Bestimmung von Spurenelementen in Gewässern mittels Flotationsspektralphotometrie am Beispiel des Arsens

Highly sensitive and selective methods for the determination of trace elements in waters and solutions are made possible by the combination of flotation and spectrophotometry (flotation spectrophotometry). The basis for it are multiply charged anion complexes of the analyte, which form sparingly soluble ion association complexes with singly charged basic dye cations in aqueous solution. Intense shaking of the aqueous solution with an organic solvent (having a low dielectric constant) results in the accumulation of these ion association complexes at the interface or on the vessel walls (flotation step). After separating the ion association complexes from the liquid phases, they are dissolved and dissociated in a polar organic solvent and the absorbance of the basic dye ions is measured as a function of the concentration of the analyte. By the example of the trace determination of arsenic in natural water, the possibilities of analytical chemistry by combination of flotation steps and spectrophotometry are demonstrated. According to the arsenic content, its determination can be performed by flotation spectrophotometry with crystal violet (detection limit 50 ng/ml As), by an indirect determination of arsenic via flotation spectrophotometry of molybdenum in the dodecamolybdoarsenic acid (detection limit 1 ng/ml As) or by the combination of collector precipitation of arsenic with zirconium hydroxide followed by froth flotation and flotation spectrophotometry as the determination technique (detection limit 0.05 ng/ml As). The reproducibilities of these variants are indicated and their accuracy is checked by comparison of methods.     

Nitrat-Bestimmung in Oberflächengewässern als Beispiel der Anwendung der UV-Derivativspektroskopie in der Umweltanalytik

Artificial nitrate solutions and a large number of membranefiltered nitrate-containing water samples from Mecklenburgian lakes and rivers were investigated in the spectral range of 200… 260 nm with a dual beam spectrophotometer. By the formation of derivative spectra there are achieved a higher spectral resolution and the elimination of undesired disturbing effects since first- and higher-order derivatives are formed. As it is known, the direct spectrophotometric nitrate determination is influenced by organic substances and some inorganic ions of natural waters. As a result, the UV derivative spectroscopy of 2nd order is recommended as a suitable technique of nitrate analysis for surface waters with a high degree of accuracy and precision – detailed reports on investigations being given. Compared with the equivalent salicylate method, however, the expenditure of the UV derivative spectroscopy described is considerably lower.     

Methode zur Bestimmung des Ammoniakstickstoffes in Gewässern

For the spectrophotometrical determination of ammonia in surface water the reaction with hypochlorite and thymol in alkaline solution is used. Compared with other techniques, expenditure is low, the reagents are stable for a long period of time and the reaction is little dependent on external conditions. In 2 cm cuvettes there can be determined 0.05… 0.5 mg/l ammonia nitrogen. Comparative investigations carried out at nine sites in the area of the lake Balaton have revealed concentrations of 0.2… 0.7 mg/l ammonia nitrogen.     

Anwendung nitratsensitiver Elektroden zur Nitratbestimmung in Grundwässern

By a comparison of methods of the nitrate determination in groundwater the correctness of the values of more than 10 mg/1 nitrate determined with a Nitratsensitrode (VEB Kombinat Keramische Werke Hermsdorf) is proved. In this range of concentrations, the rate of retrieval and the coefficient of variation are about 99.6 % and 2.5 %, respectively. Measured values from samples with less than 10 mg/1 nitrate have a larger error and are recorded as too high.     

Eine neue elektrochemische Methode zur Bestimmung von Bromidionen in natürlichen Gewässern

A New Electrochemical Method for the Determination of Bromide in Natural Waters Formation of poorly soluble Hg(I)-halides at the polarized mercury electrode was used for the development of a new electrochemical method for determination of bromide in mixed chloride and bromide solutions. Interferences due to anions, surface-active agents, and suspended matter present in natural waters were not found. The applicability of the method to natural waters was tested in the Krka River estuary in Croatia. The mass ratio Br/chlorinity = 3.320·10^?3 was calculated on the basis of recorded bromide concentrations in the estuary. As the relationship is linear, conservative behaviour of bromide ions in the Krka River estuary may be assumed.     

Untersuchung der Anwendungsmöglichkeiten von einigen komplexbildenden Ionenaustauschern zur Kupferabtrennung aus natürlichen Wässern und Abwässern

Application of Some Complexing Ion Exchangers for Copper Recovery from Natural Water and Wastewater The rational use of water resources is one of the urgent environmental control problems. These problems can be solved by the treatment of sewage. Removal of different non‐ferrous heavy metal ions from wastewater is of great importance. Besides, the selective complexing ion exchangers are of interest because of their good sorption properties. The present paper is devoted to the study of some complexing resins for copper recovery from natural water and sewage. The following carboxylic resins were studied: the cation exchangers KB‐2T, KB‐4 and the amphoteric ion exchangers ANKB 35, AMF‐2T, and AMF‐2S (manufacturer – “TOKEM” company, Kemerovo, Russia). The exchangers investigated differed from each other both by their functional groups and by their matrix physical structures. The copper recovery from CuCl₂‐, CuSO₄‐, and Cu(NO₃)₂‐solutions was studied in batch‐experiments (in presence of NaCl, Na₂SO₄, and NaNO₃). The initial copper concentration in the solutions was 0.0002...0.008 mol/L; pH values were 1.0...5.0. After equilibrium (24 h) the resins were separated from the solution. The copper concentration in the solutions after the sorption was determined by the photometrical method with pyridylazoresorcin (λ = 500 nm). On the basis of the experimental data distribution ratio, the separation factors, equilibrium constants, and stability constants of copper complexes in the exchanger phase were calculated. It was found out in this work that the amphoteric ion exchanger AMF‐2T of macroreticular structure is the most effective for the copper sorption from sewage.     

