Isomers/enantiomers of perfluorocarboxylic acids: Method development and detection in environmental samples.

Perfluoroalkyl substances are globally distributed in both urban and remote settings, and routinely are detected in wildlife, humans, and the environment. One of the most prominent and routinely detected perfluoroalkyl substances is perfluorooctanoic acid (PFOA), which has been shown to be toxic to both humans and animals. PFOA exists as both linear and branched isomers; some of the branched isomers are chiral.

Enantioselective toxicity and bioaccumulation of fipronil in fathead minnows (Pimephales promelas) following water and sediment exposures.

Fipronil is a widely used, broad-spectrum pesticide that is applied as an equal mixture of two enantiomers. As regulations on older pesticides become more stringent, production and application of fipronil is expected to grow, leading to increased inputs into aquatic environments and complex exposures to biota. To better understand the potential exposures introduced by fipronil contamination, we conducted subchronic toxicity tests with larval fathead minnows (Pimephales promelas) and waterborne fipronil and its enantiomers and exposed juvenile fathead minnows to fipronil-spiked sediment.

Loss of propiconazole and its four stereoisomers from the water phase of two soil-water slurries as measured by capillary electrophoresis.

Propiconazole is a chiral fungicide used in agriculture for control of many fungal diseases on a variety of crops. This use provides opportunities for pollution of soil and, subsequently, groundwater. The rate of loss of propiconazole from the water phase of two different soil-water slurries spiked with the fungicide at 50 mg/L was followed under aerobic conditions over five months; the t(1/2) was 45 and 51 days for the two soil slurries.

Microbial transformation of triadimefon to triadimenol in soils: selective production rates of triadimenol stereoisomers affect exposure and risk.

The microbial transformation of triadimefon, an agricultural fungicide of the 1,2,4-triazole class, was followed at a nominal concentration of 50 μg/mL over 4 months under aerobic conditions in three different soil types. Rates and products of transformation were measured, as well as enantiomer fractions of parent and products. The transformation was biotic and enantioselective, and in each soil the S-(+)-enantiomer reacted faster than the R-(-) one.

Integration of metabolomics and in vitro metabolism assays for investigating the stereoselective transformation of triadimefon in rainbow trout.

Triadimefon is a systemic agricultural fungicide of the triazole class whose major metabolite, triadimenol, also a commercial fungicide, provides the majority of the actual fungicidal activity, i.e., inhibition of steroid demethylation.

Analysis of the enantiomers of chiral pesticides and other pollutants in environmental samples by capillary electrophoresis.

The generic method described here involves typical capillary electrophoresis (CE) techniques, with the addition of cyclodextrin chiral selectors to the electrolyte for enantiomer separation and also, in the case of neutral analytes, the further addition of a micelle-forming compound such as sodium dodecyl sulfate (SDS) for separation by the micellar electrokinetic chromatography (MEKC) mode of CE. This generic method has broad application for the separation and analysis of enantiomers of chiral pesticides and other small molecules in a variety of environmental matrices. Aqueous samples such as surface water are analyzed after simple filtration, but centrifugation is sometimes necessary for soil-water slurry samples.

Enantioselective Chronic Toxicity of Fipronil to Ceriodaphnia dubia.

Fipronil is a phenylpyrazole pesticide that has greatly increased in popularity in recent years. As a chiral molecule, fipronil is released into the environment as a 1:1 mixture (called a racemate) of its two enantiomers. Previous toxicity work has indicated that the enantiomers of fipronil exhibit significantly different levels of acute toxicity to the nontarget organism Ceriodaphnia dubia.

Toxicity of fipronil and its enantiomers to marine and freshwater non-targets.

Fipronil is a phenylpyrazole insecticide used in agricultural and domestic settings for controlling various insect pests in crops, lawns, and residential structures. Fipronil is chiral; however, it is released into the environment as a racemic mixture of two enantiomers. In this study, the acute toxicity of the (S,+) and (R,-) enantiomers and the racemic mixture of fipronil were assessed using Simulium vittatum IS-7 (black fly), Xenopus laevis (African clawed frog), Procambarus clarkii (crayfish), Palaemonetes pugio (grass shrimp), Mercenaria mercenaria (hardshell clam), and Dunaliella tertiolecta (phytoplankton).

Bioaccumulation and biotransformation of chiral triazole fungicides in rainbow trout (Oncorhynchus mykiss).

There are very little data on the bioaccumulation and biotransformation of current-use pesticides (CUPs) despite the fact that such data are critical in assessing their fate and potential toxic effects in aquatic organisms. To help address this issue, juvenile rainbow trout (Oncorhynchus mykiss) were exposed to dietary concentrations of a mixture of chiral triazole fungicides (bromuconazole, cyproconazole, metconazole, myclobutanil, penconazole, propiconazole, tebuconazole, tetraconazole, and triadimefon) and a chiral legacy pesticide [alpha-hexachlorocyclohexane (alpha-HCH)] to study the bioaccumulation and biotransformation of these CUPs. Fish accumulated all triazoles rapidly during the 8 day uptake phase, and was followed by rapid elimination, which was estimated by taking accelerated sampling times during the 16 day depuration period.

Distribution of chiral PCBs in selected tissues in the laboratory rat.

The enantiomeric enrichment of polychlorinated biphenyl (PCB) atropisomers has been reported in both wildlife and in humans. The biological processes causing this enrichment are only poorly investigated, a fact that limits the use of enantiomeric fractions (EFs) as a tool to study various processes of environmental relevance. To further understand these enantioselective processes, this study investigates the tissue distribution and EFs of some PCB atropisomers after administration of PCB mixtures to immature male Sprague-Dawley rats.

Bioaccumulation, biotransformation, and metabolite formation of fipronil and chiral legacy pesticides in rainbow trout.

To assess the fate of current-use pesticides, it is important to understand their bioaccumulation and biotransformation by aquatic biota. We examined the dietary accumulation and enantioselective biotransformation of the chiral current-use pesticide fipronil, along with a mixture of selected chiral [alpha-hexachlorocyclohexane (alpha-HCH), heptachlor epoxide (HEPX), polychlorinated biphenyls (PCBs) 84, 132, 174, o,p'-DDT, and o,p'-DDD] and nonchiral (p,p'-DDT, p,p'-DDD) organochlorine compounds in juvenile rainbow trout (Oncorhynchus mykiss). Fish rapidly accumulated all compounds, as measured in the carcass (whole body minus liver and GI tract) during the 32 d uptake phase, which was followed by varying elimination rates of the chemicals (half-lives (t1/2s) ranging from 0.

Acute enantioselective toxicity of fipronil and its desulfinyl photoproduct to Ceriodaphnia dubia.

Fipronil is a phenylpyrazole insecticide increasingly used in applications such as rice culture, turf grass management, and residential pest control, with a high probability to contaminate aquatic environments. As a chiral pesticide, fipronil is released to the environment as a racemic mixture (equal amounts of optical isomers called enantiomers). Enantiomers can have different toxicological and biological activity; however, information on these differences, which is necessary for accurate risk assessment of chiral pesticides, is limited.