Extraction of permethrin from impregnated fabrics for determination by ultra-high performance liquid chromatography with diode array detection.

Permethrin is a synthetic pyrethroid insecticide that is largely used in the impregnation of fabrics employed for different purposes. This paper reports a detailed study on the conditions for its extraction from fabrics and for its determination by ultra-high performance liquid chromatography with diode array detection (UHPLC-DAD). Several parameters that could affect the extraction efficiency of permethrin were evaluated, such as the extraction time, agitating mode (mechanical or ultrasound-assisted), solvent type (methanol or acetonitrile), concentration, and volume. Under optimized conditions, the extraction was performed for 10 min using a 2 × 2 cm piece of impregnated fabric and 5 mL of pure methanol. The flask containing the sample and the solvent was shaken mechanically using a horizontal roller mixer. The accuracy of the method was assessed by a recovery test, which presented satisfactory results ranging from 86.8% to 95.2%. The method was employed in the analysis of nine samples of commercial fabrics of different colors and grammages that were impregnated with permethrin. The concentration of permethrin found in these samples varied between 25.6 ± 4.2 and 934 ± 119 mg m-2.

Diazinon and permethrin mitigation across a grass-wetland buffer.

Vegetated buffers of different designs are often used as edge-of-field treatment practices to remove pesticides that may be entrained in agricultural runoff. However, buffer system efficacy in pesticide runoff mitigation varies widely due to a multitude of factors including, but not limited to, pesticide chemistry, vegetation composition, and hydrology. Two experimental systems, a control (no vegetation) and a grass-wetland buffer system, were evaluated for their ability to retain diazinon and permethrin associated with a simulated storm runoff. The two systems were equally inefficient at retaining diazinon (mean 9.6 % retention for control and buffer). Grass-wetland buffers retained 83 % and 85 % of cis- and trans-permethrin masses, respectively, while the control only retained 39 % and 44 % of cis- and trans-permethrin masses, respectively. Half-distances (the distance required to decrease pesticide concentration by one-half) for both permethrin isomers were 26 %-30 % shorter in grass buffers (22-23 m) than in the control (32 m). The current study demonstrates treatment efficacy was a function of pesticide properties with the more strongly sorbing permethrin retained to a greater degree. The study also demonstrates challenges in remediating multiple pesticides with a single management practice. By using suites of management practices, especially those employing vegetation, better mitigation of pesticide impacts may be accomplished.

The pharmaceutical use of permethrin: sources and behavior during municipal sewage treatment.

Permethrin entered use in the 1970s as an insecticide in a wide range of applications, including agriculture, horticultural, and forestry, and has since been restricted. In the 21st century, the presence of permethrin in the aquatic environment has been attributed to its use as a human and veterinary pharmaceutical, in particular as a pedeculicide, in addition to other uses, such as a moth-proofing agent. However, as a consequence of its toxicity to fish, sources of permethrin and its fate and behavior during wastewater treatment are topics of concern. This study has established that high overall removal of permethrin (approximately 90%) was achieved during wastewater treatment and that this was strongly dependent on the extent of biological degradation in secondary treatment, with more limited subsequent removal in tertiary treatment processes. Sources of permethrin in the catchment matched well with measured values in crude sewage and indicated that domestic use accounted for more than half of the load to the treatment works. However, removal may not be consistent enough to achieve the environmental quality standards now being derived in many countries even where tertiary treatment processes are applied.

Fate and removal of permethrin by conventional activated sludge treatment.

The fate and removal of permethrin during conventional wastewater treatment were evaluated at pilot-plant scale at different concentrations of mixed liquor suspended solids (MLSS) and, hence, different solids retention times (SRT). At feed concentrations of 0.26-0.86 microg L(-1), the permethrin was removed by primary treatment at an efficiency rate of 37%, similar to previously reported data, and from 40% to 83% for secondary treatment, decreasing with decreasing SRT. Comparable ranges, from 37% up to 98%, have been reported for micropollutants with similar physicochemical properties to permethrin, such as galaxolide and tonalide. Little difference in removal was noted between the medium and low MLSS concentrations trials, the main difference in treated effluent permethrin concentration arising on changing from high to medium MLSS levels. This was attributed to the limited acclimatization period employed in these two trials, leading to higher levels of soluble organic matter in the treated water, with which the permethrin appeared to be associated.

