Extraction of soil‐available phosphate,nitrate, and sulphate ions using ion exchange membranes and determination by ion exchange chromatography

Abstract

In recent years, ion exchange membranes (IEM) have been used successfully to determine the availability of soil nutrient elements for plants. In general, the procedures proposed are applied to the determination of a single ion, and in only a few of these studies, the selectivity of these IEM was considered. Therefore, this work was conducted (a) to find the most suitable extraction conditions for phosphate (H₂PO₄ ^‐), nitrate (NO₃ ^‐), and sulfate (SO₄ ^2‐) in soils by IEM and their subsequent determination by ion chromatography, (b) to test the effectiveness and selectivity of IEM, (c) to compare the results obtained by IEM with the common procedure for determining the availability of the soil nutrient elements, and (d) to verify whether a relation exits between the concentration of phosphorus (P) extracted by IEM and the plant P requirement. The soil samples used for this study were Humic Cambisols located in four forest plots under natural conditions and four plots fertilized with 100 kg P ha^‐1 as triple superphosphate. The efficacy of the IEM was high (85% for SO₄ ^2‐, and 92% for H₂PO₄ ^‐ and NO₃ ^‐). Statistically significant correlations were obtained between the H₂PO₄ ^‐ extracted by IEM and the H₂PO₄ ^‐ obtained by the Bray P1 procedure (r²=0.936) and with the H₂PO₄ ^‐ extracted using Saunders and Williams (1955) procedure (r²=0.370). The correlation obtained between the amount of NO₃ ^‐ extracted with IEM and that obtained using 2M potassium chloride (KCl) was also highly significant (r²=0.828). The IEM extraction allowed to know in a single extraction process and a single subsequent measurement by ion chromatography the concentrations of soil available H₂PO₄ ^‐, NO₃ ^‐, and SO₄ ^2‐ ions, which are of great plant nutrition interest. Phosphorus extractable with IEM yielded a close relationship with biomass production and could be used for determining the P requirement of these forest trees.     

Microsite assessment of forest soil nitrogen,phosphorus, and potassium supply rates in‐field using ion exchange membranes

Abstract

A new method for microsite assessment of soil nutrient supply in forest soil was developed. The method involves the use of ion exchange membranes to assess differences in soil nitrogen (N), phosphorus (P), and potassium (K) supply rates in‐field over small depth increments in the forest floor (i.e., the L, F, and H horizons). Ion exchange membranes were buried and retrieved from the forest floor in an aspen forest stand in Saskatchewan, Canada. Small (6 mm diameter) sections of the membrane were cut out and ion concentration on the sections measured to provide a nutrient supply rate at that location. Soil nutrient supply rates at the site ranged from 4.6–6.0, 7.3–8.5, 11.6–21.5, and 122–196μg 10 cm²#lb2 h^‐1 for NH₄ ⁺‐N, NC₃ ^‐‐N, P, and K, respectively. On average, the highly humified H horizon had the highest N and P supply rates, followed by the F horizon, with the surface litter (L horizon) having the lowest N supply rates. The simplicity and sensitivity of the procedure make this method appropriate for in‐field assessment of differences in soil nutrient supply over small vertical and horizontal distance and was especially appropriate for the forest floor horizons in forest soils.     

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.     

Desorption of soil phosphate by anion‐exchange resin

Abstract

Kinetics of phosphate desorption from twenty soils by anion‐exchange resin were not satisfactorily explained by either film diffusion (or ion exchange mechanism) mechanism or particle diffusion mechanism. Eut the phosphate desorption process was adequately explained by a two‐constant rate equation. The two constants, the coefficient term (i.e., rate factor) and the constant term (i.e., solution P initially) were significantly correlated with amorphous Al; rate factor increased and solution P decreased with the increase in amorphous Al among the soils. Thus, influence of amorphous Al in P availability from soils must be considered.     

