东营凹陷辛镇复杂断块油藏形成机制和剩余油分布规律研究

In this paper, the complex faulted-block oil reservoir of Xinzhen area in Dongying depression is systematically studied from basic conditions forming faulted-block oil and gas reservoir integrating geology, seismic, logging and reservoir engineering information and computer; guided by petroleum geology, geomechanics, structural geology and geophysics and other theories. Based on analysis of background condition such as regional strata, structure and petroleum geology, structural research on geometry, kinemaitcs and dynamics, oil-controlling fault research on the seal features, sealing mechanism and sealing pattern, and research on enrichment rules and controlling factors of complex faulted-block oil reservoir are carried out to give out the formation mechanics of oil reservoir of Xinzhen complex faulted-block oil reservoir. As a result, the reservoir formation pattern is established. At the same time, through dissecting the characteristics and hydrocarbon enrichment law of complex faulted-block oil reservoir, and studying its distribution law of remaining oil after entering extra high water-cut period, a set of technologies are formed to predict complex faulted-block oil reservoir and its remaining oil distribution and to enhance oil recovery (EOR). Based on the time relationship between migration of hydrocarbon and trap formation, accumulating period of Xinzhen oil reservoir is determined. The formation of Xinzhen anticlinal trap was prior to the primary migration. This is favorable to formation of Xinzhen anticlinal hydrocarbon reservoir. Meanwhile, because anticline top caving isn't at the sane time as that of moving or faulted-trap forming inner anticline, oil and gas migrated many times and Xinzhen complex faulted-block oil reservoir formed from ES_3~(upper) to EG. Accumulating law and controlling factors of complex faulted-block reservoir are analyzed from many aspects such as regional structure background controlling hydrocarbon accumulating, plastic arch-open structure controlling oil-bearing series and reservoir types, sealing-opening of fault controlling hydrocarbon distribution and structure pattern controlling enriched trap types. Also, we established the structure pattern in Xinzhen a'ea: the arch-open of underlying strata cause expanding fracture. The main block groups developed here are shovel-like normal fault block group in the north area of Xinzhen and its associated graben block group. Block groups dominate the formation and distribution of reservoirs. We studied qualitatively and quantitatively the sealing characteristics, sealing history and sealing mechanism of faults, too. And, the sealing characteristics are evaluated and the distribution pattern of hydrocarbon controlled by faults is researched. Due to movement intensity of big faults, deep falling of downthrown block, high degree of repture and development of fracture, shallow layers close to the downthrown block of secondary faults are unfavorable to hydrocarbon accumulation. This is confirmed by the exploration practice in Xinzhen anticline. In terms of the downthrown blocks of sencondary contemporaneous faults lied in the south and north area of Xinzhen, hydrocarbon is poor close to fracture belt, while it is relatively abundant in tertiary companion faults. Because of long-term movement of faults that control hydrocarbon, fi'om ES3 to EG, six set of oil-bearing series formed. And their opening causes the inhomogeneity in hydrocarbon abundance among each block--in two flanks of anticline reservoirs are abundant while in the axial area, oil and gas are sporadic. There the sealing characteristics control oil-bearing area of oil/gas accumulation and the height of oil reservoir. Longitudinally, oil and gas are enriched in dip-flat areas in mid-plane of faults. It is established that there are four types of accumulating patterns in complex faulted-block oil reservoirs in Xinzhen. The first is accumulating pattern of lithologic oil reservoirs in E~S_3~(mid-lowwer), that is, self-generating-self-reserving-self-covering lithologic trap pattern. The second is drag-anticline accumulating pattern in Xinzhen. The structure traps are drag anticlines formed by the contemporaneous faults of the second basement in the north of Xinzhen, and the multiple source rocks involve Ek_2, Es_4, Es_3 and Es_1 members. The reservoirs are fluvial-delta sandstones of the upper member of Shahejie formation and Guantao formation, covered by regional thick mudstone of the upper member of Guantao formation and MingHuazhen formation. The third is the accumulating pattern of reverse listric fault, the third-degree fault of Xinzhen anticline limb and the reservoirs form reservoir screened by reverse listric faults. The forth is accumulating pattern of crossing faults which form closing or semi-closing faulted-blocks that accumulate hydrocarbon. The technologies of predicting remaining oil in complex faulted-block reservoir during the mid and late development stage is formed. Remaining oil in simple large faulted-blocks enriches in structural high, structural middle, structural low of thick bottom water reservoirs, points near bent edge-fault oftertiary faults and part the fourth ones with big falling displacement, microstructure high place of oil-sandbodies and areas where local well pattern isn't perfect. While that in small complex faulted-blocks enriches near small nose, small high point, angle of small faults, small oil-bearing faulted-blocks without well and areas with non-perfect well pattern. The technologies of enhancing recovery factor in complex faulted-block reservoir during the mid and late development stage is formed as follows: fine reservoir description, drilling adjust wells, designing directional wells, sub-dividing layer series of development, improving flooding pattern, changing water-injection direction and enhancing swept volume, cyclic waterflooding and gas-injection, etc. Here, directional wells include directional deflecting wells, lateral-drilling wells, lateral-drilling horizontal wells and horizontal wells. The results of this paper have been used in exploration and development of Shengli oilfield, and have achieved great social and economic profit, especially in predicting distribution of complex faulted-block reservoir, remaining oil distribution during middle and late stage of development, and in EOR. Applying the achievement of fault-closure research, new hydrocarbon-bearing blocks are discovered in flanks of Dongying central uplift and in complex blocks with proved reserves 15 million tons. With the study of remaining oil distribution law in complex faulted-block reservoirs, recovery factors are increased greatly in Dongxin, Xianhe and Linpan complex faulted-block reservoirs and accumulated oil production increment is 3 million tons.

