The effect of light and iron(II)/iron(III) on the distribution of Tl(I)/Tl(III) in fresh water systems

The distribution of aqueous Tl(I)/Tl(III) as a function of light exposure and solution properties was studied by quantifying the oxidation states after separation with ion chromatography and on-line detection with ICP-MS. Ultraviolet irradiation of aqueous solutions containing 1 microg l(-1) Tl(III) and in equilibrium with the atmosphere increases the reduction rate. In systems with photoreduction of Fe(III)(aq) a quantitative oxidation of Tl(I)(aq) was observed, notably at low pH. The process is reversible, as indicated by formation of Tl(I) when the irradiated systems were kept in the dark. In systems with colloidal silica-stabilised ferrihydrite, UV irradiation also leads to oxidation of Tl(I)(aq), but not quantitatively. It is suggested that adsorption of thallium to the ferrihydrite determines the rate of oxidation. Detectable, but not quantitative, oxidation of Tl(I)(aq) took place when natural water samples with 1 microg l(-1) Tl(I)(aq) were exposed to either sunlight or UV-light. For these samples, the reduction was not quantitative when they were kept in the dark for 24 h. The results suggest that the light dependent iron cycle in fresh water systems strongly influences the redox state of thallium.     

The influence on the radioxenon background during the temporary suspension of operations of three major medical isotope production facilities in the Northern Hemisphere and during the start-up of another facility in the Southern Hemisphere

Medical isotope production facilities (MIPF) have recently been identified to emit the major part of the environmental radioxenon measured at many globally distributed monitoring sites deployed to strengthen the radionuclide component of the Comprehensive Nuclear-Test-Ban Treaty (CTBT) verification regime. Efforts to raise a global radioxenon emission inventory revealed that the yearly global total emission from MIPF’s is around 15 times higher than the total radioxenon emission from nuclear power plants (NPP's).Given that situation, from mid 2008 until early 2009 two out of the ordinary hemisphere-specific events occured:1) In the Northern hemisphere, a joint temporary suspension of operations of the three largest MIPF's made it possible to quantify the effects of the emissions related to NPP’s. The average activity concentrations of ¹³³Xe measured at a monitoring station close to Freiburg, Germany, went down significantly from 4.5 ± 0.5 mBq/m³ to 1.1 ± 0.1 mBq/m³ and in Stockholm, Sweden, from 2.0 ± 0.4 mBq/m³ to 1.05 ± 0.15 mBq/m³.2) In the Southern hemisphere the only radioxenon-emitting MIPF in Australia started up test production in late November 2008. During eight test runs, up to 6.2 ± 0.2 mBq/m³ of ¹³³Xe was measured at the station in Melbourne, 700 km south-west from the facility, where no radioxenon had been observed before, originating from the isotopic production process.This paper clearly confirms the hypothesis that medical isotope production facility are at present the major emitters of radioxenon to the atmosphere. Suspension of operations of these facilities indicates the scale of their normal contribution to the European radioxenon background, which decreased two to four fold. This also gives a unique opportunity to detect and investigate the influence of other local and long distance sources on the radioxenon background. Finally the opposing effect was studied: the contribution of the start-up of a renewed radiopharmaceutical facility to the build up of a radioxenon background across Australia and the Southern hemisphere.     

Chemical-looping with oxygen uncoupling for combustion of solid fuels

Chemical-looping with oxygen uncoupling (CLOU) is a novel method to burn solid fuels in gas-phase oxygen without the need for an energy intensive air separation unit. The carbon dioxide from the combustion is inherently separated from the rest of the flue gases. CLOU is based on chemical-looping combustion (CLC) and involves three steps in two reactors, one air reactor where a metal oxide captures oxygen from the combustion air (step 1), and a fuel reactor where the metal oxide releases oxygen in the gas-phase (step 2) and where this gas-phase oxygen reacts with a fuel (step 3). In other proposed schemes for using chemical-looping combustion of solid fuels there is a need for an intermediate gasification step of the char with steam or carbon dioxide to form reactive gaseous compounds which then react with the oxygen carrier particles. The gasification of char with H₂O and CO₂ is inherently slow, resulting in slow overall rates of reaction. This slow gasification is avoided in the proposed process, since there is no intermediate gasification step needed and the char reacts directly with gas-phase oxygen. The process demands an oxygen carrier which has the ability to react with the oxygen in the combustion air in the air reactor but which decomposes to a reduced metal oxide and gas-phase oxygen in the fuel reactor. Three metal oxide systems with suitable thermodynamic properties have been identified, and a thermal analysis has shown that Mn₂O₃/Mn₃O₄ and CuO/Cu₂O have suitable thermodynamic properties, although Co₃O₄/CoO may also be a possibility. However, the latter system has the disadvantage of an overall endothermic reaction in the fuel reactor. Results from batch laboratory fluidized bed tests with CuO and a gaseous and solid fuel are presented. The reaction rate of petroleum coke is approximately a factor 50 higher using CLOU in comparison to the reaction rate of the same fuel with an iron-based oxygen carrier in normal CLC.     

