Biomass, a renewable energy source, via available thermo-chemical processes has both engineering and environmental advantages. However, the understanding of the kinetics, evolved gases, and mechanisms for biomass pyrolysis is limited. We first propose a novel temperature response mechanism for the pyrolysis of sugar cane residue using thermogravimetric analysis-Fourier transform infrared spectrometry-mass spectrometry (TG-FTIR-MS) combined with Gaussian model and two-dimensional correlation spectroscopy (2D COS). The existence and contribution of distinct peaks in TG-FTIR spectra were innovatively distinguished and quantified, and the temperature-dependent dynamics of gas amounts were determined using Gaussian deconvolution. The 2D-TG-FTIR/MS-COS results revealed for the first time that the primary sequential temperature responses of gases occurred in the order: H 2 O/CH 4 > phenols/alkanes/aromatics/alcohols > carboxylic acids/ketones > CO 2 /ethers > aldehyde groups/acetaldehyde. Subtle sequential changes even occurred within the same gases during pyrolysis. The quantity dynamics and sequential responses of gases were fitted to the combined effects of the order-based, diffusion, and chemical reaction mechanisms for the component degradation. The combination of TG-FTIR-MS, Gaussian model, and 2D COS is a promising approach for the online monitoring and real-time management of biomass pyrolysis, providing favorable strategies for pyrolysis optimization, byproduct recovery, energy generation, and gas emission control in engineering and environmental applications.

Biochar-derived dissolved black carbon (DBC) varies in chemical composition and significantly affects the environmental fate of metal ions. However, the intrinsic molecular composition of DBC fractions and their molecular interaction mechanisms with metal ions remain unclear. We propose a novel, molecular-level covariant binding mechanism to comparatively interpret the heterogeneities, active sites, and sequential responses of copper binding with molecular compounds in DBC and natural dissolved organic matter (DOM). Relatively large proportions of lipid/aliphatic/peptide-like compounds with low mass distributions and lignin-like compounds with oxidized/unsaturated groups existed in acidic-and alkaline-extracted DBC, respectively. A larger percentage of tannin-like/condensed aromatic compounds and higher average conditional stability constants (logK̅ Cu ) of visible fluorescent components were found for DOM than for DBC. Overall, 200−320 Da and 320−480 Da molecular components contributed significantly to the logK̅ Cu values of UVA and visible fluorescent components, respectively, in DBC/DOM. Nitrogenous groups likely exhibited stronger binding affinities than phenolic/carboxylic groups. The sequential copper-binding responses of molecular compounds in DBC/DOM generally followed the order lipid/aliphatic/peptide-like compounds → tannin-like compounds → condensed aromatic compounds. These insights will improve the prediction of the potential effects of DBC on various contaminants and the risks of biochar application to ecosystems.

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Volatile organic compound (VOC) emissions from pyrolysis of widely used biomass are expected to increase significantly under the carbon neutrality target. However, the dynamic emissions and evolution mechanism of biomass-VOCs remain unclear, hindered by complex reactions and offline measurements. Here, we propose a novel covariant evolution mechanism to interpret the emission heterogeneities, sequential temperature responses, and evolved correlations of both VOCs and residual functional groups (RFGs) during corn straw (CS), wood pellet (WP), and semibituminous coal (SBC) pyrolysis. An innovative combination of online thermogravimetric–Fourier transform infrared–gas chromatography/mass spectrometry and two dimensional-correlation spectroscopy was applied. The relative percentages of CS/WP-VOCs were higher than those of SBC-VOCs, and most VOCs tended to have relatively small carbon skeletons as the average carbon oxidation state increased. With the temperature increased from low to high during CS/WP pyrolysis, the primary sequential response of VOCs (acids → phenols/esters → alcohols/ethers/aldehydes/ketones → hydrocarbons/aromatics) corresponded to the RFG response (hydroxyl groups → −CH3/–CH2–/–CH groups → aliphatic ethers and conjugated ketones). Compared with the relative regularity for CS/WP responses, the gas–solid products from SBC pyrolysis exhibited complex temperature-dependent responses and high oxidation-induced variability. These insights provide favorable strategies for the online monitoring system to facilitate priority removal of coal and biomass fuels–VOCs.

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