Characterization of electrical properties of organic-rich shales at nano/micro scales

A new experimental protocol is explored to characterize electrical properties of hydrocarbon-bearing mudrocks at nano/micro scales. Two current flow regimes of peak force - tunneling atomic force microscopy (PF-TUNA) have been used: (1) the vertical out-of-plane current regime with hundred micrometer diameter top electrodes obtains homogenized conductivity quantitatively, (2) the horizontal in-plane current regime was shown powerful to visualize the conductive paths (related to connectivity and tortuosity) for heterogeneous and anisotropic shales. Results show that the approach works well with one to two layers of adsorbed water (25–55% relative humidity) under low frequency (0.5–20 Hz) for shale rocks. Current maps with sub-nanometer resolution emphasize the dominant role of hydrated ions associated with the hydrophilic clay minerals in driving the dielectric response of shales, while conductivity of pyrite and kerogen cannot be neglected for mature organic-rich shale conductive network. The acquired I-V curves at microscale provide a reliable mean to evaluate homogenized conductivity of such multiscale multi-component heterogeneous material under controlled environmental conditions. The procedure discussed herein serves as a complement for fine grained rocks and minerals of ionic-electronic hybrid conductive mechanism under partially water saturation. These results can be used to develop accurate electrical models, specifically for shale rocks with heterogeneous and sophisticated microstructure. The methodology can be also extended to other micro- or meso-porous geomaterials such as cementitious and bituminous nanoporous media.     

砂质海底沉积物压缩波速与物理参数关系试验研究

砂土是主要的海底沉积物类型之一,明确砂质沉积物声学与物理性质的关系对海底底质和地层探测至关重要.本文利用超声探测仪和自制的试样制备测试装置,模拟制备不同沉积状态的砂土试样,同步开展超声测试和物理性质测试,探讨砂质沉积物声速测试方法及影响因素,揭示砂质沉积物压缩波速与物理参数的内在联系.试验结果和分析表明:换能器接触管壁...     

Mineral assemblages occurring around hydrocarbon vents in the northern Gulf of Mexico

Magnesian calcites are the most abundant authigenic minerals associated with hydrocarbon vents at 25 sites, in water depths ranging from 100 to 600 m in the Green Canyon area and about 2200 m in the Alaminos Canyon area on the Continental Slope of the northern Gulf of Mexico. The most frequently encountered magnesian calcites have 10–15 mol% MgCO₃ and the apparent structural disorder revealed by XRD peak widths increases with Mg substitution. There are no systematic variations in Mg content with respect to water depth or geographic location. The calcite saturation state of the precipitating fluid is primarily determined by the nature of the fluids escaping from the vents, not the ambient seawater.     

Influence of export rain ratio changes on atmospheric CO<Subscript>2</Subscript> and sedimentary calcite preservation

The responses of atmospheric pCO₂ and sediment calcite content to changes in the export rain ratio of calcium carbonate to organic carbon are examined using a diffusion-advection ocean biogeochemical model coupled to a one-dimensional sediment geochemistry model. Our model shows that a 25% reduction in rain ratio decreases atmospheric pCO₂ by 59 ppm. This is caused by alkalinity redistribution by a weakened carbonate pump and an alkalinity increase in the whole ocean via carbonate compensation with decreasing calcite burial. The steady state responses of sedimentary calcite content and calcite preservation efficiency are rather insensitive to the deepening of the saturation horizon of 1.9 km. This insensitivity is a result of the reduced deposition flux that decreases calcite burial, counteracting the saturation horizon deepening that increases calcite burial. However, in the first 10,000 years the effect of reduced calcite deposition on the burial change is more prominent; while after 10,000 years, the effect of saturation horizon deepening is more dominant. The lowering of sediment calcite content for the first 10,000 years is effectively decoupled from the 1.9 km downward shift of the saturation horizon. Our results are in part a consequence of the more dominant role that respiration CO₂ plays in sediment calcite dissolution over bottom water chemistry in our control run and support the decoupling of calcite lysocline depth and saturation horizon shifts, as suggested originally by Archer and Maier-Reimer (1994) and Archer et al. (2000).     