PFAS profiles in three North Sea top predators: metabolic differences among species?

Profiles of seven compounds of perfluoro-alkyl substances (PFASs) were compared among three species of top predators from the Danish North Sea: the white-beaked dolphin (Lagenorhynchus albirostris), the harbor porpoise (Phocoena phocoena), and the harbor seal (Phoca vitulina). The seals had higher total burdens (757.8 ng g^?1 ww) than the dolphins (439.9 ng g^?1 ww) and the porpoises (355.8 ng g^?1 ww), probably a reflection of feeding closer to the shore and thus contamination sources. The most striking difference among the species was the relative contribution of perfluorooctanesulfonamide (PFOSA) to the profiles; the seals (0.1 %) had much lower levels than porpoises (8.3 %) and dolphins (26.0 %). In combination with the values obtained from the literature, this result indicates that Carnivora species including Pinnipedia have a much higher capacity of transforming PFOSA to perfluorooctane sulfonic acid (PFOS) than cetacean species. Another notable difference among the species was that the two smaller species (seals and porpoises) with supposedly higher metabolic rates had lower concentrations of the perfluorinated carboxylic acids, which are generally more easily excreted than perfluorinated sulfonamides. Species-specific characteristics should be recognized when PFAS contamination in marine mammals is investigated, for example, several previous studies of PFASs in cetaceans have not quantified PFOSA.     

Gas production, composition and emission at a modern disposal site receiving waste with a low-organic content

AV Miljø is a modern waste disposal site receiving non-combustible waste with a low-organic content. The objective of the current project was to determine the gas generation, composition, emission, and oxidation in top covers on selected waste cells as well as the total methane (CH₄) emission from the disposal site. The investigations focused particularly on three waste disposal cells containing shredder waste (cell 1.5.1), mixed industrial waste (cell 2.2.2), and mixed combustible waste (cell 1.3). Laboratory waste incubation experiments as well as gas modeling showed that significant gas generation was occurring in all three cells. Field analysis showed that the gas generated in the cell with mixed combustible waste consisted of mainly CH₄ (70%) and carbon dioxide (CO₂) (29%) whereas the gas generated within the shredder waste, primarily consisted of CH₄ (27%) and nitrogen (N₂) (71%), containing no CO₂. The results indicated that the gas composition in the shredder waste was governed by chemical reactions as well as microbial reactions. CH₄ mass balances from three individual waste cells showed that a significant part (between 15% and 67%) of the CH₄ generated in cell 1.3 and 2.2.2 was emitted through leachate collection wells, as a result of the relatively impermeable covers in place at these two cells preventing vertical migration of the gas. At cell 1.5.1, which is un-covered, the CH₄ emission through the leachate system was low due to the high gas permeability of the shredder waste. Instead the gas was emitted through the waste resulting in some hotspot observations on the shredder surface with higher emission rates. The remaining gas that was not emitted through surfaces or the leachate collection system could potentially be oxidized as the measured oxidation capacity exceeded the potential emission rate. The whole CH₄ emission from the disposal site was found to be 820 ± 202 kg CH₄ d⁻¹. The total emission rate through the leachate collection system at AV Miljø was found to be 211 kg CH₄ d⁻¹. This showed that approximately ¼ of the emitted gas was emitted through the leachate collections system making the leachate collection system an important source controlling the overall gas migration from the site. The emission pathway for the remaining part of the gas was more uncertain, but emission from open cells where waste is being disposed of or being excavated for incineration, or from horizontal leachate drainage pipes placed in permeable gravel layers in the bottom of empty cells was likely.     

