Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Combustion characteristics of Malaysian municipal solid waste and predictions of air flow in a rotary kiln incinerator

Malaysia is in dire need of alternatives to landfilling for solid waste management. Recently, landfills have faced the problems of overfilling, overflowing of leachates leading to pollution of water resources, and uncontrolled dust emissions adversely affecting the local environment. With the rising cost of urbanization coupled with the high rate of waste generation, one possible method of waste treatment that is receiving particular attention by the government is incineration. Incineration of solid waste is rather new in Malaysia, with limited usage in handling small sources of waste generation such as the municipal solid waste (MSW) of resort islands; however, its potential in ameliorating the problems associated with solid waste treatment may make it an attractive alternative to landfill. This article presents the results of test runs conducted to investigate the performance of a locally designed and manufactured rotary kiln incinerator (RKI). The test runs were conducted using MSW collected from the Shah Alam municipality. The combustion efficiency was analyzed by looking at the temperature profiles and chemical species concentrations. To complement the combustion characteristics measurements, predictions of the air flow in the incinerator during the process were also investigated. The overall performance of the RKI suggests that it is suitable for treating MSW.     

Mechanical Property Characterization of Plasticized Sugar Beet Pulp and Poly(Lactic Acid) Green Composites Using Acoustic Emission and Confocal Microscopy

Sorbitol and glycerol were used to plasticize sugar beet pulp-poly(lactic acid) green composites. The plasticizer was incorporated into sugar beet pulp (SBP) at 0%, 10%, 20%, 30% and 40% w/w at low temperature and shear and then compounded with poly(lactic acid) (PLA) using twin-screw extrusion and injection molding. The SBP:PLA ratio was maintained at 30:70. As expected, tensile strength decreased by 25% and the elongation increased. Acoustic emission (AE) showed correlated debonding and fracture mechanisms for up to 20% w/w plasticizer and uncorrelated debonding and fracture for 30–40% sorbitol and 30% glycerol content in SBP–PLA composites. All samples had a well dispersed SBP phase with some aggregation in the PLA matrix. However, at 40% glycerol plasticized SBP–PLA composites exhibited unique AE behavior and confocal microscopy revealed the plasticized SBP and PLA formed a co-continuous two phase system.

Sustainable construction--the role of environmental assessment tools

Construction has been accused of causing environmental problems ranging from excessive consumption of global resources both in terms of construction and building operation to the pollution of the surrounding environment, and research on green building design and using building materials to minimise environmental impact is already underway. However, relying on the design of a project to achieve the goal of sustainable development, or to minimise impacts through appropriate management on site, is not sufficient to handle the current problem. The aim for sustainability assessment goes even further than at the design stage of a project to consider its importance at an early stage, before any detailed design or even before a commitment is made to go ahead with a development. However, little or no concern has been given to the importance of selecting more environmentally friendly designs during the project appraisal stage; the stage when environmental matters are best incorporated. The main objectives of this paper are to examine the development, role and limitations of current environmental building assessment methods in ascertaining building sustainability used in different countries which leads to discuss the concept of developing a. sustainability model for project appraisal based on a multi-dimensional approach, that will allow alternatives to be ranked is discussed in detail in the paper.     

Comparison of models of simazine transport and fate in the subsurface environment in a citrus farm

Contamination of groundwater by agrochemicals is now widely recognized as an extremely important environmental problem. Modern agricultural practices involve the combined use of irrigation with the application of large amounts of agrochemicals to maximize crop yield. Due to flood irrigation and natural runoff, agricultural activities might generate soil, surface water and groundwater contamination problems and leaching of pesticides. Modeling of the transport and fate of pesticides, such as simazine, may help understand the long-term potential risk to the subsurface environment. This paper illustrates a comparative study via the use of three different pesticide transport simulation models and the applicability of those models in determining the groundwater vulnerability to pesticides contamination in a citrus orchard located at the Lower Rio Grande Valley (LRGV). The three models used in the study are the pesticide root zone model-3 (PRZM-3), the pesticide analytical model (PESTAN) and integrated pesticide transport modeling (IPTM). The concentration values obtained from all three models are in agreement, and they show a decreasing trend from the surface through the vadose zone. The problem is how to use this information and, specifically, how to combine the testimony of a number of experts into a single useful judgment. With the aid of the fuzzy multiattribute decision making method, PRZM-3 is deemed as the most promising one for such precision farming applications.     

