Seasonal studies of aquatic humic substances from Amazon rivers: characterization and interaction with Cu (II), Fe (II), and Al (III) using EEM-PARAFAC and 2D FTIR correlation analyses.

Aquatic humic substances (AHS) are defined as an important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (KML ranged from 0.3 to 7.9 × 105) than C2 (KML ranged from 3.1 to 10.0 × 105). 2D-COS FTIR showed that the COO- and C-O in phenolic were the most important functional groups for interaction with studied metallic ions.

Waste to Wealth Approach: Improved Antimicrobial Properties in Bioactive Hydrogels through Humic Substance-Gelatin Chemical Conjugation.

Exploring opportunities for biowaste valorization, herein, humic substances (HS) were combined with gelatin, a hydrophilic biocompatible and bioavailable polymer, to obtain 3D hydrogels. Hybrid gels (Gel HS) were prepared at different HS contents, exploiting physical or chemical cross-linking, through 1-ethyl-(3-3-dimethylaminopropyl)carbodiimide (EDC) chemistry, between HS and gelatin. Physicochemical features were assessed through rheological measurements, X-ray diffraction, attenuated total reflectance (ATR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and scanning electron microscopy (SEM). ATR and NMR spectroscopies suggested the formation of an amide bond between HS and Gel via EDC chemistry. In addition, antioxidant and antimicrobial features toward both Gram(-) and Gram(+) strains were evaluated. HS confers great antioxidant and widespread antibiotic performance to the whole gel. Furthermore, the chemical cross-linking affects the viscoelastic behavior, crystalline structures, water uptake, and functional performance and produces a marked improvement of biocide action.

Hydrochar obtained with by-products from the sugarcane industry: Molecular features and effects of extracts on maize seed germination.

Sugarcane bagasse, vinasse and a mixture of sugarcane bagasse and vinasse were hydrothermally carbonized (HTC), with and without the addition of phosphoric acid, in order to propose new applications of sucroenergetic industry by-products on soil. Detailed information on the composition and properties of hydrochars has been obtained through elemental composition, thermogravimetric analysis, nuclear magnetic resonance and, thermochemolysis GC-MS. The soluble acidic fraction from the hydrochar samples were applied to maize seeds to evaluate the agronomic potential as biostimulants and relate the molecular features with maize seed germination. The HTC treatment converted polysaccharide-based biomasses into hydrochars with hydrophobic characteristics (C-Aryl and C-Akyl). Furthermore, the addition of phosphoric acid further increased the overall hydrophobicity and shifted the thermal degradation of the hydrochars to higher temperatures. Biomass influenced the hydrochars that formed, in which the molecular features of sugarcane bagasse determined the formation of more polar hydrochar, due to the preservation of lignin and phenolic components. Meanwhile, the HTC of vinasse resulted in a more hydrophobic product with an enrichment of condensed and recalcitrant organic fractions. The germination assay showed that polar structures of bagasse may play a role in improving the maize seeds germination rate (increase of ~11%), while the hydrophobic domains showed negative effects. The responses obtained in germination seems to be related to the molecular characteristics that organic extracts can present in solution.

Insights on Molecular Characteristics of Hydrochars by 13C-NMR and Off-Line TMAH-GC/MS and Assessment of Their Potential Use as Plant Growth Promoters.

Hydrochar is a carbon-based material that can be used as soil amendment. Since the physical-chemical properties of hydrochar are mainly assigned to process parameters, we aimed at evaluating the organic fraction of different hydrochars through 13C-NMR and off-line TMAH-GC/MS. Four hydrochars produced with sugarcane bagasse, vinasse and sulfuric or phosphoric acids were analyzed to elucidate the main molecular features. Germination and initial growth of maize seedlings were assessed using hydrochar water-soluble fraction to evaluate their potential use as growth promoters. The hydrochars prepared with phosphoric acid showed larger amounts of bioavailable lignin-derived structures. Although no differences were shown about the percentage of maize seeds germination, the hydrochar produced with phosphoric acid promoted a better seedling growth. For this sample, the greatest relative percentage of benzene derivatives and phenolic compounds were associated to hormone-like effects, responsible for stimulating shoot and root elongation. The reactions parameters proved to be determinant for the organic composition of hydrochar, exerting a strict influence on molecular features and plant growth response.

Process and quality evaluation of different improved composts made with a smart laboratory pilot plant.

