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1.
Desorption experiments were conducted on 21 soils at 3 atrazine concentrations. The Freundlich isotherm was used to estimate atrazine desorption. For the relationship between Freundlich isotherm coefficients, log K F and 1 / n, 1 / n was also represented by a linear regression of log K F as in the case of atrazine adsorption. All the linear regression lines of desorption exhibited larger slopes and intercepts than those of adsorption. When the atrazine concentration was high, the slope and intercept values were smaller than those for the desorption regression lines. The results showed that the larger the capacity of a soil to adsorb atrazine, the lesser the amount of atrazine desorbed. For the cultivated soils except for Andisols, the percentages of atrazine taken from solutions using the sequential exchange method after the first adsorption experiments, were the same as those desorbed from soils in relation to the initial amount adsorbed. Thus, reversible adsorption occurred in the soils due to weak physical adsorption.  相似文献   

2.
The adsorption-desorption equilibrium of atrazine (2-chloro, 4-ethylamino, 6-isopropyl amino-1, 3, 5 triazine) was studied by the batch equilibration method at 27 ± 1 °C on four soils of Hyderabad. Adsorption isotherms conformed to the Freundlich equation (A = KC1/n ). K increased in the same order as the organic C content of the soils. Desorption studies were conducted by repeated replacement of 5 mL of the supernatant equilibrium solutions after adsorption, with 0.01 M CaCl2. Desorption isotherms showed considerable hysteresis which was more prominent when the desorption was carried out with higher adsorbed concentration of atrazine. Desorption from the lowest level of adsorbed atrazine (3 to 5 μg g?1 soil) was close to the adsorption isotherm. The cumulative desorption after four desorption steps covering five days was significantly different at the 1% level, for different initial adsorbed concentrations of atrazine. Desorption was significantly higher at the lowest adsorbed level of atrazine. The soils differed significantly at 6% level for desorption and the amount desorbed decreased in the inverse order of organic C. Desorption isotherms also conformed to Freundlich equation but K andn values were both higher than that for adsorption and increased with increase in initially adsorbed concentration of atrazine. Desorption thus confirmed the irreversible nature of the adsorption of atrazine on these soils. The quantitative factors and reasons for desorption are discussed.  相似文献   

3.
The adsorption kinetics and adsorption parameters of metolachlor, atrazine, deethylatrazine (DEA), deisopropylatrazine (DIA) and hydroxyatrazine (HA) were investigated in a soil profile in a maize field formed from recent alluvial deposits in a river basin in Greece. We used the batch equilibrium method modified to simulate field conditions as closely as possible for the use and practices related to soil applied pre‐emergence herbicides. Pseudo‐equilibrium times, determined by kinetic studies, were achieved after 16, 16, 24, 24 and 48 hours for metolachlor, DIA, DEA, HA and atrazine, respectively. At pseudo‐equilibrium the percentage of the adsorbed amount increased in the order of DEA (10%) < DIA (14%) < atrazine (27%) < metolachlor (43%) ≪ HA (94%) which indicates that more than 57% of all compounds except for HA are in solution and available for transport to deeper soil layers when conditions similar to those simulated in the laboratory exist in the field. Adsorption isotherms of all compounds and in most of the cases correlated well with the Freundlich model and adsorption coefficients (Kf) decreased with increased soil depth. Principal component and multiple regression analyses confirmed the importance of the soil organic carbon content on the adsorption capacity of soils for all compounds except HA in the plough layers (0–40 cm). In the subsurface soils (40–110 cm) variables such as clay content and pH were more important. For HA, the Kf values determined for the plough and subsurface soil layers were better correlated with clay content and pH. Also in the subsurface soils, the variation in organic carbon content was not correlated with the variation of Kf values. Thus calculated Koc‐f‐values misrepresent the adsorptive capacity of these soils towards the compounds studied.  相似文献   

