哈尔滨市降雪中溶解性有机物光谱特性分析

研究雨雪中的溶解性有机物(DOM)将有利于把握其理化性质及其在生态系统中的行为和功能.本研究运用三维荧光光谱(EEMs)技术结合平行因子分析(PARAFAC)、紫外-可见光谱技术(UV-vis),对哈尔滨市2018年3月1日降雪样品中DOM的光谱特性及来源进行解析.结果表明,降雪样品中DOM的相对分子质量较大,芳香构造...     

Effects of oxidizing environment on digestate humification and identification of substances governing the dissolved organic matter (DOM) transformation process

• Liquid digestate humification was investigated under different oxidizing environment. • Tryptophan-like substances dominated the transformation of the liquid digestate DOM. • The humification sequence of the liquid digestate DOM was identified. • UV₃₂₅ was first identified as a pre-humus intermediate during humification reaction. The formation of humic-like acids (HLAs) is an essential process for converting liquid digestate into organic soil amendments to enhance agricultural sustainability. The aim of this study was to investigate the impact of oxygen and/or MnO₂ on the production of HLAs. Herein, abiotic humification performance of the digestate dissolved organic matter (DOM) is investigated with fluxes of air and N₂ in the absence and presence of MnO₂. Our results demonstrated that the fate of digestate DOM greatly depends on the oxidizing environment, the MnO₂ enhanced nitrogen involved in the formation of HLAs. The synergistic effects of MnO₂ and oxygen effectively improved the production of HLAs, and the corresponding component evolution was analyzed using spectroscopic evidence. The two-dimensional correlation spectroscopy results demonstrated that the reaction sequence of digestate DOM followed the order of protein-like substances, substances with an absorbance at 325 nm, substances with UV absorbance at 254 nm and HLAs. Additionally, excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) showed that tryptophan-like C3 was more prone to transformation than tyrosine-like C2 and was responsible for the humification process. The substance with an absorbance at 325 nm was a reaction intermediate in the transformation process of protein-like substances to HLAs. The above findings can be used to promote the production of liquid fertilizer associated with carbon sequestration as well as the sustainable development of biogas production.     

热带滨海区不同土地利用背景下土壤溶解性有机氮的组成与粒径分布特征

溶解态有机氮(DON)是土壤中活跃的氮库,其生态环境行为与它的化学组成和粒径分布密切相关。为评估热带滨海区不同土地利用方式对不同粒径中土壤溶解性有机氮组成特征的影响,从水稻田、橡胶园、菜园和果园采集土壤样品,通过一系列微滤和超滤(0.7,0.45,0.2,0.1μm,100,10,1 kDa)对土壤溶解性有机氮分级,并使用连续流动分析仪、三维荧光光谱和红外光谱研究了滤液中溶解态有机氮、无机氮的含量及荧光组分和有机官能团特征。结果表明,4种土地利用背景下土壤DON值的范围为5.25-10.88 mg·kg^-1,其大小顺序为水稻>菜园>果树>橡胶,且DON与溶解性总氮(DTN)的比值范围为26.08%-67.11%,其中橡胶土最高,水稻土最低;不同粒径下4种土地利用类型土壤DON主要集中在<100 kDa的粒径中,其值范围为4.85-9.48 mg·kg^-1,占全量的85.89%-92.41%。三维荧光光谱(3D-EEMs)及平行因子分析表明,4种土地利用背景下土壤DON含有两种类腐殖质组分及一种类蛋白质组分,且以类腐殖质组分为主,占比54.00%-77.67%;类蛋白组分对土地利用变化敏感,且随着粒径的减小,类蛋白组分占比增加,在<1 kDa组分中比例最高。红外光谱结果表明,4种土地利用背景下土壤DON主要在6个位置有相似的吸收峰,包含3410 cm^-1、1636 cm^-1、1402 cm^-1、1138-1035 cm^-1、673 cm^-1、602 cm^-1,不同土地利用背景下各吸收峰的透光度不同,强度最大的吸收来自游离的胺类N-H伸缩振动;水稻、菜园土壤DON芳香物质含量较高,结构较复杂。了解DON的组成与粒径分布对土地利用的响应,对进一步研究其生态环境行为具有重要意义。     

