Abiotic Stream Classification as a Basis for a Surveillance Monitoring Network in Austria in Accordance with the EU Water Framework Directive

This study presents the 26 major surface water types established in Austria in accordance with the draft of the EU Water Framework Directive (WFD). These types are made up of so‐called aquatic landscape units and large rivers. The 17 aquatic landscape units were defined using a database in which all Austrian running waters with a catchment area greater than 10 km^[2] were described according to the following typological features: size of catchment area, altitude of catchment area and confluences, stream order, geology, zoogeographical regions (ecoregions), and subregions. At running waters with gauges, a classification according to flow regimes was carried out. Large rivers were defined as running waters with a stream order ⩾7 and/or a catchment area > 2500 km² and/or with an average flow >50 m³/s. These major types represent, inter alia, the basis for the establishment of a surveillance monitoring network as required by the WFD.     

Zielvorgaben für Pflanzenschutzmittelwirkstoffe und andere Schadstoffe in Oberflächengewässern

Quality Targets for Pesticides and Other Pollutants in Surface Waters Surface waters are not only adversely affected by industrial and municipal wastewaters but also by diffuse sources. For the control of the ecological water quality, so‐called quality targets are set. The quality targets are threshold concentrations for hazardous substances related to the protected goods like water ecosystems, drinking water supply, sediments, or fishing. In this paper, quality targets for the protection of aquatic life in surface waters were derived on the basis of a concept developed by the International Commission for the Protection of the Rhine (Internationale Kommission zum Schutze des Rheins – IKSR). The quality targets for the selected hazardous substances, which mainly belong to the chemical class of pesticides, were calculated using ecotoxicological results for species of bacteria, algae, fish, and small crustaceans, as the four trophic standards of the water ecosystem. In cooperation with the Federal Environmental Agency (Umweltbundesamt – UBA) the effect data were taken from ecotoxicological data bases. According to the concept of the IKSR, the lowest test result for the most sensitive species was multiplied by an assessment factor. This proceeding concerns the difficulty in describing the complex interactions in water ecosystems with toxicity data of single laboratory experiments for a few organisms. For seven pesticides quality targets below 0.1 μg/L were proposed. These results show that the ecotoxicologically based quality targets might be even lower than the limit values for pesticides in drinking water of 0.1 μg/L. But for most of the substances the determined values are significantly higher. The great concentration range of quality targets demonstrates distinctly that one standard concentration for all pesticides could not be given with regard to the different effects on aquatic organisms.     

On the Elimination of Organic Microcontaminants by Flocculation with Lime Hydrate

For the purpose of utilizing domestic flocculants for the treatment of water and of reducing by this the equivalent imports of metal salts, in this paper the result of investigations made on model waters and on a river water sample is described. The model waters contained the pesticides Atrazin, Diuron and 2,4-D, which partly were polluted in addition with different quantities of fulvic and humic acids as well as with colloidal substances causing turbidity (Friedland clay and finely dispersed cellulose). The investigations were supplemented by testing several adsorption media as γ-aluminium oxide, active carbon and diatom earth. In the presence of fulvic and humic substances one does not succeed in eliminating the investigated herbicides by flocculation with lime hydrate. Only after chemical side reactions between these contained substances the adsorbability is clearly influenced. The different elimination efficiencies at different reaction conditions are explained in detail.     

Large-scale pesticide monitoring across Great Barrier Reef catchments--Paddock to Reef Integrated Monitoring, Modelling and Reporting Program

The transport and potential toxicity of pesticides in Queensland (QLD) catchments from agricultural areas is a key concern for the Great Barrier Reef (GBR). In 2009, a pesticide monitoring program was established as part of the Australian and QLD Governments' Reef Plan (2009). Samples were collected at eight End of System sites (above the tidal zone) and three sub-catchment sites. At least two pesticides were detected at every site including insecticides, fungicides, herbicides, and the Reef Plan's (2009) five priority photosystem II (PSII) herbicides (diuron, atrazine, hexazinone, tebuthiuron and ametryn). Diuron, atrazine and metolachlor exceeded Australian and New Zealand water quality guideline trigger values (TVs) at eight sites. Accounting for PSII herbicide mixtures increased the estimated toxicity and led to larger exceedances of the TVs at more sites. This study demonstrates the widespread contamination of pesticides, particularly PSII herbicides, across the GBR catchment area which discharges to the GBR.     

