Two-compartment sorption of phenanthrene on eight soils with various organic carbon contents

Sorption characteristics of phenanthrene (PHE) were studied on eight soils with organic carbon contents spanning over an order of magnitude using phase distribution relationships (PDRs) at 1 h, 48 h, and 720 h contact times. A new algebraic method was employed to describe the sorption characteristics at different time intervals (between 1 h and 48 h, and 1 h and 720 h). It was found that nonlinearity increased with increasing contact time and sorption that occurred in the subsequent time interval following the initial 1 h exhibited stronger isotherm nonlinearity. Sorption coefficients were positively correlated with the organic carbon contents of the soils. Detailed sorption dynamics were also examined on these soils. A two-compartment, first-order model was used to describe the sorption dynamics. The rate constants of the two compartments differed 18-170 times, suggesting the dissimilar sorption behaviors of the mathematically separated compartments. These two compartments were labeled fast and slow sorption compartment according to the rate constants. Calculation showed that the fast compartment accounted for over 80% of the overall sorption at the initial 1 h, while the slow compartment predominated the total sorption in the following 47 h. By combining the discussion of PDRs and sorption dynamics, the contributions of the two compartments to linear and nonlinear sorption were differentiated. The slow sorption compartment made a major contribution to nonlinear sorption and possibly to sequestration of organic pollutants by these soils.     

Sorption kinetic characteristics of polybrominated diphenyl ethers on natural soils

Sorption kinetic characteristics of BDE-28 and BDE-47 on five natural soils with different organic carbon fractions were investigated, and could be satisfactorily described by a two (fast and slow)-compartment first-order model with the ratio of rate constants ranged from 9 to 94 times. The fast compartment made a dominant contribution (71% ∼ 94%) to the total sorption amount in the whole process, and accounted for over 90% of the increase in the total sorption amount at initial 5 h. The influence of the slow compartment on the increase in the total sorption amount became principal (above 90%) in the subsequent stage approximately from 9 h or 25 h to the apparent equilibrium at 265 h. The results proposed the different sorption behaviors of the mathematically classified compartments for BDE-28 and BDE-47, which may correspond to the different soil components, such as soil organic fractions with amorphous and condensed structures, respectively.     

Sorption kinetics of atrazine and diuron in soils from southern Brazil

Sorption kinetics of atrazine and diuron was evaluated in soil samples from a typical landscape in Paraná. Samples were collected (0-20 cm) in a no-tillage area from Mamborê, PR, which has been cultivated under a crop rotation for the last six years. Six sampling points of the slope were selected to represent a wide range of soil chemical and physical properties found in this area. Radiolabeled tracers (14C-atrazine and 14C-diuron) were used and the radioactivity was detected by liquid scintillation counting (LSC). Sorption was accomplished for increasing equilibration periods (0.5, 1.5, 3, 6, 12, 24, and 48 h). Kinetics data fitted adequately well to Elovich equation, providing evidences that soil reaction occurs in two distinct stages: a fast, initial one followed by a slower one. During the fast phase, 34-42 and 71-79% of total atrazine and diuron applied were sorbed to soil samples. No important differences were found among combinations of soil and herbicide sorption during the slow phase. The unrealistic conditions under batch experiments should be overestimating sorption in the fast phase and underestimating diffusion in the slow phase. Sorption of both herbicides was positively correlated to organic carbon and clay contents of soils, but atrazine was much less sorbed than diuron, showing its higher potential to contaminate groundwater, specially in sandy, low organic carbon soils.     

Sorption Kinetics of Atrazine and Diuron in Soils from Southern Brazil

Abstract

Sorption kinetics of atrazine and diuron was evaluated in soil samples from a typical landscape in Paraná. Samples were collected (0–20 cm) in a no-tillage area from Mamborê, PR, which has been cultivated under a crop rotation for the last six years. Six sampling points of the slope were selected to represent a wide range of soil chemical and physical properties found in this area. Radiolabeled tracers (¹⁴C-atrazine and ¹⁴C-diuron) were used and the radioactivity was detected by liquid scintillation counting (LSC). Sorption was accomplished for increasing equilibration periods (0.5, 1.5, 3, 6, 12, 24, and 48 h). Kinetics data fitted adequately well to Elovich equation, providing evidences that soil reaction occurs in two distinct stages: a fast, initial one followed by a slower one. During the fast phase, 34–42 and 71–79% of total atrazine and diuron applied were sorbed to soil samples. No important differences were found among combinations of soil and herbicide sorption during the slow phase. The unrealistic conditions under batch experiments should be overestimating sorption in the fast phase and underestimating diffusion in the slow phase. Sorption of both herbicides was positively correlated to organic carbon and clay contents of soils, but atrazine was much less sorbed than diuron, showing its higher potential to contaminate groundwater, specially in sandy, low organic carbon soils.     

