Catalytic activities and mechanism of formaldehyde oxidation over gold supported on MnO<Subscript>2</Subscript> microsphere catalysts at room temperature

MnO₂ microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO₂ catalysts were synthesized using the sol-gel method. We obtained three MnO₂ microspheres and Au/MnO₂ samples: coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO₂ are the main factor affecting the catalytic activities of these samples, and γ-MnO₂ shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO₂. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO₂. We also studied intermediate species. The dioxymethylene (DOM) and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO₂. A proposed mechanism of formaldehyde oxidation over Au/MnO₂ catalysts was also obtained.     

Exploring the risks and benefits of flexibility in biodiversity offset location in a case study of migratory shorebirds

Biodiversity offsets aim to counterbalance the residual impacts of development on species and ecosystems. Guidance documents explicitly recommend that biodiversity offset actions be located close to the location of impact because of higher potential for similar ecological conditions, but allowing greater spatial flexibility has been proposed. We examined the circumstances under which offsets distant from the impact location could be more likely to achieve no net loss or provide better ecological outcomes than offsets close to the impact area. We applied a graphical model for migratory shorebirds in the East Asian–Australasian Flyway as a case study to explore the problems that arise when incorporating spatial flexibility into offset planning. Spatially flexible offsets may alleviate impacts more effectively than local offsets; however, the risks involved can be substantial. For our case study, there were inadequate data to make robust conclusions about the effectiveness and equivalence of distant habitat-based offsets for migratory shorebirds. Decisions around offset placement should be driven by the potential to achieve equivalent ecological outcomes; however, when considering more distant offsets, there is a need to evaluate the likely increased risks alongside the potential benefits. Although spatially flexible offsets have the potential to provide more cost-effective biodiversity outcomes and more cobenefits, our case study showed the difficulty of demonstrating these benefits in practice and the potential risks that need to be considered to ensure effective offset placement.     

Trends in the development of Estonian coastal land cover and landscapes caused by natural changes and human impact

The structure of coastal land cover in Estonia is intricate and exhibits considerable differences from site to site. The diverse geomorphology of the seashores is one of the key factors affecting the speed and magnitude of land cover changes. Likewise, the history of human inhabitance on the coast has also shaped the character of land cover. The Estonian coastal zone has experienced abrupt and radical changes in land ownership and its related land use during the last century. The main objectives of this paper are: 1) to give an overview of land use and the trends of development of land cover pattern along different parts of the Estonian coast; and 2) to analyze the relationships of natural and human processes and their cumulative impact on the evolution of coastal land cover pattern in Estonia. This study is based on results obtained during fieldwork in the study areas and on the analysis of large-scale (1:10,000) historical maps. In agriculturally dominant coastal areas, the traditional open landscape of fields and grassland at the beginning of the 20th century had been replaced by woodland and grasslands with shrubs by the start of the 21st century. Expansion of reed beds in areas of former seashore grasslands is another striking phenomenon. The structure of land cover on forested coasts has been fairly stable during the last 100 years. Areas of urban sprawl are characterised by dramatic changes in land cover structure. Rapidly increasing population and expanding settlements imposes on the ecological balance of the fragile dune forests in the coastal zone.     

Effects of pharmaceuticals and personal care products on marine organisms: from single-species studies to an ecosystem-based approach

Pharmaceuticals and personal care products (PPCPs) are contaminants of emerging concern that are increasing in use and have demonstrated negative effects on aquatic organisms. There is a growing body of literature reporting the effects of PPCPs on freshwater organisms, but studies on the effects of PPCPs to marine and estuarine organisms are limited. Among effect studies, the vast majority examines subcellular or cellular effects, with far fewer studies examining organismal- and community-level effects. We reviewed the current published literature on marine and estuarine algae, invertebrates, fish, and mammals exposed to PPCPs, in order to expand upon current reviews. This paper builds on previous reviews of PPCP contamination in marine environments, filling prior literature gaps and adding consideration of ecosystem function and level of knowledge across marine habitat types. Finally, we reviewed and compiled data gaps suggested by current researchers and reviewers and propose a multi-level model to expand the focus of current PPCP research beyond laboratory studies. This model includes examination of direct ecological effects including food web and disease dynamics, biodiversity, community composition, and other ecosystem-level indicators of contaminant-driven change.     

