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1.
Previously presented evidence of Zn competition for Cd soil sorption sites has been confirmed by detailed studies of two Danish soils. Cadmium distribution between soil and solute decreases for increasing Zn solute concentrations. A Langmuir model accounting for both Cd and Zn sorption onto the same sorption sites was supported by independent experimental data on Cd and Zn distribution. The competition of Zn is governed by the product of the Zn soil sorption stability constant and the actual Zn solute concentration. Cadmium distribution coefficients may be significantly influenced by Zn at Zn solute concentrations above 100 μg Zn dm?3. This may have implications for interpreting Cd plant uptake and leaching.  相似文献   

2.
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.  相似文献   

3.
Abstract

Arsenite sorption was studied at different temperatures (30,40, and 50°C) to investigate processes that remove arsenite from soil solution (adsorption or precipitation), and if adsorption was taking place, how many sites were involved in this process, and their nature. Adsorption was the only reaction reducing levels of soluble arsenite in the two alkaline soils used in this experiment, Jijona and Agost; however, arsenite precipitation occurred in an acidic substrate (pH 4.0), Galicia soil. Iron (Fe) oxides and clay minerals were the soil components controlling arsenite sorption in the Jijona soil (pH 7.9 and high levels of Fe oxides). Calcite and clay minerals were the inorganic constituents involved in arsenite sorption in the Agost soil (pH 8.0 and high levels of CaCO3). Arsenite sorption was an endothermic and non‐spontaneous process. The fact that the higher the temperature, the higher the arsenite sorption, however, was likely due to an increase in the diffusion rate.  相似文献   

4.
Rainfall variability within a storm can have a significant impact on the amount of chemical transported by surface runoff and preferential flow. Previously, studies have evaluated only a few slowly varying rainfall patterns and related sorption capacities. We use a bounded random cascade approach to generate 50 000 realizations of realistic rainfall intensity patterns within a single storm event (96 minutes duration, mean intensity of 18.75 mm hour?1) to explore the effects on the partitioning of rainfall and linearly sorbing solutes between fast preferential flow (loading) and slow flow in the soil matrix for a silt loam and a sandy clay. Loading and infiltration are modelled by a near‐surface mixing model and Green–Ampt infiltration. The statistical properties of loading were evaluated from these simulations. For this storm the mean total of resident solute mixing from the soil to preferential flow reached a maximum for a retardation factor R ～ 5. Much smaller loadings occurred for more weakly sorbing and more strongly sorbing solutes. The variability of loading tended to decrease with increasing R. Ensemble averaged rainfall patterns were derived which related to the magnitude of loading. The patterns of rainfall generating large preferential flows did not necessarily lead to large solute loading. Early peaking, mid‐storm peaking and late peaking rainfall contributed to large solute loadings, depending upon soil and chemical properties. These patterns result from a balance between the amount of preferential flow generated and the amount of solute available when preferential flow is triggered. The results suggest that the use of R as a measure of the mobility of resident solutes depends on the flow pathway considered. In addition, characterization of flux distributions in soil with weakly sorbing, resident tracers, may underestimate the potential for rapid transport of strongly sorbing solutes subject to natural variations in rainfall.  相似文献   

5.
The consequences of slow diffusion of strongly adsorbed solutes into soil aggregates are not fully understood. The distribution of 32P after diffusing down a soil column cannot be explained from a consideration of liquid-phase impedance factor and isotopic exchange alone, as can that of 36CI. A model was developed that considers the soil to provide linked parallel intra-aggregate and inter-aggregate pathways. With this geometry, simulations agreed fairly well with experimental data when the intra-aggregate impedance factor was 0.001, using other model parameters that had been determined in independent equilibration studies. With this intra-aggregate impedance factor, the model yielded straight-line plots for chloride and the overall impedance factor derived agreed closely with the experimental one. The intra-aggregate impedance factor for 32P also agreed with the rate of reaction of the rapidly-exchanging P fraction previously determined. The slowly-exchanging P fraction has little influence on the P concentration profiles up to 10 d, but the small exchanged amount does have an effect at run times of 57 d. The slow intra-aggregate diffusion of strongly adsorbed solutes decreases the amount adsorbed from a surface source of supply, and it also decreases the amount that is taken up by a surface sink. However, the interaggregate solution concentration remote from a source of supply is considerably increased, which may be important if the solute is a pollutant or a nutrient.  相似文献   

