Degradation and persistence of gamma-HCH and chlorpyrifos-methyl in Ponderosa pine bark

Residues of gamma-HCH and chlorpyrifos-methyl in Ponderosa pine bark (Pinus ponderosa Laws.) were determined 7-300 days after spray treatment, by a rapid extraction method using ethyl acetate and sodium sulphate, and analysis by gasliquid chromatography using either an electron-capture or nitrogen-phosphorus detector. The residue data were fitted into a power curve equation, Y = ax^b, to determine the rates of insecticide disappearance. The half-life values (μg cm^?2), as interpolated from the power curve, indicate that 50% disappearance occurred in 43 (± 9) days for gamma-HCH and 102 (± 26) days for chlorpyrifos-methyl. When half-life values, however, are computed from extrapolated initial deposits, 50% disappearance occurred in 6 (± 1) days for gamma-HCH and 15 (±4) days for chlorpyrifos-methyl.     

Fate of fluroxypyr in soil

Batch adsorption K_oc values of fluroxypyr-methylheptyl ester (20000 1kg^?1) and fluroxypyr (74 1kg^?1) indicate increased mobility after hydrolysis of the ester to fluroxypyr. After 1 to 2 weeks incubation time in four soils, desorption K_oc values of fluroxypyr were 100-200 1kg^?1 but increased to 400-700 1kg^?1 after 8 weeks. The increase in desorption K_oc was related to incubation time and not to concentration, and it was interpreted as an entrapment of the fluroxypyr within the soil organic matter. Similar increases in desorption K_oc with incubation time were noticed for pyridinol and methoxypyridine metabolites of fluroxypyr. K_oc values also increased along the metabolic sequence fluroxypyr/pyridinol/methoxypyridine, with maximum K_oc values of 3000-4000 1 kg^?1 for the methoxypyridine metabolite. Hence mobility of the fluroxypyr aromatic ring strongly decreases with increased residence time in the soil.     

The effects of low-volume aeration on the residues and biological effectiveness of chlorpyrifos-methyl applied to wheat

The effects of low-volume ventilation on the persistence and biological efficacy of chlorpyrifos-methyl applied to English wheat were investigated. Four 20-tonne batches of wheat were treated with a dose of 2.5 mg kg^?1 chlorpyrifos-methyl. After treatment, two of the batches were aerated continuously at a rate of 17 m³ h^?1 tonne^?1 (10 cfm tonne^?1) for 16 weeks. The remaining two batches were not aerated. Samples were collected from both aerated and non-aerated wheat at intervals over the 16-week storage period and subjected to biological assay using laboratory multi-organophosphorus-resistant strains of Tribolium castaneum, Sitophilus granarius, Sitophilus oryzae and Oryzaephilus surinamensis. The samples were also analysed for chlorpyrifos-methyl residues. No differences in either the biological efficacy or the rate of chemical decomposition were detected between the aerated and non-aerated wheat.     

The fate of chlorpyrifos-methyl in stored wheat: A comparison of a laboratory-scale experiment with a pilot-scale treatment

An experiment was carried out in which a pilot-scale treatment of a bulk of grain with chlorpyrifos-methyl was compared with a laboratory treatment of 1 kilogram of grain with ¹⁴C-radio-labelled chlorpyrifos-methyl. The conditions under which the grain was maintained in the laboratory resembled those of the pilot-scale treatment as closely as possible, with sampling and analysis being carried out at the same time and in a similar manner in both. The results from the two experiments were in general agreement with approximately 60% of the chlorpyrifos-methyl remaining intact at the end. A satisfactory level of insect control was achieved in the pilot-scale treatment although it was not possible to assess efficacy in the radiochemical experiment. The use of the radio-label enabled more information about the fate of the degraded insecticide to be obtained from the laboratory experiment. The majority of this radioactivity comprised a fraction which remained within the grain tissue after solvent extraction. The level of activity in the grain tissues gradually increased with time but its nature is as yet unknown. The good agreement obtained between the residue profile and the breakdown patterns in both experiments would suggest that such a laboratory-scale experiment can be a satisfactory model for the situation obtaining in a larger-scale treatment.     

