Proton interactions with soil organic matter: the importance of aggregation and the weak acids of humin

Samples of three organic‐rich soils (ombrotrophic peat, podzol H‐horizon, humic ranker) were extensively washed with dilute nitric acid, dialysed against deionised water, and then subjected to acid‐base titrations over the pH range 3–10, in 0.3–300 mm NaNO₃, and with soil concentrations in the range 2–150 g l^?1. The results for the three soils were quantitatively similar. Comparison of the titration data with previously published results for humic acids isolated from the same soils showed the soil organic matter to have a greater ionic strength dependency of proton binding and to possess relatively greater buffering capacity at high pH, attributable to weak acid groups (c. 2–5 mmol g^–1) in the humin fraction of the soils. To describe the soil titration data quantitatively, we modified Humic Ion‐Binding Model VI‐FD, which utilizes a fixed Donnan volume to describe counterion accumulation, by increasing the content of weak acid groups. When artefacts in pH measurement caused by the suspension effect were taken into account, the resulting Model VI‐FD2 provided good or fair simulations of all the titration data. The results suggest that soil structure, specifically aggregation, plays a significant role in cation binding by organic soils in situ. The lack of dependence of the titration results on soil suspension concentration suggests that the findings can be applied to soils in situ.     

Study of the acid‐base properties of a peat soil and its humin and humic acid fractions

For accurate interpretation of cation binding to natural organic matter, the proton binding behaviour of both solid and dissolved natural organic matter must first be established. In the present study, potentiometric titrations of samples of humin and humic acid extracted from a peat soil were performed at different ionic strengths. Humic acid (HA) samples in solution (dissolved humic acid, DHA) and in suspension (aggregated humic acid, AHA) were titrated. The corresponding charge curves were analysed with the NICA‐Donnan model and the results were compared with those previously obtained for the peat soil. Good reproduction of the DHA charge curves was obtained, and in the case of the AHA, the exact forms of the charge curves were not reproduced at pH < 6 because of the conformational changes and dissolution of the sample that took place throughout the titration. The peat and humin displayed similar proton binding behaviour, which was different to that of the humic acid. With the Donnan approach, the value of parameter b, that relates the Donnan volume to the ionic strength, was the same for peat and humin and less than that of the humic acid, for both the dissolved samples and those in suspension, indicating that the effect of ionic strength on the charge is greater in the peat and humin than in the HA. The ratio between the contents of phenolic groups and of carboxylic groups was greater in peat and humin than in humic acid. The model used revealed that the acid‐base behaviour of the peat is closer to that of the humin than to that of the humic acid.     

Interpretation of humic acid coagulation and soluble soil organic matter using a calculated electrostatic potential

The coagulation of humic substances and its role in controlling the solubility of organic matter in soils are not well understood. We therefore studied the physico‐chemical behaviour of purified humic acid from forest soil coagulated with Na, Ca, Cu, Al at pH 4 and 6, and then modelled the behaviour with the Non‐Ideal Consistent Competitive Adsorption Donnan (NICA‐Donnan) model. We found that the coagulation of humic acid occurs when the Donnan potential is less negative than ?0.08 V. Based on this result, an empirical relation between the Donnan potential of humic acid and its concentration in solution was derived. In addition, the Donnan potential of the dissolved organic matter in the soil solution of six soil profiles from forests was calculated using the NICA‐Donnan model under the assumption that all the dissolved organic matter behaves as humic acid. The measured concentration of dissolved organic matter also decreases in a soil profile, as the calculated potential becomes less negative. The results are in many cases in semi‐quantitative agreement with the predicted concentration based on the humic acid coagulation experiment. Acid soils contain more dissolved organic matter, which may result from the presence of a fairly large fraction of more soluble organic molecules, such as fulvic acid.     

Effect of soil depth on acid properties of humic substances extracted from an ombrotrophic peat bog in northwest Spain