济阳坳陷及其南缘奥陶系碳酸盐岩潜山储集性及控制因素

The main research area of this thesis is Jiyang Depression in the Bohaiwan Basin and its southern margin. The object formation is Ordovician carbonate. The research is based on the outcrop observation and measurement of Ordovician carbonate and the drilling data of the oilfield. The internal reservoir characteristics of carbonate buried hill and its distribution were studied by comprehensive methods of sedimentology, reservoir geology and structural geology and technics of cathodoluminescence(CL)3electron microprobe,casting and C O isotope analysis etc. The influence depth of paleokarst facies formed during the Paleozoic is discriminated as 36-84m. The sollution porosity is well developed in paleokarst facies of Ordovician carbonate and is an important type of internal reservoir of buried hill. It may be infered that the fractures may be formed mainly during the Mesozoic and Cenozoic, they were not developed during the early Paleozoic when only micro-fractures might be created. The carbon and oxigen isotope analysis shows that the calcite cements in the fractures of Ordovician carbonate and secondary solution pores were related with meteoric water and three stages of fractures were divided. The reservoir space of Ordovician carbonate are mainly secondary porosity, cavern and fracture. The development of structural fracture was controlled by the lithology and tectonic background. More fractures exist in dolomite than that in limestone. There are also more fractures near the fault and the axis of fold. The development of porous reservoir is mainly controlled by the lithology and diagenesis, especially dolomitization and dissolution. It also results in the heterogeneity vertically. So the lithology is the basic factor for the forming of internal reservoir of buried hill and the tectogenesis and diagenesis are key factors to improve it. The porosity in carbonate might experienced solution-cementation-resolution or recementation. The porosity evolution history was a kind of historical dynamic equilibrium. The internal reservoir of Ordovician carbonate is the comprehensive result of constructive and/or destructive diagenesis. The worm's eye maps of the early Paleozoic and middle-upper Proterozoic were plotted. It was inferred that the paleostress field evoluted from NNW to NW during the Mesozoic and Cenozoic. Three types of buried hills can be divided: C-P/Pzi, Mz/ Pzi and E/ Pzi. The unconformity of the buried hill of E/ Pzi type, comparatively, was formed and reconstructed latestly, t he p orous r eservoir c ould b e w ell p reseved. T his c ondition w as v ery favorable t o t he migration and accumulation of oil and gas and could form upstanding association of source-reservoir-cap rocks. The buried hills of Mz/ Pzi and C-P/Pz] type were took second place.

