Catalytic upcycling of post-consumer multilayered plastic packaging wastes for the selective production of monoaromatic hydrocarbons.

In order to obtain extended storage life of food-grade materials and better barrier properties against environmental factors, a multilayer plastic packaging (MLP) is often used. The multilayer packaging plastics are labelled as "other" (SPI#7) category, and are manufactured with a combination of barrier plastics, rigid plastics and printing surface. Owing to their complex composition and difficulty in separating the layers of MLP, its mechanical recycling is challenging. In this study, MLP wastes (MLPWs) were collected from zero-waste garbage collection center of IIT Madras, India, and thoroughly characterized to determine their composition and plastic types. MLPWs were characterized using various physico-chemical methods such as thermogravimetric/differential scanning calorimetric analysis, Fourier transform infrared spectroscopy, bomb calorimetry, and proximate and ultimate analyses. The MLPWs were mainly made up of polyethylene (PE) and polyethylene terephthalate (PET). Further, the non-catalytic and zeolite-catalyzed fast pyrolysis of these MLPWs were studied using analytical pyrolysis coupled with gas chromatograph/mass spectrometer (Py-GC/MS). The non-catalytic fast pyrolysis of MLPWs primarily produced a mixture of aliphatic and alicyclic hydrocarbons, while zeolite catalyzed fast pyrolysis resulted in the formation of mono-aromatic hydrocarbons (MAHs). The activity of HZSM-5, zeolite Y (HY) and zeolite beta (Hß) catalysts were evaluated, and the salient products were quantified. The yields of MAHs like benzene, toluene, ethylbenzene and xylene using the zeolites followed the trend: HZSM-5 (14.9 wt%) > HY (8.1 wt%) > Hß (7.8 wt%), at 650 °C. The use of HZSM-5 resulted in highest yield of MAHs, viz. 16.1 wt%, at the optimum temperature of 550 °C and MLPW-to-catalyst ratio of 1:15 (w/w). The superior activity of HZSM-5 is due to its nominal acidity and larger pore size of 4.24 nm, as compared to HY and Hß. The MAHs yield from three other types of MLPWs varied in the range of 9-16 wt%. The present study demonstrates a promising pathway for the catalytic upcycling of highly heterogeneous MLPWs in the context of circular economy.

Material and Microstructure Analysis of Wood Color Paintings from Shaanxi Cangjie Temple, China.

Cangjie Temple was built to commemorate Cangjie, the legendary inventor of Chinese characters. It stands as one of the few remaining temples in China dedicated to the invention and creation of writing. In this study, the material properties of wooden paintings from the Cangjie temple were characterized using Polarized Light Microscopy (PLM), Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS), Micro-confocal Raman Spectroscopy, X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC/MS). It was confirmed that the pigments of the paintings included cinnabar, lapis lazuli, lead white, Paris green, and carbon black. The proteinaceous glue was used as an adhesive in the pigment samples, with tung oil likely being utilized as a primer for the wooden structures before painting. This study not only provides valuable data support for the conservation and restoration of the architectural features of Cangjie Temple but also provides useful reference for the maintenance and inheritance of similar ancient buildings.

Assessing the Mass Concentration of Microplastics and Nanoplastics in Wastewater Treatment Plants by Pyrolysis Gas Chromatography-Mass Spectrometry.

The level of microplastics (MPs) in wastewater treatment plants (WWTPs) has been well evaluated by the particle number, while the mass concentration of MPs and especially nanoplastics (NPs) remains unclear. In this study, pyrolysis gas chromatography-mass spectrometry was used to determine the mass concentrations of MPs and NPs with different size ranges (0.01-1, 1-50, and 50-1000 µm) across the whole treatment schemes in two WWTPs. The mass concentrations of total MPs and NPs decreased from 26.23 and 11.28 µg/L in the influent to 1.75 and 0.71 µg/L in the effluent, with removal rates of 93.3 and 93.7% in plants A and B, respectively. The proportions of NPs (0.01-1 µm) were 12.0-17.9 and 5.6-19.5% in plants A and B, respectively, and the removal efficiency of NPs was lower than that of MPs (>1 µm). Based on annual wastewater effluent discharge, it is estimated that about 0.321 and 0.052 tons of MPs and NPs were released into the river each year. Overall, this study investigated the mass concentration of MPs and NPs with a wide size range of 0.01-1000 µm in wastewater, which provided valuable information regarding the pollution level and distribution characteristics of MPs, especially NPs, in WWTPs.

