On-line introduction of high-pressure gas-liquid sample for capillary gas chromatographic analysis

An on-line sample introduction technique in capillary gas chromatograph (CGC) for the analysis of high-pressure gas-liquid mixtures has been designed and evaluated. A sample loop of 0.05 muL and a washing solvent loop of 0.5 muL are mounted on a 10-port switching valve, which serves as the injection valve. A capillary resistor was connected to the vent of sample loop in order to maintain the pressure of the sample. Both the sample and the washing solvent are transferred into the split-injection port through a narrow bore fused silica capillary inserted into the injection liner through a septum. The volume of the liner is used both as the pressure-release damper and evaporation chamber of the sample. On-line analysis of both reactants and resultants in ethylene olimer reaction mixture at 5 MPa was carried out, which demonstrated the applicability of the technique. (C) 2004 Elsevier B.V. All rights reserved.

On-line hyphenation of capillary isoelectric focusing and capillary gel electrophoresis by a dialysis interface

An on-line two-dimensional (2D) capillary electrophoresis (CE) system consisting of capillary isoelectric focusing (CIEF) and capillary gel electrophoresis (CGE) was introduced. To validate this 2D system, a dialysis interface was developed by mounting a hollow fiber on a methacrylate resin plate to hyphenate the two CE modes. The two dimensions of capillary shared a cathode fixated into a reservoir in the methacrylate plate; thus, with three electrodes and only one high-voltage source, a 2D CE framework was successfully established. A practical 2D CIEF-CGE experiment was carried out to deal with a target protein, hemoglobin (Hb). After the Hb variants with different isoelectric points (pIs) were focused in various bands in the first-dimension capillary, they were chemically mobilized one after another and fed to the second-dimension capillary for further separation in polyacrylamide gel. During this procedure, a single CIEF band was separated into several peaks due to different molecular weights. The resulting electrophoregrarn is quite different from that of either CIEF or CGE; therefore, more information about the studied Hb sample can be obtained.

On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

Scanned probe oxidation on an octadecyl-terminated silicon (111) surface with an atomic force microscope: kinetic investigations in line patterning

Scanned probe oxidation (SPO) nanolithography has been performed with an atomic force microscope (AFM) on an octadecyl-terminated silicon (111) surface to create protuberant oxide line patterns under ambient conditions in contact mode. The kinetic investigations of this SPO process indicate that the oxide line height increases linearly with applied voltage and decreases logarithmically with writing, speed. The oxide line width also tends to vary with the same law. The ambient humidity and the AFM tip state can remarkably influence this process, too. As compared with traditional octadecylsilated SiO2/Si substrate, such a substrate can guarantee the SPO with an obviously lowered voltage and a greatly increased writing speed. This study demonstrates that such alkylated silicon is a promising silicon-based substrate material for SPO nanolithography.

Determination of Hg(II) in waters by on-line preconcentration using Cyanex 923 as a sorbent - Cold vapor atomic absorption spectrometry

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (11) was then eluted with 10% HNO3 and subsequently reduced by NaBH4 to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min(-1) sample loading rate. The detection limit was 0.2 ng L-1 and much lower than that of conventional method (around 15.8 ng L-1). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L-1 of Hg and the linear working curve is from 20 to 2000 ng L-1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory.

The research of cellulose derivatives as chiral stationary phases and high performance liquid chromatography with polarimeter as on-line detector

Three cellulose derivatives were synthesized and used as chiral stationary phases based on silica gel. The effects of adsorbances on the column numbers and stabilities have been investigated. These stationary phases exhibited high chiral recognition for various racemates. At the same time, the on-line curves of polarimeter were obtained by high performance liquid chromatography with polarimeter as on-line detector.

APPLICATION OF THE MOMENT METHODS TO ANALYSIS OF X-RAY-DIFFRACTION LINE-PROFILE FOR PA1010-BMI SYSTEM

Pure X-ray diffraction profiles have been analysed for polyamide 1010 and PA1O1O-BMI system by means of multipeak fitting resolution of X-ray diffraction. The methods of variance and fourth moment have been applied to determine the particle size and strain values for the paracrystalline materials. The results indicated that both variance and fourth moment of X-ray diffraction line profile yielded approximately the same values of the particle size and the strain. The particle sizes of (100) reflection have been found to decrease with increasing BMI content, whereas the strain values increased.

ON THE SIGNIFICANCE OF WAVELENGTH POSITIONING ACCURACY IN MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper reports some definite evidence for the significance of wavelength positioning accuracy in multicomponent analysis techniques for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). Using scanning spectrometers commercially available today, a large relative error, DELTA(A) may occur in the estimated analyte concentration, owing to wavelength positioning errors, unless a procedure for data processing can eliminate the problem of optical instability. The emphasis is on the effect of the positioning error (deltalambda) in a model scan, which is evaluated theoretically and determined experimentally. A quantitative relation between DELTA(A) and deltalambda, the peak distance, and the effective widths of the analysis and interfering lines is established under the assumption of Gaussian line profiles. The agreement between calculated and experimental DELTA(A) is also illustrated. The DELTA(A) originating from deltalambda is independent of the net analyte/interferent signal ratio; this contrasts with the situation for the positioning error (dlambda) in a sample scan, where DELTA(A) decreases with an increase in the ratio. Compared with dlambda, the effect of deltalambda is generally less significant.

