Effects of variations in contact times and copper contents in a 13C CPMAS NMR study of samples of four organic soils

Contact time, T_c, was varied from 0.5 to 4 ms in a ¹³C CPMAS NMR study of samples of four organic soils differing only in copper content and degree of decomposition. Initial polarization was rapid, with maximum intensity reached at or before 0.5 ms contact time and a large decrease in intensity by 4 ms contact time. The distribution of intensity was determined by dividing the spectra into four regions, corresponding approximately to aliphatic, carbohydrate, aromatic and carboxyl carbons. Three samples, with up to 1150 p.p.m. Cu, showed small increases in aromaticity with increasing T_c, with the greatest effect between 0.5 and 1 ms, and fairly constant intensity distributions between 1 and 4 ms. The sample with 2920 p.p.m. Cu showed much greater increase in aromaticity with increasing T_c and a decrease in the 50–110 p.p.m. region, which is dominated by carbohydrate signals. T_1?^H was negatively correlated with increasing Cu content for all four regions of the spectra, but the effect was much larger and the correlation coefficient much higher for the carbohydrate region. A T_c of 1 ms appears suitable for organic soil samples; however, caution must be exercised in drawing conclusions from intensity data, especially where samples contain high concentrations of metals. These data also indicate a possible preferential localization of Cu in the carbohydrate or hydrophilic portions of the organic matter; ¹³C CPMAS NMR may provide a novel, non-perturbing method to study metal binding in organic soils.     

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.     

13C NMR studies of organic matter in whole soils: H. A case study of some Rothamsted soils

Nuclear magnetic resonance (NMR) spectra were obtained for solid samples of whole soils from three long–term field sites at Rothamsted Experimental Station, UK. In all sites, soil organic matter content was either increasing or decreasing due to contrasted long–continued treatments. Two soils were from Highfield, one from under old grassland (47 g organic C kg^?1) and one from an area kept as bare fallow following ploughing of grass 21 years previously (14 g organic C kg^?1). Three soils were taken from Broadbalk, two from plots within the Broadbalk Continuous Wheat Experiment which had received no fertilizer or animal manure annually for 148 years (7 and 27 g organic C kg^?1, respectively) and one from Broadbalk Wilderness, wooded section (38 g organic C kg^?1). Broadbalk Wilderness was arable until 1881 and has reverted to deciduous woodland in the subsequent 110 years. Two soils were from Geescroft, one from an arable field (9 g organic C kg^?1) and one from Geescroft Wilderness (35 g organic C kg^?1) which began reversion to deciduous woodland at the same time as Broadbalk Wilderness but is now acid (pH = 4.2) in contrast to Broadbalk which is calcareous (pH = 7.3). Solid–state ¹³C NMR spectra were obtained on a 300–MHz instrument using cross polarization (CP) and magic angle spinning (MAS). All samples exhibited peaks in the following spectral regions: 0–45 ppm (alkyl), 45–60 ppm (methoxyl, carbohydrate and derivatives), 60–110 ppm (carbohydrates and derivatives, C–α of peptides), 110–160 ppm (aromatics) and 160–185 ppm (carboxyl groups and derivatives). Within the spectrum of a specific sample it was not possible to determine the relative proportions of soil organic carbon in the different forms identified because a range of factors can potentially alter the relative areas of peaks in different regions of the spectrum. However, from a comparison of relative peak areas within a set of soils from a given site, differing only in organic matter content, information can be deduced regarding the forms of C that are more or less subject to change in response to land use or management. At all sites carbohydrate C appears to be the form that is most subject to change, suggesting that it is an ‘active’ fraction compared with the other forms. It was greatest where organic matter inputs were greatest (due to inputs of farmyard manure or reversion to woodland) and declined relative to other forms following ploughing of old grassland. Alkyl C increased as total C accumulated but did not decline relative to other forms following ploughing of grass. One reason for the non–quantitative nature of the soil ¹³C CPMAS spectra was a short (approximately 1 ms) component of the rotating–frame T_I relaxation time for H nuclei (T_1pH). This problem was not overcome by acquiring data at – 60°C. In principle, solid–state spectra of soils obtained by direct polarization (i.e. without CP) might produce quantitative results, but the low C content of most mineral soils (10–50 g C kg^?1) precludes this, given current instrumentation.     