4.
The adsorption of a radioisotope of caesium, 137Cs, has been interpretation and ratio and solution measured on four soils with differing clay mineralogies. All measurements have been made using unwashed soils in suspensions shaken for 2 h at 20°C. The effects of concentration in potassium and caesium, the nature of the background electrolyte and the soil:solution ratio have been investigated. The results are expressed either as the distribution coefficient, KD or as Freundlich isotherms. The distribution coefficient of each of the soils decreases markedly as the concentration of caesium increases. The adsorption properties of the soils are not determined by the dominant clay mineralogy alone. Adsorption is always lower in 0.01 m CaCl2 solution than in water. The addition of potassium has relatively little effect on adsorption of trace amounts of caesium; however, KD decreases with increasing concentrations of stable caesium. The major reason for the dependence of KD on the soil: solution ratio is found to be the non-linear adsorption isotherm; the influence of the varying compositions of the solution and exchange complex is minor. The validity of the use of a single KD value as an indicator of adsorption capacity and the meaning of the relative values of the Freundlich parameters are considered. The implications of these findings for the use of radiotracers and the usefulness of KD as an indicator of bioavailability are discussed.  相似文献   

5.
Abstract

The sorption behavior of three triazine herbicides: atrazine, metribuzin, and terbutryn was studied in two different soils. Three experimental procedures to determine the Kf values were assayed: the conventional batch equilibration method in which the sorbed concentration is calculated by difference from the change in solution concentration; an alternative mass balance equilibrium batch technique in which the solution and the sorbed phase concentration are measured directly; and the flow equilibration method in which a solution of known concentration was passed through a column of soil until the effluent reached the same concentration as the input solution. Four concentrations of each herbicide were selected and results were fitted to the linearized form of the Freundlich isotherm. Recovery of the herbicides was studied in soil and water samples using the same four concentrations employed in the sorption assays. Average recoveries ranged from 86 to 104% with standard deviations lower than 10%. The Koc (mg1–1/n kg‐1 Ll/n) values obtained ranged from 43 to 87 for atrazine, 27 to 114 for metribuzin, and 355 to 505 for terbutryn. The exponents 1/n of the Freundlich adsorption isotherms were lower than unity, with only one exception, and varied from 0.72 to 0.86 for atrazine, 0.73 to 1.12 for metribuzin, and 0.76 to 0.99 for terbutryn. The solution method gave values of Koc that were 1.25, 1.55, and 2.65 (average of both soils) times those of the mass balance method for terbutryn, atrazine and metribuzin, respectively. When adsorption was low, the mass balance calculation method is recommended if the batch equilibration method is used, since the solution method can produce a considerable overestimation of adsorption. The flow equilibration method produced similar values of adsorption than the mass balance batch equilibration method and it made the experimental procedure easier since pesticide solution concentration need not to be measured once the equilibration time has been determined to ensure that the equilibrium was reached.  相似文献   

6.
Atrazine [6-chloro-N-ethyl-N′-(1-methyl)-1,3,5 triazine-2,3-diamine] and alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide] are agricultural herbicides used in large quantities and, as a consequence, are common contaminants in groundwater and surface water. The retention of these herbicides in soils and their degradation in aqueous environments is highly dependent upon their adsorption to solid surfaces. The adsorption of atrazine and alachlor was investigated on three typical Kansas and underlying aquifers known to be vulnerable to contamination. More alachlor was adsorbed to the soils and sediments than atrazine. The adsorption coefficients for atrazine were 2 to 5 times higher for soils than for aquifer sediments. For alachlor, the adsorption coefficients were 4 to 20 times higher for soil than for aquifer solids. Both linear and Freundlich isotherms represented the adsorption data well in all cases. The slope of the Freundlich isotherms, 1/n, was close to one, with the exception of alachlor adsorption onto the Topeka aquifer sediment (1/n = 0.67). The K d values found in these studies were comparable to the lower range of those reported in the literature.  相似文献   

7.
Adsorption and desorption of the herbicides glyphosate [N-phosphonomethyl-aminoaceticacid], simazine [6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-diamine] and atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine] were studied in four sandy soils from Western Australia. Distribution coefficients (Kds) were calculated from breakthrough curves (BTCs) resulting from leaching step changes in concentrations through small saturated columns of soil at flow rates ranging from 0.3 to 30 m day–1. A comparison was made with Kds obtained after batch equilibrating solutions of the herbicides with the same soils. The Kds of herbicides in soils decreased with increasing flow rate and most strongly for glyphosate in soils rich in clay content. Resulting increases in mobility of about 40–50% were estimated for simazine and atrazine and > 50% for glyphosate at flow rates of 3 m day–1. Adsorption and desorption rates were estimated by fitting numerically simulated BTCs to experimental BTCs. Best fits were obtained with a time-dependent Freundlich adsorption equation. The resulting coefficient for time dependency in the equation suggests that the rates of adsorption and desorption are controlled mainly by diffusion in an adsorbing layer on or in soil particles.  相似文献   

