Phosphate sorption by natural hematites

Iron (hydr)oxides are active phosphate sorbents in soils and sediments, but no information exists on phosphate (P) sorption by natural hematites. In this study, we characterized the chemical, mineralogical and P-sorption properties of 14 hematite-rich natural materials of different origins. Phosphate sorption was described by a modified Freundlich equation including a time term. Phosphate sorbed at 1d at an equilibrium concentration of 1 mg P dm^?3 ranged widely (0.2–1.7 μmol m^?2). After 1 d, hematites showed a marked slow sorption. At 75 d, and an equilibrium concentration of 6mg P dm^?3, the total amount of P sorbed ranged between 0.8 and 4.1 μmol mp^?2. Phosphate-sorption capacity was influenced by the morphology of the coherently scattering domains: the shorter the domains in the crystallographic c relative to the a direction, the lower the P-sorption capacity. This has been observed by other authors in synthetic hematites and agrees with the idea that the prismatic faces, which have singly co-ordinated Fe-OH groups, are more active in P-sorption than other faces. The average P sorption capacity of hematites was similar to that of natural goethites (2.6 μmol P m^?2) but, in contrast to these, variability among samples was high. In comparison with goethites, hematites show slower sorption and lower affinity for phosphate.     

Evaluation of phosphorus sorption by an allophanic soil

Solutions containing different P concentrations were equilibrated with samples of an allophanic soil from Navarra (Spain) to determine whether P sorption conformed qualitatively and quantitatively to the Langmuir, Freundlich and Sokolowska isotherms.Phosphorus sorption conformed to the Langmuir isotherm. When the sorption d data were plotted according to the conventional and Hofstee forms, two linear relationships were obtained. At the lower equilibrium P concentrations the K₁ parameter determined by regression analysis was higher than those corresponding to higher equilibrium P concentrations. The values obtained for K₁ and K₂ by the conventional and Hofstee equations were different. A procedure for evaluating the coefficients for higher equilibrium P concentrations was proposed. The K₁ and K₂ values so obtained allowed us to generate an experimental curve by addition of calculated adsorption data. This suggests that the curve-splitting technique is satisfactory.The sorption data also conformed to the Freundlich and Sokolowska equations, but in the latter it was necessary to evaluate two different sets of parameters.The same experimental data can be adjusted to the three different equations, in one case with only one set of constants and in the other two cases with two different sets of parameters, one for the lower P concentrations and the other for the higher ones. Besides, to fit the experimental data to the Langmuir and Sokolowska equations, it was necessary to split the isotherm into two regions and these two regions were different for the Langmuir and the Sokolowska equations. This suggests that the parameters do not have any chemical signification and that they are only “curve fitting”.A study of the effect of pH on the P sorption indicated that low pH notably increased the P sorption.The soil samples had very high phosphate sorption capacity probably due to the very large specific surface and reactivity of the allophane.     

挥发性氯代烃在土壤中的吸附行为研究进展

挥发性氯代烃(Volatile chlorinated hydrocarbons,VCHs)是工业污染场地的常见污染物,在非饱和带存在于土壤气相、水相、固相或以高密度非水相液体(Dense non-aqueous phase liquids,DNAPL)的形式存在,形成一个动态平衡系统。土壤对VCHs的吸附不仅影响土壤中的污染物浓度,而且极大地影响VCHs的迁移转化行为。根据VCHs在土壤中的吸附机制,可以对土壤中的VCHs浓度进行预测,优化各种模型参数,指导污染修复及管理工作。本文总结了VCHs在非饱和带土壤中的相间分配特征,吸附机制及其影响因素,特别探讨了土壤有机碳、矿物及水分对吸附的影响,提出了当前研究中存在的问题,并对将来研究进行了展望。     

矿物对溶解性有机质及其不同组分的吸附作用

溶解性有机质(Dissolved Organic Matter,DOM)在土壤矿物表面的吸附控制着其在土壤中的迁移,会影响土壤/矿物对重金属、有机污染物等的传质过程[1～3]。已往资料揭示,土壤中黏土矿物是DOM的重要吸附质;但迄今,有关DOM在不同类型黏土矿物表面吸附的差异及机制尚很不清楚。另外,不同DOM组分在土壤矿物上的吸附各异,土壤矿物对DOM不同成分的吸附具有选择性;因此分离DOM不同组分,分别研究其在土壤矿物上的吸附有助于揭示DOM与土壤矿物的结合机理,但该研究尚待深化。此外,目前研究中DOM多以土壤中提取的为主[4],对于因污泥农用等农业管理措施而从外部引入土壤的DOM的研究还较     

