Batch sorption experiments of cesium and strontium on crushed rock and biotite for the estimation of distribution coefficients on intact crystalline rock

Tutkimustuotos: ArtikkelijulkaisuArtikkeliTieteellinenvertaisarvioitu

Kuvaus

The distribution coefficient (Kd) of radionuclides on bedrock is one of the key parameters used in the safety analysis of spent nuclear fuel repositories. Typically, distribution coefficients have been determined using crushed rock. However, recent studies have shown that crushing of the rock increases considerably the distribution coefficient compared with the values of intact rock. This study aimed to test if batch sorption experiments using different grain sizes (i.e. mean diameter of grains) can be used to evaluate the Kd of strontium (Sr) and cesium (Cs) on intact crystalline rock, which would decrease the needed experimental time compared with transport experiments. Here we report the results of the batch sorption experiments with crushed rocks and compare the results with those from a recent study performed using electromigration experiments with intact drill core samples (Puukko et al., 2018). The batch sorption experiments were done for rock samples from Olkiluoto, Finland, as a function of grain size and of Cs and Sr concentration. Furthermore, the specific surface areas of the same rock samples with different grain sizes were determined. It was shown that Cs distribution coefficients correlate with specific surface areas of the studied rocks and biotite, the correlation coefficient being 0.95. The Cs distribution coefficient was highest for biotite at about 0.1 m3/kg at 10−4 M cesium concentration and increased systematically to about 1 m3/kg at 10−8 M. Distribution coefficients for rocks were up to about two orders of magnitude lower, being lowest with the rock with the lowest biotite content (3.3%). The distribution coefficient of Sr varied from 0.04 m3/kg to 0.007 m3/kg and behaved in a different manner: it remained constant in two out of three studied rocks in the concentration range of 10−8-10−4 M and only in the case of one rock a decreasing trend was seen at the higher concentration range. It was also shown that batch sorption experiments overestimate the distribution coefficient in respect to intact rock. The decrease of the distribution coefficient as a function of grain size can be estimated using a power law function. It was also shown that estimation of distribution coefficients of Cs and Sr for intact rock by extrapolation of distribution coefficients determined for different grain sizes is not possible without increasing grain size, but in that case diffusion into the grains would also affect the results. A new method was developed for estimating the fraction of the inner surface area of the total surface area of crushed grains. For the mean grain sizes of 0.25 mm and 0.75 mm the fraction of the inner surface was found to be 35–70% and 60–90%, respectively. The inner specific surface area was highest with biotite at 1.2 m2/g and lowest with the rock with lowest biotite content (3.3%) at 0.07 m2/g. The surface area analysis revealed that crushing creates and/or allows access to additional inner surface area that is not measured in intact rock. Furthermore, it was demonstrated that sorption of Cs on crushed rock was dominated by mica minerals in multiple concentrations while the effect of mica minerals on the Kd of Sr was not as straightforward.
Alkuperäiskielienglanti
LehtiHeliyon
Vuosikerta5
Numero8
Sivute02296
ISSN2405-8440
DOI - pysyväislinkit
TilaJulkaistu - 13 elokuuta 2019
OKM-julkaisutyyppiA1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä, vertaisarvioitu

