A quantum cascade laser infrared spectrometer for CO2 stable isotope analysis: Field implementation at a hydrocarbon contaminated site under bio-remediation

Real-time methods to monitor stable isotope ratios of CO_2 are needed to identify biogeochemical origins of CO_2 emissions from the soil–air interface. An isotope ratio infra-red spectrometer(IRIS) has been developed to measure CO_2 mixing ratio with δ~13C isotopic signature, in addition to mixing ratios of other greenhouse gases(CH_4, N2_O). The original aspects of the instrument as well as its precision and accuracy for the determination of the isotopic signature δ~13C of CO_2 are discussed. A first application to biodegradation of hydrocarbons is presented, tested on a hydrocarbon contaminated site under aerobic bio-treatment. CO_2 flux measurements using closed chamber method is combined with the determination of the isotopic signature δ~13C of the CO_2 emission to propose a non-intrusive method to monitor in situ biodegradation of hydrocarbons. In the contaminated area, high CO_2 emissions have been measured with an isotopic signature δ~13C suggesting that CO_2 comes from petroleum hydrocarbon biodegradation.This first field implementation shows that rapid and accurate measurement of isotopic signature of CO_2 emissions is particularly useful in assessing the contribution of contaminant degradation to the measured CO_2 efflux and is promising as a monitoring tool for aerobic bio-treatment.     

Fluorescence Verses Radioactivity Labeling for Lab-Scale Investigation of the Fate of Water-Soluble Polymers in Wastewater Treatment Plants

Water-soluble synthetic polymers are extensively used in cosmetics, detergents and paints. Many end up in wastewater and, later on, in wastewater-treatment plants. In order to gain an insight into their fate in such plants, fluorescence and radioactivity labelings were compared using a lab-scale reactor designed to mimic industrial conditions. Two fermentation media were considered, namely a mixture of E402 and E204 micro-organisms and an activated sludge collected from a water-treatment plant located in the south of France. A sample of low molar mass commercial poly(acrylic acid) (PAA) was labeled by radioactivity with tritium and by coupling the 6-aminofluorescein fluorescent dye. Labeled PAA-containing sludges were allowed to ferment. To monitor the fate of the polymers, aliquots of the fermented mixtures were withdrawn at selected times and centrifuged. Liquid and solid phases were analyzed by scintigraphy or UV spectrometry, depending of the labeling techniques. Both techniques led to similar distributions, c.a. 75% in the supernatant and 25% in the solid phase. Distributions remained constant during the biological tests. There was no degradation of the commercial PAA after aqueous size exclusion chromatography (SEC), in agreement with literature. These features showed that fluorescence-labeling can be used instead of the complex and expensive radiolabeling. The validated fluorescence-based method was then applied to a linear poly(acrylic acid) synthesized by ATRP and labeled with 6-aminofluorescein. There was no significant difference between the commercial and the linear poly(acrylic acid)s. In contrast, a linear PAA with 5% of tert-butyl ester repeating units was predominantly found in the solid phase although adsorption or absorption by micro-organisms could not be demonstrated. The method based on fluorescence labeling should be applicable to other water soluble polymers provided that the dye remains attached to the polymer as it was the case for the studied poly(acrylic acid)s.     

Impact of storm Xynthia in 2010 on coastal agricultural areas: the Saint Laurent de la Prée research farm’s experience

Storm Xynthia crossed France’s western coast between 28th February and 1st March 2010. It hit the Vendée and Charente-Maritime departments hardest, as storm surge flooded up to 23,000 ha of coastal agricultural areas (i.e. polders), causing severe damage to farming operations. However, farm-level damage in the aftermath of seawater flooding is an issue that has rarely been explored in the literature. Here we investigated the effects of storm Xynthia on agriculture at the farm scale. We focused on the case study of Saint Laurent de la Prée research farm, a mixed crop–livestock system that was severely hit. All damages were described and economic losses were quantified for the years 2010 and 2011. The results show numerous consequences of the storm in terms of crop and fodder production losses, but also farm infrastructure repairs, crop restoration and animal health problems. Economic damage costs were high, reaching €71,720 in 2010 (€500/ha flooded) and €56,195 (€390/ha) in 2011 for the case study farm. The discussion highlights the farm-level impacts of seawater flooding and the crucial factors that can explain the damage caused to agriculture by storm events in coastal areas. The results are also discussed in the wider context of global warming which is expected to cause sea level rise and more frequent storm events in the future. The vulnerability of coastal agricultural areas to storms thus exposes broader issues of coastal flooding risk management and specifically the allied protection–remediation–adaptation measures. The conclusions underline the need for future research to address prospective scenarios and subsequent adaptive strategies.     

