<div><div><div><p>The radionuclide 10Be is produced in the atmosphere and is delivered to Earth’s surface in meteoric rain and aerosols. The stable nuclide 9Be is present in trace concentrations within rocks in Earth’s crust and is released via chemical weathering. Together, these two isotopes have been employed to study a wide range of Earth processes. Here I explore new terrestrial archives of Be isotopes: cave speleothems and terrestrial Mn-oxides. Until this point, these archives have barely been studied. Only one published dataset of Be isotopes in cave speleothems exists (Lundblad, 2006), and to my knowledge, terrestrial manganese oxides are yet to be explored. However, since speleothems and Mn-oxides precipitate from groundwater, they have the potential to encode temporal variations in the 10Be/9Be ratio of water and colloids in the vadose zone.</p><p>I develop a framework for using the 10Be/9Be ratio in the dissolved phase and/or secondary weathering products as a metric of chemical weathering rate. I am motivated by several over-arching questions:</p><ol><li><p>1) Which factor, or factors, is/are dominant in controlling Be isotopes in speleothems and terrestrial Mn-oxides?</p></li><li><p>2) Can Be isotopes in speleothems be used as a metric of weathering rate over time, particularly across glacial/interglacial cycles?</p></li><li><p>3) Can Be isotopes be used to date the formation of terrestrial Mn-oxides?</p></li></ol><p>I measure Be-isotope concentrations in speleothems from Soreq Cave, Israel. By applying an equation that I derive in this thesis, I use the temporal variation in the speleothem10Be/9Be ratio to calculate chemical weathering rates over the last 168 ka. Chemical weathering varies with independent proxies for temperature. The weathering-temperature relationship can be fit to an Arrhenius relationship, and the calculated activation energy (Ea) matches other field-based estimates for feldspar, an abundant mineral in the soil above the cave. In the Appendices I present additional results of Be-isotope measurements in a flowstone from Buffalo Cave in South Africa, as well as Mn-oxides from the Appalachians.</p></div></div></div>

One of the most essential resources for life on our planet is water. A concern for water resource sustainability has shifted towards the sustainable development of clean water body resource (SWDF, 2009). Data for the Vaal River water chemistry is in abundance. However, research on the historic natural conditions influencing the inorganic water quality, is not as extensive. Inorganic data was obtained from the Department of Water Affairs, for the period 1972 to 2011, for identified monitoring stations along the Vaal River. Water quality was evaluated using various geochemical techniques to analyse the data. The results of the study indicate that the water chemistry of the Vaal River is controlled by: 1. Chemical weathering of siliceous sediment, intrusive igneous rocks and metamorphic rocks (Na+, K+, Mg2+, Ca2+ and (HCO3)-). 2. Anthropogenic influences increasing the sulphate (SO4) concentration There is no major increase in ion concentrations for the stations. However the concentrations of bicarbonate (HCO3)- and SO4 change as it progresses downstream from the first upstream station to the last downstream station. Based on the chemical characterisation, three groups have been identified. (1) Group 1 stations appear to suggest a higher influence in chemical weathering than the group 2 stations. (2) Group 2 stations appear to suggest a greater influence from SO4. (3) Group 3 stations appear to suggest an influence from both the bicarbonate and the SO4 influences. Geographically the chemical weathering is an indication of the three different groups with strong anthropogenic influences in the middle group. The water chemistry for the Vaal River is controlled by two processes, namely chemical weathering and anthropogenic influences. The prominent indication of the difference in these two influences can be seen between group 1 and group 2. A secondary conclusion indicates that a total dissolved solid (TDS) alone is not an accurate representation of anthropogenic influence (or poor water quality) on inorganic water quality of the Vaal River. The natural weathering or geological influences appears to play a more dominant role in certain sections or catchments with lower contributions from anthropogenic influences. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2015

