Effect of paramagnetic cations on solid state 13C nuclear magnetic resonance spectra of natural organic materials

Abstract

The effect of cation (Zn²⁺, Cu²⁺, Pr³⁺) amendment on the solid state ¹³C nuclear magnetic resonance (NMR) spectral properties of organic materials was investigated. The organic materials were chosen to represent structures found in natural organic matter (NOM) from soils, waters, sediments, sewage sludges and plant residues, and included cellulose, pectin, chitin, collagen, a commercial humic acid, and charcoal. Cation amendment was shown to have little effect on the observability of ¹³C NMR signal, except for the paramagnetic amended pectin samples, for which observability was decreased from near 100% in the unamended sample to 19% for the Cu²⁺ amended sample and 71% for the Pr³⁺ amended sample. NMR relaxation parameters (T_1p H, T₁H) were more sensitive to cation amendment. For a number of the samples, a decrease in relaxation rate (increase in T_lpH and T₁H) was observed on amendment with Zn²⁺. This was ascribed to a decrease in molecular motion due to the chelating effects of Zn²⁺. An increase in relaxation rate (decrease in T_1pH and T₁H) was generally observed on amendment with Cu²⁺. The effects of amendment with Pr³⁺ varied. T₁H was more sensitive to the presence of paramagnetic species than was T_1pH. These results suggest that bound paramagnetic cations will only decrease the observability of ¹³C NMR signal in NOM samples (or domains within NOM samples) at high paramagnetic cation concentrations (>3%). There is great potential for the use of paramagnetic cation amendment to differentiate relaxation rates of domains within NOM samples, subspectra for which can then be generated using the proton spin relaxation editing (PSRE) technique.     

Quantitative solid-state 13C NMR spectroscopy of organic matter fractions in lowland rice soils

Spin counting on solid‐state ¹³C cross‐polarization (CP) nuclear magnetic resonance (NMR) spectra of two humic fractions isolated from tropical lowland soils showed that only 32–81% of potential ¹³C NMR signal was detected. The observability of ¹³C NMR signal (C_obs) was higher in the mobile humic acid (MHA) than in the calcium humate (CaHA) fraction, and increased with increasing intensity of irrigated rice cropping. NMR observability appeared to be related to the nature of the organic carbon, with phenol‐ and methoxyl‐rich samples having the higher values of C_obs. The Bloch decay (BD) technique provided more quantitatively reliable ¹³C NMR spectra, as evidenced by values of C_obs in the range 91–100% for seven of the eight humic fractions studied. The BD spectra contained considerably more aryl and carbonyl signal, and less O–alkyl and alkyl signal, with the greatest differences between CP and BD spectra observed for the samples with low C_obs(CP). The causes of low CP observability were investigated using the spectral editing technique RESTORE ( RE storation of S pectra via T _CH and T O ne R ho (T_1ρH) E diting). Rapid T_1ρH relaxation was found to be primarily responsible for the under‐representation of carbonyl carbon, whereas inefficient cross‐polarization was primarily responsible for the under‐representation of aryl carbon in CP spectra. Proton NMR relaxation rates T_1H and T_1ρH were found to correlate with other NMR properties and also with cropping management. Non‐uniform rates of T_1H relaxation in two of the CaHA fractions enabled the generation of proton spin relaxation editing subspectra.     

Spin accounting and RESTORE – two new methods to improve quantitation in solid-state 13C NMR analysis of soil organic matter

