Sample preparation solid-liquid extraction

An analyte may be present in one material phase (either a solid or liquid sample) and, as part of the sample preparation scheme, be required to be separated from the sample matrix and placed in another phase (a liquid). Such a separation is known as an extraction—the analyte is extracted from the initial phase by the liquid and is deposited (dissolved) in the liquid, while other sample components are insoluble and remain in the initial phase. If the sample is a solid, the extraction is referred to as a solid-liquid extraction. In other words, a solid sample is placed in the same container as the liquid and the analyte is separated from the solid because it dissolves in the liquid while other sample components do not. 

In order to determine chemical elements in soil, samples of the soil must undergo a solid-liquid extraction. Sometimes the extracts resulting from this procedure have analyte concentrations that are too high to be measured accurately by the chosen method. Therefore, they must be diluted. At the Natural Resources Conservation Service (NRCS) Soil Survey Laboratory in Lincoln, Nebraska, an automated diluting device is used. Using this device, the analyst accurately transfers aliquots of the extract and a certain volume of extraction solution to the same container. This dilutor may also be used to pipet standards and prepare serial dilutions. 

A pivotal step in the analytical process is sample preparation. Frequently liquid-liquid extractions (LLEs) are used. Solvents, pH, and multiple back extractions are all manipulated to increase selectivity and decrease unwanted contaminants before injection on the GC system. Solid phase extraction (SPE) is more convenient than it used to be because of an increase in commercially available SPE columns. SPE columns are packed with an inert material that binds the drug of interest, allowing impurities to pass through. As with LEE, solvent choices and pH affect retention and recovery. There are three commercially available types of SPE columns, diatomaceous earth (which uses the same principles as LLE), polystyrene-divinylbenzene copolymer, and mixed mode bonded silica (Franke and de Zeeuw, 1998). 

Before compounds in biological matrices can be analyzed by LC/MS/MS, the samples must undergo a preparation procedure. There are a variety of techniques available for sample preparation including offline sample preparation techniques (liquid-liquid extraction, protein precipitation, and solid phase extraction) and on-line sample preparation... 

Figure 9. Partial H NMR spectrum of 13 LiN03 at 213 K. Top sample prepared by solid-liquid extraction using freshly opened CDC13. Bottom sample prepared with water-saturated CDCI3. (Reprinted with permission from ref. 32. Copyright 2004 American Chemical Society.)...

Soil, sediment, and dust samples were prepared in a similar way before analysis. After the pre-cleanup steps and homogenization, FRs were extracted from samples using different solid-liquid extraction techniques. The most commonly used technique was accelerated solvent extraction (ASE), which enables the fast extraction of samples using different solvents such as hexane and dichloromethane [98-100]. Other commonly used techniques for these samples were ultrawave-assisted extraction (UAE) [97], which also enabled quick extraction, and the more time-consuming but very efficient technique, Soxhlet extraction [96]. Some authors have also described less common techniques such as microSPE [95]. There is also information that many FRs that are no longer produced (mainly PCBs and PBDEs) are present in dusts, soils, and sediments in very high amounts, even 390 pg/g [98]. 

Generally, preconcentration of pollutants from water samples and sample preparation steps are accomplished by extraction techniques based on enrichment of liquid phase (liquid/liquid extraction) or solid phase (solid/liquid extraction) ". Historically, liq-uid/liquid extraction (LEE) was used exclusively to enrich phenols from water samples. LEE is still used as a preconcentration step . However, there is an increasing tendency to replace LEE by solid phase extraction (SPE) and solid phase microextraction (SPME). Among the reasons for replacing LEE are foam formation, the large volume of organic solvents needed, the length of the analysis time and difficulties in the automation of LEE procedures. On the other hand, SPE requires incomparable smaller amounts of solvents (SPME requires no solvent at all) and can be easily automated . Finally, SPE and SPME are cheaper in comparison with LEE. 

Phase equilibrium theory is the fundamental basis for many of the separations techniques used for sample preparation, including liquid-liquid extraction, solid-phase extraction, solid-phase microextraction, and HPLC. 

