Persistence and binding of DDT and gamma-HCH in a sandy loam soil under field conditions in Delhi,India

Persistence and binding capacity of [¹⁴C]p, p′-DDT and [¹⁴C]y-HCH were studied for one year in a sandy loam soil of Delhi, India, after surface treatment during monsoon, winter and summer seasons under field conditions. Both DDT and HCH dissipated more rapidly under the Indian subtropical climate than reported for temperate regions. In all three seasons, both insecticides dissipated most rapidly during the initial 60 days. However, in the final six months there was very little change in the residue levels. After one year, the final soil burden of DDT varied from 33 to 36% and of HCH from 14 to 15% of the initial concentrations in the different experiments. HCH bound more with the soil as, out of the total residues present after one year, more than 75% of HCH was in bound form compared with only 24% of DDT. The observed time for 50% initial dissipation of DDT ranged from 60 to 120 days, while in the case of HCH it varied from 30 to 45 days. However, the rate of loss of residues which persisted for more than 6 months was equivalent to a half-life of between 500 and 10000 days for DDT, and between 700 and 2000 days for HCH, thus illustrating the very long persistence of aged residues. Since degradation of both insecticides was apparently minimal, the data indicate that dissipation of DDT and HCH was largely due to volatilisation.     

Binding of chlorpyrifos and cypermethrin to blood proteins

The features of two insecticides (chlorpyrifos and cypermethrin) binding to two blood proteins, bovine serum albumin (BSA), and bovine hemoglobin (BHb), were investigated via the fluorescence method. The results revealed that both insecticides caused the fluorescence quenching of BSA and the fluorescence enhancement of BHb. A new parameter (F_E), i.e., the fluorescence intensity when adequate insecticide was added, was introduced to obtain the association constant (K_A) and the number of binding sites (n). K_A and n of chlorpyrifos and cypermethrin binding to BSA were 2.99 × 10⁵ and 5.22 × 10⁵ L mol⁻¹, 1.25 and 0.78, respectively. K_A and n of chlorpyrifos and cypermethrin binding to BHb were 2.94 × 10⁴ and 2.48 × 10⁴ L mol⁻¹, 1.75 and 2.19, respectively. In conclusion, chlorpyrifos and cypermethrin could bind to BSA and BHb, and the binding of both insecticides to BSA was significantly stronger than that of insecticides to BHb. These could affect the distribution, metabolism, and excretion of insecticides.     

Temporal and regional variability of cumulative ecological risks of pesticides in Japanese river waters for 1990–2010

We quantitatively evaluated the cumulative ecological risks from multiple pesticides used in paddy fields in Japan. Moreover, we visualized the temporal and regional variability of those risks for 1990–2010. Considering the region-specific parameters of environmental conditions, region-specific predicted environmental concentrations were estimated at 350 river-flow monitoring sites in Japan. Then the multi-substance potentially affected fraction (msPAF) was calculated as a risk index of multiple pesticides by using the computation tool NIAES-CERAP. The median msPAF values for insecticides and herbicides decreased by 92.4% and 53.1%, respectively, from 1990 to 2010. This substantial reduction in ecological risk was attributed to the development of low-risk pesticides by manufacturers, the efforts of farmers in risk reduction, and tighter regulation by the Japanese government. In particular, the substantial reduction of the ecological risk from insecticides was largely due to the decrease in the use of organophosphorus insecticides.     

Interactions of insecticides with biological membranes

Many insecticides (e.g. DDT, lindane, pyrethroids) are hydrophobic molecules which bind extensively to biological membranes. Binding of insecticides to phospholipid bilayers frequently shows saturation, with binding increasing with increasing insecticide concentration up to some limit, beyond which no further insecticide is incorporated into the bilayer. For lindane, this limit has been shown to correspond to the concentration at which the aqueous phase becomes saturated. Simple alkanes show similar saturation phenomena, and binding of halogenated alkanes can be followed by fluorescence quenching methods. It is shown that effects of hydrophobic molecules on bilayer fluidity are small. Effects of alkanes and insecticides on the activity of the (Ca²⁺-Mg²⁺)-ATPase purified from sarcoplasmic reticulum follow from direct binding to the ATPase, at sites which are not at the lipid-protein interface of the ATPase.     

