Existing estimates of carbon fluxes for Australia primarily rely on process-based terrestrial ecosystem model simulations. Even though they are built to consider important ecosystem processes that control the exchange of CO2 between the land surface and the atmosphere, such as the connection between carbon uptake and water use by plants, their carbon flux exchange estimates are highly uncertain. Improving carbon flux estimates from global ecosystem models and its uncertainties is essential for advancing our understanding of the Earth system and carbon cycle-climate feedback. This dissertation contributes to solving this challenge through atmospheric data assimilation, also known as inverse modelling. The main structure of this thesis consists of three studies. The first study involved running a series of simulation experiments (OSSEs) to assess the potential of the Orbiting Carbon Observatory-2 (OCO-2) satellite retrievals to reduce the uncertainties in CO2 fluxes over Australia for 2015. In this study, we assumed that most of the uncertainties in the Australian carbon fluxes were driven by the net primary productivity estimated by the CABLE land surface model (Australian land biosphere model). After performing OSSEs, we found that Australian carbon flux uncertainties can be reduced by up to 90 percent at a grid-point resolution over productive ecosystems. Given that the first study showed promising results about the potential of OCO-2 data to constrain fluxes around Australia, the second study focused on the quantification of CO2 sources and sinks over the continent. The main results of this study suggest that Australia acted as a carbon sink of -0.41 +- 0.08 PgC/y compared to the prior estimate 0.09 +- 0.2 PgC/y (excluding fossil fuel emissions). Analysis of the seasonal variation of the posterior CO2 fluxes aggregated by bioclimatic regions shows that the savannas in northern Australia and the sparsely vegetated ecosystem in central Australia were the primary drivers of stronger carbon uptake in 2015. Examination of the enhanced vegetation index (EVI) indicates that the primary reason for the stronger posterior carbon uptake (relative to the prior) registered over the savanna ecosystem was due to an increase of vegetation productivity (positive EVI anomalies) caused by an anomalous increase of rainfall in summer period. Additionally, we found that a slight increase of carbon over areas with sparse vegetation (the largest ecosystem by area in Australia), was also driven by a slight increase in land productivity and had a substantial impact on the Australian carbon budget for 2015. Underestimation of the gross primary productivity flux simulated by the CABLE model over the savanna and sparsely vegetated ecosystem was also a contribution of why OCO-2 lead to a stronger carbon estimate in 2015. The final study was built upon the second study and focused on understanding the Australian carbon flux variability from 2015-2019 and evaluating how Australian semi-arid ecosystems responded to changes in rainfall and temperature anomalies. This study suggests the 2015 carbon sink's size over Australia increased in 2016 due to increased vegetation productivity in this period. Australia's 2016 carbon uptake contributed almost all the long-term mean terrestrial sink estimated for 2015-2019 (-0.33 +- 0.09 PgC/y). The ecosystems that most contributed to this carbon sink were savanna and sparsely vegetated regions driven by a higher than expected greenness in vegetation (expressed by positive EVI anomalies) strongly influenced by positive rainfall anomalies and negative air temperature anomalies.

