Verfahren zur Nitrateliminierung im Gewässer

In a storage reservoir with a hypolimnic volume of 3.5 hm³ the water contains 40 mg/l nitrate. A straw bale of 60 by 20 by 1.5 m was introduced as a reactor. Hypolimnic water having been polluted with a waste product of the fatty acid synthesis (30 … 20% formic, acetic, propionic, butyric and valeric acids) were pumped through it. By the use of a total of 43.8 t fatty acid mixture from June to August an additional oxygen depletion of 14 t O₂ is achieved and 49 t NO₃^? are removed at the same time. The ammonium concentration did not increase, the NO₂^? concentration, however, rose to 12 … 13 mg/l NO₂ at times. The fatty acids were used up save 0.1 mg/l. The increase of the NO₂^? concentration, of the number of germs and of the iron, manganese and phosphorus back solution due to the controlled anaerobic conditions is the drawback of the process.     

Die gaschromatographische Bestimmung von freien flüchtigen Fettsäuren (C2 — C6) im Sickerwasser von Hausmülldeponien

After extensive experiments aimed at determining the free volatile fatty acids (C₂ to C₆) in organically highly polluted percolation water of household refuse dumping places there proved optimum a column packed with 10% Carbowax 20 M on Chromatron N-AW-DMCS after having been conditioned for five days at 270°C and subsequently covered with 10% hard wax. On short retention times the investigated isomeric column pairs are completely separated. Equally favourable results were obtained also for liquid manure and silage extracts. The detection limits lie between 10 and 20 mg/l, the relative standard deviation is 20 … 30% in the range of the lower detection limit and 2 … 3% at 200 mg/l in the upper range. In the investigation of percolation waters with concentrations between 235 and 4300 mg/l reproducibility lies at a mean relative standard deviation of 0.5 … 2.8%. The technique is well suited for routine checking.     

Hydrochemische Ergebnisse zur Aufbereitung stark belasteter Oberflächenwässer und Uferfiltrate mit Kalkhydrat. Teil 2

Continuing the first part on this subject, the results of precipitation experiments are described by the example of the removal of humic acid and lignosulphonic acid. Moreover, to increase the number of process variants and in accordance with process methods after Haberer, there is proposed a two-stage chemical treatment, inter alia. According to the latest findings, already at the first stage a metallic salt dosing should be done, so that the purification effect can be improved. This new technique, termed “combination stage flocculation”, is based on new findings concerning the solubility behaviour of aluminium compounds at higher pH-values in the presence of magnesium salts, when slightly soluble aluminium-magnesium double hydroxides originate.     

ClT-3 — ein neues Gerät für die Chloridbestimmung in der Wasseranalytik

The device is used for the coulometric titration of chloride with electrolytically generated silver ions and biamperometric end-point indication via a second pair of silver electrodes. The device consists of the external measuring cell with the generator- and indicator-electrode systems and a magnetic stirrer as well as the titrator proper, which contains all electric and electronic components for the realization of the course of measurements up to the digital display of measured values. Four modes of operation can be chosen with the units mmol/1 Cl^? or mg Cl^? in 100 ml sample and sample volumes of 50 μ and 200 μl the compensation of systematic dosing errors or the taking into account of constant matrix effects being possible by means of a steplessly adjustable correction factor between 0.95 and 1.05. The measuring range is 25 … 2,000 mg/1 Cl^? with variability coefficients between 0.3 and 3% if a microlitre pipette with a PE pipette tip is used. An even lower variability of the results can be expected from an improved sample dosing Disturbances caused by ions subject to electrolytic redox processes were detected (Fe, S^2?, CrO₄^2?).     

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.     

