Isotope methods for assessing plant available phosphorus in acid tropical soils

Use of isotope methods to measure the availability of phosphorus (P) in soils that are well supplied with P is well established. We have evaluated such methods for acid tropical soils with very small P contents, which are less well studied. The isotopically exchangeable P in soil suspensions (E value) and that in plant growth experiments (L value) were measured in soils that had received varying amounts of P fertilizer in two field experiments in Colombia. We determined the E values over 4–5 weeks of equilibration allowing for the kinetics of isotope exchange. The decrease in radioactivity in the soil solution at a particular time, t, divided by that at the start (r_t/R) was described by three parameters (r₁/R, r_∞/R, and a coefficient n) derived from the time course of isotopic exchange over 100 minutes. Values of E_t were calculated either from measured values of r_t/R or those extrapolated until 12 weeks. Agrostis capillaris was grown on the same soils labelled with carrier‐free ³³P‐orthophosphate ions to obtain L values. Agreement between E values derived from measured and extrapolated values of r_t/R was satisfactory, but errors in n and r_∞/R limited the precision with which we could estimate E values. For most soils, the P concentrations in the soil solution were greater than the detection limit of the malachite green method (0.9 µg l^?1) but smaller than its quantification limit (3.6 µg l^?1). In the soils with the least available P, the P content of the seed limited the determination of the L value. The E values were strongly correlated, but not identical, with the L values measured for the same time of isotopic exchange. We conclude that these approaches are not precise enough to detect in these soils the ability of a plant to access slowly exchangeable forms of P or to quantify the mineralization of organic P. However, these isotope techniques can be used to estimate the total fraction of added fertilizer P that remains available to the plants.     

Methods for determining labile cadmium and zinc in soil

Isotopically exchangeable cadmium and zinc (‘E values’) were measured on soils historically contaminated by sewage sludge and ones on zinc‐rich mine spoil. The E‐value assay involves determining the distribution of an added metal isotope, e.g. ¹⁰⁹Cd, between the solid and solution phases of a soil suspension. The E values for both metals were found to be robust to changes in the position of the metal solid?solution equilibrium, even though the concentration of dissolved metal varied substantially with electrolyte composition and soil:solution ratio. Concentration of labile metal was also invariant over isotope equilibration times of 2–6 days. The use of a submicron filtration procedure, in addition to centrifuging at 2200 g , proved unnecessary if 0.1 m Ca electrolyte was used to suspend the soils. The proportion of ‘fixed’ metal, in non‐labile forms, apparently increased with increasing pH, although there was considerable variation in both sets of contaminated soil. Zinc and cadmium in the sludged soils were similarly labile. Several possible methods for the measurement of chemically reactive metal were explored for comparison with E values, including single extraction with 1 m CaCl₂ and a ‘pool depletion’ (PD) method. The latter involves comparing solid?solution metal equilibria in two electrolytes with differing degrees of (solution) complex formation, 0.1 m Ca(NO₃)₂ and CaCl₂. Both the single extraction and the PD method gave good estimates of E value for Cd, although the single extraction was more consistent. Neither technique was a useful substitute for determining labile Zn, because of weak chloro‐complexation of Zn^2+. We therefore suggest that 1 m CaCl₂ extraction of Cd alone be used as an alternative to E values to avoid the inconvenience of isotopic dilution procedures.     

Plant availability of isotopically exchangeable and isotopically nonexchangeable phosphate in soils

Isotopically exchangeable P (IEP) is usually considered to be completely plant‐available and the major source of P for plant uptake. The aim of the present study is to test whether plants can, besides IEP, also use non‐IEP and if part of the IEP has an equilibrium concentration in soil solution which is below the minimum concentration, C_Lmin, and can therefore not be taken up by plants. A pot experiment was carried out with maize for two years on two soils, an acid sandy and a neutral loamy soil, either without P fertilizer or fertilized with ten P sources of different solubility. Throughout both years of the study, pots were kept moist either without plants or planted twice with maize (Zea mays L., cv. Athletico). At the end of the experiment, plant P uptake, P concentration in the soil solution (C_L), and P accessible to isotopic exchange within 5 d (E_5d) were measured. Plant growth decreased the E_5d which was about equal to P uptake by maize for most treatments in the acid soil. But for some treatments, i.e., five in the acid and eight in the neutral soil, P uptake was up to 50% larger than the decrease of E_5d, indicating that plants had, besides IEP, also used P from non‐IEP sources. At adequate P supply, both soils had an E_5d of about 100 mg P (kg soil)^–1, but about 30 to 40 mg kg^–1 of this IEP had an equilibrium P concentration in the soil solution below C_Lmin of 0.1 μmol L^–1 at which P would actually not be plant‐available. This study shows that plants take up P mainly from IEP, but not the whole IEP is plant‐available. Furthermore, plants may also use P from non‐IEP sources.     

