Abstracts:
Kai Bester and Heinrich Hühnerfuss: Improvements
of a combined size exclusion chromatography and solid phase extraction approach
for the clean-up of marine sediment samples for trace analysis of
pesticides, Fresenius J. Anal. Chem., 358, 630-634, 1997
Two methods based on gel permeation chromatography (GPC) [size exclusion
chromatography] for the analysis of traces (ng/kg) of nitrogen and phosphorus
containing pesticides like triazines or phosphothionates from marine sediment
samples are compared: A macro GPC with Biobeads SX-3 and a chromatography
on a high performance (HP-GPC) column with UV-detection. Results for eight
triazine herbicides, two triazine metabolites, the phenylurea derivative
linuron, two acetanilides and two organophosphorus compounds are given.
Concentrations obtained with the HP-GPC are compared to those obtained with
a macro GPC approach within an earlier study.
Click on the images to see the details !
 |
Figure: Chromatogram of a sediment extract, column: Polygel
HP-GPC, eluent: cyclohexane:ethylacetate 1:1, flow 1.5 mL/min, detection:
UV 254 nm |
 |
Figure: Distribution of four triazine herbicides (atrazine,
propazine, terbutylazine and
prometryn as well as the sum of the concentrations of the herbicides and
metabolites, respectively
(atraton, simazine, atrazine, propazine, terbutylazine, prometryn, terbutryn,
desethylatrazine, desethyterbutylazine
and linuron) in Wadden Sea sediment samples obtained in summer 1994. The
concentrations are given in [ng/kg] wetweight. The respective numbers indicate
the sampling site i.e. : 1: Randzel; 2: Hilgenriedersiel; 3: Bensersiel;
4: Neuharlingersiel; 5: Horumersiel; 6: Augustgroden; 7: Sehestedt; 8: Minsen |
Kai Bester1, Heinrich
Hühnerfuss1, Wilfried Lange2 and Norbert
Theobald2 : Results of non target screening of lipophilic organic
pollutants in the German Bight I: Benzothiazoles, Sci. Total Environm.
207, 111-118, 1997
1 Institut für Organische Chemie, Martin-Luther-King-Platz
6, 20146 Hamburg, Germany
2 Bundesamt für Seeschiffahrt und
Hydrographie, Bernhard Nocht Str. 78, 20359 Hamburg, Germany
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 -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.
Figure 1a: Structural formula of benzothiazole
Figure 1b: Structural formula of methylthiobenzothiazole (MTB)
Figure 1c: Structural formula of thiocyanatomethylthiobenzothiazole (TCMTBT)
Click on the images to see the details !
 |
Figure 2: Mass spectrum of methylthiobenzothiazole obtained
from a water sample from the river Elbe estuary |
 |
Figure 3: Distribution of benzothiazole and
methylthiobenzothiazole (MTB) in water of the German Bight of the North Sea.
Data are given for 1990 and 1995, respectively. Maximum values are 4 ng/L
within the fields. The rivers Ems, Weser and Elbe are indicated. The bars
in the river Elbe estuary are eight times reduced to make them fit the graph. |
Table:Concentrations in [ng/L] of benzothiazoles in the German Bight of the
North Sea in 1990 and 1995, respectively
Sample-station No |
Benzothiazole
1990 |
Benzothiazole
1995 |
MTB
1990 |
MTB
1995 |
1 |
0.66 |
(0.24)* |
0.04 |
0.39 |
4 |
1.61 |
(0.08)* |
0.55 |
0.044 |
9 |
1.11 |
(0.03)* |
0.78 |
0.16 |
27 |
2.27 |
1.23 |
1.00 |
1.37 |
30 |
1.38 |
0.37 |
1.06 |
0.60 |
36 |
1.97 |
0.40 |
1.04 |
0.24 |
Stade/Elbe |
not analysed |
2.74 |
not analysed |
55.00 |
* values are near or beyond the blank value
Kai Bester1*, Heinrich
Hühnerfuss1, Wilfried Lange2, Gerhard G.
