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Advances in water chemistry in the last decade have improved our knowledge about the genesis, composition, and structure of dissolved organic matter, and its effect on the environment. Improvements in analytical technology, for example Fourier-transform ion cyclotron (FT-ICR) mass spectrometry (MS), homo and hetero-correlated multidimensional nuclear magnetic resonance (NMR) spectroscopy, and excitation emission matrix fluorimetry (EEMF) with parallel factor (PARAFAC) analysis for UV–fluorescence spectroscopy have resulted in these advances. Improved purification methods, for example ultrafiltration and reverse osmosis, have enabled facile desalting and concentration of freshly collected DOM samples, thereby complementing the analytical process. Although its molecular weight (MW) remains undefined, DOM is described as a complex mixture of low-MW substances and larger-MW biomolecules, for example proteins, polysaccharides, and exocellular macromolecules. There is a general consensus that marine DOM originates from terrestrial and marine sources. A combination of diagenetic and microbial processes contributes to its origin, resulting in refractory organic matter which acts as carbon sink in the ocean. Ocean DOM is derived partially from humified products of plants decay dissolved in fresh water and transported to the ocean, and partially from proteinaceous and polysaccharide material from phytoplankton metabolism, which undergoes in-situ microbial processes, becoming refractory. Some of the DOM interacts with radiation and is, therefore, defined as chromophoric DOM (CDOM). CDOM is classified as terrestrial, marine, anthropogenic, or mixed, depending on its origin. Terrestrial CDOM reaches the oceans via estuaries, whereas autochthonous CDOM is formed in sea water by microbial activity; anthropogenic CDOM is a result of human activity. CDOM also affects the quality of water, by shielding it from solar radiation, and constitutes a carbon sink pool. Evidence in support of the hypothesis that part of marine DOM is of terrestrial origin, being the result of a long-term carbon sedimentation, has been obtained from several studies discussed herein.

The soil health notion has been recently expanded to relate soil functions not only to soil fertility for a sustainable primary productivity, but also to the control of water cycling and of the soil carbon storage. Soil humus is fundamental to achieve the objectives of soil health, and it is therefore deemed necessary to enlarge the knowledge of its composition and dynamics, if a modern soil management was to be pursued. This review first describes the contemporary understanding of the supramolecular structure of soil humus and the derived modern method to identify the totality of humic components to an unprecedented extent in soils under different soil management and cropping systems. Then, it accounts on how humus, either native in soil or exogenous from sources rich in organic carbon such as lignite, compost, and lignocellulosic residues, improves the soil physical fertility, limits the risk of erosion, enhances the bioactivity of the rhizosphere microbiome, and directly stimulates plant growth. Moreover, it is highlighted the role played by humus in ecologically sound soil managements, such as in organic and biodynamic agricultural productions, which are progressively growing as alternative to conventional but environmentally unsafe practices. Graphical Abstract

Long-term exposure to air pollution has been associated with the development of some inflammatory processes related to skin. The goal of modern medicine is the development of new products with antiflammatory action deriving from natural sources to improve environmental and economic sustainability. In this study, two different humic acids (HA) were isolated from from lignite (HA-LIG) and composted artichoke wastes (HA-CYN) and characterized by infrared spectrometry, NMR spectroscopy, thermochemolysis-GC/MS, and high-performance size-exclusion chromatography (HPSEC), while their antiflammatory activity was evaluated on HaCaT cells. Spectroscopic results showing the predominance of apolar aliphatic and aromatic components in HA-LIG, whereas HA-CYN revealed a presence of polysaccharides and polyphenolic lignin residues. The HA application on human keratinocyte pre-treated with Urban Dust revealed a general increase of viability suggesting a protective effect of humic matter due to the content of aromatic, phenolic and lignin components. Conversely, the gene expression of IL-6 and IL-1β cytokines indicated a significant decrease after application of HA-LIG, thus exhibiting a greater antiflammatory power than HA-CYN. The specific combination of HA protective hydrophobic components, viable conformational arrangements, and content of bioactive molecules, suggests an innovative applicability of humic matter in dermatology as skin protectors from environmental irritants and as antiflammatory agents.

