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).     

Spatial connectivity in a large river system: resolving the sources and fate of dissolved organic matter

Large rivers are generally heterogeneous and productive systems that receive important inputs of dissolved organic matter (DOM) from terrestrial and in situ sources. Thus, they are likely to play a significant role in the biogeochemical cycling of the DOM flowing to the oceans. The asymmetric spatial gradient driven by directional flow and environmental heterogeneity contributes to the fate of DOM flowing downstream. Yet, the relative effects of spatial connectivity and environmental heterogeneity on DOM dynamics are poorly understood. For example, since environmental variables show spatial heterogeneity, the variation explained by environmental and spatial variables may be redundant. We used the St. Lawrence River (SLR) as a representative large river to resolve the unique influences of environmental heterogeneity and spatial connectivity on DOM dynamics. We used three-dimensional fluorescence matrices combined with parallel factor analysis (PARAFAC) to characterize the DOM pool in the SLR. Seven fluorophores were modeled, of which two were identified to be of terrestrial origin and three from algal exudates. We measured a set of environmental variables that are known to drive the fate of DOM in aquatic systems. Additionally, we used asymmetric eigenvector map (AEM) modeling to take spatial connectivity into account. The combination of spatial and environmental models explained 85% of the DOM variation. We show that spatial connectivity is an important driver of DOM dynamics, as a large fraction of environmental heterogeneity was attributable to the asymmetric spatial gradient. Along the longitudinal axis, we noted a rapid increase in dissolved organic carbon (DOC), mostly controlled by terrestrial input of DOM originating from the tributaries. Variance partitioning demonstrated that freshly produced protein-like DOM was found to be the preferential substrate for heterotrophic bacteria undergoing rapid proliferation, while humic-like DOM was more correlated to the diffuse attenuation coefficient of UVA radiation.     

Mediating male–male interactions: the role of the UV blue crest coloration in blue tits

Badges of status, usually color patches, are hypothesized to serve as important signals within natural populations by communicating an individual’s fighting ability or aggressiveness before an interaction ever takes place. These signals, which may evolve via sexual and/or social selection, mediate intra-specific competition by influencing the outcome or escalation of contests between individuals. The last 10 years saw the rise of interest in the role of ultraviolet (UV)-based coloration in intra-sexual communication. However, the rare experimental studies that tested this hypothesis found opposite results, which may originate from the different methodological procedures used to assess the badge of status theory. We present here the results of an experiment testing whether male blue tits (Cyanistes caeruleus) respond differently to unfamiliar conspecifics presenting contrasted UV crest coloration. In an aviary, we simultaneously presented two caged blue tits with enhanced (UV+) or reduced (UV−) crest coloration to a focal bird. We found that focal males acted more aggressively towards the UV− males than UV+ males. In addition, focal males fed more often close to males that were similar in brightness or duller than themselves. We conclude that, in blue tits, UV blue crest coloration affects both social and aggressive responses towards unfamiliar individuals, and thus it has some properties of a badge of status.     

Sampling and Analysis of Quaternary Ammonium Compounds (QACs) Traces in Indoor Atmosphere

Quaternary Ammonium Compounds (QACs) are widely found in disinfectants used in hospitals. Benzalkonium chloride (BAC) and didecyldimethylammonium chloride (DDAC) predominate in the disinfecting formulations. These compounds are strong irritants and can play a role in the induction of Occupational Asthma among the professionals of health and cleaning. In order to evaluate the potential health effect of these quaternary ammonium compounds to hospital employers, the development of an analytical method for their quantification in indoor air was developed. DDAC aerosols are trapped by adsorption on XAD-2 resin SKC tube. The air in hospital buildings was sampled using a constant debit Gillian pump at a flow of 1.0 l/min (+/-5%). Ion Chromatography (IC) was chosen for the analysis of DDAC especially for its high sensitivity and specificity. The Limit of Detection (LOD) by IC for DDAC is 0.56 mug/ml. Therefore the LOD of atmospheric DDAC is 28 microg/m(3) with an air volume of 100 l and a desorption volume of 5 ml. All DDAC air samples were lower than the LOD of the analytical method by IC. Under the standard conditions of use of the disinfecting solutions (Surfanios, Ampholysine Plus and Amphospray 41), the insignificant volatility of DDAC would not seem to be able to contaminate the indoor hospital atmosphere during the disinfection process. However, the DDAC can contaminate working atmospheres if it is put in suspension by aerosolisation.     

