1

The effect of complexing agents on the sorption and

subsequent migration of thorium in a natural sand
matrix using static batch and flow-through column
experiments.

…………………………………………………………………...

Lindsay Young

25th March 2010

Supervisor: Dr Miranda Keith-Roach

BSc (Hons) Analytical chemistry

 2

The Effect of complexing agents on the sorption and

subsequent migration of Thorium in a natural sand
matrix using static batch and flow-through column
experiments

Disclaimer:
The research presented in this thesis is original and has been carried out by
the undersigned except where otherwise stated.

…………………………………………………………………………………………
Miss Lindsay Young 25/03/2010

Word count: 10067

Lindsay Young EOE3602.

 3

List of contents

Abstract…………………………………………………………………………….. 1
1 Introduction ………………………………………………………………...3
1.1. Sellafield and nuclear wastes………………………………..3
1.2. Drigg low level waste repository……………………………4
1.3. Organic complexing agents and their role in mobilising
radionuclides……………………………………………………5
1.4. Sorption………………………………………………………….7
1.5. Methods used to determine radionuclide transport……..8
1.6. Colloidal species……………………………………………..10
1.7. Investigation focus…………………………………………..13
2. Materials and methods……………………………………………………..15
2.1. Reagents……………………………………………………….15
2.1.1. Groundwater preparation……………………….15
2.1.2. Preparation of analytes and mixtures………...16
2.2. Laboratory batch experiments……………………………..17
2.3. 2.3 Column experiments………………...……………..…...20
2.4. Analysis by ICP-MS……………………….....………………23
3. Experimental results and discussion…………………………….……..24
3.1. Batch sorption experiment results………………………..24
3.2. Column characteristics……………………………………...26
3.2.1. Bromide tracer…………………………………….26
3.2.2. Mass balance of recovered Th………………....29
3.3. Th elution profiles…………………………………………....30
3.3.1. 1:10 Th:EDTA high flow (1 day duration)…….30
3.3.2. Th only column (7 day duration)…....…………31
3.3.3. 1:10 Th:EDTA low flow (14 day duration)…….32
3.3.4. 1:10 Th:EDTA high flow (7 day duration)…….34
3.4. Solid phase digestion………………………………………..37
4. Conclusions………………………………………………………………….38
5. Applications to the environment…………………………………………40
6. Further work………………………………………………………………….41
7. References………………………………………………………………..…..41

Lindsay Young EOE3602.

 4

8. Acknowledgements…………………………………………………………44
9. Appendix……………………………………………………………………...45

Lindsay Young EOE3602.

 1

Abstract

The most likely process that can lead to the mobility of radionuclide's from a waste

repository is transport by flowing groundwater through a geological matrix. Waste

repositories often contain organic complexing agents such as EDTA and NTA that

are used in decontamination processes. The presence of complexing agents has

been found to enhance radionuclide's mobility within the geological matrix, the extent

to which is site specific due to differing soil matrices and groundwater composition.

Th-EDTA chemical species mobility’s were investigated and comparisons were made

with the transport of Th-colloids.

Static batch experiments were conducted with a sand matrix obtained from Drigg low

level waste repository in Cumbria and Th(IV) as a representative tetravalent actinide.

The Th was pre-equilibrated either alone or with equimolar or 10 fold excess of

complexing agent (EDTA & NTA) in a synthetic groundwater solution that was similar

in composition to that found at Drigg. The degree of sorption of the Th was

calculated using the ratio of the concentration adsorbed to the solid phase to the

concentration in solution phase (termed the Kd value). The Kd values obtained for

each analyte mixture suggest that equimolar concentrations of complexing agents

and Th showed a higher degree of sorption to the sand matrix when compared to a

ten-fold excess.

Flow-through column experiments were carried out using the same sand matrix to

obtain a more dynamic and representative observation of Th migration. Th in the

absence of complexing agent, and Th with a ten-fold excess of complexing agent

were pumped through a column packed with sand at two different flow rates. The

eluent was collected at timed intervals and was analysed by ICP-MS to obtain the

concentration of Th. Eluent profiles were then generated using the concentration and
volume eluted. A bromide tracer was used to gather column characteristics such as

pore volume and porosity.

The results of the column experiments show that Th in the absence of complexing

agents was highly sorbed to the sand with only 3% eluting over the experimental

period. It is assumed that slow desorption kinetics of the Th were responsible for the

low concentrations in the eluent. Th with a ten fold excess of EDTA enhanced

migration through the column with respect to the Th only. This was characterised by

a high concentration peak and 26% of the Th eluted over the experiment period.

Th with a ten fold excess of EDTA at a low flow velocity showed that the Th-EDTA

complex may have dissociated due to cation competition from solid phase surface

bound metals competing for the EDTA. The profile obtained for the low flow system

was similar to that obtained for the Th only system with only 2% Th eluting and may

be attributed to longer contact the ThEDTA complex had with the sand, thus more

time for dissociation. The concentration eluting in the low flow system was an order

of magnitude lower than was seen for the higher flow rate column. Comparisons with

EDTA mediated colloid transportation found that the formation of colloids enhanced

Th mobility.

Lindsay Young EOE3602.

1 Introduction

One of the major concerns in the operation of low-level radioactive waste repositories

is the possible migration of radionuclide's from the confines of the repository into the

near and far field environment by groundwater flow. Migration of radionuclides could

result in contamination of water supplies and may enter the food chain by uptake of

crops. Due to the differing terrestrial matrices and groundwater composition at

various waste repositories, there is no definitive answer or solution to the fate of the

radionuclides. Site-specific experiments must be carried out using representative

soil/sand matrices and groundwater composition to determine the destiny of

migrating radionuclides. This study shall look at Drigg low-level waste repository

located in Cumbria, UK.

1:1 Sellafield and nuclear wastes

The Sellafield nuclear plant in Cumbria is a large, complex nuclear chemical facility

that has supported the nuclear programme since the 1940s [ CITATION Nuc09 \l

2057 ]. The power station itself is currently undergoing decommissioning but the site

is still used for the processing of fuels removed from other nuclear power stations

and the storage of nuclear materials and radioactive wastes[ CITATION Nuc09 \l

2057 ].

Nuclear solid wastes are divided into 4 categories according to the radioactivity

content:

Lindsay Young EOE3602.

  High-level waste (heat generating) (HLW) in which the temperature may rise

due to its radioactivity.

 Intermediate Level Waste (ILW) – Lower levels of radioactivity. Heat is not a

factor when storage is considered.

 Low Level Waste (LLW). Contains some radioactive material so it is not

acceptable for disposal as ordinary refuse. Consists of contaminated

equipment, contaminated materials such as concrete and protective clothing

that has been worn within a nuclear facility. LLW is disposed of by being

compacted into large stainless steel drums that are then put into a large metal

container then encased in concrete.[ CITATION NIR03 \l 2057 ]

 Very Low Level Wastes (VLLW). Has very low radioactivity and can be

disposed of with normal refuge.[ CITATION NIR03 \l 2057 ]

Sellafield has been operational since the 1940s, and the standards for waste

management were very different then to what they are today.[ CITATION HMS03 \l

2057 ] In particular the LLW repository 6km south of Sellafield near the village of

Drigg has operated as a national LLW facility since 1959.[ CITATION HMS86 \l

2057 ].

1:2 Drigg LLW repository

LLW such as towels, paper, contaminated clothing, and items used in the

decontamination process such as spent ion exchange resins are what is typically

included in the wastes taken to Drigg.[ CITATION HMS86 \l 2057 ] Since 1959 until

the late 1980’s all wastes including uranium, radium and thorium wastes processed

at Drigg were tipped loosely into trenches approximately 8 meters deep, 25 meters

Lindsay Young EOE3602.

wide and up to 700 meters long with conditions that the waste was buried beneath at

least 1 meter of soil. This was then covered by a layer of limestone hardcore and a

fine layer of stone [ CITATION HMS86 \l 2057 ]. In later years, the trenches were

capped with an impermeable membrane reducing the amount of lechate discharged

from the trenches [ CITATION HMS86 \l 2057 ]. The lechates from the trenches in

the early days of the repository were un-segregated and corrosion was a problem.

