The synthetic pyrethroid isomers I. Preparation

Abstract

Enantiomers and racemic mixtures of selected benzilic esters using resolved and raceme permethrinic or chrysanthemic acids of high purity were synthesised via improved methods based on conventional steps. Nine basic structures of selected derivatives having hydrogen, bromo or phenoxy group at meta position were prepared including the well known insecticides of phenothrin, permethrin and cypermethrin. The optical purity of these compounds were determined via an NMR method applying chiral shift reagents. The configuration of the isomers of new a‐cyano‐benzyl esters were assigned via a rule realized by comparing the characteristic 1H NMR shifts of the dimethyl groups attached to the cyclopropane ring.     

Effects of synthetic pyrethroids and methidation on activities of some digestive enzymes in carp (Cyprinus carpio L.)

Abstract

The effects of pyrethroid pesticides (deltamethrin, permethrin and cypermethrin) and an organophosphate ester (methidation) on the activities of carp trypsin, α‐chymotrypsin, carboxypeptidase A and lipase were studied. The enzymes were isolated from the gastrointestinal tract and the effects of the pesticides were investigated during incubation for 5 min. The activity of trypsin was influenced only slightly by the presence of deltamethrin and methidation, whereas permethrin and cypermethrin caused significant inhibition. The pyrethroid pesticides at lower concentrations resulted in a slight activation of α‐chymotrypsin. Methidation inhibited the α‐chymotrypsin activity by about 20%. These pesticides modified the lipase activity to a lesser extent; the highest inhibition was measured with cypermethrin. The carboxypeptidase A activity was inhibited by both pyrethroid pesticides and methidation. The results suggest that these pesticides might interact with the active conformation of the studied hydrolytic enzymes, resulting in changes in their activities.     

Interaction effects of insecticides on microbial populations and dehydrogenase activity in a black clay soil

Three insecticides, monocrotophos, quinalphos, and cypermethrin, were applied at 0, 5, 10, and 25 microg g(-1) either singly or in combination to a black clay soil to investigate their effects on the soil microflora and dehydrogenase activity. All three insecticides significantly enhanced the proliferation of bacteria and fungi and the soil dehydrogenase activity even at the highest level of 25 microg g(-1). Monocrotophos or quinalphos in combination with cypermethrin at tested levels interacted significantly to yield additive, synergistic, and antagonistic responses toward bacteria and fungi and dehydrogenase activity in soil. Antagonistic interactions were more pronounced toward soil microflora and dehydrogenase activity when the two (monocrotophos or quinalphos + cypermethrin) insecticides were present together in the soil at highest level (25 + 25 microg g(-1)), whereas synergistic or additive responses occurred at lower level with the same combination of insecticides in soil.     

The synaptosomal membrane bound ATPase as a target for the neurotoxic effects of pyrethroids,permethrin and cypermethrin

Pyrethroids are used widely as insecticides both in agriculture and in households. A cellular target of pyrethroids is the sodium channel in the membrane. In the present study, the activity of the membrane bound integral protein ATPase was studied as a biomarker for the membrane effect of the pyrethroids permethrin and cypermethrin. Male Sprague-Dawley rats were used for cerebral synaptosome preparation. The isolation of synaptosomes was performed with the Percoll gradient method. Both total ATPase and Mg(2+) activated ATPase were studied by determining inorganic phosphate liberated from the substrate ATP. One hour exposure to permethrin (Biokill) and cypermethrin (Ripcord) insecticide products affected ATPase activities. The activity of Na(+), K(+) ATPase decreased dose-dependently in 10-50 microM concentrations of permethrin, and Mg(2+) activated ATPase increased over twofold in the same concentrations of the active components. The effect of the cypermethrin compound Ripcord was not clearly dose-dependent. The activity of total ATPase was almost entirely lost in the concentrations of 100 microM of permethrin and cypermethrin. The results support the idea that membrane ATPases are one target of the neurotoxic effect of pyrethroid compounds.     

