Determination of 10 Pyrethroids Pesticide Residues in Rice by GC-MS-MS

[Objective] A method was developed for the determination of 10 pyrethroids pesticide residues in rice by GC-MS-MS. [Method] Pyrethroids were extracted with acetonitrile, followed by a salting-out step with anhydrous magnesium sulfate and sodium chloride, cleaned up by florisil solid phase extraction （SPE） cartridge, and determined by multiple reaction monitoring mode. [Result] The method showed good linearity over the range of 0.010-0.500 mg/L for 10 pyrethroid pesticide with correlation coefficients over 0.99. The detection limits were 0.005 -0.010 mg/kg. The method was validated by analyzing samples spiked with 0.05, 0.10, 0.20 mg/kg of 10 pyrethroid pesticides, respectively. The average recoveries in rice ranged from 75.0-115.5%, and the relative standard deviations （RSD） were between 3.9%-6.9%. [Conclusion] The method is easy, accurate and reliable, which can meet the requirement for the simultaneous determination and confirmation of pyrethroid pesticide residues in rice.

Acute Toxicity of Two Pyrethroids Insecticides on Brachionus calyciflorus

[ Objective] The paper was to study the 24 and 48 h acute toxicity of common pyrethroid insecticides of eypermethrin and deltamethrin on Brachionus calyciflorus. [ Method ] With Guangzhou strain of B. colyciflorus as test animal, the standard toxicity test method was used to carry out acute toxicity test, and LC50 of cypermethrin and deltamethrin on rotifer was determined using probit method. [ Result ] LC50 of cypermethrin on rotifer was 3 376.87 and 5.87 μg/L at 24 and 48 h, respectively, and those of deltamethrin on rotifer was 594.56 and 74.17 μg/L, respectively. [Condusion] Acute toxicity of cypermethrin and dehamethrin on rotifer at 24 and 48 h was different, LC50 of cypermethrin and deltamethrin on rotifer at 48 h was more sensitive to monitor the chemical pollutants in water body than LC50 at 24 h.

Estrogenic activities of two synthetic pyrethroids and their metabolites

Synthetic pyrethroids （SPs） are among the most common pesticides in current use, and so far, several SPs have been assessed for their potential estrogenicities by various methods. Previous studies have shown that the estrogenicities partly come from their metabolites. Although considerable information is available with respect to the metabolism and environmental degradation of SPs, little is known about the estrogenicities of the metabolites. In this study, permethrin （PM） and β-cypermethrin （CP）, as well as their metabolites （3-phenoxybenzoic alcohol （PBCOH）, 3-phenoxybenzaldehyde （PBCHO） and 3-phenoxybenzoic acid （PBCOOH） were evaluated for their estrogenic activities in the MCF-7 human breast carcinoma cell line. In the MCF-7 cell proliferation assay, PM and CP exhibited significant estrogenic activities at 10-7 mol/L, comparable to 17β-estradiol （E2） of 10-9 tool/L, with the relative proliferative effect ratios of 55.4% and 56.3%, respectively. The real-time quantitative polymerase chain reaction （qRT-PCR） results confirmed the estrogenicities of PM and CP with significant alteration of pS2 and ERα mRNA levels observed at 10-6 mol/L. For the three major metabolites, PBCOH and PBCOOH exhibited estrogenic activities in all assays, while no significant estrogenic responses was observed for PBCHO compared to the vehicle control. In particular, PBCOH had even slightly stronger estrogenic activity than its parent compounds, indicating that metabolism may be one of the reasons for the estrogenicities of the SPs. Given the widespread use of SPs, the toxicological effects of parent compounds and their metabolites should be taken into consideration in the risk assessment of SPs.

Neurolemma-Injected Xenopus Oocytes: An Innovative Ex Vivo Approach to Study the Effects of Pyrethroids on Ion Channels in Their Native State

Microtransplantation of rat brain neurolemma into the plasma membrane of Xenopus laevis oocytes is an ex vivo method used to study channels and receptors in their native state using standard electrophysiological approaches.In this review,we show that oocytes injected with adult rat brain neurolemma elicited tetrodotoxin-sensitive inward ion currents upon membrane depolarization,which were increased in a concentration-dependent manner by treatment with the pyrethroid insecticides permethrin and deltamethrin.Under our initial protocols,oocyte health was reduced over time and neurolemma incorporation varied between batches of oocytes from different frogs,limiting the usefulness of the assay for regulatory issues.A collection of changes to the assay procedure,data acceptance criteria,and analysis method yield substantially improved precision and,hence,assay performance.These changes established this ex vivo approach as a toxicologically relevant assay to study the toxicodynamic action of pyrethroids on ion channels in their native state using neurolemma fragments prepared from juvenile and adult rat brains.

