Suitability of the aluminon technique for measuring phytotoxic aluminum in solutions with varying sulfate concentrations

Abstract

Considerable uncertainty prevails concerning a suitable measure that can adequately describe Al phytotoxicity in nutrient and soil solutions. A study was conducted to evaluate the ability of a modified aluminon technique to discriminate between phytotoxic and non‐phytotoxic Al in solutions containing 80 μM Al with varying levels of CaSO₄(625 to 10000 μM), at two pH levels (4.2 and 4.8). The concentration of Al measured by the modified aluminon technique ranged from 18.3 to 77.7 μM,thereby indicating substantial polymerization in some of the solutions. The greatest amount of polymerization occurred at pH 4.8 in the presence of 625 μM CaSO₄. Increasing additions of CaSO₄resulted in an increase in predicted activity of AlSO₄ ⁺at both pH levels. However, with increasing addition of CaSO₄, the predicted activity of Al³⁺decreased at pH 4.2 or remained relatively constant at pH 4.8. The relationship between the sum of predicted activities of monomeric Al (Sa_{Al mono.}) in solution and tap root length of soybean [Glvcine max(L.) Merr.] cv. Lee was extremely poor, thereby indicating the inability of the modified aluminon technique to measure phytotoxic Al in solutions employed in the current study. This difficulty was due to failure of the modified aluminon technique to exclude lesser phytotoxic AlSO₄ ⁺species. The activity of Al³⁺was closely related to tap root length (R²= 0.865). The prediction of root length response to Al was further improved (R²= 0.899) by considering the solution Al index as: S[3a_A13+ + 2a_Al(OH)2+ + a_A1(OH)+]. There was a poor relationship between tap root length and the concentration of polymeric Al, thus suggesting the lower phytotoxicity of this component under the prevailing solution conditions.     

Acid soil tolerance of leucaena species in greenhouse trials

Abstract

Lines of Leucaena leucocephala (Lam.) de Wit were grown in greenhouse pots of an acid, Al‐toxic Tatum subsoil (clayey, mixed, thermic typic Hapludult) treated with 0 or 3000 ppm CaCO₃ to give final soil pH values of 4.1 and 5.3, respectively. Lines of L. leucocephala, plus those of other Leucaena species, were also tested on an acid, Monmouth soil (clayey, mixed, mesic, typic Hapludult) treated with 0 or 1500 ppm CaCO₃ to give final soil pH values of 4.8 and 6.6, respectively. The major index of acid soil tolerance used was relative root yield (unlimed/limed %).

Relative root yields of 117 L. leucocephala lines on Tatum soil ranged from 34 to 246%. Hence, liming the soil from pH 4.1 to 5.3 was highly beneficial to some lines and highly detrimental to others. Because Tatum subsoil is 89% Al saturated at pH 4.1, line tolerance to unlimed soil indicates tolerance to Al. Causes of yield depression at pH 5.3 were not determined.

On Monmouth soil, in a test involving 148 lines of 6 Leucaena species, relative root yields (unlimed/limed %) ranged from 23 to 386%. The line showing highest tolerance to the acid soil (P.I. 279578) and that showing lowest tolerance (P.I? 281636) are both L,. leucocephala. The majority of lines used on Monmouth soil (124 of a total of 148) were from this species. Average performances of the 6 species indicated that L. diversifolia Benth. (5 lines) was most tolerant to the acid Monmouth soil and liming the soil from pH 4.8 to 6.6 actually decreased root yields. The species L.. leucocephala (124 entries) and L. pulverulenta Benth. (4 lines) were intermediate, and L. lanceolata S. Wats. (3 lines) and I., retusa Benth. (1 line) appeared more sensitive to acid Monmouth soil. The Al saturation of Monmouth soil at pH 4.8 was only 23% (compared with 89% for Tatum at pH 4.1). The major growth limiting factor in acid Monmouth soil is believed to be Al toxicity, but this soil has not been as throughly characterized as has Tatum, and other factors may well be involved in explaining differential tolerances of Leucaena lines on the unlimed versus limed soil.

Results of these studies indicate that Leucaena species and lines within species differ significantly in tolerance to acid soils having high levels of exchangeable Al. Acid soil tolerant lines of Leucaena may be useful in expanding the acreage of this crop on oxisols and ultisols of the tropics and subtropics.     