乐果及其代谢物氧乐果在不同生育期豇豆中的残留消解动态

为明确不同生育期豇豆上施用乐果可能产生的残留风险,以40%乐果乳油按有效成分设低（540 g/hm2）、中（600 g/hm2）和高（900 g/hm2）3个施药剂量,开展了苗期、结荚期2次施药和结荚期3次施药3种场景下的田间模拟试验,按照一定的时间间隔采集成熟豇豆样品,采用乙腈提取,C18分散净化,超高效液相色谱-串联质谱检测。结果表明:乐果和氧乐果在豇豆中的定量限均为0.01 mg/kg,在0.01~2 mg/kg添加水平下,乐果和氧乐果的平均回收率在77%~101%,相对标准偏差为3.1%~17%。距苗期最后一次施药后10 d,乐果在豇豆中的残留量各处理均低于中国国家标准中规定的最大允许残留限量（MRL）值0.5 mg/kg,最高为0.043 mg/kg;但其代谢物氧乐果残留量在施药后14 d,仅540 g/hm2的处理低于其MRL值0.02 mg/kg,施药后18 d仍有检出,最高为0.013 mg/kg。于结荚期2次和3次施药条件下,豇豆中乐果的残留量分别于施药后3 d和5 d即低于其MRL值（0.5 mg/kg）;而其代谢产生的氧乐果在施药后10 d仅540 g/hm2处理在豇豆中的残留量低于其MRL值。表明乐果使用后的残留超标风险主要源于其代谢物氧乐果。因此,建议豇豆结荚期不宜施用乐果,对其在苗期施用也应严格限制。     

Bioavailability of conjugated and soil-bound [14C]‘hydroxymonolinuron’-β-D-glucoside residues to earthworms and ryegrass

The β-D -glucoside conjugate of [¹⁴C]‘hydroxymonolinuron’, [phenyl-¹⁴C]-3-(4- chlorophenyl)-1-(hydroxymethyl)-1-methoxyurea-β-D -glucoside (HM-β-G) and its soil-bound residues, prepared as described, were used to estimate its bioavailability to earthworms and ryegrass plants. The results demonstrate that these bound residues were available to both earthworms and ryegrass. The concentration in the earthworms, expressed on a dry weight basis after 42 days of exposure, was equal to the surrounding soil. The earth worms were found to be more efficient in remobilising and absorbing soil-bound residues than ryegrass plants after 59 days of cultivation. Fractionation of the soil-bound residues showed that 29% of the radiocarbon was associated with fulvic acid, 20% with humic acid and 9% with the humin fraction. 4-Chlorophenylurea, a metabolite of HM-β-G proved to be a key compound in the formation of soil-bound residues. The amount of radioactivity (bound residues), recovered from soil through solubilisation by means of 0.5M -acid and alkali, seems to be a criterion for predicting the bioavailability of bound phenylurea residues. The half-life of soil-bound residues was estimated to be about 4.6 years.     

Persistence and activity of mexacarbate and its metabolites against spruce budworm larvae

This study was conducted to determine if metabolites of mexacarbate contribute to its residual toxicity to spruce budworm (Choristoneura fumiferana) larvae. Potted white spruce (Picea glauca) trees were treated with ‘Zectran’ UCZF # 19 at 100 g a.i. ha^?1 and kept in a glasshouse. Mexacarbate residues declined by 98–99% within three days and reached non-detectable levels 10 days after treatment. Mortality of larvae fed on buds from these trees declined more gradually and was still 19–27% when exposed 10 days after treatment. The very low levels of mexacarbate (<0.07 μg g^?1) found after three days did not produce such mortality. Gas chromatographic analysis of metabolites in needles revealed that after three days, 4-methylformamido-3,5-xylyl N-methylcarbamate was present at levels 20–30 times higher than the parent compound. This metabolite was about 50 times less toxic than mexacarbate to larvae when applied topically but was only 7 times less toxic when ingested. Two other methylcarbamate metabolites, the amino, and methylamino analogues were detectable for one day following treatment but not at later time points. They were as toxic as mexacarbate both topically and orally. Based on these findings, the methylformamido analogue could contribute to the residual toxicity of mexacarbate treatments of spruce.     

