Grundwasserbelastung durch Rüstungsaltlast-Emissionen Nachweis von Arsenkampfstoffen und weiteren kampfmittelspezifischen Rückst?nden

Die Ergebnisse der Untersuchung von Wasserproben aus dem Einflu?ereich der Rüstungsaltlast „Dethlinger Teich“ bei Munster/Niedersachsen werden dargestellt und bewertet. Von mehr als 50 untersuchten spezifischen Substanzen wurden Arsenkampfstoffe als Hauptkontaminanten erkannt. Im Rahmen der Gef?hrdungsabsch?tzung wird hier erstmals eine Analysenmethode zur Unterscheidung zwischen anorganisch und organisch gebundenem Arsen vorgestellt. Groundwater analyses in the area of the former munitions depository (World War II) „Dethlinger Teich“ near Munster/Niedersachsen were evaluated. Results from 50 different chemical substances showed that arsenic compounds are the main contaminating chemicals. A new method has been developed to distinguish between morganically- and organically bound compounds. This differentiation is required for risk assessment and evaluation. Also, the relationship of chemical structure and physiological effects in organo arsenic compounds is described.     

A natural analogue of high-pH cement pore waters from the Maqarin area of northern Jordan: Comparison of predicted and observed trace-element chemistry of uranium and selenium

Current design concepts for low-/intermediate-level radioactive waste disposal in many countries involve emplacement underground in a cementitious repository. The highly alkaline groundwaters at Maqarin, Jordan, are a good analogue for the cementitious pore waters that will be present within such a repository. A geochemical modelling study of these groundwaters has been carried out in order to test the applicability of equilibrium models in geochemical programs and their associated thermodynamic databases in such hyperalkaline conditions. This was achieved by comparison of elemental solubilities and speciations predicted by the programs with observations in the natural system. Five organisations took part in the study: AEA Technology, U.K.; Chalmers University of Technology, Sweden; MBT Tecnología Ambiental, Spain; Nagra, Switzerland; and SKB, Sweden. The modelling study was coordinated by the University of Berne.The results of the study showed good agreement between the predictions of the programs employed. Comparison of the observed solids with those predicted by the models has allowed limited validation of the databases. The results for U and Se are presented here.     

Comparison of two methods for the determination of total organic halogen (TOX) in receiving waters

Two methods for the determination of total organic halogen (TOX), orginating from bleaching of pulp, in receiving waters have been compared. One of the methods (AC/MC) is based on adsorption of the halogenated matter onto an activated carbon sorbent. The halogen is determined by a microcoulometric technique after combustion of the carbon. The other method (XAD/PT) uses an XAD resin as sorbent and the determination of the halogen is carried out by potentiometric titration after a schöniger combustion of the resin eluate.Both methods showed good performance for samples consisting of spent bleach liquors diluted with distilled, fresh and brackish water. The repeatability was very good with a relative standard deviation less than a few per cent. The detection limit of the AC/MC method is about 0.1 μmol/1 and for the XAD/PT method about ten times higher. The AC/MC method gave in most cases 10–20% higher TOX concentrations compared to the XAD/PT method.     

Perfluorinated chemicals in relation to other persistent organic pollutants in human blood

In order to evaluate blood levels of some perfluorinated chemicals (PFCs) and compare them to current levels of classical persistent organic pollutants (POPs) whole blood samples from Sweden were analyzed with respect to 12 PFCs, 37 polychlorinated biphenyls (PCBs), p,p'-dichlorodiphenyl-dichloroethylene (DDE), hexachlorobenzene (HCB), six chlordanes and three polybrominated diphenyl ethers (PBDEs). The median concentration, on whole blood basis, of the sum of PFCs was 20-50 times higher compared to the sum of PCBs and p,p'-DDE, 300-450 times higher than HCB, sum of chlordanes and sum of PBDEs. Estimations of the total body amount of PFCs and lipophilic POPs point at similar body burdens. While levels of for example PCBs and PBDEs are normalized to the lipid content of blood, there is no such general procedure for PFCs in blood. The distributions of a number of perfluorinated compounds between whole blood and plasma were therefore studied. Plasma concentrations were higher than whole blood concentrations for four perfluoroalkylated acids with plasma/whole blood ratios between 1.1 and 1.4, whereas the ratio for perflurooctanesulfonamide (PFOSA) was considerably lower (0.2). This suggests that the comparison of levels of PFCs determined in plasma with levels determined in whole blood should be made with caution. We also conclude that Swedish residents are exposed to a large number of PFCs to the same extent as in USA, Japan, Colombia and the few other countries from which data is available today.     

