Sample application cold trapping

In many applications, such as the analysis of mercury in open ocean seawater, where the mercury concentrations can be as small as 10 ng/1 [468,472-476], a preconcentration stage is generally necessary. A preliminary concentration step may separate mercury from interfering substances, and the lowered detection limits attained are most desirable when sample quantity is limited. Concentration of mercury prior to measurement has been commonly achieved either by amalgamation on a noble-metal metal [460,467, 469,472], or by dithizone extraction [462,472,475] or extraction with sodium diethyldithiocarbamate [475]. Preconcentration and separation of mercury has also been accomplished using a cold trap at the temperature of liquid nitrogen. 

Collection of air samples in stainless steel canisters whose surfaces have been passivated is another common collection technique for VOCs. (Aluminum has also been used but the stability of polar organics in them is poor Gholson et al., 1990.) Indeed, this method is used not only for sampling air but in medical applications as well, where they have been used to sample organics in a single breath (Pleil and Lindstrom, 1995). Passivation of the canisters is often carried out using a process called SUMMA and hence referred to as SUMMA canisters. The canisters also have to be thoroughly cleaned before use an example of one such procedure is described by Blake et al. (1994). The sample is then typically preconcentrated by transfer to a cold trap prior to injection onto the GC column (e.g., see Blake et al., 1994). 

Odanaka et al. [212] have reported that the combination of gas chromatography with multiple ion detection system and a hydride generation heptane cold trap technique is useful for the quantitative determination of arsine, monomethyl-, dimethyl- and trimethylarsenic compounds and this approach is applicable to the analysis of environmental and biological samples. 

Thermal Desorption Thermal desorption is an alternative GC inlet system particularly used for VOC analysis. However, the analytes subjected to thermal desorption must be thermally stable to achieve successful analysis. Otherwise, decomposition occurs. This technique is mainly used for determination of volatiles in the air. Such a methodology requires sample collection onto sohd sorbents, then desorption of analytes and GC analysis. Traditionally, activated charcoal was used as a sorbent followed by extraction with carbon disulfide. However, solvent desorption involves re-dilution of the VOCs, thus partially negating the enrichment effect. Therefore, the sampling method is to pump a sample of gas (air) through the sorbent tube containing certain sorbents in order to concentrate the VOC. Afterwards, the sample tube is placed in thermal desorber oven and the analytes are released from the sorbent by application of high temperature and a flow of carrier gas. Additionally, desorbed compounds are refocused in a cold trap and then released into the GC column. Such a two-step thermal desorption process provides a narrow chromatographic band at the head of the column. 

Another configuration of MAP gas-phase extraction relates to dynamic headspace sampling, often referred to as purge and trap sampling. The container can be fitted with an aperture enclosing a trap, or a sorbent, cooled by some common means. This allows the application of a prolonged, low-power irradiation, or of a multi-pulse irradiation of the sample, thus providing a means to extract all of the volatile analytes from the matrix. The contents of the trap can then be transferred (by elution for a chemical or sorbent trap, or by thermal desorption for a cold trap) to an analytical instrument, such as a... 

Flame Decomposition. Utilization of a petroleum sample as a fuel for combustion in a specially devised burner system, such as that described by Wickbold (6), can be an effective way to destroy large amounts of an organic matrix. The method is applicable to those elements which are either volatile or form volatile compounds and which can be trapped quantitatively in a suitable scrubber. This technique was used to prepare samples for cold vapor atomic absorption determination of mercury. Details are included in Chapter 12. 

For many applications, gas-phase samples can be prepared using a routine vacuum line consisting of mechanical and diffusion pumps, a cold trap, thermocouple and capacitance manometer gauges and a manifold with attachments for sample tubes and gas inlets. NMR sample tubes are either sealed with a glass torch or constructed with self-sealing top assemblies. Preparation of samples at elevated pressures requires quantitative transfer operations. With few exceptions, gas-phase NMR samples used to study conformational processes contained a volatile bath gas in addition to the sample molecule, which usually has a low vapour pressure. Molecules with low vapour pressures tend to behave nonideally even at very low pressures and this factor must be taken into consideration when converting measured gas pressures into densities. 

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