Distribution of volatile organic compounds in Madrid (Spain)

From November 1995 to October 1996, airborne concentrations of VOCs were measured in the Madrid area to study the organic pollution in general, and the correlation between different pollutants in relation to such parameters as location and season. Mean concentrations for up to 90 compounds were measured at four test sites, including both urban and suburban areas. At the urban sites, maximum concentrations occurred in the autumn and winter, whereas minimum concentrations were reached in summer and spring. Similar changes were obtained for the lesscontaminated site located in the SE of the city, whereas a different pattern was found at the site in the NW of the city due to meteorological aspects. Mean levels of hydrocarbons in Madrid were quite similar to those found in other European cities. Chemometrical techniques were applied to the set of data in order to assess the influence of such factors as traffic, temperature and seasonal variations on the VOC levels.     

CO2 transportation for carbon capture and storage: Sublimation of carbon dioxide from a dry ice bank

Climate change is being caused by greenhouse gases such as carbon dioxide (CO₂). Carbon capture and storage (CCS) is of interest to the scientific community as one way of achieving significant global reductions of atmospheric CO₂ emissions in the medium term. CO₂ would be captured from large stationary sources such as power plants and transported via pipelines under high pressure conditions to underground storage. If a downward leakage from a surface transportation system module occurs, the CO₂ would undergo a large temperature reduction and form a bank of “dry ice” on the ground surface; the sublimation of the gas from this bank represents an area source term for subsequent atmospheric dispersion, with an emission rate dependent on the energy balance at the bank surface. Gaseous CO₂ is denser than air and tends to remain close to the surface; it is an asphyxiant, a cerebral vasodilator and at high concentrations causes rapid circulatory insufficiency leading to coma and death. Hence a subliming bank of dry ice represents safety hazard. A model is presented for evaluating the energy balance and sublimation rate at the surface of a solid frozen CO₂ bank under different environmental conditions. The results suggest that subliming gas behaves as a proper dense gas (i.e. it remains close to the ground surface) only for low ambient wind speeds.     

Real-world vehicle emissions: a summary of the Seventeenth Coordinating Research Council On-Road Vehicle Emissions Workshop

The Coordinating Research Council, Inc. (CRC) held its 17th On-Road Vehicle Emissions Workshop in March 2007, where results of the most recent on-road vehicle emissions research were presented. We summarize ongoing work from researchers who are engaged in improving our understanding of the role and contribution of mobile sources to ambient air quality and emission inventories. Participants in the Workshop discussed efforts to improve mobile source emission models, light- and heavy-duty vehicle emissions measurements, on- and off-road emissions measurements, effects of fuels and lubricating oils on emissions, as well as emerging issues and topics for future research.     

Biodegradation of oxygenated and non-oxygenated imidazolium-based ionic liquids in soil

Aerobic biodegradation of ionic liquids in soil was monitored for the first time. The tests, followed over six months according to ASTM D 5988-96, were carried out on the four ionic liquids obtained from 1-R-3-methylimidazolium cations, with R=CH(3)(CH(2))(3) and CH(3)O(CH(2))(2), and the tetrafluoroborate and dicyanamide counter anions. The n-butyl derivatives, after an induction period of about two months, were found to be degradable, although the degradation rate with the dicyanamide anion was smaller. In contrast, no significant production of CO(2) was observed in the tests with the methoxyethyl derivatives. Calculations at the B3LYP/6-31G(d) level were carried out to characterize the atomic charge distributions and frontier orbital structures of 1-alkyl-3-methylimidazolium cations and point out the changes caused by replacement of a CH(2) group of the alkyl chain with an oxygen atom. The calculations predict an overall negative charge on the nitrogen atoms of the imidazolium-based cations. The energies of the highest occupied (pi) MO and lowest empty (pi( *)) MO are only slightly perturbed by the length and nature of the alkyl chain. However, the electron-donor properties of the oxy derivatives are radically increased. The HOMO becomes a lone pair orbital mainly localized on the oxygen atom, and its ionization energy is sizeably smaller than that of the outermost ring pi MO.     

