Long lived radioactive species such as ¹²⁹I⁻ and ⁹⁹TcO₄⁻ are formed as by-products of nuclear fission. These species have extremely long half-lives (1.5 million and 211,000 years respectively), are biologically assimilating and due to their anionic nature, can move freely within a geosphere. Historical disposal methods for active species are no longer considered acceptable to the general public and other ways in which to treat the waste are being explored. One remove and concentrate method to remove radioactive species from the biosphere is using alkaline-resistant materials which trap active species that can be encapsulated in a high pH concrete matrix. Layered hydroxides and layered double salts which consist of positively charged layers between which exchangeable anions and water molecules lie are good candidates for these materials due to the basic conditions in which they form. The synthesis, anion exchange properties and stability of copper, lanthanum, nickel and zinc hydroxysalts have been investigated. The structures consist of layers of edge-sharing metal hydroxide octahedra together with an interlayer space containing the anion and in some cases water molecules. Products were characterised by powder X-ray diffraction and vibrational spectroscopy to confirm the identity of structure of the material formed and the anion incorporated. Only Cu2(OH)3(NO3), Cu2(OH)3(OAc).H2O, Ni2(OH)3(NO3) and Zn5(OH)3(NO3).2H2O consistently exhibited exchange capabilities with iodide as the target anion. In terms of exchange rate and efficiency, copper hydroxyacetate is a more suitable precursor as equilibrium is achieved in 10 mins; whereas other LHS containing nitrate as the occupying require longer than 1 day to reach equilibrium. Cu2(OH)3(Ac).H2O has been shown to easily exchange acetate for monovalent anions X- (X = Ha-, NO3-, ClO4-, IO4-, SbO3-, OH-). Exchange reactions with ReO4- (used as a surrogate to TcO4-) and trigonal pyramidal monovalent anions (such as IO3-) were unsuccessful. Exposure to divalent anions (CO32-, Cr2O42-, SeO3-) resulted in no interaction whereas exposure to trivalent PO43- forms Cu3(PO4)2. Quantitative analysis has shown that, contrary to XRPD and FTIR data, full exchange of acetate for an equimolar amount of iodide within a Cu2(OH)3+ framework does not occur with 100% efficiency. Activity counting, gravimetric analysis and ion specific probe analysis suggested that only ~92-93% exchange occurs. The stability of TcO4- and I- analogues with respect to pH has been investigated. Activity counting has shown that even in pH 9.5 solution, 57-73% of 125I- and 99TcO4- immobilised with a Cu2(OH)3+ framework is leached into solution after 16 days. Exposure of Cu2(OH)3I to high carbonate, nitrate and chloride environments shows a progressive loss of iodide into solution as the anionic radius of the incoming anion decreases and the concentration of the incoming anion increases. In the case of chloride and nitrate incoming anions, only a 2:1 chloride to iodide ratio is need for full exchange whereas a ratio of 10:1 nitrate to iodide is required. In situ ion exchange experiments at Diamond allowed the exchange of the hydroxyacetate material to be investigated in flow experiments showing similar facile exchange as demonstrated under batch conditions. Rietveld refinements on deuterated samples of halide analogues of the materials have allowed accurate structure determinations for the first time (Cu2(OD)3Cl - a = 5.726Å, b = 6.125 Å, c = 5.634 Å, β = 93.100°, Cu2(OD)3Br - a = 6.085 Å, b = 6.144 Å, c = 5.650 Å, β = 93.593°, Cu2(OD)3I - a = 6.587 Å, b = 6.179 Å, c = 5.680 Å, β = 95.044°). As the size of the halide increases, the hydroxide coordination alters reflecting to changing sigma/pi donor capability of the halide.

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The Northern Cape Province of South Africa has played host to numerous mining activities for over a century. To date, most of the mining activity has ceased, leaving the area laden with derelict mine sites and unlined tailings dumps. One such site is the Spektakel mine situated to the west of the town of Springbok. The unlined copper and sulphide rich tailings at the site have the potential to leach elevated concentrations of copper and acidic water into the Buffels River downslope of the site. This poses a threat to the surrounding communities that rely mainly on the river to supply water for drinking, livestock and irrigation. The soil surrounding the tailings dumps was characterised in terms of its mineralogical and chemical properties. The results indicate that the soil contains elevated concentrations of Cu2+, which is bound in the soil in the form of the secondary copper hydroxy mineral atacamite (Cu2(OH)3Cl). No other secondary copper minerals were identified at the site. Analysis of the solution present on the surface of the tailings dumps indicate that the tailings are the main source of the high Cu2+, Mg2+ and SO42- concentrations observed in the surrounding soils. As this solution migrates through the tailings dumps, into the soil, it accumulates Cl- through halite dissolution. The resulting acidic Cu2+, Mg2+, SO42- and Cl- solution reacts with the calcite in the soil, replacing it with atacamite. To determine why only a copper chloride mineral