High nutrient, low chlorophyll (HNLC) regions, where the availability of iron (Fe) limits primary production, comprise approximately 40% of the global ocean. Variability in Fe supply to these regions has the potential to impact Earth's climate by affecting the efficiency of the biological carbon pump, and thereby carbon dioxide uptake by the oceans. Characterizing Fe sources to HNLC regions is thus crucial for a better understanding of the connections and feedbacks between the ocean and climate change. This work addresses the question of Fe supply to two HNLC regions: the Southern Ocean and the subarctic northeast (NE) Pacific Ocean. In both regions, dissolved Fe (dFe) and the reduced form of iron, Fe(II), were measured in the water column. In the Southern Ocean, measurements were undertaken under the seasonal pack ice in the East Antarctic south of Australia. The results indicate that the sea ice represents a significant dFe source for the under-ice water column in spring, and that the Fe delivered from brine drainage and sea ice-melt likely contributes to the formation of the spring bloom at the ice edge. Shelf sediments were also found to supply dFe to the water column. Their effect was most pronounced near the shelf break and at depth, but offshore transport of Fe-enriched waters was also implicated. Fe(II) concentrations in spring were very low, most likely due to a lack of electron donors in the water column and limited solar radiation underneath the sea ice. Repeat measurements along a transect in the subarctic NE Pacific indicate that shelf sediments supply dFe and Fe(II) at depth, but their influence does not appear to extend offshore beyond several hundred kilometres. Episodic events such as the passage of sub-mesoscale eddies may transport subsurface waters a limited distance from the shelf break, supplying Fe(II) in a depth range where upwelling and deep mixing could bring it to the surface. Offshore, dFe shows little variability except in June 2012, where an aerosol deposition event is suspected to have increased dFe concentrations at depth. Fe(II) concentrations offshore are generally low, but show transient maxima at depth that likely result from remineralization processes in the oxygen deficient zone that stretches from ~600 to 1400 m depth in the subarctic NE Pacific. Elevated Fe(II) concentrations at depth were also observed in conjunction with the aerosol deposition event, which might indicate Fe(II) production associated with settling particles. However, the aerosol deposition event, which most likely stemmed from forest fires in Siberia, did not appear to trigger a phytoplankton bloom in surface waters, possibly due to a lack of Fe fertilization from the deposited material, or due to toxic effects on the resident phytoplankton community. Dust deposition from the atmosphere is considered a major Fe supply mechanism to remote HNLC regions, but the factors affecting Fe solubility of dust are poorly constrained. A laboratory experiment was conducted to test whether the presence of superoxide, a reactive oxygen species, enhances the dissolution of dust from different geographic source regions. The results indicate that superoxide may promote Fe solubilization from the dust sources tested, and that the effect of exposure to superoxide is on par with the Fe solubilizing effect of photochemical reactions. Given the possibility of widespread superoxide production by heterotrophic bacteria at all depths of the ocean, this finding suggests that significant Fe dissolution of dust particles could occur throughout the water column, not only in the well-lit surface layer. / Graduate / 0425 / 0996 / cschalle@uvic.ca

The biogeochemical cycling of oceanic dissolved cadmium (dCd) has been an active area of research for the past ~40 years, due in part to the close correlation with phosphate (PO4). The global Cd:PO4 relationship has led to the use of microfossil Cd/Ca as a paleoproxy for ocean circulation and nutrient utilization; however considerable spatial and temporal variability in the relationship - particularly in surface waters - limits the utility of the proxy. Understanding the global biogeochemical cycling of Cd is an active area of research; however the Arctic Ocean is largely omitted from global models due to lack of data. This work presents depth profiles of dCd and Cd/PO4 ratios from 18 individual stations in the Canadian