In some cases, sample preparation by liquid-liquid extraction (LLE) is used. With a good solid phase extraction (SPE), a concentration factor of up to 40 can be achieved. This concentration factor also means that the detection limits for the method can be 40 times better than the detection limits for methanolic standards. This is why we use SPE to generate our calibration curves for drugs in blood. A bovine blood is spiked with the standards and afterwards prepared by SPE. By generating a calibration curve from a real matrix all matrix effects are taken into consideration. Figure 7-11 shows a calibration curve for morphine-PFP. 

There are many sample preparation procedures published in the scientific literature, and within the scope of this chapter, only the most current and popular methods will be discussed. By far, the commonest and most popular method used for pretreatment of liquid samples is solid phase extraction (SPE) [40,41]. For solid samples, several techniques are available including supercritical fluid extraction (SFE) [42,43], microwave-assisted solvent extraction (MASE) [44,45] and accelerated solvent extraction (ASE) [46,47]. Solvent extraction methods have long been established as the standard approach to sample preparation, but the increasingly demanding needs of industries like the pharmaceutical, agrochemical and petrochemical for greater productivity, faster assays, and increased automation have led to the development of newer ways of sample preparation summarised in Fig. 2.3. 

To perform that work, samples were subjected to a nonselective preparation, trying to extract the highest number of different compounds, since a metabolomics approach was pursued. The protocol followed by Hurtado and her collaborators [73] was quite simple a solid-liquid extraction with methanol, starting from lyophilized and homogenized fruit pulp followed by shaking in a vortex, centrifugation, evaporation to dryness, and reconstitution of the extract. 

Deactivated capillary chromatographic columns can now be used for injecting organically polluted water. Delicate liquid-liquid extraction preparation can thus be avoided, although it is undoubtedly necessary to clean up the water on a suitable cartridge and possibly increase sample concentration. This method should be compared from the standpoint of convenience and accuracy with the solid-liquid extraction method on cartridges followed by elution with an adequate solvent. 

Given the concerns about the use of toxic organic solvents in food chemistry, many new techniques have been developed to overcome or minimize this problem. For instance, environmentally clean extraction techniques, such as those based on the use of compressed fluids (pressurized liquids, PLE supercritical fluids, SFE and subcritical water, SWE or PHWE), are widely used as alternatives to conventional procedures, such as solid—liquid extraction (SEE), liquid—liquid extraction (LLE), and the like. These alternative processes have in common the use of lower amount of solvents (from hundred milliliters to few milliliters), the lack of toxic residues, higher efficiency extraction (in terms of yields and energy used), and the improved selectivity of the process. SFE has been used in food analysis as a sample preparation technique, mainly for lipophilic compounds, while PLE has been extensively used for many compositional food applications, because the selectivity of this technique... 

Sample preparation depends mainly on the matrix for example, liquid matrices, such as beverages, require only filtration prior to the direct injection into a LC system. For solids, steam distillation and solid—liquid extraction using solvents such as ethanol, methanol, or mixtures of acetonitrile, 2-propanol, and ethanol, are the techniques most commonly used to improve sensitivity and reduce matrix interferences. A common practice for complex samples involves precipitation of proteins and fat by the addition of methanol, followed by centrifugation or filtration, providing an extract suitable for chromatographic analysis. 

Theoretical and applied aspects of microwave heating, as well as the advantages of its application are discussed for the individual analytical processes and also for the sample preparation procedures. Special attention is paid to the various preconcentration techniques, in part, sorption and extraction. Improvement of microwave-assisted solution preconcentration is shown on the example of separation of noble metals from matrix components by complexing sorbents. Advantages of microwave-assisted extraction and principles of choice of appropriate solvent are considered for the extraction of organic contaminants from solutions and solid samples by alcohols and room-temperature ionic liquids (RTILs). 

Liquid samples might appear to be easier to prepare for LC analysis than solids, particularly if the compounds of interest are present in high concentration. In some cases this may be true and the first example given below requires virtually no sample preparation whatever. The second example, however, requires more involved treatment and when analyzing protein mixtures, the procedure can become very complex indeed involving extraction, centrifugation and fractional precipitation on reversed phases. In general, however, liquid samples become more difficult to prepare when the substances are present at very low concentrations. 

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