Cadmium sorption behavior of natural and synthetic zeolites

Abstract

The sorptive properties of zeolites (a natural zeolite and 3 synthetic zeolites) for cadmium (Cd) were investigated with the intention of selecting suitable materials, for use as amendments in contaminated soils, to reduce the uptake of Cd by field crops. The Cd sorption data were well described by the Langmuir and the Freundlich equations and the coefficients values indicated significant sorptive capacities for Cd by these minerals. Synthetic zeolites have 100 to 500 times greater sorption capacities than the natural zeolite. In all cases, sorption increased with increasing pH and this relationship was linear over the pH range between 3 and 10 for the natural zeolite whereas for the synthetic zeolites a sharp increase was observed between pH 3 and 6. The critical pH above which maximum Cd sorption occurred on synthetic zeolites coincided with the pH where mineral dissolution ceases. The natural zeolite showed an inverse relationship between particle size (<0.15–2.0 mm) and Cd sorption. In desorption experiments with natural zeolite, 10 sequential extractions with 0.01 MNaC10₄ removed 19% Cd from the lowest sorption treatment and 44% of the metal from the highest level, showing that Cd was bound more strongly with decreasing concentrations. Desorption was greater with 0.01 MKC10₄than 0.01 MNaC10₄ especially in the first 5 extractions.     

Dissolved organic matter enhances the sorption of atrazine by soil

The influence of dissolved organic matter (DOM) on the sorption of atrazine (2-chloro-4-ethylamino-6-isopylamino-1,3,5-triazine) by ten soils was investigated. Batch sorption isotherm techniques were used to evaluate the important physiochemical properties of soil determining the sorption of atrazine in the presence of DOM. The sorption of atrazine as a representative of nonionic organic contaminants (NOCs) by soil with and without DOM could be well described by the Linear and Freundlich models. The n values of the Freundlich model were generally near to 1, indicating that linear partitioning was the major mechanism of atrazine sorption by soil samples. The apparent distribution coefficient, value, for atrazine sorption in the presence of DOM initially increased and decreased thereafter as the DOM concentration increased in the equilibrium solution. DOM at relatively lower concentrations significantly enhanced the sorption of atrazine by soil, while it inhibited the atrazine sorption at higher concentrations. For all the soil samples, the maximum of was 1.1~3.1 times higher than its corresponding K _d value for the control (without DOM). The maximum enhancement of the distribution coefficient () in the presence of DOM was negatively correlated with the content of soil organic carbon (SOC) and positively correlated with the clay content. The critical concentration of DOM, below which DOM would enhance atrazine sorption, was negatively correlated with SOC. The influence of DOM on atrazine sorption could be approximately considered as the net effect of the cumulative sorption and association of atrazine with DOM in solution. Results of this study provide an insight into the retention and mobility of a NOC in the soil environment.     

The effects of phosphate on zinc sorption by a soil

Zinc sorption curves were obtained after treatment of a soil with several rates of phosphate and with two rates of lime. The lime permitted evaluation of the effects of phosphate on Zn sorption via its effects on pH. The phosphate was either incubated with the soil at a high temperature before reaction with Zn or was supplied at the same time as the Zn. This produced treatments with similar concentration of phosphate in solution but different amounts of sorbed phosphate.
Two distinct effects of phosphate addition on Zn sorption were detected. One arose from effects of phosphate on pH. This effect could be large and could either increase or decrease Zn sorption depending on the direction of the pH effect. A second effect was correlated with the amount of sorbed phosphate and was assumed to operate through the effects of phosphate on charge. The effects were small at low levels of Zn but larger at higher levels. This suggested that Zn and phosphate were sorbed at opposite ends of a spectrum of electrostatic potentials and overlap only occurred when the level of application was high. A third possible effect, due to reaction of the soil with zinc phosphate complexes in solution, was not proved.     

