A rapid method to determine cation exchange capacity and exchangeable bases in calcareous,gypsiferous, saline and sodic soils

Summary

A simple, single‐step extraction with LiEDTA for the estimation of CEC and exchangeable bases in soils has been developed. Multivalent cations are stripped from the soil adsorption sites by the strongly chelating agent EDTA, and are replaced by Li. In soils without CaCO₃ or water soluble salts, exchangeable divalent cations (Ca, Mg) are chelated by EDTA and exchangeable monovalent cations (Na, K) are replaced in a single extraction step using 0.25–2.5 g of soil and 10.0 ml of extractant.

In calcareous soils the CEC can be determined in the same way, but for the extraction of exchangeable Ca and Mg, another separate extraction is needed because dissolution of calcite by EDTA is unavoidable. This extraction is done with as much NaEDTA as needed to extract only exchangeable Ca and Mg in a 1:2 (m/V) soil/alkaline‐50% (V/V) aethanolic solution to minimize dissolution of calcite.

In gypsiferous soils gypsum is transformed into insoluble BaSO₄ and soluble CaEDTA by LiBaEDTA thus avoiding interference of Ca from dissolution of gypsum, which renders the traditional methods for determining CEC unsuitable for such soils. To determine exchangeable Ca and Mg, Na₄EDTA is used as for calcareous soils.

In saline/sodic soils replacement of Na by Li is incomplete but the Na/Li‐ratio at the complex after extraction is proportional to the molar Na/Li‐ratio in the extracts, so that the CEC and original exchangeable sodium (ESP) content can be calculated. Additional analysis of Cl and, if necessary, SO₄ in the extracts of saline soils can be used to correct for the effect of dissolution of the salts on the sum of exchangeable cations.

This new method is as convenient as the recently developed AgTU (silverthiourea), but is better suitable for calcareous and gypsiferous soils.     

Factors Influencing the Dissolution of Phosphate Rock in a Range of High P‐Fixing Soils from Cameroon

Abstract

A laboratory incubation experiment was conducted to evaluate the soil factors that influence the dissolution of two phosphate rocks (PRs) of different reactivity (Gafsa, GPR, reactive PR; and Togo‐Hahotoe, HPR, low reactivity PR) in seven agricultural soils from Cameroon having variable phosphorus (P)‐sorption capacities, organic carbon (C) contents, and exchangeable acidities. Ground PR was mixed with the soils at a rate of 500 mg P kg^?1 soil and incubated at 30°C for 85 days. Dissolution of the PRs was determined at various intervals using the ΔNaOH‐P method (the difference of the amount of P extracted by 0.5 M NaOH between the PR‐treated soils and the control). Between 4 and 27% of HPR and 33 and 50% of GPR were dissolved in the soils. Calcium (Ca) saturation of cation exchange sites and proton supply strongly affected PR dissolution in these soils. Acid soils with pH‐(H₂O)<5 (NKL, ODJ, NSM, MTF) dissolved more phosphate rock than those with pH‐(H₂O)>5 (DSC, FGT, BAF). However, the lack of a sufficient Ca sink in the former constrained the dissolution of both PRs. The dissolution of GPR in the slightly acidic soils was limited by increase in Ca saturation and that of HPR was constrained by limited supply in protons. Generally, the dissolution of GPR was higher than that of HPR for each soil. The kinetics of dissolution of PR in the soils was best described by the power function equation P=At^B. More efficient use of PR in these soils can be achieved by raising the soil cation exchange capacity, thereby increasing the Ca sink size. This could be done by amending such soils with organic materials.     

Study of the antimony species distribution in industrially contaminated soils

Purpose

The purpose of the present study was to investigate the distribution of antimony (Sb) and its species in soil fractions in order to understand better the real risk associated with Sb in the environment.

