Verringerung der Schwermetall‐ und Sulfatbelastung in sauren bergbaubelasteten Gewässern durch Aluminiumpräzipitate

Attenuation of Heavy Metals and Sulfate by Aluminium Precipitates in Acid Mine Drainage During the mixing of acid mine waters with nearly neutral tributaries, often precipitates are formed which are high in iron or aluminium. These precipitates cover the river bed for many kilometres. Near the town of Lehesten (Thuringian slate mining area), leachates of slate quarries and waste rock dumps contain high amounts of aluminium, sulfate, copper, nickel, zinc, manganese, and H⁺ ions as a result of the oxidation of incorporated pyrite. These leachates enter the brooks Loquitz, Kleine Sormitz, and Rehbach leading to the phenomenon named above. The contribution of the forming aluminium‐rich precipitates on the attenuation of sulfate and heavy metals by sorption or coprecipitation was studied by analysing the composition of water and sediment samples as well as samples of suspended matter. Sulfate is often considered as conservative tracer in acid mine drainage. However, sulfate does not behave conservatively in this system what might be explained by the adsorption of sulfate to the aluminium precipitates. Instead, conservative behaviour was found for calcium, potassium, chloride, zinc, manganese, and nickel. A formation of jurbanite can be excluded because of the low sulfate contents. The sulfate content of the sediment depends on the pH. At low pH values (4.8) the S/Al ratio corresponds to the theoretical ratio in basaluminite and decreases with rising pH. Sulfate is weakly bound to the solid phase and can easily be replaced by OH^– ions. A formation of basaluminite is possible at low pH values with a fluent transition to aluminium hydroxide. Therefore the precipitates are assumed to consist predominantly of aluminium hydroxide with sulfate being adsorbed to the surface.     

Dissolved Carbohydrate Concentration,Composition, and Bioavailability to Microbial Heterotrophs in Stream Water

Dissolved total carbohydrates (DTCH), dissolved free monosaccharides (DFMS), dissolved organic carbon (DOC), biodegradable DOC (BDOC), and humic substances (HS) were measured in White Clay Creek (WCC), a stream in southeastern Pennsylvania Piedmont, USA. Samples were collected over different seasons and under baseflow and stormflow conditions. DOC concentrations ranged from 1.0 to 12.8 mg/L C with the highest concentrations associated with stormflows. Carbohydrates ranged from 0.42 to 12.4 μM and accounted for 2.9 to 12.7% of the DOC. Humic substances represented the major DOC fraction, accounting for 55 to 72% of the DOC pool under all flow conditions. The humic fraction had a lower carbohydrate content (4.4%) than the non-humic fraction of DOC (7.2%). Stormflow DOC was enriched in carbohydrates relative to baseflow DOC, but the percentage of humic-C changed little. Carbohydrates were primarily present as dissolved polysaccharides (55%), but a significant fraction was bound to humic substances (40%), while a small proportion was present as monosaccharides (5%). The major monosaccharides in stream water, listed in order of decreasing concentration, included glucose, galactose, rhamnose, xylose, arabinose, mannose, and fucose. On average (30.6 ± 7.4)% (n = 44) of the stream water DOC was biodegradable, and carbohydrates accounted for 9.9 to 17.7% of the BDOC.     

Tracing of Peroxidase Activity in Humic Lake Water

An enzyme assay was developed for studies on peroxidase activities in humic lake water. 3,4-Dimethoxybenzyl alcohol (veratryl alcohol, VeraOH) was used as tracer substrate, and peroxidase (EC 1.11.1.7) activity was measured by high-performance liquid chromatography. The chemical stability of VeraOH and its application as peroxidase substrate was tested under light and dark conditions, different hydrogen peroxide (H₂O₂) concentrations and humic matter contents. VeraOH was stable under low UV radiation at in situ conditions in lake water (<0.010...0.25 kJ m^–2 d^–1), laboratory conditions (<0.05...0.30 kJ m^–2 d^–1), and low (1...100 μM) H₂O₂ concentrations. However, peroxides oxidized VeraOH above 1...10 mM H₂O₂ concentration in sterile Millipore-Q and humic lake water. Dark incubations showed little VeraOH oxidation products. The developed peroxidase assay was tested in the growth medium of Phanerochaete chrysosporium and a bacteria isolate (P.M.D. 20.4.3.1) from mesohumic lake Pääjärvi. Peroxidase activities were also measured in natural microbial communities under standard laboratory and under in situ conditions in humic lake water. Incubation times of about 5 to 12 days were usually needed to record significant (P < 0.05) peroxidase activities, in lake waters. In situ peroxidase activities varied in pelagial surface water (0...0.5 m) on a seasonal scale between 74 nmol L^–1 h^–1 and 273 nmol L^–1 (mean: 176 nmol L^–1 h^–1) and within the water column between 110 nmol L^–1 h^–1 and 800 nmol L^–1 h^–1 (mean: 500 nmol L^–1 h^–1) in polyhumic lake Mekkojärvi.     

