Relation between volatility rating and composition of phenoxy herbicide ester formulations

A CIPAC/AOAC test with tomato plants is used to specify the volatility ratings of herbicide ester formulations. This work compares the tomato plant test with an alternative chemical one. The concentrations of esters and the effective molecular weight and density of each formulation were used with the ester vapour pressures to calculate its herbicide vapour pressure as complete, and evaporated formulations. The range was from 28.8 mPa (at 257deg;C) for a mixture of 2,4–D esters to 0–07 mPa (at 25°C) for a 2,4,5–T-(iso-octyl) formulation, as complete formulations, and 35-5 and 0–16 mPa (at 25°C) as evaporated ones. A value of 0–6 mPa (at 25°C) was selected on the basis of the tomato plant test as the cut-off area for low-volatile esters and is recommended to be included in specifications for herbicide esters. Formulations with a herbicide vapour pressure above 3.3 mPa (at 25°C) are high-volatile ones according to the tomato plant test, while between 0–6–3.3 mPa (at 25°C) is a borderline region where the test gives mixed results. Levels of 2,4–D-ethyl and methyl were added to pure 2–ethylhexyl esters of 2,4–D and a 2,4,5–T-(iso-octyl) formulation to find what level of contamination would change the rating of these esters from low to high volatile. Formulations of 2,4–D-(iso-octyl) should not contain more than 11 g litre^?1 2,4–D as methyl ester or 2.0 g litre^?1 2,4–D as ethyl ester. Formulations of 2,4,5–T-(iso-octyl) should not contain more than 26 g litre^?1 2,4–D as methyl ester or 4.7g litre^?1 2,4–D as ethyl ester.     

The behavior of clomazone in the soil environment

BACKGROUND: Clomazone is a herbicide used to control broadleaf weeds and grasses. Clomazone use in agriculturally important crops and forests for weed control has increased and is a potential water contaminant given its high water solubility (1100 µg mL^?1). Soil sorption is an environmental fate parameter that may limit its movement to water systems. The authors used model rice and forest soils of California to test clomazone sorption affinity, capacity, desorption, interaction with soil organic matter and behavior with black carbon. RESULTS: Sorption of clomazone to the major organic matter fraction of soil, humic acid (HA) (K_d = 29–87 L kg^?1), was greater than to whole soils (K_d = 2.3–11 L kg^?1). Increased isotherm non‐linearity was observed for the whole soils (N = 0.831–0.893) when compared with the humic acids (N = 0.954–0.999). Desorption isotherm results showed hysteresis, which was greatest at the lowest solution concentration of 0.067 µg mL^?1 for all whole soils and HA extracts. Aliphatic carbon content appeared to contribute to increased isotherm linearity. CONCLUSION: The results indicate that clomazone does not sorb appreciably to sandy or clay soils. Its sorption affinity and capacity is greater in humic acid, and consequently clomazone has difficulty desorbing from soil organic matter. Sorption appears to follow processes explained by the dual‐mode model, the presence of fire residues (black carbon) and a recently proposed sorption mechanism. Copyright © 2009 Society of Chemical Industry     

Factors affecting the performance and crop phytotoxicity of a new rice herbicide,cinmethylin. I. Effects of water depth and soil type on the distribution and uptake of cinmethylin by transplanted and direct-seeded rice

Following successful glasshouse evaluation, first-year field trials showed that cinmethylin could give excellent control of barnyard grass (Echinochloa crus-galli) in rice paddies. However, for the successful development of a herbicide in rice, a thorough understanding of its distribution over time between water, soil and plants as affected by water depth and soil type is necessary. An application of an emulsifiable concentrate formulation to laboratory paddies containing transplanted rice showed that more of the cinmethylin became associated with and moved into the soil of shallow paddies than in the more usual deep paddies. After the first day this resulted in slightly higher concentrations of cinmethylin being accumulated by the apical meristem, the site of action of cinmethylin, in shallow-paddy plants and explains the higher phytotoxicities observed in this situation. Rapid removal of cinmethylin by the soil from the paddy water could reduce that available for absorption by the apical meristem of barnyard grass, just below the water surface, and might result in poorer control of this weed. Deeper paddies are therefore recommended for the use of cinmethylin in transplanted rice. An experiment involving direct-seeded rice confirmed that a decrease in paddy water depth and higher organic-matter soils increased the association of cinmethylin with the paddy soil. Thus paddy-water concentrations and availabilities of cinmethylin to various parts of plants were influenced by water depth and soil type. In contrast to transplanted rice, the apical meristem of direct-seeded rice is submerged in the paddy water and the stem concentrations of cinmethylin were then generally correlated with the paddy-water concentrations. They were highest from the shallow, sandy paddies and lowest from the deep, silt clay loam paddies. These relative concentrations correlate with observed relative phytotoxicities of direct-seeded rice, activities against barnyard grass and the narrower selectivity margins between the weeds and the direct-seeded crop. The cinmethylin concentrations in the apical meristems of the transplanted rice were always lower than those from the direct-seeded rice and give an illustration of a classical case of depth protection' of a crop from an applied herbicide.     

