Components Of Humic Substances Research Articles

The Influence of Green Manure Planting on the Spectroscopic Characteristics of Dissolved Organic Matter in Freshwater-Leached Saline–Alkali Soil at Different Depths

This study investigated the influence of green manure planting on the spectroscopic properties of dissolved organic matter (DOM) in saline–alkali soil under freshwater leaching conditions at different soil depths. The UV254, UV253/UV203, α300, α355, SUVA254, SUVA260, and SR ultraviolet parameters indicated reductions in the content of large molecular substances, benzene ring substitution degree, colored dissolved organic matter, aromaticity, and hydrophobic components in the soil leachate DOM with an increasing soil depth. Compared with the non-green manure treatment control, green manure planting mitigated the leaching of dissolved organic matter in soil during saline irrigation, with rape green manure demonstrating superior effectiveness. Utilizing three-dimensional fluorescence combined with parallel factor analysis, this study analyzed three fluorescent components of soil leachate DOM: C1 (visible-light fulvic acid), C2 (humic acid), and C3 (tyrosine-like protein). The combined contribution of the two humic substance components (C1 + C2) was approximately 70%, indicating the dominance of humic substances in leachate DOM. The fluorescence parameters of soil leachate DOM included an average of the fluorescence index (FI) values between 1.4 and 1.9, low humification index (HIX) values consistently below 4, and biological index (BIX) values ranging from 0.8 to 1.0, suggesting a mixed source, low humification degree, poor stability, and moderate self-source characteristics. Compared with the non-green manure treatment control, both the green manure treatments exhibited a relatively higher proportion of biogenic sources and humification degree in soil leachate DOM. This suggests that planting green manure can reduce the relative DOM content under freshwater leaching conditions, increase the proportion of biogenic sources in soil leachate DOM, and enhance soil humification. Planting rapeseed green manure can diminish the leaching of DOM from land sources and augment soil humification.

Effects of bisphenols and perfluoroalkylated substances on fluorescence properties of humic and amino acids substances of dissolved organic matter: EEM-PARAFAC and ATR-FTIR analysis

Abiotic, biotic, and sparingly the xenobiotic factors are considered to influence the compositional variation of dissolved organic matter (DOM) in aquatic environments. Increasing discharge of xenobiotics into water bodies necessitates the need to investigate their effects on the key components of DOM. The effects of bisphenols (BP) and perfluoroalkylated substances (PFAS) on the fluorescence characteristics of pure humic substances (HS) and amino acids (AA) of DOM were examined by using excitation-emission matrix-parallel factor analysis (EEM-PARAFAC) and the attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy in this work. The results showed that interactions of fulvic acid (FA), humic acid (HA), and tryptophan (Trp) with the xenobiotic compounds could generate some fluorescence components like both HS and AA components, whereas the interactions with tyrosine (Tyr) could only generate AA fluorescence components. In addition, it was revealed that the fluorescence intensity of HS decreases by 50–70% and 18–25% in the treatments of HA and FA, respectively, at low concentration (2.5 × 10−3 mg/L) of BP, while this increases by 350–425% and 18–25% at the same concentration of PFAS. However, both BP and PFAS increase the fluorescence intensity of AA. The findings suggest that the xenobiotic compounds are important factors affecting the compositional variation of DOM, especially in the anthropogenically-impacted water bodies.

Response of electron transfer capacity of humic substances to soil microenvironment

The humic substances (HS) - mediated electron transfer process is of great significance to the reduction and degradation of pollutants and the improvement of soil quality. Different soil conditions lead to different characteristics of HS, resulting in differences in the electron transfer capacity (ETC) of HS. It is unclear how the environmental conditions in soil affect the ETC by affecting on HS. In this study, the response relationship of soil microenvironment, HS and ETC has been studied. The results show that the ETC follows the descending order of: Langshan > Nanchang > Anqing > Beijing > Guilin. There were significant differences in ETC in soil HS in different regions. There were significant differences in electron-donating capacity (EDC) in soil HS in different regions and depths. EDC in soil was higher than electron-accepting capacity (EAC), and on average, are 22.4 times higher than the EAC. The HS components of soils in different regions are different. The most significant differences were in tyrosine-like substances and soluble microbial by-products (SMPs). The five components of the soil HS from Langshan were the most different from those in other regions. There were differences in SMPs and humic-like substances in soils of different depths in Anqing and Guilin. ETC can be affected by the composition of HS components in different regions. The composition of HS at different soil depths in the same regions had little effect on ETC. SMPs can promote ETC and EDC, and tyrosine-like substance can promote EDC. Moisture content, pH and TOC are the main factors affecting the composition of HS components. This results can provide a research basis for the sustainable and safe utilization of agricultural soil.