Fetal cerebral hemorrhage due to X-linked GATA1 gene mutation

We report a multiplex family with a GATA1 gene mutation responsible for a massive fetal cerebral hemorrhage occurring at 36 weeks. Two other stillbirth cousins presented with fetal hydrops and congenital hemochromatosis' phenotype at 37 and 12 weeks of gestation. Molecular screening revealed the presence of a c.613G>A pathogenic allelic variation in exon 4 of GATA1 gene in the 3 male siblings and their carrier mothers. The diagnosis of a GATA1 gene mutation may be suspected in cases of male fetuses with intracerebral bleeding, particularly if a history of prior fetal loss(es) and mild maternal thrombocytopenia are also present.     

A multiresidue method for the analysis of phenols and nitrophenols in the atmosphere

A method using GC-MS and derivatization with N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) was developed for the analysis of 20 phenolic compounds in atmospheric samples (gas and particles). Air sampling was carried out using a Hi-Vol sampler with glass fibre filter and XAD-2 resin at a flow rate of 60 m(3) h(-1). The particle and gas phases were collected separately over a period of 4 h. Samples were Soxhlet extracted, evaporated to dryness under nitrogen and refilled with acetonitrile. 100 microl of these extracts were derivatized with 100 microl of MTBSTFA at 80 degrees C for 1 h under strong stirring. Phenolic compounds were injected into a GC-MS in splitless mode and quantified as their TBDMS derivatives in the SIM mode. Mass spectral analysis of the derivatives of the 20 compounds studied indicates that the spectra are highly specific showing an ion at [M - 57]+ which is useful for structure confirmation or analysis at low levels using selected ion monitoring. Quantification limits varied between 5 microg l(-1) and 10 microg l(-1) which correspond to 20 pg m(-3) and 40 pg m(-3) for 250 m(3) of air sampled. This method was successfully applied to atmospheric samples.     

Radiostrontium-90 (90Sr) Ultra-Traces Measurements by Coupling Ionic Chromatography (HPIC) and on Line Liquid Scintillation Counting (OLLSC)

The important role of the beta emitter Strontium-90 in our environmental has been studied since the nuclear age. This long half-life isotope (28.1 years) is produced in a relatively high yield (5.8 % from Uranium-235) during the fission of heavy elements. It has been reported to be the major artificial source of internal irradiation of the human body. Its valence shell electron configuration is the same as Calcium and so this isotope is easily fixed in the bones. The classical analysis of this particular isotope requires several weeks since it produces Yttrium-90 which is also a beta emitter. We developed a new trace analysis method by coupling High Performance Ionic Chromatography (HPIC), to separate Strontium-90 from natural or power plant reactor water, and on-line liquid scintillation counting detector, measuring the beta emission of low concentration Strontium-90 before Yttrium-90 is formed in a significant amount. We report here some analysis parameters : HPIC setup, scintillation cocktail, window, counting efficiency, linearity, pre-concentration and detection limits. We were able to determine very low concentrations of Strontium-90. The minimum concentration detected without a pre-concentration system was 0.5 ppt from a 200 µL sample (6.3×10-12 mole/L). The analysis only requires a few hours.     

A Method for Improving the Management of Controversial Wetland

Valley bottom wetlands in agricultural landscapes often are neglected in national and regional wetland inventories. Although these areas are small, located in the bottomlands of the headwater catchments, and scattered in the rural landscape, they strongly influence hydrology, water quality, and biodiversity over the whole catchment area. Valley bottom wetlands often are considered as controversial wetlands. Awareness of the functional role of wetlands is increasing, in parallel with their progressive disappearance in intensive farming landscapes. The need to improve tools for controlling wetland management is a primary consideration for decision makers and land users. This article proposes a method for the inventory of valley bottom wetlands. The method is based on the functional analysis of potential, existing, and efficient valley bottom wetlands (the PEEW approach). Several indicators are proposed for checking the validity of such an approach. Potential wetlands are delineated by means of a topographic index using topographic and pedoclimatic criteria computed from a Digital Elevation Model and easily accessible databases. Existing wetlands are identified from observed surface moisture, the presence of specific wetland vegetation, or soil feature criteria. Efficient wetlands are defined through a given function, such as flow or pollutant regulation or biodiversity control. An analysis of areas at the limits between potential, existing, and efficient wetlands highlights land cultivated or drained in the past, which currently represents negotiating areas in which rehabilitation and other intended management actions can be implemented.