Determination of isocyanates, aminoisocyanates and amines in air formed during the thermal degradation of polyurethane

An air sampling method for the determination of isocyanates, aminoisocyanates and amines formed during the thermal degradation of polyurethane (PUR) is presented. The method is based on the collection of air samples using impinger flasks containing di-n-butylamine (DBA) in toluene with a glass fibre filter in series. Isocyanates are derivatized with DBA to urea derivatives, and amines are derivatized in a subsequent work-up procedure with ethyl chloroformate (ET) to carbamate esters. Amine, aminoisocyanate and isocyanate derivatives were characterized using liquid chromatography-time of flight mass spectrometry (LC-TOFMS) and liquid chromatography-chemiluminescent nitrogen detection (LC-CLND). Quantification was performed by LC-MS, monitoring molecular ions [MH]+ in the electrospray mode. The instrumental detection limits for amines, aminoisocyanates and isocyanates were in the ranges 30-40, 2-3 and 3-70 fmol, respectively. Thermal degradation products of PUR were observed in high concentrations during welding in district heating pipes and PUR-coated metal sheets. Eleven isocyanates, three amines and five aminoisocyanates were identified. The concentrations of isocyanates, aminoisocyanates and amines in samples collected in the smoke close to the welding spot were in the ranges 150-650, 4-290 and 1-70 ppb, respectively. In samples collected in the breathing zone, isocyanates and aminoisocyanates were observed in the ranges 9-120 and 4-19 ppb, respectively. The compounds were present in both gas and particle phases. Volatile compounds dominated in the gas phase, whereas less volatile compounds dominated in the particle phase. The method presented makes it possible to sample and determine amines and aminoisocyanates, in addition to isocyanates. The need to monitor these compounds is clearly illustrated by the high concentrations found during the thermal degradation of PUR.     

Molecular Weight Changes and Polymeric Matrix Changes Correlated with the Formation of Degradation Products in Biodegraded Polyethylene

The molecular weight changes in abiotically and biotically degraded LDPE and LDPE modified with starch and/or prooxidant were compared with the formation of degradation products. The samples were thermooxidized for 6 days at 100°C to initiate degradation and then either inoculated with Arthobacter paraffineus or kept sterile. After 3.5 years homologous series of mono- and dicarboxylic acids and ketoacids were identified by GC-MS in abiotic samples, while complete disappearance of these acids was observed in biotic environments. The molecular weights of the biotically aged samples were slightly higher than the molecular weights of the corresponding abiotically aged samples, which is exemplified by the increase in from 5200 g/mol for a sterile sample with the highest amount of prooxidant to 6000 g/mol for the corresponding biodegraded sample. The higher molecular weight in the biotic environment is explained by the assimilation of carboxylic acids and low molecular weight polyethylene chains by microorganisms. Assimilation of the low molecular weight products is further confirmed by the absence of carboxylic acids in the biotic samples. Fewer carbonyls and more double bonds were seen by FTIR in the biodegraded samples, which is in agreement with the biodegradation mechanism of polyethylene.     

Levels of brominated flame retardants in blood in relation to levels in household air and dust

Levels of tri- to decabrominated diphenyl ethers (BDEs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and 1,2-bis(pentabromophenyl)ethane (DeBDethane) were determined in air, sedimentary dust and human plasma from five households in Sweden. The levels of the individual BDEs in the plasma samples were in the same order of magnitude as in other studies of the general population in Scandinavia, and varied between non-detectable (<0.41 ng g(-1) l.w.) to 17 ng g(-1) (l.w.). BDE#28 and #47 were present in all air samples, with mean values of 0.015 and 0.12 ng m(-3), respectively, except for one sample where the BDE#47 concentration was below the limit of detection (<0.17 ng m(-3)). BDE#209 was found in one of the five air samples at a concentration of 0.26 ng m(-3). DeBDethane was also detected in one sample, in which the BDE#209 level was below LOD (<0.021 ng m(-3)), at a level of 0.023 ng m(-3). All the target compounds were found in the sedimentary dust samples at levels from 0.51 to 1600 ng g(-1), the highest concentration representing BDE#209. The most abundant components in plasma, air and dust were BDE#47, #99 and #209. In the plasma samples BDE#207 and #206 were also present at similar concentrations as BDE#47. In the sedimentary dust samples, DeBDethane was also among the most abundant BFRs. A positive relationship was found for the sumBDE concentrations in dust and plasma, although the relationship was strongly dependent on one of the five observations. BFR levels in dust and air were not dependent on the house characteristics such as living area, floor material or number of electronic devices.     

A model of ecological and evolutionary consequences of color polymorphism

We summarize direct and indirect effects on fitness components of animal color pattern and present a synthesis of theories concerning the ecological and evolutionary dynamics of chromatic multiple niche polymorphisms. Previous endeavors have aimed primarily at identifying conditions that promote the evolution and maintenance of polymorphisms. We consider in a conceptual model also the reciprocal influence of color polymorphism on population processes and propose that polymorphism entails selective advantages that may promote the ecological success of polymorphic species. The model begins with an evolutionary branching event from mono- to polymorphic condition that, under the influence of correlational selection, is predicted to promote the evolution of physical integration of coloration and other traits (cf. multi-trait coevolution and complex phenotypes). We propose that the coexistence within a population of alternative ecomorphs with coadapted gene complexes promotes utilization of diverse environmental resources, population stability and persistence, colonization success, and range expansions, and enhances the evolutionary potential and speciation. Conversely, we predict polymorphic populations to be less vulnerable to environmental change and at lower risk of range contractions and extinctions compared with monomorphic populations. We offer brief suggestions as to how these falsifiable predictions may be tested.     

