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The solubility of iron (Fe) in seawater is greatly enhanced by complexation with organic ligands, predominantly occurring as humic substances (HS) in coastal areas. Mining exploitation is believed to change the natural biogeochemical cycle of Fe in coastal waters, even though its impacts on the physical and chemical speciation of the Fe fractions are not known. Here we show that dissolved and soluble Fe concentrations in coastal waters affected by a mining catastrophe (Fundão dam, Southeast Brazil) remain very high, even almost 3 years later, with concentrations of dissolved Fe up to 2.8 μM (0.45 μm filtration) or 700 nM (0.22 μm filtration), and soluble Fe (0.02 μm) up to 40 nM. Levels of humic substances can only explain the binding of 2% and 10% (median values) of dissolved Fe (0.22 μm) and soluble Fe concentrations, respectively, which shows that processes other than complexation with humic substances are at play to maintain such high dissolved Fe concentrations. We hypothesize that the colloidal phase that dominates the dissolved Fe fraction occurs as Fe(III) oxyhydroxides while the soluble fraction is comprised of Fe(III) complexes with amine compounds (widely used in the ore extraction process). Mass balance of dissolved Fe in the water column suggests that sediment resuspension on the continental shelf is by far the dominant process delivering dissolved Fe to coastal and shelf waters. Estimates of dissolved Fe yearly fluxes highlight the sheer magnitude of this catastrophe that might provide a non-negligible amount of dissolved Fe to the open ocean.

The high N 2 fixation rate observed in the Lau Basin of the western tropical South Pacific Ocean (WTSP) is fueled by iron (Fe) released from shallow hydrothermal systems. Understanding Fe bioavailability is crucial but the controls on the stability and bioavailability of hydrothermal Fe inputs are still poorly understood. Here, we provide new data on the spatial and vertical distribution of the soluble ubiquitous humic-like ligands (L FeHS ) and their associated dissolved Fe (DFe) in the WTSP, including in samples near hydrothermal vents. Our data show that L FeHS are heterogenous ligands with binding sites of both strong and intermediate strengths. These ligands are primarily produced in surface waters and partially mineralized in mesopelagic waters. A substantial fraction of DFe was complexed by L FeHS (mean ~30%). The DFe complexed by L FeHS is likely bioavailable to phytoplankton and L FeHS stabilized Fe released by the mineralization of sinking biomass. However, unsaturation of L FeHS by Fe suggest that part of DFe is not available for complexation with L FeHS . Possible reasons are competition between DFe and other metals, such as dissolved copper, or the inability of L FeHS to access colloidal DFe. The study of two volcanic sites indicates that L FeHS were not produced in these hydrothermal systems. At the active site (DFe ~50 nmol L -1 ), L FeHS can only partially solubilize the hydrothermal DFe released in this area (1~5.5% of the total DFe). We performed controlled laboratory experiments which show that the observed low solubilization yield result from the inability of L FeHS to solubilize aged Fe oxyhydroxides (FeOx - a kinetically mediated process) and to form stable complexes with Fe(II) species. Our study provides new understanding of the role of L FeHS on the bioavailability and stabilization of hydrothermal DFe.

Iron (Fe) is an essential micronutrient for phytoplankton growth, but its scarcity in seawater limits primary productivity across much of the ocean. Most dissolved Fe (DFe) in seawater is complexed with Fe-binding organic ligands, a poorly constrained fraction of dissolved organic matter (DOM), which increase Fe residence time and impact Fe bioavailability. Here, we present the conditional concentration (L Fe ) and binding-strength (log K F e ' L c o n d ) of Fe-binding ligands in the Western Tropical South Pacific (WTSP) Ocean during the GEOTRACES TONGA cruise (GPpr14). The transect crossed the Lau basin, a region subject to shallow hydrothermal Fe inputs that fuel intense diazotrophic activity, the oligotrophic South Pacific gyre, and the Melanesian basin. Organic speciation was analyzed by competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-AdCSV) using salicylaldoxime at 25 µM. We found a high mean L Fe of 5.2 ± 1.2 nMeqFe (n = 103) across the entire transect, predominantly consisting of intermediate strength L2 ligands (84%; mean log K F e ' L c o n d of 11.6 ± 0.4), consistent with humic-like substances. DFe correlated with the humic-like component of the fluorescent DOM (HS-like FDOM), yet the electroactive Fe-binding humic-like substances (L FeHS ) accounted for only 20 ± 13% of L Fe in the mixed layer and 8 ± 6% in deep waters. Ligands were in large excess compared to DFe (mean excess ligand eL Fe = 4.6 ± 1.1 nMeqFe), suggesting poor stabilization of DFe inputs. High L Fe (up to 9 nMeqFe) in samples close to hydrothermal sites could be due to detoxification strategies from plankton communities toward hydrothermally-fueled toxic trace metals other than Fe, with an apparent dilution of the DOM from the Lau basin into neighboring regions. We also observed a different peak potential of the Fe salicylaldoxime complex detected by CLE-AdCSV between the Lau and Melanesian basins, and between surface and deep waters. To our knowledge, this change in potential has not previously been reported; whether this represents a novel detection of specificities in DOM composition merits further investigation. Competition between Fe and competing metals for ligand binding sites could favor DFe oxidation and precipitation near hydrothermal vents and explain the absence of strong Fe stabilization in the WTSP.

