Determination of organic carbon and nitrogen in particulate organic matter and particle size fractions of Brookston clay loam soil using infrared spectroscopy

The objective of this study was to determine whether models developed from infrared spectroscopy could be used to estimate organic carbon (C) content, total nitrogen (N) content and the C:N ratio in the particulate organic matter (POM) and particle size fraction samples of Brookston clay loam. The POM model was developed with 165 samples, and the particle size fraction models were developed using 221 samples. Soil organic C and total N contents in the POM and particle size fractions (sand, 2000–53 µm; silt, 53–2 µm; clay, <2 µm) were determined by using dry combustion techniques. The bulk soil samples were scanned from 4000 to 400 cm^?1 for mid‐infrared (MIR) spectra and from 8000 to 4000 cm^?1 for near‐infrared (NIR) spectra. Partial least squares regression (PLSR) analysis and the ‘leave‐one‐out' cross‐validation procedure were used for the model calibration and validation. Organic C and N content and C:N ratio in the POM were well predicted with both MIR‐ and NIR‐PLSR models ( = 0.84–0.92; = 0.78–0.87). The predictions of organic C content in soil particle size fractions were also very good for the model calibration ( = 0.84–0.94 for MIR and = 0.86–0.92 for NIR) and model validation ( = 0.79–0.94 for MIR and = 0.84–0.91 for NIR). The prediction of MIR‐ and NIR‐PLSR models for the N content and the C:N ratio in the sand and clay fractions was also satisfactory ( = 0.73–0.88; = 0.67–0.85). However, the predictions for the N content and C:N ratio in the silt fraction were poor ( = 0.23–0.55; = 0.20–0.40). The results indicate that both MIR and NIR methods can be used as alternative methods for estimating organic C and total N in the POM and particle size fractions of soil samples. However, the NIR model is better for estimating organic C and N in POM and sand fractions than the MIR model, whereas the MIR model is superior to the NIR model for estimating organic C in silt and clay fractions and N in clay fractions.     

Determination of total soil organic C and hot water‐extractable C from VIS‐NIR soil reflectance with partial least squares regression and spectral feature selection techniques

The calibration of soil organic C (SOC) and hot water‐extractable C (HWE‐C) from visible and near‐infrared soil reflectance spectra is hindered by the complex spectral interaction of soil chromophores that usually varies from one soil or soil type to another. The exploitation of spectral variables from spectroradiometer data is further affected by multicollinearity and noise. In this study, a set of soil samples (Fluvisols, Podzols, Cambisols and Chernozems; n = 48) representing a wide range of properties was analysed. Spectral readings with a fibre‐optics visible to near‐infrared instrument were used to estimate SOC and HWE‐C contents by partial least squares regression (PLS). In addition to full‐spectrum PLS, spectral feature selection techniques were applied with PLS (uninformative variable elimination, UVE‐PLS, and a genetic algorithm, GA‐PLS). On the basis of normalized spectra (mean centring + vector normalization), the order of prediction accuracy was GA‐PLS ? UVE‐PLS > PLS for SOC; for HWE‐C, it was GA‐PLS > UVE‐PLS, PLS. With GA‐PLS, acceptable cross‐validated (cv) prediction accuracies were obtained for the complete dataset (SOC, , RPD_cv = 2.42; HWE‐C_cv, , RPD_cv = 2.13). Splitting the soil data into two groups with different basic properties (Podzols compared with Fluvisols/Cambisols; n = 21 and n = 23, respectively) improved SOC predictions with GA‐PLS distinctly (Podzols, , RPD_cv = 3.14; Fluvisols/Cambisols, , RPD_cv = 3.64). This demonstrates the importance of using stratified models for successful quantitative approaches after an initial rough screening. GA selection frequencies suggest that the spectral region over 1900 nm, and in particular the hydroxyl band at 2200 nm are of great importance for the spectral prediction of both SOC and HWE‐C.     

