Comparison of phosphate adsorption on clay minerals for soilless root media

Abstract

The greenhouse industry aims to decrease phosphate discharge to help reduce eutrophication of surface waters, to reduce fertilizer consumption, and to maintain a more constant level of plant‐available phosphate. Iron and aluminum oxides and some aluminosilicate minerals are efficient sorbents for phosphate. The phosphate adsorption characteristics of synthetic hematite (α‐Fe₂O₃), goethite (α‐FeOOH), and allophane (Si₃Al₄O₁₂ nH₂O), and a commercial alumina (A1₂O₃) were evaluated to determine their potential for reducing phosphate leaching from soilless root media. The pH dependence of phosphate adsorption and maximum adsorption capacities were determined by reacting each mineral with various levels of phosphate between pH 4.0 and 9.0 in a 10 mM potassium chloride (KCl) background solution. Adsorbed phosphate was determined by loss from solution. Adsorption envelopes (adsorbed phosphate versus pH) showed a decrease in phosphate adsorption with increasing pH, particularly for alumina and allophane, and at greater added phosphate concentrations. The maximum adsorption capacities per unit mass of the minerals at pH 5.4 decreased in the order allophane > alumina ? goethite > hematite. When expressed on a surface area basis, the order of maximum adsorption capacity remains the same except that alumina exceeded that of goethite. The allophane, goethite, and alumina sorbed enough phosphate that 3 to 9 g of these minerals would retain the amount of phosphate required for a high nutrient element requiring plant such as chrysanthemum.     

Cadmium and zinc accumulation by the hyperaccumulator Thlaspi caerulescens from soils enriched with insoluble metal compounds

Abstract

The clay mineralogy of seven Dystrandepts developed on basalts in Northland (New Zealand), the French Massif Central and Western Oregon (U.S.A.) was determined by selective dissolution—differential infrared spectroscopy in combination with chemical, X-ray diffrac tion, electron microscopic and thermogravimetric analyses. Of 14 soil samples, 6 from Northland and Cantal (French Massif Central) contained allophane and imogolite, whereas the remaining 8 did not. Allophane-like constituents and/or “alumina” were found in all the samples, and opaline silica was present in three A₁ horizons. The contents of 2 : 1–2 : 1 : 1 layer silicates and their intergrades varied somewhat among the samples. Predominant volcanic glass shards in the Northland Dystrandepts and quartz in the Western Oregon Dystrandepts indicated that their parent materials were not restricted to basalt.     

Electrokinetic properties of variable charge clays in the presence of an anionic xanthan polysaccharide and inorganic electrolytes

The effect of the electrolytes (MA: NaCl, MgCl₂ , PbCl₂ , and NaH₂PO₄ ) on the polymeric (a) weak-stabilization (PWST), (b) flocculation (PFL); and (c) stabilization (PST) of allophane in the presence of xanthan polysaccharide (GX), was investigated by electrophoretic mobility (EPM) measurements. At pH 6.5 (i.e.p.), with further addition of chlorides, the decrease in the absolute value of the negative EPM (|—EPM|) of allophane in 0.01 mm MA solutions indicated the suppression of PWST and PST, respectively, probably due to the decrease in the repulsive force originating from the negatively charged GX-chains with the addition of MA. By first addition of MA, the decrease in the |—EPM| value of allophane in 0.01 mm NaCl and MgCl₂ solutions also showed the suppression of PWST and PST. In 0.01 mm PbCl₂ and NaH₂PO. solutions, the increase in the EPM and |—EPM| values of allophane reflected the dispersion due to the specific adsorption of Pb₂₊ and H₂PO₄ - ions on the negatively and positively charged sites of the surface, respectively. At pH 4.5, the decrease in the |—EPM| value of allophane in 0.1 mm NaH₂PO₄ solution indicated the suppression of PST due to the specific adsorption of H₂PO₄ - ion on the positively charged surface of the particles. The absence of (i) PWST in the presence of GX and (ii) high stability in the presence of cationic lead species for the flocculated imogolite at pH 8.5 can be attributed to the tubular structure proposed by Cradwick et al. (1972: Nature (London) Phys. Sci., 240, 187-189), namely, to the difficulty in the development of a negative charge on the outer surface of its unit particle.     