Study of apparent complexing capacities of trace heavy-metals in the Huanghe River Estuary

-By the electroanalysis method combining the complexation titrating technique with the investigation of ip-Ea* characteristic curves, this paper measures apparent complexing capacities of trace heavy-metals in water samples from the Huanghe River Estuary. The results show that the order of apparent complexing capacities of trace heavy-metals in the samples isCu>Cd>Pb,and that apparent complexing capacities of near shore sample are higher than those far from shore. The effect of ultraviolet irradiation on the dissociation of organic ligands and the adsorption effect of cell walls (cells being treated with acid and seawater respectively) are investigated. The reduction (on electrodes) mechanism of species of trace heavy-metals in seawater is approached by ip-Ea* characteristic curves.     

Effects of oxic and anoxic filtration on determined methyl mercury concentrations in sediment pore waters

Accurate determination of methyl mercury (MeHg) concentrations in sediment pore waters is crucial for an improved understanding of mercury (Hg) biogeochemistry, and for improved risk assessment of Hg contaminated sites. In the present study, effects of oxic (air) and anoxic (N₂) filtration (after centrifugation) on determined pore water MeHg concentrations were investigated in severely Hg contaminated pulp fibre sediments from two estuaries of the Bothnian Sea, Sweden. MeHg was determined in the filtrate using species-specific isotope dilution gas chromatography inductively coupled plasma mass spectrometry (SSID–GC–ICPMS), after ethylation with sodium tetraethylborate. Determined concentrations of MeHg were greater after anoxic filtration than after oxic filtration for all samples investigated, with MeHg(N₂)/MeHg(air) ratios ranging between 3.4 and 343. Adsorption to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces is proposed as the main mechanism responsible for MeHg removal during oxic filtration. This is supported by decreases in dissolved Fe and Mn concentrations during oxic filtration, and by decreases in dissolved sulphur concentrations during oxic filtration in the samples with largest effect on MeHg concentrations. The latter is explained by adsorption of SO₄²⁻ to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces. The effect of oxidation during filtration on pore water MeHg concentrations was largest in samples in which FeS(s) was not present, but with calculated pe-values below − 3. Thus, our results indicate that the largest errors with respect to pore water MeHg concentrations when filtering in air can be expected in samples with an intermediate redox potential, possibly buffered by a mixture of oxidation sensitive Fe(II/III) minerals.     

High-resolution well-log derived dielectric properties of gas-hydrate-bearing sediments, Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

A dielectric logging tool, electromagnetic propagation tool (EPT), was deployed in 2007 in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert Well), North Slope, Alaska. The measured dielectric properties in the Mount Elbert well, combined with density log measurements, result in a vertical high-resolution (cm-scale) estimate of gas hydrate saturation. Two hydrate-bearing sand reservoirs about 20 m thick were identified using the EPT log and exhibited gas-hydrate saturation estimates ranging from 45% to 85%. In hydrate-bearing zones where variation of hole size and oil-based mud invasion are minimal, EPT-based gas hydrate saturation estimates on average agree well with lower vertical resolution estimates from the nuclear magnetic resonance logs; however, saturation and porosity estimates based on EPT logs are not reliable in intervals with substantial variations in borehole diameter and oil-based invasion.EPT log interpretation reveals many thin-bedded layers at various depths, both above and below the thick continuous hydrate occurrences, which range from 30-cm to about 1-m thick. Such thin layers are not indicated in other well logs, or from the visual observation of core, with the exception of the image log recorded by the oil-base microimager. We also observe that EPT dielectric measurements can be used to accurately detect fine-scale changes in lithology and pore fluid properties of hydrate-bearing sediments where variation of hole size is minimal. EPT measurements may thus provide high-resolution in-situ hydrate saturation estimates for comparison and calibration with laboratory analysis.     

碱基对组分、电极位能及界面耦合对DNA分子I-V特性的影响

在紧束缚近似下,利用传输矩阵方法,计算研究了碱基对组分、金属电极位能及DNA分子与电极耦合强度对DNA分子I-V特征的影响.计算结果表明:由单一碱基对构成的DNA分子的饱和电流强度远大于由两种碱基对按一定组分随机分布的DNA分子的饱和电流强度,且当DNA分子中两种碱基对的含量相等时,其饱和电流强度最小.同时,富含C-G碱基对的DNA分子比富含A-T碱基对的DNA分子的电子输运能力大.金属电极位能对DNA分子电子输运的影响体现在两方面,当偏压较小时,电极位能具有阻碍电荷注入的效果,当偏压较大时     

Physical and Acoustic Properties of Gas-bearing Sediments in Jinhae Bay,the South Sea of Korea

High-resolution seismic survey and sediment core sampling were conducted to investigate acoustic characteristics of gas-bearing sediments in Jinhae Bay, the southeast of Korea. The sediment in Jinhae Bay is mostly homogenous mud deposited after the Holocene transgression. Along with the 410 km of chirp seismic profiling, five piston core samples were collected on the track lines.