SATURATION PERCENTAGE AS A MEASURE OF SOIL TEXTURE IN THE LOWER INDUS BASIN

The saturation percentage is related to the mechanical constituents of a soil: and is therefore a quantitative expression of soil texture. Profiles may be described in terms of the S.P.; thus Maps may be drawn showing quantitative changes in texture, and associated statements of the reliability of an S.P. estimate and the probable error of the position of a textural contour be made. Decomposition of the calcium carbonate component should be avoided in routine soil survey work.     

THE MECHANICAL STRENGTH OF UNSATURATED POROUS GRANULAR MATERIAL

The influence of pore-water suction on the strength of a porous material is that it contributes a compressive load which increases the shear strength. When the material is unsaturated, the normal load or effective stress is due, in part to the continuous water at measured suction in unemptied pores, and in part to isolated bodies in nominally emptied pores at suctions approximating to the suction at emptying. When the material is draining from saturation, the effective stress σ is where S is the fraction of saturation, α is the fraction of the initial water content drained at the maximum suction, _Ps_d is the prevailing pore water suction, and _Ps_d is a suction passed through in reaching _pS_d at which the reduction of S is dS. When the material is rewetting, the relationship becomes where _ps_w is now the prevailing suction during wetting and f is a distribution function of the degree of saturation such that δS is the fractional saturation removed in the suction range δs_d at s_d and regained in the suction range δs_w at s_w. _ms_d is the maximum suction attained. The effective stress is revealed experimentally by unconfined compression tests on samples with imposed pore water suctions, and the dependence on this suction confirms reasonably that which is predicted by the theoretical formulas.     

Verteilung von Stickstoff auf Sproß und Wurzel bei jungen Bohnenpflanzen nach der Aufnahme von NO und NH

Translocation of nitrogen to the shoot of young bean plants after uptake of NO and NH by the root Phaseolus vulgaris plants (var. nana, cv. Saxa) at the primary leaf stage (without nodules) were fed during 6 hours with ¹⁵NO and ¹⁵NH, respectively. 24 hours after the absorption period more ₁₅N from the absorbed NO was translocated from the root to the shoot. The presence of NH in the nutrient solution enhanced the translocation of ¹⁵NON, probably by an inhibition of nitrate reductase. NH_4-⁺¹⁵N is mainly retained in the root by a high incorporation into the root protein. It can be concluded that nitrogen from newly absorbed NO is not retained and used for protein synthesis in the root according to the root's potential to synthesize protein. Nitrate reduction in the root is considered to be the limiting factor. This is supported by the fact that withdrawal of NO in the nutrient solution prior to the ¹⁵N-experiment increased NOtranslocation to the shoot as a consequence of a lowered level of nitrate reductase. In an experiment with ¹⁴NOsupply to the roots and ¹⁵NOapplication to the primary leaves (infiltration method) a considerable amount of ¹⁵N was translocated from the leaves to the roots. This indicates that an insufficient NOreduction in the root can be substituted by a retranslocation of reduced N-compounds from leaves to the roots. The proportion of NO reduced in the root influences also the pattern of primary distribution of nitrogen in the shoot of plants at the 4 leaf stage. At a concentration of 0,2 meq/l NO in the nutrient solution as compared to 20 meq/l NO during 10 hours a relative higher amount of ₁₅N was transported from the root to the younger, growing leaves i.e. via the phloem to metabolic sinks.     

THE MEASUREMENT AND MECHANISM OF ION DIFFUSION IN SOIL

If an exchangeable ion in soil diffuses along a liquid and solid pathway, its diffusion coefficient may be expressed as where D, v, f, C are diffusion coefficient, volume fraction, impedance factor, and concentration terms and the suffixes _l,_S refer to liquid and solid. The self-diffusion coefficient of the ion is then where D′, D′_t, and D′_s, are self-diffusion coefficients. D and D′ will vary with concentration. In diffusion out of the soil to a zero sink, the appropriate average diffusion coefficient is, approximately, the self-diffusion coefficient in the undisturbed soil. Diffusion of one ion species is influenced by other ions diffusing in the system through the diffusion potential set up. When ions are diffusing to plant roots, the diffusion potential is likely to be small. A more likely, though more complicated, expression for D than the first equation above is derived by assuming the ion to follow solid and liquid pathways in series as well as in parallel.     

