Effect of soil pH on the requirement for water-soluble phosphorus in triple superphosphate fertilizers

A greenhouse study was conducted to determine if soil pH affects the requirement for water-soluble P and the tolerance of water-insoluble impurities in TSP fertilizers. Two commercial TSP fertilizers were selected to represent a range in phosphate rock sources and impurities. Phosphate fertilizer impurities were isolated as the water-washed fraction by washing whole fertilizers with deionized water. TSP fertilizers with various quantities of water-soluble P (1.2 to 99% water-soluble P) were simulated by mixing the water-washed fertilizer fractions or dicalcium phosphate (DCP) with reagent-grade monocalcium phosphate (MCP). The fertilizers were applied to supply 40 mg AOAC available P kg^–1 to a Mountview silt loam (fine-silty, siliceous, thermic Typic Paleudults). Wheat (Triticum aestivum (L.)) was harvested at 49 and 84 days after planting. Soil pH values at the final forage harvest were 5.4±0.16 and 6.4±0.15. At a soil pH of 5.4, the TSP fertilizers required only 37% water-soluble P to reach maximum yields while at pH 6.4 the fertilizers required 63% water-soluble P. Results of this study show that higher levels of water -insoluble P can be tolerated in TSP fertilizers when applied to acid soils. Phosphorus uptake was not affected by soil pH, but for the mixtures containing the fertilizer residues the source having the lowest level of Fe and Al had a higher relative agronomic effectiveness.     

Effectiveness of different phosphatic fertilizers measured using labelled superphosphate and phosphorus taken up by plants

The agronomic effectiveness of three P fertilizers (diamonium phosphate, rock phosphate and compost) was studied in a greenhouse experiment using wheat. A radioisotopic method, using triple superphosphate labelled with³²P, was used to evaluate the P in dried tops that was derived from i) the soil, ii) labelled superphosphate and iii) the fertilizer being studied.The ratio between P uptake from each fertilizer and P uptake from the soil was used to compare the effectiveness of the different fertilizers. P derived from diammonium phosphate was greater than P derived from the soil, except in one soil. P derived from rock phosphate was always lower than P derived from the soil. The effectiveness of compost depended on soil type. Compost can produce two kind of effects: i) a direct P contribution and ii) an indirect effect improving P uptake from the soil. The radioisotopic method can be used to study the effectiveness of fertilizers even when there are no differences in yield.     

Availability of banded triple superphosphate with urea and phosphorus use efficiency by corn

Phosphorus fixation results in low P use efficiency in acid soils. Increase in soil pH through urea hydrolysis may improve P availability and use efficiency. Growth chamber and field experiments were conducted to evaluate effects of urea on triple superphosphate (TSP) transformation and P use efficiency. A Ste. Rosalie clay (Typic Humaquept), an Ormstown silty clay loam (Typic Humaquept) and a Chicot sandy clay loam (Typic Hapludalf) were used in the growth chamber experiment with three rates of N (0, 200 and 400 mg N kg-1), two N sources, either urea or NH4 NO3, based on 87 mg P kg-1 soil. In the field, three rates of urea (0, 60 and 120 kg N ha-1) and two rates of TSP (26 and 52 kg P ha-1) were compared on a Ste. Rosalie clay and an Ormstown silty clay loam. Compacted or blended mixtures of urea-TSP with different ratios of N:P were used in the field experiment. In the growth chamber experiment, soil pH and dissolved organic carbon (DOC) concentration was increased by added urea, and Mehlich (3) and water extractable P thus increased with increased urea. Soil pH, DOC and available P levels were not significantly affected by added NH4 NO3. Phosphorus uptake increased with added N, either urea or NH4 NO3, but P concentration increased only with addition of urea. In the field, soil Mehlich (3)-P at day 20, P uptake and use efficiency, corn yields increased when urea was applied with TSP. Compacted mixtures of urea-TSP increased P uptake and use efficiency, corn yields in comparison with blended mixtures. The beneficial effects of banded urea with TSP on P availability and P use efficiency were primarily attributed to urea hydrolysis, subsequent pH increase and organic matter dissolution as well as synergistic effect of N and P. These results indicate that compaction of urea plus TSP may offer a significant advantage over blended mixtures.     