Rimkus3 and Norbert Theobald2 : Results of non target
screening of lipophilic organic pollutants in the German Bight II: Polycyclic
Musk Fragrances, Water Research, in press 1998
1 Institut für Organische Chemie, Martin-Luther-King-Platz
6, 20146 Hamburg, Germany
2 Bundesamt für Seeschiffahrt und
Hydrographie, Bernhard Nocht Str. 78, 20359 Hamburg, Germany
3 Lebensmittel- und
Veterinäruntersuchungsamt des Landes Schleswig-Holstein, Max-Eyth-Str.
5, 24537 Neumünster, Germany
The presence of the polycyclic musk fragrances HHCB
(1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran;
trade name, e. g., galaxolide®) and AHTN
(7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene; trade name,
e.g., tonalide®) in estuarine and marine waters is shown.
A method for the quantification of these compounds is described and the results
of the quantification in water from the North Sea are given. Concentrations
reach from 0.09 to 4.8 ng l-1 for HHCB in the North Sea (95 ng l-1 in the
river Elbe estuary), while they vary from 0.08 to 2.6 ng l-1 for AHTN in
the North Sea, (67 ng l-1 in the river Elbe estuary) . The values determined
in water samples of the years 1990 and 1995 show no statistically significant
difference for AHTN, while HHCB shows a trend towards higher concentrations
in 1995 at some stations.
Table: Concentrations in [ng/L] of polycyclic musk compounds in the water
of the German Bight
of the North Sea in 1990 and 1995, respectively and the river Elbe in 1995.
Sample-station No |
HHCB 1990 |
HHCB 1995 |
AHTN 1990 |
AHTN 1995 |
1 |
0.09 |
0.17 |
0.09 |
0.08 |
4 |
0.45 |
0.15 |
0.43 |
0.08 |
9 |
0.18 |
0.22 |
0.18 |
0.16 |
27 |
0.88 |
4.8 |
0.94 |
2.6 |
30 |
0.16 |
0.55 |
0.41 |
0.38 |
36 |
0.20 |
0.30 |
0.14 |
0.19 |
Stade/Elbe |
not quantified |
95 |
not quantified |
67 |
Kai Bester1, Scarlett Biselli1, Robert
Gatermann1, Heinrich Hühnerfuss1, Wilfried
Lange2 and Norbert Theobald2: Results of non target
screening of lipophilic organic pollutants in the German Bight III:
Identification and Quantification of 2,5-Dichloroaniline, Chemosphere,
36, 1973-1983, 1998
1 Institut für Organische Chemie, Martin-Luther-King-Platz
6, 20146 Hamburg, Germany
2 Bundesamt für Seeschiffahrt und
Hydrographie, Bernhard Nocht Str. 78, 20359 Hamburg, Germany
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 <0.01 - 0.65 ng/L in the German Bight, while
8.5 ng/L were found in the estuary of the river Elbe.
Click on the images to see the details !
Figure: EI-mass spectrum of 2,5-dichloroaniline from a water sample from
the river Elbe estuary. |
|
 |
Figure: Geographical distribution of
2,5-dichloroaniline in water of the German Bight of the North Sea in 1990
and 1995, respectively. Maximum value within the fields is 0.8 ng/L. Please
note that the bars for the concentrations at the estuarine sample (Stade)
are reduced to make them fit the graph. |
Table: Concentrations in [ng/L] of 2,5-dichloroaniline in the German Bight
of the North Sea in 1990 and 1995,
respectively. na: Not analysed, as the sample was used for identification
Sample-station No |
1990 |
1995 |
1 |
0.038 |
< 0.01 |
4 |
0.036 |
< 0.01 |
9 |
0.20 |
< 0.01 |
27 |
0.064 |
0.65 |
30 |
0.46 |
0.30 |
36 |
0.19 |
0.06 |
Stade/Elbe |
na |
8.54 |
Kai Bester1*, Scarlett Biselli1,
Thomas Ellerichmann1, Heinrich Hühnerfuss1, Kattrin
Möller1, Gerhard Rimkus2 and Manfred Wolf
2: Chlorostyrenes in fish and sediment samples from the river
Elbe, Chemosphere, 37, 9-12, 1998
1 Institut für Organische Chemie, Universität Hamburg,
Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
2 Lebensmittel- und
Veterinäruntersuchungsamt des Landes Schleswig-Holstein, Max-Eyth-Str.