Using raptors as environmental sentinels: monitoring the white-tailed sea eagle Haliaeetus albicilla in Sweden

This paper summarizes results from the monitoring of reproduction of white-tailed sea eagle in Sweden 1965-2006. Since 1989 the eagle population on the Swedish Baltic coast has been included in the National Environment Monitoring Program as an indicator species for potentially harmful chemicals. The percentage of successfully reproducing pairs and nestling brood size decreased in synchrony with rising concentrations of contaminants in the 1950s on into the 1970s. Mean productivity was 1.3 young per pair prior to 1950 and decreased to 0.3 in 1965-1985. Dichlorodiphenyldichloroethene (DDE) in eagle eggs decreased from a range of annual means in 1965-1974 of 600-1200 microg g(-1) (lipid weight) to 60-140 microg g(-1) in 1996-2005. Total polychlorinated biphenyl (PCB) concentrations averaged above 1000 microg g(-1) into the early 1980s and remained in the range of 250-500 microg g(-1) in 1996-2005. Productivity began to improve when concentrations of DDE and PCBs dropped below approximately 300 and 800 microg g(-1), respectively. Brood size remains below the pre-1950 level in one coastal region, indicating a possible impact from other contaminants. The power to detect significant trends under the program is presented and discussed: if white-tailed sea eagle reproduction had been monitored earlier during the 20th century, the negative impact of dichlorodiphenyltrichloroethane (DDT, source of DDE) would have been signaled as early as the 1950s in the Baltic Sea. The dramatic fall of white-tailed sea eagle reproduction under the influence of DDT and PCBs, and the subsequent rise following their ban, illustrates the usefulness of raptors like sea eagles as sentinels for environmental pollutants.     

Associations of variable coloration with niche breadth and conservation status among Australian reptiles

We evaluate predictions concerning the evolutionary and ecological consequences of color polymorphisms. Previous endeavors have aimed at identifying conditions that promote the evolution and maintenance within populations of alternative variants. But the polymorphic condition may also influence important population processes. We consider the prediction that populations that consist of alternative "ecomorphs" with coadapted gene complexes will utilize more diverse resources and display higher rates of colonization success, population persistence, and range expansions, while being less vulnerable to range contractions and extinctions, compared with monomorphic populations. We perform pairwise comparative analyses based on information for 323 species of Australian lizards and snakes. We find that species with variable color patterns have larger ranges, utilize a greater diversity of habitat types, and are underrepresented among species currently listed as threatened. These results are consistent with the proposition that the co-occurrence of multiple color variants may promote the ecological success of populations and species, but there are also alternative interpretations.     

Flight distance of urban birds, predation, and selection for urban life

Numerous species have adapted to humans, especially invasive species associated with humans in towns and cities. Short flight distances of populations adapted to urban environments reflect changes in behavior and physiology, reflecting phenotypic plasticity or evolution. Here, I tested the hypothesis that the decrease in flight distance to a potential predator (an approaching human) reflected adaptation to urbanization, using a data set of flight distances of 44 common species of European birds in different stages of adaptation to urban environments. Urban populations had consistently shorter flight distances than rural populations of the same species. Variation in relative flight distance of urban populations was predicted by the number of generations since urbanization, as expected by a gradual process of adaptation. Furthermore, species with relatively large populations in urban environments would be an indication of local adaptation to urban environments. Relative flight distance of urban population was shorter for species with large populations in urban compared to rural habitats. Species that had adapted to urban environments as shown by short flight distances were less susceptible to predation by the European sparrowhawk Accipiter nisus than species with relatively long flight distances in urban populations. These findings provide evidence consistent with the hypothesis that recent changes in the tameness of urban birds, as reflected by their relatively short flight distances, is an adaptation to the novel urban environment. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Temporal and spatial trends of PCBs,DDTs, HCHs,and HCB in Swedish marine biota 1969–2012

In the 1960s, the Baltic Sea was severely polluted by organic contaminants such as PCBs, HCHs, HCB, and DDTs. Elevated concentrations caused severe adverse effects in Baltic biota. Since then, these substances have been monitored temporally and spatially in Baltic biota, primarily in herring (Clupea harengus) and in guillemot (Uria aalge) egg, but also in cod (Gadus morhua), perch (Perca fluviatilis), eelpout (Zoarces viviparous), and blue mussel (Mytilus edulis). These chemicals were banned in Sweden in the late 1970s/early 1980s. Since the start of monitoring, overall significant decreases of about 70–90 % have been observed. However, concentrations are still higher in the Baltic Sea than in, for example, the North Sea. CB-118 and DDE exceed the suggested target concentrations (24 µg kg^?1 lipid weight and 5 µg kg^?1 wet weight, respectively) at certain sites in some of the monitored species, showing that concentrations may still be too high to protect the most sensitive organisms.