Materials and methods

Nine surface soil samples contaminated from lead/zinc and iron smelting operations and coal fired power plants were examined using: (1) four-step sequential extraction procedure (BCR); (2) two-step sequential extraction including ethylenediaminetetraacetic acid (EDTA), sodium hydroxide (NaOH) and NH₄F; and (3) single extraction with EDTA and NaOH. Liquid phase extraction was used for redox speciation of Sb. The distribution of Sb between soil fulvic and humic acids was determined after their chemical separation. The concentrations of Sb were measured by electrothermal atomic absorption spectrometry.

Results and discussion

The main part of total Sb (2.5–105 mg?kg^?1) was associated with the residual fraction in all soils. The exchangeable/carbonate-bound concentrations were 0.83–4.7 % of total Sb. Up to 6.8 % was in the reducible and up to 1.4 % was in the oxidizable fraction. EDTA removed 7.2–11.4 % of total content. Sb(V) was the predominant form in acetic acid and EDTA extracts. Single extraction with 0.1 mol?l^?1 NaOH released up to 13.7 % of soil antimony. The main part of Sb was complexed to the higher molecular weight fraction of soil-derived humic substances.

Conclusions

For highly contaminated soils, 4 % solubility in acetic acid could represent risk of contamination of ground water under specific conditions. Also, the relatively high phytoavailable Sb (7–11 %) can represent a significant proportion in highly polluted soils. Pentavalent antimony was the main antimony species extracted from soils. The main part of the organically antimony was found to be present as complexes with higher molecular weight humic acids fraction.     

Cation exchange capacity measurements

Abstract

Soil cation exchange capacity (CEC) measurements are important criteria for soil fertility management, vaste disposal on soils, and soil taxonomy. The objective of this research was to compare CEC values for arable Ultisols from the humid region of the United States as determined by procedures varying widely in their chemical conditions during measurement. Exchangeable cation quantities determined in the course of two of the CEC procedures were also evaluated. The six procedures evaluated were: (1) summation of N NH₄OAc (pH 7.0) exchangeable Ca, Mg, K, and Na plus BaCl₂ ‐ TEA (pH 8.0) exchangeable acidity; (2) N Ca(OAc)₂ (pH 7.0) saturation with Mg(OAc)₂ (pH 7.0) displacement of Ca²⁺; (3) N NH₄OAc (pH 7.0) saturation with NaCl displacement of NH₄ ⁺; (4) N MgCl₂ saturation with N KCl displacement of Mg²⁺; (5) compulsive exchange of Mg²⁺ for Ba²⁺; and (6) summation of N NH₄OAc (pH 7.0) exchangeable Ca, Mg, K, and Na plus N KCl exchangeable AJ. The unbuffered procedures reflect the pH dependent CEC component to a greater degree than the buffered methods. The compulsive exchange and the summation of N NH₄OAc exchangeable cations plus N KCl exchangeable Al procedures gave CEC estimates of the same magnitude that reflect differences in soil pH and texture. The buffered procedures, particularly the summation of N NH₄OAc exchangeable cations plus BaCl₂ ‐ TEA (pH 8.0) exchangeable acidity, indicated inflated CEC values for these acid Ultisols that are seldom limed above pH 6.5. Exchangeable soil Ca and Mg levels determined from extraction with 0.1 M BaCl₂ were consistently greater than values for the N NH₄Oac (pH 7.0) extractions. The Ba²⁺ ion is apparently a more efficient displacing agent than the NH₄ ⁺ ion. Also, the potential for dissolving unreacted limestone is greater for the Ba₂ ⁺ procedures than in the NH₄ ⁺ extraction.     