Occurrence,compositional distribution,and toxicity assessment of pyrethroid insecticides in sediments from the fluvial systems of Chaohu Lake,Eastern China

Surface sediment-associated synthetic pyrethroid insecticides (SPs) are known to pose high risks to the benthic organisms in Chaohu Lake, a shallow lake of Eastern China. However, the pollution status of the lake’s tributaries and estuaries is still unknown. The present study was conducted to investigate the occurrence, compositional distribution, and toxicity of 12 currently used SPs in the surface sediments from four important tributaries, as well as in the sediment cores at their estuaries, using GC-MS for quantification. All SPs selected were detectable, with cypermethrin, es/fenvalerate, and permethrin dominant in both surface and core sediments, suggesting that these compounds were extensively applied. Urban samples contained the highest summed concentrations of the 12 SPs analyzed (Σ₁₂SP) in both surface and core sediments compared with rural samples, suggesting that urban areas near aquatic environments posed high risks for SPs. The mean concentration of Σ₁₂SP in surface sediments of each river was generally higher than that found in core sediments from its corresponding estuary, perhaps implying recent increases in SP usage. Surface sediments were significantly dominated by cypermethrin and permethrin, whereas core sediments were dominated by permethrin and es/fenvalerate. The compositional distributions demonstrated a spatial variation for surface sediments because urban sediments generally contained greater percentages of permethrin and cypermethrin, but rural sediments had significant levels of es/fenvalerate and cypermethrin. In all sediment cores, the percentage of permethrin gradually increased, whereas es/fenvalerate tended to decrease, from the bottom sediments to the top, indicating that the former represented fresh input, whereas the latter represented historical residue. Most urban samples would be expected to be highly toxic to benthic organisms due to the residue of SPs based on a calculation of toxic units (TUs) using toxicity data of the amphipod Hyalella azteca. However, low TU values were found for the samples from rural areas. These results indicate that the bottom sediments were exposed to high risk largely by the residual SPs from urban areas. The summed TUs were mostly attributable to cypermethrin, followed by λ-cyhalothrin and es/fenvalerate. Despite permethrin contributing ～28.7 % of the Σ₁₂SP concentration, it only represented 6.34 % of the summed TUs. Therefore, our results suggest that high levels of urbanization can increase the accumulation of SPs in aquatic environments.     

Effects of synthetic pyrethroids and methidation on activities of some digestive enzymes in carp (Cyprinus carpio L.).

The effects of pyrethroid pesticides (deltamethrin, permethrin and cypermethrin) and an organophosphate ester (methidation) on the activities of carp trypsin, alpha-chymotrypsin, carboxypeptidase A and lipase were studied. The enzymes were isolated from the gastrointestinal tract and the effects of the pesticides were investigated during incubation for 5 min. The activity of trypsin was influenced only slightly by the presence of deltamethrin and methidation, whereas permethrin and cypermethrin caused significant inhibition. The pyrethroid pesticides at lower concentrations resulted in a slight activation of alpha-chymotrypsin. Methidation inhibited the alpha-chymotrypsin activity by about 20%. These pesticides modified the lipase activity to a lesser extent; the highest inhibition was measured with cypermethrin. The carboxypeptidase A activity was inhibited by both pyrethroid pesticides and methidation. The results suggest that these pesticides might interact with the active conformation of the studied hydrolytic enzymes, resulting in changes in their activities.     

Effects of pyrethroid insecticide seed treatments on Rhizobium japonicum and its symbiotic relationship with,and growth of soybean

Abstract

Two pyrethroid insecticides were compared with two fungicides for their effects on the rhizobial and seedling components of the N₂‐fixing symbiosis in soybeans (Glycine max Merr. variety Olinda). In vitro growth of Rhizobium japonicum RI16, was inhibited in the order of HgCl₂ > thiram > cypermethrin > permethrin. The emergence of the seedlings was stimulated by all chemicals tested. Also, none of the pesticides studied had any significant effect on N₂ fixation (acetylene reduction), at the dosages used. Consequently, yields of the various organs were also not significantly influenced by the chemicals.     

In vitro toxicity of selected pesticides on RTG-2 and RTL-W1 fish cell lines

The rainbow trout fish cell lines RTG-2 and RTL-W1 were used to determine the cytotoxic effects of the pesticides bifenthrin, cypermethrin, cyhalothrin, lambda-cyhalothrin, quinalphos and chlorpyrifos. Cytotoxicity was measured by EROD and beta-Gal enzymatic activities, the neutral red (NR) uptake assay, and the FRAME KB protein (KBP) assay. The beta-Gal activity was unaffected by the pesticide exposure. The EROD activity was induced by cyhalothrin and lambda-cyhalothrin (RTG-2 and RTL-W1) and by bifenthrin (RTL-W1). Dose dependent inhibition responses were observed for EROD activity in cells exposed to quinalphos (RTL-W1) and chlorpyrifos (RTG-2 and RTL-W1). RTL-W1 offered a better response for EROD induction. The EC50 values on EROD endpoint were more sensitive than NR and KBP. The acute fish toxicity of chlorpyrifos and quinalphos depends highly on the species; the species sensitivity distributions cover several orders of magnitude and the values obtained for EROS were within the lowest part of the reported ranges.     