This was remedied by emplacement of containerised concrete vaults of conditioned

waste that are stacked on the ground, - these are still in use today.

Although the trenches are ‘capped’ and there is double containment in places, low

levels of leakage have been reported [ CITATION HMS86 \l 2057 ] and the release of

radionuclides into the environment by the flow of groundwater is a major concern. In

1999, Bousher [ CITATION Bou99 \l 2057 ] reported that the trenches at Drigg

contain approximately 5.5x105 m3 of waste and that 5500m3 per year of water flows

through the site. The principal contaminants were found to be caesium, uranium,

americium and plutonium and these radionuclides have been found in the water and

sediment of a nearby stream and drainage system.

1:3 Organic complexing agents and their role in mobilising radionuclides.

Many studies have been carried out to determine the mobility of radionuclides

through terrestrial matrices’ and in particular, the effects that organic complexing

agents have on their migration.

Organic chelating agents, such as ethylenetriaminepentaacetic acid (EDTA), picolinic

acid and nitrilotriacetic acid (NTA) are used in the decontamination process to

remove build up of radioactive metals from the cooling systems of nuclear power

stations[ CITATION Ser96 \l 2057 ]. The complexing agents complex the

radionuclides, which are then removed onto ion exchange resins along with any

Lindsay Young EOE3602.

excess uncomplexed chelates. Spent ion resins are then classed as LLW and are

disposed of in LLW facilities such as the one at Drigg.

The role of organic complexing agents in enhancing radionuclide migration is

unquestionable. A field study by Means et al [ CITATION means \t \l 2057 ] at the

Oak ridge National Laboratory in the USA, a site for LLW disposal showed that
60 60
migration of Co was enhanced by the presence of EDTA and Co had been

observed beyond 50 meters from the waste trenches. Means also suggested that

the migration of other radionuclides such as Pu, Am and Th may also be attributed to

EDTA and other complexing agents. Radionuclide migration has also been

observed at other LLW disposal sites such as the Chalk River Laboratories in

Canada [ CITATION Rob95 \l 2057 ]. The author studied 2 sites, one being a

chemical pit, which received aqueous wastes containing various radionuclides and

chemicals, the other being a 30 year old solid low level waste storage facility’

consisting of a series of trenches containing radioactive materials. The study

concluded that radionuclide mobility is enhanced by the formation of anionic

complexes. The anionic complex species were stable and were not significantly

altered by redox conditions giving them the potential for significant far-field migration.

Complexing agents and their complexes with metals have been shown to leach from

the cement confines that hold the waste and can increase radionuclide leach rate by

factors of 10 to 100 [ CITATION Ser96 \l 2057 ]. A technical bulletin released in 1991

by the National Low Level Waste Management programme in the USA [ CITATION

Mcc91 \l 2057 ] stated that decontamination ion exchange resins containing chelating

agents were difficult to solidify in the cement used (Portland cement) and there have

been instances where the cement has failed to harden satisfactorily. This will

Lindsay Young EOE3602.

increase leaching of radionuclides and the complexing agents, which can then be

carried off by groundwater flow.

But how do complexing agents enhance the mobility of radionuclides through

terrestrial matrices?

1:4 Sorption

Sorption of complexing agents and complexes to the terrestrial matrix is a key factor

when considering the mobility of radionuclides. Sorption is the processes of

absorption and adsorption happening simultaneously[ CITATION Oxf04 \l 2057 ] and

can be described as a liquid or gas being incorporated into another material of a

different state and adhering to the surface of another molecule. The sorbent is

described as the matrix, or solid phase and the sorbate can be described as the

molecule or complex (mobile phase). The sorbent, for example, sand has ionisable

surface groups such a trace metals and OH - groups, these are termed ‘binding sites’.

The charged complexes or ligands can then covalently bond to these binding sites

affecting their mobility. The adsorption capacity for organic pollutants depends upon

3 main issues:

i) The sorbate features such as molecular size, solubility in aqueous

solutions, polarity and the functional groups that the molecule may have.

ii) The liquid matrix (ground water) characteristics such as pH and ionic

strength and ionic components.

iii) The sorbent features such as surface area.[ CITATION Ruf09 \l 2057 ]

Lindsay Young EOE3602.

1:5 Methods used to determine radionuclide transport

A study carried out by Serne et al in 2002 [ CITATION Ser \l 2057 ] used various

methods to determine the effects of complexing agents on radionuclide mobility. One

method used was a column adsorption experiment. A column adsorption experiment

uses a column packed with a representative sample of the soil/sand from around the

LLW repository in question. The soil must be free from radionuclides and complexing

agents. A simulated groundwater matrix is then pumped upwards through the column

at the required flow rate and the effluent is then collected over a set timescale and

analysed using an appropriate technique. This method has been used to determine

the velocity of a contaminant radionuclide relative to the groundwater velocity since

1979 [ CITATION JFR82 \l 2057 ] and is used for the direct measurements of

retardation factors that predict the mobility in groundwater’s and soils[ CITATION

JFR82 \l 2057 ]. The retardation factor (Rf) is a measure of the capability of a

terrestrial matrix to act as a barrier to radionuclide migration i.e. its adsorption

capacity and is calculated from the partition/distribution coefficient (K d value). The Kd

value is defined as the ratio ‘of the quantity of adsorbate adsorbed per mass of solid

to the amount of the adsorbate remaining in solution at equilibrium’[ CITATION Uni99

\l 2057 ] and is a measure of how readily one species sorbs to another surface. A

high Kd value indicates that a chemical is less likely to leach and it is strongly

adsorbed to the soil and therefore does not move through the soil matrix. The study

by Serne et al found that the K d values they obtained for radionuclides, organic

ligands and their complexes were highly variable and a strong function of pH, ligand

concentration and radionuclide concentration[ CITATION Ser \l 2057 ]. They found

that at high pH conditions, which are created by cementious wastes, mobilisation of

Ni2+ by EDTA was very significant and that adsorption of Ni 2+ by soils was zero.

Lindsay Young EOE3602.

Read et al[ CITATION Rea98 \l 2057 ] concluded in a similar study that ‘EDTA

actively promotes the migration of Uranium’ in clashach sandstone, and that the

order in which the complexing agents and radionuclides are introduced to each other

also has an effect on the mobility, for instance, when uranium was introduced to the

soil column ahead of the organic plume (EDTA) the remobilisation of radionuclides

that have sorbed to the soil is slow because of slow desorption kinetics. Read and his

co-workers also found that aqueous uranium species have a high affinity for natural

mineral surfaces and this affinity is significantly reduced when uranium and EDTA

are pre-equilibrated together, which is certainly the case in a LLW repository such as

the one at Drigg. Serne and his collegues [ CITATION Ser \l 2057 ] also investigated

the effects of the concentrations of both the radionuclide and the complexing agent.

They found that excess complexing agent in the aqueous phase had a large effect on

the solubility of the radionuclides. The complexing agents saturated the anion binding

sites of the soil matrix and prevented sorption of the radionuclide complexes

therefore allowing the radionuclide complexes to be carried by the flow of

groundwater. Equimolar solutions containing both EDTA and Ni 2+ at pH 7.5 showed

that Ni-EDTA complexes are initially, rapidly absorbed to the soil binding sites (iron

oxides). Once absorbed the Ni-EDTA complexes dissociate freeing the Ni 2+ ions and

Fe(III)-EDTA complexes form. Some Ni 2+ ions are then re-adsorbed to the binding

sites and saturation of the soil binding sites is quickly reached. Ni 2+ ions are no longer

absorbed but rather de-sorbed and the concentration of Ni 2+ relative to EDTA in the

effluent increased. The study by Serne et al [ CITATION Ser \l 2057 ] shows that the

major cations present in groundwater and soils such as Al, Mg, Fe, Ca and oxides

have a significant effect on the mobility of radionuclides in that they can displace the

radionuclide from the organic complex. The findings from another study carried out

Lindsay Young EOE3602.

by Hakem[ CITATION Hak01 \t \l 2057 ] showed that Pu(IV) highly sorbed to

Hanford soil, however in the presence of EDTA and for a ratio of EDTA/Pu(IV) >200,

the sorption decreased due to the ‘formation of the soluble and neutral complex

Pu(IV)-EDTA. The author also concluded that that EDTA must be present in

significant excess in order to alter Pu migration.

