Speciation Analysis of Organotin Compounds in Shellfish by Hyphenated Technique of High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry(HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds in the shellfish samples. Agilent TC-C-18 column was selected, mobile phase of the HPLC was CH3CN:H2O: CH3COOH = 65:23:12 (V/V), 0. 05% TEA, pH = 3.0 at flow rate 0.4 mL/min. Five mixed organotin standards from 100 mu g/L to 0. 5 mu g/L was used for the method evaluation. The experimental results indicate that the linearity (R-2) for each compound was over 0.998. The shellfish samples were treated by supersonic extraction with mobile phase for 30min. Four organotin compounds including dibutyltin (DBT), tributyltin (TBT), diphenyltin (DphT) and triphenyltin (TPhT) in shellfish samples were detected with method mentioned above. It was found that the domain compounds in the samples were tributyltin (TBT) and triphenyltin (TPhT). The recoveries test from the standard addition for trimethyltin (TMT tributyltin (TBT), and triphenyltin (TPhT) were, over 80%. However, the recoveries for diphenyltin (DPhT) and dibutyltin (DBT) were relatively low, 37.3% and 75.2% respectively. The reason might be attributed to the decomposition of those compounds during the extraction procedure. The further study on this subject is under the progress.

Depression of net ecosystem CO2 exchange in semi-arid Leymus chinensis steppe and alpine shrub

Uptake and release of carbon in grassland ecosystems is very critical to the global carbon balance and carbon storage. In this study, the dynamics of net ecosystem CO2 exchange (FNEE) of two grassland ecosystems were observed continuously using the eddy covariance technique during the growing season of 2003. One is the alpine shrub on the Tibet Plateau, and the other is the sem-arid Leymus chinensis steppe in Inner Mongolia of China. It was found that the FNEE of both ecosystems was significantly depressed under high solar radiation. Comprehensive analysis indicates that the depression of FNEE in the L. chinensis steppe was the results of decreased plant photosynthesis and increased ecosystem respiration (R-eco) under high temperature. Soil water stress in addition to the high atmospheric demand under the strong radiation was the primary factor limiting the stomatal conductance. In contrast, the depression of FNEE in the alpine shrub was closely related to the effects of temperature on both photosynthesis and ecosystem respiration, coupled with the reduction of plant photosynthesis due to partial stomatal closure under high temperature at mid-day. The R,c of the alpine shrub was sensitive to soil temperature during high turbulence (u* > 0.2 m s(-1)) but its FNEE decreased markedly when the temperature was higher than the optimal value of about 12 degrees C. Such low optimal temperature contrasted the optimal value (about 20 degrees C) for the steppe, and was likely due to the acclimation of most alpine plants to the long-term low temperature on the Tibet Plateau. We inferred that water stress was the primary factor causing depression of the FNEE in the semi-arid steppe ecosystem, while relative high temperature under strong solar radiation was the main reason for the decrease of FNEE in the alpine shrub. This study implies that different grassland ecosystems may respond differently to climate change in the future. (c) 2006 Elsevier B.V All rights reserved.

地质导向钻井关键技术及方法

On the basis of analyzing the principle and realization of geo-steering drilling system, the key technologies and methods in it are systematically studied in this paper. In order to recognize lithology, distinguish stratum and track reservoirs, the techniques of MWD and data process about natural gamma, resistivity, inductive density and porosity are researched. The methods for pre-processing and standardizing MWD data and for converting geological data in directional and horizontal drilling are discussed, consequently the methods of data conversion between MD and TVD and those of formation description and adjacent well contrast are proposed. Researching the method of identifying sub-layer yields the techniques of single well explanation, multi-well evaluation and oil reservoir description. Using the extremum and variance clustering analysis realizes logging phase analysis and stratum subdivision and explanation, which provides a theoretical method and lays a technical basis for tracing oil reservoirs and achieving geo-steering drilling. Researching the technique for exploring the reservoir top with a holdup section provides a planning method of wellpath control scheme to trace oil and gas reservoir dynamically, which solves the problem of how to control well trajectory on condition that the layer’s TVD is uncertain. The control scheme and planning method of well path for meeting the demands of target hitting, soft landing and continuous steering respectively provide the technological guarantee to land safely and drill successfully for horizontal, extended-reach and multi-target wells. The integrative design and control technologies are researched based on geology, reservoir and drilling considering reservoir disclosing ratio as a primary index, and the methods for planning and control optimum wellpath under multi-target restriction, thus which lets the target wellpath lie the favorite position in oil reservoir during the process of geo-steering drilling. The BHA (bottomhole assembly) mechanical model is discussed using the finite element method, and the BHA design methods are given on the basis of mechanical analyses according to the shape of well trajectory and the characteristics of BHA’s structure and deformation. The methods for predicting the deflection rate of bent housing motors and designing their assemblies are proposed based on the principle of minimum potential energy, which can clearly show the relation between the BHA’s structure parameters and deflection rate, especially the key factors’ effect to the deflection rate. Moreover, the interaction model between bit and formation is discussed through the process of equivalent formation and equivalent bit considering the formation anisotropy and bit anisotropy on the basis of analyzing the influence factors of well trajectory. Accordingly, the inherence relationship among well trajectory, formation, bit and drilling direction is revealed, which lays the theory basis and technique for predicting and controlling well trajectory.