Partitioning of etofenprox under simulated California rice‐growing conditions

BACKGROUND: The pyrethroid insecticide etofenprox is of current interest to rice farmers in the Sacramento Valley owing to its effectiveness against the rice water weevil, Lissorhoptrus oryzophilus Kuschel. This study aimed to describe the partitioning of etofenprox under simulated rice field conditions by determining its Henry's law constant (H) (an estimate of volatilization) and organic carbon‐normalized soil–water distribution coefficient (K_oc) at representative field temperatures. A comparison of etofenprox and λ‐cyhalothrin is presented using a level‐1 fugacity model. RESULTS: Experimental determination of H revealed that etofenprox partitioned onto the apparatus walls and did not significantly volatilize; the maximum value of H was estimated to be 6.81 × 10^?1 Pa m³ mol^?1 at 25 °C, based on its air and water method detection limits. Calculated values for H ranged from 5.6 × 10^?3 Pa m³ mol^?1 at 5 °C to 2.9 × 10^?1 Pa m³ mol^?1 at 40 °C, based on estimated solubility and vapor pressure values at various temperatures. Log K_oc values (at 25 °C) were experimentally determined to be 6.0 and 6.4 for Princeton and Richvale rice field soils, respectively, and were very similar to the values for other pyrethroids. Finally, temperature appears to have little influence on etofenprox sorption, as the log K_oc for the Princeton soil at 35 °C was 6.1. CONCLUSION: High sorption coefficients and relatively insignificant desorption and volatilization of etofenprox suggest that its insolubility drives it to partition from water by sorbing to soils with high affinity. Offsite movement is unlikely unless transported in a bound state on suspended sediments. Copyright © 2009 Society of Chemical Industry     

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     

Methods for determining the vapour pressure of active ingredients used in crop protection. Part IV. An improved thermogravimetric determination based on evaporation rate

The vapour pressure of thermally stable substances can be determined easily at ambient pressure using the evaporation rate method. It is possible to measure the evaporation by thermogravimetry in the temperature range from 30°C to 800°C. Vapour pressures as low as 10^?10 Pa (10^?12 mbar) can be determined with excellent reproducibility.     

Degradation of oxadiazon in Kalyani alluvial soil

Residual fate and behaviour of the herbicide oxadiazon in Kalyani soil, paddy straw and grain were studied under subtropical conditions, in West Bengal following application @ 1 kg and 2 kg ha⁻¹. Dissipation of oxadiazon in soil followed first-order kinetics and DT₅₀ values ranged from 44 to 45 days. Residues at harvest in paddy grains and straw were also studied. Degradation of oxadiazon after 60 days of incubation at 28(± 1) °C in alluvial soil at water holding capacity yielded 10 metabolites of which four were characterised by spectroscopy. © 1999 Society of Chemical Industry     

Long- and short-term effects of vapour of the herbicide 2,4-D butyl on the growth of tomato plants

An airflow system has been used to expose tomato plants to a range of concentrations of vapour of the herbicide 2,4-D butyl, from 5 to 50 ng l^?1. Experiments carried out at an air temperature of 20°C indicate that only short periods (less than 2.5 h) are required to produce symptoms of phytotoxicity at concentrations less than 5 ng l^?1, or approximately 2.5% of the saturated vapour pressure of the herbicide. A 5-h period of exposure to approximately 5 ng l^?1 reduced the dry weight and dry matter content of the tomato plants after 7 weeks by 18% and 9%, respectively, compared with the control. Phytotoxicity symptoms were shown by the plants in proportion to the vapour concentration during the period of exposure to herbicide. Rates of photosynthesis of treated plants had begun to decline within an hour of the commencement of exposure, slightly after leaf movement was first observed.     

