The analysis of the coherent data on nonextractable (bound) residues (NER) from the literature and EU pesticide registration dossiers allows the identification of general trends, in spite of the large variability and heterogeneity of data. About 50% of the pesticides reviewed exhibit a low proportion of NER (less than 30% of the initial amount) while only 12% of pesticides have a proportion of NER exceeding 70%. The lowest proportion of NER was found for dinitroanilines (<20%), and the largest value was obtained for carbamates, and in particular dithiocarbamates. The presence of chemical reactive groups, such as aniline or phenol, tends to yield a larger proportion of NER. NER originating from N-heteroatomic ring were found to be lower than those from phenyl-ring structures. Among the environmental factors affecting the formation of NER, microbial activity has a direct and significant effect. Concerning the NER uptake or their bioavailability, consistent data suggest that only a small percentage of the total amounts of NER can be released. The analysis of NER formation kinetics showed that incubation experiments are often stopped too early to allow a correct evaluation of the NER maturation phase. Therefore, there is a need for longer term experiments to evaluate the tail of the NER formation kinetics. Still, the heterogeneity of the NER data between pesticides and for specific pesticides calls for great care in the interpretation of the data and their generalization.

Smectites may strongly influence the fate of pesticides in soils due to their large surface area and abundance in agricultural soils. This research was undertaken to determine the effects of smectite properties on the affinity of smectitic clays for atrazine (2‐chloro‐4‐ethylamino‐6‐isopropylamino‐1, 3, 5 triazine). Samples of the <2‐µm fraction were separated by sedimentation from 13 reference smectites and treated with H2O2 for removal of organic matter. A soil smectite sample was separated (<0.02‐µm fraction) from a H2O2 and dithionite‐citrate‐bicarbonate‐treated Webster (fine‐loamy, mixed, mesic Typic Haplaquoll) soil by a dispersion‐centrifugation‐decantation technique. All 14 samples were Ca saturated, dialyzed free of excess electrolyte, and freeze dried. The mineralogy of each sample was evaluated by a combination of x‐ray diffraction and chemical analysis. Values for cation‐exchange capacity (CEC), surface charge density (SCD), surface area (SA), and percent tetrahedral charge (TC) were based on structural interpretations of the chemical analyses. Freundlich adsorption isotherms for atrazine adsorption on each sample were determined using the batch‐equilibration method. Smectite was the dominant mineral in 13 of the clay samples; the 14th sample was a mixture of interstratified smectite‐illite, quartz, and kaolinite. For the smectitic clays, atrazine adsorption ranged from 0 to 100%, and the logarithm of the Freundlich adsorption constant [log(Kf)] decreased linearly with the CEC (r2 = 0.82) of the clays. Stepwise multiple‐regression analysis indicated that log (Kf) values were correlated with SCD and SA values (r2 = 0.83). Inclusion of TC and suspension pH as independent variables in the regression analysis did not significantly improve the correlations. The results indicate that the affinity of smectites for atrazine decreases with increasing SCD, which suggests that atrazine is primarily adsorbed by smectites as a neutral species.

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In soils low in organic matter, pesticide adsorption and desorption by clay minerals may strongly influence the fate of pesticides in soil environments. Atrazine (2‐chloro‐4‐ethylamino‐6‐isopropylamino‐1,3,5‐triazine) adsorption‐desorption was determined on 11 reference smectites (<2‐µm size fraction), and a soil smectite (<0.02‐µm size fraction from the Ap horizon of a fine‐loamy, mixed, mesic Typic Haplaquoll). For each clay sample, adsorption and desorption isotherms were determined using batch equilibration. Atrazine adsorption on the clays decreased with increasing surface change density (SCD) of the smectites. The desorption isotherms indicated that adsorption was generally reversible. This suggests that atrazine is primarily adsorbed on smectite surfaces through relatively weak van der Waals or H bonds. However, a small positive hysteresis was observed with some clays, and the magnitude of the hysteresis, evaluated using the ratio of the Freundlich isotherm coefficients for adsorption and desorption, increased with SCD. This suggests that atrazine is retained by stronger binding mechanisms on smectites with high SCD, in spite of its lower adsorption capacity. On clays with high atrazine adsorption coefficients, the amount of atrazine desorbed was larger than would be predicted from the adsorption isotherms, resulting in a “negative hysteresis” whereby the desorption isotherm slope was greater than the adsorption isotherm slope. “Negative hysteresis” can be explained if atrazine is assumed to be excluded from interlayer or intraquasi‐crystal water, where only external or interquasi‐crystal water would be available during the desorption process.