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Metal distribution and mobility under alkaline conditions
Örebro University, Department of Natural Sciences.
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The adsorption of an element, expressed as its distribution between liquid (aquatic) and solid phases in the biogeosphere, largely determines its mobility and transport properties. This is of fundamental importance in the assessment of the performance of e.g. geologic repositories for hazardous elements like radionuclides. Geologic repositories for low and intermediate level nuclear waste will most likely be based on concrete constructions in a suitable bedrock, leading to a local chemical environment with pH well above 12. At this pH metal adsorption is very high, and thus the mobility is hindered. Organic complexing agents, such as natural humic matter from the ground and in the groundwater, as well as components in the waste (cleaning agents, degradation products from ion exchange resins and cellulose, cement additives etc.) would affect the sorption properties of the various elements in the waste. Trace element migration from a cementitious repository through the pH- and salinity gradient created around the repository would be affected by the presence and creation of particulate matter (colloids) that may serve as carriers that enhance the mobility.

The objective of this thesis was to describe and quantify the sorption of some selected elements representative of spent nuclear fuel (Eu, Am) and other heavy metals (Zn, Cd, Hg) in a clay/cement environment (pH 10-13) and in the pH-gradient outside this environment. The potential of organic complexing agents and colloids to enhance metal migration was also investigated. It was shown that many organic ligands are able to reduce trace metal sorption under these conditions. It was not possible to calculate the effect of well-defined organic ligands on the metal sorption in a cement environment by using stability constants from the literature. A simple method for comparing the effect of different complexing agents on metal sorption is, however, suggested.

The stability in terms of the particle size of suspended colloidal matter (clays and an iron hydroxide) was measured by photon correlation spectroscopy. In the absence of large amounts of organic material, the present colloids will, in most cases, not enhance metal migration in a cementitious environment due to agglomeration of the colloidal phase at high pH and salinities.

Place, publisher, year, edition, pages
Örebro: Örebro universitetsbibliotek , 2004. , p. 60
Series
Örebro Studies in Chemistry, ISSN 1651-4270 ; 4
Keywords [en]
Kemi, Adsorption, Colloids, Nuclear waste, Cement, Montmorillonite, miljökemi
National Category
Chemical Sciences
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:oru:diva-66ISBN: 91-7668-388-5 (print)OAI: oai:DiVA.org:oru-66DiVA, id: diva2:137083
Public defence
2004-05-19, Filmsalen, Forumhuset, Örebro universitet, Örebro, 10:00
Opponent
Supervisors
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-10-18Bibliographically approved
List of papers
1. Sorption of europium onto titanium dioxide at high pH: influence of isosaccharinic and fulvic acid
Open this publication in new window or tab >>Sorption of europium onto titanium dioxide at high pH: influence of isosaccharinic and fulvic acid
(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3125 (URN)
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-10-18Bibliographically approved
2. Effects of cement additives on radionuclide mobility
Open this publication in new window or tab >>Effects of cement additives on radionuclide mobility
2004 (English)In: Scientific basis for radioactive waste management XXVII: symposium held June 15-19, 2003, Kalmar, Sweden / [ed] Virginia M. Oversby, Lars O. Werme, Warrendale, Pa: Materials Research Society , 2004, p. 639-644Conference paper, Published paper (Other academic)
Place, publisher, year, edition, pages
Warrendale, Pa: Materials Research Society, 2004
Series
Materials Research Society symposium proceedings ; 807
National Category
Environmental Sciences Natural Sciences Chemical Sciences
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:oru:diva-3126 (URN)1558997520 (ISBN)
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-10-18Bibliographically approved
3. Effects of technical adsorbents and cleaning agents in a cement matrix: a case study
Open this publication in new window or tab >>Effects of technical adsorbents and cleaning agents in a cement matrix: a case study
2004 (English)In: Scientific basis for nuclear waste management XXVII: symposium held June 15-19, 2003, Kalmar, Sweden / [ed] Virginia M. Oversby, Lars O. Werme, Warrendale, Pa: Materials Research Society , 2004, p. 371-376Conference paper, Published paper (Other academic)
Place, publisher, year, edition, pages
Warrendale, Pa: Materials Research Society, 2004
Series
Materials Research Society symposium proceedings ; 807
National Category
Natural Sciences Chemical Sciences Environmental Sciences
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:oru:diva-3127 (URN)1558997520 (ISBN)
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-10-18Bibliographically approved
4. Sorption of europium on TiO2 and cement at high pH in the presence of organic ligands
Open this publication in new window or tab >>Sorption of europium on TiO2 and cement at high pH in the presence of organic ligands
2006 (English)In: Journal of Radioanalytical and Nuclear Chemistry, ISSN 0236-5731, E-ISSN 1588-2780, Vol. 270, no 3, p. 495-505Article in journal (Refereed) Published
Abstract [en]

Organic substances present in radioactive waste lower the sorption of metal ions at the high pH in cement matrices and, hence, enhance their possible migration. The aim of this study was to develop a method to compare organic substances or their degradation products with respect to what extent they affect metal sorption. Batch sorption studies were performed with cement or TiO2 as solid phase and Eu(III) as a model element for trivalent lanthanides and actinides at pH 12.5 (representative of a cement waste matrix during the first approximately 100,000 years). Different kinds of ligands were studied in a broad concentration range, e.g., organic acids, cement additives, cleaning agents and degradation products from ion-exchange resin.

National Category
Natural Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3128 (URN)10.1007/s10967-006-0455-4 (DOI)
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-12-14Bibliographically approved
5. Impact of some hydrochemical parameters on the size distribution of illite, kaolin and montmorillonite
Open this publication in new window or tab >>Impact of some hydrochemical parameters on the size distribution of illite, kaolin and montmorillonite
(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3129 (URN)
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-10-18Bibliographically approved
6. Sorption of europium to colloidal montmorillonite: impact of pH, an aquatic fulvic acid and calcium isosaccharinate
Open this publication in new window or tab >>Sorption of europium to colloidal montmorillonite: impact of pH, an aquatic fulvic acid and calcium isosaccharinate
(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3130 (URN)
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-10-18Bibliographically approved
7. Sorption of Cd to colloidal ferric hydroxides: impact of pH and organic acids
Open this publication in new window or tab >>Sorption of Cd to colloidal ferric hydroxides: impact of pH and organic acids
1997 (English)In: Chemical speciation and bioavailability, ISSN 0954-2299, E-ISSN 2047-6523, Vol. 9, no 1, p. 3-14Article in journal (Refereed) Published
Abstract [en]

The sorption (both ad- and desorption) of Cd to or from colloidal ferric hydroxides as a function of pH, the concentration of organic acids (acetic acid (AA), EDTA, fulvic acid (FA) and malonic acid (MA)), the precipitation procedure for the ferric hydroxide as well as the contact time were investigated in the present study. The concentrations of Cd, colloids and organic acids were chosen to be representative of natural surface waters. The ferric hydroxide were either precipitated in presence of FA or the acid was mixed with the colloids after the purification steps. The presence of FA during the precipitation of ferric hydroxide, had an impact on the size distribution of the solid phase, but it did not have any influence on the sorption behaviour of Cd. The adsorption process was found to be relatively fast and largely pH-dependent. It was fully reversible when the pH was decreased, however, with somewhat slower kinetics. The addition of up to 1 mmol L-1 AA or MA did not cause any measurable desorption of Cd, probably due to the relatively weak complexes formed between Cd(II)-ions and the anions of the acids. Thermodynamic calculations of the distribution between different soluble Cd-species indicated that EDTA and FA would form stronger complexes with Cd. This was indicated in the experiments as enhanced adsorption at low pH-values due to the adsorption of Cd(II)-organic species, and an increase in the soluble fraction at high pH-values caused by competition for Cd(II)-ions between complex forming groups on the surfaces and the soluble organic ligands.

National Category
Natural Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3131 (URN)
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-12-14Bibliographically approved
8. Effects of a fulvic acid on the adsorption of mercury and cadmium on goethite
Open this publication in new window or tab >>Effects of a fulvic acid on the adsorption of mercury and cadmium on goethite
2003 (English)In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 304, no 1-3, p. 257-268Article in journal (Refereed) Published
Abstract [en]

The effects of an aquatic fulvic acid on the pH-dependent adsorption of Hg(II) and Cd(II) to particulate goethite (alpha-FeOOH) were studied in batch systems. The ionic medium consisted of 0.01 M HClO(4) and the total concentrations of mercury and cadmium were maintained at 10(-8) M with 203Hg and 109Cd as tracers. pH In the systems was varied in the range 3-10 by addition of HClO(4) and NaOH. All commercial chemicals were of analytical grade or better. An aquatic fulvic acid (20 ppm), previously isolated and characterised in detail, was used as a model for humic substances and its adsorption to goethite is included in this study. The adsorption of the fulvic acid (20 ppm) onto goethite decreased slowly from 90% at pH 3-7.5 to 10% at pH 10. In systems without fulvic acid the adsorption of mercury increased in a linear fashion from 10% at pH 3 to 70% at pH 10. In the presence of fulvic acid (20 ppm), the adsorption was almost quantitative in the intermediate pH range (pH 5-7), and exceeded 92% over the entire pH range. Thus, association between mercury and the fulvic acid enhanced adsorption in general although the largest impact was found at low pH. Adsorption of cadmium increased from nearly 0 to almost 100% at approximately pH 6. In the presence of fulvic acid, the adsorption increased below pH 7 and decreased above pH 7. The adsorption isotherm for mercury when the concentration was increased from 10(-8) to 1.8 x 10(-4) M showed a corresponding increase of K(d) (l/g) up to a total concentration at 10(-6) M. At higher mercury concentrations K(d) was lowered. In the presence of fulvic acid the corresponding relationship of K(d) was bi-modal, i.e. high values at low and intermediate concentrations of mercury. This behaviour suggests that in the absence of fulvic acid the adsorption follow the expected behaviour, i.e. adsorption sites with similar affinity for mercury. In the presence of fulvic acid, additional adsorption sites are available by the organic molecule (possibly sulfur groups) when it is associated to the goethite. The adsorption isotherm for cadmium indicates a lowering of K(d) at 10(-4) M. Cadmium had no competitive effect on mercury and vice versa. Zinc, however, affected the adsorption of cadmium but not the adsorption of mercury.

National Category
Natural Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3132 (URN)10.1016/S0048-9697(02)00573-9 (DOI)
Available from: 2004-04-28 Created: 2004-04-28 Last updated: 2017-12-14Bibliographically approved

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