Pestizide in Oberflächenwässern — Befunde in Talsperren und in Uferfiltraten Pesticides in Surface Water — Analytical Results for Drinking Water Reservoirs and Bank Filtrate Waters

The results of a series of investigations are presented, performed by the governmental chemical laboratory Karlsruhe (CLUA) in order to determine pesticides in drinking water for purposes of food monitoring. 231 samples of 8 municipal water supplies (groundwater wells/no bank filtrate) and 34 private water supplies close to the bank of the river Rhine (groundwater wells/partly bank filtrate) were analysed. The sampling sites were located between Mannheim and Greffern, Germany. In 1986 high amounts of atrazine and simazine were determined in the drinking water wells of several private water supplies, especially at the sampling sites in the south. The likewise high chloride content of the samples was taken as a proof of bank filtrate contributing to the water. The decrease of atrazine load in the river water of the Rhine since 1987 has its parallel in the analytical results for the concerned drinking water wells. Obviously the pesticide contamination of water from bank filtrate pumping wells is mainly depending on the pesticide load of the river water. The application of fertilizers and pesticides in the fields seems not to be a significant source of the pesticide contamination of dringing waters derived from bank filtrate water. For reasons of public health a monitoring of pesticide content in bank filtrate pumping wells of private water supplies is recommended.     

Chemische Gewässerverunreinigung und Wassernutzung

Pollution by chemicals of natural water resources frequently impairs production of drinking water. Enrichment by refractory dissolved organic compounds is the main reason as can be easily observed in the river Rhine. Characterization of pollution is possible by analysis of individual compounds and by the ratios of parameters such as DOC, COD and UV-extinction. Experience shows that future water pollution control technology has to include physical-chemical processes for the elimination of refractory substances.      

International co-operation on Rhine water quality 1945-2008: An example to follow?

The management of the Rhine is often seen as an exemplary case of international river basin management. In the Rhine basin, countries that went to war with each other twice in the last century have managed to reach agreements on many issues and water quality has improved considerably. The improvement in water quality is often attributed to the activities of the International Commission for the Protection of the Rhine and in particular to its Rhine Action Plan. In order to test this assertion, this paper describes and analyzes the development of international co-operation on the water quality of the Rhine since 1945. It concludes that water quality improvement cannot be attributed to any single factor. Instead, a whole array of interrelated factors are at play, including the European Union, other international fora such as the North Sea Ministerial Conferences, domestic legislation, the activities of environmental NGOs and waterworks, growing environmental awareness, and the changing structure of the industry in the basin. Because of the importance of contextual factors, the Rhine experiences cannot simply be applied to basins with a different context. In many cases, international river basin management may be promoted most effectively by promoting co-operation at the river basin level. In many other cases, however, it may be more effective to identify and then work on the contextual factors that (1) have the biggest leverage effect in the specific case and (2) can be influenced most effectively.     

Does upward seepage of river water and storm water runoff determine water quality of urban drainage systems in lowland areas? A case study for the Rhine–Meuse delta

The water quality of urban drainage ditches in lowlands in the Rhine‐Meuse delta was analysed with principal component analysis (PCA) during a dry period and a rain storm, and related to the seepage of polluted river water and effective impervious area (EIA). This was done in order to test the hypothesis that seepage of river water and storm water runoff from impervious areas strongly determine the water quality of urban drainage systems along large lowland rivers. Our analysis revealed that upward seepage of groundwater originating from rivers Rhine and Meuse was positively correlated with nitrate, potassium, sodium and chloride and negatively correlated with alkalinity, calcium, magnesium and iron. EIA was correlated with very few environmental variables (i.e. phosphate, pH and iron in the dry period and iron during the rain storm). Nickel and zinc concentrations generally exceeded the maximum allowable concentrations (MAC), while lead and phosphorus concentrations were just above the nutrient standards and MAC in a few locations during the rain storm. To optimize water quality in urban water systems, attention should be paid to all sources of pollution and not only to EIA. The impact of local groundwater seepage originating from large rivers in lowlands on the chemistry of urban water systems is often underestimated and should be taken into account when assessing water quality and improving water quality status. Copyright © 2009 John Wiley & Sons, Ltd.     