Sorption of calcium and sulfate by sandy soils from flue‐gas desulfurization gypsum and phosphogypsum

Abstract

Increasing concern on sulfur dioxide (SO₂) pollution has prompted many coal‐fired electric power generating plants to install SO₂ scrubbing units which generate large amounts of flue‐gas desulfurization gypsum (FGDG). This source of gypsum can be an excellent amendment to supply calcium (Ca) and/or sulfate (SO₄) to sandy soils which are deficient in these nutrients. In this study, reactions of FGDG, phosphogypsum (PG), reagent grade calcium sulfate (CaSO₄), and calcium chloride (CaCl₂) were investigated using a Candler fine sand (uncoated, hyperthermic, Typic Quartzipsamment), a typical well‐drained deep sand, and a Pineda fine sand (loamy, siliceous, hyperthermic, Arenic Glossaqualf), a typical shallow poorly drained sand. Concentrations of various water‐soluble elements were similar in FGDG as well as PG, except the latter contained 11 and 15 g/kg phosphate (PO₄) and fluoride (F), respectively, while these ions were undetectable in the former. In batch‐equilibration (4 h) technique using soilrsolution ratio of 1:2, pH of equilibrium solution decreased by 0.2 and 0.8 units, while ionic strength increased by 5‐ and 15‐fold in the Pineda and Candler sand, respectively, when using FGDG or PG solution as compared to using water for equilibration. Sorption of Ca by the two soils varied from 0.56 to 0.71 Cmolc/kg regardless of source of gypsum. As compared to sorption of SO₄, that of Ca was greater by 2.5‐ and 2.6 to 4.3‐fold by the Candler and Pineda sand, respectively. With the exception of SO4 sorption by the Pineda sand, this study demonstrated that the reactions of FGDG with these sandy soils were very similar to those of PG or reagent grade CaSO4. Since much of the past research on agricultural use of gypsum was done using PG and CaSCU, we could conclude that similar response could be expected with use of FGDG.     

Spatial variation of soil test phosphorus and potassium,oxalate‐extractable iron and aluminum,phosphorus‐retention index,and organic carbon content in soils of Western Australia

Abstract

Spatial variation of bicarbonate soil test phosphorus (P) and bicarbonate soil test potassium (K) was studied by measuring soil test values for 40 individual soil samples collected from random locations within eight uniform 100 m by 100 m field sites in south‐western Australia. In addition, for five of the sites, spatial variation of the three P sorption indices (ammonium oxalate extractable iron, ammonium oxalate extractable aluminum, and the P retention index) and of organic carbon (C) was measured for 20 individual soils samples. Spatial variation was found to be large, with coefficient of variation (CV) exceeding 20% in most cases, and 50% in some cases. It is therefore essential to collect an adequate number of soil samples from uniform areas in paddocks in order to provide a representative composite sample to measure the soil properties.     

Effects of calcium lignosulphonate on Mehlich‐III extractable calcium,magnesium, and potassium quantity‐intensity relationship in the soil with or without potassium dihydrogen phosphate

Abstract

Calcium lignosulphonate (CaLS), a waste product from the pulp and paper industry, is expected to affect reaction of K fertilizer in the soil, thus influences their availability to crops. A clay soil (Typic Humaquept) was incubated with various amounts of CaLS (0 to 150 g kg^‐1 soil) and potassium dihydrogen phosphate (0–25.64 mmol kg^‐1 soil) for 240 h under moist conditions at 5 and 15°C. Subsamples were extracted with deionized water and the Mehlich‐III (M3) solution for the analyses of pH, and P, Ca, K and Mg concentrations and K adsorption (K_ad). Higher temperature reduced M3 extractable K (K_M3). CaLS and K additions increased M3 extractable Mg (Mg_M3) with Ca contributed more than did K as indicated by the standardized estimates. Additions of CaLS increased K_M3. Potassium adsorption decreased with the increases in CaLS addition rates. Significant positive linear relationships were observed between K_ad and the concentration ratio of [K⁺]/[Ca²⁺]^½, suggesting that the potassium buffering capacity of the soil was reduced by the additions of CaLS, with the desugared CaLS being more effective than the non‐desugared CaLS. The increased slope values with the increases in CaLS additions of the linear relationships between K_M3 and [K]/[Ca²⁺]^½ indicated that CaLS improved the quantity and intensity relationships and increased the power of the soil supplying plants with K.     