Evaluation of neonicotinoid, organophosphate and avermectin trunk injections for the management of avocado thrips in California avocado groves

BACKGROUND: Trunk injections of systemic insecticides were evaluated for the management of avocado thrips. Insecticide residues were quantified in leaves to determine when after treatment, and for how long, toxic concentrations of the insecticides were present. Residues in fruit were quantified to determine whether trunk injection of insecticides might present a greater risk than traditional application methods for contaminating fruit. RESULTS: Residues of imidacloprid and dinotefuran were at least tenfold higher in leaves when trees were treated via trunk injection compared with soil application. Dinotefuran uptake was more rapid than imidacloprid, and no residues were detected within fruit. Acephate was also mobilized very rapidly and gave good control of thrips in bioassays; however, residues of acephate and its insecticidal metabolite methamidophos were detected in the fruit for up to 4 weeks after injection. Avermectin uptake was very slow, and it was ineffective against avocado thrips. CONCLUSIONS: Trunk injections of acephate and dinotefuran permitted rapid uptake into avocados, and they are strong candidates as control methods for avocado thrips. However, residues of organophosphates in fruit could necessitate increased preharvest intervals. Residues of neonicotinoids were below detection limits in fruit, suggesting that neonicotinoids may be the more suitable control option of the two chemical classes. Copyright © 2012 Society of Chemical Industry     

Characterization of high affinity binding of [3H]propyl bicyclic phosphate to house fly head extracts

The head of the house fly, Musca domestica L., was found to contain saturable components of specific binding of 4-n-propyl[2,3-³H]-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide ([³H]Pr-BP). A ratio of specific to total binding of radioreceptor assays was quite favorable, being 0.89 under the standard conditions. The apparent dissociation constant and maximal binding capacity were estimated to be about 4 nM and about 30 fmol/mg of protein, respectively, although association, dissociation, and saturation analyses suggested the presence of two or more populations of binding sites. Specific [³H]Pr-BP binding showed a marked negative temperature coefficient and was little affected by pH in incubation media. Anions which pass through chloride channels attenuated specific [³H]Pr-BP binding whereas impermeable anions enhanced it. Specific binding was selectively inhibited by insecticidal bicyclic phosphorus esters. Various neuroactive chemicals such as GABA agonists, GABA antagonists, cyclodiene insecticides, and benzodiazepines had little effect on specific binding. There was a correlation between GABA content and the density of specific Pr-BP binding sites in each part of the house fly body. In many respects, however, characteristics of the current binding site were different from those of GABA receptor-coupled sites already characterized with [³H]Pr-BP and the [³⁵S]t-butyl thiono analog in the rat brain. Bicyclic phosphorus esters may act on site(s) apart from the GABA neurotransmission system in the house fly.     

Species differences in chlorantraniliprole and flubendiamide insecticide binding sites in the ryanodine receptor

Anthranilic and phthalic diamides exemplified by chlorantraniliprole (Chlo) or cyantraniliprole (Cyan) and flubendiamide (Flu), respectively, are the newest major chemotype of insecticides with outstanding potency, little or no cross resistance with other classes and low mammalian toxicity. They are activators of the ryanodine (Ry) receptor (RyR)-Ca²⁺ channel, based on Ca²⁺ flux and electrophysiology investigations. The goal of this study is to define species differences in the degree and mechanisms of diamide selective action by radioligand specific binding studies at the [³H]Ry, [³H]Chlo and [³H]Flu sites. The [³H]Ry site is observed in muscle of lobster, rabbit and four insect species (Musca domestica, Apis mellifera, Heliothis virescens and Agrotis ipsilon) whereas the [³H]Chlo site is evident in the four insects and the [³H]Flu site in only the two lepidoptera (Agrotis and Heliothis). [³H]Ry binding is significantly stimulated by Chlo, Cyan and Flu with the insects (except Flu with Musca) but not the lobster and rabbit. [³H]Chlo binding is stimulated by Ry and Flu in Musca and Apis but not in the lepidoptera, while Flu and Cyan are inhibitory. [³H]Flu binding is strongly inhibited by Chlo and Cyan in Agrotis and Heliothis. [³H]Chlo and [³H]Flu binding are not dependent on added Ca²⁺ or ATP in Heliothis and Agrotis whereas the other radioligand-receptor combinations are usually enhanced by Ca²⁺ and ATP. More generally, there are species differences in the Ry, Chlo and Flu binding sites of the RyR that may confer selective toxicity and determine target site cross resistance mechanisms.     

