Some physicochemical and environmental factors affecting transformation rates and sorption of the herbicide metamitron in soil

In addition to the molecular structure of a pesticide, environmental conditions may influence its persistence through their effect on the growth and activity of pesticide-degrading micro-organisms. As a result, transformation rates may decrease rapidly when a compound is leached into subsoil. Metamitron sorption isotherms were determined and incubation series were set up for a sandy loam soil, simulating single and combination effects that occur during transport of metamitron into subsoils. K_OC values increased with increasing depth from 185 to 700 litre kg⁻¹. A combination of conditions that are unfavourable for microbial activity, such as low temperature (5°C), low concentrations (0·5 mg kg⁻¹) and a large sorbed fraction (K_OC = 700) resulted in half-lives of over one year. Oxygen inhibition decreased the transformation rate of metamitron from 0·058 to 0·019 day⁻¹. In order of significance, the transformation of metamitron appears to be a function of temperature, oxygen availability and sorption to organic carbon. Increasing doses did not change transformation rates significantly, although different transformation pathways were observed.     

Use of bentonite and humic acid as modifying agents in alginate-based controlled-release formulations of imidacloprid

In order to prepare a formulation to be used for controlled release, imidacloprid was incorporated into alginate granules by using calcium chloride as gellant. The formulation prepared (alginate–imidacloprid–water) was modified by the addition of different sorbents. The effects on release rate of the addition of natural bentonite desiccated at 105 °C, untreated, acid-treated with sulfuric acid solutions over a concentration range between 0.5 mol dm⁻³ and 2.5 mol dm⁻³, and a commercial humic acid, were studied by immersion of the granules in water under static conditions. The time taken for 50% of the active ingredient to be released into water, (T₅₀), was calculated from the data obtained. On the other hand, the sorption–desorption processes of imidacloprid from a 0.01 M aqueous calcium chloride solution at 25 °C, by natural, acid-treated bentonite samples, and humic acid, have been studied by using batch experiments in order to evaluate the potential of these materials for their application in controlled-release formulations of pesticides. The experimental data have been fitted to the Freundlich equation in order to calculate the adsorption capacities (K_f). K_f values ranged from 1.76 mg kg⁻¹ for the untreated bentonite up to 126.9 mg kg⁻¹ for the humic acid. A correlation study was performed with T₅₀, the surface area (S) and the Freundlich parameter (K_f) of the bentonite samples in order to know the factors that affect release rate of imidacloprid from bentonite granules. A linear correlation of the T₅₀ values and both S and K_f parameters was observed. © 1999 Society of Chemical Industry     

Determination of sugarbeet herbicides in soil samples by hplc

Determination of sugarbeet herbicides such as chloridazon, metamitron and phenmedipham in soil samples is described. After extraction with acetone, pesticides were determined by HPLC on an RP-18 column using methanol/water as mobile phase. Average recoveries were 82% for chloridazon, 93% for metamitron and 77% for phenmedipham. Quantification limits were 3·5 μg kg^?1 for chloridazon, 6·3 μg kg^?1 for metamitron and 3·6 μg kg^?1 for phenmedipham.     

Pharmacokinetics of fenvalerate after intravenous administration to sheep

The pharmacokinetics of total radioactivity and of intact fenvalerate were determined in sheep treated intravenously with radiolabelled or non-radiolabelled fenvalerate. Mean residence times (MRT) of total radioactivity and intact fenvalerate in plasma were 910 (±75) and 39 (±3) min, while harmonic mean elimination-phase half-lives (TM_β) were 990 and 82 min, each respectively. Systemic clearance values (Cl_S) of total radioactivity and intact fenvalerate were 2·8 (±0·3) ml min⁻¹ kg⁻¹ and 51·3 (±5·9) ml min⁻¹ kg⁻¹, respectively. Volumes of distribution at steady state (V_SS) were each near 2500 ml kg⁻¹. Elimination of radioactivity occurred, in part (33·3 (±3·3)% of dose), by renal excretion, at a rate (0·9 (±0·1) ml min⁻¹ kg⁻¹), similar to that of glomerular filtration. These data are consistent with a disposition model according to which intact fenvalerate was rapidly distributed into a peripheral compartment, where metabolism occurred. In addition, since the elimination half-life of fenvalerate from plasma was less than 90 min after intravenous injection, ‘flip-flop’ kinetics should be considered when longer elimination half-lives are observed after oral or dermal exposures.     

