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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2020 ·Vol. 27 ·期 33 ·41437-41445 · IF 3.056

Tanning process promotes abiotic humification: separation and characterization of humic acid-like polymers complex

Zhu Chao,Wang Huiqin,Ma Hongrui,Yang Yonglin,Li Fan

Humic-like substances are essential components of soluble organic matter in tannery wastewater. However, the tannery process can promote the abiotic humification in wastewater. Therefore, it is of great significance to clarify the pathway and degree of abiotic humification and the properties of the as-derived humic acid-like (HAL) complex polymers in the tannery process in order to control the refractory organic compounds. In the present study, considering the catechol-Maillard system and commercial humic acid (HA) as control, the polyphenol-Maillard humification in the tannery process was simulated under the catalysis of MnO 2 . Moreover, physicochemical and spectroscopic techniques were used to characterize the separated fractions of HAL further. As a result, it was found that the catechol-Maillard system with small molecule organic matter as precursor had higher humification degree. Furthermore, the ultraviolet-visible (UV-Vis), Fourier transform infrared (FTIR), and excitation-emission matrix (EEM) fluorescence spectrum of humic acid-like 0 (HAL0) derived from it was different from those of humic acid-like 1 and 2 (HAL1 and HAL2) of polyphenol-Maillard system, indicating the differences of polymer structure between them. In the polyphenol-Maillard system, tannin was the skeleton of polymerization or polycondensation reaction, and the high content of N and the H/C value of HAL2 indicated that in adding to amino acids, proteins promoted the humification, forming industry-specific HAL polymers with a high degree of aliphatic nature. Therefore, it can be concluded that controlling the raw materials in the tannery process (especially tannins), in order to reduce the occurrence of abiotic humification may be the key to improve the efficiency of wastewater treatment.

CAS / MDL: 54-64-8
研究领域: 环境科学 · 化学工程 · 分析化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Ferrous salts accelerate humification and reduced carbon emissions during the co-composting of hoggery slurry and wheat husks: New insights into their biotic and abiotic functions and mechanisms

Yang Wang,Guorong Yi,Wanqiang Zhang,Jiawei Hou,Kuok Ho Daniel Tang,Bowen Wang,Hua Li,Quan Wang,Hamada Abdelrahman,Tao Zhang,Sabry M. Shaheen,Ronghua Li

In this study, the effects and mechanisms of water-soluble ferrous salts (WSFS) on the humification and carbon conversion during the co-composting of hoggery slurry (HG) and wheat husks (WH) were investigated. A composting mixture of HG and WH was treated with FeCl 2 addition (T1) and FeSO 4 addition (T2), and compared with an untreated control (CK), as a function of time (28 days). The duration of the high-temperature phase (>50 °C) for CK, T1, and T2 are 17, 15, and 15 days, respectively. Compared to the CK, T1 and T2 treatments reduced CO 2 emissions by 11.4 % and 32.0 %, respectively. The calculated total global warming potential values were 293.67 (CK), 267.69 (T1) and 207.10 (T2) g CO 2 eq kg −1 . The humus concentrations increased in all treatments: CK by 28.10 %, T1 by 53.41 % and T2 by 49.73 % in composting. WSFS addition enhanced biotic humification by elevated the abundance and distribution of Bacillus , which promotes cellulose and hemicellulose decomposition, and Tepidimicrobium , which accelerates the production of humus, through use of sugars and proteins. Besides, WSFS addition decreased the levels of pathogenic bacteria in the final compost product. Notably, WSFS addition also benefited the abiotic humification by production of •OH during oxidation of Fe(II) in composting. This study enhances the understanding of the biotic and abiotic functions of FeSO 4 and FeCl 2 in promoting humification and reducing carbon emissions during composting. The detailed role of hydroxyl radical in composting and the effectiveness of WSFS-addition in composting nitrogen transformation are still need to be addressed in future.