Einsatzmöglichkeiten von Membranprozessen zur Beseitigung organischer Substanzen aus natürlichen Wässern

Membrane-filtration or dialysis techniques are increasingly used for the partial desalting of waters, e.g. brackish waters. By the use of Bulgarian PAN and acetate-cellulose separating membranes there are eliminated also organic substances – inclusive of humic matter – from natural waters to different degrees. The experimental arrangement is described and the measured results for COD-Mn, concentrations of humic acid and specific electrolytic conductivity are summarized in tables. The humic acid concentration (2.8 mg/l) was reduced by about 79 % by ultrafiltration, 82 % by reverse osmosis and 62 % by electrodialysis. The efficiency of the investigated techniques could be increased under certain conditions.     

Die Massenentwicklung der Geißelalge Uroglena americana (Alk.) Lemm in Trinkwassertalsperren Thüringens und ihre Bekämpfung

A mass development of Uroglena americana with cellular densities of up to 13.5 · 10⁶ and 86.10⁶ cells/l, was observed in two drinking-water reservoirs. In the first case the development remained confined to the upper 20 m, in the second case there occurred a gradual shift of the maximum to deeper zones from May to July with decreasing cellular densities down to a depth of 35 m. Laboratory experiments for the control of the algae development were performed in order to protect the drinking-water resources from potential impairments of odour and taste. Samples of the storage-reservoir water with 20.10⁶ cells/l of Uroglena were concentrated up to 1.25 … 12.5 mg/l Ca(OH)₂ (pH-values of 7.2 … 9.6) by addition of calcium hydroxide and observed for 39 h. First impairment of the cells of Uroglena is detectable at 5 mg/l Ca(OH)₂ after 15 h, an immediate effect can be observed at 7.5 mg/l Ca(OH)₂ together with increased sedimentation, also Gymnodinium and Cryptomonas having been damaged. Thereupon a successful control of Uroglena by liming up to pH-values above 8.0 is possible. The application of lime to outdoor areas was not necessary, in the final analysis, since the drinking-water quality could be secured by the optimum choice of the intake depth of raw water with a maximum of 4.10³ to 77.10³ cells/l.     

Die Entfernung von Thiocyanationen aus wäßrigen Lösungen unter Verwendung stark basischer und schwach basischer Anionenaustauscher

After treatment of the anion exchanger resins from several manufacturers with FeCl₃ or CuSO₄ their capacity to take up thiocyanate ions increases by the factor 2 … 3. By regeneration with diluted sulphuric acid or hydrochloric acid after precipitation of the ferric or cupric hydroxide a thiocyanate solution of 10 and 15 g/l, respectively, is obtained, which can be reused. The hydroxides dissolved in acid are used for the treatment of the ion exchanger. The process is proposed for the regenerating of wastewaters containing thiocyanate.     

Zur Analytik von Chlorphenoxyalkansäuren und Chlorphenolen. Teil 2: Nachweis von Chlorphenoxyalkansäuren und Chlorphenolen in der Fischgalle

The bile liquid is preserved with ethanol and the protein is precipitated. Prefractionating is done by liquid-liquid extraction by chloroform and ethyl acetate. The extracts are column-chromatographically separated on Florisil and subsequently detected by thin-layer chromatography. For determining the identity of substances, the penta fluorobenzyl derivatives are prepared and chromatographed under the same conditions. Detection is carried out with the aid of ammoniacal silver nitrate reagency and ultraviolet irradiation. The highly polar conjugates of chlorophenoxyalkane acids and chlorophenols which are present in the bile are cracked by acid hydrolysis and then cleaned by re-extraction. In this way, 2, 4-D, MCPA, MCPP, 2,4-dichlorophenol and 2-methyl-4-chlorophenol were detected from Salmo gairdneri. 6… 21 d after the application of the herbicides in the catchment area their concentration in the fish bile amounted to about 200 mg/l, 90% of them having been conjugates. Thus, the biliary excretion of xenobiotic substances offers an important new aspect of biomonitoring by means of fish tests, especially in the range of subacute and chronic toxicity.     