Anion‐exchange membrane,water, and sodium bicarbonate extractions as soil tests for phosphorus

Abstract

Three techniques were evaluated as soil P tests for western Canadian soils: anion‐exchange membrane (AEM), water, and bicarbonate extraction. The AEM, water, and bicarbonate‐extractable total P represented novel approaches to compare to the widely used bicarbonate‐extractable inorganic P (traditional Olsen) soil test. In a range of Saskatchewan soils, similar trends in predicted relative P availability were observed for AEM, water extraction, bicarbonate‐extractable total P, and bicarbonate‐extractable organic P. Correlations between soil test values revealed AEM and water‐extractable P to be most closely correlated, consistent with the similar manner of P removal in the two tests.

Phosphorus availability, as predicted by the tests, was compared to actual P uptake by canola and wheat grown on 14 soils in a growth chamber experiment. P uptake by canola was highly correlated with AEM (r² = 0.86–0.90), water (0.87 ‐0.94), and bicarbonate‐extractable total (0.91) and inorganic (0.92) P. Uptake of P by wheat was not quite as highly correlated with test‐predicted values: AEM (r² = ‐0.73–0.78), water (0.72–0.77), bicarbonate total (0.82), bicarbonate‐inorganic P (0.75).

The similarity in coefficients of determination among test methods indicated nearly identical abilities of the tests to predict soil P availability in the range of soils examined. The AEM and water extractions, unlike bicarbonate, are largely independent of soil type and may prove superior when a wider range of soils is being tested. Bicarbonate‐extractable total P and water‐extractable P suffer limitations in analytical simplicity and cost. In testing for P alone, AEM was considered superior to the other methods due to low cost, simplicity, independence of soil type, and high correlation with plant uptake.     

Comparison of soil nitrate extracted by potassium chloride and adsorbed on an anion exchange membrane in situ

Abstract

The 2M potassium chloride (KCl) extraction method used to measure soil nitrate (NO₃ ^‐‐N) concentrations in soils may introduce some artifacts caused by soil sampling, processing, and handling. Furthermore, this method provides soil NO₃ ^‐‐N concentrations for soil sampled at a particular time, whereas the dynamics of this anion in situ need to be better understood. In order to develop a reliable in situ method as an alternative, an anion exchange membrane (AEM) was tested for its ability to adsorb NO₃ ^‐‐N from a soil cropped to corn (Zea mays L.) and amended with manure or inorganic nitrogen (N). In a field study, we compared the amount of NO₃ ^‐‐N adsorbed on an AEM and extracted with the 2M KCl method. The AEM was calibrated in the laboratory and placed at 15‐cm soil depth for 2‐wk periods during the corn growing season. Nitrate adsorption on the AEM and KCl‐extractable NO₃ ^‐‐N were larger in the inorganic N treatment than in the manure or the control treatments throughout the growing season. The NO₃ ^‐‐N concentrations measured by the AEM method were correlated with NO₃ ^‐‐N extracted with 2M KCl (r² = 0.78***), suggesting that the AEM method could be used to measure NO₃ ^‐‐N concentrations in agricultural soils.     

