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The Fenton reaction-based anodic Fenton treatment (AFT) was applied to three widely used organic agrochemicals, carbaryl, mecoprop, and paraquat, in a clay slurry. The adsorption and degradation behaviors of these neutral (carbaryl), anionic (mecoprop), and cationic (paraquat) agrochemicals were studied in a slurry of SWy-2 Na(+)-montmorillonite clay, and adsorption isotherms were obtained at given experimental conditions. The d spacing (d 001) of the clay layer before and after adsorption or degradation was measured by X-ray diffraction (XRD). On the basis of the change of d spacing, molecular disposition at the clay interlayer was inferred: both mecoprop and paraquat form a monolayer sitting flat and parallel to the clay siloxane surfaces. Results show that, due to different adsorption mechanisms, the adsorption effect on chemical degradation by AFT varies with pesticide: strong and tight adsorption of paraquat at the clay interlayer protects paraquat from being attacked by hydroxyl radicals; loosely adsorbed carbaryl or mecoprop is readily degraded. XRD analysis clearly indicates that AFT is capable of effectively degrading interlayer noncationic organic chemicals that are not usually available for biodegradation.

Anodic Fenton treatment (AFT) has been shown to be effective in removing pesticides from aqueous solution in batch reactors with the formation of less toxic and more biodegradable products. To facilitate practical application of AFT, carbaryl degradation in a continuously stirred tank reactor (CSTR) by AFT was investigated under different experimental conditions, such as carbaryl inlet concentration, Fenton reagent concentration/ratio, and carbaryl feeding flow rate. A higher Fe2+ delivery rate and H2O2 to Fe2+ ratio (H2O2:Fe2+) were found to favor the carbaryl degradation process, whereas flow rate was shown to be a much less significant factor to influence the degradation rate under the evaluated experimental conditions. A kinetic-based semiempirical model was developed to simulate the experimental data, and a very good fit between the model and the raw data was found (R2 > 0.99). A dimensionless parameter (k/q2) was found to be a good indicator of the degradation rate; that is, the higher the k/q2value is, the faster the degradation process is. The rate parameter (k) can be used to evaluate the degradation rate when the flow rate is invariant for a given pesticide. The shape parameter (beta) is most likely related to the availability and reactivity of Fenton reagents and hydroxyl radicals. To compare the degradation rate of different pesticides, more information other than k/q2, k, and beta values, such as the instantaneous degradation rate vs time relationship, needs to be considered.

Sorption of carbaryl (1-naphthyl-N-methyl-carbamate) from aqueous suspension to smectite was studied using Fourier transform infrared (FTIR), high-performance liquid chromatography (HPLC) (for batch sorption), and quantum chemical methods. The amount of carbaryl sorbed was strongly dependent on the surface-charge density of the smectite with more sorption occurring on the two "low" surface-charge density smectites (SHCa-1 and SWy-2) compared to that of the high surface-charge SAz-1 smectite. In addition, the amount of carbaryl sorbed was strongly dependent on the nature of the exchangeable cation and followed the order of Ba approximately Cs approximately Ca > Mg approximately K > Na approximately Li for SWy-2. A similartrend was found for hectorite (SHCa-1) of Cs > Ba > Ca > K approximately Mg > Na approximately Li. Using the shift of the carbonyl stretching band as an indicator of the strength of interaction between carbaryl and the exchangeable cation, the observed order was Mg > Ca > Ba approximately K > Na > Cs. The position of the carbonyl stretching band shifted to lower wavenumbers with increasing ionic potential of the exchangeable cation. Density functional theory predicted a cation-induced lengthening of the C=O bond, resulting from the carbonyl group interacting directly with the exchangeable cation in support of the spectroscopic observations. Further evidence was provided by a concomitant shift in the opposite direction by several vibrational bands in the 1355-1375 cm(-1) region assigned to stretching bands of the carbamate N-Ccarbonyl and Oether-Ccarbonyl bonds. These data indicate that carbaryl sorption is due, in part, to site-specific interactions between the carbamate functional group and exchangeable cations, as evidenced by the FTIR data. However, these data suggest that hydrophobic interactions also contribute to the overall amount of carbaryl sorbed. For example, the FTIR data indicated thatthe weakest interaction occurred when Cs+ was the exchangeable cation. In contrast, the highest amount of carbaryl sorption was observed on Cs-exchanged smectite. Of all the cations studied, Cs has the lowest enthalpy of hydration. It is suggested that this low hydration energy provides the carbaryl with greater access to the hydrophobic regions of the siloxane surface.

The influence of clay preparation methods on the sorption and hydrolysis of carbaryl (1-naphthyl, N-methyl carbamate) by K+-saturated reference smectite SWy-2 was studied. Four methods were utilized: (1) The reference (or specimen) clay used as received was K+-saturated (hereafter referred to as whole clay). (2) High-speed centrifugation (3295g) of whole clay resulted in a pellet with three discrete bands. The upper, light-colored, low-density band was obtained by manual separation (light fraction). The high-density, dark-colored material comprising the lower band (heavy fraction) was also obtained manually. (3) SWy-2 was subjected to overnight gravity sedimentation to obtain the <2 microm particles (clay-sed.) and then K+-saturated. (4) SWy-2 was subjected to low-speed centrifugation (58-60g) to separate the <2 microm particle size (clay-cent.) and then K+-saturated. Each preparation of mineral fractions manifested significantly different abilities to hydrolyze carbaryl to 1-naphthol, decreasing in the order whole clay > heavy fraction >> clay-sed. > light clay > clay-cent. The extent of 1-naphthol disappearance from solution, accompanied by a progressive darkening of the clay, followed the order whole clay > heavy fraction >>> light clay > clay-sed. > clay-cent. Using ring labeled [14C]carbaryl, approximately 61 and 15% of the total 14C activity added to the whole clay and light fraction, respectively, remained unextractable. X-ray diffraction of the heavy fraction revealed several peaks corresponding to minor impurities, including calcite and dolomite. Aqueous slurries of whole clay, light fraction, clay-sed., and heavy fraction were alkaline, whereas the pH of slurried clay-cent. was neutral. It was concluded that dissolution of inorganic carbonate impurities in SWy-2 caused alkaline conditions in the slurries leading to the hydrolysis of carbaryl. Dissolution of carbonates with sodium acetate buffer eliminated hydrolytic activity associated with SWy-2. None of the four preparation methods reliably removed inorganic carbonates. The use of commercial or reference smectites in surface chemistry studies should be accompanied by a treatment with acetate buffer to remove carbonate impurities.

