Applicability of solid state fast field cycling NMR relaxometry in understanding relaxation properties of leaves and leaf-litters

Abstract Inversion recovery high field solid state (SS) 1H NMR spectroscopy and fast field cycling (FFC) NMR relaxometry have been applied on dried leaves and leaf-litters from a reafforestated area in central Sicily (Italy) in order to evaluate relaxation properties in both slow ( 1 ≪ ω 0 2 τ C 2 ) and fast ( 1 ≫ ω 0 2 τ C 2 ) motion regimes. Namely, SS 1H NMR spectroscopy (i.e. slow motion regime conditions) revealed that two relaxation components (a fast and a slow one) can be identified in all the leaves and leaf-litter samples. The fast component was assigned to small sized plant metabolites, whereas the slow one was attributed to slowly tumbling macropolymeric molecules. FFC NMR relax…

Interactions between 2-Aminobenzothiazole and Natural Organic Matter as Evidenced by CPMAS Nitrogen-15 NMR Spectroscopy

Cross-polarization magic angle spinning (CPMAS) 15N nuclear magnetic resonance (NMR) spectroscopy was used to study the interactions between 2-aminobenzothiazole (ABT) and natural organic matter in the presence of the natural enzyme laccase and synthetic air. Through the use of synthesized model compounds, we were able to confirm previous findings by CPMAS 13C NMR spectroscopy that showed the formation of covalent amide bonds. We also provide evidence of the presence of two additional H bonds between ABT and the natural organic matter. Both H bonds involved the amino and thiazole groups of ABT.

Effect of RF Field Inhomogeneity and Sample Restriction on Spectral Resolution of CP/MAS-13C NMR Spectra of Natural Organic Matter

It is well known that the induced B1 magnetic field in an NMR coil is inhomogeneously distributed. However, this issue has so far received little attention in the field of environmental NMR. As this research field often aims at quanti- tative results as well as relaxation phenomena, the repercussions of such inhomogeneity on peak integrals and relaxation times need to be taken into account. The objective of the present study was to test standard recording conditions on different sample positions in an NMR coil in order to determine the effect of the RF field inhomogeneity on the spectrum of a molecularly complex humic material and on some standard molecules of known structure and conformati…

Fast field cycling NMR relaxometry characterization of biochars obtained from an industrial thermochemical process

Biochar has unique properties which make it a powerful tool to increase soil fertility and to contribute to the decrease of the amount of atmospheric carbon dioxide through the mechanisms of C sequestration in soils. Chemical and physical biochar characteristics depend upon the technique used for its production and the biomass nature. For this reason, biochar characterization is very important in order to address its use either for agricultural or environmental purposes. Three different biochars obtained from an industrial gasification process were selected in order to establish their chemical and physical peculiarities for a possible use in agronomical practices. They were obtained by char…

Preface to the Special Issue on ‘‘Applications and developments of magnetic resonance techniques in geosciences’’

Effect of Heating Time and Temperature on the Chemical Characteristics of Biochar from Poultry Manure

Poultry manure (PM) chars were obtained at different temperatures and charring times. Chemical-physical characterization of the different PM chars was conducted by cross-polarization magic angle spinning (CPMAS) (13)C NMR spectroscopy and thermal analysis. CPMAS (13)C NMR spectra showed that the chemical composition of PM char is dependent on production temperature rather than on production duration. Aromatic and alkyl domains in the PM chars obtained at the lowest temperatures remained unchanged at all heating times applied for their production. The PM char obtained at the highest temperature consisted only of aromatic structures having chemical nature that also appeared invariant with hea…

Dynamics of cross polarization in solid state nuclear magnetic resonance experiments of amorphous and heterogeneous natural organic substances

Nuclear magnetic resonance (NMR) experiments on carbon-13 in the solid state were done with cross polarization (CP) and magic angle spinning (MAS) in order to overcome the low NMR sensitivity of (13)C and the chemical shift anisotropy, respectively. In the present research, CPMAS (13)C-NMR spectra were collected by modulating the contact time needed for cross polarization (variable contact times experiments, VCT) on two different humic acids (a soil-HA and a coal-HA). VCT data were fitted by a model containing either a monotonic or a non-monotonic cross polarization term. The non-monotonic model, which fitted the experimental results better than the monotonic one, provided two cross-polariz…

Effect of Organic Amendments on the Evolution of Soil Organic Matter in Soils Stressed by Intensive Agricultural Practices

Losses of soil organic carbon often occur because of intensive agricultural practices that lead to removal of organic carbon following harvest production and to insufficient inputs. Organic amendments can be a very appropriate matrix for enhancing organic carbon content in very stressed agricultural soils. In general, they, enhancing soil organic matter, play an important role in environmental matrices due, for example, to their capacity in retaining water, in interacting with organic and inorganic pollutants, and in enhancing nutrient availability to plants. For this reason, the understanding of the mechanisms with which organic amendments interact with other chemicals in the environment i…

Effect of ramp size and sample spinning speed on CPMAS 13C NMR spectra of soil organic matter

Abstract Cross polarization (CP) magic angle spinning (MAS) 13C NMR spectroscopy is a solid state NMR technique widely applied to study the chemical composition of natural organic matter. In high magnetic fields (>7 T), fast sample spinning is required in order to reduce the influence of spinning sidebands underlying other chemical shift regions. As the spinning speed increases, the Hartmann–Hahn matching profiles break down into a series of narrow matching bands. In order to account for this instability variable amplitude cross polarization techniques (e.g. VACP, ramp-CP) have been developed. In the present study, we experimentally verified the stability of the Hartmann–Hahn condition unde…

Spatial patterns of, and environmental controls on, soil properties at a riparianepaddock interface

Abstract Riparian zones are prominent features of agricultural landscapes because they are the last point to intercept nutrients and sediments before they enter water bodies. We investigated the soil properties, nutrient dynamics and vegetation composition at the riparian–agriculture interface. Soil physicochemical and vegetation properties were spatially heterogeneous along the transition from the grazed paddock into the un-grazed and revegetated riparian zone. Soil C stocks varied considerably across the site, with values ranging from 2% in the paddock to 5% in the riparian zone. Using Bayesian model selection, a predictive model for total soil carbon was developed. By including soil mois…