This study monitored the process and investigated the quality of compost obtained from different biomasses. Five blends of agri-food waste were composted by a laboratory pilot plant named COMPOSTER, that is designed to optimize biodegradation, and produce compost efficiently. The COMPOSTER consists of two 35-liter nearly adiabatic, aerated bioreactors that simulate an industrial process involving the typical sequence of mesophilic-thermophilic-mesophilic phases. It continuously monitors and records temperature, internal pressure, and biomass weight, while controlling and quantifying oxygen consumption and carbon dioxide emissions resulting from aerobic biodegradation. All composts were characterized for their main chemical, physical, and molecular features, as well as their suppressiveness against Fusarium oxysporum f.sp. lycopersici (FOL), tested on tomato seedlings. Optimized biodegradation yielded 50-60 % mature compost with a cumulative oxygen consumption ranging from 282 to 456 gO2 per kg of dry matter, with peaks of 2.55 gO2 per kg of volatile solids per hour, and carbon dioxide emissions of 22-36 % of the initial carbon content, with peaks of 5.89 g CO2 per kg of volatile solids per hour. Blends containing more ligno-cellulosic ingredients showed higher yields and lower CO2 emissions. Most of the nitrogen present initially was retained in the final compost; indeed, all mixtures exhibited an apparent nitrogen concentration increase due to carbon loss. Composting determined deep modifications in the molecular structure of the organic matter. 13C CPMAS-NMR and off-line thermochemolysis GC-MS analyses highlighted decomposition degree of polysaccharides and peptidic moieties, selective preservation of aliphatic and aromatic recalcitrant compounds, and optimal ongoing humification. All composts were non-phytotoxic, except for that including pepper crop residues, and all resulted rich in macro- and micro-elements for plant nutrition and proved to be active in controlling FOL disease. Compost comprising 81.2 % tomato crop waste exhibited the best growth performance and pathogen control on tomato. Mature, non-phytotoxic, nutrient-rich, and suppressive composts represent promising by-products that can be successfully recycled in agriculture, including high-value applications, leading to lower use of fertilizers and pesticides.

Evaluation of Sustainable Recycled Products to Increase the Production of Nutraceutical and Antibacterial Molecules in Basil Plants by a Combined Metabolomic Approach.

BACKGROUND: An important goal of modern medicine is the development of products deriving from natural sources to improve environmental sustainability. In this study, humic substances (HS) and compost teas (CTs) extracted from artichoke (ART) and coffee grounds (COF) as recycled biomasses were employed on Ocimum basilicum plants to optimize the yield of specific metabolites with nutraceutical and antibacterial features by applying sustainable strategies. METHODS: The molecular characteristics of compost derivates were elucidated by Nuclear Magnetic Resonance spectroscopy to investigate the structure-activity relationship between organic extracts and their bioactive potential. Additionally, combined untargeted and targeted metabolomics workflows were applied to plants treated with different concentrations of compost extracts. RESULTS: The substances HS-ART and CT-COF improved both antioxidant activity (TEAC values between 39 and 55 µmol g-1) and the antimicrobial efficacy (MIC value between 3.7 and 1.3 µg mL-1) of basil metabolites. The metabolomic approach identified about 149 metabolites related to the applied treatments. Targeted metabolite quantification further highlighted the eliciting effect of HS-ART and CT-COF on the synthesis of aromatic amino acids and phenolic compounds for nutraceutical application. CONCLUSIONS: The combination of molecular characterization, biological assays, and an advanced metabolomic approach, provided innovative insight into the valorization of recycled biomass to increase the availability of natural compounds employed in the medical field.

Humic substances from composted fennel residues control the inflammation induced by Helicobacter pylori infection in AGS cells.

Helicobacter pylori (H. pylori) is a common human pathogen causing inflammation. Recent studies have suggested a sophisticated interplay between mitochondria, innate immunity and inflammatory response, thus proposing mitochondrial disfunction as the hallmark of severe inflammatory disorders. In this study, humic substances isolated from composted fennel residues (HS-FEN) were tested as potential therapeutical strategy to restore the mitochondrial physiology and control the inflammation associated with H. pylori infection. The molecular features of HS-FEN were characterized by infrared spectrometry, thermochemolysis-GC/MS, NMR spectroscopy, and high-performance size-exclusion chromatography (HPSEC), which revealed the presence of aromatic polyphenolic components arranged in a rather stable conformation. In vitro results showed antioxidant and anti-inflammatory properties of HS-FEN, that was found to increase the expression level of OPA-1 and SOD-2 genes and in AGS cells stimulated with H. pylori culture filtrate (Hpcf) and concomitantly decrease the expression level of Drp-1 gene and IL-12, IL-17 and G-CSF proteins. The hydrophobic features of HS, their conformational arrangement and large content of bioactive molecules may explain the beneficial effects of HS-FEN, that may potentially become an interesting source of anti-inflammatory agents capable to counteract or prevent the H. pylori-related inflammatory disorders.