Spontaneous Mammary Carcinomas in Female Dogs: Association between Immunohistochemical Degrees of Neoplasia Aggressiveness and Residual Pyrethroids

Of the tumors diagnosed in the female dogs have the highest mammary neoplasias incidence. These neoplasias can be influenced by environmental contaminants. Despite evidence of pyrethroid toxicity, carcinogenic potential has not yet been sufficiently elucidated, there is a need to investigate their involvement in mammary tumor. In previous studies, pyrethroid residues were detected in female dogs with mammary neoplasia, however was not investigate the influence of this insecticide in the genesis and aggressiveness of mammary cancer. This study aimed to investigate possible relations between pyrethroid residues and aggressiveness of mammary carcinoma in female dogs. Fifty selected female dogs were divided into five groups of 10 animals each: the Control group, female dogs without mammary neoplasia;the groups Luminal A, Luminal B, HER-2 Superexpression and Basal were constituted by female dogs that presented inguinal mammary carcinoma classified immunohistochemically. The aggressiveness of carcinomas was evaluated by immunohistochemistry (HER-2, p63, estrogen receptor). Residual concentrations of the pyrethroids from the mammary gland and fat tissue adjacent to it were determined by HPLC. Data were analyzed by Chi-Square test. Of the all animals, six presented residues of pyrethroids in mammary samples and 10 presented it in fat tissue samples. There was no statistical evidence that pyrethroids are involved in mammary carcinoma aggressiveness in female dogs.

Spontaneous Mammary Carcinomas in Female Dogs:Association between the Immunohistochemical Degree of Aggressiveness of Tumors,Intensity of DNA Damage and Residues of Pyrethroids

Diagnosis and biological behavior of breast cancer of female dog represent one of the biggest challenges facing the Veterinarian in recent years. Due to its exponential growth and the degree of aggressiveness, the exact cause of this tumor is probably multifactorial and it is believed that may suffer influence from environmental factors. Among the suspected environmental contaminants are the pyrethroids. Aiming to investigate the participation of pyrethroids in tumorigenesis in female dogs, a study was conducted using 50 female dogs, 22 were positive for simple breast carcinoma (Group I), 18 with a diagnosis of complex breast carcinoma (Group II) and 10 negative (Group III) for breast cancer. In order to detect DNA damage, the Comet assay was performed on mammary samples of these animals, which also had samples submitted to the technique of High Performance Liquid Chromatography (HPLC), which aimed to quantify the concentration of pyrethroids. The results of HPLC of each animal were compared with those obtained by the Comet assay analysis of variance and the means were compared by the test groups “Student T” at the significance level of p ￡ 0.05. Despite presenting correlation between the amount of DNA damage and tumor aggressiveness, no statistical differences were found in the DNA damage of different histologic types of breast carcinoma. As for pyrethroids, even these were detected in 22% of tumor tissues and peritumoral fat, there was no difference in DNA damage between cells exposed and not exposed to environmental contaminant.

A new household ultrasonic cleaning method for pyrethroids in cabbage

Pyrethroid is widely used in developing countries and is a potential threat to human health.So putting forward an effective pyrethroid cleaning method is of vital importance.Clearance of fenpropathrin,cypermethrin and deltamethrin in cabbage by using ultrasonic treatment accompanied with different baking soda concentrations were investigated in this study.The results of response surface methodology showed that the maximum clearance rate was 70.61% for fenpropathrin under the optimal power,treated time,treated temperature and baking soda concentration,which were 260.02 W,10 min,20.15◦C and 0.014 g/mL,respectively.Similarly,the maximum removal efficiency was 73.72% for cypermethrin under 240 W,13.84 min,19.53℃ and 0.014 g/mL,and 92.15%for deltamethrin under 238.99 W,12.42 min,25℃ and 0.013 g/mL.The clearance rate of pyrethroid by this method was significant higher(P<0.05)than traditional cleaning methods(bathing and running water washing).The contents of the compositions such as vitamin C,total soluble sugar,protein and dietary fiber,texture and sensory evaluation of cabbage were not found obvious changes after the ultrasonic treatment combined with baking soda(P>0.05).Results showed that ultrasonic treatment combined with baking soda was an effective way to eliminate the fenpropathrin,cypermethrin and deltamethrin in cabbage without influencing cabbage quality.

