Vergleich zwischen Perkolation und Extraktion mit 1 M NH4Cl‐Lösung zur Bestimmung der effektiven Kationenaustauschkapazität (KAKeff) von Böden

Comparison between percolation and extraction with 1 M NH₄Cl solution to determine the effective cation exchange capacity (CEC_eff) of soils A simple method is proposed for the determination of the effective cation exchange capacity (CEC_eff). The soil is extracted with 1 M NH₄Cl‐solution, manually shaken for three times, and the exchangeable cations are determined by ICP‐OES and pH‐measurement. Comparison with corresponding results of the percolation method (n = 110 samples) shows good agreement in reproducibility, exchangeable cations (except Fe and Na), base saturation and CEC_eff.     

Examination into the Accuracy of Exchangeable Cation Measurement in Saline Soils

Abstract

Despite the increasing prevalence of salinity worldwide, the measurement of exchangeable cation concentrations in saline soils remains problematic. Two soil types (Mollisol and Vertisol) were equilibrated with a range of sodium adsorption ratio (SAR) solutions at various ionic strengths. The concentrations of exchangeable cations were then determined using several different types of methods, and the measured exchangeable cation concentrations were compared to reference values. At low ionic strength (low salinity), the concentration of exchangeable cations can be accurately estimated from the total soil extractable cations. In saline soils, however, the presence of soluble salts in the soil solution precludes the use of this method. Leaching of the soil with a prewash solution (such as alcohol) was found to effectively remove the soluble salts from the soil, thus allowing the accurate measurement of the effective cation exchange capacity (ECEC). However, the dilution associated with this prewashing increased the exchangeable calcium (Ca) concentrations while simultaneously decreasing exchangeable sodium (Na). In contrast, when calculated as the difference between the total extractable cations and the soil solution cations, good correlations were found between the calculated exchangeable cation concentrations and the reference values for both Na (Mollisol: y=0.873x and Vertisol: y=0.960x) and Ca (Mollisol: y=0.901x and Vertisol: y=1.05x). Therefore, for soils with a soil solution ionic strength greater than 50 mM (electrical conductivity of 4 dS/m) (in which exchangeable cation concentrations are overestimated by the assumption they can be estimated as the total extractable cations), concentrations can be calculated as the difference between total extractable cations and soluble cations.     

Preparation of Ammonium‐15N and Nitrate‐15N Samples by Microdiffusion for Isotope Ratio Analysis by Optical Emission Spectrometry

Abstract

A diffusion method for the preparation and measurement of ¹⁵N abundance of ammonium and nitrate in KCl extracts of soil using optical emission spectrometry (OES) was compared with conventional continuous flow isotope ratio mass spectrometry (IRMS). There were highly significant correlations between the values obtained by using OES and IRMS. The 99% confidence interval of the intercept included the value 0 and the 99% confidence interval of the slope included the value 1 for both nitrate and ammonium measurements, suggesting that the results from the two methods did not differ significantly. In another experiment, ¹⁵N values of nitrate and ammonium from soil extracts prepared by using the standard distillation procedures for OES were compared against the microdiffusion preparation method. Again, there was a highly significant correlation between the values: the 95% confidence interval of the intercept included the value 0, and the 95% confidence interval of the slope included the value 1, again suggesting that the two methods did not differ significantly. It was concluded that the diffusion technique is an appropriate and simple method of sample preparation for inorganic N analysis of KCl extracts using OES.     

Development of a methodology for calcium, iron, potassium, magnesium, manganese, and zinc quantification in teas using X-ray spectroscopy and multivariate calibration

In this study an analytical methodology for food analyses combining X-ray spectroscopy (XRS) with partial least-squares (PLS) data treatment was developed. Fifteen tea samples were purchased at a local market, and XRS spectra were obtained without sample pretreatment. For comparison of the metal concentrations, the samples were also mineralized, and six elements were determined using flame atomic absorption spectrometry (Ca, Fe, Mg, and Mn), flame atomic emission spectrometry (K), and thermospray flame furnace atomic absorption spectrometry (Zn). The spectral information obtained from XRS and the metal concentrations found using the alternative techniques were employed to generate six PLS models. The Ca and Mn models required four latent variables (LV), Fe, five LV, K, two LV, and Mg and Zn, three LV. The limits of quantification for these models were 614, 134, 761, 140, 85, and 1 mg kg(-1) for Ca, Fe, K, Mg, Mn, and Zn, respectively.     

