临界流文丘里喷嘴流量计的原理与应用

提出了流出系数和临界流函数实用公式和图表对临界流文丘里喷嘴的实际应用能起到指导作用     

Determination of methylmercury in environmental matrixes by on-line flow injection and atomic fluorescence spectrometry

The precision and bias of monomethylmercury (MMHg) determinations in environmental samples can be improved by directly coupling and automating the numerous steps involved with analysis of this toxic Hg species. We developed a simple and robust mercury speciation analyzer (MSA) for measurement of MMHg in environmental matrixes. This on-line hyphenated system couples the main analytical steps, including sample introduction, aqueous-phase ethylation, Tenax preconcentration, and gas chromatographic separation, to cold vapor atomic fluorescence detection and data acquisition. Here we describe the MMHg-MSA, present results of laboratory optimization and performance tests, and compare the reproducibility between dual analytical channels. With alternating sample concentration and analysis, a dual-channel system permits six high-accuracy MMHg determinations per hour. Additional advantages compared to the traditional manual method include ease of operation and high precision (<5% relative standard deviation). The MSA is applicable to the determination of MMHg in various environmental matrixes, and it can be fully automated. This method was validated by analysis of MMHg in certified reference materials of sediment and biological tissue. Estimated detection limits for MMHg with the MSA are approximately 0.01 ng g(-1) for a 0.1-g sample of dry sediment or fish and approximately 0.01 ng L(-1) for 0.15 L of water.     

Continuous on-line monitoring of extracellular ascorbate depletion in the rat striatum induced by global ischemia with carbon nanotube-modified glassy carbon electrode integrated into a thin-layer radial flow cell

This study describes a novel analytical system integrating in vivo microdialysis sampling with a radial thin-layer flow cell with a single-walled carbon nanotube (SWNT)-modified glassy carbon electrode as working electrode for continuous and on-line monitoring of ascorbate depletion in the rat striatum induced by global ischemia. The SWNTs, especially those after vacuum heat treatment at 500 degrees C, are found to be able to enhance the electron-transfer kinetics of ascorbate oxidation at a low potential (ca. -50 mV) and possess a strong ability against electrode fouling. These properties essentially make it possible to determine ascorbate with a good stability and high selectivity against catecholamines and their metabolites and other electroactive species of physiological levels. While being integrated with in vivo microdialysis to assemble an on-line analytical system, the electrode is proved useful for continuous and sensitive monitoring of the basal dialysate level of ascorbate and its depletion in the rat striatum induced by global ischemia. The basal dialysate level of ascorbate is determined to be 5.0 +/- 0.5 microM (n = 5) and a 50 +/- 10% (n = 3) depletion is recorded for the basal ascorbate after 4 h of global ischemia.     

Laser-enhanced ionization detection of Pb in seawater by flow injection analysis with on-line preconcentration and separation

The flame laser-enhanced ionization (LEI) technique is coupled with the flow injection analysis system to measure the trace lead amounts in aqueous solution and in seawater. The flow injection (FI) manifold is incorporated with a microcolumn packed with a C18 bonded silica. The chelating agent DDPA is used to form the Pb-DDPA complex, which may be sorbed in the microcolumn and then eluted with methanol. The preconcentrated Pb is then detected by the LEI technique with either single-step or two-step excitation. At 5- and 15-mL volume-fixed sample loading, the detection limits of 0.011 and 0.0033 ng/mL (11 and 3.3 ppt) and enrichment factors of 16 and 48 are achieved, respectively, using a two-step FI-LEI. The sensitivity of the current system proves to be better by at least 1 order of magnitude than that of conventional LEI method. The FI-LEI also increases the tolerance of matrix interference. The LEI signal is slightly reduced to 80% intensity as 10,000 micrograms/mL (ppm) Na and K matrixes are mixed in the lead solution. The resistance to the alkali matrixes is enhanced approximately 4 times that reported previously using a similar water-immersed probe as a LEI collector. Finally, the FI-LEI is for the first time applied to detect the Pb content in seawater, achieving a result of 0.0112 +/- 0.0006 ng/mL (ppb) consistent with the certified value of 0.013 +/- 0.005 ng/mL (ppb).     

