Near melting point flow injection: a drastic enhancement in FAAS detection limits

The described technique is based on segregation phenomena taking place in solids near their melting point. High impurity concentration occurs in a liquid phase at the grain boundaries. A continuous flow of an adequate solvent is used in far from equilibrium conditions to reach high extraction efficiency of the analyte. As an example, the determination of trace amounts of caesium in metallic sodium is described. The 5 mg/kg detection limit of conventional FAAS is thus lowered to a few g/kg.     

Improvement of detection limits in flow injection analysis

Summary When using a conventional UV/VIS-Spectrophotometer with a large sample compartment as a detector for FIA, flow cells with longer pathlengths can be applied. Despite of a unavoidable band broadening a significant improvement of detection limit can be achieved compared to standard cells. Band broadening is compensated by slight modifications of the manifold, so that the dispersion is in the same range for long path cells and standard flow cells. With a 5 cm flow cell phosphate can be detected down to 0.005 mg/l P.     

On-line flow sample stacking in a flow injection analysis-capillary electrophoresis system: 2000-fold enhancement of detection sensitivity for priority phenol pollutants

A flow injection analysis-capillary electrophoresis system has been used for on-line flow stacking of 11 US Environmental Protection Agency priority phenol pollutants. Samples containing low concentrations of phenols dissolved in deionised water are continuously delivered to the capillary opening by means of a peristaltic pump. The sample components stack at the boundary between the highly conductive separation electrolyte and the introduced sample. By selecting an appropriate electrolyte and stacking conditions the movement of the electrolyte solution inside the capillary can be reduced, thereby improving the stacking efficiency. The electrolyte used here contained 20 mM phosphate, 8% 2-butanol, and 0.001% hexamethonium bromide at pH 11.95, and the stacking was carried out at 2 kV for 240 s. These conditions allowed up to 2000-fold preconcentration of the selected phenols. No matrix removal was necessary.     

Selectivity enhancement by flow injection analysis

Flow injection analysis offers numerous possibilities for significantly increasing the selectivity of existing methods by utilizing knowledge of the chemistry of those methods. It also enables new selective methods to be created by utilizing kinetic methods and fast separation techniques such as gas diffusion, dialysis, extraction and ion-exchange columns. Selectivity enhancements and increased sensitivity can be achieved by incorporating the kinetic techniques of kinetic discrimination and/or kinetic enhancement into the timing of the system or the reagent concentrations and conditions for a given method. Methods have been developed for quantifying ozone, chlorine dioxide, chlorate ion, and chlorite and chlorate ions sequentially. A dual-phase gas diffusion system for hydride generation provides significant decreases in the interferences observed for transition metals.     

Simultaneous multiwavelength detection in flow injection analysis

The potential of the use of the diode-array detector in conjunction with flow injection analysis is outlined. Methods for multicomponent resolution can be based on the formation of complexes absorbing at different wavelengths. The example given is the determination of mixtures of copper(II) and iron(III) with a mixed 1:10-phenanthroline/neocuproine reagent. Amplification and dilution methods are based on the sum of the absorbances at several wavelengths and on monitoring absorbances at wavelengths away from the absorption maximum, respectively. The determination of nitrite via the Griess reaction is used as an example; the viable determination range is extended to 0.002/2-60.0 μg ml^?1 nitrite. Software for the implementation of the suggested methods is outlined.     

The determination of sulfite in a flow injection system with chemiluminescence detection

The emission produced by sulfite on oxidation by permanganate in acidic solution in the presence of riboflavin phosphate or brilliant sulfaflavine is used to determine 0.9–35 ng of sulfite. Only sulfide and thiosulfate also give emissions.     

Amperometric detection for capillary flow injection analysis

Ultrasmall-volume measurements of oxidizable compounds have been accomplished by coupling a capillary flow injection system with amperometric detection. Remarkably low (femtomole) mass detection limits result from the combination of nanoliter sample volume and the inherent sensitivity of the wall-jet detector. A substantial economy of reagent consumption and disposal accrues from the operation of the nl/min flow regime. Variables influencing the physical dispersion in the capillary flow injection system, including capillary length, sample volume or flow rate, are explored and optimized.     

基于激光诱导击穿光谱(LIBS)的煤灰熔点快速检测

炉内结渣是影响火电机组和气化工艺可靠运行的关键因素之一,准确预测灰熔点可以提前调整炉膛出口温度以避免结渣。本论文采用激光诱导击穿光谱（LIBS）采集煤灰样中金属元素的光谱,分别建立煤灰中的金属元素的谱线强度与煤灰熔点的随机森林模型、支持向量机回归模型和线性回归模型,直接预测煤灰熔点温度。采用基于马氏距离(MD)的异常数据剔除算法和基于稀疏矩阵的基线估计与降噪算法（BEADS）,对粉煤灰样的全光谱数据进行了预处理。随机森林模型对粉煤灰熔点的预测平均相对误差（MRE）为54.74%,支持向量机回归模型的预测平均相对误差为60.08%,而线性回归模型的预测平均相对误差达到了9.78%。研究结果表明,线性回归模型对煤灰熔点的预测结果更准确。     

Rapid determination of subnanogram urapidil using flow injection enhancement chemiluminescence

A sensitive flow-injection (FI) chemiluminescence (CL) for the determination of urapidil is described in this paper. It is based on the enhancement effect of urapidil on the CL reaction between luminol and hydrogen peroxide. The increment of CL intensity is proportional to the concentration of urapidil in the range 0.1−10 ng/mL (R ²=0.9986), with a detection limit (3σ) of 0.03 ng/mL. The whole process, at a flow rate of 2.0 mL/min, including sampling and washing, could be completed in 0.5 min, and the relative standard deviation (RSD) at the concentration of 0.1, 1.0, and 10.0 ng/mL was less than 3.0% (n = 5). The proposed method has been successfully applied for the determination of urapidil in pharmaceutical preparation, human urine, and serum. The text was submitted by the authors in English.     

Sample preconcentration by continuous flow extraction with a flow injection atomic absorption detection system

The flow manifold described allows automatic extraction of metal ions in aqueous samples into 4-methyl-2-penthanone with ammonium pyrrolidinedithiocarbamate as an extracting agent. The organic extract is led into the loop of an injector situated in an integrated feed system of an atomic absorption spectrometer. No dispersion of the injected organic extract plug, 110 μl, occurs in the aqueous feed stream and the resulting signal from the spectrometer is a peak. An increase in sensitivity of 15–20 is achieved for copper, nickel, lead and zinc in comparison with direct aspiration of the aqueous samples. The sampling frequency is 40 h^?1 and the consumption of 4-methyl-2-pentanone is typically 0.3 ml min^?1. The detection limit for copper is about 1 μ l^?1.     

Phosphorescence in liquid solutions: a promising detection principle in liquid chromatography and flow injection analysis

A new detection technique for liquid chromatography and flow injection analysis has been developed. The technique is based on the phosphorescence of biacetyl in various eluents. It can be applied in two modes, i.e. sensitized and quenched phosphorescence. Especially the latter is widely applicable for instance to non-absorbing compounds as measured in ion chromatography.     

流动注射在线富集-FAAS测定合金钢中微量镍

提出了流动注射在线离子交换富集-火焰原子吸收光谱法测定合金钢中微量镍的分析方法.在线离子交换采用双柱正向富集和反向洗脱流路方式,使用80目732强酸型阳离子交换树脂在酸度为0.10mol/L HCl中富集样品中的Ni2+,并用2.0mol/L HCl洗脱.设计了流动注射在线离子交换富集双柱流路的操作程序,优化了各项仪器...     

Internal standard in flow injection analysis with amperometric detection

In this work, we describe for the first time the use of the internal standard method in flow injection analysis (FIA) with amperometric detection. The method is based on the application of sequential potential pulses to the working electrode in an electrochemical flow cell. The sequence of potential pulses is selected in such a way that the analyte and internal standard compound are detected and monitored individually and independently at the same working electrode. This approach compensates for random errors associated with variations of flow rate, injection volume, ionic strength difference between standards and samples, and accidental insertion or formation of air bubbles in the carrier stream. In addition, this method can overcome the major drawback of amperometric detection using solid electrodes, which is gradual electrode passivation. To illustrate the potential of this method, the flow-injection amperometric detection of uric acid using [Fe(CN)₆]^3? as an internal standard (IS) is presented as an example.     

Some applications of enthalpimetric detection in flow injection analysis

Summary A flow injection manifold is described based on a flow-through arrangement of thermistors for measuring heat effects of chemical reactions. Temperature changes down to 10^–3 °C can be measured reproducibly. The working range for the determination of a component is dependent on the reaction enthalpy and can vary from 10^–3 to 10 mol/l for acids and bases, from 10 to 1000 ppm for e.g., alkylhydroperoxides. Sample frequencies up to 150 samples per hour can be realized.