Use of Single Extraction Methods to Predict Bioavailability of Heavy Metals in Polluted Soils to Rice

Human exposure to toxic heavy metals via dietary intake is of increasing concern. Heavy-metal pollution of a rice production system can pose a threat to human health. Thus, it was necessary to develop a suitable extraction procedure that would represent the content of metal available to rice plants (Oryza sativa L.). The aim of this study was to predict, on the basis of single extraction procedures of soil heavy metals, the accumulation of heavy metals (cadium, lead, copper, and zinc) in rice plants. Six extracting agents [Mehlich 1, Mehlich 3, EDTA (ethylenediaminetetraacetic acid), DTPA–TEA (diethylenetriaminepentaacetic acid–triethanolamine), ammonium acetate (NH₄OAc), and calcium chloride (CaCl₂)] were tested to evaluate the bioavailability of heavy metals from paddy soils contaminated with lead–zinc mine tailings to rice. The extraction capacity of the metals was found to be of the order EDTA > Mehlich 3 > Mehlich 1 > DTPA–TEA > NH₄OAc > CaCl₂. The correlation analysis between metals extracted with different extractants and concentrations of the metals in the grain and stalk of the plant showed positive correlations with all metals. The greatest values of correlation coefficients were determined between the NH₄OAc- and CaCl₂-soluble fractions of soil and contents in plants in all four metals studied. Therefore, NH₄OAc and CaCl₂ were the most suitable extractants for predicting bioavailability of heavy metals in the polluted soils to rice. The results suggested that uptake of heavy metals by rice was mostly from exchangeable and water-soluble fractions of the metals in the soils. Soil-extractable metals were more significantly correlated with metal accumulation in the stalk than in the grain. The pH had more significant influence on availability of heavy metals in the soils than total content of metals and other soil properties. The bioavailability of metals for rice plants would be high in acidic soils.     

Soil organic phosphorus in tropical forests: an assessment of the NaOH–EDTA extraction procedure for quantitative analysis by solution 31P NMR spectroscopy

The extraction of soil organic phosphorus by the NaOH–EDTA procedure was assessed in detail for a tropical forest soil (clay‐loam, pH 4.3, total carbon 2.7%). Optimum conditions for the quantification of soil organic phosphorus and characterization of its composition by solution ³¹P NMR spectroscopy were extraction in a solution containing 0.25 m NaOH and 50 mm Na₂EDTA in a 1:20 solid to solution ratio for 4 hours at ambient laboratory temperature. Replicate analyses yielded a coefficient of variation of 3% for organic phosphorus as a proportion of the spectral area. There was no significant difference in total phosphorus extraction from fresh and air‐dried soil, although slightly more organic phosphorus and less paramagnetic ions were extracted from dried soil. The procedure was not improved by changing the concentration of NaOH or EDTA, extraction time, or solid to solution ratio. Pre‐extraction with HCl or Na₂EDTA did not increase subsequent organic phosphorus extraction in NaOH–EDTA or improve spectral resolution in solution ³¹P NMR spectroscopy. Post‐extraction treatment with Chelex resin did not improve spectral resolution, but removed small concentrations of phosphorus from the extracts. Increasing the pH of NaOH–EDTA extracts (up to 1.0 m NaOH) increased the concentration of phosphate monoesters, but decreased DNA to an undetectable level, indicating its hydrolysis in strong alkali. The standardized NaOH–EDTA extraction procedure is therefore recommended for the analysis of organic phosphorus in tropical forest soils.     

Importance of proton supply and calcium-sink size in the dissolution of phosphate rock materials of different reactivity in soil

The dissolution of a range of phosphate rock (PR) materials (Gafsa, GPR; Jordan, JPR; North Florida, NFPR; and Tundulu, TPR) was evaluated in three UK soils (Nercwys, Davidstow and Withnell) which differed in proton supply and P-buffer capacity. The Ca-sink size was adjusted by adding different amounts of a cation-exchange resin (CER) to the soils. In the presence of a large proton supply (pH_w 3.8–4.8, pH-buffer capacity 52.5–36.5 mmol OH^? kg^?1 pH unit^?1), the dissolution of GPR, JPR and NFPR in the Nercwys and Davidstow soil-CER mixtures was strongly influenced by the size of the Ca sink. A twofold increase in Ca-sink size in these two soils caused an increase in PR dissolution of 44–120%. Except for TPR, the increase in PR dissolution per unit increase in Ca-sink size was the same for the three PR materials. In the Withnell soil-CER mixtures, where the initial proton supply was relatively small (pH_w 4.8–6.1, pH-buffer capacity 23.7–21.4 mmol OH^? kg^?1 pH unit^?1), the increase in PR dissolution with increasing Ca-sink size was less (24–68%) than in the other two soils (44–120%). Also, for the Withnell soil, the increase in PR dissolution with increasing Ca-sink size decreased in the order GPR (68%) > JPR (49%) > NFPR (24%), a trend consistent with the decrease in PR reactivity. The maximum dissolution of TPR was only 8–22% under favourable conditions of proton supply and Ca sink, and was little affected by Ca-sink size.     

