transport at 4.5°S is southward (10.7±1.5×10⁶ m³ s⁻¹). At 7.5°N, the Western Boundary Current (WBC) (17.9±2×10⁶ m³ s⁻¹) is weaker than at 4.5°S, and the northward flow of Warm Water in the WBC is complemented by the basin-wide Ekman flow (12.3±1.0×10⁶ m³ s⁻¹), the net contribution of the geostrophic interior flow of Warm Water being southward. The equatorial Ekman divergence drives a conversion of Thermocline Water (24.58⩽σ₀<26.75) into Surface Water (σ₀<24.58) of 7.5±0.5×10⁶ m³ s⁻¹, mostly occurring west of 35°W. The Deep Water of northern origin flows southward at 7.5°N in an energetic (48±3×10⁶ m³ s⁻¹) Deep Western Boundary Current (DWBC), whose transport is in part compensated by a northward recirculation (21±4.5×10⁶ m³ s⁻¹) in the Guiana Basin. At 4.5°S, the DWBC is much less energetic (27±7×10⁶ m³ s⁻¹ southward) than at 7.5°N. It is in part balanced by a deep northward recirculation east of which alternate circulation patterns suggest the existence of an anticyclonic gyre in the central Brazil Basin and a cyclonic gyre further east. The deep equatorial Atlantic is characterized by a convergence of Lower Deep Water (45.90⩽σ₄<45.83), which creates an upward diapycnal transport of 11.0×10⁶ m³ s⁻¹ across σ₄=45.83. The amplitude of this diapycnal transport is quite sensitive to the a priori hypotheses made in the inverse model. The amplitude of the meridional overturning cell is estimated to be 22×10⁶ m³ s⁻¹ at 7.5°N and 24×10⁶ m³ s⁻¹ at 4.5°S. Northward heat transports are in the range 1.26–1.50 PW at 7.5°N and 0.97–1.29 PW at 4.5°S with best estimates of 1.35 and 1.09 PW.     

Hydrocarbon generation and expulsion characteristics of Eocene source rocks in the Huilu area,northern Pearl River Mouth basin,South China Sea: Implications for tight oil potential

In recent years, new oil reservoirs have been discovered in the Eocene tight sandstone of the Huilu area, northern part of the Pearl River Mouth basin, South China Sea, indicating good prospects for tight oil exploration in the area. Exploration has shown that the Huilu area contains two main sets of source rocks: the Eocene Wenchang (E₂w) and Enping (E₂e) formations. To satisfy the requirements for further exploration in the Huilu area, particularly for tight oil in Eocene sand reservoirs, it is necessary to re-examine and analyze the hydrocarbon generation and expulsion characteristics. Based on mass balance, this study investigated the hydrocarbon generation and expulsion characteristics as well as the tight oil resource potential using geological and geochemical data and a modified conceptual model for generation and expulsion. The results show that the threshold and peak expulsion of the E₂w source rocks are at 0.6% vitrinite reflectance and 0.9% vitrinite reflectance, respectively. There were five hydrocarbon expulsion centers, located in the western, eastern, and northern Huizhou Sag and the southern and northern Lufeng Sag. The hydrocarbon yields attributed to E₂w source rocks are 2.4 × 10¹¹ tons and 1.6 × 10¹¹ tons, respectively, with an expulsion efficiency of 65%. The E₂e source rock threshold and peak expulsion are at 0.65% vitrinite reflectance and 0.93% vitrinite reflectance, respectively, with hydrocarbon expulsion centers located in the centers of the Huizhou and Lufeng sags. The yields attributed to E₂e source rocks are 1.1 × 10¹¹ tons and 0.2 × 10¹¹ tons, respectively, with an expulsion efficiency of 20%. Using an accumulation coefficient of 7%–13%, the Eocene tight reservoirs could contain approximately 1.3 × 10¹⁰ tons to 2.3 × 10¹⁰ tons, with an average of 1.8 × 10¹⁰ tons, of in-place tight oil resources (highest recoverable coefficient can reach 17–18%), indicating that there is significant tight oil potential in the Eocene strata of the Huilu area.     