Effects of Humic Substances on the Growth of Pseudomonas plecoglossicida 2,4-D and Wheat Plants Inoculated with This Strain.

Both rhizosphere bacteria and humic substances (HSs) can promote plant growth when applied individually and even greater effects of their combination have been demonstrated. We aimed to elucidate the relative importance of the stimulating effects of HSs on bacterial growth and the effects of the combination of bacteria and HSs on plants themselves. The effects of humic (HA) and fulvic acids (FA) (components of humic substances) on the growth of Pseudomonas plecoglossicida 2,4-D in vitro were studied. We also studied the effects of this bacterial strain and HSs applied individually or in combination on the growth of wheat plants. Although the 2,4-D strain showed low ability to use HSs as the sole source of nutrition, the bacterial growth rate was increased by FA and HA, when other nutrients were available. HSs increased root colonization with bacteria, the effect being greater in the case of HA. The effects on roots and shoots increased when bacteria were associated with HSs. FA+ 2,4-D was more effective in stimulating shoot growth, while HA + 2,4-D was in the case of root growth. The latter effect is likely to be beneficial under edaphic stresses.

Effect of ventilation quantity on electron transfer capacity and spectral characteristics of humic substances during sludge composting.

Humic substances (HSs) can ameliorate soil pollution by mediating electron transfer between microorganisms and contaminants. This capability depends on the redox-active functional structure and electron transfer capacity (ETC) of HS. This study mainly aimed to analyze the effects of different ventilation quantities on the ETC and spectral characteristics of HS (including humic acids (HAs) and fulvic acids (FAs)) during sludge composting. HS was extracted from compost with different ventilation quantities (0.1, 0.2, and 0.3 L kg-1 dry matter min-1, denoted as VQ1, VQ2, and VQ3, respectively). The ETC of HS was measured by electrochemical method. Excitation-emission matrix (EEM) spectroscopy, ultraviolet and visible (UV-Vis) spectrophotometry, and Fourier transform infrared (FT-IR) spectroscopy were conducted to understand the evolution of HS composition during composting. Results indicated that the ETC of HA and FA increased during composting, and VQ2 had stronger ETC and electron recycling rate than VQ1 and VQ3 at the end of composting. UV-Vis analysis revealed that the humification degree, aromatization degree, and molecular weight of HA and FA increased during composting, while the content of lignin decreased. EEM-PARAFAC results suggested that VQ2 accelerated the degradation of protein-like substances. FT-IR revealed a decrease trend in polysaccharide and aliphatic, and the carboxyl content increased in VQ2 and VQ3 while decreased in VQ1. Correlation analysis was used to study the relationship between HS components and ETC. The results advance our further understanding of the pollution remediation mechanism of HS.

Enhanced adsorption of humic/fulvic acids onto urea-derived graphitic carbon nitride

Since humic substances (HSs) can cause environmental problems, their elimination has been attracting more and more concerns. In this study, we investigated HSs adsorption onto urea-derived graphitic carbon nitride (CNU) and elucidated adsorption mechanisms (i.e. heterogeneity, interface rearrangement, and multiple interactions). The adsorption capacity of CNUs was enhanced as increasing calcination temperature and time. Among CNUs, CNU-575–3 showed the highest adsorption capacity; the maximum adsorption capacities for humic acid (HA) and fulvic acid (FA) were 164.06 mg C/g, 14.61 L/cm·g, 91.12 mg C/g, and 5.34 L/cm·g, respectively. The adsorption affinity of CNUs mainly correlated with the amount of amino groups, and that of HSs components was dependent on aromaticity due to π-π interactions. More specifically, terrestrial humic-like and fulvic-like components within HA and FA showed the greatest adsorption affinity, respectively. HSs adsorption was remarkably affected by pH, alkali metals, and alkali earth metals via electrostatic interactions, H-bonding, cation bridge, and configurational effect. In addition, the adsorption of Elliott soil HA (ESHA) and the landfill leachate concentrate by CNUs was also highly efficient. This study shows the great promise of CNUs for HSs adsorption in waters and wastewaters.

