Solid fuels in chemical-looping combustion

The feasibility of using a number of different solid fuels in chemical-looping combustion (CLC) has been investigated. A laboratory fluidized bed reactor system for solid fuel, simulating a chemical-looping combustion system by exposing the sample to alternating reducing and oxidizing conditions, was used. In each reducing phase 0.2 g of fuel in the size range 180–250 μm was added to the reactor containing 40 g oxygen carrier of size 125–180 μm. Two different oxygen carriers were tested, a synthetic particle of 60% active material of Fe₂O₃ and 40% MgAl₂O₄ and a particle consisting of the natural mineral ilmenite. Effect of steam content in the fluidizing gas of the reactor was investigated as well as effect of temperature. A number of experiments were also made to investigate the rate of conversion of the different fuels in a CLC system. A high dependency on steam content in the fluidizing gas as well as temperature was shown. The fraction of volatiles in the fuel was also found to be important. Furthermore the presence of an oxygen carrier was shown to enhance the conversion rate of the intermediate gasification reaction. At 950 °C and with 50% steam the time needed to achieve 95% conversion of fuel particles with a diameter of 0.125–0.18 mm ranged between 4 and 15 min depending on the fuel, while 80% conversion was reached within 2–10 min. In almost all cases the synthetic Fe₂O₃ particle with 40% MgAl₂O₄ and the mineral ilmenite showed similar results with the different fuels.     

Acid mine drainage in the Iberian Pyrite Belt: 2. Lessons learned from recent passive remediation experiences

The Iberian Pyrite Belt (IPB), SW Spain and Portugal, contains about 100 abandoned mine wastes and galleries that release acid mine drainages (AMD) to the Tinto and Odiel rivers. In situ passive remediation technologies are especially suitable to remediate the drainages of these orphan sites. However, traditional remediation systems, designed for coal mines, have been demonstrated inefficient to treat the IPB mine waters. Due to their high acidity and metal loads, large amount of solids precipitate and fast clogging of porosity or passivation (coating) of the reactive grains occurs. To overcome these problems, the dispersed alkaline substrate (DAS) a mixture of fine-grained limestone sand and a coarse inert matrix (e.g., wood shavings) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate. The high porosity retards clogging. However, calcite dissolution only raises pH to values around 6.5, at which the hydroxides of trivalent metals (Al and Fe) precipitate, but it is not high enough to remove divalent metals. Caustic magnesia (MgO) buffers the solution pH between 8.5 and 10. A DAS system replacing limestone with caustic magnesia has been tested to be very efficient to remove divalent metals (Zn, Cd, Mn, Cu, Co, Ni, and Pb) from the water previously treated with calcite.     

Identification of a phytotoxic photo-transformation product of diclofenac using effect-directed analysis

The pharmaceutical diclofenac (DCF) is released in considerably high amounts to the aquatic environment. Photo-transformation of DCF was reported as the main degradation pathway in surface waters and was found to produce metabolites with enhanced toxicity to the green algae Scenedesmus vacuolatus. We identified and subsequently confirmed 2-[2-(chlorophenyl)amino]benzaldehyde (CPAB) as a transformation product with enhanced toxicity using effect-directed analysis. The EC₅₀ of CPAB (4.8 mg/L) was a factor of 10 lower than that for DCF (48.1 mg/L), due to the higher hydrophobicity of CPAB (log K_ow = 3.62) compared with DCF (log D_ow = 2.04) at pH 7.0.     

Large-scale spatial pollution patterns around the North Sea indicated by coastal bird eggs within an EcoQO programme

To categorize the marine environmental health status, the Oslo and Paris commissions have recently formulated Ecological Quality Objectives (EcoQOs) for many ecological features including the contamination of coastal bird eggs with mercury and organochlorines. In this study, we describe spatial and temporal patterns of egg contamination around the North Sea and compared them to the EcoQOs. Concentrations of mercury, polychlorinated biphenyl (??PCB) congeners, dichlorodiphenyltrichloroethane (??DDT) and derivatives, hexachlorobenzene (HCB) and hexachlorocyclohexane (??HCH) isomers were analysed in two tern species (Sterna hirundo and Sterna paradisaea) and Oystercatcher (Haematopus ostralegus) eggs collected between 2008 and 2010 in a total of 21 sites in seven countries surrounding the North Sea. Hg, ??PCB and HCB were highest in the southern sites, while ??DDT and ??HCH concentrations were greatest in eggs from the western North Sea and the Elbe estuary. There were rarely any consistent decreases over time for any compounds. In the terns, Hg, HCB and ??HCH increased at most sites, ??PCB and ??DDT in Sweden and Norway. In the Oystercatcher, HCB and ??HCH increased at more than the half of the sites, ??PCB, ??DDT and Hg at several German sites. In the terns, Hg, ??PCB and ??DDT exceeded the EcoQO in all, HCB in most years and sites. At most sites, ??HCH fulfilled the EcoQO in some study years. In the Oystercatcher, Hg, ??PCB and ??DDT exceeded the EcoQO in all or most years and sites. HCB and ??HCH fulfilled the EcoQO in some or all years at most sites. The EcoQO was exceeded most frequently in estuaries. We conclude that EcoQOs are suitable for drawing contamination patterns of the coastal North Sea in an easily understandable manner, offering the opportunity to harmonize the EcoQOs with coordinated environmental monitoring programmes.     

