Degradation of bifenthrin,chlorpyrifos and imidacloprid in soil and bedding materials at termiticidal application rates

Organophosphorus, pyrethroid and chloronicotinyl insecticides have been used to control termites in building structures in recent years. We investigated the degradation behaviour of three insecticides (bifenthrin, chlorpyrifos and imidacloprid) at termiticidal application rates under standard laboratory conditions (25 °C, 60% field moisture capacity and darkness) for 24 months. The study was carried out on one soil and two bedding materials (sand-dolomite and quarry sand), which are commonly used under housing in Australia. Experiments were also conducted to examine the effect of soil moisture on the degradation of these insecticides. Insecticide residues in the samples collected at different days after application were measured by high performance liquid chromatography (HPLC). The rate of degradation of bifenthrin and imidacloprid insecticides was adequately described by a first-order kinetic model (r² = 0.93–0.97). However, chlorpyrifos degradation was biphasic, showing an initial faster degradation followed by a slower rate. Therefore, the degradation data during the slower phase only (after a two-month period) followed the first-order law (r² = 0.95). Soil moisture had little effect on degradation of imidacloprid and bifenthrin. Among the three insecticides, bifenthrin and imidacloprid were most stable and chlorpyrifos the least. Chlorpyrifos showed a major loss (75–90%) of residue during the 24 months incubation period. In the bedding materials, simultaneous accumulation of the primary metabolite of chlorpyrifos, TCP (3,5,6-trichloro-2-pyridinol) was observed. Hydrolysis appeared to have caused the observed rapid loss of chlorpyrifos, especially in the highly alkaline bedding materials (sand-dolomite and quarry sand). © 1999 Society of Chemical Industry     

Imidacloprid mobility and longevity in soil columns at a termiticidal application rate

The mobility, longevity and termiticidal activity of imidacloprid (Premise 2 termiticide; Bayer Environmental Sciences) at the termiticidal labeled rate for perimeter treatment were tested in vegetated and non-vegetated soil columns in two tests: in cone plots and in polyvinyl chloride (PVC) pipes. Imidacloprid content in the cone plot eluate peaked at 1 month, declined rapidly by the second month and then entered a lagging phase. The concentration of imidacloprid in the cone plot soil declined from 84.5 microg g(-1) initially to 7.5 microg g(-1) (non-vegetated plots) and 8.1 microg g(-1) (vegetated plots) 6 months later. Neither eluate concentration nor soil concentration was affected by the presence of vegetation in the cone plots. In the PVC pipes, the top 15 cm of which was treated with Premise 2 at the perimeter labeled rate, imidacloprid half-life was estimated at 6-9 months for vegetated and non-vegetated soil. Extractable imidacloprid declined more rapidly in the first 15 months than afterwards. Mobility of imidacloprid into lower, untreated soil depths was higher in non-vegetated pipes, and was likely due to the effect of vegetation on soil moisture. The presence of vegetation had little effect on the termiticidal activity of treated soil in the PVC pipes.     

Bifenthrin longevity at the termiticidal application rate

BACKGROUND: The longevity, mobility and insecticidal activity of bifenthrin at the termiticidal application rate for perimeter treatment were investigated in packed-soil columns in the laboratory and greenhouse. RESULTS: Bifenthrin was not detected in the eluates of packed-soil cones over a period of 6 months. In larger pipe plots incorporating bifenthrin into the top 15 cm of the soil, the compound degraded in a biphasic fashion. Within the treated soil, the effect of vegetation on the amount of bifenthrin remaining in the soil depended on soil depth and time, and soil half-lives were longer in non-vegetated soil. Bifenthrin residues were higher in the top 7.5 cm of soil and declined over time. Movement of bifenthrin into the top untreated soil depth was observed, but much less was observed in lower depths. The soil remained toxic to termites in 3 day and 7 day forced exposure bioassays for the 30 month duration of the study. CONCLUSIONS: Concentrations of bifenthrin will remain in the soil at levels sufficient to kill termites for more than 30 months. Published 2011 by John Wiley & Sons, Ltd.     