Gassy sediments are common and occur widely in the bay. Core samples were analyzed for sediment texture, physical properties (porosity, water content, bulk density, and grain density), acoustic properties (compressional wave velocity and attenuation), and electrical resistivity. X-radiograph image analysis was also performed to observe the shape of degassing cracks. There is no significant downcore variation on physical and sediment textures regardless of existence of gas bubbles. However, compressional wave velocity dramatically decreases from average 1480 to 1380～739 m/s for the cores that penetrate the gas-bearing zones. This is probably due to degassying cracks that developed by escaping gases and free gas bubbles that are still trapped in the cores. Electrical resistivity is the only geotechnical property that increases in the gas-bearing zone where compressional wave velocity abruptly decreases. This indicates the possibility of using both electrical resistivity as an index variable as well as to compressional wave velocity to identify gassy sediment microstructure because there are little changes in texture and composition of sediment.     

Remote effects of mixed layer development on ocean acidification in the subsurface layers of the North Pacific

Using the outputs of projections under the highest emission scenario of the representative concentration pathways performed by Earth system models (ESMs), we evaluate the ocean acidification rates of subsurface layers of the western North Pacific, where the strongest sink of atmospheric CO₂ is found in the mid-latitudes. The low potential vorticity water mass called the North Pacific Subtropical Mode Water (STMW) shows large dissolved inorganic carbon (DIC) concentration increase, and is advected southwestward, so that, in the sea to the south of Japan, DIC concentration increases and ocean acidification occurs faster than in adjacent regions. In the STMW of the Izu-Ogasawara region, the ocean acidification occurs with a pH decrease of ~0.004 year^?1 , a much higher rate than the previously estimated global average (0.0023 year^?1), so that the pH decreases by 0.3–0.4 during the twenty-first century and the saturation state of calcite (Ω_Ca) decreases from ~4.8 down to ~2.4. We find that the ESMs with a deeper mixed layer in the Kuroshio Extension region show a larger increase in DIC concentration within the Izu-Ogasawara region and within the Ryukyu Islands region. Comparing model results with the mixed layer depth obtained from the Argo dataset, we estimate that DIC concentration at a depth of ~200 m increases by 1.4–1.6 μmol kg^?1 year^?1 in the Izu-Ogasawara region and by 1.1–1.4 μmol kg^?1 year^?1 in the Ryukyu Islands region toward the end of this century.     

Fluid flow equations governing primary oil migration as a separate phase

A mathematical model of primary oil migration as a separate phase out of compacting shales is presented. During burial and oil generation, source rock porosity decreases and oil saturation increases until residual oil saturation is reached. At this stage oil is expelled out by capillary and excess fluid pressure gradients. The model is a system of differential equations which relate changes in oil and water saturation in time to water and oil flow out of the source rock during burial. An additional set of equations for periods of erosion of overburden are also provided. The equations can be numerically solved by finite difference method. If oil and water flow is to be simulated during oil generation, then at each time step, changes by oil generation in oil and water saturations and porosity must be calculated. The solution procedure is briefly outlined.     

大洋河河口海域有色溶解性有机物的光学特性及遥感反演模型

有色溶解性有机物(CDOM)在河口混合过程中近似呈保守行为,可作为水团运动的示踪剂.基于2009年5月6日大洋河河口海域水体调查的实测数据,对该区域CDOM光学特性及遥感反演模型进行了研究,结果表明:研究区域CDOM主要来自河流输入,成分相对较稳定,属于典型的近岸二类水体区域;波长275～295 nm的光谱斜率和波长4...     

The ICE-MOSES experiment: Mapping permafrost zones electrically beneath the Beaufort Sea