Australia is a seismically active continent with an intraplate compressive stress field primarily driven by far-field plate boundary interactions. Major (magnitude >= 5) surface-rupturing earthquakes are primarily sourced from reverse faults. Major earthquakes perturb local-to-regional stress fields and influence the spatiotemporal properties of subsequent earthquakes. This thesis first contextualizes Australian earthquakes against global comparatives by investigating 260 finite-fault rupture models for 137 moment magnitude (Mw) 4.1 to 8.1 continental earthquakes worldwide. I find that: (i) Australian earthquakes are amongst the most kinematically and geometrically complex for their Mw, (ii) upper-bounds and variance of the number of faults that rupture co-seismically increase with increasing Mw, and (iii) multi-fault rupture populations show no dependency on strain rate or proximity to plate boundaries. The thesis then presents a suite of studies that model static and viscoelastic coulomb stress changes (dCFS) imparted by major Australian earthquakes on to receiver faults and in the surrounding crust. I find that static dCFS models provide an informative physical-statistical basis for characterising many seismic sequences in Australia, with some exceptions. Aftershocks occur predominantly within positive static stress lobes and close to the advancing viscoelastic positive stress lobes, especially over the first few decades after major earthquakes in these regions. Earthquake triggering appears to occur under stress perturbations as small as approx 0.001 to 0.01 bar, suggesting cratons contain regions of critically stressed lithosphere. The effects of varying source fault geometries and kinematics on dCFS fields and subsequent seismicity are used to show how progressive refinement of source fault models using emergent data can reduce epistemic uncertainties in the role of dCFS in earthquake triggering. In some instances, increased source model complexity does not significantly impact on dCFS results and possible relationships to aftershocks relative to simple source models. The thesis finally investigates the role of lithospheric-scale flexural bending due to eustatic sea level changes, and whether these impart dCFS perturbations on finite faults and in regions similarly to stresses imparted by preceding earthquakes. Preliminary age distributions of large paleo-earthquakes on these reverse faults are concurrent with dCFS peaks imparted by eustatic sea-level changes. dCFS of > 0.1 to > 1 bar on faults during the low-stand Marine Isotope (MIS) Stage 2 to Stage 4 interval (ca. approx 30 to approx. 70 ka) provides tentative evidence that earthquake clusters could be stimulated by sea-level lowstands. This thesis demonstrates the power and utility of dCFS modelling to improve understanding of intraplate earthquakes.

In order to meet the Paris Agreement and pursue efforts for a 1.5 degrees Celsius target, the electric power system worldwide must undergo a fundamental transformation as the main pillar for decarbonisation. The decarbonisation will almost certainly be driven largely by the massive adoption of variable renewables. The objective of this PhD project is to develop a co-optimisation model with the ability to perform comprehensive analysis to simultaneously explore the least-cost configurations of generation, storage and transmission over large geographic regions to facilitate the transition to a low carbon power system. Although applicable to any region, the capacity expansion model we developed focuses on Australia’s National Electricity Market. The capacity expansion calculated by the model satisfies prescribed demand projections and emission abatement targets from 2020 to 2050, subject to constraints including resource adequacy, system inertia and reliability, unit commitment, economic dispatch and transmission capacity. The model also takes into account the decommissioning of the existing fossil fuel generation fleets and explores a great range of renewable generation and storage options. The transmission model employs a Direct Current power flow approximation with 21 major load centres over the eastern states of Australia. We have used the model to examine various carbon abatement scenarios for Australia. We show that wind turbines and solar PV technologies combined with pumped hydro energy storage dominate the solutions, and that gas is unlikely to be a transition fuel towards a 100% renewable system by 2050. The 100% renewables systems simulated are not only technically feasible but also economically achievable. Australia’s vast wind and solar resources become increasingly valuable assets as the world decarbonises. Not only does this study consider meeting local requirements for electricity demand, but also the potential for export of green energy. Our research confirms the very real and great potential for Australia to produce cost-competitive hydrogen. In the pathways to carbon neutrality, we demonstrate there are substantial synergies between renewable hydrogen export and domestic energy transition in Australia. In particular, we show if the hydrogen industry co-locates within the National Electricity Market with shared renewable generation facilities (i.e. sector coupling), not only can the hydrogen industry produce cost-competitive hydrogen, but also that domestic electricity consumers could enjoy lower electricity costs, thereby benefiting the whole economy in the long run. Besides hydrogen export, we also conducted the first detailed least-cost optimisation studies of power system decarbonisation planning for both Australia and Indonesia that considers HVDC interconnections. We show direct electricity export to Indonesia could also benefit Australia’s domestic energy transition as any wind and solar energy not used by Indonesia could then be fed to the National Electricity Market. This could help both countries to achieve decarbonisation. Overall, our modelling suggests that a long-term system-wide perspective and orientation are critical for the design of energy policies that can secure broad energy system benefits. If planned well, Australia could become a major supplier of green hydrogen, direct renewable electricity and energy-intensive products as energy vectors in the global market. Particularly, this could be driven and strengthened by a robust commitment to “net-zero by 2050”.