Measuring reactive metal in soil: a comparison of multi‐element isotopic dilution and chemical extraction

The isotopically exchangeable metal pool (E‐value) of zinc (Zn), cadmium (Cd) and lead (Pb) were simultaneously measured, using stable isotope dilution, in soils contaminated by Pb/Zn mining activities and varying in properties likely to affect metal reactivity, including pH, organic matter content, metal concentration and land use. E‐values were compared with single and sequential extraction schemes. Results showed a wide range of metal reactivity (approximately 1–100% of total) depending on the extent of contamination and on the prevailing soil conditions. Across the range of soils, the E‐values showed no consistent correspondence to any single chemical extraction procedure (EDTA, DTPA and HNO₃) although there was reasonable agreement with the extractants 0.05 m EDTA and 0.43 m HNO₃ in acidic organic soils. Extraction with 0.005 m DTPA substantially under‐estimated the isotopically exchangeable metal content. E‐values corresponded reasonably well with the exchangeable metal (fraction 1 (F1) of the sequential extraction procedure) in calcareous soils but relatively poorly and inconsistently with F1–F2, F1–F3 or F1–F4 in acidic‐neutral soils. Operational aspects associated with determination of multi‐element E‐values are discussed.     

The importance of exchangeable cations and resin-sink characteristics in the release of soil phosphorus

The significance of exchangeable cations in the release of phosphorus by sequential extraction with water was evaluated in 11 acid (_pH 5.0–6.3) New Zealand soils contrasting in P status and P retention. The release of P from Na-saturated soil exceeded that from the original Ca-dominated soils by up to four-fold. Possible explanations for the larger P release in the Na system include: (i) desorption of P induced by increased surface negative potential associated with the exchange of Na for Ca/Mg, and/or (ii) accelerated dissolution of Ca phosphate compounds or complexes resulting from the creation of a sink for Ca.
The potential of a series of anion- and cation-exchange resin systems (AER and CER, respectively) as sinks for labile soil P was also examined. For all soils studied, P extracted by AER-HCO₃ 3 and that removed by sequential extraction with water. Also, the amounts of P extracted by AER-OH/CER-H and NaCl/ H₂O were closely correlated ( r = 0.95**), suggesting similar release mechanisms. The results obtained indicate that charge-balancing cations, particularly Ca which is the predominant exchangeable cation in the majority of soils, exerts a more significant control on soil P equilibria in acid soils than is commonly recognized.     

