Molecular-level insights into the temperature-dependent formation dynamics and mechanism of water-soluble dissolved organic carbon derived from biomass pyrolysis smoke.

Water soluble organic carbon (WSOC) derived from biomass pyrolytic smoke is deposited through atmospheric aerosols, negatively affecting aquatic ecological quality and safety. However, the temperature-dependent molecular diversity and dynamic formation of smoke-derived WSOC remain poorly understood in water. Herein, we explored the molecular-level formation mechanism of pyrolytic smoke-derived WSOC in water to explain the evolution, heterogeneous correlations, and sequential responses of molecules and functional groups to increasing pyrolysis temperature. Two-dimensional correlation spectroscopy was used to innovatively establish the characteristic correlations between spectroscopy and Fourier transform-ion cyclotron resonance mass spectrometry. Temperature-dependent formation of WSOC exhibited diversity in absorbance/fluorescent components, unique/common molecules, and their chemical parameters, showing the simultaneous formation and degradation reactions. The common WSOC molecules with lower and higher degrees of oxidation showed significant positive and negative correlations with the fluorescent components, respectively. The primary sequential response of WSOC molecules to increasing pyrolysis temperature (lignin-like molecules â†’ unsaturated hydrocarbons, condensed aromatic molecules â†’ lipid-like/aliphatic-/peptide-like molecules) corresponded to the temperature response of functional groups (carboxylic/alcoholic â†’ polysaccharides â†’ aromatics/amides/phenolic/aliphatic groups), demonstrating well synergistic relationships between them. These novel findings will contribute to the comprehensive understanding and assessments of potential environmental behavior or risks of WSOC in aquatic ecosystems.

Characteristics of solid waste from common generation source in nonferrous smelting industry reveal a new classification method.

Solid waste produced by the nonferrous smelting industry has a significant number of notable differences. The lack of recognition of solid waste characteristics is the main factor restricting its disposal and utilization. In this study, we analyzed the main production processes of the nonferrous smelting industry; identified the key production nodes of solid waste; and clarified the characteristics, including the physical, chemical, and pollution characteristics of solid wastes, through a large sample statistical analysis. We found similarities among solid wastes from a common generation source as well as notable differences among the different generation sources: slags and sludges from waste acid treatment and wastewater treatment units had a water content of 27.43-52.71% and 51.14-68.27%, respectively, which were significantly higher than those of other metallurgy and dust collection units; the pH of slags from an electrorefining unit was strongly alkaline; the mineral phase of sludges from wastewater treatment was only calcite; slags from a waste acid treatment unit were mainly in phase of gypsum, claudetite, and anglesite; the chemical composition of slags from pyrometallurgy and hydrometallurgy units was mainly SiO2 and Fe2O3. In this paper, we discuss a new classification method based on a common generation source for the first time. These results are beneficial to guide the disposal, utilization, and management of solid waste.

Molecular-level insights into the heterogeneous variations and dynamic formation mechanism of leached dissolved organic matter during the photoaging of polystyrene microplastics.

Microplastics (MPs) and their derivatives have received worldwide attention owing to their adverse effects on ecosystems. However, molecular diversity and dynamic formation of dissolved organic matter (DOM) during the photoaging of MPs remain unclear. Herein, we explored a molecular‒level formation mechanism for polystyrene MP (MPPS)‒derived DOM (PSDOM) during the photoaging of MPs to explain the evolution, heterogeneity, and sequential response of molecules to irradiation. Two‒dimensional correlation spectroscopy was applied to correlate the variations of PSDOM molecules detected by Fourier transform-ion cyclotron resonance mass spectrometry with those of MPPS functional groups detected by Fourier transform infrared spectroscopy. Irradiation‒induced PSDOM contained the most highly unsaturated structures with oxygen, but showed fewer aromatic structures than natural aquatic DOM. Photochemical transformations occurred between saturated‒reduced and oxidized molecules during PSDOM leaching, with the low‒oxidized and high‒oxidized molecules undergoing considerable changes in the normal carbon oxidation state and molecular number, respectively. The primary sequential response of PSDOM molecules to increasing irradiation time [low‒oxidized/high‒weight (450

Temperature-Dependent Molecular Evolution of Biochar-Derived Dissolved Black Carbon and Its Interaction Mechanism with Polyvinyl Chloride Microplastics.