A field study on residues of four insecticides used in strawberry protection

Abstract

In 1986 strawberry plots were treated with dimethoate, malathion, permethrin and cypermethrin at 80% bloom of primary flowers. In 1987 the plots were sprayed with dimethoate, malathion and permethrin at 30% bloom. Residue analysis of these insecticides on the flowers were analyzed using solvent extraction and gas liquid chromatography. Residue analysis at 0 to 18 days on flowers and fruit showed an exponential decrease. Organophosphates tended to degrade more quickly than synthetic pyrethroids. The results are discussed in the context of an integrated pest management program.     

A simple HPLC method for determination of permethrin residues in wine

An isocratic High Performance Liquid Chromatographic (HPLC) method was optimized for 3-phenoxybenzyl (1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate (permethrin) residues identification and quantification in wine matrix. Analytical reverse phase (RP) C-18 column was used (25 cm × 4 mm i.d., 5 μ m) with mobile phase consisting of acetonitrile and water in ratio 70 %/30 % (v v^?1), flow-rate 2.0 mL min^?1, UV-detection at 215 nm and controlled oven temperature at 25°C. The peaks of isomers were identified with the retention times as compared to standard cis-/trans- mixture and confirmed with characteristic spectra using photodiode array detector. Under these conditions, permethrin isomers were well separated with resolution 2.8 and no interference with the naturally present wine compounds was observed. The method was validated for linearity, precision, accuracy, limit of detection (LOD) and limit of quantification (LOQ). Linear regression analysis data proved a good linear relationship (correlation coefficients, r², for cis- and trans-isomer are: 0.9995 and 0.9997, respectively) between response of the detector and concentration of permethrin isomers over a wide concentration range for both isomers (0.55 mg L^?1 ?4.40 mg L^?1). Experimental data showed mean recoveries between 93.95% and 96.58% with RSD values in range: 0.89% ?3.69%. The effect of ethanol content in the solvent on permethrin isomers peak areas was also studied and 60% v v^?1 ethanol was found to be optimal for sample preparation. The method was successfully tested on 20 commercial wine samples from the market in which no permethrin was detected. Thus, it was proved that it is suitable for routine permethrin residues analysis. The proposed method is suitable for routine analysis because of the simple sample preparation, acceptable run-time, low cost and its applicability with conventional instruments.     

Toxicity of new pyrethroid in pest insects Asciamonuste and Diaphania hyalinata,predator Solenopsis saevissima and stingless bee Tetragonisca angustula

There is increasing demand for new products for vegetable pest management. Thus, the aim of this study was to assess the toxicity of pyrethroids with acid moiety modifications to measure the insecticidal activity of these compounds on the lepidopteran vegetable pests Diaphania hyalinata (L.) (Lepidoptera: Pyralidae) and Asciamonuste (Latreille) (Lepidoptera: Pieridae) and evaluate their selectivity for the predatory ant Solenopsis saevissima (F. Smith) (Hymenoptera: Formicidae) and pollinator Tetragonisca angustula (Latreille) (Hymenoptera: Apidae: Meliponinae). Racemic mixtures of five new pyrethroids (30 µg molecule mg^?1 insect body weight) resulted in high (100%) and rapid (stable LD₅₀ after 12 h) mortality in D. hyalinata and A. monuste. In A. monuste, the trans-pyrethroid [12] isomer showed similar toxicity to permethrin. For D. hyalinata, the trans-pyrethroid [9] isomer and cis-pyrethroid [10] isomer were as toxic as permethrin. Due to their low selectivity, these new pyrethroids should be applied on the basis of ecological selectivity principles to minimize impacts on nontarget organisms S. saevissima and T. angustula.     

Effect and mechanism of action of methomyl and cypermethrin insecticides on kynurenine metabolizing enzymes of mouse liver

Abstract

The effect of methomyl and cypermethrin insecticides on the B₆‐dependent kynurenine hydrolase(KH) and kynurenine aminotransferase (KATE) was studied. These insecticides induced pronounced inhibition on the (KH) and (KATE) enzymes after single dose treatment. Repeated doses of methomyl induced inhibition on the (KH) and (KATE) activities, whereas repeated treatment with cypermethrin had no effect on the activities of these enzymes. In vitro methomyl inhibited (KH) and (KATE) enzymes at 10 M up to 10^‐3 M, through a competitive mechanism. Methomyl and cypermethrin are capable of causing alterations in the kynurenine metabolizing enzymes of mouse liver.     