Long term remediation of highly polluted acid mine drainage: a sustainable approach to restore the environmental quality of the Odiel river basin

During 20 months of proper operation the full scale passive treatment in Mina Esperanza (SW Spain) produced around 100 mg/L of ferric iron in the aeration cascades, removing an average net acidity up to 1500 mg/L as CaCO₃ and not having any significant clogging problem. Complete Al, As, Cd, Cr, Cu, Ti and V removal from the water was accomplished through almost the entire operation time while Fe removal ranged between 170 and 620 mg/L. The system operated at a mean inflow rate of 43 m³/day achieving an acid load reduction of 597 g·(m² day)⁻¹, more than 10 times higher than the generally accepted 40 g·(m² day)⁻¹ value commonly used as a passive treatment system designing criteria. The high performance achieved by the passive treatment system at Mina Esperanza demonstrates that this innovative treatment design is a simple, efficient and long lasting remediation option to treat highly polluted acid mine drainage.     

Land-use legacies in the forest structure of silvopastoral oak woodlands in the Eastern Mediterranean

Eastern Mediterranean silvopastoral oak woodlands have been greatly damaged through forest conversion, illegal lumbering, overgrazing, and forest fires. The aim of this study was to assess land-use changes and the legacies that they have imprinted on the forest structure of Quercus macrolepis and accompanying Quercus pubescens and Quercus cerris woodlands on Lesvos Island, Greece. The size structures of adult oak populations were analyzed as indicators of long-term oak regeneration, while short-term recruitment was determined by counting oak seedlings and saplings. The size structure of the adult Q. macrolepis population was similar to the inverse J-shaped distribution typical for natural Mediterranean oak forests, indicating continuous recruitment with a constant mortality rate of mature individuals. Seedling and sapling densities were highly variable, but generally low in relation to adult oak densities. Recruitment of oak seedlings and saplings was positively related to determinants such as forest cover, adult oak density and basal area, woody plant richness, and litter cover. Both seedling and sapling occurrence were negatively associated with dung frequency, which suggests that sheep grazing imposes a barrier to oak recruitment. The study outlines a comprehensive land-use transition from the 1950 to 1970s, during which a complex and multifunctional agrosilvopastoral land-use system was simplified to an intensive grazing system. The discrepancy between the successful long-term regeneration and the less successful short-term recruitment of oaks illustrates that intensified livestock grazing has been a major driver of vegetation change. Grazing impact is likely to interact with increasing drought conditions, which may trigger a negative feedback cycle that undermines the capacity of woodlands to sustain ecosystem services.     

Determinants of exposure to mercury in hair from inhabitants of the largest mercury mine in the world

Mercury exposure of the local population was assessed in two areas of the Almadén mercury mining district, Spain, which has been the world’s largest producer of this element. Two groups, who are exposed to different sources of mercury, from a point source in Almadén and a diffuse source hundreds of kilometres away in the same region, were studied. Total mercury (THg) in human hair ranged from 0.20 to 9.35 mg kg⁻¹ and the mean value was 2.64 mg kg⁻¹. About 87% of subjects had THg levels in excess of the EPA reference dose (RfD = 1.0 mg kg⁻¹), while a high percentage (68%) of them live in Almadén. There was a clear increase in hair Hg with reported fish consumption and the highest mean hair mercury level was 4 times the RfD in a group who had reported the highest consumption of fish. For the whole group, there was a significant effect of age, gender and fish consumption in relation to Hg concentration in the hair. Nevertheless, when both groups were tested separately by means of a multivariate regression model, there was significant exposure in those living near the mine area. Several factors such as age, gender and fish consumption remained statistically significant and were associated with THg. The main conclusion is that people living close to the hot spot are more impacted by mercury than people living further away. The intake of Hg through consumption of fish is an important parameter for Hg exposure; however, in the case of people living close to the hot spot, their levels are related to the highly Hg-impacted living environment.     

