Zinc sorption–desorption by sand,silt and clay fractions in calcareous soils of Iran

Zinc sorption–desorption by sand, silt and clay fractions of six representative calcareous soils of Iran were measured. Sand, silt and clay particles were fractionated after dispersion of soils with an ultrasonic probe. Zinc sorption analysis was performed by adding eight rates of Zn from 6 to 120 μmol g^?1. For the desorption experiment, samples retained after the measurement of Zn sorption were resuspended sequentially in 0.01 M NaNO₃ solution and shaken for 24 h. Results indicated that Zn sorption by soil fractions increased in the order clay > silt > sand, and correlated negatively with CaCO₃ content and positively with cation exchange capacity (CEC) and smectite content. Results indicated that for all fractions, the Langmuir equation described the sorption rates fairly well. In contrast to sorption, Zn desorption from soil fractions increased in the order sand > silt > clay, and correlated positively with CaCO₃ content, CEC and smectite content. Results showed that parabolic diffusion and two constant equations adequately described the reaction rates of Zn desorption. In general, for all soils studied, the coarser the particle size, the less Zn sorption and more Zn desorption, and this reflects much higher risk of Zn leaching into groundwater or plant uptake in contaminated soils.     

SPECIFIC EFFECT OF MAGNESIUM ON THE HYDRAULIC CONDUCTIVITY OF SODIC SOILS

Exchangeable Mg does not have a specific effect on the hydraulic conductivity (HC) and clay dispersion in calcareous soils. Conversely, in well-weathered soils, which do not contain CaCO₃, a specific effect of exchangeable Mg is evident, on both HC losses and clay dispersion, when the Na/Mg soils are leached with distilled water (simulating rain water). Soil clays, when Mg-saturated, are chemically more stable and do not release electrolytes into the solutions: they thus disperse more easily when leached with distilled water. The presence of exchangeable Mg enhances the dissolution of CaCO₃ in calcareous soils, and the electrolytes prevent the dispersion of the clay and HC losses in the Na/Mg calcareous soils.     

Phosphorus sorption and availability indices as affected by properties of calcareous soils

Abstract

The Olsen solution is usually considered the best extractant for estimating P availability in calcareous soils, but predictability of the response to P fertilizers is often low under field conditions. In this study, soil characteristics influencing P sorption and extractability were evaluated. Forty‐one soils varying in CaCO₃, pH, and clay content were selected from pastures to minimize the effect of recent P additions. A P sorption index (PSI) determined from a single addition of 150 mg P/100 g soil was related to soil Ca and CaCO₃, but the correlation coefficients were rather low (r = 0.46 and 0.38, respectively). A P availability index (PAI), determined from the increase in extractable soil P after adding 50 mg P/kg to a suspension and allowing it to dry, was correlated quite well with cation exchange capacity and clay content (r = ‐0.61 for each) in soils with pH < 8.8. The PAI also had a positive relationship with the density of the processed soil sample (r = 0.60). The relationship between PAI and soil Ca (r = ‐0.51) was also better than that between PSI and soil Ca. Inclusion of initial soil P and organic carbon along with CEC increased the predictability of PAI from 37% to 59%. In soils with pH > 8.8, soil pH was the dominant factor controlling the PAI (r = 0.92).     

The effect of lime on the response of soils to sodic conditions

The role of CaC0₃ in preventing clay dispersion and losses in hydraulic conductivity (HC) of sodic soils was determined directly by mixing two lime-free soils with 0.5 and 2.0 per cent CaCO₃. Whereas the HC of the lime-free soils dropped sharply when 0.01 n solutions of SAR 20 were displaced with distilled water, mixing the soils with powdered lime prevented both HC losses and clay dispersion. The response of a sandy soil mixed with lime was similar to that of a calcareous sandy soil. The beneficial effect ofCaC0₃ was not so pronounced in soils equilibrated with solutions of SAR 30. The increase in electrolyte concentration, due to CaCO₃ dissolution, was suggested as the mechanism responsible for the beneficial effect of lime.     