Long-term residual value of North Carolina and Queensland rock phosphates compared with triple superphosphate

The effectiveness of large single applications of North Carolina reactive rock phosphate, Queensland non-reactive rock phosphate, and Calciphos, were compared to the effectiveness of superphosphate in field experiments in south-western Australia for up to 11 years after application. As measured using plant yield, superphosphate was the most effective fertilizer in the year of application, and relative to freshly-applied superphosphate, the effectiveness of the superphosphate residues declined to be about 15 to 65% as effective in the year after application, and 5 to 20% as effective 9 to 10 years after application. Relative to freshly-applied superphosphate, all the rock phosphates were 10 to 30% as effective in the year of application, and the residues remained 2 to 20% as effective in the 10 years after application. The bicarbonate soil test reagent predicted a more gradual decrease in effectiveness of superphosphate of up to 70% 10 years after application. For rock phosphate, the reagent predicted effectiveness to be always lower than for superphosphate, being initially 2 to 11% as effective in the year after application, and from 10% to equally as effective 10 years later. Therefore rock phosphates are unlikely to be economic alternatives to superphosphate in the short or long term on most lateritic soils in south-western Australia.     

Mono- and diammonium phosphates and triple superphosphate as sources of P in a calcareous soil

Recovery of phosphorus from monoammonium phosphate (MAP), diammonium phosphate (DAP) and triple superphosphate (TSP), at rates of 0, 15, 30, or 45 mg P kg^–1 was determined in a pot experiment on a Calcaric Lithosol soil (21% CaCO₃). At the 15 mg P kg^–1 rate DAP was as effective as MAP and more effective than TSP in supplying P, but it was less effective than MAP and TSP at the higher rates of 30 and 45 mg P kg^–1. At the two higher P rates residual bicarbonate extractable P was also significantly lower with DAP. Yield dry matter was not affected by the source of P.     

Interaction of urea with triple superphosphate in a simulated fertilizer band

Fertilizer nutrient diffusion from fertilizer bands and transformations in soil can affect fertilizer nutrient availability to crops and knowledge of the transformations is necessary for proper management. The interaction of urea and triple superphosphate (TSP) on urea hydrolysis and P transformations during diffusion processes from a fertilizer band was evaluated in a laboratory incubation experiment with two eastern Canadian soils (Ste Rosalie clay, Modifiers Typic Humaquept, pH 5.0; Ormstown silty clay loam, Modifiers Typic Humaquept, pH 6.0). Two fertilizer sources (urea and TSP) and three N and P rates (0, 100 and 200 kg ha^–1) were combined in a factorial arrangement. Fertilizer combinations were placed on segmented soil columns, incubated and segments were analyzed for N and P content. Acidification from dissolution of TSP retarded urea hydrolysis, and curtailed the rise in soil pH surrounding the fertilizer band. Urea hydrolysis caused dissolution of organic matter in soils, which might inhibit precipitation of insoluble phosphates. Banding urea with TSP increased 1M KCl extractable soil P, soil solution P, sorbed P concentration and total P diffused away from the band. Urea decreased 0.01M CaCl₂ extractable P, indicating probable precipitation of calcium phosphates with CaCl₂ extraction. Banding urea with TSP could benefit P diffusion to plant roots in low Ca soils and increase fertilizer P availability.     

Incubating superphosphate in ‘dry’soil can reduce its effectiveness

Single superphosphate was incubated for six months at 25°C in soil which had been subject to one of three moisture treatments. These were: dried in a glasshouse, dried at a constant temperature of 25°C, or moist soil. Phosphorus (P) effectiveness was then compared with effectiveness of P from freshly-applied superphosphate using yields of wheat (Triticum aestivum) and triticale (×Triticosecale) tops in pot experiments.Incubation in soil which had been dried at 25°C did not decrease the effectiveness of the P. Incubation in moist soil decreased it to about 20% of the effectiveness of freshly-applied P in one case and to about 50% in the other case. Incubation in soil which had been dried in a glasshouse also decreased its effectiveness. The decrease varied with conditions, but in two cases the P was 70% as effective as freshly-applied P, and in one case only 45% as effective. Presumably sufficient moisture was present in the soil dried in the glasshouse to enable water-soluble P present in the fertilizer to react with the soil.     