BackgroundThe Essential oils (EOs) are important bioactive secondary metabolites of aromatic plants, such as Basil, and find extensive utilization in pharmaceutical sector as therapeutic agents. A more eco-friendly industrial production of EOs requires new sustainable methods to improve yield and quality of these bioactive compounds in aromatic plants. Here, we evaluated the biostimulation effects of natural organic materials, such as humic substances (HS) extracted from a humified green compost made with artichoke biomasses.ResultsThe molecular characteristics of HS from green compost were determined by 13C-CPMAS NMR spectroscopy and offline pyrolysis–gas chromatography/mass spectrometry and combined to the bioactivity of the EOs extracts to investigate the structural–activity relationship. Basil plants were grown under HS treatments at different concentrations and the yield, the chemical composition and the antioxidant and antimicrobial properties were determined for EOs extracted by steam distillation method from Basil leaves. HS showed a positive effect on total extraction yield of the most bioactive EO components, with a progressive enhancement of abundance for eugenol, eucalyptol and geranyl acetate with increasing HS concentrations. Humic biostimulation influenced the EOs antioxidant proprieties, as well as their antimicrobial activity against some common Gram-negative bacterial strains such as Klebsiella pneumoniae. The HS biostimulation of Basil plants was associated to their structural hydrophobic characteristics that may have favoured the interactions with the Basil rhizome and to specific bioactive molecular components, such as a lignin-derived phenols and polar saccharidic and aminoacidic compounds.ConclusionsOur results support the potential use of humic substances from green compost as promising effective biostimulants to improve the production and bioactive properties of EOs in aromatic plants.Graphic Abstract

BackgroundGlobal market of humic substances has been increasing steadily based on the perception of the multifunctional properties as plant biostimulant, microbial vehicle and plant protective agent against environmental stress. Some field assays and many experimental observations have shown that humic matter could relieve the abiotic stress effects. Here, we explored the plant chemical priming effect concept, i.e., plant preconditioning by prior exposure to an appropriate dose of humic acids with the objective to reduce toxicity from a subsequent harmful exposure to abiotic stressor, such as salinity, drought, heavy metals and humic acids themselves.Materials and methodsThe prime state (PS) was characterized using traditional stress markers like proline content and catalase activity was well as the transcription level of mRNA of phytohormones-responsive genes, cell signaling, stress-responsive genes and transcription factors. A dose–response curve was built for stressor agents since maize seedlings in the PS were submitted to salinity, drought, chromium toxicity and humic acids concentration to reduce 50% of root fresh weight with respect to control plants.ResultsThe PS or adaptive response by biostimulation of humic substances was described at transcriptional level, where the hormonal signaling pathways including abscisic acid, gibberellic and auxins, specific abiotic functional and regulatory stress-responsive genes were positively modulated. The negative impact of stressor agents was alleviated in the maize seedlings primed by humic acids.ConclusionChemical priming by humic substances is a promising field tool in plant stress physiology and crop stress management.

We evaluated the effectiveness of natural organic surfactants such as humic acids (HA) from lignite to simultaneously wash heavy metals (HM) and polychlorobiphenyls (PCB) from a heavily contaminated industrial soil of northern Italy. Supramolecular HA promote in solution a micelle-like structure, where recalcitrant apolar organic xenobiotics are repartitioned from surfaces of soil particles during soil washing process. Concomitantly, the HA acidic functional groups enable a simultaneous complexation of HM. A single soil washing with HA removed 68 and 75% of PCB congeners for 1:1 and 10:1 solution/soil ratios, respectively. The same HA washing simultaneously and efficiently removed a cumulative average of 47% of total HM, with a maximum of 57 and 67% for Hg and Cu, respectively. We showed that washing a highly polluted soil with HA solution not only is an effective and rapid soil remediation technique but also simultaneously removes both HM and persistent organic pollutants (POP). Soil washing by humic biosurfactants is also a sustainable and eco-friendly technology, since, contrary to synthetic surfactants and solvents used in conventional washing techniques, it preserves soil biodiversity, promotes natural attenuation of unextracted POP, and accelerates further soil reclamation techniques such as bio- or phytoremediation.

BackgroundThe reliance on chemical inputs to support high yields is the Achilles’ heel of modern crop production. The soil organic matter management is as old as agriculture itself. Recently, the use of soluble humic substances as plant growth promoters has been brought to attention due to their effects on nutrient uptake and water use efficiency. Humic substances applied directly at low concentrations can trigger different molecular, biochemical, and physiological processes in plants. However, how humic substances exert this plethoric regulatory action remains unclear. The objective of this study was to evaluate changes in the transcription level of genes coding cell receptors, phosphatases, synthesis, and function of different plant hormones and transcription factors.Materials and methodsAfter seven days of humic acid treatment, we used RNAseq in maize root seedlings. The level of gene transcription was compared with control plants.ResultsPlant kinase receptors and different phosphatases were regulated by humic acids. Likewise, genes related to plant hormones (auxin, gibberellin, ethylene, cytokinin, abscisic acid, brassinosteroids, jasmonic and salicylic acids) were transcript in differential levels in maize root seedlings as well as the expression of a hundred of transcription factors modifying the signal transduction pathway via alterations of the subsequent gene response.ConclusionWe showed a general mechanism for simultaneously regulating the activity of several hormones where humic acids act as a key regulatory hub in plant responses integrating hormonal signalling and response pathways.