Influence of block and cell size,growing medium and insecticide dose on the behaviour and uptake of phorate by lettuce and uptake of carbofuran and chlorfenvinphos by calabrese

Phorate residues in peat blocks and lettuce were determined following incorporation of the insecticide into different block and ‘Speedling’ cell sizes. Between-block variability was influenced little by block size. Phorate oxidation was most extensive in the largest blocks containing the smallest dose. Total residue concentrations in the lettuce declined from the time of planting to harvest, although accumulation of insecticide continued and was related more to dose than to block or cell size. Residues in the lettuce at harvest exceeded the proposed maximum limit of 0.2 mg kg^?1 in some treatments. Residues at planting comprised mainly the parent sulphoxide and sulphone, but by harvest, the oxygen analogue sulphoxide and sulphone predominated. Lettuce weight was not influenced by dose but was related directly to block size. Carbofuran and chlorfenvinphos residues were determined in calabrese sown into two sizes of blocks. At planting time, carbofuran residue concentrations were 100 times greater than those of chlorfenvinphos but residues of both insecticides in the mature heads were < 0.01 mg kg^?1. Seedling weights in both sowings declined with increasing concentrations of the insecticides. It was concluded that manipulations of block size and the dose of insecticide need to be evaluated for individual insecticide/crop combinations to exploit the technique fully.     

Insecticide application and degradation in sultana grapes grown for drying

Four experiments using the insecticides malathion and chlorpyrifos on mature, unharvested and harvested sultana grapes provided information on the efficiency of application and the rate of loss of insecticides, through the phases of preharvest to processing. Unharvested bunches retained 3.5-8.1% of the active ingredient (a. i.), whereas harvested bunches laid out to dry retained 23% a. i. Insecticide decay was greatest immediately after application, probably due to volatilisation of unbound chemical, but the rate of loss was accelerated by the use of alkaline drying oils which stimulated hydrolytic degradation. Drying oils are conventionally applied to hasten drying. The residue on fruit at the end of drying was generally higher than that on the fresh fruit because of the concentration effect of dehydration. Processing and storage did not alter the residues, probably because the chemical migrated into the fruit and became bound to inert compounds.     

The role of glutathione S-transferases in the detoxification of some organophosphorus insecticides in larvae and pupae of the yellow mealworm,Tenebrio molitor (Coleoptera: Tenebrionidae)

The correlation between the natural levels of glutathione S-transferase (GST) and the tolerance to the organophosphorus insecticides parathion-methyl and paraoxon-methyl, as well as the interaction of affinity-purified enzyme and the insecticides were investigated in order to collect further information on the role of the glutathione S-transferase system as a mechanism of defence against insecticides in insects. The studies were carried out on the larvae and pupae of the coleopteran Tenebrio molitor L, which exhibit varying natural levels of GST activity. Stage-dependent susceptibility of the insect against insecticides was observed during the first 24 h. However, 48 h after treatment, the KD₅₀ value increased significantly due to the recovery of some individuals. Simultaneous injection of insecticide with compounds which inhibit GST activity in vitro caused an alteration in susceptibility of insects 24 or 48 h post-treatment, depending on stage and insecticide used. Inhibition studies combined with competitive fluorescence spectroscopy revealed that the insecticides probably bind to the active site of the enzyme, thus inhibiting its activity towards 1-chloro-2,4-dinitrobenzene in a competitive manner. High-performance liquid chromatography and gas chromatography revealed that T molitor GST catalyses the conjugation of the insecticides studied to a reduced form of glutathione (GSH). From the above experimental results, it is considered that GST offers a protection against the organophosphorus insecticides studied by active site binding and subsequent conjugation with GSH. © 2001 Society of Chemical Industry     

Affinities of parathion,DDT, dieldrin,and carbaryl for macromolecules in the blood of the rat and American cockroach and the competitive interaction of steroids

This investigation concerns the binding of DDT, dieldrin, parathion, and carbaryl to macromolecules of rat and roach blood. Plasma was filtered on Sephadex G-200, and the first protein peak (FPP) was used to investigate binding characteristics for the insecticides. Binding was demonstrated to be of a nonspecific hydrophobic nature, except for roach FPP and dieldrin in which, in addition to low-affinity binding, sites for high-affinity binding were also found. Competitive binding experiments were run with cholesterol, estrogen, DDT, and dieldrin. No significant competitive interactions were demonstrated.     

