Evolved Gas Analysis Research Articles

Thermal, mechanical, and electrical properties of difunctional and trifunctional epoxy blends with nanoporous materials

In the present study, the aim is to synthesize the particulate nanocomposites with difunctional and trifunctional epoxy blend as matrix and synthesized nanoporous materials as fillers. Organic/inorganic hybrid networks were prepared by the novel solvent free method. Viscoelastic, thermal, and electrical properties of di- and trifunctional epoxy and the effect of different nanoparticles in the particulate nanocomposites have been studied by dynamic mechanical analyzer, thermogravimetry (TGA), and dielectric strength. Epoxy mixed with different compositions of TGPAP and particulate nanocomposites by the addition of different types of nanomaterials shows higher storage modulus than the pure epoxy. The addition of TGPAP and nanofillers decreases the thermal stability of epoxy matrix. The evolved gas analysis (TG-FTIR) was also done in order to study the products formed during degradation. An increase in dielectric strength and impact strength (4%) was also observed in the particulate nanocomposites.

Synergistic effects during co-pyrolysis of milled wood lignin and polyolefins at the gas phase and liquid/solid phase contacting modes

Co-pyrolysis of biomass and waste plastics is the preferred technology for enhancing the production of fuels and valuable chemicals. Here, we studied the co-pyrolysis of milled wood lignin (MWL) with polyethylene (PE) and polypropylene (PP) at various weight ratios by thermogravimetry (TG), evolved gas analysis–mass spectrometry (EGA–MS), and product recovery tests using a fixed-bed reactor. Two reaction modes, liquid/solid phase (LSP) and gas phase (GP) contacting modes, were applied to investigate the physical prevention of melted polymers on the interactions between the vapored intermediates. The TG results showed that the weight losses were slightly altered in the MWL/PE and the decomposition was delayed in MWL/PP blends, whereas the EGA-MS analysis indicated that more vaporized products from the blends were detected by MS. The fixed-bed experiments showed that the yield of liquid was largely enhanced by the higher proportion of PE or PP in the blends, primarily due to the formation of lower oligomeric hydrocarbons from polyolefins. The yields of gasoline and kerosene were significantly increased in the GP mode from the co-pyrolysis of MWL with PE and PP, respectively. These results suggest that the MWL pyrolysates could enhance the cracking of PE intermediates in the GP reaction mode, whereas the rearrangement reactions of PP intermediates may be inhibited in the LSP reaction mode, converting more wax products into liquid. This paper provides a better understanding of the detailed synergistic effects during biomass and plastics co-pyrolysis.

Evolved Gas Analysis and Kinetics of Catalytic and Non-Catalytic Pyrolysis of Microalgae Chlorella sp. Biomass With Ni/θ-Al2O3 Catalyst via Thermogravimetric Analysis

This study investigates the efficacy of a prepared Ni/θ-Al2O3 catalyst during the pyrolytic conversion of Parachlorella kessleri HY-6 and compares the results with non-catalytic conversion. The catalyst was characterized by techniques such as Brunauer–Emmett–Teller (BET) for surface area, acidity, and X-ray powder diffraction (XRD). Isoconversional and combined kinetic methods were used to study the pyrolytic kinetics of the process. Ni/θ-Al2O3 was used at 10, 20, and 30% of the algal biomass. The addition of Ni/θ-Al2O3 facilitated the conversion by lowering the mean activation energy during pyrolysis. The catalytic effect was more pronounced at lower and higher conversions. The presence of the catalyst facilitated the pyrolysis as indicated by the lower value of activation energy and ∆H, and ∆G. Gases evolved during pyrolysis were qualitatively analyzed by FTIR to see the effect of catalyst on evolved gas composition during the pyrolysis process.

Disclosing the chemistry of oil curing by mass spectrometry using methyl linoleate as a model binder