Plant availability of phosphorus in the neutral ammonium citrate fraction of Brazilian acidulated phosphates

In Brazil, where the rock phosphates are high in impurities, no attempthas been made to evaluate the P supplying efficiency of the neutral ammoniumcitrate fraction (NAC) of P fertilizers, or to verify if the NAC +H₂O extraction solution (AOAC) is satisfactory for estimatingthe P availability. To attain these objectives, a greenhouse experiment wascarried out with samples of a Typic Hapludox soil. Four acidulatedphosphates obtained from Brazilian raw materials were studied; monocalciumphosphate p.a.[Ca(H₂PO₄)₂·H₂O]was included as a standard source of P, as well as leached samplescontaining no water-soluble P. The fertilizers were thoroughly mixed withthe whole soil in the pots or with only 1% of its volume, at the rateof 50 mg kg^-1 of P, soluble in NAC + H₂O. Cornplants (Zea mays, L.) were grown for 35 days and the amounts of dry matterand P accumulated in plant tops were determined. Increasing the amount ofcationic impurities in the raw materials decreased the concentration ofwater-soluble P, NAC + H₂O-soluble P and water-soluble P/NAC+H₂O soluble P ratio of the fertilizers obtained. The P in theNAC fraction was not as much available to plants as in the NAC +H₂O fraction or in pure MCP. The great variation found in drymatter (5.4 to 17.1 g pot^-1) and in P uptake (6.3 to 22.2 mgpot^-1) indicates that the AOAC method is not an adequate indexfor evaluating the P availability of fertilizers with high amounts ofcationic impurities.     

Residual value of superphosphate for oat and barley grown on a very sandy,phosphorus leaching soil

In a field experiment in a Mediterranean climate (474 mm annual rainfall, 325 mm (69%) falling in the May to October growing season) on a deep sandy soil near Kojaneerup, south-western Australia, the residual value of superphosphate was measured relative to freshly-applied superphosphate. The grain yield of five successive crops (1988–1992) was used to measure the residual value: barley (Hordeum vulgare), barley, oat (Avena sativa), lupin (Lupinus angustifolius), and barley. There was no significant yield response to superphosphate applied to the first crop (barley, cv. Moondyne). There were no results for the second crop (barley) due to weeds or the fourth crop (lupin) due to severe wind erosion which damaged the crop. The residual value of superphosphate was measured using grain yields of the third crop (oat, cv. Mortlock) for superphosphate applied one and two years previously, and the fifth crop (barley, cv. Onslow) for superphosphate applied one, two, three and four years previously. In February 1992, before sowing the fifth crop, soil samples were collected to measure bicarbonate-extractable phosphorus (P) (soil test P) which was related to the subsequent grain yields of that crop. This relationship is the soil test P calibration used to estimate the current P status of soils when providing P fertilizer recommendations.The residual value of superphosphate declined markedly. For the third crop (oat), it was 6% as effective as freshly-applied superphosphate one year after application, and 2% as effective two years after application. For the fifth crop (barley), relative to freshly-applied superphosphate, the residual value of superphosphate in successive years after application was 46%, 6%, 3% and 2% as effective. The soil has a very low capacity to sorb P, and P was found to leach down the soil profile. The largest yield for P applied one and two years previously in 1990, and two, three and four years previously in 1992, was 35 to 50% lower than the maximum yield for freshly-applied P.Soil test P was very variable (coefficient of variation was 32%) and mostly less than 8µg P/g soil. The calibration relating yield (y axis) to soil test P (x axis) differed for soil treated with superphosphate one year previously compared with soil treated two, three and four years previously. The top 10 cm of soil was used for soil P testing, the standard depth. P was leached below this depth but some of the P leached below 10 cm may still have been taken up by plant roots. Consequently soil test P underestimated the P available to plants in the soil profile. The soil test P calibration therefore provided a very crude estimate of the current P status of the soil.     

