Ladybird defence alkaloids: Structural,chemotaxonomic and biosynthetic aspects (Col.: Coccinellidae)

Summary The defensive mechanisms which protect ladybird beetles (Coccinellidae) against predators are reviewed. Besides behavioural mechanisms, such as thanatosis and reflex bleeding, chemical defence mechanisms are playing a prevalent role. Indeed, ladybirds are protected not only by their smell, but also by repulsive alkaloids, most of which are considered to be of autogenous origin. In a few cases, dietarily-acquired substances are also involved. Particular emphasis is laid on the repellent alkaloids which are contained in the haemolymph of many species. The structures of 34 nitrogen-containing compounds isolated so far are presented, and their distribution within the family is discussed in the light of the most widely accepted classification of these beetles. To conclude, the mode of release of the alkaloids, their variation through the life cycle and their repellent and toxic properties are discussed, as well as the few biosynthetic data yet available.     

Sorption of Isoproturon and Dimetomorph on lignocellulose from wheat

The adsorption of toxic chemicals on solid substates is a potential means to clean polluted waters. Here, the adsorption of two pesticides, isoproturon and dimetomorph, on lignocellulose extracted from wheat straw is investigated at 20 °C using batch adsorption experiments. Here, we show that the sorption of both pesticides is independent of pH. The sorption capacity of lignocellulose is evaluated. We show that the presence of metallic cations has no influence on the retention capacity of lignocellulose towards pesticides.     

Recycling plant wax constituents for chemical defense: hemi-biosynthesis of triterpene saponins from β-amyrin in a leaf beetle

Several species of Doryphorina leaf beetles from Central- and South America produce oleanane triterpene glycosides in their defensive glands. The presence of pentacyclic triterpenes in insects is intriguing since they lack the key enzymes necessary to synthesize these compounds. Since -amyrin is a common constituent of leaf waxes, we hypothesized that these leaf beetles use this compound as a precursor to their oleanane glycosides. To test this hypothesis we first confirmed the presence of -amyrin in Ipomoea batatas, the food plant of Platyphora kollari. Next, adults of P. kollari were fed for 10 days with I. batatas leaf disks painted with a solution of [2,2,3-²H₃]-amyrin ([2,2,3-²H₃]-1). The secretion from their defensive glands was collected and analyzed by HPLC-ESIMS. The results demonstrated that the secretion of beetles fed with an amount of [2,2,3-²H₃]-amyrin corresponding to the quantity of unlabeled (natural) -amyrin present in the leaf disks contained on average 5.1% of [2,2,3-²H₃]-3-O--d-glucopyranosyl-(1-->4)--d-glucuronopyranosyl-hederagenin ([2,2,3-²H₃]-2), whereas the secretions of beetles fed with 10 times this amount of [2,2,3-²H₃]-amyrin contained on average 23.9% of [2,2,3-²H₃]-2. In both series of experiments, the percentage of labeled versus unlabeled triterpene glycoside in the secretion was positively correlated with the amount of deuterated -amyrin ingested. These results demonstrate for the first time that some leaf beetles are able to metabolize a widespread triterpenic constituent of leaf wax into more complex glycosides that are stored in their defensive glands.     

Photochimie et environnement - V. Photohydrolyse du monochlorobenzene en solution aqueuse diluee

A primary photohydrolysis of monochlorobenzene into phenol in dilute aqueous solution is occuring quantitatively whatever the experimental conditions were: pH (1<pH<12), excitation wavelength (253.7 nm or 300 nm), presence or absence of oxygen, initial concentration (in the range 10^?4M – 4.10^?3 M). The initial quantum yield of appearance of phenol has been found to be 0.10 ± 0.02 at 253.7 nm, and 0.19 ± 0.06 at 300 nm. The excited state leading to phenol cannot be quenched by acetonitrile at concentration up to 1.9 M. An heterolytic scission of the C-Cl bond parallels the concerted scission of water; a photosubstitution mechanism cannot account for the observed phenomena, especially in acidic media.Monofluoro- and bromobenzene irradiated in degased solution undergo a similar photohydrolysis; the initial quantum yields of appearance of phenol are 0.003 ± 0.001 and 0.06 ± 0.01, respectively for fluoro- and bromobenzene.     

