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Pesticides in soil are subject to a number of processes that result in transformation and biodegradation, sorption to and desorption from soil components, and diffusion and leaching. Pesticides leaching through a soil profile will be exposed to changing environmental conditions as different horizons with distinct physical, chemical and biological properties are encountered. The many ways in which soil properties influence pesticide retention and degradation need to be addressed to allow accurate predictions of environmental fate and the potential for groundwater pollution. Degradation and sorption processes were investigated in a long-term (100 days) study of the chloroacetanilide herbicide, acetochlor. Soil cores were collected from a clay soil profile and samples taken from 0-30 cm (surface), 1.0-1.3 m (mid) and 2.7-3.0 m (deep) and treated with acetochlor (2.5, 1.25, 0.67 microg acetochlor g(-1) dry wt soil, respectively). In sterile and non-sterile conditions, acetochlor concentration in the aqueous phase declined rapidly from the surface and subsoil layers, predominantly through nonextractable residue (NER) formation on soil surfaces, but also through biodegradation and biotic transformation. Abiotic transformation was also evident in the sterile soils. Several metabolites were produced, including acetochlor-ethane sulphonic acid and acetochlor-oxanilic acid. Transformation was principally microbial in origin, as shown by the differences between non-sterile and sterile soils. NER formation increased rapidly over the first 21 days in all soils and was mainly associated with the macroaggregate (>2000 microm diameter) size fractions. It is likely that acetochlor is incorporated into the macroaggregates through oxidative coupling, as humification of particulate organic matter progresses. The dissipation (ie total loss of acetochlor) half-life values were 9.3 (surface), 12.3 (mid) and 12.6 days (deep) in the non-sterile soils, compared with 20.9 [surface], 23.5 [mid], and 24 days [deep] in the sterile soils, demonstrating the importance of microbially driven processes in the rapid dissipation of acetochlor in soil.

Degradation of the herbicide acetochlor in the unsaturated zone was quantified using two unique in situ field techniques. The DT50 values generated at two different sites on surface soil and two subsoil depths using these techniques were compared with values generated under aerobic laboratory-incubation conditions (typically 20 degrees C, 40% maximum water holding capacity). Additionally, laboratory-degradation data were generated on surface and subsoils from four other sites. All subsoils were treated with acetochlor at 5% of the surface soil application rate. Acetochlor degradation in both field- and laboratory-incubated subsoils was rapid and often exceeded surface soil rates. Field and laboratory DT50 values from all sites ranged from 2 to 88 days in subsoil, compared with a range of 1 to 18 days in surface soils. The DT50 results from in situ field techniques were comparable with those generated from laboratory incubations in the same soils, confirming the validity of performing laboratory-based degradation studies to determine pesticide DT50 values in subsoils. Microbiological characterisation of selected soils revealed that subsoils had a viable and active population, although direct counts of bacteria were consistently lower in subsoil (10(8)-10(9) g-1 dry soil) compared with surface soils (10(10) g-1 dry soil). The leaching models used to perform groundwater risk assessments (e.g. PELMO, PESTLA, MACRO-DB, PRZM and the FOCUS EU leaching scenarios) have provision for inclusion of subsoil degradation rates. However, conservative default estimates are typically used, as no other alternative is available. Results presented here show that these default values may significantly underestimate true subsoil degradation contributions, and therefore not accurately predict pesticide concentrations in groundwater. The degradation data generated for acetochlor were applied to the mathematical model PELMO to demonstrate the importance of the inclusion of subsoil degradation data in groundwater risk assessment models and thereby in the registration of pesticides in Europe.

Degradation of pesticides in aquifers has been evaluated based on a number of co-ordinated field and laboratory studies carried out in Danish aquifers. These studies included investigations of vertical and horizontal variability in degradation rates from the vadose zone to an aquifer, the effects of aerobic versus anaerobic conditions, and the importance of concentration on degradation kinetics for a selected range of herbicides. The studies were based on different experimental approaches ranging from simple batch experiments to column studies to field injection experiments and, where appropriate, results were compared. Some herbicides were degraded under aerobic conditions (some phenoxy acids, DNOC and glyphosate) and others under aerobic conditions (other phenoxy acids, DNOC; there was some indication of atrazine transformation). Certain pesticides were not degraded in any investigations (dichlobenil, the dichlobenil metabolite 2,6-dichlorobenzamide (BAM), bentazone, isoproturon, metamitron and metsulfuron-methyl). The spatial variability was substantial, since hardly any of the investigated pesticides were degraded in all comparable samples. This means that it is very difficult to claim that a given pesticide is readily degradable in aquifers. However, the experimental approaches used (with incubations lasting more than a year) may not be sensitive enough to verify the low degradation rates that may be significant as a result of the long retention time of groundwaters.