Arctic, collected during the Canadian GEOTRACES cruises GN02 and GN03, which connect the Arctic Ocean to the North Atlantic through the Canadian Arctic Archipelago (CAA). Salinity-driven water mass stratification exerts a primary control on the spatial distribution of Cd in the region, with elevated dCd and high Cd/PO4 ratios (~0.37 pM/μM) associated with waters of Pacific-origin. The elevated dCd and Cd/PO4 ratios are used as a tracer of Pacific-origin waters, identifying the presence of Pacific-origin water through the CAA and into Baffin Bay. High surface Cd/PO4 ratios were observed across the transect, consistent with a general global increase in surface water Cd/PO4 with increasing latitude. The analysis of Cd and other bioactive trace metals (Mn, Fe, Ni, Cu, Zn and Pb) still presents considerable analytical challenges due to the high-risks of contamination, low concentrations and complex matrices. I present a novel multi-element analytical method, which combines the commercially-available seaFAST pico preconcentration system with ICP-MS/MS analysis. In this work, we demonstrate that ICP-MS/MS, which combines two mass-selecting quadrupoles separated by an octopole collision/reaction cell, effectively removes common interferences (ArO+ on 56Fe and MoO+ on Cd) when pressurized with O2 gas. Accurate and precise measurements of iv the consensus references standards SAFe S and SAFe D and the certified reference material NASS-6 are presented as validation of the method. This thesis presents a novel method for the analysis of trace / Graduate

Le cobalt est un métal de transition essentiel pour la croissance du phytoplancton, et en particulier pour les cyanobactéries qui ont un besoin absolu pour cet élément. En étant l'atome central de la cobalamine (vitamine B12), le cobalt est aussi indirectement essentiel aux eucaryotes marins qui ne synthétisent pas cette vitamine. Cet élément peut se substituer au zinc et au cadmium au sein de la carbonique anhydrase, l’enzyme permettant la fixation du dioxyde de carbone dans la cellule phytoplanctonique. Il pourrait intervenir également dans l’activation de l’alcaline phosphatase. De par ses implications biologiques, le cobalt pourrait jouer un rôle important dans le cycle océanique du carbone. Cependant, les connaissances du cycle biogéochimique du cobalt en milieu marin sont encore largement limitées. Ce travail de thèse de doctorat s’inscrit dans le cadre du programme international GEOTRACES au sein duquel le cobalt y est désigné comme un élément clé de la biogéochimie marine. Au cours de ces travaux, l’un des plus larges jeux de données, rapporté à ce jour, incluant les différentes fractions du cobalt (soluble, dissous, particulaire, spéciation organique) a été produit. Les données recueillies proviennent d’échantillons collectés au sein de domaines océaniques contrastés. Une stratégie de prélèvement à haute résolution et à grande échelle a été mise en place dans diverses régions océaniques du monde lors de campagnes à la mer. Ainsi pour la première fois, une cartographie du cobalt dissous (DCo) et particulaire (PCo) a pu être définie pour l’ensemble de l’Atlantique Ouest, ainsi que des bassins Méditerranéens et de la Mer Noire. Ce jeu de données a pu être produit par l’utilisation de différentes techniques d’analyses (Flow-Injection-Analysis and Chemiluminescence detection ; Voltamétrie, SF-ICP-MS) aux limites de détections basses permettant la détermination de cet élément, présent dans l’eau de mer à des concentrations de l’ordre du pico-molaire (10-12 M). Le cobalt est en effet l’un des micro-nutritifs le moins abondant dans l’eau de mer. Les concentrations les plus faibles en DCo ont été observées dans les eaux oligotrophes de l’Atlantique Ouest (< 15 pM) alors que les plus élevées sont enregistrées dans la couche supérieure des eaux sulfidiques de la Mer Noire (> 5 nM). La distribution verticale du cobalt dissous variait selon les systèmes biogéochimiques. Ainsi, le profil vertical est de type nutritif comme les phosphates dans les eaux de surface de l’océan Atlantique. Les concentrations y augmentent avec la profondeur, jusqu’à un maximum relatif dans les eaux intermédiaires, puis décroissent dans l’océan profond. Ce comportement contraste avec le profil observé pour l’ensemble des bassins de la Mer Méditerranée. Dans cette mer, les fortes concentrations en DCo mesurées en surface (100-300 pM) diminuent en effet avec la profondeur. En Mer Noire, la distribution verticale varie selon les conditions d’oxygénation des eaux. Les concentrations y sont extrêmement élevées par comparaison aux autres systèmes marins. […] / No

