Characterization of volatile and non-volatile fractions of spices using evolved gas analysis and multi-shot analytical pyrolysis

In the present work, evolved gas analysis-mass spectrometry (EGA-MS) and analytical pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) were used to characterize both the volatile and non-volatile fractions of six commercially available spices. Analysis of spices is usually performed through the study of their headspace composition by solid phase microextraction (SPME). In this new approach, EGA-MS was used to establish thermal degradation regions, and Py-GC/MS was used to obtain compositional information on each region separately using double-shot pyrolysis. This study demonstrates that EGA-MS and Py-GC/MS provide the same advantages of solid-phase micro extraction and increase the range of detectable products by performing high-temperature desorption and degradation of the non-volatile fraction of spices. Our approach provided both qualitative and semi-quantitative data that could be used in the future to improve authentication studies by considering the results not only of headspace composition, but also on the pyrolytic behavior of the lignocellulosic matrix

A mass spectrometric study on tannin degradation within dyed woolen yarns

Natural tannins from various plants have been used throughout human history in textile dyeing, often as mordant dyes. The ageing behavior of these dyes is a challenge in conservation science, requiring a thorough knowledge of the textile–mordant-dye system. In this work, we analyzed reference wool yarns dyed with natural tannins from oak gallnuts, walnut (Juglans regia), and catechu (Acacia catechu), after artificial ageing. To gain insights on the composition of the dyestuffs and on how they aged, an analytical procedure based on extraction with Na2EDTA/DMF (ethylenediaminetetraacetic acid/dimethylformamide) and high-performance liquid chromatography (HPLC) analysis using high-resolution mass spectrometry detection was used. Since conventional reversed-phase (RP) columns usually show poor retention efficiency of highly polar compounds such as tannins, an RP-amide embedded polar group stationary phase was used to achieve optimal retention of the most polar compounds. Tannins from oak gallnuts showed little degradation after ageing, while a significant increase in the content of hydroxybenzoic acids was observed for tannins from walnut and catechu. Finally, the analytical procedure was applied to characterize the tannin dyes in historical tapestries from the 15th to 16th century, and the results were discussed in comparison with the reference yarns

Mechanistic aspects of thioflavin-T self-aggregation and DNA binding: evidence for dimer attack on DNA grooves

Thioflavin-T (TFT) is a fluorescent marker widely employed in biomedical research but the mechanism of its binding to polynucleotides has been poorly understood. This paper presents a study of the mechanisms of TFT self-aggregation and binding to DNA. Relaxation kinetics of TFT solutions show that the cyanine undergoes dimerization followed by dimer isomerisation. The interaction of TFT with DNA has been investigated using static methods, such as spectrophotometric and spectrofluorometric titrations under different conditions (salt content, temperature), fluorescence quenching, viscometric experiments and the T-jump relaxation method. The combined use of these techniques enabled us to show that the TFT monomer undergoes intercalation between the DNA base pairs and external binding according to a branched mechanism. Moreover, it has also been observed that, under dye excess conditions, the TFT dimer binds to the DNA grooves. The molecular structures of intercalated TFT and the groove-bound TFT dimer are obtained by performing QM/MM MD simulations

Chemical modification of wood induced by the traditional making procedures of bowed string musical instruments: the effect of alkaline treatments