Evaluation of the factors affecting direct polarization solid state 31P-NMR spectroscopy of bulk soils

³¹P‐NMR spectroscopy on bulk soils is a powerful tool for the identification of the different phosphorus forms in soils and for the evaluation of the dynamics of soil P. Up to now the majority of the papers dealt with liquid state ³¹P‐NMR spectroscopy on soluble soil organic substances. Only few papers were addressed to the study of the different phosphorus forms directly in bulk soils. In the present paper, some organic and inorganic phosphates of known structures, which are likely to be present in soil systems, were studied by direct polarization (DP) magic angle spinning (MAS) ³¹P‐NMR spectroscopy in order to understand the electronic factors responsible for chemical shifts of the phosphorus (P) nucleus and to serve as guidelines to assign P resonances in soil spectra. Number of hydrating water molecules, type of counter‐cation, degree of covalence, and spatial conformation of P in phosphate structures were found to affect signal positions in ³¹P‐NMR spectra. Both hydrating water and increase in degree of covalence of the X‐O‐P bonds (X=H, Na) enhanced the electronic density (E_D) around P, thereby producing up‐field shifts in ³¹P‐NMR spectra. The exchange of the Na⁺ counter‐cation with NH₄⁺ resulted in an increase of the cation potential (P_C) that is a measure of the cation polarizing power, and induced a down‐field shift of P signals, due to a corresponding reduction in E_D around the P nucleus. Both NMR down‐ and up‐field shifts were observed in organic phosphates, and were dependent on the spatial orientation of the phosphate groups that may have been fixed anisotropically in the solid state. Based on the factors that influence P chemical shifts for standard phosphates, attempts to assign ³¹P‐NMR signals in the spectra of five different unperturbed bulk soils were made.     

Radio-labile cadmium and zinc in soils as affected by pH and source of contamination

The determination of radio‐labile metals in soil has gained renewed interest for predicting metal availability. There is little information on to what extent the fraction of labile metal is affected by the soil properties and the source of metal contamination. The radio‐labile content (E value) of Cd and Zn was measured in field‐collected soils with Cd and Zn originating from different sources. The E values were erratic and sometimes even exceeded total metal content when the concentration in the soil extract was less than 8 μg Zn l^?1 or less than 3 μg Cd l^?1. Addition of EDTA (0.1 mm ) to the radio‐labelled soil suspension resulted in larger concentrations of Cd and Zn in solution and smaller E values for these soils. The E values were, however, unaffected by the presence of EDTA (0.1 mm ) in soils with larger concentrations of Cd and Zn in solution. The %E values (E value relative to metal soluble in aqua regia) ranged from 9% to 92% (mean 61%) for Cd and from 3% to 72% (mean 33%) for Zn. No correlation between soil properties and %E was observed for Cd, and the %E of Zn was negatively correlated with soil pH (r = ?0.65). There was a strong negative correlation between pH and %E in soils enriched with metals in soluble form (e.g. metal salts, corrosion of galvanized structures). In soils where Cd or Zn were added in a less soluble form, no such correlation was found, and %E values were generally less than in soils spiked with metal salts, suggesting that the source of the contamination controls mainly the labile fractions of Cd and Zn.     

Towards More Efficient Incentives for Agri‐environment Measures in Degraded and Eroded Vineyards

Evaluating the economic damage caused by soil erosion is important. In addition to increasing the awareness of the problem among farmers and policy makers, evaluation of the economic damage caused by erosion can promote the implementation of more sustainable soil management practices. In the present study, we describe a new approach to evaluate incentives for the adoption of agri‐environment measure (AEM) in degraded and eroded vineyards. To estimate this incentive, the replacement cost (RC) and the loss of income are calculated when the vineyard is managed with conventional tillage versus a cover crop (AEM). Our findings show that the incentive could range from the loss of income due to AEM adoption to the ecosystem service benefit (RC_C − RC_AEM). In our case study, the incentive ranged from 315 € ha⁻¹ (loss of income) to 1,088 € ha⁻¹ (ecosystem service benefit). Within this range, the incentive amount is determined according to efficiency criteria based on vineyard slope. We also present a conceptual model of public spending efficiency that should help policy makers decide how to allocate the incentives so as to maximize the economic return associated with ecosystem services. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Evaluation of an anion‐exchange membrane for extracting plant available phosphorus in soils

