0000000000153287
AUTHOR
Alessandro Piccolo
Influence of land use on the characteristics of humic substances in some tropical soils of Nigeria
Summary In highly weathered tropical conditions, soil organic matter is important for soil quality and productivity. We evaluated the effects of deforestation and subsequent arable cropping on the qualitative and quantitative transformation of the humic pool of the soil at three locations in Nigeria. Cultivation reduced the humic pool in the order: acetone-soluble hydrophobic fraction (HE) > humic acid (HA) > humin (HU) > fulvic acid (FA), but not to the same degree at all three sites. The C and N contents, as well as the C/N ratios of humic extracts, were large and not substantially influenced by land use. The δ13C values of the humic extracts were invariably more negative in forested soil…
NMR spectroscopy evaluation of direct relationship between soils and molecular composition of red wines from Aglanico grapes
1H NMR spectroscopy was employed to investigate the molecular quality of Aglianico red wines from the Campania region of Italy. The wines were obtained from three different Aglianico vineyards characterized by different microclimatic and pedological properties. In order to reach an objective evaluation of “terroir” influence on wine quality, grapes were subjected to the same winemaking procedures. The careful subtraction of water and ethanol signals from NMR spectra allowed to statistically recognize the metabolites to be employed in multivariate statistical methods: Principal Component Analysis (PCA), Discriminant Analysis (DA) and Hierarchical Clustering Analysis (HCA). The three wines we…
Chlamyphilone, a Novel Pochonia chlamydosporia Metabolite with Insecticidal Activity
Metabolites from a collection of selected fungal isolates have been screened for insecticidal activity against the aphid Acyrthosiphon pisum. Crude organic extracts of culture filtrates from six fungal isolates (Paecilomyces lilacinus, Pochonia chlamydosporia, Penicillium griseofulvum, Beauveria bassiana, Metarhizium anisopliae and Talaromyces pinophilus) caused mortality of aphids within 72 h after treatment. In this work, bioassay-guided fractionation has been used to characterize the main bioactive metabolites accumulated in fungal extracts. Leucinostatins A, B and D represent the bioactive compounds produced by P. lilacinus. From P. griseofulvum and B. bassiana extracts, griseofulvin an…
The Wine: typicality or mere diversity? The effect of spontaneous fermentations and biotic factors on the characteristics of wine
Abstract Wine is probably one of the main fermented beverages for which the recognition of the “territoriality” is fundamental for its appreciation. The sensory profile of wine is significantly affected by microbial activities, and indigenous microorganisms may significantly contribute to the expression of wine typicality. The microbial ecology of wines is complex and includes several species and strains of yeasts, bacteria and molds. Several works showed the positive effects of spontaneous fermentations on the quality of wine as a consequence of the growth of different species and/or strains together at high levels. Furthermore, a new style of “natural” winemaking is gaining importance, si…
Increased conformational rigidity of humic substances by oxidative biomimetic catalysis
A synthetic water-soluble meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of iron(III) chloride, Fe(TDCPPS)Cl, was employed as a biomimetic catalyst in the oxidative coupling of terrestrial humic materials. High-performance size-exclusion chromatography (HPSEC), solid-state nuclear magnetic resonance (CPMAS-(13)C NMR), electron paramagnetic resonance (EPR), and diffuse reflectance infrared spectroscopy (DRIFT) were used to follow conformational and structural changes brought about in different humic materials by the oxidative coupling. Increase in apparent weight-average molecular weight (Mw(a)) occurred invariably for all humic substances with the oxidative polymerization catalyzed …
Changes of humic substances characteristics from forested to cultivated soils in Ethiopia
The dynamics of the stable fractions of soil organic matter (SOM), the humic substances, has been rarely studied in tropical soils. We evaluated extraction yields, elemental composition, isotopic d 13 C abundance and solid-state 13 C NMR spectra of humic fractions isolated from five forested and cultivated soils in Ethiopia in order to assess the influence of deforestation and subsequent cultivation on the composition of humic fractions. In all locations, humic (HA) and fulvic (FA) acids, humin (HU) and a humic hydrophobic fraction extracted with an acetone–HCl solution (HE) were decreased as a result of deforestation and cultivation, but the magnitude of decrease was site-specific. While t…
Metabolomic by 1H NMR Spectroscopy Differentiates “Fiano Di Avellino” White Wines Obtained with Different Yeast Strains