Persistence and degradation of chlorfenvinphos,diazinon, fonofos and phorate in soils and their uptake by carrots

Analytical methods are described for the determination of residues of chlorfenvinphos, diazinon, fonofos and phorate in soils and carrots. The insecticides, applied in June 1969 at 2 kg (a.i.)/ha, persisted longer in peaty loam than in sandy loam. After 7 months, the sandy loam contained 1% of the applied diazinon and 20–30% of the applied chlorfenvinphos, fonofos and phorate, the latter as its sulphone; the corresponding figures for the peaty loam were 10, 40–50, 40–50 and 30–40% respectively. None of the residues showed any substantial change from October to January. Although high initial concentrations (up to 50 ppm) of the residues in carrots were diluted by plant growth, it is shown that concentrations >1 ppm could be present in marketable crops 12–14 weeks after application at recommended rates. Carrots harvested 26 weeks after sowing contained <0.2 ppm of all insecticides. In contrast, during the first 15 weeks of crop growth the weights of residues in the carrots increased and remained approximately proportional to the square root of the carrot mean weight. Rates of uptake declined as carrot growth declined and subsequently the amounts of chlorfenvinphos, diazinon and fonofos residues in the carrots changed very little, while phorate sulphone steadily declined.     

Benzoylphenylurea residues in peppers and zucchinis grown in greenhouses: determination of decline times and pre-harvest intervals by modelling

Residue levels and degradation rates of five benzoylphenylurea insecticides were studied in zucchinis and peppers grown in experimental greenhouses in Almería (Spain). Benzoylphenylurea residues were analyzed by HPLC using on-line post-elution photoirradiation with fluorescence detection. Mathematically defined decline curves were established by determining optimal relationships between benzoylphenylurea residues and time, using different models. The models that best fitted the experimental data were those of first-order for diflubenzuron, triflumuron, hexaflumuron and flufenoxuron in zucchini and RF first-order models for the five insecticides in peppers and for lufenuron in zucchini. Half-life times for the residues on the two vegetables were estimated from the optimal models. In order to guarantee safe consumption of the two vegetables, we have estimated suitable pre-harvest intervals complying with the maximum residue levels established by the Spanish Government. In all cases, such pre-harvest intervals were shorter than those specified by the manufacturers of commercial formulates. Experimental data for the five insecticides in peppers and for lufenuron in zucchini were also fitted to a first-order model. Even though this function was legitimized statistically, estimations of decline times (T/2) and pre-harvest intervals were quite different from those provided by the optimal model.     

Occurrence of chlorinated hydrocarbon insecticides, southern Florida--1968-72.

The frequency with which chlorinated hydrocarbon insecticides appear in samples of southern Florida surface waters decreased sharply between 1968 and 1972. Sediment analyses attest to the earlier widespread use of chlordane, DDT, and dieldrin. Insecticide residues are more frequently detected in southern Florida than in other U.S. cropland soils. Transport of DDT, DDD, and DDE from the Everglades agricultural area into water conservation areas and undeveloped parts of the Everglades of southeastern Florida is facilitated by a system of water-management canals. Canal sediments within the urban area of southern Florida have high DDD, DDE, and dieldrin residue concentrations which may reflect local use of insecticides rather than their transport from adjacent agricultural areas.     

