Application of low-energy-capable electron ionization with high-resolution mass spectrometer for characterization of pyrolysis oils from plastics.

Pyrolysis is a promising way of waste transformation into new valuable products. Pyrolytic oil is a mixture of hundreds of compounds and it requires detailed and accurate characterization for future applications. One of the most widely used techniques is mass spectrometry in combination with electron ionization. Tuneable ionization provides benefits including additional structural information and validation of molecular ion due to limited fragmentation at lower energies compared to conventional 70 eV, which provides spectral matches towards libraries. This approach was applied to the compounds identification and group characterization of virgin plastics polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), high-density polyethylene (HDPE), low-density polyethylene (LDPE) and their mixture. The use of lower ionization energy was beneficial for distinction of alkanes, iso-alkanes and aromatics. On the contrary to 70 eV, significantly higher fragmentation in branching of iso-alkanes at 12 eV was observed with higher yield of molecular ion also for n-alkane. More than 50 % of detected peaks were identified up to the retention time of icosane. The main analytes of produced pyrolysis oil were monoaromatic (from PVC and PS), alkene/cycloalkane (from PP and mixture). In the case of HDPE and LDPE the main compounds were 1-n-alkenes and n-alkanes. The applied methodology reveals compound group, carbon chain length and degree of unsaturation with higher confidence and success rate compared to traditional nominal mass 70 eV datasets.

Application of solid-phase microextraction arrows for characterizing volatile organic compounds from 3D printing of acrylonitrile-styrene-acrylate filament.

3D printing is an extensively used manufacturing technique that can pose specific health concerns due to the emission of volatile organic compounds (VOC). Herein, a detailed characterization of 3D printing-related VOC using solid-phase microextraction-gas chromatography/mass spectrometry (SPME-GC/MS) is described for the first time. The VOC were extracted in dynamic mode during the printing from the acrylonitrile-styrene-acrylate filament in an environmental chamber. The effect of extraction time on the extraction efficiency of 16 main VOC was studied for four different commercial SPME arrows. The volatile and semivolatile compounds were the most effectively extracted by carbon wide range-containing and polydimethyl siloxane arrows, respectively. The differences in extraction efficiency between arrows were further correlated to the molecular volume, octanol-water partition coefficient, and vapour pressure of observed VOC. The repeatability of SPME arrows towards the main VOC was assessed from static mode measurements of filament in headspace vials. In addition, we performed a group analysis of 57 VOC classified into 15 categories according to their chemical structure. Divinylbenzene-polydimethyl siloxane arrow turned out to be a good compromise between the total extracted amount and its distribution among tested VOC. Thus, this arrow was used to demonstrate the usefulness of SPME for the qualification of VOC emitted during printing in a real-life environment. A presented methodology can serve as a fast and reliable method for the qualification and semi-quantification of 3D printing-related VOC.

Miscanthus x giganteus stress tolerance and phytoremediation capacities in highly diesel contaminated soils.

Second generation biofuel crop Miscanthus x giganteus (Mxg) was studied as a candidate for petroleum hydrocarbons (PHs) contaminated soil phytomanagement. The soil was polluted by diesel in wide concentration gradient up to 50 g⋅kg-1 in an ex-situ pot experiment. The contaminated soil/plant interactions were investigated using plant biometric and physiological parameters, soil physico-chemical and microbial community's characteristics. The plant parameters and chlorophyll fluorescence indicators showed an inhibitory effect of diesel contamination; however much lower than expected from previously published results. Moreover, lower PHs concentrations (5 and 10 g⋅kg-1) resulted in positive reinforcement of electron transport as a result of hormesis effect. The soil pH did not change significantly during the vegetation season. The decrease of total organic carbon was significantly lower in planted pots. Soil respiration and dehydrogenases activity increased with the increasing contamination indicating ongoing PHs biodegradation. In addition, microbial biomass estimated by phospholipid fatty acids increased only at higher PHs concentrations. Higher dehydrogenases values were obtained in planted pots compared to unplanted. PHs degradation followed the first-order kinetics and for the middle range of contamination (10-40 g⋅kg-1) significantly lower PHs half-lives were determined in planted than unplanted soil pointing on phytoremediation. Diesel degradation was in range 35-70 % according to pot variant. Results confirmed the potential of Mxg for diesel contaminated soils phytomanagement mainly in PHs concentrations up to 20 g⋅kg-1 where phytoremediation was proved, and biomass yield was reduced only by 29 %.