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Publié par | universitat_bremen |
Publié le | 01 janvier 2009 |
Nombre de lectures | 33 |
Poids de l'ouvrage | 1 Mo |
Extrait
Bioavailability and biological properties
of several selected ionic liquids
DISSERTATION
zur Erlangung des akademischen Grades
eines Doktors der Naturwissenschaften
vorgelegt im Fachbereich Biologie/Chemie
der Universität Bremen
von
Ioana Anamaria Stan
im September 2009
Eingereicht am: 11. September 2009
Verteidigt am: 22. Oktober 2009
Gutachter: Prof. Dr. Bernd Jastorff
Prof. Dr. Detlef Gabel
Prüfer: Prof. Dr. Juliane Filser
Prof. Dr. Jorg Thöming
To my grandma
Pentru Buna Maia
Table of Contents
Summary……………………………………………………………………………….. VI
Zusammenfassung……………………………………………………………………... VIII
Acknowledgements……………………………………………………………………. XI
Acronyms and Symbols……………………………………………………………….. XII
1. Introduction 1
1.1. Design of sustainable industrial chemicals………………………………........ 1
1.2. Model compounds: ionic liquids – a new promising class of solvents……...... 3
1.3. Demands of the REACH process....................................................................... 5
1.4. Hazard and risk assessment: state of the art....................................................... 8
1.5. Open questions, problem outlines and aims of the thesis.................................. 11
2. Theoretical considerations 14
2.1. Rational for selection of ionic liquids tested...................................................... 14
2.2. Toxicity tests at mesocosm and microcosm level.............................................. 14
2.2.1. Microcosm toxicity studies – state of the art..................................................... 17
2.2.1.1. Indoor microcosms............................................................................................. 17
2.2.1.2. Outdoor microcosms.......................................................................................... 18
2.2.1.3. Combined microcosm and field approach......................................................... 19
2.2.1.4. Industrial chemicals – toxicity test at microcosm level.................................... 20
®2.2.2. The Aqua Hab testsystem – pros and cons..................................................... 21
2.3. Monospecies tests............................................................................................. 25
3. Experimental Part 29
3.1. Material and methods 29
3.1.1. Materials……………………………………………………………............... 29
3.1.2. Methods............................................................................................................. 34
3.1.2.1. Adsorption tests 34
3.1.2.2. Monospecies tests 35
3.1.2.2.1. Range finding tests........................................................................................... 35
3.1.2.2.2. Influence of the excretion process on IM12Cl bioconcetration........................ 39
3.1.2.2.3. Influence of light on IM12Cl bioconcentration................................................ 40
®3.1.2.3. AquaHab tests 40
3.1.2.3.1. Cation effect...................................................................................................... 40
3.1.2.3.2. Anion effect...................................................................................................... 42
3.1.2.4. Sample preparation for residue analysis.......................................................... 44
3.1.2.5. HPLC methods.................................................................................................. 44
3.2. Results and Discussions 46
3.2.1. Adsorption studies 46
3.2.1.1. Adsorption tests................................................................................................... 46
3.2.1.2. Desorption tests.................................................................................................... 47
3.2.1.3. Saturation limit tests............................................................................................ 48
3.2.2. Monospecies tests 49
3.2.2.1. Range finding tests............................................................................................... 49
3.2.2.1.1. Cation effect................................................................................................. 49
3.2.2.1.2. Anion effect................................................................................................. 61
3.2.2.2. Influence of excretion on IM12Cl bioconcentration in fish............................... 66
3.2.2.3. Influence of light on IM12Cl bioconcentration in plants................................... 67
3.2.3. AquaHab studies 68
3.2.3.1. Cation effect......................................................................................................... 68
® AquaHab test 1.................................................................................................. 68
® test 2 and 3........................................................................................ 72
® test 4.................................................................................................. 73
3.2.3.2. Anion effect......................................................................................................... 77
®
AquaHab test 5................................................................................................. 77
4. Conclusions and outlook............................................................................................. 82
References....................................................................................................................... 85
Appendix.......................................................................................................................... 102
Curriculum Vitae............................................................................................................ 120
Summary VI
Summary
Green Chemistry proposes the design of chemical products and processes that reduce or
eliminate the use and the generation of hazardous substances. The new European Guideline
(REACH) demands claim the elucidation of environmental fate pathways and
(bio)transformation data as well as the bioaccumulation potential of chemicals in order to
reduce the uncertainties in their hazard assessment.
Ionic liquids - model compounds with high ecotoxicological relevance for the future - were
tested basically at the molecular and cellular level. Some of them have been tested on more
complex and resource consuming single-species forming the second level of a flexible
biological test battery. The next step of a tiered strategy to assess the hazard potential of a
chemical compound should consist of multispecies tests at the microcosm scale having high
ecological relevance for selected chemicals, which are of high interest with respect to their
technological, economical and (eco)toxicological aspects.
Guided by the necessity to fulfill several research needs concerning the ecotoxicological
hazard assessment of some selected ionic liquids (ILs) the main aims of the present work
were defined.
®A standardized closed aquatic ecosystem at laboratory scale termed AquaHab designed by
the company OHB-System AG (Bremen, Germany) was proposed as a tool for (eco)-toxicity
investigations at microcosm level filling out the next levels of a flexible biological test
battery.
+ + + +The cation (IM12 , IM14 , Py2 , Py4 ) and the anion (Cl and BTA) effects were first
investigated in single-species tests. Data concerning the acute toxicity of the selected ionic
liquids towards four species - Ceratophyllum demersum (plants), Hyalella azteca
(crustaceans), Biomphalaria glabrata (snails), Oryzias latipes (fish) - were provided.
The cation effects indicated crustaceans as being the far most sensitive organism. In contrast,
the snails demonstrated resistance even towards very high concentrations during short and
long time exposure to the test chemical.
The anion effects were tested in single species tests with the BTA anion as lithium salt.
Hyalella azteca showed a higher resistance towards the BTA anion as compar