Immobilization of 15N in forest litter studied by 15N CPMAS NMR spectroscopy

Solutions labelled with ¹⁵N were applied as (¹⁵NH₄)₂SO₄ or K¹⁵NO₃ to isolated microplots in the floor of mountain beech forest (Nothofagus solandri var. cliffortioides) and incubated for 135 days under field conditions of moisture and temperature. Solid state ¹⁵N CPMAS NMR spectra of the forest litter layer showed that more than 80% of the total signal intensity was attributable to the secondary amide-peptide peak. The degree of ¹⁵N enrichment or form of N did not alter the relative intensity of signals attributable to ¹⁵N in peptides, nucleic acids and aliphatic amine groups (amino sugars and free NH₂ on amino acids). Combinations of ¹³C and ¹⁵N-NMR spectra, edited by a process that exploited differences in proton spin properties between distinct categories of organic matter, indicated incorporation of ¹⁵N in humified organic matter rather than partly degraded plant material. This application demonstrated that solid state ¹⁵N CPMAS NMR has potential for use in studies of N immobilization under field conditions and with materials containing little N and small ¹⁵N enrichment.     

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.     

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.     

Impacts of Soil Management Practices on the Organic Matter Structure - Investigations by CPMAS 13CNMR-Spectroscopy

Humus properties of 42 soil samples or humic extracts of Ap horizons of Cambisols and Luvisols, from different field plots, kept for a long time under continuous management conditions, have been studied by quantitative CPMAS ¹³C NMR-spectroscopy. The shift range of the spectra were divided into 8 regions, with carbon absorptions from 0–45 (aliphatics), 45–60 (OCH₃), 60–80 (CO? CN), 80–110 (anomeric carbons), 110–140 (aryl—C), 140–160 (O-aryl-C) and 160–210 (COOH? C?O) ppm, respectively. Although soil samples and humic extracts were obtained from plots from different locations and sometimes widely differing organic carbon contents, variances in the relative absorptions of the selected ranges were rather small. Several absorptions were significantly correlated among each other or with soil carbon and microbial biomass contents. These correlations were discussed with the applied management and with other results about humus formation and properties. CPMAS ¹³C NMR-spectroscopy allows a reliable and comprehensive characterization of soil organic matter from soils without previous fractionation.     

Characterization of a Mediterranean litter by 13C CPMAS NMR: relationships between litter depth, enzyme activities and temperature

Organic matter mineralization of forest litter is catalysed by the action of different extracellular enzymes produced by microorganisms. Coupling enzyme activities with data on the general macromolecular structure of organic matter, provided by cross‐polarization magic angle spinning ¹³C nuclear magnetic resonance (¹³C CPMAS NMR), allows researchers new insights into organic matter degradation processes. In this paper, the effect of the temperature of incubation on the degradation processes was evaluated in three distinct layers (OhLn, OhLv and OhLf) of an evergreen oak litter (Quercus ilex L.), located in the Mediterranean area of south‐eastern France. We studied degradation phenomena by a combination of ¹³C CPMAS NMR and microbiological analysis. In order to determine the microbial activity of litter layers, three enzyme activities (laccase, cellulase and butyrate esterase) were measured in a 6‐month mesocosm study. Results showed an increase in the alkyl C to O‐alkyl‐C ratio and an increase of the phenolic C and carboxyl C regions, indicating a preferential degradation of polysaccharides. The aromaticity also increased with litter depth and degradation, and humification processes were more elevated at 30°C. anova showed significant effects (P < 0.001) of increased temperature, depth and time of degradation on microbiological variables. Further information is needed about the variations in temperature and temperature‐litter response and soil functions to link fundamental understanding of carbon stabilization, climate change and global C cycling.     

