Robert Gatermann

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.

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.

Occurrence of musk xylene and musk ketone metabolites in the aquatic environment

Abstract Quantification of musk xylene (MX) and musk ketone (MK) was for the first time achieved in aquatic environmental samples simultaneously with their transformation products 4-amino-MX, 2-amino-MX, and 2-amino-MK at a ng/L level using liquid-liquid extraction and subsequent GC-MS and GC with AFID detection. Thus, the transformation of nitro musks to the corresponding amines could be studied in samples of the sewage plant Hamburg and of the river Elbe. In the influent of the sewage treatment plant concentrations of 150 and 550 ng/L were found for MX and MK, respectively, while in the effluent the corresponding values were 10 and 6 ng/L. The amino derivatives as transformation products were not detectable in the influent samples, however, values of 10 ng/L (2-amino-MX), 34 ng/L (4-amino-MX), and 250 ng/L (2-amino-MK) were found in the effluent samples. These latter concentrations were 4 to 40 times higher than the parent compounds. The simultaneous decrease in the nitro musk concentrations and the increase in the amino derivatives suggest that, besides adsorption at the sludge, this transformation pathway plays an important role. In the Elbe river the concentrations of 4-amino-MX attained at least 3 to 10 fold higher values (1 – 9 ng/L) than the parent compound, while 2-amino-MK exhibited a concentration of 7 ng/L. These results suggest that monitoring programmes as well as risk assessments of nitro musks in aquatic ecosystems should include the transformation products such as the amino derivatives investigated herein.

ENANTIOMERIC COMPOSITION OF THE POLYCYCLIC MUSKS HHCB AND AHTN IN DIFFERENT AQUATIC SPECIES

Synthetic polycyclic musk fragrances are mainly represented by the compounds HHCB (Galaxolide(TM)) and AHTN (Tonalide(TM)). Because of their volume of use and their bioaccumulation potential, there is concern with respect to their environmental safety. HHCB and AHTN are chiral compounds, and gas chromatography using modified cyclodextrins as chiral stationary phases coupled to high-resolution mass spectrometry enabled enantioselective analysis even under unfavorable matrix conditions. The gas chromatographic elution order of (4S,7RS)- and (4R,7RS)-HHCB was assigned using synthetic (4S, 7RS)-HHCB. Fish and mussels reared in a pond associated with a municipal waste water treatment plant and semipermeable membrane devices exposed in the pond were analyzed for HHCB and AHTN. The highest lipid concentrations of HHCB and AHTN were observed in mussels (Dreissena polymorpha), tench (Tinca tinca), and crucian carp (Carassius carassius). Pronounced deviations in enantiomeric composition from racemic HHCB were observed in crucian carp and from racemic AHTN in tench. Correlations between lipid levels, enrichment, and enantioselective biotransformation of HHCB or AHTN were not seen. Selective biotransformation depended on both the compound and the species involved. The present study gives the first account of the enantiomeric composition of HHCB and AHTN in aquatic species. The lactone, 1,3,4,6,7,8-hexahydro-4,6,6,7,8, 8-hexamethylcyclopenta[g]-2-benzopyran-1-one, an oxidation product of HHCB, has been identified for the first time in environmental samples. Copyright 1999 Wiley-Liss, Inc.

Musk xylene and musk ketone amino metabolites in the aquatic environment

The monoamino metabolites of the nitro musk fragrances musk xylene (MX) and musk ketone (MK) were analysed simultaneously with their parent compounds by GC/ECD, GC/PND and GC/EI/MS in the various compartments of the aquatic environment. In this review the data of the metabolites 4-NH2-MX, 2-NH2-MX, and 2-NH2-MK in five river water and seven sewage samples, six sediment samples and in a total of 33 biota samples are summarized and discussed. In the effluents of two municipal sewage plants low nitro musk concentrations and comparatively high levels of the amino metabolites (maximum concentrations: 34 ng 4-NH2-MX/L, 250 ng 2-NH2-MK/L) were analysed indicating that besides adsorption to the sludge the metabolization pathway plays an important role in the sewage plant. In water samples from the river Elbe the transformation products were the dominant compounds as well. In general, in water samples the concentrations of 2-NH2-MK exceeded those of the main MX metabolite 4-NH2-MX significantly. In biota samples 4-NH2-MX seems to be the main metabolite, very often its contents were higher than those of the parent compound. Maximum concentrations of 4-NH2-MX were found in tenches from a sewage pond (3600 microg/kg lipid), a species dependent bioaccumulation was discussed. The bioconcentration of 2-NH2-MK in biota samples is relatively low. There are only few toxicological studies on the mixed amino nitroaromatics, whose data indicate the relevance of the monoamino metabolites in environmental analysis and toxicology and the urgent need of further investigations.

Results of non target screening of lipophilic organic pollutants in the German Bight. IV: Identification and quantification of chloronitrobenzenes and dichloronitrobenzenes

Within this study all three monochloronitrobenzenes were identified and quantified in water of the German Bight of the North Sea. The concentrations ranged from <0.02 to 8.9 ng/L. The latter high value was found in the estuary of the River Elbe, though. Additionally, 2,5-dichloronitrobenzene and 3,4-dichloronitrobenzene were identified and quantified. The concentrations of these compounds ranged from <0.05 to 7.7 ng/L. The major path of input for the chloronitrobenzenes to this marine area is the River Elbe. A method for quantification is described.

Results of non target screening of lipophilic organic pollutants in the German Bight III: Identification and quantification of 2,5-dichloroaniline

Abstract The presence of 2,5-dichloroaniline in estuarine and marine waters is reported. A method for the quantification is described and the results of the quantification in water from the North Sea are given for 1990 and 1995. The concentrations reach from

The distribution of O,O,O,trimethylthiophosphate and O,O,S- trimethyldithiophosphate in the North Sea

Abstract An analytical approach is presented which allows quantification of thiophosphates at pg/L (ppq) levels by fluid-fluid extraction and subsequent GC-AFID detection. The high efficiency of this detector for this class of compounds is demonstrated by presenting results of O,O,O-trimethylthiophosphate (TMTP) and O,O,S-trimethyldithiophosphate (TMDTP) in North Sea water samples from two different years (1991, 1993) as well as in samples of the ljsselmeer and the Elbe river. The concentrations in the North Sea varied between 1 – 1400 pg/L and 2 – 9 400 pg/L, respectively. This is the first report about the contamination of sea water with thiophosphates and their distribution in the German Bight and the eastern part of the North Sea.