Screening for Enhancement of Permethrin Toxicity by Plant Essential Oils Against Adult Females of the Yellow Fever Mosquito (Diptera: Culicidae).

Aedes aegypti L. (Diptera: Culicidae) is one of the most medically important mosquito species, due to its ability to spread viruses of yellow fever, dengue fever, and Zika in humans. In this study, the insecticidal activity of 17 plant essential oils was evaluated via topical application against two strains of Ae. aegypti mosquito, Orlando (insecticide-susceptible) and Puerto Rico (pyrethroid-resistant). Initial screens with the Orlando strain showed that cucumber seed oil (2017 sample) was the most toxic, followed by sandalwood and thyme oil. When the essential oils were mixed with permethrin, they failed to show any significant synergism of insecticidal activity. Sandalwood and thyme oils displayed consistently high mortality against the resistant Puerto Rico strain, with low resistance ratios of 2.1 and 1.4, respectively. In contrast, cucumber seed oil showed significantly less activity against Puerto Rico mosquitoes, with a resistance ratio of 45. Bioactivity-guided fractionation of the 2017 sample of cucumber seed oil sample via flash column chromatography produced 11 fractions, and gas-chromatography/mass spectrometry analysis revealed that the three active fractions were contaminated with 0.33, 0.36, and 0.33% of chlorpyrifos-methyl, an organophosphorus insecticide, whereas inactive fractions did not show any trace of it. These results suggested that the insecticidal activity of cucumber seed oil was probably due to the presence of the insecticide, later confirmed with a clean batch of cucumber seed oil obtained in 2018, which showed negligible insecticidal activity. These findings demonstrate clearly the need for essential oil analysis to confirm purity before any claims are made about pesticidal potency.

[Determination of S-421 in Commercial Fish and Shellfish].

S-421 is a synergist of pyrethroid and organophosphorus pesticides, which are used as termiticides or household insecticides. S-421 is stable and ubiquitous in the environment. Here we describe the concentrations of S-421 in domestic and imported commercial fish collected from 2009 to 2016. Samples were extracted with acetone/hexane and S-421 was purified on a silica gel column. Quantitative analysis was performed by GC-ECD. S-421 was detected in 78 of 116 samples of domestic fish and shellfish at levels of <0.2 to 2.6 ng/g (mean: 0.4 ng/g), and in 69 of 102 imported samples at a level of <0.2 to 1.5 ng/g (mean: 0.4 ng/g). The concentrations of S-421 in fish were lower than those of p,p'-DDE and similar to those of ß-HCH.

Migration and Accumulation of Octachlorodipropyl Ether in Soil-Tea Systems in Young and Old Tea Gardens.

The migration and accumulation of octachlorodipropyl ether (OCDPE) in soil-tea systems were investigated using a gas chromatography-electron capture detector (GC-ECD) method in young and old tea gardens. When the residual concentration of OCDPE was 100 g a.i. hm-2 in soils, the peak concentrations of OCDPE in fresh leaves of young and old tea plants were 0.365 mg/kg and 0.144 mg/kg, taking 45 days and 55 days, respectively. Equations for the accumulation curves of OCDPE in fresh leaves of young and old tea plants were Ct = 0.0227e0.0566t (R² = 0.9154) and Ct = 0.0298e-0.0306t (R² = 0.7156), and were Ct = 3.8435e0.055t (R² = 0.9698) and Ct = 1.5627e-0.048t (R² = 0.9634) for dissipation curves, with a half-life of 14.4 days and 12.6 days, respectively. These results have practical guiding significance for controlling tea food safety.

Dissipation behavior of octachlorodipropyl ether residues during tea planting and brewing process.

The dissipation behavior of octachlorodipropyl ether (OCDPE) residues in fresh tea shoots and in tea prepared under field conditions was investigated, and the transfer of residues from brewed tea to tea infusion was determined. OCDPE levels in tea shoots, prepared tea, tea infusion, and spent tea leaves were determined using a sensitive and simple method. The dissipation of OCDPE is fairly slow in tea shoots and prepared tea, with half-life values of 5.10 and 5.46 days, respectively. The degradation rates of OCDPE residues in tea processing were 23.9-43.1 %. The terminal residues of OCDPE in tea shoots and prepared tea samples after 20 and 30 days of OCDPE application were higher than 0.01 mg/kg. However, OCDPE's transfer rates from brewed tea to tea infusion were only 6.0-14.8 %. Further studies on risk assessment of OCDPE residue in tea on the basis of the relationship of OCDPE in prepared tea and infusion are warranted.