Background and aimsNeutralization of adverse environmental effects of agriculture intensification to sustain population growth, requires ecologically sound alternatives for plant growth. We used as biostimulants towards germination of basil seeds and early growth of maize, two different humic materials: a potassium humate from leonardite (KH), and compost tea (CT) from a green compost made of coffee husks, and a 1:1 combination of the two (MIX). After their thorough chemical, molecular and conformational characterization, a relation between structure and bioactivity was investigated.ResultsCT showed the largest bioactivity on either seed germination or maize plantlets growth due to its great content of polar bioactive molecules including oxidized lignin fragment, saccharides and peptides. The more hydrophobic KH, rich of alkyl and aromatic moieties, also exerted a significant bioactivity on maize, though to a lesser extent. The application of MIX to hydroponically grown maize plantlets showed a smaller bioactivity of polar CT molecules due to their entrapment into new suprastructures stabilized by hydrogen bonds formed with complementary functions of KH hydrophobic components. However, while the KH hydrophobicity in MIX ensured adhesion to roots, its conformational flexibility was still sufficient to provide a greater bioactivity than control, by releasing bioactive CT components capable to enhance both biomass yield and root elongation.ConclusionsOur study suggests that a combination of humic materials with diverse and well-characterized molecular properties may become a new tool to produce innovative and ecologically viable plant growth promoters, whose bioactivity may be modulated.

Compost amendment to agricultural soils influences plant growth and soil quality by affecting activity of arbuscular mycorrhizal fungi (AMF) and composition of microbial community. We related the molecular composition of compost of different maturity added to soils to their effects on maize growth, N and P uptake, AMF root colonization and growth, and composition of soil microbial community. The characteristics of compost after different days of maturation (C60, C90, C120) were provided by 13 C-solid state NMR spectroscopy, while neutral (NLFA) and phospholipid (PLFA) fatty acid analyses were used to evaluate the effects of compost on the composition of soil microbial communities. Multivariate elaboration was used to determine the relationships between microbial groups, as identified by PLFA analysis, and molecular properties of composts. Although compost amendments increased soil total C and N, and available P, soil addition of both C60 and C120 compost samples was detrimental to plant and AMF growth. Compost amendments modified the composition of soil microbial communities. The high content of biolabile compounds in C60 and C120 compost samples decreased the C16:1ω5 NLFA that was related to AMF and Gram(+)/Gram(−) and AMF/saprotrophic fungi ratios. A linear correlation was found between the molecular indexes in compost and the microbial groups in soil, thereby suggesting that the molecular composition of compost strictly controls the development and abundance of soil microbial communities. These findings highlight the importance of controlling the molecular quality of recycled biomass added to soil, in order to predict the effect on crop yields and biotic composition of soil.

Humic-like substances (HLSs) isolated by alkaline oxidative hydrolysis from lignin-rich agro-industrial residues have been shown to exert biostimulant activity toward maize ( Zea mays L.) germination and early growth. The definition of a quantitative structure-activity relationship (QSAR) between HLS and their bioactivity could be useful to predict their biological properties and tailor plant biostimulants for specific agronomic and industrial uses. Here, we created several projection on latent structure (PLS) regression by using published analytical data on the molecular composition of lignin-derived HLS obtained by both 13C-CPMAS-NMR spectra directly on samples and 31P-NMR spectra after derivatization of hydroxyl functions with a P-containing reagent (2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane). These spectral data were used to model the effect of HLS on the elongation of primary root, lateral seminal roots, total root apparatus, and coleoptile of maize. The 13C-CPMAS-NMR data suggested that methoxyl and aromatic moieties positively affected plant growth, while the carboxyl/esterified functions showed a negative impact on the overall seedling development. Alkyl C seems to promote Col elongation while concomitantly reducing that of the root system. Additionally, 31P-NMR-derived spectra revealed that the elongation of roots and Col were enhanced by the occurrence of aliphatic hydroxyl groups, and guaiacyl and p -Hydroxyphenyl lignin monomers. The PLS models based on raw dataset from 13C-CPMAS-NMR spectra explained more than 74% of the variance for the length of lateral seminal roots, total root system and coleoptile, while other parameters derived from 13C-CPMAS-NMR spectra, namely the Hydrophobicity and Hydrophilicity of materials were necessary to explain 83% of the variance of the primary root length. The results from 31P-NMR spectra explained the observed biological variance by 90, 96, 96, and 93% for the length of primary root, lateral seminal roots, total root system and coleoptile, respectively. This work shows that different NMR spectroscopy techniques can be used to build up PLS models which can predict the bioactivity of lignin-derived HLS toward early growth of maize plants. The established QSAR may also be exploited to enhance by chemical techniques the bioactive properties of HLS and enhance their plant stimulation capacity.