Liquids analysis sample transport systems

Factors Influencing Liquid Analysis 37.3.2.1 Sample Transport Systems... 

An important factor of the sample transport system is the flow rate at the location of the optical analysis. The best results can be obtained with a laminar liquid flow. At higher Reynolds numbers. 

Membrane extraction with sorbent interface (MESI) is an interesting example of an extraction device, which is the most useful system for interfacing with GC. In this approach, the donor phase is a gas or a liquid sample, and the acceptor phase is a gas. The volatiles are continuously trapped on sorbent and then desorbed into GC [112]. Another solution is a combination of off-line GC-MESI through a cryogenic trap, which allows preparation of environmental samples in the field and performance of GC analysis after transportation to the laboratory [113,114]. MESI allows the extraction of volatile and relatively nonpolar analytes. 

The complete system can be controlled by a computer with special software designed for this type of analysis and is available from PS Analytical (UK) as a Touchstone Package (PSA 30.0). The carrier liquid and sample plug is transported using a multiroller peristaltic pump at a rate predetermined to suit the analysis of interest. Silicone tubing of 0.8 to 1.0 mm internal diameter is normally used and is found to be best for most organic solvents. A sample loop used for injection is usually in the volume range of 150 to 500 pi with an internal diameter 0.8-1.0 mm and is made of solvent resistant plastic. The best volume of loop is predetermined for a particular sample and analyte concentration. 

For conventional analysis by ICP or DCP, liquid samples are used, which are either easily prepared or commercially available. Interference problems are reduced to a minimum if the cahbration solutions are matched to the samples with respect to their content of acids and easily ionisable elements (see above). Calibration curves obtained with sparks, arcs, and laser ablation systems are usually curved so that 8—15 calibration samples or more are needed to define a suitable calibration. In the case of liquid analysis by DCP and ICP, fewer cahbration samples can be used due to the better linearity and dynamic range and absence of selfabsorption effects. With the introduction of hquids, the spray chamber is the major source of flicker noise due to aerosol formation and transport. While shot noise can easily be compensated by longer integration times, the flicker noise is of multiplicative nature so that any element can be used as an internal standard provided that a true simultaneous measurement of the analyte and internal standard line intensity is possible. 

To examine a sample by inductively coupled plasma mass spectrometry (ICP/MS) or inductively coupled plasma atomic-emission spectroscopy (ICP/AES) the sample must be transported into the flame of a plasma torch. Once in the flame, sample molecules are literally ripped apart to form ions of their constituent elements. These fragmentation and ionization processes are described in Chapters 6 and 14. To introduce samples into the center of the (plasma) flame, they must be transported there as gases, as finely dispersed droplets of a solution, or as fine particulate matter. The various methods of sample introduction are described here in three parts — A, B, and C Chapters 15, 16, and 17 — to cover gases, solutions (liquids), and solids. Some types of sample inlets are multipurpose and can be used with gases and liquids or with liquids and solids, but others have been designed specifically for only one kind of analysis. However, the principles governing the operation of inlet systems fall into a small number of categories. This chapter discusses specifically substances that are normally liquids at ambient temperatures. This sort of inlet is the commonest in analytical work. 

Enzyme linked electrochemical techniques can be carried out in two basic manners. In the first approach the enzyme is immobilized at the electrode. A second approach is to use a hydrodynamic technique, such as flow injection analysis (FIAEC) or liquid chromatography (LCEC), with the enzyme reaction being either off-line or on-line in a reactor prior to the amperometric detector. Hydrodynamic techniques provide a convenient and efficient method for transporting and mixing the substrate and enzyme, subsequent transport of product to the electrode, and rapid sample turnaround. The kinetics of the enzyme system can also be readily studied using hydrodynamic techniques. Immobilizing the enzyme at the electrode provides a simple system which is amenable to in vivo analysis. 

An alternative to direct liquid introduction is the moving belt, or moving-wire, transport interface. Because all l.c. solvents are evaporated before the sample is transported into the ion source, fewer restrictions are placed on solvent type, flow rates, or buffer composition. This system has been used for analysis of mixtures of pentoses, hexoses, and disaccha-rides. ... 

A schematic diagram of the automated FIA/DCP/OES system is shown in Fig. 7.6. The carrier liquid is transported using a peristaltic pump, at a rate predetermined to suit the particular analysis. Teflon tubing (internal diameter 0.8 mm) is used where appropriate however, silicone tubing is applied at the roller heads to accommodate both organic and inorganic solvents. Samples are introduced by the autosampler through a loop. The size of the loop is variable for most applications a 600 pi loop is sufficient. 

The two major kinds of samples analyzed for xenobiotics exposure are blood and urine. Both of these sample types are analyzed for systemic xenobiotics, which are those that are transported in the body and metabolized in various tissues. Xenobiotic substances, their metabolites, and then-adducts are absorbed into the body and transported through it in the bloodstream. Therefore, blood is of unique importance as a sample for biological monitoring. Blood is not a simple sample to process, and subjects often object to the process of taking it. Upon collection, blood may be treated with an anticoagulant, usually a salt of ethylenediaminetetraacetic acid (EDTA), and processed for analysis as whole blood. It may also be allowed to clot and be centrifuged to remove solids the liquid remaining is blood serum. 

Fig. 19. Schematic design of a flow injection analysis (FIA) system. A selection valve (top) allows a selection between sample stream and standard(s). The selected specimen is pumped through an injection loop. Repeatedly, the injection valve is switched for a short while so that the contents of the loop are transported by the carrier stream into the dispersion/reaction manifold. In this manifold, any type of chemical or physical reaction can be implemented (e.g. by addition of other chemicals, passing through an enzyme column, dilution by another injection, diffusion through a membrane, liquid-liquid extraction, etc. not shown). On its way through the manifold, the original plug undergoes axial dispersion which results in the typical shape of the finally detected signal peak...

An inductively-coupled plasma (ICP) is an effective spectroscopic excitation source, which in combination with atomic emission spectrometry (AES) is important in inorganic elemental analysis. ICP was also considered as an ion source for MS. An ICP-MS system is a special type of atmospheric-pressure ion source, where the liquid is nebulized into an atmospheric-pressure spray chamber. The larger droplets are separated from the smaller droplets and drained to waste. The aerosol of small droplets is transported by means of argon to the torch, where the ICP is generated and sustained. The analytes are atomized, and ionization of the elements takes place. Ions are sampled through an orifice into an atmospheric-pressure-vacuum interface, similar to an atmospheric-pressure ionization system for LC-MS. LC-ICP-MS is extensively reviewed, e.g., [12]. 

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