Rapid T_1ρH relaxation and inefficient cross‐polarization have long been known to affect quantitation in solid‐state ¹³C cross‐polarization (CP) NMR spectra of soil organic matter. We have developed two new techniques to overcome these problems. The first, spin accounting, enables accurate gauging of how quantitative a spectrum is likely to be. The result is expressed as the percentage of potential NMR signal that can be accounted for (C_obs). Spin accounting improves on the established spin counting technique by correcting for rapid T_1ρH relaxation and inefficient cross‐polarization. Spin accounting identifies three components: one that is well represented in CP spectra, one that is under‐represented in CP spectra due to rapid T_1ρH relaxation, and one that is under‐represented in CP spectra due to inefficient cross‐polarization. For a range of eight de‐ashed soils, C_obs was in the range 83–106%, indicating that virtually all potential signal could be accounted for after correcting for rapid T_1ρH relaxation and inefficient cross‐polarization. The second new technique, RESTORE (RE storation of S pectra via T _CH and T O ne R ho (T_1ρH) E diting), generates subspectra for the three components identified in spin accounting. The sum of the three RESTORE subspectra is essentially a corrected CP spectrum. The RESTORE spectra of all eight soils more closely resembled the corresponding, and presumably quantitative, Bloch decay spectra than did the CP spectra. RESTORE identifies the types of structures underestimated by CP, and the cause of their underestimation. Rapid T_1ρH relaxation most affected carbonyl and carbohydrate carbons, whereas inefficient cross‐polarization most affected aromatic carbons.     

The effect of water content on solid-state 13C NMR quantitation and relaxation rates of soil organic matter

Two hydrofluoric acid‐treated soils were prepared with water contents ranging up to 22% by exposing them to a range of atmospheric humidities. There was no effect of water content on the chemical shift distribution of nuclear magnetic resonance (NMR) signal in ¹³C cross‐polarization (CP) NMR spectra. The sensitivity of the ¹³C CP NMR spectra decreased slightly with increasing water content. Much of this decrease could be attributed to decreases in T_1ρH relaxation rates, caused by enhanced molecular mobility of the organic matter in the presence of absorbed water. Rates of T_1H relaxation were very sensitive to water content, and average T_1H relaxation rates decreased four‐ to five‐fold from the smallest to the largest water content. Rates of T_1H relaxation were non‐uniform, and were better modelled by two‐T_1H component fits than one‐T_1H component fits. The ratio of rapidly to slowly relaxing components increased with increasing water content. Proton spin relaxation editing (PSRE) subspectra revealed substantial changes in the nature of these two components with increasing water content. These results indicate the presence of an organic matter component that is very sensitive to water content, transforming from slowly relaxing at a small water content to rapidly relaxing at a greater water content. This component was shown to be rich in O–alkyl and carbonyl C, and may be hemicellulosic root exudates and microbial mucilages. The slowly relaxing PSRE component was a mixture of ligno‐cellulose and alkyl biopolymers, whereas the rapidly relaxing component was primarily charcoal for one of the soils, and was reminiscent of dissolved organic carbon for the other soil. These findings show that care must be taken in controlling water contents when using PSRE to study organic matter.     

Magnetic resonance imaging methods to reveal the real-time distribution of nickel in porous media

Direct and non‐destructive measurement of the sorption, diffusion and mobility of ions and molecules in porous media has applications in industry and environmental science. We used magnetic resonance imaging (MRI) to visualize the dynamic distribution of paramagnetic nickel (Ni⁺²) ions in porous media. Various MRI sequences were tested to image Ni²⁺ at small concentrations. Noisy gradient echo images had poor contrast between samples containing various Ni²⁺ concentrations. Turbo spin echo and spoiled gradient echo images showed a linear relation between Ni²⁺ concentrations and signal intensity over a wide range of concentrations. Spoiled gradient echo images resolved Ni²⁺ concentrations (down to 30 mg litre^?1) better than turbo spin echo images. However, for smaller concentrations, uncertainty in intensity values increased. A T₁ measurement, obtained using an inversion recovery sequence, showed a linear correlation between T₁ and Ni²⁺ concentration down to 1.5 mg litre^?1. In a glass bead medium with an ion exchange resin as an Ni sink, the real‐time development of the Ni²⁺ depletion zone around the resin, as Ni was sorbed into the resin, was imaged by T₁ mapping. A spatial resolution of 0.58 mm and a temporal resolution of less than a minute were achieved. The two‐dimensional Ni²⁺ gradient that was determined from MRI agreed well with geochemical modelling results. The results of this study showed that MRI, in particular T₁ mapping, can quantify microscale behaviour of paramagnetic species in porous media. However, ferromagnetic components that naturally occur in most soils can easily disturb the MRI signal.     