离散裂缝诱导各向异性粘弹性地震波模拟与特征分析

The real media always attenuate and distort seismic waves as they propagate in the earth. This behavior can be modeled with a viscoelastic and anisotropic wave equation. The real media can be described as fractured media. In this thesis, we present a high-order staggered grid finite-difference scheme for 2-D viscoelastic wave propagation in a medium containing a large number of small finite length fractures. We use the effective medium approach to compute the anisotropic parameters in each grid cell. By comparing our synthetic seismogram by staggered-grid finite-difference with that by complex-ray parameter ray tracing method, we conclude that the high-order staggered-grid finite-difference technique can effectively used to simulate seismic propagation in viscoelastic-anisotropic media. Synthetic seismograms demonstrate that strong attenuation and significant frequency dispersion due to viscosity are important factors of reducing amplitude and delaying arrival time varying with incidence angle or offset. On the other hand, the amount of scattered energy not only provides an indicator of orientation of fracture sets, but can also provide information about the fracture spacing. Analysis of synthetic seismograms from dry- and fluid-filled fractures indicates that dry-filled fractures show more significant scattering on seismic wavefields than fluid-filled ones, and offset-variations in P-wave amplitude are observable. We also analyze seismic response of an anticlinal trap model that includes a gas-filled fractured reservoir with high attenuation, which attenuates and distorts the so-called bright spot.

开发早期油藏动态地质模型与油藏工程优化研究——以埕岛油田馆上段油藏为例

In order to developing reservoir of Upper of Ng at high-speed and high-efficient in Chengdao oilfield which is located in the bally shallow sea, the paper builds up a series of theory and means predicting and descripting reservoir in earlier period of oilfield development. There are some conclusions as follows. 1. It is the first time to form a series of technique of fine geological modeling of the channel-sandy reservoir by means of mainly seismic methods. These technique include the logging restriction seismic inversion, the whole three dimension seismic interpretation, seismic properties analysis and so on which are used to the 3-dimension distributing prediction of sandy body, structure and properties of the channel reservoir by a lot of the seismic information and a small quantity of the drilling and the logging information in the earlier stage of the oil-field development. It is the first time that these methods applied to production and the high-speed development of the shallow sea oilfield. The prediction sandy body was modified by the data of new drilling, the new reservoir prediction thinking of traced inversion is built. The applied effect of the technique was very well, according to approximately 200 wells belonging to 30 well groups in Chengdao oilfield, the drilling succeeded rate of the predicting sandy body reached 100%, the error total thickness only was 8%. 2. The author advanced the thinking and methods of the forecasting residual-oil prediction at the earlier stage of production. Based on well data and seismic data, correlation of sediment units was correlated by cycle-correlation and classification control methods, and the normalization and finely interpretation of the well logging and sedimentation micro-facies were acquired. On the region of poor well, using the logging restriction inversion technique and regarding finished drilling production well as the new restriction condition, the sand body distributing and its property were predicted again and derived 3-dimension pool geologic model including structure, reservoir, fluid, reservoir engineering parameter and producing dynamic etc. According to the reservoir geologic model, the reservoir engineering design was optimized, the tracking simulation of the reservoir numerical simulation was done by means of the dynamic data (pressure, yield and water content) of development well, the production rule and oil-water distributing rule was traced, the distributing of the remaining oil was predicted and controlled. The dynamic reservoir modeling method in metaphase of development was taken out. Based on the new drilling data, the static reservoir geologic model was momentarily modified, the research of the flow units was brought up including identifying flow units, evaluating flow units capability and establishing the fine flow units model; according to the dynamic data of production and well testing data, the dynamic tracing reservoir description was realized through the constant modification of the reservoir geologic model restricted these dynamic data by the theory of well testing and the reservoir numerical simulation. It was built the dynamic tracing reservoir model, which was used to track survey of the remaining oil on earlier period. The reservoir engineering tracking analysis technique on shallow sea oilfield was founded. After renewing the structure history since tertiary in Chengdao area by the balance section technique and estimating the activity character of the Chengbei fault by the sealing fault analysis technique, the meandering stream sediment pattern of the Upper of Ng was founded in which the meandering border was the uppermost reservoir unit. Based on the specialty of the lower rock component maturity and the structure maturity, the author founded 3 kinds of pore structure pattern in the Guanshang member of Chengdao oil-field in which the storing space mainly was primary (genetic) inter-granular pore, little was secondary solution pore and the inter-crystal pore tiny pore, and the type of throat mainly distributed as the slice shape and the contract neck shape. The positive rhythmic was briefly type included the simple positive rhythm, the complex positive rhythm and the compound rhythm. Interbed mainly is mudstone widely, the physical properties and the calcite interbed distribute localized. 5. The author synthetically analyzed the influence action of the micro-heterogeneity, the macro-heterogeneity and the structure heterogeneity to the oilfield water flood development. The efficiency of water flood is well in tiny structure of convex type or even type at top and bottom in which the water breakthrough of oil well is soon at the high part of structure when inject at the low part of structure, and the efficiency of water flood is poor in tiny structure of concave type at top and bottom. The remaining oil was controlled by sedimentary facies; the water flooding efficiency is well in the border or channel bar and is bad in the floodplain or the levee. The separation and inter layer have a little influence to the non-obvious positive rhythm reservoir, in which the remaining oil commonly locate within the 1-3 meter of the lower part of the separation and inter layer with lower water flooding efficiency.