Speleothems are valuable archives recording information on past climates and processes of landscape evolution. In fact, the high preservation potential of speleothems and their ubiquity across the globe are key attributes and speleothems are now extensively used in palaeoclimate modelling as complements to the more traditional marine and ice core climate records. The real ’engine’ of speleothems science, however, lies in the ability to reliably and robustly place these archives into chronological context. Historically this has been facilitated by the highly successful U-Th geochronometer, which can accurately date speleothems that formed within the last 650 thousand years. However, many speleothems – and by extension their proxy archives – are far older than this 650 ka limit and so require a significantly longer-lived radiometric methodology: the U-Pb geochronometer has recently filled this void. The U-Pb geochronometer is well known in the geological sciences, but its application to the analytically-challenging medium of speleothems has been relatively recent. Modern mass spectrometry methods now allow the accurate and precise analysis of the extremely low-levels of U and Pb within speleothems, thus providing access to such ’deep-time’ (i.e. multi-million years and further) palaeoclimatic and landscape evolution archives. Despite these significant advances, there remain fundamental impediments to the whole-scale production of speleothem U-Pb ages. This thesis investigates some of these shortfalls with the ultimate aim of advancing the speleothem U-Pb methodology and application such that future speleothem-based studies may more rapidly and more reliably place their reconstruction models into a more robust chronology. The first half of this thesis addresses two fundamental limitations of the speleothem U-Pb method: the large expenditure of time and effort required for producing calcite U-Pb ages, and the potential limitations in the correction for initial isotopic disequilibrium effects in the U-Pb decay chain. To address the former, I provide new software for the rapid production of publication-quality U-Pb isochron figures and ages. Additionally, a new chemical separation (i.e. chromatography) procedure for generating high-purity U and Pb fractions is developed. This new ’stacked resin’ protocol can produce mass spectrometry-ready U and Pb sample aliquots in a single working day – roughly half the time of the previous method – and so accelerates the acquisition of U-Pb ages. In terms of subsequent data deconvolution, the largest hurdle to obtaining accurate speleothem U-Pb ages arguably relates to the uncertainty added from having to estimate an initial isotopic disequilibrium value after the system has returned to equilibrium. As a potential remedy to this problem, this research program develops a framework in which to calculate appropriate disequilibria values for the production of disequilibrium-corrected U-Pb ages. The second part of this thesis is designed to highlight new applications of the calcite U-Pb chronometer made possible by the methodological advances documented in the first half. This research program investigates the utility of speleothems as proxies for regional uplift rates in karst terranes. This is accomplished by producing chronologies for 120 speleothems from the Buchan karst along southeast Australia’s passive margin. The results of this study indicate that SE Australia experienced a renewed period of uplift occurring at a maximum rate of 76 +/- 7 m / Ma beginning at least 3.5 million years ago. This speleothem-derived uplift rate is consistent with other independent regional uplift estimates thus adding credibility to the utility of speleothems as proxies for uplift. The relatively straight-forward method developed here is likely applicable in many future karst studies. Additionally, this research program also investigated the potential applicability of U-Pb geochronology to another form of carbonate archive – stromatolites. The methodological advances described in this thesis were applied to stromatolites from Lake Turkana, Kenya, and the palaeo-lake Bungunnia in southern Australia. The results of this experiment suggest that stromatolites contain too much inherited Pb that simply overwhelms the radiogenic ’age signal’ and so are unlikely to be successful candidates for U-Pb dating, at least for stromatolites formed during much of the Cenozoic period.