Diapycnal nutrient fluxes on the northern boundary of Cape Ghir upwelling region

In this study we estimate diffusive nutrient fluxes in the northern region of Cape Ghir upwelling system (Northwest Africa) during autumn 2010. The contribution of two co-existing vertical mixing processes (turbulence and salt fingers) is estimated through micro- and fine-structure scale observations. The boundary between coastal upwelling and open ocean waters becomes apparent when nitrate is used as a tracer. Below the mixed layer (56.15±15.56 m), the water column is favorable to the occurrence of a salt finger regime. Vertical eddy diffusivity for salt (K_s) at the reference layer (57.86±8.51 m, CI 95%) was 3×10⁻⁵ (±1.89×10⁻⁹, CI 95%) m² s⁻¹. Average diapycnal fluxes indicate that there was a deficit in phosphate supply to the surface layer (6.61×10⁻⁴ mmol m⁻² d⁻¹), while these fluxes were 0.09 and 0.03 mmol m⁻² d⁻¹ for nitrate and silicate, respectively. There is a need to conduct more studies to obtain accurate estimations of vertical eddy diffusivity and nutrient supply in complex transitional zones, like Cape Ghir. This will provide us with information about salt and nutrients exchange in onshore–offshore zones.     

Relationships between porosity,organic matter,and mineral matter in mature organic-rich marine mudstones of the Belle Fourche and Second White Specks formations in Alberta,Canada

This study presents approaches for evaluating hybrid source rock/reservoirs within tight-rock petroleum systems. The emerging hybrid source rock/reservoir shale play in the Upper Cretaceous Second White Specks and Belle Fourche formations in central Alberta, Canada is used as an example to evaluate organic and inorganic compositions and their relationships to pore characteristics. Nineteen samples from a 77.5 m-long core were analyzed using organic petrography, organic geochemistry, several methods of pore characterization, and X-ray powder diffraction (XRD). The lower part of the studied section includes quartz- and clay-rich mudrocks of the Belle Fourche Formation with low carbonate content, whereas the upper portion contains calcareous mudrocks of the Second White Specks Formation. Strata are mineralogically composed of quartz plus albite (18–56 wt. %), carbonates (calcite, dolomite, ankerite; 1–65 wt. %), clays (illite, kaolinite, chlorite; 15–46 wt. %), and pyrite (2–12 wt. %). Petrographic examinations document that organic matter represents marine Type II kerogen partly biodegraded with limited terrestrial input. Vitrinite reflectance R_o (0.74–0.87%), T_max values (438–446 °C) and biomarkers indicate mid-maturity within the oil window. The relatively poor remaining hydrocarbon potential, expressed as an S2 value between 2.1 and 6.5 mg HC/g rock, may result from an estimated 60–83% of the original kerogen having been converted to hydrocarbons, with the bulk having migrated to adjacent sandstone reservoirs. However, the present-day remaining total organic carbon TOC_pd content remains relatively high (1.7–3.6 wt. %), compared with the estimated original TOC_o of 2.4–5.0 wt. %. The calculated transformation ratio of 60–83% suggests that the remaining 17–40 wt. % of kerogen is able to generate more hydrocarbons. The studied section is a tight reservoir with an average Swanson permeability of 3.37·10⁻⁵ mD (measured on two samples) and total porosity between 1.7 and 5.0 vol. % (3 vol. % on average). The upper part of the sandy Belle Fourche Formation, with slightly elevated porosity values (3.5–5 vol. %), likely represents the interval with the best reservoir properties in the studied core interval. Total pore volume ranges between 0.0065 and 0.0200 cm³/g (measured by a combination of helium pycnometry and mercury immersion). Mesopores (2–50 nm ∅) are the most abundant pores and occupy 34–67% of total porosity or a volume of 0.0030–0.0081 cm³/g. In comparison, micropores (<2 nm ∅) cover a wide range from 6 to 60% (volume 0.0007–0.0053 cm³/g), and macropores (>50 nm ∅) reach up to 57% with the exception of some samples failing to indicate the presence of this pore fraction (volume 0.0000–0.0107 cm³/g). Macroporosity is mostly responsible for variations in total porosity, as suggested by macroporosity's strongest correlation with total porosity within the section. The relatively narrow ranges of TOC and minerals contents among measured samples limit our ability to further deconvolute factors that influence changes in total porosity and pore size distribution.     

