Occurrence, distribution and fate of pharmaceuticals and further polar contaminants in the marine environment [Elektronische Ressource] / vorgelegt von Stefan Weigel

Informations

• Publié par: universitat_hamburg
• Publié le: 01 janvier 2004
• Nombre de lectures: 9
• Langue: English
• Poids de l'ouvrage: 5 Mo

Extrait

Occurrence, distribution and fate of
pharmaceuticals and further polar
contaminants in the marine environment









DISSERTATION



zur Erlangung des Doktorgrades
des Fachbereichs Chemie der Universit t Hamburg






vorgelegt von



Stefan Weigel

aus Hamburg





Hamburg 2003
The present thesis was carried out between August 1998 and October 2003 at
the University of Hamburg, Institute of Organic Chemistry, in the research
group of Prof. Dr. H. H hnerfuss.

University of Hamburg
Institute of Organic Chemistry
Martin-Luther-King-Platz 6
20146 Hamburg
Germany

http://www.chemie.uni-hamburg.de/oc/hfuss/



















1. Reviewer: Prof. Dr. H. H hnerfuss
2. Reviewer: Dr. h.c. W. Francke

Examen rigorosum: 12 December 2003Table of contents

1 INTRODUCTION............................................................................................................ 1
1.1 Contamination of the marine environment.......................................................... 1
1.2 Pharmaceuticals and personal care products (PPCPs) in the environment..... 4
1.2.1 Background...................................................................................................... 4
1.2.2 Relevance........................................................................................................ 7
1.2.3 Metabolism....................................................................................................... 8
1.2.4 Caffeine 9
1.3 Objectives.............................................................................................................10
2 ANALYSIS OF POLAR ORGANIC COMPOUNDS FROM AQUEOUS MATRICES .....11
2.1 Extraction1
2.1.1 SPE for marine chemistry................................................................................12
2.1.2 SPE of pharmaceuticals..................................................................................14
2.1.3 Comparison of different polymeric sorbents for the simultaneous extraction
of acidic, neutral and basic pharmaceuticals from water..................................16
2.2 Sequential elution ................................................................................................24
2.3 Clean-up, derivatisation.......................................................................................24
2.4 Instrumental analysis...........................................................................................25
2.5 Method validation.................................................................................................27
2.5.1 Quantification of pesticides, industrial chemicals and pharmaceuticals
from marine large volume samples..................................................................28
2.5.2 Quantification of PPCPs from 1 L samples......................................................31
3 NON-TARGET SCREENING OF MARINE SAMPLES..................................................35
3.1 German Bight .......................................................................................................35
3.2 North Sea..............................................................................................................47
3.3 Verification and relevance of identified compounds .........................................49
3.3.1 Pesticides........................................................................................................50
3.3.2 Industrial chemicals.........................................................................................53
3.3.3 Pharmaceuticals..............................................................................................63
3.3.4 Bromoorganic compounds...............................................................................66
3.4 Tromsø-Sound......................................................................................................70
3.5 Conclusions..........................................................................................................73
4 QUANTIFICATION OF SELECTED COMPOUNDS IN THE NORTH SEA ...................75
4.1 Pesticides .............................................................................................................76
4.2 Industrial chemicals.............................................................................................79
4.3 Pharmaceuticals and personal care products ...................................................81
4.3.1 Distribution in the North Sea............................................................................82
4.3.2 Transition river - sea........................................................................................85
4.4 Conclusions..........................................................................................................87
5 PHARMACEUTICALS IN THE ENVIRONMENT...........................................................88
5.1 Introduction ..........................................................................................................88
5.2 Determination of PPCPs in samples from Tromsø/Norway...............................89
5.2.1 Sampling campaign 2001: Seawater...............................................................89
5.2.2 Sampling campaign 2002: Sewage .................................................................90
5.2.3 Sampling campaign 2002: Seawater...............................................................93
5.3 Determination of PPCPs in samples from Hamburg/Germany .........................96
5.4 Concentration and metabolite patterns of ibuprofen.........................................99
5.5 Conclusions........................................................................................................101
6 SUMMARY..................................................................................................................102
I7 ZUSAMMENFASSUNG ..............................................................................................105
8 EXPERIMENTAL ........................................................................................................108
8.1 Instruments.........................................................................................................108
8.2 Preparation of artificial seawater ......................................................................109
8.3 Chemicals...........................................................................................................110
9 REFERENCES............................................................................................................112

ANNEX...........................................................................................................................127
IIList of figures

Figure 1: General water circulation in the North Sea ............................................................. 2
Figure 2: Anticipated exposure routes of pharmaceuticals from use in human and
veterinary medicine ................................................................................................ 6
Figure 3: Metabolism of ibuprofen in humans, including renal excretion rates and
chiral aspects ......................................................................................................... 9
Figure 4: Method for the extraction of large volume North Sea water samples .....................13
Figure 5: Method for the extraction of 1 L water samples .....................................................14
Figure 6: Chemical structures of selected polymeric sorbents ..............................................17
Figure 7: Chemical structures of the compounds included in the sorbent comparison
study......................................................................................................................18
Figure 8: HPLC-chromatogram of a standard solution of the test compounds .....................19
Figure 9: Derivatisation of acidic and phenolic analytes with methyl chloromethanoate........25
Figure 10: Modified method for the quantitative determination of neutral and acidic
analytes from 20 L seawater samples..................................................................29
Figure 11: Chemical structures of the neutral, acidic and phenolic target analytes ...............31
Figure 12: Method for the determination of basic, neutral, and acidic compounds
from water samples .............................................................................................32
Figure 13: Position of the sampling location DB30 within the German Bight.........................36
Figure 14: Sampling positions within the North Sea..............................................................47
Figure 15: Chromatograms (GC-MS, full scan, TIC and extracted ion traces) of
pesticides identified in fraction 5 of sample DB30-3.............................................51
Figure 16: Mass spectra (EI, 70 eV) of pesticides identified in fraction 5 of sample
DB30-3 and from the respective standards.........................................