Degradation Dynamics of Pyrethroids in Cigarette Production Environment

[ Objective] In order to provide a reference for safe and reasonable use of pyrethroids in cigarette production, the degradation behaviors of three kinds of pyrethroids in cigarette production environment were studied. [ Method ] Three kinds of pyrethroids （permethrin, cyfluthrin and c/s-cypermethrin） were adminis- trated to two media （cut tobacco and iron sheet surface） in cigarette production environment at MRLs concentration, and the first sampling was conducted at 24 d post administration. Afterwards, sampling was performed once every 7 d, with a total of six times. The degradation rates of insecticides in different media were cal- culated, and degradation models were established. [ Result ] The contents of three kinds of insecticides in two media gradually declined with the prolongation of time, and degradation rates presented the trend of fast-slow-fast ; the degradation rates of permethrin, cyfluthrin and c/s-cypermethrin in cut tobacco at 36 d post ad- ministration were 97.14%, 88.89% and 95.38%, respectively; the degradation rates on iron sheet surface were 29.95%, 48.99% and 40. 24%, respectively. The half lives of three kinds of insecticides in cut tobacco were 1 -2 d, while those on iron sheet surface were 6 - 10 d. [ Conclusion] The contents of three kinds of insecticides in two media gradually declined with the prolongation of time, and their degradation regularity accorded with first order kinetic equation.

Resistance risk assessment of six pyrethroids and acephate toward the resistant adult tarnished plant bug,Lygus lineolaris

Due to rapidly developed resistance,pest management relies less on pyrethroids to control economically damaging infestations of the tarnished plant bug(TPB),Lygus lineolaris(Palisot de Beauvois)in cotton fields of Mississippi.Yet,pyrethroid resistance remains prevalent in TPB populations.This study assessed the resistance levels in adult TPB to six common pyrethroids and acephate.Resistant TBPs were collected from wild host plants in late October after harvest in the Mississippi Delta region of the United States.Based on LCso values,the field-resistant TPBs displayed higher resistance to permethrin,esfenvalerate,and bifenthrin(approximately 30 fold)and moderate resistance toα-cyhalothrin,β-cyfluthrin,5-cypermethrin,and acephate(approximately 15 fold).Further investigations showed that the inhibitors of three detoxification enzyme,triphenyl phosphate(TPP),diethyl maleate(DEM),and piperonyl butoxide(PBO)had synergistic effects on permethrin,γ-cyhalothrin,and bifenthrin in resistant TPBs.Furthermore,elevated esterase,GST,and P450 activities were significantly expressed in fieldresistant TPBs.Additionally,GST and esterase were reduced after 48 h exposure to certain pyrethroids at LCso dose.The synergistic and biochemical assays consistently indicated that P450 and esterase were involved in pyrethroid detoxification in TPBs.This study provides valuable information for the continued use of pyrethroids and acephate in controlling TPBs in cotton fields in the Mississippi Delta region of the United States.

Understanding the endocrine disruption of chiral pesticides:The enantioselectivity in estrogenic activity of synthetic pyrethroids

Synthetic pyrethroids(SPs) ,a family of chiral insecticides consisting of multiple stereoismers,have been regarded as estrogenic endocrine-disrupting chemicals(EDCs) .In this study,we applied the yeast two-hybrid and molecular docking(MD) assay to assess the enantioselective estrogenic activities of three commonly used SPs,bifenthrin(cis-BF) ,permethrin(PM) and fenvalerate(Fen) .The β-galactosidase analyses indicated that all of the testing pyrethroids displayed significant(p【0.05) enantioselectivity.The results showed that the estrogenic potential of cis-BF was mainly attributed to 1S-cis-BF.Neither PM nor Fen showed estrogenic effects.However,two stereoisomers of PM possessed estrogenic potential activities.αR-2R-Fen and αS-2S-Fen also induced the β-galactosidase activity.The inability to initiate the reporter gene expression by the racemic chemicals may be due to the low ratios of these isomers or the antagonism among them.The strong hydrophobic interaction and the hydrogen bond between positive estrogenic isomers and ERα support our biological testing results.This research demonstrated that the enantioselective estrogenic activity of chiral SPs was due to selective binding between their isomers and the ERαreceptor.The data suggests that enantioselectivity of these chiral pesticides is significant to their estrogenic activities.