Fate of chlorsulfuron in the environment. 1. Laboratory evaluations

The behaviour and fate of chlorsulfuron in aqueous and soil systems were examined in laboratory studies. Aqueous hydrolysis was pH-dependent and followed pseudo-first-order degradation kinetics at 25°C, with faster hydrolysis occurring at pH 5 (half-life 24 days) than at either pH 7 or 9 (half-lives >365 days). Degradation occurred primarily by cleavage of the sulfonylurea bridge to form the major metabolites chlorobenzenesulfonamide (2-chlorobenzenesulfonamide) and triazine amine (4-methoxy-6-methyl-1,3,5-triazin-2-amine). This route is a major degradation pathway in water and soil systems. Aqueous photolysis (corrected for hydrolysis) proceeded much more slowly (half-life 198 days) than aqueous hydrolysis and is not expected to contribute significantly to overall degradation. Hydrolysis in soil thin-layer plates exposed to light (half-life 80 days), however, progressed at a much faster rate than in dark controls (half life 130 days), which suggests that a mechanism other than direct photolysis may have been operative. An aerobic soil metabolism study (25°C) in a Keyport silt loam soil (pH 6·4, 2·8% OM) showed that degradation was rapid (half-life 20 days). Dissipation in an anaerobic sediment/water system (initial pH of water phase 6·7, final pH 7·4) progressed much more slowly (half-life >365 days) than in aerobic soil systems. Major degradation products in aerobic soil included the chlorobenzenesulfonamide and triazine amine as in the aqueous hydrolysis study. Neither of these degradation products exhibited phytotoxicity to a variety of crop and weed species in a glasshouse experiment, and both exhibited an acute toxicological profile similar to that of chlorsulfuron in a battery of standard tests. Demethylation of the 4-methoxy group on the triazine moiety and subsequent cleavage of the triazine ring is another pathway found in both aqueous solution and soils, though different bonds on the triazine amine appear to be cleaved in the two systems. Hydroxylation of the benzenesulfonamide moiety is a minor degradation pathway found in soils. Two soils amended with 0·1 and 1·0 mg kg^-1 chlorsulfuron showed slight stimulation of nitrification. The 1·0 mg kg^-1 concentration of chlorsulfuron resulted in minor stimulation and inhibition of ¹⁴C-cellulose and ¹⁴C-protein degradation, respectively, in the same soils. Batch equilibrium adsorption studies conducted on four soils showed that adsorption was low in this system (K_oc 13–54). Soil thin-layer chromatography of chlorsulfuron (R_f=0·55–0·86) and its major degradation products demonstrated that the chlorobenzenesulfonamide (R_f=0·34–0·68) had slightly less mobility and that the triazine amine (R_f=0·035–0·40) was much less mobile than chlorsulfuron. In an aged column leaching study, subsamples of a Fallsington sandy loam (pH_water 5·6, OM 1·4%) or a Flanagan silt loam (pH_water 6·4, OM 4·0%) were treated with chlorsulfuron, aged moist for 30 days in a glasshouse and then placed upon a prewet column of the same soil type prior to initiation of leaching. This treatment resulted in the retention of much more total radioactivity (including degradation products) than by a prewet column, where initiation of leaching began immediately after chlorsulfuron application, without aging (primarily chlorsulfuron parent). © 1998 SCI     

Adsorption of transformation products of atrazine by soil

The adsorption of atrazine and its transformation products, desisopropylatrazine (2-chloro-4-ethylamino-6-amino-l,3,5-triazine), desethyl-atrazine (2-chloro-4-amino-6-isopropylamino-l,3,5-triazine) and hydroxyatrazine (2-hydroxy-4-ethylamino-6-isopropylamino-l,3,5-triazine) to four top-soils was measured. Adsorption coefficients decreased in the order hydroxy atrazine, atrazine, desisopropylatrazine, and desethyl-atrazine: the distribution coefficient between organic matter and water (K_OM) ranged from 40 to 100 dm³ kg^?1 for atrazine, from 30 to 60 dm³ kg^?1 for desisopropylatrazine, from 20 to 50 dm³ kg^?1 for desethylatrazine and from 100 to 590 dm³ kg^?1 for hydroxy atrazine. Data are discussed in the context of earlier literature.     

