Carbon deposition in soil rhizosphere following amendments with compost and its soluble fractions, as evaluated by combined soil-plant rhizobox and reporter gene systems

We determined the organic carbon released by roots of maize plants (Zea mays L.) when grown in soils amended with compost and its soluble fractions. In rhizobox systems, soil and roots are separated from the soil of a lower compartment by a nylon membrane. Treatments are applied to the upper compartment, while in the lower compartment luminescent biosensors measure the bioavailable organic carbon released by roots (rhizodeposition). The rhizobox-plants systems were amended with a compost (COM), its water extract (TEA), the hydrophobic (HoDOM) and hydrophilic (HiDOM) fractions of the dissolved organic matter (DOM) extracted from the compost. After root development, the lower untreated compartments were sampled and sliced into thin layers. The bioavailable organic carbon in each layer was assessed with the lux-marked biosensor Pseudomonas fluorescens 10586 pUCD607, and compared with total organic carbon (TOC) analyses. The TOC values ranged between 8.4 and 9.6 g kg(-1) and did not show any significant differences between bulk and rhizosphere soil samples in any treatment. Conversely, the biosensor detected significant differences in available C compounds for rhizosphere soils amended with various organic materials. Concentrations of available organic compounds in the first 2 mm of soil rhizosphere were 1.69 (control), 1.09 (COM), 2.87 (HiDOM), 4.73 (HoDOM) and 2.14 (TEA)micromol Cg(-1) soil g(-1) roots. The applied rhizobox-biosensor integrated method was successful in detecting and quantifying effects of organic amendments on organic carbon released by maize plant roots. This approach may become important in assessing the carbon cycle in agricultural soils and soil-atmosphere compartments.     

The molecular composition of humic substances extracted from green composts and their potential for soil remediation

Humic substances play empirically several essential functions in biogeochemical cycles such as storage of carbon, pollutants, nutrients and water, yet the underlying mechanisms remain poorly known because their precise molecular structure is largely unknown so far. Here, we extracted humic substances from biomass waste of bell pepper, fennel, artichoke, coffee ground, coffee husks, and nursery residues. We analyzed humic extracts by ultra-high resolution Orbitrap Fusion Lumos Tribrid 1 M mass spectrometry, using both positive photoionization and negative electrospray ionization modes, and by ¹³C cross polarization/magic angle spinning nuclear magnetic resonance spectroscopy. We identified 5000–7000 unique organic compounds in humic substances by integrating photoionization with electrospray ionization. The chemical distribution of all components was depicted by nuclear magnetic resonance. Humic substances from green composts are composed by a wide variety of hydrophilic and hydrophobic moieties, thus providing the required biosurfactant properties for effective soil washing capacities, with carboxyl-rich alicyclic molecules, fatty acids, and phenolic acids as major constituents. Overall, our findings provide a major insight in the molecular structure of humic substances, thus opening research on mechanisms ruling the origin, fate and behavior of humic substances.

     

Increased Sequestration of Organic Carbon in Soil by Hydrophobic Protection

 The impact of soil organic carbon dynamics on the global carbon cycle is still largely uncertain despite studies of agricultural activities and control emissions of greenhouse gases to the earth's atmosphere. Improved knowledge of organic matter dynamics should lead to reduction in CO₂ emissions. We used stable carbon isotope analysis to detect small changes in organic carbon storage and turnover upon soil treatments with a ¹³C-labeled aliphatic alcohol previously partitioned into soluble humic substances of varying hydrophobicity. We found that labeled organic carbon is increasingly protected from mineralization with increased hydrophobic character of humic matter. The stabilization of organic carbon by hydrophobic protection significantly reduced decomposition during incubation time in soil. Hydrophobic protection can become an useful tool to limit decomposition of fresh organic matter in soil and thus reduce CO₂ emission from agricultural soils on a global scale. Received: 1 March 1999 / Accepted in revised form: 16 June 1999     

Molecular properties of a fermented manure preparation used as field spray in biodynamic agriculture

