A contribution on the bio-actions of rare earth elements in the soil-plant environment [Elektronische Ressource] / von Hassan Ragab Hassan El-Ramady
275 Pages
English
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A contribution on the bio-actions of rare earth elements in the soil-plant environment [Elektronische Ressource] / von Hassan Ragab Hassan El-Ramady

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Learn all about the services we offer
275 Pages
English

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A contribution on the bio-actions of rare earth elements in the soil/plant environment 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 Hassan Ragab Hassan El-Ramady aus Kafr El-Sheikh, Ägypten 1. Referent: apl. Professor Dr. Dr. Dr. Ewald Schnug 2. Referent: apl. Professor Dr. Dirk Selmar eingereicht am: 11.06.2008 mündliche Prüfung (Disputation) am: 14.08.2008 Druckjahr 2008 Dedication I didicate this work to my great mother Nozha, my great father Ragab, my lovely wife Neama, my handsome sons Mahmoud and Abd El-Rahman. Acknowledgments I would like to express my deepest appreciation and sincere gratitude to my supervisor, Prof. Dr. Dr. Dr. Ewald Schnug, head of the Institute for Crop and Soil Science (PB), Federal Research Centre for Cultivated Plants (Julius Kuehn-Institut, JKI), Braunschweig for initially accepting me as a Ph. D. Candiddate and later on for his encouragement, and for helpful and enlightening discussions. Similarly, I am thankful to Prof. Dr.

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A contribution on the bio-actions of rare earth elements
in the soil/plant environment




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 Hassan Ragab Hassan El-Ramady
aus Kafr El-Sheikh, Ägypten

















































1. Referent: apl. Professor Dr. Dr. Dr. Ewald Schnug
2. Referent: apl. Professor Dr. Dirk Selmar
eingereicht am: 11.06.2008
mündliche Prüfung (Disputation) am: 14.08.2008

Druckjahr 2008


Dedication

I didicate this work to my great mother Nozha, my great father Ragab,
my lovely wife Neama, my handsome sons Mahmoud and Abd El-
Rahman.



































Acknowledgments

I would like to express my deepest appreciation and sincere gratitude to my
supervisor, Prof. Dr. Dr. Dr. Ewald Schnug, head of the Institute for Crop and Soil
Science (PB), Federal Research Centre for Cultivated Plants (Julius Kuehn-Institut,
JKI), Braunschweig for initially accepting me as a Ph. D. Candiddate and later on for
his encouragement, and for helpful and enlightening discussions.
Similarly, I am thankful to Prof. Dr. Silvia Haneklaus, for her kind and
endless encouragement, constructive criticism and guidance during the preparation
of this work, valuable ideas and basic editing.
I also acknowledge Dr. Kirsten Stoeven, Dr. Sylvia Kratz, Dr. Juergen
Fleckenstein, Dr. Holger Lilienthal, Dr. Susanne Schroetter, Dr. Kerstin Panten, Dr.
Elke Bloem and Prof. Dr. Jutta Rogasik for their sincere guidance and valuable
criticism during the progress of this study.
My special thanks go to Prof. Dr. Dieter Grill and Dr. Karin Herbinger (Graz
University, Institute of Plant Physiology, Austria) for the analyses all leaf disc
samples.
My special thanks also go to Prof. Helmut Sigel (University of Basel,
Switzerland), Prof. Davey Jones (University of Wales, UK), Prof. Mohamed A.
Tabatabai (Iowa State University, USA), Dr. James Hedrick (U.S. Geological Survey,
USA), Dr. Mathias Seifert (Institute for Biochemistry of Cereals and Potatoes, Detmold,
Germany ), Dr. Keiko Tagami (National Institute of Radiological Sciences, Chiba,
Japan), Prof. Zhengyi Hu (Deputy Dean of Graduate School of Chinese Academy of
Sciences, Beijing, China), Prof. Jianguo Zhu (Institute of Soil Science, Chinese Academy
of Sciences, Nanjing, China), Dr. Zhihui Yang (Hunan Agricultural University,
Changsha, China), Mr. Fuyu Yang (Chinese Agriculture University, Beijing, China),
and Mrs. Jia, Lu (Institute of Soil Science, Chinese Academy of Sciences, Nanjing, China)
for their help.
I am also grateful to Gisela Koenig, Angelika Gonser, Ursula Krueger and
Rose-Marie Rietz, for their laboratory assisstance and also Geert Oertel, Helmut
Kammerer, Detlef Siemers and Frank Przebierala for greenhouse experiment
technical assisstance.
Finally, I would like to extend my sincere appreciation and acknowledge to
all colleagues and friends with whom I shared whose names and contributions I can
not enumerate due to space limition. To you all, I say vielen Dank!.

