Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

Stabilization of the initial electrochemical potential for a metal-based potentiometric titration study of a biosorption process

An interactive metal-based potentiometric titration method has been developed using an ion selective electrode for studying the sorption of metal cations. The accuracy of this technique was verified by analyzing the metal sorption mechanism for the biomass of Rhizopus arrhizus fungus and diatomite, two dissimilar materials (organic and mineral, strong sorbent and weak sorbent) of a different order of cation exchange capacity. The problem of the initial electrochemical potential was addressed identifying the usefulness of a Na-sulfonic resin as a strong chelating agent applied before the beginning of sorption titration experiments so that the titration curves and the sorption uptake could be quantitatively compared. The resin stabilized the initial electrochemical potential to -405+/-5 mV corresponding to 2 micro gl(-1) of lead concentration in solution. The amounts of lead sorbed by R. arrhizus biomass and diatomite were 0.9 mmol g(-1) (C(e)=5.16 x 10(-2)mM) and 0.052 mmol g(-1) (C(e)=5.97 x 10(-2) mM), respectively. Lead sorption by the fungal biomass was pinpointed to at least two types of chemical active sites. The first type was distinguished by high reactivity and a low number of sites whereas the other was characterized by their higher number and lower reactivity.     

Characterization of trace organic contaminants in marine sediment from Yeongil Bay, Korea: 2. Dioxin-like and estrogenic activities

This study employed mechanism-specific in vitro bioassays to help characterize the occurrence and distribution of dioxin-like and estrogenic contaminants in sediment from Yeongil Bay, Korea. Approximately 85% of the sediments tested induced significant dioxin-like activity in the H4IIE-luc bioassay, while approximately 50% induced significant estrogenic activity in the MVLN bioassay. Instrumentally-derived estimates of 2,3,7,8-tetrachlorodibenzo-p-dioxin and 17beta-estradiol equivalents tended to underestimate the magnitude of response observed in the bioassays, suggesting that compounds detected by chemical analysis did not account for all the activity associated with Yeongil Bay sediments, or that non-additive interactions were occurring. The greatest dioxin-like and estrogenic activity was associated with the mid-polarity Florisil fractions (F2) expected to contain polycyclic aromatic hydrocarbons (PAHs) as well as chlorinated dioxins and furans. As in previous studies of Korean coastal sediment, more polar fractions (F3) generated more modest responses both in terms of magnitude and the number of samples responding.     

EPR monitoring of the bioavailability of an organic xenobiotic (4-hydroxy-TEMPO) in model clay suspensions and pastes

Electron paramagnetic resonance spectroscopy is used to monitor the bioavailability of a nitroxide spin probe, 4-hydroxy-Tempo or Tempol, in Ca-hectorite suspensions and pastes, to bacteria capable of degrading this probe co-metabolically. In nutrient solutions with an initial probe concentration of 1.2 mM and in the absence of hectorite, bacteria are able to denature Tempol and eliminate its paramagnetic signal within 48 h. In the presence of hectorite and after flocculation, the effect of bacteria is significantly delayed, but almost complete denaturation still occurs, after roughly 120 h. When hectorite is added but the bacterial/clay suspension is not centrifuged, Tempol denaturation levels off after about 24 h and reaches a plateau with approximately 45% of Tempol remaining. This plateau does not constitute evidence of limited bioavailability, as is widely assumed, since subsequent addition of nutrients causes the denaturation reaction to proceed to a second plateau, with merely 10% of Tempol remaining.     

Effects of restoration and reflooding on soil denitrification in a leveed Midwestern floodplain.

