Sample introduction flow injection

MESI operation requires processing of the whole sample to be extracted and has to reach steady-state permeation, which usually takes a long time. Thus, a new technical modification of MESI, called pulse introduction (flow injection-type) membrane extraction (PIME), has been developed, in which the sample is introduced to the membrane as a pulse pushed by a stream of eluent (usually water).55 This means that attaining a steady state is no longer crucial. PIME therefore provides not only a faster response and higher sensitivity, but also allows extraction of individual samples via discrete injections in addition to continuous on-line monitoring by sequential injection of a series of samples. Guo et al.56 described a mathematical model for the PIME permeation process, which showed that (a) there was a trade-off between the sensitivity and the time lag (the time taken to complete the permeation process) and (b) a large sample volume and a low flow rate enhance the sensitivity but also increase the time lag. 

For continuous sample introduction, gated injection was adopted. With EK flow, the analyte continually flowed in parallel with a separation buffer to the analyte waste reservoir (see Figure 4.15). Injection of the sample analyte was achieved by interrupting the flow of the buffer for a short time (known as the injection time) so that the analyte stream was injected. This scheme was achieved by four reservoirs (without considering the reagent reservoir) and two power supplies [317], Gated injection has also been achieved using one power supply and three solution reservoirs [564]. 

Principles and Characteristics As mentioned already (Section 3.5.2) solid-phase microextraction involves the use of a micro-fibre which is exposed to the analyte(s) for a prespecified time. GC-MS is an ideal detector after SPME extraction/injection for both qualitative and quantitative analysis. For SPME-GC analysis, the fibre is forced into the chromatography capillary injector, where the entire extraction is desorbed. A high linear flow-rate of the carrier gas along the fibre is essential to ensure complete desorption of the analytes. Because no solvent is injected, and the analytes are rapidly desorbed on to the column, minimum detection limits are improved and resolution is maintained. Online coupling of conventional fibre-based SPME coupled with GC is now becoming routine. Automated SPME takes the sample directly from bottle to gas chromatograph. Split/splitless, on-column and PTV injection are compatible with SPME. SPME can also be used very effectively for sample introduction to fast GC systems, provided that a dedicated injector is used for this purpose [69,70],... 

Flow-injection analysis is based on the introduction of a defined volume of sample into a carrier (or reagent) stream. This results in a sample plug bracketed by carrier (Fig. 1 (a)). 

The 1950s saw the introduction of a completely new approach to automation, in the form of continuous flow analysis. This made a significant contribution to the advance of automated analysis and subsequent development has been in the form of flow injection analysis. The original instruments were single channel and capable of measuring only one constituent in each sample. Multichannel instruments were then developed which could simultaneously carry out several different measurements on each sample. These were useful in laboratories where many samples required the same range of tests. 

An HPTC injector allows the introduction of a precise sample volume onto the column. A typical manual injector consists of a 6-port valve with a rotor, a sample loop and a needle port (Eigure 9). A sample solution is introduced into the sample loop using a 22-gauge blunt tip syringe in the TOAD position. The sample is then injected into the column by switching the valve to INJECT. The typical external sample loop size ranges from 6 pT to 2 mT. For many years, the Rheodyne 7125 injector was the industry-standard. In the early 1990s, it was replaced by the Rheodyne 7725 injector, which injects samples without momentary flow disruptions. ... 

Flow injection analysis is based on the injection of a liquid sample into a continuously flowing liquid carrier stream, where it is usually made to react to give reaction products that may be detected. FIA offers the possibility in an on-line manifold of sample handling including separation, preconcentration, masking and color reaction, and even microwave dissolution, all of which can be readily automated. The most common advantages of FIA include reduced manpower cost of laboratory operations, increased sample throughput, improved precision of results, reduced sample volumes, and the elimination of many interferences. Fully automated flow injection analysers are based on spectrophotometric detection but are readily adapted as sample preparation units for atomic spectrometric techniques. Flow injection as a sample introduction technique has been discussed previously, whereas here its full potential is briefly surveyed. In addition to a few books on FIA [168,169], several critical reviews of FIA methods for FAAS, GF AAS, and ICP-AES methods have been published [170,171]. 

TTie pneumatics also optimize the performance of the spht/sphtless inlet. Its forward pressure control in sphtless injection mode significantly reduces the risk of sample loss and maximizes accuracy and reproducibihty. TTie provision of mass flow control coupled with back pressure control in the spht injection mode maximizes reproducibihty and accuracy and also allows electronic adjustment of spht ratios. The net result is that sample-introduction conditions are optimized individually for the two most popular injection techniques. In addition, parameters are recorded in the methods file. 

