Evaluation of two adsorbents for diffusive sampling and thermal desorption-gas chromatographic analysis of monoterpenes in air

Tube type samplers with two different adsorbents, Chromosorb 106 and Tenax TA, were evaluated by laboratory experiments and field tests for simultaneous diffusive sampling of alpha-pinene, beta-pinene and delta 3-carene and subsequent thermal desorption-gas chromatographic analysis. No statistically significant effects of exposure time, concentrations of monoterpenes or relative humidity were found for samplers with Chromosorb 106 when running a factorial design, with the exception of the adsorption of delta 3-carene, for which some weak effects were noted. Samplers with Tenax TA were affected by the sampling time as well as the concentration for all terpenes, with a strong interaction effect between these two factors. The terpenes showed good storage stability on both adsorbents. No effect of back-diffusion was noted when using Chromosorb 106, while Tenax TA showed some back-diffusion effects. The uptake rates, in ml min-1, for the terpenes on Chromosorb 106 were 0.36 for alpha-pinene, 0.36 for beta-pinene and 0.40 for delta 3-carene. The corresponding average values on Tenax TA were 0.30 for alpha-pinene, 0.32 for beta-pinene and 0.38 for delta 3-carene. The field validation proved that diffusive sampling on Chromosorb 106 agreed well with pumped sampling on charcoal for stationary samples, while the personal samples indicated a discrepancy of 25% between Chromosorb 106 and charcoal samples. Tenax TA generally gave lower results than Chromosorb 106 in all field samples. Samplers packed with Chromosorb 106 could be used to monitor terpene levels in workplaces such as sawmills. The major advantages with this method are the sampling procedure, which is simple to perform compared to other techniques, the easily automated analysis procedure and the possibility to reuse the samplers.     

Impact of Climate Change on Fish Population Dynamics in the Baltic Sea: A Dynamical Downscaling Investigation

Understanding how climate change, exploitation and eutrophication will affect populations and ecosystems of the Baltic Sea can be facilitated with models which realistically combine these forcings into common frameworks. Here, we evaluate sensitivity of fish recruitment and population dynamics to past and future environmental forcings provided by three ocean-biogeochemical models of the Baltic Sea. Modeled temperature explained nearly as much variability in reproductive success of sprat (Sprattus sprattus; Clupeidae) as measured temperatures during 1973-2005, and both the spawner biomass and the temperature have influenced recruitment for at least 50 years. The three Baltic Sea models estimate relatively similar developments (increases) in biomass and fishery yield during twenty-first century climate change (ca. 28 % range among models). However, this uncertainty is exceeded by the one associated with the fish population model, and by the source of global climate data used by regional models. Knowledge of processes and biases could reduce these uncertainties.     

Photoinduced reduction of divalent mercury in ice by organic matter

Reduction of divalent mercury and subsequent emission to the atmosphere has been identified as loss process from surface snow, but its mechanism and importance are still unclear. The amount of mercury that stays in the snow pack until spring is of significance, because during snow melt it may be released to the aquatic environment and enter the food web. Better knowledge of its fate in snow might further assist the interpretation of ice core data as paleo-archive. Experiments were performed under well-controlled laboratory conditions in a coated wall flow tube at atmospheric pressure and irradiated with light between 300 nm and 420 nm. Our results show that the presence of benzophenone and of oxalic acid significantly enhances the release of mercury from the ice film during irradiation, whereas humic acid is less potent to promote the reduction. Further it was found that oxygen or chloride, and acidic conditions lowered the photolytically induced mercury release in the presence of benzophenone, while the release got larger with increasing temperatures.     

Filamentous scum bacteria in activated sludge plants: detection and identification quality by conventional activated sludge microscopy versus fluorescence in situ hybridization.

