Heinrich Hühnerfuss

Drugs and personal care products as ubiquitous pollutants: occurrence and distribution of clofibric acid, caffeine and DEET in the North Sea

An analytical method is presented, which allows the simultaneous extraction of neutral and acidic compounds from 20-L seawater samples at ambient pH (approximately 8.3). It is based on a solid-phase extraction by means of a polystyrene-divinylbenzene sorbent and gas chromatographic-mass spectrometric detection, and provides detection limits in the lower pg/L range. The method was applied to the screening of samples from different North Sea areas for clofibric acid, diclofenac, ibuprofen, ketoprofen, propyphenazone, caffeine and N,N-diethyl-3-toluamide (DEET). Whereas clofibric acid, caffeine and DEET showed to be present throughout the North Sea in concentrations of up to 1.3, 16 and 1.1 ng/L, respectively, propyphenazone could only be detected after further clean-up. Diclofenac and ibuprofen were found in the estuary of the river Elbe (6.2 and 0.6 ng/L, respectively) but in none of the marine samples. Ketoprofen was below the detection limit in all samples.

Imaging of biogenic and anthropogenic ocean surface films by the multifrequency/multipolarization SIR-C/X-SAR

Results from the analyses of several spaceborne imaging radar-C/X-band synthetic aperture radar (SIR-C/X-SAR) images are presented, which were acquired during the two SIR-C/X-SAR missions in April and October 1994 by the L-, C-, and X-band multipolarization SAR aboard the space shuttle Endeavour. The images showing natural (biogenic) surface slicks as well as man-made (anthropogenic) mineral oil spills were analyzed with the aim to study whether or not active radar techniques can be applied to discriminating between these two kinds of surface films. Controlled slick experiments were carried out during both shuttle missions in the German Bight of the North Sea as well as in the northern part of the Sea of Japan and the Kuroshio Stream region, where surface films of different viscoelastic properties were deployed within the swath of the shuttle radars. The results show that the damping behavior of the same substance is strongly dependent on wind speed. At high wind speed (8–12 m/s) the ratio of the radar backscatter from a slick-free and a slick-covered water surface (damping ratio) is smaller than at low to moderate wind speeds (4–7 m/s). At 12 m/s, only slight differences in the damping behavior of different substances were measured by SIR-C/X-SAR. Furthermore, several SAR scenes from various parts of the worlds oceans showing radar signatures of biogenic as well as anthropogenic surface films at low to moderate wind speeds are analyzed. The damping behavior of these different kinds of oceanic surface films varies particularly at Lband where the biogenic surface films exhibit larger damping characteristics. Results of polarimetric studies from multipolarization SAR images showing various surface films are presented. It can be delineated from these results that Bragg scattering as well as specular reflection contribute to the backscattered radar signal at low incidence angles (up to 30°). It is concluded that at low to moderate wind speeds, multifrequency radar techniques seem to be capable of discriminating between the different surface films, whereas at high wind conditions a discrimination seems to be difficult.

Concentrations of the antifouling compound Irgarol 1051 and of organotins in water and sediments of German North and Baltic Sea marinas

Abstract A survey of 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (Irgarol 1051) and organotins, used as biocides in antifouling paints, was carried out in German marinas of the North and Baltic Sea. Highest levels of the s-triazine herbicide were found in Baltic Sea marinas where water exchange was restricted (water up to 440 ng/l; sediment about 220 ng/g dry weight), while in the North Sea marinas with higher water exchange rates lower concentrations were encountered (water 11–170 ng/l; sediment 3–25 ng/g dry weight). Although the application of the antifouling agent tributyltin (TBT) was banned for small vessels (

Chiral Polychlorinated Biphenyl Transport, Metabolism, and Distribution: A Review

Chirality can be exploited to gain insight into enantioselective fate processes that may otherwise remain undetected because only biological, but not physical and chemical transport and transformation processes in an achiral environment will change enantiomer compositions. This review provides an in-depth overview of the application of chirality to the study of chiral polychlorinated biphenyls (PCBs), an important group of legacy pollutants. Like other chiral compounds, individual PCB enantiomers may interact enantioselectively (or enantiospecifically) with chiral macromolecules, such as cytochrome P-450 enzymes or ryanodine receptors, leading to differences in their toxicological effects and the enantioselective formation of chiral biotransformation products. Species and congener-specific enantiomer enrichment has been demonstrated in environmental compartments, wildlife, and mammals, including humans, typically due to a complex combination of biotransformation processes and uptake via the diet by passive diffusion. Changes in the enantiomer composition of chiral PCBs in the environment have been used to understand complex aerobic and anaerobic microbial transformation pathways, to delineate and quantify PCB sources and transport in the environment, to gain insight into the biotransformation of PCBs in aquatic food webs, and to investigate the enantioselective disposition of PCBs and their methylsulfonyl PCBs metabolites in rodents. Overall, changes in chiral signatures are powerful, but currently underutilized tools for studies of environmental and biological processes of PCBs.

New method for rapid solid-phase extraction of large-volume water samples and its application to non-target screening of North Sea water for organic contaminants by gas chromatography-mass spectrometry

A method has been developed that allows the solid-phase extraction of microorganic compounds from large volumes of water (10 l) for non-target analysis of filtered seawater. The filtration-extraction system is operated with glass fibre filter candles and the polymeric styrene-divinylbenzene sorbent SDB-1 at flow-rates as high as 500 ml/min. Recovery studies carried out for a couple of model substances covering a wide range of polarity and chemical classes revealed a good performance of the method. Especially for polar compounds (log Kow 3.3-0.7) quantitative recovery was achieved. Limits of detection were between 0.1 and 0.7 ng/l in the full scan mode of the MS. The suitability of the method for the analysis of marine water samples is demonstrated by the non-target screening of water from the German Bight for the presence of organic contaminants. In the course of this screening a large variety of substances was identified including pesticides, industrial chemicals and pharmaceuticals. For some of the identified compounds their occurrence in marine ecosystems has not been reported before, such as dichloropyridines, carbamazepine, propyphenazone and caffeine.

On the Reduction of the Radar Backscatter by Oceanic Surface Films: Scatterometer Measurements and Their Theoretical Interpretation

Abstract During the two SIR-C/X-SAR missions in 1994, surface film experiments were performed in the North Sea with a 5-frequency/multipolarization scatterometer flown on a helicopter, in order to investigate the reduction of the radar backscatter in the presence of quasibiogenic and anthropogenic sea surface films, particularly, at different wind speeds. Under all wind conditions encountered in this study, the measured damping ratio (i.e., the ratio of the radar backscatter from a slick-free and a slick-covered water surface) increases with increasing Bragg wavenumber. It is shown that not only Marangoni damping theory, but also wind-induced effects, primarily the energy input by the wind into the wave spectrum, also have to be taken into account. The reductions measured at low to moderate wind speeds (3.5–4 m/s and 5 m/s) are qualitatively explained by means of a comparison of the different source terms of the action balance equation. For the case of high wind speed (12 m/s) a theoretical model for the damping ratios is developed. Using this model, the experimental data can well be reproduced, and the absence of the Marangoni damping maximum at intermediate Bragg wavenumbers (approximately 100 rad/m) can be interpreted. Furthermore, the model can explain the similarities between the radar backscatter reductions measured over quasibiogenic and anthropogenic surface films under high wind conditions.

Polycyclic and nitro musks in the environment: A comparison between Canadian and European aquatic biota

Nitro and polycyclic musks were determined for the first time in Canadian aquatic fauna such as lobster, winter flounder, American eel, lake trout, clams and mussels. Samples from densely populated areas, Halifax and the industrialized Miramachi estuary, showed relatively high concentrations of musk ketone (4-acetyl-1-tert-butyl-3,5-dimethyl-2,6-dinitrobenzene, MK; maximum levels: mussels 2,200 ng/g lipid; winter flounder muscle 2,700 ng/g lipid; clams 17,700 ng/g lipid) and HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta[g]-2-benzopyrane, ‘galaxolide’; mussels 1,700 ng/g lipid; winter flounder 40 ng/g lipid; clams 3,000 ng/g lipid), while the samples from sparsely populated areas like Cap-Pele exhibited lower levels (MK maximum levels 130 ng/g lipid; HHCB maximum levels 16 ng/g lipid). Most samples contained relatively low concentrations of musk xylene (1-tert-butyl-3,5-dimetyl-2,4,6-trinitrobenzene, MX) and AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-tetrahydro-napthalene, ‘tonalide’). In contrast, in Western Europe, concentrations of the polycyclic musks HHCB and AHTN in fish presently exceed those of the nitro musks by about one to three orders of magnitude. These data seem to reflect the different application modes in Western Europe and North America with regard to the prevailing musk components in fragrances. Synthetic musks were not detectable in most commercial fish oils used in the preparation of aquaculture feed and fish lipids extracted in the 1980s in the laboratory, with the exception of a pollock (Pollachius virens) lipid from the Halifax area, which contained MX and MK at 350 and 64 ng/g lipid, respectively.

Enantioselective chromatography—A powerful tool for the discrimination of biotic and abiotic transformation processes of chiral environmental pollutants

On the basis of the general principles of chirality the characteristics of chromatograms obtained by enantioselective GC and HPLC are explained, followed by a description of different enantioselective chromatographic methods (HPLC, high-resolution GC, multidimensional GC, CE, supercritical fluid chromatography) thus far applied. The potential of enantioselective chromatography is highlighted by examples of studies on microbial, enzymatic and photochemical transformation processes, on air/sea exchange and long-range transport processes, enantioselective toxic effects as well as on the fate of emerging environmental chiral pollutants such as pharmaceuticals, personal care products and the flame retardant 1,2,5,6,9,10-hexabromocyclododecane.

The distribution of nitrobenzene and other nitroaromatic compounds in the North Sea

Abstract An analytical approach is presented that allows quantification of nitroaromatics below ng l −1 (ppt) levels by fluid-fluid extraction and subsequent GC-AFID detection. Nitrobenzene, 1-chloro-2-nitrobenzene and other nitroaromatic compounds such as musk xylene and musk ketone, synthetic fragrances used on a large scale, were analysed in 33 North Sea water samples in concentrations between 0.05 and 2.5 ng l −1 . This is the first report about the contamination of seawater with nitro musks and the distribution of nitroaromatics in the German Bight and the eastern part of the North Sea.

Radar signatures of marine mineral oil spills measured by an airborne multi-frequency radar

Radar signatures of mineral oil spills consisting of heavy and light fuel were measured by an airborne five-frequency ( L - S - C - X - and K -band) multi u polarization microwave scatterometer flown on a helicopter during a controlled oil spill experiment in the North Sea. The damping ratio, defined as the ratio of the backscattered radar power from an oil-free and an oil-covered sea surface, was measured at different radar frequencies and incidence angles such that the Bragg wavenumbers, k, between 20 radm 1 and 500 radm 1 were covered. The B following results were obtained: for the five oil spills deployed in the experiment the damping ratio, in general, increases monotonically from k 20 radm 1 to B k 500 radm 1 . At S - C - X - and K -band, the damping ratio is larger for heavy B u fuel than for light fuel spills, while at L- band it is almost the same. For heavy fuel, the damping ratio increases with increasing thickness of the oil layer. Furthermore, for wind speeds between 6 m s 1 and 10 m s 1 the ...