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Interlaboratory CEC and Exchangeable Cation Study of Bentonite Buffer Materials: I. Cu(II)-Triethylenetetramine Method

Published online by Cambridge University Press:  01 January 2024

Reiner Dohrmann ,
Dieter Genske ,
Ola Karnland ,
Stephan Kaufhold ,
Leena Kiviranta ,
Siv Olsson ,
Michael Plötze ,
Torbjörn Sandén ,
Patrik Sellin  and
Daniel Svensson
...Show all authors
Reiner Dohrmann*
Affiliation:
Landesamt für Bergbau, Energie und Geologie (LBEG), Stilleweg 2, D-30655 Hannover, Germany Bundesanstalt für Geowissenschaften und Rohstoffe (BGR), Stilleweg 2, D-30655 Hannover, Germany
Dieter Genske
Affiliation:
S&B Industrial Minerals GmbH, Schmielenfeldstrasse 78, D-45772 Marl, Germany
Ola Karnland
Affiliation:
Clay Technology AB, IDEON Research Center, SE-22370 Lund, Sweden
Stephan Kaufhold
Affiliation:
Bundesanstalt für Geowissenschaften und Rohstoffe (BGR), Stilleweg 2, D-30655 Hannover, Germany
Leena Kiviranta
Affiliation:
B+Tech Oy, Laulukuja 4, FI-00420 Helsinki, Finland
Siv Olsson
Affiliation:
Clay Technology AB, IDEON Research Center, SE-22370 Lund, Sweden
Michael Plötze
Affiliation:
ETH Zürich, Institute for Geotechnical Engineering, ClayLab, Schafmattstrasse 6, CH-8093 Zurich, Switzerland
Torbjörn Sandén
Affiliation:
Clay Technology AB, IDEON Research Center, SE-22370 Lund, Sweden
Patrik Sellin
Affiliation:
Swedish Nuclear Fuel and Waste Management Co (SKB), Pl 300, SE-57295 Figeholm, Sweden
Daniel Svensson
Affiliation:
Swedish Nuclear Fuel and Waste Management Co (SKB), Box 929, SE-57229, Oskarshamn, Sweden
Martin Valter
Affiliation:
ETH Zürich, Institute for Geotechnical Engineering, ClayLab, Schafmattstrasse 6, CH-8093 Zurich, Switzerland
*
*E-mail address of corresponding author: [email protected]
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Abstract

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Bentonites are candidate materials for encapsulation of radioactive waste. The cation exchange capacity (CEC) has proved to be one of the most sensitive parameters for detecting changes of mineral properties such as swelling capacity and illitization in alteration experiments. Whether measured differences in CEC values of bentonite buffer samples before and after an experiment are (1) actual differences caused by clay structural changes such as illitization or (2) simply data scatter due to the different methods used by international research teams is an open question. The aim of this study was to measure the CEC of clay samples in five different laboratories using the same method and to evaluate the precision of the values measured. The Cu-trien method and four reference materials of the Alternative Buffer Material (ABM) test project in Äspö, Sweden, were chosen for this interlaboratory study. The precision of the Cu-trien method, which uses visible spectroscopy, was very good with a standard deviation of ±0.7–2.1 meq/100 g for CECs that ranged from 11 to 87 meq/100 g. For the same CEC range, analysis of Cu-trien index cations using inductively coupled plasma (mass spectrometry) and atomic absorption spectroscopy were less precise with a standard deviation of ±2.8–3.9 meq/100 g. Based on the measured precision, greater measured differences in Cu-trien CEC and exchangeable cation values of bentonite buffer samples, before and after an experiment, might be actual differences. Great care must be taken when interpreting measured CEC differences, and analytical characterization of any structural changes may be needed. Compared with results from the ‘International Soil-Analytical Exchange’ (iSE) program for soils, most absolute concentrations were much larger for the clays studied; however, for the two parameters exchangeable Ca2+ and CEC the range was similar to the iSE ring test and, most importantly, the precision was comparable. Future studies should discuss the accuracy of CEC and exchangeable cation values and compare them to alternative CEC methods in which care is taken to prevent dissolution of soluble minerals, such as calcite and gypsum.

Keywords

Bentonite BufferCECCu-trienExchangeable CationsInterlaboratory Study
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 2 , April 2012 , pp. 162 - 175
Copyright
Copyright © Clay Minerals Society 2012