Degradation and adsorption of 14C-MCPA in soil—influence of concentration, temperature and moisture content on degradation

MCPA was weakly absorbed in soils with 2.4, 3.0 and 2.9% humus. K_d-values were 0.7, 0.9 and 1.0, respectively. In soil, not previously treated with MCPA, the degradation of 0.05 mg kg^?114C-MCPA followed first-order reaction kinetics whereas degradation of 5 mg kg^?1 was only first-order for 2 weeks; exponentially increasing degradation rates followed indicating enrichment of the soil with MCPA decomposers. Degradation was monitored by evolution of ¹⁴CO₂. The influence of temperature on degradation of MCPA (4 mg kg^?1) could initially be described by Q₁₀ values or by the Arrhenius equation. After 1 day of incubation in two field soils Q₁₀ values were 3.3 and 2.9, respectively, between 0°C and 29°C; the activation energies were 87 and 76 kj mol^?1. Exponentially increasing degradation rates followed with doubling times of about 4.0, 1.8, 1.2 and 0.6 days at 6,10, 15 and 21°C, respectively. After 51 days of incubation, at temperatures between 6°C and 29°C, about 60%¹⁴C was evolved in CO₂ and only traces of MCPA were left in the soil. At 0°C and at 40°C only 1% and 10%¹⁴C, respectively, were evolved as CO₂ after 51 days. ¹⁴C-MCPA (4 mg kg^?1) was incubated at moisture contents from that in air-dried soil to 2.3 times field capacity. Optimum for degradation was from 0.6 to 1.2. field capacity. Degradation was very slow where water contents were below the level of wilting point and was nil in air-dried soil. In wet soil degradation was delayed, but even in water-logged soil (2.3 times field capacity) MCPA was decomposed after 4 to 5 weeks at 10°C.     

Influence of fungicidal control of cucumber and tomato grey mould (Botrytis cinerea) on fruit yield

The fungicides tebuconazole, tebuconazole + dichlofluanid, fenethanil, diethofencarb + carbendazim, and vinclozolin combined with chlorothalonil were tested for their ability to control grey mould (Botrytis cinerea Pers. ex Fr.) of cucumber and tomato grey mould in greenhouses under commercial conditions. In winter 1987/88 the number of diseased female fruits of cucumber (Cucumis sativus L.) was reduced by diethofencarb + carbendazim (2·5 mg dm^?3 each) by 93% and by tebuconazole (2·5 mg dm^?3)(phytotoxic when alone) or tebuconazole (1 mg dm^?3) + dichlofluanid (4 mg dm^?3) by 54–57%. Vinclozolin (5 mg dm^?3) + chlorothalonil (25 mg dm^?3) significantly reduced disease incidence on fruits by 40%. Infection foci on cucumber stems were significantly decreased by vinclozolin + chlorothalonil. A more pronounced decrease was obtained with diethofencarb + carbendazim, tebuconazole, or tebuconazole + dichlofluanid. During the season of winter 1988/89, tebuconazole + dichlofluanid (1·5 + 6 and 3 + 12 mg dm^?3) and RH7592 (1 mg dm^?3) significantly reduced diseased fruits by 30–71%. Grey mould of tomato (Lycopersicon esculentum Mill.) leaves was reduced by more than 90% and on fruits by 78–87% when tebuconazole + dichlofluanid (1·5 + 6 and 3 + 12 mg dm^?3) or diethofencarb + carbendazim (2·5 mg dm^?3 each) were applied. Yields of cucumber fruits of the common parthenocarpic cv. Kasem 292 were weighed. There was no correlation between disease level and yield in any experiment, plot or date except for two measurements. Compesation in fruit production by the plant may be regarded as the reason for no positive yield response to efficient control. The possibility of reducing fungicide application is discussed. Control of grey mould on tomato resulted in yield increase.     

