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Raman spectroscopy is widely used to examine the carbonate content within bone apatite, but Raman spectra are also sensitive to orientation effects between the polarisation of the incoming laser light and the sample orientation. This may lead to discrepancies when using Raman spectroscopy to evaluate the carbonate content as the extent of crystal organisation can change depending on the type of bone, age, and presence of mineralisation disorders in the organism. It is experimentally very challenging to evaluate the effect of orientation using individual bone crystals. Therefore, we have used density functional theory to examine the effect of orientation in apatitic materials. We examined hydroxyapatite and three different types of carbonated apatite: A-type where the carbonate ion substitutes the two OH groups in the unit cell, B-type where co-substitution occurs between carbonate in a phosphate position and Na+ for Ca2+ to maintain charge balance, and AB-type where carbonate sits in both A-site and B-site. Our simulations show that the OH group in hydroxyapatite has a strong orientation dependence, consistent with previous literature. In addition, the phosphate and carbonate bands of the apatitic structures are predicted to be orientation dependent, where the maximum scattering efficiency occurs in configurations in which the laser polarisation is parallel to the crystallographic axes of the material. The intensity changes of the phosphate and carbonate bands are not consistent upon changing orientations and thus may lead to an underestimation of carbonate contents if insufficient sampling points are used during bone analysis.

The origin of Precambrian iron-formations (IF) remains contentious, particularly with respect to the mineralogy of primary precipitates and the exact processes and conditions leading to their formation. Despite the uncertainties, prevailing hypotheses range from biological precipitation of ferrihydrite to abiotic water-column formation of greenalite. By contrast, iron carbonate minerals (siderite, ankerite) in IF have traditionally been attributed to diagenetic origins based on textural and isotopic relationships. Recent studies on IF from the Neoarchaean-Paleoproterozoic Transvaal Supergroup of South Africa have revealed evidence for apparently primary, low-δ13C, Fe/Mn-bearing Mg calcite as precursor to iron carbonate formation and as a potentially underestimated pathway of isotopically light carbon burial during IF deposition. Here, we present whole-rock δ13C data and carbonate-specific geochemical analyses for samples from five drill cores that capture the entire stratigraphic extent of the Kuruman and Griquatown IF of the Transvaal Supergroup. Our results demonstrate remarkable consistency in stratigraphic profiles among the locations for the trends and magnitudes of bulk δ13C values that are independent of paragenetic association, modal mineralogy, and chemical composition of the bulk carbonate fraction of each sample. We interpret these records as resulting from water-column abiotic carbonate formation that was accompanied by kinetic isotopic effects associated with fluctuating conditions (pH, alkalinity) controlling carbonate supersaturation in ambient seawater. Although our interpretation provides strong support for abiotic, anoxic models for IF genesis prior to the Great Oxidation Event (GOE), it does not entirely preclude additional biological mechanisms of primary ferric oxyhydroxide formation and its possible role in an early biological pump.

Well designed and optimized epitaxial heterostructures lie at the foundation of materials development for photovoltaic, photocatalytic, and photoelectrochemistry applications. Heterostructure materials offer tunable control over charge separation and transport at the same time preventing recombination of photogenerated excitations at the interface. Thus, it is of paramount importance that a detailed understanding is developed as the basis for further optimization strategies and design. Oxides of copper are nontoxic, low cost, abundant materials with a straightforward and stable manufacturing process. However, in individual applications, they suffer from inefficient charge transport of photogenerated carriers. Hence, in this work, we investigate the role of the interface between epitaxially aligned CuO and Cu 2O to explore the potential benefits of such an architecture for more efficient electron and hole transfer. The CuO/Cu 2O heterojunction nature, stability, bonding mechanism, interface dipole, electronic structure, and band bending were rationalized using hybrid density functional theory calculations. New electronic states are identified at the interface itself, which are originating neither from lattice mismatch nor strained Cu-O bonds. They form as a result of a change in coordination environment of CuO surface Cu 2+ cations and an electron transfer across the interface Cu 1+-O bond. The first process creates occupied defect-like electronic states above the valence band, while the second leaves hole states below the conduction band. These are constitutional to the interface and are highly likely to contribute to recombination effects competing with the improved charged separation from the suitable band bending and alignment and thus would limit the expected output photocurrent and photovoltage. Finally, a favorable effect of interstitial oxygen defects has been shown to allow for band gap tunability at the interface but only to the point of the integral geometrical contact limit of the heterostructure itself.

