Search Results (63)

This study aimed to investigate the effect of wildfire episodes on air quality in terms of particulate matter (PM) and carbonaceous compound concentration in ambient air, and to assess deviations from typical annual patterns. The sampling was performed at a rural background site near the Adriatic coast in Croatia through 2024. To better understand contributions caused by fire events, the levels of organic carbon (OC), elemental carbon (EC), black carbon (BC), pyrolytic carbon (PyrC), optical carbon (OptC), water-soluble organic carbon (WSOC), levoglucosan (LG), mannosan (MNS), and galactosan (GA) were determined in PM₁₀ and PM_2.5 fractions (particles smaller than 10 µm and 2.5 µm, respectively). The annual mean concentrations of PM₁₀ and PM_2.5 were 14 µg/m³ and 8 µg/m³, respectively. During the fire episode, the PM_2.5 mass contribution to the total PM₁₀ mass exceeded 65%. Total carbon (TC) and OC increased by a factor of 7, EC and BC by 12, PyrC by 8, and WSOC by 12. The concentration of LG reached 1.219 μg/m³ in the PM₁₀ fractions and 0.954 μg/m³ in the PM_2.5 fractions, representing a 200-fold increase during the fire episode. Meteorological data were integrated to assess atmospheric conditions during the fire episode, and the specific ratios between fire-related compounds were analyzed. Full article

This study achieves the particle-resolved modeling of biomass pyrolysis via a novel approach of integrating the Discrete Element Method (DEM) with a semi-detailed chemical kinetic mechanism. By coupling CFD-DEM with a 36-step reaction network, the multiscale interactions between particle-scale hydrodynamics and the formation kinetics of 19 tar components under varying temperatures (630–770 °C) are elucidated. Levoglucosan (44.79%) and methanol (18.64%) are identified as primary tar components. Combined with these, furfural (C₅H₄O₂, 7.22%), methanal (CH₂O, 6.75%), and glutaric acid (C₅H₈O₄, 4.20%) account for over 80% of all the tar components. The secondary decomposition pathways are successfully captured, and changes in the reaction rates, as seen in triglycerides (R23: 307.30% rate increase at 770 °C) and tannins (R24: 265.41% acceleration), are quantified. This work provides the ability to predict intermediate products, offering critical insights into reactor optimization. Full article

The gasification of cellulose typically requires high temperatures (>600 °C) due to the thermal stability of levoglucosan, a major intermediate formed during pyrolysis. In this study, we investigated the gasification behavior of cellulose by combining infrared (IR) heating with low-power dielectric barrier discharge (DBD) plasma treatment. Cellulose filter paper was first pyrolyzed using localized IR irradiation (2 kW for 30 s), generating mist-like volatile products including levoglucosan. These volatiles were then exposed to DBD plasma (16–64 W for 1 or 3 min) under Ar flow. Despite the relatively low estimated gas temperatures below 240 °C in the plasma region, gas yields, including H₂ and CO, increased markedly with discharge power, reaching up to 72.6 wt% at 64 W for 3 min—more than four times that obtained with IR heating alone. These results indicate that DBD plasma facilitates the gasification of pyrolysis volatiles under significantly lower temperature conditions than those required in conventional thermal gasification. This approach may offer a route toward low-temperature biomass gasification with reduced tar, coke, and clinker formation. Full article

Glucose is the most abundant monosaccharide as it is the primary unit of cellulose and starch, which are the more relevant feedstocks for biorefineries. Dehydration of glucose can lead to anhydroglucoses, whose interest has been increasing due to its potential industrial use. Commercial sulfonic polymer resins and a synthesized organic–inorganic mesoporous material were taken as Brønsted acid catalysts. High hexose conversion (up to 98%) and selectivity to anhydroglucoses (~80%) could be reached, turning this process into an alternative route to carbohydrate pyrolysis that presents an energy-intensive downstream. Hexose conversion to anhydroglucoses was related to the amount of acid sites, and the removal of one molecule of water from hexoses to produce anhydroglucoses was found as the preferential dehydration route over a bare Brønsted acid catalyst in anhydrous polar aprotic solvent (DMF) at mild conditions. Product distribution changed dramatically upon catalyst deactivation with HMF and fructose emerging as relevant products. It was suggested that an additional Lewis surface is produced during the deactivation process, probably arising from the formation of insoluble high molecular weight compounds in acidic media. Full article