Monitoring pesticides in the Great Barrier Reef

Pesticide runoff from agriculture poses a threat to water quality in the world heritage listed Great Barrier Reef (GBR) and sensitive monitoring tools are needed to detect these pollutants. This study investigated the utility of passive samplers in this role through deployment during a wet and dry season at river mouths, two near-shore regions and an offshore region. The nearshore marine environment was shown to be contaminated with pesticides in both the dry and wet seasons (average water concentrations of 1.3-3.8 ng L⁻¹ and 2.2-6.4 ng L⁻¹, respectively), while no pesticides were detected further offshore. Continuous monitoring of two rivers over 13 months showed waters flowing to the GBR were contaminated with herbicides (diuron, atrazine, hexazinone) year round, with highest average concentrations present during summer (350 ng L⁻¹). The use of passive samplers has enabled identification of insecticides in GBR waters which have not been reported in the literature previously.     

Fate of Pesticides and Their Transformation Products: First Flush Effects in a Semi‐Arid Catchment

Although it is known for many years, that transformation products (TPs) of pesticides are often more persistent, mobile, and sometimes more toxic than the parent compound, former catchment scale studies of substance release and flushing effects focused only on the parent compound. In this study, four river points were sampled in the Hula Valley, Israel, and samples were analyzed in the lab for chlorpyrifos (CP) and endosulfan residues (including transformation products; TPs). Sampling results of the first rainfall in autumn 2009 identified a strong release of most substances to the rivers. First flush effects of these substances were assessed regarding the risk for drinking water supply and ecology, like fresh water invertebrates and fish. Although, these substances were found in Jordan River water during the first significant rainfall the observed levels are below international drinking water guideline values with no adverse effects on human health in the region. However, the observed CP and chlorpyrifos oxon (CPO) levels are above the acute toxicity for fresh water invertebrates and fish. The study shows that the Hula Valley was an important source of pesticides and TPs at the Upper Jordan River basin and that substance flushing is extremely important for pesticides‐monitoring campaigns.     

Bestimmung polarer Phosphorsäureester in Trink‐ und Oberflächenwasser mittels HPLC‐MS‐MS

Determination of Organophosphorus Pesticides in Water by HPLC‐MS‐MS In the EC Water Framework Directive 2000/60/EG and in CEC 76/464/EEC there are 16 organophosphorus pesticides (insecticides and acaricides) listed which belong to so‐called priority substances. The committed quality aims of these substances frequently require maximum concentrations below 0.1 μg/L. In this paper a HPLC‐MS‐method is described. The reported limits of determination of organophosphorus pesticides are lower than the demanded limits. High analytical sensitivity is reached by solid‐phase extraction (SPE) and by injecting large volumes. For some of these substances no sample enrichment is needed and low detection limits are obtained by direct injection of the original water sample.     

Ardières-Morcille in the Beaujolais,France: A research catchment dedicated to study of the transport and impacts of diffuse agricultural pollution in rivers