160 h of chemical-looping combustion in a 10 kW reactor system with a NiO-based oxygen carrier

Chemical-looping combustion, CLC, is a technology with inherent separation of the greenhouse gas CO₂. The technique uses an oxygen carrier made up of particulate metal oxide to transfer oxygen from combustion air to fuel. In this work, an oxygen carrier consisting of 60% NiO and 40% NiAl₂O₄ was used in a 10 kW CLC reactor system for 160 h of operation with fuel. The first 3 h of fuel operation excepted, the test series was accomplished with the same batch of oxygen carrier particles. The fuel used in the experiments was natural gas, and a fuel conversion to CO₂ of approximately 99% was accomplished. Combustion conditions were very stable during the test period, except for the operation at sub-stoichiometric conditions. It was shown that the methane fraction in the fuel reactor exit gas was dependent upon the rate of solids circulation, with higher circulation leading to more unconverted methane. The carbon monoxide fraction was found to follow the thermodynamical equilibrium for all investigated fuel reactor temperatures, 660–950 °C. Thermal analysis of the fuel reactor at stable conditions enabled calculation of the particle circulation which was found to be approximately 4 kg/s, MW. The loss of fines, i.e. the amount of elutriated oxygen carrier particles with diameter <45 μm, decreased during the entire test period. After 160 h of operation the fractional loss of fines was 0.00022 h⁻¹, corresponding to a particle life time of 4500 h.     

Using the Framework for Integrated Sustainability Assessment (FISA) to expand the Multiregional Input–Output analysis to account for the three pillars of sustainability

Decision makers interested in promoting sustainable development must simultaneously consider the environmental, economic and social implications of any action. This article proposes the Framework for Integrated Sustainability Assessment (FISA), a methodological framework for conducting a sustainability impact assessment of any investment project. Based on a Multiregional Input–Output (MRIO) framework, FISA links the extended MRIO results with social risk data from the Social Hotspots Database (SHDB) in order to integrate the social with the environmental and economic pillars. Resulting impacts are simultaneously considered and reported by means of FISA charts, making it possible to assess the different impacts within the three sustainability pillars across countries involved in the whole supply chain of investment projects. This methodological framework can be applied not only to compare the sustainability impacts of two alternative projects, but also to derive specific recommendations aimed at minimizing the harmful social, environmental and economic effects along the whole project supply chain.     

Functional group influences on the reactive azo dye decolorization performance by electrochemical oxidation and electro-Fenton technologies

Electrochemical water treatment technologies are highly promising to achieve complete decolorization of dyebath effluents, as demonstrated by several studies reported in the literature. However, these works are focused on the treatment of one model pollutant and generalize the performances of the processes which are not transposable since they depend on the pollutant treated. Thus, in the present study, we evaluate, for the first time, the influence of different functional groups that modify the dye structure on the electrochemical process decolorization performance. The textile azo dyes Reactive Orange 16, Reactive Violet 4, Reactive Red 228, and Reactive Black 5 have been selected because they present the same molecular basis structure with different functional groups. The results demonstrate that the functional groups that reduce the nucleophilicity of the pollutant hinder the electrophilic attack of electrogenerated hydroxyl radical. Thereby, the overall decolorization efficiency is consequently reduced as well as the decolorization rate. Moreover, the presence of an additional chromophore azo bond in the molecule enhances the recalcitrant character of the azo dyes as pollutants. The formation of a larger and more stable conjugated π system increases the activation energy required for the electrophyilic attack of ^?OH, affecting the performance of electrochemical technologies on effluent decolorization.     

Novel two-step vapor-phase synthesis of UV–Vis light active Fe2O3/WO3 nanocomposites for phenol degradation

Supported Fe₂O₃/WO₃ nanocomposites were fabricated by an original vapor phase approach, involving the chemical vapor deposition (CVD) of Fe₂O₃ on Ti sheets and the subsequent radio frequency (RF)-sputtering of WO₃. Particular attention was dedicated to the control of the W/Fe ratio, in order to tailor the composition of the resulting materials. The target systems were analyzed by the joint use of complementary techniques, that is, X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and optical absorption spectroscopy. The results showed the uniform decoration of α-Fe₂O₃ (hematite) globular particles by tiny WO₃ aggregates, whose content could be controlled by modulations of the sole sputtering time. The photocatalytic degradation of phenol in the liquid phase was selected as a test reaction for a preliminary investigation of the system behavior in wastewater treatment applications. The system activity under both UV and Vis light illumination may open doors for further material optimization in view of real-world end-uses.