Alginate and lignin-based formulations to control pesticides leaching in a calcareous soil.

Important risk of groundwater pollution has been observed as a result of rapid leaching of highly soluble pesticides when used in agronomic practices as conventional formulations. This risk can be minimized through the application of the pesticide at a set rate using controlled release formulations (CRFs). In this research, CRFs of isoproturon, imidacloprid and cyromazine have been evaluated in a calcareous soil. The effects of two natural polymers (alginate and lignin) and two modifying sorbents (bentonite and activated carbon) on pesticide release kinetics from CRFs have been investigated, as well as mobility of pesticides using soil columns. The rate of pesticide release in soil from CRFs diminished in all cases in relation to technical products. From the analysis of the time taken for 50% of the active ingredient to be released into soil (T(50 soil)), it can be deduced that the release rate of pesticides can be controlled by using activated carbon in the alginate-based CRFs and mixing the pesticide with kraft lignin. Mobility experiments showed that the use of CRFs clearly reduces the presence of isoproturon and imidacloprid in the leachate compared to technical products, and to a lesser extent for cyromacine due to its high water solubility.

Lignin-based formulations to prevent pesticides pollution.

The pesticides isoproturon, imidacloprid and cyromazine, identified as groundwater pollutants, were incorporated in lignin-based formulations to obtain controlled release (CR) properties. The formulations were prepared by mixing the pesticide with a commercially available pine kraft lignin under melting conditions. A high efficiency of the preparations was therefore reached; it oscillated between 93.36% and 98.20% for the cyromazine and the isoproturon formulations. Kinetic-release experiments carried out in water showed that the release rate of isoproturon, imidacloprid and cyromazine from CR granules diminished in all cases in relation to the technical products. From the analysis of the time taken for 50% of the active ingredient to be released into water (T(50)), it can be deduced that the release rates were much higher in cyromazine CR formulations than in those prepared with isoproturon. However, imidacloprid showed an intermediate release rate. The obtained linear regression between T(50) values and granule size can be suitable to select the most appropriate formulation to avoid the isoproturon, imidacloprid and ciromazine tendency to leach.

Adsorption of chloridazon from aqueous solution on modified kerolite-rich materials.

The adsorption of chloridazon (5-amine-4-chloro-2-phenylpyridazin-3(2H)-one) on kerolite samples heated at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400), 600 degrees C (K-600) and acid-treated with H(2)SO(4) solutions of two different concentrations (0.25 and 0.5 M) (K-0.25 and K-0.5, respectively) from pure water at 25 degrees C has been studied by using batch and column experiments. The adsorption experimental data points were fitted to the Freundlich equation in order to calculate the adsorption capacities (K(f)) of the samples; K(f) values ranged from 184.7 mg kg(-1) (K-0.5) up to 2253 mg kg(-1) (K-600). This indicated that the heat treatment given to the kerolite greatly increases its adsorption capacity for the herbicide whereas the acid treatment produces a clear decrease in the amount of chloridazon adsorbed. The removal efficiency (R) was also calculated; R values ranging from 52.8% (K-0.5) up to 88.3% (K-600). Thus, the results showed that the 600 degrees C heat-treated kerolite was more effective in relation to adsorption of chloridazon and it might be reasonably used in removing this herbicide from water.

Controlled release of isoproturon, imidacloprid, and cyromazine from alginate-bentonite-activated carbon formulations.

Different alginate-based systems of isoproturon, imidacloprid, and cyromazine have been investigated in order to obtain controlled release (CR) properties. The basic formulation [sodium alginate (1.50%), pesticide (0.30%), and water] was modified using different amounts of bentonite and activated carbon. The higher values of encapsulation efficiency corresponded to those formulations prepared with higher percentages of activated carbon, showing higher encapsulation efficiency values for isoproturon and imidacloprid than for cyromazine, which has a higher water solubility. The kinetic experiments of imidacloprid/isoproturon release in water have shown us that the release rate is higher in imidacloprid systems than in those prepared with isoproturon. Moreover, it can be deduced that the use of bentonite and/or activated carbon sorbents reduces the release rate of the isoproturon and imidacloprid in comparison with the technical product and with alginate formulation without modifying agents. The highest decrease in release rate corresponds to the formulations prepared with the highest percentage of activated carbon. The water uptake, permeability, and time taken for 50% of the active ingredient to be released into water, T50, were calculated to compare the formulations. On the basis of a parameter of an empirical equation used to fit the pesticide release data, the release of isoproturon and imidacloprid from the various formulations into water is controlled by a diffusion mechanism. The sorption capacity of the sorbents and the permeability of the formulations were the most important factors modulating pesticide release. Finally, a linear correlation of the T50 values and the content of activated carbon in formulations were obtained.