Short‐term response of the Ca cycle of a montane forest in Ecuador to low experimental CaCl2 additions

The tropical montane forests of the E Andean cordillera in Ecuador receive episodic Sahara‐dust inputs particularly increasing Ca deposition. We added CaCl₂ to isolate the effect of Ca deposition by Sahara dust to tropical montane forest from the simultaneously occurring pH effect. We examined components of the Ca cycle at four control plots and four plots with added Ca (2 × 5 kg ha^–1 Ca annually as CaCl₂) in a random arrangement. Between August 2007 and December 2009 (four applications of Ca), we determined Ca concentrations and fluxes in litter leachate, mineral soil solution (0.15 and 0.30 m depths), throughfall, and fine litterfall and Al concentrations and speciation in soil solutions. After 1 y of Ca addition, we assessed fine‐root biomass, leaf area, and tree growth. Only < 3% of the applied Ca leached below the acid organic layer (pH 3.5–4.8). The added CaCl₂ did not change electrical conductivity in the root zone after 2 y. In the second year of fertilization, Ca retention in the canopy of the Ca treatment tended to decrease relative to the control. After 2 y, 21% of the applied Ca was recycled to soil with throughfall and litterfall. One year after the first Ca addition, fine‐root biomass had decreased significantly. Decreasing fine‐root biomass might be attributed to a direct or an indirect beneficial effect of Ca on the soil decomposer community. Because of almost complete association of Al with dissolved organic matter and high free Ca²⁺ : Al³⁺ activity ratios in solution of all plots, Al toxicity was unlikely. We conclude that the added Ca was retained in the system and had beneficial effects on some plants.     

Aluminum diffusion in Oxisols as influenced by soil water matric potential,ph, lime,gypsum, potassium chloride,and calcium phosphate

Abstract

Plant root exposure to soil aluminum (Al) depends on the soil solution Al concentration and transport to the root by diffusion. Changes in Al diffusive flux for two Oxisols was measured under laboratory conditions as a function of pH, water matric potential, and applications of gypsum, potassium chloride, and calcium phosphate. Double‐faced cation exchange resin sheets served as sinks for Al transported during 10‐day incubations through chambers containing 314 cm³ of soil. Across a range of soil pH values from 4.5 to 5.5, maximum diffusive flux of Al occurred at pH values of 4.7–4.8 in both soils and corresponded to increases of 2.2–3.0% relative to the unlimed treatment. Between pH values of 4.7–4.8 and 5.4, diffusive flux of Al decreased by 38 and 46% in the two Oxisols. Diffusive flux of Al decreased by 16–20% for the two Oxisols as soil water potentials decreased from ‐10 to ‐200 kPa. Magnitude of the reductions in diffusive flux of Al with decreasing soil water potential were less than those reported for diffusive flux of phosphorus (P) in prior investigations. Diffusive flux of Al increased by as much as 4‐fold with additions of CaSO₄ and KCl, which increased the soil solution Al concentration. Additions of 400 mg P dm^‐3 of soil had no effect on Al diffusion in either Oxisol.     

Influence of surface‐applied poultry manure on topsoil and subsoil acidity and salinity: A leaching column study