Evaluation of 1H NMR relaxometry for the assessment of pore‐size distribution in soil samples

¹H NMR relaxometry is used in earth science as a non‐destructive and time‐saving method to determine pore size distributions (PSD) in porous media with pore sizes ranging from nm to mm. This is a broader range than generally reported for results from X‐ray computed tomography (X‐ray CT) scanning, which is a slower method. For successful application of ¹H NMR relaxometry in soil science, it is necessary to compare PSD results with those determined from conventional methods. The PSD of six disturbed soil samples with various textures and soil organic matter (SOM) content were determined by conventional soil water retention at matric potentials between −3 and −390 kPa (pF 1.5–3.6). These PSD were compared with those estimated from transverse relaxation time (T₂) distributions of water in soil samples at pF 1.5 using two different approaches. In the first, pore sizes were estimated using a mean surface relaxivity of each soil sample determined from the specific surface area. In the second and new approach, two surface relaxivities for each soil sample, determined from the T₂ distributions of the soil samples at different matric potentials, were used. The T₂ distributions of water in the samples changed with increasing soil matric potential and consisted of two peaks at pF 1.5 and one at pF 3.6. The shape of the T₂ distributions at pF 1.5 was strongly affected by soil texture and SOM content (R² = 0.51 − 0.95). The second approach (R² = 0.98) resulted in good consistency between PSD, determined by soil water retention, and ¹H NMR relaxometry, whereas the first approach resulted in poor consistency. Pore sizes calculated from the NMR data ranged from 100 μm to 10 nm. Therefore, the new approach allows ¹H NMR relaxometry to be applied for the determination of PSD in soil samples and for studying swelling of SOM and clay and its effects on pore size in a fast and non‐destructive way. This is not, or only partly, possible by conventional soil water retention or X‐ray CT.     

Prediction of volumetric soil organic carbon from field‐moist intact soil cores

This study investigated the potential for visible–near‐infrared (vis–NIR) spectroscopy to predict locally volumetric soil organic carbon (SOC) from spectra recorded from field‐moist soil cores. One hundred cores were collected from a 71‐ha arable field. The vis–NIR spectra were collected every centimetre along the side of the cores to a depth of 0.3 m. Cores were then divided into 0.1‐m increments for laboratory analysis. Reference SOC measurements were used to calibrate three partial least‐squares regression (PLSR) models for bulk density (ρ_b), gravimetric SOC (SOC_g) and volumetric SOC (SOC_v). Accurate predictions were obtained from averages of spectra from those 0.1‐m increments for SOC_g (ratio of performance to inter‐quartile (RPIQ) = 5.15; root mean square error (RMSE) = 0.38%) and SOC_v (RPIQ = 5.25; RMSE = 4.33 kg m^?3). The PLSR model for ρ_b performed least well, but still produced accurate results (RPIQ = 3.76; RMSE = 0.11 Mg m^?3). Predictions for ρ_b and SOC_g were combined to compare indirect and direct predictions of SOC_v. No statistical difference in accuracy between these approaches was detected, suggesting that the direct prediction of SOC_v is possible. The PLSR models calibrated on the 10‐cm depth intervals were also applied to the spectra originally recorded on a 1‐cm depth increment. While a bigger bias was observed for 1‐cm than for 10‐cm predictions (1.13 and 0.19 kg m^?3, respectively), the two populations of estimates were not distinguishable statistically. The study showed the potential for using vis–NIR spectroscopy on field‐moist soil cores to predict SOC at high depth resolutions (1 cm) with locally derived calibrations.     