This study examines the influence of biomass burning on the organic content of urban aerosols in Zagreb, Croatia, by analyzing anhydrosugars, elemental carbon (EC), organic carbon (OC), and water-soluble organic carbon (WSOC) in PM_2.5 and PM₁ fractions collected during different seasons of 2022. Seasonal trends showed that the highest average concentrations of PM_2.5 (27 µg m⁻³) and PM₁ (17 µg m⁻³) were measured during the winter and decreased in the spring, summer, and autumn, which is in accordance with the specific activities and environmental conditions typical for each season. Different sources of OC and WSOC were noticed across different seasons; levoglucosan (LG) was measured during the winter (1314 ng m⁻³ in PM_2.5 and 931 ng m⁻³ in PM₁), indicating that biomass that was mostly used for residential heating was the main source rather than the agricultural activities that are usually common during warmer seasons. The contribution of LG to PM was 5.3%, while LG contributed to OC by up to 13.4% and LG contributed to WSOC by up to 36.5%. Deviations in typical seasonal variability of LG/WSOC revealed more intense biomass burning episodes during the autumn and several times during the winter season. A back trajectories HYSPLIT model revealed a long-range transport biomass emission source. The levoglucosan-to-mannosan (LG/MNS) ratios indicated the burning of mixed softwood and hardwood during colder seasons and the burning of softwood during warmer seasons. Spearman’s correlation tests and principal component analysis showed a strong and statistically significant (p < 0.05) correlation between LG, PM, OC, EC, and WSOC only during the winter season, demonstrating that they had the same origin in the winter, while their sources in other seasons were diverse. Full article

This work focuses on the changes in the chemical composition of wood caused by impregnation with fire retardants such as guanidine carbonate (GC), urea (U), diammonium phosphate (DAP) and their mixtures. The treated wood was tested using the oxygen index (LOI), Py–GC/MS analysis and FTIR Spectroscopy. The wood was vacuum treated at a pressure of 0.8 MPa for 20 min and then subjected to thermal degradation using the LOI. This way, degraded and nondegraded layers were obtained and ground (0.2 mm). All treatment variants achieved the class of non-flammable materials based on LOI tests; the exception was the 5% urea solution, defined as a flame-retardant material. Using the analytical methods, it was found that cellulose and hemicelluloses undergo the fastest thermal degradation. This study found that the variant protected with a 5% mixture of GC and DAP before and after the degradation process had the best fire-retardant properties regarding cellulose content in the wood. The highest content of anhydrosugars characterised the same variants, the amount of which indicates a slowdown in the degradation process and, consequently, a reduction in the release of levoglucosan during combustion, suggesting potential applications in fire safety. Full article

This paper presents a novel machine learning methodology able to extend the results of detailed local emission inventories to larger domains where emission estimates are not available. The first part of this work consists in the development of an emission inventory of elemental carbon (EC), black carbon (BC), organic carbon (OC), and levoglucosan (LG) obtained from the detailed emission estimates available from the Project LIFE PREPAIR for the Po Basin in north Italy. The emissions of these chemical species in combination with particulate primary emissions and gaseous precursors are very important information in source apportionment and in the impact assessment of the different emission sources in air quality. To gain a better understanding of the origins of atmospheric pollution, it is possible to combine measurements with emission estimates for the particulate matter fractions known as EC, BC, OC, and LG. To identify the sources of emissions, it is usual practice to use the ratio of the measured EC, OC, TC (Total Carbon), and LG. The PREPAIR emission estimates and these new calculations are then used to train the Random Forest (RF) algorithm, considering a large array of local variables, such as taxes, the characteristics of urbanization and dwellings, the number of employees detailed for economic activities, occupation levels and land cover. The outcome of the comparison of the predictions of the machine learning implemented model (ML) with the estimates obtained for the same areas by two independent methods, local disaggregation of the national emission inventory and Copernicus Air Modelling Service (CAMS) emissions estimates, is extremely encouraging and confirms it also as a promising approach in terms of effort saving. The implemented modelling approach identifies the most important variables affecting the spatialization of different pollutants in agreement with the main emission source characteristics and is suitable for harmonization of the results of different local emission inventories with national emission reporting. Full article