Fe_(3)O_(4) Nanoparticle‑modified Multi‑walled Carbon Nanotubes for the Determination of Synthetic Pyrethroids in Human Blood

In this study,a sensitive and rapid magnetic solid‑phase microextraction(MSPE)procedure based on Fe_(3)O_(4) nanoparticle‑modified,multi‑walled carbon nanotubes combined with a gas chromatography/electron capture detector(GC/ECD)was developed to quantify pyrethroids in human blood samples.This study compared liquid-liquid extraction and solid‑phase extraction methods and found that the MSPE‑GC/ECD method had many advantages,such as high recovery rate,high extraction efficiency,high detection sensitivity,low limit of detection,and simple operation.It can meet the actual requirements for the determination of synthetic pyrethroids in human blood.

Synthesis and properties of pyrethroids containing phosphorous β-substituted(thio)phosphonyl vinyl cyclopropane carboxylic ester

This paper presents nine novel pyrethroids containing phosphorous and five new phos- phorous ylids.A new synthetic route of β-substituted vinyl(thio)phosphonate having E configura- tion have been developed.The compound li exhibited moderate insecticidal activities against Culex mosquitoes and Army worm.

Current resistance status of Aedes aegypti and Aedes albopictus populations in Penang Island,Malaysia

Objective:To determine the current insecticide resistance status of Aedes(Ae.)aegypti and Ae.albopictus to four insecticides,namely 0.05%deltamethrin,0.75%permethrin,5%malathion and 0.25%pirimiphos-methyl using the World Health Organisation(WHO)susceptibility test kit.Methods:Adult bioassays were carried out using the standard protocol of the World Health Organisation.All F1 generation urban and suburban field strains of Ae.aegypti and Ae.albopictus were tested against pyrethroid and organophosphate insecticides,including the presence of piperonyl butoxide(PBO)in four replicates of 25 non-blood-fed female mosquitoes ranging from 3 to 5 days old.The Vector Control Research Unit(VCRU)laboratory strain served as a reference strain.Results:In this study,0.05%deltamethrin demonstrated a lower value of knockdown time when 50%of the mosquito population died(KT50)and knockdown time when 95%of the mosquito population died(KT95),which is significantly more effective compared to 0.75%permethrin against adult female Ae.aegypti(urban and suburban)and Ae.albopictus(urban and suburban)(ANOVA,P<0.01).Meanwhile,5%malathion was a more effective insecticide,amounting to the shorter KT50 and KT95 compared to 0.25%pirimiphos-methyl against Ae.aegypti(urban and suburban)and Ae.albopictus(urban and suburban).Ae.aegypti urban and Ae.aegypti suburban performed a higher resistance ratio(RR)towards both 0.05%deltamethrin and 0.75%permethrin due to the wide use of permethrin in dengue vector control programs in Malaysia.However,Ae.albopictus urban and suburban have lower resistance than Ae.aegypti urban and suburban towards 0.05%deltamethrin and 0.75%permethrin at 24 hours post-treatment.The addition of PBO with these insecticides successfully reduced knockdown time(KT50 and KT95)values of most of the Ae.aegypti and Ae.albopictus field strains except PBO+0.75%permethrin against Ae.aegypti suburban.Conclusions:The addition of PBO to insecticides has significantly reduced the knockdown time(KT50 and KT95)values on most of Ae.aegypti and Ae.albopictus urban strain except PBO+5%malathion against Ae.albopictus urban strain and PBO+0.75%permethrin against Ae.albopictus suburban strain in comparison to exposure to insecticides without PBO.Ae.aegypti showed a higher resistance ratio of 50(RR50)when compared with the VCRU laboratory reference strain(susceptible strain)at the exposure to the deltamethrin,including with pre-exposure to PBO.This study found that the addition of PBO with organophosphates(5%malathion and 0.25%pirimiphos-methyl)was significantly more effective than pyrethroids against Ae.aegypti and Ae.albopictus(urban and suburban)due to their high mortality rate at 24 hours.It can be concluded that the usage of PBO can help reduce resistance alteration in Aedes mosquitoes.