HPLC-method for determination of permethrin enantiomers using chiral beta-cyclodextrin-based stationary phase.

The liquid chromatographic separation of permethrin enantiomers on chiral beta-cyclodextrin-based stationary phase has been investigated. All four enantiomers are obtained by using simple methanol and water mobile phase, under gradient mode. The method was optimized and validated. The relationship between temperature and chromatographic parameters: k' (capacity factor), alpha (separation factor) and Rs (resolution factor) was studied. Van't Hoff's curves for each enantiomer were plotted for temperature range 288-318 K. It was noticed that the response factor ratio of permethrin isomers differ and calculated value is found to be 1.66 (cis/trans, for n = 5). This method has been used for determining permethrin enantiomer ratio for a few samples of working standards and one formulation.

Direct high-performance liquid chromatographic method for enantioselective and diastereoselective determination of selected pyrethroic acids.

This study reports on the direct HPLC stereoisomer separation of selected pyrethroic acids employing commercial cinchona alkaloid derived chiral stationary phases (CSPs). cis/trans-Chrysanthemic acid (cis/trans-CA), cis/trans-chrysanthemum dicarboxylic acid (cis/trans-CDCA), cis/trans-permethrinic acid (cis/trans-PA), and fenvaleric acid (FA) were resolved into the individual stereoisomers, i.e. enantiomers and diastereomers as well. To achieve satisfactory baseline separation an optimisation of the variables of the chromatographic method including chemical structure of the cinchona carbamate CSP, mobile phase composition, and flow rate was required. All four stereoisomers of PA were successfully separated in a single run (alphacis = 1.20, alphatrans = 1.26, critical Rs = 1.65) with an acetonitrile (ACN)-based polar-organic eluent. The complete baseline resolution of all CA stereoisomers succeeded in polar-organic (alphacis = 1.20, alphatrans = 1.35, critical Rs = 3.03) as well as in acetonitrile-based reversed-phase media (alphacis = 1.24, alphatrans = 1.22, critical Rs = 2.73). The latter elution mode was also found to be suitable for the enantio- as well as diastereoselective resolution of CDCA (alphacis = 1.09, alphatrans = 1.50, critical Rs = 1.43), which is to the best of our knowledge the first reported enantiomer separation of this analyte. The enantiomers of FA could be baseline separated employing also reversed-phase mode (alpha = 1.16, Rs = 2.91). These separation methods may be applied for quality control processes in the production of stereoisomerically pure insecticides as well as stereoselective toxicokinetic studies, as CDCA, PA, and FA are suitable biomarkers for monitoring human pyrethroid burden.

Aqueous pesticide mitigation efficiency of Typha latifolia (L.), Leersia oryzoides (L.) Sw., and Sparganium americanum Nutt.

Agricultural pesticide use is necessary to help meet the increased demand for a safe and secure food supply for the United States, as well as the global community. Even with proper application and careful management, the possibility of pesticide leaching and detachment in runoff still exists following certain storm events. Several different management practices have been designed to reduce the impacts of pesticides on aquatic receiving systems. Many such practices focus on the use of vegetation to slow runoff and allow for sorption of the various contaminants. Three common drainage ditch macrophytes, Leersia oryzoides (cutgrass), Typha latifolia (cattail), and Sparganium americanum (bur-reed) were assessed for their ability to reduce effluent loads of atrazine, diazinon, and permethrin in simulated agricultural runoff water in 379L individual mesocosms. Of the three macrophytes examined, L. oryzoides was the most effective at mitigating atrazine, and permethrin. L. oryzoides and T. latifolia significantly reduced overall atrazine loads (45±7%, p=0.0073 and 35±8%, p=0.0421, respectively) when compared to unvegetated controls (13±20%). No significant differences in overall diazinon load retention were noted between plant species. Each plant species significantly decreased the initial load (after 6h) of trans-permethrin, while both L. oryzoides and T. latifolia significantly reduced the overall trans-permethrin loads (88±5%, p=0.0022 and 88±5%, p=0.0020, respectively) when compared to unvegetated controls (68±8%). Reversible adsorption of atrazine and diazinon to plants, noted during the flushing events, was greater than that observed in either cis- or trans-permethrin. These results demonstrate the ability of native ditch vegetation to mitigate pesticides associated with agricultural runoff. Likewise, they provide farmers and action agencies with supportive data for selection of vegetation in drainage ditches used as management practices.