Auswertung langzeitlicher Meßreihen zur aeroben Abbauleistung der Uferpassage einer Wassergewinnungsanlage am Niederrhein

Evaluation of Long-term Measurements Concerning the Aerobic Degradation Performance of the Subsoil Passage of a Water Catchment at the Lower Rhine The magnitude of the biodegradation of organics during bank filtration was investigated and exemplary quantified at a drinking water catchment in the lower river Rhine area. The catchment is situated at an undercut slope where the Rhine has a steady flow. The observed segment of the quarternary aquifer was free of iron and manganese and showed even under anaerobic conditions no heterotrophic denitrification. This facilitated the assignment and the balance of oxygen consumption and the determination of inorganic carbon due to the metabolic activity of heterotrophic organisms. In particular the progressive curve of the base neutralization capacity up to pH 8.2 of the bank filtered water proved to be a good measure for the biological activity in the river bottom. In the months from summer to autumn there was an increased biological activity. The observed oxygen consumptions could be attributed to the biodegradation of dissolved organic matter by 35 to 45% only. Obviously the particulate organic matter after the rise in temperature during summer takes part in a substantial manner considered little until now. Today the Rhine is regarded as a largely rehabilitated river with respect to oxygen consuming pollutions. The observations demonstrate, that in such flowing waters the particulate organic matter, which should mainly consist of withered organisms, may have a dominant influence on the concentration of oxygen in the bank-filtered water in summertimes.     

Modelling water fluxes for the analysis of diffuse pollution at the river basin scale

Diffuse pollution is a significant and sometimes even major component of surface water pollution. Diffuse inputs of pollutants to the surface water are related to runoff of precipitation. This means that the analysis of diffuse pollutant fluxes from the land surface to the surface water requires an analysis of water fluxes. In this paper we have modelled the average long‐term total runoff, groundwater recharge index and groundwater residence times for two large European river basins (Rhine and Elbe). We applied and compared two independently developed and recently published methods. We found that with the available large‐scale databases and methods we could simulate successfully the regional patterns of the average long‐term total runoff. The reported groundwater recharge indices and groundwater residence times should be interpreted as estimates based on available knowledge and databases. They do not represent absolute values, but illustrate the possible travel times and spatial patterns of the different runoff components that have to be taken into account for the analysis of diffuse pollution at large regional and temporal scales. Copyright © 2000 John Wiley & Sons, Ltd.     

一种水污染的综合控制模型

本文将水质预测及水污染控制措施有机地结合,选取水环境容量和污染指数作为水污染控制的参数,这样,一给对流－扩散水质方程的求解除就是实现本研究目的的关键,本研究彩和的模型在现有的水质模型基础上有所改进,因为其采用四点隐格式对水质进行预测,推求可接给污染物的环境容量值有为保证水质而陷定的污染物浓度值,从而制定相应的水污染控制措施,为整体考虑各种污染物的情况,建议彩和河流的污染指数进而推求综合污染指数,总之,本研究为水质保护提供了科学的计算方法,该法对水污染及污水对河道水质的影响是实用有效的。     

Untersuchungsergebnisse zu waschmittelrelevanten Inhaltsstoffen in ostdeutschen Fließgewässern

Results of Investigations of Substances Deriving from Detergents in Eastern German Rivers Based on detergent related parameters like surfactants, phosphate, and boron as well as general pollution parameters like TOC, DOC, COD and O₂, a differentiated picture of the loading situation of the most important rivers in Eastern Germany is drawn. In comparison with investigations previously carried out in the GDR, the development of the surface water pollution will be demonstrated, and it can be shown that a significant improvement of the water quality has taken place. Comparisons between the loads of the river Rhine and those found in East German rivers show clear differences that are obviously due to different populations in the river catchment areas as well as to different hydrographical conditions. Increased surfactant and boron concentrations can be found especially in smaller Eastern German rivers with relatively great catchment areas. The introduction of phosphate replacements in detergents in 1990 led to a drastic reduction of the phosphate concentrations in most Eastern German rivers.     

Importance sampling for efficient modelling of hydraulic loads in the Rhine–Meuse delta

During flood events, breaching of flood defences along a river system can have a significant reducing effect on downstream water levels and flood risks. This paper presents a Monte Carlo based flood risk framework for policy decision making, which takes this retention effect into account. The framework is developed to estimate societal flood risk in terms of potential numbers of fatalities and associated probabilities. It is tested on the Rhine–Meuse delta system in the Netherlands, where floods can be caused by high flows in the Rhine and Meuse rivers and/or high sea water levels in the North Sea. Importance sampling is applied in the Monte Carlo procedure to increase computational efficiency of the flood risk computations. This paper focuses on the development and testing of efficient importance sampling strategies for the framework. The development of an efficient importance sampling strategy for river deltas is more challenging than for non-tidal rivers where only discharges are relevant, because the relative influence of river discharge and sea water level on flood levels differs from location to location. As a consequence, sampling methods that are efficient and accurate for one location may be inefficient for other locations or, worse, may introduce errors in computed design water levels. Nevertheless, in the case study described in this paper the required simulation time was reduced by a factor 100 after the introduction of an efficient importance sampling method in the Monte Carlo framework, while at the same time the accuracy of the Monte Carlo estimates were improved.     