Archaeometric researches on the provenance of Mediterranean Archaic Phoenician and Punic pottery

The aim of this study is to setup a first chemical database that could represent the starting point for a reliable classification method to discriminate between Archaic Phoenician and Punic pottery on the base of their chemical data. This database up to now can discriminate between several different areas of production and provenance and can be applied also to unknown ceramic samples of comparable age and production areas. More than 100 ceramic fragments were involved in this research, coming from various archaeological sites having a crucial importance in the context of the Phoenician and Punic settlement in central and western Mediterranean: Carthage (Tunisia), Toscanos (South Andalusia, Spain), Sulci, Monte Sirai, Othoca, Tharros (Sardinia, Italy) and Pithecusa (Campania, Italy). Since long-time archaeologists hypothesised that Mediterranean Archaic Phoenician and Punic pottery had mainly a local or just a regional diffusion, with the exception of some particular class like transport amphorae. To verify the pottery provenance, statistical analyses were carried out to define the existence of different ceramic compositional groups characterised by a local origin or imported from other sites. The existing literature data are now supplemented by new archaeometric investigations both on Archaic Phoenician ceramics and clayey raw materials from Sardinia. Therefore, diffractometric analyses, optical microscopy observations and X-ray fluorescence analyses were performed to identify the mineralogical and chemical composition of Othoca ceramics and clayey raw material. The obtained results were then compared with own literature data concerning Phoenician and Punic pottery in order to find features related to the different ceramic productions and their provenance. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were also performed on the chemical compositional data in order to discriminate ceramic groups. A very complex situation was found: imported ceramics coming from Carthage, with a large-scale distribution, were found together with a predominant local production pottery. The archaeometric results demonstrate that historical and typological approach has to be supported by scientific analyses to better understand local or Mediterranean exchanges.     

Applications of Very High‐Resolution Imagery in the Study and Conservation of Large Predators in the Southern Ocean

The Southern Ocean is one of the most rapidly changing ecosystems on the planet due to the effects of climate change and commercial fishing for ecologically important krill and fish. Because sea ice loss is expected to be accompanied by declines in krill and fish predators, decoupling the effects of climate and anthropogenic changes on these predator populations is crucial for ecosystem‐based management of the Southern Ocean. We reviewed research published from 2007 to 2014 that incorporated very high‐resolution satellite imagery to assess distribution, abundance, and effects of climate and other anthropogenic changes on populations of predators in polar regions. Very high‐resolution imagery has been used to study 7 species of polar animals in 13 papers, many of which provide methods through which further research can be conducted. Use of very high‐resolution imagery in the Southern Ocean can provide a broader understanding of climate and anthropogenic forces on populations and inform management and conservation recommendations. We recommend that conservation biologists continue to integrate high‐resolution remote sensing into broad‐scale biodiversity and population studies in remote areas, where it can provide much needed detail. Aplicaciones de Imágenes de Muy Alta Resolución en el Estudio y Conservación de Grandes Depredadores en el Océano Antártico     

Environmental impact of exhaust emissions by Arctic shipping

Since 2005, a dramatic decline of the Arctic sea-ice extent is observed which results in an increase of shipping activities. Even though this provides commercial and social development opportunities, the resulting environmental impacts need to be investigated and monitored. In order to understand the impact of shipping in arctic areas, the method described in this paper determines the travel time, fuel consumption and resulting exhaust emissions of ships navigating in arctic waters. The investigated case studies are considering ship particulars as well as environmental conditions with special focus on ice scenarios. Travel time, fuel consumption and exhaust gas emission were investigated for three different vessels, using different passages of the Northern Sea Route (NSR) in different seasons of years 1960, 2000 and 2040. The presented results show the sensitivity of vessel performance and amount of exhaust emissions to optimize arctic traffic with respect to efficiency, safety and environmental impact.     

Enhanced degradation of the antibiotic tetracycline by heterogeneous electro-Fenton with pyrite catalysis

There is actually increasing concern about the accumulation of antibiotics, such as tetracycline, in soil and water bodies. There is therefore a need for efficient methods to degrade antibiotics and thus clean waters. Here we tested the degradation of tetracycline using the heterogeneous electro-Fenton-pyrite method and compared the results with the conventional electro-Fenton method. The reaction was performed with a boron-doped diamond or Pt anode and carbon-felt cathode allowing electrogeneration of H₂O₂ from O₂ reduction. Results show an increasing tetracycline mineralization using the following methods: anodic oxidation with electrogenerated H₂O₂, electro-Fenton and then electro-Fenton-pyrite using boron-doped diamond. Ion-exclusion HPLC revealed the complete removal of malic malonic, succinic, acetic, oxalic and oxamic acids. Nitrogen present in tetracycline was mainly mineralized in NH₄ ⁺. The higher efficiency of electro-Fenton-pyrite is explained by self-regulation of soluble Fe²⁺ and pH to 3.0 from pyrite catalyst favoring larger ^·OH generation from Fenton’s reaction.