8.
The mobility, bioavailability, and environmental fate of heavy metals in soil are controlled by their adsorption onto soil minerals and solid organic matter. The adsorption is strongly affected by the presence of various low-molecular-weight organic acids. In this study, effect of hydroxamate siderophore desferrioxamine B (DFOB) on cadmium (Cd) and zinc (Zn) adsorption onto two micaceous clay minerals, muscovite and phlogopite, was evaluated in batch experiments. Results showed that the presence of DFOB diminished the adsorption of Cd and Zn onto both minerals, particularly under neutral to alkaline pH conditions. For instance, at pH 8.2, the presence of DFOB caused a decrease in the adsorption of Zn onto phlogopite by nearly 50%. The equilibrium adsorption of Cd and Zn was satisfactorily described using Freundlich isotherm. The adsorption isotherms showed that the affinity of Cd and Zn onto the minerals decreased in the presence of DFOB. For example, at pH 8.0, the presence of siderophore caused a decrease in the Freundlich adsorption isotherm coefficient KF for Zn adsorption onto muscovite and phlogopite from 4.60 to 0.07 L g-1 and from 3.56 to 0.36 L g-1, respectively. These findings confirm the potential influence of siderophore on the fate of Cd and Zn in arid soils containing substantial contributions of micaceous silicate minerals.  相似文献   

9.
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   

10.
Abstract

Zinc adsorption by 10 (pH 4.0–6.5) cultivated mineral soils from Finland was studied in batch experiments. Additions of Zn ranged up to 600 mg kg?1 of soil and the corresponding equilibrium concentrations were 0.1–13 mg 1?1. In each soil, Zn adsorption conformed to the Freundlich isotherm. Despite a relatively low initial Zn adsorption by the acidic soils, each of the soils proved to have a high potential to adsorb Zn, but the capacity was highly pH dependent. In addition to the conventional Freundlich adsorption isotherms, calculated separately for each soil, extended Freundlich-type isotherms that also incorporate soil pH and other soil characteristics were used to describe Zn adsorption of several soils simultaneously in one equation. The pH-dependent Freundlich adsorption isotherm proved to serve as a practical tool to assess Zn adsorption by soils varying in pH and other characteristics.  相似文献   

11.
This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients KF increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO3)2 < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants KF and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.  相似文献   

12.
The prediction of the mobility of arsenic (As) is crucial for predicting risks in soils contaminated with As. The objective of this study is to predict the distribution of As between solid and solution in soils based on soil properties and the fraction of As in soil that is reversibly adsorbed. We studied adsorption of As(V) in suspensions at radiotrace concentrations for 30 uncontaminated soils (pH 4.4–6.6). The solid–liquid distribution coefficient of As (Kd) varied from 14 to 4430 l kg?1. The logarithm of the concentration of oxalate‐extractable Fe explained 63% of the variation in log Kd; by introducing the logarithm of the concentration of oxalate‐extractable P in the regression model, 85% of the variation in log Kd is explained. Double labelling experiments with 73As(V) and 32P(V) showed that the As to P adsorption selectivity coefficient decreased from 3.1 to 0.2 with increasing degree of P saturation of the amorphous oxides. The addition of As(V) (0–6 mmol kg?1) reduced the Kd of 73As up to 17‐fold, whereas corresponding additions of P(V) had smaller effects. These studies suggest that As(V) is adsorbed to amorphous oxides in soils and that sites of adsorption vary in their selectivity in respect of As and P. The concentration of isotopically exchangeable As in 27 contaminated soils (total As 13–1080 mg kg?1) was between 1.2 and 19% (mean 8.2%) of its total concentration, illustrating that a major fraction of As is fixed. We propose a two‐site model of competitive As(V)–P(V) sorption in which amorphous Fe and Al oxides represent the site capacity and the isotopically exchangeable As represents the adsorbed phase. This model is fitted to 73As adsorption data of uncontaminated soils and explains 69% of the variation of log Kd in these soils. The log Kd in contaminated soils predicted using this two‐site model correlated well with the observed log Kd (r = 0.75). We conclude that solubility of As is related to the available binding sites on amorphous oxides and to the fraction of As that is fixed.  相似文献   

