Characterization of organic contaminants in industrial wastewaters from direct discharges and their behavior in fluvial systems of North Rhine-Westphalia [Elektronische Ressource] / Oxana Botalova

Oxana Botalova

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2011
• Nombre de lectures: 4
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

Characterization of organic contaminants in industrial wastewaters
from direct discharges and their behavior in fluvial systems of
North Rhine-Westphalia

From the Faculty of Georesources and Materials Engineering of the
RWTH Aachen University

Submitted by
Oxana Botalova, MSc
from Semipalatinsk (Kazakhstan, USSR)
in respect of the academic degree of
Doctor of Natural Sciences
approved thesis

Advisors: Univ.-Prof. Dr.rer.nat. Jan Schwarzbauer
PD Dr.rer.nat. Christoph Hilgers

Date of the oral examination: 01.12.2010

This thesis is available in electronic format on the university library’s website






































Acknowledgements

Financial support for my research was provided by the German Research Foundation (Deutsche
Forschungsgemeinschaft (DFG) under grant no. Schw750/10-1. The work was established at the
Institute of Geology and Geochemistry of Petroleum and Coal (LEK) of the RWTH Aachen
University.
I am deeply grateful to my supervisor Prof. Dr. Jan Schwarzbauer for his continuous support,
inspiration, fruitful discussions, valuable suggestions, and encouragement during my doctoral work.
My special thanks go to my second supervisor Prof. Dr. Ralf Littke for his interest in my research,
suggestions, valuable remarks and the discussions of my work during seminars.
I am very grateful to the team of LEK’s Organic Geochemistry laboratory with whom it had a real
pleasure to work together and who kindly supported me in all difficult situations in my life in Aachen.
Especially I would like to thank Ivonne Esser, Annette Schneiderwind and Kerstin Windeck for their
unlimited assistance in the laboratory as well as Kerstin Frische, Patrick Riefer, Philipp Weniger and
Dr. Alexander Kronimus for their great help and physiological support. I would also like to
acknowledge Nadia al Sandouk, Tom Frauenrath, Sarah Illgut, Sabrina Grünelt, and Sylwana Schmidt
for their assistance and the cheerful atmosphere in the lab and during field sampling trips. Many
thanks go to Dr. Sabine Heim who let me an opportunity to extend my scientific activities and gain a
beneficial experience in a conference organization. I send my acknowledgement to BSc. students
Helena Pfunt and Sylwana Bosowski for their contribution to my research.
Last but not least, I want to thank Mrs. D. Kanellis, Dorothee Degen and Olga Schefler for their help
and support with formal questions and documentary issues at the Institute.
I highly appreciate the support in water sampling and providing technical information by the
representatives of Environmental Protection Agencies in North Rhine-Westphalia, particularly Mr. C.
Sustrath (Staatliches Umweltamt Duisburg), Dr. G. Geller (Staatliches Umweltamt Köln), Dr. H.
Rahm (Staatliches Umweltamt Herten), and Dr. F. Jörrens (Wasserverband Eifel-Rur, Düren).
Special thanks to my family for their endless encouragement as well as to my former classmates and
my friends from AEG program in Tübingen for their kindness and support they have given to me from
all over the world.