The effect of water supply on the response of subterranean clover,annual medic and wheat to superphosphate applications

The effect of water supply on the response of subterranean clover (Trifolium subterraneum), annual medic (Medicago polymorpha) and wheat (Triticum aestivum) to levels of phosphorus (P) applied to the soil (soil P) was studied in four glasshouse experiments. P was applied as powdered superphosphate. In one experiment, the effect on plant yield of P concentration in the sown seed (seed P) was also studied. There were two water treatments: the soil was returned to field capacity, by watering to weight, either daily (adequate water, W1) or weekly (water stress, W2). In three experiments: (i) P concentration or content (P concentration × yield) in plant tissue was related to plant yield, and (ii) soil samples were collected before sowing to measure bicarbonate-extractable P (soil test P) which was related to subsequent plant yields.Compared with W1, water stress consistently reduced yields of dried tops and the maximum yield plateau for the relationship between yield and the level of P applied, by up to 25 to 60% in both cases. Compared with W1, the effectiveness of superphosphate for producing dried tops decreased for W2 by 11 to 45%, for both freshly-applied and incubated superphosphate. Consequently in the field, water supply, which varies with seasonal conditions, may effect plant yield responses to freshly — and previously — applied P fertilizer.Seed P increased yields, for W1, by 40% for low soil P and 20% for high soil P; corresponding values for W2 were 20 and 12%. Consequently proportional increases due to seed P were smaller for the water-stressed treatment.The relationship between yield and P concentration or content (internal efficiency of P use) differed for W1 and W2, so that the same P concentration or content in tissue was related to different yields. Estimating the P status of plants from tissue P values evidently depends on water supply, which in the field, differs in different years depending on seasonal conditions.The relationship between yield and soil test P differed for W1 and W2. Predicting yields from soil test P can only provide a guide, because plant yields depend on both P and water supply, which in the field may vary depending on seasonal conditions.     

Effect of water supply on the response of wheat and triticale to applications of rock phosphate and superphosphate

The effect of water supply on the response of wheat (Triticum aestivum) and triticale (×Triticosecale) to levels of freshly-applied rock phosphate and superphosphate, and the residues of these fertilizers applied 9 years previously in the field, was studied in three glasshouse experiments. The < 2 mm fraction of the top 10 cm of soil was used (1.8 kg soil per pot), and in one experiment, freshly-applied fertilizer was also added to the more acidic subsoil (10 to 20 cm). There were two water treatments: the soil was returned to field capacity by watering to weight, either daily (W1, adequate water) or weekly (W2, water stress). Yield of dried tops was used to calculate fertilizer effectiveness. The phosphorus (P) concentration in dried tops was used to determine critical P, which is the P concentration related to 90% of the maximum yield. Just before sowing, soil samples were collected to measure bicarbonate-extractable (soil test) P which was related to plant yield.Water stress reduced yields and maximum yield plateaus by 20 to 40%. Water stress reduced the effectiveness of all P fertilizers by between 20 to 60%, largely because of a reduction in the maximum yield potentials. In the field, water supply is seasonally dependent and it can affect the yield response of plants to freshly-applied rock phosphate and superphosphate and the residues of these fertilizers applied to the field in previous years. Relative to placing fertilizer in the topsoil, placing fertilizer in the subsoil improved effectiveness by about 26% for rock phosphate and 12% for superphosphate.The relationship between yield and P concentration in dried tops, and critical P, differed for W1 and W2. The soil test P calibration, which relates yield to soil test P, and the soil test P required to produce the same yield also differed for W1 and W2. Consequently critical P and soil test P calibrations depend on water supply, which in the field varies within and between growing seasons. This is so for freshly- and previously-applied rock phosphate and superphosphate.     

Long-term field evaluation of phosphate rock and superphosphate use strategies in acid soils of Hungary: Two comparative field trials

The effect of two P-forms and the P fertilization system were studied in field trials set up on two moderately acidic Hungarian soils. Reactive Algerian rock phosphate and Kola superphosphate doses were based on the phosphorus equivalence. The experimental design makes it possible to compare the effect of annual 35 kg/ha P doses with initial one-time application of the 175 kg/ha P level in a five-year interval. Ammonium-lactate (AL)-, NaHCO₃ (Olsen)- and DW-P contents as well as Lakanen- Erviö (LE)- soluble Cd, Cr and Sr contents were also determined. The results of the first five-year period are reported in the paper. Responses to P fertilization were related to the original P supply of the soils. There was no significant difference between the two P forms and between the P fertilization systems on both grain yield and P-uptake. While AL- method overestimated, and Olsen-method – on the other hand – underestimated the P supply of reactive Algerian rock phosphate, distilled water (DW)-soluble P contents indicated the soil P status more accurately. Phosphorus balances were positive after the fifth year of the trials in the P treated plots. The soluble Cd and Cr contents did not increase in the Algerian rock phosphate treated plots. On the other hand, Kola superphosphate application at 175 kg/ha P level resulted in higher LE-Sr contents in soils. The Algerian rock phosphate is an economic alternative P source on the moderately or strongly acidic Hungarian soils.     

