Characterization of endocrine disruptors from a complex matrix using estrogen receptor affinity columns and high performance liquid chromatography–high resolution mass spectrometry

Complex mixtures of contaminants with potential adverse effects on human health and wildlife are found in the environment and in the food chain. These mixtures include numerous anthropogenic compounds of various origins and structures, which may behave as endocrine disruptors. Mixture’s complexity is further enhanced by biotic and abiotic transformations. It is therefore necessary to develop new strategies allowing the identification of the structure of known, as well as unknown, nuclear receptor (NR) ligands present in complex matrices. We explored the possibility to use NR-based affinity columns to characterize the presence of bioactive molecules in environmental complex mixtures. Estrogen receptor α (ERα)-based affinity columns were used to trap and purify estrogenic substances present in surface sediment samples collected in a French river under mixed anthropogenic pressure. We combined biological, biochemical and analytical approaches to characterize the structure of ligands retained on columns and demonstrate the presence of known active molecules such as bisphenol A and octylphenol, but also of unexpected ERα ligands (n-butylparaben, hydroxyl-methyl-benzofuranone). High resolution mass spectrometry results demonstrate that ERα affinity columns can be used for the isolation, purification and identification of known as well as unknown estrogenic contaminants present in complex matrices.     

Analytical model for site-specific isotope fractionation in 13C during sorption: determination by isotopic 13C NMR spectrometry with vanillin as model compound

The aim of this study was to conceive a reactive transport model capable of providing quantitative site-specific enrichment factors for fractionation in ¹³C isotopic content during sorption. As test compound the model treats vanillin, for which the ¹³C isotopic content at natural abundance at each of the 8 carbon positions can be measured by quantitative ¹³C nuclear magnetic resonance spectrometry. This technique determines the isotope ratios with a resolution better than ±1‰ (0.1%) at each carbon position. Site-specific isotope fractionations were recorded in chromatography column experiments with silica RP-18 as stationary phase. The one dimensional reactive transport model accounted for the sorption/desorption behavior of 8 individual ¹³C-isotopomers and one ¹²C-isotopomer of vanillin and reproduced satisfactorily the bulk (average over the whole compound) fractionation observed during elution. After model calibration, the enrichment factors were fitted for each carbon site where a significant fractionation was recorded. To show the interest of such a transport model for environmental studies, the model, extended to three dimensions, was exploited to simulate reactive transport in an aquifer. These results show that significant ¹³C isotope fractionation is expected for 4 out of 8 ¹³C-isotopomers in vanillin, and illustrate that bulk isotope ratios measured by conventional compound specific isotope analysis and mass spectrometry would hardly document significant isotope fractionations in vanillin. It is concluded that modeling of site-specific isotope ratios in molecules is a priori feasible and may help to quantify unknown processes in the environment.     

PBDEs in serum and blubber of harbor, grey and harp seal pups from Eastern Canada

Serum and blubber of pup harbor (Phoca vitulina), grey (Halichoerus grypus) and harp (Phoca groenlandica) seals from the Estuary and the Gulf of St. Lawrence were analyzed for polybrominated diphenyl ethers (PBDEs). Concentrations of ∑PBDEs (on lipid weight basis) in tissues of harbor seal pups inhabiting the St. Lawrence Estuary were about five times higher than in those from a colony located in the northern Gulf. Harp seal pups have the lowest levels of ∑PBDEs among the seal species born in the Gulf of St. Lawrence. Lipid normalized concentrations of ∑PBDEs in serum and blubber were strongly correlated, suggesting that the blood collection as a less invasive method could be used to monitor ∑PBDEs in pups. This study shows that fluvial inputs of PBDEs are important to the St. Lawrence marine ecosystem and that inhabiting harbor seal pups have a substantial exposure to PBDEs at a critical developmental stage. In addition, the observed difference in PBDE levels between harp and grey or harbor seal pups from the Gulf of St. Lawrence is explained by the difference in diets of their mothers which is linked with their residency time in the Gulf and their seasonal migration pattern.     

Studies on atmospheric degradation of diazinon in the EUPHORE simulation chamber

The gas phase atmospheric degradation of diazinon has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The rate constant for reaction of diazinon with OH radicals was measured using a conventional relative rate method with di-n-buthylether as reference compound being k = (3.5 ± 1.2) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ at 302 ± 10 K and atmospheric pressure. The available evidence indicates that tropospheric degradation of diazinon is mainly controlled by reaction with OH radicals, and that the tropospheric lifetime with respect to the OH reaction is estimated to be around 4 h whereas its lifetime with respect to the photolysis is higher than 1 d under our conditions. Significant aerosol formation was observed following the reaction of diazinon with OH radicals, and the main carbon-containing products detected in the particle phase were hydroxydiazinon, hydroxydiazoxon and 2-isopropyl-6-methyl-pyrimidinyl-4-ol.     