WAVELENGTH POSITIONING ERRORS AND TRUE DETECTION LIMIT IN RELATION TO MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper deals with the evaluation of the relative error (DELTA(A)) in estimated analyte concentrations originating from the wavelength positioning error in a sample scan when multicomponent analysis (MCA) techniques are used for correcting line interferences in inductively coupled plasma atomic emission spectrometry. In the theoretical part, a quantitative relation of DELTA(A) with the extent of line overlap, bandwidth and the magnitude of the positioning error is developed under the assumption of Gaussian line profiles. The measurements of eleven samples covering various typical line interferences showed that the calculated DELTA(A) generally agrees well with the experimental one. An expression of the true detection limit associated with MCA techniques was thus formulated. With MCA techniques, the determination of the analyte and interferent concentrations depend on each other while with conventional correction techniques, such as the three-point method, the estimate of interfering signals is independent of the analyte signals. Therefore. a given positioning error results in a larger DELTA(A) and hence a higher true detection limit in the case of MCA techniques than that in the case of conventional correction methods. although the latter could be a reasonable approximation of the former when the peak distance expressed in the effective width of the interfering line is larger than 0.4. In the light of the effect of wavelength positioning errors, MCA techniques have no advantages over conventional correction methods unless the former can bring an essential reduction ot the positioning error.

大别－苏鲁造山带与华北陆块东部岩石层三维速度结构

The 3-D velocity images of the crest and upper mantle beneath the region of 112° -124°E, 28°-39°N including the Dabie-Sulu orogenic belt are reconstructed by using 36405 P-wave arrivals of 3437 regional and 670 distant earthquakes during the period from 1981 to 1996, and gridding the area of 0.5° * 0.5°. The results of tomography demonstrate that: 1. The results of tomographic imaging show a broad heterogeneity in P wave velocity structure for the lithosphere beneath the Dabie-Sulu orogenic belt. 2. In the Dabie orogenic belt, the velocity patterns in the crust are different among various tectonic units. The Dabie and Qinling orogenic belts are remarkable in the tomographic images, and in mm the Hongan and Dabie blocks in the Dabie orogenic belt are also imaged very distinguishably. 3. A velocity (about 5.9～6.0 km/s) layer exists in the Dabie block at depth between 15～25 km, which is coincident with the low-resistance layer at the depth of 12-23 km, being inferred to be the tectonic detachment zone and suggesting that the extension detachment structure was formed in the middle crust. Beneath the southern and northerm Dabie tectonic units, the north-dipping high-velocity (at level of 6.5 ～ 6.6 km/s) block was developed in the crust, which might be correlated with the UHP rockswith low content of the meta-ultramafic rocks. This result is in agreement with the geological observation on the surface. 4. The velocity image at 40 km depth reveals the features at the top of mantle and the configuration of the Moho discontinuity. The depth of the Moho changes slightly along the trend of the orogenic belt. It in Hongan block is less than 40 km, but it is different in the western and eastern parts of the Dabie block, the former is more than 40 km, and the latter less than or equal to 40 km. The remnant of the mountain root exists between the Shangcheng-Macheng fault and the line of Huoshan-Yuexi-Yingshan in the Dabie orogenic belt, and beneath the southern and northern Dabie tectonic units. However, the thickness of the Moho is about 40 km and there is no obvious changes, which suggest that the Dabie orogenic belt has been experienced quite in the gravity equilibration. The Moho's depth in the Sulu is less than 40 km. 5. There is a dipping slab-like high-velocity body in the uppermost mantle. It is sandwiched by slow velocities and exists beneath the Dabie-Sulu orogenic belt in the range of depths between the Moho discontinuity and 110 km at least. This high-velocity body outlines a picture of the slab interpreted as the remnant of the Triassic subducted YZ. 6. The Sulu orogenic belt displays "crocodilian" velocity structure, the upper crust of the Yangtze thrusted over the Huabei crest, and the Huabei crust indented into the Yangtze crust, where the ancient subduction zone of the Yangtze lithosphere located. Based on the previous geological data, this structure is not related with the collision between the Yangtze and Sino-Korean Blocks, but caused by the sinistral offset of the Tan-Lu Fault. Studied on the velocity structure of the eastern Huabei lithosphere indicates: 1. The 'present-day' lithosphere of the eastern Huabei is between 40-100 km thick with greatly thinned lithosphere around the Bohai Sea. Generally, thickness of the lithosphere in this region decreased eastwards. 2. The attenuation of the lithosphere is attributed to the strongly uplift of the asthenosphere. In the area between the Taihang Mountains and the Tan-Lu Fault, there is a 'lever' with red low velocity belt, it is clearly defined, transverse continuity, depth between 100-150 km, local variations visible, and an upwards trend towards the Bohai Sea. Generally, the velocity structure in the mantle beneath the lithosphere displays irregular column-shape consisting of alternating high and low velocities, and when cold high velocity ancient lithosphere connects with the hot low velocity mantle materials forming precipitous compact structure. More heat pathways from the mantle occur towards the Tan-Lu Fault. 3. The strongly irregular characteristics of the contact between the asthenosphere and the lithosphere is induced by the long-term hot, chemical erosion and alteration on the contact. 4. There are still preserved high velocity lithosphedc root beneath Huabei with 'block-shape' distribution and surrounded by hot materials. Results of our studies indicate that the evolution models of the eastern China mantle are characterized by the direct contact between the uplifted lithosphere and the Huabei Craton accompanying the upwelling of the deep mantle materials. At the contact betwen the lithosphere and the asthenosphere, the upwelled mantle materials replaced and altered the lower lithosphere forming the metasome through the hot and chemical modifications impacted on the Craton lithosphere, and changed it into the lithosphere gradually, resulting in the lithospheric thinning. Thus, the lithospheric thinning is the result of the upwelling of the asthenosphere.