Speciation of cadmium,copper, lead,and zinc in contaminated soils

Abstract

To investigate the activity of free cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (Cd_T, Cu_T, Pb_T, and Zn_T, respectively), 0.43 MHNO₃‐extractable Cd, Cu, Pb, and Zn (Cd_N, Cu_N, Pb_N, and Zn_N, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca²⁺]. The activity of free Pb²⁺, Cd²⁺, Cu²⁺, and Zn²⁺ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L^‐1, Cu from 3.43 to 7.42 μg L^‐1, Pb from 1.23 to 5.8 μg L^‐1, and Zn from 24.5 to 34.3 μg L^‐. In saturation soil extracts, the activity of free Cd²⁺ ions constituted 42 to 82% of the dissolved fraction, for Cu²⁺the range was 0.1 to 7.8%, for Pb²⁺ 0.1 to 5.1% and for Zn²⁺2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd²⁺, Cu^2t, Pb²⁺, and Zn²⁺ ions.     

Integrated Nutrient Management Affects Fruit Yield of Sapota (Achras zapota L.) and Nutrient Availability in a Vertisol

ABSTRACT

We studied the effect of integrated nutrient management (INM) combinations on supplement of plant nutrient for quantitative and qualitative fruit production in sapota. Thus, 17 combinations of INM practices were evaluated on fruit yield of sapota and nutrient availability in a Vertisol of Chambal region, India. The results demonstrated that almost all treatment combinations comprised of recommended dose of fertilizer (RDF), i.e. 1,000:500:500 g NPK plant^?1 with application of organic and inorganic sources of nutrients had a significant effect on the fruit yield of sapota, soil microbial biomass, NPK content of leaf, fruit and soil over control (T₁). Among different treatments, application of 2/3rd part of RDF + 50 kg FYM + 250 g Azospirillum + 250 g Azotobacter plant^?1 (T₁₁) significantly enhanced the number of fruits plant^?1 (327.88), yield plant^?1 (29.03 kg) and yield ha^?1 (4.52 t). However, the soil microbial count of fungi (8.89 cfu g^?1 soil), bacteria (11.19 cfu g^?1 soil) and actinomycetes (5.60 cfu g^?1 soil) at fruit harvest was higher under the 2/3 of RDF +10 kg vermicompost + 250 g Azospirillum + 250 g Azotobacter plant^?1 (T₁₅). The leaf nitrogen content (N, 2.03%) was higher in T_15, while phosphorus (P, 0.28%) and potassium (K, 1.80%) content were higher in T₁₁. It is evident that treatment T₁₁ increased fruit yield by 32% in Sapota cv. Kalipatti compared to control. Therefore, combined application of nutrient sources proved not only beneficial for enhancing fruit yield of sapota but also sustaining soil health in Chambal region of south-eastern Rajasthan.     

Reduced activity of β‐glucosidase resulting from host‐guest interactions with dissolved fulvic acids as revealed by NMR spectroscopy

Interactions between fulvic acids (FAs) and a β‐glucosidase (GLU) enzyme and consequent modifications of enzymatic activity were investigated at pH 5.0 and 7.2 by ¹H nuclear magnetic resonance (NMR) spectroscopy. With increasing FA content, the enzyme proton signals were progressively broadened, while the relaxation (T₁ and T₂) and correlation (τ_c) times of GLU decreased and increased, respectively. Regardless of pH, these effects were greater for the hydroxy‐alkylic and aromatic protons of GLU, suggesting that the FA‐enzyme associations, which progressively limited GLU tumbling rate, resulted from weak interactions, such as H‐bonds and dispersive hydrophobic bonds. The catalytic activity of β‐D‐glucosidase, when in weakly bound complexes with FA, was studied by following the change of NMR signals of two different substrates, p‐nitrophenyl‐β‐D‐glucopyranoside (pNPG) and salicin, and their hydrolysis products. Spectral evidence suggests that enzyme activity was substantially reduced with increasing FA concentration and the rate reduction was more pronounced for salicin than for pNPG. The enzyme inhibition may be explained by either a partial cover of GLU active sites by fulvic molecules or modification of the enzyme conformational structure during formation of humic‐enzyme complexes. Our results indicate that even weak interactions of FA with GLU are sufficient to inhibit partially its catalytic activity, and that the environmental role of extracellular enzymes may be significantly reduced when coming into contact with organic matter in the soil.     

