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.     

Insektizide in Fließgewässern

In streams with an agricultural source of catchment, insecticide contamination and hydrodynamic stress increased with the rate of surface runoff. In this investigation, surface runoff was responsible for an insecticide contamination of the water of up to 6 μg/lParathion and of suspended particles of up to 302 μg/kgFenvalerate. Surface runoff also induced an increase of discharge up to one order of magnitude over one day. As a consequence, the number of macroinvertebrate species was discreased by 73% and the species composition was modified. Laboratory and field investigations pointed out that insecticide contamination is the most relevant cause of these observed biological changes. This work describes the population dynamics of a sensitive species and, in addition, the strategies of survival of a tolerant species.     

Huminstoffe in Sedimentporenwässern ausgewählter Bundeswasserstraßen

Humic substances are an important component of organic carbon in natural waters. Their character and properties are determined by the sources and the processes of their origin. Humic substances are not exclusively refractory compounds, but they are involved in several transformation processes in the water. It is not possible to directly analyze humic substances, therefore several methods were applied for their characterization. The presented LC-OCD-technique is a size-exclusion-chromatography with online UV- and carbon detection. Carbon fractions, e.?g. humic substances were differentiated by their molecular size. The portion of humic substances in sediment porewaters of the rivers Elbe, Rhine, Danube, Oder, Müritz-Elde-Waterway was determined. With only a few exceptions it ranges from 50 to 67?% of the dissolved organic carbon. The high molecular weight fraction accounts for 10 to 34?%, and the fraction of the low molecular weight substances was from 7 to 37?%. The ratio between the spectral absorption coefficient (254?nm) and the organic carbon is called SUVA (L/mg × m) and is an inidicator of the proportion of unsaturated bonds in the humic substances. Both high molecular herbal components (e.?g. cellulose, lignin) and biological degradiation products (e.?g. amino acids, sugar) are involved in sediment porewater transformation and degradiation processes. This demonstrates the distribution of the dissolved organic carbon between the fractions.     

Pharmazeutisch aktive Substanzen in kleinen Fließgewässern

Background

Current hydrological research is increasingly focusing on pharmaceutically active compounds (PhACs). Concerning the issue of quality of drinking water, this problem has also become the focus of public interest. However, in spire of the fact that the fate of chemicals in surface waters has been assessed in great detail, the influence of groundwater-exchange is yet only little known.

Goal

This study gives emphasis to the question of how transport and degradation of PhACs interact with the exchange of surface water with groundwater. Special interest is given to alternating groundwater regimes.

Methods

Based on a small stream system in the north of Berlin, Germany, a one-dimensional compartment-model was established using differential mass-balance. The stream which, at its mouth, discharges 0.3 m³ s^?1 is already well investigated and thus provides a good empirical data basis. The processes taken into account by the model were ‘exchange of surface-water with groundwater’, ‘decomposition’ as well as ‘transport’ of PhACs. Calculations were performed using the commonly used analgesic Diclofenac as an example and defining 81 scenarios by different groundwater regimes. Hasse Diagramm Technique was used to compare the scenarios.

Results

All scenarios show a big influence of groundwater-exchange to the fate and concentration of PhACs in surface waters. In the case of the modelled stream system, dilution by groundwater was more responsible for a decrease in concentration than degradation was. Furthermore, on the background of a standard scenario, the loss due to groundwater by 5.4 percent was in the same magnitude as the loss due to decomposition (9.7 percent). A crucial difference between punctual versus linear afflux of groundwater has not been observed.

Discussion

The alteration of discharge resulted in a big influence of the case differentiation between ‘constant velocity’ and ‘constant cross-section’. Furthermore, the model was based on the assumption that groundwater was unloaded with PhACs or diluted very well in comparison to the stream. In contrast, regarding measurements in the catchment, groundwater could even be a diffuse source of the contamination of the stream.

Conclusions

The fate of PhACs in our model is crucially driven by interactions with groundwater. Therefore, assessing the risk emanating from substances like Diclofenac, it is very important to regard their accessibility to decomposition as well as the morphology of the stream-system and its interactions with the groundwater.

Perspectives

In this model, the process of transport from the surface to groundwater back to the surface was dealt with insufficiently; in order to be able to observe fully developed interaction in a further step of modelling, a groundwater-transportmodel should be coupled completely with a surface-water-model.     

