Understanding the ecotoxicological risks of ionic liquids - where are we?

Transcription

1 Understanding the ecotoxicological risks of ionic liquids - where are we? Green Solvents for Processes Friedrichshafen/Germany October 8-11, J. Ranke, J. Arning, P. Behrend, A. Böschen, U. Bottin-Weber, J. Filser, T. Juffernholz, M. Matzke, A. Müller, M. Schaefer, S. Stolte, R. Störmann, K. Thiele, J. Thöming, B. Jastorff University of Bremen/D Understanding the ecotoxicological risks of ionic liquids - where are we? p.1/??

2 Understanding the ecotoxicological risks of ionic liquids - where are we? p.2/??

3 The UFT Chemical Engineering Regeneration & Recycling Prof. Thöming Environmental Process Engineering Prof. Räbiger Physiogeography Prof. Venzke Biotechnology Prof. Blohm Molecular Genetics Prof. Becker Ecology Prof. Filser Bioorganic Chemistry Prof. Jastorff Understanding the ecotoxicological risks of ionic liquids - where are we? p.3/??

4 The UFT IL team Understanding the ecotoxicological risks of ionic liquids - where are we? p.4/??

5 Sustainable Product Design Ranke J (2001) PhD Dissertation Analysis of chemical structures SAR/QSAR Synthesis / Purchase of chemical structures Examination Application Human Health Environment Evaluation Economical Social Ecological Understanding the ecotoxicological risks of ionic liquids - where are we? p.5/??

6 Technosphere vs. Environment Technosphere Environment Degree of control high low Degree of knowledge high low Understanding the ecotoxicological risks of ionic liquids - where are we? p.6/??

7 Uncertainty and Ignorance Chemistry dealing with biological and environmental systems has to deal with more complexity Understanding the ecotoxicological risks of ionic liquids - where are we? p.7/??

8 Uncertainty and Ignorance Chemistry dealing with biological and environmental systems has to deal with more complexity more uncertainty Understanding the ecotoxicological risks of ionic liquids - where are we? p.7/??

9 Uncertainty and Ignorance Chemistry dealing with biological and environmental systems has to deal with more complexity more uncertainty more ignorance Understanding the ecotoxicological risks of ionic liquids - where are we? p.7/??

10 Green and sustainable chemistry includes both technospheric and environmental chemistry: Understanding the ecotoxicological risks of ionic liquids - where are we? p.8/??

11 Green and sustainable chemistry includes both technospheric and environmental chemistry: High standards of deterministic knowledge in technospheric area Understanding the ecotoxicological risks of ionic liquids - where are we? p.8/??

12 Green and sustainable chemistry includes both technospheric and environmental chemistry: High standards of deterministic knowledge in technospheric area Great efforts to deal with uncertainty in environmental area Understanding the ecotoxicological risks of ionic liquids - where are we? p.8/??

13 Green and sustainable chemistry includes both technospheric and environmental chemistry: High standards of deterministic knowledge in technospheric area Great efforts to deal with uncertainty in environmental area Understanding ecotoxicological risks Understanding the ecotoxicological risks of ionic liquids - where are we? p.8/??

14 Elements of ecotoxicological risks Understanding the ecotoxicological risks of ionic liquids - where are we? p.9/??

15 Ranke J (2001) PhD Dissertation Five risk indicators Technosphere Decisions Environment Risk research Organisms Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

16 Ranke J (2001) PhD Dissertation Five risk indicators Technosphere Decisions Substance Environment Risk research Organisms Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

17 Ranke J (2001) PhD Dissertation Five risk indicators Technosphere Decisions Substance Release Environment Risk research Organisms Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

18 Ranke J (2001) PhD Dissertation Five risk indicators Technosphere Decisions Substance Release Environment Risk research Organisms Uncertainty Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

19 Ranke J (2001) PhD Dissertation Five risk indicators Technosphere Risk profile Decisions Risk research Uncertainty Release Substance Environment Organisms Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