Abstract

Anion‐exchange resins (AER) have been used to determine plant available phosphorus (P) since the fifties and their results have shown strong relationships with plant growth and P uptake irrespective of soil properties. However, this procedure is still not widely used by laboratories because of difficulties in handling resin beads under routine conditions. New kinds and different shapes of resins are being produced each with specific characteristics that must be evaluated before use in laboratory procedures. Thus the objective of this work was to evaluate an AER manufactured in membranes reinforced with a Modacrylic fabric. These anion‐exchange membrane (AEM) sheets are commercially available, making them suitable for soil testing. The membranes were cut in pieces (1.0×7.5 cm) identified as AEM‐strips. The AEM‐strips were soaked in 0.5M HCl for a few days and transferred, after being rinsed with deionized water (DI), to 0.5M NaHCO₃ to convert them to HCO₃ ^‐ form. The AEM‐strips and resin beads in nylon bags recovered 98.4 and 98.0% of the P content in an aqueous P solution, respectively. Three eluent solutions were evaluated with different shaking times. The 0.1M H₂SO₄ and 1.0M NaCl in 0.1M HCl were equally suitable for the molybdenum blue color development without any pH adjustment, while the pH of the 0.5M HCl was too low. The elution of P from the AEM‐strips was independent of time with a 15‐min shaking being adequate for removal of all P from the strips. A comparison of soil sample preparation demonstrated that it was not necessary to vigorously grind or sieve the soil to improve the repeatability of the results. The AEM‐strips were compared with other methods (Pi impregnated filter paper, Mehlich I and Bray 1) using 32 soils from Guatemala with widely varying physico‐chemical and mineralogical properties. Phosphorus extracted by the AEM and Pi procedures (similar principle) were highly correlated and gave similar results irrespective of soil type. The acid extraction (Mehlich I and Bray 1 methods) attacked soil components (apatites) resulting in higher and inconsistent amounts of P extracted which may not be available to plants; the correlation between these methods within soils of similar properties was good, but when all soils were considered together the relationship was not significant. This demonstrated that the acid extraction method for P is not suitable for soils containing apatites, while those based on a sink for P (AEM and Pi) can be applied irrespective of the type of soil.     

Phosphorus Availability in Soils Amended with Different Phosphate Fertilizers

Abstract

Accurate measurement and characterization of phosphate rock dissolution are important for a better understanding of phosphorus (P) availability in soils. An incubation study was carried out on two New Zealand topsoils (0–15 cm; high P buffering capacity Craigieburn and low P buffering capacity Templeton) amended with North Carolina phosphate rock (NCPR) and water‐soluble phosphate (WSP) at 218 mg P kg^?1 (equivalent to 60 kg P ha^?1). Isotopic exchange kinetics was carried out after 12 h and 28 days of incubation to characterize P availability. This study showed that sensitivity of capacity factors (r₁/R, n) to explain changes in E_1min values was affected by the P buffering capacity of the soils. The recovery of applied P in the E pool (Rec_inE%) with extended incubation time was similar from the NCPR and WSP treatments (3.1–3.3%) in the Craigieburn soil compared with the Templeton soil in which Rec_inE% values were greater in WSP (9%) than NCPR (1.3%) treatment. The higher values of P derived from the applied P fertilizers in the E pool (Pdff_inE%>80%) suggested that the NCPR application in both soils would be efficient for increasing P availability to plants.     

Effect of phosphate fertilization on crop yield and soil phosphorus status

To evaluate the effect of three phosphorus (P) fertilization regimes (no P, P input equivalent to P off‐take by crops, P input higher than P off‐take) on crop yield, P uptake, and soil P availability, seven field experiments (six in crop rotations, one under permanent grassland) were conducted in Switzerland during nine years (six trials) or 27 years (one trial). Soil total P (Pt), inorganic P (Pi), organic P (Po), and the amount of isotopically exchangeable soil P were measured in the 0–20 cm and 30–50 cm layers of the arable soils and in the 0–10 cm layer of the permanent grassland soil. Omitting P fertilization resulted in significant yield decreases only in one field crop trial as the amount of P isotopically exchangeable within one minute (E_1min) reached values lower than 5 mg P (kg soil)^–1. In the absence of P fertilization Pi decreased on average from 470 to 410 mg P (kg soil)^–1 in the upper horizon of 6 sites while Po decreased only at two sites (from 510 to 466 mg P (kg soil)^–1 on average). In all the treatments of the trials started in 1989 the E_1min values of the upper horizon decreased on average from 15.6 to 7.4 mg P (kg soil)^–1 between 1989 and 1998. These decreases were also observed when P inputs were higher than crops needs, showing that in these soils the highest P inputs were not sufficient to maintain the high initial available P levels. Finally for the six arable trials the values of the isotopic exchange kinetics parameters (R/r₁, n, C_P) and P exchangeable within 1 minute (E_1min) at the end of the experiment could be estimated from the values measured at the beginning of trial and the cumulated P balance.     