Variability of retention process of isoxaflutole and its diketonitrile metabolite in soil under conventional and conservation tillage

BACKGROUND: Sorption largely controls pesticide fate in soils because it influences its availability for biodegradation or transport in the soil water. In this study, variability of sorption and desorption of isoxaflutole (IFT) and its active metabolite diketonitrile (DKN) was investigated under conventional and conservation tillage. RESULTS: According to soil samples, IFT K_D values ranged from 1.4 to 3.2 L kg^?1 and DKN K_D values ranged from 0.02 to 0.17 L kg^?1. Positive correlations were found between organic carbon content and IFT and DKN sorption. IFT and DKN sorption was higher under conservation than under conventional tillage owing to higher organic carbon content. Under conservation tillage, measurements on maize and oat residues collected from the soil surface showed a greater sorption of IFT on plant residues than on soil samples, with the highest sorbed quantities measured on maize residues (K_D ≈ 45 L kg^?1). Desorption of IFT was hysteretic, and, after five consecutive desorptions, between 72 and 89% of the sorbed IFT was desorbed from soil samples. For maize residues, desorption was weak (<50% of the sorbed IFT), but, after two complementary desorptions allowing for IFT hydrolysis, DKN was released from maize residues. CONCLUSION: Owing to an increase in organic carbon in topsoil layers, sorption of IFT and DKN was enhanced under conservation tillage. Greater sorption capacities under conservation tillage could help in decreasing DKN leaching to groundwater. Copyright © 2012 Society of Chemical Industry     

Metabolism of the insecticide SD 8280, 2-chloro-1-(2,4-dichlorophenyl)vinyl dimethyl phosphate,following its application to rice

The metabolism of the insecticide SD 8280 [2-chloro-1-(2,4-dichlorophenyl)vinyl dimethyl phosphate] in rice plants has been examined. When rice seedlings were treated with [¹⁴C]-SD 8280 the major metabolite was 1-(2,4-dichlorophenyl)ethanol which was present mainly conjugated with plant carbohydrates. This compound was also the major metabolite present in grain and straw from rice treated with [¹⁴C]-SD 8280 and grown to maturity under paddy conditions both in the glasshouse and in an outdoor enclosure. Other metabolites detected in the mature plants included 2-chloro-1-(2,4-dichlorophenyl)vinyl methyl hydrogen phosphate and 2,4-dichloro-benzoic acid, both of which occurred in free and conjugated forms. Paddy water was sampled at intervals after the application of [¹⁴C]-SD 8280 and the total residue in the water fell from initial levels of 0.28–1.1 μg/ml (expressed as SD 8280 equivalent) immediately after treatment to <0.01 μg/ml after 2–3 weeks. The total residues in the soil from these experiments were low and did not exceed 0.20 mg/kg (SD 8280 equivalents) through the 0–15 cm profile.     

Metabolism and cell wall incorporation of phenoxyacetic acid in soybean cell suspension culture

The metabolism of [¹⁴C]phenoxyacetic acid (POA) was studied in cell suspension culture of soybean (Glycine max). POA was metabolized to 4-HO-POA, 4-HO-POA glucoside and 4-HO-POA glycosidic ester. A large part of the 4-HO-POA glucoside and small amounts of the glycosidic ester were recovered in the medium. POA was also converted to non-extractable residues bound to cell walls. Sequential extraction of cell-wall polymers showed that non-extractable residues, partly identified with 4-HO-POA and POA, were mainly associated with hemicelluloses and lignin. Comparison of the metabolism of [carboxy-¹⁴C]- and [phenyl-¹⁴C]POA revealed some degradation of the POA side-chain, followed in all probability by the incorporation of the aromatic moiety into cell walls. However, the sturdiness of the resulting bonds prevented precise identification of these bound aromatic structures. In summary, the degradation of POA in soybean cell culture provided a good model to study the formation of non-extractable residues of pesticides. © 1999 Society of Chemical Industry     

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.     