Abschätzung des Beitrages kommunaler Kläranlagen an Schadstoffkonzentrationen in Oberflächengewässern

A number of products, such as washing agents or pharmaceuticals, enter the hydrosphere mainly with municipal wastewater. In this case the predicted environmental concentrations (PEC) of substances are largely determined by their elimination in municipal wastewater treatment plants and by the dilution ratio of wastewater in the rivers. In this article some rough estimates of the wastewater ratio in German rivers are presented and as a starting point for a more complex model for calculating the PEC more exactly, data on the fluctuation of river flow rates are shown.     

GIS-basierte Modellierung von Gewässerimmissionen

Goal and Scope

Environmental assessment of aquatic micro pollutants should consider the spatial and temporal variability of emission, transport and transformation. Simulation models coupled with Geographic Information Systems (GIS) provide digital maps of concentration patterns caused by the overlay of multipoint and diffuse emissions and natural attenuation processes in river basins. The paper gives an overview on GIS-based models for river basins and demonstrates the applicability by using some illustrating examples with GREAT-ER.

Main Features

Georeferenced models have several advantages: visualization of concentration patterns, investigation of spatial and temporal concentration profiles, analysis of exceedance of environmental quality standards, embedding in integrated river basin management systems.

Results and Discussion

GIS-based models allow a more realistic assessment. Monitoring programmes should be designed to deliver appropriate measured data for the evaluation and improvement of models.

Recommendation and Perspectives

The combination of digital maps, simulation models and environmental monitoring would provide better approaches for the risk assessment and water quality management of aquatic micro pollutants.     

Abschätzung der Einträge von polyzyklischen aromatischen Kohlenwasserstoffen in deutsche Gewässer

Background, aim, and scope Polycyclic aromatic hydrocarbons (PAH) result from incomplete combustion of almost every organic materials, e.?g. due to forest fires, residential heating, combustion engines, grilling, or smoking. PAH are predominantly distributed over the air-path. Their usage in products (e.?g. moth-balls) has been limited strictly or completely forbidden in the past. In the context of the EU Water Framework Directive (WFD), the single substances anthracene, fluoranthene and naphthalene, as well as PAHs as group of substances, are listed as “priority” substances. Background of this work is a first compilation of sources of PAH emissions, and in this context, the collection of all relevant data and information to calculate the total emissions into surface waters in Germany. Materials and methods Within the scope of diverse research projects, funded by the German Environmental Agency, the available data material concerning PAH input in surface waters has been analyzed by the Fraunhofer Institute for Systems and Innovation Research. On the basis of the collected data, a first evaluation of relevance of the different sources has been conducted using the model MONERIS. Results As a result of the atmospheric deposition, PAHs enter, to a large extent, surface waters directly or indirectly through surface runoff (e.?g. urban areas, wastewater treatment plants, erosion). Discussion Although there is still additional research need for some of the covered PAH sources, a noticeable distribution pattern of relevance emerges. Conclusions The scenarios, based on the currently known sources, show that the implementation or the neglect of emission reduction measures in the field of diffuse air-borne PAHs are crucial for the further development of the deposition of PAHs in surface waters. More far-reaching studies are necessary, e.?g. concerning emissions from inland navigation/motor boats, the inhomogeneous source “products”, or the path “erosion”. Recommendations and perspectives According to the EU-WFD, all depositions, emissions and losses of “priority hazardous” classified substances, such as the group of PAHs, have to be stopped or gradually finished in the long term. Until the year 2015, environmental quality standards (EQS) have to be met for all “priority substances”. Presently, the EQS often are not completely fulfilled for many substances of the PAH group, including benzo(a)pyrene. Reduction measures are necessary within diverse areas, especially concerning diffuse atmospheric emissions (e.?g. “residential heating”).     

Verteilung und Abnahme von bodennahem Ozon in städtischen und ländlichen Regionen

The compilation of ozone data for the federal states of Hesse and Northrhine-Westphalia (NRW) in Germany indicated that the concentration of ozone level slightly decreased during the years 1990–1998. The average concentration of ozone over forest areas is significantly higher than over cities. Only the maximum figures in the years approached one another. However, values passing the legal thresholds (180 μg ozone/m³) were two to three-fold higher over forests than over cities. The ozone concentration in air is inversely proportional to the traffic density. It is suggested that the lower NOx concentration over the forest than over cities is involved in the maintenance of the higher ozone-concentration over forest areas. In the cities, the ozone is reduced by NO to almost zero at night, whereas it is reduced by only about 50% over forests with lower NO concentrations. This reduction is only partially compensated in connection with the photolysis of NO₂ and the subsequent oxidation of O₂ to O₃ during the day. The ozone situation is principally the same in the federal states of Hesse and Northrhine-Westphalia.     