Temperature Dependences of IR Spectra of Humic Substances of Brown Coal

The capabilities of temperature-monitored IR spectroscopy for studying the organic matter and mineral composition of humic substances (HS) were tested. Temperature dependences of the mid-IR spectra of humic substances heated in the air in the range 25–215 °C (298–488 K, with a step of 2.5 °C)—for three commercially available samples isolated from brown coal (leonardite)—were performed. The characteristic bands were identified, and their changes in band maxima positions and intensities were compared. From the viewpoint of interpretation of HS components, the spectra were divided into regions of quartz lattice region (800–260 cm−1), quartz overtone region (1270–800 cm−1), humic substance organic matter region (1780–1270 cm−1), quartz combination region (2800–1780 cm−1), CH-speciation region (3100–2800 cm−1), and hydrogen-speciation region (4000–3100 cm−1) thus selected to contain the dominating type of bands. For the first time, a reversible change in the frequencies of the band maxima in IR spectra upon heating was observed, which can be interpreted as forming structures with a particular order in the studied humic substances in the dry state. For a single sample, both the band-shift scale and the functional dependence of the various bands on temperature differ significantly. The approach differentiates crystalline quartz bands, amorphous silica, and HSOM/surface groups experiencing a different temperature behavior of the band maxima and their intensities. Band-maximum temperature dependence can be considered more stable to changes in experimental conditions than band maxima at a single temperature, thus providing a more detailed HS structure analysis without HS decomposition or destruction.

Insights into Adsorption of Humic Substances on Graphitic Carbon Nitride.

Graphitic carbon nitride (CN) has been widely used in environmental pollution remediation. However, the adsorption of organic compounds on CNs, which has practical significance for the environmental application of CNs, is poorly understood. For the first time, this study systematically investigated the adsorption behaviors and mechanisms of humic substances (HSs), i.e., humic acid (HA) and fulvic acid (FA), on CNs derived from four typical precursors. Intriguingly, CN derived from urea (CN-U) showed a great capacity for HS adsorption due to its porous structure and large surface area, with maximum adsorption amounts of 73.24 and 51.62 mgC/g for HA and FA, respectively. The formation, influencing factors, and relative contributions of multiple interactions to HS adsorption on CNs were thoroughly elucidated. HS adsorption on CNs was mainly mediated by electrostatic interactions, π-π interactions, and H-bonding. The dominance of electrostatic interactions resulted in HS adsorption being highly dependent on pH and ionic strength. HS components with high aromaticity and high molecular weight were preferentially adsorbed due to π-π interactions. These multiple interactions were largely affected by amino groups and tri-s-triazine units of CNs, as well as the moieties of aromatic rings and oxygen-containing groups of HSs.

Which Traits of Humic Substances Are Investigated to Improve Their Agronomical Value?

Humic substances (HSs) are chromogenic organic assemblies that are widespread in the environment, including soils, oceans, rivers, and coal-related resources. HSs are known to directly and indirectly stimulate plants based on their versatile organic structures. Their beneficial activities have led to the rapid market growth of agronomical HSs. However, there are still several technical issues and concerns to be addressed to advance sustainable agronomical practices for HSs and allow growers to use HSs reliably. First, it is necessary to elucidate the evident structure (component)–function relationship of HSs. Specifically, the core structural features of HSs corresponding to crop species, treatment method (i.e., soil, foliar, or immersion applications), and soil type-dependent plant stimulatory actions as well as specific plant responses (e.g., root genesis and stress resistance) should be detailed to identify practical crop treatment methodologies. These trials must then be accompanied by means to upgrade crop marketability to help the growers. Second, structural differences of HSs depending on extraction sources should be compared to develop quality control and assurance measures for agronomical uses of HSs. In particular, coal-related HSs obtainable in bulk amounts for large farmland applications should be structurally and functionally distinguishable from other natural HSs. The diversity of organic structures and components in coal-based HSs must thus be examined thoroughly to provide practical information to growers. Overall, there is a consensus amongst researchers that HSs have the potential to enhance soil quality and crop productivity, but appropriate research directions should be explored for growers’ needs and farmland applications.