Detection of filamentous bacteria morphotypes involved in scum formation in activated sludge wastewater treatment plants by conventional sludge microscopy is often doomed to fail because of morphological and taxonomical variations. The aim of this study is to compare detection, identification, and quantification quality of filamentous "scum bacteria" found by conventional activated sludge microscopy and fluorescence in situ hybridization (FISH). In the case of filamentous Microthrix parvicella and Eikelboom morphotypes 1863 and 1851, conventional activated sludge microscopy and FISH results correspond well. In contrast, conventional activated sludge microscopy overlooks nocardioform actinomycete and type 1863 single cells. On the other hand, FISH underestimates filamentous nocardioform actinomycetes and morphotypes 0041/0675 or 0092 because of insufficient cell wall permeability or because of their taxonomic variability, with a resulting inadequacy of previously published probes. Nostocoida limicola morphotype results are still inconclusive because of low bacteria numbers being available in situ and the enormous taxonomic variability within this group.     

Veränderungen des NO/NO2-Verhältnisses in Nordrhein-Westfalen (1984–2004) und mögliche Ursachen

Objective and Background

The nitrogen oxides NO and NO₂ and, in particular, their ratio (NO/NO₂), play important roles in the radical-system of the atmospheric boundary layer. There were various indications upon a dropping NO/NO₂-ratio in citiex over the last years, however, no proof has been given yet Especially in densely populated areas such as the federal state of North Rhine-Westphalia (NRW), such a change can have significant influences upon various atmospheric reactions. The objective of this investigation was to prove the existence of a systematic change of the NO/NO₂-ratio, to describe the development of NO_x over the past 2 decades at different locations and to determine the causes for this development.

Methods

To detect changes of the NO/NO₂-ratio we processed the data of 11 continuously operating air quality stations of the State Environment Agency (LUA NRW) with time series reaching back up to 20 years. We investigated rural stations, stations in the urban background and heavily traffic influenced locations. It was possible to calculate and assess the NO/NO₂-ratio under consideration of the fast reaction of ozone with NO. There were clear indications towards existing trends and they could be determined as statistically significant using the nonparametric Mann-Kendall Test. The analysis of possible causes for the change of the NO/NO₂-ratio focused upon the change of the global radiation, the change of the patterns of the atmosphetic circulation, and the frequency of cyclones and anticyclones meteorological conditions in Central Europe, the introduction of automotive catalytic converters, and the development of the atmospheric oxidation-capacity.

Results and conclusions

The results are indicating a decline of the ratio at traffic-influenced stations with a statistical significance over 95%. The negative trend can also be detected at most urban background stations. It was problematic to perform the trend-analysis of the rural background station in the Egge-Mountains because of the fragmentary character of the dataset. Regional differences in the development of the NO/NO₂-ratio indicate towards various causes. Crucial for the situation at the rural areas are the changed trajectories of cyclones and anticyclones as well as the decline of the atmospheric oxidation-capacity, while the traffic plays another important role at urban stations. The negative trend at the traffic-stations was intensified by the introduction of catalytic converters, which lead to a reduction in emissions of NO_x

Recommendations and prospects

The significance of the NO/NO₂-ratio for the oxidation capacity of the atmosphere shows the necessity to further monitor this development. Previous investigations detected a decline in total NO_x without examining the relative development of the two nitrogen oxides towards each other. Gaining insight into the local differences of this ratio helps to allocate sources and to develop understanding of the atmospheric processes.     

Passive sampling in combination with thermal desorption and gas chromatography as a tool for self-assessment of chemical exposure

Diffusive samplers for monitoring of air quality are user-friendly devices that can normally be operated by the user himself. Hence these samplers are suitable for self-assessment. Practical and work organisational aspects of self-assessment of chemical exposure were studied in different occupational settings. It was found that the diffusive sampler used in these studies, the Perkin-Elmer tube in combination with thermal desorption, worked well for the purpose and could be correctly handled by the individuals using it. The results from self-assessments agreed well with expert measurements carried out by an occupational hygienist. However, in order to obtain a sustainable system of self-assessment strong organizational support is needed.