多波分量地震资料处理解释方法

To deal with some key problems in multi-component seismic exploration, some methods are introduced in this thesis based on reading amounts of papers about multi-component seismic theories and methods. First, to find a solution for the detection of the fracture density and orientation in igneous, carbonate and shale reservoirs, a large amount of which exist in domestic oil fields with low exploration and development degree, a new fast and slow shear waves separation method called Ratio Method based on S-wave splitting theory is discussed in this thesis, through which the anisotropy coefficient as well as fracture parameters such as density and azimuthal angle can be acquired. Another main point in this thesis involves the application of seismic velocity ratio (Vp/Vs) to predict the Hthological parameters of subsurface medium. To deal with the unfeasibility of velocity ratio calculation method based on time ratio due to the usually low single-noise ratio of S-wave seismic data acquired on land, a new method based on detailed velocity analysis is introduced. Third, pre-stack Kirchhoff integral migration is a new method developed in recent years, through which both S and P component seismic data as well as amplitude ratio of P/S waves can be acquired. In this thesis, the research on untilizing the P and S wave sections as well as amplitude ratio sections to interpret low-amplitude structures and lithological traps is carried out. The fast and slow shear wave separation method is then be applied respectively to detect the density and azimuthal angle of fractures in an igneous rock gas reservoir and the coal formation in a coal field. Two velocity ratio-calculating methods are applied respectively in the lithological prediction at the gas and coal field after summarizing a large amount of experimental results draw domestically and abroad. P and S wave sections as well as amplitude ratio sections are used to identify low-amplitude structures and lithological traps in the slope area of a oil-bearing sedimentary basin. The calculated data concerning fracture density and azimuthal angle through the introduced method matches well with the regional stress and actual drilling data. The predicted lithological data reflects the actual drilling data. Some of the low-amplitude and lithological traps determined by Kirchhoff migration method are verified by the actual drilling data. These results indicate that these methods are very meaningful when dealing with complex oil and gas reservoir, and can be applied in other areas.

陆相砂泥岩层序的高精度检测方法研究及应用

Ordos Basin is a typical cratonic petroliferous basin with 40 oil-gas bearing bed sets. It is featured as stable multicycle sedimentation, gentle formation, and less structures. The reservoir beds in Upper Paleozoic and Mesozoicare are mainly low density, low permeability, strong lateral change, and strong vertical heterogeneous. The well-known Loess Plateau in the southern area and Maowusu Desert, Kubuqi Desert and Ordos Grasslands in the northern area cover the basin, so seismic data acquisition in this area is very difficult and the data often takes on inadequate precision, strong interference, low signal-noise ratio, and low resolution. Because of the complicated condition of the surface and the underground, it is very difficult to distinguish the thin beds and study the land facies high-resolution lithologic sequence stratigraphy according to routine seismic profile. Therefore, a method, which have clearly physical significance, based on advanced mathematical physics theory and algorithmic and can improve the precision of the detection on the thin sand-peat interbed configurations of land facies, is in demand to put forward.Generalized S Transform (GST) processing method provides a new method of phase space analysis for seismic data. Compared with wavelet transform, both of them have very good localization characteristics; however, directly related to the Fourier spectra, GST has clearer physical significance, moreover, GST adopts a technology to best approach seismic wavelets and transforms the seismic data into time-scale domain, and breaks through the limit of the fixed wavelet in S transform, so GST has extensive adaptability. Based on tracing the development of the ideas and theories from wavelet transform, S transform to GST, we studied how to improve the precision of the detection on the thin stratum by GST.Noise has strong influence on sequence detecting in GST, especially in the low signal-noise ratio data. We studied the distribution rule of colored noise in GST domain, and proposed a technology to distinguish the signal and noise in GST domain. We discussed two types of noises: white noise and red noise, in which noise satisfy statistical autoregression model. For these two model, the noise-signal detection technology based on GST all get good result. It proved that the GST domain noise-signal detection technology could be used to real seismic data, and could effectively avoid noise influence on seismic sequence detecting.On the seismic profile after GST processing, high amplitude energy intensive zone, schollen, strip and lentoid dead zone and disarray zone maybe represent specifically geologic meanings according to given geologic background. Using seismic sequence detection profile and combining other seismic interpretation technologies, we can elaborate depict the shape of palaeo-geomorphology, effectively estimate sand stretch, distinguish sedimentary facies, determine target area, and directly guide oil-gas exploration.In the lateral reservoir prediction in XF oilfield of Ordos Basin, it played very important role in the estimation of sand stretch that the study of palaeo-geomorphology of Triassic System and the partition of inner sequence of the stratum group. According to the high-resolution seismic profile after GST processing, we pointed out that the C8 Member of Yanchang Formation in DZ area and C8 Member in BM area are the same deposit. It provided the foundation for getting 430 million tons predicting reserves and unite building 3 million tons off-take potential.In tackling key problem study for SLG gas-field, according to the high-resolution seismic sequence profile, we determined that the deposit direction of H8 member is approximately N-S or NNE-SS W. Using the seismic sequence profile, combining with layer-level profile, we can interpret the shape of entrenched stream. The sunken lenticle indicates the high-energy stream channel, which has stronger hydropower. By this way we drew out three high-energy stream channels' outline, and determined the target areas for exploitation. Finding high-energy braided river by high-resolution sequence processing is the key technology in SLG area.In ZZ area, we studied the distribution of the main reservoir bed-S23, which is shallow delta thin sand bed, by GST processing. From the seismic sequence profile, we discovered that the schollen thick sand beds are only local distributed, and most of them are distributary channel sand and distributary bar deposit. Then we determined that the S23 sand deposit direction is NW-SE in west, N-S in central and NE-SW in east. The high detecting seismic sequence interpretation profiles have been tested by 14 wells, 2 wells mismatch and the coincidence rate is 85.7%. Based on the profiles we suggested 3 predicted wells, one well (Yu54) completed and the other two is still drilling. The completed on Is coincident with the forecastThe paper testified that GST is a effective technology to get high- resolution seismic sequence profile, compartmentalize deposit microfacies, confirm strike direction of sandstone and make sure of the distribution range of oil-gas bearing sandstone, and is the gordian technique for the exploration of lithologic gas-oil pool in complicated areas.