Organic N forms of a subtropical Acrisol under no-till cropping systems as assessed by acid hydrolysis and solid-state NMR spectroscopy

This study was conducted to investigate the influence of land-use systems (grassland and cropland) and of long-term no-till cropping systems [bare soil, oat/maize (O/M), pigeon pea+maize (P+M)] on the composition of organic N forms in a subtropical Acrisol. Soil samples collected from the 0- to 2.5-cm layer in the study area (Eldorado do Sul RS, Brazil) were submitted to acid hydrolysis and cross-polarization magic angle spinning (CPMAS) ¹⁵N and ¹³C nuclear magnetic resonance (NMR) spectroscopies. The legume-based cropping system P+M contained the highest contents of non-hydrolysable C and N, hydrolysable C and N, amino acid N and hydrolysed unknown N. The relative proportion of non-hydrolysable N was higher in bare soil (30.0%) and decreased incrementally in other treatments based on the total C and N contents. The amino acid N corresponded to an average of 37.2% of total N, and was not affected by land use and no-till cropping systems. The non-hydrolysable residue contained lower O-alkyl and higher aromatic C concentrations, as revealed by CPMAS ¹³C NMR spectroscopy, and higher C:N ratio than the bulk soil. No differences in the bulk soil organic matter composition could be detected among treatments, according to CPMAS ¹³C and ¹⁵N NMR spectra. In the non-hydrolysable fraction, grassland showed a lower concentration of aromatic and a higher concentration of alkyl C than other treatments. From CPMAS ¹⁵N NMR spectra, it could be concluded that amide N from peptide structures are the main organic N constituent. Amide structures are possibly protected through encapsulation into hydrophobic sites of organic matter and through organomineral interaction.     

腐熟鸡粪和农业废弃物堆肥中的芳香结构抑制了水芹种子和哈茨木霉的生长

To better understand the role of organic matter （OM） prepared from chicken manure and agriculture residues compost on the growth of plants （Lepidium sativum L.） and antagonistic fungi （Trichoderma harzianum）, we analyzed the structure and composition of extracted OM using fluorescence excitation-emission matrix （EEM） spectroscopy and solid-state 13C cross-polarization magic-angle- spinning nuclear magnetic resonance （13C CPMAS NMR） spectroscopy. The results showed that the EEM contours of water-extracted OM （WEOM） and alkali-extracted OM （AEOM） were similar. Furthermore, solid-state 13C CPMAS NMR spectroscopy demonstrated that water extraction could not proportionally pull out aromatic moieties （112-145 ppm） from compost, but the alkali method in proportion extracted both carbohydrates （65 85 ppm） and aromatic moieties. The results suggest that AEOM may better reflect the bulk OM composition of compost, and one should be cautious when applying WEOM as an alternative indicator of total compost OM. Further investigations demonstrated that, compared to carbohydrates, aromatic moieties played a predominant role in growth suppression of Lepidium sativum L. seeds and Trichoderma harzianum.     

Multivariate analysis of CPMAS 13C-NMR spectra of soils and humic matter as a tool to evaluate organic carbon quality in natural systems

A series of humic and fulvic acids isolated from different sources, size‐fractions separated from a humic acid, and three soils of different origin were subjected to CPMAS ¹³C‐NMR spectroscopy to obtain the distribution of their carbon contents. The relative areas of chemical shift regions in NMR spectra were used to apply a principal component analysis (PCA) to the three sets of samples. The multivariate analysis was successful in efficiently differentiating samples on the basis of the quality of their organic carbon content. The PC biplots based on two principal components distinguished objectively among samples as accurately as it was possible to do by subjective qualitative evaluation of the original spectra. In the case of the soils, a discriminant analysis (DA) was applied to build a classification model that allowed the validation of the three soils according to their origin. Percentage of validation in the classification model is expected to increase when a large number of NMR spectra are accumulated and/or the concentration of organic carbon in samples is enhanced. The multivariate analyses described are likely to become a useful tool to increase the importance of CPMAS ¹³C‐NMR spectra in the appraisal of natural organic matter variations in heterogeneous natural systems.     

