Wasserlösliche Huminstoffe in Wässern einiger Kiestagebaue der DDR

After an explanation of the complex composition of the system of humic substances, some gravel deposits are described from whose open-pit boundaries there were taken water samples, their content of components of humic matter having been determined. Since spectroscopic analysis techniques yield spectra which are difficult to analyse and have a relatively low detection sensitivity, an indirect polarographic method was applied by which water-soluble humic substances can be determined very selectively down to a lower limit of 5 μg/1. Thus, enrichment in water or in adsorbing columns is not required. From the results found there are derived several statements concerning the occurrence of humic substances and fulvic acids in waters and conclusions about the possible influence on the hardening of concrete are given.     

Wirkung der Chlorung auf die Abläufe einer Großkläranlage und ihres Vorfluters

To protect a water for the purpose of local recreation – inclusive of bathing – the effluent of an upstream clarification plant was chlorinated. Due to poorly controlled dosing, residual chlorine quantities exceeding the permissible level entered the receiving stream, its biocenosis having been considerably endangered. Detrimental effects on the chemical composition are graphically represented by the measured results for some waters – partly criteria of quality. There is explained that the self-purification capacity of the water decreased by about 30 % and that the hydrobiological species composition of periphyton was reduced by about 80 %. Finally, advice is given concerning the prevention of such damages to waters.     

Spectroscopic investigation of humic substances in a tropical lake during a complete hydrological cycle

Fluorescence and UV‐VIS techniques were employed for the investigation of natural organic matter (NOM) of a tropical lake. The relationships of absorbance/dissolved organic carbon (A/DOC), fluorescence intensity/dissolved organic carbon (FI/DOC), fluorescence ratio (FR), and peak wavelength with the highest intensity (PW) were used to distinguish the pedogenic or aquagenic origin of NOM. The values of FR, PW and A₂₈₅/DOC of high waters (HW) or flooded period samples and of low waters (LW) period samples of the dry season, except for September 2002, confirm the predominance of pedogenic material. The spectra of water were similar to the standard fulvic acid (FA), and the spectra of FA from the lake were similar to the nearby soils, indicative of pedogenic predominance. The results confirm that the dissolved NOM of Patos Lagoon – MS (Brazil), in all sampling periods, predominantly consisted of humic substances (FA) of pedogenic origin.     

Pestizide in Österreichs Fließgewässern – ein bundesweiter Überblick

Pesticides in Austrian Running Waters – a Country-wide Overview The analyses of pesticides in Austrian running waters are major part of the country-wide water quality monitoring system which has been established in 1991. This paper summarizes the data which were collected for 29 substances between December 1991 and June 1995. The monitoring activities focus on herbicides because they are the most important pesticide group in Austria. Substances of the triazines and phenoxyalkanecarboxylic acid group analyzed within the programme represent the major part of the total amount of herbicides applied. The most detected pesticides were atrazine and its metabolite deethylatrazine. Peak concentrations were obtained in rivers situated in the eastern and southern regions of Austria with intensive agriculture. Other substances play a minor role as contaminants in running waters. These findings correspond to the data obtained by investigations of groundwater in porous media.     

Zur derivativspektroskopischen Bestimmung der Ligninsulfonsäure in Gegenwart von Huminsäuren

A Specord M 40 device with the Date Handling 1 computer cassette was used for the derivative-spectroscopie determination of lignosulphonic acid. Because of the higher sensitivity and the better evaluable peaks, the 2nd derivation of the five possible derivations was used. The analysis method described in detail was tested with test substances on a surface water which was polluted with waste-products from the pulp industry. With the stated device parameters, the lignosulphonic acid up to 2 mg/l can be determined in the presence of humic acids and chlorolignosulphonic acids. In weakly polluted waters, as groundwaters and shore filtrates. still lignosulphonic acid concentrations of 0.1 mg/l can be detected after an adequate enrichment.     

Die neue EG‐Wasserrahmenrichtlinie: Bewertung der chemischen und ökologischen Qualität von Oberflächengewässern

The New EC Framework Water Directive: Assessment of the Chemical and Ecological Status of Surface Waters The main objective of the draft EC Framework Water Directive is the good quality of all surface waters. The directive provides for an assessment of the chemical status of surface waters (EU‐wide valid environmental quality standards for approximately 30 priority substances) and a five‐stage ecological classification of waters, comprising the stages high, good, moderate, poor, and bad. The starting point for the assessment are the reference conditions, which are defined as corresponding to high water quality and characterising a water status with no significant anthropogenic impact. The reference sites in the various water body types are to be selected using hydromorphological and physico‐chemical parameters and subsequently characterised by means of biological parameters. For surface waters, three groups of characteristics are provided for, namely: 1. with priority the biology – in the case of surface waters – with the four elements phytoplankton, macrophytes/phytobenthos, benthic invertebrate fauna, and fish fauna; 2. supporting the hydromorphology, e.g. flowing waters with the three elements hydrological regime, river continuity, and morphological conditions and 3. supporting the physico‐chemical conditions with the three elements general conditions, specific synthetic pollutants, and specific non synthetic pollutants (other than the priority substances of the chemical status).     

Elektrosorptionsanalyse: Ein empfindliches Verfahren zum Nachweis grenzflächenaktiver Stoffe im Wasser

Two examples of damages: Damages to waters caused by surfaceactive polyethylene glycolacrylate (PEGA) waste waters and a fire extinguishing substance (30 % fatty alkyl sulphate and 15 % ethylene glycol butyl ether) are analytically evaluated. A new method from polarography was described – the electrosorption analysis –, which was tested on the samples of the waste waters and waters of the events of damage. For comparison, investigations were carried out according to the conventional laboratory routine method. The described new method has shown pronounced advantages with respect to the detectability of substances contained in water and the expenditure of material and time. Individual tensides can be determined if known separation processes are applied in advance.     

Occurrence forms of metals in natural waters depending on water chemistry

The results of experimental studies of the composition and specific features of humic substance isolated from typical soils of natural zones are given. The stability constants of metal complexes with humic substance are evaluated. The obtained experimental data are used to calculate the occurrence forms of metals in natural waters in the zones of taiga, forests, and steppes. The occurrence forms of metals are shown to be determined by the general chemistry of natural waters rather than stability constants of complexes with organic matter.     

Humic Acids in the Inflows to the Fláje Reservoir after Deforestation of its Watershed

Today only 35% of the catchment area are covered by forests after deforestation, as compared with the original 70%. In connection with that, the concentration of humic matter has decreased from the original 8 mg/1 to 4 mg/1. The analysis of these changes is facilitated by the linear regressions of a high significance which exist between the COD-Mn and humic acid concentration and the colour. Parallel to deforestation, also the nitrate concentration increased, which, however, can be explained by higher nitrogen concentrations in precipitation.     

Identification et Dosages des Substances azotées obtenues par Hydrolyse d'un Acide humique après peracetique

A humic acid extracted from a peat was easily hydrolysed by 6N HCl after oxidation with peracetic acid. The proportion of amino-acids in the hydrolysate was high (11,7 g of aminoacids per 100 g of humic acid), when the proportion of NH₃ was relatively low. 17 aminoacids were identified and titrated. On the opposite, a humic acid with the same origin, which was not oxidised with peracetic acid, gave less amino-acids on hydrolysis, but tenfold more NH₃, which is probably produced by partial decomposition of the amino-acids.     

Anwendung einer enzymatischen Methode zur Charakterisierung von Huminstoffen Enzymatic Characterization of Humic Substances

A method is described for the specific hydrolysis of amino acids from humic substances by using the proteolytic enzyme “Pronase E”. The amino acids are analyzed by a fluorescence detector after precolumn derivatization and HPLC-separation. The pattern and the concentration of amino acids after the enzymatic hydrolysis are set up for humic substances of different origin. Due to the results the enzymatic hydrolysis is suitable for the characterization of humic substances with a nitrogen content higher than 3%. As shown in a kinetic study of the hydrolysis of a fulvic acid the influence of humic substances on the enzyme activity increases in case of lower nitrogen content. Due to the specificity of the proteolytic enzyme the operationally defined method is limited as shown by a protein of a known amino acid content. The amino acids leucine, valine, tyrosine and histidine are released to the highest extent. The determined total extent for the hydrolysis of Insulin B is 26.34% and for Casein 38.37%. By comparison of the enzymatic hydrolysis with the classic acid hydrolysis the advantages of the biochemical method are the simple experimental handling and the mild reaction conditions. Amino acids which are very unstable like glutamine and asparagine can only be analyzed by the enzymatic hydrolysis.     

Degradation and Transformation of Aquatic Humic Substances by Laccase-producing Fungi Cladosporium cladosporioides and Polyporus versicolor

A phenoloxidase-producing fungus – Cladosporium cladosporioides – was isolated from water of a bog lake. At high concentrations of carbon (333 mM) and nitrogen (12 mM), the fungus demonstrated the formation of a laccase and a high ligninolytic activity. After addition of riverine or groundwater humic substances into culture media (ca. 1 mg mL^–1), the fungus showed the ability of degrading (utilizing) of about 60% of these substances. However, the exact quantification of the degree of degradation was difficult because of adsorption of humic matter on fungal mycelium. Reisolated humic substances were lower in aromatic and higher in aliphatic structures. A crude enzyme from the C. cladosporioides culture showed only low activity in decolorizing humic substances, whereas decolorization up to 50% was observed when using a laccase preparation from Polyporus versicolor, and especially in the presence of a redox mediator.     

On the Elimination of Organic Microcontaminants by Flocculation with Lime Hydrate

For the purpose of utilizing domestic flocculants for the treatment of water and of reducing by this the equivalent imports of metal salts, in this paper the result of investigations made on model waters and on a river water sample is described. The model waters contained the pesticides Atrazin, Diuron and 2,4-D, which partly were polluted in addition with different quantities of fulvic and humic acids as well as with colloidal substances causing turbidity (Friedland clay and finely dispersed cellulose). The investigations were supplemented by testing several adsorption media as γ-aluminium oxide, active carbon and diatom earth. In the presence of fulvic and humic substances one does not succeed in eliminating the investigated herbicides by flocculation with lime hydrate. Only after chemical side reactions between these contained substances the adsorbability is clearly influenced. The different elimination efficiencies at different reaction conditions are explained in detail.     

Zielvorgaben für Pflanzenschutzmittelwirkstoffe und andere Schadstoffe in Oberflächengewässern

Quality Targets for Pesticides and Other Pollutants in Surface Waters Surface waters are not only adversely affected by industrial and municipal wastewaters but also by diffuse sources. For the control of the ecological water quality, so‐called quality targets are set. The quality targets are threshold concentrations for hazardous substances related to the protected goods like water ecosystems, drinking water supply, sediments, or fishing. In this paper, quality targets for the protection of aquatic life in surface waters were derived on the basis of a concept developed by the International Commission for the Protection of the Rhine (Internationale Kommission zum Schutze des Rheins – IKSR). The quality targets for the selected hazardous substances, which mainly belong to the chemical class of pesticides, were calculated using ecotoxicological results for species of bacteria, algae, fish, and small crustaceans, as the four trophic standards of the water ecosystem. In cooperation with the Federal Environmental Agency (Umweltbundesamt – UBA) the effect data were taken from ecotoxicological data bases. According to the concept of the IKSR, the lowest test result for the most sensitive species was multiplied by an assessment factor. This proceeding concerns the difficulty in describing the complex interactions in water ecosystems with toxicity data of single laboratory experiments for a few organisms. For seven pesticides quality targets below 0.1 μg/L were proposed. These results show that the ecotoxicologically based quality targets might be even lower than the limit values for pesticides in drinking water of 0.1 μg/L. But for most of the substances the determined values are significantly higher. The great concentration range of quality targets demonstrates distinctly that one standard concentration for all pesticides could not be given with regard to the different effects on aquatic organisms.     

Occurrence and Chemistry of Zinc in Freshwaters — its Toxicity and Bioaccumulation with Respect to Algae: A Review. Part 1: Occurrence and Chemistry of Zinc in Freshwaters

Zinc is a fairly abundant metal, it has been estimated that zinc represents 0.004 percent of the earth's crust and is twenty-fifth in the order of abundance. Its concentrations in surface waters vary greatly with locality; the highest concentrations of zinc have been observed in areas with acid mine drainage, but zinc enters surface waters in many other ways. Chemical thermodynamic calculations summarized by solubility graphs are given. The zinc solubility may be significantly controlled by stream sediments; Zn concentrations of sediments from various areas are given. Many techniques for extraction from sediments have been developed, they differ in efficiency.     

The removal of dissolved humic acids and iron during estuarine mixing

The estuarine chemistry of dissolved humic acids was determined by carrying out both field and laboratory studies. These approaches were combined in an investigation of the Amazon estuary while laboratory mixing experiments were performed using filtered (0.45?0.001 μm) river water fractions of the Water of Luce (Scotland).The results demonstrate that a small fraction of river dissolved organic matter is preferentially and rapidly flocculated during estuarine mixing. This fraction is the high molecular weight component of dissolved humic acids (0.45?0.1 μm filtered). Approximately 60–80% of the dissolved humic acid in these rivers flocculates during estuarine mixing. This represents a removal of only 3–6% of river dissolved organic matter and is responsible for the non-conservative behaviour of dissolved humic acid in the Amazon estuary even though total dissolved organic carbon appears conservative.The salinity dependence with which humic acid flocculates in estuaries is similar to that of iron. This implies that both constituents may be removed from river water by a common mechanism of colloid flocculation.     

Nanofiltration in Combination with Limestone Filtration for Treating a Soft Spring Water Containing High Amounts of Humic Substances

The paper presented here describes experiments with a nanofiltration pilot plant treating spring water which contains high amounts of humic substances. With this process, water components such as humic substances, iron, manganese, and aluminum may be very well removed. However, the low pH value of the NF filtrate does not conform with the German standards. This is why the pH value will be increased in a second treatment step by limestone filtration. Prior to limestone filtration, CO₂ dosage is required in order to make sure that the pH value stays below the upper limit of the German standards of 9.5. With this treatment, a drinking water results which meets the German standards and has good chemical properties with respect to corrosion. The operation of the nanofiltration pilot plant for the treatment of the very soft spring water did not require the continuous addition of chemicals in order to prevent scaling. Although the spring water entered the NF without chemical pretreatment, there was no decrease in filtrate capacity observed over a period of six months. This is in contrast to other investigations involving colour reduction from very hard surface waters. When treating very hard waters by nanofiltration, the addition of complexing agents or acid is required in order to prevent scaling of the membranes. Such intricate pretreatment procedures cause doubt of the application of nanofiltration for the treatment of hard waters in large plants. However, in the case presented here, the application of NF in combination with the hardening step is quite simple, so that the full-scale plant may be operated mainly automatically and will require only little maintenance.     

Bestimmung von Pflanzenbehandlungsmitteln in Wasser durch Online-Fest-Flüssig-Extraktion und HPLC-DAD

Determination of Pesticides in Water by On-line Solid-phase Extraction and HPLC-DAD This paper describes an HPLC on-line procedure for the determination of 29 relevant pesticides in water by diode-array detection using a compact HPLC-system with integrated column-switching. The sample – 5 mL – is injected with a large volume injection system on a precolumn cartridge (RP-C18). Enriched compounds are eluted in frontflush mode by columnswitching to a microbore column and separated with a gradient water/acetonitrile. During desorption the precolumn cartridge is heated at 80°C resulting in a comparable efficiency to the separation with direct injection. The procedure is fully automated for continuous monitoring of drinking-, ground-, and surface water with low contamination levels. Sample preparation is limited to a filtration step with an anion-exchange membrane filter to reduce natural contaminations e.g. humic acids simultaneously. For a concentration of 50 ng/L, the signal to noise ratio varies from 3:1 (Ethidimuron) up to 25:1 (Chloridazon). The standard deviations compare to the standardized HPLC-method DIN EN ISO 11369; the recovery rates are 100% and reproducible. The method was successfully tested on ruggedness with several sequences from a monitoring program. The precolumn cartridge needs replacement after 100 sample injections. Finally, this method was coupled with a benchtop mass-spectrometer (electrospray mode) without changing the chromatographic conditions. With selected ion monitoring (SIM) selectivity and detection sensitivity could be improved considerably compared to DAD-detection.     

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.     

Photochemical degradation of phenanthrene as a function of natural water variables modeling freshwater to marine environments

Photolysis rates of phenanthrene as a function of ionic strength (salinity), oxygen levels and humic acid concentrations were measured in aqueous solution over the range of conditions found in fresh to marine waters. Photolysis followed first order kinetics, with an estimated photodegradation half-life in sunlight in pure water of 10.3±0.7h, in the mid-range of published results. Photolysis rate constants decreased by a factor of 5 in solutions with humic acid concentrations from 0 to 10 mg C L(-1). This decrease could be modeled entirely based on competitive light absorption effects due to the added humics. No significant ionic strength or oxygen effects were observed, consistent with a direct photolysis mechanism. In the absence of significant solution medium effects, the photodegradation lifetime of phenanthrene will depend only on solar fluxes (i.e. temporal and seasonal changes in sunlight) and not vary with a freshwater to marine environment.