6.
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.  相似文献   

7.
In this paper I discuss sorption curves: choosing them, fitting them, and interpreting them. The Langmuir equation is not appropriate for reaction of ions with soil. Despite some disadvantages, the Freundlich equation is the best simple equation. Fitting sorption equations causes statistical difficulties because sorption is usually calculated from the change in concentration. The two variables are therefore not independent. If this is ignored, the errors in the coefficients of the fitted curves will be small, but there will be larger errors in the measures of goodness of fit and tests of significance will not be valid. If mild but nevertheless adequate mixing of soil and solution are chosen, sorption and desorption will be the opposites of each other. We can therefore learn much about the rates of desorption by studying the rates of sorption. If a sink is used to capture desorbed nutrients, the potential rate of desorption will be underestimated, as no sink can instantly and completely remove all the nutrients from solution. Especially with phosphate, continuing reaction makes the surface potential more negative. This means that re‐application is made to a soil of smaller buffering capacity. This effect has been insufficiently studied. It influences both the response to further applications, and the ability of soil to store nutrients.  相似文献   

8.
The sorption of zinc (Zn) by two acid tropical soils, Mazowe clay loam (kaolinitic, coarse, Rhodic Kandiustalf) and Bulawayo clay loam (coarse, kaolinitic, Lithic Rodustalf), was studied over a wide range of Zn solution concentrations. Samples of the two soils used in the experiments were collected at both uncleared, uncultivated (virgin) sites and cultivated sites. The two virgin soils showed similar abilities to bind Zn. Mazowe soil (40 g organic matter kg?1) presented the highest affinity for Zn. Yet, Bulawayo soil (23.5 g organic matter kg?1) sorbed almost the same amount. Bulawayo soil had higher pH and Fe and Mn-oxide content than Mazowe soil. Once cultivated, the two soils behaved quite differently. After 50 years, Mazowe soil had lost 60% of its organic matter and effective cation exchange capacity (ECEC). In this soil, Zn sorption capacity had also been decreased by 60%. Clearing and 10 years under cultivation had affected neither the organic matter content nor the ECEC of Bulawayo soil. For this soil, Zn sorption was even higher in the cultivated soil, presumably due to an increase in the amount of Fe and Mn oxide from subsoiling. Zinc sorption was dependent upon pH, with retention dramatically increasing in the pH range 6–7. Sorption occurred at pH values below the point of zero charge (PZC), indicating that the sorption reaction can proceed even in the presence of electrostatic repulsion between the positively charged soil surface and the cation. In the two soils, the reversibility of the sorption reaction was very low. More than 90% of the sorbed Zn was apparently strongly bonded.  相似文献   

9.
《Geoderma》2005,124(1-2):91-104
The bioavailability and ultimate fate of heavy metals in the environment are controlled by chemical sorption. To assess competitive sorption of Pb and Cd, batch equilibrium experiments (generating sorption isotherms) and kinetics sorption studies were performed using single and binary metal solutions in surface samples of four soils from central Spain. For comparisons between soils, as well as, single and binary metal solutions, soil chemical processes were characterized using the Langmuir equation, ionic strength, and an empirical power function for kinetic sorption. In addition, soil pH and clay mineralogy were used to explain observed sorption processes. Sorption isotherms were well described by the Langmuir equation and the sorption kinetics were well described by an empirical power function within the reaction times in this study. Soils with higher pH and clay content (characterized by having smectite) had the greatest sorption capacity as estimated by the maximum sorption parameter (Q) of the Langmuir equation. All soils exhibited greater sorption capacity for Pb than Cd and the presence of both metals reduced the tendency for either to be sorbed although Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (k) was always greater for Pb than for Cd. However, these k values tended to increase as a result of the simultaneous presence of both metals that may indicate competition for sorption sites promoting the retention of both metals on more specific sorption sites. The kinetic experiments showed that Pb sorption is initially faster than Cd sorption from both single and binary solutions although the simultaneous presence of both metals affected the sorption of Cd at short times while only a minor effect was observed on Pb. The estimated exponents of the kinetic function were in all cases smaller for Pb than for Cd, likely due to diffusion processes into micropores or interlayer space of the clay minerals which occurs more readily for Cd than Pb. Finally, the overall sorption processes of Pb and Cd in the smectitic soil with the highest sorption capacity of the studied soils are slower than in the rest of the soils with a clay mineralogy dominated by kaolinite and illite, exhibiting these soils similar sorption rates. These results demonstrate a significant interaction between Pb and Cd sorption when both metals are present that depends on important soil properties such as the clay mineralogy.  相似文献   