Kinetic study reveals weak Fe-binding ligand,which affects the solubility of Fe in the Scheldt estuary

The chemistry of dissolved Fe(III) was studied in the Scheldt estuary (The Netherlands). Two discrete size fractions of the dissolved bulk (< 0.2 μm and < 1 kDa) were considered at three salinities (S = 26, 10 and 0.3).Within the upper estuary, where fresh river water meets seawater, the dissolved Fe concentration decreases steeply with increasing salinity, for the fraction < 0.2 μm from 536 nM at S = 0.3 to 104 nM at S = 10 and for the fraction < 1 kDa from 102 nM to 36 nM Fe. Further downstream, in the middle and lower estuary, this decrease in the Fe concentration continues, but is far less pronounced. For all samples, the traditionally recognised dissolved strong organic Fe-binding ligand concentrations are lower than the dissolved Fe concentrations.Characteristics of dissolved Fe-binding ligands were determined by observing kinetic interactions with adsorptive cathodic stripping voltammetry. From these kinetic experiments we concluded that apart from the well-known strong Fe-binding organic ligands (L, logK′ = 19–22) also weak Fe-binding ligands (P) existed with an α value (binding potential = K′ · [P]) varying between 10^11.1 and 10^11.9. The presence of this relatively weak ligand explained the high concentrations of labile Fe present in both size fractions in the estuary. This weak ligand can retard or prevent a direct precipitation after an extra input of Fe.The dissociation rate constants of the weak ligand varied between 0.5 × 10^− 4 and 4.3 × 10^− 4 s^− 1. The rate constants of the strong organic ligand varied between k_d = 1.5 × 10^− 3–17 × 10^− 2 s^− 1 and k_f = 2.2 × 10⁸–2.7 × 10⁹ M^− 1 s^− 1. The dissociation rate constant of freshly amorphous Fe-hydroxide was found to be between 4.3 × 10^− 4 and 3.7 × 10^− 3 s^− 1, more labile or equal to the values found by Rose and Waite [Rose, A.L., Waite, T.D., 2003a. Kinetics of hydrolysis and precipitation of ferric iron in seawater. Environ. Sci. Technol., 37, 3897–3903.] for freshly precipitated Fe in seawater.Kinetic rate constants of Fe with the ligand TAC (2-(2-Thiazolylazo)-p-cresol) were also determined. The formation rate constant of Fe(TAC)₂ varied between 0.1 × 10⁸ and 3.6 × 10⁸ M^− 1 s^− 1, the dissociation rate constant between 0.2 × 10^− 5 and 17 × 10^− 5 s^− 1 for both S = 26 and S = 10. The conditional stability constant of Fe(TAC)₂ (β_Fe(TAC)2′) varied between 22 and 23.4 for S = 10 and S = 26 more or less equal to that known from the literature (logβ_Fe(TAC)2′ = 22.4; [Croot, P.L., Johansson, M., 2000. Determination of iron speciation by cathodic stripping voltammetry in seawater using the competing ligand 2-(2-Thiazolylazo)-p-cresol (TAC). Electroanalysis, 12, 565–576.]). However, at S = 0.3 the logβ_Fe(TAC)2′ was 25.3, three orders of magnitude higher. Apparently the application of TAC to samples of low salinity can only be done when the correct β_Fe(TAC)2′ is known.     