Land-use effects on the composition of organic matter in particle-size separates of soils: II. CPMAS and solution 13C NMR analysis

Soils from A horizons of Eutrochrepts under spruce forest (Sf), mixed deciduous forest (Df), permanent grassland (Gp), and arable rotation (Ar) were fractionated into clay- (<2 μm), silt-(2–20 μm) and sand- (20–2000 μm) sized separates. ¹³C NMR spectroscopy was used to compare SOM composition across size separates and between land-use regimes. CPMAS ¹³C NMR spectroscopy showed that the intensity of signals assigned to carbohydrates (representing most O-alkyl C) and lignin (phenolic and methoxyl C) declined with decreasing particle size. Concurrently, alkyl C and C-substitution of aromatic C increased in the order sand, silt, clay. The amount of alkyl C correlated well with microbial resynthesis of carbohydrates. Solution ¹³C NMR spectra suggested that humic acids (HA) extracted from the size separates were richer in carboxyl C and aromatic C than the bulk size separates. Also HA reflected increasing percentage of alkyl C with decreasing particle size. O-alkyl C were lower in silt HA than in clay HA whereas aromatic C tended to peak in silt HA. These results suggested that sand-sized separates were enriched in plant residues (primary resources) whereas clay-sized separates were dominated by products of microbial resynthesis (secondary resources). Silt was rich in selectively preserved and microbially transformed primary resources. ¹³C NMR spectroscopy showed only small differences in SOM composition between land-use regimes, except that silt and silt HA from Ar were richer in aromatic C than those from the other plots. But enrichment factors (E= content in fraction/content in whole soil) revealed differences in the distribution of C species across the size separates. Relatively high E_aromatic (0.9) and E_o-alkyl (1.0) for sand from Gp indicated high amounts of plant residues, probably due to intense rhizodeposition and to occlusion of plant debris within aggregates. Low E_aromatic (0.3) and E_o-alkyl (0.3) for sand from Ar suggested depletion of primary resources, which could be attributed to disintegration of soil aggregates upon cultivation. A pronounced enrichment of alkyl C in Ar clay-sized separates (E_alkyl= 3.1) suggested large amounts of microbial carbon. Microbial products attached to clay surfaces by a variety of physico-chemical bondings appeared more stable against mineralization induced by cultivation than plant residues sequestered in aggregates.     

Transformation of organic matter from maize residues into labile and humic fractions of three European soils as revealed by 13C distribution and CPMAS-NMR spectra

The dynamics of incorporation of fresh organic residues into the various fractions of soil organic matter have yet to be clarified in terms of chemical structures and mechanisms involved. We studied by ¹³C‐dilution analysis and CPMAS‐¹³C‐NMR spectroscopy the distribution of organic carbon from mixed or mulched maize residues into specific defined fractions such as carbohydrates and humic fractions isolated by selective extractants in a year‐long incubation of three European soils. The contents of carbohydrates in soil particle size fractions and relative δ¹³C values showed no retention of carbohydrates from maize but rather decomposition of those from native organic matter in the soil. By contrast, CPMAS‐¹³C‐NMR spectra of humic (HA) and fulvic acids (FA) extracted by alkaline solution generally indicated the transfer of maize C (mostly carbohydrates and peptides) into humic materials, whereas spectra of organic matter extracted with an acetone solution (HE) indicated solubilization of an aliphatic‐rich, hydrophobic fraction that seemed not to contain any C from maize. The abundance of ¹³C showed that all humic fractions behaved as a sink for C from maize residues but the FA fraction was related to the turnover of fresh organic matter more than the HA. Removal of hydrophobic components from incubated soils by acetone solution allowed a subsequent extraction of HA and, especially, FA still containing much C from maize. The combination of isotopic measurements and NMR spectra indicated that while hydrophilic compounds from maize were retained in HA and FA, hydrophobic components in the HE fraction had chemical features similar to those of humin. Our results show that the organic compounds released in soils by mineralization of fresh plant residues are stored mainly in the hydrophilic fraction of humic substances which are, in turn, stabilized against microbial degradation by the most hydrophobic humic matter. Our findings suggest that native soil humic substances contribute to the accumulation of new organic matter in soils.     