The structure of the polymeric fraction in an oil painting is believed to be strongly connected to the stability of the paint layers over time, but its molecular characterisation is extremely difficult given the complex composition of a vegetable oil-based polymer.In this study we report the implementation of a methodological approach for the systematic mass spectrometric investigation of the molecular features of the products of oxidative degradation and cross-linking of oil paint layers upon curing. The approach is based on the use of methyl linoleate as a simplified model of an oil paint binder. Gas-chromatography coupled with mass spectrometry, solid phase microextraction gas chromatography mass spectrometry, flow injection electrospray mass spectrometry and evolved gas analysis mass spectrometry, are used to analyse the evolution of compounds produced over seven months of natural ageing, from the volatile products to the macromolecular and cross-linked fractions. The aim is to improve our fundamental molecular understanding of the curing process of oil paints, and to investigate the balance between oxidative degradation and cross-linking when specific binder-pigment combinations are in place.Model paint layers were prepared using lead white and ultramarine blue as pigments. These two pigments are known to produce paint layers with different stability over time. The use of methyl linoleate as model oil binder greatly simplifies the mass spectral features of the lipid paint fraction, enabling the detection of products of oxidation and cross-linking with a new high level of molecular detail. Data clearly show that crucial differences between paints containing the two pigments establish with time, which are mostly related to the cross-linked fraction.

Assessing the thermal and fungal behavior of eco-friendly epoxy thermosets derived from vegetable oils for wood protective coatings

The paper deals with the study of the obtaining, characterization and thermal and fungal behavior of a green thermoset based on epoxidized soybean oil (ESO), castor oil maleic anhydride adduct (COMA) and methyl nadic anhydride (MNA). By varying the MNA/COMA crosslinking agent ratio, resins with different degree of stiffness can be obtained suitable for green thermosets coatings. Differential scanning calorimetry (DSC) and a simultaneous TG/FT-IR/MS coupling were used to establish the crosslinking behavior, evolved gases analysis and thermal decomposition mechanisms associated with their corresponding kinetic parameters. The non–isothermal global kinetic parameters values (activation energy and pre–exponential factor) were calculated with the aid of the Friedman and Flynn–Wall–Ozawa isoconversional methods. The curves shape of the variation of activation energy versus conversion degree and first derivative (DTG) curves shapes suggest that the thermal degradation processes occurred in multi-step kinetics. Using a multivariate linear regression method the most probable thermal decomposition and crosslinking kinetic models were established. A good concordance between experimental and simulated data was obtained, confirming the correct description of the thermal mechanisms. The main identified gaseous fragments were water, carbon dioxide, saturated and unsaturated hydrocarbons and carboxylic derivatives. The decay resistance against two wood decaying strains, P. chrysogenum and A. brasiliensis was also evaluated.

Thermal stability of polymeric carbon nitride (PCN)-Al2O3–ZrO2 nanocomposites used in photocatalysis

Polymeric carbon nitride (PCN) was recently found to have extensive applications in the field of photocatalysis. Knowledge about thermal stability of PCN nanocomposites is crucial for this application and designing the final product. In this work, the thermal stability of PCN-Al2O3–ZrO2 nanocomposites was investigated. PCN nanocomposites were obtained in two steps: (1) microwave hydrothermal synthesis of co-precipitated AlOOH and ZrO2 precursors, followed by drying; (2) mixing the nanopowders with melamine powder and annealing in air in a tube furnace at 400, and 450 °C. The PCN nanocomposites were examined by attenuated total reflection technique of Fourier transformed infrared spectroscopy. Also, the evolved gas analysis was performed combining differential scanning calorimetry and thermogravimetry coupled with mass spectroscopy and FTIR. The results show that only PCN-Al2O3–ZrO2 nanocomposite obtained at 400 °C is stable from room temperature up to 490 °C and during thermal decomposition, in one step releases ammonia (NH3), cyanic acid (HNCO), water (H2O), and carbon dioxide (CO2). The limitation of the PCN-Al2O3–ZrO2 thermal stability and performance is AlOOH–ZrO2 used as a nanocomposite component.

Review on Evolved Gas Analysis Mass Spectrometry with Soft Photoionization for the Chemical Description of Petroleum, Petroleum-Derived Materials, and Alternative Feedstocks

Modern industry strongly relies on the molecular analysis of fossil petroleum and petroleum-derived materials. In the context of a circular economy and carbon neutrality, the chemical description o...