One of the most essential resources for life on our planet is water. A concern for water resource sustainability has shifted towards the sustainable development of clean water body resource (SWDF, 2009). Data for the Vaal River water chemistry is in abundance. However, research on the historic natural conditions influencing the inorganic water quality, is not as extensive. Inorganic data was obtained from the Department of Water Affairs, for the period 1972 to 2011, for identified monitoring stations along the Vaal River. Water quality was evaluated using various geochemical techniques to analyse the data. The results of the study indicate that the water chemistry of the Vaal River is controlled by: 1. Chemical weathering of siliceous sediment, intrusive igneous rocks and metamorphic rocks (Na+, K+, Mg2+, Ca2+ and (HCO3)-). 2. Anthropogenic influences increasing the sulphate (SO4) concentration There is no major increase in ion concentrations for the stations. However the concentrations of bicarbonate (HCO3)- and SO4 change as it progresses downstream from the first upstream station to the last downstream station. Based on the chemical characterisation, three groups have been identified. (1) Group 1 stations appear to suggest a higher influence in chemical weathering than the group 2 stations. (2) Group 2 stations appear to suggest a greater influence from SO4. (3) Group 3 stations appear to suggest an influence from both the bicarbonate and the SO4 influences. Geographically the chemical weathering is an indication of the three different groups with strong anthropogenic influences in the middle group. The water chemistry for the Vaal River is controlled by two processes, namely chemical weathering and anthropogenic influences. The prominent indication of the difference in these two influences can be seen between group 1 and group 2. A secondary conclusion indicates that a total dissolved solid (TDS) alone is not an accurate representation of anthropogenic influence (or poor water quality) on inorganic water quality of the Vaal River. The natural weathering or geological influences appears to play a more dominant role in certain sections or catchments with lower contributions from anthropogenic influences. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2015

Specialized teacher preparation programs are graduating teachers with commitments to advocacy. This expanded definition of teaching stands in opposition to traditional expectations for the role of teachers that have developed during the history of U.S. education into organizational and social frames that reinforce tradition and work against reform. These influences constitute forces of professional weathering that may wear down teachers’ visions and actions for their work. This multicase study focused on four graduates from an intensive two-year teacher preparation program that included initial certification along with induction support in the second year of the program as they completed master’s degree requirements. The inquiry sought to understand how they envisioned their roles as teacher advocates and how they enacted and sustained their visions, resisting traditional teacher roles. Participants were graduates of the same cohort of the preparation program who were completing their second year of teaching in urban high-need schools and who had been nominated and confirmed as effective teachers of diverse students by faculty members of the university program and of local schools. Program materials were analyzed as background material to establish context. Primary data that were inductively and iteratively analyzed included extant course assignments, three individual interviews with each participant, three school-related observations, and three focus group interviews. Findings provide insight into the ways in which the teachers enacted a vision of anticipatory advocacy. Anticpatory advocacy includes intervening actions that are the result of a dual awareness of students’ immediate and future needs and have implications beyond boundaries of time and space in an effort to positively influence students’ lives in the immediate as well as distant future. The teachers, each of whom held beliefs that aligned with the culturally relevant foundations of the program prior to their selection, employed tools related to responsive classroom management, ambitious teaching strategies, and professional collaboration that they acquired and honed during their program. By working backward from the classrooms of effective teachers, the study links classroom practices with teacher preparation, providing direction for stakeholders concerned with the development and retention of high quality teachers for all children, especially in challenging school contexts.

