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.     

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.     

Influence of Technological Process on Biodegradation of PVA/Waxy Starch Blends in an Aerobic and Anaerobic Environment

Improving biodegradability of PVA/starch blends is a reality already documented by a number of works. Admittedly, mechanical properties of products (for example, tensile strength) are somewhat worse, but suitable composition optimizing or chemical modifying of starch may eliminate the problem to a large degree. This work is an attempt to find another potential effect influencing biodegradability, that of technological procedure for producing films from these blends on an extruder. The procedure with a so-called pre-extrusion step (two-stage) and dry-blend (single-stage) produced blends of slightest differences in achieved biodegradability (virtually within limits of experimental error) in aerobic (76 vs. 79%) as well as anaerobic breakdown (48 vs. 52%). Conversely, morphological analysis exhibited superior homogeneity of films prepared by the two-stage process; their tensile strength was also higher.     

Assisting Australian indigenous resource management and sustainable utilization of species through the use of GIS and environmental modeling techniques

Information on distribution and relative abundance of species is integral to sustainable management, especially if they are to be harvested for subsistence or commerce. In northern Australia, natural landscapes are vast, centers of population few, access is difficult, and Aboriginal resource centers and communities have limited funds and infrastructure. Consequently defining distribution and relative abundance by comprehensive ground survey is difficult and expensive. This highlights the need for simple, cheap, automated methodologies to predict the distribution of species in use, or having potential for use, in commercial enterprise. The technique applied here uses a Geographic Information System (GIS) to make predictions of probability of occurrence using an inductive modeling technique based on Bayes' theorem. The study area is in the Maningrida region, central Arnhem Land, in the Northern Territory, Australia. The species examined, Cycas arnhemica and Brachychiton diversifolius, are currently being 'wild harvested' in commercial trials, involving sale of decorative plants and use as carving wood, respectively. This study involved limited and relatively simple ground surveys requiring approximately 7 days of effort for each species. The overall model performance was evaluated using Cohen's kappa statistics. The predictive ability of the model for C. arnhemica was classified as moderate and for B. diversifolius as fair. The difference in model performance can be attributed to the pattern of distribution of these species. C. arnhemica tends to occur in a clumped distribution due to relatively short distance dispersal of its large seeds and vegetative growth from long-lived rhizomes, while B. diversifolius seeds are smaller and more widely dispersed across the landscape. The output from analysis predicts trends in species distribution that are consistent with independent on-site sampling for each species and therefore should prove useful in gauging the extent of resource availability. However, some caution needs to be applied as the models tend to over predict presence which is a function of distribution patterns and of other variables operating in the landscape such as fire histories which were not included in the model due to limited availability of data.     

Seasonal temperatures have more influence than nitrogen fertilizer rates on cucumber yield and nitrogen uptake in a double cropping system

Two-year greenhouse cucumber experiments were conducted to investigate seasonal effects on fruit yield, dry matter allocation, and N uptake in a double-cropping system with different fertilizer management. Seasonal effects were much greater than fertilizer effects, and winter-spring (WS) cucumber attained higher fruit yields and N uptake than autumn-winter (AW) cucumber due to lower cumulative air temperatures during fruit maturation in the AW season. Fertilizer N application and apparent N loss under recommended N management (Nmr) decreased by 40-78% and 33-48% without yield loss compared to conventional N management (Nmt) over four growing seasons. However, there were no seasonal differences in N recommendations, taking into consideration seasonal differences in crop N demand, critical nutrient supply in the root zone and N mineralization rate.     

Co-combustion of dried sewage sludge and coal in a pulverized coal boiler

More than 1.1 million tons of municipal and industrial sewage sludge is produced annually in Poland. Most of this sewage sludge is landfilled or used for recultivation and fertilization of soil. After accession of Poland to the EU, large investments are planned for wastewater treatment, so it is expected that the amount of sewage sludge produced in Poland will grow in the near future. It is well known that the combustion of sewage sludge is becoming a more and more popular utilization method of such waste. Unfortunately, the current situation in Poland makes it impossible to incinerate the sewage sludge because of a lack of incinerators. One possible solution for Poland is the co-firing of dried sewage sludge in existing coal-fired utility boilers. This article presents results of initial Polish industrial trials of dried municipal sewage sludge and hard coal co-combustion in an OP-230 pulverized coal boiler. Such a solution was shown to be technically viable and not to require changes to the existing technological system. Cocombustion of sewage sludge with coal in power plants seems to be the best solution for sludge utilization in the near future in Poland.     

Initial Changes in Refilled Lysimeters Built with Metal Polluted Topsoil and Acidic or Calcareous Subsoils as Indicated by Changes in Drainage Water Composition

Soil translocation for recultivation of soil removed from construction sites and for the preparation of refilled lysimeters inevitably involves disturbance of soil structure, and, if intermediate storage is included, also drying and rewetting of the soil. We report on an experiment with model forest ecosystems, where uncontaminated forest subsoils were covered with non-contaminated or freshly heavy metal (mainly Zn and Cu) contaminated topsoil in large lysimeters. Monitoring of the chemical composition of the drainage water revealed two distinct soil conditioning phases. During an initial phase of about a year strongly elevated nitrate and sulfate concentrations occurred that were attributed to a mineralisation flush caused by the increased accessability of mineralisable nitrogen and sulfur in destroyed aggregates. These effects were significantly larger in lysimeters with calcareous subsoil than in those with acidic subsoil. The second phase was characterised by a gradual decrease in dissolved organic carbon and sulfate concentrations, in particular in the acidic subsoil. This decrease may be attributed to the depletion of pools made accessible during aggregate destruction or the formation of new aggregates. These chemical changes had only little effects on the concentrations of copper and zinc in the drainage water. Based on our results, it can be concluded that large refilled lysimeters can be used for many purposes without risk of compromised results, if a conditioning phase of about 1 year with sufficiently moist soil conditions is respected. Nevertheless, gradual changes in soil chemical characteristics still occur after this initial phase. Implications for the recultivation of sites using relocated soils are discussed.     

Lysimeter Experiments to Investigate the Fate of Chemicals in Soils – Comparison of Five Different Lysimeter Systems

Several lysimeter scenarios and approaches exist to study the fate of agro-chemicals or contaminants from deposition in soil columns. In many systems just transport and leaching of the parent compound is followed, in some systems the leaching and transport of the metabolites is investigated as well. In more sophisticated lysimeter systems the volatilization and also the mineralization of the applied chemicals can be additionally monitored. Depending on the lysimeter system used and on the fact whether the applied chemicals are ¹⁴C-labeled or not, different results and various interpretations of the results might be achieved. Different lysimeter systems are described in this paper and a real dataset of a specific lysimeter experiment was transferred and evaluated in a virtual approach in the different lysimeter systems in order to show the advantages and disadvantages of the various systems.