A Rapid and Simple Manifold to Study Exchangeable Cations and Cation Exchange Capacity in 24 Soil Samples Simultaneously

ABSTRACT

The outcomes of this work highlight the development and validation of a rapid and simple manifold for determination of exchangeable cations [calcium (Ca), magnesium (Mg), sodium (Na), and potassium (K)] and cation exchange capacity (CEC) in soil. First, the performance of the manifold was evaluated to determine the best conditions to use: filter assembly, volume and number of aliquots of extracting solution, and the use of vacuum. Second, the analytical performance was study from trueness and precision analysis. For that, soil samples with assigned values, an in house reference material and unknown soil samples, were used, comparing their results with those obtained using the classical extraction method (agitation, centrifugation, and filtration). The performance study showed that a filter system assembled with S&S Nº859 type filter paper, cotton, and plastic piece is better to the other studied options. Four aliquots of 10 mL extracting solution and a few seconds of vacuum between additions is recommended to achieve the best recovery. The extraction procedure proposed using the manifold demonstrated to be accurate, and so can effectively replace the classical method for the extraction of exchangeable cations and CEC in soils. Regarding simplicity, rapidity, and simultaneity, the manifold method could be the method of choice for extraction up to 24 samples. Moreover, the manifold method significantly reduces the laboratory supplies and instrument used in the extraction steps in the classical method, attaining better efficiency and reducing costs associated to this stage of the analysis.     

武陵山地植烟土壤酸度特征及影响因素——以湖南省湘西自治州为例

为了解多年种植烤烟的山地土壤酸度特征,研究了湘西自治州的土壤酸度指标特征及其关系以及植烟年限和土壤类型、有机质、黏粒对土壤酸度的影响。结果表明:(1)植烟年限对土壤酸度的影响大于土壤类型;随植烟年限增加,土壤pH下降,潜性酸度增加,黄棕壤土的交换性盐基、阳离子交换量和盐基饱和度下降。(2)土壤pH与交换性酸为幂函数关系,交换性铝是土壤交换性酸的主体,土壤交换性酸强度随交换性铝及其相对比例的增加而增加。(3)土壤pH与交换性盐基、阳离子交换量、盐基饱和度为二次曲线关系,当pH6时,随土壤pH增加,交换性盐基和阳离子交换量下降,盐基饱和度增加;当pH6时,随土壤pH增加,交换性盐基和阳离子交换量增加,盐基饱和度变幅小。(4)土壤交换性盐基离子主要是交换性钙,其次是交换性镁;对土壤pH影响较大的盐基离子是交换性钙。(5)有机质和黏粒主要影响土壤pH、阳离子交换量、交换性盐基和交换性钙。     

Laboratory analytical methods for the determination of the hydrocarbon status of soils (a review)

Laboratory analytical methods suitable for the determination of the hydrocarbon status of soils (a specific soil characteristic involving information on the total content and qualitative features of soluble (bitumoid) carbonaceous substances and individual hydrocarbons (polycyclic aromatic hydrocarbons, alkanes, etc.) in bitumoid, as well as the composition and content of hydrocarbon gases) have been considered. Among different physicochemical methods of study, attention is focused on the methods suitable for the wide use. Luminescence-bituminological analysis, low-temperature spectrofluorimetry (Shpolskii spectroscopy), infrared (IR) spectroscopy, gas chromatography, chromatography–mass spectrometry, and some other methods have been characterized, as well as sample preparation features. Advantages and limitations of each of these methods are described; their efficiency, instrumental complexity, analysis duration, and accuracy are assessed.     