Sampling and analytical methodology development for the determination of primary and secondary low molecular weight amines in ambient air

In this project, a sampling device and an analytical method have been developed to simultaneously analyse the most frequently found low molecular weight amines, including aliphatic, aromatic and alcohol amines. These amines are diethanolamine, ethanolamine, methylamine, isopropylamine, morpholine, dimethylamine, and aniline. A sampling device was developed using a 37 mm cassette with glass fibre filters impregnated with sulfuric acid. Immediately after sampling, the filter was transferred to vials containing a solution of dansyl chloride. Dansyl chloride was used for derivatisation because it forms aromatic sulfonamides that are fluorescent and easy to protonate for MS detection. The effect of using an internal standard made with the dansylated derivative of 1-(2-methoxyphenyl)piperazine (MOPIP) on the uncertainty and efficiency of the method was also evaluated. This internal standard was spiked directly onto filters. The coupling of HPLC/ESI-MS was used for the simultaneous analysis of all the derivatives. This method showed detection limits of about 0.03 microg mL(-1) to 0.3 microg mL(-1) of amine with an average expanded uncertainty of 3% to 6% depending on the amine. The methodology recoveries are close to 100% for all the amines, and the overall estimated expanded uncertainties vary between 10% and 13% depending on the amine. This new strategy will be useful in evaluating workplace air since a unique sampling system will be used, independent of the amine to be quantified.     

Predator-prey spatial game as a tool to understand the effects of protected areas on harvester-wildlife interactions

No-take reserves are sometimes implemented for sustainable population harvesting because they offer opportunities for animals to spatially avoid harvesters, whereas harvesters can benefit in return from the reserve spillover. Here, we used the framework of predator-prey spatial games to understand how protected areas shape spatial interactions between harvesters and target species and determine animal mortality. In these spatial games, the "predator" searches for "prey" and matches their habitat use, unless it meets spatial constraints offering the opportunity for prey to avoid the mortality source. However, such prey refuges could attract predators in the surroundings, which questions the potential benefits for prey. We located, in the Geneva Basin (France), hunting dogs and wild boar Sus scrofa L. during hunting seasons with global positioning systems and very-high-frequency collars. We quantified how the proximity of the reserve shaped the matching between both habitat uses using multivariate analyses and linked these patterns to animals' mortality with a Cox regression analysis. Results showed that habitat uses by both protagonists disassociated only when hunters were spatially constrained by the reserve. In response, hunters increased hunting efforts near the reserve boundary, which induced a higher risk exposure for animals settled over the reserve. The mortality of adult wild boar decreased near the reserve as the mismatch between both habitat uses increased. However the opposite pattern was determined for younger individuals that suffered from the high level of hunting close to the reserve. The predator-prey analogy was an accurate prediction of how the protected area modified spatial relationships between harvesters and target species. Prey-searching strategies adopted by hunters around reserves strongly impacted animal mortality and the efficiency of the protected area for this harvested species. Increasing reserve sizes and/or implementing buffer areas with harvesting limitations can dampen this edge effect and helps harvesters to benefit durably from source populations of reserves. Predator-prey spatial games therefore provide a powerful theoretical background for understanding wildlife-harvester spatial interactions and developing substantial application for sustainable harvesting.     

