Distribution of steroid- and dioxin-like activities between sediments, POCIS and SPMD in a French river subject to mixed pressures

The contamination of aquatic systems by endocrine disrupting chemicals (EDCs) is now a widely established fact. Nevertheless, there is still a scarcity of knowledge concerning the source, transport, fate and bioavailability of such active compounds. In the present study we assessed the distribution of estrogenic, (anti-)androgenic, pregnane X receptor-like (PXR) and dioxin-like activities between sediment and water compartments using a polar organic compound integrative sampler (POCIS) and a semi-permeable membrane device (SPMD) passive sampler in a river where sediment has been previously described as highly and multi-contaminated. We first confirmed the contamination pattern of this river sediment between 2004, 2009 and 2010 samples, suggesting that this river is subject to a constant high contamination level. However, we showed a different distribution pattern of these activities between compartments: estrogenic activity was mainly detected in POCIS extracts and to a lesser extent in sediment and SPMD extracts; anti-androgenic activities were mainly detected in SPMD and sediment extracts while no activity was detected in POCIS extracts; PXR-like activity was detected in all three investigated compartments, with POCIS > SPMD > sediment; dioxin-like activity was mainly found in the sediment and the SPMD extracts. Overall, partitioning of the biological activities was in accordance with physicochemical properties (e.g., log K _ow) of typical known active chemicals in each bioassay. Furthermore, in order to establish whether the chemicals involved in these activities were similar between the compartments, we fractionated sediment, POCIS and SPMD extracts using a multi-step fractionation procedure. This highlighted differences in the nature of active chemicals between compartments. Altogether, our results support the need to consider different compartments in order to enhance exposure assessment.     

Emission characteristics of air pollutants from incense and candle burning in indoor atmospheres

Volatile organic compounds (VOCs) and particles emitted by incense sticks and candles combustion in an experimental room have been monitored on-line and continuously with a high time resolution using a state-of-the-art high sensitivity-proton transfer reaction-mass spectrometer (HS-PTR-MS) and a condensation particle counter (CPC), respectively. The VOC concentration–time profiles, i.e., an increase up to a maximum concentration immediately after the burning period followed by a decrease which returns to the initial concentration levels, were strongly influenced by the ventilation and surface interactions. The obtained kinetic data set allows establishing a qualitative correlation between the elimination rate constants of VOCs and their physicochemical properties such as vapor pressure and molecular weight. The emission of particles increased dramatically during the combustion, up to 9.1(±0.2)?×?10⁴ and 22.0(±0.2)?×?10⁴ part cm^?3 for incenses and candles, respectively. The performed kinetic measurements highlight the temporal evolution of the exposure level and reveal the importance of ventilation and deposition to remove the particles in a few hours in indoor environments.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs

A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9 mg L⁻¹) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ¹³C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ¹³C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ¹³C values of the DOC recovered in the reservoir (−28.5 ± 0.2‰; n = 22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ¹³C in algae = −30.1 ± 0.3‰; n = 2) being indistinguishable from the δ¹³C values of allochthonous DOC from inflowing rivers (−28.6 ± 0.1‰; n = 8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs.     

Long-term effects of clear-cutting and selective cutting on soil methane fluxes in a temperate spruce forest in southern Germany

Based on multi-year measurements of CH₄ exchange in sub-daily resolution we show that clear-cutting of a forest in Southern Germany increased soil temperature and moisture and decreased CH₄ uptake. CH₄ uptake in the first year after clear-cutting (−4.5 ± 0.2 μg C m⁻² h⁻¹) was three times lower than during the pre-harvest period (−14.2 ± 1.3 μg C m⁻² h⁻¹). In contrast, selective cutting did not significantly reduce CH₄ uptake. Annual mean uptake rates were −1.18 kg C ha⁻¹ yr⁻¹ (spruce control), −1.16 kg C ha⁻¹ yr⁻¹ (selective cut site) and −0.44 kg C ha⁻¹ yr⁻¹ (clear-cut site), respectively. Substantial seasonal and inter-annual variations in CH₄ fluxes were observed as a result of significant variability of weather conditions, demonstrating the need for long-term measurements. Our findings imply that a stepwise selective cutting instead of clear-cutting may contribute to mitigating global warming by maintaining a high CH₄ uptake capacity of the soil.     

Modeling the carbon dynamics of the La Grande hydroelectric complex in northern Quebec

A mechanistic semi-empirical carbon cycle model of the La Grande reservoir complex in northern Quebec, Canada was conceived in order to investigate the climate impact of such a large alteration of the continental water cycle. The model includes inputs from the drainage basin, organic matter release from flooded soils, CO₂ emissions across the water-atmosphere interface and sedimentation. Most input data stems from previous research by our group on those ecosystems. The model includes the seven reservoirs of the La Grande complex and was run for periods of 50 and 100 years. Terrigeneous dissolved, particulate and suspended soil carbon fluxes and concentrations were computed. Over 100 years, 31.3 × 10¹² g C are released from flooded soils, equivalent to 28-29% of inputs from the drainage basin. 40-74% of dissolved organic carbon is mineralized. CO₂ fluxes over 100 years are 50.5-79.8 × 10¹² g C, 46.4-67.9 × 10¹² g C more than in the absence of reservoirs. The increase in mineralization of organic matter and in CO₂ emissions is a result of the increase in cumulated water residence time due to the creation of the reservoirs. Changes in other carbon sinks and sources likely offset a part of this additional carbon flux to the atmosphere. In the first years following flooding of the reservoir, organic carbon release from flooded soils exceeds CO₂ emissions, implying the downstream export of large quantities of eroded soil organic carbon. After this initial period, CO₂ emissions are fuelled by organic carbon originating from the drainage basin.     

Relationships between vitamin A and PCBs in grey seal mothers and pups during lactation

A previous study has shown a simultaneous increase of vitamin A and PCBs in grey seal (Halichoerus grypus) milk at late lactation (Debier et al., 2004). Here we sought to understand this unexpected relationship by comparing the dynamics of vitamin A and PCBs in the different tissue compartments of transfer. Lactating grey seals and their pups were sampled longitudinally in Scotland during the 2006 breeding season. As blubber reserves decreased, concentrations of vitamin A and PCBs increased during lactation in the inner layer of maternal blubber. A concomitant rise was observed in milk and consequently in the serum of suckling pups. The similar dynamics of vitamin A and PCBs in milk and inner blubber suggest a common mechanism of mobilisation from maternal body stores and transfer into the milk. A panel data analysis highlighted a negative impact of PCBs in milk and pup serum on vitamin A status in pup serum.     

Experimental study of the transport properties of rough self-affine fractures

An experimental study of the transport properties of fluid-saturated joints composed of two complementary rough fracture surfaces, translated with respect to each other and brought in contact, is reported. Quantitative roughness measurements on different fractured granite samples show that the surfaces have a self-affine geometry from which the dependence of the mean aperture on the relative displacement of fracture surfaces kept in contact can be predicted. Variations of the hydraulic and electrical conductances of the joint are measured as functions of its mean aperture. A simple parallel plane model accounts for the global trend of the measurements, but significant deviations are observed when a relative lateral displacement of the surfaces is introduced. A theoretical analysis of their origin shows that they are due both to the randomness of the aperture field and to a nonzero local slope of the surface near the injection hole; the corresponding conductivity fluctuation amplitudes have power law and linear variations with the lateral displacement, and are enhanced by the radial injection geometry.