Volatile analogues of penconazole and their activity against the take-all fungus,Gaeumannomyces graminis var. tritici

Eight new sterol biosynthesis-inhibiting fungicides, structurally related to penconazole and having vapour pressures up to 118 mPa, were synthesised. Their toxicities to the cereal take-all fungus, Gaeumannomyces graminis var. tritici, on agar were measured; intrinsic activities were measured after incorporating the compounds into the agar and vapour activities were measured after their evaporation from glass and from moist soil. Vapour activity following evaporation from soil was shown to be a function of both the intrinsic activity of the compound and its partition coefficient between the air and moist soil (K_as). The latter is itself a function of vapour pressure, 1-octanol/water partition coefficient (K_ow) and the soil type. The compound most active as vapour from soil in the in-vitro test, 1-(pyridin-3-yl)-2-(4-flurorophenyl)pentane, was ineffective against take-all in wheat in a pot test in which the inoculated soil was treated unevenly, providing further evidence that the redistribution of fungicides in moist soil occurs predominantly via the water phase rather than the vapour phase.     

Changes in the concentrations of isoproturon and its degradation products in soil and soil solution during incubation at two temperatures

Changes in the concentrations of [¹⁴C]carbonyl-isoproturon 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, ¹⁴CO₂ 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-des-methyl 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. Evolution de l'isoproturon et de ses produits dégradation dans le sol et la solution du sol pendant l'incubation de Vherbicide a deux temperatures. L'évolution de l'isoproturon (marqué au ¹⁴C sur le carbonyle) et de ses produits de dégradation dans un sol argilo-limoneux et dans la solution du sol est suivie pendant 6 sêmaines d'incubation de l'herbicide à 11 et 18°C. Pour ce faire, la solution du sol est échantillonnée au moyen de filtres en fibres de verre et les composés sont extraits du sol par des solvants. Au cours de la dégradation, du ¹⁴CO₂ est libéré (jusqu'à 20%) et la radioactivité non extraite s'accroit (jusqu'à 30%). L'isoproturon monométhyle est le principal métabolite dans le sol suivi du metabolite X5 (probablement le dérivé hydroxy didéméthylé). L'isoproturon et son dérivé monométhyle sont surtout adsorbés par le sol alors que le métabolite X5 est surtout en solution. La quantite d'iso-proturon diminue simultanemént dans le sol et la solution du sol mais la fraction dissoute de l'herbicide residuel décroit de 26 à 15%. A basse température, la dégradation de l'herbicide est plus lente et les produits de dégradation sont généralement moins abondants à l'exception notable du métabolite X⁵ qui est présent a un niveau élevé, en particulier dans la solution du sol. Veränderung der Konzentration von Isoproturon und seiner Abbauprodukte im Boden und in der Bodenlösung bei Inkubation Veränderung der Konzentration von [¹⁴C]-Car-bonyl-Isoproturon und seiner Abbauprodukte in einem Lehmboden und in der Bodenlösung wurden nach 6 Wochen Inkubation bei 11 und 18°C und Extraktion bzw. Probennahme durch Glasmikrofaserfilter gemessen. Während des Herbizidabbaus wurden bis zu 20 % der Radioaktivität als ¹⁴CO2 freigesetzt, und die nichtextrahierbare Radioaktivität nahm zu (bis zu 30 %). Monomethyl-Isoproturon war der Hauptmetabolit, gefolgt vom Metabolit X₅ (möglicherweise Hydroxy-didesmethyl-Isoproturon). Isoproturon und Monomethyl-Isoproturon waren weitgehend an Bodenpartikeln adsorbiert, während der Metabolit X₅ vorwiegend in der Bodenlösung gefunden wurde. Die Isoproturon-Konzentrationen nahmen sowohl im Boden als auch in der Bodenlösung ab, aber der Anteil des Herbizidrückstands in der Bodenlösung ging von 26 auf 15 % zurück. Bei der niedrigen Temperatur wurde das Herbizid langsamer abgebaut, und die Menge der Abbauprodukte war allgemein geringer. Der Metabolit X₅ lag jedoch in unerwartet hoher Menge vor, besonders in der Bodenlösung.     