13.
On the relation of herbicide adsorption and soil organic fraction Freundlich adsorption isotherms were measured for four herbicides (atrazine, terbuthylazine, chlorotoluron, isoproturon) and 24 soil horizons, which are typical of Schleswig-Holstein, northern Germany. The relationship between the adsorption constant (KFr) of a chemical and the fraction of organic carbon (fOC) of the soil horizons was evaluated. Chemical specific K'OC-values, that are independent of soil organic carbon fraction varied considerably for each herbicide (CV about 50%); therefore these values as well as KOC-values, that are determined by linear regression of KFr and fOC should be evaluated critically before application. K'OC- and KOC-values derived from experiments showed decreasing affinity of the herbicides to soil horizons in the order terbuthylazine > chlorotoluron > atrazine ? isoproturon. Calculation of KOC from KOW or water solubility of each herbicide, however, led to changes in the above mentioned ranking. Hence, especially KOW or water solubility based KOC-values may lead to false conclusions concerning chemical mobility. For atrazine, terbuthylazine and isoproturon Freundlich adsorption constants increased overproportionally with increasing organic carbon content of soils. The relationships between KFr and fOC therefore were described better by a non-linear equation (second order polynom) than by a linear approach. Contrary, for chlorotoluron a linear relation between KFr and fOC holds at least for the range of fOC investigated in this study.  相似文献   

14.
The increasing frequency of chemically contaminated groundwater, occurring as a result of improperly managed waste disposal or accidental spills, presents a need for research on the fate of chemical mixtures in the soil. The batch equilibration technique was used to measure adsorption of 14C ring-labeled atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) for a Palouse silt loam (Pachic Ultic Haploxeroll) and a Pembroke silty clay loam (Typic Paleudalf). The solution phase consisted of mixtures of methanol-water and hexane-water containing up to 33.3 % organic solvent by volume. Aqueous solubility limited atrazine concentrations to 100 μmol L?1 except for an additional isotherm determined in 33.3 methanol-water at up to 1542 μmol L?1 The Freundlich adsorption coefficient indicated that the Palouse adsorbed more atrazine than the Pembroke with K values of 4.95 and 0.54, respectively. Both soils showed a significant decrease in K as the percentage methanol increased. Adsorption isotherms from a 33. 3 methanol-water system were of the Freundlich type for atrazine concentrations of 0.25 to 1542 μmol L?1. In the hexane-water systems, K decreased as the fraction of hexane increased and the Pembroke soil adsorbed less atrazine than the Palouse soil. These results suggest that the introduction of nonaqueous solvents such as methanol and hexane decreased adsorption and increased the potential for atrazine mobility.  相似文献   

15.

Purpose

Adsorption and desorption are important processes that influence the transport, transformation, and bioavailability of atrazine in soils. Equilibrium batch experiments were carried out to investigate the adsorption–desorption characteristics of atrazine. The objectives of this study were to (1) determine and quantify the main soil parameters governing atrazine adsorption and desorption phenomena; (2) find the correlativity between the identified soil parameters; and (3) investigate the universal desorption hysteresis traits.

Materials and methods

Fifteen soils with contrasting physico-chemical characteristics were collected from 11 provinces in eastern China. The equilibrium time was 24 h both for adsorption and desorption experiments. Atrazine was detected by Waters 2695/UV HPLC.

Results and discussion

Adsorption isotherms of atrazine could be well described by the Freundlich equation (r?≥?0.994, p?<?0.01). The total organic carbon (TOC) was the first independent variable that described 53.0 % of the total variability of K f, followed by the pH (9.9 %), and the clay (4.0 %) and silt (1.2 %) contents, separately; while the primary soil properties that affect desorption parameters included the TOC, pH, free Fe2O3 (Fed) and the sand content, with the biggest contribution achieved by the TOC (ranged from 48.5–78.1 %). The results showed that when the content ratio of clay to TOC (RCO) was less than 40, the atrazine adsorption was largely influenced by the organic matrix, while when the RCO was greater than 40, they were vital affected by the clay content.