Einsatz einer konstruierten Mischkultur zur Verwertung von Mischsubstraten mit inhibierend wirkenden Substanzen

By way of introduction the general fundamentals and kinetic setups of the competitive and non-competitive as well as substrate inhibition of cultures of microorganisms are stated. Investigated on a laboratory scale is the degradation of liquid pig slurry in a 600-1 stirring fermenter with discontinuous addition (pO₂≧=30 = saturation) of methanol as external substrate by a yeast mixed culture of Metschnikowia and Pichia membranifaceans to utilize the steam-volatile fatty acids (12 g/l) and of Acetobacter methanolicus to utilize methanol. A stable fermentation with stable residual concentrations of 235 mg/l fatty acids, 142 mg/l mH₄-N an 100 … 300 mg/l methanol for aperiod of 2400 h can be achieved.     

Immunotoxicity of the xenoestrogen 4-nonylphenol to the cockle Cerastoderma glaucum

The in vivo effects of 4-nonylphenol (NP) on functional responses of haemocytes from the cockle Cerastoderma glaucum were investigated after 7 days exposure to sublethal NP concentrations (0, 0+acetone, 0.0125, 0.025, 0.05 and 0.1 mg/l NP). Haemocytes from both controls and exposed cockles were collected, and the effects of NP on total haemocyte count (THC) and volume of circulating cells, intracellular superoxide anion (O(2)(-)) levels, acid phosphatase and lysozyme-like activities in both haemocyte lysate (HL) and cell-free haemolymph (CFH) were evaluated. Exposure of cockles to 0.1mg/l NP significantly increased THC (p<0.05) with respect to controls. Analysis of haemocyte size frequency distribution showed that the haemocyte fraction of about 7-8 microm in diameter and 250 femtolitres in volume increased markedly in cockles exposed to the highest NP concentration tested. Apoptosis resulting in cell volume reduction in NP-exposed animals cannot be excluded. No statistically significant variation in intracellular O(2)(-) levels was observed. Conversely, significant increases (p<0.05) in acid phosphatase activity were observed in CFH from 0.05 and 0.1mg/l NP-exposed animals; no significant differences in enzyme activity were recorded in HL. Lysozyme-like activity also increased significantly in CFH from cockles exposed to 0.05 mg/l NP (p<0.05) and 0.1 mg/l NP (p<0.001). Instead, lysozyme-like activity decreased significantly (p<0.05) in the HL of animals exposed to 0.05 mg/lNP. Our results suggest that NP induces variations in the functional responses of haemocytes of C. glaucum, mainly by reducing cell membrane stability and promoting cell degranulation.     

Beeinflussung der Enzymaktivität einer Protease durch Huminstoffe Influence of Humic Substances on the Activity of a Protease

This paper deals with the influence of different humic substances (HS) on the enzyme activity (EA) of the proteolytic enzyme pronase E. The EA was determined by analyzing the concentration of the amino acid valine hydrolyzed from caseine. For amino acid analysis, a flourescence detector was used after precolumn derivatization and HPLC-separation of the hydrolysis products. The data show that the presence of HS has no adverse effects on amino acid analysis. Based on this result, a decrease of EA was observed in the presence of HS acting as enzyme inhibitors. Clear inhibition effects could be seen for different fulvic acids (HO3 FA, FBR FA and FBR 1.0 FA) at concentrations of 150 mg/L. In case of FBI-2 FA, higher concentrations were necessary to decrease the EA significantly. At an inhibitor concentration of 1500 mg/L the EA was mostly found to be less than 50%. The standard deviations of the results don't allow a differentiation between the HS of different origin and treatment. Specifying HS according to their influence on EA has to remain uncertain. As shown in a kinetic study of the hydrolysis of L-Leucine-2-naphthylamide-hydrochloride, the inhibitor HO3 FA decreases the maximum velocity of the reaction but has no effect on the Michaelis constant. These results indicate that this HS acts as a noncompetitive inhibitor.     