Zinc (Zn) and cadmium (Cd) have nutrient-type vertical distributions reflecting control driven by biological uptake in surface waters and remineralization of sinking biogenic particles at depth. Both metals show strong correlations with major algal nutrients (Cd with phosphate (PO43-) and Zn with silicic acid (Si)) in the world ocean. Through their roles as micronutrients and toxins to marine phytoplankton, Zn and Cd can influence surface biological community composition. Preserved Zn and Cd records have been employed as proxies to gain insight into nutrient distributions, circulation, and organic carbon export in the paleocean. A thorough and mechanistic understanding of the biogeochemical cycling of Zn and Cd is necessary for accurate paleoceanographic reconstructions as well as predicting alterations in metal supply to the modern surface ocean and its impacts on primary productivity due to oceanic changes. My dissertation aims to further this understanding through an investigation of Zn and Cd distributions in the subarctic northeast Pacific through samples collected along the Line P transect. A major focus of this dissertation was identifying and characterizing depletions of metals in O2-depleted waters relative to global and basin scale metal:macronutrient correlations. Dissolved Cd profiles from the subarctic northeast Pacific and the eastern North Atlantic show a deficit of Cd relative to regional Cd:PO43- relationships. Particulate Cd and Cd stable isotopes (ε112/110Cd) from low-O2 North Atlantic waters and published sedimentary data from the subarctic northeast Pacific point to a previously undocumented water-column metal removal process acting in O2-depleted waters. Metal sulphide formation, likely in association with particulate microenvironments, can explain the observed deficits. Other metals with similar sulphide coordination chemistry should also form metal sulphides if this process is occurring. Dissolved Zn from Line P showed distributions and Zn:Si relationships that are consistent with the removal of metal in O2-depleted waters through sulphide formation. A first order approximation of the Cd deficit suggests that sulphide formation may be an important sink term in the global Cd cycle. Surface and upper nutricline Zn:Si and Cd:PO43- relationships in the chronically iron (Fe)-limited subarctic northeast Pacific showed distinct trends, which differ from those seen in Fe-replete regions. Distributions suggest the formation of surface biogenic particles with high Cd:PO43- and Zn:Si, leaving surface waters depleted in metals relative to macronutrients and resulting in high metal:macronutrient ratios in the nutricline as these particles sink and are remineralized. This is consistent with understandings of phytoplankton physiology and uptake of divalent metals under Fe-limitation, and corresponds well with global data for dissolved Cd:PO43- patterns in Fe-limited regions. Subsurface high Cd:PO43- and Zn:Si may also be influenced by the advection of water enriched in trace metals. The distinct shallow remineralization horizon observed for Zn compared to Si in the subarctic northeast Pacific by this and previous work presents a fundamentally different distribution than observed in global Zn:Si compilations. Directed sampling in the subarctic northeast Pacific should help elucidate the mechanism behind the oceanographically distinct distributions in this basin. Dissolved ε112/110Cd from Line P demonstrates a remarkably uniform subarctic northeast Pacific deepwater reflecting an advected source signal. Particulate ε112/110Cd samples show an active Cd cycle, which is not imprinted upon the dissolved phase. Particulate ε112/110Cd from 200-600 m depth is among the lightest ε112/110Cd ever reported for natural telluric samples. This may be an important sink for light Cd in the global ocean, which at present is heavy with respect to known sources. Line P surface waters with very low Cd concentrations are not accurately represented by a closed-system Rayleigh model, which can describe ε112/110Cd in the Southern Ocean. This suggests spatially and/or temporally variable surface ε112/110Cd fractionation. A large difference is observed in reported dissolved ε112/110Cd at very low Cd concentrations between different instrumentations. An intercalibration is necessary to determine if this is an analytical artefact or reflects real oceanic variability. / Graduate