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: The Okiep copper district in the north-western corner of South Africa is a region that has been mined for over 150 years. Most mining operations have ceased, but years of mining has left the area scattered with abandoned mining sites. Acids (as used in ore processing) together with acid mine drainage generated from tailings exposure, collectively referred to as AMD hereafter, are a contamination risk to water resources and the biodiversity of this arid area. This study focused on an abandoned copper processing pond located close to the town of Nababeep. The leaching pond is unlined and has been excavated in the shallow colluvial soils. The natural soils of the area are shallow (60 cm) (WRB – Arenosol; SA – Oakleaf). Formations of corroded granite-gneiss boulders are an indication of the corrosiveness of the AMD collecting in the pond. The AMD was collected from the pond in the dry season at its most concentrated form and the AMD had exceptionally high concentrations of Al (26.9 g/l), Fe (42.9 g/l), Mg (20.5 g/l), Cu (3.8 g/l) and Mn (3.4 g/l). Melanterite (FeSO4·7H2O), a soluble ferrous compound, was found to play an important role in the immediate release of Fe and sulfates. The pristine soils have a sandy texture (2–5.2 %clay). The minerals detected in the clay phase include illite, kaolinite, montmorillonite and quarts. Pristine soils show some degree of contamination with low pH (4.38–4.77) and high Cu and sulfate contents. Soils located in the processing pond, which have been exposed to AMD for an extended period of time, showed poorly crystalline phases to be present (indicated by a broadening of the XRD peaks for clay minerals). Saturation indices (SI) were determined for saturated paste extracts of the pond soils and the obtained SI values support the notion of dissolution of silicate clays, as the obtained SI values ranged between –1.3 and –11.77 for illite and –4.76 to 0.58 for kaolinite. Jarosite, a new phase, formed in the contaminated soil and is a sink for K. Long term weathering experiments of pristine soils exposed to AMD indicated that clay minerals are significantly weathered and altered, which was identified by observing the broadening of the clay XRD peaks. Fourier transform infrared (FTIR) spectra were generated by scanning clay samples of the weathered soil. Amorphous phases were confirmed by structured water bands with wavenumber values of 3700 and 3300 cm−1 for acid treated soil. Micrographs showed a more amorphous and corroded morphology in the acid treated soil. Metal retention experiments were conducted by exposing the pristine soil to AMD repeatedly. Iron was the predominant metal attenuated in the soil. Metals such as Al, Mn, Na, K, Ca and Co were released by the soil into solution. Removal of Si is associated with the dissolution of clay minerals. The pristine soil shows limited capacity to neutralize acidity and low capacity to retain metals when leached with AMD. Metals were predominantly extracted in the water soluble phase of the long term weathering treatments. Aluminium was the most mobile fraction, being extracted predominantly from the water soluble fraction (2035 mg/kg). Exchangeable and acid soluble fractions did not retain significant quantities of metals. In the soil from the processing pond, the reducible fraction had a high concentration of reducible Fe (21175 mg/kg) and Si (3070 mg/kg). The reducible fraction also had the highest concentration of Cr (15.85 mg/kg), Cu (41.53 mg/kg), Pb (8.0 mg/kg) and Zn (10.65 mg/kg) compared to the other fractions of this soil. For the control experiment, the concentration of Cu (77.3 mg/kg), Pb (10.8 mg/kg) and Zn (24.1 mg/kg) were higher than contaminated soil yet lower for Cr (6.05 mg/kg). From these experiments, it can be concluded that the pristine soils studied have a limited ability to retain heavy metals in the non-bioavailable fraction, and, due to the nature of AMD, they are not effective in retaining metals sufficiently. The findings of this study suggest that the capacity of these pristine soils to buffer pH and retain metals is greatly limited. This could be as a result of (1) the low clay content, (2) the low concentration of secondary carbonates and (3) the low pH of the soil. The leaching of AMD from the pond is thus not regulated by the soils and poses a risk for nearby water resources. / AFRIKAANSE OPSOMMING: Die Okiep Koper Distrik, geleë in die noord-westelike