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.     

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.     

A comparison of the convection-dispersion equation and transfer function model for predicting chloride leaching through an undisturbed, structured clay soil

The transfer function mode) (TFM) and convection-dispersion equation (CDE) were compared for predicting Cl ^? transport through a calcareous pelosol during steady, nearsaturated water flow. Large, undisturbed soil cores were used at constant irrigation intensities (q₀) between 0.3 and 3 cm h^?1, with a step-change in Cl^? concentration. The assumption of a lognormal distribution of travel times–characterized by the mean (μ) and variance (σ²)–permitted the flux-averaged breakthrough curves (BTCs) to be modelled very accurately by the TFM. The BTCs could be modelled equally well by the CDE when both the mean pore water velocity (v) and dispersion coefficient (D) were optimized simultaneously by the method of least squares, but not when v was put equal to q₀/_v, where _V was the mean volumetric water content. The best estimate of v was consistently > q₀/_v, which suggested that not all the pore water was effective in chloride transport. An operationally defined transport volume (θ_st) was calculated from the mean () or median (τ_m) travel times derived from the TFM. Chloride exclusion was not solely responsible for θ_st() being <_V: immobile water also contributed. The positive skewness of the travel time distributions meant that θ_st(τ_m) < θ_st(), indicating the effectiveness of macropore flow in solute transport. Dαv^1.42 (from the CDE), and σ²αv (from the TFM), confirmed that Cl^? dispersion increased as flow velocity increased. Flux-averaged concentrations were used to calculate the volume-averaged resident concentrations. They matched the measured Cl^? concentrations most closely when there was a gradual decrease in measured Cl ^? concentration with depth, but not when Cl ^? decreased sharply below c. 10 cm. Calculations assuming that all the water was effective in chloride transport gave less accurate results. Comparison of the measured and predicted concentrations of solute demonstrated that this must be a critical part of the evaluation of any model of solute transport.     

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.     

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 MEASUREMENT AND MECHANISM OF ION DIFFUSION IN SOILS. VIII —A THEORY FOR THE PROPAGATION OF CHANGES OF pH IN SOILS

The way pH changes in soil are propagated by movement of acids and bases is described. In acid soils the H₃O⁺-H₂O acid-base pair is most important, while in alkaline soils the H₂CO₃-HCO₃^? pair is always dominant, its effect depending directly on the pressure of CO₂. In neutral and slightly acid soils, soluble organic matter and the H₂PO₄^?-HPO²₄^? pair may also contribute. A soil acidity diffusion coefficient is derived, and defined as: where v_l= the volume fraction of the soil solution, f_l= the impedance factor for the liquid diffusion pathway, b_HS= the pH buffer capacity of the soil, b _HB= the pH buffer capacity of each mobile acid-base pair, Dl _HB= the diffusion coefficient of each mobile acid-base pair in free solution, and the sum is taken over all mobile acid-base pairs. The soil acidity diffusion coefficient may be used to predict the course of pH equilibration in practical situations. It is high in acid and alkaline soil, and at a minimum in slightly acid soil. It is little affected by variation of the ionic strength of the soil solution at concentrations less than 0.01M. When the pH buffer capacity of the soil is constant, and only the H₃O⁺-H₂O and H₂CO₃-HCO₃^? pairs are important, the soil acidity diffusion coefficient varies as cosh{2.303(pH—pH₀)}, where pH₀ is the pH at which the soil-acidity diffusion coefficient is a minimum.     

The Burns leaching equation

The simplicity and utility of Burns' leaching equation make it worthy of study. The equation may be written as where X is the fraction of initially surface-resident fertilizer leached below depth z by net rainfall I, in soil with a volumetric water content at ‘field capacity’ of θ. The equation is analysed using transfer functions. The analysis shows that Burns' equation is consistent with an ‘independent flow tube’ soil leaching model, rather than the soil solution being well-mixed at each soil depth as Burns suggested. The flux and resident soil solution soil concentration profiles are shown to be quite different. An alternative definition of θ is suggested. The behaviour of ‘a Burns soil’ for different initial and boundary conditions is discussed.     

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.     

THE VOLUME AND POROSITY OF SOIL CRUMBS

A simple and inexpensive apparatus (a test-tube, burette, and pin) is described for measuring volumes by liquid displacement to an accuracy of greater than 0.5 per cent. This has been adapted to measure soil crumb porosities, ε_c, by saturating 3–4 g samples of crumbs with kerosene, measuring the weight of kerosene retained internally, then measuring their volume by displacement. Three estimates of crumb porosity from these measurements are compared. Experimental values range from ε_c= 0.205 for the headland of an arable field to ε_c= 0.351 for a permanent pasture. Crumb porosity is proposed as a measure of structural status for soils because it assesses the degree to which soil management has succeeded in holding the constituent primary particles apart from the positions of inherent closest packing that they would ultimately assume in an unstable soil. By comparison, the inter-crumb porosity, ε_v, can be used as a measure of cultivation status. In the form expressed, these two porosities are related to the more frequently encountered total porosity ε_t by the relation      

