Oxidative Stress Response Mechanisms Sustain the Antibacterial and Antioxidant Activity of Quercus ilex.

The development of new natural antibiotics is considered as the heart of several investigations in the nutraceutical field. In this work, leaves of Quercus ilex L. treated by tropospheric ozone (O3) and nitrogen (N) deposition, exhibited a clear antimicrobial efficacy against five multi-drug resistant (MDR) bacterial strains (two gram-positive and three gram-negative). Under controlled conditions, it was studied how simulated N deposition influences the response to O3 and the antibacterial and antioxidant activity, and antioxidant performance. The extraction was performed by ultra-pure acetone using two different steps. A higher antioxidant activity was measured in the presence of interaction between O3 and N treatments on Quercus leaves. At the same time, all organic extracts tested have shown bacteriostatic activity against all the tested strains with a MIC comprised between 9 and 4 micrograms/mL, and a higher antioxidant efficacy shown by spectrophotometric assay. Stronger antimicrobial activity was found in the samples treated with O3, whereas N-treated plants exhibited an intermediate antibacterial performance. This performance is related to the stimulation of the non-enzymatic antioxidant system induced by the oxidative stress, which results in an increase in the production of antimicrobial bioactive compounds.

Effectiveness of bio-effectors on maize, wheat and tomato performance and phosphorus acquisition from greenhouse to field scales in Europe and Israel: a meta-analysis.

Biostimulants (Bio-effectors, BEs) comprise plant growth-promoting microorganisms and active natural substances that promote plant nutrient-acquisition, stress resilience, growth, crop quality and yield. Unfortunately, the effectiveness of BEs, particularly under field conditions, appears highly variable and poorly quantified. Using random model meta-analyses tools, we summarize the effects of 107 BE treatments on the performance of major crops, mainly conducted within the EU-funded project BIOFECTOR with a focus on phosphorus (P) nutrition, over five years. Our analyses comprised 94 controlled pot and 47 field experiments under different geoclimatic conditions, with variable stress levels across European countries and Israel. The results show an average growth/yield increase by 9.3% (n=945), with substantial differences between crops (tomato > maize > wheat) and growth conditions (controlled nursery + field (Seed germination and nursery under controlled conditions and young plants transplanted to the field) > controlled > field). Average crop growth responses were independent of BE type, P fertilizer type, soil pH and plant-available soil P (water-P, Olsen-P or Calcium acetate lactate-P). BE effectiveness profited from manure and other organic fertilizers, increasing soil pH and presence of abiotic stresses (cold, drought/heat or salinity). Systematic meta-studies based on published literature commonly face the inherent problem of publication bias where the most suspected form is the selective publication of statistically significant results. In this meta-analysis, however, the results obtained from all experiments within the project are included. Therefore, it is free of publication bias. In contrast to reviews of published literature, our unique study design is based on a common standardized protocol which applies to all experiments conducted within the project to reduce sources of variability. Based on data of crop growth, yield and P acquisition, we conclude that application of BEs can save fertilizer resources in the future, but the efficiency of BE application depends on cropping systems and environments.

Enhanced washing of polycyclic aromatic hydrocarbons from contaminated soils by the empowered surfactant properties of de novo O-alkylated humic matter.

Aqueous solutions of humic acid (HA) derivatized by a catalyzed O-alkylation reaction with methyl, pentyl, and benzyl groups at 40, 60, and 80% of total HA acidity were used to wash off polycyclic aromatic hydrocarbons (PAHs) from two contaminated soils. The enhanced surfactant properties enabled the alkylated HA to remove phenanthrene, anthracene, fluoranthene, and pyrene from both soils more extensively than the original unmodified HA, the 60% benzylation generally showing the greatest soil washing efficiency. For both soils, all alkylated HA revealed greater PAH removals than Triton X-100 nonionic surfactant, while the benzylated and methylated HA nearly and fully matched pollutants release by the anionic SDS in the coarse- and fine-textured soils, respectively. A consecutive second washing with 60% benzylated HA removed additional PAHs, in respect to the first washing, from the coarser-textured soil, except for fluoranthene, while removal from the finer-textured soil incremented even more for all PAHs. These findings indicate that the enhanced hydrophobicity obtained by a simple and unexpensive chemical derivatization of a natural humic surfactant can be usefully exploited in the washing of polluted soils, without being toxic to the soil biota and by potentially promoting the subsequent bio-attenuation of organic pollutants.