克拉2异常高压气藏地质特征及开发技术研究

Kela-2 gas field in Tarim Basin is the main supply source for West-to-East Pipeline project, also the largest abnormally-pressured gas field discovered in China currently. The geological characterization, fine geological modeling and field development plan are all the world-class difficult problems. This work includes an integrated geological and gas reservoir engineering study using advanced technology and approaches, the scientific development plan of Kela-2 gas field as well as the optimizations of the drilling, production and surface schemes. Then, it's expected that the Kela-2 gas field can be developed high-efficiently.Kuche depression is one part of the thrust belt of the South Tianshan Mountains, Kela-2 field is located at the Kelasu structural zone in the north of Kuche depression. The field territory is heavily rugged with deeply cut gullies, complex geological underground structure, variable rock types, thrust structure development. Therefore, considerable efforts have been made to develop an integrated technique to acquire, process and interpret the seismic data in complicated mountain region. Consequently a set of seismic-related techniques in the complicated mountain region has been developed and successfully utilized to interpret the structure of Kela-2 gas field.The main reservoir depositional system of Kela 2 gas field is a platform - fan delta - braided river system. The reservoir rocks are medium-fine and extremely fine grained sandstones with high structure maturity and low composition maturity. The pore system structure is featured by medium-small pore, medium-fine throat and medium-low assortment. The reservoir of Kela-2 gas field is characteristic of medium porosity and medium permeability. The pay zone is very thick and its lateral distribution is stable with a good connection of sand body. The overpressure is caused mainly by the strongly tectonic squash activities, and other factors including the later rapid raise and compartment of the high-pressure fluid, the injection of high-pressure fluid into the reservoir.Based on the deliverability tests available, the average binomial deliverability equation is provided applicable for the overall field. The experimental results of rock stress-sensitive tests are employed to analyze the change trend of petrophysical properties against net confining stress, and establish the stress-based average deliverability equation. The results demonstrate the effect of rock deformation on the deliverability is limited to less than 5% in the early period of Kela-2 gas field, indicating the insignificant effect on deliverability of rock deformation.In terms of the well pattern comparisons and development planning optimizations, it is recommended that the producers should be located almost linearly along the structural axis. A total of 9 producers have a stable gas supply volume of 10.76 BCMPY for 17 years. For Kela-2 gas field the total construction investment is estimated at ￥7,697,690,000 RMB with the internal earning rate of 25.02% after taxation, the net present value of ￥7,420,160,000 RMB and the payback period of 5.66 years. The high profits of this field development project are much satisfactory.

Research and development of catalytic processes for petroleum and natural gas conversions in the Dalian Institute of Chemical Physics

The Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences has a long history in the R&D of catalysts and catalytic processes for petroleum and natural gas conversions in China. In this paper, results and features of some commercialized petrochemical catalysts and processes as well as newly developed processes for natural gas conversion in the pilot-plant stage are described. (C) 1999 Elsevier Science B.V. All rights reserved.