Detektoren zur Kartierung des Redox-chemischen Gewässermilieus

For the time being, simple and reliable methods which permit the imaging of the complex topography of contaminant plumes in groundwater are missing. The conventional methods for the punctual determination of contaminant concentrations cannot fulfill this demand. To successfully implement and utilize. Natural Attenuation, these deficits have to be overwhelmed. The detectors described in the following represent only part of the probing device system the authors have developed; it shall enable their user to image different aspects of plume topography and its time dependent change by monitoring within the undisturbed groundwater aquifer in groundwater measuring levels:

? relative freights of contaminants and trace contaminants by passive samplers [4] and

? redox milieu parameters by detectors.

The detectors offer multi-purpose, tape-like probing devices of unlimited length. They are charged with a defined reserve of reactive substances. During monitoring actions, the derector tape hangs vertically stretched by a weight preferably covering from the top to the bottom of the whole water column. During the reaction period, the detector may be relaunched for repeated visual inspection. The colour changes of the detectors enable the identification of a row of parameters in the vertically (depth-) oriented profile by unbroken optical/visually perceivable imaging:

? Position of Redox potential thresholds for Mn-IV-Mn-II, Fe-III-Fe-II, Sulfate-Sulfide

? Position of ochre precipitation and iron-sulfide precipitation horizons

? Relative freights of the sum of substances effecting reduction (period until defined oxidant reserve has been reduced)

? Relative freights of the sum of substances effecting iron-sulfide oxidation (period until defined reductant reserve has been reduced)

? Position of dissolved iron-II ions containing horizons

? Position of dissolved hydrogen-sulfide ions/hydrogen-sulfide containing horizons

? Relative freights of iron-II ions (period until defined oxidant reserve has been reduced)

? Relative freights of hydrogen-sulfide ions/hydrogen-sulfide (period until defined oxidant reserve has been reduced). Furthermore, the detectors are also suitable for the examination of waters even of great depth, as for example artificial or natural lakes, sea and ocean basins.

     

Biozide in Gebäudefassaden – ökotoxikologische Effekte, Auswaschung und Belastungsabschätzung für Gewässer

Background, aim and scope Sources of organic micropollutants occuring in surface waters are often unknown. Regarding environmental risk assessments for surface waters, construction materials have as till now, not been given much consideration, although biocides used as preservatives are known to reach urban storm water runoff. The study focused on biocides for facades coatings and aimed (1) to determine ecotoxicological effect values, (2) to quantify the leaching behaviour and (3) to assess the environmental risk for surface waters using a dynamic transport model. Materials and methods Eight biocides used in resin based facade coatings were investigated. Some biocides are substances known as pesticides for agricultural purposes like diuron, carbendazim and terbutryn. Ecotoxicological effect values for aquatic organisms were determined for every biocide. Leaching of four biocides from a render under UV-irradiation has been investigated in the laboratory including the influence of varying temperatures. Using 80 irrigation intervals over 28 days, facade runoff was sampled and followed by biocide chemical analysis. The total losses were calculated based on the concentration patterns. These data were used for modelling the transport of cybutryn from facades to surface waters. Biocide specific effect values and leaching characteristics have been taken into consideration. Results Acute and chronic effect values as well as predicted no effect concentrations for the investigated biocides indicate their high potential to affect aquatic organisms. The leaching of four biocides (diuron, terbutryn, cybutryn, carbendazim) from the facade render under the experimental conditions delivers high concentrations in the beginning followed by an exponential decrease. Rising temperature increased the concentration of biocides in the runoff. The total losses were between 7?% and 29?% depending on the substances. More than half of the losses occur in the runoff within the first 15 min of runoff from a 60 min irrigation cycle. The modelling result for cybutryn underlines its high environmental risk for small surface waters. Discussion The leaching of the biocides, their potential ecotoxic effects and persistence show clearly that the environmental risk for surface waters and soils seems to be high for certain biocides; whereas for others the risk seems to be significantly lower. With respect water quality criteria, polluted facades runoff has to be diluted before runoff can enter the discharge. Diuron and carbendazim are however also used as pesticides and preservatives for other materials and cybutryn is also used as an antifouling agent. All pathways have to be evaluated in order to identify relevant sources and to act more efficiently with respect to water and soil protection. Conclusions Concentrations with high environmental risk are expected at new facades, especially at facades with thermal insulation. With the given low predicted no effect concentrations in a range of a few ng/L and large amounts of biocides applied in paints and renders, the environmental risk for common biocides used in facade coatings has to be investigated in laboratory and field scale. It seems plausible that source control measures as the most efficient and sustainable precautionary principle need to be evaluated. Recommendations and perspectives Biocides and additives applied in construction materials have to be taken into consideration as relevant sources when evaluating the quality of storm water runoff, discharge into urban areas and the impact to soil and surface waters. A sustainable construction material management and storm water management are required. It is expected that ongoing laboratory and field studies with exterior paints, renders and flat sheets for waterproofing containing biocides and additives will give further insight into their environmental impact.     