Lignin nanoparticles from hydrotropic fractionation of giant reed and eucalypt: Structural elucidation and antibacterial properties.

A hydrotropic solution of maleic acid (MA) was exploited to fractionate giant reed (AD) and eucalypt (EUC). The pre-treatment was successful for AD, while it was unsatisfactory for EUC, likely due to unoptimized reaction conditions. Interestingly, lignin nanoparticles (LNP) were produced via spontaneous aggregation following spent liquor dilution. LNP were studied by a plethora of analytical techniques, such as thermogravimetry, electron microscopy, and Nuclear Magnetic Resonance spectroscopy (NMR). Notwithstanding LNP from both AD and EUC showed similar thermal behaviour and morphology, a greater content of aliphatic hydroxyl, carboxyl, guaiacyl and p-hydroxyphenyl moieties was reported for AD-LNP, whereas EUC-LNP had a larger amount of syringyl groups and a higher S/G ratio. Also, the 1H-DOSY NMR indicated the lower size of AD-LNP. Moreover, the LNP were found to negatively impact on the development of several human or plant pathogens, and their bioactivity was related to the occurrence of guaiacyl and p-hydroxyphenyl moieties and a lower the LNP size. We therefore found that MA delignification allows both to achieve high delignification efficiency and to obtain LNP with promising antibacterial effect. Such LNP may help counteracting the antibiotics resistance and sustain the quest for finding sustainable agrochemicals.

Plastics shape the black soldier fly larvae gut microbiome and select for biodegrading functions.

BACKGROUND: In the last few years, considerable attention has been focused on the plastic-degrading capability of insects and their gut microbiota in order to develop novel, effective, and green strategies for plastic waste management. Although many analyses based on 16S rRNA gene sequencing are available, an in-depth analysis of the insect gut microbiome to identify genes with plastic-degrading potential is still lacking. RESULTS: In the present work, we aim to fill this gap using Black Soldier Fly (BSF) as insect model. BSF larvae have proven capability to efficiently bioconvert a wide variety of organic wastes but, surprisingly, have never been considered for plastic degradation. BSF larvae were reared on two widely used plastic polymers and shotgun metagenomics was exploited to evaluate if and how plastic-containing diets affect composition and functions of the gut microbial community. The high-definition picture of the BSF gut microbiome gave access for the first time to the genomes of culturable and unculturable microorganisms in the gut of insects reared on plastics and revealed that (i) plastics significantly shaped bacterial composition at species and strain level, and (ii) functions that trigger the degradation of the polymer chains, i.e., DyP-type peroxidases, multicopper oxidases, and alkane monooxygenases, were highly enriched in the metagenomes upon exposure to plastics, consistently with the evidences obtained by scanning electron microscopy and 1H nuclear magnetic resonance analyses on plastics. CONCLUSIONS: In addition to highlighting that the astonishing plasticity of the microbiota composition of BSF larvae is associated with functional shifts in the insect microbiome, the present work sets the stage for exploiting BSF larvae as "bioincubators" to isolate microbial strains and enzymes for the development of innovative plastic biodegradation strategies. However, most importantly, the larvae constitute a source of enzymes to be evolved and valorized by pioneering synthetic biology approaches. Video Abstract.

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.

Varying the hydrophobicity of humic matter by a phase-transfer-catalyzed O-alkylation reaction.

