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1.
Two previous studies suggested that part of the cation sorption sites in soil organic matter with low exchange capacity have to be considered as “lonely”, i.e., too far from each other to allow direct cross‐linking by bivalent cations. The objective of this contribution was to understand the mechanisms controlling structural rigidity and physicochemical aging of the SOM (soil organic matter) and the role of water molecule bridges (WaMB) therein. For this, we evaluated the matrix rigidity of an organic surface layer of a Haplic Podzol on a quantitative basis, by assessing WaMB transition temperature (T*) directly after treatment with bivalent cations (Mg2+, Ca2+, or Ba2+) and after eight weeks of aging. Cation loading as well as cation type influenced matrix rigidity. Ba2+ induced the most rigid matrix and Mg2+ the weakest, which is in line with their binding strength in terms of Langmuir coefficient. The matrix rigidity increased with the cross‐linking activity, which is the product of loading and Langmuir constant of the respective cation. The aging process, however, was slowed down by the initial matrix rigidity, and the rigidity of the aged matrix decreased with increasing Langmuir constant. The degree of aging increased with increasing hydration enthalpy of the cation and decreased with increasing cation loading. Thus, directly after cation treatment, direct cross‐links by multivalent cations were most relevant, but WaMB increasingly gained influence on the matrix rigidity during aging. The untreated sample revealed a considerable number of WaMB, resulting in a fairly rigid and strongly cross‐linked matrix which, however, flexibly reacts on external influences like change in cation concentration or relative humidity. With these findings, the ideas on the relevance of indirect CaB‐WaMB associations between distant sorption sites for the rigidity and flexibility of the OM matrix as proposed in previous studies were confirmed on a mechanistic basis in this study.  相似文献   

2.
Different types of cation exchange capacity (CEC) and related chemical properties were determined in the main genetic horizons of meadow-chestnut soils in the mesodepressions at the Dzhanybek Research Station of the Institute of Forestry of the Russian Academy of Sciences. In the A horizon, the CEC is mainly due to the organic matter from the clay and coarse fractions, which provides 36% of the soil CEC, and to labile silicates and other clay minerals of the clay fraction. In the Bt horizon, the CEC is mainly provided by the labile minerals of the clay fraction and organic matter of the clay and coarse fractions. The standard soil CEC was found to be significantly higher than the sum of the exchangeable cations in the A horizon and slightly lower than the sum of the exchangeable cations in the Bt and Bca2 horizons. This difference can be related to the fact that the NH4+ ion, which is selectively adsorbed by clay minerals, is used as a displacing cation during the determination of the exchangeable bases, while the Ba2+ ion, which is more selectively adsorbed by organic matter, is used during the determination of the standard CEC. In all the genetic horizons, the experimentally determined value of the standard CEC almost coincides with the CEC value obtained by summing the standard CECs of the different particle-size fractions with account for their contents; hence, this parameter is additive in nature.  相似文献   

3.
We used the specific surface area (SSA), the cation exchange capacity (CEC) and the content of dithionite‐extractable iron (Fed) to predict the content of organic carbon in illitic clay fractions of topsoils from loess. We determined SSA (BET‐N2 method) and CEC of clay fractions after removing organic C or reducing oxides or both. The CEC and the SSA of the carbon‐ and oxide‐free clay fraction explained 56% and 54% of the variation in C content, respectively. The Fed content of the clay fractions was strongly and negatively related to the C content, and with the SSA of the carbon‐free clay fraction it predicted C content almost completely (R2 = 0.96). The results indicate that the amount of cations adhering to the silicate clay minerals and the size of the silicate mineral surface area are important properties of the mineral phase for the storage potential of C. The reason for the negative relation between iron oxides and C content remains unclear.  相似文献   