formed in the sulphate rich environment a synthetic solution with the composition of a solution in equilibrium with the soil was evaporated, both in the presence and absence of calcite. The results indicate that when the solution comes into contact with calcite, atacamite immediately precipitated, removing the Cu2+ from the solution. In the absence of calcite Cu2+ remains conservative, accumulating in the solution without precipitating a copper sulphate mineral. This establishes that the elevated Mg2+ concentration of the solution induces the formation MgSO4 aqueous complexes that reduce the activity of free sulphate, thus restricting copper sulphate mineral formation. The results from the soil characterization indicate that the atacamite stabilization mechanisms (circumneutral pH, high Cl- concentration and calcite) in the soil are diminishing. During sporadic rain events the acidic tailings solutions dissolve the calcite and temporarily reduce the Cl- concentration of the soil. To determine how these decreases will influence Cu2+ mobility in the soil, the stability of atacamite was tested by reducing the pH both in the presence and the absence of chloride. The results indicate that an elevated Cl- concentration and a pH > 6 stabilizes atacamite. A decrease in either of these parameters destabilizes atacamite and favours its dissolution. The study concludes that the current chemical conditions in the soil at Spektakel favour the stability of atacamite. However, continued sporadic rain events will reduce the Cl- concentration in the soil by increasing the SO42- concentration. This acidic solution will dissolve the calcite in the soil, thus reducing the buffering capacity of the soil, leading to the instability of atacamite, resulting in the leaching of large quantities of Cu2+ into the surrounding water bodies. / AFRIKAANSE OPSOMMING: Die mynbou bedryf was die ekonomiese dryfkrag van die Noord-Kaap Provinsie van Suid-Afrika vir meer as ‘n eeu. Die area was die gasheer vir ‘n verskeidenheid mynbou aktiwiteite tot die mynmaatskappye besluit het om mynproduksie te staak en die gebied te verlaat. Die mynmaatskappye het geen rehabilitasie aan die myne en mynhope verrig nie. Die verlate myne lê verspreid in die area met oop mynhope wat koper en ander swaar metale in die grond, sowel as in die water, na omliggende areas kan versprei. Een van dié verlate myne is die Spektakel myn 40 km wes van Springbok. Die mynhope by Spektakel kan moontlik koper en ander swaar metale in die Buffelsrivier, wat langs die myn verby loop, loog. Dit dien as ‘n bedreiging vir die omliggende gemeenskappe wat staatmaak op die water vir drinkwater en besproeiing. Die grond rondom die mynhope was ge-analiseer om te bepaal hoe erg ‘n bedreiging die mynhope vir die omgewing is. Die resultate dui daarop dat die grond hoë konsentrasies Cu2+ bevat wat vasgebind is in die sekondêre koper mineral atakamiet (Cu2(OH)3Cl). Geen ander sekondêre koper minerale is in die grond geïdentifiseer. Die analise van die oplossing wat bo-op die mynhoop aangetref is dui aan dat dié oplossing suur en gekonsentreerd is t.o.v. Cu2+, Mg2+ en SO42-. Terwyl die oplossing deur die mynhoop migreer los dit haliet in die grond op wat Cl- tot die oplossing byvoeg. Wanneer hierdie suur en Cu2+, Mg2+, SO42- en Cl- ryke oplossing met die kalsiet in die grond reageer word die kalsiet vervang met atakamiet (Garrels en Stine, 1948). Om vas te stel waarom slegs 'n koperchloried mineraal vorm in die sulfaat ryke grond was ‘n oplossing, met ‘n samestelling soortgelyk aan 'n oplossing in ewewig met die grond, verdamp in beide die teenwoordigheid en afwesigheid van kalsiet. Die resultate van die eksperiment dui daarop dat wanneer die oplossing in kontak kom met kalsiet atakamiet onmiddellik neerslaan en Cu2+ uit die oplossing verwyder. In die afwesigheid van kalsiet bly Cu2+ konserwatief in die oplossing; die Cu2+ hoop op in die oplossing en slaan nooit neer nie. Daar is vasgestel dat die verhoogde Mg2+ in die grondoplossing MgSO4 water komplekse vorm wat die aktiwiteit van SO42- verlaag en verhoed dat kopersulfaat minerale kan vorm. Verdere navorsing dui aan dat die chemiese meganismes wat atakamiet in die grond stabiliseer besig is om te kwyn. Gedurende sporadiese reën buie word die kalsiet in die grond opgelos deur die suur mynhoop oplossings wat die pH van die grond verlaag. Die mynhoop oplossing verryk ook die grond t.o.v SO42- wat die Cl- konsentrasie verlaag. Om te bepaal hoe hierdie afname in Cl- konsentrasie en pH die migrasie van Cu2+ beïnvloed was atakamiet oplossbaarheid bepaal. Atakamiet was onderskeidelik geplaas in ‘n suiwer water en chloried oplossing tewyl die pH verlaag was om te bepaal hoe atakamiet oplos in elk van die oplossings. Die resultate dui aan dat 'n verhoogde Cl- konsentrasie en pH > 6 atakamiet stabiliseer. Die afname van beide hierdie veranderlikes het veroorsaak dat atakamiet makliker ontbind en Cu2+ vrystel. Die gevolgtrekking van die studie is dat die huidige chemiese toestande in die grond by Spektakel gunstig is vir die stabiliteit van atakamiet. Met sporadiese reën buie neem die Cl- konsentrasie in die grond af en los kalsiet op. Hierdie afname in pH en Cl- konsentrasie maak atakamiet meer onstabiel wat gevolglik Cu2+ in die grond en water rondom Spektakel vrystel.