Kurzzeit-Toxizitätstests zur Messung der Toxizität von Chemikalien gegenüber Belebtschlamm

Short-term Toxicity Tests for the Measurement of Toxicity of Chemicals Towards Activated Sludge. To avoid severe damage to the activated sludge of a wastewater treatment plant it is necessary to control the sludge activity by means of biological test systems. Especially the short-term respiration assay and the dehydrogenase assay with resazurin as a redox-dye seem to be appropriate for this monitoring program. The practical performance of both test systems was optimized in some essential points. With the help of several reference substances both monitoring systems were tested for practical use as short-term toxicity tests. The results of the investigations showed that the inhibitory concentrations measured in both test systems were partially very different. In monitoring experiments with laboratory-scale wastewater treatment plants it could be shown that a positive correlation between respiration activity and dehydrogenase activity is not always given. Furthermore, a pH-dependent toxicity could be demonstrated for several substituted phenols.     

Grundlagen für die Dimensionierung der Belüftung bei Belebtschlammanlagen

Summary The generally accepted theory for the calculation of the oxygen consumption caused by the microbes in an aeration basin assumes that the total of oxygen utilizedq _g is the sum of the endogenous respiration of the sludgeq _e plus a quantity for substrate respirationq _s . This theory—though physiologically probably not quite correct—, is very convenient because it allows a causal calculation of the necessary oxygen input into an activated sludge plant. Extensive data on endogenous respiration of activated sludge are presented (Table 1 and 5) and are correlated with sludge load and sludge age (Fig. 4 and 5). The term substrate respiration is discussed and a calculation method, based on the removal of organic C by the mixed liquor, is proposed. In view of the fact that nitrification is an inevitable reaction in activated sludge treatment (its extent being strictly a function of the operation parameters of a plant), oxygen consumption for the oxidation of ammonia has to be included into the term of substrate respiration. The amount of this oxygen fraction has to be predicted from the degree of nitrification to be expected at the desired operation conditions. The following formula for the calculation of the oxygen input into a completely mixed aeration basin is proposed (explanations of symbols see annex): or This same calculation method may be applied stepwise for aeration basins of the tubular reactor type (longitudinal flow basins) considering the concentration decrease of the substrates along the length profile of the basin (the term for endogenous respiration can be assumed constant for the entire aeration time).

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Optimierung des Belebungsverfahrens durch Minimierung des Volumens von Belebungs- und Nachklärbecken

The separate examination of the processes of the settling and thickening of activated sludge allows us to minimize the volumes of aeration tanks and final clarification tanks. The following initial quantities are given: wastewater quantity, inflow and outflow concentrations of BOD₅, wastewater temperature and reflux ratio of activated sludge and, in addition, three parameters of the thickening behaviour of activated sludge as well as a parameter for the bioactivity of sludge, which are to be determined in an experimental plant. From this, the optimum concentration of the activated sludge in the aeration tank is calculated at which the total of volumes for aeration tank and final clarification tank becomes a minimum. The process is carried out numerically by an example.     

Dimethylsulfoxidreduktase-Aktivität Charakterisierung der mikrobiellen Biomasseaktivität im Schlamm einer belüfteten Abwasserteichanlage

Dimethyl Sulfoxide Reduction Method for the Characterization of Biomass Activity in Sludge of an Aerated Lagoon The microbial biomass activity was studied in sludge from a wastewater lagoon (Hatzbachtal) which consisted of 4 aerated ponds and one polishing pond. The lagoon was characterized by low BOD₅ loading and high dilution because of water from the surroundings. Sludge samples were taken from 4 sampling sites of each aerated pond and from one site of the polishing pond. The biomass activity in the sludge samples was analysed with the help of dimethyl sulfoxide reductase (DRA) and dehydrogenase (DHA) activity. In addition, C_org-content was also determined. The effect of different reaction parameters on the DRA was studied in relation to incubation period, temperature and atmosphere as well as sludge weight and pH value. The results presented here show that a linear increase in the DRA occured for the sludge weight ranging from 0.1 to 0.5 g, incubation period from 0.5 to 11 h and incubation temperature from 20 to 50 °C. The pH spectrum from acidic to neutral did not effect the DMS formation in sludge. Although the values for DRA were always higher in anaerobic incubation of sludge than in aerobic incubation, the courses of the DRA in both conditions were parallel. Comparing the biomass activity in sludge from different sampling sites of the aerated ponds, the average C_org-content was found to be reflected by the DRA and DHA. Further, the variation in the DRA could represent also the influence of oxygen concentration. Therefore, a reduction in biomass activities indicated a decline in the availability of oxygen.     