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  • 116 Kemia

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@article{30d0b637489940a39f94a533f0fbc0ac,
title = "Batch sorption experiments of cesium and strontium on crushed rock and biotite for the estimation of distribution coefficients on intact crystalline rock",
abstract = "The distribution coefficient (Kd) of radionuclides on bedrock is one of the key parameters used in the safety analysis of spent nuclear fuel repositories. Typically, distribution coefficients have been determined using crushed rock. However, recent studies have shown that crushing of the rock increases considerably the distribution coefficient compared with the values of intact rock. This study aimed to test if batch sorption experiments using different grain sizes (i.e. mean diameter of grains) can be used to evaluate the Kd of strontium (Sr) and cesium (Cs) on intact crystalline rock, which would decrease the needed experimental time compared with transport experiments. Here we report the results of the batch sorption experiments with crushed rocks and compare the results with those from a recent study performed using electromigration experiments with intact drill core samples (Puukko et al., 2018). The batch sorption experiments were done for rock samples from Olkiluoto, Finland, as a function of grain size and of Cs and Sr concentration. Furthermore, the specific surface areas of the same rock samples with different grain sizes were determined. It was shown that Cs distribution coefficients correlate with specific surface areas of the studied rocks and biotite, the correlation coefficient being 0.95. The Cs distribution coefficient was highest for biotite at about 0.1 m3/kg at 10−4 M cesium concentration and increased systematically to about 1 m3/kg at 10−8 M. Distribution coefficients for rocks were up to about two orders of magnitude lower, being lowest with the rock with the lowest biotite content (3.3{\%}). The distribution coefficient of Sr varied from 0.04 m3/kg to 0.007 m3/kg and behaved in a different manner: it remained constant in two out of three studied rocks in the concentration range of 10−8-10−4 M and only in the case of one rock a decreasing trend was seen at the higher concentration range. It was also shown that batch sorption experiments overestimate the distribution coefficient in respect to intact rock. The decrease of the distribution coefficient as a function of grain size can be estimated using a power law function. It was also shown that estimation of distribution coefficients of Cs and Sr for intact rock by extrapolation of distribution coefficients determined for different grain sizes is not possible without increasing grain size, but in that case diffusion into the grains would also affect the results. A new method was developed for estimating the fraction of the inner surface area of the total surface area of crushed grains. For the mean grain sizes of 0.25 mm and 0.75 mm the fraction of the inner surface was found to be 35–70{\%} and 60–90{\%}, respectively. The inner specific surface area was highest with biotite at 1.2 m2/g and lowest with the rock with lowest biotite content (3.3{\%}) at 0.07 m2/g. The surface area analysis revealed that crushing creates and/or allows access to additional inner surface area that is not measured in intact rock. Furthermore, it was demonstrated that sorption of Cs on crushed rock was dominated by mica minerals in multiple concentrations while the effect of mica minerals on the Kd of Sr was not as straightforward.",
keywords = "Electrochemistry, Crystalline rock, Cesium, Strontium, Specific surface area, Sorption, Distribution coefficient, Radionuclide, 116 Chemical sciences",
author = "Jukka Lehto and Esa Puukko and Antero Lindberg and Mikko Voutilainen",
year = "2019",
month = "8",
day = "13",
doi = "10.1016/j.heliyon.2019.e02296",
language = "English",
volume = "5",
pages = "e02296",
journal = "Heliyon",
issn = "2405-8440",
publisher = "ELSEVIER SCI IRELAND LTD",
number = "8",

}

Batch sorption experiments of cesium and strontium on crushed rock and biotite for the estimation of distribution coefficients on intact crystalline rock. / Lehto, Jukka; Puukko, Esa; Lindberg, Antero; Voutilainen, Mikko.

julkaisussa: Heliyon, Vuosikerta 5, Nro 8, 13.08.2019, s. e02296.

Tutkimustuotos: ArtikkelijulkaisuArtikkeliTieteellinenvertaisarvioitu

TY - JOUR

T1 - Batch sorption experiments of cesium and strontium on crushed rock and biotite for the estimation of distribution coefficients on intact crystalline rock

AU - Lehto, Jukka

AU - Puukko, Esa

AU - Lindberg, Antero

AU - Voutilainen, Mikko

PY - 2019/8/13

Y1 - 2019/8/13

N2 - The distribution coefficient (Kd) of radionuclides on bedrock is one of the key parameters used in the safety analysis of spent nuclear fuel repositories. Typically, distribution coefficients have been determined using crushed rock. However, recent studies have shown that crushing of the rock increases considerably the distribution coefficient compared with the values of intact rock. This study aimed to test if batch sorption experiments using different grain sizes (i.e. mean diameter of grains) can be used to evaluate the Kd of strontium (Sr) and cesium (Cs) on intact crystalline rock, which would decrease the needed experimental time compared with transport experiments. Here we report the results of the batch sorption experiments with crushed rocks and compare the results with those from a recent study performed using electromigration experiments with intact drill core samples (Puukko et al., 2018). The batch sorption experiments were done for rock samples from Olkiluoto, Finland, as a function of grain size and of Cs and Sr concentration. Furthermore, the specific surface areas of the same rock samples with different grain sizes were determined. It was shown that Cs distribution coefficients correlate with specific surface areas of the studied rocks and biotite, the correlation coefficient being 0.95. The Cs distribution coefficient was highest for biotite at about 0.1 m3/kg at 10−4 M cesium concentration and increased systematically to about 1 m3/kg at 10−8 M. Distribution coefficients for rocks were up to about two orders of magnitude lower, being lowest with the rock with the lowest biotite content (3.3%). The distribution coefficient of Sr varied from 0.04 m3/kg to 0.007 m3/kg and behaved in a different manner: it remained constant in two out of three studied rocks in the concentration range of 10−8-10−4 M and only in the case of one rock a decreasing trend was seen at the higher concentration range. It was also shown that batch sorption experiments overestimate the distribution coefficient in respect to intact rock. The decrease of the distribution coefficient as a function of grain size can be estimated using a power law function. It was also shown that estimation of distribution coefficients of Cs and Sr for intact rock by extrapolation of distribution coefficients determined for different grain sizes is not possible without increasing grain size, but in that case diffusion into the grains would also affect the results. A new method was developed for estimating the fraction of the inner surface area of the total surface area of crushed grains. For the mean grain sizes of 0.25 mm and 0.75 mm the fraction of the inner surface was found to be 35–70% and 60–90%, respectively. The inner specific surface area was highest with biotite at 1.2 m2/g and lowest with the rock with lowest biotite content (3.3%) at 0.07 m2/g. The surface area analysis revealed that crushing creates and/or allows access to additional inner surface area that is not measured in intact rock. Furthermore, it was demonstrated that sorption of Cs on crushed rock was dominated by mica minerals in multiple concentrations while the effect of mica minerals on the Kd of Sr was not as straightforward.

AB - The distribution coefficient (Kd) of radionuclides on bedrock is one of the key parameters used in the safety analysis of spent nuclear fuel repositories. Typically, distribution coefficients have been determined using crushed rock. However, recent studies have shown that crushing of the rock increases considerably the distribution coefficient compared with the values of intact rock. This study aimed to test if batch sorption experiments using different grain sizes (i.e. mean diameter of grains) can be used to evaluate the Kd of strontium (Sr) and cesium (Cs) on intact crystalline rock, which would decrease the needed experimental time compared with transport experiments. Here we report the results of the batch sorption experiments with crushed rocks and compare the results with those from a recent study performed using electromigration experiments with intact drill core samples (Puukko et al., 2018). The batch sorption experiments were done for rock samples from Olkiluoto, Finland, as a function of grain size and of Cs and Sr concentration. Furthermore, the specific surface areas of the same rock samples with different grain sizes were determined. It was shown that Cs distribution coefficients correlate with specific surface areas of the studied rocks and biotite, the correlation coefficient being 0.95. The Cs distribution coefficient was highest for biotite at about 0.1 m3/kg at 10−4 M cesium concentration and increased systematically to about 1 m3/kg at 10−8 M. Distribution coefficients for rocks were up to about two orders of magnitude lower, being lowest with the rock with the lowest biotite content (3.3%). The distribution coefficient of Sr varied from 0.04 m3/kg to 0.007 m3/kg and behaved in a different manner: it remained constant in two out of three studied rocks in the concentration range of 10−8-10−4 M and only in the case of one rock a decreasing trend was seen at the higher concentration range. It was also shown that batch sorption experiments overestimate the distribution coefficient in respect to intact rock. The decrease of the distribution coefficient as a function of grain size can be estimated using a power law function. It was also shown that estimation of distribution coefficients of Cs and Sr for intact rock by extrapolation of distribution coefficients determined for different grain sizes is not possible without increasing grain size, but in that case diffusion into the grains would also affect the results. A new method was developed for estimating the fraction of the inner surface area of the total surface area of crushed grains. For the mean grain sizes of 0.25 mm and 0.75 mm the fraction of the inner surface was found to be 35–70% and 60–90%, respectively. The inner specific surface area was highest with biotite at 1.2 m2/g and lowest with the rock with lowest biotite content (3.3%) at 0.07 m2/g. The surface area analysis revealed that crushing creates and/or allows access to additional inner surface area that is not measured in intact rock. Furthermore, it was demonstrated that sorption of Cs on crushed rock was dominated by mica minerals in multiple concentrations while the effect of mica minerals on the Kd of Sr was not as straightforward.

KW - Electrochemistry

KW - Crystalline rock

KW - Cesium

KW - Strontium

KW - Specific surface area

KW - Sorption

KW - Distribution coefficient

KW - Radionuclide

KW - 116 Chemical sciences

U2 - 10.1016/j.heliyon.2019.e02296

DO - 10.1016/j.heliyon.2019.e02296

M3 - Article

VL - 5

SP - e02296

JO - Heliyon

JF - Heliyon

SN - 2405-8440

IS - 8

ER -