Rapid Determination of Mercury in Contaminated Soil and Plant Samples Using Portable Mercury Direct Analyzer without Sample Preparation, a Comparative Study

The objective of this study was to determine the efficiency of a portable total mercury analyzer (OhioLumex RA-915+) in comparison with traditional analytical methods, such as inductively coupled plasma atomic emission spectrometry and cold vapor atomic absorption. The quick mercury analytical procedure with the direct mercury analyzer without sample pretreatment (such as sample digestion) was optimized for a variety of environmental samples, including contaminated soil and plant samples. The efficiency was evaluated using practical parameters, such as time required for analysis, sample amount, mercury species, accuracy, and precision/reproducibility, as well as using statistical analysis. Our results demonstrate that these three instrumental methods yielded similar mercury concentration values and statistical data, while the mercury direct analyzer had the advantages of not requiring for sample digestion and only requiring a small quantity of samples for distribution of mercury in a single root, a single root hair, and sub-regions of a single leaf of plants. These factors are used to justify use of the portable direct mercury analyzer under field conditions and validation of the results.     

Decrease in Hydraulic Conductivity of Clay Soils with Salinity-Sodicity Problems due to Freezing and Thawing Effect

Abstract

Synergism and antagonism cause interactions between plant nutrients. The sum of equivalents of cations in a soil solution is equal to the sum of soluble anions. Therefore, the amount of cations in a soil solution is maintained by a synergetic effect of anions. The relations between cations are determined by the relation between the exchangeable cations, according to a derived Gapon equation. An over-optimal concentration of a cation acts antagonistically to the effect of other cations on plant nutrient uptake. Sometimes the soil solution reactions are complicated, and antagonism between anions becomes obvious.

When describing interactions between plant nutrients by synergism and antagonism, it is valuable to develop analytical methods to determine activities and concentrations in defined extracts of soils. The theory and procedure are described in this paper.     

Comparison of extractants for the determination of available phosphorus,potassium, calcium,magnesium and sodium in some Ethiopian and German soils

Abstract

A study was conducted with the purpose of comparing the efficiency of Mehlich 1, Mehlich 3, and calcium acetate lactate (CAL) extractants for the deter‐ mination of available phosphorus (P) and exchangeable cations [potassium (K), calcium (Ca), magnesium (Mg), and sodium (Na)] on 22 Ethiopian and 10 German agricultural soils. The Olsen and NH₄OAc extractants were used as standards against which P and exchangeable cations values were compared. Results showed that, in general, highly significant correlations were found between all of the methods for available P and exchangeable cations determination on the Ethiopian soils. The highest correlation was, however, found with the Mehlich 3 extractant. On the ten soils from Germany, the Olsen method did not give significant cor‐ relation with the CAL method for P determination. The CAL and Mehlich 3 extrac‐ tants were also not good indicators of Na availability when compared with the NH₄OAc method. It can be generalized that the Mehlich 3 is a suitable extractant for P, K, Ca, Mg, and Na in Ethiopian soils, but further study is recommended to confirm these findings under field conditions.     

Effect of cultivation on physical and chemical properties of a Vertisol in middle Awash Valley,Ethiopia

Abstract

An investigation was conducted to study physical and chemical change at two adjacent soil sites, one used for irrigated cotton since 1972 (cultivated) and the other for traditional grazing and browsing (uncultivated). The soil at each site, a clayey Vertisol was described and sampled for physical and chemical analyses. The result showed that the surface layer of the uncultivated soil was denser and more compact than that of the cultivated soil. Soil porosity and moisture build‐up were lower in the uncultivated than in the cultivated soil. Due to percolation of irrigation water and leaching of soluble salts, salinity, concentration of soluble cations, anions, and exchangeable cations were slightly higher at the lower soil depths in the cultivated than in the uncultivated soil. The exchangeable sodium percentage (ESP) also followed the same trend. Correlation coefficient between the values of electrical conductivity, soluble and exchangeable cations, sodium adsorption ratio (SAR), and ESP were more significant for the cultivated than for the uncultivated soil. Cultivation has reduced organic matter levels by 15%.     