Glassy State Transition and Rice Drying: Development of a Brown Rice State Diagram

The effect of moisture content (MC) on the glass transition temperature (T_g) of individual brown rice kernels of Bengal, a medium‐grain cultivar, and Cypress, a long‐grain cultivar, was studied. Three methods were investigated for measuring T_g: differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and dynamic mechanical analysis (DMA). Among these methods, TMA was chosen, because it can also measure changes in the thermal volumetric coefficient (β) of the kernel during glass transition. TMA‐measured T_g at similar MC levels for both cultivars were not significantly different and were combined to generate a brown rice state diagram. Individual kernel T_g for both cultivars increased from 22 to 58°C as MC decreased from 27 to 3% wb. Linear and sigmoid models were derived to relate T_g to MC. The linear model was sufficient to describe the property changes in the MC range encountered during rice drying. Mean β values across both cultivars in the rubbery state was 4.62 × 10^‐4/°C and was higher than the mean β value of 0.87 × 10^‐4/°C in the glassy state. A hypothetical rice drying process was mapped onto the combined state diagram generated for Bengal and Cypress.     

Quantification of long‐chain fatty acids in dissolved organic matter and soils

The objective was to develop and adapt a versatile analytical method for the quantification of solvent extractable, saturated long‐chain fatty acids in aquatic and terrestrial environments. Fulvic (FA) and humic (HA) acids, dissolved organic matter (DOM) in water, as well as organic matter in whole soils (SOM) of different horizons were investigated. The proposed methodology comprised extraction by dichloromethane/acetone and derivatization with tetramethylammonium hydroxide (TMAH) followed by gas chromatography/mass spectrometry (GC/MS) and library searches. The C_10:0 to C_34:0 methyl esters of n‐alkyl fatty acids were used as external standards for calibration. The total concentrations of C_14:0 to C_28:0 n‐alkyl fatty acids were determined in DOM obtained by reverse‐osmosis of Suwannee river water (309.3 μg g^—1), in freeze‐dried brown lake water (180.6 μg g^—1), its DOM concentrate (93.0 μg g^—1), humic acid (43.1 μg g^—1), and fulvic acid (42.5 μg g^—1). The concentrations of the methylated fatty acids (n‐C_16:0 to n‐C_28:0) were significantly (r² = 0.9999) correlated with the proportions of marker signals (% total ion intensity (TII), m/z 256 to m/z 508) in the corresponding pyrolysis‐field ionization (FI) mass spectra. The concentrations of terrestrial C_10:0 to C_34:0 n‐alkyl fatty acids from four soil samples ranged from 0.02 μg g^—1 to 11 μg g^—1. The total concentrations of the extractable fatty acids were quantified from a Podzol Bh horizon (26.2 μg g^—1), Phaeozem Ap unfertilized (48.1 μg g^—1), Phaeozem Ap fertilized (57.7 μg g^—1), and Gleysol Ap (66.7 μg g^—1). Our results demonstrate that the method is well suited to investigate the role of long‐chain fatty acids in humic fractions, whole soils and their particle‐size fractions and can be serve for the differentiation of plant growth and soil management.     

Effect of Specific Mechanical Energy on Properties of Extruded Protein‐Starch Mixtures

The effect of the specific mechanical energy (SME) during extrusion of a protein‐starch mixture was studied by analyzing the glass transition temperature (T_g) and starch gelatinization. We found that the SME values of 344 to 2108 kJ/kg did not significantly change the T_g of the product. To explain the insensitivity of T_g to SME in spite of reported fragmentation taking place during extrusion, we studied the effect of the molecular weight (MW) on T_g in a model system consisting of dextrans of varying molecular weights. We found that the effect of the molecular weight on the T_g reached a plateau at 6.7 × 10⁴. Because the reported size of the fragments created during the extrusion process is larger than this, we were able to explain the apparent insensitivity of T_g to SME in the protein‐carbohydrate matrix studied. However, we found that starch gelatinization varied with SME, the degree of gelatinization being higher for systems exposed to higher SME.     