Biologische Untersuchung der Limmat zwischen Zürichsee und Wettingen, 1974 bis 1980

Biological investigations of that part of the River Limmat lying between Quaibrücke and Wettingen were carried out from 1974 to 1980. An influence of the waste water from the Werdhölzli sewage treatment plant on the plant and animal communities of the river bed was evident. This influence was especially plain to be seen immediately below the point of introduction of the waste water. The incidence of pollution indicators decreased downriver from this point. Biotests, using periphyton from stones taken from the shore of the Zürichsee, yielded harvests which were clearly higher in Limmat water taken from points downstream from the sewage works than in water taken from points upstream.     

Sensitivity of the river Rhine discharge to environmental change,a first tentative assessment

Changes in climatic conditions may have great impact on the distribution of available water in space and time. However the results of models that describe future climate conditions are still insufficient to be used in regional hydrological simulation studies. This article describes a first tentative estimation of the sensitivity of discharge of the river Rhine to two environmental changes. Firstly, to a change in snow covered area due to a rise of 4°C in winter temperature in the upland part (Alps) of the drainage area and, secondly, to a large land use change in the lowland area (Federal Republic of Germany/France). ‘Worst case’ scenarios for discharge of the river Rhine under warmer conditions give a reduction of 10 percent for the summer discharge at Rees (Dutch/German border). The results of the estimations indicate that the reduction of the summer discharge in a warmer world could be larger.     

Biogene und nichtbiogene organische Schmutzstoffe

Analytical methods and their application on the river Rhine for the identification and determination of refractory organic compounds are reported. 18 hydrocarbons, 32 chlorinated hydrocarbons, 13 organic nitro compounds, 14 ethers, 4 alcohols, 9 phenols, 6 esters and 21 other organic compounds have been identified. In view of the tedious methods which have to be applied, a technique for determining the ratio of persistent to biodegradable organic compounds has to be found. Requirements and perspectives of microbiological assays are discussed and rules for the survey of waste discharges are proposed.     

Effects of the Black River (Cape,South Africa) on the distribution and survival of marine psammofauna

The physicochemistry of the Black River and adjacent marine beach, in terms of tidal, daily and seasonal fluctuations of temperature and salinity, presents a highly stressed environment exacerbated by canalization of the river mouth. Riverine pollution further stresses this environment, producing low densities and diversities of marine infauna adjacent to the river. No fauna were found in the river mouth where typical estuarine conditions exist only during high tide. Tolerance of the dominant marine species, Cerebratulus fuscus, to temperature, salinity and river water combinations showed that mortality was more rapid after exposure to river water dilutions than after exposure to distilled water dilutions. Computer-generated models suggested that this species should survive conditions closer to the river than were observed. This confirmed additional stress due to pollution carried in the river from urban and industrial drainage. Lower river water temperatures during winter appear to ameliorate pollution stress, enhancing survivability of the infauna.     

Parameter identification in particle models

For the simulation of the transport of dissolved matter particle models can be used. In this paper a technique is developed for the identification of uncertain parameters in these models. This model calibration is formulated as an optimization problem and is solved with a gradient based algorithm. Here adjoint particle tracks are used for the calculation of the gradient of the cost function. The performance of the calibration method is illustrated by simulations and an application to a river Rhine water quality calamity in November 1986.     

Parameter identification in particle models

For the simulation of the transport of dissolved matter particle models can be used. In this paper a technique is developed for the identification of uncertain parameters in these models. This model calibration is formulated as an optimization problem and is solved with a gradient based algorithm. Here adjoint particle tracks are used for the calculation of the gradient of the cost function. The performance of the calibration method is illustrated by simulations and an application to a river Rhine water quality calamity in November 1986.     

