Triple oxygen isotope constraints on atmospheric O2 and biological productivity during the mid-Proterozoic

Reconstructing the history of biological productivity and atmospheric oxygen partial pressure (pO2) is a fundamental goal of geobiology. Recently, the mass-independent fractionation of oxygen isotopes (O-MIF) has been used as a tool for estimating pO2 and productivity during the Proterozoic. O-MIF, reported as Δ′17O, is produced during the formation of ozone and destroyed by isotopic exchange with water by biological and chemical processes. Atmospheric O-MIF can be preserved in the geologic record when pyrite (FeS2) is oxidized during weathering, and the sulfur is redeposited as sulfate. Here, sedimentary sulfates from the ∼1.4-Ga Sibley Formation are reanalyzed using a detailed one-dimensional photochemical model that includes physical constraints on air–sea gas exchange. Previous analyses of these data concluded that pO2 at that time was <1% PAL (times the present atmospheric level). Our model shows that the upper limit on pO2 is essentially unconstrained by these data. Indeed, pO2 levels below 0.8% PAL are possible only if atmospheric methane was more abundant than today (so that pCO2 could have been lower) or if the Sibley O-MIF data were diluted by reprocessing before the sulfates were deposited. Our model also shows that, contrary to previous assertions, marine productivity cannot be reliably constrained by the O-MIF data because the exchange of molecular oxygen (O2) between the atmosphere and surface ocean is controlled more by air–sea gas transfer rates than by biological productivity. Improved estimates of pCO2 and/or improved proxies for Δ′17O of atmospheric O2 would allow tighter constraints to be placed on mid-Proterozoic pO2.

East Antarctic Ice Sheet and Southern Ocean Response to Orbital Forcing from Late Miocene to Early Pliocene, Wilkes Land, East Antarctica

<p>Geological and ice sheet models indicate that marine-based sectors of the East Antarctic Ice Sheet (EAIS) were unstable during periods of moderate climatic warmth in the past. While geological records from the Middle to Late Pliocene indicate a dynamic ice sheet, records of ice sheet variability from the comparatively warmer Late Miocene to Early Pliocene are sparse, and there are few direct records of Antarctic ice sheet variability during this time period. Sediment recovered in Integrated Ocean Drilling Program U1361 drill core from the Wilkes Land margin provides a distal but continuous glacially-influenced record of the behaviour of Antarctic Ice Sheets. This thesis presents marine sedimentological and x-ray fluorescence geochemical datasets in order to assess changes in the dynamic response of the EAIS and Southern Ocean productivity in the Wilkes Land sector during Late Miocene and Early Pliocene to climatic warming and orbital forcing between 6.2 and 4.4 Ma. Two primary lithofacies are identified which can be directly related to glacial–interglacial cycles; enhanced sedimentation during glacials is represented by low-density turbidity flows that occurred in unison with low marine productivity and reduced iceberg rafted debris. Interglacial sediments contain diatomaceous muds with short-lived, large fluxes of iceberg rafted debris preceding a more prolonged phase of enhanced marine productivity. Interglacial sediments coincide with a more mafic source of terrigenous sediment, interfered to be associated with an inland retreat of the ice margin resulting in erosion of lithologies that are currently located beneath the grounded EAIS. Poleward invigoration of the Antarctic Circumpolar Current during glacial–interglacial transitions is proposed to have intensified upwelling, enhancing nutrient availability for marine productivity, and increasing oceanic heat flux at the ice margin acting to erode marine ice sheet grounding lines and triggering retreat. Spectral analysis of the datasets indicated orbital frequencies are present in the iceberg rafted debris mass accumulation rates at all three Milankovitch frequencies, with a dominant 100 kyr eccentricity driven ice discharge. Prolonged intervals of marine productivity correlate to 100 kyr cyclicity occurring at peaks in obliquity. The response of both ice sheet and biological systems to 100 kyr cyclicity may indicate eccentricity-modulated sea ice extent controls the influx of warm water onto the continental shelf.</p>

East Antarctic Ice Sheet and Southern Ocean Response to Orbital Forcing from Late Miocene to Early Pliocene, Wilkes Land, East Antarctica