Effects of mineral surface iron on the CPMAS 13C-NMR spectroscopic detection of organic matter from soil fractions in an agricultural topsoil with different amendments

The decrease of NMR visibility of the C signal in soil samples due to the association between organic carbon (OC) and the topsoil mineral surface was investigated. CPMAS ¹³C‐NMR spectra were obtained for soil particle‐size fractions (< 2 μm, 2–20 μm, > 20 μm) and bulk soils from an agricultural topsoil (Chernozem) that had received three different amendments (no fertilization, mineral fertilization (NPK), mineral (NPK) and organic (cattle manure) fertilizations) at Bad Lauchstädt, Germany. The soil organic carbon content of the three soils depended on the degree of soil fertilization. There was no constant relationship between the total NMR signal intensity and the total amount of organic carbon (TOC) for all size fractions. Indeed, a key role played in the C signal intensity by the paramagnetic ferric ion from the clay content in soil fractions and bulk soils was confirmed. Thus, we describe the variations of C signal intensity by taking into account the distribution of clay‐associated OC and non‐associated OC pools. Depending on the amendment, the C signal visibility was weakened by a factor of 2–4 for the clay‐associated OC. This estimation was rendered possible by combining mineral specific surface area (SSA) measurements with the N₂ gas adsorption method (BET method) and determination of TOC and iron concentrations. This approach contributes to the quantitative evaluation of the CPMAS ¹³C‐NMR detection.     

Depletion of soil organic carbon and nitrogen under Pinus taeda plantations in Southern Brazilian grasslands (Campos)

Establishment of pine (Pinus spp.) plantations on grasslands could increase carbon (C) sequestration to counteract increased atmospheric carbon dioxide concentrations. In the grasslands of the southern Brazilian highland (Campos), large areas have been converted to Pinus plantations over the last 30 years. In order to assess the impact of this land‐use change on the amount and composition of soil organic matter (SOM), we investigated a grassland pasture site (G), and both an 8‐year‐old (P8) and a 30‐year‐old (P30) plantation with Pinus taeda. Soil samples down to 45 cm were analysed for texture, pH, soil organic carbon (SOC) and total nitrogen (N_tot) concentrations. Chemical composition of SOM was determined by using cross‐polarization magic angle spinning (CPMAS) ¹³C NMR spectroscopy. We analysed for stable C isotope (δ¹³C) and assessed the lignin composition by CuO oxidation. Additionally, contents of pyrogenic organic material (PyOM) were determined because the Campos is regularly burnt. Both pine plantations revealed relatively small SOC concentrations in the mineral soil of 72.6 mg g^?1 (P8) and 56.8 mg g^?1 (P30) and N_tot concentrations of 4.0 mg g^?1 (P8) and 2.9 mg g^?1 (P30) for the A horizon, while grassland showed significantly (P < 0.01) larger contents of 100.2 mg g^?1 for SOC and 5.9 mg g^?1 for N_tot. Accumulation of litter layers suggests decreased input of organic material into the mineral soil under pine, which was confirmed by the δ¹³C values and lignin composition. Smaller contents of vanillyl‐ (V), syringyl‐ (S), and cinnamyl (C)‐phenols, smaller ratios of S/V and C/V, and smaller ratios of acidic to aldehydic forms of V and S phenols indicated a high degree of decomposition of residual grass‐derived SOM in the upper part of the mineral soil (0–10 cm) under pine plantations. This was confirmed by CPMAS ¹³C NMR spectroscopy, showing an increasing Alkyl C/O‐Alkyl C ratio at the same depth. No significant changes in the contents of PyOM could be detected, but all sites tended to show the greatest concentrations at deeper soil depths > 15 cm, indicating a vertical relocation of PyOM. The results suggest that decomposition of residual SOM originating from grassland species contributes to the decrease of SOC and N_tot and to an acidification in the topsoil under pine plantations. We also suggest that slow litter decomposition and incorporation and the absence of fires at the plantations are additional reasons for the reduced amount of SOM. Depletion of SOM and the acidification of the topsoil may reduce the availability and supply of nutrients and diminish the C sequestration potential of the mineral soil.     

