The purpose of this study is to investigate the evolution of the Arctic Ocean’s carbon uptake capacity and impacts on ocean acidification with the changing sea-ice scape. In particular, I study the influence on air-ice-sea fluxes of carbon with two major updates to commonly-used carbon cycle models I have included. One, incorporation of sea ice algae to the ecosystem, and two, modification of the sea-ice carbon pump, to transport brineassociated Dissolved Inorganic Carbon (DIC) and Total Alkalinity (TA) to the depth of the bottom of the mixed layer (as opposed to releasing it in the surface model layer). I developed the ice algal ecosystem model by adding a sympagic (ice-associated) ecosystem into a 1D coupled sea ice-ocean model. The 1D model was applied to Resolute Passage in the Canadian Arctic Archipelago and evaluated with observations from a field campaign during the spring of 2010. I then implemented an inorganic carbon system into the model. The carbon system includes effects on both DIC and TA due to the coupled ice-ocean ecosystem, ikaite precipitation and dissolution, ice-air and air-sea carbon exchange, and ice-sea DIC and TA exchange through a formulation for brine rejection to depth and freshwater dilution associated with ice growth and melt. The 1D simulated ecosystem was found to compare reasonably well with observations in terms of bloom onset and seasonal progression for both the sympagic and pelagic algae. In addition, the inorganic carbon system showed reasonable agreement between observations of upper water column DIC and TA content. The simulated average ocean carbon uptake during the period of open water was 10.2 mmol C m−2 day−1 ( 11 g C m−2 over the entire open-water season). Using the developments from the 1D model, a 3D biogeochemical model of the Arctic Ocean incorporating both sea ice and the water column was developed and tested, with a focus on the pan-Arctic oceanic uptake of carbon in the recent era of Arctic sea ice decline (1980 – 2015). The model suggests the total uptake of carbon for the Arctic Ocean (north of 66.5 N) increases from 110 Tg C yr−1 in the early eighties (1980 – 1985) to 140 Tg C yr−1 for 2010 – 2015, an increase of 30%. The rise in SST accounts for 10% of the increase in simulated pan-Arctic sea surface pCO2. A regional analysis indicated large variability between regions, with the Laptev Sea exhibiting low sea surface pH relative to the pan- Arctic domain mean and seasonal undersaturation of arag by the end of the standard run. Two sensitivity studies were performed to assess the effects of sea-ice algae and the sea-ice carbon pump in the pan-Arctic, with a focus on sea surface inorganic carbon properties. Excluding the sea ice-carbon-pump showed a marked decrease in seasonal variability of sea-surface DIC and TA averaged over the Arctic Ocean compared to the standard run, but only a small change in the net total carbon uptake (of 1% by the end of the no icecarbon-pump run). Neglecting the sea ice algae, on the other hand, exhibits only a small change in sea-surface DIC and TA averaged over the pan-Arctic Ocean, but a cumulative effect on the net total carbon uptake of the Arctic Ocean (reaching 5% less than that of the standard run by the end of the no-ice-algae run). / Graduate

We use a numerical ocean model to evaluate the hypothesis that the continental shelves are significant sources of dissolved iron to the Southern Ocean. We simulate the distribution of passive tracers released from the 18 different continental shelf regions of the extra-tropical southern hemisphere oceans using an offline, eddy-permitting transport model. The circulation fields are taken from the Southern Ocean State Estimate, and we only simulate the transport of inert tracers focusing on the physical transport pathways. The resulting tracer fields are then compared with the remotely sensed ocean color data, revealing a remarkable resemblance between the distributions of shelf-source tracers and the climatological surface chlorophyll-a concentrations. We further analyze the spatial pattern of simulated tracer fields in relation to satellite ocean color data. Dynamic ocean features such as the Southern Ocean fronts and coastal waters are reflected in both the tracer model and the observed biological productivity. Our results support the overall importance of continental shelves as a potential source region for dissolved iron. The relative importance of different shelf regions is found to vary significantly depending on the relevant circulation features.