Bestimmung der Aktivität von Belebtschlamm über die Geschwindigkeit der Biosynthese von Aminopeptidasen

The authors describe a possibility of a fast determination of the metabolic activity of various activated sludge samples. There is not used the sludge property of digestion, but the biosynthesis of aminopeptidases. Egg albumin has been found to be the optimum standard indicator. The activity of the investigated activated sludge is derived from the rate of the biosynthesis of aminopeptidases. The technique proposed can be used also for determining the toxic effects of different substances on activated sludge.     

Vergleich ausgewählter Elutionsverfahren zur Beurteilung der Mobilität von Metallen

Comparison of Selected Elution Procedures for the Valuation of the Mobility of Metals from Sediment and Sewage Sludge Several methods of extraction are generally used to evaluate environmental or ecological toxicity and deposition of waste material. In this paper, the application of the German standard methods DIN 38414-S7, DIN 38414-S4, pH_stat method, “Schweizer method” (elution test, Switzerland), and some variants of the pH_stat method on two very different samples are described. A rudimental sediment and a municipal sewage sludge are chosen as sample materials. The metal contents of extract solutions are determined by ICP-OES. The results of the DIN-S4 extractions depend definitely on the mechanic way of movement, i.e. the amount of heavy metals which are mobilized out of the samples differs considerably. In fact, DIN-S7 in combination with DIN-S4 is not sufficient to estimate the mobility of heavy metals. Solid samples should only be evaluated by applying a combination of several methods of extraction. The usefulness of the pH_stat method for an evaluation is discussed.     

Biologisch-chemisches Verfahren zur Prüfung des Abbau- und Eliminierungsverhaltens organischer Abwasserinhaltsstoffe

After the checking for the toxic inhibition of degradation, the testing of the degradation behaviour at concentrations below the toxicological threshold value should be performed. For this, activated sludge with 1.5 … 2 g/l organic dry weight in special reaction vessels with a stirring and aeration equipment as well as electrochemical oxygen measurement is used. The possibly necessary adaptation is effected by a repeated change of the aqueous phase with the test substance as the single carbon source. Measurements are carried out in three vessels: control, experimental vessel and another experimental vessel for the makeup of volume at sampling. The increase of biomass and the consumption of substrate are determined from samples. Determinations of totals as COD and/or C_organic are recommended, since the determination of the pure substrate allows only statements on the persistence, but not on the full degradation. The technique, represented with the schematic diagram and examples of application, can be automated easily.     

Schwermetallbestimmung in Klärwerksschlämmen mittels Röntgenfluoreszenzanalyse

The X-ray fluorescence analysis is an important means for the determination of the heavy metal concentrations in sewage sludges and for the evaluation of their usability in agriculture. Analysis devices from the GDR were used for that. For the investigations there was used as the zero sample a sludge which was not loaded with heavy metals, homogeneous and constantly dried at 105 °C. The drying bed sludge samples were treated with different heavy metal solutions with different concentrations. Preparation of samples, measuring conditions and general spectra are described. The measuring results of tests up to 100 g heavy metal in 1 kg dry substance are critically evaluated. The analysis of a sewer sludge sample takes only about ten minutes. There are determined: Cr, Ni, Cu, Zn, Mo, Cd, Hg and Pb.     

Treatment of Malting Wastewater in a Granular Sludge Sequencing Batch Reactor (SBR)

Aerobic granular sludge was successfully cultivated in a sequencing batch reactor (SBR) treating wastewater from the malting process with a high content of particulate organic matter. At an organic loading rate of 3.2 kg/(m³ d) COD_total and an influent particle concentration of 0.95 g/L MLSS an average removal of 50% in COD_total and 80% in COD_dissolved could be achieved. A comparison of granular and flocculent sludge grown under the same operating conditions showed no significant difference in removal efficiency although granules exhibited a higher metabolic activity in terms of specific oxygen uptake rate (r_{O2, X}). Two distinct mechanisms of particle removal were observed for granular sludge: during initial granule formation, particles were incorporated into the biofilm matrix. For mature granules, a high level of protozoa growth on the granule surface accounted for the ability to remove particulate COD. Combined evaluation of the development in MLSS content and sludge bed settling rate (i.e., mean derivative of the normalized sludge volume) was found to be an adequate method for monitoring the characteristic settling properties of a granulizing sludge bed. By means of this method, a distinct substrate gradient out of several operating conditions was concluded to have the biggest impact on the formation of aerobic granular sludge.     

