Comparison of a hot water and cold 0.01 M Cacl2 extraction procedures for the determination of boron in soil

Abstract

In 100 different soils, hot (100C) water extractable boron was determined and the results were compared with boron data after extraction of the same soil samples with cold (20C) 0.01 M CaCl₂. Since the boron concentrations in cold soil extracts are too low for direct determination, the extracted boron was converted into BF4‐ and subsequently extracted with a liquid anion exchanger, Aliquat 336, into xylene, and measured by ICP‐AES. A linear relation with R² = 0.74 was found between the two tested procedures. It is, therefore, concluded that with a cold 0.01 M CaCl₂ extraction equally valuable soil boron values can be obtained as with the more difficult to standardize hot water extraction procedure.     

Extractable Concentrations of Cobalt from Serpentine Soils with Several Single‐Extraction Procedures

In this study, we selected three soil pedons on the shoulder, backslope, and footslope along a serpentine toposequence to measure cobalt (Co) extractability using six single‐extraction procedures. These extraction procedures are distilled water, 0.11 M acetic acid in the first step of the BCR sequential extraction (BCR1), 1 M ammonium acetate (NH₄OAc; pH 7.0), 0.01 M calcium chloride (CaCl₂), diethylenetriamine pentaacetic acid (DTPA), and 0.1 M hydrochloric acid (HCl). Although the Co concentrations in the water extracts of the study soils ranged from 0.15 to 0.93 mg kg^?1, those with HCl extraction can be up to 22.1 mg kg^?1. The extractable Co concentrations in the study soils demonstrate that the extraction capacity is in the order HCl > DTPA > CaCl₂ ? NH₄OAc > BCR1 > H₂O. The percentages of extractable Co after applying the six single‐extraction procedures reveal that Co mobility is greatest in the soils on the backslope, moderate on the footslope, and least mobile on the shoulder.     

Estimation of Plant‐Available Nitrogen in Soils using Rapid Chemical and Biological Methods

The relationships between potential laboratory indices for plant‐available nitrogen (N) and the plant N uptake in a pot experiment with ryegrass were assessed for 13 mineral soils and 2 peat soils. The methods included aerobic soil incubation, soil incubation in a bioreactor, hot potassium chloride (KCl)–extractable mineral N, 0.01 M calcium chloride (CaCl₂)–extractable N, and N loss at heating. The indices for total plant‐available N accounted for 63–93% of the variance in N uptake in a statistical analysis with all soils (n = 15) and 27–89% for the mineral soils (n = 13). Most indices were not a direct quantitative measure of the plant N uptake. The N mineralization indices accounted for 57–86% of the variance in N mineralization for all soils and 5–50% for the mineral soils. Hot KCl‐extractable mineral N and 0.01 M CaCl₂–extractable N were the most promising rapid indices for plant‐available N.     

Nitrogen compounds extracted by electroultrafiltration (EUF) or CaCl2 solution and their relationships to nitrogen mineralization in soils

The objective of the investigation was to identify the most important organic N-containing fractions extracted from soils by electroultrafiltration (EUF) or a CaCl₂ solution, respectively, and their importance for nitrogen mineralization. The investigation comprised 19 agricultural and one forest top soil. Net N mineralization was tested in Mitscherlich pot experiments with three treatments: (1) fallow soil without N fertilizer, (2) soil cultivated with rye grass without N fertilizer, (3) soil cultivated with rye grass with N fertilizer. The highest proportion of N in the extracts was the amino N fraction (amino acids + peptides) amounting to approximately 60% of the total N extracted by CaCl₂ and to about 40% of the total N extracted by EUF. The proportion of amino sugars from total N extracted was in average 10% for the CaCl₂ and 5.2% for the EUF extracts. The proportion of heterocyclic N bases derived from nucleic acids amounted in average to 4.8% and 3.6% for the CaCl₂ and EUF extract, respectively. Amino N (amino acids + peptides) were correlated best with net N mineralization (EUF, r = 0.81***, CaCl₂, r = 0.86***). The correlation between amino sugars and net N mineralization was r = 0.55* for the EUF extract and r = 0.49* for the CaCl₂ extract. The heterocyclic N bases did not correlate with net N mineralization. Correlations between Norg extracted by CaCl₂ versus net N mineralization were higher than those obtained by the EUF extract. Net N mineralization was about four times higher in the fallow soils than in the treatment with grass and no N fertilizer. In the treatment with grass + N fertilizer on average no net N mineralization occurred, moreover there was a tendency of N immobilization. It is assumend that in the treatments with grass cultivation, organic C released by roots stimulated the assimilation of mineral N and amino acids by soil microorganisms resulting in a low net N mineralization. Net N mineralization led to a highly significant depletion in the Norg pools and particularly in the amino N and amino sugar pools in the treatment with grass and without N fertilizer. This depletion was particularly evident in the CaCl₂ extracts. The results justify the conclusion that the Norg obtained with both extraction methods originates from a dynamic N pool into which N flows in and out. The amino N extractable with EUF or CaCl₂ is a reliable indicator for the net N mineralization potential of soils.     