Table of contents i

Table of Contents

Table of Contents................................................................................................... i
List of Tables......................................................................................................... ii
List of Figures........................................................................................................ v
1 Introduction........................................................................................................... 1
2 Literature Review.................................................................................................. 6
2.1 REEs in Parent Materials and Soils………………………………………………. 10
2.2 REEs in Plants........................................................................................................ 32
2.3 Ecotoxicology of REEs........................................................................................... 49
2.4 REEs in Humans and Animals………………………………………………….. 55
3 Material and Methods........................................................................................... 57
3.1 Soil Characteristics.................................................................................................. 57
3.2 Experimental Design............................................................................................... 58
3.3 Analytical Methods................................................................................................. 59
3.4 Statistical Analysis.................................................................................................. 71
4 Results.................................................................................................................... 72
4.1 Influence of REEs on Chemical Soil Characteristics……………………………. 74
4.2 Influence of REEs on Soil Microbiological Parameters…………………………. 75
4.2.1 Influence of REEs on Soil Microbial Counts……………………………………. 76
4.2.2 Influence of REEs on Soil Enzyme Activities…………………………………… 82
4.3 Influence of REEs on Plant Features…………………………………………….. 86
4.3.1 Influence of REEs on Yield Parameters…………………………………………. 87
4.3.2 Influence of REE Applications on the Uptake of Macro and Micro-Nutrients….. 93
4.3.3 Influence of REEs on Stress-related Enzyme Activities in maize and oilseed rape 108
5 Discussion............................................................................................................... 111
5.1 Dose/effect relationships of REEs on Soil Characteristics………………………. 111
5.2 EEs on Plant Characteristics……………………… 120
5.3 Evaluation of Chances and Ecotoxicological Risks of REEs in Agriculture…….. 130
6 Summary/Zusammenfassung............................................................................... 135
References……………………………………………………………………….. 7 144
8 Appendix................................................................................................................. 174







List of tables ii
LIST OF TABLES


1.1 Discovery and origins of names of REEs ……………………………………………………... 2
1.2 World mine production reserves and reserves base of REEs ………………………. 4
2.1 Milestones in agricultural research on REEs………………………………………………… 7
2.2a Characterization of REEs ........................................................................................................... 8
2.2b ........................................................................................................ 8
2.2c REEs ........................................................................................................... 9
2.2d ........................................................................................................ 9
-12.3 REE concentrations (µg g ) in the earth’s crust, sea water, atmosphere and biosphere ……… 10
2.4 Mean total REE content in soils from different types of parent materials ……………………. 10
-12.5 Content of REEs in different types of soils (µg g ) in China and some factors affecting it
……………………………………………………………………………………………. 11
-12.6 Concentration (µg g ) of REEs in soils of some selected countries …………........... 12
-12.7 Effects of amendment with CaCO or CaSO × 2H O on pH, EC (dS m ), and mean REE 3 4 2
concentrations in soil solutions extracted from 10 Australian acid soils……………………. 17
2.8 Comparison of maximum biosorption capacities of various micro-organisms for several rare
earth metal ions from different authors ………………………………………………………. 20
-12.9 Total content of REEs in soils of experimental sites in China ( μg g ) with and without REE
fertilizer ………………………………………………………………………………………. 26
2.10 Concentrations of REEs as ranges and mean values in control and fertilized 15 Chinese soils 27
compared with concentration of REEs in roots and shoots of wheat……………………........
2.11 Desorption of adsorbed REEs by soils and minerals …………………………………………... 31
2.12 Average concentrations of REEs in some plant species and the used soil …………. 33
-12.13 REE content (ng g ) in edible parts of vegetables, wheat and rice grown in Beijing site
(China) with and without REEs fertilizer application ………………….................................... 39
2.14 Yield increases (positive increasing effects and relative to control) observed after REE
applications to different crops ………………………………………………………………… 48
2.15 Effects of REEs on crops pasture grasses, and trees …………………….. 49
2.16 Single REEs content (%) in Changel-Yizhisu, CY ………………………………………. 52
2.17 52 Single REEs content (%) in Nongle “NL”, RECl × xH O ……………………........ 3 2
2.18 Application methods and the used concentrations of REEs for some selected crops ……......... 53
2.19 Mean REE concentration in sewage sludge, compost, food industry sludge, chemical industry 54
sludge and soils in Japan ………………………….....................................................
-12.20 Mean REE concentrations ( μg g ) in various waste ashes ……………………………….. ..... 54
2.21 Concentrations of REEs in organs of different mammals ………………. 56
3.1 Selected some chemical, physical and microbial characteristics of the soil used in
experimentation ……………………………………………………………………………….. 57
-13.2 Rates ( μg g dry soil) of essential nutrients which were added to both maize and oil seed
oilseed rape ……………………………………………………………………………………. 58
3.3 REE application rates in green house experimentation ………………….. 59
3.4 61 The composition of Chinese REE fertilizer (RECl × xH O) .................................................... 3 2
3.5 Composition of fungi, bacteria and actinomycetes media ……………………………………. 63
3.6 Chemical composition of wort broth, Standard I and trace element solution ………………… 63
4.1 Influence of graded REE applications on some chemical soil characteristics (averaged effects
over all treatments) of maize and oilseed rape 66 days after sowing (2005 and 2006) ………. 74
4.2 Influence of graded REE applications on mean of soil pH (1:2.5) and soil electro-chemical
-1conductivity (mS m ) of maize and oilseed rape 66 days after sowing (2006) ……………… 75
4.3 Influence of graded REE applications on soil microbial counts (averaged effects over all
treatments) of maize and oilseed rape 66 days after sowing (2005 and 2006)………………... 77
4.4 Influence of graded REE applications on mean of soil microbial counts (CFU) of maize and
oilseed rape 66 days after sowing (2005) ……………………………………………………... 78
4.5 Correlation coefficients (r) for the relationship between soil pH and EC, AlP, DHA and
microbial counts for maize 66 days after sowing (2005) (n=84) ……………………………... 78
4.6 Correlation coefficients (r) for the relationship between soil pH and EC, AlP, DHA and
microbial counts for oilseed rape 66 days after sowing (2005) ………………………………. 79
4.7 Influence of graded REE applications on some soil enzyme activities of maize and oilseed
rape 66 days after sowing (2005 and 2006) (averaged effects over all treatments) …………. 83
4.8 Influence of graded REE applications on mean of soil enzyme activities of maize and oilseed
List of tables iii

rape 66 days after sowing (2006) ……………………………………………………... ……… 84
4.9a Correlation coefficients (r) for the relationship between soil pH and EC, AlP and DHA on
soils grown with oilseed rape and non-vegetated soil 66 days after sowing (2005) ………….. 85
4.9b Correlation coefficients (r) for the relationship between soil pH and EC, AlP and DHA on
soils grown with maize and non-vegetated soil 66 days after sowing (2005) ………………… 85
4.10a Correlation coefficients (r) for the relationship between soil pH and EC, AlP and DHA on
soils grown with oilseed rape and non-vegetated soil 66 days after sowing (2006) ………….. 85
4.10b Correlation coefficients (r) for the relationship between soil pH and EC, AlP and DHA on
soils grown with maize and non-vegetated soil 66 days after sowing (2006) ………………… 86
4.11 Influence of graded REE applications on mean values for germination rate and plant height of
maize and oilseed rape 66 days after sowing (2006) ………………………………………….. 88
4.12 Influence of graded REE applications on plant biomass production (averaged effects over all
treatments) of maize and oilseed rape 66 days after sowing (2005 and 2006) ……………….. 88
-14.13 Influence of graded REE applications on mean of biomass production (g pot ) of maize and
oilseed rape 66 days after sowing (2006) ……………………………………………………... 89
4.14 Correlation coefficients (r) for the relationship between biomass production, germination rate
and plant height when maize was grown 66 days after sowing (2005) (n= 84) ………………. 90
4.15 Correlation coefficients (r) for the relationship between biomass production, germination rate
and plant height when oilseed rape was grown 66 days after sowing (2005) (n= 84) ………... 91
4.16 Correlation coefficients (r) for the relationship between biomass production, germination rate
and plant height when maize was grown 66 days after sowing (2006) (n= 102) …………….. 91
4.17 Correlation coefficients (r) for the relationship between biomass production, germination rate
and plant height when oilseed rape was grown 66 days after sowing (2006) (n= 102) ………. 91
-14.18a Influence of graded REE-fertilizer application rates on mean REE concentration ( μg g ) in
roots and shoots of maize and oilseed rape 66 days after sowing (2005) ……………………. 94
-14.18b Influence of graded REE-fertilizer application rates on mean of REE uptake ( μg pot ) by
maize and oilseed rape 66 days after sowing (2005) …………………………………………. 94
4.19a Correlation coefficients (r) for the relationship between concentration of REEs in maize roots
and soil pH and EC 66 days after sowing (2006) (n= 102) ……………………………... 95
4.19b Correlation coefficients (r) for the relationship between concentration of REEs in maize
shoots and soil pH and EC 66 days after sowing (2006) (n= 102) …………………………… 95
4.20a Correlation coefficients (r) for the relationship between uptake of REEs for maize roots and
soil pH and EC after 66 days of sowing (2006) (n= 102) …………………………………….. 95
4.20b Correlation coefficients (r) for the relationship between uptake of REEs for maize shoots and
soil pH and EC after 66 days of sowing (2006) (n= 102) …………………………………….. 95
4.21a Influence of graded REE-fertilizer application rates on mean of essential nutrients
concentration in roots and shoots of maize 66 days after sowing (2006) …………………….. 101
4.21b Influence of graded REE-fertilizer application rates on mean of essents
concentration in roots and shoots of oilseed rape 66 days after sowing (2006) ………………. 102
4.22a Influence of graded REE-fertilizer application rates on the mean uptake of essential nutrients
by roots and shoots of maize 66 days after sowing (2006) …………………………………... 105
4.22b Influence of graded REE-fertion the mean uptake of essential nutrients
bshoots of oilseed rape 66 days after sowing (2006) …………………………….. 105
4.23a Influence of graded REE-fertilizer application rates on the mean of transfer factors (TF, μg
-1μg ) of individual REEs and the sum of REEs (total) in roots and shoots of maize 66 days
after sowing (2006) …………………………………………………………………………… 107
-14.23b Influence of graded REE-fertilizer application rates on mean of transfer factors (TF, μg μg )
of individual REEs and the sum of REEs (total) in roots and shoots of oilseed rape 66 days
after sowing (2006) …………………………………………………………………………... 108
-14.24 Influence of graded REE applications on TFs ( μg μg ) of individual REEs and sum of REEs
in roots and shoots of oilseed rape 66 days after sowing (2006) (averaged effects over all
treatments)………………………………………………………………………………………. 108
-14.25 Influence of rated REE applications on α-tocopherol ( μg g DW) and total chlorophyll ( μmol
-1g DW) in leaf discs of maize and oilseed rape after 66 days of sowing (2005) (averaged
effects over all treatments) ……………………………………………………………………. 110
-14.26 Influence of REE-fertilizer application rates on mean of α-tocopherol ( μg g DW) and total
-1chlorophyll ( μmol g DW) in leaf discs of maize and oilseed rape after 66 days of sowing
(2005) ………………………………………………………………………………………… 110



List of tables iv
5.1 Transfer factors (TF-GMs) for non-REEs (Mn, Co, Zn, Sr, and Cs) comparing with TF of
REEs (La, Ce, Pr, Nd, and Sm) for some crops collected in Japan and the present work (dry
weight basis) …………………………………………………………………………………. 127
-15.2 Influence of graded REE applications on mean of REEs utilization rates (%) of shoots ( μg g )
of maize and oilseed rape 66 days after sowing (2006) …………………………………… 132




List of figures v

LIST OF FIGURES


61.1 Global REE production (1kt =10 kg) from 1950 through 2000 ………………………….. 3
2.1 Factors affecting the bioavailability of REEs in soils ………………………………….. 15
2.2 Biological effects of REEs ………………………………………………………………... 55
3.1 Some experimental performance stages ................................................................................ 60
3.2 Some relevant stages for counting soil microbial numbers ……………………………….. 64
3.3 Leaf discs performance stages .............................................................................................. 69
4.1 Relation between soil EC and number of fungi in a soil grown with maize 66 days after
sowing in 2005 (n= 84) ………………………………………………………………. 80
4.2 Comparison of the effect of graded Cu applications on microbial counts (heterotrophic
bacteria, fungi and actinomycetes) for maize and oilseed rape 66 days after sowing in
2005 ……………………………………………………………………………………….. 81
4.3 Relation between soil EC and DHA on a soil grown with maize 66 days after sowing in
2005 (n= 84) …………………………………………………………………………….. 85
4.4 Effect of graded REE-fertilizer application rates on maize and oilseed rape biomass
production in 2005 and 2006.……………………………………………………………..
90
4.5 Influence of graded REE-fertilizer applications on biomass production of maize in 2006... 92
4.6 Influence of graded REE-fertilizer application rates on biomass production of oilseed
rape in 2006………………………………………………………………………………… 92
4.7 Influence of graded La applications on biomass production of maize in 2006 92
4.8 Relation between REE and Ca concentrations in maize shoots 66 days after sowing in
2006 ………………………………………………………………………………………... 96
4.9 Relation between REE (La, Ce, Pr and Nd) concentrations in maize roots and shoots 66
days after sowing in 2006 (n= 102) ……………………………………………………. 97
4.10 Relation between REE (La, Ce, Pr and Nd) concentrations of oilseed rape roots and
shoots 66 days after sowing in 2006 (n= 102) …………………………………………….. 98
4.11 Relation between REE (La, Ce, Pr and Nd) uptake by maize roots and shoots 66 days
after sowing in 2006 (n= 102) ……………………………………………………………... 99
4.12 Relation between REE (La, Ce, Pr and Nd) uptake by oilseed rape roots and shoots 66
days after sowing in 2006 (n= 102) ……………………………………………………. 100
4.13 Relation between B concentration in oilseed rape roots and REE (La, Ce and Nd)
concentrations in oilseed rape roots and shoots 66 days after sowing in 2006 (n= 102) …. 104
5.1 Dose-effect relationship of essential and non-essential metals for plant growth …………. 112
5.2 Conceptive model of REE fractionations in plants ……………………………………….. 121