Hexavalent chromium reduction kinetics in rodent stomach contents

Reduction of hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)) in the stomach prior to absorption is a well-recognized detoxification process thought to limit the toxicity of ingested Cr(VI). However, administration of high concentrations of Cr(VI) in drinking water cause mouse small intestinal tumors, and quantitative measures of Cr(VI) reduction rate and capacity for rodent stomach contents are needed for interspecies extrapolation using physiologically-based toxicokinetic (PBTK) models. Ex vivo studies using stomach contents of rats and mice were conducted to quantify Cr(VI) reduction rate and capacity for loading rates (1-400 mg Cr(VI) L⁻¹ stomach contents) in the range of recent bioassays. Cr(VI) reduction was measured with speciated isotope dilution mass spectrometry to quantify dynamic Cr(VI) and Cr(III) concentrations in stomach contents at select time points over 1 h. Cr(VI) reduction followed mixed second-order kinetics, dependent upon concentrations of both Cr(VI) and the native reducing agents. Approximately 16 mg Cr(VI)-equivalents of reducing capacity per L of fed stomach contents (containing gastric secretions, saliva, water and food) was found for both species. The second-order rate constants were 0.2 and 0.3 L mg⁻¹ h⁻¹ for mice and rats, respectively. These findings support that, at the doses that caused cancer in the mouse small intestine (?20 mg Cr(VI) L⁻¹ in drinking water), the reducing capacity of stomach contents was likely exceeded. Thus, for extrapolation of target tissue dose in risk assessment, PBTK models are necessary to account for competing kinetic rates including second order capacity-limited reduction of Cr(VI) to Cr(III).     

The front basitarsal brush in Pachycondyla apicalis and its role in hydrocarbon circulation

Summary. Worker postpharyngeal gland (PPG) chemistry of Pachycondyla apicalis constitutes a blend of hydrocarbons including alkanes, alkenes, and alkadienes, with 5,9-pentacosadiene, 5,9-heptacosadiene and 5,9-nonacosadiene as the major products as well as fatty acids. There is a large congruency between the PPG and cuticular hydrocarbons, however the latter had higher proportion of tricosane and pentacosane, but only traces of fatty acids. These ants have a well-developed cuticular hair brush on the front legs that they frequently pass through the mouth while grooming. Since these brushes have higher amounts of hydrocarbons than either the middle or hind legs, we hypothesized that they are involved in hydrocarbon circulation. We assessed the role of the front basitarsal brush in hydrocarbon circulation by isolating them from the buccal cavity, either by restraining the front legs or by blocking the mouth with glue. In both experiments, preventing contacts between the basitarsal brushes and the mouth for 24 hrs resulted in a considerable increase in hydrocarbon amounts in the brushes with a parallel decrease in the PPG. When the ants were kept alive for an additional 24 hrs after their legs were freed, hydrocarbon amounts in both the PPG and the front legs returned to normal. Analyses of crop content revealed the same hydrocarbons profile as in the PPG, but their amounts were very variable and there were no differences in amounts between the treatment and the control. We assume that part of the PPG hydrocarbons are cleared via the alimentary canal. Grooming behavior of ants restrained for 24 hrs and then freed was followed for four hours thereafter. There was a significant increase in total grooming during the first third and fourth hour, but not during the second. Grooming involving the front legs-mouth, and front legs-antennae, and the front and hind legs was especially intensive during the first hour. Grooming involving the hind legs - body was more intensive in the treated ants during the third hour following their release. We conclude that the front basitarsal brush is a site of hydrocarbon accumulation and that the PPG receives frequent charging during self-grooming.     

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). Results showed that S. vittatum IS-7 was the most sensitive freshwater species to the racemic mixture of fipronil (LC50 = 0.65 microg/L) while P. pugio was the most sensitive marine species (LC50 = 0.32 microg/L). Procambarus clarkii were significantly more sensitive to the (S,+) enantiomer while larval P. pugio were significantly more sensitive to the (R,-) enantiomer. Enantioselective toxicity was not observed in the other organisms tested. Increased mortality and minimal recovery was observed in all species tested for recovery from fipronil exposure. These results indicate that the most toxic isomer of fipronil is organism-specific and that enantioselective toxicity may be more common in crustaceans than in other aquatic organisms.     

Nitrate and nitrite injection during municipal solid waste anaerobic biodegradation

Nitrified leachate recirculation has been proposed as a promising strategy for sustainable landfill management. In four test reactors, nitrate or nitrite was added (250 mg N-NO(x)(-)L(-1)) during municipal solid waste biodegradation. Nitrogen-oxides reduction reactions were monitored. Denitrification was the main nitrogen reducing reaction observed. On one hand, during the acidogenic waste degradation phase, as high amounts of volatile fatty acids (VFA) were present, nitrogen-oxides reductions were interpreted as heterotrophic denitrifications. On the other hand, denitrification reactions occurring during the late methanogenic phase were accompanied by sulphate productions and, as VFA were not detected, it was probably an autotrophic reaction. Denitrification inhibition was observed once. Ammonium concentration increased suggesting the occurrence of a dissimilatory nitrate reduction to ammonium (DNRA). Statistical treatment of analytical data revealed that only H(2)S concentration had a significant negative effect on N(2) production in our system. NO production was observed once when nitrite was injected during the acidogenic phase resulting in a total waste degradation inhibition. These results indicate that the consequences of nitrified leachate recirculation in full-scale landfills need to be carefully examined especially during the acidogenic phase or in the presence of waste containing high quantities of sulphur.     

A Stereoselective Route to R-(+)-Limonene-Based Non-isocyanate Poly(hydroxyurethanes)

Journal of Polymers and the Environment - Bio-based non-isocyanate poly(hydroxyurethanes) (NIPUs) have recently gained significant interest due to increasing awareness of the health and...     

Using spatial smoothing to model a functional regression estimator to points on a lattice with application to surface-level ozone in the Eastern United States

Environmental and Ecological Statistics - Spatial functional regression methods allow researchers to model spatially dependent functional random variables, often using a kriging-based interpolation...