10.
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.  相似文献   

11.
Soil water repellency (SWR) is known to lead to preferential flow and to degrade the soil's filtering efficiency. However, no method is available to quantify directly how SWR affects the transport of reactive solutes. We propose a new method for conducting solute transport experiments in water‐repellent soils. It involves sequentially applying two liquids, one water, the other a reference fully wetting liquid, namely aqueous ethanol, to the same intact soil core with air‐drying between liquids. We applied this approach to quantify the impact of SWR on the filtering of the herbicide 2,4‐Dichlorophenoxyacetic acid (2,4‐D) in two Andosols. In batch experiments conducted prior to the transport experiments, 2,4‐D sorption was not influenced by aqueous ethanol for one soil. However, sorption in the second soil followed the co‐solvency theory, which predicts decreasing sorption with increasing solvent fractions. Thus, sorption experiments are necessary to complement our new method. Breakthrough curves were characterized by preferential flow with large initial concentrations, tailing and a long prevalence of solutes remaining in the soil. In the soil in which 2,4‐D sorption was unaffected by aqueous ethanol, SWR increased 2,4‐D losses by four and 50 times in the first 5‐mm outflow compared with the 2,4‐D losses with water. After 50‐mm outflow, the 2,4‐D losses were similar for one core, but in the other core they were still about four times greater with water than with aqueous ethanol. This method to quantify the reduction of the soil's filtering efficiency by SWR is needed for assessing the increased risk of groundwater contamination by solutes exogenously applied to water‐repellent soils.  相似文献   

12.
Sorption of Cd at low concentrations onto two Danish soils (loamy sand, sandy loam) was examined in terms of kinetics and governing factors. From an environmental point of view soil sorption of Cd is a fast process: More than 95% of the sorption takes place within 10 min, equilibrium is reached in 1 hr, and exposures up to 67 wk did not reveal any long term changes in Cd sorption capacities. The soils have very high affinity for Cd at pH = 6.00 (10?3 M CaCl2) exhibiting distribution coefficients in the order of 200 to 250 (soil Cd concentration/solute Cd concentration). However, the sorption isotherms describing the distribution of Cd between soil and solute are slightly curvelinear. In the pH-interval 4 to 7.7, the sorption capacity of the soil approximately increases 3 times for a pH increase of one unit. Increasing the Ca concentration from 10?3 to 10?2 M reduces the sorption capacity of the sandy loam to one third.  相似文献   

13.
Abstract

The competitive sorption of copper (Cu), nickel (Ni), and zinc (Zn) in an Oxisol suspension was investigated using the Sheindrof‐Rebhun‐Sheituch (SRS) equation. Experimental data were obtained for a system containing these cations as single components, binary, and ternary mixtures. The associated competitive coefficients aij can be viewed as a way to quantify competitive interaction. The competition coefficients obtained for the cations indicated that the sorption of Ni and Zn by the soil was significantly inhibited by the presence of Cu, while the inhibition exerted in the reverse situation was milder. After a ij ‐values were substituted in the SRS equation, the sorption values predicated by this equation for the ternary solute mixture Cu‐Ni‐Zn, were compared to values determined experimentally. The SRS equation modeled sorption successfully for the range of solute concentrations used.  相似文献   

14.
The Taihu Lake region in East China has become prone to soil acidification, which changes heavy metals such as copper(Cu) in soil into water-soluble species and increases the mobility and contamination risks of heavy metals in the biological environment. In this study, the kinetics of Cu2+sorption by the bulk soil and the aggregate size fractions of an acidic paddy soil collected from the Taihu Lake region, the effects of temperature on Cu2+sorption, and the p H changes of the solution were investigated by static sorption and magnetic stirring. The aggregate size fractions were prepared by low-energy ultrasonic dispersing and freeze-drying. The total sorption amounts of the bulk soil and the aggregate size fractions for Cu2+followed a descending order of clay > coarse sand > bulk soil > silt> sand, corresponding to those of organic matter content, free iron oxide content, free aluminum oxide content, and cation exchange capacity. The kinetic sorption curves of Cu2+by the bulk soil and the aggregates, which were divided into two stages(rapid and slow sequentially), were well fitted by the first-order equation, the diffusion equation, and the Elovich equation, showing significant correlations(P < 0.05). Specific and non-specific sorption dominated in the fast and slow stages, respectively, and the former was predominant throughout the sorption process. The specific sorption accelerated and the non-specific sorption decelerated with rising temperature. The p H of the solution decreased significantly during the specific sorption and remained unchanged or increased slightly during the non-specific sorption. When the specific sorption terminated, the p H of the solution was minimized nearly simultaneously.The sorption progress of Cu2+by the bulk soil significantly preceded that by the aggregates. Therefore, heavy metal contamination may be another factor reducing soil p H and metal sorption forms should be taken into consideration in studies of mitigating soil heavy metal pollution or determining environmental capacity of heavy metal in soil.  相似文献   

15.
Abstract

The influence of soil organic matter on selenite sorption was investigated in the selenite adsorption capacity and the surface particle charge change by ligand exchange reaction using the hydrogen peroxide (H2O2) treatment and the ignition treatment of two Andosols. The removal of organic carbon (C) in soils accelerated selenite sorption, implying that organic matter of soils had negative influence on the selenite adsorption on the soils. Positive charge decrease on soil particles, concomitant proton consumption, and release of silicon (Si), sulfate (SO4 2‐), and organic C were observed in selenite sorption by the soils. The development of surface particle negative charge with selenite sorption was smaller in the H2O2‐treated soil than in the original soils and was scarcely observed in the ignition‐treated soil. It can be assumed that the increase of negative charge by selenite sorption was attributed to new negative sites borne by released insoluble organic matter and negative charge development directly by selenite sorption was small.  相似文献   

