Bromine in the Natural Environments of the Tomsk Region and Its Toxicity Assessment
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THESE pour l’obtention du grade de DOCTEUR de l’UNIVERSITE DE TECHNOLOGIE DE TROYES Spécialité : INGENIERIE SOCIOTECHNIQUE DES CONNAISSANCES, DES RESEAUX ET DU DEVELOPPEMENT DURABLE présentée et soutenue par Tatiana PERMINOVA le 26 octobre 2017 Bromine in the Natural Environments of the Tomsk Region and its Toxicity Assessment JURY M. L. RIKHVANOV PROFESSOR OF UNIVERSITIES Président M. S. ARBUZOV PROFESSOR OF UNIVERSITIES Examinateur Mme N. BARANOVSKAYA PROFESSOR OF UNIVERSITIES Directeur de thèse Mme G. KONARBAEVA PROFESSOR OF UNIVERSITIES Rapporteur M. B. LARATTE MAITRE DE CONFERENCES ASSOCIE Directeur de thèse Mme G. QUARANTA MAITRE DE CONFERENCES - HDR Rapporteur Mme V. STRAKHOVENKO PROFESSOR OF UNIVERSITIES Rapporteur M. E. YAZIKOV PROFESSOR OF UNIVERSITIES Examinateur BROMINE IN THE NATURAL ENVIRONMENTS OF THE TOMSK REGION AND ITS TOXICITY ASSESSMENT A dissertation thesis for the degree of Doctor of University of technology of Troyes and Candidate of geological-mineralogical sciences (the Earth sciences) by Tatiana PERMINOVA 2017 _______________ JURY Mme G. QUARANTA Maitre de conférences – HDR Rapporteur Université de Strasbourg Professor of universities Mme Institute of Soil Science and Rapporteur G.KONARBAEVA Agrochemistry, Siberian Branch of RAS (ISSA SB RAS) Professor of universities Mme V.S. Sobolev Institute of Geology Rapporteur V.STRAHOVENKO and Mineralogy of the Russian Academy of Sciences (IGM SB RAS) M. B. LARATTE Enseignant-Chercheur Directeur de thèse Arts et Métiers ParisTech, Talence Mme N. Professor of universities Directeur de thèse BARANOVSKAYA Tomsk Polytechnic University M. L. RIKHVANOV Professor of universities Examinateur Tomsk Polytechnic University M. E.G. YAZIKOV Professor of universities Examinateur Tomsk Polytechnic University M. S.I. ARBUZOV Professor of universities Examinateur Tomsk Polytechnic University ACKNOWLEDGEMENTS I would like to express my sincerest gratitude to my research supervisors: Prof. BARANOVSKAYA Natalia, and Dr. LARATTE Bertrand for their support, understanding, motivation and assistance at all stages of the work. Special gratitude also to Prof. RIKHVANOV Leonid P. and Prof. TROUSSIER Nadège for their valuable advice and help. I would like to thank all colleagues of the GEGH department of TPU and CREIDD of UTT for their advice and suggestions. Thanks to Prof. Regis LENGELLE, Prof. Khemais SAANOUNI, Mme. Isabelle LECLERCQ, Mme. Pascal DENIS and Mme. Thérèse Kazarian of the UTT PhD school for their help. I would also thank the secretaries: Stephanie JACOTIN, Christine HENRY and Sophie LÉVÊQUE for their operational efficiency. I am also grateful to all members of the laboratory of hydrology and geochemistry of the University of Strasbourg for their valuable advice. I would like to thank Peter FANTKE, Nienke MÜLLER and Olivier JOILLET for their active support in working with the USEtox model. I am thankful to Natalia SIRINA for joint cooperation and help. Thanks also to Florian BRATEC for his patience, help and support. I would like also to express my gratitude to Muriel WHITCHURCH for her constant assistance with the English. i ABSTRACT Abstract in English Bromine in contrast to other, even less common chemical elements, still remains one of the least studied. However, a great number of works show that it can be extremely toxic, exerting a negative impact on important physiological functions of living organisms and participating in the development and formation of certain types of diseases. The objective of this thesis is to establish accumulation and distribution features of bromine in the components of the natural environment of the Tomsk region, and to characterize its human and ecotoxicological impacts according to the USEtox model. This is achieved by combining two approaches: sampling methods and ecological modeling technics. Within the framework of the thesis, the content of bromine in 2709 samples is considered. The reliability of the work is provided by a statistically significant number of samples, analyzed by modern highly sensitive analytical methods (INAA, ICP-MS, X-ray fluorescence analysis, scanning electron microscopy) in accredited laboratories. Also for the first time, characterization factors for bromine have been calculated within the USEtox model. The results obtained could be useful in the future when evaluating the environmental impacts of chemicals and the associated risks for ecosystems and human health as well as for geoecological monitoring of the territory. Key words: – Bromine – Environmental impact analysis – Environmental geochemistry – Life cycle analysis – Risk assessment ii Abstract in French Le brome, contrairement à d'autres éléments chimiques, reste l'un des moins étudiés à ce jour. Cependant, un grand nombre de travaux montrent qu'il peut être extrêmement toxique, exerçant un impact négatif sur les fonctions physiologiques importantes des organismes vivants et participant au développement et à la formation de certains types de maladies. L'objectif de cette thèse est d'établir les caractéristiques d'accumulation et de distribution du brome dans les composantes de l'environnement naturel de la région de Tomsk et de caractériser ses impacts toxicologiques sur la santé humaine et les écosystèmes selon le modèle USEtox. Elle est réalisée en combinant deux approches : les méthodes d'échantillonnage et les techniques de modélisation écologique. Dans le cadre de la thèse, la teneur en brome dans 2709 échantillons est considérée. La fiabilité du travail est garantie par un nombre statistiquement significatif d'échantillons, analysés par des méthodes modernes et hautement sensibles (INAA, ICP-MS, Analyse de fluorescence aux rayons X, Microscopie électronique à balayage) dans des laboratoires accrédités. De plus, pour la première fois, les facteurs de caractérisation d’impact du brome ont été calculés dans le modèle USEtox. Les résultats obtenus pourraient être utiles à l'avenir lors de l'évaluation des impacts environnementaux des produits chimiques et des risques associés pour les écosystèmes et la santé humaine, ainsi que pour le suivi géoécologique d’un territoire. Mots clés – Brome – Environnement - Etudes d’impact – Géochimie de l’environnement – Analyse du cycle de vie – Evaluation de risque iii TABLE OF CONTENTS ACKNOWLEDGEMENTS ........................................................................................... i ABSTRACT .................................................................................................................. ii LIST OF FIGURES ..................................................................................................... vii LIST OF TABLES ...................................................................................................... xii INTRODUCTON ......................................................................................................... 1 Relevancy .................................................................................................................... 1 Study objective ............................................................................................................ 3 Principle tasks ............................................................................................................ 3 Principal propositions to be confirmed in this thesis ................................................ 4 Materials and research methods ................................................................................ 4 Reliability of proposition ............................................................................................ 5 Scientific novelty ........................................................................................................ 5 Practical significance ................................................................................................. 6 Work approbation ...................................................................................................... 7 Publications ................................................................................................................ 7 Thesis structure and volume ....................................................................................... 8 Personal author’s contribution .................................................................................. 9 CHAPTER 1. ECOLOGICAL AND GEOCHEMICAL PECULIARITIES OF BROMINE .................................................................................................................. 10 1.1 General characteristic of the element ................................................................. 11 1.2 Influence on living organisms ............................................................................ 13 1.2.1 Toxicity ........................................................................................................ 13 1.2.2 Bromine and human health .......................................................................... 15 1.3 Hygienic standards in Russia ............................................................................. 19 References ................................................................................................................... 20 CHAPTER 2. GEOECOLOGICAL ASPECTS OF ACCUMULATION AND DISTRIBUTION OF BROMINE IN NATURAL AND TECHNOGENIC SYSTEMS .................................................................................................................. 26 2.2 About the variability of bromine concentrations in the lithosphere .................. 35 2.3. Bromine in living