Humic Substances Isolated from Recycled Biomass Trigger Jasmonic Acid Biosynthesis and Signalling.

Intensive agriculture maintains high crop yields through chemical inputs, which are well known for their adverse effects on environmental quality and human health. Innovative technologies are required to reduce the risk generated by the extensive and harmful use of pesticides. The plant biostimulants made from humic substances isolated from recyclable biomass offer an alternative approach to address the need for replacing conventional agrochemicals without compromising the crop yield. The stimulatory effects of humic substances are commonly associated with plant hormones, particularly auxins. However, jasmonic acid (JA) is crucial metabolite in mediating the defence responses and governing plant growth and development. This work aimed to evaluate the changes in the biosynthesis and signalling pathway of JA in tomato seedlings treated with humic acids (HA) isolated from vermicompost. We use the tomato model system cultivar Micro-Tom (MT) harbouring a reporter gene fused to a synthetic promoter that responds to jasmonic acid (JERE::GUS). The transcript levels of genes involved in JA generation and activity were also determined using qRT-PCR. The application of HA promoted plant growth and altered the JA status, as revealed by both GUS and qRT-PCR assays. Both JA enzymatic synthesis (LOX, OPR3) and JA signalling genes (JAZ and JAR) were found in higher transcription levels in plants treated with HA. In addition, ethylene (ETR4) and auxin (ARF6) signalling components were positively modulated by HA, revealing a hormonal cross-talk. Our results prove that the plant defence system linked to JA can be emulated by HA application without growth inhibition.

Use of Natural Agents and Agrifood Wastes for the Treatment of Skin Photoaging.

Photoaging is the premature aging of the skin caused by repeated exposure to ultraviolet (UV) rays. The harmful effects of UV rays-from the sun or from artificial sources-alter normal skin structures and cause visible damage, especially in the most exposed areas. Fighting premature aging is one of the most important challenges of the medical landscape. Additionally, consumers are looking for care products that offer multiple benefits with reduced environmental and economic impact. The growing requests for bioactive compounds from aromatic plants for pharmaceutical and cosmetic applications have to find new sustainable methods to increase the effectiveness of new active formulations derived from eco-compatible technologies. The principle of sustainable practices and the circular economy favor the use of bioactive components derived from recycled biomass. The guidelines of the European Commission support the reuse of various types of organic biomass and organic waste, thus transforming waste management problems into economic opportunities. This review aims to elucidate the main mechanisms of photoaging and how these can be managed using natural renewable sources and specific bioactive derivatives, such as humic extracts from recycled organic biomass, as potential new actors in modern medicine.

Use of a new hybrid sol-gel zirconia matrix in the removal of the herbicide MCPA: a sorption/degradation process.

A class II hybrid sol-gel material was prepared starting from zirconium(IV) propoxide and 2,4-pentanedione and its catalytic activity in the removal of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) was revealed. The thermal and structural characterization, performed by thermogravimetry, differential thermal analysis, and diffuse reflectance Fourier transform infrared spectroscopy, demonstrated the hybrid nature of the material. The structure of the material can be described as a polymeric network of zirconium oxo clusters, on the surface of which large part of Zr(4+) ions are involved in strong complexation equilibria with acetylacetonate (acac) ligands. The incubation of MCPA in the presence of this material yielded an herbicide removal fraction up to 98%. A two-step mechanism was proposed for the MCPA removal, in which a reversible first-order adsorption of the herbicide is followed by its catalytic degradation. The nature of the products of the MCPA catalytic degradation as well as the reaction conditions adopted do not support typical oxidation pathways involving radicals, suggesting the existence of a different mechanism in which the Zr(4+):acac enol-type complex can act as Lewis acid catalyst.

Carbon sequestration in soil by in situ catalyzed photo-oxidative polymerization of soil organic matter.