Another method to determine Kd values is the laboratory batch method. This method

is very straightforward and involves taking a known mass of sediment/sand and

adding to a beaker, then adding a known volume and concentration of the aqueous

analyte mixture. The beaker is sealed and agitated until sorption is assumed to be

complete (approx 1-7days)[ CITATION Uni99 \l 2057 ]. The samples are then filtered

or centrifuged and the remaining contaminant concentration is measured. The Kd

value is calculated using a simple equation shown in equation 1.

Vw (C0 – C1)
Equation 1: Kd (ml/g) = Msed C1
[ CITATION Uni99 \l
2057 ]

Where, Vw = Known volume added (ml)

C0 = Known concentration of contaminant (μg/ml)
C1 = Concentration of contaminant in supernatant (μg/ml)
Msed = Mass of sediment (g)

Many previous studies have employed this method along with column experiments to

determine the Kd of a contaminant. [ CITATION May09 \l 2057 ], [ CITATION Lis08 \l

2057 ][ CITATION Ser \l 2057 ],[ CITATION Rea98 \l 2057 ],[ CITATION JFR82 \l

2057 ]

1.6 Colloidal species

Lindsay Young EOE3602.

Tetravalent actinides such as Th4+ tend to form polymeric colloidal

hydroxides[ CITATION Doz93 \l 2057 ]. Colloids are molecules or polymolecular

particles that have ‘at least in one direction, a dimension between 1nm and 1um’

[ CITATION IUP02 \l 2057 ] which are dispersed within a continuous medium (i.e.

groundwater) in a manner that prevents them from being filtered easily or settled

rapidly. A number of investigations have documented that mobile contaminants

associate with solid colloidal particles in the flowing fluid phase and have provided

evidence that suspended colloids act as contaminant carriers. Colloids can be

described as ‘mobile solid phase’ [ CITATION FHF07 \l 2057 ]

A schematic representation of colloidal facilitated transport is shown in Fig 1.

Fig 1: The contaminants are either dissolved in the mobile phase or adsorbed to the solid phase (sand

matrix). Colloids can form and be released from the solid phase becoming mobile and then act as

carriers for contaminants. [ CITATION FHF07 \l 2057 ]

A report conducted by Fjeld[ CITATION Fje00 \l 2057 ] found that 99% of thorium in

the absence of EDTA had low mobility in the column adsorption experiment and

probably formed the highly insoluble Th(OH) 4 species, the results also suggested that

colloidal species were present enhancing the mobility of Th as an un-dissolved

suspended species in groundwater. A study conducted by Allard[ CITATION All83 \l

2057 ] suggested that the species could be composed of ‘highly polymerised hydroxy

complexes with large residual charges which prevent them from aggregation

Lindsay Young EOE3602.

because of electrostatic repulsion’. - and because of this, the solubility may ‘exceed

the expected equilibrium solubility by many orders of magnitude’[ CITATION All83 \l

2057 ] . Allard also suggested that stable polymeric species could exist at low pH and

high actinide concentrations and these species would carry a positive net charge.

The studies mentioned here show that the adsorption of radionuclides and their

complexes are very difficult to predict due to numerous factors that are site specific.

Factors such as pH, concentration of complexing agents, and concentration of

competing ions in the groundwater and soil and oxidation state of the actinide all

affect adsorption and hence, the mobility of radionuclides. Soils and sands are very

different in composition from one LLW repository to another. Adsorbing surfaces

include iron and aluminium oxides, minerals such as kaolinate and surface bound

organic substances that each has a variety of different binding sites [ CITATION

Ser96 \l 2057 ]. The surface properties of the soil/sand are affected by physico-

chemical conditions mentioned above, such as pH and ionic strength of the

groundwater and these conditions can facilitate numerous reactions with the soil

binding sites and the complexes such as oxidation/reduction reactions.

The results of previous studies all suggest that complexing agents such as EDTA can

increase the mobility of radionuclides by forming stable complexes with the

radionuclides. All of the above experiments are site specific and cannot be applied to

another LLW repository due to the differing soil/sand matrices that affect adsorption.

A pHD thesis written by May [ CITATION May09 \l 2057 ] explored the mobility of

thorium and complexing agents using column and batch experiments. May found that

Lindsay Young EOE3602.

Th in the absence of complexing agent, had a high affinity for sand surface binding

sites and was highly sorbed to the sand, thus reducing mobility. Th in a 1:10 ratio

with EDTA (4 and 40 millimolar respectively) migration was enhanced by the

interaction of EDTA with Th colloidial species. He concluded that colloidal species

were formed because the concentration of Th was greater than its solubility. He also

concluded that ligand concentration played an important role, with both NTA and

EDTA enhancing the mobility of Th. Experiments were carried out with two different

flow rates (consistant with high and low end groundwater velocities for sand

aquifiers) through the column to look at the effect that flow rate had upon the

migration, but due to colloidal species forming the elution profiles were not effected

and were therefore carried as a function of groundwater flow.

1.7 Investigation focus.

Given the above discussion and Mays colloidal issues in the experiments conducted,

this investigation will focus on the effect of NTA and EDTA on Th(IV) mobility through

a natural sand matrix, representative of sand from Drigg. The concentrations of the

complexing agents will be varied in a 1:1 and 1:10 ratio Th-complexing agent as in

the previous study by May but will try to avoid colloid facilitated transport by using

concentrations an order of magnitude lower. This will allow the behaviour of the

chemical species to be investigated. The experiment will use a pulse input with the

column method with a simulated groundwater similar in composition to that found at

Drigg.

Batch sorption experiments will be carried out to determine Kd values for each

analyte mixture and these will be used to determine the approximate residence time

Lindsay Young EOE3602.

within the column, and thus the run time for each column experiment. Column

characteristics will be determined using a bromide tracer.

The overall aims of this study are to:

i) Determine the effect of Th complexation by EDTA and NTA (as a chemical

species) on the migration of Th through a sand matrix relevant to a low-

level waste repository avoiding colloidal facilitated transport of the

radionuclide's. ii)

ii) To explore the effects differing flow velocities have upon Th sorption, and

subsequently the migration of Th.

iii) To compare data obtained from Mays experiments [ CITATION

Placeholder1 \l 2057 ] for colloidal facilitated transport , with Th-EDTA

species transport

iv) To determine the fate of tetravalent radionuclides at Drigg low level waste

repository.

Lindsay Young EOE3602.

2 Material and methods.

2.1 Reagents

2.1.1 Groundwater preparation

A synthetic groundwater similar in composition to that found at the Drigg repository

was made using a recipe obtained from Dr Colin May, pers.Comm, October 2009.

Ionic concentrations are shown in Table 1.

Ion millimolar concentration (mM)

Ca 2+ 0.7
Mg2+ 0.2
Na+ 0.7
K+ 0.1
Cl+ 0.8
SO42- 0.2
NO3- 0.6
HCO3- 0.8
Table 1. Ionic concentrations for simulated groundwater.

The ground water was made up in 5L volumetric flasks using Analar grade salts and

Milli-Q water. All salts were weighed using a calibrated four figure analytical balance

(Salter ER183A) Masses required and masses used are shown in table 2.

Salt Company Mass required for Mass used (g)

ionic concentration
(g)
KHCO3 Sigma Aldrich 0.0500 0.0504
Mg(NO3)2•6H2O BDH-GPR 0.2564 0.2558
NaHCO3 Fisher Scientific 0.2940 0.2980
CaCl2•2H2O Fisher Scientific 0.5881 0.5884
CaSO4•2H2O Sigma Aldrich 0.1722 0.1732
Ca(NO3)2•4H2O Sigma Aldrich 0.1741 0.1886

Table 2. Salts and masses used in preparation of synthetic groundwater.