Characterization of the dissolved organic matter in sewage effluent of sequence batch reactor: the impact of carbon source

Dissolved organic matter (DOM) transformation in sequence batch reactor (SBR) fed with carbon sources of different biodegradability was investigated. During the biologic degradation process, the low molecular weight (MW) fraction (< 1 kDa) gradually decreased, while the refractory compounds with higher aromaticity were aggregated. Size exclusion chromatography (SEC) and fluorescence of excitation emission matrices (EEM) demonstrated that more biopolymers (polysaccharides or proteins) and humic-like substances were presented in the extracellular polymeric substance (EPS) extracted from the SBR fed with sodium acetate or glucose, while the EPS from SBR fed with slowly biodegradable dissolved organic carbon (DOC) substratestarch had relatively less biopolymers. Comparing the EfOM in sewage effluent of three SBRs, the effluent from SBR fed with starch is more aromatic. Organic carbon with MW>1 kDa as well as the hydrophobic fraction in DOM gradually increased with the carbon sources changing from sodium acetate to glucose and starch. The DOC fractionation and the EEM all demonstrated that EfOM from the effluent of the SBR fed with starch contained more fulvic acid-like substances comparing with the SBR fed with sodium acetate and glucose.     

Characterization of dissolved organic matter from saline soils by fluorescence spectroscopy

In this paper hydrophilic (HI) and hydrophobic (HO) fractions of dissolved organic matter (DOM) extracted from soils at different degrees of salinisation were characterised by means of fluorescence spectroscopy in the emission, excitation and synchronous-scan modes. Results provided evidence of the different chemical nature of DOM fractions and allowed to distinguish hydrophilic and hydrophobic fractions extracted from the same soil substrate. The strong decrease in fluorescence intensity observed with the increasing salinity of the soils can be utilised to obtain information on the salinity level of different soil substrates by comparison of spectral fluorescence intensities.     

Photosensitivity sources of dissolved organic matter from wastewater treatment plants and their mediation effect on 17α-ethinylestradiol photodegradation

● EE2 photodegradation behavior in the presence of four WWTPs’ DOM was explored. ● The ³DOM* played a major role in the EE2 photodegradation mediated by WWTPs’ DOM. ● The A²/O process DOM contained more aromatic and oxygen-containing substances. ● Possible photosensitivity sources of DOM in the A²/O process were proposed. Dissolved organic matter (DOM) from each treatment process of wastewater treatment plants (WWTPs) contains abundant photosensitive substances, which could significantly affect the photodegradation of 17α-ethinylestradiol (EE2). Nevertheless, information about EE2 photodegradation behavior mediated by DOM from diverse WWTPs and the photosensitivity sources of such DOM are inadequate. This study explored the photodegradation behavior of EE2 mediated by four typical WWTPs’ DOM solutions and investigated the photosensitivity sources of DOM in the anaerobic-anoxic-oxic (A²/O) process. The parallel factor analysis identified three varying fluorescing components of these DOM, tryptophan-like substances or protein-like substances, microbial humus-like substances, and humic-like components. The photodegradation rate constants of EE2 were positively associated with the humification degree of DOM (P < 0.05). The triplet state substances were responsible for the degradation of EE2. DOM extracted from the A²/O process, especially in the secondary treatment process had the fastest EE2 photodegradation rate compared to that of the other three processes. Four types of components (water-soluble organic matter (WSOM), extracellular polymeric substance, humic acid, and fulvic acid) were separated from the A²/O process DOM. WSOM had the highest promotion effect on EE2 photodegradation. Fulvic acid-like components and humic acid-like organic compounds in WSOM were speculated to be important photosensitivity substances that can generate triplet state substances. This research explored the physicochemical properties and photosensitive sources of DOM in WWTPs, and explained the fate of estrogens photodegradation in natural waters.     