hoek van Suid-Afrika, is ‘n streek waar mynbou al vir meer as 150 jaar plaasvind. Die meeste mynbou aktiwiteite is gestaak, maar jare van mynbou het die streek nagelaat met verskeie verlate mynbouterreine. Sure, wat in die prosessering van erts gebruik word, en suurmynwater wat gegenereer word uit die mynuitskot (gesamentlik verwys na as suurmynwater) is ‘n besoedelingsrisiko vir waterbronne en biodiversiteit in hierdie dorre area. Die studie fokus op ‘n verlate koper prosesserings aanleg naby die dorpie Nababeep. Die logingsdam is nie geseël nie en is uitgegrawe in vlak, kolluviale grond. Die natuurlike gronde van hierdie area is vlak (60 cm) (WRB – Arenosol; SA – Oakleaf). Formasies van weggevrete graniet-gneis rotse in die opgaardam is ‘n aanduiding van die bytende potensiaal van hierdie suurmynwater. Suurmynwater was versamel in die dam gedurendie die droë seisoen in die mees gekonsentreerde vorm. Die suurmynwater het besonderse hoë konsentrasies van Al (26.9 g/l), Fe (42.9 g/l), Mg (20.5 g/l), Cu (3.8 g/l) en Mn (3.4 g/l). Melanteriet (FeSO4·7H2O) is ‘n ysterhoudende verbinding en, alhoewel dit oplosbaar is, speel dit ‘n belangrike rol in die onmiddelike vrylating van Fe en sulfate. Die onversteurde grond het ‘n sand tekstuur (2–5.2 % klei). Die minerale wat in die klei fraksie ge-identifiseer is sluit illiet, kaoliniet, montmorilloniet en kwarts in. Die ongerepte gronde dui egter op ‘n mate van besoedeling deurdat dit ‘n lae pH (4.38–4.77) enhoë Cu en sulfaat inhoud het. Die grond wat geleë is naby die prosesseringsaanleg en ook blootgestel is aan suurmynwater vir ‘n verlengde tyd, dui daarop dat swak kristallyne fases teenwoordig is in die grond. Dit word bevestig deur ‘n verbreding van die XRD pieke van kleiminerale. Versadiging indekse (VI), wat bepaal is in versadigde grondekstraksies van die damgrond, ondersteun die oplossing van die silikaatkleie en word gereflekteer deur VI waardes wissel tussen –1.3 en –11.77 vir illiet en –4.76 tot 0.58 vir kaoliniet. Jarosiet is ‘n nuwe fase wat gevorm het in die besoedelde grond en is ‘n sink vir K. Langtermyn verweringseksperimente wat gedoen is deur die onversteurde grond bloot te stel aan suurmynwater wys beduidende verwering en verandering van klei-minerale deur verbreding van die XRD pieke. Fourier transform infrarooi (FTIR) spektra is op kleimonsters van die verweerde grond gegenereer. Amorfe fases is bevestig deur gestruktureerde waterbindings met frekwensies tussen 3700 en 3300 cm−1 vir suurbehandelde grond. Metaal-vasleggings eksperimente is uitgevoer deur herhaaldelik die onversteurde grond aan die suurmynwater bloot te stel. Yster is die metaal wat hoofsaaklik in die grond vasgehou is. Metale soos Al, Mn, Na, K, Ca en Co was vrygestel in oplossing deur die grond. Die vrylating van Si deur die grond word geassosiëer met die oplossing van kleiminerale. Die onversteurde grond toon beperkte vermoë om suur te neutraliseer en metale te bind in die grond wanneer dit met suurmynwater geloog word. Metale was hoofsaaklik ge-ekstraëer in die wateroplosbare fase vir die langtermyn verweringsbehandelings. Aluminium was die mees mobiele fraksie wat ontrek is van die water oplosbare fraksie (2035 mg/kg). Uituilbare en suuroplosbare fraksies het nie ‘n groot hoeveelheid metale vasgehou nie. Gronde wat versamel is naby die prosesseringsdam het die hoë konsentrasies vanFe (21175 mg/kg) en Si (3070 mg/kg) in die gereduseerde fraksie gehad. Die reduserende fraksie het ook die hoogste konsentrasie van Cr (15.85 mg/kg), Cu (41.53 mg/kg), Pb (8.0 mg/kg) en Zn (10.65 mg/kg) gehad in vergelyking met ander fraksies in die grond. Vir die beheer eksperiment was die konsentrasie van Cu (77.3 mg/kg), Pb (10.8 mg/kg) en Zn (24.1 mg/kg) hoër as in die besoedelde grond en laer vir Cr (6.05 mg/kg). Dus kan daar van hierdie eksperimente afgelei word dat die onversteurde grond beperkte kapasiteit het om swaar metale in grond vas te hou in die nie-biobeskikbare fraksie. As gevolg van die aard van die suurmynwater, is die grond nie voldoende om die metale effektief in grond te behou nie. Die bevindinge van hierdie studie dui daarop dat die kapasiteit van die ongerepte grond om pH te buffer en metale in grond te behou baie beperk is. Dit kan toegeskryf word aan die lae kleiinhoud, lae konsentrasie van sekondêre karbonate en die lae pH van die grond. Die loging van suurmynwater van die logingsdam is dus nie gereguleer deur die gronde nie en stel die naasliggende waterbronne in gevaar.

