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.     

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.     

UV-Derivativ-Spektren zur Vorabschätzung des Gehaltes von polycyclischen aromatischen Kohlenwasserstoffen in Schwebstoffen und Sedimenten der Gewässer Derivative UV Spectra for Estimating the Contents of Polycyclic Aromatic Hydrocarbons in Suspended Solids and Sediments of Waters

By means of UV spectra of cyclohexane extracts from aquatic sediments it is possible to distinguish: “normal” mineral oil aromatics (e. g. of the middle distillation fraction), used oils, and highboiling raffinates, tar oils, and — as representative of aromatics listed in the German drinking water ordinance — fluoranthene. Starting with less selective extractants and the basic UV spectra, it is shown that spectra of higher orders frequently allow a quantitative determination of fluoranthene. If it is justified to assume a constant conversion factor, the result of the measurement can be used to calculate the contents of the whole group of aromatics listed in the German drinking water ordinance. A comparison with other methods (HPLC etc.) and with results from other laboratories showed good agreement. Finally, the diagnostic capacity (fingerprint) of derived spectra is pointed out.     

Untersuchungen zur Abtrennung von Schwermetallen aus Abwasser mit frisch hergestelltem Magnetit Studies for Separation of Heavy Metals from Wastewater with Freshly Precipitated Magnetite

The separation of heavy metals from wastewater may be improved by precipitation/flocculation with iron- or aluminium salts. Often, the resulting products are voluminous, water-containing, amorphous hydroxides which show only limited flocculation properties and may possibly pose problems with the technical separation from the aqueous phase. The application of magnetite could be advantageous because magnetite is ferromagnetic and can be separated very quickly in a magnetic field. First of all, a simple preparation method for magnetite was studied. Pure magnetite could be prepared by mixing an iron(II) salt solution with an equivalent amount of sodium hydroxide at room temperature without oxidation by air. The required reaction time was only 3 hours. For the precipitation of heavy metals from an electroplating wastewater, a better metal elimination and smaller sludge volumes resulted with that artificially produced magnetite in comparison with a precipitation by NaOH. Thereby not only the adsorption of metals was established but also coagulation effects of the magnetite sludge with small metal hydroxide particles. By means of the experimental results. sorption of nickel and chromium was compiled as function of pH and precipitation time. Because freshly precipitated magnetite shows very good sorption and flocculation properties, and pH of precipitation may be lower, its use in high gradient magnetic separation (HGMS) could be more effective for metal elimination than magnetite powder.     

Degradation of organic matter from wastewater using advanced primary treatment by O3 and O3/UV in a pilot plant

The oxidation of organic matter from wastewater using ozone, ultraviolet radiation and ozone/UV oxidation was evaluated in a pilot plant, applying a continuous effluent arising from the Autonomous Metropolitan University wastewater treatment plant. The oxidation was measured as the efficiency to remove organic load, measured as chemical oxygen demand. The use of ozone and UV was evaluated separately and in combination through a continuous process. Three different ozone doses (0.6–1.2 mg O₃/L) and three different UV radiation fluencies (6.7–20.12 mJ/cm²) were assessed. A synergistic effect of the combined process ozone/UV was demonstrated, and a maximal chemical oxygen demand reduction was achieved both processes. Due to residence times used (less than 1 min), 36% of chemical oxygen demand reduction was obtained when ozone treatment was evaluate separately and only 9% using ultraviolet radiation.     

An alternative method for aerosol optical thickness retrieval in the UV range

Atmospheric aerosol particle size distribution data derived from almucantar scans performed by the CIMEL sunphotometer at Belsk, Poland, in 2005 are used for the estimation of aerosol optical thickness (AOT) in the UV range by applying the Mie theory. The results obtained are compared with the direct Sun measurement data from the CIMEL sunphotometer and collocated Brewer spectrophotometer No. 064, as well as with AOT obtained by Angström extrapolation from the direct Sun measurements performed by the CIMEL sunphotometer in the visible range of wavelengths. Mean differences between calculated and measured values of AOT are up to about 8% in the UV-B range, which is close to the measurement uncertainty of the Brewer spectrophotometer and much less than that obtained by means of Angstrom extrapolation (over 24% in the UV-B range).     

Kinetics of Methyldiethanolamine Mineralization by Using UV/H2O2 Process

The UV/H₂O₂ is one of the popular techniques in the advanced oxidation processes (AOPs) and has been applied in the wastewater treatment during recent two decades. UV exposure on the H₂O₂ generate highly reactive hydroxyl radicals (OH^?), which are used to degrade organic contaminants through oxidation processes in wastewater. This present study involves the estimation of hydroxyl radical rate constants of methyldiethanolamine (MDEA) mineralization at different temperatures by using UV/H₂O₂ in aqueous solution. Laboratory experiments have been conducted and the profile of MDEA mineralization has been established. The hydroxyl radical rate constants and the activation energy of mineralization process have been calculated. The estimated hydroxyl rate constants and the activation energy are in good agreement with those reported in the literature.     

