Oxidative degradation of chlorophenol derivatives promoted by microwaves or power ultrasound: a mechanism investigation

Background, aim, and scope

Phenols are the most common pollutants in industrial wastewaters (particularly from oil refineries, resin manufacture, and coal processing). In the last two decades, it has become common knowledge that they can be effectively destroyed by nonconventional techniques such as power ultrasound (US) and/or microwave (MW) irradiation. Both techniques may strongly promote advanced oxidation processes (AOPs). The present study aimed to shed light on the effect and mechanism of US- and MW-promoted oxidative degradation of chlorophenols; 2,4-dichlorophenoxyacetic acid (2,4-D), a pesticide widespread in the environment, was chosen as the model compound.

Materials and methods

2,4-D degradation by AOPs was carried out either under US (20 and 300 kHz) in aqueous solutions (with and without the addition of Fenton reagent) or solvent-free under MW with sodium percarbonate (SPC). All these reactions were monitored by gas chromatography–mass spectrometry (GC–MS) analysis and compared with the classical Fenton reaction in water under magnetic stirring. The same set of treatments was also applied to 2,4-dichlorophenol (2,4-DCP) and phenol, the first two products that occur a step down in the degradation sequence. Fenton and Fenton-like reagents were employed at the lowest active concentration.

Results

The effects of US and MW irradiation were investigated and compared with those of conventional treatments. Detailed mechanisms of Fenton-type reactions were suggested for 2,4-D, 2,4-DCP, and phenol, underlining the principal degradation products identified. MW-promoted degradation under solvent-free conditions with solid Fenton-like reagents (viz. SPC) is extremely efficient and mainly follows pyrolytic pathways. Power US strongly accelerates the degradation of 2,4-D in water through a rapid generation of highly reactive radicals; it does not lead to the formation of more toxic dimers.

Discussion

We show that US and MW enhance the oxidative degradation of 2,4-D and that a considerable saving of oxidants and cutting down of reaction times is thereby achieved. The results support the interpretation of previously published data and improve the understanding of the factors of direct degradation along different pathways.

Conclusions

Oxidative pathways for 2,4-D, 2,4-DCP, and phenol were proposed by a careful monitoring of the reactions and detection of intermediates by GC–MS.

Recommendations and perspectives

The understanding of the factors that affect chlorophenols degradation along different pathways may facilitate the optimization of the treatment. Type of energy source (US or MW), power, and frequency to be applied could be designed in function of the operative scenario (amount of pollutant in soil, water, or oils).     

Village pubs as a social propellant in rural areas: an econometric study

There is no place like England to witness the role of pubs as a social networking hotspot. Social networks lie at the foundations of most of the social and economic interactions of individuals. The aim of this paper is to assess the importance of pubs as natural locations for the development of social networks and how their presence affects the socio-economic activity of a given area or region. The econometric analysis conducted on rural parishes in Cumbria, a peripheral county in Northern England, reveals that village pubs have a positive influence on the socio-economic activity of local communities.     

Climate hotspots: key vulnerable regions,climate change and limits to warming

This paper reviews scientific and gray literature addressing climate change vulnerability and adaptation in the Inuvialuit Settlement Region (ISR) in the western Canadian Arctic. The review is structured using a vulnerability framework, and 420 documents related directly or indirectly to climate change are analyzed to provide insights on the current state of knowledge on climate change vulnerability in the ISR as a basis for supporting future research and long-term adaptation planning in the region. The literature documents evidence of climate change in the ISR which is compromising food security and health status, limiting transportation access and travel routes to hunting grounds, and damaging municipal infrastructure. Adaptations are being employed to manage changing conditions; however, many of the adaptations being undertaken are short term, ad-hoc, and reactive in nature. Limited long-term strategic planning for climate change is being undertaken. Current climate change risks are expected to continue in the future with further implications for communities but less is known about the adaptive capacity of communities. This review identifies the importance of targeted vulnerability research that works closely with community members and decision makers to understand the interactions between current and projected climate change and the factors which condition vulnerability and influence adaptation. Research gaps are identified, and recommendations for advancing adaptation planning are outlined.     

