Equilibrium Sampling to Determine the Thermodynamic Potential for Bioaccumulation of Persistent Organic Pollutants from Sediment
Equilibrium partitioning (EqP) theory is currently the most widely used approach for linking sediment pollution by persistent hydrophobic organic chemicals to bioaccumulation. Most applications of the EqP approach assume (I) a generic relationship between organic carbon-normalized chemical concentrations in sediments and lipid-normalized concentrations in biota and (II) that bioaccumulation does not induce levels exceeding those expected from equilibrium partitioning. Here, we demonstrate that assumption I can be obviated by equilibrating a silicone sampler with chemicals in sediment, measuring chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic pollutants (polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB)) to lipid-normalized concentrations for a range of biota from a Swedish background lake. PCBs in duck mussels, roach, eel, pikeperch, perch and pike were mostly below the equilibrium partitioning level relative to the sediment, i.e., lipid-normalized concentrations were ≤CLip⇌Sed, whereas HCB was near equilibrium between biota and sediment. Equilibrium sampling allows straightforward, sensitive and precise measurement of CLip⇌Sed. We propose CLip⇌Sed as a metric of the thermodynamic potential for bioaccumulation of persistent organic chemicals from sediment useful to prioritize management actions to remediate contaminated sites.
Effects of sources and meteorology on particulate matter in the Western Mediterranean Basin: An overview of the DAURE campaign
Preferential burial of permafrost-derived organic carbon in Siberian-Arctic shelf waters
The rapidly changing East Siberian Arctic Shelf (ESAS) receives large amounts of terrestrial organic carbon (OC) from coastal erosion and Russian-Arctic rivers. Climate warming increases thawing of coastal Ice Complex Deposits (ICD) and can change both the amount of released OC, as well as its propensity to be converted to greenhouse gases (fueling further global warming) or to be buried in coastal sediments. This study aimed to unravel the susceptibility to degradation, and transport and dispersal patterns of OC delivered to the ESAS. Bulk and molecular radiocarbon analyses on surface particulate matter (PM), sinking PM and underlying surface sediments illustrate the active release of old OC from coastal permafrost. Molecular tracers for recalcitrant soil OC showed ages of 3.4-13 C-14-ky in surface PM and 5.5-18 C-14-ky in surface sediments. The age difference of these markers between surface PM and surface sediments is larger (i) in regions with low OC accumulation rates, suggesting a weaker exchange between water column and sediments, and (ii) with increasing distance from the Lena River, suggesting preferential settling of fluvially derived old OC nearshore. A dual-carbon end-member mixing model showed that (i) contemporary terrestrial OC is dispersed mainly by horizontal transport while being subject to active degradation, (ii) marine OC is most affected by vertical transport and also actively degraded in the water column, and (iii) OC from ICD settles rapidly and dominates surface sediments. Preferential burial of ICD-OC released into ESAS coastal waters might therefore lower the suggested carbon cycle climate feedback from thawing ICD permafrost.
Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension
The water vapor interface of aqueous solutions of succinic acid, where pH values and bulk concentrations were varied, has been studied using surface sensitive X-ray photoelectron spectroscopy (XPS) and molecular dynamics (MD) simulations. It was found that succinic acid has a considerably higher propensity to reside in the aqueous surface region than its deprotonated form, which is effectively depleted from the surface due to the two strongly hydrated carboxylate groups. From both XPS experiments and MD simulations a strongly increased concentration of the acid form in the surface region compared to the bulk concentration was found and quantified. Detailed analysis of the surface of succinic acid solutions at different bulk concentrations led to the conclusion that succinic acid saturates the aqueous surface at high bulk concentrations. With the aid of MD simulations the thickness of the surface layer could be estimated, which enabled the quantification of surface concentration of succinic acid as a multiple of the known bulk concentration. The obtained enrichment factors were successfully used to model the surface tension of these binary aqueous solutions using two different models that account for the surface enrichment. This underlines the close correlation of increased concentration at the surface relative to the bulk and reduced surface tension of aqueous solutions of succinic acid. The results of this study shed light on the microscopic origin of surface tension, a macroscopic property. Furthermore, the impact of the results from this study on atmospheric modeling is discussed.
Separation and identification of lipid classes by normal phase LC-ESI/MS/MS on a cyanopropyl column
In order to establish a versatile and convenient method for the analysis of lipids, electrospray ionization tandem mass spectrometry (ESI-MS/MS) was applied to a HPLC separation on a cyanopropyl-bonded stationary phase. A binary gradient mobile phase system consisting of hexane, toluene, methanol and a stable electrospray yielding sodium adduct ions could be used to generate specific product ions in MS/MS mode. By applying the LC/ESI-MS/MS method on an egg yolk sample, 29 different molecular species of phosphatidylethanolamines, phosphatidylcholines, and lysophosphatidylcholines could be detected within 25 min.