A liquid phosphorous flame retardant combined with expandable graphite or melamine in flexible polyurethane foam

AbstractA systematic series of flexible polyurethane foams (FPUF) with different concentrations of flame retardants, bis([dimethoxyphosphoryl]methyl) phenyl phosphate (BDMPP), and melamine (MA) or expandable graphite (EG) was prepared. The mechanical properties of the FPUFs were evaluated by a universal testing machine. The pyrolysis behaviors and the evolved gas analysis were done by thermogravimetric analysis (TGA) and TGA coupled with Fourier‐transform infrared (TG‐FTIR), respectively. The fire behaviors were studied by limiting oxygen index (LOI), UL 94 test for horizontal burning of cellular materials (UL 94 HBF), and cone calorimeter measurement. Scanning electronic microscopy (SEM) was used to examine the cellular structure's morphology and the postfire char residue of the FPUFs. LOI and UL 94 HBF tests of all the flame retarded samples show improved flame retardancy. BDMPP plays an essential role in the gas phase because it significantly reduces the effective heat of combustion (EHC). This study highlights the synergistic effect caused by the combination of BDMPP and EG. The measured char yield from TGA is greater than the sum of individual effects. No dripping phenomenon occurs during burning for FPUF‐BDMPP‐EGs, as demonstrated by the result of the UL 94 HBF test. EG performs excellently on smoke suppression during burning, as evident in the result of the cone calorimeter test. MA reduces the peak heat release rate (pHRR) significantly. The synergistic effect of the combination of BDMPP and EG as well as MA offers an approach to enhance flame retardancy and smoke suppression.

Investigation of steam gasification in thermogravimetric analysis by means of evolved gas analysis and machine learning

The syngas distribution from steam gasification depends on both the feedstock and the gasification conditions. Therefore, it is of utmost importance to increase the know-how about the overall picture of steam gasification. Thermogravimetric analysis (TGA) is a commonly used method that provides valuable information about the gasification process. The TGA designed for steam gasification and its auxiliary equipment are comparatively expensive, the experiments take a long time and need a qualified operator. Therefore, the development of an easily applicable computational method for thermogravimetric behavior during steam gasification is very important. Although there are some works on predicting the pyrolysis and combustion behavior using artificial neural network (ANN), a model that predicts gasification behavior by TGA has not been studied. In this study, the gasification behavior and gas product characteristics of solid fuels were investigated by TGA coupled with mass spectrometry. Moreover, we report the first comprehensive model to estimate the thermogravimetric behavior of steam gasification using ANN as a machine learning approach. The ANN model provides a reliable estimation with an R2 value of greater than 0.999. Moreover, MAPE values are reported to average less than 1%, while 6.5% for pyrolysis and 33.6% for extrapolated validation conditions.

Waste not, want not: The use of leather waste in flame retarded EVA

Leather is among the most ancient, widely used materials worldwide. Industrial-scale leather production produces large quantities of organic waste attained during shaving and buffing steps during processing. In this study, leather wastes (LW) are used as fillers in flame retarded polymer composites. LW is investigated as a multifunctional bio-filler that enhances the fire performance of flame retarded poly(ethylene–vinyl acetate) (EVA) containing phosphorus flame retardants (P-FRs) ammonium polyphosphate (APP) or a melamine-encapsulated APP (eAPP). Using LW from tanneries as adjuvants to enhance P-FRs in EVA reduces industrial wastes that otherwise require costly waste management solutions. Materials are characterized multi-methodically via mechanical tests, electron microscopy, rheology, thermogravimetric analysis, evolved gas analysis, and condensed phase FTIR, also reaction-to-small-flames and cone calorimeter tests. EVA containing 10 wt-% LW and 20 wt-% P-FRs achieve 20% reductions in fire loads versus EVA, and up to 10% reduction in effective heats of combustion versus EVA with equal (30 wt-%) P-FR loadings. Enhanced char stabilization of EVA composites with LW and P-FRs lowered peaks of heat release rates up to 53% compared to EVA, and up to 40% compared to equal P-FRs loadings. Synergisms between LW and P-FRs in EVA are quantified. A chemical decomposition mechanism is proposed.

Geochemical, Geotechnical, and Microbiological Changes in Mg/Ca Bentonite after Thermal Loading at 150 °C

Bentonite buffers at temperatures beyond 100 °C could reduce the amount of high-level radioactive waste in a deep geological repository. However, it is necessary to demonstrate that the buffer surrounding the canisters withstands such elevated temperatures, while maintaining its safety functions (regarding long-term performance). For this reason, an experiment with thermal loading of bentonite powder at 150 °C was arranged. The paper presents changes that the Czech Mg/Ca bentonite underwent during heating for one year. These changes were examined by X-ray diffraction (XRD), thermal analysis with evolved gas analysis (TA-EGA), aqueous leachates, Cs sorption, cation exchange capacity (CEC), specific surface area (SSA), free swelling, saturated hydraulic conductivity, water retention curves (WRC), quantitative polymerase chain reaction (qPCR), and next-generation sequencing (NGS). It was concluded that montmorillonite was partially altered, in terms of the magnitude of the surface charge density of montmorillonite particles, based on the measurement interpretations of CEC, SSA, and Cs sorption. Montmorillonite alteration towards low- or non-swelling clay structures corresponded well to significantly lower swelling ability and water uptake ability, and higher saturated hydraulic conductivity of thermally loaded samples. Microbial survivability decreased with the thermal loading time, but it was not completely diminished, even in samples heated for one year.

