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.     

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.     

Alternative amendment for soluble phosphorus removal from poultry litter

Background, aim, and scope  

Alum (aluminum sulfate) is the currently preferred chemical amendment for phosphorus (P) treatment in poultry litter (PL). Aluminum-based drinking-water treatment residuals (Al-WTRs) are the waste by-product of the drinking-water treatment process and have been effectively used to remove P from aqueous solutions, but their effectiveness in PL water extracts has not been studied in detail. Elevated cost associated with alum could be minimized by using the equally effective WTRs to remove soluble P from PL, and they can be obtained at a minimal cost from drinking-water treatment plants.     

Chitosan-polypropylene imine dendrimer hybrid: a new ecological biomordant for cochineal dyeing of wool

The classical use of synthetic dyes is causing issues of environmental pollution and heath risk. As a consequence natural dyes are gaining interest, but the use of natural dyes still includes toxic reagents such as metals as mordants and acids to enhance color and yield. Therefore, we designed a new chitosan-polypropylene imine dendrimer hybrid at 0–2000 mg/L to treat wool before dyeing with cochineal. We compared dye exhaustion, color depth, color characteristics, and color fastness of the new process with dyed pristine and metal mordanted wool. Results show that wool pretreatment improved dye exhaustion from 48 to 88 %, shifted saturation point toward lower dye concentration from 3000 to 1000 mg/L, and improved color depth from 13.68 for pristine wool and 15.17 for metal mordanted wool to 23.89 for the new process.     

International Environmental Agreements: Design of Optimal Transfers Under Heterogeneity

International environmental agreements (IEAs) can coordinate abatement of transboundary pollutants. This paper investigates how heterogeneous countries facing a stock pollutant might structure such an agreement. In particular, we examine how an IEA might be implemented with a set of monetary transfers. The focus is on transfers that are time invariant, linear in emissions, and consistent with budget balance. There is a range of such schemes that would induce efficient emissions. We provide a simple and intuitive characterization of these penalties and describe how specific proposals might be chosen in order to facilitate compliance and implementation. Our proposals are illustrated with a simple example. We show that heterogeneity reduces the scope for penalty schemes to jointly satisfy desirable properties.     

Triterpene saponin hemi-biosynthesis of a leaf beetle’s (<Emphasis Type="Italic">Platyphora kollari</Emphasis>) defensive secretion

The adults of the leaf beetle Platyphora kollari (Chrysomelidae) are able to metabolise the oleanane triterpene β-amyrin (1) into the glycoside 3-O-β-d-glucopyranosyl-(1→4)-β-d-glucuronopyranosyl-hederagenin (2) that is stored in their defensive glands. The aim of this study was to test the hypothesis that oleanolic acid (3) is an intermediate in the conversion of 1 into 2 and to check whether the sequestration of pentacyclic triterpenes is selective in favour of β-amyrin (1). To this end, adults of P. kollari were fed with Ipomoea batatas leaf disks painted with a solution of [2,2,3-²H₃]oleanolic acid or [2,2,3-²H₃]α-amyrin and the secretion of their defensive glands analysed by HPLC–ESIMS. The data presented in this work indicated that the first step of the transformation of β-amyrin (1) into the sequestered glycoside 2 is its oxidation into oleanolic acid (3) and that this conversion is selective but not specific in favour of β-amyrin (1).     

How Plants Cope with Foreign Compounds. Translocation of xenobiotic glutathione conjugates in roots of barley (Hordeum vulgare) (9 pp)

