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.     

Nickel induced alteration of hen body weight,egg production and egg quality after an experimental peroral administration

In this study the effects of nickel (NiCl₂) administered in drinking water (0.02; 0.2 and 2.0 mg NiCl₂/L for 28 days) on laying hen body weight, egg production and egg quality is reported. Growth parameters during the experiment were significantly decreased mainly in the group with the highest nickel concentration. In total egg production dose–dependent decrease in all experimental groups was found. Egg weight was mainly affected in the group with the highest nickel concentration. Specific egg weight was not altered. Albumen weight and albumen content was significantly decreased in groups with the highest nickel concentration in comparison with the control group.

Egg yolk analysis detected significantly decreased yolk weight in the group with the highest nickel experimental level. In yolk color a significant difference was detected between the group receiving 0.02 and 0.2 mg NiCl₂/mL. Eggshell compactness was increased in all experimental groups what could be induced by altered mineralization of eggshell. Results of this study clearly report a negative effect of nickel as an environmental pollutant on laying hen body weight, egg production as well as egg quality.     

Occurrence of perfluorinated organic acids in the North and Baltic seas. Part 1: distribution in sea water

Purpose  

Due to their high water solubilities and mobilities, persistent, polar perfluorinated compounds (PFCs) such as perfluorinated carboxylates and sulfonates are likely to end up in the oceans. In part 1 of this study, their distribution in North and Baltic Sea water is reported, being of special interest because these seas are surrounded by highly industrialized countries with high population densities.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.     

A status report on the U.S. national dioxin study

In 1983, the US Environmental Protection Agency (EPA) embarked on an extensive investigation of the presence and extent of contamination of the national environment by CDDs/CDFs. This status report is a prelude to a final report to be delivered to the US Congress in December, 1985.     

Xenoestrogens in the River Elbe and its tributaries

4-Alkylphenols, 4-alkylphenol ethoxylates, 4-alkylphenoxy carboxylates, bisphenol A, bisphenol F, 4-hydroxyacetophenon, 4-hydroxybenzoic acid and steroid hormones were analyzed in water samples of the River Elbe and its tributaries Schwarze Elster, Mulde, Saale, Havel and Schwinge. Additionally, freshly deposited sediments (FDS, composite samples) of the River Elbe and its tributaries were analyzed. The concentrations in water samples ranged from (in ng/l): bisphenol A 4 to 92, branched nonylphenol 13 to 87, branched nonylphenol ethoxylates <0.5 to 120, 4-tert. nonylphenoxy carboxylates <10 to 940 and 4-hydroxybenzoic acid 4 to 12. Steroid hormones were only detected in the Czech tributaries Jizera and Vltava in concentrations near the limit of quantification. In FDS samples the concentrations amounted to (in g/kg d.w.): bisphenol A 10-380, branched nonylphenol 27-430, branched nonylphenol ethoxylates 24-3700, nonylphenoxy carboxylates <50 and 4-hydroxybenzoic acid 23-4400. Increased bisphenol A concentrations were found in water and FDS samples taken from the Czech-German border at Schmilka and the mouth of the Schwinge (only water sample). According to studies conducted in the Elbe Estuary and the German Bight, the River Elbe must be considered as a major source of pollution for the North Sea in respect of the compounds analyzed. A comparison of bisphenol A concentrations, 4-alkylphenols and the corresponding ethoxylates analyzed in the River Elbe and its tributaries with those found in other German surface waters indicated a low level of contamination. The evaluation of the data based on LOEC-values indicated that the concentrations were well below the effectivity threshold for some 4-alkylphenols. According to recent ecotoxicological investigations, for example, with prosobranch snails, bisphenol A concentrations found in water samples of the River Elbe and its tributaries may well be detrimental to aquatic organisms. On the basis of the monitoring data and its implications for estrogenic potency the inclusion of bisphenol A in the list of priority substances (European Union Directive 2000/60/EC, Annex X) should be considered.     

The BIOTA Biodiversity Observatories in Africa—a standardized framework for large-scale environmental monitoring

The international, interdisciplinary biodiversity research project BIOTA AFRICA initiated a standardized biodiversity monitoring network along climatic gradients across the African continent. Due to an identified lack of adequate monitoring designs, BIOTA AFRICA developed and implemented the standardized BIOTA Biodiversity Observatories, that meet the following criteria (a) enable long-term monitoring of biodiversity, potential driving factors, and relevant indicators with adequate spatial and temporal resolution, (b) facilitate comparability of data generated within different ecosystems, (c) allow integration of many disciplines, (d) allow spatial up-scaling, and (e) be applicable within a network approach. A BIOTA Observatory encompasses an area of 1?km² and is subdivided into 100 1-ha plots. For meeting the needs of sampling of different organism groups, the hectare plot is again subdivided into standardized subplots, whose sizes follow a geometric series. To allow for different sampling intensities but at the same time to characterize the whole square kilometer, the number of hectare plots to be sampled depends on the requirements of the respective discipline. A hierarchical ranking of the hectare plots ensures that all disciplines monitor as many hectare plots jointly as possible. The BIOTA Observatory design assures repeated, multidisciplinary standardized inventories of biodiversity and its environmental drivers, including options for spatial up- and downscaling and different sampling intensities. BIOTA Observatories have been installed along climatic and landscape gradients in Morocco, West Africa, and southern Africa. In regions with varying land use, several BIOTA Observatories are situated close to each other to analyze management effects.     

Benzene Exposure Assessment at Indoor, Outdoor and Personal Levels. The French Contribution to the Life MACBETH Programme

Many VOC represent hazards to human health through chronic exposure. Recent European and world-wide legislation proposes limit values for ambient concentrations of these compounds. However, very little experimental data exists for true population exposure. In 1996, the European MACBETH initiative set out to measure population exposure to benzene in six European cities. This study details the French contribution to this program. Six campaigns were carried out, each comprising measurements at 100 outdoor sites and the participation of 50 non-smoking volunteers who wore personal samplers and had passive monitors installed in their homes. Iso-concentration maps were drawn for each campaign and the results showed that outdoor concentrations were significantly lower than indoors. Almost 75% of the volunteers were exposed to mean concentrations higher than the limit value of 5µgm³. It is demonstrated that personal exposure levels cannot be deduced simply by combining indoor and outdoor background concentrations. It is also shown that there is need for better knowledge of the contributions to overall exposure of outdoor microenvironments and the authors hope that future European directives will take this into account.     

The impact of global change on economic values of water for Public Irrigation Schemes at the São Francisco River Basin in Brazil

Economic values of water for the main Public Irrigation Schemes in the sub-middle region of the São Francisco River Basin, in northeastern Brazil, are determined in this study using an integration of a global agro-economic land and water use (MAgPIE) with a local economic model (Positive Mathematical Programming). As in the latter, the water values depend on the crops grown, and as Brazilian agriculture is strongly influenced by the global market, we used a regionalized version of the global model adapted to the region in order to simulate the crop land use, which is in turn determined by changes in global demand, trade barriers, and climate. The allocation of sugarcane and fruit crops projected with climate change by the global model, showed an impact on the average yields and on the water costs in the main schemes resulting in changes in the water values locally. The economic values for all schemes in the baseline year were higher than the water prices established for agricultural use in the basin. In the future, these water values will be higher in all the schemes. The highest water values currently and in the future were identified in municipalities with a significant proportion of area growing irrigated sugarcane. Being aware of current water values of each user in a baseline year and in a projected future under global climate and socioeconomic changes, decision makers should improve water allocation policies at local scale, in order to avoid conflicts and unsustainable development in the future.