Extraction of soil phosphorus with calcium chloride solution for prediction of plant availability

Abstract

Soil and vegetative samples of ley and cereals were collected four times during the growing season from field and pot trials with different phosphorus (P) fertilisation levels. The soil samples, dried and of field moisture condition, respectively, were extracted by 0.01M calcium chloride (CaCl₂) at two different soil:extractant ratios (1:2 and 1:10), and analysed by inductively coupled plasma emission spectrometry (ICP) for content of P. The plant samples were digested in concentrated nitric acid (HNO₃) and the P content determined by ICP. Calcium chloride‐extractable P content was lowest in the middle of the growing season, while plant P was highest in the beginning of the season. Phosphorus extracted by CaCl₂ solution was higher at a soil:extractant ratio of 1:10 than at 1:2, and also when drying the soil before extraction. A soil:extractant ratio of 1:2 minimizes the risk of coming too near the limit of determination. However, if organic soils are also to be included, a ratio of 1:10 has to be used in order not to have all the solution absorbed by some types of soils. The solution of ammonium lactate/acetic acid (AL) extracted nearly two powers of ten more P than CaCl₂ solution. There was a good relationship between the methods. If calcareous or very acid soils had been included, a less good relation would have been expected. Plant P content varied more in straw than in grain between different treatments. Measuring CaCl₂‐extractable P with ICP might be able to predict plant uptake of P by plants. This would be a great advantage when using 0.01M CaCl₂ as a universal extradant.     

Applicability of 0.01 M CaCl2 as a single extraction solution for the assessment of the nutrient status of soils and other diagnostic purposes

Abstract

The applicability of 0.01 M CaCl₂ solution as a single extraction agent for soils as a basis for fertilizer recommendation was tested on a variety of soils both from the Netherlands and from some tropical countries. Air‐dry soil samples were subjected to extraction with 0.01 M CaCl₂ and to several conventional extraction procedures, and the results were compared. In the soil suspensions pH was measured, whereas in the extracts Na, K, Mg, P, different extractable N‐forms and Zn were measured. The values found in CaCl₂ extracts are discussed in relation to results of other extraction procedures and as to their potential value in soil quality assessment. It is concluded that a single extraction procedure with 0.01 M CaCl₂ can be applied for fertilizer recommendation purposes. The possibility of determining different extractable N‐forms (NH₄, NO₃, soluble organic N) significantly enhances the value of the method in predicting the N‐fertilizer needs. Furthermore it was found that the concentration of Zn in 0.01 M CaCl₂ extracts was a good indicator of phytotoxicity in a polluted area. Additional advantages of this extraction are low costs, simplicity and repro‐ducibility.     

Extraction with 0.01 m CaCl2 underestimates the concentration of phosphorus in the soil solution

The aim of this paper was to compare the concentration of P in soil extracts prepared with water and a ‘soil solution proxy’ (‘SSP’, that is, a salt solution similar in ionic composition and strength to the actual soil solution) with that in 0.01 m CaCl₂ extracts, which is usually taken as a measure of soil P intensity. Seventy widely ranging agricultural soils from the Mediterranean part of Spain were used. Soil/solution ratio was 1:10 and extraction time 3 days. For 0.01 m CaCl₂, a short extraction time of 30 min was also used as the reference method. CaCl₂‐P(3 days) and CaCl₂‐P(30 min) were not significantly different for the 40 noncalcareous soils group, but CaCl₂‐P(3 days) was significantly larger than CaCl₂‐P(30 min) for the 30 calcareous soils group. The Water‐P/CaCl₂‐P(30 min) ratio was not significantly related to any soil property, its mean being 6.3 for the noncalcareous and 5.8 for the calcareous soils group. The mean SSP‐P/CaCl₂‐P(30 min) ratio was 2.6 for the noncalcareous and 3.1 for the calcareous soils group, and decreased slightly with increasing ionic strength of the soil solution in the noncalcareous soils group. These results are consistent with the promoting influence of the Ca ion and ionic strength on P adsorption by permanent‐charge soils. The fact that extraction with 0.01 m CaCl₂ generally results in underestimation of the actual concentration of P in the soil solution should be considered when CaCl₂‐P is used as a soil P test.     