The most southerly ombrotrophic peat bogs in Europe are in Galicia (northwest Spain). The humic matter in them originates from chemical processes in anaerobic conditions. We studied the acid properties of fulvic acids and humic acids isolated from two peat horizons of an ombrotrophic peat bog by potentiometric titration. Solutions containing 25, 50 and 100 mg l⁻¹ of each humic substance were titrated at ionic strengths 0.005 m , 0.01 m and 0.1 m (with KNO₃ as the inert electrolyte). Charge curves were analysed with a Donnan model to determine the intrinsic proton binding parameters. The concentration of the humic substance affected the charge curves more significantly at pH exceeding 6, and tended to disappear at greater concentrations. The proton binding conditional constants decreased with increasing ionic strength, this effect being more significant in the carboxylic groups with less affinity for protons. The proton binding constant of the carboxyl groups in a fulvic acid was one order of magnitude less than the value for the corresponding humic acid, whereas for the phenolic groups the values for both fractions were similar. The total content of acid groups was approximately 2 mol kg⁻¹ greater in the fulvic fraction than in the humic fraction. Both humic fractions from the lower horizon contained more acid groups than those from the upper horizon, mainly because the content of carboxyl groups increases with soil depth. Therefore, the humic substances in the lower horizon of the peat will be more negatively charged, which will affect their solubility and the binding of metal ions.     

Partitioning of organic carbon, aluminium and cadmium between solid and solution in soils: application of a mineral–humic particle additivity model

The partitioning of chemical elements between the solid and solution phases in soil is fundamental in understanding processes such as leaching and bioavailability. Here I present a model in which the partitioning of Cd, Al and carbon in both mineral and organic soils can be simulated in the pH range 2–8. A two‐phase additivity approach simulates ion adsorption by the soils using a hydrous ferric oxide and humic type surface. A model for the partitioning of soil humic matter has also been developed in which the NICA–Donnan model calculates humic surface charge. Other key processes represented include mineral solubilization and solution speciation. Methods for deriving model input parameters either from analytical data or by parameter optimization were used. Acid ammonium‐oxalate‐extractable Fe was used to estimate the amount of hydrous ferric oxide, and reactive humic substances were estimated by a scaled down version of the International Humic Substances Society method for the extraction of humic and fulvic acid. For initial calculation the 0.1 m HCl‐extractable Al was used to estimate reactive Al. Optimization of reactive Al improved the fit of both the total dissolved Al data and the adsorbed Cd. The model for the solid–solution partitioning of humic substances could simulate reasonably well the release of carbon in the pH range 4–8 for both the organic and mineral soils.     

Cation binding by acid-washed peat, interpreted with Humic Ion-Binding Model VI-FD

A sample of ombrotrophic peat from Moor House in northern England was extensively extracted with dilute nitric acid (pH 1) to free it of bound cations. Suspensions of the acid‐washed peat (5–30 g l^?1), prepared with different concentrations of background electrolyte (NaCl and KCl), were used to conduct batch acid–base titrations. A strong dependence of proton release on ionic strength (I) was observed, the apparent acid dissociation constant (pK_app) being found to decrease by approximately 1.0 for each tenfold increase in I. This behaviour could not be explained satisfactorily with Humic Ion‐Binding Model VI, a discrete‐site/electrostatic model of cation binding by humic substances, parameterized with data from laboratory studies on isolated samples. More success was obtained by abandoning the impermeable‐sphere electrostatic submodel used in Model VI, and instead assuming the peat to consist of aggregates with fixed internal volume, and with counterion accumulation described by the Donnan model, as proposed by Marinsky and colleagues. The fixed‐volume Donnan model (Model VI‐FD) could also approximately explain other reported results from acid–base titrations of peat, including the effects on the titrations of complexing cations (Al, Ca, Cu). Copper titrations of the Moor House sample were performed using an ion‐selective electrode, with peat suspensions in the acid pH range, at two ionic strengths, and in the presence of Al and Ca. The measured concentrations of Cu²⁺ were in the range 10^?13?10^?5 m . Model VI‐FD provided reasonable fits of the experimental data, after optimization of the intrinsic binding constant for Cu, the optimized value being close to the default value derived previously from data referring to isolated humic substances. The optimized constants for Al and Ca, derived from their competition effects, were also close to their default values. Additional experiments were performed in which the centrifugation‐depletion method was used to measure the binding of a cocktail of metals (Al, Ni, Cu, Zn, Cd, Eu, Pb) at a single pH. The model correctly predicted strong binding of Al, Cu, Eu and Pb, and weaker binding of Ni, Zn and Cd. For the strongly binding metals, the dissolved forms were calculated to be mainly due to complexes with dissolved humic matter, whereas the free ions (Ni²⁺, Zn²⁺, Cd²⁺) dominated for the weakly binding metals. Acid‐washed soil appears to provide a valuable intermediate between isolated humic substances and untreated soil for the investigation of cation binding by natural organic matter in the natural environment.     