井间地震技术研究和应用

Cross well seismic technique is a new type of geophysical method, which observes the seismic wave of the geologic body by placing both the source and receiver in the wells. By applying this method, it averted the absorption to high-frequency component of seismic signal caused by low weathering layers, thus, an extremely high-resolution seismic signal can be acquired. And extremely fine image of cross well formations, structure, and reservoir can be achieved as well. An integrated research is conducted to the high-frequency S-wave and P-wave data and some other data to determine the small faults, small structure and resolving the issues concerning the thin bed and reservoir's connectivity, fluid distribution, steam injection and fracture. This method connects the high-resolution surface seismic, logging and reservoir engineering. In this paper, based on the E & P situation in the oilfield and the theory of geophysical exploration, a research is conducted on cross well seismic technology in general and its important issues in cross well seismic technology in particular. A technological series of integrated field acquisition, data processing and interpretation and its integrated application research were developed and this new method can be applied to oilfield development and optimizing oilfield development scheme. The contents and results in this paper are as listed follows: An overview was given on the status quo and development of the cross well seismic method and problems concerning the cross well seismic technology and the difference in cross well seismic technology between China and international levels; And an analysis and comparison are given on foreign-made field data acquisition systems for cross-well seismic and pointed out the pros and cons of the field systems manufactured by these two foreign companies and this is highly valuable to import foreign-made cross well seismic field acquisition system for China. After analyses were conducted to the geometry design and field data for the cross well seismic method, a common wave field time-depth curve equation was derived and three types of pipe waves were discovered for the first time. Then, a research was conducted on the mechanism for its generation. Based on the wave field separation theory for cross well seismic method, we believe that different type of wave fields in different gather domain has different attributes characteristics, multiple methods (for instance, F-K filtering and median filtering) were applied in eliminating and suppressing the cross well disturbances and successfully separated the upgoing and downgoing waves and a satisfactory result has been achieved. In the area of wave field numerical simulation for cross well seismic method, a analysis was conducted on conventional ray tracing method and its shortcomings and proposed a minimum travel time ray tracing method based on Feraiat theory in this paper. This method is not only has high-speed calculation, but also with no rays enter into "dead end" or "blinded spot" after numerous iterations and it is become more adequate for complex velocity model. This is first time that the travel time interpolation has been brought into consideration, a dynamic ray tracing method with shortest possible path has been developed for the first arrivals of any complex mediums, such as transmission, diffraction and refraction, etc and eliminated the limitation for only traveling from one node to another node and increases the calculation accuracy for minimum travel time and ray tracing path and derives solution and corresponding edge conditions to the fourth-order differential sonic wave equation. The final step is to calculate cross well seismic synthetics for given source and receivers from multiple geological bodies. Thus, real cross-well seismic wave field can be recognized through scientific means and provides important foundation to guide the cross well seismic field geometry designing. A velocity tomographic inversion of the least square conjugated gradient method was developed for cross well seismic velocity tomopgraphic inversion and a modification has been made to object function of the old high frequency ray tracing method and put forward a thin bed oriented model for finite frequency velocity tomographic inversion method. As the theory model and results demonstrates that the method is simple and effective and is very important in seismic ray tomographic imaging for the complex geological body. Based on the characteristics of the cross well seismic algorithm, a processing flow for cross well seismic data processing has been built and optimized and applied to the production, a good section of velocity tomopgrphic inversion and cross well reflection imaging has been acquired. The cross well seismic data is acquired from the depth domain and how to interprets the depth domain data and retrieve the attributes is a brand new subject. After research was conducted on synthetics and trace integration from depth domain for the cross well seismic data interpretation, first of all, a research was conducted on logging constraint wave impedance of cross well seismic data and initially set up cross well seismic data interpretation flows. After it applied and interpreted to the cross well seismic data and a good geological results has been achieved in velocity tomographic inversion and reflection depth imaging and a lot of difficult problems for oilfield development has been resolved. This powerful, new method is good for oilfield development scheme optimization and increasing EOR. Based on conventional reservoir geological model building from logging data, a new method is also discussed on constraining the accuracy of reservoir geological model by applying the high resolution cross well seismic data and it has applied to Fan 124 project and a good results has been achieved which it presents a bight future for the cross well seismic technology.