The exploitation of metallic sulfide ores produces vast quantities of fine-grained wastes hosting potentially toxic elements (PTEs). There are concerns that, if improperly disposed of and managed, waste mineral particles can behave as vectors that disperse PTEs via aeolian and fluvial transport, subsequently contaminating soils and crops used to support human populations. The importance of these particles, as sources and influencers of PTE biogeochemistry in productive soils, has received limited research. Long-term (365 d) batch incubation experiments, field weathering experiments and phytoavailability trials, were performed to establish the rate, patterns and factors limiting PTE (Cd, As, Hg) release from grains of sphalerite (Zn(Fe,Cd)S), arsenopyrite (FeAsS) and cinnabar (HgS) into soil matrices (0.1 % mineral:soil m/m), and the bioavailability of the liberated PTEs to important food crops (Tricitum aestivum, wheat and Oryza sativa, rice). All three of the ores underwent chemical weathering in oxic agricultural soils of both temperate and sub-tropical provenance, during which nonessential PTEs (cadmium, mercury, arsenic) were released in bioavailable forms, at rates relevant to agricultural production. Sphalerite weathered at a rate of 0.6 to 1.2 % a-1 (Cd basis) in the experimental soils, releasing 0.5 to 1 μmol Cd g-1 ZnS a-1 into the soil matrix. Cinnabar weathering reached a maximum of 12.0 – 13.5 % (Hg basis) after 90 days exposure in oxic soils, whereas arsenopyrite weathering was rapid and extensive, reaching 56 to 66 % (S basis) after 180 days. The PTE concentrations accumulated in edible grains of wheat and rice grown in the sulfide-contaminated soils were higher than international food safety limits by factors of 8 (Cd in rice), 10 – 30 (Hg in wheat and rice) and 8 – 12 (As in wheat and rice). The primary geochemical factors controlling PTE release and bioavailability were solid-phase associations (i.e. PTEs complexed by clays, metal oxyhydroxides and organic matter) and the precipitation of secondary mineral phases. Weathering arsenopyrite grains were passivated from further oxidation by secondary iron-arsenate phases, which also co-precipitated arsenic liberated from the ore. Secondary phase formation was identified as the cause of decreasing extractable Hg (liberated from cinnabar) after mercury release from cinnabar peaked (≤ 90 days exposure). For sphalerite, the evidence indicates that secondary sulfide phases formed under flooded (sulfate-reducing) soil conditions (paddy rice), limited the bioavailability of cadmium previously liberated under oxic conditions. These key findings demonstrate a potential human health hazard relating to the dispersal of PTE-hosting sulfide ore particles produced by mining activities into soils supporting human populations via crop contamination. This work also highlights differences in ore geochemistry, showing the need for additional research on different ore minerals and their alteration products.