Compaction model for quartzose sandstones application to the Garn Formation,Haltenbanken, Mid-Norwegian Continental Shelf

The compaction of quartzose sandstones is described by a macroscopical visco–elasto–plastic model, derived from microscopical considerations. This model considers that the reduction of total porosity (the relative pore volume) is related to the changes in the relative cemented volume and the relative intergrain volume. Furthermore, we consider that the variations of these two petrophysical parameters result from two physical mechanisms, mechanical compaction and closed system chemical compaction.The model has been calibrated for the Middle Jurassic Garn Formation from the Haltenbanken area of the Mid-Norwegian Continental Shelf. Around 300 data points from 17 wells have been used in this study. The viscous parameters have been optimised against the present day data. With total porosity data the best fit is obtained for an activation energy between 14 and 16 kJ/mole and a macroscopical viscosity at 15°C between 39 and 46 GpaMa (1.210²⁴–1.410²⁴ Pa.s). If quartz cement data are used, the best fit is obtained for an activation energy between 16 and 18 kJ/mole and a macroscopical viscosity at 15°C between 47 and 56 GpaMa (1.510²⁴–17.10²⁴ Pa.s).The visco–elasto–plastic compaction model has been tested in the Haltenbanken area of Mid Norway, with the result that observed porosity trends and pore pressures can be modelled. Using multiple 2-D basin modelling simulations the results of this model and its implications for fluid flow and petroleum systems analysis can be seen. The compaction method has significant impact on the simulated fluid flow and petroleum migration pattern.     

Picophytoplankton in the equatorial Pacific: vertical distributions in the warm pool and in the high nutrient low chlorophyll conditions

Abundance distribution and cellular characteristics of picophytoplankton were studied in two distinct regions of the equatorial Pacific: the western warm pool (0°, 167°E), where oligotrophic conditions prevail, and the equatorial upwelling at 150°W characterized by high-nutrient low-chlorophyll (HNLC) conditions. The study was done in September–October 1994 during abnormally warm conditions. Populations of Prochlorococcus, orange fluorescing Synechococcus and picoeukaryotes were enumerated by flow cytometry. Pigment concentrations were studied by spectrofluorometry. In the warm pool, Prochlorococcus were clearly the dominant organisms in terms of cell abundance, estimated carbon biomass and measured pigment concentration. Integrated concentrations of Prochlorococcus, Synechococcus and picoeukaryotes were 1.5×10¹³, 1.3×10¹¹ and 1.5×10¹¹ cells m⁻², respectively. Integrated estimated carbon biomass of picophytoplankton was 1 g m⁻², and the respective contributions of each group to the biomass were 69, 3 and 28%. In the HNLC waters, Prochlorococcus cells were slightly less numerous than in the warm pool, whereas the other groups were several times more abundant (from 3 to 5 times). Abundance of Prochlorococcus, Synechococcus and picoeukaryotes were 1.2×10¹³, 6.2×10¹¹ and 5.1×10¹¹ cells m⁻², respectively. The integrated biomass was 1.9 g C m⁻². Prochlorococcus was again the dominant group in terms of abundance and biomass (chlorophyll, carbon); the respective contributions of each group to the carbon biomass were 58, 7 and 35%. In the warm pool the total chlorophyll biomass was 28 mg m⁻², 57% of which was divinyl chlorophyll a. In the HNLC waters, the total chlorophyll biomass was 38 mg m⁻², 44% of which was divinyl chlorophyll a. Estimates of Prochlorococcus, Synechococcus and picoeukaryotes cell size were made in both hydrological conditions.     

Coccolithophorids on the continental slope of the Bay of Biscay – production,transport and contribution to mass fluxes