An O-alkylation reaction catalyzed by tetrabutylammonium hydroxide (TBAH) as a phase-transfer agent was applied to a humic acid (HA) to modify its hydrophobic properties. The carboxyl and hydroxyl functional groups of HA acted as nucleophiles in substitution reactions (Sn2) with methyl iodide, pentyl bromide and benzyl bromide added in amounts equimolar to 20, 60 and 80% of HA total nucleophilic sites. The occurrence of O-alkylation was shown by DRIFT spectrometry, NMR spectroscopy, High Performance Size Exclusion Chromatography (HPSEC) and elemental analysis of reaction products. DRIFT spectra showed changes in C-H stretching and bending regions following the insertion of methyl and pentyl groups, while the incorporation of benzyl groups revealed the characteristics aromatic C-H stretching bands. Both liquid- and solid-state NMR spectra revealed characteristic signals for alkyl/aryl esters and ethers. HPSEC chromatograms of alkylated materials invariably displayed an increase in hydrodynamic volume in respect to the original HA, thereby suggesting that the enhanced hydrophobicity conveyed further associations among humic molecules. Analytical, HPSEC and spectroscopic results suggest that benzylation was the most effective reaction at all percentages of HA total nucleophilicity, followed, in the order, by pentylation and methylation, The benzylation reaction was used to improve reaction and work-up conditions and show that HA could be efficiently alkylated also with substantial reduction of TBAH amount, with no THF addition, increase of reaction time and of washing cycles to remove catalyst impurities. These findings indicate that the hydrophobicity of humic substances can be modulated through a mild O-alkylation reaction under a phase-transfer catalysis according to the extent of exposed HA nucleophilic sites. Such a structural modification of humic matter may have multiple chemical, environmental and biological applications.

Valorization of lignins from energy crops and agro-industrial byproducts as antioxidant and antibacterial materials.

BACKGROUND: Developing eco-friendly antioxidant and antimicrobial substances originating from biomass residues has recently attracted considerable interest. In this study, two lignosulfonates and various oxidized water-soluble lignins were investigated for their antioxidant properties, as assessed by ABTS, DPPH and Folin-Ciocalteu methods, and their antimicrobial activity against some bacterial strains responsible for human pathologies. RESULTS: The lignosulfonates showed the largest antiradical/antimicrobial capacity, whereas the other substrates were less effective. The observed antioxidant/antibacterial properties were positively correlated with lignin aromatic/phenolic content. The positive correlation between antiradical and antimicrobial activities suggests that lignin scavenging capacity was also involved in its antibacterial activity. A greater antimicrobial performance was generally observed against Gram-positive bacterial strains, and it was attributed to the intrinsic larger susceptibility of Gram-positive bacteria to lignin phenols. A significant though lesser inhibitory activity was also found against Escherichia coli. CONCLUSION: Our results confirmed the dependence of lignin antioxidant/antibacterial power on its extraction method and chemical structure, as well as on the type of bacterial strains. Identifying the relationship between lignin molecular composition and its antioxidant/antibacterial features represents an advance on the potential future use of renewable and eco-compatible lignin materials in nutraceutical, pharmaceutical and cosmetic sectors. © 2021 Society of Chemical Industry.

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.

Quantitative Structure-Activity Relationship of Humic-Like Biostimulants Derived From Agro-Industrial Byproducts and Energy Crops.

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.

The Form of N Supply Determines Plant Growth Promotion by P-Solubilizing Microorganisms in Maize.

