Validation of a dynamic model of hydrogen permeation through Pd-based membranes

Pd-based membranes have been studied for pure hydrogen separation from syngas: in particular, a mathematical model of a Pd membrane for hydrogen separation has been developed.This model can be used in process and assessment studies of the parameters which characterize the mass transfer phenomena (such as: hydrogen permeability, surface coverage and limiting step). By coupling the permeation and water gas shift reaction kinetics, it can also be used to evaluate the performances of the membrane reactor. Further, it can be helpful to evaluate the best assembly and sizing of a H₂/CO₂ separation system.The model takes into account the kinetics of H₂ adsorption/desorption on Pd surface, the H₂ permeation into the palladium bulk and in the porous layer, and the kinetics of CO, CO₂, H₂O, O₂, H₂S competitive adsorption/desorption on Pd surface. It is also comprehensive of flux equations and bulk mass, momentum and energy balance.The results released by the model were compared to the experimental data during both the transient phase and the steady state conditions. A satisfactory agreement between model and experimental data was found.     

Comparative Evaluation of Biomonitoring Techniques of Tropospheric Ozone

During a survey of tropospheric ozone pollution carried out using tobacco plants (Nicotiana tabacum L.) cv. Bel-W3, ozone- supersensitive, and cv. Bel-B, ozone-resistant, as bioindicators, the effectiveness of the traditional biomonitoring method, based on the use of adult plants, was compared with an innovative miniaturized kit of seedlings. The ratio of foliar and cotyledonar necrosis, respectively, was estimated as ozone injury rate. The miniaturized kit proved to be advantageous, since seedlings need only easy growth procedures and a large number of individuals can be placed in a small space, supplying good data amounts for statistical elaboration. Moreover, correlation studies among cotyledonar and foliar injury index and ozone levels monitored through physico-chemical measurements and results of analysis of variance tests highlighted the high sensitivity of the innovative methodology.     

Electrochemical remediation of copper (II) from an industrial effluent Part II: three-dimensional foam electrodes

A batch recycle removal of copper ions from an industrial effluent by means of copper foam cathodes was tested. A constant current of 750 A was applied to the cell in order to perform the reduction. Copper depletion was investigated at different solution flow rates and a removal greater than 98% was obtained with a flow rate of 1000 l/h. The influence of initial metal concentration on copper deposition and current efficiency is also discussed.     

Simultaneous determination of Cd(II), Cu(II), Pb(II) and Zn(II) by derivative stripping chronopotentiometry in Pittosporum tobira leaves: a measurement of local atmospheric pollution in Messina (Sicily, Italy)

The purpose of this study is to investigate the bio-accumulation of Cd(II), Cu(II), Pb(II) and Zn(II) in Pittosporum tobira (Thunb.) Aiton leaves sampled in different zones of Messina, in order to assess the level of atmospheric metal deposition in correlation with the traffic volume. Derivative stripping chronopotentiometry was used as a practical, precise and sensitive technique to determine simultaneously Cd, Cu, Pb and Zn levels in Pittosporum leaves. In the optimised electro-chemical conditions, detection limits lower than 0.05 microg kg(-1) were achieved, whereas the accuracy, expressed as obtained recoveries from certified materials, was in the range 93.5-102.7%. The obtained data provided evidence that Cd and Pb levels significantly decreased from high to low traffic density zones (p < 0.005, ANOVA), whereas Cu and Zn are accumulated by plants particularly from the soil and their contents is not related to the traffic volume.     

Assessment of state-of-the-art models for predicting the remobilisation of radionuclides following the flooding of heavily contaminated areas: the case of Pripyat River floodplain

The performances of models are assessed to predict the wash-off of radionuclides from contaminated flooded areas. This process should be accounted for in the proper management of the aftermath of a nuclear accident. The contamination of the Pripyat River water following the inundation of a floodplain heavily contaminated by (90)Sr and (137)Cs of Chernobyl origin is used as the basis for modelling. The available experimental evidence demonstrated that remobilisation of radiostrontium is an important process implying a significant secondary radioactive load of water flowing over the contaminated floodplain. On the contrary, there is no empirical evidence of a similar behaviour for radiocaesium. In general, state-of-the-art models properly predicted the remobilisation of strontium, whereas they significantly overestimated radiocaesium concentrations in water. The necessary model improvements for a more accurate prediction of radiocaesium contamination levels include a reassessment of the values of the model parameters controlling the remobilisation process.     