Washing procedure for mixed‐bed ion exchange resin decontamination for in situ nutrient adsorption

Abstract

Mixed‐bed cation + anion exchange resin bags are frequently used to assess in situ nutrient availability in forest soils, and have demonstrated their utility for comparing the impacts of different disturbances associated with treatments. They are generally installed in organic or mineral soil horizons for a certain time period, then recovered and extracted, to inform about nutrient availability during that period. For the method to be effective, the ion exchange sites of resins must be clear from any contaminants prior to installation in the soil. A washing procedure to be conducted before in situ burial of mixed‐bed resins was developed and is described. The IONAC NM‐60 H⁺/OH^‐ resins are consecutively washed with 2 N NaCl, deionized water, and 0.1 N NaOH. Finally, resins are rinsed with deionized water and stored moist and cold until bag preparation and burial in the soil.     

Comparison of mehlich 3, mehlich 1, ammonium bicarbonate‐DTPA, 1.0M ammonium acetate,and 0.2M ammonium chloride for extraction of calcium,magnesium, phosphorus,and potassium for a wide range of soils

Abstract

Extractants employed for routine soil analysis vary from one laboratory to another. Lack of a universal soil extractant is a serious limitation for interpretation of analytical results from various laboratories on nutritional status of a given soil. This limitation can be overcome by developing functional relationships for concentrations of a given nutrient extractable by various extradants. In this study, extractability of Ca, Mg, P, and K in a wide range of soils (0–15 cm) from citrus groves in Florida representing 21 soil series, with varying cultural operations, were compared using Mehlich 3 (M3), Mehlich 1 (M1), ammonium acetate (NH₄AOc), pH = 7.0 (AA), 0.2M ammonium chloride (NH₄Cl), and ammonium bicarbonate‐DTPA (AB‐DTPA) extractants. Soil pH (0.01M CaCl₂) varied from 3.57 to 7.28. The concentrations of Ca or Mg extractable by M3, M1, AA, and NH₄Cl were strongly correlated with soil pH (r² = 0.381–0.482). Weak but significant correlations were also found between AB‐DTPA extractable Ca or Mg and soil pH (r² = 0.235–0.278). Soil pH relationships with extractable K were rather weak (r² = < 0.131) for M1 and NH₄Cl but non‐significant for M3, AB‐DTPA, and AA. Concentrations of Ca, Mg, and K extractable by M3 were significantly correlated with those by either M1, AA, or NH₄Cl extractants. Mehlich 3‐P was significantly correlated with P extractable by M1 extractant only. Mehlich 3 versus AB‐DTPA relationship was strong for K (r² = 0.964), weaker for Mg and P (r² = 0.180–0.319), and non‐significant for Ca. With the increasing emphasis on possible use of M3 as an universal soil extractant, data from this study support the hypothesis that M3 can be adapted as a suitable extractant for routine soil analysis.     

Determination of total organic‐C in soils by an improved chromic acid digestion and spectrophotometric procedure

Abstract

An improvement to the Walkley‐Black wet digestion method for the rapid determination of organic carbon over the range 0.2–5.5% in air‐dry soil is described. It permits total recovery of the organic‐C in finely ground soil samples digested with the heat of dilution from mixing N K₂ Cr₂ O₇ with concentrated H₂SO₄. in test tubes followed by external heating from a hot‐plate digestor. The organic‐C concentrations are determined directly, as the Cr product in diluted soil digests, by absorptiometry at 600 nm with calibration against similarly treated sucrose standards in solution. For the soils tested, there were negligible interferences from carbonates, wood charcoal, coke, Fe⁺² and readily reducible Mn; Cl does not interfere with the organic‐C assay in non‐saline soils but for saline soils a correction based on 1/12 Cl^‐ assay of the soil is necessary. The present method is compared with Tabatabai and Bremner's dry combustion procedure and Allison's manometric adaptation for calcareous soils. The procedure described here does not require carbonate to be determined and is therefore simpler. In addition it is cheaper, faster and more effective in controlling interferences than dry combustion procedures.     

The determination of ammonium and chloride by an auto‐analyser for the measurement of cation exchange capacity of soils

Abstract

An auto‐analyser method has been developed for the simultaneous determination of NH₄ ⁺ and Cl^‐ in Ca(NO₃)₂/KNO₃ extracts of NH₄Cl treated soils for cation exchange capacity measurements. The method gives satisfactory agreement with manual titration procedures.     