Acid properties of fulvic and humic acids isolated from two acid forest soils under different vegetation cover and soil depth

We studied the acid‐base properties of 16 fulvic acids and 16 humic acids isolated from the surface (3–15 cm) and subsurface (> 45 cm) horizons of two types of acid forest soils, derived respectively from amphibolite and granite rocks, under five different types of vegetation. The observed differences between the contents of humic substances in the two types of soils were related to the degree of Al‐saturation of the soil organic matter, as indicated by the molar ratio between pyrophosphate extractable Al and C. Humic fractions were characterized in terms of elemental composition, and CPMAS ¹³C NMR spectrometry. The contents of carboxylic and phenolic groups were estimated by potentiometric titrations conducted in 0.1 m KNO₃ in a nitrogen atmosphere. The fulvic acids contained more carboxylic groups but less phenolic groups than the humic acids: the ratio of phenolic to carboxylic groups in the humic acids was 0.48 ± 0.10 and in the fulvic acids 0.23 ± 0.05. The mean values of the protonation constants of each of the humic substance fractions can be used as generic parameters for describing the proton binding properties. The fulvic acids isolated from the subsurface horizon of the soil contained between 2.6 and 23% more carboxylic groups, and the humic acids between 8 and 43% more carboxylic groups than those isolated from the surface horizon of the same soil.     

Assessment of degradation and generation of humus in a coffee soil affected by weed cover by means of a stable carbon isotopic ratio

We evaluated the effect of soil conservation by weeds on the degradation and generation of humic acids, fulvic acids, and water‐soluble non‐humic substances (WS‐NHS) in a red‐acid soil (Vertic Dystrudept) (Indonesia) from the changes in humus composition and stable carbon isotopic ratio (δ¹³C). Three plots, a weeded plot (T‐1; the common practice), a plot covered with Paspalum conjugatum Berg., a C₄ plant (T‐2), and a plot in which native weeds were allowed to grow (T‐3), were prepared. An incubation experiment determined the δ¹³C values of the humus fractions generated from Paspalum in soil. Based on the increase in δ¹³C value, the proportion of total C that originated from Paspalum C after 4 years under coffee was 16 ± 4% in the T‐2 topsoil (0–10 cm). Humic and fulvic acids in the T‐1 topsoil decreased to 46 and 84%, respectively, whilst both increased or remained constant in the T‐2 and T‐3 soils. The WS‐NHS content varied little and was independent of land management. The preferential loss of the humic acids with a smaller degree of humification as assessed by their darkness in colour was shown in T‐1. The decrease in the degree of humification suggested the accumulation of the weed‐derived humic acids in T‐2 and T‐3. In the T‐2 topsoil, 36 ± 2%, 13 ± 3% and 15 ± 2% of C in the humic acids, fulvic acids and WS‐NHS, respectively, were estimated to be Paspalum‐derived after 4 years. The estimated initial C loss during the same period was 17 ± 3%, 14 ± 2% and 7 ± 2%, respectively, for those fractions, which suggests the fastest turnover rate for the humic acids and significant retardation of their degradation in soil colonized by weeds.     

An Experimental and Modelling Study of Cu2+ Binding on Humic Acids at Various Solution Conditions. Application of the NICA-Donnan Model

Humic substances are characterized by a strong binding capacity for both metals and organic pollutants, affecting their mobility and bioavailability. The understanding of the mechanisms of proton and metal binding to humic substances is of fundamental importance in geochemical modelling and prediction of cation speciation in the environment. This work reports results on copper binding on humic acids obtained through a thorough experimental and modelling approach. Two humic acids, a reference purified peat humic acid isolated by the International Humic Substances Society (IHSS) and a humic acid from a Greek soil, were experimentally studied at various pH values (4, 6 and 8), humic acid concentrations (ranging from 20 to 200 mg?L^?1) and ionic strength (0.1 and 0.01 M NaNO₃). The binding of copper to humic acids was determined over wide ranges of copper ion concentrations using a copper ion selective electrode. The copper binding isotherms obtained at different conditions have shown that copper binding is dependent on the pH and ionic strength of the solution and on the concentration of both humic acids. Copper binding experimental data were fitted to non-ideal competitive adsorption NICA-Donnan model and the model parameter values were calculated. Both Cu²⁺ and CuOH⁺ species binding to humic acid with different binding affinities were considered. Two sets of the NICA-Donnan parameters have been calculated: one for humic acid concentrations of ??100 mg?L^?1and one for humic acid concentration of 20 mg?L^?1. The meaning of the parameters values for each concentration level is also discussed.     