Effect of long‐term combined nitrogen and phosphorus fertilizer application on 13C CPMAS NMR spectra of humin in a Typic Hapludoll of northeast China

Because of its insolubility, heterogeneity and structural complexity, humin is the least understood among the three fractions of soil humic substances. This research aimed to evaluate the long‐term effect of combined nitrogen and phosphorus (NP) fertilizer addition on the chemical structure of humin under maize (Zea mays L.) monoculture in a Typic Hapludoll of northeast China. Soil samples were collected 12 and 25 years after the initiation of the fertilizer treatment. Soil humin was isolated using NaOH‐Na₄P₂O₇ extraction to remove humic and fulvic acids, which was followed by HF‐HCl treatment to remove most of the inorganic minerals. Solid‐state ¹³C cross‐polarization magic angle spinning nuclear magnetic resonance (¹³C CPMAS NMR) spectroscopy was used to characterize the chemical structure of the humin isolates. Results showed that the organic carbon (C) content of humin increased after NP fertilizer addition, compared with a no‐fertilizer (CK) treatment. ¹³C CPMAS NMR indicated that O‐alkyl C and aromatic C of humin decreased, while alkyl C and the ratios of alkyl C/O‐alkyl C, aliphatic C/aromatic C and hydrophobic C/hydrophilic C all increased in the NP fertilizer treatment. The long‐term application of NP fertilizer changed the molecular structure of soil humin to be more alkyl and hydrophobic, and was thus beneficial to the sequestration and stability of organic C in soil.     

A rapid procedure to calculate lime requirements based on single titration with base

The lime requirement (LR) in 39 surface acid soil samples (0–30 cm) from western Greece was calculated using a single-addition titration of successive 3-mL 0.022 M calcium hydroxide [Ca(OH)₂]. Soil pH measurements and titrations were performed in soil/water (1:2) and in a soil/0.01 M CaCl₂ (1:2) suspension while being stirred. The results were referred to as ‘pH data group I’ and ‘pH data group II’, respectively. In each ‘pH data group’, the samples were separated into ‘pH data subgroups’, according to the total volume (mL) of 0.022 M Ca(OH)₂ added to increase the initial pH (pH_a) to a target value of 6.5 (pH_t). The fitted linear regression equation pH_t = b × volume + pH_a was used for each ‘pH data group’ to determine the slope b. The b-weighted mean for each ‘pH data group’ was calculated. The LR was then calculated as follows: Mg CaCO₃ ha^?1 = 0.495 (pH_t – pH_a)/b, where b is the average weighted mean from the two ‘pH data groups’ and is equal to 0.227. The validity of the above equation was confirmed after incubation with Ca(OH)₂ for 72 h. This procedure is simple and gives a rapid and accurate estimation of LR with respect to the environment.     

Predicting bare soil temperature. I. Theory and models for the multi-day mean diurnal variation

The energy balance equation for the soil-air interface is expressed, by suitable approximations, in a form linear in the surface temperature T₀. This forms the basis of two predictive models for the diurnal variation of T₀, averaged over a many-day interval, for potentially evaporating bare soil. Input data include total solar radiation, air temperature and vapour pressure, windspeed u_a, cloud cover c, and soil radiative, aerodynamic and thermal properties (the latter assumed uniform). In the simpler model, based on harmonic analysis, u_a and c are assumed constant. For N_t observations per day, an algebraic solution is found as a set of equations for the parameters of up to the first N_t/2 harmonics. In the second model, dynamic wind-speed is introduced, and a more complicated linear algebraic method of solution is required. The models have agroclimatic value, since by averaging they predict the thermal ‘climate’ of soil, in contrast to instantaneous models which describe the time-specific thermal ‘weather’.     

