Large-volume samples concentration methods

Thorinm-232 is the only non-radiogenic thorium isotope of the U/Th decay series. Thorinm-232 enters the ocean by continental weathering and is mostly in the particulate form. Early measurements of Th were by alpha-spectrometry and required large volume samples ca. 1000 T). Not only did this make sample collection difficult, but the signal-to-noise ratio was often low and uncertain. With the development of a neutron activation analysis " and amass spectrometry method " the quality of the data greatly improved, and the required volume for mass spectrometry was reduced to less than a liter. Surface ocean waters typically have elevated concentrations of dissolved and particulate 17,3 7,62... 

A great deal of discussion about elemental determination methods focuses on minor, trace, ultra-trace levels of analyte presence in relatively large volume samples. There is another area equally challenging and that involves elemental determination at major and minor concentration in very small volume/low mass samples. Lochmuller and Galbraith used PIXE to study the metal content of carbonic anhydrase... 

There are basically three methods of liquid sampling in GC direct sampling, solid-phase extraction and liquid extraction. The traditional method of treating liquid samples prior to GC injection is liquid-liquid extraction (LLE), but several alternative methods, which reduce or eliminate the use of solvents, are preferred nowadays, such as static and dynamic headspace (DHS) for volatile compounds and supercritical fluid extraction (SFE) and solid-phase extraction (SPE) for semivolatiles. The method chosen depends on concentration and nature of the substances of interest that are present in the liquid. Direct sampling is used when the substances to be assayed are major components of the liquid. The other two extraction procedures are used when the pertinent solutes are present in very low concentration. Modem automated on-line SPE-GC-MS is configured either for at-column conditions or rapid large-volume injection (RLVI). 

The methylene blue reaction can also be used in a fractionation procedure for surfactants. The complexes with methylene blue can be collected in an organic solvent, concentrated, dissolved in methanol, and separated by high-performance liquid chromatography [205]. A variation of this method, permitting the collection of surfactant from large volumes of sample, should be workable in seawater. 

Figure 3.2 Three major methods in chromatography. The commonest form of chromatography involves the introduction of a small volume of sample onto a column and is known as zonal chromatography. Movement down the column is effected by the mobile phase, which may be simply a solvent (A) allowing partition of the test molecules between the stationary and mobile phases. Alternatively, the mobile phase may be a solvent containing solute molecules (B), which actively displace test molecules from the stationary phase. A less frequently used method known as frontal separation (C) does not involve a separate mobile phase but a large volume of the sample is allowed to pass through the column and as the various components separate, concentration fronts develop and their movement can be monitored.

Soxhlet extraction (EPA SW-846 3540) is a very efficient extraction process that is commonly used for semivolatile petroleum constituents. In the method, the solvent is heated and refluxed (recirculated) through the soil sample continuously for 16 hours, or overnight. This method generates a relatively large volume of extract that needs to be concentrated. Thus, it is more appropriate for semivolatile constituents than for volatile constituents. Sonication extraction (EPA SW-846 3550) can also be used for semivolatile compounds, and as the name suggests, involves the use of sound waves to enhance analyte transfer from sample to solvent. Sonication is a faster technique than Soxhlet extraction and can require less solvent. 

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