Residues in apples and sweet cherries after methyl bromide fumigation

Methyl bromide fumigations are used to treat apples, Malus domestica Borkh, and sweet cherries, Prunus avium (L), before export to Japan. In order to expand existing markets, additional cultivars are being prepared for export to Japan. As part of the approval process, residue analyses must be conducted and residues must be at acceptable levels. Five apple cultivars (‘Braeburn,’ ‘Fuji,’ ‘Gala,’ ‘Jonagold,’ and ‘Granny Smith’) were fumigated at 40 g m⁻³ for 2 h at 10 °C, and six sweet cherry cultivars (‘Brooks,’ ‘Garnet,’ ‘Lapin,’ ‘Rainier,’ ‘Sweetheart,’ and ‘Tulare’) were fumigated for 2 h with 64 g m⁻³ at 6 °C, 48 g m⁻³ at 12 °C, 40 g m⁻³ at 17 °C, and 32 g m⁻³ at 22 °C. Three replicates of fruit from each fumigation were analyzed for methyl bromide and bromide ion residues periodically with time. Methyl bromide residues for both apples and cherries were the highest immediately after fumigation, but rapidly declined so that only ‘Braeburn’ had residues >8 µg kg⁻¹ after 13 days and, except for ‘Lapin,’ all cherries were <1 µg kg⁻¹ after seven days. Average bromide ion residues were between 3.3 and 4.9 mg kg⁻¹ among apple cultivars, and between 3.7 and 8.0 µg kg⁻¹ among cherry cultivars. Published in 2000 for SCI by John Wiley & Sons, Ltd     

Characterization of triadimefon sorption in soils using supercritical fluid (SFE) and accelerated solvent (ASE) extraction techniques

Sorption–desorption of the fungicide triadimefon in field‐moist silt loam and sandy loam soils were determined using low‐density supercritical fluid extraction (SFE). The selectivity of SFE enables extraction of triadimefon from the soil water phase only, thus allowing calculation of sorption coefficients (K_d) at field‐moist or unsaturated conditions. Triadimefon sorption was influenced by factors such as soil moisture content and temperature; sorption increased with increased moisture content up to saturation, and decreased with increased temperature. For instance, K_d values for triadimefon on the silt loam and the sandy loam soils at 40 °C and 10% water content were 1.9 and 2.5 ml g⁻¹, respectively, and at 18% water content, 3.3 and 6.4 ml g⁻¹, respectively. Isosteric heats of sorption (ΔH_i) were −42 and −7 kJ mol⁻¹ for the silt loam and sandy loam soils, respectively. Sorption–desorption was also determined using an automated accelerated solvent extraction system (ASE), in which triadimefon was extracted from silt loam soil by 0.01 M CaCl₂. Using the ASE system, which is basically a fast alternative to the batch equilibration system, gave a similar ΔH_i value (−29 kJ mol⁻¹) for the silt loam soil (K_f = 27 µg^{1 − 1/n} ml^1/n g⁻¹). In order to predict transport of pesticides through the soil profile more accurately on the basis of these data, information is needed on sorption as a function of soil water content. © 2000 Society of Chemical Industry     

Aerobic Metabolism of Flupropacil in Sandy Loam Soil

The aerobic soil metabolism of [¹⁴C]flupropacil (isopropyl 2-chloro-5-(1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoate) was determined in microbially active, sieved (2-mm) sandy loam soil with a soil moisture content of 75% at 1/3 bar. The soil was treated with [¹⁴C]flupropacil at 0·5 mg kg⁻¹ (twice the field use rate) and placed in incubation flasks connected to a series of traps (50 g litre⁻¹ NaOH, 0·5M H₂SO₄, ethylene glycol) and incubated at 25(±1)°C. Soil was sampled at 0, 3, 9, 20, 30, 48, 76, 120, 181 and 238 days of aerobic incubation. Volatiles were collected once every two weeks and on the day of soil sampling. Flupropacil metabolized with a half-life of 79 days under aerobic conditions. The major metabolite was flupropacil acid which accounted for up to 69·1% of the initially applied radioactivity at Day 238. Each of the two minor metabolites detected at the end of the study accounted for less than 0·5%. One of the minor metabolites was identified as C4242 acid (2-chloro-5-(1,2,3,6-tetrahydro-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoic acid). Only a negligible portion (less than 0·3%) of the applied flupropacil was mineralized to [¹⁴C]carbon dioxide. Extractable radioactivity ranged from 78·9% to 95·5%, with bound residues accounting for 3·2%–23·4%. The material balance ranged from 91·6% to 104·4%.     

