Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part I: Drug Residues and other Polar Contaminants in Berlin Surface and Groundwater

Several polar contaminants were found in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. Residues of pharmaceuticals and N-(phenylsulfonyl)-sarcosine originating from various sewage treatment plants effluents were found at concentrations up to the μg/L-level in the surface water, whereas the concentrations of polar pesticides such as dichlorprop and mecoprop were always below 0.1 μg/L. The pharmaceuticals most frequently detected in the surface water samples include clofibric acid, diclofenac, ibuprofen, propiphenazone, and two other drug metabolites. Additional investigations of groundwater wells of a drinking water plant have shown that polar contaminants such as drug residues or N-(phenylsulfonyl)-sarcosine easily leach through the subsoil into the groundwater aquifers when contaminated surface water is used for groundwater recharge in drinking water production.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part III: Determination of Synthetic Musks in Berlin Surface Water Applying Solid-phase Microextraction (SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)

Polycyclic musks and nitro musks were found as environmental pollutants in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. These synthetic musks, which are used as fragrances in cosmetics, detergents, and other products, are discharged by the municipal sewage treatment plants into Berlinπs surface waters. In particular, the polycyclic musks 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyrane (HHCB; Galaxolide®, Abbalide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetraline (AHTN; Tonalide®, Fixolide®) were found in the receiving surface waters at considerable concentrations up to the μg/L-level. In the Wuhle, a small brook almost totally consisting of sewage effluents, maximum concentrations were 12.5 μg/L for HHCB and 6.8 μg/L for AHTN. Additionally, the polycyclic musk 4-acetyl-1,1-dimethyl-6-tert-butylindane (ADBI; Celestolide®, Crysolide®) and 1-tert-butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzene (musk ketone) were detected at low concentrations in most of the samples. Two other nitro musks, namely 1,1,3,3,5-pentamethyl-4,6-dinitroindene (musk moskene) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), were only detected in a single surface water sample. Solid-phase microextraction (SPME) with detection by gas chromatography-mass spectrometry (GC-MS) has proven to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples. Internal calibration with a suitable internal standard enables reproducible quantitation of the analytes down to the low ng/L-level.     

Production of Drinking Water from Highly Contaminated Surface Waters: Removal of Organic,Inorganic, and Microbial Contaminants Applying Mobile Membrane Filtration Units

In military out of area missions of the Bundeswehr, it can be necessary to produce drinking water even from highly polluted surface waters containing a variety of organic, inorganic, and microbiological contaminants. Thus, mobile drinking water purification systems must be able to remove such contaminants as far as possible to meet the requirements of the German and European drinking water regulation/directive. Presently, two novel drinking water purification units applying membrane filtration undergo intensive long‐term trials carried out by the Bundeswehr. If these trials positively proof the functionality of these units and their ability to remove all possible contaminants they shall substitute so far available devices which use large amounts of chemicals and charcoal filtration for water purification.In the course of a research project, the functionality of the new devices and their efficacy to remove high amounts of algae, microbes, and organic and inorganic pollutants are additionally tested in “worst‐case” field studies. In September 2000, the first mobile drinking water purification unit was tested at the Teltowkanal in Berlin, Germany.This canal was chosen because it carries high burdens of municipal sewage effluents. The results from the fatigue test confirmed the ability of the water purification unit to reduce the concentrations of all contaminants meeting the maximum tolerance levels set by the German/European drinking water regulation.The pre‐filtration device was very effective in removing algae and solid particles to protect the membranes from clogging and to enable an almost maintenance‐free operation. Residues of pharmaceuticals and some other organic contaminants have almost totally been removed from the surface water where they were detected at individual concentrations up to the μg/L‐level.     

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.     

Physico‐chemical Assessment of the Reference Status in German Surface Waters: A Contribution to the Establishment of the EC Water Framework Directive 2000/60/EG in Germany

For the establishment of the EC Water Framework Directive in Germany the physico‐chemical reference conditions of surface waters in Germany had to be determined. The results of the statistical analysis of 3500 data sets of 31 surface water catchment types show that water body types can be aggregated to bogs and bog riverside meadows, saliniferous type, carbonatic‐dolomitic type, sandy‐clayey type, silicatic type, and metallogenic type. The data base allows an assessment of the plausibility of the surface water quality classification and quality targets of the LAWA (Länderarbeitsgemeinschaft Wasser). The investigated reference status of the natural surface waters for the considered elements in the suspended particulate matter, except in metallogenic landscapes, corresponds to the water quality class I of the LAWA. The reference conditions of cadmium and mercury in the total water phase are significantly higher than the quality targets of the LAWA. The evaluated reference data of the other physico‐chemical parameters in the total water phase show, that assessable physico‐chemical parameters refer to a quality class of I, mainly and quality class II, locally. Mainly, the data reached the quality targets of the LAWA. In spite of the hard evaluation criteria to separate reference sites a special enrichment of nitrate and cadmium was found in many German surface water reference catchment types.     

Application of AMD to the Determination of Crop Protection Agents in Drinking Water. Part IV: Fundamentals of a Confirmatory Test

A method is described for the determination of fifteen active ingredients of plant protecting products in ground-, raw, and drinking water. After extraction and enrichment of the pesticides from the water sample with solid-phase extraction, the extract is fractionated on silica-coated TLC plates, first in a so-called screening gradient by AMD (automated multiple development). The detection of the pesticides is performed by UV multidetection. Positive results from the first separation are confirmed by a second separation on silica in an AMD gradient of distinctly different selectivity, compared to the first separation. Following this strategy, it is possible to distinguish nearly all nonvolatile, from water extractable, active ingredients of plant protecting products in the market. UV spectra are taken for further confirmation of positive results. In most cases, this is possible even at the limit of determination. All chromatograms and spectra shown are raw data, resulting from the confirmatory test DIN 38407 part 11, in the laboratory of one participant*). The method is standardized in the meantime as DIN V 38407-11.     

Arsenic — a Review. Part II: Oxidation of Arsenic and its Removal in Water Treatment

In natural waters arsenic normally occurs in the oxidation states +III (arsenite) and +V (arsenate). The removal of As(III) is more difficult than the removal of As(V). Therefore, As(III) has to be oxidized to As(V) prior to its removal. The oxidation in the presence of air or pure oxygen is slow. The oxidation rate can be increased by ozone, chlorine, hypochlorite, chlorine dioxide, or H₂O₂. The oxidation of As(III) is also possible in the presence of manganese oxide coated sands or by advanced oxidation processes. Arsenic can be removed from waters by coprecipitation with Fe(OH)₃, MnO₂ or during water softening. Fixed‐bed filters have successfully been applied for the removal of arsenic.The effectiveness of arsenic removal was tested in the presence of adsorbents such as FeOOH, activated alumina, ferruginous manganese ore, granular activated carbon, or natural zeolites. Other removal technologies are anion exchange, electrocoagulation, and membrane filtration by ultrafiltration, nanofiltration or reverse osmosis.