Phosphate fixation by ando soils different in their clay mineral composition

The phosphate fixation capacity at pH 4.5 and an equilibrium concentration of 250 mM phosphate was measured. The soil samples were divided into five groups according to their clay mineralogical composition. The first group soils contain opaline silica and allophanelike constituents, and some unidentified minerals, the second opaline silica and crystalline layer .i1icates, the third opaline silica and crystalline layer silicates with additional allophanelike constituents or aluminarich gel-like materials, the fourth allophanelike constituents, allophane and imogolite and the fifth crystalline layer silicates, allophanelike constituents and alumina-rich gel-like materials, plus some halloysite-like minerals, respectively. The first group soils had phosphate fixation capacities of 3,000 to 8,000, the second group soils 1,000 to 3,000, the third group loib 2,000 to 13,000, the fourth group soils 8,000 to 15,000 and the fifth group soil. 5,000 to 12,000 mg P₂O₅/100 g oven-dry soil, respectively. The fourth group soils in which allophane and imogolite predominated showed the highest phosphate fixation capacity.

The fractions which dissolved from almost all soil samples by treatments with 6% H₂O₂ Na₂S₂O₄-NaHCO₂-Na citrate and 2% Na₂CO₃ were estimated to have very high phosphate fixation capacities (8,000 to 19,000 mg P₂O₅/100 g dry-matter), and there was not much difference among the soil samples examined. Iron and aluminum combined with humus, allophanelike constituents, alumina-rich gel-like materials and halloysite-like minerals in addition to allophane and imogolite contribute to the phosphate fixation of Ando soils.     

Distribution of allophane and organic matter in podzol B horizons: reply to Buurman & Van Reeuwijk

The macromorphology, micromorphology and chemical nature of illuvial material in podzol B horizons and subsoils can be explained by contributions from two different migrating species: (a) a positively-charged mixed Al₂O₃-Fe₂O₃-SiO₂-H₂O sol incorporating minor amounts of adsorbed organic matter and silicate clay, and (b) negatively charged organic sols and solutions, carrying minor amounts of Al, Fe and clay. These species can also be generated within B horizons of high root activity. An alternative theory, that requires allophane to be formed in situ in the B horizon by microbial decomposition of precipitated organic complexes, fails to predict the observed distribution of allophane.     

Influence of allophane and organic matter contents on surface properties of Andosols

The aim of this study was to use nitrogen gas adsorption to study the complex surface properties of a wide range of Andosol Ah and Bw horizons; N₂ gas adsorption not only provides specific surface area, SSA, but it also yields complementary information about micropore volume and hydrophilic and/or hydrophobic surface properties. Total SSAs were positively related to micropore SSA which was, in its turn, positively interrelated to the dimensionless parameter C of the Brunauer‐Emmett‐Teller (BET) equation (micropore N₂ filling) and microporous allophane content. The more allophanic the Andosol horizon sample, the larger were its total, micropore and mesopore SSAs. On the other hand, strong negative exponential relationships were obtained between either total or micropore or mesopore SSA and soil organic carbon content, with a SSA threshold at an organic carbon content of c. 8–10%, the SSAs being extremely small at larger organic carbon content values. Both SSA_BET and C_BET decreased non‐linearly as a function of the organic C/allophane ratio, with either a SSA_BET or a C_BET threshold at an organic C/allophane ratio value of 3–5, above which both SSA_BET and C_BET were very small (mostly the aluandic Andosol Ah horizons). The more the soil allophanes are assumed to be coated, the more hydrophobic the soil surfaces become and the smaller both SSA_BET and C_BET become; nitrogen gas has a permanent quadrupole moment and therefore acts as a polar probe when surfaces are sufficiently hydrophobic. The antagonistic roles played by allophanes and organic matter in both the SSAs and the values of the dimensionless parameter C in the BET equation were also highlighted by (i) multiple linear regressions between the SSAs and both allophane and organic carbon contents and (ii) principal‐component analysis of SSA_BET, C_BET and soil constituent (allophane, ferrihydrite and organic C) contents.     