Selective Removal of Lead from Calcareous Polluted Soils using the Ca-EDTA Salt

EDTA is a powerful chelating reagentwhich has been often proposed for the decontaminationof lead polluted soils. Despite the pronouncedselectivity of this reagent for Pb, a low degree ofutilisation is observed when treating calcareoussoils, due to the co-dissolution of calcite. Thisstudy demonstrates that it is possible to suppresscalcite dissolution and optimise the degree of EDTAutilisation, using the calcium salt of EDTA, insteadof the common sodium salts. Initial experiments, whichwere carried out mixing pure cerrusite (PbCO₃)with a Na₂CaEDTA solution, have shown that Pb isquantitatively solubilised, while calcium precipitatesin the form of aragonite. The performance of thisreagent in the decontamination of soils has beentested on a soil sample from Lavrion (Greece)containing 7.3–8.8% of Ca and heavily polluted withPb at levels up to 3.5%. The parameters which weretested include the reaction time, the stoichiometricexcess of Na₂CaEDTA with respect to Pb and theeffect of successive treatment stages with freshNa₂CaEDTA solutions. The experimental resultshave shown that long reaction times, exceeding 24 hr, are required in order to obtain sufficient Pbremoval and preserve the calcium content of the soil.Lead extraction increases from 27 to 40% prolongingthe reaction time from 1 to 24 hr atNa₂CaEDTA/Pb = 1 mol/mol. Increasing theNa₂CaEDTA/Pb molar ratio from 1 to 3.5 mol/mol,enhances the dissolution of Pb from 40 to 53%, whichis not proportional to the stoichiometric excesssupplied. The efficiency of Pb removal is maximized,up to 75%, applying three successive leaching stages.The major benefit of Na₂CaEDTA in comparison withthe disodium EDTA salt is the preservation of soilcalcite. The initial calcium content of the soil wasfound to increase by 4% using the Ca salt; on thecontrary, the treatment with Na₂H₂EDTA undersimilar experimental conditions has resulted indissolving 27% of soil Ca.     

Comparison of four extractants and chemical fractions for assessing available zinc and copper in soils of India

Abstract

Relative suitability of different extraction procedures for estimating available zinc (Zn) and copper (Cu) in soils was assessed using DTPA, 0.1 N HCl, ammonium acetate+EDTA, and double acid (HCl+ H₂SO₄) as extractants and rice as a test crop in Neubauer experiment. The relationships between Zn concentration and uptake of Zn by rice plants and Zn extracted by the different methods showed that DTPA‐TEA, pH 7.3, could very suitably be used to assess Zn availability in soils. However, 0.1 N HCl was better for assessing the Cu availability in soils to the rice plants. Water‐soluble and exchangeable fractions of Zn and Cu had significant positive correlations with Zn and Cu concentrations, respectively obtained by all the four extractants tested. The results also showed that DTPA and ammonium acetate+EDTA extracted organically bound Zn, whereas DTPA, 0.1 N HCl and ammonium acetate+EDTA extracted organically bound Cu. Water‐soluble, exchangeable and organic matter bound fractions exhibited significant relationships with Zn and Cu concentrations, their uptake and rice dry matter yield.     

The effect of EDTA on the extractability of Zinc (Zn), Cadmium (Cd) and Nickel (Ni) in Vertisol and Alluvial soils

Ethylendiamintetraacetic acid (EDTA) is persistent in the environment. The presence of EDTA in soil may alter the mobility and transport of Zn, Cd and Ni in soils because of the formation of water soluble chelates, thus increasing the potential for metal pollution of natural waters. Mobility of metals is related to their extractability. To investigate metal extractability affected by EDTA, Zn, Cd and Ni were added to Vertisol and Alluvial soil at rates of 50, 2 and 5 mg kg^-1, respectively. Both natural and metal amended soils were treated with Na₂EDTA at rates of 0; 0.2 and 0.5 mg kg^-1. After five months of incubation soil samples were extracted with 0.1 N HCl, 0.005 M DTPA + 0.01 M CaCl₂ + 0.1 M TEA (0.005 M Diethylenetriaminepentaacetic acid + 0.01 M Calcium cloride + 0.1 M Triethanolamine) and 1 M Mg(NO₃)₂, the latter of which extracts the exchangeable from of metald (Zn, Cd and Ni).

According to experiment results, Zn, Cd and Ni in all extraction increased with increasing rates of EDTA in the natural and metal amended soils.     