Effect of long-term fertilization on the K-fixing capacity of soils

The comparative analysis of potassium fixation by soddy-podzolic and chernozemic soils with different nutrient supplies was performed using a standard ammonium acetate solution and 0.25 and 0.01 M CaCl₂ solutions. It was found that the application of potassium to soils unfertilized for a long time increased the fixation of potassium. When the application rate of potassium fertilizers increased, the amount of fixed potassium increased and its portion (in percentage of the rate) decreased. At any application rate of potassium, the fixing capacity of the soils increased as the soil texture became finer. It was found that a 0.01 M CaCl₂ solution is suitable for studying the K-fixing capacity of soils.     

Lime potential of soils as directly measured with two ion-selective electrodes

A pH-glass and calcium-selective electrode pair was used for the measurement of lime potential of soils. The lime potential was higher when measured in CaCl₂ solutions of high concentration and with high solution to soil ratio for soils with considerable positive charge. Water or 10^?3 M CaCl₂ solution and a solution to soil ratio of 1:1 is suggested. Some examples of the application of the proposed method in soil research are given.     

Comparison of extractable phosphorus from two sulfuric acid methods with the Mehlich phosphorus test number one

Abstract

All mineral phosphates in soil dissolve more completely when HCl is mixed with H₂SO₄ than with the HCl alone. It was hypothesized that a new extracting solution of H₂SO₄ alone with the same ionic strength or the same acidity as the Mehlich P1 extractant would extract similar amounts of soil phosphorus (P) as the Mehlich P1 soil test. Thirty six acid soils from Alabama, Georgia, North Carolina, South Carolina, and Colorado were used in this study. These acid soils reflect wide ranges in parent materials, texture, pH, organic matter, and available soil P. They were analyzed for available soil P with the Mehlich P1 soil test and with the two H₂SO₄ methods: Method A has an extracting solution of same ionic strength (0.0875M) as the Mehlich P1 extractant, and Method B was an extracting solution of the same acidity (0.0375M) as the Mehlich P1 extractant. Correlations between the results of Mehlich P1 with Method A and Method B were 0.994 and 0.997, respectively. The measured test precision was <3.5% for all three methods. The new H₂SO₄ methods are simple and faster to conduct under routine operations than the original Mehlich P1 extractant, and because of the high correlations, the H₂SO₄ methods should predict crop response to P as well as the original Mehlich P1 extractant for acid soils.     

Evaluation of soil sulfate extractants and methods of analysis for plant available sulfur

Abstract

A steady decline in sulfur additions to Atlantic Canadian soils has prompted the need for an accurate method of determining their plant available sulfur status. Three soils were extracted with five soil extractants ‐ 0.01M Ca(H2PO₄)₂‐H₂O in 2M HOAc, 0.1M CaCl₂, Bray‐1 and de‐ionized water. The soil extracts were analyzed for sulfur or sulfate using inductively coupled argon plasma emission spectrometry (ICAP), AutoAnalyzer (AAN), anion exchange‐high performance liquid chromatography (HPLC‐CD) or atomic absorption spectroscopy (AAS). Results were compared with plant response of sulfur treatments to red clover, ryegrass, canola and wheat in a growth room. Instrument reproducibility and crop response indicated the ideal method of determining plant available soil sulfur was HPLC‐CD using the extractant Ca(H2PO₄)₂‐H₂O.     

Chloroform-labile trace elements in soil via fumigation-extraction: Steps towards the soil microbial ionome beyond C:N:P

Secondary and trace elements may be limiting soil microbial functioning, albeit microbial demand and content remain largely unknown and methods for their in situ detection are limited. Thus, the objective of the present study was to take the first step towards the method development for the assessment of the soil microbial ionome, that is, the elemental composition of soil microbial communities. Chloroform (CHCl₃) fumigation extraction was used for the detection of microbial CHCl₃-labile secondary and trace element concentrations in soils. The suitability of two extractants (NH₄NO₃, CaCl₂) for the quantification of CHCl₃-labile concentrations of phosphorus, sulphur, potassium, sodium, and magnesium, as well as selenium, iron, zinc, manganese, copper, cobalt, nickel, molybdenum, vanadium, boron, silicon, barium, arsenic, and cadmium, were tested in six agricultural soils. Additionally, three soil to extractant ratios (1:5, 1:10, and 1:20) and two extraction durations, 1 or 2 h, were tested in a subset of two soils. Out of the two extractants tested, 0.01 M CaCl₂ was found to be the best-suited extractant. For CaCl₂, a soil-to-extractant ratio of 1:20 with an extraction time of 1 h was best for the majority of elements in the two soils tested. In a limited number of agricultural soils, we were able to show that CHCl₃ fumigation extraction can successfully be applied to the elements phosphorus, sulphur, potassium, sodium, magnesium, zinc, manganese, copper, nickel, vanadium, boron, silicon, and barium to yield a CHCl₃-labile element fraction. Conversion values to microbial biomass, accounting for elements contained in the cell envelope components, which are mostly not extractable, and to account for adsorption to soil colloids during extraction are yet to be determined in a larger variety of soils. To overcome some of the limitations of the fumigation extraction approach for secondary and trace elements, a pre-extraction step may provide a suitable solution.     