Identification of sources,characteristics and photochemical transformations of dissolved organic matter with EEM-PARAFAC in the Wei River of China

• The source of DOM in surface water and sediment is inconsistent. • The DOC content changes differently in surface water and sediment. • The content of DOC in the surface water is lower than that in the sediment. • The DOM in the surface water had higher photodegradation potentials than sediment. Dissolved organic matter (DOM) in rivers is a critical regulator of the cycling and toxicity of pollutants and the behavior of DOM is a key indicator for the health of the environment. We investigated the sources and characteristics of DOM in surface water and sediment samples of the Wei River, China. Dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm (UV₂₅₄) increased in the surface water and were decreased in the sediment downstream, indicating that the source of DOM in the water differed from the sediment. Parallel factor (PARAFAC) analysis of the excitation-emission matrices (EEM) revealed the presence of terrestrial humus-like, microbial humus-like and tryptophan-like proteins in the surface water, whereas the sediment contained UVA humic-like, UVC humic-like and fulvic-like in the sediment. The DOM in the surface water and sediment were mainly derived from microbial metabolic activity and the surrounding soil. Surface water DOM displayed greater photodegradation potential than sediment DOM. PARAFAC analysis indicated that the terrestrial humic-like substance in the water and the fulvic-like component in the sediment decomposed more rapidly. These data describe the characteristics of DOM in the Wei River and are crucial to understanding the fluctuations in environmental patterns.     

施肥对不同肥力春玉米田土壤溶解性有机质的影响

选取辽河灌区不同肥力水平春玉米（Zea mays ssp. mays L.）农田土壤为研究对象,通过连续3年田间定位试验,采用三维荧光光谱法分析了不同层次土壤溶解性有机质组分含量,研究施肥对不同肥力农田土壤溶解性有机质组分（DOM、DOC、DON、DOP）的影响,分析土壤DOM及其组分的土壤肥力效应。结果表明,施肥使高（产量12.75±0.75 t·hm^-2）、中（产量10.50±0.75 t·hm^-2）、低（产量8.25±0.75 t·hm^-2）产田土壤DOM的∑Fex/em分别增加了2.84%、3.56%和-1.52%,平均增加了1.08%,土壤w（DOC）分别增加了20.43%、16.43%和-29.11%,平均增加了9.36%,土壤w（DOP）分别增加了-22.87%、10.30%和4.15%,平均增加了-3.39%,土壤 w（DON）分别增加了-20.63%、6.97%和-8.41%,平均增加了-7.54%。施肥显著增加中产田土壤中w（DOM）,中产田底层（20-40 cm）和高产田表层（0-10 cm）、中层（10-20 cm）土壤w（DOC）,中产田中层和低产田表层土壤w（DOP）,中产田中层土壤w（DON）。施肥增加了低产田土壤FI值（荧光指数）,降低了高产田土壤FI值,施肥增加了高产田土壤HIX（腐殖化指数）,降低了中低产田土壤HIX。施肥显著增加中产田土壤DOM组分含量,降低高、低产田土壤DOM组分含量。施肥主要增加10-20 cm土壤DOM组分含量,耗损20-0 cm土壤DOM组分。施肥促进高产田土壤DOM陆源化,低产田土壤DOM生物源化,施肥使中低产田土壤DOM腐殖化程度降低。施肥不仅是土壤DOM的重要来源,同时通过影响微生物及作物根系活力促进土壤DOM的耗损,因农田土壤质地的差异,施肥对土壤DOM的影响不同。DOM荧光强度与产量呈显著正相关,具有土壤肥力指示作用。     

长江重庆段溶解性有机物的荧光特性分析

利用三维荧光光谱(EEMs),并结合平行因子分析(PARAFAC)及主成分分析(PCA),研究了长江重庆段溶解有机物(DOM)的荧光组分特征及其污染来源,并探讨了荧光强度同溶解性有机碳(DOC)及溶解氧(DO)的相关性.结果表明,PARAFAC模型识别出长江重庆段DOM由2类6个荧光组分组成,即类腐殖质荧光组分C1(350/422 nm)、C4(245,305/395 nm)、C5(260,340/420 nm)、C6(260/480 nm)及类蛋白荧光组分C2(275/300 nm)、C3(227,278/329 nm).在DOM来源组成中,陆源的类腐殖质含量占62.56%,类蛋白物质含量占31.31%.类腐殖质组分的荧光强度同DOC的含量存在明显的线性正相关(r=0.73),类蛋白组分的荧光强度同DO的含量呈明显的线性负相关(r=0.80).EEMs-PARAFAC不仅可以表征长江重庆段DOM的光谱特征,示踪长江重庆段的有机污染程度,还可以为三峡库区水体保护提供依据.     