刚性轮-月壤相互作用预测模型及试验研究

研究在月球表面特殊环境下的月球车牵引通过性能,对保证月球车的正常探测工作具有重要意义。在分析传统地面车辆理论与研究方法的基础上,给出了刚性轮与月壤相互作用的预测模型;使用辉南一带火山灰制备了应用于月面车辆力学基础试验中的模拟月壤;设计制造了月壤一车轮土槽试验系统。最后,在该土槽试验系统下对有轮刺轮与无轮刺轮进行了牵引性能试验,并与模型计算值进行对比。结果表明,所给模型的预测值与实测值有较好的一致性。     

Stabilization of dissolved organic matter by sorption to the mineral soil

The main process by which dissolved organic matter (DOM) is retained in forest soils is likely to be sorption in the mineral horizons that adds to stabilized organic matter (OM) pools. The objectives of this study were to determine the extent of degradation of sorbed OM and to investigate changes in its composition during degradation. DOM of different origins was sorbed to a subsoil and incubated for 1 year. We quantified mineralized C by frequent CO₂ measurements in the headspace of the incubation vessels and calculated mean residence times by a double exponential model. Mineralization of C of the corresponding DOM in solution was used as a control to estimate the extent of DOM stabilization by sorption. Changes in the composition of sorbed OM during the incubation were studied by spectroscopic (UV, fluorescence) and isotope (¹³C, ¹⁴C) measurements after hot-water extraction of OM.The fraction of sorbed organic C mineralized during the incubation was only one-third to one-sixth of that mineralized in solution. The mean residence time of the most stable OM sample was estimated to increase from 28 years in solution to 91 years after sorption. For highly degradable DOM samples, the portion of stable C calculated by a double exponential model nearly doubled upon sorption. With less degradable DOM the stability increased by only 20% after sorption. Therefore, the increase in stability due to sorption is large for labile DOM high in carbohydrates and relatively small for stable DOM high in aromatic and complex molecules. Nevertheless, in terms of stability the rank order of OM types after sorption was the same as in solution. Furthermore, the extent of sorption of recalcitrant compounds was much larger than sorption of labile compounds. Thus, sorptive stabilization of this stable DOM sample was four times larger than for the labile ones. We conclude that stabilization of OM by sorption depends on the intrinsic stability of organic compounds sorbed. We propose that the main stabilization processes are selective sorption of intrinsically stable compounds and strong chemical bonds to the mineral soil and/or a physical inaccessibility of OM to microorganisms. The UV, fluorescence and ¹³C measurements indicated that aromatic and complex compounds, probably derived from lignin, were preferentially stabilized by sorption of DOM. The ¹³C and ¹⁴C data showed that degradation of the indigenous OM in the mineral soil decreased after sorption of DOM. We estimated DOM sorption stabilizes about 24 Mg C ha⁻¹ highlighting the importance of sorption for accumulation and preservation of OM in soil.     

Effects of soil organic matter on pH-dependent phosphate sorption by soils

Effects of soil organic matter (80M) on P sorption of soils still remain to be clarified because contradictory results have been reported in the literature. In the present study, pH-dependent P sorption on an allophanic Andisol and an alluvial soil was compared with that on hydrogen peroxide (H₂0₂)-treated, acid-oxalate (OX)-treated, and dithionite-citrate- bicarbonate (DCB)-treated soils. Removal of 80M increased or decreased P sorption depending on the equilibrium pH values and soil types. In the H₂O₂ OX-, and DCB-treated soils, P sorption was pH-dependent, but this trend was not conspicuous in the untreated soils. It is likely that 80M affects P sorption of soils through three factors, competitive sorption, inhibition of polymerization and crystallization of metals such as AI and Fe, and flexible structure of metal-80M complexes. As a result, the number of available sites for P sorption would remain relatively constant in the wide range of equilibrium pH values in the presence of 80M. The P sorption characteristics were analyzed at constant equilibrium pH values (4.0 to 7.0) using the Langmuir equation as a local isotherm. The maximum number of available sites for P sorption (Q _max) was pH-dependent in the H₂0₂-, OX-, and DCBtreated soils, while this trend was not conspicuous in the untreated soils. Affinity constants related to binding strength (K) were less affected by the equilibrium pH values, soil types, and soil treatments, and were almost constant (log K ≈ 4.5). These findings support the hypothesis that 80M plays a role in keeping the number of available sites for P sorption relatively constant but does not affect the P sorption affinity. By estimating the Q _max and K values as a function of equilibrium pH values, pH-dependent P sorption was well simulated with four or two adjustable parameters. This empirical model could be useful and convenient for a rough estimation of the pH-dependent P sorption of soils.     