Evaluation of the factors affecting direct polarization solid state 31P-NMR spectroscopy of bulk soils

³¹P‐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 ³¹P‐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) ³¹P‐NMR spectroscopy in order to understand the electronic factors responsible for chemical shifts of the phosphorus (P) nucleus and to serve as guidelines to assign P resonances in soil spectra. Number of hydrating water molecules, type of counter‐cation, degree of covalence, and spatial conformation of P in phosphate structures were found to affect signal positions in ³¹P‐NMR spectra. Both hydrating water and increase in degree of covalence of the X‐O‐P bonds (X=H, Na) enhanced the electronic density (E_D) around P, thereby producing up‐field shifts in ³¹P‐NMR spectra. The exchange of the Na⁺ counter‐cation with NH₄⁺ resulted in an increase of the cation potential (P_C) that is a measure of the cation polarizing power, and induced a down‐field shift of P signals, due to a corresponding reduction in E_D around the P nucleus. Both NMR down‐ and up‐field shifts were observed in organic phosphates, and were dependent on the spatial orientation of the phosphate groups that may have been fixed anisotropically in the solid state. Based on the factors that influence P chemical shifts for standard phosphates, attempts to assign ³¹P‐NMR signals in the spectra of five different unperturbed bulk soils were made.     

Building and testing conceptual and empirical models for predicting soil bulk density

The development of pedotransfer functions offers a potential means of alleviating cost and labour burdens associated with bulk‐density determinations. As a means of incorporating a priori knowledge into the model‐building process, we propose a conceptual model for predicting soil bulk density from other more regularly measured properties. The model considers soil bulk density to be a function of soil mineral packing structures (ρ_m) and soil structure (Δρ). Bulk‐density maxima were found for soils with approximately 80% sand. Bulk densities were also observed to increase with depth, suggesting the influence of over‐burden pressure. Residuals from the ρ_m model, hereby known as Δρ, correlated with organic carbon. All models were trained using Australian soil data, with limits set at bulk densities between 0.7 and 1.8 g cm^?3 and containing organic carbon levels below 12%. Performance of the conceptual model (r² = 0.49) was found to be comparable with a multiple linear regression model (r² = 0.49) and outperformed models developed using an artificial neural network (r² = 0.47) and a regression tree (r² = 0.43). Further development of the conceptual model should allow the inclusion of soil morphological data to improve bulk‐density predictions.     

1H Nuclear Magnetic Resonance (NMR) and Differential Scanning Calorimetry (DSC) Studies of Water Mobility in Dough Systems Containing Barley Flour

This study used ¹H nuclear magnetic resonance (NMR) spin‐spin relaxation time (T₂) and differential scanning calorimetric (DSC) measurements of unfreezable water content (UFW), to assess water behavior in freshly prepared (25°C), refrigerator‐stored (4°C, one day), or freezer‐stored (–35°C, one day) doughs containing 5, 10, or 30% whole grain, air‐classified β‐glucan‐diminished, and air‐classified β‐glucan‐enriched (BGB‐E) barley flours. Three populations of water were detected by NMR, depending on moisture content of dough, namely, tightly (T₂₁, 2–5 msec), less tightly (T₂₂, 20–50 msec), and weakly (T₂₃, 100–200 msec) bound water. T₂₂ peak was always detectable, and T₂₂ peak time linearly correlated to moisture content of dough in a range of 0.7–2.0 g/g db (r = 0.99, P < 0.05). Freezer storage showed less effect on water mobility in dough compared with refrigerator storage, whereas cooking and cool storage of cooked dough significantly decreased the water mobility (P < 0.05). Adding barley flour steadily decreased the water mobility in dough, and the reduction was more significant with adding BGB‐E (P < 0.05). Immobile water content was calculated by extrapolating T₂₂ peak time versus total moisture content in dough and significantly correlated to the UFW content measured by DSC (r = 0.72, P < 0.05).     

