Advanced REACH Tool (ART): calibration of the mechanistic model

The mechanistic model of the Advanced Reach Tool (ART) provides a relative ranking of exposure levels from different scenarios. The objectives of the calibration described in this paper are threefold: to study whether the mechanistic model scores are accurately ranked in relation to exposure measurements; to enable the mechanistic model to estimate actual exposure levels rather than relative scores; and to provide a method of quantifying model uncertainty. Stringent data quality guidelines were applied to the collated data. Linear mixed effects models were used to evaluate the association between relative ART model scores and measurements. A random scenario and company component of variance were introduced to reflect the model uncertainty. Stratified analyses were conducted for different forms of exposure (abrasive dust, dust, vapours and mists). In total more than 2000 good quality measurements were available for the calibration of the mechanistic model. The calibration showed that after calibration the mechanistic model of ART was able to estimate geometric mean (GM) exposure levels with 90% confidence for a given scenario to lie within a factor between two and six of the measured GM depending upon the form of exposure.     

Presence and partitioning properties of the flame retardants pentabromotoluene, pentabromoethylbenzene and hexabromobenzene near suspected source zones in Norway

The brominated flame retardants (BFRs), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB) and hexabromobenzene (HBB), exhibit physical-chemical properties similar to other persistent organic pollutants, and have been in use as flame retardants for several decades. Data on these BFRs in diverse environmental samples can be found in studies from the 1970s and 1980s, as well as in recent years, though very little in the years in between. Due to a lack of data, the cause for the apparent re-emergence of these BFRs in recent studies is unclear, and could reflect changes in production volumes, accumulation of transformation products from BFR precursors, improved analytical techniques or simply a re-emergence in concern. Very little data are available on their environmentally relevant partitioning properties, which could help to explain the occurrence and fate of these BFRs. In this study we analysed for the presence of HBB, PBT, and PBEB in diverse environmental samples from potential Norwegian BFR source zones. Additionally, environmental partitioning properties of these BFRs as well as brominated benzenes were estimated and validated using experimental data for brominated benzenes. Of the three BFRs, HBB was identified in detectable quantities at most source zones, PBEB only near a metal recycling factory, and PBT only in a few additional locations from where PBEB was detected. Data from this study show that HBB is likely widely distributed, as verified both by chemical analysis and estimated properties. Measured HBB levels in wastewater treatment plants indicate that the treatment practices used in the study locations are not effective at lowering HBB levels, perhaps due to association with low density suspended solids (e.g. microplastics).     

Characterization of municipal solid waste combustion in a grate furnace

The objective of this paper is to evaluate the combustion process of municipal solid waste combustion in a grate furnace both experimentally and numerically by using data of a reference experiment with over-stoichiometric primary air supply. Measurements were carried out inside the combustion chamber of a pilot plant by monitoring temperatures and sampling gaseous combustion products along the bed surface. The data were assessed using elemental and energy balances. Experimental data of the axial temperature profiles of the flue gas, the fuel bed and the grate bars, as well as local gas flows and the flue gas composition measured above the fuel bed along the grate were used to describe the conversion process, including drying and carbon burnout. These data served as input to model the thermo- and fluid dynamic processes of the gas phase above the bed inside the combustion chamber. For this purpose the commercial code FLUENT was employed to carry out the simulations. Thus, the turbulent temperature, flow and species distributions in the combustion chamber of the pilot waste incinerator TAMARA were predicted. The results of the FLUENT modeling showed that under the prevailing conditions the flue gas burnout is almost completed before entering the first flue due to high temperatures, effective mixing and sufficient residence times of the flue gas inside the combustion chamber. This agrees well with the experimental results inside the first flue. On the basis of the above mentioned results, design and parametric studies can be carried out in a more efficient way by saving cost and time.     

Sulfide assimilation by ectosymbionts of the sessile ciliate, <Emphasis Type="Italic">Zoothamnium niveum</Emphasis>

We investigated the constraints on sulfide uptake by bacterial ectosymbionts on the marine peritrich ciliate Zoothamnium niveum by a combination of experimental and numerical methods. Protists with symbionts were collected on large blocks of mangrove-peat. The blocks were placed in a flow cell with flow adjusted to in situ velocity. The water motion around the colonies was then characterized by particle tracking velocimetry. This shows that the feather-shaped colony of Z. niveum generates a unidirectional flow of seawater through the colony with no recirculation. The source of the feeding current was the free-flowing water although the size of the colonies suggests that they live partly submerged in the diffusive boundary layer. We showed that the filtered volume allows Z. niveum to assimilate sufficient sulfide to sustain the symbiosis at a few micromoles per liter in ambient concentration. Numerical modeling shows that sulfide oxidizing bacteria on the surfaces of Z. niveum can sustain 100-times higher sulfide uptake than bacteria on flat surfaces, such as microbial mats. The study demonstrates that the filter feeding zooids of Z. niveum are preadapted to be prime habitats for sulfide oxidizing bacteria due to Z. niveum’s habitat preference and due to the feeding current. Z. niveum is capable of exploiting low concentrations of sulfide in near norm-oxic seawater. This links its otherwise dissimilar habitats and makes it functionally similar to invertebrates with thiotrophic symbionts in filtering organs. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Uranium in stream and mineral water of the Federal Republic of Germany