It has been suggested that surface applications of animal manure can ameliorate both top and subsoil acidity. For that reason, the effects of surface incorporation (0–5 cm) of a high rate of poultry manure to an acid soil on pH and exchangeable and soluble Al in the top‐ and subsoil were investigated in a leaching column study. During the experimental period of 108 d, columns received a total of 875 mm with leaching events occurring after 9, 37, 58, and 86 d. Incorporation of poultry manure into the surface 5 cm resulted in a large rise in pH measured in both 1M KCl and in soil solution. This liming effect was attributed primarily to the substantial CaCO₃ content of poultry manure. In the 15–45 cm layer, pH_KCl was not significantly different between poultry manure and control treatments but surprisingly, soil‐solution pH was substantially less in the poultry‐manure treatments. Exchangeable Al was significantly less in poultry manure than in control in all soil layers although the effect was most marked in the 0–5 cm layer. However, although concentrations and activities of monomeric Al (Al_mono), and the proportion of total Al present as Al_mono, in soil solution were lower under poultry manure than in control in the 0–5 cm layer, the reverse was, in fact, the case in lower soil horizons. This was attributed to a soluble‐salt effect, originating from the large cation content of poultry manure, displacing exchangeable Al³⁺ and H⁺ back into soil solution. Indeed, electrical conductivity and concentrations of Ca²⁺, Mg²⁺_, K⁺, and Na⁺ in soil solution were substantially higher in the poultry‐manure than in the control treatments at all soil depths. Poultry‐manure applications also resulted in substantial increases in the concentrations of Ca²⁺_, Mg²⁺_, K⁺, Na⁺, Al_mono, NH , and NO in leachates, particularly at the fourth leaching. It was concluded that although surface application of poultry manure can raise soil pH in the topsoil, increases in soluble‐salt concentrations in soil solution can greatly modify this effect in the subsoil.     

Maize yield response as affected by phosphorus,sulfur and nitrogen as banded applications on a volcanic ash derived tropical soil

Abstract

Phosphorus and sulfur deficiencies have been observed on many of the volcanic ash derived soils in Central America. One exploratory experiment was initiated in 1987 to examine maize (Zea mays L.) grain yield response to phosphorus, sulfur and nitrogen applied together on a volcanic ash derived soil in the Pacific coastal plain of Guatemala. Four cycles of yield data were collected in 2 rainy and 2 dry seasons. Treatments consisted of rate combinations of N (0, 100 kg ha^‐1 as urea), P (0, 22 kg ha^‐1 as triple superphosphate) and S (0, 57 and 114 kg ha^‐1 as CaSO₄.2H₂O) applied together in continuous bands in a randomized complete block design. Residual P and S response was measured during the last two cycles, whereby only urea was applied at a constant rate to all plots. The combined analysis of the first two cycles demonstrated a linear response of yield to applied S when no P was applied (4.95, 5.75 and 5.95 Mg ha^‐1 at 0, 57 and 114 kg S ha^‐1 respectively), while yield response was quadratic when S as CaSO₄2H₂O and P as triple superphosphate were applied together in a continuous band at 100 kg N ha^‐1 (5.38, 6.38 and 5.48 Mg ha^‐1 at the same S rates respectively). Response of yield to S was linear without and with P for the combined residual analysis of the last two cycles at the same N rate (4.65, 4.94, 5.26 and 4.68, 5.53, 5.56 Mg ha^‐1 respectively). Grain yields were maximized over the four cycle period using a joint N, P, S band (100 kg of N as urea, 22 kg P as triple superphosphate, and 57 kg S as CaSO₄.2H₂O ha^‐1). It is hypothesized that precipitation of dicalcium phosphate dihydrate (DCPD) and dicalcium phosphate (DCP) took place within the joint N‐P‐S band subsequently reducing the amount of P fixed as Fe or Al hydroxides and/or amounts of P complexed with amorphous allophane. The precipitation and subsequent dissolution of DCPD and DCP within the band could have increased P availability with time. Alternatively, SO₄ ⁼ blocking of adsorption sites could have increased P availability by reducing the amount of P fixed by the soil. It is possible that both of the previously mentioned mechanisms played a role in first cycle yield responses since increases were noted at the low S rate (57 kg S ha^‐1), while reductions were found when the S rate was doubled (114 kg S ha^‐1). Significant residual response for the last two cycles was observed for the joint triple superphosphate, CaSO₄.2H₂O, urea band, especially at the high S rate. This suggests that excess precipitation of DCP and DCPD could have occurred and that this provided delayed dissolution of the precipitated P reaction products. Chemical characterization of precipitated reaction products within the band is needed as well as further verification on similar soils in order to validate the observed response.     