5, 24537 Neumünster, Germany
Chlorinated styrenes were identified in fish (bream) and sediment samples
from the river Elbe. Four hexachlorostyrenes, four heptachlorostyrenes
(concentrations in fish 1-10 ng/g wet weight) and octachlorostyrene (10-45
ng/g wet weight) were analysed. The gas chromatographic retention times and
the electron impact (EI) mass spectra of the respective hepta- and hexachloro
congeners found in the environment as well as those of some synthesised compounds
are presented and discussed. The comparison of the chromatograms from the
samples in the upper part of the river with those from the estuary revealed
a possible difference in the pattern of chlorostyrenes.
Kai Bester1, Robert Gatermann1,
Heinrich Hühnerfuss1, Wilfried Lange2 and Norbert
Theobald2: Results of non target screening of lipophilic organic
pollutants in the German Bight IV: Chloronitrobenzenes and
Dichloronitrobenzenes, Environmental Pollution, 102, 163-169, 1998
1 Institut für Organische Chemie, Martin-Luther-King-Platz
6, 20146 Hamburg, Germany
2 Bundesamt für Seeschifffahrt und
Hydrographie, Bernhard Nocht Str. 78, 20359 Hamburg, Germany
Within this study all three chloronitrobenzenes are identified to be present
in water of the German Bight of the North Sea. The concentrations ranged
from < 0.02 to 8.9 ng/L. Additionally 2,5-dichloronitrobenzene and
3,4-dichloronitrobenzene were identified at concentrations from < 0.05
to 2.78 ng/L. The mayor path of input to this marine area is the river Elbe.
A method for quantification is described.
Table 2a Concentrations in [ng/L] of chlorobenzenes in the German Bight of
the North Sea in 1990 and 1995.
3-CNB = 3-Chloronitrobenzene, 4-CNB = 4-Chloronitrobenzene, 2-CNB =
2-Chloronitrobenzene
|
3-CBN (1990) |
3-CBN (1995) |
4-CBN (1990) |
4-CBN (1995) |
2-CBN (1990) |
2-CBN (1995) |
Station No |
|
|
|
|
|
|
1 |
0.061 |
<LOD |
0.14 |
<LOD |
0.13 |
<LOD |
4 |
0.11 |
<LOD |
0.19 |
<LOD |
0.18 |
<LOD |
9 |
0.063 |
<LOD |
0.32 |
0.018 |
0.20 |
<LOD |
27 |
0.19 |
0.076 |
0.44 |
0.61 |
0.28 |
0.59 |
30 |
0.077 |
0.033 |
0.30 |
0.13 |
0.26 |
0.14 |
36 |
0.018 |
0.013 |
0.18 |
0.12 |
0.17 |
0.068 |
Stade/Elbe |
nq |
0.73 |
nq |
8.8 |
nq |
8.9 |
K. Bester: Results of experiments for the identification
of organic pollutants in the German Bight, Dt. Hydrogr. Zt., 8, 51-64,
1998
Institut für Organische Chemie, Martin-Luther-King-Platz 6, 20146 Hamburg,
Germany
Compounds such as benzothiazole derivatives, polycyclic musk fragrances,
2,5-dichloroaniline, all monochloronitrobenzenes as well as xanthen-9-on,
and nonylphenol were identified and verified in the water of the German Bight.
some of these compounds were quantified in the water of the German Bight:
Concentrations were observed in the North Sea in the ng/L scale: Benzothiazoles,
like methylthiobenzothiazole: 0.04 -1.37 ng/L, benzothiazole: 0.25 - 2.7
ng/L; polycyclic musk fragrances like galaxolide (HHCB): 0.09 - 4.8 ng/L
and tonalide (AHTN): 0.08 - 2.6 ng/L; Chloroanilines such as 2,5-dichloraniline
0.01 - 0.65 ng/L. The concentrations in the estuary of the river Elbe are
much higher. The origin of the respective compounds are diverse: While
benzothiazoles are emitted from automobile tyres and some biocides, polycyclic
musk fragrances are components of washing powders, perfumes, deodorants etc.,
these compounds reach the rivers (and the North Sea) via sewage plants. On
the other hand 2,5-dichloroaniline is used for the production of one red
dye and is obviously released from this plant.