不同氮肥用量下乙草胺对土壤氮转化过程的影响

在实验室培养条件下,研究了不同氮肥用量水平下土壤中分别添加除草剂乙草胺对尿素态氮的水解、硝化及反硝化等氮素转化过程的影响。试验设7个处理,分别为施氮量0、75、150和300mg/kg以及氮75、150、300mg/kg+乙草胺(有效成分10mg/kg)处理。结果表明:当施氮量为75mg/kg时,乙草胺对尿素态氮的水解和硝化作用无明显影响;施氮量为150和300mg/kg时,乙草胺可抑制尿素态氮的水解过程(PP<0.01)。研究表明,施用乙草胺对土壤中氮素的转化过程具有一定影响,然而在不同的施氮量条件下,其影响效果差异较大,高氮时影响更明显。     

Effect of vegetation on the longevity,mobility and activity of fipronil applied at the termiticidal rate in laboratory soil columns

BACKGROUND: Termiticides are applied at concentrations much higher than those used in agricultural settings. The longevity of fipronil has not yet been examined at the rates used for termite control, nor has the compound's movement in the soil been addressed. RESULTS: Fipronil was detected in the eluates of treated soil cones, increasing initially and then decreasing to a steady concentration of about 1 µg mL^?1. In larger PVC pipe plots, fipronil in the top treated soil depth (0–7.5 cm) dissipated more rapidly (half‐life of 11–13 months) than in treated soil at the next treated depth (7.5–15 cm; half‐life of 20–29 months). The presence of vegetation had no significant effect on the mobility, longevity or movement into untreated depths. Treated soil remained toxic to termites throughout the duration of the study. Fipronil moved into the 15–22.5 cm soil depth in sufficient concentration to cause 100% mortality to eastern subterranean termites in 3 day bioassays. CONCLUSION: Fipronil remains in treated soil at levels toxic to termites for at least 30 months. Movement of the active ingredient was observed in sufficient amounts to kill termites in non‐treated soil directly below the treated soil. Published 2010 by John Wiley & Sons, Ltd.     

Spatial variability in the degradation rates of isoproturon and chlorotoluron in a clay soil

Thirty separate soil samples were taken from different locations at the Brimstone farm experimental site, Oxfordshire, UK. Incubations of isoproturon under standard conditions (15 °C; ?33 kPa soil water potential) indicated considerable variation in degradation rate in the soil, with the time to 50% loss (DT₅₀) varying from 6 to 30 days. These differences were confirmed in a second comparative experiment in which degradation rates were assessed in 11 samples of the same soil in two separate laboratories using an identical protocol. There was a significant negative linear relationship (r²= 0.746) between the DT₅₀ values and soil pH in this group of soils. In a third experiment, degradation rates of the related compound chlorotoluron were compared with those of isoproturon in 12 separate soil samples, six of which had been stored for several months, and six of which were freshly collected from the field. Degradation of both herbicides occurred more slowly in the stored samples than in the fresh samples but, in all of them, chlorotoluron degraded more slowly than isoproturon, and there was a highly significant linear relationship (r²=0.916) between the respective DT₅₀ values.     

Longevity of a mixture of acetamiprid and bifenthrin (Transport(TM) ) at the termiticidal application rate

BACKGROUND: The 30 month longevity, mobility and insecticidal activity of a combination of acetamiprid and bifenthrin currently marketed in the United States for the prevention of termite infestation in buildings was investigated in greenhouse and laboratory studies. RESULTS: Acetamiprid dissipated to below the limit of detection within 7 months of application, while bifenthrin remained in the soil at levels sufficient to kill termites for the duration of the study. Acetamiprid was detected in decreasing amounts in eluates of treated soil from months 1 to 4, while no bifenthrin was detected in eluates at any time. The treated soil remained toxic to termites for the 30 month duration of the study. Two indices of synergy between technical‐grade acetamiprid and bifenthrin demonstrated that it is unlikely that there would be any synergism between the two active ingredients in the field. The presence of vegetation did not have a significant effect on the longevity of bifenthrin, except at intermediate times, where residues in the treated soil were higher in vegetated plots, depending on depth and time. CONCLUSIONS: Acetamiprid has a short residual time in soil, and this formulation's effectiveness beyond about 7 months against subterranean termites is due to the bifenthrin content. Copyright © 2011 Society of Chemical Industry     

Mobility,longevity and activity of chlorfenapyr in soils treated at a termiticidal rate