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 organic amendment on amount and chemical characteristics of humic acids in upland field soils

To assess the effect of continuous organic material (OM) application on soil humic acids, the amount and chemical characteristics of humic acids in various types of soils (n = 10) were compared between plots treated with farmyard manure (FYM) or rice straw compost (RSC) plus chemical fertilizer (CF) and plots treated with CF alone. The degree of humification (degree of darkening), molecular size distribution and ¹³C cross polarization/magic angle spinning nuclear magnetic resonance spectra of humic acids from CF‐treated soils showed wide variation among the soils. Humic acid content was generally larger in OM + CF soils than in corresponding CF soils, and the stable C isotopic ratio suggested partial replacement of indigenous humic acids with OM‐derived ones even where no apparent increase in humic acid content was observed. The rate of OM application and the indigenous humic acid content were related positively and negatively, respectively, to the apparent accumulation rate of humic acids among soils. The degree of humification of humic acids was generally smaller in OM + CF soils than in CF soils. Humic acids extracted from FYM and RSC exhibited chemical characteristics typical of humic acids having a smaller degree of humification, which suggested the contribution of OM‐derived humic acids to the differences between OM + CF and CF soil humic acids, such as larger average molecular sizes and smaller and larger proportions of aromatic C and O‐alkyl C, respectively, relative to total C in the OM + CF soil humic acids. Little change was observed in the chemical characteristics of humic acids when the degree of humification of indigenous humic acids was small. The effect of OM application on the chemical characteristics of humic acids was most conspicuous in soils containing humic acids having an intermediate degree of humification, possibly resulting from the combination of accelerated degradation of indigenous humic acids and the accumulation of OM‐derived humic acids.     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

Soil Organic Matter Quality and Zinc and Lead Sorption as Affected by a Sewage Sludge Or a Sewage Sludge Compost Application

Sewage sludge (SS) or sewage sludge compost (SSC) were applied to soil under controlled conditions, at rates of 0 or 200 Mg ha^?1, to investigate changes in dissolved organic matter (DOM), humic acids (HA), and Pb and Zn sorption in the soil. Infrared spectroscopy, visible spectrophotometry, and sorption isotherms (mono-metal and competitive sorption systems) methods were used to assess the changer. The E₄/E₆ ratio (λ at 465 / λ at 665 nm) and the infrared spectra of DOM and HA showed aromatic behaviour in compost-soil (SSC-S); in contrast sewage sludge-soil (SS-S) showed an aliphatic behaviour. Application of either SS or SSC increased the Pb and Zn sorption capacity of soil. The Pb and Zn sorption increased in soil and soil mixtures with a competitive metal system. The metal affinity sequence for soil, SS-S, and SSC-S was compared with the predicted affinity sequences obtained from metal properties. Poor correspondence was observed between the metal affinity sequence and the metal affinity sequence predicted by ionic potential, indicating that metals bonding to soils were not predominantly electrostatic. An affinity sequence based on Pearson's theory agreed with the metal affinity sequences for soils. A statistical analysis showed that the bands assigned to esters (1080 cm^?1) of DOM, phenolic OH (1420 cm^?1), amide I (1650 cm^?1), carboxyl and carbonyl C=O stretches of different nature, C=O stretch of aromatic esters, aliphatic cetone, aldehyde (1720 cm^?1), ethers and esters (1230 cm^?1), aliphatic alcohols (1125 cm^?1), and lignin (1380 cm^?1) of HA were correlated with Zn constants of Langmuir adsorption isotherm (P < 0.05).     

Influence of natural and synthetic humic substances on the activity of urease

The activity of a purified urease, obtained from Bacillus pasteurii, was inhibited by humic and fulvic acids obtained from an agricultural soil. Enzyme kinetic studies showed that the humic substances affected the affinity of the enzyme for its substrate (K_m) and the maximum velocity of the reaction (V_max). The V_max was inhibited to the same extent by both humic (HA) and fulvic (FA) acids, the precise effect depending on the pH and concentration of humic substance. At pH 4.0, HA concentrations of 25 pg cm^?3 and 10 μg cm^?3 inhibited the V_max by 38.5% and 20% respectively. HA and FA had similar effects on the K_m but in this case the lowering of the affinity of the enzyme for its substrate was not concentration dependent in the range 0–25 μg cm^?3 of humic substance. Typically, the affinity was decreased from a K_M of 50 mM in the control to 67 mM in the presence of HA and FA. The effects were not due primarily to the ash or N contents of the humic substances because de-ashed humic acid and synthetic model humic (made from catechol, guaiacol, pyrogallol, resorcinol and protocatechuic acid) and fulvic acid (made from polymaleic acid), containing virtually no ash or N, were equally as effective. The effect was not related to the phenolic monomers which, before polymerization, had no effect on urease activity.     

A model of solid-solution interactions in acid organic soils, based on the complexation properties of humic substances

CHAOS (Complexation by Humic Acids in Organic Soils) is a quantitative chemical model of organic soils that incorporates complexation by the functional groups of humic substances and non-specific ion-exchange reactions. The two types of interaction are linked by the net humic charge, Z, which depends on the extents of proton and metal complexation, and which in turn determines ionic concentrations in the diffuse part of the electrical double layer, by a Donnan equilibrium. CHAOS was found to account satisfactorily for the results of acid-base titration experiments (pH range 3–5) with soil samples, giving reasonable simultaneous predictions of solution pH and concentration of A1³⁺. Predictive calculations with CHAOS suggest that organic soils acidified by acid rain would respond on a time-scale of years-to-decades to reductions in rain acidity. An associated effect might be an increase in the concentration of dissolved organic matter in the soil solution.     

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

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

Microbial community changes during humification of 14C-labelled maize straw in heat-treated and native Orthic Luvisol

The microbial communities in agricultural soils are responsible for nutrient cycling and thus for maintaining soil fertility. However, there is still a considerable lack of knowledge on anthropogenic impacts on soils, their microflora, and the associated nutrient cycles. In this microcosm study, microorganisms involved in the conversion of crop residues were investigated by means of classical microbiological and molecular methods such as denaturing gradient gel electrophoresis (DGGE) of PCR (polymerase chain reaction) amplified 16S rRNA genes. ¹⁴C‐labelled maize straw was humified by the naturally occurring microflora in native and in ashed soils, from which organic carbon was removed by heating at 600°C. The humic acids synthesized in the microcosms served as indicators of the humification process and were analysed by ¹³C‐NMR spectroscopy. Ashed, autoclaved and native soil exhibited similar microbial and physicochemical dynamics after inoculation with a soil suspension. Bacterial counts and DGGE analyses showed that in the first few weeks a small number of rapidly growing r‐strategists were principally responsible for the conversion of maize straw. As the incubation continued, the bacterial diversity increased as well as the fungal biomass. ¹³C‐NMR spectroscopy of 26‐week old soil extracts revealed that structures typical of humic substances also evolved from the plant material.     

Measurement of the potentially available charge and the dissociation behaviour of humic acid from cobaltihexammine adsorption

The use of a new method for characterizing humic acids based on the measurement of the cobaltihexammine cation exchange capacity (CEC) vs. pH is examined. The method was first verified on a macroporous weak-acid cation exchange resin: charge vs. pH curves and pK values from cobaltihexammine adsorption identify with results from discontinuous acid-base titrations at high ionic strength (5 M). Similar agreement was obtained for humic acids from a Podzol soil: the cobaltihexammine-CEC identifies with the macromolecular charge (from continuous acid-base titrations) at ionic strength of 3 and 5 M, but slightly underestimates (5%) the humic acid charge at 1 M ionic strength. The cobaltihexammine method is suitable for determining the potentially available charge in the pH range 2 to 12 and the intrinsic pK values of humic acids.     

Residual Effect of Phosphorus Fertilizer in a Low‐Humic Andosol with Low Extractable Phosphorus

Abstract

Phosphorus (P) fertilization is quite important for crop production grown on Andosols. Fertilizer P‐use efficiency was 17% in a long‐term wheat experiment on a low‐humic Andosol. Residual effects of P fertilization were investigated using field soils in pot experiments. Topsoil was collected from the plots with or without annual P fertilizer at the rate of 65 kg‐P ha^?1 for 23 years (nitrogen phosphorous potassium (NPK) soil and nitrogen potassium (NK) soil, respectively). There was no significant difference in dry matter of wheat and P uptake between NPK and NK soils. However, dry matter of rice and P uptake were higher in NPK soil than in NK soil. Inorganic aluminum P (Al‐P_i) and iron P (Fe‐P_i) increased in NPK soil. Increase in Al‐P_i and Fe‐P_i during 23 years contributed little to P uptake by wheat, and repeated P fertilization is indispensable to obtain acceptable grain yield.