Continuous flow microfluidic demixing of electrolytes by induced charge electrokinetics in structured electrode arrays

A continuous flow microfluidic demixing process is realized. It utilizes high external electrical fields that are applied over electrically floating noble metal electrodes in an otherwise straight microchannel. The process converts axial electrical potential gradients into lateral molecular selective transport via a structure oriented ensemble of numerous electrodes. While the individual electrodes locally modify the electrolyte distribution by nonlinear electrokinetic effects and concentration polarization, the directed orientation of the electrode array combines the individual polarization zones to a dedicated molecular enrichment against the generated concentration gradient. A homogeneously concentrated electrolyte can be separated into arbitrarily shaped laminae of increased and depleted concentration by the presented microfluidic demixer.     

Speciation and determination of thallium by on-line microcolumn separation/preconcentration by flow injection-flame atomic absorption spectrometry using immobilized oxine as sorbent

A flow injection analysis (FIA) system incorporation a microcolumn of immobilized oxine on surfactant-coated alumina had been devised for performing rapid thallium enrichment/matrix removal in flame atomic absorption spectrometry (FAA). The preconcentration is based on the deposition of thallium(I) on microcolumn and subsequent elution with 500 microl of sodium thiosulfate (1 moll(-1)). In the presence of EDTA, only Tl(I) was retained on the microcolumn. Total thallium was determined after reduction of Tl(III) to Tl(I) by hydroxyl amine hydrochloride. A sample volume of 25 ml resulted in a preconcentration factor of 77. Precision at 30 microgl(-1) was 2.6% RSD (n=10). With 25 ml sampling volume a detection limit of 2.5 microgl(-1) was determined. The effect of potential interfering ions on the determination was studied. The method was applied for the determination of thallium in water, waste water, hair, nail, coal, and standard reference alloys. The accuracy was assessed through recovery experiment, independent analysis by Furnace-AAS, and analysis of certified reference alloys.     

Development of non-gel-based two-dimensional separation of intact proteins by an on-line hyphenation of capillary isoelectric focusing and hollow fiber flow field-flow fractionation

A rapid, non-gel-based, on-line, two-dimensional separation method is introduced for proteome analysis. Protein fractionation was carried out by first exploiting the differences in their respective isoelectric points (pI) in a Teflon capillary using isoelectric focusing (IEF), followed by a molecular weight (MW)-based separation in a hollow fiber by flow field-flow fractionation (FlFFF). The method developed here (CIEF-HFFlFFF) may be a powerful alternative to two-dimensional polyacrylamide gel electrophoresis, which is currently used for the separation and purification of proteins. In CIEF-HFFlFFF, proteins can be collected as a fraction of a certain pI and MW interval without being denatured. Additionally, the ampholyte solution is simultaneously removed during separation in the hollow fiber, and the overall process time is significantly reduced. This method was applied to a human urinary proteome sample, leading to the identification of 114 proteins with the subsequent off-line use of nanoflow liquid chromatography-tandem mass spectrometry after the tryptic digestion of each collected protein fraction.     

The flow of a fluid film entrained by a supersonic flow of gas

We have conducted an experimental study into the flow of a high-viscosity fluid directed through an orifice of small diameter onto the surface of a body contained within a supersonic flow of air.Notation M Mach number for the outlet cross section of the nozzle - Re_D Reynolds number calculated from the parameters of the unperturbed flow at the outlet section of the nozzle and from the diameter of model rounding - P₀ total pressure in the pressure chamber of the wind tunnel, Pa - T₀ deceleration temperature - sweepback angle of leading edge of plate (between the normal to the direction of the unperturbed flow and the generatrix of the leading edge), deg - d orifice diameter, mm - angle between direction of unperturbed flow and radius vector of orifice, deg - frictional stress at boundary separating fluid and gas, Pa - Q volumetric fluid flow rate, cm³/sec - kinematic viscosity of fluid, cSt - q /q_g ratio of the velocity head of the fluid at the outlet from the orifice to the local velocity head of the gas - thickness of fluid film, mm - b width of fluid film, mm - angle between tangents to the side boundaries of the fluid film, deg - s coordinate calculated from the center of the orifice along the midline of the film or along the axis of wedge symmetry, mm - z coordinate calculated along the normal to the axis, mm Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 59, No. 2, pp. 181–186, August, 1990.     