The Influence of the Concentration of Dissolved Oxygen on the Determination of the Dehydrogenase Activity of Activated Sludge Using the Method of TTC Test

Due to its oxidation-reduction potential, oxygen occurs in the TTC test for the determination of the dehydrogenase activity as a competitive hydrogen acceptor. At different oxygen concentrations in the solution to be tested and also at varying rates of oxygen depletion, e.g. in activated sludge samples, thus the formazan formation from TTC shows differences. Under similar anaerobic conditions, the test results of the dehydrogenase activity are higher in most cases and show a smaller range of variation than under aerobic conditions. The importance of the oxygen concentration is demonstrated in investigations with activated sludge, anaerobic conditions being set by addition of Na₂SO₃.     

Untersuchungen zum Abbau von Pharmaka in kommunalen Kläranlagen mit HPLC-Electrospray-Massenspektrometrie

Examination of the Degradation of Drugs in Municipal Sewage Plants Using Liquid Chromatography-Electrospray Mass Spectrometry Numerous drugs can be identified in the secondary effluent of municipal sewage plants. In order to obtain information about the degree of elimination (adsorption, aerobic degradation) of these compounds, a batch reactor containing different drugs in environmentally relevant concentrations and a suspension of activated sludge was coupled to a HPLC-MS-MS system. During a testing period of three days concentration-time-curves were recorded. For most of the examined drugs (acetamidoantipyrine, crotamiton, diclofenac, primidone, propyphenazone) solely a strong decrease of the initial concentration within the first 15 minutes was observed, which was interpreted primarily as adsorption to the activated sludge. For acetaminophenol and pentoxifyllin an additional slower decrease in concentration within several hours was observed. This slower elimination was interpreted to be caused mainly by primary degradation. It could be shown that dihydrocodeine is oxidized to hydrocodone in the batch reactor. The conjugate acetaminophen glucuronide was cleaved.     

Biodegradation of Nonylphenol Ethoxylate Surfactants in Biofilm Reactors

The primary degradation of a technical nonylphenol ethoxylate surfactant with an average chain length of 10 ethoxylate units (NPEO‐10) was studied in a flow‐through system by means of miniaturized biofilm reactors (mBFR) with bacteria from an activated sludge plant. 5 mg/L of the test compound (total EO concentration) were spiked in synthetic wastewater (SWW) and fed to the reactors continuously for 64 days. Compound removal and the formation of degradation products (DP) were monitored under both oxic and anoxic conditions. Solid‐phase extraction and RP‐HPLC with fluorescence detection were employed for sample preparation and analysis. Better removal of the parent compound was seen with the oxic reactors (50 to 70%) than with the anoxic reactors (30 to 50%). Compared to SWW organic matter, the test compound proved to be of refractory nature. The appearance of degradation products in the effluent was earlier with anoxic reactors despite their lower elimination efficiency. After extraction of biomass only minor amounts of NPEO‐10 and metabolites were found, indicating that small amounts were present in adsorbed or intracellular form. Ultimate biodegradation of NPEO‐10 and of octylphenol ethoxylates (OPEO‐9.5; average chain length of 9.5 EO units) was tested by means of manometric respirometry at a theoretical oxygen demand (ThOD) of 100 mg/L. Whereas NPEO‐10 was biodegraded by only 26%, at best, in 28 days, OPEO‐9.5 degradation amounted to (40 ± 5)%.     

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?).     

Auswahl der Inkubationszeit bei Bestimmung der Belebtschlammaktivität mit Hilfe des TTC-Tests

The general assumption that the quantity of the formazan formed is linearly proportional to the time of incubation cannot be confirmed in practice. A formation of formazan which is too low initially is due to the initially passive transport of TTC to the sites of action. A formazan formation which is initially very high occurs through non-enzymatic reduction of TTC by reducing substances in the environment outside the bacterial cells. During longer periods of incubation, especially during toxicological tests, the substrate may get exhausted, so that less formazan will be formed. For the correct determination of the dehydrogenase activity by means of TTC it is necessary to determine the period of incubation within which the increase of formazan is linearly proportional to time. The dehydrogenase activity can be exactly determined only from this period of time of incubation.     

Simulation von Variablen der Fließgewässerqualität mittels Mehrfachregressionen

There are investigated the variables O₂, BOD₅, seston, NO₃-N, NH₄-N and o-PO₄ from at least five-year series of five stations along a river section of 50 km. After exclusion of a linear trend and substraction of the individual monthly mean values from the monthly mean of many years in order to eliminate the effect of the annual variation as well as testing for normal distribution, first the correlation coefficients of the variables to the flow rate Q and the temperatures of air and water are determined, which show directional changes just in the longitudinal profile of the river. The same holds for the correlation of the variables between the measuring points. From this the model structure is derived, according to which the concentration at one measuring station can be simulated by multiple regression to Q and T at the same level as well as the concentration at the upper level. The results are discussed in detail and evaluated with respect to their inclusion in longterm management models of water quantity management.     

Nährstoff- und Sauerstoffbilanz eines hochbelasteten Klärwerksableiters unter besonderer Berücksichtigung der submersen Makrophyten

Nutrient and Oxygen Balance of a Highly Polluted Treated Sewage Channel with Special Regard to the Submerged Macrophytes The changes of the concentrations of inorganic nitrogen compounds, orthophosphate, and oxygen were measured in the flowing wave along the flowing stretch of the Berlin treated sewage channel Wuhle monthly over a period of two years (1993/94) to estimate the nutrient and oxygen balances. This treated sewage channel is rich in nutrients and densely covered with submerged macrophytes. During the period of investigation in 1993 (1994), the effluent of the sewage treatment plant Falkenberg, which is lacking in adjustable nitrification and denitrification. contained in average 16.1 (12.7) mg/L of NH-N, 13.7 (9.4) mg/L of NO₃^?-N. 0.94 (0.69) mg/L of NO-N. and 0.36 (0.26) mg/L of PO-P. Due to the neglectable influence of other processes like nutrient uptake by submerged macrophytes and algae, desorption of ammonia or dilution, the changes of the concentrations of the inorganic nitrogen compounds are mainly influenced by nitrification and denitrification. The nitrification is mainly done by sessile nitrifiers in the treated sewage channel Wuhle. The nitrification rates. calculated from the decrease of the ammonium concentrations, were between 0.5 and 20 g/(m²d) related to the flowing stretch area. The ammonium concentrations decreased along the flowing stretch in average by 20 to 44%. The highest nitrification rates could be found at the stretches with a dense colonization with submerged macrophytes and a good oxygen supply due to low water depth and high flowing velocities. The denitrification rates, calculated from the decrease of the total of the concentrations of the inorganic nitrogen compounds, were between 0.5 and 23 g/(m²d) related to the flowing stretch area. The total loss of nitrogen due to denitrification was between 10 and 20% along the flowing stretch of the treated sewage channel Wuhle. This corresponds to a total amount of up to 530 kg nitrogen per day. The main part of the phosphorus occured as orthophosphate in concentrations between 0.04 and 0.87 mg/L of PO-P in the effluent of the treatment sewage plant Falkenberg. The orthophosphate concentration changed along the flowing stretch mostly in such a manner that it were at the same level at the end of the flowing stretch at the mouth into the river Spree. The self-purification capacity of the channel does not lead to a relevant reduction of the very high nutrient load under the present conditions. The rates of the photosynthetic production (P) and the community respiration (R) were calculated from the rates of the total changes of oxygen with regard to the physical aeration. The rates of the photosynthetic production were between 0 and 33 g/(m²d), the rates of the community respiration between 15 and 75 g/(m²d). Therewith, the Wuhle treatment sewage channel belongs to the very productive waters. A positive balance (P > R) could only be measured on two segments in May. The rates of oxygen production depend on the ratio width to depth of the water. It is possible that the positive influence of the submerged macrophytes on the oxygen balance also at higher biomasses than 250 g/m² (as dry weight) predominates at the segments with a favourable ratio. The portion of the oxygen input through diffusion along the flowing stretch and at the weirs was 30%, respectively, that of the photosynthic production 40% in summer. The rates of community respiration decreased along the flowing stretch by 50 to 90%. The nitrification had the main portion of the oxygen depletion in the Wuhle treated sewage channel with 60…80%. Despite the high biomass, the respiration of the submerged macrophytes had only a small portion of the total oxygen depletion. Nevertheless, the submerged macrophytes contributed to the nearly total oxygen depletion at the most densely covered segment 2 at night. The decrease of the content of particular organic material and the ammonia concentrations at the effluent of the sewage treatment plant, a diminishing of the biomass of submerged macrophytes by shading, and the widening of a few flowing stretches are demanded for the improvement of the oxygen balance of the Wuhle treated sewage channel.     

Abschätzung und Beeinflussbarkeit der Arsenmobilität in kontaminierten Böden

Assessment and Modification of Arsenic Mobility in Contaminated Soil Arsenic concentration in the seepage of contaminated soils of an old tannery site is assessed using batch and column experiments. The effect of reducing conditions, pH, and ionic strength is also investigated. The iron oxide rich subsoil (C‐horizon) is the main source of groundwater pollution with arsenic. In this horizon, mobilization can increase as a result of reducing conditions upon periodical water saturation. Therefore, the potentially mobile arsenic is determined by a reductive dissolution of the poorly crystalline iron oxide fraction using 0.1 M ascorbic acid. Arsenic concentration can be reduced from 100 μg/L to below 20 μg/L by an increase of ionic strength (e.g. by a 0.01 M CaCl₂ solution). Arsenic contaminated soils should be limed regularly in order to maintain the highest possible calcium concentration in the soil solution.     

Untersuchung des biologischen Abbaus von polycyclischen aromatischen Kohlenwasserstoffen in einer Labor-Kläranlage

Study of the Biological Degradation of Polycyclic Aromatic Hydrocarbons in a Laboratory-scale Plant A one-stage laboratory-scale wastewater treatment plant composed of a bubble column reactor with sedimentor and sludge recycle is fed with an oil/water emulsion from a contaminated site. The oil phase is highly contaminated with polycyclic aromatic hydrocarbons (PAH). The samples are taken regularly at defined points of the treatment plant (influent, reactor, return sludge, effluent). The analysis of PAH is performed by HPLC. We can show that all analysed PAH including the poorly degradable carcinogenic substances such as benzo[a]pyrene are biologically transformed. Additional measurements of the toxic and mutagenic potential of the wastewater show that in the laboratory-scale plant full removal of the carcinogenic potential is not achieved. This is due to the fact that during the biological transformation of higher condensated PAH mutagenic dead-end metabolites are produced.     

Einfluß einiger Umweltfaktoren auf die N2O-Bildung durch Belebtschlamm unter anoxischen Bedingungen Influence of Some Environmental Conditions on N2O-Release by Activated Sludge under Anoxic Conditions

The release of nitrous oxide during denitrification in activated sludge is influenced by various environmental factors. Experiments with different electron acceptors showed that under anoxic conditions increasing concentrations of nitrate as well as nitrite enhance the production of N₂O. The N₂O concentration in the gas phase increases for 2 h, then decreases. Nitrite causes a higher release of N₂O than nitrate. Acetate in high concentration can stimulate N₂O-release. Without addition of acetate nitrate and nitrite reduction are delayed, and hence N₂O-release and consumption are much slower. In activated sludge sulfide can play a role as an inhibitor of the nitrous oxide reductase (like in soil and pure cultures), but is inactivated very rapidly. Repeated addition of sulfide can cause a new release of nitrous oxide. At low pH (less than 6.5) denitrification is slightly inhibited and N₂O-release is 100 times higher than at pH 7.0 to 8.0. Under oxygen-limiting conditions N₂O-release and denitrification starts at 0.5–1.0 mg/L DO, but it is not always accompanied by accumulation of nitrite. Further reduction of the oxygen concentration reduces N₂O-release.     

Biochemische Abbaubarkeit ausgewählter alicyclischer Verbindungen

Thirteen alicyclic compounds (C₅… C₇) are examined for their biochemical degradability in a laboratory activating tank and in two respirometers (Warburg, Sapromat). The tests were performed with adapted and nonadapted activated sludge. In addition, the COD was determined by three different methods. With the exception of cycloheptane (BOD < 25% of the BOD_theor.), six compounds prove to be easily degradable (BOD > 45% of the BOD_theor.) and six compounds prove to be degradable (BOD 45… 25% of the BOD_theor.).