Conclusions

Adsorption–desorption isotherms of atrazine in soils were nonlinear. The content of TOC, clay, and iron oxides, as well as the pH value were the key soil parameters affecting the adsorption–desorption of atrazine in soil, among which the RCO especially exhibited relevance. Additionally, the desorption hysteresis existed for atrazine retention in all 15 tested soils, and the hysteretic effect enhanced with the increasing time for desorption. This would be ascribed to the heterogeneity physical–chemical properties of these soils.  相似文献   

16.
叶炳  王虹 《土壤学报》1984,21(1):21-28
目前应用Langmuir吸附等温式来探讨土壤对磷酸离子的吸附作用,较为广泛.自从Olsen(1957)系统地报道以来,从机理到结合生产实际的研究已有大量的报道,我国近年来也有研究.由于土壤本身组成的复杂性,多数学者用纯物质(如纯粘土或铁与铝的含水氧化物等)进行吸附等温式的机理研究,已取得了很多结果.  相似文献   

17.
This study was carried out to investigate the sorption properties of man‐made soil developed from sewage sludge, municipal wastes, brick and mortar debris, harbour sludge, sand fills, fly ash, and wastes from coking plants and coal mines. The composition of organic matter in the samples was analysed, and the sorption isotherms of four reference chemicals (nitrobenzene, atrazine, 2,4‐D, pentachlorophenol) were determined. Fly ash, which contains up to 89% of its carbon as Black Carbon, showed a strong affinity to all four chemicals. For the other waste materials, a strong correlation between the logarithm of the Freundlich adsorption constant, Kf, and the logarithm of organic carbon, Co, was established (r = 0.85–0.96). This holds for the non‐ionic nitrobenzene and also, within a certain pH range depending on the pKa of the compound, for the three ionizable organic compounds (atrazine: pH > 4; 2,4‐D: pH > 5; PCP: pH > 6). At pH near the pKa value the sorption is sensitive to pH. There were no statistically significant differences between the waste materials and the natural soils in the relations between logKf and logCo for either ionic or non‐ionic chemicals. This result suggests that the method devised for estimating the sorption of organic chemicals in natural soils based on their content of organic carbon is equally valuable for the waste materials, with the exception of fly ash which contains a large amount of Black Carbon.  相似文献   

18.
Dissolved organic matter enhances the sorption of atrazine by soil   总被引：6，自引：0，他引：6  
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.  相似文献   

19.
乙草胺和异丙甲草胺在土壤中吸附的研究   总被引：29，自引：1，他引：28  
王琪全  刘维屏 《土壤学报》2000,37(1):95-101
本文研究比较了乙草胺和异丙甲草胺在６种土壤中的吸附,采用Ｆｒｅｕｎｄｌｉｃｈ方程对其吸附等温线进行描述,对Ｆｒｅｕｎｄｌｉｃｈ方程吸附常数Ｋａｔ和Γ／ｎ的乘积与土壤理化性质的相关性进行了分析,并探讨乙草胺和异丙甲草胺在腐殖酸上的吸附机理。结果表明,乙草胺和异丙甲草胺在土壤中吸附主要受土壤有机质支配,有机质含含量越高越有利于这两种除草剂在土壤上的吸附。异丙甲草胺在土壤中的吸附明显弱于乙草胺。氢键是乙  相似文献   

20.
Batch adsorption experiments were carried out with samples from an A-, Bh- and C-horizon of contaminated sandy soil of podzolic character from the Kempen region at the Dutch-Belgian border. Cadmium sorption was studied on 3 soil samples at 3 different pH-levels (3.6, 4.3 and soil buffered pH) and 3 different additions of zinc (0–40 mg l-1). Adsorption of cadmium by acid sandy soils can be fitted by a Freundlich adsorption isotherm. Although zinc competes with cadmium for the sorption sites, we observe a two to three times stronger competition effect of the proton cation, which is explained by the chemical properties of both ions. The cadmium adsorption coefficient KF decreases considerably by an increase of the proton activity used in the sorption experiments. Organic matter content explains for a large part the variation of KF of te three soil samples. Desorption data do not fit the proposed regression model for adssorption. Not all the cadmium, intitially present in the polluted soil, will fylly desorb reversibly. Thus, part of the cadmium may be irreversible bound.  相似文献   

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