On the origin of seasonal variation of aerosol optical thickness in UV range over Belsk,Poland

Aerosol optical thickness (AOT) and seasonal variation of AOT over Belsk, Poland, in the UV wavelength range (310–380 nm) have been analysed using results of measurements by Brewer spectrophotometer No. 064 and Cimel sunphotometer data for the 2002–2007 period. The comparison of AOT derived from direct Sun measurements by Brewer spectrophotometer in the 310–320 nm range and retrieved from Cimel measurements at longer wavelengths shows good correlation (R = 0.96), with overestimation of retrieved values compared to the measured ones by about 6%. Basing on aerosol microphysical properties taken from almucantar retrievals and Mie theory, optical properties of aerosol in the UV range has been calculated. Analysis of seasonal variation of AOT at Belsk reveals two maxima: in April and July–August. Analysis of back-trajectories in conjunction with analysis of fire maps from Fire Information For Resource Management System shows that these seasonal maxima are connected with seasonal biomass burning in Eastern and Southern Europe.     

Association of Humic Substances: Verification of Lambert‐Beer Law

The precision UV/Vis‐absorption spectra of a naturally occurring aquatic humic substance were measured in the range of concentration 0.003 to 1.4 g/L DOC (dissolved organic carbon). Lambert‐Beer law is well obeyed at low concentrations whereas deviations have been observed for DOC concentrations above 0.1 g/L: they are interpreted in terms of self‐solvation and formation of micelles.     

Synthesis of Sulfonated Naphthalene-Formaldehyde Condensates and their Trace-analytical Determination in Wastewater and River Water

Naphthalenesulfonates and their condensates with formaldehyde (SNFC) are widely used in industrial processes, e.g. as plasticizers for concrete or as tanning agents. Based on their high aqueous solubility these compounds are expected to be eliminated incompletely in mechanical-biological treatment plants and to end up in the aquatic environment. Due to the lack of reference compounds the identification and quantification of these condensates in the aquatic environment was impossible in the past. This paper describes the synthesis of several condensates of 2-naphthalenesulfonate with formaldehyde. With the synthesized products as reference compounds it was possible for the first time to detect and quantify some sulfonated naphthalene-formaldehyde condensates in the aquatic environment. For this purpose characteristic peaks in the HPLC screening of wastewater and river water samples were compared with the corresponding peaks of a technical SNFC product. Three out of several paths on which these compounds enter the aquatic environment were identified. The identified compounds in the analyzed wastewater samples have concentrations between 0.14 and 110 μg/L.     

Adsorbed and Bound Residues in Fulvic Acid Fractions of a Contaminated Groundwater – Isolation:, Chromatographic and Spectroscopic Characterization

Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.     

Characterization of industrial wastewaters using gel-permeation chromatography with multicomponent detection

The gel-permeation chromatography system with multicomponent detection of organic carbon, organic nitrogen, organic halogen, and UV/vis absorption measurement is shown to be a useful tool for characterization of industrial wastewaters and wastewater treatment processes. The proposed system was used to investigate biologically treated wastewater from chemical industry, whereby one branch stream was identified to be the main source of persistent halogenated organics. Various treatment processes of pulp mill wastewater were also evaluated revealing that precipitation with aluminium is very effective for the removal of the high molecular fraction whereas the biological treatment is generally less selective. In the biological treatment of tannery wastewaters, it has been shown that the aerobic treatment, in contrast to anaerobic step, causes evident alterations of the composition of the polar DOC fraction. The nitrogen containing compounds are also better decomposed in the aerobic step compared to the anaerobic one.     

Konzentrationsprofile in Rotationsscheibenreaktoren und deren Modellierung am Beispiel des anaeroben Acetatabbaus mit experimenteller Überprüfung

Concentration Profiles in Rotating Disc Reactors. Their Mathematical Model for the Anaerobic Digestion of Acetic Acid Including an Experimental Verification This paper presents rotating disc reactors for aerobic and anaerobic wastewater treatment. Unlike the activated sludge or contact processes, this reactor allows higher concentrations of biomass and lesser danger of the reactor becoming blocked. The reduced backmixing within the reactor leads to axial concentration profiles when continuously operated. These are presented for various biological processes. The axial concentration profiles generated during the continuous anaerobic degradation of acetic acid are measured and described by a mathematical model. A refined dispersion model is created on the basis of tracer experiments taking into account the actual construction of the reactor as well as the physical conditions in it. To determine the biodegradation a Haldane kinetics is used, in which the undissociated acetic acid is the substrate. The model takes into consideration all the local parameters (pH value, concentration of acetic acid, biomass, and ion activity). The difficult measurement of the concentration of the active biomass which is immobilized on the disk is accomplished by carrying out batch experiments. The results of the experiments are 22 concentration profiles with influent DOC concentrations from 200 to 2000 mg L^–1 which were measured and modelled. Some examples are shown to illustrate the influence of the ion activity and the refinement of the dispersion model.     

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.     

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

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

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.     

Optimization of a Photo‐assisted Fenton Oxidation Process: A Statistical Model for MDF Effluent Treatment

In the present study, the effects of initial COD (chemical oxygen demand), initial pH, Fe²⁺/H₂O₂ molar ratio and UV contact time on COD removal from medium density fiberboard (MDF) wastewater using photo‐assisted Fenton oxidation treatment were investigated. In order to optimize the removal efficiency, batch operations were carried out. The influence of the aforementioned parameters on COD removal efficiency was studied using response surface methodology (RSM). The optimal conditions for maximum COD removal efficiency from MDF wastewater under experimental conditions were obtained at initial COD of 4000 mg/L, Fe²⁺/H₂O₂ molar ratio of 0.11, initial solution pH of 6.5 and UV contact time of 70 min. The obtained results for maximum COD removal efficiency of 96% revealed that photo‐assisted Fenton oxidation is very effective for treating MDF wastewater.     

Alkaline Degradation of Dissolved Organic Matter

The degradation of dissolved organic matter (DOM) was studied in alkaline solution. The products were characterised using UV/vis spectroscopy, size‐exclusion chromatography (SEC), and by the analysis of low‐molecular‐weight organic acids (LMWOA). The degradation experiments were performed with water from a brown water lake or its isolated fulvic acid fraction and sodium hydroxide at different reaction times and temperatures. Depending on the wavelength and the reaction time, the UV/vis absorbance between 230 nm and 600 nm increased or decreased. The behaviour of model compounds during reactions in alkaline media was compared to the UV/vis spectroscopic behaviour of DOM. The release of LMWOA was described by kinetic data and compared to the data of model reactions. Evidence was given for the carboxylic esters playing a significant role in the release of LMWOA only during the beginning of the alkaline degradation. The results gained by SEC with on‐line UV and DOC detection showed that the average size of DOM was decreasing, and that a major part of the degradation products consisted of low‐molecular‐weight mono‐ and dicarboxylic acids.     

Assessment of Cyto‐ and Genotoxic Effects of a Variety of Chemicals Using Saccharomyces cerevisiae

Saccharomyces cerevisiae as the most simple eukaryotic organism is broadly accepted as a laboratory model organism. For the detection of potential toxic effects of pure compounds and complex composed samples like wastewater a miniaturised short‐term in vitro cyto‐ and genotoxicity screening assay was developed. The assay based on genetically modified S. cerevisiae cells deleted in the prominent drug efflux transporters Pdr5, Snq2, and Yor1 that facilitate pleiotropic drug resistance. The yeast strain devoid of these proteins that mediate the efflux of structurally diverse hydrophobic compounds exhibited an increased sensitivity to a variety of organic compounds. The DNA damage inducible RAD54 promoter fused to a yeast optimized derivative of the GFP (green fluorescent protein) gene from the jelly fish Aequorea victoria served as an indicator of DNA damage in this strain. Various pure compounds including the direct‐acting genotoxins methyl‐N‐nitro‐N‐nitrosoguanidine (MNNG), 4‐nitroquinoline‐N‐oxide (4‐NQO), methyl methanesulfonate (MMS) and hydroxyurea as well as the heavy metals cadmium and chromium(VI), the insecticide lindane and the central nervous system stimulant caffeine were tested exhibiting dose dependent induction of green fluorescence. All compounds were in parallel examined for chronic toxicity. A bioassay detecting simultaneously geno‐ and cytotoxic effects of potential toxicants in a single assay can be an important tool with a variety of applications in environmental monitoring and aquatic ecotoxicology. By partial automation and miniaturisation to microtitration scale this bioassay enables sensitive and fast biomonitoring for a multitude of samples.     

Hospital Laundry Wastewater Disinfection with Catalytic Photoozonation

Wastewater production in a hospital laundry and the treatment of the most critical wastewater stream, are assessed. Hospital laundry wastewaters are hazardous to the environment due to their high pollutant concentrations and the chemicals added during the clothes washing process. Heterogeneous photocatalysis with UV, O₃ and TiO₂ and their possible combinations were used for disinfection purposes. A ramp‐type reactor was used for TiO₂ (P25 Degussa) fixation and for photochemical diffusion of the ozonized air. After assessing 5‐day biological oxygen demand, chemical oxygen demand, pH, turbidity, and surfactant content, and checking for the presence of thermotolerant coliforms and Escherichia coli, it was concluded that UV/O₃/TiO₂ was the best process/combination, yielding a 100% disinfection rate and a microbiological inactivation of 0.5070 min^–1 for E. coli and of 0.5505 min^–1 for thermotolerant coliforms.