Development of mixed conducting membranes for clean coal energy delivery

Mixed conducting membranes can be used for the separation of oxygen from air in both coal gasification and oxy-fuel power plants. In this review paper, the basic perovskite and non-perovskite structures, composition, properties and performance are addressed. Two typical perovskite materials, BSCF and LSCF, show promise in industrial applications as their oxygen fluxes are at least one order of magnitude higher than non-perovskite membranes. BSCF membranes are now delivering oxygen fluxes in excess of 5 ml min^?1 cm^?2. Latest developments in perovskite composition, effects of impurities in membrane performance and membrane geometry are discussed giving an insight into the potential utilisation in clean energy delivery processes. Strategies for improving membranes performance using unit operations with different geometries and possible future technologies are also addressed.     

Chemical and biochemical tools to assess pollution exposure in cultured fish

There is little information regarding pollutant levels in farmed fish, and the risks associated to consumption. This study was designed to assess levels of exposure to metals, organochlorinated compounds, polycyclic aromatic hydrocarbons (PAHs) and alkylphenols (APEs) in farmed sea bass Dicentrarchus labrax from five aquacultures located in Southern Europe. Additionally, several biochemical responses (metallothionein, 7-ethoxyresorufin O-deethylase, vitellogenin) were determined as complementary tools. The obtained data indicate that pollutants exposure in farmed fish is similar to the levels reported in wild specimens from the area. Nonetheless, some biochemical responses were observed in the studied organisms, viz. metallothionein induction in Cu exposed organisms, and 7-ethoxyresorufin O-deethylase (EROD) and vitellogenin induction in PAHs and APEs exposed ones. The study further supports the usefulness of the biomarker approach as a first screening method to discriminate between basal and high levels of exposure in cultured fish.     

Copper, nickel and lead in lichen and tree bark transplants over different periods of time

This work aimed at comparing the dynamics of atmospheric metal accumulation by the lichen Flavoparmelia caperata and bark of Platanus hybrida over different periods of time. Transplants were exposed in three Portuguese coastal cities. Samples were retrieved (1) every 2 months (discontinuous exposure), or (2) after 2-, 4-, 6-, 8- and 10-month periods (continuous exposure), and analysed for Cu, Ni and Pb. Airborne accumulation of metals was essentially independent of climatic factors. For both biomonitors [Pb]>[Ni]>[Cu] but Pb was the only element for which a consistent pattern of accumulation was observed, with the bark outperforming the lichen. The longest exposure periods hardly ever corresponded to the highest accumulation. This might have been partly because the biomonitors bound and released metals throughout the exposure, each with its own dynamics of accumulation, but both according to the environmental metal availability.     

Methane release from wetlands and watercourses in Europe

This study was conducted to estimate annual CH₄ efflux from wetlands and watercourses in Europe and some adjacent areas. Wet ecosystems were divided into seven categories: ombrotrophic mires, minerotrophic mires, freshwater marshes, saltwater marshes, small lakes, large lakes and rivers. The geographical distribution and total area coverage for each of these respective ecosystems were taken from CORINE 2000, Global Land Cover 2000 [JRC, 2003. Harmonisation, mosaicing and production of the Global Land Cover 2000 database (Beta Version). EUR 20849 EN, Joint Research Center, Ispra, Italy] and ESRI 2003 databases. CH₄ release factors were obtained from an extensive overview of published literature. Less than 3% of the study area of 22,560,000 km² consisted of wetlands and watercourses. Large lakes (40%), minerotrophic mires (24%) and ombrotrophic mires (20%) covered almost 85% of the total area of wetlands and watercourses. The total CH₄ release from European wetlands and watercourses was estimated to be 5.2 Tg a^?1. CH₄ release from minerotrophic mires (48%), large lakes (24%), and ombrotrophic mires (12%) composed most of the total CH₄ efflux. High variation in the rate of CH₄ release within the main ecosystem types, small number of studies in some ecosystems and ecologically inadequate land-cover classification are the main reasons for the uncertainties of the estimate. A better estimation of European CH₄ effluxes from natural sources, now and future, would require: a much more detailed and ecologically relevant mapping of the area of different types of wetlands and watercourses, and long-term measurements of CH₄ fluxes and their controlling environmental factors in poorly studied types of wetlands and watercourses. Finally, the data could be used for dynamic modelling of CH₄ fluxes in the current and changing environmental conditions.     