Humic matter isolated from soils and water by the XAD‐8 resin and conventional NaOH methods

Abstract

Differences were studied in humic (HA) and fulvic acid (FA) extracted from soils and streams in South Georgia by the Amberlite XAD‐8 resin and conventional NaOH method. Characterization analysis was performed by liquid ¹³C NMR, infrared (IR) spectroscopy, scanning electron microscopy (SEM), and chemical analysis. The NMR spectra indicated that the resin method yielded black water HA and FA with spectroscopic, chemical and elemental characteristics different from those isolated by the conventional NaOH method. Humic acids from both the resin and conventional NaOH methods were composed of aliphatic, aromatics and carboxyl groups, but the “resin”; HA contained more aliphatic groups. These differences were also noticed between the FA fractions obtained by the two methods. The differences corresponded to differences in IR spectra. The IR spectrum of “resin”; FA exhibited only a weak shoulder at 1625/cm for the COO”; stretching vibration, in contrast to that of FA isolated by the conventional NaOH procedure. Apparently, the high aliphatic‐CH₃ group content has blocked the vibration above, as evidenced by methylation of HA. Fulvic acid extracted by the resin method was also higher in total acidity, but considerably lower in N content than FA obtained by the conventional NaOH method. Both methods yielded black water FA which was less aromatic in nature than black water HA, or soil FA.     

No‐tillage corn response to placement of fertilizer nitrogen,phosphorus, and potassium

Abstract

Fertilizer placement for corn (Zea mays L.) has been a major concern for no‐tillage production systems. This 3‐yr study (1994 to 1996) evaluated fertilizer phosphorus (P) or potassium (K) rates and placement for no‐tillage corn on farmers’ fields. There were two sites for each experiment involving fertilizer P or K. Treatments consisted ofthe following fertilizer rates: 0,19,and 39 kg P ha^‐1 or 0, 51, and 102 kg K ha^‐I. The fertilizer was broadcast or added as a subsurface band 5 cm beside and 5 cm below the seed at planting. Early plant growth, nutrient concentrations, and grain yields were measured. At the initiation of the study, soil test levels for P and K at the 0–1 5 cm depths ranged from optimum (medium) to very high across sites. Effects of added fertilizer and placement on early plant growth and nutrient concentrations were inconsistent. Added fertilizer had a significant effect on grain yields in two of twelve site‐years. Therefore, on no‐tillage soils with high fertility, nutrient addition, and placement affected early plant growth and nutrient utilization, but had limited effect on grain yield. Consequently, crop responses to the additions of single element P or K fertilizers under no‐tillage practices and high testing soils may not result in grain yield advantages for corn producers in the Northern cornbelt regardless of placement method.     

Factors affecting the adsorption of micro‐amounts of tagged phosphorus by soils

Abstract

Adsorption of a small amount of P by soil from a solution, which delivers concentrations approximating the composition of soil solution systems, was measured for a heterogeneous group of 343 soils using ³²P‐labelled KH₂PO₄ solution. The method allowed accurate determination of small quantities of P and identified the P under consideration as that added from solution. Simple correlations and stepvise linear regression analyses indicated that soil pH, Ca, P, Al, Fe, organic matter and particle size significantly influenced the amount of P adsorbed by the soils.     

Semi‐micro determination of total phosphorus in soils,sediments, and organic materials: A simplified perchloric acid digestion procedure

Abstract

A semi‐micro modification of perchloric acid digestion method for the determination of total P in soils, sediments, and organic materials is described. Samples are digested for 30 minutes with nitric acid at 115 °C and then for 2 hours with perchloric acid at 170 °C in an aluminum heating block. After dilution, samples are hydrolyzed at 100 °C for 1 hour in order to decompose pyrophosphate, and the liberated orthophosphate is determined without a neutralization step by the phosphomolybdate blue method of Murphy and Riley (1962). Comparability with the method of Sommers and Nelson (1972) is demonstrated using nine samples of different types. The same reaction conditions of digestion and color development as in the determination of total P in waters (Kopá?ek and Hejzlar, 1993) enable a comparable estimate of total P in solid and water samples in complex environmental studies.     