20 Ranke J (2001) PhD Dissertation Five risk indicators Influence Technosphere Risk profile Decisions Risk research Uncertainty Release Substance Environment Organisms Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

21 Ranke J (2001) PhD Dissertation Five risk indicators Influence Technosphere Decisions Substance Risk profile Release Spatiotemporal range Environment Risk research Organisms Uncertainty Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

22 Ranke J (2001) PhD Dissertation Five risk indicators Influence Technosphere Decisions Release Risk profile Spatiotemporal range Risk research Substance Environment Organisms Substance + Transformation products Uncertainty Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

23 Ranke J (2001) PhD Dissertation Five risk indicators Influence Technosphere Decisions Substance Risk profile Risk research Uncertainty Release Spatiotemporal range Bioaccumulation Environment Organisms Substance + Transformation products Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

24 Ranke J (2001) PhD Dissertation Five risk indicators Influence Technosphere Decisions Substance Risk profile Risk research Uncertainty Release Spatiotemporal range Bioaccumulation Biological Activity Environment Organisms Substance + Transformation products Understanding the ecotoxicological risks of ionic liquids - where are we? p.10/??

25 Release of ionic liquids Gaseous release (impurities, decomposition products) Understanding the ecotoxicological risks of ionic liquids - where are we? p.11/??

26 Release of ionic liquids Gaseous release (impurities, decomposition products) Waste water Understanding the ecotoxicological risks of ionic liquids - where are we? p.11/??

27 Release of ionic liquids Gaseous release (impurities, decomposition products) Waste water Accidental releases to soil or water Understanding the ecotoxicological risks of ionic liquids - where are we? p.11/??

28 Release Chemical production process Residue Heated water Product Waste Gas Water Utilization Disposal Treatment Treatment Cooling Closed cooling system Incineration Landfill Leachate Sewage sludge Receiving water Slag, ash according to Christ, C. Chem Eng Technol 1999, 22, Understanding the ecotoxicological risks of ionic liquids - where are we? p.12/??

29 Release Chemical production process Residue Heated water Product Waste Gas Water Utilization Disposal Treatment Treatment Cooling Closed cooling system Incineration Landfill Leachate Sewage sludge Receiving water Slag, ash Understanding the ecotoxicological risks of ionic liquids - where are we? p.12/??

30 Global production scale ionic liquids LAS Production in t/a Understanding the ecotoxicological risks of ionic liquids - where are we? p.13/??

31 Release factors 0.01 to 0.5 for LAS Understanding the ecotoxicological risks of ionic liquids - where are we? p.14/??

32 Release factors 0.01 to 0.5 for LAS to 0.5 for IL Understanding the ecotoxicological risks of ionic liquids - where are we? p.14/??

33 Global release scale ionic liquids LAS Release in t/a Understanding the ecotoxicological risks of ionic liquids - where are we? p.15/??

34 Global release scale ionic liquids? LAS Release in t/a Understanding the ecotoxicological risks of ionic liquids - where are we? p.15/??

35 Release of ionic liquids Impurities can be controlled Understanding the ecotoxicological risks of ionic liquids - where are we? p.16/??

36 Release of ionic liquids Impurities can be controlled Decomposition can be avoided Understanding the ecotoxicological risks of ionic liquids - where are we? p.16/??

37 Release of ionic liquids Impurities can be controlled Decomposition can be avoided IL in waste water could be removed Understanding the ecotoxicological risks of ionic liquids - where are we? p.16/??

38 Release of ionic liquids Impurities can be controlled Decomposition can be avoided IL in waste water could be removed Accidental releases must be considered Understanding the ecotoxicological risks of ionic liquids - where are we? p.16/??

39 Are IL readily biodegradable? N + N Cl Br H 3 C F CH 3 F B F F - F F F P F F F % N + O N H 3 C O S O C CH 3 O H 3 25 % O CH 3 N + Br N O H 3 32 / 41 % C C H 3 N N + O CH 3 O O O S O H 3 54 / 67 % C O N. Gathergood, M. T. Garcia, and P. J. Scammells. Green Chem 2004, 2005, 2006 Understanding the ecotoxicological risks of ionic liquids - where are we? p.17/??