River floodplains have the potential to remove nitrate from water through denitrification, the anaerobic microbial conversion of nitrate to nitrogen gas. An important factor in this process is the interaction of river water with floodplain soil; however, many rivers have been disconnected from their historic floodplains by levees. To test the effect of reflooding a degraded floodplain on nitrate removal, we studied changes in soil denitrification rates on the Baraboo River floodplain in Wisconsin, USA, as it underwent restoration. Prior to this study, the site had been leveed, drained, and farmed for more than 50 years. In late fall 2002, the field drainage system was removed, and a gate structure was installed to allow controlled flooding of this site with river water. Soil moisture was extremely variable among zones and months and reflected local weather. Soil organic matter was stable over the study period with differences occurring along the elevation gradient. High soil nitrate concentrations occurred in dry, relatively organic-poor soil samples and, conversely, all samples with high moisture soils characterized by low nitrate. We measured denitrification in static cores and potential denitrification in bulk samples amended with carbon and nitrogen, one year before and two years following the manipulation. Denitrification rates showed high temporal and spatial variability. Static core rates of individual sites ranged widely (from 0.00 to 16.7 microg N2O-N x [kg soil](-1) x h(-1), mean +/- SD = 1.10 +/- 3.02), and denitrification enzyme activity (DEA) rates were similar with a slightly higher mean (from 0.00 to 15.0 microg N2O-N x [kg soil](-1) x h(-1), 1.41 +/- 1.98). Denitrification was not well-correlated with soil nitrate, organic matter content, or moisture levels, the three parameters typically thought to control denitrification. Static core denitrification rates were not significantly different across years, and DEA rates decreased slightly the second year after restoration. These results demonstrate that restored agricultural soil has the potential for denitrification, but that floodplain restoration did not immediately improve this potential. Future floodplain restorations should be designed to test alternative methods of increasing denitrification.     

Recognition of individual-specific marked parasitized hosts by the solitary parasitoid Epidinocarsis lopezi

Summary In parasitoid wasps, self-superparasitism (oviposition into a host already parasitized by the female herself) often contributes less to the reproductive success of the parasitoid than oviposition into a host previously parasitized by a conspecific (conspecific superparasitism). It could therefore often be profitable for parasitoids to avoid self-superparasitism. This requires a mechanism for either (1) the avoidance of previously searched areas and/or (2) the rejection of hosts containing eggs laid by the searching female. We investigated whether the solitary parasitoid Epidinocarsis lopezi is able to avoid self-superparasitism. We show that visits to previously searched patches were shorter than visits to unsearched patches and conclude that E. lopezi females leave a trail odour on patches they have searched. No differences were found between the time on patches previously searched by the wasp itself and on patches visited by conspecifics. However, E. lopezi superparasitizes fewer hosts previously parasitized by itself than hosts parasitized by a conspecific. Thus, they recognize an individual-specific mark in or on the host. We discuss how patch marking and host marking enable E. lopezi to avoid self-superparasitism.     

Production primaire au niveau de la thermocline en zone néritique de Méditerranée Nord-Occidentale

Vertical profiles of physical, chemical and phytoplanktonic parameters are described, at the level of the thermocline, in the area of Banyuls-sur-Mer, France. The results show that the thermocline divides two masses of water: (1) Mediterranean surface water with low nutrient concentrations and a salinity below 38.00 ‰; (2) deep, nutrient-rich upwelled water (N?NO₃ >3 μat-g·l^-1, P?PO₄>0.3 μat-g·l^-1, >38.30 ‰ S), which comes from the upper limit of the Mediterranean intermediate water, usually located at the 200 m level. Consequently, conditions are suitable for high production rates at the bottom of the thermocline, where Chl a is above 0.5 mg·m^-3; dominant species are Nitzschia delicatissima and N. pungens. A diagram is presented explaining the different effects of the pycnoclines on primary production: eutrophication at the pycnocline levels is the result of passive accumulation of phytoplankton and organic matter during sedimentation, and/or of reduced diffusion of nutrients from deep waters towards the surface.     

Replacement of reproductives in Nasutitermes princeps (Desneux) (Isoptera: Termitidae)

Summary The production of replacement reproductives in experimentally orphaned societies was investigated in Nasutitermes princeps (Desneux). From 1 to 180 replacement queens and multiple kings, all adultoids, were found in the 13 nests that were re-collected. Normal imagos, microimagos, or a mixture of the two forms were present, depending on colony composition at the time of orphaning. In colonies with alates, the corresponding forms were found as replacement reproductives. Where only young nymphs were present, microimagos differentiated. Neither the number of queens nor their level of physogastry was correlated with the time elapsed since orphaning, but the total egg-laying rates were. We suggest that competition among queens rather than time determines individual physogastric development. Observations show that the most likely cause of accidental queen death in nature is probably nest fall from the supporting tree. Even in this case, the queen may be able to migrate to a newly rebuilt nest. An experimental simulation of this situation showed that colony migration can occur. The data indicate that the replacement of the primary queen after her accidental death cannot by itself account for the high rate of polygyny (60%) encountered in N. princeps. Two other possible causes are the replacement of the ageing foundress as a normal event of colony life, and colony reproduction by budding off new nests with adultoid reproductives.King Léopold III Biological Station, Laing Island, Papua New Guinea, contribution no. 84Research Assistant of the National Fund for Scientific Research (Belgium)     

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.