Chlorphenole und Nonylphenole in Klärschlämmen. Teil I: Vorkommen in Klärschlämmen westdeutscher Kläranlagen aus den Jahren 1987 bis 1989

Chlorophenols and Nonylphenols in Sewage Sludges. Part I: Occurence in Sewage Sludges of Western German Treatment Plants from 1987 to 1989 Sewage sludges originating from all western German states from 1987 till 1989 have been analyzed for two groups of organic pollutants, which are not specified in the German sewage sludge regulations (Klärschlammverordnung) from 1992: the isomeric 4-nonylphenols and the chlorophenols. The applied analytical methods are presented, as well as the analytical results. In almost all 149 analyzed samples nonylphenols could be found, at an average of 128.2 mg/kg dry matter. In the case of chlorophenols, pentachlorophenol was the most pronounced in respect to amount and to frequency of positive results: i.e. in 85 samples investigated, the mean value was 59.5 μg/kg. Results are reported in percentils. The data correspond to sewage sludges from the past and will be used as a guideline in evaluating all following studies of sludges. Investigations will be continued.     

Polarographische Bestimmung von Nickel und Chrom in Klärschlämmen Polarographic Determination of Nickel and Chromium in Sewage Sludge

The contents of Ni and Cr in sewage sludge with high and low amounts of heavy metals were investigated by polarography. The DIN-digestion (aqua regia) was used, and the resulting solution was treated with H₂O₂/UV (90 °C, 60 min) for further destroying of the organic material. Besides, the solution of the DIN-digestion was examined with AAS (flame) and ICP-OES. With the determination of Ni it was shown that after digestion with aqua regia no further treatment with H₂O₂/UV is necessary. Contrariwise it was found that for the determination of Cr a H₂O₂/UV photolysis is necessary followed by further steps to get good agreement with AAS and ICP results as well as with the certified values of a sludge of the Community Bureau of Standards.     

Beitrag zur Phosphorbestimmung im Klärschlamm

As the introduction, the advantages and drawbacks of a large number of phosphorus determination methods and digestion techniques for particulate matter, as e. g. sewage sludge, used in practice are described. The results of some investigations concerning the techniques of digestion as well as the further preparation of the extracts for the phosphorus determination proper are graphically and in tabular form represented and interpreted. The investigated photo-metric methods may be disturbed by iron and silicic-acid components. Advice about, and possibilities for avoiding such disturbances are given. In the case of the simultaneous application of the Kjeldahl digestion for the determination of nitrogen as well as of phosphorus there should be paid attention to possible disturbances by the selenium- or mercury-containing catalyst additives in the further processing of samples due to the formation of deposits.     

Untersuchungen zum Schadstoffpotential von Wasserwerksschlämmen

Investigation on the Pollution Potential of Waterworks Sludges Several contaminated sludges from water treatment plants with known or estimated concentrations of trace elements were investigated for their leaching characteristics and long-term stability using standard and advanced test procedures. Potentially hazardous elements in the sludge are zinc, nickel, and arsenic with concentrations of up to 1.2 g/kg dry matter (mass). Preliminary sorption tests with synthetic sludge components like iron hydroxide, manganese oxide, silicate clay minerals, and chitine powder as a model organic component showed that Cu is associated with the organic phase wheras arsenic is predominantly bound to the iron oxide minerals. The recently suggested pH_stat test procedure was used to assess the leaching characteristics of metals at typical pH values. This procedure was compared with the DEV-S4 test, the current standard test in Germany, consisting of a simple lixiviation of the solids with water, without pH control. The pH_stat test yields results which are much better to interprete than those obtained by the DEV-S4 procedure. The iron and manganese sludges are well buffered against changes in pH and redox potential so that low pH values and/or reducing conditions can hardly occur. Thus, in deposited material a sudden leaching of heavy metals is unlikely and due to the presence of iron and manganese oxides the pentavalent arsenic is protected against conversion into the highly mobile trivalent form at neutral to low pH. Co-deposition with reducing organic matter and alkaline stabilisation material or waste (like fly ash) could influence the binding properties and should be strictly avoided.     

Das Entwässerungsverhalten von Klärschlamm in Gegenwart von Polyelektrolyten

Dewatering Behaviour of Sludge in the Presence of Polyelectrolytes Interactions of sludge particles with well defined synthetic polyelectrolytes of different charge, molecular mass, and molecular geometry were investigated by means of zeta- and streaming potential measurements and polyelectrolyte titrations. Different mechanisms of flocculation were discussed with regard to the dewatering behaviour of the sludge. In dependence on the flocculation procedure (cationic monoflocculation, anionic-cationic, and cationicanionic dual flocculation) as well as on the chain length and branching of the polyelectrolytes used, different mechanisms of sludge dewatering were discussed: Polyanions are not adsorbed on the sludge particles and lead to a decline of the dewatering results. Linear short chain polycations result in a flocculation after surface charge neutralization of the particles according to a patch mechanism. Long chain linear polycations cause a bridging of the particles leading to a flocculation without charge neutralization of the aggregates formed. With branched polycations, a flocculation according to a patch mechanism is observed. These polycations form sludge particle aggregates which are surface charge neutralized at the flocculation point. In anionic-cationic dual flocculations using long chain polycations, an inclusion flocculation due to polyanion-polycation complex formation is the predominating mechanism. The cationic-anionic dual flocculation with complete covering of the particles with polycations in the first step can be discussed by a patch mechanism quite similar to an anionic monoflocculation of cationic particles. By knowing the mechanism of interaction for a given flocculation agent, an optimal sludge dewatering procedure can be predicted.     

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.     

Bestimmung von Organochlorpestiziden in Schlämmen und Sedimenten

A method for the determination of organohalogens by gas chromatography using electron capture (EDC) and mass-spectrometric (MS) detection was developed for sediments from lakes and sludges of water treatment plants. The method was described and separate techniques for sample preparation were investigated to compare the retrieval rates and the best approach to the “real value”. With the help of solid-liquid-phase- and liquid-liquid-phase extraction sulphur, most of the organosulphur compounds and carbon acids were effectively removed. The compounds were identified by comparing temperature programmed retention indices with those of reference compounds and by high-resolution GC/MS.     

Bestimmung geringer Wassergehalte in getrocknetem Klärschlamm mit Hilfe der Karl-Fischer-Titration

Determination of Low Water Contents in Dried Sludge with the Help of Karl Fischer Titration The accomplished investigations lead to the conclusion that direct water detection in sludge is impossible. This is due to the numerous possible reactants present. Even the extraction of the water by an inert solvent did not permit any realistic deductions. The water detection in sludge requires an external extraction. This may be realized by means of an additional extracting gas or the gaseous phase of the Karl Fischer reagent. The latter method was realized with the apparatus made by the company ECH Elektrochemie Halle. This alternative offers the benefit of avoiding a separate desiccation of the extracting gas. By means of a temperature gradient, the optimum heating conditions for the extraction of water from sludge may be determined. As there are only small quantities of water to be detected in the dried sludges, the best possible method seems to be microcoulometry.     

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.     

Beitrag zur Charakterisierung und Identifizierung organischer Stoffe niederer molarer Massen in biologischen Kläranlagenabläufen

Contribution to the characterization and identification of low molecular weight organic substances in biologically treated effluent. In a review it is shown that by determination of sum parameters only 25% of low molecular weight substances <1000 Dalton in biologically treated effluent can be divided into different classes of compounds. A method is described to separate the low molecular weight compounds (freeze concentration, electrodialysis, vacuum evaporation, freeze drying) in order to identify single compounds. In a first GC-MS analysis 87 compounds, among them a high proportion of substances with hetero atoms, could be identified. Their concentrations lie between 0,1 and 3 μg/1. Only 3% of the low molecular weight fraction related to the DOC value is covered by the identified substances. Therefore it can be assumed, that a broad variety of low molecular weight compounds in very low concentrations is present in the effluent of biological treatment plants.     

Beschaffenheitslängsschnitt eines Flußgebietes mittels Regressionsanalyse

Following a general representation of the regression analysis, especially concerning the relations between flow and concentrations of matter and loads, these relations are represented and discussed for the suspended solids, nitrate concentration, chloride content and oxygen concentration for seven sections of the Spree river. There result clear connections to the structure and utilizations of all of the parts of the river basin. Finally, the covering of the total river basin by models of water quality management in the form of regression, self-purification and eutrophication models-and their coupling is represented.     

Reduzierung von Bakterien- und Coliphagen-Konzentrationen auf der Fließstrecke eines Klärwerksableiters

Reduction of the Concentration of Bacteria and Coliphages along the Flowing Stretch of a Treated Sewage Channel The efficiency of surface waters to eliminate E. coli, fecal streptococci, Salmonella spp., and coliphages was evaluated in a small river which receives treated wastewater and which is rich in submerged macrophytes. The study took place between April and December, 1994. Total colony count, BOD₅, O₂ concentration and water temperature were determined in the river as well. As the river does not receive additional water downwards along its 17.2 km course, dilution effects could be ruled out as the cause for the elimination of the microorganisms. The reduction is assumed to happen rather due to sedimentation, grazing, and adsorption to the submerged waterplants. Immediately after discharge of the wastewater, the river water contained about 10⁵ cfu/100 mL E. coli and 10⁴ cfu/100 mL fecal streptococci, about 1000 pfu/100 mL coliphages, and, as a rule, was positive for salmonella in 10 mL. The reduction of E. coli, fecal streptococci, salmonella, clostridia, and coliphages at the end of the course was 1 to 2 orders of magnitude. This reduction took place mainly within the first 4.7 km, a part in which, due to low flowing velocities, suspended solids settle down efficiently. Besides, at the end of this part the submerged waterplants are especially abundant. The reduction of suspended solids correlated positively with that of BOD₅, bacteria, and coliphages. The reduction of microorganisms was not sufficient to fulfill the requirements of the European Community guidelines for bathing waters and for surface waters used as drinking water source. The regenerating capacity of surface waters is not sufficient to eliminate pathogens from convenionally treated wastewater. Therefore, tertiary treatment is necessary to keep receiving waters reasonably free from pathogens.     

Identifizierung von Stickstoffverbindungen niederer molarer Masse in Abläufen einer kommunalen Kläranlage mit biologischer Reinigungsstufe

Identification of Nitrogen-containing Compounds of Low Molecular Weight in Effluents of Biologically Treated Municipal Wastewater Enriching methods based on reversed phases were developed for the investigation of low-molecular compounds containing nitrogen in municipal wastewater effluent. The enriched mixtures were treated gas chromatographically without derivatization under different conditions. By application of the PBM-algorithm to the GC/MS spectra of the enriched samples (concentration factor 1000...20000), 133 nitrogen-containing compounds could be identified with a probability of occurence of at least 30% put out. Seventeen of these compounds were identified with > 90% probability and another ten with 80...90% probability. 9-Methylacridine was found in nine of ten processed samples investigated. The nitrogen content of the 133 identified compounds was estimated at about 20% of the low-molecular fraction of DON (dissolved organic nitrogen).     

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.