The photochemical evolution of polycyclic aromatic hydrocarbons (PAHs), an abundant form of meteoritic organic carbon, is of great interest to early Earth and Mars origin-of-life studies and current organic molecule detection efforts on Mars. Fe-rich clay environments were abundant on early Earth and Mars, and may have played a role in prebiotic chemistry, catalyzing the breakdown of PAHs and freeing up carbon for subsequent chemical complexification. Current Mars is abundant in clay-rich environments, which are most promising for harboring organic molecules and have comprised the main studied features by the Curiosity rover in search of them. In this work we studied the photocatalytic effects of the Fe-rich clay nontronite on adsorbed PAHs. We tested the effect of ultraviolet radiation on pyrene, fluoranthene, perylene, triphenylene, and coronene adsorbed to nontronite using the spike technique, and in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in a Mars simulation chamber. We studied the infrared vibrational PAH bands with first order reaction kinetics and observed an extensive decrease of bands of pyrene, fluoranthene, and perylene, accompanied by the formation of PAH cations, while triphenylene and coronene remained preserved. We further analyzed our irradiated samples with nuclear magnetic resonance (NMR). Our study showed certain PAHs to be degraded via the (photo)Fenton mechanism, even under a dry, hypoxic atmosphere. Using solar spectra representative of early Earth, early Mars, and current Mars surface illumination up to 400 nm, the processes occurring in our set up are indicative of the UV-induced photochemistry taking place in Fe-rich clay environments on early Earth and Mars.

Calcium carbonate and cadmium-rich fluid interactions have been studied at the nano and microscale with fluid flow and static fluid conditions for three forms of CaCO3: calcite in single crystals of Iceland Spar, calcite in a polycrystalline Carrara marble, and aragonite single crystals. Atomic Force Microscopy (AFM) showed the nanoscale effect of cadmium on CaCO3 dissolution and growth under flow-through conditions at ambient temperature, with the modification of calcite dissolution behaviour and simultaneous precipitation of a Cd-rich phase on all the different samples. Hydrothermal experiments at 200°C revealed that the reactivity of single calcite crystals is passivated by epitaxial growth of the less soluble Cd-rich endmember of the (Ca,Cd)CO3 solid-solution on the sample surface due to the similar crystallographic structures of calcite and otavite (CdCO3). Conversely, the presence of grain boundaries in Carrara marble or the change of crystallographic structure and reaction-induced fracturing in aragonite allowed, to some extent, the pseudomorphic replacement of Carrara marble and aragonite samples by a porous (Ca,Cd)CO3 solid-solution phase of variable composition. These phenomena have been observed in solutions undersaturated with respect to all solid phases and are the result of an interface-coupled dissolution-precipitation mechanism where the dissolving CaCO3 provides ions to supersaturate the mineral-fluid interfacial layer, leading to the precipitation of a Cd-containing phase on the samples’ surfaces. This coupled dissolution-precipitation mechanism could potentially be used as a remediation process to sequester cadmium from contaminated effluents.

Radar and spacecraft observations show the permanently shadowed regions around Mercury's North Pole to contain water ice and complex organic material. One possible source of this material are impacts by interplanetary dust particles (IDPs), asteroids, and comets. We have performed numerical simulations of the dynamical evolution of asteroids and comets over the few Myr and checked for their impacts with Mercury. We use the N-body integrator RMVS/Swifter to propagate the Sun and the eight planets from their current positions. We add comets and asteroids to the simulations as massless test particles, based on their current orbital distributions. Asteroid impactors are assigned a probability of being water-rich (C-class) based on the measured distribution of taxonomic types. For comets, we assume a constant water fraction. For IDPs, we use a dynamical meteoroid model to compute the dust flux on Mercury. Relative to previous work on asteroid and comet impacts (Moses et al. 1999), we leverage 20 years of progress in minor body surveys. Immediate post-impact ejection of impactor material into outer space is taken into account as is the migration efficiency of water across Mercury's surface to the polar cold traps. We find that asteroids deliver $\sim 1 \times 10^{3}$ kg/yr of water to Mercury, comets deliver $\sim 1 \times 10^{3}$ kg/yr and IDPs deliver $\sim 16 \times 10^{3}$ kg/yr within a factor of several. Over a timescale of $\sim 1$ Gyr, this is enough to deliver the minimum amount of water required by the radar and MESSENGER observations. While other sources of water on Mercury are not ruled out by our analysis, we show that they are not required to explain the currently available observational lower limits., 38 pages, 10 figures, published in Icarus

A little-studied p-type ternary oxide semiconductor, copper(I) tungstate (Cu2WO4), was assessed by a combined theoretical/experimental approach. A detailed computational study was performed to solve the long-standing debate on the space group of Cu2WO4, which was determined to be triclinic P1. Cu2WO4 was synthesized by a time-efficient, arc-melting method, and the crystalline reddish particulate product showed broad-band absorption in the UV-visible spectral region, thermal stability up to ∼260 °C, and cathodic photoelectrochemical activity. Controlled thermal oxidation of copper from the Cu(I) to Cu(II) oxidation state showed that the crystal lattice could accommodate Cu2+ cations up to ∼260 °C, beyond which the compound was converted to CuO and CuWO4. This process was monitored by powder X-ray diffraction and X-ray photoelectron spectroscopy. The electronic band structure of Cu2WO4 was contrasted with that of the Cu(II) counterpart, CuWO4 using spin-polarized density functional theory (DFT). Finally, the compound Cu2WO4 was determined to have a high-lying (negative potential) conduction band edge underlining its promise for driving energetic photoredox reactions.

Mars missions and Martian analog systems inform each other in an iterative fashion: the insights gleaned from laboratory and field analogs guides mission concepts while the data acquired by missions improves analog designs. As space missions only grant us a small subset of everything we desire to study on Mars, support from simulations in the laboratory and field expeditions to analog environments is a natural follow-up. In this way we can expand our limited data sets, better interpret the results, and plan the next mission in a more informed manner. Laboratory and field analogs have aided us in our investigations of the mineralogy of Mars, and the search for water, organic molecules, and life that have been some of the primary objectives of Mars missions in the last decades, and questions relevant to fundamental science. In a time of scientific exploration when the frontier is frequented by only a few, our efforts in space exploration are largely accomplished on Earth with relatively low-cost, targeted techniques. This thesis is a collection of four distinct laboratory and field analog studies. It describes several experimental designs used to study the stability of organic molecules in various surface environments on Mars and the significance of those environments to Martian prebiotic chemistry, and includes a field campaign to a Martian analog environment (Icelandic lava tubes) undertaken to gain insight into potential geochemical signatures of life in the subsurface of Mars. The works are presented in the larger context of analogs in planetary research and astrobiology.

Predicting the fate and transport of pharmaceuticals in terrestrial environments requires knowledge of their interactions with complex mineral assemblages. To advance knowledge along this front, we examined the reactivity of pipemidic acid (PIP), a typical quinolone antibiotic, with quartz particles coated with a mixture of manganese oxide (MnO2) and goethite (α-FeOOH) under static and dynamic flow conditions. Batch and dynamic column experiments showed that PIP binding to MnO2 proceeded through a heterogeneous redox reaction, while binding to goethite was not redox-reactive. Mixed columns of aggregated goethite-manganese particles however enhanced redox reactivity because (i) goethite facilitated the transport of dissolved Mn(II) ion and increased the retention of PIP oxidation products, and (ii) MnO2 was protected from passivation. This mobility behavior was predicted using transport models accounting for adsorption and transformation kinetics of PIP on both goethite and MnO2. This work sheds new light on reactivity changes of mixtures of Fe and Mn oxides under flow-through conditions and will have important implications in predicting the fate and transport of redox-active organic compounds as well as development of new geomedia filters for environmental remediation.