An empirical equation for the calculation of retention time with extrapolation of temperature in gas chromatography

An empirical equation is proposed to accurately correlate isothermal data over a wide range of temperature With the equation ln k = A* + B*/T-lambda the retention times of different solutes tested on OV-101, SE-54 and PEG 20M capillary columns have been achieved even when lambda is assigned a constant value of 1.7 Comparison with ln k = A + B/T and in k = c + d/T+ h/T-2, shows that the proposed equation is of higher accuracy and is applicable to extrapolation calculation, especially from data at high temperature to those at low temperature. Parameters A* and B* as well as A and B are also discussed. The linear correlation of A* and B* is weaker than that of A and B.

Empirical analysis and improved modelling of natural gas demand in Ireland

Countries across the world are being challenged to decarbonise their energy systems in response to diminishing fossil fuel reserves, rising GHG emissions and the dangerous threat of climate change. There has been a renewed interest in energy efficiency, renewable energy and low carbon energy as policy‐makers seek to identify and put in place the most robust sustainable energy system that can address this challenge. This thesis seeks to improve the evidence base underpinning energy policy decisions in Ireland with a particular focus on natural gas, which in 2011 grew to have a 30% share of Ireland’s TPER. Natural gas is used in all sectors of the Irish economy and is seen by many as a transition fuel to a low-carbon energy system; it is also a uniquely excellent source of data for many aspects of energy consumption. A detailed decomposition analysis of natural gas consumption in the residential sector quantifies many of the structural drives of change, with activity (R2 = 0.97) and intensity (R2 = 0.69) being the best explainers of changing gas demand. The 2002 residential building regulations are subject to an ex-post evaluation, which using empirical data finds a 44 ±9.5% shortfall in expected energy savings as well as a 13±1.6% level of non-compliance. A detailed energy demand model of the entire Irish energy system is presented together with scenario analysis of a large number of energy efficiency policies, which show an aggregate reduction in TFC of 8.9% compared to a reference scenario. The role for natural gas as a transition fuel over a long time horizon (2005-2050) is analysed using an energy systems model and a decomposition analysis, which shows the contribution of fuel switching to natural gas to be worth 12 percentage points of an overall 80% reduction in CO2 emissions. Finally, an analysis of the potential for CCS in Ireland finds gas CCS to be more robust than coal CCS for changes in fuel prices, capital costs and emissions reduction and the cost optimal location for a gas CCS plant in Ireland is found to be in Cork with sequestration in the depleted gas field of Kinsale.

Ocean-atmosphere trace gas exchange

The oceans contribute significantly to the global emissions of a number of atmospherically important volatile gases, notably those containing sulfur, nitrogen and halogens. Such gases play critical roles not only in global biogeochemical cycling but also in a wide range of atmospheric processes including marine aerosol formation and modification, tropospheric ozone formation and destruction, photooxidant cycling and stratospheric ozone loss. A number of marine emissions are greenhouse gases, others influence the Earth's radiative budget indirectly through aerosol formation and/or by modifying oxidant levels and thus changing the atmospheric lifetime of gases such as methane. In this article we review current literature concerning the physical, chemical and biological controls on the sea-air emissions of a wide range of gases including dimethyl sulphide (DMS), halocarbons, nitrogen-containing gases including ammonia (NH3), amines (including dimethylamine, DMA, and diethylamine, DEA), alkyl nitrates (RONO2) and nitrous oxide (N2O), non-methane hydrocarbons (NMHC) including isoprene and oxygenated (O)VOCs, methane (CH4) and carbon monoxide (CO). Where possible we review the current global emission budgets of these gases as well as known mechanisms for their formation and loss in the surface ocean.

Lagrangian evolution of DMS during the Southern Ocean gas exchange experiment: The effects of vertical mixing and biological community shift

Concentrations of dimethylsulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) are highly variable in time and space. What is driving the variability in DMS(P), and can those variability be explained by physical processes and changes in the biological community? During the Southern Ocean Gas Exchange Experiment (SO GasEx) in the austral fall of 2008, two 3He/SF6 labeled patches were created in the surface water. SF6 and DMS were surveyed continuously in a Lagrangian framework, while direct measurements of air-sea exchange further constrained the gas budgets. Turbulent diffusivity at the base of the mixed layer was estimated from SF6 profiles and used to calculate the vertical fluxes of DMS and nutrients. Increasing mixed layer nutrient concentrations due to mixing were associated with a shift in the phytoplankton community structure, which in turned likely affected the sulfur dynamics on timescales of days. DMS concentration as well as air-sea DMS flux appeared to be decoupled from the DMSP concentration, possibly due to grazing and bacterial DMS production. Contrary to expectations, in an environment with high winds and modest productivity, physical processes (air-sea exchange, photochemistry, vertical mixing) only accounted for a small fraction of DMS loss from the surface water. Among the DMS sinks, inferred biological consumption most likely dominated during SO GasEx.