研究领域: 环境科学 · 微生物学
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Agronomy-Basel · 2024 ·Vol. 14 ·期 9 ·1951 · IF 3.3

Biochar Catalysis for the Enhanced Abiotic Humification of Polyphenols: An Important Mechanism Helping Sequester Carbon

Jiangmin Zhou,Ziru Zhou,Chuanqing Yao,Yujie Zhang,Han Ren,Guining Lu,Hualin Chen

Abiotic humification, dominated by catalytic oxidation, is one of the critical mechanisms for organic carbon preservation in nature. However, the effects of biochar catalysis on abiotic humification have not yet been elucidated. This study investigated the catalytic power of biochar from walnut shells at different temperatures (300 °C, 600 °C, and 900 °C) for the abiotic transformation of hydroquinone (HQ) as a representative polyphenol. All the biochar samples catalyzed HQ polymerization, resulting in the formation of humic polymers such as fulvic acids (FAs) and humic acids (HAs). Light and oxygen promoted HA formation. HO•was detected in the BC600–HQ reaction system, and HO•quenching resulted in a 41.22% decrease in HA production, indicating that HO•plays a major role in the oxidative polymerization. In the proposed pathway for the abiotic humification, biochar active sites and generated reactive oxygen species accept an electron from HQ, resulting in oxidation to (semi)quinone radicals, which subsequently undergo cleavage or a coupling reaction to form the oligomerized products. Under BC600 catalysis, the weight-average molecular weight (Mw) of the reaction products of HQ, glucose, and glycine reached 14,449 Da. These findings provide new insights into the application potential of biochar for promoting soil carbon sequestration.

研究领域: 环境科学 · 土壤学
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ENVIRONMENT INTERNATIONAL · 2024 · IF 10.3

Novel insights into the mechanism of laccase-driven rhizosphere humification for alleviating wheat 17β-estradiol contamination

Xuemin Qi,Ziyan Niu,Shenghua Xiao,Michael Gatheru Waigi,Hui Lin,Kai Sun

Global-scale crop contamination with environmental estrogens has posed a huge risk to agri-food safety and human health. Laccase is regarded as an unexceptionable biocatalyst for regulating pollution and expediting humification, but the knowledge of estrogen bioremediation and C storage strengthened by laccase-driven rhizosphere humification (LDRH) remains largely unknown. Herein, a greenhouse microcosm was performed to explore the migration and fate of 17 β -estradiol (E2) in water-wheat ( Triticum aestivum L.) matrices by LDRH. Compared to the non-added laccase, the pseudo-first-order decay rate constants of E2 in the rhizosphere solution after 10 and 50 μM exposures by LDRH increased from 0.03 and 0.02 h −1 to 0.36 and 0.09 h −1 , respectively. Furthermore, LDRH conferred higher yield, polymerizability, O-containing groups, and functional-C signals in the humified precipitates, because it accelerated the formation of highly complex precipitates by radical-controlled continuous polymerization. In particular, not only did LDRH mitigate the phytotoxicity of E2, but it also diminished the metabolic load of E2 in wheat tissues. This was attributed to the rapid attenuation of E2 in the rhizosphere solution during LDRH, which limited E2 uptake and accumulation in each subcellular fraction of the wheat roots and shoots. Although several typical intermediate products such as estrone, estriol, and E2 oligomers were detected in roots, only small-molecule species were found in shoots, evidencing that the polymeric products of E2 were unable to be translocated acropetally due to the vast hydrophobicity and biounavailability. For the first time, our study highlights a novel, eco-friendly, and sustainable candidate for increasing the low-C treatment of organics in rhizosphere microenvironments and alleviating the potential risks of estrogenic contaminants in agroenvironments.

研究领域: 环境科学 · 植物学 · 土壤生物学
✓ 已验证 DOI PubMed 高影响因子
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JOURNAL OF HAZARDOUS MATERIALS · 2021 · IF 10.588

Fungal laccase-triggered 17β-estradiol humification kinetics and mechanisms in the presence of humic precursors

Qingzhu Liu,Jie Liu,Dan Hong,Kai Sun,Shunyao Li,Abdul Latif,Xiongyuan Si,Youbin Si

Naturally-occurring phenolic acids (PAs) act as humic precursors that participate in the conversion behaviors and coupling pathways of steroidal estrogens (SEs) during laccase-triggered humification processes (L-THPs). Herein, the influences and mechanisms of PAs on Trametes versicolor laccase-evoked 17 β -estradiol (E2) conversion kinetics and humification routes were explored. Fungal laccase was fleet in converting > 99% of E2, and the calculated pseudo-first-order velocity constant and half-time values were respectively 0.039 min −1 and 17.906 min. PAs containing an O -dihydroxy moiety such as gallic acid and caffeic acid evidently hampered E2 humification owning to the yielded highly reactive O -quinones reversed E2 radicals by hydrogen transfer mechanism, implying that the inhibition effect was enormously dependent upon the number and position of the phenolic –OH present in humic precursors. Oligomers and polymers with carbon-carbon/oxygen links were tentatively found as E2 main humified species resulting from laccase-evoked successive oxidative-coupling. Note that PAs participating in the humification also encountered oxydehydrogenation, self-polymerization, and cross-binding to E2. Interestingly, the –COOH and –OCH 3 groups of PAs could be deprived in radical-caused self/co-polymerization. The generation of humified products not only circumvented the environmental risks of parent compounds but accelerated global carbon sequestration . To our knowledge, this is the first in-depth revelation of the humification pathways and related mechanisms of SEs with humic precursors in aquatic ecosystems by L-THPs.