Aminocyclopyrachlor sorption–desorption and leaching in soil amended with organic materials from sugar cane cultivation

The correct application of a new herbicide depends on knowledge concerning its behaviour within the cultivation system. The objective of this study was to evaluate the sorption–desorption process of aminocyclopyrachlor in soils with the addition of three aged organic materials from sugar cane and their transport via leaching. Sugar cane straw (12 t/ha), filter cake (90 t/ha) and vinasse (200 m³/ha) were added to a clayey soil 15, 30 and 60 days before herbicide application. Sorption and desorption were evaluated by the batch equilibrium method. For leaching assessments, the materials were applied to the soil surface. Sorption was relatively low in all treatments (K_d = 0.17–0.41 L/kg), although significantly higher in soil without organic material addition. A negative correlation between herbicide sorption and increased soil base saturation was observed, indicating competition for sorption sites. With the addition of vinasse, 71% of the herbicide reached the leachate, while <50% reached the leachate in the other treatments. Aminocyclopyrachlor availability was not reduced with organic material addition to the soil, which may be favourable for weed control. However, the presence of vinasse leads to the risk of leaching to deeper soil layers than the seed bank.     

Influence of temperature on the volatilization of triallate and terbutryn from two soils

The rate of volatilization of the formulated herbicides triallate and terbutryn was studied in a volatilization chamber under controlled laboratory conditions using two soils with sand and loam textures, respectively. The influence of the most relevant experimental variables was investigated by measuring the amount of volatilized herbicides after their incorporation to the soils. The effect of soil temperature was studied in the range from 5 °C to 25 °C. Initial soil water content was fixed at field capacity depending on the physical characteristics of each soil. The volatilized herbicide was trapped in C18 cartridges during different time intervals and analyzed by HPLC. The volatilization losses for triallate ranged from 7 to 58%, whereas the losses for terbutryn ranged from 1 to 6%. Sorption and volatilization resulted in two coupled effects of major importance in these experiments: the sorption process was favoured as temperature decreased, whereas volatilization increased as temperature increased. © 2000 Society of Chemical Industry     

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     

Reduced metribuzin pollution with phosphatidylcholine-clay formulations

BACKGROUND: Metribuzin is a widely used herbicide that has been identified as a groundwater contaminant. In this study, slow‐release formulations of metribuzin were designed by encapsulating the active ingredient in phosphatidylcholine (PC) vesicles and adsorbing the vesicles onto montmorillonite. RESULTS: The maximum active ingredient content in the slow‐release formulations was 246 g kg^?1. Infrared spectroscopy results revealed that the hydrophobic interactions between metribuzin and the alkyl chains on PC were necessary for encapsulation. In addition, water bridges connecting the herbicide and the PC headgroup enhanced the solubility of metribuzin in PC. Adsorption experiments in soils were performed to evaluate the relationship between sorption and leaching. Funnel experiments in a sandy soil revealed that the herbicide was not irreversibly retained in the formulation matrix. In soil column experiments, PC–clay formulations enhanced herbicide accumulation and biological activity in the top soil layer relative to a commercial formulation. PC–clay formulations also reduced the dissipation of metribuzin by a factor of 1.6–2.5. CONCLUSIONS: A reduction in the recommended dose of metribuzin can be achieved by employing PC–clay formulations, which reduces the environmental risk associated with herbicide applications. Moreover, PC and montmorillonite are non‐toxic and do not negatively affect the environment. Copyright © 2010 Society of Chemical Industry     

Perfusion studies with bromoxynil octanoate in soil

The breakdown of bromoxynil octanoate in 5 different soil types has been studied in a soil perfusion apparatus using herbicide labelled with ¹⁴C either in the cyano group or in the aromatic ring. Even when applied at rates equivalent to 5 to 25 times those used commercially, the herbicide was fairly rapidly and extensively degraded at 15°. After 12 to 13 weeks, up to 80% of the radioactivity in the ¹⁴CN group and up to 63 % of the ¹⁴C in the ring were liberated as carbon dioxide. A small proportion (16 to 19%) of the radioactivity from ring-labelled herbicide remained attached to the soil, probably not as the original herbicide, but in a form not readily leached. Only trace quantities of 3,5-dibromo-4-hydroxy-benzamide (0.5%) and 3,5-dibromo-4-hydroxybenzoic acid (0.1%) were detectable during these soil perfusions.     

