On the effect of pH in aromatic photonitration upon nitrate photolysis

This paper studies the pH effect on the photonitration of catechol, 1-naphthol, naphthalene, and benzene. The pH trend is influenced by the generation of HNO(2) and peroxynitrous acid (HOONO) upon nitrate photolysis. HNO(2) can be involved in a direct and an indirect nitration process. Direct nitration follows the pH distribution of HNO(2) (flexus around 3). Indirect nitration, possibly involving nitrosation+oxidation, would be highest around pH3. HOONO can be involved in electrophilic nitration, where the initial formation rate of the nitroderivatives is proportional to [H(+)], or take part in nitration directly, in which case a less important pH effect in photonitration is observed. The relative importance of the various nitration pathways for each substrate determines the resulting pH effect in photonitration upon nitrate photolysis.     

Phenol nitration upon oxidation of nitrite by Mn(III,IV) (hydr)oxides

An interesting aspect of the chemistry of nitrite is the possibility for this compound to interact with other environmental factors and many oxidising species, which results in the oxidation of nitrite to nitrogen dioxide. This is a potentially interesting process that can lead to the formation of nitroaromatic compounds in the environment. In previous papers we have shown that nitrite can interact with dissolved Fe(III) and nitrate under irradiation, Fenton and heterogeneous photo-Fenton reagents, and semiconductor oxides such as TiO2, alpha-Fe2O3, and beta-FeOOH under irradiation. This paper reports on the interaction between nitrite/nitrous acid and the Mn(III,IV) (hydr)oxides beta-MnO2 and gamma-MnOOH, both in neutral solution under irradiation and in acidic conditions in the dark. beta-MnO2 and gamma-MnOOH originate from the oxidation of Mn(II) and play a key role in the redox cycling of manganese in the environment. These Mn(III,IV) (hydr)oxides show some photocatalytic activity, and they can act as thermal oxidants at acidic pH. The photoinduced oxidation of nitrite and the thermal oxidation of nitrous acid by Mn(III,IV) (hydr)oxides yield nitrogen dioxide and lead to the formation of nitrophenols in the presence of phenol. These processes can take place at the water-sediment or water-colloid interface in natural waters and on the surface of atmospheric particulate. Furthermore, the phenol/gamma-MnOOH/HNO2 system in dark acidic solution is an interesting model due to the formation of phenoxyl radical upon phenol monoelectronic oxidation by gamma-MnOOH. The kinetics of nitrophenol generation under such conditions indicates that phenol nitration is unlikely to take place upon reaction between phenoxyl and *NO2 and suggests a solution to a literature debate on the subject.     

Crown condition surveys in Italian forests: issues in reporting findings

This study examines defoliation and discoloration findings collected throughout the Italian Level I network between 1997 and 2000. Prior to this period no Quality Assurance procedures had been implemented, so that earlier findings cannot be considered reliable. The aim of the study is to compare differentindices used in reporting findings, in order to determine the full potential and limitations of each. In international surveys,findings are normally expressed in terms of individual trees presenting a defoliation level greater than 2 %; this criterion,however, has been challenged since it is not based on scientificevidence. By analysing the distribution of defoliation values(grouped in 5% classes) relating to the main species (Fagus sylvatica, Quercus pubescens, Quercus cerris, Picea abies), the study examines the behaviour of statistical indices such as the median, the mode and the mean. Instead of using the traditional 25% threshold to determine the part of the population with the highest defoliation values, a procedureis suggested whereby a different threshold can be determined foreach species. It is established based on the 90° percentile of cumulative defoliation values recorded over the four-year period. Each index used to report findings possessesits own information potential, and the findings may at times appear contradictory. The use of a combined defoliation and discoloration index (Ilce = Lacking Crown Equivalent Index) is also proposed, but the results obtained do not differin substance from the results relating to defoliation alone. Thefunctional limitations of this index are due mainly to the way the data are collected: for this reason suggestions are made onhow to improve the procedure in future surveys.     

Photochemical reaction of peroxynitrite and carbon dioxide could account for up to 15 % of carbonate radicals generation in surface waters

The carbonate radical (CO ₃ ^?· ) is a photoinduced transient species occurring in surface waters. The carbonate radical can transform both natural compounds and xenobiotics. For instance, it can react with electron-rich substrates such as anilines, phenols and organic sulfur compounds. Here we used the APEX software to assess photochemical reactions, including the formation rates of transient species, based on water chemistry and depth, under summertime irradiation conditions. We found that the reaction between peroxynitrite and carbon dioxide is a potentially significant source of CO ₃ ^?· in sunlit surface waters, and could account for up to 10–15 % of the total CO ₃ ^?· formation. The peroxynitrite pathway to CO ₃ ^?· would be most significant at pH 7–8 and would be enhanced in waters with elevated nitrate and low alkalinity. Therefore, the proposed process could add to the known photochemical sources of CO ₃ ^?· in surface-water environments.     

Inventory and conservation assessment for the management of coastal dunes,Veneto coasts,Italy

Management of coastal dunes on developed coasts could effectively take advantage of comprehensive and multitemporal georeferenced data collection, which offers the possibility to relate dune data with the natural and cultural characteristics of the beach and hinterland. The recent implementation of a coastal management geodatabase for the Veneto region provides the opportunity for improving knowledge on coastal dunes on developed littoral as well as a basis for appropriate future coastal planning in the study area. The geodatabase gathers data concerning different physical, evolutionary and human aspects of the coastal zone, with a special focus on coastal dunes. Established foredunes, human-altered dunes and relict dunes are irregularly distributed along 59 km, 38% of the entire coastal length. Their distribution and characteristics are the result of favourable natural conditions as well as long-lasting tourism exploitation (evaluated through an index of Land Use Pressure) and fragmentary and diversified uses of beaches (evaluated through an index of Tourism Pressure on the beach). At the same time, beach/dune nourishment intervention allowed the presence of artificial or sand fenced dunes along 17 km of coast. High dune elevation up to 8–10 m is promoted by the onshore exposition of the beach to dominant wind (from ENE), by stable-to-slowly negative sedimentary budget or by the re-activation of high relict foredunes in the case of shoreline retreat associated with strong negative budget. Present sedimentary budget (evaluated through the code ASPE – Accretion, Stable, Precarious, Erosive) is the tool used for dividing coasts in sedimentary compartments or cells. Past and present sedimentary budget and different human responses to erosive cases (hard and soft interventions) give the foredunes different means to form, grow, survive and evolve over time. The assessment of Human Impact and Active Management Practices on the dunes allows a first evaluation of the Management Effectiveness, which shows strong shortcomings for 81% of the dunes. The great variability of beach usage, human impact and management practises on the different dune stretches highlight the lack of effective and systematic management actions being correctly scheduled and performed.     

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.