Coccoliths collected by sediment traps deployed on the slope of the Bay of Biscay (northeastern Atlantic), from June 1990 to August 1991, were examined to determine their contribution to the transport of carbonate on a mid-latitude continental margin. They also were used as tracers of particle transfer processes on this slope. Two traps located at 1900 m, respectively at 2300 (Mooring Site 1) and 3000 m (Mooring Site 2) water depths provided high-resolution (4–7 days) time-series samples covering a 14-month period at MS2 and a 3-month period at MS1. Coccoliths from 28 species were identified over the course of the experiment, among which Emiliania huxleyi was always dominant (relative abundance range: 59–93%). Total coccoliths number fluxes were high but variable, ranging from 390×10⁶ to 1610×10⁶ coccoliths m⁻² day⁻¹ at MS1, and from 58×10⁶ to 1500×10⁶ coccoliths m⁻² day⁻¹ at MS2. The time-weighted mean flux, calculated for the whole experiment at MS2, was 499×10⁶ coccoliths m⁻² day⁻¹. Estimate of coccoliths minimal contribution to total carbonate flux at 1900 m depth averaged 12%, which represented a weighted mean flux of 7.3 mg m⁻² day⁻¹ (2.7 g m⁻² yr⁻¹). Lateral transport of coccoliths resuspended from shelf and/or upper slope sediments seems to be the dominant transfer process to depth on this northeastern Atlantic slope. Nevertheless, the clear seasonal succession observed in the species composition implies that the deposition/resuspension/transport sequence is rapid (presumably less than a few months). Several short and unsmoothed signals directly issued from coccoliths bloom events also were recorded in our traps, a result that indicates rapid settling rates. The overall coccolith sedimentation processes appear as being quite diversified, but quantitative and qualitative analyses of aggregates collected by the traps suggest that they are important carriers of coccoliths in this margin environment.     

A sediment and organic carbon budget for the greater Strait of Georgia

Recent efforts to construct global ocean budgets for carbon have recognized the importance of continental margins. In this study, we constructed budgets for the Strait of Georgia, a temperate, North American west coast basin that receives the inflow of one of the world's major rivers. Drawing from published and unpublished data, we have estimated the magnitude of the various sources and sinks of fresh water, sediment and organic carbon.The Fraser River is the dominant source of fresh water and particles to the strait, contributing approximately 73% of the 158×10⁹ m³ year⁻¹ of water and 64% of the 30×10⁹ kg year⁻¹ of particles. Other rivers supply most of the remainder, while rain, groundwater and anthropogenic sources of water and particles are negligible in comparison. Fresh water escapes the Strait of Georgia through Juan de Fuca Strait, but particulate inputs are approximately balanced by sedimentation within the greater Strait of Georgia, implying almost complete trapping of particles.Dissolved and particulate organic carbon are derived mainly from in situ primary production (855×10⁶ kg year⁻¹) and from the Fraser River (550×10⁶ kg year⁻¹). Other rivers contribute 200×10⁶ kg year⁻¹ of organic carbon, and anthropogenic sources (ocean dumping, sewage, pulp mills and aquaculture) a further 119×10⁶ kg year⁻¹. Particulate organic carbon is predominantly buried (428×10⁶ kg year⁻¹) or oxidized (90×10⁶ kg year⁻¹) in the sediments of the strait. About 70% of the organic carbon that enters or is produced in the strait is dissolved. Most of the dissolved organic carbon is oxidized within the strait (784×10⁶ kg year⁻¹), but the remainder (400×10⁶ kg year⁻¹) is exported to the Pacific Ocean. Although the particulate organic carbon budget by itself implies net autotrophy, dissolved organic carbon oxidation may make the Strait of Georgia slightly net heterotrophic.     

Experimental study of fluid transport processes in the matrix system of the European organic-rich shales: I. Scandinavian Alum Shale