Polarographische Bestimmung von Schwermetallen im Klärschlamm

The differential-pulse polarography (DPP) and the stripping voltametry (SV) are investigated in detail with respect to their suitability for the quantitative detection of individual traces of heavy metals in sewage sludge. The results are checked on the basis of AAS analyses and by the standard-addition method. From the hydrochloric-acid extracts of fused sludge samples down to 1 μg/l can be detected by the SV, whereas the DPP reaches a sensitivity of 100 μg/l. The following basic electrolytes are used: Zn: 2 … 3 mol/l H₃PO₄; Cu: 0.4 mol/l K₂CO₃, 0.2 mol/l Na-K-tartrate, 0.1 mol/l HCl; Ni: 1 mol/l NH₄OH, 1 mol/l NH₄Cl, 25 ml/l triethylamine; Pb and Cd: 0.1 … 0.2 mol/l HCl.     

Zur Schlußreinigung konzentrierter Zuckerfabrikabwässer

The most important measure is that the freshwater demand of 0.5 m³ per t beet processing is strictly kept to or fallen below, to which a catalogue of measures with ten points is presented. The wastewaters which cannot be used again have to be stored prior to the final purification in order to compensate for quantities and concentrations, aerated storage ponds being successful for small sugar factories as the purification technology. For this, three cases are described as examples: supplementary equipment of two anaerobic ponds with a rod-roll aeration, by which within two months (May to July) the BOD₃ is reduced from 1,200 to 11 mg/l. The aeration of a pond of 12.5 ha (370,000 … 500,000 m³) by means of a centrifugal aerator (45 kW) does not lead to completely aerobic conditions: Accumulation up to 350 t BOD₅, 200 t organic acids at a reduction of 100 t sulphate, 45 t of which being converted via sulphides by photoautotrophic sulphur bacteria. This combination of anaerobic and aerobic processes is very economical. At aeration with ca. 1 W/m³ in the third case in summer there are achieved wastewater loads which are of a receiving-water quality.     

Die gaschromatographische Bestimmung von Diethylentriaminpentaessigsäure in Oberflächenwasser

Gaschromatographic Determination of Diethylenetriaminepentaacetic Acid in Surface Water. A method for the determination of diethylenetriaminepentaacetic acid (DTPA) is reported. The determination is based on the preconcentration on a strong base anion exchange resin, esterification with n-propanol and following gaschromatographic separation using a N-selective detector. The sensitivity of the method, including enrichment, is 1 μg/L in river water. The identity of DTPA in river water was proved by mass spectrography. The method can be used also for the quantitative determination of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetic acid (CDTA) and ethyleneglycolbis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid (EGTA). The method was used to examine river water. An investigation along the river Rhine, taking grab samples from January and february 1992 showed that DTPA was present in some sampling places in similiar concentrations as NTA and EDTA.     

Human‐induced sedimentation patterns of a channelized lowland river

Channelization of the severely polluted Odra and Vistula Rivers in Poland induced intensive accumulation of fine‐grained deposits rich in organic matter and heavy metals. These sediments have been identified in vertical profiles in a narrow zone along river banks both in groyne‐created basins and on the floodplain. Grain size, organic matter, zinc (Zn), lead (Pb), copper (Cu) content and cesium‐137 (¹³⁷Cs) was used for sediment dating and, stratigraphy and chemistry have been diagnostic features for these deposits, named industrial alluvium. In the most polluted river reaches stabilized by bank reinforcements and groynes, 2‐m‐thick slack water groyne deposits are composed of uniform strata of polluted silts with organic matter content over 10%, Zn content over 1000 mg/kg and average Cu and Pb over 100 mg/kg. The average rate of sediment accretion in groynes is higher than on the floodplain and reaches 5 cm/yr. Stratification which appears at higher levels in the groyne fields and on the levees reflects a change from in‐channel to overbank deposition and is typified by dark layers separated by bright, sandy, and less polluted strata. Stratified, 4‐m‐thick, sediment sequences have been found in groyne fields of incised river reaches. The average rate of sediment accretion in these reaches is of the order of 5 cm/yr. In stable and relatively less polluted river reaches, vertical‐accretion organic deposits are finely laminated and the average rate of deposition amounts to a few millimeters per year. Investigations indicate that groyne construction favors conditions for long‐term storage of sediments at channel banks. For this reason, groynes should be considered as structures that efficiently limit sudden release of sediment‐associated heavy metals stored in channels and in floodplains of the historically polluted rivers. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Zum Leistungsvermögen makroporöser Adsorberpolymere bei der Elimination organischer Mikroverunreinigungen