Here we describe an innovative mechanism for carbon sequestration in soil by in situ photopolymerization of soil organic matter under biomimetic catalysis. Three different Mediterranean soils were added with a synthetic water-soluble iron-porphyrin, irradiated by solar light, and subjected first to 5 days incubation and, then, 15, and 30 wetting and drying (w/d) cycles. The in situ catalyst-assisted photopolymerization of soil organic carbon (SOC) increased water stability of soil aggregates both after 5 days incubation and 15 w/d cycles, but not after 30 w/d cycles. Particle-size distribution of all treated soils confirmed the induced soil physical improvement, by showing a concomitant lower yield of the clay-sized fraction and larger yields of either coarse sand- or fine sand-size fractions, depending on soil texture, though only after 5 days incubation. The gain in soil physical quality was reflected by the shift of OC content from small to large soil aggregates, thereby suggesting that photopolymerization stabilized OC by both chemical and physical processes. A further evidence of the carbon sequestration capacity of the photocatalytic treatment was provided by the significant reduction of CO(2) respired by all soils after both incubation and w/d cycles. Our findings suggest that "green" catalytic technologies may potentially be the bases for future practices to increase soil carbon stabilization and mitigate CO(2) emissions from arable soils.

Molecular properties of the Humeome of two calcareous grassland soils as revealed by GC/qTOF-MS and NMR spectroscopy.

A Humeomic fractionation revealed the humus molecular composition of two uncropped calcareous soils of Northern France and differentiated the soils Humeome by extracting humic components first unbound to the organo-mineral matrix and then liberated from their progressively stronger intermolecular and intramolecular ester and ether linkages. We separated organo- (ORG1-3) and water-soluble (AQU2 and AQU4) fractions, a final extractable fraction (RESOM) and soil residues. Organo-soluble fractions were studied by GC coupled with high-resolution mass spectrometry (GC/qTOF-MS), all fractions underwent mono- and two-dimensional liquid-state NMR (except for the iron-rich AQU4 fraction), while solid-state 13C-CPMAS-NMR spectroscopy analyzed soil residues. The Calcaric Leptosol (A) showed a larger mass extraction than the Calcaric Cambisol (B), and a greater cumulative C and N content in its Humeome. Both soils showed the greatest weight yield for AQU4 fraction, followed by ORG2, RESOM, ORG1, AQU2, and ORG3. ORG2 was the most differentiating fraction between the two soils for both compound concentration and diversity, showing a larger C content for soil A than for soil B and a different distribution in aromatic compounds, fatty acids, and dicarboxylic acids. No significant differences between soils were found for ORG 3, suggesting similar processes of OM stabilization for its recalcitrant components, mostly hydrophobic esters of alkanoic, hydroxy, and aromatic acids with linear alkanols. We confirmed that Humeomic fractionation coupled to advanced analytical instrumentations enabled a detailed molecular characterization of the soil Humeome and differentiated between the two calcareous grassland soils and the other soils previously subjected to Humeomics.

Efficient simultaneous removal of heavy metals and polychlorobiphenyls from a polluted industrial site by washing the soil with natural humic surfactants.

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.

Bioactivity and antimicrobial properties of chemically characterized compost teas from different green composts.

The acknowledgement of bioactive functions of compost teas promotes the research on characteristics and potential application of these heterogeneous water-soluble extracts from recycled biomasses. In this work, compost teas were isolated from on-farm composts made with agro-industrial residues of artichoke, pepper and coffee husks with the aim to evaluate the structural-activity relationship of dissolved bioactive molecules. The molecular features of compost teas were determined by 13C-CPMAS NMR spectroscopy, Infrared spectroscopy, and off-line pyrolysis-Gas Chromatography/Mass Spectrometry. Bioactivity of different compost teas was tested on Basil seeds germination, while the antioxidant capacity was measured by ABTS and DDPH spectrophotometric assays. The antimicrobial activity was measured against some pathogenic human bacterial strains. The seed germination experiment showed no phytotoxic effects and a significant increase of both root and epicotyls upon application of coffee husks and pepper CT samples. The same compost teas revealed the largest antioxidant activity and a clear antimicrobial effect determined by MIC (Minimal Inhibitory Concentration) against some gram-negative bacterial strains such as Pseudomonas aeruginosa, Escherichia coli, and Klebsiella pneumoniae. The bioactivity of CT-samples was related to their general hydrophobic features and to specific molecular composition. In particular, 13C-CPMAS NMR spectra and off-line thermochemolysis GC-MS highlighted a close correlation between radical scavenger activity and antibacterial bioactive functions with bio-available soluble aromatic compounds, such as lignin and phenols derivatives. The antioxidant and, antibacterial properties of compost teas from green composts encourages an innovative potential application of these eco-friendly products not only in agricultural applications but also in nutraceutical and pharmaceutical fields.