Sorption kinetics of chlorinated hydrophobic organic chemicals

This is the second of a two-part series describing the sorption kinetics of hydrophobic organic chemicals. Part I “The Use of First-Order Kinetic Multi-Compartment Models” is published in issue 1 of this journal, pp. 21–28. Sorption kinetics of chlorinated benzenes from a natural lake sediment have been investigated in gas-purge desorption experiments. Biphasic desorption curves, with an initial “fast” part and a subsequent “slow” part, were found for all tested chlorobenzenes. From these results first-order sorption uptake and desorption rate constants were calculated with a two-sediment compartment model, which is presented in the first paper. In three sets of experiments the sorption uptake period and sediment/water ratio were varied. Rate constants are not influenced by these experimental conditions, which supports the partitioning concept for the sorption of hydrophobic organic chemicals in sediments.     

Influences of preparative methods of humic acids on the sorption of 2,4,6-trichlorophenol

Humic acids (HAs) are a major component of soil organic matter which strongly affects the sorption behavior of organic contaminants in soils. To assess the sorption-desorption characteristics of organic compounds on HAs, the organic adsorbent is usually isolated using an acid-base extraction method followed by air-drying or freeze-drying. In this study, a peat soil from the Yangming mountain area of Taiwan was sampled and repeatedly extracted followed by either air-drying or a non-drying treatment (denoted DHAs and NDHAs, respectively). The sorption of 2,4,6-TCP on HAs was evaluated using the batch method. Kinetic sorption results indicated that DHAs exhibited a two-step first-order sorption behavior, involving a rapid sorption followed by a slow sorption. The slow sorption may be attributed to the diffusion of 2,4,6-TCP through the condensed aromatic domains of HAs. On the contrary, the sorption of 2,4,6-TCP on NDHAs was extremely rapid, and the sorption data did not fit existing kinetic models. Each HA sample exhibited a nonlinear sorption isotherm. Sorption nonlinearity (represented by Freundlich N values) and K(oc) had a positive relationship with aliphaticity for DHAs; however, nonlinearity and K(oc) correlated positively with aromaticity when NDHAs adsorbents were used. We conclude that the air-drying technique may artificially create a more condensed area, which strongly affects the sorption characteristics of HAs. Thus, an incorrect evaluation of the sorption capacity and its relationship with the chemical composition of HAs would arise following use of the air-drying method.     

Long-term tillage effects on soil metolachlor sorption and desorption behavior

Sorption and desorption are two important processes that influence the amount of pesticides retained by soils. However, the detailed sorption mechanisms as influenced by soil tillage management are unclear. This study examined the sorption and desorption characteristics of metolachlor [2-chloro-N-(2-ethyl-6-methyphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] using the soil samples collected from the long-term conservation tillage (CnT) and conventional tillage (CT) research plots established in 1979 in Darlinton, SC. Humic acid (HA) and humin were extracted from the soils and used in the sorption experiments along with the whole soil samples. The sorption experiments were conducted using a batch-equilibration method. Three sequential desorption rinses were carried out following the sorption experiments. By comparing metolachlor sorption and desorption results we observed hysteresis for all soil samples and their organic matter fractions. Sorption nonlinearity (N) and hysteresis were dependent on the structure and composition of soil organic matter (SOM), e.g., Freundlich isotherm exponents (N) of HA and humin from CnT were higher than those of CT treatment, which may be related to high aromaticity of SOM fractions in CT treatment. Sorption capacity (K'f) was positively correlated with soil organic carbon (SOC) content. These results show that long-term tillage management can greatly affect metolachlor sorption and desorption behavior probably by qualitative differences in the structural characteristics of the humic substances.     