Lately, pyrolysis has attracted significant attention due to its substantial potential for bio-oil production, with the ability to serve as a renewable energy source and/or facilitate the production of valuable chemical compounds. The chemical compounds generated and their amounts are completely influenced by the traits and chemical makeup of the initial biomass. In this work, the catalytic fast pyrolysis of Eucalyptus urograndis canopy was carried out using a pyrolyzer coupled to gas chromatography/mass spectrometry (Py-GC/MS) at different temperatures and in the presence and absence of catalysts. Elemental composition analysis was employed to characterize the chemical composition of the biomass. The results showed a biomass with a carbon percentage of 50.20%, oxygen of 43.21%, and hydrogen of 6.34%, as well as a lower calorific power of 17.51 MJ/kg. The Py-GC/MS analyses revealed the presence of several noteworthy compounds, including acetic acid (C₂H₄O₂) and, in smaller quantities, hydrogen (H₂), furfural (C₅H₄O₂), and levoglucosan (C₆H₁₀O₅). The technical-economic evaluation revealed that the production of acetic acid, furfural, hydrogen, and levoglucosan commands a high market price. Additionally, a single production cycle is anticipated to yield a favorable technical-economic balance, generating approximately USD 466.10 /ton of processed biomass. This outcome is achieved through the process of catalytic fast pyrolysis, where CuO has been identified as the most suitable catalyst. Full article

This study is focused on the detailed examination of the combustion properties and kinetic analysis of a cellulose acetate fibrous bundle (CAFB), separated from used cigarette filters. It was shown that the faster rate of CAFB heating allows a large amount of heat to be supplied to a combustion system in the initial stages, where the increase in heating rate has a positive response to ignition behavior. The best combustion stability of CAFB is achieved at the lowest heating rate. Through the use of different kinetic methods, it was shown that combustion takes place through two series of consecutive reaction steps and one independent single-step reaction. By optimizing the kinetic parameters within the proposed reaction models, it was found that the steps related to the generation of levoglucosenone (LGO) (by catalytic dehydration of levoglucosan (LG)) and acrolein (by breakdown of glycerol during CAFB burning—which was carried out through glycerol adsorption on a TiO₂ surface in a the developed dehydration mechanism) represent rate-controlling steps, which are strongly controlled by applied heating rate. Isothermal predictions have shown that CAFB manifests very good long-term stability at 60 °C (which corresponds to storage in a sea shipping container), while at 200 °C, it shows a sudden loss in thermal stability, which is related to the physical properties of the sample. Full article

This study investigated the aerosol particle properties and light absorption properties of brown carbon (BrC) by utilizing a seven-wavelength aethalometer, and analyzed NH₄⁺, NO₃⁻, SO₄²⁻, K⁺, K, organic carbon, elemental carbon, levoglucosan, and mannosan in PM_2.5. The research was conducted in a rural area of Jeonnam, South Korea, during the winter season. In addition, the dithiothreitol assay-oxidative potential normalized to 9,10-phenanthrenequinone (QDTT-OP) was investigated throughout the study period. The absorption coefficient was found to be 2.6 to 5.6 times higher at 370 nm compared to 880 nm, suggesting the presence of light-absorbing substances in addition to black carbon (BC) particles. The estimated absorption coefficient of BrC₃₇₀ was 29.9% of the total light absorption coefficient at 370 nm. Furthermore, BrC₃₇₀ exhibited a strong affinity with levoglucosan while showing a weak correlation with K⁺, confirming the suitability of levoglucosan as a tracer for biomass burning. The QDTT-OP was 5.3 nM m⁻³, and highly correlated with the carbonaceous components levoglucosan and mannosan, suggesting a relatively high contribution of biomass combustion emissions to oxidative potential. Further research should be conducted to assess the health risks associated with future PM_2.5 exposure related to biomass burning in the atmosphere. Full article

