Synthesis of [13C]- and [14C]-labeled phenolic humus and lignin monomers

Natural phenolic monomers are ubiquitous in the environment and are involved in the stabilization of atmospheric carbon and the transformation of xenobiotics. Investigations on the stabilization of phenolic carbons and their environmental fate are hampered by the unavailability of commercial [13C]- and [14C]-labeled phenols. Here we report the complete chemical synthesis of the lignin and humus structural monomers p-coumaric, ferulic, and caffeic acids, p-hydroxybenzaldehyde, protocatechualdehyde, vanillin, catechol, and guaiacol, uniformly [13C]- or [14C]-labeled in the aromatic ring, starting from commercially available [U-ring-13C]- or [U-ring-14C]-labeled phenol. The synthesis of these compounds involved selective ortho-hydroxylation of the aromatic ring, Friedel-Crafts alkylation, and Knoevenagel condensation. [U-ring-13C]- or [U-ring-14C]-p-coumaric acid was synthesized via p-hydroxybenzaldehyde with a 75% yield with respect to phenol. Synthesis of [U-ring-13C]- or [U-ring-14C]-ferulic acid, consisting of six single steps via guaiacol and vanillin, had an overall yield of up to 45%. Uniformly ring-labeled caffeic acid was synthesized either via catechol and protocatechualdehyde in five single steps, yielding [U-ring-14C]-caffeic acid with a 37% yield, or via guaiacol, vanillin, and ferulic acid in seven steps, yielding [U-ring-13C]-caffeic acid with an 18% yield. Ferulic acid, [14C]-labeled at beta-C of the propenoic side chain, was synthesized from [2-14C]-malonic acid under Knoevenagel conditions with a 67% yield with respect to malonic acid. Demethylation of the [beta-14C]-ferulic acid with BBr3 in CH3CN resulted in [beta-14C]-caffeic acid with a 62% yield. All [U-ring-13C]-labeled phenolic products were analyzed by 13C nuclear magnetic resonance (13C-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).     

Diuron mobility through vineyard soils contaminated with copper

The herbicide diuron is frequently applied to vineyard soils in Burgundy, along with repeated treatments with Bordeaux mixture (a blend of copper sulfate and calcium hydroxide) that result in elevated copper concentrations. Cu could in principle affect the fate and transport of diuron or its metabolites in the soil either directly by complexation or indirectly by altering the populations or activity of microbes involved in their degradation. To assess the effect of high Cu concentrations on diuron transport, an experiment was designed with ten undisturbed columns of calcareous and acidic soils contaminated with 17--509 mg kg(-1) total Cu (field-applied). Grass was planted on three columns. Diuron was applied to the soils in early May and in-ground lysimeters were exposed to outdoor conditions until November. Less than 1.2% of the diuron applied was found in the leachates as diuron or its metabolites. Higher concentrations were found in the effluents from the grass-covered columns (0.1--0.45%) than from the bare-soil columns (0.02--0.14%), and they were correlated with increases in dissolved organic carbon. The highest amounts of herbicide were measured in acidic-soil column leachates (0.98--1.14%) due to the low clay and organic matter contents of these soils. Cu also leached more readily through the acidic soils (32.8--1042 microg) than in the calcareous soils (9.5--63.4 microg). Unlike in the leachates, the amount of diuron remaining in the soils at the end of the experiment was weakly related to the Cu concentrations in the soils.     

Environmental impact of two successive chemical treatments in a small shallow eutrophied lake: Part I. Case of aluminium sulphate

This paper deals with the efficiency and effects of addition of aluminium sulphate on soft water quality of a shallow eutrophic lake. Almost all the controlled variables improved with treatment, especially nutrient concentrations such as soluble reactive phosphorus (SRP) and transparency. However, aluminium sulphate was not added in sufficient quantity to reduce the total phosphorus content. SRP concentration was significantly reduced in the short term. Moreover, external loading of phosphorus was high and not taken into account by the in-lake treatments. Finally, resuspension of sediment (polymictic lake) removed the alum hydroxide layer on the sediment surface, which reduced treatment effectiveness. No significant pH decrease was noted following alum addition. According to bibliographical toxicological data, monomeric aluminium content does not show any toxic effect on aquatic fauna and flora. In spite of low SRP in the water column, the treatment did not prevent appearance of Microcystis sp. colony (> 10 colony per ml) approximately 30 days after alum application.     