新烟碱类杀虫剂在苹果果实不同部位中的残留

为了明确噻虫嗪、烯啶虫胺、吡虫啉、啶虫脒、噻虫胺和呋虫胺6种新烟碱类杀虫剂在苹果果实不同部位中的迁移转化规律,以10年生红富士苹果树为试材,分别于蚜虫发生期 (7月10日) 和果实采收前1 d (9月25日) 通过整株喷雾施药,随机取样,采用高效液相色谱仪测定,外标法定量,分析各杀虫剂在生长期套袋果实和不套袋果实及储藏期果实不同部位中的残留量及迁移规律。结果表明:在果实套袋情况下,施药后72 h内果实不同部位各新烟碱类杀虫剂的含量均呈现先逐渐上升而后下降的趋势,且在果皮中的残留量最低 (均低于0.08 mg/kg),其中烯啶虫胺和吡虫啉在果皮中的残留量低于最低检测浓度,而在果柄和果肉中的残留量明显高于果皮中的,表明套袋果实中药剂主要来源于枝叶运输,经果柄进入果实后易向果肉累积;在果实未套袋情况下,施药后72 h 6种杀虫剂在果肉中的含量均高于套袋果实果肉中的,分别是套袋果实果肉中含量的7.75、3.52、3.36、6.57、2.92和3.06倍,表明套袋可有效降低果实中该类药剂的残留量。储藏试验结果表明:直接向果面喷施6种新烟碱类杀虫剂后,药剂主要存在于果皮中,施药后14和21 d在果肉中的含量均低于最低检测浓度,表明储藏期果皮为该类药剂的主要残留部位,且不易向果肉中转移。     

Action of pyrazoline-type insecticides at neuronal target sites

Pyrazoline-type insecticides were discovered in the early 1970s, but did not readily yield commercial insecticide products due to their unfavorable toxicity profiles and environmental properties. The recent registration of indoxacarb, a compound derived from pyrazolines, has drawn renewed attention to this insecticide class. This review summarizes the development of the pyrazoline-type insecticides and examines the mechanism of action of these compounds based on available electrophysiological, pharmacological, and toxicological information.     

Persistence and degradation of chlorfenvinphos,chlormephos, disulfoton,phorate and pirimiphos-ethyl following spring and late-summer soil application

Granular formulations of chlorfenvinphos, chlormephos, disulfoton, phorate and pirimiphos-ethyl were broadcast at 2 kg a.i./ha and incorporated to 100 mm into a sandy-loam soil either in May or in September 1971. The relative persistence of their residues, including insecticidally active oxidation products, after both application dates was disulfoton > chlorfenvinphos > phorate > pirimiphos-ethyl > chlormephos. When applied in September all the insecticides persisted for longer than when applied in May. Degradation was slower during the winter while the mean soil temperature at 100 mm depth remained below 6 to 7°C. Rising soil temperature in the following spring rapidly increased the rates of degradation of chlorfenvinphos, chlormephos and pirimiphos-ethyl residues but not of disulfoton- and phorate-derived residues, predominantly the parent sulphones, which had been leached deeper. Ten months after the September application, half the total residues derived from disulfoton and phorate were found below the initial incorporation depth, whereas the other insecticides showed relatively little downward movement. It was concluded that late summer/early autumn applications for carrot fly control would leave appreciable residues of some insecticides in the soil at the beginning of the next growing season which may contribute to the terminal residues in crops. These would be minimised if moderately persistent compounds were used or if doses of persistent ones were substantially reduced.     

Insecticidal and binding activities of N3-substituted imidacloprid derivatives against the housefly Musca domestica and the alpha-bungarotoxin binding sites of nicotinic acetylcholine receptors

N3-substituted imidacloprid congeners containing C1-C6 alkyl groups or various analogous groups, and their corresponding nitromethylene analogues, were used in this study. Their insecticidal activity against the housefly, Musca domestica, and their binding activity toward the nicotinic acetylcholine receptor were determined. The insecticidal test was conducted using the synergists piperonyl butoxide and propargyl propyl phenylphosphonate. The binding assay was performed with housefly head membrane preparations using radio-labelled alpha-bungarotoxin. Both insecticidal and binding activities were drastically lowered by the introduction of alkyl/allyl groups at the imidazolidine NH sites of both nitroimino and nitromethylene compounds. The binding activity of N3-substituted nitromethylene analogues was much higher than that of the corresponding nitroimino analogues. However, the insecticidal activity of both series of compounds with a given substituent was nearly identical. The insecticidal activity correlated positively with the binding activity after taking into account the structural difference of the nitroimino and nitromethylene moieties and a structural feature of the N3-substituents.     