Coastal oceans play an important role in the carbon cycle and are hotspots of ocean primary production and ocean acidification. These coastal regions are strongly influenced by rives, especially in the Arctic. Despite the importance of the riverine delivery of carbon and nutrients, their effect on the Arctic Ocean is still poorly understood due to hostile conditions and the consequently low number of observations. This thesis aims at improving our understanding of the influence of Arctic riverine delivery of carbon and nutrients by using ocean biogeochemical models.The first part of the thesis evaluated the model skills of the ocean biogeochemical model NEMO-PISCES in the Arctic Ocean. By analyzing model results at different horizontal resolutions, the importance of lateral influx from the adjacent oceans for anthropogenic carbon cycle in the Arctic Ocean wasdemonstrated. These results were then used to adjust a previously published data-based estimate of anthropogenic carbon storage in the Arctic Ocean and the corresponding ocean acidification.In the second part, a pan-Arctic observation-based dataset of riverine carbon and nutrient fluxes was created. This dataset was then used to force the ocean biogeochemical model and the river fluxes were quantified. River fluxes have been shown to sustain up to 24% of Arctic Ocean primary production, to reduce the air-sea CO2 uptake by 20%, and to reduce surface ocean acidification seasonally. Eventually, idealized simulations were made to quantify the sensitivity of the Arctic Ocean biogeochemistry to future changes in riverine delivery of carbon and nutrients. Sensitivities are of small magnitude on a pan-Arctic scale, importance in the coastal areas, and the dominant factor close to river mouths. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Ocean nitrogen fixation and denitrification are crucial nitrogen source and sink mechanisms for the global ocean environment. While recent studies have reported that oceanic denitrification has increased over the last few decades, others have suggested that global ocean nitrogen fixation rates have been underestimated, and still others that anthropogenic perturbations have altered the global nitrogen cycle. This implies that the current estimates of the oceanic nitrogen inventory are incomplete and they need to be revised with more information. In addition, current denitrification estimates need to be reexamined due to their large associated uncertainties. Thus, I have conducted research estimating denitrification rates in three different locations: the northern Gulf of Mexico (GOM), the East/Japan Sea (EJS), and the South Pacific: from coastal to marginal to open ocean scale in different oceanographic conditions. Denitrification rates in the bottom layer (including bottom waters+sediments) at the shallow and often hypoxic northern GOM ranged from 103-544 [mu]mol N m⁻² d⁻¹ (=1.4 to 7.4 Gg N mon⁻¹ with area=3.24x10¹⁰m²), and were controlled not only by biogeochemical factors (i.e. organic matter supply and remineralization), but also by physical factors (i.e. stratification and relative contributions from different water masses). Despite high dissolved oxygen concentrations, the significant decrease in nitrate concentrations below the expected levels, low N/P ratio (<12.4), and deep nitrite peak in the bottom layer indicate a presence of denitrification in EJS, confined at the Tatar Strait and the Ulleung Basin areas. The estimated denitrification rates range from 0.3 to 33.2 [mu]mol N m⁻² d⁻¹, and was comparable to the directly measured denitrification rates from sediment samples. The high-quality repeat hydrographic datasets observed at 32°S of the South Pacific Ocean offer an opportunity to estimate water column denitrification rates on a basin-scale in the open ocean away from the Eastern Tropical Pacific oxygen minimum zones. The mean water column denitrification rates in the oxygen minimum layer of P06 line (32°S) were estimated to range between 7.1 and 18.5 [mu]mol N m⁻² d⁻¹. The results imply that, although very small at any particular site, once integrated over a basin-scale, the open ocean water column denitrification can be a significant component of the oceanic nitrogen budget. Denitrification is subject to seasonal, decadal and possibly climate scale variations. While it is commonly estimated at the oxygen minimum zones or sediments, denitrification is not merely confined to such regions only, and small amounts of denitrification occur in other oceanic parts. Once integrated, it may be quantitatively significant for the world's oceans. Denitrification is playing a significant role in local, regional, and global ocean scales. In the future, we need to consider variability of denitrification in coastal regions, and to investigate denitrification in unexpected and unexplored regions, in order to improve our knowledge on global oceanic mass balance. / text

The western Antarctic Peninsula (WAP) is a hotspot of climatic and oceanographic change, with a 6°C rise in winter atmospheric temperatures and >1°C warming of the surface ocean since the 1950s. These trends are having a profound impact on the physical environment at the WAP, with widespread glacial retreat, a 40% decline in sea ice coverage and intensification of deep water upwelling. The main objective of this study is to assess the response of phytoplankton productivity to these changes, and implications for the marine carbon and nitrogen cycles in the WAP coastal zone. An extensive suite of biogeochemical and physical oceanographic data was collected over five austral summer growing seasons in northern Marguerite Bay between 2004 and 2010. Concentrations and isotopic compositions ( 15N, 13C, 14C) of dissolved nitrate, dissolved inorganic carbon species, particulate nitrogen, organic carbon and chlorophyll a are used in the context of a substantial ancillary dataset to investigate nutrient supply, phytoplankton productivity and nutrient uptake, export flux and the fate of organic material, and the factors underpinning pronounced seasonal and interannual variability. High-resolution biogeochemical time-series data for surface and underlying seawater, sea ice brine, sediment trap