We employed (1)H NMR spectroscopy to examine the molecular profile of a white "Fiano di Avellino" wine obtained through fermentation by either a commercial or a selected autochthonous Saccharomyces cerevisiae yeast starter. The latter was isolated from the same grape variety used in the wine-making process in order to strengthen the relationship between wine molecular quality and its geographical origin. (1)H NMR spectra, where water and ethanol signals were suppressed by a presaturated T1-edited NMR pulse sequence, allowed for definition of the metabolic content of the two differently treated wines. Elaboration of NMR spectral data by multivariate statistical analyses showed that the two d…
Advanced CPMAS-13C NMR techniques for molecular characterization of size-separated fractions from a soil humic acid
A humic acid extracted from a volcanic soil was subjected to preparative high-performance size-exclusion chromatography (HPSEC) to reduce its molecular complexity and eleven different size fractions were obtained. Cross-polarization magic-angle spinning 13C NMR (CPMAS 13C NMR) analysis performed with variable contact-time (VCT) pulse sequences showed that the largest molecular-size fractions contained aromatic, alkyl, and carbohydrate-like components. The carbohydrate-like content and the alkyl chain length seemed to decrease with decreasing molecular size. Progressive reduction of aromatic carbon atoms was also observed with decreasing molecular size of the separated fractions. Mathematica…
Soil remediation: humic acids as natural surfactants in the washings of highly contaminated soils
The remediation of the highly contaminated site around the former chemical plant of ACNA (near Savona) in Northern Italy is a top priority in Italy. The aim of the present work was to contribute in finding innovative and environmental-friendly technology to remediate soils from the ACNA contaminated site. Two soils sampled from the ACNA site (A and B), differing in texture and amount and type of organic contaminants, were subjected to soil washings by comparing the removal efficiency of water, two synthetic surfactants, sodium dodecylsulphate (SDS) and Triton X-100 (TX100), and a solution of a natural surfactant, a humic acid (HA) at its critical micelle concentration (CMC). The extraction …
NMR-investigation of the mechanism of silver mercaptide thermolysis in amorphous polystyrene
Polymer-embedded silver clusters have been prepared by thermal decomposition of silver dodecylmercaptide previously dissolved in amorphous polystyrene. The morphology and structure of silver clusters have been determined by transmission electron microscopy (TEM) and large angle X-ray diffractometry (XRD), respectively. The mechanism involved in the thermolysis reaction was elucidated by different NMR techniques. The thermolysis produced thiol-derivatized silver clusters (i.e., silver clusters coated with a self-organized thiol monolayer, Agx(SC12H25)y) and had the effect of increasing the branching degree of polystyrene due to enhanced cross-linking.
O-Alkylation of a lignite humic acid by phase-transfer catalysis
A mild phase-transfer catalytic reaction has been conducted to O-alkylate the acidic functions of a lignite humic acid (HA), using tetrabutylammonium hydroxide as the phase-transfer catalyst. The HA acidic functional groups were made to react, in tetrahydrofuran, by nucleophilic substitution with several alkyl halides-methyl iodide, and ethyl, propyl, and butyl, and benzyl bromide. The occurrence of the O-alkylation reaction was assessed by elemental analysis and 1H NMR, CPMAS 13C NMR, and FTIR spectroscopy. Bonding of alkyl groups increased the carbon and hydrogen content and the H/C ratios of all the humic reaction products. Increased nitrogen in the reaction products suggested incomplete…
Spectroscopic and conformational properties of size-fractions separated from a lignite humic acid
Abstract A lignite humic acid (HA) was fractionated by preparative high performance size-exclusion chromatography (HPSEC) in seven different size-fractions. The size-fractions were characterized by cross polarization (CP) magic angle spinning (MAS) 13 C NMR spectroscopy and a further analytical HPSEC elution under UV and fluorescence detection. The alkyl hydrophobic components mainly distributed in the largest molecular-size-fraction, whereas the amount of oxidized carbons increased with decreasing size of fractions. Cross polarization time ( T CH ) and proton spin-lattice relaxation time in the rotating frame ( T 1 ρ (H)) were measured from variable contact time (VCT) experiments. The bulk…
Effects of Humic Substances and Soya Lecithin on the Aerobic Bioremediation of a Soil Historically Contaminated by Polycyclic Aromatic Hydrocarbons (PAHs)
The high hydrophobicity of polycyclic aromatic hydrocarbons (PAHs) strongly reduces their bioavailability in aged contaminated soils, thus limiting their bioremediation. The biodegradation of PAHs in soils can be enhanced by employing surface-active agents. However, chemical surfactants are often recalcitrant and exert toxic effects in the amended soils. The effects of two biogenic materials as pollutant-mobilizing agents on the aerobic bioremediation of an aged-contaminated soil were investigated here. A soil historically contaminated by about 13 g kg(-1) of a large variety of PAHs, was amended with soya lecithin (SL) or humic substances (HS) at 1.5% w/w and incubated in aerobic solid-phas…
In situ polymerization of soil organic matter by oxidative biomimetic catalysis