Humus composition and humification degree of humic acids of alpine meadow soils in the northeastern part of the Qinghai–Tibet Plateau

The characteristics of humus composition are important for understanding the mechanism of carbon storage in the Qinghai–Tibet Plateau. The aim of this study was to characterize the quality of soil organic matter (SOM) in this region. Soil samples from four soil profiles in fenced study sites in the alpine grassland were collected at altitudes of 4200, 4000, 3800, and 3400 m, along the southwest facing slope in the Qilian Mountains. The humus composition and humification degree of the humic acid (HA) were determined by two methods: (1) extraction with 0.5% sodium hydroxide (NaOH) followed by 0.1 M sodium pyrophosphate (Na₄P₂O₇) (OH-PP method); and (2) treating once with 0.1 M hydrochloric acid (HCl) followed by extracting with 0.5% NaOH (Cl-OH method). Physico-chemical analysis revealed higher exchangeable cation content and higher base saturation ratios could be related to slightly acidic to neutral soils, which could be regarded as calcium (Ca)-rich soils. The amounts of combined-form HAs obtained by HCl pretreatment (HA_Cl – HA_OH; ?HA_Cl) were remarkably higher than those extracted with Na₄P₂O₇ (HA_PP), indicating that the combined form of HAs is mainly Ca. In addition, the proportion of HA_PP in the total HAs extracted with both NaOH and Na₄P₂O₇ (HA_OH + HA_PP) obtained in the OH-PP method increased with soil depth and decreasing elevation, indicating that HAs associated with aluminum (Al) and iron (Fe) were distinguished in the subsoils of lower elevation. Therefore, the formation of the organo-mineral complex may contribute to stabilizing SOM in the Qinghai–Tibet Plateau. Moreover, Type A-HA with the highest degree of humification was obtained from the deeper horizons with the Cl-OH method and almost all horizons by extraction with Na₄P₂O₇ in the OH-PP method. Further studies using various spectroscopic analyses are necessary to elucidate the chemical properties of SOM in this region.     

Evaluation of Nutrient Release in Salt‐Saturated Soils

Abstract

The effects of irrigating with saline water on native soil fertility and nutrient relationships are not well understood. In a laboratory experiment, we determined the extent of indigenous nutrient [calcium (Ca), magnesium (Mg), potassium (K), manganese (Mn), and zinc (Zn)] release in salt-saturated soils. Soils were saturated with 0, 75, and 150 mmolc L^?1 sodium chloride (NaCl) solution and incubated for 1, 5, 10, and 15 days. The saturation extracts were analyzed for pH, ECe, and water‐soluble Ca, Mg, K, Mn, and Zn, and the remainder soil samples were analyzed for exchangeable forms of these elements. In a subexperiment, three soil types (masa, red‐yellow, and andosol) were saturated individually either with 100 mmolc L^?1 of NaCl, sodium nitrate (NaNO₃), or sodium sulfate (Na₂SO₄) salt. These salts were also compared for nutrient release. Soils treated with NaCl released higher amounts of water‐soluble than exchangeable nutrients. Except for Zn, the average concentrations of these nutrients in the soil solution increased significantly with time of incubation, but concentrations of the exchangeable forms varied inversely with time of incubation. The masa soil exhibited the highest concentrations of Ca and Mg, whereas K was highest in andosol. The extract from soils treated with NaCl contained greater amounts of soluble cations, whereas soils treated with Na₂SO₄ produced the lowest concentration of these elements irrespective of the type of soil used.     

Comparative study of selected lime requirement methods for some acid Ghanaian soils

Abstract

The acid soils of the western region of Ghana which hitherto have been relegated to forest and tree crops production are becoming increasingly important for agricultural food crop production in the country. However, on account of their strongly acidic properties, there is the need to apply agricultural lime to the soils to improve upon their productivity. At present, however, information on the lime requirement and appropriate liming practice for these soils is lacking. The objective of this study was to compare the suitability of selected chemical methods for the determination of the lime requirement to predict lime needs of these naturally occurring acid soils. The lime requirement of six acid soils were determined by calcium hydroxide [Ca(OH)₂] titration, exchangeable aluminum (Al), and Shoemaker, McLean, and Pratt (SMP) buffer methods. Correlation analysis showed that all the methods were highly correlated with one another. The SMP method was found to be somewhat better than either exchangeable Al or Ca(OH)₂ titration method for estimating the lime requirement of the soils. Hence, the SMP method is recommended for use as the diagnostic index of lime requirement of these soils because of its speed and simplicity. Regression studies on the lime requirement values by the three methods and selected soil properties showed that exchangeable Al and organic carbon were the most important soil factors contributing to the lime requirement of these soils. Clay content was significantly correlated only with the Ca(OH)₂‐based lime requirement values (r = 0.81*).     