Cosorption study of organic pollutants and dissolved organic matter in a soil.

In this study we have evaluated the effects of dissolved organic matter (DOM) on sorption of imidacloprid, 3,4-dichloroaniline (3,4-DCA) and 4-bromoaniline (4-BA) on a typical calcareous soil (Luvic Xerosol) from south-eastern Spain. Two different types of DOM were used, that is to say, dissolved natural organic matter extracts from a commercial peat (DNOM) and a high-purity tannic acid (TA) solution. The experiments were carried out in a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results indicated that the presence of both DNOM and TA, over a concentration range of 15-100 mg L(-1), produced an increase in the amount of 3,4-DCA and 4-BA sorbed and a decrease in the amount of imidacloprid retained on the soil studied. A modified distribution coefficient, K(doc), has been proposed as a safer parameter for soil sorption predictions of organic pollutants and it could be of help to model the fate of these in the environment.

Adsorption of chloridazon from aqueous solution on heat and acid treated sepiolites.

The adsorption of chloridazon on heat treated sepiolite samples at 110 degrees C (S-110), 200 degrees C (S-200), 400 degrees C (S-400), 600 degrees C (S-600) and acid treated samples with H2SO4 solutions of two different concentrations (0.25 and 1.0M) (S-0.25 and S-1.0, respectively) from pure water at 25 degrees C has been studied by using batch experiments. In addition, column experiments were carried out with the natural (S-110) and 600 degrees C (S-600) heat treated samples, using a 10.30 mg l-1 aqueous solution of chloridazon. The adsorption experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (Kf) of the samples; Kf values range from 2.89 mg kg-1 for the S-1.0 sample up to 164 mg kg-1 for the S-600 sample; so, the heat treatment given to the sepiolite greatly increases its adsorption capacity for the herbicide chloridazon whereas the acid treatment produces a clear decrease in the amount of chloridazon adsorbed. The removal efficiency (R) has also been calculated; R values ranging from 5.08% for S-1.0 up to 60.9% for S-600. The batch experiments showed that the strongest heat treatment is more effective than the natural and acid treated sepiolite in relation to adsorption of chloridazon. The column experiments also showed that 600 degrees C heat treated sepiolite might be reasonably used in removing chloridazon from water. Thus, as this type of clay is relatively plentiful, these activated samples might be reasonably used in order to remove chloridazon from water.

Effects of dissolved organic carbon on sorption of 3,4-dichloroaniline and 4-bromoaniline in a calcareous soil.

To evaluate the effects of dissolved organic carbon on sorption of 3,4-dichloroaniline (3,4-DCA) and 4-bromoaniline (4-BA) on soils, batch sorption experiments were carried out. The soil used was a typical calcareous soil from south-eastern Spain. Two different types of dissolved organic carbon were used, that is, dissolved organic carbon extracts from a commercial peat (DOC-PE) and high-purity tannic acid (DOC-TA). The experiments were carried out in a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results obtained from the sorption experiments show that the presence of both DOC-PE and DOC-TA, over a concentration range of 15-100 mg l-1, produced in all cases, an increase in the amount of 3,4-DCA and 4-BA adsorbed on the soil studied.

Effects of ionic strength and temperature on adsorption of atrazine by a heat treated kerolite.

The adsorption of 6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on a heat treated kerolite sample at 600 degrees C (K-600) from pure water solution at 10 degrees C, 25 degrees C and 40 degrees C has been studied. The influence of the presence of 0.1 M KCl in the medium was also investigated for a better understanding of variables affecting the adsorption of this herbicide. The experimental adsorption data points were fitted to the Langmuir equation in order to calculate the adsorption capacities (Xm) of the samples; Xm values range from 2.3x10(3) mg kg-1 (pure water solution at 40 degrees C) up to 15.2x10(3) mg kg-1 (0.1 M KCl solution at 10 degrees C). The adsorption data were also fitted to the Freundlich equation in order to clarify the influence of the presence of 0.1 M KCl on atrazine adsorption. The parameter K10 obtained from this equation (adsorption capacity at an equilibrium solution concentration of atrazine equal to 10 mg l-1) shows clearly that the presence of 0.1 M KCl in the medium tends to increase the adsorption of atrazine in the range of temperature studied. The adsorption experiment also showed that the lower temperature, the more effective the adsorption of atrazine from both, pure water and 0.1 M KCl solutions. The values of the removal efficiency (R) obtained ranged from 39% at 40 degrees C (pure water solution) up to 93% at 10 degrees C (0.1 M KCl solution).