QUALITY CONTROL IN SOIL SURVEY

The paper examines 66 Australian soil surveys in a variety of terrains (but not close forest), by several survey procedures, and published at a range of map scales. It relates the Survey Effort (E) of professional staff (in man-days per km²) to (I) survey procedure, (2) the kind of mapping unit, and (3) the intricacy of the soil pattern mapped. Intricacy (I), the average number of mapped soil boundaries crossed by 1 km of random linear traverse, is related to the total length of mapped boundary (km per km²). When the surveys are grouped according to survey procedure and mapping unit, the survey effort for each group may be described by a regression of the form . B could not be shown to differ significantly between groups. D varied in the ratio 0.5: I, according to whether or not surveys used air photograph interpretation, and in the ratio 0.3:0.7:1.o, according to whether they mapped land systems, other compound mapping units, or simple mapping units. Since the choice of survey procedure and mapping unit is usually governed by the intricacy of the soil pattern the effect of these factors can be summarized in a single regression for all 66 surveys: There is a significant (P≤ 0.001) log-log regression between I and map scale.     

Lead sorption to selected Portuguese soils

We studied the interaction of lead with seven Portuguese soils with different physical and chemical properties in order to elucidate more fully the behaviour of Pb in soil. We studied these adsorption phenomena by voltammetric titrations with differential pulse polarography (DPP) at different pH (6.0–7.2) and ionic strengths, I (0.010–0.50 m ) in order to clarify some of the factors that might control soil sorption capacity for Pb. From the voltammetric data, average formation constants, , and binding capacity, C_c, have been estimated according to a surface complexation model based on Scatchard and van den Berg–R?zic methods. Linear Scatchard and van den Berg–R?zic plots (r≥ 0.99) indicated that the results can be interpreted according to the existence of just one predominant active site for Pb(II) adsorption. The values from both procedures () agreed in all cases (r= 0.938, n= 66, P < 0.001). The same happened with C_c values that were statistically equivalent (r= 0.9998; n= 66; P < 0.001). The C_c values were found to depend on the pH and I, as well as on the soil properties. Either Langmuir or Freundlich isotherms fitted the experimental data well (r > 0.90, P < 0.05). The lead binding capacities were strongly and significantly correlated (P < 0.05) with pH, cation exchange capacity, organic carbon, loss‐on‐ignition, total Al₂O₃ content, extractable forms of Al and pyrophosphate extractable Fe, [Fe_p]. From a forward, stepwise regression model we concluded that [Al₂O₃], [Pb′] (concentration of labile lead in solution), [Fe_p], pH and I are able to explain more than 99.7% of the variation in lead sorption in our soils. The soils’ surface groups with special affinity to Pb(II) are in the inorganic fraction associated with aluminium.     

Nitratammonifizierung im Boden mit Abwasserverrieselung

Nitrate Reduction to Ammonium in a Soil with Wastewater Irrigation Flooding with wastewaters including 48 mg/l NH-N, 15 mg/l organic N and 63 mg/l K¹⁵NO-N has led to strong nitrogen losses by denitrification from a sandy Cambisol. Beside this ¹⁵NH was formed also. Possible reasons of the nitrate reduction to ammonium are discussed and conclusions for practical wastewater irrigation are drawn.     

Soil wetting‐drying and water‐retention properties in a mine‐soil treated with composted and thermally‐dried sludges

The main objective of this study was to analyse how different sewage sludges influence soil wetting and drying dynamics. Three composted and three thermally‐dried municipal sludges from different wastewater plants located in Catalonia (NE Spain) were mixed with a mine‐soil obtained from a limestone quarry. Measurements of the time required to reach zero contact angle () and water holding time (WHT) provided information on the time required for a mine‐soil to reach its complete wettability and the residence time of water stored between ?0.75 and ?25 MPa of soil suction, respectively. One month after sludge amendments, one composted and one thermally‐dried sludge significantly increased . WHT was increased in the mine‐soil treated by composted sludges (50.6% by Blanes' sludge, 65.5% by Manresa's sludge and 52.5% by Vilaseca's sludge) one month after sludge amendments. The amount of water retained in the mine‐soil was increased by all composted sludges and one thermally‐dried sludge after one month (by 42.3% with Blanes' sludge, 42.3% with Manresa's sludge, 65.7% with Vilaseca's sludge and 23.9% with Mataró's sludge) and one year after sludge amendments and at a small suction. Increments in WHT corresponded with the amount of water retained so the time‐scale of soil water availability should also be considered. The value was modified mainly by increments in carbon stock and microbial biomass, while the WHT was modified mainly by increments in pH and electrical conductivity. Under similar air‐drying conditions, mine‐soil treated with composted sludges retained more water for longer compared with thermally‐dried sludges.     