Involvement of laccase-like enzymes in humic substance degradation by diverse polar soil bacteria.

Humic substances (HS) in soil are widely distributed in cold environments and account for a significant fraction of soil's organic carbon. Bacterial strains (n=281) were isolated at 15°C using medium containing humic acids (HA), a principal component of HS, from a variety of polar soil samples: 217 from the Antarctic and 64 from the Arctic. We identified 73 potential HA-degrading bacteria based on 16S rRNA sequence similarity, and these sequences were affiliated with phyla Proteobacteria (73.9%), Actinobacteria (20.5%), and Bacteroidetes (5.5%). HA-degrading strains were further classified into the genera Pseudomonas (51 strains), Rhodococcus (10 strains), or others (12 strains). Most strains degraded HA between 10 and 25°C, but not above 30°C, indicating cold-adapted degradation. Thirty unique laccase-like multicopper oxidase (LMCO) gene fragments were PCR-amplified from 71% of the 73 HA-degrading bacterial strains, all of which included conserved copper-binding regions (CBR) I and II, both essential for laccase activity. Bacterial LMCO sequences differed from known fungal laccases; for example, a cysteine residue between CBR I and CBR II in fungal laccases was not detected in bacterial LMCOs. This suggests a bacterial biomarker role for LMCO to predict changes in HS-degradation rates in tundra regions as global climate changes. Computer-aided molecular modeling showed these LMCOs contain a highly-conserved copper-dependent active site formed by three histidine residues between CBR I and CBR II. Phylogenetic- and modeling-based methods confirmed the wide occurrence of LMCO genes in HA-degrading polar soil bacteria and linked their putative gene functions with initial HS-degradation processes.

Multi-proxy approach involving ultrahigh resolution mass spectrometry and self-organising maps to investigate the origin and quality of sedimentary organic matter across a subtropical reservoir

Humic substances (HS) in sediments play an important role in carbon and nutrient biogeochemical cycles and fate of contaminants in the environment. However, information regarding HS quality and transformations that may affect their behaviour in reservoirs is still limited. The aim of this investigation was to track sources and changes in sedimentary HS across a subtropical reservoir, connecting them to in-lake processes and land-use influences. Surface sediments were collected at seven sampling sites in Itupararanga Reservoir (Brazil). Humic (HA) and fulvic (FA) acids (components of HS) were extracted from the sediment samples followed by in-depth characterisation via UV/VIS, fluorescence spectroscopy, elemental (C, N) and isotopic analysis (δ13C, δ15N), nuclear magnetic resonance (13CNMR) and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). All data were analysed by self-organising maps. The results showed that samples from the upstream part of the reservoir were older and more decomposed. They likely originated from C3 land-plants (δ13C varied from −26.3‰ to −22.4‰), having more aromatic, oxygen-poor (O/C < 0.5) and unsaturated compounds (H/C < 1.1). In contrast, near-dam samples were younger and had larger contributions of autochthonous material. This was confirmed by oxygen-rich (O/C > 0.5) and partly more unsaturated compounds for FA as well as oxygen-poor and saturated compounds with H/C > 1.1 for HA. Self-organising maps pointed out these differences between upstream and dam areas and indicated that agriculture lands were related to microbially-derived HS. Changes in HS composition revealed that internal reservoir processes may have influenced HS quality across the reservoir.

Bioactivity of Size-Fractionated and Unfractionated Humic Substances From Two Forest Soils and Comparative Effects on N and S Metabolism, Nutrition, and Root Anatomy of Allium sativum L.

