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.     

Decreasing lead levels in Swedish biota revealed by 36 years (1969-2004) of environmental monitoring

Since the 1980s, lead levels decreased significantly in most marine biota from the Baltic Sea, the Kattegatt and the Skagerrack and in terrestrial biota from south and central Sweden, analysed in the National Swedish Environmental Monitoring Programme. In herring and cod liver, the decrease was 4.2-7.1% annually 1981-2003 and in perch liver and guillemot eggs analysed since the middle of the 1990s the decrease was 10-13%. In kidneys of young starlings from south and central Sweden, lead levels decreased 6.2-12% annually and the annual decrease in liver and kidney from young moose was 8.8% and 6.5%, respectively. In northern Sweden, lead levels decreased in pike liver by 2.8% between 1969 and 1994 and in reindeer liver by 3.5% annually while a significant increase (5% annually 1981-1994) has been detected in arctic char. In some marine biota, there were indications of a larger decrease during the last ten years compared to the whole period. The large decline in lead emission to the atmosphere during the last twenty years, mainly because of decreasing use of leaded gasoline has obviously resulted in decreasing lead levels in biota.     

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.     

Levels and homologue profiles of PCDD/Fs in sediments along the Swedish coast of the Baltic Sea

Background, aim, and scope  The primary aim of this study was to explore the variations in PCDD/F levels and homologue profiles of Baltic surface sediments by comprehensively analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in samples from a large number of sites, encompassing not only previously known hotspot areas, but also sites near other potential PCDD/F sources, in pristine reference areas (in which there was no industrial activity) and offshore sites. Materials and methods  Surface sediment samples (146 in total) were collected at various points along the Swedish coast and offshore areas. In addition, bulk deposition was sampled, monthly, at a single site in northern Sweden during 1 year. The concentrations of tetra- through octa-substituted CDD/Fs were determined in both matrices. Results  Highly elevated concentrations of PCDD/Fs were found at many sites in coastal areas and concentrations were also slightly elevated in some offshore areas. Homologue profiles varied substantially amongst samples from coastal sites, while those from offshore and other pristine sediments were relatively similar. The offshore sediments showed different profiles from those observed in the deposition samples. Sediment levels of PCDD/Fs were not generally significantly correlated to organic carbon levels, except in some pristine areas. Comparison of data obtained in this and previous studies suggest that both their levels and profiles are similar today to those observed 20 years ago in coastal and offshore areas. The only detected trend is that their levels appear to have decreased slightly in the offshore area of the Bothnian Sea. Discussion  The localization of hotspot areas along the coast, the lack of consensus between PCDD/F profiles of sediments and general background, and their weak correlations with organic carbon suggest that PCDD/Fs in the study area largely originate from local/regional emissions. However, due to complicating factors such as sediment dynamics and land upheaval, it is not possible to conclude whether these pollutants derive from recent emissions or from a combination of recent emissions and re-distribution of previous inputs. Conclusions  The results show that: elevated levels of PCDD/Fs are present in both coastal and offshore areas of the Baltic Sea, the major hotspots are close to the shore, and there are large variations in profiles, indicating that local emissions are (or have been) the major causes of pollution. Recommendations and perspectives  In order to identify other hotspot areas and trace sources, comprehensive analysis of PCDD/Fs in surface sediments is needed in all areas of the Baltic Sea that have not been previously investigated. The high levels of PCDD/Fs observed in surface sediments also indicate a need to elucidate whether they are due mainly to current emissions or a combination of recent pollution and re-distribution of historically deposited pollutants. To do so, better understanding of sediment dynamics and present-day inputs, such as riverine inputs, industrial effluents, and leakage from contaminated soil is required. There are indications that contaminated sediments have a regional impact on fish contamination levels. However, as yet there is no statistically robust evidence linking contaminated sediments with elevated levels in Baltic biota. It should also be noted that the Baltic Sea is being massively invaded by the deep-burrowing polychaete Marenzielleria ssp., whose presence in sediments has been shown to increase water concentrations of hydrophobic pollutants. In awareness of this, it is clear that high levels in sediments cannot be ignored in risk assessments. In order to investigate the emission trends more thoroughly, analysis of PCDD/Fs in offshore sediment cores throughout the Baltic Sea is also recommended. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Temporal pessimism and spatial optimism in environmental assessments: An 18-nation study