Chemical characterization of conducive and suppressive soils for potato scab in Hokkaido,Japan

Potato common scab induced by Streptomyces scabies is a serious constraint for potato-producing farmers and the incidence of potato scab depends on the soil chemical properties. We examined the chemical characteristics of conducive and suppressive soils to potato common scab with reference to the chemical properties of nonallophanic Andosols, recently incorporated into the classification system of cultivated soils in Japan. Allophanic Andosols with a ratio of pyrophosphate-extractable aluminum (Al_p) to oxalate-extractable aluminum (Al_o) of less than 0.3–0.4 were “conducive” soils with a high allophane content of more than 3%. On the other hand, nonallophanic Andosols with a Al_p/Al_a ratio higher than this critical value were “suppressive” soils, and their allophane content was less than 2%. The concentration of water-soluble aluminum (AI) was also a useful index for separating conducive from suppressive soils as well as the Al_p/Al_a value and allophane content. The suppressive soils showed a much higher concentration of water-soluble Al at pH 4.5 to 5.5 than the conducive soils. The high concentration of water-soluble Al may be responsible for the control of the incidence of potato common scab in Andosols.     

Mechanisms of pentachlorophenol adsorption by soils

The precipitation and adsorption of pentachlorophenol (PCP) on allophane was confirmed by adsorption experiments carried out at various pll values. The precipitation of PCP took place around base-unsaturated clay particles when the concentration of PCP exceeded solubility. The adsorption of PCP involves anion exchange reaction as well as physical adsorption due to van der Waals' force, and the PCP adsorbed as anions is released with greater when washed with deionized water.

Allopbane of Andosols appears to adsorb PCP largely as anions, while humus, balloysite, and allophane (molar SiO₂/Al₂O₃ ratio about 2) seem to adsorb PCP mostly as molecules. The precipitation of PCP in mlcell might participate in the adsorption. PCP mixed with layer silicate day minerals such as illite, montmorillonite, and kaolinite sublimated by about 200°C. In contrast to this, PCP mixed or adsorbed on allophane did not sublimate by 200°C but burnt out between 250 and 500°C showing a strong exothermic reaction.     

Effect of phosphogypsum application on the chemical properties of Andosols,and the growth and Ca uptake of melon seedlings

Abstract

Allophanic Andosols are widely used as a major material in commercial nursery media for fruit vegetables in Japan because of their remarkable physical properties, such as a high water-holding capacity. In the present study, our objectives were: (1) to examine the effect of phosphogypsum (PG) on the chemical properties of Andosols, (2) to investigate the effect of PG on the growth and Ca uptake of melon seedlings. The effect of PG on chemical properties of Andosols was studied using five Andosols with different inorganic and organic colloidal components. The change in soil pH (H₂O) was dependent on the soil samples; an increase was observed in the case of Kawatabi 3Bw soil; a sharp decrease in Kawatabi A2 soil; and almost no change or a slight decrease in Kameoka A1, A2 and Bw soils. The water-soluble Ca content was examined as an index of Ca availability in Andosols treated with PG. The increment in water-soluble Ca by PG application was depressed by allophane. The effect of PG application to the nursery media prepared from Andosols on growth and Ca uptake of melon (Cucumis melo L.) was examined in 2002. Three different varieties, Amusu, Earl's and Midorishima, were used in this experiment. The pH value of nursery media was stable at 6.4 ± 0.1 regardless of PG application rate. In contrast, electrical conductivity was clearly increased by PG application, and was reached at 1.2 dS m^?1 in 4.0 g L^?1 application. The application of PG increased water soluble Ca of nursery media from 1.7 to 5.2 cmol_c L^?1. Both top and root growth of melon seedlings were enhanced regardless of varieties, dry matter weights were maximized at 4 g L^?1 PG application. The Ca uptake of melon seedlings was promoted by PG application in all the varieties. It was suggested that the relative root growth rate of melon seedlings was closely related to the Ca uptake of melon seedlings.     

