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.     

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.     

Female reproductive qualities affect male painted turtle (Chrysemys picta marginata) reproductive success

Male reproductive success (RS) in polygamous species with minimal social systems is often determined by the number of mates. However, because male RS is translated through females, the number of offspring sired can also be influenced by female qualities. Empirically sufficient data to document how tradeoffs between mate number and quality influence male RS are seldom available for long-lived, iteroparous species. We combined long-term life history data (1983–2006) on the E. S. George Reserve (ESGR, MI, USA) with parentage data from 155 clutches of 59 female painted turtles (Chrysemys picta marginata) of varying reproductive frequencies (2003–2006) to determine the relative contribution of female numbers and qualities on male RS. One previously documented trait of female painted turtles that can have substantial influences on male RS is repeat paternity through the use of stored sperm to fertilize over 95 % of within-year clutches. In addition, our study found that second-clutch producing female painted turtles on the ESGR have higher among-year reproductive frequencies than do first-clutch only females. Multiple paternity was detected in 14.1 % of clutches (min-max?=?6.1–30.0 % annually), and the number of mates of both sexes was low annually (males 1.0; females 1.2) and over 4 years (males 1.1; females 1.7). Among successful males, RS varied substantially (1–32 offspring) and was strongly influenced by the combination of female reproductive frequency and repeat paternity (>38 % among years), but not mate number. Low mate number for both sexes was unexpected in a species without complex mating behaviors or parental care.