References

Ammann, L. Bergaya, F. and Lagaly, G., 2005 Determination of the cation exchange capacity of clays with copper complexes revisited Clay Minerals 40 441–453.CrossRefGoogle Scholar
Bache, B.W., 1976 The measurement of cation exchange capacity of soils Journal of the Science of Food and Agriculture 27 273–280.CrossRefGoogle Scholar
Bascomb, C.L., 1964 Rapid method for the determination of the cation exchange capacity of calcareous and noncalcareous soils Journal of the Science of Food and Agriculture 15 821–823.CrossRefGoogle Scholar
Bergaya, F. and Vayer, M., 1997 CEC of clays measurements by adsorption of a copper ethylenediamine complex Applied Clay Science 12 275–280.CrossRefGoogle Scholar
Ciesielski, H. and Sterckeman, T., 1997 A comparison between three methods for the determination of cation exchange capacity and exchangeable cations in soils Agronomie 17 9–15.CrossRefGoogle Scholar
Dohrmann, R., 2006 Cation Exchange Capacity Methodology I: An Efficient Model for the Detection of Incorrect Cation Exchange Capacity and Exchangeable Cation Results Applied Clay Science 34 31–37.CrossRefGoogle Scholar
Dohrmann, R., 2006 Cation Exchange Capacity Methodology III: Correct exchangeable calcium determination of calcareous clays using a new silver-thiourea method Applied Clay Science 34 47–57.CrossRefGoogle Scholar
Dohrmann, R. and Kaufhold, S., 2009 Three new, quick CEC methods for determining the amounts of exchangeable calcium cations in calcareous clays Clays and Clay Minerals 57 338–352.CrossRefGoogle Scholar
Dohrmann, R. and Kaufhold, S., 2010 Determination of exchangeable calcium of calcareous and gypsiferous bentonites Clays and Clay Minerals 58 79–88.CrossRefGoogle Scholar
Dohrmann, R. Genske, D. Karnland, O. Kaufhold, S. Kiviranta, L. Olsson, S. Plötze, M. Sandén, T. Sellin, P. Svensson, D. and Valter, M., 2012 Interlaboratory CEC and exchangeable cation study of bentonite buffer materials: II. Alternative methods Clays and Clay Minerals 60 176–185.CrossRefGoogle Scholar
Eng, A. Nilsson, U. and Svensson, D., 2007 ÄspöHard Rock Laboratory Alternative Buffer Material, Installation report, IPR-07-15 67.Google Scholar
Houba, V.J.G. Uittenbogaard, J. and Pellen, P., 1996 Wageningen Evaluating programs for Analytical Laboratories (WEPAL), organization and purpose Communications in Soil Science and Plant Analysis 27 421–431.CrossRefGoogle Scholar
iSE, 2006 International Soil-Analytical Exchange (iSE) program, annual report 2006 Wageningen Evaluating programs for Analytical Laboratories (WEPAL) .Google Scholar
iSE, 2008 International Soil-Analytical Exchange (iSE) program, annual report 2008 Wageningen Evaluating programs for Analytical Laboratories (WEPAL) .Google Scholar
Kahr, G. Meier, L., Wolf, D. Starke, R. and Kleeberg, R., 1996 Einfache Bestimmungsmethode des Kationenaustauschver-mögens von Tonen mit den Komplexverbindungen des Kupfer(II)-Ions mit Triethylentetramin und Tetraethylenpentamin Berichte der DTTG 1996 122–126.Google Scholar
Kaufhold, S. and Dohrmann, R., 2003 Beyond the Methylene Blue method: determination of the smectite content using the Cu-triene method Zeitschrift für Angewandte Geologie 49 13–17.Google Scholar
Kaufhold, S. and Dohrmann, R., 2010 Effect of extensive drying on the cation exchange capacity of bentonites Clay Minerals 45 441–448.CrossRefGoogle Scholar
Kaufhold, S. and Dohrmann, R., 2010 Stability of bentonites in salt solutions II Potassium chloride solution - Initial step of illitization? Applied Clay Science 49 98–107.Google Scholar
Lim, C.H. Jackson, M.L. Koons, R.D. and Helmke, P.A., 1980 Kaolins: Sources of differences in cation-exchange capacities and cesium retention Clays and Clay Minerals 28 223–229.CrossRefGoogle Scholar
Matsue, N. and Wada, K., 1985 A new equilibration method for cation exchange capacity measurement Soil Science Society of America Journal 49 574–578.CrossRefGoogle Scholar
Meier, L.P. and Kahr, G., 1999 Determination of the Cation Exchange Capacity (CEC) of clay minerals using the complexes of copper (II) ion with triethylenetetramine and tetraethylenepentamine Clays and Clay Minerals 47 386–388.CrossRefGoogle Scholar
Muurinen, A., 2010 Studies on the chemical conditions and microstructure in package 1 of alternative buffer materials project (ABM) in Äspö Posiva WR 2010-11 Olkiluoto, Finland Posiva Oy 44.Google Scholar
Okazaki, R. Smith, H.W. and Moodie, C.D., 1962 Development of a cation-exchange capacity procedure with few inherent errors Soil Science 93 343–349.CrossRefGoogle Scholar
Rhodes, J.D., Page, A.L. Miller, R.H. and Keeney, D.R., 1982 Cation exchange capacity Methods of Soil Analysis. Part 2. Chemical and Microbiological Properties 2nd edition Madison, Wisconsin, USA American Society of Agronomy 149–157.Google Scholar
SKB 2007() RD&D Programme 2007. Programme for research, development and demonstration of methods for the management and disposal of nuclear waste. TR-07-12, Swedish Nuclear Fuel and Waste Management Company (SKB), Stockholm, Sweden. .Google Scholar
Steel, R.G.D. and Torrie, J.H., 1980 Principles and Procedures of Statistics: a Biometrical Approach New York McGraw-Hill Book Company 54–55.Google Scholar
Svensson, D., 2010 Mineralogical analysis ABM Project meeting, Lund, April 27–28, 2010, SKB 46.Google Scholar
Tucker, B.M., 1954 The determination of exchangeable calcium and magnesium in carbonate soils Australian Journal of Agricultural Research 5 706–715.CrossRefGoogle Scholar
Vieillard, P. Ramirez, S. Bouchet, A. Cassagnabere, A. Meunier, A. and Jacquot, E., 2004 Alteration of the Callovo-Oxfordian clay from Meuse-Haute Marne Underground Laboratory (France) by alkaline solution: II. Modelling of mineral reactions Applied Geochemistry 19 1699–1709.CrossRefGoogle Scholar
Way, J.T., 1852 On the power of soils to adsorb manure Journal of the Royal Agricultural Society of England 13 123–143.Google Scholar
Weiss, A., 1958 Über das Kationenaustauschvermögen der Tonminerale. I. Vergleich der Untersuchungsmethoden Zeitschrift für Anorganische und Allgemeine Chemie 297 232–255.CrossRefGoogle Scholar