研究领域: 环境科学 · 生物化学
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PNAS Nexus · 2024 ·Vol. 3 ·期 4 · IF 2.2

Laccase-induced decontamination and humification mechanisms of estrogen in water–crop matrices

Sun Kai,Dai Ling-Zhi,Chen Mei-Hua,Si You-Bin,Fang Guo-Dong,Li Shun-Yao,Yu Han-Qing

Enzymatic humification plays a crucial biogeochemical role in eliminating steroidal estrogens and expanding organic carbon stocks. Estrogenic contaminants in agroecosystems can be taken up and acropetally translocated by crops, but the roles of laccase-triggered rhizospheric humification (L-TRH) in pollutant dissipation and plant uptake remain poorly understood. In this study, the laccase-induced decontamination and humification mechanisms of 17β-estradiol (E2) in water–crop media were investigated by performing greenhouse pot experiments with maize seedlings (Zea mays L.). The results demonstrated that L-TRH effectively dissipated E2 in the rhizosphere solution and achieved the kinetic constants of E2 dissipation at 10 and 50 μM by 8.05 and 2.75 times as much as the treatments without laccase addition, respectively. The copolymerization of E2 and root exudates (i.e. phenols and amino acids) consolidated by L-TRH produced a larger amount of humified precipitates with the richly functional carbon architectures. The growth parameters and photosynthetic pigment levels of maize seedlings were greatly impeded after a 120-h exposure to 50 μM E2, but L-TRH motivated the detoxication process and thus mitigated the phytotoxicity and bioavailability of E2. The tested E2 contents in the maize tissues initially increased sharply with the cultivation time but decreased steadily. Compared with the treatment without laccase addition, the uptake and accumulation of E2 in the maize tissues were obviously diminished by L-TRH. E2 oligomers such as dimer, trimer, and tetramer recognized in the rhizosphere solution were also detected in the root tissues but not in the shoots, demonstrating that the acropetal translocation of E2 oligomers was interrupted. These results highlight a promising strategy for decontaminating estrogenic pollutants, boosting rhizospheric humification, and realizing low-carbon emissions, which would be beneficial for agroenvironmental bioremediation and sustainability.

研究领域: 环境科学 · 农业科学 · 生物化学
✓ 已验证 DOI PubMed 高影响因子
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Eco-Environment & Health · 2023 · IF 0

Lignin precursors enhance exolaccase-started humification of bisphenol A to form functional polymers

Shunyao Li,Dan Hong,Kai Sun

Humification plays a significant role in converting phenolic pollutants and forming heterogeneous polymers, but few studies have been performed to investigate exolaccase-started humification (ESH). Herein, the influences of lignin precursors (LPs) on exolaccase-induced bisphenol A (BPA) removal and humification were explored. In particular, the architectural features and botanical effects of the formed humification products were also tested. ESH was extremely beneficial in boosting BPA removal in the presence of LPs. Compared with LP-free (58.49%), 100% of BPA was eliminated after the reaction with ESH for 72 h. Such a process was controlled by an exolaccase-caused random assembly of radicals, which generated a large number of hydrophobic polymers through nonspecific covalent binding of C–C and/or C–O. These humified polymers were extremely stable at pH 2.0–10.0 and −20 °C to 80 °C and displayed unique functions, i.e. , scavenged 2,2-diphenyl-1-picrylhydrazyl/2,2′-azino-bis3-ethylbenzothiazoline-6-sulphonic acid radicals and exerted antioxidant capacities. More importantly, the functional polymers could act as auxin analogs to increase the germination index (>100%), plant biomass, and salt tolerance of radish seedlings. Our findings disclosed that ESH could not only be optimized to mitigate the ecological risks of phenolic pollutants and sequester organic carbon in environmental bioremediation, but the resulting abundant auxin analogs also contributed to agricultural productivity.