This study aimed to identify the characteristics of atmospheric pollutants emitted by agricultural activities and to evaluate factors that may cause harm to human health. For the research, atmospheric pollutants were measured over the course of a year in representative rice farming and field crop farming areas in South Korea. The results confirmed that the characteristics of atmospheric pollutants in agricultural areas are influenced by the nature of agricultural activities. Specifically, when comparing rice paddies and field crop areas, during summer, the correlation between oxidative potential and levoglucosan—a marker for biomass burning—weakens due to less burning activity in the rice-growing season, leading to lower oxidative potential despite different PM_2.5 across areas. The study also finds that methyl sulfonic acid, indicating marine influence, plays a big role in keeping oxidative potential low in summer. This suggests that the main causes of PM_2.5-related health risks in the area are from biomass burning and external sources, with burning being a significant factor in increasing oxidative potential. Based on these results, it is hoped that measures can be taken in the future to reduce atmospheric pollutants in agricultural areas. Full article

Intraspecific macromolecule variation in stemwood, knotwood, and branchwood was studied using analytical pyrolysis with the intention of introducing a rapid working method to assess the variance in lignin content using analytical pyrolysis and highlight variability markers. The study was performed on Picea abies, Abies alba, and Pseudotsuga menziesii. Lignin determined via analytical pyrolysis–GC/MS (Py-lignin) can be used to identify variations in lignin content, compared to using classical Klason lignin values as a reference method for lignin determination, which requires a correction factor. Principal component analysis (PCA) was performed to identify biopolymer pyrolysis product markers for different species, tissues, or heights that could help highlight structural differences. Douglas fir was differentiated from spruce and silver fir in the levoglucosan amount. Guaiacol was more present in spruce wood, and creosol was more present in Douglas fir. Knotwood was structurally close to stemwood in spruce and silver fir, but there was a clear transition between stemwood and branchwood tissue in Douglas fir. Knotwood was differentiated by higher furan compounds. Branchwood was clearly separate from stemwood and knotwood and presented the same markers as compression wood in the form of phenylpropanoid lignins (H-lignin) as well as isoeugenol and vinyl guaiacol, the two most produced lignin pyrolysis products. Full article

The molecular characteristics and formation mechanism of biogenic secondary organic aerosols (BSOAs) in the forested atmosphere are poorly known. Here, we report the temporal variations in and formation processes of BSOA tracers derived from isoprene, monoterpenes, and β caryophyllene in PM_2.5 samples collected at the foot of Mt. Huang (483 m a. s. l) in East China during the summer of 2019 with a 3 h time resolution. The concentrations of nearly all of the detected species, including organic carbon (OC), elemental carbon (EC), levoglucosan, and SIA (sum of SO₄²⁻, NO₃⁻, and NH₄⁺), were higher at night (19:00–7:00 of the next day) than in the daytime (7:00–19:00). In addition, air pollutants that accumulated by the dynamic transport of the mountain breeze at night were also a crucial reason for the higher BSOA tracers. Most of the BSOA tracers exhibited higher concentrations at night than in the daytime and peaked at 1:00 to 4:00 or 4:00 to 7:00. Those BSOA tracers presented strong correlations with O₃ in the daytime rather than at night, indicating that BSOAs in the daytime were primarily derived from the photo-oxidation of BVOCs with O₃. The close correlations of BSOA tracers with SO₄²⁻ and particle acidity (pH_is) suggest that BSOAs were primarily derived from the acid-catalyzed aqueous-phase oxidation. Considering the higher relative humidity and LWC concentration at night, the promoted aqueous oxidation was the essential reason for the higher concentrations of BSOA tracers at night. Moreover, levoglucosan exhibited a robust correlation with BSOA tracers, especially β-caryophyllinic acid, suggesting that biomass burning from long-distance transport exerted a significant impact on BSOA formation. Based on a tracer-based method, the estimated concentrations of secondary organic carbon (SOC) derived from isoprene, monoterpenes, and β caryophyllene at night (0.90 ± 0.57 µgC m⁻³) were higher than those (0.53 ± 0.34 µgC m⁻³) in the daytime, accounting for 14.5 ± 8.5% and 12.2 ± 5.0% of OC, respectively. Our results reveal that the BSOA formation at the foot of Mt. Huang was promoted by the mountain-valley breezes and anthropogenic pollutants from long-range transport. Full article

