Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

Community based initiatives to mainstream climate change adaptation into disaster risk reduction: evidence from the Hunter Valley (Australia)

In Australia, local communities often enact Community-Based Initiatives (CBIs) to respond to climate change through Climate Change Adaptation (CCA). CBIs can also be integrated into the Disaster Risk Reduction (DRR) agenda. The paper explores the extent to which CBIs promote the mainstreaming of CCA into DRR. Primary data were obtained from interviews with representatives of CBIs and supporting organisations in three local governments of the Hunter Valley (New South Wales, Australia). Findings show that CBIs recognise the potential contribution of climate change in modifying the local hazard profile. CBIs mainstream CCA into DRR by following four approaches: environmental and social justice; sustainability and transition; ecosystem-based approach; and adaptive planning. Partnerships were identified both among CBIs and between CBIs and City Councils; however, conflicts between CBIs, City Councils and business actors emerged, and a lack of commitment by multi-level governments in responding to climate change was revealed. The findings show that CBIs consider CCA and DRR within a broad everyday context related to vulnerability and local development. But we argue that assigning responsibility for climate change issues to CBIs is not a panacea and should not be the only local climate change response. Instead, CBIs need to be included in a larger and long-term commitment by actors that possess access to resources, such as higher levels of government. The paper provides a local Australian perspective on the effectiveness of mainstreaming CCA into DRR and furthers the conversation for the benefit of other communities facing similar challenges.     

Visible-light driven oxidation of gaseous aliphatic alcohols to the corresponding carbonyls via TiO2 sensitized by a perylene derivative

Sensitized P25 TiO₂ was prepared by wet impregnation with a home-prepared perylene dye, i.e., N,N′-bis(2-(1-piperazino)ethyl)-3,4,9,10-perylene-tetracarboxylic acid diimide dichloride (PZPER). Energy levels of PZPER were found to be compatible with those of TiO₂ allowing fast electron transfer. The obtained catalyst has been characterized and used in the gas-phase partial oxidation of aliphatic primary and secondary alcohols, i.e., methanol, ethanol, and 2-propanol. The reaction was carried out under cut-off (λ?>?400 nm) simulated solar radiation in O₂ atmosphere. The perylene derivative allowed a good absorbance of visible radiation thanks to its low optical energy gap (2.6 eV) which was evaluated by cyclic voltammetry. The optimal organic sensitizing amount was found to be 5.6 % w/w in terms of yield in carbonyl derivatives. Moreover, no change in reactivity/selectivity was observed after 10-h irradiation thus confirming the catalyst stability. Yields into formaldehyde, acetaldehyde, and acetone were 67, 70, and 96 %, respectively. No significant amounts of organic byproducts were detected but for methanol oxidation, whereas a minor amount of the substrate degraded to CO₂.     

Effect of vegetative filter strips on herbicide runoff under various types of rainfall

Narrow vegetative filter strips proved to effectively reduce herbicide runoff from cultivated fields mainly due to the ability of vegetation to delay surface runoff, promote infiltration and adsorb herbicides. A field trial was conducted from 2007 to 2009 in north-east Italy in order to evaluate the effectiveness of various types of vegetative filter strips to reduce spring-summer runoff of the herbicides mesotrione, metolachlor and terbuthylazine, widely used in maize, and to evaluate the effect of the rainfall characteristics on the runoff volume and concentration. Results show that without vegetative filter strip the herbicide load that reaches the surface water is about 5-6 g ha⁻¹ year⁻¹ for metolachlor and terbuthylazine (i.e. 0.5-0.9% of the applied rate), confirming that runoff from flat fields as in the Po Valley can have a minor effect on the water quality, and that most of the risk is posed by a few, or even just one extreme rainfall event with a return period of about 25-27 years, causing runoff with a maximum concentration of 64-77 μg L⁻¹. Mesotrione instead showed rapid soil disappearance and was observed at a concentration of 1.0-3.8 μg L⁻¹ only after one extreme (artificial) rainfall. Vegetative filter strips of any type are generally effective and can reduce herbicide runoff by 80-88%. Their effectiveness is steady even under severe rainfall conditions, and this supports their implementation in an environmental regulatory scheme at a catchment or regional scale.     