Remediation of waters contaminated with MCPA by the yeasts Lipomyces starkeyi entrapped in a sol-gel zirconia matrix.

A single-stage sol-gel route was set to entrap yeast cells of Lipomyces starkeyi in a zirconia (ZrO(2)) matrix, and the remediation ability of the resulting catalyst toward a phenoxy acid herbicide, 4-chloro-2-methylphenoxyacetic acid (MCPA), was studied. It was found that the experimental procedure allowed a high dispersion of the microorganisms into the zirconia gel matrix; the ZrO(2) matrix exhibited a significant sorption capacity of the herbicide, and the entrapped cells showed a degradative activity toward MCPA. The combination of these effects leads to a nearly total removal efficiency (>97%) of the herbicide at 30 °C within 1 h incubation time from a solution containing a very high concentration of MCPA (200 mg L(-1)). On the basis of the experimental evidence, a removal mechanism was proposed involving in the first step the sorption of the herbicide molecules on the ZrO(2) matrix, followed by the microbial degradation operated by the entrapped yeasts, the metabolic activity of which appear enhanced under the microenvironmental conditions established within the zirconia matrix. Repeated batch tests of sorption/degradation of entrapped Lipomyces showed that the removal efficiency retained almost the same value of 97.3% after 3 batch tests, with only a subsequent slight decrease, probably due to the progressive saturation of the zirconia matrix.

Humic extracts of hydrochar and Amazonian Dark Earth: Molecular characteristics and effects on maize seed germination.

Inspired by the presence of anthropogenic organic matter in highly fertile Amazonian Dark Earth (ADE), which is attributed to the transformation of organic matter over thousands of years, we explored hydrothermal carbonization as an alternative for humic-like substances (HLS) production. Hydrothermal carbonization of sugarcane industry byproducts (bagasse and vinasse) in the presence and absence of H3PO4 afforded HLS, which were isolated and compared with humic substances (HS) isolated from ADE in terms of molecular composition and maize seed germination activity. HLS isolated from sugarcane bagasse hydrochar produced in the presence or absence of H3PO4 comprised both hydrophobic and hydrophilic moieties, differing from other HLS mainly in terms of phenolic content, while HLS isolated from vinasse hydrochar featured hydrophobic structures mainly comprising aliphatic moieties. Compared to that of HLS, the structure of soil-derived HS reflected an increased contribution of fresh organic matter input and, hence, featured a higher content of O-alkyl moieties. HLS derived from lignocellulosic biomass were rich in phenolics and promoted maize seed germination more effectively than HLS comprising alkyl moieties. Thus, HLS isolated from bagasse hydrochar had the highest bioactivity, as the presence of amphiphilic moieties therein seemed to facilitate the release of bioactive molecules from supramolecular structures and stimulate seed germination. Based on the above results, the hydrothermal carbonization of lignocellulosic biomass was concluded to be a viable method of producing amphiphilic HLS for use as plant growth promoters.

Humic extracts from hydrochar and Amazonian Anthrosol: Molecular features and metal binding properties using EEM-PARAFAC and 2D FTIR correlation analyses.

Organic matter plays many roles in the soil ecosystem. One property of the substance concerns the metal complexation and interaction with organic contaminants. In this sense, the humic substances (HS), a heterogeneous mixture of compounds, naturally derived from degradation of biomass, have been widely studied in environmental sciences. Recent advances showed a new way to produce humic-like substances (HLS) through hydrothermal carbonization of biomass. Thus, this study aimed to evaluate the HLS of hydrochars, produced by using a mixture of sugarcane bagasse and vinasse with sulfuric acid added (1 and 4% v/v), and to assess their interactions with metal ions, (Fe(III), Al(III), Cu(II) and Co(II)) using EEM-PARAFAC and a two-dimensional FTIR correlation analysis. The results were compared to the humic substances extracted from the Amazonian Anthrosol, as a model of anthropogenic organic matter. NMR analysis showed that humic-like extracts from hydrochar are mainly hydrophobic, while the soil has a greater contribution of polar moieties. The HLS and HS showed similar complexation capacities for Fe(III), Al(III) and Cu(II) assays. For Co(II) HLS exhibited larger affinities than HS. Two-dimensional correlation analysis FTIR showed that chemical groups may undergo conformational alteration with metal additions to achieve more stable arrangements (higher stability constant). Therefore, these results contribute more knowledge about the mechanism of HS and metal ion interaction, as well as showing that HTC can be an interesting option for HLS production, to be used as humic based materials.

