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Boom Clay Natural Organic Matter EXTERNAL REPORT SCK•CEN-ER-206 12/CBr/P-37 Boom Clay natural organic matter Status Report 2011 Christophe Bruggeman and Mieke De Craen SCK•CEN Contract: CO-90-08-2214-00 NIRAS/ONDRAF contract: CCHO 2009- 0940000 Research Plan Geosynthesis June, 2012 SCK•CEN RDD Boeretang 200 BE-2400 Mol Belgium EXTERNAL REPORT OF THE BELGIAN NUCLEAR RESEARCH CENTRE SCK•CEN-ER-206 12/CBr/P-37 Boom Clay natural organic matter Status Report 2011 Christophe Bruggeman and Mieke De Craen SCK•CEN Contract: CO-90-08-2214-00 NIRAS/ONDRAF contract: CCHO 2009- 0940000 Research Plan Geosynthesis June, 2012 Status: Unclassified ISSN 1782-2335 SCK•CEN Boeretang 200 BE-2400 Mol Belgium © SCK•CEN Studiecentrum voor Kernenergie Centre d’étude de l’énergie Nucléaire Boeretang 200 BE-2400 Mol Belgium Phone +32 14 33 21 11 Fax +32 14 31 50 21 http://www.sckcen.be Contact: Knowledge Centre [email protected] COPYRIGHT RULES All property rights and copyright are reserved to SCK•CEN. In case of a contractual arrangement with SCK•CEN, the use of this information by a Third Party, or for any purpose other than for which it is intended on the basis of the contract, is not authorized. With respect to any unauthorized use, SCK•CEN makes no representation or warranty, expressed or implied, and assumes no liability as to the completeness, accuracy or usefulness of the information contained in this document, or that its use may not infringe privately owned rights. SCK•CEN, Studiecentrum voor Kernenergie/Centre d'Etude de l'Energie Nucléaire Stichting van Openbaar Nut – Fondation d'Utilité Publique ‐ Foundation of Public Utility Registered Office: Avenue Herrmann Debroux 40 – BE‐1160 BRUSSEL Operational Office: Boeretang 200 – BE‐2400 MOL Table of Contents Abstract ...................................................................................................................................... 7 1. Introduction ........................................................................................................................ 9 1.1. Natural organic matter: background and definitions ............................................... 9 1.2. Natural organic matter in the Boom Clay .............................................................. 10 2. Solid Boom Clay organic matter ...................................................................................... 11 2.1. Geochemistry of kerogen - general ........................................................................... 11 2.1.1. Isolation and analysis of kerogen ....................................................................... 12 2.1.2. The classification of kerogens............................................................................ 14 2.1.3. Kerogen transformation on burial and its evolution path .................................. 15 2.1.4. Kerogen conceptual models ............................................................................... 16 2.2 Studies on Boom Clay organic matter and kerogen ....................................................... 20 2.2.1 PhD thesis of Noël Vandenberghe .......................................................................... 20 2.2.2 PhD thesis of Ben Laenen ....................................................................................... 21 2.2.3 PhD thesis and Post-doc of Isabelle Deniau ........................................................... 31 2.2.4 TRANCOM-II studies............................................................................................. 34 2.2.5 PhD thesis of Pascale Blanchart.............................................................................. 37 2.3.Comparison of kerogens from Boom Clay, Callovo-Oxfordian argillite and Toarcian shales .................................................................................................................................... 38 2.4. Conclusion on the solid Boom Clay organic matter ..................................................... 41 3. Dissolved organic matter ................................................................................................. 43 3.1. Dissolved organic matter – definitions and background ........................................... 43 3.2. Functional group content of dissolved organic matter in Boom Clay ....................... 47 3.2.1 Introduction ............................................................................................................. 47 3.2.2 Elemental and spectroscopic characterisation of Boom Clay dissolved organic matter ............................................................................................................................... 48 3.2.3 Potentiometric characterisation of Boom Clay dissolved organic matter ............... 51 3.2.4 Modelling of potentiometric titrations .................................................................... 58 3.3 Composition and source of Boom Clay dissolved organic matter ............................ 61 3.3.1 Introduction ............................................................................................................. 61 3.3.2 Work performed during TRANCOM-II (MORPHEUS piezometer) ..................... 61 3.3.3 PhD of Pascale Blanchart ........................................................................................ 69 3.3.4 Conclusion with respect to the source and composition of dissolved organic matter in Boom Clay ................................................................................................................... 72 3.4 Redox reactivity of dissolved organic matter ............................................................ 73 3.5 Size distribution of dissolved organic matter in Boom Clay ..................................... 76 3.5.1 Introduction ............................................................................................................. 76 3.5.2 Characterisation of Boom Clay dissolved organic matter size distribution ............ 76 3.5.3 Conclusion: mobile organic matter concentration in Boom Clay ........................... 85 3.6 Migration of dissolved Boom Clay organic matter ................................................... 87 3.6.1 Sorption of dissolved organic matter onto Boom Clay ...................................... 87 3.6.2 Overview of migration experiments with Boom Clay dissolved organic matter 89 3.6.3 Conclusion on the migration of dissolved organic matter in Boom Clay ........ 111 4. Perturbations and evolving conditions related to Boom Clay organic matter ............... 115 4.1 Thermal perturbation .................................................................................................... 115 4.1.1. Release of thermolabile components ............................................................... 115 4.1.2. Production of CO2 from the Boom Clay kerogen under thermal stress ........... 117 5 4.1.3. Comparison to other geological formations. .................................................... 123 4.2. Impact of alkaline perturbation ............................................................................... 125 4.3. Impact of ionic strength perturbation ...................................................................... 127 4.4 Impact of oxidation ...................................................................................................... 130 4.4.1 Introduction ........................................................................................................... 130 4.4.2 Impact of oxidation on the compositions of kerogen and bitumen ....................... 130 4.4.3 Impact of oxidation on the fraction of dissolved organic matter .......................... 132 4.5 Impact of compaction................................................................................................... 136 5. General conclusions and recommendations ................................................................... 140 6. References ...................................................................................................................... 141 6 Abstract Boom Clay contains an appreciable amount of low-maturity natural organic matter. This organic matter may be operationally subdivided into different pools, which have various impacts on, among others, the pore water chemistry and radionuclide geochemistry. Moreover, the creation and operation of a geological repository located in the Boom Clay will cause perturbations to the organic matter, which need to be properly assessed. This state-of- the-art report aims at bringing together the results obtained from various scientific sources and communities involved in the study of Boom Clay organic matter. Both origins, preservation pathways, nowadays in situ situation (Mol-Dessel reference site) and expected future evolutions of Boom Clay natural organic matter (and important subfractions thereof) are evaluated and discussed. Keywords Boom clay, geological disposal, natural organic matter, perturbations 7 1. Introduction 1.1. Natural organic matter: background and definitions Natural organic matter is all the organic matter in a reservoir or natural ecosystem, other than living organisms and compounds of man-made origin (BUFFLE, 1988). It is ubiquitous in the environment, occurring in all soils, waters and sediments of the ecosphere. The natural organic matter found in soils and sediments possesses a large variety of properties and is composed of an extremely complex mixture of compounds, most of which are not yet identified. Indeed, the number of compounds making up natural organic matter can be considered as "infinite"
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