Phosphate-(P)-solubilizing microorganisms (PSM) are important drivers of P cycling in natural and agro-ecosystems. Their use as plant inoculants to improve P acquisition of crops has been investigated for decades. However, limited reproducibility of the expected effects, particularly under field conditions, remains a major challenge. This study demonstrates that the form of nitrogen fertilization has a significant impact on the performance of various fungal and bacterial PSM inoculants in maize grown on neutral to alkaline soils with limited P availability. Under these conditions, a high soil pH-buffering capacity frequently limits the efficiency of nutrient mobilization, mediated by plant roots and microorganisms via rhizosphere acidification. In a soil pH range between 7.0 and 8.0, nitrate fertilization promoting rhizosphere alkalinisation further aggravates this problem. Accordingly, in greenhouse experiments, six strains of Pseudomonas, Bacillus, Paenibacillus, Streptomyces, and Penicillium with proven P-solubilizing potential, completely failed to promote P acquisition in maize grown on a calcareous Loess sub-soil pH 7.6 with nitrate fertilization and rock phosphate (Rock-P) as a sparingly soluble P source. However, after replacement of nitrate fertilization by ammonium, stabilized with the nitrification inhibitor 3,4-dimethylpyrazole-phosphate (DMPP), five out of seven investigated PSM inoculants (comprising 12 fungal and bacterial PSM strains) exerted beneficial effects on plant growth and reached up to 88% of the shoot biomass production of a control supplied with soluble triple-superphosphate (TSP). Stabilized ammonium combined with PSM-inoculants improved P acquisition (Trichoderma harzianum T22, Pseudomonas sp. DMSZ 13134), while other strains particularly stimulated root growth (T. harzianum OMG16, Bacillus amyloliquefaciens FZB42), which promoted the acquisition also of other mineral nutrients, such as N, K, and Mn. A similar effect was recorded under field conditions on an alkaline clay-loam soil pH 8.6. The combination of stabilized ammonium with a range of consortium products based on T. harzianum OMG16, B. amyloliquefaciens, micronutrients, and humic acids completely compensated the effect of a TSP fertilization on field establishment, nutrient acquisition, and yield formation in maize, while non-stabilized urea-di-ammonium phosphate fertilization was largely ineffective. These findings suggest that the efficiency of PSM-plant interactions can be influenced by the form of N fertilization, offering promising perspectives for synergistic effects with stabilized ammonium fertilizers.

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.

Replacing calcium with ammonium counterion in lignosulfonates from paper mills affects their molecular properties and bioactivity.

Lignosulfonates are important by-products of the paper industry and may be transformed into different commodities. We studied the molecular properties of ammonium (LS-AM) and calcium Lignosulfonates (LS-C) and evaluated their bioactivity towards the early development of maize plantlets. The FT-IR, 13C NMR and 1H-13C-HSQC-NMR spectra showed that the two lignosulfonates varied in hydroxyl, sulfonate and phenolic content, while DOSY-NMR spectroscopy suggested a similar diffusivity. High Performance Size Exclusion Chromatography (HPSEC) was used to simulate the effects of root-exuded acids and describe the conformational dynamics of both LS substrates in acidic aqueous solutions. This technique showed that LS-C was stabilized by the divalent Ca2+ counterion, thus showing a greater conformational stability than LS-AM, whose components could not be as efficiently aggregated by the monovalent NH4+ counter-ion. The plant bioassays revealed that LS-AM enhanced the elongation of the root system, whereas LS-C significantly increased both total and shoot plant weights. We concluded that the lignosulfonate bioactivity on plant growth depended on the applied concentrations, their molecular properties and conformational stability.

High-Resolution Magic-Angle-Spinning NMR and Magnetic Resonance Imaging Spectroscopies Distinguish Metabolome and Structural Properties of Maize Seeds from Plants Treated with Different Fertilizers and Arbuscular mycorrhizal fungi.

Both high-resolution magic-angle-spinning (HRMAS) and magnetic resonance imaging (MRI) NMR spectroscopies were applied here to identify the changes of metabolome, morphology, and structural properties induced in seeds (caryopses) of maize plants grown at field level under either mineral or compost fertilization in combination with the inoculation by arbuscular mycorrhizal fungi (AMF). The metabolome of intact caryopses was examined by HRMAS-NMR, while the morphological aspects, endosperm properties and seed water distribution were investigated by MRI. Principal component analysis (PCA) was applied to evaluate 1H CPMG (Carr-Purcel-Meiboom-Gill) HRMAS spectra as well as several MRI-derived parameters ( T1, T2, and self-diffusion coefficients) of intact maize caryopses. PCA score-plots from spectral results indicated that both seeds metabolome and structural properties depended on the specific field treatment undergone by maize plants. Our findings show that a combination of multivariate statistical analyses with advanced and nondestructive NMR techniques, such as HRMAS and MRI, enables the evaluation of the effects induced on maize caryopses by different fertilization and management practices at field level. The spectroscopic approach adopted here may become useful for the objective appraisal of the quality of seeds produced under a sustainable agriculture.