研究领域: 环境生物修复 · 植物学 · 生物化学 · 农业科学
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SCIENCE OF THE TOTAL ENVIRONMENT · 2021 · IF 7.963

Extracellular laccase-activated humification of phenolic pollutants and its application in plant growth

Shunyao Li,Dan Hong,Wenjun Chen,Jun Wang,Kai Sun

Humification processes of phenolic pollutants may play a profound role in environment purification and plant growth. However, little literature is performed to explore exoenzyme-driven humification to polymerize 17 β -estradiol (E2) and humic constituents (HCs), and the effects of their polymeric precipitates on plant growth are usually overlooked. Herein, E2 conversion and radish ( Raphanus sativus L.) growth were systematically investigated under humification mediated by extracellular laccase (EL) of Trametes versicolor . Results disclosed that EL-assisted humification achieved a wonderful E2 conversion efficiency (>99%) within 2-h, but the presence of HCs such as humic acid (HA), vanillic acid (VA), and ferulic acid (FA) impeded E2 elimination significantly. Compared with HC-free, the kinetics constants declined by 2.84-, 5.72-, and 5.22-fold with HA, VA, and FA present, respectively. Intriguingly, three close-knit self/cross-linked precipitates ( i.e. , E2-HA, E2-VA, and E2-FA hybrid precipitates) in dark gray, dark brown, and deep yellow were created after a continuous humification by phenolic radical-initiated polymerization mechanisms. The formation of these humified precipitates was extremely effective on circumventing phytotoxicity caused by monomeric E2, VA, or FA. Furthermore, they acted as humic-like organic fertilizers , accelerating seed germination, root elongation, and enhancing NaCl-tolerance of radish through the combination of oxygen-contained functional components and auxin structural analogues with unstable and stubborn carbon skeletons. This is the first study reporting the pollution purification and plant growth promotion in EL-activated humification. Our findings frame valuable perspectives regarding the natural detoxification and carbon sequestration of phenolic pollutants and the application of their polymeric precipitates in global crop production.

CAS / MDL: 123-76-2 72-18-4
研究领域: 环境科学 · 植物学 · 生物化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2023 · IF 6.1

Exolaccase Propels Humification to Decontaminate Bisphenol A and Create Humic-like Biostimulants

Shunyao Li,Yuehui Sheng,Shenghua Xiao,Qingzhu Liu,Kai Sun

Exolaccase-propelled humification (E-PH) helps eliminate phenolic pollutants and produce macromolecular precipitates. Herein, we investigated the influencing mechanism of 12 humic precursors (HPs) on exolaccase-enabled bisphenol A (BPA) decontamination and humification. Catechol, vanillic acid, caffeic acid, and gentian acid not only expedited BPA removal but also created large amounts of copolymeric precipitates. These precipitates had rich functional groups similar to natural humic substances, which presented great aromatic and acidic characteristics. The releasing amounts of BPA monomer from four precipitates were 0.08–12.87% at pH 2.0–11.0, suggesting that BPA-HP copolymers had pH stability. More excitingly, certain copolymeric precipitates could stimulate the growth and development of radish seedlings. The radish growth-promotion mechanisms of copolymers were involved in two aspects: (1) Copolymers interacted with root exudates to accelerate nutrient uptake; (2) Copolymers released auxins to provoke radish growth. These results may provide an innovative strategy for decontaminating phenolic pollutants and yielding humic-like biostimulants in E-PH.

研究领域: 环境科学 · 生物化学 · 植物学
✓ 已验证 DOI PubMed 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Hydrothermal humification of lignocellulosic components: Who is doing what?