The synthesis and characterization of a novel catalyst for the photodecomposition of carbaryl (1-naphthyl, N-methylcarbamate) is reported. In the absence of a catalyst, but in the presence of UV light a 30 ppm solution of carbaryl decomposes with a first-order rate constant of (5.6 +/- 0.3) x 10(-5) s(-1) (298 K) and a quantum efficiency of 4.8 x 10(-3) molecules/photon. In the presence of the Ag-zeolite Y catalyst with 2.42% Ag by weight, the photodecomposition rate becomes 80 times faster. The addition of Suwannee River natural organic matter (NOM), which can inactivate photocatalysts, has a minimal effect on this system. In the presence of three different concentrations of NOM and 30 ppm carbaryl, our results indicate that the NOM increases or decreases the catalytic photodecomposition rate by only a factor of 3 at most.

The photoinduced degradation of carbaryl (1-naphthyl-N-methyl carbamate) was studied in a wetland's surface water to examine the photochemical processes influencing its transformation. For this particular wetland water, at high pH, it was difficult to delineate the photolytic contribution to the overall degradation of carbaryl. At lower pH values, the extent of the degradation attributable to indirect pathways, that is, in the presence of naturally occurring photosensitizers, increased significantly. Moreover, the photoenhanced degradation at the lower pH values was found to be seasonally and spatially dependent. Analysis of water samples revealed two primary constituents responsible for the observed indirect photolytic processes: nitrate and dissolved natural organic matter (NOM). Nitrate in the wetland appears at high concentrations (> or =1 mM) seasonally after the application of fertilizers in the watershed and promotes contaminant destruction through the photochemical production of the hydroxyl radical (HO*). The extent of the observed indirect photolysis pathway appears to be dependent upon the concentration of nitrates and the presence of HO* scavengers such as dissolved NOM and carbonate alkalinity. Paradoxically, during low-nitrate events (<50 microM), NOM becomes the principal photosensitizer through either the production of HO*, direct energy transfer from the excited triplet state, and/or production of an unidentified transient species.

Carbaryl, a commonly used insecticide, was used in this study as a probe to investigate a new Fenton treatment technology, ion exchange membrane anodic Fenton treatment (membrane AFT). It was found that the degradation kinetics of carbaryl by membrane AFT obeys a previously published AFT model quite well. The NaCl (electrolyte) concentration in two half-cells was optimized for two kinds of membrane. Effects of the H(2)O(2)/Fe(2+) ratio and the Fenton reagent delivery rate were also investigated. The treatment efficiency for anion membrane AFT is higher than for salt-bridge AFT under the same operating conditions. Decreasing the delivery rate of Fenton reagents and increasing the treatment temperature also increase the treatment efficiency. The activation energy for carbaryl degradation by anion membrane AFT was estimated to be 14.7 kJ x mol(-1). 1-Naphthol, 1,4-naphthoquinone, and (phthalic acid-O-)yl N-methylcarbamate were detected by GC-MS as the degradation products of carbaryl by Fenton treatment. No decrease in carbaryl degradation rate was found during repeated use (100 times) of the anion exchange membrane. High and stable treatment efficiency can be achieved using an anion exchange membrane rather than a salt-bridge in the AFT system. Because of its effectiveness and convenience, the use of an ion exchange membrane as a substitute for the salt-bridge used in the previous AFT system has brought the AFT technology a major step closer to practical application.

A controlled-release system with reduced environmental impact was produced by encapsulating the pesticide carbaryl in the waxy lipophilic material Gelucire 54/02. The microspheres were prepared by a modified hydrophobic congealable disperse-phase method. The influence of experimental parameters, such as the reciprocal ratio between the amounts of pesticide and wax employed, on size, morphology, loading efficiency, and release behavior of the particles was evaluated. Microspheres were free-flowing and showed a nonporous scaly surface at SEM analysis. The mean particle size ranged from 15.8 to 19.8 microm and was independent of the amount of Gelucire used to prepare the microspheres. At a fixed Gelucire content, the increase in theoretical carbaryl content yielded up to 72% loading efficiency, whereas at a fixed carbaryl content the increase in Gelucire amount produced a 64% increase in encapsulation efficiency. These data were accounted for by the carbaryl leakage from molten Gelucire toward the dispersing aqueous phase. The release profiles of carbaryl from microspheres showed that the use of increasing amounts of waxy material decreased the carbaryl release rate, whereas at a fixed Gelucire content, the release was the slowest when carbaryl was not completely dissolved within the matrix. The possibility to achieve different burst effects by simply varying the formulation parameters offers an efficient tool to ensure the fast release of an active dose of insecticide. The lower vertical mobility of carbaryl encapsulated in waxy microspheres compared to the vertical mobility of the technical-grade product showed that the controlled-release system has a lower potential risk for groundwater contamination.