BACKGROUND: The mobility, longevity and termiticidal activity of chlorfenapyr applied to soils at the termiticidal labeled rate was evaluated for 30 months after treatment (MAT) in a greenhouse study. RESULTS: There was little dissipation of chlorfenapyr in soil treated at the labeled rate for perimeter treatments for the prevention and control of termite infestations. Chlorfenapyr was detected in soil immediately below the initially treated soil in the packed soil columns. This was likely due to settling of soil. The treated soil remained toxic to subterranean termites in 3 and 7 day bioassays over the duration of the study. The treated soil displayed slow‐acting properties regarding toxicity to termites. Trace amounts of chlorfenapyr were detected in the eluates of packed soil cones. CONCLUSION: The commercial formulation of chlorfenapyr used in this study (21.45% concentrate diluted to 0.125% prior to application) killed 100% of the tested subterranean termites for at least 30 months. Copyright © 2012 Society of Chemical Industry     

Effects of microbial inhibitors on the degradation rates of metamitron,metazachlor and metribuzin in soil

Rates of carbon dioxide evolution and degradation rates of metamitron, metazachlor and metribuzin were measured in two soils in the presence of three microbial inhibitors. The nonselective microbial inhibitor sodium azide reduced both carbon dioxide evolution and the rate of loss of all three herbicides in both soils, although the reduction in degradation rate of metamitron was small. The antibacterial antibiotic novobiocin enhanced carbon dioxide evolution from both soils but had variable effects on the rates of herbicide degradation. It inhibited degradation of metazachlor and metribuzin, and in one of the soils its effects on metazachlor degradation were similar to those of sodium azide. Novobiocin inhibited degradation of metamitron to a small extent in one soil only. The antifungal antibiotic cycloheximide also enhanced carbon dioxide evolution from both soils. In general, its effects on herbicide degradation were similar to those of novobiocin, although the extent of inhibition was usually less pronounced. The results are discussed in terms of the relative involvement of microorganisms in degradation of the three herbicides.     

Factors affecting degradation rates of five triazole fungicides in two soil types: 1. Laboratory incubations

Triazole fungicides are now widely used commercially and several are known to be persistent in soil. The degradation rates of five such fungicides were measured in laboratory tests with two soils over 720 days, with analysis of soil extracts by high-pressure liquid chromatography. Behaviour in a sandy loam and a clay loam were similar, and incubation of the compounds either singly or in admixture did not influence loss rates except for those of flutriafol which were lower in the latter. Triadimefon was quite rapidly reduced to triadimenol, though traces of the former were always found, indicating a possible redox equilibrium. Flutriafol, epoxiconazole and triadimenol (derived from triadimefon) were very persistent, breakdown following first-order kinetics with half-lives greater than two years at 10 °C and 80% field capacity. Propiconazole was moderately persistent, with a half-life of about 200 days under these conditions. Degradation rates increased about 3-fold as the temperature was increased from 5 to 18 °C, though decreasing soil moisture to 60% field capacity only slightly slowed degradation. The rate constants obtained are used in a companion paper describing field studies on these two soils to compare laboratory-measured degradation rates with losses in the field following commercial sprays. © 1999 Society of Chemical Industry     

Enhanced degradation in soil of tri-allate and other carbamate pesticides following application of tri-allate

Tri-allate degraded faster in soil from a site (T1) that had received 1·7 kg ha^?1 of tri-allate annually for 23 years than in soil from an adjacent site (TO) that had received no pesticide application. Soil from the untreated site, which had been removed to a glasshouse and treated three times per annum with tri-allate at 1·7 kg ha^?1 for 7 years (T2), also showed faster degradation. Soil previously treated with tri-allate showed an increased degradation rate for carbofuran and EPTC but not for aldicarb. A further experiment, 2 years after the last treatment with tri-allate, showed that the enhanced degradation effect was still present. Degradation rates were always in the order T1 > T2 > T0 for tri-allate, EPTC and carbofuran. Half-life for degradation was reduced for tri-allate and carbofuran by approximately 40% in the previously treated soils and for EPTC by approximately 80% when compared with the previously untreated soil.     