The toxicity of pyrene in the fish : Synergism by piperonyl butoxide and by ultraviolet light

A saturated solution of pyrene in water was not toxic to the fish , even in the presence of ultraviolet light. A survival curve possessing one minimum, and therefore defining two LC₅₀ values, was obtained when fish placed in water containing increasing amounts of a pyrene solution in dimethylsulfoxide were exposed to ultraviolet light after a short incubation period. The phototoxicity was linked to the presence of undissolved pyrene. A normal survival curve with only one LC₅₀ value was found when pyrene was solubilized with the surfactant Tween-20. Practically no phototoxicity was produced when the pyrene mixtures were filtered before use, or when a saturated aqueous solution of pyrene was used. Piperonyl butoxide, present at a concentration where it was not toxic, synergized the toxicity of pyrene . The environmental significance of this observation may be considerable.     

Assessing the recovery of lakes in southeastern Canada from the effects of acidic deposition

Reductions in North American sulfur dioxide (SO2) emissions promoted expectations that aquatic ecosystems in southeastern Canada would soon recover from acidification. Only lakes located near smelters that have dramatically reduced emissions approach this expectation. Lakes in the Atlantic provinces, Quebec and Ontario affected only by long-range sources show a general decline in sulfate (SO4(2-)) concentrations, but with a relatively smaller compensating increase in pH or alkalinity. Several factors may contribute to the constrained (or most likely delayed) acidity response: declining base cation concentrations, drought-induced mobilization of SO4(2-), damaged internal alkalinity generation mechanisms, and perhaps increasing nitrate or organic anion levels. Monitoring to detect biological recovery in southeastern Canada is extremely limited, but where it occurs, there is little evidence of recovery outside of the Sudbury/Killarney area. Both the occurrence of Atlantic salmon in Nova Scotia rivers and the breeding success of Common Loons in Ontario lakes are in fact declining although factors beyond acidification also play a role. Chemical and biological models predict that much greater SO2 emission reductions than those presently required by legislation will be needed to promote widespread chemical and latterly, biological recovery. It may be unrealistic to expect that pre-industrial chemical and biological conditions can ever be reestablished in many lakes of southeastern Canada.     

Concentrations and fluxes of organic compounds in the atmosphere of the Swedish west coast

Measurements of organic compounds in air and deposition have been carried out in parallel on the Swedish west coast. In this investigation the importance of long-range transport for the occurrence of organic compounds in deposition has been studied. Air samples were collected using a high volume sampler (HVS) and the deposition was sampled on a 1 m² Teflon-coated horizontal surface with runoff for the precipitation to an adsorbent. The samples were analyzed in order to identify and quantify different semivolatile compounds such as PAH and petrogenic hydrocarbons and chlorinated compounds such as PCB, HCH and HCB. Qualitative differences between the content of organic compounds in air and deposition during periods with varying levels of air pollution and different meteorological conditions have been studied and a comparison with other air pollutants, such as soot, has been carried out. The results of the measurements show that deposition of PAH and other hydrocarbons takes place continuously but the greatest amounts are measured in the deposition in connection with episodes together with heavy precipitation. The highest concentrations of PCB and HCH in the air were obtained during a warm dry period in May and the greatest amounts were deposited in a period in May with heavy precipitation.     

Environmental risk assessment for trisodium [S,S]-ethylene diamine disuccinate, a biodegradable chelator used in detergent applications

Environmental safety data are presented for [S,S]-Ethylene Diamine Disuccinate ([S,S]EDDS), a new, biodegradable, strong transition metal chelator. An environmental risk assessment for its use in detergent applications, which takes into account the chelating properties of [S,S]-EDDS, is proposed.