Relationship between equivalent salt solution series of different soils

Equivalent salt solution series have been previously defined as solutions with combinations of sodium absorption ratio (SAR) and electrolyte concentration (E_c) producing the same extent of clay swelling in a given soil. The present study shows that there is a high (r²>0.96) positive correlation between log E_c and log SAR of equivalent salt solutions series, in the equation: where a₁ and b₁ are constants for each equivalent salt solution series for a given soil. Log a₁ could also be represented as a linear function of b₁ resulting in the equation: where a₂ and b₂ are constants for a given soil. Solving this equation using any given value of b₁ yields the combinations of SAR and E_c which make up each equivalent salt solution series for a given soil. The relationship between log a₁ and b₂ for three soils from western United States, namely Waukena, Pachappa and Grangeville, was similar, with their combined data having a r² value of 0.96. This indicated that a single set of equivalent salt solution series values could be used for these three soils which have different clay contents and clay mineralogy. Prediction of hydraulic conductivity decreases with E_c reduction at given values of SAR in red-brown and alluvial soils from southern Tasmania, using the equivalent salt solution series values for Waukena soil, showed similar patterns to measured values and also to those predicted using the equivalent salt solution values applicable to the respective Tasmanian soils. Thus, available data indicate that the same set of equivalent salt series could be applied to the five soils studied. If further testing shows that a single set of equivalent salt solutions values could be applied to all or large groups of soils, this would facilitate the application of the equivalent salt solution concept to predict salt solution flow in the field.     

Comparison of urease inhibitor N‐(n‐butyl) thiophosphoric triamide and oxidized charcoal for conserving urea‐N in soil

Charcoal‐based amendments have a potential use in controlling NH₃ volatilization from urea fertilization, owing to a high cation‐exchange capacity (CEC) that enhances the retention of NH . An incubation study was conducted to evaluate the potential of oxidized charcoal (OCh) for controlling soil transformations of urea‐N, in comparison to urease inhibition by N‐(n‐butyl) thiophosphoric triamide (NBPT). Four soils, ranging widely in texture and CEC, were incubated aerobically for 0, 1, 3, 7, and 14 d after application of ¹⁵N‐labeled urea with or without OCh (150 g kg^?1 fertilizer) or NBPT (0.5 g kg^?1 fertilizer), and analyses were performed to determine residual urea and ¹⁵N recovery as volatilized NH₃, mineral N (as exchangeable NH , NO , and NO ), and immobilized organic N. The OCh amendment reduced NH₃ volatilization by up to 12% but had no effect on urea hydrolysis, NH and NO concentrations, NO accumulation, or immobilization. In contrast, the use of NBPT to inhibit urea hydrolysis was markedly effective for moderating the accumulation of NH , which reduced immobilization and also controlled NH₃ toxicity to nitrifying microorganisms that otherwise caused the accumulation of NO instead of NO . Oxidized charcoal is not a viable alternative to NBPT for increasing the efficiency of urea fertilization.     

A LANGMUIR TWO-SURFACE EQUATION AS A MODEL FOR PHOSPHATE ADSORPTION BY SOILS

For forty-one soils (pH > 5.0) from southern England and eastern Australia, the Langmuir equation was an excellent model for describing P adsorption from solutions < 10^-3M P, if it was assumed that adsorption occurs on two types of surface of contrasting bonding energies. For most of these soils, which were relatively undersaturated with P, this equation may be written as: where x = adsorption, k = adsorption/desorption equilibrium constant, x_m= monolayer adsorption capacity, and c = equilibrium solution concentration. The relative magnitude of the parameters for each surface were approximately: x_m= 0.3 x^″_m=0.3 and k′= 100 k. More than 90 per cent of the native adsorbed P occurs on the high-energy surface in most soils.     

