The contributions of “minimum primary emissions” and “new particle formation enhancements” to the particle number concentration in urban air

In an urban site affected by fresh vehicle exhaust emissions, the ambient air number concentrations of particles coarser than 3 nm (N) was split into two components, N=N1+N2. This was done using a method based on the high correlation between black-carbon (BC) and number (N) concentrations which is typically observed in ambient air and is the result of vehicle exhaust emissions. The component N1 accounts for “those aerosol components directly emitted in the particle phase” and “those components nucleating immediately after emission”. The component N2 accounts for the new particle formation enhancements during the “dilution and cooling of the vehicle exhaust” and is also influenced by “in situ new particle formation in ambient air”. The contribution of N1 to N exhibits a maximum of 55% during the morning rush hours (07:00–08:00). The contribution of N2 to N exhibits a daily evolution with a broad maximum during daylight (as solar radiation intensity), while for about 7 h (11:00–17:00) the N2 contribution to N is about 70%. During some “afternoon N2 events”, N2 contributions exceeded 90%. Enhancements in the new particle formation processes may increase the N/BC concentrations ratio in one order of magnitude, from 4.82×10⁶ particles/ng BC to 47×10⁶ particles/ng BC and during some events up to 97×10⁶ particles/ng BC. The results show evidence of the high potential of the vehicle exhausts and of the urban atmosphere to trigger new particle formation if the ambient air conditions are favourable. The method used in this study is useful in assessing future changes in the number to BC relationship due to forthcoming regulations in the vehicle exhaust emissions.     

Kinetics of mechanically induced anatase-to-rutile phase transformations under inelastic impact conditions

This work investigates the kinetics of the anatase-to-rutile phase transformation of TiO₂ powders during ball milling. Two elementary stages are observed, namely the transformation of anatase to the TiO₂ II phase and of this latter to rutile. Such consecutive reactions were studied under inelastic impact regimes. Based on a suitable modeling of transformation kinetics, the fraction of powder processed on average at each collision was estimated. The mass of powder involved in phase transformation and microstructural refinement processes at each collision was then worked out by a systematic variation of the powder charge inside the reactor.     

Linking ecological information and radiative transfer models to estimate fuel moisture content in the Mediterranean region of Spain: Solving the ill-posed inverse problem

Live fuel moisture content (FMC) is a key factor required to evaluate fire risk and its operative and accurate estimation is essential for allocating pre-fire resources as a part of fire prevention. This paper presents an operative and accurate procedure to estimate FMC though MODIS (moderate resolution imaging spectrometer) data and simulation models. The new aspects of the method are its consideration of several ecological criteria to parameterize the models and consistently avoid simulating unrealistic spectra which might produce indetermination (ill-posed) problems when inverting the model. The methodology was operatively applicable to 12 shrubland plots located in different provinces of the Mediterranean region of Spain and tested with field data collected in those areas. The results showed that the proposed method efficiently tracks changes of FMC with average errors around 15%. However the model under-estimates FMC values higher than 135.68% since those situations were not included in the simulation scheme and the inversion precision is also dependent on an accurate estimation of LAI. These limitations will be overcome in future work mainly by including spectral signatures of vegetation with FMC values higher than 135.68% in the simulations, and by exploring new methods for LAI retrieval. Further efforts will also be devoted to extend this approach to other ecosystems.     

Synthesis and properties of aliphatic spirodilactam diphenol containing polyesters

A series of aromatic polyesters containing 1,6-diazaspiro[4,4]-nonane-2,7-dione were synthesized under phase-transfer conditions. The copolymers were obtained in essentially quantitative yield, theses were soluble in common organic solvents, and would readily form clear, colorless films from solution. The optimum conditions of polymerization, was obtained via polycondensation at room temperature and reaction time of 4 h in chloroform. All polymers were characterized by FTIR, GPC, viscosity, water contact angle, water absorption, TGA, DSC and TMA. The prepared polyesters showed excellent thermal stability, as measured by TGA (10 wt% loss), are only moderate due to the alicyclic component and range from 365 to 401 °C in air; however, glass transition temperatures are quite high (245-309 °C). The inherent viscosities of these solutions ranged from 0.77 to 1.40 dl g⁻¹, depending on the polyester structure. The structures of the polyesters were confirmed by FTIR spectroscopy.     