This contribution presents results from a laboratory study investigating the fluid (gas/water) transport properties in the matrix system of the Scandinavian Alum Shale. The maturity of the organic matter of the shale samples ranged between 0.5 and 2.4% vitrinite reflectance (VR_r). Gas (He, Ar, CH₄) and water flow properties were determined at effective stresses ranging between 5 and 30 MPa and a temperature of 45 °C. The effects of different controlling factors/parameters on the fluid conductivity including permeating fluid, moisture content, anisotropy, heterogeneity, effective stress, pore pressure, and load cycling were analyzed and discussed. Pore volume measurements by helium expansion were conducted under controlled “in situ” effective stress conditions on a limited number of plugs drilled parallel and perpendicular to bedding.For Alum Shale the intrinsic permeability coefficients measured parallel and perpendicular to bedding (6·10⁻²²–8·10⁻¹⁸ m²) were within the range previously reported for other shales and mudstones. Permeability coefficients were strongly dependent on permeating fluid, moisture content, anisotropy, effective stress and other sample-to-sample variations. The intrinsic/absolute permeabilities measured with helium were consistently, higher (up to five times) than those measured with argon and methane. Permeability coefficients (He, CH₄) measured on a dry sample were up to six times higher than those measured on an “as-received” sample, depending on effective stress. The effect of moisture on measured permeability coefficients became more significant as effective stress increased. Permeability coefficients (He, CH₄) measured parallel to bedding were up to more than one order of magnitude higher than those measured perpendicular to bedding. Parallel to bedding, all samples showed a nonlinear reduction in permeability with increasing effective stress (5–30 MPa). The stress dependence of permeability could be well described by an exponential relationship.     

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.     

Growth history of fault-related folds and interaction with seabed channels in the toe-thrust region of the deep-water Niger delta

The deep-water fold and thrust belt of the southern Niger Delta has prominent thrusts and folds oriented perpendicular to the regional slope that formed as a result of the thin-skinned gravitational collapse of the delta above overpressured shale. The thrust-related folds have grown in the last 12.8 Ma and many of the thrusts are still actively growing and influencing the pathways of modern seabed channels. We use 3D seismic reflection data to constrain and analyse the spatial and temporal variation in shortening of four thrusts and folds having seabed relief in a study area of 2600 km² size in 2200–3800 m water depth. Using these shortening measurements, we have quantified the variation in strain rates through time for both fault-propagation and detachment folds in the area, and we relate this to submarine channel response. The total amount of shortening on the individual structures investigated ranges from 1 to 4 km, giving a time-averaged maximum shortening rate of between 90 ± 10 and 350 ± 50 m/Myr (0.1 and 0.4 mm/yr). Fold shortening varies both spatially and temporally: The maximum interval shortening rate occurred between 9.5 Ma and 3.7 Ma, and has reduced significantly in the last 3.7 Ma. We suggest that the reduction in the Pliocene-Recent fold shortening rate is a response to the slow-down in extension observed in the up-dip extensional domain of the Niger Delta gravitational system in the same time interval. In the area dominated by the fault-propagation folds, the channels are able to cross the structures, but the detachment fold is a more significant barrier and has caused a channel to divert for 25 km parallel to the fold axis. The two sets of structures have positive bathymetric expressions, with an associated present day uphill slope of between 1.5° and 2°. However, the shorter uphill slopes of the fault-propagation folds and increased sediment blanketing allow channels to cross these structures. Channels that develop coevally with structural growth and that cross structures, do so in positions of recent strain minima and at interval strain rates that are generally less than −0.02 Ma⁻¹ (−1 × 10⁻¹⁶ s⁻¹). However, the broad detachment fold has caused channel diversion at an even lower strain rate of c. −0.002 Ma⁻¹ (−7 × 10⁻¹⁷ s⁻¹).     

Denitrification prevails over anammox in tropical mangrove sediments (Goa,India)

Denitrification, anammox (Anx) and di-nitrogen fixation were examined in two mangrove ecosystems- the anthropogenically influenced Divar and the relatively pristine Tuvem. Stratified sampling at 2 cm increments from 0 to 10 cm depth revealed denitrification as the main process of N₂ production in mangrove sediments. At Divar, denitrification was ∼3 times higher than at Tuvem with maximum activity of 224.51 ± 6.63 nmol N₂ g⁻¹ h⁻¹ at 0–2 cm. Denitrifying genes (nosZ) numbered up to 2 × 10⁷ copies g⁻¹ sediment and belonged to uncultured microorganisms clustering within Proteobacteria. Anammox was more prominent at deeper depths (8–10 cm) mainly in Divar with highest activity of 101.15 ± 87.73 nmol N₂ g⁻¹ h⁻¹ which was 5 times higher than at Tuvem. Di-nitrogen fixation was detected only at Tuvem with a maximum of 12.47 ± 8.36 nmol N₂ g⁻¹ h⁻¹. Thus, in these estuarine habitats prone to high nutrient input, N₂-fixation is minimal and denitrification rather than Anx serves as an important mechanism for counteracting N loading.     