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 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.     

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

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

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

A procedure for the determination of soluble boron in soils ranging widely in boron concentrations,sodicity, and pH.

Abstract

Soils in southern Australia within the Mediterranean‐type climate zone vary widely in boron concentrations, from potentially deficient to toxic for plant growth. A general method is needed for the determination of boron in soils ranging from acidic to alkaline, with wide ranges of clay content and sodicity.

The amounts of boron extracted were compared following boiling in 0.01M CaCl₂ in test tubes in temperature‐controlled programmable digestion blocks, or in Erienmeyer flasks on hot plates under different analytical conditions. Comparisons were also made between CaCl₂, hot water, and mannitol extractable boron. All analyses of boron were made by inductively coupled plasma spectrometry (ICPS).

The extraction of boron was dependent on extraction time and temperature of the heating block. Addition of 20 ml of 0.01M CaCl₂ to 10g of soil in 250 ml test tubes fitted with air condensers and placed in a pre‐heated temperature‐controlled digestion block set at 140°C and boiled for 30 minutes. This method was found to be a suitable extractant of boron in soils with a wide range of sodicity, pH and extractable boron (from concentrations potentially deficient to toxic for plant growth).     

Fractionation and colorimetric determination of boron in soils

We attempted to modify and evaluate existing sequential fractionation schemes for B involving the use of chemicals, which subsequently do not interfere with the measurement of B by colorimetry. Also evaluated was the contribution of various soil B fractions to the amount of B extracted by hot CaCl₂, CaCl₂‐mannitol, salicylic acid, ammonium acetate, HCl, and tartaric acid. For this purpose, 17 soils with diverse properties were used. The extraction scheme proposed here partitioned B into five pools, (i) readily soluble, (ii) specifically adsorbed, (iii) oxide bound, (iv) organically bound, and (v) residual boron, respectively extracted with 0.01 M CaCl₂, 0.05 M KH₂PO₄, 0.175 M NH4‐oxalate (pH 3.25), 0.5 M NaOH, and HF + H₂SO₄ + HClO₄. The procedure of elimination of color from extracts of oxide bound, organically bound, and residual B fractions was also evolved. Relationships of individual B fractions with physicochemical properties of the experimental soils confirmed the general validity of the proposed fractionation scheme. The relationships of different B fractions with extractable B in soils suggest that hot CaCl₂ and salicylic acid may be better extractants for available B in soils.     

Effects of heavy metals on the structure and functioning of detritivore communities in a contaminated floodplain area

The aim of this study was to determine the effects of heavy metal pollution on the structure and functioning of detritivore soil communities that consist of isopods, millipedes and earthworms, in 15 heavily polluted flood plain soils, located in the delta area of the rivers Rhine and Meuse, in the Netherlands. The 15 study sites represent a gradient in Zn, Cu and Cd concentrations. The structural attributes of the detritivore community, which were assessed, were the species richness and densities in the field sites. The functioning of the detritivore community was studied by determining organic matter decomposition using litter bags and feeding activity with the bait-lamina method. Concentrations of Cd, Cu and Zn were measured in soil, pore water and 0.01 M CaCl₂ extracts of the soil, in adult earthworms and plant leaves. Results show that metal pollution is not a dominating factor determining the species richness and densities of the selected detritivore groups, although the biomass of the earthworm Lumbricus rubellus was positively and significantly correlated to Zn concentrations in pore water and 0.01 M CaCl₂ extracts. Litter decomposition was significantly and positively correlated to detritivore biomass and 0.01 M CaCl₂ extractable Cd concentrations in soil and negatively to pH-CaCl₂, although the range of pH values was very small. It can be concluded that in spite of high metal levels in the soil, bioavailable concentrations are too low to result in clear negative effects on the structure and functioning of detritivores in the Biesbosch, the Netherlands.     

