Impact of ocean acidification and ocean warming on the oxidation of dissolved Fe(II) in coastal and open Southern Ocean water

The Southern Ocean is the largest region where major nutrients such as nitrate, silicate and phosphate are present in excess, yet the crucial micronutrient element iron (Fe) is scarce. It is well established that the Southern Ocean is key in exporting carbon to greater depths through biomass production by phytoplankton, but Fe is metabolically required for photosynthesis. Changes in uptake of carbon and heat to the ocean will impact ocean acidification and ocean warming. These anthropogenically linked processes are projected to lead to a drop in ocean pH by 0.2 units and an increase in the ocean‚ÄövÑv¥s temperature by 2¬¨‚àûC by the end of the century and are already known to have tremendous ecological impacts on the ocean‚ÄövÑv¥s flora and fauna. However, little is known about how changes in ocean temperature and pH could alter the nutrient composition in future oceans. Regarding nutrients, this work focuses on the dissolved (d) element Fe. It is essential for photosynthesis, but also a limiting element in the Southern Ocean due to limiting sources leading to low availability. Iron exists in two redox states in seawater. While the species dFe(III) is stable in seawater and occurs in relatively higher concentrations, its redox partner dFe(II) is tied to several physico-chemical processes impacting its oxidation time and overall presence. The importance of dFe(II) also lies with its accessibility for phytoplankton in its reduced oxidative state. The overall aim of this study was to investigate changes in concentration, speciation, and availability of the ‚ÄövÑv=more‚ÄövÑv¥ bioavailable, rapidly oxidizing Fe species dFe(II) under a changing Southern Ocean scenario. Chapter 2 addressed the redox behaviour of dFe(II) and dFe(III), where several questions were explored for further experimental planning. The main question was how the coastal and open ocean systems differ in their dFe(II) concentrations and how ocean acidification and ocean warming impact Fe redox chemistry in both systems. I therefore performed controlled acidification and temperature alteration experiments in coastal and open ocean water taken from the Tasmanian coast and the Southern Ocean. This large dataset enabled us to project for future ocean dFe(II) concentrations and oxidation rates. I observed that a reduction in ocean pH by 0.2 units doubles the dFe(II) oxidation time in the open ocean and tripled in coastal water through model-based experiments. In contrast to these high impacts from pH, an increase in temperature by 1¬¨‚àûC accelerated the oxidation by ~ 1.1 times (13% in coastal water and 8% in open ocean water). Therefore, realistic changes in temperature are likely to have small impacts on the oxidation of dFe(II) in both water systems compared to the proposed changes in pH. For phytoplankton, these results pose contradicting outcomes, and studies display mixed results once parameters such as ocean warming, and acidification are combined. An increase in temperature might lead to less or no growth once a certain temperature threshold is crossed. Similarly, a decrease in pH is also thought to impact phytoplankton physiology. It also depends on the severity of acidification and the phytoplankton species itself. Ocean warming could reduce phytoplankton growth, despite increased Fe availability due to higher solubility in warmer water. Regarding ocean acidification, on the other hand, dFe(II) could become available for an extended time, therefore enabling further uptake of dFe(II) by phytoplankton for that time. When comparing mixed effects of ocean acidification and warming, a reduction in pH might have a greater impact on the dFe(II) oxidation than just temperature. Temperature changes, however, might be a greater concern in the near future before ocean acidification becomes relevant. Due to this projection of temperature being a more imminent concern, I targeted the limiting element Fe in its less investigated form dFe(II). I observed how temperature alone impacts growth of two Southern Ocean phytoplankton species. I therefore ran an dFe(II)-enrichment incubation experiment in Chapter 3 with differing temperatures (3¬¨‚àûC, 5¬¨‚àûC, and 7¬¨‚àûC) in coastal and open ocean water from the Southern Ocean using the well-studied haptophyte Phaeocystis antarctica and the diatom Fragilariopsis cylindrus. These enrichment experiments with altered temperatures overall confirmed that phytoplankton growth was elevated once 5 nM dFe(II) were added. In other words, freely available dFe(II) was present, almost regardless of the temperature increase from 3¬¨‚àûC to 7¬¨‚àûC. This could implicate that an increase in temperature has beneficial effects on growth in the case of higher concentrations of freely available dFe(II). However, these values of future dFe(II) concentrations and oxidation rates under acidified and warmer scenarios are only laboratory-based projections, to better understand the dFe(II) presence and demand by phytoplankton species in a future Southern Ocean. In Chapter 4, a one-month field study onboard the RV Investigator was conducted east of the Australian continent along the East Australian Current (EAC) into nutrient-rich but Fe poor water in the Southern Ocean. I observed the overall distribution of dFe(II) and hydrogen peroxide in this understudied region. The findings suggest that dFe(II) concentrations are very low in the observed area of the open Southern Ocean (< 0.1 nM) compared to coastal waters (> 0.5 nM), likely driven by differences in terrestrial Fe inputs. Hydrogen peroxide was generally higher in the southern stations within the upper 200 m (~60 nM) while the dFe(II) : dFe ratios are 10 % higher than reported for previous Southern Ocean studies. High biological activity in the upper water extending to the frontal mixing zone where the two major currents meet (EAC and STF), may further have led to the observed low dFe concentrations and high H\\(_2\\)O\\(_2\\) concentrations. Occasional higher dFe(II) peaks found in this area in surface water may be the result of several external sources such as rain or vertical transport from seamounts but also due to biological or physico-chemical impacts such as photochemical reduction or uptake by phytoplankton. Overall, the work in this study advances our understanding of the coupled effects of the climate change parameters ocean acidification and ocean warming on the dFe(II) oxidation, with implications for its availability to phytoplankton and overall sources in the region east and south-east of Tasmania in coastal and open ocean water. The experimental approaches taken suggest a higher impact of ocean acidification compared to ocean warming and a potential benefit for phytoplankton species preferring dFe(II).