Laser microdissection pressure catapulting (LMPC): a new technique to handle single microplastic particles for number-based validation strategies.

This study examines laser microdissection pressure catapulting (LMPC) as an innovative method for microplastic research. Laser pressure catapulting as part of commercially available LMPC microscopes enables the precise handling of microplastic particles without any mechanical contact. In fact, individual particles with sizes between several micrometers and several hundred micrometers can be transported over centimeter-wide distances into a collection vial. Therefore, the technology enables the exact handling of defined numbers of small microplastics (or even individual ones) with the greatest precision. Herewith, it allows the production of particle number-based spike suspensions for method validation. Proof-of-principle LMPC experiments with polyethylene and polyethylene terephthalate model particles in the size range from 20 to 63 µm and polystyrene microspheres (10 µm diameter) demonstrated precise particle handling without fragmentation. Furthermore, the ablated particles showed no evidence of chemical alteration as seen in the particles' IR spectra acquired via laser direct infrared analysis. We propose LMPC as a promising new tool to produce future microplastic reference materials such as particle-number spiked suspensions, since LMPC circumvents the uncertainties resulting from the potentially heterogeneous behavior or inappropriate sampling from microplastic suspensions. Furthermore, LMPC could be advantageous for the generation of very accurate calibration series of spherical particles for microplastic analysis via pyrolysis-gas chromatography-mass spectrometry (down to 0.54 ng), as it omits the dissolution of bulk polymers.

Relating mineral-organic matter stabilization mechanisms to carbon quality and age distributions using ramped thermal analysis.

Organic carbon (OC) association with soil minerals stabilizes OC on timescales reflecting the strength of mineral-C interactions. We applied ramped thermal oxidation to subsoil B horizons with different mineral-C associations to separate OC according to increasing temperature of oxidation, i.e. thermal activation energy. Generally, OC released at lower temperatures was richer in bioavailable forms like polysaccharides, while OC released at higher temperatures was more aromatic. Organic carbon associated with pedogenic oxides was released at lower temperatures and had a narrow range of 14C content. By contrast, N-rich compounds were released at higher temperatures from samples with 2 : 1 clays and short-range ordered (SRO) amorphous minerals. Temperatures of release overlapped for SRO minerals and crystalline oxides, although the mean age of OC released was older for the SRO. In soils with more mixed mineralogy, the added presence of older OC released at temperatures greater than 450°C from clays resulted in a broader distribution of OC ages within the sample, especially for soils rich in 2 : 1 layer expandable clays such as smectite. While pedogenic setting affects mineral stability and absolute OC age, mineralogy controls the structure of OC age distribution within a sample, which may provide insight into model structures and OC dynamics under changing conditions. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

Resource recovery from discarded COVID-19 PPE kit through catalytic fast pyrolysis.

During the COVID-19 pandemic, the world saw an exponential surge in the production of Personal Protective Equipment (PPE) kits, which eventually got discarded in the biomedical waste stream. In this study, thirteen different polymer samples from the PPE kit were collected and characterized using Fourier transform infrared spectrometer, thermogravimetric analysis, and analytical pyrolysis-gas chromatograph/mass spectrometry. The characterization data showed that about 94 % by mass of components were made of only three polymers, viz. polypropylene (PP, 75.6 wt %), polyethylene terephthalate (PET, 12.5 wt %), and polycarbonate (PC, 6 wt %). The analytical pyrolysis of the PPE coverall suit (PP) yielded mainly alkenes containing 2,4-dimethyl-1-heptene as the major compound with 17 wt % yield at 600 °C. The pyrolysates from face shield (PET) were rich in benzoic acid (5.8 wt %) and acetophenone (4.8 wt %), while those from safety goggles (PC) were rich in phenol (17.6 wt %) and p-cresol (12.4 wt %) at 600 °C. HZSM-5 and HY zeolites were used for the catalytic upgradation of pyrolysates especially from PP, PET and PC. The temperature and feed-to-catalyst ratio were optimized by performing catalytic fast pyrolysis experiments at 500 °C, 600 °C and 700 °C with different feed-to-catalyst ratios 1:2, 1:4, and 1:6 (w/w). The yield of aromatic hydrocarbons, viz., BTEX (benzene, toluene, ethylbenzene, xylenes) and naphthalene, was maximum (∼25.7 wt %) from PP coverall when HY catalyst was used at 600 °C and 1:6 (w/w) loading. In the case of PET face shield, the total yield of BTEX, naphthalene and biphenyl was maximum (27.9 wt %) at 600 °C and 1:4 (w/w) of HZSM-5, while in the case of PC goggles, it was maximum (18.6 wt %) at 700 °C and 1:4 (w/w) of HY. This study shows that the entire PPE kit can be valorized via catalytic fast pyrolysis to generate petrochemical products and platform molecules like monoaromatic hydrocarbons at high selectivities.

Pyrolytic kinetics, reaction mechanisms and gas emissions of waste automotive paint sludge via TG-FTIR and Py-GC/MS.

The present study experimentally quantified the pyrolysis behaviors of waste solvent-based automotive paint sludge (OAPS) and water-based automotive paint sludge (WAPS) at four different heating rates using thermogravimetric-Fourier transform infrared (TG-FTIR) spectrometry and pyrolysis-gas chromatography-mass (Py-GC/MS) spectrometry analyses. Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods combined with the master-plots method were employed to investigate the pyrolysis kinetics and reaction mechanisms of waste automotive paint sludge. Three reaction stages and three reaction peaks in stage 2 were distinguished for both OAPS and WAPS degradation. The average activation energy (Ea) estimates for OAPS (FWO: 179.09 kJ/mol; KAS: 168.28 kJ/mol) were slightly higher than WAPS (FWO: 175.90 kJ/mol; KAS: 164.80 kJ/mol) according to FWO and KAS methods. The main pyrolysis reaction mechanisms of both OAPS and WAPS closely matched with the order-based model corresponding to 3rd and 2nd order random nucleation on an individual particle. The evolved gas species of CH4, CO2, phenols, NH3, H2O, and CO from OAPS and WAPS pyrolysis were identified by TG-FTIR. According to Py-GC/MS, hydrocarbons (47.2%) and O-components (42.7%) were relatively large after OAPS and WAPS pyrolysis, respectively. Melamine was the most abundant N-component product after pyrolysis of OAPS (5.8%) and WAPS (4.8%).

Effect of Solvent Treatment on the Composition and Structure of Santanghu Long Flame Coal and Its Rapid Pyrolysis Products.

Easily soluble organic components in Santanghu long flame coal (SLFC) from Hami (Xinjiang, China) were separated by CS2 and acetone mixed solvent (v/v = 1:1) under ultrasonic condition, and the extract residue was stratified by carbon tetrachloride to obtain the light raffinate component (SLFC-L). The effect of solvent treatment on the composition and structure of the coal and its rapid pyrolysis products was analyzed. Solvent treatment can reduce the moisture content in coal from 9.48% to 6.45% and increase the volatile matter from 26.59% to 28.78%, while the macromolecular structure of the coal changed slightly, demonstrating the stability of coal's complex organic structure. Compared with raw coal, the relative contents of oxygen-containing functional groups and aromatic groups in SLFC-L are higher, and the weight loss rates of both SLFC and SLFC-L reached the maximum at about 450 °C. In contrast, the loss rate of SLFC-L is more obvious, being 33.62% higher than that of SLFC. Pyrolysis products from SLFC at 450 °C by Py-GC/MS are mainly aliphatic hydrocarbons and oxygenated compounds, and the relative contents of aliphatic hydrocarbons decreased from 48.48% to 36.13%, while the contents of oxygenates increased from 39.07% to 44.95%. Overall, the composition and functional group in the coal sample were changed after solvent treatment, resulting in a difference in the composition and distribution of its pyrolysis products.

A Study of Pigment, Adhesive, and Firing Temperature in Pottery Figurines Excavated from the Tomb of Qibi Ming, China.

Some painted pottery figurines were excavated from the tomb of Qibi Ming of the Tang Dynasty. A series of analytical techniques were employed to understand the craftsmanship of these painted pottery figurines. The pigment, cross-section, adhesive, and firing temperature were analyzed using microscopy (OM), energy X-ray fluorescence spectrometry (EDX), micro-Raman spectroscopy, pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS), and a dilatometer (DIL). The results demonstrated that the surface of the pigment layers had degraded to different degrees. The pigment particles were litharge, gypsum, malachite, cinnabar, hematite, minium, white lead, and carbon black. The cross-sectional images show that the painted layer of figurines 10-0966 and 10-0678 included a pigment layer and a preparation layer. The preparation layer of both pigments was lead white. Animal glue was used as an adhesive. The firing temperature of the pottery figurines was likely 1080 °C. This study can provide more accurate information with regard to the composition of the raw materials utilized in the making of these artifacts and support the selection of appropriate substances for the purposes of conservation and restoration of the painted pottery figurines.

A Review on Catalytic Fast Co-Pyrolysis Using Analytical Py-GC/MS.

Py-GC/MS combines pyrolysis with analytical tools of gas chromatography (GC) and mass spectrometry (MS) and is a quick and highly effective method to analyse the volatiles generated from small amounts of feeds. The review focuses on using zeolites and other catalysts in the fast co-pyrolysis of various feedstocks, including biomass wastes (plants and animals) and municipal waste materials, to improve the yield of specific volatile products. The utilisation of zeolite catalysts, including HZSM-5 and nMFI, results in a synergistic reduction of oxygen and an increase in the hydrocarbon content of pyrolysis products. The literature works also indicate HZSM-5 produced the most bio-oil and had the least coke deposition among the zeolites tested. Other catalysts, such as metals and metal oxides, and feedstocks that act as catalysts (self-catalysis), such as red mud and oil shale, are also discussed in the review. Combining catalysts, such as metal oxides and HZSM-5, further improves the yields of aromatics during co-pyrolysis. The review highlights the need for further research on the kinetics of the processes, optimisation of feed-to-catalyst ratios, and stability of catalysts and products.

Primary Products from Fast Co-Pyrolysis of Palm Kernel Shell and Sawdust.

Co-pyrolysis is one possible method to handle different biomass leftovers. The success of the implementation depends on several factors, of which the quality of the produced bio-oil is of the highest importance, together with the throughput and constraints of the feedstock. In this study, the fast co-pyrolysis of palm kernel shell (PKS) and woody biomass was conducted in a micro-pyrolyser connected to a Gas Chromatograph-Mass Spectrometer/Flame Ionisation Detector (GC-MS/FID) at 600 °C and 5 s. Different blend ratios were studied to reveal interactions on the primary products formed from the co-pyrolysis, specifically PKS and two woody biomasses. A comparison of the experimental and predicted yields showed that the co-pyrolysis of the binary blends in equal proportions, PKS with mahogany (MAH) or iroko (IRO) sawdust, resulted in a decrease in the relative yield of the phenols by 19%, while HAA was promoted by 43% for the PKS:IRO-1:1 pyrolysis blend, and the saccharides were strongly inhibited for the PKS:MAH-1:1 pyrolysis blend. However, no difference was observed in the yields for the different groups of compounds when the two woody biomasses (MAH:IRO-1:1) were co-pyrolysed. In contrast to the binary blend, the pyrolysis of the ternary blends showed that the yield of the saccharides was promoted to a large extent, while the acids were inhibited for the PKS:MAH:IRO-1:1:1 pyrolysis blend. However, the relative yield of the saccharides was inhibited to a large extent for the PKS:MAH:IRO-1:2:2 pyrolysis blend, while no major difference was observed in the yields across the different groups of compounds when PKS and the woody biomass were blended in equal amounts and pyrolysed (PKS:MAH:IRO-2:1:1). This study showed evidence of a synergistic interaction when co-pyrolysing different biomasses. It also shows that it is possible to enhance the production of a valuable group of compounds with the right biomass composition and blend ratio.

Characterizing natural variability of lignin abundance and composition in fine roots across temperate trees: a comparison of analytical methods.