L'Océan Austral est connu pour être la plus vaste zone "High-Nutrient, Low-Chlorophyll" de l'océan mondial. Bien que les concentrations en nutriments (nitrates, phosphates, silicates) soient élevées, le développement du phytoplancton est paradoxalement limité principalement par les faibles concentrations en fer (Martin et al. 1990). Les archipels de Crozet et des Kerguelen, situés dans le secteur Indien de l'océan Austral, constituent deux obstacles topographiques importants à l'écoulement vers l'Est du Courant Circumpolaire Antarctique. L'interaction du courant avec les sédiments des plateaux peu profonds alimente en fer les eaux en aval de ces îles, générant ainsi d'importants blooms phytoplanctoniques (Blain et al. 2007, Pollard et al. 2007). Ceux-ci constituent des laboratoires à ciel ouvert uniques pour étudier la réponse des écosystèmes et l'impact de la fertilisation naturelle en fer sur les cycles biogéochimiques. Cette thèse s'inscrit sans le cadre du projet KEOPS-2. Les isotopes du radium (223Ra, 224Ra, 226Ra et 228Ra), qui constituent de puissants outils pour étudier la circulation océanique et le mélange, sont les principaux outils utilisés ici. Les quatre isotopes du radium ont des périodes radioactives allant de quelques jours à plus d'un millier d'années et sont produits par la décroissance radioactive du thorium dans le sédiment. Ils sont apportés à l'océan par des processus de diffusion et d'advection où ils se comportent comme des traceurs conservatifs de telle manière que la masse d'eau garde la signature de son contact avec les sédiments modulée par la période radioactive des isotopes du radium. Par conséquent, les isotopes du radium ont été utilisés pour (i) tracer l'origine et la dispersion des éléments chimiques - y compris le fer - libérés par les sédiments et (ii) estimer les échelles de temps du transit des eaux de surface depuis les plateaux continentaux vers le large. Les informations acquises avec les isotopes du radium ont été comparées aux informations issues d'outils physiques (flotteurs dérivant de surface et modèle Lagrangien dérivé de l'altimétrie). Premièrement, la comparaison de ces trois méthodes indépendantes - géochimiques et physiques - dans la région de Crozet a permis de valider leur utilisation. Deuxièmement, nous avons montré que le panache de phytoplancton associé aux îles Crozet est alimenté par deux sources différentes d'eau qui ont interagi avec soit le plateau ouest soit le plateau est. Troisièmement, cette approche couplée physique-géochimique a également été utilisée dans la région des Kerguelen et a aidé à contraindre l'origine de la fertilisation en fer dans cette zone. L'observation d'activités significatives de 223Ra et 224Ra dans les eaux de surface à l'est des îles Kerguelen indique que ces eaux ont récemment interagi avec des sédiments peu profonds. La variabilité spatiale de ces activités en surface au sud du Front Polaire (PF) suggère que le passage des eaux et des éléments chimiques à travers ou via le PF peut varier à la fois spatialement et temporellement. Cette voie constituerait donc un mécanisme de fertilisation (en fer et autres micronutriments) du bloom phytoplanctonique qui se développe au large des îles Kerguelen. Ces résultats indiquent que le PF n'agirait donc pas comme une barrière physique aussi forte qu'on le pensait, pour les masses d'eau et les éléments chimiques. Ces conclusions pourraient également s'appliquer à d'autres systèmes de fronts de l'océan mondial. Finalement, j'ai compilé les distributions de 226Ra et de baryum dissous (Ba) au large des îles Crozet et Kerguelen dans le but de fournir des contraintes supplémentaires sur la circulation locale. En particulier, des variations temporelles des rapports 226Ra/Ba dans la phase dissoute ont été observées. Parmi les hypothèses potentielles, on peut évoquer (i) des changements de la circulation ou (ii) un impact des processus biologiques sur les concentrations de Ra et Ba de la phase dissoute. / The Southern Ocean is known to be the largest High-Nutrient, Low-Chlorophyll region of the global ocean. While nutrient concentrations (nitrate, phosphate, silicate) are high, the phytoplankton