4.
The determination of the effective cation exchange capacity of rocks The extractable cations (1 N NH4Cl) of broken, mortared, and ground rocks (Sandstone, Clay schist, Diabase, Alkali-Olivinbasalt) were determined using vibration extraction and percolation. These methods were evaluated by re-exchange experiments. In addition mineralogical components, specific surface and effective porosity of the rocks were determined. Al-silicates which are cation exchangers like Illite and Zeolite minerals were found in these rocks. Mortaring and grinding increased the specific surface and the exchange capacity of the rocks which have a low porosity (Clay schist and Basalt). For example, the CEC of broken Clay schist was 27 μmolc g?1 and increased to ≈ 40 μmolc g?1 after mortaring. The CEC of the rocks with a high porosity (Diabase and Sandstone) did not depend on the particle size. Therefore we assume, that inner parts of the broken rocks were reached by extraction. The CEC amounts to ≈ 50–80% of the sum of the cations, which could be extracted with NH4Cl. This difference is probably due to the dissolution of salts. Mortaring and grinding increased the amount of cations derived from dissolving of salts. The results show, that rocks are of signficance not only for silicate weathering, but also for the cation exchange.  相似文献   

5.
Laboratory and greenhouse experiments were conducted to determine the influence of soil properties on adsorption and desorption of boron (B) as well as to estimate the degree of reversibility of adsorption reactions. The utility of Freundlich and Langmuir equations for characterizing the plant availability of applied B in soils was established using soybean [Glycine max (L.) Merr.] as a test crop. The adsorption-desorption study revealed that Fe2O3 and clay were primarily responsible for retaining added B in all the 25 different soils under investigation. Organic carbon, pH and cation exchange capacity (CEC) positively influenced the adsorption of B while free Fe2O3, organic carbon and clay retarded release of B from these soils. The degree of irreversibility (hysteresis) of B adsorption/desorption increased with increase in organic carbon and CEC of these soils. Freundlich isotherm proved more effective in describing B adsorption in soils as compared to Langmuir equation. The split Langmuir isotherm demonstrated that any of the adsorption maxima, calculated from lower, upper or entire isotherm, could be of practical use. Contrary, bonding energy coefficient, calculated either at lower or higher equilibrium concentration failed to show any practical benefit. Regression models as a function of B application rate and adsorption equation parameters to predict B uptake from applied B, demonstrated the utility of Langmuir and Freundlich equation parameters.  相似文献   

6.
Abstract

The adsorption of nutrient elements is one of the most important solid‐ and liquid‐phase interactions determining the retention and release of applied plant nutrients and the efficiency of fertilization. The study showed that the soils with high cation exchange capacity (CEC), CaCO3, organic matter contents, and heavy texture adsorbed more zinc (Zn). The alkaline soils from Pakistan adsorbed more Zn than English acidic soils. Langmuir and Freundlich isotherm fit was excellent, and r2 values for the Langmuir isotherm were highly significant (r2=0.84 to 0.99). The Langmuir b values, representing the adsorptive capacity of a soil, increased as the texture fineness increased in the soil, with increases in the concentration of adsorptive material (such as organic matter and CaCO3) and with increases in CEC and pH. The alkaline soils from Pakistan had higher bonding energy constant and higher log Kf values than the acidic English soils. Sequential extraction of Zn in these soils showed that most of the Zn was held in CaCO3 pool in the alkaline soils, whereas in acidic soils adsorbed Zn was in exchangeable form.  相似文献   

7.
On the determination of exchangeable cations in acid forest soils Different samples from acid forest soils were percolated with large amounts of H2O. Significant amounts of anions, especially sulfate, were found in the percolates mainly accompanied by Na. K, Ca and Mg (Mb-cations). The dissolution of Al-Sulfates and subsequent exchange of Mb-cations by Al as dominant mechanism is proposed. Thus the common method for determination of the cation exchange capacity (CEC) of acid forest soils, the percolation with NH4Cl may overestimate the CEC. The overestimation may be related to the sulfate content of the soil and also influences the calculation of relative CEC proportions of individual cations.  相似文献   

8.
CADMIUM ADSORPTION BY SOILS   总被引：4，自引：0，他引：4  
The Langmuir adsorption equation was found to describe Cd adsorption from dilute solutions at 5°C and 25°C for ten soils from Tuscany. The calculated Langmuir adsorption maxima (Q) and bonding energy coefficients (K) were well correlated with CEC and organic matter content. On the basis of the temperature effect on Q and K, the mechanism of Cd adsorption is discussed.  相似文献   