Over the last few decades, chemical and physical studies on bowed string musical instruments have provided a better understanding of their wooden finished surface. Nevertheless, until now only a few of them investigated the effects of the chemical pre-treatments in the traditional making procedures. Those treatments are believed to affect wood properties, its interaction with the following treatments (i.e. varnish application) and its vibro-mechanical behaviour (that may contribute to the acoustical properties of musical instruments). In this study, two traditional alkaline treatments were applied to reference samples of spruce wood, the wood commonly used to make violins’ soundboards. An integrated analytical strategy, which combines infrared spectroscopy, analytical pyrolysis coupled to gas chromatography-mass spectrometry, and gel permeation chromatography, was employed to investigate the chemical alterations of lignocellulosic polymers (cellulose, hemicellulose, and lignin). Results have shown that the selected alkaline treatments induce the partial hydrolysis of the hemicellulose chains and a slight decrease in the crystallinity of cellulose. We could also prove: (i) the cleavage of lignin-carbohydrate complexes formed by the covalent bonds between hemicellulose and lignin in spruce wood, and (ii) the partial breaking of the hydrogen bonds network in cellulose. According to the literature, the alteration of the lignin-carbohydrate complexes is responsible for changes in wood mechanical behaviour. Hence, future perspectives of this research could outline new knowledge on the vibro-mechanical behaviour of the violin soundboard and the consequent acoustics

The submarine Congo Canyon as a conduit for microplastics to the deep sea

The increasing plastic pollution of the world’s oceans represents a serious threat to marine ecosystems and has become a well-known topic garnering growing public attention. The global input of plastic waste into the oceans is estimated to be approximately 10 million tons per year and predicted to rise by one order of magnitude by 2025. More than 90% of the plastic that enters the oceans is thought to end up on the seafloor, and seafloor sediment samples show that plastics are concentrated in confined morphologies and sedimentary environments such as submarine canyons. These canyons are occasionally flushed by powerful gravity-driven sediment flows called turbidity currents, which transport vast volumes of sediment to the deep sea and deposit sediment in deep-sea fans. As such, turbidity currents may also transport plastics present in the canyon and bury plastics in deep-sea fans. These fans may therefore act as sinks for seafloor plastics. Here we present a comprehensive dataset showing the spatial distribution of microplastics in seafloor sediments from the Congo Canyon, offshore West Africa. Multicores taken from 16 locations along the canyon, sampled different sedimentary sub-environments including the canyon thalweg, canyon terraces, and distal lobe. Microplastics were extracted from the sediments by density separation and the polymer type, size, and shape of all individual microplastic particles were analysed using laser-direct infrared-spectroscopy (LDIR). Microplastic number concentrations in the sediments of the distal lobe are significantly higher than in the canyon, indicating that the Congo Canyon system is a highly efficient conduit for microplastic transport to the deep sea. Moreover, microplastic concentrations of >20,000 particles per kg of dry sediment were recorded in the lobe, which represent some of the highest ever recorded microplastic number concentrations in seafloor sediments. This shows that deep-sea fans can serve as hotspots and potential terminal sinks for seafloor microplastics

Pyrolysate composition and silylation efficiency in analytical pyrolysis of glucans as a function of pyrolysis time

The pyrolytic behaviour of two oligosaccharides – cellobiose and cellohexose – was studied using reactive pyrolysis-GC/MS with in situ hexamethyldisilazane derivatisation. Pyrolysis was conducted in a sealed vessel at various times ranging from 0.2 to 60 min. Semi-quantitative calculations were carried out on integrated peak areas to obtain information on derivatisation efficiency and composition of the pyrolysate as a function of pyrolysis time. The results were compared with a previous work by us in which glucose and cellulose were studied with the same procedure. The relative areas of anhydrosugars were found to decrease with the increase of the degree of polymerisation of the substrate, while the derivatisation efficiency showed an opposite trend. The results were explained by considering the role of both the sealed environment and water molecules freed during the pyrolysis process. We hypothesised that higher amounts of water were released from glucans with low degrees of polymerization, hindering both secondary pyrolysis reactions and derivatisation efficiency. Glucans with high degrees of polymerization, on the contrary, showed high signals of secondary pyrolysis products, consistent with a lower amount of water and the formation of a liquid phase

Evolved gas analysis-mass spectrometry and isoconversional methods for the estimation of component-specific kinetic data in wood pyrolysis