Amino acids and polycyclic aromatic hydrocarbons (PAHs) belong to the range of organic compounds detected in meteorites. In this study, we tested empirically and theoretically if PAHs are precursors for amino acids in carbonaceous chondrites, as previously suggested. We conducted experiments to synthesize amino acids from fluoranthene (PAH), with ammonium bicarbonate as a source for ammonia and carbon dioxide under mimicked asteroidal conditions. In our thermodynamic calculations, we extended our analysis to additional PAH-amino acid combinations. We explored 36 reactions involving the PAHs naphthalene, anthracene, fluoranthene, pyrene, triphenylene, and coronene and the amino acids glycine, alanine, valine, leucine, phenylalanine, and tyrosine. Our experiments do not show the formation of amino acids, whereas our theoretical results hint that PAHs could be precursors of amino acids in carbonaceous chondrites at low temperatures.

Serpentinization may provide a unique environment for the abiotic formation of condensed carbonaceous matter. This could support the deep biosphere and contribute to the deep carbon cycle, and may have provided the first building blocks for life. However, thus far, condensed carbonaceous matter has been found only in association with the minor mineral constituents of serpentinites. In contrast, here we show the direct association between carbonaceous matter and the dominant Fe oxide in serpentinites, magnetite. Our samples were recovered from the Yap Trench, western Pacific Ocean, with a human-occupied vehicle at a depth of 6413 m below sea level. The carbonaceous matter coincides with some micron-sized magnetite grains, but particularly with nanosized Fe oxides within serpentinite nanopores. Vibrational spectroscopy reveals that the condensed carbonaceous matter contains both aliphatic and aromatic compounds, but there is no evidence for functional groups typical for biological organics. Based on these observations, we suggest that physicochemical phenomena in serpentinite nanopores and nanosized catalytically active minerals may play a key role in the abiotic synthesis of complex carbonaceous matter.

Selenium (Se) isotope fractionation has been widely used for constraining redox conditions and microbial processes in both modern and ancient environments, but our knowledge of the controls on fractionation during microbial reduction of Se-oxyanions is based on a limited number of studies. Here we complement and expand the currently available pure culture data for Se isotope fractionation by investigating for the first time six phylogenetically diverse, mesophilic, and non-respiring bacterial strains that reduce Se-oxyanions to elemental Se [Se(0)]. Experiments were performed with either selenate [Se(VI)] or selenite [Se(IV)] at lower, more environmentally-relevant Se (9–47 μM) and carbon (500 μM) concentrations than previously investigated. Enterobacter cloacae SLD1a-1, Desulfitobacterium chlororespirans Co23 and Desulfitobacterium sp. Viet-1 were incubated with Se(VI) and Se(IV). Geobacter sulfurreducens PCA, Anaeromyxobacter dehalogenans FRC-W and Shewanella sp. (NR) were examined for their ability reducing Se(IV) to Se(0). Our data confirm that microbial reduction of both Se-oxyanions is accompanied by large kinetic isotopic fractionation (reported as 82/76e = 1000×(82/76α-1) in ‰). Under our experimental conditions, microbial reduction of Se(VI) shows consistently greater isotope fractionation (e = −9.2‰ to −11.8‰) than reduction of Se(IV) (e = −6.2 to −7.8‰) confirming the difference in metabolic pathways for the reduction of the two Se-oxyanions. For Se(VI), an inverse relationship between normalized cell specific reduction rate (cSRR) and Se isotope fractionation suggests that the kinetic isotope effect for Se(VI) reduction is governed by an enzymatically-specific pathway related to the bacterial strain-specific physiology. In contrast, the lack of correlation between normalized cSRR and isotope fractionation for Se(IV) reduction indicates a non-enzyme specific pathway which is dominantly extracellular. Our study highlights the importance to understand microbially-mediated Se isotope fractionation depending on Se species, and cell-specific reduction rates before Se isotope ratios can become a fully applicable tool to interpret Se isotopic changes in modern and ancient environments.

