On the thermally induced isomerisation of hexabromocyclododecane stereoisomers

The interconversion of the stereoisomers contained in technical 1,2,5,6,9,10-hexabromocyclododecane, a major brominated flame retardant increasingly found in the environment and in biota, was investigated at elevated temperatures. The application of pure enantiomers of the three constituents alpha-, beta-, and gamma-HBCD enabled the unambiguous elucidation of the individual isomerisation reactions as well as the quantification of all respective rate constants. At 160 degrees C the rate constants range over two orders of magnitude from 1.50x10(-3) to 1.88x10(-5)mol(%)s(-1). A preliminary mechanistic explanation for the differences of the rate constants which govern the composition of HBCD diastereomers at equilibrium is given.     

Effect of ortho-chlorine substitution on the partition behavior of chlorophenols

Chlorophenol isomers are known to possess substantially different octanol/water and octane/water partition constants depending on whether the chlorine substituents are in the ortho or meta/para position. Here we show that the same is also true for environmental partition processes such as water/air and humic acid/air partitioning. Quantitative structure property relationships (QSPR) such as those in the widely used EPI-suite or SPARC fail to correctly predict this influence of the substituent position on the compound's partitioning. Only a more sophisticated quantum chemical software, called COSMOtherm, correctly reproduced these effects. Based on this and earlier experiences we conclude that COSMOtherm may be a better tool for screening large sets of chemicals for which no experimental data on their partitioning yet exist.     

Inorganic and carbonaceous components in indoor/outdoor particulate matter in two residential houses in Oslo, Norway

A detailed analysis of indoor/outdoor physicochemical aerosol properties has been performed. Aerosol measurements were taken at two dwellings, one in the city center and the other in the suburbs of the Oslo metropolitan area, during summer/fall and winter/spring periods of 2002-2003. In this paper, emphasis is placed on the chemical characteristics (water-soluble ions and carbonaceous components) of fine (PM2.5) and coarse (PM2.5-10) particles and their indoor/outdoor relationship. Results demonstrate that the carbonaceous species were dominant in all fractions of the PM10 particles (cut off size: 0.09-11.31 microm) during all measurement periods, except winter 2003, when increased concentrations of water-soluble inorganic ions were predominant because of sea salt transport. The concentration of organic carbon was higher in the fine and coarse PM10 fractions indoors, whereas elemental carbon was higher indoors only in the coarse fraction. In regards to the carbonaceous species, local traffic and secondary organic aerosol formation were, probably, the main sources outdoors, whereas indoors combustion activities such as preparation of food, burning of candles, and cigarette smoking were the main sources. In contrast, the concentrations of water-soluble inorganic ions were higher outdoors than indoors. The variability of water-soluble inorganic ion concentrations outdoors was related to changes in emissions from local anthropogenic sources, long-range transport of particles, sea salt emissions, and resuspension of roadside and soil dusts. In the indoor environment the infiltration of the outdoor air indoors was the major source of inorganic ions.     

Multi-generation studies with Chironomus riparius--effects of low tributyltin concentrations on life history parameters and genetic diversity

While toxicological data are available for numerous chemicals from standard tests, little is known on effects of pollutants over several generations or regarding chronic effects of chemicals on genetic diversity. Within the experiments, effects of the model pollutant tributyltin (TBT) were investigated over eleven generations at a sublethal TBT concentration of 4.46 μg as Sn kg⁻¹ sediment dw on life-cycle parameters and genetic variability of Chironomus riparius. Moreover, the adaptation potential towards TBT was determined. This experimental design enables the identification of TBT effects on life-cycle parameters and the determination of a potential extinction risk caused by chronic exposure. Furthermore, effects on the genetic structure can be determined, which are not predictable based solely on knowledge of the toxic mode of action of the chemical.

Genetic variety was determined via microsatellite analysis, measuring individual length differences of highly variable satellite DNA fragments. For the identification of changes in tolerances towards the stressor, acute and chronic toxicity experiments were conducted.

During the multi-generation study, significant effects on development and reproduction were determined. For some generations, the emergence was significantly (p < 0.05) delayed under TBT exposure. Reproduction seems to be a sensitive parameter as well, whereby females laid significantly larger egg masses (p < 0.05) in the latter generations. TBT did not affect the population growth rate nor the genetic variability, while clear deviations from the Hardy–Weinberg equilibrium appeared. The study also provides strong evidence for the acquirement of a higher tolerance towards the stressor in the TBT-exposed group.     