Gaseous sample introduction into an ICP-MS presents different problems. Owing to its extremely sensitive nature, Dean et al. [13] introduced the sample as the gaseous hydride by a flow-injection approach. This was reasonably effective because lower volumes of samples and reagents were in use. They utibzed nitric acid as a carrier stream to prevent the formation of argon chloride species in the plasma. Argon chloride has the same mass as arsenic which is mono-isotopic, and this severely bmits arsenic determination. An additional problem was that the sensitivity was extremely dependent on the purity of reagents. 

Flow-injection sample introduction has been successfully applied in the analysis of standard reference materials and in the measurement of accurate and precise isotope ratios, and, hence, isotope dilution analysis. The rapid sample throughput possible with FI should allow a four-fold increase in the sampling rate compared with conventional nebufization techniques. Also, the amount of sample consumed per analytical measurement by FI is considerably less than continuous nebufization. TTiese considerations are of particular importance for the cost-effective operation of ICP-MS. 

Automation is especially advantageous for analysing large numbers of samples on a routine basis. The flow injection method requires low sample volumes, hut even the recommended 600 pi loop size can be reduced to approximately 100 pi without substantial losses in sensitivity, accuracy or precision. In certain applications involving ICPs samples as small as 20 pi have been reported [7]. There is Httle doubt that sample introduction with a flow-injection valve and driven by a peristaltic pump or another... 

CONTENTS Preface, Joseph Sneddon. Analyte Excitation Mechanisms in the Inductively Coupled Plasma, Kuang-Pang Li and J.D. Winefordner. Laser-Induced Ionization Spectrometry, Robert B. Green and Michael D. Seltzer. Sample Introduction in Atomic Spectroscopy, Joseph Sneddon. Background Correction Techniques in Atomic Absorption Spectrometry, G. Delude. Flow Injection Techniques for Atomic Spectrometry, Julian F. Tyson. 

Because of its capability for rapid multielement analysis, ICP-MS is particularly suited to sample introduction methods which give rise to transient signals. For example, electrothermal vaporization, flow injection and chromatographic methods can be interfaced and many elements monitored in a single run (see Chapter 7). 

A further miniaturization of solution introduction into ICP-MS allows the analysis of nanolitre sample volumes so that 100% transport efficiency is achieved and dead volume is minimized using nanovolume ( 50 nl) flow injection together with a total consumption nebulizer operating at uptake rates significantly below the 10p,lmin 1 level. The microflow nebulizer (DS 5 developed... 

Calibration and quantification procedures are easier in LA-ICP-MS compared to other solid-state mass spectrometric techniques because the laser ablation and the ICP ion source operate at normal pressure and the laser ablation of solid samples and ionization of analytes are separated in space and time. Therefore the advantage of solution calibration in ICP-MS can be applied in this solid-state analytical technique. The introduction of solution based calibration, which is only possible in LA-ICP-MS, was an innovative step in the development of this sensitive mass spectrometric technique. A number of different calibration approaches using aqueous standard solutions in the dual gas flow technique have been discussed by various authors.74 75 In the dual gas flow injection technique , the nebulized standard solution and the laser ablated sample material are mixed in the -piece and the two gas flows from the nebulizer (e.g. ultrasonic nebulizer) and laser ablation chamber are added. Using solution based calibration with the addition of a standard solution, Leach et alP determined minor elements in steel reference materials with a relative accuracy of a few %. In comparison to the so-called dual gas flow technique proposed in the literature, where the argon flow rates through the nebulizer and ablation cell add up to 11 min-1 (e.g. 0.451 min-1 and... 

A short guard column containing the same stationary phase as the analytical column is placed before the analytical column to protect it from contamination with particles or irreversibly adsorbed solutes. A high-quality pump provides smooth solvent flow. The injection valve allows rapid, precise sample introduction. The column is best housed in an oven to maintain a reproducible temperature. Column efficiency increases at elevated temperature because the rate of mass transfer between phases is increased. Mass spectro-metric detection provides quantitative and qualitative information for each substance eluted from the column. Ultraviolet detection is most common and it can provide qualitative information if a photodiode array is used to record a full spectrum of each analyte. Refractive index detection has universal response but is not very sensitive. Evaporative light scattering responds to the mass of each... 

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