Effect of aluminum, zinc, copper, and lead on the acid-base properties of water extracts from soils

The potentiometric titration of water extracts from the upper horizons of taiga-zone soils by salt solutions of heavy metals (Pb, Cu, and Zn) showed that their addition is an additional source of the extract acidity because of the involvement of the metal ions in complexation with water-soluble organic substances (WSOSs). At the addition of 0.01 M water solutions of Al(NO₃)₃ to water extracts from soils, Al³⁺ ions are also involved in complexes with WSOSs, which is accompanied by stronger acidification of the extracts from the upper horizon of soddy soils (with a near-neutral reaction) than from the litter of bog-podzolic soil (with a strongly acid reaction). The effect of the Al³⁺ hydrolysis on the acidity of the extracts is insignificantly low in both cases. A quantitative relationship was revealed between the release of protons and the ratio of free Cu²⁺ ions to those complexed with WSOSs at the titration of water extracts from soils by a solution of copper salt.     

Mobilization of Cu and Zn in contaminated soil by nitrilotriacetic acid

Batch and upflow column leaching experiments were used to evaluate the nature and extent of Cu and Zn solubilization from contaminated soil by nitrilotriacetic acid (NTA) in 0.025 M NaClO₄. In batch soil suspensions, NTA levels of 10^?5 to 10^?3 M substantially promoted Cu and Zn release from the metal-enriched soil. The ability of NTA to enhance Cu and Zn solubility decreased with increasing solution acidity probably due to competitive binding of NTA by protons and Fe released by hydrous oxide dissolution. However, in the pH range typically encountered in northeastern U.S. soils, soluble metal levels were nearly constant for a given NTA concentration. Leaching soil columns with NTA solutions enhanced Cu release more than Zn, as the enrichment ratio (cumulative metal leached by NTA compared to the 0.025 M NaClO₄ control leachate) after 85 pore volumes displacements was 23.6 and 4.3 for Cu and Zn, respectively. While Cu release by 0.01 M CaCl₂ differed little from the control, 0.01 M CaCl₂ was substantially more effective than 10^?5 M NTA in displacing bound Zn. The data reflect different retention mechanisms for Cu and Zn in this soil.     

Sorption of Phosphorus from Swine,Dairy, and Poultry Manures

In most phosphorus (P) sorption studies, P is added as an inorganic salt to a predefined background solution such as calcium chloride (CaCl₂) or potassium chloride (KCl); however, in many regions, the application of P to agricultural fields is in the form of animal manure. The purpose of this study, therefore, was to compare the sorption behavior of dissolved reactive P (DRP) in monopotassium phosphate (KH₂PO₄)–amended CaCl₂ and KCl solutions with sorption behavior of DRP in three different animal manure extracts. Phosphorus single‐point isotherms (PSI) were conducted on eight soils with the following solutions: KH₂PO₄‐amended 0.01 M CaCl₂ solution, KH₂PO₄‐amended 0.03 M KCl solution, water‐extracted dairy manure, water‐extracted poultry litter, and swine lagoon effluent. The PSI values for the dairy manure extract were significantly lower than the CaCl₂ solution for all eight soils and lower than the KCl solution for six soils. The PSI values were significantly higher, on the other hand, for poultry litter extract and swine effluent than the inorganic solutions in four and five of the soils, respectively. Our observations that the sorption of DRP in manure solutions differs significantly from that of KH₂PO₄‐amended CaCl₂ and KCl solutions indicates that manure application rates based on sorption data collected from inorganic P salt experiments may be inaccurate.     