Effects of droplet density and concentration on the efficacy of bacillus thuringiensis and carbaryl against gypsy moth larvae (Lymantria dispar L.)

Abstract

The feeding behavior of gypsy moth larvae exposed to two pesticide deposits (Bt and carbaryl) on oak leaf disks was monitored to determine the relationships between its efficacy and application parameters (droplet density and pesticide concentration). A range of pesticide concentrations and droplet densities (from 9 to 149 droplets/cm²) was used to simulate high and low application rates produced by different methods of application in the field.

The LD₅₀ and the LC₅₀, appeared to be affected by the spatial distribution of the deposit on the leaf surface. Both Bt and carbaryl showed a decreasing LD₅₀ at increasing time after spray. The LD₅₀ of Bt decreased from 14.1 BIU/liter to 3.1 BIU/Iiter between 48 and 144 hours after spray. The results show that feeding inhibition by Bt is more closely related to concentration than to droplet density and dose per unit area with the highest feeding inhibition occurring at 10 BIU/liter at 9 droplets/cm². With carbaryl, an increase in both concentration and droplet density was necessary to cause a decrease in leaf area eaten by larvae.     

Introduction

Abstract

Eight pairs of O‐methyl and O‐ethyl O‐(substituted‐phenyl) phenylphosphonothionates were evaluated with respect to their delayed neurotoxic activity in hens. O‐methyl compounds were in all cases more active than their O‐ethyl analogs. The neurotoxic potential of the O‐methyl phenylphosphonothionates was 2,5‐diCl >4‐NO₂ >2,4,5‐triCl and 2,4,6‐triCl >2,4‐diCl >2,5‐diCl‐4‐Br >4‐CN, when single oral doses were given. Both EPN‐ethyl and leptophos‐raethyl were more neurotoxic in multiple dermal than multiple oral dosing regimens. LD₅₀s for mice and flies were established.     

Acute toxicity and ecotoxicological risk assessment of rice pesticides to Lithobates catesbeianus tadpoles

The objective of this study was to determine the acute toxicity of some pesticides used in irrigated rice farming to Lithobates catesbeianus tadpoles. The LC_50-96h for commercial formulations containing bentazon, penoxsulam, vegetable oil, permethrin and carbofuran, separately and their mixtures, were determined at the proportions commonly used in the field. The limits of risk concentrations of these products for the studied species were also established. The LC_50-96h for tadpoles was 4,530 mg L^?1 for bentazon; 7.52 mg L^?1 for penoxsulam + 145.66 mg L^?1 of vegetable oil; 81.57 mg L^?1 for vegetable oil; 0.10 mg L^?1 for permethrin; 29.90 mg L^?1 for carbofuran (active ingredients), and 38.79 times the dose used in the field for the mixture of these products. The environmental risk was determined only for permethrin, and care should be taken when using the vegetable oil.     

Sublethal Effects of Monocrotophos on Locomotor Behavior and Gill Architecture of the Mosquito Fish,Gambusia affinis

Subacute studies of monocrotophos [Dimethyl (E)-1-methyl-2-(methyl-carbamoyl) vinyl phosphate] on mosquito fish, Gambusia affinis, were carried out in vivo for 24 days to assess the locomotor behavior, structural integrity of gill, and targeted enzyme acetylcholinesterase (AChE, EC: 3.1.1.7) interactions. Monocrotophos (MCP) can be rated as moderately toxic to G. affinis, with a median lethal concentration (LC₅₀) of 20.49 ± 2.45 mgL^?1. The fish exposed to sublethal concentration of LC₁₀ (7.74 mgL^?1) were under stress and altered their locomotor behavior, such as distance traveled per unit time (m min^?1) and swimming speed (cm sec^?1) with respect to the length of exposure. Inhibition in the activity of brain AChE and deformities in the primary and secondary lamellae of gill may have resulted in failure of exchange of gases. The maximum inhibition of 95% of AChE activity was observed on days 20 and 24.

Morphological aberrations in the gills were also studied during exposure to the sublethal concentration of monocrotophos for a period ranging from 8 to 24 days. The extent of damage in gill was dependent on the duration of exposure. The findings revealed that inhibition in brain AChE activity and structural alteration in gill were responsible for altering the locomotor behavior of exposed fish.     