Sequential fractionation of chromium and nickel from some serpentinite‐derived soils from the eastern Transvaal

Abstract

Soils derived from ultramafic serpentinitic rocks are inherently infertile. These soils support plant species that are able to hyperaccumulate both chromium (Cr) and nickel (Ni). This study was conducted to determine the efficacy of a sequential extraction technique in explaining sources of Cr and Ni that are taken up by plant species growing on these soils. The sequential extraction of soil samples obtained from the eastern Transvaal involved the following reagents: H₂O and 0.5M KNO₃, 0.5M NaOH, 0.05M Na₂EDTA, and 4M HNO₃. More than 95% of the total Cr was extracted by HNO₃ while the remaining extractants fell into the order NaOH > EDTA ? KNO₃ + H₂O. There would appear to be a loose correlation between easily soluble Cr (KNO₃ + H₂O) and the uptake of Cr by the plant. A somewhat higher proportion of Ni was extracted prior to the HNO₃ treatment although amounts removed by KNO₃ + H₂O were all less than 1% of the total. It would appear that plant species growing on these soils are able to accumulate these elements from sources other than those considered easily available. A highly significant coefficient of determination was obtained between Ni extracted by oxalate and EDTA extractable. The fraction extracted by the steps in the sequential procedure can be related to exchangeable and sorbed (KNO₃ and H₂O) and an easily acid soluble inorganic fraction (HNO₃). The NaOH and EDTA fractions are probably related to the Cr and Ni bound in the form of organic complexes and associated with iron oxides.     

Evaluation of anion exchange membranes to estimate bioavailable phosphorus in native grasslands of semi‐arid Northwestern Australia

Abstract

Anion exchange membranes (AEMs) were used to assess the P status of semi‐arid sub‐tropical soils of high P sorption capacity from the Pilbara region in northwestern Australia. We determined the most appropriate procedure for using AEMs in these soils using a factorial of extraction ratios and shaking times and compared the method with extraction by water. Significantly more inorganic P (Pi) was extracted by the membranes (AEM‐Pi) than by water, and the amount extracted increased with extraction time but was generally independent of the extraction ratio. Maximum AEM‐Pi was 3.61 μg g^‐1 after eight hour extraction. The AEM procedure was compared with traditional extraction procedures using 0.5 M sodium bicarbonate (NaHCO₃) and 0.1 M sodium hydroxide (NaOH) to assess ability to detect spatial heterogeneity. The amount of Pi extracted decreased in the order: AEM>NaOH>NaHCO_3* The AEM method detected a significant effect of depth on Pi (P=0.0001), while the NaOH method detected both site and treatment effects (P<0.05). Inorganic P extracted by NaHCO₃ did not vary by site, treatment, or depth. Coefficients of variation were generally least using the AEM method. We recommend that studies of spatial and temporal dynamics of P on highly‐weathered soils in semi‐arid regions include measurement of both AEM‐Pi and NaOH‐extractable Pi.     

Validation of Soil Phosphate Removal by Alkaline and Acidic Reagents in a Vertosol Soil using XANES Spectroscopy

There is a paucity of information on the soil phosphorus (P) forms removed by alkaline and acidic reagents in Vertosols. The first aim of this study was to identify which soil phosphates are removed by a two-step sequential fractionation (0.1 M NaOH and 1 M HCl) and by a dilute acid extractant (0.005 M H₂SO₄; Bureau of Sugar Experiment Stations (BSES) soil P test) on an “untreated” Vertosol using P K-edge x-ray absorption near-edge structure (XANES) at the Australian Synchrotron. There was supporting evidence that the 0.1 M sodium hydroxide (NaOH), 1 M hydrochloric acid (HCl), and 0.005M sulfuric acid (H₂SO₄) extractants remove soil phosphates according to the chemical solubility of known P minerals. The XANES spectra revealed the 1 M HCl and 0.005 M H₂SO₄ extractants remove calcium (Ca) phosphates from Vertosols, suggesting the latter extractant could be used as an alternative for a rapid and cost-effective measure of Ca phosphates in Vertosols.     