iii
Contents


Acknowlegements……………………………………………………………………………………iii
Contents………………………………………………………………………………………………iv
Abstract………………………………………………………………………………………………vii
Zusammenfassung…………………………………………………………………………………..viii
List of Tables…………………………………………………………………………………………ix
List of Figures………………………………………………………………………………………..xi
List of Abbreviations………………………………………………………………………………..xiii
1 Introduction……………………………………………………………………………………...1
1.1 Anthropogenic impact on fluvial systems: sources of pollution …………………………...1
1.2 Environmental fate of contaminants under natural conditions……………………………. 2
1.3 Toxicological characterization of organic constituents in industrial effluents …………….3
1.4 Environmental analytical investigations of wastewaters from various industrial
branches…………………………………………………………………………………….4
1.5 Monitoring of industrial contaminants in surface waters………………………………….6
1.6 Scope of the research……………………………………………………………………….7
2 Identification and chemical characterization of specific organic constituents of
petrochemical effluents……………………………………………………………………….....8
2.1 Introduction………………………………………………………………………………...8
2.2 Methods and matherials…………………………………………………………………...10
2.2.1 Samples………………………………………………………………………………..10
2.2.2 Chemicals and glassware……………………………...11
2.2.3 Extraction……………………………………………………………………………..12
2.2.4 Derivatization………………………………12
2.2.5 Gas chromatography (GC) and gas chromatography-mass spectromenty (GC/MS)…12
2.2.6 Identification and quantification……………………………………………………...13
2.3 Results and discussion………………………………………………………………….....14
2.3.1 Constituents of petrochemical effluents……………………………………………....15
2.3.1.1 Non-specific compounds……………………………………………………....15
2.3.1.2 Indicative industrial compounds……………………………………………...21
2.3.2 Contaminant distribution in petrochemical complex B………………………………23
2.3.3 Monitoring of petrochemical marker compounds in an affected river system ………29
2.4 Conclusion………………………………………………………………………………...31
iv
3 Identification and chemical characterization of specific organic markers in the effluents
from chemical production
sites……………………………………………………………………………………………...32
3.1 Introduction………………………………………………………………………………..32
3.2 Methods and materials………………………………………………………………….....34
3.2.1 Samples……………………………………………………………………………......34
3.2.2 Chemicals and glassware……………………………………………………………...35
3.2.3 Extraction……………………………………………………………………………...35
3.2.4 Derivatization………………………………………………………………………....36
3.2.5 Gas chromatography (GC) and gas chromatography-mass spectromenty (GC/MS)…36
3.2.6 Identification and quantification……………………………………………………...36
3.3 Results and discussion…………………………………………………………………….38
3.3.1 Constituents of the effluents from chemical production plants……………………….39
3.3.1.1 Non-specific compounds……………………………………………………....47
3.3.1.2 Indicative industrial compounds……………………………………………….51
3.3.2 Contaminant distribution in the wastewater within chemical complex A…………….55
3.4 Conclusion………………………………………………………………………………...61
4 Geochemical characterization of organic pollutants in effluents discharged from various
industrial sources to riverine systems…………………………………………………………..63
4.1 Introduction………………………………………………………………………………..63
4.2 Methods and materials…………………………………………………………………….65
4.2.1 Samples……………………………………………………………………………….65
4.2.2 Chemicals and glassware……………………………..66
4.2.3 Extraction……………………………………………………………………
4.2.4 Derivatization………………………………67
4.2.5 Gas chromatography (GC) and gas chromatography-mass spectromenty (GC/MS)…67
4.2.6 Identification and quantification……………………………………………………...67
4.3 Results and discussion…………………………………………………………………….68
4.3.1 Constituents of industrial effluents…………………………………………………...69
4.3.1.1 Petroleum refinery effluent……………………………………………………72
4.3.1.2 Effluent from a paper production plant…………………..75
4.3.1.3 Effluents from meat production site and power station……………………….77
4.3.2 Monitoring of industrial compounds in the contaminated river systems……………..78
4.3.2.1 Contamination profile in river 1……………………………………………….79
4.3.2.2 Contamination profile in river 2……………….81
4.3.2.3 Contamination profile in river 3……………………………………………….84
4.4 Conclusion………………………………………………………………………………...88
v
5 Final discussion………………………………………………………………………………...89
6 Bibliography……………………………………………………………………………………92
7 Appendix………………………………………………………………………………………111
8 Curriculum Vitae……………………………………………………………………………...127





































vi
Abstract

Intensive anthropogenic exploration of surface waters has lead to the significant contamination of
fluvial systems in highly industrialized and densely populated regions. Besides municipal discharges,
industrial point sources make substantial contribution to the pollution of river waters emitting a wide
range of organic contaminants. Specific character of industrial effluents is represented by high
contaminant concentration values and their strong fluctuations, as well as by a wide range of chemical
substances because of the high molecular variety of the types of production activities. Their unique
appearance within a spatially defined river section receiving wastewater discharge from a particular
industrial source allows detection of compounds that can be characteristic for a certain industrial
branch or production process.
Despite large amount of studies performed on the characterization of industrial effluents from various
industrial branches, there is a gap in information on the specificity of contaminants in terms of their
molecular structure. At t