Unravelling the interactions of boron with natural organic matter (NOM) on a molecular level [Elektronische Ressource] / András Gáspár

Andras.Gaspar

Informations

• Publié par: technische_universitat_munchen
• Publié le: 01 janvier 2008
• Nombre de lectures: 15
• Langue: English
• Poids de l'ouvrage: 4 Mo

Extrait

TECHNISCHE UNIVERSITÄT MÜNCHEN

Lehrstuhl für Ökologische Chemie und Umweltanalytik



Unravelling the interactions of Boron with natural
organic matter (NOM) on a molecular level


András Gáspár


Vollständiger Abdruck der von der Fakultät Wissenschaftszentrum Weihenstephan für Ernährung,
Landnutzung und Umwelt der Technischen Universität München zur Erlangung des akademischen
Grades eines
Doktors der Naturwissenschaften
genehmigten Dissertation.



Vorsitzender: Univ.-Prof. Dr. W. Huber

Prüfer der Dissertation:

1. Priv.-Doz. Dr. Dr. Ph. Schmitt-Kopplin
2. Univ.-Prof. Dr. Dr. h. c. H. Parlar
3. Univ.-Prof. Dr. I. Kögel-Knabner


Die Dissertation wurde am 22.07.2008 bei der Technischen Universität München eingereicht und
durch die Fakultät Wissenschaftszentrum Weihenstephan für Ernährung, Landnutzung und Umwelt
am 24.11.2008 angenommen.


















To my beloved grandparents...







2Acknowledgements


First of all I gratefully acknowledge Philippe Schmitt-Kopplin for his extraordinary
enthusiasm that encouraged me all along my study, from the odd interview till the mind-
boggling final touch.

I am also grateful to my nearest and dearest colleagues of “room 25” for their
friendship, help, and discussion throughout the study.

I also wish to thank my colleagues of “BioGeoAnalysts” for providing an
exceptionally pleasant and productive working atmosphere.

Special thanks are due to Agnes, who willingly shared her local expertise and greatly
assisted in all matters.

The author gratefully acknowledges the
-German-Israeli Foundation for Scientific Research and Development (GIF) for
financial support of this work. GIF Research Grant Agreement No. G-798-175.8/2003
-Deutsche Akademische Austauschdienst (DAAD) for travel support. No. D/06/29417








st stThe dissertation was prepared from May, 1 2005 to July 31 2008 at the Institute of
Ecological Chemistry at the Helmholtz Zentrum München National Research Center for
Environment and Health in the Helmholtz Association in Neuherberg.



3Publications

Articles

[I] A. Gaspar, M. Englmann, A. Fekete, M. Harir and Ph. Schmitt-Kopplin. Trends in
Capillary Electrophoresis-Mass Spectrometry 2005 - 2006. Review Electrophoresis. 29, 66-
79, 2008 (presented in the Introduction)

[II] A. Gaspar, M. Harir, M. Lucio, Ph. Schmitt-Kopplin. Preparative Free-flow
electrophoretic separation and off-line ESI-FTICR/MS analysis of Suwannee River Fulvic
Acid. Electrophoresis (submitted) (presented in Chapter 2.1.)

[III] A. Gaspar, E. V. Kunenkov, R. Lock, M. Desor, I. Perminova, Ph. Schmitt-Kopplin.
Combined utilization of Ion Mobility- and ultra high resolution-MS to identify multiply
charged constituents in natural organic matter. Rapid Communication in Mass
Spectrometry (accepted) (presented in Chapter 2.3.)

[IV] A. Gaspar, M. Harir, M. Lucio, Ph. Schmitt-Kopplin. Targeted borate complex
formation as followed with electrospray Fourier transform ion cyclotron mass
spectrometry: monomolecular model system and polyborate formation. Rapid
Communication in Mass Spectrometry 22, 3119-3129, 2008 (presented in Chapter 4.2.)

[V] A. Gaspar, M. Lucio, M. Harir, Ph. Schmitt-Kopplin. Targeted and non-targeted borate
complex formation as followed with electrospray Fourier transform ion cyclotron mass
spectrometry: Novel approach for identifying borate complexes with natural organic matter
Analytical Chemistry (under revision) (presented in Chapter 4.3.)