Role of the soil particle-size fractions in the sorption and desorption of potassium

The sorption and desorption capacities of two soils (a loamy soddy-podzolic soil and a sandy clay chernozem) were analyzed. Both the entire soils and their particle-size fractions were studied. Samples were taken from the soils of long-term field experiments with fertilizers. A 0.01 M CaCl₂ solution was used as the extractant. The soil fractions <10 ??m were found to have the maximum capacities for sorption-desorption of potassium. The soil fractions <0.2 ??m were the most enriched with potassium. The use of kinetic methods of analysis allowed assessing the contributions of the particle-size fractions to the potassium status of soils with different degrees of fertilization. It was noted that different fertilizing systems had no effect on the rates of potassium desorption from the colloidal fraction, while appreciable differences among the different treatments were observed for the fractions of 0.2?C1.0 and 1?C10 ??m.     

Optimization of DTPA and calcium chloride extractants for assessing extractable metal fraction in polluted soils

Abstract

Metal availability in soils is often assessed by means of extraction with chemical solutions, among others the chelating agent DTPA (diethylenetriaminepentaacetic acid) and the non‐buffered salt calcium chloride (CaCl₂). The same procedures are used for polluted soils that were originally created to assess the nutrient status of arable soils. We studied the influence of various parameters (type of shaker, shaking time, soil to solution ratio, and concentration of chemical extractant) and modify the DTPA and CaCl₂ extraction procedures to make them suitable for the study of polluted soils. The chosen extraction ratio and extractant concentration were the followings: 8 g/20 mL of 0.1 MCaCl₂ and 2 g/20 mL of 0.005 M DTPA. The optimized procedures were applied to nine soil samples affected by different sources of pollution (mine works, vehicle emissions, and various industries). Cadmium (Cd) showed the highest extractability with both extractants. Depending on the soil, copper (Cu) and zinc (Zn) (using DPTA) and Cu and manganese (Mn) (using CaCl₂) were the followings in the extractable amounts. Cadmium, Cu, and Zn were highly correlated in both extractions and with total contents.     

Extraction of soil boron for predicting its availability to plants

Abstract

Field and greenhouse studies were conducted in Prince Edward Island (P.E.I.) on soybean (Glycine max (L.) Merr.), red clover (Trifolium pratense L.), alfalfa (Medicago sativa L.), and rutabaga (Brassica napobrassica, Mill). Plant B concentrations were compared to soil B extracted by hot water, 0.05M HCl, 1.5M CH₃COOH, and 0.01M CaCl₂. The r values for extractable soil B versus plant B were: hot water (0.67), 0.05M HCl (0.82), 1.5M CH₃COOH (0.78), and hot 0.01M CaCl₂(0.61). Results of soil B from the 0.05M HCl extracts were generally found to give the best correlation and linear regression among the four extractants tested for predicting the B availability to plants. Overall, the 0.05M HCl proved to be the best extractant and is recommended for predicting the available B status of acid soils. The probability of error with 0.05M HCl is less since it is shaken for a fixed period of time as opposed to subjective error which could be introduced in monitoring the boiling time using hot water. Since HCl is the cheapest among the chemical extractants used it would be most suited for determining soil B in countries with poor economic resources.     

Effects of equilibrating salt solutions on phosphate sorption by soils

Abstract

Several equilibrating salt solutions have been used in the studies of P sorption by soils and sediments. This study was conducted to evaluate the effects of 10 salt solutions on estimation of P sorption by soils. Results obtained showed that, when the equilibrating solution was made to contain 0.01M with respect to CaCl₂, Ca(NO₃)₂, CaSO₄, MgCl₂, KCl, LiCl, Nacl, or KHCO₃, the amount of P sorbed by soil always exceeded the amount sorbed from the soil‐water system. In comparison with the amount of P sorbed from water, 0.01M NaHCO₃ reduced P sorption by soils. Use of THAM buffer (0.05M pH 7.0) to control the pH increased P sorption by some soils and decreased P sorption by others, relative to that sorbed from the soil‐water system. The results indicated that inclusion of salts in the equilibrating solution for P‐sorption studies should be avoided, especially in studies related to water quality.     