Total organic and inorganic carbon exchange through the Strait of Gibraltar in September 1997

The total organic carbon (TOC) and total inorganic carbon (C_T) exchange between the Atlantic Ocean and the Mediterranean Sea was studied in the Strait of Gibraltar in September 1997. Samples were taken at eight stations from western and eastern entrances of the Strait and at the middle of the Strait (Tarifa Narrows). TOC was analyzed by a high-temperature catalytic oxidation method, and C_T was calculated from alkalinity–pH_T pairs and appropriate thermodynamic relationships. The results are used in a two-layer model of water mass exchange through the Strait, which includes the Atlantic inflow, the Mediterranean outflow and the interface layer in between. Our observations show a decrease of TOC and an increase of C_T concentrations from the surface to the bottom: 71–132 μM C and 2068–2150 μmol kg⁻¹ in the Surface Atlantic Water, 74–95 μM C and 2119–2148 μmol kg⁻¹ in the North Atlantic Central Water, 63–116 μM C and 2123–2312 μmol kg⁻¹ in the interface layer, and 61–78 μM C and 2307–2325 μmol kg⁻¹ in the Mediterranean waters. However, within the Mediterranean outflow, we found that the concentrations of carbon were higher at the western side of the Strait (75–78 μM C, 2068–2318 μmol kg⁻¹) than at the eastern side (61–69 μM C, 2082–2324 μmol kg⁻¹). This difference is due to the mixing between the Atlantic inflow and the Mediterranean outflow on the west of the Strait, which results in a flux of organic carbon from the inflow to the outflow and an opposite flux of inorganic carbon. We estimate that the TOC input from the Atlantic Ocean to the Mediterranean Sea through the Strait of Gibraltar varies from (0.97±0.8)10⁴ to (1.81±0.90)10⁴ mol C s⁻¹ (0.3×10¹² to 0.56×10¹² mol C yr⁻¹), while outflow of inorganic carbon ranges from (12.5±0.4)10⁴ to (15.6±0.4)10⁴ mol C s⁻¹ (3.99–4.90×10¹² mol C yr⁻¹). The high variability of carbon exchange within the Strait is due to the variability of vertical mixing between inflow and outflow along the Strait. The prevalence of organic carbon inflow and inorganic carbon outflow shows the Mediterranean Sea to be a basin of active remineralization of organic material.     

Computations of the energy flux to mixing processes via baroclinic wave drag on barotropic tides

The geographical distribution of barotropic to baroclinic transfer of tidal energy by baroclinic wave drag in the abyssal ocean is estimated. Using tidal velocities from a state-of-the-art numerical tidal model, the total loss of barotropic tidal energy in the deep ocean (between 70°S and 70°N and at depths greater than 1000 m) is estimated to be about 0.7 TW (M₂) corresponding to a mean value of the energy flux (e) of 2.4×10⁻³ W/m². The distribution of e is however highly skewed with a median of about 10⁻⁶ W/m². Only 10% of the area is responsible for more than 97% of the total energy transfer.To assess the possible influence of the relatively coarse bathymetry representation upon the present estimate, complementary calculations using better resolved sea floor topography are carried out over a control area around the Hawaiian Ridge. There are no major differences between the results achieved using the two different bathymetry databases. Fluxes of about 16 GW or 6×10⁻³ W/m² are computed in both cases, and the main contributions to the total fluxes originate in the same range of e-values and cover equally large parts of the total area.It is not clear whether the present model is valid at flat or subcritical bottom slopes. However, for the Hawaiian region, only 2% of the total energy flux as calculated in the present study originates in areas of critical and subcritical slopes.