Effect of environmental factors on herbicidal activity of diphenamid

Diphenamid (N,N-dimethyl-2,2-diphenylacetamide) in an aqueous solution in plastic bottles was partially detoxified when exposed to sunlight for 1 week. Varying spray volumes from 300 to 1,800 I/ha did not have an appreciable effect on the phytotoxicity of diphenamid, sprayed on a coarse or fine soil surface. The marked dissipation of diphenamid which occurred from the soil surface was attributed to photodecomposition and volatilization. Diphenamid phytotoxicity was greater when the first irrigation after spraying was applied in four increments of 100 m³/ha or two increments of 200 m¹/ha than when it was applied in a single 400 m¹/h watering; the latter caused more leaching of the herbicide. The diphenamid fraction leached out of a 4-cm soil layer increased as the organic matter content in the soil decreased, from 25% in peat (22.3% o.m.) to >88% in sandy loam (0.9% o.m.). The herbicidal activity remaining after leaching was lower in sandy loam and in peat than in soil with medium organic matter content (11.6% and 6.2%). Diphenamid degradation rate in soil at 50% field capacity moisture level, increased when temperature was increased from 10° to 30°C. After 4 months of incubation at 10°C, 40-50% of the original herbicide was detoxified, while at 20° and 30°C the loss exceeded 90%. Within the range of day-temperatures of 10° to 40°C in soil and of 10° to 35°C in nutrient solution, diphenamid phytotoxicity to tomato seedlings increased with temperature.     

Degradation of triasulfuron in soil under laboratory conditions

Degradation of triasulfuron in non-autoclaved and autoclaved soil incubated at different temperatures and moisture contents was evaluated in the laboratory using a maize root growth bioassay. Disappearance of triasulfuron was faster in non-autoclaved than in autoclaved soil, indicating the importance of microorganisms in the breakdown process. Degradation of the herbicide was faster at 30°C than at 10°C, with half-lives of 11–13 days at 30°C and 30–79 days at 10°C. Degradation of the herbicide was influenced more by temperature than by variation in soil moisture. Disappearance of the herbicide was rapid in the non-autoclaved soil at 30°C during the initial 30 days of incubation, but low levels of residues persisted for up to 90 days. A second application of the herbicide, to soil in which an initial dose of triasulfuron had degraded, disappeared at the same rate as herbicide added to previously untreated soil, indicating that there was no enhancement of degradation with repeated application of herbicide. Dégradation du triasulfuron dans le sol en conditions de laboratoire La dégradation du triasulfuron dans des sols non autoclavés et autoclavés, incubés à des températures et à des teneurs en humidité différentes, a étéévaluée au laboratoire en utilisant un bio essai sur la croissance d'une racine de maïs. La disparition du triasulfuron a été plus rapide en sol non autoclavé qu'en sol autoclavé, soulignant l'importance des microorganismes dans le processus de dégradation. La dégradation de l'herbicide a été plus rapide à 30°C qu'à 10°C avec des demi-vies respectives de 11–13 jours et de 30–79 jours. La dégradation de l'herbicide a été plus influencée par la température que par les variations d'humidité du sol. La disparition de l'herbicide a été rapide dans le sol non autoclavéà 30°C pendant les 30 premiers jours d'incubation, mais de faibles résidus persistaient au delà de 90 jours. Une seconde application d'herbicide sur un sol dans lequel une dose initiate de triasulfuron avait été dégradée, a disparu de la même façon qu'une dose appliquée sur un sol non traitd, montrant qu'il n'y avait pas d'augmentation de la dégradation à la suite d'une répétition d'application. Abbau von Triasulfuron im Boden unter Laborbedingungen Der Abbau von Triasulfuron in nicht sterilisiertem und sterilisiertem Boden bei verschiedener Temperatur und Bodenfeuchte wurde mit einem Maiswurzel-Wachstumstest untersucht. Die Menge des Triasulfurons nahm im nicht-sterilisierten Boden schneller ab als im sterilisierten, was auf mikrobiellen Abbau hinweist. Das Herbizid wurde bei 30 °C mit einer Halbwertszeit von 11 bis 13 Tagen schneller abgebaut als bei 10 °C mit einer von 30 bis 79 Tagen. Der Abbau wurde durch die Temperatur stärker beeinflußt als durch Änderung der Bodenfeuchte. Das Herbizid unterlag in den ersten 30 Tagen bei 30 °C im nichtsterilisierten Boden einem schnellen Abbau, doch geringe Rückstände wurden bis zu 90 Tagen gefunden. Bei einer zweiten Applikation des Herbizids auf Boden, in dem schon eine erste Dosis von Triasulfuron abgebaut worden war, nahm der Wirkstoff im selben Maße wie zuvor ab, so daß bei wiederholter Anwendung nicht mit einem verstärkten Abbau gerechnet werden kann.     