三峡库区2种土地利用方式下土壤盐基离子及碳氮含量对氮添加的响应

为探究三峡库区2种土地利用方式下土壤交换性盐基离子及土壤碳氮含量对氮添加的响应,以湖北省秭归县的林地和果园土壤为研究对象,进行室内土柱淋溶模拟试验,研究4种不同氮添加量(0,50,120,200 kg/(hm²·a))下,土壤中交换性Ca²⁺、Mg²⁺、Na⁺、K⁺以及NO₃^--N、DOC的变化。结果表明：随着氮添加量的增加,林地土壤中的交换性盐基离子淋失量显著增加(p<0.05),而果园土壤中的交换性盐基离子淋失量无显著变化,且林地土壤中交换性盐基离子淋失总量与各盐基离子淋失量均高于果园土壤;经N1、N2、N3处理后,与对照组(N0)相比,林地土壤中的交换性盐基离子淋失总量分别增加1.78%,4.45%,8.49%,且NO₃^--N淋失量分别增加89.21%,77.73%,157.25%,说明氮添加通过加剧土壤中NO₃^--N的淋失带走土壤中交...     

Ammonium nitrate as extractant for soil exchangeable cations,exchangeable acidity and aluminum

Abstract

NH₄NO₃ (1 M) has been used as an extractant for soil exchangeable cations, exchangeable acidity and aluminum. The results obtained using NH₄NO₃ were identical to those using KC1 and NH₄Cl as extractants for the purpose of evaluating soil chemical status. The NH₄NO₃ extraction has practical analytical advantages.     

Comparison of five methods to determine the cation exchange capacity of soil

Background

Cation exchange capacity (CEC) is a routinely measured soil fertility indicator. The standard NH₄OAc (pH 7) extraction procedure is time-consuming and overestimates actual CEC values of variable charge soils. Unbuffered extractants have been developed to measure the effective CEC (eCEC), but they differ in the type of index cation and extraction procedures.

Aim

This study was set up to systematically compare CEC values and exchangeable cation concentrations among different procedures and evaluate their practical aspects.

Methods

Five procedures were compared for (e)CEC, that is, silver thiourea (AgTU), cobalt(III) hexamine (Cohex), compulsive exchange (CE, i.e., BaCl₂/MgSO₄), BaCl₂ (sum of cations in single-extract), and NH₄OAc (pH 7). We applied these methods to a set of 25 samples of clay minerals, peat, or samples from soils with contrasting properties.

Results

The CEC values correlated well among methods (R² = 0.92–0.98). Median ratios of eCEC (AgTU as well as CE) to the corresponding eCEC (Cohex) value were 1.0, showing good agreement between eCEC methods, but NH₄OAc exceeded Cohex values (ratios up to 2.5 in acid soil). For BaCl₂-extracteable cations, the ratio ranged from low (<1.0) in acid soils (acid cations not measured) to high (>1.0) in high-pH soil (dissolution of carbonates). Multiple-extraction methods (CE and NH₄OAc) yielded more variation and increased labor.

Conclusions

The chemical properties of the sample cause method-specific interactions with chemical components of extractants. We found the Cohex method with ICP-MS detection to be the most efficient and cost-effective technique for determination of eCEC and exchangeable cations.     

A rapid method to determine cation exchange capacity and exchangeable bases in calcareous,gypsiferous, saline and sodic soils

Summary

A simple, single‐step extraction with LiEDTA for the estimation of CEC and exchangeable bases in soils has been developed. Multivalent cations are stripped from the soil adsorption sites by the strongly chelating agent EDTA, and are replaced by Li. In soils without CaCO₃ or water soluble salts, exchangeable divalent cations (Ca, Mg) are chelated by EDTA and exchangeable monovalent cations (Na, K) are replaced in a single extraction step using 0.25–2.5 g of soil and 10.0 ml of extractant.