Impact of aluminium stress on oxalate and other metabolites in Rumex obtusifolius

To understand alterations of oxalate and other metabolite levels induced by aluminium ion (Al³⁺) stress in Rumex plants, we measured the metabolites in R. obtusifolius using the capillary electrophoresis–mass spectrometry. Oxalate and its precursors (isocitrate and citrate) accumulated in leaves of R. obtusifolius after the Al³⁺ treatment at pH 4.5. Such increase was not observed under the acidic condition (pH 4.5) without Al³⁺. Principal component analysis showed organ‐specific changes in metabolite levels in R. obtusifolius by the Al³⁺ treatment. Highly positive correlations between oxalate and its precursors were revealed by hierarchical clustering and correlation analyses. An increase in oxalate content was consistently observed for three Rumex species (R. obtusifolius, R. crispus and R. japonicus) grown in the presence of Al³⁺. On the other hand, multivariate analyses revealed the differential alterations of other metabolite levels between R. obtusifolius and the other two Rumex species.     

The nature of bound residues derived from triforine in barley plants

The shoots of barley plants root-treated with [³H]-triforine fungicide (uniformly labelled in the piperazine ring) were analysed 30 days after treatment. Methanol extraction left a solid plant residue which contained 33% of the total ³H which had been incorporated into the shoots. Methanol acidified with hydrochloric acid extracted a further 18% of the triforine-derived bound residues as N-[2,2,2-trichloro-1-(piperazin-1-yl)ethyl]formamide (8%), and piperazine (10%). In the plants, these compounds had thus been complexed to plant constituents. Hot dimethyl sulphoxide (DMSO) extracted a further 13% of the total ³H, leaving a solid residue (mainly cellulose) which contained 2% of ³H, perhaps incorporated into the cellulose. Evaporation of the solvent from the DMSO extract gave a solid, the radioactivity of which (13%) could not be extracted by methanol. A part (7%) of this radioactivity could be released by successive hydrolysis with amyloglucosidase and β-glucosidase, which generated a complex mixture of polar and water soluble unknown radioactive compounds not including piperazine. These latter compounds would be the products of extensive metabolism of triforine (and its metabolite piperazine) bound to, or incorporated into starch. Most (11%) of the radioactivity of this solid could be released by hydrochloric acid hydrolysis, which also generated a complex mixture of polar and water soluble unknown radioactive compounds not including piperazine; a part (4%) of them could have been associated with lignin in the plant.     

The uptake of metabolites of permethrin by plants grown in soil treated with [14C]permethrin

Sugar beet, wheat, lettuce and cotton were grown in soil treated with [¹⁴C]permethrin, the crops being sown at intervals of 30, 60 and 120 days after treatment of the soil. The uptake of radioactive residues into these crops was measured. Low radioactive residues (up to 0.86 μg g^?1) were detected in the mature plants sown 30 days after soil treatment, and this uptake declined significantly as the interval between soil treatment and sowing increased. Metabolites derived from the acid moiety of the permethrin molecule were shown to constitute the greater part of the residue transferring from the soil to the crops. (1RS)-cis- and (1RS)-trans-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropanecarboxylic acid and 3-(2,2-dichlorovinyl)-1-methylcyclopropane-1,2-dicarboxylic acid were identified as the major acidic metabolites. The latter compound is a metabolite of permethrin which has not previously been identified in soil or plants.     