Chemical hydrolysis of 2-chloro-4,6-bis(alkylamino)-1,3,5-triazine herbicides and their breakdown in soil under the influence of adsorption

The determination of rate constants and the calculation of the activation parameters [activation energy (E_a), free energy of activation(ΔG^≠)and entropy of activation (ΔS^≠)] demonstrated the identity of the reaction kinetics of chemical hydrolysis of the chlorinated triazine herbicides simazine, atrazine, propazine and terbuthylazine. Persistence in soil could be estimated, from the hydrolytic half-life time, only in pH regions where these compounds were also sensitive to chemical hydrolysis. In general, the rate of hydrolysis increased in the presence of soil as the result of a catalysing effect of the soil in their breakdown. When half-lives in soil of these triazine herbicides were compared with adsorption constants, a functional relationship was observed in both soil types; as adsorption increased the half-life in soil also increased.     

Adsorption-leaching study of the herbicides metamitron and chloridazon

Freundlich isotherms were obtained for the adsorption equilibrium of the herbicides metamitron and chloridazon with the components of a representative soil in a pesticide concentration range of 10-1000 γg ml^?1 for metamitron and 10-500 μg ml^?1 for chloridazon. The mobility of these herbicides through soil columns was also studied using the displacement technique described by Davidson (Soil Sci. Soc. Amer. Proc., 32 (1968) 629). The experiment was carried out simultaneously in three columns, two of which were fed with solutions of the herbicides while the third was used as a control. The herbicide solutions flowed down by gravity and were collected at the outlet at different times. The herbicide content of these outlet solutions was determined by Differential Pulse Polarography.     

The effect of the annual use of some pesticides on soil microorganisms,pesticide residues in soil and carrot yields

The study deals with the effect of common, annually-used pesticides on soil microorganisms, pesticide residues in soil, and carrot (Daucus carota) yields in Central Finland. Linuron residues in carrot roots were also analysed. Thiram+lindane and dimethoate were applied from 1973–1981 at the commercially recommended doses on experimental plots of carrots, linuron was applied at twice the recommended rate from 1973–1979 and at the normal rate thereafter and in addition TCA was applied in 1978. Maleic hydrazide was used in the years 1973–1976, and glyphosate after 1977. The numbers of different soil microorganisms, their activities and the pesticide residues were studied from autumn 1978 to 1981. The pesticide treatments reduced the growth of soil algae but increased the total number of microorganisms and the number of aerobic spore-forming bacteria. Linuron residues in the soil were 0.9–2.8 mg kg^?1 in the growing season and 1.2–1.7 mg kg^?1 in the autumn, 3 months after application. The residues of glyphosate in the soil were 0.7 mg kg^?1 in the autumn, 41 days after the treatment, and had declined to a level of about 0.2 mg kg^?1 by the following summer. In the pesticide-treated plots the carrot yield was only 20–60% of the yield in the hand-weeded plots. The herbicide programme controlled most of the annual weeds but not couchgrass Elymus repens and milk sow-thistle Sonchus arvensis.     