Human exposure to insecticide products containing pyrethrins and piperonyl butoxide (2001-2003).

Pyrethrum, used as an insecticide for centuries, is derived from dried and ground flowers of Chrysanthemum cinerariaefolium. Its current major use is in insecticide products to the control insects in the home and food handling establishments. We investigated human incidents reported through the American Association of Poison Control Centers (AAPCC) Toxic Exposure Surveillance System (TESS) associated with regulated insecticides containing pyrethrins and piperonyl butoxide (PY/PBO) from 2001 to 2003. Special attention was paid to dermal and respiratory effects. Although there are limitations associated with TESS data, we observed that In view of their widespread use, the data indicates that PY/PBO products can be used with a relatively low risk of adverse effects. Moreover, the data suggest that they are not likely to cause reactions in people with asthma or allergies.

A human-health risk assessment for West Nile virus and insecticides used in mosquito management.

West Nile virus (WNV) has been a major public health concern in North America since 1999, when the first outbreak in the Western Hemisphere occurred in New York City. As a result of this ongoing disease outbreak, management of mosquitoes that vector WNV throughout the United States and Canada has necessitated using insecticides in areas where they traditionally have not been used or have been used less frequently. This has resulted in concerns by the public about the risks from insecticide use. The objective of this study was to use reasonable worst-case risk assessment methodologies to evaluate human-health risks for WNV and the insecticides most commonly used to control adult mosquitoes. We evaluated documented health effects from WNV infection and determined potential population risks based on reported frequencies. We determined potential acute (1-day) and subchronic (90-day) multiroute residential exposures from each insecticide for several human subgroups during a WNV disease outbreak scenario. We then compared potential insecticide exposures to toxicologic and regulatory effect levels. Risk quotients (RQs, the ratio of exposure to toxicologic effect) were < 1.0 for all subgroups. Acute RQs ranged from 0.0004 to 0.4726, and subchronic RQs ranged from 0.00014 to 0.2074. Results from our risk assessment and the current weight of scientific evidence indicate that human-health risks from residential exposure to mosquito insecticides are low and are not likely to exceed levels of concern. Further, our results indicate that, based on human-health criteria, the risks from WNV exceed the risks from exposure to mosquito insecticides.

Pyrethrins and piperonyl butoxide adsorption to soil organic matter.

The adsorption and mobility of pyrethrins (Pys), the major insecticidal components obtained from the pyrethrum daisy Tanacetum cinerariifolium, and piperonyl butoxide (PBO), a pyrethrum synergist, were determined in soil using batch-equilibrium and reverse-phase thin-layer chromatographic techniques. Two soil management practices were used, soil mixed with yard waste compost (COM) at 50 t acre(-1) on dry weight basis and no-mulch (NM) bare soil. Adsorption isotherm experiments were carried out using known concentrations of Pys (Py-I and Py-II) and PBO mixed with known amounts of COM or NM soil at constant temperature and pressure until equilibrium was attained. Pys and PBO in soil extracts were purified and concentrated using solid-phase extraction cartridges containing C18-octadecyl bonded silica. Pys and PBO residues were quantified using a high-performance liquid chromatograph equipped with a UV detector. Adsorption studies showed that compost amended soil adsorbed more Pys and PBO than native (NM) soil. Py-I adsorption was greater than Py-II and PBO. Adsorption of Pys and PBO to humic and fulvic acids was also studied by reverse-phase thin layer chromatography (RPTLC). Results indicated that humic acid, a significant component of organic matter, reduced Pys and PBO mobility. Pys and PBO mobility decreased as the concentration of humic acid in the mobile phase increased.

Toxicity of synthetic piperonyl compounds to leaf-cutting ants and their symbiotic fungus.