A novel variation of the geophysical technique known as MOSES, for Magnetometric Off-Shore Electrical Sounding, has been developed to map the electrical properties of the sea floor in Aretic regions. The particular target is the permafrost layer under the Beaufort Sea, a layer containing frozen or partially frozen sediment from 100 to 600 m thick underlying shallow sea water, typically 10 to 100 m deep, and several tens of metres of soft sediment. A detailed knowledge of the location and physical properties of the permafrost layer is essential for accurate interpretation of reflection seismic data. The permafrost can contain pockets, regions or layers of gas hydrate. The latter is both a possible resource and a hazard to drilling operations or hydrocarbon production. A local map of the permafrost zone is essential geotechnical information required prior to the construction of an offshore structure or pipeline.The MOSES method is particularly suitable for offshore electrical mapping as it can be made relatively insensitive to the shielding effects of the highly conductive sea water, in sharp contrast to many other electrical techniques. The transmitter is a vertical, long-wire bipole, extending from the sea surface to the sea floor. A commutated current is fed to two large electrodes: one near the sea surface and the other on the sea floor. The return current is through the sea water and the subjacent sediment. The receiver consists of two horizontal orthogonal coils located on the sea floor, and the data are measurements of two components of the magnetic field as a function of frequency and transmitter-receiver horizontal separation.The electrical conductivity of a sample of frozen material is much smaller than that of unfrozen or partially frozen sediment of the same type. Frozen and unfrozen thin layers are often observed sequentially throughout the geological section. The resistivity measured as a function of depth by an electrical logging tool is consequently highly variable. The resulting depth-averaged resistivity, the resistivity resolved by a surface electrical method, is macro-an-isotropic. An experimental design study reveals that both the vertical and horizontal averaged resistivities could be determined in a MOSES sounding without vertical scale distortion.A test of the methodology in very shallow water was conducted in the spring of 1986 at a site, approximate coordinates (70° N, 134.5° W), 85 km north-west of the town of Tuktoyaktuk. The instrumentation was lowered and subsequently recovered through holes in the ice which covers the Beaufort Sea at that time of the year. The transmitter power was obtained from a single lead-acid battery. Transmitter-receiver separations ranged from 10 to 300 m. A rapid increase in sediment resistivity with depth was observed. The higher resistivity values are consistent with those expected for a partially frozen zone.     

Laboratory investigation on wave transmission through two rows of perforated hollow piles

Experimental investigations on perforated hollow piles in two rows were conducted in a two dimensional wave flume. The influence of water depth, incident wave steepness, clear spacing between the piles and the spacing of pile rows on transmission coefficient have been studied. The effect of staggering of piles in rows is investigated. The results are also compared with the results of experiments on piles without perforations. The investigations have revealed that perforated piles attenuate more wave energy than non-perforated piles. The transmission coefficient K_t decreases as the wave steepness increases for both non-perforated and perforated piles. For non-perforated piles as relative clear spacing between the piles (b/D) decreases, for waves of higher steepness, K_t decreases while for perforated piles as b/D decreases, K_t is decreasing for all the steepness considered. As the relative clear spacing between the pile rows (B/D) increases K_t initially decreases till B/D is around one and later it starts increasing for both non-perforated and perforated piles. Staggering of piles has little effect on K_t. It is also found that water depth has insignificant influence on transmission coefficient at higher steepness for both perforated and non-perforated piles. Wave period alone does not directly influence transmission coefficient K_t.     

DETERMINATION OF RESIDUAL MALATHION IN NATURAL WATER

A method for determination of malathion in natural water by cathodic stripping voltammetry using mercury film electrode is suggested in this paper. The method is based on the quantitativeformation of group generated by malathion as a result of elimination reaction inthe ethanol solution of sodium hydroxide. The group is similar to sulphide in electrochemical properties, and can be determined by cathodic stripping voltammetry. Interference from inorganic sulphide is prevented by the addition of Hg (NO3)2. This method has been applied to the determination of residual malathion in natural water (e. g. the sea, rivers, lakes, etc.). The waveheight is directly proportional to the malathion concentration within the range 5×10-9 - 1×10-7 mol/L. The method is simple and rapid, and the results of water sample determination is quite in accord with those of Gas Chromatograph.     

Apparent calcite supersaturation at the ocean surface: Why the present solubility product of pure calcite in seawater does not predict the correct solubility of the salt in nature

It is generally accepted that seawaters near the ocean surface are supersaturated with calcite and that increasing atmospheric CO₂ will not overcome this condition until late in the 21st century. These expectations are based on comparisons of the ion activity products (IAPs) of various seawaters to the solubility product (K) of seawater saturated with pure calcite at 1 atm and a given temperature. It has been shown in recent papers, however, that calcites in contact with natural seawater in the surface oceans are not pure, but are magnesian calcite compositions. As a result, the presently accepted values of the solubility product of calcite in seawater cannot be used to obtain a correct, or even a reasonable estimate of the saturation state of sea water relative to either pure or magnesian calcite. Data are presented demonstrating that use of the currently accepted solubility product of calcite in seawater to determine seawater's relative calcite saturation leads to gross overestimates of its extent.     