Butyl-Methyl-Pyridinium Tetrafluoroborate Confined in Mesoporous Silica Xerogels: Thermal Behaviour and Matrix-Template Interaction.

Organic-inorganic silica composites have been prepared via acid catalyzed sol-gel route using tetramethoxysilan (TMOS) and methyl-trimethoxysilane (MTMS) as silica precursors and n-butyl-3-methylpyridinium tetrafluoroborate ([bmPy][BF4]) as co-solvent and pore template, by varying the content of the ionic liquid (IL). Morphology of the xerogels prepared using the ionic liquid templating agent were investigated using scanning electron microscopy and small angle neutron scattering (SANS). Thermal analysis has been used in order to evaluate the thermal and structural stability of the materials, in both nitrogen and synthetic air atmosphere. In nitrogen atmosphere, the IL decomposition took place in one step starting above 150 °C and completed in the 150–460 °C temperature interval. In synthetic air atmosphere, the IL decomposition produced two-step mass loss, mainly in the 170–430 °C temperature interval. The decomposition mechanism of the IL inside the silica matrix was studied by mass spectrometric evolved gas analysis (MSEGA). The measurements showed that the degradation of the IL’s longer side chain (butyl) starts at low temperature (above 150 °C) through a C-N bond cleavage, initiated by the nucleophilic attack of a fluorine ion.

Analytical Techniques for Detection of Oil Presence in Mortar

Oils, e.g. linseed oil, has been used as mortar admixtures or components of lime-oil mastic since ancient times. The reason was either to increase the mortar durability and/or to prolong the mortar/mastic workability. Historic mortars are conventionally analyzed by means of X-ray diffraction and thermal analysis, but these methods are not able to detect the organic compounds directly. The goal of the present research was to evaluate the applicability of thermal analysis, infra-red spectroscopy, solid state NMR spectroscopy and gas chromatography for detection and possible quantification of linseed oil in prepared mortar containing, beyond the oil, just lime and calcite. Both applied spectroscopies were able not only detect the presence of oil but may be used also for study of the oil chemical transformation in the alkaline environment of the lime mortar. Thermal analysis is not able to identify kind of organic admixture, but when it is known that it is e.g. linseed oil, its quantification by help of Evolved Gas Analysis is very good. The results of gas chromatography of mortar’s extract are affected by the polymerization of oil in mortar. The total organic content analysis is providing good information about the total amount of organics in mortar. There in not any single method, which could provide all information about the oil admixture in mortar (kind of oil, content of oil, fate of oil after mortar’s mixing) by itself; the combination of techniques must be used.

Integrating Thermal Analysis and Reaction Modeling for Rational Design of Pyrolytic Processes to Remediate Soils Contaminated with Heavy Crude Oil.

We developed a novel methodology that combines thermo-analytical measurements and mathematical methods to inform the reliable pyrolytic treatment of specific soil/contaminant systems. Our approach improves upon current "black-box" design methods that may overestimate the required treatment intensity and hinder cost efficacy. We used thermogravimetry and evolved gas analysis to characterize the complex network of soil mineral transformations, contaminant desorption, and pyrolytic reactions occurring when contaminated soils are heated in an anoxic atmosphere. The kinetics of these reactions were quantified using a distributed activation energy (DAE) approach with six pseudocomponents and used in a mathematical model for continuous-flow reactors to predict the removal of hydrocarbon contaminants without other fitting parameters. This model was tested with pilot-scale data from pyrolytic treatment of soils contaminated with crude oil and found to be a good predictor of the total petroleum hydrocarbon (TPH) removal for temperatures between 370 and 470 °C and residence times from 15 to 60 min. The light hydrocarbon fraction desorbed quickly, and over 99.7% removal was achieved at 420 °C and 15 min residence time. However, 95% removal of the heavy hydrocarbon fraction, which is a good proxy for polyaromatic hydrocarbons (PAHs), required 470 °C with 15 min residence time. This model can be employed to select operating conditions (e.g., reactor size, treatment time, and temperature) to reliably achieve remediation objectives for specific hydrocarbon/soil mixtures without inflating energy requirements, which would lower operating costs and decrease the process carbon footprint on a system-specific basis.