Time and pH-dependent sorption of the veterinary antimicrobial sulfathiazole to clay minerals and ferrihydrite

Substantial amounts of sulfonamides, ionizable, polar veterinary antimicrobials, may reach the environment by spreading of manure. Sorption to soils and sediments is a crucial but not sufficiently understood process influencing the environmental fate of sulfonamides. Therefore, we investigated sorption of sulfathiazole to clay minerals (montmorillonite, illite) and ferrihydrite for varying pH values and two contact times (1d, 14 d) under sterile conditions. Results were compared to sulfathiazole sorption to organic sorbents. Sulfathiazole sorption to inorganic sorbents exhibited pronounced pH dependence consistent with sorbate speciation and sorbent charge properties. While sulfathiazole cations were most important for sorption to clay minerals, followed by neutral species, ferrihydrite was a specific anion sorbent, showing significant sorption only between pH 5.5-7. Experiments revealed a substantial increase of sorption with time for ferrihydrite (pH 5.5-7) and illite (pH<5.5). Reasons may be disaggregation of clay minerals and, for ferrihydrite, diffusion and sorption of sulfathiazole in micropores. Independent of contact time and pH, sorption to inorganic sorbents was more than an order of magnitude lower than to organic sorbents. This implies that in many topsoils and sediments inorganic sorbents play a minor role. Our results highlight the need to account for contact time and speciation when predicting sulfonamide sorption in the environment.     

Toxicity and hazard of a mixture of SSRIs to zooplankton communities evaluated in aquatic microcosms

The toxicity and hazard of a mixture of selective serotonin reuptake inhibitors (SSRIs), including fluoxetine, fluvoxamine, and sertraline, to zooplankton communities were evaluated using 120,00l outdoor microcosms. Acute (day 4) and chronic (day 35) zooplankton abundance and species richness were assessed for Rotifera, Cladocera, and Copepoda. For acute SSRI exposures, rotifers were the most sensitive zooplankton taxa to changes in abundance (predicted no effect concentration (PNEC)=19 nM); however, no effects in zooplankton species richness were observed for this treatment period. A decrease in Copepoda abundance and species richness was observed following chronic exposures of SSRIs (PNEC=9.1 nM). A 99th-centile predicted environmental concentration (PEC=0.51 nM) yielded HQs at least two orders of magnitude below 1. Therefore, mixtures of SSRIs do not appear to present a hazard to zooplankton communities at environmentally relevant concentrations.     

Stabilization of Pb- and Cu-contaminated soil using coal fly ash and peat

The stabilization of metal contaminated soil is being tested as an alternative remediation method to landfilling. An evaluation of the changes in Cu and Pb mobility and bioavailability in soil induced by the addition of coal fly ash and natural organic matter (peat) revealed that the amount of leached Cu decreased by 98.2% and Pb by 99.9%, as assessed by a batch test. Metal leaching from the treated soil was lower by two orders of magnitude compared to the untreated soil in the field lysimeters. A possible formation of mineral Cu- and Pb-bearing phases and active surface with oxides were identified by chemical equilibrium calculations. Low metal leaching during a two-year observation period, increased seed germination rate, reduced metal accumulation in plant shoots, and decreased toxicity to plants and bacteria, thereby demonstrating this stabilization method to be a promising technique for in situ remediation of Cu and Pb contaminated soil.     

Environmental assessment of waste incineration in a life-cycle-perspective (EASEWASTE).

A model for life-cycle assessment of waste incinerators is described and applied to a case study for illustrative purposes. As life-cycle thinking becomes more integrated into waste management, quantitative tools for assessing waste management technologies are needed. The presented model is a module in the life-cycle assessment model EASEWASTE. The module accounts for all uses of materials and energy and credits the incinerator for electricity and heat recovered. The energy recovered is defined by the user as a percentage of the energy produced, calculated on the lower heating value of the wet waste incinerated. Emissions are either process-specific (related to the amount of waste incinerated) or input-specific (related to the composition of the waste incinerated), while mass transfer to solid outputs are governed by transfer coefficients specified by the user. The waste input is defined by 48 material fractions and their chemical composition. The model was used to quantify the environmental performance of the incineration plant in Aarhus, Denmark before and after its upgrading in terms of improved flue gas cleaning and energy recovery. It demonstrated its usefulness in identifying the various processes and substances that contributed to environmental loadings as well as to environmental savings. The model was instrumental in demonstrating the importance of the energy recovery system not only for electricity but also heat from the incinerator.     

Chemical composition of material fractions in Danish household waste

The chemical composition of Danish household waste was determined by two approaches: a direct method where the chemical composition (61 substances) of 48 material fractions was determined after hand sorting of about 20 tonnes of waste collected from 2200 households; and an indirect method where batches of 80–1200 tonnes of unsorted household waste was incinerated and the content of the waste determined from the content of the outputs from the incinerator. The indirect method is believed to better represent the small but highly contaminated material fractions (e.g., batteries) than the direct method, because of the larger quantities included and the more homogenous material to sample from. Differences between the direct and the direct methods led to corrections in the of heavy metal concentration of a few fractions.The majority of the energy content of the waste originates from organic waste like paper, cardboard and organic fractions. The single fraction contributing most to the total energy content is the non-recyclable plastic fraction, contributing 21% of the energy content and 60% of the chlorine content, although this fraction comprises less than 7% by weight. Heavy metals originate mainly from inert fractions, primarily batteries.