Pyrolysis degradation products

It would be helpful to develop data determining the accuracy of PBDE determinations (e.g., percent recovery) in environmental samples. Methods for determining degradation products and metabolites of PBDE are needed. There is no information in the literature of detectable biodegradation of PBDEs in the environment under aerobic or anaerobic conditions. The analysis of PBDE pyrolysis degradation products, such as polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), is often disturbed by the presence of PBDEs. Ebert et al. (1999) demonstrated that by using a Florisil column ina sample clean-up process, almost complete separation of PBDEs and PBDD/Fs is achieved before analysis by GC-MS. 

Both NAT1 and NAT2 N-acetylate benzidine and O-acetylate the N-hydroxy metabolite. Because NAT2 and, to a lesser extent, NAT1 both show variation in the human population, this influences susceptibility to the carcinogenic effects of arylamines such as benzidine. With other aromatic amines, such as the heterocyclic amines found as food pyrolysis degradation products, N-acetylation is not favored, N-oxidation being the primary route followed by O-acetylation. This seems to take place in the colon. 

Chopra NM, Campbell BS, Hurley JC. 1978. Systematic studies on the breakdown of endosulfan in tobacco smokes Isolation and identification of the degradation products from the pyrolysis of endosulfan I in a nitrogen atmosphere. J Agric Food Chem 26 255-258. 

Applications Applications of IC extend beyond the measurement of anions and cations that initially contributed to the success of the technique. Polar organic and inorganic species can also be measured. Ion chromatography can profitably be used for the analysis of ionic degradation products. For example, IC permits determination of the elemental composition of additives in polymers from the products of pyrolysis or oxidative thermal degradation. The lower detection limit for additives in polymers are 0.1% by PyGC... 

Mass spectrometry (MS) coupled with pyrolysis has been a key technique in detecting the thermal degradation products of polymers, and thereby elucidating their thermal decomposition pathways [69]. In pyrolysis-MS, a sample is thermally decomposed in a reproducible manner by a pyrolysis source that is interfaced with a mass spectrometer. The volatile products formed can then be analysed either as a mixture by MS or after separation by GC/MS [70]. 

On the basis of the data obtained from the early thermal analysis and tube furnace pyrolysis experiments performed during the initial phases of this investigation, it became apparent that in order to establish the principal reaction pathways to the generation of volatile antimony species, the volatile degradation products of the DBDPO itself would need to be characterized (24, 25). 

Implementation The GC-MS of the sample headspace finds no perfume compounds. The cream is found to be greater than 80-wt% organic matter. Pyrolysis-GC-MS identified significant levels of glucose polymers, which were confirmed by FTIR to be either cellulose or starch. The iodine test revealed that the glucose polymer was starch. Further GC-MS analysis did not find cholesterol, but did find trace levels of a cholesterol degradation product. 

Fig. 15. Chromatograms of degradation products of polycaproamide by pyrolysis correlation chromatography.

A more promising way of obtaining more uniform degradation products is pyrolysis at high temperature. Synthesis gas is obtained at ever higher temperatures (700-1000°C), but according to Nimz, at the present it is not competitive with the corresponding processes based on coal (2). 

Flash vacuum pyrolysis of cocaine 1 at 550°C results in complete conversion to thermal degradation products. The major products isolated were benzoic acid (100%), N-methylpyrrole (74%) and methyl 3-butenoate (60%). 

Several compounds were also found to have a seasonal distribution. Kubatova et al. (2002) found that concentrations of lignin and cellulose pyrolysis products from wood burning were higher in aerosol samples collected during low-temperature conditions. On the other hand, concentrations of dicarboxylic acids and related products that are believed to be the oxidation products of hydrocarbons and fatty acids were highest in summer aerosols. PAHs, which are susceptible to atmospheric oxidation, were also more prevalent in winter than in summer. These results suggest that atmospheric oxidation of VOCs into secondary OAs and related oxidative degradation products are key factors in any OA mass closure, source identification, and source apportionment study. However, additional work is much desirable to assess the extent and seasonal variation of these processes. 

While there is controversy as to whether or not this Cellulose species exists, experimental evidence for the Cellulose species was obtained by Price et al.,60 who suggested that it could be a free radical in nature. At lower temperatures, oxygen plays a dominant role in cellulose degradation, and pyrolysis is faster in an oxidative atmosphere than in an inert one.61 Oxygen catalyzes the formation of both volatiles and char-promoting reactions.62 At higher temperatures, the degradation products are little affected.61... 

---