The potential removal of imidacloprid from water by heat-treated kerolites.

The adsorption of imidacloprid [1-(6-chloro-3-pyridinylmethyl)-N-nitroimidazolidin-2-ylideneamine] on heat-treated kerolite samples at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400) and 600 degrees C (K-600) from pure water solution at 25 degrees C has been studied. The evolution of the surface properties of the kerolite samples, such as specific surface area and porosity, after heat treatment were analysed. The clays were characterised by using FTIR spectroscopy, X-ray diffraction, thermogravimetric and differential thermogravimetric analysis, surface analysis and Hg porosimetry. The experimental adsorption data points were fitted to the Freundlich equation in order to calculate the adsorption capacities (Kf) of the samples; Kf values ranged from 242 mg kg(-1) for the K-110 sample to 1005 mg kg(-1) for the K-600 sample. The values obtained for the removal efficiency (R) ranged from 62.8% for K-110 to 87.2% for K-600. The adsorption experiments showed that the stronger the heat treatment, the more effective was the adsorption of imidacloprid from pure water. This work shows the potential use of heat-activated kerolite for the removal of imidacloprid from environmental waters and drinking water resources.

Adsorption of atrazine from aqueous solution on heat treated kerolites.

The adsorption of 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on heat treated kerolite samples at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400) and 600 degrees C (K-600) from aqueous solution at 25 degrees C has been studied. The evolution of surface properties of kerolite samples such as specific surface area and porosity after heat treatment was analysed. The clays were characterised by using usual techniques: FTIR spectroscopy, XRD diffraction, TG and DTG analysis, surface analysis and Hg porosimetry. The adsorption experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (K(f)) of the samples; K(f) values range from 468 mgkg(-1) for the K-110 sample up to 2291 mgkg(-1) for the K-600 sample. The values obtained for the removal efficiency (R), (percentage of pesticide removed), ranged from 48% for K-110 up to 78% for K-600. The adsorption experiments showed that the stronger heat treatment, the most effective adsorption of atrazine, so, as this type of clay is relatively plentiful, these activated samples might be used in order to remove this pesticide from water.

Effects of dissolved organic carbon on sorption and mobility of imidacloprid in soil.

To evaluate the effects of dissolved organic carbon on sorption and mobility of the insecticide imidacloprid [1-(6-chloro-3-pyridinyl) methyl-N-nitro-2-imidazolidinimine] in soils, adsorption and column experiments were performed by using a typical calcareous soil from southeastern Spain and two different types of dissolved organic carbon, that is, dissolved organic carbon extracts from a commercial peat (DOC-PE) and high-purity tannic acid (DOC-TA). The experiments were carried out from a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results obtained from the sorption experiments show that the presence of both DOC-PE and DOC-TA, over a concentration range of 15 to 100 mg L(-1), produces in all cases a decreasing amount of imidacloprid adsorbed in the soil studied. From the column experiments the retardation coefficients (RC) were calculated for imidacloprid by using either 0.01 M CaCl2 aqueous solution (RC = 2.10), 0.01 M CaCl2 DOC-PE solution (RC = 1.65), or 0.01 M CaCl2 DOC-TA solution (RC = 1.87). The results indicate that mobility of imidacloprid is increased 21.4 and 11.0% in the presence of DOC-PE and DOC-TA solutions, respectively. Dissolved organic carbon reduces imidacloprid sorption by competing with the pesticide molecules for sorption sites on the soil surface, allowing enhanced leaching of imidacloprid and potentially increasing ground water contamination.

Application of a single model to study the adsorption kinetics of prednisolone on six carbonaceous materials.

The knowledge of the adsorption processes of nonelectrolytes from liquid solution on solid materials involves the study of their kinetic and equilibrium aspects as well as the understanding of their thermodynamic functions. However, in most published papers adsorption isotherms are analyzed by using the Giles classification and other proposed equations which are either empirical or based on kinetic or thermodynamic criteria. Our opinion is that both the kinetic and the equilibrium studies must be complementary and that, in general, equations describing the adsorption isotherms come from the kinetic laws governing the different partial processes which determine the global process. These kinetic laws may be derived from single models. In this paper a single model is proposed, which makes it possible to establish a kinetic law satisfactorily fitting a great number of C (concentration) vs t (time) isotherms. This model has been applied to study the adsorption process of prednisolone by six carbonaceous materials from ethanol solution, the specific adsorption rate, and the activation thermodynamic functions being calculated. The results obtained have also been used to analyze the influence of the intraparticle diffusion on the kinetics of the process.

