Bildungsbedingungen von Zinkferriten im Hinblick auf die Entfernung von Schwermetallen aus Abwässern durch Magnetseparation

Conditions of the Formation of Zinc-bearing Ferrites in Regard of Heavy Metal Removal from Wastewater by Magnetic Separation Magnetic separation techniques can be applied for heavy metal removal from wastewater if it is reached to link together the heavy metals with a substance which is sufficiently influenced by a magnetic field. Such a substance is the ferrimagnetic magnetite which can be prepared under special conditions – by oxidation of ferrous hydroxide – in wastewater. In this paper, zinc was chosen as an example for technically relevant, diamagnetic heavy metals. The investigations deal with the influence of zinc onto the structure and the magnetic properties of the reaction products produced by oxidation of zink-bearing ferrous hydroxide in aqueous solutions at room temperature. The oxidation was caused by synthetic air passing through the suspension. During the reaction, the parameters pH value, redox potential, and concentration of dissolved oxygen were observed continuously. The plots of these parameters versus time yield typical courses which can be used as measurement for the progress of the reaction. The results show that magnet ite can only be prepared if the molar ferrous concentration at the beginning is four times higher than the concentration of the dissolved oxygen. Furthermore, the oxidation rate must be slow, a condition which could be achieved by mass transfer controlled kinetics. The products of the oxidation of zinc-bearing ferrous hydroxide show a colour between black and brown. They consist of magnetite, zinc-bearing ferrite and amorphous iron hydroxide. It can be observed that with increasing initial zinc concentrations, increasing amounts of zinc-bearing ferrite but also of amorphous iron hydroxide are produced. Therefore, it seems that the impact of zinc on the reaction is in such a way that more amorphous compounds instead of the thermodynamically stabile ferrite are formed; The magnetic properties show also a dependence on the initial zinc concentration: The saturation magnetization decreases with an increase of the zinc concentration. The reaction product which results from the experiment with an initial mole ratio of Zn:Fe = 1:1 points out only paramagnetic behaviour.     

Sorption von Schwermetallen durch Eisenphosphat-Kolloide in essigsauren Bodenextrakten

Sorption of Heavy Metals from Acetic Acid Extracts by Ferric Phosphate Colloids A conceivable procedure to remedy heavy metal contaminated soil materials is given with extraction of organic acids, i. e. by the use of a biological degradable extraction agent. The following concentration step of heavy metal extracts should be carried out to a great extent without a change of the low pH values. A conventional precipitation of the heavy metals by rising the pH should be avoided in order to introduce no large amounts of salts into the wastewaters of the process and furthermore, to reduce the amount of sludge to be deposited. The process scheme developed with the objective of heavy metals recycling consists of the following steps: the extraction of the heavy metal contaminated soils with weak organic acids like acetic acid or citric acid, the electrolysis of the extract, and a concentration step in order to treat metal concentrations not fully removed by electrolysis. This third step, e.g. could contain sorption on iron phosphate colloids and precipitation within the acidic environment. It has been examined whether a removal of the heavy metals Pb, Cd, Cu, Sb, Cr, Ni and Zn from acetic aqueous solutions of pH between 2 and 3 can be carried out.     

Use of Magnet Technology for Phosphate Elimination from Municipal Sewage

The present report describes the set-up and first operation results of a novel carousel magnetic separator. This carousel magnetic separator is suitable for continuous separation of magnetized particles from water. Continuous operation is achieved by a segmented rotating separation matrix. This matrix also allows the use of low-cost permanent magnets, by means of which magnetic fields of up to 0.5 T can be generated without energy consumption. The suitability of a first prototype of this carousel magnetic separator was tested for elimination of magnetite-containing iron phosphate and iron hydroxide flocs. These flocs result from conventional precipitation/flocculation of municipal sewage with FeCl₃ and the addition of magnetite particles generated by wet-chemical processes. First results demonstrate that the carousel magnetic separator can reduce phosphate concentrations of up to 14 mg/L PO₄^3–-P in the inlet to below 1 mg/L PO₄^3–-P in the outlet at filtration rates of about 40 m/h. Magnetite dosage in the range of 50 mg/L affects phosphate precipitation positively via a slight reduction of the precipitant volume. However, the total amount of chemicals required for phosphate elimination is increased by the substances needed for magnetite production. Therefore, a further reduction of magnetite dosage must be achieved.     

Cd(II), Pb(II) and Zn(II) Removal from Contaminated Water by Biosorption Using Activated Sludge Biomass

Biosorption using activated sludge biomass (ASB) as a potentially sustainable technology for the treatment of wastewater containing different metal ions (Cd(II), Pb(II) and Zn(II)) was investigated. ASB metal uptake clearly competed with protons consumed by microbial biomass compared with control tests with non‐activated sludge biomass. Biosorption tests confirmed maximum exchange between metal ions and protons at pH 2.0–4.5. It was revealed by the study that the amount of metal ions released from the biomass increased with biomass sludge concentration. The result showed that maximum absorption of metal ions was observed for Cd(II) at pH 3.5, Pb(II) at pH 4.0, and pH 4.5 for Zn(II) ions. The maximum absorption capacities of ASB for Cd(II), Pb(II) and Zn(II) were determined to be 59.3, 68.5 and 86.5%, respectively. The biosorption of heavy metals was directly proportional to ASB stabilization corresponding to a reduction in heavy metals in the order of Cd < Pb < Zn. The order of increase of biosorption of metal ions in ASB was Zn(II) < Pb(II) < Cd(II), and this was opposite to that of non active sludge. The results indicate that ASB is a sustainable tools for the bioremediation of Cd(II), Pb(II) and Zn(II) ions from industrial sludge and wastewater treatment plants.     

Sorption of ionic forms of metals on suspension in the case of a volley of wastewater into a channel flow

The sorption kinetics of heavy metal ions by organic suspension is considered in the case of a volley of wastewater into a channel flow. The characteristic time scales of the major kinetic stages of ionic sorption are estimated by using a model of matter sorption by particulate matter involving macrokinetic parameters and field data. The sorption on organic suspension and iron hydroxides is virtually instantaneous, whereas the characteristic time of sorption on clay particles is of the order of hours and days. A concept of sorption capacity of natural water is introduced. This capacity depends on the concentration of the sorbing suspension and the distribution coefficient of the dissolved forms of substances that can be sorbed, in particular, heavy metals. When the sorption capacity is small or sorption kinetics is slow, the dilution of wastewater becomes the main mechanism reducing the concentration of metal ionic forms.     

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.     

Removal of Heavy Metals from Synthetic Mixture as well as Pharmaceutical Sample Via Cation Exchange Resin Modified with Rhodamine B: Its Thermodynamic and Kinetic Studies

A new sorbent was prepared by loading rhodamine B on Amberlite IR‐120. Various physico‐chemical parameters such as effects of adsorbate concentration, contact time, pH, and temperature on the sorption of the dye have been studied. Thermodynamic parameters (ΔH° and ΔS°) were also evaluated for the sorption of dye. Kinetic studies revealed that the sorption of the dye was best fit for pseudo‐second‐order kinetic. The metal ion uptake in different solvent systems has been explored through column studies. On the basis of distribution coefficient (K_d), some heavy metal ions of analytical interest from binary mixtures have been separated. The limit of detection (LOD) for the Ni²⁺ and Fe³⁺ metal ions was 0.81 and 0.60 µg L^?1, and the limit of quantification (LOQ) was found to be 2.72 and 2.0 µg L^?1. This sorbent has also been successfully applied in the analysis of multivitamin formulation. The applicability of the modified resin in the separation of heavy metals constituting real and synthetic samples has been explored.     

Application of Agro‐Based Biomasses for Zinc Removal from Wastewater – A Review

Zinc remediation of aqueous streams is of special concern due to its highly toxic and persistent nature. Conventional treatment technologies for the removal of zinc are not economical and further generate huge quantity of toxic chemical sludge. Biosorption is emerging as a potential alternative to the existing conventional technologies for the removal of metal ions from aqueous solutions. Mechanisms involved in the biosorption process include chemisorption, complexation, adsorption–complexation on surface and pores, ion exchange, microprecipitation, heavy metal hydroxide condensation onto the bio surface, and surface adsorption. Biosorption largely depends on parameters such as pH, the initial metal ion concentration, biomass concentration, presence of various competitive metal ions in solution, and to a limited extent on temperature. Biosorption using biomass such as agricultural wastes, industrial residues, municipal solid waste, biosolids, food processing waste, aquatic plants, animal wastes, etc., is regarded as a cost‐effective technique for the treatment of high volume and low concentration complex wastewaters containing zinc metal. Very few reviews are available where readers can get an overview of the sorption capacities of agro based biomasses used for zinc remediation together with the traditional remediation methods. The purpose of this review article is to provide the scattered available information on various aspects of utilization of the agro based biomasses for zinc metal ions removal. An extensive table summarizes the sorption capacities of various adsorbents. These biosorbents can be modified using various methods for better efficiency and multiple reuses to enhance their applicability at industrial scale. We have incorporated most of the valuable available literature on zinc removal from waste water using agro based biomasses in this review.     

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.     

Eliminierung und Rückgewinnung von Metallionen aus Abwässern — eine Übersicht

The present state and the trends of the recovery of heavy metals from wastewaters are presented. The classical precipitation techniques are insatisfactory due to increases of solubility in the presence of impurity ions and/or complexing agents. At present, ion-exchange processes constitute the most frequently used method of metal recycling with an effective enrichment of metal ions. For the effective separation of metals from solutions of a low concentration the electrolytic reduction demands large electrode surface areas. In cells with fixed-bed or fluidized cathodes one can obtain specific electrode surface areas of some 10³ m²/m^m3. For the future, processes of extraction and especially membrane separation will gain in importance. In the past few years, a large number of highly selective metal extracting agents as well as the liquid membrane permeation with suitable carriers were developed. Combinations of membrane separation processes with chemical reactions may attain the same importance, as e.g. ultrafiltration in connection with the fixation of metal ions to watersoluble polymers. In the long run, especially techniques will prevail which will not only result in metal enrichment but also in the recovery of the raw material water.     

Heavy metals in the hydrological cycle: Trends and explanation

This paper reviews the major sources and transport characteristics of heavy metals in the hydrological cycle. It is demonstrated that heavy metal releases to the environment have changed from 19th and early 20th century production-related activities to consumption-oriented factors in more recent times. The relative roles of particle size, sorption and desorption processes, partitioning and the chemical speciation of heavy metals on fine sediments are identified to understand the likely fate of heavy metals released into fluvial systems. It is argued that the spatial and temporal distribution of heavy metals in the river corridor depends not only on an understanding of metal solubility and speciation, but also on an understanding of sediment dynamics which control, for example, floodplain alluviation and the accumulation of metals in the bottom sediments of contaminated rivers, lakes and reservoirs. Existing long- and short-term records are examined to identify the current state of knowledge about the factors which affect heavy metal releases into aquatic environments. With limited exceptions, it is shown that few long-term studies of trends in heavy metal transport are available although, for some major rivers, limited data on trends in metal concentration exists. Palaeolimnological reconstruction techniques, based on an analysis of lake and reservoir sediments, are identified as a possible means of supplementing monitored records of heavy metal transport. Although numerous studies have suggested that trends in atmospheric contamination, mining and urbanization may be identified in the bottom sediment record, other research has shown that the radionuclide-based chronology and the heavy metal distribution within the sediment are more likely to be a function of post-depositional remobilization than the history of metal loading to the basin. Despite these limitations, it is shown that the incorporation of reservoir bottom sediment analysis into a heavy metal research programme, based in river corridors of Midland England, provides an opportunity to identify and quantify the relative contribution of point and non-point contributions to the heavy metal budget and to relate trends in metal contamination to specific periods of catchment disturbance.     

Study of Heavy Metal Compound Transformations in Surface Waters

Results of studying Fe(III) hydrolysis and sorption of heavy metal compounds by organic matter of bottom sediments are discussed. The rate of Fe(III) hydrolysis is found to be largely determined by the concentration of dissolved organic substances. Values of kinetic parameters are obtained for heavy metal compounds sorption under static and dynamic conditions. Calculating the solubility of Fe, Cu, Cd, Zn, and Pb sulfides allowed the assessment of the amount of metals lost by bottom sediments due to the formation of metal complexes with dissolved organic substances contained in natural waters.     

Behavior of Steroid Hormones and Conjugates During Wastewater Treatment – A Comparison of Three Sewage Treatment Plants

The fate of the steroid hormones 17 β‐estradiol, estrone, estriol, 16 α‐hydroxyestrone, and β‐estradiol 17‐acetate, the hormone‐conjugates β‐estradiol 3‐sulfate and estrone 3‐sulfate, and the oral contraceptives 17 α‐ethinylestradiol and mestranol were studied during wastewater treatment as wastewater treatment plants are the major source contamination of urban surface waters with steroid hormones. The elimination efficiencies of three different concepts of WWTPs, i. e., activated sludge versus trickling filter, were compared over four weeks at different weather conditions. While larger WWTPs operating on activated sludge eliminated hormones more constantly than smaller WWTPs, heavy rainfall events led to a collapse of the elimination efficiency. By using trickling filter techniques for the treatment of wastewater an elimination of the steroid hormones could not be observed. Additionally, mass flows on a per person basis are compared. In the three experiments, which ran continuously for four weeks each, it turned out that the concentrations of ethinylestradiol and mestranol were below 6 ng/L in all samples. The inflow concentrations were 70 to 82 ng/L (estrone), 17 to 44 ng/L (estradiol), 61 to 130 ng/L (hydroxyestrone), 189 to 255 ng/L (estriol), 10 to 17 ng/L (estrone‐3‐sulfate) and about 28 ng/L (estradiol‐3‐ sulfate). While in the activated sludge treatment plants the elimination of estrone was 90 and 50%, respectively, estrone was formed from precursors in the trickling filter plant. A similar situation occurred for 17β‐estradiol, estrone 3‐sulfate, and estradiol 3‐sulfate. Hydroxyestrone was eliminated with similar efficiencies in all wastewater treatment plants (64 to 82%), as well as estriol (34 to 69%). Accordingly, the emissions of the wastewater treatment plants differed largely and were not attributed to the size of the respective plant, only.     

Preparative isolation and characterization of heavy metal complexes from acid mine drainage and surface wastewater

A preparative method was developed to sample dissolved organic carbon (DOC) and heavy metals (Ni, Mn) from polluted surface waters. Main focus was set on the preparative production of freeze‐dried samples mainly composed of organic ligands from heavy metal complexes. First characterizations were done in the aqueous phase. Finally, freeze‐dried samples provide stable organic matter for multiple characterizations. Acid mine drainage of the former mining area of Ronneburg (Germany) hold elevated concentrations of heavy metals and low concentrations of DOC. Municipal wastewater, passing the spoil pile, held elevated concentrations of DOC and low concentrations of heavy metals. Dissolved components smaller than 0.45 μm and larger than 1 nm were concentrated by nanofiltration. Organic heavy metal complexes were isolated from this solution by size‐exclusion chromatography (SEC). Different size classes of molecules were collected from the column effluent, depending on their elution time, and were characterized by UV spectroscopy, ICP‐OES, and DOC measurements. All samples held organic heavy metal compounds with different retention times. The organic heavy metal complexes in acid mine drainage had higher retention times than complexes from municipal wastewater. Most interestingly, we found different affinities of heavy metals to different size classes of DOC. This affinity of the heavy metals differs with size and origin of the DOC.     

Demobilization of Heavy Metals from Mine Waters

The present study elucidates the remediation of mine waters by means of geochemical barriers („active barriers“). Active barrier systems (ABS) are developed, which can prevent heavy metal dispersion by introducing the barrier into the mine. Therefore, low‐cost materials are investigated which can remove contaminants by chemical, and/or physical mechanisms from water. The materials investigated are industrial by‐products (e.g. fly ash, red mud, scale arrears), natural wastes (e.g. tree bark), and relatively cheap natural products (bentonite, zeolites). Red mud and fly ash show the best results for the removal of Zn, Cd, Ni, and Mn from model water. Cd seems to have the strongest binding of the investigated metals on the sorption sites. The main mechanisms of metal removal from solution in this case are sorption and precipitation. Both materials have very good sorption and acid neutralization capacities (ANC), but ANC seems to be the determining factor.     

Development of Bench‐Scale Bio‐Packed Column for Wastewater Treatment from Optical Emission Spectrometry

An eco‐friendly and inexpensive technique for wastewater treatment originated from inductively coupled plasma‐optical emission spectrometry (ICP‐OES) is presented within this paper. The proposed process comprised of loading waste crab shells in packed column for adsorption of heavy metal ions, followed by desorption using 0.01 M HCl. An exhaustive physical and chemical characterization of ICP‐OES wastewater revealed the complex nature of effluent, including the presence of 15 different metals and metalloid under strong acidic condition (pH 1.3). Based on the preliminary batch experiments, it was identified that solution pH played a major role in metal sequestration by crab shell with pH 3.5 identified as optimum pH. Rapid metal biosorption kinetics along with complete desorption and subsequent reuse for three cycles was possible with crab shell‐based treatment process. Continuous flow‐through column experiments confirmed the high performance of crab shell towards multiple metal ions with the column able to operate for 22 h at a flow rate of 10 mL/min before outlet concentration of arsenic reached 0.25 times of its inlet concentration. Other metal ions such as Cu, Cd, Co, Cr, Pb, Ni, Zn, Mn, Al, and Fe were only in trace levels in the treated water until 22 h. The performance of the treatment process was compared with trade effluent discharge standards, and the process flow diagram along with cost analysis was suggested.     

Magnetic Removal of Reactive Black 5 from Wastewater Using Ionic Liquid Grafted‐Magnetic Nanoparticles

Due to the unique chemical properties and therefore wide range of applications, significant amounts of reactive dyes often end up in waste waters and this issue raises the need for more efficient treatment technologies. This work investigates the ability of magnetite nanoparticles functionalized with imidazolium based ionic liquid (IL) as an efficient sorbent for the removal of the Reactive black 5 from wastewater. Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, thermo‐gravimetric analysis, and zeta potential measurement were used to characterize the synthesized nanosorbent. The results showed that under optimal conditions, the dye removal efficiency of the grafted IL is 98.5% after a single run. Regeneration of the used sorbent could be possible and the modified magnetic nanoparticles exhibited good reusability. The isothermal data of RB5 sorption conformed well to the Langmuir model and the maximum sorption capacity of IL@Fe₃O₄ for RB5 was 161.29 mg g^?1. Thermodynamic study indicated that the adsorption is endothermic and spontaneous. The use of such a system can provide fast and efficient removal of the reactive dyes from wastewater by using an external magnetic field.     

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).     

Partitioning of Fluoroquinolones on Wastewater Sludge

Laboratory‐scale batch experiments were conducted to investigate the adsorption behavior of eight fluoroquinolones (FQs) on aerobic, anoxic, and anaerobic sludge, under different adsorpiton time, pH, and temperature conditions. Results indicated that adsorption of FQs onto all sludge was a physical sorption process. The relationship of the partitioning coefficient (K_d) and the octanol/water partition coefficient (K_ow) for each FQ was established. The adsorbed fraction of FQs on sludge could then be predicted with the K_d. It was calculated that about 50–72% of the FQs were adsorbed on the sludge. Therefore, the adsorption effect must be considered when studying the fate and occurrence of FQs in wastewater treatment systems.     

Einfluß algenbürtiger organischer Substanzen auf Flockung und Filtration

The treatment of water from eutrophic lakes is disturbed by extensive development of plankton, which is caused by particulate algogenic organic substances and frequently also by dissolved ones. They are released by excretion, diffusion, cell destruction, separation of cell wall substances and metabolic processes in the course of the cellular reproduction in dependence on the physiological state of the algae. At a sufficient dosage of metallic salts as a flocculant, the extracellular organic substance (EOS) may act as an anionic flocculation aid in the concentration range of 1 … 2 mg/1 C. There is decisive the mass ratio: Me (metal as flocculant)/EOS (as TOC). Below a mass ratio Fe : TOC =2 … 3 the EOS disturbs the process of flocculation and filtration. Flocculation and filtration tests are carried out with the centrifugate of the culture liquid of eight algae species in flocculation test apparatus in order to clarify the disturbance of flocculation and filtration. The following essential reaction mechanisms influencing flocculation have been found: complexation of the metal-ions added as flocculation aids, precipitation reactions, neutralization of the positive charge of the metal hydroxo complexes of the flocculant with formation of surface complexes, increasing of the negative charge concentration and formation of protective colloids. The following counter-measures may be technically used with success: increasing of the addition of flocculant (Fe : TOC =2 … 3), shifting of the pH-value below the iso-electric point, addition of calcium-ions (1 … 2 mmol/l) and limited application of ozone prior to flocculation.