Effects of organic manure on solubility and mobility of different phosphate fertilizers in two paddy soils

The solubility and mobility of three phosphate fertilizers [superphosphate (SP), Ca-Mg phosphate (Ca-Mg-P) and diammonium phosphate (DAP)] with or without combination of farmyard manure (FYM) and/or farmyard manure juice (FYMJ) in two paddy soils (Ultisol and Entisol) from the Zhejiang Province of China were determined. Incubation experiments were conducted under controlled greenhouse conditions in the Institute of Agricultural Chemistry, Bonn University, Germany. The results showed that water soluble P and Olsen P in both the application band and the adjacent zones (10 and 20 mm from the application band) was highest with DAP, and lowest with Ca-Mg-P. Both FYM and FYMJ increased water soluble P (100–300%) and Olsen P (80–300%) for the application band in both soils. Moreover, the combination of FYM significantly increased water soluble P and Olsen P for the adjacent zones (20 mm for the Ultisol and 10 mm for the Entisol), but such effects were not significant in combination with FYMJ. Consequently, the main effect of FYM is due to organic substances from decomposition rather than organic compounds in the FYMJ. Also, the combination of FYMJ with SP and DAP significantly increased the pH value in the application band. The pH in the adjacent zone (10 mm) was slightly increased by the combination of FYM with each of three P fertilizers. The solubility and mobility of phosphate in soils differed greatly among phosphate fertilizers. The combinations of organic manure with mineral phosphate fertilizers increased solubility and mobility of phosphate in both paddy soils, especially in the Ultisol.This paper is dedicated to Professor Xi Sun.     

Comparison of single and coastal superphosphate for subterranean clover on phosphorus leaching soils

Coastal superphosphate, a partially acidulated rock phosphate (PARP), is being considered as an alternative fertilizer to single superphosphate for pastures in high rainfall (> 800 mm annual average) areas of south-western Australia. The effectiveness of single and coastal superphosphate, as P fertilizers, was measured in two field experiments using dry herbage yield of subterranean clover (Trifolium subterraneum). The experiments were started in April 1990 and were terminated at the end of 1993. In the years after P applications, soil samples were collected each January to measure Colwell soil-test P, which was related to plant yields measured later on that year, to provide soil P test calibrations.Relative to freshly-applied single superphosphate, the effectiveness of freshly-applied coastal superphosphate and the residues of previously-applied single and coastal superphosphate were less effective in some years (from 3% as effective to equally effective), and up to 100% more effective in other years. This large range in effectiveness values in different years is attributed to different climatic conditions. Soil P test calibrations were different for soils treated with single or coastal superphosphate. The calibrations were also different for different yield assessments (harvests) in the same year, and in different years. Consequently soil P testing can only provide a very crude estimate of the current P status of the soils.     

The effect of apatite and elemental sulphur mixtures on growth and P content ofCentrocema pubescens

Two glasshouse pot experiments and one incubation experiment were undertaken to measure the effectiveness of Sri Lanka (Eppawala) apatite rock phosphate as a fertilizer for the perennial legumeCentrocema pubescens. The apatite was applied alone, or as a mixture with elemental sulphur and soil containingThiobacelli bacteria either as powder or pellets that were either uncoated or coated with rubber (to reduce the rate of release of P thereby increasing P release for a longer-term).Application of apatite to the soil significantly increased DM yields of shoots and P content (yield × P concentration) in shoots. Application of sulphur andThiobacelli bacteria with the apatite caused further increases in yield and P contents of shoots. Pelletizing the apatite and sulphur together with a soil inoculum ofThiobacillus did not increase dry matter yields of shoots or P content of shoots compared to a mixture of apatite and sulphur in the powder form. Incubating the mixture in powder or pellet form in the laboratory increased water-soluble P extracted and decreased the pH of these mixtures. Pellets of the mixture when coated with rubber released P more slowly during incubation, but growth ofCentrocema pubescens treated with coated pellets was comparable with that for uncoated pellets.     