Kationenaustauschkapazität als Grundlage für die Schätzung der Schwermetallmigration im Boden

The adsorption/desorption ratio is an important quantity of the displacement of heavy metals in the soil. Adsorption isotherms as controlled quantities are suitable for the development of a transport model. With the aid of the T value the sorption coefficients and distribution quotients can be determined for different soils. By two examples of simulation the migrations of Cd and Pb were calculated with soil samples of warp clay/gley and loam/para-brown earth. It was found, inter alia, that with increasing time of input the concentration of dissolved and adsorbed heavy metals grows and that the added heavy-metal ions are absorbed in the uppermost layers already. For cases of continuous input the simulation model is recommended for the practice to estimate the migration of heavy metals in soils.     

Bakterienvermehrungsmessungen in aufbereiteten Wässern verschiedener Herkunft

Bacterial growth measurements in treated waters from different origins. Measuring growth curves of bacteria in a drinking water gives information on the regrowth potential of the water in the pipe system. The method which was developed by Werner was used for analyzing drinking waters from different origins. As a negative control high purity water and as positive control acetate were used. It is proposed to use acetate-C-equivalents for quantification because the biodegradable part of total dissolved organic carbon (DOC) is mostly below 0,1 mg/1 in treated waters. The analyses of treated surface waters showed results from 40–80 μg/1 acetate-C-equivalents, whereas in treated waters from ground water and bankfiltrates the concentration of easily biodegradable organic carbon was between 10 and 20 μg/1 acetate-C-equivalents. This is in the region of high purity water, where in average 9 μg/1 acetate-C-equivalents are detected, which therefore is the detection limit of the method. These waters normally do not show any regrowth problems.     

Verfahren zur katalytisch-oxydativen Entsulfidierung von Abwässern

The oxidative conversion of strongly alkaline sulphide concentrations in wastewaters from the wet molybdenite enrichment is successfully performed within a relatively short time by the application of atmospheric oxygen, “Winkler adsorbent” (activated form of ash from Winkler generators) or “Winkler generator ash” and chlorinated lime at the same time. The reaction times were 60… 90 min at residual sulphide concentrations of 1… 10 mg/l. The initial concentrations of sulphide were between 400 and 1,200 mg/l. It was proved by comparative investigations that the “Winkler absorbent” or the “Winkler generator ash” have a catalytical effect during the oxidation by air. Therefore, also, e.g., at an initial concentration of sulphide of 600 mg/l only 4 g/l chlorinated lime were required, which corresponded to only about 0.13 times the stoichiometrically calculated quantity with the available chlorine content being taken into account. Flotation cells are suitable as reactors.     

Untersuchungen an Fließgewässern im Raum Leipzig

Salmonella, mainly S. manhattan and S. agona, were detected in about 40 = of the 133 flowing waters which were investigated in the District of Leipzig from June 1988 to June 1989 Possible causes of the occurrence of salmonella were discussed. Within the framework of statistical evaluations, correlation investigations were carried out on findings of chemical and biological examinations and relations found so far were confirmed. The applicability of the standard TGL 6466/01 “quality demands on irrigation water” is critically checked on the basis of the results of investigation; as derived from the result, the necessity of a revision of this TGL is proved.     

Immersionskalorimetrische Einschätzung der Adsorptionsfähigkeit von Aktivkohlen gegenüber organischen Stoffen aus wäßrigen Lösungen

In comparison with the conventional methods for testing the adsorptive capacity of active charcoals, the author presents a new technique. The measuring possibilities of the immersion calorimetry are used. This measuring technique is based on the determination of the interaction of active charcoal with liquid adsorptives. The immersion heat referred to one mol adsorptive is used as the measure. Due to simplifying assumptions and a micropore volume of active charcoal measured with water vapour, immersion-calorimetrically relative equilibrium constants can be determined. By the example of phenol and indol, the adsorptive capacity of several domestic and foreign samples of active charcoal is assessed on the basis of the difference of the immersion heats in benzene and water.     

Biologische Behandlung von synthetischen Abwässern mit Azofarbstoffen

Purification of Wastewaters Containing Azo Dyes This study describes the degradability of the azo dye C.I. Reactive Violet 5 by a continuous flow biological treatment system consisting of three rotating disc reactors. The azo dye was first decolorized in an anaerobic reactor. Decolorization was improved by adding an auxiliary substrate (yeast extract and acetic acid). Although severe operating conditions were experienced due to failures in the temperature and pH-controllers, the reactor recovered quickly and continued to decolorize reliably. The removal of the auxiliary substrate in the anaerobic reactor was not satisfactory, probably due to the copper in the azo dye. Batch experiments showed that copper was removed from the dye molecule and precipitated during the decolorization. In the continuous flow reactor, the copper precipitate on the disc can redissolve due to a pH-gradient in the fixed biomass becoming toxic again for the bacteria. In the following two aerobic reactors, the auxiliary substrate was degraded, but mineralization of the dye metabolites was insufficient. The aromatic amines produced by the anaerobic decolorization are more toxic in the bacterial luminescence test than the azo dye. Therefore, decolorization alone cannot be used to treat colored wastewater. Since the amines can also be produced in anaerobic parts of rivers, the dyes have to be removed in a more efficient way. That is the reason why in further experiments ozonation is being tested to increase the biological degradability of the azo dye for a following aerobic stage. Either ozonation can be used after the two stage treatment of the dye in anaerobic/aerobic reactors or the dye can be oxidized directly, making the addition of auxiliary substrate unnecessary. These configurations are being tested with the goal to degrade the dye with the least ozone consumption.     

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.     

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.