在实验酸性硫酸盐条件和酸性硫酸盐土壤上可溶性铝的控制

The controls of soluble Al concentration were examined in three situations of acid sulfate conditions:1) experimental acid sulfate conditions by addition of varying amounts of Al(OH)3(gibbsite) into a sequence of H2SO4 solutions;2)experimental acid sulfate conditions by addition of the same sequence of H2SO4 solutions into two non-cid sulfacte soil samples with known amounts of acid oxalate extractable Al; and 3) actual acid sulfate soil conditions.The experiment using gibbsite as an Al-bearing mineral showed that increase in the concentration of H2SO4 solution increased the soluble Al concentration,accompanied by a decrease i the solution pH, Increasing amount of gibbsite added to the H2SO4 solutions also increased soluble Al concentration,but resulted in an increase in solution pH.Within the H2SO4 concentration range of 0.0005-0.5mol L^-1 and the Al(OH)3 range of 0.01-0.5g(in 25 mL of H2SO4 solutions),the input of H2SO4 had the major control on soluble Al Concentration and pH .The availability of Al(OH)3，however,was responsible for the spread fo the various sample points,with a tendency that the samples containing more gibbsite had a higher soluble Al concentration than those containing less gibbsite at equivalent pH levels.The experimental results from treatment of soil samples with H2SO4 solutions and the analytical results of acid sulfate soils also showed the similar trend.     

Calcium alleviation of hydrogen and aluminum inhibition of soybean root extension from limed soil into acid subsurface solutions

Alleviation by calcium (Ca) of inhibition of soybean [Glycine max (L.) Merr. cv. ‘Ransom'] root elongation by hydrogen (H) and aluminum (Al) was evaluated in a vertical split‐root system. Roots extending from a limed and fertilized soil compartment grew for 12 days into a subsurface compartment containing nutrient solution with treatments consisting of factorial combinations of either pH (4.0, 4.6, and 5.5) and Ca (0.2, 2.0, 10, and 20 mM), Al (7.5, 15, and 30 μM) and Ca (2.0,10, and 20 mM) at pH 4.6, or Ca (2, 7, and 12 mM) levels and counter ions (SO₄ and Cl) at pH 4.6 and 15 μM Al. Length of tap roots and their laterals increased with solution Ca concentration and pH value, but decreased with increasing Al level. Length of both tap and lateral roots were greater when Ca was supplied as CaSO₄ than as CaCl₂, but increasing Ca concentration from 2 to 12 mM had a greater effect on alleviating Al toxicity than Ca source. In the absence of Al, relative root length (RRL) of tap and lateral roots among pH and Ca treatments was related to the Ca:H molar activity ratio of solutions (R²≥0.82). Tap and lateral RRL among solutions with variable concentrations of Al and Ca at pH 4.6 were related to both the sum of the predicted activities of monomeric Al (R²≥0.92) and a log‐transformed and valence‐weighted balance between activities of Ca and selected monomeric Al species (R²≥0.95). In solutions with 15 μM Al at pH 4.6, response of tap and lateral RRL to variable concentrations of CaSO₄ and CaCl₂ were related to predicted molar activity ratios of both Ca:Al³⁺ (R²≥0.89) and Ca:3 monomeric Al (R²≥0.90), provided that AISO₄ and AI(SO₄)₂ species were excluded from the latter index. In all experiments H and Al inhibited length of lateral roots more than tap roots, and a greater Ca:H or Ca:Al concentration ratio was required in solutions to achieve similar RRL values as tap roots.     

Soil pH,extractable aluminum and tree growth on acid minesoils

Abstract

Paper birch and hybrid poplar were grown in acid minesoils amended with different rates and types of lime. Growth of the trees was correlated with soil pH, Ca, Mg, K, P and three measures of extractable Al ‐ 1 N KCl, 0.01 M CaCl₂ and H₂O extractable Al. Correlations between soil pH and extractable Al and between the three measures of extractable Al were also determined. Soil pH accounted for the largest share of the total variation in root and shoot growth of both species over all soils. Correlations between tree growth and extractable Al for all soils combined were low and generally non‐significant. Significant correlations were obtained between soil pH and extractable Al and between the three measures of extractable Al, however, the relationships varied among soils.     

