Th. Heberer

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. Vorkommen und Verteilung organischer Kontaminanten im aquatischen System in Berlin. Teil I: Arzneimittelruckstande und weitere polare Kontaminanten im Berliner Oberflachen- und Grundwasser Im Rahmen eines Screenings von 30 reprasentativen Oberflachenwasserproben aus Flussen, Seen und Kanalen Berlins wurden eine Reihe polarer organischer Kontaminanten detektiert. Ruckstande von Arzneimitteln und von N-(Phenylsulfonyl)-sarcosin, die uber die verschiedenen Klarwerke in die Oberflachengewasser eingetragen werden, wurden in Konzentrationen bis in den μg/L-Bereich in den Proben gefunden. Zu den am haufigsten gefundenen Pharmazeutika gehorten Clofibrinsaure, Diclofenac, Ibuprofen und Propiphenazon sowie zwei weitere Metabolite von Arzneimitteln. Die Konzentrationen der ebenfalls gefundenen polaren Pestizide Dichlorprop und Mecoprop lagen hingegen immer unterhalb von 0.1 μg/L. Zusatzliche Untersuchungen von Wasserproben, die den Grundwasserbrunnen bzw. den Grundwasserbeobachtungsrohren eines Wasserwerkes entnommen wurden, zeigten, das polare Kontaminanten wie Arzneimittelruckstande oder N-(Phenylsulfonyl)-sarcosin aus kontaminierten Oberflachengewassern in die Grundwasseraquifere eingetragen werden konnen, wenn die Uferfiltration oder die kunstliche Grundwasseranreicherung zur Trinkwassergewinnung eingesetzt wird.

Determination of polar pharmaceuticals in sewage water of Greece by gas chromatography–mass spectrometry ☆

Sewage influents and effluents of different urban areas of Greece, were analyzed for polar pharmaceutical residues, used in human medicine. Drugs investigated were the anti-inflammatory drugs diclofenac and ibuprofen, the metabolite of the drugs clofibrates used as blood lipid regulators, clofibric acid and the analgesics phenazone and propyphenazone. Analysis was carried out using capillary gas chromatography-mass spectrometry with selected ion monitoring. The method used was involved solid phase extraction (C(18)) and derivatization with pentafluorobenzyl bromide. Diclofenac was detected in every sewage effluent sample.

Determination of clofibric acid and N-(phenylsulfonyl)-sarcosine in sewage, river and drinking water

Abstract Two polar compounds, the drug metabolite clofibric acid (2-(4)-chlorophenoxy-2-methyl propionic acid) and N-(phenylsulfonyl)-sarcosine, were detected as organic contaminants in groundwater samples from sewage farm areas near Berlin at maximum concentrations of 4 μg/l and 150 μg/l, respectively. Contaminations by these two compounds were also found in most of the drinking water samples collected from the 14 waterworks in the Berlin area. The maximum concentrations in drinking water samples were 270 ng/l for clofibric acid and 105 ng/l for N-(phenylsulfonyl)-sarcosine. The analytical results obtained correlate well with the percentage values of artificial groundwater enrichment and bank filtrate used by any particular water treatment plant in drinking water production. Thus, it can be assumed that both polar contaminants commonly leach into drinking water and are not eliminated by the drinking water treatment used by the Berlin waterworks. Positive findings in screening analyses of surface water sa...

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. Vorkommen und Verteilung organischer Kontaminanten im aquatischen System Berlins. Teil III: Bestimmung von synthetischen Moschusverbindungen im Berliner Oberflachenwasser mittels Festphasenmikroextraktion (SPME) und Gaschromatographie-Massenspektrometrie (GC-MS) Polycyclische Moschusverbindungen und Nitromoschusverbindungen, die vor allem fur die Parfumierung von kosmetischen Mitteln und Bedarfsgegenstanden Verwendung finden, werden uber kommunale Abwasser durch Klarwerke in die Berliner Oberflachengewasser eingetragen. Im Rahmen eines Screenings von 30 reprasentativen Oberflachenwasserproben aus Flussen, Seen und Kanalen Berlins wurden insbesondere die polycyclischen Moschusduftstoffe-1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran (HHCB; Galaxolide®, Abbalide®) und 7-Acetyl-1,1,3,4,4,6-hexamethyltetralin (AHTN; Tonalide®, Fixolide®) in Konzentrationen bis in den μg/L-Bereich im Oberflachenwasser detektiert. In der Wuhle, einem kleinen Gewasser, das zu grosen Teilen aus Abwassereinleitungen besteht, wurden maximale Konzentrationen von 12.5 bzw. 6.8 μg/L fur HHCB und AHTN gemessen. Weiterhin wurden die polycyclische Moschusverbindung 4-Acetyl-1,1-dimethyl-6-tert-butylindan (ADBI; Celestolide®, Crysolide®) und die Nitromoschusverbindung 1-tert-Butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzol (Moschus Keton) in den meisten der Proben gefunden. Zwei weitere Nitromoschusverbindungen, 1,1,3,3,5-Pentamethyl-4,6-dinitroindol (Moschus Mosken) und 1-tert-Butyl-3,5-dimethyl-2,4,6-trinitrobenzol (Moschus Xylol) wurden lediglich in einer Probe gefunden. Die Festphasenmikroextraktion (SPME) erwies sich in Verbindung mit der Kapillargaschromatographie-Massenspektrometrie (GC-MS) als schnelle und zuverlassige Methode fur das Screening von synthetischen Moschusverbindungen in Oberflachen- und Abwasserproben. Die interne Kalibrierung unter Verwendung eines geeigneten internen Standards ermoglichte die reproduzierbare Quantifizierung der Analyten bis in den unteren ng/L-Bereich.

Analysis of Phenoxycarboxylic Acids and Other Acidic Compounds in Tap, Ground, Surface and Sewage Water at the Low ng/1 Level

Abstract Solid-phase extraction with RP-C18 phase has been successfully applied for the determination of more than 30 acidic herbicides and related compounds from environmental water samples. Detection of these contaminants was performed after pentafluorobenzylation at the low ng per liter level using gas chromatography/mass spectrometry. With multiple-component SIM programming simultaneous detection of all compounds in one single gas chromatographic run was possible. Increased reliability of acidic herbicide analysis from water samples with high matrix content was achieved by using a surrogate as well as an internal standard. 2-(4-chlorophenoxy) butyric acid, being a structural isomer of clofibric acid and mecoprop, was chosen as surrogate standard because cloflbric acid was found to be a widespread contaminant in environmental water samples from the Berlin area. Mecoprop, dichlorprop and 1-naphthylacetic acid were also found in field studies of some of these samples. A few examples of positive findings ...

Determination of phenoxyalkanoic acids and other acidic herbicides at the low ppt level in water applying solid-phase extraction with RP-C18 materi

Abstract A method for the determination of 34 phenoxyalkanoic acids and other acidic compounds in water samples was developed. Recoveries were made from 11 of d

Formation of an artifact of diclofenac during acidic extraction of environmental water samples

Solid-phase extraction at an acidic pH is used as a common sample preparation method for analyzing residues of the analgesic drug diclofenac (2-[(2,6-dichlorophenyl)amino] benzeneacetic acid) in environmental water samples. This paper describes the matrix-dependent formation of an artifact of diclofenac during sample preparation resulting in an up to 40% underestimation of diclofenac concentrations especially in matrix-prone samples such as sewage effluents or surface water. The artifact most likely being formed during acidification of the sample was unequivocally identified as 1-(2,6-dichlorophenyl)indolin-2-one by capillary gas chromatography-mass spectrometry. To avoid an underestimation of the analytical results quantification of both diclofenac and its artifact is recommended.

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin.Part II: Substituted Phenols in Berlin Surface Water

In a surface water screening, 30 representative surface water samples collected from rivers, canals, and lakes in Berlin were investigated for the presence of 22 substituted phenols. The phenols selected include the 11 phenols considered as “priority pollutants” by the US Environmental Protection Agency (US-EPA). Surface water samples were extracted applying solid-phase extraction with styrenedivinylbenzene adsorbent. The recoveries, determined in spiking experiments, were between 80 % and 103 %. After derivatization with N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) the samples were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). Phenol, cresols, 2-ethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, 2-nitrophenol, and 4-nitrophenol were detected in the surface water samples at concentrations between 0.02 μg/L and 7.8 μg/L, respectively. The distribution of these residues in the Berlin surface waters showed that the phenolic residues, with the exception of pentachlorophenol and 2-ethylphenol, do not originate primarily from municipal sewage treatment plants discharges. Some of the phenols are formed naturally or occur as ubiquitous anthropogenic contaminants in the aquatic system. Vorkommen und Verteilung organischer Kontaminanten im aquatischen System Berlins. Teil II: Substituierte Phenole im Berliner Oberflachenwasser Im Rahmen eines Screenings der Berliner Oberflachenwasser wurden 30 reprasentative Wasserproben aus Flussen, Seen und Kanalen auf 22 substituierte Phenole hin untersucht. Die elf von der U.S.-amerikanischen Umweltbehorde (?US-Environmental Protection Agency – EPA“) in die Liste wichtiger Umweltkontaminanten aufgenommenen Phenole wurden dabei in die Untersuchung mit einbezogen. Die Phenole wurden mittels Festphasenextraktion mit Styrol-Dinvinylbenzol-Polymermaterial extrahiert. Die Wiederfindungsraten, die durch Dotierung der Original-Wasserproben bestimmt wurden, lagen zwischen 80 % und 103 %. Die Analyten wurden nach Derivatisierung mit N-(tert-Butyldimethylsilyl)-N-methyl-trifluoracetamid (MTBSTFA) mittels Kapillargaschromatographie-Massenspektrometrie bestimmt. In den Oberflachenwasserproben wurden Phenol, Kresole, 2-Ethylphenol, 2-Chlorphenol, 4-Chlor-3-methylphenol, Pentachlorphenol, 2-Nitrophenol und 4-Nitrophenol nachgewiesen. Die Einzelkonzentrationen lagen jeweils zwischen 0.02 μg/L und 7.8 μg/L. Die Verteilung der Phenolruckstande in den Berliner Oberflachengewassern zeigt jedoch, das sie, mit Ausnahme von Pentachlorphenol bzw. 2-Ethylphenol, nicht auf die Einleitung von kommunalen Abwassern zuruckzufuhren sind. Viele der gefundenen Phenole werden vielmehr naturlich gebildet oder ubiquitar aus anderen anthropogenen Quellen eingetragen.

Automated recognition of target compounds at low levels in environmental samples by means of capillary gas chromatography—mass spectrometry with dedi: II. Application to pesticides in groundwater samples

Abstract The use of the macro program AUTARG in the daily routine analysis of pesticides in groundwater was investigated. AUTARG Level 1 proved to be a valuable