南海北部大陆边缘盆地热演化史及其与油气关系

This thesis focuses on the present-day thermal field features, evolution and their connections to hydrocarbon generation of the three continental margin basins-the Yinggehai (Yingge Sea), Qiongdongnan(southeast Qiong), and Pear River Mouth basins-in northern South China Sea, based on available data from drillings, loggings, seismic cross-sections, BHTs, thermal indicators (Ro%, inclusion, etc) and geopressure measurements. After studying of present-day distribution of geothermal field and thermal disturbance of fluid in the sedimentary strata, the author discovered that the distribution of gas fields in Yinggehai Basin are closely related to the distribution of anomalously high thermal gradient area, whereas it is not the case for the Pear River Mouse Basin. And detailed processing of the fluid inclusion data indicates that geothermal fluids activated frequently in this area, and they may mainly be derived upward from the overpressure and hydrocarbon-generating beds, 3000-4500 m in depth. Therefore, the abnormal gradients in sedimentary beds were mainly caused by the active geothermal fluids related to hydrocarbon migrating and accumulating in this area. Because of the effect of overpressure retarding on vitrinite reflectance, the thermal indicators for thermal history reconstruction should be assessed before put into use. Although some factors, such as different types of kerogen, heating ratio, activities of thermal fluids and overpressure, may have effects on the vitrinite reflectance, under the circumstance that thermal fluids and overpressure co-exist, overpressure retarding is dominant. And the depth and correction method of overpressure retarding were also determined in this paper. On the basis of reviewing the methods of thermal history studies as well as existing problems, the author believes that the combination of thermal-indicator-inversion and tectono-thermal modeling is an effective method of the thermal history reconstruction for sedimentary basins. Also, a software BaTherMod for modeling thermal history of basins was successfully developed in this work. The Yinggehai Basin has been active since Tertiary, and this was obviously due to its tectonic position-the plate transition zone. Under the background of high thermal flow, long-term quick subsidence and fluid activities were the main reasons that lead to high temperature and overpressure in this basin. The Zhujiangkou Basin, a Tertiary fault-basin within the circum-Pacific tectonic realm, was tectonically controlled by the motion of the Pacific Plate and resembles the other petroliferous basins in eastern China. This basin developed early, and characterized intensive extension in the early stage and weak activity in the later stage of its development. Whereas the Qiongdongnan Basin was in a weak extension early and intensity of extension increased gradually. The relative geographical locations and the extensional histories of three basins ilustrate that the northern continental margin of South China Sea spread from south to north. On the other hand, the Qiongdongnan and Yinggehai Basins may have been controlled by the same tectonic regime since later Tertiary, whereas the Zhujiangkou Basin was not meaningfully influenced. So, the tectono-thermal evolution character of the Qiongdonnan basin should be closely to the other two. It may be concluded that the three basins have been developed within the active continental margin since Tertiary, and the local lithosphere might undergo intensive extension-perhaps two or three times of episodic extension occurred. Extension lead to large tectonoc subsidence and extreme thick Tertiary sediments for hydrocarbon generation in the basins. In response to the periodic extension of the basins, the palaeothermal flow were also periodical. The three basins all have the characteristics of multi-phase thermal evolutions that is good for oil-gas generation. And the overpressure expands the depth range of oil-gas habitat, which is meaningful to petroleum exploration in this region.