The 8-km² Morcille catchment, which is a sub-catchment of the 150-km² Ardières catchment in the Beaujolais region of France, is one of the first sites in Europe where research has been conducted on surface water contamination by pesticides. A consolidated hydrological and chemical dataset has been set up with data collected since 2002 on the Morcille River and since 2011 on the Ardières River. Additional data on the ecotoxicological and ecological impacts of pesticides on aquatic microbial communities and macroinvertebrates has also been recorded in both rivers since 2005. The ‘Site Atelier Ardières-Morcille Dataset’ described here combines rainfall and stream water height measurements at gauged stations with concentrations of two trace elements and nine pesticides (mainly herbicides, fungicides and some of their metabolites) in both the Ardières and Morcille rivers. All contaminant concentration data showed spatial and temporal variability in water quality associated with pesticide use and rainfall patterns. This long-term monitoring framework made it possible to estimate the persistence of two herbicides (diuron and norflurazon) after legislation banning them. It took 4 years for diuron and more than 10 years for norflurazon concentrations to fall below 0.1 μg/L. Concurrent biological data showed a gradient of impacts consistent with chemical anthropogenic pressure, and rapid recovery of phototrophic microbial communities after the diuron ban. Finally, monitoring data on pesticide transport in a grassed strip set on a slope of the Morcille catchment confirmed that vegetative filter strips can effectively reduce diuron fluxes in surface runoff (>80% abatement) and infiltration water (>70% abatement). The full dataset offers a valuable resource for the validation of hydrological models and the development of global approaches to better understand the pressure–transport–exposure–impact chain and aquatic community resilience at the small catchment scale.     

The influence of a season of extreme wet weather events on exposure of the World Heritage Area Great Barrier Reef to pesticides

The 2010-2011 wet season was one of extreme weather for the State of Queensland, Australia. Major rivers adjacent to the Great Barrier Reef (GBR) were discharging at rates 1.5 to >3 times higher than their long term median. Exposure to photosystem II herbicides has been routinely monitored over a period of up to 5 years at 12 inshore GBR sites. The influence of this wet season on exposure to photosystem II herbicides was examined in the context of this long-term monitoring record and during flood plume events in specific regions. Median exposures expressed as diuron equivalent concentration were an average factor of 2.3 times higher but mostly not significantly different (p<0.05) to the median for the long-term monitoring record. The herbicides metolachlor and tebuthiuron were frequently detected in flood plume waters at concentrations that reached or exceeded relevant water quality guidelines (by up to 4.5 times).     

Long-term trends of physical, chemical and biological variables in the River Danube 1957–1995: A statistical approach

: A 39-year series (1957 – 1995) of data on fourteen physical, chemical and biological variables from the Austrian section of the River Danube west of Vienna – Nußdorf was analysed statistically to detect long-term trends of the variables in relation to human activities (represented by time), discharge and water temperature. ¶ Principal component analysis distinguished four main components explaining 72 % of the total variance: PC1 contains total phosphorus, soluble reactive phosphorus, ammonium and potassium permanganate values, PC2 contains nitrate-N, chloride and oxygen, PC3 contains BOD5 and nitrite-N, and PC4 contains numbers of bacteria. Trends in time were most pronounced for variables in PC1, but also occurred in PC2; variables in PC3 and PC4 had no trends. Seasonal patterns were marked for variables in PC2, slightly less in PC1, and least in PC3 and PC4. Concentrations were minimal in summer and maximal in winter, inversely related to discharge (maximal in summer). Following reductions in point-source nutrient inputs to the Danube, in both Germany and Austria, mean concentrations in the river have fallen by at least half since the 1980s. Chloride and nitrate-N also show trends towards lower concentrations. The Danube is well-oxygenated, with concentrations near air saturation values.¶ A mathematical relationship between concentrations of the variables and river discharge (Q), water temperature (T) and time (t), was established to determine mean trends and predictions against a background of considerable seasonal and stochastic variability; for the single variables Q explained 0 – 20 % and T explained 2 – 58 % of the variation in the concentrations. The relationship was highest for variables in PC2 and lowest for those in PC3 and PC4, where Q and T had little or no influence.¶ Reasons for rising and falling long-term trends with time are discussed in detail. Austria now contributes only minor proportions to the nutrient load of the Danube, which is causing eutrophication of the Black Sea downstream, and water quality of the Austrian section of the river is good.¶ The advantages and problems of statistical process analysis are discussed in relation to environmental monitoring programs and the different specific requirements of compliance monitoring.     