This thesis explores relationships between the structure, rheology, and rupture properties of seismogenic faulting in continental lithosphere from four different perspectives. First, I derive a scaling relationship that links the spacing between two nearly parallel strike-slip faults to the frictional strength, fault width, and lower crust viscosity for strike-slip shear zones. Based on the scaling law, I estimate a possible range of lower crust viscosity in the San Andreas Fault system (California), the Marlborough Fault Zone (New Zealand) and central Tibet (China). Second, using numerical modelling methods, I explore how lower crust rheology contrast may affect the long-term evolution of a major plate boundary fault. The case study is based on the San Andreas Fault, which is found to vary dipping angles (~50-90 degree) along strike. The moderately dipping strike-slip fault is not consistent with Anderson faulting theory. This inconsistency may be reconciled if there are lateral variations in the lower crustal rheology across the fault plane that decrease fault dip with time. Third, in addition to strike-slip faults in active tectonic settings, my study also includes reverse faults in stable cratonic regions, especially for the cratonic areas of western and southern Australia. I apply statistical methods to investigate the co-seismic slip distribution of 11 surface-rupturing earthquakes in Australian stable regions and provide a link between the shape and characteristics of co-seismic slip distributions and the geophysical properties of the host crust. Fourth, using a comprehensive geophysical survey with the co-located 13GA-EG1 and 12GA-AF3 seismic reflection profiles and magnetotelluric profiles and regional gravity and magnetic maps in the Nullarbor Plain (Australia), I find that faults initiated back to the Proterozoic could still be reactivated in a Cenozoic convergent setting, especially for those major faults cutting to deep crust. Those deep-penetrating faults at terrane boundaries could be a potential channel for fluids to pass through, and thus further weakened by the fluids, which is revealed by high-conductivity anomaly in magnetotelluric profiles. The last research chapter of this thesis addresses a technical issue in the particle-in-cell finite element method, which is widely used in geodynamic numerical modelling. As mixing materials with contrasting viscosity within one element results in stress fluctuations, I assess different smoothing methods to reduce the spurious stress in mixed-material elements.

For over 100 years the genus Monostychia (Echinoidea: Clypeasteroida) and its type species M. australis Laube, 1869 have been a taxonomic home for a wide range of genera and species with the commonality of a rounded to pentagonal, discoidal test and a submarginal periproct. The specimens comprising this group are all extinct and from the Tertiary strata of southern Australia. While there have been a few minor species identified beyond M. australis, notably M. etheridgei Woods, 1877 and P. loveni (Duncan, 1877), it has been clear to many researchers that the variability remaining in M. australis was representative of numerous other taxa awaiting discovery. Recent taxonomic works on the Clypeasteroida suggested that the number of interambulacral plates on the oral surface of the test of some species was a useful diagnostic character. Of interest were the plates that first come into contact with the periproct. However, there appeared little evidence in the literature that it had been established that the number of such plates remained constant with test length and age, or that the variability in each taxon, of those plate numbers, has been determined. Without understanding those two issues the utility of plate numbers was questionable. This study set out to resolve some of those issues for Monostychia and its relatives. It was found that the number of interambulacral and ambulacral plates on the oral surface was fixed and did not change with increasing test length and therefore there was potential utility for plate numbers as a taxonomic tool. However, there was substantial variability in the numbers. As a result, the use of plate numbers in the paired interambulacra, paired ambulacra, and ambulacrum III on the oral surface appears to have limited utility at genus level. At the species level, however, such numbers can be quite useful diagnostically, particularly when paired interambulacral, paired ambulacral and ambulacrum III plate numbers are used in combination. The plates that first come into contact with the periproct was shown to have little value taxonomically at the genus or species level within the monostychioids, largely because most species had the same plate number dominating, but also because of the variability. At subfamily level the taxonomic value of this feature is yet to be established. A previously unreported structural feature was identified in many of the specimens. This was a thin circumferential wall of stereom present on the right-hand side of the test, lying half way between the marginal and central buttressing. It was a form of intestinal buttressing referred to hereafter as the intermurum. Its presence enabled the establishment of a new subfamily, Monostychinae in the family Arachnoididae. Four genera have been placed in the Monostychinae; Monostychia Laube, 1869, Quinquestychia gen. nov., Rotundastychia gen. nov. and Deltoidstychia gen. nov. A key to these genera is provided. Several species have been established and others redescribed in this study. In Monostychia there are seven species; M. australis Laube, 1869, M. macnamarai Sadler et al. 2017, M. alanrixi Sadler et al. 2017, M. merrimanensis Sadler et al. 2019, M. etheridgei Woods, 1877, M. glenelgensis Sadler et al. 2019 and M. robheathi sp. nov. A new genus, Quinquestychia gen.nov., has also been established. It contains four species: Q. mannumensis sp. nov., Q. gigas sp. nov., Q. berylmorrisae sp. nov. and Q. robertirwini (Sadler et al. 2017). The last of these species was published as a Monostychia earlier in this study but reassigned later on the basis of further data. A second new genus, Rotundastychia gen. nov., has also been established. It contains three species: R. pledgei sp. nov., R. aquilaensis sp. nov. and R. eyriei sp. nov. A third new genus, Deltoidstychia gen. nov., has also been established. It currently contains a single species, D. erioaster sp. nov. In addition to the above, two other new genera were established but they do not belong in the subfamily Monostychinae. Instead they are tentatively placed in the subfamily Ammotrophinae. The first of these is Obscurostychia gen. nov. with two new species: O. spirographica sp. nov. and O. curtus sp. nov. Keys to all the genera discussed above that contain more than one species have been provided.