Comparison of indirect methods for the determination of percent exchangeable aluminium in acid soils of Galicia (NW Spain)

Abstract

Ten easily determined soil parameters related to soil acidity were evaluated for their potential to provide simple, indirect estimates of the exchangeable aluminium percentage (PAL). These parameters were correlated with the PAL in 0.6N BaCl₂ extracts of soils collected from lime trials on 4 different parent materials. Six rates of lime (0, 0.75, 1.5, 3, 6, 12 t/ha) were added 3–4 years prior to collection of the samples. The soil parameters examined were the pH of soil suspensions with SMP, Woodruff and New Woodruff buffer solutions; the pH of 1, 5 and 10mM CaCl₂ and 0.6N BaCl₂ soil extracts, and the aluminium content of 1, 5 and 10mM CaCl₂ soil extracts. The best correlations with the exchangeable aluminium percentage for all soils considered, were those based on the aluminium content of the 5mM CaCl₂ extract (r=0.976, n=24) followed by the pH of the 0.6N BaCl₂ extract (r=0.945, n= 24). Both these methods are suggested as reliable indirect estimates of soil exchangeable alumimium percentage where availability of staff or equipment restrict direct determinations.     

Organic matter extracted with 0.01 M CaCl2 or with 0.01 M NaHCO3 as indices of N mineralisation and microbial biomass

A pot experiment was carried out with three soils at ambient temperature in which temporal changes in fractions of soil organic matter that were extractable with either 0.01 M CaCl₂ or 0.01 M NaHCO₃ were compared with changes in N mineralisation and microbial biomass C. UV spectral analysis of soil extracts was also carried out on sub-samples taken at the beginning of the experiment. The objective was to quantify the fractions of extractable soil organic matter and determine whether these could be used to estimate the mineralisable organic N content of the soils. The results suggested that part of the NaHCO₃-extractable organic matter originated in the microbial biomass but that non-biomass material was also present. The non-biomass material was not identified directly, but was composed of compounds with high UV absorbance. In the case of CaCl₂, the results suggested that extracellular proteins were contained in the extract and that some material released from the actively growing microbial biomass may also have been present. A supplementary study with 16 soils was carried out to determine the ability of the organic matter solubilised by either extractant to predict soil N uptake by barley seedlings. A significant relationship (P<0.01) was found between N uptake and CaCl₂-extractable material only.     

THE DETERMINATION OF DESORPTION ISOTHERMS FOR SOIL PHOSPHATE USING LOW VOLUMES OF SOLUTION AND AN ANION EXCHANGE RESIN

Phosphate desorption isotherms were determined (a) by shaking 1 g soil with 3 ml 0.01M CaCl₂ solution plus different amounts of an anion exchange resin, and (b) by diluting soil with different volumes of 0.01M CaCl₂ solution. Adsorption isotherms were determined using a soil to solution ratio of 1 g to 3 ml. In soils of intermediate P status adsorption isotherms appeared continuous with desorption by method (a), but not with desorption by method (b), which predicted lower buffer powers than did (a). Method (a) led to increases and (b) to decreases in pH. Additions of dissolved silica had no influence on P desorption by method (b).     

A re‐examination of exchangeable acidity as extracted by potassium chloride and potassium fluoride

Abstract

In order to better understand some of the factors likely to affect measurements of KC1 extractable acidity, experiments were conducted using synthetic solutions and extracts from a wide range of contrasting soils. The reagents used for measuring exchangeable acidity (i.e., KC1 and KF) were also examined to evaluate the effects of chemical impurities on acidity measurements. Two commonly used titrimetric methods were adapted and tested to determine the accuracy and precision of acidity measurements. The exchangeable acidity of soil extracts was investigated by extraction methods, extractant concentration, and extractant volume. Results from the soil extract experiments indicated that continuous shaking has no significant effect on acidity measurements. Filtration, however, is critical, especially for acidic organic‐rich soils, since aluminum (Al) ions can be lost during centrifugation. Extractant concentration and volume had variable effects on the acidity measurements for individual soils. In general, the modified Yuan's method is preferable to the modified Thomas’ method for estimating exchangeable Al. To ensure successful determination of exchangeable acidity, we recommend using a wider KCl:soil ratio (>15:1, v/w) for organic soils with low base saturation and allophanic Andisols. In sum, potassium chloride and potassium fluoride extraction for estimating exchangeable acidity is applicable for most soils.