A method for the analysis of the δ18O of inorganic phosphate extracted from soils with HCl

The oxygen isotope composition of phosphate (δ¹⁸O‐PO₄) has successfully been used to study the biological cycling of phosphorus (P) in seawater and marine sediments. However, only a few studies have used this approach in soils. In order to analyse δ¹⁸O‐PO₄, phosphate must be extracted from the soil, purified and converted to silver phosphate (Ag₃PO₄). The published extraction methods, successfully applied to marine waters and sediments, lead to the precipitation of impure Ag₃PO₄when used with soils or organic‐rich samples. Here we present an improved purification protocol, designed for soils and other organic‐rich samples. After extraction with HCl, phosphate is purified with multiple mineral precipitations that do not require extreme pH adjustments of the solutions. We show that contaminant‐free Ag₃PO₄ can be produced from fertilizers and various soils with different chemical and physical characteristics. Our first isotopic results confirm that differences in P status and availability in soils are expressed in the δ¹⁸O‐PO₄ signal, indicating the potential of this isotopic tracer to understand P dynamics in soil systems.     

Transformation and recovery of fertilizer phosphorus applied to five Quebec Humaquepts

Abstract

Improving phosphorus (P) fertilizer efficiency while minimizing environmental impacts requires better understanding of the dynamics of applied P in soils. This study assessed the fate of fertilizer P applied in Quebec Humaquepts. A pot experiment with five textural Humaquepts, each receiving 0 (P0), 10 (P10), 20 (P20) and 40 (P40) mg P kg^?1 soil was conducted under barley (Hordeum vulgare L.)-soybean (Glycine max L.) rotations. A modified Hedley procedure was used for soil P fractionation. The clayey soils reached a plateau of dry matter at less P applied than the coarser-textured soils. Plant P uptake, soil labile inorganic P (resin-P?+?NaHCO₃-P_i) and moderately labile inorganic P (NaOH-P_i) increased proportionally with P rate. The coarser-textured soils had lower contents of labile and moderately labile P_i, but a larger increase in labile P_i than the finer-textured soils after receiving P additions. The applied P was retained primarily as soil labile P_i, accounting for 43–69% of total soil recovery of applied P, compared to 20–30% recovered as moderately labile P_i, and 7–29% assumed to be sparingly soluble P (HCl-P?+?H₂SO₄-P). The labile P_i recovery of applied P was linearly depressed with clay content, compared to a quadratic relation for the moderately labile P_i recovery. The results suggest the importance of accounting for soil texture along with soil P adsorption capacity when assessing the efficiency of applied P, P accumulation in soils and subsequently P nutrient management.     

Labile lead in polluted soils measured by stable isotope dilution

It is well known that lead (Pb) is strongly immobilized in soil by adsorption or precipitation. However, the reversibility of these reactions is poorly documented. In this study, the isotopically exchangeable Pb concentration in soils (E‐value) was measured using a stable isotope (²⁰⁸Pb). Soils were collected at three industrialized sites where historical Pb emissions have resulted in elevated Pb concentrations in the surrounding soil. Lead concentrations ranged from background values, in the control soils collected far from the emission source, to highly elevated concentrations (5460–14440 mg Pb kg^?1). The control soil of each site was amended in the laboratory with Pb(NO₃)₂ to the same total Pb concentrations as the field‐contaminated soils. The %E values (E‐value relative to total Pb content) were greater than 84% in the laboratory‐amended soils, and ranged from 45% to 78% (mean 58%) in the field‐contaminated soils. The relatively large labile fractions of Pb in the field‐contaminated soils show that the majority of Pb is reversibly bound despite the fact that the binding strength is large. The Pb concentrations in soil solution were up to 3500‐fold larger for the laboratory‐amended soils than for field‐contaminated soils at corresponding total Pb concentrations. These differences cannot be explained by differences in labile fractions of Pb but are attributed to the decrease in soil solution pH upon addition of Pb²⁺‐salt.     