High-Time Resolution Analysis of Diel Variation in Methane Emission from Flooded Rice Fields

Methane (CH₄) emission from flooded rice fields was measured hourly over 24 h for rice (Oryza sativa L.) seasons in 2008 and 2009. The objectives of this study were to identify typical diel variation in CH₄ emission and to estimate the best time of day for optimum extrapolation of daily CH₄ emission. Our results showed distinct diel variation in CH₄ emission, which exhibited a maximum at 14:00–15:00 and a minimum at midnight. About 5.2–5.6% of total CH₄ emitted per day (110–160 mg CH₄ m^?2 d^?1) was released at 14:00–15:00. The diel pattern of CH₄ emission resembled that of air temperature (T_a). The T_a coupled with solar radiation could cause a difference in partial pressure of CH₄ (DPPC) through the gas conduit of the plant. The best extrapolation of daily CH₄ emission was achieved with data observed at 10:00–11:00. We concluded that DPPC-induced CH₄ emission is an important mechanism causing diel variation.     

Determination of nuclear magnetic resonance T2 cutoff in remoulded loess by the freezing point

Proton nuclear magnetic resonance (NMR) is widely applied to characterize the microscopic properties of hydrogen-containing porous media. The transverse relaxation time cutoff (T_2c) value is the crucial parameter for the quantitative analysis of NMR data. Currently, there is no universal method for the determination of the T_2c in clayey soils. This study aimed to develop a laboratory method for determining the T_2c of remoulded loess by the freezing point of loosely bound water. Malan loess, a kind of typical clayey silt, was used as test material. Based on the soil freezing characteristic, NMR measurements were performed on remoulded loess with different macro-parameter controls during the cooling process to obtain the T₂ spectrum at each target temperature. By analysing the variation of unfrozen water content with temperature reduction, the freezing point of loosely bound water and the T_2c value within the freezing-point range was determined. The freezing point of loosely bound water in remoulded loess is about −3 to −5°C and that of firmly bound water is less than −5°C. Accordingly, the T_2c value of remoulded loess is determined to be 1.5–1.8 ms. The assessment of heating and cooling process and different methods for determining the T_2c shows that the laboratory method by the freezing point is effective and reliable, and the T_2c determined by statistical methods is worthy of further study and improvement. The saturated permeability of remoulded loess is evaluated according to the determined T_2c, and two NMR-based permeability equations can well reflect pore water distribution in remoulded loess, but to a certain extent, both equations ignore soil microstructure, pore connectivity and chemical effects of pore solution. The laboratory method by the freezing point and the determined T_2c value of remoulded loess fill the gap of NMR measurement in loess analysis and are of great significance for low-plastic clays and clay types.     

Increases in pH and soluble salts influence the effect that additions of organic residues have on concentrations of exchangeable and soil solution aluminium

It has been suggested that additions of organic residues to acid soils can ameliorate Al toxicity. For this reason the effects of additions of four organic residues to an acid soil on pH and exchangeable and soil solution Al were investigated. The residues were grass, household compost, filter cake (a waste product from sugar mills) and poultry manure, and they were added at rates equivalent to 10 and 20 t ha^?1. Additions of residues increased soil pH measured in KCl (pH_(KCl)) and decreased exchangeable Al³⁺ in the order poultry manure > filter cake > household compost > grass. The mechanism responsible for the increase in pH differed for the different residues. Poultry manure treatment resulted in lower soil pH measured in water (pH_(water)) and larger concentrations of total (Al_T) and monomeric (Al_mono) Al in soil solution than did filter cake. This was attributed to a soluble salt effect, originating from the large cation content of poultry manure, displacing exchangeable Al³⁺ and H⁺ back into soil solution. The considerably larger concentrations of soluble C in soil solution originating from the poultry manure may also have maintained greater concentrations of Al in soluble complexed form. There was a significant negative correlation (r = ?0.94) between pH_(KCl) and exchangeable Al. Concentrations of Al_T and Al_mono in soil solution were not closely related with pH or exchangeable Al. The results suggest that although additions of organic residues can increase soil pH and decrease Al solubility, increases in soluble salt and soluble C concentrations in soil solution can substantially modify these effects.