Comparative responses of annual pasture legume species to superphosphate applications in medium and high rainfall areas of Western Australia

The comparative phosphorus (P) requirement of different annual pasture legume species was measured in seven field experiments in south-western Australia. Superphosphate was applied once only, at the start of each experiment. The duration of the experiments was from one to three years. The amount of P required to produce 90% of the maximum yield of each legume was used to estimate the comparative P requirements of the legumes at each harvest. Ornithopus spp. (O. compressus, O. perpusillus andO. pinnatus) required less P thanTrifolium subterraneum, the most widely sown pasture legume in Western Australia. The P requirements ofMedicago polymorpha varied with soil type when compared to that ofT. subterraneum. M. polymorpha required less P on a soil with a neutral pH value, but had a similar P requirement on a more acidic soil.M. murex, generally required more P thanT. subterraneum. In some experiments, the comparative P requirement of the different legumes varied for different harvests.At each harvest in each experiment, the relationship between yield and P concentration in tissue (internal efficiency curves) usually differed for different legumes. Presumably different legumes take up P from the soil at different rates within each harvest, and utilize the absorbed P differently to produce herbage and seed. The exceptions were that similar internal efficiency curves were measured forO. compressus andT. subterraneum in one experiment, and three cultivars ofO. compressus in another experiment.     

Effectiveness of two partially acidulated rock phosphates,coastal superphosphate and Ecophos,compared with North Carolina reactive rock phosphate and superphosphate

The effectiveness of coastal superphosphate, a partially acidulated rock phosphate (PARP) made from apatite, and Ecophos, a PARP made from calcium iron aluminium (crandallite millisite) rock phosphate, was compared in pot experiments with the effectiveness of ordinary superphosphate (OSP) and North Carolina reactive apatite rock phosphate (NCRP). There were three experiments using different lateritic soils collected in Western Australia. Fertilizer effectiveness was measured using yield of dried wheat (Triticum aestivum) tops grown for 28 days. Three successive crops were grown. The phosphorous (P) fertilizers were applied and mixed with the soils before sowing the first crop. In addition, OSP was added to extra pots before sowing crops 2 and 3 in order to measure the effectiveness of the original P fertilizers relative to freshly-applied OSP for these crops.As measured using plant yield, coastal superphosphate was the most effective P fertilizer for three crops on an acidic peaty sand (pH water 5.0). Relative to freshly-applied OSP, it was 154% as effective for crop 1, 75% as effective for crop 2, and 36% as effective for crop 3. Corresponding values for Ecophos were 44, 29 and 19%, and for NCRP, 77, 67 and 29%, with the original OSP treatment being 61 and 56% as effective for crops 2 and 3. For three crops on a lateritic gravel loam (pH 6.5), both coastal superphosphate and OSP were the most effective fertilizers, and were equally effective for crop 1, and relative to freshly-applied OSP, were about 31% as effective for crop 2, and 16 and 21 % as effective for crop 3. Corresponding values for Ecophos were 47,15 and 11%, and NCRP, 33,15 and 5%. For two crops in a loamy sand (pH 5.4), OSP was the most effective fertilizer, and, relative to fresh OSP, it was 36% as effective for crop 2. Relative to fresh OSP, the effectiveness for crops 1 and 2 of coastal superphosphate was 57 and 18%, for Ecophos 71 and 27%, and for NCRP 50 and 36%.     

A comparison of triple superphosphate and Gafsa ground rock phosphate fertilisers as P-sources for grass-clover swards on a poorly-drained acid clay soil

Organic farming practice prohibits the use of triple superphosphate (TSP) as a source of phosphorus. As basic slag is not now generally available, interest is focused on the relative value of ground rock phosphate (GRP). A comparison of TSP and Gafsa GRP was made during 1988–92 as to their ability to increase DM production under cutting from newly sown grass/white clover swards established in 1987 on an acid clay soil in SW England. Averaged over the different P fertiliser inputs and years, the DM yield was 8.0 t ha-1 y-1 (range 6.93–9.81) compared to 6.3t ha-1y-1 (range 6.00–7.71) without added P. Lime was added at either 3 or 6t ha-1 in 1987, and at half these rates in 1990. Whereas the yield improved by 45% with P at the lower rate of lime, it improved only by 12% at the higher rate. When P fertiliser was applied annually at 30 kg ha-1, TSP was superior to GRP, but when applied in one initial dose of 120 kg ha-1, GRP was superior over the subsequent 4 year period. There was no consistent effect of the addition of either P or lime on the clover content of the sward. The alkaline bicarbonate soil test (Olsen P) was a good predictor of available P within a given year; there was a general reduction of P availability over the course of the experiment. Mechanisms to explain the longer term effectiveness of GRP are postulated and discussed. It is concluded that farmers who are limited to using GRP rather than TSP would suffer a yield penalty over the longer term of 11.5%, and that P fertilizer for the ley phase in a rotation should be incorporated in one dose at the outset.     