Recovery of MSWI and soil washing residues as concrete aggregates

The aim of the present work was to study if municipal solid waste incinerator (MSWI) residues and aggregates derived from contaminated soil washing could be used as alternative aggregates for concrete production.Initially, chemical, physical and geometric characteristics (according to UNI EN 12620) of municipal solid waste incineration bottom ashes and some contaminated soils were evaluated; moreover, the pollutants release was evaluated by means of leaching tests. The results showed that the reuse of pre-treated MSWI bottom ash and washed soil is possible, either from technical or environmental point of view, while it is not possible for the raw wastes.Then, the natural aggregate was partially and totally replaced with these recycled aggregates for the production of concrete mixtures that were characterized by conventional mechanical and leaching tests. Good results were obtained using the same dosage of a high resistance cement (42.5R calcareous Portland cement instead of 32.5R); the concrete mixture containing 400 kg/m³ of washed bottom ash and high resistance cement was classified as structural concrete (C25/30 class). Regarding the pollutants leaching, all concrete mixtures respected the limit values according to the Italian regulation.     

Comparative study of the urban quality of life in Cuban first-level cities from an objective dimension

The urban quality of life (UQoL) from objective dimension was analyzed in the main Cuban cities. An Urban Quality of Life Index (UQoLI) was developed in collaboration with 60 experts (five in each city). These experts belong to one of two categories: in charge of the planning of the city and members of the Municipal Council of Administration. One hundred and forty-two directors of the Local District Administration also participated in the analysis. The UQoLI includes three dimensions: social services, economic performance, and urban services, the importance of which is weighed according to expert criteria. A Ranking of the studied cities, sorted by the UQoLI, shows a tendency of increase it UQoL in the west even and central regions. This tendency contradicts one of the foundations of the Cuban sustainable development framework, i.e., equity.     

Cardiac flow after fetal blood sampling in normally grown and growth-retarded fetuses

The objective of this study was to evaluate the effect of fetal blood sampling on cardiac flow velocity waveforms. Flow velocity waveforms were measured from the ascending aorta and pulmonary artery immediately before and after fetal blood sampling in 29 normally grown and 12 growth-retarded fetuses. The latter group was characterized by abnormal Doppler indices in the umbilical artery and middle cerebral artery suggestive of uteroplacental insufficiency as the causative factor of the impaired growth. The flow velocity parameters studied were the peak velocity, the time to peak velocity, and the left and right cardiac output and their ratio. In normally grown fetuses, the peak velocity and right and left cardiac output values increased significantly after fetal blood sampling, while no significant changes were observed in the other indices considered. The gestational age at the time of the procedure was positively related to the amplitude of these changes. In growth-retarded fetuses, fetal blood sampling did not induce any significant increase in cardiac output or peak velocities, while in more than 50 per cent of the fetuses these Doppler indices decreased. The amplitude of the decrease was significantly related to the severity of acidosis in the umbilical vein. In conclusion, the cardiac haemodynamic response to fetal blood sampling differs between normally grown and growth-retarded fetuses. This difference may explain the higher rate of complications occurring in the latter group of fetuses after blood sampling.     