Background, Aim and Scope Numerous herbicides and xenobiotic organic pollutants are detoxified in plants to glutathione conjugates. Following this enzyme catalyzed reaction, xenobiotic GS-conjugates are thought to be compartmentalized in the vacuole of plant cells. In the present study, evidence is presented for long range transport of these conjugates in plants, rather than storage in the vacuole. To our knowledge this is the first report about the unidirectional long range transport of xenobiotic conjugates in plants and the exudation of a glutathione conjugate from the root tips. This could mean that plants possess an excretion system for unwanted compounds which give them similar advantages as animals. Materials and Methods: Barley plants (Hordeum vulgare L. cv. Cherie) were grown in Petri dishes soaked with tap water in the greenhouse. - Fluorescence Microscopy. Monobromo- and Monochlorobimane, two model xenobiotics that are conjugated rapidly in plant cells with glutathione, hereby forming fluorescent metabolites, were used as markers for our experiments. Their transport in the root could be followed sensitively with very good temporal and spatial resolution. Roots of barley seedlings were cut under water and the end at which xenobiotics were applied was fixed in an aperture with a thin latex foil and transferred into a drop of water on a cover slide. The cover slide was fixed in a measuring chamber on the stage of an inverse fluorescence microscope (Zeiss Axiovert 100). - Spectrometric enzyme assay. Glutathione S-transferase (GST) activity was determined in the protein extracts following established methods. Aliquots of the enzyme extract were incubated with 1-chloro-2,4-dinitrobenzene (CDNB), or monochlorobimane. Controls lacking enzyme or GSH were measured. - Pitman chamber experiments. Ten days old barley plants or detached roots were inserted into special incubation chambers, either complete with tips or decapitated, as well as 10 days old barley plants without root tips. Compartment A was filled with a transport medium and GSH conjugate or L-cysteine conjugate. Compartments B and C contained sugar free media. Samples were taken from the root tip containing compartment C and the amount of conjugate transported was determined spectro-photometrically. Results: The transport in roots is unidirectional towards the root tips and leads to exsudation of the conjugates at rates between 20 and 200 nmol min-1. The microscopic studies have been complemented by transport studies in small root chambers and spectroscopic quantification of dinitrobenzene-conjugates. The latter experiments confirm the microscopic studies. Furthermore it was shown that glutathione conjugates are transported at higher rates than cysteine conjugates, despite of their higher molecular weights. This observation points to the existence of glutathione specific carriers and a specific role of glutathione in the root. Discussion: It can be assumed that long distance transport of glutathione conjugates within the plant proceeds like GSH or amino acid transport in both, phloem and xylem. The high velocity of this translocation of the GS-X is indicative of an active transport. For free glutathione, a rapid transport-system is essential because an accumulation of GSH in the root tip inhibits further uptake of sulfur. Taking into account that all described MRP transporters and also the GSH plasmalemma ATPases have side activities for glutathione derivatives and conjugates, co-transport of these xenobiotic metabolites seems credible. - On the other hand, when GS-B was applied to the root tips from the outside, no significant uptake was observed. Thus it can be concluded that only those conjugates can be transported in the xylem which are formed inside the root apex. Having left the root once, there seems to be no return into the root vessels, probably because of a lack of inward directed transporters. Conclusions: Plants seem to possess the capability to store glutathione conjugates in the vacuole, but under certain conditions, these metabolites might also undergo long range transport, predominantly into the plant root. The transport seems dependent on specific carriers and is unidirectional, this means that xenobiotic conjugates from the rhizosphere are not taken up again. The exudation of xenobiotic metabolites offers an opportunity to avoid the accumulation of such compounds in the plant. Recommendations and Perspectives: The role of glutathione and glutathione related metabolites in the rhizosphere has not been studied in any detail, and only scattered data are available on interactions between the plant root and rhizosphere bacteria that encounter such conjugates. The final fate of these compounds in the root zone has also not been addressed so far. It will be interesting to study effects of the exuded metabolites on the biology of rhizosphere bacteria and fungi.     

Gasification characteristics of biomass for tar removal by secondary oxidant injection

Gasification experiments for sawdust were conducted using a fixed bed reactor at 900 °C by varying the secondary oxidant injection ratio to determine the optimal conditions for tar removal along with the enhancement of gasification efficiency. Secondary oxidant was injected as an oxidant at the top zone of the gasifier in varying ratios of 10–30% of the total amount of oxidant. This method was based on the primary method of tar removal and gasification efficiency improvement by thermal cracking of tar. Various gasification performance parameters were evaluated and tar content was estimated by measuring the fluctuation of weight of the activated carbon filter. The results showed that the concentration of tar in the producer gas decreased by injecting the secondary oxidant, even though syngas yield decreased. The recycling potential of the char produced in the gasification experiments was also assessed with the purpose of utilizing char as an adsorbent by determining its surface area and pore volume. The results demonstrated that the char produced from the gasification experiment had similar quality to that of the activated carbon used in this experiment.     

Production of natural and recycled aggregates: the environmental impacts of energy consumption and CO<Subscript>2</Subscript> emissions

Natural aggregates (NA) are crushed and processed in crushing plants after the extraction stage in quarries. In the present study, the aggregates are divided into three scenarios, depending on the production methods. The first scenario considers the production of NA, the second scenario deals with the production of recycled aggregates (RA) with respect to construction and demolition waste, and the third scenario, which is a hybrid scenario, handles the combination of NA and RA by assuming a 50% mixing percentage. In this research, we assess the environmental impacts on the production of aggregates via each scenario, using life cycle assessment; in addition, energy consumption and CO₂ emissions are considered as the environmental variables. We conclude that Iran’s current policy with an annual energy consumption of 1.48 million tons of oil equivalent (toe) can have a footprint of 2.88 million tons of CO₂ eq emissions per year (the first scenario). Achieving 30 and 36% reduction in annual energy consumption and CO₂ emissions, respectively, by the third scenario compared to the first scenario indicates the destructive effect of the first scenario from the environmental outlook.