A critical assessment of methods for determining organic phosphorus in savanna soils

 Two newly introduced extraction techniques for determining total organic P (P₀) were compared with the standard high-temperature ignition method in selected savanna soils of Nigeria. The two extraction techniques were: (1) concentrated H₂SO₄ and dilute base sequential extraction (18 N H₂SO₄ and 0.5 N NaOH) and (2) basic EDTA method (0.25 M NaOH plus 0.05 M Na₂EDTA). The concentrated H₂SO₄ and dilute base method extracted significantly higher total P₀ than the high-temperature ignition method and the basic EDTA extraction. The high-temperature ignition and the basic EDTA extraction gave similar total P₀ values (mean=91 mg kg^–1 for ignition and 90 mg kg^–1 for basic EDTA). The precision of the methods, determined by coefficients of variation (CV, %) associated with each P₀ determination method in the soils, was better for the concentrated H₂SO₄ and dilute base extraction method (CV=13%) than the ignition method (CV=18%) and the basic EDTA method (CV=15%). The high C : P₀ ratios determined for the high-temperature ignition and basic EDTA extraction indicated that the two methods underestimated total P₀ in the soils. The concentrated H₂SO₄ and dilute base sequential extraction appears to be suitable for the rapid determination of P₀ in savanna soils because the method can be simplified to a single-step analysis. Received: 14 November 1997     

Comparative Effects of Two Forage Species on Rhizosphere Acidification and Solubilization of Phosphate Rocks of Different Reactivity

ABSTRACT

Dissolution of phosphate rocks (PR) in soils requires an adequate supply of acid (H⁺) and the removal of the dissolved products [calcium (Ca^{2 +}) and dihydrogen phosphate (H₂PO₄ ^?)]. Plant roots may excrete H⁺ or OH^? in quantities that are stoichiometrically equal to excess cation or anion uptake in order to maintain internal electroneutrality. Extrusion of H⁺ or OH^? may affect rhizosphere pH and PR dissolution. Differences in rhizosphere acidity and solubilization of three PRs were compared with triple superphosphate between a grass (Brachiaria decumbens) and a legume (Stylosanthes guianensis) forage species at two pH levels (4.9 and 5.8) in a phosphorus (P)-deficient Ultisol with low Ca content. The experiment was performed in a growth chamber with pots designed to isolate rhizosphere and non-rhizosphere soil. Assessment of P solubility with chemical extractants led to ranking the PRs investigated as either low (Monte Fresco) or high solubility (Riecito and North Carolina). Solubilization of the PRs was influenced by both forage species and mineral composition of the PR. The low solubility PR had a higher content of calcite than the high solubility PRs, which led to increased soil pH values (> 7.0) and exchangeable Ca, and relatively little change in bicarbonate-extractable soil P. Rhizosphere soil pH decreased under Stylosanthes but increased under Brachiaria. The greater ability of Stylosanthes to acidify rhizosphere soil and solubilize PR relative to Brachiaria is attributed to differences between species in net ion uptake. Stylosanthes had an excess cation uptake, defined by a large Ca uptake and its dependence on N₂ fixation, which induced a significant H⁺ extrusion from roots to maintain cell electroneutrality. Brachiaria had an excess of anion uptake, with nitrate (NO₃ ^?) comprising 92% of total anion uptake. Nitrate and sulfate (SO₄ ^{2 ?}) reduction in Brachiaria root cells may have generated a significant amount of cytoplasmic hydroxide (OH^?), which could have increased cytoplasmic pH and induced synthesis of organic acids and OH^? extrusion from roots.