Yuchao Shao,Weizhong Huo,Rong Ye,Yanqing Liu,Muhammad Ajmal,Wenjing Lu

The humification behavior of lignocellulosic components ( i.e. , cellulose, hemicellulose and lignin) under acid-alkali two-step hydrothermal treatment was investigated with particular interest of revealing the contribution of single components as well as their interaction to hydrothermal humic acid (HHA). Lignin with its rich aromatic structures, had the highest HHA contribution (51.8 ± ± 1.0 wt%), while cellulose and hemicellulose only contributed 8.8 ± ± 1.6 wt% and 20.1 ± ± 4.4 wt% HHA yields, respectively. The conversion pathway of these components toward humification indicated that the hydrochar (HC) rather than the hydrothermal solution (HS) had higher humification capability under alkaline hydrothermal conditions because the hydrochar-derived HHA yields of 40.8 ± ± 2.0 wt% (cellulose), 66.2 ± ± 6.4 wt% (hemicellulose) and 55.4 ± ± 6.1 wt% (lignin) were achieved. In addition, co-hydrothermal treatment of cellulose, hemicellulose and lignin under this process improved the HHA production ascribing to the increased HC yield (23.1–53.1 %). The chemical characteristics of HHA products from lignocellulosic components (cellulose, hemicellulose, lignin) and their combinations were similar to the acknowledged natural humic acids. The hydrothermal humification of biowaste mainly passes through a top-down pathway ( i.e. , HHA forms from the oxidation of large fragments of hydrochar) as well as two bottom-up pathways ( i.e. , the soluble chemicals conduct the polymerization reaction for HHA production and react with the fragments from HC to synthesize the HHA). This study filled the lack of knowledge in the field of biowaste humification.

研究领域: 环境科学 · 化学工程 · 生物技术
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Effects of exogenously added humic acid on the fate of aminoglycoside antibiotics and humification process during aerobic compost

Guoxu Ao,Zhaoxuan Wang,Yueqi Shi,Hongzhi Ling,Shanshan Sun,Wenxiang Ping

Efficient elimination of antibiotics, particularly aminoglycosides, and Antibiotic resistance genes (ARGs) from agricultural and livestock waste, as well as enhancing the level of humification, remains a major challenge in the pursuit of high-value utilization of agricultural waste. Here, the roles of bacteria and fungus in the dissipation of aminoglycoside antibiotics, ARGs and the enhancement of humification with the addition of humic acid (HA) to compost systems were investigated. Compared to the control, the contents of humus (HS) and HA were increased by 41.3 and 143.3 %, respectively, and the content of fulvic acid (FA) was decreased by 74.1 % with HA addition. Interestingly, the abundance of aminoglycoside ARGs was decreased significantly ( p  < 0.05) as well as the abundance of functional genes involved in oxidative stress response and type IV secretion system (T4SS). The bacterium Nocardiopsis related to carbon cycle, and the fungi Ascomycota and Basidiomycota associated with ligocellulose degradation were significantly enriched ( p  < 0.05). Structural equation models revealed that the decrease in aminoglycoside ARGs abundance was attributed to bacteria promoting HA synthesis, thereby inhibiting the multiplication of aminoglycoside ARGs and ultimately mitigating oxidative damage to microbial cells. These findings shed light on the mechanism by which HA removes aminoglycoside ARGs, and provide valuable insights into enhancing the biosafety of compost products.

CAS / MDL: 1415-93-6
研究领域: 环境科学 · 微生物学
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SCIENCE OF THE TOTAL ENVIRONMENT · 2020 · IF 6.551

Transformation of catechol coupled to redox alteration of humic acids and the effects of Cu and Fe cations

Xiong Jia,Yujie He,Philippe F.-X. Corvini,Rong Ji

Humic substances are reactive during redox alteration. However, the role of this reactivity in the transformation of organic compounds and in carbon cycling in the environment is still unclear. Here, we used 14 C-radioactive tracer to study abiotic transformation and humification of catechol, a representative of naturally occurring monomeric phenols and phenolic pollutants, in suspensions of humic acids (HAs) at original and H 2 /Pd-reduced redox states with flux of air (HA org -Air and HA red -Air, respectively) or N 2 (HA org -N 2 and HA red -N 2 , respectively) for 20 min in absence and presence of Cu(II) and Fe(II). Both HA org and HA red can transform catechol in the absence of O 2 to 19% and 25% of the initially applied amount, respectively. The transformation of catechol strongly increased when air was introduced, amounting to 75% in HA red -Air treatment and 43% in HA org -Air treatment, owing to the generation of reactive oxygen species . Considerable amounts of catecholic carbons were incorporated into HAs (26% for HA red -Air and 19% for HA org -Air), constituting humification of catechol. The presence of Cu(II) strongly inhibited the overall transformation and humification of catechol, although it significantly increased humification at the start of incubation. The presence of Fe(II) overall enhanced both the transformation and humification. The results provide first insights into the impacts of redox alteration of humic substances together with the presence of metal ions with variable valences on the fate of phenolic compounds in the environment. This study points out that redox alteration-induced abiotic transformation may be one important process for dissipation of phenolic pollutants and humification of phenolic carbons in environments rich in HAs and subject to redox fluctuation.

CAS / MDL: 120-80-9 3317-61-1
研究领域: 环境科学 · 有机化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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