Antarctic Bottom Water (AABW) is known as a long-term sink for anthropogenic CO2 (Cant), but the sink is hardly quantified because of the scarcity of observations, specifically at an interannual scale. We present in this paper an original dataset combining 40 years of carbonate system observations in the Indian sector of the Southern Ocean (Enderby Basin) to evaluate and interpret the interannual variability ofCant in the AABW. This investigation is based on regular observations collected at the same location (63∘ E–56.5∘ S) in the framework of the French observatory OISO from 1998 to 2018 extended by GEOSECS and INDIGO observations (1978, 1985 and 1987).At this location the main sources of AABW sampled is the low-salinity Cape Darnley Bottom Water (CDBW) and the Weddell Sea Deep Water (WSDW). Our calculations reveal that Cant concentrations increased significantly in the AABW, from an average concentration of 7 µmol kg-1 calculated for the period 1978–1987 to an average concentration of 13 µmol kg-1 for the period 2010–2018. This is comparable to previous estimates in other Southern Ocean (SO) basins, with the exception of bottom water close to formation sites where Cant concentrations are about twice as large. Our analysis shows that total carbon (CT) and Cant increasing rates in the AABW are about the same over the period 1978–2018, and we conclude that the long-term change inCT is mainly due to the uptake of Cant in the different formation regions. This is, however, modulated by significant interannual to multi-annual variability associated with variations in hydrographic (potential temperature, Θ; salinity, S) and biogeochemical (CT; total alkalinity, AT; dissolved oxygen, O2) properties. A surprising result is the apparent stability of Cant concentrations in recent years despite the increase in CT and the gradual acceleration of atmospheric CO2. The interannual variability at play in AABW needs to be carefully considered in the extrapolated estimation of Cant sequestration based on sparse observations over several years.

Antarctic Bottom Water (AABW) is known as a long-term sink for anthropogenic CO.sub.2 (C.sub.ant ), but the sink is hardly quantified because of the scarcity of observations, specifically at an interannual scale. We present in this paper an original dataset combining 40 years of carbonate system observations in the Indian sector of the Southern Ocean (Enderby Basin) to evaluate and interpret the interannual variability of C.sub.ant in the AABW. This investigation is based on regular observations collected at the same location (63.sup.\" E-56.5.sup.\" S) in the framework of the French observatory OISO from 1998 to 2018 extended by GEOSECS and INDIGO observations (1978, 1985 and 1987).

Antarctic Bottom Water (AABW) is known as a long-term sink for anthropogenic CO2 (Cant), but the sink is hardly quantified because of the scarcity of observations, specifically at an interannual scale. We present in this paper an original dataset combining 40 years of carbonate system observations in the Indian sector of the Southern Ocean (Enderby Basin) to evaluate and interpret the interannual variability of Cant in the AABW. This investigation is based on regular observations collected at the same location (63∘ E–56.5∘ S) in the framework of the French observatory OISO from 1998 to 2018 extended by GEOSECS and INDIGO observations (1978, 1985 and 1987). At this location the main sources of AABW sampled is the low-salinity Cape Darnley Bottom Water (CDBW) and the Weddell Sea Deep Water (WSDW). Our calculations reveal that Cant concentrations increased significantly in the AABW, from an average concentration of 7 µmol kg−1 calculated for the period 1978–1987 to an average concentration of 13 µmol kg−1 for the period 2010–2018. This is comparable to previous estimates in other Southern Ocean (SO) basins, with the exception of bottom water close to formation sites where Cant concentrations are about twice as large. Our analysis shows that total carbon (CT) and Cant increasing rates in the AABW are about the same over the period 1978–2018, and we conclude that the long-term change in CT is mainly due to the uptake of Cant in the different formation regions. This is, however, modulated by significant interannual to multi-annual variability associated with variations in hydrographic (potential temperature, Θ; salinity, S) and biogeochemical (CT; total alkalinity, AT; dissolved oxygen, O2) properties. A surprising result is the apparent stability of Cant concentrations in recent years despite the increase in CT and the gradual acceleration of atmospheric CO2. The interannual variability at play in AABW needs to be carefully considered in the extrapolated estimation of Cant sequestration based on sparse observations over several years.

We investigated the evolution of anthropogenic CO2 (Cant) in the Antarctic Bottom Water in the Southern Indian Ocean since 1978 based on observations from 16 reocupations. We found that the Cant and the dissolved inorganic carbon increased at about the same rate over the 40-years period. However, the data also show large interannual variations and a surprising stability of Cant in the last decade likely reflecting the variability of bottom waters formations and circulation in the Southern Ocean.