<p>Geological and ice sheet models indicate that marine-based sectors of the East Antarctic Ice Sheet (EAIS) were unstable during periods of moderate climatic warmth in the past. While geological records from the Middle to Late Pliocene indicate a dynamic ice sheet, records of ice sheet variability from the comparatively warmer Late Miocene to Early Pliocene are sparse, and there are few direct records of Antarctic ice sheet variability during this time period. Sediment recovered in Integrated Ocean Drilling Program U1361 drill core from the Wilkes Land margin provides a distal but continuous glacially-influenced record of the behaviour of Antarctic Ice Sheets. This thesis presents marine sedimentological and x-ray fluorescence geochemical datasets in order to assess changes in the dynamic response of the EAIS and Southern Ocean productivity in the Wilkes Land sector during Late Miocene and Early Pliocene to climatic warming and orbital forcing between 6.2 and 4.4 Ma. Two primary lithofacies are identified which can be directly related to glacial–interglacial cycles; enhanced sedimentation during glacials is represented by low-density turbidity flows that occurred in unison with low marine productivity and reduced iceberg rafted debris. Interglacial sediments contain diatomaceous muds with short-lived, large fluxes of iceberg rafted debris preceding a more prolonged phase of enhanced marine productivity. Interglacial sediments coincide with a more mafic source of terrigenous sediment, interfered to be associated with an inland retreat of the ice margin resulting in erosion of lithologies that are currently located beneath the grounded EAIS. Poleward invigoration of the Antarctic Circumpolar Current during glacial–interglacial transitions is proposed to have intensified upwelling, enhancing nutrient availability for marine productivity, and increasing oceanic heat flux at the ice margin acting to erode marine ice sheet grounding lines and triggering retreat. Spectral analysis of the datasets indicated orbital frequencies are present in the iceberg rafted debris mass accumulation rates at all three Milankovitch frequencies, with a dominant 100 kyr eccentricity driven ice discharge. Prolonged intervals of marine productivity correlate to 100 kyr cyclicity occurring at peaks in obliquity. The response of both ice sheet and biological systems to 100 kyr cyclicity may indicate eccentricity-modulated sea ice extent controls the influx of warm water onto the continental shelf.</p>

Marine phytoplankton functional types exhibit diverse responses to thermal change

Marine phytoplankton generate half of global primary production, making them essential to ecosystem functioning and biogeochemical cycling. Though phytoplankton are phylogenetically diverse, studies rarely designate unique thermal traits to different taxa, resulting in coarse representations of phytoplankton thermal responses. Here we assessed phytoplankton functional responses to temperature using empirically derived thermal growth rates from four principal contributors to marine productivity: diatoms, dinoflagellates, cyanobacteria, and coccolithophores. Using modeled sea surface temperatures for 1950–1970 and 2080–2100, we explored potential alterations to each group’s growth rates and geographical distribution under a future climate change scenario. Contrary to the commonly applied Eppley formulation, our data suggest phytoplankton functional types may be characterized by different temperature coefficients (Q10), growth maxima thermal dependencies, and thermal ranges which would drive dissimilar responses to each degree of temperature change. These differences, when applied in response to global simulations of future temperature, result in taxon-specific projections of growth and geographic distribution, with low-latitude coccolithophores facing considerable decreases and cyanobacteria substantial increases in growth rates. These results suggest that the singular effect of changing temperature may alter phytoplankton global community structure, owing to the significant variability in thermal response between phytoplankton functional types.

Controls on Terrigenous Detritus Deposition and Oceanography Changes in the Central Okhotsk Sea Over the Past 1550 ka

The Okhotsk Sea, which connects the high latitude Asian continent and the North Pacific, plays an important role in modern and past climate changes due to seasonal sea ice coverage and as a precursor of the North Pacific Intermediate Water. The long-term glacial-interglacial changes of sea ice coverage and its impacts on terrigenous transport and surface primary productivity in the Okhotsk Sea remain, however, not well constrained. Base on the paleomagnetic, rock magnetic, micropaleontological (diatom), and geochemical studies of the marine sediment core MD01-2414 (53°11.77′N, 149°34.80′E, water depth: 1,123 m) taken in the central Okhotsk Sea, we reconstruct the terrigenous sediment transport and paleoceanographic variations during the past 1550 thousand years (kyr). Seventeen geomagnetic excursions are identified from the paleomagnetic directional record. Close to the bottom of the core, an excursion was observed, which is proposed to be the Gilsa event ∼1550 thousand years ago (ka). During glacial intervals, our records reveal a wide extension of sea ice coverage and low marine productivity. We observed ice-rafted debris from mountain icebergs composed of coarse and high magnetic terrigenous detritus which were derived from the Kamchatka Peninsula to the central Okhotsk basin. Still during glacial intervals, the initiation (i.e., at ∼900 ka) of the Mid-Pleistocene Transition marks the changes to even lower marine productivity, suggesting that sea-ice coverage became larger during the last 900 ka. During interglacial intervals, the central Okhotsk Sea was either devoid of sea-ice or the ice was at best seasonal; resulting in high marine productivity. The weaker formation of Okhotsk Sea Intermediate Water, lower ventilation, and microbial degradation of organic matter depleted the oxygen concentration in the bottom water and created a reduced environment condition in the sea basin. The freshwater supplied by snow or glacier melting from Siberia and Kamchatka delivered fine grain sediments to the Okhotsk Sea. During the stronger interglacial intervals after the Mid-Brunhes Transition (i.e., Marine Isotope Stages 1, 5e, 9, and 11), strong freshwater discharges from Amur River drainage area are in association with intensified East Asian Summer Monsoon. This process may have enhanced the input of fine-grained terrigenous sediments to the central Okhotsk Sea.