Biochar-derived dissolved black carbon (DBC) molecules are dependent on the BC formation temperature and affect the fate of emerging contaminants in waters, such as polyvinyl chloride microplastic (MPPVC). However, the temperature-dependent evolution and MPPVC-interaction of DBC molecules remain unclear. Herein, we propose a novel DBC-MPPVC interaction mechanism by systematically interpreting heterogeneous correlations, sequential responses, and synergistic relationships of thousands of molecules and their linking functional groups. Two-dimensional correlation spectroscopy was proposed to combine Fourier transform-ion cyclotron resonance mass spectrometry and spectroscopic datasets. Increased temperature caused diverse DBC molecules and fluorophores, accompanied by molecular transformation from saturation/reduction to unsaturation/oxidation with high carbon oxidation states, especially for molecules with acidic functional groups. The temperature response of DBC molecules detected via negative-/positive-ion electrospray ionization sequentially occurred in unsaturated hydrocarbons → lignin-like → condensed aromatic → lipid-/aliphatic-/peptide-like → tannin-like → carbohydrate-like molecules. DBC molecular changes induced by temperature and MPPVC interaction were closely coordinated, with lignin-like molecules contributing the most to the interaction. Functional groups in DBC molecules with m/z < 500 showed a sequential MPPVC-interaction response of phenol/aromatic ether C-O, alkene C═C/amide C═O → polysaccharides C-O → alcohol/ether/carbohydrate C-O groups. These findings help to elucidate the critical role of DBCs in MP environmental behaviors.

Integrated assessment of land-to-river Cd fluxes and riverine Cd loads using SWAT-HM to guide management strategies.

In 2011, China invested US$9.8 billion to combat the severe heavy metal pollution in the Xiang River basin (XRB), aiming to reduce 50% of the 2008 industrial metal emissions by 2015. However, river pollution mitigation requires a holistic accounting of both point and diffuse sources, yet the detailed land-to-river metal fluxes in the XRB remain unclear. Here, by combining emissions inventories with the SWAT-HM model, we quantified the land-to-river cadmium (Cd) fluxes and riverine Cd loads across the XRB from 2000 to 2015. The model was validated against long-term historical observations of monthly streamflow and sediment load and Cd concentrations at 42, 11, and 10 gauges, respectively. The analysis of the simulation results showed that the soil erosion flux dominated the Cd exports (23.56-80.14 Mg yr-1). The industrial point flux decreased by 85.5% from 20.84 Mg in 2000 to 3.02 Mg in 2015. Of all the Cd inputs, approximately 54.9% (37.40 Mg yr-1) was finally drained into Dongting Lake; the remaining 45.1% (30.79 Mg yr-1) was deposited within the XRB, increasing the Cd concentration in riverbed sediment. Furthermore, in XRB's 5-order river network, the Cd concentrations in small streams (1st order and 2nd order) showed larger variability due to their low dilution capacity and intense Cd inputs. Our findings highlight the need for multi-path transport modeling to guide future management strategies and better monitoring schemes to restore the small polluted streams.

Effects of biochar on the phytotoxicity of polyvinyl chloride microplastics.

Polyvinyl chloride microplastics (PVC-MPs) are toxic to crops, resulting in economic losses during agricultural production. Owing to its strong adsorption capacity, biochar can effectively remove MPs from water. It is presumed that biochar can alleviate the phytotoxicity of PVC-MPs. To verify this hypothesis, the effects of different concentrations of corncob biochar (CCBC) on the phytotoxicity of PVC-MPs were investigated using hydroponic experiments. The results showed that PVC-MPs attached to lettuce roots substantially inhibited the growth and quality of lettuce. The tested CCBC adsorbed the PVC-MPs. At appropriate concentrations, CCBC alleviated the inhibitory effect of PVC-MPs on lettuce yield; however, it decreased some quality indicators. The single PVC-MPs induced oxidative damage to lettuce, as demonstrated by the increased hydrogen peroxide (H2O2) and malondialdehyde (MDA) content. Addition of CCBC considerably decreased the contents of H2O2 and MDA in the lettuce shoots but increased the H2O2 content in the roots. These findings indicate that CCBC may alleviate the adverse effects caused by PVC-MPs to the lettuce shoots but aggravate the toxic effects on the lettuce roots. This study provides a basis for understanding the removal of the phytotoxicity of MPs.

Heterogeneous Dynamic Behavior and Synergetic Evolution Mechanism of Internal Components and Released Gases during the Pyrolysis of Aquatic Biomass.

