Identifizierung toxischer Verbindungen in Sedimenten: Ansätze zur Integration von Wirkung und Bioverfügbarkeit

Sediments play an important role for aquatic ecosystem functions. However, they also act as sink, storage and source of lipophilic toxicants and metals. Effect-directed analysis (EDA) is a powerful tool to identify compounds causing adverse effects. In order to avoid misinterpretations and biased prioritization bioavailability needs to be considered together with effects. Bioavailability is a complex process finally resulting in the transfer of a so far particle bound molecule to the target location within the organism where it causes an effect. In order to operationalize this concept for EDA it can be divided into several partial processes. These include desorption from sediments and thus bioaccessibility, equilibrium partitioning of desorbable compounds between sediment, water and organisms driven by activity, and toxicological bioavailability as a result of toxicokinetics including resorption, transport, metabolization and excretion. Bioaccessibility is based on desorption kinetics and can be simulated with mild extraction methods e.?g. using TENAX. Equilibrium partitioning can be simulated with partition-based dosing techniques. First results with these approaches indicate that consideration of bioavailability increases the significance of polar sediment-associated toxicants relative to classical non-polar contaminants such as polycyclic aromatic hydrocarbons.     

Screening zur Mobilisierbarkeit von Kupfer aus Böden und Schlämmen

In the presented paper, the pHstat-procedure is compared with four simple extraction procedures. These procedures make use of the following extraction solutions: distilled water (based on DIN 38414 part 4, DIN-S4), 1 mol/L ammonium nitrate, 1 mol/L ammonium acetate at pH 7.0 and 1 mol/L sodium acetate at pH 5.0, respectively. The extraction procedures were applied to 10 different soil samples and 2 sludges. The DIN-S4-procedure shows the lowest amounts of mobilized copper. The highest parts are extracted by sodium acetate solution. For the procedures investigated, the mobilized amounts extracted by ammonium acetate solution are most comparable with those of the pHstat-procedure. The simple sodium acetate procedure is useful for screening to select significant samples from a large number of soils. Thus, the high effort caused by the pHstat-procedure can be reduced to a minimum through the application of this screening procedure. The application of this screening, however, is difficult for samples containing large parts of organic compounds, e.g. sewage sludge. These samples show a different extracting behaviour.     

Beurteilung von Bodenkontaminationen mit Radioaktivität im Gebiet Hannover-List nach Maßstäben und Ansätzen der BBodSchV

Background, aim, and scope In Part 1 of this paper test thresholds for radionuclides in soil have been derived on the basis of methods and scales of the German Ordinance on Soil Protection (BBodSchV). In this paper, these test thresholds are checked with regard to their plausibility. Materials, methods, results are described in Part 1 of this paper. Discussion This contribution demonstrates that the test thresholds derived in Part 1 are plausible and feasible according to the requirements of the established methods. The epidemiological basis for the treatment of ionizing radiation is well founded. Risks can be quantified via the knowledge of cancer risks due to radiation. As a reference value the overall fatal risk coefficient of 5?% per Sv recommended by ICRP is used. The test thresholds obtained are sufficiently far from background levels in soils of northern Germany. Consequently, the test thresholds are applicable without any background corrections. Exposures by external radiation outdoors and exposures by inhalation of radon in cellar rooms result in calculated test thresholds in the order of background levels. Nevertheless, feasible results are obtained because in the case of toxic substances without threshold levels the additional exposures are considered for determination of test thresholds. Conclusions The approach of test thresholds for radioactive soil contamination presented in Part 1 of this paper complies with the criteria of the German methods for calculation of test thresholds in soil protection regarding plausibility and feasibility. It enables the soil protection authorities to assess radioactive contaminations of the ground according to the established rules in the field of soil protection and to make decisions according to Articles 9 and 10 of the German Soil Protection Act. Part 3 of this paper discusses the application of the test thresholds and the possibilities of determining the need for remediation actions.     