In laboratory experiments the adsorption of eleven different organic substances in water is individually tested in the range of concentration of 0.2… 5.0 mg/l on EP 60 and EP 61 (styrene-divinylbenzene, non-polar) and EP 62 and Y 59 (acrylic-acid-ester-divinylbenzene, polar). In batch experiments the elimination at 1… 2 g/l adsorber quantity was 35… 80%, strongly dissociated anionic substances as benzoic acid being adsorbed only to a low degree and weakly cationic and undissociated substances being adsorbed well. Within a homologous series adsorption increases with the molar mass until the pore diameter will become too small for the taking up of substances. Under dynamic conditions (filtration technology) an elimination of 90… 100% can be expected. As a whole, the adsorption on activated carbon was better in all cases than the adsorption on the polymers. The desorption for the regeneration of the polymers is the more difficult the better the substance contained is adsorbed. By repeated loading and regeneration only a slight influence on the adsorption and desorption of a substance was found.     

Auswirkung von Schwermetallgemischen auf die biologische Behandlung naphthalinsulfonsäurehaltiger Abwässer

Effect of Mixtures of Heavy Metals on the Biological Treatment of Sewages Containing Naphthalenesulfonic Acid Biological wastewater treatment processes can be destabilized considerably by heavy metals. In this investigation, the effect of loadings of heavy metals on the degradation of naphthalene-2-sulfonic acid (2NS) by immobilized bacteria in continuously operated airlift-loop reactors was studied. Shock loadings with mixtures of cadmium and nickel, or cadmium and zinc, respectively, resulted in increases in inhibition compared to those observed with the single metals. In contrast, the 2NS-degradation was less inhibited by shock loadings with mixtures of nickel and zinc than by the single metal ions. Repeated shock loadings up to 100 mg L^?1 nickel and 1000 mg L^?1 zinc effected an adaptation of the microorganisms. Continuous loadings with up to 10 mg L^?1 cadmium and nickel each, or with 50 mg L^?1 nickel and 210 mg L^?1 zinc, respectively, did not inhibit the degradation of 2NS. The permanent loadings led to an adaptation of the bacteria with an increased biosynthesis of proteins from 0.2 to 0.5 g g^?1 cell dry weight. However, if the immobilized cells were incubated with mixtures of cadmium and nickel, the specific polysaccharide content decreased to less than 0.2 g g^?1 cell dry weight, resulting in a detachment of the biofilms.     

Zur akuten Toxizität von Trichlorfon gegenüber ausgewählten Wasserorganismen

Two different formulations of Trichlorfon were examined for their acute toxicity in laboratory tests. Cyprinus carpio L., Salmo gairdneri Rich. and the fish food organisms Cyclops spec., Diaptomus spec. and Chironomus spec. were used as test objects. The differences in toxicity between crystalline and technical Trichlorfon were not very large. The recorded lethal concentrations are summarized in graphical representations and tables. After exposure for several hours to lower concentrations of active constituents, the toxicant-damaged fishes regained their original activity of life during a subsequent phase of recovery Tests of fish food organisms with 100 … 200 μg/l Trichlorfon led to death within 48 hours. Also on chironomid larvae Trichlorfon has a lethal effect at 0.2 mg/l within 48 hours. Toxicity is increased by the hardness constituents of the water. As experiments conducted with Crustacea have shown, growth is inhibited only at a certain concentration in the body.