M. Harir, M. Frommberger, A. Gaspar, D. Martens, A. Kettrup, M. El Azzouzi, Ph.
Schmitt-Kopplin. Characterization of imazamox degradation by-products by using liquid
chromatography mass spectrometry and high-resolution Fourier transform ion cyclotron
resonance mass spectrometry. Anal. Bioanal. Chem. 389, 1459-1467 (2007)

M. Harir, A. Gaspar, M. Frommberger, M. Lucio, D. Martens, A. Kettrup, M. El Azzouzi,
Ph. Schmitt-Kopplin. Photolysis pathway of Imazapic in aqueous solution: ultrahigh
resolution mass spectrometry analysis of intermediates. J. Agric. Food. Chem. 55(24),
9936-9943 (2007)

M. Harir, A. Gaspar, M. Frommberger, D. Martens, A. Kettrup, M. El Azzouzi, Ph. Schmitt-
Kopplin. Photocatalytic reactions of imazamox at TiO2, H2O2 and TiO2/H2O2 in water
interfaces: Kinetic and photoproducts study. Appl. Catal. B-Environ. (in press)








4Book Chapters

[VI] I. Perminova, A. Gaspar, N. Hertkorn, Ph. Schmitt-Kopplin. Separation techniques as
powerful tools for unfolding molecular complexity of natural organic matter and humic
substance. Biophysico-Chemical processes in environmental systems, IUPAC Series
(accepted) (presented in the Introduction)

Posters and presentations

A. Gaspar, E.Kunenkov, R. Lock, M. Desor, I. Perminova, Ph. Schmitt-Kopplin: Multiple
thcharged constituents in Suwannee river natural organic matter, 14 IHSS Conference,
Sept. 15 - 19, 2008, Moscow (Presentation)

A. Gaspar, Perminova, Ph. Schmitt-Kopplin: Evidences
of the existence of multiple charged constituents in Suwannee river dissolved organic
thmatter, 56 ASMS Conference, June 1 - 5, 2008 in Denver (Poster)

Kovács K., Sajgó Cs., Brukner-Wein A., Kárpáti Z., Gáspár A., Tombácz E., Schmitt-
Kopplin Ph.: Preliminary results on molecular characterization of humic substances from
thermal waters as an unexplored biogeosystem, P32. 9th Conference on Colloid Chemistry
(9CCC), October 3-5. 2007. Siofok, Hungary, Book of Abstracts p. 120 (Poster)

A. Gaspar, E. Belyaeva, M. Meuller, I. V. Perminova, F. Frimmel, M. Frommberger, N.
Hertkorn, Ph. Schmitt-Kopplin: Analysis of Suwannee river fulvic acid with ESI-ICR/FTMS
after fractionation with free-flow electrophoresis and size exclusion chromatography, First
International Symposium on Ultrahigh Resolution Mass Spectrometry for the Molecular
Level Analysis of Complex(BioGeo)Systems, 6-7 November, 2006, Neuherberg, Germany
(Poster)

E. V. Kunenkov, A. S. Kononikhin, A. Gaspar, Ph. Schmitt-Kopplin, I. V. Perminova, A. V.
Garmash, N. Hertkorn, I. A. Popov, E. N. Nikolaev: Comparison of FTICR Data on the
Suwannee river humic and fulvic acid, First International Symposium on Ultrahigh
Resolution Mass Spectrometry for the Molecular Level Analysis of
Complex(BioGeo)Systems, 6-7 November, 2006, Neuherberg, Germany (Poster)

A. Gaspar, J. Junkers, Ph. Schmitt-Kopplin, N. Hertkorn: ESI ICR FTMS and NMR analysis
thof Free-Flow Electrophoresis fractions of Suwannee river NOM, 17 International Mass
Spectrometry Conference, 27 Aug.- 1 Sept., 2006, Prague, Czech Republic (Poster)

A. Gaspar, M. Frommberger, J. Junkers, Ph. Schmitt-Kopplin, N. Hertkorn; Molecular-level
analysis of Suwannee river NOM derived from organic structural spectroscopy and
rdfractionation studies, 3 Symposium on NMR spectroscopy in soil and geo sciences, 6-9
August, 2006 Freising, Germany, (Poster)



5Abstract

Boron, known as micronutrient, is necessary for full-functionality of plants. B plays an
important role in cell development, elongation and structural integrity of plant cell walls.
However this type of role only favourable, if the available boron concentration in soil does
not exceed the maximal tolerable level. If the concentration in the surrounded soil either
exceeds or does not reach the well defined narrow band of the B level can result many types
of malfunction.
Higher concentration of Boron might be discharged either from natural or
anthropogenic sources. Beside the rare volcanic activities, the usage of seawaters, with the
elevated B content, represent a common threat for plantation in arid countries, where water
sources are limited. Unfortunately the elimination of B during the desalination process is
rather challenging than plausible. Further problem is a continuous discharge of elevated B
content from industrial and domestic processed water sources. These general sources might
increase the level of B in soil and produce a toxic environment for the vegetation.
If natural organic matter is considered as inexhaustible and exploitable material that
might and adsorb Boron, than the generally existing low cost-effective adsorbents could be
replaced. For instance cheap composted materials with significant organic matter content,
could be a possibility.
However the first step to find a proper organic matter, and beside the adsorption
behaviour, is to understand on molecular level the mechanism of boron complexation with
such a complex material. And based on the obtained results, the expected properties, that
might preferentially favourable for B complexation, could be exploited by the screening of the