Soil washing with solutions of humic substances from manure compost removes heavy metal contaminants as a function of humic molecular composition.

Humic Substances (HS) from Leonardite and two different composts were used as biosurfactants to wash heavy metals (Cu, Pb, Zn, Cd, Cr) from a soil added with two metals concentrations and aged for 4 and 12 months. Composts were obtained by mixing manure with either 40 (CM-I) and 20 (CM-II) % of straw as structuring material. For both aging periods and both metal concentrations, HS from CM-I removed more metals than from Leonardite, whereas the washing capacity of HS from CM-II was negligible. 13C-CPMAS-NMR spectra of HS indicated that while aromatic moieties for CM-I and Leonardite were more abundant than CM-II, HS from CM-I was largest in carboxyl and phenolic carbons. Hence, HS from CM-I had a greater complexing capacity than from both Leonardite and CM-II and effectively displaced heavy metals from soil during the washing treatment. Moreover, the amount of metals removed by solutions of ammonium acetate (AA) and diethylenetriaminepentaacetic acid (DTPA), was found invariably smaller than by HS from CM-I, thereby indicating that HS removed more than one metal specie. The combined washing with HS from CM-I before and after soil treatment by either AA and DTPA revealed significant larger metal removals than by single solutions alone. This shows that humic soil washing also renders residual metals potentially more available to subsequent soil remediation approaches, such as phytoextraction. These results suggest a novel, efficient, and molecularly-based technology to remediate soils from heavy metals can be based on a low-cost and sustainable humic matter produced from recycled biomasses.

Molecular characterization of a compost and its water-soluble fractions.

A sequential chemical fractionation was applied to a compost, with its dissolved organic matter (DOM) extracted in water and separated in hydrophilic (HiDOM) and hydrophobic (HoDOM) components and a water extract, following oxidation of compost suspension with an oxygen flux (TEA). The components sequentially isolated by mild extractions and hydrolyses as structurally unbound (SU), weakly bound (WB), and strongly bound (SB) to the matrix of the bulk compost and its water-soluble fractions were identified in their molecular structure. The bulk compost was rich with components derived from both aromatic (phenolic compounds) and aliphatic (long-chain fatty acids, hydroxy acids, diacids, and alcohols) structures of suberins, whereas components derived from cutins were especially extracted from TEA, HoDOM, and HiDOM. The TEA sample also yielded a significant amount of oxidized products that was dominated by dehydroabietic acids. The fractionation sequence highlighted the different intermolecular interactions that bound the isolated molecular components to the compost complex matrix. While a significant part of the bulk compost was still present as a solid residue at the end of the sequential fractionation, all water-soluble fractions were almost completely hydrolyzed. These results indicate that the water-soluble components of compost may be readily separated from the compost matrix and contribute to the environmental dynamics of natural organic matter.

An alternative to mineral phosphorus fertilizers: The combined effects of Trichoderma harzianum and compost on Zea mays, as revealed by 1H NMR and GC-MS metabolomics.

The ability of Trichoderma harzianum (strain OMG-08) as plant growth promoting fungus (PGPF), was tested on Zea mays plants grown in soil pots added with different inorganic (triple superphosphate and rock phosphate) and organic (cow and horse manure composts) P fertilizers. The effect of treatments was evaluated by following the variations of plants dry biomass and nutrient content, as well as the metabolic changes in plant leaves by both GC-MS and NMR spectroscopy. A synergic effect was observed in treatments with both composts and fungus inoculation, in which not only plant growth and P uptake were enhanced, but also the expression of different metabolites related to an improved photosynthetic activity. Conversely, the combination of Trichoderma with inorganic fertilizers was less effective and even showed a reduction of plants shoot biomass and N content. The corresponding plant metabolome revealed metabolic compounds typical of biotic or abiotic stresses, which may be attributed to a reduced capacity of inorganic fertilizers to provide a sufficient P availability during plant growth. Our findings also indicate that the molecular composition of compost differentiated the Trichoderma activity in sustaining plant growth. The positive effects of the combined Trichoderma and compost treatment suggest that it may become an alternative to the phosphorus mineral fertilization.