Vergleichende aquatoxikologische Ergebnisse mit ausgewählten Wasserschadstoff-Gruppen und repräsentativen Wasserorganismen

Salmo gairdneri, Cyprinus carpio, Poecilia reticulata, Leuciscus idus melanotus, Asellus aquaticus, Ankistrodesmus falcatus and Monoraphidium griffithii were exposed to four growth regulating herbicides, four photosynthesis toxicants, lindane, an anionactive tenside, KCN and Na₃[Cu(CN)₄] in standardized toxicity tests. The biochemical degradability of the substances was tested with activated sludge. In order to test the possible effects in waters there should be used Salmo for the oligosaprobic zone. Poecilia as well as Ankistrodesmus and Monoraphidium provide reliable estimations for β-mesosaprobic waters. With respect to the longer-term permission of plant protection products, besides Salmo there can be recommended also Leuciscus.     

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.     

Gulfwatch: monitoring spatial and temporal patterns of trace metal and organic contaminants in the Gulf of Maine (1991-1997) with the blue mussel, Mytilus edulis L

Gulfwatch, established in 1991, is an international contaminant monitoring program in which the blue mussel, Mytilus edulis, is used as an indicator of the level and extent of contamination in the Gulf of Maine. Since 1991, trace metals, PAHs, PCBs, and OC pesticides have been measured in mussel tissues at 56 sites. The distribution of most metals was relatively uniform throughout the Gulf with the exception of Ag, Pb and Cr. However, the concentration of organic contaminants increased in a north-to-south direction. High concentrations of contaminants were correlated with large human population density and proximity to large rivers. Temporal analysis of five sites revealed that the majority of contaminant concentrations were either unchanged or decreasing. The concentrations of most contaminants were lower than the median of the National Status and Trends (NS & T) Mussel Watch with the exceptions of Cr, Hg, Pb and sigma PCB24. Hg concentrations at > 80% of the Gulfwatch sites exceeded the NS & T median +1 SD. Gulfwatch continues as a primary contaminant monitoring program in the Gulf of Maine.     

Zur Bewertung der Analytik und Interpretation des Gruppenparameters “Extrahierbares organisch gebundenes Halogen” von Wässern

Organohalogen compounds are gaining in importance in the control of surface and drinking water due to their unwholesome properties. An accumulation of the organohalogen compounds, occurring mostly at low concentrations, is possible in different ways. The author discusses the possibility and problems of the extractability from waters with the aid of organic solvents. The group parameter EOX that can be determined does not allow any statement concerning components of individual substances, but gives some clues to the state of surface and drinking waters which are mostly anthropogenically polluted. Results of practical examples as well as theoretical considerations indicate the importance of the different distribution coefficients in the solvent/water extraction system. The degree of extraction can be considerably increased by the application of suitable mixtures of solvents. In waters with a known composition, the probably detectable EOX-quantity can be calculated by means of theoretical degrees of extraction.     

Biodegradation of Herbicide Propanil and Its Subproduct 3,4‐Dichloroaniline in Water

The rational use of pesticides generates an impact which is normally reversed and eliminated by the environment itself. However, the indiscriminate use of pesticides makes its natural degradation rhythm difficult, prolonging their presence in the soil for a great deal of time. Aiming towards a decrease in the environmental impact of pesticides, soil microorganisms capable of degrading pesticides, such as propanil, were investigated. An Enterobacter cloacae strain, isolated from rice field soil, was exposed to the herbicide propanil alone and in a mixture containing also bentazone, clomazone, quinclorac, and 2,4‐D. This bacterium was able to eliminate 100% of the applied propanil in 28 days. Propanil degradation in the 5‐herbicide mixture was much lower than that of individual pesticide degradation. The aeration of the system helped to degrade propanil and its subproduct 3,4‐dichloroaniline much faster. LC with UV detection was used to determine the remaining concentrations of the herbicides and their subproducts.     