Elemental Carbon and Its Fractions during Evolved Gas Analysis with Respect to Pyrolytic Carbon and Split Time

We demonstrated the relationships between elemental carbon (EC) and EC fractions during evolved gas analysis (EGA) for PM2.5 sampled at KOREATECH from 29 March 2018 to 12 May 2018. The EC concentrations were compared to the concentrations of equivalent black carbon to confirm that the level of EC concentrations analyzed in this study was valid. Among various EC fractions and their combination, EC1+EC3 fractions were best correlated with the EC concentrations. Especially, dominant EC fraction was related with the dependence of carbon oxidation quantity on the oxidation temperature. We also examined the relationships between pyrolytic carbon (PyC) and EC concentration with respect to the split time. PyC was correlated with the split time in the phase of oxygen-helium mixture. PyC was close to zero for the split time in the helium phase. It is novel, as far as the authors know, that the correlation between PyC and the split time under NIOSH 5040 protocol was reported with regard to EGA. We believe that our study helps to identify what causes uncertainty in the quantification of PyC.

Thermal study, temperature diffraction patterns and evolved gas analysis during pyrolysis and oxidative decomposition of novel ternary complexes of light lanthanides with mefenamic acid and 1,10-phenanthroline

New ternary lanthanide complexes with mefenamic acid (Hmef) and phenanthroline with the stoichiometry Ln2(mef)5(phen)(OH)·nH2O (Ln = La and Ce) and Ln2(mef)4(phen)(OH)2·nH2O (Ln = Pr, Nd, Sm, Eu and Gd) were synthesized and fully characterized by an elemental analysis, infrared spectroscopy, powder X-Ray diffraction (PXRD), combined thermogravimetry and differential scanning calorimetry (TG-DSC) in air and nitrogen atmospheres, evolved gas analysis by combined TG-FTIR-MS techniques as well as temperature controlled X-ray diffraction.The PXRD data suggest that the compounds are crystalline or amorphous and no isomorphic series were obtained. The FTIR spectra suggested the coordination of the lanthanide ions by the bidentate carboxylate groups of mefenamates as well as nitrogen atoms of phenanthroline.The thermal decomposition pathways of the complexes depended on the metal center and differed in air atmosphere and nitrogen atmosphere. From the temperature diffraction patterns, it was experimentally confirmed that in-air degradation of the complexes proceeded with the formation of various lanthanide oxycarbonates as intermediate solids and the decomposition was completed up to 1000 °C with the formation of the appropriate lanthanide oxides as a final solid product. It was proved that during degradation of the tested compounds in nitrogen atmosphere, a mixture of lanthanide oxide, lanthanide oxycarbonate, and soot is formed as an intermediate solid product at around 800 °C and pyrolysis is not finished for all compounds up to 1000 °C. The main gaseous products released during the thermal decomposition of these compounds were water vapor, carbon dioxide, carbon monoxide, nitrogen oxide and ammonia (in air atmosphere), as well as water vapor, carbon oxides, ammonia and a mixture of hydrocarbons from mefenamate ligand degradation (in nitrogen atmosphere).

Synthesis, structure, optical and thermal analysis of the new compound of the new compound organo-metallic (C5H6N)2TeCl6

A new organic-inorganic phase compound (C5H6N)2TeCl6, was synthesized and its structure was determined at room temperature in the monoclinic system (C2/m space group) with the following lattice parameters: a = 12.9000(18) Å, b = 8.4777(12)Å, c = 8.0127(11)Å and β = 96.860(2)°. The final refinement cycle of all isotropic and anisotropic thermal parameters led to R = 0.026 and wR = 0.03. The anion and cation chains are linked by N-H…Cl hydrogen bonds.The infrared spectra were recorded in the 4000–400 cm−1 frequency region. The Raman spectra were recorded in the external region of the anionic sublattice vibration 50–1500 cm−1. The optical band gap was calculated from the UV-Vis absorbance spectra using classical Tauc relation which was found to be 2.48 eV. Several thermal analysis techniques such as thermogravimetric analysis, differential scanning calorimetric analysis and evolved gas analysis were used. We observe that the decomposition of (C5H6N)2TeCl6 occurs between 473 and 573 K with the formation of pyridine, HCl, Cl2 and N2 as volatiles.