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.

A study on the ignition process for the catalytic partial oxidation of methane to synthesis gas by MS-TPSR technique

The ignition processes for the catalytic partial oxidation of methane (POM) to synthesis gas over oxidic nickel catalyst (NiO/Al2O3), reduced nickel catalyst (Ni-0/Al2O3), and Pt-promoted oxidic nickel catalyst (Pt-NiO/Al2O3) were studied by the temperature-programmed surface reaction (TPSR) technique. The complete oxidation of methane usually took place on the NiO catalyst during the CH4/O-2 reaction, even with a pre-reduced nickel catalyst, and Ni-0 is inevitably first oxidized to NiO if the temperature is below the ignition temperature. It is above a certain temperature that Ni-0 is formed again, which leads to the start of the POM. The POM can be initiated at a much lower temperature on a Pt-NiO catalyst because of Pt promotion of the reduction of NiO. The POM in a fluidized bed can be easily initiated due to the addition of Pt.

On the evaluation of diffusivities in gels using the diffusion cell technique

Modeling of the gel-immobilized cell system requires accurate measurement of diffusion coefficients. Three methods of the quasi-steady-state (QSS) method, the time-lag (TL) method and a variant quasi-steady-state (VQSS) method were critically assessed and compared for the evaluation of diffusivities using the diffusion cell technique. Experimental data from our laboratory were used for the analysis of the influence of crucial theoretical assumptions not being fulfilled in each method. The results highlighted a risk in obtaining highly variable diffusion coefficients by not validating the QSS and the accuracy of the measurements. In the TL method, the estimation of diffusivities based on the plot intercept that was mostly used in the literature, results in a many fold lower value when compared to that based on the plot slope. The comparison with the QSS and VQSS methods confirmed similar diffusivity obtained by the TL method based on the plot slope. It thus suggested that the correct estimation of diffusivities by the TL method could be based on the plot slope only. Furthermore, the errors associated with the solute mass in the gel, the sample withdrawal and the non-negligible concentration changes in the chambers were also discussed. It is concluded that diffusion cell technique has to be employed cautiously for a correct evaluation of diffusivities. (C) 2001 Elsevier Science B.V. All rights reserved.

Drug-protein interaction studied by technique of microdialysis combined with high performance liquid chromatography

Drug-protein binding is an important process in determining the activity and fate of a pharmaceutical agent once it has entered the body. This review examines the method of microdialysis combined with high-performance liquid chromatography (HPLC) that has been developed;by ours to study such interactions, in which the microdialysis was applied to sample the free drug in the mixed solution of drug with protein, and HPLC to quantify the concentration of free drug in the microdialysate. This technique has successfully been used for determining various types of binding interactions between the low affinity drugs, high affinity drugs and enantiomers to HSA. For the case of competitive binding of two drugs to a protein in solution, a displacement equation has been derived and examined with four nonsteroidal anti-inflammatory drugs and HSA as model drugs and protein, respectively. Microdialysis with HPLC was adopted to determine simultaneously the free solute and displacing agent in drug-protein solutions. The method is able to locate the binding site and determine affinity constants even up to 10(7) L/mol accurately.