16.
A simple mechanistic model is developed for predicting the fate of radioactive caesium in the soil beneath grassland. A continuity equation is derived describing the diffusion, leaching and reaction of caesium in soil, with uptake by a uniformly distributed root system. The soil reaction is characterized by three phases: an instantaneous exchange, a moderately-fast reversible reaction and a slow reversible reaction. The time-dependent reactions and root uptake have first-order kinetics. It is shown that caesium is unlikely to be removed from the root zone by leaching and diffusion, even under prolonged high rainfall. Therefore, since the rates of the soil reactions and root uptake are much greater than the rates of diffusion and leaching, it is not necessary to calculate the concentration profile to find the rate of uptake. The computer program for the model is just 30 lines of fortran , and requires only a few seconds of micro-computer CPU time for each year of simulation.
Some predicted rates of plant uptake and distributions in the soil are given. It is seen that the fate of the caesium is markedly influenced by soil parameters dependent on soil clay content, clay mineralogy, organic matter content, cation saturation and pH, and by the rooting density. The predicted rates of uptake vary from about 0.5% to 50% per annum, which is compatible with data reported elsewhere. The predictions are intended to expose gaps in knowledge of the fate of caesium in soil: in particular, the mobility of sorbed radio-nuclides on soil surfaces needs further study. Predictions are not given for the fate of caesium in any real situations because insufficient data are available.  相似文献   

17.
Changes in sorption/bioavailability of two metabolites, imidacloprid-urea {1-[(6-chloro-3-pyridinyl)methyl]-2-imidazolidinone} and imidacloprid-guanidine {1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine} of the insecticide imidacloprid {1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine} with aging in different soils were determined. Soil moisture was adjusted to -33 kPa and 14C- and analytical-grade imidacloprid-urea and imidacloprid-guanidine were added to the soil at a rate of 1.0 mg kg-1. Spiked soils were incubated at 25°C for 8 weeks. Replicate soil samples were periodically extracted successively with 0.01 N CaCl2, acetonitrile, and 1 N HCl. Imidacloprid-urea sorption, as indicated by sorption coefficient values, was highest in the soil with highest organic C content, and increased by an average factor of 2.6 in three soils during the 8-week incubation period. Imidacloprid-guanidine sorption increased by a factor of 2.3 in the same soils. The increase in sorption was the result of a decrease in the metabolite extractable with CaCl2 (solution phase); the amount of metabolite extractable with acetonitrile and HCl (sorbed phase) did not significantly change with incubation time. It appears the increase in sorption was because the rate of degradation in solution and on labile sites was faster than the rate of desorption from the soil particles. It may have also been due to metabolite diffusion to less accessible or stronger binding sites with time. Regardless of the mechanism, these results are further evidence that increases in sorption during pesticide aging should be taken into account during characterization of the sorption process for mathematical models of pesticide degradation and transport.  相似文献   

18.
《Geoderma》2001,99(3-4):225-243
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19.
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20.
Pesticide leaching from soil has been shown to decrease with increasing time from application to irrigation. It is hypothesized that the availability of compounds for leaching decreases due to diffusion and sorption inside soil aggregates. Previous work showed that pesticide sorption inside soil aggregates increases significantly during the first days after application. The study presented here tested if diffusion into aggregates could explain the leaching of four aged pesticides from manually irrigated soil cores. Azoxystrobin, chlorotoluron, cyanazine, and bentazone were applied to 30 undisturbed cores (25 cm long, 23.7 cm diameter) from a clay loam soil. The soil cores were irrigated 1, 3, 7, 14, and 28 days after application. Leachate was collected and analyzed. The amount of pesticide found in leachate decreased rapidly with time from application. Pesticide losses in leachate declined 2.5-27 times faster than total residues in soil. The decline was 4-5 times faster for the more strongly sorbed pesticides (azoxystrobin, chlorotoluron, and cyanazine) than for bentazone. In previous work, we derived a model to describe sorption and diffusion of the pesticides in small aggregates from the same soil. The diffusion model was used here to describe sorption inside the large aggregates in the soil cores and extended to describe pesticide leaching by interaggregate flow. The model showed a significant decline in leaching with time from application, which supports the theory that diffusion-limited sorption in aggregates influences the availability for pesticide leaching, although it does not exclude alternative explanations for this decline. The model well described the decline in leaching for three out of four pesticides. The interaggregate transport model could, however, not account for the amount of preferential flow in the cores and underestimated the leaching of bentazone.  相似文献   

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