Beurteilung von Bodenkontaminationen mit Radioaktivität im Gebiet Hannover-List nach Maßstäben und Ansätzen der BBodSchV

Background, aim, and scope In the district List of Hanover (Lower Saxony) radioactive contaminations of the ground were detected at a site of a former chemical plant. Due to the lack of an ordinance regarding intervention regulations in the case of radioactive contaminations in Germany this situation had to be assessed on the basis of scales and methods of the German regulations concerning soil protection and contaminated sites. In particular it was necessary to develop methods and levels for the assessment of radioactive contaminations. Materials and methods Because radioactivity can be considered as a carcinogenic substance the methodical approaches of the BBodSchV for this group of substances were used in order to derive test thresholds for radioactive contaminations at children’s play areas, residential areas as well as parks and recreation facilities. Results For the assessment of radioactive soil contaminations with naturally occurring radionuclides at children’s play areas and residential areas the ingestion of soil is the decisive pathway of exposure. For children’s play areas a threshold level of 0.2?Bq/g for the sum U-238,max?+?Th-232,max was obtained. At areas with only impacts of ambient radiation from the contaminated ground test thresholds of 0.5?µSv/h are recommended. A special pathway is the migration of radon from the contaminated soil into basement floors of buildings. Taking into account the natural background levels of radon a concentration of 260?Bq/m³ is suggested as a test threshold in the framework of soil protection benchmarks. Discussion and conclusions will be described in Part 2 of the paper.     

Bestimmung von leicht freisetzbarem Cyanid in Böden und Wässern mit der Mikrodestillation

Easy-liberatable cyanide has to be analysed if soils and waters are contaminated by cyanide. The aim of this study was to determine easy-liberatable cyanide in these environmental samples using a micro-distillation apparatus by means of a modified digestion vessel. Pure aqueous solutions of different cyanide species, five contaminated and uncontaminated soil samples and two water samples were analysed by micro-distillation according to the German standards. Recovery was determined by analysis of spiked samples. When using the modified digestion vessels, the pH of 4 which is demanded by the standard method can be adjusted. The recovery of potassium cyanide and weakly-complexed zinc-cyanide ranged from 93–101% for standards, and from 87–98% for spiked samples. In contrast, the recovery of strong iron-cyanide complexes was below 4% both for pure solutions and spiked samples. The precision of the method expressed as a relative standard deviation was 25% in cases of very low easy-liberatable cyanide contents (< 1 mg CN kg^?1) and below 12% in case of high easy-liberatable cyanide contents (> 1 mg CN kg^?1) for contaminated soils. The determination of easily-liberatable cyanide in soils and waters using micro-distillation combined with the modified digestion sample is an alternative to other distillation methods.     

Cäsium-137 in Böden saarländischer Waldökosysteme

Scopes and main features

In order to explain the behaviour of the artificial radioisotope¹³⁷Cs towards landscape resources in the Saar-Lor-Lux-Region, the cross-border region between southwestern Germany/ Saarland, France/Lorraine and Luxembourg, regional distribution as well as downward translocation and depth functions of¹³⁷Cs in the main soil substrates of forest ecosystems in the Saarland were investigated.

Results

The study shows that the highest¹³⁷Cs activities are found in the north of the Saarland, whereas the south and south-eastern regions show distinctly lower concentrations of¹³⁷Cs. Migration rates range between 0.25 cm/a and 1.0 cm/a. On an average, the highest migration rates were found in the clayey-silty substrates of the lime stone areas in theMuschelkalk regions (Middle Triassic) (0.66 cm/a), followed by the loamy substrates of Lower Permian clastic sediments (Unterrotliegendes) (0.53 cm/a) and the sandy substrates of theBuntsandstein areas (Lower Triassic sandstone) (0.41 cm/a). 90 to 95% of the¹³⁷Cs activities in the clay-poor soils of the Unterrotliegendes and the Buntsandstein were traced in the upper 10 cm of the humus topsoil. The substrates of the lime stone areas (Muschelkalk), in contrast to this, reveal a¹³⁷Cs activity of only 70–76% at the same depth.

Conclusions

Due to the fact that the primary and secondary pores of the soil pore system, in their function as translocation pathways, decrease with increasing soil depth, a significant reduction in the migration rates of¹³⁷Cs can be expected with increasing soil depth. On the other hand, the maximal migration depth of 40 cm found in shallow soils on jointed parent material, as well as on sites with high groundwater tables, implies a possible contamination of near-surface groundwater.

Future outlook

Based on the results of this study, a permanent monitoring of¹³⁷Cs was added to the long-term Soil Monitoring Program run by the Federal Administrative Office of Environment of the Saarland (Landesamt für Umweltschutz des Saarlandes)     

Chlorcarbazole in Böden

Goal and Scope

In soil samples taken from several locations throughout Bavaria, the detection of p,p′-DDT by GC/MS was impeded by a superimposed peak. The authenticity of this compound, which has been identified as dichlorocarbazole by mass spectra databases, is confirmed and some characteristics of its occurrence in soils are described.