Iron (Fe) is an essential micronutrient for marine phytoplankton, but its poor solubility in oxic waters is responsible for limited primary production across large parts of the ocean. It has been shown that organic compounds are able to bind with Fe to keep it in the dissolved phase (DFe), thought to be the most bioavailable for phytoplankton. The compounds composing the fraction of the dissolved organic matter (DOM) able to bind with Fe are referred to as Fe-binding ligands. While > 99% of DFe is bound to Fe-binding ligands, the knowledge on their identity and cycling is limited as they represent a very small and diverse fraction of the DOM. There is a one-thousand factor difference between the range of concentrations of Fe-binding ligands and the wider DOM pool (nanomolar and micromolar, respectively), the composition and structure of which is impacted by multiple biological and physical processes. One method to investigate Fe-binding properties of the DOM is to titrate Fe-binding ligands against a calibrated added ligand at different DFe concentrations. This method is called Competitive Ligand Exchange (CLE) using Cathodic Stripping Voltammetry (ACSV). The CLE-ACSV approach allows the estimation of the Fe-binding ligand concentration ([L]), and of their average binding strength (Kcond). This approach, however, suffers from technical and practical limitations. In this work, I address several limitations of the CLE-ACSV approach and present techniques to improve accessibility for new users and minimise the risk of user subjectivity within data selection. I then apply these to samples collected from the subtropical South Pacific to assess the role of Fe-binding ligands in the distribution and cycling of DFe in waters impacted by intense diazotrophic and hydrothermal activities.In Chapter 1, I introduce the general background of my work by reviewing the inorganic and organic aspects of DFe speciation. I present in Chapter 2 a description of the CLE-ACSV approach; the concept, the theory, the apparatus, and the technical limitations are discussed to provide general knowledge on the different aspects hampering the application of the CLE-ACSV. In Chapter 3, I address the limitation of the CLE-ACSV approach related to the pH buffering of the sample, a technical requirement of the current methods which are potentially impacting and hampering our understanding of the DFe speciation. In Chapter 4, limitations related to the interpretation and comparability of the CLE-CSV titrations are addressed. I present a procedure developed to limit the subjectivity of the analyst on the results produced, aiming to ease the comparability of the results between laboratories. Finally, in Chapter 5, I present the application of my CLE-ACSV development on natural samples collected in the Western Tropical South Pacific. Fe-binding ligand data are combined with electrochemical and fluorescence data of the humic fraction, a known contributor to the Fe-binding ligand pool, to interpret the composition and cycling of the fraction of the DOM implicated in DFe distribution in this region. I finally conclude this thesis by sharing some thoughts about how to move forward in this challenging but important research area that marine Fe speciation is.

Soil P composition can be conveniently determined in alkaline extracts using solution ³¹P nuclear magnetic resonance (NMR) spectroscopy, but spectral assignments are based on fragmentary literature reports of model compounds in various extraction matrices. We report solution ³¹P NMR chemical shifts of model P compounds, including inorganic phosphates, orthophosphate monoesters and diesters, phosphonates, and organic polyphosphates, determined in a standardized soil P extractant (0.25 M NaOH and 0.05 M EDTA). Signals from nucleic acids (DNA -0.37 ppm, RNA 0.54 ppm) and phospholipids (phosphatidyl choline 0.78 ppm, phosphatidyl serine 1.57 ppm, phosphatidyl ethanolamine 1.75 ppm) could be differentiated in the orthophosphate diester region, and were identified in a sample of cultured soil bacteria. Inorganic and organic polyphosphates could be differentiated by the presence of a signal at -9 ppm from the phosphate of organic polyphosphates. Some orthophosphate diesters, notably RNA and phosphatidyl choline, degraded rapidly to orthophosphate monoesters in NaOH–EDTA although DNA, other phospholipids, and orthophosphate monoesters were more stable. Changes in probe temperature had a marked influence on signal intensities and the relative magnitude of signals from orthophosphate monoesters and inorganic orthophosphate, and we suggest that solution ³¹P NMR spectroscopy of soil extracts be performed at 20°C.

Composition and effects of additions of fibric (Oi) and hemic/sapric (Oe + Oa) layer extracts collected from a 20-year-old stand of radiata pine (Pinus radiata) on soil carbon dioxide (CO₂) evolution were investigated in a 94-day aerobic incubation. The ¹³C nuclear magnetic resonance spectroscopy indicated that Oi layer extract contained greater concentrations of alkyl C while Oe + Oa layer extract was rich in carboxyl C. Extracts from Oi and Oe + Oa layers were added to a forest soil at two different polyphenol concentrations (43 and 85 μg g-¹ soil) along with tannic acid (TA) and glucose solutions to evaluate effects on soil CO₂ efflux. CO₂ evolution was greater in amended soils than control (deionized water) indicating that water-soluble organic carbon (WSOC) was readily available to microbial degradation. However, addition of WSOC extracted from both Oi and Oe + Oa layers containing 85 μg polyphenols g-¹ soil severely inhibited microbial activity. Soils amended with extracts containing lower concentrations of polyphenols (43 μg polyphenols g-¹ soil), TA solutions, and glucose solutions released 2 to 22 times more CO₂-C than added WSOC, indicating a strong positive priming effect. The differences in CO₂ evolution rates were attributed to chemical composition of the forest floor extracts.