The systematic position of some boring sponges (Demospongiae,Hadromerida) studied by molecular analysis

A phylogenetic analysis of some bioeroding sponges of the family Clionaidae (Order Hadromerida) was performed to resolve some taxonomic problems both at the specific and the supraspecific level using the D2 and D3 regions of 28S rDNA. Species belonging to the genera Cliona, Cliothosa, Spheciospongia (fam. Clionaidae) and Diplastrella (fam. Spirastrellidae) from the Mediterranean Sea and Celebes Sea (Indonesia) were analysed. In the phylogenetic tree, the species clustered on two main branches, one comprising Cliona celata, C. rhodensis, C. utricularis, and Cliothosa hancocki, and the other made up of C. viridis, C. nigricans, C. schmidti, C. jullieni, Spheciospongia solida and S. vagabunda. Above the species level, data do not support the separation of the genus Cliothosa from Cliona, while they do support the inclusion of some massive boring species, previously assigned to the genus Spirastrella, in the family Clionaidae. At the species level, data demonstrated the genetic identity of taxa C. viridis and C. nigricans, in spite of their considerable morphological differences. In contrast, the yellow species commonly attributed to C. celata are probably to be considered as a complex of sibling species with a number of distinct taxa present in the Mediterranean. Data also showed the identity of the Mediterranean and Pacific populations of C. schmidti, suggesting the status of a Tethyan relict for this species.     

A stratified model for the assessment of meteorologically adjusted trends of surface ozone

We consider the problem of assessing long-term trends of ozone concentrations measured on a single site located in an urban area. Among the many methods proposed in the literature to eliminate the confounding effect of changing weather conditions, we employ a stratification of daily maxima based on regression trees. Within each stratum conditional independence and Weilbull distribution are assumed for maxima. Long-term trend is defined non-parametrically by the sequence of yearly medians. Models are estimated following the Bayesian approach. The alternative assumptions of common and stratum specific trends are compared and a model with common trend for all strata is selected for the analyzed real dataset. The conditional independence assumption is checked by the comparison with a model including an autoregressive component.     

Safeguarding Wetlands and Their Connections within Wetlandscapes to Improve Conservation Outcomes for Threatened Amphibian Species

Wetlands should not be considered as independent objects but as dynamically connected objects, collectively known as wetlandscapes. We developed a framework that analyzes the influences of wetland suitability and connectivity on amphibian distributions. We defined two indices: a Wetland Suitability Index describing wetland quality and a Movement Permeability Index characterizing wetland connectivity for amphibian population dynamics. These indices were calculated from raster datasets and time‐varying inundation estimates. The indices were used to define a wetlandscape and an amphibian model was used to simulate population dynamics within the wetlandscape. The framework was applied to the Nose Creek watershed, a highly modified wetlandscape in Alberta, Canada. Two amphibian species were selected with different habitat preferences: the Northern Leopard Frog that prefers wet habitats and has high mobility over land, and the Great Plains Toad that prefers terrestrial habitats and has low mobility over land. We found each amphibian species had a “preferred” wetlandscape, reflecting their life cycle traits and migration strategies which in turn were dependent on the hydrological and ecological connections within the wetlandscape. This study highlights the importance of investigating both individual wetlands and the wetlandscape and considering both wetland habitat quality and connectivity as non‐substitutable properties that act jointly, but differently, on population dynamics.     

Tensile Behavior of Thermoplastic Films from Wheat Flours as Function of Raw Material Baking Properties

The production of bioplastics directly from wheat flour has been demonstrated to be reliable, but scarce knowledge is available on how flour characteristics may affect the performance of thermoplastic films. In this work, we first established the most suitable recipe and process for the production of extruded films and then we used eight single-cultivar wheat flours with different baking technological properties to assess how they affect the mechanical properties of thermoplastic films. The results have shown that flours from soft grain cultivars offered more rigid and deformable films than flours from hard grain cultivars. For similar hardness, the alveographic P/L ratio of the dough was inversely related to rigidity and directly related to deformability of plastic films, while the deformation energy of the dough (W) played a role only for great differences of it. The subsequent fabrication of blends between each of the flours that yielded the best film properties and polycaprolactone (PCL) at different proportions indicated that a wheat flour/PCL ratio (TWF/PCL) of 75/25 offered the most suitable films for further application. Our results are likely to be useful for improving the plasticization of flour, in that selection of wheat flours could be tailored on the properties desired for the bioplastic films.