Evaluation of soil P‐test values of canton Geneva/Switzerland in relation to P loss risks

The P status of the soils of Geneva is routinely determined by two independent chemical extractions. The P amounts extracted independently by an aqueous solution of ammonium acetate 0.5 M + EDTA 0.02 M (pH 4.65) (1:10 solid weight : solution volume, 60 minutes) and by H₂O (1 : 10 solid weight : solution volume, 60 minutes) were assumed to represent mobilizable and mobile phosphorus pools. The best correlations with the data from 1023 crop field soil samples in Geneva canton during the years 1994 to 2000 were obtained by power functions if the data were grouped in two distinct pH ranges: pH 4.6–6.5: (P‐AAE) = 16.436 (P‐H₂O) ^0.6083; R² = 0.625; n = 166, pH 6.6–8.6: (P‐AAE) = 25.582 (P‐H₂O) ^0.6518; R² = 0.47; n = 857. The derivatives of these functions are representative of apparent P‐buffering power. Environmentally sound threshold values for P‐H₂O and P‐AAE are estimated by calculating the change points first of these P‐AAE (quantity) against P‐H₂O (intensity) curves and second P‐buffering power against P‐H₂O or P‐AAE curves. The change points obtained from the smoothed quantity‐intensity data were: pH 4.6–6.5: P‐H₂O = 3.8 mg kg^–1 and P‐AAE = 16.436 (3.8)^0.6083 = 37.0 mg kg^–1; n = 166, pH 6.6–8.6: P‐H₂O = 2.5 mg kg^–1 and P‐AAE = 25.582 (2.5)^0.6518 = 46.5 mg kg^–1; n = 857. The change‐points for P‐buffering power curves occurred at pH 4.6–6.5: P‐H₂O = 1.3 mg kg^–1; P‐AAE = 19.7 mg kg^–1; n = 166, pH 6.6–8.6: P‐H₂O = 1.3 mg kg^–1; P‐AAE = 20.6 mg kg^–1; n = 857. The threshold buffering powers were: pH 4.6–6.5: d(P‐AAE)/d(P‐H₂O) = 9.998 (P‐H₂O) ^–0.3917 = 9.0, pH 6.6–8.6: d(P‐AAE)/d(P‐H₂O) = 16.674 (P‐H₂O) ^–0.3482 = 15.2. These results show that presently only about 25 % of the crop soils of Geneva canton were within these safe limits. The possibility of applying values of this magnitude which are significantly lower than officially recommended reference levels for phosphorus fertilizer recommendations is supported by recent agronomic investigations.     

Calcium Sulphate versus Lime as Fertilizer Filler: Effects on Ammonium and Nitrate Uptake by Perennial Ryegrass

Abstract

The recovery of ¹⁵N‐labelled nitrogen (N) by perennial ryegrass can be significantly increased by mixing gypsum (CaSO₄ · 2H₂O) into soil rooting medium at rates equivalent to 0.7 t ha^?1. Similar improvements in fertilizer N efficiency might be achieved, at less cost and more conveniently, by applying smaller amounts of CaSO₄ anhydrite more strategically to fertilizer microsites as a fertilizer filler or diluting agent, in calcium ammonium nitrate (CAN), in place of CaCO₃. With this in mind, two complementary pot experiments were conducted under simulated spring conditions in a controlled environment chamber. Use of CaSO₄ as diluting agent, in place of CaCO₃, appreciably enhanced (>30%) the uptake of labeled N by perennial ryegrass plants within the second week of regrowth, but thereafter, because losses of ¹⁵N‐labeled NO₃ ^?‐N from pots by denitrification or leaching had been minimal, plants in both treatments eventually recovered equal amounts of this N form from the soil.     

pH and solubility of aluminium in acidic forest soils: a consequence of reactions between organic acidity and aluminium alkalinity