Selective measurement of ultratrace methylmercury in fish by flow injection on-line microcolumn displacement sorption preconcentration and separation coupled with electrothermal atomic absorption spectrometry

A novel nonchromatographic speciation technique for ultratrace methylmercury in biological materials was developed by flow injection microcolumn displacement sorption preconcentration and separation coupled on-line with electrothermal atomic absorption spectrometry (ETAAS). In the developed technique, Cu(II) was first on-line complexed with diethyldithiocarbamate (DDTC), and the resultant Cu-DDTC was presorbed onto a microcolumn packed with the sorbent from a cigarette filter. Selective preconcentration of methylmercury (MeHg) in the presence of Hg(II), ethylmercury (EtHg), and phenylmercury (PhHg) was achieved at pH 6.8 through loading the sample solution onto the microcolumn due to a displacement reaction between MeHg and the presorbed Cu-DDTC. The retained MeHg was subsequently eluted with 50 microL of ethanol and on-line determined by ETAAS. Interferences from coexisting heavy metal ions with lower stability of their DDTC complexes relative to Cu-DDTC were minimized without the need of any masking reagents. No interferences from 5.5 mg L(-1) Cu(II), 4.5 mg L(-1) Cd(II), 2.5 mg L(-1) Cr(III), 3 mg L(-1) Fe(III), 10 mg L(-1) Ni(II), 10 mg L(-1) Pb(II), and at least 25 mg L(-1) Zn(II) were observed for the determination of MeHg at the 50 ng L(-1) level (as Hg). With the consumption of only 3.4 mL of sample solution, an enhancement factor of 75, a detection limit of 6.8 ng L(-1) (as Hg) in the digest (corresponding to 3.4 ng g(-1) in original solid sample for a final 50 mL of digest of 0.1 g of solid material), and a precision (RSD, n = 13) of 2.3% for the determination of methylmercury at the 50 ng L(-1) (as Hg) level were achieved at a sample throughput of 30 samples h(-1). The recoveries of methylmercury spike in real fish samples ranged from 97 to 108%. The developed technique was validated by determination of methylmercury in a certified reference material (DORM-2, dogfish muscle), and was shown to be useful for the determination of methylmercury in real fish samples.     

Rapid determination of aspartate enantiomers in tissue samples by microdialysis coupled on-line with capillary electrophoresis.

Microdialysis was coupled on-line with derivatization by o-phthalaldehyde and beta-mercaptoethanol and optically gated capillary electrophoresis to determine D- and L-aspartate in tissue samples obtained from rats. The microdialysis probe was inserted into a homogenized tissue sample which allowed generation of a continuous sample stream that was filtered and deproteinated. With 7.5 mM beta-cyclodextrin (CD) in the electrophoresis buffer, the enantiomers of interest could be resolved in 3 s with an electric field of 2500 V/cm over a separation length of 15 mm. Values of D- and L-aspartate in different tissues agreed well with those obtained by an HPLC procedure that required protein precipitation, centrifugation, and extraction. The speed and compatibility with automation of the microdialysis/CE method may make it a general approach for a variety of applications involving high-throughput analysis or sensorlike operation.     

在线气相色谱仪间接法测量天然气热值的不确定度评估

随着能量计量方式不断被提出,间接法测量天然气热值成为能量计量过程中必不可少的步骤。在天然气场站中大多选用在线气相色谱仪对管道天然气组成进行持续分析检测,并通过GB/T 11062——2014规定的计算方法来间接测量天然气的发热量,这也是最快速可行的方法。以济南输气站在线气相色谱仪为研究对象,结合间接法测量天然气热值的过程,对过程中存在的每一个能对最终结果造成影响的因素进行分析探讨,并按照不确定度传递原则,对最终结果的不确定度进行评估,最终该文中天然气热值测量结果的相对扩展不确定度为0.88%(k=2),对应于热值的不确定度为0.34 MJ/m~3。     

Managing the integrity of design data generated by multiple applications: The principle of patching

The purpose of this work is to develop automatic methods of semantic integrity maintenance, in support of concurrent engineering. Semantic integrity relations in any final engineering design are built up incrementally, through the use of different computer applications. Here, the structure of these integrity relations are formalised for representation within a database. When changes to a design have to be made, they can invalidate integrity relations in other parts of the design. Formal methods are defined for identifying what data and integrity relations are invalidated by any change. Methods for making changes that minimise re-design are described and formalised. Opportunities for using semantic integrity to assess progress on a design are reviewed.Research supported by NSF grant IRI-9319982.     