Sucralose Induces Biochemical Responses in Daphnia magna
The intense artificial sweetener sucralose has no bioconcentration properties, and no adverse acute toxic effects have been observed in standard ecotoxicity tests, suggesting negligible environmental risk. However, significant feeding and behavioural alterations have been reported in non-standard tests using aquatic crustaceans, indicating possible sublethal effects. We hypothesized that these effects are related to alterations in acetylcholinesterase (AChE) and oxidative status in the exposed animals and investigated changes in AChE and oxidative biomarkers (oxygen radical absorbing capacity, ORAC, and lipid peroxidation, TBARS) in the crustacean Daphnia magna exposed to sucralose (0.0001–5 mg L−1). The sucralose concentration was a significant positive predictor for ORAC, TBARS and AChE in the daphnids. Moreover, the AChE response was linked to both oxidative biomarkers, with positive and negative relationships for TBARS and ORAC, respectively. These joint responses support our hypothesis and suggest that exposure to sucralose may induce neurological and oxidative mechanisms with potentially important consequences for animal behaviour and physiology.
Feeding of the Arctic ctenophore Mertensia ovum in the Baltic Sea: evidence of the use of microbial prey
Since its first reported appearance in the Baltic Sea in 2007, there has been a little research on the role of the Arctic ctenophore Mertensia ovum in this ecosystem. We provide results from the first feeding experiments of M. ovum from the northern Baltic Sea. Experiments were conducted with various prey types; picocyanobacteria Synechococcus bacillaris, ciliates Mesodinium rubrum, nauplii of mixed copepod species and copepodites of Eurytemora affinis. Molecular gut content analyses were also used to measure in situ feeding of M. ovum on the picocyanobacteria. The observed clearance rates on M. rubrum (< 9.0 mL predator(-1) h(-1)), and S. bacillaris (<7.5 mL predator(-1) h(-1)) were lower than those reported for similar-sized ctenophore species feeding on similar prey. Similarly, clearance rates of M. ovum on copepodites and copepod nauplii were close to zero, implying significantly lower predation on crustacean prey compared with other ctenophores. Overall, M. ovum predation rates were relatively low with a maximum daily consumption of 0.95 mu g C ind.(-1) day(-1) (similar to 15.8% of estimated predator carbon content). In addition, we examined the vertical distribution of M. ovum in relation to that of micro- and mesozooplankton and found greater overlap with potential microplankton prey than with mesozooplankton. Taken together, these results imply that in the Baltic Sea, M. ovum feed mainly on bacterio-and microplankton, thus potentially contributing to the coupling between the microbial loop and higher consumers in the pelagic food web.
Hygroscopicity, CCN and volatility properties of submicron atmospheric aerosol in a boreal forest environment during the summer of 2010
A Volatility-Hygroscopicity Tandem Differential Mobility Analyzer (VH-TDMA) was applied to study the hygroscopicity and volatility properties of submicron atmospheric aerosol particles in a boreal forest environment in Hyytiala, Finland during the summer of 2010. Aitken and accumulation mode internally mixed particles (50 nm, 75 nm and 110 nm in diameter) were investigated. Hygroscopicity was found to increase with particle size. The relative mass fraction of organics and SO42- is probably the major contributor to the fluctuation of the hygroscopicity for all particle sizes. The Cloud Condensation Nuclei Counter (CCNC)-derived hygroscopicity parameter kappa was observed to be slightly higher than kappa calculated from VH-TDMA data under sub-saturated conditions, potential reasons for this behavior are discussed shortly. Also, the size-resolved volatility properties of particles were investigated. Upon heating, more small particles evaporated compared to large particles. There was a significant amount of aerosol volume (non-volatile material) left, even at heating temperatures of 280 degrees C. Using size resolved volatility-hygroscopicity analysis, we concluded that there was always hygroscopic material remaining in the particles at different heating temperatures, even at 280 degrees C. This indicates that the observed non-volatile aerosol material did not consist solely of black carbon.
Distinctive metabolite profiles in in-migrating Sockeye salmon suggest sex-linked endocrine perturbation
The health of Skeena River Sockeye salmon (Onchorhychus nerka) has been of increasing concern due to declining stock returns over the past decade. In the present work, in-migrating Sockeye from the 2008 run were evaluated using a mass spectrometry-based, targeted metabolomics platform. Our objectives were to (a) investigate natural changes in a subset of the hepatic metabolome arising from migration-associated changes in osmoregulation, locomotion, and gametogenesis, and (b) compare the resultant profiles with animals displaying altered hepatic vitellogenin A (vtg) expression at the spawning grounds, which was previously hypothesized as a marker of xenobiotic exposure. Of 203 metabolites monitored, 95 were consistently observed in Sockeye salmon livers and over half of these changed significantly during in-migration. Among the most dramatic changes in both sexes were a decrease in concentrations of taurine (a major organic osmolyte), carnitine (involved in fatty acid transport), and two major polyunsaturated fatty acids (eicosapentaenoic acid and docosahexaenoic acid). In females, an increase in amino acids was attributed to protein catabolism associated with vitellogenesis. Animals with atypical vtg mRNA expression demonstrated unusual hepatic amino acid, fatty acid, taurine, and carnitine profiles. The cause of these molecular perturbations remains unclear, but may include xenobiotic exposure, natural senescence, and/or interindividual variability. These data provide a benchmark for further investigation into the long-term health of migrating Skeena Sockeye.