Data from two Podzol O and E horizons, sampled in 1-cm layers at 13 points within 2 m × 2 m plots, were used to test the hypothesis that the composition of hydrogen ions (H) and aluminium (Al) adsorbed to the solid-phase soil organic matter (SOM) determines pH and Al solubility in organic-rich acidic forest soils. Organically adsorbed Al was extracted sequentially with 0.5 m CuCl₂ and organically adsorbed H was determined as the difference between total acidity titrated to pH 8.2 and Al extracted in 0.5 m CuCl₂. The quotient between fractions of SOM sites binding Al and H (N_Al/N_H) is shown to determine the variation in pH and Al solubility. It is furthermore shown that models in which pH and Al solubility are linked via a pH-dependent solubility of an Al hydroxide and in which cation exchange between Al³⁺ and Ca²⁺, rather than cation exchange between Al³⁺ and H⁺, is the main pH-buffering process cannot be used to simulate pH or Al solubility in O and E horizons. The fraction of SOM sites adsorbing Al increased by depth in the lower O and throughout the E horizon at the same magnitude as sites adsorbing H decreased. The fraction of sites binding the cations Ca²⁺ + Mg²⁺ + K⁺ + Na⁺ remained constant. It is suggested that a net reaction between Al silicates (proton acceptors) and protonated functional groups in SOM (proton donors) is the long-term chemical process determining the composition of organically adsorbed H and Al in the lower part of the O and in the E horizon of Podzols. Thus, in the long term, pH and Al solubility are determined by the interaction between organic acidity and Al alkalinity.     

The effects of leaching surface‐applied amendments on subsoil aluminum and alfalfa growth in a Louisiana Ultisol

Abstract

A greenhouse leaching column study was conducted to compare the effects of surface‐applied langbeinite (LB), phosphogypsum (PG), Ca‐ silicate slag (SS), and calcitic lime (CL) on subsoil Al and growth of alfalfa (Medicago sativa L. ‘Florida 77') in Toula silt loam soil (Typic Fragiudult). Langbeinite was found to be more effective than PG in the reduction of subsoil exchangeable Al, apparently through SO₄ ^2‐‐induced Al precipitation. This study demonstrated that high exchangeable Al levels are not always indicative of Al toxicity in the soil solution phase. The primary factors limiting alfalfa growth in the Toula soil were found to be surface soil pH and Mn toxicity rather than subsoil Al toxicity. The liming materials, SS and CL, effectively corrected the surface soil Mn and pH problems, but had no effect on subsoil chemical properties.     

Fluoro‐mobilization of metals in a Slovak forest soil affected by the emissions of an aluminum smelter

Depositions originating from a central Slovak Al smelter may increase metal solubility in adjacent soils because they contain F (mainly HF). The reason for fluoro‐mobilization of metals may be the formation of soluble fluoro‐metal complexes or the mobilization of organic matter and subsequent formation of organo‐metal complexes. The objectives of our work were (1) to assess the extent of metal mobilization by fluoride in a Slovak Lithic Eutrochrept affected by the emissions of an Al smelter and (2) to model the dissolved metal species with the help of a chemical equilibrium model (MINEQL+). The O (Moder), A, and B horizons were equilibrated with solutions at F concentrations of 0, 0.9, 2.7, and 9.0 mmol l^—1. In the extracts, the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Zn, dissolved organic carbon (DOC), free and complexed F, and the pH and electrical conductivity (EC) were determined. The heavy metal concentrations in the O horizon (Cd: 0.99, Cr: 18.0, Cu: 44, Ni: 26, Pb: 110, and Zn: 84 mg kg^—1) were 2.5 to 9 times larger than those in the A and B horizons. The concentrations of H₂O‐soluble F decreased from the O (261 mg kg^—1) to the A (103 mg kg^—1) and B horizon (92 mg kg^—1). In batch experiments increasing addition of F increased the equilibrium concentrations of Al, Cr, Cu, Fe, Ni, Pb, and DOC in all samples, of Cd in the A, and of K in the B horizon. At the same time the concentrations of complexed F and pH increased whereas EC decreased. Chemical equilibrium modelling indicated that the mobilizing effect of F resulted from the formation of fluoro‐Al complexes and organo‐complexes of all other metals.     

Production of blue hydrangea flowers without aluminum drenches

Abstract

Hydrangea ‘R.F. Felton’ plants were grown to flowering in a soilless potting medium that had been amended with aluminum nitrate [Al(NO₃)₃.9H₂O], Kaolite (a calcined clay mineral, of which about 70% is amorphous cristobalite, tridymite, and mullite), or an aluminum (Al)‐rich water clarification sludge, or left unamended. Inclusion of 10% Kaolite (v/v) in the medium led to a marked increase in the Al content of the flowers and a corresponding increase in their blueness. Flower phosphorus (P) content was negatively correlated with blue color. High calcium (Ca) and potassium (K) contents of the flowers also contributed to blueness. High concentrations of manganese (Mn) had a small negative effect on blueness. Media that produced blue flowers had pH values of less than 4.9. DTPA extracts (2 mM; 1:1.5 v/v) of these low‐pH media contained at least 12 mg Al L^‐1 at potting, rising to about 21 mg Al L^‐1 at harvest.     