Changes in some soil phosphorus availability parameters as induced by phosphorus addition and soil sorption properties

Abstract

Changes in agronomic and environmental soil phosphorus (P) availability parameters, i.e., Mehlich‐ and Olsen‐extractable P, reversibly‐adsorbed P, soil‐solution P, and equilibrium‐P concentration were determined following equilibration of 13 Italian soils with five rates of P application (0, 12.5, 25, 50, and 100 mg P kg^‐1 soil). Soil P availability as determined by each parameter increased with added P. The relative change in soil P availability with added P was a function of soil sorption index silicon (SI), according to the equation DP=(P_added)^a*exp(b+g*SI). This equation accounted for 94 to 98% of the variance in soil‐P availability. The inclusion of SI in a soil testing program may increase the reliability in assessing both soil‐P fertilizer requirements and the vulnerability of a soil to P loss in runoff following land application of fertilizer or manure P.     

Nomographic estimation and evaluation of soil erodibility under simulated and natural rainfall conditions

To evaluate soil erodibility under different land uses and to study the applicability of nomograph for estimation of soil erodibility a field experiment was conducted under both natural and simulated rainfall conditions under four land uses viz. barren, cultivated, grassland, and forest in the sub‐mountainous tract of Punjab (India). Measured soil erodibility (K) values varied from 0·33 to 0·67 under natural rainfall conditions and from 0·23 to 0·40 under simulated rainfall conditions. Among different land uses, measured K was in the order of barren > cultivated > grassland > forest soils. The values of the K estimated by nomograph were very low as compared to the observed values. The trends were also in contrast to these observed values of K under simulated and natural rainfall conditions. To modify nomograph equation, different ranges of aggregate sizes were correlated with soil loss. It was observed that water stable aggregates (WSA) <2 mm size had a significant correlation with soil loss under both natural (r = 0·88) and simulated (r = 0·76) rainfall conditions. So the nomograph equation was modified to include the M parameter based on WSA <2 mm size. The value of K estimated from the modified nomograph had a significant correlation with measured values of K under both the natural and simulated rainfall conditions. Copyright © 2009 John Wiley & Sons, Ltd.     

Enhanced sorption of polycyclic aromatic hydrocarbons by soil amended with biochar

Purpose  

Polycyclic aromatic hydrocarbon (PAHs) are ubiquitous pollutants in agricultural soils in China. Biochar is the charred product of biomass pyrolysis, which is widely applied to soils to sequestrate atmospheric carbon dioxide and guarantees a long-term benefit for soil fertility. Knowledge about the impacts of various biochars on soil sorption affinity remains obscure. In this study, we evaluated the effects of various biochars on PAHs sorption to biochar-amended agricultural soil.     

A mechanistic model for describing the sorption and desorption of phosphate by soil

A model of phosphate reaction is constructed and its output compared with observations for the sorption and desorption of phosphate by soil. The model has three components: first, the reaction between divalent phosphate ions and a variable-charge surface; second, the assumption that there is a range of values of surface properties and that these are normally distributed; third, the assumption that the initial adsorption induces a diffusion gradient towards the interior of the particle which begins a solid-state diffusion process. The model closely describes the effects on sorption of phosphate of: concentration of phosphate, pH, temperature, and time of contact. It also reproduces the effects on desorption of phosphate of: period of prior contact, period and temperature of desorption, and soil: solution ratio. The model is general and should apply to other specifically adsorbed anions and cations. It suggests that phosphate that has reacted with soil for a long period is not ‘fixed’ but has mostly penetrated into the soil particles. The phosphorus can be recovered slowly if a low enough surface activity is induced.     