Separation and aquatic toxicity of enantiomers of synthetic pyrethroid insecticides.

Synthetic pyrethroid insecticides are chiral compounds with multiple asymmetric positions. In this study, isomers of four commonly used pyrethroids were separated at the enantiomeric level by enantioselective high-performance liquid chromatography (HPLC), and differences between enantiomers in aquatic toxicity were characterized using individual isomers. Isomers of cis-bifenthrin and permethrin were completely resolved on a Sumichiral OA-2500-I column. All eight isomers of cypermethrin and cyfluthrin were completely separated on two chained Chirex 00G-3019-DO columns. Great differences were found between enantiomers in the acute toxicity to aquatic invertebrates Ceriodaphnia dubia or Daphnia magna. In cis-bifenthrin (cis-BF) and cis-permethrin (cis-PM), the 1R-cis isomer was 15-38 times more active than the 1S-cis enantiomer, while in trans-PM, the 1R-trans isomer was substantially more toxic than the 1S-trans enantiomer. In cypermethrin or cyfluthrin, two of the eight isomers, 1R-cis-alphaS and 1R-trans-alphaS, contributed for almost all the toxicity in the racemate, while the other six enantiomers were inactive. These results suggest that significant enantioselectivity occurs for pyrethroids in aquatic toxicity, and such enantiomeric differences must be considered when evaluating ecological effects of pyrethroid insecticides.

Chiral separation of pyrethroic acids with single isomer permethyl monoamino beta-cyclodextrin selector.

Enantiomers and diastereomers of chrysanthemic, permethrinic, and deltamethrinic pyrethroic acids were separated from each other, using positively ionizable permethyl monoamino beta-cyclodextrin (PMMAbetaCD). The highest chiral resolution value was 20.0. The optimum conditions of separation were found to be 16 mM PMMAbetaCD concentration and pH 6.5, where analytes and selector were in oppositely ionized states. Selectivity of PMMAbetaCD proved to be the best among the cyclodextrin derivatives studied.

Influence of (hydroxy)alkylamino substituents on enantioseparation ability of single-isomer amino-beta-cyclodextrin derivatives in chiral capillary electrophoresis.

A family of single-isomer amino-beta-cyclodextrin (amino-beta-CD) derivatives containing an amino or (hydroxy)alkylamino group in one of the primary positions has been synthesized. The steric effect and hydrogen bond forming ability of the different substituents on enantioseparation of acidic enantiomers has been studied by capillary electrophoresis (CE). Three enantiomeric model compounds (mandelic acid, cis-permethrinic acid, and cis-deltamethrinic acid) having significantly different apparent complex stability constants with beta-CD were applied in the experiments. Dependence of separation selectivity, resolution as well as mobility difference on chiral selector concentration (0.1-20 mM, pH 6.0) was investigated. Each amino-beta-CD showed higher enantioselectivity than the native beta-CD. One hydroxyalkyl group attached to the primary amino N-atom significantly increased both the enantioselectivity and the resolution compared to the primary amino-beta-CD, while two hydroxyalkyl moieties decreased them due to the predominance of steric hindrance. The value of the apparent complex stability constants obtained suited well the mobility difference model (by Wren). On the other hand, the optimum selector concentrations calculated according to the model were slightly lower than the experienced concentrations giving the maximum enantioresolution of enantiomers.