Effects of soil flooding and organic matter addition on plant accessible phosphorus in a tropical paddy soil: an isotope dilution study

Plant growth experiments were conducted to reveal the mechanism by which organic matter (OM) and soil flooding enhance phosphorus (P) bioavailability for rice. It was postulated that reductive dissolution of iron‐(III) [Fe(III)] oxyhydroxides in soil releases occluded phosphate ions (PO₄), i.e., PO₄ that is not isotopically exchangeable in the original soil prior to flooding. Rice was grown in P‐deficient soil treated with factorial combinations of addition of mineral P (0, 50 mg P kg^?1), OM (0, ≈ 20.5 g OM kg^?1 as cattle manure +/– rice straw) and water treatments (flooded vs. non‐flooded). The OM was either freshly added just before flooding or incubated moist in soil for 6 months prior to flooding; nitrogen and potassium were added in all treatments. The soil exchangeable P was labeled with ³³PO₄ prior to flooding. The plant accessible P in soil, the so‐called L‐value, was determined from the ³³P/³¹P ratio in the plants. The L‐values were inconsistently affected by flooding in contrast with the starting hypothesis. The OM and P addition to soil clearly increased the L‐value and, surprisingly, the increase due to OM application was larger than the total P addition to soil. An additional isotope exchange study in a soil extract (E‐value) at the end of the experiment showed that the E‐value increased less than the total P addition with OM. This suggests that plants preferentially take up unlabeled P from the OM in the rhizosphere compared to labeled labile inorganic P. The effects of soil flooding on P bioavailability is unlikely related to an increase of the quantity of bio‐accessible P in soil (L‐value) but is likely explained by differences in P mobility in soil.     

Anion and cation exchange resin membranes to assess the phosphorus status of some Portuguese soils

Abstract

Ion exchange resin methods were applied to 78 different soils to assess their phosphorus (P) status for predicting their response to P fertilization. The techniques used were anion exchange resin membranes eluted with hydrochloric acid (HCl) (AEM) and cation‐anion exchange resin membranes eluted with HCl (CAEM‐HC1), sodium chloride (NaCl) (CAEM‐NaCl) or water with directly color development (CAEM‐H₂O). Greenhouse studies were conducted with the same soils in order to validate laboratory data. Ryegrass was grown with two levels of P: nil and 150 mg P kg^‐1 of soil. Results indicate that soil P levels are significantly correlated (p<0.001) if extracted with AEM or CAEM, both eluted with HCl, although the CAEM technique had extracted larger amounts of P. Concerning the type of elution, results did not show significant differences (p<0.05) between CAEM‐HC1 and CAEM‐NaCl, but both were significantly correlated (p<0.001) with the results obtained with CAEM‐H₂O. All the techniques used to measure extractable P correlated significantly with relative yield and P uptake by ryegrass, showing their ability to predict soil P availability. Nevertheless, CAEM extraction had higher values of r². Among the three techniques for elution, the levels of correlation with the biological parameters were equivalent. From these results, it was concluded that: (i) exchange resins, specially CAEM, is an accurate method to assess the P fertility status of soils, and (ii) the traditional step of elution can be avoided, allowing the process to be less time consuming, thus more suitable for routine use.     