孤南-三合村洼陷含油气系统研究

The development petroleum geology has made people from studying and studying and predicting in statically and respectively the pool-forming conditions of an area such as oil source bed, reservoir, overlying formation, migration, trap and preservation, etc. to regarding these conditions as well as roles of generation, reservation and accumulation as an integrated dynamic evolution development system to do study .Meanwhile apply various simulating means to try to predict from quantitative angle. Undoubtedly, the solution of these questions will accumulate exploration process, cut down exploration cost and obtain remarkable economic and social benefits. This paper which take sedimentology ,structural geology and petroleum geology as guides and take petroleum system theory as nucleus and carry out study thinking of beginning with static factor and integration of point and face as well as regarding dynamic state factor as factor and apply study methods of integration of geology, Lab research and numerical modeling proceed integrated dissect and systematic analysis to GuNan-SanHeCun depression. Also apply methods of integration of sequence stratigraphy, biostratigraphy, petrostratigraphy and seismic data to found the time-contour stratigraphic framework and reveal time-space distribution of depositional system and meantime clarify oil-source bed, reservoir and overlying distribution regular patterns. Also use basin analysis means to study precisely the depositional history, packed sequences and evolution. Meanwhile analyze systematically and totally the fracture sequence and fault quality and fault feature, study the structural form, activity JiCi and time-space juxtaposion as well as roles of fault in migration and accumulation of oil and gas of different rank and different quality fault. Simultaneously, utilize seismic, log, analysis testing data and reservoir geology theory to do systematic study and prediction to GuNan-SanHeCun reservoir, study the reservoir types macroscopic distribution and major controlling factors, reservoir rock, filler and porosity structural features as well as distribution of reservoir physical property in 3D space and do comprehensive study and prediction to major controlling and influential factors of reservoir. Furthermore, develop deepingly organic geochemistry comprehensive study, emphasis on two overlaps of oil source rock (ESI, ES3) organic geochemistry features, including types, maturity and spatial variations of organic matter to predict their source potential .Also apply biological marks to proceed oil-to-source correlation ,thereby establish bases for distribution of petroleum system. This study recover the oil generation history of oil source rocks, evaluate source and hydrocarbon discharge potential ,infer pool-forming stages and point out the accumulation direction as well as discover the forming relations of mature oil-source rock and oil reservoir and develop research to study dynamic features of petroleum system. Meanwhile use systematic view, integrate every feature and role of pool forming and the evolution history and pool-forming history, thereby lead people from static conditions such as oil source bed, reservoir, overlying formation, migration, trap and preservation to dynamically analyzing pool-forming process. Also divide GuNan-SanHeCun depression into two second petroleum system, firstly propose to divide second petroleum system according to fluid tress, structural axis and larger faults of cutting depression, and divide lower part of petroleum system into five secondary systems. Meanwhile establish layer analysis and quantitative prediction model of petroleum model, and do quantitative prediction to secondary petroleum system.

准噶尔盆地三个泉凸起油气成藏条件及动力学研究

Sangequan Uplift in Junggar Basin is an inherited positive structure, which has undergone many times of violent tectonic movements, with high tectonic setting, and far away from the oil-source sag, reservoir forming condition is complex. Combining sequence stratigraphy, depositional facies, reservoir formation theory with seismic and well logging analysis, this paper conducted integrated study on the hydrocarbon migration, accumulation, entrapment conditions, the reservoir forming dynamics and the forming model, and acquired the following recognition: (1) The special reservoir formation conditions that enable Sangequan Uplift to form a giant oil-gas field of over 100 million tons of reserves are as follows: (D Deltaic frontal sandbody is developed in Jurassic Xishanyao Formation, Toutunhe Formation and Lower Cretaceous Hutubihe Formation, with good reservoir quality;? Abundant hydrocarbon resources are found in Western Well Pen-1 Sag, which provides sufficient oil sources for reservoir formation of Sagequan Uplift; ?The unconformity-fault-sandbody system has formed a favorable space transporting system and an open conduit for long-distance hydrocarbon migration; ?fault, low amplitude anticline and lithological traps were well developed, providing a favorable space for hydrocarbon accumulation. (2) The most significant source beds in the Western Well Pen-1 Sag are the Mid-Permian Lower Wuerhe Formation and Lower-Permian Fengcheng Formation. The oil in the Well Block Lu-9 and Shinan Oilfield all originated from the hydrocarbon source beds of Fengcheng Formation and Lower Wuerhe Formation in the Western Well Pen-1 Sag and migrated through Jidong and Jinan deep faults linking unconformity of different regions from sources to structural highs of the uplift and shallow horizons. (3) There were 2 reservoir formation periods in District Sangequan: the first was in late Cretaceous during which the upper part of Xishanyao Formation and Toutunhe Formation; the second was in Triassic, the main resources are high-maturity oil and gas from Fengcheng Formation and Wuerhe Formation in Western Pen-1 Well sag and the gas from coal measure strata of Xishanyao Formation, that were accumulated in Hutubihehe Formation. (4) Model of the hydrocarbon migration, accumulation, reservoir formation of the study area are categorized as three types starting from the hydrocarbon source areas, focusing on the faults and unconformity and aiming at reservoirs: ① Model of accumulation and formation of reservoir through faults or unconformities along the "beam" outside source; ②Model of migration, accumulation and reservoir formation through on-slope near source;③Model of migration, accumulation and reservoir formation of marginal mid-shallow burial biogas-intermediate gas. (5) Pinchout, overlap and lithologic traps are developed in transitional zones between Western Well Pen-1 sag and Luliang uplift. Many faulted blocks and faulted nose-like traps are associated with large structures on Sangequan uplift. Above traps will be new prospecting areas for further hydrocarbon exploration in future.

