Impedance Factor for Chloride Diffusion in Soil as Affected by Bulk Density and Water Content

The influence of soil bulk density and water content on the impedance factor (f) was studied by measuring bulk diffusion of chloride from one soil block to another differing in Cl^?-concentration. An increase in bulk density from 1.38 to 1.76 g cm^?3 at a constant gravimetric moisture content of 7% decreased f by a factor of 3, at 10% to 12% there was nearly no effect on f, while at higher soil moistures of 16% to 20%, f increased almost linearly with increasing bulk density. With increasing soil volumetric water content, (θ), f increased linearly at all soil bulk densities. At the same θ, the impedance factor decreased with increasing soil bulk density. The relationship between θ and f as established by Barraclough and Tinker (1981) agrees well with the results obtained here for bulk densities of 1.38 and 1.56 g cm^?3 and water contents higher than 18% (v/v). However, at lower values of θ, measured f values were higher than predicted by these authors. On the other hand, f values for a bulk density of 1.76 g cm^?1 at all water contents were clearly below the values of these authors.     

Diffusion of Zinc as Influenced by Physical and Chemical Properties of Soils

The self diffusion coefficients of zinc (D_aZn), determined by half cell technique, were found to be greatly influenced by variations in soil characteristics such as volumetric moisture content, bulk density, temperature, carrier zinc concentration and soil pH. The D_aZn values showed exponential decrease with increase in soil pH but with increasing volumetric moisture content, D_aZn values showed logarithmic increase. The highest D_aZn value was obtained at a compaction of 1.50 g/cm³. Increase in temperature from 5°C to 30°C showed 4 to 20 times increase in D_aZn values. An attempt was made to study the relationship between soil characteristics and D_aZn values for 87 illitic soils differing in physical and chemical properties. The simple and multiple correlation coefficients did not account for more than 21 per cent of variations indicating that D_aZn values cannot be predicted accurately from soil properties.     

Estimation of the diffusion coefficients of adsorbed and non-adsorbed solutes in soil

A method is proposed which follows Darrah's experimental procedure and takes advantage of a mathematical solution provided by Carslaw & Jaeger to estimate the diffusion coefficients of adsorbed and non-adsorbed solutes in soil. The method requires only the values of the concentration of the solute at the input face of a uniform column of soil, C^s, and of the total amount, Q_t, that has entered the soil after a specified time during which the surface of the block is in contact with a thin porous pad containing a known initial amount of solute, Q₀, at concentration C₀, expressed in the same units as C^s. In the C^s/C₀ vs. Q_t/Q₀ space there is a unique relationship between the effective diffusion coefficient, D_e, of the solute in the soil and the contact conductance for this solute, h, between the pad and the soil surface. The proposed procedure is firstly to determine D_e, and h for a non-adsorbed solute in the experimental soil using the experimental values of C^s/C₀ and Q/_Q for that solute. This value of D_e, gives the diffusion impedance factor for the solute in the soil, f, which is assumed also to apply to adsorbed solutes. A first estimate of the effective diffusion coefficient of an adsorbed solute, ¹D_ea, is then made using f and the diffusion coefficient of the free solute in water, D_L, obtained from the literature (i.e. ¹D_ea= D_Lf). Only if the solute is weakly adsorbed will the values of C^s/C₀, and Q_t/Q₀ lie in C^s/C₀, vs. Q_t/Q₀, space as defined by ¹D_ea and the contact conductance, h. Instead a second space relating C^s/C₀ and Q_t/Q₀, is now constructed from nominated values of h and D_e, where D_e, is defined in terms of ¹D_ea, the adsorption coefficient, F , and the volumetric moisture content of the soil, θ. The position of the experimental values of C^s/C₀, and Q_t/Q₀ within this new space defines h and the actual D_e, and F of the solute as it diffuses and is adsorbed in the soil. The advantages and limitations of the method are discussed. In particular, the method assumes that the adsorption process is linear and reversible.     