The personal assessments of the current and expected future state of the environment by 3232 community respondents in 18 nations were investigated at the local, national, and global spatial levels. These assessments were compared to a ranking of each country's environmental quality by an expert panel. Temporal pessimism (“things will get worse”) was found in the assessments at all three spatial levels. Spatial optimism bias (“things are better here than there”) was found in the assessments of current environmental conditions in 15 of 18 countries, but not in the assessments of the future. All countries except one exhibited temporal pessimism, but significant differences between them were common. Evaluations of current environmental conditions also differed by country. Citizens' assessments of current conditions, and the degree of comparative optimism, were strongly correlated with the expert panel's assessments of national environmental quality. Aside from the value of understanding global trends in environmental assessments, the results have important implications for environmental policy and risk management strategies.     

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.     

Emissions from simulated deep-seated fires in domestic waste

The emissions from deep-seated fires in domestic waste have been investigated. The gas phase yields of PAH, PCDD/F, PCB, HCB, particles, and metals associated to the particulate matter were analysed during a series of simulated deep-seated fires. The method of extinguishment was varied and in cases where water was used for extinguishment, the runoff water was analysed for PAH, PCDD/F, PCB, hexachlorobenzene, and metals. In total six tests were performed. In four of the tests, samples of the fire residue were analysed for PCDD/F, PCBs, and chlorobenzenes.     

Estrogenicity profile and estrogenic compounds determined in river sediments by chemical analysis, ELISA and yeast assays

An effects-directed strategy was applied to bed sediments of a polluted tributary in order to isolate and identify the major estrogenic chemicals it discharges into the River Po, the principal Italian watercourse. Sediment extract was concentrated by solid phase extraction and then fractioned into 10 fractions by reversed phase high performance liquid chromatography (RP-HPLC). Estrogenic activity of whole extract and fractions were determined using a recombinant yeast assay containing the human estrogen receptor (YES). The 10 fractions and whole extract were analysed for target compounds, e.g. estrone (E1), 17beta-estradiol (E2), estriol (E3), 4-nonylphenol (NP), 4-tert-octylphenol (t-OP), bisphenol A (BPA), using both liquid chromatography-tandem mass spectrometry (LC-MS/MS) and non-competitive enzyme-linked immunosorbent assays (ELISA). The YES assay determined high estrogenic activity in whole sediment (15.6 ng/g EE2 equivalents), and positive results for fractions nr 1, 2, 6, 7 and 8. E1, E3 and NP were the main estrogenic chemicals, however, other unidentified compounds contributed to sediment estrogenicity, particularly for polar fractions nr 1 and 2. A GC-MS screening performed in scan mode identified other potential contributors such as phthalates (DBP, BBP), and OP isomers. A next sampling campaign extended to other tributaries and receiving stretches of the River Po confirmed E1, E3 and NP as major estrogenic chemicals potentially threatening other sites of the main river. In general, target compound ELISAs have been shown to be suitable tools for a rapid screening of wide areas or large numbers of environmental samples for estrogenic risk. The potential for interferences suggests however to use cautiously the concentration values obtained from some of the immunoassays.     

Spatial variation in concentrations and patterns of the PCDD/F and dioxin-like-PCB content in herring from the northern Baltic Sea

The purpose of the current study was to investigate spatial and seasonal variation of dioxin and dioxin-like PCB (dl-PCB) content in herring sampled along the northern Baltic Sea coast and map out risk zones for dioxins and dl-PCBs. We further aimed to investigate relationships between congener distribution (pattern) and sampling location and season. The results showed that there were distinct geographical differences in concentrations of dioxins, dibenzofurans and dl-PCBs along the Swedish coast, from the Bothnian Bay to north Baltic Proper, with the highest levels detected in the southern Bothnian Sea. The majority of the locations showed concentrations above the prescribed maximum for dioxin residues (4 TEQ pg g(-1) wet weight [w.w.]). If all the edible parts of the fish (muscle, subcutaneous fat and skin) are considered, the estimated concentrations exceeded the prescribed maximum level in the whole study area for herring collected during spring-summer. Concentrations in herring caught during spring-summer compared to concentrations in herring sampled in the autumn indicated seasonal variation. The pattern analysis showed a variation in relative congener concentration at the different sampling locations (spring-summer). Pattern differences were also noticed between seasons.