Waste surgical masks to fuels via thermochemical co-processing with waste motor oil and biomass.

In this work, the co-processing of waste surgical masks, waste motor oil, and biomass was investigated to reduce the environmental impacts of the increasing medical-derived plastic pollution as well as to elucidate its effect on the production of chemicals . The results showed high yields towards an oily product with an interesting hydrocarbon content in the diesel range. Furthermore, although the initial waste motor oil had a high sulfur content, the oily products showed a low sulfur content, that was logically distributed in the solid and gas phases. In addition, all oily products presented HHVs ​​higher than 44 MJ/Kg, with cetane indices, densities, and viscosities lower than those of petroleum-derived diesel. This work could impact on the management of waste surgical masks and the joint recovery of everyday waste towards high value-added products.

Characterization of biomass and biochar by LDI-FTICRMS - Effect of the laser wavelength and biomass material.

The pyrolysis of the lignocellulosic biomass is a promising process to produce biofuels or green chemicals. Specific analytical methods have to be developed in order to better understand the composition of biomass and of its pyrolysis products and therefore to optimize the design of pyrolysis processes. For this purpose, different biomasses (Douglas and Miscanthus) and one biochar were analyzed by laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (LDI FT-ICR MS). This method allowed the biomass and biochar to be analyzed without any sample preparation and with a spatial resolution of about 100 µm. The influence of LDI conditions (laser wavelength and laser irradiance) and the nature of the biomass and biochar on the obtained mass spectrum were investigated. The nature and origin of the observed ions highly depended on LDI conditions. In the softest laser-biomass interaction conditions (low laser irradiance), the detected ions were related to the nature of the investigated biomass. Indeed, the main part of the detected species came from the different biomass subunits and was produced by photolysis of covalent bonds. When more severe laser irradiation conditions were used, the obtained mass spectra gathered the ions relative to (i) the chemical components of the investigated samples, (ii) the recombination products of these species in the gas phase after their ejection from the sample surface, and (iii) the compounds produced by laser pyrolysis of the sample. This was expected to be useful to mimic thermal pyrolysis. Graphical Abstract.

Characterization of crude oil asphaltenes by coupling size-exclusion chromatography directly to an ultrahigh-resolution mass spectrometer.

RATIONALE: Fossil fuels are one of the most important energy resources until new sustainable materials become available. To optimize the upgrading processes of these materials characterization of the remaining heavy materials is of great importance. METHODS: Asphaltenes are the most difficult fraction of crude oil to process due to the limited number of solvents in which they can be dissolved. Chromatographic separation methods need to consider the difficulties associated with these limitations. Size-exclusion chromatography (SEC) in combination with Fourier transform Orbitrap mass spectrometry (MS) combines the capabilities of ultrahigh resolution and very high mass accuracy with a separation method that allows using solvents as mobile phase for asphaltene separation. RESULTS: A chromatographic method was developed that shows the separation of asphaltenes according to their molecular mass. A simplification of the samples was achieved by reducing the number of compounds present in a single spectrum compared to infusion data. Direct detection by mass spectrometry additionally allows a distinction of different isomers present in the complex samples. CONCLUSIONS: Direct coupling of SEC with ultrahigh-resolution mass spectrometry allows the study of the most difficult to analyze fraction of crude oil, the asphaltene fraction. Separation reduces the complexity of individual spectra and, therefore, also reduces suppression and discrimination effects. The separation of structural isomers which cannot be characterized by MS alone gives an added dimension to the analysis of asphaltenes. Copyright © 2016 John Wiley & Sons, Ltd.

Effect of Potassium on the Mechanisms of Biomass Pyrolysis Studied using Complementary Analytical Techniques.

Complementary analytical methods have been used to study the effect of potassium on the pyrolysis mechanisms of cellulose and lignocellulosic biomasses. Thermogravimetry, calorimetry, high-temperature (1) H NMR spectroscopy (in situ and real-time analysis of the fluid phase formed during pyrolysis), and water extraction of quenched char followed by size-exclusion chromatography coupled with mass spectrometry have been combined. Potassium impregnated in cellulose suppresses the formation of anhydrosugars, reduces the formation of mobile protons, and gives rise to a mainly exothermic signal. The evolution of mobile protons formed from K-impregnated cellulose has a very similar pattern to the evolution of the mass loss rate. This methodology has been also applied to analyze miscanthus, demineralized miscanthus, miscanthus re-impregnated with potassium after demineralization, raw oak, and Douglas fir. Hydrogen mobility and transfer are of high importance in the mechanisms of biomass pyrolysis.

Detection and monitoring of PAH and oxy-PAHs by high resolution mass spectrometry: comparison of ESI, APCI and APPI source detection.

The objective of this work was to compare direct infusion in a Q-TOF mass spectrometer through three different atmospheric pressure sources, electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) coupled to a high resolution Q-TOF mass spectrometer. A complex mixture of PAH and oxy-PAHs, obtained after the air oxidation of fluoranthene on mineral substrates, was used to compare the different ionization abilities of these sources. Here, we propose analytical methods for the use of all sources. Final goal was to provide background to the choice of the most appropriate source in order to analyze complex organic mixtures as those encountered in polluted soils, water, sediments, as well as in petroleum.

Low temperature oxidation of a coking plant soil organic matter and its major constituents: an experimental approach to simulate a long term evolution.

In contaminated soils, several natural processes (biodegradation, oxidation, etc.) can induce degradation of organic pollutants. The aim of this work was to evaluate the impact of an abiotic low-temperature oxidation on a coking plant soil and its main organic constituents (coal, coke, coal tar and road asphalts) in order to understand its long term evolution. This natural process was experimentally reproduced by oxidizing the soil and isolated organic matrices at 100 °C during 180 days. The samples were analyzed by total organic carbon measurements and elemental analyses, and the solvent-extractable organic matter was quantified by GC-MS (gas chromatography-mass spectrometry). Oxidation experiments on coal, coal tar and coking plant soil samples lead to the decrease in polycyclic aromatic hydrocarbon (PAH) concentrations correlated to an incorporation of oxygen evidenced by the production of oxygenated PAHs. The increasing amount of polar macromolecules and the decrease in solvent-extractable organic matter suggest a molecular growth through ether/ester cross-linking. The chemical environment of organic compounds and the presence of a reactive mineral fraction are important parameters that improve the efficiency of oxidation. This work reveals that abiotic low temperature oxidation, can strongly contribute to pollutant removal especially by a stabilization process and should be considered in the long term evolution of a soil.

Low-temperature, mineral-catalyzed air oxidation: a possible new pathway for PAH stabilization in sediments and soils.

Reactivity of polycyclic aromatic hydrocarbons (PAHs) in the subsurface is of importance to environmental assessment, as they constitute a highly toxic hazard. Understanding their reactivity in the long term in natural recovering systems is thus a key issue. This article describes an experimental investigation on the air oxidation of fluoranthene (a PAH abundant in natural systems polluted by industrial coal use) at 100°C on different mineral substrates commonly found in soils and sediments (quartz sand, limestone, and clay). Results demonstrate that fluoranthene is readily oxidized in the presence of limestone and clay, leading to the formation of high molecular weight compounds and a carbonaceous residue as end product especially for clay experiments. As demonstrated elsewhere, the experimental conditions used permitted the reproduction of the geochemical pathway of organic matter observed under natural conditions. It is therefore suggested that low-temperature, mineral-catalyzed air oxidation is a mechanism relevant to the stabilization of PAHs in sediments and soils.