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.     

Medikamentenentsorgung in privaten Haushalten: Ein Faktor bei der Gewässerbelastung mit Arzneimittelwirkstoffen?

Background

Residues of pharmaceuticals are meanwhile detected widely in the aquatic environment. Waste water treatment plants are the main route of entry: after intake the agents or their metabolites are excreted predominantly via urine into the sewage. Largely unknown is, however, if the improper disposal of unused medicines via domestic sanitary devices (toilet or sink) contributes to the measured concentrations in the environment. Aim of this investigation was to clarify to what extent consumers in Germany dispose of unused medicines directly via domestic sewage. In July and August 2006 a representative survey of the population with 2.000 interviewees was performed for this purpose.

Results

The analysis of the survey shows that the disposal of unused medicines via domestic sewage takes place on relevant scales: approx. 16% of the population dispose at least occasionally of unused or expired tablets in the toilet whereas 43% proceed alike with liquid drugs (toilet or sink).

Discussion

A possible reason for this disposal behaviour is the widely inconsistent waste disposal communication by the municipalities and the federal states. The resulting uncertainty about the correct way to dispose of unused medicines gains in importance in the context of the high recycling willingness of the (German) population: appropriate disposal options for drug residues (tablets or liquids) arising from waste separation are often not realised.

Conclusions

Quantitative assessments on the basis of the collected data demonstrate that the established frequency of direct disposal of unused medicines via domestic sewage can partly contribute significantly to the occurrence of pharmaceuticals in the aquatic environment. Crucial parameters are here the excretion rate of the active pharmaceutical ingredient considered and the actual amount of medication waste.

Recommendations

Based on the inquiry results, measures that lead to a more adequate handling of pharmaceutical waste disposal are demanded. The establishment of a consistent and binding disposal standard for unused medicines via return in pharmacies is recommended. This measure needs to be accompanied by a simplification of the established take back systems which partly cause high time and effort for pharmacies.     

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.     

Mikrobiologische Volatilisierung von anorganischem Selen aus Deponiesickerwässern bei umweltrelevanten Konzentrationen

Background, aim, and scope Determination of the rates of microbial alkylation are of interest with respect to natural attenuation of harmful selenium concentrations or selenium charges in contaminated ecosystems. Materials and methods Landfill gas and the headspace of microbial microcosm incubation vessels were sampled in Tedlar^® bags. On-line hyphenation of an efficient enrichment method (cryotrapping-cryofocusing), a gaschromatographic separation technique, and the sensitive ICP-MS detection system was used for speciation of volatile organoselenium compounds. A detection limit at the ultra trace level (pg Se) was achieved with this CT-CF-GC-ICP-MS technique. Results Incubation of landfill leachate with Alternata alternata as an active methylating organism showed a production of volatile selenium compounds (DMSe, DMDSe, EMDSe, DEDSe) over the whole range of applied inorganic selenium concentrations (10?µg?L^–1 to 10?mg?L^–1), with volatilization rates of up to 10?mg m^–3?d^–1. For selenium concentrations of 1?mg?L^–1 in the nutrient broth, up to 7?% of the inorganic selenium was volatilized after one week. The same volatile selenium compounds were observed in landfill gas. Discussion The amount of volatilized selenium was comparable to that found in other studies with microbial pure cultures as well as isolates from waters or soils, but at much lower initial concentrations used in the incubations. Conclusions The alkylation of selenium in the enriched mixed culture from landfill leachate at environmentally relevant concentrations indicates that the organoselenium compounds of same species composition and distribution determined in landfill gas are produced by microorganisms. Recommendations and perspectives The microbial alkylation of toxic inorganic selenium species to less toxic or non-toxic, volatile compounds is an efficient method for bioremediation of contaminated sites even at relatively low Se concentrations.