Conservation resource allocation,small population resiliency,and the fallacy of conservation triage

Some conservation prioritization methods are based on the assumption that conservation needs overwhelm current resources and not all species can be conserved; therefore, a conservation triage scheme (i.e., when the system is overwhelmed, species should be divided into three groups based on likelihood of survival, and efforts should be focused on those species in the group with the best survival prospects and reduced or denied to those in the group with no survival prospects and to those in the group not needing special efforts for their conservation) is necessary to guide resource allocation. We argue that this decision-making strategy is not appropriate because resources are not as limited as often assumed, and it is not evident that there are species that cannot be conserved. Small population size alone, for example, does not doom a species to extinction; plants, reptiles, birds, and mammals offer examples. Although resources dedicated to conserving all threatened species are insufficient at present, the world's economic resources are vast, and greater resources could be dedicated toward species conservation. The political framework for species conservation has improved, with initiatives such as the UN Sustainable Development Goals and other international agreements, funding mechanisms such as The Global Environment Facility, and the rise of many nongovernmental organizations with nimble, rapid-response small grants programs. For a prioritization system to allow no extinctions, zero extinctions must be an explicit goal of the system. Extinction is not inevitable, and should not be acceptable. A goal of no human-induced extinctions is imperative given the irreversibility of species loss.     

Increasing UV-B radiation at the earth's surface and potential effects on aqueous mercury cycling and toxicity

In the past two decades, a great deal of attention has been paid to the environmental fate of mercury (Hg), and this is exemplified by the growing number of international conferences devoted uniquely to Hg cycling and its impacts on ecosystem functions and life. This interest in the biogeochemistry of Hg has resulted in a significant improvement of our understanding of its impact on the environment and human health. However, both past and current research, have been primarily oriented toward the study of direct impact of anthropogenic activities on Hg cycling. Besides a few indirect effects such as the increase in Hg methylation observed in acid-rain impacted aquatic systems or the reported enhanced Hg bioaccumulation in newly flooded water reservoirs; changes in Hg transformations/fluxes that may be related to global change have received little attention. A case in point is the depletion of stratospheric ozone and the resulting increase in solar UV-radiation reaching the Earth. This review and critical discussion suggest that increasing UV-B radiation at earth's surface could have a significant and complex impact on Hg cycling including effects on Hg volatilization (photo-reduction), solubilization (photo-oxidation), methyl-Hg demethylation, and Hg methylation. Therefore, this paper is written to provoke discussions, and more importantly, to stimulate research on potential impacts of incoming solar UV-radiation on global Hg fluxes and any toxicity aspects of Hg that may become exacerbated by UV-radiation.     

Solvent toxicity to amphibian embryos and larvae

Organic micropollutants are often damaging for aquatic organisms. Being usually hydrophobic compounds, they are often dissolved in an organic co-solvent which increases their solubility in water. The aim of this study was to study the toxicity of various solvents on embryos (protected or not by jelly coat) and on tadpoles of the common frog (Rana temporaria). Tested solvents were methanol (MeOH), methylene chloride (CH(2)Cl(2)), dimethyl sulfoxyde (DMSO), acetone (Ac) and ethanol (EtOH). Embryos exhibited higher mortality rates than tadpoles. Embryos with jelly were more sensitive to high concentration of solvents than embryos without jelly (except for acetone). According to these results, Ac, DMSO and CH(2)Cl(2) can be used as co-solvents in water to help the dissolution of micropollutants at concentration equal to or lower than 0.001 ml/l for frog embryos, and EtOH, Ac and CH(2)Cl(2) at concentration equal to or lower than 0.01 ml/l for Rana temporaria tadpoles.     

Spatial variations and temporal trends between 1994 and 2005 in polychlorinated biphenyls, organochlorine pesticides and heavy metals in European eel (Anguilla anguilla L.) in Flanders, Belgium

In Flanders, the northern region of Belgium, European yellow eel muscle tissue was used as an indicator of environmental and potential human dietary exposure by hazardous chemicals of surface waters and sediments. Between 1994 and 2005, over 2800 eel captured at 365 stations were analysed for PCBs, pesticides and heavy metals. Contamination of eel in Flanders fell within the range of reported concentrations in other watersheds of Western Europe. A spatial analysis of the data demonstrated that the variation in pollutant concentration tended towards higher values. This was especially evident for PCBs, lindane, endrin, dieldrin and DDE. The concentration of almost all banned substances decreased significantly during the study period.