Simulation of the Unsteady Gas Flow through a Three-way Automotive Catalyst

This paper describes a model of a 1.8-litre four-cylinder four-stroke gasoline engine fitted with a close-coupled three-way catalyst (TWC). Designed to meet EURO 3 emissions standards, the engine includes some advanced emission control features in addition to the TWC, namely: variable valve timing (VVT), swirl control plates, and exhaust gas recirculation (EGR). Gas flow is treated as one-dimensional (1D) and unsteady in the engine ducting and in the catalyst. Reflection and transmission of pressure waves at the boundaries of the catalyst monolith are modelled. In-cylinder combustion is represented by a two-zone burn model with dissociation and reaction kinetics. A single Wiebe analysis of measured in-cylinder pressure data is used to determine the mass fraction burned as a function of crank angle (CA) at each engine speed. Measured data from steady-state dynamometer tests are presented for operation at wide open throttle (WOT) over a range of engine speeds. These results include CA-resolved traces of pressure at various locations throughout the engine together with cycle-averaged traces of gas composition entering the catalyst as indicated by a fast-response emissions analyser. Simulated engine performance and pressure wave action throughout the engine are well validated by the measured data.

Development of a modified flyash as a permeable reactive barrier media for a former manufactured gas plant site Northern Ireland

A sequential biological permeable reactive barrier (PRB) was determined to be the best option for remediating groundwater that has become contaminated with a wide range of organic contaminants (i.e., benzene, toluene, ethylbenzene, xylene and polyaromatic hydrocarbons), heavy metals (i.e., lead and arsenic), and cyanide at a former manufactured gas plant after 150 years of operation in Portadown, Northern Ireland. The objective of this study was to develop a modified flyash that could be used in the initial cell within a sequential biological PRB to filter complex contaminated groundwater containing ammonium. Flyash modified with lime (CaOH) and alum was subjected to a series of batch tests which investigated the modified cation exchange capacity (CEC) and rate of removal of anions and cations from the solution. These tests showed that a high flyash composition medium (80%) could remove 8.65 mol of ammonium contaminant for every kilogram of medium. The modified CEC procedure ruled out the possibility of cation exchange as the major removal mechanism. The medium could also adsorb anions as well as cations (i.e., Pb and Cr), but not with the same capacity. The initial mechanism for Pb and Cr removal is probably precipitation. This is followed by sorption, which is possibly the only mechanism for the removal of dichromate anions. Scanning electron microscopic analysis revealed very small (

Palaeoclimate change recorded in Upper Cretaceous (Albian-Cenomanian) Kazhdumi Formation Borehole spectral Gamma-Ray Logs, South Pars Gas field, Persian Gulf

Th/U and Th/K data from spectral gamma-ray logs obtained from outcrop successions have been used as a rapid and inexpensive proxy for determining possible episodes of humid-arid palaeoclimate change. Such outcrop-based measurements have never been tested using spectral gamma-ray data obtained from wireline logs in subsurface boreholes. Th/K and Th/U ratios have traditionally been used to decipher sequence stratigraphic patterns, at outcrop and in borehole. The possible influence of palaeoclimate on such ratio changes has yet to be proven, especially from borehole data. In this work, we compare borehole-derived Th/K (and to a lesser extent Th/U) to palaeoenvironmental changes inferred from palynology and deduce that both sea level and changing hinterland weathering regimes caused discrete fluctuations observed in the spectral gamma-ray logs. This is the first time such subsurface information has been used in this way. Interpretation of wireline logs in terms of palaeoclimate as well as sea level may now be considered, and the use of such logs in palaeoclimate reconstruction is strengthened.

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

GAS-PHASE REACTIONS AND RATE COEFFICIENTS FOR USE IN ASTROCHEMISTRY - THE UMIST RATEFILE

We present the rate coefficients of 2880 gas-phase reactions among 313 species involving 12 elements for use in astrochemical models. We describe the motivation behind this work and the caveats which attach to the data in general as well as to specific reactions. We give the permanent electric dipole moments of nearly all the 112 neutral molecules contained in the data set, so that rate coefficients can be calculated at the low temperatures of dark interstellar dust clouds. We have used the data to calculate the pseudo-time-dependent chemical evolution of a dark, dense interstellar cloud and present both early time and steady-state abundances for all 313 species.