Humic substances (HS) are powerful natural plant biostimulants. However, there is still a lack of knowledge about the relationship between their structure and bioactivity in plants. We extracted HS (THE1-2) from two forest soils covered with Pinus mugo (1) or Pinus sylvestris (2). The extracts were subjected to weak acid treatment to produce size-fractionated HS (high molecular size, HMS1-2; low molecular size, LMS1-2). HS were characterized for total acidity, functional groups, element and auxin (IAA) contents, and hormone-like activity. HS concentrations ranging from 0 to 5 mg C L−1 were applied to garlic (Allium sativum L.) plantlets in hydroponics to ascertain differences between unfractionated and size-fractionated HS in the capacity to promote mineral nutrition, root growth and cell differentiation, activity of enzymes related to plant development (invertase, peroxidase, and esterase), and N (nitrate reductase, glutamine synthetase) and S (O-acetylserine sulphydrylase) assimilation into amino acids. A positive linear dose-response relationship was determined for all HS in the range 0–1 mg C L−1, while higher HS doses were less effective or ineffective in promoting physiological-biochemical attributes of garlic. Bioactivity was higher for size-fractionated HS according to the trend LMS1-2>HMS1-2>THE1-2, with LMS2 and HMS2 being overall more bioactive than LMS1 and HMS1, respectively. LMS1-2 contained more N, oxygenated functional groups and IAA compared to THE1-2 and HMS1-2. Also, they exhibited higher hormone-like activities. Such chemical properties likely accounted for the greater biostimulant action of LMS1-2. Beside plant growth, nutrition and N metabolism, HS stimulated S assimilation by promoting the enrichment of garlic plantlets with the S amino acid alliin, which has recognized beneficial properties in human health. Concluding, this study endorses that i) treating THE with a weak acid produced sized-fractionated HS with higher bioactivity and differing in properties, perhaps because of novel molecular arrangements of HS components that better interacted with garlic roots; ii) LMS from forest soils covered with P. mugo or P. sylvestris were the most bioactive; iii) the cover vegetation affected HS bioactivity iv); HS stimulated N and S metabolism with relevant benefits to crop nutritional quality.

The effect of organic matter humification (aromaticity and oxidation degree) on structural and nanomorphological characteristics of humic nanocomposites of metallic platinum

BackgroundIt has been previously found that humic substances (HSs) can serve as the environmentally benign non-toxic agent for the preparation of magnetic and noble metals nanoparticles that are increasingly used in biomedicine. The structure of HSs and, hence, their synthetic potential depend on the source of their origin. Thus, humification character, determined by conditions and duration of complex transformation of organic remains in HSs can evidence their structure, in particular their aromaticity and oxidation degree. The incorporation of platinum nanoparticles in a shell of HSs allows obtaining aggregate-stable nanomaterials with directly controlled structural and nanomorphological characteristics, which combine the properties of platinum nanoparticles (selective cytotoxicity, anti-inflammatory activity, etc. And a complex of biological properties of HSs (antioxidant, immunomodulatory and anti-inflammatory activity. At the same time, the expression of valuable properties of platinum nanoparticles can be varied directly by changing their nanomorphological characteristics that strongly depend on the conditions of synthesis, in particular on the HSs type which is used for the synthesis. AimTo study the effect of humification (aromaticity and oxidation degree) of three types of humic substances extracted from natural Mongolia sources (therapeutic muds of Gurvan Nuur Lake, brown coal of Baganuur coal deposit and shale of Shine Hudag deposit) on structural and nanomorphological characteristics of Pt0-containing nanocomposites produced on their basis. MethodsNanocomposites with Pt0 content 1.2–6.5% were synthesized by reduction of hydrogen hexachloroplatinate with HSs in an aqueous-alkaline medium upon heating (90 °C). The yield of nanocomposites varied depending on type of HSs in the range 75–96%. The structure, composition and morphology of obtained nanocomposites were characterized by complex of modern physical and chemical methods (elemental analysis, XRD, SEM, TEM, IR- and optical-spectroscopy, DLS). ResultsThe platinum-containing nanocomposites have been synthesized using the reduction and stabilizing potentials of HSs with different degrees of humification (aromaticity and oxidation degree) and isolated from three natural Mongolian sources. The effect of functional composition, including oxidation and aromaticity degrees of HSs on the yield, quantitative and nanomorphological characteristics of produced platinum nanocomposites has been found. It is established that under the same reaction conditions platinum nanoparticles with face-centered cubic lattice and the smallest average size (9–15 nm) are formed from humic substances extracted from coal, while HSs derived from mud and shale afford the nanoparticles of larger size (18–28 and 16–26 nm respectively). The increase of platinum content in nanocomposites enlarges their average size, decreases their aggregate stability, as well as augments oxidation degree of HSs macromolecules. The reduction of platinum from precursor to the zero-valent state occurs due to oxidation of the phenolic and alcoholic hydroxyl groups, which are major components of HSs, as well as carbonyl groups. At the same time, HSs cover individual platinum nanoparticles, making them water soluble and preventing their aggregation. ConclusionThus, we have synthesized a series Pt0-containing nanocomposites containing 1.2–6.5% with use as reducing and stabilizing matrix of natural available HSs with different humification characteristics (aromaticity and oxidation degree) and isolated from three natural Mongolia sources It is found that obtained nanocomposites are formed in form of platinum nanoparticles mainly of spherical shape and size of 3–42 nm distributed in a matrix of HSs. Polyfunctional composition of HSs is determined by conditions of their transformation and degree of humification, which provides their reducing and stabilizing properties during the synthesis of platinum metallic nanocomposites. It is established that Pt0 nanoparticles with the smallest average size and the highest aggregate stability are generated from HSs-coal with the lowest oxidation degree. These data contribute significantly to understanding of possible control of the nanomaterials synthesis and prediction of their properties.