The concentration of uranium was determined in 944 samples from stream water by the inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) method and represented on a color-shaded contour map. Uranium concentrations in surface water were determined to be between 0.007 μg/l and 43.7 μg/l with median of 0.33 μg/l. The regional distribution of uranium is influenced primarily by lithological and anthropogenic factors. In Mecklenburg, northern Brandenburg, and eastern Schleswig-Holstein, elevated uranium concentrations coincide with the extent of the last Weichselian ice sheet. The maximum concentrations are observed in the surface waters of the old mining districts in the western part of the Ore Mountains and in eastern Thuringia. Elevated concentrations are found in areas of agriculturally used loess soils. These concentrations correlate with the use of phosphate fertilizers. There is a zone of elevated concentrations up to 10.0 μg U/l in the Keuper Sandstone area south of the Thuringian Forest and from northwest of Stuttgart as far as Coburg. The distribution of elevated values in mineral water shows a clear correlation with the elevated values in surface water and the geology of those locations. Bunter and Keuper strata are the most important uranium source.     

Ökotoxikologische Charakterisierung von Nonylphenol Isomeren

Background, Aim and Scope

Acute toxicity and estrogenic potency of six nonylphenol isomers, with nearly the same chemical structure and the same physico-chemical properties, were investigated in this study. Thes datasets give some insight into how far structure activity relationships can be used for these modes of action.

Methods

The toxicity of the isomers was investigated by the daphnia immobilisation test as well as the duckweed growth inhibition test. The estrogenic potency of the p-NP isomers was analyzed by MVLN-Reportergen-Assay.

Results

No differences between the isomers were found for baseline toxicity, neither in the daphnia immobilisation test nor in the duckweed growth inhibition test. Estrogenic potency of the isomers in the MVLN reportergen assay was markedly different for the tested isomers. The highest estrogenic potency was found for p353-NP, whereas p262-NP and p22-NP exhibited no estrogenic, but partial antagonistic potency in this assay.

Discussion

The results from this study clearly indicate how far simplification and structure activity relationships can be used in risk analysis. For bioconcentration and baseline toxicity structure activity relationships are possible and will allow simplification of the risk analysis. For special modes of action simple structure activity relationships are per se impossible. This was shown especially for the estrogen receptor interactions, where only small structural differences can lead to different modes of action.

Conclusions

It seems possible to reduce the effort for risk analysis, using combinations of measured data and predictive models. At the moment it seems unlikely that predictive models alone will and can be used for risk analysis.     

U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

Relationship Between Crown Condition and Tree Diameter Growth in Southern Swedish Oaks

We studied correlation between crown conditions and tree-ring widths in 260 trees of pedunculate oak (Quercus robur L.) growing on 33 sites in southern Sweden. The tree-ring increment over 1998-2002 was highest in trees with healthy crowns, intermediate in trees with moderately declined crowns, and lowest in trees with heavily declining crowns. The time period with significant correlation between crown status and tree-ring increment varied between 10 years (given autocorrelation in tree-ring chronologies preserved) and 4 years (autocorrelation removed). In pairwise comparisons of three crown classes, differences in tree-ring increment between trees with healthy crowns and trees with heavily declining crowns were the most pronounced, Fisher LSD P value staying below 0.05 over 13 years (autocorrelation preserved ) or 4 years (autocorrelation removed). Over two 5-year periods (1993-1997 vs. 1998-2002) the cumulative increment increased significantly for trees with healthy crowns, did not change in trees with moderately declining crowns, and significantly decreased in trees with heavily declining crowns. For trees with healthy crowns, this dynamics may represent growth recovery after 1992 drought. Instead, oaks with defoliation above 60% appear to reach a threshold in their ability to recover growth. At sites on nutrient-poor soils cumulative increments over 1998-2002 differed significantly among trees with different crown condition and no differences were observed at sites on nutrient-rich soils. Analyses and interpretation of the oak growth trends as recovered from tree-ring chronologies may be improved by controlling for the crown status of the trees sampled, e.g., by using sampling strategy that would represent the average crown and growth conditions of the sites.