Thermo-chemical conversion via the pyrolysis of cigarette butt (CB) filters was successfully valorized and upcycled in the pre-carbonization and carbonization stages. The pre-carbonization stage (devolatilization) of the precursor material (cellulose acetate filter, r-CAcF) was analyzed by micro-scale experiments under non-isothermal conditions using TG-DTG-DTA and DSC techniques. The results of a detailed kinetic study showed that the decomposition of r-CAcF takes place via complex mechanisms, including consecutive reaction steps and two single-step reactions. Consecutive stages include the α-transition referred to as a cellulose polymorphic transformation (cellulose I → II) through crystallization mechanism changes, where a more thermodynamically ordered system was obtained. It was found that the transformation rate of cellulose I → II (‘cellulose regeneration’) is strongly affected by the presence of alkali metals and the deacetylation process. Two single-step reactions showed significant overlapping behavior, which involves a nucleation-controlled scission mechanism (producing levoglucosan, gaseous products, and abundant radicals) and hydrolytic decomposition of cellulose by catalytic cleavage of glycosidic bonds with the presence of an acidic catalyst. A macro-scale experiment showed that the operating temperature and heating rate had the most notable effects on the total surface area of the manufactured carbon. A substantial degree of mesoporosity with a median pore radius of 3.1695 nm was identified. The presence of macroporosity on the carbon surface and acidic surface functional groups was observed. Full article

Utilization of lignin is among the most pressing problems for biorefineries that convert lignocellulosic biomass to fuels and chemicals. Recently “lignin-first” biomass fractionation has received increasing attention. In most biorefining concepts, carbohydrate portions of the biomass are separated, and their monomeric sugar components released, while the relatively chemically stable lignin rich byproduct remains underutilized. Conversely, in lignin-first processes, a one-pot fractionation and depolymerization is performed, leading to an oil rich in phenolic compounds and a cellulosic pulp. Usually, the pulp is considered as a fermentation feedstock to produce ethanol. Herein, the results of a study where various cellulosic pulps are tested for their potential to produce valuable products via pyrolysis processes, assessed via analytical pyrolysis (py-GC), are presented. Samples of herbaceous (switchgrass) and woody biomass (oak) were subjected to both an acid-catalyzed and a supported-metal-catalyzed reductive lignin-first depolymerization, and the pulps were compared. Fast pyrolysis of the pulps produced levoglucosan in yields of up to about 35 wt %. When normalized for the amount of biomass entering the entire process, performing the lignin-first reductive depolymerization resulted in 4.0–4.6 times the yield of levoglucosan than pyrolysis of raw biomass. Pulps derived from switchgrass were better feedstocks for levoglucosan production compared with pulps from oak, and pulps produced from metal-on-carbon catalyzed depolymerization produced more levoglucosan than those from acid-catalyzed depolymerization. Catalytic pyrolysis over HZSM-5 produced aromatic hydrocarbons from the pulps. In this case, the yields were similar from both feedstocks and catalyst types, suggesting that there is no advantage to lignin fractionation prior to zeolite-catalyzed catalytic pyrolysis for hydrocarbons. Full article