威廉腔环蚓(Metaphire guillelmi)对~(14)C-土壤有机质转化的研究

土壤有机碳是全球碳循环的重要组成部分,而大型土壤动物对土壤碳库的稳定性起着重要的决定作用。利用14C示踪技术,以14C-葡萄糖制备微生物源的土壤有机质(Soil organic matter,SOM),以蚯蚓威廉腔环蚓(Metaphire guillelmi)为代表,研究了14C-SOM在含有蚯蚓的两种土壤、不含蚯蚓的对照土壤和不含蚯蚓的蚓粪中的矿化、残留物在土壤和蚓粪中分布以及蚯蚓对14C-SOM的吸收。结果显示,15 d的培育期内蚯蚓显著加快了14C-SOM的矿化,在土壤中的矿化量是不含蚯蚓的对照土壤中矿化量的1.5～1.7倍,然而当移出蚯蚓后,残留14C-SOM在两种土壤中40 d内的矿化都比对照土壤中低。大约有4.2%～4.8%的14C-SOM被蚯蚓吸收利用。在有蚯蚓存在的土壤中,14C-SOM残留物在胡敏素中的含量有所增高,而在溶解有机物(DOM)中的含量显著降低。14C-SOM在不含蚯蚓的蚓粪中55 d内的矿化量和矿化动力学以及残留分布与在对照土壤中均没有显著区别。这些结果表明,蚯蚓对微生物源14C-SOM转化的影响主要是蚯蚓的肠道作用,这种作用可表现在两个方面,即初期对14C-SOM矿化的促进作...     

土壤溶解性有机质的生态环境效应

土壤生态环境是一个复杂的多介质多界面体系。现有的研究表明，DOM作为环境中重要的天然配位体和吸着载体，是一种非常活跃的化学物质，它将土壤中的矿物质、有机质与生物成分联系在一起，通过物理或化学作用改变金属与外源性化合物的环境行为，促进温室气体的排放，调节土壤养分流失，指示土壤质量，并对成土过程、微生物的生长代谢过程、土壤有机质分解和转化过程有着重要作用，已经成为土壤科学、生态科学和环境科学交叉领域的研究热点。文章系统地评述了DOM的组成特点及其环境效应，同时介绍了未来的研究方向及一些有待于进一步研究的问题。     

夏季渭河西安段溶解性有机质(DOM)的特征、分布及来源分析

通过紫外吸收光谱,三维荧光光谱结合平行因子分析(EEMs-PARAFAC)方法及主成分分析(PCA),研究了夏季渭河西安段水体中的溶解性有机质(DOM)的组成、来源,及其与水质指标的相关性.在研究区域共检出2种类别5个不同的DOM组分,分别为类腐殖质荧光组分C1、C2、C3、C5和1个类蛋白类荧光组分C4,5个组分具有...     

Influence of Dissolved Organic Matter On the Bio-Availability and Toxicity of Metals in Soils and Aquatic Systems

Cations in soil are essential for the growth of plants and micro-organisms. Their availability is dependent on soil organic matter. Soil organic matter (SOM) is heterogeneous comprising amino, aliphatic and phenolic acids, but particularly humic substances. All these substances can complex cations selectively. Mechanisms of complexation with dissolved organic matter are discussed. Such complexation can lead to the apparently contradictory observations that dissolved organic matter (DOM) can either increase the concentration of some less soluble nutrients, making them more available for plant uptake, or make them less available and hence less toxic. the importance of DOM is discussed in relation to soil solution, particularly the rhizosphere, and also in relation to aquatic systems. the latter systems contain mainly dissolved humic substances whereas in the soil, non-humic substances assume a greater importance.

SOM in the rhizosphere is derived from plant, microbial and animal remains but much, especially the water-soluble compounds, are acquired through root exudation. Exudation has important consequences for enhanced nutrient availability as a result of the production of non-humic substances such as amino, aliphatic and phenolic acids. in future, the role of root exudation in relation to DOM and nutrient availability should be investigated more fully, particularly as predicted elevated CO₂ levels are likely to have a major impact on root exudation, nutrient availability, and possibly ecosystem community structure and functioning. It is likely that more information will become available on aquatic systems as more highly sensitive techniques and equipment capable of dealing with low concentrations of DOM in these systems become available.     