Lifetime reproductive success and composition of the home range in a large herbivore

The relationship between individual performance and nonrandom use of habitat is fundamental to ecology; however, empirical tests of this relationship remain limited, especially for higher orders of selection like that of the home range. We quantified the association between lifetime reproductive success (LRS) and variables describing lifetime home ranges during the period of maternal care (spring to autumn) for 77 female roe deer (Capreolus capreolus) at Trois-Fontaines, Champagne-Ardenne, France (1976-2000). We maintained population growth rate (adjusted to account for removals of non-focal animals) near rmax, which enabled us to define the fitness-habitat relationship in the absence of density effects. Using a negative binomial model, we showed that a roe deer's incorporation into its home range of habitat components important to food, cover, and edge (meadows, thickets, and increased density of road allowances) was significantly related to LRS. Further, LRS decreased with increasing age of naturally reclaimed meadows at the time of a deer's birth, which may have reflected a cohort effect related to, but not entirely explained by, a decline in quality of meadows through time. Predictive capacity of the selected model, estimated as the median correlation (rs) between predicted and observed LRS among deer of cross-validation samples, was 0.55. The strength of this relationship suggests that processes like selection of the site of a home range during dispersal may play a more important role in determining fitness of individuals than previously thought. Individual fitness of highly sedentary income breeders with high reproductive output such as roe deer should be more dependent on home range quality during the period of maternal care compared to capital breeders with low reproductive output. Identification of the most important habitat attributes to survival and reproduction at low density (low levels of intraspecific competition) may prove useful for defining habitat value ("intrinsic habitat value").     

Characterization of spatial and temporal patterns in surface water quality: a case study of four major Lebanese rivers

In this work, four major Lebanese rivers were investigated, the Damour, Ibrahim, Kadisha, and Orontes, which are located in South, Central, and North Lebanon and Bekaa Valley, respectively. Five sampling sites were considered from upstream to downstream, and 12 sampling campaigns over four seasons were conducted during 2010–2011. Thirty-seven physicochemical parameters and five microbial tests were evaluated. A principal component analysis (PCA) was used for data evaluation. The first PCA, applied to the matrix-containing data that was acquired on all four rivers, showed that each river was distinct in terms of trophic state and pollution sources. The Ibrahim River was more likely to be polluted with industrial and human discharges, while the Kadisha River was severely polluted with anthropogenic human wastes. The Orontes and Damour rivers seemed to have the lowest rates of water pollution, especially the Orontes, which had the best water quality. PCA was also performed on individual data matrices for each river. In all cases, the results showed that the springs of each river have good water quality and are free from severe contamination. The other monitoring sites on each river were likely exposed to human activities and showed important spatial evolution. Through this work, a spatiotemporal fingerprint was obtained for each studied river, defining a “water mass reference” for each one. This model could be used as a monitoring tool for subsequent water quality surveys to highlight any temporal evolution of water quality.

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Evolution of biodegradation of deinking by-products used as alternative cover material

Deinking by-products (DBP) have been used as alternative cover material for landfills and mine tailings. Since DBP is biodegradable because of its high cellulose and hemicellulose content, a laboratory experimental program was performed to monitor the evolution of biodegradation and changes in the physico-chemical and geotechnical properties of DBP samples submitted to accelerated biodegradation for 1460 days at 38 degrees C. The evolution of gas and leachate production was monitored in terms of both quality and quantity, which allowed for the calculation of mass loss with time. Under the conditions of the tests (no load applied), 19.6% of the mass was lost as gas, whereas 6.1% was leached out. The results show that biodegradation did not significantly alter the compaction behavior of DBP. The void ratio and water content increased significantly, while the volume of the samples slightly decreased. This seem to indicate that the porous structure of the samples was no longer the same after 1460 d of accelerated biodegradation. A slight increase in the relative density indicates that the organic/inorganic matter ratio increased. The results of permeability tests performed with samples at various stages of biodegradation and at various confining stresses show that the saturated hydraulic conductivity of recompacted biodegraded DBP decreased from 7 x 10(-7)cm/s to approximately 2 x 10(-7)cm/s, as biodegradation advanced.     

Modeling the stream water nitrate dynamics in a 60,000-km2 European catchment, the Garonne, southwest France

The spatial and temporal dynamics in the stream water NO(3)-N concentrations in a major European river-system, the Garonne (62,700 km(2)), are described and related to variations in climate, land management, and effluent point-sources using multivariate statistics. Building on this, the Hydrologiska Byr?ns Vattenbalansavdelning (HBV) rainfall-runoff model and the Integrated Catchment Model of Nitrogen (INCA-N) are applied to simulate the observed flow and N dynamics. This is done to help us to understand which factors and processes control the flow and N dynamics in different climate zones and to assess the relative inputs from diffuse and point sources across the catchment. This is the first application of the linked HBV and INCA-N models to a major European river system commensurate with the largest basins to be managed under the Water Framework Directive. The simulations suggest that in the lowlands, seasonal patterns in the stream water NO(3)-N concentrations emerge and are dominated by diffuse agricultural inputs, with an estimated 75% of the river load in the lowlands derived from arable farming. The results confirm earlier European catchment studies. Namely, current semi-distributed catchment-scale dynamic models, which integrate variations in land cover, climate, and a simple representation of the terrestrial and in-stream N cycle, are able to simulate seasonal NO(3)-N patterns at large spatial (>300 km(2)) and temporal (> or = monthly) scales using available national datasets.