Long-term greenhouse evaluation of partially acidulated phosphate rock fertilizers

The agronomic effectiveness (yield and P uptake) of twelve granular, partially acidulated phosphate rock fertilizers (PAPR) and two finely ground, unacidulated phosphate rocks (PR) were compared to that of a single superphosphate in a long-term greenhouse experiment with lucerne (Medicago sativa L., cv. CUF101), grown in a low P sorbing, moderately acid, sandy loam soil of moderate P status (Paleustaf). The PAPRs were prepared from two unreactive PRs (Christmas Is. A grade and Duchess rock from Queensland) and acidulated at two rates (25% and 50% on a H₂SO₄ to single superphosphate basis) with either H₂SO₄ or H₃PO₄. Additional products included H₂SO₄ PAPRs cogranulated with elemental S (10% w/w).Superphosphate was consistently superior to all PRs and PAPRs in agronomic effectiveness throughout this two-year study. The most effective of the PAPRs were those that were 50% acidulated with H₂SO₄ and cogranulated with elemental S; this type of fertilizer from both rocks was approximately 2/3 as effective as superphosphate when relative agronomic effectiveness indices (RAE) were calculated from cumulative yields. The increase in agronomic effectiveness relative to superphosphate (RAE value) by the partial acidulation of the PR could be attributed to its effect of increasing the P solubility in the PAPR. A curvilinear relationship existed between the RAE values of PRs and PAPRs, measured from cumulative yield or P uptake data, and the percentage of the total P in each fertilizer that was in a soluble (water + citrate soluble) form. Cogranulation with elemental S (10% w/w) significantly displaced this relationship upwards by increasing the RAE of H₂SO₄ PAPRs by more than 50%. The maximum cumulative recovery of applied P by lucerne tops after five bulked harvests (fifteen consecutive harvests) was 61.5%, which occurred at the low application rate of superphosphate. The decline in the substitution value of PRs for superphosphate, that occurred with increasing P rates tended to be offset both by increasing the level of acidulation and by cogranulating the PAPR with elemental S.     

On the Substrate Binding of Linoleate 9-Lipoxygenases

Lipoxygenases (LOX; linoleate:oxygen oxidoreductase EC 1.13.11.12) consist of a class of enzymes that catalyze the regio- and stereo specific dioxygenation of polyunsaturated fatty acids. Here we characterize two proteins that belong to the less studied class of 9-LOXs, Solanum tuberosum StLOX1 and Arabidopsis thaliana AtLOX1. The proteins were recombinantly expressed in E. coli and the product specificity of the enzymes was tested against different fatty acid substrates. Both enzymes showed high specificity against all tested C18 fatty acids and produced (9S)-hydroperoxides. However, incubation of the C20 fatty acid arachidonic acid with AtLOX1 gave a mixture of racemic hydroperoxides. On the other hand, with StLOX1 we observed the formation of a mixture of products among which the (5S)-hydroperoxy eicosatetraenoic acid (5S-H(P)ETE) was the most abundant. Esterified fatty acids were no substrates. We used site directed mutagenesis to modify a conserved valine residue in the active site of StLOX1 and examine the importance of space within the active site, which has been shown to play a role in determining the positional specificity. The Val576Phe mutant still catalyzed the formation of (9S)-hydroperoxides with C18 fatty acids, while it exhibited altered specificity against arachidonic acid and produced mainly (11S)-H(P)ETE. These data confirm the model that in case of linoleate 9-LOX binding of the substrate takes place with the carboxyl-group first. Sequence data: The nucleotide sequences reported in this paper are annotated in the GenBank/EMBL data bank under the accession numbers Q06327 and S73865.