Influence of Dissolved Organic Matter On the Bio-Availability and Toxicity of Metals in Soils and Aquatic Systems

Cations in soil are essential for the growth of plants and micro-organisms. Their availability is dependent on soil organic matter. Soil organic matter (SOM) is heterogeneous comprising amino, aliphatic and phenolic acids, but particularly humic substances. All these substances can complex cations selectively. Mechanisms of complexation with dissolved organic matter are discussed. Such complexation can lead to the apparently contradictory observations that dissolved organic matter (DOM) can either increase the concentration of some less soluble nutrients, making them more available for plant uptake, or make them less available and hence less toxic. the importance of DOM is discussed in relation to soil solution, particularly the rhizosphere, and also in relation to aquatic systems. the latter systems contain mainly dissolved humic substances whereas in the soil, non-humic substances assume a greater importance.

SOM in the rhizosphere is derived from plant, microbial and animal remains but much, especially the water-soluble compounds, are acquired through root exudation. Exudation has important consequences for enhanced nutrient availability as a result of the production of non-humic substances such as amino, aliphatic and phenolic acids. in future, the role of root exudation in relation to DOM and nutrient availability should be investigated more fully, particularly as predicted elevated CO₂ levels are likely to have a major impact on root exudation, nutrient availability, and possibly ecosystem community structure and functioning. It is likely that more information will become available on aquatic systems as more highly sensitive techniques and equipment capable of dealing with low concentrations of DOM in these systems become available.     

High amounts of free aromatic amino acids in the protein-like fluorescence of water-dissolved organic matter

Fluorescence spectroscopy is widely used to study water pollution. The fluorescence of water natural organic matter can be classified into two groups: the protein-like fluorescence originating from aromatic amino acids and the humic fluorescence originating from humic substances. Actually, the precise molecular origin of the protein-like fluorescence is unknown because this fluorescence may be caused by either free amino acids, peptides or proteins. Therefore, we studied the molecular origin of the protein-like fluorescence of Suwannee River natural organic matter and fractions A, B and C + D obtained by size exclusion chromatography/polyacrylamide gel electrophoresis. Fractions were analyzed by reversed-phase high-performance liquid chromatography. The electrophoretic mobilities of fractions varied in the order C + D > B > A and the molecular size in the opposite order. Our results show that the protein-like fluorescence is almost exclusively located in high molecular size fraction A and medium molecular size fraction B. Retention times and fluorescence emission spectra of authentic free aromatic amino acids tyrosine and tryptophan were identical with the retention times and emission spectra of several chromatographic peaks of fractions A and B. More than 50 % of the protein-like fluorescence is due to free aromatic amino acids incorporated in water natural organic matter.     

Spatial connectivity in a large river system: resolving the sources and fate of dissolved organic matter

Large rivers are generally heterogeneous and productive systems that receive important inputs of dissolved organic matter (DOM) from terrestrial and in situ sources. Thus, they are likely to play a significant role in the biogeochemical cycling of the DOM flowing to the oceans. The asymmetric spatial gradient driven by directional flow and environmental heterogeneity contributes to the fate of DOM flowing downstream. Yet, the relative effects of spatial connectivity and environmental heterogeneity on DOM dynamics are poorly understood. For example, since environmental variables show spatial heterogeneity, the variation explained by environmental and spatial variables may be redundant. We used the St. Lawrence River (SLR) as a representative large river to resolve the unique influences of environmental heterogeneity and spatial connectivity on DOM dynamics. We used three-dimensional fluorescence matrices combined with parallel factor analysis (PARAFAC) to characterize the DOM pool in the SLR. Seven fluorophores were modeled, of which two were identified to be of terrestrial origin and three from algal exudates. We measured a set of environmental variables that are known to drive the fate of DOM in aquatic systems. Additionally, we used asymmetric eigenvector map (AEM) modeling to take spatial connectivity into account. The combination of spatial and environmental models explained 85% of the DOM variation. We show that spatial connectivity is an important driver of DOM dynamics, as a large fraction of environmental heterogeneity was attributable to the asymmetric spatial gradient. Along the longitudinal axis, we noted a rapid increase in dissolved organic carbon (DOC), mostly controlled by terrestrial input of DOM originating from the tributaries. Variance partitioning demonstrated that freshly produced protein-like DOM was found to be the preferential substrate for heterotrophic bacteria undergoing rapid proliferation, while humic-like DOM was more correlated to the diffuse attenuation coefficient of UVA radiation.     