2.1.2 Preparation of analytes and mixtures.

Lindsay Young EOE3602.

The analyte mixtures required are shown in Table 3.

Analyte mixture Th concentration (mM) Complexing agent

concentration (mM)
1:1 Th:EDTA 0.4 0.4

1:10 Th:EDTA 0.4 4

1:1 Th:NTA 0.4 0.4

1:10 Th:NTA 0.4 4

Table 3. Analyte mixture used in experiments with corresponding concentrations.

The complexing agents were first prepared as 40 mM in 50 ml volumetric flasks using

the synthetic groundwater, and diluted down to the required concentrations. Table 4

shows the required masses of the salts and the actual masses used.

Salt Company Mass required (g) Mass used (g)

EDTA Fisher Scientific 0.7445 0.7451
NTA (trisodium Sigma Aldrich 0.5502 0.5587
monohydrate salt)
Table 4. Complexing agents used to prepare 40mM solutions

Thorium nitrate hydrate (39-45% Th) was dispensed in a fume hood into a pre-

weighed container with a known amount of groundwater. The concentration was then

calculated. Using the 40mM complexing agent solutions and the thorium solution, the

required analyte mixtures shown in table 3 were made in volumetric flasks using the

groundwater.

The potassium bromide tracer (250mM) was also prepared using Analar grade BDH

KBr salts.

2.2 Laboratory batch experiments.

Lindsay Young EOE3602.

Batch sorption experiments were carried out as described in numerous studies, eg

[ CITATION Placeholder1 \l 2057 ][ CITATION Placeholder2 \l 2057 ][ CITATION

Placeholder3 \l 2057 ] to calculate a Kd value.

All batch experiments were carried out in triplicate and performed at room

temperature under normal atmospheric conditions. For each analyte mixture a set of

control solutions were prepared under the same conditions but without the sand. This

was to monitor any sorption to the wall of the container and to also check the initial

concentration of Th put in. Drigg sand was first sieved with a 2 mm sieve. The large

fines were discarded. 100 g of the <2 mm sand was then mechanically sieved using

an orbital shaker (165 rpm) and 63 μm sieve for 24 hrs. The <63 μm portion was the

pre-equilibrated with groundwater >24 hrs.

1 g ± 0.01 g of the pre-equilbrated sand was put into acid washed 50 ml centrifuge

tubes. 2 ml of each analyte mixture was added to the sand and was left on an orbital

shaker for 7 days.

The samples were then centrifuged using a Sorvall Legend RT centrifuge for

45minutes at 3010rpm to remove the very fine soil particles in the supernatent, as the

particles have a high specific area that could distort measurements due to strong Th

sorption [ CITATION Placeholder2 \l 2057 ]. 0.5 ml of the supernatent was taken

from the centrifuge tubes and was diluted with 2%HNO 3 for analysis by ICP-MS. The

ICP-MS calibration method is explained in section 2.4

Kd values using the experimental data were calculated using the following equation:

Vw (C0 – C1)
Kd (ml/g) = Msed C1
Lindsay Young EOE3602.
Equation 1: [ CITATION Uni99 \l 2057 ]

Where, Vw = Known volume added (ml)

C0 = Known concentration of contaminant (mol/ml)

C1 = Concentration of contaminant in supernatant (mol/ml)

Msed = Mass of sediment (g)

The calculated Kd values were then used to calculate the approximate residence

time of thorium within the column. See section 2.3 This was calculated using a

spreadsheet equation obtained by Dr Miranda-Keith Roach pers.Comm, Nov 2009

and required an approximate pore volume for the packed column. This was obtained

by packing a column full of sand as described in section 2.3 and injecting 50μl of

250mM bromide tracer. A conservative tracer does not interact with the geological

medium, degrade or change during the passage through the sand packed column. It

mimics the movement of water and by comparing the behavior of the tracer to that of

the contaminant it is possible to determine if the contaminant is adsorbed during the

passage through the column. A study conducted by Levy concluded that bromide

showed no sorption to terrestrial matrices under batch experiment conditions

[ CITATION Lev06 \l 2057 ]. The collection vials were all acid washed and pre-

weighed and the pump was set to 006. The fraction collector was set to collect every

10 minutes and was initially allowed to run for 6 hrs to ensure all bromide had eluted.

The vials were all reweighed and the volume calculated as described in section 2.3.

The samples were then diluted with 2% HNO3. This was then analysed using ICP-

Lindsay Young EOE3602.

MS and an elution profile was drawn using the total flow volume vs concentration of

bromide. The pore volume was taken from the elution profile (total volume of eluent

at just before the Br eluted). Using the pore volume and the calculated flow-rate the

residence time for water was calculated using equation 2.

Residence time = Pore volume (ml)

water (hr) Flow-rate (ml/hr)
Equation 2

The residence time for thorium was then calculated using the experimental Kd value

for the relevant batch sorption and the calculated residence time for water using

equation 3.

Residence time = (Kd (ml/g) +1) x residence time for water (hr)
for Th (hr)
Equation 3

The residence time for Th was then used to determine the collection timings for each

vial.

2.3 Column experiments.

Lindsay Young EOE3602.

Column experiments were carried out using a method obtained from May

[ CITATION Placeholder1 \l 2057 ]. Numerous studies have employed the flow-

through column method with a pulse input eg [ CITATION Mar02 \l 2057 ][ CITATION

Han09 \l 2057 ][ CITATION Han09 \l 2057 ] to study the transport of various species

through terrestrial matrices.

A self-pack® PEEK™ polyetheretherketone column (50mm x 10 mm, vol 3.93 cm 3)

with a 0.2 μm in-line filter frit was used in all column transport experiments. A

peristaltic pump and fraction collector was used (Lambda Omnicoll) to pump

synthetic groundwater through the column in an upward direction. Pumping upwards

was to ensure full column saturation. A 50 μl injection loop was used to measure the

volume of analyte mixture injected into the column and PVC tubing was used to carry

the groundwater and mixture. Flow-rates similar to those used in Mays experiment

[ CITATION Placeholder1 \l 2057 ] were used and can be found in Table 5.

In each column experiment, the tubing was flushed through with 10% HCl >24 hrs

then milli-Q water >24 hrs, to remove all traces of previous experiments ensuring that

no Th residue was left inside the tubing. The synthetic groundwater was then

pumped through the tubing. The column was packed with pre-equilibrated sand and

tapped down to ensure no air pockets were inside. This was then pressed down with

a plastic plunger to remove excess water and to ensure uniform packing between

each experiment. This was repeated until the column was full of sand (5.8 ± 0.2 g).

The packed column was sealed, then pre-conditioned with the ground water flowing

in an upward direction >24 hrs. In each experiment the inflow and outflow pH was

measured using Mettler Delta 340 pH instrument. In each case the inflow ground

water pH was 7.0 ± 0.2 and outflow pH was 7.3 ± 0.2.

Lindsay Young EOE3602.

The peristaltic pump was set to 006 to begin with and a short experiment using just

the groundwater was carried out to attain the flow-rate. Six acid-washed pre-weighed

vessels were put on the collection grid and the fraction collector was set to move

every 10 minutes. The density of the ground water was calculated and found to be

0.9950g ml-1 ± 3.9x10-3. Using the density and the mass of the groundwater in the

pre-weighed collection vials, the volume in each vial could be calculated. This was

repeated 3 times and each time a different volume of groundwater was found in each

vial with relative standard deviations between each set of data being 10-16%.

It was decided that every collection vial had to be pre-weighed in order to accurately

determine the volume of eluent and therefore determine the dilution factor with HNO 3

that each sample had before analysis with ICP-MS. This was repeated for each

experiment that was run. The experiments runs are shown in table 5

Experiment Sample Flow rate RSD % Collectio Experiment

column mixture ml/h associated n duration
number with flow frequency (days)
rate
1 1:10 0.81 10.9 10mins 1
Th:EDTA
2 1:10 0.88 5.6 2hrs 7
Th:EDTA
3 1:10 0.19 39.7 4hrs 14
Th:EDTA
4 Th on own 0.88 7.7 2hrs 7

Table 5: Column experiments ran with flow-rates and collection timings

For each column experiment, the residence time of Th was calculated using the

batch experimental Kd value and equations 1 and 2 and fraction collector timings

were based upon this to ensure best elution curve resolution.

Lindsay Young EOE3602.

The analyte mixture in each experiment was injected using the 50 ul injection loop

and left to run for the relevant experiment duration (table 5). The experiment duration

time was decided by the residence time of Th in the column (determined by batch

experiments (section 2.2) and also to see if any elution curve tailing occurred which

could indicate ‘slow kinetic desorption processes’ [ CITATION Placeholder1 \l 2057 ].

Immediately after injection 3 aliquots of the analyte mixture was taken for analysis to

determine total Th concentration.

At the end of the experiment duration time, the vials were reweighed and the volume

calculated. Each vial was then diluted with 3mls 2% HNO 3 for analysis by ICP-MS.

50 ul of 250 mM potassium bromide solution was then injected onto the column. This

was to determine column characteristics such as pore volume and is described in

section 2.2. The bromide tracer was left to run for 6 hours for experiments 1,2 & 4

(table 5) on the same flow-rate and the fraction collector was set to collect every 10

minutes to ensure good peak resolution. On experiment 3 (low flow rate) the fraction

collector was set to collect every 20 minutes on the same low flow-rate. This resulted

in a very small volume of eluent in each vial and over the course of the experiment

the eluent evaporated. It was decided that the column should be washed through

with ground water >24 hrs and the bromide tracer repeated but with a higher flow rate

in order to attain more eluent volume.

At the conclusion of the bromide tracer for each experiment, the column was

unscrewed and the sand pushed out as a single core using a plastic plunger. The

sand was then cut into 5 x 1 cm sections and put into pre-weighed digestion vials

(polyfluoroalkoxy vessels). The sand was freeze dried, re-weighed and then digested

using concentrated HNO3 at a temperature of ≥ 140 ºC for >8hrs. The supernatent

was pipetted out of the digestion vial using a glass pasture pipette and diluted with

Lindsay Young EOE3602.

2% HNO3 for analysis of Th by ICP-MS. 3 x 1 g of the sand was digested and

analysed for total thorium content. The mean sand blank value was then subtracted

from the column sand results.

2.4 Analysis by ICP-MS

All column outflow samples, Batch samples and analyte mixture aliquots were

analysed for Th 232 by ICP-MS. The operating conditions are shown below in Table

6.

Thermo Scientific X series 2 with concentric glass nebuliser

Nebuliser gas flow rate 1.02 L/min
Coolant 13 L/min
Auxilary 0.7 L/min
Forward power 1.4 Kw
Wash 2% HNO3
Uptake / wash timings 25 seconds
Table 6: Operating parameters for ThermoScientific X series ICP-MS

All samples were spiked with Bismuth internal standard, to help overcome the

transport effects of the sample during uptake and takes into account the slight

variation in volume. A 1 ppm Bi standard was made and each sample was spiked

with a volume so that the concentration of Bi in the sample was 1 ppb (x101 dilution

factor) for example, a sample had a total volume (inc HNO 3) of 3.1 mls, therefore 31

μl of 1ppm Bi was added. All calibration standards (in 25ml volumetric flasks) were

also spiked with the corresponding volume (250 μl). All Th samples analysed were

above the instrumental limit of detection (0.01nM)

All bromide tracer (Br 81) samples were analysed using the parameters in table 6 but

with an extended wash time of 45 seconds due to the Br affinity with glass. The

internal standard Bi was also added in the same concentration.

Lindsay Young EOE3602.

 3. Experimental Results & discussion.

3.1 Batch sorption experiments results

The calculated Kd values for each analyte mixture are shown in table 7.
Experiment Mass Moles of Th Moles of Th left in Moles of Th sorbed Kd value
run of sand added ± RSD % solution ± RSD % to sand ± RSD % (ml/g) ±
used (n=3) (n=3) (n=3) RSD %
(g) ± 1 (n=3)
SD
(n=3)
1:10 1.0965 1.28 x 10-6 ±
Th:EDTA 9.36 x 10-8 ± 28.7 1.19 x 10-6 ± 2.3 24.6 ± 27.6
± 0.09 0.02
1:1 Th:EDTA 1.1456 1.42 x 10-6 ±
4.36 x 10-8 ± 38.1 1.37 x 10-6 ± 1.2 55.0 ± 26.2
± 0.150 0.007
1:10 Th:NTA 1.0817 1.22 x 10-6 ±
1.63 x 10-7 ± 15.2 1.05 x 10-6 ± 2.4 11.9 ± 25.2
± 0.106 0.80
1:1 Th:NTA † 1.2101 1.22 x 10-6 ±
6.32 x 10-9 ± 49.8 1.21 x 10-6 ± 0.26 369.2 ± 56.3
± 0.088 0.01
0.4 mM Th 1.000 ± 8.41 x 10-7 ± 5.12 x 10-8 ± 43.9 7.90 x 10-7 ± 2.8 33.8 ± 37.8
0.100 0.003

Table 7: Batch sorption experiment results (2 ml/1g)

† For 1:1 Th:NTA batch experiment n=2

The batch sorption experiments were carried out to determine the Kd value thus

estimating the approximate residence time of each of the analyte mixtures within the

transport column This was accomplished as explained in section 2.1.

The batch experiment Kd values (table 7) were all relatively low in comparison with

Mays calculated values [ CITATION Placeholder1 \l 2057 ], in particular the 0.4 mM

Th only experiment. Mays calculated Kd value was 670 L/kg, in this study the

calculated Kd was 33.8 ml/g. The same solid to liquid ratio (1 g:2 ml) was used in

both experiments and the same time elapsed for the system to reach equilibrium (7

days).

Mays results show that Th in the absence of ligands showed the highest Kd value,

with decreasing Kd values for 1:1 Th:EDTA and 1:10 Th:EDTA, with the 1:10 Th:NTA

having the lowest Kd. The batch Kd values in this study has a similar trend as Mays,

Lindsay Young EOE3602.

with the 1:10 Th:NTA showing the lowest Kd value, followed by the 1:10 Th:EDTA,

discrepancies occur with the 1:1Th:EDTA and the Th only.

The highest Kd value calculated in this experiment was for the 1:1 Th:EDTA,

whereas in Mays experiment Th only had the highest Kd value. It has been

documented by the US EPA[ CITATION Uni99 \l 2057 ] that calculated Kd values for

exactly the same system can vary as much as 3 orders of magnitude when carried

out by 9 different laboratories and concluded that the variability was due to numerous

factors including solid-solution ratio, solid-solution separation method and

temperature [ CITATION Uni99 \l 2057 ], therefore to compare Kd values directly to

Mays would not be viable, but using the overall trend between the values gives an

indication that the results are in agreement that Th only showed a higher degree of

sorption to the sand than Th in a 1:10 ratio with EDTA.

It is also apparent from the batch experiments that the concentration of ligand also

plays an important part in the sorption of Th. In the 1:1 systems for both NTA and

EDTA the Kd values were significantly higher than the corresponding 1:10 ratio

systems, indicating that the Th in the 1:1 systems was more highly sorbed to the

sand. According to May [ CITATION Placeholder1 \l 2057 ], the formation of the

soluble and stable [ThEDTA2]4- species in the excess system allowed the Th to

remain in the solution phase, in the equimolar system the predominant species

[ThEDTA] is not as soluble and may have dissociated due to competition form

surface bound metals displacing the Th from the complex. The solubilisation of the

matrix metals would have increased the number of binding sites for the Th thus

allowing more Th sorption [ CITATION Placeholder1 \l 2057 ].

The columns to run were decided by the batch experiment Kd results. It was decided

that 1:10 Th:EDTA and Th on it own should be compared and also the effect of flow

Lindsay Young EOE3602.

velocity. It was deemed unfeasible to run column experiments for the 1:1 Th:EDTA,

1:1 Th:NTA and 1:10 Th:NTA due to the long residence times calculated from the

batch experiments.

3.2 Column characteristics

3.2.1 Bromide Tracer

In each experiment, the ICP-MS concentration was multiplied by the dilution factor to

give the concentration of Th or Br in each sample pot. The concentration of the

analyte mixture aliquots was calculated and the number of moles injected on to the

column was calculated. An elution curve was then generated using the total volume

of eluent vs molar concentration of Th or Br. The Br elution curve (fig 2) was used to

determine if the Th analyte mixture was retarded in the column relative to the

bromide tracer. Column characteristics were also calculated from the Br tracer

profiles. Pore volume was taken as the volume just before the bromide eluted (fig 2) ,

and the porosity was calculated using equation 4

pore volume (cm3)

Porosity = Volume of column (cm3)†

Equation 4. † Volume of column

3
=3.93cm

The bulk density of the soil was calculated for each column along with flow velocity in
meters per year. Column characteristics for each column are shown in table 8 and Br
elution profiles for each column are shown in Fig 2

Lindsay Young EOE3602.

 Physical properties of experimental columns
Column Mass of Flow Pore Porosity () Bulk density
experimen sand (g) velocity ± volume (calculated (g/cm3)
t 1SD (ml) using eq4)
(m/year)†
A 5.9013 91 ± 7.7 2.13 0.54 1.50
B 5.0126 97.6 ± 7.5 2.23 0.56 1.28
C 5.7355 99 ± 4.4 1.21 0.31 1.46
D 4.9844 21 ± 6.5 1.54 0.39 1.27

Table 8. Physical properties of the experimental columns A) 1:10 Th:EDTA high flow, 1 day duration:
B) Th only, high flow: C) 1:10 Th:EDTA high flow, 7 day duration: D) 1:10 Th:EDTA low flow, 14 day
duration. † Flow velocity for Th column not Br column

A
B
450
30000
400
Concentration of Br (uM)
Concentration Br (uM)

350 25000
300 20000
250
200 15000
150 10000
100
5000
50
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Total flow volume (ml) Total flow volume (ml)

14000 D
20000 12000
Concentration of Br (uM)

18000
Concentration of Br (uM)

16000 10000
14000 8000
12000
10000 6000
8000
4000
6000
4000 2000
2000
0 0
0.00 0.50 1.00 1.50 2.00 2.50
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Total flow volume (ml) Total flow volume (ml)

Lindsay Young EOE3602.

Fig 2 Bromide tracer elution data for columns: A) 1:10 Th:EDTA (high flow, 1day duration) B) Th only
(high flow, 7 day duration) C)1:10 Th:EDTA (high flow, 7 day duration) D) 1:10 Th:EDTA (low flow, 14
day duration)

As concluded by Levy, bromide is an efficient conservative tracer in that it does not

interact with geological mediums; therefore a sharp narrow peak should characterize

a conservative tracer profile. However the profiles seen in fig 2, the peaks have

differing widths. The width of a peak gives an indication of dispersion within the

column whereby the pulse input spreads due to different flow paths [ CITATION

USD04 \l 2057 ]. The different flow paths are attributed to column packing with a

tightly packed column resulting in less dispersivity. It can be seen in fig 2B and 2C

that the peaks are wide in comparison with fig 2 A, it can also be seen from table 8

that column A had the greatest mass of sand and was therefore better packed with a

larger bulk density of sand. In a lesser-packed column, such as fig 2C, the sand

particles are not as tightly packed together and different flow paths through the

porous medium can be taken by the groundwater. This results in a small pore volume

as can be seen in table 8 and higher concentrations seen earlier

It has been noted by Reyla [ CITATION Placeholder4 \l 2057 ] that at very low

ground water velocities, diffusion becomes a significant transport mechanism.

According to Rasilainen [ CITATION Ras97 \l 2057 ] diffusion can retard

radionuclide's migration by spreading them physically from the slow flowing

groundwater into areas where there is no preferential flow path of water and because

of this, more surface binding sites are available for the radionuclide’s to sorb onto.

Lindsay Young EOE3602.

3.2.2 Mass balance of recovered Th

The number of moles of Th injected onto each column along with moles eluted and
solid phase moles for the experiment duration is shown in table 9. A mass balance
was calculated for each column.

Column Moles Moles eluted Solid phase Mass balance

injected moles † (%)
A 2.10 x 10-8 6.31 x 10 -11
3.86 x 10-8 184
B 2.10 x 10-8 7.60 x 10-10 1.72 x 10-8 86
C 2.11 x 10-8 5.39 x 10-9 1.54 x 10-8 99
D 2.06 x 10-8 4.22 x 10-10 2.76 x 10-8 136

Table 9 Mass balance for each column: A) 1:10 Th:EDTA, high flow, 1 day duration: B) Th only,
highflow, 7 day duration: C) 1:10 Th:EDTA, high flow, 7 day duration: D) 1:10 Th:EDTA, low flow, 14
day duration
† Sand blank subtracted (2.8 x 10-8 moles)

Lindsay Young EOE3602.

3.3 Th elution profiles

3.3.1. 1:10 Th:EDTA high flow rate (1 day duration)

40
12 B
10
30
Concentration Th (nM)

[Th] µM
20
6

4 10
2
0
0 0 5 10 15
0 5 10 15 20 25
Total flow volume(ml) Flow volume mL

Fig 3: A) Elution profiles for 1:10 Th:EDTA (higher flow rate, 1 day duration)
B) Elution profile for 1:10 Th:EDTA obtained by May [ CITATION Placeholder1 \l 2057 ]

The 1 day experiment of the 1:10 Th:EDTA column showed no elution peak (fig 3 A).

This is consistent with the calculated batch Kd value that showed that the Th in a

1:10 system should be retained in the column for approximately 2 days.

When compared to Mays data (fig 3 B) [ CITATION Placeholder1 \l 2057 ] for 1:10

Th:EDTA column at the same flow rate, the high concentration peak occurred at

approximately 4.5 ml and all Th had eluted after approximately 15 mls. It is important

to note that the concentrations used by May were an order of magnitude greater than

used in this study. May concluded that colloidal Th species were responsible for the

enhanced migration. The one-day column experiment showed that no colloidal

facilitated transport was taking place and that simple chemical species kinetics was

in action. It is evident from the comparison of the two profiles that concentration of Th

Lindsay Young EOE3602.

and complexing agent plays an important role in whether Th-colloids or Th-EDTA

species form. In higher concentration systems, Th-colloids form, that enhances Th

migration and binding site availability will be reduced therefore reducing sorption of

the Th.

3.3.2. Th only column

B
18 5.E-05
16
14 4.E-05
Concentration Th (nM)

12
10
3.E-05
[Th]µM

8
2.E-05
6
4 1.E-05
2
0 0.E+00
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80
Total flow volume (ml) Flow volume mL
Fig 4: Th only elution profiles: A) Obtained from this study (7 day duration)
B) Obtained from Mays study (4 day duration) [ CITATION Placeholder1 \l 2057 ]

The Th only column showed no clear elution peak and low concentrations of Th were

detected throughout the 7 day experiment (fig 4 A). A similar profile was seen by May

(fig 4 B). Over the entire experimental period only 3% of the Th injected onto the

column eluted. As was seen in Mays experiment the Th only column (fig 4 A) showed

a high degree of sorption to the sand which also reinforces Hakems and Means

conclusion that tetravalent actinides without complexing agents are highly sorbed to

Lindsay Young EOE3602.

the soil and migration will be limited [ CITATION Placeholder2 \t \l 2057 ]

[ CITATION Placeholder5 \t \l 2057 ].

3.3.3. 1:10 Th:EDTA low flow column (14 day duration)

The 1:10 Th:EDTA low flow rate column profile (fig 5A) showed very small

concentrations of Th eluting throughout the experiment duration time of 14 days with

no resolved peak of maximum concentration.

After visual inspection, the profiles of the Th only column and the 1:10 Th:EDTA low

flow rate column (fig 4A & 5A respectively) looked similar in that low concentrations

were seen throughout the duration and both had a slight ‘tailing’ of lower

concentrations.

The 1:10 Th:EDTA low flow rate column had a maximum total elution volume of 60

mls, so the Th only data was used up to 60 ml elution volume for a comparison of the

two profiles. The comparison profile is shown in fig 5B

16 B
16
14
14
12
12
concentration Th (nM)

10
10
[Th] (nM)

8
8
6
6
4
4
2 2

0 0
0 20 40 60 80 0 10 20 30 40 50 60 70
Total flow volume (ml) Total flow volume (ml)
Th only data 1:10 Th:EDTA low flow data

Fig 5: A) 1:10 Th:EDTA low flow elution profile B) Comparison of elution profiles for Th only column
and 1:10 Th:EDTA low flow column up to 60 ml total eluent volume

Lindsay Young EOE3602.

Using the number of moles injected and eluted up to 60 mls, comparisons could be

made between the profiles to see if Th was retarded within the columns and also

to highlight any similarities of the desorption kinetics. Table 10 highlights data up to

60 mls total eluted volume for the 3 columns.

Column Moles injected Moles eluted up to % eluted

60mls

Th only 2.11 x 10-8 4.36 x 10-10 2.07

1:10 Th:EDTA low flow 2.06 x 10 -8 4.22 x 10-10 2.05

1:10 Th:EDTA higher 2.11 x 10-8 3.47 x 10-9 17.73

flow
Table 10: Data for each column up to 60 ml elution volume

The profiles of the Th only column and the 1:10 Th:EDTA low flow rate were similar

(fig 5B), with 2.1 % of the total Th injected eluting in up to 60mls of groundwater in

both cases (table 10) . This suggests that the Th:EDTA is dissociating from the EDTA

in the column. This could be attributed to the longer time the ThEDTA complex spent

in the column in the low flow system, thus longer contact with the sand. The metals

that are bound to surface binding sites in the sand will compete for the EDTA

[ CITATION Placeholder6 \l 2057 ] [ CITATION Placeholder7 \l 2057 ]and may be

able to displace Th from the complex [ CITATION Placeholder1 \l 2057 ]. The

displaced Th can then be adsorbed to sand surface binding sites allowing for limited

transport of Th. This could explain the low concentrations of Th throughout the

experiment and the slight tailing of the profiles as Th is slowly released from these

binding sites.

Over the entire experimental duration (7 days for Th only and 14 days for low flow

system) 3% of the total Th injected eluted from the Th only column and 2% from the

low flow column. As was seen in Mays experiment the Th only column (fig 4 A)

Lindsay Young EOE3602.

showed a high degree of sorption to the sand which also reinforces Hakems and

Means conclusion that tetravalent actinides without complexing agents are highly

sorbed to the soil and migration will be limited [ CITATION Placeholder2 \t \l 2057 ] [

CITATION Placeholder5 \t \l 2057 ]. Contrary to Hakems findings that EDTA in

excess promoted the migration of radionuclide's, it was not the case in the low flow

rate system in this study and the Th behaved more like the Th only system.

3.3.4 1:10 Th:EDTA high flow rate column (7 day duration)

16 140
140
14 120
120
Concentration Th (nM)

[Th] normal flow (nM)

12
100
[Th] low flow (nM)

100
10
80 80
8
60 60
6
40 40
4
20 20
2
0
0 0
0 20 40 60 80 100 120 140 160
0 10 20 30 40 50 60 70
Total flow volume (ml)
Total eluent volume (ml)

Low flow Normal flow

Fig 6: A) 1:10 Th:EDTA elution profile (7 day duration, higher flow rate) B) Comparison of low flow
rate and higher flow rate profiles

The 1:10 Th:EDTA higher flow rate column (7 day duration) (fig 6A ) elution profile

shows that the Th was delayed compared to the Br tracer profile (fig 2 C) showing

non-conservative behaviour. About 100 pore volumes (pore volume = 1.21 mls) were

necessary to remove 95.9% of the total Th that eluted. The breakthrough flow volume

was 14.4 mls (12 pore volumes) and the maximum Th concentration in the eluent

reached 118.3nM at 29.2 ml. The profile was characterised by a maximum

Lindsay Young EOE3602.

concentration peak followed by a long elution tail of lowering concentrations showing

a clear indication of Th retardation by sorption onto the sand.

The shape of the profile (fig 6) suggests that initially (up to 12 pore volumes) the

ThEDTA complex was rapidly adsorbed as a species to the sand surface binding

sites producing an exchangeable sorbed fraction that may desorb immediately (ie

reversible)[ CITATION Han09 \l 2057 ]. The kinetics of the adsorption and desorption

of the complex are a function of the Kd of the species whereby the amount in solution

and the amount sorbed are in equilibrium. At the maximum concentration peak

(118.3 nM) 0.95% of the total Th injected had eluted with the rest still inside the

column. The concentration of Th then decreased slowly due to slow Th desorption

kinetics [ CITATION Han09 \l 2057 ][ CITATION Placeholder1 \l 2057 ] producing a

long ‘tail’ on the profile. The profile seen by May [ CITATION Placeholder1 \l 2057 ]

for the 1:10 Th:EDTA system (fig 3B) also showed tailing and a maximum

concentration peak at 4.5 ml. The early concentration peak seen by May could be

attributed to EDTA mediated colloidal facilitated transport of the Th. This shows that

the formation of Th-colloids enhances Th migration quite considerably.

Over the experiment time (7 days), 26% of the Th injected eluted with 73% remaining

in the column (total recovery = 98%). Similar percentages were also obtained by May

with 35% of total Th injected eluted with 64% remaining on the column suggesting

that colloidal facilitated transport only enhanced the migration of Th and did not affect

sorption-desorption kinetics.

Comparing the data (fig 6A) with the Th only column (fig 4A) (up to 140 mls elution

volume where 3.3% eluted in Th only column and 25.2% in 1:10 Th:EDTA column) it

is clear that EDTA enhanced the migration of Th which is also in agreement with

previous study’s conclusions[ CITATION Placeholder2 \l 2057 ],[ CITATION

Lindsay Young EOE3602.

Placeholder6 \l 2057 ], [ CITATION Placeholder8 \l 2057 ],[ CITATION Placeholder1

\l 2057 ].

Comparing the low flow column with the 1:10 Th:EDTA normal flow column (fig 6B),

the concentrations of Th in the eluent in the normal flow system was an order of

magnitude greater than the low flow system even though the same amount was

injected. The kinetics of cation exchange between the ThEDTA complex and

competing surface bound metals are too slow to be seen in the higher flow system

due to the less time spent in the column resulting in less contact with the sand and

therefore less sorption of the Th to the binding sites.

In both systems, Th breakthrough was approximately 14 mls, thereafter a steady

increase of Th was seen in the eluent but with an order of magnitude difference. After

maximum elution concentrations (118.3 nM – normal flow and 14.0 nM – low flow),

desorption of the Th occurred at a similar rate but again with an order of magnitude

difference between the concentrations. At 60 mls 2.05% of the Th injected had

eluted in the low flow system, with 17.7% eluting in the normal flow system. The

results suggests that flow rate plays an important part in the migration of Th in that at

low flow rates Th is retarded due to cation exchange and sorption to available binding

sites whereas in higher flow systems the slow cation exchange kinetics do not

happen as readily and therefore Th is more mobile.

As discussed in Mays study the predominant species in 1:10 Th:EDTA systems is the

[ThEDTA2 ]4- species [ CITATION Placeholder1 \l 2057 ]. Robertson concluded that

the formation of soluble anionic complexes with radionuclide's enhances the mobility

in groundwaters [ CITATION Placeholder7 \l 2057 ]. In the low flow system, the

[ThEDTA2 ]4 species dissociated allowing for sorption of the Th, while in the higher

Lindsay Young EOE3602.

flow system dissociation couldn’t happen as readily due to the slow cation exchange

kinetics, therefore the principal species in the higher flow system will have been the

soluble anionic complex, increasing Th mobility.

3.4 Solid phase digestion

Each sand section of the column was analysed for total Th content. The sand blank
(3.28 ± 0.11 nmoles/g) was subtracted from the value. The error bars show 10%
RSD from experimental and analytical uncertainty.

14.00
12.00
Conc of Th (nmol/g)

10.00 Low flow

rate
8.00
1:10
6.00 Th:EDTA

4.00
2.00
0.00
0-1 1-2 2-3 3-4 4-5
Distance travelled from column inflow (cm)

Fig 6: Column sand digestion results showing Th distribution along the length of the column.

The distribution of Th throughout the low flow rate column (fig 6) shows a high

concentration of Th in the sand at 0-1cm from the inflow. This shows that Th quickly

dissociated from the EDTA soon after entering the column due to the competition

from the solid phase surface bound metals, freeing up binding sites for the displaced

Th. 60% of the total solid phase Th remained in the 0-1 cm section, with 40%

migrating beyond this suggesting, that the Th had some mobility. This could be

attributed to the binding sites being saturated in the 0-1 cm section.

Column distribution of Th in the higher flow system showed that the first section (0-1

cm from inflow) (fig6) had the highest concentration of Th with 42.7 ± 4.9% of the

Lindsay Young EOE3602.

total sand phase Th . This trend was also the low flow rate column and Mays column

[ CITATION Placeholder1 \l 2057 ]. The concentration gradient was much reduced

over the sections and Th was distributed more evenly with 26.6 ± 0.6% in the 1-2 cm

section and 21.6 ± 1.7% in the 2-3 cm section, showing that the Th was more mobile

in the column than in the low flow one.

No column distribution data was available for the Th only system due to difficulties

removing the sand as a core. Comparisons of the low flow rate system in this study

with Mays Th only column distribution [ CITATION Placeholder1 \l 2057 ] also

support the theory that the Th in the low flow system dissociated from the EDTA

allowing sorption and slow desorption of Th to the sand.

The column experiments are in agreement with the static batch tests in that the Kd

calculated for Th only was higher than the 1:10 ThEDTA (33.8 ml/g ± 37.8% and 24.6

ml/g ± 27,6%, respectively) and therefore the Th being more retarded in Th only

system.

4. Conclusions

The column experiments provided a dynamic and representative method to study the

transport behaviour of Th whereby the kinetics of sorption and desorption processes

were taken into account.

The Th only column showed that the Th was highly sorbed to the sand and that

desorption of Th was kinetically slow, which limited the concentration in the eluent

and hence Th mobility. Only 3% of the Th injected was eluted. Similar findings that

tetravalent actinides in the absence of complexing agents have a high affinity for soil

surface binding sites have been reported in previous studies (i.e.) [ CITATION

Lindsay Young EOE3602.

Placeholder1 \l 2057 ][ CITATION Placeholder5 \l 2057 ][ CITATION Placeholder2 \l

2057 ]

The 1:10 column experiment at the higher flow rate showed that EDTA enhanced Th

migration through the column. This is evident by the maximum concentration peak

(118nM) seen at 29.2 ml. The Th only column showed no peak and very low

concentrations of Th throughout showing limited mobility of the Th.

26% of the total Th injected eluted over the experimental period of 7 days. Compared

with Mays profile with an early elution peak at 4.5 ml [ CITATION Placeholder1 \l

2057 ] in which EDTA mediated Th-colloids were transported, it is apparent that Th-

EDTA species are more retarded and less mobile than Th-colloids.

Contrary to the conclusion that EDTA enhanced Th migration in the higher flow

system, the column experiment for 1:10 Th:EDTA at low flow rate showed that Th

migration was limited, much like in the Th only column. It is apparent from these

results that hydrodynamic properties of the system can govern the extent of Th

sorption to the sand. The higher water velocity means less time in the column for the

Th-EDTA, hence less time for cation exchange processes to occur between the

surface bound metals and Th [ CITATION May09 \l 2057 ]. This leads to the

[ThEDTA2]4- being the predominant species in the system with the negative charge

on the complex making it more soluble than the Th 4+ ion, thus more mobile.

In the low flow system the ThEDTA complex had more time to dissociate reducing

the stability of the [ThEDTA2]-4 species. The free Th4+ was then able to adsorb to

available surface binding sites. The kinetics of desorption are too slow to be seen in

the higher flow system, but in the low flow system the slow desorption kinetics

reduced the eluent concentration of Th by an order of magnitude.

Lindsay Young EOE3602.

The batch sorption experiments showed that the concentration of ligands played an

important role in the sorption and subsequent migration of Th. Equimolar

concentrations of complexing agent and Th showed higher Kd values, thus a higher

degree of sorption when compared to a 10 fold excess of complexing agents.

The formation of the highly soluble and stable [ThEDTA 2]4- species may have

contributed to the reduced sorption of the Th in the excess system, whereas

dissociation of the ThEDTA complex and more binding sites being available due to

increased surface bound metal solubilisation would have allowed Th to sorb more

readily to available binding sites in the equimolar system.

5. Applications to the Environment

When predicting the fate of tetravalent radionuclides the concentration of the

radionuclide and complexing agents is an important factor. Th in the absence of

complexing agents is highly immobilised as seen in this study and Mays [ CITATION

Placeholder1 \l 2057 ]. The order of magnitude difference between the

concentrations of Th used in both studies did not make a marked difference between

the sorption of Th to the sand. When Th is pre-equilibrated with complexing agents,

the concentration of complexing agent becomes an issue. It has been seen that high

concentrations of complexing agent with respect to Th (i.e.1:10 ratio), migration of Th

is increased. When both the Th and complexing agent concentration are increased

an order of magnitude (as seen in Mays study), colloidal species form, which, when

compared to the results in this study, are more mobile than chemical species.

The velocity of groundwater is also an essential consideration. As seen in this study,

low groundwater flow results in the destabilisation and dissolution of the [ThEDTA 2]4-

Lindsay Young EOE3602.

species in a 1:10 system. The dissolution is a result of surface bound metal

competition for the EDTA because of longer contact with the sand. Th is then able to

bind to available binding sites, however at higher flow rates contact time with the

sand is limited, less dissolution occurs, resulting in the highly soluble [ThEDTA 2]4-

migrating with the ground water.

The results from this study are site specific i.e. Drigg low level waste repository, and

could not be applied to any LLW site because of the differing geological media and

ground water composition found else where. The results could be used for analogous

tetravalent actinides i.e. Plutonium(IV) migration at Drigg LLW repository.

6. Further work.

Due to time constraints, transport modelling of Th-EDTA could not be carried out.

Modelling of the data obtained from the column experiments using the k1D computer

code [ CITATION Han09 \l 2057 ][ CITATION May09 \l 2057 ] can be used to make

field scale predictions in the mobility of Th and also give an idea of chemical

processes and mechanisms responsible for retardation or mobility.

7. References

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1983.

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Dozel, M, and R Hagermann. “RADIONUCLIDE MIGRATION IN
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Martin-Garin, A, J P Gaudet, L Charlet, and X Vitart. “A dynamic study of the sorption
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Rasilainen, Kari. Matrix diffusion model: in-situ tests using natural analogues. PhD
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Read D, Ross D, Sims RJ. “The migration of uranium through Clashach Sandstone:
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Robertson DE, Schilk AJ, Lepel C, Thomas CW, Pratt SL, Cooper EL, Hartwig P,
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8. Acknowledgements
I would like to thank my supervisor, Dr Miranda Keith-Roach for her continual
support, encouragement and guidance throughout my dissertation. I also want to
thank Dr Andy Fisher for all his help and expertise in ICP-MS, Jane Eagling for
making my laugh when things got too much and finally my family, without whom none
of this would have been possible!

Lindsay Young EOE3602.

Appendices

Appendix 1

Photograph of the column experiment set up. Showing the peristaltic pump
and fraction collector

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Apendix 2

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