WATER MOVEMENT IN DRY SOILS

Semi-infinite columns of dry soil closed at one end had the other exposed to a turbulent atmosphere at constant relative humidity (0.98) and a range of constant temperatures. After varied times the water content of the columns was measured gravimetrically, in 1 cm layers, from which the total quantity taken up Q and the distribution of water content Ø with time t and distance x were found. Assuming that the Boltzmann transform, λ=xt^?t can be applied to the standard diffusion equation, two soil parameters are derived. A test of the assumption is that Ø should be uniquely dependent on λ, and then the diffusivity is calculable from where Ø_t is the initial uniform water content. The second parameter—the sorptivity, S= Qt^?½—and is not independent of Ø_t or the value maintained at x= 0. Results show that in a clay soil, between pF 5.8 and pF 4.2, water moves predominantly as vapour: in a non-swelling silicate mineral (sepiolite) there is significant liquid movement between pF 5.1 and pF 4.2. Long-continued use of organic manure has little effect on either D or S; aggregate size has some effect, in opposite senses for a sand and a clay; a mulch or a still atmosphere affects S but not D; evaporation suppressants decrease S; ignition decreases S and greatly alters D; and degradation of structure causes small changes in D.     

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.     

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.     

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.     

The solid solution equilibria of lead and cadmium in polluted soils

A method for the measurement of Pb and Cd in equilibrium soil solutions involving soil equilibration with a dilute Ca electrolyte, centrifugation and filtration to <0.2 μm was evaluated. The procedure was subsequently used for the analysis of 100 Pb- and 30 Cd-contaminated soils. Solutions were analysed for Pb- and Cd using graphite-furnace AAS and the concentrations of Pb²⁺ and Cd²⁺ were estimated using standard speciation calculations. The concentrations of Pb and Cd found in the soil solutions were in the range 3.5–3600 μg dmp ^?3 and 2.7–1278 μg dm ^?3 respectively; both ranges represented less than 0.1% of the total metal concentration in the soils. Depending on solution pH, Pb ⁺² accounted for between 42–78% of Pb in solution while about 65% of Cd in solution was present as Cd⁺². The concentrations of Pb²⁺ and Cd²⁺ in solution suggested that the soil solutions were undersaturated with respect to the solid phases PbC0₃ and CdC0₃ but supersaturated with respect to Pb₅(P0₄)₃Cl and, for some samples, Cd₃(P0₄)₂ respectively. However, for both metals, a good empirical relationship was obtained between the total metal concentration in soil (mol kg^?1), free metal concentration in solution (mol dm^?3) and solution pH. The relationships took the general form of a pH-dependent Freundlich adsorption equation: For both lead and cadmium relationships, the values ofn and K₁ were close to unity, so that the distribution coefficient could be estimated from pH and a single metal-dependent constant, K₂. The algorithms appeared to be valid over a metal concentration range of four logarithmic units and pH range of 3.5–7.5.     

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.     

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.     

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.     

A new method for the estimation of total dissolved salts in saturation extracts of soils from electrical conductivity

We have determined electrical conductivity (E_e) and total dissolved salts (S) in saturation extracts from 39 soil samples from the Baza basin (Province of Granada, south-east Spain). E_e ranged from 2.8 to 110dS m^?3, and S from 2 to 444 8 dm^?3. The relationship between S and E_e was not linear. When the saturation extracts were diluted with progressively larger quantities of distilled water and their electrical conductivity calculated (E_ec) with the equation where E_d and E_w are the conductivity of the diluted extract and the distilled water and f is the dilution factor, the relationship between S and E_ec tended to become linear. The highest linear correlation coefficient relating S (mg dm^?3) and E_ec (dS m^?1) was reached when E_ec, values were calculated for dilutions with a conductivity (E_d) between 0.1 and 0.3 dS m^?1 (E*_ec). The regression equation was S= 490 E*_ec with r²= 0.999. This relationship can be used in all saturation extracts, regardless of the concentration and type of ions present.     

Humic substances in acid organic soils: modelling their release to the soil solution in terms of humic charge

Batch titration experiments were carried out with organic soil samples in order to investigate the release to the solution phase of humic substances (HS). Measurements were made of pH, dissolved organic carbon (DOC) concentration, and the concentration of mono-meric (inorganic + organic) aluminium, as functions of added acid or base. DOC was taken to be entirely due to HS. The results can be interpreted in terms of a model in which the soil is considered to contain two types of HS–mobile or potentially mobile (HSM), and immobile (HSI). The binding of inorganic ions by the HS is calculated using humic ion-binding model IV, previously developed in this laboratory. Model IV allows the charges on the HS (Z_HSM, Z_HST) to be calculated; these are determined mainly by the binding of H+ and A13+. Concentrations of HS in solution, [HS_aq], are given by the equation: where |Z_HSM| is the modulus of Z_HSM, n_HSM is the carboxyl group content of HSM, c_HSM is the soil content of HSM, β is a fitting parameter, and square brackets, [ ], indicate concentrations. For most of the soils a value for β of 3 gives acceptable agreements between measured and calculated values of [HS_aq], indicating a major influence of charge on release. The optimized value of c_HSM differs considerably among soils, whereas c_HIS varies by only a factor of about two. Total humic contents (c_HSM+ c_HSI estimated by model optimization are in approximate agreement with values estimated by extraction of the soils with NaOH.