Evolution of gaseous contaminants from biomass pyrolysis has drawn increasing attention. However, the thermal degradation, dynamics, and synergetic evolution mechanisms during real-time biomass pyrolysis remain unclear. Herein, a novel method using thermogravimetry-Fourier transform infrared spectrometry-gas chromatography/mass spectrometry (TG-FTIR-GC/MS) combined with thermal kinetics and two-dimensional correlation spectroscopy was proposed to explore the chemical properties and temperature response mechanisms of gaseous species released during Phragmites communis (PC) and Typha angustifolia (TA) pyrolysis. The thermal degradation mechanisms of PC/TA pyrolysis were mainly associated with the sigmoidal rate and random nucleation mechanisms. The formation intensities of alcohols/ethers, phenols/esters, acids, aldehydes, and ketones were higher during low-temperature TA pyrolysis and high-temperature PC pyrolysis. The average carbon oxidation state (OS¯C) of gaseous species mainly ranged from -1.5 to -0.5, and the OS¯C slope of most gaseous species was greater than -2.0, which was related to the reduction of aldehyde/ketone groups. Two-dimensional (2D)-TG-FTIR-COS analysis revealed that the sequential temperature response of gaseous species followed: acids → phenols, esters → aldehydes → hydrocarbons → alcohols, ethers → aromatics during PC/TA pyrolysis. The establishment of relationships between the sequential response of gases and degraded components provides an important basis for online monitoring/recovery of gaseous contaminants during biomass pyrolysis.

Identification priority source of soil heavy metals pollution based on source-specific ecological and human health risk analysis in a typical smelting and mining region of South China.

An in-depth understanding of the ecological and health risks posed by heavy metals originating from various pollution sources is critical for foresighted soil-quality management. Based on 220 grid samples (2 × 2 km) analyzed for eight heavy metals (Cd, Hg, As, Pb, Cr, Ni, Cu, and Zn) in the Chenshui (CS) watershed of Hunan Province, China, we applied an integrated approach for identifying and apportioning pollution sources of soil heavy metals and exploring their source-specific pollution risks. This approach consists of three sequential steps: (1) source identification by combining the positive matrix factorization model with geostatistical analysis; (2) quantification of ecological, carcinogenic, and non-carcinogenic risks in a source-specific manner; (3) prioritization of sources in a holistic manner, considering both ecological risks and human health risks. Cd (68.0%) and Hg (13.3%) dominated the ecological risk in terms of ecological risk index; As dominated the non-carcinogenic health risk in terms of total hazard index (THI; adults: 84.8%, children: 84.7%) and the carcinogenic health risk in terms of total carcinogenic risk index (TCRI; adults: 69.0%, children: 68.8%). Among three exposure routes, oral ingestion (89.4-95.2%) was the predominant route for both adults and children. Compared with adults (THI = 0.41, TCRI = 7.01E-05), children (THI = 2.81, TCRI = 1.22E-04) had greater non-carcinogenic and carcinogenic risks. Four sources (F1-4) were identified for the CS watershed: atmospheric deposition related to coal-burning and traffic emissions (F1, 18.0%), natural sources from parent materials (F2, 34.3%), non-ferrous mining and smelting industry (F3, 37.9%), and historical arsenic-related activity (F4, 9.8%). The F3 source contributed the largest (45.2%) to the ecological risks, and the F4 source was the predominant contributor to non-carcinogenic (52.4%) and carcinogenic (64.6%) risks. The results highlight the importance of considering legacy As pollution from abandoned industries when developing risk reduction strategies in this region. The proposed methodology for source and risk identification and apportionment formulates the multidimensional concerns of pollution and the various associated risks into a tangible decision-making process to support soil pollution control.

Influence of CaO on the thermal kinetics and formation mechanism of high value-added products during waste tire pyrolysis.

There is a lack of detailed research on the production of isoprene and D-limonene by solid base-catalysed thermal depolymerization of waste tires (WTs). This work aimed to investigate the thermal decomposition characteristics, reaction kinetics, high value-added products production and potential mechanisms during WT pyrolysis in the presence of calcium oxide (CaO) via Thermogravimetry-Fourier Transform Infrared spectrometer (TG-FTIR) and Pyrolyzer-Gas Chromatography/Mass spectrometry (Py-GC/MS). The results obtained from TG indicated that CaO accelerated depolymerization in terms of reducing the reaction temperature, which is also reflected in the kinetic parameters. It can be found that the content of D-limonene increased by 13.76% and that of isoprene increased by 37.57%, which were attributed to differences in the depolymerization mechanisms in the presence of CaO. Furthermore, CaO had a profound impact on desulfurization by reducing benzothiazole, sulfoacid, and thiophene. The potential catalytic mechanisms of isoprene and D-limonene production and desulfurization were also proposed. This work deepens the understanding of the catalytic pyrolysis of WT under CaO and unambiguously demonstrates the great potential of CaO in enhancing isoprene and D-limonene production, providing new insight for the cleaner production of high value-added products from WT.