Urease-Hemmtest für wirkungsbezogene Untersuchungen der Bindungsformen von Kupfer in Wässern und Bodeneluaten

Urease Inhibition Test for Effect-related Investigations of Copper Speciation in Water and Soil Extracts In 80 different water samples, the inhibition effect of cupric ions was measured by application of a simple urease inhibition test. In relation to the total copper concentration, the inhibition permits an effect-related classification of drinking water, rain water, spring water, surface water, leakage water, wastewater, and soil extracts. Drinking water contains high parts of cupric ions in the free hydrated form. Their copper content results in high urease inhibition and is caused by using copper pipes in house plumbing. In leakage water, wastewater, and soil extracts, cupric ions are mainly complexed by organic compounds in the sample matrix. Hence, the inhibition effects are low. In soil extracts, the urease inhibition increased after an UV-decomposition procedure, but a decreasing effect was observed for a surface and a drinking water sample, respectively. The chemical oxygen demand and UV-absorbance at 255 nm measured before and after the procedure were correlated to the content of organic compounds, i.e., humic acid. In most samples, the organic matrix was not decomposed completely. The oxidizing decomposition apparently forms further complexing agents, which suppress the inhibition effect of cupric ions. In the rain water samples investigated, the content of organic compounds depended on rain intensity. The chemical oxygen demand and UV-absorbance, respectively, were low for rain water collected during strong rain periods and increased with decreasing rain intensity. The rain water trickled over sheet-lead roof showed an increase of urease inhibition compared with the simultaneously collected rain. Consequently, a decomposition of organic matrix could be demonstrated in rain water by use of the urease inhibition test.     

Arsenic — a Review. Part I: Occurrence,Toxicity, Speciation,Mobility

In natural waters arsenic concentrations up to a few milligrams per litre were measured. The natural content of arsenic found in soils varies between 0.01 mg/kg and a few hundred milligrams per kilogram. Anthropogenic sources of arsenic in the environment are the smelting of ores, the burning of coal, and the use of arsenic compounds in many products and production processes in the past. A lot of arsenic compounds are toxic and cause acute and chronic poisoning. In aqueous environment the inorganic arsenic species arsenite (As(III)) and arsenate (As(V)) are the most abundant species. The mobility of these species is influenced by the pH value, the redox potential, and the presence of adsorbents such as oxides and hydroxides of Fe(III), Al(III), Mn(III/IV), humic substances, and clay minerals.     

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.     

The Impact of Human Activities on Freshwater Aquatic Systems

The roles of oxygen and its activated species (superoxide radicals, hydrogen peroxide, hydroxyl radicals), as well as that of sulfur compounds, are considered in relation to biological quality and the self-cleaning capacity of freshwater aquatic systems. The effects on the aquatic redox-processes are discussed in terms of atmospheric fallout of sulfur compounds, bottom sediment composition, and input of wastewaters containing reducing substances. It is shown that the totality of anthropogenic influences, and/or unfavourable natural geochemical conditions, as well as climatic effects in a region can increase the significance of one-electron transfer processes in bio-geochemical cycles of oxygen, sulfur and manganese, compared with the significance of two-electron transfer processes. The resulting, reactive intermediate products of one-electron transfer processes are very important with respect to the composition and properties of aquatic systems. Examples are given of practical applications of wastewater treatment, using hydrogen peroxide and UV-irradiation, and of regulation of consumers’ activities which affect natural waters.     