气相色谱-质谱联用对浓缩苹果汁中多种拟除虫菊酯类农药的快速测定

A GC-MS method was established for determination of 10 pyrethroids in apple juice concentrate.The sample was extracted by acetone and hexane,and the 10 pyrethroids were separated on a capillary column(DB-5,30 m×250 μm×0.25 μm) and determined by GC-MSD.The recoveries of pyrethroids were range of 84%-96% with the detection limits of 3-46 μg/kg.The relative standard deviations were range of 0.68%-5.11%.

The Entomological Efficacy of Piperonyl Butoxide (PBO) Combined with a Pyrethroid in Insecticide-Treated Nets for Malaria Prevention: A Village-Based Cohort Study Prior to Large-Scale Deployment of New Generation Mosquito Nets in Burkina Faso

The efficacy of insecticide-treated nets (ITNs) is increasingly compromised by the prevalence of malaria vectors resistant to pyrethroids. In response to this issue, a new generation of ITNs has been developed that incorporate synergistic components, such as piperonyl butoxide (PBO). The purpose of this study is to provide entomological evidence for the efficacy of a PBO-based ITN brand at the village level, serving as a basis for decision-making before large-scale net deployment. During the high malaria transmission period, ITNs were distributed in each group and vector sampling was conducted biweekly in selected households. Bionomic data were collected to assess the resistance of wild An. gambiae populations to various chemical insecticides. There was a significant disparity in total An. gambiae sl. collected between the ITN arms, the intervention arm (ITN arms), and the control arm (P = 0.003). An. coluzzi was identified as the predominant species in the study area, as confirmed by PCR analysis. Analysis of the blood-feeding inhibition rate revealed that 100% permethrin + PBO ITN exhibited significantly greater inhibition than 66.81% permethrin only ITN. According to the log-time probit regression analysis, permethrin exhibited a knockdown time of 256 min without synergists, while it decreased to 139 min (P = 0.001) when pre-exposed to PBO. The evidence from this trial supports the use of PBO ITNs over standard ITNs for pyrethroids to combat pyrethroid resistance and improve protection against malaria for both individuals and communities, particularly in areas with high pyrethroid resistance.

混配农药中毒防治研究

首次在我国开展大规模的混配农药中毒流行病学调查,发现接触混配农药是当前发生农药中毒的重要危险因素,为针对性的预防提供了科学依据。毒理学研究证实多数农药混剂呈增毒效应或协同作用,且与其毒代动力学变化有密切关系,为今后开发高效、低毒的混配农药提供了毒理学依据。在国内外首次建立甲基对硫磷单克隆抗体酶联免疫测定法,并成功研制便携式血胆碱酯酶快速测定仪;这些检测接触、效应生物标志物的灵敏、特异、便捷的方法已试用于现场,并具有开发为产品的前景。同时还发现对氧磷酶基因在192位点的单核苷酸多态性,可能是甲基对硫磷免疫毒性作用的易感性生物标志物之一。在总结不同类别农药混配后所致中毒的临床表现特点和规律的基础上,修订现行的农药中毒诊断标准,增添了有机磷单剂及混剂中毒所致“中间期肌无力综合征”的新内容,将提高我国农药中毒的诊治水平。本研究主要成果达国内领先和国际先进水平。

凝胶渗透色谱和气相色谱-质谱法测定动物食品中27种有机氯和15种拟除虫菊酯类农药残留量

A GC-MS method for the determination of 27 organochlorine pesticides and 15 Pyrethroid pesticides in animal food is established.The method was based on Gel Permeation chromatography combined with solid-phase extraction for sample preparation.Rapid qualitative and quantitative analyses was carried out by gas chromatography-mass spectrometry under the selective-ion monitoring mode.The experimental results showed that the correlation coefficients were better than 0.99,the recoveries for spiked standards were 70%-104%,the relative standard deviations were 2.1%-15.9%.

