Anreicherung und Verteilung von Schwermetallen und anderen Elementen in Oberflächensedimenten der Berliner Gewässer und ihres Umlands Enrichment and Distribution of Heavy Metals and Other Elements in Surface Sediments of Berlin Waters (Germany) and their Surroundings

For a wide variety of substances aquatic systems are the medium of origin, or sinks in a longer or shorter lasting stay or even in geological periods. For surface sediments of Berlin waters and their surroundings this paper describes the enrichment and distribution of heavy metals (SM), which have a high priority under international aspects and a marked capability to geoaccumulation. From the 25 metals investigated Hg, Pb, Cu, Cd and Zn are of anthropogenic origin, all others are of geochemical provenience and correspond to background values. Some metals (Hg, Cd, Ni, Co, Cu, Cr and Pb) have specific concentration profiles with increasing depth of water and sediment. The study of correlation of SM in sediments demonstrates generally a strong relation to macroelements and between some metals themselves.     

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.     

The Flood in the Odra River 1997 – Impact of Suspended Solids on Water Quality

The flood in the Odra river in 1997 has led to considerable additional pollution of the Stettin Lagoon and the Baltic Sea with contaminated suspended solids. For some priority substances, the pollutant entries via suspended solids during the flood period are estimated to be approximately 1/3 of the usual annual load. Among these priority pollutants there are total organic carbon (TOC), nitrogen, and the heavy metals Cu, Pb and Zn. For the concentrations of the priority pollutants in suspended solids accumulation factors from 2 to 4 in the comparison with normal conditions were observed. On the basis of the analysis of sediments sampled after the flood, main sources of the pollutants should be evaluated. As reference area with an industrial background as well as a typical pollutant pattern the region around Glogow/Legnica is proposed.     

Comparison of 24 h and Long-term pHstat Leaching Tests for Heavy Metal Mobilization from Solid Matrices

The dynamic leaching behaviour of environmentally relevant heavy metals makes it difficult to fix a suitable elution time of leaching tests. With ten different solid materials which were characterized by wavelength-dispersive X-ray fluorescence analysis and by the determination of aqua regia soluble amounts of heavy metals we performed 24 h and long-term leaching tests using the pH_stat procedure at pH 4 to be able to compare the resulting acid neutralization capacities (ANC) and heavy metal mobilization. This comparison demonstrates firstly the limitations in predicting the extent of heavy metal release after a longer (geological) time period only from the leached amounts after 24 hours and the ratio of the ANC values measured in the 24 h test and in a long-term experiment, respectively. Secondly, the effect of elution time on the leachability is not uniform but element specific and matrix dependent. Hence, the pH_stat leaching test performed in the usual manner does not seem to be suitable particularly for assessing long-term mobilization of heavy metals under acidic conditions. Additional experiments under variation of shaking frequency and time clearly demonstrate the dominant influence of the first parameter on the resulting ANC and support the necessity of further studies to optimize the pH_stat leaching procedure before the test can be recommended in regulations for environmental protection.     

Applicability of Single and Sequential Extractions for Assessing the Potential Mobility of Heavy Metals in Contaminated Soils

Heavy metal polluted sites are bearing an acute hazardous risk for the groundwater, but also a potential one. While the acute risk can be assessed directly via seepage water measurements, determination of the potential risk is much more complex. It results from the sum of all reactions that are capable to mobilize heavy metals under worst case environ-mental conditions. Using a fourfold sequential extraction (SE₄) such a worst case was simulated for four soils highly contaminated with Pb, Zn, and Cu. The resulting potential mobilizable amounts ϕ_pm have been compared with those derived from 6 single extractions. By means of variance analyses, it is shown that ϕ_pm of lead can be represented by a single extraction with NH₂OH. In contrary, ϕ_pm of zinc can be represented using the pH_stat test or an extraction with aqua regia, while ϕ_pm of copper can be represented only by aqua regia extraction. The water-soluble amounts deriving from the DEV-S4 test do not correlate with the potential mobilizable amounts of any metal. Therefore, an assessment of contaminated sites should include an aqua regia extraction additionally to the seepage water analysis.     

Untersuchungen zur Abtrennung von Schwermetallen aus Abwasser mit frisch hergestelltem Magnetit Studies for Separation of Heavy Metals from Wastewater with Freshly Precipitated Magnetite

The separation of heavy metals from wastewater may be improved by precipitation/flocculation with iron- or aluminium salts. Often, the resulting products are voluminous, water-containing, amorphous hydroxides which show only limited flocculation properties and may possibly pose problems with the technical separation from the aqueous phase. The application of magnetite could be advantageous because magnetite is ferromagnetic and can be separated very quickly in a magnetic field. First of all, a simple preparation method for magnetite was studied. Pure magnetite could be prepared by mixing an iron(II) salt solution with an equivalent amount of sodium hydroxide at room temperature without oxidation by air. The required reaction time was only 3 hours. For the precipitation of heavy metals from an electroplating wastewater, a better metal elimination and smaller sludge volumes resulted with that artificially produced magnetite in comparison with a precipitation by NaOH. Thereby not only the adsorption of metals was established but also coagulation effects of the magnetite sludge with small metal hydroxide particles. By means of the experimental results. sorption of nickel and chromium was compiled as function of pH and precipitation time. Because freshly precipitated magnetite shows very good sorption and flocculation properties, and pH of precipitation may be lower, its use in high gradient magnetic separation (HGMS) could be more effective for metal elimination than magnetite powder.     