The atomization of a liquid by a rapid gas flow

In calculating the sedimentation of dust on the drops formed by the atomization of a liquid in a rapid gas flow, the most probable drop size 2r_m should be used rather than the Sauter diameter D₀.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 19, No. 1, pp. 116–119, July, 1970.     

Development of an on-line flow injection Sr/matrix separation method for accurate, high-throughput determination of Sr isotope ratios by multiple collector-inductively coupled plasma-mass spectrometry

This work introduces a newly developed on-line flow injection (FI) Sr/Rb separation method as an alternative to the common, manual Sr/matrix batch separation procedure, since total analysis time is often limited by sample preparation despite the fast rate of data acquisition possible by inductively coupled plasma-mass spectrometers (ICPMS). Separation columns containing approximately 100 muL of Sr-specific resin were used for on-line FI Sr/matrix separation with subsequent determination of (87)Sr/(86)Sr isotope ratios by multiple collector ICPMS. The occurrence of memory effects exhibited by the Sr-specific resin, a major restriction to the repetitive use of this costly material, could successfully be overcome. The method was fully validated by means of certified reference materials. A set of two biological and six geological Sr- and Rb-bearing samples was successfully characterized for its (87)Sr/(86)Sr isotope ratios with precisions of 0.01-0.04% 2 RSD (n = 5-10). Based on our measurements we suggest (87)Sr/(86)Sr isotope ratios of 0.713 15 +/- 0.000 16 (2 SD) and 0.709 31 +/- 0.000 06 (2 SD) for the NIST SRM 1400 bone ash and the NIST SRM 1486 bone meal, respectively. Measured (87)Sr/(86)Sr isotope ratios for five basalt samples are in excellent agreement with published data with deviations from the published value ranging from 0 to 0.03%. A mica sample with a Rb/Sr ratio of approximately 1 was successfully characterized for its (87)Sr/(86)Sr isotope signature to be 0.718 24 +/- 0.000 29 (2 SD) by the proposed method. Synthetic samples with Rb/Sr ratios of up to 10/1 could successfully be measured without significant interferences on mass 87, which would otherwise bias the accuracy and uncertainty of the obtained data.     

Indirect determination of sulfide at ultratrace levels in natural waters by flow injection on-line sorption in a knotted reactor coupled with hydride generation atomic fluorescence spectrometry

A simple and sensitive nonchromatographic approach for indirect determination of sulfide at ultratrace levels in natural waters based on its selective precipitation with Hg2+ on the inner wall of a knotted reactor (KR) was developed for flow injection on-line sorption coupled with hydride generation atomic fluorescence spectrometry (HG-AFS). With the Hg2+ pH kept at 2.0, the HgS precipitation was formed in the KR after a reaction time of 120 s. A 10% (v/v) HCl was introduced to elute the remnant inorganic mercury and to merge with the KBH4 solution (0.05% m/v) for HG-AFS detection. Under the optimal experimental conditions, the sample throughputs were 20 h(-1). The detection limit was found to be 0.05 microg L(-1), and the relative standard deviation (RSD, n = 11) for determination of 2.0 microg L(-1) sulfide was 3.3%. The developed method was successfully applied to the determination of sulfide in a variety of natural water samples and wastewater samples with the gas-phase separation and sorption apparatus.     

The flow of a solid by viscous slip between elastic domains

Summary A mathematical investigation is presented of the plane strain viscoplastic flow of a polycrystalline solid, which deforms by slip along microscopic deformation banales. It is demonstrated that the shear angle obeys Laplaces equation and that over the range of strain rates corresponding to thermally activated flow the principal shear stress also remains harmonic. The equation governing the normal stress is also derived. A brief discussion follows concerning the domain of application of these equations.     

平晶表面形状加压分析判断法的原理与应用探讨

平晶表面形状的判断对于平晶平面度的计算非常重要,错误的判断将会直接导致计算错误。该文通过对加压分析判断法原理的介绍,讨论在实际检定工作中的注意事项。灵活掌握该方法不仅对于平晶检定工作,而且在使用平晶测量量具或工件表面平面度时都非常重要。