Potassium release from sand,silt and clay fractions in calcareous soils of southern Iran

The release of non-exchangeable potassium from 24 calcareous soils of divergent mineralogy, from southern Iran, was examined. Sand, silt and clay particles were fractionated after dispersion with an ultrasonic probe. Samples were extracted with 0.01 M CaCl₂ for 30 successive 2-h periods. The clay fraction released the largest amount of K in each soil. Cumulative K released ranged from 175 to 723, 35 to 128, and 71 to 146 mg kg^?1 contributing 20–90, 4–39 and 2–54% for clay, silt and sand fractions, respectively. The lower proportion of K released from sand and silt fractions can be explained by the presence of a high content of CaCO₃ and quartz in these fractions. The release kinetics for the non-exchangeable K data showed that parabolic diffusion and power function were the best fitting kinetic models. This indicated that slow diffusion of K from the mica interlayer positions is the main rate-controlling process. Cumulative K released and constant b values of parabolic diffusion model correlated significantly with the mica content of the clay fraction.     

Zinc and copper in some soils of Egypt as related to other soil properties

Total Zn in alluvial and calcareous soils (average 138 and 70 ppm respectively) was significantly related to their contents of CaCO₃ (negatively), O.M. and clay (positively). Extracting Zn by Na₂EDTA gave the highest values for both soil types. Total Cu contents varied widely from 26 to 111 ppm in alluvial and from 15 to 30 ppm in calcareous soils. They were negatively correlated with the CaCO₃ contents. The pot experiments showed that EDTA(NH₄)₂CO₃, Na₂EDTA and DTPA are reasonable extractants for available Zn from both soil types. DTPA was efficient for all soils investigated, while Na₂ EDTA and EDTA-citrate were specific for extracting Cu from calcareous soils.     

Clay,Organic Carbon,Available P and Calcium Carbonate Effects on Phosphorus Release and Sorption–Desorption Kinetics in Alluvial Soils

Information on phosphorus (P) release kinetics and sorption–desorption in soils is important for understanding how quickly reaction approaches equilibrium and replenishes the depleted soil solution. Laboratory experiments were conducted to study the P release and sorption–desorption kinetics in soils differing in clay, soil organic carbon (SOC), available P, and calcium carbonate (CaCO₃) contents. Phosphorus release from soils proceeded in two phases: initially faster phase followed by a slower phase as equilibration progressed. Elovich equation (R² ≥ 0.97**) described well the P release versus time data. P release coefficients for power function were significantly correlated with available P and SOC. Freundlich sorption constants increased with increase in clay and CaCO₃ content. With increase in SOC and available P concentration in soils, substantial reduction in sorption constants was observed. It was concluded that for efficient P management, it is important to take into account soil texture, the existing soil P level, SOC content, and soil calcareousness.     

Density fractionation of organic matter in dolomite‐derived soils

Dolomite (CaMg(CO₃)₂) constitutes half of the global carbonates. Thus, many calcareous soils have been developing rather from dolomitic rocks than from calcite (CaCO₃)‐dominated limestone. We developed a physical fractionation procedure based on three fractionation steps, using sonication with subsequent density fractionation to separate soil organic matter (SOM) from dolomite‐derived soil constituents. The method avoids acidic pretreatment for destruction of carbonates but aims at separating out carbonate minerals according to density. The fractionation was tested on three soils developed on dolostone parent material (alluvial gravel and solid rock), differing in organic‐C (OC) and inorganic‐C (IC) concentrations and degree of carbonate weathering. Soil samples were suspended and centrifuged in Na‐polytungstate (SPT) solutions of increasing density, resulting in five different fractions: two light fractions < 1.8 g cm^–3 (> 20 μm and < 20 μm), rich in OC and free of carbonate, and two organomineral fractions (1.8–2.4 g cm^–3 and 2.4–2.6 g cm^–3), containing 66–145 mg g^–1 and 16–29 mg g^–1 OC. The organomineral fractions consist of residual clay from carbonate weathering such as clay minerals and iron oxides associated with SOM. The fifth fraction (> 2.6 g cm^–3) was dominated by dolomite (85%–95%). The density separation yielded fractions differing in mineral compositions, as well as in SOM, indicated by soil‐type‐specific OC distributions and decreasing OC : N ratios with increasing density of fractions. The presented method is applicable to a wide range of dolomitic and most likely to all other calcareous soils.     