Effect of brominated flame retardant on the pyrolysis products of polymers originating in WEEE.

Chemical recycling is an environmentally friendly method, which is often used for the recycling of plastics included in waste electric and electronic equipment (WEEE), since fuels and secondary valuable materials can be produced. Brominated flame retardants (BFRs) are usually added into these plastics to reduce their flammability; but they are toxic substances. The aim of this work is to examine the thermal behaviour and the products obtained after pyrolysis of polymer blends that consist of acrylonitrile-butadiene-styrene (ABS), high-impact polystyrene (HIPS), polycarbonate (PC) and polypropylene (PP) with composition that simulates real WEEE, in the absence and presence of a common BFR, tetrabromobisphenol A (TBBPA), in order to investigate its effect on pyrolysis products. Blends were prepared via the solvent casting method and the melt-mixing in an extruder; it was revealed that the latter method may be a better choice for blends preparation, since it did not affect the products obtained. The chemical structure of each polymeric blend was identified by Fourier transform infrared spectroscopy (FTIR). Thermal degradation of the blends was evaluated by thermogravimetric (TG) experiments performed using a thermal analyser (TGA) and a pyrolyser for evolved gas analysis (EGA). It was observed that blends had a similar behaviour during their thermal degradation; and in most cases, they followed a one-step mechanism. Pyrolysis products were identified by the pyrolyser combined with a gas chromatographer/mass spectrometer (GC/MS), and comprised various useful compounds, such as monomers, aromatic hydrocarbons and phenolic compounds that could be used as chemical feedstock. Furthermore, it was found that TBBPA affected products distribution by enhancing the formation of phenolic compounds and on the other hand by resulting in brominated compounds, such as dibromophenol.

TG pyrolysis of a mixture of dried sludge from urban wastewater and wood pellets and identification of the composition of the resulting gases by infrared spectroscopy

The recent tendency of sewage sludge disposal is targeted towards the gasification for heat generation in small towns far from waste incineration plants. The scope of this article is to present the investigation into the mixture of dried sewage sludge and wood pellets during pyrolysis by thermogravimetry (TG) with evolved gas analysis by TG-coupled Fourier transformation infrared spectroscopy (FTIR) method. The maximum intensity of mass loss of sewage sludge material occurs at 300–310°C temperature and it differs from wood cellulose case of 360°C. The 50:50% mixture of these materials was investigated in more details. Pyrolysis reaction kinetics is described by a variation of three constituent parts from TG data. Prefactor A and activation energy E of the Arrhenius law were found, and reaction order n was determined by the Ozawa method employing Avrami phase change. The maximum of gas evolution is always related to the most intense mass loss, and gas composition correlates with the initial material.

Analytical pyrolysis and thermal analysis to chemically characterise bitumen from Italian geological deposits and Neolithic stone tools

The chemical study of bitumen from stone tools from Italian Neolithic sites was carried out using analytical pyrolysis-based techniques, EGA-MS (evolved gas analysis mass spectrometry) and DSPy-GC/MS (double shot pyrolysis-gas chromatography/mass spectrometry). The study was mainly aimed at demonstrating the suitability of analytical pyrolysis for studying archaeological bitumen and for obtaining information regarding its origin. EGA-MS was employed to obtain information on the thermal complexity, that is the set of thermal properties and behaviours, of the samples and on their thermal degradation areas and DSPy-GC/MS along with Principal Component Analysis (PCA) were tested for biomarker analysis to assess bitumen source in archaeological objects. Geological bituminous rocks from Central-Southern Italy were selected and used as reference materials to both optimize experimental parameters and to support data interpretation for archaeological samples. Geological samples were also preliminary characterised by thermogravimetric analysis coupled with FTIR spectroscopy (TG-FTIR) under nitrogen and by TG analysis under oxygen to quantify their relative content of organic and inorganic species.The combination of thermal analysis and analytical pyrolysis-based techniques allowed us to quantify the organic content of the bitumen samples and to obtain information on both soluble and insoluble organic fractions. In addition, the proposed approach highlighted the main degradative patterns and the main differences among samples coming from different geographical areas as well as differences between geological and archaeological bitumen. Finally, DSPy-GC/MS associated with PCA proved to be successful in assessing the bitumen source in archaeological objects by the detection of terpanes, distinctive biomarkers.