Sorption, degradation and mobility of ptaquiloside, a carcinogenic Bracken (Pteridium sp.) constituent, in the soil environment

Ptaquiloside (PTA) is a carcinogenic norsesquiterpene glucoside produced by Bracken in amounts up to at least 500 mg m(-2). The toxin is transferred from Bracken to the underlying soil from where it may leach to surface and groundwater's impairing the quality of drinking water. The objectives of the present study were to characterize the solubility, degradation and retention of PTA in soils in order to evaluate the risk for groundwater contamination. PTA was isolated from Bracken. The logarithmic octanol-water and ethyl acetate-water partitioning coefficients for PTA were -0.63 and -0.88, respectively, in agreement with the high water solubility of the compound. PTA hydrolysed rapidly in aqueous solution at pH 4 or lower, but was stable above pH 4. Incubation of PTA with 10 different soils at 25 degrees C showed three different first order degradation patterns: (i) rapid degradation observed for acid sandy soils with half life's ranging between 8 and 30 h decreasing with the soil content of organic matter, (ii) slow degradation in less acid sandy soils with half-lives of several days, and (iii) fast initial degradation with a concurrent solid phase-water partitioning reaction observed for non-acid, mostly clayey soils. The presence of clay silicates appears to retard the degradation of PTA, possibly through sorption. Degradation at 4 degrees C was generally of type (iii) and degradation rates were up to 800 times lower than at 25 degrees C. Sorption isotherms for the same set of soils were almost linear and generally showed very low sorption affinity with distribution coefficients in the range 0.01-0.22 l kg(-1) at a solution concentration of 1 mg l(-1) except for the most acid soil; Freundlich affinity coefficients increased linearly with clay and organic matter contents. Negligible sorption was also observed in column studies where PTA and a non-sorbing tracer showed almost coincident break-through. Leaching of PTA to the aqueous environment will be most extensive on sandy soils, having pH >4 and poor in organic matter which are exposed to high precipitation rates during cold seasons.     

Sorption of small metabolites of nonylphenol polyethoxylates in single and complex systems on aquatic suspended particulate matter

Sorption of nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) as well as their binary and ternary mixtures were studied and compared on three simulated suspended particulate matters (SPMs). Sorption dynamics of NP on the three SPMs could be divided into two phases, the rapid sorption phase and the slow sorption phase. A third phase, 'apparent desorption' occurred before the slow sorption phase for NP1EO and NP2EO as well as for all mixtures. Initial sorption rate increased with the OC% content of the SPMs. At low concentration, the sorption of NP, NP1EO and NP2EO (only at low concentration for 3# SPM) followed linear isotherm on the three SPMs. The linear Kd value of NP or NP1EO increased with the OC% content of SPM. In mixtures, sorption of NP, NP1EO and NP2EO increased significantly, and a 'critical point', after which sorption increased significantly, was observed in certain sorption isotherms.     

Formulation of a soil-pesticide transport model based on a compartmental approach

A semianalytical soil-pesticide transport model is formulated based on a compartmental approach to determine spatial and temporal variations of pesticide residues across a soil profile. The compartmental model is implemented by drawing an analogy between a series of continuous-flow stirred tank reactors and a soil horizon that consists of multiple perfectly mixed compartments. The analogy is strengthened by exploiting a relation between the compartment series and the conventional convective-dispersive equation (CDE) for vertical transport in the soil. Consequently, the number of compartments in the model formulation is not free, but dictated as a function of transport parameters. The model formulation allows consideration of arbitrary boundary value specifications and also, for some cases, spatially varying initial concentration profiles. Sorption kinetics is represented via a two-site model that involves a linear sorption isotherm and a first-order irreversible sorption or a radial diffusive penetrating model. For these three cases, analysis of the compartmental model allows the resultant concentration profiles to be expressed in terms of the Poisson distribution. When a nonlinear kinetic sorption model is used to simulate the sorption processes, an analytical solution is not found and a numerical approach is required.     