Comparison of concentrations [ng/L] of pollutants in the German Bight (area
of station 30 within this study. Not all values originate from the same year,
though.
xanthen-9-on |
2,5-DCA |
a -HCH |
4-CNB |
MTB |
polycyclic musk fragrances |
atrazine |
terbutyl- azine |
Nonylphenol (Data published on poster, only) |
Thiophos-phates |
0.21-0.37 |
0.4 |
0.5 |
0.3 |
0.4 - 1.4 |
0.2 - 0.6 |
42 |
360 |
2.5 |
1 - 8 |
Kai Bester1, and Norbert
Theobald2: Results of non target screening of lipophilic organic
pollutants in the German Bight V: Xanthen-9-on, Water Research, 34, 2277-2282,
2000
-
Institute of Organic Chemistry, Martin-Luther-King-Platz 6, 20146 Hamburg,
Germany,
currently: Institute for Environmental Research, University of Dortmund,
Otto Hahn Str. 6, 44221 Dortmund, Germany
-
Federal Maritime and Hydrographic Agency of Germany, Bernhard Nocht Str.
78, 20359 Hamburg, Germany
The presence of xanthen-9-one in estuarine and marine waters is shown for
the first time. A method for the quantification of this oxy-PAH is described
and results are given for water samples from the North Sea. The concentrations
range from 0.08 to 0.68 ng*L-1 in the sea, while 3.7
ng*L-1 were detected in the water of the estuary of the river
Elbe. Possibly this compound can be used as a tracer for anthropogenic
contamination attributed to the combustion of fossil fuels, especially in
automobile engines.
Concentrations in [ng*L-1] of xanthen-9-on in the German Bight
of the North Sea in 1990 and 1995, respectively. na: Not analysed
Sample-station |
1990 |
1995 |
No |
|
|
1 |
0.09 |
0.08 |
4 |
0.29 |
0.10 |
9 |
0.29 |
0.22 |
27 |
0.68 |
0.67 |
30 |
0.37 |
0.21 |
36 |
0.35 |
Na |
Stade/Elbe |
na |
3.7 |
K. Bester: Effects of pesticides on seagrass beds, Helgoland
Marine Research, 54, 95-98, 2000
Comparison of effects on seagrass to the sum of concentration of relevant
herbicides classes of damage are defined as destroyed (T), diminished (K)
or healthy (G), (samples from 1993).
Stefan Weigel, Kai Bester, Heinrich Hühnerfuss: A new method
for rapid solid-phase extraction of large volume water samples and its
application in the screening of North Sea water for organic contaminants
by GC/MS, J. Chromatogr., A 912, 151-161, 2001
A method has been developed that allows the solid-phase extraction of
microorganic compounds from large volumes of water (>10 L) 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. 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 micropollutants. 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, like, e.g.,
dichloropyridines, carbamazepine, propyphenazone and caffeine.
K. Bester, P. de Vos, L. Le Guern, S. Harbeck, F. Hendrickx, G. N.
Kramer, T. Linsinger, I. Mertens, H. Schimmel, B. Sejerøe-Olsen, J.
Pauwels, G. De Poorter, G.G. Rimkus and M. Schlabach: Preparation and
certification of a reference material on PCBs in pig fat and application
in quality control in monitoring laboratories during the Belgian
"PCB-crisis", Chemosphere, 44, 529-537, 2001
In this article the production and validation of a new certified reference
material "PCBs in animal fat" for the control of the maximum level of 200
ng/g set up by the European Communities for veterinary products from Belgium
is described. Three materials are established: a blank, one material with
about 100 ng/g and one with about 200 ng/g (sum of seven PCBs). Data on the
production and certification are given. Additionally this material was used
as an unknown test material in the quality assurance program of the Belgium
meat monitoring system (before the certification of the material). While
the certification was performed with an uncertainty of less than ten percent,
the round robin exhibited larger deviations. However, these deviations were
less than 20 % for most of the 30 participating laboratories. Only two had
significantly higher deviations
Table 7 Certified values of PCBs in IRMM-444, IRMM-445 and IRMM-446.
