Kai Bester

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 (

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.

Triazines in the Baltic and North Sea

A new analytical approach is presented that allows quantification of triazines in sea-water at ng I−1 (ppt)-levels by fluid-fluid extraction and subsequent GC-AFID detection. Limits of quantifications and recovery rates are reported. The concentrations of atrazine, simazine and terbuthylazine in the German Bight range from 1 ng I−1 to 1100 ng I−1, while in the western Baltic Sea values between 1 ng I−1 and 13 ng I−1 are found. These concentration values imply that the Elbe estuary and the German Bight north of the Elbe estuary along the German coast must be regarded as highly contaminated.

Biological effects of triazine herbicide contamination on marine phytoplankton

The effects of the herbicide atrazine on marine phytoplankton typical of the German Bight (North Sea) were investigated by means of four mesocosm (tank) experiments. Three tanks were spiked with atrazine (120, 560, and 5,800 ng/L, respectively). These concentrations cover the range found in the German Bight, in coastal waters, and in the estuary of the river Elbe. The lowest atrazine concentration applied was of the same order of magnitude as the background concentration of triazine herbicides in North Sea water near the island of Heligoland. A relationship between concentration of atrazine (dosis) and concentration of “excreted” dissolved organic phosphorus (DOP) as well as dissolved organic nitrogen (DON) (effect) can be inferred, where high concentrations of triazines lead to high concentrations of DON and DOP. Furthermore, the decrease in the pH-value from 9.2 to about 8.7–8.9 in the three tanks spiked with atrazine during the “stationary growth phase” in comparison with the fourth tank (control, i.e., background levels) implies that photosynthesis is reduced. This effect is accompanied by lower chlorophyll concentrations, reduced primary production, and higher concentrations of amino acids in the water.

Bioassay-directed chemical analysis of River Elbe surface water including large volume extractions and high performance fractionation

A bioassay-directed fractionation and identification (toxicity identification evaluation procedure) was performed on extracts of 10 1 River Elbe water samples. The experimental method included a SDB-1 solid phase extraction followed by RP-HPLC fractionation and subfractionation. Chemical analysis by GC-MS as well as acute toxicity testing using a luminescent bacteria assay were conducted in the respective fractions. Many substances were identified, among which were pesticides and pharmaceuticals, but many compounds remained unknown.

Results of non-target screening of lipophilic organic pollutants in the German Bight I: benzothiazoles

Abstract The presence of benzothiazole and methylthiobenzothiazole in estuarine and marine waters is shown for the first time. A method for the quantification of these compounds is described and the results of the quantification in water from the North Sea are given. The concentrations range from 0.04 to 1.37 ng/l methylthiobenzothiazole in the North Sea, while 55 ng/l were found in the Elbe river. The values for benzothiazole vary from 0.25 to 2.7 ng/l.

Annual balances of hexachlorocyclohexanes, polychlorinated biphenyls and triazines in the German Bight☆

Abstract During the PRISMA-Project concentrations of hexachlorocyclohexanes (α-HCH, γ-HCH), polychlorinated biphenyls (the ‘DIN-PCBs’: PCB 28, PCB 52, PCB 101, PCB 153, PCB 138, PCB 180), and triazines (atrazine, simazine, terbutylazine) were determined in the German Bight within the water column and in rain water. In addition, the HCHs, and PCBs were also analysed in sediment samples. The concentration values were combined with average lateral inflow and outflow rates of water masses into and out of the German Bight and with the respective inflow rates of the rivers Elbe, Weser and Ems. Thus an estimation of the annual balances of these compounds was accessible that allowed the following conclusions: a loss of 2 t yr−1 γ-HCH between input into and output out of the German Bight has to be stated, while more α-HCH is leaving this area at its northern boundary. This phenomenon can be explained by the different stability of the two HCH isomers. The mobility of PCBs has to be largely attributed to sediment transport, where during the summer period a larger amount is being transported into than out of the German Bight, while during spring the opposite observation was made. Furthermore, evidence is presented that stresses the importance of the riverine input of triazines to the German Bight. The role of their atmospheric input is not very pronounced within the coastal area, however, it has to be taken into consideration for the more distant North Sea regions. This holds, in particular, for the triazines, where atmospheric transport may become significant already in North Sea areas outside the plume of the river Elbe.

Bromocyclen contamination of surface water, waste water and fish from Northern Germany, and gas chromatographic chiral separation

The concentrations of bromocyclen were determined in the water and muscle tissue of trout and bream from the river Stor (northern Germany), to locate the source of this contaminant. The concentrations in water varied between n.d. and 261 pg/L, while in the fish samples concentrations between 0.01 and 0.24 mg/kg fat were determined. In addition, remarkably high concentrations of bromocyclen were found in waste water from sewage plants discharging into the river Stor and at the city of Hamburg. Sewage plants can be, therefore, assumed to be the main source of bromocyclen contamination. This is the first report about the contamination of river water and waste water with bromocyclen. Determination by chiral capillary gas chromatography using a modified cyclodextrin phase showed no significant enantiomeric excess in the water samples, but a preferential degradation of (+)-bromocyclen in the fish muscle tissue of breams.

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.

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.