The Capture of Heavy Metals from Incineration Using a Spray Dryer Integrated with a Fabric Filter Using Various Additives

ABSTRACT

This study investigated the effects of feedstock additives [polyvinyl chloride (PVC) and NaCl] and spray dryer additives (SiO₂, CaCl₂, NaHCO₃) on heavy metal and fly ash removal efficiencies, and on particle size distribution of heavy metals. A spray dryer with an integrated fabric filter was used as an air pollution control device (APCD). Removal efficiencies for fly ash and heavy metals were greater than 95 and 90%, respectively. When additives of PVC or NaCl were used, the concentration of heavy metals distributed in fly ash apparently varied when the particle diameter was <1 μm. Although the effects of the additives SiO₂, CaCl₂, and NaHCO₃ on the elemental size distribution of Cr were insignificant, these additives did slightly increase concentrations of Cd, Zn, and Pb partitioning in coarser particles (>1μm).     

Nickel Speciation of Residual Oil Fly Ash and Ambient Particulate Matter Using X-ray Absorption Spectroscopy

ABSTRACT

The chemical speciation of Ni in fly ash produced from ~0.85 wt % S residual (no. 6 fuel) oils in laboratory (7 kW)- and utility (400 MW)-scale combustion systems was investigated using X-ray absorption fine structure (XAFS) spectroscopy, X-ray diffraction (XRD), and acetate extraction [1 M NaOAc-0.5 M HOAc (pH 5) at 25 °C]-anodic stripping voltammetry (ASV). XAFS was also used to determine the Ni speciation of ambient particulate matter (PM) sampled near the 400-MW system. Based on XAFS analyses of bulk fly ash and their corresponding acetate extraction residue, it is estimated that >99% of the total Ni (0.38 wt %) in the experimentally produced fly ash occurs as NiSO₄-xH₂O, whereas >95% of the total Ni (1.70 and 2.25 wt %) in two fly ash samples from the 400-MW system occurs as NiSO₄-xH₂O and Ni-bearing spinel, possibly NiFe₂O₄. Spinel was also detected using XRD. Acetate extracts most of the NiSO₄-xH₂O and concentrates insoluble NiFe₂O₄ in extraction residue. Similar to fly ash, ambient PM contains NiSO₄-xH₂O and NiFe₂O₄;

however, the proportion of NiSO₄-xH₂O relative to NiFe₂O₄ is much greater in the PM. Results from this and previous investigations indicate that residual oil ash produced in the 7-kW combustion system lack insoluble Ni (e.g., NiFe₂O₄) but are enriched in soluble NiSO₄-xH₂O relative to fly ash from utility-scale systems. This difference in Ni speciation is most likely related to the lack of additive [e.g., Mg(OH)₂] injection and residence time in the 7-kW combustion system.     

Endosulfan and Quinalphos Residues and Toxicity to Soil Microarthropods after Repeated Applications in a Field Investigation

Endosulfan (1,4,5,6,7,7-hexachloro-8,9,10-trinorborn-5-en-2,3-ylenedimethylsulphite) and quinalphos (O,O-diethyl O-quinoxalin-2-yl phosphorothioate) persistence and their effect on soil microarthropods were studied after repeated applications in cotton fields. Dissipation behavior of insecticides after repeated applications was observed from 78 to 292 days after the first insecticide treatment. At any given time the concentrations of endosulfan β residues were always higher as compared to endosulfan α. From 78 to 85 days, 5.0% and 20.4% decrease in α and β endosulfan residues was observed, respectively. Endosulfan β isomer decreased up to 93.0% in 292 days. Endosulfan sulfate was detected as a major metabolite in the soil samples. Total endosulfan residues decreased by 86.6% from 78 to 292 days. The amounts of quinalphos residues were less as compared to endosulfan at any given time. The residues observed after 78 days of application were 0.88 ng g^?1 d wt. soil. At the end of 145 days, a 35.0% decrease in quinalphos residue was observed, which decreased further by 50.9% in 292 days. Among the soil microarthropods studied, Acarina was more sensitive to the applied insecticides as compared to Collembola. Three days after the last treatment, up to 94.5% (p < 0.01) and 71.2% (p < 0.05) decrease in Acarina population was observed in endosulfan and quinalphos treated fields, respectively, compared to control field. In general, no noticeable change in Collembola population was observed after the insecticide treatments.