Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol

Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared.     

Chiral pharmaceuticals in the environment

Many pharmaceutical pollutants are chiral, existing in the environment as a single enantiomer or as mixtures of the two enantiomers. In spite of their similar physical and chemical properties, the different spatial configurations lead the enantiomers to have different interactions with enzymes, receptors or other chiral molecules, which can give diverse biological response. Consequently, biodegradation process and ecotoxicity tend to be enantioselective. Despite numerous ongoing research regarding analysis and monitorization of pharmaceutical ingredients in the environment, the fate and effects of single enantiomers of chiral pharmaceuticals (CP) in the environment are still largely unknown. There are only few chiral analytical methods to accurately measure the enantiomeric fraction (EF) in environmental matrices and during biodegradation processes. Furthermore, the ecotoxicity studies usually consider the enantiomeric pair as unique compound. We reviewed the current knowledge about CP in the environment, as well as the chiral analytical methods to determine the EF in environmental matrices. The degradation and removal processes of CP of important therapeutic classes, usually detected in the environment, and their toxicity to aquatic organisms were also reviewed. On the other hand, this review demonstrate that despite the great importance of the stereochemistry in pharmaceutical science, pharmacology and organic chemistry, this is normally neglected in environmental studies. Therefore, CP in the environment need much more attention from the scientific community, and more research within this subject is required.     

Temporal separation of two fin whale call types across the eastern North Pacific

Fin whales (Balaenoptera physalus) produce a variety of low-frequency, short-duration, frequency-modulated calls. The differences in temporal patterns between two fin whale call types are described from long-term passive acoustic data collected intermittently between 2005 and 2011 at three locations across the eastern North Pacific: the Bering Sea, off Southern California, and in Canal de Ballenas in the northern Gulf of California. Fin whale calls were detected at all sites year-round, during all periods with recordings. At all three locations, 40-Hz calls peaked in June, preceding a peak in 20-Hz calls by 3–5 months. Monitoring both call types may provide a more accurate insight into the seasonal presence of fin whales across the eastern North Pacific than can be obtained from a single call type. The 40-Hz call may be associated with a foraging function, and temporal separation between 40- and 20-Hz calls may indicate the separation between predominately feeding behavior and other social interactions.     

Use of isoperibolic calorimetry for the study of the effect of water concentration,temperature and reactor venting on the rate of hydroxylamine thermal decomposition

Hydroxylamine, NH₂OH, thermal decomposition has been responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting the rate of its decomposition are not understood. In this work, isoperibolic calorimetric measurements were performed in a metal reactor, in the temperature range 130–150 °C, employing 30–80 ml solutions containing 1.4–20 g of pure hydroxylamine (2.8–40 g of the supplied reagent). The calorimetric measurements were performed in order to assess the effects that NH₂OH concentration, temperature and reactor venting has on NH₂OH rate of decomposition. The measurements showed that increased concentration or temperature, results in faster reactions and probably higher pressure generation per mass of reactant, with concentration having a more pronounced effect. However, when both factors work synergistically the result is dramatically worse in terms of reaction rate. The pressure generation is also different, thus indicating that different reaction pathways predominate each time. Venting the produced gases in stages resulted in the highest mass loss of the solution.     

Exploring socio-cultural values of ecosystem service categories in the Central Alps: the influence of socio-demographic factors and landscape type

The socio-cultural assessment of ecosystem services has been proposed as a promising tool for eliciting people’s preferences towards ecosystem services. Despite an increasing integration of the socio-cultural perspective in ecosystem service research, little knowledge exists about linkages between landscape and the socio-cultural values people assign to ecosystem services. This paper combines a socio-cultural valuation approach with the use of landscape pictures to analyse and compare people’s perceived importance of the provisioning, regulating, and cultural ecosystem service categories across three landscape types (i.e. larch meadows, spruce forests, and hay meadow). A survey with 470 tourists visiting the region of South Tyrol (Italy) was conducted to link people’s perceived importance to their socio-demographic background and to the landscape types explored. The results show that regulating ecosystem services are preferred over provisioning and cultural services, whereby environmental awareness is found to be more influential than formal education levels regarding the perceived importance of regulating services. The results further demonstrate that cultural background is an important driver in determining people’s perceived importance of cultural services. The underlying landscape types, however, exert an even stronger influence on people’s socio-cultural valuation of ecosystem service categories. This finding suggests that the focus of most ecosystem services assessments on the study area as a whole risks mistakenly attributing differences in people’s socio-cultural values to socio-demographic characteristics only. A better knowledge of the spatial integration of socio-cultural values, however, could help with anticipating the consequences of changes in the landscape and provide better guidance for future landscape planning.     