Long‐term phosphorus solubility in soils receiving poultry litter treated with aluminum,calcium, and iron amendments

Abstract

Phosphorus (P) runoff from poultry litter applied to fields can adversely impact water quality. The majority of P in runoff from poultry litter is soluble, so decreasing the solubility of P could lessen the impact of poultry litter on water quality. The objective of this study was to determine long‐term P solubility in soils receiving poultry litter treated with aluminum (Al), calcium (Ca), and iron (Fe) amendments at various soil pHs. Soil pH was adjusted to 4.0, 5.0, 6.0, 7.0, and 8.0 using elemental sulfur (S) or CaCO₃ with some soil left at its native pH. The pH‐adjusted soil was then incubated with either no litter (control), litter alone (litter control), or litter amended with alum, A1₂(SO₄)₃.16H₂O, (100 or 200 g/kg), Ca(OH)₂ (25 or 50 g/kg), or FeSO₄ .7H₂O (100 or 200 g/kg). The soil was then allowed to equilibrate in the dark at room temperature for 0, 7, 49, 98, and 294 days. After equilibration, soils were extracted with deionized water and soluble reactive P levels were determined. Water‐soluble P levels decreased with time in all treatments, including the control and litter control treatments. Soil pH also affected soluble reactive P levels, with the lowest levels generally observed at pH 8.0. Addition of both unamended and chemically‐amended litter to soil significantly increased P concentrations at all combinations of pH and sampling time. Addition of chemically‐amended litter to soil significantly reduced soluble reactive P compared to unamended litter. With all treatments, an apparent equilibrium was reached at 98 d after treatment. Amendment of litter with either FeSO₄ .7H₂O or alum resulted in the lowest soluble reactive P levels after 294 days. Use of chemical amendments to limit P solubility has potential and should be pursued as a means of reducing eutrophication of sensitive surface waters where poultry litter is applied as a fertilizer.     

Comparisons of phosphorus availability between anion exchange resin and mehlich‐1 extractions among Oxisols with different capacity factors

Abstract

Acid and dilute‐salt chemical extractants are commonly used to assess and adjust phosphorus (P) availability in soils. Soybean was grown for 45 days under greenhouse conditions on samples of 10 Oxisols treated with variable levels of soluble P to compare critical soil P levels between an anion exchange resin (AER) and the Mehlich‐1 extractant, and to evaluate the influence of the soil P capacity factor (PCF) on the critical soil P levels. Variation among soils in the quantities of extracted P and critical P levels with the AER was less than that with Mehlich‐1. Low correlation values between soil characteristics related to PCF and measurements of AER soil P suggested that the AER method was not as sensitive to variations in soil PCF as Mehlich‐1. Interpretations of AER critical P levels, therefore, do not need auxiliary measures of PCF as with the Mehlich‐1 extractant. The reverse was true, however, for P uptake. Therefore, the criteria used to assess plant response to P (P uptake or dry matter production) in soils with variable PCF will influence the results obtained in correlations between methods used to extract soil P.     

A comparison of hot water extraction to standard extraction methods for nitrate,potassium, phosphorus,and sulfate in arid‐zone soils

Abstract

Increasing demand for soil analysis prompted by environmental and economic factors has intensified the need for an inexpensive, fast, convenient and precise extraction. Current soil analysis procedures require several extractants which limit their use in many small commercial and residential applications. This paper reports the results of tests conducted with an innovative hot water extraction method to meet these needs in the soils of the arid Western United States. Hot water under pressure generated by commonly available espresso makers was used, with an appropriate proper soil/water ratio, to extract nitrate, potassium (K), sulfate, and phosphorus (P) in as many as 38 soils. The same extract was also used to measure pH. There were high and significant correlations when comparing standard soil analysis extraction methods and the hot water extraction for nitrate, sulfate, K, and P [r=0.99, 0.92, 0.85, and 0.60, respectively (p=0.001)]. The time of extraction varied with each soil, ranging from 0.3 minutes with a sandy soil to 4.5 minutes for a clay soil, and averaged 1.4 minutes. This extraction procedure coupled with available analytical equipment shows promise as an acceptable process for measuring nitrate, K, sulfate, P, and pH in soils.     

Nitrogen,phosphorus, potassium and magnesium contents of field vegetables — Recent data for fertiliser recommendations and nutrient balances

When calculating fertiliser recommendations and nutrient balances, growers and advisers usually do not do site specific measurements but use data from look up tables. Data given by older literature sources, however, do not take into account today's cropping practices. Therefore a databank on nutrient contents of total yields, marketable yields and harvest residues of 22 field vegetable crops is presented. This databank was compiled using results from topical field experiments and from recent literature.