Estimation of CO2 diffusion coefficient at 0–10 cm depth in undisturbed and tilled soils

Diffusion coefficients (D) of CO₂ at 0–10 cm layers in undisturbed and tilled soil conditions were estimated using the Penman (Penman HL. 1940. Gas and vapor movement in soil, 1. The diffusion of vapours through porous solids. J Agric Sci. 30:437–463), Millington–Quirk (Millington RJ, Quirk JP. 1960. Transport in porous media. In: Van Baren FA, editor. Transactions of the 7th International Congress of Soil Science. Vol. 1. Amsterdam: Elsevier. p. 97–106), Ridgwell et al. (Ridgwell AJ, Marshall SJ, Gregson K. 1999. Consumption of atmospheric methane by soils: A process-based model. Global Biogeochem Cy. 13:59–70), Troeh et al. (Troeh FR, Jabro JD, Kirkham D. 1982. Gaseous diffusion equations for porous materials. Geoderma. 27:239–258) and Moldrup et al. (Moldrup P, Kruse CW, Rolston DE, Yamaguchi T. 1996. Modeling diffusion and reaction in soils: III. Predicting gas diffusivity from the Campbell soil–water retention model. Soil Sci. 161:366–375) models. Soil bulk density and volumetric soil water content (θ_v) at 0–10 cm were measured on 14 April, 2 June and 12 July 2005 at 0–10 cm depth in no-till (NT) and conventional till (CT) malt barley and undisturbed soil grass–alfalfa (UGA) systems. Air-filled porosity (ε) was calculated from total soil porosity and θ_v measurements. Both soil air porosity and estimated CO₂ diffusivity at the 0–10 cm depth were significantly affected by tillage. Results of CO₂ diffusion coefficients in the soil followed trends similar to those for soil ε data. The CT tended to have significantly greater estimated soil CO₂ diffusion coefficients than the NT and UGA treatments. The relationship between D/D ₀, and air-filled porosity was well described by a power (R ² = 0.985) function. The model is useful for predicting CO₂ gas-diffusion coefficients in undisturbed and tilled soils at various ranges of ε where actual gas D measurements are time-consuming, costly and infeasible.     

Measurement and Prediction of the Oxygen Diffusion Coefficient in Unsaturated Media, with Applications to Soil Covers

Molecular diffusion is an important mechanism for gas transport in various natural and man-made systems. This is particularly the case with soil covers installed on acid-generating mine tailings, where oxygen availability has to be controlled. One of the most important roles of such covers is to limit gas flux, which depends on the effective diffusion coefficient D _e of the cover materials. This paper presents an experimental procedure and results from oxygen diffusion tests performed on different types of materials, at various degrees of saturation. The determination of D _e in the laboratory from the test data is based on analytical and numerical solutions to Ficks laws. The ensuing values of D _e are compared to values calculated from available models that relate D _e to basic material properties, including porosity and degree of saturation. Statistical indicators are used to evaluate the accuracy of selected models, individually and on a comparative basis. It is shown that modified versions of the Millington–Quirk (M-Q) and Millington–Shearer (M-S) models provide D _e values close to the measured data. A semi-empirical expression, ensuing from these models and measurements, is proposed as a simple means of estimating D _e.     

Gas diffusion through soil crumbs: the effects of compaction and wetting

Samples of 1–2 mm crumbs from a clay loam under permanent pasture were equilibrated at -5 kPa water potential then compacted to varying degrees. Gas diffusion coefficients D, (hydrogen through air), were measured immediately on compaction, again after re-equilibration at -5 kPa, then at other water contents between saturation and dryness. The relationship between diffusion coefficient and air content, was, as elsewhere, in two parts (dD/d small for drainage of pores within crumbs; large for pores between crumbs), but the transition from one part to the other occurred at smaller air contents with increased compaction. The air content at which D approached zero as the samples wetted was greatest in the loosest soil. Compaction from a bulk density of 0.86–1.29 g cm^?3 decreased the relative diffusion coefficient, D/D₀ (D₀ is the diffusion coefficient without impedance), from 0.35 to 0.22 (by 38%) at complete dryness, but from 0.19 to 0.035 (by 82%) in the soil initially at -5 kPa. On re-wetting and re-equilibrating at ?5 kPa, D/D₀ decreased further to 0.008 (total 97%) because of extra water held in the now smaller pores of the compacted soil. No single relationship between D/D₀ and fitted the results for even this one soil.     

The variability of the apparent diffusion coefficient in undisturbed soil columns

In column studies in the laboratory the apparent diffusion coefficients(D)of chloride and TOH for undisturbed and unsaturated soils were determined as a function of the pore water velocity. Parallel the effective diffusion coefficients (D⁺) of Cl^? were measured as a function of water content. It was found that the values of D varied significantly between soil layers and soil types. This findings also held for the low flow velocities studied (0.3 and 1.0 cm/d). The impedance factors to calculate the effective diffusion coefficients (D⁺) from D values in the bulk water, decreased with decreasing bulk densities. In model calculations it was demonstrated that in spite of the differences of D values measured, for many purposes in the field good estimates of the solute distribution in the soils can be obtained by using simple relations between D and v_o.     