material and coretop sediments allow detailed examination of carbon and nitrogen cycle processes under contrasting oceanographic conditions and the interaction between these marine processes and air-sea exchange of climate-relevant CO2. This study shows that the WAP marine environment is currently a summertime sink for atmospheric CO2 in most years due to high productivity and biological carbon uptake sufficient to offset the CO2 supply from circumpolar deep waters, which act as a persistent source of heat, nutrients and CO2 across the shelf. For the first time, CO2 sink/source behaviour is parameterised in terms of nitrate utilisation, by exploiting the relationship between CO2 and nitrate concentrations, and deriving the nitrate depletion at which surface ocean CO2 is undersaturated relative to atmosphere and carbon sink behaviour is achieved. This could have vast utility in examining CO2 sink/source dynamics over greater spatial and temporal scales than by direct CO2 measurements, of which availability is more limited. This study documents abrupt changes in phytoplankton productivity, nitrate utilisation and biological CO2 uptake during a period of rapid sea ice decline. In fact, nitrate utilisation, particulate organic matter production and biological CO2 uptake all decrease by at least 50 % between a sea ice-influenced, high productivity season and one of low sea ice and low productivity. The key driver of interannual variability in production and export of organic material is found to be upper ocean stratification and its regulation of light availability to phytoplankton. Productivity, CO2 uptake and export are maximal when stratification is sufficient to provide a stable well-lit surface environment for phytoplankton growth, but with some degree of mixing to promote export of suspended organic matter. Strong stratification causes intense initial production, but retention of suspended organic particles in the surface ocean induces a self-shading effect, and overall productivity, CO2 uptake and export fluxes are low. When stratification is weak, mixing of phytoplankton over a larger depth range exposes cells to a wider range of light levels and reduces photosynthetic efficiency, thus total productivity and CO2 uptake. A conceptual model is developed here, which attempts to describe the mechanism by which sea ice dynamics exert the principal control on stratification and therefore productivity and CO2 uptake at the WAP, with potential application to other regions of the Antarctic continental shelf. Although meteoric waters (glacial melt and precipitation) are more prevalent in surface waters throughout the study, sea ice meltwater variability is driven by large and rapid spring/early summer pulses, which stabilise the upper ocean and initiate phytoplankton growth. The timing and magnitude of these sea ice melt pulses then exert the key control on stratification and seasonal productivity. In a low sea ice year of this study, the sea ice trigger mechanism was absent and productivity was low. This strongly suggests that ongoing sea ice decline at the WAP and greater frequency of such low sea ice years is likely to drive a dramatic reduction in productivity and export, which would substantially reduce the capacity of the summertime CO2 sink in this region. Ongoing warming and ecosystem change are thus likely to have severe impacts on net CO2 sink/source behaviour at the WAP over the annual cycle, and the role of the Southern Ocean in regulating atmospheric CO2 and global climate. Finally, factors influencing the stable isotopic signature of particulate organic carbon ( 13CPOC), a common paleo-proxy, are assessed. 13CPOC is greatly influenced by seasonal shifts in diatom assemblages and isotopically heavy sea ice material, so cannot be used as a robust proxy for ambient CO2 in the coastal Southern Ocean.

Diatoms play a fundamental role in marine food webs, and significantly contribute to global primary production and carbon sequestration into the deep ocean. In many offshore areas of the open ocean, iron (Fe) input is low, and its availability often limits phytoplankton biomass. Recently, gene sequences encoding ferritin, a nearly ubiquitous iron storage and detoxifying protein, have been identified in pennate diatoms such as Pseudo-nitzschia, but not in other Stramenopiles (which include centric diatoms, brown algae and some protist plant parasites) or Cryptophyte relatives. Members of this genus readily bloom upon addition of iron to Fe-limited waters, and are known to produce the neurotoxin domoic acid. Until now, the reason for the success of pennate diatoms in the open ocean was uncertain; however, expressing ferritin would allow pennate species to store Fe after a transient input, using it to dominate Fe stimulated algal blooms. Here, the ferritin gene was cloned from the coastal pennate diatom Pseudonitzschia multiseries, overexpressed in Escherichia coli, and purified using liquid chromatography. The ferritin protein sequence appears to encode a non-heme, ferritinlike di-iron carboxylate protein, while gel filtration chromatography and SDS-PAGE indicate that this ferritin is part of the 24 subunit maxi-ferritins. Spectroscopically monitoring the addition of Fe(II) to a buffered ferritin solution shows that the P. multiseries protein demonstrates ferroxidase activity, binding iron and storing it as Fe(III) in excess of 600 equivalents per protein shell. In keeping with the typical stoichiometry of the ferroxidase reaction, oxygen (O₂) is consumed in a 2 Fe:O₂ratio while hydrogen peroxide is produced concurrently. iii Diatoms evolved from secondary endosymbiosis involving eukaryotic red algae; however, a broad phylogenetic comparison suggests that P. multiseries ferritin was likely acquired via lateral gene transfer from cyanobacteria – not from its ancestral endosymbionts. Until recently, no other ferritins have been identified in diatoms, and the protein characterized here is unique in that it seems to be derived from a prokaryotic organism yet it occurs in a marine eukaryote. These findings have direct implications for the success of pennate diatoms in both Fe rich coastal waters and upon Fe addition in the open ocean.

