Chemical defense of the ladybird beetle Epilachna paenulata

Summary. The defensive chemistry of the ladybird beetle Epilachna paenulata (Coleoptera: Coccinellidae) was characterized as a mixture of piperidine, homotropane and pyrrolidine alkaloids. Whole body extracts of adult beetles contain four major alkaloids: 1-(6-Methyl-2,3,4,5-tetrahydro-pyridin-2-yl)-propan-2-one; 1-(6-methyl-2-piperidyl)-propan-2-one; 9-aza-1-methyl-bicyclo[3.3.1]nonan-3-one and 1- (2′′- hydroxyethyl)-2-(12′-aminotridecyl)-pyrrolidine. Comparative studies of the defensive chemistry of eggs, larvae, pupae and adults showed both qualitative and quantitative differences in alkaloid composition among the four life stages, and also within adult age. Laboratory predation bioassays with wolf spiders showed that the adults are better protected than the larvae and pupae. Field tests showed the adult alkaloid extract to be deterrent to ants.     

Elemental composition of otolith growth marks in three geographically separated populations of European hake (Merluccius merluccius)

The composition of the opaque and translucent bands in the otoliths of European hake (Merluccius merluccius) from three different populations (Celtic Sea, Galicia shelf and Cretan Sea) was analysed with wavelength dispersive spectrometry (WDS) and differences in Ca, Sr and Na were compared. The translucent bands (annual marks and checks altogether) were significantly richer in Sr and Ca and significantly poorer in Na than opaque bands. Results support the idea of a more compact arrangement of crystals in translucent bands compared to opaque. Analyses did not help to discriminate between putative annual marks and checks. Clear differences in the range of Sr/Ca variation across the otolith as well as in the composition of the otolith core were observed among the three populations. As a result it was possible to discriminate the natal origin of each fish using the composition of the otolith core in Ca, Sr and Na. Nevertheless, the overall pattern across the otolith was similar among the three populations suggesting the existence of ontogenetic trends. Variation of Na/Ca ratios was largely uninformative. Based on these results, a conceptual model for hake is proposed which integrates the different sources of otolith Sr/Ca variation: ambient Sr/Ca, endogenous cues (ontogeny) and exogenous cues (environment).     

Studies on the defensive behaviour ofHypselodoris species (Gastropoda: Nudibranchia): Ultrastructure and chemical analysis of mantle dermal formations (MDFs)

The mantle dermal formations (MDFs) ofHypselodoris webbi (D'orbigny, 1839), andH. cantabrica (Bouchet and Ortea, 1980) are globular sub-epidermal structures located in the cephalic and caudal regions. Histologically they consist of an accumulation of vacuolate cells surrounded by a basal lamina and an outer muscular capsule. Chemical analysis ofH. webbi MDFs reveals the presence of high concentrations of longifolin, a well known deterrent furanosesquiterpenoid that had been previously isolated from this species. In the present paper it is demonstrated that the great majority of longifolin accumulated in the mantle ofH. webbi is stored in the MDF vacuolar cells. This finding strongly suggests that such structures act as chemical weapons against predation, mainly protecting vital organs such as the head, rhinophores and gills.     

Increased mortality and photoinhibition in the symbiotic dinoflagellates of the Indo–Pacific coral Stylophora pistillata (Esper) after summer bleaching

Coral bleaching (the loss of symbiotic dinoflagellates from reef-building corals) is most frequently caused by high-light and temperature conditions. We exposed the explants of the hermatypic coral Stylophora pistillata to four combinations of light and temperature in late spring and also in late summer. During mid-summer, two NOAA bleaching warnings were issued for Heron Island reef (Southern Great Barrier Reef, Australia) when sea temperature exceeded the NOAA bleaching threshold, and a ‘mild’ (in terms of the whole coral community) bleaching event occurred, resulting in widespread S. pistillata bleaching and mortality. Symbiotic dinoflagellate biomass decreased by more than half from late spring to late summer (from 2.5×10⁶ to 0.8×10⁶ dinoflagellates cm² coral tissue), and those dinoflagellates that remained after summer became photoinhibited more readily (dark-adapted F _V : F _M decreased to (0.3 compared with 0.4 in spring), and died in greater numbers (up to 17% dinoflagellate mortality compared with 5% in the spring) when exposed to artificially elevated light and temperature. Adding exogenous antioxidants (d-mannitol and l-ascorbic acid) to the water surrounding the coral had no clear effect on either photoinhibition or symbiont mortality. These data show that light and temperature stress cause mortality of the dinoflagellate symbionts within the coral, and that susceptibility to light and temperature stress is strongly related to coral condition. Photoinhibitory mechanisms are clearly involved, and will increase through a positive feedback mechanism: symbiont loss promotes further symbiont loss as the light microenvironment becomes progressively harsher.     

Degradation of juvenile hormone analog by soil microbial isolates

Juvenoids are efficient pesticides with relatively low toxicity to humans. However, few studies have evaluated the effect of degradation by soil microorganisms on their toxicity. The effects of bacterial, fungal and yeast isolates on aerobic decomposition of ethyl N-[2-[4-(2,2-ethylenedioxy-1-cyclohexylmethyl)phenoxy]ethyl] carbamate during eight weeks were determined. The effect of different concentration of glucose on their degradation activity is also analyzed.     