Application of a single model to study the adsorption equilibrium of prednisolone on six carbonaceous materials.

The knowledge of sorption processes of nonelectrolytes in solution by solid adsorbents implies the study of kinetics, equilibrium, and thermodynamic functions. However, quite frequently the equilibrium isotherms are studied by comparing them with those corresponding to the Giles et al. classification (1); these isotherms are also analyzed by fitting them to equations based on thermodynamic or kinetic criteria, and even to empirical equations. Nevertheless, information obtained is more coherent and satisfactory if the adsorption isotherms are fitted by using an equation describing the equilibrium isotherms according to the kinetic laws. These mentioned laws would determine each one of the unitary processes (one or more) which condition the global process. In this paper, an adsorption process of prednisolone in solution by six carbonaceous materials is explained according to a previously proposed single model, which allows to establish a kinetic law which fits satisfactorily most of C vs t isotherms (2). According to the above-mentioned kinetic law, equations describing sorption equilibrium processes have been deducted, and experimental data points have been fitted to these equations; such a fitting yields to different values of adsorption capacity and kinetic equilibrium constants for the different processes at several temperatures. However, in spite of their practical interest, these constants have no thermodynamic signification. Thus, the thermodynamic equilibrium constant (K) has been calculated by using a modified expression of the Gaines et al. equation (3). Global average values of the thermodynamic functions have also been calculated from the K values. Information related to variations of DeltaH and DeltaS with the surface coverage fraction was obtained by using the corresponding Clausius-Clapeyron equations.

Limitations on the role of incorporated organic matter in reducing pesticide leaching.

The use of organic amendments has been suggested as a method of controlling pesticide leaching through soils. The enarenados soils of the intensive horticulture of the Almeria province of southern Spain contain buried organic matter horizons above a soil layer amended with clay. This region is ideal for understanding the potential for and limitations of organic amendments in preventing pesticide pollution. This study measured the sorption and degradation potential of carbofuran in this soil system and the hydrological behaviour of the soil horizons. The sorption of carbofuran was controlled by the organic carbon content, the degradation was strongly pH-dependent and the acidic organic layer protected the sorbed carbofuran against degradation. Hydrologically, the soil system is dominated by ponding above an amended clay layer and by the presence of macropores that can transport water through this clay. A simple model is proposed on this basis and shows that although high levels of dissolved organic carbon can be released by buried organic horizons, the major control on re-release of sorbed pesticide is the potential for sorption hysteresis in this organic layer. A comparison of sorption and degradation data for carbamate insecticides used in the region with groundwater observations for these compounds shows that no amount of incorporated organic would protect against pollution from highly water-soluble compounds.

Mobility of atrazine from alginate-bentonite controlled release formulations in layered soil.

The mobility of atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine] from alginate-bentonite-based controlled release (CR) formulations was investigated by using soil columns. Two CR formulations based on sodium alginate (14.0 g kg(-1), atrazine (6.0 g kg(-1), natural or acid-treated bentonite (50 g kg(-1), and water (924 g kg(-1) were compared to technical grade product and commercial liquid (CL) formulation (Gesaprim 500FW). All herbicide treatments were applied to duplicate layered bed systems simulating the typical arrangement under a plastic greenhouse, which is composed of sand (10 cm), peat (2 cm), amended soil (20 cm) and native soil (20 cm). The columns were leached with 39 cm (1500 ml) and 156 cm (6000 ml) of 0.02 M CaCl2 solution to evaluate the effect of water volume applied on herbicide movement. When 39 cm of 0.02 M CaCl2 solution was applied, there was no presence of herbicide in the leachate for the alginate-bentonite CR treatments. However, 0.11% and 0.14% of atrazine appeared in the leachate when the treatment was carried out with technical grade and CL formulations, respectively. When 156 cm of 0.02 M CaCl2 solution was applied, the use of the alginate-acid treated bentonite CR formulation retards and reduces the presence of atrazine in the leachate as compared to technical product. Analysis of the soil columns showed the highest atrazine concentration in the peat layer. Alginate-bentonite CR formulations might be an efficient system for reducing atrazine leaching in layered soil and thus, it could reduce the risks of pollution of groundwater.

