Chemisch-analytische Untersuchung von Arsenkampfstoffen und ihren Metaboliten

Arsenic containing chemical warfare agents (cwa) are persistent in the environment and continue to contaminte soil and ground water. In this paper the chemical rections of the cwa diphenylarsine chloride (CLARK I), phenylarsine dichloride (PFIFFIKUS), ethylarsine dichloride (DICK) and of chlorovinyl arsenic compounds (LEWISITE) are shown. The posibilities of the detection and determination of this cwa and their metabolites are presented.     

Persistente organische Schadstoffe in Böden, Gewässern und in Firn der Region nördliches Piringebirge (Bulgarien)

Systematic environmental screenings are still the exception in South-Eastern Europe. Especially, there is a decisive lack of information concerning the occurrence and behaviour of xenobiotic and toxic compounds like volatile-and non volatile halogenated organics, suppressed by the surrogate AOX, synthetic chelating agents, pesticides, like DDT as well as chlorate in the biosphere. The analysis of soils, waters and firns of a representative area in Bulgaria, the Pirin mountains, indicate a relatively low back ground pollution. The accumulation of the xenobiotics in this high mountain region is recognised to be low. Nevertheless, traces of pesticides and chelating agents like EDTA and NTA in ice (firns) and soils were found. The surrogate AOX should be a parameter, suitable for routine environmental screenings of such areas.     

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.     

Anticipating Climate Threshold Damages

Several integrated assessment studies have concluded that future learning about the uncertainties involved in climate change has a considerable effect on welfare but only a small effect on optimal short-term emissions. In other words, learning is important but anticipation of learning is not. We confirm this result in the integrated assessment model “model of investment and technological development” for learning about climate sensitivity and climate damages. If learning about an irreversible threshold is included, though, we show that anticipation can become crucial both in terms of necessary adjustments of pre-learning emissions and resulting welfare gains. We specify conditions on the time of learning and the threshold characteristic, for which this is the case. They can be summarized as a narrow “anticipation window.”     

Impacts of “metals” on human health: a comparison between nine different methodologies for Life Cycle Impact Assessment (LCIA)

This paper looks into the differences and uncertainties in determining the impact of “metals’” emissions on human health, in Life Cycle Impact Assessment (LCIA). Metals are diverse substances, with different properties and characteristics, considered important in LCIA because of their toxicity to humans and ecosystems. First, we defined a list of the most significant metals in terms of impacts on human health. This was done according to precise criteria accounting for both physical and toxic properties of the metals. Second, we performed an LCIA on different key processes using various existing LCIA methodologies and including also USEtox: the recently developed consensus-model for LCIA. Last, we compared the results in relative terms using a contribution analysis. The analysis showed poor or no agreement between the methods: the relative contribution of each metal and of the metals in total to the total impact on human health changes greatly according to the LCIA method used. These differences are due mainly to the number of metals included in each method and to the technique used to calculate the characterization factors. Results obtained with USEtox show no apparent correlation with results calculated with other methods. At present time USEtox is recommended as the best model for LCIA on human toxicity, but mainly because of the large consensus behind it, because its uncertainties regarding metals are still high. The study gives a good and simple overview regarding the way different methods address the impact assessment for metals, and helps in the interpretation of LCIA results for actual LCA studies where metal emissions are involved.     

Distribution,fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, ¹⁴C- and ¹³C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied ¹⁴C was mineralized. The bioavailable, water extractable portion was low (9 % of applied ¹⁴C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied ¹⁴C was incorporated into organo-clay complexes as NER, whereas 9 % of applied ¹⁴C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Variation of the Relative Humidity of Air Released from Canisters after Ambient Sampling

ABSTRACT

Dalton's law of partial pressures and the hypothesis that water vapor equilibrium in a canister is identical to that established above liquid water are used to predict the variation of the percent relative humidity (%RH) of air released from canisters used in ambient air sampling, typically 6-L canisters pressurized with 18 L of air. When (and if) the water vapor partial pressure in a canister exceeds its saturation vapor pressure, water vapor condensation begins and the condensation rate equals the sampling rate of water vapor into the canister. Under constant temperature conditions, the air subsequently released from the canister is less humid than the original sample, following the relationship %RH = 100% (6 L/V_s) for V_s> V_r, where V_s is the residual air volume (referenced to atmospheric pressure), and V_r is shown to depend on the %RH of the ambient air sample. V_r is the residual air volume at which water is completely removed (except for adsorbed water vapor) from the canister wall. For V_s < V_r, the predicted %RH is constant and equal to its value at V_r. Experimental values agree reasonably well with predictions at both high (90%) and low (34%) RH. However, experimental values are often slightly displaced (usually towards lower values of %RH) for mid-range %RH (61%) and variations in %RH near V_r change from canister to canister.     

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ¹³C, δ²H and δ¹⁸O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration.We found significant differences in the δ¹³C-value of the dissolved inorganic carbon (δ¹³C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ¹³C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ¹³C-DIC of ?20‰ to ?25‰. The production of methane under anaerobic conditions caused an increase in δ¹³C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ¹³C-DIC of about ?20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation–reduction status of MSW landfills.Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration.     

Concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil in the vicinity of a landfill

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64-2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans.