Microbial Alkalinity Production and Silicate Alteration in Methane Charged Marine Sediments: Implications for Porewater Chemistry and Diagenetic Carbonate Formation

A numerical reaction-transport model was developed to simulate the effects of microbial activity and mineral reactions on the composition of porewater in a 230-m-thick Pleistocene interval drilled in the Peru-Chile Trench (Ocean Drilling Program, Site 1230). This site has porewater profiles similar to those along many continental margins, where intense methanogenesis occurs and alkalinity surpasses 100 mmol/L. Simulations show that microbial sulphate reduction, anaerobic oxidation of methane, and ammonium release from organic matter degradation only account for parts of total alkalinity, and excess CO2 produced during methanogenesis leads to acidification of porewater. Additional alkalinity is produced by slow alteration of primary aluminosilicate minerals to kaolinite and SiO2. Overall, alkalinity production in the methanogenic zone is sufficient to prevent dissolution of carbonate minerals; indeed, it contributes to the formation of cemented carbonate layers at a supersaturation front near the sulphate-methane transition zone. Within the methanogenic zone, carbonate formation is largely inhibited by cation diffusion but occurs rapidly if cations are transported into the zone via fluid conduits, such as faults. The simulation presented here provides fundamental insight into the diagenetic effects of the deep biosphere and may also be applicable for the long-term prediction of the stability and safety of deep CO2 storage reservoirs.

Cenozoic evolution of the Campbell Plateau, Subantarctic New Zealand: Insights from sub-bottom profile data

<p>The Campbell Plateau represents ~30% of the submerged continent of Zealandia and represents part of the Gondwana super-continent that began to break-up ~98Ma. The focus of this MSc thesis is to use sub-bottom, profile data collected in 2017 and 2018 from Campbell Plateau to improve our understanding of the Cenozoic evolution of the region. The sub-bottom profiles show a rugged basement overlain by a variety of sedimentary sequences and subsurface features such as volcanoes, onlap, and downlap surfaces as well as multiple unconformities that can be traced throughout the Cenozoic (65Ma). The sub-bottom profiles are compared to 2 drill cores; Ocean Drilling Program (ODP) site 1120 on the eastern side of the plateau and Deep Sea Drilling Program (DSDP) site 277 in the south. These drill cores indicate that the lithology from the Cretaceous onwards is predominantly biogenic calcareous sandstone and mudstone, which changes to nannofossil-rich oozes in the Miocene and foraminiferal oozes and nannofossil oozes dated early to late Pleistocene. The northern plateau appears to be relatively quiescent with thin, relatively uniform strata, only influenced by small reverse faults. Sedimentary deposits such as wedges and contourites are also evident in the central and north-western part of the study area. The southern plateau appears to be have been highly dynamic with onlap/downlap surfaces, interpreted as current scours, and erosional surfaces. There is a plateau-wide unconformity during the Pliocene, as derived from the nannofossils of the ODP1120 drill core, which appears to have been a large-scale erosional event. The Southern Ocean circulation, dominated by Antarctic Circumpolar Current, the Subtropical Front, and local wind-driven currents, are the main drivers of these lithological changes and plateau-wide sedimentological structures. Previous interpretations of the sub-surface structure of the plateau are seen to be invalid in relation to this study, with the sub-surface seen to be relatively undeformed with only minor reverse faulting present. Areas of possible uplifted basement seen near Campbell Island also indicate that the Campbell Plateau has been through substantial erosion and deformation since its’ separation from Gondwana ~98Ma and movement to its modern-day position.</p>

Cenozoic evolution of the Campbell Plateau, Subantarctic New Zealand: Insights from sub-bottom profile data

<p>The Campbell Plateau represents ~30% of the submerged continent of Zealandia and represents part of the Gondwana super-continent that began to break-up ~98Ma. The focus of this MSc thesis is to use sub-bottom, profile data collected in 2017 and 2018 from Campbell Plateau to improve our understanding of the Cenozoic evolution of the region. The sub-bottom profiles show a rugged basement overlain by a variety of sedimentary sequences and subsurface features such as volcanoes, onlap, and downlap surfaces as well as multiple unconformities that can be traced throughout the Cenozoic (65Ma). The sub-bottom profiles are compared to 2 drill cores; Ocean Drilling Program (ODP) site 1120 on the eastern side of the plateau and Deep Sea Drilling Program (DSDP) site 277 in the south. These drill cores indicate that the lithology from the Cretaceous onwards is predominantly biogenic calcareous sandstone and mudstone, which changes to nannofossil-rich oozes in the Miocene and foraminiferal oozes and nannofossil oozes dated early to late Pleistocene. The northern plateau appears to be relatively quiescent with thin, relatively uniform strata, only influenced by small reverse faults. Sedimentary deposits such as wedges and contourites are also evident in the central and north-western part of the study area. The southern plateau appears to be have been highly dynamic with onlap/downlap surfaces, interpreted as current scours, and erosional surfaces. There is a plateau-wide unconformity during the Pliocene, as derived from the nannofossils of the ODP1120 drill core, which appears to have been a large-scale erosional event. The Southern Ocean circulation, dominated by Antarctic Circumpolar Current, the Subtropical Front, and local wind-driven currents, are the main drivers of these lithological changes and plateau-wide sedimentological structures. Previous interpretations of the sub-surface structure of the plateau are seen to be invalid in relation to this study, with the sub-surface seen to be relatively undeformed with only minor reverse faulting present. Areas of possible uplifted basement seen near Campbell Island also indicate that the Campbell Plateau has been through substantial erosion and deformation since its’ separation from Gondwana ~98Ma and movement to its modern-day position.</p>

Maastrichtian–Rupelian paleoclimates in the southwest Pacific – a critical re-evaluation of biomarker paleothermometry and dinoflagellate cyst paleoecology at Ocean Drilling Program Site 1172

Sea surface temperature (SST) reconstructions based on isoprenoid glycerol dialkyl glycerol tetraether (isoGDGT) distributions from the Eocene southwest (SW) Pacific Ocean are unequivocally warmer than can be reconciled with state-of-the-art fully coupled climate models. However, the SST signal preserved in sedimentary archives can be affected by contributions of additional isoGDGT sources. Methods now exist to identify and possibly correct for overprinting effects on the isoGDGT distribution in marine sediments. Here, we use the current proxy insights to (re-)assess the reliability of the isoGDGT-based SST signal in 69 newly analyzed and 242 reanalyzed sediments at Ocean Drilling Program (ODP) Site 1172 (East Tasman Plateau, Australia) following state-of-the-art chromatographic techniques. We compare our results with paleoenvironmental and paleoclimatologic reconstructions based on dinoflagellate cysts. The resulting ∼ 130 kyr resolution Maastrichtian–Oligocene SST record based on the TetraEther indeX of tetraethers with 86 carbon atoms (TEX86) confirms previous conclusions of anomalous warmth in the early Eocene SW Pacific and remarkably cool conditions during the mid-Paleocene. Dinocyst diversity and assemblages show a strong response to the local SST evolution, supporting the robustness of the TEX86 record. Soil-derived branched GDGTs stored in the same sediments are used to reconstruct mean annual air temperature (MAAT) of the nearby land using the Methylation index of Branched Tetraethers with 5-methyl bonds (MBT'5me) proxy. MAAT is consistently lower than SST during the early Eocene, independent of the calibration chosen. General trends in SST and MAAT are similar, except for (1) an enigmatic absence of MAAT rise during the Paleocene–Eocene Thermal Maximum and Middle Eocene Climatic Optimum, and (2) a subdued middle–late Eocene MAAT cooling relative to SST. Both dinocysts and GDGT signals suggest a mid-shelf depositional environment with strong river runoff during the Paleocene–early Eocene progressively becoming more marine thereafter. This trend reflects gradual subsidence and more pronounced wet/dry seasons in the northward-drifting Australian hinterland, which may also explain the subdued middle Eocene MAAT cooling relative to that of SST. The overall correlation between dinocyst assemblages, marine biodiversity and SST changes suggests that temperature exerted a strong influence on the surface-water ecosystem. Finally, we find support for a potential temperature control on compositional changes of branched glycerol monoalkyl glycerol tetraethers (brGMGTs) in marine sediments. It is encouraging that a critical evaluation of the GDGT signals confirms that most of the generated data are reliable. However, this also implies that the high TEX86-based SSTs for the Eocene SW Pacific and the systematic offset between absolute TEX86-based SST and MBT'5me-based MAAT estimates remain without definitive explanation.

The response of Antarctic ice volume, global sea-level and southwest Pacific Ocean circulation to orbital variations during the Pliocene to Early Pleistocene

<p>This thesis investigates orbitally-paced variations in the extent of East Antarctic Ice Sheet (EAIS), and the “downstream” influence of these ice sheet variations on ocean circulation and sea level variability during the Pliocene and Early Pleistocene - a time period characterised by a major global cooling step that culminated in the development of a bipolar glaciated world. Three unique records are examined from (1) the Antarctic margin, (2) the southwest Pacific Ocean, and (3) shallow-marine sedimentary strata exposed in Wangnaui Basin, New Zealand. The Integrated Ocean Drilling Program (IODP) Site U1361 recovered a continuous sedimentary Early Pliocene to Early Pleistocene (4.3 to 2.0 Ma) record from the lowermost continental rise on the Wilkes Land margin offshore of the EAIS. A facies model and stratigraphic framework were developed that allowed for the identification of glacial advances (massive and laminated mudstones) and retreats (diatom-rich mudstones) across the continental shelf, with evidence for prolonged retreats spanning several glacial to interglacial cycles throughout the Pliocene. These cycles are followed by an extensive Early Pleistocene interval (~2.6 Ma) of diatom-rich mudstone with evidence for reworking by bottom currents, interpreted to be the consequence of downslope density currents associated with increased sea ice production after 2.6 Ma. Frequency analysis on Iceberg Rafted Debris (IBRD) from Site U1361 reveals that under an Early Pliocene warm climate state (4.3 to 3.3 Ma), that ice discharge off the EAIS occurred in response to climate change paced by the 40-kyr cycles of obliquity. Whereas, the colder climate state of Late Pliocene to Early Pleistocene (3.3 to 2.0 Ma) resulted in a transferral of orbital variance to 20-kyr-duration, precession-dominated variability in IBRD preceding the development of a more stable marine-based margin of the EAIS at ~2.6 Ma, which is hypothesized to reflect the declining influence of oceanic forcing as the high-latitude Southern Ocean cooled thereby increasing the seasonal duration and extent of sea-ice. The precession-paced influence on IBRD and ice volume variability of the EAIS was strongly modulated by 100-kyr-eccentricity, which is expressed lithologically in cycles of two alternating lithofacies 1) diatom-rich mudstones and 2) massive and laminted mudstones in the Site U1361 record. A compilation of benthic stable isotope records from Ocean Drilling Program (ODP) Site 1123 in the southwest Pacific Ocean was also developed. The δ18O record identified a 40-kyr obliquity pacing, consistent with other benthic δ18O records globally for this time period, thus allowing for an orbitally-tuned timescale to be developed for this site. Long-term trends in both the δ18O and δ13C records at ODP Site 1123 coincide with major developments of the Antarctic Ice Sheet and Northern Hemisphere glaciation at 3.33 Ma and ~2.6 Ma respectively. A gradual reduction in the deep water δ13C gradient between the southwest Pacific (ODP Site 1123) and equatorial Pacific (ODP Site 849) between 3.33 and 2.6 Ma coincides with expansion of the Antarctic Ice Sheet, enhanced Antarctic Bottom Water (AABW) production, invigorated atmospheric zonal circulation in the southern hemisphere mid-latitudes, and increased meridional sea surface temperature (SST) gradients in the Pacific Ocean. Finally, a shallow-marine, continental margin stratigraphic section from the Turakina River Valley in the Wanganui Basin, New Zealand, was used to record local sea-level changes, dominated by orbitally-driven, global glacio-eustasy, during the mid-Pliocene interval (3.2 to 3.0 Ma). This interval was selected as it precedes the build-up of significant Northern Hemisphere Ice Sheet, thus allowing for an independent assessment of the orbtial-scale variability of Antarctic Ice Sheet volume. Grain size based proxy of percent mud was employed to reconstruct paleobathymetric changes, which displayed 100-kyr cycles consistent with ~20 m variations in local water depths during the mid-Pliocene. Combined with IBRD record from Site U1361, this reconstruction suggests that the marine margins of East Antarctica varied at orbital timescale, and provided a significant contribution to global eustatic sea-level variations during the mid Pliocene (consistent with global mean sea-level estimates of up to ~+20 m above present from related studies).</p>

The response of Antarctic ice volume, global sea-level and southwest Pacific Ocean circulation to orbital variations during the Pliocene to Early Pleistocene

<p>This thesis investigates orbitally-paced variations in the extent of East Antarctic Ice Sheet (EAIS), and the “downstream” influence of these ice sheet variations on ocean circulation and sea level variability during the Pliocene and Early Pleistocene - a time period characterised by a major global cooling step that culminated in the development of a bipolar glaciated world. Three unique records are examined from (1) the Antarctic margin, (2) the southwest Pacific Ocean, and (3) shallow-marine sedimentary strata exposed in Wangnaui Basin, New Zealand. The Integrated Ocean Drilling Program (IODP) Site U1361 recovered a continuous sedimentary Early Pliocene to Early Pleistocene (4.3 to 2.0 Ma) record from the lowermost continental rise on the Wilkes Land margin offshore of the EAIS. A facies model and stratigraphic framework were developed that allowed for the identification of glacial advances (massive and laminated mudstones) and retreats (diatom-rich mudstones) across the continental shelf, with evidence for prolonged retreats spanning several glacial to interglacial cycles throughout the Pliocene. These cycles are followed by an extensive Early Pleistocene interval (~2.6 Ma) of diatom-rich mudstone with evidence for reworking by bottom currents, interpreted to be the consequence of downslope density currents associated with increased sea ice production after 2.6 Ma. Frequency analysis on Iceberg Rafted Debris (IBRD) from Site U1361 reveals that under an Early Pliocene warm climate state (4.3 to 3.3 Ma), that ice discharge off the EAIS occurred in response to climate change paced by the 40-kyr cycles of obliquity. Whereas, the colder climate state of Late Pliocene to Early Pleistocene (3.3 to 2.0 Ma) resulted in a transferral of orbital variance to 20-kyr-duration, precession-dominated variability in IBRD preceding the development of a more stable marine-based margin of the EAIS at ~2.6 Ma, which is hypothesized to reflect the declining influence of oceanic forcing as the high-latitude Southern Ocean cooled thereby increasing the seasonal duration and extent of sea-ice. The precession-paced influence on IBRD and ice volume variability of the EAIS was strongly modulated by 100-kyr-eccentricity, which is expressed lithologically in cycles of two alternating lithofacies 1) diatom-rich mudstones and 2) massive and laminted mudstones in the Site U1361 record. A compilation of benthic stable isotope records from Ocean Drilling Program (ODP) Site 1123 in the southwest Pacific Ocean was also developed. The δ18O record identified a 40-kyr obliquity pacing, consistent with other benthic δ18O records globally for this time period, thus allowing for an orbitally-tuned timescale to be developed for this site. Long-term trends in both the δ18O and δ13C records at ODP Site 1123 coincide with major developments of the Antarctic Ice Sheet and Northern Hemisphere glaciation at 3.33 Ma and ~2.6 Ma respectively. A gradual reduction in the deep water δ13C gradient between the southwest Pacific (ODP Site 1123) and equatorial Pacific (ODP Site 849) between 3.33 and 2.6 Ma coincides with expansion of the Antarctic Ice Sheet, enhanced Antarctic Bottom Water (AABW) production, invigorated atmospheric zonal circulation in the southern hemisphere mid-latitudes, and increased meridional sea surface temperature (SST) gradients in the Pacific Ocean. Finally, a shallow-marine, continental margin stratigraphic section from the Turakina River Valley in the Wanganui Basin, New Zealand, was used to record local sea-level changes, dominated by orbitally-driven, global glacio-eustasy, during the mid-Pliocene interval (3.2 to 3.0 Ma). This interval was selected as it precedes the build-up of significant Northern Hemisphere Ice Sheet, thus allowing for an independent assessment of the orbtial-scale variability of Antarctic Ice Sheet volume. Grain size based proxy of percent mud was employed to reconstruct paleobathymetric changes, which displayed 100-kyr cycles consistent with ~20 m variations in local water depths during the mid-Pliocene. Combined with IBRD record from Site U1361, this reconstruction suggests that the marine margins of East Antarctica varied at orbital timescale, and provided a significant contribution to global eustatic sea-level variations during the mid Pliocene (consistent with global mean sea-level estimates of up to ~+20 m above present from related studies).</p>

The Nazca Drift System – palaeoceanographic significance of a giant sleeping on the SE Pacific Ocean floor

The evolution and resulting morphology of a contourite drift system in the SE Pacific oceanic basin is investigated in detail using seismic imaging and an age-calibrated borehole section. The Nazca Drift System covers an area of 204 500 km2 and stands above the abyssal basins of Peru and Chile. The drift is spread along the Nazca Ridge in water depths between 2090 and 5330 m. The Nazca Drift System was drilled at Ocean Drilling Program Site 1237. This deep-water drift overlies faulted oceanic crust and onlaps associated volcanic highs. Its thickness ranges from 104 to 375 m. The seismic sheet facies observed are associated with bottom current processes. The main lithologies are pelagic carbonates reflecting the distal position relative to South America and water depth above the carbonate compensation depth during Oligocene time. The Nazca Drift System developed under the influence of bottom currents sourced from the Circumpolar Deep Water and Pacific Central Water, and is the largest yet identified abyssal drift system of the Pacific Ocean, ranking third in all abyssal contourite drift systems globally. Subduction since late Miocene time and the excess of sediments and water associated with the Nazca Drift System may have contributed to the Andean orogeny and associated metallogenesis. The Nazca Drift System records the evolution in interactions between deep-sea currents and the eastward motion of the Nazca Plate through erosive surfaces and sediment remobilization.

Late Eocene–early Miocene evolution of the southern Australian subtropical front: a marine palynological approach

Improvements in our capability to reconstruct ancient surface-ocean conditions based on organic-walled dinoflagellate cyst (dinocyst) assemblages from the Southern Ocean provide an opportunity to better establish past position, strength and oceanography of the subtropical front (STF). Here, we aim to reconstruct the late Eocene to early Miocene (37–20 Ma) depositional and palaeoceanographic history of the STF in the context of the evolving Tasmanian Gateway as well as the potential influence of Antarctic circumpolar flow and intense waxing and waning of ice. We approach this by combining information from seismic lines (revisiting existing data and generating new marine palynological data from Ocean Drilling Program (ODP) Hole 1168A) in the western Tasmanian continental slope. We apply improved taxonomic insights and palaeoecological models to reconstruct the sea surface palaeoenvironmental evolution. Late Eocene–early Oligocene (37–30.5 Ma) assemblages show a progressive transition from dominant terrestrial palynomorphs and inner-neritic dinocyst taxa as well as cysts produced by heterotrophic dinoflagellates to predominantly outer-neritic/oceanic autotrophic taxa. This transition reflects the progressive deepening of the western Tasmanian continental margin, an interpretation supported by our new seismic investigations. The dominance of autotrophic species like Spiniferites spp. and Operculodinium spp. reflects relatively oligotrophic conditions, like those of regions north of the modern-day STF. The increased abundance in the earliest Miocene of Nematosphaeropsis labyrinthus, typical for modern subantarctic zone (frontal) conditions, indicates a cooling and/or closer proximity of the STF to the site . The absence of major shifts in dinocyst assemblages contrasts with other records in the region and suggests that small changes in surface oceanographic conditions occurred during the Oligocene. Despite the relatively southerly (63–55∘ S) location of Site 1168, the rather stable oceanographic conditions reflect the continued influence of the proto-Leeuwin Current along the southern Australian coast as Australia continued to drift northward. The relatively “warm” dinocyst assemblages at ODP Site 1168, compared with the cold assemblages at Antarctic Integrated Ocean Drilling Program (IODP) Site U1356, testify to the establishment of a pronounced latitudinal temperature gradient in the Oligocene Southern Ocean.

Southern Ocean bottom-water cooling and ice sheet expansion during the middle Miocene climate transition

The middle Miocene climate transition (MMCT), around 14 Ma, was associated with a significant climatic shift, but the mechanisms triggering the event remain enigmatic. We present a clumped isotope (Δ47) bottom-water temperature (BWT) record from 16.0 to 12.2 Ma from Ocean Drilling Program (ODP) Site 747 in the Southern Ocean and compare it to existing BWT records from different latitudes. We show that BWTs in the Southern Ocean reached 8–10 ∘C during the Miocene climatic optimum. These high BWT values indicate considerably warmer bottom-water conditions than today. Nonetheless, bottom-water δ18O (calculated from foraminiferal δ18O and Δ47) suggests substantial amounts of land ice throughout the interval of the study. Our dataset further demonstrates that BWTs at Site 747 were variable with an overall cooling trend across the MMCT. Notably, a cooling of around 3–5 ∘C preceded the stepped main increase in benthic δ18O, interpreted as global ice volume expansion, and appears to have been followed by a transient bottom-water warming starting during or slightly after the main ice volume increase. We speculate that a regional freshening of the upper water column at this time may have increased stratification and reduced bottom-water heat loss to the atmosphere, counteracting global cooling in the bottom waters of the Southern Ocean and possibly even at larger scales. Feedbacks required for substantial ice growth and/or tectonic processes may have contributed to the observed decoupling of global ice volume and Southern Ocean BWT.

Quaternary equatorial Atlantic deep-sea ostracodes: evidence for a distinct tropical fauna in the deep sea

Low-latitude, deep-sea faunas remain poorly understood and described. Here, we systematically describe Quaternary deep-sea ostracodes from the Ocean Drilling Program (ODP) Site 925 (Ceara Rise; 4°12.2'N, 43°29.3′W; 3040 m water depth) in the equatorial Atlantic Ocean. Twenty-six genera and 52 species were examined and illustrated with high-resolution scanning electron microscopy images. Six new species are described herein: Pseudocythere spinae, Hemiparacytheridea zarikiani, Pedicythere canis, Xylocythere denticulata, Paracytherois obtusa, and Poseidonamicus sculptus. The results show that deep-sea ostracodes have a tropical faunal element that is distinctive from higher latitude ostracodes, and that is globally distributed in low latitudes. This tropical faunal component is possibly a Tethyan legacy of a fauna that was widely distributed in tropical and extratropical latitudes in deep waters during greenhouse conditions in the Cretaceous and early Cenozoic. Global cooling thereafter shrank its distribution, limiting it to tropical latitudes, perhaps with the relatively warm uppermost bathyal area acting as the source or refuge of this faunal component. Because similar present-day biogeographic patterns (i.e., presence and wide distribution of tropical deep-sea fauna) are known in other deep-sea benthic groups, this scenario might be applicable to the deep-sea benthos more broadly. UUID: http://zoobank.org/552d4cb2-c0db-463a-ae3f-b2efcc0985df.