Heavy metal transport in large river systems: heavy metal emissions and loads in the Rhine and Elbe river basins

Pollutant transport and management in the Rhine and Elbe basins is still of international concern, since certain target levels set by the international committees for protection of both rivers have not been reached. The analysis of the chain of emissions of point and diffuse sources to river loads will provide policy makers with a tool for effective management of river basins. The analysis of large river basins such as the Elbe and Rhine requires information on the spatial and temporal characteristics of both emissions and physical information of the entire river basin. In this paper, an analysis has been made of heavy metal emissions from various point and diffuse sources in the Rhine and Elbe drainage areas. Different point and diffuse pathways are considered in the model, such as inputs from industry, wastewater treatment plants, urban areas, erosion, groundwater, atmospheric deposition, tile drainage, and runoff. In most cases the measured heavy metal loads at monitoring stations are lower than the sum of the heavy metal emissions. This behaviour in large river systems can largely be explained by retention processes (e.g. sedimentation) and is dependent on the specific runoff of a catchment. Independent of the method used to estimate emissions, the source apportionment analysis of observed loads was used to determine the share of point and diffuse sources in the heavy metal load at a monitoring station by establishing a discharge dependency. The results from both the emission analysis and the source apportionment analysis of observed loads were compared and gave similar results. Between 51% (for Hg) and 74% (for Pb) of the total transport in the Elbe basin is supplied by inputs from diffuse sources. In the Rhine basin diffuse source inputs dominate the total transport and deliver more than 70% of the total transport. The diffuse hydrological pathways with the highest share are erosion and urban areas. Copyright © 2002 John Wiley & Sons, Ltd.     

Copper,zinc, cadmium,nickel, iron and manganese in the Southern Bight of the North Sea

Ni, Cd, Cu, Zn, and Fe were determined in water and suspended matter samples and Mn in suspended matter samples from the Southern Bight region of the North Sea. Four distinct areas, comprising the Rhine estuary, the Dutch coastal waters, the centre of the Bight, and the English coastal water can be distinguished on the basis of the distribution of the trace metals. The total concentrations of all metals were high in the Rhine estuary, decreased in a seaward direction to reach very low values, comparable to continental shelf water, in the centre of the Bight, and increased again towards the English coast. Elevated concentrations of dissolved Cu, Ni, Cd and Zn near the English coast are not only due to river inputs. Over the entire region, the fraction of Cd, Ni and Zn in solution was consistently more important than the fraction in the suspended particulate phase. In contast, the fraction of Fe and Mn in the solid phase was consistently greater than the fraction in solution. Total concentrations of Fe, Mn and Cu are more dictated by the suspended particulate matter concentration than Cd, Ni and Zn.     

Nachweis von Industriechemikalien (HPS,BPS und SPS) im Oberflächenwasser

Occurrence of Industrial Chemicals (HPS, BPS, and SPS) in Surface Water The paper gives the results of water examinations for different phenylsulfonamides. Random samples taken every month between May 1999 and August 2000 from surface water out of the river Rhine (kilometer 838), the river Ruhr (Mülheim Styrum) and the river Emscher (Oberhausen center) were tested for the corrosion inhibiting agent 6‐[methyl(phenylsulfonyl)amino]‐hexanoic acid (HPS) as well as its metabolites 4‐[methyl‐(phenylsulfonyl)amino]‐butanoic acid (BPS) and sarkosin‐N‐(phenylsulfonyl) (SPS). Furthermore, the sewage plant effluents of two municipal wastewater treatment plants from the rural area were also included in the monitoring program. The analytical method includes solid‐phase extraction (SPE), a derivatization step as well as gas chromatography mass spectrometry (GC‐MS). SPS is regularly found in all investigated surface waters, but only occasionally in the effluents of the two rural sewage plants. The median values for SPS amount to 0.09 μg/L in the river Rhine, 0.60 μg/L in the river Ruhr, and 0.70 μg/L in the river Emscher. BPS can only be found in the river Ruhr (median value: 0.08 μg/L) and in the river Emscher (median value: 0.41 μg/L). HPS was regularly found in a surface water for the first time. This substance can be detected in the Emscher through the whole measurement period. The median value for HPS amounts to 1.78 μg/L. Aditionally, the validation characteristics of an alternative analytical method including solid‐phase microextraction (SPME) is worked out. The fully automated process includes an on‐fiber methylation step and the GC‐MS. The repeatability standard deviation of the process amounts to RSD < 12%. Detection limits between 0.07 and 0.70 μg/L are achieved.