Sorption mechanism of DDT from aqueous phase

Sorption is one among the many techniques available for the removal of organic materials from potable water and waste water. Use of locally available Wood Charcoal (WC) is essential in place of costly activated charcoal to make the process more economical and lucrative. The vital objective of this investigation was to assess the performance of WC for the removal of DDT from the aqueous phase. The influence of important factors like, particle size, pH, and time of contact, which affects the sorption process was studied in this investigation using batch experiments. The removal kinetics were carried out under the temperature 27 degrees +/- 1 degrees C (room temperature) and the sorption kinetics constants were evaluated. Sorption equilibria study has also been carried out to develop the Freudlich's sorption isotherm equation from which the ultimate sorption capacity of WC for sorption of DDT was calculated.     

The influence of organic matter on sorption and fate of glyphosate in soil - Comparing different soils and humic substances

Soil organic matter (SOM) is generally believed not to influence the sorption of glyphosate in soil. To get a closer look on the dynamics between glyphosate and SOM, we used three approaches: I. Sorption studies with seven purified soil humic fractions showed that these could sorb glyphosate and that the aromatic content, possibly phenolic groups, seems to aid the sorption. II. Sorption studies with six whole soils and with SOM removed showed that several soil parameters including SOM are responsible for the strong sorption of glyphosate in soils. III. After an 80 day fate experiment, ∼40% of the added glyphosate was associated with the humic and fulvic acid fractions in the sandy soils, while this was the case for only ∼10% of the added glyphosate in the clayey soils. Glyphosate sorbed to humic substances in the natural soils seemed to be easier desorbed than glyphosate sorbed to amorphous Fe/Al-oxides.     

Sorption kinetics and its effects on retention and leaching.

Sorption of pesticides to substrates used in biopurification systems is important as it controls the system's efficiency. Ideally, pesticide sorption should occur fast so that leaching of the pesticide in the biopurification system is minimized. Although modeling of pesticide transport commonly assumes equilibrium, this may not always be true in practice. Sorption kinetics have to be taken into account. This study investigated the batch sorption kinetics of linuron, isoproturon, metalaxyl, isoxaben and lenacil on substrates commonly used in a biopurification system, i.e. cow manure, straw, willow chopping, sandy loam soil, coconut chips, garden waste compost and peat mix. The first-order sorption kinetics model was fitted to the observed pesticide concentrations versus time resulting in an estimated kinetic rate constant alpha. Sorption appeared to be fast for the pesticides linuron and isoxaben, pesticides which were classified as immobile, while less mobile pesticides displayed an overall slower sorption. However, the substrate does not seem to be the main parameter influencing the sorption kinetics. Coconut chips, which is a substrate with a high organic matter content showed slow sorption for most of the pesticides. The effect of different estimated alpha values on the breakthrough of pesticides through a biopurification system was evaluated using the HYDRUS 1D model. Significant differences in leaching behavior were observed as a result of the obtained differences in sorption kinetics.     

Sorption of imazaquin in soils with positive balance of charges

The herbicide imazaquin has both an acid and a basic ionizable groups, and its sorption depends upon the pH, the electric potential (psi0), and the oxide and the organic carbon (OC) contents of the soil. Sorption and extraction experiments using 14C-imazaquin were performed in surface and subsurface samples of two acric oxisols (an anionic "rhodic" acrudox and an anionic "xanthic" acrudox) and one non-acric alfisol (a rhodic kandiudalf), treated at four different pH values. Imazaquin showed low to moderate sorption to the soils. Sorption decreased and aqueous extraction increased as pH increased. Up to pH 5.8, sorption was higher in subsurface than in surface layers of the acric soils, due to the positive balance of charges resulted from the high Fe and Al oxide and the low OC contents. It favored electrostatic interactions with anionic molecules of imazaquin. For the subsurface samples of these highly weathered soils, where psi0 was positive and OC was low, it was not possible to predict sorption just by considering imazaquin speciation and its hydrophobic partition to the organic domains of the soil. Moreover, if Koc measured for thesurface samples were assumed to represent the whole profile in predictive models for leaching potential, then it would result in underestimation of sorption potential in subsurface, and consequently result in overestimation of the leaching potential.     