Exchange of sulfur pollution between Bulgaria and Greece

The EMAP model (Eulerian Model for Air Pollution) is applied for calculating the sulfur concentration and deposition fields for 1995 as based upon Bulgarian and Greek sources. The country-to-country budgets show that about 4% of the sulfur oxides emitted by Bulgaria are deposited over Greek territory, estimated at 28 kt S. Only 2% of sulfur compounds emitted by Greece are deposited over Bulgaria, estimated at 6.2 kt S for 1995. This data is in agreement with EMEP/MSC-W estimates and provides more details concerning time and space. The results can be used in decision-making, negotiating and the development of contamination strategies.     

Joint use of data and modeling in coastal wave transformation

In the framework of a research project entitled ??BRISA??BReaking waves and Induced SAnd transport??, a methodology was devised to characterize the waves joining together in-situ measurements and numerical wave propagation models. With this goal in mind, a number of in-situ measurements were made, for selected positions in front of Praia de Faro (South Portugal), during four days (25th to 28th March, 2009) by using different types of equipments (e.g., resistive wave gauges, pressure sensors, currentmeters and a new prototype pore pressure sensor using optical fibre). Wave records were obtained simultaneously offshore (at a water depth of 11.7?m below mean sea level, MSL) and at the surf and swash zones. The data processing and analysis were made by applying classical time domain techniques. Numerical simulations of the wave propagation between offshore and inshore for the measurement period were performed with two numerical models, a 1D model based on linear theory and a nonlinear Boussinesq-type model, COULWAVE, both forced by the measured offshore wave conditions of 27th March 2009. Comparisons between numerical results and field data for the pressure sensors placed in the surf and swash zones were made and discussed. This approach enables to evaluate the performance of those models to simulate those specific conditions, but also to validate the models by gaining confidence on their use in other conditions.     

Characterization and Properties of Hydrophilic Cellulose Acetate Propionate Derivative

The chemical modification of Acrylamidomethyl Cellulose Acetate Propionate (AMCAP) was carried out by radical addition of acrylic acid. The structural modification was confirmed with the aid of FTIR, MS and NMR techniques. Thermal properties of hydrophilic cellulose derivative (AMCAP–H₂O₂) such as glass transition (T_g 153 °C) and thermal stability (372.7 °C) were determined by DSC and TGA techniques, respectively. These thermal properties confirmed the introduction of carboxylic groups into AMCAP structure, which causes an impact in their properties. The AMCAP–H₂O₂ shows minor contact angle compared to AMCAP, giving a more hydrophilic characteristic, due to acrylic acid addition into the side chains of AMCAP polymer.     

Valuation of ecotoxicological impacts from tributyltin based on a quantitative environmental assessment framework

In the scientific literature, few valuations of biodiversity and ecosystem services following the impacts of toxicity are available, hampered by the lack of ecotoxicological documentation. Here, tributyltin is used to conduct a contingent valuation study as well as cost–benefit analysis (CBA) of measures for improving the environmental status in Swedish coastal waters of the Baltic Sea. Benefits considering different dimensions when assessing environmental status are highlighted and a quantitative environmental assessment framework based on available technology, ecological conditions, and economic valuation methodology is developed. Two scenarios are used in the valuation study: (a) achieving good environmental status by 2020 in accordance with EU legislation (USD 119 household⁻¹ year⁻¹) and (b) achieving visible improvements by 2100 due to natural degradation (USD 108 household⁻¹ year⁻¹) during 8 years. The later scenario was used to illustrate an application of the assessment framework. The CBA results indicate that both scenarios might generate a welfare improvement.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-015-0682-4) contains supplementary material, which is available to authorized users.