Factors affecting the soil sorption of iodine

Iodine-129 is an important radionuclide released from nuclear facilities because of its long radioactive half-life and its environmental mobility. Its retention in surface soils has been linked to pH, organic matter, and Fe and Al oxides. Its inorganic solution chemistry indicates I will most likely exist as an anion. Three investigations were carried out to provide information on the role of the inorganic and organic chemistry during sorption of I by soil. Anion competition using Cl^? showed that anion exchange plays a role in I sorption in both mineral and organic soils. The presence of Cl decreased the loss of I^? from solution by 30 and 50% for an organic and a carbonated sandy soil respectively. The I remaining in solution was associated primarily with dissolved organic carbon (DOC). The loss rate from solution appears to depend on two reactions of I with the soil solids (both mineral and organic) creating both a release to and a loss from solution, and the reaction of I with the DOC (from very low to high molecular weight). Composition analyses of the pore water and the geochemical modelling indicate that I sorption affects the double-charged anion species in solution the most, particularly SO₄ ^?. Iodide introduced to natural bog groundwater at three concentrations (10^?3, 10^?1 and 10 meq L^?1) remained as I^? and was not lost from solution quickly, indicating that the association of I with DOC is slow and does not depend on the DOC or I concentration. If sorption of I to soil solids or DOC is not sensitive to concentration, then stable I studies, which by necessity must be carried out at high environmental concentrations, can be linearly extrapolated to radioactive I at much lower molar concentrations.     

Pesticide sorption and diffusion in natural clay loam aggregates

Pesticide sorption in soils is controlled by time-dependent processes such as diffusion into soil aggregates and microscopic sorbent particles. This study examines the rate-controlling step for time-dependent sorption in clay loam aggregates. Aggregates (5 mm) were stabilized with alginate, and adsorption of azoxystrobin, chlorotoluron, and cyanazine was measured in batch systems equilibrated for periods between 1 h and 7 days. Stepwise desorption was measured at 1- or 3-day intervals following 1 or 7 days of adsorption. Time-dependent adsorption was also measured on dispersed soil. Results were interpreted using process-based modeling. Adsorption on dispersed soil was described by intraparticle sorption and diffusion. Adsorption in the aggregates was much less than in suspension, suggesting that part of the sorption capacity of the dispersed soil was not available within the aggregates (approximately 50%). Adsorption and desorption were reversible and could be described by pore diffusion into the aggregate with effective diffusion coefficients between 0.5 x 10(-10) and 1 x 10(-10) m2 s(-1), a factor 3-6 slower than estimated theoretically. Intraparticle diffusion did not seem to contribute to sorption in the aggregates at this time scale. Apparent hysteresis was explained by nonattainment of equilibrium during the adsorption and desorption steps.     

Effect of soil microorganisms on the sorption of zinc and lead compounds by goethite

The objectives of this study were (1) to determine the effect of microorganisms during in‐vitro incubation on the amount of Zn and Pb from solution retained on goethite precipitated as coatings on a sand matrix and (2) to evaluate accumulation of heavy metals in the biomass of soil microorganisms in the fresh soil samples using an extractive approach. A mixture of colonies of cultivated microorganisms extracted from a Haplic Luvisol (Russia) and an Antropi‐urbic Regosol (Germany) were used to prepare the cell and the microbial‐debris suspensions. The concentrations of Zn and Pb in the studied solutions supplied with microbial suspensions and/or goethite coated sand were 0.1 mM (130.8 and 414 mg kg^–1 of sand, respectively). Exchangeable forms of metals were determined by extraction with 10 mL of 1.0 M KNO₃. Nonexchangeable forms of Zn and Pb were recovered using 40 mL of 0.3 M NH₂OH‐HCl in 1 M HNO₃. Concentrations of Pb increased in the solutions and decreased on the surface of the Fe‐mineral due to living microorganisms. In comparison to incubation of heavy‐metal solutions with goethite only, the absolute concentrations of nonexchangeable forms of metal were reduced by microbial suspension to a greater extent than those of the exchangeable forms, whereas the relative content of both fractions decreased by a factor of almost two. Sorption of Pb by goethite was inversely correlated with the concentration of organic C in the solution. Microorganisms clearly influenced the Zn sorption by goethite at concentrations of C_org > 400 mg L^–1. The amount of Zn retained was decreased primarily due to decreasing Zn portions in the exchangeable fraction. Microbial debris prepared by autoclaving reduced the Pb sorption by goethite similar to the results for living cells. Living microorganisms accumulated more Zn than did microbial debris. The data of this paper show that a direct determination of heavy‐metal accumulation in soil microorganisms by extraction with 2.0 M KCl as well as by extraction with 1 M CH₃COONH₄ at the natural pH of the soils after chloroform fumigation of fresh soils samples with different concentrations of organic C was not possible.