Geotechnical Properties of Surface Sediments in the INDEX Area

As a part of the environmental impact assessment studies, geotechnical properties of sediments were determined in the Central Indian Basin. The undrained shear strength and index properties of the siliceous sediments were determined on 20 box cores of uniform dimension collected from various locations in five preselected sites. The maximum core length encountered was 41 cm and most of the sediments were siliceous oozes consisting of radiolarian or diatomaceous tests. The shear strength measurements revealed that surface sediments deposited in recent times (0-10 cm) have a shear strength of 0-1 kPa; this value increases with depth, reaching 10 kPa at 40 cm deep. Older sediments have greater strength because of compaction. Water content varies in the wide range of 312-577% and decreases with depth. The clay minerals such as smectite and illite are dominant and show some control over water content. Wet density, specific gravity, and porosity do not indicate any notable variation with depth, thereby indicating a uniform, slow rate of sedimentation. The average porosity of sediments is 90.2%, specific gravity 2.18, and wet bulk density 1.12 g/cm 3 . Sediments exhibit medium to high plasticity characteristics, with the average plasticity index varying between 105% and 136%. Preliminary studies on postdisturbance samples showed an increase in natural water content and a decrease in undrained shear strength of sediments in the top 10- to 15-cm layer.     

Geotechnical Properties of Surface Sediments in the INDEX Area

Abstract

As a part of the environmental impact assessment studies, geotechnical properties of sediments were determined in the Central Indian Basin. The undrained shear strength and index properties of the siliceous sediments were determined on 20 box cores of uniform dimension collected from various locations in five preselected sites. The maximum core length encountered was 41 cm and most of the sediments were siliceous oozes consisting of radiolarian or diatomaceous tests. The shear strength measurements revealed that surface sediments deposited in recent times (0–10 cm) have a shear strength of 0–1 kPa; this value increases with depth, reaching 10 kPa at 40 cm deep. Older sediments have greater strength because of compaction. Water content varies in the wide range of 312–577% and decreases with depth. The clay minerals such as smectite and illite are dominant and show some control over water content. Wet density, specific gravity, and porosity do not indicate any notable variation with depth, thereby indicating a uniform, slow rate of sedimentation. The average porosity of sediments is 90.2%, specific gravity 2.18, and wet bulk density 1.12 g/cm³. Sediments exhibit medium to high plasticity characteristics, with the average plasticity index varying between 105% and 136%. Preliminary studies on postdisturbance samples showed an increase in natural water content and a decrease in undrained shear strength of sediments in the top 10- to 15-cm layer.     

Electrical Resistivity Features of Compacted Expansive Soils

An electrical resistance apparatus with a highly sensitive alternate current bridge was developed in the paper for the purpose of measuring the electrical resistivity of soils and eliminating the low frequency polarization. The electrical resistivity of Guangxi expansive soils was measured in the laboratory using the developed apparatus. The investigation result demonstrates that the electrical resistivity of the Guangxi expansive soil is a function of the electrical resistivity of soil skeleton and pore water, water content, degree of saturation and void ratio. Along with electrical resistivity, the matrix suction was measured, and the relationship between the electrical resistivity and matrix suction was analyzed. The electrical resistivity-volumetric water content curves are compared with the matrix suction-volumetric water content curves for these soils. The relationship of matrix suction-volumetric water content is observed to be the similar feature to that of the electrical resistivity-volumetric water content curve.     

Laboratory study of shear strength response of Chlef natural sand: Effect of saturation

Abstract

The study of the unsaturated soils is a very complex field to which several researches in laboratory and on site are directed these last years. An experimental study aims to quantify the influence of the Skempton coefficient B characterizing the degree of saturation on the behavior of the granular sand to the liquefaction resistance of sand. The study is based on undrained triaxial tests performed on natural Chlef sand carried out at an initial relative density Dr = 50% under a confining pressure of 50, 100 and 200?kPa for Skempton coefficient B?=?10 to 92%. The results of the tests show that an increase of confining pressure leads to an increase of the shear stress of the samples. For the lower value of the degree of saturation results of our findings indicate an increase of the resistance to liquefaction; our results are in good agreement with others observed in several research projects conducted with other sands. The increase of Skempton coefficient B induces an increase of pore water pressure and a decrease of the shear strength. The pore pressure (u) increases with an exponential manner with the increase of the degree of saturation; while the residual shear strength (Rs) decreases with logarithmic manner with the increase of degree of saturation (B).