Manmade climate change has expressed a plethora of complex effects on Earth's biogeochemical compartments. Climate change may also affect the mobilisation of natural metal sources, with potential ecological consequences beyond mountains' geographical limits; however, this question has remained largely unexplored. We investigated this by analysing a number of key climatic factors in relationship with trace metal accumulation in the sediment core of a Pyrenean lake. The sediment metal contents showed increasing accumulation trend over time, and their levels varied in step with recent climate change. The findings further revealed that a rise in the elevation of freezing level, a general increase in the frequency of drier periods, changes in the frequency of winter freezing days and a reducing snow cover since the early 1980s, together are responsible for the observed variability and augmented accumulation of trace metals. Our results provide clear evidence of increased mobilisation of natural metal sources - an overlooked effect of climate change on the environment. With further alterations in climate equilibrium predicted over the ensuing decades, it is likely that mountain catchments in metamorphic areas may become significant sources of trace metals, with potentially harmful consequences for the wider environment.

Chemical weathering reactions are important for the physical, chemical, and biological development of the critical zone. We present findings from aqueous phase chemical analyses of surface and soil pore waters during a 15 month study in a small semi-arid mountain catchment of the Santa Catalina Mountain Critical Zone Observatory. Stream water geochemical solutes are sourced to two distinct locations - fractured bedrock baseflow stores and soil quickflow stores. Solid phase observations of albite, anorthite, and K-feldspar transformation to Ca-montmorillonite and kaolinite are supported by stream water saturation states calculated via a PHREEQC geochemical model. While differences in mineral assemblages, soil depths, and horizonation suggest greater weathering in schist versus granite lithologies and in hillslope divergent versus convergent zones, soil pore water solute ratio analysis does not readily distinguish these differences. However, preliminary investigation of aqueous rare earth elements suggests detectable lithologic and landscape positional differences warranting focus for future research efforts.

Electrical Resistivity Tomography (ERT) is a novel technique which can be used to build up a 2D pseudo-section of resistivity distribution of a porous material. Here, it is used to visualise internal moisture regimes by measuring the resistivity distribution of transects within sandstone, inferring that high resistivity equals low moisture content and vice versa. This method was used to perform two intermediate complexity laboratory tests; the first one to determine high-resolution, multi-scale drying patterns of sandstone, the second to determine capillary ingress of moisture within a sandstone block and the influence of temperature on moisture distribution. It was found that moisture behaviour showed far more complex patterns than previously acknowledged. A new model is therefore proposed which describes the influence of increased near-surface temperatures on capillary rise. This series of tests bridge the gap between field observations and mathematical models, as well as confirm the validity of ERT as a geomorphological tool. This research was continued by investigating the role of internal moisture in sandstone weathering using the Golden Gate Highlands National Park (GGHNP), South Africa as a case study. The ERT data was correlated with Equotip (rock surface hardness) and Protimeter (rock surface saturation) measurements. Seven sites were investigated, which showed that there is a non-linear correlation between rock surface hardness and internal moisture patterns. In addition, annual change measurements confirmed that the fluctuating patterns of internal moisture can be correlated to strengthening or weakening of the rock surface. This research therefore proposes two new conceptual weathering models. The first correlates ‘optimal moisture content’ to rock surface strength. The second correlates the development of shelters and changing weathering patterns to the non-linear interaction between case hardening and internal moisture. This new approach to sandstone weathering can be incorporated into conservation methods, as rock surface loss is one of the main causes of the San Rock Art deterioration observed in the GGHNP.

In many events affecting our civil infrastructure, such as contamination or weathering, it is likely that only the surfaces of the affected building materials will be available for non-destructive measurements. In this work, we describe and analyze surface gas permeability measurements on a variety of natural and engineered building materials using two types of relatively new, non-destructive surface permeameters. It is shown that the surface gas permeability measurements correlate well with each other and could provide rapid estimates of macroscopic gas permeability and degradation of materials due to weathering. It is hypothesized that surface permeability can be used to predict macroscopic wicking of water. The results indicated that macroscopic wicking correlated reasonably well with surface permeability measurements of uniform materials with low permeabilities such as sandstones and clay brick.