Lignin is an important root chemical component that is widely used in biogeochemical models to predict root decomposition. Across ecological studies, lignin abundance has been characterized using both proximate and lignin-specific methods, without much understanding of their comparability. This uncertainty in estimating lignin limits our ability to comprehend the mechanisms regulating root decomposition and to integrate lignin data for large-scale syntheses. We compared five methods of estimating lignin abundance and composition in fine roots across 34 phylogenetically diverse tree species. We also assessed the feasibility of high-throughput techniques for fast-screening of root lignin. Although acid-insoluble fraction (AIF) has been used to infer root lignin and decomposition, AIF-defined lignin content was disconnected from the lignin abundance estimated by techniques that specifically measure lignin-derived monomers. While lignin-specific techniques indicated lignin contents of 2-10% (w/w) in roots, AIF-defined lignin contents were c. 5-10-fold higher, and their interspecific variation was found to be largely unrelated to that determined using lignin-specific techniques. High-throughput pyrolysis-gas chromatography-mass spectrometry, when combined with quantitative modeling, accurately predicted lignin abundance and composition, highlighting its feasibility for quicker assessment of lignin in roots. We demonstrate that AIF should be interpreted separately from lignin in fine roots as its abundance is unrelated to that of lignin polymers. This study provides the basis for informed decision-making with respect to lignin methodology in ecology.

Identification and Quantification of Nanoplastics in Surface Water and Groundwater by Pyrolysis Gas Chromatography-Mass Spectrometry.

Nanoplastics (NPs) are currently considered an environmental pollutant of concern, but the actual extent of NP pollution in environmental water bodies remains unclear and there is not enough quantitative data to conduct proper risk assessments. In this study, a pretreatment method combining ultrafiltration (UF, 100 kDa) with hydrogen peroxide digestion and subsequent detection with pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) was developed and used to identify and quantify six selected NPs in surface water (SW) and groundwater (GW), including poly(vinylchloride) (PVC), poly(methyl methacrylate) (PMMA), polypropylene (PP), polystyrene (PS), polyethylene (PE), and poly(ethylene terephthalate) (PET). The results show that the proposed method could detect NPs in environmental water samples. Nearly all selected NPs could be detected in the surface water at all locations, while PVC, PMMA, PS, and PET NPs were frequently below the detection limit in the groundwater. PP (32.9-69.9%) and PE (21.3-44.3%) NPs were the dominant components in both surface water and groundwater, although there were significant differences in the pollution levels attributed to the filtration efficiency of riverbank, with total mass concentrations of 0.283-0.793 µg/L (SW) and 0.021-0.203 µg/L (GW). Overall, this study quantified the NPs in complex aquatic environments for the first time, filling in gaps in our knowledge about NP pollution levels and providing a useful methodology and important reference data for future research.

Biodeterioration of carbographic ribbon: Isolation, identification of causal agents and forensic implications.

This study is part of a comprehensive investigation that was performed in regard to a case of alterations on a carbographic ribbon used in a typewriter that was found and seized by inner security operations of the Arma dei Carabinieri, Italy. Thirty-six coded scripts possessing potentially and criminally liable content were present on the tape; however, only the 6th and 7th scripts exhibited alterations of an uncertain nature. The study included sampling that was performed under sterile conditions of a large surface area of carbographic ribbons. A protocol based on physico-chemical, microbiological, and biomolecular tools was established. Preliminary results revealed the presence of fungal contamination that was primarily located on the inner surface of the 6th and 7th scripts on the black carbographic ribbon. One fungal strain was isolated and identified by universal ITS-PCR primer and rDNA sequencing as Alternaria infectoria strain NIS4. Fungal growth was monitored for 3 weeks in the laboratory under different environmental conditions (temperature, open-closed system, and substrate). The A. infectoria NIS4 strain exhibited the best growth at 28°C under a closed system with RH near saturation. We also noted that the fungal growth was abundant at 15°C. Moreover, this fungus (a potential human pathogen) possessed the ability to colonize the surface of the new carbographic ribbon even when using mineral medium; however, this only occurred in a closed system environment and not in open systems due to rapid desiccation. Under our experimental conditions, the A. infectoria NIS4 strain could degrade gelatin as an organic matter present in trace amounts that are often used as a binder in a carbographic ribbon emulsions. The results revealed that the isolated microorganism was the major biological candidate capable of altering the investigated carbographic ribbon; however, these alterations could only occur under favourable environmental conditions. AIMS: Identify the cause of microbial alterations on a carbographic ribbon in a typewriter used in a hypogean Italian criminal house named "covo." METHODS AND RESULTS: The isolation and identification of biodeteriogens (Alternaria infectoria NIS4) were performed using both culture-dependent and-independent methods, including ITS regions-primed PCR and rDNA techniques. Environmental scanning electron microscopy (ESEM) and optical observations were also performed. Growth tests and biodeterioration simulation tests on carbographic ribbons at the lab scale were performed under different environmental conditions. The A. infectoria NIS4 strain exhibited biodeterioration activity on carbographic ribbons under environmental conditions that were extremely favourable for growth. A high ability to colonize carbographic ribbon surfaces with fast and abundant growth at both 15°C and 28°C under lab-scale conditions at RH near saturation was observed. CONCLUSIONS: In this forensic case study, the ability of the isolated micromycetes A. infectoria NIS4 strain to colonize and induce alterations and degradation in a carbographic ribbon stored under indoor environmental conditions was examined. When favourable conditions change over time, the risk of microbial colonization and the damage produced by the fungal biodeterioration processes on the synthetic material objects has been confirmed. SIGNIFICANCE AND IMPACT OF STUDY: The current study contributes to the knowledge of biodeterioration processes in carbographic ribbon and the responsible agents, and our study provides an example of how environmental microbiology can also aid in forensic studies.