The influence of soil properties on the rates of degradation of metamitron,metazachlor and metribuzin

The rates of degradation of metamitron, metazachlor and metribuzin were measured in 12 mineral soils and the first order rate constants were compared with soil properties by regression analysis. Rates of metamitron degradation were best described by a multiple regression involving the silt content of the soil and the fraction of the total herbicide content which was available in the soil solution. Metazachlor degradation was best described by a multiple regression involving the sand content of the soil, the availability of the herbicide in the soil solution and soil microbial respiration. There was evidence that metribuzin degradation in any one soil was closely related to microbial activity, and rate constants per unit microbial respiration were derived for each soil. These rate constants were best described by a multiple regression involving the Freundlich adsorption constant and the sand content of the soils. The best regression equations for each herbicide were tested against observed degradation rates in an additional group of six soils. The calculated rates compared favourably with those observed for both metamitron and metazachlor, but with metribuzin, there was good agreement with one soil only.     

二月兰不同翻压量对土壤肥力的影响

通过室内土壤培养试验,研究了绿肥二月兰（Orychophragmus violaceus）不同翻压量对土壤肥力的影响。结果表明,翻压二月兰可有效降低石灰性土壤pH值,45 000 kg·hm^-2（处理Ⅰ）和90 000 kg·hm^-2（处理Ⅱ）翻压量的土壤pH值在培养结束时（120 d）分别比对照降低了0.24和0.41个单位;翻压二月兰可显著提高土壤全氮、速效磷和速效钾含量,培养结束时处理Ⅰ、Ⅱ的土壤全氮、速效磷和速效钾含量分别比对照增加了0.06 g·kg^-1、2.00 mg·kg^-1、26.28 mg·kg^-1和0.09 g·kg^-1、3.32 mg·kg^-1、63.00 mg·kg^-1;土壤有效氮含量在翻压15天时达到峰值,此时处理Ⅰ、Ⅱ的有效氮含量分别比对照增加了12.95 mg·kg^-1和21.70 mg·kg^-1,但培养60天后各处理有效氮含量相近;翻压二月兰可在培养前期（22 d）较大幅度提高土壤有机碳含量,但22天后处理间差异缩小,培养结束时处理Ⅰ、Ⅱ的有机碳含量分别比对照增加了-0.06 g·kg^-1和0.33 g·kg^-1;翻压二月兰可降低土壤碳氮比,培养结束时处理Ⅰ、Ⅱ的碳氮比分别比对照下降了2.02和1.51个单位,降幅分别达到20.82%和15.58%。     

Effect of long‐term field application of pendimethalin: enhanced degradation in soil

The effect of long‐term application of pendimethalin in a maize–wheat rotation on herbicide persistence was investigated. Pendimethalin was applied at 1.5 kg AI ha⁻¹ separately as one or two annual applications for five consecutive years in the same plots. Residues of pendimethalin were determined by gas chromatography. Harvest‐time residues of the herbicide decreased gradually over the years and at the end of five years less than 3% of applied pendimethalin was recovered from soil as against 18% in the first year. Residues were found distributed in the soil profile up to 90 cm depth at the end of the experiment with peak distribution of 0.03 µg g⁻¹ in the surface layer of soil treated with 10 herbicide applications. The minimum distribution was, however, in the deepest soil (75–90 cm) profile. Some of the metabolites of pendimethalin ie dealkylated pendimethalin derivative, partially reduced derivative and cyclized product were also traced in surface and sub‐surface soils up to 90 cm. A study of the rate of degradation of pendimethalin in field‐treated soils under laboratory conditions revealed faster degradation compared to control soils. Only the surface soil (0–15 cm) showed this enhanced degradation of the herbicide, which could be due to the adaptability of the aerobic micro‐organisms to degrade pendimethalin. Microbes capable of degrading herbicide were isolated, identified and pendimethalin degradation was confirmed in nutrient broth. © 2000 Society of Chemical Industry     

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.     

Influence of application methods on the degradation of permethrin in laboratory,soil aerobic metabolism studies

The effects of application rate, volume, solvent and soil moisture content on the kinetics of mineralization and degradation, of [¹⁴C] permethrin have been studied in a sandy loam soil under standard laboratory conditions. During the incubation period, up to 32 days, the temperature and moisture level of the soil were controlled. Apart from the effects of application rate, which have been widely reported, application volume had the most significant effect on mineralization rate and T_1/2. [¹⁴C]Permethrin, at a level of a 1 mg kg^?1 in the soil, applied in 100 μl of methanol, resulted in the evolution of 14% of the applied radiochemical as [¹⁴C] carbon dioxide over 30 days. The same level applied in 1000 μl mineralized at a faster rate, with 30% [¹⁴C]carbon dioxide evolved over 30 days. The test chemical applied to soil in methanol mineralized at a significantly faster rate than a similar concentration applied in ethanol. There was no significant difference when comparing applications made using acetonitrile with those using methanol or ethanol. The addition of formulation ingredients resulted in little or no variation in mineralisation rate compared to an equivalent application volume of methanol/water.     