development is paradoxically limited mostly because of the low dissolved iron concentrations of the Southern Ocean waters (Martin_iron_1990). The Crozet and Kerguelen Archipelagos, located in the Indian sector of the Southern Ocean, constitute two major topographic obstacles to the eastward-flowing Antarctic Circumpolar Current. The interaction of the current with the sediments of the shallow Crozet and Kerguelen plateaus contributes to the supply of iron downstream of these islands, thus leading to large phytoplankton blooms in these regions (Blain et al. 2007, Pollard et al. 2007). These phytoplankton blooms constitute unique open-air laboratories to study the response of the ecosystems and the impact on biogeochemical cycles to natural iron fertilization. This PhD thesis was done in the framework of the KEOPS-2 project. Radium isotopes (223Ra, 224Ra, 226Ra and 228Ra), that are powerful tools to study the ocean circulation and mixing, are the main tools used here. The four natural occurring isotopes display half-lives ranging from a few days to thousands of years and are produced by the decay of particle-bound thorium isotopes in sediments. They are delivered to the open ocean by diffusion and advection processes where they behave as conservative tracers in such a way that the water body keeps the signature of its contact with the sediments modulated by the half-lives of the radium isotopes. Therefore, we used Ra isotopes to (i) investigate the origin and the dispersion of the sediment-derived inputs - including iron - and (ii) to estimate the timescales of the transfer of surface waters between the shelf and offshore waters. We compared the Ra dataset with data acquired using physical tools (surface drifters and Lagrangian model derived from altimetry). Firstly, the use of three independent methods - including geochemical and physical methods - in the Crozet region allowed us to validate each method. Secondly, we show that the Crozet Island phytoplankton plume is fed by two different flows of water that interacted with either the western plateau or the eastern plateau. Thirdly, this physical-geochemical coupled approach was also used in the Kerguelen region and helped us to constrain the origin of the iron fertilization in that area. The observation of 223Ra and 224Ra in surface waters east of the Kerguelen Islands, south of the polar front (PF), indicates that these waters have recently interacted with shallow sediments. The spatial variability observed in the 223Ra and 224Ra distribution in surface waters south of the PF suggests that the input of waters and associated chemical elements across or via the PF - potentially driven by wind stress or eddies - act as sporadic pulses that may highly vary in both space and time. This pathway may thus constitute a mechanism that contributes to fertilizing the phytoplankton bloom with iron and other micronutrients east of the Kerguelen Islands. This finding also suggest that the PF may not act as a strong barrier for surface waters and associated chemical elements, a finding that may also apply for other frontal systems of the world's ocean. Finally, we investigated the 226Ra and barium (Ba) distributions offshore from the Crozet and Kerguelen islands, with the aim to provide additional constraints on the circulation patterns in this area. In particular, we observed temporal changes in the dissolved 226Ra/Ba ratios. Among potential hypothesis, one can invoke (i) changes in the circulation patterns or (ii) the impact of biological processes on the dissolved Ra and Ba concentrations.

Multi-proxy approach for the reconstruction of paleo-redox conditions is attempted on a radiocarbon (C-14) dated sediment core near the equatorial Indian Ocean. Based on the behavior and distribution of redox sensitive and productivity proxies, study demonstrates prevalence of anoxic bottom water conditions during LGM due to poorly ventilated bottom waters augmented by high surface productivity resulting in better preservation of organic carbon (OC). During early Holocene, the equatorial Indian Ocean witnessed high sedimentation rates resulting in high organic carbon (OC) with depleted redox sensitive elements thereby causing better preservation of OC. The study underscores poor bottom water ventilation during LGM and preservation of OC as a result of high sedimentation rate in early Holocene.

No description available.