Solubility control of KCl extractable aluminum in soils with variable charge

Abstract

Solubility and kinetic data indicated that concentrations of aluminum (Al) extracted with 1 M KCl are determined by the solubility of a precipitated A1(OH)₃ phase in soils dominated by variable charge minerals. Kinetic studies examining the release of Al on non‐treated and KCl treated residues indicated the precipitation of an acid‐labile Al phase during the extraction procedure. The log ion activity products estimated for the KCl extracts ranged between 8.1–8.6 for the reaction Al(OH)₃ + 3H⁺ < = > Al³⁺+ 3H₂O, which was similar to the solubility product of several Al(OH)₃phases. The mechanism proposed for Al precipitation indicated that Al released by exchange with added K⁺ hydrolyzed and released H⁺ that was readily adsorbed on surfaces of variable charge minerals. The increased ionic strength of the extracting solution further increased the amount of H⁺adsorbed to the variable charge surface and reduced the H⁺ concentration in the aqueous phase. Consumption of H⁺ induced further hydrolysis of Al, resulting in supersaturation of the extracting solution and formation of polynuclear hydroxy Al species. It was concluded that the 1 M KCl extraction does not quantitatively extract salt exchangeable Al from variable‐charge soils.     

Using Organic Matter with Chemical Amendments to Improve Calcareous Sodic Soil

Abstract

Kangping soil in northeast China is a sodic soil characterized by a high pH and excessive sodium. The high pH and excessive sodium in sodic soils generally cause loss of soil structure, reduce hydraulic conductivity (HC), increase soil hardness, and make the soil unproductive land. After we mixed organic matter (rice straw) and chemical amendments (H₂SO₄, CaSO₄, and FeSO₄), a column experiment was conducted to evaluate the physical and chemical properties of the soil influenced by the changes in HC, penetrability of soil s`urface, pH, electrical conductivity, CO₃ ^2‐, HCO₃ ^?, Ca²⁺, Na⁺, sodium adsorption rate (SAR), available phosphorus (P) and iron (Fe), and leached P.

Organic matter decreased the concentrations of CO₃ ^2‐, HCO₃ ^?, and Na⁺ in soil solution and increased the total volume of the leachate. Organic matter also reduced the amount of available Fe and increased the available P. However, organic matter did not affect the penetrability of the soil surface as much as soil hardness, HC, and SAR within the short period of this experiment. Among the chemical amendments, H₂SO₄ and FeSO₄ were more effective than CaSO₄ to restore HC, electrical conductivity, Na⁺, and SAR. The chemical amendments, compared with organic matter, significantly leached P from the soil in this study, but the leaching was independent of the concentration of available P in the soil. The CaSO₄ had the strongest effect in increasing leached P from the soil without changing the concentration of available P in the soil. Organic matter with added CaSO₄ leached P from the soil more than all other treatments.     

Extraction of water‐soluble organic matter from mineral horizons of forest soils

Dissolved organic matter (DOM) is involved in many important biogeochemical processes in soil. As its collection is laborious, very often water‐soluble organic matter (WSOM) obtained by extracting organic or mineral soil horizons with a dilute salt solution has been used as a substitute of DOM. We extracted WSOM (measured as water‐soluble organic C, WSOC) from seven mineral horizons of three forest soils from North‐Rhine Westphalia, Germany, with demineralized H₂O, 0.01 M CaCl₂, and 0.5 M K₂SO₄. We investigated the quantitative and qualitative effects of the extractants on WSOM and compared it with DOM collected with ceramic suction cups from the same horizons. The amounts of WSOC extracted differed significantly between both the extractants and the horizons. With two exceptions, K₂SO₄ extracted the largest amounts of WSOC (up to 126 mg C kg^–1) followed by H₂O followed by CaCl₂. The H₂O extracts revealed by far the highest molar UV absorptivities at 254 nm (up to 5834 L mol^–1 cm^–1) compared to the salt solutions which is attributed to solubilization of highly aromatic compounds. The amounts of WSOC extracted did not depend on the amounts of Fe and Al oxides as well as on soil organic C and pH. Water‐soluble organic matter extracted by K₂SO₄ bore the largest similarity to DOM due to relatively analogue molar absorptivities. Therefore, we recommend to use this extractant when trying to obtain a substitute for DOM, but as WSOM extraction is a rate‐limited process, the suitability of extraction procedures to obtain a surrogate of DOM remains ambiguous.     

