Long-term sorption of diuron and isoproturon by a clay loam soil was investigated for nine weeks at two herbicide doses (0.6 or 3 mg kg-') and two soil moisture contents (35 or 62% w/w, i.e. 3.16 or 1 kPa) by measuring changes in herbicide concentrations in the soil solution sampled by means of glass microfibre filters in presence of sodium azide (200 mg litre-') which inhibited biodegradation for more than four weeks. After the first day equilibration period, where adsorption mainly occurred ( > 70% adsorbed), herbicide concentrations in the soil solution decreased (about 50% for diuron; up to 38% for isoproturon) for two weeks but equilibration required about one month. Small amounts of herbicides were sorbed during this process (

The adsorption of diuron and isoproturon by a clay loam soil at 35% (3‐16 kPa) and 62% (1 kPa) soil moisture content was studied by means of glass microfibre filters capable of sampling soil solution for herbicide analysis. Adsorption was rapid, with 40–80% of the final (24 h) sorption being achieved within 2 min. These equilibria were achieved more rapidly for diuron, which was also the more highly adsorbed. Adsorption of both herbicides was favoured by low soil moisture initially, but was enhanced by higher soil moistures at sorption times greater than 30 min. However, increasing the soil moisture from 31% (10 kPa) to 62% (1 kPa) had little effect on the final soil sorption capacity. Regarding the water status in the soil, it is thought that adsorption took place in small pores (<3 μm). Herbicides diffused rapidly into small pores and adsorption by wet soil was delayed for a short period of time (about 30 min).

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Changes in the concentrations of [''*C]carbonylisoproturon and its degradation products in a clay-loam soil and in soil solution during incubation at 11°C and 18°C for 6 weeks, were measured following solvent extraction and soil solution sampling with glass microfibre filters. During herbicide degradation, ' "^CCh was released (up to 20%) and unextractable radioactivity increased (up to 30%). Monomethyl isoproturon was the main metabolite in soil followed by metabolite X5 (possibly hydroxy di-desmethyl isoproturon). Isoproturon and monomethyl isoproturon were mainly adsorbed by soil whereas metabolite X5 was found mainly in the soil solution. Isoproturon concentrations declined in both soil and soil solution, but the percentage of the residual herbicide dissolved in the soil solution decreased from 26 to 15%. At low temperature, herbicide degradation occurred more slowly, and the degradation products were generally less abundant. However metabolite X5 was present at unexpectedly high levels, particularly in the soil solution.

Summary: The foliar surface of 4‐leaf maize plants was found to be poorly wettable and retained 106 μl g−1 dry matter when sprayed with a U46D (2,4‐D formulation) blank. The third leaf retained 141 μl g−1. A 7‐day cold spell (17/9°C) increased retention per unit dry matter by 53% (135% on the third leaf). Cold stress lowered epicuticular wax quantity by 29% on the third leaf. Contact angles of formulated 2,4‐D lay between 115 and 125° and were not significantly affected by cold stress. 2,4‐D rapidly entered into maize third leaf (66% in 24 h) but migration from it was less than 1.5%. 2,4‐D was readily degraded in maize (80% in 72 h). The most abundant metabolite was probably an ester conjugate; little of the hydroxy derivatives were found. Cold stress reduced 2,4‐D degradation, and 72 h after treatment the amount of undegraded 2,4‐D was 78% higher in cold‐stressed maize plants. It was concluded that 2,4‐D selectivity in maize results from low spray retention per unit dry matter and active degradation of penetrated herbicide. Cold stress affects both factors.

Summary Influence of 2,4‐D on toxicity of diclofop‐methyl to Avena sativa (cv. Selma) and Arena fatua at 2·5 leaf stage has been evaluated under controlled conditions. Effects of 2,4‐D on the fate of diclofop‐methyl in cultivated oat have also been studied. Mixture with 2,4‐D reduced the toxicity of diclofop‐methyl to both species. When applied immediately after diclofop‐methyl treatment, 2,4‐D still reduced herbicide toxicity to wild oat. This reduction was smaller in cultivated oat. and was only observed at higher phytotoxicity. No interaction was observed when a 10‐day period separated the two applications. In mixture, 2,4‐D enhanced diclofop‐methyl penetration and diclofop acid conjugation in cultivated oat, and it slightly increased conjugation when applied separately. None of these effects clearly explain the reduction of diclofop‐methyl toxicity by 2, 4‐D in cultivated oat. Other processes are possibly involved and could be connected with the site of action of diclofop‐methyl.

We investigated the sorption of ®ve widely used sterol biosynthesis inhibitor fungicides (SBIs:¯usilazole, propiconazole, epoxiconazole, fenpropimorph and prochloraz) on a loam soil to assess availability of the SBI residues that are usually left in soil after crop treatments. We focused particularly on the soil moisture content effect, which is poorly documented and is dif®cult to investigate under realistic conditions. SBI sorption was determined (using diuron as a reference) at two soil moisture contents (26.1% and 46.6% w/w) over a period of 3 weeks using a direct soil solution sampling method.After 24 h of contact,`1% of each applied fungicide was recovered in the soil solution. Despite their low availability in the liquid phase, long-term sorption was observed for all the compounds, reducing concentrations in the soil solution and doubling the value of the partition coef®cient. Signi®cant effects of soil moisture on long-term sorption were observed, depending on the properties of the chemicals and the sorption mechanisms. Wershaw's humus model (humic substances have a membrane-like structure) was adapted to ®t our observations. Low soil moisture content is assumed to modify the structure of humic substances and to generate hydrophobic surfaces, which favour sorption of hydrophobic fungicides (¯usilazole, propiconazole and epoxiconazole). This effect is likely to decrease with the increase in the hydrophobic character of non-ionic pesticides. It becomes adverse for the more hydrophilic compounds (diuron), which are more sorbed at high soil moisture content due to their higher af®nity for hydrophilic regions of humus and to diffusion. Soil moisture effects are more complex when compounds are likely to be protonated in soil. Weakly basic compounds (prochloraz) may partition rapidly into the liquid-like interior of humus at low soil moisture content but increased diffusion at high soil moisture content may cause additional sorption by ion exchange at colloid surfaces. Strongly basic compounds (fenpropimorph) may essentially adsorb due to ionic interactions with colloids, and their sorption is enhanced at high soil moisture content due to diffusion. Consequences for environmental fate and biological activity of pesticides are brie¯y discussed.

Summary: Retention by a glass fibre filter of the liquid phase of a clay loam soil treated with 14C‐diuron provides a novel method for analysis of the herbicide in soil solution. At 26.3% (w/w) soil moisture content, less than 10% of the applied diuron was found in solution, and this percentage decreased slightly with diuron dose. The herbicide was rapidly adsorbed on soil during the first day, but adsorption continued and the concentration of diuron in solution could be further reduced by 36–50% during the following 6 days. Drying the soil after treatment, with possible crystallization of herbicide applied at high doses, tended to fix the solution concentrations. Ethanol (3% v/v) in soil water favoured herbicide dissolution. Increasing soil moisture to 36.3% (w/w) slightly decreased the concentration of the herbicide in solution, but increased the percentage held in solution. Frost and a drying‐rewetting cycle had little or no subsequent effect on diuron concentration in soil solution.