The effects of temperature and humidity on the toxicity of three organophosphorus insecticides to adult Oryzaephilus surinamensis (L.)

The toxicities, to a laboratory susceptible strain and to a resistant strain of Oryzaephilus surinamensis (L.), of water-dispersible powder formulations of pirimiphos-methyl, fenitrothion or chlorpyrifos-methyl under constant conditions of 25°C and 70% r. h. were compared to the toxicities when the insects were exposed to a diurnal cycle of 12.5–20–12.5°C and 70–50–70% r. h. to simulate grain store conditions in the UK during spring and autumn. All the insecticides were more effective at 25°C and 70% r. h. The LD₅₀ values for the susceptible strain were low, being 4.4 and 1.4 mg m^?2 at 12.5-20°C and 25°C, respectively, for chlorpyrifos-methyl, 18.3 and 4.1 mg m^?2, respectively, for pirimiphos-methyl, and 4.0 and < 1.O mg m^?2, respectively, for fenitrothion. The LD₅₀ values obtained from the two sets of environmental conditions for a resistant strain (484) differed by factors of 1.8 for chlorpyrifos-methyl, 4.8 for pirimiphos-methyl, and 7.3 for fenitrothion. Toxicity studies were also made with chlorpyrifos-methyl under various constant conditions of temperature and humidity from 5–30°C (5°C intervals) and 30, 50, 70 and 90% r. h., and also at O°C and 60% r. h. Chlorpyrifos-methyl was very effective and there was little or no cross resistance to chlorpyrifos-methyl in the resistant strain. From 15 to 30°C, mortality was high, and differences in mortality at the LD₅₀ level for the various humidities were slight, but there was a decrease in mortality with decreasing humidity at any one temperature, in particular, at 5°C, 50 and 70% r. h., and 10°C and 50% r. h. Chlorpyrifosmethyl was more toxic to both strains at the highest humidity (90%) throughout the whole temperature range. The LD₅₀ values for each strain decreased at each temperature as the water vapour concentration was increased. At O°C and 60% r. h., all the insects from both strains died but the cause of death was not clear.     

Persistence of pyrazosulfuron in rice-field and laboratory soil under Indian tropical conditions

BACKGROUND: Pyrazosulfuron ethyl, a new rice herbicide belonging to the sulfonylurea group, has recently been registered in India for weed control in rice crops. Many field experiments revealed the bioefficacy of this herbicide; however, no information is available on the persistence of this herbicide in paddy soil under Indian tropical conditions. Therefore, a field experiment was undertaken to investigate the fate of pyrazosulfuron ethyl in soil and water of rice fields. Persistence studies were also carried out under laboratory conditions in sterile and non‐sterile soil to evaluate the microbial contribution to degradation. RESULTS: High‐performance liquid chromatography (HPLC) of pyrazosulfuron ethyl gave a single sharp peak at 3.41 min. The instrument detection limit (IDL) for pyrazosulfuron ethyl by HPLC was 0.1 µg mL^?1, with a sensitivity of 2 ng. The estimated method detection limit (EMDL) was 0.001 µg mL^?1 and 0.002 µg g^?1 for water and soil respectively. Two applications at an interval of 10 days gave good weed control. The herbicide residues dissipated faster in water than in soil. In the present study, with a field‐soil pH of 8.2 and an organic matter content of 0.5%, the pyrazosulfuron ethyl residues dissipated with a half‐life of 5.4 and 0.9 days in soil and water respectively. Dissipation followed first‐order kinetics. Under laboratory conditions, degradation of pyrazosulfuron ethyl was faster in non‐sterile soil (t_1/2 = 9.7 days) than in sterile soil (t_1/2 = 16.9 days). CONCLUSION: Pyrazosulfuron ethyl is a short‐lived molecule, and it dissipated rapidly in field soil and water. The faster degradation of pyrazosulfuron in non‐sterile soil than in sterile soil indicated microbial degradation of this herbicide. Copyright © 2012 Society of Chemical Industry