Throughout the world, ancient rock art records some of the earliest attempts at complex human communication. However, constraining the age of older rock art has remained a largely intractable scientific problem thereby limiting our ability to integrate rock art into the rest of the archaeological record. Researchers have studied the globally significant Aboriginal rock art in the Kimberley region of Western Australia for more than 40 years and have comprehensively documented a sequence of rock art stylistic periods. It has long been thought that the oldest styles in this sequence date back to the Pleistocene but only two such dates, relating to identifiable motifs, have been published and both are problematic. The surviving pigment in paintings of all but the most recent Kimberley rock art style contains no material that can be radiometrically dated. There are, however, mineral accretions and mud wasp nests in the same Kimberley rock shelters that house rock art and, occasionally, these under or overlie paintings. This study explores the development of radiocarbon dating techniques to reliably date remnant mud wasp nests found to be in contact with rock art. Recently constructed mud wasp nests were collected and analysed to understand the source and age of carbon-bearing material they contain. Unburned plant material and charcoal were found in similar volumes, but charcoal is the carbon-bearing constituent most likely to provide a reliable radiocarbon age for old nests. Old wasp nests were analysed using a wide range of techniques to determine how taphonomic processes alter their physical and chemical composition. These results guided experimentation with pretreatment methods designed to remove sources of carbon contamination while preserving as much of the carbon in the original charcoal as possible. A total of 120 old mud wasp nests were prepared for radiocarbon dating of which 75 contained sufficient carbon for measurement. The distribution of the 75 ages indicated nests were built quasi-continuously over, at least, the last 20,000 years. The motifs in contact with the 75 nests were classified into one of the six main Kimberley rock art stylistic periods by two subject matter experts. Just 3 nests overlay motifs from each of the Cupules and Wanjina periods suggesting only that some motifs in these styles are older than 7,200 years and 500 years, respectively. The 4 dates available for each of the Static Polychrome and Painted Hand periods permit a very tentative hypothesis for their chronology while the 16 dates relating to Irregular Infill Animal Period (IIAP) motifs and the 20 dates for Gwion motifs provide a more secure estimate. The concise hypothesis proposed for the chronology of the Kimberley rock art styles is that the IIAP style was in use from at least 17,000 to 13,000 years ago. It was followed by the Gwion period from 13,000 – 12, 000 years ago and then the Static Polychrome period 11,000 to 9,000 years ago. The Painted Hand period followed at around 8,500 to 9,000 years ago.

