Sensitive Detection and Quantification of Oxygenated Compounds in Complex Samples Using GC-Combustion-MS.

This work introduces a new element-selective gas chromatography detector for the accurate quantification of traces of volatile oxygen-containing compounds in complex samples without the need for specific standards. The key to this approach is the use of oxygen highly enriched in 18O as the oxidizing gas in a combustion unit (800 °C) that allows us to directly and unambiguously detect the natural oxygen present in the GC-separated compounds through its incorporation into the volatile species formed after their combustion and their subsequent degradation to 16O in the ion source. The unspecific signal due to the low 16O abundance in the oxidizing gas could be compensated by measuring the m/z 12 that comes as well from the CO2 degradation. Equimolarity was proved with several O-containing compounds with different sizes and functionalities. A detection limit of 28 pg of injected O was achieved, which is the lowest ever reported for any GC detector, which barely worsened to 55 and 214 pg of O when the oxygenate partially or completely coeluted with a very abundant matrix compound. Validation was attained by the analysis of a SRM to obtain accurate (99-103%) and precise (1-4% RSD) results. Robustness was tested after spiking a hydrotreated diesel with 10 O-compounds at the ppm level, which could be discriminated from the matrix crowd and quantified (mean recovery of 102 ± 9%) with a single generic standard. Finally, it was also successfully applied to easily spot and quantify the 33 oxygenates naturally present in a complex wood bio-oil sample.

Hydrothermal liquefaction of oil mill wastewater for bio-oil production in subcritical conditions.

The main purpose of this study is to investigate the direct hydrothermal liquefaction of oil mill wastewater (OMWW). Experiments were carried out at different temperatures (240-300°C), water contents (58-88wt.%) and reaction times (15-45min). Results show that the highest bio-oil yield was about 58wt.%, resulting in a higher heating value of 38MJ/kg. This was conducted at the following optimal conditions: water content 88wt.%, a temperature of 280°C, and 30min as reaction time. To put bio-oil into wide application, the various physical and chemical characteristics were determined. A detailed chemical composition analysis of bio-oil was performed by gas chromatography-mass spectrometry (GC-MS) coupled with a flame ionization detector (FID). The dominant compounds were identified by using NIST library. Analyses show that the bio-oil contains mainly oleic acid, hexadecanoic acid, fatty acid methyl ester, fatty acid ethyl ester, amino acid derived compounds and phenolic compounds.