Sorption isotherms of brominated diphenyl ethers on natural soils with different organic carbon fractions

Sorption isotherms of BDE-28 and BDE-47 on natural soils with different contents of soil organic matter (SOM) were investigated. Due to low water solubility of BDEs and resulted narrow ranges of aqueous equilibrium concentration, the linear distribution model showed similar and good fitting efficiency to the linear portion of nonlinear Freundlich curve. For the same sample, the linear and nonlinear model fitting sorption coefficients were close. At the statistically significant level of 0.05 or 0.1, significant relationships of total organic carbon fraction (fOC) with the fitting sorption coefficients can be observed. As for BDE-28, the relationships of fOC and SOM fractions with the single point partition coefficients at different aqueous concentrations of BDEs were significant; while for BDE-47, the relationships became less significant or insignificant, especially at higher aqueous concentrations. The findings in this study may facilitate more understanding on transport and fate of studied BDEs in soil systems.     

Sorption and desorption kinetics of diuron, fluometuron, prometryn and pyrithiobac sodium in soils

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac-sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r2 value > 0.98. The herbicide sorption as measured by the distribution coefficient (Kd) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac-sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the Kd values were normalised to organic carbon content of the soils (Koc), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac-sodium < fluometuron < prometryn < or = diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac-sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step (omega = [nad/nde - 1] x 100). Soil type and initial concentration had significant effect on omega. The effect of sorption and desorption properties of these four herbicides on the off-site transport to contaminate surface and groundwater are also discussed in this paper.     

Role of pH in partitioning and cation exchange of aromatic amines on water-saturated soils

Predicting the reversible interactions between aromatic amines and soil is essential for assessing the mobility, bioavailability and exposure from contaminated sites. Reversible sorption mechanisms of aniline and alpha-naphthylamine were investigated by using single and binary solute sorption to five soils at several pH values, and by applying a distributed parameter (DP) model. The DP model assumes linear partitioning of the neutral species into soil organic matter domains and organic cation binding on negative-charged sites with the exchange coefficients represented by a Gaussian probability distribution. Sorption nonlinearity was attributed to cation exchange with varying site affinities, which was adequately simulated using the DP model. Greater uptake by hydrophobic partitioning and selectivity for cation exchange sites was observed for alpha-naphthylamine compared to aniline. Sorption of alpha-naphthylamine was not impacted quantitatively by aniline under those conditions examined; however, aniline sorption was reduced by alpha-naphthylamine with the largest reduction occurring in the soil with the lowest pH. DP model simulations showed that although hydrophobic partitioning increases with soil-solution pH, cation exchange still contributes significantly to the total sorption even at soil-solution pH values greater than pKa + 2.     

Thermodynamics of interaction of lindane on silty loam and silty clay loam Indian soils

Abstract

Interaction of lindane with silty loam and silty clay loam soils was studied in batch tests at 23, 30 and 37° C. Sorption experiments were carried out at four concentrations and for varying time of contact upto 72 hours. This was followed by desorption studies. No desorption was observed. The sorption data was analysed using sorption equations and evaluating the thermodynamic parameters. The sorption was found to be predominantly entropic in nature and a combined effect of adsorption and chemisorption. The effect of organic matter and other chemical and mineralogical constituents of soils has also been discussed. The sorption with single application of lindane with the two soil types indicates that the insecticide is less likely to reach groundwater.     

Sorption of ametryn and imazethapyr in twenty-five soils from Pakistan and Australia.

Sorption of ametryn and imazethapyr in 25 soils from Pakistan and Australia was investigated using the batch method. The soils varied widely in their intrinsic capacities to sorb these herbicides as shown by the sorption coefficients, Kd, which ranged from 0.59 to 47.6 for ametryn and 0.02 to 6.94 for imazethapyr. Generally the alkaline soils of Pakistan had much lower Kd values of both herbicides than the soils of Australia. Both soil pH and soil organic carbon (SOC) were correlated significantly with the sorption of ametryn, whereas only soil pH was strongly correlated with imazethapyr sorption. No correlation was found between Kd values of the herbicides and the clay contents of the soils. Multiple regression analysis showed that Kd values were better correlated (r2=0.94 and 0.89 for ametryn and imazethapyr, respectively) if SOC and pH were simultaneously taken into account. The study indicated that sorption of these herbicides in the alkaline soils of Pakistan was low and consequently there is considerable risk of groundwater contamination.     

Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48–72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K _d) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.