东营凹陷中央隆起带次生油藏成藏机制和预测

It is the key project of SINOPEC at ninth five years period with a lot of work and very difficult, which the main object are the study of pool-forming mechanism, distribution rule and pool-forming model of complex secondary pool at Dongying formation in high mature exploration area, and building theories and methods of research, description and prediction of secondary fault block pool. This paper apply comprehensively with various theories, method and techniques of geology, seismic, well log, reservoir engineering, meanwhile apply with computer means, then adopt combination of quality and quantitative to develop studies of pool-forming mechanism, model and pool prediction of fault block pool. On the based of stretch, strike-slip, reversal structure theories, integrated the geometry, kinematics, and dynamics of structure, it is show that the structure framework, the structure evolve, formation mechanism of central uplift belt of Dongying depression and control to formation and distribute of secondary complex fault block pool. The opening and sealing properties, sealing mechanism and sealing models of pool-controlling fault are shown by using quality, direction of normal stress, relations between interface and rock of two sides of fault and shale smear factor (SSF), as well as the juxtaposition of fault motion stage and hydrocarbon migration, etc. The sealing history of controlling fault, formation mechanism and distribute the regulation are established by combining together with bury history, structure evolve history, fault growth history stress field evolve history, which can be guide exploration and production oil field. It were bring up for the first time the dynamics mechanism of Dongying central uplift which were the result of compound tress field of stretch, strike-slip and reversal, companion with reversal drag structure, arcogenesis of paste and salt beds. The dual function of migration and sealing of fault were demonstrated in the research area. The ability of migration and sealing oil of pool-controlling fault is controlled by those factors of style of fault combination, activity regulation and intensity of fault at the period of oil migration. The four kinds of sealing model of pool-controlling fault were established in the research area, which the sealing mechanism of fault and distribution regulation of oil in time and space. The sealing ability of fault were controlled by quality, direction of normal stress, relations between interface and rock of two sides of fault and shale smear factor (SSF), as well as the juxtaposition of fault motion stage and hydrocarbon migration, etc. The fuzzy judge of fault sealing is the base of prediction of secondary pool. The pool-forming model of secondary was established in the research area, which the main factors are ability migration and sealing. The transform zone of fault, inner of arc fault and the compound area of multi fault are enrichment region of secondary pool of Dongying formation, which are confirm by exploration with economic performance and social performance.

西南天山托云盆地白垩-新生代古地磁结果及其构造意义

Western China is regarded as an assemblage of blocks or microplates. The India/Asia postcollisional kinematics of these blocks has attracted many geologists to pay attentions, especially on the geodynamics and intracontinental deformation of Tibetan and adjoining parts of central Asia. So far there are still many debates on the amount of continental shortening and extrusion within Western China blocks. Paleomagnetism plays a very important role in the paleogeographic reconstruction and depiction of kinematics of the blocks, however the unequilibrium of paleomagentic data obtained from Western China prevents paleomagnetists from studying the kinematics and intracontinental deformation on the Tibetan plateau and the central Asia. Moreover, shallower inclinations observed in the Cretaceous and Cenozoic terrestrial red sediments in central Asia makes it difficult to precisely estimate the northward convergence of Tibetan plateau and its adjacent areas since the onset of the Indian/Asian collision. In this thesis, detailed rock magnetic, chronological and paleomagnetic studies have been carried out on the Tuoyun Basin in the southwestern Tianshan to discuss the possible continental shortening and tectonic movements since the Cretaceous-Tertiary. Ar-Ar geochronological study has been conducted on the upper and lower basalt series from the Tuoyun Basin, yielding that the lower and upper basalt series were extruded during 115-113 Ma and 61.8-56.9 Ma, respectively. Both the age spectrum and inverse isochron show that the samples from the upper and lower basalt series have experienced no significant thermal events since extrusion of the baslts. Rock magnetic studies including temperature dependence of magnetization and susceptibility during a heating-cooling cycle from temperature up to 600 ℃ suggest that the baslt samples from the lower and upper basalt series are ferromagnetically predominant of magnetite and a subordinate hematite with a few sites of titanomagnetite. The predominant magnetic mineral of the intercalated red beds is magnetite and hematite. Anisotropy of magnetic susceptibility shows that both the baslts and the intercalated red beds are unlikely to have undergone significant strain due to compaction or tectonic stress since formation of the rocks. The stable characteristic remanent magnetization (ChRM) isolated from the most samples of the upper and lower basalt series and intercalated red beds, passes fold test at the 99% confidence level. Together with the geochronological results, we interpret the characteristic component as a primary magnetization acquired in the formation of rocks. Some sites from both the upper and lower basalts yielded shallower inclinations than the reference field computed from the Eurasia APW, we prefer to argue that these shallow inclinations might be related to geomagnetic secular variation, whereas the shallow inclination in the intercalated red beds is likely to be related to detrital remanent magnetization. Paleomagnetic results from the early Cretaceous-Paleogene basalts indicate that no significant N-S convergence has taken place between the Tuoyun Basin and the south margin of Siberia. Furthermore, the Cretaceous and Tertiary paleomagnetic results suggest that the Tuoyun Basin was subjected to a local clockwise rotation of 20°-30° with respect to Eurasia since the Paleocene time, which is probably subsequent to the Cenozoic northward compression of the Pamir arc.