Lithological heterogeneity at mm- to cm-scale exists in the form of sedimentary structures such as cross bedding and planar bedding in heterogeneous siliciclastic reservoirs. At this scale, sedimentary structures typically consist of two lithologies with significant differences in their porosity, permeability, capillary entry pressure and mineral composition. The lithology with high porosity, high permeability, low capillary entry pressure and a high abundance of quartz and feldspar characterizes the reservoir rock and is conducive to fluid flow. On the other hand, the lithology with low porosity, low permeability, high capillary entry pressure and a high abundance of clay and carbonate minerals characterizes the intraformational baffle and acts as flow barrier. The presence of both lithologies at mm- to cm-scale govern local fluid flow and geochemical reactions. This is especially important in CO2 storage reservoirs where CO2 flow and mineralization might be significantly affected. Hence, it is necessary to account for lithological heterogeneity at sub-meter scale in regional scale dynamic simulations. However, intraformational baffles are typically neglected in static reservoir models primarily because small scale intraformational baffles are not commonly resolved by wireline logs. Therefore, their lithological properties are not accounted for in reservoir models. This study addresses the characterization and incorporation of intraformational baffles in reservoir models so that the reservoir scale estimation of carbon mineral trapping capacity can be improved. Firstly, rocks from the CO2CRC’s Otway Research Facility were characterised using a range of sample and data analysis methods. The variability in porosity, permeability, capillary entry pressure, grain size and mineral composition was used to classify five homogeneous rock type classes: coarse sandstone, fine sandstone, siltstone, mudstone and carbonate-cemented sandstone. A new workflow was developed where homogeneous rock types and composite rock types consisting of two lithologies characteristic of intraformational baffles were represented. Rock properties for composite rock types were derived so that mm-scale heterogeneity can be upscaled for integration in coarser discretised reservoir models. Lithotype logs of composite rock types were derived and used to build a high resolution 2D static reservoir model of the site. Multiphase fluid flow and reactive transport simulations were run on 120 and 8 realizations, respectively, to develop a detailed understanding of CO2 flow and geochemical reactions at mm-scale. It was found that the capillary entry pressure characteristic of the reservoir rock significantly governed the range of turning point saturations while the amount of clay and carbonate content of the baffle governed the amount of carbon mineralized. Reactive transport simulations were also run on two 2D reservoir models to quantify the error associated with the estimation of carbon mineral trapping at reservoir scales if intraformational baffles are not accounted for in dynamic simulations. The results show that the neglection of intraformational baffles in reservoir rocks might lead to an underestimation of mineral trapping capacity by nearly 2.5 times.

A major uncertainty in future projections of tropical cyclone (TC) frequency is due to inadequate understanding of the atmospheric mechanisms leading to a reduction in the TC formation in warmer climates. Although the recently proposed “marsupial pouch theory,” of TC formation indicates that a semi-enclosed recirculating region known as a “pouch” within large-scale disturbances provides necessary conditions for TC formation, it is important to link the frequency of the pouch environments to the evolving climate conditions. Therefore, this thesis examines the changes in the marsupial pouch TC formation environments and their relationship to the large-scale environmental conditions in the current climate and idealized warmer climates. Here we use ERA-interim reanalysis data and high-resolution Australian Community Climate and Earth-System Simulator (ACCESS) climate model simulations of the current climate and idealized warmer climates (aqua-planet simulations) with two fundamentally different TC tracking schemes. The first scheme is the Okubo-Weiss Zeta Parameter (OWZP), a phenomenon-based tracking scheme that detects TC-favorable locations within marsupial pouches using resolution-independent thresholds. The other scheme is the Commonwealth Scientific and Industrial Research Organization (CSIRO), a traditional TC tracking scheme that uses resolution-dependent thresholds. Environmental and structural composite analysis of developing and non-developing tropical depressions (TDs) 48 hours before TD formation, which are detected using the OWZP scheme in the reanalysis, showed that developing circulations have a strong protective layer around the core from the lower to mid troposphere that protects it from external disruptive influences. The relative importance of the environmental variables influencing tropical storm (TS) formation varies across ocean basins due to differences in the large-scale disturbances and surrounding environmental conditions. Statistical TS prediction schemes are also developed using the environmental conditions of developing and non-developing TDs. This analysis notes that random forests and support vector machine algorithms have higher accuracy than decision trees (DTs). Additionally, the hybrid approach of DTs and Markov decision process is proposed which indicates that developing TDs have a higher likelihood of remaining in more favorable environmental conditions than non-developing TDs. In current climate simulation using the climate model, the TCs detected within marsupial pouches are a subset of the traditionally detected TCs. Also, the OWZP scheme performs better in representing the TC frequency statistics and has stronger relationships with the surrounding environmental conditions in the current climate than the CSIRO scheme. In idealized aquaplanet model simulations, we observe both reduced marsupial pouch environments and traditionally detected TCs with increasing sea surface temperatures (SSTs). The increased saturation deficit and increased stability explain the reduction in the frequency of formations with increased SST. The present study also notes a decrease in the frequency of low-intensity storms and an increase in the frequency of intense storms with increasing SSTs. In a drier and more stable atmosphere, the initial vortices need to be stronger for TC formation to occur, with higher low-deformation vorticity and higher upward mass flux. This research indicates that the marsupial pouch theory may be a fundamental paradigm of TC formation due to its better relationships with the large-scale environmental conditions in different climates.

