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

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Learn all about the services we offer
194 Pages
English

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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.

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Published 01 January 2007
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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 identify their geographical origins 81
87 865.6.2 Transfer of R( Sr/ Sr) from rock phosphates to P-fertilisers ................................ 83
4.6.3 Natural Sr isotope ratio variation as a tool to trace backs the origin of P-fertilisers
of different manufacturers........................................................................................ 85
4.7 U isotope ratios in rock phosphates and P-containing fertilisers................................... 92
234 2384.7.1 Natural R( U/ U) in rock phosphates from different origin and P-fertilisers..... 92
234 238 4.7.2 Transfer of R( U/ U) from rock phosphates to P-fertilisers ............................... 95
4.7.3 Determination of the origin of P-fertilisers of different manufacturers based on
234 238natural R( U/ U) ................................................................................................. 97
234 2384.7.4 R( U/ U) in farmyard manures and organo-mineral fertilisers .......................... 99
235 2384.7.5 R( U/ U) as tool to detect contamination with anthropogenic U ..................... 100

5 Discussion.................................................................................................................... 103
5.1 Fingerprinting the origin of rock phosphates and P-fertilisers by their heavy metal
pattern .......................................................................................................................... 103
5.1.1 Identifying the origin of rock phosphate to reduce the heavy metals and
radionuclides in P-fertilisers and to avoid environmental pollution...................... 103
5.1.2 Factors affecting U concentration in rock phosphates and P-containing fertilisers105
5.1.3 Heavy metal pattern as indicator to rock phosphate origins .................................. 107
5.1.4 etal pattern as indicator to the origins of P-fertilisers ............................. 110
Table of contents iii

5.1.5 Influence of declining quality of rock phosphates on U content in P-fertilisers ... 111
5.2 Use of Sr isotopes to identify the origin of rock phosphates and P-fertilisers............. 114
5.2.1 Identifying the origin of rock phosphates and P-fertilisers using the Sr isotope ratio
and total Sr concentrations..................................................................................... 114
5.2.2 Factors affecting the Sr isotope ratio in rock phosphates ...................................... 115
5.2.3 Tracing back the origin of P-fertilisers of different manufacturers based on
87 86R( Sr/ Sr)............................................................................................................. 117
5.3 Use of U isotopes to identify the origin of rock phosphates and P-fertilisers and as an
indicator of natural or anthropogenic U....................................................................... 120
234 2385.3.1 Identifying the origin of rock phosphates and P-fertilisers using R( U/ U) and
total U concentrations ............................................................................................ 121
5.3.2 Tracing back the origin of P-fertilisers of different manufacturers based on
234 238R( U/ U) ........................................................................................................... 123
235 2385.3.3 R( U/ U) as an indicator to natural or anthropogenic U.................................. 124
5.4 Application of Sr and U isotope ratios together to identify the sources of phosphorus in
compound mineral fertilisers ....................................................................................... 126

6 Summary/Zusammenfassung.................................................................................... 131
7 References.................................................................................................................. 137
8 Glossary ...................................................................................................................... 151
9 Appendix..................................................................................................................... 155

















Table of contents iv










List of tables v

LIST OF TABLES
Table.1.1: Characterisation of the geographical origin of different materials using
87 86R( Sr/ Sr) and other elements.......................................................................... 3
Table 2.1: Main varieties of apatite and their formulae....................................................... 7
Table.2.2: Average phosphorus and heavy metal concentrations in rock phosphate from
different origin . ................................................................................................. 9
Table.2.3: Variability of heavy metal concentrations in P-fertilisers depending on the
origin of their rock phosphate source .............................................................. 12
Table 2.4: The toxicity of heavy metals for humans ........................................................ 14
Table 2.5: Isotopic masses and half-lives of Sr radioisotopes .......................................... 17
Table 2.6: The most important isotopes of U and their half-lives .................................... 18
238 235 232Table 2.7: U, U and Th decay chain ...................................................................... 18
Table.2.8: Some of the important long-life radioactive elements and their daughter
isotopes (radiogenic) which can be used to date rocks and minerals .............. 22
Table 2.9: Isotopic masses and natural abundance of Sr isotopes on earth ....................... 23
Table 2.10: Isotopic masses, natural abundance and isotope ratios for natural U isotopes23
234 238Table 2.11: Typical range in R( U/ U) activity ratios for various natural materials.... 23
Table.3.1: Rock phosphates and different type of P-containing fertilisers analysed for
heavy metal contents and isotope ratios of Sr and U....................................... 32
Table 3.2: Steps to chemical separation between Sr and Ca in cation exchange column.. 38
Table 3.3: Activities and half-lives and natural abundances of U isotopes....................... 41
Table.4.1:.Phosphorous and microelement concentrations in P-fertilisers and
corresponding rock phosphates........................................................................ 55
Table 4.2: Heavy metal contents in P-fertilisers and corresponding rock phosphates ...... 55
Table 4.3: Average concentrations and ranges of U and P O as well as U/P O ratio in 2 5 2
different types of P-containing fertilisers ........................................................ 56
Table 4.4: Average and ranges of U concentration measured in this study in comparison to
literature values................................................................................................ 57
Table 4.5: U and P O contents and U/P O in rock phosphates from different origin..... 58 2 5 2 5
Table 4.6: P O and U concentration and U/P O ratio in farmyard manures and organo-2 5 2 5
mineral fertilisers ............................................................................................. 59
Table 4.7: Content of N, P O , K O and U as well as U/P O in different types of mineral 2 5 2 2 5



List of tables vi

P-fertilisers from different manufacturers ....................................................... 60
Table 4.8: Concentration of P O and Sr and Sr/P O ratio in different P-containing 2 5 2 5
fertilisers .......................................................................................................... 63
Table 4.9: Comparison of Sr-content in rock phosphate samples from different origin
analysed in this study with data from literature............................................... 65
Table 4.10: N, P O , K O and Sr contents and Sr/P O ratio in different types of P-2 5 2 2 5
containing mineral fertilisers from different manufacturers............................ 67
Table 4.11: The discriminating strength of each variable for the identification the origin of
rock phosphates based on Wilks' Lambda test and univariate F- test.............. 71
Table 4.12: Classification results of discriminate analysis with cross validation.............. 73
Table 4.13: Results of the rotated component matrix for rock phosphate samples including
loading matrix and proportions of variance for each component .................... 75
Table 4.14: Ranges of heavy metal concentrations in rock phosphates analysed by ICP-
MS, suitable as indicators for the characterisation of rock phosphates ........... 77
Table 4.15: Range of Bi, Pb and Co in rock phosphates from different origin ................. 78
Table 4.16: Average concentration of Cu, Mn, Tl and Se in RP from different origin..... 79
87 86Table 4.17: R( Sr/ Sr) for rock phosphates and P-fertilisers from different origin......... 81
Table 4.18: Ranges of Sr isotope ratios in rock phosphates and P-fertilisers.................... 82
Table 4.19: Sr isotope ratio, Sr- and P- content in different types of P-containing mineral
fertilisers of different manufacturers ............................................................... 86
87 86Table 4.20: Sr concentrations and R( Sr/ Sr) in K-fertilisers.......................................... 87
87 86Table 4.21: Sr-content and R( Sr/ Sr) in P-containing mineral fertilisers of different
manufacturers................................................................................................... 88
Table 4.22: Sr concentration, P/K ratio and Sr isotope ratio in organo-mineral fertilisers 89
Table 4.23: P- and Sr-content and Sr isotope ratios in different animal manures ............. 90
234 238Table 4.24: R( U/ U) in rock phosphates and P-fertiliser samples............................... 92
Table 4.25: U isotope ratios in P-containing fertilisers from different manufacturers...... 99
234 238Table 4.26: R( U/ U) in farmyard manures and organo-mineral fertilisers ............... 100
-1 -1Table 5.1: Number of years to add 1 kg U or Sr ha with an annual rate of 20 kg P ha for
rock phosphates from different origin............................................................ 104
Table 5.2: Groups of rock phosphates to be distinguished and elements that can be used to
identify their origins based on PCA............................................................... 109
Table 5.3: Average concentration of some heavy metals in North Carolina phosphates