THE HIGH- AND LOW-ENERGY PHOSPHATE ADSORBING SURFACES IN CALCAREOUS SOILS

The two-surface Langmuir equation was used to study P adsorption by 24 calcareous soils (pH 7.2-7.6; 0.8-24.2 per cent CaCO₃) from the Sherborne soil series, which are derived from Jurassic limestone. High-energy P adsorption capacities (x″_m) ranged from 140–345 μg P/g and were most closely correlated with dithionite-soluble Fe. Hydrous oxides therefore appear to provide the principal sites, even in calcareous soils, on which P is strongly adsorbed (x″_m 6–51 ml/μg P). The low-energy adsorption capacities (x″_m) ranged from 400–663 μg P/g and were correlated with organic matter contents and the total surface areas of CaCO₃ but not with per cent CaCO₃, pH, or dithionite-soluble Fe. Total surface areas of CaCO₃ in the soils ranged from 4.0 to 8.5 m²/g soil. Low-energy P adsorption capacities agree reasonably with values (100 pg P/m²) for the sorption of phosphate on Jurassic limestones but phosphate was bonded much less strongly by soil carbonates (k″= 0.08–0.45 ml/μg P) than by limestones (k～10.0 ml/μg P). Low-energy P adsorption in these soils is tentatively ascribed to adsorption on sites already occupied by organic anions (and probably also by bicarbonate and silicate ions) which lessen the bonding energy of co-adsorbed P.     

EFFECT OF pH ON PHOSPHATE ADSORPTION AND ISOTOPIC EXCHANGE IN ACID SOILS AT LOW AND HIGH ADDITIONS OF SOLUBLE PHOSPHATE

Measurements of equilibrium phosphate concentrations, adsorbed phosphate and isotopically exchangeable phosphate (E_t) were made on suspensions of acid soils at initial P concentrations ranging from 1–1000 μM and pH values between 4.2 and 6.8. At low P concentrations (1–100 μM), the affinity of the adsorption reaction was greatest at pH 5.2–5.5. This result, which was inconsistent with the ligand-exchange hypothesis of Kingston et al. (1967, 1972, 1974), was interpreted in terms of the formation of basic aluminium phosphates of varying composition that depended on the OH/P ratio in solution. At the highest P concentrations (1000 μM), when the affinity of adsorption was least at pH 5.2–5.5, it appeared that basic calcium phosphates were precipitating at pH values > 5.5. In suspensions containing 1–100 μM P initially, values of E_t did not change consonantly with values of adsorbed P over the pH range 4.8 to 5.5. It is suggested that the E_t values were underestimated due to the presence of labelled complexes in solution which were detected by scintillation counting but not by the analysis for orthophos-phate. Evidence from solution studies (White et al., 1976) suggested that as much as one-third of the phosphate could be complexed with aluminium in solutions between pH 4.7 and 5.4 at P/A1 mole ratios of 0.075 to 7.5. It was apparent that the interpretation of the physical significance of E values in acid soils is complex and requires careful appraisal of the experimental techniques used.     

Management effects on forms of phosphorus in soil and leaching losses

We should know the effects of soil use and management on the contents and forms of soil phosphorus (P) and the resulting potential for leaching losses of P to prevent eutrophication of surface water. We determined P test values, amounts of sequentially extracted forms of P, P sorption capacities and degrees of P saturation in 20 differently treated soils and compared these data with leaching losses in lysimeters. One-way analyses of variance indicated that most fractions of P were significantly influenced by soil texture, land use (grassland, arable or fallow or reafforestation), mineral fertilization and intensity of soil management. Generally, sandy soils under grass and given large amounts of P fertilizer contained the most labile P and showed the largest P test values. Fallow and reafforestation led to smallest labile P fractions and relative increases of P extractable by H₂SO₄ and residual P. Arable soils with organic and mineral P fertilization given to crop rotations had the largest amounts of total P, labile P fractions and P test values. The mean annual concentrations of P in the lysimeter leachates varied from 0 to 0.81 mg l^–1 (mean 0.16 mg l^–1) and the corresponding leaching losses of P from < 0.01 to 3.2 kg ha^–1 year^–1 (mean 0.3 kg P ha^–1 year^–1). These two sets of data were correlated and a significant exponential function (R² = 0.676) described this relation. Different soil textures, land uses and management practices resulted in similar values for P leaching losses as those for the amounts of labile P fractions. Surprisingly, larger rates of mineral P fertilizer did not necessarily result in greater leaching losses. The contents of P extracted by NaHCO₃ and acid oxalate and the degrees of P saturation were positively correlated with the concentrations of P in leachates and leaching losses. As the P sorption capacity and degree of P saturation predicted leaching losses of P better than did routinely determined soil P tests, they possibly can be developed as novel P tests that meet the requirements of plant nutrition and of water protection.