The pyrolysis reactions of hardwood and softwood were investigated using evolved gas analysis and mass spectrometry (EGA-MS) and by treating the experimental data with isoconversional methods to obtain kinetic information. Mass spectrometric detection allowed the identification of the pyrolysis products to be performed and component-specific thermograms were obtained by the extraction of appropriate m/z values without the need of peak-fitting. Finally, isoconversional methods, both an integral and a differential method, were used on compound-specific thermograms to calculate apparent activation energies of the carbohydrate and lignin fractions separately. The results showed that the two isoconversional methods provide comparable results, and that there are significant differences between the activation energies of the holocellulose and lignin fractions. This work shows that EGA-MS can provide reliable kinetic data for multi-component samples without the need of chemical pre-treatments or signal deconvolution

Effects of Milling and UV Pretreatment on the Pyrolytic Behavior and Thermal Stability of Softwood and Hardwood

UV/visible light is a promising radiation source for biomass pretreatment, but very little knowledge is available on the effect of UV on the thermal behavior of lignocellulose in comparison with more classical, physical pretreatment methods. In this paper, we investigate the effects of ball-milling and UV irradiation on two species of softwood and two species of hardwood, using X-ray diffractometry (XRD), evolved gas analysis-mass spectrometry (EGA-MS), and pyrolysis-gas chromatography coupled to mass spectrometry (Py-GC/MS). The XRD data showed that the crystalline fraction of cellulose was destroyed by milling, but not by irradiation. The EGA-MS data and isoconversional kinetic analysis showed that both milling and irradiation can reduce the thermal stability of wood up to a limit value. The Py-GC/MS data showed that irradiation caused the most significant changes in the pyrolytic behavior of the wood species, increasing the ratio of holocellulose to lignin pyrolysis products and the reactivity of cellulose toward the derivatizing agent. Softwoods were more affected by irradiation than hardwoods. This paper shows that UV irradiation can decrease the recalcitrance of biomass toward pyrolysis, but its efficiency is highly dependent on the type of lignocellulosic substrate

Degradation of wood by UV light: A study by EGA-MS and Py-GC/MS with on line irradiation system

UV degradation of wood is an important phenomenon that entails loss of aesthetic and mechanic properties. The changes are usually studied with artificial ageing followed by spectroscopy, and focus on colour changes. Analytical pyrolysis coupled with gas chromatography-mass spectrometry (Py-GC/MS) and evolved gas analysis-mass spectrometry (EGA-MS) are powerful tools for wood characterisation, but the change in pyrolytic behaviour of wood after UV irradiation is not well documented. In this work, a new instrumental setup was used to perform UV irradiation on line with EGA-MS and Py-GC/MS with in situ derivatisation of fir and chestnut wood. The effect of UV exposure was evaluated in terms of thermal stability and composition of the pyrolysate. TThe results showed that UV degradation of the samples was mainly related to the lignin fraction, and significant differences were observed between the two species. Fir wood, showed extensive degradation after 4 hours of irradiation, while chestnut wood, showed very small changes. Qualitative comparison of the EGA-MS profiles and semi-quantitative analyses of the composition of the pyrolysates revealed that these techniques could be used as a fast monitoring tool to assess the UV degradation of wood

Co-pyrolysis of wood and plastic: Evaluation of synergistic effects and kinetic data by evolved gas analysis-mass spectrometry (EGA-MS)

Co-pyrolysis of biomass and plastics gives rise to synergistic effects that can improve the properties of the resulting bio-oil. In this paper, the co-pyrolysis of lignocellulose (softwoods and hardwoods) and plastic (polyethylene and polystyrene) mixtures at different ratios was investigated by evolved gas analysis-mass spectrometry (EGA-MS). Through the extraction of specific sets of m/z values, we were able to build component-specific thermograms representative of each component of the mixtures. Such thermograms were used to evaluate the presence of synergistic effects by the comparison with the theoretical thermograms. The shift of the peak temperatures and the differences between the integrated area of the two thermograms showed that both biomass and plastic influence the pyrolytic behaviour of the other component. Finally, the KAS model-free isoconversional method was used on component-specific thermograms to determine apparent activation energies of the biomass and plastic fractions