Toxic levels of metals in Ferralsols under natural vegetation and crops in New Caledonia

The chemistry of soil solutions and the potential toxicity of trace metals (Co, Cr, Cu, Ni and Mn) were investigated on soils formed on ultramafic rocks. Soil solutions were collected along a soil toposequence under natural vegetation and under a cropped field. In the latter, metal speciation and species activity were computed with the WHAM 6 model. Total element concentrations varied with the soil topographic position. Upslope, in well‐drained soils, they were relatively small with mean concentrations of <0.2 µmol l⁻¹ for Co and Cr and <2 µmol l⁻¹ for Ni and Mn. Downslope, in temporarily waterlogged soils, concentrations reached 37 (Mn), 5.6 (Ni), 1.9 (Co) and 0.1 (Cr) µmol l⁻¹. Under crops, Ni, Mn and Co concentrations were similar to those under natural vegetation, but Cr concentration averaged 5 µmol l⁻¹. Cu concentration was close to 1 µmol l⁻¹. Free‐ion species amounted to 53–71% of all species for Co, Ni and Mn but only 5% for Cu. Cr was almost entirely in the Cr(VI) form (CrO, HCrO. The free‐metal‐ion activities were in the range 26–81% of the corresponding free‐metal‐ion concentration. Comparing our data with levels that are toxic to crops, Ni and Cr are potentially toxic in the well‐drained and the poorly‐drained soils. In the latter, Co and Mn are also potentially toxic. Both the large concentration of metals and the chemical species in which they occur in solution could limit the use of the land for agricultural purpose.     

EFFECTS OF CATION EXCHANGE MATERIAL ON ZINC ADSORPTION BY SOILS

The adsorption of Zn by soils which are different in their major cation-exchange materials was measured at equilibrium Zn concentrations up to 10^?2 M in 10^?2 to 10^?3 M CaCl₂. The results are interpreted on K^Zn_Ca[Zn]_soil plots, where K^Zn_Ca is the selectivity coefficient defined by the equation All natural samples except those containing halloysite exhibited no or very small specific Zn adsorption. All Ca-saturated samples exhibited specific Zn adsorption dependent on cation-exchange materials. The cation-exchange sites with high selectivities for Zn (K^Zn_Ca > 10) constitute more than 40 per cent of the total exchange sites in soils containing allophane, imogolite, and halloysite, whereas those with moderate to low selectivities for Zn (K^Za_Ca < 10) predominate in montmorillonitic, vermiculitic, and humic soils. Differences in the contribution of the respective cation-exchange materials to specific Zn adsorption are discussed relating to differences in the origin of their negative charge.     

THE EFFECT OF ORGANIC MATTER ON THE BULK AND TRUE DENSITIES OF SOME UNCULTIVATED PODZOLIC SOILS

Organic matter content was found to have a dominant effect on both the bulk and true densities of soil in the organic and eluvial horizons of the podzolic soils examined. The soils were stone-free, structureless, and of similar texture. The effects of organic matter on bulk density were described by the equation: A similar equation was devised for true density. Use of these equations indicated that, in the soils examined, total pore space could be predicted from organic matter content measured as per cent loss on ignition.     

THE RESPONSE OF UNSATURATED SOILS TO ISOTROPIC STRESS

Soil compression is caused in agriculture by tillage implements, plant roots, treading by animals, and by wheels and tracks of vehicles. Increases in soil density resulting from compression usually reduce crop growth and yield. Compression and expansion of samples of five remoulded soils, each at several moisture contents, were investigated. Soil samples were subjected to isotropic stress of up to 3.5 MN m^?2 in a pressure cell. Volume changes were measured by the volume of pore fluid effused or infused through one of the sample surfaces. Particle packing densities, D, were well described by the equation where D₀ is the maximum limiting value of D, P is the applied isotropic stress, and B, C, K, L are adjustable parameters. One of the exponential terms in this equation describes deformation of soil crumbs and the other describes rearrangement of individual particles. Two sample sizes gave similar values for the equation parameters. A small increase in moisture content results in a large increase in soil compressibility. It is hypothesized that resistance to compression may be one of the principal influences in the mechanical restriction of root growth.     