Methods

The authenticity of the unknown compound has been checked by comparing the low resolution mass spectra and chromatographic retention times with those of standard compounds. Some methodical studies concerning extraction and clean-up were also carried out.

Results and Conclusion

Mass spectra and retention of the unknown compound are identical with that of the 3,6-dichlorocarbazole standard compound; additionally, a second chlorocarbazole was found with mass spectrum and retention similar to 3-chlorocarbazole. In many topsoils (A-horizons) and subsoils (B-horizons) from 200 locations of different land-uses, the dichlorocarbazole could be detected. In contrast to PAH and other POPs, maximum concentrations occurred in the A- and upper B-horizons of forest soils rather than in the organic layers. Assuming the environmental distribution properties of the chlorocarbazoles to be similar to those of the PAH, this could indicate that the chlorocarbazoles are not deposited from the atmosphere as a result of anthropogenic activities but might be generated by natural processes in situ.

Recommendation and Perspective

To our knowledge, the occurrence of chlorocarbazoles in soils of unpolluted sites has not been previously described. Their widespread occurrence in relatively high concentrations and their detection using analytical standard procedures is surprising and requires further examination.     

Beurteilung von Gefahren aus militärischen Altlasten in Einzugsgebieten von Trinkwassergewinnungsanlagen auf der Basis eines Kriterienkataloges

To include consequences emanating from former military sites on the drinking water supply, a catalog of criteria has been developed which permits the determination and assessment of the hazards in general and their impact on human health in particular. The assessment criteria correspond to the special requirements and standards for drinking water hygiene and protection in Germany. The criterion catalog is a completion module to the usual praxis and existing conceptions, and has proved its practical value in the initial assessment of military sites in the new federal states of Germany. The scheme is a control instrument suitable for obtaining an assessment concerning the extent to which drinking-water resources are and will be affected by former waste disposal and other contaminated sites at the present and in the future.     

Konzentration und Verteilung von Platingruppenelementen (PGE) in Böden

In Germany automobile exhaust control by platinum-group element (PGE) loaded catalysts is now well established. By mechanical or chemical attrition, these catalysts could act as a potential source for a significant increase of PGE abundances in the environment. During a recent research program concentrations and distributions of PGE in different soils were measured along the highway A66 Frankfurt-Wiesbaden. 71 nearsurface soil samples were analysed by graphite furnace atomic absorption spectrometry (GFAAS). The results revealed average abundances of 10 ppb platinum and 3 ppb ruthenium. Palladium as well as rhodium were below the analytical detection limit of 2 ppb. With increasing distance from the highway edge PGE values gradually decreased. Only the upmost soil layer, down to 20 cm depth, contains measurable PGE concentrations. Results: There are irregular PGE concentrations of anthropogenic origin in different soils along the highway A66 Frankfurt-Wiesbaden possibly arising from automobile exhaust catalysts. Further monitoring could help to avoid potential environmental hazards. *** DIRECT SUPPORT *** A00HP020 00002     

Einschätzung der Konzentrationsprofile polyzyklischer aromatischer Kohlenwasserstoffe (PAK) in Böden des Biosphärenreservates Spreewald

To work out background values, the information of concentration profiles of PAHs in soils of uncontaminated territories is indispensable. This investigation shows PAH concentrations of different soil samples like agricultural soils, grassland, forest and litter from the biosphere reserve in Spreewald, Germany. The mean values of the soil samples are about 460 μg Σ-PAK/kg d.m. A top value of 7.2 mg Σ-PAK/kg d.m. shows a sample of a flooded grassland area. The relation of the concentrations in the litter, forest, grassland and agricultural soil samples is about 5∶3∶2∶1. Compared to the other samples, the litter samples contain a higher amount of low molecular PAHs. Increasing distance to the former power plants Lübbenau and Vetschau (brown coal) lead to decreasing PAH contents in the soil samples of forests from 2190.9 after 4 km to 294.8 Σ-PAK/kg d.m. after 16 km. In comparison to results obtained in Nordrhein-Westfalen and Bayern, the PAH measurements indicate Spreewald to be an uncontaminated and rural area.     

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.     