Solution chemistry in acid forest soils: Are the BC : Al ratios as critical as expected in Switzerland?

The molar ratio of base nutrient cations to total dissolved aluminum (BC : Al_tot) in the soil solution was measured at six forest sites in Switzerland in acid mineral soils to determine whether the ratio measured in the field was lower than the critical value of 1, as predicted by the mapping of exceedances of critical loads of acidity. The soil chemistry was then related to the soil solution composition to characterize the typical effective base saturation (BS) and BC : Al ratio in soil leading to critical BC : Al_tot in the soil solution. The median BC : Al_tot ratio in the soil solution never reached the critical value in the root zone at any sites for the whole observation period (1999–2002), suggesting that the BC : Al_tot ratios measured in the field might be higher than those modeled for the determination of critical loads of acidity. The gibbsite model usually applied for the calculation of critical loads was a poor predictor of the Al³⁺ activity at the study sites. A curvilinear pH‐pAl³⁺ relationship was found over the whole range of pH (3.8–6.5). Above a pH of 5.5, the slope of the pH‐pAl³⁺ relation was close to 3, suggesting equilibrium with Al(OH)₃. It decreased to values smaller than 1.3 below a pH of 5.5, indicating complexation reactions with soil organic matter. The BS and the BC : Al ratios in the soils were significantly correlated to the BC : Al_tot ratios in the soil solution. The soil solutions with the lowest BC : Al_tot ratios (≤ 2) were typically found in mineral soils with a BS below 10 % and a BC : Al ratio in the soil lower than 0.2. In acid pseudogleyed horizons overlying a calcareous substrate, the soil solution chemistry was strongly influenced by the composition of the underlying soil layers. The soil solutions at 80 cm had pH values and BC : Al_tot ratios much higher than expected. This situation should be taken into account for the calculations of critical loads of acidity.     

Acid soil tolerances of two wheat cultivars related to soil Ph,KCl‐extractable aluminum and degree of aluminum saturation

Aluminum toxicity, associated with soil acidity, is a major growth‐limiting factor for plants in many parts of the world. More precise criteria are needed for the identification of potential Al toxicity in acid soils. The objective of the current study was to relate the acid soil tolerances of two wheat cultivars to three characteristics of an acid Tatum subsoil (clayey, mixed, thermic, typic Hapludult): pH in a 1:1 soil to water suspension; KCl‐extractable Al; and degree of Al saturation. Aluminum‐tolerant ‘BH 1146’ (Brazil) and Al‐sensitive ‘Sonora 63’ (Mexico) wheat cultivars were grown in greenhouse pots of soil treated with CaCO₃ to establish final soil pH levels of 4.1, 4.6, 4.7, 4.9, 5.2 and 7.3. Soil Al, Ca and Mg were extracted with 1 N KCl, and Al saturation was calculated as KCl‐Al/KCl Al + Ca + Mg%.

Within the soil pH range of 4.1 to 4.9, BH 1146 tops and roots produced significantly more dry matter than did those of Sonora 63; however, at pH 5.2 and 7.3, the top and root yields of the two cultivars were not significantly different. Significant cultivar differences in yield occurred over a range of 36 to 82% saturation of the Tatum soil. Graphs of relative top or root yields against soil pH, KCl‐extractable Al and Al saturation indicated that the two cultivars could be separated for tolerance to Tatum soil under the following conditions: pH less than 5.2 (1:1 soil‐water); KCl‐Al levels greater than 2 c mole kg^‐1 and Al saturations greater than 20%. Results demonstrated that any soil test used to predict Al toxicity in acid soils must take into account the Al tolerances of the plant cultivars involved.