Effects of mercury binding by humic acid and humic acid resistance on mercury stress in rice plants under high Hg/humic acid concentration ratios.

Due to the nonsystematic nature of previous studies on mercury (Hg) mobility with humic substances (HS) in terrestrial ecosystems and the uncertainty of Hg accumulation in plants, oxygen-rich humic acid (HA), which is the main component of HS, was used as the target in this study. Batch sorption tests and a series of pot experiments were designed to investigate the effect of HS on Hg binding and therefore Hg uptake in rice plants under extreme conditions, i.e., a high Hg/HS concentration ratio. The results showed that HA was eligible for Hg binding, though it has a tiny proportion of sulfur according to its characteristics analysis. The binding of HA and Hg was a chemisorption process in a single layer that followed the pseudo-second order and Langmuir models, and it was also verified that the pH was dependent on the ion strength associated with high Hg/HA concentration ratios. Based on the pot experiments, the performance of HA with Hg was investigated. The Hg in the toxicity characteristic leaching procedure (TCLP) leachate under high Hg/HA concentration ratios declined significantly, and accordingly, all treatments met the concentration criteria of 0.1mg/l (GB 5085.3-2007) for wastes after 30days of exposure. At concentration ratios of 50, 25, and 10μgHg/mg HA, we observed that HA application promoted rice plant growth, as reflected in the increase of fresh weight of different organs. Regarding accumulation in the soil-plant system, the degradation of HA to smaller molecules by rhizosphere microorganisms and organic acids in roots made HA available for plant uptake through the vascular bundle in roots, thus promoting Hg transformation in plants to a certain extent. However, considering the decline in available Hg in the soil, the Hg concentrations of roots, straw, and grains in the ripening stage were found to be lower than those in the standalone Hg treatments. HA clearly has a direct effect on Hg and an indirect influence on plants exposed to Hg under extreme conditions (very high Hg/HA concentration ratios); thus, the biogeochemical behavior of Hg at high Hg/HA concentration ratios should be considered and further investigated.

Dissolved Organic Matter and Associated Trace Metal Dynamics from River to Lake, Under Ice-Covered and Ice-Free Conditions.

The present study investigates the changes in dissolved organic matter (DOM) composition and its influences on trace metal dispersion from the Shuya River (SR) in the Petrozavodsk Bay of Lake Onega during ice-covered and ice-free periods. Humic substances (HS) found in the SR dominated the composition of DOM through the river-bay-lake continuum in both periods. When the bay was ice-covered, both the aromaticity and the size of HS varied in the water column according to a horizontal stratification and decreased in the bay, while under ice-free conditions, they decreased along the river-lake gradient, suggesting in both cases a decrease in the proportion of HS with high aromatic character. These findings were associated with an overall decrease in the proportion of HS components that have the highest molecular masses. The quantification of metal bound to HS revealed that these characteristics were associated with a decrease in the binding capacity of the HS for Fe and Al but not Cu while dispersing in the bay to the lake. Pb was found to bind on HS, but its behavior in the bay could not be related to the HS dispersion nor to the changes in HS properties.