Comparison of Four Equations to Describe the Kinetics of Lead Desorption from Soils

The rate of Pb desorption was investigated from clay (Silty clay, Torrifluvent), CaCO₃-rich (Sandy clay, Calciorthid), and sandy (Sandy loam, Quartzipsamment) soils at two different temperatures. Lead has not been released from CaCO₃-rich soils which suggests irreversible Pb sorption by the soil. The desorption was quite hysteretic from sand and clay soils. The total amount of Pb released from the clay soil exceeded that released from the sandy soil. The lower Pb desorption associated with the sandy soil is probably due to its higher calcium carbonate content relative to the clay soil. The kinetics of Pb desorption were evaluated using the Elovich, modified Freundlich, parabolic diffusion, and first order equations. The first order and parabolic diffusion equations adequately described the kinetics of Pb desorption from clay and sandy soils under isothermal conditions. The choice of first order and parabolic equations among others investigated was based on the goodness of fit and the more scientific theoretical assumptions of the equations. The apparent Pb diffusion rate coefficient (D_d) and desorption rate coefficient (k_d) values from the clay and sandy soils increased with increasing temperature.     

Prediction of the water sorption isotherm in air dry soils

Within this work we present a revised pedotransfer function (PTF) that predicts water sorption isotherms for dry soils based on the clay content of the soils. When the water sorption isotherm is plotted as a water retention curve (log water potential plotted against the water content) it typically results in a log linear function as described by Campbell and Shiozawa (1992). The linear function is defined by its slope and a fixed endpoint at zero water content. The reciprocal of the slope shows a strong correlation with the clay fraction. For the calibration of a PTF we measured water sorption data for 18 soils with clay contents from 2% to 61%. The final predictions of the water sorption isotherms from the clay mass fraction were very good if the clay content was higher than 7%. The use of a revised theoretical endpoint at the dry end of the WRC did improve the prediction as compared to the endpoint that has been used in the literature before. In addition Literature data for 22 soils and 3 pure clay minerals were used for validation. The good performance of the PTF only occurred if the clay fraction was dominated by 2:1 clay minerals. The water retention isotherm of soils rich in the 1:1 clay mineral kaolinite could not be predicted by this approach; the actual water content was strongly over-predicted and the water retention curve did not follow a log linear relationship.     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

Soil hydrophobicity: a contribution of diuron sorption experiments

Retention processes play a major role in the fate and impact of organic contaminants in soils. The main goal of this study was to determine the influence of soil hydrophobic properties on the retention of diuron by using plots of a long‐term experiment in Versailles. We selected seven plots with pH 3.4 to 8.2 and low organic content. Sorption isotherms were obtained on soil slurries and kinetic measurements of diuron sorption were performed on undisturbed soil samples. The results showed that the Freundlich coefficient k_f decreased as pH increased and that the K_oc coefficient, k_f/TOC, was linearly related to the contact angle measured on the clay fraction over a wide range of pH. A low initial adsorption rate and low adsorption equilibrium were observed for the plot treated with NaNO₃. In this case, the structure in micro‐aggregates was assumed to limit the accessibility of adsorption sites. The CaCO₃ and CaO treated plots had similar organic matter contents, pHs, CECs and bulk densities, although their < 2 μm:C ratio differed. The higher retention of diuron in the CaCO₃ plot is attributed to the higher hydrophobicity of the < 2 μm fraction, probably masking part of the permanent clay negative charges. Thus, in addition to the different treatments, organic matter composition and distribution should also be included as specific soil properties. We conclude that the sorption properties of pesticides such as diuron can be a good tool to obtain greater understanding of soil properties and the degree of soil hydrophobicity/hydrophilicity in particular.     

Phosphorus Adsorption Isotherm: A Key Aspect for Effective Use and Environmentally Friendly Management of Phosphorus Fertilizers in Calcareous Soils

Crop response to the phosphorus (P) application is often erratic in most soil types in the world. In Algeria, there is no information on the P behavior in calcareous soils. The purposes of this work were to investigate the degree of P fixing capacity and to predict P fertilizer requirements of crops according to calcareous levels in the soil. Soil samples (at 0–30 cm depth) were collected and spiked with 0, 25 and 50% of lime (CaCO₃). Phosphate sorption curves were well fitted to the Freundlich equation. Results indicated that the calcareous level was predominantly controlled the P sorption indices [sorption capacity (a), and P sorption energy (n)] to affect the estimation of external d P requirement (EPR_0.2) and P fertilizer rates. The understanding of P sorption and desorption by soils and extrapolating the developed relationship between soil calcareous contents and P fertilizer rates would be quite promising and accurate approach for the economic and effective use of P fertilizers in calcareous soils of Algeria.     

