Biomonitoring von Stickstoffimmissionen

Background and aim

Air pollution caused by oxidized and reduced nitrogen is distributed over wide areas of Europe at a high level. As an alternative or complement to physical measurements and modelling calculations, biomonitoring with plants provides techniques to assess amounts and effects of pollution from oxidized and reduced nitrogen compounds (depositions and concentrations). Many of the previously implemented techniques are based on well-proven standardised methods, e.g. documented in VDI guidelines, modified more or less for a biomonitoring of atmospheric nitrogen pollution. This paper gives a review of the techniques for a biomonitoring of atmospheric nitrogen pollution, their possibilities as well as their limitations.

Main features

-diversity of the ground vegetation

-nitrogen accumulation in vascular plants

-exposure of vascular plants

-mapping of epiphytic lichens, bryophytes and algae

-nitrogen accumulation in lichens and bryophytes

-exposure of lichens and bryophytes

Results and Discussion

Important response parameters are nitrogen concentrations in plant tissue (shoot, needle, leave) and biodiversity of plant species. These responses of vascular plants in many cases are influenced by other local varying conditions, in particular the soil. The exposure of vascular plants over a short period provides a standardised quantification of the total atmospheric nitrogen input in a model ecosystem. The enrichment of nitrogen in the plant tissue of bryophytes and lichens from the ground vegetation is closely correlated with the amount of nitrogen deposition. The diversity of epiphytic lichens and the response of exposed Hypogymnia physodes is more sensitive to ammonia than to nitrous oxide, whereas with the diversity of epiphytic bryophytes or the abundance of algae no significant correlation with atmospheric N pollution were found.

Conclusions

Some bioindication techniques provide a causeeffect related, partly standardised biomonitoring of nitrogen pollution. In some cases varying experiences with some biomonitors like the biodiversity of the ground vegetation, exposure of lichens, moss bags and grass cultures stress the need for more research in this subject.     

Chemistry and aerosols in the marine boundary layer: 1-D modelling of the three ACE-2 Lagrangian experiments

Three Lagrangian experiments were conducted during IGAC's second aerosol characterization experiment (ACE-2) in the area between Portugal, Tenerife and Madeira in June/July 1997. During each Lagrangian experiment, a boundary layer air mass was followed for about 30 h, and the temporal evolution of its chemical and aerosol composition was documented by a series of vertical profiles and horizontal box pattern flown by the Meteorological Research Flight research aircraft Hercules C130. The wealth of observational data that has been collected during these three Lagrangian experiments is the basis for the development and testing of a one-dimensional Lagrangian boundary layer model with coupled gas, aqueous, and aerosol phase chemistry. The focus of this paper is on current model limitations and strengths. We show that the model is able to represent the dynamical and chemical evolution of the marine boundary layer, in some cases requiring adjustments of the subsidence velocity and of the surface heat fluxes. Entrainment of a layer rich in ozone and carbon monoxide from a residual continental boundary layer into the marine boundary layer as well as in-cloud oxidation of sulphur dioxide by hydrogen peroxide are simulated, and coherent results are obtained, concerning the evolution of the small, presumably sulphate–ammonia aerosol mode.     

Pyrolysis of EVA and its application in recycling of photovoltaic modules

The basic pyrolysis behaviour of ethylene vinyl acetate(EVA) copolymer, which is often used as a lamination agent in solar modules, was investigated in thermogravimetry, differential thermal analysis(DTA) and thermovolumetry. The TG analysis showed that the EVA pyrolysis can be accelerated under the partial oxidizing atmosphere but the end pyrolysis temperature must be higher than in nitrogen, to eliminate the coke formed. Meanwhile, a strong exothermal peak occurs at about 450% under the air condition and gets weaker obviously at the oxygen content lower than 10 vol. %. The mass balance of EVA pyrolysis was given through the thermovolumetry with the output of l0 wt. % permanent gas, 89.9 wt. % condensate and 0.1% residual coke. Besides, the composition of the permanent gas and condensate at different pyrolysis stages were analysed and interpreted on the known pyrolysis mechanism.     

Fate of β-blockers in aquifer material under nitrate reducing conditions: Batch experiments

The fate of the three environmentally relevant β-blockers atenolol, metoprolol and propranolol has been studied in batch experiments involving aquifer material and nitrate reducing conditions. Results from the about 90 d long tests indicate that abiotic processes, most likely sorption, jointly with biotransformation to atenololic acid were responsible for the 65% overall removal observed for atenolol. Zero order kinetics, typical of enzyme-limited reactions, controlled the transformation of this beta blocker to its corresponding carboxylic acid. The mass balance evidences that no mineralization of atenolol occurs in the biotic experiment and that atenololic acid is more stable than its parent compound under the studied conditions. This finding stresses the importance of considering atenololic acid as target compound in the environmental studies on the fate of atenolol. For metoprolol and propranolol the results from the experiment suggest a slower sorption to be the dominant removal process, which led to final decreases in concentrations of 25-30% and 40-45%, respectively. Overall, the removals observed in the experiments suggest that subsurface processes potentially constitute an alternative water treatment for the target beta-blockers, when compared to the removals reported for conventional wastewater treatment plants.     

Uranium uptake and depuration in the aquatic invertebrate Chironomus tentans

Evaluation of aqueous uranium (U) uptake and depuration in larvae of the midge Chironomus tentans were investigated in two separated experiments. First, a static-renewal experiment was performed with 10-d old C. tentans larvae exposed to 300 μg U/L. The animals steadily accumulated U (K_u = 20.3) approaching steady-state conditions (BAF = 56) in approximately 9-11 d. However, accumulated U was readily depurated (K_d = 0.36) with U tissue concentration decreasing rapidly within 3 d of the larvae being placed in clean water (t_1/2 = 1.9 d). Also, the growth of C. tentans larvae appeared to decrease after 6-11 d of U exposure, probably due to the reallocation of resources into U detoxification mechanisms. However, growth significantly increased once C. tentans were transferred to clean water. A separate short-term experiment was performed to evaluate the possible mechanism of U uptake in this invertebrate. Results suggested a passive mechanism of U uptake coupled with an active mechanism of U depuration but no details related to the type of mechanisms or pathway was investigated.     

Arsenic concentration and speciation in five freshwater fish species from Back Bay near Yellowknife, NT, CANADA

The concentration of total arsenic and five different arsenic species [As(III), As(V), monomethylarsonic acid (MMA), dimethylarsenic acid (DMA), and arsenobetaine (AsB)], were measured in the muscle, liver and gastrointestinal tract (GIT) of five different fish species [lake whitefish (Coregonus clupeaformis), walleye (Stizostedion vitreum), northern pike (Esox lucius), white sucker (Catostomus commersoni) and longnose sucker (Catostomus catostomus)] from Back Bay, Great Slave Lake, near the city of Yellowknife, NT, Canada. The total concentration (dry weight) of arsenic in muscle ranged from 0.57 to 1.15 mg/kg, in the liver from 0.42 to 2.52 mg/kg and in the GIT from 1.48 to 8.92 mg/kg. Among fish species, C. commersoni had significantly higher total arsenic concentrations in the GIT than S. vitreum, E. lucius and C. clupeaformis, and higher total arsenic concentrations in the liver than C. clupeaformis. The mean concentration of As(III) and As(V) in the muscle of all fish ranged from < or =0.01 to 0.05 mg/kg and < or =0.01 to 0.02 mg/kg, respectively, and together comprised < or =7.5% of the total arsenic measured in muscle. The concentrations of MMA were below detection in the muscle of all five fish species. However, AsB and DMA were measured in all fish species and nearly all fish tissues. The concentrations of AsB ranged from 0.01 to 0.13 mg/kg and the concentrations of DMA ranged from <0.02 to 0.45 mg/kg. The majority (>50%) of organic arsenic in almost all of the tissues from fish caught in Back Bay was not directly identified. Evidence from the literature suggests that most of these other organic arsenic species were likely trimethylated arsenic compounds, however, further analytical work would need to be performed to verify this hypothesis.     

Effect of sampling method on contaminant measurement in pore-water and surface water at two uranium operations: can method affect conclusions?

This paper describes a comparison of two methods of sediment pore-water sampling and two methods of surface water sampling that were used in a broader investigation of cause(s) of adverse effects on benthic invertebrate communities at two Saskatchewan uranium operations (Key Lake and Rabbit Lake). Variables measured and compared included pH, ammonia, DOC, and trace metals. The two types of sediment pore-water samples that were compared are centrifuged and 0.45-microm filtered sediment core samples vs. 0.2-microm dialysis (peeper) samples. The two types of surface water samples that were compared are 53-microm filtered Van Dorn horizontal beta samples vs. 0.2-microm dialysis (peeper) samples. Results showed that 62% of the sediment core pore water values were higher than the corresponding peeper pore-water measurements, and that 63% of the Van Dorn surface water measurements were lower than corresponding peeper surface water measurements. Furthermore, only 24% and 14% of surface water and pore-water measurements, respectively, fell within +/-10% range of one another; 73% and 50%, respectively, fell within +/-50%. Although somewhat confounded by differences in filtering method, the observed differences are believed to primarily be related to small, vertical differences in the environment sampled. Despite observed differences in concentrations of toxicologically relevant variables generated by the different sampling methods, the weight of evidence (WOE) conclusions drawn from each set of exposure data on the possible cause(s) of in situ toxicity to Hyalella azteca from a related study were the same at each uranium operation. However, this concurrence was largely due to other dominant lines of evidence. The WOE conclusions at Key Lake were dominated by the toxicity response of H. azteca in relation to exposure chemistry, where as the WOE conclusions at Rabbit Lake were informed by exposure chemistry, the toxicological response of H. azteca, and whole-body contaminant concentrations in the test organisms. Had these multiple lines of evidence not been available, differences in exposure chemistry generated by the different sampling methods could have substantially influenced the identification of potential causes of in situ toxicity.     

Investigation of partitioning mechanism for volatile organic compounds in a multiphase system

Laboratory experiments were performed to investigate the partitioning behavior of a set of diverse volatile organic compounds (VOCs). After equilibration at a temperature of 25 °C, the VOC concentrations were measured by headspace method in combination with gas chromatography/mass spectrometry (GC/MS). The obtained data were used to determine the partition coefficients (K_P) of VOCs in a gas-liguid-solid system. The results have shown that the presence and nature of solid materials in the working solution control the air-water partitioning of dissolved VOCs. The air/solution partitioning of BTEX and C₉-C₁₀ aldehydes was most affected in the presence of diesel soot. K_P values decreased by a factor ranging from 1.5 for toluene to 3.0 for ethylbenzene. The addition of mineral dust in the working solution exhibited greater influence on the partitioning of short aldehydes. K_P values decreased by a factor of 1.8. The experimental partition coefficients were used to develop a predictive model for partitioning of BTEX and n-aldehydes between air, water and solid phases.     

Selenium speciation and localization in chironomids from lakes receiving treated metal mine effluent

A lake system in northern Saskatchewan receiving treated metal mine and mill effluent contains elevated levels of selenium (Se). An important step in the trophic transfer of Se is the bioaccumulation of Se by benthic invertebrates, especially primary consumers serving as a food source for higher trophic level organisms. Chironomids, ubiquitous components of many northern aquatic ecosystems, were sampled at lakes downstream of the milling operation and were found to contain Se concentrations ranging from 7 to 80 mg kg⁻¹ dry weight. For comparison, laboratory-reared Chironomus dilutus were exposed to waterborne selenate, selenite, or seleno-DL-methionine under laboratory conditions at the average total Se concentrations found in lakes near the operation. Similarities in Se localization and speciation in laboratory and field chironomids were observed using synchrotron-based X-ray fluorescence (XRF) imaging and X-ray absorption spectroscopy (XAS). Selenium localized primarily in the head capsule, brain, salivary glands and gut lining, with organic Se species modeled as selenocystine and selenomethionine being the most abundant. Similarities between field chironomids and C. dilutus exposed in the laboratory to waterborne selenomethionine suggest that selenomethionine-like species are most readily accumulated, whether from diet or water.