Riverine nitrogen supply to the global ocean and its limited impact on global marine primary production: a feedback study using an Earth system model

A common notion is that negative feedbacks stabilize the natural marine nitrogen inventory. Recent modeling studies have shown, however, some potential for localized positive feedbacks leading to substantial nitrogen losses in regions where nitrogen fixation and denitrification occur in proximity to each other. Here we include dissolved nitrogen from river discharge in a global 3-D ocean biogeochemistry model and study the effects on near-coastal and remote-open-ocean biogeochemistry. We find that at a steady state the biogeochemical feedbacks in the marine nitrogen cycle, nitrogen input from biological N2 fixation, and nitrogen loss via denitrification mostly compensate for the imposed yearly addition of 22.8 to 45.6 Tg of riverine nitrogen and limit the impact on global marine productivity to < 2 %. Global experiments that regionally isolate river nutrient input show that the sign and strength of the feedbacks depend on the location of the river discharge and the oxygen status of the receiving marine environment. Marine productivity generally increases in proximity to the nitrogen input, but we also find a decline in productivity in the modeled Bay of Bengal and near the mouth of the Amazon River. While most of the changes are located in shelf and near-coastal oceans, nitrogen supply from the rivers can impact the open ocean, due to feedbacks or knock-on effects.

Mid- to late-Holocene analysis of the influence of the La Plata River plume on the southwestern Atlantic shelf: A paleoenvironmental reconstruction based on lipid biomarkers and benthic foraminifera

A combined analysis of sedimentological, molecular, and microfossil proxies was used to determine paleoclimatic and paleoceanographic variations and assess sediment transport pathways along the last c.a. 6300 years in a sedimentary record collected on the inner shelf of the southwestern Atlantic Ocean. The combined use of terrestrial and marine proxies enables a more complete environmental perspective of the La Plata River plume influence on the southwestern Atlantic shelf, regarding the relationship between climate, productivity, as well as hydrodynamic. Variations in marine productivity, lipid biomarkers of terrestrial plants, diagnostic geochemical indices, and sea-surface temperature point to three phases within the core. The first interval (6300–5200 cal yr BP) was characterized by low marine and terrigenous organic matter input, with pulses of phytodetritus indicated by benthic foraminifera. These features suggested dry climatic conditions over the southeastern portion of South America, with the influence of sediments from the adjacent continent and, on a smaller scale, transported from the Argentinian shelf due to the high relative sea level. The second interval (5200–2800 cal yr BP) was distinguished by a slight increase in marine productivity and terrigenous input, indicating a transition period with an increase of total rainfall influenced by an intensified South American Monsoon System (SAMS) and the modern El Niño-Southern Oscillation (ENSO) phenomenon. These features, associated with the changes in wind patterns and the lower relative sea level, suggest the onset of the influence of the La Plata River (LPR) plume over the southern regions of the Brazilian continental shelf for the last 6300 cal yr BP. The last interval (2800–890 cal yr BP) had the highest contents of marine and terrigenous proxies, suggesting less climatic variability, as the long-term intensification of the SAMS and a further increase in the amplitude of the ENSO resulted in the modern establishment and dominant influence of the LPR plume on the core site. Variations in sea-surface temperature up to 3.3°C were related to the influence of the LPR plume on the shelf off southern Brazil.

Weathering controls on the Phanerozoic phosphate cycle

Although phosphate is an essential macronutrient for marine biota, critical to our understanding of marine productivity, biogeochemistry, and evolution, its long-timescale geologic history is poorly constrained. We constrain weathering-derived fluxes and seawater concentrations of phosphate throughout the Phanerozoic (541 Ma to present), by developing a model for the coupled, long-term biogeochemical cycles of phosphate, carbon, oxygen, and calcium. We find that the relative contribution of continental and seafloor weathering to the total weathering rate exerts a first-order control on ocean productivity, through a previously uninvestigated mechanism. Specifically, continental weathering is a source of the limiting nutrient phosphate, but seafloor weathering is not. As a result, times in Earth history in which seafloor weathering constitutes a large fraction of the total weathering rate (e.g., the early Paleozoic and Mesozoic), are also times in which phosphate delivery to the ocean is relatively low. A lower concentration of phosphate in seawater likely affected primary productivity, oceanic and atmospheric oxygen concentrations, with possible implications for the evolution of marine fauna over Earth history.

Changing atmospheric acidity as a modulator of nutrient deposition and ocean biogeochemistry

Anthropogenic emissions to the atmosphere have increased the flux of nutrients, especially nitrogen, to the ocean, but they have also altered the acidity of aerosol, cloud water, and precipitation over much of the marine atmosphere. For nitrogen, acidity-driven changes in chemical speciation result in altered partitioning between the gas and particulate phases that subsequently affect long-range transport. Other important nutrients, notably iron and phosphorus, are affected, because their soluble fractions increase upon exposure to acidic environments during atmospheric transport. These changes affect the magnitude, distribution, and deposition mode of individual nutrients supplied to the ocean, the extent to which nutrient deposition interacts with the sea surface microlayer during its passage into bulk seawater, and the relative abundances of soluble nutrients in atmospheric deposition. Atmospheric acidity change therefore affects ecosystem composition, in addition to overall marine productivity, and these effects will continue to evolve with changing anthropogenic emissions in the future.