Abstract Background Agricultural practices that enhance organic matter content in soil can play a central role in sequestering soil organic carbon (SOC) and reducing greenhouse gases emissions. Methods We used a water-soluble iron-porphyrin to catalyze directly in situ oxidative polymerization of soil organic matter in the presence of H2O2 oxidant, with the aim to enhance OC stabilization, and, consequently, reduce CO2 emissions from soil. The occurred SOC stabilization was assessed by monitoring soil aggregate stability, OC distribution in water-soluble aggregates, soil respiration, and extraction yields of humic and fulvic acids. Results Soil treatment with H2O2 and iron-porphyrin increas…
State of the art of CPMAS 13C-NMR spectroscopy applied to natural organic matter
A number of different techniques are presently available for characterizing humified natural organic matter (NOM). Carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR) in the solid state using cross-polarization (CP) and magic angle spinning (MAS) represents the most powerful experimental approach used to collect direct information on the structural and conformational characteristics of humic carbon backbones. Despite the problems due to the presence of paramagnetic impurities and the generally low organic matter concentration, cross-polarization magic angle spinning 13C-NMR spectroscopy (CPMAS 13C-NMR) is applied in soil chemistry and geochemistry mainly because of its relevance in …
Evaluation of the factors affecting direct polarization solid state (31)P-NMR spectroscopy of bulk soils
Summary 31 P-NMR spectroscopy on bulk soils is a powerful tool for the identification of the different phosphorus forms in soils and for the evaluation of the dynamics of soil P. Up to now the majority of the papers dealt with liquid state 31 P-NMR spectroscopy on soluble soil organic substances. Only few papers were addressed to the study of the different phosphorus forms directly in bulk soils. In the present paper, some organic and inorganic phosphates of known structures, which are likely to be present in soil systems, were studied by direct polarization (DP) magic angle spinning (MAS) 31 P-NMR spectroscopy in order to understand the electronic factors responsible for chemical shifts of…
Structural Characterization of Isomeric Dimers from the Oxidative Oligomerization of Catechol with a Biomimetic Catalyst
In a previous paper, it has been reported about the formation of catechol di-, tri- and tetramers within an oxidative polymerization catalyzed by synthetic water-soluble iron-porphyrin as an efficient alternative to bio-labile natural peroxidase. It has also been demonstrated the occurrence of both C-C and C-O-C coupling mechanisms. However, since the coupling products were determined by mass spectroscopy, the exact bonding position could not have been precisely ascertained for the C-C bonded isomeric dimers that are the dominant products of catechol oligomerization. Therefore, here isolation and characterization of catechol isomeric dimers, obtained by oxidative coupling under the catalysi…
Solid state nuclear magnetic resonance spectroscopy as a tool to characterize natural organic matter and soil samples. The basic principles
Basic principles of solid state nuclear magnetic resonance spectroscopy (SS-NMR) are presented here. This paper is not pretending to provide an exhaustive treatment of the basics of SS-NMR. However, it will give an overview of the main applications in the characterization of environmental systems and will describe the problems related to the acquisition of quantitative solid state NMR spectra.
Precise measurement of 1H 90° pulse in solid-state NMR spectroscopy for complex and heterogeneous molecular systems
The 90 degrees pulse calibration is essential in NMR spectroscopy to prevent artefacts in the liquid state or to enhance cross-polarization efficiency in the solid state. We verified pulse-angle (PA) errors due to circuit impedances in solid-state NMR and suggested a possible solution to prevent the inconvenience of PA errors. The classic pulse sequences used to calibrate (1)H 90 degrees pulse lengths by direct detection of protons or by cross-polarization were modified in order to replace single (1)H pulses with (1)H pulse trains. Pulse trains were found to decrease the effect of PA imperfections in the calibration of basic pulses (i.e. 90 degrees and 180 degrees ) for a number of organic …
Response of Soil Microbial Communities to Iron-Porphyrin Catalytic Amendments.
Intensive agricultural practices strongly increase CO2 emission from soil. Synthetic metal-porphyrins were shown to significantly decreased CO2 emission from soil due to an in-situ catalysis of oxidative polymerization of soil organic matter. This research aimed to assess the effects of iron-porphyrin (POR) amendments on soil microbial communities in three arable soils under wheat and maize cropping located in Naples, Turin and Piacenza, characterized by different pedological and climatic conditions. Bulk-soil and rhizo-soil were sampled during 4 years and the microbial groups directly involved in organic matter (OM) mineralization and in key processes of the nitrogen cycle were examined. M…