Guidelines for routine mercury speciation analysis in seafood by gas chromatography coupled to a home-modified AFS detector. Application to the Andalusian coast (south Spain)

A home-modified atomic fluorescence detector (mAFS) has been employed for mercury and methylmercury determination in bivalves from the Andalusian coast (south Spain). This modification consists on the inclusion of a quartz flow cell into the detector, which increases the concentration of mercury atoms in the detector and therefore enhances sensitivity about two fold. Two analytical approaches for mercury speciation based on the coupling of gas chromatography on-line pyrolysis and mAFS (GC-Pyro-mAFS) have been tested. The first approach (Method 1) is based on aqueous ethylation followed by extraction into an organic solvent, and the second one (Method 2) in the extraction of monoalkylated mercury as chloride. Method 1 is a rapid procedure but not sensitive enough for the analysis of methylmercury in non-polluted sites (detection limit: 20 ng g(-1) as mercury, wet basis). The second one is quite more sensitive (detection limit: 0.2 ng g(-1), wet weight), but sample treatment is cumbersome and time-consuming. The optimum range for mercury determination for both methods are complementary and exhibit an overlapping measurable concentration range (OMCR) in which methylmercury can be indistinctly determined (75-100 ng g(-1) as mercury, wet basis). The suitability of both methods has been assayed with spiking experiences at levels within the OMCR with good recoveries. Both approaches have been validated with two certified reference materials (BCR-463, mercury and methylmercury in tuna fish; and NIST-2977, organic contaminants and trace metals in mussel tissue). Both procedures have been used for the analysis of three species of bivalve molluscs collected along the Andalusian coast (south Spain), all of them employed for human consumption (Chamelea gallina, Donax trunculus and Scrobicularia plana), and their potential use in routine analysis has been established.     

Analysis of PM2.5 and PM10 in the atmosphere of Mexico City during 2000-2002

During the last 10 years, high atmospheric concentrations of airborne particles recorded in the Mexico City metropolitan area have caused concern because of their potential harmful effects on human health. Four monitoring campaigns have been carried out in the Mexico City metropolitan area during 2000-2002 at three sites: (1) Xalostoc, located in an industrial region; (2) La Merced, located in a commercial area; and (3) Pedregal, located in a residential area. Results of gravimetric and chemical analyses of 330 samples of particulate matter (PM) with an aerodynamic diameter less than 2.5 microm (PM2.5) and PM with an aerodynamic diameter less than 10 microm (PM10) indicate that (1) PM2.5/PM10 average ratios were 0.42, 0.46, and 0.52 for Xalostoc, La Merced, and Pedregal, respectively; (2) the highest PM2.5 and PM10 concentrations were found at the industrial site; (3) PM2.5 and PM10 concentrations were lower at nighttime; (4) PM2.5 and PM10 spatial averages concentrations were 35 and 76 microg/m3, respectively; and (5) when the PM2.5 standard was exceeded, nitrate, sulfate, ammonium, organic carbon, and elemental carbon concentrations were high. Twenty-four hour averaged PM2.5 concentrations in Mexico City and Sao Paulo were similar to those recorded in the 1980s in Los Angeles. PM10 concentrations were comparable in Sao Paulo and Mexico City but 3-fold lower than those found in Santiago.     

Distribution of Pb, V, Cr, Ni, Cd, Cu and Fe in particles formed from the combustion of waste oils

The determination of Pb, V, Cr, Ni, Cd, Cu and Fe in particles of different size obtained from the combustion of waste oils has been carried out. The study consists of the separation of several fractions according to the size of particles, the wet digestion and the individual analysis by graphite furnace atomic absorption spectrometry of the mentioned metals. Taking into account the volatilization temperature of different compounds containing the metals and their distribution on the size fractions, the mineral speciation of metals is proposed.     

Semiconductor-assisted photodegradation of lignin, dye, and kraft effluent by Ag-doped ZnO

This work reports a preliminary study of semiconductor-assisted photochemical degradation of lignin, Remazol Brilliant Blue R and Kraft E1 paper effluent by using ZnO and Ag-doped ZnO photocatalysts. The doped semiconductor was prepared in the reaction media by photoreduction of silver nitrate. With the use of 100 mg of ZnO and 15 mg of Ag-ZnO, almost total decolorization of the dye and lignin samples in reaction times lower than 60 min were observed. Extending the photochemical reaction up to 120 min, the total organic carbon content (TOC) was reduced in 90%. For the paper effluent, a fast decolorization was obtained for relatively short reaction times. However, de TOC reduction was negligible (near of 10%) up to high reaction times (300 min). By using the Ag-ZnO photocatalyst, the toxicity of lignin and Kraft E1 effluent toward E. Coli was completely removed. For the dye, the formation of transient toxic species was observed.     

Copper(II) complexation by humic and fulvic acids from pig slurry and amended and non-amended soils

The effect of the consecutive annual additions of pig slurry at rates of 0 (control), 90 and 150 m3 ha(-1) y(-1) over a 4-year period on the binding affinity for Cu(II) of soil humic acids (HAs) and fulvic acids (FAs) was investigated in a field plot experiment under semiarid conditions. A ligand potentiometric titration method and a single site model were used for determining the Cu(II) complexing capacities and the stability constants of Cu(II) complexes of HAs and FAs isolated from pig slurry and control and amended soils. The HAs complexing capacities and stability constants were larger than those of the corresponding FA fractions. With respect to the control soil HA, pig-slurry HA was characterized by a much smaller binding capacity and stability constant. Amendment with pig slurry decreased the binding affinity of soil HAs. Similar to the corresponding HAs, the binding affinity of pig-slurry FA was much smaller while that of amended-soil FAs were slightly smaller when compared to the control soil FA. The latter effect was, however, more evident with increasing the amount of pig slurry applied to soil per year and the number of years of pig slurry application.