QuEChERS multiresidue method validation and mass spectrometric assessment for the novel anthranilic diamide insecticides chlorantraniliprole and cyantraniliprole

The gas-phase dissociation reactions of chlorantraniliprole (Rynaxypyr) and cyantraniliprole (Cyazypyr) have been studied in triple-quadrupole, ion trap, and orbitrap mass spectrometers equipped with electrospray and desorption electrospray ion sources, revealing the formation of odd-electron fragment ions, the structures of which were elucidated. The odd-electron fragments were unusually abundant, and their formation is proposed to occur via a tricyclic intermediate. The applicability of the QuEChERS multiresidue method for the quantitation of chlorantraniliprole and cyantraniliprole was also assessed in this study. Four matrices representative of oily, watery, acidic, and dry crop groups were tested, with a targeted limit of quantitation (LOQ) of 0.01 mg/kg. Average recoveries ranged between 87 and 107%, with relative standard deviations (RSD) of ≤ 8%. Linear calibration functions with correlation coefficients r > 0.99 were obtained. The study provides an expansion of the QuEChERS method to include anthranilic diamides and a mass spectrometric assessment for these two novel agrochemical active ingredients.     

Alterations in activated T‐cell cytokine expression in healthy dogs over the initial 7 days of twice daily dosing with oral cyclosporine

Cyclosporine is a powerful T‐cell inhibitor used in the treatment of immune‐mediated and inflammatory diseases in the dog. There is limited information on how to best monitor patients on cyclosporine therapy. Currently, pharmacokinetic and pharmacodynamic assays are available. Pharmacokinetic assays that measure the concentration of cyclosporine in the blood are used to assess if an appropriate drug concentration has been achieved; however, target blood drug concentrations have not been shown to reliably correlate with suppression of T‐cell function in the dog. In human transplant recipients, therapeutic drug monitoring has shifted to include pharmacodynamic‐based monitoring. Our laboratory has validated a RT‐qPCR assay to measure the pharmacodynamic effects of cyclosporine in the dog. In this study, activated T‐cell expression of IL‐2 and IFN‐γ was measured using RT‐qPCR daily for 7 consecutive days in 8 healthy Walker hounds receiving oral cyclosporine at a dosage of 10 mg/kg every 12 hr. Cytokine production was found to be markedly decreased within 24 hr after the initiation of cyclosporine and remained significantly decreased for the duration of the project. Based on these results, cyclosporine causes a rapid drop in T‐cell cytokine production that is sustained with continued dosing in healthy dogs. Although performed in healthy dogs, this study demonstrated a marked decrease in cytokine suppression within 24 hr of drug administration, suggesting that pharmacodynamic monitoring of cyclosporine's effects on T cells could be considered within several days of commencing therapy in dogs suffering from life‐threatening immune‐mediated disorders.     

Water and nutrient dynamics and tree growth

The balance in the investment of assimilate at any time into leaves and roots may depend on whether water, nutrients or radiation are limiting to growth. Also, for the same investment of assimilate into roots, the root configuration may range from intensive to extensive in both space and time, to take best advantage of the distribution and amount of water and nutrients. Intensive root configurations, which include mycorrhizas and proteoid roots, assist in the uptake of nutrients (such as phosphorus) which are rate-limiting in soil. Mycorrhizas may assist in water uptake in dry or coarse textured soils with low unsaturated hydraulic conductivities.

Adaptations which assist trees to survive in dry and nutrient-deficient environments are discussed. These mechanisms may reduce, maintain or increase growth. In production forestry, it is desirable to exploit those mechanisms which increase growth. When soil water and nutrients limit tree growth, productivity may be improved by increasing the amount of uptake of water and nutrients, or by increasing the efficiency by which they are used in growth. Maximizing water-use efficiency when soil water supply is limiting may be dependent on whether the trees are in mixed stands or in monoculture. Selecting trees with relatively less root may improve productivity in monocultures when weeds are controlled and fertilizer is added. It is well known that trees can ‘re-use’ nutrients by retranslocating them within the tree to zones of demand. Relatively little is known, though, about differences in the biochemical involvement of nutrients at the cellular and subcellular level which contribute to differences in nutrient-use efficiency in trees.     

Ingestion, Absorption, and Gonad Production of Adult Strongylocentrotus franciscanus Fed Different Rations of a Prepared Diet