Characterization and variation of dissolved organic matter in composting: a critical review

● Effect of composting approaches on dissolved organic matter (DOM). ● Effect of composting conditions on the properties of DOM. ● Character indexes of DOM varied in composting. ● The size, hydrophobicity, humification, and electron transfer capacity increased. ● The hydrophilicity, protein-like materials, and aliphatic components reduced. As the most motive organic fraction in composting, dissolved organic matter (DOM) can contribute to the transfer and dispersal of pollutants and facilitate the global carbon cycle in aquatic ecosystems. However, it is still unclear how composting approaches and conditions influence the properties of compost-derived DOM. Further details on the shift of DOM character indexes are required. In this study, the change in properties of compost-derived DOM at different composting approaches and the effect of composting conditions on the DOM characteristics are summarized. Thereafter, the change in DOM character indexes’ in composting was comprehensively reviewed. Along with composting, the elements and spectral properties (chromophoric DOM (CDOM) and fluorescent DOM (FDOM)) were altered, size and hydrophobicity increased, and aromatic-C and electron transfer capacity were promoted. Finally, some prospects to improve this study were put forward. This paper should facilitate the people who have an interest in tracing the fate of DOM in composting.     

Effects of dissolved organic matter on the desorption of Cd in freeze–thaw treated Cd-contaminated soils

Lab-scale experiments were conducted to investigate the effects of dissolved organic matter (DOM) on the desorption of Cd in freeze–thaw treated Cd-contaminated soils. The results indicated that DOM significantly facilitated the desorption of Cd from freeze–thaw treated soils when comparing with that of non-frozen soils. Effects of DOM on the Cd desorption were highly dependent on the soil type and contamination concentration. The maximum desorption ratios of Cd by DOM generated from straw and sludge were 15.6% and 13.65%, respectively, in brown soils, and the maximum desorption ratios reached 14.7% and 9.3%, respectively, when using black soils through the same treatment. The higher the Cd contamination concentration in soils, the higher the ratio of Cd desorption by DOM. This was because of the integrated effects of the soil properties changed by the freeze–thaw treatment and the species transformation of Cd. The characteristics of DOM, such as its concentration and properties, had shown obvious impacts on the Cd desorption by DOM. The desorption was promoted with the increased DOM concentration and the hydrophilic fraction, and lowered pH and the low-molecular-weight of DOM.     

Excitation-emission matrix (EEM) fluorescence spectroscopy for characterization of organic matter in membrane bioreactors: Principles,methods and applications

• Principles and methods for fluorescence EEM are systematically outlined. • Fluorophore peak/region/component and energy information can be extracted from EEM. • EEM can fingerprint the physical/chemical/biological properties of DOM in MBRs. • EEM is useful for tracking pollutant transformation and membrane retention/fouling. • Improvements are still needed to overcome limitations for further studies. The membrane bioreactor (MBR) technology is a rising star for wastewater treatment. The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter (DOM) in the system. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, a powerful tool for the rapid and sensitive characterization of DOM, has been extensively applied in MBR studies; however, only a limited portion of the EEM fingerprinting information was utilized. This paper revisits the principles and methods of fluorescence EEM, and reviews the recent progress in applying EEM to characterize DOM in MBR studies. We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity, wavelength regional distribution, and spectral deconvolution (giving fluorescent component loadings/scores), and discussed how to use the information to interpret the chemical compositions, physiochemical properties, biological activities, membrane retention/fouling behaviors, and migration/transformation fates of DOM in MBR systems. In addition to conventional EEM indicators, novel fluorescent parameters are summarized for potential use, including quantum yield, Stokes shift, excited energy state, and fluorescence lifetime. The current limitations of EEM-based DOM characterization are also discussed, with possible measures proposed to improve applications in MBR monitoring.     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.