GAMMA RADIATION FOR MEASURING WATER CONTENTS IN SOIL COLUMNS WITH CHANGING BULK DENSITY

Water profiles in soil columns were measured by the single-source gamma radiation method. Together with the normal attenuation equation, linear or parabolic equations for the relation between bulk density and volumetric water content were used. To compensate for moderate changes in the bulk density during the experiment both initial and final bulk density and the water content were used in the water profile estimations. For a sandy loam soil, the radiation method without any corrections for bulk density changes resulted in a mean error of the volumetric water content estimation of 0.035 cm³ cm^?3, when the water content changed from 0.35 to 0.15 cm³ cm^?3. By correction for changing bulk density by means of a linear or a parabolic equation the maximum difference between real and estimated water content was 0.009 and 0.002 cm³ cm^?3, respectively. Applying the latter method and a count of 10⁵ the error of a single water content measurement was 0–004 cm³ cm^?3.     

Simulation of effects of soil bulk density and p addition on k uptake by soybeans

Abstract

Increasing soil bulk density has been shown to reduce root growth and decrease K uptake by soybeans (Glycine max L. Merrill). Changing soil bulk density also affects soil buffer power, b, and effective diffusion coefficient, De, which affect K influx. The relative decrease in K uptake due to reduced root growth as compared to reduced K influx is not known. Addition of P may affect root growth and P influx properties of plant roots. The objectives of this paper were (1) to use the Cushman mechanistic model to simulate the effect of changing soil bulk density and soil P on K uptake by soybeans, and (2) to determine the parameters that are changed by changes in bulk density and added P and their effect on K uptake. Plant and soil data of an experiment where Williams soybeans were grown for 21 days in pots of Raub (Aquic Argiudoll) silt loam with factorial treatments of two rates of K (0 and 100 mg K kg^‐1 soil), two rates of P (0 and 100 mg P kg^‐1 soil), and two bulk densities (1.25 and 1.45 g cm^‐3 ) were used to verify the model. Plant and soil parameters for the model were measured independently of the verification experiment. Predicted K (y) uptake agreed with observed uptake (x) (y = 1.09x‐0.19; r = 0.97) for the P x K factorial and (y = 1.19X‐0.22; r = 0.90) for the K x soil bulk density factorial treatments. In a sensitivity analysis, the model predicted a maximal K influx at a soil bulk density of 1.38 g cm^‐3. The greatest effect of soil bulk density on K uptake was due to reduction of root growth. Increased K uptake as a result of P addition was because of the effect on root growth.     

Influence of gravimetric water content and bulk density on the dielectric properties of soil

Moisture content and bulk density largely characterize physical and mechanical soil status and behaviour. A nondestructive determination of these soil properties is essential. Time domain reflectometry (TDR), although widely accepted for determination of volumetric water content, θ, has its limitations, and recently a frequency domain (FD) sensor has been developed and tested. An equation relating relative permittivity, ?′, to gravimetric water content, w, and bulk density, p, was established for three soil types (sand, sandy loam and clay). If ?′ and w are known, our model can be used to calculate bulk density and associated volumetric water content, θ, keeping in mind that θ= pw. Utilization is found in long-term monitoring of moisture fluctuations or short-term detection of traffic-induced soil compaction.     

Spatial variation of ammonia volatilization from soil and its scale‐dependent correlation with soil properties

Quantitative predictions of ammonia volatilization from soil are useful to environmental managers and policy makers and empirical models have been used with some success. Spatial analysis of the soil properties and their relationship to the ammonia volatilization process is important as predictions will be required at disparate scales from the field to the catchment and beyond. These relationships are known to change across scales and this may affect the performance of an empirical model. This study is concerned with the variation of ammonia volatilization and some controlling soil properties: bulk density, volumetric water content, pH, CEC, soil pH buffer power, and urease activity, over distances of 2, 50, 500, and >2000 m. We sampled a 16 km × 16 km region in eastern England and analyzed the results by a nested analysis of (co)variance, from which variance components and correlations for each scale were obtained. The overall correlations between ammonia volatilization and the soil properties were generally weak: –0.09 for bulk density, 0.04 for volumetric water content, –0.22 for CEC, –0.08 for urease activity, –0.22 for pH and 0.18 for the soil pH buffer power. Variation in ammonia volatilization was scale‐dependent, with substantial variance components at the 2‐ and 500‐m scales. The results from the analysis of covariance show that the relationships between ammonia volatilization and soil properties are complex. At the >2000 m scale, ammonia volatilization was strongly correlated with pH (–0.82) and CEC (–0.55), which is probably the result of differences in parent material. We also observed weaker correlations at the 500‐m scale with bulk density (–0.61), volumetric water content (0.48), urease activity (–0.42), pH (–0.55) and soil pH buffer power (0.38). Nested analysis showed that overall correlations may mask relationships at scales of interest and the effect of soil variables on these soil processes is scale‐dependent.     

土壤磷扩散规律及其能量特征的研究 Ⅲ.土壤磷扩散的动力学及能量特征

用³²P标记扩散池法测定了不同时间下土壤磷的扩散量,并用5种动力学模型对其拟合,结果表明土壤磷扩散过程最符合抛物线扩散方程。20%含水量下,磷扩散速率温度商Q₁₀。为1.20左右,与扩散是一个物理过程相吻合。由阿尼乌斯公式求得的磷扩散活化能(E_a^D)随土壤水分增加而降低;在土壤水低吸力范围内(<10⁵Pa水吸力)为12-34kJ/mol,平均为25kJ/mol左右,与溶液中离子扩散活化能较接近,说明低吸力下磷扩散主要在液相进行。将绝对反应速率理论移植用于磷扩散,所求出的磷扩散净活化能、活化熵变、活化焓变和活化自由能变在供试土壤中相同含水量下均呈规律性变化,且与E_a^D变化趋势基本一致,证明这些参数可用于表征磷扩散的能量特征。     

The effect of bulk density, water content and soil type on the diffusion of chloride in soil

The relative importance of soil bulk density, water content and potential on the self-diffusion and impedance factors of ³⁶C1 in a sandy loam and loamy clay were studied. The soil bulk densities used represented a range of conditions from freshly tilled seedbeds to compacted soils. The volumetric water contents and pF were the main factors controlling the soil impedance factors, with bulk density making a small but significant contribution.
Soil type affects the impedance factors through differences in anion exclusion volumes, the water contents of poorly connected pores that contribute little to the diffusion process, and tortuosity of the diffusion pathways.     

Soil Ammonium Diffusion Constraints Contribute to Large Differences in Nitrogen Supply to Rice in the Southern United States

This study was to determine if diffusion of soil ammonium may explain why many sandy soils have greater nitrogen (N)–supplying capacity to rice than clay soils. A laboratory procedure using transient-state methods measured the linear movement of soil ammonium (NH₄) in tubes packed with five field soils under aerobic conditions. Ammonium diffusion was measured by sectioning tubes after 48 h of equilibration and then measuring NH₄ by steam distillation. Effective diffusion coefficients, D_e, and NH₄ diffusion distance, d, per day ranged from D_e = 4.6 × 10^?5 cm² d^?1 and 1.5 cm d^?1 for Katy sandy loam to D_e = 2.9 × 10^?7 cm² d^?1 and 0.11 cm d^?1 for League clay. Ammonium diffusion distance d was strongly related to soil clay content and hence was predicted by d = Y × {[100/(% clay)] ? 1}, where Y is set to 0.1. Predicted d and measured d were highly related (R² = 0.99).     

氯离子在土壤中的扩散: Ⅱ.动力学及热力学性质

The amounts of chloride ions diffused in four soils of different textures at the same water content under different temperature and at varied time were measured by the diffusion cell method using ³⁶Cl-labelled CaCl₂ solution. Five kinetic models were used to fit the dynamic process of the diffusion of chloride ions in the soils. It was found that Elovich equation or power function equation was the best model to describe the process. The pseudothermodynamic parameters, i.e. the net reaction energy, the activation entropy, activation enthalpy and activation free energy of the diffusion, were derived from the absolute reaction-rate theory. The results showed that these parameters decreased in the order of loessal soil > black lu soil > lou soil > yellow cinnamon soil, which indicated that the force and the heat-energy barrier to be overcome for diffusion decreased, the diffusion rate increased and the disorder of the soil-solution-ion system due to diffusion decreased successively with the texture becoming heavier in the four soils.     

