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.     

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.     

Colloid-enhanced ultrafiltration in removal of traces amounts of borates from water

The use of colloid-enhanced ultrafiltration for boron removal from water is investigated. Biodegradable surfactant, 1,4-sorbitol oleate, was applied to obtain micelles and high molecular weight chitosan to reinforce their stability. Two kind of membranes were compared: neat porous polysulfone membrane and charged porous sulfonated polysylfone membrane; both with similar average pore diameter of 5 nm. The studies revealed that two key factors affect the boron rejection: presence of surfactant in the colloidal mixture and a repulsion effect of sulfone groups on the membrane surface. Both have a positive effect on boron removal.     

CFD Investigation of Particle Deposition in a Horizontal Looped Turbulent Pipe Flow

This paper presents comprehensive 3D numerical investigations on depositions of particles flowing through a horizontal pipe loop consisting of four bends. The multiphase mixture model available in FLUENT 6.2 was used in this study. In this numerical simulation, five different particle sizes have been used as secondary phases to calculate real multiphase effect in which inter-particle interaction has been considered. The deposition of particles along the periphery of the pipe wall was investigated as a function of particle size and fluid velocity. The simulations showed that near the upstream of the bends, maximum particle concentration occurred at the bottom of the pipe. However, downstream the bends, the maximum particle concentration occurred at an angle of 60° from the bottom. The larger particles clearly showed deposition near the bottom wall except downstream. As expected, the smaller particles showed less tendency of deposition and lesser at higher velocity. This numerical investigation showed qualitative agreement with the experiments conducted by Commonwealth Scientific and Industrial Research Organisation, Melbourne team for similar conditions.     

Climate changes and tree stand dynamics at the upper limit of their growth in the North Ural mountains

The composition and structure of tree stands near the timberline have been studied on different slopes and at different elevations in the Tylaisko-Konzhakovsko-Serebryanskii Massif, the North Urals. It has been found that the upper limits of tree stands with different degrees of canopy closure have risen considerably (by about 100 m of elevation) since the mid-19th century, although the formation of these stands started as early as the late 18th century. Woodless areas in the eastern part of the massif started to be colonized by Larix sibirica in the late 18th to early 19th centuries; those in the western part, by Picea obovata in the mid-19th century; and in the southern part, by Betula tortuosa in the late 19th century. Analysis of meteorological data provides evidence for warming and increasing humidity of the climate since the late 19th century. Favorable climatic changes that facilitated the expansion of the forest have taken place both in the summer (prolongation of the growing period) and in winter seasons (increase of air temperature and precipitation). The observed differences in the composition and dynamics of tree stands between the studied areas of the mountain range are most probably explained by different requirements of tree species for the depth of snow cover and the degree of soil freezing.