A comparative assessment of land cover dynamics of three protected forest areas in tropical eastern Africa

Processes of deforestation, known to threaten tropical forest biodiversity, have not yet been studied sufficiently in East Africa. To shed light on the patterns and causes of human influences on protected forest ecosystems, comparisons of different study areas regarding land cover dynamics and potential drivers are needed. We analyze the development of land cover since the early 1970s for three protected East African rainforests and their surrounding farmlands and assess the relationship between the observed changes in the context of the protection status of the forests. Processing of Landsat satellite imagery of eight or seven time steps in regular intervals results in 12 land cover classes for the Kakamega–Nandi forests (Kenya) and Budongo Forest (Uganda) whereas ten are distinguished for Mabira Forest (Uganda). The overall classification accuracy assessed for the year 2001 or 2003 is similarly high for all three study areas (81% to 85%). The time series reveal that, despite their protection status, Kakamega–Nandi forests and Mabira Forest experienced major forest decrease, the first a continuous forest loss of 31% between 1972/1973 and 2001, the latter an abrupt loss of 24% in the late 1970s/early 1980s. For both forests, the temporally dense time series show short-term fluctuations in forest classes (e.g., areas of forest regrowth since the 1980s or exotic secondary bushland species from the 1990s onwards). Although selectively logged, Budongo Forest shows a much more stable forest cover extent. A visual overlay with population distribution for all three regions clearly indicates a relationship between forest loss and areas of high population density, suggesting population pressure as a main driver of deforestation. The revealed forest losses due to local and commercial exploitation further demonstrate that weak management impedes effective forest protection in East Africa.     

The impact of lynx and wolf on roe deer hunting benefits in Sweden

Large carnivores provide ecosystem and cultural benefits but also impose costs on hunters due to the competition for game. The aim of this paper was to identify the marginal impact of lynx (Lynx lynx) and wolf (Canis lupus) on the harvest of roe deer (Capreolus capreolus) in Sweden and the value of this impact. We applied a production function approach, using a bioeconomic model where the annual number of roe deer harvested was assumed to be determined by hunting effort, abundance of predators, availability of other game, and winter severity. The impact of the predators on the roe deer harvests was estimated econometrically, and carnivore marginal impacts were derived. The results showed that if the roe deer resource was harvested under open access, the marginal cost in terms of hunting values foregone varied between different counties, and ranged between 18,000 and 58,000 EUR for an additional lynx family, and 79,000 and 336,000 EUR for an additional wolf individual. Larger marginal costs of the wolf, in terms of the impact on roe deer hunting, were found in counties where the hunting effort was high and the abundance of moose (Alces alces) was low. If instead, hunters could exert private property rights to the resource, the average marginal cost was about 20% lower than it would have been if there was open access, and the difference in wolf impact between counties with high and low moose density was smaller. Together, results suggest that the current plan for expanding the wolf population in south Sweden can be associated with a substantial cost.

     

Ökotoxikologische Untersuchung von Sedimenten und Schwebstoffen

The potential risk of ground-water contamination through the infiltration of contaminants originating from suspended matter and sediments deposited within flood retention areas in the Upper Rhine valley, as well as subsequent problems for drinking water production, were analyzed by means of the bacterial dehydrogenase activity (DHA; sediment contact test) assay with Arthrobacter globiformis and in a prolonged embryo toxicity assay using zebrafish (Danio rerio). Since the direct uptake of contaminants from particle-bound sources has usually been assumed to play only a minor role in bioaccumulation, the availability of organic extracts to biota has generally been regarded as being overestimated. In order to confirm or discard this hypothesis, organic (acetone) extracts of recently suspended, freeze-dried matter, as well as freeze-dried sediments collected from Rhine flood plains (i.e. soil samples) were compared to corresponding native samples in order to screen for the relative availability of particle-bound contaminants. Whereas a significantly higher ecotoxicological burden was observed for some native soil samples, organic extracts of suspended matter proved to be more toxic than corresponding native samples when compared to organic extracts using each test system. With respect to organic extracts, the suspended matter samples were more toxic than soil samples taken from a rarely flooded site. In contrast to the native samples, the rarely flooded soils revealed a higher toxicity than suspended matter. Therefore, organic extracts did not necessarily overestimate the toxicity of soil and suspended matter samples. Moreover, considerable toxicity of particle-bound contaminants to both bacteria and fish embryos, even in native samples, corroborate the hypothesis that particle-bound contaminants may be more readily available than is generally assumed.