9.
This study investigated the suitability of mid‐infrared diffuse reflectance Fourier transform (MIR‐DRIFT) spectroscopy, with partial least squares (PLS) regression, for the determination of variations in soil properties typical of Italian Mediterranean off‐shore environments. Pianosa, Elba and Sardinia are typical of islands from this environment, but developed on different geological substrates. Principal components analysis (PCA) showed that spectra could be grouped according to the soil composition of the islands. PLS full cross‐validation of soil property predictions was assessed by the coefficient of determination (R2), the root mean square error of cross‐validation and prediction (RMSECV and RMSEP), the standard error (SECV for cross‐validation and SEP for prediction), and the residual predictive deviation (RPD). Although full cross‐validation appeared to be the most accurate (R2 = 0.95 for organic carbon (OC), 0.96 for inorganic carbon (IC), 0.87 for CEC, 0.72 for pH and 0.74 for clay; RPD = 4.4, 6.0, 2.7, 1.9 and 2.0, respectively), the prediction errors were considered to be optimistic and so alternative calibrations considered to be more similar to ‘true’ predictions were tested. Predictions using individual calibrations from each island were the least efficient, while predictions using calibration selection based on a Euclidian distance ranking method, using as few as 10 samples selected from each island, were almost as accurate as full cross‐validation for OC and IC (R2 = 0.93 for OC and 0.96 for IC; RPD = 3.9 and 4.7, respectively). Prediction accuracy for CEC, pH and clay was less accurate than expected, especially for clay (R2 = 0.73 for CEC, 0.50 for pH and 0.41 for clay; RPD = 1.8, 1.5 and 1.4, respectively). This study confirmed that the DRIFT PLS method was suitable for characterizing important properties for soils typical of islands in a Mediterranean environment and capable of discriminating between the variations in soil properties from different parent materials.  相似文献   

10.
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.  相似文献   

11.
Comparison between percolation and extraction with 1 M NH4Cl solution to determine the effective cation exchange capacity (CECeff) of soils A simple method is proposed for the determination of the effective cation exchange capacity (CECeff). 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 CECeff.  相似文献   

12.

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.  相似文献   

13.
胡敏酸对铵钾在粘土矿物上交互作用的影响   总被引：1，自引：0，他引：1  
Interaction of ammonium (NH+4) and potassium (K+) is typical in field soils. However, the effects of organic matter on interaction of NH+4 and K+have not been thoroughly investigated. In this study, we examined the changes in major physicochemical properties of three clay minerals (kaolinite, illite, and montmorillonite) after humic acid (HA) coating and evaluated the influences of these changes on the interaction of NH+4 and K+on clay minerals using batch experiments. After HA coating, the cation exchange capacity (CEC) and specific surface area (SSA) of montmorillonite decreased significantly, while little decrease in CEC and SSA occurred in illite and only a slight increase in CEC was found in kaolinite. Humic acid coating significantly increased cation adsorption and preference for NH+4, and this effect was more obvious on clay minerals with a lower CEC. Results of Fourier transform infrared spectrometry analysis showed that HA coating promoted the formation of H-bonds between the adsorbed NH+4 and the organo-mineral complexes. HA coating increased cation fixation capacity on montmorillonite and kaolinite, but the opposite occurred on illite. In addition, HA coating increased the competitiveness of NH+4 on fixation sites. These results showed that HA coating affected both the nature of clay mineral surfaces and the reactions of NH+4 and K+with clay minerals, which might influence the availability of nutrient cations to plants in field soils amended with organic matter.  相似文献   

14.
Abstract

In soil samples from two study sites in southern Norway, exchangeable cations were determined using two different ammonium (NH4)‐salts as extractant. As expected, the cation exchange capacity (CEC) determined in 1M ammonium acetate (NH4OAc), buffered at pH 7.0 was higher than the CEC measured in ammonium nitrate (NH4NO3). By contrast, the amount of exchangeable calcium (Ca), magnesium (Mg), and barium (Ba) was lowest in the NH4OAc extract, in particular in the upper soil horizons high in organic matter (O‐ and E‐horizon). This suggests that NH4 in 1M NH4OAc does not compete effectively with multivalent base cations. The relatively high levels of exchangeable base cations in NH4NO3 could not be explained by increased weathering. An increase in selectivity of especially divalent cations may explain the relatively low amount of exchangeable base cations extracted by NH4OAc, as this involves increased deprotonation and thus a higher negative charge.  相似文献   

15.
Abstract

Soil cation exchange capacity (CEC) measurements are important criteria for soil fertility management, vaste disposal on soils, and soil taxonomy. The objective of this research was to compare CEC values for arable Ultisols from the humid region of the United States as determined by procedures varying widely in their chemical conditions during measurement. Exchangeable cation quantities determined in the course of two of the CEC procedures were also evaluated. The six procedures evaluated were: (1) summation of N NH4OAc (pH 7.0) exchangeable Ca, Mg, K, and Na plus BaCl2 ‐ TEA (pH 8.0) exchangeable acidity; (2) N Ca(OAc)2 (pH 7.0) saturation with Mg(OAc)2 (pH 7.0) displacement of Ca2+; (3) N NH4OAc (pH 7.0) saturation with NaCl displacement of NH4 +; (4) N MgCl2 saturation with N KCl displacement of Mg2+; (5) compulsive exchange of Mg2+ for Ba2+; and (6) summation of N NH4OAc (pH 7.0) exchangeable Ca, Mg, K, and Na plus N KCl exchangeable AJ. The unbuffered procedures reflect the pH dependent CEC component to a greater degree than the buffered methods. The compulsive exchange and the summation of N NH4OAc exchangeable cations plus N KCl exchangeable Al procedures gave CEC estimates of the same magnitude that reflect differences in soil pH and texture. The buffered procedures, particularly the summation of N NH4OAc exchangeable cations plus BaCl2 ‐ TEA (pH 8.0) exchangeable acidity, indicated inflated CEC values for these acid Ultisols that are seldom limed above pH 6.5. Exchangeable soil Ca and Mg levels determined from extraction with 0.1 M BaCl2 were consistently greater than values for the N NH4Oac (pH 7.0) extractions. The Ba2+ ion is apparently a more efficient displacing agent than the NH4 + ion. Also, the potential for dissolving unreacted limestone is greater for the Ba2 + procedures than in the NH4 + extraction.  相似文献   

16.
Soils of the humid tropics are poor in available potassium due to intensive weathering and leaching of nutrients. A study was conducted to investigate the mineralogy and potassium supplying capacity of a forest soil developed on a weathered schist regolith. The quantity–intensity (Q/I) approach was used in thisstudy. The schist regolith showed deep weathering and intense leaching throughout the profile, resulting in low cation exchange capacity (CEC) and available K in soil and saprolite layers. The mineralogy of the regolith was dominanted by kaolinite, gibbsite and goethite. Feldspar, mica and mica–smectite minerals were observed in the lower saprolite layers. The Q/I parameters showed that the soils and saprolites were low in K supply power. This observation was attributed to weathering and intense leaching. The free energy values of K replacement (ΔG r°) also suggest that soils and saprolites of the schist regolith were deficient in K. The Q/I parameters significantly correlated with organic carbon and clay content, CEC, pH and exchangeable K.  相似文献   

17.
Knowledge of phosphorus(P) sorption dynamics across different soil types could direct agronomic and environmental management of P. The objective of this study was to predict P isotherm parameters for a national soil population using data of routine laboratory tests. Langmuir and Freundlich sorption parameters were calculated from two different ranges(0–25 and 0–50 mg P L~(-1)) using an archive of representative agricultural soil types from Ireland.Multiple linear regression(MLR) identified labile forms of aluminium(Al) and iron(Fe), organic matter(OM), cation exchange capacity(CEC), and clay as significant drivers. Langmuir and Freundlich sorption capacities, Freundlich affinity constant, and Langmuir buffer capacity were predicted reliably, with R~2 of independent validation 0.9. Sorption isotherm parameters were predicted from P sorbed at a single concentration of 50 mg P L~(-1)(S_(50)). An MLR prediction of P sorption maximum in the 0–50 mg P L~(-1) range was achieved, to an accurate standard, using S_(50), OM, and Mehlich-3 Fe(R~2 of independent calibration and validation being 0.91 and 0.95, respectively). Using Giles' four shapes of isotherms(C, L, H, and S), L non-strict-and C-shaped isotherm curves accounted for 64% and 27% of the soils, respectively. Hierarchical clustering identified a separation of isotherm curves influenced by two ranges of Mehlich-3 Al. Soils with a low range of Mehlich-3 Al(2.5–698 mg kg~(-1)) had no incidence of rapid sorption(C shape). Single point indices, Al, or available soil data make the regression approach a feasible way of predicting Langmuir parameters that could be included with standard agronomic soil P testing.  相似文献   

18.
通过盆栽试验研究了施用动物粪便、动物残体、草本残体、木本残体4种不同有机物料对黑土胶体及黑土阳离子交换量(CEC)的影响。结果表明:不同来源有机物料对黑土胶体及黑土CEC的影响存在差异。与CK相比,动物粪便处理下黑土胶体比表面降低7.33%,而动物残体处理下提高了59.58%,木本残体提高了57.46%,草本残体提高了100.18%。pH<6时,各处理土壤胶体表面可变电荷量(Q表面)的曲线大致相似;在pH>6时,各有机处理土壤胶体样的表面电荷(Q样)均高于CK,并且动物粪便与木本残体的Q表面曲线相似且数值较高,CK与动物残体Q表面的曲线大致相同且数值较低。在pH为8～10时,各处理Q样由大到小依次为:动物粪便>木本残体>动物残体>草本残体>CK,动物粪便土壤胶体参比的表面电荷(Q参)与动物残体Q参的曲线大致相同并且数值较高,CK与草本残体Q参曲线相似且数值较低。不同来源有机物料对黑土CEC的影响也有所不同,动物粪便、动物残体、木本残体显著提高黑土CEC,而草本残体作用不明显。  相似文献   

19.
The aim of this study was to provide knowledge of the prediction efficiency of two pedotransfer functions for soil cation‐exchange capacity (CEC), i.e., the approaches of Krogh et al. (2000) and Scheinost (1995). Potential CEC, i.e., CEC at pH 8.1, was predicted for 30 samples of German soils showing a strong variation of soil organic C and clay content which are important soil characteristics for CEC. The results were compared to analyzed potential CEC of the samples by coefficient‐of‐efficiency (EC) criterion of Nash and Sutcliffe (1970). Significant deviations between observed and measured CEC were found for both functions. The approach of Scheinost (1995) showed a higher prediction efficiency (EC = 0.77 in comparison to EC = 0.26 for Krogh et al., 2000) and better results under extrapolative conditions.  相似文献   

20.
A humic lake of pH 5.6 was acidified with H2SO4 to pH 4.1. Measurements of total and hollow-fiber ultrafiltered samples were made after three different times of storage, before and after the acid treatment. The nominal molecular weight cutoff of the hollow-fiber membrane was 10 kDalton. Assuming a linear molecular weight distribution of the organic complexes present in solution, the average organic molecule had an average molecular weight of 12.8?08 kDalton (n=6). Not only Ca2+ and Mg2+, but also detectable amounts of Na+ and K+ was found to be present on high molecular weight forms. No significant change in the molecular weight distribution of these elements were observed after the pH decrease. Changes in the molecular weight distribution after the acid treatment were only observed for Fe and Al. Significant amounts of SO4 2? were present on high molecular weight forms. A small, but significant increase in the relative amounts of SO4 2? present on high molecular weight forms was observed after the pH lowering. Kinetic constraints were demonstrated for dissolution of Al and Fe. To some extent, kinetic constraints in the equilibrium distribution of cation/anion exchange reactions of Al, Fe, and SO4 2? were also observed. After the acid treatment, the cation exchange capacity (CEC) of the organic pool present was estimated to be at least 18.2±1.4 (n=3) μeq of positive charges per mg C, probably because the negative sites on the organic pool are either not totally protonated or occupied by other cations at pH 4.09. This CEC is of the same order as industrially made cation exchange resins.  相似文献   

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