In calcareous soils the CEC can be determined in the same way, but for the extraction of exchangeable Ca and Mg, another separate extraction is needed because dissolution of calcite by EDTA is unavoidable. This extraction is done with as much NaEDTA as needed to extract only exchangeable Ca and Mg in a 1:2 (m/V) soil/alkaline‐50% (V/V) aethanolic solution to minimize dissolution of calcite.

In gypsiferous soils gypsum is transformed into insoluble BaSO₄ and soluble CaEDTA by LiBaEDTA thus avoiding interference of Ca from dissolution of gypsum, which renders the traditional methods for determining CEC unsuitable for such soils. To determine exchangeable Ca and Mg, Na₄EDTA is used as for calcareous soils.

In saline/sodic soils replacement of Na by Li is incomplete but the Na/Li‐ratio at the complex after extraction is proportional to the molar Na/Li‐ratio in the extracts, so that the CEC and original exchangeable sodium (ESP) content can be calculated. Additional analysis of Cl and, if necessary, SO₄ in the extracts of saline soils can be used to correct for the effect of dissolution of the salts on the sum of exchangeable cations.

This new method is as convenient as the recently developed AgTU (silverthiourea), but is better suitable for calcareous and gypsiferous soils.     

Development of Analytical Procedure for the Determination of Exchangeable Cr(VI) in Soils by Anion-exchange Fast Protein Liquid Chromatography with Electrothermal Atomic Absorption Spectrometry Detection

Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄–K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l^?1), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l^?1 and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g^?1 of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g^?1.     

Exchangeable cations and CEC determinations of some highly weathered soils

Abstract

Eight methods to determine exchangeable cations and cation exchange capacity (CEC) were compared for some highly weathered benchmark soils of Alabama. The methods were: (1) 1N NH₄OAc at pH 7.0 by replacement (for CEC only), (2) 1N NH₄OAc at pH 7.0 (summation of basic cations plus 1N KCl extractable Al), (3) 1N NH₄OAc at pH 7.0 (summation of basic cations plus exchangeable H⁺), (4) 0.1M BaCl₂ (summation of basic cations plus exchangeable Mn, Fe and Al), (5) Mehlich 1 (summation of basic cations plus 1N KCl extractable Al), (6) Mehlich 1 (summation of basic cations plus exchangeable H⁺), (7) Mehlich 3 (summation of basic cations plus 1N KCl extractable Al), and (8) Mehlich 3 (summation of basic cations plus exchangeable H⁺). The 0.1M BaCl₂ was chosen as the standard method for the highly weathered soils and the other methods compared to it. The results indicated that the 1N NH₄OAc replacement method gave significantly higher CEC values compared to the summation methods. This was probably due to the overestimation of the field CEC caused by measurement of pH dependent cation exchange sites in these soils. There was, however, close agreement between the BaCl₂ method and the summation methods that included extractable Al. The generally good agreement between these summation methods suggests that the Mehlich 1 and Mehlich 3 extractants, commonly used to determine available nutrients in the southeastem USA, may also be used to measure effective CEC of some acid‐rich sesquioxide benchmark soils of Alabama. However, 1N KCl extractable Al as opposed to exchangeable H⁺ should be included in the computation.     

Relative role of soil nutrients vs. carbon availability on soil carbon mineralization in grassland receiving long-term N addition