甜菜夜蛾细胞色素P450(CYP9A11)与3种杀虫剂的结合机理研究

细胞色素P450(以下简称CYP)与昆虫的抗药性密切相关。本研究运用AutoDock分子对接技术和分子力学泊松-波尔兹曼表面积法(molecular mechanics Poisson-Boltzmann surface area,MM-PBSA)结合自由能计算方法,分析了甜菜夜蛾CYP9A11与3种杀虫剂结合的作用位点、作用力类型和大小。结果表明:CYP9A11与毒死蜱结合形成两个氢键,有8个氨基酸残基参与形成疏水作用力,二者结合自由能为-3659.80 kJ/mol;CYP9A11与灭多威结合形成5个氢键,有3个氨基酸残基形成疏水作用力,结合自由能为-470.92 kJ/mol;CYP9A11中有7个氨基酸残基与氯氰菊酯结合形成疏水作用力,结合自由能为-473.44 kJ/mol。范德华力是CYP9A11与毒死蜱结合的主要驱动力,极性溶剂化能是CYP9A11与氯氰菊酯和灭多威结合的主要驱动力,这些结果为阐明甜菜夜蛾CYP9A11与3种杀虫剂的结合机理提供了参考。     

Differential susceptibility to abamectin and two bioactive avermectin analogs in abamectin-resistant and -susceptible strains of Colorado potato beetle, Leptinotarsa decemlineata (Say) (Coleoptera: Chrysomelidae)

As resistance to currently used insecticides increases in the Colorado potato beetle (CPB), Leptinotarsa decemlineata (Say), abamectin and its 4″-epi and 8,9-oxide analogs may serve as likely replacements if proven effective. We previously selected an abamectin-resistant strain of CPB (AB-F) that is suitable for the determination of cross-resistance to these two bioactive avermectin analogs. Using bioassay and logit analysis, the present work shows that, on average and following normalization by weight, the larval stages of the insecticide-susceptible SS strain are equally sensitive to the toxic action of abamectin and its 4″-epi and 8,9-oxide analogs, indicating that all three compounds retain high bioactivity towards the susceptible larval stages. Abamectin and the two analogs also are similar in toxicity to the larval stages of the AB-F strain. However, the AB-F larval stages are significantly less sensitive on average to these insecticides than the SS larval stages, indicating resistance to abamectin and cross-resistance to both the two analogs tested. Likewise, adults of the AB-F strain are significantly less sensitive to the toxic action of abamectin and the two analogs compared to SS adults, also indicative of resistance and cross-resistance. Abamectin is significantly more toxic, however, to both SS and AB-F adults, respectively, than either of the two analogs. The reduction in sensitivity was particularly evident in SS adults to both the 4″-epi and 8,9-oxide analogs. Additionally, adults of the SS strain are significantly less sensitive to the toxic action of abamectin and the two analogs when compared to SS larval stages. There is no significant differences, however, in the toxicity of these three insecticides, respectively, between larval and adults stages of the AB-F strain. This phenomenon results in lower resistance ratio (RR) values calculated for the two avermectin analogs compared to those calculated for abamectin regardless of the insect stage examined but is particularly evident and significant in the adult stage. This relative decrease in resistance levels is primarily associated with SS adults that are less sensitive to the toxic action of these insecticides. The decrease in abamectin toxicity is apparently due to significantly increased levels of P450 associated with SS adults versus forth instars and to similar levels in adults of the SS and AB-F strains. Because abamectin resistance in CPB is due in large part to enhanced oxidative metabolism of abamectin, it is likely that the SS adults are more tolerant to abamectin due to an enhanced level of oxidative detoxification. Finally, neither abamectin nor the two analogs are structurally protected at the specific molecular locations, C₃″, C₂₄, and C₂₆ carbons, which leads to enhanced oxidative metabolism, resistance and cross-resistance. Structurally-protected avermectin analogs at these vulnerable intramolecular sites are likely to be more effective insecticides in suppressing the development of oxidative detoxification-based resistance to abamectin, as would the use of oxidative synergists.