Manipulation of nest-box density affects extra-pair paternity in a population of blue tits (<Emphasis Type="Italic">Parus caeruleus</Emphasis>)

We tested the effect of manipulation of breeding density on the occurrence of extra-pair paternity in a blue tit (Parus caeruleus) population during two consecutive years. In a homogeneous oak forest, nest-box manipulation provided a high density plot (plot A, 1.10 and 1.32 pairs/ha) and a low density plot (plot B, 0.43 and 0.46 pairs/ha). Microsatellite analysis on 91 broods revealed a higher proportion of extra-pair paternity in broods in plot A (mean of 17.2%) than in plot B (mean of 11.4%). A correlative approach showed that the proportion of extra-pair young in broods was affected by the number of breeding neighbours within 100 m around the nest-box, by the distance to the nearest breeding neighbour and by an additional plot effect. However, the nearest neighbours accounted for only 39.3% of extra-pair paternities and distance to extra-pair fathers was significantly higher than the nearest neighbour distance in both plots. This implies that the effect of density on the occurrence of extra-pair paternities is associated with active female choice to enhance the brood fitness. Although there were more extra-pair young in broods when density was high, the number of extra-pair fathers did not increase and stayed close to one. We suggest that density increases the cost of mate guarding by males, thereby increasing the possibility for females to solicit extra-pair paternities to the cuckolding male they have chosen. Finally, we discuss why correlatives approaches do not always show evidence for an effect of breeding density on extra-pair paternity occurrence.Communicated by M. Soler     

Influence of ozone on the sampling and storage of volatile organic compounds in canisters

A dynamic dilution system was used for the study of the influence of ozone on the sampling and storage of volatile organic compounds (VOCs) at 0, 4, 7 and 14 days in “TO-Can” canisters at two ozone concentrations, 60 and 150 ppbv. Among the 31 ozone precursors VOCs, a representative mixture containing five alkenes, five aromatics, acetylene and 1,3 butadiene was selected using the Clausius–Clapeyron equation. Here, we demonstrate that the presence of ozone have no influence on the concentrations of VOCs after 14 days storage period and consequently no problem of representativity of the sampling appears after 14 days of storage. The main explanation is the degradation of ozone in contact with deactivated walls of canisters.     

Gravitational Microlensing

   Gravitational lensing – i.e. light deflection by gravity – has become an important tool for exploring our Universe, in particular to determine its matter content. There are cases in which the deflection angles are tiny, of the order of milliarcseconds or smaller, such that the multiple images are not observable. However, lensing magnifies the affected source, and since the lens and the source are moving relative to each other, this can be detected as a time-variable brightness. This behaviour is referred to as gravitational microlensing, a very powerful method to search for dark matter in the halo of our own Galaxy, if it consists of massive astrophysical compact halo objects (MACHOs), and to study the content of low-mass stars in the galactic disk. Since the discovery of the first microlensing events in September 1993 by monitoring millions of stars in the Large Magellanic Cloud (LMC) and in the direction of the galactic centre, more than 200 events have been found. Preliminary analysis of the events towards the LMC indicate that the halo dark-matter fraction in the form of MACHOs is of the order of 50%, assuming a standard spherical halo model. This article provides an overview of gravitational microlensing and of the main results achieved so far. Indeed, gravitational microlensing research has expanded very rapidly in the last few years, and many new applications have been suggested, including the detection of Earth-like planets around stars in our Galaxy.     

Detection of Hepatitis E Virus in Sewage After an Outbreak on a French Island

A hepatitis E outbreak, which occurred on a small isolated island, provided an opportunity to evaluate the association between the number of hepatitis E cases in the community and the concentration of virus detected in sewage. Samples were collected from the different sewage treatment plants from the island and analyzed for the presence of hepatitis E (HEV) virus using real-time RT-PCR. We demonstrated that if 1–4 % of inhabitants connected to a WWTP were infected with HEV, raw sewage contained HEV at detectable levels. The finding that such a small number of infected people can contaminate municipal sewage works raises the potential of the further distribution of the virus. Indeed, investigating the routes of transmission of HEV, including the potential for sewage effluent to contain infectious HEV, may help us to better understand the epidemiology of this pathogen, which is considered to be an emerging concern in Europe.