Accelerated and Natural Aging of Cellulose-Based Paper: Py-GC/MS Method.

Samples of papers artificially (2 to 60 days) and naturally (10, 45, and 56 years) aged were studied by the Py-GC/MS method to identify decomposition products. Possible reaction scenarios for cellulose degradation were developed. One of the degradation products is acetic acid, which can (auto)catalyze the cleavage of cellulose ß(1→4)-glycosidic bonds of cellulose polymer chains. However, during 20 s of Py-GC/MS analysis, temperatures of up to 300 °C did not significantly increase or modify the formation of decomposition products of paper components. At 300 °C, the amount of several cellulose decomposition products increased regularly depending on the number of days of artificial aging and natural aging, demonstrated mainly by the generation of 2-furancarboxaldehyde, 5-hydroxymethylfurfural, and levoglucosan and its consecutive dehydration products. No correlation between the amount of lignin decomposition products and the time of aging was found when the pyrolysis was performed at 300 °C and 500 °C. Compounds present in the products of decomposition at 500 °C bear the imprint of the chemical composition of the sampled paper. Pyrograms taken at 300 °C using the Py-GC/MS method can give additional information on the changes in the chemical structure of paper during natural or artificial aging, mainly about the cleavage of ß(1→4)-glycosidic bonds during aging.

Gold Mine Wooden Artefacts: Multianalytical Investigations for the Selection of Appropriate Consolidation Treatments.

Environmental conditions present in mines generally are very favourable to decay; high temperature, high humidity, variable oxygen content, numerous metal-wood connections and the presence of a high content of inorganic compounds typical of mines have a significant impact on the biotic and abiotic degradation factors. The state of conservation of wooden artefacts from the Zloty Stok (Poland) gold mine was investigated using a multi-analytical approach. The aim was to select the conservation treatments that would stop decay and improve the conditions and dimensional stability of the wood. FT-IR and Py-GC/MS were used to assess the state of preservation of lignocellulosic material. ED-XRF and SEM-EDS were used to determine-and XRD to identify crystalline phases-salts and minerals in the wood structure or efflorescence on the surface. Highly degraded lignocellulosic material that had undergone depolymerisation and oxidation was found to be severely contaminated by iron-based mineral substances, mainly pyrite, and in some cases greigite and magnetite. The presence of inorganic salts made it difficult to choose the best consolidating material to reduce the level of decay and improve the dimensional stability of the wood.

Potential of Staphylea holocarpa Wood for Renewable Bioenergy.

Energy is indispensable in human life and social development, but this has led to an overconsumption of non-renewable energy. Sustainable energy is needed to maintain the global energy balance. Lignocellulose from agriculture or forestry is often discarded or directly incinerated. It is abundantly available to be discovered and studied as a biomass energy source. Therefore, this research uses Staphylea holocarpa wood as feedstock to evaluate its potential as energy source. We characterized Staphylea holocarpa wood by utilizing FT-IR, GC-MS, TGA, Py/GC-MS and NMR. The results showed that Staphylea holocarpa wood contained a large amount of oxygenated volatiles, indicating that it has the ability to act as biomass energy sources which can achieve green chemistry and sustainable development.