Dimethyl sulfide (DMS) is a naturally occurring aerosol precursor gas which plays an important role in the global sulfur budget, aerosol formation and climate. While DMS is produced predominantly by phytoplankton, recent observational literature has suggested that corals and their symbionts produce a significant amount of DMS, which is currently unaccounted for in modelling studies. It has further been hypothesised that the coral reef source of DMS may modulate the climate. In this thesis, two atmospheric models coupled to online chemistry and aerosol schemes were used for the first time to explore the influence of coral reef-derived DMS on atmospheric composition and meteorology across temporal and spatial scales. A simple non-varying representation of coral reef-derived DMS was developed and added to a common DMS surface water climatology. By comparing the differences between simulations with and without coral reef-derived DMS, the role of coral reef-derived DMS was quantified. The Australian Community Climate Earth System Simulator coupled to the United Kingdom Chemistry and Aerosol model (ACCESS-UKCA) was used to quantify the influence of coral reefs at the global scale. ACCESS-UKCA was evaluated against satellite observations and other global climate models and the sensitivity of aerosol, clouds and radiation to large scale perturbations of DMS was tested. ACCESS-UKCA was found to have similar biases and DMS sensitivity compared to other models and it was estimated that marine DMS contributes 0.45K cooling to the present climate. The influence of coral reef-derived DMS on global to regional scale climate was then investigated. In the Maritime Continent-Australian region, where the highest density of coral reefs exist, a small decrease in nucleation and Aitken mode aerosol was found when coral reefs were removed from the system. However, these small responses were found to have no robust effect on global or regional climate. The Weather Research Forecast model coupled to the CBMZ-MOSAIC (Carbon Bond Mechanism Z - Model for Simulating Aerosol Interactions and Chemistry) chemistry-aerosol scheme (WRF-Chem) was then used to study the same question at higher spatial and temporal scales. WRF-Chem was run to coincide with an October 2016 field campaign over the Great Barrier Reef, Australia, against which the model was evaluated. After halving the DMS surface water climatology, the model performed well for DMS and sulfur processes, though aerosol number was overestimated. The inclusion of coral reef-derived DMS resulted in no compositional change in sulfate aerosol mass or total aerosol number. No direct or indirect aerosol effects were detected. Throughout this work, the complexities of the aerosol-climate system have been emphasised and the limitations of current modelling capabilities highlighted. In conclusion, while total marine DMS was found to have an important climatic influence, this thesis has found no robust link between coral reef-derived DMS and climate or weather. Thus, these results do not support hypotheses around the ability of coral reefs to modulate global or regional climate.