不同浸提剂以及保存方法对土壤矿质氮测定的影响

为探明影响土壤矿质氮测定的因素,从棕壤、潮土和黄棕壤3种类型土壤中各采集10个经不同施肥处理的土样,用连续流动注射分析仪测定经不同浸提剂以及不同保存方法处理后土样的NO3-N和NH4-N含量。结果表明:不论是棕壤、潮土还是黄棕壤,2 mol.L?1 KCl提取硝态氮的数量与0.01 mol.L?1 CaCl2提取的数量相关性均达到P<0.01水平;3种土壤各个土样硝态氮含量的测定值多表现为新鲜土<冷冻土<风干土;将鲜样浸提后作短时间的冷冻处理,其效果与鲜样24 h内的测定结果较接近;土样不同保存方式以及浸提液的保存时间对3种土壤NH4-N测定结果的影响规律不及NO3-N明显。     

Soil pH,extractable aluminum and tree growth on acid minesoils

Abstract

Paper birch and hybrid poplar were grown in acid minesoils amended with different rates and types of lime. Growth of the trees was correlated with soil pH, Ca, Mg, K, P and three measures of extractable Al ‐ 1 N KCl, 0.01 M CaCl₂ and H₂O extractable Al. Correlations between soil pH and extractable Al and between the three measures of extractable Al were also determined. Soil pH accounted for the largest share of the total variation in root and shoot growth of both species over all soils. Correlations between tree growth and extractable Al for all soils combined were low and generally non‐significant. Significant correlations were obtained between soil pH and extractable Al and between the three measures of extractable Al, however, the relationships varied among soils.     

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 hot‐water‐soluble boron in some acid Oregon soils using a modified azomethine‐H procedure

Abstract

A method is proposed for determination of hot‐water‐soluble boron in acid soils from western Oregon. The soil sample is boiled in 0.02 M CaCl₂, filtered, and B determined using azomethine‐H. Soils extracted in this way yielded extracts with little color in them and the predicted error due to this color was 0.00–0.07 ppm B. The use of charcoal as a decolorizing agent resulted in comparatively high predicted errors.

Inductively‐coupled plasma emission spectroscopic (ICP) analysis of distilled water and 0.02 M CaCl₂ extracts indicated that the extractable B level was not affected by the presence of CaCl₂. Azomethine‐H yielded comparable values to ICP but the curcumin method tended to give high values for hot‐water‐soluble B.     

Influence of residual phosphate fertilizer on labile and extractable zinc in hawaii soils

Abstract

Zinc availability was studied using five soils from Hawaii which had histories of massive phosphorus applications. Heavy phosphate fertilization usually increased extractable Zn, irrespective of the extractant used. The extra extractable Zn associated with the added P probably came from Zn as an accessory element in the fertilizer. Treble superphosphate commonly used in Hawaii contains about 1400 ppm Zn. The Zn content of phosphate fertilizers must be considered before making statements about the effect of fertilizer P on Zn solubility and availability in soils.

Two solutions (0.1N HCl and 0.005M DTPA) were compared as Zn extractants for Hawaii soils. DTPA extracted less Zn than 0.1N HCl. Zinc extracted by repeated HCl treatment was more closely related to the labile Zn pool (E‐values and L‐values) than was DTPA‐extractable Zn. The results suggest that 0.1N HCl extractable Zn, Zn E‐value and Zn L‐value measured the quantity of a single fraction of soil Zn.

Repeated extraction of soil with 0.1N HCl seems to be a suitable procedure for evaluating the Zn status of acid, highly weathered soils of Hawaii.     

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.     