Manure products fermented underground in cow horns and commonly used as field spray (preparation 500) in the biodynamic farming system, were characterized for molecular composition by solid-state nuclear magnetic resonance [¹³?C cross-polarization magic-angle-spinning NMR (¹³?C-CPMAS-NMR)] spectroscopy and offline tetramethylammonium hydroxide thermochemolysis gas chromatography-mass spectrometry. Both thermochemolysis and NMR spectroscopy revealed a complex molecular structure, with lignin aromatic derivatives, polysaccharides, and alkyl compounds as the predominant components. CPMAS-NMR spectra of biodynamic preparations showed a carbon distribution with an overall low hydrophobic character and significant contribution of lignocellulosic derivatives. The results of thermochemolysis confirmed the characteristic highlighted by NMR spectroscopy, revealing a molecular composition based on alkyl components of plant and microbial origin and the stable incorporation of lignin derivatives. The presence of biolabile components and of undecomposed lignin compounds in the preparation 500 should be accounted to its particularly slow maturation process, as compared to common composting procedures. Our results provide, for the first time, a scientific characterization of an essential product in biodynamic agriculture, and show that biodynamic products appear to be enriched of biolabile components and, therefore, potentially conducive to plant growth stimulation.     

Prenatal magnetic resonance imaging detection of temporal lobes and hippocampal anomalies in hypochondroplasia

Hypochondroplasia (HCH) is a genetic skeletal dysplasia, inherited in an autosomal dominant fashion. About 50–70% of HCH patients have a mutation in FGFR3 gene and in the majority of cases it is a de novo mutation. Recent magnetic resonance imaging studies on relative large cohorts of HCH patients have showed a central nervous system involvement with a high incidence of characteristic temporal lobe and hippocampal abnormalities. To the best of our knowledge, this report shows the first magnetic resonance imaging prenatal detection of characteristic brain anomalies in a case of HCH, molecularly confirmed through postnatal FGFR3 analysis. © 2014 John Wiley & Sons, Ltd.     

Spectroscopic and conformational properties of size-fractions separated from a lignite humic acid

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(1rho)(H)) were measured from variable contact time (VCT) experiments. The bulk HA was characterized by the shortest T(CH) values and the longest T(1rho)(H) values which suggested, respectively, one. an aggregation of components in a large conformation that favored a fast H-C cross polarization, and, two. consequent steric hindrances that prevented fast local molecular motions and decreased proton relaxation rates. Conversely, the separated size-fractions showed longer T(CH) values and shorter T(1rho)(H) values than the bulk HA, thereby indicating that they were constituted by a larger number of mobile molecular conformations. The UV and fluorescence absorptions were both low in the large size-fractions that mainly contained alkyl carbons, whereas they increased in the olephinic- and aromatic-rich fractions with intermediate molecular-size, and decreased again in the smaller fractions which were predominantly composed by oxidized carbons. These results support the supramolecular structure of humic substances and indicate that the observed variation in conformational distribution in humic association may be used to explain environmental processes with additional precision.     

Polymerization of humic substances by an enzyme-catalyzed oxidative coupling

 A novel understanding of the structural features of humic substances supports the self-assembly supramolecular association of relatively small molecules rather than their polymeric nature. An increase in the conformational stability of humus may thus be achieved through promotion of intermolecular covalent bondings between heterogeneous humic molecules by an enzyme-catalyzed oxidative reaction. We present evidence from high performance size exclusion chromatography (HPSEC) and diffuse reflectance infrared spectrometry (DRIFT) that oxidation of a humic material catalyzed by horseradish peroxidase stabilizes the humic structure by the formation of aryl and alkyl ethers and permanently enhances its molecular size. Received: 15 May 2000 / Accepted in revised form: 14 July 2000     

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 of pollutants by sonication and soxhlet was conducted before and after the soil washings. Soil A was richer in polycyclic aromatic hydrocarbons, whereas soil B had a larger content of thiophenes. Sonication resulted more analytically efficient in the fine-textured soil B. The coarse-textured soil A was extracted with a general equal efficiency also by soxhlet. Clean-up by water was unable to exhaustively remove contaminants from the two soils, whereas all the organic surfactants revealed very similar efficiencies (up to 90%) in the removal of the contaminants from the soils. Hence, the use of solutions of natural HAs appears as a better choice for soil washings of highly polluted soils due to their additional capacity to promote microbial activity, in contrast to synthetic surfactants, for a further natural attenuation in washed soils.