Trophieindikation in Fließgewässern mit Hilfe des TIM (Trophie‐Index Makrophyten) – Erprobung eines neu entwickelten Index im Inninger Bach

Indicating the Trophic State of Running Waters by Using TIM (Trophic Index of Macrophytes) – Exemplary Implementation of a New Index in the River Inninger Bach The river Inninger Bach represents the outflow of the lake Wörthsee (Bavaria). The mean pH of the calcareous river has a value of ca. 8 during the vegetation period, the mean conductivity is about 350 to 400 μS/cm. The macrophyte vegetation of the river course was mapped and the nutrient concentrations of both the water body and the sediment were measured. In every mapping section the Trophic Index of Macrophytes (TIM) was calculated. By cluster analysis the mapping sections were grouped into three zones which differed in macrophyte vegetation. These differences are not associated with varying nutrient concentrations but are mainly due to differences in the degree of shading. In spite of the characterisation of the lake Wörthsee as oligo‐mesotrophic the river Inninger Bach, which represents the outflow of the lake Wörthsee, is classified as meso‐eutrophic by the Trophic Index of Macrophytes TIM. The increased trophic state of the river compared to the lake is caused by the river Krebsbach, a small tributary flowing into the river Inninger Bach only a short stretch downstream of its outflow of the lake Wörthsee. The river Krebsbach shows a total phosphorus concentration of about 56 μg/L P. The input of diaspores of submerged macrophytes both from the oligo‐mesotrophic lake Wörthsee and the eutrophic river Krebsbach leads to a submerged vegetation comprising species with different optima in regard to the trophic situation. This is one of the main reasons why many values of the TIM have to be labeled as “not sure”.     

Entwicklung von Enzymimmunoassays zum Nachweis von Phenoxycarbonsäure-Herbiziden in Trink- und Grundwässern Development of Enzyme Immunoassays for the Detection of Phenoxycarboxylic Acid Herbicides in Drinking Water and Groundwater

Competitive solid phase enzyme immunoassays using polyclonal antibodies were developed for the detection of the phenoxycaboxylic acids MCPB [4-(4-chloro-2-methylphenoxy)butyric acid], Mecoprop [2-(4-chloro-2-methylphenoxy)propionic acid], and 2,4-D [(2,4-dichloro-phenoxy)acetic acid] in drinking water and ground water. The carrier protein for the immunization was bovine serum albumin, horseradish peroxidase conjugates were employed as enzyme tracer. For the three antisera, the optimization of detection limits and test sensitivities was our first consideration. For the mecoprop and 2,4-D antisera, the strongest influences were the pH value and the ionic strength, as much as the use of enzyme tracers with lower affinities. The MCPB antiserum reacted with 2,4-DB[4-(2,4-dichlorophenoxy)butyric acid] with equal specificity, either could be detected at 0.02 μg/L (80% B/B₀), middle of the test (50 B/B₀) lying at 0.1 μg/L. The detection limit with mecoprop antiserum was optimized to 0.02 μg/L, the prescribed limit for drinking water of 0.1 μg/L ling at 60 % B/B₀. The strongest cross-reactivity was found for mecoprop methyl ester. MCPB. 2,4-DB, and dichloroprop have crossreactivities of 50%, 6.7%, and 6.3%, respectively. The 2,4-D antiserum reacts less sensitively with 2,4-D, the detection limit being 0.4 μg/L. The 2,4-D isooctyl ester and 2,4-D methyl ester demonstrate as cross-reacting compounds high cross-reactivites of 3630% and 2230%. The cross-reactions of the compounds 2,4-DB, MCPB, and MCPA [(4-chloro-2-methylphenoxy)acetic acid] lie at 52%, 69%, and 41%. 100 ground water tests were spiked within laboratory. All positive samples were correctly identified. Falsely negative results did not appear.     

Nitrifikation – Grundlagen des Stoffwechsels und Probleme bei der Nutzung von Ammoniakoxidanten

Nitrification – Fundamentals of the Metabolism and Problems at the Use of Ammonia Oxidizers From an ecological point of view, a great problem results from the release of increasing amounts of inorganic and organic nitrogen compounds. Apart from gaseous nitrogen compounds, such as the greenhouse gas N₂O, soluble nitrogen compounds such as ammonium cause difficulties. In recent years, great progress has been made regarding the reduction of the emission of sulfur and phosphorus compounds. Since there are no effective strategies for the decrease of nitrogen releases, the emission of such compounds has even been increasing. Therefore, great efforts are being made to eliminate the soluble nitrogen compounds in particular, for example in wastewater treatment plants. A decisive meaning befits the chemolithoautotrophic ammonia oxidizers. This review focuses on the ecological consequences of the release of ammonia in particular, the metabolism of the ammonia oxidizing microorganisms under consideration of the latest research results, and the problems that arise in the context of using these bacteria for the removal of ammonia.