Bakterielle Mineralisierung von Dibenzofuran,Dibenzo-p-dioxin und 1,2,4,5-Tetrachlorbenzol in Böden

Quantitative degradation of dibenzofuran (DBF), dibenzo-p-dioxin (DBD), and 1,2,4,5-tetrachlorbenzene (TeCB) by the bacterial strains sphingomonas sp. HH 69, sphingomonas sp. RW1 and pseudomonas sp. PS 14 was investigated by radio-tracer techniques in liquid cultures and especially in samples of different soils. Pure strains converted DBF, DBD and TeCB up to 80% to CO₂ within few days. This degradation occurred not only in aerated liquid cultures but also in heterogeneous soils, with low levels of other pollutatns at favourable pH-values. Rate and degree of the mineralization of DBF, DBD and TeCB were independent of the DBF-, DBD-, or TeCB-concentration in the soils within a broad range. There was obviously a close correlation between the starting concentration of active cells (starting bacterial count) and the rate of degradation of the test substances in soil; by raising the starting bacterial count in the soil samples, mineralization of DBF, DBD, and TeCB, respectively, was clearly accelerated. However, under nearly the same coniditions in more acid soils (pH-values < 4) no significant degradation of DBF, DBD, and TeCB to CO₂ took place. As expected, this difficulty can be overcome by mixing CaCO₂ into the acid soils (liming). Easily utilizable substances like peptone, triolein, and glucose added as special carbon and energy sources to low contaminated soils, had only a small—if any—effect on the mineralization of DBF, DBD, and TeCB. In soils contaminated by a mixture of pollutants, the bacterial strains could develop their degradation capacity only to a limited extent and showed different degradation effects depending on the basic type of contamination. The efficiency of the degradation specialists was thus dependent on the “Chemical Environment” (type and concentration of contaminants present).     

Bestimmung von Mineralölkohlenwasserstoffen in Bodenproben mit Hilfe der Dünnschichtchromatographie

A thin-layer chromatographic method for the determination of mineral oil hydrocarbons (aliphatic compounds and naphtenes) of medium and low volatility in soil samples is presented which is based on their separation and quantitative determination. The extraction of the soil samples is effected by means of an n-hexane-acetone mixture (10∶1) supported by ultrasonics. The evaluation can be made visually or densitometrically by means of a thin-layer scanner. The applicability and restrictions of the method are shown. The advantage of the method lies in its low requirements pertaining to apparatus and chemicals, as well as in its rapidness which makes it suitable for quick in-situ analyses as, for example, for the assessment of the mineral oil content of a contaminated site.     

Analyse „stetigkeitsbasierter“ Methoden zur Bestimmung von Stofffrachten in Fließgewässern

Aim and background

Increasing ecological awareness puts the load as a tool for water quality assessment in the foreground. Therefore it is very desirable to find optimal procedures for any given situation on basis of existing data. Criteria will be derived to fill that desire.

Method

The load for a water ingredient is an integrated entity of time-continuous loads (product of concentration and flow) for a given time, i.?e. a year (yearly load). Normally you can only observe a sample (in a statistical meaning) of these data. Therefore, load calculations vary with the concrete sample given. Each such calculation represents an estimation of the load, afflicted with some uncertainty. This uncertainty can be quantified, at least approximatively, by adding variance (scatter around “expected” mean) and the square of bias (divergence of “expected” mean from true mean). This quantity is called “mean squared error”. The methodological results will be illustrated by examples.

Focus

The main focus lies on the methodologies, which, besides data of concentrations observed discretely in time, additionally use quasi-continuously recorded data of other variates, namely the flow. For that situation, statistical models are developed and the load derived and estimated according to existing data. Hereby it is seen that all model based estimation formulae can be described as standard sampling formulae plus some additional terms which stem from comparison of some measurements (i.?e. mean) for quasi-continuous and discrete samples. This way a “continuity-correction” is performed on the standard formulae for the sampling case. This method is called “continuity-based” load determination.

Results

A surprising result is that no complicated mathematical-statistical models are necessary to determine the load. A simple linear concentration- or load-flow-model is sufficient. Additional variates lead, most of the time, to a larger mean squared error in load estimation, even when it is well known that they cannot detoriate the model fit. Only models which describe the concentration extraordinarily precise, near perfection, result in a smaller error.

Implications

It is enough to use one of the given formulae with some “continuity correction” to calculate a load. That can be done without using any software.