p: number of accepted sets of results, U: uncertainty
| CRM |
IRMM-444
Blank |
IRMM-445
Very low level |
IRMM-446
Low level |
|
Concentration
[ng/g fat] |
p |
Concentration
± U
[ng /g fat] |
p |
Concentration
± U
[ng /g fat] |
p |
| PCB 28 |
< 2 |
3 |
14.8 ± 2.3 |
8 |
29.6 ± 2.1 |
7 |
| PCB 52 |
< 2 |
3 |
12.9 ± 0.9 |
8 |
25.5 ± 1.8 |
7 |
| PCB 101 |
< 2 |
3 |
12.5 ± 1.2 |
8 |
30 ± 4 |
7 |
| PCB 118 |
< 2 |
3 |
12.7 ± 1.3 |
8 |
30.2 ± 2.7 |
7 |
| PCB 138 |
< 2 |
3 |
14.6 ± 1.6 |
8 |
32 ± 4 |
7 |
| PCB 153 |
< 2 |
3 |
13.1 ± 1.1 |
8 |
30.8 ± 2.4 |
7 |
| PCB 180 |
< 2 |
3 |
12.6 ± 0.9 |
8 |
29.8 ± 2.5 |
7 |
| Sum of seven |
< 14 |
3 |
93 ± 7 |
8 |
207 ± 11 |
7 |
K. Bester, N. Theobald and H.Fr. Schröder: Nonylphenols,
Nonylphenol-ethoxylates, Linear Alkybenzenesulfonates (LAS) and Bis
(4-chlorophenyl)-sulfone in the German Bight of the North Sea, Chemosphere
2001 in press
Nonylphenols and nonylphenolethoxylates were detected in the water and sediment
samples from the German Bight of the North Sea. Additionally bis
(4-chlorophenyl)-sulfone and LAS (linear alkyl benzenesulfonates) were detected
in marine waters. Proof of identification is given by comparison of spectral
and chromatographic data from the compounds in sample extracts to those obtained
from pure standards.
In extracts obtained from water samples taken in 1990 and 1995 the concentrations
of nonylphenols and bis-(4-chlorophenyl)-sulfone were compared for each year.
The concentrations for nonylphenols in seawater varied from 0,7 to 4.4 ng/L
while in the Elbe estuary about 33 ng/L were found. In water samples taken
in 1998 nonylphenolepolyethoxylates could not be determined, whereas LAS
concentrations of 30 ng/L were confirmed by HPLC-MS/MS. The concentrations
for bis (4-chlorophenyl)-sulfone ranged from 0,18-2,2 ng/L. In sediment samples
LAS concentrations of 39-109 ng/g dry weight were determined.
Concentrations of nonylphenols in the water of the German Bight of the North
Sea [ng/L]. Values for 1990 and 1995 are given in
comparison.
Spectrum of Bis (4-chlorphenyl)-sulfone obtained from a water sample of the
river Elbe estuary in 1995
K. Bester, G. Bordin, A. Rodriguez, H. Schimmel, J. Pauwels, G. VanVyncht:
How to overcome matrix effects in HPLC-ESI-MS/MS for the analysis of pesticides
in fruit, Fresenius J. Anal. Chem., in press 2001
A method for the determination of thiabendazole, carbendazime, and phenylurea
pesticides from fruit matrices using high performance liquid chromatography
with electrospray ionisation tandem mass spectrometry (HPLC-ESI-MS/MS) for
detection was elaborated. During the validation process the method was tested
for matrix effects, blanks, and stability of the system. Considerable unspecific
matrix effects in the ESI (+) process were detected by comparing standard
calibration, and matrix calibration, though blank values were very low and
the specific calibration functions showed only small standard deviations.
This effect was overcome by utilising a more complex clean-up, i.e. an additional
size-exclusion step.
Comparison of calibration with and without matrix in HPLC-ESI-MS/MS
last modified 8/2001, KB
I really acknowledge the help of
Frank
Hoffman in constructing this page
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