Organic Markers of Tire and Road Wear Particles in Sediments and Soils: Transformation Products of Major Antiozonants as Promising Candidates.

Tire and road wear particles (TRWPs) are one of the main sources of particulate traffic emissions, but measured data on TRWP contents in the environment are scarce. This study aims at identifying organic compounds suitable as quantitative markers for TRWPs by a tiered multistep selection process involving nontarget screening and subsequent identification by liquid-chromatography high-resolution mass spectrometry. Starting from several thousands of signals recorded in the extract of tire particles, the rigorous selection process considered source specificity, tendency of leaching, analytical sensitivity and precision, and stability during aging. It led to three transformation products of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6-PPD) as the most suitable marker candidates: N-formyl-6-PPD, hydroxylated N-1,3-dimethylbutyl-N-phenyl quinone diimine, and 6-PPD-quinone. A linear response in standard addition experiments with tire particles and the correlation with TRWP contents in a diverse set of environmental samples imply that these compounds are promising candidates as markers for the quantification of TRWPs. Organic markers for TRWP contents in the environment would allow TRWP quantification with the traditional tandem MS (LC-MS/MS) equipment of an organic trace analytical laboratory and, thus, allow easy generation of data on TRWP occurrence in sediments and soils and other environmental matrices.

Comparison of pyrolysis gas chromatography/mass spectrometry and hyperspectral FTIR imaging spectroscopy for the analysis of microplastics.

Analysis of microplastics (MP) in environmental samples is an emerging field, which is performed with various methods and instruments based either on spectroscopy or thermoanalytical methods. In general, both approaches result in two different types of data sets that are either mass or particle number related. Depending on detection limits of the respective method and instrumentation the derived polymer composition trends may vary. In this study, we compare the results of hyperspectral Fourier-transform infrared (FTIR) imaging analysis and pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) analysis performed on a set of environmental samples that differ in complexity and degree of microplastic contamination. The measurements were conducted consecutively, and on exactly the same sample. First, the samples were investigated with FTIR using aluminum oxide filters; subsequently, these were crushed, transferred to glass fiber filters, in pyrolysis cups, and measured via Py-GC/MS. After a general data harmonization step, the trends in MP contamination were thoroughly investigated with regard to the respective sample set and the derived polymer compositions. While the overall trends in MP contamination were very similar, differences were observed in the polymer compositions. Furthermore, polymer masses were empirically calculated from FTIR data and compared with the Py-GC/MS results. Here, a most plausible shape-related overestimation of the calculated polymer masses was observed in samples with larger particles and increased particle numbers. Taking into account the different measurement principles of both methods, all results were examined and discussed, and future needs for harmonization of intermethodological results were identified and highlighted. Graphical abstract.

Microplastics from lagooning sludge to composts as revealed by fluorescent staining- image analysis, Raman spectroscopy and pyrolysis-GC/MS.

Lagooning sludge (LS), which is used as soil amendment in Morocco, may contain microplastics (MPs). The aim of this study was to examine the effect of dewatering and co-composting of LS with green waste (GW) on the MPs' evolution. In this context the present study proposes fast-preliminary steps to detect plastics in lagooning sewage sludge before the extraction and identification process. We used pyrolysis GC/MS spectrometry to investigate the presence of chemical compounds possibly derived from plastics, and fluorescence staining by Nile Red to detect fluorescent particles suspected as plastics. Thereafter, we quantified the MPs particles after density fractionation and investigated their nature by Raman spectroscopy. RESULTS: indicated the presence of an average of 40.5 ± 11.9 × 103 MPs particles/kg (dry matter) and 36 ± 9.7 × 103 MPs particles/kg (dry matter) in fresh sludge and dewatered sludge respectively. Sludge dewatering in drying beds resulted a loss of small MPs (<500 µm). In co-composts, the quantity of MPs varied with the proportion of sewage sludge. The distribution of MPs types differentiated by colour and types (polypropylene, polyethylene, polyamide and polyester) evolved differently. Conventional co-composting did not have any effect on MPs quantity, indicating that they are not biodegradable under these temperature conditions, but it influenced their particle size. The risks of these pollutants after repeated field application and the possibility of their reduction through others co-composting procedures and techniques would be further investigated.