Maturation of work attitudes: Correlated change with big five personality traits and reciprocal effects over 15 years

As employees grow older, do their attitudes regarding work change over time? Can such long‐term changes be understood from a personality development perspective? The present study addressed these fundamental questions by tracking 504 young professionals' work attitudes (i.e., job satisfaction and work involvement) and Big Five personality traits over the first 15 years of their professional career. We specifically investigated whether trait changes drive peoples' changing attitudes, a mechanism we called maturation of work attitudes. Latent change models first indicated significant associations between traits and attitudes at the beginning of the career, and mean‐level changes in Big Five traits (i.e., increases in Agreeableness and Conscientiousness and decreases in Neuroticism) in the direction of greater functional maturity. Although no significant mean‐level changes in work attitudes were observed, results regarding correlated change indicated that variability in attitude change was related to variability in trait change and that this indeed signaled a maturational process. Finally, reciprocal effect estimates highlighted bidirectional relations between personality and attitudes over time. It is discussed how these results (i) provide a better understanding of potential age effects on work‐related attitudes and (ii) imply a revision of the traditional dispositional approach to attitudes. Copyright © 2013 John Wiley & Sons, Ltd.     

Chain-Length Shortening of Methyl Ethyl Hydroxyethyl Cellulose: An Evaluation of the Material Properties and Effect on Foaming Ability

During the past century, plastics have become a natural element in our every-day life. Lately however, an awareness about the fossil origin and often non-degradable nature of many plastics is rising. This has resulted in the emergence of some bio-based and/or biodegradable plastics, often produced from renewable resources. One possible candidate for bioplastics production could be found in cellulose. This paper aims at contributing information regarding a cellulose derivative, which could possibly be used in foamed plastics applications. Therefore, the reduction of the chain-length of a methyl ethyl hydroxyethyl cellulose (MEHEC), assessed by size exclusion chromatography, and the effect of chain-length on the foaming behaviour were studied. The foaming was accomplished with a hot-mould technique using aqueous polymer solutions. The generated steam was here used as the blowing agent and important parameters were polymer concentration and solution viscosity. The density of the produced foams was assessed and was in some cases comparable to that of commodity foams. It was found that reducing the chain-length enabled an increase of the initial polymer concentration for the foaming process. This is believed to be beneficial for creating more structurally stable foams of this type.     

The UN climate change negotiations and the role of the United States: assessing American leadership from Copenhagen to Paris

The role of American leadership in the UN climate negotiations that produced the 2015 Paris Agreement is examined. First, United States (US) climate goals are identified. Then, utilizing unique survey data collected at eight UN climate summits between 2008 and 2015, the extent to which the US was recognized as a leader by potential followers is investigated. Finally, the extent to which US goals are reflected in negotiation outcomes is evaluated. Recognition of the US as a leader varied over time, peaking at the UN climate meetings in Copenhagen and Paris, reflecting US leadership in shaping the outcomes of both meetings. Although the results reveal a divided leadership landscape in which the US must compete for leadership with other actors, such as the European Union and China, US leadership was crucial to the successful adoption of the Paris Agreement.     

Reduced European emissions of S and N--effects on air concentrations, deposition and soil water chemistry in Swedish forests

Changes in sulphur and nitrogen pollution in Swedish forests have been assessed in relation to European emission reductions, based on measurements in the Swedish Throughfall Monitoring Network. Measurements were analysed over 20 years with a focus on the 12-year period 1996 to 2008. Air concentrations of SO₂ and NO₂, have decreased. The SO₄-deposition has decreased in parallel with the European emission reductions. Soil water SO₄-concentrations have decreased at most sites but the pH, ANC and inorganic Al-concentrations indicated acidification recovery only at some of the sites. No changes in the bulk deposition of inorganic nitrogen could be demonstrated. Elevated NO₃-concentrations in the soil water occurred at irregular occasions at some southern sites. Despite considerable air pollution emission reductions in Europe, acidification recovery in Swedish forests soils is slow. Nitrogen deposition to Swedish forests continues at elevated levels that may lead to leaching of nitrate to surface waters.     

Governance of Complex Socio-Environmental Risks: The Case of Hazardous Chemicals in the Baltic Sea

Complex socio-environmental risks challenge society. In response to scientific uncertainty and socio-political controversies, environmental governance, precaution, and the ecosystem approach to management are held forward as complements to governmental risk-based sector-restricted regulation. We analyze this development for hazardous substances in the Baltic Sea. Based on interviews and policy analysis, we study informal governance and, in particular, four central EU and international policies, and investigate how present governance relates to risks and objectives at hand. While showing emergence of broader governance approaches, we conclude that central objectives will not likely be met. Furthermore, we question the quest for broad environmental governance and emphasize the value of command and control regulation, if it implements precaution. These findings contribute to the theorizing on environmental (risk) governance. Finally, we provide some ideas that could help development and implementation of risk policies for hazardous chemicals in the Baltic Sea as well as other complex risks.