Molecular characteristics of water-extractable organic matter from different composted biomasses and their effects on seed germination and early growth of maize.

Four water extractable organic matter (WEOM) were obtained from composts made out of residues of: 1. artichoke (C-CYN), 2. artichoke/fennel (C-CYNF), 3. tomato/woodchips (C-TOM), 4. Municipal solid waste (C-MSW), and their bioactivity was tested for maize seed germination and maize seedling growth. The molecular properties of both original composts and their WEOM were characterized by spectroscopic (13C-CPMAS- and 1H NMR, FTIR-ATR), thermochemolysis-GC/MS, and thermal methods (TGA, DSC). While all WEOM had significant effects on plant growth, CYN-WEOM was the only material that concomitantly increased germination rate and primary and lateral root length of maize seedlings. The lignin-rich WEOM from green composts were generally more effective than those obtained from equally hydrophobic, but mainly alkyl-rich municipal organic wastes. A flexible conformational structure, due to the balanced content of aromatic compounds and carbohydrates, appeared to facilitate the release of bioactive molecules from WEOM suprastructures and stimulate plant growth.

Water-Soluble Lignins from Different Bioenergy Crops Stimulate the Early Development of Maize (Zea mays, L.).

The molecular composition of water-soluble lignins isolated from four non-food bioenergy crops (cardoon CAR, eucalyptus EUC, and two black poplars RIP and LIM) was characterized in detail, and their potential bioactivity towards maize germination and early growth evaluated. Lignins were found to not affect seed germination rates, but stimulated the maize seedling development, though to a different extent. RIP promoted root elongation, while CAR only stimulated the length of lateral seminal roots and coleoptile, and LIM improved only the coleoptile development. The most significant bioactivity of CAR was related to its large content of aliphatic OH groups, C-O carbons and lowest hydrophobicity, as assessed by (31)P-NMR and (13)C-CPMAS-NMR spectroscopies. Less bioactive RIP and LIM lignins were similar in composition, but their stimulation of maize seedling was different. This was accounted to their diverse content of aliphatic OH groups and S- and G-type molecules. The poorest bioactivity of the EUC lignin was attributed to its smallest content of aliphatic OH groups and largest hydrophobicity. Both these features may be conducive of a EUC conformational structure tight enough to prevent its alteration by organic acids exuded from vegetal tissues. Conversely the more labile conformational arrangements of the other more hydrophilic lignin extracts promoted their bioactivity by releasing biologically active molecules upon the action of exuded organic acids. Our findings indicate that water-soluble lignins from non-food crops may be effectively used as plant biostimulants, thus contributing to increase the economic and ecological liability of bio-based industries.

Molecular evaluation of soil organic matter characteristics in three agricultural soils by improved off-line thermochemolysis: the effect of hydrofluoric acid demineralisation treatment.

The molecular composition of soil organic matter (SOM) in three agricultural fields under different managements, was evaluated by off-line thermochemolysis followed by gas chromatography mass spectrometry analysis (THM-GC-MS). While this technique enabled the characterization of SOM components in coarse textured soil, its efficiency in heavy textured soils was seriously affected by the interference of clay minerals, which catalyzed the formation of secondary artifacts in pyrolysates. Soil demineralization with hydrofluoric acid (HF) solutions effectively improved the reliable characterization of organic compounds in clayey soils by thermochemolysis, while did not alter significantly the results of coarse textured soil. A wide range of lignin monomers and lipids molecules, of plant and microbial origin, were identified in the pyrograms of HF treated soils, thereby revealing interesting molecular differences between SOM management practices. Our results indicated that clay removal provided by HF pretreatment enhanced the capacity of thermochemolysis to be a valuable and accurate technique to study the SOM dynamics also in heavy-textured and OC-depleted cultivated soils.