Determination of residues of endosulfan and endosulfan sulfate on eggplant,mustard and chickpea

Extractable residues of endosulfan stereoisomers and its toxic metabolite, endosulfan sulfate, on a vegetable, an oilseed and a pulse crop were determined by gas-liquid chromatography. The study revealed that the alpha isomer degraded faster than the beta isomer. Beta-endosulfan accumulated during the first three days following the treatment. Endosulfan sulfate residues appeared a few days after application and decreased with time. The total endosulfan residues in the seeds from treated mustard ranged from 0.08 to 0.12 mg kg^?1 and were at or below the limit of determination (0.02 mg kg^?1) in chickpea seeds following harvest.     

Residues and fate of endosulfan on field-grown pepper and tomato

Endosulfan (Thiodan 3 EC), a mixture of α- and β-isomers, was sprayed on 92-day-old field-grown pepper and tomato at the recommended rate of 0·61 kg AI ha^-1. Plant tissue samples were collected at 1 h to 14 days after application and analysed to determine the content and dissipation rate of endosulfan isomers (α- and β-endosulfan) and the major metabolite, endosulfan sulfate. Analysis of samples was accomplished using gas chromatography-mass selective detection (GC-MSD). The results indicated the formation of endosulfan sulfate as a residue component on the plant tissues and also the relatively higher persistence of the β-isomer as compared to the α-isomer on pepper fruits. The initial total residues (α- and β-endosulfan isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper fruits, the α-isomer, which is the more toxic to mammals, dissipated faster than the less toxic β-isomer. Total residues (α- and β-endosulfan isomers plus the sulfate metabolite) on tomato leaves revealed longer persistence (t_1/2 4·6 days) compared to the total residues detected on pepper leaves (t_1/2 2·0 days) 3–14 days following spraying. Persistence of the β-isomer on pepper fruits was high 3–14 days following spraying compared to on tomato fruits. This long persistence increases risk of exposure of the consumer. In addition, the longer persistence of the total residues on tomato foliage should be considered of importance for timing the safe entry of tomato harvesters due to the high mammalian toxicity of endosulfan. © 1998 Society of Chemical Industry     

Efficacy of plant metabolites of imidacloprid against Myzus persicae and Aphis gossypii (Homoptera: Aphididae)

The metabolism of the chloronicotinyl insecticide imidacloprid is strongly influenced by the method of application. Whilst in foliar application most of the residues on the leaf surface display unchanged parent compound, most of the imidacloprid administered to plants by soil application or seed treatment is metabolized more or less completely, depending on plant species and time. The present study revealed that certain metabolites of imidacloprid which have been described in crop plants are highly active against aphid pests in different types of bioassays. Some of these metabolites showed a high oral activity against the green peach aphid (Myzus persicae), and the cotton aphid (Aphis gossypii). The aphicidal potency of the metabolites investigated was weaker in aphid dip tests than in oral ingestion bioassays using artificial double membranes. The most active plant metabolite was the imidazoline derivative of imidacloprid. The LC₅₀ values of this metabolite for M. persicae and A. gossypii in oral ingestion bioassays were in the lower ppb-range, i.e. 0·0044 and 0·0068 mg litre^-1, respectively. Most of the other reported metabolites showed much weaker activity. Compared to imidacloprid, the imidazoline derivative showed superior affinity to housefly (Musca domestica) head nicotinic acetylcholine receptors, while all other metabolites were less specific than imidacloprid. It seems possible that, after seed treatment or soil application, a few of the biologically active metabolites arising are acting in concert with remaining levels of the parent compound imidacloprid, thus providing good control and long-lasting residual activity against plant-sucking pests in certain crops. © 1998 SCI.     