Bestimmung von Umweltqualitätsnormen für potenziell gewässerrelevante Stoffe

With the Water Framework Directive (WFD) the European Commission (EC) is requested to define environmental quality standards for pollutants to protect aquatic life in surface waters. Quality standards have to be derived by a scientific risk assessment and should not be exceeded. The recommended quality standards are mainly based on long term toxicological tests with algae, crustaceans and fish. The lowest effect concentration is divided by an assessment factor between 10 and 1000, which considers the data quality and quantity. In this work funded by the German Länder Working Party on Water (Länderarbeitsgemeinschaft Wasser – LAWA) environmental quality standards for 40 considered relevant substances were derived for aquatic ecosystems. The data sheets cover the identification of the compounds, their behaviour in the environment (physical‐chemical properties, biotic and abiotic degradation, sorption, bioaccumulation), information about mode of action, uses, analytical determination and available quality criteria. Ecotoxicological effect concentrations for bacteria, algae, protozoa, aquatic plants, crustaceans, fish, amphibians, insects and molluscs are listed. For 17 of the 40 hazardous substances investigated, quality objectives above 1 μg/L were derived. For 12 substances the values were between 0.1 μg/L and 1 μg/L and for 5 substances lower than 0.1 μg/L. Incomplete ecotoxicological data sets of the remaining compounds do not allow the derivation of quality standards. Especially for drugs further ecotoxicological test results are needed.     

Occurrence of priority pollutants in WWTP effluents and Mediterranean coastal waters of Spain

A comprehensive study aimed at evaluating the occurrence, significance of concentrations and spatial distribution of priority pollutants (PPs) along the Comunidad Valenciana coastal waters (Spain) was carried out in order to fulfil the European Water Framework Directive (WFD). Additionally, PP concentrations were also analysed in the effluent of 28 WWTPs distributed along the studied area. In coastal waters 36 organic pollutants of the 71 analysed, including 26 PPs were detected although many of them with low frequency of occurrence. Only 13 compounds, which belong to four different classes (VOCs, organochlorinated pesticides, phthalates and tributyltin compounds (TBT)) showed a frequency of occurrence above 20% in coastal waters. In the results obtained until now, octylphenol, pentachlorobenzene, DEHP and TBT exceeded the annual average concentration (EQS-AAC), and only TBT surpassed the maximum allowable concentration (EQS-MAC). The most frequent contaminants determined in coastal waters were also present in WWTP effluents.     

Mikrobiologische Untersuchungen an deponiebeeinflußten Wässern unter besonderer Berücksichtigung sulfatreduzierender Bakterien

In seepage waters of eight different dumping sites, counts on agar and gelatine of endobacteria, coliforms, Escherichia coli, enterococci and sulphate reducers are determined and the influences exerted on them by various chemical criteria are discussed. Locations of dumping sites which can be regarded as dumping sites of noxious substances due to the Eh and pH values of their seepage waters indicate this status by low or lacking bacterial counts. The bacterial counts of the sulphate reducers correlate with the Eh/pH values. In fourty samples partly high numbers for sulphate reducers were found also above the limit of BAAS-BECKING Eh = 4–115 mV. Considerably reduced conditions with high concentrations of sulphide and ammonium lead to the death of sulphate reducers. By impoundage of water in municipal refuse disposal sites there are created conditions for sulphuretes due to which these refuse disposal sites develop into sites of noxious substances.     

Norian magnetostratigraphy from the Scheiblkogel section, Austria: constraint on the origin of the Antalya Nappes, Turkey

Late Triassic magnetostratigraphic investigations in southwestern Turkey have suggested that parts of the Antalya Nappes are constituted of a melange of blocks originally deposited either in the vicinity of the northern tip of Arabia or, more surprisingly, directly north of India, in the southern hemisphere. In order to ascertain this result more clearly, we have correlated the Turkish series with Austrian sections of corresponding age from the Northern Calcareous Alps, for which the hemisphere of deposition is beyond doubt. The new magnetostratigraphic results obtained from the Scheiblkogel section (Austria) confirm the previously suggested middle to late Norian magnetic polarity sequence and support the heterogeneous character of the Antalya Nappes.