Diatoms play a fundamental role in marine food webs, and significantly contribute to global primary production and carbon sequestration into the deep ocean. In many offshore areas of the open ocean, iron (Fe) input is low, and its availability often limits phytoplankton biomass. Recently, gene sequences encoding ferritin, a nearly ubiquitous iron storage and detoxifying protein, have been identified in pennate diatoms such as Pseudo-nitzschia, but not in other Stramenopiles (which include centric diatoms, brown algae and some protist plant parasites) or Cryptophyte relatives. Members of this genus readily bloom upon addition of iron to Fe-limited waters, and are known to produce the neurotoxin domoic acid. Until now, the reason for the success of pennate diatoms in the open ocean was uncertain; however, expressing ferritin would allow pennate species to store Fe after a transient input, using it to dominate Fe stimulated algal blooms. Here, the ferritin gene was cloned from the coastal pennate diatom Pseudonitzschia multiseries, overexpressed in Escherichia coli, and purified using liquid chromatography. The ferritin protein sequence appears to encode a non-heme, ferritinlike di-iron carboxylate protein, while gel filtration chromatography and SDS-PAGE indicate that this ferritin is part of the 24 subunit maxi-ferritins. Spectroscopically monitoring the addition of Fe(II) to a buffered ferritin solution shows that the P. multiseries protein demonstrates ferroxidase activity, binding iron and storing it as Fe(III) in excess of 600 equivalents per protein shell. In keeping with the typical stoichiometry of the ferroxidase reaction, oxygen (O₂) is consumed in a 2 Fe:O₂ratio while hydrogen peroxide is produced concurrently. iii Diatoms evolved from secondary endosymbiosis involving eukaryotic red algae; however, a broad phylogenetic comparison suggests that P. multiseries ferritin was likely acquired via lateral gene transfer from cyanobacteria – not from its ancestral endosymbionts. Until recently, no other ferritins have been identified in diatoms, and the protein characterized here is unique in that it seems to be derived from a prokaryotic organism yet it occurs in a marine eukaryote. These findings have direct implications for the success of pennate diatoms in both Fe rich coastal waters and upon Fe addition in the open ocean.

Diatoms play a fundamental role in marine food webs, and significantly contribute to global primary production and carbon sequestration into the deep ocean. In many offshore areas of the open ocean, iron (Fe) input is low, and its availability often limits phytoplankton biomass. Recently, gene sequences encoding ferritin, a nearly ubiquitous iron storage and detoxifying protein, have been identified in pennate diatoms such as Pseudo-nitzschia, but not in other Stramenopiles (which include centric diatoms, brown algae and some protist plant parasites) or Cryptophyte relatives. Members of this genus readily bloom upon addition of iron to Fe-limited waters, and are known to produce the neurotoxin domoic acid. Until now, the reason for the success of pennate diatoms in the open ocean was uncertain; however, expressing ferritin would allow pennate species to store Fe after a transient input, using it to dominate Fe stimulated algal blooms. Here, the ferritin gene was cloned from the coastal pennate diatom Pseudonitzschia multiseries, overexpressed in Escherichia coli, and purified using liquid chromatography. The ferritin protein sequence appears to encode a non-heme, ferritinlike di-iron carboxylate protein, while gel filtration chromatography and SDS-PAGE indicate that this ferritin is part of the 24 subunit maxi-ferritins. Spectroscopically monitoring the addition of Fe(II) to a buffered ferritin solution shows that the P. multiseries protein demonstrates ferroxidase activity, binding iron and storing it as Fe(III) in excess of 600 equivalents per protein shell. In keeping with the typical stoichiometry of the ferroxidase reaction, oxygen (O₂) is consumed in a 2 Fe:O₂ratio while hydrogen peroxide is produced concurrently. iii Diatoms evolved from secondary endosymbiosis involving eukaryotic red algae; however, a broad phylogenetic comparison suggests that P. multiseries ferritin was likely acquired via lateral gene transfer from cyanobacteria – not from its ancestral endosymbionts. Until recently, no other ferritins have been identified in diatoms, and the protein characterized here is unique in that it seems to be derived from a prokaryotic organism yet it occurs in a marine eukaryote. These findings have direct implications for the success of pennate diatoms in both Fe rich coastal waters and upon Fe addition in the open ocean. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate