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.”     

Bioavailability of copper,cadmium, zinc,and lead in tropical savanna soils assessed by diffusive gradient in thin films (DGT) and ion exchange resin membranes

The technique of diffusion gradient in thin films (DGT) for assessing bioavailable metals has not been tested under field conditions. We assessed the relationships of DGT- and cation exchange resin-membrane-measured concentrations of Cd, Cu, Pb, and Zn with plant uptake of the metals under greenhouse and field conditions. In the greenhouse, the effective concentrations of Cu, Pb, and Zn by DGT correlated significantly with uptake by sorghum (Sorghum bicolor), but cation exchange resin-membrane-measured concentrations of Cd, Pb, and Zn did not correlate with sorghum uptake. In the field, the DGT-measured concentrations of Cd, Pb, and Zn were not linearly related to uptake Cd, Pb, and Zn by lettuce (Lactuca sativa) except for Cu uptake (r = 0.87, p < 0.05). Similarly, it was only the resin-membrane-extractable Pb that correlated with Pb uptake by lettuce (r = 0.77; p < 0.05). However, fitting non-linear regression models improved the plant metal uptake predictions by DGT-measured bioavailable Cd, Cu, Pb, and Zn under field conditions. In conclusion, the DGT technique was fairly predictive of bioavailability in the greenhouse, but not in the field.     

The determination of the extractability of selected elements from agricultural soil

Concentrations of Ag, Al, Ba, Cd, Co, Cr, Cu, Fe, K, Mn, Na, Ni, Pb, Sr, and Zn—isolated by sequential extraction steps from apple orchard soil—were analyzed by inductively coupled plasma-atomic emission spectroscopy and compared to the total amount of metal in soil determined by XRF. The extractable amount of each metal was calculated by the extraction yields of the four steps. The LODs of the different elements in all extracts ware below 3 μg/L except for Ba (steps 1 and 2), Cu (step 1), Fe (all steps), K (steps 1–3), Mn (step 2), Na (steps 1–3), Ni (step 1), Pb (steps 1 and 4), and Zn (steps 1 and 2). The highest LOD (>10 μg/L) was found for Fe, K, and Na (step 1). The recovery of all metals after four sequential extraction steps was 90–112%. The repeatability (<1.1%), the intermediate precision (<5.3%), the day-to-day reproducibility (<6.2%), and the overall uncertainty of measurement (approximately 4–8.5%) for all analyzed metals supports the choice of the method used.     

Seasonal baseline of nutrients and stable isotopes in a saline lake of Argentina: biogeochemical processes and river runoff effects

The seasonal variability of inorganic and organic nutrients and stable isotopes and their relations with plankton and environmental conditions were monitored in Lake Chasicó. Principal component analysis evidenced the strong influence of the river runoff on several biogeochemical variables. Silicate concentrations were controlled by diatom biomass and river discharge. Higher values of nitrate and soluble reactive phosphorus (SRP) indicated agricultural uses in the river basin. Elevated pH values (～9) inhibiting nitrification in the lake explained partially the dominance of ammonium: ～83 % of dissolved inorganic nitrogen (DIN). The low DIN/SRP ratio inferred nitrogen limitation, although the hypotheses of iron and CO₂ limitation are relevant in alkaline lakes. Particulate organic matter (POM) and dissolved organic matter (DOM) were mainly of autochthonous origin. The main allochthonous input was imported by the river as POM owning to the arid conditions. Dissolved organic carbon was likely top-down regulated by the bacterioplankton grazer Brachionus plicatilis. The δ¹³C signature was a good indicator of primary production and its values were influenced probably by CO₂ limitation. The δ¹⁵N did not evidence nitrogen fixation and suggested the effects of anthropogenic activities. The preservation of a good water quality in the lake is crucial for resource management.     

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.