Dynamic Evolution and Covariant Response Mechanism of Volatile Organic Compounds and Residual Functional Groups during the Online Pyrolysis of Coal and Biomass Fuels.

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.

Pyrogenic dissolved organic matter produced at higher temperature is more photoactive: Insight into molecular changes and reactive oxygen species generation.

Pyrogenic dissolved organic matter (pyDOM) is the photolabile fraction in the dissolved organic matter pool. However, the molecular changes and reactive oxygen species generation of pyDOMs under continuous irradiation, and how these vary with feedstock type and pyrolysis temperature, are not well understood. In this study, the soluble fractions of 300 and 450 ºC biochars (pyDOM300 and pyDOM450) were subjected to photo-irradiation. PyDOM450 was of higher aromaticity, molecular variety, but lower unsaturation than pyDOM300. The molecular weight, aromaticity, and double bond equivalents of pyDOMs generally decreased after photo-irradiation. The degradation pattern of pyDOMs can be divided into two stages. In the initial 24 h, pyDOM300 degraded faster than pyDOM450, with the more profound transformation of condensed aromatics and carbohydrate into aliphatic/proteins, lignins, and tannins in pyDOM300. After 720 h irradiation, however, the degradation ratio of pyDOM450 (36.2-43.9%) exceeded that of pyDOM300 (23.7-30.3%), with the initially preserved condensed aromatics in pyDOM450 further transforming into aliphatic/proteins and tannins. This was potentially attributed to the generation of more reactive oxygen species (·OH and 1O2) in pyDOM450. This study uncovered the photodegradation mechanisms of pyDOMs at molecular scale and helped to understand their cycling and effects on environment.

Novel Insights into the Molecular-Level Mechanism Linking the Chemical Diversity and Copper Binding Heterogeneity of Biochar-Derived Dissolved Black Carbon and Dissolved Organic Matter.

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 (logK̅Cu) 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 logK̅Cu 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.

Photochemical Reactivity of Humic Substances in an Aquatic System Revealed by Excitation-Emission Matrix Fluorescence.

The photochemical reactivity of humic substances plays a critical role in the global carbon cycle, and influences the toxicity, mobility, and bioavailability of contaminants by altering their molecular structure and the mineralization of organic carbon to CO2. Here, we examined the simulated irradiation process of Chinese standard fulvic acid (FA) and humic acid (HA) by using excitation-emission matrix fluorescence combined with fluorescence regional integration (FRI), parallel factor (PARAFAC) analysis, and kinetic models. Humic-like and fulvic-like materials were the main materials (constituting more than 90%) of both FA and HA, according to the FRI analysis. Four components were identified by the PARAFAC analysis: fulvic-like components composed of both carboxylic-like and phenolic-like chromophores (C1), terrestrial humic-like components primarily composed of carboxylic-like chromophores (C2), microbial humic-like overwhelming composed of phenolic-like fluorophores (C3), and protein-like components (C4). After irradiation for 72 h, the maximum fluorescence intensity (F max) of C1 and C2 of FA was reduced to 36.01-58.34%, while the F max of C3 of both FA and HA also decreased to 0-9.63%. By contrast, for HA, the F max of its C1 and C2 increased to 236.18-294.77% when irradiated for 72 h due to greater aromaticity and photorefractive tendencies. The first-order kinetic model (R 2 = 0.908-0.990) fitted better than zero-order kinetic model (R 2 = 0-0.754) for the C1, C2, and C3, of both FA and HA, during their photochemical reactivity. The photodegradation rate constant (k 1) of C1 had values (0.105 for FA; 0.154 for HA) that surpassed those of C2 (0.059 for FA, 0.079 for HA) and C3 (0.079 for both FA and HA) based on the first-order kinetic model. The half-life times of C1, C2, and C3 ranged from 6.61-11.77 h to 4.50-8.81 h for FA and HA, respectively. Combining an excitation-emission matrix with FRI and PARAFAC analyses is a powerful approach for elucidating changes to humic substances during their irradiation, which is helpful for predicting the environmental toxicity of contaminants in natural ecosystems.

Composition characterization and biotransformation of dissolved, particulate and algae organic phosphorus in eutrophic lakes.

Characteristics and transformation of organic phosphorus in water are vital to biogeochemical cycling of phosphorus and support of blooms of phytoplankton and cyanobacteria. Using solution 31P nuclear magnetic resonance (NMR), combined with field surveys and lab analyses, composition and structural characteristics of dissolved phosphorus (DP), particulate phosphorus (PP) and organic P in algae were studied in two eutrophic lakes in China, Tai Lake and Chao Lake. Factors influencing migration and transformation of these constituents in lake ecosystems were also investigated. A method was developed to extract, flocculate and concentrate DP and PP from lake water samples. Results showed that orthophosphate (Ortho-P) constituted 32.4%-81.3% of DP and 43.7%-54.9% of PP, respectively; while monoester phosphorus (Mono-P) was 13.2%-54.0% of DP and 32.9%-43.7% of PP, respectively. Phosphorus in algae was mostly organic P, especially Mono-P, which was ≥50% of TP. Environmental factors and water quality parameters such as temperature (T), electrical conductivity (EC), pH, secchi depth (SD), dissolved oxygen (DO), chemical oxygen demand (CODcr), chlorophyll-a (Chl-a), affected the absolute and relative concentrations of various P components in the two lakes. Increased temperature promoted bioavailable P (Ortho-P and Mono-P) release to the lake waters. The results can provide an important theoretical basis for the mutual conversion process of organic P components between various media in the lake water environment.

Simulated photo-degradation of dissolved organic matter in lakes revealed by three-dimensional excitation-emission matrix with regional integration and parallel factor analysis.

Simulated photo-degradation of fluorescent dissolved organic matter (FDOM) in Lake Baihua (BH) and Lake Hongfeng (HF) was investigated with three-dimensional excitation-emission matrix (3DEEM) fluorescence combined with the fluorescence regional integration (FRI), parallel factor (PARAFAC) analysis, and multi-order kinetic models. In the FRI analysis, fulvic-like and humic-like materials were the main constituents for both BH-FDOM and HF-FDOM. Four individual components were identified by use of PARAFAC analysis as humic-like components (C1), fulvic-like components (C2), protein-like components (C3) and unidentified components (C4). The maximum 3DEEM fluorescence intensity of PARAFAC components C1-C3 decreased by about 60%, 70% and 90%, respectively after photo-degradation. The multi-order kinetic model was acceptable to represent the photo-degradation of FDOM with correlation coefficient (Radj2) (0.963-0.998). The photo-degradation rate constants (kn) showed differences of three orders of magnitude, from 1.09 × 10-6 to 4.02 × 10-4 min-1, and half-life of multi-order model ( T1/2n) ranged from 5.26 to 64.01 min. The decreased values of fluorescence index (FI) and biogenic index (BI), the fact that of percent fluorescence response parameter of Region I (PI,n) showed the greatest change ratio, followed by percent fluorescence response parameter of Region II (PII,n), while the largest decrease ratio was found for C3 components, and the lowest T1/2n was observed for C3, indicated preferential degradation of protein-like materials/components derived from biological sources during photo-degradation. This research on the degradation of FDOM by 3DEEM/FRI-PARAFAC would be beneficial to understanding the photo-degradation of FDOM in natural environments and accurately predicting the environmental behaviors of contaminants in the presence of FDOM.

Investigation of eluted characteristics of fulvic acids using differential spectroscopy combined with Gaussian deconvolution and spectral indices.

The characteristics of subfractions of soil fulvic acid (FA3, FA5, FA7, FA9, and FA13) using stepwise elution from XAD-8 resin with pyrophosphate buffers were investigated by differential absorption spectroscopy (DAS) and differential fluorescence spectroscopy (DFS) combined with mathematical deconvolution and spectral indices. The log-transformed absorbance spectra (LTAS) exhibited three regions for both acidic-buffer-eluted subfractions (AESF) and neutral-buffer-eluted subfraction (NESF) and four regions for basic-buffer-eluted subfractions (BESF) according to the differences in spectral slopes. The DAS spectra of FA subfractions were closely fitted with seven Gaussian bands with maxima location at 199.66, 216.18 ± 1.50, 246.20 ± 3.85, 285.22 ± 7.26, 345.64 ± 5.30, 389.27, and 307.37 nm, respectively (R2 > 0.993). The content of salicylic-like and carboxyl groups in FA subfractions decreased, while the phenolic chromophore increased with elution sequence. From the 11 spectral indices, AESF had greater molecular weight, condensation, polymerization, hydroxyl radical production, humification degree, and terrigenous contribution, as well as contained more conjugated aromatic structures and less N-containing groups than NESF and BESF. The humification degree and humic characters of FA subfractions were closely associated to the aromaticity, molecular condensation, and DOM-metal-bound functional groups. The proper separation of FA into subfractions is beneficial for reducing its complexity and heterogeneity, which helps us to further explore its chemical properties and interactions with various contaminants in soil environments. Graphical abstract.

