Identifying the origin of rock phosphates and phosphorus fertilisers using isotope ratio techniques and heavy metal patterns [Elektronische Ressource] / von Mamdoh Sattouf

X Djai

Informations

• Publié par: technische_universitat_carolo-wilhelmina_zu_braunschweig
• Publié le: 01 janvier 2007
• Nombre de lectures: 9
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

Identifying the Origin of Rock Phosphates and Phosphorus Fertilisers Using
Isotope Ratio Techniques and Heavy Metal Patterns





Von der Fakultät für Lebenswissenschaften

der Technischen Universität Carolo-Wilhelmina


zu Braunschweig

zur Erlangung des Grades eines

Doktors der Naturwissenschaften


(Dr. rer. nat.)

genehmigte

D i s s e r t a t i o n







von Mamdoh Sattouf

aus Homs / Syrien



































1. Referent: apl. Professor Dr. Dr. Ewald Schnug
2. Referent: apl. Professor Dr. Robert Kreuzig
eingereicht am: 25.06.2007
mündliche Prüfung (Disputation) am: 30.08.2007
Druckjahr 2007


Vorveröffentlichungen der Dissertation

Teilergebnisse aus dieser Arbeit wurden mit Genehmigung der Fakultät für
Lebenswissenschaften, vertreten durch den Mentor der Arbeit, in folgenden Beiträgen vorab
veröffentlicht:


Publikationen

Sattouf M., Kratz S., Diemer K., Rienitz O., Fleckenstein J., Schiel D., & Schnug E. (2007)
Identifying the origin of rock phosphates and phosphorus fertilizers through high-
87 86precision measurement of the strontium isotopes Sr and Sr. Landbauforschung, 57
(1): 1-11.
Sattouf M., Kratz S., Diemer K., Fleckenstein J., Rienitz O., Schiel D. & Schnug E. (2007)
Significance of uranium and strontium isotope ratios for tracking the fate of uranium
during the processing of phosphate fertilizers from rock phosphates. In: Int.
Symposium Protecting Water Bodies from Negative Impacts of Agriculture. Loads and
Fate of fertilizer Derived Uranium (in press)


Tagungsbeiträge

Sattouf M., Kratz S., Diemer K., Fleckenstein J., Rienitz O., Schiel D. & Schnug E. (2007)
Significance of uranium and strontium isotope ratios for tracking the fate of uranium
during the processing of phosphate fertilizers from rock phosphates. In: Int.
Symposium Protecting Water Bodies from Negative Impacts of Agriculture. Loads and
Fate of fertilizer Derived Uranium 4-6, June, 2007









Acknowledgement

On this page, I would like to express my gratitude to all those who gave me the
possibility to complete this thesis.
First of all, thanks to my supervisor Prof. Dr. Dr. Ewald Schnug who gave me an
opportunity to work under his supervision and gave me this topic to work on it. I would like
to thank the other members of my committee, Prof. Dr. Robert Kreuzig, Prof. Dr. Dirk
Selmar and Prof. Dr. Wolfgang Durner for their interest in my work, reviewing my thesis
and taking time out to attend my oral defence.
I would also like to thank Dr. rer. nat. Sylvia Kratz, who gave me very good suggestions
and useful comments on how to improve my thesis. Thanks are due for her patience, for
sharing her ideas with me and for her advice. Her remarks on the first draft helped me a lot
to learn and improve my thesis.
Many thanks go to all members and colleagues of the institute of plant nutrition and soil
science (FAL). In particular, Dr. rer. nat. Jürgen Fleckenstein for their guidance and
valuable ideas.
I would like to express my gratitude to all members in this institute Physikalisch-
Technische Bundesanstalt (PTB), Department 3.1 Metrology in Chemistry, Inorganic
Analysis in Brauschweig for their helps. Special thanks go to Dr. Katrin Diemer from PTB
institute who spent a lot of time working to measure U and Sr isotopes by TIMS.
I am thankful to Dr. Detlef Schiel and Dr. Olaf Rienitz from PTB institute. This work
would not have been completed without their help
Finally, I am forever indebted to my parents, sisters, my wife, my daughter and all my
family for their support, understanding, encouragement, and endless love.








Table of contents i

TABLE OF CONTENT

Table of content…………...………..……….....………………………...………………..…..i
List of tables............................................................................................................................. v
List of figures.......................................................................................................................... ix
List of symbols, acronyms and abbreviations ..................................................................... xi
1 Introduction....................................................................................................................1

2 Literature review and objectives of this study ............................................................ 7
2.1 Heavy metals in rock phosphates and P-fertilisers .......................................................... 7
2.1.1 Types and world production of rock phosphates ....................................................... 7
2.1.2 Heavy metals in rock phosphates from different origin............................................. 8
2.1.3 Transfer of radionuclides and heavy metals from rock phosphates to P-fertilisers
during the production process.................................................................................. 10
2.1.4 Effects of heavy metals applied with P-fertilisers on soil-plant-human system...... 12
2.2 Isotopic fingerprint method (isotopic signature)............................................................ 16
2.2.1 Definition and types of isotopes .............................................................................. 16
2.2.2 Abundance of the isotopes on earth......................................................................... 22
2.2.3 Isotopic fractionation...............................................................................................24
2.2.4 Isotope ratios as a fingerprint to identify the origin of different materials.............. 25
2.3 Objectives of this study.................................................................................................. 28

3 Material and methods 31
3.1 Selection of samples ...................................................................................................... 31
3.2 Analytical methods of heavy metal determination ........................................................ 33
3.3 Measurements of Sr and U isotopes using Thermal Ionisation Mass Spectrometry
(TIMS) ........................................................................................................................... 33
87 863.3.1 Measurements of R( Sr/ Sr) in rock phosphates and P-fertilisers by Thermal
Ionisation Mass Spectrometry.................................................................................. 34
234 238 235 2383.3.2 Measurements of R( U/ U)- and R( U/ U) in rock phosphates and P-
fertilisers by thermal ionisation mass spectrometry................................................. 41
3.5 Calculation and statistical analysis ................................................................................ 47
3.5.1 Cluster analysis........................................................................................................47
3.5.2 Discriminant function analysis 47
3.5.3 Principal components and factor analysis................................................................ 48



Table of contents ii

3.5.4 Calculation of isotope ratios in P-fertilisers or rock phosphates used to produce
compound fertilisers in order to trace back the origin of P-components in
compound fertilisers................................................................................................. 49

4 Results .......................................................................................................................... 51
4.1 Phosphorus and microelements in rock phosphates from different origin..................... 51
4.2 Heavy metals in rock phosphates and P-fertilisers from different origin ...................... 52
4.3 U concentration in different types of rock phosphates and P-containing fertilisers...... 56
4.4 Sr concentration in different types of rock phosphates and P-containing fertilisers ..... 63
4.5 Fingerprinting the geographical origin of rock phosphates according to their content of
heavy metals using multivariate statistical analysis....................................................... 69
4.5.1 Classification of rock phosphates using discriminant analysis and hierarchical
cluster analysis......................................................................................................... 69
4.5.2 Natural relationships among heavy metals in different rock phosphates as
determined by cluster analysis................................................................................. 73
4.5.3 Determination of heavy metal pattern by principal component analysis (PCA) ..... 75
4.6 Sr isotope ratios in rock phosphates and P-containing fertilisers .................................. 81
4.6.1 Sr isotope ratio in rock phosphates as a tool to id