Zinc Diffusion and Self-Diffusion Coefficient in Alkaline Soils as Affected by Soil Properties and Zinc Carrier

The apparent diffusion coefficients, D_p/b+ø, of Zn and ZnEDTA were linear functions of added Zn, and were related to the adsorption and fixation capacities of soils rather than their pH. Lower apparent diffusion coefficient values were found in an Haplustoll soil that had higher clay and humus contents inspite of its lower pH. At comparable rates of added Zn, the apparent diffusion of ZnEDTA was 930–1010 (Bakyria), 700–1330 (Dirab), and 730–1880 (Baha) times that of Zn in the soils. The adsorbed Zn per cm³ of soil/Zn per cm³ of the equilibrium solution at the water content existing in the diffusion experiment approximated the capacity factor and was determined by extrapolation. The self-diffusion coefficient of Zn in Baha soil (5 × 10^?7 cm²sec^?1) of higher clay and water content was higher than in Bakyria or Dirab soil (2 × 10^?7 cm²sec^?1). These values were similar to the self-diffusion coefficient of P in soils of similar texture at similar water content.     

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.     

青海云杉造林密度与水源涵养功能的响应关系

以青海省大通县安门滩小流域7种造林密度的青海云杉人工林为研究对象,利用浸水法、环刀法测定林下枯落物、草本层及0—60cm土壤层的持水量,定量评价不同密度的青海云杉人工林水源涵养功能。结果表明:(1)不同造林密度下的林分枯落物最大持水量变化范围为1.97～7.60m3/hm2,枯落物持水量最大的造林密度为1 725株/hm2,造林密度为2 300株/hm2的枯落物持水量最小;不同造林密度的林下草本层持水量变化范围为1.97～7.17m3/hm2,林下草本层持水量最大的造林密度为1 575株/hm2。(2)0—60cm土层的水源涵养功能与土壤物理性质、土壤渗透性及贮水性密切相关,土壤容重的变化范围为1.20～1.43g/cm~3,土壤总孔隙度变化范围为46.53%～53.30%,土壤容重与土壤总孔隙度随造林密度变化趋势呈负相关,密度1 575株/hm~2的林地具有最小的土壤容重和最大的土壤总孔隙度;土壤渗透性能主要取决于土壤的非毛管孔隙度,二者呈显著性相关,密度为1 575株/hm~2的土壤渗透性能最强,密度为2 300株/hm2的林分土壤渗透性最差;0—60cm土层的饱和蓄水量变化范围为2 792.50～3 197.90m3/hm2,造林密度为1 575株/hm2的土壤饱和蓄水量最大。(3)利用林地总贮水量评价水源涵养功能,林地总贮水量大小依次为D1575(3 207.37m3/hm2)D2300(3 164.67m3/hm2)D1900(3 157.17m3/hm~2)D1650(3 141.12m3/hm2)D1475(3 105.91m3/hm2)D1725(2 998.32m3/hm2)D1350(2 803.68m3/hm2)。研究结果说明造林密度为1 575株/hm2的青海云杉林水源涵养能力较好,这与当地2m×3m的造林规格相匹配,为青海黄土高原高寒区的青海云杉人工林可持续经营提供理论依据。     

Influence of soil properties on the response to phosphorus in some tropical soils: I. Initial response to fertilizer

The availability of fertilizer P in six P-deficient tropical soils from Brazil, Kenya, Malaysia and Indonesia was assessed by grass in a pot experiment. Grass dry matter yield (D) and fertilizer P(F) were fitted to a Mitscherlich equation: D= a?b exp(?cF), and P uptake (U) and F to the linear equation: U=α+βF. Fitted parameter β equals the proportion of P recovered in one crop and it varied widely between soils, ranging from 12 to 51%. Quantitative assessments of fertilizer-P availability could also be made using dry-matter data alone if the rates of fertilizer used were well distributed along the response curve, when Mitscherlich parameter c was correlated well with β. Chemical measurements were made on uncropped soil. Phosphate sorption isotherms were measured, using ³²P to assess exchangeable and non-exchangeable phosphate. The availability parameters c and β were correlated best with parameter b_e, the phosphate buffer capacity derived from the fitted Freundlich isotherm for exchangeable phosphate, suggesting that the mobility of exchangeable phosphate is a major influence on P availability. Al and Fe were extracted with acid oxalate, citrate-dithionite and pyrophosphate reagents, and parameters c and β correlated best with Al extracted by acid oxalate. These relationships were inverse, showing that Al in disordered mineral forms lowers the availability of fertilizer P.