Pyrolysis characteristics of soil humic substances using TG-FTIR-MS combined with kinetic models.

The incorporation and cycling of pyrogenic organic matter in soil is a potential carbon sink, while the pyrolysis behaviors of soil organic matter are still lacking. Pyrolysis characteristics of soil fulvic acid (FA) and humic acid (HA) were investigated using thermogravimetry combined with Fourier transform infrared spectrometer-mass spectrometer (TG-FTIR-MS) and kinetic models. Four reaction stages corresponding to four pseudo-components were distinguished for both FA and HA. FA exhibited greater transformation contributions of hemicellulose-like and cellulose-like pseudo-components, while HA exhibited greater transformation contributions of lignin-like pseudo-components. Compared to HA, higher levels of heat-resistant aromatic compounds, phenolic groups, and carboxylic groups were recognized in FA. Values of both activation energy (Ea, 246.13-661.40 kJ·mol-1) and pre-exponential factor (lnA, 53.49-107.16 min-1) of FA were greater than corresponding Ea (241.74-466.70 kJ·mol-1) and lnA (51.99-74.36 min-1) values of HA determined by Flynn-Wall-Ozawa method and Distributed Activation Energy Model. The main pyrolysis reaction mechanisms of both FA and HA closely matched with the order-based model corresponding to 2nd and 3rd order random nucleation on an individual particle. The evolved gas species of H2, CH4, H2O, and CO2 were dominant for FA and HA pyrolysis. Generally, the total H2/CO2 and CH4/H2O releases were relatively larger for FA and HA pyrolysis, respectively. TG-FTIR-MS is shown to be an effective method to provide valuable and qualitative analysis of the gaseous volatile species evolved during HS pyrolysis. Findings from this systematic study of soil organic matter responding to pyrolysis will be critical for predicting the changes of soil systems or carbon cycle affected by future climate and fire regimes.

Experimental and modeling study of proton and copper binding properties onto fulvic acid fractions using spectroscopic techniques combined with two-dimensional correlation analysis.

Fulvic acid (FA) significantly influences the bioavailability and fate of heavy metals in environments, while its acid-base characters and metal binding processes are still unclear. Here, spectroscopic techniques combined with multiple models (e.g., NICA-Donnan model) and two-dimensional correlation spectroscopy (2D COS) were applied to explore the proton and copper binding properties of FA sub-fractions (FA3-FA13). The charge densities, average contents of carboxylic and phenolic groups, average dissociation constants pKa1 and pKa2 of sub-fractions ranged 0-16 meq∙g∙C-1, 5.03-9.58 meq∙g∙C-1, 2.52-4.67 meq∙g∙C-1, 4.15-4.33 and 8.52-9.72, respectively. FA sub-fractions had a relatively narrow distribution of carboxyl group and a broad distribution of phenolic group. FA sub-fractions also exhibited roughly two phenolic hydroxyl groups per every 1-3 phenyl rings. Differential absorbance spectra (DAS) derived Gaussian bands were associated to the inter-chromophore interactions, the changes of molecular conformations and functional groups with copper addition. Differential spectra slopes (DSlope275-295&325-375) were more significant with higher copper concentration and copper amounts bonded to carboxylic groups. UV-Vis and fluorescence spectra with 2D heterospectral COS revealed the copper binding heterogeneities and sequential orders of chromophores and fluorophores, quantitatively confirming by the order of conditional stability constants (log KCu: 4.64-5.56). Salicylic-/polyhydroxyphenolic, hydroxyl and amino groups were strongly associated to the basic units for fluorophores. Sequential changes followed the order of humic-like→fulvic-like materials for FA3/FA5, humic-like→fulvic-like→tryptophan-like materials for FA7, and humic-like→tryptophan-like→fulvic-like→tyrosine-like materials for FA9/FA13. Spectroscopic techniques combined with various models (especially for 2D COS) are beneficial to elucidate the binding heterogeneity and sensitivity for metal-organic matters at the functional group level.