The development of Leucoagaricus gongylophorus, the fungus cultured by the leaf-cutting ant Atta sexdens was inhibited in vitro by synthetic compounds containing the piperonyl group. In addition, worker ants that were fed daily on an artificial diet to which these compounds were added had a higher mortality rate than the controls. The inhibition of the fungal growth increased with the size of the carbon side chain ranging from C1 through C8 and decreasing thereafter. 1-(3,4-Methylenedioxybenzyloxy)octane (compound 5) was the most active compound and inhibited the fungal development by 80% at a concentration of 15 micrograms ml-1. With worker ants the toxic effects started with compound 5 and increased with the number of carbons in the side chain. Thus, for the same concentration (100 micrograms ml-1) the mortality rates observed after 8 days of diet ingestion were 82%, 66% and 42%, for 1-(3,4-methylenedioxybenzyloxy)decane, 1-(3,4-methylenedioxybenzyloxy)dodecane and compound 5, respectively, whereas with commercial piperonyl butoxide the mortality was 68%. The latter compound, which is known as a synergist insecticide, was as inhibitory to the symbiotic fungus as the synthetic compound 5. The possibility of controlling these insects in the future using compounds that can target simultaneously both organisms is discussed.

Determination of rotenoids and piperonyl butoxide in water, sediments and piscicide formulations.

Rotenone is a naturally occurring insecticide and piscicide (fish poison) found in many leguminous plants. This paper describes high-performance liquid chromatography (HPLC) methods for the quantitative analysis of rotenone's principal biologically active components (rotenone, tephrosin, rotenolone, deguelin) and the synergist piperonyl butoxide (PBO) in various media. Compounds were separated on a C18 reversed phase column with an acetonitrile-0.025 M phosphoric acid mobile phase and detected by UV absorbance or fluorescence (PBO only). Solid phase extraction (SPE) was used in either coupled (on-line) mode with a C18 concentrator column or automated off-line mode using Empore C18 disks. The on-line extraction efficiency was improved significantly by adding small amounts of methanol to water. Method detection limits (MDLs) for rotenoids and PBO in reagent water were 0.3 and 2 micrograms L-1, respectively, with optimal recoveries ranging from 90% to 99%. Aquatic sediments were extracted with methanol and the extracts were diluted in water prior to analysis by coupled SPE-HPLC. In wet sediments, detection limits were approximately 20-100 micrograms kg-1 with recoveries of 71% to 87%. Sonication in dimethyl sulfoxide (DMSO) followed by dilution in acetonitrile and filtration allowed determination of the active ingredients in powdered rotenone formulations. Details of sample preparation, cartridge column cleanup and analyte confirmation are provided.

Residue levels of pyrethrins and piperonyl butoxide in soil and runoff water.

Simultaneous analysis of pyrethrins (Py-I and Py-II) and piperonyl butoxide (PBO) in soil and runoff water samples following field application of a new pyrethrum formulation containing pyrethrins (Py's) and PBO is described. Residues of total Py's and PBO were extracted from soil samples using hexane-acetone (9:1). A solid phase extraction (SPE) column containing C18-octadecyl bonded silica was used to separate Py's and PBO residues from runoff water. Residues in soil and water were quantitated by high performance liquid chromatography (HPLC) equipped with C18-column and a UV detector. Concentration of Py-II in soil was 100 times higher than that of Py-I 1 h following treatment and 9.6 times higher than Py-I in runoff surface water 11 days following treatment. Results indicated that Py's are non-persistent in soil (even though lipophillic) and water when applied at the recommended rate of 6 lbs (5.31 g A.I.) per acre. There was a consistent decrease in total Py's residues as time after spraying increased. Py's residues in soil decreased from 0.91 to 0.11 ppm 4 days following treatment and one month after treatment only 0.002 ppm were detected. The highest concentration of Py's in runoff water was 36.09 ng/liter following the first rainfall (11 days following treatment). PBO initial residues detected in soil samples were low (0.84 microgram/g soil) while no residues of PBO were detected in runoff water.

Analysis of insecticide synergists.

The utility of a variety of chromatographic procedures (GLC, TLC, and GLC/MS) has been described for the determination of a variety of methylene dioxyphenyl insecticide synergists. Particular focus was placed on chromatographic aspects of the principal synergist, piperonyl butoxide, in relation to its trace impurities, determination in formulations, metabolism, residues, and stability.