Simulation of flow patterns and ion-exchange in soil percolation experiments

An increased understanding of ion-exchange processes in raw-humus was obtained by simulations using quantitative mathematical models. The work is based on a series of percolation experiments with a water flow of about 1 mm min^?1 through raw-humus samples of 4 cm thickness. For the input solutions consisting of 10^?3 N H₂SO₄, HNO₃, HCl and NaCl the results indicate that cation-exchange reactions are the most important processes for the chemical composition of the run-off. Since a large part of the water flows quickly through the soil, both the water residence time and the ion-exchange kinetics must be taken into account. As a basis for the chemical model, a hydrologic sub-model reproducing the residence time distribution of the flow in the soil is used. Considering the ions H⁺, M⁺ (monovalent metal ions) and M²⁺ (divalent metal ions), four different chemical models were tried but only one of them gave satisfactory agreement with the experimental results. This model has 5 independent parameters and consists of first and second order chemical processes.     

Weathering and allophane neoformation in soils developed on volcanic ash in the Azores

On Faial and Pico islands (Azores), we studied two profiles on basaltic pyroclasts that contain buried horizons, and we focussed on petrography, micropedology and mineralogy. Emphasis was given to weathering of the lapilli and ashes, and the neoformation of allophane. A combination of optical studies, in situ chemical analyses, X‐ray diffraction and infrared spectroscopy of clay fractions revealed that allophane is present both in the micromass of the groundmass, in alteromorphs after lapilli or pumice, and in clay coatings. Whereas most studies describe allophane as a colloidal fraction formed by the congruent and total dissolution of the ashes, this study shows evidence for the formation of allophane alteromorphs, due to leaching of Si and cations, with preservation of the original shapes of the tephra. The allophane alteromorphs often display optical characteristics that resemble those of palagonite. Increasing alteration is observed through three steps: (i) hydration of the glass associated with strong cation and Si leaching, (ii) allophane hypocoatings, and (iii) allophane alteromorphs with development of intragrain bridges. The chemical signature of the alteromorphs varies from a pure alumino‐silicate at one extreme to an Fe(Ti) enriched alumino‐silicate at the other. Between those two extremes, the colour grades from yellow to dark orange, with microzonations. An Al‐rich allophane composition is associated with gibbsite in the EUR6‐Pico profile, whereas at the base of the EUR5‐Faial profile, Si‐rich allophane is associated with halloysite. Some variations of the palaeo‐environment are also suggested by strong iron segregation observed with various secondary phases (ferrihydrite, haematite, iddingsite).     

Cold and hot water–extractable organic matter as indicators of litter decomposition in forest soils

Mild extractions were used as indicators of easily decomposable organic matter (OM). However, the chemical composition of extracted OM often remained unclear. Therefore, the composition of cold and hot water–extractable OM was investigated in the O horizons (Oi, Oe, Oa) of a 170 y old beech stand (Fagus sylvatica) in the Ore Mtns., SE Germany. To simulate litter decomposition, the O horizon samples were incubated for 1 week under defined conditions. Cold‐ and hot‐water extracts were analyzed and chemically characterized by pyrolysis–field ionization mass spectrometry (Py‐FIMS). The C and N concentrations were always lower in the cold‐(C: 2.69 to 3.95 g kg^–1; N: 0.14 to 0.29 g kg^–1) than in the hot‐water extracts (C: 13.77 to 15.51 g kg^–1; N: 0.34 to 0.83 g kg^–1). The C : N ratios of both extracts increased with increasing depth. Incubation increased the concentrations of C and N in all water extracts, while C : N ratios of extracts decreased. The molecular‐chemical composition of cold and hot water–extracted OM revealed distinct differences. Generally, cold water–extracted OM was thermally more stable than hot water–extracted OM. The mass spectra of the hot water–extracted organic matter revealed more intensive signals of carbohydrates, phenols, and lignin monomers. Additionally, the n‐C₂₈ fatty acid and the n‐C₃₈–to–n‐C₅₂ alkyl monoesters clearly distinguished the hot‐ from the cold‐water extract. A principle‐component analysis visualized (1) alterations in the molecular‐chemical composition of cold‐ and hot‐water extracts due to previous incubation of the solid O horizon samples and (2) a decomposition from the Oi to the Oh horizon. This provides evidence that the macromorphological litter decomposition was reflected by the chemical composition of water extracts, and that Py‐FIMS is well‐suited to explain at the molecular level why OM decomposability is correlated with water‐extracted C.     