Mobility of isoproturon from an alginate-bentonite controlled release formulation in layered soil.

The mobility of isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea] from an alginate-based controlled release (CR) formulation was investigated by using soil columns. A layered bed system simulating the typical arrangement under a plastic greenhouse, which is composed of sand, peat, amended soil and native soil was used. The CR formulation was based on sodium alginate (1.87%), isoproturon (1.19%), natural bentonite (3.28%), and water (93.66%), and was compared to technical grade isoproturon. The use of the alginate-bentonite CR formulation produced less vertical mobility of the active ingredient as compared to the technical product. There was no presence of herbicide in the leachate when the alginate-bentonite CR formulation was used. However, 0.90% of isoproturon appeared when the treatment was carried out with technical grade material. Isoproturon mobility was modelled using the programme CMLS, which showed the peat layer to retard pesticide leaching. Analysis of the soil columns showed the highest isoproturon concentration in the peat layer.

Controlled release of carbofuran from an alginate-bentonite formulation: water release kinetics and soil mobility.

The insecticide-nematicide carbofuran was incorporated in alginate-based granules to obtain controlled-release (CR) properties. The basic formulation [sodium alginate (1.61%)-carbofuran (0. 59%)-water] was modified by addition of sorbents. The effect on carbofuran release rate, caused by the incorporation of natural and acid-treated bentonite (0.5 and 1.0 M H(2)SO(4)) in alginate formulation, was studied by immersion of the granules in water under shaking. The time taken for 50% of the active ingredient to be released into water, t(50), was longer for those formulations containing natural bentonite (6.1 h) or acid-treated bentonite (9.0 and 11.7 h for 0.5 and 1.0 M H(2)SO(4) treatments, respectively) than for the preparation without bentonite (4.7 h). It appears from the results that the release of carbofuran from the various formulations is controlled by a diffusion mechanism according to the n values obtained, which were close to 0.5 in all cases. The mobility of carbofuran from alginate-based CR formulations was investigated by using soil columns packed with a clay soil (53% clay and 0.08% organic matter). Two alginate-based CR formulations containing natural bentonite or acid-treated bentonite (0.5 M H(2)SO(4)) were compared to technical grade carbofuran. The use of alginate-based CR formulations resulted in a reduction of the leached amount of carbofuran compared with the total amount of pesticide leached using the technical product (50 and 75% for CR granules containing natural and acid-treated bentonite, respectively). Alginate-bentonite CR formulations might be efficient systems for reducing carbofuran leaching in clay soils, which would reduce the risk of groundwater pollution.

Sorption and leaching of atrazine and MCPA in natural and peat-amended calcareous soils from Spain.

The sorption and leaching of atrazine and MCPA (0.02 M CaCl(2) aqueous solution at 25 degrees C) by a calcareous soil from Southeastern Spain, after organic carbon (OC) amendment with a commercial peat (from 0.18% to 4.61% OC), were studied in batch and soil column experiments. Adsorption capacity (K(f)) values, obtained by fitting the experimental data to the Freundlich equation, ranged from 0.24 mg kg(-)(1) for MCPA sorption on the original soil to 5.47 mg kg(-)(1) for atrazine sorption on the peat-amended soil containing 4.61% OC. The breakthrough curves obtained from the step-function soil column experiments indicated that the amount of herbicide adsorbed ranged from 17.5 mg kg(-)(1) for MCPA in the original soil to 331 mg kg(-)(1) for atrazine in the peat-amended soil containing 1.67% OC. The results obtained from the pulse experiments indicate that the mobility of MCPA is much greater than that corresponding to atrazine.

Controlled release of diuron from an alginate-bentonite formulation: water release kinetics and soil mobility study.

The herbicide diuron was incorporated in alginate-based granules to obtain controlled release (CR) properties. The standard formulation (alginate-herbicide-water) was modified by the addition of different sorbents. The effect on diuron release rate caused by incorporation of natural and acid-treated bentonites in alginate formulation was studied by immersion of the granules in water under static conditions. The release of diuron was diffusion-controlled. The time taken for 50% release of active ingredient to be released into water, T(50), was calculated for the comparison of formulations. The addition of bentonite to the alginate-based formulation produced the higher T(50) values, indicating slower release of the diuron. The mobility of technical and formulated diuron was compared by using soil columns. The use of alginate-based CR formulations containing bentonite produced a less vertical distribution of the active ingredient as compared to the technical product and commercial formulation. Sorption capacities of the various soil constituents for diuron were also determined using batch experiments.