A property of [S,S]-EDDS that distinguishes it from other strong transition metal chelators is its, “ready” and transparent (no recalcitrant metabolites) biodegradation profile. Because its sorption to activated sludge solids is low ( Kp of 40 1/kg), removal of [S,S]EDDS during sewage treatment, which is greater than 96% as determined by the Continuous Activated Sludge test , is mainly ascribed to biodegradation. At projected use volumes in detergent applications [S,S] - EDDS predicted steady-state concentration in rivers leaving the mixing zone will be below 5 pg/I due to rapid biodegradation. [S,S]-EDDS exhibits low toxicity to fish and Daphnia ( both EC₅₀s> 1000 mg/l). By contrast, due to limitation of the algal test for chelators apparent toxicity was observed (EC₅₀ = 0.290 mg/l, NOEC - No observable Effect Concentration = 0.125 mg/l). Schowanek et al. [1] demonstrated that this is not toxicity sensu stricto but a chelation effect of trace metals in the test medium and of resulting essential nutrients limitation. This requires specific attention when the results of algal toxicity are to be extrapolated to a field situation to perform realistic risk assessment. Metal speciation calculations, using MINEQL+, show that at the predicted environmental concentrations of [S,S] - EDDS (1–5 μg/l), such a chelation effect would be insignificant. These calculations allow to estimate the NOEC for chelation effects in the field to be in the range of 0.250-0.500 mg/l, depending on the background water chemistry. These values are well above the laboratory NOEC.

An environmental risk assessment was performed using the EUSES (1.0) program. EUSES is currently the EU recommended tool for conducting risk assessments (TGD 1995). It was applied to estimate the river water and soil concentrations from production, formulation and private use life stages. The estimated PEC/PNEC ratio in all relevant environmental compartments is smaller than 1, indicating “no immediate concern” at the anticipated usage level.     

Carbon emission associated with respiration and calcification of nine gastropod species from the intertidal rocky shore of Western Europe

Intertidal rocky shores are characterized by vertical zonation that results from the interplay between environmental conditions, organism physiology, and species interactions. Metabolism of intertidal organisms is highly variable between species and it changes with vertical position along the intertidal gradient. The present study aimed to quantify the carbon metabolism of nine intertidal rocky shore gastropods, in order to clarify their respective roles in carbon production during emersion and immersion. The influences of monthly temperature variation and tidal level were tested for each species. Analyses were performed in the laboratory using the infrared gas analyzer method for measuring aerial respiration rates, and the dissolved inorganic carbon and total alkalinity technique for measuring aquatic respiration rate and calcification. Hourly carbon fluxes were calculated for the mean annual temperature of 13 °C measured in both air and underwater in the study area. Respiration rates were similar for emersion (8–25 μmol CO₂ g AFDW^?1 h^?1) and immersion (10–23 μmol DIC g AFDW^?1 h^?1). For all species, underwater respiration fluxes were more influenced by monthly temperature variation than by air fluxes, probably as an adaptation to the rapid changes occurring during emersion. Calcification was an important factor influencing annual carbon fluxes for all studied species; every species showed different calcification rates according to its size and position on the intertidal zone. Annual carbon emissions were calculated using the mean immersion/emersion time of each species. Intertidal gastropod carbon emission was primarily influenced by body biomass and their vertical position within the intertidal zone.     

Comparison of four methods to estimate meiobenthic copepod Amonardia normani ingestion rates

Four different methods were used in the control conditions of laboratory to estimate the ingestion rate of a female meiobenthic harpacticoid copepod Amonardia normani: (1) reduction of algal biomass, (2) the quantification of total pigments in fecal pellets, (3) the gut fluorescence method, (4) the percentage of assimilation and the total egestion rate. The food used during all experiments was the diatom Nitzschia constricta in an axenic condition at the concentration of 0.13 μg Chl-a mL^?1 at stationary growth phase. All experiments were made at 20 °C and 30 salinity. All tested methods excepted the quantification of total pigments in fecal pellets resulted in similar estimatives. The gut fluorescence method indicated that during the day gut contents are smaller than during the night but the gut passage time was faster, resulting in similar ingestion rates during the day and the night. The reduction of algal biomass and the percentage of assimilation and the total egestion rate also indicated similar ingestion rates in the day and in the night. The daily ingestion rate represents 107 % of female carbon weight per day (903 ng C cop^?1day^?1).