Factors controlling degradation of pesticides in soil

Rates of pesticide degradation in soil exhibit a high degree of variability, the sources of which are usually unclear. Combining data from incubations performed using a range of soil properties and environmental conditions has resulted in greater understanding of factors controlling such degradation. The herbicides clomazone, flumetsulam, atrazine, and cloransulam-methyl, as well as the former insecticide naphthalene offer examples of degradation kinetics controlled by coupling competing processes which may in turn be regulated separately by environmental conditions and soil properties. The processes of degradation and volatilization appear to compete for clomazone in solution; sorbed clomazone is degraded only after the solution phase is depleted. Similarly, volatilization of naphthalene is enhanced when degradation has been inhibited by high nutrient levels. Degradation of the herbicide flumetsulam has been shown to be regulated by sorption, even though the compound has a relatively low affinity for the soil. The fate pathway for cloransulam-methyl shifts from mineralization to formation of metabolities, bound residues and physically occluded material as temperature increases. Atrazine degradation in soil may be controlled in part by the presence of inorganic nitrogen, as the herbicide appears to be used as a nitrogen source by micro-organisms. New insight gained from measurement of multiple fate processes is demonstrated by these examples.     

Stereoselective degradation of ethofumesate in turfgrass and soil

The stereoselective degradation of ethofumesate in turfgrasses and several agricultural soils was investigated to provide details of the fate of this chiral herbicide. Racemic ethofumesate was either foliar applied to two species of turfgrass or fortified into four types of agricultural soils. (+)- and (−)-Enantiomers were extracted and analyzed by a validated chiral HPLC method which involved extraction of samples with organic solvent followed by separation on cellulose-Tris-(3,5-dimethylphenylcarbamate)-based chiral column and quantification by UV absorbance at 230 nm. Mean recoveries of each enantiomer fortified at 0.5, 5, and 10 μg g⁻¹ ranged from 82.3 ± 5.84 to 92.5 ± 2.87% in turfgrasses and from 86.0 ± 5.09 to 98.1 ± 2.51% in soil. As a measure of this composition, the enantiomeric ratio (ER) was used, defined as the concentration ratio of (+)/(−)-enantiomer. Similarly, preferential degradation of the (−)-enantiomer was observed in both grass species with the largest ER of about 3 and in one of the test soil with ER = 1.65, resulting in residues enriched with (+)-enantiomer. This stereoselective degradation in this soil led to significant difference on half-lives between the two enantiomers. No stereoselective degradation was observed in other soils.     

Kinetics of linuron and metribuzin degradation in soil

The disappearance of linuron and metribuzin was studied during laboratory incubation of soil samples which had been taken from several depths at three sites, and treated with the pesticides. Temperature and water content of the soils were varied. There was a tendency for the rate of loss to be slower in soil taken from deeper horizons than in surface soil but the differences were not large. In only ten out of forty experiments did the value 1 for the apparent order of reaction fall within 95% confidence limits. In the remaining experiments the apparent reaction order was greater than 1 with eight values higher than 4. For one soil, the reaction order for linuron was markedly lower for incubation at 22°C compared with incubations at 10°C. The results could be explained on the basis that the systems were complex, involving consecutive or competing reactions. An alternative possibility is that the apparent complexities were artifacts brought about by the inherent limitations of the laboratory incubation system.     

Peroxidase activity and propanil degradation in soil*

The herbicide N-(3,4-dichloropxhenyl)-propionamide (propanil) and a metabolite of propanil, 3,4-dichloroaniline (DCA), were mixed with Nixon loam soil which was subjected to moisture and air-drying treatments. Degradation of propanil was altered by subjecting the treated soil samples to storage conditions of moisture, drying and chloroform. The peroxidase activity in fresh soil was very low when soil samples were collected during the cold season. The amount of 3,3′,4,4′- tetrachloroazobenzene (TCAB) produced from DCA increased with a simultaneous increase in the peroxidase activity in preincubated soil where carbon and nitrogen sources were added.