High nitrogen (N) input often induces soil carbon (C) limitation, eutrophication of macronutrients, deficiency of base cations, and accumulation of toxic micronutrients. These changes are perceived to be critical factors in regulating soil C mineralization. Previous studies primarily focused on the individual effects of C, macronutrients, exchangeable base cations, and micronutrients on soil C mineralization. However, the relative importance of those factors in regulating soil C mineralization, especially in N-enriched ecosystems, remains unclear. To disentangle the relative contributions of aforementioned factors, lime and/or glucose were added to soils that were collected from a field experiment with historical N addition (6 years) at seven rates (0–50 g N m⁻² year⁻¹) in a grassland ecosystem. Lime and glucose were added to improve the soil C and key nutrient conditions. The responses of soil C mineralization rate to changes in soil C and macronutrients (N and P), exchangeable base cations (K⁺, Na⁺ and Mg²⁺), and micronutrients (Fe²⁺, Mn²⁺, Cu²⁺ and Zn²⁺) were examined. We found that lime addition decreased soil micronutrients, while glucose addition improved the soil available P and exchangeable base cations, especially at high historical N addition rates. The soil C mineralization was weakly associated with changes in soil nutrients, including the availability of N, P, exchangeable base cations, and micronutrients, which were conventionally and previously considered as the vital drivers of soil C mineralization. However, soil C mineralization strongly increased with glucose-induced enhancement of C availability and the subsequent enhancement of microbial biomass under increasing N addition rates. Based on the Structural Equation Model, the standardized total effects of C, macronutrients (N and P), base cations and micronutrients on soil C mineralization were 0.86, − 0.29, 0.15 and − 0.08, respectively. Findings from this study demonstrated that the N-induced significant changes in soil nutrients (e.g., eutrophication of N and P, base cations deficiency and accumulation of toxic macronutrients) mediated soil C mineralization, with C availability being the most critical driver for C mineralization in N-enriched soil. This study provides insight into the mechanistic understanding of the relationship between N input and terrestrial C cycling.     

A computer‐assisted method for CEC estimation and quality control in a routine soil‐test operation

Abstract

Cation‐exchange capacity (CEC) of 30 Alabama soils was estimated by two different methods based or routine soil‐test results consisting of soil‐water pH, Adams‐Evans buffer pH, and Mehlich‐1 extractable cations (K, Mg, and Ca), which were obtained automatically by a computerized data acquisition system. In one method, CEC was calculated by solving a quadratic equation involving soil‐water and buffer pH's; in the other, CEC was estimated as the summation of extractable cations and exchangeable acidity. The two estimated CEC's agreed well with each other and also had the same magnitude as CEC determined by the normal NaOAc, pH 8.2 method. By averaging the two calculated values, an even closer estimation of the measured CEC was found. These calculations and comparisons can be accomplished quickly and efficiently by a minicomputer via a simple FORTRAN program.

In addition, a discrepancy between the two estimated CEC's would indicate possible errors in analytical determinations and/or the inadequacy of the soil testing procedures. Therefore, an additional means for quality control in a routine soil‐test operation can be obtained by comparing the two CEC values.     

Relationship between water soluble and exchangeable soil cations for estimating plant uptake and leaching potential

Abstract

The relationship between water soluble and exchangeable cations (Ca, Mg, Na, and K) was investigated for surface horizons of 195 soils including many taxonomic categories and a wide range in physical and chemical properties from around the world. This will provide information on exchangeable soil cation solubility for use in estimating plant uptake and leaching potential. Amounts of water soluble and exchangeable cations were not consistently related (r² of 0.50, 0.08, 0.77, and 0.49 for Ca, Mg, Na, and K). High correlations were biased by high water soluble and exchangeable cation levels of a few soils that had 3.8‐ and 2.5‐fold greater mean than median values. The ratio of exchangeable to water soluble cations was closely related to cation saturation (r² of 0.87, 0.95, 0.95, and 0.93 for Ca, Mg, Na, and K, respectively). As the degree of saturation of the exchange complex by a certain cation increased, solubility Increased. A change in saturation had less effect on K than on Na, Mg, and Ca solubility. Only exchangeable soil cations (NH₄OAc extractable) are routinely measured and reported in soil survey reports, thus, water soluble levels may be determined from cation saturation. This will allow estimation of the amounts of cation that can potentially move in solution through the soil or be taken up by plants. Use of cation saturation, in addition to exchangeable content, will better characterize soil cation availability by representing quantity, intensity, and buffer factors.