Application and sensitivity testing of a eutrophication assessment method on coastal systems in the United States and European Union

The Assessment of Estuarine Trophic Status (ASSETS) screening model has been extended to allow its application to both estuarine and coastal systems. The model, which combines elements of pressure, state and response, was tested on four systems: Maryland Coastal Bays and Long Island Sound in the United States and The Firth of Clyde (Scotland) and Tagus Estuary (Portugal) in the European Union. The overall scores were: Maryland Coastal Bays: Bad; Firth of Clyde: Poor; Tagus Estuary: Good. Long Island Sound was modelled along a timeline, using 1991 data (score: Bad) and 2002 data (score: Moderate). The improvement registered for Long Island Sound is a consequence of the reduction in nutrient loading, and the ASSETS score changed accordingly. The two main areas where developments are needed are (a) In the definition of type-specific ranges for eutrophication parameters, due to the recognition that natural or pristine conditions may vary widely, and the use of a uniform set of thresholds artificially penalizes some systems and potentially leads to misclassification; (b) In the definition and quantification of measures which will result in an improved state through a change in pressures, as well as in the definition of appropriate metrics through which response may be assessed. One possibility is the use of detailed research models where different response scenarios potentially produce changes in pressure and state. These outputs may be used to drive screening models and analyze the suitability of candidate metrics for evaluating management options.     

Simple and sequential extractions of heavy metals from different sewage sludges

The presence of heavy metals in the sludges produced in waste-water treatment plants restricts their use for agricultural purposes. This study looks at different types of sludges (aerobic, anaerobic, unstabilised and sludge from a waste stabilisation pond) and compares the distribution of the heavy metals they contain according to the treatment that they have undergone. Some agronomic parameters necessary for characterising a sludge as suitable for use as amendment were determined. The aim of this study is to compare the availability and the localisation of heavy metals in different sewage sludges using simple (water and DTPA) extraction and the BCR (Community Bureau of Reference) sequential extraction procedure. It was confirmed that the total concentration of heavy metals did not exceed the limits set out by European legislation and that the stabilisation treatment undergone by the sludges strongly influenced the heavy metal distribution and the phases to which they were associated and their bioavailability level. The DTPA extraction procedure is cheap and easy to perform and the obtained results are similar to those obtained with the sequential procedure.     

Emission of polycyclic aromatic hydrocarbons from gasohol and ethanol vehicles

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20–25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A – Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application.Results showed that the total PAH emission factor varied from 41.9 μg km^?1 to 612 μg km^?1 in the gasohol vehicle, and from 11.7 μg km^?1 to 27.4 μg km^?1 in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 μg TEQ km^?1 to 4.61 μg TEQ km^?1 for the gasohol vehicle and from 0.0117 μg TEQ km^?1 to 0.0218 μg TEQ km^?1 in the ethanol vehicle.For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission.     

Modelling of geochemical and isotopic changes in a column experiment for degradation of TCE by zero-valent iron

Zero-valent iron (ZVI) permeable-reactive barriers have become an increasingly used remediation option for the in situ removal of various organic and inorganic chemicals from contaminated groundwater. In the present study a process-based numerical model for the transport and reactions of chlorinated hydrocarbon in the presence of ZVI has been developed and applied to analyse a comprehensive data set from laboratory-scale flow-through experiments. The model formulation includes a reaction network for the individual sequential and/or parallel transformation of chlorinated hydrocarbons by ZVI, for the resulting geochemical changes such as mineral precipitation, and for the carbon isotope fractionation that occurs during each of the transformation reactions of the organic compounds. The isotopic fractionation was modelled by formulating separate reaction networks for lighter ((12)C) and heavier ((13)C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and beta-elimination can conclusively reproduce the observed concentration profiles of all collected organic and inorganic data as well as the observed carbon isotope ratios of TCE and its daughter products.     

Efficient adsorption of carbon dioxide and methane on activated carbon prepared from glycerol with potassium acetate

In the context of global warming and the energy crisis, emissions to the atmosphere of greenhouse gases such as carbon dioxide (CO₂) and methane (CH₄) should be reduced, and biomethane from landfill biogas should be recycled. For this, there is a need for affordable technologies to capture carbon dioxide, such as adsorption of biogas on activated carbon produced from industrial wastes. Here we converted glycerol, a largely available by-product from biodiesel production, into activated carbon with the first use of potassium acetate as an activating agent. We studied adsorption of CO₂ and CH₄ on activated carbon. The results show that activated carbon adsorb CO₂ up to 20% activated carbon weight at 250 kPa, and 9% at atmospheric pressure. This is explained by high specific surface areas up to 1115 m²g⁻¹. Moreover, selectivity values up to 10.6 are observed for the separation of CO₂/CH₄. We also found that the equivalent CO₂ emissions from activated carbon synthesis are easily neutralized by their use, even in a small biogas production unit.