The use of cation activity ratios to estimate the intensity of soil acidity

Soil solution extracts can be relatively difficult to obtain and to handle. The aim of this study was to investigate whether a simple 0.01 M CaCI, extraction could be used to estimate the intensity factor of soil acidity by employing the Schofield Ratio Law. Activity ratios of H, Ca and A1 were compared in soil solutions and in 0.01 M CaCI, extracts on four soils adjusted to a range of pH values with acid and lime. The ratios pH-1/2pCa (0.01 M CaCl₂) and pH-1/2p(Ca + Mg) (soil solution) were not statistically significantly different. The ratio pH-1/3pAl was less strongly correlated, but again was not significantly different between the soil solution and extractant. The Schofield Ratio Law did not hold over the entire range of data for pCa-+2/3pAl, but the values in the two solutions correlated closely. Cation activity ratios in 0.01 M CaCl₂ can be used to estimate the intensity factors of acidity in a soil, even though the extractant has a higher ionic strength than many soil solutions in variable charge soils. Therefore pH and A1 as measured in 0.01 Cacl₂ extracts may be useful tests for routine diagnostic purposes and soil surveys.     

Metal Extractability in Binary and Multi-metals Spiked Calcareous Soils

In the present study, a laboratory experiment was designed to compare the 0.01 M calcium chloride (CaCl₂) and diethylenetriaminepentaacetic acid (DTPA) extraction methods for their ability to predict cadmium (Cd), copper (Cu), iron (Fe), Manganese (Mn), nickel (Ni), and zinc (Zn) availability and mobility in five calcareous soils. The soils were spiked with different amounts of metals (0, 50, 100, 200, and 400 mg kg^?1) both in binary (Cu and Zn; Ni and Cd; Fe and Mn) and in multi-systems (Cd, Cu, Fe, Mn, Ni, and Zn) and incubated for 1 months at field capacity. In metal-spiked soils, both extraction methods showed a linear relationship of extractable to total metals for all soils. The fraction of total metals extracted by DTPA was much higher than the fraction extracted by CaCl₂, which was attributed to the formation of soluble metal-complexes in the complexing extracts calculated by the Visual Minteq program. DTPA extraction method showed higher selectivity for Cu over other metals both in binary and in multi-systems. Different order of metals extractability was found in binary and multi-systems for both extraction methods. Solid/solution distribution coefficient (K_d) was calculated by the ratio of the solid phase to soil solution concentration of metals extracted by CaCl₂ or DTPA extraction methods. Both in binary and in multi-systems, the average K_d (l kg^?1) of metals by soils were in the order of Mn (5398) > Fe (4413) > Zn (3376) > Cu (2520) > Ni (969) > Cd (350) in the CaCl₂-extractable metals and Fe (35) ≥ Ni (34) > Zn (18) > Mn (11.2) > Cu (6.3) > Cd (4) in the DTPA-extractable metals. Results showed that among the six studied metals, Cd had the lowest K_d, implying a relative higher mobility in these calcareous soils. The Visual Minteq indicated that in the CaCl₂-extraction method and in both binary and multi-systems the dominant species for Cu, Mn, Ni, and Zn were Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺, respectively, while for Cd and Fe, the dominant species were CdCl⁺ and Fe(OH)²⁺, respectively.     

Evaluation of Selected Extractants for Plant-Available Silicon in Rice Soils of Southern India

The extractable silicon (Si) using selected extractants irrespective of the soils used for the study was in the order of 0.005 M sulfuric acid (H₂SO₄) > 0.1 M citric acid > N sodium acetate (NaOAc) 2 > N NaOAc 1 > 0.5 M acetic acid 3 > 0.5 M acetic acid 2 > 0.5 M acetic acid 1> 0.01 M calcium chloride (CaCl₂) > 0.5 M ammonium acetate (NH4OAc) > distilled water 4 > distilled water 1. Silicon extraction with N NaOAc 1 appeared to be the most suitable for evaluating Si, followed by extraction with 0.5 M acetic acid 2 and N NaOAc 2. These extractants showed the greatest degree of significant correlation with the percentage of Si in straw and grain, as well as Si uptake by straw and grain. These methods also rapidly extract soil Si in comparison to the other methods and appear to be the most suitable for routine soil testing for plant-available Si in the rice soils of southern India.