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.

Simultaneous chiral separation using a combinatorial molecular imprinting phase

Molecular imprinting chiral stationary phase against Cbz-L-Serine (Cbz-L-Ser) and Cbz-L-Alaine (Cbz-L-Ala) were prepared utilizing acrylamide + 2-vinylpyridine as combined basic functional monomers. Cross-selectivity was used to obtain simultaneous chiral separations of Cbz-DL-Ser and Cbz-DL-Ala by connecting two columns packed with Cbz-L-Ser and Cbz-L-Ala imprinted chiral stationary phase, respectively.

Capillary electrochromatography using a strong cation-exchange column with a dynamically modified cationic surfactant

A novel mode of capillary electrochromatography (CEC), called dynamically modified strong cation-exchange CEC (DMSCX-CEC), is described in this paper. A column packed with a strong cation-exchange (SCX) packing material was dynamically modified with a long-chain quaternary ammonium salt, cetyltrimethylammonium bromide (CTAB), which was added to the mobile phase. CTAB ions were adsorbed onto the surface of the SCX packing material, and the resulting hydrophobic layer on this packing was used as the stationary phase. Using the dynamically modified SCX column, neutral solutes were separated with the CEC mode. The highest number of theoretical plates obtained was about 190 000/m, and the relative standard deviations (RSD's) for migration times and capacity factors of alkylbenzenes were less than 1.0% and 2.0% for five consecutive runs, respectively. The effects of CTAB and methanol concentrations and the pH value of the mobile phase on the electroosmotic flow and the separation mechanism were investigated. Excellent simultaneous separation of the basic and neutral solutes in DMSCX-CEC with a high-pH mobile phase was obtained, A mixture containing the acidic, basic, and neutral compounds was well separated in this mode with a low-pH mobile phase; however, peak tailing for basic compounds was observed in this mobile phase.

Alkaline treatment of the cellulose fiber affecting membrane column behaviour for high-performance immunoaffinity chromatography

The original cellulose fibers and those treated by alkaline solution were both used to prepare the acrylic membranes. The two kinds of membranes were packed into the columns for high-performance immunoaffinity chromatography by the immobilization of protein A on them. It was observed that the alkaline treatment of the cellulose fiber decreased the pressure resistance of the membrane to the mobile phases and greatly increased the accessible volume to the proteins, but affected the adsorption capacity of human IgG on the protein A membrane columns less. There is little difference between those two kinds of membranes on the adsorption capacities of HIgG, which means that the alkaline treatment of the cellulose fiber only significantly changes the void volume inter-membrane, and the porosity and surface area of membrane less. Alkaline treatment of the cellulose fiber reduced the membrane-column efficiency significantly. Some typical examples for the immunoaffinity analysis of IgG from human and dog plasma on the protein A membrane columns are illustrated. Copyright (C) 2000 John Wiley & Sons, Ltd.

Influence of methanol on retention of hydrophobic organic chemicals in soil leaching column chromatography

The influence of methanol in methanol-water mixed eluents on the capacity factor (P), an important parameter which could depict leaching potential of hydrophobic organic chemicals (HOCs) in soil leaching column chromatography (SLCC), was investigated. Two reference soils, GSE 17201 obtained from Bayer Landwirtschaftszentrum, Monheim, Germany and SP 14696 from LUFA, Spencer, Germany, were used as packing materials in soil columns, and isocratic elution with methanol-water mixtures at different volume fractions of methanol (phi) were tested. Shortterm exposure of the column (packed with the GSE 17201 soil) to the eluents increased solute retention by a certain (23% log-unit) degree evaluated through a correlation with the retention on the same soil column but unpreconditioned by methanol-containing eluents. Long-term exposure of soil columns to the eluents did not influence the solute retention. A log-linear equation, log k' = log k'(w) - Sphi, could well and generally describe the retention of HOCs in SLCC. For the compounds of homologous series, logk'(w), had good linear relationship with S, indicating the hydrophobic partition mechanism existing in the retention process. (C) 2002 Elsevier Science Ltd. All rights reserved.