Residualwirkung von Chlortriazin-Herbiziden im Boden an drei rumänischen Standorten. II. Prognose möglicher Folgekulturen bei Atrazinrükständen im Boden

Residual effects of chlorotriazine herbicides in soil at three Rumanian sites. II. Prediction of the phytotoxicity of atrazine residues to following crops Total and plant-available atrazine residues in the top 10 cm soil were measured 120 days after application of 3 kg ai ha^?1 to maize (Zea mays L.) at three sites in Rumania. At one site, similar measurements were made 3?5 years after application of 100 kg ai ha^?1. Plant-available atrazine residues were estimated by extraction of soil samples with water, and by bioassay using Brassica rapa as the test plant. It was calculated that between 30 and 120μg atrazine 1^?1 was potentially available to plants in the different soils. Dose-response relationships for atrazine and the most important rotational crops with maize in Rumania—sunflower, winter wheat, soybean and flax—were determined in hydroponic culture using herbicide concentrations corresponding with the plant-available fractions measured in the different soils. ED₅₀ values were determined by probit analysis and the results showed that sunflower (ED₅₀, 22μg 1^?1) was the most sensitive crop, and soybean (ED₅₀, 78μg 1^?1) was the least. The residual phytotoxicity of atrazine to succeeding crops in the different soils was predicted using the appropriate availability and phytotoxicity data, and the results showed good agreement with those observed. The results suggest that measurements of plant-available herbicide residues afford a rapid method of assessing possible phytotoxicity to following crops.     

The estimation of residue levels of promacyl and its metabolites in beef tissue and fat by high-performance liquid chromatography with electrochemical detection

A method is described for the estimation of residues of the carbamate insecticide promacyl [5-methyl-m-cumenyl butyryl(methyl)carbamate] and its metabolites that are hydrolysable to isothymol (m-cymen-5-ol), using high-performance liquid chromatography with electrochemical detection to determine the isothymol. Clean-up of samples relied on the steam volatility of phenols. Recoveries at the 0.1 mg kg^?1 level varied from 72–88% for fat tissue and 81–91% for liver. The limits of detection were found to be 0.01 mg kg^?1 for and 0.02 mg kg^?1 for liver. A comparative study of the chromatography of sample extracts using both ultraviolet detection and electrochemical detection showed a substantial decrease in the level of interfering co-eluates in the latter method. A field trial, involving a single spray application of the formulated acaricide on milking cattle, revealed residues in the butter fat comparable with those found in a previous investigation.     

Bromoxynil degradation in a Mississippi silt loam soil

BACKGROUND: The objectives of these laboratory experiments were: (1) to assess bromoxynil sorption, mineralization, bound residue formation and extractable residue persistence in a Dundee silt loam collected from 0–2 cm and 2–10 cm depths under continuous conventional tillage and no‐tillage; (2) to assess the effects of autoclaving on bromoxynil mineralization and bound residue formation; (3) to determine the partitioning of non‐extractable residues; and (4) to ascertain the effects of bromoxynil concentration on extractable and bound residues and metabolite formation. RESULTS: Bromoxynil K_d values ranged from 0.7 to 1.4 L kg^?1 and were positively correlated with soil organic carbon. Cumulative mineralization (38.5% ± 1.5), bound residue formation (46.5% ± 0.5) and persistence of extractable residues (T_1/2 < 1 day) in non‐autoclaved soils were independent of tillage and depth. Autoclaving decreased mineralization and bound residue formation 257‐fold and 6.0‐fold respectively. Bromoxynil persistence in soil was rate independent (T_1/2 < 1 day), and the majority of non‐extractable residues (87%) were associated with the humic acid fraction of soil organic matter. CONCLUSIONS: Irrespective of tillage or depth, bromoxynil half‐life in native soil is less than 1 day owing to rapid incorporation of the herbicide into non‐extractable residues. Bound residue formation is governed principally by biochemical metabolite formation and primarily associated with soil humic acids that are moderately bioavailable for mineralization. These data indicate that the risk of off‐site transport of bromoxynil residues is low owing to rapid incorporation into non‐extractable residues. Published 2009 by John Wiley & Sons, Ltd