Influence of compost on the mobility of arsenic in soil and its uptake by bean plants (Phaseolus vulgaris L.) irrigated with arsenite-contaminated water.

The influence of compost on the growth of bean plants irrigated with As-contaminated waters and its influence on the mobility of As in the soils and the uptake of As (as NaAs(III)O2) by plant components was studied at various compost application rates (3·10(4) and 6·10(4) kg ha(-1)) and at three As concentrations (1, 2 and 3 mg kg(-1)). The biomass and As and P concentrations of the roots, shoots and beans were determined at harvest time, as well as the chlorophyll content of the leaves and nonspecific and specifically bound As in the soil. The bean plants exposed to As showed typical phytotoxicity symptoms; no plants however died over the study. The biomass of the bean plants increased with the increasing amounts of compost added to the soil, attributed to the phytonutritive capacity of compost. Biomass decreased with increasing As concentrations, however, the reduction in the biomass was significantly lower with the addition of compost, indicating that the As phytotoxicity was alleviated by the compost. For the same As concentration, the As content of the roots, shoots and beans decreased with increasing compost added compared to the Control. This is due to partial immobilization of the As by the organic functional groups on the compost, either directly or through cation bridging. Most of the As adsorbed by the bean plants accumulated in the roots, while a scant allocation of As occurred in the beans. Hence, the addition of compost to soils could be used as an effective means to limit As accumulation in crops from As-contaminated waters.

Sorption of Cu, Pb and Cr on Na-montmorillonite: competition and effect of major elements.

The competitive sorption among Cu, Pb and Cr in ternary system on Na-montmorillonite at pH 3.5, 4.5 and 5.5 and at different heavy metal concentrations, and the effect of varying concentrations of Al, Fe, Ca and Mg on the sorption of heavy metals were studied. Competitive sorption of Cu, Pb and Cr in ternary system on montmorillonite followed the sequence of Cr≫Cu>Pb. Moreover, the competition was weakened by the increase of pH while was intensified by the increase of heavy metal concentration. The sorption of heavy metal on montmorillonite was inhibited by the presence of Ca and Mg, while Al and Fe showed different patterns in affecting heavy metal sorption. Aluminum and Fe generally inhibited the sorption of heavy metal when the pH and/or concentration of major elements were relatively low. However, promoting effects on heavy metal sorption by Al and Fe were found at relatively high pH and/or great concentration of major elements. The inhibition of major elements on heavy metal sorption generally followed the order of Al>Fe>Ca⩾Mg, while Fe was more efficient than Al in promoting the sorption of heavy metals. These findings are of fundamental significance for evaluating the mobility of heavy metals in polluted environments.

Sorption of arsenite and arsenate on ferrihydrite: effect of organic and inorganic ligands.

We studied the sorption of As(III) and As(V) onto ferrihydrite as affected by pH, nature and concentration of organic [oxalic (OX), malic (MAL), tartaric (TAR), and citric (CIT) acid] and inorganic [phosphate (PO(4)), sulphate (SO(4)), selenate (SeO(4)) and selenite (SeO(3))] ligands, and the sequence of anion addition. The sorption capacity of As(III) was greater than that of As(V) in the range of pH 4.0-11.0. The capability of organic and inorganic ligands in preventing As sorption follows the sequence: SeO(4) ≈ SO(4) < OX < MAL ≈ TAR < CIT < SeO(3) ≪ PO(4). The efficiency of most of the competing ligands in preventing As(III) and As(V) sorption increased by decreasing pH, but PO(4) whose efficiency increased by increasing pH. In acidic systems all the competing ligands inhibited the sorption of As(III) more than As(V), but in alkaline environments As(III) and As(V) seem to be retained with the same strength on the Fe-oxide. Finally, the competing anions prevented As(III) and As(V) sorption more when added before than together or after As(III) or As(V).