Acid modified bamboo‐type carbon nanotubes and cup‐stacked‐type carbon nanofibres as adsorbent materials: cadmium removal from aqueous solution

BACKGROUND: Nitrogen‐doped multi‐walled carbon nanotubes (CN_x) and cup‐stacked‐type carbon nanofibres (CST) were modified with nitric acid, at 85 °C, for 1–3 h to enhance their cation adsorption capacity, and were used for cadmium removal from aqueous solutions. These carbon nanostructures were characterized by SEM, EDX, FTIR, BET surface area, TGA and acid/base titrations. In addition, cadmium adsorption experiments were carried out at different pH values and constant temperature. RESULTS: EDX and FTIR revealed a 0.4 times increase in oxygen content after acid treatment, which was reflected in an increment of up to 1.93 mmol g^?1 of acid sites and in a shift of about two units of the zero point charge to lower pH values. The BET surface area, in general, decreased as the oxidation time increased. Finally, batch sorption experiments indicated that CN_x are more effective than CST to sequester Cd²⁺ at pH 7; the sorption capacities of these materials increased as pH rose. CONCLUSIONS: The results obtained indicate that it is feasible to modify both physical and chemical properties of the carbon nanostructures CN_x and CST by HNO₃ in such a way that they can be used to adsorb cations present in aqueous solutions. Copyright © 2008 Society of Chemical Industry     

Study on the interaction of diarylbutadiynes with free radicals: Interaction with propagating radicals of some vinyl monomers

In order to study the nature of interaction of arylbutadiynes with transient free radicals, polymerization and copolymerization of some vinyl monomers such as methyl methacrylate (MMA), styrene (ST), methacrylonitrile (MAN), vinylidene chloride (VCl₂), ethyl acrylate (EA) and acrylonitrile (AN), were carried out in the presence of diphenylbutadiyne (DPB), 4,4'-butadiynylene-N,N,N',N'-tetra-n-butyl-dibenzamide (BBA), and 4,4'-dibromodiphenylbutadiyne (BPB). MMA gave an intense ESR signal at the polymerization temperature when the polymerization system became viscous, and the number of radicals increased with polymerization time. Strong signals of polyEA and polyMAN radicals were also observed in the presence of DPB when the polymerization system became almost solid. This is a unique case where active transient propagating radicals such as that of polyEA can be detected at polymerization temperature. The rates of polymerization decreased by the presence of the diacetylenes, but the molecular weights did not change with the diacetylene concentrations. UV spectroscopy revealed that there was no diacetylene unit bonded to the obtained polymers, indicating that degradative chain transfer is not the case. The monomer reactivity ratios for MMA-ST and MMA-AN systems did not vary significantly in the presence of the diacetylenes, although some difference was observed. It seems that some arylbutadiynes interact with free radicals but do not form bonds. Received: 4 June 1999/Revised version: 29 September 1999/Accepted: 29 September 1999     

A New Distance Measure for Model-Based Sequence Clustering

We review the existing alternatives for defining model-based distances for clustering sequences and propose a new one based on the Kullback-Leibler divergence. This distance is shown to be especially useful in combination with spectral clustering. For improved performance in real-world scenarios, a model selection scheme is also proposed.     

Dynamic vegetation model as a tool for ecological impact assessments of dam operation

This study presented the results of an application of a floodplain dynamic model to the Nakdong River, South Korea. At the Nakdong River, high flows are reduced by dams and the river bed is degraded. Both changes contribute toward the same result: the floodplain is hydraulically disconnected from the main channel and the morphology of the river has been modified. Such changes brought also to a deep modification in the riparian vegetation distribution, abundance and composition. The focus of the study is on the relationship between the hydrology alterations induced by dams and the successional changes in riparian vegetation. More in detail, the study attempts to adapt an existing dynamic floodplain vegetation model to the Nakdong ecosystem characteristics in order to single out what were the effects of the dam operations that led to a change in the riparian landscape. The dynamic model is targeted on Monsoon floodplain vegetation, it is developed upon a custom developed geoprocessing framework and supported by a standalone user interface. It simulates dynamics of floodplain vegetation communities based on different physical parameters. The general concept of the model is that a vegetation community will either undergo toward a maturation stage or will be destroyed (recycling or retrogression) if the magnitude of key physical parameters is greater than the threshold value for a specific community. The model has been calibrated using hydraulic data spanning the time period 1952–2007. The calibration results have been also used to investigate the impacts on the riparian vegetation given by dams operations. The findings of the research highlight that consecutive years of reduced maximum discharge allowed consistent vegetation colonization of riverine areas that were bare before the dam construction.