石灰化水稻土的形成

石灰化水稻土在我国约有400多万亩。CaCO₃含量10—20%,CaCO₃/MgCO₃之比10—30不等。土壤板结,有石灰结核,有时形成石灰盘。土壤缺磷,少钾,有效态硼、锌、钼、锰也不足。是华南的一种中低产水稻土。石灰化水稻土中的钙主要来自年复一年的施用石灰和引灌含钙高的石灰岩溶洞水;石灰积聚的条件是土壤pH高,土壤CO₂分压低和通透性不良;根据土壤中石灰含量和¹⁴C测定估算,石灰化水稻土的形成至少有360年以上的历史。石灰化水稻土施用石灰不起中和酸性的作用。所以,必须停施石灰,增施有机肥以根本上改良这种土壤,在未改良前应对症施肥以提高产量。     

在DAP-CaCO3体系与DAP-石灰性土壤体系中NH3的挥发与磷的吸附之间的关系

本工作是研究在CaCO₃体系和石灰性土壤体系中NH₃的挥发与磷的吸附之间相互作用的化学变化,结果表明:在NH₄Cl—CaCO₃体系中,通气的pH值比不通气的低,但溶液中Ca²⁺浓度正好相反。在K₂HPO₄-CaCO₃体系中,在24小时内,通气与不通气的,CaCO₃吸附磷没有差异。在24小时反应期间,在DAP-CaCO₃体系中,因溶液pH值不断增高,NH₃的挥发对CaCO₃吸附磷的影响也就逐渐降低。在石灰性土壤体系中,施用尿素加过磷酸钙或单施尿素时,几乎没有发现NH₃的挥发,而施DAP时,在6天后,NH₃的挥发损失占加入的56%,且DAP处理的土壤,其水溶性磷未通气比通气的高。尿素加过磷酸钙处理的,其水溶性磷通气与未通气的没有差异。另外,尿素加过磷酸钙或过磷酸钙单独处理的土壤,水溶性磷含量均相同。所有这些均表明,在石灰质体系中,NH₃的挥发(如果发生的话)能够加强CaCO₃对磷的吸附,而磷的吸附又能加强NH₃的挥发,两者是相互影响和相互促进的过程。     

Untersuchungen zur Charakterisierung des pflanzenverfügbaren Phosphats in Thüringer Carbonatböden

Investigations on the characterization of plant available phosphate in Thuringian calcareous soils Phosphate availability in Thuringian calcareous soils and its characterization by CAL‒, NaHCO₃-, H₂O- and CaCl₂-soil tests was investigated in laboratory and pot experiments. Soil CaCO₃ contents > 10% increase the pH value of CAL solution and thus decrease phosphate extractability. The increase of pH also causes an inadequate assessment of plant available phosphate by H₂O- and CaCl₂-soil tests. The CAL soluble P content of the soil corrected by the pH value of the extraction solution was most suitable for the forecast of P uptake of corn in a pot trial. From both parameters P availability indices for calcareous soils can be calculated which are comparable with those in soils containing < 5% CaCO₃. The equation, which still has to be verified in field experiments, reads as CAL-P_corrected = CAL-P_measured · (1 + 0.83·〈pH-value_{CAL solution} — 4.1〉).     

Effect of iron oxide on phosphate sorption by calcite and calcareous soils

Pure calcite (AR grade CaCO₃) was treated with ferrous perchlorate solution to give a surface coating of iron (Fe) oxide. Maximum sorption (x_m) of phosphate (P) by the calcite increased from 18.2 to 160 mg P kg^?1 as the amount of coating increased from 0.00 to 16.0 g Fe₂O₃, kg^?1 CaCO₃. Evidence for Fe oxide coatings on carbonate minerals in two Sudanese soils was obtained by optical microscopy and electron-probe microanalysis. The relative contributions of carbonate and Fe oxide minerals, and Fe oxide coatings to P sorption in these soils were calculated, based on an assumed model of oxide distribution. Separate-phase Fe oxide was the major contributor (30–40%) to P sorption in the soils; the Fe oxide coatings on carbonate minerals were only minor contributors (< 6%), and the contribution of uncoated carbonate minerals was found to be negligible (<1 %). These results suggest a very minor role for carbonate minerals, even when coated with Fe oxide, in the sorption of P by these calcareous, Sudanese soils.     