Abstract.— Feed costs are a major portion of aqua-culture operations. Accurate estimates of daily ration are vital to prevent overfeeding which results in wasted feed. poor water quality, underfeeding, and reduced growth. Understanding the relationship of ingestion rate and absorption efficiency of Strongylocentrotus franciscanus should improve the cost effectiveness of aquaculture of this candidate species. Adult S. franciscanus were collected from a subtidal area devoid of algae and fed two rations of an extruded diet for 62 d. Mean test diameter and whole weight of an initial sample were 91 ± 2 mm and 295 ± 18.4 g (mean ± SEM; N = 16). The two rations used were l-g dry feed/d or 3 g/d. An unfed control group was also maintained. Eight urchins per treatment showed significant differences in food ingestion rate, total organic absorption, gonad index, gut index, and moisture content of the gonad (P < 0.001). Food intake was greatest in the high ration treatment, while total organic absorption was greatest in the low ration treatment. The gonad index of S. franciscanus in the high food ration was significantly greater than the initial gonad index and was also greater than the index of animals in the low ration and unfed treatments. The gonad index of animals in the low food ration treatment was significantly greater than the index of the initial sample and the index of animals in the unfed treatment. The gut index of urchins in the high food ration treatment was significantly greater than initially and was also greater than the gut index for animals in the low ration and unfed treatments. The gut index for urchins in the unfed treatment was significantly less than the initial index. The moisture content of the gonad of urchins fed the prepared diet was significantly greater than the gonad moisture content of the initial sample or unfed group. Test diameter. whole animal weight, and gonad production efficiency (increase in g dry gonad weight/g dry feed intake) were not significantly different (P > 0.200). Histological examination of the gonads showed S. franciscanus in the two ration treatments developed from the spent to the growing or premature stage while the unfed controls lost nutritive tissue and contained only relict gametes or remained in the spent condition. The results suggest S. franciscanus from food-limited environments can be fed appropriate rations to control gonad production.     

Comparing the impact of conventional pesticide and use of a transgenic pest-resistant crop on the beneficial carabid beetle Pterostichus melanarius

The potential impact of a chemical pesticide control method has been compared with that of transgenic plants expressing a protease inhibitor conferring insect resistance by utilising a tritrophic system comprising the crop plant Brassica napus (L.) (Oilseed rape), the pest mollusc Deroceras reticulatum (Müller) and the predatory carabid beetle Pterostichus melanarius (Illiger). Cypermethrin, as the most widely used pesticide in UK oilseed rape (OSR) cultivation, was selected as the conventional treatment. OSR expressing a cysteine protease inhibitor, oryzacystatin-1 (OC-1), was the transgenic comparator. In feeding trials, D. reticulatum showed no significant long-term effects on measured life history parameters (survival, weight gain, food consumption) as a result of exposure to either the cypermethrin or OC-1 treatment. However, D. reticulatum was able to respond to the presence of the dietary inhibitor by producing two novel proteases following exposure to OC-1-expressing OSR. Similarly, P. melanarius showed no detectable alterations in mortality, weight gain or food consumption when feeding on D. reticulatum previously fed either pesticide-contaminated or GM plant material. Furthermore, as with the slug, a novel form of protease, approximately M(r) 27 kDa, was induced in the carabid in response to feeding on slugs fed OC-1-expressing OSR.     

Lupinus arcticus Wats. Grown from Seeds of Pleistocene Age

Seeds of the arctic tundra lupine (Lupinus arcticus) at least 10,000 years old were found in lemming burrows deeply buried in permanently frozen silt of Pleistocene age in unglaciated central Yukon. They readily germinated in the laboratory and have since grown into normal, healthy plants.     

Rhamnolipid Foam Enhanced Remediation of Cadmium and Nickel Contaminated Soil

Column experiments were conducted to evaluate the feasibility of using a rhamnolipid foam to remove heavy metals (Cd and Ni) from a sandy soil contaminated with Cd (1706 ppm) and Ni (2010 ppm). Best results were obtained from the foam generated by a 0.5% rhamnolipid solution with an initial pH value of 10.0 after flushing with 20-pore-volume of solution. These conditions removed 73.2% of the Cd and 68.1% of the Ni. Removal efficiencies by foam generated by a chemical surfactant, Triton X-100, were investigated as a comparison. It removed 65.5% of the Cd and 57.3% of the Ni under the same conditions. After a 20-pore-volume liquid solution flushing, 0.5% rhamnolipid (initial pH 10.0) without foam generation removed 61.7% of the Cd and 51.0% of the Ni, whereas 0.5% Triton X-100 (initial pH 10.0) removed 52.8% of the Cd and 45.2% of the Ni. Distilled water with adjusted pH only was also used to flush through the contaminated soil column as a control. It removed 17.8% of the Cd and 18.7% of the Ni. This study shows that rhamnolipid foam technology can be an effective means for the remediation of cadmium and nickel contaminated soil.     

Sequential in vivo measurements of body composition of calves exposed to natural infection with gastrointestinal nematodes

Sequential in vivo measurements of total body water, exchangeable sodium and exchangeable potassium, made by radioisotopic dilution techniques, were used to determine changes in body composition in calves exposed to natural infections with gastrointestinal nematodes during their first grazing season. Two groups of calves were studied, one of which received a sustained release anthelmintic bolus at turn out. Over the grazing season the bolus-treated calves showed a significantly improved pattern of bodyweight gain, compared with the untreated control calves. There were also significant increases in both total body water and exchangeable potassium, as a percentage of the bodyweight, in the bolus calves compared with the controls. These findings indicated that body protein as a percentage of bodyweight was increased in the bolus animals. The bolus-treated calves also had significantly lower serum pepsinogen concentrations, faecal egg counts and worm burdens.