40 Are IL readily biodegradable? N + N Cl Br H 3 C F CH 3 F B F F - F F F P F F F % N + O N H 3 C O S O C CH 3 O H 3 25 % O CH 3 N + Br N O H 3 32 / 41 % C C H 3 N N + O CH 3 O O O S O H 3 54 / 67 % C O N. Gathergood, M. T. Garcia, and P. J. Scammells. Green Chem 2004, 2005, 2006 Understanding the ecotoxicological risks of ionic liquids - where are we? p.17/??

41 Release via wastewater Fate of cations and anions in STP has to be judged separately! Degradation in sewage treatment plants (STP) presumably higher Understanding the ecotoxicological risks of ionic liquids - where are we? p.18/??

42 Release via wastewater Fate of cations and anions in STP has to be judged separately! Degradation in sewage treatment plants (STP) presumably higher Sorption of 1-butyl-3-methylimidazolium (bmim) cation presumably low Understanding the ecotoxicological risks of ionic liquids - where are we? p.18/??

43 Release via wastewater Fate of cations and anions in STP has to be judged separately! Degradation in sewage treatment plants (STP) presumably higher Sorption of 1-butyl-3-methylimidazolium (bmim) cation presumably low Overall removal of bmim presumably incomplete Understanding the ecotoxicological risks of ionic liquids - where are we? p.18/??

44 Release via wastewater Fate of cations and anions in STP has to be judged separately! Degradation in sewage treatment plants (STP) presumably higher Sorption of 1-butyl-3-methylimidazolium (bmim) cation presumably low Overall removal of bmim presumably incomplete Good removal of alkyl sulfates Understanding the ecotoxicological risks of ionic liquids - where are we? p.18/??

45 Spatiotemporal range of IL Interplay of Hydrolysis Understanding the ecotoxicological risks of ionic liquids - where are we? p.19/??

46 Spatiotemporal range of IL Interplay of Hydrolysis Biodegradation Understanding the ecotoxicological risks of ionic liquids - where are we? p.19/??

47 Spatiotemporal range of IL Interplay of Hydrolysis Biodegradation Sorption to organic material and various surfaces Understanding the ecotoxicological risks of ionic liquids - where are we? p.19/??

48 Spatiotemporal range of IL Interplay of Hydrolysis Biodegradation Sorption to organic material and various surfaces No fate modelling carried out yet, High uncertainty Understanding the ecotoxicological risks of ionic liquids - where are we? p.19/??

49 Bioaccumulation of IL Analogy to ionic surfactants Understanding the ecotoxicological risks of ionic liquids - where are we? p.20/??

50 Bioaccumulation of IL Analogy to ionic surfactants BCF estimation method [1] [1] Meylan et al. Environ Toxicol Chem Understanding the ecotoxicological risks of ionic liquids - where are we? p.20/??

51 Bioaccumulation of IL Analogy to ionic surfactants BCF estimation method [1] Some log K ow values [2] [1] Meylan et al. Environ Toxicol Chem [2] Ropel et al. Green Chem Understanding the ecotoxicological risks of ionic liquids - where are we? p.20/??

52 Bioaccumulation of IL Analogy to ionic surfactants BCF estimation method [1] Some log K ow values [2] Partitioning to mammalian cells [3] [1] Meylan et al. Environ Toxicol Chem [2] Ropel et al. Green Chem [3] Ranke et al. Toxicol Env Chem Understanding the ecotoxicological risks of ionic liquids - where are we? p.20/??

53 Bioaccumulation of IL Analogy to ionic surfactants BCF estimation method [1] Some log K ow values [2] Partitioning to mammalian cells [3] k 0 values from HPLC [4] [1] Meylan et al. Environ Toxicol Chem [2] Ropel et al. Green Chem [3] Ranke et al. Toxicol Env Chem [4] Ranke et al. Ecotoxicol Environ Safety 2006 in press Understanding the ecotoxicological risks of ionic liquids - where are we? p.20/??

54 Problems with log K ow for IL Experimental difficulties in the case of surface activity Understanding the ecotoxicological risks of ionic liquids - where are we? p.21/??

55 Problems with log K ow for IL Experimental difficulties in the case of surface activity Dependence on presence of counter-ions Understanding the ecotoxicological risks of ionic liquids - where are we? p.21/??

56 Problems with log K ow for IL Experimental difficulties in the case of surface activity Dependence on presence of counter-ions Shake-flask experiments are time-consuming Understanding the ecotoxicological risks of ionic liquids - where are we? p.21/??

57 log k 0 values from gradient HPLC Describe distribution between stationary phase and water (ideally) Understanding the ecotoxicological risks of ionic liquids - where are we? p.22/??

58 log k 0 values from gradient HPLC Describe distribution between stationary phase and water (ideally) Easily generated by one or more gradient runs Understanding the ecotoxicological risks of ionic liquids - where are we? p.22/??

59 log k 0 values from gradient HPLC Describe distribution between stationary phase and water (ideally) Easily generated by one or more gradient runs Separate lipophilicity assessment of cations and anions Understanding the ecotoxicological risks of ionic liquids - where are we? p.22/??

60 log k 0 values from gradient HPLC Describe distribution between stationary phase and water (ideally) Easily generated by one or more gradient runs Separate lipophilicity assessment of cations and anions Good correlation with cytotoxicity Understanding the ecotoxicological risks of ionic liquids - where are we? p.22/??

61 Biological activity of IL (UFT) Tests on different levels of biological organisation Enzymes (AChE, GST, GR) Understanding the ecotoxicological risks of ionic liquids - where are we? p.23/??

62 Biological activity of IL (UFT) Tests on different levels of biological organisation Enzymes (AChE, GST, GR) Cells (rat leukemia cell line IPC-81, others) Understanding the ecotoxicological risks of ionic liquids - where are we? p.23/??

63 Biological activity of IL (UFT) Tests on different levels of biological organisation Enzymes (AChE, GST, GR) Cells (rat leukemia cell line IPC-81, others) Aquatic organisms (luminescent bacteria, monocellular algae, duckweed) Understanding the ecotoxicological risks of ionic liquids - where are we? p.23/??

64 Biological activity of IL (UFT) Tests on different levels of biological organisation Enzymes (AChE, GST, GR) Cells (rat leukemia cell line IPC-81, others) Aquatic organisms (luminescent bacteria, monocellular algae, duckweed) Terrestrial organisms (springtails, enchytraeids, earthworms, terrestrial plants) Understanding the ecotoxicological risks of ionic liquids - where are we? p.23/??

65 Acetylcholinesterase inhibition Stock et al. Green Chem Arning et al. in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.24/??

66 Cell viability assay IPC 81 leucemia cells Viabilities C5MIM C6MIM C7MIM C8MIM C9MIM C10MIM Decadic Logarithm of the concentration in µm Ranke et al. Ecotoxicol Environ Safety Stolte et al. Green Chem Understanding the ecotoxicological risks of ionic liquids - where are we? p.25/??

67 Luminescence inhibition Marine bacteria Vibrio fischeri, DIN L 341 Ranke et al. Ecotoxicol Environ Safety Understanding the ecotoxicological risks of ionic liquids - where are we? p.26/??

68 Algae growth inhibition? Monocellular algae Scenedesmus vacuolatus Understanding the ecotoxicological risks of ionic liquids - where are we? p.27/??

69 Duckweed growth inhibition Lemna minor, ISO TC 147/SC 5 N draft Understanding the ecotoxicological risks of ionic liquids - where are we? p.28/??

70 Plant growth inhibition Lepidium sativum, ISO Jastorff et al. Green Chem Understanding the ecotoxicological risks of ionic liquids - where are we? p.29/??

71 Inhibition of springtail reproduction Folsomia candida ISO Understanding the ecotoxicological risks of ionic liquids - where are we? p.30/??

72 Biological activity of IL (literature) Tests with different organisms Aquatic organisms (Luminescent bacteria, monocellular algae, water fleas, zebra fish) Understanding the ecotoxicological risks of ionic liquids - where are we? p.31/??

73 Biological activity of IL (literature) Tests with different organisms Aquatic organisms (Luminescent bacteria, monocellular algae, water fleas, zebra fish) Terrestrial organisms (Nematodes, rats, rabbits, mice) Understanding the ecotoxicological risks of ionic liquids - where are we? p.31/??

74 Ranke J (2001) PhD Dissertation Five risk indicators Influence Technosphere Decisions Substance Risk profile Risk research Uncertainty Release Spatiotemporal range Bioaccumulation Biological Activity Environment Organisms Substance + Transformation products Understanding the ecotoxicological risks of ionic liquids - where are we? p.32/??

75 Understanding risk related properties Understanding the ecotoxicological risks of ionic liquids - where are we? p.33/??

76 Concepts Molecular interaction potentials Understanding the ecotoxicological risks of ionic liquids - where are we? p.34/??

77 Concepts Molecular interaction potentials Linear free enthalpy relationships (LFER) Understanding the ecotoxicological risks of ionic liquids - where are we? p.34/??

78 Concepts Molecular interaction potentials Linear free enthalpy relationships (LFER) Basal cytotoxicity Understanding the ecotoxicological risks of ionic liquids - where are we? p.34/??

79 Concepts Molecular interaction potentials Linear free enthalpy relationships (LFER) Basal cytotoxicity Baseline toxicity Understanding the ecotoxicological risks of ionic liquids - where are we? p.34/??

80 Concepts Molecular interaction potentials Linear free enthalpy relationships (LFER) Basal cytotoxicity Baseline toxicity Mixture toxicity Understanding the ecotoxicological risks of ionic liquids - where are we? p.34/??

81 Concepts Molecular interaction potentials Linear free enthalpy relationships (LFER) Basal cytotoxicity Baseline toxicity Mixture toxicity Bioavailability Understanding the ecotoxicological risks of ionic liquids - where are we? p.34/??

82 Concepts Molecular interaction potentials Linear free enthalpy relationships (LFER) Basal cytotoxicity Baseline toxicity Mixture toxicity Bioavailability Molecular biology Understanding the ecotoxicological risks of ionic liquids - where are we? p.34/??

83 Molecular interaction potentials O O N N + O MTBE IM1-1COO5 Jastorff, B., Störmann, R., Wölcke, U.: Struktur-Wirkungs-Denken in der Chemie eine Chance für mehr Nachhaltigkeit. Aschenbeck & Isensee, 2003 Understanding the ecotoxicological risks of ionic liquids - where are we? p.35/??

84 Linear Free Energy Relationships LFERs correlate Gibbs free energies of IL transfer between water and pure IL (log c sat w ) Understanding the ecotoxicological risks of ionic liquids - where are we? p.36/??

85 Linear Free Energy Relationships LFERs correlate Gibbs free energies of IL transfer between water and pure IL (log c sat w ) water and octanol (log K ow ) Understanding the ecotoxicological risks of ionic liquids - where are we? p.36/??

86 Linear Free Energy Relationships LFERs correlate Gibbs free energies of IL transfer between water and pure IL (log c sat w ) water and octanol (log K ow ) water and air-water surfaces (surface tension) Understanding the ecotoxicological risks of ionic liquids - where are we? p.36/??

87 Linear Free Energy Relationships LFERs correlate Gibbs free energies of IL transfer between water and pure IL (log c sat w ) water and octanol (log K ow ) water and air-water surfaces (surface tension) water and C18-silica (log k 0 ) Understanding the ecotoxicological risks of ionic liquids - where are we? p.36/??

88 Linear Free Energy Relationships LFERs correlate Gibbs free energies of IL transfer between water and pure IL (log c sat w ) water and octanol (log K ow ) water and air-water surfaces (surface tension) water and C18-silica (log k 0 ) water and artificial membranes or biota Understanding the ecotoxicological risks of ionic liquids - where are we? p.36/??

89 Linear Free Energy Relationships LFERs correlate Gibbs free energies of IL transfer between water and pure IL (log c sat w ) water and octanol (log K ow ) water and air-water surfaces (surface tension) water and C18-silica (log k 0 ) water and artificial membranes or biota water and cytotoxicity target sites (log EC 50 ) Understanding the ecotoxicological risks of ionic liquids - where are we? p.36/??

90 Linear Free Energy Relationships LFERs correlate Gibbs free energies of IL transfer between water and pure IL (log c sat w ) water and octanol (log K ow ) water and air-water surfaces (surface tension) water and C18-silica (log k 0 ) water and artificial membranes or biota water and cytotoxicity target sites (log EC 50 ) Understanding the ecotoxicological risks of ionic liquids - where are we? p.36/??

91 The hypothesis of a basal cytotoxicity toxicity to basal functions of all cells of an organism Ekwall Acta Pharmacol Toxicol Suppl Understanding the ecotoxicological risks of ionic liquids - where are we? p.37/??

92 The hypothesis of a basal cytotoxicity toxicity to basal functions of all cells of an organism as opposed to organ specific or extracellular toxicity Ekwall Acta Pharmacol Toxicol Suppl Understanding the ecotoxicological risks of ionic liquids - where are we? p.37/??

93 The hypothesis of a basal cytotoxicity toxicity to basal functions of all cells of an organism as opposed to organ specific or extracellular toxicity similar across many in-vitro cytotoxicity tests Ekwall Acta Pharmacol Toxicol Suppl Understanding the ecotoxicological risks of ionic liquids - where are we? p.37/??

94 The hypothesis of a basal cytotoxicity toxicity to basal functions of all cells of an organism as opposed to organ specific or extracellular toxicity similar across many in-vitro cytotoxicity tests similar across very different organisms Ekwall Acta Pharmacol Toxicol Suppl Understanding the ecotoxicological risks of ionic liquids - where are we? p.37/??

95 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] all log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.38/??

96 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] all Cl and Br log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.38/??

97 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] all Cl and Br [QuinX] + [Py4 2NMe] + [IM1 1O2] + [IM18OH] log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.38/??

98 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] selected Cl and Br log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.38/??

99 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] selected Cl and Br selected [PF 6 ] log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.38/??

100 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] selected Cl and Br selected [PF 6 ] selected [BF 4 ] log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.38/??

101 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] selected Cl and Br selected [PF 6 ] selected [BF 4 ] selected [(CF 3 SO 2 ) 2 N] log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.38/??

102 Mixture toxicity Binary 1:1 mixtures of cations and anions Understanding the ecotoxicological risks of ionic liquids - where are we? p.39/??

103 Mixture toxicity Binary 1:1 mixtures of cations and anions If concentration addition is assumed: EC = EC1 50 EC2 50 EC EC2 50 Understanding the ecotoxicological risks of ionic liquids - where are we? p.39/??

104 Mixture toxicity Binary 1:1 mixtures of cations and anions If concentration addition is assumed: Examples: EC = EC1 50 EC2 50 EC EC2 50 EC 1 50= EC 2 50= 10µM: EC = 5µM EC 1 50 = 100µM and EC2 50 = 1µM: EC = 0.99µM Understanding the ecotoxicological risks of ionic liquids - where are we? p.39/??

105 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] selected Cl and Br selected [PF 6 ] selected [BF 4 ] selected [(CF 3 SO 2 ) 2 N] log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.40/??

106 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] all selected Cl and Br selected [PF 6 ] selected [BF 4 ] [(CF 3 SO 2 ) 2 N] [(C 2 F 5 ) 3 PF 3 ] [(C 3 F 7 ) 3 PF 3 ] log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.40/??

107 Cation lipophilicity and cytotoxicity log 10 EC 50 [µm] all selected Cl and Br selected [PF 6 ] selected [BF 4 ] [(CF 3 SO 2 ) 2 N] [(C 2 F 5 ) 3 PF 3 ] [(C 3 F 7 ) 3 PF 3 ] [QuinX] log 10 (k 0 ) Ranke et al. Ecotoxicol Environ Safety 2006 in press Stolte et al., in preparation Understanding the ecotoxicological risks of ionic liquids - where are we? p.40/??

108 IL baseline cytotoxicity Exceptions to the rule: quinolinium or dimethylaminopyridinium headgroup Understanding the ecotoxicological risks of ionic liquids - where are we? p.41/??

109 IL baseline cytotoxicity Exceptions to the rule: quinolinium or dimethylaminopyridinium headgroup hydrophobic or reactive anions Understanding the ecotoxicological risks of ionic liquids - where are we? p.41/??

110 Conclusions Understanding the ecotoxicological risks of ionic liquids - where are we? p.42/??

111 Conclusions I Many IL are not inherently green there is a possibility of thermal decomposition to unknown products Understanding the ecotoxicological risks of ionic liquids - where are we? p.43/??

112 Conclusions I Many IL are not inherently green there is a possibility of thermal decomposition to unknown products most of the ions used are not readily biodegradable Understanding the ecotoxicological risks of ionic liquids - where are we? p.43/??

113 Conclusions I Many IL are not inherently green there is a possibility of thermal decomposition to unknown products most of the ions used are not readily biodegradable some of the ions have a high basal cytotoxicity Understanding the ecotoxicological risks of ionic liquids - where are we? p.43/??

114 Conclusions I Many IL are not inherently green there is a possibility of thermal decomposition to unknown products most of the ions used are not readily biodegradable some of the ions have a high basal cytotoxicity some IL have a high aquatic toxicity Understanding the ecotoxicological risks of ionic liquids - where are we? p.43/??

115 Conclusions II But there are good news! knowledge about long term thermal stability is building up Understanding the ecotoxicological risks of ionic liquids - where are we? p.44/??

116 Conclusions II But there are good news! knowledge about long term thermal stability is building up IL are being optimized for biodegradability Understanding the ecotoxicological risks of ionic liquids - where are we? p.44/??

117 Conclusions II But there are good news! knowledge about long term thermal stability is building up IL are being optimized for biodegradability many of the ions have a low basal cytotoxicity Understanding the ecotoxicological risks of ionic liquids - where are we? p.44/??

118 Conclusions II But there are good news! knowledge about long term thermal stability is building up IL are being optimized for biodegradability many of the ions have a low basal cytotoxicity some IL have low aquatic and terrestrial toxicity Understanding the ecotoxicological risks of ionic liquids - where are we? p.44/??

119 Acknowledgments Coauthors Understanding the ecotoxicological risks of ionic liquids - where are we? p.45/??

120 Acknowledgments Coauthors Merck KGaA, Darmstadt Understanding the ecotoxicological risks of ionic liquids - where are we? p.45/??

121 Acknowledgments Coauthors Merck KGaA, Darmstadt FSU Jena Understanding the ecotoxicological risks of ionic liquids - where are we? p.45/??

122 Acknowledgments Coauthors Merck KGaA, Darmstadt FSU Jena IOLITEC, Solvent innovation and other cooperation partners Understanding the ecotoxicological risks of ionic liquids - where are we? p.45/??

123 Acknowledgments Coauthors Merck KGaA, Darmstadt FSU Jena IOLITEC, Solvent innovation and other cooperation partners Prof. R. Schwarzenbach and Prof. K. Hungerbühler, ETH Zürich Understanding the ecotoxicological risks of ionic liquids - where are we? p.45/??

124 Acknowledgments Coauthors Merck KGaA, Darmstadt FSU Jena IOLITEC, Solvent innovation and other cooperation partners Prof. R. Schwarzenbach and Prof. K. Hungerbühler, ETH Zürich Prof. B. Jastorff, Universität Bremen Understanding the ecotoxicological risks of ionic liquids - where are we? p.45/??