The Odra Estuary as a Filter and Transformation Area

The Odra Estuary is one of the most polluted coastal waters of the southern Baltic. To investigate how and whether the estuary acts as a filter and transformation area for the fluviogenic material, different models were developed and an intensive monitoring programme was carried out. Summarizing different methodological approaches, it could be shown that the total system filter capacity reaches 2...5% for nutrients and 10...15% for some heavy metals related to the current mean annual input. In the western part of the estuary, the retention is more important and amounts to 10...40% of the annual nutrient yield. Carbon flux studies revealed that both a reduction of the inputs and more internal and external nutrient sinks are needed to reverse the anthropogenic eutrophication process.     

Historische Entwicklung einer Sedimentbelastung: Gedächtnis einer Industrieregion Historical Trends of Sediment Loads: Memory of an Industrial Region

The chronologies are shown of sediment load on the banks of a river of the Ruhr district (Lippe) with radionuclides of radium, lead and cesium and preliminary chemical measurements for lead, zinc, arsenic, mercury, cadmium, barium, PAHs, PCDDs, PCDFs, PCBs, TOC, AOX and EOX. A new method of dating is developed and proved, which is especially suitable for rivers with radioactivity from coal mines. The method improves the well-known excess-²¹⁰Pb-dating for the use with rivers in industrial regions and allows the preparation of load histories (chronologies). Conclusions are made on the historical trend of emissions in the region from the trend of the sediment load of known age and regular sedimentation without perturbation.     

Langzeitprognosen zum Sickerwasseraustrag von Schwermetallen aus Deponien von Müllverbrennungsschlacken

Long‐term Assessment for the Leachate Release of Heavy Metals from Municipal Solid Waste Incineration Bottom Ash Monofills Municipal solid waste incineration (MSWI) bottom ash was investigated by chemical, mineralogical, and microbiological methods as well as leaching‐ and laboratory lysimeter tests. Compared to geological material bottom ash shows a high content of soluble salts, organic carbon, and heavy metals. The heavy metals are mainly bound in alloys and glas. Addition of oxic and acetic solutions quickly oxigenize the metal‐phases and alloys. Only fixation in newly formed phases like carbonates or hydroxides prevents heavy metal release till pH 7 in case of pH‐reduce. In the long‐term the acid buffer is reduced by the environmental acid input in combination with the release of buffering phases (mostly calcite). Internal acid producing processes like decay of organic matter or oxidation of sulfides are not important for the pH‐decrease. Cu, Ni, and Zn are first released between pH 7 and 6 (mainly Zn) and a second time at pH values below 5 (mainly Cu). Pb is significantly released at pH values below 5, Cr only at pH < 4. Mainly metals, alloys, and the rims of glas are destroyed by leaching. Phases like metal hydroxides (mainly Fe‐phases) or amorphous, water bearing Fe‐Al‐Si‐oxides are finally formed. Long‐term leaching by acetic fluids increases the total availability of heavy metals (except Cr) with increasing time. Kinetic effects including changing of metal binding forms seem to be responsible for this development. Within deposit conditions of limited gas exchange (closed system) the pH of the carbonate buffering zone can drop below pH 7 in case of very strong acid input and quickly cause an enhanced metal release. But in reality such a strong acid input is not to be expected. Calcite will buffer between pH 8 and 7 for a long time. Depending on the environmental conditions (water balance, acidity of rain) and landfill design (compaction, permeability, cover, thickness) it can take hundreds till thousands of years until metal release will start. The long‐term metal release of matter with an acid buffer like carbonates can be approximately determined only by short‐term tests with powder (e.g. pH_static tests at pH 4).     

The Odra River Load of Heavy Metals at Hohenwutzen during the Flood in 1997

The Odra river flood of 1997 was a rare hydrological as well as an interesting sedimentological event. At Hohenwutzen (Lower Odra River) we observed the suspended particulate matter transport and the temporal development of water and solidsπ pollution with heavy metals and As. While the suspended particulate matter concentration decreased the trace element concentrations increased during the flood by fractionation of particles and solution processes. Because of a successive flooding of differently contaminated sedimentary sources and polluted regions the contents of heavy metals developed irregularly. Their median particulate concentrations did not exceed the values of older samples taken under mean discharge conditions between 1989 and 1995. The dissolved amounts correspond to those of the Elbe river in 1990. During the flood the dissolved share of all analyzed total element contents increased. The total loads increased 4fold (Cr) to 17fold (Cd).