Late Pleistocene tephras derived by large explosive volcanic eruptions are widespread in the Mediterranean and surrounding areas. They are important isochronous markers in stratigraphic sections and therefore it is important to constrain their sources. We report here tephrochronology results using multiple criteria to characterize the volcanic products of the Late Pleistocene Ciomadul volcano in eastern-central Europe. This dacitic volcano had an explosive eruption stage between 57 and 30 ka. The specific petrological character (ash texture, occurrence of plagioclase and amphibole phenocrysts and their composition), the high-K calc-alkaline major element composition and particularly the distinct trace element characteristics provide a strong fingerprinting of the Ciomadul volcano. This can be used for correlating tephra and cryptotephra occurrences within this timeframe. Remarkably, during this time there were several volcanic eruptions produced tephras with similar glass major element composition. However, these tephras differ from Ciomadul ones by glass trace element abundances, ratios of strongly incompatible trace elements and distinctive mineral cargo that serve as discrimination tools. We used (U-Th)/He zircon dates combined with U-Th in-situ rim dates along with luminescence and radiocarbon dating to constrain the age of the explosive eruptions of Ciomadul that yielded distal tephra layers, but lack of identified proximal deposits.

Reconstructing the emergence and weathering of continental crust in the Archaean eon is crucial for our understanding of early ocean chemistry, biosphere evolution and the onset of plate tectonics. However, considerable disagreement exists between elemental and isotopic proxies that have been used to trace crustal input into marine sediments, and data are scarce before 3 Ga. Here we show that chemical weathering modified the Sr isotopic composition of seawater as recorded in 3.52–3.20 Ga stratiform barite deposits from three different cratons. Using a combination of Sr, S and O isotope data, barite petrography and a hydrothermal mixing model, we calculate a Sr isotope evolution trend of Palaeoarchaean seawater that is much more radiogenic than the curve previously determined from carbonate rocks. Our findings suggest that evolved crust containing high Rb/Sr was subaerial and weathering into the oceans from approximately 3.7 ± 0.15 Ga onwards with impacts on ocean chemistry and the nutrient supply to the marine biosphere.

Lava tubes on Mars hold exciting potential for the preservation of biosignatures, which may survive on geological timescales in these isolated, stable environments. To support the development of future astrobiological mission concepts, we turn to terrestrial lava tubes, host to a variety of microbial communities and secondary minerals. Following a multidisciplinary sampling protocol, we retrieved biological, molecular, and mineralogical data from several lava tubes in Iceland. We report on blue-colored copper-rich secondary minerals and their associated bacterial communities using a multi-method approach, and an amalgam of 16S rRNA gene sequencing, Raman spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy data sets. We found numerous bacterial genera known for their high metal resistance and ability to survive in low-nutrient environments. Both are characteristics to be expected for any potential life in Martian lava tubes, and should be considered when checking for contaminants in Mars mission preparations. Associated with the microbial mats, we identified several types of copper-rich secondary minerals, indicating localized copper enrichments in the groundwater, possibly stemming from overlying ash deposits and nearby hyaloclastite formations. Molecular analysis revealed carotenoid signals preserved within the copper speleothems. If found in Martian lava tubes, blue copper-rich mineral precipitates would be deserving of astrobiological investigation, as they have potential to preserve biosignatures and harbor life. Plain Language Summary Subterranean lava tubes on Mars are exciting locations to study in the potential discovery of signs of life outside of Earth, as the surface of Mars does not have conditions conducive to the preservation of life as we know it. In order to better study these Martian environments we look first to comparable lava tubes on Earth. Within Icelandic lava tubes we found blue-colored copper minerals, host to microbial life. The microbes that thrive in these caves are able to withstand extreme conditions, and leave behind detectable molecular traces indicative of life, a type of biosignature. Using a variety of tools and techniques, we describe the nature of the blue minerals and their provenance, the role of the microbial populations within them, and the value of the molecular traces as biosignatures. We discuss the potential for such minerals and microbes in Martian lava tubes, and how we might successfully sample them in future missions to Mars.