Ferrous and ferric iron ratio in normal and chlorotic bean plants (Vicia faba L.)

The objective of this study was to determine the ratio and amount of Fe II and Fe III iron in different parts of 20 and 40 day old bean plants grown in pots under normal and HCO-treatment. The Fe II and Fe III iron determination was carried out by a modification of a method described by Vogel (1969). The Fe II and Fe III concentrations in the plant varied according to its age, the plant part, the order of leaves and HCO-treatment. At the second sampling date, the lower total iron content in the lower leaf particularly under the HCO-treatment suggests that the supply of iron from the roots was restricted. The iron content of the different leaves was almost evenly divided into Fe II and Fe III at the first date. At the second date, most of the iron in the bud leaf was present as Fe II. Under HCO-treatment the Fe II content of the bud leaf and the flower was similar as in the corresponding parts of the normal green plants whereas the Fe III content was considerably lowered in these plant parts as result of the HCO-treatment. The results indicate a substantial retranslocation of iron from older to younger leaves and a higher Fe II/Fe III ratio in flowers and bud leaves particularly under HCO-induced chlorosis.     

How does the application of different nitrification inhibitors affect nitrous oxide emissions and nitrate leaching from cow urine in grazed pastures?

Nitrous oxide (N₂O) is a potent greenhouse gas, and nitrate () is a water contaminant. In grazed grassland, the major source of both leaching and N₂O emissions is nitrogen (N) deposited in animal excreta, particularly in the urine. The objective of this study was to determine the effectiveness of two nitrification inhibitors: (i) a solution of dicyandiamide (DCD) and (ii) a liquid formulation of 3,4‐dimethylpyrazole phosphate (DMPP) for reducing N₂O emissions and leaching from urine patch areas in two grazed pasture soils under different environmental conditions. In the Canterbury Templeton soil, the nitrification rate of ammonium from the animal urine applied at 1000 kg N/ha was significantly decreased by the application of DCD (10 kg/ha) and DMPP (5 kg/ha). N₂O emissions, measured over a 3‐month period, from dairy cow urine applied to the Canterbury Templeton soil were 1.14 kg N₂O‐N/ha, and this was reduced to 0.43 and 0.39 kg N₂O‐N/ha by DCD and the liquid DMPP, respectively. These are equivalent to 62–66% reductions in the total N₂O emissions. Nitrate leaching losses from dairy cow urine applied to the Waikato Horotiu soil lysimeters were reduced from 628.6 kg ‐N/ha to 400.6 and 451.5 kg ‐N/ha by the application of DCD (10 kg/ha) or DMPP (1 kg/ha), respectively. There was no significant difference between the DCD solution and the liquid DMPP in terms of their effectiveness in reducing N₂O emissions or leaching under the experimental conditions of this study. These results suggest that both the liquid formulations of DCD and DMPP have the potential to be used as nitrification inhibitors to reduce N₂O emissions and leaching in grazed pasture soils.     

KINETICS OF ISOTOPIC EXCHANGE OF PHOSPHATE ADSORBED ON GIBBSITE

An Elovich-type equation has been used to describe the kinetics of isotopic exchange of phosphate adsorbed on the surface of gibbsite. The equation is where A and B are parameters; θ=bF/[b+a(I-F]; a and b are the molar concentrations of the phosphate on the crystal surface and in solution respectively and F is the fraction exchange of the radio-isotope at time t. First-order rate constants were obtained from the equation. The reference state for the first-order rate constants, and the distribution of activation energies, for exchange can be related to the Elovich equation parameters. The kinetic results are consistent with S_N1 dissociation or S_N2 bimolecular solvolysis for the phosphate ligand. The eschange reaction is subject to an acid-base catalysis the exact nature of which could not be determined from the available data.