High-pressure digestion

Fig. 14.8 Simplified schematic diagram of a high-pressure digestion vessel with an EDL. A. plug and seal, B. quartz pressure reaction vessel with a sample solution, C. EDL with an antenna, D. vessel jacket with a screw cap, E. airflow. Adapted from Ref. [44],...

Dynamic systems for high-pressure microwave treatment were developed much later than open-vessel systems. Operating under a high pressure reduces the flexibility afforded by working at atmospheric pressure. However, some recently developed devices allow microwave-assisted high-pressure digestion and extraction in a dynamic manner [33,34]. 

Microwave digestion systems have become very popular for decomposing samples. The photo shown is a closed-vessel microwave digestion system for high-pressure digestions. A microwave oven with a built-in fume exhaust system is shown along with sample trays that contain up to 1 2 samples. Teflon sample vessels can be operated at temperatures up to 2300 C and 625 psi. 

Low results obtained by DPASV for cadmium were suspected to be due to an incomplete decomposition of the organic matter in addition, losses of volatile fractions were assumed with the dry ashing technique used (450°C, open system, instead of high pressure digestion). The set was consequently withdrawn. 

High-Pressure Digestion, The introduction of a high-pressure ashing (HPA) technique by Knapp [45] has not only reduced the effective ashing time to ca. two hours but also opened the way to digestion of extremely resistant materials [46J. High-... 

An improved procedure has been described for atmospheric-pressure combustion of samples from high-purity metals [74]. High-pressure digestion with nitric and hydrofluoric acids 75], [76] and combustion techniques have both been shown to be suitable for the decomposition of samples of silicate-containing materials and fuels. Combustion in this case is carried out either in a stream of oxygen [77] or, to provide a closed system, in an oxygen bomb [78]. Mercury can be satisfactorily determined after prior Wickbold ashing [79]. 

While additive analysis of polyamides is usually carried out by dissolution in HFIP and hydrolysis in 6N HC1, polyphthalamides (PPAs) are quite insoluble in many solvents and very resistant to hydrolysis. The highly thermally stable PPAs can be adequately hydrolysed by means of high pressure microwave acid digestion (at 140-180 °C) in 10 mL Teflon vessels. This procedure allows simultaneous analysis of polymer composition and additives [643]. Also the polymer, oligomer and additive composition of polycarbonates can be examined after hydrolysis. However, it is necessary to optimise the reaction conditions in order to avoid degradation of bisphenol A. In the procedures for the analysis of dialkyltin stabilisers in PVC, described by Udris [644], in some instances the methods can be put on a quantitative basis, e.g. the GC determination of alcohols produced by hydrolysis of ester groups. 

Method development for high-pressure ashing and closed microwave digestion was reported for wet oxidation and extraction of Pb, Cd, Cr and Hg from various food packaging materials [57]. Use of HPA resulted in the highest median recoveries of the spiked elements (Pb and Cd, 92% Cr, 97% Hg, 83%). The use of In as an internal standard improved the accuracy... 

Matusiewicz [63,68] has reported the development of a high-pressure, high-temperature, focused-microwave-heated acid (HNO3) digestion system. This microwave technique requires only about 3 % of the time necessary for the thermal high-pressure (HPA) technique. The technique of microwave heating samples in sealed containers to speed up acid digestion has been in widespread use for the past few years [69,70]. 

Numerous microwave applications have been published on decomposition, fusion, dry and wet mineralisation, ashing and extraction. Knapp et al. [67] have reported decomposition efficiencies of over 96% for PE, PVC, PS and PB, using PMD. Boron in polyolefins was determined after high-pressure microwave digestion followed by ICP-MS [80]. 

As to the analysis of trace elements in paper, cardboard and raw materials for the production of paper, high concentration elements such as Cu, Fe or Ti can easily be determined by FAAS Cd and Pb are frequently analysed by GFAAS. Cadmium in pulp and paper was determined by AAS after pressurised digestion with nitric acid [145]. An interlaboratory comparison of Cd in wrapping paper was reported, mainly based on pressure digestion in FIFE bombs with sub-boiled nitric acid, followed by ETAAS [59]. For wrapping paper used for foodstuffs, next to the total content of toxic heavy metals, the soluble or leachable fraction is of particular interest. 

A microwave-assisted, high-temperature, and high-pressure UV digestion reactor has been developed by Florian and Knapp [44] for analytical purposes. The apparatus consists of the immersed electrodeless discharge lamp operating as a result of the MW field in the oven cavity (Fig. 14.8). An antenna fixed to the top of EDL enhanced the EDL excitation efficiency. Another interesting MW-UV reactor has... 

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