The Earth-abundant kesterite Cu2ZnSnS4 (CZTS) exhibits outstanding structural, optical, and electronic properties for a wide range of optoelectronic applications. However, the efficiency of CZTS thin-film solar cells is limited due to a range of factors, including electronic disorder, secondary phases, and the presence of anti-site defects, which is a key factor limiting the Voc. The complete substitution of Zn lattice sites in CZTS nanocrystals (NCs) with Cd atoms offers a promising approach to overcome several of these intrinsic limitations. Herein, we investigate the effects of substituting Cd2+ into Zn2+ lattice sites in CZTS NCs through a facile solution-based method. The structural, morphological, optoelectronic, and power conversion efficiencies (PCEs) of the NCs synthesized have been systematically characterized using various experimental techniques, and the results are corroborated by first-principles density functional theory (DFT) calculations. The successful substitution of Zn by Cd is demonstrated to induce a structural transformation from the kesterite phase to the stannite phase, which results in the bandgap reduction from 1.51 eV (kesterite) to 1.1 eV (stannite), which is closer to the optimum bandgap value for outdoor photovoltaic applications. Furthermore, the PCE of the novel Cd-substituted liquid junction solar cell underwent a four-fold increase, reaching 1.1%. These results highlight the importance of substitutional doping strategies in optimizing existing CZTS-based materials to achieve improved device characteristics.

Metal sulphides, including zinc sulphide (ZnS), are semiconductor photocatalysts that have been investigated for the photocatalytic degradation of organic pollutants as well as their activity during the hydrogen evolution reaction and water splitting. However, devising ZnS photocatalysts with a high overall quantum efficiency has been a challenge due to the rapid recombination rates of charge carriers. Various strategies, including the control of size and morphology of ZnS nanoparticles, have been proposed to overcome these drawbacks. In this work, ZnS samples with different morphologies were prepared from zinc and sulphur powders via a facile hydrothermal method by varying the amount of sodium borohydride used as a reducing agent. The structural properties of the ZnS nanoparticles were analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques. All-electron hybrid density functional theory calculations were employed to elucidate the effect of sulphur and zinc vacancies occurring in the bulk as well as (220) surface on the overall electronic properties and absorption of ZnS. Considerable differences in the defect level positions were observed between the bulk and surface of ZnS while the adsorption of NaBH4 was found to be highly favourable but without any significant effect on the band gap of ZnS. The photocatalytic activity of ZnS was evaluated for the degradation of rhodamine B dye under UV irradiation and hydrogen generation from water. The ZnS nanoparticles photo-catalytically degraded Rhodamine B dye effectively, with the sample containing 0.01 mol NaBH4 being the most efficient. The samples also showed activity for hydrogen evolution, but with less H2 produced compared to when untreated samples of ZnS were used. These findings suggest that ZnS nanoparticles are effective photocatalysts for the degradation of rhodamine B dyes as well as the hydrogen evolution, but rapid recombination of charge carriers remains a factor that needs future optimization.

The astronomical theory of climate change resulting from quasi-periodic variations in the Earth’s orbit and spin axis (Milankovitch forcing) is now widely accepted for the Phanerozoic, the most recent ~0.5 billion years of Earth history. However, much older, Precambrian intervals remain largely unexplored. In this thesis, we investigated the influence of Milankovitch forcing on banded iron formations (BIFs) deposited during the earliest Paleoproterozoic, ~2.48 - 2.46 billion years ago. We show, based on cyclostratigraphic analysis combined with high-precision uranium-lead dating, that regular variations in the Kuruman Iron Formation (IF) in South Africa are related to the long (405 kyr) and very long (~1.2 - 1.6 Myr) eccentricity cycles of Earth’s orbit. Using the same approach, we identify the expression of short (~100 kyr) eccentricity and climatic precession in the slightly younger Joffre Member of the Brockman IF in Western Australia. The precession-related cycles are subsequently targeted for high-resolution geochemical analysis and modelling to unravel their origin. As such, we find evidence for dynamical redox changes in the BIF-forming marine environment, which may have been caused by monsoonal-driven changes in oxygenic photosynthesis, before the onset of atmospheric oxygenation ~2.4 billion years ago. Using the ratio between the eccentricity- and precession-related cycles, we further arrive at a reconstruction of the precession frequency, Earth-Moon distance and length-of-day at that time. Finally, we attempt to establish an astrochronological framework for the Kuruman IF and time-equivalent Dales Gorge Member of the Brockman IF.