Oxidation reactions provide the fundamental mechanism for chemical cycling of atmospheric constituents. Understanding the key chemical and meteorological factors determining atmospheric oxidation chemistry has important implications for air pollution and climate change. With strong but isolated urban pollution sources and endemic plants known to emit high levels of volatile organic compounds (VOCs), Australasia is a fascinating place to study atmospheric oxidation chemistry in a range of remote, coastal and urban environments. To date however, Australia is vastly under represented in the observational atmospheric chemistry literature. In this thesis, the passive solar multi-axis differential optical absorption spectroscopic (MAX-DOAS) technique is used to study key molecules in the atmospheric oxidation cycle including nitrogen dioxide (NO2), formaldehyde (HCHO), nitrous acid (HONO), glyoxal (CHOCHO) and iodine monoxide (IO). In particular, the role of these molecules in forming hydroxyl radicals (OH) and ozone (O3), two key daytime tropospheric oxidants, is studied using urban measurements at Broadmeadows, Victoria and at Garden Island in Western Australia. In the first comprehensive study demonstrating the MAX-DOAS technique in Australasia, the technique is verified using a range of analysis sensitivity studies, inter-instrument comparison and validation against in-situ and remote sensing methods. This includes the first long term MAX-DOAS-satellite comparison in the Southern Hemisphere, where MAX-DOAS measurements were in excellent agreement with Tropospheric Monitoring Instrument (TROPOMI) results in Melbourne, Australia and at Lauder in New Zealand. The HONO observed at Broadmeadows was consistently at daytime concentrations exceeding what is expected given the known mechanisms. The maximum daytime HONO levels correlated with soil moisture levels indicating that soil-based emissions may play a role in the missing HONO source. The exponential dependence on temperature observed for HCHO at Broadmeadows suggests that the primary formaldehyde source there is oxidation of biogenic VOCs. In contrast, glyoxal appears to be more dependent on biomass burning or anthropogenic emissions. Chemical trajectory modelling studies at Garden Island suggest that isoprene oxidation is expected to be the dominant HCHO source, while anthropogenic emissions are expected to be the dominant CHOCHO source. At Broadmeadows, HONO photolysis was found to be the greatest boundary-layer OH source in all months, contributing on average between 45-50 % of OH production. HCHO and ozone (O3) were often present at sufficient levels in summer to be commensurate with HONO as surface OH producers. The vertical profiling capability of the MAX-DOAS technique showed that while HONO typically dominated the OH production close to the surface, ozone and formaldehyde photolysis were the dominant mechanisms at higher altitudes. At Garden Island, a background marine boundary layer level of IO was detected which did not appear to have a locally significant O3-destruction orOH-formation role, but nevertheless provide evidence of ubiquitous iodine chemistry in the marine boundary layer. Using the ratio of HCHO to NO2, significant VOC emissions on hot summer days (as indicated by high observed HCHO levels), were found to shift the ozone production regime from VOC-limited to NOx-limited. The ozone production regime was found to be mostly NOx-limited at Garden Island. This has important implications for air pollution, for while NO2 was not found in exceedance of guideline pollution levels, O3 smog could still be reduced on hot days by curbing nitrogen oxide emissions.

Continental flood basalts have been considered as an unconventional reservoir for geological carbon storage where vesiculated basalt intervals serve as reservoirs and massive basalt zones as a caprock. However, the presence of fractures in the massive layer may lead to CO2 leakage. The objective of this study is to understand the reactions of CO2-saturated fluid on fractured basalt and the respective changes in the fracture and adjacent connected pore network geometry at an early stage of the evolving geochemical system. Batch reaction experiments, high-resolution sample characterisation, and modeling are used to better evaluate basalts as CO2 storage reservoirs. The nature and extent of initial reactions between CO2-rich water and fractures including the connected pore network were determined. Reactions of CO2-saturated water with powdered massive (MB) and with vesicular basalts (VB) was studied at three different P/T conditions to understand the mobilisation of ions from crystalline basalt at far-from-equilibrium conditions. Reaction path modeling was undertaken for experiments involving MB to estimate the amount of dissolved and precipitated minerals. Mobilisation of ions was unexpectedly low at high experimental pressure and temperature conditions suggesting concurrent mineral precipitation, which was confirmed by the model. Secondary minerals formed a coating on the surface of the primary minerals, which controlled the primary mineral dissolution rate. The nature of secondary minerals was studied in a separate experiment involving basalt wafers at pressure and temperature conditions representing a depth of approximately 800 m. Mostly clay minerals and zeolites were observed at the surface of the wafers and in suspension, which agreed with the change in water composition. Certain clay minerals and zeolites were highly supersaturated based on the outlet fluid composition. Siderite (FeCO3) was close to equilibrium. The volume of dissolved and precipitated minerals was quantified in a third experiment using an artificially fractured basalt core at pressure and temperature conditions representing a depth of approximately 800 m. Net mineral precipitation occurred and the pore network structure changed, while only a very minor reduction in the net connected pore network volume was observed. These observations provide evidence for concurrent dissolution and precipitation processes leading to complex changes in the pore network geometry In conclusion, precipitation of secondary silicate minerals dominants at an early stage of CO2 -saturated water and basalt reaction and the presence of fractures in basalt enhances the geochemical reactions.