Fenvalerate-induced Alterations in Calcium Homeostasis in Rat Ovary

Objective To observe the effects of fenv＇,derate on calcium homeostasis in rat ovary. Methods Female SpragueDawley rats were orally given fenvalerate at dally doses of 0.00, 1.91, 9.55, and 31.80 mg/kg for four weeks. The ovary ultrastucture was observed by electron microscopy. Serum free calcium concentration was measured by atomic absorption spectrophotometry. The activities of phosphorylase a in rat ovary were evaluated by the chromatometry. The total content of calmodulin in ovary was estimated by ELISA at each stage of estrous cycle. Radioimmunoassay （R/A） was used to evaluate the level of serum progesterone. Results Histopathologically, damages of ovarian corpus luteum cells were observed. An increase in serum fi＇ee calcium concentration was observed in rats treated with 31.80mg/kg fenvalerate. The activities of phosphorylase a enhanced in all treated groups, and fenvalerate increased the total content of calmodulin significantly in estrus period. Serum progesterone levels declined in fenvalerate exposed rats in diestrus. Conclusion Fenvalerate interferes with calcium homeostasis in rat ovary. Also, the inhibitory effects of fenvalerate on serum progesterone levels may be mediated partly through calcium signals.

Toxicity and horizontal transfer of bifenthrin and dimefluthrin against the red imported fire ant, Solenopsis invicta Buren(Hymenoptera: Formicidae), and the efficacy of their dust applications in the field

The red imported fire ant,Solenopsis invicta Buren,poses a significant threat to biodiversity,agriculture,and public health in its introduced ranges.While chemicals such as toxic baits and dust are the main methods for S.invicta control,toxic baits are slow,requiring approximately one or two weeks,but dust can eliminate the colony of fire ants rapidly in just three to five days.To explore more active ingredients for fire ant control using dusts,the toxicity of bifenthrin and dimefluthrin,the horizontal transfer of bifenthrin and dimefluthrin dust and their efficacy in the field were tested.The results showed that the LD50(lethal dose) values of bifenthrin and dimefluthrin were 3.40 and 1.57 ng/ant,respectively.The KT50(median knockdown time) and KT95(95%knockdown time) values of a 20μg mL^(–1)bifenthrin dose were 7.179and 16.611 min,respectively.The KT50and KT95of a 5μg mL^(–1)dimefluthrin dose were 1.538 and 2.825 min,respectively.The horizontal transfers of bifenthrin and dimefluthrin among workers were effective.The mortality of recipients (secondary mortality) and secondary recipients (tertiary mortality) were both over 80%at 48 h after 0.25,0.50 and 1.00%bifenthrin dust treatments.The secondary mortality of recipients was over 99%at 48 h after 0.25,0.50 and 1.00% dimefluthrin dust treatments,but the tertiary mortality was below 20%.The field trial results showed that both bifenthrin and dimefluthrin exhibited excellent fire ant control effects,and the comprehensive control effects of 1.00%bifenthrin and dimefluthrin dusts at 14 d post-treatment were 95.87 and 85.70%,respectively.

Resistance status of main malaria vector, Liston (Diptera:Culicidae) to insecticides in a malaria Endemic Area,Southern Iran

Objective: To evaluate the susceptibility of Anopheles stephensi(An. stephensi) Liston, the main malaria vector in southern Iran, to WHO recommended insecticides. Methods: Larvae of An. stephensi were collected from three different larval habitats in both urban and rural area of Bandar Abbas city and one rural area in Rudan county southern Iran. WHO standard method was used for evaluation of adult and larval mosquito susceptibility. Bendiocarb, permethrin, lambda-cyhalothrin, deltamethrin as insecticide and temephos and chlorpyriphos as larvicide were used at the diagnostic dosages recommended by WHO. Results: Findings of this study showed all larval populations of An. stephensi were completely susceptible to temephos and candidate for resistance to chlorpyriphos. Adult mosquitoes in rural areas of Bandar Abbas city were resistant to pyrethroid and carbamate insecticides. Conclusion: Comparison of the results of this survey with previous studies indicates that the resistance to pyrethroids and carbamates in this malaria endemic region is increasing. Wide use of pesticides in agriculture is certainly effective in increasing resistance. The inter-sectoral coordination and collaboration in health and agriculture seem to be necessary to manage insecticide resistance in malaria vectors.