Retention behavior of hydrophobic organic chemicals as a function of temperature in soil leaching column chromatography

To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degreesC was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degreesC (k'(30)/k'(40)) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C-18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former. (C) 2002 Elsevier Science Ltd. All rights reserved.

Fast analysis of capillary electrochromatography with non-porous ODS as the stationary phase

High-speed capillary electrochromatography was developed on both short and long packed columns with 2 mu m non-porous ODS as the stationary phase. Factors that affect the analysis time of samples, such as voltage, electrolyte concentration, pH and organic modifier concentration in the mobile phase, were studied systematically. Fast analysis of aromatic compounds within 13 seconds was realized with column efficiency of 573,000 plates/m and a R.S.D.% of the retention times of all components in 8 consecutive injections below 1.0%. which demonstrated the high efficiency and high reproducibility of such a technique. In addition, DNPH derived aldehydes and ketones in both standards and environmental samples were separated with high speed.

Capillary electrochromatography with a silica column with a dynamically modified cationic surfactant

A novel mode of capillary electrochromatography (CEC), called dynamically modified silica-capillary electrochromatography, is described in this paper. The column packed with bare silica was dynamically modified with long chain quaternary ammonium salt, cetyltrimethylammonium bromide (CTAB), which was added into the mobile phase. CTAB ions were adsorbed onto the surface of bare silica, and the resulted hydrophobic layer on the silica gel was used as the stationary phase; Using the dynamically modified silica column, neutral solutes were separated by CEC. The highest number of theoretical plates obtained was about 71 500/m and the relative standard deviations for t(0) and capacity factor of toluene were 4.7% and 4.9% for 20 consecutive runs, respectively. The separation mechanism of neutral solutes and the influence of mobile phase composition on the separation was investigated. The separation of nitrogen-containing solutes was carried out with this mode and the peak tailing of basic solute was effectively eliminated because the adsorption of basic solute on silica was blocked by the preferred adsorption of CTAB. (C) 1999 Elsevier Science B.V. All rights reserved.

Separation of neutral compounds by high speed capillary electrochromatography

With using short capillary column packed with porous and non-porous ODS stationary phases, high speed separation of 6 neutral aromatic compounds within 36 s by capillary electrochromatography (CEC) has been performed. Good reproducibility of the migration times for those solutes in high speed CEC was observed with RSD less than 1%. Both the linear velocity of EOF and the current linearly increases with the applied voltage, which means that the thermal effect by Joule heating was small. However, the capacity factor of solutes was found to decrease with the increase of the applied voltage, which was caused by the fact that about several seconds needed for the increase of voltage from 0 to applied value on a commercial CE instrument made larger contributions to the migration times of the early eluted compounds than those of lately eluted ones during high speed CEC, and voltage effect would increase with the higher applied voltage used. The linear relationship between the logarithm of capacity factor and the number of carbon for homologous compounds was observed, and positive value of slope means that the hydrophobicity of solutes is one of the main contribution factors to retention in high speed CEC packed with ODS stationary phases.

Prediction of soil organic partition coefficients by a soil leaching column chromatographic method

The soil organic partition coefficient (K-oc) is one of the most important parameters to depict the transfer and fate of a chemical in the soil-water system. Predicting K-oc by using a chromatographic technique has been developing into a convenient and low-cost method. In this paper, a soil leaching column chromatograpy (SLCC) method employing the soil column packed with reference soil GSE 17201 (obtained from Bayer Landwirtschaftszentrum, Monheim, Germany) and methanol-water eluents was developed to predict the K-oc of hydrophobic organic chemicals (HOCs), over a log K-oc range of 4.8 orders of magnitude, from their capacity factors. The capacity factor with water as an eluent (k(w)') could be obtained by linearly extrapolating capacity factors in methanol-water eluents (k') with various volume fractions of methanol (phi). The important effects of solute activity coefficients in water on k(w)' and K-oc were illustrated. Hence, the correlation between log K-oc and log k(w)' (and log k') exists in the soil. The correlation coefficient (r) of the log K-oc vs. log k(w)' correlation for 58 apolar and polar compounds could reach 0.987, while the correlation coefficients of the log K-oc-log k' correlations were no less than 0.968, with phi ranging from 0 to 0.50. The smaller the phi, the higher the r. Therefore, it is recommended that the eluent of smaller phi, such as water, be used for accurately estimating K-oc. Correspondingly, the r value of the log K-oc-log k(w)' correlation on a reversed-phase Hypersil ODS (Thermo Hypersil, Kleinostheim, Germany) column was less than 0.940 for the same solutes. The SLCC method could provide a more reliable route to predict K-oc indirectly from a correlation with k(w)' than the reversed-phase liquid chromatographic (RPLC) one.