Examination of molecular space and feasible structures of bioactive components of humic substances by FTICR MS data mining in ChEMBL database

Humic substances (HS) are complex natural mixtures comprising a large variety of compounds produced during decomposition of decaying biomass. The molecular composition of HS is extremely diverse as it was demonstrated with the use of high resolution mass spectrometry. The building blocks of HS are mostly represented by plant-derived biomolecules (lignins, lipids, tannins, carbohydrates, etc.). As a result, HS show a wide spectrum of biological activity. Despite that, HS remain a ‘biological activity black-box’ due to unknown structures of constituents responsible for the interaction with molecular targets. In this study, we investigated the antiviral activity of eight HS fractions isolated from peat and coal, as well as of two synthetic humic-like materials. We determined molecular compositions of the corresponding samples using ultra-high resolution Fourier-transform ion cyclotron resonance mass-spectrometry (FTICR MS). Inhibitory activity of HS was studied with respect to reproduction of tick-borne encephalitis virus (TBEV), which is a representative of Flavivirus genus, and to a panel of enteroviruses (EVs). The samples of natural HS inhibited TBEV reproduction already at a concentration of 1 µg/mL, but they did not inhibit reproduction of EVs. We found that the total relative intensity of FTICR MS formulae within elemental composition range commonly attributed to flavonoid-like structures is correlating with the activity of the samples. In order to surmise on possible active structural components of HS, we mined formulae within FTICR MS assignments in the ChEMBL database. Out of 6502 formulae within FTICR MS assignments, 3852 were found in ChEMBL. There were more than 71 thousand compounds related to these formulae in ChEMBL. To support chemical relevance of these compounds to natural HS we applied the previously developed approach of selective isotopic exchange coupled to FTICR MS to obtain structural information on the individual components of HS. This enabled to propose compounds from ChEMBL, which corroborated the labeling data. The obtained results provide the first insight onto the possible structures, which comprise antiviral components of HS and, respectively, can be used for further disclosure of antiviral activity mechanism of HS.

Effects of aeration rates on the structural changes in humic substance during co-composting of digestates and chicken manure

High humidity and potential threat of pathogen of anaerobic digestates are unfavorable to the environment by direct utilization. To achieve the sustainable utilization of digestates, composting might be a good choice. Meanwhile, the aeration rate of composting has been optimized. Co-composting of digestates and chicken manure was performed under different aeration conditions (0.05, 0.1 and 0.15 L·min−1·kg−1·organic matter (OM)). During composting, internal transformation of humic substance (HS) has been studied for obtaining the potential application value of the co-composting products. Results suggested that the HS concentration was increased by 21.1%, 26.4% and 22.4% with the aeration rates were 0.05, 0.1 and 0.15 L·min−1·kg−1·OM, respectively. The aeration rate of 0.15 L·min−1·kg−1·OM was more conducive to germination. Parallel factor analysis and dimensional correlation spectra (2DCOS) have been combined to reveal the conversion relationships of HS components for understanding the compost application pattern. Hetero-2DCOS indicated that aeration of 0.05 min−1·kg−1·OM and 0.1 L·min−1·kg−1·OM contributed to the formation of complex compounds at long wavelength, and aeration of 0.15 L·min−1·kg−1·OM was beneficial for labile compounds formation at short wavelength. In views of the aeration of 0.1 L·min−1·kg−1·OM was more beneficial to improve HS concentration than 0.05 L·min−1·kg−1·OM, 0.1 L·min−1·kg−1·OM and 0.15 L·min−1·kg−1·OM were consider as the most important aeration rate to conduct digestates composting. Overall, the aeration affected the HS composition which, in turn, might affect the application ways of composting products. This study could provide a reference for industrial composting production and applications.

Remediation of Cd(II)-contaminated soil via humin-enhanced electrokinetic technology.

