La spéciation des métaux Enjeux REACH. Solutions Analytiques. Olivier F.X. Donard

Transcription

1 La spéciation des métaux Enjeux REACH Solutions Analytiques Olivier F.X. Donard Laboratoire de Chimie Analytique Bioinorganique et Environnement IPREM CNRS UMR 5254 Pau (64053) FRANCE

2 REACH Registration, Evaluation, Authorisation and Restriction of Chemicals EU Directive 2006/121/CE Published in 30 December 2006 REACH is operational starting from 1 June 2007 Objectives Improve human health and the environment together with Preservation of EU chemical industry competitivness Improved risk management of chemical REACH aims at reducing animal experimentation and promotes alternative methods (QSARs)

3 What we have to do! (Adapted from P. Toulhoat) Existing data basis Speciation Distribution and Speciation of Toxic species Distribution and speciation of Toxic species QSAR Test in vitro Cell cultures Artificial organs Integration in whole organisms Validation : Tests in vivo Identification of physico chemical properties RMN Chromato Proteomique Metabolomique Biomarkers Proteomique Metabolomique

4 QSAR Quantitative Structure Activity Relationship QSAR are theorotical models that can be used to predict the physicochemical, biological and environmental fate properties of molecules Information provided by QSARs Physico chemical properties Eco toxic potential and potency Environmental distribution and fate Biokinetic processes Basic assumption is that similar molecules have similar properties

5 REACH Registration, Evaluation, Authorisation and Restriction of Chemicals (Adapted for P. Toulhoat) Development of predictive approaches in toxicology and ecotoxicology Validation of the methodes : in vivo (animal test to be minimized) Specifique analytical requirements Identification of affinities and physi cochemical properties (ex K OW or logp) Speciation in solution and reactivity Speciation in biological medium Identification and quantification of biomarkers

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8 Biochemical transformations of arsenic in aquatic environments Water AsIII, AsV MMAA, DMAA,TMAO S adenosylmethionine CH 3 H 2 N SAM CO 2 Algua S + O N N OH OH N H N Microbial degradation 2 N O (CH 3 ) 2 As Methylation O OR Fishs, molluscs, crustaceans Arsenobetaine Acide dimethylarsinylacitic Oxydation Dimethylarsinylethanol Oxydation Arsenocholine Methylation Anaerobic microbial decomposition Francesconi OH OH Arseno sugars

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10 / w w w.epa.gov/ oppt/ exposure/ pubs/ episuite.htm

11 As species physicochemical properties TMAO AsB Arsenosugar OH Compound log Kow pred log Kow exp BP pred BP exp MP pred MP exp Arsenosugar 2,79 n.a. 481,97 n.a. 204,18 n.a. MMA 1,18 n.a. 243,14 n.a. 54,52 n.a. DMA 0,36 n.a. 175,56 >200 12,53 195,00 AsC 1,89 n.a. 194,76 n.a. 4,45 n.a. AsB 2,12 n.a. 239,79 n.a. 47,84 n.a. TMAO 2,32 n.a. 97,03 n.a. 11,48 n.a. TETRA 2,87 n.a. 88,99 n.a. 71,38 n.a.

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13 Hg species physico chemical properties Me2Hg Et2Hg Compound log Kow pred log Kow exp BP pred BP exp MP pred MP exp MeHgCl 0,39 0,41 116,77 n.a 43,84 167,00 Me2Hg 0,62 2,59 104, ,61 <25 MeEtHg 1,11 n.a. 128,36 n.a 44,25 n.a Et2Hg 1,61 n.a. 150, ,95 <25

14 Organotin species physico chemical properties Me3Sn+ MeBu3Sn Ph4Sn Compound log Kow pred log Kow exp BP pred BP exp MP pred MP exp LD 50* Cl MeSnCl3 1,29 n.a. 114,99 171,00 35,81 49, Me2SnCl2 1,06 n.a. 103,16 189,00 48,59 106,50 74 EtSnCl 0,08 n.a. 138,00 n.a. 23,46 n.a. 13 Et2SnCl2 0,07 n.a. 149,17 n.a. 23,89 84,50 n.a. BuSnCl3 0,18 0,41 181,29 79,00 0,45 63, Me3SnCl 0,28 n.a. 91,11 148,00 61,44 38,50 n.a. Et3SnCl 1,75 n.a. 160,11 n.a. 24,39 n.a. n.a. Bu2SnCl2 1,89 1,56 230,33 135,00 22,34 42, Me4Sn 3,48 3,48 78,83 78,00 74,35 54,80 n.a. Bu3SnCl 4,70 4,76 273,72 19,00 42,59 53, Me3BuSn 4,95 n.a. 149,19 n.a. 36,90 n.a. n.a. Me2Bu2Sn 6,42 n.a. 211,41 n.a. 1,83 n.a. n.a. MeBu3Sn 7,90 n.a. 265,50 n.a. 3,87 n.a. n.a. * : LD 50 to rats

15 Compound log Kow pred Bu3SnCl 4,70 MeBu3Sn 7,90 Methyl TriButylTin

16 Partition of hexachlorobenzene in the environment Cl Cl Cl Cl Cl Cl Hexachlorobenzène Emissions Reactivity Exchanges Advection 200 Kg/h 450 Kg/h 28.3 Kg/h 2.2 Kg/h Air 0.4% 5.3 Kg/h 192 Kg/h Soil Water 516 ng/g 0,55 ng/l 176 Kg/h (After Mackay 1994) 2.5 Kg/h 89.1 Kg/h 34.7 Kg/h Sediments 2608 ng/l 655 Kg/h 2.7 Kg/h 350 Kg/h 110 Kg/h 1.4 Kg/h 33.4 Kg/h 21 Kg/h Kg/h

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18 Experiment of Kirchoff and Busen investigating for line reversal in the Sodium spectrum. The Sodium D line appears as a black discontinuity in the continuous spectrum

19 Beginning of modern atomic spectroscopy February 1952 «Internal report» Sir A. W alsh «Assuming that the sample is vaporised by the usual methods, e.g. flame, arc, or spark, then the emission spectrum is «removed» by means of the chopper principle. Thus the emission spectrum produces no output signal and only the atomic spectrum is recorded.»

20 P ublication trend Atomic spectrometr ic techniques used for speciation Publication rate Others (below 10) HG AAS GC MS SFC ICP MS CE ICP MS FI HG AAS FI GFAAS FI FAAS LC ICP MS GC ICP MS GC MIP AES LC ICP AES LC ET AAS LC FAAS GC AAS VG CT GC AAS LC CVG AAS LC HG AAS P ELIDAS Michael Sperling, 1998 Year of publication SF FFFF FF: B28 M. Sperling

21 Sensitivity Dialysis Electrochemistry Inorganic Organometallics Natural versus Anthropogenic Biomolecules Humics complexed Sensitivity GC ICP/MS GC AFS GC MS HPLC ICP/MS HPLC HG AFS LC MS ESI MS NMR

22 Analytical domains Information Level Molecular integrity LC/GC/MS/MS GC/IT/MS LC/MS/MS GC/MS LC/MS GC/FPD LC/UV Molecular destruction C, H, N, P analysers... Elemental Analysis Cd, Zn, Se, As,.. ICP/MS, HR/ICP/MS analysers AAS, ICP/AES, Organic analysis Increasing instrument complexity Increasing sensitivity Inorganic analysis 2000 LCABIE

23 Analytical chemistry should deliver information Information Level Molecular integrity GC/AED GC/IT/MS GC/FPD GC/MS Species determination GC/ICP/MS/MC GC/ICP/MS CT/AFS GC/ICP/AES LC/GC/MS/MS LC/MS/MS HPLC/HG/AFS HPLC/ICP/MS LC/MS LC/UV C, H, N, P analysers... Cd, Zn, Se,.. ICP/MS, HR/ICP/MS analysers AAS, ICP/AES, AFS Organic analysis Increasing instrument complexity Increasing sensitivity Inorganic analysis LCABIE

24 «Heavy Metal?» «Heavy Metal»

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