“Bats,snakes and spiders,Oh my!” How aesthetic and negativistic attitudes,and other concepts predict support for species protection

This research investigates whether species are perceived differently based on aesthetic and negativistic attitudes, and whether these and other attitudes, naturalistic activities, and gender predict support for the protection of threatened species. 228 undergraduate students completed a survey in which they rated pictures of 10 endangered species on aesthetic and negativistic attitudes, and support for protection. Findings showed that the two-striped garter snake, Ozark big-eared bat, and dolloff cave spider were conceptualized differently than other species, which may be the result of “irrational” fears linked to animal phobias, culture, and emotional reactions to pictures. The regression results support the common belief that aesthetics is an important determinant in perceptions of endangered species and that the importance of negativistic attitudes may be waning. Moralistic worldviews and attitudes toward landowner rights and the Endangered Species Act were significantly related to support for governmental protection of species. Surprisingly, naturalistic activities and gender were not significantly associated with support for governmental protection of species. In general, the results were consistent across both models. However, the amount of variance explained by aesthetic and negativistic attitudes was 23 percent higher in the other species models than in the bat, snake, and spider models.     

Plant and Soil System Responses to Ozone After 3 Years in a Lysimeter Study with Juvenile Beech (Fagus sylvatica L.)

A lysimeter study was performed to monitor effects of elevated ozone on juvenile trees of Fagus sylvatica L. as well as on the plant–soil system. During a fumigation period over almost three growing seasons, parameters related to plant growth, phenological development and physiology as well as soil functions were studied. The data analyses identified elevated ozone to delay leaf phenology at early and to accelerate it at late developmental stages, to reduce growth, some leaf nutrients (Ca, K) as well as some soluble phenolics (hydroxycinnamic acid derivatives, total flavonol glycosides). No or very weak ozone effects were found in mobile carbon pools of leaves (starch, sucrose), and other phenolic compounds (flavans). Altered gene expression related to stress and carbon cycling corresponded well with findings from leaf phenology and chemical composition analyses indicating earlier senescence and oxidative stress in leaves under elevated ozone. Conversely in the soil system, no effects of ozone were detected on soil enzyme activities, rates of litter degradation and lysimeter water balances. Despite the fact that the three reported years 2003–2005 were climatically very contrasting including a hot and dry as well as an extremely wet summer, and also mild as well as cold winters, the influence of ozone on a number of plant parameters is remarkably consistent, further underlining the phytotoxic potential of elevated tropospheric ozone levels.     

Substance Flow Analyses of Organic Pollutants in Stockholm

This paper summarizes substance flow analyses for four organic substances in the City of Stockholm, Sweden: diethylhexyl phthalate (DEHP), alkylphenolethoxylates (APEO), polybrominated diphenylethers (PBDE) and chlorinated paraffins (CP). The results indicate that the stocks of APEO, PBDE and CP all are approximately 200–250 tonnes, whereas the DEHP stock is two orders of magnitude larger. Emissions can be linked to imported consumer goods such as electronics (PBDE) and textiles (APEO), and to construction materials (DEHP, CP). For several of the substances considerable amounts remain in the technosphere for a long time, even after use of the substance in new products has been eliminated. For example, the use of DEHP as plasticizer for PVC plastics in cables and floorings has more or less been phased-out, but still these applications make up a stock of some 20,000 tonnes (85% of the total DEHP stock in Stockholm) and emit 28 tonnes of DEHP annually (93% of overall emissions). Likewise, the use of chlorinated paraffins in sealants has been radically reduced, but there are 170 tonnes of CP in sealants in Stockholm making up 75% of the stock, and causing half of the emissions to water and air. These emissions are likely to continue for decades, and the stocks therefore have to be considered when analysing and managing the impact of urban substance flows on the environment.