Humin is the component of humic substances that is recalcitrant to extraction by either strong bases or strong acids, which contains a variety of functional groups that may combine with heavy metal ions. The present study employed humin as an adsorbent to investigate the efficacy of a remediation strategy under the effects of humin-enhanced electrokinetics. Because the cations gravitate toward cathode and anions are transferred to anode, humin was placed in close proximity to the cathode in the form of a package. The humin was taken out after the experiments to determine whether a target pollutant (cadmium) might be completely removed from soil. Acetic acid-sodium acetate was selected as the electrolyte for these experiments, which was circulated between the two electrode chambers via a peristaltic pump, in order to control the pH of the soil. The results indicated that when the remediation duration was extended to 240h, the removal of acid extractable Cd(II) could be up to 43.86% efficiency, and the adsorption of the heavy metal within the humin was 86.15mg/kg. Further, the recycling of the electrolyte exhibited a good control of the pH of the soil. When comparing the pH of the soil with the circulating electrolyte during remediation, in contrast to when it was not being recycled, the pH of the soil at the anode increased from 3.89 to 5.63, whereas the soil at the cathode decreased from 8.06 to 7.10. This indicated that the electrolyte recycling had the capacity to stabilize the pH of the soil.

Moisture effect on soil humus characteristics in a laboratory incubation experiment

Li C., Gao S., Zhang J., Zhao L., Wang L. (2016): Moisture effect on soil humus characteristics in a laboratory incuba tion experiment. Soil & Water Res., 11: 37–43. A 180-day laboratory incubation experiment (30°C) was conducted to investigate the quantitative and qualitative characteristics of humic fractions in a Mollisol at different moisture conditions. The soil moisture contents were 30, 60, and 250% field water-holding capacity (WHC), which represented the low, middle, and high moisture levels, respectively. The results showed that the carbon contents of the total soil and corresponding humic fractions gener ally decreased with increasing soil moisture. A significant difference was observed between the 250% WHC and the two other moisture levels. By contrast, the carbon content of the water soluble fraction significantly increased with increasing soil moisture levels. The solid-state 13 C nuclear magnetic resonance (NMR) spectra showed that the alkyl C/O-alkyl C, aliphatic C/aromatic C, and hydrophobic C/hydrophilic C ratios were in the order of 250% WHC > 30% WHC ≈ 60% WHC, 30% WHC ≈ 60% WHC > 250% WHC and 250% WHC > 60% WHC ≈ 30% WHC for humic acid, and 250% WHC > 30% WHC ≈ 60% WHC, 60% WHC ≈ 250 % WHC > 30% WHC and 30% WHC ≈ 250% WHC > 60% WHC for humin, respectively. These results indicated that a high moisture level was unfavourable for the carbon accumulation of the total soil and humic fractions, whereas it was favourable for the accumulation of water soluble carbon. Although soil moisture levels had a distinct effect on the chemical composition of humic acid and humin, the decomposition degree of the two humic substances components, as indicated by the alkyl C/ O-alkyl C ratio, were both higher at a high moisture level than at a low moisture level. Therefore, the lower soil organic carbon content at a high moisture level than at a low moisture level can be ascribed to the higher water soluble carbon content and larger decomposition degree of humic acid and humin in the former. Our results are important for understanding the behaviour and mechanisms of humic substances at specific soil moisture conditions.

The effects of fulvic acid on microbial denitrification: promotion of NADH generation, electron transfer, and consumption.

The heterotrophic denitrification requires the participation of electrons which are derived from direct electron donor (usually nicotinamide adenine dinucleotide (NADH)), and the electrons are transferred via electron transport system in denitrifiers and then consumed by denitrifying enzymes. Despite the reported electron transfer ability of humic substances (HS), the influences of fulvic acid (FA), an ubiquitous major component of HS, on promoting NADH generation, electron transfer, and consumption in denitrification process have never been reported. The presence of FA, compared with the control, was found not only significantly improved the total nitrogen (TN) removal efficiency (99.9% versus 74.8%) but remarkably reduced the nitrite accumulation (0.2 against 43.8mg/L) and N2O emission (0.003 against 0.240mg nitrogen/mg TN removed). The mechanisms study showed that FA increased the metabolism of carbon source via glycolysis and tricarboxylic acid (TCA) cycle pathways to produce more available NADH. FA also facilitated the electron transfer activities from NADH to denitrifying enzymes via complex I and complex III in electron transport system, which improved the reduction of nitrate and accelerated the transformations of nitrite and N2O, and lower nitrite and N2O accumulations were therefore observed. In addition, the consumption of electrons in denitrification was enhanced due to FA stimulating the synthesis and the catalytic activity of key denitrifying enzymes, especially nitrite reductase and N2O reductase. It will provide an important new insight into the potential effect of FA on microbial denitrification metabolism process and even nitrogen cycle in nature niches.