Melamine-based organoclay to sequester atrazine

Sequestration of aqueous atrazine by organoclays prepared from the surfactant 6-piperazin-1-yl-N,N'-bis-(1,1,3,3-tetramethyl-butyl)-(1,3,5)triazine-2,4-diamine and Gonzales bentonite was assessed using 14C-labeled atrazine. Organoclays with varying ratios of surfactant to clay were evaluated with respect to their ability to sequester atrazine from an aqueous solution. Organoclays containing 100-200 g kg-1 surfactant on a total weight basis provided the most efficient adsorption of atrazine, with apparent KOC values exceeding 5000 l kg-1 at these loading fractions. Less than 12% of sequestered atrazine was released during four sequential day long washings, supporting our expectation that the majority of the reaction of atrazine with the surfactant lead to irreversible chemical bond formation through nucleophilic aromatic substitution.     

Prediction of ozone concentrations in Oporto city with statistical approaches

The performance of three statistical methods: time-series, multiple linear regression and feedforward artificial neural networks models were compared to predict the daily mean ozone concentrations. The study here reported was based on data from one urban site with traffic influences and one rural background site. The studies were performed for the year 2002 and the respective four trimesters separately. In the multiple linear regression and feedforward artificial neural network models, the concentrations of ozone, the concentrations of its precursors (nitrogen oxides) and some meteorological variables for one and two days before the prediction day were used as predictors. For the application of these models in the validation step, the inputs of ozone concentration for one and two days before were replaced by the ozone concentrations predicted by the models. The results showed that time-series modelling was not profitable. In the development step, similar performances were obtained with multiple linear regression and feedforward artificial neural network. Better performance indexes were achieved with feedforward artificial neural network models in validation step. Concluding, feedforward artificial neural network models were more efficient to predict ozone concentrations.     

Characterization of organic compounds in aerosol particles from a coniferous forest by GC-MS

Atmospheric aerosol particles were collected in a Finnish Scots pine forest as part of a European Union project. Sampling was done in March-April 2003 with a high-volume sampler. Dynamic ultrasonic-assisted solvent extraction and gas chromatography-mass spectrometry (GC-MS) were applied to the analysis of aerosol samples for analytes such as n-alkanes, polycyclic aromatic hydrocarbons (PAH), oxidized polycyclic aromatic hydrocarbons (oxy-PAHs), sesquiterpenes (SQT) and oxidized sesquiterpenes (oxy-SQT). The highest concentrations were found for the n-alkanes, which were present in a wide range (C11-C32) indicating both biogenic and anthropogenic sources. PAH compounds were found in every sample while oxy-PAH compounds were present in low concentrations in a few samples. A few oxidized monoterpenes, most notably (-)-verbenone and pinonaldehyde, were found in several samples in concentrations clearly exceeding the PAH concentrations. The effect of temperature could be seen in most samples, where the concentrations of n-alkanes declined with decreasing temperatures. Particle formation events were accompanied by higher concentrations of heavy n-alkanes, verbenone and pinonaldehyde.     

Organochlorine contaminants in complete clutches of Morelet's crocodile (Crocodylus moreletii) eggs from Belize

Seven complete clutches of Morelet's crocodile (Crocodylus moreletii) eggs were collected in northern Belize and examined for organochlorine (OC) pesticide residues. The primary OC detected, p,p-DDE, was found in every egg analyzed (n=175). Other OCs detected included p,p-DDT, p,p-DDD, methoxychlor, aldrin, and endosulfan I. Concentrations of individual OCs ranged from 4 ppb (ng chemical/g egg wet weight) to greater than 500 ppb. A statistical evaluation of p,p-DDE levels in three complete clutches was used to derive the minimum number of eggs needed from a clutch to precisely determine the mean p,p-DDE concentration representative of that clutch. Sample sizes of 8 (80% confidence level) and 11 (90% confidence level) were determined to yield an accurate estimate of contaminant levels in a full clutch of eggs. The statistically recommended sample size of 11 eggs (at 90% confidence level) was successfully tested on the four additional clutches.