SYNTHETIC ALLOPHANE AND IMOGOLITE

In order to prepare allophane and imogolite in the laboratory, solutions containing l–2× 10^–3 M orthosilicic acid and 4–0.5 × 10^–3 M A1C1₃ (SiO₂/Al₂O₃ molar ratio; 0.5, 1.0, 2.0, 4.0 and 8.0) were heated at 95–100°C for 113 hours after addition of NaOH (NaOH/Al molar ratio; 1.0, 2.0, 2.8 and 3.0). Boehmite was found in the precipitates from all solutions with initial SiO₂/Al₂O₃ ratios of 0.5. Imogolite was found with allophane II in the products from solutions with SiO₂/Al₂O₃ ratios of 1.0 or greater and with NaOH/Al ratios of 2.8 or less (final pH 5.0), whereas allophane I was found in the precipitates from solutions with the same SiO₂/Al₂O₃ ratios but with the NaOH/Al ratio of 3.0 (final pH = 5.0–6.3). The mode of formation, chemical composition, infrared spectra, electron micrographs, electron diffraction patterns and differential thermal analysis curves of synthetic imogolite and allophanes (I and II) were compared with those of their natural counterparts.     

Potassium Selectivity in Transported Volcanic Soils (Sorribas) under Banana Cultivation in Relation to Banana-Wilt Expression Caused by Fusarium oxysporum f. sp. Cubense

The bases for the microbiological nature of certain soils to suppress plant diseases caused by soil pathogens are well established. However, the microbial origin of the suppressiveness does not exclude edaphic factors and soil-management strategies, which need to be studied under field conditions. With respect to abiotic factors, we investigated the importance of potassium (K) selectivity on soil conduciveness and suppressiveness to banana wilt (positive or negative disease expression) caused by soil fungus Fusarium oxysporum f. sp. cubense in Sorribas field plots (transported volcanic soils) from the Canary Islands that are naturally affected by Fusarium wilt. To facilitate comparison among sites, soil K variables were normalized using Z scores and tested by one-way analysis of variance within each soil sample type (soil areas where banana plants show positive or negative wilting symptoms characteristic of Panama disease), with the site as the block factor. Variations of Z scores within the same plot were explained mostly by the differences between soil K indices between areas with and without disease. In fact, soil conduciveness or suppressiveness to Fusarium wilt seemed to be substantially affected by changes in exchangeable and solution K indices. Potassium selectivity coefficients (K_G) were always greater in areas without disease than in those with disease. The differences between samples can be related to allophane composition and clay mineral distribution in disease and disease-free soils. The larger selectivity of suppressive soils for K can be partly attributed to the K-fixing capacity of silicon-rich allophane. Moreover, there was a clear separation between available iron (Fe) [extracted by diethylenetriaminepentaacetic acid (DTPA)] and the mass of stable aggregate in water (WSA) in conducive and suppressive soil samples by K_G. These results suggest that WSA and Fe-DTPA in soils of volcanic nature affected by F. oxysporum f. sp. cubense seem to depend on K selectivity characteristics associated with these soils.     