Aerobic soil metabolism of metsulfuron-methyl

A laboratory study was conducted to determine the degradation rates and identify major metabolites of the herbicide metsulfuron-methyl in sterile and non-sterile aerobic soils in the dark at 20°C. Both [phenyl-U-¹⁴C]- and [triazine-2-¹⁴C]metsulfuron-methyl were used. The soil was treated with [¹⁴C]metsulfuron-methyl (0.1 mg kg⁻¹) and incubated in flow-through systems for one year. The degradation rate constants, DT₅₀, and DT₉₀ were obtained based on the first-order and biphasic models. The DT₅₀ (time required for 50% of applied chemical to degrade) for metsulfuron-methyl, estimated using a biphasic model, was approximately 10 days (9–11 days, 95% confidence limits) in the non-sterile soil and 20 days (12–32 days, 95% confidence limits) in the sterile soil. One-year cumulative carbon dioxide accounted for approximately 48% and 23% of the applied radioactivity in the [phenyl-U-¹⁴C] and [triazine-2-¹⁴C]metsulfuron-methyl systems, respectively. Seven metabolites were identified by HPLC or LC/MS with synthetic standards. The degradation pathways included O-demethylation, cleavage of the sulfonylurea bridge, and triazine ring opening. The triazine ring-opened products were methyl 2-[[[[[[[(acetylamino)carbohyl]amino]carbonyl]amino] carbonyl]-amino]sulfonyl]benzoate in the sterile soil and methyl 2-[[[[[amino[(aminocarbonyl)imino]methyl] amino]carbonyl]amino]sulfonyl]benzoate in the non-sterile soil, indicating that different pathways were operable. © 1999 Society of Chemical Industry     

Co‐solvent effects on the adsorption of carbofuran by two Indian soils

The adsorption of carbofuran on soils from water‐methanol mixtures has been evaluated by batch shake testing. Two uncontaminated soils having different physicochemical properties were used in these experiments. The volume fraction of methanol in the liquid phase (f_s) was varied from 0.25 to 1.0. Higher adsorption of carbofuran was observed in medium black (silt loam) soil than in alluvial (sandy loam) soil; calculated values of the Freundlich constant (K^m) and distribution coefficient (K_d) showed that adsorption of carbofuran in both soils decreased with increase in f_S values. The decreased carbofuran adsorption in methanol–water mixtures meant a greater potential of ground‐water contamination through leaching from potential sites. The data have been used to evaluate the co‐solvent theory for describing adsorption of carbofuran in methanol–water mixtures. The aqueous phase partition coefficient K_dw (mol g⁻¹) normalized with respect to f_oc and the aqueous phase adsorption constant K_w for carbofuran were evaluated by extrapolating to f_S = 0. © 2000 Society of Chemical Industry     

The effect of initial concentration of carbofuran on the development and stability of its enhanced biodegradation in top‐soil and sub‐soil

Carbofuran was incubated in top‐soil and sub‐soil samples from a pesticide‐free site at a range of initial concentrations from 0.1 to 10 mg kg⁻¹. Amounts of the incubated soils were removed at intervals over the subsequent 12 months, and the rate of degradation of a second carbofuran dose at 10 mg kg⁻¹ was assessed. An applied concentration as low as 0.1 mg kg⁻¹ to top‐soil resulted in more rapid degradation of the fresh addition of carbofuran for at least 12 months. The degree of enhancement was generally more pronounced with the higher initial concentrations. When the same study was conducted in sub‐soil samples from the same site, an initial dose of carbofuran at 0.1 mg kg⁻¹ resulted in only small increases in rates of degradation of a second carbofuran dose. However, degradation rates in the sub‐soil samples were, in many instances, considerably greater than in the corresponding top‐soil samples, irrespective of pre‐treatment concentration or pre‐incubation period. Initial doses of 0.5 mg kg⁻¹ and higher applied to sub‐soil successfully activated the sub‐soil microflora. Application of the VARLEACH model to simulate carbofuran movement through the soil profile indicated that approximately 0.01 mg kg⁻¹ of carbofuran may reach a depth of 70 cm 400 days after a standard field application. The results therefore imply that adaptation of the sub‐soil microflora (c 1 m depth) by normal field rate applications of carbofuran is unlikely to occur. In experiments to investigate this in soils exposed to carbofuran in the field, there was no apparent relationship between top‐soil exposure and degradation rates in the corresponding sub‐soils. The results further confirmed that some sub‐soil samples have an inherent capacity for rapid biodegradation of carbofuran. The high levels of variability observed between replicates in some of the sub‐soil samples were attributed to the uneven distribution of a low population of carbofuran‐degrading micro‐organisms in sub‐surface soil. There was no apparent relationship between soil microbial biomass and degradation rates within or between top‐soil and sub‐soil samples. © 2001 Society of Chemical Industry     

Leaching of Methyl Isothiocyanate in Plainfield Sand Chemigated with Metam-Sodium