Levels and congener profiles of PCBs and PCDD/Fs in blue shark (Prionace glauca) liver from the South-Eastern Mediterranean Sea (Italy)

Liver of blue shark (Prionace glauca) specimens from the South-Eastern Mediterranean Sea were analyzed for the presence of polychlorinated biphenyls (PCBs), including coplanar congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). PCBs were the dominant chemicals, followed by PCDFs and PCDDs. The pattern of PCB congener concentrations in the hepatic tissue was dominated by higher chlorinated compounds. The specific profile of toxic PCDD/F congeners was characterized mainly by 2,3,7,8-TCDF and 2,3,7,8-TCDD, followed by 1,2,3,6,7,8-HxCDD and 2,3,4,6,7,8-HxCDF. The total 2,3,7,8-TCDD toxic equivalent (TEQs) was 149 pg g⁻¹ lipid wt. The profile of TEQ shows that PCDDs present the greatest risk to this species contributing to total toxicity with a percentage approximately of 60%, while the contribution of PCDFs and DL-PCBs is almost the same being 22.4% and 21.6%, respectively. Further investigations are urgently needed to characterize the PCDD/Fs contamination levels not only in elasmobranch fish but in all Mediterranean marine biota.     

Terbuthylazine Contamination of the Aquifer North of Vicenza (North-East Italy) (5 pp)

- DOI: http://dx.doi/10.1065/espr2006.01.016 Background and Goal Agricultural practices can affect the quality of aquifers given that they are often located in cropped areas, so significant amounts of pesticides can be found in the water. In particular, triazine herbicides are always carefully checked by the official monitoring systems. The goal of this study was to find the mean concentration of terbuthylazine in an Italian aquifer and to set up a mass balance of this compound. Methods Terbuthylazine concentrations in the aquifer were measured in various check-wells during 1998–2004, and the value of censored data were estimated using a Gompertz inverse in order to evaluate the overall mean concentration. The total terbuthylazine load in the recharge area was calculated on the basis of surveys of cropped land and the main weed control techniques applied in the area. Data on aquifer water balance were obtained from previous studies. Results and Discussion The herbicide terbuthylazine applied in the recharge zone can be transported by surface water and enter the aquifer. Detected concentrations were always well below the EU drinking water limit and the fraction that can reach the groundwater under normal cropping practices is small, very likely less than 0.2%. Recommendations and Outlook The use and application rates of pesticides should be strictly regulated in recharge areas. Vegetated buffer strips can mitigate the impact of herbicides on surface water through reducing drift and early-spring runoff. Attention should also be paid to the fate of the main metabolites from soil biochemical processes.     

Solicitation displays reliably reflect oxidative damage in barn swallow nestlings

Reproduction entails parental decisions over allocation of limiting resources. ‘Begging’ solicitation displays by the offspring have been hypothesised to evolve as reliable indicators of quality, allowing parents to adopt optimal allocation strategies. To function as such, however, begging signals must covary with offspring traits that affect viability. Here we tested whether oxidative damage of nestling barn swallows predicts begging bout duration, call amplitude and intensity of postural displays both under normal food provisioning and under food shortage. Oxidative damage as determined by normal metabolism, pathological conditions and functioning of the immune system can serve as a comprehensive indicator of offspring condition because it can profoundly affect viability, senescence and reproduction. Begging bout duration was negatively predicted by oxidative damage but only after food deprivation. Postural begging negatively covaried with oxidative damage, at least when nestlings were confronted with related nest mates. Plasma antioxidant capacity did not predict begging behaviour. Thus, we show for the first time that behavioural begging covaries with a comprehensive index of chick condition, lending support to reliability of such begging traits also as signals of quality rather than need or hunger only. Future studies are candidate to decouple the effect of hunger state and individual condition on behavioural begging.     

Wind- and tide-induced currents in the Stagnone lagoon (Sicily)

The hydrodynamic circulation is analyzed in the coastal lagoon of Stagnone di Marsala, a natural reserve located in the north-western part of Sicily, using both experimental measurements and numerical simulations. Field measurements of velocities and water levels, carried out using an ultrasound sensor (3D), are used to validate the numerical model. A 3D finite-volume model is used to solve the Reynolds-averaged momentum and mass balance differential equations on a curvilinear structured grid, employing the k–e{\varepsilon} turbulence model for the Reynolds stresses. The numerical analysis allows to identify the relative contribution of the forces affecting the hydrodynamic circulation inside the lagoon. In the simulations only wind and tide forces are considered, neglecting the effects of water density changes. Two different conditions are considered. In the first both the wind stress over the free-surface and the tidal motion are imposed. In the second the wind action is neglected, to separately analyze the tide-induced circulation. The comparison between the two test cases highlights the fundamental role of the wind on the hydrodynamics of the Stagnone lagoon, producing a strong vertical recirculation pattern that is not observed when the flow is driven by tides only.