Foliar response of an Ailanthus altissima clone in two sites with different levels of ozone-pollution

Potted plants of Ailanthus altissima, produced by root suckers coming from a single symptomatic mother tree, were placed in two sites in the vicinity of Florence (central Italy), with different levels of ozone pollution. These plants were kept in well watered conditions during the period May-September 1999. In the high pollution site (Settignano-SET) the level of ozone exposure (AOT40) reached at the end of the season a value of 31 ppm h, whereas in the "low pollution" site (Cascine-CAS) the exposure to ozone was 11 ppm h. A. altissima showed foliar symptoms in early July at SET and in the second half of July at CAS when exposure values reached 5 ppm h at both sites. However, at the end of August the conditions of the plantlets were rather similar in both sites. Microscopic and ultrastructural analysis were performed at the first onset of symptoms at SET (the CAS leaflets were asymptomatic). Observing the upper leaf surface where the brown stipples were visible, it was found that the cells of the palisade mesophyll displayed loss of chlorophyll and the organelles in the cytoplasm were damaged. Swelling of thylacoids was observed in the CAS leaflets, thus indicating the possible onset of a pre-visual damage. The injured cells were separated from the healthy ones by a layer of callose. We conclude that the sensitivity to ozone of A. altissima leaves is related to its leaf structure, with low leaf density and large intercellular spaces. Cell walls, as well as acting as mechanical barriers against the spread of ozone within the cell, also provide important detoxifying processes.     

Development of processes for environmental protection based on self-propagating reactions

The possibility of exploiting self-propagating reactions for environmental protection is discussed in this paper. In particular, results obtained at the laboratory scale and related to the fixation and consolidation of high level radioactive wastes, the recycling of silicon sludge and aluminum dross produced by semiconductor industries and aluminum foundries, the treating and recycling of a highly toxic solid waste from electrolytic zinc plants, and the degradation of chlorinated aromatics, are examined with particular emphasis on the latter case. Specifically, the self-propagating destruction of hexachlorobenzene and 2-(2-4-dichlorophenoxy)-propanoic acid with calcium hydride as reductive substrate is demonstrated. In fact, the heat liberated by the reactions involved is large enough to guarantee the self-sustaining character of the process within a wide range of reactants compositions. Moreover, no residual chlorinated organic compounds were found in the final solid product. Some reactor engineering aspects, as well as other significant future scientific and technological issues, are also addressed in view of large-scale applicability of processes based on self-propagating reactions. To date, the batch reactor technology seems to be more easily applicable, although the use of continuous reactors is not excluded in the next future.     

An experimental and numerical investigation into the impact of dissolution/precipitation mechanisms on CO2 injectivity in the wellbore and far field regions

Carbon dioxide capture and storage (CCS) technology is gaining credibility as the best short to medium term solution for significantly reducing net carbon emissions into the atmosphere. From a capacity point of view, deep saline aquifers offer the greatest potential for CO₂ storage. In this respect, well injectivity is considered a key technical and economical issue. Rock/fluid interactions – dissolution/precipitation of minerals, in particular carbonates – are currently considered as one of the principal reasons for wellbore injectivity changes in aquifers.This research investigated the mechanisms involved in injectivity losses through experimental and theoretical methods. The impact on injectivity of permeability changes occurring at various distances from the wellbore was studied using an idealised CO₂ injection well flow model. A new experimental set-up was used to investigate the effect on dissolution/precipitation mechanisms of the pressure and temperature changes that the fluid is subjected to as it advances from the wellbore.Numerical modelling of the injection wellbore has shown that changes in the petrophysical properties of the reservoir several metres away from the wellbore can still have a significant impact on injectivity. As indicated by the experimental research carried out, pressure and temperature gradients that exist inside the reservoirs may lead to re-precipitation in the far field, however no significant permeability and porosity changes were detected to suggest major losses of injectivity due to these effects.     

Living close, doing differently: small-scale asynchrony in demography of two species of seabirds

Studies on spatiotemporal pattern of population abundance predict that close populations should exhibit a high level of synchrony, reflected in a parallel time variation of at least one demographic parameter. We tested this prediction for two threatened species of Procellariiformes sharing similar life history traits: the European Storm Petrel (Hydrobates pelagicus) and the Balearic Shearwater (Puffinus mauretanicus). Within each species, we compared adult survival, proportion of transients (breeders that do not settle), and average productivity at two neighboring colonies. Physical and environmental features (e.g., food availability) of the breeding sites were similar. However, while Balearic Shearwater colonies were free of predators, aerial predators occurred especially in one colony of the European Storm Petrel. Despite this difference, we found similar results for the two species. A high proportion of transient birds was detected in only one colony of each species, ranging between 0.00-0.38 and 0.10-0.63 for the petrels and shearwaters, respectively. This seems to be an emergent feature of spatially structured populations of seabirds, unrelated to colony size or predator pressure, that can have important demographic consequences for local population dynamics and their synchrony. Local survival of resident birds was different at each colony, an unexpected result, especially for predator-free colonies of Balearic Shearwater. Productivity varied between the two colonies of European Storm Petrels, but not between the two colonies of Balearic Shearwaters. We demonstrated that within each species, several demographic parameters were colony specific and sufficiently different to generate short-term asynchronous dynamics. Our findings suggest that, in spatially structured populations, local factors, such as predation or small-scale habitat features, or population factors, such as individual quality or age structure, can generate unexpected asynchrony between neighboring populations.