Soil column studies were undertaken to investigate the influence of soil water content and irrigation on leaching, distribution and persistence of methyl isothiocyanate (MITC) in a sandy soil chemigated with the soil fumigant metam-sodium. No leaching was obtained from columns at low water content (0·042 or 0·074 cm³ cm⁻³). However, 8·4 (±2·8), 34·2 (±7·4) and 119·4 (±8·3) μg of MITC leached from columns at 0·105, 0·137 and 0·168 cm³ cm⁻³ water content, respectively. Increased leaching resulted from sprinkler application of 25-mm of water to columns at 0·137 cm³ cm⁻³ water content. Leaching of MITC constituted only a small fraction of the amount applied even in the worst case. Methyl isothiocyanate persisted in soil for 15 days at 2°C in varying amounts under the different water regimes. Relatively high amounts of MITC residues (8–12 mg kg⁻¹ soil) were detected in the top 25-cm layer of all the soil columns. Degradation was the major pathway of dissipation for the chemical despite the soil water regime.     

Germination response of Orobanche seeds subjected to conditioning temperature, water potential and growth regulator treatments

Broomrapes (Orobanche spp.) are parasitic weeds that cause significant losses of crop yield. Experiments were conducted to investigate the seed response to the artificial germination stimulant GR₂₄ in three species of Orobanche subjected to preconditioning under various temperatures, water potentials and with plant growth regulators. The highest germination percentages were observed in Orobanche ramosa, Orobanche aegyptiaca and Orobanche minor seeds conditioned at 18°C for 7 days followed by germination stimulation at 18°C. With the increase of the conditioning period (7, 14, 21 and 28 days), the germination percentage of O. ramosa and O. aegyptiaca progressively decreased. When conditioned at −2 MPa, the germination percentage was lower than at 0 and −1 MPa, especially at 13 and 28°C. Orobanche minor seeds could retain relatively high germination if conditioned at 18, 23 or 28°C, even after significantly extended conditioning periods (up to 84 days). GA₃ (30–100 mg L⁻¹), norflurazon and fluridone (10–100 mg L⁻¹), and brassinolide (0.5–1.0 mg L⁻¹) increased seed germination, while 0.01 mg L⁻¹ uniconazole significantly reduced germination rates of all three Orobanche spp. The promotional effects of GA₃ and norflurazon and the inhibitory effect of uniconazole were evident, even when they were treated for 3 days. Germination of Orobanche seeds was much lower when the unconditioned seeds were directly exposed to GR₂₄ at 10⁻⁶ m . This early GR₂₄-induced inhibition was however alleviated or even eliminated by the inclusion of GA₃ or norflurazon (10–50 mg L⁻¹) in the conditioning medium. On the contrary, the inclusion of uniconazole increased the inhibitory effect of GR₂₄, particularly in the case of O. ramosa.     

Measurement and simulation of the movement of thiazafluron, clopyralid and metamitron in soil columns

Adsorption and leaching of the herbicides thiazafluron (1,3-dimethyl-1(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)urea), metamitron (4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-tri azin-5-one) and clopyralid (3,6-dichloropicolinic acid) were studied in one sandy and two silty-clay soils. Equilibrium adsorption coefficients (K_d) were measured using a batch equilibration procedure, and mobility was studied in repacked columns of the soils under fluctuating saturated/unsaturated flow conditions. Breakthrough curves (BTCs) were consistent with an inverse relationship between leaching and adsorption with greater mobility of the weakly-adsorbed clopyralid than the more strongly adsorbed thiazafluron or metamitron. The BTC data were used to evaluate the LEACHP simulation model. Following model calibration with respect to hydrological parameters and some of the herbicide degradation rates, the best fits between predicted and observed data were with the less adsorptive and highly mobile clopyralid. In general, the model gave acceptable predictions of the timing of the concentration maxima and the shapes of the BTCs, although earlier breakthrough than that observed was predicted with the less mobile herbicides, thiazafluron and metamitron, in the silty-clay soils. For metamitron, the total amounts leached were not predicted accurately, suggesting more rapid degradation of the herbicide in the soil columns than in the kinetic studies performed in a 1:1 soil:solution ratio shaken system.