Studies on Japanese acid earth

Japanese acid earth was discovered about fifty years ago, in Niigata Prefecture. The properties of this earth resemble those of Fuller's Earth showing distinct acid reaction; it is believed that it consists of montmorillonite or beidellite.^{1, 2, 3)} The author took samples from lmai, Niigata Prefecture and studied the chemical properties and clay mineral composition of the acid earth. The soil profile of the spot where the samples were taken is shown in Fig. 1. It consists of 12 layers, but the top 7 layers are alluvial deposits unconformably covering the acid earth. The lower earth deposits are divided into 5 layers viz., G₁ G₂ , H₁, H₂ and the parent rock P. This mother rock is estimated to be liparitic tuff or glassy liparite by microscopic and macroscopic investigation.     

Organic matter stabilization in two Andisols of contrasting age under temperate rain forest

Recent studies with Andisols show that the carbon (C) stabilization capacity evolves with soil age relative to the evolution of the mineral phase. However, it is not clear how soil mineralogical changes during pedogenesis are related to the composition of soil organic matter (SOM) and ¹⁴C activity as an indicator for the mean residence time of soil organic matter (SOM). In the present study, we analyzed the contribution of allophane and metal–SOM complexes to soil C stabilization. Soil organic matter was analyzed with solid-state ¹³C nuclear magnetic resonance spectroscopy. Additionally, the soil was extracted with Na-pyrophosphate (Al_p, Fe_p) and oxalate (Al_o, Si_o, and Fe_o). Results supported the hypothesis that allophane plays a key role for SOM stabilization in deep and oldest soil, while SOM stabilization by metal (Al and Fe) complexation is more important in the surface horizons and in younger soils. The metal/C_p ratio (C_p extracted in Na-pyrophosphate), soil pH, and radiocarbon age seemed to be important indicators for formation of SOM–metal complexes or allophane in top- and subsoils of Andisols. Changes in main mineral stabilization agents with soil age do not influence SOM composition. We suggest that the combination of several chemical parameters (Al_p, Fe_p and C_p, metal/C_p ratio, and pH) which change through soil age controls SOM stabilization.     

Hydrogen consumption and carbon monoxide production in soils with different properties

 Soils are the dominant sink in the global budget of atmospheric H₂, and can be an important local source of atmospheric CO. In order to understand which soil characteristics affect the rates of H₂ consumption and CO production, we measured these activities in 16 different soils at 30% and 60% of their maximum water holding capacity (whc). The soils were obtained from forests, meadows and agricultural fields in Germany and exhibited different characteristics with respect to texture, pH, total C, substrate-induced respiration (SIR), respiration, total and inorganic N, N mineralization, nitrification, N₂O production and NO turnover. The H₂ consumption rate constants were generally lower at 60% than at 30% whc, whereas the CO production rates were not influenced by the whc. Spearman correlation analysis showed that H₂ consumption correlated significantly (r>0.5, P<0.05) at both water contents only with SIR and potential nitrification. The correlation with these variables that are largely dominated by soil microorganisms is consistent with our understanding that atmospheric H₂ is oxidized by soil hydrogenases. Multiple regression analysis and factor analysis gave similar results. Production of CO, on the other hand, was significantly correlated to soil total C, respiration, total N and NH₄ ⁺. The correlation with these variables that are largely dominated by a soil's chemical composition is consistent with our understanding that CO is produced by chemical oxidation of soil organic C. CO production was also influenced by soil usage, with rates increasing in the order: arable<meadow<forest. H₂ consumption was not influenced by soil usage. Received: 28 October 1999     

A re-interpretation of 'Aluminium solubility mechanisms in moderately acid Bs horizons of podzolized soils' by Gustafsson et al.

Gustafsson et al. in a recent paper in this Journal reported the effects of adding HCl, AlCl₃ and Si(OH)₄ on the pH and concentrations of Al and Si in 1:1 soil:solution systems at three different temperatures, using samples of soil from an allophanic Bs horizon. Contrary to their conclusions, their observations are compatible with Al in the soil solution being in equilibrium with a proto‐imogolite allophane; it is neither necessary nor even plausible to postulate a hypothetical Al hydroxide. Concentrations of 0.2–0.4 mm Si in the equilibrated solutions at pH 5 could arise from an amorphous silica, probably phytoliths. They cannot come from the allophane.     

Measuring Oxidative Gelation of Aqueous Flour Suspensions Using the Rapid Visco Analyzer

The Rapid Visco Analyzer (RVA) was investigated as a tool to measure oxidative gelation capacity (OGC) of aqueous wheat flour suspensions. One club wheat patent flour was used to determine optimal hydration time, and 33 straight‐grade flours (representing 12 hard and 21 soft varieties) were used to observe varietal differences in OGC. A 33.3% w/w flour–water suspension was tested in the RVA at 30°C and 160 rpm for 1 min to establish the flour–water baseline viscosity, and then 65 μL of 3% H₂O₂ was added and the viscosity of the suspension measured at 160 rpm for a further 5 min. Flour from the club wheat showed that 20 min of prehydration was needed to observe full OGC potential. For the 33 straight‐grade flours, final RVA water baseline viscosity was correlated with Bostwick Consistometer (BC) flow (r = −0.93, P ≤ 0.01), and RVA H₂O₂ peak viscosity was correlated with H₂O₂ BC flow (r = –0.81, P ≤ 0.01). The RVA was able to differentiate H₂O₂‐reactive from nonreactive flours. The RVA can observe phenomena not observable with the BC method (e.g., viscosity reduction over time at constant shear rate), which can provide potentially valuable additional information about the nature of OGC in wheat flour suspensions.     

Influence of cationic impurities in acidulated phosphates on the availability of phosphorus to two corn crops

Abstract

Based on the problems that arises from the presence of cationic impurities in rock phosphates for fertilizer production, a greenhouse experiment consisting of two consecutive corn crops was conducted in order to evaluate the plant availability of phosphorus (P) in the fraction soluble only in neutral ammonium citrate (NAC) and also in the NAC+H₂O fraction of acidulated phosphate fertilizers produced from Brazilian raw materials with different amounts of cationic impurities. The experiment was conducted with samples of a Red‐Yellow Latosol (Typic Hapludox) in a completely randomized design with four replications. Four acidulated phosphates obtained by sulfuric acid (H₂SO₄) solubilization of different Brazilian raw materials were studied. Monocalcium phosphate [Ca(H₂PO₄)H₂O] (MCP) was included as a standard source of P as well as samples which were previously leached to remove the water‐soluble P, and therefore, contained essentially the NAC‐soluble fraction. The fertilizers were thoroughly mixed with the whole soil in the pots (mixed application), or with only 1% of its volume (localized application), at the rates of 50 and 100 mg P kg^‐1, based on the calculated content of P soluble in NAC+H₂O. Corn (Zea mays L.) was the test crop grown in two sequences of 35 days. After each 35‐day period, dry matter yield and P accumulated in the plant tops were determined. Results were evaluated by analysis of variance considering the factors, (i) acidulated phosphates, (ii) rate of P application, (iii) leaching, and (iv) methods of application. In a second analysis, the leached phosphates were considered as additional levels of the phosphate factor as well as for MCP. The Tukey test at the 0.05 significance level was utilized for mean separation. Results from this study clearly demonstrated that increasing the amounts of cationic impurities in the raw materials decreased the concentration of water‐soluble P and NAC+H₂O‐soluble P as well as water‐soluble P and NAC+H₂O‐soluble P ratio of the fertilizer obtained. From the results in the first corn cropping, the P in the NAC fraction for the studied Brazilian phosphate was not as available to plants as was the P in the NAC+H₂O fraction or in the pure MCP. The NAC+H₂O method was not an adequate index for evaluating the P availability of the studied sources. No interaction between P sources, leaching, and method of application was found in the second corn cropping.