Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

Changes in sewage sludge carbon forms along a treatment stream

The behaviour and fate of macronutrients and pollutants in sewage sludge applied to the land are affected by the chemical composition of the sludge organic matter, which in turn is influenced by both sewage source and by sewage treatment processes. In this study, (13)C nuclear magnetic resonance (NMR) spectroscopy was used to characterise the organic matter of sludges collected at three different points along the treatment stream of a municipal sewage works with a domestic catchment. Sludge at the first point, an undigested liquid (UL) sludge, had a substantially different composition to the anaerobically digested (AD) and dewatered sludge cake (DC) materials, which were similar to each other. In particular, the UL sludge contained more alkyl C than the AD or DC sludges. All three sludges were found to contain mobile alkyl C that is poorly observed using the cross polarisation (CP) technique, necessitating the use of the less sensitive, but more quantitatively reliable direct polarisation (DP) technique to obtain accurate distributions of C types.     

Horizontal mergers in the iron ore industry—An application of PCAIDS

The purpose of this paper is to estimate and analyse the price effects of the iron ore mergers between Rio Tinto and North Ltd in 2000, and CVRD and Caemi in 2001. The analyses are conducted using a merger simulation model that, based on the pre-merger situation, estimates the post-merger outcome. This paper applies the so-called proportionality-calibrated almost ideal demand system (PCAIDS) model, which assumes that the product is differentiated and that the strategic variable is price. The results from the merger simulations show that in the case of the merger between Rio Tinto and North Ltd, the merged firm has a combined market share of almost 20%. However, the estimated market weighted average price effect is only 2.6%. Regarding the merger between CVRD and Caemi, the merged firm's market share is about 29%, and the estimated market weighted average price effect is 4.6%. When removing Caemi's Canadian asset, which was the Commission decision in order to allow the merger, the market price effect decreases to 3.1%. Overall the results in this study support the Commission's decisions regarding both merger cases, and shows that merger simulations of price effects can be valuable tools in merger assessments.     

Relationships between street characteristics and perceived attractiveness for walking reported by elderly people

Walking is important for the health of elderly people. Previous studies have found a relationship between neighbourhood characteristics, physical activity and related health aspects. The multivariate linear regression model presented here describes the relationships between the perceived attractiveness of streets for walking along and (physical) street characteristics. Two hundred and eighty-eight independently living elderly people (between 55 and 80 years old) participated in the study. Street characteristics were assessed along homogeneous street subsections defined as ‘links’. Positively related to perceived attractiveness of links were the following street characteristics: slopes and/or stairs, zebra crossings, trees along the route, front gardens, bus and tram stops, shops, business buildings, catering establishments, passing through parks or the city centre, and traffic volume. Litter on the street, high-rise buildings, and neighbourhood density of dwellings were negatively related to perceived link attractiveness. Overall, the results suggest that three main aspects affect perceived attractiveness of streets for walking, namely tidiness of the street, its scenic value and the presence of activity or other people along the street. The results are discussed within the context of these three aspects.     

Effect of long-term changes in soil chemistry induced by road salt applications on N-transformations in roadside soils

Of several impacts of road salting on roadside soils, the potential disruption of the nitrogen cycle has been largely ignored. Therefore the fates of low-level ammonium-N and nitrate-N inputs to roadside soils impacted by salting over an extended period (decades) in the field have been studied. The use of road salts disrupts the proportional contributions of nitrate-N and ammonium-N to the mineral inorganic fraction of roadside soils. It is highly probable that the degree of salt exposure of the soil, in the longer term, controls the rates of key microbial N transformation processes, primarily by increasing soil pH. Additional influxes of ammonium-N to salt-impacted soils are rapidly nitrified therefore and, thereafter, increased leaching of nitrate-N to the local waterways occurs, which has particular relevance to the Water Framework Directive. The results reported are important when assessing the fate of inputs of ammonia to soils from atmospheric pollution.     

A design tool for planning emulsified oil‐injection systems

Emulsified oils have been used to stimulate anaerobic bioremediation at hundreds of sites contaminated with chlorinated solvents, perchlorate, heavy metals, and nitrate. A simple spreadsheet‐based tool has been developed to assist in the design of injection‐only systems for distributing emulsified oils in barriers and area treatments. This tool allows users to quickly compare the relative costs and performance of different injection alternatives and identify a design that is best suited to site‐specific conditions. Contact efficiency is estimated using results of prior numerical model simulations and dimensionless scaling factors that relate the volume of oil and water injected to treatment‐zone dimensions. Sensitivity analysis results indicate that maximum oil retention is one of the most important factors controlling system performance and cost. © 2008 Wiley Periodicals, Inc.     

Biodegradation of microcystins and nodularin in freshwaters

Microcystin-LR (MC-LR) was readily biodegraded on addition to six different water samples irrespective of their previous exposure to microcystins. Subsequent studies with water from three of these water bodies confirmed the degradation of MC-LR and also demonstrated the biodegradation of MC-LF, nodularin and mixture of microcystins and nodularin. Rates of degradation of MC-LR, MC-LF and NOD in individual water samples ranged from a half-life of 4 to 18d. Analysis by HPLC-PDA-ESI+ and MALDI MS/MS revealed novel intermediate degradation products of MC-LF and nodularin which included demethylation, hydrolysis, decarboxylation and condensation of the parent compound(s). Our study suggests a possible diversity of micro-organisms and/or pathways which has not been previously observed.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Anti-sense expression of putrescine N-methyltransferase confirms defensive role of nicotine in Nicotiana sylvestris against Manduca sexta

Summary. Several lines of evidence support the defensive function of nicotine production in the Nicotiana genus against a range of herbivores, but the evidence is largely correlative. To suppress nicotine production in planta and to test its defensive function, we expressed DNA of putrescine N-methyl transferase in an anti-sense orientation (AS-PMT) in N. sylvestris and fed leaf material from two lines of transformed and wild type plants to Manduca sexta larvae. Larvae consumed more leaf area and gained more mass on the foliage of plants with low PMT expression and low nicotine levels as compared to plants with high PMT expression and high nicotine levels and wild type plants. Overall, larval consumption and performance were negatively correlated with constitutive nicotine levels. We conclude that nicotine decreases the palatability of N. sylvestris leaves to the nicotine-resistant M. sexta larvae.     

Metal concentrations in American oyster <Emphasis Type="Italic">Crassotrea virginica</Emphasis> and adjacent sediments from harvestable and non-harvestable sites in the Southeastern USA

Human population growth in coastal areas continues to threaten estuarine ecosystems and resources. Populations of Crassostrea virginica have declined across the USA due to water quality degradation, disease pressure, alteration of habitat, and other changes related to anthropogenic impacts. Metals that may be present in estuarine habitats can bioaccumulate in oysters, with potential consequences to the health of oysters and humans consumers. This study (1) evaluated the occurrence and relationships of metal concentrations in oyster tissue versus estuarine sediments, (2) examined oyster tissue concentrations in relation to state water quality designations, and (3) evaluated the potential risk for humans from oyster consumption related to metal concentrations from harvestable waters. Results indicated metal concentrations in sediments and oysters along coastal South Carolina remain low compared to other areas and that concentrations in oyster tissue and adjacent sediments were not highly correlated with each other. However, high concentrations of some metals occurred in oysters sampled from areas designated as Approved for Harvesting. This is important because most harvest area designation systems rely on regular bacterial monitoring when evaluating the safety of consumption. Others safety measurements may be necessary as part of routine monitoring.