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Einige Anwendungen der enthalpimetrischen Detektion in der Fließinjektionsanalyse

     

Determination of zinc by flow injection with fluorimetric detection in a micellar medium

A room-temperature flow injection spectrofluorimetric method is presented for the determination of Zn(II), based on the use of salicylaldehyde thiocarbohydrazone in the presence of Triton X-100 and sodium acetate-acetic acid buffer. Various physical and chemical variables affecting the reaction in the flow system were evaluated. The proposed method is very selective. The calibration graph is linear over the range 10-1000 ng/ml, with a detection limit of 5 ng/ml and a relative standard deviation at the 50 ng/ml level of 1.8 %. The method was successfully applied to the determination of Zn(II) in drinking waters and biological samples.     

Determination of zinc by flow injection with fluorimetric detection in a micellar medium

A room-temperature flow injection spectrofluorimetric method is presented for the determination of Zn(II), based on the use of salicylaldehyde thiocarbohydrazone in the presence of Triton X-100 and sodium acetate-acetic acid buffer. Various physical and chemical variables affecting the reaction in the flow system were evaluated. The proposed method is very selective. The calibration graph is linear over the range 10–1000 ng/ml, with a detection limit of 5 ng/ml and a relative standard deviation at the 50 ng/ml level of 1.8 %. The method was successfully applied to the determination of Zn(II) in drinking waters and biological samples.     

Capillary batch injection analysis and capillary flow injection analysis with electrochemical detection: a comparative study of both methods

Capillary batch injection analysis (CBIA) and capillary flow injection analysis (CFIA) in combination with electrochemical detection as well as optical detection methods were studied and compared with respect to their performance. Despite the differences in technical equipment both techniques share the same idea of reproducible transport and washout of nanolitre samples over sensing surfaces. Thus the same electrochemical flow cell can be used for both CBIA and CFIA. The amperometric and potentiometric CBIA responses were studied under various experimental conditions in order to optimise the CBIA set-up. In particular, the density of the sample solution relative to that of the cell electrolyte had a remarkable effect on the hydrodynamic characteristics of CBIA. Dispersion in CFIA was investigated using on column UV-detection for electroosmotic flow (EOF) conditions as well as for gravity flow conditions. It is demonstrated for a 75 μm capillary that the relative band broadening of the sample plug under gravity flow is only about twice as large as under EOF. Furthermore, dispersion in a system that involves a chemical reaction between the sample and the carrier solution, namely CrO₇ ^2– and Fe²⁺ has been investigated by amperometric detection and exploited for the determination of dichromate microsamples. Received: 28 November 1997 / Revised: 23 February 1998 / Accepted: 26 February 1998     

Capillary batch injection analysis and capillary flow injection analysis with electrochemical detection: a comparative study of both methods

Capillary batch injection analysis (CBIA) and capillary flow injection analysis (CFIA) in combination with electrochemical detection as well as optical detection methods were studied and compared with respect to their performance. Despite the differences in technical equipment both techniques share the same idea of reproducible transport and washout of nanolitre samples over sensing surfaces. Thus the same electrochemical flow cell can be used for both CBIA and CFIA. The amperometric and potentiometric CBIA responses were studied under various experimental conditions in order to optimise the CBIA set-up. In particular, the density of the sample solution relative to that of the cell electrolyte had a remarkable effect on the hydrodynamic characteristics of CBIA. Dispersion in CFIA was investigated using on column UV-detection for electroosmotic flow (EOF) conditions as well as for gravity flow conditions. It is demonstrated for a 75 μm capillary that the relative band broadening of the sample plug under gravity flow is only about twice as large as under EOF. Furthermore, dispersion in a system that involves a chemical reaction between the sample and the carrier solution, namely CrO₇ ^2– and Fe²⁺ has been investigated by amperometric detection and exploited for the determination of dichromate microsamples.     

Optosensing at active surfaces — a new detection principle in flow injection analysis

Reflectance spectrophotometry is applied to flow-injection measurements of pH and the assays of ammonia and urea with the aim of demonstrating the principle and testing the performance of optosensors integrated into microconduits. A novel injection approach, the split-loop technique, is applied. For pH measurements, detection is based on commercial non-bleeding acid-base indicator papers situated in the flow stream at the tip of the fibre optic. Measurements of pH in the range 4–10 are possible at a rate of 120 h^?1. Special attention is given to the physiological pH range; the standard deviation is 0.004 at pH 7.2. For the determinations of ammonia and urea (via urease), a bromothymol blue stream is used with a miniature gas-diffusion device.