Loading of VO2+ and Cu2+ to partially oxidized charcoal fines rejected from Brazilian metallurgical industry

Purpose

Charcoal is utilized in Brazil for the metallurgical industry. Small size pieces, called charcoal fines, are rejected and sometimes are used to produce energy by burning. This charcoal can be used as soil conditioner to improve retention of metal ions in soil. However, changing the charcoal's surface chemistry via oxidation may increase retention of metal ions.

Materials and methods

Two kinds of oxidants were employed, nitric acid and selenium dioxide/hydrogen peroxide. Vanadyl ion (VO²⁺) and copper ion (Cu²⁺) were utilized as probe to study the metal ion complexation by the partially oxidized charcoal obtained. FTIR and EPR spectroscopy were used to characterize the materials.

Results and discussion

Oxidation with nitric acid increased nitrogen content, while oxidation with SeO₂/H₂O₂ elevated carbon content of treated charcoals. Organic free radicals (OFRs) with the unpaired electron in p orbitals of aromatic structures were confirmed by the EPR g-factors that ranged from 2.0038 to 2.0031. The oxidation with selenium dioxide/hydrogen peroxide formed charcoal with largest quantity of OFR. Loading charcoal with VO²⁺ and Cu²⁺ resulted in formation of complexes were oxygen acted as coordination atom. The formed complexes were of axial symmetry. The configurations around the Cu²⁺ ions were: CUNCu²⁺ complex (more stable square planar symmetry) and CFNCu²⁺ complex (less stable distorted tetrahedral configuration). Both complexes had oxygen as coordinating atoms. CFNVO²⁺ and CFSeVO²⁺ complexes presented complexation sites of axial symmetry, C_4v, with oxygen as coordinating atoms.

Conclusions

The oxidative treatment of charcoal with SeO₂/H₂O₂ is more appropriate to produce soil organic conditioner for complexation of metal ions.     

Measurement and Comparison of Glass Transition and Sticky Point Temperatures of Distillers Dried Grains with Solubles (DDGS) with Varying Condensed Distillers Solubles (CDS) and Drying Temperature Levels

Distillers dried grains with solubles (DDGS) is the main coproduct of the U.S. fuel ethanol industry and has significantly impacted the livestock feed markets in recent years. Particle agglomeration and subsequent flowability problems during storage and transport are often a hindrance, a nuisance, and expensive. This paper aims at characterizing the glass transition (T_g) and sticky point (T_s) temperatures of DDGS samples prepared with varying condensed distillers solubles (CDS) levels (10, 15, and 20%, wb), drying temperatures (100, 200, and 300°C), and moisture contents (0, 10, and 20%, db), and it discusses implications on DDGS flowability behavior. Distillers wet grains were combined with specified levels of CDS and dried in a convection‐style laboratory oven to produce DDGS. Subsequently, predetermined amounts of water were added to the DDGS to achieve desired moisture content levels. To determine T_g (°C), a differential scanning calorimeter was used, whereas T_s (°C) was determined through a novel technique with a rheometer. Results indicated high correlations between observed T_s and observed T_g (R² = 0.87) data for DDGS samples. Also, the empirical model for predicted T_g = f (drying temperature, CDS level, and moisture content) based on the Gordon–Taylor model showed favorable R² (0.74). Stickiness of DDGS increased with an increase in moisture content, indicating flow problems resulting from moisture. It was found that drying temperatures and CDS levels each had significant effects on T_g and T_s as well.