Black carbon estimation in French calcareous soils using chemo‐thermal oxidation method

We studied the black carbon (BC) content of ca. 405 samples from French topsoil and artificial soil and carbonate mixtures. Our protocol involved three main steps: (i) decarbonation by HCl, (ii) elimination of non‐pyrogenic organic carbon in a furnace at 375 °C, and (iii) quantification of residual carbon by CHN analysis. BC content increased for calcareous soils according to their carbonates content. Subsequent analyses confirmed the existence of a methodological artefact for BC determination only in calcareous soils. Decarbonation changes the thermal properties of organic matter, creating more recalcitrant carbon than in the initial sample. Higher CaCO₃ and organic carbon content results in a more pronounced artefact. The reversal of the first two steps of the chemo‐thermal oxidation method (i.e. thermal oxidation before soil decarbonation) eliminates this artefact. Overall, our results suggest that BC content may have been overestimated in a large number of studies on calcareous soils.     

Evaluation of 1H NMR relaxometry for the assessment of pore‐size distribution in soil samples

¹H NMR relaxometry is used in earth science as a non‐destructive and time‐saving method to determine pore size distributions (PSD) in porous media with pore sizes ranging from nm to mm. This is a broader range than generally reported for results from X‐ray computed tomography (X‐ray CT) scanning, which is a slower method. For successful application of ¹H NMR relaxometry in soil science, it is necessary to compare PSD results with those determined from conventional methods. The PSD of six disturbed soil samples with various textures and soil organic matter (SOM) content were determined by conventional soil water retention at matric potentials between −3 and −390 kPa (pF 1.5–3.6). These PSD were compared with those estimated from transverse relaxation time (T₂) distributions of water in soil samples at pF 1.5 using two different approaches. In the first, pore sizes were estimated using a mean surface relaxivity of each soil sample determined from the specific surface area. In the second and new approach, two surface relaxivities for each soil sample, determined from the T₂ distributions of the soil samples at different matric potentials, were used. The T₂ distributions of water in the samples changed with increasing soil matric potential and consisted of two peaks at pF 1.5 and one at pF 3.6. The shape of the T₂ distributions at pF 1.5 was strongly affected by soil texture and SOM content (R² = 0.51 − 0.95). The second approach (R² = 0.98) resulted in good consistency between PSD, determined by soil water retention, and ¹H NMR relaxometry, whereas the first approach resulted in poor consistency. Pore sizes calculated from the NMR data ranged from 100 μm to 10 nm. Therefore, the new approach allows ¹H NMR relaxometry to be applied for the determination of PSD in soil samples and for studying swelling of SOM and clay and its effects on pore size in a fast and non‐destructive way. This is not, or only partly, possible by conventional soil water retention or X‐ray CT.     

Comparing tests for soil fertility: 1. Conversion equations between olsen and mehlich 3 as phosphorus extractants for 120 soils of south italy

Abstract

The multiple‐element extractant Mehlich 3 (M3) has not been tested extensively in Europe. In this Land, soil‐P test recommendations are based, since decades, on the evaluation of the Olsen‐extractable P, and the optimal soil‐P levels have been established to range between 1.5 and 3.0 mg of Olsen‐P per 100 g of soil. A research programme was started in order to assess the suitability of M3 as routine soil‐P test in European laboratories. As a first approach, we develop conversion equations from Olsen‐P to M3‐P, in order to assess the agreement and the consistency of the measurements under a wide range of chemical and physical soil properties. To this aim, 120 samples with drastically contrasting features were selected within 206 soils collected from all the regions of South Italy. Soil‐P ranges were 0.07–60.53 for M3, and 0.08–21.47 mg/100 g for Olsen. The results showed that M3‐P was a P extractant more efficient than Olsen. The amounts of M3‐P were, on the average, twice as large as the Olsen‐P ones, with mean values of 5.70 and 2.75 mg/100g, respectively. The soil properties exerted a great influence, as well as showed a contrasting effect, on the extraction efficiency of each method. For neutral‐alkaline calcareous soils, the average M3‐P/Olsen‐P ratio increased to 2.52, and the efficiency of M3 poorly varied according to soil pH and CaCO₃ content. On the contrary, in CaCO₃‐free acidic soils, the M3‐P/Olsen‐P ratio decreased to 1.63. In particular, anomalous ratio values less than 1.0 were observed for acidic soils with high content of organo‐mineral complexes with be shifted to 3.7–7.7 for calcareous soils, and to 2.7–4.9 for CaCO₃‐free soils. Field calibrations would give more information to establish the proper values according to either the soil properties and plant requirements. The results encourage the introduction of M3 as routine soil‐P test in our Countries. One must take into account, however, that some soil properties, in particular the CaCO₃ content, migth be considered for a more precise comparative evaluation with existing laboratory data.